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as) United States a2) Patent Application Publication co) Pub. No.: US 2024/0120506 Al TOUR et al. US 20240120506A1 (43) Pub. Date: Apr. 11, 2024 (4) (71) (72) (73) (21) (22) (86) (60) Capacit Carbon Flash Joule Spent Cathode Heating Particle TO FLASH RECYCLING OF BATTERIES Applicant: William Marsh Rice University, Houston, TX (US) Inventors: James Mitchell TOUR, Houston, TX (US); Weiyin CHEN, Houston, TX (US); Duy X. LUONG, Houston, TX (US); Carter KITTRELL, Houston, TX (US) WILLIAM MARSH RICE UNIVERSITY, Houston, TX (US) Assignee: Appl. No. 18/264,646 PCT Filed: Feb. 8, 2022 PCT No.: § 371 ©), (2) Date: PCT/US22/15616 Aug. 8, 2023 Related U.S. Application Data Provisional application No. 63/285,952, filed on Dec. 3, 2021, provisional application No. 63/147,069, filed on Feb. 8, 2021. Cathode Waste Cooper Electrode Publication Classification (51) Int. Cl. HOIM 6/52 (2006.01) ©25C 108 (2006.01) (52) U.S. CL. CPC cressssssseee HOIM 6/52 (2013.01); C25C 1/08 (2013.01) (57) ABSTRACT Method and system for flash recycling of batteries, including lithium-ion batteries, other metal (sodium, potassium, zinc, magnesium, and aluminum)-ion batteries, metal batteries, batteries having all metal oxide cathodes, and batteries having graphite-containing anodes. The method and system include a solvent-free and water-free flash Joule heating (FJH) method performed upon a mixture that includes materials from the batteries done in millisecond for recy- cling the materials. In some embodiments, the FIH method is combined with magnetic separation to recover lithium, cobalt, nickel, and manganese with high yields up to 98%. In some embodiments, the FJH method is followed by rinsing with dilute acid, such a 0.01 M HCl. In other embodiments, the FJH method is utilized to purify the graphite in the battery, such as for use in the anode of the battery. Magnetic Separation Magnetic Quartz Tube Ko Graphite Electrode Nonmagnetic Flash Cathode Waste
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Capacitors: Carbon Flash Joule ~ Magnetic Spent Cathode Heating Separation () Particle ~N as - Magnetic cE Quartz Tube &5 Cathode Waste F Graphite Electrode Nonmagnetic Cooper Electrode Flash Cathode Waste ee High Temperature 3 a Sintering SS Reagent —__ Cathode Waste Metal Alloy Chunk Leaching Ni2 _| —_—— ro) 2+ Co Oo@ Mn2t Mixed metal ion solution FIG, 1C FIG. 1B Cathode Waste uoneayqng uoyvoyddy yuaeg TTI JO T 320U 207 ‘TT “Ady TV 9080710/r207 SA.
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US 2024/0120506 Al Apr. 11, 2024 Sheet 2 of 121 Patent Application Publication O00E iT (20,01) Pleld dT Old JT ‘Dl (y) aunjesadway 0002 1 = 3 3 ry 3 Cc a, Bewuou Md —O— ~ oe Loz Bew May -<O-- (s) Ow, Q001 v'0 £0 Z'0 10 0'0 1 1 1 1 1 1 1 1 = 3 3 s xXxZv g p54 pO X27 = om 3 d]SeM apoujed - 00ST t oooz L oosz L oove Loose L ooor | oosp (y) eunqevedwa
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Patent Application Publication Apr. 11,2024 Sheet 3 of 121 US 2024/0120506 Al Brass screw : Control environment Copper wool wi ri C Graphite spacer Cathode mixture 24v Inductor = Z\ Ovo. —— Arduino 250 Kill = Power switch switch 1 l N J Capacitor bank 100.0 | [ Charging Power z supply Current 50 Discharging 100 ka FIG. 2A
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Patent Application Publication Apr. 11,2024 Sheet 8 of 121 US 2024/0120506 Al ~~ FIG. 6A FIG. 6B & a BEY DLE EABRGLYL GOL 04 42% FIG. 6C FIG. 6D
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Patent Application Publication Apr. 11, 2024 Sheet 11 of 121 US 2024/0120506 Al FIG, 8D Sum Spectrum Relative intensity (a.u) Energy (keV) FIG. 8E
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Apr. 11, 2024 Sheet 13 of 121 US 2024/0120506 Al Patent Application Publication LCO large batch (800 mg per batch) FIG. 10B LCO small batch (200 mg per batch) FIG. 10A NMC large batch (200 mg per batch) FIG. 10D NMC small batch (200 mg per batch) FIG, 10C
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Patent Application Publication Apr. 11,2024 Sheet 15 of 121 US 2024/0120506 Al method FIG. 11G Structure Factor Hydrometallurgical method FIG. 11F Structure Factor Pyrometallurgical Flash recycling FIG. 11E Structure Factor
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Patent Application Publication Apr. 11, 2024 Sheet 19 of 121 US 2024/0120506 Al FIG. 13G FIG. 13F
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Patent Application Publication Apr. 11,2024 Sheet 21 of 121 US 2024/0120506 Al 2500K 0-9 g/cm FIG. 131
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Patent Application Publication Apr. 11, 2024 Sheet 67 of 121 US 2024/0120506 Al FIG. 37] FIG. 371 FIG. 37H
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Apr. 11, 2024 Sheet 68 of 121 US 2024/0120506 Al Patent Application Publication G8e “OIA V8E SIA
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Apr. 11, 2024 Sheet 69 of 121 US 2024/0120506 Al Patent Application Publication Cd8e SI IEE SI
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Apr. 11, 2024 Sheet 70 of 121 US 2024/0120506 Al Patent Application Publication A6E SIA C6Ee SIA
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Apr. 11,2024 Sheet 72 of 121 US 2024/0120506 Al Patent Application Publication G0r ‘Id J0¢ ‘DIF A270 =4V 4
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Patent Application Publication Apr. 11, 2024 Sheet 73 of 121 US 2024/0120506 Al Synthesis Cathode Active Materials ee XXX) KWWWWG Assembly Elements or Solutions Flash recycling Mining and processing Recycling Batteries FIG. 41A
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Apr. 11,2024 Sheet 77 of 121 US 2024/0120506 Al Patent Application Publication Recycle “LO Reconstitution f / va a ve Q Cathode Active Materials Use Phase New Batteries FIG. 42A
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Patent Application Publication Apr. 11,2024 Sheet 81 of 121 US 2024/0120506 Al Brass screw : Control environment Graphite spacer ‘a wi wit Reactant source 24V Pp Inductor = Z\ ° — Arduino 250 Kill = Power switch switch 1 l N J Capacitor bank 100.0 | | Charging Power z supply Current 50 Discharging 100 ka FIG, 43A
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US 2024/0120506 Al FLASH RECYCLING OF BATTERIES CROSS-REFERENCE TO RELATED PATENT APPLICATIONS [0001] This application claims priority to (a) U.S. Patent Appl. Ser. No. 63/147,069, filed Feb. 8, 2021, entitled “Recycling Of Spent Batteries By Flash Joule Heating,” to James M. Tour, et al., and (b) U.S. Patent Appl. Ser. No. 63/285,952, filed Dec. 3, 2021, entitled “Flash Recycling Of Batteries.” to James M. Tour, et al. Each of these patent applications is commonly owned by the owner of the present invention. These patent applications are incorporated herein in their entirety. STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH [0002] This invention was made with government support under Grant No. FA9550-19-1-0296 awarded by the United States Air Force Office of Scientific Research, and Grant No. DE-FE0031794 awarded by the United States Department of Energy, National Energy Technology Laboratory. The gov- ernment has certain rights in the invention. TECHNICAL FIELD [0003] The present invention relates to the flash recycling of batteries, including lithium-ion batteries, other metal (sodium, potassium, zinc, magnesium, and aluminum)-ion batteries, metal batteries (such as solid lithium batteries), batteries having all metal oxide cathodes, and batteries having all graphite-containing anodes. The flash recycling features solvent-free and water-free flash Joule heating (FJH) methods, sometimes performed in combination with magnetic separation to recover lithium, cobalt, nickel, man- ganese, etc., such as in the cathode, and FJH methods for purifying graphite in the batteries, such as the graphite in the anode. BACKGROUND [0004] The continuous accumulation of spent Li-ion bat- teries (LIBs) and the growing scarcity of their valuable metal sources have resulted in an urgent call for an effective recycling strategy. [Tran 2019; Lv 2018; Xu 2020]. The current recycling methods can achieve high recovery yields for the valuable metals, but they require high-temperature furnaces or harsh wet extraction methods, and they destroy the entire 3-dimensional (3D) morphology of the cathode, rendering them economically and environmentally unat- tractive. [Lv 2018; Natarajan 2018]. Hence, less than 5% of LIBs are recycled which results in a constant need to mine metals from their ores. [Recycle 2019; Velazquez 2019; Li 2017). [0005] The ever-increasing demand for portable electronic devices and electric vehicles has accelerated the production of commercial secondary batteries, especially LIBs. [Re- cycle 2019; Andre 2015]. The market for rechargeable LIBs reached —$50 billion in 2020 and it is projected to be —$70 billion in 2022. [Zou 2013]. Since the expected life of most LIBs is less than 10 years, and often only 2 years [Salvatierra 2021; Chen 2020], the foreseeable staggering accumulation of spent LIBs is disconcerting. [Recycle 2019; Velazquez, 2019; Li 2017]. Furthermore, at the projected pace of Li and Co mining, the world’s reserves of these elements are predicted to deplete by 2050 and 2030, respectively. [Nat- Apr. 11, 2024 arajan 2018; Jacoby 2020]. The spent cathode consists of Li and transition metals, accounting for ~35% of the total weight and ~45% of the cost of LIBs. [Salvatierra 2021]. An effective recycling of the spent cathodes will lessen the need for remote mining of these metals, diminish the environ- mental consequences of LIB disposal, and provide an eco- nomic incentive to recycle. [He 2016]. The anode, although graphite and less expensive than the cathode, uses a form of graphite that is battery-grade, and thus costs $10,000 per ton for the natural sources of battery-grade graphite and as much as $20,000 per ton for the preferred synthetic battery-grade graphite. Additionally, the spent anode has several percent by weight lithium and the leached cathodic metals remaining in it, which is higher in metal content than even the mined ores. Hence, from an environmental standpoint it cannot be merely landfilled, and from an economic standpoint it is attractive to recycle that component as well. SUMMARY OF THE INVENTION [0006] The present invention relates to a method and system for a solvent-free and water-free flash Joule heating (FJH) method performed upon a mixture that includes materials from lithium-ion batteries, other metal-ion batter- ies, metal batteries, batteries having all metal oxide cath- odes, and batteries having all graphite-containing anodes done in milliseconds. In some embodiments, the FJH method is combined with magnetic separation to recover lithium, cobalt, nickel, manganese, etc., with high yields up to 98%. The process is called “flash recycling.” LIBs pos- sessing different chemistries, namely lithium cobalt oxide (LCO), lithium nickel-manganese-cobalt oxide (NMC) and spent LIBs with both LCO and NMC mixed together, can be effectively flash recycled. Characterization of the flash recy- cling products reveal intact 3D layered core structures with hierarchical features, so their reconstitution into new cath- odes is greatly simplified. It has further been shown that the flash process produces a lithium-ion permeable conductive carbon coating on the flash cathode material, thereby afford- ing it with improved electrochemical stability. Life-cycle analysis against current recycling processes highlight that flash recycling can significantly reduce the total energy and greenhouse gas (GHG) emissions while turning it into an economically advantageous process. [0007] In other embodiments, the FJH methods is used for purifying graphite in the metal-ion batteries, such as the graphite in the anode. [0008] In general, in one embodiment, the invention fea- tures a method of recovering metal. The method includes forming a mixture including a cathode material. The cathode material is prepared from one or more batteries. The method further includes applying a voltage across the mixture to obtain metals and cathode waste from the cathode material. The voltage is applied in one or more voltage pulses. Duration of each of the one or more voltage pulses is for a duration period. The method further includes magnetically separating the metal and the cathode waste. [0009] Implementations of the invention can include one or more of the following features: [0010] The metal can include cathode metal selected from the group consisting of lithium, cobalt, nickel, manganese, iron, and combinations thereof. [0011] The metal can include cathode metal selected from the group consisting of be metal oxides, metal salts, metal carbonates, metal phosphates, and combinations thereof.
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US 2024/0120506 Al (0012) [0013] (0014) [0015] [0016] The cathode metal can include metal oxide. The metal oxide can include cobalt oxide. The cathode metal can include metal carbonate. The metal carbonate can include lithium carbonate. The cathode metal can include metal phosphate. [0017] The metal phosphate can include iron phosphate. [0018] The one or more batteries can include batteries selected from the group consisting of lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, zinc-ion bat- teries, magnesium-ion batteries, aluminum-ion batteries, metal-ion batteries, metal batteries, anode-free batteries, metal oxygen batteries, metal air batteries, and combinations thereof. [0019] The one or more batteries can include one or more lithium-ion batteries. [0020] The one or more lithium-ion batteries can include lithium-ion batteries each having a lithium cobalt oxide (LCO) cathode or a lithium nickel-manganese-cobalt oxide (NMC) cathode. [0021] Each of the one or more lithium-ion batteries can each include an LCO cathode. [0022] Each the one or more lithium-ion batteries can each include an NMC cathode. [0023] The metal obtained by applying the voltage can include a cathode metal including metal phosphate. [0024] The metal phosphate can include iron phosphate. [0025] Each of some of the one or more lithium-ion batteries can include an LCO cathode and each of some of the one or more lithium-ion batteries can include an NMC cathode. [0026] The one or more lithium-ion batteries can include lithium-ion batteries having a cathode including a mixture of lithium cobalt oxide (LCO) and lithium nickel-manganese- cobalt oxide (NMC). [0027] The mixture can further include a conductive addi- tive. [0028] The conductive additive can be a carbon source. [0029] The conductive additive can be selected from the group consisting of graphite, anodic graphite, battery-grade graphite, elemental carbon, carbon black, graphene, flash graphene, turbostratic graphene, coal, anthracite, coke, met- allurgical coke, calcined coke, activated charcoal, biochar, natural gas carbon that had been stripped of its hydrogen atoms, activated charcoal, shungite, plastic waste, plastic waste-derived carbon char, food waste, food waste-derived carbon char, biomass, biomass-derived carbon char, hydro- carbon gas-derived carbon char, and mixtures therefrom. [0030] The conductive additive can be carbon black. [0031] The conductive additive can be predominately elemental carbon. [0032] The conductive additive can be selected from the group consisting of metals, metal salts, metal oxides, met- alloids, metal complexes, conductive phosphorus, and non- metal conductive materials. [0033] The conductive additive can be selected from the group consisting of metals, metal salts, metal oxides, met- alloids, and metal complexes. [0034] The conductive additive can be a metalloid. [0035] The metalloid can be selected from the group consisting of B, Si, As, Te, and At. [0036] The conductive additive can be prepared from the anode material of the one or more batteries. [0037] The conductive additive can be not prepared from the one or more batteries. Apr. 11, 2024 [0038] The cathode material and the conductive additive can be mixed at a weight ratio in a range of 1:2 and 25:1. [0039] The voltage applied can be in a range of 15 V and 300 V. [0040] The mass of the mixture to which the voltage is applied can be more than 1 kg. The voltage applied can be between 100 V and 100,000 V. [0041] The mass of the mixture to which the voltage is applied can be more than 100 kg. [0042] The mass of the mixture to which the voltage is applied can be more than 1 kg. The current applied can be between 1,000 amps and 30,000 amps. [0043] The mass of the mixture to which the voltage is applied can be more than 100 kg. [0044] The mixture can have a resistance in the range of 0.1 ohms and 25 ohms when the voltage is applied. [0045] The duration period for the duration of each of the one or more voltage pulses can be between | microsecond and 25 seconds. [0046] The duration period for the duration of each of the one or more voltage pulses can be between | microsecond and 10 seconds. [0047] The duration period for the duration of each of the one or more voltage pulses can be between | microsecond and 1 second. [0048] The duration of each of the one or voltage pulses can be between 100 microseconds and 500 microseconds. [0049] The one or more voltage pulses can be between 2 voltage pulses and 100 voltage pulses. [0050] The voltage pulse can be performed using direct current (DC). [0051] The method can be performed utilizing a pulsed direct current (PDC) Joule heating process. [0052] The voltage pulse can be performed using alternat- ing current (AC). [0053] The voltage pulse can be performed by using both direct current (DC) and alternating current. [0054] The method can switch back and forth between the use of direct current (DC) and alternating current (AC). [0055] The method can concurrently use direct current (DC) and alternating current (AC). [0056] The one or more voltage pulses can increase the temperature of the mixture to at least 3000 K. [0057] The metals obtained by applying a voltage across the mixture can include metal particles that have a carbon coating. [0058] The carbon coating can be conductive. [0059] The carbon coating can be ion permeable. [0060] The carbon coating can be conductive and ion permeable. [0061] The carbon coating can be ion permeable for a metal ion. [0062] The metal ion can be selected from the group consisting of lithium-ions, sodium-ions, potassium-ions, magnesium-ions, zinc-ions, and aluminum-ions. [0063] The carbon coating can be amorphous. [0064] The carbon coating can include graphene. [0065] The method can preserve the 3D layer structure of the cathodes in the cathode material. [0066] The method can preserve the 3D morphology of the cathodes in the cathode material. [0067] The method can destroy the 3D morphology of the cathodes in the cathode material.
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US 2024/0120506 Al [0068] The method can further include a cooling step. The cooling step can cool the metals and the cathode waste before the step of magnetically separating the metals and the cathode waste. [0069] The metals and cathode waste can be at a weight ratio between 20:1 and 5:1. [0070] The metals and cathode waste can be at a weight ratio between 10:1 and 8:1. [0071] The method can further include, after the step of mechanical separating, applying a second voltage across the cathode waste. The second voltage can be applied in one or more second voltage pulses. Duration of each of the one or more second voltage pulses can be for a second duration period. [0072] The second voltage can be the same as the voltage applied across the cathode material. The second duration period can be the same as the duration period for the voltage applied across the cathode material. [0073] The applying of the second voltage across the cathode waste can obtain further metals and a reduced portion of the cathode waste. The method can further include magnetically separating the additional metals and the reduced portion of the cathode waste. [0074] The further metals and reduced portion of the cathode waste can be at a weight ratio of at least 1:1. [0075] The further metals and reduced portion of the cathode waste can be at a weight ratio of at least 1.5:1. [0076] The method can further include recovering the metals by collecting the metals after separation from the cathode waste. [0077] The cathode material can include a first mass of cathode metals selected from the group consisting of lithium, cobalt, nickel, magnesium, and combination thereof. The collected metals can include at least 70 wt % of the first mass of cathode metals. [0078] The collected metals can include at least 70 wt % of the lithium in the first mass of cathode metals. [0079] The collected metals can include at least 70 wt % of the cobalt in the first mass of cathode metals. [0080] The collected metals can include at least 70 wt % of the nickel in the first mass of cathode metals. [0081] The collected metals can include at least 70 wt % of the magnesium in the first mass of cathode metals. [0082] The collected metals can include at least 70 wt % of each of the lithium, cobalt, nickel, and magnesium in the first mass of cathode metals. [0083] The collected metals can include at least 90 wt % of the lithium in the first mass of cathode metals. [0084] The collected metals can include at least 90 wt % of the cobalt in the first mass of cathode metals. [0085] The collected metals can include at least 90 wt % of the nickel in the first mass of cathode metals. [0086] The collected metals can include at least 90 wt % of the magnesium in the first mass of cathode metals. [0087] The collected metals can include at least 90 wt % of each of the lithium, cobalt, nickel, and magnesium in the first mass of cathode metals. [0088] The method can be performed in a continuous process or automated process. [0089] The metals can be recycled in new metal-ion or metal batteries. [0090] The metals can be recycled as cathode materials in the new metal-ion or metal batteries. Apr. 11, 2024 [0091] In general, in another embodiment, the invention features a method of recovering metal. The method includes forming a mixture including a cathode material. The cathode material is prepared from one or more batteries. The method further includes applying a voltage across the mixture to obtain metals and cathode waste from the cathode material. The voltage is applied in one or more voltage pulses. Duration of each of the one or more voltage pulses is for a duration period. The method further includes magnetically separating the metal and the cathode waste. [0092] Implementations of the invention can include one or more of the following features: The one or more batteries can be one or more non-lithium metal-ion batteries. [0093] The one or more batteries can include one or more batteries selected from the group consisting of lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, zinc-ion batteries, magnesium-ion batteries, aluminum-ion batteries, metal-ion batteries, metal batteries, anode-free batteries, metal oxygen batteries, metal air batteries, and combinations thereof. [0094] In general, in another embodiment, the invention features a system for performing the method of recovering metal utilizing at least one of the above-described methods for recovering metals. The system includes a source of the mixture including the cathode material. The system further includes a cell operably connected to the source such that the mixture can be flowed into the cell and held under com- pression. The system further includes electrodes operatively connected to the cell. The system further includes a flash power supply for applying a voltage across the mixture to obtain metals and cathode waste from the cathode material. The system further includes a magnet in operable contact with the metals and cathode waste. The magnet is operable for magnetically separating the metals and the cathode waste. [0095] Implementations of the invention can include one or more of the following features: [0096] In general, in another embodiment, the invention features a... [0097] Implementations of the invention can include one or more of the following features: [0098] The mixture can further include a conductive addi- tive, [0099] The system can be operable to perform a continu- ous process or automated process. [0100] In general, in another embodiment, the invention features a method of recovering metal. The method includes forming a mixture including a battery material. The battery material is prepared from one or more batteries. The method further includes applying a voltage across the mixture to obtain metals and battery waste from the battery material. The voltage is applied in one or more voltage pulses. Duration of each of the one or more voltage pulses is for a duration period. The method further includes magnetically separating the metals and the battery waste. [0101] Implementations of the invention can include one or more of the following features: [0102] The one or more batteries can include one or more lithium-ion batteries. [0103] The one or more batteries can include one or more non-lithium metal-ion batteries selected from the group consisting of lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, zinc-ion batteries, magnesium-ion batteries, aluminum-ion batteries, metal-ion batteries, metal
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US 2024/0120506 Al batteries, anode-free batteries, metal oxygen batteries, metal air batteries, and combinations thereof. [0104] The mixture can further include a conductive addi- tive. [0105] In general, in another embodiment, the invention features a system for performing the method of recovering metal utilizing the above-described method for recovering metal. The system includes a source of the mixture including the battery material. The system further includes a cell operably connected to the source such that the mixture can be flowed into the cell and held under compression. The system further includes electrodes operatively connected to the cell. The system further includes a flash power supply for applying a voltage across the mixture to obtain metals and battery waste from the battery material. The system further includes a magnet in operable contact with the metals and battery waste. The magnet is operable for magnetically separating the metals and the battery waste. [0106] Implementations of the invention can include one or more of the following features: [0107] The battery material can include lithium-ion bat- tery material. [0108] The battery material can be non-lithium metal-ion battery material selected from the group consisting of sodium-ion battery material, potassium-ion battery material, zinc-ion battery material, magnesium-ion battery material, aluminum-ion battery material, and combinations thereof. [0109] The mixture can further include a conductive addi- tive. [0110] The system can be operable to perform a continu- ous process or automated process. [0111] In general, in another embodiment, the invention features a method of recovering metal. The method includes forming a mixture including a cathode material. The cathode material is prepared from one or more batteries including cathodes. The method further includes applying a voltage across the mixture to obtain metals and cathode waste from the cathode material. The voltage is applied in one or more voltage pulses. Duration of each of the one or more voltage pulses is for a duration period. The method destroys 3D morphology of the cathodes in the cathode material. The method further includes extracting the metal from the cath- ode waste using an aqueous solution. [0112] Implementations of the invention can include one or more of the following features: [0113] The metals can be selected from the group consist- ing of lithium, cobalt, nickel, manganese, copper, and iron. [0114] The metals can be in the form of one or more metal salts. [0115] The one or more metal salts can be in the form one or more oxides. [0116] The aqueous solution can include an acid. [0117] The acid can be HCI in the range of between 0.01 M and 12 M. [0118] The acid can be HCI in the range of between 0.01 M and 0.1 M. [0119] The acid can be in the range of between 0.01 M and 15M. [0120] 0.1 M. [0121] The voltage can be applied in between one voltage pulse and 100 voltage pulses. The acid can be the range of between 0.01 M and Apr. 11, 2024 [0122] The one or more batteries including cathodes can include cathodes selected from the group consisting of LCO cathodes and NMC cathodes. [0123] In general, in another embodiment, the invention features a system for performing the method of recovering metal utilizing at least one of the above-described methods. The system includes a source of the mixture including the cathode material. The system further includes a cell operably connected to the source such that the mixture can be flowed into the cell and held under compression. The system further includes electrodes operatively connected to the cell. The system further includes a flash power supply for applying a voltage across the mixture to obtain metals and cathode waste from the cathode material. The system further includes a source of am aqueous solution. The aqueous solution is operable for extracting the metal from the cath- ode waste. [0124] Implementations of the invention can include one or more of the following features: [0125] The mixture can further include a conductive addi- tive. [0126] The system can be operable to perform a continu- ous process or automated process. [0127] In general, in another embodiment, the invention features a method of recycling anode material. The method includes obtaining a mixture including anode material from one or more batteries. The anode material includes graphite. The method further includes applying a voltage across the mixture to purify the graphite in the mixture. The voltage is applied in one or more voltage pulses. Duration of each of the one or more voltage pulses is for a duration period. The method further includes utilizing the graphite purified by the step of applying the voltage in one or more new batteries. [0128] Implementations of the invention can include one or more of the following features: [0129] The one or more batteries can include one or more lithium-ion batteries. [0130] The one or more batteries can include one or more batteries selected from the group consisting of lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, zinc-ion batteries, magnesium-ion batteries, aluminum-ion batteries, metal-ion batteries, and combinations thereof. [0131] The one or more new batteries can include one or more new lithium-ion batteries. [0132] The one or more new batteries can include one or more new lithium-ion batteries. [0133] The one or more batteries can include one or more batteries selected from the group consisting of lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, zinc-ion batteries, magnesium-ion batteries, aluminum-ion batteries, metal-ion batteries, metal batteries, anode-free batteries, metal oxygen batteries, metal air batteries, and combinations thereof. [0134] The mixture can consist of anode material. [0135] The mixture further can include cathode materials from the one or more batteries. [0136] The mixture can include the anode material mixed with a conductive additive that is not the anode material. [0137] The conductive additive can be a carbon source. [0138] The conductive additive can be selected from the group consisting of graphite, anodic graphite, battery-grade graphite, elemental carbon, carbon black, graphene, flash graphene, turbostratic graphene, coal, anthracite, coke, met- allurgical coke, calcined coke, activated charcoal, biochar,
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US 2024/0120506 Al natural gas carbon that had been stripped of its hydrogen atoms, activated charcoal, shungite, plastic waste, plastic waste-derived carbon char, food waste, food waste-derived carbon char, biomass, biomass-derived carbon char, hydro- carbon gas-derived carbon, and mixtures therefrom. [0139] The conductive additive can be carbon black. [0140] The conductive additive can be predominately elemental carbon. [0141] In general, in another embodiment, the invention features a system for performing the method of recycling anode material utilizing at least one of the above-described methods of recycling anode material. The system includes a source of the mixture including the anode material including graphite. The system further includes a cell operably con- nected to the source such that the mixture can be flowed into the cell and held under compression. The system further includes electrodes operatively connected to the cell. The system further includes a flash power supply for applying a voltage across the mixture to purify the graphite in the anode material. [0142] Implementations of the invention can include one or more of the following features: [0143] The anode material can include lithium-ion battery anode material. [0144] The anode material can include non-lithium metal- ion battery anode material selected from the group consist- ing of lithium-ion battery anode material, sodium-ion bat- tery anode material, potassium-ion battery anode material, zinc-ion battery anode material, magnesium-ion battery anode material, aluminum-ion battery anode material, and combinations thereof. [0145] The mixture can include the anode material mixed with a conductive additive that is not the anode material. [0146] The system can be operable to perform a continu- ous process or automated process. [0147] In general, in another embodiment, the invention features a method that includes selecting a graphite anode material from a battery. The method further includes apply- ing flash Joule heating to the graphite anode material to form flashed graphite anode material. The application of flash Joule heating purifies the graphite anode material. [0148] Implementations of the invention can include one or more of the following features: [0149] The battery can be a lithium-ion battery. [0150] The battery can be a battery selected from the group consisting of lithium-ion batteries, sodium-ion batter- ies, potassium-ion batteries, zinc-ion batteries, magnesium- ion batteries, aluminum-ion batteries, and combinations thereof. [0151] The flash Joule heating can include applying a voltage across the graphite anode material. The voltage can be applied in one or more voltage pulses. Duration of each of the one or more voltage pulses can be for a duration period. [0152] The method can further include using the flashed graphite anode material in a second battery. [0153] The second battery can be a second lithium-ion battery. [0154] The battery can be a lithium-ion battery. [0155] The second battery can be a second non-lithium metal-ion battery selected from the group consisting of sodium-ion batteries, potassium-ion batteries, zinc-ion bat- teries, magnesium-ion batteries, aluminum-ion batteries, and combinations thereof. Apr. 11, 2024 [0156] The battery can be a non-lithium metal-ion battery selected from the group consisting of sodium-ion batteries, potassium-ion batteries, zinc-ion batteries, magnesium-ion batteries, aluminum-ion batteries, and combinations thereof. [0157] The method can further include washing the flashed graphite anode material to obtain inorganic metals and salts separate from the graphite in the flashed graphite anode material. [0158] The method can further include using the flashed graphite anode material after washing in a second battery. [0159] The second battery can be a second lithium-ion battery. [0160] The battery can be a lithium-ion battery. [0161] The second battery can be a battery selected from the group consisting of lithium-ion batteries, sodium-ion batteries, potassium-ion batteries, zinc-ion batteries, mag- nesium-ion batteries, aluminum-ion batteries, and combina- tions thereof. [0162] The battery can be a battery selected from the group consisting of lithium-ion batteries, sodium-ion batter- ies, potassium-ion batteries, zinc-ion batteries, magnesium- ion batteries, aluminum-ion batteries, and combinations thereof. [0163] In general, in another embodiment, the invention features a method of resynthesizing cathode material. The method includes performing a flash Joule heating process on cathode material to form a ferromagnetic flash product. The method further includes performing a hydrothermal and calcination process on the ferromagnetic flash product to form the resynthesized cathode material. BRIEF DESCRIPTION OF THE DRAWINGS [0164] FIGS. 1A-1F are schematics and graphs for flash recycling of cathode waste. FIG. 1A is a schematics of a flash recycling of cathode waste method. FIGS. 1B-1C are, respectively, schematics of traditional hydrometallurgical and pyrometallurgical methods. FIG. 1D is a graph showing, real-time temperature measurement by fitting the blackbody radiation from the sample during the flash recycling process, listing the rapid cooling, all complete in less than 0.5 seconds. FIG. 1E is a graph showing temperature-vapor pressure relationships for various metals involved in cathode waste. FIG. 1F is a graph showing the magnetic response of unflashed cathode waste, flash recycled cathode waste fer- romagnetic portion (which is ~90% of the product), and the flash recycled cathode waste non-ferromagnetic portion (which is ~10% of the product). [0165] FIGS. 2A-2B show the scheme of a FJH system. FIG, 2A is an electrical schematic of the FJH system. FIG. 2B is a photograph of a FJH reaction box. [0166] FIGS. 3A-3C show current-time curves during the flash reaction. FIG. 3A is a graph of new lithium cobalt oxide (LiCoO,) (LCO) cathode material. FIG. 3B is a graph of new lithium nickel-manganese-cobalt oxide (LiNi,Mn,- Co_O,, normally referred as NMCxyz, such as NMC811) (NMC) cathode material. FIG. 3C is a graph of cathode waste obtained from spent LIB. The vertical lines during the current sweep reflect the 1000 Hz cycling of the electrical input. [0167] FIG. 4 shows the spectra recorded by a spectrom- eter with 16-channel optical fibers. The wavelengths of these channels range from 1000 nm to 640 nm with equal interval
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US 2024/0120506 Al
of 24 nm. Black body radiation (BBR) fitting was subse-
quently used to obtain the temperature at each time point as
shown in FIG. 1D.
[0168] FIGS. 5A-5B show magnetic response of cathode
materials. FIG. 5A is a graph of a magnified hysteresis loop
for CW, the non-ferromagnetic portion of the flash recycled
CW (fCW nonmag) and the ferromagnetic portion of the
flash recycled CW (f{CW mag). FIG. 5B is a graph showing
behavior of the hysteresis loop around the origin for the {CW
mag.
[0169] FIGS. 6A-6D show magnetic response of cathode
waste and flash product. FIGS. 6A-6B are photographs
showing that the cathode waste was not attracted by a bar
magnet. FIGS. 6C-6D show that the flash recycled CW is
predominantly ferromagnetic.
[0170] FIG. 7 shows magnetic response of re-flashed
cathode materials. The magnetic response is of the re-flash
recycled cathode waste ferromagnetic portion, which is ~60
wt % of the product, and the re-flash recycled cathode waste
non-ferromagnetic portion, which is ~40 wt % of the prod-
uct. Similar magnetization behavior of re-flash recycled
cathode waste ferromagnetic portions ensures the effective
separation of them by the same magnet with magnetic field
strength ~5000 Oe.
[0171] FIG. 8A-8E shows structures and chemical com-
ponents of re-flash recycled products. FIG. 8A is the FTIR
spectra of nonferromagnetic portion of the flash recycled
CW (LCO plus NMC), ferromagnetic portion of the re-flash
recycled CW, and nonferromagnetic portion of the re-flash
recycled CW. FIG. 8B is the XRD spectra of ferromagnetic
portion of the re-flash recycled CW. FIG. 8C is an SEM
image of ferromagnetic portion of the re-flash recycled CW.
[0172] FIG. 8D is the energy dispersive analysis element
mapping. FIG. 8E is the corresponding spectrum of the
ferromagnetic portion of the re-flash recycled CW.
[0173] FIGS. 94-9D shows magnetic response of various
cathode materials. FIG. 9A shows room temperature (300 K)
hysteresis loops for NMC and the ferromagnetic portion of
flash recycled NMC (f{NMC mag). FIG. 9B shows behavior
of the hysteresis loop around the origin for NMC and {NMC.
FIG. 9C shows room temperature (300 K) hysteresis loops
for LCO and the ferromagnetic portion of flash recycled
LCO ({LCO mag). FIG. 9D shows behavior of the hysteresis
loop around the origin for LCO and fLCO.
[0174] FIGS. 10A-10B are optical images of the ferro-
magnetic portions of LCO from, respectively, a ~200 mg
scale and a ~800 mg scale.
[0175] FIGS. 10C-10D are optical images of the ferro-
magnetic portions of NMC811 from, respectively, a ~200
mg scale and a ~800 mg scale.
[0176] FIGS. 11A-11G show recovery efficiencies of vari-
ous cathode materials. FIG. 11A is a graph showing recovery
yields (1.0=100%) of Li and Co in the ferromagnetic portion
of flash recycled LCO products after a single flash. The
number of samples N=5 and the bars show the standard
deviations between runs. FIG. 11B is a graph showing
comparison of recovery yields of Li and Co by different
recycling methods, with references noted. FIG. 11C is a
graph showing recovery yields of Li, Co, Ni and Mn in the
ferromagnetic portion of flashed NMC811. N=5. FIG. 11D
is a graph showing recovery yields of Li, Co, Ni and Mn in
the ferromagnetic portion of flashed commercial cathode
waste (fCW) from a spent LIB. N=5. For FIGS. 11C-11D,
the yields can occasionally exceed 1.0 because they are
Apr. 11, 2024
compared against the recovered metal content through aque-
ous acid digestion. FIGS. 11E-11G are radar plots reporting
the recovery yields of various metals from cathode waste
using, respectively, the flash recycling method and tradi-
tional hydrometallurgical and pyrometallurgical methods.
For FIG, 11B, the darker shade is the recovery after a single
flash and the lighter shade is the recovery after a second
flash.
[0177] FIGS. 12A-12C are radar plots reporting the com-
parison of recovery yields of various metals from LCO
using, respectively, the flash recycling method and tradi-
tional hydrometallurgical and pyrometallurgical methods.
The structure retention factor R value is 7.77/3.03=2.57 for
LCO.
[0178] FIGS. 12D-12F are radar plots reporting the com-
parison of recovery yields of various metals from NMC
using, respectively, the flash recycling method and tradi-
tional hydrometallurgical and pyrometallurgical methods.
The structure retention factor R value is 0.29/0.57-0.51 for
NMC.
[0179] FIGS. 134-13] show structures and chemical com-
ponents of flash recycled products. FIG. 13A is high reso-
lution XPS spectra of Co 2p at the surface and subsurface
area of the ferromagnetic portion of the flash recycled CW
(fCW). FIG. 13B is a graph that shows the elemental ratios
at different depths of the ferromagnetic portion of the {CW
(LCO+NMC). Spectra were acquired at different depths
after surface etching. Electrolyte-derived fluoride was
deposited during CEI formation in the spent LIB. FIG. 13C
is a schematic of the ferromagnetic portion of the {CW
particle with hierarchical structure. FIG. 13D is an HAADF
image and corresponding energy dispersive analysis element
mapping of the ferromagnetic portion of the [LCO. FIG. 13E
shows atomistic structure of partially de-lithiated Li,CoO,
before flash recycling and high-quality LiCoO,, Co,O, and
CoO obtained after flash recycling. The right panel demon-
strated the magnetization of Co,O, by plotting the difference
between spin density distribution for a spin up and spin
down configurations at 0.02 e/A*, maximum magnetic
moment of ~70 emu/g. FIG. 13F is an HR-TEM image of
R-LCO reporting the existence of the layered structure at the
surface. The inset of FIG. 13F is the corresponding FFT
pattern. FIG. 13G is an atomic-resolution HAADF-STEM
image of R-LCO. FIG. 13H is an HAADF image and
corresponding energy dispersive analysis element mapping
of R-CW. FIG. 131 is an image of Li-ion permeable partially
graphitized amorphous carbon structure at the end of 9 ns
annealing at 2500 K, with the line indicated possible Li-ion
trajectory. FIG. 13] is a graph showing electrochemical
performances of spent CW, resynthesized cathode materials
and new LCO in prepared half cells. The rate is 0.2 C for
testing.
[0180] FIGS. 14A-14E show chemical components of
ferromagnetic flash recycled CW (fCW) derived from a mix
of LCO and NMC as contained in spent commercial laptop
computer batteries. FIG. 14A is the full scan XPS result of
the ferromagnetic f{CW. FIGS. 14B-14E show, respectively,
high resolution XPS spectra of C 1s, O 1s, F 1s, and Li 1s,
at the surface and subsurface area of ferromagnetic {CW.
Spectra were acquired at different depths after surface etch-
ing.
[0181] FIG. 15A-15G show chemical components of CW
derived from a mix of LCO and NMC as obtained from
spent commercial laptop computer batteries. FIG. 154Page 129
US 2024/0120506 Al
shows the full scan XPS result of the CW. FIGS. 15B-15F
show, respectively, high resolution XPS spectra of C 1s, Co
2p, F 1s, Li 1s, and O 1s at the surface and subsurface area
of CW. Spectra were acquired at different depths after
surface etching. FIG. 15G shows the elemental ratios at
different depths of CW.
[0182] FIGS. 16A-16F show chemical components of the
ferromagnetic portion of flash recycled LCO (fLCO) from 0
nm to 500 nm. FIG. 16A shows the full scan XPS result of
the ferromagnetic {LCO. FIGS. 16B-16E show, respectively,
high resolution XPS spectra of C 1s, Co 2p, Li 1s, and O 1s
at the surface and subsurface area of fLCO. Spectra were
acquired at different depths after surface etching. FIG. 16F
shows the elemental ratios at different depths of ferromag-
netic {LCO.
[0183] FIGS. 17A-17F show chemical components of the
ferromagnetic portion of flash recycled LCO (fLCO) from 0
nm to 100 nm. FIG. 17A shows the full scan XPS result of
the ferromagnetic {LCO. FIGS. 17B-17E show, respectively,
high resolution XPS spectra of C 1s, Co 2p, Li 1s, and O 1s
at the surface and subsurface area of flash LCO. Spectra
were acquired at different depths after surface etching. FIG.
17F shows the elemental ratios at different depths of ferro-
magnetic {LCO.
[0184] FIGS. 184-1811 show chemical components of the
ferromagnetic portion from flash recycled NMC (fNMC)
from 0 nm to 500 nm. FIG. 18A shows the full scan XPS
result of the ferromagnetic f{NMC. FIGS. 18B-18G show,
respectively, high resolution XPS spectra of C 1s, Co 2p, Li
1s, O 1s, Ni 2p and Mn 2p at the surface and subsurface area
of f{NMC. Spectra were acquired at different depths after
surface etching. FIG. 18H shows the elemental ratios at
different depths of ferromagnetic {NMC.
[0185] FIGS. 194-1911 show chemical components of the
ferromagnetic portion from flash recycled NMC (f{NMC)
from 0 nm to 100 nm. FIG. 19A shows the full scan XPS
result of the ferromagnetic f{NMC. FIGS. 19B-19G show,
respectively, high resolution XPS spectra of C 1s, Co 2p, Li
1s, O 1s, Ni 2p and Mn 2p at the surface and subsurface area
of f{NMC. Spectra were acquired at different depths after
surface etching. FIG. 19H shows the elemental ratios at
different depths of ferromagnetic {NMC.
[0186] FIG. 20A shows the X-ray diffraction spectra of
CW, ferromagnetic {CW, and non-ferromagnetic [CW.
[0187] FIG. 20B shows the magnified X-ray diffraction
spectra in the low angle range as shown by the dashed
rectangle in FIG. 20A.
[0188] FIG. 21A shows the X-ray diffraction spectra of
new lithium cobalt oxide (LCO), ferromagnetic f{LCO, and
non-ferromagnetic fLCO.
[0189] FIG. 21B shows the magnified X-ray diffraction
spectra in the low angle range as shown by the dashed
rectangle in FIG. 21A.
[0190] FIG. 22A shows the X-ray diffraction spectra of
new lithium nickel-manganese-cobalt oxide, and ferromag-
netic {NMC.
[0191] FIG. 22B shows the magnified X-ray diffraction
spectra in the low angle range as shown by the dashed
rectangle in FIG. 22A shows.
[0192] FIG. 23A shows the FTIR spectra of CW and
ferromagnetic portion of the f{CW.
Apr. 11, 2024
[0193] FIG. 23B shows the size distribution of starting
CW particles and ferromagnetic portion of {CW particles for
the materials shown in FIG, 23A. The number of particles
N=100.
[0194] FIGS. 23C-23D show SEM images of, respec-
tively, ferromagnetic portion of the {CW and starting CW
particles for the materials shown in FIG. 23A.
[0195] FIGS. 24A-24D are images obtained from a mix of
LCO and NMC. FIG. 24A is a SEM image of the CW
derived from the mix of LCO and NMC before flash
recycling. FIG. 24B is a higher resolution SEM image of the
CW before flash recycling. FIG, 24C is an SEM image of the
ferromagnetic portion of f{CW. FIG. 24D is a higher reso-
lution SEM images of the ferromagnetic portion of f{CW.
[0196] FIGS. 25A-25F are images obtained from LCO.
FIG. 25A shows an SEM image of the LCO before flash
recycling. FIG, 25B shows a higher resolution SEM image
of the LCO before flash recycling. FIG. 25C shows an SEM
image of the ferromagnetic portion of f{LCO.
[0197] FIG. 25D shows the higher resolution SEM images
of the ferromagnetic portion of fLCO.
[0198] FIG. 25E shows the size distribution of new LCO
and ferromagnetic portion of {LCO particles. The number of
samples N=100 FIG. 25F shows the FTIR spectra of the
LCO and ferromagnetic {LCO.
[0199] FIGS. 26A-26F are images obtained from NMC.
FIG. 26A shows an SEM image of the NMC before flash
recycling. FIG. 26B shows a higher resolution SEM image
of the NMC before flash recycling. FIG. 26C shows an SEM
image of the ferromagnetic portion of fNMC.
[0200] FIG. 26D shows the higher resolution SEM images
of the ferromagnetic portion of flash NMC.
[0201] FIG. 26E shows the size distribution of NMC and
ferromagnetic portion of {NMC particles. The number of
samples N=100 FIG. 26F shows the FTIR spectra of the
NMC and ferromagnetic [{NMC.
[0202] FIGS. 27A-27E show FIB-SEM images of the
carbon coated structure. FIG. 27A is the top-view SEM
image showing the ferromagnetic [CW particles after the
FIB cutting. FIGS. 27B-27C are cross-section SEM images
showing the boundary between the surface carbon coating
and the underlying ferromagnetic {CW particles. The dash
line is used to underscore the boundary. FIG. 27D is the
cross-section SEM image of ferromagnetic {CW particles
after FIB cutting and the corresponding elemental distribu-
tions for 0, C, and Co. FIG. 27E is the top-view SEM image
of ferromagnetic {CW particles after FIB cutting and cor-
responding elemental distributions for O, C, and Co.
[0203] FIGS. 28A-28B are schemes of, respectively,
1LCO mag and LCO showing the hierarchical structure of
the flash cathode particles.
[0204] FIGS. 29A-2911 are TEM images of the ferromag-
netic portion of fLCO particles. FIGS. 29A-29B are HR-
TEM images of the ferromagnetic fLCO particles. FIGS.
29C-29D are Fast Fourier transform results of the ferromag-
netic {LCO particles. FIGS. 29E-29F are HR-TEM images
of the new LCO particles. FIGS. 29F-29G are SAED
patterns of the new LCO particles.
[0205] FIG. 30 is a graph showing energy preference
towards phase segregation of partially delithiated CW mate-
rial.
[0206] FIG. 31A is the X-ray diffraction spectra of com-
mercial cathode materials at the charge state and discharge
state.Page 130
US 2024/0120506 Al [0207] FIGS. 31B-31C are the magnified X-ray diffraction spectra in different angle ranges as shown by, respectively the left and right dashed rectangles in FIG. 31A. [0208] FIG. 32 shows the characterization of Li sources, with the curves for LiOH-H,O reactant and recovered Li materials, respectively. The heating rate was set to 10° C. min‘, and the N2 flow was maintained at 80 mL min7’ throughout the run. [0209] FIGS. 33A-33E show characterization for resyn- thesis conditions. FIG. 33A shows the Ellingham diagram of relevant reactions. FIG. 33B is the XRD results of cathode materials resynthesized with a calcination temperature 400° C. (R-CW-400) and 500° C. (R-CW-500). [0210] FIGS. 33C-33E are the thermogravimetric curve and corresponding differential scanning calorimetry analysis of LCO and the ferromagnetic portion of the fLCO. The heating rate was set to 10° C. min”, and the air flow was maintained at 80 mL min7’ throughout the run. To test the thermal stability at 500° C., the temperature was held at 500° C. for 30 min In FIG. 33E. [0211] FIGS. 344-341 show the morphology of resynthe- sized cathodes. FIGS. 34A-34C are SEM images of R-CW reporting the homogeneous carbon coating and layered structure. FIGS. 34D-34E are HR-TEM images of the R-LCO particles reporting recovered cathode layered struc- ture. FIG. 34F is an HAADF-STEM image of the R-LCO particles. FIGS. 34G-34] are the corresponding energy dis- persive analysis element mapping of the R-LCO particles. [0212] FIGS. 35A-35E show characterization of resynthe- sized cathodes. FIG. 35A shows the FTIR spectra of cathode waste and re-synthesized cathode materials (R-CW). FIG. 35B shows the FTIR spectra of LCO and re-synthesized cathode materials (R-LCO). FIG. 35C is the room tempera- ture (300 K) hysteresis loops for the ferromagnetic portion of flash recycled NMC (fCW mag), flash CW after hydro- thermal reaction (after hydro) and re-synthesized cathode materials (R-CW). FIG. 35D is the behavior of the hysteresis loop around the origin for these three samples. FIG. 35E shows electrochemical performances of new NMC (NMC) in prepared half cells. The rate was 0.2 C for testing. [0213] FIGS. 36A-36C shows the morphology of carbon coating structure. FIG. 36A is a TEM image of R-CW particle. FIG. 36B-36C are HR-TEM images of R-CW particle reporting the amorphous feature of the carbon coating at the surface. [0214] FIGS. 37A-37J show elemental distribution of resynthesized cathode materials. FIG. 37A is the energy- dispersive X-ray spectrum of an R-CW particle. FIG. 37B is an HAADF-STEM image of the R-CW particle. FIG. 37C is a BF-STEM image of the R-CW particle. FIG. 37D-37] are corresponding elemental mapping of the R-CW particle. [0215] FIGS. 38A-38D show crystal structure of resyn- thesized cathode materials. FIG. 38A is an HR-TEM image of R-LCO reporting the existence of the layered structure at the surface of cathode particle. FIG. S38B is the correspond- ing FFT pattern of R-LCO as shown in FIG. 38A. FIGS. 38C-38D are atomic-resolution HAADF-STEM images of R-LCO reporting the existence of the layered structure at the surface of cathode particle. [0216] FIGS. 39A-39E show carbon crust configuration after annealing at various temperatures (700 K, 1000 K, 1500 K, 2000 K, and 2500 K, respectively) for 9 ns. [0217] FIGS. 40A-40D shows diffusion barrier for Lit on various features within amorphous carbon shell. FIG. 404 Apr. 11, 2024 shows the unpassivated single-layer graphene edge. FIG. 40B shows the unpassivated double-layer graphene edge. FIG. 40C shows over the reconstructed di-vacancy forming 5-8-5 defect (largest barrier corresponds to diffusion through the 8-ring defect to the other side of the plane, steps 7-10. FIG. 40D shows diffusion over the reconstructed edge of double-layer graphene shows barrier almost identical to that for diffusion on the plane graphene ~0,34 eV. [0218] FIGS. 41A-41F show economic and environmental analysis of pyrometallurgical (pyro), hydrometallurgical (hydro), and flash recycling processes. FIG. 41A is a scheme of a life cycle analysis of Li-ion batteries showing that flashing is a more direct route to recycling. [0219] FIG. 41B is the recycle revenue and recycle cost per kilogram of cathode resynthesized by the various meth- ods. FIG. 41C shows net profit per kilogram of cathode resynthesized by the various methods. FIG. 41D shows total energy consumption of resynthesizing 1 kg of cathode materials with pyrometallurgical, hydrometallurgical, and flash recycling methods. The energy cost from mining the virgin ores is given as a comparison. FIG. 41E shows GHG emissions in resynthesizing 1 kg of cathode materials with pyrometallurgical, hydrometallurgical, and flash recycling methods. The GHG emissions using virgin ores is given as a comparison. FIG. 41F shows net profit per kilogram of various cathodes resynthesized by the pyrometallurgical, hydrometallurgical, and flash recycling methods. [0220] FIG. 42A is a scheme of life cycle analysis of lithium-ion batteries. [0221] FIG. 42B is a simplified flow chart of the pyro- metallurgical method. [0222] FIG. 42C is a simplified flow chart of the hydro- metallurgical method. [0223] FIG. 42D is a simplified flow chart of the flash recycling method. [0224] FIGS. 43A-43B show the scheme of a FJH system. FIG. 43A is an electrical schematic of the FJH system. FIG. 43B is a photograph of the large FJH reaction box [0225] FIGS. 44A-44C show flash recycling of graphite anodes. FIG. 44A-44B are, respectively, schematics of flash recycling of anode waste and resistance-dependent Joule heating effects in multiple phase systems. FIG. 44C is the corresponding current-time curve during the flash recycling process. [0226] FIGS. 45A-45B show, respectively, general proce- dures for conventional high temperature calcination method and real-time temperature curve from the sample during the flash recycling process. [0227] FIGS. 46A-46D show thermal stability results of various anode materials. FIGS. 46A-46B are, respectively, TGA and DSC results of anode waste (AW), calcinated anode waste (cAW), flash anode waste (fAW), and graphite. FIGS. 46C-46D are, respectively, TGA and DSC results of AW, fAW 100 V, fAW 120 V, and fAW 120 Vx2. TGA and DSC data was collected from 25 to 1000° C. under air. The heating rate was set to 10° C./min and the air flow was maintained at 80 mL/min throughout the run. [0228] FIG. 47 shows thermal stability tests results by TGA. The remained mass ratio of various treated graphite anode materials at T=773 K. [0229] FIGS. 48A-48D are, respectively, the optical images of anode waste, calcinated anode waste, flash anode waste (200 mg per batch), and flash anode waste (1 g per batch).
Page 131
US 2024/0120506 Al
[0230] FIGS. 48E-48F are, respectively, TGA and DSC
results of AW and fAW gram-scale. TGA and DSC data was
collected from 25 to 1000° C. under air. The heating rate was
set to 10° C/min and the air flow was maintained at 80
mL/min throughout the run.
[0231] FIG. 49 shows thermal stability tests by TGA. The
remained mass ratio of various treated graphite anode mate-
rials at T=1273 K.
[0232] FIG. 50 shows crystal structures of cAW, fAW, and
AW.
[0233] FIGS. 51A-51B are high resolution XRD spectra of
various anode materials (AW, cAW, and fAW).
[0234] FIGS. 52A-52C are high resolution XRD spectra of
LAW (gram-scale).
[0235] FIG. 53 shows surface compositions of {AW and
AW.
[0236] FIG. 54 shows surface compositions of cAW.
[0237] FIGS. 55A, 55C, and 55E show chemical compo-
nents of anode materials from 0 nm (surface) to 450 nm
depth for AW, £AW, and cAW, respectively. Spectra were
acquired at different depths after surface etching.
[0238] FIGS. 55B, 55D, and 55F show the elemental
distributions of, respectively, AW, fAW, and cAW micropar-
ticles at the subsurface area from 0 to 500 nm.
[0239] FIG. 56 is UV-vis spectra of the aqueous leaching
solution of fAW and AW. The optical images show the
yellowish solution and transparent solution derived from
AW and fAW, respectively.
[0240] FIGS. 57A-571 are SEM images of various anode
materials. FIGS. 57A-57C are AW, FIGS. 57D-57F are fAW,
and FIGS. 57G-57I are cAW.
[0241] FIGS. 57J-57K are statistical survey showing,
respectively, the AW sizes, the fAW sizes, and the cAW
sizes. For each, the number of samples N=50. The size
distribution results indicate that AW, fAW and cAW have
similar average particle sizes.
[0242] FIGS. 58A4-58D are images of anode waste. FIGS.
58A-58B are TEM images; and FIGS. 58C-58D are HR-
TEM images. The average thickness of the SEI around the
graphite particles is ~145 nm. Under the SEI region, the
lattice of the graphite can be seen as shown in FIG. 16c. And
there are many small crystals embedded within the SEI,
which matches with the mosaic model of the SEI structure.
[0243] FIGS. 59A-59D are images of flash anode waste.
FIGS. 59A-59B are TEM images; and FIGS. 59C-59D are
HR-TEM images. The decomposition of the SEI and the
formation of the graphene shell and nanoparticles, such as
LiF and Co,0,, can be seen, which matches with the results
of elemental distributions and XRD spectra. Also, the aver-
age thickness of the layer shrinks from ~145 nm to ~65 nm.
This SEI-derived layer is composed of graphene layer and
embedded nanoparticles, which indicates that flash method
can be an effective method to decompose the SEI and
convert it into protective graphene layer afterwards.
[0244] FIG. 60 are STEM images and the corresponding
elemental distributions of anode waste. The scale bars are
the same for all the images. The metal elements such as Co
(~0.2 at %), are distributed homogeneously within the anode
SEI for pristine AW, which can result from transition metals
dissolution and transporting from the cathode side and get
trapped within SEI at the anode side.
[0245] FIG. 61 are STEM images and respective element
mapping results of {AW microparticles.
Apr. 11, 2024
[0246] FIGS. 62A-62E show metal-ion leaching tests.
FIG. 62A shows recovery efficiency and excess yield Y/Y,
of total metal ions for flash anode waste by HCl with
different concentrations. The number of samples N=3 and
the bars show the standard derivations between runs, the
same below. FIG. 62B shows recovery efficiency and excess
yield Y/Y, of various metal ions for flash anode waste by 0.1
M HCI. FIG. 62C shows recovery efficiency and excess
yield Y/Y, of total metal ions for calcinated anode waste by
HCI with different concentrations. FIG. 62D shows recovery
efficiency and excess yield Y/Y, of total metal ions for flash
anode waste after TGA treatment by HCI with different
concentrations. FIG. 62E shows total amounts of metal ions
and excess yields Y/Y, of various treated anode waste by
concentrated HCI.
[0247] FIGS. 63A-63B are, respectively, TGA and DSC
results of AW, fAW-W, and AW-W. TGA and DSC data was
collected from 25 to 1000° C. under air. The heating rate was
set to 10° C./min and the air flow was maintained at 80
mL/min throughout the run. [AW-W represents [AW after
rinsing with 0.1 M HCI to recollect the valuable metal ions.
The same for other anode materials.
[0248] FIGS. 64A-64C are images of f[AW-W. FIG. 64 is
a TEM image of fAW-W, and FIGS. 64B-64C are HR-TEM.
images of f[AW-W.
[0249] FIG. 64D is corresponding FFT patterns along the
zone axis for fAW-W shown in FIGS. 64A-64C. The
absence of embedded nanoparticles indicates diluted acid
post-treatment can be used to effectively collect the valuable
metals. Besides, there is only one set of 6-fold diffraction
patterns, which reflects the well-graphitized structure of the
anode microparticles.
[0250] FIG. 65 shows the first cycle voltage profiles of
AW, cAW, fAW, and graphite at 0.05 C. The areal capacity
is ~3.0 mAh cm”.
[0251] FIGS. 66A-66C show the voltage profiles of graph-
ite and £AW (in FIG. 66A), cAW (in FIG. 66B) and AW (in
FIG. 66C) at different rates. The areal capacity is ~2.0 mAh
cm”.
[0252] FIG. 67 shows rate performances of AW, cAW,
fAW, and graphite.
[0253] FIGS. 68A-68C show, respectively, preparation of
synthetic graphite, flash recycling method, and high tem-
perature calcination method.
[0254] FIGS. 69A-69C show, respectively, GHG emis-
sions, water consumption, and total energy consumption in
producing 1 kg anode materials with flash recycling method
(flash), high temperature calcination method (HTC) and 1 kg
synthetic graphite.
[0255] FIGS. 69D-69E show the cost and the net profit
about preparing 1 kg of synthetic graphite, 1 kg anode
materials with flash recycling method (flash) and high
temperature calcination method (HTC)
[0256] FIG. 70 shows weight percent of Li, Co, Ni and Mn
that can be collected from a cell including quartz tube,
graphite spacers and copper wool electrodes but without any
loaded sample (i.e., a blank group).
[0257] FIG. 71 shows the total amount of Li and Co in
1,00 g of sample.
[0258] FIGS. 72A-72B show, respectively, recovery effi-
ciency of (a) Li and (b) Co from LCO and flash LCO in HCI
solutions with different concentrations.Page 132
US 2024/0120506 Al [0259] FIG. 73 shows distribution of Li and Co from LCO and flash LCO after dissolving in 0.1 M HCI solutions and rinsing from the quartz tube, graphite spacers, and copper wool electrodes. [0260] FIG. 74 shows total amount of Li, Co, Ni and Mn in 1.00 g sample. (Left bars) before flashing. (Right bars) after flashing [0261] FIGS. 75A-75D show, respectively, recovery effi- ciency of (a) Li, (b) Co, (c) Ni, and (d) Mn from NMC and flash NMC in HCI solutions with different concentrations. DETAILED DESCRIPTION [0262] The present invention relates to the flash recycling of batteries, including lithium-ion batteries, other metal (sodium, potassium, zinc, magnesium, and aluminum)-ion batteries, metal batteries, batteries having all metal oxide cathodes, and batteries having all graphite-containing anodes, including solvent-free and water-free flash Joule heating (FJH) methods performed in combined with mag- netic separation to recover lithium, cobalt, nickel, and man- ganese. The solvent and water-free FJH method combined with magnetic separation can be utilized to recycle spent batteries, i.e., spent lithium-ion batteries (LIBs), other spent metal-ion batteries, and spent metal batteries. The FJH methods disclosed and discussed herein will be focused upon lithium-ion batteries (LIBs). Similar methods can be applied to other metal-ion batteries (and their cathodes and anodes), such as sodium-, potassium-, zinc-, magnesium-, and aluminum-ion batteries, and metal battery anodes and cathodes, which include anode-free batteries (which means there is no excess anodic metal) and metal oxygen and metal air batteries. [0263] This method is ultra-fast and retains the particle morphology (FIG. 1A). Prior recycling strategies to collect the valuable metals contained in spent cathode waste (CW) include pyrometallurgy and hydrometallurgy [Tran 2018}, requiring harsh conditions such as extreme furnace tempera- tures greater than 1400° C. [Lv 2018; Li 2016] or caustic reagents including hydrochloric, nitric, and sulfuric acids (FIGS. 1B-1C). [Chagnes 2013]. In addition, these methods demand high energy, generate much greenhouse gas (GHG) and secondary wastes, and lead to the destruction of the material down to its elements or ionic solutions during the recycling, thereby increasing the cost of conversion back into the cathode morphologies. [Xu 2020]. In the flash method of the present invention, the hierarchical cathode morphology is preserved, while the other components of the CW, such as cathode electrolyte interphase (CEI), are decomposed (FIG, 1A). Apr. 11, 2024 Flash Recycling Process for Cathode Materials [0264] Flash recycling of LIBs is an environmentally cleaner method to reclaim the metals in secondary batteries. The method preserves the 3D layered structure of the cathode and provides an efficient reuse of the elemental inventory. The fast process also produces a convenient carbon coating on the recycled cathode particles that permits Li-ion transport while stabilizing the overall structure of the cathode, thereby affording superior performance to the recycled batteries over new batteries. Since the FJH process is being industrially scaled to the multi-ton scale per facility [Universal Matter 2021], manufacturability is attainable while minimizing dependence on freshly mined metal ores for the production of LIBs. [0265] Ina flash recycling process, a mixture of cathode material and a conductive additive (such as around 10 wt % and such as carbon black) or graphite from the spent anode (such as around 20 wt %), is slightly compressed inside a quartz tube between two electrodes. [Luong 2020; Chen 2021]. The carbon additives are used to increase the elec- trical conductivity of the mixture. The capacitor banks in the circuit can be used to provide electrothermal energy to the reactants for ~300 ms. See FIGS. 2A-2B. [0266] For example, spent Li-ion batteries were dis- charged on a circuit until the voltage was below 2.5 V and then the electrodes were collected by manually disassem- bling the spent batteries. The cathode waste was used after directly removing it from the spent electrodes. Unless speci- fied otherwise, the cathode materials and the conductive additive (10 wt % carbon black or 20 wt % spent anode graphite) were mixed evenly by grinding with a mortar and pestle for ~10 min. The reactants were loaded into a quartz tube with an inner diameter of 4 or 8 mm. The mass loads in 4- and 8-mm tube were 200 mg and 800 mg, respectively. Graphite rods and copper wool were used as electrodes and spacers, respectively. They were used to compress the reac- tants as shown in FIG. 1A. The graphite rods were in contact with the sample in the quartz tube. The electrical energy was provided by a capacitor bank in the circuit with a total capacitance of 60 mF (4 mm tube) or 132 mF (8 mm tube). The capacitor bank was charged by a DC supply that could reach 400 V. The flash duration was controlled by an Arduino controller relay in the circuit acting as a high-speed switch. [0267] Various cathode materials, LCO and cathodes com- bination of NMC were also used to demonstrate the versa- tility of flash recycling method. TABLES I-II show the flash conditions of different cathode materials in a small batch and in a large batch, respectively. TABLE I The flash conditions of different cathode materials in a small batch New LCO New NMC cw Reactant component 90 wt % LCO and 10 90 wt % NMC and 80 wt % NMC and wt % CB 10 wt % CB 20 wt % spent graphite Mass 200 mg per batch «200 mg per bateh 150 mg per batch Reaction atmosphere Ar Ar Ar Reactant 3 3 3 resistance/ohm VoltagelV 120 120 150 Reaction time/ms 300 150 300 Capacitance/mF 60 60 60
Page 133
US 2024/0120506 Al
TABLE II
Apr. 11, 2024
11
The flash conditions of different cathode materials in a large batch
New LCO. New NMC
cw
Reactant component
wt % CB 10 wt % CB
Mass 800 mg per batch 800 mg per batch
Reaction atmosphere AD Ar
Reactant 3 3
resistance/ohm
Voliage/V 120 120
Reaction time/ms 300 150
Capacitance/mE 132 132
90 wt % LCO and 10 90 wt % NMC and 80 wt % NMC and
20 wt % spent
graphite
600 mg per batch
Ar
3
150
300
132
[0268] After the FJH reaction, the reaction was permitted
to cool for 3 min whereupon a commercial bar magnet with
magnetic field strength 5000 Oe was used to separate the
ferromagnetic portion of the flash products. The mass ratio
of the ferromagnetic portion was ~90 wt % and that of the
nonmagnetic portion was ~10 wt %. The remaining ~10 wt
% of flash product which was not captured by the magnet
was collected and combined with minor portions from other
FJH nuns to be re-flashed, and the flash condition was the
same as the one used for the primary flash. For the re-flash
experiments, the small batch experiments were used as the
demonstration. Thereby, ~60 wt % of re-flashed product can
be magnetically recovered.
[0269] In this flash recycling process, having a voltage of
150 V and a resistance of 3Q, the current passing through the
sample is recorded to reach ~40 A in ~300 ms discharge time
(FIGS. 3A-3C). The temperature can be measured through a
16-channel optical fiber spectrometer by black-body radia-
tion fitting (FIG. 4). The temperature was estimated to be
2500 K and the ultrafast cooling rate is also recorded at
~1.2x10* K s' (FIG. 1D). While the pyrometallurgical
method causes loss of the more volatile Li (FIG. 1B) and
irreversible cathode structure collapse [Lv 2018], the
momentary high temperature in flash recycling avoids loss
of Li and preserves the particle morphology and the cathode
3D layered structure.
[0270] CW from spent LIBs, LCO (LiCoO,) and NMC
(LiNi,Mn,Co,0,, normally referred as NMCxyz, such as
NMC;,,,) was tested. The CW was composed of a mixture
of LCO and NMC. The flash recycling product included a
mixture of the ferromagnetic portion (~90 wt %) and non-
ferromagnetic portion (~10 wt %) (FIGS. 1A, 1F, and
5A-5B). The ferromagnetic portions of the flash recycled
products showed a sharp response to the external magnetic
field while the reactants had no ferromagnetic response. This
magnetization was strong enough to ensure the effective
separation of the ferromagnetic portion by a normal hand-
held magnet with magnetic field strength 5000 Oc.
[0271] A simple magnet was used to extract the desired
ferromagnetic portion (FIGS. 1A and 6A-6D). The extracted
ferromagnetic product contained the Li and the transition
metals where the Li is intimately associated with the ferro-
magnetic metals and thereby conveniently extracted with the
magnet.
[0272] Further, the remaining 10% non-ferromagnetic
portion could be re-flashed, as shown in FIGS. 7 and 8A-8E.
This process works with LCO, NMC and mixtures thereof
(FIGS. 9A-9D), as it is found in commercial CW, recovered
from spent LIBs from old laptop computer batteries.
[0273] As shown in FIGS. 1F and 5A-5B, the ferromag-
netic portion of the flash cathode waste ((CW mag, orange
curve) had a sharp response to the external magnetic field
(~10 emu g™ at 1900 Oe) and the magnetic moment reaches
saturation (~17 emu g7') at 8000 Oe. This magnetization
was strong enough to ensure the effective separation of the
ferromagnetic portion by a normal hand-held magnet with
magnetic field strength 5000 Oe. The coercivity force, as
calculated from FIG. 5B, was small, which indicated that the
material’s magnetization can easily reverse direction with-
out dissipating significant energy (hysteresis losses). Con-
trastingly, the {CW nonmag and the intrinsic CW show a
weak magnetic response to the external magnetic field, and
they are paramagnetic and diamagnetic materials, respec-
tively. Therefore, a normal magnet can be used to capture the
ferromagnetic portion of the flash recycled cathode waste to
reclaim the metals, Co, Li, Ni, Mn from the spent batteries.
Li, though non-magnetic, was captured in the microparticles
of the ferromagnetic portion.
[0274] With regard to the reflashing of the non-magnetic
portion, the remaining ~10 wt % of flash product which was
not captured by the magnet could be combined with minor
portions from other FJH runs to be re-flashed, and the flash
condition was the same as the one used for flash recycling
cathode waste. Thereby, ~60 wt % of this could be mag-
netically recovered. And it is similar in behavior to the
originally flashed magnetic portion. The ICP-OES results
show good recovery yields from the re-flash process, includ-
ing Li (79%), Co (77%), Ni (73%) and Mn (84%). As a
consequence, further use of the remaining 10 wt % of the
nonmagnetic portion in the re-flash recycling process can
achieve a high recovery yield for all the valuable metals,
including Li (92%), Co (93%), Ni (96%) and Mn (98%).
[0275] Recovery Efficiency
[0276] High recovery yields are essential for an effective
recycling strategy. [Xiao I 2017]. Recovery efficiency (ct) is
defined in Eq. (1).
N, flash product) 1
= MN, Tash proded 100% 0
m(N, reactant)
[0277] The m(N, flash product) and m(N, reactant) repre-
sent the weight of studied species N in flash product and
reactant, respectively. The amounts are determined by the
ICP-OES and calculated by Eq. (2).Page 134
US 2024/0120506 Al m(N, pro) CN. pro) my(N. pro) ma(N, ree) —m3(N. pro) — (2) inl, reac) ~ CON, rec) my (W, rec) ™ ma(N, pro) ms(N, rec) [0278] The C (N, pro) and C(N, rec) represent the mass concentration of M species in the diluted solution of flash product and reactant, respectively. The m, (N, pro) and m, (N, rec) represent the mass of the diluted solutions for flash product and reactant. The m, (N, rec) and m, (N, pro) represent the mass of sample used in the ICP-OES experi- ment. The m, (N, rec) and m; (N, pro) represent the total mass of sample before the flash reaction and the mass of sample after the magnetic separation, respectively. [0279] The molar ratio () is determined in eq. 3. AN) 100% % ial) [0280] The n(N) and n,(N) represent the actual amount and theoretical mole of studied species N in cathode mate- rials, respectively. The actual moles are determined by the ICP-OES and calculated by eq. 4. Apr. 11, 2024 12 nN) = WV) Xm (NY XV) ic) NX MUN) [0281] MN) represents the molar mass of the species N. [0282] The recovery efficiency from various flash prod- ucts (FIGS. 10A-10D) are quantified using inductively coupled plasma optical emission spectroscopy (ICP-OES). For flash recycling of LCO, the average yields are 92% for Co and 77% for Li (FIG. 11A) after a single flash. These efficiencies can be improved after re-flashing of the non- ferromagnetic portion, so that the total recovery for Co and Li are 98% and 85%, respectively, after one re-flash. Com- pared with conventional pyrometallurgical methods, a higher Li recovery yield can be achieved without compro- mising the yield of Co. [Velazquez 2019; Hu 2021: Xiao II 2017; Wang 2018; Assefi 2020]. These values are also close to the leaching efficiencies of hydrometallurgical methods as shown in the blue region of FIG. 11B and TABLE III, but flash recycling has no generation of the caustic aqueous wastes. [Zhang 1998; Swain 2007; Pinna 2017; Lee 2002; Chen 2015]. TABLE III The recovery efficiencies of metals by different recycle methods Recovery efficiency (%, Method Materials Details Li Co Mn Ni Ref Pyro Spent LIB 1200-1450" C. (2-6 h) 85 Velazquez 2019 Spent LIB 1600° C. 3 h) ~100' 100-100-100 Hu 2021 (NMC 700° C. (0.5 h), vacuum — ~66 / ! J Xiao 2017 type) condition Spent LIB 700°C. (0.5 h), vacuum ~83 / _ — Xiao 2017 (LCO type) condition 600° C.(0.5 h) “1 -B = — Wang 2018 1200~1450° C. (2~6 h) 38 99 Lv 2018 Hydro Spent LIB 4M HC, 80° C for Th 99 99 — — Zhang (LCO type) 1998 2M H,SO, +5 Vol % 95 94 — — Swain H,0,, 75° C for 0.5 h 2007 2% H,SO, + 2 Vol % 88 99 — — Pinna HO, 90° C. for 1h 2017 1M HNO; + 1.7 Vol % 95 95 _ — Lee 2002 H,O,, 75° C for 1h 2M citric acid + 0.6 98 96 _ — Chen H,Os/g solid, 70° C for 2015 =1Sh Spent LIB 1.5M lactic acid, ~0.5 h 98 99 98 98 Li 2017 (NMC type) Others New LCO choline chloride and I 94 — — Tran 2019 ethylene glycol New NMC choline chloride and ~36 -71 f / Tran 2019 ethylene glycol FIR new LCO Voltage 120 V(300ms) 77792? — Herein method 353 98 new NMC Voltage 120 V (150 ms) 94 o4 92 98 Herein Spent LIB Voltage 150 V (300 ms) 832,862 O?_—«89?Herein (mix LCO. 923 939 983 968 and NMC) Notes: ‘= The Li source was from the flue dust which was needed to be collected from a cone-shape stainless steel cover placed atthe outlet of the furnace. 2 The recovery yields by one flash experiment 3 The total recovery yields, including the yields from the re-lash experiment ‘= Not mentioned in the literature reference. =~ 0%
Page 135
US 2024/0120506 Al
[0283] The same tendencies can be found in flash NMC
({NMC) and actual CW with mixed ingredients obtained
from spent LIBs. A single flash of NMC affords high average
recovery yields for all the valuable metals (FIG. 11C),
including Li (94%), Co (94%), Ni (98%) and Mn (92%).
High average recovery yields are also achieved in flash CW
(ECW, FIG. 11D), including Li (92%), Co (93%). Ni (96%)
and Mn (98%). Radar plots (FIGS. 11E-11G and 12A-12F)
compare the metal recovery of the flash method with typical
efficiencies found in the pyrometallurgical and hydrometal-
lurgical methods.
[0284] Structure Retention Factor (R)
[0285] The structure retention factor is defined as the
existing 3D layered cathode structure after the recycling
method. The structure retention factor is only present in the
flash recycling. It highlights the retention of the particle
morphology and crystalline structure after the flash process,
which can be quantified by X-ray diffraction (XRD).
[0286] Structure retention factor (R) is defined in Eq. (5).
_ 2(003)/1(104) (5)
© 19(003)/1o(104)
[0287] The 1(003) and 4104) represent the intensity of
(003) and (104) peaks in the XRD spectrum. I, and T
represent the peak intensity of the reactants and products
derived from different recycling processes. In the XRD
results, (003) peaks indicate the property of layered structure
in lithiated metal oxides, and (104) peaks reflect the property
of transition metal-oxygen bond basic units which forms the
layered compounds. The intensity ratio between (003) and
(104) peaks indicate the efficiency of crystallization. The
lower value of 1(003)/1(104) reflects the cation mixing
between transition metal and lithium and generally a decom-
position of the layered character.
[0288] (1) R=0, when the layered structure disappears
[0289] (2) O<R<1, when the crystallinity degrades
while the layered structure is preserved.
[0290] (3) R21, when the crystallinity improves, and the
layered structure is preserved.
[0291] For the hydrometallurgical and pyrometallurgical
methods, the layered structure of cathode waste materials no
longer exists, and R=0. On the contrary, the flash recycling
method can preserve the structure and R=3.29/3.22=1.02.
This value reflects the layered structure was preserved while
the crystallinity did not degrade during the flash recycling
method.
[0292] Hierarchical Structure of The Microparticles of
Cathode Materials
[0293] The efficiency of the flash recycling process on the
cathode materials was determined by analyzing the subsur-
face region and bulk crystal structure of the ferromagnetic
portion by elemental depth analysis and XRD, respectively.
[Andre 2015]. Distinct elemental ratios and valence states
from the surface to the subsurface revealed the hierarchical
structure of the cathode microparticles derived from flash
recycling process.
[0294] For fCW, the atomic ratio of Co increases dramati-
cally from <1% to ~20% when processing from the surface
to 500 nm depth, and the binding energy downshifts from
782.2 eV at the surface to 779.3 eV (below 200 nm, FIGS.
13A-13B), while the carbon content decreases in the corre-
sponding region (FIG. 13B). The splitting of the O is spectra
Apr. 11, 2024
to Og, (532.6 eV) and Og (530.3 eV), show a transition from
adsorbed oxygen species to lattice oxygen species (FIGS.
14A-14E). [Chen 2015].
[0295] Combined with the unchanged binding energy of
Co 2p spectra below 200 nm, this confirmed the existence of
intact lithiated metal oxides in this region (FIG. 13C). On the
contrary, the unflashed CW had no significant change of
binding energies or elemental contents below the solid
electrolyte interface that had formed during battery cycling
process (FIGS. 154-15G). This result confirms that there is
a hierarchical structure of cathode microparticles formed
due to the flash recycling process. The similar topological
structures are found in flash recycled LCO and NMC (FIGS.
16A-16F, 17A-17F, 18A-18H, and 19A-19H), which
showed the wide applicability of the flash recycling method
to treat different cathode materials.
[0296] The layered structure of the magnetic portion of
flash recycled CW is further corroborated by the (003)
diffraction peaks at ~18.9° [Dai 2019], while the nonmag-
netic portion is mainly composed of the graphite conductive
additive with some residual metal signals (FIGS. 20A-20B).
Similarly, there are intact layered structures in flash LCO
(FLCO) and f{NMC (FIGS. 21A-21B and 19A-19B). The
appearance of magnetic properties in the {CW underscores
one pertinent aspect of the flash method. The localized rapid
heating and cooling maintain the integrity of the particle,
while triggering a thermal decomposition limited to the
surface only. This process affects the CEI, cathode surface,
carbon coating and the ability to resynthesize the new
cathode.
[0297] The CEI is decomposed into salts coating the
particles. The existence of the carbonate can be confirmed
by the stretching mode of CO,’- in the FTIR spectrum
(FIGS. 23A-23D, 24A-24D, 25A-25F, and 26A-26F) and
the high binding energy in the XPS C is spectra. [Li 2019].
The carbon existing in the electrode is also re-arranged at
high temperature on the surface of the particles as a thin
coating, as evidenced by elemental mapping (FIG. 13D).
The carbon thickness is 20 to 50 nm, distinguished by
focused ion beam milling combined with SEM images
(FIGS. 27A-27E) and the elemental depth analysis as shown
in XPS results (FIGS. 14A-14E). As shown in FIGS. 27D-
27E, the elements Co and O are concentrated at the cross-
section without the presence of C, while the top surface
shows the existence of the C and the absence of Co and O.
This shows that the carbon coating on the surface of ferro-
magnetic fCW particles and that the thickness is 20~50 nm
estimated from the cross-section SEM images and XPS
depth analysis. The carbon coating is derived from the flash
reaction between the cathode particles and conductive car-
bon additives. During the flash reaction, happening in 10 to
30 ms, the hot spots form only at the interfaces between
conductive carbon and the insulating cathode materials.
These hot spots cause the formation of the thin carbon
coating (20~50 nm) on the cathode particles and the forma-
tion of the subsurface metal oxide (~200 nm) after Li*
diffusion towards the interface, without the irreversible
layered structure collapse.
[0298] The cathode surface reactions can be particularly
important. The flash induces the generation of a metal oxide
film from two sources, rearrangement and decomposition.
The flash process thermally decomposes the particle surface,
with release of O, and de-lithiation. This surface modifica-
tion leads to the formation of Co' containing species at thePage 136
US 2024/0120506 Al
surface, such as Co,O, and CoO, with enhanced magnetic
susceptibility compared to the lithiated species. [Sharifi
2017]. It has been shown that in aged cathodes, this process
can happen at temperatures lower than 300° C. [Furushima
2011]. Oxides can also be formed naturally as part of the
cycling and can be rearranged by the flash process. As a
result of repeated cycles of charge/discharge, the surface of
CW particles is composed of areas of crystalline LiCoO,,
partially delithiated LixCoO,, and small inclusions of the
Co,0, and CoO phases. [Kabir 2017].
[0299] During the FJH process, this heterogeneous mate-
rial undergoes an annealing process while being encapsu-
lated with a carbon shell that prevent significant mass loss.
Driven by structural relaxation, Co,O,, and CoO undergo an
outward segregation (FIG. 13E), forming a shell over the
restored and crystalline LiCoO,. Part of this surface metal
oxide can be distinguished in high resolution transmission
electron microscopy (HR-TEM) images (FIGS. 28A-28B
and FIGS. 29A-2911).
[0300] First principle calculations show the energy pref-
erence, AE, of such segregation (FIG. 30). First principle
calculations allowed for the demonstration of a possible
route for annealing process of partially delithiated LixCoO,
through phase segregation of high quality LiCoO,, Co,0,
and release of O, gas [Furushimna 2011]:
Li,CoO,-xLiCoO+(1-x)/3 Co3044(1-x)/3 > ()
[0301] Reaction energy AE=Ezi¢,02+Eco304tEo2-
Exxcoo2 for various values of x is plotted on FIG. 30 and
indicates energetic preference towards phase segregation. It
is interesting to note that at low-to-moderate delithiation
levels energy preference towards segregation is minimal
[0302] Relatively lower AE are observed in fresh cathodes
compared to aged ones, showing that the annealing during
flash recycling is more effective in aged cathodes because of
the more pronounced delithiation. This mechanism is con-
sistent with increased structure retention factor as can be
seen in FIGS. 11H, 12A, and 12D. The flash cathode
materials retain ~93% of the original particle size distribu-
tion of cathode materials (FIGS. 23A-23D, 24A-24D, 25A-
25F, and 26A-26F). The surface decomposition is further
evidenced by x-ray diffraction (XRD). The downshift of the
diffraction peak (003) (expansion of interlayer spacing),
observed in the ferromagnetic portion of {CW (FIGS. 20A-
20B), is consistent with a partial de-lithiation process (FIG.
31A-31C).
[0303] The magnetic properties of Co;0,/CoO film were
simulated (FIG. 13E), presenting a magnetic moment of ~70
emu/g for bulk phase (magnetic moment about one third of
219 emu/g for Fe). The magnetic characteristics of oxide
shells are somewhat reduced due to inherent disorder and
size-effects displaying characteristics consistent with that of
thin Co,0, films. [Apatiga 2006; Moro 2013; Zhang 2015].
The formation of this layer is useful (and can be utilized) for
the magnetic separation. The gradual nature of annealing is
consistent with the ability to improve recycling yield
through the repeated FJH of non-magnetic material observed
in the experiment.
[0304] Resynthesized Cathode Materials
[0305] The cathode materials can be resynthesized from
the ferromagnetic flash products and in the context, they are
named “resynthesized cathodes” (R-CW). For example, ~1
g flash product was mixed with 10 mL 4 mol L~* LiOH
aqueous solution, and then the mixture was poured into a
Apr. 11, 2024
hydrothermal vessel. The hydrothermal vessel was made of
polytetrafluoroethylene and the volume was 40 mL. Then
the vessel was sealed in a well-fitted stainless-steel auto-
clave and put into the oven under 180° C. for 12 hours.
Subsequently, vacuum filtration was used to dry the solid
powder. Then, the solid was calcinated at 400° C. for 3 hours
in air before it was used to prepare the battery slurry.
[0306] In terms of synthesizing new cathodes, the flash
process offers a more efficient use of Li. Compared with
solid-state reactions to prepare the resynthesized cathode,
the hydrothermal methods disclosed and described herein
can avoid the direct use the solid Li source, which is hard to
remove after the resynthesis process and acts as the impurity
to affect the electrochemical performance of the cathode
materials. As reported in literature [Zhao 2020; Zhang
2014], the chemical potential can drive the chemical lithi-
ation of the layered flash product Lip g,CoO, (the stoichio-
metric ratio is calculated from ICP-OES) to form the final
resynthesized cathode materials. Since there is no funda-
mental structure change, the optimized condition can be
milder compared to the synthesis condition starting from
rock-type metal oxide, such as Co,0,. LiOH is used as Li
source, since it has good solubility in water to form a
concentrate solution. Other Li sources, like Li,CO3, which
has been also reported [Zhao 2020] as a Li source for the
synthesis of LCO, can also be considered in an industrialized
process. A purpose of the final calcination step is to increase
the crystallinity and improve the electrochemical perfor-
mance of the resynthesized cathode materials, and the reason
for choosing 400° C. in embodiments can be explained by
the results, because the carbothermal reduction starts if the
temperature is greater than 450° C. [Wang 2018]
[0307] The formation of the lithium carbonate at the
surface of the ferromagnetic flashed particles minimizes the
need for supplemental Li-ion precursor to reconstitute a
newly recycled cathode stoichiometry. See FIG. 32.
[0308] To calculate the consumed Li sources in the resyn-
thesized process, the solvent after the hydrothermal reaction
is collected. TGA is carried out (FIG. 32) to calculate the
impurities in remaining Li sources, such as the crystal water.
There is one mass loss stage by TGA in the LiOH:'H,O
reactant at ~120° C., which is related to the loss of the crystal
water in the reactant. For the recovered Li materials, there
are three stages. (1) At ~100° C., the loss (~5.6%) is related
to the loss of the crystal water. (2) At ~600° C., the loss
(~31.0%) is associated with the decomposition of LiOH. (3)
At -860° C., the loss (~8.9%) is associated with the decom-
position of Li,CO, and the remained powder is Li,O. [Beyer
2013]. The mass of the recovered powder is 1.0259 g. Thus,
the mass of Li in the recovered powder is 0.2686 g. Since the
mass of Li in the reactant powder is 0.2804 g and ~1.0 g
flash powder is used, the ratio of consumed Li is 18.4%.
[0309] Only 10% to 20% of fresh Li-ion is required to
fully lithiate and rebuild the cathode materials (FIGS. 33A-
33E, where the corresponding cobalt complexes are pre-
sented with their requisite Gibbs free energies), since 80% to
90% is already present in the ferromagnetic flash product as
indicated by ICP-OES. Fresh cathode materials can be
resynthesized from ferromagnetic f{CW by a simple hydro-
thermal reaction followed by calcination at 400° C. in air.
[0310] For certain embodiments, the optimized calcina-
tion temperature is 400° C. and a higher temperature, ~500°
C., will result in the carbothermal reduction. Thus, the
following characterizations are for R-CW-400 and for sim-Page 137
US 2024/0120506 Al
plicity, it is called R-CW. The possible reactions of LCO and
the corresponding Gibbs free energy relationship can be
calculated as follows:
ALiC0O,(s)=2Li,0(s)+4C00(s)+0,(e)
A,Gz'-604,78-0.557xT a
C(s)+2CoO{s)=CO,(g}+2Cols)
Gp2=18.52-0.17683xP (8)
C(s)402(g)-CO,(g)
A,G2=-393,98+0.20891x7 (9)
Li,O(S)+CO,(g)=Li,CO3(s)
A,GpP—210.4740.13483x7 (10)
6CoO(s}+02(g)-2C0;0,4(5)
A,G 2-407 3940.33709xT (11)
2LICOO3(s)+C(s)=LizCO4(s)+CoO(s}+Cos)
A,GP=-65.81-0.12763xE (12)
12LiC00,(8}46C{s}+503(g}=6Li,CO4(s)+4C0304(s)
A,GP=-2627.1441.06592xT (13)
[0311] The Ellingham diagram of the above reactions were
plotted, which confirmation the thermodynamic relation-
ship. [Wang 2018]. The carbothermal reduction between the
carbon and LCO is thermodynamically favorable under inert
atmosphere or in air. Thus, the high temperature calcination
can cause the reduction of the Co species and it is not good
for cathode material resynthesis. Similarly, direct high tem-
perature treatment in pyrometallurgical method can only get
Co,0, metal chunk derived from the above carbothermal
reaction. The thermogravimetric curves also demonstrate
that LCO itself is stable in air when the temperature exceeds
1000° C., while the ferromagnetic portion of f{LCO, which
is coated with carbon, shows a greater than 10 wt % weight
loss when the temperature increases from 600° C. to 800° C.
This can also be explained by the above carbothermal
reaction. If holding the temperature at 500° C. for 30 min,
the obvious mass loss can still be observed as shown in FIG.
33E. This is consistent with the XRD in FIG. 33B.
[0312] In order to coat the cathode materials with carbon,
a low calcination temperature should be used at the last step
of the resynthesis process. However, the resynthesized cath-
ode derived from pyrometallurgical or hydrometallurgical
methods need a high calcination temperature (greater than
750° C.) to build the ordered layer structure of the cathode.
[Zhao 2020; Zhang 2014; Nie 2015]. This feature renders it
more difficult to directly achieve the surface carbon coating
in those classical resynthesis processes, and more complex
post-treatment should be necessary if the carbon coating is
needed after a pyrometallurgical or hydrometallurgical
recycle protocol.
[0313] The resynthesized cathode materials (R-CW) lose
the ferromagnetism and show a 3D layered structure with
high crystallinity. FIGS, 344-341, 35A-35E, 36A-36C, and
37A-37]. For FIGS. 36A-36C, the amorphous carbon coat-
ing can prevent the direct exposure of NMC cathode particle
in the corrosive carbonate electrolyte and reduce the para-
Apr. 11, 2024
sitic reaction between NMC and electrolyte under high
voltage condition. It has also been confirmed that, unlike
well-graphitized carbon coating, the amorphous carbon
coating is Li-ion permeable. Thus, the flash Joule heating
method can be used to coat cathode materials. For FIGS.
37A-37], it can be seen there is a thin carbon coating at the
surface of the R-CW particle.
[0314] The high-resolution TEM image of FIG. 13F and
corresponding fast Fourier transform (FFT) patterns indicate
the existence of the layered structure at the surface of
cathode particle.
[0315] Atomic resolution high-angle annular dark-field
scanning transmission electron microscopy (HAADF-
STEM) imaging (FIGS. 13G and 38A-38D) shows the
existence of trigonal lattice with the space group R3m.
(Compared with {LCO with spinel structure as shown in
FIGS. 29A-29H, FIGS. 384-38D show there is a recovered
layered structure in the resynthesized cathode materials).
[0316] These results reflect the recovered layered structure
in the resynthesized cathode materials. The amorphous
carbon coating on the R-CW particles is also retained after
the resynthesis process as shown by SEM (FIGS. 34A-341),
HR-TEM (FIGS. 36A-36C), STEM and corresponding
elemental mapping (FIGS. 13H and 37A-37J). Similarly, the
layered structure appears in R-LCO, and the energy mapping
showed the existence of a carbon coating (FIGS. 34A-34]).
[0317] Atomistic Simulations
[0318] The partially graphitized carbon crust also can be
important in the cell performance, as its permeability to
Li-ion is a factor for the electrochemical processes. High
temperature annealing during flash recycling was simulated
for large amorphous carbon structure containing over 30000
atoms using AIREBO interatomic potential. Initial configu-
rations included small graphitic domains of arbitrary shape
in the 8 A-22 A size range and up to 3 layers thick that were
misaligned by up to 50 degrees and randomly positioned
within the periodic cell. Remaining 65% of atoms were
provided as individual carbon atoms randomly positioned
within the unit cell. Resulting configurations were pre-
annealed, slowly heated up to the target temperature. For
comparison, FIGS. 39A-39E show the results of annealing at
TOOK, 1000K, 1500K, 2000K and 2500K.
[0319] The simulation at high temperature (2500 K) indi-
cate a fully amorphous carbon with the density of 0.9 g em™>
(FIG. 131). Using first principle calculations, diffusion of Li*
ion was compared over various features of carbon structures
to identify effect of annealing of Li* permeability of carbon
crust. A particular role is played by elimination of unpassi-
vated graphitic edges during annealing. As demonstrated in
FIGS. 40A-40D, the diffusion barrier over these structural
elements can reach 1.5 eV in comparison with 0.34 eV
barrier for perfect graphitic plane. Furthermore, unpassi-
vated edges present potential energy traps that would cap-
ture Li-ions negatively affecting battery characteristics.
[0320] In plane diffusion over reconstructed di-vacancy is
characterized with 0.5 eV barrier similar to that of graphitic
plane. Additionally, larger octagonal defects allow for trans-
mission through the surface but large barrier of 1.6 eV must
be overcome. Furthermore, fully reconstructed graphitic
edges, forming a bulb like shape [Zhang 2012] do not
obstruct Li* diffusion acting as a smooth surface continua-
tion with diffusion barrier of 0.4 eV.
[0321] _First-principle calculations show significant differ-
ences in the effect of various structural elements within thePage 138
US 2024/0120506 Al amorphous carbon crust on the Li-ion diffusion. FIGS. 39A-39E and FIGS. 40A-40D. The annealing eliminates unpassivated graphitic edges and point defects, thus improv- ing Li-ion permeability of the crust (see FIG. 131), as observed. [0322] Life Cycle of Flash Recycling Process [0323] The electrochemical cycling performance of the flash recycled R-CW was studied in a half-cell with initial configuration R-CW/Li. Although the R-CW shows an obvi- ous decay in the first 10 cycles, a slower capacity decay from 25 to 200 cycles is observed, compared to a new LCO and new NMC cathode without the flash-generated carbon coat- ing as assembled under the same laboratory conditions. FIGS. 13] and 35A-35E. The R-CW is far more stable than the origin CW. [0324] This improved cycling performance of the R-CW can be attributed to the carbon coating, which acts as the artificial CEI to avoid the direct exposure of cathode par- ticles, while possessing high oxidative stability in the elec- trolyte. This lessens the irreversible active materials loss during electrochemical cycling process. Further optimiza- tion to minimize the decay in the first 10 cycles would increase the efliciency, but even at this preliminary level of study, the R-CW outperforms new cathode materials in similarly constructed systems. The ability to rapidly, and without solvent or paste, generate such a stabilizing and Li-ion permeable carbon coating can be particularly impor- tant in the newer higher capacity but less stable NMC cathodes, and it could result in this flash approach to be used even on new cathodes rather than solely on recycled mate- rials. [0325] Using the EverBatt 2020 software package devel- oped by Argonne National Laboratory for determining the closed-loop life cycle analysis of LIBs [Everbatt 2020], the flash method was compared with different types of recycling processes and their efficiencies. FIGS. 41A-41F and 42A- 42D. [0326] The scheme of the closed-loop life cycle analysis of LIBs illustrates the various phases in the recycling processes. FIG. 42A. Direct recycling processes, such as refurbishment and repurpose, are easily operating, but gen- erally result in downcycled and downregulated cathode materials. On the contrary, current recycling processes, such as pyrometallurgical or hydrometallurgical methods, involve complex steps to recover the valuable metals with the form of elements and compounds. However, these methods irre- versibly destroy structures of the high-performance cathode and bring in extra resynthesis steps before they can go back to the use phase. The FJH method achieves a high recovery yield without the loss of cathode layered-structure and reduces the operation phases. [0327] The flash recycling does not destroy the cathode layered structure while facilitating reuse in well-performing batteries. FIG. 13J. By using the LCO-type cathode as the model, flash recycling reduces the recycling cost by ~45%, reduces recycling energy by ~70%, and reduces GHG emis- sions by ~70%, while increasing the profitability of recy- cling by ~$25 per kg-cathode and ~$18 per kg-cathode compared with pyrometallurgical or hydrometallurgical methods, respectively. See FIGS. 41B-41E. With increased interest in cathode materials possessing lower Co content, such as NMC622, NMC811 and NCA, and non-Co-based systems such as LiFePO, and LiNiO,, more efficient recy- Apr. 11, 2024 cling with increased profit margins might be attainable by flash recycling using these other ferromagnetic metals. FIG. 41F. [0328] _ It should be noted that there is a revenue difference between pyrometallurgical and the others due to the burning for energy rather than the sale. This utilization of the feed materials in the different recycle methods is shown in TABLE IV. TABLE IV The fate of feed materials in different recycle methods Flash Materials Pyrometallurgical Hydrometallurgical recycling Cathode materials Recycle Recycle Recycle Graphite Bum for energy Recycle Recycle cu Recycle Recycle Recycle Al Intermediate, Recycle Recycle Fe Recycle Recycle Plastic Bum for energy Bum for energy Electrolyte Bum for energy Bum for energy Carbon black Bum for energy Bum for energy PVDF Bum for energy Bum forenergy _Intermediate Note: “Plastic can be flash Joule heated to form the flash graphene. [Algozeeb 2020], [0329] Accordingly, flash recycling of LIBs is an environ- mentally cleaner method to reclaim the metals in secondary batteries. The method preserves the 3D layered structure of the cathode and provides an efficient reuse of the elemental inventory. The fast process also produces a convenient carbon coating on the recycled cathode particles that permits Li-ion transport while stabilizing the overall structure of the cathode, thereby affording superior performance to the recycled batteries over new batteries. Since the FJH process is being industrially scaled to the multi-ton scale per facility [Universal Matter 2021], manufacturability is attainable while minimizing dependence on freshly mined metal ores for the production of LIBs. Flash Recycling Process for Anode Materials [0330] High temperature calcinations (1200~3000 K) are still the mainstream process to regenerate the graphite, which is time- and energy-consuming, accounting for more than 50% of the recycling cost. The use of strong caustic acids, such as HCI and H,SO,, poses the serious concerns about the secondary waste as well. Besides, calcinations incur the formation of the toxic and corrosive exhausted gases, such as HF, making these methods less promising for dealing with pristine anode waste (AW) that is directly recovered from lithium-ion batteries LIBs. [0331] A solvent and water-free flash recycling method has been discovered that rejuvenates the AW directly col- lected from spent LIBs, which is done within seconds and retains the graphite particle morphology. The estimated energy cost is only ~$67 to flash recycle 1-ton pristine AW. After the flash recycling process, the mosaic-like SEI can be decomposed and graphene shell forms on the surface of graphite microparticles. The formation of the SEI-derived graphitic layer embedded with inorganic salts, such as LiF, Li,CO, and Co,O, can be observed. These inorganic salts can be easily recollected by a post-treatment with 0.1 M HCI solution from graphite. The flash anode products show the recovered specific capacity (358.9 mAh g™ at 0.2 C), compared with pristine AW and commercial graphite mate-
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US 2024/0120506 Al rials. Life-cycle-analysis (LCA) and comparison to the cur- rent calcination method indicates that flash recycling method can significantly reduce the total energy and water consump- tions, and greenhouse gas (GHG) emissions, which shows the environmental and economic potential of flash recycling method. [0332] In embodiments, ultrafast solvent-free flash Joule heating (FJH) methods regenerate battery graphite anodes in bulk dry powder form from battery anode waste. Charac- terization of flash recycling products show the intact 3D-lay- ered graphite core structure coated with a solid electrolyte interphase (SEI)-derived graphene shell. The valuable met- als, lithium, cobalt, nickel, and manganese can be easily recovered from the flash anode products by a dilute acid post-treatment. The flash anode materials show recovered electrochemical performance when compared to anode waste and new commercial graphite. Life-cycle-analysis relative to current calcination methods highlight that flash recycling can significantly reduce the total energy and greenhouse gas emissions while turning anode recycling into an economically advantageous process. [0333] The FJH system is similar to that previously described above. [See also Luong 2020; Chen 2021]. The circuit diagram of a FTH setup and a photo of a FJH reaction box are shown in FIGS. 43A-43B. In an exemplary embodi- ment, Ar gas (~1 atm) was used as an inert atmosphere to avoid sample oxidation during the FJH reaction. The reac- tant was the graphite anode waste collected from the anode side in spent Li-ion batteries. The reactant powder was ground and mixed homogeneously by a mortar and pestle before being loaded into the reaction tube with an inner diameter of 8 or 16 mm. The reaction tube can be a quartz or a ceramic tube, or concrete, or other non-conductive material. The mass loadings in the 8-mm and 16-mm tube were 200 mg and 1 g, respectively. Graphite rods were used as electrodes in this reaction. The compressing force was controlled by a small vise connected to a rotary knob as shown in FIG. 43B, to tune the sample resistance to ~2Q. The Arduino controller with a programmable millisecond- level delay time was used to control the discharge time and the electric energy was provided by a capacitor bank with a total capacitance of 60 to 222 mF. The capacitor bank was charged by a DC power supply capable of reaching 400 V. The FJH reaction was carried out with voltage 120 V and optimized duration of 1000 ms for an 8-mm tube reaction. (More details are shown in TABLE V) After the FJH reaction, the apparatus was allowed to cool and vent for 3 min. The product is called flash anode waste (fAW) in this context. TABLE V Flash parameter for different systems Small bateh Large batch Reactant Graphite anode waste Graphite anode waste Sample mass 200 mg lg Sample resistance ~13 Q ~1.0Q Discharge voltage 120 V 164 V Flash duration 1000 ms 1000 ms Total capacitance 168 mF 222 mF Number of times flash 2 3 was applied Chamber pressure Ar (~1 atm) ‘Ar (1 atm) Apr. 11, 2024 [0334] In a typical flash recycling process, the AW col- lected from spent lithium-ion batteries (LIBs) is directly used as the reactant without further treatment. The AW, in the powder form, is slight compressed inside a quartz tube between two graphite electrodes (FIGS. 43A-43B). The capacitor banks in the circuit are used to provide electro- thermal energy to the AW reactants for ~1000 ms (FIGS. 44A-44B). During the typical flash recycling process with a voltage of 120 V and a resistance of ~1.3Q, the current passing through the sample reaches ~350 A in ~1000 ms discharge time (FIG. 44C). The total amount of electrical energy is 1210 J g”!, the majority (>80%) of which is targeted to heat and decompose the SEI (continuous phase), while the graphite microparticles (disperse phase) only receive <20% of the electrical energy according to the Joule heating distribution rule (FIG. 44C). This continuous phase Joule heating effect reflects the selective reaction of inter- facial resistive layer (continuous phase), in our case, the graphitization of the SEI. [0335] In traditional calcination processes (FIG. 45A- 45B), the entire system, including environment and anode waste, is subjected to high temperature (>1300 K) for several hours under inert atmosphere protection, which demands high energy consumption, generate more GHG and further generation of secondary waste. [Yu 2021]. Flash recycling process achieves the momentary and local heating of the AW with desired selectivity and the environment facilitates the subsequent rapid heating transfer from the reactant to avoid thermal expansion and defects formation. The temperature is measured through a high-temperature infrared thermometer with the maximum temperature ~2850 K. There are ultrafast heating rate ~1.6x10° K s7! and cooling rate ~9.2x10* K s~! during the flash process (FIG. 45A-45B), [0336] To confirm the decomposition of SEI structure and evaluate the removal of “dead mass” in the flash recycling process, thermogravimetric analysis (TGA) is used since the thermal stabilities of the SEI, binder, and other components, such as graphite or inorganic salts are distinct (FIGS. 46A-46D). [Beyer 2013; Advincula 2021]. [0337] For pristine AW, there is ~16.3% mass loss at 773 K (FIG. 47), while after flash reaction, the mass loss decreases dramatically. After flashing at 120 V for two cycles, the mass loss becomes negligible (~1.2%), which can be caused by the decomposition of lithium salt, such as LiOH [Beyer 2013], as shown in differential scanning calo- rimetry (DSC) results (FIG. 46B). The similar result is observed for calcinated AW (cAW), which is prepared by calcination at 1323 K for | h under argon protection, with minimal mass loss at 773 K. The pronounced decrease of mass loss can also be found after scaling the system up to gram-level and the optical images of various anode materials can be seen in FIGS. 48A-48F. Therefore, the flash process can effectively decompose the SEI and remove of the “dead mass” accumulated in the pristine AW. Notably, at 1273 K, remained solid accounts for ~12.1% of flash products, while it is <4.0% for cAW. (FIG. 49) The difference of remained weight indicates flash recycling method preserves the inor- ganic salts and facilitates the subsequent metals collection. [0338] To explore the changes after flash process, the bulk crystal structures and surface/subsurface regions of the flash products are analyzed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. The crystal structures of the flash AW (fAW) and cAW are compared
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US 2024/0120506 Al with pristine AW in FIGS. 50 and 51A-51B. High tempera- ture calcination removes most of the organic and inorganic impurities left on the pristine AW and only the diffraction peaks of graphite can be distinguished. [Advincula 2021]. The flash recycling process can decompose the SE] structure with the conversion to other species, such as LiF, which is absent in pristine AW. The (002) diffraction peaks of both cAW and fAW are centered at ~26.5°, which indicates the interlayer distance is ~3.36 A and matches with the layered structure of graphite. The existence of LiF and Li,;CO, and the layered structure of graphite with similar interlayer distance (~3.36 A) are also observed for fAW synthesized from large batch (FIGS. 52A-52C). [0339] Compared to AW, which is rich in F (23.8%), O (14.4%) and P (1.9%) on the surface, fAW shows a relatively higher content of C (89.6%) and decrease of the other nonmetal elements, such as F (5.7%), O (2.9%) and P (<0.1%) (FIG. 53 and TABLE V). cAW also has a high content of C (92.8%) and reduced content of other elements, such as F (1.1%) and O (6.1%) at the surface (FIG. 54). The depth analysis of pristine AW shows the obvious ratio changes of various elements, such as Li and F from 0 to 200 nm and becomes relatively constant below 200 nm (FIGS. 55A-55F), which reflects the elemental composition and SEI atop the graphite microparticle. [0340] While the flash recycling process can decompose the SEI structure and modify the subsurface region, at least 500 nm of depth, reducing the content of nonmetals, includ- ing O, F and P at the surface (FIGS. 55A-55F). The reduction of nonmetal contents observed in the fAW is comparable to the results with cAW, prepared by high temperature calcination. The removal of the original organic SEI and electrolyte residue on pristine AW can be further confirmed by UV-vis spectra. After dispersing the pristine AW within deionized water, the supernatant shows yellow- ish color and has a broad peak centered at ~220 nm, which could result from the oxidized carbonate electrolyte and organic SEI. [Bouteau 2019]. In comparison, fAW dispersed in water at the same concentration (~5 mg mL~') produces a clear solution. A small transition peak located at ~230 nm is observed from fAW, which results from the presence of LiF salt (FIG. 56). [Baldacchini 2004]. [0341] The bulk structures of the graphite microparticles are preserved and the average sizes (~15 jm) are similar after flash recycling process as shown in scanning electron microscopy (SEM) and corresponding size distribution (FIGS. 57A-57L). [0342] To pinpoint the change of surface structures, high resolution transmission electron microscopy (HR-TEM) is conducted as shown in FIGS. 58A-58D and 59A-59D. For AW (FIGS. 584-58D), there is an amorphous layer outside of the graphite microparticles and the average thickness of the layer reaches ~145 nm. The lattice fringes of graphite can be distinguished below this layer. Within the amorphous layer, there are several embedded small Li,CO, crystal, which matches with the mosaic model of the SEI structure. [0343] After the flash reaction (FIGS. 59A-59D), the SEI layer is thermally decomposed, the carbon portion is graphi- tized, and the average thickness shrinks to ~65 nm. The graphene shell can be seen at the outermost region with embedded nanoparticles, such as Co;O, and LiF, formed from the elements in the pristine AW SEI layer. This can be inferred by the scanning TEM (STEM) and corresponding elemental distributions result (FIGS. 60-61). Apr. 11, 2024 [0344] Metal Recovery [0345] Although these metal nanoparticles and salts seem trapped by the reformed graphene layer, they can be removed by rinsing the material with diluted acid. There- fore, the valuable metals, such as Co and Li, can be recovered from fAW by simple acid post-treatment. The presence of Co within the SEI at anode side is not unex- pected. Cobalt dissolution from lithiated metal oxide cath- odes have been observed in cells at the end of their lifespan. [Li 2020]. As SEI traps electrolyte it would also host a concentration of dissolved Co ions, which are converted to metal oxide nanoparticles upon flash recycling. [0346] To recover the valuable metal ions from flash products, HC] solutions with different concentrations are used for comparison. Two factors, recovery efliciency (a) and excess yield Y/Y, are defined to evaluate the recovery results. a is the recovery of one species (a metal from AW, fAW, or cAW) relative to the recovery done by the concen- trated acid and Y/Y, is the yield obtained from various treated anode materials ([AW or cAW) relative to the yield obtained from pristine AW using the same recovery proce- dure. [0347] Compared with concentrated HCI (10 to 11 M) used presently in the battery recycle industry, diluted HC] (0.01~1 M) can also effectively recollect the metal ions from the flash products and the average recovery efficiency reaches ~97.5% by using 0.1 M HCI (FIG. 62A). The total amounts of metal ions recovered from fAW was also higher than the recovery from pristine AW, and the average excess yield was 1.12 by using 0.1 M HCl, which indicated 12% more metal ions can be collected from flash products. This result is supported by the STEM images and elemental mapping, which shows the formation of the metal oxides nanoparticles and polar salts, such as Co,;O, and LiF after flash reaction. [0348] Compared with organic salts formed within the SEI, these inorganic metal oxides and polar salts can be completely dissolved in the more diluted acid solution. Therefore, the average recovery efficiencies for respective metal ions, such as Li (99.4%) and Co (80.1%) are high (FIG. 62B) even treated with 0.1 M HCI solution. The average excess yields for Li and Co were 1.10 and 1.19, which reflected that 10% more Li, and 19% more Co can be recollected from flash product than pristine AW. [0349] By comparison, direct high temperature calcination causes the evaporation of these metal sources, which con- dense downstream and might be corrosive to the devices, such as metal chamber and glass pipeline. Thus, only <15% of total metal ions can be collected at different HCI solutions (FIG. 62C). TGA results show the weight percent was 10-15 wt % for pristine AW and £fAW afier heating under air to 1273 K, the remained solids are the main sources for different metal ions (FIG. 62D). [0350] FIG. 62E shows the absolute quantities of different metal ions within the materials and compares the degrees of recovery and excess yields obtained from different recycling, conditions and materials. The total concentrations of Li, Co and Ni reach 15314, 898 and 124 ppm in £AW, which are more concentrated than natural sources, such as ores and brines (100~1000 ppm for Li) or seawater (<0.21 ppm for Li). Besides, these metal species can be easily recollected by diluted acid solution and there are little interfering ions, such as Na* (~13000 ppm for seawater), Ca’*, Mg** and K* within the fAW. After rinsing [AW with 0.1 M HCI solution,
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US 2024/0120506 Al there is little mass remained after heating under air to 1273 K and only diffraction peaks of graphite can be distin- guished, which indicates effective recovery of various valu- able metal ions from fAW relative to pristine AW (FIGS. 63A-63B). The HR-TEM and corresponding fast Fourier transform (FFT) results of rinsed fAW samples (fAW-W) shows the disappearance of these nanoparticles and a set of 6-fold diffraction patterns along the [002] zone axis, which confirms the recollection of various valuable metal ions and preservation of well-graphitized anode particles (FIGS. 64A-64D). Since the usage of diluted HCI solution greatly alleviates the possible corrosion to the equipment and miti- gates the potential danger to operators and environment, the flash recycling method has the potential to be applied for anode regeneration and metal sources recovery. [0351] Effectiveness [0352] To evaluate the effectiveness of flash recycling method, the electrochemical properties of various anode materials, including bulk resistivity, rate performance and electrochemical stability, were tested. Polarization build-up during the charge and discharge process, caused by the accumulation of the SEI and surface amorphization, is one of the major reasons for anode failure. As listed in TABLE VI, the pronounced decrease (~63%) of the bulk resistivity from AW to £AW indicates the decomposition of the resistive SEI and owing to the surface coating of fluorinated layer derived from flash process, the resistance of [AW is still larger than intrinsic graphite materials. This fluorinated layer can act as the artificial SEI layer to improve the reversibility in the first cycle, which is associated with the formation of new SEI and is a factor for electrochemical stability in the subsequent charging and discharging process. TABLE VI Bulk resistivity of various anode materials Materials Resistivity (ohm m) Commercial graphite 12x 104 AW 57x 10% fAW-120 V 43x 107 fAW-120 V x 2 (FAW) 21x 103 fAW-W 11x 10% cAW 63x 104 [0353] The skeletal density of the anode materials is ~2.2 gcm”*. As shown in FIG. 65, the Coulombic efficiency (CE) of £AW, cAW and graphite at their first cycle are 84.4%, 74.3% and 80.3%, respectively. The areal capacities of the tested anodes are ~3.0 mAh cm~?. This result indicates [AW has smaller irreversible loss of electrochemically active Li species relative to cAW and commercial graphite. [0354] Since the reduction of solution components, including solvent and salt anions, and the simultaneous growth of SEI occurs at 0.5-1.5 V (vs. Li/Li*), there is the smallest irreversible capacity loss (~20 mAh g~') for fAW, relative to AW (~46 mAh g™') and commercial graphite (~37 mAh g7'). cAW (~55 mAh g7) has the largest irreversible capacity loss, which is associated with CE at the first cycle. The formation of favorable SEI for fAW alleviates the cycling polarization and lowers the overpotential, especially at a larger rate (>0.5 C) compared to graphite, pristine AW and cAW (FIGS. 66A-66C). [0355] The average specific capacity of [AW is 341.5, 331.9, 233.1 and 154.1 mAh g™! at rates of 0.05 C, 0.1C, 0.4 Apr. 11, 2024 C and 0.8 C, respectively (FIG. 67). This result indicates the enhanced rate performance relative to pristine AW and is comparable to new graphite or cAW, owing to the removal of resistive SEI by flash procedure. Once the rate is back to 0.2 C, the £AW has a capacity of 358.9 mAh g™'. [0356] Economic and Environmental Impact [0357] GREET 2020 and Everbatt 2020 developed by Argonne National Laboratory are used to compare the economic and environmental impacts to prepare synthetic graphite, cAW and fAW. The flow charts are shown in FIGS. 68A-68C. By providing local and momentary heating to the pristine AW, the SEI can be effectively decomposed within seconds in flash the recycling method. There is no need to carbonize or graphitize the carbonaceous materials as shown. in preparing synthetic graphite, or to heat the environment for several hours by high temperature calcination methods. Therefore, the flash recycling method reduces the recycling cost by ~48%, the GHG emissions by ~39% the water by ~98%, and the energy by ~48% (FIGS. 69A-69E). [0358] Since the average price for natural graphite mate- rial (battery grade) is ~10 USD per kg [Advincula 2021], there is a negative profit (-1.75 USD per kg) for synthetic graphite. Therefore, the price of synthetic graphite is higher in the current market (~20 USD per kg) and it is less competitive. By comparison, the high temperature calcina- tion method shows a slightly positive profit (0.70 USD per kg) and flash recycling method has the highest positive profit (3.90 USD per kg), which also reflects the potential for the present methods to increase the profit margin from battery recycling. [0359] Utilization [0360] Spent graphite anodes can be regenerated by the ultrafast and solvent-free flash recycling methods disclosed and taught herein. [0361] The obtained flash anode materials show intact 3D layered graphite core structure coated with solid-electrolyte interphase (SET)-derived layer. The valuable metals, lithium, cobalt, nickel, and manganese can be easily recovered from the flash anode products by a dilute acid post-treatment. The flash anode materials show the recovered electrochemical performance, compared with anode waste and new commer- cial graphite. [0362] Life-cycle analysis against current calcination method highlights that flash recycling method can signifi- cantly reduce the total energy and greenhouse gas emissions while turning it into an economically advantageous process. [0363] The formation of coating structure around graphite microparticles shows the feasibility about preparing the core-shell or other hierarchical topological structure by a solvent-free flash method within seconds. [0364] In embodiments, the electrolyte can be removed from the anode material as well as the separator and current collector. In other embodiments one or more of the electro- lyte, separator, and current collector can be retained and flashed with the anode materials in the mixture. Destroying 3D Morphology of The Cathode [0365] In some embodiments as discussed and described above, the 3D structure of the cathode can be maintained during the flash Joule heating. However, in some circum- stances, there is no care to retain the 3D structure of the cathode, such as because the former 3D structure is no longer compatible with the newer battery technologies. This can be especially the circumstance because battery designs
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US 2024/0120506 Al tend to be upgraded every two to three years. In such circumstances (when there is no need to retain the 3D morphology), the only desire would be to easily obtain the metals, Li, Co, plus Mn, Ni, and Cu, as well as other metals as applicable. [0366] It has been discovered that by using a flash Joule heating pulse that is higher in current than previously used and described, this will form easily dissolved metal oxides, while decomposing the 3D cathode morphology. The reuse of valuable metals such as Li, Co, Mn and Ni, reduces the need for mining from ores, and protects the environment. Moreover, acid concentration is far less than required by typical hydrometallurgical recycling, and the energy requirements are far less than those needed for pyrometal- lurgical recycling. Still further, such higher current FJH method can obtain the lithium salts, unlike the pyrometal- lurgical methods (described hereinabove) afford. Formerly, when retaining the 3D structure of the cathode, 120 V and 30 A for 150 milliseconds to 300 milliseconds was utilized, and this used 10 wt % conductive carbon additive. Using the same flash vessel size, to destroy the 3D cathode structure, leaving the more easily dissolved metals in the flash vessel, substantially as metal oxides and metal(0), was performed by increasing the conditions to 120 V and 90 A to 100 A for 500 milliseconds while using 33.3 wt % conductive carbon additive. Using the same vessel size, volatilizing out the metals from the flash container and into a trap can be obtained by utilizing 120 V at approximately 200 A to 300 A for 500 ms to 1 second, using 33.3 wt % carbon additive. [0367] Such high current FJH method can decompose the cathode materials into simple metal oxides and even metal (0), which are easy to dissolve in dilute acids such as 0.1 M HCI and even 0.01 M HCI. This acid is far less corrosive than the reagents used in current hydrometallurgical meth- ods, such as 12 M HC] and peroxides and NaOH rinses. [0368] By way of comparison, FJH was performed under conditions (A) to retain the 3D structure and (B) destroy the 3D structure. For the former (flash conditions to retain the 3D structure), the conditions were 10 wt % conductive carbon added, 120 V, 30 Amps, 300 ms flash time for LCO and 150 ms for NMC, and magnetic extraction of the desired contents. For the latter (flash condition to destroy the 3D structure), the conditions were 33 wt % conductive carbon added, 120 V, 100 Amps, 500 ms flash time for both LCO and NMC, no magnetic extraction, instead the contents are rinsed with dilute acid to obtain the desired metal oxides. [0369] The FJH method provided rapid electrical energy within 500 ms thereby avoiding the weight loss of metals with a low boiling point, such as Li. The metal contents in the flash Joule heating reactor remained in the reactor when the graphite electrode spacers were snuggly fitting. Loss of the metals by sublimation was not a problem as seen in FIG. 70. [0370] The total amounts of Li and Co from LCO and flash LCO were measured by leaching with concentrated HCI solutions. After flash treatment, the Li and Co recovery ratio were ~100% as shown in FIG. 71, which indicated there was no obvious metal loss by FJH treatment. [0371] Different concentrations of HCI were used to leach the metal salts, and the recovery efficiencies are compared in FIGS. 72A-72B. As shown in FIG, 72<, for Li, by changing the concentration, Li can be effectively recovered from LCO and flash LCO (curves 7201-7202, respectively) with an efficiency >90%, and a slightly higher efficiency can be seen Apr. 11, 2024 from flash LCO. As shown in FIG. 72B, for Co, as the concentration of the acid decreases, the recovery efficiency decreases in LCO (curves 7203-7204, for LCO and flash LCO, respectively). [0372] However, the efliciency of Co does not decrease for flash LCO. [0373] The distribution of the metal after FJH was also analyzed separately from the powdered FJH product in the chamber, the quartz tube cell, and the graphite electrodes. See FIG. 73. ~30% of the metal ions adhered to the quartz tube and graphite and the remaining 70% was within the powdered product. [0374] The total amounts of Li, Co, Ni and Mn from NMC. and flash NMC were also measured by leaching with con- centrated HCI solutions. After flash treatment, the Li, Co, Ni and Mn recovery ratio could be ~100%, as shown in FIG. 74, which indicated there was no obvious metal loss by FJH treatment. Note that a quartz tube is only used here as a convenient transparent vessel for the research scale. Upon scaling, quartz tubes would typically not be used due to their cost and fragility. Other reactor cells would be used, such as ceramic, concrete, and high temperature concrete. Teflon and polyphenenylene sulfide tubes, which are high-tempera- ture-stable plastics, can even be used since the electrical current does not pass through these insulating materials so that their temperature increase is little. [0375] In FIGS. 75A-75D, curves 7501-7504 show, respectively, the recovery yield of Li, Co, Ni and Mn from NMC in HC! solutions with different concentrations, and curves 7505-7508 show, respectively, the recovery yield of Li, Co, Ni and Mn from flash NMC in HCI solutions with different concentrations. These curves reveal that 0.1 M HCI was suflicient to remove the metal salts from the flashed cathodes. [0376] While embodiments of the invention have been shown and described, modifications thereof can be made by one skilled in the art without departing from the spirit and teachings of the invention. The embodiments described and the examples provided herein are exemplary only, and are not intended to be limiting. Many variations and modifica- tions of the invention disclosed herein are possible and are within the scope of the invention. The scope of protection is not limited by the description set out above, but is only limited by the claims which follow, that scope including all equivalents of the subject matter of the claims. [0377] The disclosures of all patents, patent applications, and publications cited herein are hereby incorporated herein by reference in their entirety, to the extent that they provide exemplary, procedural, or other details supplementary to those set forth herein. [0378] Amounts and other numerical data may be pre- sented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of approximately | to approxi- mately 4.5 should be interpreted to include not only the explicitly recited limits of 1 to approximately 4.5, but also to include individual numerals such as 2, 3, 4, and sub- ranges such as | to 3, 2 to 4, etc. The same principle applies to ranges reciting only one numerical value, such as “less
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US 2024/0120506 Al 21 than approximately 4.5,” which should be interpreted to include all of the above-recited values and ranges. Further, such an interpretation should apply regardless of the breadth of the range or the characteristic being described. [0379] Unless defined otherwise, all technical and scien- tific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the presently disclosed subject matter belongs. Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the presently disclosed subject matter, representative methods, devices, and materials are now described [0380] Following long-standing patent law convention, the terms “a” and “an” mean “one or more” when used in this application, including the claims. [0381] Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Accord- ingly, unless indicated to the contrary, the numerical param- eters set forth in this specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the presently disclosed subject matter. [0382] As used herein, the term “about” and “substan- tially” when referring to a value or to an amount of mass, weight, time, volume, concentration or percentage is meant to encompass variations of in some embodiments +20%, in some embodiments +10%, in some embodiments +5%, in some embodiments +1%, in some embodiments +0.5%, and in some embodiments +0.1% from the specified amount, as such variations are appropriate to perform the disclosed method. [0383] As used herein, the term “substantially perpendicu- lar” and “substantially parallel” is meant to encompass variations of in some embodiments within +10° of the perpendicular and parallel directions, respectively, in some embodiments within +5° of the perpendicular and parallel directions, respectively, in some embodiments within +1 of the perpendicular and parallel directions, respectively, and in some embodiments within +0.5° of the perpendicular and parallel directions, respectively. [0384] As used herein, the term “and/or” when used in the context of a listing of entities, refers to the entities being present singly or in combination. Thus, for example, the phrase “A, B, C, and/or D” includes A, B, C, and D individually, but also includes any and all combinations and subcombinations of A, B, C, and D. Abbreviations [0385] Abbreviations used throughout this application are further provided below. [0386] AW: Anode Waste [0387] cAW: Calcinated AW [0388] CB: Carbon black [0389] CEI: Cathode electrolyte interphase [0390] CW: Cathode waste [0391] fAW: Flash AW [0392] fCW: Flash CW [0393] fLCO: Flash LCO [0394] fNMC: Flash NMC [0395] FJH: Flash Joule heating [0396] GHG: Greenhouse gas [0397] Hydro: Hydrometallurgical Apr. 11, 2024 ife cycle analysis ithium cobalt oxide (LiCoO,) [0400] LIB: Li-ion battery [0401] NMC: Lithium nickel-manganese-cobalt oxide (LiNi,Mn,Co.0,, normally referred as NMCxyz, such as NMC811) [0402] R-CW: Resynthesized cathode material [0403] Pyro: Pyrometallurgical [0404] SET: solid electrolyte interphase [0405] It should be noted that the nomenclature for the terms “LCO” and “NMC” utilized herein is consistent with the terminology used in the art. For cathodes of lithium cobalt oxide, the term LCO includes lithium within the acronym. However, for cathodes of lithium nickel-manga- nese-cobalt oxide, the term NMC does not include lithium within the acronym. To avoid any confusion, as used herein, the term “NMC” is synonymous with the terms “Li-NMC” and “LNMC,” which are examples of alternative terms used in the art for lithium nickel-manganese-cobalt oxide (used in cathodes). In the battery fully charged state, much of the lithium resides in the anode. In the battery discharged state, much of the lithium resides in the cathode and little in the anode. So the quantity of lithium in the cathode depends on the state of the charge. In general, batteries would be discharged before recycling. This would drive most of the lithium ions into the cathode. Hence, in the case of NMC cathodes, it would contain much lithium upon battery dis- charge and could be described well as lithium nickel man- ganese cobalt. In the case of LCO, a portion of the lithium migrates from the cathode to the anode. 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[0454] Zou, H., et al, “A Novel Method To Recycle Mixed Cathode Materials For Lithium Ion Batteries,” Green Chem., 2013, 15, 1183 (“Zou 2013”). 1. A method of recovering metal, wherein the method comprises: (a) forming a mixture comprising a cathode material, wherein the cathode material is prepared from one or more batteries; (b) applying a voltage across the mixture to obtain metals and cathode waste from the cathode material, wherein (i) the voltage is applied in one or more voltage pulses, and Gi) duration of each of the one or more voltage pulses is for a duration period; and (c) magnetically separating the metal and the cathode waste. 2. The method of claim 1, wherein the metal comprises cathode metal selected from the group consisting of lithium, cobalt, nickel, manganese, iron, and combinations thereof. 3. The method of claim 1, wherein the metal comprises cathode metal selected from the group consisting of be metal oxides, metal salts, metal carbonates, metal phosphates, and combinations thereof. 4. The method of claim 3, wherein the cathode metal comprises metal oxide. 5. The method of claim 4, wherein the metal oxide comprises cobalt oxide. 6. The method of claim 3, wherein the cathode metal comprises metal carbonate. 7. The method of claim 6, wherein the metal carbonate comprises lithium carbonate. 8. The method of claim 3, wherein the cathode metal comprises metal phosphate. 9. The method of claim 8, wherein the metal phosphate comprises iron phosphate. 10. (canceled) 11. The method of claim 1, wherein the one or more batteries comprise one or more lithium-ion batteries. 12. The method of claim 11, wherein the one or more lithium-ion batteries comprise lithium-ion batteries each having a lithium cobalt oxide (LCO) cathode or a lithium nickel-manganese-cobalt oxide (NMC) cathode. 13. The method of claim 12, wherein each of the one or more lithium-ion batteries each comprise an LCO cathode. Apr. 11, 2024 14. The method of claim 12, wherein each the one or more lithium-ion batteries each comprise an NMC cathode. 15-18. (canceled) 19. The method of claim 1, wherein the mixture further comprises a conductive additive. 20-56. 57. The method of claim 1, wherein the method preserves the 3D layer structure of the cathodes in the cathode mate- rial. 58. The method of claim 1, wherein the method preserves the 3D morphology of the cathodes in the cathode material. 59. The method of claim 1, wherein the method destroys the 3D morphology of the cathodes in the cathode material. 60. The method of claim 1 further comprising a cooling step, wherein the cooling step cools the metals and the cathode waste before the step of magnetically separating the metals and the cathode waste. 61-62. (canceled) 63. The method of claim 1, wherein the method further comprises, after the step of mechanical separating, applying a second voltage across the cathode waste, wherein (a) the second voltage is applied in one or more second voltage pulses; and (b) duration of each of the one or more second voltage pulses is for a second duration period. 64. (canceled) 65. The method of claim 63, wherein (a) the applying of the second voltage across the cathode waste obtains further metals and a reduced portion of the cathode waste, and (b) the method further comprises magnetically separating the additional metals and the reduced portion of the cathode waste. 66. The method of claim 65, wherein the further metals and reduced portion of the cathode waste are at a weight ratio of at least 1:1. 67-85. (canceled) 86. A system for performing the method of recovering metal utilizing the method of claim 1, wherein the system comprises: (a) a source of the mixture comprising the cathode mate- rial; (b) a cell operably connected to the source such that the mixture can be flowed into the cell and held under compression; (c) electrodes operatively connected to the cell; (d) a flash power supply for applying a voltage across the mixture to obtain metals and cathode waste from the cathode material; (e) a magnet in operable contact with the metals and cathode waste, wherein the magnet is operable for magnetically separating the metals and the cathode waste. 87. The system of claim 86, wherein the mixture further comprises a conductive additive. 88-97. (canceled) 98. A method of recovering metal, wherein the method comprises (a) forming a mixture comprising a cathode material, wherein the cathode material is prepared from one or more batteries comprising cathodes, (b) applying a voltage across the mixture to obtain metals and cathode waste from the cathode material, wherein (i) the voltage is applied in one or more voltage pulses,
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US 2024/0120506 Al Apr. 11, 2024 24 (ii) duration of each of the one or more voltage pulses is for a duration period, (iii) the method destroys 3D morphology of the cath- odes in the cathode material; and (c) extracting the metal from the cathode waste using an aqueous solution. 99. The method of claim 98, wherein the metals are selected from the group consisting of lithium, cobalt, nickel, manganese, copper, and iron. 100. The method of claim 99, where the metals are in the form of one or more metal salts. 101. The method of claim 100, wherein the one or more metal salts are in the form one or more oxides. 102. The method of claim 98, wherein the aqueous solution comprises an acid. 103-107. (canceled) 108. The method of claim 98, wherein the one or more batteries comprising cathodes comprises cathodes selected from the group consisting of LCO lithium cobalt oxide (LCO) cathodes and NMC lithium nickel-manganese-cobalt oxide (NMC) cathodes. 109-145. (canceled) + 8 ke &
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