Flash Battery Recycling

Abstract

A method and system for flash recycling of batteries, such as lithium ion batteries, other metal (sodium, potassium, zinc, magnesium, and aluminum) ion batteries, metal batteries, batteries with all metal oxide cathodes, and batteries with anodes containing graphite. The method and system includes a solvent-free and water-free flash joule heating (FJH) method performed on a mixture containing materials from the battery, which is performed in milliseconds to recycle the materials. In some embodiments, the FJH method can be combined with magnetic separation to recover lithium, cobalt, nickel, and manganese in yields as high as 98%. In some embodiments, the FJH method is followed by a rinse with a dilute acid, such as 0.01M HCl. In other embodiments, the FJH method is utilized to purify graphite in batteries, for example, for use in battery anodes.

Description

Related Applications

[0001] Cross-reference to related patent applications

[0001] This application claims priority to (a) U.S. Patent Application No. 63 / 147,069, entitled "Recycling Of Spent Batteries By Flash Joule Heating," filed February 8, 2021, to James M. Tour et al., and (b) U.S. Patent Application No. 63 / 285,952, entitled "Flash Recycling Of Batteries," filed December 3, 2021, to James M. Tour et al., each of which is commonly owned by the owner of the present invention. These patent applications are incorporated herein in their entireties. [Technical Field]

[0002] STATEMENT REGARDING FEDERALLY FUNDED RESEARCH 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 government has certain rights in this invention.

[0003] This invention relates to flash recycling of batteries, including lithium-ion batteries, other metal (sodium, potassium, zinc, magnesium, and aluminum)-ion batteries, metal batteries (e.g., solid-state lithium batteries), batteries with all-metal oxide cathodes, and batteries with all-graphite-containing anodes. Flash recycling is characterized by a solvent-free and water-free flash joule heating (FJH) process, sometimes performed in combination with magnetic separation to recover lithium, cobalt, nickel, manganese, etc., at the cathode, and further characterized by the FJH process to purify graphite in the battery, e.g., the graphite in the anode. [Background technology]

[0004] background

[0004] Due to the continuous accumulation of spent lithium-ion batteries (LIBs) and the increasing scarcity of their valuable metal sources, effective recycling strategies have been urgently needed [Tran 2019; Lv 2018; Xu 2020]. Current recycling methods can achieve high recovery rates of valuable metals, but they require high-temperature furnaces or harsh wet extraction methods, destroying the entire three-dimensional (3D) morphology of the cathode, making these methods economically and environmentally unattractive [Lv 2018; Natarajan 2018]. Therefore, with less than 5% of LIBs being recycled, there will always be a need to mine metals from their ores [Recycle 2019; Velazquez 2019; Li 2017].

[0005]

[0005] Demand for portable electronic devices and electric vehicles is ever-increasing, accelerating commercial production of secondary batteries, particularly LIBs. [Recycle 2019; Andre 2015] The market for rechargeable LIBs is expected to reach approximately $50 billion in 2020 and $70 billion in 2022. [Zou 2013] Given that the expected lifespan of most LIBs is less than 10 years, often as little as 2 years. [Salvatierra 2021; Chen 2020], the foreseeable staggering accumulation of used LIBs is disconcerting. [Recycle 2019; Velazquez 2019; Li 2017] Furthermore, at the projected pace of Li and Co mining, global reserves of these elements are projected to be depleted by 2050 and 2030, respectively. [Natarajan 2018; Jacoby 2020] Spent cathodes consist of lithium and transition metals, which account for approximately 35% of the total weight and 45% of the cost of LIBs. Effective recycling of spent cathodes would reduce the need for remote mining of these metals, reduce the environmental impact of LIB disposal, and provide an economic incentive for recycling [He 2016]. Anodes are graphite, which is cheaper than cathodes; however, the use of a form of battery-grade graphite is necessary, as natural sources of battery-grade graphite cost $10,000 per ton, and preferred synthetic battery-grade graphite can cost as much as $20,000 per ton. In addition, spent anodes contain several weight percent lithium and retain leached cathode metals, which have a higher metal content than mined ores. Therefore, from an environmental perspective, they cannot simply be landfilled, and recycling the components is attractive from an economic perspective 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) process performed on a mixture containing materials from lithium-ion batteries, other metal-ion batteries, metal batteries, batteries with all-metal oxide cathodes, and batteries with all-graphite-containing anodes, all in milliseconds. In some embodiments, the FJH process is combined with magnetic separation to recover lithium, cobalt, nickel, manganese, and other elements in yields as high as 98%. This process is called "flash recycling." Used LIBs with different chemistries, namely lithium cobalt oxide (LCO), lithium nickel-manganese-cobalt oxide (NMC), and both LCO and NMC mixed together, can be effectively flash recycled. Characterization of the flash recycling product revealed an intact 3D layered core structure with a hierarchical architecture, greatly simplifying reconstitution into new cathodes. The flash process has further been shown to produce a lithium-ion permeable conductive carbon coating on the flash cathode material, thereby imparting improved electrochemical stability to the flash cathode material. A life cycle analysis of current recycling processes highlights that flash recycling can be an economically advantageous process while significantly reducing total energy and greenhouse gas (GHG) emissions.

[0007] In another embodiment, the FJH method is used to purify graphite in metal ion batteries, such as graphite in anodes.

[0008] In general, in one embodiment, the invention features a method for recovering metals. 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 the metal and cathode waste from the cathode material. The voltage is applied in one or more voltage pulses. The duration of each of the one or more voltage pulses is for a predetermined period of time. The method further includes magnetically separating the metal and the cathode waste.

[0008]

[0009] Implementations of the invention may include one or more of the following features.

[0010] The metal may include a cathode metal selected from the group consisting of lithium, cobalt, nickel, manganese, iron, and combinations thereof.

[0009]

[0011] The metal comprises a cathode metal selected from the group consisting of metal oxides, metal salts, metal carbonates, metal phosphates, and combinations thereof.

[0012] The cathode metal may include a metal oxide.

[0010]

[0013] The metal oxide may include cobalt oxide.

[0014] The cathode metal may include a metal carbonate.

[0015] The metal carbonate may include lithium carbonate.

[0011]

[0016] The cathode metal may include a metal phosphate.

[0017] The metal phosphate may include iron phosphate.

[0018] The one or more batteries can include a battery selected from the group consisting of a lithium ion battery, a sodium ion battery, a potassium ion battery, a zinc ion battery, a magnesium ion battery, an aluminum ion battery, a metal ion battery, a metal battery, an anodeless battery, a metal oxygen battery, a metal air battery, and combinations thereof.

[0012]

[0019] The one or more batteries may include one or more lithium ion batteries.

[0020] The one or more lithium-ion cells may each include a lithium-ion cell having a lithium cobalt oxide (LCO) cathode or a lithium nickel-manganese-cobalt oxide (NMC) cathode.

[0013]

[0021] Each of the one or more lithium ion cells may include a respective LCO cathode.

[0022] Each of the one or more lithium-ion batteries may include a respective NMC cathode.

[0014]

[0023] The metal obtained by applying the voltage may include a cathodic metal including a metal phosphate.

[0024] The metal phosphate may include iron phosphate.

[0015]

[0025] Each of the portions of the one or more lithium ion batteries may include an LCO cathode, and each of the portions of the one or more lithium ion batteries may include an NMC cathode.

[0016]

[0026] The one or more lithium-ion batteries may include a lithium-ion battery having a cathode comprising a mixture of lithium cobalt oxide (LCO) and lithium nickel-manganese-cobalt oxide (NMC).

[0017]

[0027] The mixture may further include a conductive additive.

[0028] The conductive additive may be a carbon source.

[0029] The conductive additive may be selected from the group consisting of graphite, anode graphite, battery grade graphite, elemental carbon, carbon black, graphene, flash graphene, turbostratic graphene, coal, anthracite, coke, metallurgical coke, calcined coke, activated carbon, biochar, carbon from natural gas with hydrogen atoms removed, activated carbon, shungite, plastic waste, carbon char derived from plastic waste, food waste, carbon char derived from food waste, biomass, biomass-derived carbon char, carbon char derived from hydrocarbon gas, and mixtures thereof.

[0018]

[0030] The conductive additive may be carbon black.

[0031] The conductive additive may be primarily elemental carbon.

[0032] The conductive additive may be selected from the group consisting of metals, metal salts, metal oxides, metalloids, metal complexes, conductive phosphorus, and non-metallic conductive materials.

[0019]

[0033] The conductive additive may be selected from the group consisting of metals, metal salts, metal oxides, metalloids, and metal complexes.

[0034] The conductive additive may be a metalloid.

[0020]

[0035] The metalloid may be selected from the group consisting of B, Si, As, Te, and At.

[0036] The conductive additive can be prepared from one or more of the battery's anode materials.

[0021]

[0037] The conductive additive may be prepared from one or more batteries.

[0038] The cathode material and the conductive additive may be mixed in a weight ratio ranging from 1:2 to 25:1.

[0022]

[0039] The applied voltage may be in the range of 15V to 300V.

[0040] The mass of the mixture to which the voltage is applied may be greater than 1 kg. The applied voltage may be between 100V and 100,000V.

[0023]

[0041] The mass of the mixture to which the voltage is applied may be greater than 100 kg.

[0042] The mass of the mixture to which the voltage is applied may be greater than 1 kg, and the applied current may be between 1,000 amp and 30,000 amp.

[0024]

[0043] The mass of the mixture to which the voltage is applied may be greater than 100 kg.

[0044] The mixture may have a resistance in the range of 0.1 ohms to 25 ohms when a voltage is applied.

[0025]

[0045] The period of time for each duration of the one or more voltage pulses may be between 1 microsecond and 25 seconds.

[0046] The period of time for each duration of the one or more voltage pulses may be between 1 microsecond and 10 seconds.

[0026]

[0047] The period of time for each duration of the one or more voltage pulses may be between 1 microsecond and 1 second.

[0048] The duration of each of the one or more voltage pulses may be between 100 microseconds and 500 microseconds.

[0027]

[0049] The one or more voltage pulses may be between 2 voltage pulses and 100 voltage pulses.

[0050] The voltage pulses can be implemented using direct current (DC).

[0028]

[0051] The method may be carried out using a pulsed direct current (PDC) Joule heating process.

[0052] The voltage pulses can be implemented using alternating current (AC).

[0029]

[0053] The voltage pulses can be implemented using both direct current (DC) and alternating current.

[0054] The method can alternate between using direct current (DC) and alternating current (AC).

[0030]

[0055] The method can use direct current (DC) and alternating current (AC) simultaneously.

[0056] One or more voltage pulses can increase the temperature of the mixture to at least 3000K.

[0031]

[0057] The metal obtained by applying a voltage across the mixture may include metal particles having a carbon coating.

[0058] The carbon coating may be electrically conductive.

[0032]

[0059] The carbon coating may be ion-permeable.

[0060] The carbon coating may be electrically conductive and may be ion-permeable.

[0061] The carbon coating may be ion-permeable to metal ions.

[0033]

[0062] The metal ions may be selected from the group consisting of lithium ions, sodium ions, potassium ions, magnesium ions, zinc ions, and aluminum ions.

[0034]

[0063] The carbon coating may be amorphous.

[0064] The carbon coating may include graphene.

[0065] The method can preserve the 3D layer structure of the cathode in the cathode material.

[0035]

[0066] The method can preserve the 3D morphology of the cathode in the cathode material.

[0067] The method can destroy the 3D morphology of the cathode in the cathode material.

[0068] The method may further comprise a cooling step, which may cool the metal and cathode waste prior to the step of magnetically separating the metal and cathode waste.

[0036]

[0069] The metal and cathode waste may be in a weight ratio of 20:1 to 5:1.

[0070] The metal and cathode waste may be in a weight ratio of 10:1 to 8:1.

[0071] The method may further include applying a second voltage across the cathode waste after the mechanical separating step. The second voltage may be applied in one or more second voltage pulses. The duration of each of the one or more second voltage pulses may be for a period of the second duration.

[0037]

[0072] The second voltage may be the same as the voltage applied across the cathode material. The period of the second duration may be the same as the period of the voltage applied across the cathode material.

[0038]

[0073] Applying a second voltage across the cathode waste can capture additional metal and a reduced portion of the cathode waste. The method may further include magnetically separating the additional metal and the reduced portion of the cathode waste.

[0039]

[0074] The further metal and the reduced portion of the cathode waste may be in a weight ratio of at least 1:1.

[0075] The further metal and the reduced portion of the cathode waste may be in a weight ratio of at least 1.5:1.

[0040]

[0076] The method may further comprise recovering the metals by separating them from the cathode waste and then collecting them.

[0077] The cathode material may include a first mass of a cathode metal selected from the group consisting of lithium, cobalt, nickel, magnesium, and combinations thereof, and the collected metal may comprise at least 70 wt% of the first mass of the cathode metal.

[0041]

[0078] The collected metal may comprise at least 70 wt% of the lithium in the first mass of the cathode metal.

[0079] The collected metal may comprise at least 70 wt% of the cobalt in the first mass of cathode metal.

[0042]

[0080] The collected metal may comprise at least 70 wt% of the nickel in the first mass of cathode metal.

[0081] The collected metal may comprise at least 70 wt% of the magnesium in the first mass of cathode metal.

[0043]

[0082] The collected metal may include at least 70 wt% of each of the lithium, cobalt, nickel, and magnesium in the first mass of cathode metal.

[0083] The collected metal may comprise at least 90 wt% of the lithium in the first mass of the cathode metal.

[0044]

[0084] The collected metal may comprise at least 90 wt% of the cobalt in the first mass of cathode metal.

[0085] The collected metal may comprise at least 90 wt% of the nickel in the first mass of cathode metal.

[0045]

[0086] The collected metal may comprise at least 90 wt% of the magnesium in the first mass of cathode metal.

[0087] The collected metals may include at least 90 wt% of each of the lithium, cobalt, nickel, and magnesium in the first mass of cathode metal.

[0046]

[0088] The method can be carried out in a continuous or automated process.

[0089] The metal may be recycled into new metal-ion or metal batteries.

[0090] The metal may be recycled as a cathode material in new metal-ion or metal batteries.

[0047]

[0091] In general, in another embodiment, the invention features a method for recovering metals. 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 the metal and cathode waste from the cathode material. The voltage is applied in one or more voltage pulses. The duration of each of the one or more voltage pulses is for a predetermined period of time. The method further includes magnetically separating the metal and the cathode waste.

[0048]

[0092] Implementations of the invention may include one or more of the following features.

[0093] The one or more batteries may be one or more non-lithium metal ion batteries.

[0049]

[0094] The one or more batteries may 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-less batteries, metal oxygen batteries, metal air batteries, and combinations thereof.

[0050]

[0095] In general, in another embodiment, the invention features a system for carrying out a method for recovering metals utilizing at least one of the above-described methods for recovering metals. The system includes a source of a mixture including a cathode material. The system further includes a cell operably connected to the source, such that the mixture flows through the cell and is held under compression. The system further includes electrodes operably connected to the cell. The system further includes a flash power supply for applying a voltage across the mixture to obtain metal and cathode waste from the cathode material. The system further includes a magnet in operable contact with the metal and cathode waste. The magnet is operable in response to magnetically separating the metal and cathode waste.

[0051]

[0096] Implementations of the invention may include one or more of the following features.

[0097] In general, in another embodiment, the invention features.

[0098] Implementations of the invention may include one or more of the following features.

[0052]

[0099] The mixture may further include a conductive additive.

[0100] The system may be operable to carry out a continuous or automated process.

[0053]

[0101] In general, in another embodiment, the invention features a method for recovering metals. The method includes forming a mixture including battery material. The battery material is prepared from one or more batteries. The method further includes applying a voltage across the mixture to obtain the metal and battery waste from the battery material. The voltage is applied in one or more voltage pulses. The duration of each of the one or more voltage pulses is for a predetermined period of time. The method further includes magnetically separating the metal and battery waste.

[0054]

[0102] Implementations of the invention may include one or more of the following features.

[0103] The one or more batteries may include one or more lithium ion batteries.

[0055]

[0104] The one or more batteries may 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 batteries, anode-less batteries, metal oxygen batteries, metal air batteries, and combinations thereof.

[0056]

[0105] The mixture may further include a conductive additive.

[0106] In general, in another embodiment, the invention features a system for carrying out a method for recovering metals utilizing the above-described methods for recovering metals. The system includes a source of a mixture including battery material. The system further includes a cell operably connected to the source, such that the mixture flows through the cell and is held under compression. The system further includes electrodes operably connected to the cell. The system further includes a flash power supply for applying a voltage across the mixture to obtain the metal and battery waste from the battery material. The system further includes a magnet in operable contact with the metal and battery waste. The magnet is operable in response to magnetically separating the metal and battery waste.

[0057]

[0107] Implementations of the invention may include one or more of the following features.

[0108] The battery material may include lithium ion battery material.

[0109] The battery material may be a non-lithium metal ion battery material selected from the group consisting of sodium ion battery materials, potassium ion battery materials, zinc ion battery materials, magnesium ion battery materials, aluminum ion battery materials, and combinations thereof.

[0058]

[0110] The mixture may further include a conductive additive.

[0111] The system may be operable to carry out a continuous or automated process.

[0059]

[0112] In general, in another embodiment, the invention features a method for recovering metals. The method includes forming a mixture including a cathode material. The cathode material is prepared from one or more batteries including a cathode. The method further includes applying a voltage across the mixture to obtain the metal and cathode waste from the cathode material. The voltage is applied in one or more voltage pulses. The duration of each of the one or more voltage pulses is for a predetermined period of time. The method disrupts the 3D morphology of the cathode in the cathode material. The method further includes extracting the metal from the cathode waste using an aqueous solution.

[0060]

[0113] Implementations of the invention may include one or more of the following features.

[0114] The metal may be selected from the group consisting of lithium, cobalt, nickel, manganese, copper, and iron.

[0061]

[0115] The metal may be in the form of one or more metal salts.

[0116] The one or more metal salts may be in the form of one or more oxides.

[0062]

[0117] The aqueous solution may contain an acid.

[0118] The acid may be HCl in the range of 0.01M to 12M.

[0119] The acid may be HCl in the range of 0.01M to 0.1M.

[0063]

[0120] The acid may range from 0.01M to 15M.

[0121] The acid may range from 0.01M to 0.1M.

[0122] The voltage can be applied in the range of 1 to 100 voltage pulses.

[0064]

[0123] The one or more cells that include a cathode may include a cathode selected from the group consisting of an LCO cathode and an NMC cathode.

[0124] In general, in another embodiment, the invention features a system for carrying out a method for recovering metals utilizing at least one of the methods described above. The system includes a source of a mixture including a cathode material. The system further includes a cell operably connected to the source, such that the mixture flows through the cell and is held under compression. The system further includes electrodes operably 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 an aqueous solution. The aqueous solution is operative in response to extracting metals from the cathode waste.

[0065]

[0125] Implementations of the invention may include one or more of the following features.

[0126] The mixture may further include a conductive additive.

[0127] The system may be operable to carry out a continuous or automated process.

[0066]

[0128] In general, in another embodiment, the invention features a method for 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 refine the graphite in the mixture. The voltage is applied in one or more voltage pulses. The duration of each of the one or more voltage pulses is for a predetermined period of time. The method further includes utilizing the refined graphite by applying the voltage in one or more new batteries.

[0067]

[0129] Implementations of the invention may include one or more of the following features.

[0130] The one or more batteries may include one or more lithium ion batteries.

[0068]

[0131] The one or more batteries may 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.

[0069]

[0132] The one or more new batteries may include one or more new lithium ion batteries.

[0133] The one or more new batteries may include one or more new lithium ion batteries.

[0070]

[0134] The one or more batteries may 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-less batteries, metal oxygen batteries, metal air batteries, and combinations thereof.

[0071]

[0135] The mixture may consist of an anode material.

[0136] The mixture may further include cathode materials from one or more batteries.

[0072]

[0137] The mixture may include an anode material mixed with a conductive additive that is not an anode material.

[0138] The conductive additive may be a carbon source.

[0073]

[0139] The conductive additive may be selected from the group consisting of graphite, anode graphite, battery grade graphite, elemental carbon, carbon black, graphene, flash graphene, turbostratic graphene, coal, anthracite, coke, metallurgical coke, calcined coke, activated carbon, biochar, carbon from natural gas with hydrogen atoms removed, activated carbon, shungite, plastic waste, carbon char derived from plastic waste, food waste, carbon char derived from food waste, biomass, biomass-derived carbon char, carbon from hydrocarbon gas, and mixtures thereof.

[0074]

[0140] The conductive additive may be carbon black.

[0141] The conductive additive may be primarily elemental carbon.

[0142] In general, in another embodiment, the invention features a system for carrying out a method for recycling anode material utilizing at least one of the methods for recycling anode material described above. The system includes a source of a mixture including anode material including graphite. The system further includes a cell operably connected to the source, such that the mixture flows through the cell and is held under compression. The system further includes electrodes operably connected to the cell. The system further includes a flash power supply for applying a voltage across the mixture to refine the graphite in the anode material.

[0075]

[0143] Implementations of the invention may include one or more of the following features.

[0144] The anode material may include a lithium ion battery anode material.

[0145] The anode material may comprise a non-lithium metal-ion battery anode material selected from the group consisting of a lithium-ion battery anode material, a sodium-ion battery anode material, a potassium-ion battery anode material, a zinc-ion battery anode material, a magnesium-ion battery anode material, an aluminum-ion battery anode material, and combinations thereof.

[0076]

[0146] The mixture may include an anode material mixed with a conductive additive that is not an anode material.

[0147] The system may be operable to carry out a continuous or automated process.

[0077]

[0148] In general, in another embodiment, the invention features a method that includes selecting a graphite anode material from a battery. The method further includes applying flash Joule heating to the graphite anode material to form a flashed graphite anode material. The application of flash Joule heating purifies the graphite anode material.

[0078]

[0149] Implementations of the invention may include one or more of the following features.

[0150] The battery may be a lithium ion battery.

[0151] The battery may be a battery selected from the group consisting of a lithium ion battery, a sodium ion battery, a potassium ion battery, a zinc ion battery, a magnesium ion battery, an aluminum ion battery, and combinations thereof.

[0079]

[0152] Flash Joule heating may include applying a voltage across the graphite anode material. The voltage may be applied in one or more voltage pulses. The duration of each of the one or more voltage pulses may be for a period of predetermined duration.

[0080]

[0153] The method may further include using the flashed graphite anode material in a second battery.

[0154] The second battery may be a second lithium ion battery.

[0081]

[0155] The battery may be a lithium ion battery.

[0156] The second battery may be a second non-lithium metal ion battery selected from the group consisting of a sodium ion battery, a potassium ion battery, a zinc ion battery, a magnesium ion battery, an aluminum ion battery, and combinations thereof.

[0082]

[0157] The battery may be a non-lithium metal ion battery selected from the group consisting of a sodium ion battery, a potassium ion battery, a zinc ion battery, a magnesium ion battery, an aluminum ion battery, and combinations thereof.

[0083]

[0158] The method may further include washing the flashed graphite anode material to separate inorganic metals and salts in the flashed graphite anode material from the graphite.

[0084]

[0159] The method may further include using the flashed graphite anode material in a second battery after cleaning.

[0160] The second battery may be a second lithium ion battery.

[0085]

[0161] The battery may be a lithium ion battery.

[0162] The second battery may be a battery selected from the group consisting of a lithium ion battery, a sodium ion battery, a potassium ion battery, a zinc ion battery, a magnesium ion battery, an aluminum ion battery, and combinations thereof.

[0086]

[0163] The battery may be a battery selected from the group consisting of a lithium ion battery, a sodium ion battery, a potassium ion battery, a zinc ion battery, a magnesium ion battery, an aluminum ion battery, and combinations thereof.

[0087]

[0164] In general, in another embodiment, the invention features a method for resynthesizing a cathode material. The method includes subjecting the cathode material to a flash Joule heating process to form a ferromagnetic flash product. The method further includes subjecting the ferromagnetic flash product to a hydrothermal and calcination process to form a resynthesized cathode material. [Brief explanation of the drawings]

[0088] [Figure 1-1]

[0165] 1A-1F are schematic diagrams and graphs relating to flash recycling of cathode waste. Figure 1A is a schematic diagram of a flash recycling process for cathode waste. Figures 1B-1C are schematic diagrams of conventional hydrometallurgical and pyrometallurgical processes, respectively. [Figure 1-2] Figure 1D is a graph showing real-time temperature measurements by fitting blackbody radiation from samples during the flash recycling process and enumerating rapid cooling, all completed in less than 0.5 seconds. Figure 1E is a graph showing the temperature-vapor pressure relationship for various metals contained in the cathode waste. Figure 1F is a graph showing the magnetic response of the unflashed cathode waste, the ferromagnetic portion of the flash-recycled cathode waste (which is approximately 90% of the product), and the non-ferromagnetic portion of the flash-recycled cathode waste (which is approximately 10% of the product). [Figure 2-1]

[0166] Figures 2A-2B show a scheme of the FJH system. Figure 2A is an electrical schematic diagram of the FJH system. Figure 2B is a photograph of the FJH reaction box. [Figure 2-2]

[0166] Figures 2A-2B show a scheme of the FJH system. Figure 2A is an electrical schematic of the FJH system. Figure 2B is a diagram of the FJH reaction box. [Figure 3]

[0167] Figures 3A-3C show current-time curves during flash reactions. Figure 3A is a graph of a new lithium cobalt oxide (LiCoO) (LCO) cathode material. Figure 3B is a graph of a new lithium nickel-manganese-cobalt oxide (LiNixMnyCozO2, commonly referred to as NMCxyz, e.g., NMC811) (NMC) cathode material. Figure 3C is a graph of cathode waste obtained from a spent LIB. The vertical lines in the current sweep reflect 1000 Hz cycling of the electrical input. [Figure 4]

[0168] Figure 4 shows the spectra recorded by a spectrometer with 16 optical channels. The wavelengths of these channels range from 1000 nm to 640 nm at equal intervals of 24 nm. Then, fitting of blackbody radiation (BBR) was used to obtain the temperature at each time point shown in Figure 1D. [Figure 5]

[0169] Figures 5A-5B show the magnetic response of the cathode material. Figure 5A shows the enlarged hysteresis loops of the CW, the non-ferromagnetic portion of the flash-recycled CW (fCW non-magnetic), and the ferromagnetic portion of the flash-recycled CW (fCW magnetic). Figure 5B shows the behavior of the hysteresis loops around the onset of fCW magnetism. [Figure 6]

[0170] Figures 6A-6D show the magnetic response of the cathode waste and flash products. Figures 6A-6B are illustrations showing that the cathode waste was not attracted by a bar magnet. Figures 6C-6D show that the flash-recycled CW is predominantly ferromagnetic. [Figure 7]

[0171] Figure 7 shows the magnetic response of the reflashed cathode material. The magnetic response is for the ferromagnetic portion of the reflashed recycled cathode waste, which is about 60 wt% of the product, and the non-ferromagnetic portion of the reflashed recycled cathode waste, which is about 40 wt% of the product. The similar magnetization behavior of the ferromagnetic portion of the reflashed recycled cathode waste confirms their effective separation with the same magnet having a field strength of about 5000 Oe. [Figure 8-1]

[0172] Figures 8A-8E show the structure and chemical composition of the reflash-recycled product. Figure 8A shows the FTIR spectra of the non-ferromagnetic portion of the reflash-recycled CW (LCO plus NMC), the ferromagnetic portion of the reflash-recycled CW, and the non-ferromagnetic portion of the reflash-recycled CW. Figure 8B shows the XRD spectrum of the ferromagnetic portion of the reflash-recycled CW. Figure 8C shows an SEM image of the ferromagnetic portion of the reflash-recycled CW. [Figure 8-2] Figure 8D is the energy dispersive analysis elemental mapping, and Figure 8E is the corresponding spectrum of the ferromagnetic part of the reflash-recycled CW. [Figure 9]

[0173] Figures 9A-9D show the magnetic response of various cathode materials. Figure 9A shows the hysteresis loops at room temperature (300 K) for NMC and the ferromagnetic portion of flash-recycled NMC (fNMC magnetic). Figure 9B shows the behavior of the hysteresis loops around the onset for NMC and fNMC. Figure 9C shows the hysteresis loops at room temperature (300 K) for LCO and the ferromagnetic portion of flash-recycled LCO (fLCO magnetic). Figure 9D shows the behavior of the hysteresis loops around the onset for LCO and fLCO. [Figure 10]

[0174] 10A-10B are visual images of the ferromagnetic portion of LCO from approximately 200 mg scale and approximately 800 mg scale, respectively.

[0175] 10C-10D are visual images of the ferromagnetic portion of NMC811 from approximately 200 mg scale and approximately 800 mg scale, respectively. [Figure 11-1]

[0176] Figures 11A-11G show the recovery efficiencies of various cathode materials. Figure 11A is a graph showing the recovery rates of Li and Co in the ferromagnetic fraction of flash-recycled LCO products after a single flash (1.0 = 100%). The number of samples is N=5, and the bars indicate the standard deviation between runs. Figure 11B is a graph showing a comparison of the recovery rates of Li and Co using different recycling methods, along with references. Figure 11C is a graph showing the recovery rates of Li, Co, Ni, and Mn in the ferromagnetic fraction of flashed NMC811 (N=5). Figure 11D is a graph showing the recovery rates of Li, Co, Ni, and Mn in the ferromagnetic fraction of flashed commercial cathode waste (fCW) from spent LIBs (N=5). For Figures 11C-11D, the yields are compared to the content of metals recovered by aqueous acid digestion, and therefore may exceed 1.0 in some cases. [Figure 11-2] 11E-11G are radar plots reporting the recovery of various metals from cathode waste using flash recycling and traditional hydrometallurgical and pyrometallurgical methods, respectively. For FIG. 11E, the darker shading is recovery after a single flash, and the lighter shading is recovery after a second flash. [Figure 12]

[0177] 12A-12C are radar plots reporting a comparison of the recovery of various metals from LCO using flash recycling and traditional hydrometallurgical and pyrometallurgical methods, respectively. The structural retention factor R value is 7.77 / 3.03=2.57 for LCO.

[0178] 12D-12F are radar plots reporting a comparison of the recovery of various metals from NMC using flash recycling and traditional hydrometallurgical and pyrometallurgical methods, respectively. The structural retention factor R value is 0.29 / 0.57 = 0.51 for NMC. [Figure 13-1]

[0179] Figures 13A-13J show the structure and chemical composition of flash-recycled products. Figure 13A shows high-resolution XPS spectra of Co 2p in the surface and subsurface regions of the ferromagnetic portion of flash-recycled CW (fCW). Figure 13B shows a graph showing the elemental ratios at different depths in the ferromagnetic portion of fCW (LCO+NMC). The spectra were acquired at different depths after surface etching. Electrolyte-derived fluoride was deposited during CEI formation in the spent LIB. Figure 13C shows a schematic diagram of the ferromagnetic portion of an fCW particle with a hierarchical structure. [Figure 13-2] Figure 13D shows an HAADF image and corresponding energy-dispersive analysis elemental mapping of the ferromagnetic portion of fLCO. Figure 13E shows the atomistic structures of partially delithiated LiCoO before flash recycling and the high-quality LiCoO, CoO, and CoO obtained after flash recycling. The right panel demonstrates the magnetization of CoO by plotting the difference between the spin density distributions of the spin-up and spin-down configurations at a maximum magnetic moment of 0.02 e / Å, approximately 70 emu / g. [Figure 13-3] Figure 13F is an HR-TEM image of R-LCO reporting the presence of a layered structure at the surface. The inset in Figure 13F is the corresponding FFT pattern. Figure 13G is an atomic resolution HAADF-STEM image of R-LCO. [Figure 13-4] FIG. 13H is the HAADF image of R-CW and the corresponding energy dispersive analysis elemental mapping. [Figure 13-5] FIG. 13I is an image of the Li-ion permeable partially graphitized amorphous carbon structure at the end of 9 ns of annealing at 2500 K, where the lines shown are potential Li-ion trajectories. [Figure 13-6] Figure 13J is a graph showing the electrochemical performance of spent CW, resynthesized cathode material, and fresh LCO in the prepared half-cells. The rate for testing is 0.2 C. [Figure 14-1]

[0180] Figures 14A-14E show the chemical composition of ferromagnetic flash-recycled CW (fCW) derived from a mixture of LCO and NMC contained in a used commercial laptop computer battery. Figure 14A shows the full-scan XPS results of the ferromagnetic fCW. Figures 14B-14E show the high-resolution XPS spectra of C 1s, O 1s, F 1s, and Li 1s at the surface and subsurface regions of the ferromagnetic fCW, respectively. After surface etching, the spectra were acquired at different depths. [Figure 14-2] Figures 14A-14E show the chemical composition of ferromagnetic flash-recycled CW (fCW) derived from a mixture of LCO and NMC contained in a used commercial laptop computer battery. Figure 14A shows the full-scan XPS results of the ferromagnetic fCW. Figures 14B-14E show the high-resolution XPS spectra of C 1s, O 1s, F 1s, and Li 1s at the surface and subsurface regions of the ferromagnetic fCW, respectively. After surface etching, the spectra were acquired at different depths. [Figure 15-1]

[0181] Figures 15A-15G show the chemical composition of CWs derived from a mixture of LCO and NMC obtained from a used commercial laptop computer battery. Figure 15A shows the full-scan XPS results of the CWs. Figures 15B-15F show the high-resolution XPS spectra of C 1s, Co 2p, F 1s, Li 1s, and O 1s at the surface and subsurface regions of the CWs, respectively. After surface etching, the spectra were acquired at different depths. Figure 15G shows the elemental ratios at different depths in the CWs. [Figure 15-2]

[0181] Figures 15A-15G show the chemical composition of CWs derived from a mixture of LCO and NMC obtained from a used commercial laptop computer battery. Figure 15A shows the full-scan XPS results of the CWs. Figures 15B-15F show the high-resolution XPS spectra of C 1s, Co 2p, F 1s, Li 1s, and O 1s at the surface and subsurface regions of the CWs, respectively. After surface etching, the spectra were acquired at different depths. Figure 15G shows the elemental ratios at different depths in the CWs. [Figure 16-1]

[0182] Figures 16A-16F show the chemical composition of the ferromagnetic portion (fLCO) of flash-recycled LCO from 0 nm to 500 nm. Figure 16A shows the full-scan XPS results of ferromagnetic fLCO. Figures 16B-16E show the high-resolution XPS spectra of C 1s, Co 2p, Li 1s, and O 1s in the surface and subsurface regions of fLCO, respectively. After surface etching, the spectra were acquired at different depths. Figure 16F shows the elemental ratios at different depths in ferromagnetic fLCO. [Figure 16-2]

[0182] Figures 16A-16F show the chemical composition of the ferromagnetic portion (fLCO) of flash-recycled LCO from 0 nm to 500 nm. Figure 16A shows the full-scan XPS results of ferromagnetic fLCO. Figures 16B-16E show the high-resolution XPS spectra of C 1s, Co 2p, Li 1s, and O 1s in the surface and subsurface regions of fLCO, respectively. After surface etching, the spectra were acquired at different depths. Figure 16F shows the elemental ratios at different depths of ferromagnetic fLCO. [Figure 17-1]

[0183] Figures 17A-17F show the chemical composition of the ferromagnetic portion (fLCO) of flash-recycled LCO from 0 nm to 100 nm. Figure 17A shows the full-scan XPS results of ferromagnetic fLCO. Figures 17B-17E show high-resolution XPS spectra of C 1s, Co 2p, Li 1s, and O 1s in the surface and subsurface regions of flash LCO, respectively. After surface etching, the spectra were acquired at different depths. Figure 17F shows the elemental ratios at different depths in ferromagnetic fLCO. [Figure 17-2]

[0183] Figures 17A-17F show the chemical composition of the ferromagnetic portion (fLCO) of flash-recycled LCO from 0 nm to 100 nm. Figure 17A shows the full-scan XPS results of ferromagnetic fLCO. Figures 17B-17E show the high-resolution XPS spectra of C 1s, Co 2p, Li 1s, and O 1s in the surface and subsurface regions of flash LCO, respectively. After surface etching, the spectra were acquired at different depths. Figure 17F shows the elemental ratios at different depths of ferromagnetic fLCO. [Figure 18-1]

[0184] Figures 18A-18H show the chemical composition of the ferromagnetic portion (fNMC) from flash-recycled NMC from 0 nm to 500 nm. Figure 18A shows the full-scan XPS results of the ferromagnetic fNMC. Figures 18B-18G show the high-resolution XPS spectra of C 1s, Co 2p, Li 1s, O 1s, Ni 2p, and Mn 2p at the surface and subsurface regions of the fNMC, respectively. After surface etching, the spectra were acquired at different depths. Figure 18H shows the elemental ratios at different depths in the ferromagnetic fNMC. [Figure 18-2]

[0184] Figures 18A-18H show the chemical composition of the ferromagnetic portion (fNMC) from flash-recycled NMC from 0 nm to 500 nm. Figure 18A shows the full-scan XPS results of the ferromagnetic fNMC. Figures 18B-18G show the high-resolution XPS spectra of C 1s, Co 2p, Li 1s, O 1s, Ni 2p, and Mn 2p at the surface and subsurface regions of the fNMC, respectively. After surface etching, the spectra were acquired at different depths. Figure 18H shows the elemental ratios at different depths of the ferromagnetic fNMC. [Figure 18-3]

[0184] Figures 18A-18H show the chemical composition of the ferromagnetic portion (fNMC) from flash-recycled NMC from 0 nm to 500 nm. Figure 18A shows the full-scan XPS results of the ferromagnetic fNMC. Figures 18B-18G show the high-resolution XPS spectra of C 1s, Co 2p, Li 1s, O 1s, Ni 2p, and Mn 2p at the surface and subsurface regions of the fNMC, respectively. After surface etching, the spectra were acquired at different depths. Figure 18H shows the elemental ratios at different depths of the ferromagnetic fNMC. [Figure 19-1]

[0185] Figures 19A-19H show the chemical composition of the ferromagnetic portion (fNMC) from flash-recycled NMC from 0 nm to 100 nm. Figure 19A shows the full-scan XPS results of the ferromagnetic fNMC. Figures 19B-19G show the high-resolution XPS spectra of C 1s, Co 2p, Li 1s, O 1s, Ni 2p, and Mn 2p at the surface and subsurface regions of the fNMC, respectively. After surface etching, the spectra were acquired at different depths. Figure 19H shows the elemental ratios at different depths of the ferromagnetic fNMC. [Figure 19-2]

[0185] Figures 19A-19H show the chemical composition of the ferromagnetic portion (fNMC) from 0 nm to 100 nm of flash-recycled NMC. Figure 19A shows the full-scan XPS results of the ferromagnetic fNMC. Figures 19B-19G show the high-resolution XPS spectra of C 1s, Co 2p, Li 1s, O 1s, Ni 2p, and Mn 2p at the surface and subsurface regions of the fNMC, respectively. After surface etching, the spectra were acquired at different depths. Figure 19H shows the elemental ratios at different depths of the ferromagnetic fNMC. [Figure 19-3]

[0185] Figures 19A-19H show the chemical composition of the ferromagnetic portion (fNMC) from 0 nm to 100 nm of flash-recycled NMC. Figure 19A shows the full-scan XPS results of the ferromagnetic fNMC. Figures 19B-19G show the high-resolution XPS spectra of C 1s, Co 2p, Li 1s, O 1s, Ni 2p, and Mn 2p at the surface and subsurface regions of the fNMC, respectively. After surface etching, the spectra were acquired at different depths. Figure 19H shows the elemental ratios at different depths of the ferromagnetic fNMC. [Figure 20]

[0186] FIG. 20A shows the X-ray diffraction spectra of CW, ferromagnetic fCW, and non-ferromagnetic fCW.

[0187] FIG. 20B shows an expanded X-ray diffraction spectrum in the low angle range indicated by the dashed rectangle in FIG. 20A. [Figure 21]

[0188] FIG. 21A shows the X-ray diffraction spectra of new lithium cobalt oxide (LCO), ferromagnetic fLCO, and non-ferromagnetic fLCO.

[0189] FIG. 21B shows an expanded X-ray diffraction spectrum in the low angle range indicated by the dashed rectangle in FIG. 21A. [Figure 22]

[0190] FIG. 22A shows the X-ray diffraction spectra of the new lithium nickel-manganese-cobalt oxide and ferromagnetic fNMC.

[0191] FIG. 22B shows an expanded X-ray diffraction spectrum in the low angle range indicated by the dashed rectangle in FIG. 22A. [Figure 23-1]

[0192] FIG. 23A shows the FTIR spectra of the CW and fCW ferromagnetic portions.

[0193] Figure 23B shows the size distribution of the ferromagnetic fraction of the starting CW and fCW particles of the material shown in Figure 23A, where the number of particles is N=100. [Figure 23-2]

[0194] 23C-23D show SEM images of the fCW ferromagnetic portion and the starting CW grains, respectively, of the material shown in FIG. 23A. [Figure 24]

[0195] Figures 24A-24D are images obtained from a mixture of LCO and NMC. Figure 24A is an SEM image of a CW from a mixture of LCO and NMC before flash recycling. Figure 24B is a higher-resolution SEM image of the CW before flash recycling. Figure 24C is an SEM image of the ferromagnetic portion of the fCW. Figure 24D is a higher-resolution SEM image of the ferromagnetic portion of the fCW. [Figure 25-1]

[0196] Figures 25A-25F are images obtained from LCO. Figure 25A shows an SEM image of LCO before flash recycling. Figure 25B shows a higher resolution SEM image of LCO before flash recycling. Figure 25C shows an SEM image of the ferromagnetic portion of fLCO. Figure 25D shows a higher resolution SEM image of the ferromagnetic portion of fLCO. [Figure 25-2] Figure 25E shows the particle size distribution of the ferromagnetic fraction of new LCO and fLCO particles. Number of samples N = 100. Figure 25F shows the FTIR spectra of LCO and ferromagnetic fLCO. [Figure 26-1]

[0197] Figures 26A-26F are images obtained from the NMC. Figure 26A shows an SEM image of the NMC before flash recycling. Figure 26B shows a higher resolution SEM image of the NMC before flash recycling. Figure 26C shows an SEM image of the ferromagnetic portion of the fNMC. Figure 26D shows a higher resolution SEM image of the ferromagnetic portion of the flash NMC. [Figure 26-2] Figure 26E shows the particle size distribution of the ferromagnetic portion of NMC and fNMC particles. Number of samples N=100. Figure 26F shows the FTIR spectra of NMC and ferromagnetic fNMC. [Figure 27-1]

[0198] Figures 27A-27E show FIB-SEM images of the carbon-coated structures. Figure 27A is a top-down SEM image showing the ferromagnetic fCW particle after FIB cutting. Figures 27B-27C are cross-sectional SEM images showing the boundary between the surface carbon coating and the underlying ferromagnetic fCW particle. Dashed lines are used to clarify the boundary. [Figure 27-2] Figure 27D is an SEM image of the cross section of a ferromagnetic fCW particle after FIB cutting and the corresponding elemental distribution of O, C, and Co. Figure 27E is an SEM image of the top view of a ferromagnetic fCW particle after FIB cutting and the corresponding elemental distribution of O, C, and Co. [Figure 28]

[0199] 28A-28B are fLCO magnetic and LCO schemes, respectively, showing the hierarchical structure of flash cathode particles. [Figure 29-1]

[0200] Figures 29A-29H are TEM images of the ferromagnetic portion of fLCO particles, Figures 29A-29B are HR-TEM images of ferromagnetic fLCO particles, and Figures 29C-29D are fast Fourier transform results of ferromagnetic fLCO particles. [Figure 29-2] Figures 29E-29F are HR-TEM images of the new LCO particles, and Figures 29F-29G are SAED patterns of the new LCO particles. [Figure 30]

[0201] FIG. 30 is a graph showing the energy trends for phase segregation in partially delithiated CW material. [Figure 31-1]

[0202] FIG. 31A is an X-ray diffraction spectrum of a commercial cathode material in the charged and discharged states. [Figure 31-2]

[0203] 31B-31C are expanded X-ray diffraction spectra at different angular ranges indicated by the dashed rectangles on the left and right, respectively, in FIG. 31A. [Figure 32]

[0204] Figure 32 shows the characterization of the Li source with curves for the LiOH·HO reactant and the recovered Li material, respectively. The heating rate was set at 10 °C / min and the N flow was maintained at 80 mL / min throughout the run. [Figure 33-1]

[0205] Figures 33A-33E show the characterization of the resynthesis conditions: Figure 33A shows an Ellingham diagram of the relevant reactions. [Figure 33-2]Figure 33B shows the XRD results for the resynthesized cathode materials using calcination temperatures of 400 °C (R-CW-400) and 500 °C (R-CW-500). Figures 33C-33E show the thermogravimetric curves and corresponding differential scanning calorimetry analyses of the ferromagnetic portions of LCO and fLCO. The heating rate was set at 10 °C / min and the air flow was maintained at 80 mL / min throughout the run. In Figure 33E, the temperature was held at 500 °C for 30 min to test the thermal stability at 500 °C. [Figure 33-3] Figures 33C-33E show the thermogravimetric curves and corresponding differential scanning calorimetry analyses of the ferromagnetic portions of LCO and fLCO. The heating rate was set at 10 °C / min and the air flow was maintained at 80 mL / min throughout the run. In Figure 33E, to test the thermal stability at 500 °C, the temperature was held at 500 °C for 30 min. [Figure 34-1]

[0206] Figures 34A-34I show the morphology of the resynthesized cathode. Figures 34A-34C are SEM images of R-CW, reporting a uniform carbon coating and layered structure. [Figure 34-2] Figures 34D-34E are HR-TEM images of R-LCO particles reporting the layered structure of the recovered cathode, and Figure 34F is a HAADF-STEM image of an R-LCO particle. [Figure 34-3] 34G-34I are the corresponding energy dispersive analysis elemental mappings of the R-LCO particles. [Figure 35-1]

[0207] Figures 35A-35E show the characterization of the resynthesized cathode. Figure 35A shows the FTIR spectra of the cathode waste and the resynthesized cathode material (R-CW). Figure 35B shows the FTIR spectra of the LCO and the resynthesized cathode material (R-LCO). [Figure 35-2] Figure 35C shows the room temperature (300 K) hysteresis loops of the flash-recycled NMC ferromagnetic portion (fCW magnetic), the flash-CW after hydrothermal reaction (post-hydrothermal), and the resynthesized cathode material (R-CW). Figure 35D shows the behavior of the hysteresis loops around the origin for these three samples. [Figure 35-3]Figure 35E shows the electrochemical performance of the fresh NMC (NMC) in the prepared half-cell. The rate for testing was 0.2 C. [Figure 36]

[0208] Figures 36A-36C show the morphology of the carbon coating structure: Figure 36A is a TEM image of an R-CW particle, and Figures 36B-36C are HR-TEM images of an R-CW particle reporting the amorphous character of the carbon coating at the surface. [Figure 37-1]

[0209] Figures 37A-37J show the elemental distribution of the resynthesized cathode material. Figure 37A is an energy dispersive X-ray spectrum of an R-CW particle. Figure 37B is an HAADF-STEM image of an R-CW particle. Figure 37C is a BF-STEM image of an R-CW particle. Figures 37D-37J are the corresponding elemental mappings of the R-CW particle. [Figure 37-2] 37D-37J are the corresponding elemental mappings of the R-CW particles. [Figure 38-1]

[0210] Figures 38A-38D show the crystal structure of the resynthesized cathode material. Figure 38A is an HR-TEM image of R-LCO, reporting the presence of a layered structure on the surface of the cathode particles. Figure 38B is the corresponding FFT pattern of the R-LCO shown in Figure 38A. [Figure 38-2] 38C-38D are atomic resolution HAADF-STEM images of R-LCO reporting the presence of layered structures on the surface of the cathode particles. [Figure 39]

[0211] Figures 39A-39E show the configurations of the carbon crust after annealing at various temperatures (700K, 1000K, 1500K, 2000K, and 2500K, respectively) over 9 ns. [Figure 40-1]

[0212] Figures 40A-40D show the diffusion barrier of Li+ for various structures within an amorphous carbon shell. Figure 40A shows the edge of an unpassivated monolayer of graphene. Figure 40B shows the edge of an unpassivated bilayer of graphene. [Figure 40-2]Figure 40C shows the reconstructed divacancy forming a 5-8-5 defect (the largest barrier corresponds to diffusion through the 8-ring defect to the other side of the plane; steps 7-10). Figure 40D shows that diffusion across the reconstructed edge of bilayer graphene exhibits a barrier nearly identical to that for diffusion into planar graphene, at about 0.34 eV. [Figure 41-1]

[0213] Figures 41A-41F show economic and environmental analyses of pyrometallurgical (pyro), hydrometallurgical (hydro), and flash recycling processes. Figure 41A is a scheme of a life cycle analysis of a Li-ion battery showing that flashing is a more direct route to recycling. [Figure 41-2] Figure 41B shows the recycling revenue and recycling cost per kilogram of cathode resynthesized by various methods. Figure 41C shows the net profit per kilogram of cathode resynthesized by various methods. [Figure 41-3] Figure 41D shows the total energy consumption of resynthesizing 1 kg of cathode material using pyrometallurgical, hydrometallurgical, and flash recycling methods. As a comparison, the energy cost from mining unprocessed ore is shown. Figure 41E shows the GHG emissions in resynthesizing 1 kg of cathode material using pyrometallurgical, hydrometallurgical, and flash recycling methods. As a comparison, the GHG emissions using unprocessed ore are shown. [Figure 41-4] FIG. 41F shows the net profit per kilogram of various cathodes resynthesized by pyrometallurgical, hydrometallurgical, and flash recycling methods. [Figure 42-1]

[0214] FIG. 42A is a scheme of a life cycle analysis of a lithium-ion battery. [Figure 42-2]

[0215] FIG. 42B is a simplified flow chart of a pyrometallurgical process. [Figure 42-3]

[0216] FIG. 42C is a simplified flow chart of the hydrometallurgical process. [Figure 42-4]

[0217] FIG. 42D is a simplified flowchart of a flash recycling method. [Figure 43-1]

[0218] Figures 43A-43B show a scheme of the FJH system: Figure 43A is an electrical schematic diagram of the FJH system. [Figure 43-2] Figure 43B is a diagram of the large FJH reaction box. [Figure 44-1]

[0219] Figures 44A-44C show flash recycling of a graphite anode, and Figures 44A-44B are schematic illustrations of flash recycling of anode waste and the effect of resistance-dependent Joule heating in a multiphase system, respectively. [Figure 44-2] FIG. 44C is the corresponding current-time curve during the flash recycling process. [Figure 45]

[0220] 45A-45B show the general procedure of the conventional high-temperature calcination method and the real-time temperature curves from a sample during the flash recycling process, respectively. [Figure 46]

[0221] Figures 46A-46D show the thermal stability results for various anode materials. Figures 46A-46B show the TGA and DSC results for anode waste (AW), calcined anode waste (cAW), flash anode waste (fAW), and graphite, respectively. Figures 46C-46D show the TGA and DSC results for AW, fAW100V, fAW120V, and fAW120V x 2, respectively. TGA and DSC data were collected from 25 to 1000 °C under air. The heating rate was set at 10 °C / min, and the air flow was maintained at 80 mL / min throughout the run. [Figure 47]

[0222] Figure 47 shows the results of thermal stability tests by TGA: remaining mass fraction of various treated graphite anode materials at T = 773K. [Figure 48-1]

[0223] Figures 48A-48D are visual images of anode waste, calcined anode waste, flash anode waste (200 mg / batch), and flash anode waste (1 g / batch), respectively. [Figure 48-2]

[0224] Figures 48E-48F are TGA and DSC results of AW and fAW, respectively, on a gram scale. TGA and DSC data were collected from 25 to 1000 °C under air. The heating rate was set at 10 °C / min and the air flow was maintained at 80 mL / min throughout the run. [Figure 49]

[0225] Figure 49 shows the thermal stability test by TGA: remaining mass fraction of various treated graphite anode materials at T = 1273K. [Figure 50]

[0226] Figure 50 shows the crystal structures of cAW, fAW, and AW. [Figure 51]

[0227] 51A-51B are high-resolution XRD spectra of various anode materials (AW, cAW, and fAW). [Figure 52]

[0228] 52A-52C are high-resolution XRD spectra of fAW (gram scale). [Figure 53]

[0229] Figure 53 shows the surface composition of fAW and AW. [Figure 54]

[0230] Figure 54 shows the surface composition of cAW. [Figure 55-1]

[0231] Figures 55A, 55C, and 55E show the chemical composition of the anode materials from 0 nm (surface) to a depth of 450 nm for AW, fAW, and cAW, respectively. After surface etching, spectra were acquired at different depths.

[0232] Figures 55B, 55D, and 55F show the elemental distribution of AW, fAW, and cAW particles, respectively, in the 0-500 nm subsurface region. [Figure 55-2]

[0231] Figures 55A, 55C, and 55E show the chemical composition of the anode materials from 0 nm (surface) to a depth of 450 nm for AW, fAW, and cAW, respectively. After surface etching, spectra were acquired at different depths.

[0232] Figures 55B, 55D, and 55F show the elemental distribution of AW, fAW, and cAW microparticles, respectively, in the 0-500 nm subsurface region. [Figure 56]

[0233] Figure 56 shows the UV-vis spectra of aqueous leaching solutions of fAW and AW. The visual images show yellowish and clear solutions obtained from AW and fAW, respectively. [Figure 57-1]

[0234] Figures 57A-57I are SEM images of various anode materials. Figures 57A-57C are AW and Figures 57D-57F are fAW. [Figure 57-2] Figures 57G to 57I are cAWs.

[0235] Figures 57J-57K are statistical studies showing the size of AW, fAW, and cAW, respectively. For each, the number of samples is N=50. The particle size distribution results show that AW, fAW, and cAW have similar average particle sizes. [Figure 58]

[0236] Figures 58A-58D are images of the anode waste. Figures 58A-58B are TEM images, and Figures 58C-58D are HR-TEM images. The average thickness of the SEI around the graphite particles is about 145 nm. Beneath the SEI region, the graphite crystal lattice can be observed, as shown in Figure 16c. Additionally, there are many small crystals embedded within the SEI, which is consistent with the mosaic model of the SEI structure. [Figure 59]

[0237] Figures 59A-59D are images of flash anode waste. Figures 59A-59B are TEM images; Figures 59C-59D are HR-TEM images. The decomposition of the SEI and the formation of graphene shells and nanoparticles, such as LiF and Co3O4, can be observed, which is consistent with the elemental distribution and XRD spectrum results. The average thickness of the layer also decreases from approximately 145 nm to approximately 65 nm. This SEI-derived layer is composed of graphene layers and embedded nanoparticles, indicating that the flash method can be an effective method for decomposing the SEI and subsequently converting it into a protective graphene layer. [Figure 60]

[0238] Figure 60 shows STEM images of the anode waste and the corresponding element distribution. The scale bar is the same for all images. Metal elements, such as Co (approximately 0.2 at%), are uniformly distributed in the anode SEI for the pristine AW, which may be due to the dissolution and transport of transition metals from the cathode side and their subsequent trapping in the SEI at the anode side. [Figure 61]

[0239] FIG. 61 shows the STEM images of the fAW particles and the results of their respective elemental mapping. [Figure 62-1]

[0240] Figures 62A-62E show metal ion leaching tests. Figure 62A shows the recovery efficiency and excess yield Y / Y of flash anode waste with HCl at different concentrations. The number of samples is N=3, and the bars indicate the standard deviation between runs, and so on. Figure 62B shows the recovery efficiency and excess yield Y / Y of various metal ions of flash anode waste with 0.1 M HCl. Figure 62C shows the recovery efficiency and excess yield Y / Y of total metal ions of calcined anode waste with HCl at different concentrations. Figure 62D shows the recovery efficiency and excess yield Y / Y of total metal ions of flash anode waste after TGA treatment with HCl at different concentrations. [Figure 62-2] FIG. 62E shows the total amount of metal ions and excess yield Y / Y0 of various treated anode wastes with concentrated hydrochloric acid. [Figure 63]

[0241] Figures 63A-63B show the TGA and DSC results for AW, fAW-W, and AW-W, respectively. TGA and DSC data were collected from 25 to 1000 °C under air. The heating rate was set at 10 °C / min and the air flow was maintained at 80 mL / min throughout the run. fAW-W represents fAW after rinsing with 0.1 M HCl to recollect the useful metal ions. The same applies to other anode materials. [Figure 64]

[0242] Figures 64A to 64C are images of fAW-W. Figure 64A is a TEM image of fAW-W, and Figures 64B to 64C are HR-TEM images of fAW-W.

[0243] Figure 64D is the corresponding FFT pattern along the fAW-W 0002 zone axis shown in Figures 64A-64C. The absence of embedded nanoparticles indicates that post-treatment with dilute acid can be used to effectively collect the useful metal. There is also a unique set of 6x diffraction patterns, reflecting the well-graphitized structure of the anodic particles. [Figure 65]

[0244] Figure 65 shows the first cycle voltage profiles of AW, cAW, fAW, and graphite at 0.05 C. The areal capacity is about 3.0 mAh / cm. [Figure 66]

[0245] Figures 66A-66C show the voltage profiles of graphite and fAW (Figure 66A), cAW (Figure 66B), and AW (Figure 66C) at different rates. The areal capacity is approximately 2.0 mAh / cm. [Figure 67]

[0246] Figure 67 shows the rate performance of AW, cAW, fAW, and graphite. [Figure 68-1]

[0247] Figures 68A-68C show the preparation of synthetic graphite, the flash recycling method, and the high-temperature calcination method, respectively. [Figure 68-2]

[0247] Figures 68A-68C show the preparation of synthetic graphite, the flash recycling method, and the high-temperature calcination method, respectively. [Figure 69-1]

[0248] 69A-69C show the GHG emissions, water consumption, and total energy consumption in producing 1 kg of anode material using the flash recycling method (Flash), the high temperature calcination method (HTC), and 1 kg of synthetic graphite, respectively. [Figure 69-2]

[0249] 69D-69E show the costs and net benefits associated with preparing 1 kg of synthetic graphite, 1 kg of anode material by the flash recycling method (flash) and the high-temperature calcination method (HTC). [Figure 70]

[0250] FIG. 70 shows that the weight percentages of Li, Co, Ni, and Mn can be collected from a cell containing a quartz tube, graphite spacer, and copper wool electrode, but not filled with any sample (i.e., the blank group). [Figure 71]

[0251] Figure 71 shows the total amount of Li and Co in a 1.00 g sample. [Figure 72]

[0252] 72A-72B show the recovery efficiencies of (a) Li and (b) Co from LCO and flash LCO in HCl solutions at different concentrations, respectively. [Figure 73]

[0253] Figure 73 shows the distribution of Li and Co from LCO and flash LCO after dissolution in 0.1 M HCl solution and rinsing from the quartz tube, graphite spacer, and copper wool electrode. [Figure 74]

[0254] Figure 74 shows the total amount of Li, Co, Ni, and Mn in a 1.00 g sample. (Left bar) Before flushing. (Right bar) After flushing. [Figure 75]

[0255] 75A-75D show the recovery efficiencies of (a) Li, (b) Co, (c) Ni, and (d) Mn from NMC and flash NMC in HCl solutions at different concentrations, respectively. DETAILED DESCRIPTION OF THE INVENTION

[0089]

[0256] The present invention relates to flash recycling of batteries, such as lithium-ion batteries, other metal-ion batteries (sodium, potassium, zinc, magnesium, and aluminum), metal batteries, batteries with all-metal oxide cathodes, and batteries with all-graphite-containing anodes, including a solvent- and water-free flash joule heating (FJH) method performed in combination with magnetic separation to recover lithium, cobalt, nickel, and manganese. The combination of the solvent- and water-free FJH method and 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 method disclosed and discussed herein will focus on 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, as well as the anodes and cathodes of metal batteries, including batteries without an anode (meaning there is no excess anode metal) and metal-oxygen and metal-air batteries.

[0090]

[0257] This method is extremely rapid and preserves the particle morphology (Figure 1A). Conventional recycling strategies for recovering useful metals contained in spent cathode waste (CW) include pyrometallurgy and hydrometallurgy [Tran 2018], which require harsh conditions, such as extreme furnace temperatures above 1400 °C [Lv 2018; Li 2016] or corrosive agents such as hydrochloric acid, nitric acid, and sulfuric acid (Figures 1B-1C) [Chagnes 2013]. In addition, these methods require high energy, generate significant greenhouse gas (GHG) emissions and secondary waste, and lead to the decomposition of materials into their elemental or ionic solutions during recycling, thereby increasing the cost of returning them to their cathode morphology [Xu 2020]. In the flash method of the present invention, the hierarchical cathode morphology is preserved while other components of CW, such as the cathode electrolyte interphase (CEI), decompose (Figure 1A).

[0091] Flash recycling process for cathode materials.

[0258] Flash recycling of LIBs is an environmentally cleaner way to reclaim metals in secondary batteries. The method preserves the 3D layered structure of the cathode, providing efficient reuse of elemental inventories. The rapid process also results in a convenient carbon coating on the recycled cathode particles that stabilizes the overall structure of the cathode while allowing Li-ion transport, thereby providing recycled batteries with superior performance over new batteries. The FJH process can be industrially scaled to multi-ton capacity per facility [Universal Matter 2021], enabling ease of manufacturing while minimizing reliance on newly mined metal ores for LIB production.

[0092]

[0259] In the flash recycling process, a mixture of cathode material and conductive additive (e.g., about 10 wt%, e.g., carbon black) or graphite from used anodes (e.g., about 20 wt%) is slightly compressed inside a quartz tube between two electrodes. [Luong 2020; Chen 2021]. The carbon additive is used to increase the conductivity of the mixture. A capacitor bank in the circuit can be used to provide electrothermal energy to the reactants for about 300 ms. See Figures 2A-2B.

[0093]

[0260] For example, electrodes were collected by discharging used Li-ion batteries in a circuit until the voltage fell below 2.5 V and then manually dismantling the batteries. The cathode waste was removed directly from the used electrodes before use. Unless otherwise specified, the cathode material and conductive additive (10 wt% carbon black or 20 wt% used anode graphite) were homogeneously mixed by grinding with a mortar and pestle for approximately 10 minutes. The reactants were packed into quartz tubes with an inner diameter of 4 or 8 mm. The packed masses in the 4 and 8 mm tubes 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 reactants as shown in Figure 1A. In the quartz tube, the graphite rod was placed in contact with the sample. 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 power supply that could reach 400 V. The duration of the flash was controlled by an Arduino controller relay in the circuit, which acted as a high-speed switch.

[0094]

[0261] Various cathode materials, LCO and NMC cathode combinations were also used to demonstrate the versatility of the flash recycling method. Tables I-II show the flash conditions for different cathode materials in small and large batches, respectively.

[0095] [Table 1]

[0096] [Table 2]

[0097]

[0262] After the FJH reaction, the reaction was allowed to cool for 3 minutes, and then the ferromagnetic portion of the flashed product was immediately separated using a commercial bar magnet with a magnetic field strength of approximately 5000 Oe. The mass ratio of the ferromagnetic portion was approximately 90 wt%, and the mass ratio of the non-magnetic portion was approximately 10 wt%. The remaining approximately 10 wt% of the flashed product that was not captured by the magnet was collected and combined with a small portion from another FJH run for reflashing. The flashing conditions were the same as those used for the primary flashing. For the reflashing experiment, a small-batch experiment was used as a demonstration. Approximately 60 wt% of the reflashed product could be magnetically recovered.

[0098]

[0263] In this flash recycling process, with a voltage of 150 V and a resistance of 3 Ω, the current passing through the sample is recorded to reach approximately 40 A with a discharge time of approximately 300 ms (Figures 3A-3C). The temperature can be measured via a 16-channel fiber optic spectrometer by fitting blackbody radiation (Figure 4). The temperature was estimated to be approximately 2500 K. The ultrafast cooling rate was also observed, approximately 1.2 × 10 4 The temperature is recorded in K / s (Figure 1D). While pyrometallurgical methods cause the loss of the more volatile Li (Figure 1B) and irreversible collapse of the cathode structure [Lv 2018], the instantaneous high temperatures in flash recycling avoid the loss of Li and preserve the particle morphology and the 3D layered structure of the cathode.

[0099]

[0264] Used LIB, LCO (LiCoO2) and NMC (LiNi x Mn y Co z O2, usually referred to as NMCxyz, e.g. NMC 811CW from a flash-recycled product (Figure 1A, 1F, and 5A-5B) was tested. The CW consisted of a mixture of LCO and NMC. The flash-recycled product contained a mixture of ferromagnetic (approximately 90 wt%) and non-ferromagnetic (approximately 10 wt%) fractions (Figures 1A, 1F, and 5A-5B). The ferromagnetic fraction of the flash-recycled product exhibited a sharp response to an external magnetic field, whereas the reactant did not. This magnetization was strong enough to ensure effective separation of the ferromagnetic fraction with a conventional hand-held magnet with a field strength of approximately 5000 Oe.

[0100]

[0265] A simple magnet was used to extract the desired ferromagnetic fraction (Figures 1A and 6A-6D). The extracted ferromagnetic product contained Li and transition metals. In this case, Li was successfully extracted with the magnet because it is closely associated with ferromagnetic metals.

[0101]

[0266] Additionally, the remaining 10% non-ferromagnetic fraction may be reflashed as shown in Figures 7 and 8A-8E. This process works with LCO, NMC, and mixtures thereof, as found in commercial CWs recovered from spent LIBs from old laptop computer batteries (Figures 9A-9D).

[0102]

[0267] As shown in Figures 1F and 5A-5B, the ferromagnetic portion of flash cathode waste (fCW magnetism, orange curve) had a sharp response to an external magnetic field (approximately 10 emu / g at 1900 Oe). The magnetic moment reached saturation (approximately 17 emu / g) at 8000 Oe. This magnetization was strong enough to ensure effective separation of the ferromagnetic portion with a conventional handheld magnet with a field strength of approximately 5000 Oe. The coercive force, calculated from Figure 5B, was small, indicating that the magnetization of the material could easily reverse direction without significant energy dissipation (hysteresis losses). In contrast, the fCW nonmagnetic and intrinsic CW exhibited weak magnetic responses to external magnetic fields; they are paramagnetic and diamagnetic materials, respectively. Therefore, a conventional magnet can be used to capture the ferromagnetic portion of flash-recycled cathode waste and recover the metals Co, Li, Ni, and Mn from used batteries. Li, which is non-magnetic, was captured by the particles in the ferromagnetic portion.

[0103]

[0268] Regarding the reflashing of the non-magnetic fraction, the remaining approximately 10 wt% of flash product not captured by the magnet was combined with a small fraction from other FJH runs to be reflashed, and the flashing conditions were the same as those used for flash recycling of cathode waste. Approximately 60 wt% of this could be magnetically recovered, and its behavior is similar to that of the initially flashed magnetic fraction. ICP-OES results show excellent recoveries from the reflash process, including Li (79%), Co (77%), Ni (73%), and Mn (84%). As a result, further use of the remaining 10 wt% non-magnetic fraction in the reflash recycling process can achieve high recoveries of all useful metals, including Li (92%), Co (93%), Ni (96%), and Mn (98%).

[0104] Recovery efficiency

[0269] A high recovery rate is essential for an effective recycling strategy [XiaoI 2017]. The recovery efficiency (a) is defined by equation (1):

[0105] [ka]

[0106]

[0270] m(N, flash product) and m(N, reactant) represent the weight of the studied species N in the flash product and reactant, respectively. The amount is determined by ICP-OES and calculated by equation (2).

[0107] [ka]

[0108]

[0271] C(N, product) and C(N, reactant) represent the mass concentrations of M species in the dilute solutions of flash products and reactants, respectively. m t (N, product) and m1(N, reactant) represent the mass of the diluted solution of flash products and reactants. m2(N, reactant) and m2(N, product) represent the mass of the sample used in the ICP-OES experiment. m3(N, reactant) and m3(N, product) represent the total mass of the sample before the flash reaction and the mass of the sample after magnetic separation, respectively.

[0109]

[0272] The molar ratio (β) is determined by Equation 3.

[0110] [ka]

[0111]

[0273] n (N) and n0 (N) represent the actual amount and theoretical moles of the studied species N in the cathode material, respectively. The actual moles are determined by ICP-OES and calculated by Equation 4.

[0112] [ka]

[0113]

[0274] M(N) represents the molar mass of species N.

[0275] Recovery efficiencies from various flash products (Figures 10A-10D) are quantified using inductively coupled plasma optical emission spectroscopy (ICP-OES). For flash recycling of LCO, average yields are 92% for Co and 77% for Li after a single flash (Figure 11A). These efficiencies can be improved after reflashing the non-ferromagnetic fraction, such that total recoveries of Co and Li are 98% and 85%, respectively, after a single reflash. Compared to traditional pyrometallurgical methods, higher Li recoveries can be achieved without sacrificing Co yield. [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 Figure 11B and Table III, but flash recycling eliminates the production of corrosive aqueous waste. [Zhang 1998;Swain 2007;Pinna 2017;Lee 2002;Chen 2015].

[0114] [Table 3]

[0115]

[0276] The same trend can be seen in flash NMC (fNMC) and actual CW, which contain mixed components obtained from spent LIBs. A single flash of NMC resulted in high average recoveries for all valuable metals (Figure 11C), including Li (94%), Co (94%), Ni (98%), and Mn (92%). High average recoveries were also achieved with flash CW (fCW, Figure 11D), including Li (92%), Co (93%), Ni (96%), and Mn (98%). Radar plots (Figures 11E-11G and 12A-12F) compare metal recoveries for the flash method with efficiencies typical of those found in pyrometallurgical and hydrometallurgical methods.

[0116] Structure retention factor (R)

[0277] The structural retention factor is defined as the existing 3D layered cathode structure after the recycling method. The structural retention factor only exists in flash recycling. It emphasizes the retention of particle morphology and crystalline structure after the flash process and can be quantified by X-ray diffraction (XRD).

[0117]

[0278] The structural retention factor (R) is defined by equation (5).

[0118] [ka]

[0119]

[0279] I(003) and I(104) represent the intensities of the (003) and (104) peaks in the XRD spectrum. I0 and I represent the peak intensities of the reactants and products from different recycling processes. In the XRD results, the (003) peak is characteristic of the layered structure in lithiated metal oxides, while the (104) peak reflects the characteristics of the basic unit of transition metal-oxygen bonding that forms layered compounds. The intensity ratio between the (003) and (104) peaks indicates the efficiency of crystallization. A lower value of I(003) / I(104) reflects cation intermixing between the transition metal and lithium, and generally the decomposition of the layered features.

[0120] (1) When R = 0, the layered structure disappears. (2) When 0 < R < 1, the layered structure is preserved, but the crystallinity deteriorates. (3) When R ≥ 1, the crystallinity is improved and the layered structure is preserved.

[0121]

[0280] In the case of hydrometallurgy and pyrometallurgy methods, the layered structure of the cathode waste material no longer exists and R = 0. In contrast, the flash recycling method can preserve the structure and R = 3.29 / 3.22 = 1.02. This value reflects that the layered structure was preserved without deterioration of the crystallinity during the flash recycling method.

[0122] Hierarchical structure of fine particles in cathode materials

[0281] The efficiency of the flash recycling process in the cathode material was determined by analyzing the subsurface region of the ferromagnetic part and the crystal structure of the bulk by elemental depth analysis and XRD, respectively [Andre 2015]. The distinct elemental ratios and valence states from the surface to the subsurface elucidated the hierarchical structure of the cathode microparticles resulting from the flash recycling process.

[0123]

[0282] In the case of fCW, the atomic ratio of Co dramatically increases from <1% to about 20% when processed at a depth of 500 nm from the surface, and the binding energy shifts down from 782.2 eV at the surface to 779.3 eV (less than 200 nm, Figures 13A - 13B), while the carbon content decreases in the corresponding region (Figure 13B). The splitting of the O 1s spectrum into O α (at about 532.6 eV) and O β (at about 530.3 eV) indicates the transition from adsorbed oxygen species to lattice oxygen species (Figures 14A - 14E) [Chen 2015].

[0124] ​​This, combined with the unchanged binding energy of the Co 2p spectrum below 200 nm, confirmed the presence of intact lithiated metal oxides in this region (Figure 13C). Conversely, the unflashed CW showed no significant changes in binding energy or elemental content below the solid electrolyte boundary formed during the battery cycling process (Figures 15A-15G). This result confirms the layered structure of the cathode particles formed by the flash recycling process. Similar topological structures were found in flash-recycled LCO and NMC (Figures 16A-16F, 17A-17F, 18A-18H, and 19A-19H), demonstrating the broad applicability of the flash recycling method to process different cathode materials.

[0125]

[0284] The layered structure of the magnetic portion of the flash-recycled CW is further confirmed by the (003) diffraction peak at approximately 18.9° [Dai 2019], while the nonmagnetic portion is primarily composed of graphite conductive additives, with some residual metallic signals (Figures 20A-20B). Similarly, the layered structure remains intact in flash-recycled LCO (fLCO) and fNMC (Figures 21A-21B and 19A-19B). The emergence of magnetic properties in fCW clarifies one relevant aspect of the flash method: rapid localized heating and cooling induces thermal decomposition that is limited to the surface while maintaining particle integrity. This process affects the CEI, cathode surface, carbon coating, and the ability to resynthesize new cathodes.

[0126]

[0285] CEI breaks down into salts that coat the particles. The presence of carbonates is indicated by the CO3 2-This can be confirmed by the stretching modes (Figures 23A-23D, 24A-24D, 25A-25F, and 26A-26F) and the high binding energy in the XPS C 1s spectra [Li 2019]. The carbon present in the electrode also rearranges as a thin coating on the surface of the particles at high temperatures, as evidenced by elemental mapping (Figure 13D). The carbon thickness is 20-50 nm, as identified by focused ion beam milling combined with SEM images (Figures 27A-27E) and elemental depth analysis shown in the XPS results (Figures 14A-14E). As shown in Figures 27D-27E, the elements Co and O are enriched in the cross section, where C is absent, while the top surface shows the presence of C and the absence of Co and O. This indicates that there is a carbon coating on the surface of the ferromagnetic fCW particles, and the thickness is 20-50 nm, as estimated from the cross-sectional SEM images and XPS depth analysis. The carbon coating is derived from a flash reaction between the cathode particles and the conductive carbon additive. During the flash reaction, which takes 10-30 ms, hot spots are formed only at the interface between the conductive carbon and the insulating cathode material. These hot spots are formed without irreversible layered structure collapse, resulting in the formation of a thin carbon coating (20-50 nm) on the cathode particles and the dissolution of Li at the interface. + This leads to the formation of a subsurface metal oxide (approximately 200 nm) after diffusion.

[0127]

[0286] The cathodic surface reaction can be particularly important. Flashing induces the formation of a metal oxide film from two sources: rearrangement and decomposition. The flashing process thermally decomposes the particle surface with the release of O2 and delithiation. This surface modification results in the formation of Co at the surface. 2+This leads to the formation of species containing LiCoO, such as Co3O4 and CoO, which results in enhanced magnetic susceptibility compared to lithiated species [Sharifi 2017]. This process has been shown to occur at temperatures below 300°C in aged cathodes [Furushima 2011]. Oxides may also form naturally as part of cycling or may be rearranged by the flash process. As a result of repeated charge / discharge cycles, the surface of the CW particles develops into regions of crystalline LiCoO, partially delithiated LiCoO, and partially delithiated LiCoO. x It consists of domains of CoO2 and small inclusions of Co3O4 and CoO phases. [Kabir 2017]

[0128]

[0287] During the FJH process, this heterogeneous material undergoes an annealing process during which it is encapsulated with a carbon shell that prevents significant mass loss. Upon structural relaxation, CoO and CoO undergo outward segregation (Figure 13E), forming a shell on the restored crystalline LiCoO. Some of this surface metal oxide can be identified in high-resolution transmission electron microscopy (HR-TEM) images (Figures 28A-28B and 29A-29H).

[0129]

[0288] First-principles calculations show the energy direction of such segregation, ΔE (Figure 30). First-principles calculations show that the partially delithiated LiCoO phase segregates into high-quality LiCoO, CoO, and LiO via the release of O gas. x This allowed the demonstration of possible pathways for the annealing process of CoO2 [Furushimna 2011]:

[0130] [ka]

[0131]

[0289] Reaction energy ΔE = E for various values ​​of x LiCoO2 +E Co3O4 +E O2 -E LixCoO2is plotted in Figure 30 and shows the energy orientation towards phase segregation. Interestingly, note that the energy orientation towards segregation is minimal at low to moderate delithiation levels.

[0132]

[0290] A relatively lower ΔE was observed for the new cathode compared to the old cathode, indicating that annealing during flash recycling is more effective for the aged cathode due to more pronounced delithiation. This mechanism is consistent with an increase in the structural retention factor, as can be observed in Figures 11E, 12A, and 12D. The flash cathode material retains approximately 93% of the original particle size distribution of the cathode material (Figures 23A-23D, 24A-24D, 25A-25F, and 26A-26F). Surface decomposition is further evidenced by X-ray diffraction (XRD). A downshift of the (003) diffraction peak (widening of the interlayer spacing) was observed in the ferromagnetic portion of the fCW (Figures 20A-20B), which is consistent with a partial delithiation process (Figures 31A-31C).

[0133]

[0291] Simulated magnetic properties of the Co3O4 / CoO film (Figure 13E) indicate a magnetic moment of approximately 70 emu / g compared to the bulk phase (approximately one-third of the 219 emu / g of Fe). The magnetic signature of the oxide shell is somewhat reduced by inherent disorder and size effects, characteristics consistent with those of thin Co3O4 films [Apatiga 2006; Moro 2013; Zhang 2015]. The formation of this layer is useful (and can be exploited) for magnetic separation. The gradual nature of the annealing is consistent with its ability to improve recycling yields through repeated FJH of nonmagnetic materials observed in experiments.

[0134] Re-synthesized cathode material

[0292] The cathode material may be resynthesized from the ferromagnetic flash product, and in this context, the cathode material is referred to as a "re-synthesized cathode" (R-CW). For example, approximately 1 g of the flash product was mixed with 10 mL of a 4 mol / L LiOH aqueous solution, and then the mixture was poured into a hot water container. The hot water container was made of polytetrafluoroethylene and had a volume of 40 mL. The container was then sealed in a tightly fitting stainless steel autoclave and placed in an oven at 180 °C for 12 hours. The solid powder was then dried using vacuum filtration. The solid was then calcined in air at 400 °C for 3 hours before being used to prepare a battery slurry.

[0135]

[0293] In terms of synthesizing new cathodes, the flash process results in more efficient use of Li. Compared with solid-state reactions for preparing resynthesized cathodes, the hydrothermal method disclosed and described herein can avoid the direct use of solid Li sources, which are difficult to remove after the resynthesis process and act as impurities, affecting the electrochemical performance of the cathode material. As reported in the literature [Zhao 2020; Zhang 2014], the chemical potential of the layered flash product Li 0.84 Chemical lithiation of CoO2 (the stoichiometric ratio is calculated from ICP-OES) can be driven to form the final resynthesized cathode material. Because there is no fundamental structural change, the optimization conditions can be milder compared to synthesis conditions starting from rock-type metal oxides such as Co3O4. LiOH is used as the Li source because of its excellent aqueous solubility to form concentrated solutions. Other Li sources, such as Li2CO3, have also been reported as Li sources for the synthesis of LCO [Zhao 2020], and these could also be considered for industrialized processes. The purpose of the final calcination step is to increase the crystallinity of the resynthesized cathode material and improve its electrochemical performance. The reason for choosing 400°C in this embodiment can be explained by the results, because carbothermal reduction begins at temperatures higher than 450°C [Wang 2018].

[0136]

[0294] The formation of lithium carbonate on the surface of the ferromagnetic flushed particles minimizes the need for replenished Li-ion precursors to reconstitute the stoichiometry of the newly recycled cathode, see Figure 32.

[0137]

[0295] To calculate the Li source consumed in the resynthesis process, the solvent after the hydrothermal reaction is collected. TGA (Figure 32) can be performed to calculate the remaining Li source, e.g., impurities in the water of crystallization. There is one mass loss step by TGA for the LiOH·H2O reaction mixture at approximately 120 °C, which is related to the loss of water of crystallization in the reaction mixture. For the recovered Li material, there are three steps: (1) at approximately 100 °C, the loss (approximately 5.6%) is related to the loss of water of crystallization; (2) at approximately 600 °C, the loss (approximately 31.0%) is related to the decomposition of LiOH; and (3) at approximately 860 °C, the loss (approximately 8.9%) is related to the decomposition of Li2CO3, and the remaining powder is Li2O. [Beyer 2013] The mass of the recovered powder is 1.0259 g. Therefore, 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 about 1.0 g of flash powder is used, the percentage of Li consumed is 18.4%.

[0138]

[0296] Only 10%–20% of the new Li ions are required to fully lithiate and reconstruct the cathode material, since 80%–90% are already present in the ferromagnetic flash product, as shown by ICP-OES (Figures 33A–33E, in which the corresponding cobalt complex is shown along with its required Gibbs free energy). New cathode material may be resynthesized from the ferromagnetic fCW by a simple hydrothermal reaction followed by calcination at 400 °C in air.

[0139]

[0297] For certain embodiments, the optimized calcination temperature is 400°C, with higher temperatures, around 500°C, expected to result in carbothermal reduction. Therefore, the following characterization will be for R-CW-400, which will be referred to as R-CW for simplicity. The possible reactions of LCO and the corresponding Gibbs free energy relationships can be calculated as follows:

[0140] [ka]

[0141]

[0298] An Ellingham diagram of the above reaction was plotted, which confirms the thermodynamic relationship [Wang 2018]. The carbothermal reduction of carbon and LCO is thermodynamically favorable in an inert atmosphere or in air. Therefore, high-temperature calcination may cause the reduction of Co species, which is unfavorable for cathode material resynthesis. Similarly, direct high-temperature treatment using pyrometallurgical methods may only yield the Co3O4 metal mass resulting from the above carbothermal reaction. The thermogravimetric curve also demonstrates that LCO itself is stable in air above 1000°C, but the ferromagnetic portion of fLCO, coated with carbon, exhibits a weight loss of more than 10 wt% when the temperature is increased from 600°C to 800°C. This can also be explained by the above carbothermal reaction. When the temperature is held at 500°C for 30 minutes, a clear mass loss can still be observed, as shown in Figure 33E. This is consistent with the XRD in Figure 33B.

[0142]

[0299] To coat the cathode material with carbon, a low calcination temperature should be used in the final step of the resynthesis process. However, resynthesized cathodes obtained by pyrometallurgical or hydrometallurgical methods require high calcination temperatures (higher than 750 °C) to establish an ordered layer structure of the cathode. [Zhao 2020; Moro 2013; Nie 2015] This characteristic makes it more difficult to directly achieve a surface carbon coating in such a classical resynthesis process. If carbon coating is required after pyrometallurgical or hydrometallurgical recycling protocols, more complex post-treatment is expected to be required.

[0143]

[0300] The resynthesized cathode material (R-CW) lost its ferromagnetism and exhibited a highly crystalline 3D layered structure. Figures 34A-34I, 35A-35E, 36A-36C, and 37A-37J. Regarding Figures 36A-36C, the amorphous carbon coating prevents direct exposure of the NMC cathode particles to the corrosive carbonate electrolyte and reduces parasitic reactions between the NMC and the electrolyte under high voltage conditions. It was also confirmed that, unlike fully graphitized carbon coatings, the amorphous carbon coating is permeable to Li ions. Therefore, the flash Joule heating method can be used to coat the cathode material. Regarding Figures 37A-37J, the presence of a thin carbon coating on the surface of the R-CW particles can be seen.

[0144]

[0301] The high-resolution TEM image and corresponding fast Fourier transform (FFT) pattern in Figure 13F show the presence of a layered structure on the surface of the cathode particles.

[0302] Atomic resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) imaging (Figures 13G and 38A-38D) shows the presence of a trigonal lattice with a space group (compared to fLCO, which has a spinel structure as shown in Figures 29A-29H, Figures 38A-38D show the presence of a recovered layered structure in the resynthesized cathode material).

[0145]

[0303] These results reflect the recovered layered structure in the resynthesized cathode material. The amorphous carbon coating on the R-CW particles is also retained after the resynthesis process, as shown by SEM (Figures 34A-34I), HR-TEM (Figures 36A-36C), STEM, and corresponding elemental mapping (Figures 13H and 37A-37J). Similarly, a layered structure was observed in R-LCO, and energy mapping indicated the presence of a carbon coating (Figures 34A-34I).

[0146] Atomistic simulation

[0304] The partially graphitized carbon crust may also be important in cell performance, since its permeability to Li ions is a factor in electrochemical processes. Using the AIREBO interatomic potential, we simulated high-temperature annealing during flash recycling for large amorphous carbon structures containing over 30,000 atoms. The initial configurations included small graphitic domains of arbitrary shape, ranging in size from 8 Å to 22 Å and up to three layers thick, randomly positioned within the periodic cell with offsets of up to 50°. The remaining 65% of the atoms were provided as individual carbon atoms randomly positioned within the unit cell. The resulting configurations were pre-annealed and slowly heated to the target temperature. For comparison, Figures 39A-39E show the results of annealing at 700 K, 1000 K, 1500 K, 2000 K, and 2500 K.

[0147]

[0305] Simulation at high temperature (2500K) was 0.9g / cm 3 The figure shows a completely amorphous carbon with a density of Li in the carbon crust using first-principles calculations. + To confirm the effect of annealing on permeability, Li +The diffusion of ions was compared across various features of the carbon structure. A particular role is played by the elimination of unpassivated graphitic edges during annealing. As demonstrated in Figures 40A-40D, the diffusion barrier on these structural elements can reach 1.5 eV, compared to a barrier of 0.34 eV for a perfect graphitic surface. Furthermore, unpassivated edges provide potential energy traps that are expected to capture Li ions, negatively impacting battery performance.

[0148]

[0306] In the surface, diffusion into the reconstructed divacancies is characterized by a 0.5 eV barrier, similar to that of the graphite surface. In addition, larger octagonal defects allow penetration through the surface, but a larger barrier of 1.6 eV must be overcome. Furthermore, the edges of well-reconstructed graphite form spherical shapes [Zhang 2012], acting as a continuation of the smooth surface with a 0.4 eV diffusion barrier. + Does not block diffusion.

[0149]

[0307] First-principles calculations show significant differences in the effect of various structural elements within amorphous carbon crusts on Li-ion diffusion (Figures 39A-39E and 40A-40D). Annealing improves the Li-ion permeability of the crusts, as observed, by eliminating unpassivated graphitic edge and point defects (see Figure 13I).

[0150] Flash Recycling Process Lifecycle

[0308] The electrochemical cycling performance of flash-recycled R-CW was studied in half-cells with an initial configuration of R-CW / Li. R-CW shows obvious decay in the first 10 cycles, but slower capacity fade is observed from cycles 25 to 200 compared to virgin LCO and virgin NMC cathodes without the flash-produced carbon coating, assembled under the same laboratory conditions (Figures 13J and 35A–35E). R-CW is much more stable than pristine CW.

[0151]

[0309] The improved cycling performance of this R-CW may be due to the carbon coating acting as an artificial CEI to avoid direct exposure of the cathode particles while maintaining high oxidative stability in the electrolyte. This reduces irreversible loss of active material during the electrochemical cycling process. Further optimization to minimize decay over the first 10 cycles is expected to increase efficiency, but even in this preliminary study, R-CW outperforms new cathode materials in similarly constructed systems. The ability to rapidly generate such a stabilized, Li-ion-permeable carbon coating without solvents or pastes may be particularly important for newer, higher-capacity, but less stable, NMC cathodes. This flash approach can be used not only for recycled materials but also for new cathodes.

[0152]

[0310] Using the Everbatt 2020 software package developed by Argonne National Laboratory for determining closed-loop life cycle analysis of LIBs [Everbatt 2020], the flash method was compared to different types of recycling processes and their efficiencies (Figures 41A-41F and 42A-42D).

[0153]

[0311] A closed-loop life cycle analysis scheme for LIBs illustrates the various phases during the recycling process (Figure 42A). Direct recycling processes, such as repair and repurposing, are easily operated but typically result in cycle-depleted and down-regulated cathode material. In contrast, current recycling processes, such as pyrometallurgical or hydrometallurgical methods, involve complex steps to recover useful metals in elemental and compound forms. However, these methods irreversibly destroy the structure of high-performance cathodes, requiring additional recomposition steps before they can be returned to service. The FJH method achieves high recovery rates without losing the layered structure of the cathode, reducing the operating period.

[0154]

[0312] Flash recycling facilitates reuse in fully functional batteries without destroying the layered structure of the cathode. (See Figure 13J.) Using an LCO-type cathode as a model, flash recycling reduces recycling costs by approximately 45%, recycling energy by approximately 70%, and GHG emissions by approximately 70%, while increasing recycling profitability by approximately $25 per kg of cathode and $18 per kg of cathode, respectively, compared with pyrometallurgical or hydrometallurgical methods. See Figures 41B-41E. With growing interest in cathode materials with lower Co content, such as NMC622, NMC811, and NCA, as well as non-Co-based systems, such as LiFePO4 and LiNiO2, flash recycling using these other ferromagnetic metals may bring more efficient recycling with increased profit margins within reach. (See Figure 41F.)

[0155]

[0313] It should be noted that there is a difference in revenue between pyrometallurgy and non-pyrometallurgy due to combustion for energy rather than sale. The utilization of this feedstock in different recycling methods is shown in Table IV.

[0156] [Table 4]

[0157]

[0314] Flash recycling of LIBs is therefore an environmentally cleaner way to reclaim metals in secondary batteries. The method preserves the 3D layered structure of the cathode, providing efficient reuse of elemental inventories. The rapid process also results in a convenient carbon coating on the recycled cathode particles that stabilizes the overall structure of the cathode while allowing Li-ion transport, thereby providing recycled batteries with superior performance over new batteries. The FJH process can be industrially scaled to multi-ton capacity per facility [Universal Matter 2021], enabling ease of manufacturing while minimizing reliance on newly mined metal ores for LIB production.

[0158] Flash recycling process for anode materials.

[0315] High-temperature calcination (1200-3000 K) remains the predominant process for regenerating graphite, but it is time- and energy-consuming, accounting for more than 50% of the recycling cost. The use of strong corrosive acids such as HCl and H2SO4 also raises serious concerns about secondary waste. Additionally, calcination leads to the formation of toxic and corrosive exhaust gases, such as HF, making these methods less promising for the treatment of original anode waste (AW) recovered directly from lithium-ion batteries (LIBs).

[0159]

[0316] A solvent- and water-free flash recycling method has been discovered to reactivate AW directly collected from spent LIBs. The method is completed within seconds and preserves the morphology of the graphite particles. The estimated energy cost is only approximately $67 to flash recycle one ton of original AW. After the flash recycling process, the mosaic-like SEI can be decomposed, and a graphene shell forms on the surface of the graphite particles. The formation of graphite layers derived from the SEI embedded with inorganic salts, such as LiF, Li2CO3, and Co3O4, can be observed. These inorganic salts can be easily recollected from the graphite by post-treatment with a 0.1 M HCl solution. The flash anode product exhibits a recovered specific capacity (358.9 mAh / g at 0.2 C) compared to the original AW and commercial graphite materials. Life cycle analysis (LCA) and comparison with current calcination methods show that the flash recycling method can significantly reduce total energy and water consumption, as well as greenhouse gas (GHG) emissions, demonstrating the environmental and economic potential of the flash recycling method.

[0160]

[0317] In an embodiment, an ultra-rapid, solvent-free flash Joule heating (FJH) method regenerates battery graphite anodes in bulk, dry powder form from battery anode waste. Characterization of the flash recycled product reveals an intact 3D layered graphite core structure coated with graphene shells derived from the solid electrolyte interphase (SEI). Valuable metals, lithium, cobalt, nickel, and manganese, can be easily recovered from the flash anode product by post-treatment with dilute acid. The flash anode material exhibits restored electrochemical performance compared to anode waste and virgin commercial graphite. A life cycle analysis compared to current calcination methods highlights that flash recycling can transform anode recycling into an economically advantageous process while significantly reducing total energy and greenhouse gas emissions.

[0161]

[0318] The FJH system is similar to those previously described. [See also Luong 2020; Chen 2021] Figures 43A-43B show a schematic diagram of the FTH setup and a diagram of the FJH reaction box. In the exemplary embodiment, Ar gas (approximately 1 atm) was used as an inert atmosphere to avoid sample oxidation during the FJH reaction. The reactants were graphite anode waste collected from the anode side of used Li-ion batteries. The reactant powders were ground and uniformly mixed using a mortar and pestle, then loaded into reaction tubes with an inner diameter of 8 or 16 mm. The reaction tubes could be quartz or ceramic tubes, or concrete or other non-conductive materials. The masses loaded into the 8 mm and 16 mm tubes were 200 mg and 1 g, respectively. Graphite rods were used as electrodes in this reaction. The compression force was controlled by a small vice connected to a rotary knob, as shown in Figure 43B, and the sample resistance was adjusted to approximately 2 Ω. An Arduino controller with a programmable millisecond-level delay time was used to control the discharge time, and the electricity 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. For the 8 mm tube reaction, the FJH reaction was performed using a voltage of 120 V and an optimized duration of 1000 ms (further details are shown in Table V). After the FJH reaction, the device was allowed to cool and evacuated for 3 minutes. In this context, the product is referred to as flash anode waste (fAW).

[0162] [Table 5]

[0163]

[0319] In a typical flash recycling process, AW collected from spent lithium-ion batteries (LIBs) is used directly as a reactant without further processing. The AW, in powder form, is slightly compressed inside a quartz tube between two graphite electrodes (Figures 43A-43B). A capacitor bank in the circuit is used to provide electrical heating energy to the AW reactant for approximately 1000 ms (Figures 44A-44B). During a typical flash recycling process using a voltage of 120 V and a resistance of approximately 1.3 Ω, the current passing through the sample reaches approximately 350 A with a discharge time of approximately 1000 ms (Figure 44C). The total amount of electrical energy is 1210 J / g, most of which (>80%) is targeted to heating and decomposing the SEI (continuous phase), while the graphite particles (dispersed phase) receive only <20% of the electrical energy, according to the Joule heating distribution law (Figure 44C). This effect of Joule heating of the continuous phase reflects the selective reaction of the resistive layer (continuous phase) at the interface, in our case graphitization of the SEI.

[0164]

[0320] In the conventional calcination process (Figures 45A-45B), the entire system, including the environment and anode waste, is subjected to high temperatures (>1300 K) for several hours under inert atmosphere protection, which requires high energy consumption, generates more GHGs, and also generates secondary waste. [Yu 2021]. The flash recycling process achieves instantaneous, localized heating of the AW with the desired selectivity, and the environment facilitates rapid heat transfer from the subsequent reactants, avoiding thermal expansion and defect formation. The temperature is measured with a high-temperature infrared thermometer, with a maximum temperature of approximately 2850 K. During the flash process, the ultrafast heating rate is approximately 1.6 × 10 5 K / s, and the cooling rate is approximately 9.2 × 10 3 K / s (Figures 45A-45B).

[0165]

[0321] To confirm the decomposition of the SEI structure and evaluate the removal of "dead mass" in the flash recycling process, thermogravimetric analysis (TGA) is used due to the distinct thermal stabilities of the SEI, binder, and other components, such as graphite or inorganic salts (Figures 46A-46D) [Beyer 2013; Advincula 2021].

[0166]

[0322] For pristine AW, there is a mass loss of approximately 16.3% at 773 K (Figure 47), but after the flash reaction, the mass loss is dramatically reduced. After two cycles of flashing at 120 V, the mass loss, which may be caused by the decomposition of lithium salts such as LiOH, is negligible (approximately 1.2%), as shown by differential scanning calorimetry (DSC) results (Figure 46B) [Beyer 2013]. Similar results are observed for calcined AW (cAW), prepared by calcination at 1323 K for 1 h under argon protection, which shows minimal mass loss at 773 K. A significant reduction in mass loss can also be found after scaling up this system to the gram level. Visual images of various anode materials can be seen in Figures 48A–48F. Therefore, the flash process can effectively decompose the SEI and remove the "dead mass" accumulated in pristine AW. Notably, at 1273 K, the remaining solids comprise approximately 12.1% of the flash product, compared to <4.0% for cAW (Figure 49). The difference in remaining weight indicates that the flash recycling method preserves inorganic salts and facilitates subsequent metal collection.

[0167]

[0323] To investigate the changes after the flash process, the bulk crystal structure and the surface / subsurface regions of the flashed products are analyzed by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. In Figures 50 and 51A-51B, the crystal structures of flashed AW (fAW) and cAW are compared with those of the original AW. High-temperature calcination removes most of the organic and inorganic impurities remaining in the original AW, allowing only the diffraction peaks of graphite to be identified [Advincula 2021]. The flash recycling process can decompose the SEI structure, accompanied by the conversion of other species, such as LiF, not present in the original AW. The (002) diffraction peaks of both cAW and fAW are centered at approximately 26.5°, indicating an interlayer distance of approximately 3.36 Å, consistent with the layered structure of graphite. The presence of LiF and Li2CO3, as well as a layered structure of graphite with a similar interlayer distance (about 3.36 Å), is also observed in fAW synthesized from large batches (Figures 52A-52C).

[0168]

[0324] Compared to AW, which is enriched in F (23.8%), O (14.4%), and P (1.9%) on the surface, fAW exhibits a relatively high content of C (89.6%) and a reduction in other nonmetallic elements, such as F (5.7%), O (2.9%), and P (<0.1%) (Figure 53 and Table V). cAW also has a high content of C (92.8%) and reduced contents of other elements, such as F (1.1%) and O (6.1%), on the surface (Figure 54). Depth analysis of the pristine AW shows clear ratio changes of various elements, such as Li and F, from 0 to 200 nm, which become relatively constant below 200 nm (Figures 55A-55F), reflecting the elemental composition and SEI at the top of the graphite microparticles.

[0169]

[0325] The flash recycling process decomposes the SEI structure and alters the subsurface region to a depth of at least 500 nm, while reducing the content of nonmetals such as O, F, and P at the surface (Figures 55A-55F). The reduction in nonmetal content observed in fAW is comparable to that observed in cAW prepared by high-temperature calcination. The removal of the original organic SEI and electrolyte residues on the original AW can be further confirmed by UV-vis spectroscopy. After dispersing the original AW in deionized water, the supernatant exhibited a yellowish color with a broad peak centered at approximately 220 nm, which may be attributed to the oxidized carbonate electrolyte and organic SEI [Bouteau 2019]. In comparison, fAW dispersed in water at the same concentration (approximately 5 mg / mL) yielded a clear solution. A small transition peak located at approximately 230 nm was observed from the fAW, which is attributed to the presence of LiF salt (Figure 56) [Baldacchini 2004].

[0170]

[0326] As shown by scanning electron microscopy (SEM) and the corresponding particle size distributions (Figures 57A-57L), the bulk structure of the graphite microparticles is preserved and the average size (approximately 15 μm) is similar after the flash recycling process.

[0171]

[0327] To identify changes in the surface structure, high-resolution transmission electron microscopy (HR-TEM) was performed, as shown in Figures 58A-58D and 59A-59D. In the case of AW (Figures 58A-58D), there is an amorphous layer outside the graphite microparticles, with an average thickness of approximately 145 nm. Graphite lattice fringes can be identified below this layer. Within the amorphous layer, there are several small embedded Li2CO3 crystals, which is consistent with the mosaic model of the SEI structure.

[0172]

[0328] After the flash reaction (Figures 59A-59D), the SEI layer is pyrolyzed, the carbon portion is graphitized, and the average thickness is reduced to approximately 65 nm. A graphene shell can be seen in the outermost region with embedded nanoparticles such as Co3O4 and LiF formed from elements in the SEI layer of the original AW. This can be inferred from the scanning transmission electron microscope (STEM) and corresponding element distribution results (Figures 60-61).

[0173] Metal recovery

[0329] These metal nanoparticles and salts appear to be trapped by the modified graphene layers, but they can be removed by rinsing the material with dilute acid. Therefore, useful metals, such as Co and Li, can be recovered from the fAW by simple acid post-treatment. The presence of Co within the SEI on the anode side is not unexpected. Cobalt dissolution from lithiated metal oxide cathodes has been observed in end-of-life batteries [Li 2020]. Because the SEI traps electrolyte, it is also expected to host a concentration of dissolved Co ions, which are converted to metal oxide nanoparticles during flash recycling.

[0174]

[0330] To recover useful metal ions from the flash product, HCl solutions with different concentrations are used for comparison. Two factors, recovery efficiency (α) and excess yield Y / Y0, are defined to evaluate the recovery results. α is the recovery rate of one species (metal from AW, fAW, or cAW) relative to the recovery rate achieved by concentrated acid, and Y / Y0 is the yield obtained from various treated anode materials (fAW or cAW) relative to the yield obtained from the original AW using the same recovery procedure.

[0175]

[0331] Compared to the concentrated hydrochloric acid (10-11 M) currently used in the battery recycling industry, dilute hydrochloric acid (0.01-1 M) can also effectively recollect metal ions from the flash product, with an average recovery efficiency reaching approximately 97.5% by using 0.1 M HCl (Figure 62A). By using 0.1 M HCl, the total amount of metal ions recovered from the fAW was also higher than that recovered from the original AW, with an average excess yield of 1.12, indicating that 12% more metal ions could be collected from the flash product. This result is supported by STEM images and elemental mapping, which show the formation of metal oxide nanoparticles and polar salts such as Co3O4 and LiF after the flash reaction.

[0176]

[0332] Compared with the organic salts formed within the SEI, these inorganic metal oxides and polar salts can be completely dissolved in more dilute acid solutions. Therefore, the average recovery efficiency for each metal ion, e.g., Li (99.4%) and Co (80.1%), was high even when treated with a 0.1 M HCl solution (Figure 62B). The average excess yields of Li and Co were 1.10 and 1.19, reflecting the recovery of 10% more Li and 19% more Co from the flash product than from the original AW.

[0177]

[0333] In comparison, direct high-temperature calcination causes the evaporation of these metal sources, which can become concentrated downstream and corrosive to devices such as metal chambers and glass pipelines. Therefore, only <15% of the total metal ions can be collected in the different HCl solutions (Figure 62C). TGA results show that for pristine AW and fAW, after heating to 1273 K under air, the weight percentages were 10–15 wt%, and the remaining solids are the primary source for the different metal ions (Figure 62D).

[0178]

[0334] Figure 62E shows the absolute amounts of different metal ions in the material and compares the extent 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 the fAW, which are higher than those found in natural sources such as ores and brines (100-1000 ppm for Li) or seawater (<0.21 ppm for Li). Additionally, these metal species can be easily recollected with dilute acid solutions, and the presence of Na in the fAW is also evident. + (approximately 13,000 ppm in seawater), Ca 2+ , Mg 2+ and K. + After rinsing the fAW with 0.1 M HCl solution and then heating it to 1273 K under air, almost no mass remained and only graphite diffraction peaks could be identified, indicating effective recovery of various useful metal ions from the fAW compared to the pristine AW (Figures 63A-63B). HR-TEM and corresponding fast Fourier transform (FFT) results of the rinsed fAW sample (fAW-W) show the disappearance of these nanoparticles and a series of six-fold diffraction patterns along the 0002 zone axis, thereby confirming the recollection of various useful metal ions and the preservation of well-graphitized anode particles (Figures 64A-64D). Because the use of dilute HCl solution significantly reduces potential tool erosion and mitigates potential hazards to workers and the environment, the flush recycling method may be applied to anode regeneration and metal source recovery.

[0179] Effectiveness

[0335] To evaluate the effectiveness of the flash recycling method, we tested the electrochemical properties of various anode materials, including bulk resistivity, rate capability, and electrochemical stability. Polarization 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 significant decrease in bulk resistivity (approximately 63%) from AW to fAW indicates the decomposition of the resistive SEI. Due to the surface coating of a fluorinated layer obtained by the flash process, the resistance of fAW is still greater than that of intrinsic graphite materials. This fluorinated layer can act as an artificial SEI layer to improve reversibility during the first cycle associated with the formation of a new SEI, which contributes to the electrochemical stability during subsequent charge and discharge processes.

[0180] [Table 6]

[0181]

[0336] The skeletal density of the anode material is approximately 2.2 g / cm 3 As shown in Figure 65, the coulombic efficiencies (CE) of fAW, cAW, and graphite in the first cycle are 84.4%, 74.3%, and 80.3%, respectively. The areal capacity of the tested anodes is about 3.0 mAh / cm. 2 This result indicates that fAW exhibits a smaller irreversible loss of electrochemically active Li species compared to cAW and commercial graphite.

[0182]

[0337] The reduction of solution components, including solvent and salt anions, and the simultaneous growth of the SEI are observed at 0.5–1.5 V (Li / Li +Because the irreversible capacity loss occurs at a rate of 1000 kJ / s (relative to the charge transport rate), fAW exhibits the smallest irreversible capacity loss (approximately 20 mAh / g) compared to AW (approximately 46 mAh / g) and commercial graphite (approximately 37 mAh / g). cAW exhibits the largest irreversible capacity loss (approximately 55 mAh / g), which is associated with the CE during the first cycle. The favorable SEI formation for fAW reduces polarization with cycling and leads to lower overpotentials, especially at higher rates (>0.5 C), compared to graphite, pristine AW, and cAW (Figures 66A-66C).

[0183]

[0338] The average specific capacities of fAW are 341.5, 331.9, 233.1, and 154.1 mAh / g at rates of 0.05 C, 0.1 C, 0.4 C, and 0.8 C, respectively (Figure 67). This result shows enhanced rate performance compared to pristine AW and is comparable to virgin graphite or cAW due to the removal of the resistive SEI by the flash method. When the rate is returned to 0.2 C, the fAW has a capacity of 358.9 mAh / g.

[0184] Economic and environmental impacts

[0339] We compare the economic and environmental impacts of preparing synthetic graphite, cAW, and fAW using GREET 2020 and Everbatt 2020, developed by Argonne National Laboratory. Figures 68A-68C show the flowcharts. SEI can be effectively decomposed within seconds in the flash recycling method by providing localized and instantaneous heating to the original AW. As shown in the preparation of synthetic graphite, there is no need to carbonize or graphitize carbonaceous materials or heat the environment for several hours through high-temperature calcination methods. Therefore, the flash recycling method reduces recycling costs by approximately 48%, GHG emissions by approximately 39%, water by approximately 98%, and energy by approximately 48% (Figures 69A-69E).

[0185]

[0340] Since the average price of natural graphite material (battery grade) is approximately 10 USD / kg [Advincula 2021], the profit margin for synthetic graphite is negative (-1.75 USD / kg). Therefore, in the modern market, the price of synthetic graphite is higher (approximately 20 USD / kg) and less competitive. In comparison, the high-temperature calcination method shows a slightly positive profit (0.70 USD / kg), and the flash recycling method has the largest positive profit (3.90 USD / kg), again reflecting the potential of the method of the present invention to increase profit margins from battery recycling.

[0186] use

[0341] Spent graphite anodes can be regenerated by the ultra-high rate and solvent-free flash recycling method disclosed and taught herein.

[0187]

[0342] The resulting flash anode material exhibits an intact 3D layered graphite core structure coated with layers derived from the solid electrolyte interphase (SEI). Valuable metals, lithium, cobalt, nickel, and manganese, can be easily recovered from the flash anode product by post-treatment with dilute acid. The flash anode material exhibits restored electrochemical performance compared to anode waste and new commercial graphite.

[0188]

[0343] A life cycle analysis of current calcination methods highlights that flash recycling methods can be an economically advantageous process while significantly reducing total energy and greenhouse gas emissions.

[0189]

[0344] The formation of coating structures around graphite microparticles demonstrates the feasibility of preparing core-shell or other hierarchical topological structures within seconds by a solvent-free flash method.

[0190]

[0345] In embodiments, the electrolyte may be removed from the anode material, as well as the separator and current collector, hi other embodiments, one or more of the electrolyte, separator, and current collector may be retained with the anode material in the mixture or may be flushed.

[0191] Destruction of the 3D morphology of the cathode

[0346] In some embodiments discussed and described above, the 3D structure of the cathode can be maintained during flash Joule heating. However, in some circumstances, care is not taken to preserve the 3D structure of the cathode, for example, because the former 3D structure is no longer compatible with newer battery technologies. This may be particularly the case since battery designs tend to be upgraded every 2-3 years. In such circumstances (where there is no need to preserve the 3D morphology), the only requirement would be to easily obtain the metals Li, Co, Mn, Ni, and Cu, as well as other metals if applicable.

[0192]

[0347] The use of higher current flash Joule heating pulses than previously used and described, which would be expected to readily form dissolved metal oxides, has been found to decompose 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. Furthermore, the acid concentrations are much lower than those required for typical hydrometallurgical recycling, and the energy requirements are far less than those required for pyrometallurgical recycling. Furthermore, this higher current FJH method can produce lithium salts unlike those provided by pyrometallurgical methods (described above). Previously, 120 V and 30 A pulses were used for 150 to 300 milliseconds to preserve the 3D structure of the cathode, using a 10 wt% conductive carbon additive. Using the same flash vessel size to destroy the 3D cathode structure, dissolving the metal more readily in the flash vessel as substantially metal oxide and metal(0) was accomplished by increasing the conditions from 120 V and 90 A to 100 A for 500 ms while using a 33.3 wt% conductive carbon additive. Using the same vessel size, volatilizing the metal from the flash container into a trap can be achieved by utilizing 120 V at approximately 200 A to 300 A for 500 ms to 1 s while using a 33.3 wt% carbon additive.

[0193]

[0348] Such high current FJH processes can decompose cathode materials into simple metal oxides and even metal(0) that are easily dissolved in dilute acids, such as 0.1 M HCl, and even 0.01 M HCl. The acid is much less corrosive than the reagents used in current hydrometallurgical processes, such as 12 M HCl and peroxides, and NaOH rinses.

[0194]

[0349] For comparison purposes, FJH was performed under conditions for preserving the 3D structure (A) and for destroying the 3D structure (B). In the former case (flush conditions for preserving the 3D structure), the conditions were 10 wt% conductive carbon addition, 120 V, 30 Amp, 300 ms for LCO and 150 ms for NMC, and magnetic extraction of the desired contents. In the latter case (flush conditions for destroying the 3D structure), the conditions were 33 wt% conductive carbon addition, 120 V, 100 Amp, 500 ms for both LCO and NMC, and no magnetic extraction was performed; instead, a dilute acid rinse was used to obtain the desired metal oxides.

[0195]

[0350] The FJH method provided rapid electrical energy within 500 ms, thereby avoiding weight loss of metals with low boiling points, such as Li. The metal contents in the flash joule-heated reactor remained in the reactor if the graphite electrode spacers were snugly fitted. As can be seen in Figure 70, metal loss due to sublimation was not an issue.

[0196]

[0351] The total amounts of Li and Co from LCO and flashed LCO were measured by leaching with concentrated hydrochloric acid solution. As shown in Figure 71, the recovery rates of Li and Co were approximately 100% after flashing, indicating no obvious metal loss due to the FJH process.

[0197]

[0352] Metal salts were leached using different concentrations of HCl. The recovery efficiencies are compared in Figures 72A-72B. As shown in Figure 72A, in the case of Li, by varying the concentration, Li can be effectively recovered from LCO and flash LCO with efficiencies >90% (curves 7201-7202, respectively), with slightly higher efficiencies observed from flash LCO. As shown in Figure 72B, in the case of Co, as the acid concentration decreases, the recovery efficiency decreases in LCO (curves 7203-7204 for LCO and flash LCO, respectively). However, the efficiency of Co does not decrease in flash LCO.

[0198]

[0353] The distribution of metals after FJH was also analyzed separately from the chamber, the quartz tube cell, and the powdered FJH product in the graphite electrode, see Figure 73. Approximately 30% of the metal ions were attached to the quartz tube and graphite, and the remaining 70% were in the powdered product.

[0199]

[0354] The total amounts of Li, Co, Ni, and Mn from NMC and flashed NMC were also measured by leaching with concentrated hydrochloric acid. After flashing, the recovery rates of Li, Co, Ni, and Mn were often approximately 100%, as shown in Figure 74, indicating no obvious metal loss due to the FJH process. Note that the quartz tube is used here only as a convenient transparent container at the research scale. Upon scaling up, quartz tubes would typically not be used due to their cost and fragility. Other reactor cells, such as ceramic, concrete, and high-temperature concrete, would be used. High-temperature stable plastics such as Teflon and polyphenylene sulfide tubes could also be used because the current does not pass through these insulating materials, and therefore their temperature increase is negligible.

[0200]

[0355] In Figures 75A-75D, curves 7501-7504 show the recovery of Li, Co, Ni, and Mn from NMC in HCl solutions at different concentrations, respectively, and curves 7505-7508 show the recovery of Li, Co, Ni, and Mn from flashed NMC in HCl solutions at different concentrations, respectively. These curves reveal that 0.1 M HCl was sufficient to remove metal salts from the flashed cathode.

[0201]

[0356] While embodiments of the present invention have been shown and described, modifications thereof can be made by those skilled in the art without departing from the spirit and teachings of the present invention. The embodiments described herein and examples provided are merely illustrative and are not intended to be limiting. Many variations and modifications of the invention disclosed herein are contemplated and are within the scope of the present invention. The scope of protection is not limited by the above description, but is limited only by the following claims, which scope includes all equivalents of the subject matter of the claims.

[0202]

[0357] The disclosures of all patents, patent applications, and publications cited herein, to the extent that they provide exemplary, procedural, or other details supplementary to those set forth herein, are hereby incorporated by reference in their entireties.

[0203]

[0358] Quantities and other numerical data may be presented in range format herein. It is 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 range limits, but also all individual numerical values ​​or subranges subsumed within the range, as if each numerical value and subrange were explicitly recited. For example, a numerical range of about 1 to about 4.5 should be interpreted not only to include the explicitly recited limits of 1 to about 4.5, but also to include individual numbers, e.g., 2, 3, 4, and subranges, e.g., 1-3, 2-4, etc. The same principle applies to ranges reciting only a single numerical value, such as "less than about 4.5," which should be interpreted as including all of the values ​​and ranges recited above. Furthermore, such interpretation should apply regardless of the breadth of the range or the characteristics described.

[0204]

[0359] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by 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.

[0205]

[0360] Following long-standing patent law convention, the terms "a" and "an" mean "one or more" when used in this application, including the claims.

[0206]

[0361] Unless otherwise indicated, all numerical values ​​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." Accordingly, unless otherwise indicated, the numerical parameters set forth in the specification and appended claims are approximations that may vary depending upon the desired properties sought to be achieved by the presently disclosed subject matter.

[0207]

[0362] As used herein, the terms "about" and "substantially," when referring to a mass, weight, time, volume, concentration, or percentage value or amount, are meant to encompass variations from the specified amount 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%, as such variations are appropriate for performing the disclosed methods.

[0208]

[0363] As used herein, the terms "substantially perpendicular" and "substantially parallel" are meant to encompass variations within ±10° of each of the perpendicular and parallel directions in some embodiments, within ±5° of each of the perpendicular and parallel directions in some embodiments, within ±1° of each of the perpendicular and parallel directions in some embodiments, and within ±0.5° of each of the perpendicular and parallel directions in some embodiments.

[0209]

[0364] As used herein, the term "and / or," when used in the context of listing entities, refers to the entities being present singly or in combination. Thus, for example, the phrase "A, B, C, and / or D" includes not only A, B, C, and D individually, but also any and all combinations and subcombinations of A, B, C, and D.

[0210] Abbreviation

[0365] Further abbreviations used throughout this application are listed below.

[0366] AW: Anode waste

[0367] cAW: calcined AW

[0368] CB: Carbon black

[0369] CEI: cathode electrolyte interphase

[0370] CW: cathode waste

[0371] fAW: Flash AW

[0372] fCW: Flash CW

[0373] fLCO: Flash LCO

[0374] fNMC: Flash NMC

[0375] FJH: Flash Joule Heating

[0376] GHG: Greenhouse gas

[0377] Hydro: Hydrometallurgy

[0378] LCA: Life Cycle Analysis

[0379] LCO: Lithium cobalt oxide (LiCoO2)

[0380] LIB: Li-ion battery

[0381] NMC: Lithium nickel-manganese-cobalt oxide (LiNi x Mn y Co z O2, usually referred to as NMCxyz, e.g. NMC811)

[0382] R-CW: Recombined cathode material

[0383] Pyro: Pyrometallurgy

[0384] SEI: Solid electrolyte interphase.

[0211]

[0385] It should be noted that the nomenclature of the terms "LCO" and "NMC" used herein is consistent with that used in the industry. In the case of a lithium cobalt oxide cathode, the term LCO includes lithium in the acronym. However, in the case of a lithium nickel-manganese-cobalt oxide cathode, the term NMC does not include lithium in the acronym. To avoid confusion, the term "NMC" as used herein is synonymous with the terms "Li-NMC" and "LNMC," which are examples of alternative terms used in the industry for lithium nickel-manganese-cobalt oxide (used in the cathode). In a fully charged battery, most of the lithium is present in the anode. In a discharged battery, most of the lithium is present in the cathode, with little present in the anode. Thus, the amount of lithium in the cathode depends on the state of charge. Generally, batteries are expected to be discharged before recycling, so most of the lithium ions are expected to be pushed to the cathode. Therefore, in the case of an NMC cathode, the battery can be adequately described as lithium nickel manganese cobalt, since it is expected to contain a large amount of lithium as the battery discharges. In the case of LCO, some of the lithium migrates from the cathode to the anode. However, even when the battery is fully charged, some lithium is always present in the cathode, and this is especially true for LCO structures.

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[0434] 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 for recovering metals, comprising: (a) forming a mixture including a cathode material, the cathode material being prepared from one or more batteries; (b) applying a voltage across the mixture to obtain metal and cathode waste from the cathode material; (i) the voltage is applied in one or more voltage pulses; (ii) the duration of each of the one or more voltage pulses is for a period of predetermined duration; and (c) magnetically separating the metal and the cathode waste. The above method, comprising: [2] The method of [1], wherein the metal comprises a cathode metal selected from the group consisting of lithium, cobalt, nickel, manganese, iron, and combinations thereof. [3] The method of [1], wherein the metal comprises a cathode metal selected from the group consisting of metal oxides, metal salts, metal carbonates, metal phosphates, and combinations thereof. [4] The method according to [3], wherein the cathode metal comprises a metal oxide. [5] The method according to [4], wherein the metal oxide comprises cobalt oxide. [6] The method of [3], wherein the cathode metal comprises a metal carbonate. [7] The method according to [6], wherein the metal carbonate comprises lithium carbonate. [8] The method of [3], wherein the cathode metal comprises a metal phosphate. [9] The method according to [8], wherein the metal phosphate comprises iron phosphate.

[10] The method of [1], wherein the one or more batteries comprise a battery 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, anodeless batteries, metal oxygen batteries, metal air batteries, and combinations thereof.

[11] The method of [1], wherein the one or more batteries comprise one or more lithium-ion batteries.

[12] The method of

[11] , wherein the one or more lithium-ion batteries comprise lithium-ion batteries having a lithium cobalt oxide (LCO) cathode or a lithium nickel-manganese-cobalt oxide (NMC) cathode, respectively.

[13] The method of

[12] , wherein each of the one or more lithium ion batteries comprises a respective LCO cathode.

[14] The method of

[12] , wherein each of the one or more lithium-ion batteries comprises an NMC cathode.

[15] The method of

[12] , wherein the metal obtained by applying the voltage comprises a cathode metal comprising a metal phosphate.

[16] The method of

[15] , wherein the metal phosphate comprises iron phosphate.

[17] The method of

[12] , wherein each of the portions of the one or more lithium ion batteries comprises an LCO cathode and each of the portions of the one or more lithium ion batteries comprises an NMC cathode.

[18] The method of

[12] , wherein the one or more lithium-ion batteries include a lithium-ion battery having a cathode comprising a mixture of lithium cobalt oxide (LCO) and lithium nickel manganese cobalt oxide (NMC).

[19] The method of [1], wherein the mixture further comprises a conductive additive.

[20] The method according to

[19] , wherein the conductive additive is a carbon source.

[21] The method of

[19] , wherein the conductive additive is selected from the group consisting of graphite, anode graphite, battery grade graphite, elemental carbon, carbon black, graphene, flash graphene, turbostratic graphene, coal, anthracite, coke, metallurgical coke, calcined coke, activated carbon, biochar, carbon from natural gas with hydrogen atoms removed, activated carbon, shungite, plastic waste, carbon char derived from plastic waste, food waste, carbon char derived from food waste, biomass, biomass-derived carbon char, carbon char derived from hydrocarbon gas, and mixtures thereof.

[22] The method according to

[19] , wherein the conductive additive is carbon black.

[23] The method of

[19] , wherein the conductive additive is primarily elemental carbon.

[24] The method of

[19] , wherein the conductive additive is selected from the group consisting of metals, metal salts, metal oxides, metalloids, metal complexes, conductive phosphorus, and non-metallic conductive materials.

[25] The method of

[24] , wherein the conductive additive is selected from the group consisting of metals, metal salts, metal oxides, metalloids, and metal complexes.

[26] The method according to

[24] , wherein the conductive additive is a metalloid.

[27] The method according to

[26] , wherein the metalloid is selected from the group consisting of B, Si, As, Te, and At.

[28] The method of

[19] , wherein the conductive additive is prepared from the anode material of the one or more batteries.

[29] The method of

[19] , wherein the conductive additive is not prepared from the one or more batteries.

[30] The method according to

[19] , wherein the cathode material and the conductive additive are mixed in a weight ratio ranging from 1:2 to 25:1.

[31] The method according to [1], wherein the applied voltage is in the range of 15V to 300V.

[32] (a) the mass of the mixture to which the voltage is applied is greater than 1 kg; (b) The method according to [1], wherein the applied voltage is 100V to 100,000V.

[33] The method according to

[32] , wherein the mass of the mixture to which the voltage is applied is greater than 100 kg.

[34] (a) the mass of the mixture to which the voltage is applied is greater than 1 kg; (b) The method according to [1], wherein the applied current is between 1,000 amp and 30,000 amp.

[35] The method according to

[34] , wherein the mass of the mixture to which the voltage is applied is greater than 100 kg.

[36] The method of [1], wherein the mixture has a resistance in the range of 0.1 ohms to 25 ohms when the voltage is applied.

[37] The method of [1], wherein the period of each duration of the one or more voltage pulses is between 1 microsecond and 25 seconds.

[38] The method of [1], wherein the period of each duration of the one or more voltage pulses is between 1 microsecond and 10 seconds.

[39] The method of [1], wherein the period of each duration of the one or more voltage pulses is between 1 microsecond and 1 second.

[40] The method of [1], wherein the duration of each of the one or more voltage pulses is between 100 microseconds and 500 microseconds.

[41] The method according to [1], wherein the one or more voltage pulses are between two voltage pulses and 100 voltage pulses.

[42] The method according to [1], wherein the voltage pulse is performed using direct current (DC).

[43] The method of [1], carried out using a pulsed direct current (PDC) Joule heating process.

[44] The method of [1], wherein the voltage pulse is performed using alternating current (AC).

[45] The method according to [1], wherein the voltage pulse is performed by using both direct current (DC) and alternating current.

[46] The method of

[45] , which alternates between using direct current (DC) and alternating current (AC).

[47] The method described in

[45] , using direct current (DC) and alternating current (AC) simultaneously.

[48] ​​The method of [1], wherein the one or more voltage pulses increase the temperature of the mixture to at least 3000K.

[49] The method of [1], wherein the metal obtained by applying a voltage across the mixture comprises metal particles having a carbon coating.

[50] The method of

[49] , wherein the carbon coating is electrically conductive.

[51] The method of

[49] , wherein the carbon coating is ion-permeable.

[52] The method of

[49] , wherein the carbon coating is electrically conductive and ion-permeable.

[53] The method of

[49] , wherein the carbon coating is ion-permeable to metal ions.

[54] The method according to

[53] , wherein the metal ions are selected from the group consisting of lithium ions, sodium ions, potassium ions, magnesium ions, zinc ions, and aluminum ions.

[55] The method of

[49] , wherein the carbon coating is amorphous.

[56] The method of

[49] , wherein the carbon coating comprises graphene.

[57] The method of [1], wherein the cathode material maintains the 3D layer structure of the cathode.

[58] The method of [1], wherein the cathode material retains the 3D morphology of the cathode.

[59] The method of [1], wherein the cathode material destroys the 3D morphology of the cathode.

[60] The method of [1], further comprising a cooling step, wherein the cooling step cools the metal and the cathode waste prior to the step of magnetically separating the metal and the cathode waste.

[61] The method according to [1], wherein the metal and cathode waste are in a weight ratio of 20:1 to 5:1.

[62] The method according to

[61] , wherein the metal and cathode waste are in a weight ratio of 10:1 to 8:1.

[63] Further comprising applying a second voltage across the cathode waste after the mechanically separating step; (a) the second voltage is applied in one or more second voltage pulses; (b) the duration of each of the one or more second voltage pulses is for a second predetermined duration period.

[64] (a) the second voltage is the same as the voltage applied across the cathode material; (b) the duration of the second duration is the same as the duration of the voltage applied across the cathode material.

[65] (a) applying the second voltage across the cathode waste captures additional metal and a reduced portion of the cathode waste; (b) The method according to

[63] , wherein the method further comprises a step of magnetically separating the additional metal and the reduced portion of the cathode waste.

[66] The method of

[65] , wherein the further metal and the reduced portion of the cathode waste are in a weight ratio of at least 1:1.

[67] The method of

[66] , wherein the further metal and the reduced portion of the cathode waste are in a weight ratio of at least 1.5:1.

[68] The method of [1], further comprising recovering the metal by collecting the metal after separating it from the cathode waste.

[69] (a) the cathode material comprises a first mass of a cathode metal selected from the group consisting of lithium, cobalt, nickel, magnesium, and combinations thereof; (b) the collected metal comprises at least 70 wt% of the first mass of the cathode metal.

[70] The method of

[69] , wherein the collected metal comprises at least 70 wt% of the lithium in the first mass of the cathode metal.

[71] The method of

[69] , wherein the collected metal comprises at least 70 wt% of the cobalt in the first mass of the cathode metal.

[72] The method of

[69] , wherein the collected metal comprises at least 70 wt% of the nickel in the first mass of the cathode metal.

[73] The method of

[69] , wherein the collected metal comprises at least 70 wt% of the magnesium in the first mass of the cathode metal.

[74] The method of

[69] , wherein the collected metal comprises at least 70 wt% of each of lithium, cobalt, nickel, and magnesium in the first mass of cathode metal.

[75] The method of

[69] , wherein the collected metal comprises at least 90 wt% of the lithium in the first mass of the cathode metal.

[76] The method of

[69] , wherein the collected metal comprises at least 90 wt% of the cobalt in the first mass of the cathode metal.

[77] The method of

[69] , wherein the collected metal comprises at least 90 wt% of the nickel in the first mass of the cathode metal.

[78] The method of

[69] , wherein the collected metal comprises at least 90 wt% of the magnesium in the first mass of the cathode metal.

[79] The method of

[69] , wherein the collected metal comprises at least 90 wt% of each of lithium, cobalt, nickel, and magnesium in the first mass of cathode metal.

[80] The method of [1], carried out in a continuous or automated process.

[81] The method according to any one of [1] to

[80] , wherein the metal is recycled into a new metal-ion or metal battery.

[82] The method of

[81] , wherein the metal is recycled as a cathode material in a new metal-ion or metal battery.

[83] A method for recovering metals, comprising: (a) forming a mixture including a cathode material, the cathode material being prepared from one or more batteries; (b) applying a voltage across the mixture to obtain metal and cathode waste from the cathode material; (i) the voltage is applied in one or more voltage pulses; (ii) the duration of each of the one or more voltage pulses is for a period of predetermined duration; and (c) magnetically separating the metal and the cathode waste. The above method, comprising:

[84] The method of

[83] , wherein the one or more batteries are one or more non-lithium metal ion batteries.

[85] The method of

[83] , wherein the one or more batteries comprise 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, anodeless batteries, metal oxygen batteries, metal air batteries, and combinations thereof.

[86] A system for carrying out a method for recovering metals using at least one of the methods described in [1] to

[85] , (a) a source of a mixture containing a cathode material; (b) a cell operably connected to the source, the mixture flowing into the cell and being held under compression; (c) an electrode operably connected to the cell; (d) a flash power supply for applying a voltage across the mixture to obtain metal and cathode waste from the cathode material; (e) a magnet in operative contact with the metal and the cathode waste, the magnet being operable in response to magnetically separating the metal and the cathode waste. The system as described above.

[87] The system of

[86] , wherein the mixture further comprises a conductive additive.

[88] The system of

[86] , operable to perform a continuous or automated process.

[89] A method for recovering metals, comprising: (a) forming a mixture including battery materials, the battery materials being prepared from one or more batteries; (b) applying a voltage across the mixture to obtain metals and battery waste from the battery materials, (i) the voltage is applied in one or more voltage pulses; (ii) the duration of each of the one or more voltage pulses is for a period of predetermined duration; and (c) magnetically separating the metal from the battery waste The above method, comprising:

[90] The method of

[89] , wherein the one or more batteries comprise one or more lithium ion batteries.

[91] The method of

[89] , wherein the one or more batteries comprise 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 batteries, anode-less batteries, metal-oxygen batteries, metal-air batteries, and combinations thereof.

[92] The method of

[89] , wherein the mixture further comprises a conductive additive.

[93] A system for carrying out a method for recovering metals using the method described in

[89] , comprising: (a) A source of a mixture containing battery materials; (b) a cell operably connected to the source, the mixture flowing into the cell and being held under compression; (c) an electrode operably connected to said cell; (d) a flash power supply for applying a voltage across the mixture to obtain metals and battery waste from the battery material; (e) a magnet in operable contact with the metal and the battery waste, the magnet being operable in response to the step of magnetically separating the metal and the battery waste. The system described above.

[94] The system of

[93] , wherein the battery material comprises a lithium ion battery material.

[95] The system of

[93] , wherein the battery material comprises a non-lithium metal ion battery material selected from the group consisting of sodium ion battery materials, potassium ion battery materials, zinc ion battery materials, magnesium ion battery materials, aluminum ion battery materials, and combinations thereof.

[96] The system of

[93] , wherein the mixture further comprises a conductive additive.

[97] The system of

[93] , operable to perform a continuous or automated process.

[98] A method for recovering metals, comprising: (a) forming a mixture including a cathode material, the cathode material being prepared from one or more batteries including a cathode; (b) applying a voltage across the mixture to obtain metal and cathode waste from the cathode material; (i) the voltage is applied in one or more voltage pulses; (ii) the duration of each of the one or more voltage pulses is for a period of predetermined duration; (iii) the method destroys the 3D morphology of the cathode in the cathode material; (c) extracting the metal from the cathode waste using an aqueous solution. The above method, comprising:

[99] The method of

[98] , wherein the metal is selected from the group consisting of lithium, cobalt, nickel, manganese, copper, and iron.

[0100] The method of

[99] , wherein the metal is in the form of one or more metal salts.

[0101] The method according to

[0100] , wherein the one or more metal salts are in the form of one or more oxides.

[0102] The method according to

[98] , wherein the aqueous solution contains an acid.

[0103] The method according to

[0102] , wherein the acid is HCl in the range of 0.01M to 12M.

[0104] The method according to

[0102] , wherein the acid is HCl in the range of 0.01M to 0.1M.

[0105] The method according to

[0102] , wherein the acid is in the range of 0.01M to 15M.

[0106] The method according to

[0102] , wherein the acid is in the range of 0.01M to 0.1M.

[0107] The method according to

[98] , wherein the voltage is applied in the range of 1 voltage pulse to 100 voltage pulses.

[0108] The method of

[98] , wherein the one or more batteries comprising a cathode comprise a cathode selected from the group consisting of an LCO cathode and an NMC cathode.

[0109] A system for carrying out a method for recovering metals using at least one of the methods described in

[98] to

[0108] , comprising: (a) a source of a mixture containing a cathode material; (b) a cell operably connected to the source, the mixture flowing into the cell and being held under compression; (c) an electrode operably connected to said cell; (d) a flash power supply for applying a voltage across the mixture to obtain metal and cathode waste from the cathode material; (e) a source of aqueous solution, the aqueous solution operable to extract the metal from the cathode waste; The system described above.

[0110] The system described in

[0109] , wherein the mixture further contains a conductive additive.

[0111] A system as described in

[0109] that is operable to perform a continuous or automatic process.

[0112] A method for recycling anode materials, comprising: (a) obtaining a mixture comprising an anode material from one or more batteries, the anode material comprising graphite; (b) applying a voltage across the mixture to refine graphite in the mixture; (i) the voltage is applied in one or more voltage pulses; (ii) the duration of each of the one or more voltage pulses is over a period of time; (c) utilizing the purified graphite by applying a voltage in one or more fresh batteries. The above method, comprising:

[0113] The method of

[0112] , wherein the one or more batteries include one or more lithium ion batteries.

[0114] The method described in

[0112] , wherein the one or more batteries 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.

[0115] The method of

[0112] , wherein the one or more new batteries include one or more new lithium ion batteries.

[0116] The method of

[0112] , wherein the one or more new batteries include one or more new lithium ion batteries.

[0117] The method described in

[0112] , wherein the one or more batteries 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, batteries without anodes, metal oxygen batteries, metal air batteries, and combinations thereof.

[0118] The method described in

[0112] , wherein the mixture consists of an anode material.

[0119] The method of

[0112] , wherein the mixture further comprises a cathode material from the one or more batteries.

[0120] The method of

[0112] , wherein the mixture comprises an anode material mixed with a conductive additive that is not the anode material.

[0121] The method described in

[0120] , wherein the conductive additive is a carbon source.

[0122] The method according to

[0120] , wherein the conductive additive is selected from the group consisting of graphite, anode graphite, battery grade graphite, elemental carbon, carbon black, graphene, flash graphene, turbostratic graphene, coal, anthracite, coke, metallurgical coke, calcined coke, activated carbon, biochar, carbon from natural gas with hydrogen atoms removed, activated carbon, shungite, plastic waste, carbon char derived from plastic waste, food waste, carbon char derived from food waste, biomass, carbon char derived from biomass, carbon derived from hydrocarbon gas, and mixtures thereof.

[0123] The method described in

[0120] , wherein the conductive additive is carbon black.

[0124] The method described in

[0120] , wherein the conductive additive is primarily elemental carbon.

[0125] A system for carrying out a method for recycling anode material utilizing at least one of the methods of

[0112] to

[0124] , comprising: (a) a source of a mixture containing an anode material including graphite; (b) a cell operably connected to the source, the mixture flowing into the cell and being held under compression; (c) electrodes operably connected to the cell; and (d) a flash power supply for applying a voltage across the mixture to refine the graphite in the anode material. The system described above.

[0126] The system described in

[0125] , wherein the anode material comprises an anode material for a lithium ion battery.

[0127] The system described in

[0125] , wherein the anode material comprises a non-lithium metal ion battery anode material selected from the group consisting of a lithium ion battery anode material, a sodium ion battery anode material, a potassium ion battery anode material, a zinc ion battery anode material, a magnesium ion battery anode material, an aluminum ion battery anode material, and combinations thereof.

[0128] The system described in

[0125] , wherein the mixture includes an anode material mixed with a conductive additive that is not the anode material.

[0129] A system as described in

[0125] that is operable to perform a continuous or automatic process. (a) selecting a graphite anode material from a battery; (b) applying flash Joule heating to the graphite anode material to form a flashed graphite anode material, wherein the application of flash Joule heating refines the graphite anode material. A method comprising:

[0131] The method described in

[0130] , wherein the battery is a lithium ion battery.

[0132] The method described in

[0130] , wherein the battery is a battery selected from the group consisting of lithium ion batteries, sodium ion batteries, potassium ion batteries, zinc ion batteries, magnesium ion batteries, aluminum ion batteries, and combinations thereof.

[0133] the flash joule heating comprises applying a voltage across the graphite anode material; (i) the voltage is applied in one or more voltage pulses; (ii) The method described in

[0130] , wherein the duration of each of the one or more voltage pulses is for a predetermined period of time.

[0134] The method of

[0130] further comprising using the flashed graphite anode material in a second battery.

[0135] The method described in

[0134] , wherein the second battery is a second lithium ion battery.

[0136] The method described in

[0135] , wherein the battery is a lithium ion battery.

[0137] The method described in

[0134] , wherein the second battery is a second non-lithium metal ion battery selected from the group consisting of a sodium ion battery, a potassium ion battery, a zinc ion battery, a magnesium ion battery, an aluminum ion battery, and combinations thereof.

[0138] The method described in

[0137] , wherein the battery is 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.

[0139] The method described in

[0130] , further comprising a step of washing the flashed graphite anode material to separate the inorganic metals and salts in the flashed graphite anode material from the graphite.

[0140] The method of

[0139] , further comprising using the flashed graphite anode material in a second battery after washing.

[0141] The method described in

[0140] , wherein the second battery is a second lithium ion battery.

[0142] The method described in

[0141] , wherein the battery is a lithium ion battery.

[0143] The method described in

[0140] , wherein the second battery is a battery selected from the group consisting of a lithium ion battery, a sodium ion battery, a potassium ion battery, a zinc ion battery, a magnesium ion battery, an aluminum ion battery, and combinations thereof.

[0144] The method described in

[0143] , wherein the battery is a battery selected from the group consisting of lithium ion batteries, sodium ion batteries, potassium ion batteries, zinc ion batteries, magnesium ion batteries, aluminum ion batteries, and combinations thereof. A method for resynthesizing a cathode material, comprising: (a) subjecting the cathode material to a flash Joule heating process to form a ferromagnetic flash product; and (b) subjecting the ferromagnetic flash product to a hydrothermal and calcination process to form a resynthesized cathode material. The above method, comprising:

Claims

1. 1. A method for recovering metals, comprising: (a) forming a mixture including a cathode material, the cathode material being prepared from one or more batteries; (b) applying a voltage across the mixture to obtain metal and cathode waste from the cathode material; (i) the voltage is applied in one or more voltage pulses; (ii) the duration of each of the one or more voltage pulses is for a period of predetermined duration; and (c) magnetically separating the metal and the cathode waste; The above method, comprising:

2. 10. The method of claim 1, wherein the metal comprises a 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 a cathode metal selected from the group consisting of metal oxides, metal salts, metal carbonates, metal phosphates, and combinations thereof.

4. The method of claim 3 , wherein the cathode metal comprises a metal oxide.

5. The method of claim 3 , wherein the cathode metal comprises a metal carbonate.

6. The method of claim 3 , wherein the cathode metal comprises a metal phosphate.

7. The method of claim 1 , wherein the one or more batteries comprise one or more lithium ion batteries.

8. 8. The method of claim 7, wherein each of the one or more lithium ion batteries comprises a respective LCO cathode.

9. 8. The method of claim 7, wherein each of the one or more lithium ion batteries comprises an NMC cathode.

10. The method of claim 1 , wherein the mixture further comprises a conductive additive.

11. The method of claim 1 , wherein the cathode material retains the 3D layer structure of the cathode.

12. 10. The method of claim 1, further comprising a cooling step, wherein the cooling step cools the metal and the cathode waste prior to the step of magnetically separating the metal and the cathode waste.

13. further comprising applying a second voltage across the cathode waste after the mechanically separating step; (a) the second voltage is applied in one or more second voltage pulses; 10. The method of claim 1, wherein (b) the duration of each of the one or more second voltage pulses is for a second predetermined period of time.

14. (a) applying the second voltage across the cathode waste captures additional metal and a reduced portion of the cathode waste; 14. The method of claim 13, wherein the method further comprises the step of: (b) magnetically separating the additional metal and the reduced portion of the cathode waste.

15. A system for carrying out a method for recovering metals using at least one of the methods according to claims 1 to 14, comprising: (a) a source of a mixture comprising a cathode material; (b) a cell operably connected to said source such that said mixture flows into said cell and is held under compression; (c) an electrode operably connected to the cell; (d) a flash power supply for applying a voltage across the mixture to obtain metal and cathode waste from the cathode material; (e) a magnet in operative contact with the metal and the cathode waste, the magnet being operable in response to magnetically separating the metal and the cathode waste; The system described above.

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