A resource recovery method for sulfide all-solid-state batteries

Abstract

The present invention relates to a resource recovery method for sulfide all-solid-state batteries, which belongs to the field of solid-state battery technology. The main process is: retired sulfide all-solid-state battery cells undergo sulfur-heat reaction to obtain pyrolysis slag and current collectors, the pyrolysis slag undergoes water immersion treatment, and is separated to obtain water leaching liquid and water leaching slag, the water leaching liquid is concentrated and lithium precipitation is treated to separate lithium carbonate and alkali metal hydroxide solution, the water leaching slag undergoes acid leaching treatment to separate acid leaching slag and acid leaching liquid, the acid leaching liquid undergoes phosphorus precipitation treatment to separate hydroxyphosphate and phosphorus removal liquid, the phosphorus removal liquid undergoes nickel-cobalt-manganese precipitation treatment to separate nickel-cobalt-manganese coprecipitate and neutral alkali metal halide solution, the acid leaching slag undergoes dissolution treatment to separate graphite and sulfur, and the non-polar organic solvent is recycled. This method can effectively achieve high-value-added recovery of energy metals in retired sulfide all-solid-state batteries, synergistically achieve the recovery of graphite and sulfur, with low energy consumption and emissions and high raw material utilization.

Description

Technical Field

[0001] The present invention relates to a resource recovery method for a sulfide all-solid-state battery, belonging to the technical field of solid-state batteries and solid waste resource recovery. Background Art

[0002] All-solid-state batteries, with their advantages of high safety and high energy density, have become a key area of ​​focus for countries, with companies competing for investment and research. Solid-state electrolytes, the key components of all-solid-state batteries, are mainly divided into polymers, oxides, halides, and sulfides. Sulfide solid-state electrolytes, among others, are highly deformable, easily cold-formed, and possess high ionic conductivity, making them a key advantage in the competition for next-generation battery technology. Sulfide all-solid-state batteries will become the mainstream secondary battery of the future. Due to battery capacity decay and abnormal damage, a large number of retired sulfide all-solid-state batteries will inevitably be produced in the future. Retired sulfide all-solid-state batteries are prone to producing highly toxic gases such as hydrogen fluoride and hydrogen sulfide, and also contain a variety of high-value-added energy metals such as lithium, nickel, cobalt, and manganese. Their resource recovery is a key issue for the healthy development of the battery industry.

[0003] Currently, there are few methods for resource recovery of retired sulfide all-solid-state batteries, and the main idea is to prioritize the recovery of sulfide solid electrolytes. Patent application CN110661051A uses organic solvents to dissolve sulfide solid electrolytes such as lithium phosphorus sulfur and lithium phosphorus sulfur chlorine, but the battery usually contains polymer binders that are easily soluble in organic solvents, making it impossible to effectively separate the solid electrolyte. Patent CN101919107B and the paper "Chemical speciation changes of an all-solid-state lithium-ion battery caused by roasting determined by sequential acid leaching, Waste Management 2023, 166, 122-132" use water to recover sulfide solid electrolytes, but the hydrolysis process will produce hydrogen sulfide waste gas. Patent application CN115863820A uses pyrolysis to remove the binder in the sulfide all-solid-state battery, and then uses acid to recover the sulfide solid electrolyte, but the acid leaching process also produces hydrogen sulfide waste gas. In addition, the slag phase obtained by the above method is graphite negative electrode material and ternary positive electrode material. The subsequent process is usually to deconstruct the ternary material at high temperature (above 650°C) of the graphite material, recover energy metals, and emit carbon-oxygen waste gas.

[0004] In summary, existing recycling methods for sulfide all-solid-state batteries suffer from high energy consumption and emissions, and the potential role of solid-state electrolytes in the recovery of positive and negative electrode materials has not been explored in depth. With the gradual establishment of the concept of high-quality development, the development of a resource-based recycling method for sulfide all-solid-state batteries with low energy consumption, low emissions, and high raw material utilization is of great significance to this field. Summary of the Invention

[0005] In light of this, the present invention aims to provide a method for recycling sulfide all-solid-state batteries. This method can fully recycle retired sulfide all-solid-state batteries, achieving a cascaded recycling of energy metals and valuable substances. It features low energy consumption, low emissions, and high utilization of battery components. It offers excellent environmental, economic, and social benefits and holds promising prospects for industrialization.

[0006] To achieve the above objectives, the technical solutions of the present invention are as follows.

[0007] A method for recycling sulfide all-solid-state batteries, comprising the following steps:

[0008] (1) Sulfur thermal reaction: The retired sulfide all-solid-state battery cell is subjected to overall pyrolysis treatment, and the cell includes a nickel-cobalt-manganese ternary positive electrode material, a phosphorus-based sulfide solid electrolyte, a graphite negative electrode material, a binder and a current collector; during the pyrolysis treatment, the nickel-cobalt-manganese ternary positive electrode material and the phosphorus-based sulfide solid electrolyte undergo a sulfur thermal reaction, the molar ratio of the nickel-cobalt-manganese ternary positive electrode material and the phosphorus-based sulfide solid electrolyte is greater than or equal to 2:1, the sulfur thermal reaction temperature is 300-550°C, and the sulfur thermal reaction time is greater than or equal to 20 minutes. After the reaction is completed, pyrolysis slag and a naturally detached current collector are obtained;

[0009] (2) Water immersion: The pyrolysis residue is added to water for water immersion treatment. After the treatment, the solid and liquid are separated to obtain a water immersion liquid and water immersion residue;

[0010] (3) Concentration treatment: Concentrating the water extract to obtain a concentrated water extract;

[0011] (4) lithium precipitation: adding soluble carbonate to the concentrated water extract for precipitation treatment, and after the treatment, solid-liquid separation to obtain lithium carbonate and soluble hydroxide solution;

[0012] (5) acid leaching: adding hydrochloric acid to the water leaching residue in step (2) to carry out acid leaching treatment. After the treatment, solid-liquid separation is completed to obtain acid leaching residue and acid leaching liquid;

[0013] (6) Phosphorus precipitation: adding hydroxide to the acid leaching solution to perform precipitation treatment, and after the treatment, solid-liquid separation to obtain hydroxyphosphate and phosphorus removal solution;

[0014] (7) Precipitating nickel, cobalt and manganese: adding the soluble hydroxide solution described in step (4) to the dephosphorization solution, and supplementing with the same soluble hydroxide, to carry out precipitation treatment. After the treatment is completed, solid-liquid separation is performed to obtain nickel, cobalt and manganese coprecipitate and halide solution;

[0015] (8) Dissolving: adding a non-polar organic solvent to the acid leaching residue of step (5), and after sufficient dissolution, separating the solid and the liquid to obtain graphite and a sulfur-containing solution, and evaporating and separating the sulfur-containing solution to obtain sulfur and a non-polar organic solvent.

[0016] Preferably, in step (1), during the sulfur-heat reaction, the binder degrades to produce hydrogen fluoride, which is neutralized with calcium hydroxide to obtain calcium fluoride.

[0017] Preferably, in step (1), the chemical formula of the nickel-cobalt-manganese ternary positive electrode material is Li[Ni (1-x-y) Mn x Co y ]O2, 0<x<1, 0<y<1, 0.3≤(1-xy)<1.

[0018] Preferably, in step (1), the chemical formula of the phosphorus-based sulfide solid electrolyte is Li6PS5X, where X is Cl, Br or I.

[0019] Preferably, in step (1), in the sulfur thermal reaction, the molar ratio of the nickel-cobalt-manganese ternary positive electrode material and the phosphorus-based sulfide solid electrolyte is 2 to 30:1, and the sulfur thermal reaction time is 20 to 300 minutes.

[0020] Preferably, in step (2), the water immersion treatment temperature is 10 to 90° C., and the treatment time is 20 to 300 minutes.

[0021] Preferably, in step (2), the liquid-to-solid ratio of the water immersion treatment is 8 to 20 mL / g.

[0022] Preferably, in step (3), the concentration of lithium ions in the concentrated water extract is 3 to 19 g / L.

[0023] Preferably, in step (4), the molar ratio of soluble carbonate to lithium ions in the concentrated aqueous solution is 1:2.

[0024] Preferably, in step (4), the soluble carbonate is one or more of lithium carbonate, sodium carbonate and potassium carbonate.

[0025] Preferably, in step (4), the lithium precipitation treatment time is 20 to 300 minutes.

[0026] Preferably, in step (5), the ratio of the molar amount of HCl in the hydrochloric acid to the total molar amount of nickel, cobalt and manganese elements in the water-leached residue is 2 to 10:1.

[0027] Preferably, in step (5), the molar concentration of hydrochloric acid is 0.1 to 3 mol / L.

[0028] Preferably, in step (5), the acid leaching treatment temperature is 10 to 90° C., and the treatment time is 20 to 300 minutes.

[0029] Preferably, in step (6), the hydroxide is a hydroxide that can form a colloid in a weakly acidic environment, including one or more of aluminum hydroxide, iron hydroxide, lanthanum hydroxide, copper hydroxide, zinc hydroxide and zirconium hydroxide.

[0030] Preferably, in step (6), the ratio of the molar amount of the hydroxide to the total molar amount of nickel, cobalt and manganese elements in the acid leaching solution is greater than or equal to 1:1.

[0031] Preferably, in step (6), the temperature of the phosphorus precipitation treatment is 10-50° C., and the treatment time is 20-300 min.

[0032] Preferably, in step (7), the ratio of the total molar amount of the soluble hydroxide to the total molar amount of nickel, cobalt and manganese elements in the phosphorus removal solution is 2:1.

[0033] Preferably, in step (7), the temperature of the nickel-cobalt-manganese precipitation treatment is 10-90° C., and the treatment time is 20-300 min.

[0034] Preferably, in step (8), the non-polar organic solvent is one or more of petroleum ether, hexane, carbon disulfide, carbon tetrachloride, benzene, toluene, dichloroethane, chloroform and dichloromethane.

[0035] Beneficial effects

[0036] The present invention provides a resource recovery method for sulfide all-solid-state batteries, including the process steps of sulfur thermal reaction, water leaching, concentration, lithium precipitation, acid leaching, phosphorus precipitation, nickel, cobalt and manganese precipitation, and dissolution. The main process is as follows: retired sulfide all-solid-state battery cells are subjected to sulfur thermal reaction to obtain pyrolysis slag and current collectors, the pyrolysis slag is subjected to water leaching treatment to separate the leaching liquid and leaching slag, the leaching liquid is concentrated and treated for lithium precipitation to separate lithium carbonate and alkali metal hydroxide solution, the leaching slag is subjected to acid leaching to separate the acid leaching slag and the acid leaching liquid, the acid leaching liquid is subjected to phosphorus precipitation to separate hydroxyphosphate and phosphorus removal liquid, the phosphorus removal liquid is subjected to nickel, cobalt and manganese precipitation to separate nickel, cobalt and manganese coprecipitate and neutral alkali metal halide solution, the acid leaching slag is subjected to dissolution treatment to separate graphite and sulfur, and the non-polar organic solvent is recycled. The method provided by the present invention can effectively achieve high-value-added recovery of energy metals in retired sulfide all-solid-state batteries, synergistically achieve the recovery of graphite and sulfur, with low energy consumption, low emissions, and high raw material utilization.

[0037] The present invention provides a resource recovery method for sulfide all-solid-state batteries. The sulfur-thermal reaction of nickel-cobalt-manganese ternary positive electrode materials and phosphorus-based sulfide solid electrolytes is LiMO2+Li6PS5X→Li2O+MO+M2PO4X+S (M refers to Ni x Co y Mn z , the total valence is +3, where the ratio of x, y, and z can be adjusted), and this process requires strict control of the amount of reactants, reaction temperature, and reaction time; the main components of the obtained pyrolysis slag are Li2O, MO, M2PO4X, S, and C (C includes carbon materials such as graphite, conductive carbon, and polymer-degraded carbon). BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is a schematic diagram of the process flow of the resource recovery method of the sulfide all-solid-state battery described in the present invention. DETAILED DESCRIPTION

[0039] The present invention will be further described in detail below with reference to specific embodiments.

[0040] A method for recycling sulfide all-solid-state batteries, comprising the following steps:

[0041] (1) Sulfur thermal reaction: The retired sulfide all-solid-state battery cell is subjected to overall pyrolysis treatment, and the cell includes a nickel-cobalt-manganese ternary positive electrode material, a phosphorus-based sulfide solid electrolyte, a graphite negative electrode material, a binder and a current collector; during the pyrolysis treatment, the nickel-cobalt-manganese ternary positive electrode material and the phosphorus-based sulfide solid electrolyte undergo a sulfur thermal reaction, the molar ratio of the nickel-cobalt-manganese ternary positive electrode material and the phosphorus-based sulfide solid electrolyte is greater than or equal to 2:1, the sulfur thermal reaction temperature is 300-550°C, and the sulfur thermal reaction time is greater than or equal to 20 minutes. After the reaction is completed, pyrolysis slag and a naturally detached current collector are obtained;

[0042] (2) Water immersion: The pyrolysis residue is added to water for water immersion treatment. After the treatment, the solid and liquid are separated to obtain a water immersion liquid and water immersion residue;

[0043] (3) Concentration treatment: Concentrating the water extract to obtain a concentrated water extract;

[0044] (4) lithium precipitation: adding soluble carbonate to the concentrated water extract for precipitation treatment, and after the treatment, solid-liquid separation to obtain lithium carbonate and soluble hydroxide solution;

[0045] (5) acid leaching: adding hydrochloric acid to the water leaching residue in step (2) to carry out acid leaching treatment. After the treatment, solid-liquid separation is completed to obtain acid leaching residue and acid leaching liquid;

[0046] (6) Phosphorus precipitation: adding hydroxide to the acid leaching solution to perform precipitation treatment, and after the treatment, solid-liquid separation to obtain hydroxyphosphate and phosphorus removal solution;

[0047] (7) Precipitating nickel, cobalt and manganese: adding the soluble hydroxide solution described in step (4) to the dephosphorization solution, and supplementing with the same soluble hydroxide, to carry out precipitation treatment. After the treatment is completed, solid-liquid separation is performed to obtain nickel, cobalt and manganese coprecipitate and halide solution;

[0048] (8) Dissolving: adding a non-polar organic solvent to the acid leaching residue of step (5), and after sufficient dissolution, separating the solid and the liquid to obtain graphite and a sulfur-containing solution, and evaporating and separating the sulfur-containing solution to obtain sulfur and a non-polar organic solvent.

[0049] In some embodiments, in step (1), during the sulfur-heat reaction, the binder degrades to produce hydrogen fluoride, which is neutralized with calcium hydroxide to obtain calcium fluoride.

[0050] In some embodiments, in step (1), the chemical formula of the nickel-cobalt-manganese ternary cathode material is Li[Ni (1-x-y) Mn x Co y ]O2, 0<x<1, 0<y<1, 0.3≤(1-xy)<1. For example, it can be 811 type lithium nickel cobalt manganese oxide, 622 type lithium nickel cobalt manganese oxide, 523 type lithium nickel cobalt manganese oxide, 111 type lithium nickel cobalt manganese oxide, etc.

[0051] In some embodiments, in step (1), the chemical formula of the phosphorus-based sulfide solid electrolyte is Li6PS5X, where X is Cl, Br, or I. For example, it can be lithium phosphorus sulfur chlorine, lithium phosphorus sulfur bromine, or lithium phosphorus sulfur iodine.

[0052] In some embodiments, in step (1), in the sulfur-thermal reaction, the molar ratio of the nickel-cobalt-manganese ternary cathode material to the phosphorus-based sulfide solid electrolyte is 2 to 30:1, for example, 2:1, 6:1, 10:1, 14:1, 18:1, 22:1, 26:1, 30:1, etc.

[0053] In some embodiments, in step (1), during the sulfur thermal reaction, the reaction temperature is 300-550°C, for example, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, etc.

[0054] In some embodiments, in step (1), the sulfur thermal reaction time is 20 to 300 min, for example, 20 min, 40 min, 60 min, 80 min, 100 min, 120 min, 140 min, 160 min, 180 min, 200 min, 220 min, 240 min, 260 min, 280 min, 300 min, etc.

[0055] In some embodiments, in step (2), the temperature of the water immersion treatment is 10-90° C. For example, it can be 10° C., 20° C., 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., etc.

[0056] In some embodiments, in step (2), the water immersion treatment time is 20 to 300 min, for example, 20 min, 40 min, 60 min, 80 min, 100 min, 120 min, 140 min, 160 min, 180 min, 200 min, 220 min, 240 min, 260 min, 280 min, 300 min, etc.

[0057] In some embodiments, in step (2), the liquid-to-solid ratio of the water immersion treatment is 8 to 20 mL / g, for example, 8 mL / g, 9 mL / g, 10 mL / g, 11 mL / g, 12 mL / g, 13 mL / g, 14 mL / g, 15 mL / g, 16 mL / g, 17 mL / g, 18 mL / g, 19 mL / g, 20 mL / g, etc.

[0058] In some embodiments, in step (3), the concentration of lithium ions in the concentrated aqueous solution is 3 to 19 g / L, for example, 3 g / L, 5 g / L, 7 g / L, 9 g / L, 11 g / L, 13 g / L, 15 g / L, 17 g / L, 19 g / L, etc.

[0059] In some embodiments, in step (4), the molar ratio of soluble carbonate to lithium ions in the concentrated aqueous solution is 1:2.

[0060] In some embodiments, in step (4), the soluble carbonate is one or more of lithium carbonate, sodium carbonate and potassium carbonate.

[0061] In some embodiments, in step (4), the lithium precipitation treatment time is 20 to 300 minutes, for example, 20 minutes, 40 minutes, 60 minutes, 80 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes, 180 minutes, 200 minutes, 220 minutes, 240 minutes, 260 minutes, 280 minutes, 300 minutes, etc.

[0062] In some embodiments, in step (5), the ratio of the molar amount of HCl in the hydrochloric acid to the total molar amount of nickel, cobalt and manganese in the water-leached residue is 2 to 10:1. For example, it can be 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, etc.

[0063] In some embodiments, in step (5), the molar concentration of hydrochloric acid is 0.1 to 3 mol / L. For example, it can be 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.5 mol / L, 0.7 mol / L, 0.9 mol / L, 1.1 mol / L, 1.3 mol / L, 1.5 mol / L, 1.7 mol / L, 1.9 mol / L, 2.1 mol / L, 2.3 mol / L, 2.5 mol / L, 2.7 mol / L, 2.9 mol / L, 3.0 mol / L, etc.

[0064] In some embodiments, in step (5), the temperature of the acid leaching treatment is 10-90° C. For example, it can be 10° C., 20° C., 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., etc.

[0065] In some embodiments, in step (5), the acid leaching treatment time is 20 to 300 minutes, for example, 20 minutes, 40 minutes, 60 minutes, 80 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes, 180 minutes, 200 minutes, 220 minutes, 240 minutes, 260 minutes, 280 minutes, 300 minutes, etc.

[0066] In some embodiments, in step (6), the hydroxide is a hydroxide that can form a colloid in a weakly acidic environment, including one or more of aluminum hydroxide, iron hydroxide, lanthanum hydroxide, copper hydroxide, zinc hydroxide and zirconium hydroxide.

[0067] In some embodiments, in step (6), the ratio of the molar amount of the hydroxide to the total molar amount of nickel, cobalt and manganese elements in the acid leaching solution is greater than or equal to 1:1. For example, it can be 1:1, 1:2, 1:3, etc.

[0068] In some embodiments, in step (6), the temperature of the phosphorus precipitation treatment is 10-50° C. For example, it can be 10° C., 20° C., 30° C., 40° C., 50° C., etc.

[0069] In some embodiments, in step (6), the phosphorus precipitation treatment time is 20 to 300 minutes, for example, 20 minutes, 40 minutes, 60 minutes, 80 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes, 180 minutes, 200 minutes, 220 minutes, 240 minutes, 260 minutes, 280 minutes, 300 minutes, etc.

[0070] In some embodiments, in step (7), the ratio of the total molar amount of the soluble hydroxide to the total molar amount of nickel, cobalt and manganese elements in the phosphorus removal solution is 2:1.

[0071] In some embodiments, in step (7), the temperature of the nickel-cobalt-manganese precipitation treatment is 10-90° C. For example, it can be 10° C., 20° C., 30° C., 40° C., 50° C., 60° C., 70° C., 80° C., 90° C., etc.

[0072] In some embodiments, in step (7), the nickel, cobalt and manganese precipitation treatment time is 20 to 300 minutes, for example, 20 minutes, 40 minutes, 60 minutes, 80 minutes, 100 minutes, 120 minutes, 140 minutes, 160 minutes, 180 minutes, 200 minutes, 220 minutes, 240 minutes, 260 minutes, 280 minutes, 300 minutes, etc.

[0073] In some embodiments, in step (8), the non-polar organic solvent is one or more of petroleum ether, hexane, carbon disulfide, carbon tetrachloride, benzene, toluene, dichloroethane, chloroform and dichloromethane.

[0074] Example 1

[0075] This embodiment provides a method for recycling retired sulfide all-solid-state batteries, and the steps are as follows:

[0076] (1) Collect retired sulfide all-solid-state batteries (solid electrolyte is Li6PS5Br, ternary cathode material is LiNi 0.3 Co 0.3 Mn 0.3 O2), equipped with solid electrolyte Li6PS5Br and ternary cathode material LiNi 0.3 Co 0.3 Mn 0.3 The molar ratio of O2 is 1:2, the reaction temperature is set at 300℃, and the reaction time is 20min to carry out sulfur thermal reaction, and the retired sulfide all-solid-state battery cells are subjected to overall pyrolysis treatment to obtain pyrolysis slag and naturally detached current collectors. The generated hydrogen fluoride gas is introduced into the tail gas treatment section and neutralized with calcium hydroxide to obtain calcium fluoride;

[0077] (2) 100 g of pyrolysis residue was mixed with water at a liquid-to-solid ratio of 14 mL / g, and the temperature was set at 50 °C and the time was 160 min for water immersion reaction. After solid-liquid separation, the water immersion liquid and water immersion residue were obtained;

[0078] (3) concentrating the water extract until the lithium concentration reaches 19 g / L to obtain a concentrated water extract;

[0079] (4) 1 L of concentrated water extract was added with 144 g of sodium carbonate, and the temperature was set at 60° C. for 20 min to carry out precipitation reaction, followed by solid-liquid separation to obtain lithium carbonate and sodium hydroxide solution;

[0080] (5) 100 g of water-leached residue was mixed with hydrochloric acid in a molar ratio of hydrogen chloride to nickel, cobalt and manganese of 10:1, and the acid leaching reaction was performed at a hydrochloric acid concentration of 3.0 mol / L, a temperature of 90°C and a time of 300 min. The acid leaching residue and the acid leaching liquid were then obtained by solid-liquid separation;

[0081] (6) 1 L of the acid leaching solution was mixed with aluminum hydroxide in a molar ratio of aluminum hydroxide to nickel, cobalt, and manganese of 2:1, and the precipitation reaction was performed at 10°C for 20 min. After solid-liquid separation, aluminum hydroxyphosphate and phosphorus removal solution were obtained;

[0082] (7) Sodium hydroxide was added to the aforementioned sodium hydroxide solution, 1 L of the dephosphorization solution was taken, and the mixture was mixed with sodium hydroxide in a molar ratio of sodium hydroxide to nickel, cobalt, and manganese of 2:1. The temperature was set to 50° C. and the time was 160 min for precipitation reaction. After solid-liquid separation, nickel, cobalt, and manganese coprecipitates and sodium halide solution were obtained;

[0083] (8) 10 g of acid leaching residue was mixed with carbon tetrachloride at a liquid-solid ratio of 1.0 mL / g and dissolved at 100 °C. After solid-liquid separation, 8.13 g of graphite was obtained. The carbon tetrachloride was evaporated and reused to obtain 1.87 g of sulfur.

[0084] In this embodiment, during the sulfur thermal reaction, the conversion rate of sulfur ions to elemental sulfur is 90%, during water leaching, the lithium leaching rate is 92%, during acid leaching, the total leaching rate of nickel, cobalt and manganese is 91%, and during lithium and nickel, cobalt and manganese precipitation, through the recycling and reuse of the mother liquor, the total precipitation rate of lithium, nickel, cobalt and manganese is 99%, and the recovery rate of graphite is 93%; this embodiment realizes the cascade leaching and cascade recovery of complex energy metals, and synergistically recovers sulfur and graphite. The overall process is pollution-free, and the resource recovery of sulfide all-solid-state batteries is realized.

[0085] Example 2

[0086] This embodiment provides a method for recycling retired sulfide all-solid-state batteries, and the steps are as follows:

[0087] (1) Collect retired sulfide all-solid-state batteries (solid electrolyte is Li6PS5Cl, ternary cathode material is LiNi 0.8 Co 0.1 Mn 0.1 O2), configured with solid electrolyte Li6PS5Cl and ternary cathode material LiNi 0.8 Co 0.1 Mn 0.1 The molar ratio of O2 is 1:16, the reaction temperature is set at 425°C and the reaction time is 160 min to carry out a sulfur thermal reaction, and the retired sulfide all-solid-state battery cells are subjected to overall pyrolysis treatment to obtain pyrolysis slag and naturally detached current collectors. The generated hydrogen fluoride gas is introduced into the tail gas treatment section and neutralized with calcium hydroxide to obtain calcium fluoride;

[0088] (2) 100 g of pyrolysis residue was mixed with water at a liquid-solid ratio of 20 mL / g, and the temperature was set at 90 °C for 300 min to perform water immersion reaction. After solid-liquid separation, the water immersion liquid and water immersion residue were obtained;

[0089] (3) concentrating the water extract until the lithium concentration reaches 3 g / L to obtain a concentrated water extract;

[0090] (4) 1 L of concentrated water extract was added with 30 g of potassium carbonate, and the temperature was set at 80° C. for 160 min to carry out precipitation reaction, followed by solid-liquid separation to obtain lithium carbonate and potassium hydroxide solution;

[0091] (5) 100 g of water-leached residue was mixed with hydrochloric acid in a molar ratio of hydrogen chloride to nickel, cobalt and manganese of 2:1, and the acid leaching reaction was performed at a hydrochloric acid concentration of 0.1 mol / L, a temperature of 10°C and a time of 20 min. The acid leaching residue and the acid leaching liquid were then obtained by solid-liquid separation;

[0092] (6) 1 L of the acid leaching solution was mixed with ferric hydroxide in a molar ratio of 1:1 between ferric hydroxide and nickel, cobalt and manganese, and the temperature was set at 30°C for 160 min to carry out precipitation reaction, followed by solid-liquid separation to obtain hydroxyferric phosphate and dephosphorization solution;

[0093] (7) adding potassium hydroxide to the aforementioned potassium hydroxide solution, taking 1 L of the dephosphorization solution, mixing it with potassium hydroxide in a molar ratio of potassium hydroxide to nickel, cobalt, and manganese of 2:1, setting the temperature at 90° C. and the time for 300 min for precipitation reaction, and then performing solid-liquid separation to obtain nickel, cobalt, and manganese coprecipitate and potassium halide solution;

[0094] (8) 10 g of acid leaching residue was mixed with carbon disulfide at a liquid-solid ratio of 0.7 mL / g and dissolved at 0 °C. After solid-liquid separation, 7.47 g of graphite was obtained. The carbon disulfide was evaporated and reused to obtain 2.53 g of sulfur.

[0095] In this embodiment, during the sulfur thermal reaction, the conversion rate of sulfur ions to elemental sulfur is 94%, during water leaching, the lithium leaching rate is 97%, during acid leaching, the total leaching rate of nickel, cobalt and manganese is 94%, and during lithium and nickel, cobalt and manganese precipitation, through the recycling and reuse of the mother liquor, the total precipitation rate of lithium, nickel, cobalt and manganese is 99%, and the recovery rate of graphite is 95%. This embodiment realizes the cascade leaching and cascade recovery of complex energy metals, and synergistically recovers sulfur and graphite. The overall process is pollution-free, and the resource recovery of sulfide all-solid-state batteries is realized.

[0096] Example 3

[0097] This embodiment provides a method for recycling retired sulfide all-solid-state batteries, and the steps are as follows:

[0098] (1) Collect retired sulfide all-solid-state batteries (solid electrolyte is Li6PS5I, ternary cathode material is LiNi 0.6 Co 0.2 Mn 0.2 O2), equipped with solid electrolyte Li6PS5I and ternary cathode material LiNi 0.6 Co 0.2 Mn 0.2 The molar ratio of O2 is 1:30, the reaction temperature is set at 550°C and the reaction time is 300 min to carry out a sulfur thermal reaction, and the retired sulfide all-solid-state battery cells are subjected to overall pyrolysis treatment to obtain pyrolysis slag and naturally detached current collectors. The generated hydrogen fluoride gas is introduced into the tail gas treatment section and neutralized with calcium hydroxide to obtain calcium fluoride;

[0099] (2) 100 g of pyrolysis residue was mixed with water at a liquid-solid ratio of 8 mL / g, and the temperature was set at 10 °C and the time was 20 min for water immersion reaction. After solid-liquid separation, the water immersion liquid and water immersion residue were obtained;

[0100] (3) concentrating the water extract until the lithium concentration reaches 11 g / L to obtain a concentrated water extract;

[0101] (4) 1 L of concentrated aqueous extract was added with 84 g of sodium carbonate, and the temperature was set at 100° C. for 300 min to carry out precipitation reaction, followed by solid-liquid separation to obtain lithium carbonate and sodium hydroxide solution;

[0102] (5) 100 g of water-leached residue was mixed with hydrochloric acid in a molar ratio of hydrogen chloride to nickel, cobalt and manganese of 5:1, and the acid leaching reaction was carried out at a hydrochloric acid concentration of 1.5 mol / L, a temperature of 50°C and a time of 160 min. The acid leaching residue and the acid leaching liquid were then obtained by solid-liquid separation;

[0103] (6) 1 L of the acid leaching solution was mixed with copper hydroxide in a molar ratio of copper hydroxide to nickel, cobalt and manganese of 3:1, and the precipitation reaction was performed at 50°C for 300 min. After solid-liquid separation, copper hydroxyphosphate and dephosphorization solution were obtained;

[0104] (7) Sodium hydroxide was added to the aforementioned sodium hydroxide solution, 1 L of the dephosphorization solution was taken, and the mixture was mixed with sodium hydroxide in a molar ratio of sodium hydroxide to nickel, cobalt, and manganese of 2:1. The precipitation reaction was performed at a temperature of 10° C. and a time of 20 min. After solid-liquid separation, nickel, cobalt, and manganese coprecipitates and a sodium halide solution were obtained;

[0105] (8) 10 g of the acid leaching residue was mixed with petroleum ether at a liquid-to-solid ratio of 1.3 mL / g and dissolved at 50 °C. After solid-liquid separation, 6.98 g of graphite was obtained. The petroleum ether was evaporated and reused to obtain 3.02 g of sulfur.

[0106] In this embodiment, during the sulfur thermal reaction, the conversion rate of sulfur ions to elemental sulfur is 97%, during water leaching, the lithium leaching rate is 99%, during acid leaching, the total leaching rate of nickel, cobalt and manganese is 97%, and during lithium and nickel, cobalt and manganese precipitation, through the recycling and reuse of the mother liquor, the total precipitation rate of lithium, nickel, cobalt and manganese is 99%, and the recovery rate of graphite is 97%. This embodiment realizes the cascade leaching and cascade recovery of complex energy metals, and synergistically recovers sulfur and graphite. The overall process is pollution-free, and the resource recovery of sulfide all-solid-state batteries is realized.

[0107] Example 4

[0108] This embodiment provides a method for recycling retired sulfide all-solid-state batteries, and the steps are as follows:

[0109] (1) Collect retired sulfide all-solid-state batteries (solid electrolyte is Li6PS5Cl, ternary cathode material is LiNi 0.5 Co 0.2 Mn 0.3 O2), configured with solid electrolyte Li6PS5Cl and ternary cathode material LiNi 0.5 Co 0.2 Mn 0.3 The molar ratio of O2 is 1:12, the reaction temperature is set at 460°C and the reaction time is 110 min to carry out a sulfur thermal reaction, and the retired sulfide all-solid-state battery cells are subjected to overall pyrolysis treatment to obtain pyrolysis slag and naturally detached current collectors. The generated hydrogen fluoride gas is introduced into the tail gas treatment section and neutralized with calcium hydroxide to obtain calcium fluoride;

[0110] (2) 100 g of pyrolysis residue was mixed with water at a liquid-to-solid ratio of 17 mL / g, and the temperature was set at 30 °C and the time was 240 min for water immersion reaction. After solid-liquid separation, the water immersion liquid and water immersion residue were obtained;

[0111] (3) concentrating the water extract until the lithium concentration reaches 6 g / L to obtain a concentrated water extract;

[0112] (4) Take 1 L of concentrated water extract, add 60 g of potassium carbonate, set the temperature to 90 ° C, and perform precipitation reaction for 40 min, and then obtain lithium carbonate and potassium hydroxide solution by solid-liquid separation;

[0113] (5) 100 g of water-leached residue was mixed with hydrochloric acid in a molar ratio of hydrogen chloride to nickel, cobalt and manganese of 9:1, and the acid leaching reaction was carried out at a hydrochloric acid concentration of 0.4 mol / L, a temperature of 70°C and a time of 60 min. The acid leaching residue and the acid leaching liquid were then obtained by solid-liquid separation;

[0114] (6) 1 L of the acid leaching solution was mixed with lanthanum hydroxide in a molar ratio of lanthanum hydroxide to nickel, cobalt and manganese of 1:1, and the temperature was set at 40°C for 70 min to carry out precipitation reaction, and then solid-liquid separation was performed to obtain lanthanum hydroxyphosphate and phosphorus removal solution;

[0115] (7) adding potassium hydroxide to the aforementioned potassium hydroxide solution, taking 1 L of the dephosphorization solution, mixing it with potassium hydroxide in a molar ratio of potassium hydroxide to nickel, cobalt, and manganese of 2:1, setting the temperature to 80° C. and the time to 50 min for precipitation reaction, and then performing solid-liquid separation to obtain nickel, cobalt, and manganese coprecipitate and potassium halide solution;

[0116] (8) 10 g of acid leaching residue was mixed with hexane at a liquid-to-solid ratio of 1.7 mL / g and dissolved at 20 °C. After solid-liquid separation, 8.11 g of graphite was obtained. The hexane was evaporated and reused to obtain 1.89 g of sulfur.

[0117] In this embodiment, during the sulfur thermal reaction, the conversion rate of sulfur ions to elemental sulfur is 96%, during water leaching, the lithium leaching rate is 98%, during acid leaching, the total leaching rate of nickel, cobalt and manganese is 97%, and during lithium and nickel, cobalt and manganese precipitation, through the recycling and reuse of the mother liquor, the total precipitation rate of lithium, nickel, cobalt and manganese is 99%, and the recovery rate of graphite is 96%. This embodiment realizes the cascade leaching and cascade recovery of complex energy metals, and synergistically recovers sulfur and graphite. The overall process is pollution-free, and the resource recovery of sulfide all-solid-state batteries is realized.

[0118] Example 5

[0119] This embodiment provides a method for recycling retired sulfide all-solid-state batteries, and the steps are as follows:

[0120] (1) Collect retired sulfide all-solid-state batteries (solid electrolyte is Li6PS5Br, ternary cathode material is LiNi 0.6 Co 0.2 Mn 0.2 O2), equipped with solid electrolyte Li6PS5Br and ternary cathode material LiNi 0.6 Co 0.2 Mn 0.2 The molar ratio of O2 is 1:27, the reaction temperature is set at 330°C and the reaction time is 240 min to carry out sulfur thermal reaction, and the retired sulfide all-solid-state battery cells are subjected to overall pyrolysis treatment to obtain pyrolysis slag and naturally detached current collectors. The generated hydrogen fluoride gas is introduced into the tail gas treatment section and neutralized with calcium hydroxide to obtain calcium fluoride;

[0121] (2) 100 g of pyrolysis residue was mixed with water at a liquid-solid ratio of 9 mL / g, and the temperature was set at 70 °C for 50 min to perform water immersion reaction. After solid-liquid separation, the water immersion liquid and water immersion residue were obtained;

[0122] (3) concentrating the water extract until the lithium concentration reaches 14 g / L to obtain a concentrated water extract;

[0123] (4) 1 L of concentrated water extract was added with 106 g of sodium carbonate, and the temperature was set at 70° C. for 250 min to carry out precipitation reaction, followed by solid-liquid separation to obtain lithium carbonate and sodium hydroxide solution;

[0124] (5) 100 g of water-leached residue was mixed with hydrochloric acid in a molar ratio of hydrogen chloride to nickel, cobalt and manganese of 3:1, and the acid leaching reaction was carried out at a hydrochloric acid concentration of 2.4 mol / L, a temperature of 20°C and a time of 260 min. The acid leaching residue and the acid leaching liquid were then obtained by solid-liquid separation;

[0125] (6) 1 L of the acid leaching solution was mixed with zinc hydroxide in a molar ratio of zinc hydroxide to nickel, cobalt and manganese of 3:1, and the precipitation reaction was performed at 20°C for 270 min. After solid-liquid separation, zinc hydroxyphosphate and phosphorus removal solution were obtained;

[0126] (7) Sodium hydroxide was added to the aforementioned sodium hydroxide solution, 1 L of the dephosphorization solution was taken, and the mixture was mixed with sodium hydroxide in a molar ratio of sodium hydroxide to nickel, cobalt, and manganese of 2:1. The temperature was set at 40° C. and the time was 220 min for precipitation reaction. After solid-liquid separation, nickel, cobalt, and manganese coprecipitates and sodium halide solution were obtained;

[0127] (8) 10 g of the acid leaching residue was mixed with hexane at a liquid-to-solid ratio of 0.9 mL / g and dissolved at 90 °C. After solid-liquid separation, 7.15 g of graphite was obtained. The hexane was evaporated and reused to obtain 2.85 g of sulfur.

[0128] In this embodiment, during the sulfur thermal reaction, the conversion rate of sulfur ions to elemental sulfur is 95%, during water leaching, the lithium leaching rate is 97%, during acid leaching, the total leaching rate of nickel, cobalt and manganese is 96%, and when lithium and nickel, cobalt and manganese are precipitated, the total precipitation rate of lithium, nickel, cobalt and manganese is 99% through the recycling and reuse of the mother liquor, and the recovery rate of graphite is 95%. This embodiment realizes the cascade leaching and cascade recovery of complex energy metals, and synergistically recovers sulfur and graphite. The overall process is pollution-free, and the resource recovery of sulfide all-solid-state batteries is realized.

[0129] Example 6

[0130] This embodiment provides a method for recycling retired sulfide all-solid-state batteries, and the steps are as follows:

[0131] (1) Collect retired sulfide all-solid-state batteries (solid electrolyte is Li6PS5I, ternary cathode material is LiNi 0.3 Co 0.3 Mn 0.3 O2), equipped with solid electrolyte Li6PS5I and ternary cathode material LiNi 0.3 Co0.3 Mn 0.3 The molar ratio of O2 is 1:17, the reaction temperature is set at 410°C and the reaction time is 150 min to carry out a sulfur thermal reaction, and the retired sulfide all-solid-state battery cells are subjected to overall pyrolysis treatment to obtain pyrolysis slag and naturally detached current collectors. The generated hydrogen fluoride gas is introduced into the tail gas treatment section and neutralized with calcium hydroxide to obtain calcium fluoride;

[0132] (2) 100 g of pyrolysis residue was mixed with water at a liquid-to-solid ratio of 12 mL / g, and the temperature was set at 60 °C and the time was 140 min for water immersion reaction. After solid-liquid separation, the water immersion liquid and water immersion residue were obtained;

[0133] (3) concentrating the water extract until the lithium concentration reaches 12 g / L to obtain a concentrated water extract;

[0134] (4) 1 L of concentrated water extract was added with 119 g of potassium carbonate, and the temperature was set at 85° C. for 130 min to carry out precipitation reaction, followed by solid-liquid separation to obtain lithium carbonate and potassium hydroxide solution;

[0135] (5) 100 g of water-leached residue was mixed with hydrochloric acid in a molar ratio of hydrogen chloride to nickel, cobalt and manganese of 6:1, and the acid leaching reaction was carried out at a hydrochloric acid concentration of 1.7 mol / L, a temperature of 40°C and a time of 190 min. The acid leaching residue and the acid leaching liquid were then obtained by solid-liquid separation;

[0136] (6) 1 L of the acid leaching solution was mixed with zirconium hydroxide in a molar ratio of zirconium hydroxide to nickel, cobalt and manganese of 2:1, and the temperature was set at 35° C. for 110 min to carry out precipitation reaction, and then solid-liquid separation was performed to obtain zirconium hydroxyphosphate and phosphorus removal solution;

[0137] (7) Potassium hydroxide was added to the sodium hydroxide solution, 1 L of the phosphorus removal solution was taken, and the mixture was mixed with potassium hydroxide in a molar ratio of potassium hydroxide to nickel, cobalt and manganese of 2:1. The temperature was set at 45° C. and the time was 130 min for precipitation reaction. After solid-liquid separation, nickel, cobalt and manganese coprecipitate and potassium halide solution were obtained;

[0138] (8) 10 g of acid leaching residue was mixed with toluene at a liquid-solid ratio of 1.1 mL / g and dissolved at 60 °C. After solid-liquid separation, 7.78 g of graphite was obtained. The toluene was evaporated and reused to obtain 2.22 g of sulfur.

[0139] In this embodiment, during the sulfur thermal reaction, the conversion rate of sulfur ions to elemental sulfur is 96%, during water leaching, the lithium leaching rate is 98%, during acid leaching, the total leaching rate of nickel, cobalt and manganese is 97%, and during lithium and nickel, cobalt and manganese precipitation, through the recycling and reuse of the mother liquor, the total precipitation rate of lithium, nickel, cobalt and manganese is 99%, and the recovery rate of graphite is 96%. This embodiment realizes the cascade leaching and cascade recovery of complex energy metals, and synergistically recovers sulfur and graphite. The overall process is pollution-free, and the resource recovery of sulfide all-solid-state batteries is realized.

[0140] Comparative Example 1

[0141] Except that the temperature of the sulfur thermal reaction in step (1) is set to 200° C., the remaining steps and conditions are the same as those in Example 2.

[0142] In this comparative example, during the sulfur thermal reaction, the conversion rate of sulfide ions to elemental sulfur was 2%, during water leaching, the leaching rate of lithium was 22%, accompanied by the generation of hydrogen sulfide gas, and during acid leaching, the total leaching rate of nickel, cobalt and manganese was 9%.

[0143] Comparative Example 2

[0144] Except that the molar ratio of the solid electrolyte of the sulfur thermal reaction to the ternary positive electrode material in step (1) is set to 1:1, the other conditions are the same as those in Example 2.

[0145] In this comparative example, during the sulfur thermal reaction, the conversion rate of sulfur ions to elemental sulfur was 34%, during water leaching, the leaching rate of lithium was 94%, accompanied by the generation of hydrogen sulfide gas, and during acid leaching, the total leaching rate of nickel, cobalt and manganese was 98%.

[0146] Comparative Example 3

[0147] Except that the time of the sulfur thermal reaction in step (1) is set to 5 min, the other conditions are the same as those in Example 2.

[0148] In this comparative example, during the sulfur thermal reaction, the conversion rate of sulfur ions to elemental sulfur was 84%, during water leaching, the leaching rate of lithium was 89%, accompanied by the generation of hydrogen sulfide gas, and during acid leaching, the total leaching rate of nickel, cobalt and manganese was 88%.

[0149] The key indicators of the above embodiments and comparative examples are summarized, and the results are shown in Table 1.

[0150] Table 1

[0151]

[0152]

[0153] By comparing Examples 1-6, it can be seen that when the reaction parameters are set within the reaction conditions of the present invention, the sulfur thermal reaction can be fully carried out, thereby achieving a high leaching rate and high precipitation rate of lithium nickel cobalt manganese, and synergistically achieving efficient recovery of graphite and sulfur.

[0154] By comparing Example 2 with Comparative Example 1, it can be seen that when the pyrolysis temperature is lower than 300°C, the sulfur thermal reaction basically does not occur, and the sulfur conversion rate is only 2%, resulting in the inability of nickel, cobalt and manganese in the ternary positive electrode material to be reduced and decomposed, and the leaching rate is as low as 9%. The unreactive phosphorus-based sulfide solid electrolyte undergoes a hydrolysis reaction during the water immersion process, and a small amount of lithium is leached, accompanied by the production of hydrogen sulfide.

[0155] By comparing Example 2 with Comparative Example 2, it can be seen that when the molar ratio of the solid electrolyte to the ternary positive electrode material is higher than 1:2, the solid electrolyte is excessive, the nickel, cobalt and manganese in the ternary positive electrode material can be fully reduced and deconstructed, and the lithium can also be fully leached, but the sulfur conversion rate is only 34%, and part of the sulfur is hydrolyzed into hydrogen sulfide.

[0156] By comparing Example 2 with Comparative Example 3, it can be seen that when the pyrolysis time is less than 20 minutes, the sulfur thermal reaction fails to proceed fully, and the sulfur conversion rate is 74%, resulting in the inability of nickel, cobalt and manganese in the ternary positive electrode material to be fully reduced and decomposed, the leaching rate is 78%, and a small amount of sulfur is hydrolyzed into hydrogen sulfide.

[0157] In summary, the invention includes but is not limited to the above embodiments. Any equivalent replacement or partial improvement made under the spirit and principle of the present invention shall be deemed to be within the scope of protection of the present invention.

Claims

1. A method for recycling sulfide all-solid-state batteries, characterized by: The method steps include: (1) Sulfur thermal reaction: The retired sulfide all-solid-state battery cell is subjected to overall pyrolysis treatment, and the cell includes a nickel-cobalt-manganese ternary positive electrode material, a phosphorus-based sulfide solid electrolyte, a graphite negative electrode material, a binder and a current collector; during the pyrolysis treatment, the nickel-cobalt-manganese ternary positive electrode material and the phosphorus-based sulfide solid electrolyte undergo a sulfur thermal reaction, the molar ratio of the nickel-cobalt-manganese ternary positive electrode material and the phosphorus-based sulfide solid electrolyte is greater than or equal to 2:1, the sulfur thermal reaction temperature is 300-550°C, the sulfur thermal reaction time is greater than or equal to 20 minutes, and after the reaction is completed, pyrolysis slag and naturally detached current collector are obtained; wherein, the chemical formula of the nickel-cobalt-manganese ternary positive electrode material is Li[Ni (1-x-y) Mn x Co y ]O2, 0<x<1, 0<y<1, 0.3≤(1-xy)<1; the chemical formula of the phosphorus-based sulfide solid electrolyte is Li6PS5X, where X is Cl, Br or I; (2) Water immersion: The pyrolysis slag is added to water for water immersion treatment. After the treatment, the solid and liquid are separated to obtain water immersion liquid and water immersion slag; (3) Concentration treatment: Concentrating the water extract to obtain a concentrated water extract; (4) lithium precipitation: adding soluble carbonate to the concentrated aqueous solution for precipitation treatment, and after the treatment, separating the solid and the liquid to obtain lithium carbonate and a soluble hydroxide solution; (5) Acid leaching: adding hydrochloric acid to the water leaching residue in step (2) to carry out acid leaching treatment. After the treatment, solid-liquid separation is performed to obtain acid leaching residue and acid leaching liquid; (6) Phosphorus precipitation: adding hydroxide to the acid leaching solution to carry out precipitation treatment. After the treatment, the solid and liquid are separated to obtain hydroxyphosphate and phosphorus removal liquid; (7) Precipitating nickel, cobalt and manganese: adding the soluble hydroxide solution of step (4) to the dephosphorization solution, and supplementing with the same soluble hydroxide, and performing precipitation treatment. After the treatment is completed, solid-liquid separation is performed to obtain nickel, cobalt and manganese coprecipitate and halide solution; (8) Dissolution: adding a non-polar organic solvent to the acid leaching residue of step (5), and after sufficient dissolution, performing solid-liquid separation to obtain graphite and a sulfur-containing solution, and evaporating and separating the sulfur-containing solution to obtain sulfur and a non-polar organic solvent.

2. The resource recovery method of a sulfide all-solid-state battery according to claim 1, characterized in that: In step (1), during the sulfur-heat reaction, the binder degrades to produce hydrogen fluoride, which is neutralized with calcium hydroxide to obtain calcium fluoride.

3. The resource recovery method of a sulfide all-solid-state battery according to claim 1, characterized in that: In step (1), in the sulfur thermal reaction, the molar ratio of the nickel-cobalt-manganese ternary positive electrode material and the phosphorus-based sulfide solid electrolyte is 2-30:1, and the sulfur thermal reaction time is 20-300 min.

4. The resource recovery method of a sulfide all-solid-state battery according to claim 1, characterized in that: In step (2), the water immersion treatment temperature is 10-90°C and the treatment time is 20-300 min; The liquid-to-solid ratio of water immersion treatment is 8~20mL / g.

5. The resource recovery method of a sulfide all-solid-state battery according to claim 1, characterized in that: In step (3), the concentration of lithium ions in the concentrated water extract is 3-19 g / L.

6. The resource recovery method of a sulfide all-solid-state battery according to claim 1, characterized in that: In step (4), the molar ratio of soluble carbonate to lithium ions in the concentrated aqueous solution is 1:2; The soluble carbonate is one or more of lithium carbonate, sodium carbonate and potassium carbonate; In step (4), the lithium precipitation treatment time is 20 to 300 minutes.

7. The resource recovery method of a sulfide all-solid-state battery according to claim 1, characterized in that: In step (5), the ratio of the molar amount of HCl in the hydrochloric acid to the total molar amount of nickel, cobalt and manganese elements in the water-leached residue is 2 to 10:1; The molar concentration of hydrochloric acid is 0.1~3mol / L; The temperature of the acid leaching treatment is 10~90℃, and the treatment time is 20~300min.

8. The resource recovery method of a sulfide all-solid-state battery according to claim 1, characterized in that: In step (6), the hydroxide is a hydroxide that can form a colloid in a weakly acidic environment, including one or more of aluminum hydroxide, iron hydroxide, lanthanum hydroxide, copper hydroxide, zinc hydroxide and zirconium hydroxide; The ratio of the molar amount of the hydroxide to the total molar amount of nickel, cobalt and manganese elements in the acid leaching solution is greater than or equal to 1:1; The temperature for phosphorus precipitation treatment is 10~50℃, and the treatment time is 20~300min.

9. The resource recovery method of a sulfide all-solid-state battery according to claim 1, characterized in that: In step (7), the ratio of the total molar amount of the soluble hydroxide to the total molar amount of nickel, cobalt and manganese elements in the dephosphorization solution is 2:1; The temperature of the nickel-cobalt-manganese precipitation treatment is 10-90° C., and the treatment time is 20-300 minutes.

10. The resource recovery method of a sulfide all-solid-state battery according to claim 1, characterized in that: In step (8), the non-polar organic solvent is one or more of petroleum ether, hexane, carbon disulfide, carbon tetrachloride, benzene, toluene, dichloroethane, chloroform and dichloromethane.

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