A resource recycling method of an all-solid-state battery

Abstract

The present application relates to a kind of resource recycling method of all-solid-state battery, belong to solid-state battery technical field.Retired polymer all-solid-state battery cell is separated to current collector, one-step dissolution liquid and one-step dissolution residue after one-step dissolution process;One-step dissolution liquid is separated to crystallization mother liquor and small amount of matrix after crystallization process;Small amount of matrix is separated to two-step evaporation residue after two-step dissolution, mixed with one-step dissolution residue, two-step evaporation process;Two-step evaporation residue is separated to pyrolysis residue after catalytic fluidized pyrolysis treatment;Pyrolysis residue is separated to acid leaching liquid and inorganic carbon material after acid leaching treatment;Acid leaching liquid is separated to precipitation and precipitation mother liquor after precipitation treatment;Precipitation mother liquor is treated after neutralization, concentration, lithium precipitation. This method effectively realizes the high value-added recovery of energy metal and conducting agent in retired polymer all-solid-state battery, and cooperatively realizes the recovery of graphite and other inorganic carbon.

Description

Technical Field

[0001] This invention relates to a method for the resource recycling of all-solid-state batteries, belonging to the technical fields of solid-state batteries and solid waste resource utilization. Background Technology

[0002] Solid-state batteries are an emerging clean energy conversion device, attracting active investment from well-known domestic and international companies in their research and industrialization. The key material for all-solid-state batteries, the solid electrolyte, is mainly composed of sulfides, oxides, halides, and polymers. Among these, polymer solid electrolytes offer good flexibility, excellent electrochemical performance, mature manufacturing processes, and relatively low cost, with the potential for high ionic conductivity. Polymer all-solid-state batteries prepared from polymer electrolytes exhibit high safety, high energy density, and strong temperature adaptability, showing broad application prospects. Given the normal capacity decay and abnormal damage associated with batteries, a large number of retired polymer all-solid-state batteries are inevitable in the future. These retired polymer all-solid-state batteries are prone to producing hazardous substances such as hydrogen fluoride and heavy metal salts, while also containing high-value-added energy metals such as lithium. Their resource recycling will generate significant economic benefits and strategic importance.

[0003] Currently, there are few methods for the resource recovery of retired polymer solid-state batteries, and the main approach is to prioritize the treatment of polymer solid electrolytes. Polymer solid electrolytes consist of a matrix and a conductor. One research team, focusing on polymer solid electrolytes with polyethylene oxide as the matrix, proposed in invention patent CN117276729A, SCI paper "Thermally depolymerizable polyether electrolytes for convenient and low-cost recycling of LiTFSI, Angewandte Chemie International Edition 2022, 61, e202209169," and dissertation "Research on the Recovery and Reuse of Lithium Bis(trifluoromethanesulfonyl)imide and PEO in PEO Electrolytes, Beijing University of Chemical Technology, 2023," that by utilizing the difference in solubility between the matrix and the conductor in solvents, an optimized dissolution-crystallization process can recover approximately 96% of the matrix first. The remaining 4% of the matrix, mixed with all the conductor, is then subjected to a pyrolysis process to remove the matrix and recover 65% of the conductor. However, the recovery rate of the conductive agent described in this method is low, and the pyrolysis process of the conductive agent generates hazardous fluorine-containing waste gas. Furthermore, this method only involves treating the polymer solid electrolyte, and the slag phase obtained after treating the polymer solid electrolyte includes inorganic carbon materials such as graphite and acetylene black, as well as high-value-added cathode materials; further processing may result in high energy consumption.

[0004] In summary, existing recycling methods for polymer all-solid-state batteries suffer from low yields, high pollution, and high energy consumption, and have not thoroughly explored the potential role of the solid electrolyte in the recycling of positive and negative electrode materials. With the gradual establishment of the high-quality development concept, developing a resource-based recycling method for polymer all-solid-state batteries that achieves high yields, zero pollution, low energy consumption, and high raw material utilization is of great significance to this field. Summary of the Invention

[0005] In view of this, the purpose of this invention is to provide a resource recycling method for all-solid-state batteries. This method can recycle retired polymer all-solid-state batteries with high added value, achieving high yield, zero pollution, low energy consumption, and high raw material utilization, thus possessing good environmental, economic, and social benefits and promising industrialization prospects.

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

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

[0008] (1) One-step dissolution: The retired polymer solid-state battery cell is subjected to one-step dissolution treatment. After the treatment, solid and liquid are separated to obtain current collector, one-step dissolution solution and one-step dissolution residue. The retired polymer solid-state battery cell includes current collector, polymer solid electrolyte matrix, conductive agent and waste positive electrode material. The waste positive electrode material is composed of nickel cobalt manganese ternary material or FePO4 (when the positive electrode active material of the polymer solid-state battery is lithium iron phosphate, after long-term use, lithium iron phosphate will lose lithium and become FePO4); the polymer solid electrolyte matrix is ​​polyethylene oxide.

[0009] (2) Crystallization: The solution from the first step is crystallized at a temperature below 20°C. After the treatment, the solid and liquid are separated to obtain the mother liquor and a small amount of polymer matrix.

[0010] (3) One-step vacuum evaporation: The crystallization mother liquor is subjected to one-step vacuum evaporation. After the treatment, solvent vapor, residual polymer matrix and conductive agent are obtained.

[0011] (4) Two-step dissolution: The small amount of polymer matrix obtained in step (2) is subjected to a two-step dissolution treatment. After the treatment is completed, a two-step dissolution solution is obtained.

[0012] (5) Two-step vacuum evaporation: The two-step solution and the one-step solution residue are mixed and then subjected to two-step vacuum evaporation treatment; the mass ratio of polymer matrix in the two-step solution to waste positive electrode material in the one-step solution residue is greater than or equal to 1:22; after the treatment, solvent vapor and two-step vacuum evaporation residue are obtained.

[0013] (6) Catalytic fluidized bed pyrolysis: The two-step vacuum evaporation residue is pyrolyzed; during the pyrolysis process, the polymer matrix and the waste positive electrode material in the two-step vacuum evaporation residue undergo a catalytic fluidized bed carbothermal reduction reaction. The reaction temperature is 250-450℃ and the reaction time is greater than or equal to 20min. After the reaction is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0014] (7) Acid leaching: The pyrolysis residue is subjected to acid leaching treatment. After the treatment, the solid and liquid are separated to obtain acid leaching solution and inorganic carbon material.

[0015] (8) Precipitation: Add strong alkali to precipitate the acid leaching solution. After the treatment, separate the solid and liquid to obtain the precipitate and the mother liquor.

[0016] (9) Neutralization: The mother liquor of the precipitate is neutralized to obtain a dilute lithium-containing solution; then the dilute lithium-containing solution is concentrated to obtain a concentrated lithium-containing solution; finally, the concentrated lithium-containing solution is subjected to lithium precipitation treatment. After the treatment is completed, the solid and liquid are separated to obtain lithium carbonate and a neutral salt solution.

[0017] Preferably, the solvent vapor in step (3) is condensed and can be reused in step (1); the solvent vapor in step (5) is condensed and can be reused in step (4).

[0018] Preferably, in step (1), the solvent used for dissolution is one or more of methanol, ethanol and ethylene glycol, the dissolution temperature is 40 to 100°C, and the time is 1 to 24 hours.

[0019] Preferably, in step (2), the crystallization temperature is -20 to 20°C and the time is 1 to 24 hours.

[0020] Preferably, in step (3), the pressure of the reduced pressure evaporation is 0 to 0.1 MPa, the temperature is 20 to 100°C, and the time is 1 to 24 hours.

[0021] Preferably, in step (4), the solvent used for dissolution is one or more of water, dichloroethane, chloroform, acetonitrile, acetone, methanol, ethanol and ethylene glycol, the dissolution temperature is 20 to 100°C, and the time is 1 to 24 hours.

[0022] Preferably, in step (5), the mass ratio of the substrate to the waste cathode material in the first-step dissolution residue is 1-20:22, the second-step depressurization evaporation pressure is 0-0.1 MPa, the temperature is 20-100℃, and the time is 1-24 h.

[0023] Preferably, in step (6), the temperature of the catalytic fluidized carbothermal reduction reaction is 300-450°C and the time is 20-300 min.

[0024] Preferably, in step (7), the inorganic acid is one or more of hydrochloric acid, sulfuric acid and nitric acid, the ratio of the molar amount of protons in the inorganic acid to the total molar amount of metal elements in the pyrolysis residue is 3 to 10:2, the molar concentration of protons in the inorganic acid is 0.1 to 3 mol / L, the acid leaching temperature is 20 to 90°C, and the time is 20 to 300 min.

[0025] Preferably, in step (8), the strong alkali is one or more of sodium hydroxide and potassium hydroxide. When the main elements in the pyrolysis residue in step (7) are lithium, nickel, cobalt, and manganese, the pH of the acid leaching solution is adjusted to 8-14 by adding a strong alkali, and the temperature for precipitating nickel, cobalt, and manganese is 20-90°C for 20-300 min. When the main elements in the pyrolysis residue in step (7) are lithium, phosphorus, and iron, the pH of the acid leaching solution is adjusted to 2-6 by adding a strong alkali, and the temperature for precipitating phosphorus and iron is 20-90°C for 20-300 min.

[0026] Preferably, in step (9), during the neutralization process, when the elements in the pyrolysis residue in step (7) are lithium, nickel, cobalt, and manganese, one or more inorganic acids from hydrochloric acid, sulfuric acid, and nitric acid are added to adjust the pH of the precipitate mother liquor to 7, the neutralization temperature is 20–90°C, and the time is 2–30 min; when the elements in the pyrolysis residue in step (7) are lithium, phosphorus, and iron, sodium hydroxide and / or potassium hydroxide strong base are added to adjust the pH of the precipitate mother liquor to 7, the neutralization temperature is 20–90°C, and the time is 2–30 min.

[0027] Preferably, in step (9), the concentration of lithium ions in the lithium-containing concentrated solution after concentration treatment is 3 to 19 g / L.

[0028] Preferably, in step (9), a soluble carbonate is added to precipitate lithium in the concentrated lithium solution. After the treatment, the solid and liquid are separated to obtain lithium carbonate and a neutral salt solution. The soluble carbonate is one or more of sodium carbonate and potassium carbonate. The molar ratio of carbonate ions in the soluble carbonate to lithium ions in the concentrated lithium solution is 1:2. The precipitation temperature is 75-95°C and the precipitation time is 20-300 min.

[0029] Beneficial effects

[0030] This invention provides a method for the resource recycling of all-solid-state batteries, comprising the following steps: one-step dissolution, crystallization, one-step vacuum evaporation, two-step dissolution, two-step vacuum evaporation, catalytic fluidized bed pyrolysis, acid leaching, nickel-cobalt-manganese / phosphorus-iron precipitation, neutralization, concentration, and lithium precipitation. The main process is as follows: retired polymer all-solid-state battery cells undergo a one-step dissolution process to separate current collectors, a one-step dissolution solution, and a one-step dissolution residue; the one-step dissolution solution undergoes a crystallization process to separate crystallization mother liquor and a small amount of matrix; the crystallization mother liquor undergoes a one-step vacuum evaporation process to separate solvent vapor, multiple portions of matrix, and a conductive agent. The solvent vapor, after condensation, can be recycled back to the one-step dissolution process; the multiple portions of matrix and conductive agent can be used for the reprocessing of polymer solid-state electrolytes; and the small amount of matrix... The process involves a two-step dissolution process to obtain a two-step dissolution solution. The two-step dissolution solution and the first-step dissolution residue are then mixed and subjected to a two-step vacuum evaporation process to separate solvent vapor and the second-step vacuum evaporation residue. The solvent vapor is condensed and recycled for reuse in the second-step dissolution process. The second-step vacuum evaporation residue undergoes catalytic fluidized bed pyrolysis to separate water, carbon dioxide, and pyrolysis residue. The pyrolysis residue is then acid-leached to separate an acid leaching solution and inorganic carbon materials. The acid leaching solution undergoes nickel-cobalt-manganese or phosphorus-iron precipitation to separate nickel-cobalt-manganese co-precipitate or phosphorus-iron precipitate, and a mother liquor. The mother liquor is neutralized to obtain a dilute lithium-containing solution. The dilute lithium-containing solution is concentrated to obtain a concentrated lithium-containing solution. The concentrated lithium-containing solution undergoes lithium precipitation to separate lithium carbonate and a neutral salt solution. This invention fully utilizes the polymer solid-state electrolyte matrix, effectively achieving high-value-added recovery of energy metals and conductive agents from retired polymer all-solid-state batteries, and synergistically recovering inorganic carbons such as graphite and acetylene black, meeting the standards of high yield, zero pollution, low energy consumption, and high raw material utilization in new energy production.

[0031] The present invention provides a resource recovery method for all-solid-state batteries. Through a series of steps including one-step dissolution, crystallization, one-step vacuum evaporation, two-step dissolution, and two-step vacuum evaporation, the recovery of polymer solid electrolyte can be precisely controlled, and a portion of the polymer solid electrolyte matrix can be directed for use in subsequent catalytic fluidized bed pyrolysis steps. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the process flow for the resource recycling method of the all-solid-state battery described in this invention. Detailed Implementation

[0033] The present invention will be further described in detail below with reference to specific embodiments.

[0034] A method for resource recycling of all-solid-state batteries, comprising the following steps:

[0035] (1) One-step dissolution: The polymer all-solid battery cell is subjected to one-step dissolution treatment. After the treatment, solid and liquid are separated to obtain current collector, one-step dissolution solution and one-step dissolution residue; wherein, the retired polymer all-solid battery cell includes current collector, polymer solid electrolyte matrix, conductive agent and waste positive electrode material. The composition of waste positive electrode material is nickel cobalt manganese ternary positive electrode material or FePO4; the polymer solid electrolyte matrix is ​​polyethylene oxide;

[0036] (2) Crystallization: The solution from the first step is crystallized at a temperature below 20°C. After the treatment, the solid and liquid are separated to obtain the mother liquor and a small amount of polymer matrix.

[0037] (3) One-step vacuum evaporation: The crystallization mother liquor is subjected to one-step vacuum evaporation. After the treatment, solvent vapor, residual polymer matrix and conductive agent are obtained. The solvent vapor can be recycled for step (1) after condensation treatment.

[0038] (4) Two-step dissolution: A small portion of the matrix obtained in step (2) is subjected to a two-step dissolution treatment. After the treatment is completed, a two-step dissolution solution is obtained.

[0039] (5) Two-step vacuum evaporation: The two-step solution and the one-step solution residue are mixed and subjected to two-step vacuum evaporation; the mass ratio of the polymer matrix in the two-step solution to the positive electrode material in the one-step solution residue is greater than or equal to 1:22; after the treatment, solvent vapor and two-step vacuum evaporation residue are obtained; the solvent vapor can be recycled to step (4) after condensation treatment.

[0040] (6) Catalytic fluidized bed pyrolysis: The two-step vacuum evaporation residue is pyrolyzed; during the pyrolysis process, the matrix and the positive electrode material in the two-step vacuum evaporation residue undergo a catalytic fluidized bed carbothermal reduction reaction. The reaction temperature is less than or equal to 450℃ and the time is greater than or equal to 20min. After the reaction is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0041] (7) Acid leaching: Add inorganic acid to leach the pyrolysis residue. After the treatment, separate the solid and liquid to obtain acid leaching solution and inorganic carbon material.

[0042] (8) Nickel cobalt manganese precipitation / phosphorus iron precipitation: Add strong alkali to treat the acid leaching solution to precipitate nickel cobalt manganese or phosphorus iron. After the treatment, separate the solid and liquid to obtain nickel cobalt manganese coprecipitate or phosphorus iron precipitate and precipitate mother liquor.

[0043] (9) Neutralization: Add inorganic acid or strong base to neutralize the mother liquor of the precipitate. After the treatment, a dilute lithium-containing solution is obtained.

[0044] (10) Concentration: The lithium-containing dilute solution is concentrated to obtain a lithium-containing concentrated solution after the treatment is completed;

[0045] (11) Lithium precipitation: Add soluble carbonate to precipitate lithium in the concentrated lithium solution. After the treatment, separate the solid and liquid to obtain lithium carbonate and a neutral salt solution.

[0046] In some embodiments, in step (1), the molecular weight of the polymer matrix polyethylene oxide is 10. 5 ~10 6 .

[0047] In some embodiments, in step (1), the chemical formula of the waste 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 could be Li[Ni 0.8 Mn 0.1 Co 0.1 O2, Li[Ni 0.6 Mn 0.2 Co 0.2 O2, Li[Ni 0.5 Mn 0.3 Co 0.2 O2, Li[Ni 0.3 Mn 0.3 Co 0.3 O2, etc.

[0048] In some embodiments, in step (1), the dissolving solvent is methanol, ethanol, ethylene glycol, etc.

[0049] In some embodiments, the dissolution temperature in step (1) is 40 to 100°C. For example, it can be 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, etc.

[0050] In some embodiments, the dissolution time in step (1) is 1 to 24 hours. For example, it can be 1 hour, 4 hours, 7 hours, 11 hours, 14 hours, 17 hours, 21 hours, 24 hours, etc.

[0051] In some embodiments, the crystallization temperature in step (2) is -20 to 20°C. For example, it can be -20°C, -15°C, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, etc.

[0052] In some embodiments, the crystallization time in step (2) is 1 to 24 hours. For example, it can be 1 hour, 4 hours, 7 hours, 11 hours, 14 hours, 17 hours, 21 hours, 24 hours, etc.

[0053] In some embodiments, the reduced pressure evaporation pressure in step (3) is 0 to 0.1 MPa. For example, it can be 0.00001 MPa, 0.0001 MPa, 0.001 MPa, 0.01 MPa, 0.1 MPa, etc.

[0054] In some embodiments, the reduced pressure evaporation temperature in step (3) is 20–100°C. For example, it can be 20°C, 40°C, 60°C, 80°C, 100°C, etc.

[0055] In some embodiments, the reduced pressure evaporation time in step (3) is 1 to 24 hours. For example, it can be 1 hour, 4 hours, 7 hours, 11 hours, 14 hours, 17 hours, 21 hours, 24 hours, etc.

[0056] In some embodiments, in step (4), the dissolving solvent is water, dichloroethane, chloroform, acetonitrile, acetone, methanol, ethanol, ethylene glycol, etc.

[0057] In some embodiments, the dissolution temperature in step (4) is 20 to 100°C. For example, it can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, etc.

[0058] In some embodiments, the dissolution time in step (4) is 1 to 24 hours. For example, it can be 1 hour, 4 hours, 7 hours, 11 hours, 14 hours, 17 hours, 21 hours, 24 hours, etc.

[0059] In some embodiments, the reduced pressure evaporation pressure in step (5) is 0 to 0.1 MPa. For example, it can be 0.00001 MPa, 0.0001 MPa, 0.001 MPa, 0.01 MPa, 0.1 MPa, etc.

[0060] In some embodiments, the reduced pressure evaporation temperature in step (5) is 20–100°C. For example, it can be 20°C, 40°C, 60°C, 80°C, 100°C, etc.

[0061] In some embodiments, the reduced pressure evaporation time in step (5) is 1 to 24 hours. For example, it can be 1 hour, 4 hours, 7 hours, 11 hours, 14 hours, 17 hours, 21 hours, 24 hours, etc.

[0062] In some embodiments, in step (5), before the catalytic fluidized carbothermal reduction reaction, the mass ratio of the polymer matrix to the waste cathode material is 1 to 20:22. For example, it can be 1:22, 3:22, 5:22, 7:22, 9:22, 12:22, 14:22, 16:22, 18:22, 20:22, etc.

[0063] In some embodiments, in step (6), during the catalytic fluidized carbothermal reduction reaction, the reaction temperature of the polymer matrix and the waste cathode material is 250–450°C, for example, 250°C, 300°C, 350°C, 400°C, 450°C, etc. When the cathode active material is a ternary material, the polymer solid electrolyte matrix and the ternary material undergo a key catalytic fluidized carbothermal reduction reaction, specifically (C₂H₄O). n H₂O reduces M in LiMO₂ (M represents Ni). x Co y Mn z The total oxidation state is +3, where the ratio of x, y, and z can be adjusted, and when lithium is missing in LiMO2, the total oxidation state of M will be greater than +3; at the same time, (C2H4O) n • H2O is fluidized under the catalysis of LiMO2 in a heated environment. This process requires strict control of the amount of each reactant, the reaction temperature, and the time. The main components of the resulting pyrolysis residue are Li2O, MO, CO2, Li2CO3, H2O, and C (C includes inorganic carbon materials such as graphite and acetylene black). When the positive electrode active material is lithium iron phosphate, the polymer solid electrolyte matrix and the main component of the waste lithium iron phosphate material, FePO4, undergo a key catalytic fluidized carbothermal reduction reaction, specifically (C2H4O). n H2O reduces the Fe in FePO4 that has been oxidized due to localized lithium deficiency (the Fe in this part has a +3 oxidation state); simultaneously, (C2H4O) n H2O is fluidized under the catalysis of FePO4 in a heated environment. This process requires strict control of the amount of each reactant, the reaction temperature and time. The main components of the resulting pyrolysis residue are Fe3(PO4)2, P2O5, CO2, H2O and C (C includes inorganic carbon materials such as graphite and acetylene black).

[0064] In some embodiments, in step (6), the reaction time of the matrix and the waste cathode material in the catalytic fluidized carbothermal reduction reaction is 20 to 300 min. For example, it can be 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.

[0065] In some embodiments, in step (7), the inorganic acid is hydrochloric acid, sulfuric acid, nitric acid, etc.

[0066] In some embodiments, in step (7), the ratio of the molar amount of protons in the inorganic acid to the total molar amount of lithium, nickel, cobalt, and manganese elements (or the total molar amount of lithium and iron elements) in the pyrolysis slag is 3 to 10:2. For example, it can be 3:2, 4:2, 5:2, 6:2, 7:2, 8:2, 9:2, 10:2, etc.

[0067] In some embodiments, in step (7), the molar concentration of protons in the inorganic acid is 0.1–3 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.

[0068] In some embodiments, the acid leaching temperature in step (7) is 20 to 90°C. For example, it can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, etc.

[0069] In some embodiments, the acid leaching time in step (7) is 20 to 300 minutes. For example, it can be 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 (8), the strong alkali is sodium hydroxide, potassium hydroxide, etc.

[0071] In some embodiments, in step (8), when the elements in the pyrolysis slag in step (7) are mainly lithium, nickel, cobalt, and manganese, the amount of strong alkali added in this step can adjust the pH of the acid leaching solution to 8-14. For example, it can be 8, 9, 10, 11, 12, 13, 14, etc. When the elements in the pyrolysis slag in step (7) are mainly lithium, phosphorus, and iron, the amount of strong alkali added in this step can adjust the pH of the acid leaching solution to 2-6. For example, it can be 2, 3, 4, 5, 6, etc.

[0072] In some embodiments, in step (8), the temperature of the immersion nickel-cobalt-manganese or immersion phosphorus-iron is 20 to 90°C. For example, it can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, etc.

[0073] In some embodiments, in step (8), the time for immersing nickel-cobalt-manganese or immersing phosphorus-iron is 20 to 300 minutes. For example, it can be 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.

[0074] In some embodiments, in step (9), the inorganic acid is hydrochloric acid, sulfuric acid, nitric acid, etc., and the strong base is sodium hydroxide, potassium hydroxide, etc.

[0075] In some embodiments, in step (9), the amount of inorganic acid or strong base added can adjust the pH of the precipitate mother liquor to 7.

[0076] In some embodiments, the neutralization temperature in step (9) is 20 to 90°C. For example, it can be 20°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, etc.

[0077] In some embodiments, the neutralization time in step (9) is 2 to 30 minutes. For example, it can be 2 minutes, 4 minutes, 6 minutes, 8 minutes, 10 minutes, 12 minutes, 14 minutes, 16 minutes, 18 minutes, 20 minutes, 22 minutes, 24 minutes, 26 minutes, 28 minutes, 30 minutes, etc.

[0078] In some embodiments, in step (10), the concentration of lithium ions in the lithium-containing concentrated solution is 3 to 19 g / L. For example, it can be 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.

[0079] In some embodiments, in step (11), the soluble carbonate is sodium carbonate, potassium carbonate, etc.

[0080] In some embodiments, in step (11), the molar ratio of carbonate ions in the soluble carbonate to lithium ions in the lithium-containing concentrated solution is 1:2.

[0081] In some embodiments, the temperature of lithium deposition in step (11) is 75–95°C. For example, it can be 75°C, 80°C, 85°C, 90°C, 95°C, etc.

[0082] In some embodiments, the lithium deposition time in step (11) is 20 to 300 minutes. For example, it can be 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.

[0083] Example 1

[0084] This embodiment provides a method for the resource recycling of retired polymer solid-state batteries, the steps of which are as follows:

[0085] (1) Collect retired polymer all-solid-state battery cells (polymer solid electrolyte matrix is ​​polyethylene oxide, molecular weight is 10). 5 ~10 6 The waste cathode material is LiNi. 0.8 Mn 0.1 Co 0.1 O2), using ethylene glycol as solvent, the temperature was set to 100℃ and the time to 11h for one-step dissolution treatment. After the treatment, solid and liquid were separated to obtain a current collector, a one-step dissolution solution and a one-step dissolution residue.

[0086] (2) Take the solution from the first step, set the temperature to 0℃ and the time to 24h, and carry out crystallization treatment. After the treatment is completed, the solid and liquid are separated to obtain a small part of the matrix and the mother liquor of crystallization.

[0087] (3) Take the crystallization mother liquor, set the pressure to 0.001MPa, the temperature to 100℃ and the time to 1h, and carry out a one-step vacuum evaporation treatment. After the treatment is completed, solvent vapor, multiple matrix and conductive agent are obtained. The solvent vapor is recycled to step (1) after condensation treatment.

[0088] (4) Take a small portion of the matrix, use water as the solvent, set the temperature to 50℃ and the time to 14h, and carry out a two-step dissolution treatment. After the treatment is completed, a two-step dissolution solution is obtained.

[0089] (5) Take the two-step dissolution solution and the one-step dissolution residue, and set the matrix in the two-step dissolution solution and the LiNi in the one-step dissolution residue. 0.8 Mn 0.1 Co 0.1 The mass ratio of O2 is 1:22. The pressure is set to 0.001MPa, the temperature to 100℃ and the time to 1h. Two-step vacuum evaporation is carried out. After the treatment is completed, solvent vapor and two-step vacuum evaporation residue are obtained. The solvent vapor is recycled to step (4) after condensation treatment.

[0090] (6) Take the two-step vacuum evaporation residue, set the temperature to 350℃ and the time to 160min, and carry out catalytic fluidized carbothermic reduction reaction for pyrolysis treatment. After the treatment is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0091] (7) Take pyrolysis residue and hydrochloric acid, set the ratio of the molar amount of protons in hydrochloric acid to the total molar amount of lithium, nickel, cobalt and manganese elements in pyrolysis residue to 3:2, set the molar concentration of protons in hydrochloric acid to 0.1 mol / L, the temperature to 50℃ and the time to 300 min, and carry out acid leaching treatment. After the treatment is completed, the solid and liquid are separated to obtain acid leaching solution and inorganic carbon material.

[0092] (8) Take acid leaching solution and potassium hydroxide, adjust the pH of acid leaching solution to 11 with potassium hydroxide, set the temperature to 50℃ and the time to 180min, carry out nickel cobalt manganese precipitation treatment, after the treatment is completed, solid and liquid separation is performed to obtain nickel cobalt manganese coprecipitate and precipitate mother liquor.

[0093] (9) Take the precipitate mother liquor and hydrochloric acid, adjust the pH of the precipitate mother liquor to 7 with hydrochloric acid, set the temperature to 70℃ and the time to 30min, and perform neutralization treatment. After the treatment is completed, a lithium-containing dilute solution is obtained.

[0094] (10) Take a lithium-containing dilute solution, set the target lithium concentration to 13 g / L, and concentrate it. After the treatment is completed, a lithium-containing concentrated solution is obtained.

[0095] (11) Take a lithium-containing concentrated solution and potassium carbonate, set the molar ratio of lithium ions in potassium carbonate and lithium-containing concentrated solution to 1:2, set the temperature to 95℃ and the time to 200min, and carry out lithium precipitation treatment. After the treatment is completed, lithium carbonate and neutral salt solution are obtained.

[0096] In this embodiment, the recovery rate of the polymer solid electrolyte conductor is 99%, and the recovery rate of the matrix is ​​directionally controlled. After the catalytic fluidized carbothermal reduction reaction, LiNi 0.8 Mn 0.1 Co 0.1 The reduction and decomposition rate of O2 was 96%, the total leaching rate of lithium, nickel, cobalt, and manganese was 98%, the total precipitation rate was 93%, and the recovery rate of inorganic carbon such as graphite was 99%. This embodiment achieves high-value-added recovery of energy metals and conductors from retired polymer solid-state batteries, and synergistically realizes the recovery of inorganic carbon such as graphite.

[0097] Example 2

[0098] This embodiment provides a method for the resource recycling of retired polymer solid-state batteries, the steps of which are as follows:

[0099] (1) Collect retired polymer all-solid-state battery cells (polymer solid electrolyte matrix is ​​polyethylene oxide, molecular weight is 10). 5 ~106 The waste cathode material is LiNi. 0.6 Mn 0.2 Co 0.2 O2), methanol was used as solvent, the temperature was set at 40℃ and the time was 1h, and a one-step dissolution process was carried out. After the process was completed, solid and liquid were separated to obtain a current collector, a one-step dissolution solution and a one-step dissolution residue.

[0100] (2) Take the one-step solution, set the temperature to 20℃ and the time to 1h, and carry out crystallization treatment. After the treatment is completed, the solid and liquid are separated to obtain a small part of matrix and crystallization mother liquor.

[0101] (3) Take the crystallization mother liquor, set the pressure to 0.00001MPa, the temperature to 60℃ and the time to 17h, and carry out one-step vacuum evaporation treatment. After the treatment is completed, solvent vapor, multiple matrix and conductive agent are obtained. The solvent vapor is recycled to step (1) after condensation treatment.

[0102] (4) Take a small portion of the matrix, use ethanol as the solvent, set the temperature to 70℃ and the time to 1h, and carry out a two-step dissolution process. After the process is completed, a two-step solution is obtained.

[0103] (5) Take the two-step dissolution solution and the one-step dissolution residue, and set the matrix in the two-step dissolution solution and the LiNi in the one-step dissolution residue. 0.6 Mn 0.2 Co 0.2 The mass ratio of O2 is 20:22. The pressure is set to 0.1MPa, the temperature to 80℃ and the time to 11h. Two-step vacuum evaporation is carried out. After the treatment is completed, solvent vapor and two-step vacuum evaporation residue are obtained. The solvent vapor is recycled to step (4) after condensation treatment.

[0104] (6) Take the two-step vacuum evaporation residue, set the temperature to 450℃ and the time to 20min, and carry out catalytic fluidized carbothermal reduction reaction for pyrolysis treatment. After the treatment is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0105] (7) Take pyrolysis residue and nitric acid, set the ratio of the molar amount of protons in nitric acid to the total molar amount of lithium, nickel, cobalt and manganese elements in pyrolysis residue to be 10:2, set the molar concentration of protons in nitric acid to be 3.0 mol / L, the temperature to be 20℃ and the time to be 280 min, and carry out acid leaching treatment. After the treatment is completed, the solid and liquid are separated to obtain acid leaching solution and inorganic carbon material.

[0106] (8) Take the acid leaching solution and sodium hydroxide, adjust the pH of the acid leaching solution to 14 with sodium hydroxide, set the temperature to 90℃ and the time to 20min, and carry out the nickel cobalt manganese precipitation treatment. After the treatment is completed, the solid and liquid are separated to obtain nickel cobalt manganese coprecipitate and precipitate mother liquor.

[0107] (9) Take the precipitate mother liquor and nitric acid, adjust the pH of the precipitate mother liquor to 7 with nitric acid, set the temperature to 30℃ and the time to 28min, and perform neutralization treatment. After the treatment is completed, a lithium-containing dilute solution is obtained.

[0108] (10) Take a lithium-containing dilute solution, set the target lithium concentration to 19 g / L, and concentrate it. After the treatment is completed, a lithium-containing concentrated solution is obtained.

[0109] (11) Take a lithium-containing concentrated solution and sodium carbonate, set the molar ratio of lithium ions in sodium carbonate and lithium-containing concentrated solution to 1:2, set the temperature to 90℃ and the time to 20min, and carry out lithium precipitation treatment. After the treatment is completed, lithium carbonate and neutral salt solution are obtained.

[0110] In this embodiment, the recovery rate of the polymer solid electrolyte conductor is 99%, and the recovery rate of the matrix is ​​directionally controlled. After the catalytic fluidized carbothermal reduction reaction, LiNi 0.6 Mn 0.2 Co 0.2 The reduction and decomposition rate of O2 was 91%, the total leaching rate of lithium, nickel, cobalt, and manganese was 96%, the total precipitation rate was 91%, and the recovery rate of inorganic carbon such as graphite was 98%. This embodiment achieves high-value-added recovery of energy metals and conductors from retired polymer solid-state batteries, and synergistically realizes the recovery of inorganic carbon such as graphite.

[0111] Example 3

[0112] This embodiment provides a method for the resource recycling of retired polymer solid-state batteries, the steps of which are as follows:

[0113] (1) Collect retired polymer all-solid-state battery cells (polymer solid electrolyte matrix is ​​polyethylene oxide, molecular weight is 10). 5 ~10 6 The waste cathode material is LiNi. 0.5 Mn 0.3 Co 0.2 O2), using ethanol as solvent, the temperature was set at 70℃ and the time was 17h for one-step dissolution treatment. After the treatment was completed, solid and liquid were separated to obtain a current collector, a one-step dissolution solution and a one-step dissolution residue.

[0114] (2) Take the one-step solution, set the temperature to -20℃ and the time to 7h, and carry out crystallization treatment. After the treatment is completed, the solid and liquid are separated to obtain a small part of matrix and crystallization mother liquor.

[0115] (3) Take the crystallization mother liquor, set the pressure to 0.1MPa, the temperature to 80℃ and the time to 24h, and carry out one-step vacuum evaporation treatment. After the treatment is completed, solvent vapor, multiple matrix and conductive agent are obtained. The solvent vapor is recycled to step (1) after condensation treatment.

[0116] (4) Take a small portion of the matrix, use acetonitrile as solvent, set the temperature to 50℃ and the time to 21h, and carry out a two-step dissolution treatment. After the treatment is completed, a two-step solution is obtained.

[0117] (5) Take the two-step dissolution solution and the one-step dissolution residue, and set the matrix in the two-step dissolution solution and the LiNi in the one-step dissolution residue. 0.5 Mn 0.3 Co 0.2 The mass ratio of O2 is 12:22. The pressure is set to 0.0001MPa, the temperature to 60℃ and the time to 21h. Two-step vacuum evaporation is carried out. After the treatment is completed, solvent vapor and two-step vacuum evaporation residue are obtained. The solvent vapor is recycled to step (4) after condensation treatment.

[0118] (6) Take the two-step vacuum evaporation residue, set the temperature to 250℃ and the time to 300min, and carry out catalytic fluidized carbothermal reduction reaction for pyrolysis treatment. After the treatment is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0119] (7) Take pyrolysis residue and sulfuric acid, set the ratio of the molar amount of protons in sulfuric acid to the total molar amount of lithium, nickel, cobalt and manganese elements in pyrolysis residue to 7:2, set the molar concentration of protons in sulfuric acid to 1.7 mol / L, the temperature to 40℃ and the time to 220 min, and carry out acid leaching treatment. After the treatment is completed, the solid and liquid are separated to obtain acid leaching solution and inorganic carbon material.

[0120] (8) Take acid leaching solution and potassium hydroxide, adjust the pH of acid leaching solution to 8 with potassium hydroxide, set the temperature to 30℃ and the time to 300 min, carry out nickel cobalt manganese precipitation treatment, after the treatment is completed, solid and liquid separation is performed to obtain nickel cobalt manganese coprecipitate and precipitate mother liquor.

[0121] (9) Take the mother liquor of precipitation and sulfuric acid, adjust the pH of the mother liquor of precipitation to 7 with sulfuric acid, set the temperature to 20℃ and the time to 4min, and perform neutralization treatment. After the treatment is completed, a lithium-containing dilute solution is obtained.

[0122] (10) Take a lithium-containing dilute solution, set the target lithium concentration to 3 g / L, and concentrate it. After the treatment is completed, a lithium-containing concentrated solution is obtained.

[0123] (11) Take a lithium-containing concentrated solution and potassium carbonate, set the molar ratio of lithium ions in potassium carbonate and lithium-containing concentrated solution to 1:2, set the temperature to 75℃ and the time to 300min, and carry out lithium precipitation treatment. After the treatment is completed, lithium carbonate and neutral salt solution are obtained.

[0124] In this embodiment, the recovery rate of the polymer solid electrolyte conductor is 99%, and the recovery rate of the matrix is ​​directionally controlled. After the catalytic fluidized carbothermal reduction reaction, LiNi 0.5 Mn 0.3Co 0.2 The reduction and decomposition rate of O2 was 92%, the total leaching rate of lithium, nickel, cobalt, and manganese was 97%, the total precipitation rate was 92%, and the recovery rate of inorganic carbon such as graphite was 97%. This embodiment achieves high-value-added recovery of energy metals and conductors from retired polymer solid-state batteries, and synergistically realizes the recovery of inorganic carbon such as graphite.

[0125] Example 4

[0126] This embodiment provides a method for the resource recycling of retired polymer solid-state batteries, the steps of which are as follows:

[0127] (1) Collect retired polymer all-solid-state battery cells (polymer solid electrolyte matrix is ​​polyethylene oxide, molecular weight is 10). 5 ~10 6 The waste cathode material is LiNi. 0.3 Mn 0.3 Co 0.3 O2), using ethylene glycol as solvent, the temperature was set at 90℃ and the time was 21h for one-step dissolution treatment. After the treatment was completed, solid and liquid were separated to obtain a current collector, a one-step dissolution solution and a one-step dissolution residue.

[0128] (2) Take the one-step solution, set the temperature to 5℃ and the time to 17h, and carry out crystallization treatment. After the treatment is completed, the solid and liquid are separated to obtain a small part of matrix and crystallization mother liquor.

[0129] (3) Take the crystallization mother liquor, set the pressure to 0.0001MPa, the temperature to 80℃ and the time to 4h, and carry out a one-step vacuum evaporation treatment. After the treatment is completed, solvent vapor, multiple matrix and conductive agent are obtained. The solvent vapor is recycled to step (1) after condensation treatment.

[0130] (4) Take a small portion of the matrix, use dichloroethane as solvent, set the temperature to 20℃ and the time to 14h, and carry out a two-step dissolution treatment. After the treatment is completed, a two-step solution is obtained.

[0131] (5) Take the two-step dissolution solution and the one-step dissolution residue, and set the matrix in the two-step dissolution solution and the LiNi in the one-step dissolution residue. 0.3 Mn 0.3 Co 0.3 The mass ratio of O2 is 5:22. The pressure is set to 0.0001MPa, the temperature to 20℃ and the time to 1h. Two-step vacuum evaporation is carried out. After the treatment is completed, solvent vapor and two-step vacuum evaporation residue are obtained. The solvent vapor is recycled to step (4) after condensation treatment.

[0132] (6) Take the two-step vacuum evaporation residue, set the temperature to 300℃ and the time to 80min, and carry out catalytic fluidized carbothermic reduction reaction for pyrolysis treatment. After the treatment is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0133] (7) Take pyrolysis residue and hydrochloric acid, set the ratio of the molar amount of protons in hydrochloric acid to the total molar amount of lithium, nickel, cobalt and manganese elements in pyrolysis residue to 4:2, set the molar concentration of protons in hydrochloric acid to 0.2 mol / L, the temperature to 80℃ and the time to 60 min, and carry out acid leaching treatment. After the treatment is completed, the solid and liquid are separated to obtain acid leaching solution and inorganic carbon material.

[0134] (8) Take the acid leaching solution and sodium hydroxide, adjust the pH of the acid leaching solution to 10 with sodium hydroxide, set the temperature to 70℃ and the time to 100min, and carry out the nickel cobalt manganese precipitation treatment. After the treatment is completed, the solid and liquid are separated to obtain nickel cobalt manganese coprecipitate and precipitate mother liquor.

[0135] (9) Take the precipitate mother liquor and hydrochloric acid, adjust the pH of the precipitate mother liquor to 7 with hydrochloric acid, set the temperature to 90℃ and the time to 6min, and perform neutralization treatment. After the treatment is completed, a lithium-containing dilute solution is obtained.

[0136] (10) Take a lithium-containing dilute solution, set the target lithium concentration to 11 g / L, and concentrate it. After the treatment is completed, a lithium-containing concentrated solution is obtained.

[0137] (11) Take a lithium-containing concentrated solution and sodium carbonate, set the molar ratio of lithium ions in sodium carbonate and lithium-containing concentrated solution to 1:2, set the temperature to 80℃ and the time to 240min, and carry out lithium precipitation treatment. After the treatment is completed, lithium carbonate and neutral salt solution are obtained.

[0138] In this embodiment, the recovery rate of the polymer solid electrolyte conductor is 99%, and the recovery rate of the matrix is ​​directionally controlled. After the catalytic fluidized carbothermal reduction reaction, LiNi 0.3 Mn 0.3 Co 0.3 The reduction and decomposition rate of O2 was 97%, the total leaching rate of lithium, nickel, cobalt, and manganese was 99%, the total precipitation rate was 95%, and the recovery rate of inorganic carbon such as graphite was 99%. This embodiment achieves high-value-added recovery of energy metals and conductors from retired polymer solid-state batteries, and synergistically realizes the recovery of inorganic carbon such as graphite.

[0139] Example 5

[0140] This embodiment provides a method for the resource recycling of retired polymer solid-state batteries, the steps of which are as follows:

[0141] (1) Collect retired polymer all-solid-state battery cells (polymer solid electrolyte matrix is ​​polyethylene oxide, molecular weight is 10). 5 ~106 The waste cathode material is LiNi. 0.8 Mn 0.1 Co 0.1 O2), using ethanol as solvent, the temperature was set at 50℃ and the time was 24h for one-step dissolution treatment. After the treatment was completed, solid and liquid were separated to obtain a current collector, a one-step dissolution solution and a one-step dissolution residue.

[0142] (2) Take the one-step solution, set the temperature to -15℃ and the time to 21h, and carry out crystallization treatment. After the treatment is completed, the solid and liquid are separated to obtain a small part of matrix and crystallization mother liquor.

[0143] (3) Take the crystallization mother liquor, set the pressure to 0.00001MPa, the temperature to 80℃ and the time to 11h, and carry out a one-step vacuum evaporation treatment. After the treatment is completed, solvent vapor, multiple matrix and conductive agent are obtained. The solvent vapor is recycled to step (1) after condensation treatment.

[0144] (4) Take a small portion of the matrix, use acetone as solvent, set the temperature to 20℃ and the time to 14h, and carry out a two-step dissolution treatment. After the treatment is completed, a two-step solution is obtained.

[0145] (5) Take the two-step dissolution solution and the one-step dissolution residue, and set the matrix in the two-step dissolution solution and the LiNi in the one-step dissolution residue. 0.8 Mn 0.1 Co 0.1 The mass ratio of O2 is 16:22. The pressure is set to 0.0001MPa, the temperature to 20℃ and the time to 4h. Two-step vacuum evaporation is carried out. After the treatment is completed, solvent vapor and two-step vacuum evaporation residue are obtained. The solvent vapor is recycled to step (4) after condensation treatment.

[0146] (6) Take the two-step vacuum evaporation residue, set the temperature to 300℃ and the time to 60min, and carry out catalytic fluidized carbothermic reduction reaction for pyrolysis treatment. After the treatment is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0147] (7) Take pyrolysis residue and nitric acid, set the ratio of the molar amount of protons in nitric acid to the total molar amount of lithium, nickel, cobalt and manganese elements in pyrolysis residue to 6:2, set the molar concentration of protons in nitric acid to 1.9 mol / L, the temperature to 40℃ and the time to 260 min, and carry out acid leaching treatment. After the treatment is completed, the solid and liquid are separated to obtain acid leaching solution and inorganic carbon material.

[0148] (8) Take acid leaching solution and potassium hydroxide, adjust the pH of acid leaching solution to 9 with potassium hydroxide, set the temperature to 30℃ and the time to 140min, carry out nickel cobalt manganese precipitation treatment, after the treatment is completed, solid and liquid separation is performed to obtain nickel cobalt manganese coprecipitate and precipitate mother liquor.

[0149] (9) Take the precipitate mother liquor and nitric acid, adjust the pH of the precipitate mother liquor to 7 with nitric acid, set the temperature to 80℃ and the time to 12min, and perform neutralization treatment. After the treatment is completed, a lithium-containing dilute solution is obtained.

[0150] (10) Take a lithium-containing dilute solution, set the target lithium concentration to 15 g / L, and concentrate it. After the treatment is completed, a lithium-containing concentrated solution is obtained.

[0151] (11) Take a lithium-containing concentrated solution and potassium carbonate, set the molar ratio of lithium ions in potassium carbonate and lithium-containing concentrated solution to 1:2, set the temperature to 95℃ and the time to 20min, and carry out lithium precipitation treatment. After the treatment is completed, lithium carbonate and neutral salt solution are obtained.

[0152] In this embodiment, the recovery rate of the polymer solid electrolyte conductor is 99%, and the recovery rate of the matrix is ​​directionally controlled. After the catalytic fluidized carbothermal reduction reaction, LiNi 0.8 Mn 0.1 Co 0.1 The reduction and decomposition rate of O2 was 98%, the total leaching rate of lithium, nickel, cobalt, and manganese was 99%, the total precipitation rate was 96%, and the recovery rate of inorganic carbon such as graphite was 99%. This embodiment achieves high-value-added recovery of energy metals and conductors from retired polymer solid-state batteries, and synergistically realizes the recovery of inorganic carbon such as graphite.

[0153] Example 6

[0154] This embodiment provides a method for the resource recycling of retired polymer solid-state batteries, the steps of which are as follows:

[0155] (1) Collect retired polymer all-solid-state battery cells (polymer solid electrolyte matrix is ​​polyethylene oxide, molecular weight is 10). 5 ~10 6 The waste cathode material is LiNi. 0.8 Mn 0.1 Co 0.1 O2), using methanol as solvent, the temperature was set at 20℃ and the time was 21h for one-step dissolution treatment. After the treatment was completed, solid and liquid were separated to obtain a current collector, a one-step dissolution solution and a one-step dissolution residue.

[0156] (2) Take the one-step solution, set the temperature to 15℃ and the time to 17h, and carry out crystallization treatment. After the treatment is completed, the solid and liquid are separated to obtain a small part of matrix and crystallization mother liquor.

[0157] (3) Take the crystallization mother liquor, set the pressure to 0.00001MPa, the temperature to 20℃ and the time to 14h, and carry out a one-step vacuum evaporation treatment. After the treatment is completed, solvent vapor, multiple matrix and conductive agent are obtained. The solvent vapor is recycled to step (1) after condensation treatment.

[0158] (4) Take a small portion of the matrix, use ethylene glycol as the solvent, set the temperature to 100℃ and the time to 24h, and carry out a two-step dissolution treatment. After the treatment is completed, a two-step solution is obtained.

[0159] (5) Take the two-step dissolution solution and the one-step dissolution residue, and set the matrix in the two-step dissolution solution and the LiNi in the one-step dissolution residue. 0.8 Mn 0.1 Co 0.1 The mass ratio of O2 is 7:22. The pressure is set to 0.00001MPa, the temperature to 100℃ and the time to 24h. Two-step vacuum evaporation is carried out. After the treatment is completed, solvent vapor and two-step vacuum evaporation residue are obtained. The solvent vapor is recycled to step (4) after condensation treatment.

[0160] (6) Take the two-step vacuum evaporation residue, set the temperature to 450℃ and the time to 100min, and carry out catalytic fluidized carbothermal reduction reaction for pyrolysis treatment. After the treatment is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0161] (7) Take pyrolysis residue and sulfuric acid, set the ratio of the molar amount of protons in sulfuric acid to the total molar amount of lithium, nickel, cobalt and manganese elements in pyrolysis residue to 9:2, set the molar concentration of protons in sulfuric acid to 0.7 mol / L, the temperature to 90℃ and the time to 20 min, and carry out acid leaching treatment. After the treatment is completed, the solid and liquid are separated to obtain acid leaching solution and inorganic carbon material.

[0162] (8) Take the acid leaching solution and sodium hydroxide, adjust the pH of the acid leaching solution to 13 with sodium hydroxide, set the temperature to 20℃ and the time to 240min, and carry out the nickel cobalt manganese precipitation treatment. After the treatment is completed, the solid and liquid are separated to obtain nickel cobalt manganese coprecipitate and precipitate mother liquor.

[0163] (9) Take the precipitate mother liquor and sulfuric acid, adjust the pH of the precipitate mother liquor to 7 with sulfuric acid, set the temperature to 40℃ and the time to 2min, and perform neutralization treatment. After the treatment is completed, a lithium-containing dilute solution is obtained.

[0164] (10) Take a lithium-containing dilute solution, set the target lithium concentration to 17 g / L, and concentrate it. After the treatment is completed, a lithium-containing concentrated solution is obtained.

[0165] (11) Take a lithium-containing concentrated solution and sodium carbonate, set the molar ratio of lithium ions in sodium carbonate and lithium-containing concentrated solution to 1:2, set the temperature to 75℃ and the time to 300min, and carry out lithium precipitation treatment. After the treatment is completed, lithium carbonate and neutral salt solution are obtained.

[0166] In this embodiment, the recovery rate of the polymer solid electrolyte conductor is 99%, and the recovery rate of the matrix is ​​directionally controlled. After the catalytic fluidized carbothermal reduction reaction, LiNi 0.8 Mn0.1 Co 0.1 The reduction and decomposition rate of O2 was 99%, the total leaching rate of lithium, nickel, cobalt, and manganese was 99%, the total precipitation rate was 97%, and the recovery rate of inorganic carbon such as graphite was 99%. This embodiment achieves high-value-added recovery of energy metals and conductors from retired polymer solid-state batteries, and synergistically realizes the recovery of inorganic carbon such as graphite.

[0167] Example 7

[0168] This embodiment provides a method for the resource recycling of retired polymer solid-state batteries, the steps of which are as follows:

[0169] (1) Collect retired polymer all-solid-state battery cells (polymer solid electrolyte matrix is ​​polyethylene oxide, molecular weight is 10). 5 ~10 6 The waste cathode material is FePO4. Ethylene glycol is used as the solvent. The temperature is set at 100℃ and the time is 11h for one-step dissolution treatment. After the treatment is completed, solid and liquid are separated to obtain current collector, one-step dissolution solution and one-step dissolution residue.

[0170] (2) Take the solution from the first step, set the temperature to 0℃ and the time to 24h, and carry out crystallization treatment. After the treatment is completed, the solid and liquid are separated to obtain a small part of the matrix and the mother liquor of crystallization.

[0171] (3) Take the crystallization mother liquor, set the pressure to 0.001MPa, the temperature to 100℃ and the time to 1h, and carry out a one-step vacuum evaporation treatment. After the treatment is completed, solvent vapor, multiple matrix and conductive agent are obtained. The solvent vapor is recycled to step (1) after condensation treatment.

[0172] (4) Take a small portion of the matrix, use water as the solvent, set the temperature to 50℃ and the time to 14h, and carry out a two-step dissolution treatment. After the treatment is completed, a two-step dissolution solution is obtained.

[0173] (5) Take the two-step dissolution solution and the one-step dissolution residue, set the mass ratio of the matrix in the two-step dissolution solution to the FePO4 in the one-step dissolution residue to be 1:22, set the pressure to be 0.001MPa, the temperature to be 100℃ and the time to be 1h, and carry out the two-step vacuum evaporation treatment. After the treatment is completed, solvent vapor and two-step vacuum evaporation residue are obtained. The solvent vapor is recycled to step (4) after condensation treatment.

[0174] (6) Take the two-step vacuum evaporation residue, set the temperature to 350℃ and the time to 160min, and carry out catalytic fluidized carbothermic reduction reaction for pyrolysis treatment. After the treatment is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0175] (7) Take pyrolysis residue and hydrochloric acid, set the ratio of the molar amount of protons in hydrochloric acid to the total molar amount of lithium iron element in pyrolysis residue to be 3:2, set the molar concentration of protons in hydrochloric acid to be 0.1 mol / L, the temperature to be 50℃ and the time to be 300 min, and carry out acid leaching treatment. After the treatment is completed, the solid and liquid are separated to obtain acid leaching solution and inorganic carbon material.

[0176] (8) Take the acid leaching solution and potassium hydroxide, adjust the pH of the acid leaching solution to 2 with potassium hydroxide, set the temperature to 50℃ and the time to 180min, and carry out the precipitation of ferric phosphorus. After the treatment is completed, the solid and liquid are separated to obtain ferric phosphorus precipitate and precipitate mother liquor.

[0177] (9) Take the precipitate mother liquor and potassium hydroxide, adjust the pH of the precipitate mother liquor to 7 with potassium hydroxide, set the temperature to 70℃ and the time to 30min, and perform neutralization treatment. After the treatment is completed, a lithium-containing dilute solution is obtained.

[0178] (10) Take a lithium-containing dilute solution, set the target lithium concentration to 13 g / L, and concentrate it. After the treatment is completed, a lithium-containing concentrated solution is obtained.

[0179] (11) Take a lithium-containing concentrated solution and potassium carbonate, set the molar ratio of lithium ions in potassium carbonate and lithium-containing concentrated solution to 1:2, set the temperature to 95℃ and the time to 200min, and carry out lithium precipitation treatment. After the treatment is completed, lithium carbonate and neutral salt solution are obtained.

[0180] In this embodiment, the recovery rate of the polymer solid electrolyte conductor is 99%, and the recovery rate of the matrix is ​​directionally controlled. After the catalytic fluidized carbothermal reduction reaction, the reduction and decomposition rate of FePO4 is 96%, the total leaching rate of lithium iron phosphate is 99%, the total precipitation rate is 95%, and the recovery rate of inorganic carbon such as graphite is 99%. This embodiment achieves high-value-added recovery of energy metals and conductors from retired polymer all-solid-state batteries, and synergistically achieves the recovery of inorganic carbon such as graphite.

[0181] Example 8

[0182] This embodiment provides a method for the resource recycling of retired polymer solid-state batteries, the steps of which are as follows:

[0183] (1) Collect retired polymer all-solid-state battery cells (polymer solid electrolyte matrix is ​​polyethylene oxide, molecular weight is 10). 5 ~10 6 The waste positive electrode material is composed of FePO4. Methanol is used as the solvent. The temperature is set at 40℃ and the time is 1h for one-step dissolution treatment. After the treatment is completed, solid and liquid are separated to obtain current collector, one-step dissolution solution and one-step dissolution residue.

[0184] (2) Take the one-step solution, set the temperature to 20℃ and the time to 1h, and carry out crystallization treatment. After the treatment is completed, the solid and liquid are separated to obtain a small part of matrix and crystallization mother liquor.

[0185] (3) Take the crystallization mother liquor, set the pressure to 0.00001MPa, the temperature to 60℃ and the time to 17h, and carry out one-step vacuum evaporation treatment. After the treatment is completed, solvent vapor, multiple matrix and conductive agent are obtained. The solvent vapor is recycled to step (1) after condensation treatment.

[0186] (4) Take a small portion of the matrix, use ethanol as the solvent, set the temperature to 70℃ and the time to 1h, and carry out a two-step dissolution process. After the process is completed, a two-step solution is obtained.

[0187] (5) Take the two-step dissolution solution and the one-step dissolution residue, set the mass ratio of the matrix in the two-step dissolution solution to the FePO4 in the one-step dissolution residue to be 20:22, set the pressure to be 0.1MPa, the temperature to be 80℃ and the time to be 11h, and carry out the two-step vacuum evaporation treatment. After the treatment is completed, solvent vapor and two-step vacuum evaporation residue are obtained. The solvent vapor is recycled to step (4) after condensation treatment.

[0188] (6) Take the two-step vacuum evaporation residue, set the temperature to 450℃ and the time to 20min, and carry out catalytic fluidized carbothermal reduction reaction for pyrolysis treatment. After the treatment is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0189] (7) Take pyrolysis residue and nitric acid, set the ratio of the molar amount of protons in nitric acid to the total molar amount of lithium iron in pyrolysis residue to be 10:2, set the molar concentration of protons in nitric acid to be 3.0 mol / L, the temperature to be 20℃ and the time to be 280 min, and carry out acid leaching treatment. After the treatment is completed, the solid and liquid are separated to obtain acid leaching solution and inorganic carbon material.

[0190] (8) Take the acid leaching solution and sodium hydroxide, adjust the pH of the acid leaching solution to 4 with sodium hydroxide, set the temperature to 90℃ and the time to 20min, and carry out the precipitation of ferric phosphorus. After the treatment is completed, the solid and liquid are separated to obtain ferric phosphorus precipitate and precipitate mother liquor.

[0191] (9) Take the mother liquor of precipitation and sodium hydroxide, adjust the pH of the mother liquor of precipitation to 7 with sodium hydroxide, set the temperature to 30℃ and the time to 28min, and perform neutralization treatment. After the treatment is completed, a lithium-containing dilute solution is obtained.

[0192] (10) Take a lithium-containing dilute solution, set the target lithium concentration to 19 g / L, and concentrate it. After the treatment is completed, a lithium-containing concentrated solution is obtained.

[0193] (11) Take a lithium-containing concentrated solution and sodium carbonate, set the molar ratio of lithium ions in sodium carbonate and lithium-containing concentrated solution to 1:2, set the temperature to 90℃ and the time to 20min, and carry out lithium precipitation treatment. After the treatment is completed, lithium carbonate and neutral salt solution are obtained.

[0194] In this embodiment, the recovery rate of the polymer solid electrolyte conductor is 99%, and the recovery rate of the matrix is ​​directionally controlled. After the catalytic fluidized carbothermal reduction reaction, the reduction and decomposition rate of FePO4 is 91%, the total leaching rate of lithium iron phosphate is 97%, the total precipitation rate is 92%, and the recovery rate of inorganic carbon such as graphite is 97%. This embodiment achieves high-value-added recovery of energy metals and conductors from retired polymer all-solid-state batteries, and synergistically achieves the recovery of inorganic carbon such as graphite.

[0195] Example 9

[0196] This embodiment provides a method for the resource recycling of retired polymer solid-state batteries, the steps of which are as follows:

[0197] (1) Collect retired polymer solid-state battery cells (the polymer solid electrolyte matrix is ​​polyethylene oxide with a molecular weight of 10). 5 ~10 6 The waste positive electrode material is composed of FePO4. Ethanol is used as the solvent. The temperature is set at 70℃ and the time is 17h for one-step dissolution treatment. After the treatment is completed, solid and liquid are separated to obtain current collector, one-step dissolution solution and one-step dissolution residue.

[0198] (2) Take the one-step solution, set the temperature to -20℃ and the time to 7h, and carry out crystallization treatment. After the treatment is completed, the solid and liquid are separated to obtain a small part of matrix and crystallization mother liquor.

[0199] (3) Take the crystallization mother liquor, set the pressure to 0.1MPa, the temperature to 80℃ and the time to 24h, and carry out one-step vacuum evaporation treatment. After the treatment is completed, solvent vapor, multiple matrix and conductive agent are obtained. The solvent vapor is recycled to step (1) after condensation treatment.

[0200] (4) Take a small portion of the matrix, use acetonitrile as solvent, set the temperature to 50℃ and the time to 21h, and carry out a two-step dissolution treatment. After the treatment is completed, a two-step solution is obtained.

[0201] (5) Take the two-step dissolution solution and the one-step dissolution residue, set the mass ratio of the matrix in the two-step dissolution solution to the FePO4 in the one-step dissolution residue to be 12:22, set the pressure to be 0.0001MPa, the temperature to be 60℃ and the time to be 21h, and carry out the two-step vacuum evaporation treatment. After the treatment is completed, solvent vapor and two-step vacuum evaporation residue are obtained. The solvent vapor is recycled to step (4) after condensation treatment.

[0202] (6) Take the two-step vacuum evaporation residue, set the temperature to 250℃ and the time to 300min, and carry out catalytic fluidized carbothermal reduction reaction for pyrolysis treatment. After the treatment is completed, water, carbon dioxide and pyrolysis residue are obtained.

[0203] (7) Take pyrolysis residue and sulfuric acid, set the ratio of the molar amount of protons in sulfuric acid to the total molar amount of lithium iron in pyrolysis residue to 7:2, set the molar concentration of protons in sulfuric acid to 1.7 mol / L, the temperature to 40℃ and the time to 220 min, and carry out acid leaching treatment. After the treatment is completed, the solid and liquid are separated to obtain acid leaching solution and inorganic carbon material.

[0204] (8) Take the acid leaching solution and potassium hydroxide, adjust the pH of the acid leaching solution to 6 with potassium hydroxide, set the temperature to 30℃ and the time to 300min, and carry out the precipitation of ferric phosphorus. After the treatment is completed, the solid and liquid are separated to obtain ferric phosphorus precipitate and precipitate mother liquor.

[0205] (9) Take the mother liquor of precipitation and potassium hydroxide, adjust the pH of the mother liquor of precipitation to 7 with potassium hydroxide, set the temperature to 20℃ and the time to 4min, and perform neutralization treatment. After the treatment is completed, a lithium-containing dilute solution is obtained.

[0206] (10) Take a lithium-containing dilute solution, set the target lithium concentration to 3 g / L, and concentrate it. After the treatment is completed, a lithium-containing concentrated solution is obtained.

[0207] (11) Take a lithium-containing concentrated solution and potassium carbonate, set the molar ratio of lithium ions in potassium carbonate and lithium-containing concentrated solution to 1:2, set the temperature to 75℃ and the time to 300min, and carry out lithium precipitation treatment. After the treatment is completed, lithium carbonate and neutral salt solution are obtained.

[0208] In this embodiment, the recovery rate of the polymer solid electrolyte conductor is 99%, and the recovery rate of the matrix is ​​directionally controlled. After the catalytic fluidized carbothermal reduction reaction, the reduction and decomposition rate of FePO4 is 92%, the total leaching rate of lithium iron phosphate is 98%, the total precipitation rate is 94%, and the recovery rate of inorganic carbon such as graphite is 98%. This embodiment achieves high-value-added recovery of energy metals and conductors from retired polymer all-solid-state batteries, and synergistically achieves the recovery of inorganic carbon such as graphite.

[0209] Comparative Example 1

[0210] In addition to the matrix and LiNi in step (5) 0.8 Mn 0.1 Co 0.1 The mass ratio of O2 was set to 1:44, and the remaining steps and conditions were the same as in Example 1.

[0211] In this comparative example, the recovery rate of the polymer solid electrolyte conductor was 99%, and the recovery rate of the matrix was directionally controlled. However, during the catalytic fluidized carbothermal reduction reaction, LiNi... 0.8 Mn 0.1 Co 0.1 The reduction and decomposition rate of O2 was 38%, the total leaching rate of lithium, nickel, cobalt, and manganese was 56%, and the total precipitation rate was 50%.

[0212] Comparative Example 2

[0213] Except for setting the temperature of the catalytic fluidized carbothermal reduction reaction in step (6) to 150°C, the other steps and conditions are the same as in Example 3.

[0214] In this comparative example, the recovery rate of the polymer solid electrolyte conductor was 99%, and the recovery rate of the matrix was directionally controlled. However, during the catalytic fluidized carbothermal reduction reaction, LiNi... 0.5 Mn 0.3 Co 0.2 The reduction and decomposition rate of O2 was 6%, the total leaching rate of lithium, nickel, cobalt, and manganese was 27%, and the total precipitation rate was 22%.

[0215] Comparative Example 3

[0216] Except for setting the time for the catalytic fluidized carbothermal reduction reaction in step (6) to 5 min, the other steps and conditions are the same as in Example 7.

[0217] In this comparative example, the recovery rate of the polymer solid electrolyte conductor was 99%, and the recovery rate of the matrix was directionally controlled. However, during the catalytic fluidized carbothermal reduction reaction, the reduction decomposition rate of FePO4 was 59%, the total leaching rate of lithium phosphate iron was 72%, and the total precipitation rate was 64%.

[0218] The key indicators of the above embodiments and comparative examples are summarized, and the results are shown in Table 1.

[0219] Table 1

[0220]

[0221] The comparison of Examples 1-9 shows that when the reaction parameters are set within the reaction conditions of the present invention, the catalytic fluidized carbon thermal reduction reaction can be fully carried out, thereby achieving a high decomposition rate of waste cathode materials, a high leaching rate and a high precipitation rate of lithium nickel cobalt manganese (lithium phosphorus iron), and synergistically achieving efficient recovery of inorganic carbon.

[0222] By comparing Comparative Example 1 with Example 1, it can be seen that when the mass ratio of polymer solid electrolyte matrix to ternary material is less than 1:22, the waste cathode material cannot be fully reduced and deconstructed, so that it still has a certain degree of acid resistance and the lithium nickel cobalt manganese leaching rate is 56%.

[0223] By comparing Comparative Example 2 and Example 3, it can be seen that when the pyrolysis temperature is below 250°C, the catalytic fluidized carbothermal reduction reaction cannot be fully activated, and the waste cathode material cannot be fully reduced and decomposed, so that it still has a certain degree of acid resistance, and the lithium nickel cobalt manganese leaching rate is 27%.

[0224] By comparing Comparative Example 3 and Example 7, it can be seen that when the pyrolysis time is less than 20 min, the catalytic fluidized carbothermal reduction reaction cannot be fully completed, and the waste cathode material cannot be fully reduced and decomposed, so that it still has a certain degree of acid resistance and the lithium iron phosphate leaching rate is 59%.

[0225] In summary, the invention includes, but is not limited to, the above embodiments. Any equivalent substitutions or partial improvements made under the spirit and principles of this invention shall be considered to be within the protection scope of this invention.

Claims

1. A method of resource recovery of an all-solid-state battery, characterized by: The method steps include: (1) One-step dissolution: the retired polymer full-solid-state battery cell is subjected to one-step dissolution treatment, and after the treatment is completed, solid-liquid separation is performed to obtain a current collector, one-step dissolution solution and one-step dissolution residue; wherein the retired polymer full-solid-state battery cell includes a current collector, a polymer solid electrolyte matrix, a conductive agent and a waste positive electrode material, the composition of the waste positive electrode material is a nickel-cobalt-manganese ternary material or FePO4, and the polymer solid electrolyte matrix is polyethylene oxide; (2) Crystallization: the one-step dissolution solution is subjected to crystallization treatment below 20°C, and after the treatment is completed, solid-liquid separation is performed to obtain a crystallization mother liquor and a small amount of polymer solid electrolyte matrix; (3) One-step reduced pressure evaporation: the crystallization mother liquor is subjected to one-step reduced pressure evaporation treatment, and after the treatment is completed, solvent vapor, residual polymer solid electrolyte matrix and a conductive agent are obtained; (4) Two-step dissolution: the small amount of polymer solid electrolyte matrix obtained in step (2) is subjected to two-step dissolution treatment, and after the treatment is completed, two-step dissolution solution is obtained; (5) Two-step reduced pressure evaporation: the two-step dissolution solution is mixed with the one-step dissolution residue and subjected to two-step reduced pressure evaporation treatment; the mass ratio of the polymer solid electrolyte matrix in the two-step dissolution solution to the waste positive electrode material in the one-step dissolution residue is greater than or equal to 1:22; after the treatment is completed, solvent vapor and two-step reduced pressure evaporation residue are obtained; (6) Catalytic fluidized pyrolysis: the two-step reduced pressure evaporation residue is subjected to pyrolysis treatment; during the pyrolysis process, the polymer solid electrolyte matrix and the waste positive electrode material in the two-step reduced pressure evaporation residue undergo catalytic fluidized carbon thermal reduction reaction, the reaction temperature is 250-450°C, the reaction time is greater than or equal to 20 min, and after the reaction is completed, water, carbon dioxide and pyrolysis residue are obtained; (7) Acid leaching: an inorganic acid is added to perform acid leaching treatment on the pyrolysis residue, and after the treatment is completed, solid-liquid separation is performed to obtain an acid leaching solution and an inorganic carbon material; (8) Precipitation: a strong base is added to perform precipitation treatment on the acid leaching solution, and after the treatment is completed, solid-liquid separation is performed to obtain a precipitate and a precipitation mother liquor; (9) Neutralization: the precipitation mother liquor is subjected to neutralization treatment to obtain a lithium-containing dilute solution; then the lithium-containing dilute solution is concentrated to obtain a lithium-containing concentrated solution; finally, the lithium-containing concentrated solution is subjected to lithium precipitation treatment, and after the treatment is completed, solid-liquid separation is performed to obtain lithium carbonate and a neutral salt solution.

2. A method of resource recovery of an all-solid-state battery according to claim 1, characterized by: The solvent vapor in step (3) is subjected to condensation treatment and can be reused in step (1); the solvent vapor in step (5) is subjected to condensation treatment and can be reused in step (4).

3. A method of resource recycling of an all-solid-state battery according to claim 1 or 2, characterized by: In step (1), the solvent used for dissolution is one or more of methanol, ethanol and ethylene glycol, the dissolution temperature is 40-100°C, and the time is 1-24 h; And / or, in step (4), the solvent used for dissolution is one or more of water, dichloroethane, chloroform, acetonitrile, acetone, methanol, ethanol and ethylene glycol, the dissolution temperature is 20-100°C, and the time is 1-24 h.

4. A method of resource recycling of an all-solid-state battery according to claim 1 or 2, characterized by: In step (2), the crystallization temperature is -20-20°C, and the time is 1-24 h.

5. A method of resource recycling of an all-solid-state battery according to claim 1 or 2, characterized by: In step (3), the reduced pressure evaporation pressure is 0-0.1 MPa, the temperature is 20-100°C, and the time is 1-24 h.

6. A method of resource recovery of an all-solid-state battery according to claim 1 or 2, characterized by: In step (5), the mass ratio of the polymer solid-state electrolyte matrix to the waste positive electrode material in the one-step dissolution residue is 1-20:22, the two-step evaporation pressure is 0-0.1 MPa, the temperature is 20-100 °C, and the time is 1-24 h.

7. A method of resource recovery of a solid-state battery according to claim 1 or 2, characterized in that: In step (6), the catalytic fluidized carbon thermal reduction reaction temperature is 300-450 °C, and the time is 20-300 min.

8. A method of resource recovery of an all-solid-state battery according to claim 1 or 2, characterized by: In step (7), the inorganic acid is one or more of hydrochloric acid, sulfuric acid, and nitric acid, the ratio of the molar amount of protons in the inorganic acid to the total molar amount of metal elements in the pyrolysis residue is 3-10:2, the molar concentration of protons in the inorganic acid is 0.1-3 mol / L, the acid leaching temperature is 20-90 °C, and the time is 20-300 min.

9. A method of resource recovery of a solid-state battery according to claim 1 or 2, wherein: In step (8), the strong base is one or more of sodium hydroxide and potassium hydroxide, when the elements in the pyrolysis residue in step (7) are mainly lithium, nickel, cobalt, and manganese, the strong base is added to adjust the pH of the acid leaching solution to 8-14, the nickel, cobalt, and manganese precipitation temperature is 20-90 °C, and the time is 20-300 min; when the elements in the pyrolysis residue in step (7) are mainly lithium, phosphorus, and iron, the strong base is added to adjust the pH of the acid leaching solution to 2-6, the phosphorus and iron precipitation temperature is 20-90 °C, and the time is 20-300 min.

10. A method of resource recovery of a solid-state battery as claimed in claim 1 or 2, wherein: In step (9), during neutralization, when the elements in the pyrolysis residue in step (7) are lithium, nickel, cobalt, and manganese, one or more of inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid is added to adjust the pH of the precipitation mother liquor to 7, the neutralization temperature is 20-90 °C, and the time is 2-30 min; when the elements in the pyrolysis residue in step (7) are lithium, phosphorus, and iron, sodium hydroxide and / or potassium hydroxide strong base is added to adjust the pH of the precipitation mother liquor to 7, the neutralization temperature is 20-90 °C, and the time is 2-30 min; In step (9), after concentration, the concentration of lithium ions in the lithium-containing concentrated solution is 3-19 g / L. In step (9), soluble carbonates are added to the lithium-containing concentrated solution for lithium precipitation treatment, and after the treatment, solid-liquid separation is performed to obtain lithium carbonate and a neutral salt solution; the soluble carbonates are one or more of sodium carbonate and potassium carbonate, the molar ratio of carbonate ions in the soluble carbonates to lithium ions in the lithium-containing concentrated solution is 1:2, the lithium precipitation temperature is 75-95 °C, and the time is 20-300 min.

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