CN109524735B - Recovery method of waste lithium iron phosphate-lithium titanate battery - Google Patents
Recovery method of waste lithium iron phosphate-lithium titanate battery Download PDFInfo
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- CN109524735B CN109524735B CN201811222624.2A CN201811222624A CN109524735B CN 109524735 B CN109524735 B CN 109524735B CN 201811222624 A CN201811222624 A CN 201811222624A CN 109524735 B CN109524735 B CN 109524735B
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- lithium
- iron phosphate
- lithium titanate
- lithium iron
- titanate battery
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002699 waste material Substances 0.000 title claims abstract description 30
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 title claims abstract description 29
- 238000011084 recovery Methods 0.000 title abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 35
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 11
- 239000000706 filtrate Substances 0.000 claims description 20
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 238000004537 pulping Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 10
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011888 foil Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001447 ferric ion Inorganic materials 0.000 claims description 2
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 150000002739 metals Chemical class 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 23
- 229910052744 lithium Inorganic materials 0.000 description 23
- 239000000243 solution Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for recycling waste lithium iron phosphate-lithium titanate batteries. The method realizes the simultaneous recovery of the positive and negative electrode powder materials in the lithium iron phosphate-lithium titanate battery, reduces the difficulty of separating the positive and negative electrode mixed materials in the battery crushing and sorting process, reduces the consumption of inorganic acid in the simultaneous recovery process of the positive and negative electrode powder materials, simplifies the recovery process, improves the concentration of Li ions in the solution, realizes the recovery of valuable metals in the positive and negative electrode powder materials of the lithium iron phosphate-lithium titanate battery, and improves the purity of the obtained product.
Description
Technical Field
The invention relates to the field of battery recovery, in particular to a recovery method of waste lithium iron phosphate-lithium titanate batteries.
Background
The lithium titanate has a three-dimensional lithium ion diffusion channel unique to a spinel structure, and has the advantages of excellent power characteristics, good high-temperature and low-temperature performances and the like. The lithium titanate battery is used as a negative electrode material of a lithium ion battery, namely lithium titanate, and can be combined with lithium manganate, ternary materials or lithium iron phosphate and other positive electrode materials to form a 2.4V or 1.9V lithium ion secondary battery. In addition, it can be used as a positive electrode, and constitutes a 1.5V lithium secondary battery with a metallic lithium or lithium alloy negative electrode. The lithium titanate cathode lithium ion battery has good reversibility in charge-discharge reaction, thereby ensuring the cycle life and the safety performance of the battery to a certain extent. Compared with common ternary lithium batteries, the lithium titanate negative lithium ion battery has low discharging efficiency attenuation in a low-temperature environment, strong quick charging efficiency and cycle life of more than 3 ten thousand times. Due to the characteristics of high safety, high stability, long service life and environmental protection of lithium titanate, the following characteristics can be predicted: after 2 to 3 years, the lithium titanate material must become a negative electrode material of a new generation of lithium ion battery and be widely applied to new energy automobiles, electric motorcycles and application fields requiring high safety, high stability and long period, and accordingly, the number of waste lithium titanate batteries is increased year by year.
In recent years, a great deal of work is done by many researchers on recycling and regenerating waste lithium titanate negative electrode materials. Chinese patent application No.: 201610665778.3 discloses a method for recycling lithium titanate electrode plates, which comprises the steps of carrying out high-temperature roasting separation on negative active substances and aluminum foil electrode plates, and crushing, roasting and screening the negative active substances to obtain a lithium titanate negative electrode material. Chinese patent application No.: 201710226858.3 discloses a method for recycling and preparing lithium titanate negative electrode material from waste lithium titanate battery, which comprises discharging waste lithium titanate battery, splitting shell, sorting out pole pieces, heating and dipping, sintering the separated lithium titanate battery material slurry to remove conductive carbon material, mixing with conductive coating agent, doping agent and lithium salt material, and calcining to prepare lithium titanate negative electrode material. However, in the recovery of waste lithium titanate batteries, the positive electrode material and the negative electrode material are often bonded and mixed together and are difficult to separate, so that when only the recovered powder is subjected to regeneration treatment according to the recovery method of the lithium titanate material, the obtained lithium titanate material contains corresponding impurities, and the waste of Li and nonferrous metals in the positive electrode material is caused. When lithium iron phosphate is used as the anode material of the lithium titanate battery, a large amount of inorganic acid is consumed during recovery, and meanwhile, a large amount of phosphate radical and iron ion impurities are contained in the solution, so that the subsequent purification process is complicated, and the prepared material is impure.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for recovering waste lithium iron phosphate-lithium titanate batteries, which realizes simultaneous recovery of positive and negative electrode powder materials in the lithium iron phosphate-lithium titanate batteries.
The technical scheme of the invention is as follows:
a method for recovering waste lithium iron phosphate-lithium titanate batteries specifically comprises the following steps:
(1) discharging the waste lithium iron phosphate-lithium titanate battery, crushing and sorting the battery after the discharging is finished, and respectively obtaining a shell, copper foil, aluminum foil and mixed materials of a positive electrode and a negative electrode;
(2) carrying out high-temperature heat treatment on the mixed material of the positive electrode and the negative electrode in the air to oxidize ferrous ions in the mixed material of the positive electrode and the negative electrode into ferric ions;
(3) adding the anode and cathode mixed material subjected to high-temperature heat treatment into water for pulping to obtain pulping liquid, then adding inorganic acid, stirring for reaction, and filtering the reactant to remove insoluble substances to obtain filtrate A;
(4) adjusting the pH value of the filtrate A to 2.0-3.0, adding a proper amount of Fe powder to remove Cu impurities, removing Fe and Al impurities in the solution by using an aluminoferrite method, and filtering to obtain a filtrate B;
(5) and concentrating, hydrolyzing and precipitating the obtained filtrate B containing titanium and lithium ions to obtain a metatitanic acid and lithium sulfate solution C.
The waste lithium iron phosphate-lithium titanate battery discharges in a discharging cabinet discharging mode, a resistance discharging mode or a salt water discharging mode.
The crushing and sorting mode in the step (1) is magnetic sorting, wind sorting or gravity sorting.
The temperature of the high-temperature heat treatment in the step (2) is 300-900 ℃, and the treatment time is 1-6 hours.
In the slurry obtained in the step (3), the mass ratio of the anode and cathode mixed materials to the water is 1: 4-10.
The temperature of stirring reaction after adding the inorganic acid in the step (3) is set to be 60-95 ℃ and the time is 0.5-3 hours.
The inorganic acid in the step (3) is hydrochloric acid or sulfuric acid, the volume ratio of the molar weight of the inorganic acid to the pulping liquid is 1-3mol/L, namely 1-3mol of the inorganic acid is added into 1L of the pulping liquid.
In the metatitanic acid and lithium sulfate solution C obtained in the step (5), the concentration of lithium ions is 10-20 g/L.
The invention has the advantages that:
the method realizes the simultaneous recovery of the positive and negative electrode powder materials in the lithium iron phosphate-lithium titanate battery, reduces the difficulty of separating the positive and negative electrode mixed materials in the battery crushing and sorting process, reduces the consumption of inorganic acid in the simultaneous recovery process of the positive and negative electrode powder materials, simplifies the recovery process, improves the concentration of Li ions in the solution, realizes the recovery of valuable metals in the positive and negative electrode powder materials of the lithium iron phosphate-lithium titanate battery, and improves the purity of the obtained product.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for recovering waste lithium iron phosphate-lithium titanate batteries specifically comprises the following steps:
(1) placing the waste lithium iron phosphate-lithium titanate battery into a discharge cabinet to discharge below 1.0V, crushing the battery after the discharge is finished, respectively obtaining a shell, a copper foil, an aluminum foil and mixed materials of a positive electrode and a negative electrode by adopting magnetic separation, and respectively collecting and processing the shell, the copper foil and the aluminum foil;
(2) carrying out high-temperature heat treatment on the mixed material of the positive electrode and the negative electrode in the air at the temperature of 300 ℃, wherein the treatment time is 6 hours;
(3) mixing the anode and cathode mixed materials subjected to high-temperature heat treatment with water according to the mass ratio of 1: 4, pulping for 30 minutes after mixing to obtain pulping liquid, then adding hydrochloric acid with the concentration of 3mol/L, stirring at 90 ℃ for reaction, and filtering reactants to remove insoluble substances to obtain filtrate A;
(4) adjusting the pH value of the filtrate A to 2.0, adding a proper amount of Fe powder to remove Cu impurities, removing Fe and Al impurities in the solution by using an aluminoferrite method, and filtering to obtain a filtrate B;
(5) and concentrating, hydrolyzing and precipitating the obtained filtrate B containing titanium and lithium ions to obtain a metatitanic acid and lithium sulfate solution C, wherein the concentration of the lithium ions in the metatitanic acid and lithium sulfate solution C is 15.4 g/L.
Example 2
A method for recovering waste lithium iron phosphate-lithium titanate batteries specifically comprises the following steps:
(1) placing the waste lithium iron phosphate-lithium titanate battery into a resistor to discharge below 1.0V, crushing the battery after the discharge is finished, adopting wind power to sort, respectively obtaining a shell, a copper foil, an aluminum foil and a mixed material of a positive electrode and a negative electrode, and respectively collecting and processing the shell, the copper foil and the aluminum foil;
(2) carrying out high-temperature heat treatment on the mixed material of the positive electrode and the negative electrode in the air at 900 ℃, wherein the treatment time is 1 hour;
(3) mixing the anode and cathode mixed materials subjected to high-temperature heat treatment with water according to the mass ratio of 1: 10, pulping for 30 minutes after mixing to obtain pulping liquid, then adding 3mol/L sulfuric acid, stirring at 60 ℃ for reaction, and filtering reactants to remove insoluble substances to obtain filtrate A;
(4) adjusting the pH value of the filtrate A to 2.0, adding a proper amount of Fe powder to remove Cu impurities, removing Fe and Al impurities in the solution by using an aluminoferrite method, and filtering to obtain a filtrate B;
(5) and concentrating, hydrolyzing and precipitating the obtained filtrate B containing titanium and lithium ions to obtain a metatitanic acid and lithium sulfate solution C, wherein the concentration of the lithium ions in the metatitanic acid and lithium sulfate solution C is 18.5 g/L.
Example 3
A method for recovering waste lithium iron phosphate-lithium titanate batteries specifically comprises the following steps:
(1) placing the waste lithium iron phosphate-lithium titanate battery into a brine tank for discharging for 12 hours, crushing the battery after discharging, respectively obtaining a shell, a copper foil, an aluminum foil and a mixed material of a positive electrode and a negative electrode by adopting gravity separation, and respectively collecting and treating the shell, the copper foil and the aluminum foil;
(2) carrying out high-temperature heat treatment on the mixed materials of the positive electrode and the negative electrode in the air at 500 ℃, wherein the treatment time is 3 hours;
(3) mixing the anode and cathode mixed materials subjected to high-temperature heat treatment with water according to the mass ratio of 1: 6, pulping for 30 minutes after mixing to obtain pulping liquid, then adding sulfuric acid with the concentration of 1.5mol/L, stirring at 80 ℃ for reaction, and filtering reactants to remove insoluble substances to obtain filtrate A;
(4) adjusting the pH value of the filtrate A to 2.0, adding a proper amount of Fe powder to remove Cu impurities, removing Fe and Al impurities in the solution by using an aluminoferrite method, and filtering to obtain a filtrate B;
(5) and concentrating, hydrolyzing and precipitating the obtained filtrate B containing titanium and lithium ions to obtain a metatitanic acid and lithium sulfate solution C, wherein the concentration of the lithium ions in the metatitanic acid and lithium sulfate solution C is 19.5 g/L.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A method for recovering waste lithium iron phosphate-lithium titanate batteries is characterized by comprising the following steps: the method specifically comprises the following steps:
(1) discharging the waste lithium iron phosphate-lithium titanate battery, crushing and sorting the battery after the discharging is finished, and respectively obtaining a shell, copper foil, aluminum foil and mixed materials of a positive electrode and a negative electrode;
(2) carrying out high-temperature heat treatment on the mixed material of the positive electrode and the negative electrode in the air to oxidize ferrous ions in the mixed material of the positive electrode and the negative electrode into ferric ions;
(3) adding the anode and cathode mixed material subjected to high-temperature heat treatment into water for pulping to obtain pulping liquid, then adding inorganic acid, stirring for reaction, and filtering the reactant to remove insoluble substances to obtain filtrate A;
(4) adjusting the pH value of the filtrate A to 2.0-3.0, adding a proper amount of Fe powder to remove Cu impurities, removing Fe and Al impurities in the solution by using an aluminoferrite method, and filtering to obtain a filtrate B;
(5) and concentrating, hydrolyzing and precipitating the obtained filtrate B containing titanium and lithium ions to obtain a metatitanic acid and lithium sulfate solution C.
2. The method for recycling the waste lithium iron phosphate-lithium titanate battery according to claim 1, characterized by comprising the following steps: the waste lithium iron phosphate-lithium titanate battery discharges in a discharging cabinet discharging mode, a resistance discharging mode or a salt water discharging mode.
3. The method for recycling the waste lithium iron phosphate-lithium titanate battery according to claim 1, characterized by comprising the following steps: the crushing and sorting mode in the step (1) is magnetic sorting, wind sorting or gravity sorting.
4. The method for recycling the waste lithium iron phosphate-lithium titanate battery according to claim 1, characterized by comprising the following steps: the temperature of the high-temperature heat treatment in the step (2) is 300-900 ℃, and the treatment time is 1-6 hours.
5. The method for recycling the waste lithium iron phosphate-lithium titanate battery according to claim 1, characterized by comprising the following steps: in the slurry obtained in the step (3), the mass ratio of the anode and cathode mixed materials to the water is 1: 4-10.
6. The method for recycling the waste lithium iron phosphate-lithium titanate battery according to claim 1, characterized by comprising the following steps: the temperature of stirring reaction after adding the inorganic acid in the step (3) is set to be 60-95 ℃ and the time is 0.5-3 hours.
7. The method for recycling the waste lithium iron phosphate-lithium titanate battery according to claim 1, characterized by comprising the following steps: the inorganic acid in the step (3) is hydrochloric acid or sulfuric acid, the volume ratio of the molar weight of the inorganic acid to the pulping liquid is 1-3mol/L, namely 1-3mol of the inorganic acid is added into 1L of the pulping liquid.
8. The method for recycling the waste lithium iron phosphate-lithium titanate battery according to claim 1, characterized by comprising the following steps: in the metatitanic acid and lithium sulfate solution C obtained in the step (5), the concentration of lithium ions is 10-20 g/L.
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| CN110581323B (en) * | 2019-09-25 | 2021-10-22 | 深圳清华大学研究院 | In-situ regeneration method of waste lithium iron phosphate battery positive electrode material |
| CN111129632B (en) * | 2019-11-22 | 2021-07-23 | 深圳清华大学研究院 | Method for recycling anode and cathode mixed materials of waste ternary lithium ion battery |
| CN114024057B (en) * | 2021-11-10 | 2023-08-04 | 湖南金凯循环科技有限公司 | Recycling method of waste nickel cobalt lithium manganate-lithium titanate battery |
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| CN106981699A (en) * | 2017-05-13 | 2017-07-25 | 合肥国轩高科动力能源有限公司 | A kind of method that lithium is reclaimed from waste lithium iron phosphate battery |
| CN107267759B (en) * | 2017-06-12 | 2018-09-18 | 合肥国轩高科动力能源有限公司 | A kind of comprehensive recovering process of anode material for lithium-ion batteries |
| CN108190922A (en) * | 2017-12-14 | 2018-06-22 | 合肥国轩高科动力能源有限公司 | A kind of recovery method of waste and old lithium titanate anode piece |
| CN108390119B (en) * | 2018-03-23 | 2020-04-21 | 上海应用技术大学 | Recovery processing method of lithium iron phosphate/ternary-lithium titanate battery |
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