CN111003700A - Method for recycling waste lithium iron phosphate batteries - Google Patents
Method for recycling waste lithium iron phosphate batteries Download PDFInfo
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- CN111003700A CN111003700A CN201911174082.0A CN201911174082A CN111003700A CN 111003700 A CN111003700 A CN 111003700A CN 201911174082 A CN201911174082 A CN 201911174082A CN 111003700 A CN111003700 A CN 111003700A
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- iron phosphate
- lithium iron
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 29
- 229910052744 lithium Inorganic materials 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- 238000005245 sintering Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- ZTOZIUYGNMLJES-UHFFFAOYSA-K [Li+].[C+4].[Fe+2].[O-]P([O-])([O-])=O Chemical compound [Li+].[C+4].[Fe+2].[O-]P([O-])([O-])=O ZTOZIUYGNMLJES-UHFFFAOYSA-K 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 3
- 239000011654 magnesium acetate Substances 0.000 claims description 3
- 229940069446 magnesium acetate Drugs 0.000 claims description 3
- 235000011285 magnesium acetate Nutrition 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims 9
- 239000010926 waste battery Substances 0.000 claims 8
- 239000005955 Ferric phosphate Substances 0.000 claims 1
- 229960005191 ferric oxide Drugs 0.000 claims 1
- 229940032958 ferric phosphate Drugs 0.000 claims 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 4
- 229910000398 iron phosphate Inorganic materials 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- H01M4/58—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 belongs to the field of resource utilization and environmental protection of waste electronic devices, and particularly relates to a recycling method of a waste lithium iron phosphate battery; the method comprises the following specific steps: high-temperature calcining, separating, grinding ingredients and calcining again; according to the invention, the waste lithium iron phosphate battery is calcined at high temperature in a closed environment, so that tail gas treatment is facilitated, the pollution problem in the disassembly process of the waste lithium iron phosphate battery is solved, the production efficiency is improved, and the following production process does not need management and control substances such as acid, alkali and the like, and the lithium iron phosphate anode material is obtained by only adding raw materials and additives for regeneration, so that the comprehensive utilization and clean production of the waste lithium iron phosphate anode material are realized.
Description
The technical field is as follows:
the invention belongs to the field of resource utilization and environmental protection of waste electronic devices, and particularly relates to a recycling method of a waste lithium iron phosphate battery.
Background art:
GGII data shows that the sales volume of new energy automobiles in China is greatly increased from 2012, and the sales volume is increased from 1.2 ten thousand to 78 ten thousand in 2017; in 2017, the market scale of the Chinese lithium battery is 1350 million yuan, the output value of the power battery is 725 million yuan, the output value of the power battery accounts for 54 percent, and the digital lithium battery scale is exceeded, so that the lithium battery becomes the largest area in a lithium battery consumption structure. According to the plan, the accumulated output and sales volume of new energy vehicles in China can reach 500 thousands in 2020, and the power battery market in China can continue to keep the situation of high-speed development in the middle and long term.
The service life of the lithium battery is long, and compared with the traditional digital lithium battery, the service life of the lithium battery is about 300 times, the performance of the lithium battery is obviously degraded after 1 year of normal use, and the lithium battery is basically in a scrapped state after 3 years; for a power lithium battery, the cycle life is theoretically required to be more than 2000 times, the service cycle is 7-8 years, and the battery pack is seriously degraded after 5 years in practice. According to the actual situation of the current development, the total scrappage of the traditional digital lithium battery in 2018 can be calculated according to the production and marketing data of the lithium battery cathode material in recent years, the total scrappage of the traditional digital lithium battery is not lower than 5 ten thousand tons in 2019, and the total scrappage of the traditional digital lithium battery exceeds 12 ten thousand tons in 2020.
If the scrapped lithium battery cannot be properly treated, not only can resources be wasted, but also huge pollution is caused to the environment, and although the waste lithium battery does not contain heavy metal elements with high toxicity such as mercury, cadmium and lead in a dry battery and a lead-acid battery, the waste lithium battery contains lithium hexafluorophosphate (LiPF6), benzene compounds and ester compounds and is difficult to degrade by microorganisms.
At present, the recovery mode of the scrapped lithium battery is mainly to separate the shell, the positive pole piece and the negative pole piece in a manual disassembly mode, and then the battery pole pieces are used as raw materials for wet smelting in the subsequent process. Because the volatility and toxicity of the electrolyte are greatly harmful to people and environment in the disassembling process, the existing recovery process has certain defects.
Aiming at the problems faced by the waste lithium iron phosphate battery in the recovery process at present, the method has great practical significance for finding a lithium iron phosphate anode material which is more environment-friendly and economic and realizes clean production.
The invention content is as follows:
the invention aims to provide a method for recycling waste lithium iron phosphate batteries, which comprises the following steps:
(1) performing high-temperature calcination on the waste lithium iron phosphate battery in a closed inert atmosphere, cooling to normal temperature, and taking out the remainder;
(2) crushing, screening and magnetically separating the residues obtained in the step 1 to obtain lithium iron phosphate coarse powder;
(3) obtaining carbon powder and lithium iron phosphate fine powder from the lithium iron phosphate coarse powder obtained in the step 2 through an air flow sorting device;
(4) adding an iron source, a phosphorus source, a lithium source and an additive into the lithium iron phosphate fine powder obtained in the step 3; mixing the mixture according to a ratio, using water or ethanol as a dispersing agent, and using zirconium dioxide as a medium for grinding and mixing;
(5) placing the mixture obtained in the step 4 in an inert atmosphere, and sintering at a high temperature to obtain a lithium iron phosphate carbon composite material;
preferably, the inert atmosphere in step 1 and step 4 is one or a mixture of nitrogen and argon;
preferably, the temperature of the high-temperature calcination in the step 1 is 300-650 ℃, and the calcination time is 0.5-6 h.
Preferably, the iron source is one or a mixture of more than one of iron phosphate, ferrous oxalate and ferric oxide.
Preferably, the phosphorus source is one or a mixture of ammonium dihydrogen phosphate and industrial phosphoric acid.
Preferably, the lithium source is one or a mixture of more than one of lithium carbonate, lithium hydroxide, lithium fluoride and lithium acetate.
Preferably, the additive is one or a mixture of more than one of magnesium acetate, nano-magnesia, nano-alumina, sucrose, glucose and soluble starch.
Preferably, the iron source, the phosphorus source and the lithium source are added to satisfy the following conditions: phosphorus element: the molar ratio of lithium elements is 1: 0.97-1.03: 1-1.03.
Preferably, the additive accounts for 0-2% of the mixture by mass.
Preferably, the high-temperature sintering temperature in the step 4 is 650-800 ℃, and the sintering time is 4-20 hours.
The implementation effect of the invention is as follows: according to the invention, the waste lithium iron phosphate battery is calcined at high temperature in a closed environment, so that tail gas treatment is facilitated, the pollution problem in the disassembly process of the waste lithium iron phosphate battery is solved, the production efficiency is improved, and the following production process does not need management and control substances such as acid, alkali and the like, and the lithium iron phosphate anode material is obtained by only adding raw materials and additives for regeneration, so that the comprehensive utilization and clean production of the waste lithium iron phosphate anode material are realized.
Description of the drawings:
fig. 1 is a graph of the rate discharge curve of a lithium iron phosphate battery.
Fig. 2 is a graph showing the rate cycle of the lithium iron phosphate battery 1C.
The specific implementation mode is as follows:
the first embodiment is as follows:
(1) 100 scrapped lithium iron phosphate batteries are put into a box-type atmosphere resistance furnace, the inlet is closed, nitrogen is introduced, and the gas flow is 10m3Heating to 300 ℃ after 60min, calcining at high temperature, keeping the temperature for 6 hours, naturally cooling, and taking out the waste lithium iron phosphate battery residues after the temperature of a hearth is reduced to 60 ℃;
(2) separating the shell and the powder material from the remainder obtained in the step 1 through crushing and screening treatment, and removing the shell to obtain lithium iron phosphate coarse powder;
(3) separating the lithium iron phosphate coarse powder obtained in the step (2) by using an air flow sorting device to obtain carbon powder and lithium iron phosphate fine powder; the iron content in the lithium iron phosphate fine powder is 28.5 percent, the phosphorus content is 19.7 percent, the lithium content is 3.9 percent and the carbon content is 5.8 percent through analysis and determination;
(4) taking 100g of lithium iron phosphate fine powder, adding 18.65g of anhydrous iron phosphate (battery grade, Guangxi Bimo), 2.50g of ammonium dihydrogen phosphate, 2.66g of battery grade lithium carbonate and 0.1g of magnesium acetate, wherein: so that the mixture has the following iron element: phosphorus element: molar ratio of lithium element 1: 0.97: 1, proportioning and mixing; adding the mixture into 200ml of deionized water, using zirconium dioxide as a grinding medium, and grinding and mixing the mixture by using a circulating stirring mill according to a ball-to-material ratio of 6:1 for 8 hours.
(5) And (4) placing the mixture obtained in the step (4) in a nitrogen box-type atmosphere furnace for high-temperature sintering at the sintering temperature of 650 ℃ for 20 hours, and naturally cooling to obtain the lithium iron phosphate carbon composite material.
Example two:
(1) 100 scrapped lithium iron phosphate batteries are put into a box-type atmosphere resistance furnace, the inlet is closed, nitrogen is introduced, and the gas flow is 15m3Heating to 500 ℃ after 80min, calcining at high temperature, keeping the temperature for 4 hours, naturally cooling, and taking out the waste lithium iron phosphate battery residues after the temperature of a hearth is reduced to 50 ℃;
(2) separating the shell and the powder material from the remainder obtained in the step 1 through crushing and screening treatment, and removing the shell to obtain lithium iron phosphate coarse powder;
(3) separating the lithium iron phosphate coarse powder obtained in the step (2) by using an air flow sorting device to obtain carbon powder and lithium iron phosphate fine powder; the iron content in the lithium iron phosphate fine powder is 28.5 percent, the phosphorus content is 19.7 percent, the lithium content is 3.9 percent and the carbon content is 5.8 percent through analysis and determination;
(4) taking 100g of lithium iron phosphate fine powder, adding 20g of a mixture of anhydrous iron phosphate, ferrous oxalate and ferric oxide (battery grade, Guangxi Bimo ratio), 3g of a mixture of ammonium dihydrogen phosphate and industrial phosphoric acid, 3g of a mixture of battery grade lithium carbonate and lithium hydroxide, and a mixture of 0.2 nanometer magnesium oxide and nanometer aluminum oxide, wherein: so that the mixture has the following iron element: phosphorus element: lithium element molar ratio 1: 1.03: 1.03, mixing in proportion; adding the mixture into 200ml of deionized water, using zirconium dioxide as a grinding medium, and grinding and mixing the mixture by using a circulating stirring mill according to a ball-to-material ratio of 6:1 for 9 hours.
(5) And (4) placing the mixture obtained in the step (4) in an argon box-type atmosphere furnace for high-temperature sintering at the sintering temperature of 750 ℃ for 15 hours, and naturally cooling to obtain the lithium iron phosphate carbon composite material.
Example three:
(1) 200 scrapped lithium iron phosphate batteries are put into a box-type atmosphere resistance furnace, the inlet is sealed, nitrogen is introduced, and the gas flow is 25m3Heating to 650 ℃ after 90min, calcining at high temperature, keeping the temperature for 0.5 h, naturally cooling, and taking out the waste lithium iron phosphate battery residues after the temperature of a hearth is reduced to 40 ℃;
(2) separating the shell and the powder material from the remainder obtained in the step 1 through crushing and screening treatment, and removing the shell to obtain lithium iron phosphate coarse powder;
(3) separating the lithium iron phosphate coarse powder obtained in the step (2) by using an air flow sorting device to obtain carbon powder and lithium iron phosphate fine powder; the iron content in the lithium iron phosphate fine powder is 28.5 percent, the phosphorus content is 20 percent, the lithium content is 4 percent and the carbon content is 6 percent through analysis and determination;
(4) taking 110g of lithium iron phosphate fine powder, adding 19g of a mixture of anhydrous iron phosphate and iron oxide (battery grade, Guangxi Bimo), 3g of a mixture of industrial phosphoric acid, 3g of a mixture of battery grade lithium carbonate, lithium hydroxide, lithium fluoride and lithium acetate, and 0.3g of sucrose, glucose and soluble starch, wherein: so that the mixture has the following iron element: phosphorus element: molar ratio of lithium element 1: 0.97: 1.03, mixing in proportion; adding the mixture into 200ml of deionized water, using zirconium dioxide as a grinding medium, and grinding and mixing the mixture by using a circulating stirring mill according to a ball-to-material ratio of 6:1 for 8 hours.
(5) And (4) placing the mixture obtained in the step (4) in a nitrogen box-type atmosphere furnace for high-temperature sintering at 800 ℃ for 15 hours, and naturally cooling to obtain the lithium iron phosphate carbon composite material.
The lithium iron phosphate composite material prepared in the above embodiment is used as a positive electrode, natural graphite is used as a negative electrode, and a 26650 type cylindrical lithium iron phosphate battery (voltage interval 2.0V-4.0V, room temperature) is assembled by using the electrolyte special for lithium iron phosphate, which is gorgeon, national jazz, and the rate discharge curve of the battery is shown in fig. 1, wherein the 1C rate cycle curve is shown in fig. 2.
Claims (10)
1. A method for recycling waste lithium iron phosphate batteries is characterized by comprising the following steps:
1) performing high-temperature calcination on the waste lithium iron phosphate battery in a closed inert atmosphere, cooling to normal temperature, and taking out the remainder;
2) crushing, screening and magnetically separating the residues obtained in the step 1 to obtain lithium iron phosphate coarse powder;
3) obtaining carbon powder and lithium iron phosphate fine powder from the lithium iron phosphate coarse powder obtained in the step 2 through an air flow sorting device;
4) adding an iron source, a phosphorus source, a lithium source and an additive into the lithium iron phosphate fine powder obtained in the step 3; mixing the mixture according to a ratio, using water or ethanol as a dispersing agent, and using zirconium dioxide as a medium for grinding and mixing;
5) and (4) placing the mixture obtained in the step (4) in an inert atmosphere, and sintering at a high temperature to obtain the lithium iron phosphate carbon composite material.
2. The method for recycling and regenerating the lithium iron phosphate waste battery according to claim 1, characterized in that: in step 1 and step 4, the inert atmosphere is one or a mixture of nitrogen and argon.
3. The method for recycling and regenerating the lithium iron phosphate waste battery according to claim 1, characterized in that: the temperature of the high-temperature calcination in the step 1 is 300-650 ℃, and the calcination time is 0.5-6 h.
4. The method for recycling and regenerating the lithium iron phosphate waste battery according to claim 1, characterized in that: in the step 3, the iron source is one or a mixture of more than one of ferric phosphate, ferrous oxalate and ferric oxide.
5. The method for recycling and regenerating the lithium iron phosphate waste battery according to claim 1, characterized in that: in the step 4, the phosphorus source is one or a mixture of ammonium dihydrogen phosphate and industrial phosphoric acid.
6. The method for recycling and regenerating the lithium iron phosphate waste battery according to claim 1, wherein the lithium source in the step 4 is one or a mixture of more than one of lithium carbonate, lithium hydroxide, lithium fluoride and lithium acetate.
7. The method for recycling and regenerating the lithium iron phosphate waste battery according to claim 1, characterized in that: in the step 4, the additive is one or a mixture of more than one of magnesium acetate, nano magnesium oxide, nano aluminum oxide, sucrose, glucose and soluble starch.
8. The method for recycling and regenerating the waste lithium iron phosphate battery according to claim 1, wherein in the step 4, the iron source, the phosphorus source and the lithium source are added to satisfy the following condition: phosphorus element: the molar ratio of lithium elements is 1: 0.97-1.03: 1: 1.03.
9. the method for recycling and regenerating the lithium iron phosphate waste battery according to claim 1, characterized in that: in the step 4, the additive accounts for 0-2% of the mass ratio of the mixture.
10. The method for recycling and regenerating the lithium iron phosphate waste battery according to claim 1, characterized in that: the temperature of the high-temperature sintering in the step 5 is 650-800 ℃, and the sintering time is 4-20 hours.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111540901A (en) * | 2020-06-29 | 2020-08-14 | 株洲冶炼集团科技开发有限责任公司 | Method for preparing lithium iron phosphate (LEP) by using lithium iron (III) phosphate |
| CN111816861A (en) * | 2020-07-29 | 2020-10-23 | 湖北融通高科先进材料有限公司 | Method for preparing lithium iron phosphate positive electrode material by using waste lithium iron phosphate pole pieces |
| CN112575203A (en) * | 2020-12-07 | 2021-03-30 | 金川集团股份有限公司 | Method for recycling lithium in waste power lithium battery |
| CN112768799A (en) * | 2021-01-25 | 2021-05-07 | 湖北融通高科先进材料有限公司 | Method for recycling waste lithium iron phosphate positive pole piece by dry method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110165324A (en) * | 2019-06-24 | 2019-08-23 | 中国科学院青海盐湖研究所 | A kind of method and system recycling anode and Regeneration and Repair from waste lithium cell |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110165324A (en) * | 2019-06-24 | 2019-08-23 | 中国科学院青海盐湖研究所 | A kind of method and system recycling anode and Regeneration and Repair from waste lithium cell |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111540901A (en) * | 2020-06-29 | 2020-08-14 | 株洲冶炼集团科技开发有限责任公司 | Method for preparing lithium iron phosphate (LEP) by using lithium iron (III) phosphate |
| CN111816861A (en) * | 2020-07-29 | 2020-10-23 | 湖北融通高科先进材料有限公司 | Method for preparing lithium iron phosphate positive electrode material by using waste lithium iron phosphate pole pieces |
| CN112575203A (en) * | 2020-12-07 | 2021-03-30 | 金川集团股份有限公司 | Method for recycling lithium in waste power lithium battery |
| CN112575203B (en) * | 2020-12-07 | 2022-11-04 | 金川集团股份有限公司 | Method for recycling lithium in waste power lithium battery |
| CN112768799A (en) * | 2021-01-25 | 2021-05-07 | 湖北融通高科先进材料有限公司 | Method for recycling waste lithium iron phosphate positive pole piece by dry method |
| CN112768799B (en) * | 2021-01-25 | 2022-04-29 | 湖北融通高科先进材料有限公司 | Method for recycling waste lithium iron phosphate positive pole piece by dry method |
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