CN115347265A - Method for preparing copper-aluminum co-doped modified lithium iron phosphate positive electrode material from waste lithium iron phosphate battery - Google Patents
Method for preparing copper-aluminum co-doped modified lithium iron phosphate positive electrode material from waste lithium iron phosphate battery Download PDFInfo
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- CN115347265A CN115347265A CN202211123654.4A CN202211123654A CN115347265A CN 115347265 A CN115347265 A CN 115347265A CN 202211123654 A CN202211123654 A CN 202211123654A CN 115347265 A CN115347265 A CN 115347265A
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- aluminum
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- iron phosphate
- lithium
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 76
- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 38
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000007774 positive electrode material Substances 0.000 title claims description 23
- 239000010949 copper Substances 0.000 claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052802 copper Inorganic materials 0.000 claims abstract description 60
- 239000000843 powder Substances 0.000 claims abstract description 52
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 46
- 239000011812 mixed powder Substances 0.000 claims abstract description 39
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010406 cathode material Substances 0.000 claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000002386 leaching Methods 0.000 claims abstract description 8
- 239000007790 solid phase Substances 0.000 claims abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000007885 magnetic separation Methods 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 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
- 239000007788 liquid Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000005955 Ferric phosphate Substances 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 4
- 229940032958 ferric phosphate Drugs 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 4
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 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
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- 229960002413 ferric citrate Drugs 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 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
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 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
- 239000005720 sucrose Substances 0.000 claims description 3
- FRHBOQMZUOWXQL-UHFFFAOYSA-L ammonium ferric citrate Chemical compound [NH4+].[Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FRHBOQMZUOWXQL-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 claims description 2
- 229960004642 ferric ammonium citrate Drugs 0.000 claims description 2
- 235000000011 iron ammonium citrate Nutrition 0.000 claims description 2
- 239000004313 iron ammonium citrate Substances 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229910000398 iron phosphate Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 239000010405 anode material Substances 0.000 abstract description 14
- 239000012535 impurity Substances 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 238000013461 design Methods 0.000 abstract description 3
- 230000001502 supplementing effect Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910001416 lithium ion Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 210000004027 cell Anatomy 0.000 description 10
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 8
- 238000007600 charging Methods 0.000 description 8
- 229910001431 copper ion Inorganic materials 0.000 description 8
- 238000004064 recycling Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 210000002858 crystal cell Anatomy 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002480 Cu-O Inorganic materials 0.000 description 1
- 229910006715 Li—O Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940108928 copper Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000003546 flue gas Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940006116 lithium hydroxide Drugs 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
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- 238000003860 storage Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910021654 trace metal Inorganic materials 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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
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Abstract
The invention discloses a method for preparing a copper-aluminum co-doped modified lithium iron phosphate anode material from waste lithium iron phosphate batteries, which comprises the steps of firstly pretreating retired lithium iron phosphate batteries through a series of steps to obtain waste anode powder, grinding and uniformly mixing the waste anode powder, then measuring the content of each element in the mixed powder, taking trace copper and aluminum in the waste anode powder as a doped copper source and an aluminum source, properly supplementing the lithium source, the iron source, the phosphorus source, the copper source and the aluminum source to enable each element in the waste anode powder to meet the design requirement of stoichiometric ratio, and then carrying out acid leaching, adding the carbon source and a reducing agent and roasting to obtain the copper-aluminum co-doped modified lithium iron phosphate anode material. The method can effectively solve the problems of short material cycle life and poor rate capability of the recycled and re-prepared cathode material caused by metal copper impurities, and the problem that the solid-phase direct regeneration material is difficult to meet the commercial application requirement.
Description
Technical Field
The invention relates to a method for preparing a copper-aluminum co-doped modified lithium iron phosphate positive electrode material from a waste lithium iron phosphate battery, belonging to the field of lithium ion battery recovery and positive electrode material preparation.
Background
Lithium ion batteries are widely used in new energy automobile power storage batteries due to their advantages of high energy density and low cost. Due to capacity fading, lithium ion power batteries will face decommissioning after 3-5 years of use. The ex-service power lithium battery in 2025 is expected to reach 134.49GWh, and the ex-service amount reaches 80.36 ten thousand tons. The recovery processing and the remanufacturing of the lithium ion battery electrode material of the waste lithium battery are important measures for realizing the sustainable development of the lithium ion battery.
At present, the mainstream methods for recycling the lithium ion battery comprise hydrometallurgy and pyrometallurgy. However, the hydrometallurgical recovery procedure is complex, producing large amounts of waste water; the pyrometallurgy has large energy consumption, is difficult to remove metal impurities, discharges toxic flue gas, and has certain differences between the capacity, rate capability and cycle performance of the recycled and regenerated anode material and fresh materials. The difficulty of the current research is how to reduce the impurity content in the waste anode mixed powder on the basis of green environmental protection and how to improve the discharge specific capacity, the multiplying power and the cycle performance of the regenerated anode material by modifying and modifying the regenerated anode material.
Most of the existing technologies for recycling the waste lithium ion battery anode materials by adopting a solid phase method and then preparing new anode materials are waste anode materials obtained based on manual or automatic fine sorting, and the problem of treatment of metal impurities is not involved. And discharging and disassembling the retired lithium iron phosphate battery to obtain a battery core, removing residual electrolyte and decomposed binder in the battery core by using 500 ℃ negative pressure pyrolysis treatment under inert atmosphere such as nitrogen, and then crushing, screening, winnowing and magnetic separation to obtain waste and old positive electrode powder (mainly lithium iron phosphate positive electrode powder, a small amount of carbon, graphite powder and trace aluminum and copper). When the recycled waste anode powder is used as a raw material and an anode material obtained by supplementing a proper amount of lithium source, iron source and phosphorus source is applied to a lithium ion battery, trace metal impurities in the anode material can make the crystal structure of the anode material tend to a metastable state in the charging and discharging processes of the battery, so that the performance of the battery is attenuated. The influence of copper metal impurities is most obvious, when the voltage of a battery formation stage reaches the oxidation-reduction potential of the copper metal impurities, copper metal is oxidized at a positive electrode and then reduced and deposited at a negative electrode, and after reciprocating accumulation, the copper metal deposition dendrite can pierce a diaphragm to cause self-discharge of the battery. For the above reasons, it is difficult to meet the requirement of commercial application for the electrochemical performance of lithium ion batteries made of recycled and re-prepared cathode materials.
Disclosure of Invention
The invention aims to overcome the defects in the prior art, provides a method for preparing a copper-aluminum co-doped modified lithium iron phosphate positive electrode material from a waste lithium iron phosphate battery, and aims to solve the problems of short cycle life and poor rate capability of the recycled positive electrode material due to metal copper impurities. Copper in the crystal grains is converted into copper ions, and the copper ions are doped into the crystal cells of the lithium iron phosphate through ion diffusion in the subsequent calcining and re-preparing process, so that the defects of copper metal impurities are overcome, and the conductivity of the crystal grains of the material is improved; and the aluminum simple substance is subjected to uniform dispersion and content optimization, the intercrystalline conductivity of the material can be improved, the multiplying power performance and the cycling stability of the remanufactured material can be improved through copper and aluminum co-doping modification, and the method is suitable for being applied to energy storage batteries.
In order to realize the purpose of the invention, the following technical scheme is adopted:
a method for preparing a copper-aluminum co-doped modified lithium iron phosphate positive electrode material from a waste lithium iron phosphate battery comprises the following steps:
step 1: discharging and disassembling a waste lithium iron phosphate battery to obtain a battery core, removing residual electrolyte and decomposition binder in the battery core by using negative pressure pyrolysis treatment at 500 ℃ under inert atmosphere such as nitrogen, and then crushing, screening, winnowing and magnetic separation to obtain waste positive electrode powder (mainly lithium iron phosphate positive electrode powder, and a small amount of carbon, graphite powder and trace aluminum and copper);
step 2: taking the waste anode powder obtained in the step 1 as a raw material, and grinding and uniformly mixing the waste anode powder by adopting a solid-phase ball milling method to obtain mixed powder A;
and step 3: measuring the content of each element in the mixed powder A obtained in the step 2 by using an inductively coupled plasma spectrometer, and adjusting the stoichiometric ratio of lithium, iron, phosphorus, copper and aluminum in the mixed powder A to be 1-1.05 by adding a lithium source, an iron source, a phosphorus source, a copper source and an aluminum source: 1:1:0.001 to 0.02: within the range of 0.001-0.02, obtaining mixed powder B; adopting acetic acid containing hydrogen peroxide to perform acid leaching on the mixed powder B under the conditions that the reaction temperature is room temperature to 90 ℃, the reaction time is 10 to 120min and the solid-to-liquid ratio is 10 to 300g/L, so as to convert simple substance copper into copper acetate, further to realize that copper ions are doped into lithium iron phosphate unit cells, aluminum exists in the material in the form of the simple substance to play a role in enhancing the conductivity of the material, and the mixed powder C is obtained through evaporation and drying;
and 4, step 4: adding glucose or sucrose which accounts for 10-30% of the mass ratio of the mixed powder C as a carbon source and a reducing agent, grinding and mixing, and roasting in inert atmosphere such as nitrogen or argon to obtain the copper-aluminum co-doped modified lithium iron phosphate cathode material.
Further, in the step 1, based on the total mass of the waste anode powder, the content of lithium iron phosphate in the waste anode powder is within a range of 85-95 wt%, the content of carbon and graphite is within a range of 1-15 wt%, the content of copper is within a range of 0-1 wt%, and the content of aluminum is within a range of 0-0.5 wt%.
Furthermore, in the step 2, the ball milling speed is 150-1500 rpm, and the ball milling time is 0.5-10 h.
Further, in step 3: the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium oxalate, lithium phosphate, lithium acetate and lithium dihydrogen phosphate; the iron source is one or more of ferrous oxalate, ferric oxide, ferric acetate, ferric phosphate, ferric citrate and ferric ammonium citrate; the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ferric phosphate, lithium phosphate and lithium dihydrogen phosphate; the copper source is one or more of copper acetate, copper oxalate, copper oxide and copper simple substance; the aluminum source is aluminum simple substance powder with the particle size of less than 1 micron.
Further, in the step 3, in the acetic acid containing hydrogen peroxide used for acid leaching, the mass concentration of the hydrogen peroxide is 1-10%, and the concentration of the acetic acid is 0.1-6 mol/L.
Further, in step 4, the baking is performed in two steps: firstly, heating to 300-450 ℃ at a heating rate of 1-6 ℃/min, and carrying out heat preservation treatment for 2-8 h; then heating to 650-750 ℃ at the heating rate of 1-6 ℃/min, and carrying out heat preservation treatment for 3-24 h; and finally naturally cooling to room temperature.
According to the method, copper and aluminum impurities generated in the pretreatment process of the waste battery are used as doping raw materials, and the waste positive electrode material is regenerated into the copper and aluminum co-doped modified positive electrode material, so that the problems of short cycle life and poor rate capability of the recycled and prepared positive electrode material due to metal copper impurities and the problem that the solid-phase directly regenerated material is difficult to meet the commercial application requirements can be effectively solved, and the cyclic utilization of lithium, iron, phosphorus, copper and aluminum elements in the retired lithium ion battery can be realized.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a method for recycling and preparing a copper-aluminum co-doped modified lithium iron phosphate cathode material from waste lithium iron phosphate batteries, which comprises the following steps: discharging and disassembling a retired lithium iron phosphate battery to obtain a battery core, removing residual electrolyte and decomposed binder in the battery core by using negative pressure pyrolysis treatment at 500 ℃ under inert atmosphere such as nitrogen, and then crushing, screening, winnowing and magnetic separation to obtain waste and old positive electrode powder (mainly lithium iron phosphate positive electrode powder, a small amount of carbon, graphite powder and trace aluminum and copper); the waste anode powder containing a small amount of carbon and graphite powder and trace aluminum and copper is used as a raw material, and the waste anode powder is ground and uniformly mixed by adopting a solid-phase ball milling method; measuring the content of each element in the mixed powder by using an inductively coupled plasma spectrometer, and adjusting the lithium, iron and phosphorus elements in the mixed powder to meet the design requirement of the stoichiometric ratio by adding a proper amount of lithium source, iron source and phosphorus source; meanwhile, trace copper and aluminum in the recycled powder are used as a doped copper source and an aluminum source, and the problems of short material cycle life and poor rate capability of the recycled and remanufactured positive electrode material caused by metal copper impurities are solved. Copper in the crystal grains is converted into copper ions, and the copper ions are doped into the crystal cells of the lithium iron phosphate through ion diffusion in the subsequent calcining and re-preparing process, so that the defects of copper metal impurities are overcome, and the conductivity of the crystal grains of the material is improved; the elemental aluminum is uniformly dispersed and optimized in content, so that the intercrystalline conductivity of the material can be improved, the multiplying power performance and the cycling stability of the remanufactured material can be improved through copper and aluminum co-doping modification, and the method is suitable for being applied to energy storage batteries, so that the recycling of lithium, iron, phosphorus, copper and aluminum elements in the retired lithium ion batteries is realized.
Drawings
FIG. 1 is an XRD pattern of waste cathode powder obtained by pretreatment in example 1 of the present invention;
fig. 2 is an XRD chart of the copper-aluminum co-doped modified lithium iron phosphate positive electrode material obtained in example 1 of the present invention;
FIG. 3 is an FESEM photograph of the waste cathode powder obtained in example 1 of the present invention;
fig. 4 is an FESEM photograph of the copper-aluminum co-doped modified lithium iron phosphate positive electrode material obtained in example 1 of the present invention;
fig. 5 is an XPS spectrum of the copper and aluminum co-doped modified lithium iron phosphate positive electrode material obtained in example 1 of the present invention;
fig. 6 is an EDS spectrum of the copper-aluminum co-doped modified lithium iron phosphate positive electrode material obtained in example 1 of the present invention;
FIG. 7 is a charging and discharging curve of the waste cathode powder obtained in example 1 of the present invention at current densities of 0.1C and 5C, respectively;
fig. 8 is a charge-discharge curve of the copper-aluminum co-doped modified lithium iron phosphate positive electrode material obtained in example 1 of the present invention at a current density of 0.1C and a current density of 5C, respectively;
fig. 9 is a cycle performance diagram of the copper and aluminum co-doped modified lithium iron phosphate positive electrode material and the waste positive electrode powder obtained in example 1 of the present invention at a current density of 5C.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1: method for recycling and preparing copper-aluminum co-doped modified lithium iron phosphate cathode material from waste lithium iron phosphate battery
Step 1: the method comprises the steps of discharging and disassembling retired lithium iron phosphate batteries to obtain a battery core, removing residual electrolyte and decomposed binder in the batteries by using 500-DEG C negative pressure pyrolysis treatment in a nitrogen atmosphere, and then crushing, screening, winnowing and magnetic separation to obtain waste and old positive electrode powder (mainly lithium iron phosphate positive electrode powder, a small amount of carbon, graphite powder and trace aluminum and copper).
Step 2: taking the waste anode powder (the content of lithium iron phosphate is 94.5wt%, the content of graphite is 4.6wt%, the content of copper is 0.5wt%, and the content of aluminum is 0.2 wt%) obtained in the step 1 as a raw material, grinding the waste anode powder and uniformly mixing the powder by a solid-phase ball milling method under the conditions that the rotating speed is 1200rpm and the ball milling time is 6.5 hours, so as to obtain mixed powder A.
And 3, step 3: measuring the content of each element in the mixed powder A by using an inductively coupled plasma spectrometer, and adjusting the stoichiometric ratio of lithium, iron, phosphorus, copper and aluminum in the mixed powder A to be 1.05 by adding a proper amount of lithium carbonate, ferric oxide, ammonium dihydrogen phosphate, copper acetate and spherical aluminum powder with the average particle size of 600 nm: 1:1:0.003:0.003 to obtain mixed powder B; and then, carrying out acid leaching on the mixed powder B by adopting acetic acid containing 5wt% of hydrogen peroxide and having the concentration of 0.8mol/L under the conditions that the reaction temperature is 85 ℃, the reaction time is 30min and the solid-to-liquid ratio is 50g/L, converting the simple substance copper into copper acetate so as to realize that copper ions are doped into lithium iron phosphate unit cells, and aluminum exists in the material in the form of the simple substance, so that the mixed powder C is obtained through evaporation and drying.
And 4, step 4: adding glucose which accounts for 30% of the mass ratio of the mixed powder C as a carbon source and a reducing agent, grinding, mixing, and roasting in a nitrogen atmosphere in two steps (firstly heating to 350 ℃ at a heating rate of 4 ℃/min, performing heat preservation treatment for 4 hours, then heating to 700 ℃ at a heating rate of 2 ℃/min, performing heat preservation treatment for 10 hours, and finally naturally cooling to room temperature) to obtain the copper and aluminum co-doped modified lithium iron phosphate cathode material.
The waste cathode powder obtained by the pretreatment in the step 1 of the embodiment and the copper-aluminum co-doped modified lithium iron phosphate cathode material obtained in the step 4 are fully mixed with acetylene black and polyvinylidene fluoride (PVDF) according to a ratio of 8 (mass ratio). A metal lithium sheet is used as a negative electrode, a Cellgard 2400 type polypropylene film is used as a diaphragm, lithium hexafluorophosphate is used as electrolyte, an experimental battery is assembled in an argon glove box, and then a constant-voltage constant-current charge-discharge test is carried out on the battery at 25 ℃.
Fig. 1 and fig. 2 are XRD charts of the waste anode powder obtained by pretreatment in step 1 and the copper-aluminum co-doped modified lithium iron phosphate anode material obtained in step 4 in this embodiment, respectively, and it can be seen from the XRD charts that both materials can be indexed to an orthorhombic olivine structure, and the space group is Pnma. Wherein Fe 2+ Occupying the 4a position of the octahedron, li + Occupying the 4c position of the octahedron. Edge-shared LiO 4 FeO shared with corners 6 The octahedrons are all parallel to the c axis and are arranged along the b axis direction.
Table 1 shows the cell parameters of the copper-aluminum co-doped modified lithium iron phosphate anode material and the waste anode powder;
TABLE 1
Table 1 may show that co-doped sample unit cell parameters a, b, c and unit cell volume are all reduced due to Cu 2+ Doping may occur predominantly with Li + Substituted in the position, cu 2+ Has a radius (0.073 nm) smaller than Li + Radius (0.076 nm) of (A), resulting in a reduction of the unit cell parameterAnd simultaneously, the Cu-O bond energy is larger than the Li-O bond energy, so that the unit cell volume is reduced. Reduction of the lattice parameter b shortens Li + The diffusion distance of the lithium iron phosphate electrode material is increased, and the electronic conductivity and the lithium ion diffusion rate of the lithium iron phosphate electrode material are improved.
Fig. 3 and fig. 4 are FESEM images of the waste cathode powder and the copper-aluminum co-doped modified lithium iron phosphate cathode material in this embodiment, respectively, the particle size of the waste cathode powder is between 0.5 μm and 4 μm, and the particle size of the copper-aluminum co-doped modified lithium iron phosphate cathode material is reduced and uniform (particle size is between 0.5 μm and 1 μm). The reduction of the particle size is beneficial to reducing the lithium ion diffusion path and increasing the high-rate discharge performance of the lithium iron phosphate.
Fig. 5 is an XPS spectrum of the copper-aluminum co-doped modified lithium iron phosphate cathode material in this embodiment, in which 2p of Cu can be observed 3/2 And 2p 1/2 Spin splitting orbits, and observing satellite peak characteristics specific to bivalent copper, prove that copper is doped into the unit cell of the lithium iron phosphate material in the form of bivalent ions.
Fig. 6 is an EDS spectrum of the copper-aluminum co-doped modified lithium iron phosphate positive electrode material of this embodiment, where the stoichiometric ratio Fe: p: cu: al: c ≈ 1:1:0.006:0.012:0.76, and substantially meets the design value within the error range.
Fig. 7 is a charging and discharging curve of the waste cathode powder in this embodiment at current densities of 0.1C and 5C, respectively, and it can be observed that a stable charging voltage platform at a constant current charging stage is formed at a voltage of 3.45V, while a discharging voltage platform at a current density of 5C is about 3.10V, a polarization voltage Δ V =0.35v, and specific discharge capacities of 0.1c and 5C reach 123.7mAh/g and 89.9mAh/g, respectively.
Fig. 8 is a charging and discharging curve of the copper-aluminum co-doped modified lithium iron phosphate positive electrode material in the embodiment at current densities of 0.1C and 5C, it can be observed that a stable charging voltage platform in a constant current charging stage exists at a voltage of 3.45V, and a charging voltage platform at a current density of 5C is about 3.25V, a polarization voltage Δ V =0.20v, and discharging specific capacities of 0.1c and 5C respectively reach 151.5mAh/g and 121.5mAh/g, which indicates that the electrode polarization degree of the copper-aluminum co-doped modified lithium iron phosphate positive electrode material is obviously smaller than that of waste positive electrode powder in a high-rate charging and discharging process, and the discharging specific capacity is obviously higher than that of the waste positive electrode powder.
Fig. 9 is a cycle performance diagram of the copper and aluminum co-doped modified lithium iron phosphate positive material and the waste positive powder under the current density of 5C. As can be seen from the figure, the initial discharge capacity of the copper-aluminum co-doped modified lithium iron phosphate positive electrode material is 120.7mAh/g, which is obviously higher than 89.2mAh/g of the waste positive electrode powder. In addition, after 100 circles of charge and discharge tests, the discharge capacity of the copper and aluminum co-doped modified lithium iron phosphate positive electrode material is hardly attenuated. Electrochemical test results show that a proper amount of copper and aluminum codoping modification is beneficial to improving the discharge capacity and the cycle performance of the regenerated lithium iron phosphate anode material.
Example 2: copper-aluminum co-doped modified lithium iron phosphate cathode material prepared by recycling waste lithium iron phosphate batteries
Step 1: the method comprises the steps of discharging and disassembling the retired lithium iron phosphate battery to obtain a battery core, removing residual electrolyte and decomposed binder in the battery core by means of negative-pressure pyrolysis treatment at 500 ℃ in inert atmosphere such as nitrogen, and then crushing, screening, winnowing and magnetic separation to obtain waste and old positive powder (mainly lithium iron phosphate positive powder, a small amount of carbon and graphite powder and trace aluminum and copper).
Step 2: and (2) taking the waste anode powder (the content of lithium iron phosphate is 89.7wt%, the content of graphite is 8.5wt%, the content of copper is 1wt% and the content of aluminum is 0.5 wt%) obtained in the step (1) as a raw material, and grinding and uniformly mixing the waste anode powder by adopting a solid-phase ball milling method under the conditions that the rotating speed is 1000rpm and the ball milling time is 4 hours to obtain mixed powder A.
And step 3: measuring the content of each element in the mixed powder A by using an inductive coupling plasma spectrometer, and adding a proper amount of lithium oxalate, ferrous oxalate, diammonium hydrogen phosphate, copper oxide and spherical aluminum powder with the average particle size of 900nm to adjust the stoichiometric ratio of lithium, iron, phosphorus, copper and aluminum in the mixed powder A to be 1:1:1:0.01:0.01, obtaining mixed powder B; and then, carrying out acid leaching on the mixed powder B by adopting 10wt% of hydrogen peroxide and 1mol/L acetic acid under the conditions of reaction temperature of 70 ℃, reaction time of 60min and solid-to-liquid ratio of 100g/L, converting elemental copper into copper acetate so as to realize doping of copper ions into lithium iron phosphate unit cells, enabling aluminum to exist in the material in the form of elemental substances, and obtaining mixed powder C through evaporation and drying.
And 4, step 4: adding glucose which accounts for 20% of the mass ratio of the mixed powder C as a carbon source and a reducing agent, grinding, mixing, and roasting in an argon atmosphere in two steps (firstly heating to 300 ℃ at a heating rate of 1 ℃/min, performing heat preservation treatment for 6 hours, then heating to 650 ℃ at a heating rate of 1 ℃/min, performing heat preservation treatment for 20 hours, and finally naturally cooling to room temperature) to obtain the copper-aluminum co-doped modified lithium iron phosphate cathode material.
Example 3: copper-aluminum co-doped modified lithium iron phosphate cathode material prepared by recycling waste lithium iron phosphate batteries
Step 1: the method comprises the steps of discharging and disassembling the retired lithium iron phosphate battery to obtain a battery core, removing residual electrolyte and decomposed binder in the battery core by means of negative-pressure pyrolysis treatment at 500 ℃ in inert atmosphere such as nitrogen, and then crushing, screening, winnowing and magnetic separation to obtain waste and old positive powder (mainly lithium iron phosphate positive powder, a small amount of carbon and graphite powder and trace aluminum and copper).
Step 2: and (2) taking the waste anode powder (the content of the lithium iron phosphate is 88.7wt%, the content of the graphite is 10.5wt%, the content of the copper is 0.2wt% and the content of the aluminum is 0.2 wt%) obtained in the step (1) as a raw material, and grinding and uniformly mixing the waste anode powder by adopting a solid-phase ball milling method under the conditions that the rotating speed is 800rpm and the ball milling time is 10 hours to obtain mixed powder A.
And 3, step 3: measuring the content of each element in the mixed powder A by using an inductive coupling plasma spectrometer, and adding a proper amount of lithium hydroxide, ferric citrate, ferric phosphate, copper simple substance and spherical aluminum powder with the average particle size of 900nm to adjust the stoichiometric ratio of lithium, iron, phosphorus, copper and aluminum in the mixed powder A to be 1:1:1:0.02:0.02, obtaining mixed powder B; and then, carrying out acid leaching on the mixed powder B by adopting 2.5wt% of hydrogen peroxide and 0.5mol/L acetic acid under the conditions of reaction temperature of 90 ℃, reaction time of 120min and solid-to-liquid ratio of 200g/L, converting elemental copper into copper acetate so as to realize doping of copper ions into lithium iron phosphate unit cells, enabling aluminum to exist in the material in an elemental form, and obtaining mixed powder C through evaporation and drying.
And 4, step 4: adding sucrose accounting for 25% of the mass ratio of the mixed powder C as a reducing agent, grinding and mixing, and roasting in a nitrogen atmosphere in two steps (firstly heating to 450 ℃ at a heating rate of 5 ℃/min, performing heat preservation treatment for 4 hours, then heating to 750 ℃ at a heating rate of 2 ℃/min, performing heat preservation treatment for 5 hours, and finally naturally cooling to room temperature) to obtain the copper-aluminum co-doped modified lithium iron phosphate cathode material.
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention should be included in the protection scope of the invention.
Claims (10)
1. A method for preparing a copper-aluminum co-doped modified lithium iron phosphate positive electrode material from a waste lithium iron phosphate battery is characterized by comprising the following steps of:
step 1: discharging and disassembling the waste lithium iron phosphate battery to obtain a battery core, performing negative-pressure pyrolysis treatment at 500 ℃ under an inert atmosphere to remove residual electrolyte and decomposed binder, and crushing, screening, winnowing and magnetic separation to obtain waste positive electrode powder;
step 2: taking the waste anode powder obtained in the step 1 as a raw material, and grinding and uniformly mixing the waste anode powder by adopting a solid-phase ball milling method to obtain mixed powder A;
and step 3: measuring the content of each element in the mixed powder A obtained in the step 2, adding a lithium source, an iron source, a phosphorus source, a copper source and an aluminum source, and adjusting the stoichiometric ratio of lithium, iron, phosphorus, copper and aluminum in the mixed powder A to be 1-1.05: 1:1:0.001 to 0.02: within the range of 0.001-0.02, obtaining mixed powder B; adopting acetic acid containing hydrogen peroxide to perform acid leaching on the mixed powder B under the conditions that the reaction temperature is between room temperature and 90 ℃, the reaction time is between 10 and 120min and the solid-to-liquid ratio is between 10 and 300g/L, converting the single copper into copper acetate, and evaporating and drying to obtain mixed powder C;
and 4, step 4: adding glucose or sucrose which accounts for 10-30% of the mass ratio of the mixed powder C as a carbon source and a reducing agent, grinding and mixing, and roasting in an inert atmosphere to obtain the copper-aluminum co-doped modified lithium iron phosphate cathode material.
2. The method of claim 1, wherein: in the step 1, based on the total mass of the waste anode powder, the content of lithium iron phosphate in the waste anode powder is within the range of 85-95 wt%, the content of carbon and graphite is within the range of 1-15 wt%, the content of copper is within the range of 0-1 wt%, and the content of aluminum is within the range of 0-0.5 wt%.
3. The method of claim 1, wherein: in the step 2, the ball milling speed is 150-1500 rpm, and the ball milling time is 0.5-10 h.
4. The method of claim 1, wherein: in step 3, the lithium source is one or more of lithium carbonate, lithium hydroxide, lithium oxalate, lithium phosphate, lithium acetate and lithium dihydrogen phosphate.
5. The method of claim 1, wherein: in the step 3, the iron source is one or more of ferrous oxalate, ferric oxide, ferric acetate, ferric phosphate, ferric citrate and ferric ammonium citrate.
6. The method of claim 1, wherein: in step 3, the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, iron phosphate, lithium phosphate and lithium dihydrogen phosphate.
7. The method of claim 1, wherein: in the step 3, the copper source is one or more of copper acetate, copper oxalate, copper oxide and copper simple substance.
8. The method of claim 1, wherein: in the step 3, the aluminum source is aluminum simple substance powder with the particle size smaller than 1 micron.
9. The method of claim 1, wherein: in the step 3, in the acetic acid containing hydrogen peroxide used for acid leaching, the mass concentration of the hydrogen peroxide is 1 to 10 percent, and the concentration of the acetic acid is 0.1 to 6mol/L.
10. The method of claim 1, wherein: in step 4, the roasting is carried out in two steps: firstly, heating to 300-450 ℃ at a heating rate of 1-6 ℃/min, and carrying out heat preservation treatment for 2-8 h; then heating to 650-750 ℃ at the heating rate of 1-6 ℃/min, and carrying out heat preservation treatment for 3-24 h; and finally, naturally cooling to room temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116715213A (en) * | 2023-08-10 | 2023-09-08 | 河北顺境环保科技有限公司 | Recycling treatment method of non-injected lithium iron phosphate waste sheet |
| CN117712544A (en) * | 2024-02-06 | 2024-03-15 | 邢东(河北)锂电科技有限公司 | Resource utilization method of waste lithium iron phosphate battery |
| CN117894979A (en) * | 2024-03-18 | 2024-04-16 | 四川易纳能新能源科技有限公司 | High-entropy doped sodium iron phosphate positive electrode material, preparation method thereof, sodium ion battery positive electrode plate and sodium ion battery |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116715213A (en) * | 2023-08-10 | 2023-09-08 | 河北顺境环保科技有限公司 | Recycling treatment method of non-injected lithium iron phosphate waste sheet |
| CN117712544A (en) * | 2024-02-06 | 2024-03-15 | 邢东(河北)锂电科技有限公司 | Resource utilization method of waste lithium iron phosphate battery |
| CN117712544B (en) * | 2024-02-06 | 2024-04-12 | 邢东(河北)锂电科技有限公司 | Resource utilization method of waste lithium iron phosphate battery |
| CN117894979A (en) * | 2024-03-18 | 2024-04-16 | 四川易纳能新能源科技有限公司 | High-entropy doped sodium iron phosphate positive electrode material, preparation method thereof, sodium ion battery positive electrode plate and sodium ion battery |
| CN117894979B (en) * | 2024-03-18 | 2024-05-31 | 四川易纳能新能源科技有限公司 | High-entropy doped sodium iron phosphate positive electrode material, preparation method thereof, sodium ion battery positive electrode plate and sodium ion battery |
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