CN116525819A - Preparation method for regenerating waste lithium iron phosphate positive electrode material based on nitrogen doping - Google Patents
Preparation method for regenerating waste lithium iron phosphate positive electrode material based on nitrogen doping Download PDFInfo
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- CN116525819A CN116525819A CN202310800359.6A CN202310800359A CN116525819A CN 116525819 A CN116525819 A CN 116525819A CN 202310800359 A CN202310800359 A CN 202310800359A CN 116525819 A CN116525819 A CN 116525819A
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- Prior art keywords
- iron phosphate
- lithium iron
- positive electrode
- electrode material
- nitrogen
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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 165
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 77
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 71
- 239000002699 waste material Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000001172 regenerating effect Effects 0.000 title description 10
- 239000000843 powder Substances 0.000 claims abstract description 74
- 238000001354 calcination Methods 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910001868 water Inorganic materials 0.000 claims abstract description 47
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 38
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 238000000576 coating method Methods 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 239000006229 carbon black Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 22
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 22
- BXDMTLVCACMNJO-UHFFFAOYSA-N 5-amino-1,3-dihydrobenzimidazole-2-thione Chemical compound NC1=CC=C2NC(S)=NC2=C1 BXDMTLVCACMNJO-UHFFFAOYSA-N 0.000 claims abstract description 20
- YQOKLYTXVFAUCW-UHFFFAOYSA-N guanidine;isothiocyanic acid Chemical compound N=C=S.NC(N)=N YQOKLYTXVFAUCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims abstract description 11
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000006183 anode active material Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 72
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 54
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 30
- 229910052786 argon Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 229960004106 citric acid Drugs 0.000 claims description 24
- 235000015165 citric acid Nutrition 0.000 claims description 24
- 239000011247 coating layer Substances 0.000 claims description 24
- 238000000227 grinding Methods 0.000 claims description 18
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 17
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 17
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 17
- 238000007873 sieving Methods 0.000 claims description 12
- 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 10
- 239000008103 glucose Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 239000010406 cathode material Substances 0.000 claims description 6
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
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- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 3
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 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
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 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
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 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
- 229930182830 galactose Natural products 0.000 claims description 3
- 239000008101 lactose Substances 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
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 229940099690 malic acid Drugs 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 229960001367 tartaric acid Drugs 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 17
- 239000010405 anode material Substances 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 230000008439 repair process Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 34
- 238000001694 spray drying Methods 0.000 description 20
- 230000008569 process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000006012 monoammonium phosphate Substances 0.000 description 7
- 239000004576 sand Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000002626 targeted therapy Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007787 solid Substances 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
- 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
-
- 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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium iron phosphate anode materials, and discloses a preparation method of a regenerated waste lithium iron phosphate anode material based on nitrogen doping, which comprises the following steps: s1, pretreating a waste lithium iron phosphate battery to obtain anode active material powder; s2, carrying out hydrothermal reaction on the positive electrode active material powder, water, phosphoric acid or hydrogen phosphate, a lithium compound and an organic reducing agent to obtain a mixture; s3, heating the mixture with isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform for reaction to obtain nitrogen source coated lithium iron phosphate powder; s4, adding the superconducting carbon black, polyethylene glycol and water into the mixture for primary calcination to obtain a primary coated calcined product; and S5, calcining the lithium iron phosphate and an organic carbon source again to obtain the regenerated lithium iron phosphate positive electrode material. The invention greatly improves the overall performance of the regenerated material by a targeted repair lattice and secondary coating method, and has high recycling rate.
Description
Technical Field
The invention relates to the technical field of lithium iron phosphate anode materials, in particular to a preparation method of a regenerated waste lithium iron phosphate anode material based on nitrogen doping.
Background
Lithium Ion Batteries (LIBs) are widely used for power supply of portable electronic devices such as mobile phones and notebook computers, and are increasingly demanded due to large-scale application in the fields of electric vehicles and renewable energy storage. Among them, since olivine-type lithium iron phosphate (LiFePO 4 ) The lithium ion battery serving as the positive electrode material has stable structure, high theoretical capacity (170 mAh/g), good cycle performance, environmental protection, high safety coefficient and wide material source, so that LiFePO 4 The yield of materials is rapidly increasing, and correspondingly, the number of waste lithium iron phosphate batteries is rapidly increasing, and a large amount of LiFePO is available each year 4 Batteries are retired from electric vehicles.
For environmental protection and resource utilization requirements, decommissioned LiFePO is required 4 The battery is recycled. Most of the methods are to disassemble the lithium ion battery and then recover valuable elements, or recover waste lithium ion batteries by recovery processes such as an extraction method, a chemical precipitation method, an electrolytic method, a coprecipitation method and the like, but most of the processes are only applicable to the waste lithium ion batteries containing Ni and Co elements, and are not applicable to the waste lithium ion batteries without Ni and Co elements. In addition, itThere are also some obvious disadvantages in the recovery process: electrolytes containing harmful substances cannot be recovered or treated well; the use of inorganic acid and organic extractant can cause secondary pollution; the steps are complex, the equipment requirement is high, the cost is high, and the added value is low. Thus, retired LiFePO 4 The gradient utilization of the battery is the first choice of the recycling of the battery, and the function of the battery can be fully or partially recovered through the doping repair process in the continuous use process, so that the recycling efficiency can be effectively improved.
The Chinese patent publication No. CN115924872A discloses a method for regenerating a waste lithium iron phosphate positive electrode material based on a hydrothermal method, which comprises the following steps: calcining the lithium iron phosphate positive plate at high temperature to obtain active material powder to be treated; uniformly mixing active material powder to be treated with an organic reducing agent to obtain a mixture to be treated; placing the mixture to be treated in an oven for heating to obtain powder to be treated; uniformly mixing powder to be treated with a carbon source; calcining at high temperature in an inert gas protection atmosphere to obtain the regenerated lithium iron phosphate powder material. Although the patent can realize gradient utilization, the phase structure and the chemical composition of the nitrogen-doped carbon are not guaranteed to be compact and uniform, the coating integrity is not high, the conductivity, the multiplying power and the recycling performance of the material are not obviously improved, and the recycling efficiency is low.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a regenerated waste lithium iron phosphate positive electrode material based on nitrogen doping, which can directly regenerate and repair the waste lithium iron phosphate positive electrode material, and is different from the traditional method for recovering lithium iron phosphate or regenerating lithium iron phosphate, the method can recover the waste lithium iron phosphate positive electrode material in a low cost, high value and green way, the lattice defect of the lithium iron phosphate is repaired in a targeted treatment way, and the electrochemical performance of the regenerated lithium iron phosphate is improved through nitrogen doping, so that the electrochemical performance of the assembled battery reaches the commercial battery standard.
The aim of the invention is realized by the following technical scheme: a preparation method for regenerating a waste lithium iron phosphate positive electrode material based on nitrogen doping comprises the following steps:
s1, pretreating a waste lithium iron phosphate battery to obtain anode active material powder;
s2, mixing the positive electrode active material powder with water, phosphoric acid or hydrogen phosphate, a lithium compound and an organic reducing agent, performing hydrothermal reaction, and performing reduced pressure distillation to obtain a mixture;
s3, mixing the mixture with isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform, and heating for reaction to obtain nitrogen source coated lithium iron phosphate powder;
s4, adding the nitrogen source coated lithium iron phosphate powder into the superconducting carbon black, polyethylene glycol and water, dispersing, and performing primary calcination in an inert gas protection atmosphere to obtain a primary coated calcination product;
and S5, mixing the calcined product with an organic carbon source, and calcining again in an inert gas protection atmosphere to obtain a secondary coated calcined product, namely the regenerated lithium iron phosphate positive electrode material.
According to the method disclosed by the invention, the waste lithium iron phosphate anode material can be subjected to targeted therapy and repair, and the compound of phosphoric acid or hydrogen phosphate and lithium can not neutralize the phosphorus and lithium elements in the lithium iron phosphate anode material, so that the organic reducing agent is helpful for directly and accurately repairing the lattice defect of the lithium iron phosphate, and the primary repair of the lithium iron phosphate material is performed. And then, 5-amino-2-mercaptobenzimidazole is used as a sulfur nitrogen source, amino can be combined with the preliminarily repaired positive electrode material, guanidine isothiocyanate can be combined with the auxiliary nitrogen source, and a more uniform nitrogen source coating layer is formed on the surface of the positive electrode material through crosslinking, so that the coating integrity is higher. In addition, as the nitrogen source coating contains rich groups, the super-conductive carbon black has better attraction and affinity, and further a compact and uniform nitrogen-doped carbon primary coating is obtained. The nitrogen source can not only improve the compactness of the carbon coating on the surface of the lithium iron phosphate, but also improve the electronic conductivity of the coating and lithium iron phosphate particles by forming carbon-nitrogen conjugated structure groups, and the surface of the lithium iron phosphate is coated with the nitrogen-doped carbon coating, so that a good continuous electronic conducting layer is formed, and the multiplying power performance and the circulation capacity of the material are improved. Further, a secondary coating layer is formed on the nitrogen-doped carbon primary coating layer through an organic carbon source, the secondary coating layer can be additionally coated on the basis of the primary coating layer, the material carbon content is increased while the secondary coating layer is beneficial to reducing the lithium iron phosphate as a reducing agent, the organic carbon source has better cohesiveness, the structural stability can be improved, the two carbon source coatings can produce a synergistic effect, and the electrochemical performance of the material is greatly improved.
In addition, the sulfur nitrogen source and the auxiliary nitrogen source are combined on molecules and form effective uniform coating through crosslinking, so that the granularity and the morphology of the lithium iron phosphate can be effectively regulated and controlled, the phase structure and the chemical composition of the regenerated lithium iron phosphate positive electrode material are uniform, and the compactness and the uniformity of the secondary coating are also higher.
Preferably, in S3, the mass ratio of the mixture, isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform is 100:120: 20-30: 7-12: 20-30.
Preferably, in the step S3, the heating reaction is carried out at 30-40 ℃ for 2-3 hours with stirring.
Preferably, in S4, the mass ratio of the nitrogen source coated lithium iron phosphate powder, the superconducting carbon black, the polyethylene glycol and the water is 100: 0.1-1: 2-2.5: 150; the specific resistance of the superconducting carbon black is 0.8-1.0Ω & m.
Polyethylene glycol not only can play a role in dispersing the superconducting carbon black, but also can be coated outside the positive electrode material due to stronger hydrogen bond interaction generated by rich groups contained in the nitrogen source, and a carbon layer is formed by carbonization in the primary calcination process, so that the synergistic effect of coating three carbon sources can be achieved by adjusting the addition amount of the carbon source and the calcination parameters.
Preferably, in the step S4, the primary calcination is divided into two steps, namely, the temperature is raised to 300-400 ℃ for calcination for 1-2 hours, and then the temperature is raised to 550-600 ℃ for calcination for 2-3 hours.
Dividing the primary calcination into two steps can make the effect of nitrogen doping carbon better and carbonization more complete.
Preferably, the thickness of the coating layer of the secondary coating is 100-300 nm, and the coating amount is 1-3 wt%.
As a best effortIn the step S2, the mass ratio of the positive electrode active material powder to the water to the organic reducing agent is 1:20: 2-2.5; PO in the phosphoric acid or hydrogen phosphate 4 - Li in lithium Compound + The molar ratio of the organic reducing agent is 1:1: 1.1-1.2; the hydrothermal reaction is carried out by heating to 120-150 ℃ in a reaction kettle for 6-8 h.
The size of the regenerated phosphoric acid crystal can be controlled by selecting proper temperature and time, and the addition amount of the organic reducing agent can influence the repairing effect on the lattice defect of the lithium iron phosphate.
Preferably, in S2, the hydrogen phosphate is one of lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, and lithium dihydrogen phosphate; the lithium compound is one of lithium hydroxide, lithium carbonate, lithium phosphate and lithium oxide; the organic reducing agent is one of citric acid, ascorbic acid, succinic acid, malic acid, tartaric acid and salicylic acid.
Preferably, in S5, the organic carbon source is one of lactose, sucrose, fructose, glucose, galactose, and maltose; the inert gas is nitrogen or argon; the temperature of the re-calcination is 600-800 ℃, and the calcination time is 5-9 h.
Preferably, in S1, the pretreatment is: and disassembling the waste lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, performing preliminary calcination on the lithium iron phosphate positive plate in an inert gas protection atmosphere, and sequentially performing oscillating separation, grinding and sieving to obtain positive active material powder.
Preferably, the temperature of the preliminary calcination is 300-500 ℃; the sieving is performed in a sieve with 100-400 meshes.
According to the invention, firstly, after the waste lithium iron phosphate battery is disassembled, a lithium iron phosphate positive plate and a negative graphite plate are separated by using a manual or mechanical method, and the lithium iron phosphate positive plate is used as a material to be treated. Calcining the lithium iron phosphate positive electrode plate which is the material to be treated in the first step under the protective atmosphere of argon or nitrogen at 300-500 ℃ to deactivate and carbonize organic matters or binders in the active substances, separating lithium iron phosphate powder from the plate by vibration and the like, grinding the lithium iron phosphate powder by a manual or mechanical method, and sieving the lithium iron phosphate powder in a sieve with 100-400 meshes to obtain black powder of the active substance of the positive electrode to be treated in the second step.
Compared with the prior art, the invention has the following beneficial effects:
(1) The regeneration method is to recover the waste lithium iron phosphate cathode material by repairing the lithium iron phosphate crystal lattice through targeted therapy, has simple process flow and has greater economic benefit compared with wet recovery and fire recovery; the energy consumption and the emission of greenhouse gases can be obviously reduced, and the method has great environmental benefit;
(2) In the process of repairing the regenerated lithium iron phosphate crystal lattice, nitrogen is doped in the lithium iron phosphate carbon coating layer to form a carbon-nitrogen conjugated structure group, so that the electronic conductivity of the coating layer and lithium iron phosphate particles is greatly improved, the overall performance of the regenerated material is improved, the process flow is simple, and the efficiency-cost ratio is high;
(3) The secondary coating layer is formed on the nitrogen-doped carbon primary coating layer through an organic carbon source, so that the secondary coating layer can be additionally coated on the basis of the primary coating, the carbon content of the material is increased while the material is reduced by using the secondary coating layer as a reducing agent, the organic carbon source has better cohesiveness, the structural stability can be improved, the coating of the two carbon sources can produce a synergistic effect, and the electrochemical performance of the material is greatly improved;
(4) The nitrogen-doped carbon primary coating layer is formed into an effective uniform coating through molecular combination and crosslinking, so that the granularity and the morphology of the lithium iron phosphate can be effectively regulated and controlled, the phase structure and the chemical composition of the regenerated lithium iron phosphate positive electrode material are uniform, and the compactness and the uniformity of the secondary coating layer are also higher.
Drawings
FIG. 1 is an SEM image of a waste lithium iron phosphate and regenerated lithium iron phosphate positive electrode material of the invention;
FIG. 2 is a graph showing charge-discharge cycle performance tests of a lithium iron phosphate positive electrode material (R-LFP) and a spent lithium iron phosphate positive electrode material (S-LFP) of the present invention and a commercial lithium iron phosphate positive electrode material (LFP) (Canrd-lithium iron phosphate (D-3)) assembled button cell;
fig. 3 is a graph of charge-discharge rate performance tests of the assembled button cell of the regenerated lithium iron phosphate and spent lithium iron phosphate positive electrode material and commercial lithium iron phosphate positive electrode material of the present invention.
Detailed Description
The technical scheme of the present invention is described below by using specific examples, but the scope of the present invention is not limited thereto:
a preparation method for regenerating a waste lithium iron phosphate positive electrode material based on nitrogen doping comprises the following steps:
s1, pretreating a waste lithium iron phosphate battery, disassembling the waste lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, performing preliminary calcination on the lithium iron phosphate positive plate in a nitrogen or argon protection atmosphere at 300-500 ℃, sequentially performing oscillating separation and grinding, and sieving in a screen mesh with 100-400 meshes to obtain positive active material powder;
s2, mixing positive electrode active material powder, water, phosphoric acid or hydrogen phosphate, a lithium compound and an organic reducing agent in a reaction kettle, wherein the mass ratio of the positive electrode active material powder to the water to the organic reducing agent is 1:20: 2-2.5, PO in the phosphoric acid or hydrogen phosphate 4 - Li in lithium Compound + The molar ratio of the organic reducing agent is 1:1: 1.1-1.2, placing the reaction kettle in an oven, heating to 120-150 ℃ for reaction for 6-8 hours, and performing reduced pressure distillation to obtain a mixture;
s3, mixing the mixture with isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform, wherein the mass ratio of the mixture to the isopropanol to the 5-amino-2-mercaptobenzimidazole to the guanidine isothiocyanate to the chloroform is 100:120: 20-30: 7-12: 20-30, and stirring and reacting for 2-3 hours at the temperature of 30-40 ℃ to obtain nitrogen source coated lithium iron phosphate powder;
s4, adding the nitrogen source coated lithium iron phosphate powder into the superconducting carbon black (resistivity is 0.8-1.0Ω & m), polyethylene glycol and water for dispersion, wherein the mass ratio of the nitrogen source coated lithium iron phosphate powder to the superconducting carbon black to the polyethylene glycol to the water is 100: 0.1-1: 2-2.5: 150, performing primary calcination in a nitrogen or argon protection atmosphere, firstly heating to 300-400 ℃, calcining for 1-2 h, then heating to 550-600 ℃, and calcining for 2-3 h to obtain a primary coated calcined product;
and S5, mixing the calcined product with an organic carbon source, and calcining again in a nitrogen or argon protection atmosphere at 600-800 ℃ for 5-9 hours to obtain a secondary coated calcined product, wherein the thickness of a secondary coated coating layer is 100-300 nm, and the coating amount is 1-3 wt%, so that the regenerated lithium iron phosphate positive electrode material is obtained.
Wherein the hydrogen phosphate is one of lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and lithium dihydrogen phosphate; the lithium compound is one of lithium hydroxide, lithium carbonate, lithium phosphate and lithium oxide; the organic reducing agent is one of citric acid, ascorbic acid, succinic acid, malic acid, tartaric acid and salicylic acid; the nitrogen source compound is one of urea, polyvinylpyrrolidone, polyacrylamide and melamine. The organic carbon source is one of lactose, sucrose, fructose, glucose, galactose and maltose.
Example 1
A preparation method for regenerating a waste lithium iron phosphate positive electrode material based on nitrogen doping comprises the following steps:
s1, pretreating a waste lithium iron phosphate battery, disassembling the waste lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, performing preliminary calcination on the lithium iron phosphate positive plate in an argon protection atmosphere at 400 ℃, sequentially performing oscillating separation and grinding, and sieving in a sieve with 100-400 meshes to obtain positive active material powder;
s2, mixing the positive electrode active material powder with water, ammonium dihydrogen phosphate, lithium hydroxide and citric acid in a hydrothermal kettle, wherein the mass ratio of the positive electrode active material powder to the water to the citric acid is 1:20:2.2 PO in monoammonium phosphate 4 - Li in lithium hydroxide + The molar ratio of citric acid is 1:1:1.1, placing the hydrothermal kettle in an oven for heating, taking out the product in the reaction kettle after reacting for 7 hours at 140 ℃,removing the solvent by reduced pressure distillation to obtain a mixture;
s3, mixing the mixture with isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform, wherein the mass ratio of the mixture to the isopropanol to the 5-amino-2-mercaptobenzimidazole to the guanidine isothiocyanate to the chloroform is 100:120:30:11:30, stirring and reacting for 3 hours at 35 ℃, and then performing spray drying to obtain nitrogen source coated lithium iron phosphate powder;
s4, adding the nitrogen source coated lithium iron phosphate powder into the superconducting carbon black (resistivity is 0.8-1.0 omega-m), polyethylene glycol and water for dispersion, wherein the mass ratio of the nitrogen source coated lithium iron phosphate powder to the superconducting carbon black to the polyethylene glycol to the water is 100:0.8:2.3:150, after sanding and spray drying, performing primary calcination in an argon protection atmosphere, firstly heating to 350 ℃, calcining for 1h, then heating to 580 ℃ and calcining for 3h to obtain a primary coated calcined product;
and S5, carrying out sand grinding and mixing on the calcined product, glucose and water, carrying out spray drying, and then carrying out secondary calcination in an argon protection atmosphere at the temperature of 750 ℃ for 6 h to obtain a secondary coated calcined product, wherein the thickness of a secondary coated coating layer is 180+/-20 nm, and the coating amount is 1.5wt%, namely the regenerated lithium iron phosphate positive electrode material.
Example 2
A preparation method for regenerating a waste lithium iron phosphate positive electrode material based on nitrogen doping comprises the following steps:
s1, pretreating a waste lithium iron phosphate battery, disassembling the waste lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, performing preliminary calcination on the lithium iron phosphate positive plate in an argon protection atmosphere at 400 ℃, sequentially performing oscillating separation and grinding, and sieving in a sieve with 100-400 meshes to obtain positive active material powder;
s2, mixing the positive electrode active material powder with water, ammonium dihydrogen phosphate, lithium hydroxide and citric acid in a reaction kettle, wherein the mass ratio of the positive electrode active material powder to the water to the citric acid is 1:20:2.5 PO in monoammonium phosphate 4 - Li in lithium hydroxide + The molar ratio of citric acid is 1:1:1.2, will be reversedHeating the reaction kettle in an oven to 150 ℃ for 7 hours, taking out a product in the reaction kettle, and removing a solvent through reduced pressure distillation to obtain a mixture;
s3, mixing the mixture with isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform, wherein the mass ratio of the mixture to the isopropanol to the 5-amino-2-mercaptobenzimidazole to the guanidine isothiocyanate to the chloroform is 100:120:25:7:25, stirring and reacting for 3 hours at 30 ℃, and then spray drying to obtain nitrogen source coated lithium iron phosphate powder;
s4, adding the nitrogen source coated lithium iron phosphate powder into the superconducting carbon black (resistivity is 0.8-1.0 omega-m), polyethylene glycol and water for dispersion, wherein the mass ratio of the nitrogen source coated lithium iron phosphate powder to the superconducting carbon black to the polyethylene glycol to the water is 100:0.5:2.5:150, after sanding and spray drying, performing primary calcination in an argon protection atmosphere, firstly heating to 400 ℃, calcining for 1h, then heating to 550 ℃, and calcining for 3h to obtain a primary coated calcined product;
and S5, carrying out sand grinding and mixing on the calcined product, glucose and water, carrying out spray drying, and then carrying out secondary calcination in an argon protection atmosphere at the temperature of 750 ℃ for 9 h to obtain a secondary coated calcined product, wherein the thickness of the secondary coated coating layer is 250+/-20 nm, and the coating amount is 3wt%, namely the regenerated lithium iron phosphate positive electrode material.
Example 3
A preparation method for regenerating a waste lithium iron phosphate positive electrode material based on nitrogen doping comprises the following steps:
s1, pretreating a waste lithium iron phosphate battery, disassembling the waste lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, performing preliminary calcination on the lithium iron phosphate positive plate in an argon protection atmosphere at 400 ℃, sequentially performing oscillating separation and grinding, and sieving in a sieve with 100-400 meshes to obtain positive active material powder;
s2, mixing the positive electrode active material powder with water, ammonium dihydrogen phosphate, lithium hydroxide and citric acid in a reaction kettle, wherein the mass ratio of the positive electrode active material powder to the water to the citric acid is 1:20: PO in ammonium dihydrogen phosphate 4 - Hydrogen oxidationLi in lithium + The molar ratio of citric acid is 1:1:1.2, placing the reaction kettle in an oven, heating to 140 ℃ for reaction for 8 hours, taking out a product in the reaction kettle, and removing a solvent through reduced pressure distillation to obtain a mixture;
s3, mixing the mixture with isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform, wherein the mass ratio of the mixture to the isopropanol to the 5-amino-2-mercaptobenzimidazole to the guanidine isothiocyanate to the chloroform is 100:120:20:12:20, stirring and reacting for 2-3 hours at 30-40 ℃, and then performing spray drying to obtain nitrogen source coated lithium iron phosphate powder;
s4, adding the nitrogen source coated lithium iron phosphate powder into the superconducting carbon black (resistivity is 0.8-1.0 omega-m), polyethylene glycol and water for dispersion, wherein the mass ratio of the nitrogen source coated lithium iron phosphate powder to the superconducting carbon black to the polyethylene glycol to the water is 100:1:2:150, after sanding and spray drying, performing primary calcination in an argon protection atmosphere, firstly heating to 300 ℃, calcining for 2 hours, then heating to 550 ℃, and calcining for 2 hours to obtain a primary coated calcined product;
and S5, carrying out sand grinding and mixing on the calcined product, glucose and water, carrying out spray drying, and then carrying out secondary calcination in an argon protection atmosphere at the temperature of 600 ℃ for 8h to obtain a secondary coated calcined product, wherein the thickness of the secondary coated coating layer is 120+/-20 nm, and the coating amount is 1wt%, namely the regenerated lithium iron phosphate positive electrode material.
Comparative example 1
The difference from example 1 is that: and doping and coating by adopting other nitrogen sources.
The method comprises the following steps:
s1, pretreating a waste lithium iron phosphate battery, disassembling the waste lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, performing preliminary calcination on the lithium iron phosphate positive plate in an argon protection atmosphere at 400 ℃, sequentially performing oscillating separation and grinding, and sieving in a sieve with 100-400 meshes to obtain positive active material powder;
s2, mixing the positive electrode active material powder with water, monoammonium phosphate, lithium hydroxide, citric acid and urea in a hydrothermal kettle, wherein the positive electrode active materialThe mass ratio of the powder to the water to the citric acid is 1:20:2.2 PO in monoammonium phosphate 4 - Li in lithium hydroxide + The molar ratio of citric acid is 1:1:1.1, placing a hydrothermal kettle in an oven for heating, reacting for 7 hours at 140 ℃, taking out a product in the reaction kettle, and performing spray drying to obtain nitrogen source coated lithium iron phosphate powder;
s3, adding the nitrogen source coated lithium iron phosphate powder into the superconducting carbon black (resistivity is 0.8-1.0 omega-m), polyethylene glycol and water for dispersion, wherein the mass ratio of the nitrogen source coated lithium iron phosphate powder to the superconducting carbon black to the polyethylene glycol to the water is 100:0.8:2.3:150, after sanding and spray drying, performing primary calcination in an argon protection atmosphere, firstly heating to 350 ℃, calcining for 1h, then heating to 580 ℃ and calcining for 3h to obtain a primary coated calcined product;
and S5, carrying out sand grinding and mixing on the calcined product, glucose and water, carrying out spray drying, and then carrying out secondary calcination in an argon protection atmosphere at the temperature of 750 ℃ for 6 h to obtain a secondary coated calcined product, wherein the thickness of a secondary coated coating layer is 180+/-20 nm, and the coating amount is 1.5wt%, namely the regenerated lithium iron phosphate positive electrode material.
Comparative example 2
The difference from example 1 is that: guanidine isothiocyanate was not added.
The method comprises the following steps:
s1, pretreating a waste lithium iron phosphate battery, disassembling the waste lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, performing preliminary calcination on the lithium iron phosphate positive plate in an argon protection atmosphere at 400 ℃, sequentially performing oscillating separation and grinding, and sieving in a sieve with 100-400 meshes to obtain positive active material powder;
s2, mixing the positive electrode active material powder with water, ammonium dihydrogen phosphate, lithium hydroxide and citric acid in a hydrothermal kettle, wherein the mass ratio of the positive electrode active material powder to the water to the citric acid is 1:20:2.2 PO in monoammonium phosphate 4 - Li in lithium hydroxide + The molar ratio of citric acid is 1:1:1.1, placing the hydrothermal kettle in an oven for heating at 140 DEG CAfter 7h of reaction, taking out the product in the reaction kettle, and removing the solvent by reduced pressure distillation to obtain a mixture;
s3, mixing the mixture with isopropanol, 5-amino-2-mercaptobenzimidazole and chloroform, wherein the mass ratio of the mixture to the isopropanol to the 5-amino-2-mercaptobenzimidazole to the chloroform is 100:120:30: 30, stirring and reacting for 3 hours at 35 ℃, and then performing spray drying to obtain nitrogen source coated lithium iron phosphate powder;
s4, adding the nitrogen source coated lithium iron phosphate powder into the superconducting carbon black (resistivity is 0.8-1.0 omega-m), polyethylene glycol and water for dispersion, wherein the mass ratio of the nitrogen source coated lithium iron phosphate powder to the superconducting carbon black to the polyethylene glycol to the water is 100:0.8:2.3:150, after sanding and spray drying, performing primary calcination in an argon protection atmosphere, firstly heating to 350 ℃, calcining for 1h, then heating to 580 ℃ and calcining for 3h to obtain a primary coated calcined product;
and S5, carrying out sand grinding and mixing on the calcined product, glucose and water, carrying out spray drying, and then carrying out secondary calcination in an argon protection atmosphere at the temperature of 750 ℃ for 6 h to obtain a secondary coated calcined product, wherein the thickness of a secondary coated coating layer is 180+/-20 nm, and the coating amount is 1.5wt%, namely the regenerated lithium iron phosphate positive electrode material.
Comparative example 3
The difference from example 1 is that: the addition amount of polyethylene glycol is small, and the parameters of primary calcination are controlled differently.
A preparation method for regenerating a waste lithium iron phosphate positive electrode material based on nitrogen doping comprises the following steps:
s1, pretreating a waste lithium iron phosphate battery, disassembling the waste lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, performing preliminary calcination on the lithium iron phosphate positive plate in an argon protection atmosphere at 400 ℃, sequentially performing oscillating separation and grinding, and sieving in a sieve with 100-400 meshes to obtain positive active material powder;
s2, mixing the positive electrode active material powder with water, ammonium dihydrogen phosphate, lithium hydroxide and citric acid in a hydrothermal kettle, wherein the mass ratio of the positive electrode active material powder to the water to the citric acid is 1:20:2.2 PO in monoammonium phosphate 4 - Li in lithium hydroxide + The molar ratio of citric acid is 1:1:1.1, placing a hydrothermal kettle in an oven for heating, reacting for 7 hours at 140 ℃, taking out a product in the reaction kettle, and removing a solvent through reduced pressure distillation to obtain a mixture;
s3, mixing the mixture with isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform, wherein the mass ratio of the mixture to the isopropanol to the 5-amino-2-mercaptobenzimidazole to the guanidine isothiocyanate to the chloroform is 100:120:30:11:30, stirring and reacting for 3 hours at 35 ℃, and then performing spray drying to obtain nitrogen source coated lithium iron phosphate powder;
s4, adding the nitrogen source coated lithium iron phosphate powder into the superconducting carbon black (resistivity is 0.8-1.0 omega-m), polyethylene glycol and water for dispersion, wherein the mass ratio of the nitrogen source coated lithium iron phosphate powder to the superconducting carbon black to the polyethylene glycol to the water is 100:0.8:1.5:150, performing primary calcination in an argon protection atmosphere after sanding and spray drying, heating to 500 ℃, and calcining for 4 hours to obtain a primary coated calcined product;
and S5, carrying out sand grinding and mixing on the calcined product, glucose and water, carrying out spray drying, and then carrying out secondary calcination in an argon protection atmosphere at the temperature of 750 ℃ for 6 h to obtain a secondary coated calcined product, wherein the thickness of a secondary coated coating layer is 180+/-20 nm, and the coating amount is 1.5wt%, namely the regenerated lithium iron phosphate positive electrode material.
Comparative example 4
The difference from example 1 is that: no superconducting carbon black was added.
The method comprises the following steps:
s1, pretreating a waste lithium iron phosphate battery, disassembling the waste lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, performing preliminary calcination on the lithium iron phosphate positive plate in an argon protection atmosphere at 400 ℃, sequentially performing oscillating separation and grinding, and sieving in a sieve with 100-400 meshes to obtain positive active material powder;
s2, mixing the anode active material powder with water, ammonium dihydrogen phosphate, lithium hydroxide and citric acid in a hydrothermal kettle,wherein the mass ratio of the positive electrode active material powder to the water to the citric acid is 1:20:2.2 PO in monoammonium phosphate 4 - Li in lithium hydroxide + The molar ratio of citric acid is 1:1:1.1, placing a hydrothermal kettle in an oven for heating, reacting for 7 hours at 140 ℃, taking out a product in the reaction kettle, and removing a solvent through reduced pressure distillation to obtain a mixture;
s3, mixing the mixture with isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform, wherein the mass ratio of the mixture to the isopropanol to the 5-amino-2-mercaptobenzimidazole to the guanidine isothiocyanate to the chloroform is 100:120:30:11:30, stirring and reacting for 3 hours at 35 ℃, and then performing spray drying to obtain nitrogen source coated lithium iron phosphate powder;
s4, primary calcination is carried out on the lithium iron phosphate powder coated by the nitrogen source in an argon protection atmosphere, the temperature is firstly increased to 350 ℃, the calcination is carried out for 1h, then the temperature is increased to 580 ℃, and the calcination is carried out for 3h, so that a primary coated calcination product is obtained;
and S5, carrying out sand grinding and mixing on the calcined product, glucose and water, carrying out spray drying, and then carrying out secondary calcination in an argon protection atmosphere at the temperature of 750 ℃ for 6 h to obtain a secondary coated calcined product, wherein the thickness of a secondary coated coating layer is 180+/-20 nm, and the coating amount is 1.5wt%, namely the regenerated lithium iron phosphate positive electrode material.
Button cell: the NMP is used as a solvent, and regenerated lithium iron phosphate positive electrode materials are prepared by the following steps: SP: pvdf=8: 1:1 (mass ratio) to prepare slurry with the solid content of 70, uniformly coating the slurry on foil to prepare the anode. The anode adopts a metal lithium sheet with the diameter of 14mm, and the electrolyte adopts 1mol LiFP 6 (EC: DMC: emc=1:1:1, volume ratio), the battery is packaged in the order of negative electrode case-shrapnel-gasket-lithium sheet-electrolyte-separator-positive electrode sheet-gasket-positive electrode case, and the whole process is completed in a glove box filled with hydrogen.
Test conditions: the test voltage range is 2.5V-4.3V, the charge-discharge capacity and the cycle performance of the assembled button cell are tested under the current density of 1C, and the multiplying power performance of the assembled button cell is tested under the current densities of 0.2C, 0.5C, 1C, 2C and 5C.
TABLE 1
As shown in fig. 1, which is an SEM image of the spent lithium iron phosphate cathode material of the present invention (cathode active material powder, left image) and the regenerated lithium iron phosphate cathode material of example 1 (right image), it can be seen that spent lithium iron phosphate particles are relatively random, and regenerated lithium iron phosphate particles are relatively uniform. Fig. 2 shows a charge-discharge cycle performance test chart of the regenerated lithium iron phosphate positive electrode material (R-LFP) and the spent lithium iron phosphate positive electrode material (S-LFP) of the embodiment 1 and the commercial lithium iron phosphate positive electrode material (LFP) assembled button cell of the invention, and the comparison of the specific discharge capacities of the two is proved that the regenerated and repaired waste lithium iron phosphate. As shown in fig. 3, the charge-discharge rate performance test chart of the assembled button cell of the regenerated lithium iron phosphate and the spent lithium iron phosphate cathode material and the commercial lithium iron phosphate cathode material according to the embodiment 1 of the present invention shows that the electrochemical performance of the regenerated lithium iron phosphate doped with nitrogen is superior to that of the waste lithium iron phosphate and is close to that of the commercial lithium iron phosphate.
As shown in table 1, the electrochemical performance of the regenerated lithium iron phosphate when the comparative example 1 was doped with other nitrogen sources was poor because better synergistic performance and uniform coating could not be formed, resulting in poor rate capability and cycle ability of the material. Comparative example 2 shows that guanidine isothiocyanate is not added as an auxiliary nitrogen source, and cannot be crosslinked to form a more uniform nitrogen source coating, and coating integrity and uniformity are affected. Comparative examples 3-4 demonstrate that polyethylene glycol and superconducting carbon black contribute to the synergistic effect of multiple carbon sources, and that both the parameters of the coating process conditions and the amount added affect the electrochemical properties of the final material.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures disclosed herein or modifications in the equivalent processes, or any application of the structures disclosed herein, directly or indirectly, in other related arts.
Claims (10)
1. The preparation method of the regenerated waste lithium iron phosphate cathode material based on nitrogen doping is characterized by comprising the following steps:
s1, pretreating a waste lithium iron phosphate battery to obtain anode active material powder;
s2, mixing the positive electrode active material powder with water, phosphoric acid or hydrogen phosphate, a lithium compound and an organic reducing agent, performing hydrothermal reaction, and performing reduced pressure distillation to obtain a mixture;
s3, mixing the mixture with isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform, and heating for reaction to obtain nitrogen source coated lithium iron phosphate powder;
s4, adding the nitrogen source coated lithium iron phosphate powder into the superconducting carbon black, polyethylene glycol and water, dispersing, and performing primary calcination in an inert gas protection atmosphere to obtain a primary coated calcination product;
and S5, mixing the calcined product with an organic carbon source, and calcining again in an inert gas protection atmosphere to obtain a secondary coated calcined product, namely the regenerated lithium iron phosphate positive electrode material.
2. The preparation method of the regenerated waste lithium iron phosphate positive electrode material based on nitrogen doping according to claim 1, wherein in S3, the mass ratio of the mixture, isopropanol, 5-amino-2-mercaptobenzimidazole, guanidine isothiocyanate and chloroform is 100:120: 20-30: 7-12: 20-30.
3. The method for preparing the regenerated waste lithium iron phosphate positive electrode material based on nitrogen doping according to claim 1 or 2, wherein in the step S3, the heating reaction is carried out at 30-40 ℃ for 2-3 hours by stirring.
4. The preparation method of the regenerated waste lithium iron phosphate positive electrode material based on nitrogen doping according to claim 1, wherein in S4, the mass ratio of the nitrogen source coated lithium iron phosphate powder to the superconducting carbon black to the polyethylene glycol to the water is 100: 0.1-1: 2-2.5: 150; the specific resistance of the superconducting carbon black is 0.8-1.0Ω & m.
5. The method for preparing the regenerated waste lithium iron phosphate positive electrode material based on nitrogen doping according to claim 1 or 4, wherein in S4, the primary calcination is divided into two steps, namely heating to 300-400 ℃, calcining for 1-2 hours, heating to 550-600 ℃ and calcining for 2-3 hours.
6. The method for preparing the regenerated waste lithium iron phosphate positive electrode material based on nitrogen doping according to claim 1, wherein the thickness of the coating layer of the secondary coating is 100-300 nm, and the coating amount is 1-3 wt%.
7. The method for preparing the regenerated waste lithium iron phosphate positive electrode material based on nitrogen doping according to claim 1, wherein in S2, the mass ratio of the positive electrode active material powder to water to the organic reducing agent is 1:20: 2-2.5; PO in the phosphoric acid or hydrogen phosphate 4 - Li in lithium Compound + The molar ratio of the organic reducing agent is 1:1: 1.1-1.2; the hydrothermal reaction is carried out by heating to 120-150 ℃ in a reaction kettle for 6-8 h.
8. The method for preparing the regenerated waste lithium iron phosphate positive electrode material based on nitrogen doping according to claim 1 or 7, wherein in the step S2, the hydrogen phosphate is one of lithium dihydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and lithium dihydrogen phosphate; the lithium compound is one of lithium hydroxide, lithium carbonate, lithium phosphate and lithium oxide; the organic reducing agent is one of citric acid, ascorbic acid, succinic acid, malic acid, tartaric acid and salicylic acid.
9. The method for preparing the nitrogen-doped regenerated waste lithium iron phosphate-based positive electrode material according to claim 1, 6 or 7, wherein in S5, the organic carbon source is one of lactose, sucrose, fructose, glucose, galactose and maltose; the inert gas is nitrogen or argon; the temperature of the re-calcination is 600-800 ℃, and the calcination time is 5-9 h.
10. The method for preparing the regenerated waste lithium iron phosphate positive electrode material based on nitrogen doping according to claim 1, wherein in the step S1, the pretreatment is as follows: and disassembling the waste lithium iron phosphate battery to obtain a lithium iron phosphate positive plate, performing preliminary calcination on the lithium iron phosphate positive plate in an inert gas protection atmosphere, and sequentially performing oscillating separation, grinding and sieving to obtain positive active material powder.
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