CN117525650A - Lithium iron manganese phosphate active material regenerated by waste lithium iron phosphate positive electrode powder, and regeneration method and application thereof - Google Patents
Lithium iron manganese phosphate active material regenerated by waste lithium iron phosphate positive electrode powder, and regeneration method and application thereof Download PDFInfo
- Publication number
- CN117525650A CN117525650A CN202311479954.0A CN202311479954A CN117525650A CN 117525650 A CN117525650 A CN 117525650A CN 202311479954 A CN202311479954 A CN 202311479954A CN 117525650 A CN117525650 A CN 117525650A
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- China
- Prior art keywords
- lithium iron
- positive electrode
- iron phosphate
- phosphate
- manganese
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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 73
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 title claims abstract description 65
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 239000000843 powder Substances 0.000 title claims abstract description 28
- 239000011149 active material Substances 0.000 title claims abstract description 20
- 238000011069 regeneration method Methods 0.000 title description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011572 manganese Substances 0.000 claims abstract description 40
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000002386 leaching Methods 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 230000001172 regenerating effect Effects 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims abstract description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 4
- 238000000576 coating method Methods 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002671 adjuvant Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 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 5
- 239000011230 binding agent Substances 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 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
- 238000001354 calcination Methods 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004472 Lysine Substances 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000005429 filling process Methods 0.000 claims description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 2
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 39
- 238000011084 recovery Methods 0.000 abstract description 6
- 239000012761 high-performance material Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 15
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000005955 Ferric phosphate Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229940032958 ferric phosphate Drugs 0.000 description 3
- 230000001939 inductive effect Effects 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 3
- 239000011268 mixed slurry Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000009647 facial growth Effects 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 229910011570 LiFe 1-x Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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- 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)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of battery material recovery, and particularly relates to a method for preparing lithium iron phosphate by regenerating waste lithium iron phosphate positive electrode powder, which comprises the steps of carrying out reduction acid leaching treatment on the waste lithium iron phosphate positive electrode powder, and then carrying out solid-liquid separation to obtain leaching liquid in which Fe, P and Li are dissolved; adding a manganese source and an auxiliary agent into the leaching solution, and controlling the mole ratio of Li (Fe+Mn): P in the obtained mixed solution to be 2.7-3.2: 1:0.98 to 1.05, the molar concentration ratio of Fe/Mn is 9:1 to 3:7, the volume ratio of water to the auxiliary agent is 5-10:1, and the total molar concentration of Fe+Mn is 0.4-1.5M; the auxiliary agent comprises at least one of ethanol, n-propanol and isopropanol; filling and sealing the mixed solution in a pressure-resistant reaction container, heating to more than 110 ℃, preserving heat and pressure for reaction, and then carrying out solid-liquid separation to obtain an LFMP precursor; and (3) carrying out carbon coating treatment on the LFMP precursor to obtain the regenerated lithium iron manganese phosphate active material. The invention can regenerate the waste material to obtain the high-performance material.
Description
Technical Field
The invention belongs to the technical field of waste lithium battery anode material recovery, and particularly relates to the field of recovery and regeneration of waste lithium iron phosphate anode powder.
Background
The lithium iron phosphate battery has the advantages of long cycle life, low cost, good safety performance and the like, and is widely applied to electric automobiles and energy storage systems. With the continuous expansion of electric vehicles and energy storage markets, the yield of lithium iron phosphate batteries continues to increase. At the same time, a large number of retired batteries will be generated. The retired battery contains a large amount of toxic components and valuable metals, and if the retired battery is not properly treated, the retired battery can cause resource waste and environmental pollution.
At present, the recovery of waste lithium iron phosphate batteries mainly adopts a wet process to recover valuable components in the anode material, and products such as ferric phosphate, lithium carbonate, regenerated lithium iron phosphate and the like are obtained. Lithium iron manganese phosphate has been a market share because of its higher energy density relative to lithium iron phosphate.
The prior art discloses a method for regenerating waste materials, for example, chinese patent document with publication number of CN116374983A discloses a method for circularly regenerating lithium iron manganese phosphate waste powder, which comprises the following steps: powdering a lithium iron manganese phosphate pole piece, sieving and collecting dust to obtain lithium iron manganese phosphate pole piece powder; calcining lithium iron manganese phosphate electrode powder, and cooling to obtain an oxidation mixture; mixing the oxidation mixture with a lithium source, a phosphorus source, an iron source and a carbon source, adding the mixture into pure water, and performing ball milling and spray drying to obtain a lithium iron manganese phosphate precursor; and sintering and purifying the lithium iron manganese phosphate precursor under the protection of inert gas to synthesize the lithium iron manganese phosphate anode material. For another example, chinese patent publication No. CN115224379A discloses a lithium iron manganese phosphate composite material and a preparation method thereofThe method comprises the following steps: respectively obtaining a lithium iron manganese phosphate reclaimed material, a conductive agent reclaimed material and a fluorine-containing reclaimed material; preparing a precursor from the recovered lithium iron manganese phosphate material, lithium iron phosphate and a lithium source; and (3) sintering the precursor, mixing the precursor with a conductive agent reclaimed material and a fluorine-containing reclaimed material, and performing secondary sintering to obtain the carbon-coated lithium iron manganese phosphate composite material with the core-shell structure. The Chinese patent document with publication number of CN108565522A discloses an electrochemical activity restoration method of failure lithium iron manganese phosphate, wherein lithium element, manganese element, iron element and carbon source are added into the failure lithium iron manganese phosphate, and the materials are uniformly mixed, and finally calcined under inert atmosphere, so that the electrochemical activity restoration can be realized. The Chinese patent document with publication number of CN108923090A discloses a method for recycling waste lithium iron phosphate batteries, which comprises the following steps: (1) Separating out an anode mixture from the waste lithium iron phosphate battery; (2) Fully dissolving the positive electrode mixture by sulfuric acid, filtering to obtain a first filtrate, adding ammonia water into the filtrate, stirring until the pH value of the system is 1.0-1.9, continuously stirring, and filtering to obtain a second filtrate and ferric phosphate precipitate; (3) Adding barium hydroxide or barium nitrate into the second filtrate, and filtering to obtain a third filtrate; (4) According to the product to be prepared, lithium iron manganese phosphate LiFe 1-x Mn x PO 4 Adding the third filtrate, ferric phosphate precipitate, a manganese source, a phosphorus source and a carbon source according to the molar ratio of the elements to obtain a mixed solution; (5) Ball milling, drying and crushing the mixed solution, presintering in an inert atmosphere at a first temperature, and sintering at a second temperature to obtain the carbon-coated lithium iron manganese phosphate anode material.
Although the prior art discloses some regeneration modes of waste lithium iron manganese phosphate materials, the existing modes still have difficulty in utilizing electrochemical beneficial elements and non-beneficial elements in the waste materials with high selectivity, and the problems of non-ideal electrochemical performance of the regenerated materials caused by factors such as low crystallinity of lithium iron manganese phosphate, easy collapse of a crystal structure, difficult control of crystal faces and the like caused by impurities in the waste materials are difficult to solve.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing lithium iron manganese phosphate by regenerating waste lithium iron phosphate positive electrode powder, which aims to solve the problems faced by the formation of LFMP by regenerating waste LFP and prepare a lithium iron manganese phosphate active material with excellent electrochemical performance.
A second object of the present invention is to provide a regenerated lithium iron manganese phosphate active material prepared by the method and its use in a lithium secondary battery.
A third object of the present invention is to provide a lithium secondary battery and a positive electrode thereof, and the like, comprising the regenerated lithium iron manganese phosphate active material.
Compared with pure-phase raw materials, the waste lithium iron phosphate material has a plurality of non-electrode material components which are caused by electrochemical circulation and are introduced in the recovery process, and the non-electrode material components contain components beneficial to the electrochemical performance and do not have a great deal of components adverse to the electrochemical performance. If these non-electrode material components are not well treated, they will interfere with the crystallization, crystal plane orientation, morphology of the recycled material, and thus the electrochemical properties of the recycled material. In addition, compared with lithium iron phosphate, the introduction of Mn can further increase the degree of crystallinity, crystal face and morphology regulation difficulty to a certain extent. Therefore, when the waste lithium iron phosphate is used for regenerating the lithium iron manganese phosphate material, the problems of selective utilization of beneficial components and non-beneficial components in the waste lithium iron phosphate material and interference of the components on crystallization, orientation and morphology of the lithium iron manganese phosphate are required to be properly solved. Aiming at the problem, the invention provides the following improvement scheme through intensive research:
a method for preparing lithium iron phosphate by regenerating waste lithium iron phosphate positive electrode powder comprises the steps of carrying out reduction acid leaching treatment on the waste lithium iron phosphate positive electrode powder, and then carrying out solid-liquid separation to obtain leaching liquid in which Fe, P and Li are dissolved;
adding a manganese source and an auxiliary agent into the leaching solution, and controlling the mole ratio of Li (Fe+Mn): P in the obtained mixed solution to be 2.7-3.2: 1:0.98 to 1.05, the molar concentration ratio of Fe/Mn is 9:1 to 3:7, the volume ratio of water to the auxiliary agent is 5-10:1, and the total molar concentration of Fe+Mn is 0.4-1.5M; the auxiliary agent comprises at least one of ethanol, n-propanol and isopropanol; filling and sealing the mixed solution in a pressure-resistant reaction container, heating to more than 110 ℃, preserving heat and pressure for reaction, and then carrying out solid-liquid separation to obtain an LFMP precursor;
and (3) carrying out carbon coating treatment on the LFMP precursor to obtain the regenerated lithium iron manganese phosphate active material.
The invention provides a thought for preparing lithium iron manganese phosphate based on regeneration of waste lithium iron phosphate, and aims at the problem of selective utilization of waste components in the waste lithium iron phosphate, the invention innovatively carries out reduction leaching on the waste lithium iron phosphate, then carries out reaction under the assistance of an auxiliary agent after manganese is matched, further cooperates with the combined control of the proportion of the auxiliary agent and water and the concentration of Fe and Mn in the treatment stage, can selectively utilize beneficial trace elements in the waste lithium iron phosphate, and can assist in inducing crystallization of the lithium iron manganese phosphate, improve the crystallinity of the lithium iron manganese phosphate, induce (010) dominant crystal face orientation and assist morphology control, and not only can self-hybridize the crystal structure of the lithium iron phosphate in an adapting way, but also can synergistically improve the electrochemical performance of the regenerated lithium iron manganese phosphate material.
In the invention, the waste lithium iron phosphate positive electrode powder is a positive electrode material obtained by stripping a positive electrode plate of a waste lithium iron phosphate battery;
in the invention, the waste lithium iron phosphate positive electrode powder contains 60-95 wt.% of lithium iron phosphate active material and at least one of conductive agent, binder, diaphragm and electrolyte.
In the invention, waste lithium iron phosphate anode powder, a reducing agent and acid liquor are mixed for carrying out the reduction acid leaching treatment;
preferably, the reducing agent is at least one of ascorbic acid, citric acid and lysine;
preferably, the reducing agent is waste lithium iron phosphate anode powder with the weight percentage of 2-15%, and further can be 5-10%;
preferably, the acid liquid is at least one of sulfuric acid and hydrochloric acid;
preferably, the concentration of the solute of the acid solution is 1-5M, preferably 2-3M;
preferably, the liquid-solid ratio in the leaching stage is 5-20 ml/g;
preferably, the temperature of the leaching stage is 60-90 ℃;
preferably, the leaching time is more than 1h, preferably 1-10 h;
in the invention, at least one of a manganese source, a lithium source and a phosphorus source is adopted in the mixed solution to regulate and control the element proportion in the mixed solution;
preferably, the manganese source is at least one of manganese sulfate, manganese acetate and manganese chloride;
preferably, the lithium source is at least one of lithium sulfate, lithium hydroxide and lithium dihydrogen phosphate;
preferably, the phosphorus source is at least one of diammonium hydrogen phosphate, monoammonium hydrogen phosphate, ammonium phosphate and phosphoric acid;
preferably, the auxiliary agent also comprises at least one auxiliary agent selected from diethyl ether and acetone;
the research of the invention also shows that the combination of the auxiliary agent and the auxiliary agent can be used for accidently and synergistically inducing the crystallization of the lithium iron manganese phosphate, inducing the (010) crystal face growth and jointly controlling the morphology, and can further synergistically improve the electrochemical performance of the prepared material.
Preferably, said adjuvant comprises ethanol and said adjuvant;
further preferably, the volume ratio of the ethanol to the auxiliary agent is 1:0.5 to 1.5.
In the invention, the mole ratio of Li (Fe+Mn): P in the mixed solution is 3-3.1: 1:1 to 1.02;
preferably, the molar concentration ratio of Fe/Mn is 4: 6-6: 4, a step of;
preferably, the volume ratio of water to auxiliary agent is 5-8: 1, a step of; it was found that at this ratio, the electrochemical properties of the regenerated material can be further improved.
Preferably, the total molar concentration of Fe+Mn is 0.5 to 1.0M, and more preferably 0.5 to 0.6M. It was found that under this preferred condition, the electrochemical properties of the regenerated material can be further improved.
Preferably, the pH of the mixed solution is controlled to be 6 to 9, more preferably 7 to 8, and the subsequent reaction is carried out.
In the invention, the filling volume of the mixed solvent in the pressure-resistant reaction container is 50-80%;
preferably, the atmosphere in the filling process is at least one of nitrogen and argon;
preferably, the temperature of the reaction stage is 150 to 210 ℃, more preferably 170 to 190 ℃.
Preferably, the time of the incubation and pressure maintaining reaction stage is 2 to 14 hours, more preferably 6 to 8 hours.
In the invention, the heat-preserving and pressure-maintaining reaction stage comprises two sections of heat-preserving platforms, wherein the temperature of the first section of heat-preserving platform is 110-140 ℃ and the time is 1-3 h; the temperature of the second section of heat preservation platform is 170-190 ℃ and the time is 4-10 h.
According to the invention, due to the combination of the leaching of the waste lithium iron phosphate and the subsequent reaction system, the double-platform gradient reaction mechanism is further matched, the crystallization of the lithium iron phosphate, the induction of (010) crystal face growth and the morphology regulation can be unexpectedly and synergistically improved, and the electrochemical performance of the prepared material can be further and synergistically improved.
In the present invention, the precursor may be subjected to carbon-coating treatment in a known manner.
According to one enumerated embodiment of the invention, the precursor and the carbon source are roasted, and carbon-coated treatment is carried out, so that the regenerated lithium iron manganese phosphate active material is prepared;
preferably, the carbon source is at least one of glucose, polyvinylpyrrolidone, melamine and polyvinylidene fluoride;
preferably, the weight ratio of the precursor to the carbon source is 1:0.1-0.2;
preferably, the atmosphere of the calcination stage is a protective atmosphere;
preferably, the temperature of the roasting treatment stage is 300-900 ℃;
preferably, the roasting time is 2-14 hours, preferably 4-10 hours, and more preferably 5-7 hours; preferably, the roasting treatment stage comprises a first-stage heat preservation process and a second-stage heat preservation process, wherein the temperature of the first-stage heat preservation process is 300-500 ℃, and the temperature of the second-stage heat preservation process is 600-800 ℃.
The time of the first section of heat preservation process can be 1-3 h, and the time of the second section of heat preservation process can be 3-7 h.
The invention also provides a regenerated lithium iron manganese phosphate active material prepared by the regeneration method.
In the invention, the combination of the preparation process and the parameters can realize the synergistic effect to endow the material with special physical and chemical structural characteristics, and the material with the characteristics can show excellent electrochemical performance.
The invention also provides a positive electrode of the lithium secondary battery, which comprises a current collector and a positive electrode material compounded on the surface of the current collector, wherein the positive electrode material comprises the regenerated lithium iron manganese phosphate active material prepared by the method;
preferably, the positive electrode material further comprises a binder and a conductive agent;
preferably, in the positive electrode material, the content of the regenerated lithium iron manganese phosphate active material is 60 to 90wt.%.
The invention also provides a lithium secondary battery comprising the positive electrode.
In the present invention, the lithium secondary battery and the positive electrode and positive electrode materials thereof may be conventional in all the components and parts except for the regenerated lithium iron manganese phosphate material of the present invention.
Advantageous effects
According to the invention, the waste lithium iron phosphate is subjected to reduction acid leaching recovery, and is reacted under the assistance of an auxiliary agent after manganese is matched, and the auxiliary agent and water proportion and the concentration of Fe and Mn are further matched for joint control in a treatment stage, so that beneficial trace elements in the waste lithium iron phosphate can be selectively utilized, the crystallization of the lithium iron phosphate is assisted to be induced, the crystallinity of the lithium iron phosphate is improved, the growth of a (010) dominant crystal face and the control of the auxiliary morphology are induced, the self-hybridization of the crystal structure can be adapted, and the electrochemical performance of the regenerated lithium iron phosphate material can be synergistically improved.
According to the invention, the combination of the leaching process of the waste lithium iron phosphate, the type of the auxiliary agent and/or the reaction gradient mechanism can realize unexpected synergy, and the electrochemical performance of the regenerated material can be further synergistically improved.
Drawings
Fig. 1 is an XRD pattern of lithium iron manganese phosphate of example 1.
Fig. 2 is an XRD pattern of lithium manganese iron phosphate of example 2-comparative group B.
Fig. 3 is an XRD pattern of lithium manganese iron phosphate of example 3-comparative group a.
FIG. 4 is a charge-discharge curve diagram of example 1 and example 3 comparative group A;
FIG. 5 is a cycle chart of example 1, example 3-comparative group A.
Detailed Description
The present invention will be specifically described with reference to the following examples.
The lithium iron phosphate positive electrode waste material can be peeled from the positive electrode sheet of the waste lithium iron phosphate battery based on a known process, and comprises the lithium iron phosphate active material, and also allows the existence of a conductive agent, a binder and the like, and in the following cases, the content of the lithium iron phosphate active material in the lithium iron phosphate positive electrode waste material is 80-90 wt% unless specifically stated as a typical list.
The invention relates to a method for preparing lithium iron manganese phosphate by regenerating waste lithium iron phosphate anode powder, which comprises the following steps:
(1) Carrying out acid leaching treatment on waste lithium iron phosphate, a reducing agent and sulfuric acid, carrying out solid-liquid separation to obtain a leaching solution, weighing a certain volume of the leaching solution, and recording the leaching solution as a solution A;
(2) Adding a certain amount of auxiliary agent into the solution A,
(3) Weighing manganese salt according to iron and manganese with different molar ratios by taking the molar quantity of iron ions as a reference, adding the manganese salt into the solution A, and stirring for dissolution;
(4) Weighing three times of lithium salt based on the total molar quantity of iron and manganese to prepare a solution (subtracting the lithium content in the leaching solution), and marking the solution as a solution B;
(5) Taking the total molar quantity of iron and manganese as a reference, weighing phosphate with corresponding molar quantity to prepare a solution (subtracting the content of phosphate radical in the leaching solution), and marking the solution as solution C;
(6) Preparing ammonia water solution with a certain concentration, and recording as solution D;
(7) And simultaneously adding the solution B and the solution C into the solution A at a certain feeding speed by utilizing a peristaltic pump under stirring, measuring the pH value of the mixed slurry by using a pH meter after the dosing is finished, slowly dripping the solution D into the mixed slurry, and controlling the pH value within a certain range. When the pH value is stable and the stirring is uniform, the solution is ready for use;
(8) Filling and sealing the mixed solution in the step (7) in a pressure-resistant container, wherein the filling volume is 50-80% by volume, heating to above 110 ℃ for reaction, decompressing and cooling after the reaction, and carrying out solid-liquid separation to obtain a precursor;
(9): and compounding and carbonizing the precursor and a carbon source to prepare the regenerated lithium iron manganese phosphate material.
The electrochemical performance of the regenerated lithium iron manganese phosphate is tested by adopting a blue electric tester at normal temperature and normal pressure. The positive plate is prepared by uniformly mixing and drying regenerated lithium iron phosphate material, conductive carbon black and PVDF (polyvinylidene fluoride), wherein the mass ratio is 8:1:1. The battery shell model adopted in the assembly of the button battery is CR2016, the electrolyte model is LX-345, the adopted diaphragm component is polypropylene, and lithium metal is used as a battery cathode. Next, a charge-discharge cycle test was performed on a button cell assembled using the regenerated lithium iron manganese phosphate material at 25 ℃ with a current of 1C.
The following are typical cases:
example 1:
step (1):
8wt.% of lithium iron phosphate, ascorbic acid and sulfuric acid solution with the concentration of 2mol/L are respectively added into a 500mL beaker, the temperature of a water bath kettle is set to 60 ℃, and the stirring speed is set to be equal to 400rpm. When the temperature of the water bath kettle is increased to a set temperature, taking lithium iron phosphate anode waste with a solid-to-liquid ratio of 10ml/g, adding the lithium iron phosphate anode waste into a beaker, setting the reaction time to be 2 hours, and filtering after the reaction is finished to obtain leaching liquid.
Step (2):
adding manganese sulfate and an auxiliary agent (ethanol) into the leaching solution, regulating the element proportion, concentration and pH of the mixed solution through lithium hydroxide, diammonium hydrogen phosphate and ammonia water, and controlling Li (Fe+Mn) in the finally obtained mixed solution: the molar ratio of P is 3:1:1, fe and Mn in a molar ratio of 1:1, a total molar concentration of iron and manganese of 0.5mol/L, a water and adjuvant (ethanol) volume ratio of 6:1, pH 8.
Step (3):
the mixed slurry was filled and sealed in a pressure-resistant vessel under argon atmosphere at a filling stage of 60% by volume, and then heated to 180℃for reaction (reaction temperature) for 6 hours. After the reaction is finished, cooling to room temperature and filtering to obtain lithium manganese phosphate (LFMP precursor).
Step (4):
and (3) taking and dissolving quantitative glucose, adding lithium iron manganese phosphate into a glucose aqueous solution (the weight ratio of the lithium iron manganese phosphate to the glucose is 1:0.15), uniformly mixing by ultrasonic, evaporating to dryness, roasting for 2 hours at 350 ℃ in Ar atmosphere, and roasting for 5 hours at 650 ℃ in Ar atmosphere to obtain the carbon-coated lithium iron manganese phosphate.
Through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 138.4mAh/g, and the capacity retention rate is 93.57% after 100 circles of 1C circulation.
Example 2:
the only difference compared to example 1 is that the total molar concentration of iron and manganese in the solution mixed in step (2) was varied, the experimental groups being:
group A: the total molar concentration of iron and manganese was 1.5M;
group B: the total molar concentration of iron and manganese was 1M;
comparative group a: the total molar concentration of iron and manganese was 0.2M;
performance testing was performed as in example 1, with the following results:
group A: through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 121.28mAh/g, and the capacity retention rate is 91.62% after the 1C is cycled for 100 circles.
Group B: through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 130.9mAh/g, and after 100 circles of 1C circulation, the capacity retention rate is 93.22 percent
Comparative group a: through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 87.48mAh/g, and the capacity retention rate is 82.5% after 100 circles of 1C circulation.
Example 3:
the difference compared with example 1 is that the total amount of water and auxiliary agent is unchanged, the type of auxiliary agent and the proportion of water and auxiliary agent in the step (2) are changed, other operations and parameters are the same as those in example 1, and the groups are as follows:
group A: the ratio of water to auxiliary agent is 8:1;
group B: the auxiliary agent is ethanol and acetone with the volume ratio of 1:1;
comparative group a: no auxiliary agent is added. The amount of water was the same as the total amount of water and adjuvants of example 1;
comparative group B: the ratio of water to auxiliary agent is 2:1;
performance testing was performed as in example 1, with the following results:
group A: through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 131.4mAh/g, and after 100 circles of 1C circulation, the capacity retention rate is 92.64%;
group B: through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 141.3mAh/g, and after 100 circles of 1C circulation, the capacity retention rate is 94.56%;
comparative group a: through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 112.3mAh/g, and after 100 circles of 1C circulation, the capacity retention rate is 92.64%;
comparative group B: through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 126.36mAh/g, and the capacity retention rate is 92.68% after 100 circles of 1C circulation;
example 4:
the only difference compared to example 1 is that the conditions of step (3) are changed, the group is:
group A: the reaction temperature is 160 ℃ and the reaction time is 8 hours;
group B: in the reaction stage, preserving heat at 120 ℃ for 1.5 hours in advance, then heating to 180 ℃ at a speed of 5 ℃/min, and preserving heat for 4 hours continuously;
performance testing was performed as in example 1, with the following results:
group A: through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 133.47mAh/g, and after 100 circles of 1C circulation, the capacity retention rate is 92.83%;
group B: through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 139.25mAh/g, and after 100 circles of 1C circulation, the capacity retention rate is 93.42%;
example 5:
the difference from example 1 is that the concentration of sulfuric acid at the time of leaching in the step (1) was 2.5mol/L and the solid-liquid ratio was 8ml/g; the Fe/Mn molar ratio in the step (2) is 4:6; and (4) taking polyvinylpyrrolidone as a carbon source, and roasting for 2 hours at 500 ℃ under Ar atmosphere and 4 hours at 750 ℃ under Ar atmosphere to obtain the carbon-coated lithium manganese iron phosphate.
Through testing, the prepared lithium iron manganese phosphate material is charged and discharged at 1C, the specific capacity of the first discharge is 138.25mAh/g, and the capacity retention rate is 92.05% after the 1C is cycled for 100 circles.
Claims (10)
1. A method for preparing lithium iron phosphate by regenerating waste lithium iron phosphate positive electrode powder is characterized in that the waste lithium iron phosphate positive electrode powder is subjected to reduction acid leaching treatment, and then solid-liquid separation is carried out to obtain leaching liquid in which Fe, P and Li are dissolved;
adding a manganese source and an auxiliary agent into the leaching solution, and controlling the mole ratio of Li (Fe+Mn): P in the obtained mixed solution to be 2.7-3.2: 1:0.98 to 1.05, the molar concentration ratio of Fe/Mn is 9:1 to 3:7, the volume ratio of water to the auxiliary agent is 5-10:1, and the total molar concentration of Fe+Mn is 0.4-1.5M; the auxiliary agent comprises at least one of ethanol, n-propanol and isopropanol;
filling and sealing the mixed solution in a pressure-resistant reaction container, heating to more than 110 ℃, preserving heat and pressure for reaction, and then carrying out solid-liquid separation to obtain an LFMP precursor;
and (3) carrying out carbon coating treatment on the LFMP precursor to obtain the regenerated lithium iron manganese phosphate active material.
2. The method for preparing lithium iron phosphate by regenerating waste lithium iron phosphate positive electrode powder according to claim 1, wherein the waste lithium iron phosphate positive electrode powder is a positive electrode material obtained by stripping waste lithium iron phosphate battery positive electrode sheets;
preferably, the waste lithium iron phosphate positive electrode powder contains 60-95 wt.% of lithium iron phosphate active material and also allows at least one of a conductive agent, a binder, a separator and an electrolyte.
3. The method for preparing lithium iron phosphate from the waste lithium iron phosphate positive electrode powder according to claim 1, wherein the waste lithium iron phosphate positive electrode powder, a reducing agent and an acid solution are mixed for carrying out the reduction acid leaching treatment;
preferably, the reducing agent is at least one of ascorbic acid, citric acid and lysine;
preferably, the reducing agent is waste lithium iron phosphate anode powder with the weight percentage of 2-15%;
preferably, the acid liquid is at least one of sulfuric acid and hydrochloric acid;
preferably, the concentration of the solute of the acid liquor is 1-5M;
preferably, the liquid-solid ratio in the leaching stage is 5-20 ml/g;
preferably, the temperature of the leaching stage is 60-90 ℃;
preferably, the leaching time is more than 1h, preferably 1-10 h.
4. The method for preparing lithium iron phosphate from the waste lithium iron phosphate positive electrode powder according to claim 1, wherein at least one of a manganese source, a lithium source and a phosphorus source is adopted in the mixed solution to regulate and control the element proportion in the mixed solution;
preferably, the manganese source is at least one of manganese sulfate, manganese acetate and manganese chloride;
preferably, the lithium source is at least one of lithium sulfate, lithium hydroxide and lithium dihydrogen phosphate;
preferably, the phosphorus source is at least one of diammonium hydrogen phosphate, monoammonium hydrogen phosphate, ammonium phosphate and phosphoric acid;
preferably, the auxiliary agent also comprises at least one auxiliary agent selected from diethyl ether and acetone;
preferably, said adjuvant comprises ethanol and said adjuvant;
further preferably, the volume ratio of the ethanol to the auxiliary agent is 1:0.5 to 1.5.
5. The method for preparing lithium iron phosphate from the waste lithium iron phosphate positive electrode powder according to claim 1, wherein the molar ratio of Li (Fe+Mn): P in the mixed solution is 3-3.1: 1:1 to 1.02;
preferably, the molar concentration of Fe/Mn is 4: 6-6: 4, a step of;
preferably, the volume ratio of water to the auxiliary agent is 5-8:1;
preferably, the total molar concentration of Fe+Mn is 0.4 to 1.5M;
preferably, the pH of the mixed solution is controlled to be 6 to 9, more preferably 7 to 8, and the subsequent reaction is carried out.
6. The method for preparing lithium iron phosphate from the waste lithium iron phosphate anode powder according to claim 1, wherein the filling volume of the mixed solvent in the pressure-resistant reaction container is 50-80%;
preferably, the atmosphere in the filling process is at least one of nitrogen and argon;
preferably, the temperature of the reaction stage is 150 to 210 ℃, further preferably 170 to 190 ℃; the reaction stage is preferably carried out for a period of 2 to 14 hours, more preferably 6 to 8 hours.
7. The method for preparing lithium iron phosphate from waste lithium iron phosphate anode powder according to claim 1, wherein the heat-preserving and pressure-maintaining reaction stage comprises two heat-preserving platforms, wherein the temperature of the first heat-preserving platform is 110-140 ℃ and the time is 1-3 h; the temperature of the second section of heat preservation platform is 170-190 ℃ and the time is 4-10 h;
preferably, roasting the precursor and a carbon source, and carrying out carbon-coated treatment to obtain the regenerated lithium iron manganese phosphate active material;
preferably, the carbon source is at least one of glucose, polyvinylpyrrolidone, melamine and polyvinylidene fluoride;
preferably, the weight ratio of the precursor to the carbon source is 1:0.1-0.2;
preferably, the atmosphere of the calcination stage is a protective atmosphere;
preferably, the temperature of the roasting treatment stage is 300-900 ℃;
preferably, the roasting time is 2-14 hours, preferably 4-10 hours, and more preferably 5-7 hours; preferably, the roasting treatment stage comprises a first-stage heat preservation process and a second-stage heat preservation process, wherein the temperature of the first-stage heat preservation process is 300-500 ℃, and the temperature of the second-stage heat preservation process is 600-800 ℃.
8. A regenerated lithium iron manganese phosphate active material made by the method of any one of claims 1-7.
9. A positive electrode of a lithium secondary battery, comprising a current collector and a positive electrode material compounded on the surface of the current collector, wherein the positive electrode material comprises the regenerated lithium iron manganese phosphate active material prepared by the method of any one of claims 1 to 7;
preferably, the positive electrode material further comprises a binder and a conductive agent;
preferably, in the positive electrode material, the content of the regenerated lithium iron manganese phosphate active material is 60 to 90wt.%.
10. A lithium secondary battery comprising the positive electrode of claim 9.
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