WO2023240613A1 - 正极活性材料及制备方法、正极极片、二次电池、电池模块、电池包及用电装置 - Google Patents
正极活性材料及制备方法、正极极片、二次电池、电池模块、电池包及用电装置 Download PDFInfo
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- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- AUBNQVSSTJZVMY-UHFFFAOYSA-M P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] Chemical compound P(=O)([O-])(O)O.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.C(C(=O)O)(=O)F.[Li+] AUBNQVSSTJZVMY-UHFFFAOYSA-M 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021549 Vanadium(II) chloride Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical class [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
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- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
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- 230000000712 assembly Effects 0.000 description 1
- 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 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- NPAXBRSUVYCZGM-UHFFFAOYSA-N carbonic acid;propane-1,2-diol Chemical compound OC(O)=O.CC(O)CO NPAXBRSUVYCZGM-UHFFFAOYSA-N 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- QKBJDEGZZJWPJA-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound [CH2]COC(=O)OCCC QKBJDEGZZJWPJA-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- XLDXZSVHMLAQMY-UHFFFAOYSA-N lithium;dioxalooxyborinate Chemical compound [Li+].OC(=O)C(=O)OB([O-])OC(=O)C(O)=O XLDXZSVHMLAQMY-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- ITAKKORXEUJTBC-UHFFFAOYSA-L vanadium(ii) chloride Chemical compound Cl[V]Cl ITAKKORXEUJTBC-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
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- 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
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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
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
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- 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
- H01M4/5805—Phosphides
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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
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- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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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
- C01P2006/10—Solid density
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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
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- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present application relates to the technical field of secondary batteries, and in particular to positive active materials, preparation methods of positive active materials, positive electrode sheets, secondary batteries, battery modules, battery packs and electrical devices.
- secondary batteries are widely used in energy storage power systems such as hydraulic, thermal, wind and solar power stations, as well as power tools, electric bicycles, electric motorcycles, electric vehicles, Military equipment, aerospace and other fields. Due to the great development of secondary batteries, higher requirements have been put forward for their energy density, cycle performance and safety performance.
- As the existing cathode active material for secondary batteries Li/Mn anti-site defects are prone to occur during the charge and discharge process of lithium manganese phosphate, and manganese dissolution is serious, affecting the gram capacity of the secondary battery and resulting in the safety performance of the secondary battery. and cycle performance deteriorates.
- This application was made in view of the above-mentioned issues, and its purpose is to provide a positive electrode active material, a preparation method of the positive electrode active material, a positive electrode plate, a secondary battery, a battery module, a battery pack and an electrical device to solve the existing problems.
- the lithium manganese phosphate cathode active material is prone to Li/Mn anti-site defects during the charge and discharge process, and the manganese dissolution is a serious problem, thereby solving the problems of low capacity, poor safety performance and poor cycle performance of secondary batteries.
- the first aspect of the present application provides a cathode active material with a core-shell structure, which includes a core and a shell covering the core,
- the kernel contains Li 1+x Mn 1-y A y P 1-z R z O 4 , where x is any value in the range -0.100-0.100, y is any value in the range 0.001-0.600, and z is 0.001- Any value within the range of 0.100,
- A is one selected from Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge Or multiple elements, optionally one or more elements selected from Fe, V, Ni, Co and Mg, R is one or more elements selected from B, Si, N and S, optionally Ground is one or more elements selected from Si, N and S;
- the shell includes a first cladding layer covering the core, a second cladding layer covering the first cladding layer, and a third cladding layer covering the second cladding layer, wherein,
- the first coating layer includes crystalline pyrophosphate Li a MP 2 O 7 and/or M b (P 2 O 7 ) c , where a is greater than 0 and less than or equal to 2, and b is any in the range of 1-4 Value, c is any value in the range of 1-3, M in crystalline pyrophosphate Li a MP 2 O 7 and M b (P 2 O 7 ) c is each independently selected from Fe, Ni, Mg, Co , one or more elements among Cu, Zn, Ti, Ag, Zr, Nb and Al, optionally selected from Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr and Al one or more elements;
- the second cladding layer includes crystalline oxide M′ d O e , where d is greater than 0 and less than or equal to 2, e is greater than 0 and less than or equal to 5, and M′ is selected from alkali metals, alkaline earth metals, transition metals, One or more elements from Group IIIA elements, Group IVA elements, lanthanide elements and Sb, optionally selected from Li, Be, B, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, One or more elements from Cd, In, Sn, Sb, Te, W, La and Ce, more optionally selected from Mg, Al, Si, Ti, V, Ni, Cu, Zr and W one or more elements;
- the third cladding layer contains carbon.
- the inventor of the present application found in actual operations that Li/Mn anti-site defects are easily generated in the lithium manganese phosphate cathode active material during deep charge and discharge processes, and manganese dissolution is relatively serious.
- the eluted manganese is reduced to metallic manganese after migrating to the negative electrode.
- the metal manganese produced is equivalent to a "catalyst", which can catalyze the decomposition of the SEI film (solid electrolyte interphase, solid electrolyte interface film) on the surface of the negative electrode.
- Part of the by-products produced are gases, which can easily cause the battery to expand and affect the safety of the secondary battery.
- Performance and the other part is deposited on the surface of the negative electrode, blocking the passage of lithium ions in and out of the negative electrode, causing the impedance of the secondary battery to increase and affecting the dynamic performance and cycle performance of the battery.
- the electrolyte and active lithium inside the battery are continuously consumed, which has an irreversible impact on the capacity retention rate of the secondary battery.
- crystalline means that the degree of crystallinity is above 50%, that is, between 50% and 100%. Crystallinity less than 50% is called glassy state.
- the crystallinity of the crystalline pyrophosphate of the present application ranges from 50% to 100%. Pyrophosphate with a certain degree of crystallinity is not only conducive to giving full play to the ability of the pyrophosphate coating to hinder manganese dissolution and reducing interface side reactions, but also enables the pyrophosphate coating and oxide coating to be better. The lattice matching is performed to achieve a tight bond between the cladding layer and the cladding layer.
- the above limitation on the numerical range of y is not only for each element as A
- the limitation of the stoichiometry of the element is also the limitation of the sum of the stoichiometry of each element as A.
- the stoichiometric numbers y1, y2...yn of A1, A2...An each need to fall within the numerical range of y defined in this application, and y1 , y2...yn and the sum must also fall within this numerical range.
- R is two or more elements
- the limitation on the numerical range of the R stoichiometric number in this application also has the above meaning.
- the above-mentioned limitation on the numerical range of b is not only a limitation on the stoichiometric number of each element as M, It is also a limitation on the sum of the stoichiometric numbers of each element as M.
- M is two or more elements M1, M2...Mn
- the stoichiometric numbers b1, b2...bn of M1, M2...Mn must each fall within the numerical range of b defined in this application, and b1 The sum of , b2...bn must also fall within this numerical range.
- M' in the chemical formula M' d O e is two or more elements
- the limitation on the numerical range of the stoichiometric number d of M' in this application also has the above meaning.
- the interplanar distance of the crystalline pyrophosphate in the first coating layer ranges from 0.293 to 0.470 nm, and the angle range of the crystal direction (111) ranges from 18.00° to 32.00°;
- the interplanar spacing range of the crystalline pyrophosphate in the first coating layer is 0.297-0.462nm; and/or,
- the angle range of the crystal orientation (111) of the crystalline pyrophosphate in the first coating layer is 19.211°-30.846°.
- the first coating layer in the cathode active material of the present application uses crystalline materials, and their crystal plane spacing and included angle range are within the above range. As a result, the impurity phase in the coating layer can be effectively avoided, thereby increasing the gram capacity of the material and improving the cycle performance and rate performance of the secondary battery.
- the ratio of y to 1-y is 1:10 to 1:1, optionally 1:4 to 1:1.
- the cycle performance and rate performance of the secondary battery are further improved.
- the ratio of z to 1-z is from 1:9 to 1:999, optionally from 1:499 to 1:249. As a result, the cycle performance and rate performance of the secondary battery are further improved.
- the carbon in the third coating layer is a mixture of SP2 form carbon and SP3 form carbon; optionally, the molar ratio of SP2 form carbon to SP3 form carbon is in the range of 0.07-13 Any value can be selected as any value in the range of 0.1-10, and further can be selected as any value in the range of 2.0-3.0.
- This application improves the overall performance of the secondary battery by limiting the molar ratio of SP2 form carbon to SP3 form carbon within the above range.
- the coating amount of the first coating layer is greater than 0 and less than or equal to 6% by weight, optionally greater than 0 and less than or equal to 5.5% by weight, more preferably greater than 0 and less than or equal to 5.5% by weight. Less than or equal to 2% by weight, based on the weight of the core; and/or
- the coating amount of the second coating layer is greater than 0 and less than or equal to 6% by weight, optionally greater than 0 and less than or equal to 5.5% by weight, more optionally 2%-4% by weight, based on the weight of the core ;and / or
- the coating amount of the third coating layer is greater than 0 and less than or equal to 6 wt%, optionally greater than 0 and less than or equal to 5.5 wt%, more optionally greater than 0 and less than or equal to 2 wt%, based on the core Weight scale.
- the coating amount of the three coating layers is preferably within the above range, so that the core can be fully coated without sacrificing the gram capacity of the cathode active material. to further improve the kinetic performance and safety performance of secondary batteries.
- the thickness of the first cladding layer is 2-10 nm.
- the thickness of the first coating layer ranges from 2 to 10 nm, the dissolution and migration of transition metal ions can be further reduced and the dynamic performance of the secondary battery can be improved.
- the thickness of the second cladding layer is 3-15 nm.
- the thickness of the second coating layer is in the range of 3-15 nm, the surface structure of the second coating layer is stable and the side reaction with the electrolyte is small. Therefore, the interface side reaction can be effectively reduced, thereby improving the high-temperature performance of the secondary battery. .
- the thickness of the third cladding layer is 5-25 nm.
- the electrical conductivity of the material can be improved and the compaction density performance of the battery pole piece prepared using the cathode active material can be improved.
- the manganese element content is in the range of 10% by weight - 35% by weight, optionally in the range of 15% by weight - 30% by weight, and more optionally in the range of 17% by weight - 20% by weight.
- the content of phosphorus element is in the range of 12% by weight - 25% by weight, optionally in the range of 15% by weight - 20% by weight;
- the weight ratio of manganese element to phosphorus element is in the range of 0.90-1.25, more optionally in the range of 0.95-1.20.
- the content of manganese element is within the above range, which can effectively improve the structural stability and density of the cathode active material, thereby improving the cycle, storage and compaction density of the secondary battery. performance; and can maintain a certain voltage platform height, thereby improving the energy density of secondary batteries.
- the content of phosphorus element is within the above range, which can effectively improve the conductivity of the cathode active material and improve the structural stability of the cathode active material.
- the weight ratio of manganese element to phosphorus element is within the above range, which can reduce the dissolution of transition metals and improve the stability of the cathode active material and the cycle and storage of secondary batteries. performance, and can maintain a certain discharge voltage platform height, thereby improving the energy density of secondary batteries.
- the lattice change rate of the cathode active material before and after complete deintercalation of lithium is 50% or less, optionally 4% or less, more preferably 3.8% or less, further optionally 2.0% -3.8%.
- the cathode active material with a core-shell structure of the present application can achieve a lower lattice change rate before and after deintercalation of lithium. Therefore, the use of positive active materials can improve the gram capacity and rate performance of secondary batteries.
- the Li/Mn anti-site defect concentration of the cathode active material is 5.3% or less, optionally 4% or less, more optionally 2.2% or less, further optionally 1.5%-2.2% .
- the transport of Li + can be improved, while the gram capacity of the cathode active material and the rate performance of the secondary battery can be improved.
- the compacted density of the positive active material at 3T is 1.95g/cm or more, optionally 2.2g/cm or more, further optionally 2.2g/cm or more and 2.8 g/cm 3 or less, and further optional, 2.2 g/cm 3 or more and 2.65 g/cm 3 or less. Therefore, by increasing the compaction density, the weight of the positive electrode active material per unit volume increases, which is beneficial to increasing the volumetric energy density of the secondary battery.
- the surface oxygen valence state of the cathode active material is -1.89 or less, optionally -1.90 to -1.98. Therefore, by limiting the surface oxygen valence state of the positive electrode active material within the above range, the interface side reaction between the positive electrode material and the electrolyte can be reduced, thereby improving the battery cell cycle, high-temperature storage gas production and other performances.
- a second aspect of this application provides a method for preparing a cathode active material, including the following steps:
- the core material contains Li 1+x Mn 1-y A y P 1-z R z O 4 , where x is any value in the range of -0.100-0.100, and y is any value in the range of 0.001-0.600 Value, z is any value in the range of 0.001-0.100,
- A is selected from Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and one or more elements in Ge, optionally one or more elements selected from Fe, V, Ni, Co and Mg
- R is one or more elements selected from B, Si, N and S or Multiple elements, optionally one or more elements selected from Si, N and S;
- the first coating step providing a first mixture containing pyrophosphate Li a MP 2 O 7 and/or M b (P 2 O 7 ) c , mixing the core material with the first mixture, drying, and sintering to obtain the first Material covered by the coating layer; where a is greater than 0 and less than or equal to 2, b is any value in the range of 1-4, c is any value in the range of 1-3; pyrophosphate Li a MP 2 O 7 M in and M b (P 2 O 7 ) c is each independently one or more elements selected from Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb and Al. Optionally is one or more elements selected from Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr and Al;
- the second coating step providing a second mixture containing the oxide M' d O e , mixing the material covered by the first coating layer with the second mixture, drying, and sintering to obtain a material covered by two layers of coating layer ; wherein, d is greater than 0 and less than or equal to 2, e is greater than 0 and less than or equal to 5, and M′ is selected from alkali metals, alkaline earth metals, transition metals, Group IIIA elements, Group IVA elements, lanthanide elements and Sb
- M′ is selected from alkali metals, alkaline earth metals, transition metals, Group IIIA elements, Group IVA elements, lanthanide elements and Sb
- M′ is selected from alkali metals, alkaline earth metals, transition metals, Group IIIA elements, Group IVA elements, lanthanide elements and Sb
- M′ is selected from alkali metals, alkaline earth metals, transition metals, Group IIIA elements, Group IVA elements, lanthanide elements and S
- the third coating step providing a third mixture containing a carbon source, mixing the material covered by the two coating layers with the third mixture, drying, and sintering to obtain a positive active material;
- the positive active material has a core-shell structure, which includes a core and a shell covering the core.
- the core includes Li 1+x Mn 1-y A y P 1-z R z O 4
- the shell includes a first layer covering the core.
- the second cladding layer contains crystalline oxide M′ d O e
- the third cladding layer contains carbon.
- this application provides a new type of lithium manganese phosphate core by doping element A at the manganese position and doping element R at the phosphorus position, and sequentially performs three-layer coating on the surface of the core.
- the cathode active material with a core-shell structure can greatly reduce the generation of Li/Mn anti-site defects, significantly reduce manganese dissolution, reduce the lattice change rate, and increase the compaction density.
- it can improve the performance of secondary batteries. capacity and improve the cycle performance, high-temperature storage performance and safety performance of secondary batteries.
- the step of providing the core material includes the following steps:
- Step (1) Mix a manganese source, a source of element A and an acid to obtain a mixture;
- Step (2) Mix the mixture obtained in step (1) with a lithium source, a phosphorus source, a source of element R and an optional solvent, and sinter under the protection of an inert gas to obtain Li 1+x Mn 1-y A y Core material of P 1-z R z O 4 .
- step (1) is performed at 20°C-120°C, optionally 40°C-120°C; and/or, in step (1), by rotating at 400-700 rpm Stir for 1-9h to mix.
- step (2) mixing is performed at a temperature of 20-120°C, optionally 40-120°C, for 1-10 hours.
- a first mixture is obtained by mixing a source of element M, a phosphorus source, an acid, an optional lithium source and an optional solvent; and/or,
- a second mixture is obtained by mixing the source of element M' with a solvent; and/or,
- a third mixture is obtained by mixing the carbon source and the solvent.
- the source of element M, the phosphorus source, the acid, the optional lithium source and the optional solvent are mixed at room temperature for 1-5 hours, and then heated to 50 °C-120 °C and keep mixing at this temperature for 2-10 hours.
- the above mixing is carried out under the condition of pH 3.5-6.5.
- the source of element M' and the solvent are mixed at room temperature for 1-10 hours, and then heated to 60°C-150°C and maintained at this temperature for 2-10 hours.
- the source of element A is one selected from the group consisting of elemental elements, carbonates, sulfates, halides, nitrates, organic acid salts, oxides and hydroxides of element A. or more; and/or,
- the source of element R is one or more selected from the group consisting of inorganic acids, organic acids, sulfates, halides, nitrates, organic acid salts, oxides and hydroxides of element R.
- sintering in the first coating step, sintering is performed at 650-800°C for 2-8 hours; and/or in the second coating step, sintering is performed at 400-750°C. 6-10 hours; and/or, in the third coating step, sintering is performed at 600-850°C for 6-10 hours.
- the third aspect of the present application provides a positive electrode sheet, which includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector.
- the positive electrode film layer includes the positive electrode active material of the first aspect of the present application or is formed by the positive electrode active material of the first aspect of the present application.
- a fourth aspect of the present application provides a secondary battery, including the positive active material of the first aspect of the present application or the positive active material prepared by the preparation method of the second aspect of the present application or the positive electrode sheet of the third aspect of the present application.
- a fifth aspect of the present application provides a battery module including the secondary battery of the fourth aspect of the present application.
- a sixth aspect of the present application provides a battery pack, including the battery module of the fifth aspect of the present application.
- a seventh aspect of the present application provides an electrical device, including at least one selected from the group consisting of the secondary battery of the fourth aspect of the present application, the battery module of the fifth aspect of the present application, and the battery pack of the sixth aspect of the present application. kind.
- Figure 1 is a schematic diagram of a positive electrode active material with a three-layer coating structure according to an embodiment of the present application.
- FIG. 2 is a schematic diagram of a secondary battery according to an embodiment of the present application.
- FIG. 3 is an exploded view of the secondary battery according to the embodiment of the present application shown in FIG. 2 .
- Figure 4 is a schematic diagram of a battery module according to an embodiment of the present application.
- Figure 5 is a schematic diagram of a battery pack according to an embodiment of the present application.
- FIG. 6 is an exploded view of the battery pack according to an embodiment of the present application shown in FIG. 5 .
- FIG. 7 is a schematic diagram of a power consumption device using a secondary battery as a power source according to an embodiment of the present application.
- Ranges disclosed herein are defined in terms of lower and upper limits. A given range is defined by selecting a lower limit and an upper limit that define the boundaries of the particular range. Ranges defined in this manner may be inclusive or exclusive of the endpoints, and may be arbitrarily combined, that is, any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, understand that ranges of 60-110 and 80-120 are also expected. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3, 4, and 5 are listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2- 3, 2-4 and 2-5.
- the numerical range “a-b” represents an abbreviated representation of any combination of real numbers between a and b, where a and b are both real numbers.
- the numerical range “0-5" means that all real numbers between "0-5" have been listed in this article, and "0-5" is just an abbreviation of these numerical combinations.
- a certain parameter is an integer ⁇ 2
- a method includes steps (a) and (b), which means that the method may include steps (a) and (b) performed sequentially, or may include steps (b) and (a) performed sequentially.
- step (c) means that step (c) can be added to the method in any order.
- the method may include steps (a), (b) and (c), and may also include step (a). , (c) and (b), and may also include steps (c), (a) and (b), etc.
- condition "A or B” is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists) ; Or both A and B are true (or exist).
- coating layer refers to the material layer coating the core.
- the material layer can completely or partially cover the core.
- coating layer is only for convenience of description. It is not intended to limit the invention.
- the term “thickness of the cladding layer” refers to the thickness of the cladding layer in the radial direction of the core.
- the term “cladding layer” is defined as above.
- Secondary batteries also known as rechargeable batteries or storage batteries, refer to batteries that can be recharged to activate active materials and continue to be used after the battery is discharged.
- a secondary battery normally includes a positive electrode plate, a negative electrode plate, a separator and an electrolyte.
- active ions such as lithium ions
- the isolation film is placed between the positive electrode piece and the negative electrode piece. It mainly prevents the positive and negative electrodes from short-circuiting and allows active ions to pass through.
- the electrolyte is between the positive electrode piece and the negative electrode piece and mainly plays the role of conducting active ions.
- the present application provides a cathode active material with a core-shell structure, which includes a core and a shell covering the core.
- the kernel contains Li 1+x Mn 1-y A y P 1-z R z O 4 , where x is any value in the range -0.100-0.100, y is any value in the range 0.001-0.600, and z is 0.001- Any value within the range of 0.100,
- A is one selected from Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge Or multiple elements, optionally one or more elements selected from Fe, V, Ni, Co and Mg, R is one or more elements selected from B, Si, N and S, optionally Ground is one or more elements selected from Si, N and S;
- the shell includes a first cladding layer covering the core, a second cladding layer covering the first cladding layer, and a third cladding layer covering the second cladding layer, wherein,
- the first coating layer includes crystalline pyrophosphate Li a MP 2 O 7 and/or M b (P 2 O 7 ) c , where a is greater than 0 and less than or equal to 2, and b is any in the range of 1-4 Value, c is any value in the range of 1-3, M in crystalline pyrophosphate Li a MP 2 O 7 and M b (P 2 O 7 ) c is each independently selected from Fe, Ni, Mg, Co , one or more elements among Cu, Zn, Ti, Ag, Zr, Nb and Al, optionally selected from Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr and Al one or more elements;
- the second cladding layer includes crystalline oxide M′ d O e , where d is greater than 0 and less than or equal to 2, e is greater than 0 and less than or equal to 5, and M′ is selected from alkali metals, alkaline earth metals, transition metals, One or more elements from Group IIIA elements, Group IVA elements, lanthanide elements and Sb, optionally selected from Li, Be, B, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, One or more elements from Cd, In, Sn, Sb, Te, W, La and Ce, more optionally selected from Mg, Al, Si, Ti, V, Ni, Cu, Zr and W one or more elements;
- the third cladding layer contains carbon.
- the cathode active material of the present application can improve the gram capacity, cycle performance and safety performance of the secondary battery. Although the mechanism is not yet clear, it is speculated that the cathode active material of the present application has a core-shell structure.
- the cathode active material of the present application has a core-shell structure.
- the element A doped at the manganese position of lithium manganese phosphate also helps to reduce the lattice change rate of lithium manganese phosphate during the process of deintercalating lithium, improves the structural stability of the cathode material, and greatly improves the structural stability of the cathode material.
- Reduce the dissolution of manganese and reduce the oxygen activity on the particle surface; the element R doped at the phosphorus site also helps to change the ease of Mn-O bond length change, thereby improving electronic conductivity and lowering the lithium ion migration barrier, promoting lithium Ion migration improves the rate performance of secondary batteries.
- the above limitation on the numerical range of y is not only for each element as The limitation of the stoichiometry of the element A is also the limitation of the sum of the stoichiometry of each element that is A.
- the stoichiometric numbers y1, y2...yn of A1, A2...An each need to fall within the numerical range of y defined in this application, and y1 , y2...yn and the sum must also fall within this numerical range.
- R is two or more elements
- the limitation on the numerical range of the R stoichiometric number in this application also has the above meaning.
- A is one selected from the group consisting of Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and Ge , two, three or four elements
- Q, D, E and K are each independently selected from Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and A kind of Ge, optionally, at least one of Q, D, E, and K is Fe.
- one of n1, n2, n3, and n4 is zero, and the rest are not zero; more optionally, two of n1, n2, n3, and n4 are zero, and the rest are not zero; also optionally, Three of n1, n2, n3, and n4 are zero, and the rest are not zero.
- doping One, two or three of the above-mentioned A elements in addition, it is advantageous to dope one or two R elements at the phosphorus site, which is beneficial to uniform distribution of doping elements.
- the values of x, y, and z are such that the entire core remains electrically neutral.
- the size of x is affected by the valence sizes of A and R and the sizes of y and z to ensure that the entire system is electrically neutral. If the value of x is too small, the lithium content of the entire core system will be reduced, affecting the gram capacity of the material.
- the y value will limit the total amount of all doping elements. If y is too small, that is, the doping amount is too small, the doping elements will have no effect. If y exceeds 0.5, the Mn content in the system will be less, affecting the material's properties. voltage platform.
- the R element is doped at the P position. Since the PO tetrahedron is relatively stable, and an excessive z value will affect the stability of the material, the z value is limited to 0.001-0.100.
- the entire core system remains electrically neutral, ensuring that there are as few defects and impurities in the cathode active material as possible. If there is an excess of transition metal (such as manganese) in the cathode active material, since the structure of the material system itself is relatively stable, the excess transition metal is likely to precipitate in the form of elemental substances, or form a heterogeneous phase inside the crystal lattice, maintaining the electrical neutrality. Sex can make such impurities as small as possible. In addition, ensuring the electrical neutrality of the system can also generate lithium vacancies in the material in some cases, thereby making the material's dynamic properties better.
- transition metal such as manganese
- the inventor of the present application cut out the middle region of the prepared cathode active material particles using a focused ion beam (FIB for short), and analyzed it through a transmission electron microscope (TEM for short) and X-ray energy spectroscopy (EDS for short). Tests were conducted and it was found that each element was evenly distributed and no aggregation occurred.
- FIB focused ion beam
- EDS X-ray energy spectroscopy
- a, b, and c have values such that the crystalline pyrophosphate Li a MP 2 O 7 or M b (P 2 O 7 ) c remains electrically neutral.
- the values of d and e are such that the crystalline state M′dOe remains electrically neutral.
- crystalline means that the degree of crystallinity is above 50%, that is, between 50% and 100%. Crystallinity less than 50% is called glassy state.
- the crystalline pyrophosphate salts of the present application have a crystallinity of 50% to 100%. Pyrophosphate with a certain degree of crystallinity is not only conducive to giving full play to the ability of the pyrophosphate coating to hinder manganese dissolution and reducing interface side reactions, but also enables the pyrophosphate coating and oxide coating to be better The lattice matching is performed to achieve a tighter combination of the cladding layers.
- the crystallinity of the crystalline pyrophosphate material of the first coating layer of the cathode active material can be tested by conventional technical means in the art, such as by density method, infrared spectroscopy, and differential scanning calorimetry. and nuclear magnetic resonance absorption methods, and can also be tested by, for example, X-ray diffraction.
- a specific X-ray diffraction method for testing the crystallinity of the first coating layer crystalline pyrophosphate of the cathode active material may include the following steps:
- the crystallinity is the ratio of the crystalline part scattering to the total scattering intensity.
- the crystallinity of the pyrophosphate in the coating layer can be adjusted, for example, by adjusting the process conditions of the sintering process, such as sintering temperature, sintering time, and the like.
- pyrophosphate as the first coating layer can effectively isolate the doped metal ions from the electrolyte.
- the structure of crystalline pyrophosphate is stable. Therefore, crystalline pyrophosphate coating can effectively inhibit the dissolution of transition metals and improve cycle performance.
- the bond between the first cladding layer and the core is similar to a heterojunction, and the strength of the bond is limited by the degree of lattice matching.
- the degree of bonding between the first cladding layer and the core is measured mainly by calculating the mismatch between the lattice constants of the core and the cladding. In this application, after the A and R elements are doped in the core, compared with undoped elements, the matching between the core and the first cladding layer is improved, and the core and the pyrophosphate cladding layer can be closer ground together.
- Crystalline oxide was selected as the second coating layer, firstly, because it has a high lattice match with the crystalline pyrophosphate of the first coating layer (the mismatch degree is only 3%); secondly, as the third coating layer
- the crystalline oxide of the second coating layer itself has better stability than pyrophosphate, and coating pyrophosphate with it is beneficial to improving the stability of the material.
- the structure of the crystalline oxide as the second coating layer is very stable. Therefore, coating with crystalline oxide can effectively reduce the interface side reactions on the surface of the positive electrode active material, thereby improving the high-temperature cycle and performance of the secondary battery. Storage performance.
- the lattice matching between the second cladding layer and the first cladding layer is similar to the above-mentioned combination between the first cladding layer and the core.
- the lattice mismatch is less than 5%, the lattice matching is relatively small. Well, the two are easily combined closely.
- carbon is used as the third layer of coating. Since electrochemical reactions occur when used in secondary batteries, electrons are required to participate. Therefore, in order to increase electron transmission between particles and at different locations on the particles, materials with excellent conductive properties can be used. Carbon coating. Carbon coating can effectively improve the conductive properties and desolvation ability of cathode active materials.
- Figure 1 is a schematic diagram of an ideal cathode active material with a three-layer coating structure.
- the innermost circle schematically represents the core, which is the first cladding layer, the second cladding layer, and the third cladding layer from the inside to the outside.
- This figure represents the ideal state where each layer is completely covered. In practice, each coating layer can be fully covered or partially covered.
- the interplanar distance of the crystalline pyrophosphate in the first coating layer ranges from 0.293 to 0.470 nm, and the included angle of the crystal orientation (111) ranges from 18.00° to 32.00°;
- the interplanar spacing range of the crystalline pyrophosphate in the first coating layer is 0.297-0.462nm; and/or,
- the angle range of the crystal orientation (111) of the crystalline pyrophosphate in the first coating layer is 19.211°-30.846°.
- the crystalline pyrophosphate in the first coating layer can be characterized by conventional technical means in the art, or can be characterized by, for example, transmission electron microscopy (TEM). Under TEM, the core and cladding layers can be distinguished by testing the interplanar spacing.
- TEM transmission electron microscopy
- the specific testing method for the interplanar spacing and included angle of the crystalline pyrophosphate in the first coating layer may include the following steps:
- Crystalline pyrophosphate within the above-mentioned crystal plane spacing and angle range can more effectively suppress the lattice change rate and Mn dissolution of lithium manganese phosphate during the lithium deintercalation process, thereby improving the high-temperature cycle performance and rate of secondary batteries. performance, cycling stability and high temperature storage performance.
- the ratio of y to 1-y is 1:10 to 1:1, optionally 1:4 to 1:1.
- y represents the sum of the stoichiometric numbers of the Mn-site doping element A.
- the ratio of z to 1-z is 1:9 to 1:999, optionally 1:499 to 1:249.
- z represents the sum of stoichiometric numbers of the P-site doping elements R.
- the carbon in the third coating layer is a mixture of SP2 form carbon and SP3 form carbon; optionally, the molar ratio of SP2 form carbon to SP3 form carbon is any value in the range of 0.07-13, more It can be any value in the range of 0.1-10, and further can be any value in the range of 2.0-3.0.
- the molar ratio of SP2 form carbon to SP3 form carbon can be about 0.1, about 0.2, about 03, about 0.4, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1, about 2 , about 3, about 4, about 5, about 6, about 7, about 8, about 9, or about 10, or within any range of any of the above values.
- the overall electrical performance of the secondary battery is improved. Specifically, by using a mixed form of SP2 form carbon and SP3 form carbon and limiting the ratio of SP2 form carbon to SP3 form carbon within a certain range, good conductivity can be achieved while ensuring the passage of lithium ions, so there is It is beneficial to the realization of secondary battery functions and its cycle performance.
- the mixing ratio of the SP2 form and the SP3 form of the third cladding carbon can be controlled by sintering conditions such as sintering temperature and sintering time.
- sintering conditions such as sintering temperature and sintering time.
- sucrose is used as the carbon source to prepare the third coating layer
- the sucrose is cracked at high temperature and deposited on the second coating layer.
- both SP3 and SP2 forms will be produced. of carbon coating.
- the ratio of SP2 form carbon and SP3 form carbon can be controlled by selecting high temperature cracking conditions and sintering conditions.
- the structure and characteristics of the carbon in the third coating layer can be measured by Raman spectroscopy.
- the specific test method is as follows: by peak splitting the energy spectrum of the Raman test, Id/Ig is obtained (where Id is the peak of SP3 form carbon Intensity, Ig is the peak intensity of SP2 form carbon), thereby confirming the molar ratio of the two.
- the coating amount of the first coating layer is greater than 0 and less than or equal to 6% by weight, optionally greater than 0 and less than or equal to 5.5% by weight, and more optionally greater than 0 and less than or equal to 2 % by weight, based on weight of core; and/or
- the coating amount of the second coating layer is greater than 0 and less than or equal to 6% by weight, optionally greater than 0 and less than or equal to 5.5% by weight, more optionally 2%-4% by weight, based on the weight of the core ;and / or
- the coating amount of the third coating layer is greater than 0 and less than or equal to 6 wt%, optionally greater than 0 and less than or equal to 5.5 wt%, more optionally greater than 0 and less than or equal to 2 wt%, based on the core Weight scale.
- the coating amount of each layer is not zero.
- the coating amount of the three coating layers is preferably within the above range, so that the core can be fully coated without sacrificing the gram capacity of the cathode active material. Under the premise, the dynamic performance and safety performance of secondary batteries can be further improved.
- the coating amount is within the above range, the dissolution of the transition metal can be reduced, ensuring the smooth migration of lithium ions, thereby improving the rate performance of the cathode active material.
- the positive active material can maintain a certain platform voltage and ensure the coating effect.
- the carbon coating mainly plays the role of enhancing electron transmission between particles.
- the structure also contains a large amount of amorphous carbon, the density of carbon is low.
- the coating amount is within the above range. Within, the compaction density of the pole pieces can be guaranteed.
- the thickness of the first cladding layer is 2-10 nm; and/or
- the thickness of the second cladding layer is 3-15nm; and/or
- the thickness of the third cladding layer is 5-25nm.
- the thickness of the first cladding layer may be about 2 nm, about 3 nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, or about 10 nm, or any range of any of the above values.
- the thickness of the second cladding layer may be about 3 nm, about 4 nm, about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm, about 11 nm, about 12 nm, about 13 nm, about 14 nm. , about 15nm, or within any range of any of the above values.
- the thickness of the third cladding layer may be about 5 nm, about 6 nm, about 7 nm, about 8 nm, about 9 nm, about 10 nm, about 11 nm, about 12 nm, about 13 nm, about 14 nm, about 15 nm, About 16 nm, about 17 nm, about 18 nm, about 19 nm, about 20 nm, about 21 nm, about 22 nm, about 23 nm, about 24 nm, or about 25 nm, or within any range of any of the above values.
- the thickness of the first coating layer ranges from 2 to 10 nm, it can effectively reduce the dissolution of transition metals and ensure the dynamic performance of the secondary battery.
- the thickness of the second coating layer is in the range of 3-15 nm, the surface structure of the second coating layer is stable and the side reaction with the electrolyte is small. Therefore, the interface side reaction can be effectively reduced, thereby improving the high-temperature performance of the secondary battery. .
- the electrical conductivity of the material can be improved and the compaction performance of the battery pole piece prepared using the positive active material can be improved.
- the thickness test of the coating layer is mainly carried out through FIB.
- the specific method may include the following steps: randomly select a single particle from the positive electrode active material powder to be tested, cut a slice with a thickness of about 100nm from the middle position or near the middle position of the selected particle, and then Conduct TEM test on the sheet, measure the thickness of the coating layer, measure 3-5 positions, and take the average value.
- the manganese element content is in the range of 10%-35% by weight, optionally in the range of 15%-30% by weight, more optionally in the range of 17%-20% by weight, based on the weight of the cathode active material.
- the content of phosphorus element is in the range of 12% by weight - 25% by weight, optionally in the range of 15% by weight - 20% by weight, and the weight ratio range of manganese element and phosphorus element is 0.90-1.25, optionally in the range of 0.90-1.25. 0.95-1.20.
- the content of manganese may correspond to the content of the core.
- limiting the content of manganese element within the above range can ensure the stability and high density of the positive active material, thereby improving the cycle, storage and compaction performance of the secondary battery, and maintaining a certain voltage. Platform height, thereby increasing the energy density of secondary batteries.
- limiting the content of phosphorus element within the above range can effectively improve the electrical conductivity of the material and improve the overall stability of the material.
- the weight ratio of manganese to phosphorus content is within the above range, which can effectively reduce the dissolution of transition metal manganese, improve the stability and gram capacity of the positive active material, thereby improving the cycle performance and storage performance of the secondary battery, and at the same time help In order to reduce the impurity phase in the material and maintain the discharge voltage platform height of the material, the energy density of the secondary battery is improved.
- the measurement of manganese and phosphorus elements can be carried out using conventional technical means in this field.
- the following method is used to determine the content of manganese and phosphorus: dissolve the material in dilute hydrochloric acid (concentration 10-30%), use ICP to test the content of each element in the solution, and then measure and convert the content of manganese. Get its weight ratio.
- the lattice change rate of the cathode active material with a core-shell structure before and after complete deintercalation of lithium is 50% or less, optionally 4% or less, more preferably 3.8% or less, further optionally: 2.0%-3.8%.
- the lithium deintercalation process of lithium manganese phosphate is a two-phase reaction.
- the interfacial stress of the two phases is determined by the lattice change rate before and after lithium deintercalation.
- the cathode active material with a core-shell structure of the present application can achieve a lower lattice change rate before and after deintercalation of lithium, so the use of the cathode active material can improve the rate performance of the secondary battery.
- the lattice change rate can be measured by methods known in the art, such as X-ray diffraction (XRD).
- the Li/Mn anti-site defect concentration of the cathode active material having a core-shell structure is 5.3% or less, optionally 4% or less, more optionally 2.2% or less, further optionally 1.5%- 2.2%.
- the Li/Mn anti-site defect in this application refers to the interchange of positions of Li + and Mn 2+ in the LiMnPO 4 crystal lattice.
- the Li/Mn antisite defect concentration refers to the percentage of Li + exchanged with Mn 2+ to the total amount of Li + .
- the Li/Mn antisite defect concentration can be tested in accordance with JIS K 0131-1996, for example.
- the cathode active material with a core-shell structure of the present application can achieve the above-mentioned lower Li/Mn anti-site defect concentration.
- the inventor of the present application speculates that because Li + and Mn 2+ will exchange positions in the LiMnPO 4 lattice, and the Li + transmission channel is a one-dimensional channel, Mn 2+ is in Li + It will be difficult to migrate in the channel, thus hindering the transport of Li + . Therefore, the cathode active material with a core-shell structure of the present application has a low Li/Mn anti-site defect concentration within the above range. Therefore, it can reduce the Mn 2+ hindrance to the transport of Li + and at the same time improve the performance of the cathode active material. Capacity play and rate performance.
- the compacted density of the positive active material at 3T is 1.95g/cm 3 or more, optionally 2.2g/cm 3 or more, further optionally 2.2g/cm 3 or more and 2.8g/cm 3
- further options are 2.2g/ cm3 or more and 2.65g/ cm3 or less.
- the higher the compaction density the greater the weight of the active material per unit volume. Therefore, increasing the compaction density is beneficial to increasing the volumetric energy density of the battery core.
- the compacted density can be measured according to GB/T 24533-2009.
- the surface oxygen valence state of the cathode active material is -1.89 or less, optionally -1.90 to -1.98.
- the stable valence state of oxygen is originally -2.
- its surface valence state is below -1.7.
- the surface oxygen valence state of the cathode active material of the present application is within the above range, which can reduce the interface side reaction between the cathode material and the electrolyte, thereby improving the circulation of the battery core, high-temperature storage gas production and other performances.
- EELS electron energy loss spectroscopy
- doping elements it is beneficial to enhance the doping effect. On the one hand, it further reduces the lattice change rate, thereby inhibiting the dissolution of manganese and reducing the consumption of electrolyte and active lithium. On the other hand, it is also beneficial to Further reduce surface oxygen activity and reduce interface side reactions between the positive electrode active material and the electrolyte, thereby improving the cycle performance and high-temperature storage performance of the secondary battery.
- x is any value within the range of -0.005-0.002, such as -0.004, -0.003, -0.002, -0.001, 0, 0.001, 0.002.
- y in the core of the cathode active material, y may be, for example, 0.001, 0.002, 0.3, 0.35, 0.4, 0.5.
- z in the core of the cathode active material, z may be, for example, 0.001, 0.002, 0.003, 0.005, 0.1.
- d is any value in the range of 1-2.
- e in the second coating layer of the cathode active material, e is any value in the range of 1-5.
- This application provides a preparation method of cathode active material, including the following steps:
- the core material contains Li 1+x Mn 1-y A y P 1-z R z O 4 , where x is any value in the range of -0.100-0.100, and y is any value in the range of 0.001-0.600 Value, z is any value in the range of 0.001-0.100,
- A is selected from Zn, Al, Na, K, Mg, Mo, W, Ti, V, Zr, Fe, Ni, Co, Ga, Sn, Sb, Nb and one or more elements in Ge, optionally one or more elements selected from Fe, V, Ni, Co and Mg
- R is one or more elements selected from B, Si, N and S or Multiple elements, optionally one or more elements selected from Si, N and S;
- the first coating step providing a first mixture containing pyrophosphate Li a MP 2 O 7 and/or M b (P 2 O 7 ) c , mixing the core material with the first mixture, drying, and sintering to obtain the first Material covered by the coating layer; where a is greater than 0 and less than or equal to 2, b is any value in the range of 1-4, c is any value in the range of 1-3; pyrophosphate Li a MP 2 O 7 M in and M b (P 2 O 7 ) c is each independently one or more elements selected from Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr, Nb and Al. Optionally is one or more elements selected from Fe, Ni, Mg, Co, Cu, Zn, Ti, Ag, Zr and Al;
- the second coating step providing a second mixture containing the oxide M' d O e , mixing the material covered by the first coating layer with the second mixture, drying, and sintering to obtain a material covered by two layers of coating layer ; wherein, d is greater than 0 and less than or equal to 2, e is greater than 0 and less than or equal to 5, and M′ is selected from alkali metals, alkaline earth metals, transition metals, Group IIIA elements, Group IVA elements, lanthanide elements and Sb
- M′ is selected from alkali metals, alkaline earth metals, transition metals, Group IIIA elements, Group IVA elements, lanthanide elements and Sb
- M′ is selected from alkali metals, alkaline earth metals, transition metals, Group IIIA elements, Group IVA elements, lanthanide elements and Sb
- M′ is selected from alkali metals, alkaline earth metals, transition metals, Group IIIA elements, Group IVA elements, lanthanide elements and S
- the third coating step providing a third mixture containing a carbon source, mixing the material covered by the two coating layers with the third mixture, drying, and sintering to obtain a positive active material;
- the positive active material has a core-shell structure, which includes a core and a shell covering the core.
- the core includes Li 1+x Mn 1-y A y P 1-z R z O 4
- the shell includes a first layer covering the core.
- the second cladding layer contains crystalline oxide M′ d O e
- the third cladding layer contains carbon.
- A, R, M, M′, x, y, z, a, b, c, d, e are as defined above.
- this application provides a new type of lithium manganese phosphate core by doping element A at the manganese position and doping element R at the phosphorus position, and sequentially performs three-layer coating on the surface of the core.
- the cathode active material with a core-shell structure can greatly reduce the generation of Li/Mn anti-site defects, significantly reduce manganese dissolution, reduce the lattice change rate, and increase the compaction density.
- it can improve the performance of secondary batteries. capacity and improve the cycle performance, high-temperature storage performance and safety performance of secondary batteries.
- the step of providing core material includes the following steps:
- Step (1) Mix a manganese source, a source of element A and an acid to obtain a mixture;
- Step (2) Mix the mixture obtained in step (1) with a lithium source, a phosphorus source, a source of element R and an optional solvent, and sinter under the protection of an inert gas to obtain Li 1+x Mn 1-y A y Core material of P 1-z R z O 4 .
- a and R are as defined above.
- step (1) is performed at 20°C-120°C, optionally at 40°C-120°C (eg, about 30°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C °C, about 100 °C, about 110 °C or about 120 °C); and/or, in step (1), by stirring at 400-700 rpm for 1-9h (optional 3-7h, for example, about 2 hours, About 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, or about 9 hours) for mixing.
- 1-9h optional 3-7h, for example, about 2 hours, About 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, or about 9 hours
- the temperature is 20-120°C, optionally 40-120°C (for example, about 30°C, about 50°C, about 60°C, about 70°C, about 80°C, about 90°C , about 100°C, about 110°C or about 120°C) for 1-10h (for example, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, About 9 hours, about 10 hours, about 11 hours or about 12 hours).
- 1-10h for example, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, About 9 hours, about 10 hours, about 11 hours or about 12 hours.
- the prepared core and the cathode active material produced therefrom have fewer lattice defects, which is beneficial to inhibiting manganese dissolution and reducing the interaction between the cathode active material and the electrolyte. Interfacial side reactions, thereby improving the cycle performance and safety performance of secondary batteries.
- step (2) mixing is performed at a pH of 3.5-6, optionally a pH of 4-6, more optionally a pH of 4-5.
- the pH can be adjusted by methods commonly used in the art, for example, by adding acid or alkali.
- the mixture obtained in step (1) is filtered, dried, and sand-ground to obtain element A-doped manganese salt particles with a particle size of 50-200 nm, and the element A-doped manganese salt particles are
- the manganese salt particles are used in step (2) to be mixed with a lithium source, a phosphorus source, a source of element R and an optional solvent.
- the molar ratio of the mixture or element A-doped manganese salt particles to the lithium source and phosphorus source is 1:0.5-2.1:0.5-2.1, optionally It’s about 1:1:1.
- step (2) sintering is performed at 600-950°C for 4-10 hours under an inert gas or a mixed atmosphere of inert gas and hydrogen; optionally, the protective atmosphere is 70-90 volume % nitrogen and A mixed gas of 10-30% hydrogen by volume; optionally, sintering can be performed at about 650°C, about 700°C, about 750°C, about 800°C, about 850°C or about 900°C for about 2 hours, about 3 hours, About 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours or about 10 hours; optionally, the sintering temperature and sintering time can be within any range of any of the above values, and can be improved
- the crystallinity of the core reduces the generation of impurities, allowing the core to maintain a certain particle size, thereby increasing the gram capacity and compaction density of the positive active material, and improving the overall performance of the secondary battery, including rate performance.
- the mixed materials in step (2) are dried to obtain powder, and then the powder is sintered to obtain a core containing Li 1+x Mn 1-y A y P 1-z R z O 4 Material.
- the first mixture is obtained by mixing a source of element M, a phosphorus source, an acid, an optional lithium source, and an optional solvent; and/or,
- a second mixture is obtained by mixing the source of element M' with a solvent; and/or,
- a third mixture is obtained by mixing the carbon source and the solvent.
- the first mixture, the second mixture, and the third mixture may be provided in the form of suspensions.
- the source of element M, the phosphorus source, the acid, the optional lithium source, and the optional solvent are mixed at room temperature for 1-5 hours (eg, about 1.5 hours, about 2 hours , about 3 hours, about 4 hours, about 4.5 hours or about 5 hours), and then raise the temperature to 50°C-120°C (such as 55°C, about 60°C, about 70°C, about 80°C, about 90°C, about 100°C , about 110°C or about 120°C) and keep mixing at this temperature for 2-10 hours (for example, about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours or about 10 hours), and the above mixing is performed under the condition that the pH is 3.5-6.5 (for example, 4-6).
- the source of element M' is mixed with the solvent at room temperature for 1-10 hours (e.g., 1.5 hours, about 2 hours, about 3 hours, about 4 hours, about 4.5 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours or about 10 hours), and then raise the temperature to 60°C-150°C (for example, about 65°C, about 70°C, about 80°C, about 90°C, About 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C) and maintain the temperature for mixing for 2-10 hours (for example, about 2 hours, about 3 hours, about 4 hours, about 5 hours , about 6 hours, about 7 hours, about 8 hours, about 9 hours or about 10 hours).
- 1-10 hours e.g., 1.5 hours, about 2 hours, about 3 hours, about 4 hours, about 4.5 hours, about 5 hours, about 6 hours, about 7 hours, about 8 hours, about 9 hours or about 10 hours
- 60°C-150°C for example, about
- the preparation method of the present application has no particular limitation on the source of materials.
- the source of a certain element may include one of the elements, sulfates, halides, nitrates, organic acid salts, oxides or hydroxides of the element. or more, provided that the source can achieve the purpose of the preparation method of the present application.
- the source of element A is one or more selected from the group consisting of elemental elements, carbonates, sulfates, halides, nitrates, organic acid salts, oxides and hydroxides of element A; and /or,
- the source of element R is one or more selected from the group consisting of inorganic acids, organic acids, sulfates, halides, nitrates, organic acid salts, oxides and hydroxides of element R.
- the source of element M is one or more selected from the group consisting of elemental elements, carbonates, sulfates, halides, nitrates, organic acid salts, oxides and hydroxides of element M.
- the source of element M' is one or more selected from the group consisting of elemental substances, carbonates, sulfates, halides, nitrates, organic acid salts, oxides and hydroxides of element M' .
- the addition amounts of the respective sources of elements A, R, M, and M' depend on the target doping amount, and the ratio of the amounts of lithium source, manganese source, and phosphorus source complies with the stoichiometric ratio.
- the manganese source may be a manganese-containing material known in the art that can be used to prepare lithium manganese phosphate.
- the manganese source may be one or more selected from the group consisting of elemental manganese, manganese dioxide, manganese phosphate, manganese oxalate, and manganese carbonate.
- the acid may be one or more selected from organic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, silicic acid, silicic acid, etc., and organic acids such as oxalic acid.
- the acid is a dilute organic acid with a concentration of 60% by weight or less.
- the lithium source may be a lithium-containing substance known in the art that can be used to prepare lithium manganese phosphate.
- the lithium source is one or more selected from lithium carbonate, lithium hydroxide, lithium phosphate, and lithium dihydrogen phosphate.
- the phosphorus source may be a phosphorus-containing material known in the art that can be used to prepare lithium manganese phosphate.
- the phosphorus source is one or more selected from diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate and phosphoric acid.
- the carbon source is one or more selected from starch, sucrose, glucose, polyvinyl alcohol, polyethylene glycol, and citric acid.
- sintering is performed at 650-800°C (eg, about 650°C, about 700°C, about 750°C, or about 800°C) for 2-8 hours (about 2 hours, about 3 hours, about 4 hours, about 5 hours, about 6 hours, about 8 hours); and/or,
- sintering is performed at 400-750°C (for example, about 400°C, about 450°C, about 500°C, about 550°C, about 600°C, about 700°C, about 750°C) for 6-10 hours ( For example, about 6 hours, about 7 hours, about 8 hours, about 9 hours, or about 10 hours); and/or,
- sintering is performed at 600-850°C (eg, about 600°C, about 650°C, about 700°C, about 750°C, about 800°C, about 850°C) for 6-10 hours (eg, about 6 hours , about 7 hours, about 8 hours, about 9 hours or about 10 hours).
- drying is performed at 80°C to 200°C, optionally 80°C to 190°C, more optionally 120°C to 180°C, or even
- the optional drying temperature is 120°C to 170°C
- the most optional is 120°C to 160°C
- the drying time is 3-9h
- the optional 4-8h is the most optional is 5-7h
- the present application provides a positive electrode sheet, which includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector.
- the positive electrode film layer includes the aforementioned positive electrode active material or the positive electrode active material prepared by the aforementioned preparation method;
- the content of the positive electrode active material in the positive electrode film layer is more than 10% by weight, based on the total weight of the positive electrode film layer.
- the content of the cathode active material in the cathode film layer is 90-99.5% by weight, based on the total weight of the cathode film layer. Ensure that the secondary battery has higher capacity and better cycle performance, high-temperature storage performance and safety performance.
- the positive electrode current collector may be a metal foil or a composite current collector.
- the metal foil aluminum foil can be used.
- the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer.
- the composite current collector can be formed by forming metal materials (aluminum, aluminum alloys, nickel, nickel alloys, titanium, titanium alloys, silver and silver alloys, etc.) on polymer material substrates (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
- PP polypropylene
- PBT polybutylene terephthalate
- PS polystyrene
- PE polyethylene
- the positive electrode film layer may also include other positive electrode active materials known in the art for use in batteries.
- the cathode active material may include at least one of the following materials: an olivine-structured lithium-containing phosphate and modified compounds thereof.
- the present application is not limited to these materials, and other traditional materials that can be used as positive electrode active materials of batteries can also be used. Only one type of these positive electrode active materials may be used alone, or two or more types may be used in combination.
- lithium-containing phosphates with an olivine structure may include, but are not limited to, lithium iron phosphate (such as LiFePO 4 (also referred to as LFP)), composite materials of lithium iron phosphate and carbon, lithium manganese phosphate (such as LiMnPO 4 ) , at least one composite material of lithium manganese phosphate and carbon.
- lithium iron phosphate such as LiFePO 4 (also referred to as LFP)
- composite materials of lithium iron phosphate and carbon such as LiMnPO 4
- LiMnPO 4 lithium manganese phosphate
- the positive electrode film layer optionally further includes a binder.
- the binder may include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene tripolymer. At least one of a meta-copolymer, a tetrafluoroethylene-hexafluoropropylene copolymer and a fluorine-containing acrylate resin.
- the positive electrode film layer optionally further includes a conductive agent.
- the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
- the negative electrode sheet includes a negative electrode current collector and a negative electrode film layer disposed on at least one surface of the negative electrode current collector.
- the negative electrode film layer includes a negative electrode active material.
- the negative electrode current collector has two opposite surfaces in its own thickness direction, and the negative electrode film layer is disposed on any one or both of the two opposite surfaces of the negative electrode current collector.
- the negative electrode current collector may be a metal foil or a composite current collector.
- the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base material.
- the composite current collector can be formed by forming metal materials (copper, copper alloy, nickel, nickel alloy, titanium, titanium alloy, silver and silver alloy, etc.) on a polymer material substrate (such as polypropylene (PP), polyterephthalate It is formed on substrates such as ethylene glycol ester (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
- PP polypropylene
- PBT polybutylene terephthalate
- PS polystyrene
- PE polyethylene
- the negative active material may be a negative active material known in the art for batteries.
- the negative active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate, and the like.
- the silicon-based material may be selected from at least one of elemental silicon, silicon oxide compounds, silicon carbon composites, silicon nitrogen composites and silicon alloys.
- the tin-based material may be selected from at least one of elemental tin, tin oxide compounds and tin alloys.
- the present application is not limited to these materials, and other traditional materials that can be used as battery negative electrode active materials can also be used. Only one type of these negative electrode active materials may be used alone, or two or more types may be used in combination.
- the negative electrode film layer optionally further includes a binder.
- the binder may be selected from styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), At least one of polymethacrylic acid (PMAA) and carboxymethyl chitosan (CMCS).
- the negative electrode film layer optionally further includes a conductive agent.
- the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene and carbon nanofibers.
- the negative electrode film layer optionally includes other auxiliaries, such as thickeners (such as sodium carboxymethylcellulose (CMC-Na)) and the like.
- thickeners such as sodium carboxymethylcellulose (CMC-Na)
- the negative electrode sheet can be prepared by dispersing the above-mentioned components for preparing the negative electrode sheet, such as negative active materials, conductive agents, binders and any other components in a solvent (such as deionized water) to form a negative electrode slurry; the negative electrode slurry is coated on the negative electrode current collector, and after drying, cold pressing and other processes, the negative electrode piece can be obtained.
- a solvent such as deionized water
- the electrolyte plays a role in conducting ions between the positive and negative electrodes.
- the type of electrolyte in this application can be selected according to needs.
- the electrolyte can be liquid, gel, or completely solid.
- the electrolyte is liquid and includes an electrolyte salt and a solvent.
- the electrolyte salt may be selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bisfluorosulfonimide, lithium bistrifluoromethanesulfonimide, trifluoromethane At least one of lithium sulfonate, lithium difluorophosphate, lithium difluoroborate, lithium dioxaloborate, lithium difluorodioxalate phosphate and lithium tetrafluoroxalate phosphate.
- the solvent may be selected from the group consisting of ethylene carbonate, propylene carbonate, methylethyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, Butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate At least one of ester, 1,4-butyrolactone, sulfolane, dimethyl sulfone, methyl ethyl sulfone and diethyl sulfone.
- the electrolyte optionally also includes additives.
- additives may include negative electrode film-forming additives, positive electrode film-forming additives, and may also include additives that can improve certain properties of the battery, such as additives that improve battery overcharge performance, additives that improve battery high-temperature or low-temperature performance, etc.
- the secondary battery further includes a separator film.
- a separator film There is no particular restriction on the type of isolation membrane in this application. Any well-known porous structure isolation membrane with good chemical stability and mechanical stability can be used.
- the material of the isolation membrane can be selected from at least one of glass fiber, non-woven fabric, polyethylene, polypropylene and polyvinylidene fluoride.
- the isolation film can be a single-layer film or a multi-layer composite film, with no special restrictions. When the isolation film is a multi-layer composite film, the materials of each layer can be the same or different, and there is no particular limitation.
- the positive electrode piece, the negative electrode piece and the separator film can be made into an electrode assembly through a winding process or a lamination process.
- the secondary battery may include an outer packaging.
- the outer packaging can be used to package the above-mentioned electrode assembly and electrolyte.
- the outer packaging of the secondary battery may be a hard shell, such as a hard plastic shell, an aluminum shell, a steel shell, etc.
- the outer packaging of the secondary battery may also be a soft bag, such as a bag-type soft bag.
- the material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
- FIG. 2 shows a square-structured secondary battery 5 as an example.
- the outer package may include a housing 51 and a cover 53 .
- the housing 51 may include a bottom plate and side plates connected to the bottom plate, and the bottom plate and the side plates enclose a receiving cavity.
- the housing 51 has an opening communicating with the accommodation cavity, and the cover plate 53 can cover the opening to close the accommodation cavity.
- the positive electrode piece, the negative electrode piece and the isolation film can be formed into the electrode assembly 52 through a winding process or a lamination process.
- the electrode assembly 52 is packaged in the containing cavity.
- the electrolyte soaks into the electrode assembly 52 .
- the number of electrode assemblies 52 contained in the secondary battery 5 can be one or more, and those skilled in the art can select according to specific actual needs.
- secondary batteries can be assembled into battery modules, and the number of secondary batteries contained in the battery module can be one or more. The specific number can be selected by those skilled in the art according to the application and capacity of the battery module.
- FIG. 4 is a battery module 4 as an example.
- a plurality of secondary batteries 5 may be arranged in sequence along the length direction of the battery module 4 .
- the plurality of secondary batteries 5 can be fixed by fasteners.
- the battery module 4 may further include a housing having a receiving space in which a plurality of secondary batteries 5 are received.
- the above-mentioned battery modules can also be assembled into a battery pack.
- the number of battery modules contained in the battery pack can be one or more. Those skilled in the art can select the specific number according to the application and capacity of the battery pack.
- the battery pack 1 may include a battery box and a plurality of battery modules 4 disposed in the battery box.
- the battery box includes an upper box 2 and a lower box 3 .
- the upper box 2 can be covered with the lower box 3 and form a closed space for accommodating the battery module 4 .
- Multiple battery modules 4 can be arranged in the battery box in any manner.
- the present application also provides an electrical device, which includes at least one of the secondary battery, battery module, or battery pack provided by the present application.
- the secondary battery, battery module, or battery pack can be used as a power source for the power-consuming device, or as an energy storage unit of the power-consuming device.
- Electric devices may include mobile devices (such as mobile phones, laptops, etc.), electric vehicles (such as pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric Trucks, etc.), electric trains, ships and satellites, energy storage systems, etc., but are not limited to these.
- secondary batteries, battery modules or battery packs can be selected according to its usage requirements.
- Fig. 7 is an electrical device as an example.
- the electric device is a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, etc.
- a battery pack or battery module can be used.
- Step S1 Preparation of Fe, Co, V and S co-doped manganese oxalate
- Step S2 Preparation of core Li 0.997 Mn 0.60 Fe 0.393 V 0.004 Co 0.003 P 0.997 S 0.003 O 4
- Step S3 Preparation of the first coating layer suspension
- Li 2 FeP 2 O 7 solution Dissolve 7.4g lithium carbonate, 11.6g ferrous carbonate, 23.0g ammonium dihydrogen phosphate and 12.6g oxalic acid dihydrate in 500mL deionized water, control the pH to 5, then stir and keep at room temperature The reaction was carried out for 2 hours to obtain a solution, and then the temperature of the solution was raised to 80°C and maintained at this temperature for 4 hours to obtain a first coating layer suspension.
- Step S4 Coating of the first coating layer
- step S2 Add 1571.9g of the doped lithium manganese phosphate core material obtained in step S2 to the first coating layer suspension (coating material content is 15.7g) obtained in step S3, stir and mix thoroughly for 6 hours, and mix evenly Finally, it was transferred to an oven at 120°C for drying for 6 hours, and then sintered at 650°C for 6 hours to obtain the pyrophosphate-coated material.
- Step S5 Preparation of the second coating layer suspension
- Step S6 Coating of the second coating layer
- step S4 Add 1586.8g of the pyrophosphate-coated material obtained in step S4 to the second coating layer suspension obtained in step S5 (coating material content is 47.1g), stir and mix thoroughly for 6 hours, and mix evenly Finally, it was transferred to an oven at 120°C for drying for 6 hours, and then sintered at 700°C for 8 hours to obtain a two-layer coated material.
- Step S7 Preparation of the third coating layer aqueous solution
- sucrose aqueous solution Dissolve 37.3g of sucrose in 500g of deionized water, then stir and fully dissolve to obtain a sucrose aqueous solution.
- Step S8 Coating of the third coating layer
- step S6 Add 1633.9g of the two-layer coating material obtained in step S6 to the sucrose solution obtained in step S7, stir and mix together for 6 hours. After mixing evenly, transfer to a 150°C oven to dry for 6 hours, and then sinter at 700°C for 10 hours. A three-layer coated material is obtained.
- the cathode active materials of Examples 2 to 56 and Comparative Examples 1 to 17 were prepared in a method similar to Example 1. The differences in the preparation of the cathode active materials are shown in Tables 1-6.
- Comparative Examples 1-2, 4-10 and 12 are not coated with the first layer, so there are no steps S3-S4; Comparative Example 1-11 is not coated with the second layer, so there are no steps S5-S6.
- the three-layer-coated cathode active material prepared above, the conductive agent acetylene black, and the binder polyvinylidene fluoride (PVDF) were added to N-methylpyrrolidone (NMP) in a weight ratio of 97.0:1.2:1.8 , stir and mix evenly to obtain the positive electrode slurry. Then, the positive electrode slurry is evenly coated on the aluminum foil at a density of 0.280g/ 1540.25mm2 , dried, cold pressed, and cut to obtain the positive electrode piece.
- NMP N-methylpyrrolidone
- the mass ratio of the negative active material artificial graphite, conductive agent superconducting carbon black (Super-P), binder styrene-butadiene rubber (SBR), and thickener sodium carboxymethylcellulose (CMC-Na) is 95%: Dissolve 1.5%: 1.8%: 1.7% in deionized water, stir thoroughly and mix evenly to obtain a negative electrode slurry with a viscosity of 3000 mPa.s and a solid content of 52%; coat the negative electrode slurry on a 6 ⁇ m negative electrode current collector copper foil , then baked at 100°C for 4 hours to dry, and rolled to obtain a negative electrode piece with a compacted density of 1.75g/cm3.
- the positive electrode piece, isolation film, and negative electrode piece obtained above are stacked in order, so that the isolation film is between the positive and negative electrodes to play an isolation role, and the bare battery core is obtained by winding.
- the bare battery core is placed in the outer packaging, the above-mentioned electrolyte is injected and packaged to obtain a full battery (hereinafter also referred to as "full battery").
- the positive active material sample is prepared into a buckle, and the above buckle is charged at a small rate of 0.05C until the current is reduced to 0.01C. Then take out the positive electrode piece from the battery and soak it in dimethyl carbonate (DMC) for 8 hours. Then it is dried, scraped into powder, and particles with a particle size less than 500nm are screened out. Take a sample and calculate its unit cell volume v1 in the same way as the above-mentioned test of fresh samples, and use (v0-v1)/v0 ⁇ 100% as the lattice change rate (unit cell volume change rate) before and after complete deintercalation of lithium.
- DMC dimethyl carbonate
- the fresh full batteries prepared in the above examples and comparative examples were allowed to stand for 5 minutes, and then discharged to 2.5V at 1/3C. Let it stand for 5 minutes, charge at 1/3C to 4.3V, and then charge at a constant voltage of 4.3V until the current is less than or equal to 0.05mA. Let it stand for 5 minutes, and record the charging capacity at this time as C0. Discharge to 2.5V according to 1/3C, let it sit for 5 minutes, then charge to 4.3V according to 3C, let it stand for 5 minutes, record the charging capacity at this time as C1.
- the 3C charging constant current ratio is C1/C0 ⁇ 100%.
- the full battery made of the positive electrode active material of each of the above embodiments and comparative examples was discharged to a cut-off voltage of 2.0V using a 0.1C rate. Then disassemble the battery, take out the negative electrode piece, randomly pick 30 discs of unit area (1540.25mm 2 ) on the negative electrode piece, and use Agilent ICP-OES730 to test the inductively coupled plasma emission spectrum (ICP). Calculate the amounts of Fe (if the Mn site of the cathode active material is doped with Fe) and Mn based on the ICP results, and then calculate the dissolution amount of Mn (and Fe doped at the Mn site) after cycles. The test standard is based on EPA-6010D-2014.
- the cathode active material sample prepared above Take 5 g of the cathode active material sample prepared above and prepare a buckle according to the above preparation method of buckle. Charge with a small rate of 0.05C until the current is reduced to 0.01C. Then take out the positive electrode piece from the battery and soak it in DMC for 8 hours. Then it is dried, scraped into powder, and particles with a particle size less than 500nm are screened out. The obtained particles were measured with electron energy loss spectroscopy (EELS, the instrument model used was Talos F200S) to obtain the energy loss near-edge structure (ELNES), which reflects the density of states and energy level distribution of the element. According to the density of states and energy level distribution, the number of occupied electrons is calculated by integrating the valence band density of states data, thereby deducing the valence state of the charged surface oxygen.
- EELS electron energy loss spectroscopy
- Dissolve 5g of the positive active material prepared above in 100ml aqua regia (concentrated hydrochloric acid: concentrated nitric acid 1:3) (concentrated hydrochloric acid concentration ⁇ 37%, concentrated nitric acid concentration ⁇ 65%), and use ICP to test the content of each element of the solution. content, and then measure and convert the content of manganese element or phosphorus element (amount of manganese element or phosphorus element/amount of cathode active material * 100%) to obtain its weight ratio.
- the button batteries prepared in the above examples and comparative examples were charged to 4.3V at 0.1C, then charged at a constant voltage at 4.3V until the current was less than or equal to 0.05mA, left to stand for 5 minutes, and then charged at 0.1 C is discharged to 2.0V.
- the discharge capacity at this time is the initial gram capacity, recorded as D0.
- the full cells prepared in each of the above-described Examples and Comparative Examples were stored at 60° C. at 100% state of charge (SOC). Measure the open circuit voltage (OCV) and AC internal resistance (IMP) of the battery cells before, after and during storage to monitor SOC, and measure the volume of the battery cells. The full battery was taken out after every 48 hours of storage, and the open circuit voltage (OCV) and internal resistance (IMP) were tested after leaving it for 1 hour. After cooling to room temperature, the cell volume was measured using the drainage method.
- SOC state of charge
- the drainage method is to first separately measure the gravity F 1 of the battery cell using a balance that automatically converts units based on the dial data, then completely places the battery core in deionized water (density is known to be 1g/cm 3 ), and measures the battery core at this time.
- the thickness test of the coating layer mainly uses FIB to cut a slice with a thickness of about 100nm from the middle of a single particle of the cathode active material prepared above, and then perform a TEM test on the slice to obtain the original TEM test picture and save the original picture format (xx.dm3) .
- the thickness of the selected particles was measured at three locations and averaged.
- This test is performed by Raman spectroscopy. By peak splitting the energy spectrum of the Raman test, Id/Ig is obtained, where Id is the peak intensity of SP3 form carbon, and Ig is the peak intensity of SP2 form carbon, thereby confirming the molar ratio of the two.
- ACSTEM Spherical aberration electron microscopy
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Abstract
Description
Claims (22)
- 一种具有核-壳结构的正极活性材料,其包括内核及包覆所述内核的壳,所述内核包含Li 1+xMn 1-yA yP 1-zR zO 4,其中,所述x为-0.100-0.100范围内的任意数值,所述y为0.001-0.600范围内的任意数值,所述z为0.001-0.100范围内的任意数值,所述A为选自Zn、Al、Na、K、Mg、Mo、W、Ti、V、Zr、Fe、Ni、Co、Ga、Sn、Sb、Nb和Ge中的一种或多种元素、可选地为选自Fe、V、Ni、Co和Mg中一种或多种元素,所述R为选自B、Si、N和S中的一种或多种元素、可选地为选自Si、N和S中的一种或多种元素;所述壳包括包覆所述内核的第一包覆层、包覆所述第一包覆层的第二包覆层以及包覆所述第二包覆层的第三包覆层,其中,所述第一包覆层包含晶态焦磷酸盐Li aMP 2O 7和/或M b(P 2O 7) c,其中,所述a大于0且小于或等于2,所述b为1-4范围内的任意数值,所述c为1-3范围内的任意数值,所述晶态焦磷酸盐Li aMP 2O 7和M b(P 2O 7) c中的M各自独立地为选自Fe、Ni、Mg、Co、Cu、Zn、Ti、Ag、Zr、Nb和Al中的一种或多种元素、可选地为选自Fe、Ni、Mg、Co、Cu、Zn、Ti、Ag、Zr和Al中的一种或多种元素;所述第二包覆层包含晶态氧化物M′ dO e,其中,所述d大于0且小于或等于2,所述e大于0且小于或等于5,所述M′为选自碱金属、碱土金属、过渡金属、第IIIA族元素、第IVA族元素、镧系元素和Sb中的一种或多种元素,可选地为选自Li、Be、B、Na、Mg、Al、Si、P、S、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、As、Se、Sr、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Cd、In、Sn、Sb、Te、W、La和Ce中的一种或多种元素,更可选地为选自Mg、Al、Si、Ti、V、Ni、Cu、Zr和W中的一种或多种元素;所述第三包覆层包含碳。
- 根据权利要求1所述的正极活性材料,其中,在所述内核中, y与1-y的比值为1:10至1:1,可选为1:4至1:1。
- 根据权利要求1或2所述的正极活性材料,其中,在所述内核中,z与1-z的比值为1:9至1:999,可选为1:499至1:249。
- 根据权利要求1-3中任一项所述的正极活性材料,其中,所述第三包覆层中的碳为SP2形态碳与SP3形态碳的混合物;可选地,所述SP2形态碳与SP3形态碳的摩尔比为0.07-13范围内的任意数值,更可选为0.1-10范围内的任意数值,进一步可选为2.0-3.0范围内的任意数值。
- 根据权利要求1-4中任一项所述的正极活性材料,其中,所述第一包覆层的包覆量为大于0且小于或等于6重量%,可选为大于0且小于或等于5.5重量%,更可选为大于0且小于或等于2重量%,基于所述内核的重量计;和/或所述第二包覆层的包覆量为大于0且小于或等于6重量%,可选为大于0且小于或等于5.5重量%,更可选为2重量%-4重量%,基于所述内核的重量计;和/或所述第三包覆层的包覆量为大于0且小于或等于6重量%,可选为大于0且小于或等于5.5重量%,更可选为大于0且小于或等于2重量%,基于所述内核的重量计。
- 根据权利要求1-5中任一项所述的正极活性材料,其中,所述第一包覆层的厚度为2-10nm;和/或所述第二包覆层的厚度为3-15nm;和/或所述第三包覆层的厚度为5-25nm。
- 根据权利要求1-6中任一项所述的正极活性材料,其中,所述第一包覆层中的晶态焦磷酸盐的晶面间距范围为0.293-0.470nm,晶向(111)的夹角范围为18.00°-32.00°;可选地,所述第一包覆层中的晶态焦磷酸盐的晶面间距范围为0.297-0.462nm;和/或,可选地,所述第一包覆层中的晶态焦磷酸盐的晶向(111)的夹角范围为19.211°-30.846°。
- 根据权利要求1-7中任一项所述的正极活性材料,其中,基于正极活性材料的重量计,锰元素含量在10重量%-35重量%范围内,可选在15重量%-30重量%范围内,更可选在17重量%-20重量%范围内,磷元素的含量在12重量%-25重量%范围内,可选在15重量%-20重量%范围内;可选地,锰元素和磷元素的重量比在0.90-1.25范围内,更可选为0.95-1.20范围内。
- 根据权利要求1-8中任一项所述的正极活性材料,其中,所述正极活性材料在完全脱嵌锂前后的晶格变化率为50%以下,可选为4%以下,更可选为3.8%以下,进一步可选为2.0%-3.8%。
- 根据权利要求1-9中任一项所述的正极活性材料,其中,所述正极活性材料的Li/Mn反位缺陷浓度为5.3%以下,可选为4%以下,更可选为2.2%以下,进一步可选为1.5%-2.2%。
- 根据权利要求1-10中任一项所述的正极活性材料,其中,所述正极活性材料在3T下的压实密度为1.95g/cm 3以上,可选为2.2g/cm 3以上,进一步可选为2.2g/cm 3以上且2.8g/cm 3以下,更进一步可选为2.2g/cm 3以上且2.65g/cm 3以下。
- 根据权利要求1-11中任一项所述的正极活性材料,其中,所述正极活性材料的表面氧价态为-1.89以下,可选地为-1.90至-1.98。
- 一种正极活性材料的制备方法,包括以下步骤:提供内核材料的步骤:所述内核材料包含Li 1+xMn 1-yA yP 1-zR zO 4,其中,所述x为-0.100-0.100范围内的任意数值,所述y为0.001-0.600范围内的任意数值,所述z为0.001-0.100范围内的任意数值,所述A为选自Zn、Al、Na、K、Mg、Mo、W、Ti、V、Zr、Fe、Ni、Co、Ga、Sn、Sb、Nb和Ge中的一种或多种元素、可选地为选自Fe、V、Ni、Co和Mg中一种或多种元素,所述R为选自B、Si、N和S中的一种或多种元素、可选地为选自Si、N和S中的一种或多种元素;第一包覆步骤:提供包含焦磷酸盐Li aMP 2O 7和/或M b(P 2O 7) c的第一混合物,将内核材料与第一混合物混合,干燥,烧结,得到第一包覆层包覆的材料;其中,所述a大于0且小于或等于2,所述b为1-4范围内的任意数值,所述c为1-3范围内的任意数值;所述焦磷酸盐Li aMP 2O 7和M b(P 2O 7) c中的M各自独立地为选自Fe、Ni、Mg、Co、Cu、Zn、Ti、Ag、Zr、Nb和Al中的一种或多种元素、可选地为选自Fe、Ni、Mg、Co、Cu、Zn、Ti、Ag、Zr和Al中的一种或多种元素;第二包覆步骤:提供包含氧化物M′ dO e的第二混合物,将所述第一包覆层包覆的材料与第二混合物混合,干燥,烧结,得到两层包覆层包覆的材料;其中,所述d大于0且小于或等于2,所述e大于0且小于或等于5,所述M′为碱金属、碱土金属、过渡金属、第IIIA族元素、第IVA族元素、镧系元素和Sb中的一种或多种元素,可选地为选自Li、Be、B、Na、Mg、Al、Si、P、S、K、Ca、Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Zn、Ga、Ge、As、Se、Sr、Y、Zr、Nb、Mo、Tc、Ru、Rh、Pd、Ag、Cd、In、Sn、Sb、Te、W、La和Ce中的一种或多种元素,更可选地为选自Mg、Al、Si、Ti、V、Ni、Cu、Zr和W中的一种或多种元素;第三包覆步骤:提供包含碳源的第三混合物,将所述两层包覆层包覆的材料与第三混合物混合,干燥,烧结,得到正极活性材料;其中,所述正极活性材料具有核-壳结构,其包括所述内核及包覆所述内核的壳,所述内核包含Li 1+xMn 1-yA yP 1-zR zO 4,所述壳包括包覆所述内核的第一包覆层、包覆所述第一包覆层的第二包覆层以及包 覆所述第二包覆层的第三包覆层,所述第一包覆层包含晶态焦磷酸盐Li aMP 2O 7和/或M b(P 2O 7) c,所述第二包覆层包含晶态氧化物M′ dO e,所述第三包覆层包含碳。
- 根据权利要求13所述的制备方法,所述提供内核材料的步骤包括以下步骤:步骤(1):将锰源、元素A的源和酸混合,得到混合物;步骤(2):将所述步骤(1)得到的混合物与锂源、磷源、元素R的源及可选的溶剂混合,在惰性气体保护下烧结,得到包含Li 1+xMn 1-yA yP 1-zR zO 4的内核材料;可选地,所述步骤(1)在20℃-120℃、更可选为在40℃-120℃下进行;和/或,所述步骤(1)中,通过以400-700rpm转速搅拌1-9h进行混合;可选地,所述步骤(2)中,在20-120℃、可选为40-120℃的温度下混合1-10h。
- 根据权利要求13或14所述的制备方法,其中,所述第一包覆步骤中,通过将元素M的源、磷源、酸、任选的锂源和任选的溶剂混合得到所述第一混合物;和/或,所述第二包覆步骤中,通过将元素M′的源与溶剂混合得到第二混合物;和/或,所述第三包覆步骤中,通过将碳源与溶剂混合得到第三混合物;可选地,所述第一包覆步骤中,所述元素M的源、磷源、酸、任选的锂源和任选的溶剂在室温下混合1-5h,再升温至50℃-120℃并保持该温度混合2-10h,上述混合均在pH为3.5-6.5条件下进行;可选地,所述第二包覆步骤中,所述元素M′的源与溶剂在室温下混合1-10h,再升温至60℃-150℃并保持该温度混合2-10h。
- 根据权利要求13-15中任一项所述的制备方法,其中,所述元素A的源为选自元素A的单质、碳酸盐、硫酸盐、卤化 物、硝酸盐、有机酸盐、氧化物和氢氧化物中的一种或多种;和/或,所述元素R的源为选自元素R的无机酸、有机酸、硫酸盐、卤化物、硝酸盐、有机酸盐、氧化物和氢氧化物中的一种或多种。
- 根据权利要求13-16中任一项所述的制备方法,其中,所述第一包覆步骤中,所述烧结在650-800℃下进行2-8小时;和/或,所述第二包覆步骤中,所述烧结在400-750℃下进行6-10小时;和/或,所述第三包覆步骤中,所述烧结在600-850℃下进行6-10小时。
- 一种正极极片,其包括正极集流体以及设置在正极集流体至少一个表面的正极膜层,所述正极膜层包括权利要求1-12中任一项所述的正极活性材料或通过权利要求13-17中任一项所述的制备方法制备的正极活性材料;可选地,所述正极活性材料在所述正极膜层中的含量为90-99.5重量%,更可选为95-99.5重量%,基于所述正极膜层的总重量计。
- 一种二次电池,包括权利要求1-12中任一项所述的正极活性材料或者通过权利要求13-17中任一项所述的制备方法制备的正极活性材料或者权利要求18所述的正极极片。
- 一种电池模块,其包括权利要求19所述的二次电池。
- 一种电池包,其包括权利要求20所述的电池模块。
- 一种用电装置,其包括选自权利要求19所述的二次电池、权利要求20所述的电池模块和权利要求21所述的电池包中的至少一种。
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EP22933866.0A EP4318655A1 (en) | 2022-06-17 | 2022-06-17 | Positive electrode active material and preparation method therefor, positive electrode sheet, secondary battery, battery module, battery pack and electrical device |
CN202280082206.6A CN118414724A (zh) | 2022-06-17 | 2022-06-17 | 正极活性材料及制备方法、正极极片、二次电池、电池模块、电池包及用电装置 |
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PCT/CN2022/099516 WO2023240613A1 (zh) | 2022-06-17 | 2022-06-17 | 正极活性材料及制备方法、正极极片、二次电池、电池模块、电池包及用电装置 |
KR1020247007998A KR20240046889A (ko) | 2021-10-22 | 2022-10-21 | 양극 활물질, 양극 극판, 이차 전지, 전지 모듈, 전지 팩 및 전기 장치 |
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EP22882998.2A EP4418363A1 (en) | 2021-10-22 | 2022-10-21 | Positive electrode active material, positive electrode sheet, secondary battery, battery module, battery pack, and electric device |
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PCT/CN2022/126838 WO2023066394A1 (zh) | 2021-10-22 | 2022-10-21 | 正极活性材料、正极极片、二次电池、电池模块、电池包和用电装置 |
US18/527,290 US20240294392A1 (en) | 2022-06-17 | 2023-12-03 | Positive electrode active material and preparation method thereof, positive electrode plate, secondary battery, battery module, battery pack, and electric apparatus |
US18/641,410 US20240282969A1 (en) | 2021-10-22 | 2024-04-21 | Positive electrode active material, positive electrode plate, secondary battery, battery module, battery pack and power consuming device |
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CN102931404A (zh) * | 2012-11-12 | 2013-02-13 | 复旦大学 | 磷位硼掺杂磷酸锰锂/碳复合材料及其制备方法 |
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