CN114927659B - Multielement positive electrode material, preparation method and application thereof - Google Patents
Multielement positive electrode material, preparation method and application thereof Download PDFInfo
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- CN114927659B CN114927659B CN202210492025.2A CN202210492025A CN114927659B CN 114927659 B CN114927659 B CN 114927659B CN 202210492025 A CN202210492025 A CN 202210492025A CN 114927659 B CN114927659 B CN 114927659B
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- electrode material
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 152
- 238000002360 preparation method Methods 0.000 title abstract description 44
- 239000002245 particle Substances 0.000 claims abstract description 242
- 239000013078 crystal Substances 0.000 claims abstract description 82
- 239000010405 anode material Substances 0.000 claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- 239000002243 precursor Substances 0.000 claims description 27
- 239000011572 manganese Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 238000005245 sintering Methods 0.000 claims description 21
- 229910052721 tungsten Inorganic materials 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052720 vanadium Inorganic materials 0.000 claims description 16
- 238000012360 testing method Methods 0.000 claims description 15
- 229910003002 lithium salt Inorganic materials 0.000 claims description 14
- 159000000002 lithium salts Chemical class 0.000 claims description 14
- 239000002019 doping agent Substances 0.000 claims description 13
- 239000008139 complexing agent Substances 0.000 claims description 12
- 150000001868 cobalt Chemical class 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
- 150000002815 nickel Chemical class 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- 229910052727 yttrium Inorganic materials 0.000 claims description 10
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 229910052715 tantalum Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000012716 precipitator Substances 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 39
- 238000005056 compaction Methods 0.000 abstract description 14
- 230000000295 complement effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000047 product Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000010406 cathode material Substances 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 229940044175 cobalt sulfate Drugs 0.000 description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229940053662 nickel sulfate Drugs 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001679 gibbsite Inorganic materials 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 2
- 229910001947 lithium oxide Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003571 electronic cigarette Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery anode materials, and discloses a multi-element anode material, a preparation method and application thereof. The multi-element positive electrode material comprises single crystal particles A and polycrystalline particles B; wherein the median particle diameter D 50(A) of the single crystal particles A is 2-6 mu m; the median diameter D 50(B) of the polycrystalline particles B is 2-6 mu m; the weight ratio of the monocrystalline particles A to the polycrystalline particles B is 1:9-9:1. The multi-element positive electrode material comprises small-particle-size monocrystalline particles A and small-particle-size polycrystalline particles B, wherein the monocrystalline particles A and the polycrystalline particles B have equivalent particle sizes, and the monocrystalline particles A and the polycrystalline particles B can realize complementary advantages, so that the multi-element positive electrode material formed by matching the two particles not only maintains the high pole piece compaction density, stable structure, excellent cycle performance and good safety of the monocrystalline material, but also has the advantages of high capacity and good power output of the small-particle polycrystalline material.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a multi-element anode material and a preparation method and application thereof.
Background
Currently, the lithium ion battery industry develops rapidly, and along with the development of electronic products, the market also puts higher demands on lithium ion power batteries, especially considering the energy density, high-current discharge and safety performance, and the cost is low. As is well known, the lithium cobaltate cathode material has high gram capacity and high compaction density, and excellent cycle performance, and particularly has high discharge capacity and high plateau during high-rate discharge, so that the lithium cobaltate cathode material is widely used as a power source of electronic cigarettes, electronic models, toys, wireless electric tools and small-sized electric appliances. However, cobalt resources are used as scarce resources, the price of the cobalt resources is always high, and the cost advantage is not obvious.
For the existing power type positive electrode material, the compressive strength is improved, the power output is improved, the safety performance of the material is guaranteed, and the method is an important development direction and has great significance for improving the performance of the nickel cobalt lithium manganate ternary lithium ion battery.
CN109888235A discloses a graded high nickel ternary positive electrode material, a preparation method and application thereof. The graded high-nickel ternary positive electrode material is prepared by mixing a high-nickel polycrystalline material and a ternary monocrystalline material, or mixing the mixture with a coating additive and sintering. Compared with single polycrystalline material, the prepared graded material has higher compaction and circulation stability, higher capacity than single monocrystal, and can effectively improve the problems of gas production and service life of the battery after graded modification. But the polycrystalline material is large particles, the compression resistance is poor, the problem of cracking balls can occur after the pole pieces are rolled, the long-term circulation stability is poor, and the large-particle power performance is poor.
Disclosure of Invention
The invention aims to solve the problems of poor power performance, low mechanical strength, poor thermal stability and poor cycle performance of a single crystal positive electrode material and a polycrystalline positive electrode material in the prior art, and provides a multi-element positive electrode material and a preparation method and application thereof. The multi-element positive electrode material comprises small-particle-size monocrystalline particles A and small-particle-size polycrystalline particles B, wherein the monocrystalline particles A and the polycrystalline particles B have equivalent particle sizes, and the monocrystalline particles A and the polycrystalline particles B can realize complementary advantages, so that the multi-element positive electrode material formed by matching the two particles not only maintains the high pole piece compaction density, stable structure, excellent cycle performance and good safety of the monocrystalline material, but also has the advantages of high capacity and good power output of the small-particle polycrystalline material.
In order to achieve the above object, a first aspect of the present invention provides a multi-component positive electrode material characterized in that the multi-component positive electrode material comprises single crystal particles a and polycrystalline particles B;
Wherein the median particle diameter D 50(A) of the single crystal particles A is 2-6 mu m; the median diameter D 50(B) of the polycrystalline particles B is 2-6 mu m;
the weight ratio of the monocrystalline particles A to the polycrystalline particles B is 1:9-9:1.
The second aspect of the present invention provides a method for preparing the multi-component positive electrode material, which is characterized in that the preparation method comprises:
and mixing the monocrystalline particles A with the polycrystalline particles B to obtain the multi-element positive electrode material.
The third aspect of the invention provides an application of the multi-element positive electrode material in a lithium ion battery.
Through the technical scheme, the multi-element positive electrode material provided by the invention and the preparation method and application thereof have the following beneficial effects:
(1) The multi-component positive electrode material contains monocrystalline particles A and polycrystalline particles B, the advantages of the monocrystalline particles A and the polycrystalline particles B are complementary, the median particle diameter D 50 (A) of the monocrystalline particles A is equivalent to the median particle diameter D 50 (B) of the polycrystalline particles B, and particularly, the difference of the median particle diameters of the monocrystalline particles A and the polycrystalline particles B is within 1 mu m. The monocrystal particle A positive electrode material has high mechanical strength, provides particle support after blending, can inhibit the breakage of polycrystal particles, reduces side reaction with electrolyte, and has stable material structure, good cycle performance and safety; the single crystal material has good compression resistance, and can improve the compaction density of the pole piece, thereby ensuring the capacity; the polycrystalline particle B positive electrode material is small-particle polycrystalline particles, the multiplying power performance of larger-particle polycrystalline particles and single-crystal particles is excellent, the power output is good, the particles with two structures are matched with each other, the high pole piece compaction density, the structure stability, the excellent cycle performance and the good safety of the single-crystal material are ensured, and meanwhile, the advantages of high capacity and good power output of the small-particle polycrystalline material are considered;
(2) The Ni content of the monocrystal grain A is higher than that of the polycrystal grain B, so that the charge and discharge depth and discharge capacity of the monocrystal A under small current are not lower than those of the polycrystal grain B. And under large current, the polycrystalline discharge capacity is higher, and the internal resistance of the polycrystalline causes heat generation, so that the single crystal can be heated and activated, more lithium ions are removed, the higher capacity is exerted, and the defect of low capacity of the single crystal is overcome.
(3) The performance of the multi-element positive electrode material has the characteristic of adjustability, and according to the application requirements of products, single crystal particles A and polycrystalline particles B can be mixed in different proportions, so that the power performance and the like of the material are exerted to the maximum extent, and the requirements of rapid charge and discharge of the material are met;
(4) In the method for preparing the multi-element positive electrode material, the coating additive is adopted, so that the defects on the surface of the positive electrode material can be repaired, the residual alkali quantity on the surface can be controlled, the stability of the structure can be enhanced, the side reaction between the multi-element positive electrode material and electrolyte can be reduced, the gas production rate can be reduced, and the safety of the battery can be improved. The synergistic effect of the composite anode material and the doping additive can further improve the structural stability, the cycle performance and the power performance of the multi-element anode material, and the method has strong controllability and low cost and is convenient for batch production.
Drawings
FIG. 1 is an SEM image of a precursor of a single crystal positive electrode material A prepared in example 1;
FIG. 2 is an SEM image of a precursor of a polycrystalline cathode material B prepared in example 1;
FIG. 3 is an SEM image of single crystal particles A prepared according to example 1;
FIG. 4 is an SEM image of polycrystalline pellets B prepared in example 1;
FIG. 5 is an SEM image of a multi-component positive electrode material prepared in example 1;
FIG. 6 is a graph showing the cycle performance of the multi-component positive electrode materials prepared in example 1 and comparative examples 1-2 at a 1C rate, wherein the test temperature was 45℃and the voltage range was 3-4.3V.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a multi-component positive electrode material, which is characterized in that the multi-component positive electrode material comprises single crystal particles A and polycrystalline particles B;
Wherein the median particle diameter D 50(A) of the single crystal particles A is 2-6 mu m; the median diameter D 50(B) of the polycrystalline particles B is 2-6 mu m;
the weight ratio of the monocrystalline particles A to the polycrystalline particles B is 1:9-9:1.
In the invention, the multi-element positive electrode material simultaneously comprises the single crystal particles A with small particle sizes and the polycrystalline particles B with small particle sizes, and the median particle size D 50(A) of the single crystal particles A is equivalent to the median particle size D 50(B) of the polycrystalline particles B, and the advantages of the single crystal particles A and the polycrystalline particles D 50(B) are complementary, so that the multi-element positive electrode material has a stable structure, and a positive plate prepared from the multi-element positive electrode material has high compaction density, so that a lithium ion battery comprising the multi-element positive electrode material has more excellent cycle performance and safety performance, and simultaneously has high battery capacity and excellent power output performance.
Specifically, the monocrystal particle A positive electrode material has high mechanical strength, provides particle support after blending, can inhibit the breakage of polycrystal particles, reduces side reaction with electrolyte, and has stable material structure, good cycle performance and safety; the single crystal material has good compression resistance, and can improve the compaction density of the pole piece, thereby ensuring the capacity; the polycrystalline particle B positive electrode material is small-particle polycrystalline particles, the multiplying power performance of larger-particle polycrystalline particles and single-crystal particles is excellent, the power output is good, and the mutual matching of the two structural particles not only maintains the high pole piece compaction density, stable structure, excellent cycle performance and good safety of the single-crystal material, but also has the advantages of high capacity and good power output of the small-particle polycrystalline material.
Further, the median diameter D 50(A) of the single crystal particles A is 3 to 5 μm.
Further, the median diameter D 50(B) of the polycrystalline particles B is 3 to 5 μm.
Further, the weight ratio of the monocrystalline particles A to the polycrystalline particles B is 2:8-8:2.
According to the invention, the median particle diameter D 50 of the multi-element positive electrode material is 2-6 mu m.
In the invention, when the median particle diameter of the multi-element positive electrode material provided by the invention meets the range, the multi-element positive electrode material has good multiplying power performance.
Further, the median particle diameter D 50 of the multi-element positive electrode material is 3-5 mu m.
According to the present invention, the absolute value of the difference between the median diameter D 50(A) of the single crystal grains A and the median diameter D 50(B) of the polycrystalline grains B is 1 μm or less.
According to the invention, when the absolute value of the difference between the median particle diameters of the monocrystalline particles A and the polycrystalline particles B meets the above range, the mechanical strength of the multi-element positive electrode material can be further improved, the side reaction with the electrolyte is reduced, the structural stability of the multi-element positive electrode material is improved, the multi-element positive electrode material is ensured to have excellent compression resistance, the positive electrode sheet prepared from the multi-element positive electrode material has high compaction density, and further the lithium ion battery containing the multi-element positive electrode material has more excellent cycle performance and safety performance, and simultaneously has high battery capacity, excellent power output performance and rate capability.
Further, the absolute value of the difference between the median diameter D 50(A) of the single crystal grains A and the median diameter D 50(B) of the polycrystalline grains B is 0.8 μm or less.
According to the invention, the single crystal particles A have a specific surface area S A of 0.4-1m 2/g.
In the present invention, when the specific surface area of the single crystal particle a satisfies the above range, the single crystal particle size is moderate, and not only can a high discharge capacity be exhibited, but also good structural stability can be obtained.
Further, the specific surface area S A of the single crystal particle A is 0.5-0.9m 2/g.
According to the invention, the polycrystalline granules B have a specific surface area S B of 0.9-2m 2/g.
In the invention, when the specific surface area of the polycrystalline particles B meets the range, the polycrystalline particles have good rate capability and stable structure.
Further, the specific surface area S B of the polycrystalline particles B is 1.1-1.6m 2/g.
According to the invention, the monocrystalline particles a have a composition represented by formula I:
Li 1+a1(Nix1Coy1Mnz1M1m1)J1j1O2 formula I;
Wherein ,-0.1≤a1≤0.1,0＜x1＜1,0＜y1≤0.4,0＜z1≤0.6,0≤m1≤0.1,0≤j1≤0.02;M1 is an element selected from at least one of Ta, cr, mo, W, la, al, Y, ti, zr, V, nb, ce, er, mg, sr, ba and B; j 1 is at least one element selected from W, mo, zr, al, V, ti, B, co and Nb.
Further ,0.01≤a1≤0.08,0.3＜x1＜1,0.01＜y1≤0.3,0.01＜z1≤0.5,0≤m1≤0.05,0≤j1≤0.015;M1 an element selected from at least one of Cr, mo, W, la, al, Y, ti and Zr; j 1 is at least one element selected from W, mo, zr, al and Ti.
According to the invention, the polycrystalline granules B have a composition of formula II:
li 1+a2(Nix2Coy2Mnz2M2m2)J2j2O2 formula II;
Wherein ,-0.1≤a2≤0.1,0＜x2＜1,0＜y2≤0.4,0＜z2≤0.6,0≤m2≤0.1,0≤j2≤0.02;M2 is an element selected from at least one of Ta, cr, mo, W, la, al, Y, ti, zr, V, nb, ce, er, mg, sr, ba and B; j 2 is an element selected from at least one of W, mo, zr, al, V, ti, B, co and Nb.
Further ,0.01≤a2≤0.08,0.3＜x2＜1,0.01＜y2≤0.3,0.01＜z2≤0.5,0≤m2≤0.05,0≤j2≤0.015;M2 an element selected from at least one of Cr, mo, W, la, al, Y, ti and Zr; j 2 selects an element of at least one of W, mo, zr, al and Ti.
According to the invention x 1＞x2.
In the invention, the Ni content in the monocrystalline particles A is controlled to be higher than that in the polycrystalline particles B, namely x 1＞x2, so that the charge-discharge depth and discharge capacity of the monocrystalline particles A under a small current can be ensured to be not lower than those of the polycrystalline particles B. Under large current, the discharge capacity of the polycrystalline particles is higher, and the internal impedance of the polycrystalline particles causes heating, so that the monocrystalline particles can be heated to activate the monocrystalline particles, more lithium ions are removed, the higher capacity is exerted, and the defect of low capacity of the monocrystalline particles is overcome.
Further, x 1-x2 is 0.01 to 0.1, more preferably 0.01 to 0.05.
According to the invention, the specific surface area of the multi-element positive electrode material is S 0, and after 4.5T pressure fracturing, the specific surface area of the multi-element positive electrode material is S 1;
wherein, (S 1-S0)/S0.
In the invention, when the specific surface areas of the multi-element positive electrode material before and after pressure fracturing meet the range, the mechanical strength of the material is high, and the positive electrode material is not easy to fracture in the pole piece manufacturing process, so that the material has good electrochemical performance.
Further, (S 1-S0)/S0 x 100% is 10-150%.
According to the invention, the particle size corresponding to 5% of the volume distribution of the multi-element positive electrode material obtained by the particle size test is D 5 0, and the particle size corresponding to 5% of the volume distribution of the multi-element positive electrode material obtained by the particle size test after pressure fracturing of 4.5T is D 5 1;
Wherein, (D 5 0-D5 1)/D5 0 X100) is 1-30%.
In the invention, when the granularity corresponding to 5% of volume distribution of the multi-element positive electrode material before and after pressure fracturing meets the range, the positive electrode material has high mechanical strength, the positive electrode material is not easy to fracture in the pole piece manufacturing process, and fine powder is not easy to be discharged under strong pressure, so that the material has good processing performance and electrochemical performance.
Further, (D 5 0-D5 1)/D5 0 X100% is 1-25%.
According to the invention, the performance of the multi-element positive electrode material has the characteristic of adjustability, and according to the application requirements of products, monocrystalline particles A and polycrystalline particles B can be mixed in different proportions, so that the power performance of the material is maximally exerted, and the like, and the requirements of rapid charge and discharge of the material are met.
In one specific embodiment of the present invention, when the weight ratio of the single crystal grain a to the polycrystalline grain B is 1.1 to 9:1, the multi-component positive electrode material satisfies at least one of the following conditions:
(i)0.5≤S0≤1.2m2/g；
(ii)(S1-S0)/S0×100％≤120％；
(iii) (D 5 0-D5 1)/D5 0 X100% is 1-15%;
(iv)0≤(S0-SA)/SA×100％≤50％；
wherein S A is the specific surface area of the single crystal particle a.
In the invention, when the weight ratio of the monocrystalline particles A to the polycrystalline particles B in the multi-element positive electrode material meets the above range, namely, the content of the monocrystalline particles A in the multi-element positive electrode material is more than that of the polycrystalline particles B, and the multi-element positive electrode material meets at least one of the above conditions, the multi-element positive electrode material has stable structure and good cycle performance and thermal stability.
Further, the multi-element positive electrode material satisfies at least one of the following conditions:
(i)0.5≤S0≤1m2/g；
(ii) (S 1-S0)/S0 X100% is 10-100%;
(iii) (D 5 0-D5 1)/D5 0 X100% is 1-10%;
(iv)0≤(S0-SA)/SA×100％≤30％；
wherein S A is the specific surface area of the single crystal particle a.
In one embodiment of the present invention, when the weight ratio of the single crystal grain a to the polycrystalline grain B satisfies 1:1.1-9, the multi-component positive electrode material satisfies at least one of the following conditions:
(1)0.8≤S0≤1.4m2/g；
(ii)(S1-S0)/S0×100％≤200％；
(iii) (D 5 0-D5 1)/D5 0 X100% is 10-30%;
(iv)0≤(SB-S0)/SB×100％≤50％；
Wherein S B is the specific surface area of the polycrystalline particle B.
In the present invention, when the weight ratio of the single crystal particles a to the polycrystalline particles B in the multi-component positive electrode material satisfies the above range, that is, the multi-component positive electrode material has a content of the polycrystalline particles B more than that of the single crystal particles a, and the multi-component positive electrode material satisfies at least one of the above conditions, the multi-component positive electrode material has good rate performance.
Further, the multi-element positive electrode material satisfies at least one of the following conditions:
(1)1≤S0≤1.3m2/g；
(ii) (S 1-S0)/S0 X100% is 90-180%;
(iii) (D 5 0-D5 1)/D5 0 X100% is 10-25%;
(iv)0≤(SB-S0)/SB×100％≤30％；
Wherein S B is the specific surface area of the polycrystalline particle B.
The second aspect of the present invention provides a method for preparing the multi-component positive electrode material, which is characterized in that the preparation method comprises:
and mixing the monocrystalline particles A with the polycrystalline particles B to obtain the multi-element positive electrode material.
In the present invention, the sources of the single crystal grains a and the polycrystalline grains B are not particularly limited, and may be commercially available or self-made.
In order to further secure excellent electrochemical performance of the multi-component positive electrode material, it is preferable that the single crystal particles a and the polycrystalline particles B are prepared according to the preparation method provided by the present invention. So long as the median particle diameter of the single crystal particles a and the polycrystalline particles B is ensured to satisfy the requirements of the present invention.
Monocrystalline particles A
According to the invention, the monocrystalline particles a are prepared according to the following steps:
S1, mixing nickel salt, cobalt salt, manganese salt, a first precipitator and a first complexing agent in the presence of a solvent, adding the mixture into a reaction kettle for a first continuous reaction, and performing filter pressing, washing and drying to obtain a precursor of a monocrystal anode material A;
S2, mixing the precursor of the single crystal positive electrode material A with a first lithium salt and a first doping agent M 1, and obtaining a process product of the single crystal positive electrode material A through first sintering, crushing and screening;
s3, performing second sintering on the process product of the monocrystalline anode material A and a first coating agent J 1 to obtain monocrystalline particles A;
Wherein M 1 is at least one element selected from Ta, cr, mo, W, la, al, Y, ti, zr, V, nb, ce, er, mg, sr, ba and B, and J 1 is at least one element selected from W, mo, zr, al, V, ti, B, co and Nb.
According to the preparation method provided by the invention, the monocrystalline particles A are prepared by coating the process product of the monocrystalline positive electrode material A by adopting the first coating agent, so that the defects on the surface of the positive electrode material can be repaired, the residual alkali quantity on the surface is controlled, the stability of the structure is enhanced, meanwhile, the side reaction between the multi-element positive electrode material and electrolyte is reduced, the gas production rate is reduced, the safety of the battery is improved, and the structural stability, the cycle performance and the power performance of the multi-element positive electrode material can be further improved by the mutual cooperation of the multi-element positive electrode material and the first doping agent introduced in the process product preparation process of the positive electrode material.
Furthermore, the preparation method of the monocrystalline particles A provided by the invention has strong controllability and low cost, and is convenient for batch production.
In some embodiments of the present invention, the first lithium salt is used in an amount of 0.9.ltoreq.n (Li)/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.1.1, more preferably, the first lithium salt is used in an amount of 1.01.ltoreq.n (Li) ]/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.1.08.
In some embodiments of the present invention, in order to obtain a precursor of the single crystal cathode material a, preferably, in step S1, the first continuous reaction includes: the temperature is 40-80 ℃, the time is 5-40h, the rotating speed is 300-900rpm, and the pH is 10-13.
In some embodiments of the present invention, it is preferable that the precursor of the single crystal positive electrode material a has a median particle diameter D 50 of 2 to 6 μm and a specific surface area of 5 to 25m 2/g.
In some embodiments of the present invention, preferably, in step S2, the first sintering is performed in an air or oxygen atmosphere, and the conditions of the first sintering include: the temperature is 600-1100 ℃ and the time is 6-30h.
In some embodiments of the present invention, preferably, in step S3, the second sintering is performed in an air or oxygen atmosphere, and conditions of the second sintering include: the temperature is 200-900 ℃ and the time is 6-30h.
In some embodiments of the present invention, preferably, in step S1, the nickel salt, the cobalt salt, and the manganese salt are each independently selected from at least one of sulfate, chloride, nitrate, and acetate, for example, the nickel salt may be selected from at least one of nickel sulfate, nickel chloride, nickel nitrate, and nickel acetate; the cobalt salt may be selected from at least one of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese salt may be selected from at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
In some embodiments of the present invention, preferably, in step S1, the nickel salt, the cobalt salt, and the manganese salt are used in such an amount that n (Ni): n (Co) =x 1:y1:z1.
In some embodiments of the invention, preferably, the first precipitant is selected from sodium hydroxide and/or potassium hydroxide; the first complexing agent is selected from at least one of ammonia water, disodium ethylenediamine tetraacetate, ammonium nitrate, ammonium chloride and ammonium sulfate.
In some embodiments of the invention, the first precipitant and the first complexing agent are used in amounts such that the pH of the system is between 10 and 13 when the first continuous reaction is carried out in step S1.
In some embodiments of the present invention, in step S2, the first lithium salt may be various conventional lithium salts in the art. For example, the first lithium salt may be at least one selected from lithium carbonate, lithium hydroxide, lithium nitrate, and lithium oxide.
In some embodiments of the present invention, the first dopant refers to at least one of an oxide, a hydroxide, and a carbonate containing M 1 element, and for example, the first dopant may be selected from at least one of TiO2、ZrO2、Al2O3、Al(OH)3、Nb2O5、Y2O3、WO3、Ta2O5、V2O5、Cr2O3、MoO3、La2O3、CeO、Er2O3、MgO and B 2O3.
In some embodiments of the present invention, it is preferable that the amount of the first dopant M 1 in step S2 satisfies 0.ltoreq.n (M 1) ]/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.0.1, and more preferable that the amount of the first dopant M 1 satisfies 0.ltoreq.n (M 1) ]/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.0.05.
In some embodiments of the invention, the first coating agent comprises at least one J 1 selected from ZrO2、Al2O3、Al(OH)3、TiO2、V2O5、H3BO3、Co(OH)2 and WO 3.
In some embodiments of the present invention, in the step S3, the amount of the first coating agent satisfies 0.ltoreq.n (J 1) ]/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.0.02, more preferably, the amount of the first coating agent J 1 satisfies 0.ltoreq.n (J 1) ]/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.0.015, and it is possible to achieve just repairing defects on the surface of the particles while consuming residual alkali on part of the surface, and at the same time, prevent the coating amount from being excessively large, change the morphology of the surface of the particles, and affect the performance of the multi-component positive electrode material.
Polycrystalline grain B
According to the invention, the polycrystalline granules B are prepared according to the following steps:
(a) Mixing nickel salt, cobalt salt, manganese salt, a second precipitator and a second complexing agent in the presence of a solvent, adding the mixture into a reaction kettle for a second continuous reaction, and performing filter pressing, washing and drying to obtain a precursor of the polycrystalline anode material B;
(b) Mixing the precursor of the polycrystalline anode material B with a second lithium salt and a second doping agent M 2, and performing third sintering, crushing and screening to obtain a process product of the polycrystalline anode material B;
(c) Performing fourth sintering on the processed product of the polycrystalline anode material B and a second coating agent J 2 to obtain polycrystalline particles B;
wherein M 2 is at least one element selected from Ta, cr, mo, W, la, al, Y, ti, zr, V, nb, ce, er, mg, sr, ba and B, and J 2 is at least one element selected from W, mo, zr, al, V, ti, B, co and Nb.
In some embodiments of the present invention, the second lithium salt is used in an amount of 0.9.ltoreq.n (Li)/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.1.1, more preferably, the second lithium salt is used in an amount of 1.01.ltoreq.n (Li) ]/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.1.08.
In some embodiments of the present invention, in order to obtain a precursor of the polycrystalline cathode material B, preferably, in step (a), the second continuous reaction, the reaction conditions include: the temperature is 45-70 ℃, the time is 10-30h, the rotating speed is 300-900rpm, and the pH is 10.2-13.2.
In the present invention, preferably, the pH of the second continuous reaction is higher than the pH of the first continuous reaction.
In the invention, when the pH of the second continuous reaction is controlled to be higher than that of the first continuous reaction, the prepared polycrystalline particle precursor has compact structure, and the monocrystalline particle precursor has loose structure, so that the monocrystalline particles and the polycrystalline particles in the first aspect of the invention are obtained.
Further, the pH of the second continuous reaction is 0.1 to 2 higher than the pH of the first continuous reaction.
In some embodiments of the present invention, it is preferable that the precursor of the polycrystalline cathode material B has a median particle diameter D 50 of 2 to 6 μm and a specific surface area of 4 to 20m 2/g.
In some embodiments of the present invention, preferably, in step (b), the third sintering is performed in an air or oxygen atmosphere, provided that: the temperature is 500-1000 ℃ and the time is 6-30h.
In some embodiments of the present invention, preferably, in step (c), the fourth sintering is performed in an air or oxygen atmosphere, provided that: the temperature is 200-900 ℃ and the time is 6-30h.
In some embodiments of the present invention, preferably, in step (a), the nickel salt, the cobalt salt, and the manganese salt are each independently selected from at least one of sulfate, chloride, nitrate, and acetate, for example, the nickel salt may be selected from at least one of nickel sulfate, nickel chloride, nickel nitrate, and nickel acetate; the cobalt salt may be selected from at least one of cobalt sulfate, cobalt chloride, cobalt nitrate and cobalt acetate; the manganese salt may be selected from at least one of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
In some embodiments of the present invention, preferably, in step S1, the nickel salt, the cobalt salt, and the manganese salt are used in such an amount that n (Ni): n (Co) =x 2:y2:z2.
In some embodiments of the invention, preferably, the second precipitant is selected from sodium hydroxide and/or potassium hydroxide; the second complexing agent is selected from at least one of ammonia water, disodium ethylenediamine tetraacetate, ammonium nitrate, ammonium chloride and ammonium sulfate.
In some embodiments of the invention, the second precipitant and the second complexing agent are used in amounts such that the pH of the system is between 10.2 and 13.2 when step (a) is performed with the second continuous reaction.
In some embodiments of the present invention, in step (b), the second lithium salt may be various conventional lithium salts in the art, for example, the second lithium salt may be at least one selected from lithium carbonate, lithium hydroxide, lithium nitrate, and lithium oxide.
In some embodiments of the present invention, the second dopant refers to at least one of an oxide, a hydroxide, and a carbonate containing M 2 element, and for example, the first dopant may be selected from at least one of TiO2、ZrO2、Al2O3、AlPO4、AlCl3、Nb2O5、Y2O3、WO3、Ta2O5、V2O5、Cr2O3、MoO3、La2O3、CeO、Er2O3、MgO、 and B 2O3.
In some embodiments of the present invention, preferably, in the step (b), the amount of the first dopant M 2 satisfies 0.ltoreq.n (M 2) ]/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.0.1, more preferably, the amount of the first dopant M 2 satisfies 0.ltoreq.n (M 2) ]/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.0.05.
In some embodiments of the invention, the second coating agent comprises at least one J 2 selected from ZrO2、Al2O3、Al(OH)3、V2O5、TiO2、H3BO3、Co(OH)2 and WO 3.
In some embodiments of the present invention, in the step (c), the second coating agent J 2 is used in an amount of 0.ltoreq.n (J 2) ]/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.0.02, preferably, the second coating agent J 2 is used in an amount of 0.ltoreq.n (J 2) ]/[ n (Ni) +n (Co) +n (Mn) ].ltoreq.0.015, so that it can be ensured that the coating agent consumes a part of the residual alkali amount of the surface while just repairing the defect of the particle surface, and at the same time, the coating amount is prevented from being excessively large, the morphology of the particle surface is changed, and the performance of the multi-component positive electrode material is affected.
In some embodiments of the invention, the corresponding monocrystalline anode material A and the polycrystalline anode material B are prepared by controlling the conditions of the dosage of raw materials, the synthesis temperature, the stirring rotation speed, the pH, the lithium proportion, the sintering temperature, the sintering time and the like.
In some embodiments of the present invention, the preparation method of the single crystal grain a and the polycrystalline grain B preferably further includes post-treatment means known in the art, such as suction filtration, washing, drying, crushing, sieving, etc., which will not be described herein, and those skilled in the art should not understand the limitation of the present invention.
The third aspect of the invention provides an application of the multi-element positive electrode material in a lithium ion battery.
The present invention will be described in detail by examples.
In the following examples, all materials were commercially available unless otherwise specified.
The room temperature according to the invention means 25.+ -. 2 ℃ unless otherwise specified.
In the following examples and comparative examples, the relevant parameters were tested by the following methods:
(1) Morphology testing: obtained by a scanning electron microscope test of model S-4800 of Hitachi CHI, japan;
(2) Median particle diameter D 50: is tested by a Marvern Hydro 2000mu model laser particle sizer;
(3) Specific surface test: is obtained by a specific surface meter test of a model Tristar 3020 of Micromeritics company;
(4) Compaction density: the test is carried out by a BT-30 tap density tester of the Baite company;
(5) Electrochemical performance test:
in the following examples and comparative examples, electrochemical performance of the multi-element positive electrode material was tested using 2025 type button cell.
The 2025 type button cell is prepared by the following steps:
Preparing a pole piece: a multi-component positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) were prepared according to a ratio of 95:3:2 and a proper amount of N-methyl pyrrolidone (NMP) are fully mixed to form uniform slurry, the slurry is coated on an aluminum foil and dried for 12 hours at 120 ℃, and then is subjected to stamping forming by using 100MPa pressure to prepare the positive electrode plate with the diameter of 12mm and the thickness of 120 mu m, wherein the loading capacity of the multi-element positive electrode material is 15-16mg/cm 2.
And (3) battery assembly: in an argon-filled glove box with water content and oxygen content less than 5ppm, assembling a positive electrode plate, a diaphragm, a negative electrode plate and electrolyte into a 2025 button cell, and standing for 6h. Wherein, the negative electrode plate uses a metal lithium plate with the diameter of 17mm and the thickness of 1 mm; the separator used was a polyethylene porous film (Celgard 2325) with a thickness of 25 μm; as the electrolyte, 1mol/L of an equivalent mixture of LiPF 6, ethylene Carbonate (EC) and diethyl carbonate (DEC) was used.
Electrochemical performance test:
In the following examples and comparative examples, electrochemical performance test was conducted on 2025 type button cell using a Shenzhen New Will cell test system, and the charge-discharge current density of 0.1C was 200mA/g.
And controlling the charge-discharge voltage interval to be 3.0-4.3V, and performing charge-discharge test on the button cell at the temperature of 0.1C at room temperature to evaluate the primary charge-discharge specific capacity and primary charge-discharge efficiency of the multi-element positive electrode material.
And (3) testing the cycle performance: the charge-discharge voltage interval is controlled to be 3.0-4.3V, the button cell is subjected to charge-discharge cycle for 2 times at 0.1C at the constant temperature of 45 ℃, then is subjected to charge-discharge cycle for 80 times at 1C, and the high Wen Rongliang retention rate of the multi-element positive electrode material is evaluated.
And (3) multiplying power performance test: the charge-discharge voltage interval is controlled to be 3.0-4.3V, the button cell is subjected to charge-discharge circulation for 2 times at 0.1C at room temperature, then is subjected to charge-discharge circulation for 1 time at 0.2C, 0.33C, 0.5C and 1C respectively, and the rate capability of the multi-element positive electrode material is evaluated according to the ratio of the initial discharge specific capacity of 0.1C to the discharge specific capacity of 1C. Wherein, the first discharge specific capacity of 0.1C is the discharge specific capacity of the button cell in the 1 st cycle, and the 1C discharge specific capacity is the discharge specific capacity of the button cell in the 6 th cycle.
Preparation example A1
S1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the mole ratio of the elements of nickel, cobalt and manganese of 82:10:8, obtaining mixed salt solution with the concentration of 2 mol/L; dissolving sodium hydroxide into a precipitant solution with the concentration of 8 mol/L; ammonia water was dissolved to a complexing agent solution at a concentration of 5.2 mol/L. Introducing 100L of mixed salt solution, precipitator solution and complexing agent solution into a reaction kettle in a parallel flow mode, carrying out a first continuous reaction for 20h under the conditions of 60 ℃ temperature, 11.38 pH value and 600rpm stirring speed, and then carrying out suction filtration and washing on precursor slurry under the protection of nitrogen atmosphere, drying a filter cake at 115 ℃ and screening to obtain a precursor of the monocrystalline anode material A1;
S2: the precursor of the single crystal positive electrode material a prepared in S1 was mixed with LiOH, zrO 2, and SrCO 3 in accordance with Li/(ni+co+mn)/Zr/sr=1.05: 1:0.003: the molar ratio of 0.002 is increased from room temperature to 830 ℃ in oxygen atmosphere, the temperature is kept for 18h for the first sintering, and the single crystal anode material A process product is obtained after cooling, crushing and screening;
And S3, heating the monocrystalline cathode material A process product prepared in the step S2 and a coating agent V 2O5 according to the molar ratio of (Ni+Co+Mn)/V=1:0.002 in an air atmosphere from room temperature to 750 ℃, preserving heat for 10 hours, performing second sintering, and cooling, crushing and screening to obtain monocrystalline particles A1. The composition and structural parameters of single crystal particle A1 are shown in tables 2 and 3, respectively.
Scanning electron microscope images (SEM) of the precursor of the single crystal positive electrode material A1, the single crystal particles A1 are shown in fig. 1 and 3. As can be seen from fig. 1 and 3, the surface of the precursor of the single crystal positive electrode material A1 is more loose, the single crystal particles A1 have better single crystallization degree, and the surface is smooth and round.
Preparation A2-A5 and comparative preparation DA1
The procedure of preparation A1 was followed, except that: the formulation and process parameters used were different, as shown in Table 1, and the remainder were the same as in preparation A1, to prepare monocrystalline particles A2-A3. The compositions and structural parameters of monocrystalline particles A2-A5 and monocrystalline particle DA1 are shown in tables 2 and 3, respectively.
TABLE 1
TABLE 2
TABLE 3 Table 3
| D50(A)(μm) | SA(m2/g) | |
| Preparation example A1 | 3.56 | 0.62 |
| Preparation example A2 | 4.21 | 0.65 |
| Preparation example A3 | 3.32 | 0.69 |
| Preparation example A4 | 5.71 | 0.51 |
| Preparation example A5 | 2.64 | 0.97 |
| Comparative preparation DA1 | 1.64 | 0.83 |
Preparation example B1
S1: nickel sulfate, cobalt sulfate and manganese sulfate are mixed according to the mole ratio of nickel, cobalt and manganese elements of 80:10:10 to obtain mixed salt solution with the concentration of 2 mol/L; dissolving sodium hydroxide into a precipitant solution with the concentration of 8 mol/L; ammonia water was dissolved to a complexing agent solution at a concentration of 5.2 mol/L. Introducing 100L of mixed salt solution, precipitator solution and complexing agent solution into a reaction kettle in a parallel flow mode, carrying out a second continuous reaction for 16 hours under the conditions of 60 ℃ temperature, 11.60 pH value and 600rpm stirring speed, and then carrying out suction filtration and washing on precursor slurry in a nitrogen protection atmosphere, drying a filter cake at 115 ℃ and screening to obtain a precursor of the polycrystalline anode material B1;
S2: the precursor of the polycrystalline cathode material B prepared in S1 was mixed with LiOH, zrO 2 and SrCO 3 according to Li/(ni+co+mn)/Zr/sr=1.05: 1:0.002: heating to 800 ℃ from room temperature in an oxygen atmosphere at a molar ratio of 0.001, preserving heat for 14h, performing third sintering, and cooling, crushing and screening to obtain a polycrystalline anode material B process product;
And S3, heating the processed product of the polycrystalline positive electrode material B prepared in the step S2 and a coating agent V 2O5 according to the molar ratio of (Ni+Co+Mn)/V=1:0.002 in an air atmosphere from room temperature to 720 ℃, preserving heat for 10 hours, performing fourth sintering, and obtaining polycrystalline particles B1 after cooling, crushing and screening. The composition and structural parameters of the polycrystalline table B1 are shown in tables 5 and 6, respectively.
Scanning Electron Microscope (SEM) images of the precursor of the polycrystalline cathode material B1, the polycrystalline particles B1, are shown in fig. 2 and 4. As can be seen from fig. 2 and 4, the precursor of the polycrystalline cathode material B1 has a large and round particle structure and a dense particle surface, relative to the precursor of the single crystal cathode material A1. The polycrystalline grains B1 are better in uniformity and uniform in grain size than the single crystal grains A1.
Preparation examples B2 to B5 and comparative preparation example DB1
Preparation examples B2 to B3 were prepared in the same manner as in preparation example B1 except that the formulation and process parameters used were different, as shown in Table 4. The compositions and structural parameters of the polycrystalline pellets B2 to B5 and the polycrystalline pellets DB1 are shown in tables 5 and 6, respectively.
TABLE 4 Table 4
TABLE 5
| Composition of polycrystalline particles B | |
| Preparation example B1 | Li1.05Ni0.80Co0.10Mn0.10Zr0.002Sr0.001V0.002O2 |
| Preparation example B2 | Li1.04Ni0.60Co0.20Mn0.20Y0.002Ba0.002Al0.001O2 |
| Preparation example B3 | Li1.06Ni0.90Co0.05Mn0.05Al0.0025Ta0.0025B0.003O2 |
| Preparation example B4 | Li1.05Ni0.80Co0.10Mn0.10Zr0.002Sr0.001V0.002O2 |
| Preparation example B5 | Li1.05Ni0.80Co0.10Mn0.10Zr0.002Sr0.001V0.002O2 |
| Comparative preparation example DB1 | Li1.05Ni0.80Co0.10Mn0.10Zr0.002Sr0.001V0.002O2 |
TABLE 6
| D50(B)(μm) | SB(m2/g) | |
| Preparation example B1 | 3.62 | 1.35 |
| Preparation example B2 | 4.15 | 1.38 |
| Preparation example B3 | 3.25 | 1.47 |
| Preparation example B4 | 5.77 | 1.26 |
| Preparation example B5 | 2.12 | 1.54 |
| Comparative preparation example DB1 | 13.54 | 1.09 |
Example 1
Monocrystalline particles A1 prepared in preparation example A1 and polycrystalline particles B1 prepared in preparation example B1 were prepared according to a ratio of 7:3, and obtaining the multi-element positive electrode material P1. The structural parameters of the multi-element positive electrode material are shown in table 8.
A scanning electron microscope image (SEM) of the multi-element positive electrode material P1 is shown in fig. 5. As can be seen from fig. 5, in the multi-component positive electrode material P1, the single crystal particles A1 and the polycrystalline particles B1 are mixed to achieve uniform distribution of the polycrystalline material and the single crystal material in the multi-component positive electrode material P1.
Examples 2 to 12 and comparative examples 1 to 4
The procedure of example 1 was followed, except that: the specific types of single crystal grains and polycrystalline grains, and the blending ratio of single crystal grains to polycrystalline grains were different, and are shown in table 7. The structure parameters and the compaction densities of the multi-element positive electrode materials P2 to P12 and DP1 to DP5 were measured, and the results are shown in Table 8. And (3) fracturing the multi-element positive electrode material under the pressure of 4.5T. Specific surface areas of the multi-component positive electrode material before and after 4.5T pressure, namely S 0、S1, and D 5 0、D5 1 of the positive electrode material before and after 4.5T pressure are shown in table 9.
TABLE 7
| Monocrystalline particles | Polycrystalline particles | A/B | ∣D50(A)-D50(B)∣ | x1-x2 | |
| Example 1 | A1 | B1 | 7：3 | 0.06 | 0.02 |
| Example 2 | A1 | B1 | 5：5 | 0.06 | 0.02 |
| Example 3 | A1 | B1 | 3：7 | 0.06 | 0.02 |
| Example 4 | A1 | B1 | 9：1 | 0.06 | 0.02 |
| Example 5 | A1 | B1 | 1：9 | 0.06 | 0.02 |
| Example 6 | A2 | B2 | 7：3 | 0.06 | 0.02 |
| Example 7 | A3 | B3 | 7：3 | 0.07 | 0.02 |
| Example 8 | A5 | B1 | 7：3 | 0.98 | 0.02 |
| Example 9 | A5 | B4 | 7：3 | 1.51 | 0.02 |
| Example 10 | A4 | B5 | 7：3 | 3.59 | 0.02 |
| Example 11 | A3 | B1 | 7：3 | 0.30 | 0.12 |
| Example 12 | A2 | B1 | 7：3 | 0.59 | -0.18 |
| Comparative example 1 | A1 | / | 1：0 | / | / |
| Comparative example 2 | / | B1 | 0：1 | / | / |
| Comparative example 3 | A1 | DB1 | 7：3 | 9.98 | 0.02 |
| Comparative example 4 | DA1 | B1 | 7：3 | 1.98 | 0.02 |
| Comparative example 5 | A1 | B1 | 9.8：0.2 | 0.06 | 0.02 |
TABLE 8
As can be seen from the results of table 8, the powder compacted density and the pole piece compacted density of the multi-element positive electrode material after blending are both greater than those of single crystal material and polycrystalline material alone, and the compacted density of the material after blending increases with the increase of single crystal material; and the larger the amount of single crystal particles, the larger the median particle diameter D 50, the larger the compacted density of the multi-element positive electrode material.
TABLE 9
As can be seen from the results in table 9, the specific surface area of the blended multi-element positive electrode material increases with the increase of the content of the polycrystalline positive electrode material B after 4.5T pressure fracturing, and D 5 becomes smaller, which indicates that the multi-element material is more disintegrated after fracturing; the more the single crystal positive electrode material A, the smaller the change of the specific surface area and D 5, which shows that the single crystal material can improve the compaction strength of the positive electrode material and make the material difficult to fracture. And D 50 of the monocrystalline particles is not easy to fracture; if the polycrystalline grain D 50 is larger than the monocrystalline grain D 50, it is more likely to be fractured, and the larger the difference in D 50, the more likely to be fractured.
Test case
The electrochemical properties of the multi-element positive electrode materials prepared in the above examples and comparative examples were tested, including the initial discharge specific capacity of 0.1C, the specific discharge capacity of 1C, the cycle performance and the rate performance, and the specific test results are shown in table 10.
Table 10
As can be seen from the results of table 10, when the multi-component positive electrode material prepared in comparative example 1 using single crystal particles alone was used for assembling a battery, the cycle performance of the battery was good, but the rate performance was poor; when the multi-component positive electrode material prepared in comparative example 2 using the polycrystalline particles alone was used to assemble a battery, the rate performance of the battery was good, but the cycle performance was poor.
The multi-element positive electrode materials provided in examples 1 to 5 have better cycle performance due to the high content of single crystal particles A, and the addition of the polycrystalline particles B can obviously improve the rate performance of the battery; the content of the polycrystalline particles B is high, the multiplying power performance of the battery is better, and the circulating performance of the material can be improved by adding the monocrystalline particles A; the mixed material of the two can keep better cycle performance of the monocrystalline material and has better multiplying power performance of the polycrystalline material.
In the multi-element positive electrode materials provided in examples 8 to 9, the median particle diameter of the single crystal particles is small, the rate performance is slightly good, but the cycle performance is poor; in the multi-component positive electrode material provided in example 9, since the median particle diameter of the polycrystalline particles is large, the median particle diameter of the single crystal particles is small, and the D 50 difference is large, the rate performance and the cycle performance of the battery including the multi-component positive electrode material are both inferior to those of example 1.
In the multi-component positive electrode material provided in example 10, the median particle diameter of the single crystal particles was large, and the median particle diameter of the polycrystalline particles was small, resulting in low discharge capacity and poor rate performance of the battery assembled from the multi-component positive electrode material.
In the multi-element positive electrode material provided in example 11, the difference between the nickel content of the single crystal particles and the nickel content of the polycrystalline particles is large, and in the multi-element positive electrode material provided in example 12, the nickel content of the single crystal particles is lower than the nickel content of the polycrystalline particles, so that the capacities of the single crystal particles and the polycrystalline particles are not matched, and when the multi-element positive electrode material is used for assembling a battery, the nickel content is high and is easy to fail in the circulating process, so that the capacity and the circulating performance are not facilitated.
In the multi-element positive electrode material provided in comparative example 3, the multi-element positive electrode material is easily crushed due to the excessively large median particle diameter of the polycrystalline particles, and finally, the battery capacity and the multiplying power obtained by assembling the multi-element positive electrode material are poor.
In the multi-component positive electrode material provided in comparative example 4, since the median particle diameter of the single crystal particles is too small to play a supporting role, the multi-component positive electrode material is liable to be crushed, and finally the cycle retention rate of the battery capacity assembled from the multi-component positive electrode material is poor.
In the multi-element positive electrode material provided in comparative example 5, the use amount of the polycrystalline particles is small, so that the effect of improving the multiplying power of the battery cannot be achieved.
As shown in fig. 6, the results of the high-temperature cycle performance test of the multi-component positive electrode materials prepared in example 1 and comparative examples 1 and 2 show that the multi-component positive electrode material of the present invention has a high cycle capacity retention rate and a good cycle performance, and can achieve both the capacity retention rate and the cycle stability, and the compaction density of example 1 is higher and the pressure resistance is more excellent than those of the multi-component positive electrode materials prepared in comparative examples 1 and 2 alone.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A multi-element positive electrode material, characterized in that the multi-element positive electrode material comprises single crystal particles a and polycrystalline particles B;
Wherein the median particle diameter D 50(A) of the single crystal particles A is 3-5 mu m; the median diameter D 50(B) of the polycrystalline particles B is 3-5 mu m;
the weight ratio of the monocrystalline particles A to the polycrystalline particles B is 7:3-9:1;
the multi-component positive electrode material satisfies at least one of the following conditions:
（i）0.5≤S0≤1.2 m2/g；
（ii）(S1-S0)/S0×100%≤120%；
(iii) (D 5 0-D5 1)/ D5 0 X100% is 1-15%;
（iv）0≤(S0-SA)/SA×100%≤50%；
Wherein S A is the specific surface area of the single crystal particle a;
the specific surface area of the multi-element positive electrode material is S 0, and after pressure fracturing of 4.5T, the specific surface area of the multi-element positive electrode material is S 1;
The particle size corresponding to 5% of the volume distribution of the multi-element positive electrode material obtained by the particle size test is D 5 0, and after 4.5T pressure fracturing, the particle size corresponding to 5% of the volume distribution of the multi-element positive electrode material obtained by the particle size test is D 5 1;
the single crystal particle A has a composition represented by formula I:
Li 1+a1(Nix1Coy1Mnz1M1m1)J1j1O2 formula I;
Wherein ,-0.1≤a1≤0.1,0＜x1≤0.82,0＜y1≤0.4,0＜z1≤0.6,0≤m1≤0.1,0≤j1≤0.02;M1 is an element selected from at least one of Ta, cr, mo, W, la, al, Y, ti, zr, V, nb, ce, er, mg, sr, ba and B; j 1 is at least one element selected from W, mo, zr, al, V, ti, B, co and Nb;
the polycrystalline particles B have a composition represented by formula II:
li 1+a2(Nix2Coy2Mnz2M2m2)J2j2O2 formula II;
Wherein ,-0.1≤a2≤0.1,0＜x2≤0.8,0＜y2≤0.4,0＜z2≤0.6,0≤m2≤0.1,0≤j2≤0.02;M2 is an element selected from at least one of Ta, cr, mo, W, la, al, Y, ti, zr, V, nb, ce, er, mg, sr, ba and B; j 2 is an element selected from at least one of W, mo, zr, al, V, ti, B, co and Nb;
x 1-x2 is 0.01-0.05.
2. The multi-element positive electrode material according to claim 1, wherein a weight ratio of the single crystal particles a to the polycrystalline particles B is 7:3 to 8:2;
And/or, the median particle diameter D 50 of the multi-element positive electrode material is 2-6 mu m.
3. The multi-component positive electrode material according to claim 2, wherein the multi-component positive electrode material has a median particle diameter D 50 of 3 to 5 μm.
4. The multi-component positive electrode material according to any one of claims 1 to 3, wherein an absolute value of a difference between a median diameter D 50(A) of the single crystal particles a and a median diameter D 50(B) of the polycrystalline particles B is 1 μm or less;
And/or the specific surface area S A of the single crystal particle A is 0.4-1m 2/g;
and/or the specific surface area S B of the polycrystalline particles B is 0.9-2m 2/g.
5. The multi-component positive electrode material according to claim 4, wherein an absolute value of a difference between a median particle diameter D 50(A) of the single crystal particles a and a median particle diameter D 50(B) of the polycrystalline particles B is 0.8 μm or less;
And/or the specific surface area S A of the single crystal particle A is 0.5-0.9m 2/g;
and/or the specific surface area S B of the polycrystalline particles B is 1.1-1.6m 2/g.
6. The multi-element positive electrode material according to any one of claims 1 to 3, wherein (S 1-S0)/S0 x 100%) is 10 to 120%.
7. The multi-component positive electrode material according to any one of claims 1 to 3, wherein the multi-component positive electrode material satisfies the following condition:
（i）0.5≤S0≤1m2/g；
(ii) (S 1-S0)/S0 X100% is 10-100%;
(iii) (D 5 0-D5 1)/ D5 0 X100% is 1-10%;
（iv）0≤(S0-SA)/SA×100%≤30%；
wherein S A is the specific surface area of the single crystal particle a.
8. A method for preparing the multi-element positive electrode material according to any one of claims 1 to 7, comprising:
and mixing the monocrystalline particles A with the polycrystalline particles B to obtain the multi-element positive electrode material.
9. The method for preparing a multi-element positive electrode material according to claim 8, wherein the single crystal particles a are prepared by:
S1, mixing nickel salt, cobalt salt, manganese salt, a first precipitator and a first complexing agent in the presence of a solvent, adding the mixture into a reaction kettle for a first continuous reaction, and performing filter pressing, washing and drying to obtain a precursor of a monocrystal anode material A;
S2, mixing the precursor of the single crystal positive electrode material A with a first lithium salt and a first doping agent M 1, and obtaining a process product of the single crystal positive electrode material A through first sintering, crushing and screening;
s3, performing second sintering on the process product of the monocrystalline anode material A and a first coating agent J 1 to obtain monocrystalline particles A;
Wherein M 1 is at least one element selected from Ta, cr, mo, W, la, al, Y, ti, zr, V, nb, ce, er, mg, sr, ba and B, and J 1 is at least one element selected from W, mo, zr, al, V, ti, B, co and Nb;
and/or, the polycrystalline particles B are prepared according to the following steps:
(a) Mixing nickel salt, cobalt salt, manganese salt, a second precipitator and a second complexing agent in the presence of a solvent, adding the mixture into a reaction kettle for a second continuous reaction, and performing filter pressing, washing and drying to obtain a precursor of the polycrystalline anode material B;
(b) Mixing the precursor of the polycrystalline anode material B with a second lithium salt and a second doping agent M 2, and performing third sintering, crushing and screening to obtain a process product of the polycrystalline anode material B;
(c) Performing fourth sintering on the processed product of the polycrystalline anode material B and a second coating agent J 2 to obtain polycrystalline particles B;
wherein M 2 is at least one element selected from Ta, cr, mo, W, la, al, Y, ti, zr, V, nb, ce, er, mg, sr, ba and B, and J 2 is at least one element selected from W, mo, zr, al, V, ti, B, co and Nb.
10. Use of the multi-element positive electrode material according to any one of claims 1 to 7 in a lithium ion battery.
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