CN115566162A - Lithium-containing oxide positive electrode material precursor, lithium-containing oxide positive electrode material, preparation method and application of lithium-containing oxide positive electrode material, positive plate and application of positive plate - Google Patents
Lithium-containing oxide positive electrode material precursor, lithium-containing oxide positive electrode material, preparation method and application of lithium-containing oxide positive electrode material, positive plate and application of positive plate Download PDFInfo
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- CN115566162A CN115566162A CN202211166346.XA CN202211166346A CN115566162A CN 115566162 A CN115566162 A CN 115566162A CN 202211166346 A CN202211166346 A CN 202211166346A CN 115566162 A CN115566162 A CN 115566162A
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- lithium
- positive electrode
- electrode material
- containing oxide
- sintering
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 92
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 67
- 239000002243 precursor Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000010406 cathode material Substances 0.000 claims abstract description 33
- 230000006835 compression Effects 0.000 claims abstract description 21
- 238000007906 compression Methods 0.000 claims abstract description 21
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 68
- 238000005245 sintering Methods 0.000 claims description 57
- 239000000654 additive Substances 0.000 claims description 26
- 229910052721 tungsten Inorganic materials 0.000 claims description 26
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 230000000996 additive effect Effects 0.000 claims description 21
- 229910052727 yttrium Inorganic materials 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 14
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 10
- 239000013078 crystal Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 7
- 150000004706 metal oxides Chemical class 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 239000010405 anode material Substances 0.000 abstract description 6
- 238000000605 extraction Methods 0.000 abstract 1
- 238000006713 insertion reaction Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 87
- 239000011572 manganese Substances 0.000 description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 239000002245 particle Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 230000014759 maintenance of location Effects 0.000 description 13
- 239000008139 complexing agent Substances 0.000 description 9
- 239000012266 salt solution Substances 0.000 description 9
- -1 transition metal cations Chemical class 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 3
- 150000002696 manganese Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 3
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 239000012716 precipitator Substances 0.000 description 3
- 229910003449 rhenium oxide Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 150000004679 hydroxides Chemical class 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
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 241000877463 Lanio Species 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 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
- 238000004891 communication Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 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
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- 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
- H01M4/48—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
-
- 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
- H01M4/48—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
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to the technical field of lithium ion batteries, and discloses a lithium-containing oxide positive electrode material precursor, a lithium-containing oxide positive electrode material, a preparation method and application of the lithium-containing oxide positive electrode material precursor, a positive plate and application of the positive plate. The compression resistance index Delta lambda (P) of the anode material 100 ) Satisfies the following conditions: delta lambda (P) 100 ) Not less than 60% + (y/x). Times.5%; wherein y/x is the molar ratio of Mn/Ni in the positive electrode material. The lithium-containing oxide cathode material has high performanceThe electrode plate has the advantages of high compressive strength and stability, can be broken to a small extent under the condition of bearing high pressure in the electrode plate manufacturing process, and can continuously carry out lithium ion extraction/insertion reaction without serious breakage.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium oxide-containing positive electrode material precursor, a lithium oxide-containing positive electrode material, a preparation method and application of the lithium oxide-containing positive electrode material precursor, a positive plate and application of the positive plate.
Background
In recent years, new energy automobiles are emerging as a national strategy industry for dealing with environmental pollution and energy crisis, and show a good situation of vigorous development, and lithium ion batteries are widely applied to markets such as electric automobiles, energy storage power stations, communication and digital electronic products as new energy carriers with excellent comprehensive performance.
In a lithium ion battery, the positive electrode is used as a key core material of the lithium ion battery, and directly determines the technical performance level of the battery. Among the commonly used positive electrode materials for lithium ion batteries, liNi having a layered structure 1-x-y Co x Mn y O 2 (NCM) and LiNi 1-x-y Co x Al y O 2 (NCA) and lithium-rich manganese-based materials (LMR) are of great interest and research due to their high specific capacity and energy density. However, in order to obtain higher volumetric energy density and comprehensive electrochemical performance, the positive electrode material needs to be rolled with higher strength in the manufacturing process of the battery pole piece so as to obtain high electrode density. The low-strength cathode material can be cracked or crushed in the process, so that the contact area with the electrolyte is increased, side reactions are caused, and the cycle performance and the rate performance are deteriorated. In addition, during battery use, li + The repeated deintercalation of (2) causes the volume expansion and contraction of a layered structure, so that the anode material with low strength is pulverized, the contact among particles is insufficient, a new electrolyte layer is continuously formed, side reactions are increased, and the performance of the battery is deteriorated and failed.
Therefore, the development of a novel preparation method and the regulation of the microstructure of the layered positive electrode material enhance the compressive strength or the particle strength of the positive electrode material, and have very important significance for realizing long cycle life, high specific capacity, high rate performance and the like of the battery.
Disclosure of Invention
The invention aims to overcome the defects of poor rate performance, poor cycle performance and reduced safety performance caused by the fact that a lithium-containing metal oxide material is broken in the manufacturing process of an electrode plate or secondary particles are broken in the charging and discharging cycle process in the prior art, and provides a lithium-containing oxide positive electrode material precursor, a lithium-containing oxide positive electrode material, a preparation method and application thereof, a positive electrode plate and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a lithium oxide-containing positive electrode material, wherein the positive electrode material has a compressive index Δ λ (P) 100 ) Satisfies the following conditions: delta lambda (P) 100 )≥60％+(y/x)×5％；
Wherein y/x is the molar ratio of Mn/Ni in the positive electrode material.
The invention provides a lithium oxide-containing positive electrode material precursor in a second aspect, wherein the compressive index delta lambda' (P) of the precursor 50 ) Satisfies the following conditions: Δ λ' (P) 50 )≥35％+(v/u)×8％；
Wherein v/u is the molar ratio of Mn/Ni in the precursor.
The third aspect of the present invention provides a method for preparing a lithium oxide-containing positive electrode material, wherein the method comprises:
s1: a precursor having a chemical formula shown in formula (1), a lithium source, and optionally an element M 2 The additive is uniformly mixed and is sintered for the first time in an atmosphere furnace to obtain a primary sintering material with a chemical formula shown in a formula (2);
s2: uniformly mixing the primary sintering material with an additive containing an element M', and carrying out secondary sintering on the mixed material in an atmosphere furnace to obtain a lithium-containing metal oxide with a chemical formula shown in a formula (3);
Ni u Mn v M 1γ (OH) 2 formula (1);
wherein u + v + γ =1,0.2<u<1，0<v≤0.75，0≤γ≤0.35，M 1 Selected from Al, zr, nb, ti, Y, sc, cr, co, W, mg,At least one element selected from Na, la, os, pr, re, ru, sr, sm, ta and B;
Li[Li a Ni x Mn y M j ]O 2 formula (2);
Li[Li a Ni x Mn y M j ]O 2 @ M', formula (3);
wherein, in formula (2) and formula (3):
a+x+y+j＝1，0≤a≤0.3，0.2<x<1，0<y≤0.75，0<j≤0.35；
m includes M in the precursor 1 Element and incorporation of M in the first sintering 2 An element;
M 1 、M 2 at least one element, which is the same or different, each selected from the group consisting of Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta and B;
in formula (3):
m 'is oxide, phosphide, sulfide, fluoride or chloride containing at least one element of Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta and B, the mole content of cation in M' is W, 0<w/(a + x + Y + j) is less than or equal to 0.1.
The invention provides a lithium-containing oxide cathode material prepared by the preparation method of the lithium-containing oxide cathode material.
The fifth aspect of the present invention provides a positive electrode sheet, wherein the positive electrode sheet comprises at least 90wt% of a lithium-containing oxide positive electrode material, based on the total weight of the positive electrode sheet;
wherein, the lithium-containing oxide cathode material is the lithium-containing oxide cathode material.
The invention provides an application of the lithium-containing oxide cathode material, the lithium-containing oxide cathode material precursor or the cathode sheet in a lithium ion battery.
Through the technical scheme, the invention has the following advantages:
(1) The lithium-containing oxide positive electrode material and the precursor provided by the invention realize high crystallinity and densification of the precursor through the control of a specific microstructure, so that the compression resistance index of the positive electrode material is improved;
(2) The invention can improve the compression resistance index, cycle life and safety performance of the material through proper modifier and doping elements;
(3) The sintering system in the preparation process of the lithium-containing metal oxide influences the compression resistance index of the material, so that the cost, the compression resistance index of the material, the physical indexes and the electrochemical performance of the material are considered when the sintering system is selected.
Drawings
FIG. 1 is a schematic diagram comparing charge and discharge curves of example 5 and comparative example 1;
FIG. 2 is a comparison of cycle performance for example 5 and comparative example 1;
FIG. 3 is a comparative graph showing charge and discharge curves of example 5 and comparative example 2;
FIG. 4 is a comparative graph of cycle performance of example 5 and comparative example 2;
FIG. 5 is a graph showing a comparison of charge and discharge curves of example 5 and comparative example 3;
FIG. 6 is a comparative graph of cycle performance of example 5 and comparative example 3;
FIG. 7 is a comparative graph of the charge and discharge curves of example 5 and comparative example 4;
FIG. 8 is a comparative graph of cycle performance of example 5 and comparative example 4;
FIG. 9 is a comparative graph of the charge and discharge curves of example 9 and comparative example 5;
FIG. 10 is a comparative graph of cycle performance of example 9 and comparative example 5;
FIG. 11 is a comparative graph of the charge and discharge curves of example 9 and comparative example 6;
FIG. 12 is a comparison of cycle performance for example 9 and comparative example 6;
FIG. 13 is a comparative graph of the charge and discharge curves of example 9 and comparative example 7;
FIG. 14 is a comparative graph of cycle performance of example 9 and comparative example 7.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
For the conventional lithium-containing metal oxide material for the lithium ion battery, the material is cracked due to insufficient compressive strength or unstable structure in the preparation process of an electrode plate and the continuous charge-discharge cycle process, so that the side reaction with the electrolyte is increased, the consumption of the electrolyte and the dissolution of transition metal cations in the anode material are accelerated, the cycle performance, the safety performance and the capacity are reduced, and even the battery fails.
As described above, the first aspect of the present invention provides a lithium oxide-containing positive electrode material, wherein the positive electrode material has a compressive index Δ λ (P) 100 ) Satisfies the following conditions: delta lambda (P) 100 )≥60％+(y/x)×5％；
Wherein y/x is the molar ratio of Mn/Ni in the positive electrode material.
In addition, in the present invention:
wherein
Refers to the particle cumulative distribution D of the material under the natural state without external mechanical pressure (namely P =0 Mpa) 5 Value of,
refers to the cumulative particle distribution D of the material at P = n MPa 5 Value, D 5 Refers to the particle diameter with 5% of the cumulative volume distribution of the particlesThe value is obtained.
For example, the compression resistance index Δ λ (P) 100 ) The calculation method is as follows:
according to the present invention, the positive electrode material preferably has a compressive resistance index Δ λ (P) 200 ) Satisfies the following conditions: delta lambda (P) 200 )≥45％+(y/x)×5％。
According to the present invention, more preferably, the positive electrode material has a compression resistance index Δ λ (P) 300 ) Satisfies the following conditions: delta lambda (P) 300 )≥35％+(y/x)×5％。
According to the present invention, it is noted that Δ λ (P) 100 ) The pressure resistance index of the material is shown when the pressure P =100 MPa; delta lambda (P) 200 ) The pressure resistance index of the material is shown when the pressure P =200 MPa; and so on.
The positive electrode material provided by the invention has excellent compressive strength, is not easy to crack, and has stable structure, less side reaction, excellent safety performance and capacity retention rate in the application process of being used as a positive electrode.
According to the present invention, the lithium-containing oxide positive electrode material has a chemical formula shown in formula (3):
Li[Li a Ni x Mn y M j ]O 2 @ M', formula (3);
wherein a + x + Y + j =1,0 ≤ a ≤ 0.3, 0.2-straw x is 1, 0-straw Y ≤ 0.75, 0-straw j ≤ 0.35, M is at least one element selected from the group consisting of Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta, and B, M 'is an oxide, phosphide, sulfide, fluoride or chloride containing at least one element selected from the group consisting of Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta, and B, the molar content of cations in M' is W, 0<w/(a + x + Y + j) ≤ 0.1.
According to the present invention, it is preferable that 0.02. Ltoreq. A.ltoreq.0.3, 0.3 yarn-over-x yarn-over-0.9, 0.05 yarn-over-y.ltoreq.0.68, 0 yarn-over-j.ltoreq.0.3, 0.001 yarn-over-w/(a + x + y + j) ltoreq.0.02.
According to the invention, M is at least one element selected from the group consisting of Zr, nb, ti, Y, sc, cr, co, W, mg, la, ta and B, and M' is an oxide, phosphide, sulfide or fluoride containing at least one element selected from the group consisting of Zr, nb, ti, Y, sc, cr, co, W, mg, la, ta and B.
In the present invention, the inventors of the present invention found that:
by adopting the proper modifier, the compressive strength and stability of the material particles can be enhanced, the direct-current internal resistance value and the gas production rate of the material in the circulating process are reduced, and the circulating life of the material is prolonged.
The crystal structure of the material can be stabilized by doping elements such as Ti, sc, zr, W, mg, Y, co, cr, ta and the like, the micro-area structure of the material is improved, and the compression resistance index, the cycle life and the safety performance of the material are improved; doping elements such as Ti, zr, nb, la, W, co, B and the like can form lithium-containing compounds (such as LiNbO) on the surfaces of material particles or at interfaces among the particles 3 Or Li 2 ZrO 3 Or Li 4 Ti 5 O 12 Or Li 3 BO 3 Or LaNiO 3 And the like), the surface structure of the material particles, the interface strength among the particles or the crystal boundary structure among primary particles are stabilized, the compression resistance index and the cycle life of the material are improved, the transmission of lithium ions among the particles and among the interfaces can be accelerated, and the rate capability of the material is improved. The positive electrode material provided by the invention is also characterized in that:
according to the invention, the tap density of the cathode material is more than or equal to 1.7g/cm 3 Preferably ≥ 2g/cm 3 More preferably not less than 2.4g/cm 3 。
According to the invention, the compacted density of the cathode material is more than or equal to 2.8g/cm 3 Preferably ≥ 3g/cm 3 More preferably not less than 3.2g/cm 3 。
According to the present invention, the content of the surface-soluble alkali of the positive electrode material satisfies the following condition:
Li 2 CO 3 ≤1wt％，LiOH≤0.5wt％；
preferably Li 2 CO 3 ≤0.5wt％，LiOH≤0.4wt％；
Further preferred is Li 2 CO 3 ≤0.3wt％，LiOH≤0.3wt％；
Even more preferably Li 2 CO 3 ≤0.2wt％，LiOH≤0.2wt％。
According to the present invention, the positive electrode material has a full width at half maximum FWHM of a (003) plane obtained by XRD (003) And FWHM of full width at half maximum of (104) crystal plane (104) The following conditions are satisfied:
0.10≤FWHM (003) 0.25 or less, preferably 0.13 or less FWHM (003) ≤0.22；
0.20≤FWHM (104) 0.50 or less, preferably 0.22 or less FWHM (104) ≤0.42。
According to the invention, the positive electrode material has a peak area S of a (003) plane obtained by XRD (003) Peak area S of (104) and (Z) plane (104) The following conditions are satisfied:
1.1≤S (003) /S (104) 1.8, preferably 1.2S (003) /S (104) ≤1.6。
Besides the adoption of proper additives, the method also realizes the high crystallinity and densification of the precursor by controlling the morphology and microstructure of the precursor, thereby improving the compression resistance index of the cathode material.
The invention provides a lithium oxide-containing positive electrode material precursor in a second aspect, wherein the compressive index delta lambda' (P) of the precursor 50 ) Satisfies the following conditions: Δ λ' (P) 50 )≥35％+(v/u)×8％；
Wherein v/u is the molar ratio of Mn/Ni in the precursor.
According to the invention, the compressive index Δ λ' (P) of the precursor is preferably 100 ) Satisfies the following conditions: Δ λ' (P) 100 )≥25％+(v/u)×8％。
According to the present invention, Δ λ' (P) is defined as 50 ) The compressive index of the precursor material is shown when the pressure P =50 MPa; Δ λ' (P) 100 ) The compressive index of the precursor material is expressed when the pressure P =100 MPa; and so on.
In the present invention, in the case of the present invention,
wherein
Refers to the particle cumulative distribution D of the precursor material under the condition of no external mechanical pressure (namely P =0 MPa) in the natural state 5 Value of,
refers to the particle cumulative distribution D of the precursor material at P = nMPa 5 The value is obtained.
For example, the compressive index Δ λ' (P) of the precursor 50 ) The calculation method of (c) is as follows:
according to the invention, the precursor has the chemical formula shown in formula (1):
Ni u Mn v M γ (OH) 2 formula (1);
<xnotran> , u + v + γ =1,0.2<u<1,0<v ≤ 4736 zxft 4736 ≤ γ ≤ 0.35,M Al, zr, nb, ti, Y, sc, cr, co, W, mg, na, la, os, pr, re, ru, sr, sm, ta B ; </xnotran>
Preferably, 0.3. Ltoreq. U.ltoreq. 0.9,0.05. Ltoreq. V.ltoreq. 0.68,0. Ltoreq. Gamma.ltoreq.0.3, M is at least one element selected from the group consisting of Ti, al, zr, W, co, nb, la, na and Mg. In the invention, the internal or surface structure of the precursor micro-region can be stabilized by doping elements such as Ti, al, zr, W, co, nb, la, na, mg and the like.
The precursor material provided by the invention is also characterized in that:
according to the present invention, more preferably, the tap density of the precursor is not less than 1.2g/cm 3 Preferably ≥ 1.6g/cm 3 More preferably not less than 2g/cm 3 。
According to the invention, the BET value of the specific surface area of the precursor satisfies: BET is less than or equal to 30m 2 Per g, preferably BET ≦ 25m 2 /g。
According to the invention, the particle size distribution coefficient K of the precursor 90 Satisfies the following conditions: k is more than or equal to 0.5 90 Less than or equal to 1.6; wherein K 90 ＝(D 90 -D 10 )/D 50 ，D 10 、D 50 And D 90 Refer to the particle size values at 10%, 50% and 90% cumulative volume distribution of the particles, respectively.
According to the invention, the precursor has a full width at half maximum FWHM of a (001) crystal face obtained by XRD (001) FWHM of full width at half maximum of (100) crystal plane (100) FWHM of full width at half maximum of (1) and (101) crystal planes (101) The following conditions are satisfied:
0.3≤FWHM (001) 1 or less, preferably 0.5 or less FWHM (001) Less than or equal to 0.8; namely, the FWHM of the precursor material provided by the invention is measured by an X-ray diffractometer (001) 2 θ of (a) is not less than 0.3 and not more than 1, preferably not less than 0.5 and not more than 0.8;
0.10≤FWHM (100) 0.5 or less, preferably 0.25 or less FWHM (100) ≤0.35；
0.30≤FWHM (101) 1.0 or less, preferably 0.4 or less FWHM (101) ≤0.8。
According to the invention, the peak area S of the (001) crystal face of the precursor is obtained by XRD (101) Peak area S of (101) plane (104) The following conditions are satisfied: s (001) /S (101) ≥2.0。
According to the invention, the integral area S of the (001) crystal plane obtained by XRD of the precursor (101) Integral area S with (101) plane (104) The following conditions are satisfied: s (001) /S (101) ≥2.0。
In the invention, the preparation method of the lithium oxide-containing positive electrode material precursor is also provided, wherein the preparation method comprises the following steps:
(1) Contacting and mixing a nickel salt, a manganese salt and a solution or suspension of a compound containing M to obtain a mixed salt solution;
(2) And (3) enabling the mixed salt solution, the precipitator solution and the complexing agent solution to flow into a reaction kettle in parallel for crystallization reaction, and then carrying out solid-liquid separation, washing, heat treatment and screening on the obtained slurry to obtain the precursor of the lithium-containing oxide cathode material.
In the present invention, the inventors of the present invention found that: for the precursor of the metal hydroxide, the compressive strength of the precursor is not enough to crack in the process of mixing and sintering, so that the compressive strength of the prepared anode material is reduced, the tap density is reduced, and the electrochemical performance is reduced. In the invention, the synthesis of the precursor with high crystallinity and densification can be realized by controlling the synthesis process of the precursor, such as the concentration and variety of complexing agents, the concentration of precipitating agents, the stirring strength, the reaction temperature, additives, solid content, the feeding rate and the like, and the particle size distribution and the specific surface area of the precursor are regulated and controlled, so that the crystallinity, the tap density and the compression resistance index of the precursor material are improved; and the compressive index of the precursor can be improved by adding a proper additive and regulating and controlling the microstructure and the morphology of the precursor.
According to the invention, nickel salt, manganese salt or an additive containing M element are dissolved into a mixed salt solution with the concentration of 1-3mol/L according to the molar ratio u: v: gamma, a compound containing M is added into water to prepare an M solution or suspension with a certain concentration, alkali is dissolved into an alkali solution with the concentration of 2-10mol/L, and a complexing agent is dissolved into a complexing agent solution with the concentration of 2-13 mol/L.
According to the invention, the solids content of the slurry is from 200 to 1000g/L, preferably from 300 to 800g/L.
According to the invention, mixed salt solution of Ni and Mn, alkali liquor, complexing agent solution and M solution are respectively added into a reaction kettle with an overflow pipeline through respective liquid inlet pipelines in parallel flow, the stirring speed is kept constant, and the liquid inlet flow rates of the mixed salt solution, the precipitator solution, the complexing agent solution and the M solution are controlled.
According to the invention, the conditions of the reaction include: the reaction temperature is 40-70 ℃, the reaction pH is 10.6-12.5, and the reaction time is 5-100h.
According to the invention, the nickel salt is one or more of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate.
According to the invention, the manganese salt is one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
According to the invention, the compound containing M is one or more of sulfate, chloride, nitrate, acetate, citrate, carbonate, phosphate, oxalate and fluoride containing M element.
According to the invention, the precipitator is an alkali substance, and the alkali is one or more of sodium hydroxide, potassium hydroxide and lithium hydroxide.
According to the invention, the complexing agent is one or more of salicylic acid, ammonium sulfate, ammonium chloride, ammonia water, sulfosalicylic acid and ethylenediamine tetraacetic acid.
According to the present invention, the sintering regime (including sintering temperature, heating rate, sintering atmosphere, etc.) during the preparation of the lithium-containing metal oxide is also very important, and can affect the compressive index of the material.
The third aspect of the present invention provides a method for preparing a lithium oxide-containing positive electrode material, wherein the method comprises:
s1: a precursor having a chemical formula shown in formula (1), a lithium source, and optionally an element M 2 The additive is uniformly mixed, and the mixed material is sintered for the first time in an atmosphere furnace to obtain a primary sintered material with a chemical formula shown in a formula (2);
s2: uniformly mixing the primary sintering material with an additive containing an element M', and carrying out secondary sintering on the mixed material in an atmosphere furnace to obtain a lithium-containing metal oxide with a chemical formula shown in a formula (3);
Ni u Mn v M 1γ (OH) 2 formula (1);
wherein u + v + γ =1,0.2<u<1，0<v≤0.75，0≤γ≤0.35，M 1 At least one element selected from the group consisting of Al, zr, nb, ti, Y, sc, cr, co, W, mg, na, la, os, pr, re, ru, sr, sm, ta and B;
Li[Li a Ni x Mn y M j ]O 2 (ii) a Formula (2);
Li[Li a Ni x Mn y M j ]O 2 @ M', formula (3);
wherein in formula (2) and formula (3):
0≤a≤0.3，0.2<x<1，0<y≤0.75，0<j≤0.35；
m includes M in the precursor 1 Element and M in the first sintering process 2 An element;
M 1 、M 2 at least one element, which is the same or different, each selected from the group consisting of Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta and B;
in formula (3):
m 'is oxide, phosphide, sulfide, fluoride or chloride containing at least one element of Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta and B, the molar content of cations in M' is W, 0<w/(a + x + Y + j) is not more than 0.1.
According to the invention, the source of the M element in the positive electrode material comprises M in the precursor 1 Element and M in the first sintering process 2 An additive of an element.
According to the invention, the lithium source is at least one of lithium hydroxide, lithium carbonate and lithium nitrate;
according to the invention, said compound contains M 2 The additive of the element is selected from the group consisting of M 2 At least one of oxides, hydroxides, oxyhydroxides, phosphates, fluorides, borides, and carbonates.
According to the invention, said M 1 Element, said M 2 The element is the same as or different from the M element, and each is at least one element selected from the group consisting of Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta, and B.
According to the invention, the additive containing the element M 'is selected from at least one of oxides, hydroxides, oxyhydroxides, phosphates, fluorides, borides, nitrides, carbonates and oxalates containing the element M'.
According to the invention, the lithium source is used in a quantity corresponding to the quantity of the precursor and the element M 2 In a molar ratio of the sum of the additive amounts of Li/(Ni + Mn + M) 1 +M 2 ) Is 1 to 1.85, preferably 1 to 1.5.
According to the invention, said element M is contained 2 In accordance with M 2 /(Ni+Mn+M 1 +M 2 ) The amount of the additive is 0.0005-0.3, preferably 0.001-0.2.
According to the invention, the molar ratio M '/(Ni + Mn + M) of the amount of the additive containing the element M' to the amount of the primary sinter is 1 +M 2 ) Is 0 to 0.1, preferably 0.001 to 0.02.
According to the invention, when the molar ratio Ni/Mn is greater than 1, i.e. x/y>1, said first sintering temperature T 1 The relationship with the Ni content satisfies: t is more than or equal to 550 x (2-x) 1 Less than or equal to 400 x (3-x) DEG C, the sintering time is 6-20h, preferably 8-15h.
According to the invention, when the molar ratio of Ni/Mn is less than or equal to 1, namely y/x is more than or equal to 1, the first sintering temperature T 2 The relation with the Mn content satisfies: t not more than 500 x (1+y) 2 650 x (1+y) DEG C or less, and the sintering time is 6-20h, preferably 8-15h.
According to the invention, when x is less than 0.5, the first and second sintering atmospheres are air; when x is more than or equal to 0.5 and less than 0.6, the atmosphere of the first sintering and the second sintering is air or mixed gas of air and oxygen; when x is more than or equal to 0.6, the atmosphere of the first sintering and the second sintering is oxygen or mixed gas of oxygen and air.
The invention provides a lithium-containing oxide cathode material prepared by the preparation method of the lithium-containing oxide cathode material.
The fifth aspect of the present invention provides a positive electrode sheet, wherein the positive electrode sheet comprises at least 90wt% of a lithium-containing oxide positive electrode material, based on the total weight of the positive electrode sheet; the lithium-containing oxide cathode material is the lithium-containing oxide cathode material.
According to the present invention, it is preferable that the positive electrode material accounts for not less than 95% by mass.
According to the invention, the pole piece density of the positive plate is more than or equal to 2.8g/cm 3 Preferably ≥ 3.2g/cm 3 More preferably not less than 3.5g/cm 3 。
The invention provides an application of the lithium-containing oxide cathode material, the lithium-containing oxide cathode material precursor or the cathode sheet in a lithium ion battery.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
all the raw materials are commercially available unless otherwise specified.
In the following examples, the properties involved are obtained in the following manner:
(1) Phase testing: obtained by testing with an X-ray diffractometer of SmartLab 9kW model of Japan science;
(2) And (3) morphology testing: obtained by a scanning electron microscope test of type S-4800 of Hitachi, japan;
(3) And (3) particle size testing: obtained by testing a laser particle size analyzer with a model number of Hydro 2000mu of Marvern company;
(4) Specific surface area: obtained by testing with a specific surface tester model Tristar II3020 of micromeritics, USA;
(5) Tap density: the test result is obtained by a tap density tester of BT-30 model of Baite company;
(6) Compacting density: obtained by testing with a powder impedance tester of MCP-PD51 model of Mitsubishi chemical;
(7) And (3) testing the compression resistance index: compressing the material by a manual tablet press of 4350 model of Carver company in America under specific pressure, testing the particle size of the fractured material, and substituting the particle size into a compression resistance index formula for calculation;
(8) Surface residual alkali test: titrating by a Metrohmm888 professional Tirando intelligent potentiometric titrator;
(9) And (3) testing thermal stability: the test result is obtained by a thermogravimetric analysis tester with a Mettler TGA-DSC3 model;
(10) And (3) electrochemical performance testing:
the electrochemical performance of the prepared lithium-containing oxide cathode material is obtained by testing a 2025 button cell by using a Xinwei cell testing system, and specifically comprises the following steps:
1) The preparation process of the 2025 button cell comprises the following steps:
preparing a pole piece: the lithium-containing oxide positive electrode material, carbon black and polyvinylidene fluoride are fully mixed with a proper amount of N-methyl pyrrolidone according to a certain mass ratio to form uniform slurry, and the uniform slurry is coated on an aluminum foil and dried, rolled and punched at 120 ℃ to be prepared into a positive electrode sheet with the diameter of 11 mm.
Assembling the battery: the negative electrode uses a Li metal sheet with the diameter of 17mm and the thickness of 1 mm; the separator used was a polyethylene porous film having a thickness of 25 μm; liPF of 1mol/L is used as electrolyte 6 And a mixture of Ethylene Carbonate (EC) and diethyl carbonate (DEC) in equal amounts.
Assembling the positive pole piece, the diaphragm, the negative pole piece and the electrolyte into a 2025 type button cell in an Ar gas glove box with the water content and the oxygen content of less than 5ppm, and taking the cell as an unactivated cell.
2) And electrochemical performance test:
when the molar ratio of Ni/Mn is more than 1, namely x/y is more than 1, the button cell test conditions are as follows: placing for 2h after manufacturing the button cell, after the open-circuit voltage is stable, charging to the cut-off voltage of 4.3V in a mode that the current density of the anode is 0.1C, then charging for 30min at constant voltage, and then discharging to the cut-off voltage of 3.0V at the same current density; the same procedure was repeated 1 more time, and the battery at this time was regarded as an activated battery. Using an activated battery, and carrying out a charge-discharge test to evaluate the charge-discharge capacity of the material at a voltage range of 3.0-4.3V, a charge-discharge range of 3.0-4.3V and a temperature of 0.1 ℃ at 25 ℃; using the activated cell, charge and discharge tests were performed at 0.1C, 0.2C, 0.33C, 0.5C, 1C, and the rate performance of the material was evaluated by the ratio of 1C capacity to 0.1C capacity; the cycle performance of the material was evaluated 80 times at 1C cycle in the interval of 3.0-4.4V.
When the molar ratio of Ni/Mn is not more than 1, namely x/y is not more than 1, the button cell test conditions are as follows: placing for 2h after manufacturing the button cell, after the open-circuit voltage is stable, charging to the cut-off voltage of 4.6V in a mode that the current density of the anode is 0.1C, then charging for 30min at constant voltage, and then discharging to the cut-off voltage of 2.0V at the same current density; the same procedure was repeated 1 more time, and the battery at this time was regarded as an activated battery. Using an activated battery, and carrying out a charge-discharge test to evaluate the charge-discharge capacity of the material at a voltage range of 2.0-4.6V, a charge-discharge range of 2.0-4.6V and a temperature of 0.1 ℃ at 25 ℃; using the activated cell, charge and discharge tests were performed at 0.1C, 0.2C, 0.33C, 0.5C, 1C, and the rate performance of the material was evaluated by the ratio of 1C capacity to 0.1C capacity; the cycle performance of the material was evaluated at 0.5C for 80 cycles between 2.0 and 4.6V.
Example 1
This example is intended to illustrate a lithium-containing oxide positive electrode material prepared in accordance with the present invention.
Dissolving nickel sulfate and manganese sulfate according to the metal molar ratio of 5:3 to obtain a 2mol/L mixed salt solution, dissolving cobalt sulfate and aluminum sulfate according to the metal molar ratio of Co/(Ni + Mn + Co + Al) =0.18 and Al/(Ni + Mn + Co + Al) =0.02 to obtain a 2mol/L mixed salt solution, dissolving sodium hydroxide into an alkali solution with the concentration of 6mol/L, and dissolving ammonia water into a complexing agent solution with the concentration of 5 mol/L.
Then, 20L of mixed salt solution, alkali solution and complexing agent solution are added into a reaction kettle in a parallel flow mode to carry out reaction, the stirring rotating speed is kept constant at 600 revolutions per minute, meanwhile, the liquid inlet flow of the mixed salt solution is controlled to be 300mL/h, the reaction pH is controlled to be 11.6, the reaction temperature is 50 ℃, the concentration of ammonia in a reaction system is controlled to be 9g/L, and the reaction is carried out in N 2 The reaction is carried out in air, the reaction is kept for 60 hours, the solid content is 500g/L, the slurry obtained by the precipitation crystallization reaction is subjected to solid-liquid separation and washing, then the slurry is dried for 10 hours at 105 ℃, and the spherical Ni is obtained after sieving 0.5 Mn 0.3 Co 0.18 Al 0.02 (OH) 2 Precursor material, denoted as P-1.
Precursor P-1, lithium carbonate and additive TiO 2 And WO 3 According to the weight ratio of Li (Ni + Mn + Co + Al + Ti + W) =1.03, ti:(Ni + Mn + Co + Al + Ti + W) =0.003, W (Ni + Mn + Co + Al + Ti + W) =0.002 are mixed evenly in a high-speed mixer; heating to 920 ℃ in air atmosphere, keeping for 10h, and naturally cooling to obtain a primary sintering anode material Li [ Li ] 0 Ni 0.4975 Mn 0.2985 Co 0.1791 Al 0.0199 Ti 0.003 W 0.002 ]O 2 And is marked as S-1.
The primary sintering material S-1 and the additive Nb 2 O 5 And La 2 O 3 Uniformly mixing Nb (Ni + Mn + Co + Al + Ti + W) =0.002 and La (Ni + Mn + Co + Al + Ti + W) = 0.002; heating to 650 ℃ in air atmosphere, keeping for 6h, and naturally cooling to obtain a secondary sintering anode material Li [ Li ] 0 Ni 0.4975 Mn 0.2985 Co 0.1791 Al 0.0199 Ti 0.003 W 0.002 ]O 2 @Nb 0.002 La 0.002 And is denoted as FS-1.
Examples 2 to 14
This example is intended to illustrate a lithium-containing oxide positive electrode material prepared in accordance with the present invention.
A lithium oxide-containing positive electrode material was prepared in the same manner as in example 1, except that: the preparation process of the precursor, the preparation process of the primary sintered cathode material and the preparation process of the secondary sintered cathode material are different, and are specifically shown in table 1.
TABLE 1
TABLE 1 (continuation)
TABLE 1 (continuation)
In table 1, the ratios and the amount ratios are molar ratios unless otherwise specified.
Comparative example 1
The same synthesis method and conditions as in example 5 were used, and only the first sintering temperature was adjusted to 600 ℃, and the obtained positive electrode material was denoted as D-1, as shown in table 2.
Comparative example 2
The same synthesis method and conditions as in example 5 were used, and only the first sintering temperature was adjusted to 900 ℃, and the obtained positive electrode material was denoted as D-2, as shown in table 2.
Comparative example 3
The same synthesis method and conditions as in example 5 were used, and rhenium oxide and alumina oxide were not added to the process for preparing the single-sintering positive electrode material, and the obtained positive electrode material was denoted as D-3, as shown in table 2.
Comparative example 4
The same synthesis method and conditions as in example 5 were used, and no additive, namely tungsten nitride and aluminum fluoride, was added in the preparation process of the secondary sintered positive electrode material, and the obtained positive electrode material was denoted as D-4, as shown in table 2.
Comparative example 5
The solid content was adjusted to 150g/L only in the precursor preparation process using the same synthesis method and conditions as in example 9, and the obtained cathode material was denoted as D-5, as shown in table 2.
Comparative example 6
The same synthesis method and conditions as in example 9 were used, and no additive, namely tungsten oxide and aluminum oxyhydroxide, was added in the preparation process of the single-sintering positive electrode material, and the obtained positive electrode material was denoted as D-6, as shown in table 2.
Comparative example 7
The same synthesis and conditions as in example 9 were used, except that the secondary sintering process was removed to obtain a cathode material designated as D-7, as shown in Table 2.
TABLE 2
Table 2 (continuation)
Test example 1
The lithium oxide-containing positive electrode material precursors prepared in examples 1 to 14 and comparative examples 1 to 7 were tested for their properties, and the results are shown in table 3; and the lithium oxide-containing positive electrode materials prepared in examples 1 to 14 and comparative examples 1 to 7 were tested for their properties, and the results are shown in tables 4 and 5.
TABLE 3
TABLE 4
TABLE 4 (continue)
Table 4 (continuation)
TABLE 5
Test example 2
The lithium ion batteries were prepared by using the lithium-containing oxide positive electrode materials prepared in examples 1 to 14 and comparative examples 1 to 7 as positive electrode sheets of lithium ion batteries, and the performance of the lithium ion batteries was tested, with the results shown in table 6.
TABLE 6
| Lithium ion battery | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Pole piece density (g/cm) 3 ) | 3.2 | 3.2 | 3.5 | 3.4 | 3.6 | 3.3 | 3.5 |
| 0.1C discharge capacity (mAh/g) | 173.1 | 181.3 | 192.3 | 208.7 | 225.2 | 228.3 | 233.5 |
| 1C discharge capacity (mAh/g) | 158.6 | 167.1 | 176.5 | 192.2 | 214.3 | 216.2 | 218.5 |
| 1C Capacity/0.1C Capacity (%) | 91.6 | 92.2 | 91.8 | 92.1 | 95.1 | 94.7 | 93.6 |
| Capacity retention (%) | 99.1 | 95.2 | 94.8 | 99.0 | 94.6 | 96.3 | 93.3 |
Table 6 (continue)
Table 6 (continue)
| Lithium ion battery | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 |
| Pole piece density (g/cm) 3 ) | 3.2 | 3.6 | 3.5 | 3.3 | 2.8 | 2.8 | 2.9 |
| 0.1C discharge capacity (mAh/g) | 216.9 | 208.3 | 221.7 | 214.3 | 240.9 | 241.9 | 233.0 |
| 1C discharge capacity (mAh/g) | 190.9 | 188.5 | 200.2 | 194.4 | 203.3 | 198.8 | 190.3 |
| 1C Capacity/0.1C Capacity (%) | 88.0 | 90.5 | 90.3 | 90.7 | 84.4 | 82.2 | 81.7 |
| Capacity retention (%) | 86.7 | 85.9 | 87.5 | 86.6 | 88.0 | 89.0 | 89.9 |
In addition, in the present invention, fig. 1 is a comparative graph of charge and discharge curves of example 5 and comparative example 1; as can be seen from fig. 1, it can be seen from the charge and discharge curves of comparative example 5 and comparative example 1 that the 0.1C discharge capacity (225.2 mAh/g) of the positive electrode material provided in example 5 is higher than the 0.1C discharge capacity (216.9 mAh/g) of the positive electrode material D-1 obtained when the first sintering temperature is excessively low (600 ℃).
FIG. 2 is a comparison of cycle performance for example 5 and comparative example 1; as can be seen from fig. 2, by comparing the cycle performance of example 5 with that of comparative example 1, it can be seen that the capacity retention rate (94.6%) of example 5 is significantly higher than that (86.7%) of the positive electrode material provided by D-1. This is because when the sintering temperature is too low, primary grain growth is incomplete, resulting in a low compressive index and structural instability, thus exhibiting low capacity and cycle performance.
FIG. 3 is a graph showing a comparison of charge and discharge curves of example 5 and comparative example 2; as can be seen from fig. 3, it can be seen from the charge and discharge curves of comparative example 5 and comparative example 2 that the 0.1C discharge capacity (225.2 mAh/g) of the positive electrode material provided in example 5 is higher than the 0.1C discharge capacity (208.3 mAh/g) of the obtained positive electrode material D-2 when the first sintering temperature is excessively high (900 ℃).
FIG. 4 is a comparative graph of cycle performance of example 5 and comparative example 2; from fig. 4, it can be seen that the capacity retention rate (94.6%) of example 5 is significantly higher than that (85.9%) of the positive electrode material provided by D-2 by comparing the cycle performance of example 5 and comparative example 2. This is because when the sintering temperature is too high, the primary grain growth develops excessively, which also results in a low compressive index and structural instability, thus exhibiting low capacity and cycle performance.
FIG. 5 is a comparative graph showing charge and discharge curves of example 5 and comparative example 3; as can be seen from fig. 5, from the charge and discharge curves of comparative example 5 and comparative example 3, it can be seen that the 0.1C discharge capacity (225.2 mAh/g) of example 5 is higher than the 0.1C discharge capacity (221.7 mAh/g) of the positive electrode material D-3 obtained without adding rhenium oxide and the oxidant additive in the first sintering.
FIG. 6 is a comparative graph of cycle performance of example 5 and comparative example 3; from fig. 6, it can be seen that the capacity retention rate (94.6%) of example 5 is significantly higher than that (87.5%) of the positive electrode material provided by D-3 by comparing the cycle performance of example 5 and comparative example 3. The above shows that the addition of rhenium oxide and the oxidized alumina additive in the first sintering can improve the capacity, the cycle performance and the like of the material, because the proper doping modification can improve the micro-domain structure of the material and form a lithium-containing compound on the surfaces of particles or among the particles, which both contribute to improving the compression resistance index of the material, thereby improving the electrochemical properties such as the capacity, the cycle performance and the like of the cathode material.
FIG. 7 is a comparative graph of the charge and discharge curves of example 5 and comparative example 4; from fig. 7, it can be seen that the 0.1C discharge capacity (225.2 mAh/g) of example 5 is significantly higher than the 0.1C discharge capacity (214.3 mAh/g) of the positive electrode material D-4 obtained without the addition of the tungsten nitride, aluminum fluoride additive in the second sintering, as seen from the charge and discharge curves of comparative example 5 and comparative example 4.
FIG. 8 is a comparative graph of cycle performance of example 5 and comparative example 4; from fig. 8, it can be seen that the capacity retention rate (94.6%) of example 5 is significantly higher than the capacity retention rate (86.6%) of the positive electrode material provided by D-4 by comparing the cycle performance of example 5 and comparative example 4. The addition of the tungsten nitride and aluminum fluoride additives in the second sintering process is shown to improve the capacity, the cycle performance and the like of the material, because a stable coating layer can be formed on the surface of the material, the surface micro-area structure of the material is improved, the surface side reaction of the material is reduced, and the improvement of the compression resistance index of the material is also facilitated, so that the electrochemical properties such as the capacity, the cycle performance and the like of the cathode material are improved.
FIG. 9 is a comparative graph of the charge and discharge curves of example 9 and comparative example 5; as can be seen from FIG. 9, from the charge and discharge curves of comparative example 9 and comparative example 5, it can be seen that the 0.1C discharge capacity (250.7 mAh/g) of example 9 is significantly higher than the 0.1C discharge capacity (240.9 mAh/g) of the positive electrode material D-5 obtained when the solid content is reduced to 150g/L in the precursor preparation process.
FIG. 10 is a comparative graph of cycle performance of example 9 and comparative example 5; from fig. 10, it can be seen that the capacity retention rate (93.9%) of example 9 is significantly higher than that (88.0%) of the positive electrode material provided by D-5 by comparing the cycle performance of example 9 and comparative example 5. This is because low solid content results in poor crystallinity and compactness of the precursor, and changes in morphology and microstructure, thus exhibiting a low compressive index, resulting in deterioration of electrochemical properties such as capacity and cycle performance of the material.
FIG. 11 is a comparative graph of the charge and discharge curves of example 9 and comparative example 6; as can be seen from fig. 11, from the charge and discharge curves of comparative example 9 and comparative example 6, it can be seen that the 0.1C discharge capacity (250.7 mAh/g) of example 9 is significantly higher than the 0.1C discharge capacity (241.9 mAh/g) of the positive electrode material D-6 obtained without adding the tungsten oxide and aluminum oxyhydroxide additives in the first sintering.
FIG. 12 is a comparison of cycle performance for example 9 and comparative example 6; as can be seen from fig. 12, by comparing the cycle performance of example 9 and comparative example 6, it can be seen that the capacity retention rate (93.9%) of example 9 is significantly higher than the capacity retention rate (89.0%) of the positive electrode material provided by D-6. The above shows that the addition of the tungsten oxide and aluminum oxyhydroxide additives in the first sintering can improve the capacity, cycle performance and the like of the material, because the proper doping modification can improve the micro-domain structure of the material and form a lithium-containing compound on the particle surface or among the particles, which both contribute to improving the compression index of the material, thereby improving the electrochemical properties such as the capacity, cycle performance and the like of the cathode material.
FIG. 13 is a comparative graph of the charge and discharge curves of example 9 and comparative example 7; from fig. 13, it can be seen that the 0.1C discharge capacity (250.7 mAh/g) of example 9 is significantly higher than the 0.1C discharge capacity (233.0 mAh/g) of the positive electrode material D-7 without the second sintering process by comparing the charge and discharge curves of example 9 and comparative example 7.
FIG. 14 is a comparative graph of cycle performance of example 9 and comparative example 7; as can be seen from fig. 14, by comparing the cycle performance of example 9 and comparative example 7, it can be seen that the capacity retention rate (93.9%) of example 9 is significantly higher than the capacity retention rate (89.9%) of the positive electrode material provided by D-7. The above shows that the second sintering can effectively improve the capacity, the cycle performance and the like of the material, because the second sintering process can form a stable coating layer on the surface of the material and rearrange atoms on the surface of the material, improve the surface micro-domain structure of the material, reduce the surface side reaction of the material, and improve the compression resistance index of the material, thereby improving the electrochemical properties such as the capacity, the cycle performance and the like of the cathode material.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A lithium oxide-containing positive electrode material characterized in that the positive electrode material has a compression resistance index [ Delta ]λ(P 100 ) Satisfies the following conditions: delta lambda (P) 100 )≥60％+(y/x)×5％；
Wherein y/x is the molar ratio of Mn/Ni in the positive electrode material.
2. The positive electrode material according to claim 1, wherein the positive electrode material has a compression resistance index Δ λ (P) 200 ) Satisfies the following conditions: delta lambda (P) 200 )≥45％+(y/x)×5％；
And/or the compression resistance index delta lambda (P) of the cathode material 300 ) Satisfies the following conditions: delta lambda (P) 300 )≥35％+(y/x)×5％。
3. The lithium-containing oxide positive electrode material according to claim 1 or 2, wherein the lithium-containing oxide positive electrode material has a chemical formula represented by formula (3):
Li[Li a Ni x Mn y M j ]O 2 @ M', formula (3);
wherein a is not less than 0 and not more than 0.3, x is not more than 0.2 and not more than 1, Y is not more than 0 and not more than 0.75, j is not more than 0 and not more than 0.35, M is at least one element selected from Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta and B, M 'is an oxide, phosphide, sulfide, fluoride or chloride containing at least one element selected from Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta and B, the molar content of the cation in M' is W, 0<w/(a + x + Y + j) is not more than 0.1;
preferably, 0.02. Ltoreq. A.ltoreq.0.2, 0.3. Ltoreq. X.ltoreq.0.9, 0.05. Ltoreq. Y.ltoreq.0.68, 0. Ltoreq. J.ltoreq.0.3, 0.001. Ltoreq. W/(a + x + Y + j) 0.02, M is at least one element selected from Zr, nb, ti, Y, sc, cr, co, W, mg, la, ta and B, and M' is an oxide, phosphide, sulfide or fluoride containing at least one element selected from Zr, nb, ti, Y, sc, cr, co, W, mg, la, ta and B.
4. The lithium-containing oxide positive electrode material according to any one of claims 1 to 3, wherein the lithium-containing oxide positive electrode material has a compacted density of not less than 2.8g/cm 3 Preferably ≥ 3g/cm 3 More preferably ≧3.2g/cm 3 ；
And/or the tap density of the lithium-containing oxide cathode material is more than or equal to 1.7g/cm 3 Preferably ≥ 2g/cm 3 More preferably not less than 2.4g/cm 3 ；
And/or the content of the surface soluble alkali of the lithium-containing oxide cathode material meets the following conditions:
Li 2 CO 3 ≤1wt％，LiOH≤0.5wt％；
preferably Li 2 CO 3 ≤0.5wt％，LiOH≤0.4wt％；
Further preferred is Li 2 CO 3 ≤0.3wt％，LiOH≤0.3wt％；
Even more preferred is Li 2 CO 3 ≤0.2wt％，LiOH≤0.2wt％；
And/or the presence of a gas in the gas,
the lithium-containing oxide cathode material has a full width at half maximum FWHM of a (003) crystal plane obtained by XRD (003) And FWHM of full width at half maximum of (104) crystal plane (104) The following conditions are satisfied:
0.10≤FWHM (003) 0.25 or less, preferably 0.13 or less FWHM (003) ≤0.22；
0.20≤FWHM (104) 0.50 or less, preferably 0.22 or less FWHM (104) ≤0.42；
And/or the presence of a gas in the gas,
the lithium-containing oxide cathode material has a peak area S of a (003) plane obtained by XRD (003) Peak area S of (104) and (Z) plane (104) The following conditions are satisfied:
1.1≤S (003) /S (104) 1.8, preferably 1.2S (003) /S (104) ≤1.6。
5. A lithium-containing oxide positive electrode material precursor is characterized in that the compression resistance index delta lambda' (P) of the precursor 50 ) Satisfies the following conditions: Δ λ' (P) 50 )≥35％+(v/u)×8％；
Wherein v/u is the molar ratio of Mn/Ni in the precursor.
6. According toThe precursor of claim 5, wherein the precursor has a crush resistance index Δ λ' (P) 100 ) Satisfies the following conditions: Δ λ' (P) 100 )≥25％+(v/u)×8％。
7. A method for preparing a lithium-containing oxide cathode material is characterized by comprising the following steps:
s1: a precursor having a chemical formula shown in formula (1), a lithium source, and optionally an element M 2 The additive is uniformly mixed and is sintered for the first time in an atmosphere furnace to obtain a primary sintered material with a chemical formula shown in a formula (2);
s2: uniformly mixing the primary sintered material with an additive containing an element M', and carrying out secondary sintering on the mixed material in an atmosphere furnace to obtain a lithium-containing metal oxide with a chemical formula shown in a formula (3);
Ni u Mn v M 1γ (OH) 2 formula (1);
wherein u + v + γ =1,0.2<u<1，0<v≤0.75，0≤γ≤0.35，M 1 At least one element selected from the group consisting of Al, zr, nb, ti, Y, sc, cr, co, W, mg, na, la, os, pr, re, ru, sr, sm, ta and B;
Li[Li a Ni x Mn y M j ]O 2 (ii) a Formula (2);
Li[Li a Ni x Mn y M j ]O 2 @ M', formula (3);
wherein, in formula (2) and formula (3):
a+x+y+j＝1，0≤a≤0.3，0.2<x<1，0<y≤0.75，0<j≤0.35；
m includes M in the precursor 1 Element and M in the first sintering process 2 An element;
M 1 、M 2 at least one element, which is the same or different, each selected from the group consisting of Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta and B;
in formula (3):
m 'is oxide, phosphide, sulfide, fluoride or chloride containing at least one element of Al, zr, nb, ti, Y, sc, cr, co, W, mg, la, os, pr, re, ru, sr, sm, ta and B, the mole content of cation in M' is W, 0<w/(a + x + Y + j) is less than or equal to 0.1.
8. The production method according to claim 7, wherein when the molar ratio of Ni/Mn is more than 1, i.e., x/y>1, sintering temperature T of the first sintering 1 The relationship with the Ni content satisfies: t is more than or equal to 550 x (2-x) 1 Less than or equal to 400 x (3-x) DEG C, the sintering time is 6-20h, preferably 8-15h;
and/or when the molar ratio of Ni to Mn is less than or equal to 1, namely y/x is more than or equal to 1, the sintering temperature T of the first sintering 2 The relation with the Mn content satisfies: t not more than 500 x (1+y) 2 650 x (1+y) DEG C or less, the sintering time is 6-20h, preferably 8-15h;
and/or, when x is less than 0.5, the atmosphere of the first and second sintering is air; when x is more than or equal to 0.5 and less than 0.6, the atmosphere of the first sintering and the second sintering is air or mixed gas of air and oxygen; when x is more than or equal to 0.6, the atmosphere of the first sintering and the second sintering is oxygen or mixed gas of oxygen and air.
9. A lithium-containing oxide positive electrode material produced by the method for producing a lithium-containing oxide positive electrode material according to claim 7 or 8.
10. A positive electrode sheet, comprising at least 90wt% of a lithium-containing oxide positive electrode material, based on the total weight of the positive electrode sheet;
wherein the lithium-containing oxide positive electrode material is the lithium-containing oxide positive electrode material according to any one of claims 1 to 4 and 9.
11. The positive plate according to claim 10, wherein the positive plate has a plate density of 2.8g/cm or more 3 Preferably ≥ 3.2g/cm 3 More preferably not less than 3.5g/cm 3 。
12. Use of a lithium-containing oxide positive electrode material according to any one of claims 1 to 4 and 9, a lithium-containing oxide positive electrode material precursor according to claim 5 or 6, or a positive electrode sheet according to claim 10 or 11 in a lithium ion battery.
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