WO2022267187A1 - Composite coated modified high-nickel nca positive electrode material and preparation method therefor - Google Patents
Composite coated modified high-nickel nca positive electrode material and preparation method therefor Download PDFInfo
- Publication number
- WO2022267187A1 WO2022267187A1 PCT/CN2021/111204 CN2021111204W WO2022267187A1 WO 2022267187 A1 WO2022267187 A1 WO 2022267187A1 CN 2021111204 W CN2021111204 W CN 2021111204W WO 2022267187 A1 WO2022267187 A1 WO 2022267187A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- nickel
- cobalt
- positive electrode
- preparation
- electrode material
- Prior art date
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 58
- 239000011248 coating agent Substances 0.000 claims abstract description 57
- 238000005245 sintering Methods 0.000 claims abstract description 51
- 239000011159 matrix material Substances 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000001816 cooling Methods 0.000 claims abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims abstract description 7
- 150000002815 nickel Chemical class 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 239000010406 cathode material Substances 0.000 claims description 40
- 229910012851 LiCoO 2 Inorganic materials 0.000 claims description 33
- 238000012986 modification Methods 0.000 claims description 31
- 230000004048 modification Effects 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 27
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 12
- 229940044175 cobalt sulfate Drugs 0.000 claims description 12
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 11
- 238000001035 drying Methods 0.000 abstract description 8
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 abstract description 4
- 229910032387 LiCoO2 Inorganic materials 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 40
- 239000011259 mixed solution Substances 0.000 description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 14
- 229910001416 lithium ion Inorganic materials 0.000 description 14
- 230000014759 maintenance of location Effects 0.000 description 12
- 238000003756 stirring Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 10
- 239000011247 coating layer Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 4
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910017381 Ni0.94Co0.06(OH)2 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 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 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- IWTZGPIJFJBSBX-UHFFFAOYSA-G aluminum;cobalt(2+);nickel(2+);heptahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Co+2].[Ni+2] IWTZGPIJFJBSBX-UHFFFAOYSA-G 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 230000000295 complement effect Effects 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
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M4/36—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the invention belongs to the technical field of lithium-ion battery materials, and in particular relates to a compound coated and modified high-nickel NCA cathode material and a preparation method thereof.
- Lithium-ion batteries have many advantages such as high energy density, relatively stable discharge voltage, no memory effect, wide operating temperature range, no pollution, long cycle life, and good safety performance. Since their inception, they have been used in various power-consuming equipment middle. In recent years, lithium-ion batteries have also been widely used in electric vehicles, electric bicycles and other electric tools. However, with the upgrading of electric tools, higher requirements have been put forward for lithium-ion battery capacity, service life and safety performance. Therefore, the current research and development of lithium-ion batteries is mainly divided into two directions: one is to gradually increase the energy density of lithium-ion batteries, and the other is to improve the service life and safety performance of lithium-ion batteries while meeting the energy density of batteries.
- cathode materials In lithium-ion battery systems, the capacity and cycle performance of cathode materials largely limit the energy density and service life of full batteries. Compared with traditional lithium cobalt oxide cathode materials and lithium iron phosphate cathode materials, high-nickel ternary NCA cathode materials have potential advantages such as high theoretical capacity, low cost and high voltage, and are currently a research hotspot in the field of lithium-ion battery cathode materials. wide market potential.
- the Chinese patent with the notification number CN 107946578 B discloses a lithium cobalt oxide-coated nickel-cobalt-lithium-aluminate positive electrode material and its preparation method. This method successfully improves the capacity of the positive electrode material, but its cycle performance cannot Meet existing application standards.
- Li + will be extracted and intercalated from the positive electrode material during the charging and discharging process of lithium-ion batteries, and further research has found that Li + of LiCoO 2 as the coating layer will also participate in this process. Its chemical properties are relatively stable, and it should improve the cycle while increasing the capacity.
- the present invention provides a composite coated and modified NCA positive electrode material and a preparation method thereof to solve the problems of low capacity and poor cycle performance of the NCA positive electrode material.
- the technical scheme adopted by the present invention to solve the technical problem is as follows: a composite coating modified high-nickel NCA positive electrode material, the NCA positive electrode material uses a ternary material as a matrix, and the surface of the substrate is wrapped with a composite coating modification Floor;
- the chemical formula of the ternary material is Li a Ni x Co y Al z N b O 2 , where 1.005 ⁇ a ⁇ 1.06, 0.80 ⁇ x ⁇ 0.97, 0.02 ⁇ y ⁇ 0.15, 0 ⁇ z ⁇ 0.10, 0 ⁇ b ⁇ 0.10, N is one or more of Zr, Cr, Mg, V, Ti, Sr, Sb, Y, W, Nb, Zn, Ce, Al, B, Ba, Sn;
- the composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 , and the content of the composite coating modification layer is 0.2wt%-3wt% of the total weight of the matrix.
- the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modified layer is 1:(0.5-3).
- the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 1:(1.5 ⁇ 2).
- the preparation method of the above-mentioned composite coating modified NCA cathode material comprises the following steps:
- step S2 Preparation of an alkane matrix: Mix the nickel-cobalt hydroxide precursor, lithium source, aluminum source, and N source obtained in step S1 evenly, then sinter in an oxygen atmosphere, and then cool to room temperature, pulverize and sieve to obtain an alkane matrix. base body;
- NCA positive electrode material Mix the monoalkyl body obtained in step S2 with deionized water to obtain a solid-liquid mixture, add cobalt source, and adjust the pH value to 7.0-8.5, then filter, dry, and place in an oxygen atmosphere Sintering, cooling to room temperature after sintering, and sieving to obtain a composite-coated modified high-nickel NCA positive electrode material.
- the above-mentioned sintering in step S3 includes a preheating process and multiple repeated heating and cooling processes.
- the preheating process increases the temperature from room temperature to 400-450° C., and the preheating time is 1 to 3 hours.
- the valley temperature is between 400°C and 450°C, and the peak temperature is controlled between 700°C and 750°C.
- the material composition of the modified layer formed on the surface layer of the NCA cathode material is different, through multi-stage temperature rise and fall, LiCoO 2 and Co 2 O 3 in the composite coating modified layer can form an alternating coating layer , can improve the coating effect.
- the ratio of heating time to cooling time in each heating and cooling cycle is 1:(1-3).
- the time control of heating and cooling is complementary to the multi-stage heating and cooling. By adjusting the holding time of a suitable temperature section, it can play a role in adjusting the proportion of the coating layer.
- the nickel salt is selected from one or more of nickel sulfate, nickel nitrate or nickel chloride;
- the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate or cobalt chloride one or more species; the molar ratio of the nickel salt to the cobalt salt is (0.85-0.97): (0.03-0.15).
- step S1 the temperature of the reactor is controlled at 40-80° C., and the pH value is controlled at 10-14.
- the lithium source is one or both of lithium carbonate and lithium hydroxide;
- the aluminum source is selected from one or both of aluminum hydroxide and aluminum oxide.
- the sintering time is 5-28 hours, and the sintering temperature is controlled at 700-850°C.
- the cobalt source is selected from one or more of cobalt nitrate, cobalt sulfate, and cobalt chloride; the cobalt source accounts for 2wt% to 8wt% of the weight of the alkyl base.
- the solid-to-liquid ratio of the monoalkyl body to the deionized water is: (0.5-1.0):1.
- the temperature of the solid-liquid mixture is controlled to be 25 ⁇ 3°C.
- the nickel-cobalt hydroxide precursor is doped with aluminum, and aluminum exists as Al3 + , which does not participate in the electrochemical reaction, and plays a role in stabilizing the structure of the crystal for the skeleton of the material, Thus, the crystal structure can be effectively controlled.
- the composite coating modified layer in the present invention is composed of LiCoO 2 and Co 2 O 3.
- the presence of LiCoO 2 coating layer can facilitate the transmission of lithium ions and effectively improve the material capacity. It also has a certain effect on the cycle performance; in the process of charging and discharging, when the lithium ions in the LiCoO 2 in the cladding layer are extracted more than 50%, the O 2- may be reduced, which will lead to the loss of oxygen in the lattice, resulting in a loss of cycle performance.
- the oxygen atoms in it can migrate into the LiCoO 2 crystal structure under the concentration gradient, reducing the loss of oxygen in the crystal structure during charge and discharge, thereby stabilizing the crystal of LiCoO 2 structure, thereby improving the cycle performance; while Co 2 O 3 is an inorganic compound material with relatively stable chemical properties, which can hinder the direct contact of the electrolyte to the material to the greatest extent, reduce the side reactions on the surface of the material, and is conducive to the improvement of cycle performance. promote.
- the coating technology in the present invention improves the capacity through LiCoO 2 , and the Co 2 O 3 coating layer not only has the effect of reducing the side reaction of the positive electrode material itself, but also can effectively solve the problem of lithium ions coming out of the LiCoO 2 coating layer during charging and discharging. It can also improve the thermal stability of the positive electrode material.
- the synergistic effect of the two can significantly improve the capacity and cycle performance of the cathode material.
- the present invention adopts multi-stage temperature rise and fall and temperature control, so as to facilitate the regulation of the ratio of coatings in the surface layer, and finally help to form a specific ratio of LiCoO 2 and Co 2 O 3 composite coating modified layer. Because there is a concentration gradient and atomic migration of atoms during the formation process, there is no obvious interface layer between the two, but interdependent crossing exists in the cladding layer, which is conducive to improving the structural stability of the composite cladding layer and improving cycle performance.
- Fig. 1 is the electron microprobe analysis diagram (EPMA) of positive electrode material obtained in Example 1 of the present invention
- Fig. 2 is the transmission electron microscope analysis diagram (TEM) of positive electrode material obtained in Example 1 of the present invention
- Fig. 3 is the X-ray photoelectron energy spectrum analysis figure (XPS) of positive electrode material obtained in Example 1 of the present invention
- Fig. 4 is the differential scanning calorimetry contrast chart (DSC) of positive electrode material obtained in Example 1 of the present invention and Comparative Example 1;
- Fig. 5 is a graph showing the variation of the discharge capacity retention rate of the cathode materials obtained in Example 1 and Comparative Example 1 of the present invention at 45°C.
- a composite coating modified high-nickel NCA positive electrode material uses nickel-cobalt lithium aluminate as a matrix, and a composite coating modification layer is wrapped on the surface of the substrate.
- the composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 composition, the content of the composite coating modification layer is 1.0wt% of the total weight of the matrix.
- the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 1:1.5.
- the chemical formula of lithium nickel cobalt aluminate is Li 1.01 Ni 0.913 Co 0.069 Al 0.015 Ti 0.003 O 2 .
- the method for preparing the above-mentioned NCA cathode material comprises the following steps:
- the metal molar concentration of the nickel-cobalt mixed solution is 1.0mol/L, and then the sodium hydroxide precipitant and ammonia water
- the complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the reactor is controlled to be 45° C., the pH value of the mixed solution in the controlled reactor is 13.5, and the solution in the reactor is stirred for precipitation reaction. After the reaction is completed, the After aging, carry out solid-liquid separation, then use deionized water to wash repeatedly, and obtain Ni 0.93 Co 0.07 (OH) 2 precursor after vacuum drying;
- Button electricity test Mix the obtained active material, acetylene black and polyvinylidene fluoride (PVDF), use N-methylpyrrolidone (NMP) as a solvent to make the mixture into a paste, and then evenly coat it on the aluminum foil of the current collector , rolled after drying to make a positive electrode sheet, and the negative electrode is a disc-shaped lithium metal with a diameter of 12mm; the separator is a microporous polypropylene film (Celgard - 2300) with a diameter of 14mm; Ethyl ester and dimethyl carbonate mixed solution, the volume ratio is 1:2:1, the moisture content of the electrolyte is less than 30ppm; the test battery is a 2032 button battery, and the voltage test range is 3.0-4.3V.
- PVDF polyvinylidene fluoride
- NMP N-methylpyrrolidone
- the specific capacity of the first discharge capacity is 217.8mAh/g, as shown in Figure 5, after 50 cycles at a high temperature of 45°C, the discharge capacity retention rate is 96.1%.
- a composite coating modified high-nickel NCA positive electrode material uses nickel-cobalt lithium manganese oxide as a matrix, and a composite coating modification layer is wrapped on the surface of the substrate.
- the composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 , the content of the composite coating modification layer is 1.0wt% of the total weight of the matrix.
- the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 1:2.
- the chemical formula of nickel cobalt lithium manganate is Li 1.01 Ni 0.913 Co 0.069 Al 0.015 Ti 0.003 O 2 .
- the method for preparing the above-mentioned NCA cathode material comprises the following steps:
- the metal molar concentration of the nickel-cobalt mixed solution is 1.0mol/L, and then sodium hydroxide precipitant and ammonia water
- the complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the reactor is controlled to be 55° C., the pH value of the mixed solution in the controlled reactor is 13.0, and the solution in the reactor is stirred for precipitation reaction. After the reaction is completed, the After aging, carry out solid-liquid separation, then use deionized water to wash repeatedly, and obtain Ni 0.93 Co 0.07 (OH) 2 precursor after vacuum drying;
- the material was placed in an oxygen atmosphere furnace Carry out sintering, the sintering time is 10h, the sintering system is raised from room temperature to 420°C for 2h, then raised to 700°C for 2h, then lowered to 420°C for 2h, then raised to 600°C for 1h, cooled to 420°C for 1h, and finally After cooling down to room temperature for 2 hours, the composite coated and modified high-nickel NCA positive electrode material was obtained after sieving.
- a composite coating modified high-nickel NCA positive electrode material uses nickel-cobalt lithium aluminate as a matrix, and a composite coating modification layer is wrapped on the surface of the substrate.
- the composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 composition, the content of the composite coating modification layer is 0.6wt% of the total weight of the matrix.
- the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 1:1.
- the chemical formula of lithium nickel cobalt aluminate is Li 1.05 Ni 0.923 Co 0.049 Al 0.026 Y 0.002 O 2 .
- the method for preparing the above-mentioned NCA cathode material comprises the following steps:
- the nickel nitrate solution and the cobalt chloride solution are mixed as raw materials, the metal molar concentration of the nickel-cobalt mixed solution is 1.0mol/L, and then the sodium hydroxide precipitating agent and The ammonia water complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the controlled reactor is 65°C, the pH value of the mixed solution in the controlled reactor is 13.0, and the solution in the stirred reactor is subjected to precipitation reaction. After the reaction is completed, Separation of solid and liquid after aging, repeated washing with deionized water, and vacuum drying to obtain the Ni 0.95 Co 0.05 (OH) 2 precursor;
- the material was placed in an oxygen atmosphere Sintering in the furnace, the sintering time is 9h, the sintering system is heated from room temperature to 410°C for 1.5h, then raised to 730°C for 1.5h, then cooled to 410°C for 1.5h, then raised to 730°C for 1h, and cooled to 410°C, and finally cooled down to room temperature for 2.5 hours to take out the furnace, and after sieving, a composite-coated modified high-nickel NCA positive electrode material was obtained.
- a composite coating modified high-nickel NCA positive electrode material uses nickel-cobalt lithium manganese oxide as a matrix, and a composite coating modification layer is wrapped on the surface of the substrate.
- the composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 , the content of the composite coating modification layer is 0.6wt% of the total weight of the matrix.
- the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 2:1.
- the chemical formula of nickel cobalt lithium manganate is Li 1.05 Ni 0.923 Co 0.049 Al 0.026 Y 0.002 O 2 .
- the method for preparing the above-mentioned NCA cathode material comprises the following steps:
- Ni:Co 95:5 Under the condition of the molar ratio of Ni:Co 95:5, nickel nitrate solution and cobalt sulfate solution are mixed as raw materials.
- the complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the reactor is controlled to be 55° C., the pH value of the mixed solution in the controlled reactor is 13.0, and the solution in the reactor is stirred for precipitation reaction. After the reaction is completed, the After aging, carry out solid-liquid separation, then use deionized water to wash repeatedly, and obtain Ni 0.95 Co 0.05 (OH) 2 precursor after vacuum drying;
- the material was placed in an oxygen atmosphere furnace Sintering, the sintering time is 10h, the sintering system is heated from room temperature to 420°C for 2h, then raised to 700°C in 1h, then cooled to 420°C in 2h, then raised to 600°C in 1.5h, and cooled to 420°C in 3.0h. Finally, the temperature was lowered to room temperature for 2 hours, and the compound-coated modified high-nickel NCA positive electrode material was obtained after sieving.
- a composite coating modified high-nickel NCA positive electrode material uses nickel-cobalt lithium aluminate as a matrix, and a composite coating modification layer is wrapped on the surface of the substrate.
- the composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 composition, the content of the composite coating modification layer is 2.6wt% of the total weight of the matrix.
- the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 1:3.
- the chemical formula of lithium nickel cobalt aluminate is Li 1.05 Ni 0.911 Co 0.058 Al 0.012 Mg 0.019 O 2 .
- the method for preparing the above-mentioned NCA cathode material comprises the following steps:
- the metal molar concentration of the nickel-cobalt mixed solution is 1.0mol/L, and then the sodium hydroxide precipitating agent and The ammonia water complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the controlled reactor is 65°C, the pH value of the mixed solution in the controlled reactor is 13.0, and the solution in the stirred reactor is subjected to precipitation reaction. After the reaction is completed, Separation of solid and liquid after aging, repeated washing with deionized water, and vacuum drying to obtain the Ni 0.94 Co 0.06 (OH) 2 precursor;
- the material was placed in an oxygen atmosphere Sintering in the furnace, the sintering time is 9h, the sintering system is heated from room temperature to 410°C for 2h, then raised to 730°C for 2h, then cooled to 410°C for 2h, then raised to 730°C for 1h, and cooled to 410°C for 1h, Finally, the temperature was lowered to room temperature for 2 hours, and the compound-coated modified high-nickel NCA positive electrode material was obtained after sieving.
- NCA positive electrode material is based on nickel cobalt lithium aluminate, and the chemical formula of nickel cobalt lithium aluminate is Li 1.01 Ni 0.913 Co 0.069 Al 0.015 Ti 0.003 O 2 .
- the method for preparing the above-mentioned NCA cathode material comprises the following steps:
- the metal molar concentration of the nickel-cobalt mixed solution is 1.0mol/L, and then the sodium hydroxide precipitant and ammonia water
- the complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the reactor is controlled to be 45° C., the pH value of the mixed solution in the controlled reactor is 13.5, and the solution in the reactor is stirred for precipitation reaction. After the reaction is completed, the After aging, carry out solid-liquid separation, then use deionized water to wash repeatedly, and obtain Ni 0.93 Co 0.07 (OH) 2 precursor after vacuum drying;
- a nickel-cobalt-lithium-aluminate positive electrode material coated with lithium cobaltate obtained by referring to CN 107946578 B in the background technology, the positive electrode material is based on nickel-cobalt lithium-aluminate, and the chemical formula of nickel-cobalt lithium-aluminate is Li 1.01 Ni 0.913 Co 0.069 Al 0.015 Ti 0.003 O 2 , a LiCoO 2 coating modification layer is wrapped on the surface of the substrate, and the content of the coating modification layer is 1 wt% of the total weight of the substrate.
- step (1) (2) Add 10g (108.96mmol) nickel cobalt aluminum hydroxide, 0.2714g (1.09mmol) cobalt acetate tetrahydrate, 11.781g (115.48mmol) lithium acetate dihydrate, and 0.02518g (0.3178mmol) titanium oxide to step (1) simultaneously ) in the obtained surface active solution, placed in a magnetic stirrer equipped with an ultrasonic device, heated to 50 ° C, and ultrasonically stirred for 3 hours at an ultrasonic frequency of 20 kHz and a stirring speed of 1000 r/min to obtain a suspension;
- step (3) The suspension obtained in step (2) is under ultrasonic stirring with an ultrasonic frequency of 20kHz and a stirring speed of 1000r/min, and at a feed rate of 500mL/h, an air inlet temperature of 250°C, and an air outlet temperature of 250°C. Spray-dry at 120°C to obtain the precursor powder of nickel-cobalt-lithium-aluminate cathode material coated with lithium cobaltate;
- step (3) Place the precursor powder of the lithium cobaltate-coated nickel-cobalt-lithium-aluminate positive electrode material obtained in step (3) in a tube furnace. Raise the temperature to 480°C at a high rate, sinter for 5 hours, then raise the temperature to 800°C at a rate of 4°C/min, and sinter for 15 hours to obtain a lithium cobaltate-coated nickel-cobalt-lithium-aluminate cathode material.
- the discharge capacity and cycle retention rate of Examples 1-5 are significantly better than those of Comparative Example 1 which is not coated.
- the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer in Example 1 is 1:1.5, the discharge capacity can reach 217.8mAh/g, and the cycle retention rate is 96.1%;
- the composite coating modification layer in Example 2 The molar ratio of LiCoO 2 to Co 2 O 3 in the active layer is 1:2, the discharge capacity can reach 216.3mAh/g, and the cycle retention rate is 96.7%.
- Example 3 and Example 4 the molar ratio of LiCoO 2 to Co 2 O 3 is greater than 1:1.5, the discharge capacity is not significantly improved compared to Example 1, but the cycle performance is reduced rapidly; the LiCoO in Example 5 The molar ratio of 2 to Co 2 O 3 is 1:3, and the test value of its cycle performance has not improved compared with Example 2, but the capacity has reached 215.0mAh/g.
- Comparative Example 2 which is only coated with lithium cobaltate, is indeed beneficial to increase the capacity compared with no coating, but compared with Example 1, due to the single lithium cobaltate coating layer is prone to crystallization during charging and discharging. The change of the lattice structure will lead to the obvious deterioration of its cycle performance.
Abstract
Provided in the present invention is a composite coated modified high-nickel NCA positive electrode material and a preparation method therefor. The NCA positive electrode material has a ternary material as a matrix, and the surface of the matrix is coated with a composite coating modifying layer composed of LiCoO2 and Co2O3. The preparation method comprises: subjecting a nickel salt solution, a cobalt salt solution, a sodium hydroxide solution and an ammonia water solution to a co-precipitation reaction to obtain a nickel-cobalt hydroxide precursor; uniformly mixing the resulting nickel-cobalt hydroxide precursor with a lithium source and an M source, then sintering same in an oxygen atmosphere, then cooling same to room temperature, and crushing and sieving same to obtain a primary sintered matrix; and mixing the resulting primary sintered matrix with deionized water, adding a cobalt source, adjusting the pH value, then filtering and drying same, placing same in an oxygen atmosphere for repeated heating and cooling sintering, then cooling same after the sintering, and sieving same to obtain the composite coated modified high-nickel NCA positive electrode material. The resulting NCA positive electrode material has a high capacity and a good cycle performance.
Description
本发明属于锂离子电池材料技术领域，尤其涉及一种复合包覆改性的高镍NCA正极材料及其制备方法。The invention belongs to the technical field of lithium-ion battery materials, and in particular relates to a compound coated and modified high-nickel NCA cathode material and a preparation method thereof.
锂离子电池由于具有能量密度高、放电电压较为稳定、无记忆效应、工作温度范围宽、无污染、循环寿命长、安全性能好等诸多优点，自问世以来，即被应用于各种耗电设备中。近年来锂离子电池在电动汽车、电动自行车等电动工具上也被广泛应用，但随着电动工具的升级换代，对锂离子电池容量、使用寿命及安全性能也提出了更高的要求。因而目前锂离子电池的研发主要分为两个方向：一是逐步提高锂离子电池的能量密度，二是在满足电池能量密度的同时，提高锂离子电池的使用寿命和安全性能。锂离子电池体系中，正极材料的容量和循环性能很大程度上限制了全电池的能量密度与使用寿命。相较传统钴酸锂正极材料和磷酸铁锂正极材料，高镍三元NCA正极材料具有高理论容量、低成本以及高电压等潜在优势，是目前锂离子电池正极材料领域的研究热点，有非常广的市场潜力。Lithium-ion batteries have many advantages such as high energy density, relatively stable discharge voltage, no memory effect, wide operating temperature range, no pollution, long cycle life, and good safety performance. Since their inception, they have been used in various power-consuming equipment middle. In recent years, lithium-ion batteries have also been widely used in electric vehicles, electric bicycles and other electric tools. However, with the upgrading of electric tools, higher requirements have been put forward for lithium-ion battery capacity, service life and safety performance. Therefore, the current research and development of lithium-ion batteries is mainly divided into two directions: one is to gradually increase the energy density of lithium-ion batteries, and the other is to improve the service life and safety performance of lithium-ion batteries while meeting the energy density of batteries. In lithium-ion battery systems, the capacity and cycle performance of cathode materials largely limit the energy density and service life of full batteries. Compared with traditional lithium cobalt oxide cathode materials and lithium iron phosphate cathode materials, high-nickel ternary NCA cathode materials have potential advantages such as high theoretical capacity, low cost and high voltage, and are currently a research hotspot in the field of lithium-ion battery cathode materials. wide market potential.
为了改善高镍三元NCA正极材料的容量、循环以及安全性能，常用的改性手段包括利用各种金属元素或非金属元素进行掺杂和包覆。公开号为CN106532038A的中国专利，公开了一种镍钴铝酸锂正极材料的制备方法，其通过在烧结工艺中加入自铝、镁、钡、锆等金属元素，提高了循环性能和高温存储性能，但是其容量偏低。上述专利中所列举的几种包覆元素，虽然实现产业化已有较长时间，但是各大正极材料厂商在此基础上进行研发，包括调控锂配比、包覆量、烧结温度、其他工艺参数以及引入新工艺，均难以突破容量偏低的桎梏。In order to improve the capacity, cycle, and safety performance of high-nickel ternary NCA cathode materials, commonly used modification methods include doping and coating with various metal elements or non-metal elements. The Chinese patent with the publication number CN106532038A discloses a method for preparing a nickel-cobalt lithium aluminate positive electrode material, which improves cycle performance and high-temperature storage performance by adding metal elements such as aluminum, magnesium, barium, and zirconium in the sintering process , but its capacity is low. Although several coating elements listed in the above patents have been industrialized for a long time, major cathode material manufacturers have carried out research and development on this basis, including adjusting the ratio of lithium, coating amount, sintering temperature, and other processes. parameters and the introduction of new processes, it is difficult to break through the shackles of low capacity.
由此，为了提高NCA正极材料的容量，有研究者想到利用同为正极材料的钴酸锂作为包覆物质。如公告号为CN 107946578 B的中国专利，公开了一种钴酸锂包覆的镍钴铝酸锂正极材料及其制备方法，该方法成功地提高了正极材料的容量，但是其循环性能却无法满足现有应用标准。Li
+在锂离子电池的充放电过程中会从正极材料中脱出和嵌入，而进一步研究发现作为包覆层的LiCoO
2的Li
+也会参与此过程，看似钴酸锂作为包覆层其本身化学性质较为稳定，理应在提高容量的同时还能改善循环。但是，实际上当包裹层中的LiCoO
2中的锂离子脱出大于50％时，O
2-可能被还原，进而导致晶格中氧损失，循环性能衰减，安全性能下降。即包覆层中的钴酸锂在变成缺锂态后，其晶格结构也将发生逐渐发生变化，使其包覆层不再稳定，从而难以阻止正极材料和电解液之间发生的副反应。因此，如何研发一种容量高、循环性能好的NCA正极材料成为当今社会亟待解决的问题。
Therefore, in order to increase the capacity of the NCA cathode material, some researchers thought of using lithium cobaltate, which is also the cathode material, as the coating material. For example, the Chinese patent with the notification number CN 107946578 B discloses a lithium cobalt oxide-coated nickel-cobalt-lithium-aluminate positive electrode material and its preparation method. This method successfully improves the capacity of the positive electrode material, but its cycle performance cannot Meet existing application standards. Li + will be extracted and intercalated from the positive electrode material during the charging and discharging process of lithium-ion batteries, and further research has found that Li + of LiCoO 2 as the coating layer will also participate in this process. Its chemical properties are relatively stable, and it should improve the cycle while increasing the capacity. However, in fact, when more than 50% of the lithium ions in LiCoO 2 in the cladding layer are extracted, O 2- may be reduced, which will lead to the loss of oxygen in the lattice, the degradation of cycle performance, and the decrease of safety performance. That is to say, after the lithium cobalt oxide in the coating layer becomes lithium-deficient, its lattice structure will gradually change, making the coating layer no longer stable, making it difficult to prevent the occurrence of side effects between the positive electrode material and the electrolyte. reaction. Therefore, how to develop a NCA cathode material with high capacity and good cycle performance has become an urgent problem to be solved in today's society.
发明内容Contents of the invention
本发明正是基于现有技术的技术缺陷，提供了一种复合包覆改性的的NCA正极材料及其制备方法，以解决NCA正极材料容量低、循环性能差的问题。Based on the technical defects of the prior art, the present invention provides a composite coated and modified NCA positive electrode material and a preparation method thereof to solve the problems of low capacity and poor cycle performance of the NCA positive electrode material.
本发明解决其技术问题所采用的技术方案如下：一种复合包覆改性的高镍NCA正极材料，所述NCA正极材料以三元材料为基体，在基体的表面包裹有复合包覆改性层；The technical scheme adopted by the present invention to solve the technical problem is as follows: a composite coating modified high-nickel NCA positive electrode material, the NCA positive electrode material uses a ternary material as a matrix, and the surface of the substrate is wrapped with a composite coating modification Floor;
所述三元材料的化学式为Li
aNi
xCo
yAl
zN
bO
2，其中1.005≤a≤1.06，0.80≤x≤0.97，0.02≤y≤0.15，0<z≤0.10，0≤b≤0.10，N为Zr、Cr、Mg、V、Ti、Sr、Sb、Y、W、Nb、Zn、Ce、Al、B、Ba、Sn中的一种或多种；
The chemical formula of the ternary material is Li a Ni x Co y Al z N b O 2 , where 1.005≤a≤1.06, 0.80≤x≤0.97, 0.02≤y≤0.15, 0<z≤0.10, 0≤b≤ 0.10, N is one or more of Zr, Cr, Mg, V, Ti, Sr, Sb, Y, W, Nb, Zn, Ce, Al, B, Ba, Sn;
所述复合包覆改性层由LiCoO
2与Co
2O
3组成，所述复合包覆改性层的含量为基体总重量的0.2wt％～3wt％。
The composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 , and the content of the composite coating modification layer is 0.2wt%-3wt% of the total weight of the matrix.
优选的，上述复合包覆改性层中LiCoO
2与Co
2O
3的摩尔比为1:(0.5～3)。
Preferably, the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modified layer is 1:(0.5-3).
进一步优选的，所述复合包覆改性层中LiCoO
2与Co
2O
3的摩尔比为1:(1.5～2)。
Further preferably, the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 1:(1.5˜2).
上述复合包覆改性的NCA正极材料的制备方法，包括以下步骤：The preparation method of the above-mentioned composite coating modified NCA cathode material comprises the following steps:
S1、氢氧化物前驱体制备：将镍盐溶液、钴盐溶液、氢氧化钠溶液及氨水溶液泵入反应釜中，发生共沉淀反应，得到镍钴氢氧化物前驱体；S1. Preparation of hydroxide precursor: pump nickel salt solution, cobalt salt solution, sodium hydroxide solution and ammonia solution into the reaction kettle, and a co-precipitation reaction occurs to obtain a nickel-cobalt hydroxide precursor;
S2、一烧基体的制备：将步骤S1得到的镍钴氢氧化物前驱体、锂源、铝源、N源混合均匀，然后在氧气气氛中烧结，后冷却至室温，粉碎过筛后得到一烧基体；S2. Preparation of an alkane matrix: Mix the nickel-cobalt hydroxide precursor, lithium source, aluminum source, and N source obtained in step S1 evenly, then sinter in an oxygen atmosphere, and then cool to room temperature, pulverize and sieve to obtain an alkane matrix. base body;
S3、NCA正极材料的制备：将步骤S2得到的一烧基体与去离子水混合得到固液混合物，加入钴源，并调节pH值至7.0-8.5，然后过滤、干燥，再置于氧气气氛中烧结，烧结后冷却至室温，过筛后即可得到复合包覆改性的高镍NCA正极材料。S3. Preparation of NCA positive electrode material: Mix the monoalkyl body obtained in step S2 with deionized water to obtain a solid-liquid mixture, add cobalt source, and adjust the pH value to 7.0-8.5, then filter, dry, and place in an oxygen atmosphere Sintering, cooling to room temperature after sintering, and sieving to obtain a composite-coated modified high-nickel NCA positive electrode material.
进一步优选的，上述所述步骤S3的烧结包括预热过程以及多个反复的升温降温过程，预热过程使温度由室温上升至400～450℃，预热时间为1～3h，升温降温过程中波谷温度在400℃～450℃，波峰温度控制在700℃～750℃。在不同的温度下反应，NCA正极材料表面层生成的改性层的物质成分不一样，通过多段的升降温可以将复合包覆改性层中的LiCoO
2与Co
2O
3形成交互包覆层，能够提高包覆效果。
Further preferably, the above-mentioned sintering in step S3 includes a preheating process and multiple repeated heating and cooling processes. The preheating process increases the temperature from room temperature to 400-450° C., and the preheating time is 1 to 3 hours. During the heating and cooling process, The valley temperature is between 400°C and 450°C, and the peak temperature is controlled between 700°C and 750°C. Reaction at different temperatures, the material composition of the modified layer formed on the surface layer of the NCA cathode material is different, through multi-stage temperature rise and fall, LiCoO 2 and Co 2 O 3 in the composite coating modified layer can form an alternating coating layer , can improve the coating effect.
进一步优选的，上述步骤S3中，所述反复的升温降温过程中，每个升温降温的周期内升温时间与降温时间比为1:(1～3)。升降温的时间控制同多段升降温是相辅相成，通过调节合适的温度段的保持时间，能够起到调整包覆层比例的作用。Further preferably, in the above step S3, in the repeated heating and cooling process, the ratio of heating time to cooling time in each heating and cooling cycle is 1:(1-3). The time control of heating and cooling is complementary to the multi-stage heating and cooling. By adjusting the holding time of a suitable temperature section, it can play a role in adjusting the proportion of the coating layer.
进一步优选的，上述步骤S1中，所述镍盐选自硫酸镍、硝酸镍或氯化镍中的一种或多种；所述钴盐选自硫酸钴、硝酸钴或氯化钴中的一种或多种；所述镍盐和钴盐的摩尔比为(0.85～0.97):(0.03～0.15)。Further preferably, in the above step S1, the nickel salt is selected from one or more of nickel sulfate, nickel nitrate or nickel chloride; the cobalt salt is selected from one or more of cobalt sulfate, cobalt nitrate or cobalt chloride one or more species; the molar ratio of the nickel salt to the cobalt salt is (0.85-0.97): (0.03-0.15).
步骤S1中，反应釜的温度控制为40-80℃，pH值控制为10-14。In step S1, the temperature of the reactor is controlled at 40-80° C., and the pH value is controlled at 10-14.
进一步优选的，上述步骤S2中，所述锂源为碳酸锂、氢氧化锂中的一种或两种；所述铝源选自氢氧化铝、氧化铝中的一种或两种。Further preferably, in the above step S2, the lithium source is one or both of lithium carbonate and lithium hydroxide; the aluminum source is selected from one or both of aluminum hydroxide and aluminum oxide.
进一步优选的，上述步骤S2中，烧结时间为5-28h，烧结温度控制在700-850℃。Further preferably, in the above step S2, the sintering time is 5-28 hours, and the sintering temperature is controlled at 700-850°C.
进一步优选的，上述步骤S3中，所述钴源选自硝酸钴、硫酸钴、氯化钴中的一种或几种；所述钴源占一烧基体重量的2wt％～8wt％。Further preferably, in the above step S3, the cobalt source is selected from one or more of cobalt nitrate, cobalt sulfate, and cobalt chloride; the cobalt source accounts for 2wt% to 8wt% of the weight of the alkyl base.
进一步优选的，上述步骤S3中，所述一烧基体与去离子水的固液比为：(0.5～1.0):1。加入钴源时控制所述固液混合物的温度为25±3℃。Further preferably, in the above step S3, the solid-to-liquid ratio of the monoalkyl body to the deionized water is: (0.5-1.0):1. When adding the cobalt source, the temperature of the solid-liquid mixture is controlled to be 25±3°C.
与现有技术相比，本发明的技术优点在于：Compared with prior art, technical advantage of the present invention is:
(1)本发明在一烧基体的制备过程中，镍钴氢氧化物前驱体掺入铝，铝以Al
3+存在，不参加电化学反应，对材料的骨架起到稳定晶体的结构的作用，从而使晶体结构得到有效控制。
(1) In the preparation process of an alkane matrix in the present invention, the nickel-cobalt hydroxide precursor is doped with aluminum, and aluminum exists as Al3 + , which does not participate in the electrochemical reaction, and plays a role in stabilizing the structure of the crystal for the skeleton of the material, Thus, the crystal structure can be effectively controlled.
(2)本发明中的复合包覆改性层由LiCoO
2与Co
2O
3复合而成，在充放电的过程中，LiCoO
2包裹层存在能够有利于锂离子的传输，有效提高材料容量，对循环性能也有一定的效果；在充放电的过程中，当包裹层中的LiCoO
2中的锂离子脱出大于50％时，O
2-可能被还原，进而导致晶格中氧损失，致使循环性能衰减，而包裹层是LiCoO
2与Co
2O
3混合物，其中的氧原子在浓度梯度下能够迁移到LiCoO
2晶体结构中，减少充放电过程中晶体结构中氧的损失，进而稳定LiCoO
2的晶体结构，从而提高循环性能；而Co
2O
3是一种化学性质较为稳定的无机化合物材料，能够最大限度的阻碍电解液对材料的直接接触，减少材料表面发生的副反应，有利于循环性能的提升。本发明中的包覆技术通过LiCoO
2提高容量，Co
2O
3包覆层不仅自身具有减少正极材料副反应的作用，而且还能有效解决LiCoO
2包覆层在充放电过程中锂离子脱出而导致循环性能衰减的问题，同时也可改善正极材料的热稳定性。两者协同作用，可显著提升正极材料的容量和循环性能。
(2) The composite coating modified layer in the present invention is composed of LiCoO 2 and Co 2 O 3. In the process of charging and discharging, the presence of LiCoO 2 coating layer can facilitate the transmission of lithium ions and effectively improve the material capacity. It also has a certain effect on the cycle performance; in the process of charging and discharging, when the lithium ions in the LiCoO 2 in the cladding layer are extracted more than 50%, the O 2- may be reduced, which will lead to the loss of oxygen in the lattice, resulting in a loss of cycle performance. Attenuation, while the cladding layer is a mixture of LiCoO 2 and Co 2 O 3 , the oxygen atoms in it can migrate into the LiCoO 2 crystal structure under the concentration gradient, reducing the loss of oxygen in the crystal structure during charge and discharge, thereby stabilizing the crystal of LiCoO 2 structure, thereby improving the cycle performance; while Co 2 O 3 is an inorganic compound material with relatively stable chemical properties, which can hinder the direct contact of the electrolyte to the material to the greatest extent, reduce the side reactions on the surface of the material, and is conducive to the improvement of cycle performance. promote. The coating technology in the present invention improves the capacity through LiCoO 2 , and the Co 2 O 3 coating layer not only has the effect of reducing the side reaction of the positive electrode material itself, but also can effectively solve the problem of lithium ions coming out of the LiCoO 2 coating layer during charging and discharging. It can also improve the thermal stability of the positive electrode material. The synergistic effect of the two can significantly improve the capacity and cycle performance of the cathode material.
(3)本发明通过在烧结阶段采用多段升温降温并进行控温，便于对表面层中包覆物的比例进行调控，最终有助于形成特定比例的LiCoO
2与Co
2O
3的复合包覆改性层。由于形成的过程中原子存在浓度梯度和原子迁移，故两者之间不存在明显的界面层，而是相互依存交叉存在于包裹层中，从而有利于提高复合包覆层的结构稳定性，提高循环性能。
(3) In the sintering stage, the present invention adopts multi-stage temperature rise and fall and temperature control, so as to facilitate the regulation of the ratio of coatings in the surface layer, and finally help to form a specific ratio of LiCoO 2 and Co 2 O 3 composite coating modified layer. Because there is a concentration gradient and atomic migration of atoms during the formation process, there is no obvious interface layer between the two, but interdependent crossing exists in the cladding layer, which is conducive to improving the structural stability of the composite cladding layer and improving cycle performance.
图1为本发明实施例1所得正极材料的电子显微探针分析图(EPMA)；Fig. 1 is the electron microprobe analysis diagram (EPMA) of positive electrode material obtained in Example 1 of the present invention;
图2为本发明实施例1所得正极材料的透射电子显微镜分析图(TEM)；Fig. 2 is the transmission electron microscope analysis diagram (TEM) of positive electrode material obtained in Example 1 of the present invention;
图3为本发明实施例1所得正极材料的X射线光电子能谱分析图(XPS)；Fig. 3 is the X-ray photoelectron energy spectrum analysis figure (XPS) of positive electrode material obtained in Example 1 of the present invention;
图4为本发明实施例1与对比例1所得正极材料的差示扫描量热对比图(DSC)；Fig. 4 is the differential scanning calorimetry contrast chart (DSC) of positive electrode material obtained in Example 1 of the present invention and Comparative Example 1;
图5为本发明实施例1与对比例1所得正极材料在45℃时放电容量保持率变化图。Fig. 5 is a graph showing the variation of the discharge capacity retention rate of the cathode materials obtained in Example 1 and Comparative Example 1 of the present invention at 45°C.
为了便于理解本发明，下文将以实施例的方式对本发明做更全面、细致地描述，但本发明的保护范围并不限于以下具体实施例。除非另有定义，下文中所使用的所有专业术语与本领域技术人员通常理解含义相同。下文中所使用的专业术语只是为了描述具体实施例的目的，并不是旨在限制本发明的保护范围。除非另有特别说明，本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。In order to facilitate understanding of the present invention, the following will describe the present invention more fully and in detail by means of examples, but the protection scope of the present invention is not limited to the following specific examples. Unless otherwise defined, all technical terms used hereinafter have the same meanings as commonly understood by those skilled in the art. The technical terms used below are only for the purpose of describing specific embodiments, and are not intended to limit the protection scope of the present invention. Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.
实施例1：Example 1:
一种复合包覆改性的高镍NCA正极材料，NCA正极材料以镍钴铝酸锂为基体，在基体的表面包裹有复合包覆改性层，复合包覆改性层由LiCoO
2与Co
2O
3组成，复合包覆改性层的含量为基体总重量的1.0wt％。复合包覆改性层中LiCoO
2与Co
2O
3的摩尔比为1:1.5。
A composite coating modified high-nickel NCA positive electrode material. The NCA positive electrode material uses nickel-cobalt lithium aluminate as a matrix, and a composite coating modification layer is wrapped on the surface of the substrate. The composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 composition, the content of the composite coating modification layer is 1.0wt% of the total weight of the matrix. The molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 1:1.5.
镍钴铝酸锂的化学式为Li
1.01Ni
0.913Co
0.069Al
0.015Ti
0.003O
2。
The chemical formula of lithium nickel cobalt aluminate is Li 1.01 Ni 0.913 Co 0.069 Al 0.015 Ti 0.003 O 2 .
制备上述NCA正极材料的方法，包括以下步骤：The method for preparing the above-mentioned NCA cathode material comprises the following steps:
S1、前驱体的制备：S1. Preparation of precursors:
按照Ni：Co的摩尔比93:7的条件下，以硫酸镍溶液、硫酸钴溶液为原料进行混合，镍钴混合溶液的金属摩尔浓度为1.0mol/L，再将氢氧化钠沉淀剂和氨水络合剂同时加入到反应釜中，控制反应釜中混合溶液的温度为45℃，控制反应釜中混合溶液的pH值为13.5，搅拌反应釜中的溶液进行沉淀反应，待反应完成后，经陈化后进行固液分离，然后使用去离子水进行反复洗涤，真空干燥后得到Ni
0.93Co
0.07(OH)
2前驱体；
According to the condition of the molar ratio of Ni:Co 93:7, nickel sulfate solution and cobalt sulfate solution are mixed as raw materials, the metal molar concentration of the nickel-cobalt mixed solution is 1.0mol/L, and then the sodium hydroxide precipitant and ammonia water The complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the reactor is controlled to be 45° C., the pH value of the mixed solution in the controlled reactor is 13.5, and the solution in the reactor is stirred for precipitation reaction. After the reaction is completed, the After aging, carry out solid-liquid separation, then use deionized water to wash repeatedly, and obtain Ni 0.93 Co 0.07 (OH) 2 precursor after vacuum drying;
S2、一烧基体的制备：S2, the preparation of alkane matrix:
将制备的Ni
0.93Co
0.07(OH)
2前驱体、氢氧化锂、氢氧化铝、氧化钛按照摩尔比为1:1.02:0.015：0.003的比例加入，高速混合均匀，混料速度为800rpm/min,混料30min后进入氧气气氛炉中进行烧结，烧结时间20h，烧结温度为730℃，自然冷却至室温后取出物料，粉碎过筛后得到一烧基体；
Add the prepared Ni 0.93 Co 0.07 (OH) 2 precursor, lithium hydroxide, aluminum hydroxide, and titanium oxide according to the molar ratio of 1:1.02:0.015:0.003, and mix evenly at high speed. The mixing speed is 800rpm/min , After mixing the materials for 30 minutes, put them into an oxygen atmosphere furnace for sintering, the sintering time is 20 hours, and the sintering temperature is 730°C. After natural cooling to room temperature, take out the materials, crush and sieve to obtain a sintered matrix;
S3、复合包覆改性的高镍NCA正极材料制备：S3. Preparation of composite coating modified high-nickel NCA cathode material:
将一烧基体与去离子水按照0.5:1的比例加入到反应器中，一烧基体加入后搅拌，反应器中的固液混合物的温度控制在25℃，然后将硝酸钴溶液加入到反应器中，其中硝酸钴的重量占一烧基体的重量为7wt％，使用氨水调节溶液的pH至7.5，反应20min后进行过滤，在150℃下进行真空干燥，干燥完成后将物料至于氧气气氛炉中进行烧结，烧结时间13h，烧结制度由室温2h升温至450℃，然后再用1h升温至600℃，然后2h降温至450℃，再以2h升温至720℃，以4h降温至450℃，最后以2h降温至室温出炉，过筛后得到复合包覆改性的高镍 NCA正极材料。Add an alkyl base and deionized water into the reactor at a ratio of 0.5:1, stir after adding an alkyl base, control the temperature of the solid-liquid mixture in the reactor at 25°C, and then add the cobalt nitrate solution into the reactor Among them, the weight of cobalt nitrate accounted for 7wt% of the weight of the alkyl body, the pH of the solution was adjusted to 7.5 with ammonia water, filtered after 20 minutes of reaction, vacuum dried at 150 ° C, and the material was placed in an oxygen atmosphere furnace after drying Carry out sintering, the sintering time is 13h, the sintering system is heated up from room temperature to 450°C for 2h, then raised to 600°C in 1h, then lowered to 450°C in 2h, then raised to 720°C in 2h, cooled to 450°C in 4h, and finally After cooling down to room temperature for 2 hours, the composite coated and modified high-nickel NCA positive electrode material was obtained after sieving.
由图1-2可知，有明显的改性层包覆在正极材料表面；由图3可知NCA正极材料表层是由LiCoO
2和Co
2O
3组成的混合物，其比例为2:3。由图4可知，经过复合包覆改性的高镍NCA正极材料的热稳定性明显优于表面未改性的NCA正极材料。
It can be seen from Figure 1-2 that there is an obvious modified layer covering the surface of the positive electrode material; it can be seen from Figure 3 that the surface layer of the NCA positive electrode material is a mixture of LiCoO 2 and Co 2 O 3 with a ratio of 2:3. It can be seen from Figure 4 that the thermal stability of the high-nickel NCA cathode material modified by composite coating is significantly better than that of the NCA cathode material without surface modification.
扣电测试：将所得活性物质、乙炔黑和聚偏二氟乙烯(PVDF)混合，以N-甲基吡咯烷酮(NMP)为溶剂将混合物调成糊状，然后均匀的涂覆在集流体铝箔上，干燥后滚压，制成正极片，负极为圆片状金属锂，直径为12mm；隔膜为微孔聚丙烯膜(Celgard-2300)，直径为14mm；1.0MLiPF
6的碳酸乙烯酯、碳酸二乙酯和碳酸二甲酯混合液，体积比比为1:2:1，电解液水分含量小于30ppm；测试电池采用2032型扣式电池，电压测试范围：3.0-4.3V。
Button electricity test: Mix the obtained active material, acetylene black and polyvinylidene fluoride (PVDF), use N-methylpyrrolidone (NMP) as a solvent to make the mixture into a paste, and then evenly coat it on the aluminum foil of the current collector , rolled after drying to make a positive electrode sheet, and the negative electrode is a disc-shaped lithium metal with a diameter of 12mm; the separator is a microporous polypropylene film (Celgard - 2300) with a diameter of 14mm; Ethyl ester and dimethyl carbonate mixed solution, the volume ratio is 1:2:1, the moisture content of the electrolyte is less than 30ppm; the test battery is a 2032 button battery, and the voltage test range is 3.0-4.3V.
经测试，首次放电容量比容量为217.8mAh/g，如图5所示，高温45℃的条件下经过50次循环后，放电容量保持率在96.1％。After testing, the specific capacity of the first discharge capacity is 217.8mAh/g, as shown in Figure 5, after 50 cycles at a high temperature of 45°C, the discharge capacity retention rate is 96.1%.
实施例2：Example 2:
一种复合包覆改性的高镍NCA正极材料，NCA正极材料以镍钴锰酸锂为基体，在基体的表面包裹有复合包覆改性层，复合包覆改性层由LiCoO
2与Co
2O
3组成,复合包覆改性层的含量为基体总重量的1.0wt％。复合包覆改性层中LiCoO
2与Co
2O
3的摩尔比为1:2。
A composite coating modified high-nickel NCA positive electrode material. The NCA positive electrode material uses nickel-cobalt lithium manganese oxide as a matrix, and a composite coating modification layer is wrapped on the surface of the substrate. The composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 , the content of the composite coating modification layer is 1.0wt% of the total weight of the matrix. The molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 1:2.
镍钴锰酸锂的化学式为Li
1.01Ni
0.913Co
0.069Al
0.015Ti
0.003O
2。
The chemical formula of nickel cobalt lithium manganate is Li 1.01 Ni 0.913 Co 0.069 Al 0.015 Ti 0.003 O 2 .
制备上述NCA正极材料的方法，包括以下步骤：The method for preparing the above-mentioned NCA cathode material comprises the following steps:
S1、前驱体的制备：S1. Preparation of precursors:
按照Ni：Co的摩尔比93:7的条件下，以硝酸镍溶液、硫酸钴溶液为原料进行混合，镍钴混合溶液的金属摩尔浓度为1.0mol/L,再将氢氧化钠沉淀剂和氨水络合剂同时加入到反应釜中，控制反应釜中混合溶液的温度为55℃、控制反应釜中混合溶液的pH值为13.0,搅拌反应釜中的溶液进行沉淀反应，待反应完成后，经陈化后进行固液分离，然后使用去离子水进行反复洗涤，真空干燥后得到Ni
0.93Co
0.07(OH)
2前驱体；
Under the condition of the molar ratio of Ni:Co 93:7, nickel nitrate solution and cobalt sulfate solution are mixed as raw materials, the metal molar concentration of the nickel-cobalt mixed solution is 1.0mol/L, and then sodium hydroxide precipitant and ammonia water The complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the reactor is controlled to be 55° C., the pH value of the mixed solution in the controlled reactor is 13.0, and the solution in the reactor is stirred for precipitation reaction. After the reaction is completed, the After aging, carry out solid-liquid separation, then use deionized water to wash repeatedly, and obtain Ni 0.93 Co 0.07 (OH) 2 precursor after vacuum drying;
S2、一烧基体的制备：S2, the preparation of alkane matrix:
将制备的Ni
0.93Co
0.07(OH)
2前驱体、碳酸锂、氢氧化铝、氧化钛按照摩尔比为1:1.02:0.015：0.003的比例，高速混合均匀，混料速度为800rpm/min,混料30min后进入氧气气氛炉中进行烧结，烧结时间15h，烧结温度为800℃，自然冷却至室温后取出物料，粉碎过筛后得到一烧基体；
Mix the prepared Ni 0.93 Co 0.07 (OH) 2 precursor, lithium carbonate, aluminum hydroxide, and titanium oxide at a molar ratio of 1:1.02:0.015:0.003 at a high speed, and the mixing speed is 800rpm/min. After 30 minutes, the material was put into an oxygen atmosphere furnace for sintering. The sintering time was 15 hours, and the sintering temperature was 800°C. After natural cooling to room temperature, the material was taken out, crushed and sieved to obtain a sintered matrix;
S3、复合包覆改性的高镍NCA正极材料制备：S3. Preparation of composite coating modified high-nickel NCA cathode material:
将一烧基体与去离子水按照1:1的比例加入到反应器中，一烧基体加入后搅拌，反应器中的固液混合物的温度控制在25℃，然后将硫酸钴溶液加入到反应器中，其中硫酸钴的重量占 一烧基体的重量为5wt％，使用氨水调节溶液的pH至8.5，反应20min后进行过滤，在150℃下进行真空干燥，干燥完成后将物料至于氧气气氛炉中进行烧结，烧结时间10h，烧结制度由室温2h升温至420℃，然后再用2h升温至700℃，然后2h降温至420℃，再以1h升温至600℃，以1h降温至420℃，最后以2h降温至室温出炉，过筛后得到复合包覆改性的高镍NCA正极材料。Add an alkyl base and deionized water into the reactor at a ratio of 1:1, stir after adding an alkyl base, control the temperature of the solid-liquid mixture in the reactor at 25°C, and then add the cobalt sulfate solution into the reactor Among them, the weight of cobalt sulfate accounted for 5wt% of the weight of an alkyl body, the pH of the solution was adjusted to 8.5 with ammonia water, filtered after 20 minutes of reaction, and vacuum dried at 150 ° C. After drying, the material was placed in an oxygen atmosphere furnace Carry out sintering, the sintering time is 10h, the sintering system is raised from room temperature to 420°C for 2h, then raised to 700°C for 2h, then lowered to 420°C for 2h, then raised to 600°C for 1h, cooled to 420°C for 1h, and finally After cooling down to room temperature for 2 hours, the composite coated and modified high-nickel NCA positive electrode material was obtained after sieving.
按照实施例1扣电测试方式评价材料。经测试，首次放电容量比容量216.3mAh/g，高温45℃的条件下经过50次循环后，放电容量保持率在96.7％。Evaluate the material according to the button electric test method of Example 1. After testing, the specific capacity of the first discharge capacity is 216.3mAh/g, and after 50 cycles at a high temperature of 45°C, the discharge capacity retention rate is 96.7%.
实施例3：Example 3:
一种复合包覆改性的高镍NCA正极材料，NCA正极材料以镍钴铝酸锂为基体，在基体的表面包裹有复合包覆改性层，复合包覆改性层由LiCoO
2与Co
2O
3组成，复合包覆改性层的含量为基体总重量的0.6wt％。复合包覆改性层中LiCoO
2与Co
2O
3的摩尔比为1:1。
A composite coating modified high-nickel NCA positive electrode material. The NCA positive electrode material uses nickel-cobalt lithium aluminate as a matrix, and a composite coating modification layer is wrapped on the surface of the substrate. The composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 composition, the content of the composite coating modification layer is 0.6wt% of the total weight of the matrix. The molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 1:1.
镍钴铝酸锂的化学式为Li
1.05Ni
0.923Co
0.049Al
0.026Y
0.002O
2。
The chemical formula of lithium nickel cobalt aluminate is Li 1.05 Ni 0.923 Co 0.049 Al 0.026 Y 0.002 O 2 .
制备上述NCA正极材料的方法，包括以下步骤：The method for preparing the above-mentioned NCA cathode material comprises the following steps:
S1、前驱体的制备：S1. Preparation of precursors:
按照Ni：Co的摩尔比95:5的条件下，以硝酸镍溶液、氯化钴溶液为原料进行混合，镍钴混合溶液的金属摩尔浓度为1.0mol/L,再将氢氧化钠沉淀剂和氨水络合剂同时加入到反应釜中，控制反应釜中混合溶液的温度为65℃、控制反应釜中混合溶液的pH值为13.0，搅拌反应釜中的溶液进行沉淀反应，待反应完成后，经陈化后进行固液分离，然后使用去离子水进行反复洗涤，真空干燥后得到Ni
0.95Co
0.05(OH)
2前驱体；
Under the condition of the molar ratio of Ni:Co 95:5, the nickel nitrate solution and the cobalt chloride solution are mixed as raw materials, the metal molar concentration of the nickel-cobalt mixed solution is 1.0mol/L, and then the sodium hydroxide precipitating agent and The ammonia water complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the controlled reactor is 65°C, the pH value of the mixed solution in the controlled reactor is 13.0, and the solution in the stirred reactor is subjected to precipitation reaction. After the reaction is completed, Separation of solid and liquid after aging, repeated washing with deionized water, and vacuum drying to obtain the Ni 0.95 Co 0.05 (OH) 2 precursor;
S2、一烧基体的制备：S2, the preparation of alkane matrix:
将制备的Ni
0.95Co
0.05(OH)
2前驱体、氢氧化锂、氢氧化铝、氧化钇按照摩尔比为1:1.06:0.013:0.001的比例，高速混合均匀，混料速度为800rpm/min,混料30min后进入氧气气氛炉中进行烧结，烧结时间8h，烧结温度为750℃，自然冷却至室温后取出物料，粉碎过筛后得到一烧基体；
Mix the prepared Ni 0.95 Co 0.05 (OH) 2 precursor, lithium hydroxide, aluminum hydroxide, and yttrium oxide at a molar ratio of 1:1.06:0.013:0.001 at a high speed, and the mixing speed is 800rpm/min. After mixing for 30 minutes, enter into an oxygen atmosphere furnace for sintering. The sintering time is 8 hours, and the sintering temperature is 750°C. After natural cooling to room temperature, the materials are taken out, crushed and sieved to obtain a sintered matrix;
S3、复合包覆改性的高镍NCA正极材料制备：S3. Preparation of composite coating modified high-nickel NCA cathode material:
将一烧基体与去离子水按照0.75:1的比例加入到反应器中，一烧基体加入后搅拌，反应器中的固液混合物的温度控制在25℃，然后将氯化钴溶液加入到反应器中，其中氯化钴的重量占一烧基体的重量为3wt％，使用氨水调节溶液的pH至8.0，反应20min后进行过滤，在150℃下进行真空干燥，干燥完成后将物料至于氧气气氛炉中进行烧结，烧结时间9h，烧结制度由室温1.5h升温至410℃，然后再用1.5h升温至730℃，然后1.5h降温至410℃，再以1h升温至730℃，以1h降温至410℃，最后以2.5h降温至室温出炉，过筛后得到复合包覆改 性的高镍NCA正极材料。Add an alkyl base and deionized water into the reactor at a ratio of 0.75:1, stir after adding an alkyl base, control the temperature of the solid-liquid mixture in the reactor at 25°C, and then add the cobalt chloride solution to the reaction In the container, wherein the weight of cobalt chloride accounted for 3wt% of the weight of the alkyl body, the pH of the solution was adjusted to 8.0 with ammonia water, filtered after 20 minutes of reaction, and vacuum dried at 150 ° C. After drying, the material was placed in an oxygen atmosphere Sintering in the furnace, the sintering time is 9h, the sintering system is heated from room temperature to 410°C for 1.5h, then raised to 730°C for 1.5h, then cooled to 410°C for 1.5h, then raised to 730°C for 1h, and cooled to 410°C, and finally cooled down to room temperature for 2.5 hours to take out the furnace, and after sieving, a composite-coated modified high-nickel NCA positive electrode material was obtained.
按照实施例1扣电测试方式评价材料。经测试，首次放电容量比容量218.0mAh/g，高温45℃的条件下经过50次循环后，放电容量保持率在95.3％。Evaluate the material according to the button electric test method of Example 1. After testing, the specific capacity of the first discharge capacity is 218.0mAh/g, and after 50 cycles at a high temperature of 45°C, the discharge capacity retention rate is 95.3%.
实施例4：Example 4:
一种复合包覆改性的高镍NCA正极材料，NCA正极材料以镍钴锰酸锂为基体，在基体的表面包裹有复合包覆改性层，复合包覆改性层由LiCoO
2与Co
2O
3组成,复合包覆改性层的含量为基体总重量的0.6wt％。复合包覆改性层中LiCoO
2与Co
2O
3的摩尔比为2:1。
A composite coating modified high-nickel NCA positive electrode material. The NCA positive electrode material uses nickel-cobalt lithium manganese oxide as a matrix, and a composite coating modification layer is wrapped on the surface of the substrate. The composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 , the content of the composite coating modification layer is 0.6wt% of the total weight of the matrix. The molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 2:1.
镍钴锰酸锂的化学式为Li
1.05Ni
0.923Co
0.049Al
0.026Y
0.002O
2。
The chemical formula of nickel cobalt lithium manganate is Li 1.05 Ni 0.923 Co 0.049 Al 0.026 Y 0.002 O 2 .
制备上述NCA正极材料的方法，包括以下步骤：The method for preparing the above-mentioned NCA cathode material comprises the following steps:
S1、前驱体的制备：S1. Preparation of precursors:
按照Ni：Co的摩尔比95:5的条件下，以硝酸镍溶液、硫酸钴溶液为原料进行混合，镍钴混合溶液的金属摩尔浓度为1.0mol/L,再将氢氧化钠沉淀剂和氨水络合剂同时加入到反应釜中，控制反应釜中混合溶液的温度为55℃、控制反应釜中混合溶液的pH值为13.0,搅拌反应釜中的溶液进行沉淀反应，待反应完成后，经陈化后进行固液分离，然后使用去离子水进行反复洗涤，真空干燥后得到Ni
0.95Co
0.05(OH)
2前驱体；
Under the condition of the molar ratio of Ni:Co 95:5, nickel nitrate solution and cobalt sulfate solution are mixed as raw materials. The complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the reactor is controlled to be 55° C., the pH value of the mixed solution in the controlled reactor is 13.0, and the solution in the reactor is stirred for precipitation reaction. After the reaction is completed, the After aging, carry out solid-liquid separation, then use deionized water to wash repeatedly, and obtain Ni 0.95 Co 0.05 (OH) 2 precursor after vacuum drying;
S2、一烧基体的制备：S2, the preparation of alkane matrix:
将制备的Ni
0.95Co
0.05(OH)
2前驱体、碳酸锂、氧化铝、氧化钇按照摩尔比为1:1.06:0.013:0.001的比例，高速混合均匀，混料速度为800rpm/min,混料30min后进入氧气气氛炉中进行烧结，烧结时间15h，烧结温度为800℃，自然冷却至室温后取出物料，粉碎过筛后得到一烧基体；
Mix the prepared Ni 0.95 Co 0.05 (OH) 2 precursor, lithium carbonate, aluminum oxide, and yttrium oxide at a molar ratio of 1:1.06:0.013:0.001 at a high speed, and the mixing speed is 800rpm/min. After 30 minutes, enter into an oxygen atmosphere furnace for sintering. The sintering time is 15 hours, and the sintering temperature is 800°C. After natural cooling to room temperature, the material is taken out, crushed and sieved to obtain a sintered matrix;
S3、复合包覆改性的高镍NCA正极材料制备：S3. Preparation of composite coating modified high-nickel NCA cathode material:
将一烧基体与去离子水按照1:1的比例加入到反应器中，一烧基体加入后搅拌，反应器中的固液混合物的温度控制在25℃，然后将硫酸钴溶液加入到反应器中，其中硫酸钴的重量占一烧基体的重量为3wt％，使用氨水调节溶液的pH至8.5，反应20min后进行过滤，在150℃下进行真空干燥，干燥完成后将物料至于氧气气氛炉中进行烧结，烧结时间10h，烧结制度由室温2h升温至420℃，然后再用1h升温至700℃，然后2h降温至420℃，再以1.5h升温至600℃，以3.0h降温至420℃，最后以2h降温至室温出炉，过筛后得到复合包覆改性的高镍NCA正极材料。Add an alkyl base and deionized water into the reactor at a ratio of 1:1, stir after adding an alkyl base, control the temperature of the solid-liquid mixture in the reactor at 25°C, and then add the cobalt sulfate solution into the reactor Among them, the weight of cobalt sulfate accounted for 3wt% of the weight of an alkyl body, the pH of the solution was adjusted to 8.5 with ammonia water, filtered after 20 minutes of reaction, and vacuum dried at 150 ° C. After drying, the material was placed in an oxygen atmosphere furnace Sintering, the sintering time is 10h, the sintering system is heated from room temperature to 420°C for 2h, then raised to 700°C in 1h, then cooled to 420°C in 2h, then raised to 600°C in 1.5h, and cooled to 420°C in 3.0h. Finally, the temperature was lowered to room temperature for 2 hours, and the compound-coated modified high-nickel NCA positive electrode material was obtained after sieving.
按照实施例1扣电测试方式评价材料。经测试，首次放电容量比容量218.5mAh/g，高温45℃的条件下经过50次循环后，放电容量保持率在94.4％。Evaluate the material according to the button electric test method of Example 1. After testing, the specific capacity of the first discharge capacity is 218.5mAh/g, and after 50 cycles at a high temperature of 45°C, the discharge capacity retention rate is 94.4%.
实施例5：Example 5:
一种复合包覆改性的高镍NCA正极材料，NCA正极材料以镍钴铝酸锂为基体，在基体的表面包裹有复合包覆改性层，复合包覆改性层由LiCoO
2与Co
2O
3组成，复合包覆改性层的含量为基体总重量的2.6wt％。复合包覆改性层中LiCoO
2与Co
2O
3的摩尔比为1:3。
A composite coating modified high-nickel NCA positive electrode material. The NCA positive electrode material uses nickel-cobalt lithium aluminate as a matrix, and a composite coating modification layer is wrapped on the surface of the substrate. The composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 composition, the content of the composite coating modification layer is 2.6wt% of the total weight of the matrix. The molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer is 1:3.
镍钴铝酸锂的化学式为Li
1.05Ni
0.911Co
0.058Al
0.012Mg
0.019O
2。
The chemical formula of lithium nickel cobalt aluminate is Li 1.05 Ni 0.911 Co 0.058 Al 0.012 Mg 0.019 O 2 .
制备上述NCA正极材料的方法，包括以下步骤：The method for preparing the above-mentioned NCA cathode material comprises the following steps:
S1、前驱体的制备：S1. Preparation of precursors:
按照Ni：Co的摩尔比94:6的条件下，以硝酸镍溶液、氯化钴溶液为原料进行混合，镍钴混合溶液的金属摩尔浓度为1.0mol/L,再将氢氧化钠沉淀剂和氨水络合剂同时加入到反应釜中，控制反应釜中混合溶液的温度为65℃、控制反应釜中混合溶液的pH值为13.0，搅拌反应釜中的溶液进行沉淀反应，待反应完成后，经陈化后进行固液分离，然后使用去离子水进行反复洗涤，真空干燥后得到Ni
0.94Co
0.06(OH)
2前驱体；
Under the condition of the molar ratio of Ni:Co 94:6, the nickel nitrate solution and the cobalt chloride solution are mixed as raw materials, the metal molar concentration of the nickel-cobalt mixed solution is 1.0mol/L, and then the sodium hydroxide precipitating agent and The ammonia water complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the controlled reactor is 65°C, the pH value of the mixed solution in the controlled reactor is 13.0, and the solution in the stirred reactor is subjected to precipitation reaction. After the reaction is completed, Separation of solid and liquid after aging, repeated washing with deionized water, and vacuum drying to obtain the Ni 0.94 Co 0.06 (OH) 2 precursor;
S2、一烧基体的制备：S2, the preparation of alkane matrix:
将制备的Ni
0.94Co
0.06(OH)
2前驱体、氢氧化锂、氧化铝、氧化镁按照摩尔比为1:1.06:0.006:0.019的比例，高速混合均匀，混料速度为800rpm/min,混料30min后进入氧气气氛炉中进行烧结，烧结时间8h，烧结温度为750℃，自然冷却至室温后取出物料，粉碎过筛后得到一烧基体；
Mix the prepared Ni 0.94 Co 0.06 (OH) 2 precursor, lithium hydroxide, aluminum oxide, and magnesium oxide at a molar ratio of 1:1.06:0.006:0.019 at a high speed, and the mixing speed is 800rpm/min. After 30 minutes, the material was put into an oxygen atmosphere furnace for sintering. The sintering time was 8 hours, and the sintering temperature was 750°C. After natural cooling to room temperature, the material was taken out, crushed and sieved to obtain a sintered matrix;
S3、复合包覆改性的高镍NCA正极材料制备：S3. Preparation of composite coating modified high-nickel NCA cathode material:
将一烧基体与去离子水按照0.75:1的比例加入到反应器中，一烧基体加入后搅拌，反应器中的固液混合物的温度控制在25℃，然后将氯化钴溶液加入到反应器中，其中氯化钴的重量占一烧基体的重量为7wt％，使用氨水调节溶液的pH至8.0，反应20min后进行过滤，在150℃下进行真空干燥，干燥完成后将物料至于氧气气氛炉中进行烧结，烧结时间9h，烧结制度由室温2h升温至410℃，然后再用2h升温至730℃，然后2h降温至410℃，再以1h升温至730℃，以1h降温至410℃，最后以2h降温至室温出炉，过筛后得到复合包覆改性的高镍NCA正极材料。Add an alkyl base and deionized water into the reactor at a ratio of 0.75:1, stir after adding an alkyl base, control the temperature of the solid-liquid mixture in the reactor at 25°C, and then add the cobalt chloride solution to the reaction In the container, wherein the weight of cobalt chloride accounted for 7wt% of the weight of the alkyl body, the pH of the solution was adjusted to 8.0 with ammonia water, filtered after 20 minutes of reaction, and vacuum-dried at 150 ° C. After the drying was completed, the material was placed in an oxygen atmosphere Sintering in the furnace, the sintering time is 9h, the sintering system is heated from room temperature to 410°C for 2h, then raised to 730°C for 2h, then cooled to 410°C for 2h, then raised to 730°C for 1h, and cooled to 410°C for 1h, Finally, the temperature was lowered to room temperature for 2 hours, and the compound-coated modified high-nickel NCA positive electrode material was obtained after sieving.
按照实施例1扣电测试方式评价材料。经测试，首次放电容量比容量215.0mAh/g，高温45℃的条件下经过50次循环后，放电容量保持率在96.7％。Evaluate the material according to the button electric test method of Example 1. After testing, the specific capacity of the first discharge capacity is 215.0mAh/g, and after 50 cycles at a high temperature of 45°C, the discharge capacity retention rate is 96.7%.
对比例1：Comparative example 1:
一种表面未改性的NCA正极材料，NCA正极材料以镍钴铝酸锂为基体，镍钴铝酸锂的化学式为Li
1.01Ni
0.913Co
0.069Al
0.015Ti
0.003O
2。
An unmodified NCA positive electrode material, the NCA positive electrode material is based on nickel cobalt lithium aluminate, and the chemical formula of nickel cobalt lithium aluminate is Li 1.01 Ni 0.913 Co 0.069 Al 0.015 Ti 0.003 O 2 .
制备上述NCA正极材料的方法，包括以下步骤：The method for preparing the above-mentioned NCA cathode material comprises the following steps:
S1、前驱体的制备：S1. Preparation of precursors:
按照Ni：Co的摩尔比93:7的条件下，以硫酸镍溶液、硫酸钴溶液为原料进行混合，镍钴混合溶液的金属摩尔浓度为1.0mol/L，再将氢氧化钠沉淀剂和氨水络合剂同时加入到反应釜中，控制反应釜中混合溶液的温度为45℃、控制反应釜中混合溶液的pH值为13.5，搅拌反应釜中的溶液进行沉淀反应，待反应完成后，经陈化后进行固液分离，然后使用去离子水进行反复洗涤，真空干燥后得到Ni
0.93Co
0.07(OH)
2前驱体；
According to the condition of the molar ratio of Ni:Co 93:7, nickel sulfate solution and cobalt sulfate solution are mixed as raw materials, the metal molar concentration of the nickel-cobalt mixed solution is 1.0mol/L, and then the sodium hydroxide precipitant and ammonia water The complexing agent is added into the reactor at the same time, the temperature of the mixed solution in the reactor is controlled to be 45° C., the pH value of the mixed solution in the controlled reactor is 13.5, and the solution in the reactor is stirred for precipitation reaction. After the reaction is completed, the After aging, carry out solid-liquid separation, then use deionized water to wash repeatedly, and obtain Ni 0.93 Co 0.07 (OH) 2 precursor after vacuum drying;
S2、一烧基体的制备：S2, the preparation of alkane matrix:
将制备的Ni
0.93Co
0.07(OH)
2前驱体、氢氧化锂、氢氧化铝、氧化钛按照摩尔比为1:1.02:0.015：0.003的比例加入，高速混合均匀，混料速度为800rpm/min,混料30min后进入氧气气氛炉中进行烧结，烧结时间20h，烧结温度为730℃，自然冷却至室温后取出物料，粉碎过筛后得到一烧基体；
Add the prepared Ni 0.93 Co 0.07 (OH) 2 precursor, lithium hydroxide, aluminum hydroxide, and titanium oxide according to the molar ratio of 1:1.02:0.015:0.003, and mix evenly at high speed. The mixing speed is 800rpm/min , After mixing the materials for 30 minutes, put them into an oxygen atmosphere furnace for sintering, the sintering time is 20 hours, and the sintering temperature is 730°C. After natural cooling to room temperature, take out the materials, crush and sieve to obtain a sintered matrix;
S3、表面未改性的NCA正极材料制备：S3. Preparation of NCA cathode material with unmodified surface:
将一烧基体与去离子水按照0.5:1的比例加入到反应器中，一烧基体加入后搅拌，反应器中的固液混合物的温度控制在25℃，使用氨水调节溶液的pH至7.5，反应20min后进行过滤，在150℃下进行真空干燥，干燥完成后将物料至于氧气气氛炉中进行烧结，烧结时间13h，烧结制度由室温2h升温至450℃，继续由1h升温至600℃，然后2h降温至450℃，再以2h升温至720℃，以4h降温至450℃，最后以2h降温至室温出炉，过筛后得到复合包覆改性的高镍NCA正极材料。Add an alkyl base and deionized water into the reactor at a ratio of 0.5:1, stir after adding an alkyl base, control the temperature of the solid-liquid mixture in the reactor at 25°C, use ammonia water to adjust the pH of the solution to 7.5, After reacting for 20 minutes, filter and vacuum dry at 150°C. After drying, put the material in an oxygen atmosphere furnace for sintering. The sintering time is 13 hours. Cool down to 450°C for 2 hours, then raise the temperature to 720°C for 2 hours, cool down to 450°C for 4 hours, and finally cool down to room temperature for 2 hours, and then sieve to obtain a composite-coated modified high-nickel NCA cathode material.
按照实施例1扣电测试方式评价材料。经测试，首次放电容量比容量210.3mAh/g，高温45℃的条件下经过50次循环后，放电容量保持率在90.5％。Evaluate the material according to the button electric test method of Example 1. After testing, the specific capacity of the first discharge capacity is 210.3mAh/g, and after 50 cycles at a high temperature of 45°C, the discharge capacity retention rate is 90.5%.
对比例2：Comparative example 2:
一种钴酸锂包覆的镍钴铝酸锂正极材料，参考背景技术中CN 107946578 B得到，该正极材料以镍钴铝酸锂为基体，镍钴铝酸锂的化学式为Li
1.01Ni
0.913Co
0.069Al
0.015Ti
0.003O
2，在基体的表面包裹有LiCoO
2包覆改性层，包覆改性层的含量为基体总重量的1wt％。
A nickel-cobalt-lithium-aluminate positive electrode material coated with lithium cobaltate, obtained by referring to CN 107946578 B in the background technology, the positive electrode material is based on nickel-cobalt lithium-aluminate, and the chemical formula of nickel-cobalt lithium-aluminate is Li 1.01 Ni 0.913 Co 0.069 Al 0.015 Ti 0.003 O 2 , a LiCoO 2 coating modification layer is wrapped on the surface of the substrate, and the content of the coating modification layer is 1 wt% of the total weight of the substrate.
一种钴酸锂包覆的镍钴铝酸锂正极材料的制备方法：A preparation method of nickel cobalt lithium aluminate cathode material coated with lithium cobalt oxide:
(1)将5g聚乙烯吡咯烷酮溶于100mL去离子水中，置于带有超声装置的磁力搅拌器中，加热至50℃，在超声频率为20kHz，搅拌速度为800r/min下，超声搅拌反应1h，得表面活性溶液；(1) Dissolve 5g of polyvinylpyrrolidone in 100mL of deionized water, place it in a magnetic stirrer with an ultrasonic device, heat it to 50°C, and react with ultrasonic stirring for 1h at an ultrasonic frequency of 20kHz and a stirring speed of 800r/min , to obtain a surface active solution;
(2)将10g(108.96mmol)氢氧化镍钴铝、0.2714g(1.09mmol)四水合乙酸钴和11.781g(115.48mmol)二水合乙酸锂、0.02518g(0.3178mmol)氧化钛同时加入步骤(1)所得表面活性溶液中，置于带有超声装置的磁力搅拌器中，加热至50℃，在超声频率为20kHz， 搅拌速度为1000r/min下，超声搅拌反应3h，得悬浊液；(2) Add 10g (108.96mmol) nickel cobalt aluminum hydroxide, 0.2714g (1.09mmol) cobalt acetate tetrahydrate, 11.781g (115.48mmol) lithium acetate dihydrate, and 0.02518g (0.3178mmol) titanium oxide to step (1) simultaneously ) in the obtained surface active solution, placed in a magnetic stirrer equipped with an ultrasonic device, heated to 50 ° C, and ultrasonically stirred for 3 hours at an ultrasonic frequency of 20 kHz and a stirring speed of 1000 r/min to obtain a suspension;
(3)将步骤(2)所得悬浊液在超声频率为20kHz，搅拌速度为1000r/min的超声搅拌下，并于进料速度为500mL/h，进风温度为250℃，出风温度为120℃下，进行喷雾干燥，得钴酸锂包覆的镍钴铝酸锂正极材料的前驱体粉体；(3) The suspension obtained in step (2) is under ultrasonic stirring with an ultrasonic frequency of 20kHz and a stirring speed of 1000r/min, and at a feed rate of 500mL/h, an air inlet temperature of 250°C, and an air outlet temperature of 250°C. Spray-dry at 120°C to obtain the precursor powder of nickel-cobalt-lithium-aluminate cathode material coated with lithium cobaltate;
(4)将步骤(3)所得钴酸锂包覆的镍钴铝酸锂正极材料的前驱体粉体置于管式炉中，在纯度为99.9％的氧气气氛下，先以4℃/min的速率升温至480℃，烧结5h，再以4℃/min的速率升温至800℃，烧结15h，得钴酸锂包覆的镍钴铝酸锂正极材料。(4) Place the precursor powder of the lithium cobaltate-coated nickel-cobalt-lithium-aluminate positive electrode material obtained in step (3) in a tube furnace. Raise the temperature to 480°C at a high rate, sinter for 5 hours, then raise the temperature to 800°C at a rate of 4°C/min, and sinter for 15 hours to obtain a lithium cobaltate-coated nickel-cobalt-lithium-aluminate cathode material.
按照实施例1扣电测试方式评价材料。经测试，首次放电容量比容量212.6mAh/g，高温45℃的条件下经过50次循环后，放电容量保持率在88.6％。Evaluate the material according to the button electric test method of Example 1. After testing, the specific capacity of the first discharge capacity is 212.6mAh/g, and after 50 cycles at a high temperature of 45°C, the discharge capacity retention rate is 88.6%.
实施例1-5和对比例1的放电容量和循环性能测试如下表1所示。The discharge capacity and cycle performance tests of Examples 1-5 and Comparative Example 1 are shown in Table 1 below.
表1Table 1
| the | LiCoO 2与Co 2O 3的摩尔比 Molar ratio of LiCoO2 to Co2O3 | 放电容量(0.1C，mAh/g)Discharge capacity (0.1C, mAh/g) | 50周循环保持率(0.1C充放电，45℃)％50-cycle cycle retention (0.1C charge and discharge, 45°C)% |
| 实施例1Example 1 | 1：1.51:1.5 | 217.8217.8 | 96.196.1 |
| 实施例2Example 2 | 1：21:2 | 216.3216.3 | 96.796.7 |
| 实施例3Example 3 | 1：11:1 | 218.0218.0 | 95.395.3 |
| 实施例4Example 4 | 2：12:1 | 218.5218.5 | 94.494.4 |
| 实施例5Example 5 | 1：31:3 | 215.0215.0 | 96.796.7 |
| 对比例1Comparative example 1 | // | 210.3210.3 | 90.590.5 |
| 对比例2Comparative example 2 | // | 212.6212.6 | 88.688.6 |
如上表1所示，实施例1-5的放电容量和循环保持率明显优于未包覆的对比例1。其中，实施例1复合包覆改性层中LiCoO
2与Co
2O
3的摩尔比为1：1.5，放电容量可达到217.8mAh/g，循环保持率为96.1％；实施例2复合包覆改性层中LiCoO
2与Co
2O
3的摩尔比为1：2，放电容量可达到216.3mAh/g，循环保持率为96.7％。实施例3和实施例4中LiCoO
2与Co
2O
3的摩尔比大于1：1.5，放电容量相比于实施例1提高并不明显，而循环性能却降低较快；实施例5中的LiCoO
2与Co
2O
3的摩尔比为1：3，其循环性能的测试值相对于实施例2已无提高，容量却至215.0mAh/g。
As shown in Table 1 above, the discharge capacity and cycle retention rate of Examples 1-5 are significantly better than those of Comparative Example 1 which is not coated. Among them, the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modification layer in Example 1 is 1:1.5, the discharge capacity can reach 217.8mAh/g, and the cycle retention rate is 96.1%; the composite coating modification layer in Example 2 The molar ratio of LiCoO 2 to Co 2 O 3 in the active layer is 1:2, the discharge capacity can reach 216.3mAh/g, and the cycle retention rate is 96.7%. In Example 3 and Example 4, the molar ratio of LiCoO 2 to Co 2 O 3 is greater than 1:1.5, the discharge capacity is not significantly improved compared to Example 1, but the cycle performance is reduced rapidly; the LiCoO in Example 5 The molar ratio of 2 to Co 2 O 3 is 1:3, and the test value of its cycle performance has not improved compared with Example 2, but the capacity has reached 215.0mAh/g.
另外，仅包覆钴酸锂的对比例2相比于未包覆，的确有利于提升容量，但是和实施例1相比，由于单独的钴酸锂包覆层在充放电过程中容易发生晶格结构变化，将导致其循环性能明显变劣。In addition, Comparative Example 2, which is only coated with lithium cobaltate, is indeed beneficial to increase the capacity compared with no coating, but compared with Example 1, due to the single lithium cobaltate coating layer is prone to crystallization during charging and discharging. The change of the lattice structure will lead to the obvious deterioration of its cycle performance.
Claims (10)
- 一种复合包覆改性的高镍NCA正极材料，其特征在于：所述NCA正极材料以三元材料为基体，在基体的表面包裹有复合包覆改性层；A compound-coated modified high-nickel NCA positive electrode material, characterized in that: the NCA positive electrode material uses a ternary material as a matrix, and a compound-coated modified layer is wrapped on the surface of the matrix;所述三元材料的化学式为Li aNi xCo yAl zN bO 2，其中1.005≤a≤1.06，0.80≤x≤0.97，0.02≤y≤0.15，0<z≤0.10，0≤b≤0.10，N为Zr、Cr、Mg、V、Ti、Sr、Sb、Y、W、Nb、Zn、Ce、Al、B、Ba、Sn中的一种或多种； The chemical formula of the ternary material is Li a Ni x Co y Al z N b O 2 , where 1.005≤a≤1.06, 0.80≤x≤0.97, 0.02≤y≤0.15, 0<z≤0.10, 0≤b≤ 0.10, N is one or more of Zr, Cr, Mg, V, Ti, Sr, Sb, Y, W, Nb, Zn, Ce, Al, B, Ba, Sn;所述复合包覆改性层由LiCoO 2与Co 2O 3组成，所述复合包覆改性层的含量为基体总重量的0.2wt％～3wt％。 The composite coating modification layer is composed of LiCoO 2 and Co 2 O 3 , and the content of the composite coating modification layer is 0.2wt%-3wt% of the total weight of the matrix.
- 根据权利要求1所述的NCA正极材料，其特征在于：所述复合包覆改性层中LiCoO 2与Co 2O 3的摩尔比为1:(0.5～3)。 The NCA cathode material according to claim 1, characterized in that: the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modified layer is 1:(0.5-3).
- 根据权利要求2所述的NCA正极材料，其特征在于：所述复合包覆改性层中LiCoO 2与Co 2O 3的摩尔比为1:(1.5～2)。 The NCA cathode material according to claim 2, characterized in that: the molar ratio of LiCoO 2 to Co 2 O 3 in the composite coating modified layer is 1:(1.5-2).
- 如权利要求1-3任一项所述的NCA正极材料的制备方法，其特征在于，包括以下步骤：The preparation method of NCA cathode material as described in any one of claim 1-3, is characterized in that, comprises the following steps:S1、氢氧化物前驱体制备：将镍盐溶液、钴盐溶液、氢氧化钠溶液及氨水溶液泵入反应釜中，发生共沉淀反应，得到镍钴氢氧化物前驱体；S1. Preparation of hydroxide precursor: pump nickel salt solution, cobalt salt solution, sodium hydroxide solution and ammonia solution into the reaction kettle, and a co-precipitation reaction occurs to obtain a nickel-cobalt hydroxide precursor;S2、一烧基体的制备：将步骤S1得到的镍钴氢氧化物前驱体、锂源、铝源、N源混合均匀，然后在氧气气氛中烧结，后冷却至室温，粉碎过筛后得到一烧基体；S2. Preparation of an alkane matrix: Mix the nickel-cobalt hydroxide precursor, lithium source, aluminum source, and N source obtained in step S1 evenly, then sinter in an oxygen atmosphere, cool to room temperature, pulverize and sieve to obtain an alkane matrix. base body;S3、NCA正极材料的制备：将步骤S2得到的一烧基体与去离子水混合得到固液混合物，加入钴源，并调节pH值至7.0-8.5，然后过滤、干燥，再置于氧气气氛中烧结，烧结后冷却至室温，过筛后即可得到复合包覆改性的高镍NCA正极材料。S3. Preparation of NCA positive electrode material: Mix the monoalkyl body obtained in step S2 with deionized water to obtain a solid-liquid mixture, add cobalt source, and adjust the pH value to 7.0-8.5, then filter, dry, and place in an oxygen atmosphere Sintering, cooling to room temperature after sintering, and sieving to obtain a composite-coated modified high-nickel NCA positive electrode material.
- 根据权利要求4所述的NCA正极材料的制备方法，其特征在于：所述步骤S3的烧结包括预热过程以及多个反复的升温降温过程，预热过程使温度由室温上升至400～450℃，预热时间为1～3h，升温降温过程中波谷温度控制在400℃～450℃，波峰温度控制在700℃～750℃。The preparation method of NCA cathode material according to claim 4, characterized in that: the sintering in the step S3 includes a preheating process and a plurality of repeated heating and cooling processes, and the preheating process increases the temperature from room temperature to 400-450°C , The preheating time is 1~3h, the valley temperature is controlled at 400℃~450℃ during the heating and cooling process, and the peak temperature is controlled at 700℃~750℃.
- 根据权利要求5所述的NCA正极材料的制备方法，其特征在于：步骤S3中，所述反复的升温降温过程中，每个升温降温的周期内升温时间与降温时间比为1:(1～3)。The preparation method of NCA positive electrode material according to claim 5, it is characterized in that: in step S3, in the described repeated heating and cooling process, the ratio of heating time to cooling time in each heating and cooling cycle is 1:(1～ 3).
- 根据权利要求4所述的NCA正极材料的制备方法，其特征在于：步骤S1中，所述镍盐选自硫酸镍、硝酸镍或氯化镍中的一种或多种；所述钴盐选自硫酸钴、硝酸钴或氯化钴中的一种或多种；所述镍盐和钴盐的摩尔比为(0.85～0.97):(0.03～0.15)；The preparation method of NCA positive electrode material according to claim 4, is characterized in that: in step S1, described nickel salt is selected from one or more in nickel sulfate, nickel nitrate or nickel chloride; Described cobalt salt is selected from One or more of cobalt sulfate, cobalt nitrate or cobalt chloride; the molar ratio of the nickel salt to the cobalt salt is (0.85～0.97):(0.03～0.15);步骤S1中，反应釜的温度控制为40-80℃，pH值控制为10-14。In step S1, the temperature of the reactor is controlled at 40-80° C., and the pH value is controlled at 10-14.
- 根据权利要求4所述的NCA正极材料的制备方法，其特征在于：步骤S2中，所述锂源为碳酸锂、氢氧化锂中的一种或两种；所述铝源选自氢氧化铝、氧化铝中的一种或两种；The preparation method of NCA cathode material according to claim 4, characterized in that: in step S2, the lithium source is one or both of lithium carbonate and lithium hydroxide; the aluminum source is selected from aluminum hydroxide , one or two of alumina;步骤S2中，烧结时间为5-28h，烧结温度控制在700-850℃。In step S2, the sintering time is 5-28 hours, and the sintering temperature is controlled at 700-850°C.
- 根据权利要求4所述的NCA正极材料的制备方法，其特征在于：步骤S3中，所述钴源选自硝酸钴、硫酸钴、氯化钴中的一种或几种；所述钴源占一烧基体重量的2wt％～8wt％。The preparation method of NCA cathode material according to claim 4, characterized in that: in step S3, the cobalt source is selected from one or more of cobalt nitrate, cobalt sulfate, and cobalt chloride; 2wt% to 8wt% of the weight of the alkyl base body.
- 根据权利要求4所述的NCA正极材料的制备方法，其特征在于：步骤S3中，所述一烧基体与去离子水的固液比为：(0.5～1.0):1。The preparation method of NCA cathode material according to claim 4, characterized in that: in step S3, the solid-to-liquid ratio of the monoalkyl body to deionized water is: (0.5-1.0):1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110703573.0 | 2021-06-24 | ||
| CN202110703573.0A CN113363492B (en) | 2021-06-24 | 2021-06-24 | Composite coating modified high-nickel NCA positive electrode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022267187A1 true WO2022267187A1 (en) | 2022-12-29 |
Family
ID=77536258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2021/111204 WO2022267187A1 (en) | 2021-06-24 | 2021-08-06 | Composite coated modified high-nickel nca positive electrode material and preparation method therefor |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113363492B (en) |
| WO (1) | WO2022267187A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115548479A (en) * | 2022-10-24 | 2022-12-30 | 无锡零一未来新材料技术研究院有限公司 | Lithium supplement material and preparation method and application thereof |
| CN115849467A (en) * | 2023-02-28 | 2023-03-28 | 宜宾锂宝新材料有限公司 | Method for removing residual alkali from high-nickel material, ternary material, and preparation method and application thereof |
| CN116525816A (en) * | 2023-07-03 | 2023-08-01 | 英德市科恒新能源科技有限公司 | Ultrahigh nickel-cobalt-aluminum ternary positive electrode material and preparation method thereof |
| CN116759583A (en) * | 2023-08-23 | 2023-09-15 | 浙江帕瓦新能源股份有限公司 | Coating modified precursor, preparation method thereof, positive electrode material and lithium ion battery |
| CN117038996A (en) * | 2023-10-10 | 2023-11-10 | 浙江帕瓦新能源股份有限公司 | α-NaVOPO 4 Coated sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114094068B (en) * | 2021-11-09 | 2023-07-25 | 远景动力技术(江苏)有限公司 | Cobalt-coated positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery |
| CN116741980A (en) * | 2022-03-02 | 2023-09-12 | 巴斯夫杉杉电池材料有限公司 | Ternary positive electrode material for lithium ion battery and preparation method thereof |
| CN115092972B (en) * | 2022-05-27 | 2023-08-08 | 宜宾光原锂电材料有限公司 | Cerium-tungsten co-doped ternary cathode material precursor and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008117729A (en) * | 2006-11-08 | 2008-05-22 | Sumitomo Metal Mining Co Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery, its manufacturing method, and non-aqueous type electrolyte secondary battery using it |
| CN105489886A (en) * | 2016-01-11 | 2016-04-13 | 山东玉皇新能源科技有限公司 | Nickel-cobalt-aluminum ternary cathode material with high tap-density and preparation method of nickel-cobalt-aluminum ternary cathode material |
| CN106532006A (en) * | 2016-12-16 | 2017-03-22 | 无锡晶石新型能源有限公司 | Preparation method of cobaltous oxide coated ternary anode material |
| CN107946578A (en) * | 2017-11-27 | 2018-04-20 | 中南大学 | A kind of nickel cobalt lithium aluminate cathode material of cobalt acid lithium cladding and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006012433A (en) * | 2004-06-22 | 2006-01-12 | Nichia Chem Ind Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery |
| KR101264337B1 (en) * | 2010-08-13 | 2013-05-14 | 삼성에스디아이 주식회사 | Positive active material and lithium battery using it |
| CN103606671B (en) * | 2013-12-09 | 2015-09-09 | 湖南杉杉新材料有限公司 | A kind of positive electrode material of high-capacity dynamic-type nickel-rich lithium ion battery and preparation method thereof |
| CN105226256A (en) * | 2015-10-26 | 2016-01-06 | 河南师范大学 | For modified cathode material and the lithium titanate battery of lithium titanate battery |
| US10361423B2 (en) * | 2016-01-18 | 2019-07-23 | Grst International Limited | Method of preparing battery electrodes |
| JP6812941B2 (en) * | 2017-09-29 | 2021-01-13 | トヨタ自動車株式会社 | Positive electrode active material, positive electrode mixture, positive electrode active material manufacturing method, positive electrode manufacturing method, and oxide solid-state battery manufacturing method |
| KR20200046749A (en) * | 2018-10-25 | 2020-05-07 | 삼성전자주식회사 | Composite cathode active material, cathode and lithium battery containing composite cathode active material, and preparation method thereof |
| CN114586201A (en) * | 2019-10-22 | 2022-06-03 | 巴斯夫欧洲公司 | Electrode active material and method for preparing the same |
| CN111477859A (en) * | 2020-05-09 | 2020-07-31 | 宁波锋成纳米科技有限公司 | Composite positive electrode material, preparation method thereof and water-based secondary battery |
-
2021
- 2021-06-24 CN CN202110703573.0A patent/CN113363492B/en active Active
- 2021-08-06 WO PCT/CN2021/111204 patent/WO2022267187A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008117729A (en) * | 2006-11-08 | 2008-05-22 | Sumitomo Metal Mining Co Ltd | Positive electrode active material for nonaqueous electrolyte secondary battery, its manufacturing method, and non-aqueous type electrolyte secondary battery using it |
| CN105489886A (en) * | 2016-01-11 | 2016-04-13 | 山东玉皇新能源科技有限公司 | Nickel-cobalt-aluminum ternary cathode material with high tap-density and preparation method of nickel-cobalt-aluminum ternary cathode material |
| CN106532006A (en) * | 2016-12-16 | 2017-03-22 | 无锡晶石新型能源有限公司 | Preparation method of cobaltous oxide coated ternary anode material |
| CN107946578A (en) * | 2017-11-27 | 2018-04-20 | 中南大学 | A kind of nickel cobalt lithium aluminate cathode material of cobalt acid lithium cladding and preparation method thereof |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115548479A (en) * | 2022-10-24 | 2022-12-30 | 无锡零一未来新材料技术研究院有限公司 | Lithium supplement material and preparation method and application thereof |
| CN115548479B (en) * | 2022-10-24 | 2024-03-22 | 无锡零一未来新材料技术研究院有限公司 | Lithium supplementing material and preparation method and application thereof |
| CN115849467A (en) * | 2023-02-28 | 2023-03-28 | 宜宾锂宝新材料有限公司 | Method for removing residual alkali from high-nickel material, ternary material, and preparation method and application thereof |
| CN116525816A (en) * | 2023-07-03 | 2023-08-01 | 英德市科恒新能源科技有限公司 | Ultrahigh nickel-cobalt-aluminum ternary positive electrode material and preparation method thereof |
| CN116525816B (en) * | 2023-07-03 | 2023-09-05 | 英德市科恒新能源科技有限公司 | Ultrahigh nickel-cobalt-aluminum ternary positive electrode material and preparation method thereof |
| CN116759583A (en) * | 2023-08-23 | 2023-09-15 | 浙江帕瓦新能源股份有限公司 | Coating modified precursor, preparation method thereof, positive electrode material and lithium ion battery |
| CN116759583B (en) * | 2023-08-23 | 2023-11-10 | 浙江帕瓦新能源股份有限公司 | Coating modified precursor, preparation method thereof, positive electrode material and lithium ion battery |
| CN117038996A (en) * | 2023-10-10 | 2023-11-10 | 浙江帕瓦新能源股份有限公司 | α-NaVOPO 4 Coated sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
| CN117038996B (en) * | 2023-10-10 | 2024-01-23 | 浙江帕瓦新能源股份有限公司 | α-NaVOPO 4 Coated sodium ion battery positive electrode material, preparation method thereof and sodium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113363492B (en) | 2022-11-01 |
| CN113363492A (en) | 2021-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2022267187A1 (en) | Composite coated modified high-nickel nca positive electrode material and preparation method therefor | |
| CN112750999B (en) | Cathode material, preparation method thereof and lithium ion battery | |
| WO2023169591A1 (en) | Sodium-containing oxide positive electrode material and preparation method therefor and use thereof, and positive electrode plate and use thereof | |
| CN110931768A (en) | Ternary positive electrode material of high-nickel monocrystal lithium ion battery and preparation method | |
| CN111916727B (en) | Dual-ion wet-doped ternary high-nickel cathode material and preparation method thereof | |
| WO2007131411A1 (en) | A positive electrode material for secondary battery and the preparation method of the same | |
| CN111762768B (en) | Spinel type lithium manganate-phosphate composite cathode material and preparation method thereof | |
| CN111785960B (en) | Vanadium pentoxide/rGO coated nickel cobalt lithium manganate positive electrode material and preparation method thereof | |
| WO2021175233A1 (en) | Lithium-manganese-rich material, preparation method for same, and applications thereof | |
| CN112928253B (en) | Nickel-manganese-titanium composite material and preparation method and application thereof | |
| CN112018335B (en) | Composite lithium ion battery anode material, lithium ion battery anode, lithium battery, battery module, battery pack and vehicle | |
| WO2023130779A1 (en) | High-voltage ternary positive electrode material with core-shell structure and preparation method therefor | |
| WO2021136490A1 (en) | Lithium-rich manganese-based material, preparation method therefor and application thereof | |
| WO2023179245A1 (en) | High-nickel ternary positive electrode material and preparation method therefor and application thereof | |
| CN112993241B (en) | Preparation method of single-crystal lithium manganate material | |
| WO2023221625A1 (en) | Large-particle-size single-crystal ternary positive electrode material, and preparation method therefor and use thereof | |
| CN112054166A (en) | Core-shell structure electrochemical active material, preparation method and battery | |
| CN116014104A (en) | Lithium-rich nickel positive electrode material, preparation method thereof, positive electrode sheet and secondary battery | |
| CN115207342A (en) | Nickel-cobalt-manganese ternary positive electrode material with lithium-deficient and oxygen-deficient rock salt phase structure on surface layer | |
| CN115810757B (en) | Positive electrode active material and lithium ion battery containing same | |
| WO2023165160A1 (en) | Positive electrode material, and preparation method therefor and use thereof | |
| WO2023216453A1 (en) | Core-shell gradient ternary precursor, and preparation method therefor and use thereof | |
| CN112838208B (en) | Preparation method and application of lithium ion battery anode material | |
| CN114864911A (en) | Modified high-nickel ternary cathode material and preparation method and application thereof | |
| CN113745478A (en) | Electrode material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 21946672 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |