CN117525403A - High-voltage high-capacity medium-high nickel monocrystal ternary positive electrode material, preparation method thereof and battery - Google Patents
High-voltage high-capacity medium-high nickel monocrystal ternary positive electrode material, preparation method thereof and battery Download PDFInfo
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- CN117525403A CN117525403A CN202311283201.2A CN202311283201A CN117525403A CN 117525403 A CN117525403 A CN 117525403A CN 202311283201 A CN202311283201 A CN 202311283201A CN 117525403 A CN117525403 A CN 117525403A
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 79
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 65
- 239000011248 coating agent Substances 0.000 claims abstract description 62
- 239000011247 coating layer Substances 0.000 claims abstract description 37
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 20
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 239000012792 core layer Substances 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims abstract description 14
- 239000010941 cobalt Substances 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011572 manganese Substances 0.000 claims abstract description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 56
- 238000003756 stirring Methods 0.000 claims description 30
- 238000005245 sintering Methods 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000010410 layer Substances 0.000 claims description 20
- 239000010406 cathode material Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 16
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 15
- 239000004327 boric acid Substances 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 13
- 229910052810 boron oxide Inorganic materials 0.000 claims description 12
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005253 cladding Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- JOMGYQRFIJXMJV-UHFFFAOYSA-N [B].OOO Chemical compound [B].OOO JOMGYQRFIJXMJV-UHFFFAOYSA-N 0.000 claims description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical group O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 20
- 238000002156 mixing Methods 0.000 description 20
- 229910052744 lithium Inorganic materials 0.000 description 19
- 229910052782 aluminium Inorganic materials 0.000 description 17
- 239000002344 surface layer Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000003513 alkali Substances 0.000 description 9
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 9
- 229910008291 Li—B—O Inorganic materials 0.000 description 8
- 230000001603 reducing effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 229910013716 LiNi Inorganic materials 0.000 description 7
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 7
- 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 7
- 238000001816 cooling Methods 0.000 description 7
- 238000007086 side reaction Methods 0.000 description 7
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 6
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 6
- 229910018516 Al—O Inorganic materials 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000006255 coating slurry Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- -1 aluminum compound Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010280 constant potential charging Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010416 ion conductor Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- XDVOLDOITVSJGL-UHFFFAOYSA-N 3,7-dihydroxy-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B(O)OB2OB(O)OB1O2 XDVOLDOITVSJGL-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910015118 LiMO Inorganic materials 0.000 description 1
- CHHOPPGAFVFXFS-UHFFFAOYSA-M [Li+].[O-]S(F)(=O)=O Chemical compound [Li+].[O-]S(F)(=O)=O CHHOPPGAFVFXFS-UHFFFAOYSA-M 0.000 description 1
- QMPLWDJCEVRQNQ-UHFFFAOYSA-E [Li+].[Ti+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[Ti+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QMPLWDJCEVRQNQ-UHFFFAOYSA-E 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- CRGGPIWCSGOBDN-UHFFFAOYSA-N magnesium;dioxido(dioxo)chromium Chemical compound [Mg+2].[O-][Cr]([O-])(=O)=O CRGGPIWCSGOBDN-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000000153 supplemental effect Effects 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
Abstract
The invention belongs to the field of new energy sources, and discloses a high-voltage high-capacity medium-high nickel monocrystal ternary anode material which is characterized by comprising a core layer, an inner coating layer and an outer coating layer, wherein the inner coating layer is formed by coating aluminum hydroxide on the surface of the core layer by a wet coating method at 0-10 ℃; the outer coating layer is formed by coating a boron source on the surface of the inner coating layer by a dry coating method; the molar content of nickel in the core layer accounts for more than 60 percent of the total molar amount of nickel, cobalt and manganese. The positive electrode material has excellent first charge and discharge capacity. Meanwhile, the invention also provides a preparation method of the positive electrode material and a lithium ion battery.
Description
Technical Field
The invention relates to the field of new energy, in particular to a high-voltage high-capacity medium-high nickel monocrystal ternary anode material, a preparation method thereof and a battery.
Background
Along with the progress of human society and the upgrading of consumption, the consumer end puts forward higher and higher requirements on an energy storage device, and the currently mainstream energy storage device is a lithium ion battery, and is divided into a power type lithium ion battery and a consumer electronic product lithium ion battery, so that the commercial lithium ion battery not only has good safety requirements, but also has the characteristics of high energy density and low economic cost. The key way of limiting the energy density of the lithium ion battery is to improve the performance of the positive electrode material, and the nickel-increasing, single crystallization and high voltage of the positive electrode material are the main current technical routes for improving the energy density, but the problems are that the nickel-increasing causes the residual lithium on the surface of the material to be increased, a series of problems of safety, storage, processing and the like are caused, the single crystallization causes the problems of lengthening of the lithium ion transmission path of the material, deterioration of the uniformity of particles and the like, the stability of the surface and the internal structure of the material is poor under high voltage, the side reaction is increased, the structural collapse is caused, the cycle life is short and the like. Therefore, in order to obtain a high-voltage high-capacity medium-high nickel single crystal ternary cathode material, the above problems need to be solved with a strong force.
D1: 202210721702.3 discloses a low-temperature high-power ternary cathode material and a preparation method thereof, and belongs to the technical field of lithium ion batteries. The preparation method of the low-temperature high-power ternary positive electrode material comprises the following steps: uniformly mixing the ternary precursor, lithium salt, magnesium chromate, titanium zirconium lithium phosphate to obtain a mixed material; sintering the mixed material in an oxygen-containing atmosphere, and crushing a sintered sample to obtain a crushed material; and finally, layering and coating the outer surface of the crushed material to form an aluminum fluoride layer and a boron oxide layer, thereby obtaining a target product.
The description is as follows: the boron oxide and aluminum fluoride double-layer coating is utilized, the aluminum fluoride coating layer is blocked from contacting with electrolyte in the battery charging and discharging process, the side reaction on the surface of the material is reduced, and the cycle performance of the material is improved. The boric acid is generated by the boron oxide which absorbs water in the air more easily, so that the water absorption of lithium oxide on the surface of the material is reduced to be converted into lithium hydroxide and lithium carbonate, the effect of reducing residual alkali on the surface of the material is further achieved, the generated boric acid can acidize the surface of the material, the corrosion of electrolyte on the surface of the material is reduced, and the cycle performance of the material is further improved.
Example 1 describes: the method for coating the aluminum fluoride layer and the boron oxide layer on the outer surface of the crushed material in a layering way comprises the following steps: aluminum fluoride and pulverized material in a mass ratio of 0.015:1, then placing the materials in a muffle furnace to sinter for 8 hours at 650 ℃, crushing the materials in a universal crusher for 30 seconds after sintering, and sieving the materials in a 400-mesh screen to obtain the material coated with the aluminum fluoride layer.
It can be seen that this solution is carried out by dry coating.
D2: 201910959426.2 discloses a quaternary positive electrode material for a lithium ion battery, a preparation method thereof and the lithium ion battery. The quaternary positive electrode material comprises a core and a coating layer, wherein the coating layer is formed on at least part of the surface of the core, the quaternary positive electrode material has a composition shown as a formula (I), in the formula (I), lixNiaCobMncAldMyO2 (I), x is more than or equal to 1.00 and less than or equal to 1.05, y is more than or equal to 0.00 and less than or equal to 0.05, a is more than or equal to 0.3 and less than or equal to 0.92, b is more than or equal to 0.03 and less than or equal to 0.06, c is more than or equal to 0.01 and less than or equal to 0.03, d is more than or equal to 0.01, a+b+c+d=1, and M is at least one selected from a second main group element, a third main group element, a fourth subgroup element and a fifth subgroup element.
The description is as follows: a method of quaternary positive electrode material comprising:
(1) Mixing a quaternary positive electrode material precursor, a lithium source and a doping agent to obtain a first mixed material;
(2) Performing first sintering treatment on the first mixed material to obtain a quaternary positive electrode material core;
(3) Mixing the quaternary positive electrode material inner core with a first coating agent to obtain a second mixed material;
(4) Performing second sintering treatment on the second mixed material to obtain a primary coating product;
(5) Mixing the primary coated product with a second coating agent to obtain a third mixed material;
(6) And calcining the third mixed material to obtain the quaternary positive electrode material.
The first coating agent comprises at least one selected from aluminum oxide, aluminum hydroxide, aluminum nitrate and aluminum oxyhydroxide;
the second coating agent comprises at least one selected from boric acid, boron oxide, lithium phosphate and lithium niobate.
The description is as follows: in order to further improve the quality of the prepared quaternary positive electrode material, according to the embodiment of the present invention, the primary coated product may be subjected to a water washing treatment and a drying treatment prior to S500. Thus, impurities contained in the primary coated product can be effectively removed. The inventors found in the study that the primary coated product contains some impurities such as residual alkali Li2CO3, liOH, li2O and the like. If the impurities are not removed, the viscosity of the battery slurry is increased or even gel or jelly is formed in the process of manufacturing the battery, and the material cannot enter the next step.
Examples of this are described in which alumina is used for dry coating.
From this document, we can find that this document tends to wash out residual lithium by water.
D3: 201910831610.9 discloses a positive electrode material, the chemical formula of the positive electrode material is Li1.01-1.12 NixCoyMn (1-x-y) M0.001-0.008B0.001-0.015O2, wherein 0.45<x<0.75，0.15<y<0.35，0<x+y<1, M is one or more than one of Al, ti, sn, nb, the positive electrode materialThe material comprises a lithium nickel cobalt manganese oxide matrix and LiMO coated on the lithium nickel cobalt manganese oxide matrix 2 -B 2 O 3 Is a glass state composite coating layer.
The description is as follows: s2: and (3) putting the lithium nickel cobalt manganese oxide matrix and the metal compound containing M into a ball milling tank for ball milling, and obtaining the lithium nickel cobalt manganese oxide coated matrix coated with the metal oxide film after the first heat treatment, wherein M is at least one or more than one of Al, ti, sn, nb. The M-containing metal compound is one or more of aluminum nitrate, aluminum acetate, aluminum hydroxide, titanium dioxide, titanium hydroxide, tin oxide and niobium pentoxide. The molar ratio of the metal compound to the lithium nickel cobalt manganese oxide matrix is 0.001-0.008: 1. the ball milling time is 1-3 h. The ball-to-material ratio is 1.3:1. The first heat treatment temperature is 600-900 ℃, and the first heat treatment time is 8-16 h.
S3: and uniformly mixing the lithium nickel cobalt manganese oxide coating matrix coated with the metal oxide film with the boron-containing compound in a high-speed mixer, and performing secondary heat treatment to obtain the anode material.
The boron-containing compound is boric acid, metaboric acid, pyroboric acid (H) 2 B 4 O 7 ) One of boron oxide. The molar ratio of the boron-containing compound to the lithium nickel cobalt manganese oxide coated substrate is 0.001-0.015:1. The mixing time is 5-15 min. The temperature of the second heat treatment is 300-600 ℃, and the time of the second heat treatment is 4-12 h.
D4: 202210287611.3 discloses a preparation method of an Al/B co-coated cathode material. Uniformly mixing a precursor material with a lithium source, and sintering in an air or oxygen atmosphere to obtain a positive electrode material matrix; mixing the anode material matrix with a nanoscale Al source at a high speed in a mixer, and then adding a lithium source and a micron-sized B source for low-speed mixing to obtain a mixture; and sintering the mixture in air or oxygen atmosphere to obtain the Al/B co-coated positive electrode material. The Al source is at least one of nanoscale aluminum oxide, hydroxyl aluminum oxide and aluminum hydroxide; the B source is at least one of micron-sized boron oxide, boron nitride and boric acid.
The description is as follows: the invention adopts a pure dry coating process to form Al/B co-coating on the surface of the anode material. Coating an Al source on the surface of a positive electrode material matrix under the condition of high-speed mixing, wherein the Al source is uniformly adhered to the surface of the particles; and then coating the B source on the surface of the positive electrode material matrix under the low-speed condition, and supplementing the lithium source. The coated Al source is combined with the residual alkali on the surface, the coated B source is combined with the supplemental Li source, and double-layer coating films of Li-Al-O/Li-B-O are respectively formed after secondary sintering, so that the ionic conductivity of the positive electrode material is further improved, and meanwhile, the positive electrode material is less contacted with electrolyte under the uniform coating of the double-layer films, the HF corrosion resistance is enhanced, and the cycle and rate performance are improved.
D5: 201610223367.9 discloses a high-voltage monocrystal-like ternary cathode material and a preparation method thereof. The general formula of the material can be expressed as LixNi1-m-nComMnnO 2 (0.96<x<1.12，0<m<1，0<n<1, and m+n<1). The preparation method comprises the steps of taking nickel salt, cobalt salt and manganese salt as raw materials, preparing a precursor by adopting a coprecipitation method or a chemical synthesis method, mixing the precursor with a lithium source, adding a modifier into the mixture after pretreatment, and obtaining the high-voltage monocrystal-like ternary anode material through sintering, crushing and sieving after uniform mixing. The grain size of the prepared high-voltage monocrystal-like ternary cathode material is 2-15 mu m, and the compaction density reaches 3.8-3.9 g/cm < 3 >. Meanwhile, the ternary positive electrode material is subjected to surface modification through wet-process Al-coated, so that the material structure is stabilized, and side reactions of the material and electrolyte are inhibited.
The description is as follows: (4) Carrying out wet coating on the obtained material LixNi1-m-nComMnnO2 in the step (3): slowly adding the prepared solution containing the aluminum compound into the LixNi1-m-nComMnnO2 obtained in the step (3) through a peristaltic pump in a water phase system or an organic phase system, controlling the pH value of the reaction within a range of 5.5-10.5, and controlling the reaction temperature within a range of 25-65 ℃; stirring for 0.5-4 h at the stirring speed of 300-800 r/min, then carrying out suction filtration and drying, and finally calcining at 400-800 ℃ for 5-10 h to obtain the LixNi1-m-nComMnnO2 material with the surface uniformly coated with aluminum.
The aluminum-containing compound solution adopts more than one of aluminum nitrate, aluminum isopropoxide, aluminum ethoxide, aluminum acetylacetonate, aluminum stearate, aluminum oxyhydroxide, aluminum chloride and nano aluminum oxide, and the coating amount of the aluminum is 0.01-5wt%.
After Al is coated by a wet method, a uniform coating layer exists on the surface of the crystal grain, so that the reaction of materials and electrolyte can be prevented, and the cycle performance, high-temperature storage performance and safety performance of the lithium ion battery under high voltage are effectively improved. The practical detection of the wet-process package Al effectively improves the cycle performance, the high-temperature storage performance and the safety performance of the lithium ion battery under the high voltage of 4.4V and 4.5V.
D6: the positive electrode disclosed in CN202010842563.0 includes a positive electrode current collector and a positive electrode active material layer provided on the positive electrode current collector. The nonaqueous electrolyte contains lithium fluorosulfonate. The positive electrode active material layer contains a positive electrode active material, and the positive electrode active material layer contains alumina hydrate at least in a surface layer portion. The alumina hydrate is aluminum hydroxide or aluminum oxyhydroxide.
The following conclusions can be drawn from the above documents:
conclusion 1: the coating of aluminum and boron is disclosed in D1-D4, and the boron is mainly used for reducing residual alkali and reducing corrosion of electrolyte to the surface of the material, so that the cycle performance of the material is further improved; in some comparison documents, it is considered that Al can be combined with residual alkali, and a double-layer coating film of Li-Al-O/Li-B-O can be formed by matching with boron; but dry coating is used in all of D1-D4.
Conclusion 2: d5 discloses wet coating of Al and D6 does not disclose what method it uses for coating.
From the analysis, the aluminum and the boron have residual alkali reducing effect, the inner layer is aluminum and can play a role in isolation, and the aluminum and the boron can form a double-coating film.
Meanwhile, the wet-process coated aluminum has a uniform coating layer on the surface of the crystal grain, so that the reaction of materials and electrolyte can be prevented, and the cycle performance, high-temperature storage performance and safety performance of the lithium ion battery under high voltage are effectively improved.
But there is no significant difference between dry and wet aluminum inclusion as a whole.
The technical problem that the present case solves is: how to further improve the first charge-discharge capacity of the positive electrode material.
Disclosure of Invention
The invention aims to provide a high-voltage high-capacity medium-high nickel monocrystal ternary positive electrode material, which has excellent first charge and discharge capacity.
Meanwhile, the invention also provides a preparation method of the positive electrode material and a lithium ion battery.
In order to achieve the above purpose, the present invention provides the following technical solutions: the high-voltage high-capacity medium-high nickel monocrystal ternary anode material comprises a core layer, an inner cladding layer and an outer cladding layer, wherein the inner cladding layer is formed by cladding aluminum hydroxide on the surface of the core layer by a wet cladding method at 0-10 ℃; the outer coating layer is formed by coating a boron source on the surface of the inner coating layer by a dry coating method; the molar content of nickel in the core layer accounts for more than 60 percent of the total molar amount of nickel, cobalt and manganese.
After the positive electrode material is treated by a special coating process, the residual lithium hydroxide on the surface can be reduced to below 500ppm, the total residual lithium is reduced to below 2500ppm, and the lower residual lithium can not only reduce the processing difficulty of the subsequent preparation of lithium ion battery slurry, but also improve the high-temperature storage performance of the battery. Al in the solution can be fully and efficiently combined with residual lithium to form a 'Li-Al-O' structural substance, the content of the residual lithium is reduced, a uniform and compact coating layer is formed on the inner surface layer of the material, the core of the positive electrode material can be effectively isolated from being in direct contact with electrolyte, the side reaction activity is reduced, the side reaction is effectively inhibited, the electrolyte is consumed, and the elements of the positive electrode material are dissolved out, so that the circulation under the high-voltage condition is improved. The outer surface layer is coated with LixBO 3-containing substances, B-containing substances on the outer surface layer are isolated on the outer surface layer by the Al coating layer, so that the combination with structural Li in a material inner core can be avoided, the combination with residual Li which does not react with Al is preferential, and part of Li in Li-Al-O is extracted, so that a Li-B-O structural substance is formed, and the Li in the Li-B-O structure can be preferentially used for generating a positive CEI film and migrating to a negative electrode for generating an SEI film because of being positioned on the outermost surface layer, thereby reducing the loss of active lithium in primary charge and discharge, and the formed Li-B-O substance is a fast ion conductor layer, accelerating the deintercalation of lithium ions on the surface of the positive electrode material, further reducing polarization and improving primary charge and discharge capacity.
In the high-voltage high-capacity medium-high-nickel monocrystal ternary cathode material, the coating amount of the inner coating layer is 1% -5%. Preferably 2.86-4.29%; the% herein represents 100g of the positive electrode material and the amount of aluminum oxyhydroxide required corresponds to the percentage content of the positive electrode material;
in the high-voltage high-capacity medium-high-nickel monocrystal ternary cathode material, the cladding amount of the outer cladding layer is 0.1% -0.6%, and the boron source is boron oxide or boron oxyhydroxide. The% herein represents 100g of the positive electrode material and the amount of boron source required corresponds to the percentage content of the positive electrode material; preferably, the coating amount of the outer coating layer is 0.11% -0.35%.
In the high-voltage high-capacity medium-high nickel monocrystal ternary cathode material, the chemical formula of the core layer is as follows: liNi x Co y Mn 1-x-y O 2 Wherein, 0.6<x<0.8，0.05≤y≤0.10。
Although only the specific cases where x is 0.72 and y is 0.07 are shown in the examples of the present invention, it was found that the method of the present invention can exhibit the same trend of variation within the above range for the high nickel single crystal ternary material in the course of repeated experiments.
Meanwhile, the invention also discloses a preparation method of the positive electrode material, which comprises the following steps:
step 1: coating the surface of the core layer with aluminum hydroxide in a wet coating mode to form an inner coating layer; the wet coating temperature is 0-10 ℃;
step 2: and coating boric acid on the surface of the inner coating layer in a dry coating mode to form the outer coating layer.
In the above preparation method of the positive electrode material, in the step 1, the ratio of the core layer to the solvent is 0.5-2:1.
in the preparation method of the positive electrode material, the solvent is water or absolute ethyl alcohol or hydrous ethyl alcohol with any concentration;
the coating time is 5-60min;
the wet coating comprises the following steps: adding the aluminum hydroxide solution into a solvent, stirring, then adding a positive electrode material, and continuing stirring;
and (3) filtering the treated material with the step (1) to obtain a material with an inner coating layer, and drying the material and then carrying out the step (2).
In the preparation method of the positive electrode material, the weight ratio of the boric acid to the material with the outer coating layer obtained in the step 1 is 1000:1-6.
In the preparation method of the positive electrode material, a ball mill is adopted for dry coating, and then sintering is carried out at the temperature of 300-450 ℃.
Finally, the invention also discloses a lithium ion battery which is characterized by comprising a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the active ingredients in the positive electrode are any one of the above.
Compared with the prior art, the invention has the beneficial effects that:
the residual lithium hydroxide on the surface of the positive electrode material can be reduced to below 500ppm, the total residual lithium is reduced to below 2500ppm, and the lower residual lithium on the surface can not only reduce the processing difficulty of the subsequent preparation of lithium ion battery slurry, but also improve the high-temperature storage performance of the battery. Al in the solution can be fully and efficiently combined with residual lithium to form a 'Li-Al-O' structural substance, the content of the residual lithium is reduced, a uniform and compact coating layer is formed on the inner surface layer of the material, the core of the positive electrode material can be effectively isolated from being in direct contact with electrolyte, the side reaction activity is reduced, the side reaction is effectively inhibited, the electrolyte is consumed, and the elements of the positive electrode material are dissolved out, so that the circulation under the high-voltage condition is improved. The outer surface layer is coated with LixBO 3-containing substances, B-containing substances on the outer surface layer are isolated on the outer surface layer by the Al coating layer, so that the combination with structural Li in a material inner core can be avoided, the combination with residual Li which does not react with Al is preferential, and part of Li in Li-Al-O is extracted, so that a Li-B-O structural substance is formed, and the Li in the Li-B-O structure can be preferentially used for generating a positive CEI film and migrating to a negative electrode for generating an SEI film because of being positioned on the outermost surface layer, thereby reducing the loss of active lithium in primary charge and discharge, and the formed Li-B-O substance is a fast ion conductor layer, accelerating the deintercalation of lithium ions on the surface of the positive electrode material, further reducing polarization and improving primary charge and discharge capacity.
Drawings
FIG. 1 is a scanning electron microscope image of a high voltage single crystal low cobalt ternary positive electrode material of example 1;
FIG. 2 is a scanning electron microscope image of the high voltage single crystal low cobalt ternary positive electrode material of example 2;
FIG. 3 is a scanning electron microscope image of the high voltage single crystal low cobalt ternary positive electrode material of example 3;
FIG. 4 is a scanning electron microscope image of the high voltage single crystal low cobalt ternary positive electrode material of example 4;
FIG. 5 is a scanning electron microscope image of the high voltage single crystal low cobalt ternary positive electrode material of example 5;
FIG. 6 is a scanning electron microscope image of the high voltage single crystal low cobalt ternary positive electrode material of comparative example 1;
FIG. 7 is a scanning electron microscope image of the high voltage single crystal low cobalt ternary positive electrode material of comparative example 2;
FIG. 8 is a scanning electron microscope image of the high voltage single crystal low cobalt ternary cathode material of comparative example 3.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
A preparation method of a high-voltage high-capacity medium-high nickel monocrystal ternary cathode material comprises the following steps:
1) Adding a solution containing 2.86g of aluminum hydroxide into 100ml of deionized water, controlling the water temperature to be within 0-10 ℃, and stirring for 15min;
2) Then adding 100g of positive electrode material, and continuously stirring for 30min; the chemical formula of the positive electrode material is (LiNi 0.72 Co 0.07 Mn 0.21 O 2 )
3) Stirring while using ice bath to ensure that the solution is in a range of 0-10 ℃, and vacuumizing and dehydrating to obtain primary inner surface layer coating slurry;
4) Transferring the mixture into a constant temperature drying oven, and thoroughly drying the mixture at 100 ℃/3 hours;
5) Mixing the thoroughly dried coating with 0.18g boric acid for 30min by a ball mill, transferring into a muffle furnace, and sintering at 350 ℃/6 h;
6) And cooling to room temperature, and taking out to obtain the surface-coated high-voltage high-capacity medium-high-nickel monocrystal ternary anode material.
Example 2
A preparation method of a high-voltage high-capacity medium-high nickel monocrystal ternary cathode material comprises the following steps:
1) Adding a solution containing 2.86g of aluminum hydroxide into 100ml of absolute ethyl alcohol, controlling the temperature within 0-10 ℃ and stirring for 15min;
2) Then adding 100g of positive electrode material, and continuously stirring for 30min; the chemical formula of the positive electrode material is (LiNi 0.72 Co 0.07 Mn 0.21 O 2 )
3) Stirring while using ice bath to ensure that the solution is in a range of 0-10 ℃, and vacuumizing and dehydrating to obtain primary inner surface layer coating slurry;
4) Transferring the mixture into a constant temperature drying oven, and thoroughly drying the mixture at 100 ℃/3 hours;
5) Mixing the thoroughly dried coating with 0.18g boric acid for 30min by a ball mill, transferring into a muffle furnace, and sintering at 300 ℃/6 h;
6) And cooling to room temperature, and taking out to obtain the surface-coated high-voltage high-capacity medium-high-nickel monocrystal ternary anode material.
Example 3
A preparation method of a high-voltage high-capacity medium-high nickel monocrystal ternary cathode material comprises the following steps:
1) Adding a solution containing 4.29g of aluminum hydroxide into 100ml of deionized water, controlling the temperature within 0-10 ℃ and stirring for 15min;
2) Then adding 100g of positive electrode material, and continuously stirring for 30min; the chemical formula of the positive electrode material is (LiNi 0.72 Co 0.07 Mn 0.21 O 2 )
3) Stirring while using ice bath to ensure that the solution is in a range of 0-10 ℃, and vacuumizing and dehydrating to obtain primary inner surface layer coating slurry;
4) Transferring the mixture into a constant temperature drying oven, and thoroughly drying the mixture at 100 ℃/3 hours;
5) Mixing the thoroughly dried coating with 0.18g boric acid for 30min by a ball mill, transferring into a muffle furnace, and sintering at 350 ℃/6 h;
6) And cooling to room temperature, and taking out to obtain the surface-coated high-voltage high-capacity medium-high-nickel monocrystal ternary anode material.
Example 4
A preparation method of a high-voltage high-capacity medium-high nickel monocrystal ternary cathode material comprises the following steps:
1) Adding a solution containing 2.86g of aluminum hydroxide into 100ml of deionized water, controlling the temperature within 0-10 ℃ and stirring for 15min;
2) Then adding 100g of positive electrode material, and continuously stirring for 30min; the chemical formula of the positive electrode material is (LiNi 0.72 Co 0.07 Mn 0.21 O 2 )
3) Stirring while using ice bath to ensure that the solution is in a range of 0-10 ℃, and vacuumizing and dehydrating to obtain primary inner surface layer coating slurry;
4) Transferring the mixture into a constant temperature drying oven, and thoroughly drying the mixture at 100 ℃/3 hours;
5) Mixing the thoroughly dried coating with 0.18g of nano boron oxide for 30min by a ball mill, transferring into a muffle furnace, and sintering at 350 ℃/6 h;
6) And cooling to room temperature, and taking out to obtain the surface-coated high-voltage high-capacity medium-high-nickel monocrystal ternary anode material.
Example 5
A preparation method of a high-voltage high-capacity medium-high nickel monocrystal ternary cathode material comprises the following steps:
1) Adding a solution containing 2.86g of aluminum hydroxide into 100ml of deionized water, controlling the temperature within 0-10 ℃ and stirring for 15min;
2) Then adding 100g of positive electrode material, and continuously stirring for 30min;
3) Stirring while using ice bath to ensure that the solution is in a range of 0-10 ℃, and vacuumizing and dehydrating to obtain primary inner surface layer coating slurry;
4) Transferring the mixture into a constant temperature drying oven, and thoroughly drying the mixture at 100 ℃/3 hours;
5) Mixing the thoroughly dried coating with 0.27g of nano boron oxide for 30min by a ball mill, transferring into a muffle furnace, and sintering at 350 ℃/6 h;
6) And cooling to room temperature, and taking out to obtain the surface-coated high-voltage high-capacity medium-high-nickel monocrystal ternary anode material.
Example 6
The same operation as in example 1 was conducted except that 3g of aluminum oxyhydroxide was used and 0.11g of boric acid was used. The stirring time in step 1 was 20 minutes, and the stirring time in step 2 was 20 minutes. The sintering temperature in the step 5 is 300 ℃ and the sintering time is 5h.
Example 7
The same operation as in example 1 was conducted except that the amount of aluminum oxyhydroxide used was 3.5g and the amount of boric acid used was 0.22g. The stirring time in step 1 was 10 minutes, and the stirring time in step 2 was 15 minutes. The sintering temperature in the step 5 is 350 ℃ and the sintering time is 6h.
Example 8
The same operation as in example 1 was conducted except that the amount of aluminum oxyhydroxide used was 3.8g and the amount of boric acid used was 0.35g. The stirring time in step 1 was 30 minutes, and the stirring time in step 2 was 30 minutes. The sintering temperature in the step 5 is 400 ℃ and the sintering time is 4 hours.
Comparative example 1
The preparation method of the ternary positive electrode material comprises the following steps:
1) Adding 2.86g of aluminum hydroxide solution into 100ml of deionized water, controlling the water temperature to be within 0-10 ℃, and stirring for 15min;
2) Subsequently, 100g of a positive electrode material (LiNi 0.72 Co 0.07 Mn 0.21 O 2 ) Stirring is continued for 30min;
3) Stirring while using ice bath to ensure that the solution is in a range of 0-10 ℃, and vacuumizing and dehydrating to obtain primary inner surface layer coating slurry;
4) Transferring the mixture into a constant temperature drying oven, and thoroughly drying the mixture at 100 ℃/3 hours;
5) Sintering in a muffle furnace at 350 ℃/6h, cooling to room temperature, and taking out to obtain the monocrystal ternary anode material of the comparative example 1.
Comparative example 2
The preparation method of the ternary positive electrode material comprises the following steps:
1) Mixing 100g of a primary sintered matrix with 0.18g of nano boron oxide for 30min through a ball mill, transferring into a muffle furnace, and sintering at 350 ℃/6 h; the chemical formula of the primary burned matrix is LiNi 0.72 Co 0.07 Mn 0.21 O 2 ；
2) And cooling to room temperature, and taking out to obtain the ternary cathode material of the comparative example 2.
Comparative example 3
Substantially as in example 1, except that the temperature of the final sinter clad was 500 ℃/6 hours.
Comparative example 4
A preparation method of a ternary positive electrode material comprises the following steps: 0.23g of nano alumina (same as Al content in 2.86g of hydroxy alumina solution) and 100g of positive electrode material (LiNi 0.72 Co 0.07 Mn 0.21 O 2 ) Mixing, ball milling, and sintering in a muffle furnace at 350 ℃/6h.
Comparative example 5
Substantially the same as in example 1, except that aluminum hydroxide was replaced with an equivalent molar amount of aluminum nitrate.
Comparative example 6
Substantially the same as in example 1, except that aluminum hydroxide was used instead of aluminum hydroxide in an equivalent molar amount.
Comparative example 7
Generally as in example 1, except that steps 1-3 were performed at normal temperature.
Performance testing
Test items: 0.1C initial charge, 0.1C initial discharge, 0.1C initial effect, 50-week cycle retention rate and residual alkali detection.
The testing method comprises the following steps:
0.1C initial charge test: constant-current charging is carried out to 4.45V at the constant temperature with the multiplying power of 0.1C, the constant-voltage charging is carried out to the cutoff current of less than 0.05C, and the sum of the constant-current charging and the constant-voltage charging capacity is measured by the first charge capacity;
0.1C first test: at normal temperature, 0.1C constant current discharge is carried out to 3.0V;
0.1C first effect test: the ratio of the first discharge capacity to the first charge capacity;
50 week cycle retention test: at normal temperature, 1C charge-discharge cycle was 50 weeks.
The test results are shown in tables 1 and 2
Table 1 shows the buckling capacity of the high-voltage monocrystal low-cobalt ternary positive electrode material of the examples and the comparative examples
Table 2 comparison of lithium residue of the high voltage single crystal low cobalt ternary cathode materials of examples and comparative examples
Conclusion analysis:
1. as can be seen from the analysis of comparative examples 1 and 4, the wet-process coated aluminum and the dry-process coated aluminum are adopted only, and the two are greatly different in terms of reduction of residual alkali in electrical properties;
2. as can be seen from the comparison of example 1 and comparative example 1, without coating with boron, the initial, initial and cycle retention rates thereof are deteriorated; as can be seen from a comparison of example 1 and comparative example 2, without coating the aluminum oxyhydroxide, the initial, initial and cycle retention rates are further deteriorated.
3. As can be seen from the comparison of example 1 and comparative example 3, the material is relatively sensitive to sintering temperature, and the coating failure can be caused by the excessive temperature;
4. as can be seen from the comparison of example 1 and comparative examples 5 and 6, other aluminum sources were inferior to aluminum oxyhydroxide in electrical properties and residual alkali improvement effects;
5. as can be seen from a comparison of example 1 and comparative example 7, the wet coating temperature is a very important process parameter for the whole experiment.
FIGS. 1-8 are electron microscope images of examples 1-5 and comparative examples 1-3, as can be seen from FIGS. 1-8: compared with a dry method material mixing method, the wet method coating can obviously reduce residual lithium on the surface of the material and improve the uniformity of the surface coating;
based on the analysis, we consider that wet coating is favorable for lithium to be dissociated into liquid at low temperature, and can be uniformly combined with aluminum on the surface of the material along with coating, which is beneficial for first charge, first discharge, first effect and cycle maintenance;
compared with free aluminum ions and aluminum hydroxide, the aluminum hydroxide has the characteristics of molecular structure, is insoluble in water and can not be pumped and filtered through Cheng Daizou, and when the aluminum hydroxide is coated on the surface of the positive electrode material, the aluminum hydroxide shows uniform and stable coating; the composite material is combined with a boron source coated by a dry method to form an inner coating layer and an outer coating layer, so that the electrical property is further improved.
Claims (10)
1. The high-voltage high-capacity medium-high nickel monocrystal ternary anode material is characterized by comprising a core layer, an inner coating layer and an outer coating layer, wherein the inner coating layer is formed by coating hydroxyl aluminum oxide on the surface of the core layer by a wet coating method at the temperature of 0-10 ℃; the outer coating layer is formed by coating a boron source on the surface of the inner coating layer by a dry coating method; the molar content of nickel in the core layer accounts for more than 60 percent of the total molar amount of nickel, cobalt and manganese.
2. The high-voltage high-capacity medium-high nickel single crystal ternary cathode material according to claim 1, wherein the coating amount of the inner coating layer is 1% -5%.
3. The high-voltage high-capacity medium-high nickel single crystal ternary cathode material according to claim 1, wherein the cladding amount of the outer cladding layer is 0.1% -0.6%, and the boron source is boron oxide or boron oxyhydroxide.
4. The high-voltage high-capacity medium-high nickel single crystal ternary cathode material according to claim 1, wherein the chemical formula of the core layer is: liNi x Co y Mn 1-x-y O 2 Wherein, 0.6<x<0.8，0.05≤y≤0.10。
5. A method for producing the positive electrode material according to any one of claims 1 to 4, comprising the steps of:
step 1: coating the surface of the core layer with aluminum hydroxide in a wet coating mode to form an inner coating layer; the wet coating temperature is 0-10 ℃;
step 2: and coating boric acid on the surface of the inner coating layer in a dry coating mode to form the outer coating layer.
6. The method according to claim 5, wherein in the step 1, the ratio of the core layer to the solvent is 0.5-2:1.
7. the method for producing a positive electrode material according to claim 6, wherein the solvent is water or absolute ethanol or aqueous ethanol of any concentration;
the coating time is 5-60min;
the wet coating comprises the following steps: adding the aluminum hydroxide solution into a solvent, stirring, then adding a positive electrode material, and continuing stirring;
and (3) filtering the treated material with the step (1) to obtain a material with an inner coating layer, and drying the material and then carrying out the step (2).
8. The method for preparing a positive electrode material according to claim 5, wherein the weight ratio of the material with an inner coating layer obtained in step 1 to boric acid is 1000:1-6.
9. The method for producing a positive electrode material according to claim 5, wherein the positive electrode material is produced by dry coating with a ball mill and then sintering at 300 to 450 ℃.
10. A lithium ion battery comprising a positive electrode, a negative electrode, an electrolyte and a separator, wherein the active component in the positive electrode is as claimed in any one of claims 1 to 4.
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| CN116487553A (en) * | 2023-04-26 | 2023-07-25 | 贵州振华新材料有限公司 | Double-coating high-nickel lithium ion positive electrode 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116487553A (en) * | 2023-04-26 | 2023-07-25 | 贵州振华新材料有限公司 | Double-coating high-nickel lithium ion positive electrode 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 |
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| CN117832626A (en) * | 2024-03-06 | 2024-04-05 | 宁德新能源科技有限公司 | Electrolyte, electrochemical device, and electronic apparatus |
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