CN109461928A - A kind of high-energy density polynary positive pole material and preparation method thereof - Google Patents
A kind of high-energy density polynary positive pole material and preparation method thereof Download PDFInfo
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- CN109461928A CN109461928A CN201811091824.9A CN201811091824A CN109461928A CN 109461928 A CN109461928 A CN 109461928A CN 201811091824 A CN201811091824 A CN 201811091824A CN 109461928 A CN109461928 A CN 109461928A
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- pole material
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- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011159 matrix material Substances 0.000 claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000010416 ion conductor Substances 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 9
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 26
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 229910009677 Li8ZrO6 Inorganic materials 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000005253 cladding Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910007822 Li2ZrO3 Inorganic materials 0.000 claims description 8
- 229910010883 Li6Zr2O7 Inorganic materials 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000012216 screening Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910010565 Li4ZrO4 Inorganic materials 0.000 claims description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 229910002986 Li4Ti5O12 Inorganic materials 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910001556 Li2Si2O5 Inorganic materials 0.000 claims description 2
- 229910007562 Li2SiO3 Inorganic materials 0.000 claims description 2
- 229910007626 Li2SnO3 Inorganic materials 0.000 claims description 2
- 229910007848 Li2TiO3 Inorganic materials 0.000 claims description 2
- 229910010488 Li4TiO4 Inorganic materials 0.000 claims description 2
- 229910010682 Li5AlO4 Inorganic materials 0.000 claims description 2
- 229910010215 LiAl5O8 Inorganic materials 0.000 claims description 2
- 229910010092 LiAlO2 Inorganic materials 0.000 claims description 2
- 229910052789 astatine Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 claims description 2
- 239000000320 mechanical mixture Substances 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 32
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 229910052744 lithium Inorganic materials 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000010936 titanium Substances 0.000 description 7
- 238000009831 deintercalation Methods 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910017246 Ni0.8Co0.1Mn0.1 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WYDJZNNBDSIQFP-UHFFFAOYSA-N [O-2].[Zr+4].[Li+] Chemical compound [O-2].[Zr+4].[Li+] WYDJZNNBDSIQFP-UHFFFAOYSA-N 0.000 description 1
- JOMNYEIYSNJMSL-UHFFFAOYSA-N [O].[Zr].[Li] Chemical compound [O].[Zr].[Li] JOMNYEIYSNJMSL-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of high-energy density polynary positive pole material and preparation method thereof, and it is Li that the positive electrode, which is by chemical formula,1+a[(Ni1‑2x Co x Mn x )1‑y M y ]1‑zM′ z O2Matrix and be coated on the Li on described matrix surface8ZrO6With lithium ion conductor Li u M″ v O w Composition, wherein -0.5≤a≤0.3, M and M ' are at least one of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B, Al element, M " is at least one of Zr, Ti, Al, Si, Mn, Sn element；Composite oxides coat 0.01~3% that total amount is matrix mole.Positive electrode of the invention energy density with higher and cyclical stability, can be used for lithium-ion-power cell.The preparation method simple process and low cost of the material is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of high-energy density polynary positive pole material and preparation methods, belong to lithium ion battery technology neck
Domain.
Background technique
High-energy is developed in raising along with people to demands such as electronic product cruise duration, electric car course continuation mileages
The lithium ion battery of density becomes the urgent need of Vehicles Collected from Market.In lithium ion battery, the superiority and inferiority of positive electrode performance is determined
The characteristics of performance of battery entirety, wherein multicomponent material is due to high voltage, height ratio capacity is considered most promising
One of anode material of lithium battery.With the increase of nickel content, the nonactive remaining lithium on surface gradually increases multicomponent material, seriously
Influence the performances such as capacity, the multiplying power of multicomponent material；Particle internal fissure, material dusting etc. are easy to happen in high voltage charge and discharge process
Problem causes its cycle performance to reduce rapidly.Boundary can be effectively reduced by constructing lithium ion conductor clad on the surface of the material
Face impedance increases lithium ion tunnel, inhibits to improve the chemical properties such as capacity, multiplying power, circulation with the side reaction between electrolyte.
However, lithium ion conductor usually requires to synthesize in advance as clad in previous research and patent report, on the one hand prepared
Journey is more complicated, on the other hand can not solve the problems, such as that the nonactive remaining lithium of material surface reduces material capacity, high rate performance.
Chinese patent CN107706390A discloses the lithium ion of a kind of fast-ionic conductor and the dual modification of conducting polymer
The preparation method of battery polynary positive pole material, oxide is first passed through in patent or acid reacts generation fast-ionic conductor with hydroxide
Then product is mixed simultaneously high-temperature calcination by finished product with ternary material again, obtain the multicomponent material of fast-ionic conductor cladding.The party
Method preparation process is complicated, and required sintering temperature is higher.
Chinese patent CN105789565A discloses a kind of Li2ZrO3And Li4ZrO4Coated lithium ion battery is lithium-rich manganese-based just
The preparation method of pole material.By Zr (OC in patent4H9)4ZrO is obtained using hydro-thermal method after mixing with positive electrode material precursor2Packet
Then it is obtained Li with lithium salts mixed sintering by the anode material precursor covered2ZrO3And Li4ZrO4The positive electrode of cladding leads to
The cladding of peroxychromic acid lithium effectively improves the cycle performance of sample.But the yield of hydro-thermal method is lower, the requirement to equipment is high, and
The source organic matter Zr higher cost used in the patent, therefore can not large-scale application.
Summary of the invention
For above-mentioned problems of the prior art, the present invention provides a kind of high-energy density nickel-cobalt-manganese multi anode material
There is the Li with electro-chemical activity in material and preparation method, nickel-cobalt-manganese multi material surface clad provided by the invention8ZrO6,
And other lithium ion conductors.Wherein Li8ZrO6It is all hexagonal crystal system with nickel-cobalt-manganese multi positive electrode, is being higher than 4.0V voltage
Lower there are the deintercalations of lithium ion, and when occurring two lithium ion deintercalations in molecule, charging and discharging capacity can achieve 220mAh/
g；Interface impedance of the battery in charge and discharge process can be effectively reduced in other lithium ion conductors in clad, constructs lithium ion
Channel, the ingredient in above-mentioned clad can make material have preferable high rate performance and higher energy density.
The present invention also provides the preparation method of above-mentioned metal hydroxides presoma and positive electrode, simple process, processes
It is easy stability contorting, production cost is low, is suitable for large-scale industrial production.
To achieve the goals above, the invention adopts the following technical scheme:
High-energy density polynary positive pole material provided by the invention, including matrix and the combined oxidation for being coated on described matrix surface
Object clad；The chemical formula of described matrix is Li1+a[(Ni1-2x Co x Mn x )1-y M y ]1-zM′ z O2, wherein -0.5≤a≤1.3,0.05
≤x≤ 0.3,0≤y≤ 0.01,0≤z≤ 0.01, the clad includes Li8ZrO6It is Li with chemical formula u M″ v O w Composite oxygen
Compound, wherein 0≤u≤ 8,1≤v≤ 5,2≤w≤ 12, M and M ' be La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W,
At least one of Nb, Sm, V, Mg, B, Al element, M " are at least one of Zr, Ti, Al, Si, Mn, Sn, W element；
The composite oxides clad is fine and close or un-densified；The amount of the substance of clad accounts for the 0.01~3% of matrix.
The average grain diameter D of the high-energy density polynary positive pole material50It is 5~20 μm.
Preferably, the Li u M″ v O w For LiAl5O8、LiAlO2、Li5AlO4、Li2SiO3、Li2Si2O5、Li4SiO4、
Li2SnO3、Li2TiO3、Li4TiO4、Li4Ti5O12、Li2ZrO3、Li6Zr2O7、Li8ZrO6、Li4ZrO4At least one of.
The present invention also provides the preparation methods of above-mentioned high-energy density polynary positive pole material, comprising the following steps:
(1) salt solution of nickel, cobalt, manganese and doped chemical is obtained into the mixing salt solution of 1~3mol/L；By sodium hydroxide
It is dissolved into the aqueous slkali that concentration is 4~10mol/L；The enveloping agent solution for being 2~10mol/L at concentration by ammonia solvent.It will mix
Closing salting liquid, aqueous slkali, enveloping agent solution, cocurrent is added in reaction kettle and is reacted together, is kept stirring in the process, simultaneously
Control pH value in reaction and reaction temperature, precursor pulp obtained obtain spherical shape after separation of solid and liquid, washing, drying, screening
Nickel cobalt manganese hydroxide (Ni1-2x Co x Mn x )1-y M y (OH)2；
(2) (the Ni for obtaining step (1)1-2x Co x Mn x )1-y M y (OH)2Be uniformly mixed with the oxide of lithium salts, M ', in air or
In oxygen atmosphere, 4~20h is calcined at 600~1000 DEG C, by broken, screening, obtains anode material for lithium ion battery base
Body Li1+a[(Ni1-2x Co x Mn x )1-y M y ]1-zM′ z O2；
(3) by ZrO2, the oxide of M ", lithium salts and the positive electrode matrix carry out mechanical mixture, then mixture is put into
In Muffle furnace, it is heat-treated 0.5~12h in 450~800 DEG C of temperature ranges, is made by Li8ZrO6And lithium ion conductor Li u M″ v O w
The polynary positive pole material of composite oxides cladding；
- 0.5≤a≤1.3,0.05≤x≤ 0.3,0≤y≤ 0.01,0≤z≤ 0.01,0≤u≤ 8,1≤v≤ 5,2≤w
≤ 12, M and M ' are that at least one of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B, Al are first
Element, M " are at least one of Zr, Ti, Al, Si, Mn, Sn, W element.
Preferably, the oxide of the M ', M " oxide particle average grain diameter D50For 1~50nm, specific surface area is greater than
10m2/g。
Preferably, the oxide of the M ', M " oxide be HfO2、TiO2、Y2O3、ZrO2、SiO2、W2O3、Nb2O5、
Sm2O3、V2O5、MgO、Al2O3At least one of.
Preferably, step (1) the reaction pH range is 10~13, and temperature is 50~70 DEG C.
Preferably, step (2), (3) described lithium salts are one or both of lithium carbonate, lithium hydroxide.
Preferably, the additional amount of step (2) described lithium salts is molar ratio=0.95~1.3 of Li/ (Ni+Co+Mn+M+M ').
Preferably, step (3) the mixed equipment is ball grinder, Ball-stirring mill, colter mixer, V-type batch mixer, high speed
One of mixing machine.
Preferably, step (3) heat-treating atmosphere is air or oxygen, and heat treatment temperature is 500~750 DEG C, the time
For 4~10h.
Present invention has the advantage that
(1) the high-energy density nickel-cobalt-manganese multi positive electrode that the present invention obtains has preferable structure in charge and discharge process
Stability, cycle performance are excellent.
(2) the high-energy density nickel-cobalt-manganese multi positive electrode that the present invention obtains, after Overheating Treatment, the packet of surface formation
Coating contains Li8ZrO6, Li8ZrO6In the case where being higher than 4.0V voltage with the electro-chemical activity of lithium ion deintercalation, to be obviously improved
The capacity of product.
(3) the high-energy density nickel-cobalt-manganese multi positive electrode that the present invention obtains, it is effective by the cladding of composite oxides
Reduce the residual non-reactive lithium content and interface impedance of positive electrode particle surface, hence it is evident that improve the forthright again of positive electrode
Energy.
(4) preparation method simple process of the present invention, pollution-free.Doped chemical and clad incorporation way are simple, and dosage is few,
Heat-treating atmosphere is without particular/special requirement.
Detailed description of the invention
In order to illustrate the technical solution of the embodiments of the present invention more clearly, required use in being described below to embodiment
Attached drawing be briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill in field, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is the scanning electron microscope (SEM) photograph of nickel-cobalt-manganese multi positive electrode matrix prepared by comparative example 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of high-energy density nickel-cobalt-manganese multi positive electrode prepared by embodiment 1.
Fig. 3 is the XRD spectrum that comparative example 1, embodiment 1 and embodiment 4 prepare sample.
Fig. 4 is charging and discharging curve figure of the half-cell of comparative example 1, embodiment 1 and the preparation of embodiment 4 at 0.1C.
Fig. 5 is specific discharge capacity figure of the half-cell of comparative example 1, embodiment 1 and the preparation of embodiment 4 under different multiplying.
Fig. 6 is cycle performance figure of the half-cell of comparative example 1, embodiment 1 and the preparation of embodiment 4 at 1C.
Fig. 7 is half-cell AC impedance figure prepared by comparative example 1, embodiment 1 and embodiment 4.
Specific embodiment
With reference to the attached drawing in the embodiment of the present invention, technical solution in the embodiment of the present invention carries out clear, complete
Ground description, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on this
The embodiment of invention, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, belongs to protection scope of the present invention.
Comparative example 1
Step 1: dissolving nickel sulfate, cobaltous sulfate, manganese sulfate to obtain the mixed of 2mol/L according to the ratio of metal molar ratio 3:1:1
Salting liquid is closed, sodium hydroxide is dissolved into the aqueous slkali that concentration is 8mol/L；The complexing for being 6mol/L at concentration by ammonia solvent
Agent solution.100L mixing salt solution, aqueous slkali, enveloping agent solution together cocurrent are added in reaction kettle and reacted, process
It is constant to be kept stirring revolving speed 120rpm, control pH is 11.5~11.7, and temperature is 60 DEG C, when reaction completion, keeps temperature, stirring
Revolving speed is constant, continues to stir 20min, is then separated by solid-liquid separation nickel cobalt manganese hydroxide slurry obtained, washs, filter cake
It is sieved after 105 DEG C of drying 5h, obtains spherical nickel cobalt manganese hydroxide.
Step 2: the spherical nickel cobalt manganese hydroxide that step 1 obtains is uniformly mixed with lithium carbonate, wherein lithium carbonate is pressed
It is added according to molar ratio Li/ (Ni+Co+Mn)=1.03.Then mixture is calcined 10 hours at 850 DEG C, after broken, screening
Obtain average grain diameter D50For 13 μm of nickel-cobalt-manganese multi positive electrode matrix Li1.03Ni0.6Co0.2Mn0.2O2.Surface is carried out to it
Remaining lithium titration, surface residual lithium content accounts for the 0.2% of matrix as the result is shown.
Step 3: by ZrO2The positive electrode matrix obtained with step 2 according to 0.2:100 the mass ratio of the material and meanwhile put
Enter and carry out dry mixed in ball milling mixing tank, is then placed in Muffle furnace and is heat-treated, 800 DEG C of heating under oxygen atmosphere
10h obtains the nickel-cobalt-manganese multi material of lithium Zirconium oxide cladding.
As shown in Figure 1, the nickel-cobalt-manganese multi positive electrode matrix microscopic appearance prepared in this comparative example is near-spherical particle.
As shown in figure 3, except multicomponent material main phase is special in the nickel-cobalt-manganese multi positive electrode XRD spectrum prepared in this comparative example
It levies without other dephasign peaks outside peak, this is because material surface can be with ZrO2The remaining lithium of reaction is less, the lithium zirconium oxygen of formation
Compound content is low, and XRD can not be detected.
Material is assembled into half-cell and carries out electrochemical property test, the electric discharge ratio under 3.0~4.5V, 0.1C multiplying power
Capacity is 201.3mAh/g, energy density 905.8Wh/kg.
Comparative example 2
Step 1 and step 2 are consistent with 1 preparation step of comparative example.
Step 3: by ZrO2, the obtained positive electrode matrix of lithium hydroxide and step 2 according to 0.3:2.2:100 substance
Amount ratio simultaneously be put into high speed mixer, mix 15min under the revolving speed of 800rpm, be then placed in Muffle furnace and carry out hot place
Reason, 400 DEG C of heating 10h, obtain the nickel-cobalt-manganese multi material of zirconium cladding after being sieved in air atmosphere.
Since heat treatment temperature is lower, the ingredient of positive electrode clad is mainly ZrO2.Material is assembled into half
Battery carries out electrochemical property test, and the specific discharge capacity under 3.0~4.5V, 0.1C multiplying power is 198.7 mAh/g, energy
Density is 894.2Wh/kg.
Embodiment 1
Step 1 and step 2 are consistent with 1 preparation step of comparative example.
Step 3: by ZrO2, the obtained positive electrode matrix of lithium hydroxide and step 2 according to 0.5:3.8:100 substance
Amount ratio simultaneously be put into high speed mixer, mix 10min under the revolving speed of 1200rpm, be then placed in Muffle furnace carry out heat
Processing, 600 DEG C of heating 8h, obtain average grain diameter D in air atmosphere50For 10 μm, clad main component be Li8ZrO6Nickel
Cobalt-manganese multi material.
As shown in Fig. 2, the positive electrode second particle surface prepared in the present embodiment is uniformly attached with tiny cladding
Grain, forms un-densified clad.
As shown in figure 3, except multicomponent material main phase is special in the nickel-cobalt-manganese multi positive electrode XRD spectrum prepared in the present embodiment
There is also Li outside sign peak8ZrO6Characteristic peak, show there is Li on the surface of the material8ZrO6Phase.
As shown in figure 4, the nickel-cobalt-manganese multi positive electrode prepared in the present embodiment, which is assembled into half-cell, carries out electrochemistry
Can test, specific discharge capacity under 3.0~4.5V, 0.1C multiplying power is 206.1mAh/g, energy density 927.5Wh/kg,
11.7Wh/kg is improved than 1 sample of comparative example.This is because Li8ZrO6It is all hexagonal crystal system with nickel-cobalt-manganese multi positive electrode,
In the case where being higher than 4.0V voltage, there are the deintercalations of lithium ion, therefore can significantly improve the discharge capacity and energy density of material.
As shown in figure 5, the nickel-cobalt-manganese multi positive electrode prepared in the present embodiment putting under 3.0~4.5V, 1C multiplying power
Electric specific capacity is 192.6mAh/g, improves 9.0mAh/g than 1 sample of comparative example.
As shown in fig. 6, the nickel-cobalt-manganese multi positive electrode prepared in the present embodiment, which is assembled into half-cell, carries out electrochemistry
It can test, specific discharge capacity reaches 175.9mAh/g after recycling under 3.0~4.5V, 1C multiplying power 100 weeks, relative to comparative example
1 improves 5.9mAh/g.
As shown in fig. 7, half circular diameter of the nickel-cobalt-manganese multi positive electrode medium-high frequency part prepared in the present embodiment is less than
The positive electrode prepared in comparative example 1, this illustrates Li8ZrO6Cladding significantly reduces the interface impedance of material.
Embodiment 2
Step 1: nickel sulfate, cobaltous sulfate, manganese sulfate are dissolved to obtain 1.5mol/L's according to the ratio of metal molar ratio 2:1:1
Aluminum sulfate and sodium hydroxide are obtained the aluminium of aluminium ion concentration 0.2mol/L according to molar ratio 1:10 mixed preparing by mixing salt solution
Solution；Sodium hydroxide is dissolved into the aqueous slkali that concentration is 5mol/L；Ammonia solvent is molten at the complexing agent that concentration is 2mol/L
Liquid.Mixing salt solution, aluminum solutions, aqueous slkali, enveloping agent solution together cocurrent are added in reaction kettle and reacted, process is protected
It is constant to hold speed of agitator 115rpm, control pH is 11.8~12.0, and temperature is 55 DEG C, when reaction completion, temperature, stirring is kept to turn
Speed is constant, continues to stir 20min, is then separated by solid-liquid separation nickel cobalt manganese aluminium hydroxide slurry obtained, washs, filter cake
It is sieved after 110 DEG C of drying 3h, obtains the spherical nickel cobalt manganese hydroxide materials of aluminium element Uniform Doped.
Step 2: the spherical nickel cobalt manganese hydroxide materials for the aluminium element Uniform Doped that step 1 obtains are mixed with lithium carbonate
It closes uniformly, wherein lithium carbonate is added according to molar ratio Li/ (Ni+Co+Mn+Al)=0.95.In air atmosphere, 900 DEG C of sintering
8h obtains anode material for lithium ion battery matrix Li by broken, screening0.95(Ni0.5Co0.25Mn0.25)0.995Al0.005O2。
Step 3: by ZrO2、TiO2, the obtained positive electrode matrix of lithium hydroxide and step 2 is according to 0.3:0.2::1.3:
100 the mass ratio of the material is put into high speed mixer simultaneously, is mixed 10min under the revolving speed of 1200rpm, is then placed in Muffle furnace
In be heat-treated, 500 DEG C of heating 10h, obtain average grain diameter D in air atmosphere50It is 6 μm, cladding composition of layer contains
Li2ZrO3、Li8ZrO6、Li4Ti5O12Nickel-cobalt-manganese multi material.
The nickel-cobalt-manganese multi positive electrode prepared in the present embodiment is assembled into half-cell and carries out electrochemical property test,
Specific discharge capacity under 3.0~4.5V, 0.1C multiplying power reaches 180.4mAh/g, energy density 811.8Wh/kg.Under 1C multiplying power
Capacity retention ratio after recycling 80 weeks reaches 94.6%.
Embodiment 3
Step 1: nickel sulfate, cobaltous sulfate, manganese sulfate are dissolved to obtain 2.5mol/L's according to the ratio of metal molar ratio 8:1:1
Sodium hydroxide is dissolved into the aqueous slkali that concentration is 6mol/L, the network for being 6mol/L at concentration by ammonia solvent by mixing salt solution
Mixture solution.Mixing salt solution, aqueous slkali, enveloping agent solution together cocurrent are added in reaction kettle and reacted, process is protected
It is constant to hold speed of agitator 125rpm, control pH is 11.9~12.1, and temperature is 65 DEG C, when reaction completion, temperature, stirring is kept to turn
Speed is constant, continues to stir 20min, is then separated by solid-liquid separation nickel cobalt manganese hydroxide slurry obtained, washs, filter cake 120
DEG C drying 4h after sieve, obtain spherical nickel cobalt manganese hydroxide materials.
Step 2: the spherical nickel cobalt manganese hydroxide materials that step 1 is obtained and Nano-sized Alumina Powder, nano-silica
Change titanium powder to mix according to the ratio of molar ratio (Ni+Co+Mn): Al: Ti=99:0.4:0.6.By above-mentioned mixture again with
Lithium hydroxide is uniformly mixed, and wherein lithium hydroxide is added according to molar ratio Li/ (Ni+Co+Mn+Al+Ti)=1.25.In oxygen gas
In atmosphere, 750 DEG C of sintering 16h obtain anode material for lithium ion battery matrix Li by broken, screening1.25
(Ni0.8Co0.1Mn0.1)0.99Al0.004Ti0.006O2。
Step 3: by ZrO2, the obtained positive electrode matrix of lithium hydroxide and step 2 according to 0.2:1.4:100 mole
Than simultaneously be put into high speed mixer, mix 15min under the revolving speed of 1000rpm, be then placed in Muffle furnace and be heat-treated,
The lower 700 DEG C of heating 1h of oxygen atmosphere, obtains average grain diameter D50Contain Li for 15 μm, clad8ZrO6、Li6Zr2O7Compound nickel
Cobalt-manganese multi material.
The compound nickel-cobalt-manganese multi positive electrode prepared in the present embodiment is assembled into half-cell and carries out electrochemical property test,
Its specific discharge capacity under 3.0~4.5V, 0.1C multiplying power reaches 220.3mAh/g, energy density 991.3Wh/kg.
Embodiment 4
Step 1 is consistent with 1 preparation step of comparative example.
Step 2: the spherical nickel cobalt manganese hydroxide materials that step 1 is obtained and nano oxidized hafnium powder, nano oxidized
Zirconium powder is mixed according to the ratio of molar ratio (Ni+Co+Mn): Hf:Zr=99:0.4:0.6.By above-mentioned mixture again with carbonic acid
It is uniformly mixed, wherein lithium hydroxide is added according to molar ratio Li/ (Ni+Co+Mn+Hf+Zr)=1.03.In oxygen atmosphere, 750
DEG C sintering 16h obtains anode material for lithium ion battery matrix Li by broken, screening1.03(Ni0.6Co0.2Mn0.2)0.99Hf0.004Zr0.006O2。
Step 3: by ZrO2, the obtained positive electrode matrix of lithium hydroxide and step 2 it is same according to the molar ratio of 1:3:100
When be put into dry ball mill mixing tank, ball milling mixing 4 hours under the revolving speed of 100rpm are then placed in Muffle furnace and carry out hot place
It manages, heats 10h at 750 DEG C in air atmosphere, obtain average grain diameter D50It is 13 μm, clad contains Li8ZrO6、Li6Zr2O7's
Nickel-cobalt-manganese multi material.
As shown in figure 3, except ternary material main phase is special in the nickel-cobalt-manganese multi positive electrode XRD spectrum prepared in the present embodiment
There is also Li outside sign peak8ZrO6、Li6Zr2O7、Li2ZrO3Characteristic peak, show there is Li on the surface of the material8ZrO6、Li6Zr2O7、
Li2ZrO3Etc. phases.
As shown in figure 4, the nickel-cobalt-manganese multi positive electrode prepared in the present embodiment, which is assembled into half-cell, carries out electrochemistry
It can test, the specific discharge capacity under 3.0~4.5V, 0.1C multiplying power is 204.2mAh/g, and energy density reaches 918.9Wh/
kg.One side Li8ZrO6Be higher than 4.0V voltage under there are the deintercalations of lithium ion, therefore can be improved material discharge capacity and
Energy density；Another aspect Li6Zr2O7、Li2ZrO3The interface resistance in battery charge and discharge process is significantly reduced as lithium ion conductor
It is anti-, the polarization of material is reduced, and then improve discharge capacity.
As shown in figure 5, the nickel-cobalt-manganese multi positive electrode prepared in the present embodiment putting under 3.0~4.5V, 1C multiplying power
Electric specific capacity is 187.8mAh/g, improves 4.2mAh/g than 1 sample of comparative example.
As shown in fig. 6, the nickel-cobalt-manganese multi positive electrode prepared in the present embodiment, which is assembled into half-cell, carries out electrochemistry
It can test, specific discharge capacity reaches 180.6mAh/g after recycling under 3.0~4.5V, 1C multiplying power 100 weeks, relative to comparative example
1 improves 10.8 mAh/g, and capacity retention ratio improves 3.7%.Higher heat treatment temperature can make material surface gradient occur
Doping, stabilizes the structure of material, and then improve its capacity retention ratio.
As shown in fig. 7, half circular diameter of the nickel-cobalt-manganese multi positive electrode medium-high frequency part prepared in the present embodiment is less than
The positive electrode prepared in comparative example 1, this illustrates Li8ZrO6、Li6Zr2O7、Li2ZrO3Cladding significantly reduces the interface of material
Impedance.
The surface residual lithium content of material carries out titration test by potentiometric titrimeter in above-mentioned comparative example.
The microscopic appearance of material passes through scanning electron microscopy measurement in above-described embodiment and comparative example.
The electrochemical AC impedance of material is measured by electrochemical workstation in above-described embodiment and comparative example.
Positive active material in above-described embodiment and comparative example has carried out electric property assessment to it by the following method.
The assembling of button cell:
Firstly, by the compound nickel-cobalt-manganese multi positive active material of non-aqueous electrolyte secondary battery, acetylene black and gathering inclined difluoro
Ethylene (PVDF) is mixed according to mass ratio 95%:2.5%:2.5%, coated on aluminium foil and drying and processing is carried out, uses 100Mpa
Pressure punch forming be diameter 12mm, thick 120 μm of anode pole piece, then anode pole piece is put into 120 in vacuum drying box
DEG C drying 12h.
Cathode is 17mm using diameter, with a thickness of the Li sheet metal of 1mm；The polyethylene porous that diaphragm uses with a thickness of 25 μm
Film；Electrolyte uses the LiPF of 1mol/L6, ethylene carbonate (EC) and diethyl carbonate (DEC) equivalent mixed liquor.
Anode pole piece, diaphragm, cathode pole piece and electrolyte are respectively less than to the Ar gas gloves of 5ppm in water content and oxygen content
2025 type button cells are assembled into case, using battery at this time as unactivated battery.
It is placed for 24 hours after production button cell, after open-circuit voltage is stablized, cut-off electricity is charged to using the current density of 20mA/g
4.3V is pressed, in 4.3V constant-voltage charge to cut-off current 0.024mA.Blanking voltage is then discharged to same current density
3.0V is repeated in a manner described once, using battery at this time as active cell.
The performance evaluation of button cell is as follows:
(1) high rate performance test: 25 DEG C of temperature, using active cell, in the voltage range of 3.0~4.5V, respectively with 0.1C,
The current density of 0.2C, 1C, 2C, 5C recycle the high rate performance of 1 investigation material.
(2) cycle performance is tested: 25 DEG C of temperature, using active cell, in the voltage zone of 3.0~4.4V, 3.0~4.5V
Between, the cycle performance of material is investigated under the current density of 1C.
(3) unactivated battery, within the scope of 0.1Hz~100kHz test frequency, 5mV AC impedance performance test: are used
Ac impedance measurement is carried out under amplitude.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by anyone skilled in the art,
It should be covered by the protection scope of the present invention.Therefore, protection scope of the present invention should be with the protection model of claims
Subject to enclosing.
Claims (10)
1. a kind of high-energy density polynary positive pole material, it is characterised in that: including matrix and be coated on answering for described matrix surface
Close oxide cladding layers；The chemical formula of described matrix is Li1+a[(Ni1-2x Co x Mn x )1-y M y ]1-zM′ z O2, wherein -0.5≤a≤
0.3, 0.05≤x≤ 0.3,0≤y≤ 0.01,0≤z≤ 0.01, the clad includes Li8ZrO6It is Li with chemical formula u M″ v O w
Composite oxides, wherein 0≤u≤ 8,1≤v≤ 5,2≤w≤ 12, M and M ' be La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y,
At least one of Zr, Si, W, Nb, Sm, V, Mg, B, Al element, M " are at least one of Zr, Ti, Al, Si, Mn, Sn, W member
Element；
High-energy density polynary positive pole material according to claim 1, it is characterised in that: the composite oxides clad
It is fine and close or un-densified；The amount of the substance of clad accounts for the 0.01~3% of matrix.
2. high-energy density polynary positive pole material according to claim 1, it is characterised in that: the high-energy density is polynary
The average grain diameter D of positive electrode50It is 5~20 μm.
3. high-energy density polynary positive pole material according to claim 1, it is characterised in that: the Li u M″ v O w For
LiAl5O8、LiAlO2、Li5AlO4、Li2SiO3、Li2Si2O5、Li4SiO4、Li2SnO3、Li2TiO3、Li4TiO4、Li4Ti5O12、
Li2ZrO3、Li6Zr2O7、Li8ZrO6、Li4ZrO4At least one of.
4. a kind of preparation method of high-energy density polynary positive pole material, it is characterised in that the following steps are included:
(1) salt solution of nickel, cobalt, manganese and doped chemical is obtained into the mixing salt solution of 1~3mol/L；By sodium hydroxide
It is dissolved into the aqueous slkali that concentration is 4~10mol/L；The enveloping agent solution for being 2~10mol/L at concentration by ammonia solvent.
It reacts 5. mixing salt solution, aqueous slkali, enveloping agent solution together cocurrent are added in reaction kettle, keeps in the process
Stirring, while pH value in reaction and reaction temperature are controlled, precursor pulp obtained is by separation of solid and liquid, washing, drying, screening
Afterwards, spherical nickel cobalt manganese hydroxide (Ni is obtained1-2x Co x Mn x )1-y M y (OH)2；
(2) (the Ni for obtaining step (1)1-2x Co x Mn x )1-y M y (OH)2Be uniformly mixed with the oxide of lithium salts, M ', in air or
In oxygen atmosphere, 4~20h is calcined at 600~1000 DEG C, by broken, screening, obtains anode material for lithium ion battery matrix
Li1+a[(Ni1-2x Co x Mn x )1-y M y ]1-zM′ z O2；
(3) by ZrO2, the oxide of M ", lithium salts and the positive electrode matrix carry out mechanical mixture, mixture is then put into horse
Not in furnace, it is heat-treated 0.5~12h in 450~800 DEG C of temperature ranges, is made by Li8ZrO6And lithium ion conductor Li u M″ v O w It is multiple
Close the polynary positive pole material of oxide cladding；
- 0.5≤a≤1.3,0.05≤x≤ 0.3,0≤y≤ 0.01,0≤z≤ 0.01,0≤u≤ 8,1≤v≤ 5,2≤w
≤ 12, M and M ' are that at least one of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, Si, W, Nb, Sm, V, Mg, B, Al are first
Element, M " are at least one of Zr, Ti, Al, Si, Mn, Sn, W element.
6. the preparation method of high-energy density polynary positive pole material according to claim 5, it is characterised in that: the M's '
Oxide, M " oxide particle average grain diameter D50For 1~50nm, specific surface area is greater than 10m2/g。
7. the preparation method of high-energy density polynary positive pole material according to claim 5, it is characterised in that: the M's '
Oxide, M " oxide be HfO2、TiO2、Y2O3、ZrO2、SiO2、W2O3、Nb2O5、Sm2O3、V2O5、MgO、Al2O3In extremely
Few one kind.
8. the preparation method of high-energy density polynary positive pole material according to claim 5, it is characterised in that: the reaction
PH range is 10~13, and temperature is 50~70 DEG C.
9. the preparation method of high-energy density polynary positive pole material according to claim 5, it is characterised in that: step (2)
The additional amount of the lithium salts is molar ratio=0.95~1.3 of Li/ (Ni+Co+Mn+M+M ').
10. the preparation method of high-energy density polynary positive pole material according to claim 5, it is characterised in that: step (3)
The heat-treating atmosphere is air or oxygen, and heat treatment temperature is 500~750 DEG C, and the time is 4~10h.
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