CN109461927A - A kind of compound nickel-cobalt-manganese multi positive electrode of high magnification and preparation method thereof - Google Patents
A kind of compound nickel-cobalt-manganese multi positive electrode of high magnification and preparation method thereof Download PDFInfo
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- CN109461927A CN109461927A CN201711393239.XA CN201711393239A CN109461927A CN 109461927 A CN109461927 A CN 109461927A CN 201711393239 A CN201711393239 A CN 201711393239A CN 109461927 A CN109461927 A CN 109461927A
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- manganese
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- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000011159 matrix material Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000011572 manganese Substances 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 12
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 229910052796 boron Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 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 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000012266 salt solution Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 3
- 238000009938 salting Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 239000011248 coating agent Substances 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
- 238000004090 dissolution Methods 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims description 2
- 230000002687 intercalation Effects 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000000320 mechanical mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000001241 arc-discharge method Methods 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 239000002245 particle Substances 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000010406 cathode material 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
- 239000012065 filter cake Substances 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 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
- 239000002002 slurry Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- WFLOTYSKFUPZQB-UHFFFAOYSA-N 1,2-difluoroethene Chemical group FC=CF WFLOTYSKFUPZQB-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 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
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000010291 electrical method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 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
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of compound nickel-cobalt-manganese multi positive electrode of high magnification and preparation method thereof, and it is Li (Ni that the positive electrode, which is by chemical formula,1‑2x Co x Mn x )1‑y M y O2Matrix and be coated on the graphene composition on described matrix surface, wherein M is at least one of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, W, Nb, Sm, V, Mg, B, Al element, and graphene coated amount is the 0.01~3% of matrix weight.Positive electrode of the invention has good high rate performance 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 compound nickel-cobalt-manganese multi positive electrode of high magnification and preparation methods, belong to lithium ion battery skill
Art field.
Background technique
Along with the fast development in the fields such as new-energy automobile, unmanned plane, develop high rate capability, high-energy density it is dynamic
Power type lithium ion battery becomes the urgent need of Vehicles Collected from Market.Because of its high voltage, the characteristics of height ratio capacity, is considered multicomponent material
It is one of most promising anode material of lithium battery.But since multicomponent material conductivity itself is low, between aggregate inevitably
Interface impedance hinders its application under the conditions of high magnification.Graphene has good conductivity and lithium ionic mobility, as
Clad can improve the above problem to a certain degree.However, graphene is deposited as clad in previous research and patent report
Active force is weak between oxide particle, easy to fall off in cyclic process, causes high rate performance to be promoted unobvious, cyclical stability is not
The problems such as good.
Chinese patent CN104157854A discloses a kind of preparation of graphene composite lithium ion cell tertiary cathode material
Method is different from dodecyl phenol polyethenoxy ether and ethyl alcohol etc. by graphene film after preparing tertiary cathode material in patent
The solution allocation of ingredient is finally sintered at dispersion liquid by ternary material with dispersion liquid high-speed stirred and drying under an argon atmosphere
Obtain finished product.This preparation method process is complicated, needs to introduce a large amount of organic solvents, and have special want to heat-treating atmosphere
It asks, higher cost；Positive electrode obtained performance improvement under 1C and 2C multiplying power is unobvious.
Chinese patent CN106935830A discloses a kind of lithium ion battery composite cathode material and preparation method thereof, patent
It is middle that three-dimensional grapheme is prepared using chemical reaction method, graphite is dilute under nitrogen protection with ternary material in high energy ball mill
Interior carry out ball milling.This method preparation condition is harsh, equipment and atmosphere are required it is harsher, and the dosage of graphene be up to 4%~
10%, preparation and higher operating costs, the cell active materials accounting of assembling are lower than 80%, with industrial application requirement gap compared with
Greatly.
Summary of the invention
The present invention provides a kind of compound nickel-cobalt-manganese multi positive electrode of high magnification and preparation method, provided by the invention compound
Nickel-cobalt-manganese multi material has excellent high rate performance and good cyclical stability under the premise of keeping height ratio capacity.
To achieve the goals above, the invention adopts the following technical scheme:
The compound nickel-cobalt-manganese multi positive electrode of high magnification provided by the invention, including matrix and the stone for being coated on described matrix surface
Black alkene clad；The chemical formula of described matrix is Li (Ni1-2x Co x Mn x )1-y M y O2, wherein 0.05≤x≤0.3,0≤y≤0.01,
M is at least one of La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, W, Nb, Sm, V, Mg, B, Al element；
The graphene coated layer is without containing the functional groups such as hydroxyl, carboxyl, average grain diameter D50It is 0.1~25 μm；The weight of clad
Amount accounts for the 0.01~3% of matrix weight, and coating thickness is 0.3~500nm.
The average grain diameter D of the compound nickel-cobalt-manganese multi positive electrode of high magnification50It is 5~20 μm.
The present invention also provides the preparation methods of the compound nickel-cobalt-manganese multi positive electrode of above-mentioned high magnification, including following step
It is rapid:
(1) by the salting liquid of nickel, cobalt, manganese and doped chemical according to chemical formula Li (Ni1-2x Co x Mn x )1-y M y O2Middle metal molar
The mixing salt solution of 1~3mol/L is obtained than dissolution；Sodium hydroxide is dissolved into the aqueous slkali that concentration is 4~10mol/L；By ammonia
Water is dissolved into the enveloping agent solution that concentration is 2~10mol/L.Mixing salt solution, aqueous slkali, enveloping agent solution together cocurrent are added
Enter and reacted into reaction kettle, is kept stirring in the process, while controlling ph value of reaction and reaction temperature, forerunner's somaplasm obtained
Material obtains spherical nickel cobalt manganese hydroxide (Ni after separation of solid and liquid, washing, drying, screening1-2x 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)2It is uniformly mixed with lithium salts, in air or oxygen atmosphere,
4~20h is calcined at 600~1000 DEG C, by broken, screening, obtains anode material for lithium ion battery matrix Li (Ni1- 2x Co x Mn x )1-y M y O2；
(3) graphene and the positive electrode matrix are subjected to mechanical mixture, then mixture are put into Muffle furnace, 100
It is heat-treated 0.5~4h in~500 DEG C of temperature ranges, the compound nickel-cobalt-manganese multi positive electrode of graphene coated is made.
Preferably, the graphene is put by graphite mechanical stripping method, graphite intercalation method, chemical vapour deposition technique, electric arc
Any one method in electrical method is made.
Preferably, the graphene average grain diameter D50It is 10~30 μm, specific surface area is greater than 20m2/ g, graphene thickness≤
5nm, 1~10 layer of graphene number of plies average out to.
Preferably, step (1) the reaction pH range is 10~13, and temperature is 50~70 DEG C.
Preferably, step (2) lithium salts is one or both of lithium carbonate, lithium hydroxide.
Preferably, the additional amount of step (2) described lithium salts be Li/(Ni+Co+Mn) molar ratio=0.95~1.1.
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 100~350 DEG C, the time
For 0.5~4h.It is further preferred that heat treatment temperature is 150~200 DEG C.
Present invention has the advantage that
(1) the compound nickel-cobalt-manganese multi positive electrode of high magnification that the present invention obtains, is effectively reduced just by the cladding of graphene
The interface impedance on pole material granule surface, hence it is evident that improve the high rate performance of positive electrode.
(2) the compound nickel-cobalt-manganese multi positive electrode of high magnification that the present invention obtains improves graphene after Overheating Treatment
Clad reduces polarization of the positive electrode in charge and discharge process, improves product with the binding force of positive electrode particle
Cyclical stability.
(3) preparation method simple process of the present invention, pollution-free.Graphene incorporation way is simple, and dosage is few, heat-treating atmosphere
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 the compound nickel-cobalt-manganese multi positive electrode of high magnification prepared by embodiment 1.
Specific discharge capacity figure of the half-cell that Fig. 3 is comparative example 1, prepared by embodiment 1 under different multiplying.
Fig. 4 is the electrochemical AC impedance figure that half-cell prepared by comparative example 1, comparative example 2 and embodiment 1 measures.
Specific discharge capacity cycle performance figure of the Fig. 5 for comparative example 1 and the half-cell of the preparation of embodiment 1 at 1C.
Charging and discharging curve of the Fig. 6 for comparative example 1 and the half-cell of the preparation of embodiment 1 at 1C.
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)=1.05.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 LiNi0.6Co0.2Mn0.2O2。
As shown in Figure 1, the nickel-cobalt-manganese multi positive electrode matrix microscopic appearance prepared in this comparative example is near-spherical particle.
The nickel-cobalt-manganese multi positive electrode matrix prepared in this comparative example is assembled into half-cell and carries out electrochemical property test,
Specific discharge capacity under its 2C multiplying power reaches 152mAh/g；Specific discharge capacity under its 4C multiplying power reaches 124mAh/g.
Comparative example 2
Step 1 and step 2 are consistent with 1 preparation step of comparative example.
Step 3: positive electrode matrix that graphene and step 2 obtain according to the mass ratio of 0.5:100 while being put into
Dry ball mill mixing tank, ball milling mixing 4 hours under the revolving speed of 100rpm obtain compound nickel-cobalt-manganese multi positive electrode.
As shown in figure 4, the compound nickel-cobalt-manganese multi positive electrode surface membrane impedance prepared in this comparative example is significantly less than pair
The positive electrode surface membrane impedance prepared in ratio, this illustrate the cladding of graphene effectively improve active material particle surface and
Electron transfer rate between particle, therefore have for the high rate capability of material and be obviously improved effect.
The compound nickel-cobalt-manganese multi positive electrode prepared in this comparative example is assembled into half-cell and carries out electrochemical property test,
Specific discharge capacity under its 2C multiplying power reaches 158mAh/g, improves 6 mAh/g relative to comparative example 1；Putting under its 4C multiplying power
Electric specific capacity reaches 140mAh/g, improves 13% relative to comparative example 1.
Embodiment 1
Step 1 and step 2 are consistent with 1 preparation step of comparative example.
Step 3: positive electrode matrix that graphene and step 2 obtain according to the mass ratio of 0.5:100 while being put into
Dry ball mill mixing tank, ball milling mixing 4 hours, are then placed in Muffle furnace and are heat-treated under the revolving speed of 100rpm, empty
2h is heated at 200 DEG C in gas atmosphere, obtains average grain diameter D50For the compound nickel-cobalt-manganese multi material of 13 μm of graphene coateds.
As shown in Fig. 2, the graphene film reunited is not found between the positive electrode second particle prepared in the present embodiment, it is secondary
There are coarse coatings on particle agglomeration surface, may infer that graphene coated on second particle aggregate surface.
As shown in figure 3, the compound nickel-cobalt-manganese multi positive electrode prepared in the present embodiment, which is assembled into half-cell, carries out electrification
Performance test is learned, the specific discharge capacity under 2C multiplying power reaches 160mAh/g, improves 8 mAh/g relative to comparative example 1；Its 4C
Specific discharge capacity under multiplying power reaches 143mAh/g, improves 15% relative to comparative example 1.
As shown in figure 4, the compound nickel-cobalt-manganese multi positive electrode surface membrane impedance prepared in the present embodiment is less than comparative example 2
The positive electrode surface membrane impedance of middle preparation, this illustrates that heat treatment process effectively increases the binding force with oxide particle, into
One step improves the electron transfer rate between active material particle surface and particle, thus for the high rate capability of material and
Specific discharge capacity, which has, is obviously improved effect.
As shown in figure 5, the compound nickel-cobalt-manganese multi positive electrode prepared in the present embodiment, which is assembled into half-cell, carries out electrification
Performance test is learned, specific discharge capacity reaches 178mAh/g after recycling 100 weeks under 1C multiplying power, improves 20 relative to comparative example 1
MAh/g, capacity retention ratio improve 7.6%.
As shown in fig. 6, the compound nickel-cobalt-manganese multi positive electrode prepared in the present embodiment, which is assembled into half-cell, carries out electrification
Performance test is learned, the charging and discharging curve under 1C multiplying power shows that the cladding of graphene significantly weakens material in charge and discharge process
Polarity effect.Therefore, the graphene of cladding, which has the specific discharge capacity of material, is obviously improved effect.
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)=1.03.In air atmosphere, 900 DEG C of sintering 8h, warp
Broken, screening is crossed, anode material for lithium ion battery matrix Li (Ni is obtained0.5Co0.25Mn0.25)0.995Al0.005O2。
Step 3: positive electrode matrix that graphene and step 1 obtain according to the mass ratio of 0.2:100 while being put into
In high speed mixer, 10min is mixed under the revolving speed of 1200rpm, is then placed in Muffle furnace and is heat-treated, in air atmosphere
Lower 180 DEG C of heating 4h, obtains average grain diameter D50For the compound nickel-cobalt-manganese multi material of 6 μm of graphene coateds.
The compound 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 its 2C multiplying power reaches 156mAh/g, and the specific discharge capacity under 4C multiplying power reaches 140mAh/g.
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 hydrogen-oxygen
Change lithium to be uniformly mixed, wherein lithium hydroxide is added according to molar ratio Li/(Ni+Co+Mn)=1.05.In oxygen atmosphere, 750 DEG C
It is sintered 16h, by broken, screening, obtains anode material for lithium ion battery matrix Li (Ni0.8Co0.1Mn0.1)0.99Al0.004Ti0.006O2。
Step 3: positive electrode matrix that graphene and step 2 obtain according to the mass ratio of 3:100 while being put into height
In fast batch mixer, 15min is mixed under the revolving speed of 1000rpm, is then placed in Muffle furnace and is heat-treated, under oxygen atmosphere
150 DEG C of heating 1h, obtain average grain diameter D50For the compound nickel-cobalt-manganese multi material of 15 μm of graphene coateds.
The compound 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 its 2C multiplying power reaches 180mAh/g, and the specific discharge capacity under 4C multiplying power reaches 156mAh/g.
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 3.0~4.3V, respectively with 0.1C,
The current density of 0.2C, 1C, 2C, 4C 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 range of 3.0~4.5V, with 1C's
Current density recycles the cycle performance of 100 investigation materials.
(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, and it is any
Within the technical scope of the present disclosure, any changes or substitutions that can be easily thought of by those familiar with the art, all answers
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be with the protection scope of claims
It is quasi-.
Claims (10)
1. a kind of compound nickel-cobalt-manganese multi positive electrode of high magnification, it is characterised in that: including matrix and be coated on described matrix table
The graphene coated layer in face；The chemical formula of described matrix is Li (Ni1-2x Co x Mn x )1-y M y O2, wherein 0.05≤x≤0.3,0≤y
At least one of≤0.01, M La, Cr, Mo, Ca, Fe, Hf, Ti, Zn, Y, Zr, W, Nb, Sm, V, Mg, B, Al element；
The graphene coated layer is without containing the functional groups such as hydroxyl, carboxyl, average grain diameter D50It is 0.1~25 μm；The weight of clad
Amount accounts for the 0.01~3% of matrix weight, and coating thickness is 0.3~500nm.
2. the compound nickel-cobalt-manganese multi positive electrode of high magnification according to claim 1, it is characterised in that the multielement cathode
The average grain diameter D of material50It is 5~20 μm.
3. a kind of preparation method of the compound nickel-cobalt-manganese multi positive electrode of high magnification, it is characterised in that the following steps are included:
(1) by the salting liquid of nickel, cobalt, manganese and doped chemical according to chemical formula Li (Ni1-2x Co x Mn x )1-y M y O2Middle metal molar
The mixing salt solution of 1~3mol/L is obtained than dissolution；Sodium hydroxide is dissolved into the aqueous slkali that concentration is 4~10mol/L；By ammonia
Water is dissolved into the enveloping agent solution that concentration is 2~10mol/L；Mixing salt solution, aqueous slkali, enveloping agent solution together cocurrent are added
Enter and reacted into reaction kettle, is kept stirring in the process, while controlling ph value of reaction and reaction temperature, forerunner's somaplasm obtained
Material obtains spherical nickel cobalt manganese hydroxide (Ni after separation of solid and liquid, washing, drying, screening1-2x 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)2It is uniformly mixed with lithium salts, in air or oxygen atmosphere,
4~20h is calcined at 600~1000 DEG C, by broken, screening, obtains anode material for lithium ion battery matrix Li (Ni1- 2x Co x Mn x )1-y M y O2；
(3) graphene and the positive electrode matrix are subjected to mechanical mixture, then mixture are put into Muffle furnace, 100
It is heat-treated 0.5~4h in~500 DEG C of temperature ranges, the compound nickel-cobalt-manganese multi positive electrode of graphene coated is made.
4. the preparation method of the compound nickel-cobalt-manganese multi positive electrode of high magnification according to claim 3, it is characterised in that institute
It states graphene and passes through any one side in graphite mechanical stripping method, graphite intercalation method, chemical vapour deposition technique, arc discharge method
Method is made.
5. the preparation method of the compound nickel-cobalt-manganese multi positive electrode of high magnification according to claim 3, it is characterised in that stone
Black alkene average grain diameter D50It is 10~30 μm, specific surface area is greater than 20m2/ g, graphene thickness≤5nm, graphene number of plies average out to 1
~10 layers.
6. the preparation method of the compound nickel-cobalt-manganese multi positive electrode of high magnification according to claim 3, it is characterised in that step
Suddenly (1) described pH value in reaction is 10~13, and temperature is 50~70 DEG C.
7. the preparation method of the compound nickel-cobalt-manganese multi positive electrode of high magnification according to claim 3, it is characterised in that step
Suddenly (2) described lithium salts is one or both of lithium carbonate, lithium hydroxide, additional amount the rubbing for Li/(Ni+Co+Mn) of lithium salts
That ratio=0.95~1.1.
8. the preparation method of the compound nickel-cobalt-manganese multi positive electrode of high magnification according to claim 3, it is characterised in that step
Suddenly (3) described mixed equipment is one of ball grinder, Ball-stirring mill, colter mixer, V-type batch mixer, high-speed mixer.
9. the preparation method of the compound nickel-cobalt-manganese multi positive electrode of high magnification according to claim 3, it is characterised in that step
Suddenly (3) described heat-treating atmosphere is air or oxygen, and heat treatment temperature is 100~350 DEG C, and the time is 0.5~4h.
10. the preparation method of the compound nickel-cobalt-manganese multi positive electrode of high magnification according to claim 9, it is characterised in that institute
Stating heat treatment temperature is 150~200 DEG C.
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Application publication date: 20190312 |