CN105762345B - A kind of composite positive pole, preparation method and lithium ion battery - Google Patents
A kind of composite positive pole, preparation method and lithium ion battery Download PDFInfo
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- CN105762345B CN105762345B CN201610280950.3A CN201610280950A CN105762345B CN 105762345 B CN105762345 B CN 105762345B CN 201610280950 A CN201610280950 A CN 201610280950A CN 105762345 B CN105762345 B CN 105762345B
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 138
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 136
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 32
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 27
- 229910052744 lithium Inorganic materials 0.000 claims description 27
- 239000012298 atmosphere Substances 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000005416 organic matter Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 13
- 238000010008 shearing Methods 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000889 atomisation Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 230000002572 peristaltic effect Effects 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- IEQAICDLOKRSRL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-dodecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO IEQAICDLOKRSRL-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical group CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000006258 conductive agent Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 238000010438 heat treatment Methods 0.000 description 24
- 239000011259 mixed solution Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000007921 spray Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- -1 graphite alkene Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 5
- 238000005253 cladding Methods 0.000 description 5
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 230000002045 lasting effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 150000004040 pyrrolidinones Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000002345 surface coating layer Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- NXPZICSHDHGMGT-UHFFFAOYSA-N [Co].[Mn].[Li] Chemical compound [Co].[Mn].[Li] NXPZICSHDHGMGT-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical class [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
-
- 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
Abstract
The present invention provides a kind of composite positive pole, preparation method and lithium ion batteries, the composite positive pole includes positive electrode and the clad for being coated on positive electrode surface, clad is agraphitic carbon-graphene layer, and agraphitic carbon is evenly distributed on the surface of graphene.The composite positive pole is made by the way that positive electrode is sprayed into progress heat-treating methods in the vertical calcining furnace full of protective gas with the mixed liquor of graphene dispersing solution using sprayer.The composite positive pole can be improved the uniformity of graphene coated positive electrode；Solves the problems, such as restricted problem of the graphene with the anisotropy of the reaction of positive electrode oxide and graphene to graphene conductive under high temperature；The easy stack-up issue of graphene is effectively improved, the electric conductivity of positive electrode is improved；The specific capacity of battery can also be improved by reducing the additive amount of conductive agent in anode pole piece formula；Can continuous production, greatly improve production efficiency, can be with large-scale serial production.
Description
Technical field
The invention belongs to the preparation technical field of material, it is related to a kind of composite positive pole, preparation method and lithium ion
Battery.
Background technique
In recent years, under the support of national policy, electric car industry is rapidly developed.High-energy-density, longevity
Life, the novel anode material of low cost and its battery are particularly important.Lithium ion battery high, specific energy with its operating voltage
Greatly, it has extended cycle life, pollute the advantages that small and show one's talent in numerous electrochmical power sources.
But the positive electrode being commercialized at present cannot be considered in terms of circulation, specific energy, voltage and security problems.Some materials are such as
There is also cyclical stabilities for lithium-rich manganese base material, nickel cobalt aluminium and nickel cobalt manganese series, especially stable circulation under the high temperature conditions
The defects of property is not good enough, limits the service life of the material.This is because the positive electrode in battery can directly connect with electrolyte
The problems such as concurrent biochemical reaction of touching, causes positive electrode surface texture to collapse, and the embedding de- performance of lithium ion substantially reduces.Therefore,
Best method in order to solve the above problem is to carry out the processing of surface cladding, to reduce directly connecing for positive electrode and electrolyte
Touching.The coating of commodity positive electrode includes carbon coating, metal oxide (such as ZnO, Al at present2O3Deng), phosphate (such as AlPO4
Deng) and anion (such as F-Deng).Phosphate non-electroactive substance, phosphatic cladding increase between material and electrolyte
Resistance hinders the insertion and abjection of lithium ion.Though the above covering material has obstructed the direct of nickel ion doped material and electrolyte
But there is the problems such as reducing specific capacity, corrosion material surface and increasing resistance in contact.
Graphene is a kind of tightly packed two-dimensional sheet nano-carbon material at monolayer honeycomb shape structure of carbon atom, have compared with
High theoretical specific surface area (2630m2/ g), excellent calorifics, mechanics, optics, electric property and broad application prospect.Graphite
The resistivity of alkene only has about 10-6Ω cm, it is lower than copper or silver, it is the smallest material of world resistivity.But only graphene
The resistivity of two-dimensional surface xy axial direction is 10-6Ω cm, and the resistivity in the z-axis vertical direction of two-dimensional surface is higher.Therefore
The resistivity of actual graphene powder is up to 10-4Ω·cm.This anisotropy of graphene significantly limits it each
The utilization in field.Especially in field of batteries, when using graphene as conductive agent, xy it is axial to lead electronic capability obviously strong
In z-axis mode, so that improvement effect very little of the graphene conductive additive relative to carbon nanotube.Moreover, graphene film
Interlayer has very strong interaction force, and graphene sheet layer is caused easily to stack, and forms interlamellar spacing and only has 0.334 nanometer more
Layer graphene-structured.This characteristic easily stacked reduces the specific surface area of graphene, limits the efficient utilization at its interface, unfavorable
In the performance of the electric conductivity of graphene.
Existing graphene coated scheme is simply by the mode of stirring or ball milling by positive electrode and graphene
Mix and then carries out high-temperature process again.Not in view of preparation process is to the easy stack properties of graphene, the packet of graphene
Covering uniformity and high-temperature process influences the performance of positive electrode.
Many defects are still had using graphene and positive electrode composite preparation process disclosed in existing:
The preparation method that 104538620 A of CN discloses a kind of fluorinated graphene cladding manganese cobalt lithium anode material will be ultrasonic
Scattered fluorinated graphene is stirred with active material, then is centrifuged heat treatment and is obtained the product for being coated with graphene.The skill
There are greatest drawbacks to be for art: since graphene specific surface is very big, easily group stacks, is poly-, simple stirring and centrifugation heat treatment
Process can not make the surface for being covered on positive electrode of graphene uniform.
104393282 A of CN discloses a kind of preparation method of the polynary positive pole material of graphene coated, passes through planet ball
The mode admixed graphite alkene and positive electrode of mill, then pass through the heat treatment of 750-800 DEG C of Isothermal sinter 10-15h high pure nitrogen, it obtains
To the product for being finally coated with graphene.There are greatest drawbacks to be for the technology: 1, the mode of planetary ball mill can not uniformly will just
Pole material and graphite mix.Meanwhile the too long meeting of heat treatment time is so that graphene seriously stacks, reunites.2, it is heat-treated
High pure nitrogen environment avoid the problem of oxidation of graphene well.But the anode of oxygen atmosphere sintering synthesis is needed originally
Material, 750-800 DEG C of Isothermal sinter 10-15h will seriously affect the performance of material itself under high pure nitrogen environment.Exist simultaneously
Under the hot environment of 10-15h, graphene most probably reacts with the positive electrode of oxide properties and influences end properties.
CN 102623708A discloses a kind of preparation method of the nickel ion doped material of graphene coated, will be mixed with certain
300-600 DEG C of precalcining 2-5h of presoma of ratio graphene, then calcines 6-10h under the conditions of 700-900 DEG C.The technology is deposited
Be in greatest drawback: the sintering atmosphere of nickel ion doped material needs oxygen, and 700-900 DEG C of sintering 6-10h can make big portion
The graphene divided is oxidized.
CN 102544491A discloses a kind of lithium iron phosphate positive material and preparation method thereof of doped graphene.It is described
Method includes: that soluble lithium compounds, phosphate and ferrous salt are mixed in dispersing agent and obtain dispersion liquid a by (1)；(2) by stone
Black alkene derived material aoxidizes to obtain graphene oxide derived material, and ultrasonic disperse obtains dispersion liquid b；(3) by dispersion liquid a and dispersion
Liquid b mixing, stirs evenly, through spraying heat treatment, calcining, obtains the lithium iron phosphate positive material of doped graphene.But the party
Method does not simultaneously solve the problem of graphene easily stacks, reunites.
Summary of the invention
In view of the problems of the existing technology, the purpose of the present invention is to provide a kind of composite positive poles, its preparation side
Method and lithium ion battery, agraphitic carbon-graphene layer is high to the being evenly coated property of positive electrode in the composite positive pole, keeps away
Graphene is exempted from the reaction of positive electrode oxide, and has solved the anisotropy of graphene and stack to reunite and graphene is led
Electrical restricted problem.
To achieve this purpose, the present invention adopts the following technical scheme:
One of the objects of the present invention is to provide a kind of composite positive pole, the composite positive pole includes positive electrode
And it is coated on the clad on the positive electrode surface, the clad is amorphous carbon-graphene layer, the amorphous carbon point
Cloth is on the surface of graphene.
Graphene forms conductive network by being distributed in the amorphous carbon on its surface；Meanwhile amorphous carbon can also be used as stone
Interlayer between black alkene prevents the stacking between graphene from reuniting.
In the clad mass ratio of amorphous carbon and graphene be (1~5): 1, as mass ratio be 1.5:1,2.5:1,
3:1 or 4.5:1 etc..
The mass ratio of clad and positive electrode is (0.01~0.2) in the composite positive pole: 1, as mass ratio is
0.02:1,0.05:1,0.08:1,0.1:1,0.15:1 or 0.18:1 etc..
Preferably, the positive electrode be cobalt acid lithium (LCO), nickel cobalt lithium aluminate (NCA), nickle cobalt lithium manganate (NCM), nickel acid
In lithium (LNO), LiMn2O4 (LMO) or lithium-rich manganese base material any one or at least two combination.It is typical but non-limiting
Combination are as follows: LCO and NCA, NCA and NCM, NCM, LNO and LMO, NCA, NCM and LNO.
Preferably, the graphene is the graphene being prepared by the method for preparing graphene by using supercritical fluid.Institute
Graphene is stated preferably by graphene made from method disclosed in 102115078 A of CN.
The second object of the present invention is to provide a kind of preparation method of composite positive pole, and the method includes walking as follows
It is rapid:
(1) it disperses organic matter dispersing agent in solvent, obtains dispersant solution；
(2) it disperses graphene in dispersant solution, obtains graphene dispersing solution；
(3) positive electrode is mixed with graphene dispersing solution made from step (2), obtains mixed liquor；
(4) mixed liquor is atomized, is heat-treated in protective atmosphere, obtain the composite positive pole.
The concentration of organic matter dispersing agent is 20~100g/L in dispersant solution described in step (1), such as 25g/L, 40g/
L, 60g/L or 80g/L etc..The concentration of dispersant solution is mainly adjusted according to the ratio and graphene concentration of itself and graphene
Control.
The ratio of organic matter dispersing agent will affect graphene dispersion effect, and heat treatment temperature is also required to according to dispersing agent
Ratio is regulated and controled.Because the molecular weight of organic matter dispersing agent is bigger, it is more difficult to be carbonized, needs higher heat treatment temperature.It is preferred that
Ground, organic matter dispersing agent described in step (1) are gamma-butyrolacton, propene carbonate, ethylene carbonate, ethyl acetate, polyethylene
In pyrrolidones, Brij-35 or polyvinyl alcohol any one or at least two combination.Typical but non-limit
The combination of property processed are as follows: gamma-butyrolacton and propene carbonate, ethylene carbonate and ethyl acetate, polyvinylpyrrolidone and 12
Alkyl polyglycol ether, polyvinylpyrrolidone and polyvinyl alcohol, Brij-35 and polyvinyl alcohol, polyethylene pyrrole
Pyrrolidone, Brij-35 and polyvinyl alcohol, gamma-butyrolacton, propene carbonate, ethylene carbonate and acetic acid second
Ester, gamma-butyrolacton, ethylene carbonate, polyvinylpyrrolidone and Brij-35.
Preferably, solvent described in step (1) is N-Methyl pyrrolidone, deionized water, dehydrated alcohol, propyl alcohol or isopropyl
In alcohol any one or at least two combination.Typical but non-limiting combination can are as follows: N-Methyl pyrrolidone and go from
Sub- water, dehydrated alcohol and isopropanol, N-Methyl pyrrolidone, deionized water and dehydrated alcohol, deionized water, propyl alcohol, anhydrous second
Alcohol and isopropanol, N-Methyl pyrrolidone, deionized water, dehydrated alcohol and isopropanol.Solvent in dispersion liquid can be subsequent
It volatilizees, the performance of final products will not be impacted in heat treatment process.
In graphene dispersing solution described in step (2) concentration of graphene be 4~20g/L, as 5g/L, 8g/L, 10g/L,
13g/L, 15g/L, 17g/L or 18g/L etc..Since graphene specific surface area is very big, easily reunite when dispersing in a fluid, and
Graphene film interlayer has very strong interaction force, and graphene sheet layer is caused easily to stack.Even if it joined dispersing agent, but
The concentration of graphene is also unsuitable excessively high.Excessive concentration can then aggravate the reunion and stacking of graphene.
Preferably, graphene dispersing solution described in step (2) is prepared via a method which to obtain: graphene is added to point
In dispersant solution, dispersed using shearing dispersal device.It, can not using common dispersing apparatus since graphene is nanoscale microplate
Disperse the graphene reunited, graphene could only be broken up by high-speed shearing machine.
Preferably, it is described shearing dispersal device revolving speed be 1000~10000rpm, as 1500rpm, 2000rpm,
5000rpm, 8000rpm or 9000rpm etc..
Preferably, the graphene is prepared by the method for preparing graphene by using supercritical fluid.The graphene is excellent
It is selected as graphene made from the method as disclosed in CN 102115078A.
Positive electrode concentration in mixed liquor described in step (3) is 100~1200g/L, as 150g/L, 200g/L,
500g/L, 600g/L, 700g/L, 800g/L, 900g/L or 1100g/L etc..The concentration of positive electrode mainly influences sprayer
Spray effect, excessive concentration can make spraying granule excessive, cause to calcine in heat treatment process insufficient；Meanwhile high concentration
Mixed liquor is easy plug nozzle when passing through spray nozzle.The concentration of the positive electrode can also be lower.
Preferably, it is cobalt acid lithium (LCO), nickel cobalt lithium aluminate that positive electrode described in step (3), which is the positive electrode,
(NCA), any one in nickle cobalt lithium manganate (NCM), lithium nickelate (LNO), LiMn2O4 (LMO) or lithium-rich manganese base material or at least
Two kinds of combination.Typical but non-limiting combination are as follows: LCO and NCA, NCA and NCM, NCM, LNO and LMO, NCA, NCM with
LNO。
Preferably, described be blended under lasting stirring condition of step (3) carries out.
Heat treatment temperature described in step (4) is 400-1000 DEG C, such as 500 DEG C, 600 DEG C, 800 DEG C or 900 DEG C.
Preferably, heat treatment time described in step (4) be 0.05-3min, as 0.05min, 0.2min, 0.5min,
0.8min, 1min, 2min or 2.5min etc..
Heat treatment time is too short or heat treatment temperature is too low, can all make the dispersing agent on surface be carbonized insufficient, finally
Seriously affect the electric conductivity of surface coating layer；It handles overlong time or heat treatment temperature is excessively high, it is possible to cause positive material
Material is reacted with clad, influences material property.
Preferably, step (4) heat treatment carries out in vertical atmosphere furnace.
Step (4) atomization is realized by peristaltic pump and atomizer.
Preferably, the peristaltic pump according to 0.01~10L/min flow velocity by mixed liquor import atomizer in, such as according to
0.02L/min、0.05L/min、0.08L/min、0.1L/min、0.5L/min、0.8L/min、1L/min、2L/min、3L/
The flow velocity of min, 5L/min, 8L/min or 9L/min etc..Flow velocity is bigger, and the mist droplet particle size of ejection is bigger；Flow velocity is smaller, ejection
Mist droplet particle size is smaller.
Preferably, the droplet maximum particle diameter sprayed by atomizer is controlled at 30~60 μm, such as 30 μm, 35 μm, 40 μm, 45
μm, 50 μm, 55 μm or 60 μm etc..Partial size is bigger, wherein the positive electrode particle reunited is more, is unfavorable for dispersing agent during heat treatment
Sufficiently carbonization；Partial size is smaller, and the large particle surface covering amount in positive electrode can be made too low, be unfavorable for performance boost.
Preferably, step (4) protective atmosphere is argon gas and/or nitrogen atmosphere.The protective atmosphere is effectively prevented
The oxidation reaction of agraphitic carbon, graphene during heat treatment.
Described method includes following steps as a preferred technical solution:
(1) it disperses organic matter dispersing agent in solvent, obtaining organic matter dispersant concentration is 20~100g/L dispersing agent
Solution；
(2) graphene is added in dispersant solution, is dispersed using shearing dispersal device, shears dispersal device
Revolving speed is 1000~10000rpm, obtains the graphene dispersing solution that graphene concentration is 4~20g/L；
(3) positive electrode is added in the graphene dispersing solution that step (2) obtain and continues to stir, it is dense to obtain positive electrode
Degree is the mixed liquor of 100~1200g/L；
(4) mixed liquor is imported in atomizer according to the flow velocity of 0.01~10L/min and is atomized by peristaltic pump, the atomization
The droplet maximum particle diameter that device sprays is 30~60 μm, and atomization air flow is downwardly into vertical atmosphere furnace, is heat-treated at 400~1000 DEG C
0.05~3min obtains composite positive pole.
The third object of the present invention is to provide lithium ion battery made from a kind of utilization composite positive pole as described above.
Compared with prior art, the invention has the benefit that
1, composite positive pole provided by the invention can be improved the uniformity of graphene coated positive electrode, solve simultaneously
The problem of graphene is reacted with positive electrode oxide under high temperature: by way of adding organic matter dispersing agent, graphene is reduced
The stacking of graphene is reunited in dispersion liquid；Simultaneously in such a way that the spraying and short time is heat-treated, avoid surface coating layer and
The reaction of positive electrode.
2, composite positive pole provided by the invention is able to solve the anisotropy and heap overlay graphene conductive of graphene
The restricted problem of property.The present invention is by high-temperature heat treatment in a protected environment, so that the organic matter point in graphene dispersing solution
Powder carbonization, forms amorphous carbon；Since the heat treatment time in Spray calcination furnace is very short, graphene point can be effectively kept
Graphene and dispersing agent are uniformly distributed in dispersion liquid, therefore calcined dispersing agent is evenly distributed on around graphene, in graphite
The bridge of guidance electronics circulation has been constructed between alkene x/y plane.Amorphous carbon can also be prevented as the interlayer between graphene simultaneously
Only the stacking between graphene is reunited.Thus graphene conductive limited performance is solved the problems, such as.
3, composite positive pole provided by the invention can pass through agraphitic carbon-graphene packet with superior electrical conductivity energy
Coating effectively improves the electric conductivity of positive electrode；Simultaneously, moreover it is possible to by reduce anode pole piece formula in conductive agent dosage come
Improve the specific capacity of battery.
4, the present invention realizes consecutive production using spraying heat-treating methods, and dispersion stabilization is high, easy to operate, greatly
Improve production efficiency, being capable of large-scale serial production.
Detailed description of the invention
Fig. 1 be the positive electrode that the composite positive pole obtained using embodiment 1, comparative example 1-3 are obtained and without cladding just
Voltage-capacity curve graph of the soft-package battery of pole material preparation under 5C discharge-rate.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
A kind of composite positive pole including positive electrode and is coated on the clad on the positive electrode surface, the packet
Coating is amorphous carbon-graphene layer, and amorphous carbon is distributed on the surface of graphene.In the composite positive pole amorphous carbon with
The mass ratio of graphene is 3:1；The mass ratio of clad and positive electrode is 0.1:1.The positive electrode is nickel cobalt lithium aluminate.
The preparation method of the composite positive pole includes the following steps:
(1) polyethylene of dispersing agent pyrrolidones is added in aqueous solvent, by being dispersed with stirring uniformly, forming concentration is 50g/
The dispersant solution of L；
(2) graphene is added in dispersant solution and is uniformly mixed, dispersed using shearing dispersal device, shearing dispersion
Head revolving speed is 5000rpm, obtains the graphene dispersing solution that graphene concentration is 4g/L；
(3) under lasting stirring condition, nickel cobalt lithium aluminate is added in graphene dispersing solution and forms nickel cobalt aluminic acid lithium concentration
For the mixed solution of 160g/L, wherein graphene quality is the 2.5% of nickel cobalt lithium aluminate quality in mixed solution；
(4) mixed solution is imported in atomizer spraying vertically downward according to 5L/min flow velocity by peristaltic pump, atomization
The droplet maximum particle diameter that device sprays is 45 μm, and atomization air flow passes downwardly through 600 DEG C of vertical atmosphere furnaces and is heat-treated, when heat treatment
Between be 0.5min, wherein be connected in vertical atmosphere furnace argon gas protection, the solid particle collected, i.e. composite positive pole.
The mixed solution that nickel cobalt aluminic acid lithium concentration in step (3) is 160g/L, which is replaced with nickel cobalt aluminic acid lithium concentration, is
The mixed solution of 100g/L can equally obtain composite positive pole.
Embodiment 2
A kind of composite positive pole including positive electrode and is coated on the clad on the positive electrode surface, the packet
Coating is amorphous carbon-graphene layer, and amorphous carbon is distributed on the surface of graphene.In the composite positive pole amorphous carbon with
The mass ratio of graphene is 5:1；The mass ratio of clad and positive electrode is 0.15:1.The positive electrode is nickel cobalt mangaic acid
Lithium.
The preparation method of the composite positive pole includes the following steps:
(1) N- crassitude is added in the mixture of polyethylene of dispersing agent pyrrolidones and Brij-35
The in the mixed solvent of ketone, dehydrated alcohol and isopropanol uniformly forms the dispersant solution that concentration is 20g/L by being dispersed with stirring；
(2) graphene is added in dispersant solution and is uniformly mixed, dispersed using shearing dispersal device, shearing dispersion
Head revolving speed is 10000rpm, obtains the graphene dispersing solution that graphene concentration is 20g/L；
(3) under lasting stirring condition, graphene dispersing solution is added in cobalt acid lithium, obtaining cobalt acid lithium concentration is 800g/L's
Mixed solution, wherein graphene quality is the 0.075% of cobalt acid lithium quality in mixed solution；
(4) mixed solution is imported in atomizer spraying vertically downward according to 10L/min flow velocity by peristaltic pump, atomization
The mist droplet particle size that device sprays is 30 μm, and atomization air flow passes downwardly through 400 DEG C of vertical atmosphere furnaces and is heat-treated, and heat treatment time is
3min, wherein being connected with argon gas protection, the solid particle collected, i.e. composite positive pole in vertical atmosphere furnace.
Embodiment 3
A kind of composite positive pole including positive electrode and is coated on the clad on the positive electrode surface, the packet
Coating is amorphous carbon-graphene layer, and amorphous carbon is distributed on the surface of graphene.In the composite positive pole amorphous carbon with
The mass ratio of graphene is 1:1；The mass ratio of clad and positive electrode is 0.02:1.The positive electrode is nickel cobalt mangaic acid
The combination of lithium, lithium nickelate and LiMn2O4.
The preparation method of the composite positive pole includes the following steps:
(1) polyethylene of dispersing agent pyrrolidones is added in aqueous solvent, by being dispersed with stirring uniformly, forming concentration is
The dispersant solution of 100g/L；
(2) graphene is added in dispersant solution and is uniformly mixed, dispersed using shearing dispersal device, shearing dispersion
Head revolving speed is 1000rpm, obtains the graphene dispersing solution that graphene concentration is 12g/L；
(3) under lasting stirring condition, positive electrode is added in graphene dispersing solution, obtaining positive electrode concentration is
The mixed solution of 1200g/L, wherein graphene quality is the 1% of positive electrode quality in mixed solution, and the positive electrode is
The combination of nickle cobalt lithium manganate and cobalt acid lithium；
(4) mixed solution is imported in atomizer spraying vertically downward according to 0.01L/min flow velocity by peristaltic pump, mist
Changing the mist droplet particle size that device sprays is 60 μm, and atomization air flow passes downwardly through 1000 DEG C of vertical atmosphere furnaces and is heat-treated, when heat treatment
Between be 0.05min, wherein be connected in vertical atmosphere furnace argon gas protection, the solid particle collected, i.e. composite positive pole.
Comparative example 1
Except step (4) are as follows: import in spray drying device mixed solution and be dried；Place into the atmosphere for being connected with argon gas
In furnace carry out temperature be 800 DEG C, the heat treatment that the time is 10h, remaining is same as Example 1.
Comparative example 2
Except by addition to argon atmosphere replaces with air atmosphere in step (4), remaining is same as Example 1.
Comparative example 3
Except the dispersant solution in step (2) is replaced with ethyl alcohol, while shearing dispersion process is changed to ultrasonic 30min,
Remaining is same as Example 1.
By positive electrode made from embodiment 1 and comparative example 1-3 and without clad anode material respectively with conductive carbon black, bonding
Agent is applied on aluminium foil after example and organic solvent N-Methyl pyrrolidone stir according to a certain mass ratio, and pole piece is made.
Wherein, all samples binder ratio is set as 2.5%, and conductive carbon black and positive electrode proportion and be 98%.
72530 soft-package batteries are fabricated to graphite cathode after pole piece is sufficiently dry, and carry out capacity and high rate performance test respectively, are surveyed
Test result is as shown in table 1 and Fig. 1.
Table 1
To sum up data can be seen that compares with existing uncoated G group material, positive electrode that embodiment 1 obtains (i.e. A,
B and C group material) there is apparent performance advantage.
Option A is under the conditions of conductive additive in proportion, though material 1C capacity is 12mAh/g fewer than G group, 5C electric discharge is held
Amount is but opposite with G group, shows very excellent high rate performance.Option b and C reduce conductive agent dosage on the basis of A, to have
Effect improves 5C discharge capacity, completely solves cladding bring capacitance loss problem.
The performance of comparative example 1,2 and 3 is below embodiment 1, and the difference of they and embodiment 1 is to be heat-treated work respectively
The use of skill, heat-treating atmosphere and dispersing agent.Respectively illustrate following several points: 1, in embodiment 1 Spray calcination heat treatment work
Skill is better than spray drying+calcining technique, solves the problems, such as clad and positive electrode reaction；2, in embodiment 1
Argon gas effectively prevent the oxidation of graphene；3, the use of dispersing agent efficiently solves graphene conductive in embodiment
Limitation.And in comparative example 3, although graphene content doubles, the stacking that dispersing technology can not solve graphene is reunited, and is caused
3 experimental group battery performance of comparative example is relatively low.
The mixed solution that the nickel cobalt aluminic acid lithium concentration in step (3) is 160g/L is replaced with into nickel cobalt aluminic acid in embodiment 1
Lithium concentration is the composite positive pole that the mixed solution of 100g/L obtains and the anode composite that embodiment 2 and embodiment 3 obtain
The performance similar with the composite positive pole that embodiment 1 obtains that material equally has.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (11)
1. a kind of composite positive pole, including positive electrode and it is coated on the clad on the positive electrode surface, feature exists
In the clad is amorphous carbon-graphene layer, and amorphous carbon is distributed on the surface of graphene, amorphous in the clad
The mass ratio of carbon and graphene is (1 ~ 5): 1；
The preparation method of the composite positive pole includes the following steps:
(1) it disperses organic matter dispersing agent in solvent, obtaining organic matter dispersant concentration is 20 ~ 100g/L dispersant solution；
(2) graphene is added in the dispersant solution that step (1) obtains, is dispersed using shearing dispersal device, is sheared
The revolving speed of dispersal device is 1000 ~ 10000rpm, obtains the graphene dispersing solution that graphene concentration is 4 ~ 20g/L；
(3) positive electrode is added in the graphene dispersing solution that step (2) obtain and continues to stir, obtaining positive electrode concentration is
The mixed liquor of 100 ~ 1200g/L；
(4) mixed liquor is imported in atomizer according to the flow velocity of 0.01 ~ 10L/min and is atomized by peristaltic pump, what atomizer sprayed
Droplet maximum particle diameter is 30 ~ 60 μm, and atomization air flow is downwardly into vertical atmosphere furnace, in protective atmosphere under the conditions of 400 ~ 1000 DEG C
It is heat-treated 0.05 ~ 3min, obtains composite positive pole.
2. composite positive pole according to claim 1, which is characterized in that in the composite positive pole clad with just
The mass ratio of pole material is (0.01 ~ 0.2): 1.
3. composite positive pole according to claim 1, which is characterized in that the positive electrode is cobalt acid lithium, nickel cobalt aluminium
In sour lithium, nickle cobalt lithium manganate, lithium nickelate, LiMn2O4 or lithium-rich manganese base material any one or at least two combination.
4. composite positive pole according to claim 1, which is characterized in that the graphene is to pass through super critical fluid
The graphene that the method for standby graphene is prepared.
5. the preparation method of composite positive pole according to claim 1, which is characterized in that the method includes walking as follows
It is rapid:
(1) it disperses organic matter dispersing agent in solvent, obtaining organic matter dispersant concentration is 20 ~ 100g/L dispersant solution；
(2) graphene is added in the dispersant solution that step (1) obtains, is dispersed using shearing dispersal device, is sheared
The revolving speed of dispersal device is 1000 ~ 10000rpm, obtains the graphene dispersing solution that graphene concentration is 4 ~ 20g/L；
(3) positive electrode is added in the graphene dispersing solution that step (2) obtain and continues to stir, obtaining positive electrode concentration is
The mixed liquor of 100 ~ 1200g/L；
(4) mixed liquor is imported in atomizer according to the flow velocity of 0.01 ~ 10L/min and is atomized by peristaltic pump, what atomizer sprayed
Droplet maximum particle diameter is 30 ~ 60 μm, and atomization air flow is downwardly into vertical atmosphere furnace, in protective atmosphere under the conditions of 400 ~ 1000 DEG C
It is heat-treated 0.05 ~ 3min, obtains composite positive pole.
6. according to the method described in claim 5, it is characterized in that, organic matter dispersing agent described in step (1) is γ-Ding Nei
Ester, propene carbonate, ethylene carbonate, ethyl acetate, polyvinylpyrrolidone, Brij-35 or polyvinyl alcohol
In any one or at least two combination.
7. according to the method described in claim 5, it is characterized in that, solvent described in step (1) is N-Methyl pyrrolidone, goes
In ionized water, dehydrated alcohol, propyl alcohol or isopropanol any one or at least two combination.
8. according to the method described in claim 5, it is characterized in that, step (2) graphene is prepared by supercritical fluid
The method of graphene is prepared.
9. according to the method described in claim 5, it is characterized in that, positive electrode described in step (3) is cobalt acid lithium, nickel cobalt aluminium
In sour lithium, nickle cobalt lithium manganate, lithium nickelate, LiMn2O4 or lithium-rich manganese base material any one or at least two combination.
10. according to the method described in claim 5, it is characterized in that, protective atmosphere described in step (4) is argon gas and/or nitrogen
Gas atmosphere.
11. utilizing lithium ion battery made from composite positive pole described in claim 1.
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| CN106992286B (en) * | 2017-03-24 | 2019-08-13 | 江苏乐能电池股份有限公司 | A kind of preparation method of high capacity trielement composite material |
| CN107017399A (en) * | 2017-06-02 | 2017-08-04 | 青岛乾运高科新材料股份有限公司 | A kind of doping type lithium vanadate anode material and its synthetic method |
| CN108091863A (en) * | 2017-12-18 | 2018-05-29 | 江苏双登富朗特新能源有限公司 | Graphene is modified lithium-rich manganese-based anode material and preparation method thereof |
| CN112635728B (en) * | 2020-12-16 | 2022-03-25 | 中国科学院宁波材料技术与工程研究所 | Graphene composite lithium-rich manganese-based positive electrode material, reconstruction preparation method thereof and lithium ion battery |
| CN114314549A (en) * | 2021-12-28 | 2022-04-12 | 陕西煤业化工技术研究院有限责任公司 | Graphene-coated lithium ion battery positive electrode material and preparation method thereof |
| CN114709404B (en) * | 2022-04-22 | 2023-02-03 | 宁波市稻禾科技有限公司 | NASICON titanium sodium phosphate coated sodium iron phosphate cathode material and preparation method thereof |
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