CN105762345A - Composite cathode material and preparation method thereof and lithium ion battery - Google Patents
Composite cathode material and preparation method thereof and lithium ion battery Download PDFInfo
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- CN105762345A CN105762345A CN201610280950.3A CN201610280950A CN105762345A CN 105762345 A CN105762345 A CN 105762345A CN 201610280950 A CN201610280950 A CN 201610280950A CN 105762345 A CN105762345 A CN 105762345A
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- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 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
- 239000010406 cathode material Substances 0.000 title abstract 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 137
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 130
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims description 45
- 238000010438 heat treatment Methods 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 30
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052744 lithium Inorganic materials 0.000 claims description 22
- 239000012298 atmosphere Substances 0.000 claims description 21
- 239000006199 nebulizer Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 238000010008 shearing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 230000002572 peristaltic effect Effects 0.000 claims description 9
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 8
- -1 alkene ester Chemical class 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 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 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 7
- 238000000889 atomisation Methods 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 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 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 239000003595 mist Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 238000005253 cladding Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical compound C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- 239000002344 surface layer Substances 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
- 239000011247 coating layer Substances 0.000 abstract 2
- 238000010924 continuous production Methods 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 239000011259 mixed solution Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000003647 oxidation Effects 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
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 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
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-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
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002482 conductive additive Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008187 granular material Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 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
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002345 surface coating layer Substances 0.000 description 2
- 238000012360 testing method Methods 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 compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 239000005030 aluminium foil Substances 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement 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
- 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
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 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
- 238000001694 spray drying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a composite cathode material and a preparation method thereof and a lithium ion battery.The composite cathode material comprises a cathode material body and a coating layer with which the surface of the cathode material body is coated, the coating layer is an amorphous carbon and graphene layer, and amorphous carbon is uniformly distributed on the surface of graphene.The composite cathode material is prepared through the steps that mixed liquid of the cathode material body and graphene dispersion liquid is sprayed into a vertical calcining furnace filled with protection gas through a sprayer, and then thermal treatment is conducted.By means of the composite cathode material, the uniformity of the graphene-coated cathode material body can be improved; the problem that graphene reacts with cathode material oxide at high temperature is solved, and the limitation problem of anisotropy of graphene to electrical conductivity of graphene is solved; the problem that graphene is prone to stacking is effectively relieved, and the electrical conductivity of the cathode material body is improved; the specific capacity of the battery can be improved by reducing the addition amount of a conductive agent in a formula of a cathode piece; continuous production can be achieved, the production efficiency is greatly improved, and large-scale batched production can be achieved.
Description
Technical field
The invention belongs to the preparing technical field of material, relate to a kind of composite positive pole, its preparation method and
Lithium ion battery.
Background technology
In recent years, under the support of national policy, electric automobile industry has obtained rapid development.High specific energy
Amount, long-life, the novel anode material of low cost and battery thereof are particularly important.Lithium ion battery is with it
Running voltage is high, specific energy big, have extended cycle life, pollute the advantage such as little in numerous electrochmical power sources de-grain husk and
Go out.
But the positive electrode of commercialization at present cannot take into account circulation, specific energy, voltage and security problems.Portion
Divide material such as lithium-rich manganese base material, nickel cobalt al and ni cobalt manganese systems row to there is also cyclical stability, especially exist
The defect such as under hot conditions cyclical stability is not good enough, limits the service life of this material.This is because battery
In positive electrode directly and the concurrent biochemical reaction of electrolyte contacts positive electrode surface texture can be caused to collapse
Collapsing, lithium ion embedding de-performance such as is substantially reduced at the problem.Therefore, for solve the problems referred to above best method be into
Row Surface coating processes, thus reduces positive electrode and contact with the direct of electrolyte.Commodity positive electrode at present
Coating include carbon cladding, metal-oxide is (such as ZnO, Al2O3Deng), phosphate is (such as AlPO4Deng)
With anion (such as F-Deng).Phosphate non-electroactive material, phosphatic cladding increases material and electricity
Solve the resistance between liquid, hinder embedding and the abjection of lithium ion.Though above covering material has intercepted nickel mangaic acid
Lithium material directly contacts with electrolyte, but exists and reduces specific capacity, corrosion material surface and increase resistance etc.
Problem.
Graphene is the two-dimensional sheet nano-carbon material of a kind of carbon atom tightly packed one-tenth monolayer honeycomb shape structure,
There is higher theoretical specific surface area (2630m2/ g), the calorifics of excellence, mechanics, optics, electric property
And it is widely applied prospect.The resistivity of Graphene only about 10-6Ω cm is lower than copper or silver, in the world
The material that resistivity is minimum.But only axial for Graphene two dimensional surface xy resistivity is 10-6Ω cm, and
Resistivity in the z-axis vertical direction of two dimensional surface is higher.The resistivity of therefore actual graphene powder is high
Reach 10-4Ω·cm.This anisotropy of Graphene significantly limit its utilization in every field.Especially
In field of batteries, when using Graphene as conductive agent, what xy was axial lead electronic capability is significantly stronger than z-axis
Mode so that graphene conductive additive is the least relative to the improvement effect of CNT.Moreover, stone
Ink alkene sheet interlayer has the strongest interaction force, causes graphene sheet layer easily to stack, cambium layer spacing
Only have the multi-layer graphene structure of 0.334 nanometer.The characteristic of this easy stacking reduces the specific surface of Graphene
Long-pending, limit the efficient utilization at its interface, be unfavorable for the performance of the electric conductivity of Graphene.
Existing graphene coated scheme simply simply by the mode of stirring or ball milling by positive electrode and stone
Ink alkene carries out mixing and carries out high-temperature process the most again.And do not take into account preparation technology Graphene easily stacked spy
Property, the being evenly coated property of Graphene and the high-temperature process performance impact to positive electrode.
Existing disclosed Graphene and positive electrode composite preparation process is used to yet suffer from a lot of defect:
CN 104538620 A discloses the preparation method of a kind of fluorinated graphene cladding manganese cobalt lithium anode material will
The fluorinated graphene that ultrasonic disperse is good is stirred with active substance, more centrifugal being thermally treated resulting in is coated with graphite
The product of alkene.There is greatest drawback in this technology: owing to Graphene specific surface is very big, easily roll into a ball stacking,
Gathering, the process that simple stirring and centrifugal heat process cannot make the covering table at positive electrode of graphene uniform
Face.
CN 104393282 A discloses the preparation method of the polynary positive pole material of a kind of graphene coated, passes through
The mode admixed graphite alkene of planetary ball mill and positive electrode, higher by 750-800 DEG C of Isothermal sinter 10-15h
The heat treatment of pure nitrogen gas, is finally coated with the product of Graphene.There is greatest drawback in this technology:
1, positive electrode and graphite cannot be mixed by the mode of planetary ball mill uniformly.Meanwhile, heat treatment
Overlong time can make Graphene seriously stack, reunite.2, the high pure nitrogen environment of heat treatment is well kept away
Exempt from the problem of oxidation of Graphene.But originally need the positive electrode of oxygen atmosphere sintering synthesis, high-purity
Under nitrogen environment, 750-800 DEG C of Isothermal sinter 10-15h will have a strong impact on the performance of material itself.Exist simultaneously
Under the hot environment of 10-15h, Graphene reacts with the positive electrode of oxide properties most probably and affects
End properties.
CN 102623708A discloses the preparation method of the nickel ion doped material of a kind of graphene coated, will be mixed
There is 300-600 DEG C of precalcining 2-5h of presoma of certain proportion Graphene, then forge under the conditions of 700-900 DEG C
Burn 6-10h.There is greatest drawback in this technology: the sintering atmosphere of nickel ion doped material needs oxygen, and
700-900 DEG C of sintering 6-10h can make most Graphene oxidized.
CN 102544491A discloses lithium iron phosphate positive material and the preparation side thereof of a kind of doped graphene
Method.Described method includes: soluble lithium compounds, phosphate and ferrous salt are mixed in dispersant by (1)
Obtain dispersion liquid a；(2) oxidation of Graphene derived material is obtained graphene oxide derived material, ultrasonic point
Dissipate, obtain dispersion liquid b；(3) dispersion liquid a and dispersion liquid b are mixed, stir, through spraying heat treatment,
Calcining, obtains the lithium iron phosphate positive material of doped graphene.But the method the easy heap of unresolved Graphene
Problem folded, that reunite.
Summary of the invention
The problem existed for prior art, it is an object of the invention to provide a kind of composite positive pole, its
Preparation method and lithium ion battery, in described composite positive pole, agraphitic carbon-graphene layer is to positive electrode
Being evenly coated property is high, it is to avoid the Graphene reaction with positive electrode oxide, and solves Graphene
Anisotropy and the stacking reunion restricted problem to graphene conductive.
For reaching this purpose, the present invention by the following technical solutions:
An object of the present invention is to provide a kind of composite positive pole, and described composite positive pole just includes
Pole material and be coated on the clad on described positive electrode surface, described clad is amorphous carbon-Graphene
Layer, described amorphous carbon is distributed in graphenic surface.
Graphene forms conductive network by being distributed in the amorphous carbon on its surface；Meanwhile, amorphous carbon can also
As the interlayer between Graphene, prevent the stacking between Graphene from reuniting.
In described clad, the mass ratio of amorphous carbon and Graphene is (1～5): 1, as mass ratio be 1.5:1,
2.5:1,3:1 or 4.5:1 etc..
In described composite positive pole, clad is (0.01～0.2) with the mass ratio of positive electrode: 1, such as mass ratio
For 0.02:1,0.05:1,0.08:1,0.1:1,0.15:1 or 0.18:1 etc..
Preferably, described positive electrode is cobalt acid lithium (LCO), nickel cobalt lithium aluminate (NCA), nickel cobalt manganese
Any one in acid lithium (NCM), lithium nickelate (LNO), LiMn2O4 (LMO) or lithium-rich manganese base material
Plant or the combination of at least two.Typical but non-limiting be combined as: LCO and NCA, NCA with
NCM, NCM, LNO and LMO, NCA, NCM and LNO.
Preferably, described Graphene is the graphite that the method by preparing graphene by using supercritical fluid prepares
Alkene.The Graphene that described Graphene prepares preferably by method disclosed in CN 102115078 A.
The two of the purpose of the present invention are to provide the preparation method of a kind of composite positive pole, described method to include
Following steps:
(1) by Organic substance dispersant in solvent, dispersant solution is obtained；
(2) disperse graphene in dispersant solution, obtain graphene dispersing solution；
(3) graphene dispersing solution that positive electrode prepares with step (2) is mixed, obtain mixed liquor；
(4) mixed liquor is atomized, protective atmosphere carries out heat treatment, obtains described composite positive pole.
Described in step (1), in dispersant solution, the concentration of Organic substance dispersant is 20～100g/L, such as 25
G/L, 40g/L, 60g/L or 80g/L etc..The concentration of dispersant solution is mainly according to its ratio with Graphene
Example and Graphene concentration regulate and control.
The ratio regular meeting of Organic substance dispersant affects graphene dispersion effect, and heat treatment temperature is also required to according to dividing
The ratio of powder regulates and controls.Because the molecular weight of Organic substance dispersant is the biggest, it is more difficult to carbonization, needs higher
Heat treatment temperature.Preferably, described in step (1), Organic substance dispersant is gamma-butyrolacton, propylene carbonate
Ester, ethylene carbonate, ethyl acetate, polyvinylpyrrolidone, Brij-35 or polyethylene
Any one or the combination of at least two in alcohol.Typical but non-limiting it is combined as: gamma-butyrolacton and carbon
Acid propylene ester, ethylene carbonate and ethyl acetate, polyvinylpyrrolidone and Brij-35,
Polyvinylpyrrolidone and polyvinyl alcohol, Brij-35 and polyvinyl alcohol, polyvinylpyrrolidine
Ketone, Brij-35 and polyvinyl alcohol, gamma-butyrolacton, Allyl carbonate, ethylene carbonate with
Ethyl acetate, gamma-butyrolacton, ethylene carbonate, polyvinylpyrrolidone and Brij-35.
Preferably, solvent described in step (1) be N-Methyl pyrrolidone, deionized water, dehydrated alcohol,
Any one or the combination of at least two in propanol or isopropanol.Typical but non-limiting combination can be:
N-Methyl pyrrolidone and deionized water, dehydrated alcohol and isopropanol, N-Methyl pyrrolidone, deionized water
With dehydrated alcohol, deionized water, propanol, dehydrated alcohol and isopropanol, N-Methyl pyrrolidone, deionization
Water, dehydrated alcohol and isopropanol.Solvent in dispersion liquid can volatilize in follow-up heat treatment process, will not
The performance of final products is impacted.
Described in step (2), in graphene dispersing solution, the concentration of Graphene is 4～20g/L, as 5g/L, 8
G/L, 10g/L, 13g/L, 15g/L, 17g/L or 18g/L etc..Owing to Graphene specific surface area is very big,
Easily reunite during dispersion in a fluid, and graphene film interlayer has the strongest interaction force, causes
Graphene sheet layer easily stacks.Even if adding dispersant, but the concentration of Graphene is also unsuitable too high.Concentration
Too high, reunion and the stacking of Graphene can be aggravated.
Preferably, described in step (2), graphene dispersing solution is prepared via a method which to obtain: by Graphene
Join in dispersant solution, utilize and shear dispersal device dispersion.Owing to Graphene is nanoscale microplate, make
The Graphene reunited cannot be disperseed with common dispersing apparatus, only could be by Graphene by high-speed shearing machine
Break up.
Preferably, the rotating speed of described shearing dispersal device is 1000～10000rpm, as 1500rpm, 2000
Rpm, 5000rpm, 8000rpm or 9000rpm etc..
Preferably, described Graphene is prepared by the method for preparing graphene by using supercritical fluid.Described stone
The Graphene that ink alkene prepares preferably by method disclosed in CN 102115078A.
Described in step (3), the positive electrode concentration in mixed liquor is 100～1200g/L, as 150g/L, 200
G/L, 500g/L, 600g/L, 700g/L, 800g/L, 900g/L or 1100g/L etc..Positive electrode
Concentration mainly affects the spray effect of aerosol apparatus, and excessive concentration can make spraying granule excessive, causes heat treatment
During calcine insufficient；Meanwhile, the mixed liquor of high concentration is through the easy plug nozzle of spray nozzle.Institute
The concentration stating positive electrode can also be lower.
Preferably, positive electrode described in step (3) be described positive electrode be cobalt acid lithium (LCO), nickel
Cobalt lithium aluminate (NCA), nickle cobalt lithium manganate (NCM), lithium nickelate (LNO), LiMn2O4 (LMO)
Or any one or the combination of at least two in lithium-rich manganese base material.Typical but non-limiting it is combined as:
LCO and NCA, NCA and NCM, NCM, LNO and LMO, NCA, NCM and LNO.
Preferably, be blended in described in step (3) continuously stirred under the conditions of carry out.
Described in step (4), heat treatment temperature is 400-1000 DEG C, as 500 DEG C, 600 DEG C, 800 DEG C or
900 DEG C etc..
Preferably, described in step (4), heat treatment time is 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, and the dispersant carbonization on surface all can be made not fill
Point, finally have a strong impact on the electric conductivity of surface coating layer；Process overlong time, or heat treatment temperature mistake
High, it is possible to cause positive electrode to react with clad, affect material property.
Preferably, step (4) described heat treatment is carried out in vertical atmosphere furnace.
Step (4) described atomization is realized by peristaltic pump and nebulizer.
Preferably, mixed liquor is imported in nebulizer according to the flow velocity of 0.01～10L/min by described peristaltic pump, as
According to 0.02L/min, 0.05L/min, 0.08L/min, 0.1L/min, 0.5L/min, 0.8L/min,
The flow velocity of 1L/min, 2L/min, 3L/min, 5L/min, 8L/min or 9L/min etc..Flow velocity is the biggest, spray
The mist droplet particle size gone out is the biggest；Flow velocity is the least, and the mist droplet particle size of ejection is the least.
Preferably, the droplet maximum particle diameter sprayed by nebulizer controls in 30～60 μm, as 30 μm,
35 μm, 40 μm, 45 μm, 50 μm, 55 μm or 60 μm etc..Particle diameter is the biggest, the positive pole wherein reunited
Grain is many, is unfavorable for dispersant abundant carbonization in heat treatment process；Particle diameter is the least, can make in positive electrode
Large particle surface covering amount too low, be unfavorable for performance boost.
Preferably, step (4) described protective atmosphere is argon and/or nitrogen atmosphere.Described protective atmosphere is effective
Prevent agraphitic carbon, the Graphene oxidation reaction in heat treatment process.
As preferred technical scheme, described method comprises the steps:
(1) by Organic substance dispersant in solvent, obtaining Organic substance dispersant concentration is 20～100g/L
Dispersant solution；
(2) Graphene is joined in dispersant solution, utilize shearing dispersal device to disperse, shear and divide
The rotating speed put in bulk is 1000～10000rpm, obtains the graphene dispersion that Graphene concentration is 4～20g/L
Liquid；
(3) positive electrode is added in the graphene dispersing solution that step (2) obtains and continuously stirred, obtain
Positive electrode concentration is the mixed liquor of 100～1200g/L；
(4) mixed liquor is imported in nebulizer according to the flow velocity of 0.01～10L/min and is atomized by peristaltic pump, institute
The droplet maximum particle diameter stating nebulizer ejection is 30～60 μm, and atomization air flow is downwardly into vertical atmosphere furnace,
400～1000 DEG C of heat treatments 0.05～3min, obtain composite positive pole.
The three of the purpose of the present invention are to provide a kind of lithium ion utilizing composite positive pole described above to prepare
Battery.
Compared with prior art, the invention have the benefit that
1, the composite positive pole that the present invention provides can improve the uniformity of graphene coated positive electrode,
Solve the problem that under high temperature, Graphene reacts with positive electrode oxide: by adding Organic substance dispersant simultaneously
Mode, reduce the stacking of Graphene in graphene dispersing solution and reunite；Utilize at spraying and short time heat simultaneously
The mode of reason, it is to avoid the reaction of surface coating layer and positive electrode.
2, the composite positive pole that the present invention provides can solve the problem that anisotropy and the heap overlay graphite of Graphene
The restricted problem of alkene electric conductivity.The present invention is by the high-temperature heat treatment under protection environment so that Graphene divides
Dissipate the Organic substance dispersant carbonization in liquid, form amorphous carbon；During due to heat treatment in Spray calcination stove
Between the shortest, it is possible to effectively keep being uniformly distributed of Graphene and dispersant in graphene dispersing solution, therefore calcine
After dispersant be evenly distributed on around Graphene, constructed between Graphene x/y plane guiding electronics circulation
Bridge.Amorphous carbon can also prevent the stacking group between Graphene as the interlayer between Graphene simultaneously
Poly-.The problem thus solving graphene conductive limited performance.
3, the composite positive pole that the present invention provides can be by having the agraphitic carbon-stone of superior electrical conductivity energy
Ink alkene clad, improves the electric conductivity of positive electrode effectively；Simultaneously, moreover it is possible to join by reducing anode pole piece
In side, the consumption of conductive agent improves the specific capacity of battery.
4, the present invention uses spraying heat-treating methods to realize consecutive production, and dispersion stabilization is high, operation letter
Single, greatly improve production efficiency, it is possible to large-scale mass production.
Accompanying drawing explanation
Fig. 1 is the positive electrode and nothing using the composite positive pole that obtains of embodiment 1, comparative example 1-3 to obtain
Soft-package battery prepared by the clad anode material voltage-capacity curve chart under 5C discharge-rate.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
Embodiment 1
A kind of composite positive pole, including positive electrode and the clad that is coated on described positive electrode surface,
Described clad is amorphous carbon-graphene layer, and amorphous carbon is distributed in graphenic surface.Described anode composite
In material, amorphous carbon is 3:1 with the mass ratio of Graphene；Clad with the mass ratio of positive electrode is
0.1:1.Described positive electrode is nickel cobalt lithium aluminate.
The preparation method of described composite positive pole comprises the steps:
(1) polyethylene of dispersing agent ketopyrrolidine is added in aqueous solvent, uniform by dispersed with stirring, formed dense
Degree is the dispersant solution of 50g/L；
(2) Graphene is added mix homogeneously in dispersant solution, utilizes shearing dispersal device to disperse,
Shearing dispersing head rotating speed is 5000rpm, obtains the graphene dispersing solution that Graphene concentration is 4g/L；
(3) under the conditions of continuously stirred, nickel cobalt lithium aluminate is added in graphene dispersing solution and form nickel cobalt aluminic acid
Lithium concentration is the mixed solution of 160g/L, and wherein, in mixed solution, Graphene quality is nickel cobalt lithium aluminate quality
2.5%；
(4) by peristaltic pump, mixed solution is imported according to 5L/min flow velocity the nebulizer sprayed vertically downward
In, the droplet maximum particle diameter of nebulizer ejection is 45 μm, and atomization air flow passes downwardly through 600 DEG C of vertical atmosphere furnace
Carrying out heat treatment, heat treatment time is 0.5min, is wherein connected with argon shield in vertical atmosphere furnace, collects
The solid particle arrived, i.e. composite positive pole.
The mixed solution that nickel cobalt lithium aluminate concentration is 160g/L in step (3) is replaced with nickel cobalt lithium aluminate dense
Degree is the mixed solution of 100g/L, can obtain composite positive pole equally.
Embodiment 2
A kind of composite positive pole, including positive electrode and the clad that is coated on described positive electrode surface,
Described clad is amorphous carbon-graphene layer, and amorphous carbon is distributed in graphenic surface.Described anode composite
In material, amorphous carbon is 5:1 with the mass ratio of Graphene；Clad with the mass ratio of positive electrode is
0.15:1.Described positive electrode is nickle cobalt lithium manganate.
The preparation method of described composite positive pole comprises the steps:
(1) mixture of polyethylene of dispersing agent ketopyrrolidine with Brij-35 is added N-methyl
Ketopyrrolidine, dehydrated alcohol are with the mixed solvent of isopropanol, and uniform by dispersed with stirring, forming concentration is
The dispersant solution of 20g/L；
(2) Graphene is added mix homogeneously in dispersant solution, utilizes shearing dispersal device to disperse,
Shearing dispersing head rotating speed is 10000rpm, obtains the graphene dispersing solution that Graphene concentration is 20g/L；
(3) under the conditions of continuously stirred, cobalt acid lithium being added graphene dispersing solution, obtaining cobalt acid lithium concentration is
The mixed solution of 800g/L, wherein, in mixed solution, Graphene quality is the 0.075% of cobalt acid lithium quality；
(4) by peristaltic pump, mixed solution is imported according to 10L/min flow velocity the nebulizer sprayed vertically downward
In, the mist droplet particle size of nebulizer ejection is 30 μm, and atomization air flow passes downwardly through 400 DEG C of vertical atmosphere furnace to be carried out
Heat treatment, heat treatment time is 3min, is wherein connected with argon shield in vertical atmosphere furnace, and what collection obtained consolidates
Body granule, i.e. composite positive pole.
Embodiment 3
A kind of composite positive pole, including positive electrode and the clad that is coated on described positive electrode surface,
Described clad is amorphous carbon-graphene layer, and amorphous carbon is distributed in graphenic surface.Described anode composite
In material, amorphous carbon is 1:1 with the mass ratio of Graphene；Clad with the mass ratio of positive electrode is
0.02:1.Described positive electrode is the combination of nickle cobalt lithium manganate, lithium nickelate and LiMn2O4.
The preparation method of described composite positive pole comprises the steps:
(1) polyethylene of dispersing agent ketopyrrolidine is added in aqueous solvent, uniform by dispersed with stirring, formed dense
Degree is the dispersant solution of 100g/L；
(2) Graphene is added mix homogeneously in dispersant solution, utilizes shearing dispersal device to disperse,
Shearing dispersing head rotating speed is 1000rpm, obtains the graphene dispersing solution that Graphene concentration is 12g/L；
(3) under the conditions of continuously stirred, positive electrode is added in graphene dispersing solution, obtain positive electrode
Concentration is the mixed solution of 1200g/L, and wherein, in mixed solution, Graphene quality is positive electrode quality
1%, described positive electrode is the combination of nickle cobalt lithium manganate and cobalt acid lithium；
(4) by peristaltic pump, mixed solution is imported according to 0.01L/min flow velocity the atomization sprayed vertically downward
In device, the mist droplet particle size of nebulizer ejection is 60 μm, and atomization air flow passes downwardly through 1000 DEG C of vertical atmosphere furnace
Carrying out heat treatment, heat treatment time is 0.05min, is wherein connected with argon shield in vertical atmosphere furnace, collects
The solid particle obtained, i.e. composite positive pole.
Comparative example 1
Except step (4) is: mixed solution is imported in spray drying device and is dried；Place into and be connected with argon
The atmosphere furnace of gas is carried out temperature be 800 DEG C, the time be the heat treatment of 10h, remaining is same as in Example 1.
Comparative example 2
Except by addition in step (4), argon gas atmosphere replaces with air atmosphere, remaining is same as in Example 1.
Comparative example 3
Except the dispersant solution in step (2) is replaced with ethanol, shearing dispersive process is changed into ultrasonic simultaneously
30min, remaining is same as in Example 1.
Positive electrode that embodiment 1 and comparative example 1-3 are prepared and without clad anode material respectively with conductive carbon
Black, binding agent is applied to after stirring with organic solvent N-Methyl pyrrolidone by certain mass ratio
On aluminium foil, prepare pole piece.Wherein, all samples binding agent ratio is all set as 2.5%, and conductive carbon black and
Positive electrode proportion and be 98%.Treat that pole piece is fabricated to 72530 with graphite cathode fully after drying soft
Bag battery, and carry out capacity and high rate performance test respectively, test result is as shown in table 1 and Fig. 1.
Table 1
To sum up data it can be seen that with existing uncoated G group material contrast, the positive pole that embodiment 1 obtains
Material (i.e. A, B and C group material) has obvious performance advantage.
Option A is under the conditions of conductive additive in proportion, though material 1C capacity 12mAh/g fewer than G group,
But 5C discharge capacity is but relative with G group, demonstrate the most excellent high rate performance.Option b and C exist
Reduce conductive agent consumption on the basis of A, thus effectively raise 5C discharge capacity, completely solve clad strip
The capacitance loss problem come.
The performance of comparative example 1,2 and 3 is below embodiment 1, and they are respectively with the difference of embodiment 1
The use of Technology for Heating Processing, heat-treating atmosphere and dispersant.Respectively illustrate following some: 1, embodiment 1
The Technology for Heating Processing of middle Spray calcination is better than spray-dried+technique of calcining, efficiently solve clad and
The problem of positive electrode reaction；2, the argon in embodiment 1 is effectively prevented the oxidation of Graphene；3、
In embodiment, the use of dispersant efficiently solves the restriction of graphene conductive.And in comparative example 3, although
Graphene content doubles, but the stacking that dispersing technology cannot solve Graphene is reunited, and causes comparative example 3 real
Test Battery pack performance on the low side.
The mixed solution that nickel cobalt lithium aluminate concentration is 160g/L in step (3) is replaced with nickel by embodiment 1
Cobalt lithium aluminate concentration is the composite positive pole that obtains of the mixed solution of 100g/L and embodiment 2 and embodiment
The performance that 3 composite positive poles that the composite positive pole obtained has equally with embodiment 1 obtains are similar.
Applicant states, the foregoing is only the detailed description of the invention of the present invention, but protection scope of the present invention
Being not limited thereto, person of ordinary skill in the field is it will be clearly understood that any skill belonging to the art
Art personnel in the technical scope that the invention discloses, the change that can readily occur in or replacement, all fall within the present invention
Protection domain and open within the scope of.
Claims (10)
1. a composite positive pole, including positive electrode and the cladding that is coated on described positive electrode surface
Layer, it is characterised in that described clad is amorphous carbon-graphene layer, and amorphous carbon is distributed in Graphene
Surface.
Composite positive pole the most according to claim 1, it is characterised in that nothing in described clad
Setting carbon is (1～5) with the mass ratio of Graphene: 1；
Preferably, in described composite positive pole, the mass ratio of clad and positive electrode is (0.01～0.2): 1；
Preferably, described positive electrode is cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate, lithium nickelate, manganese
Any one or the combination of at least two in acid lithium or lithium-rich manganese base material；
Preferably, described Graphene is the graphite that the method by preparing graphene by using supercritical fluid prepares
Alkene.
The preparation method of composite positive pole the most according to claim 1 and 2, it is characterised in that institute
The method of stating comprises the steps:
(1) by Organic substance dispersant in solvent, dispersant solution is obtained；
(2) disperse graphene in dispersant solution, obtain graphene dispersing solution；
(3) graphene dispersing solution that positive electrode prepares with step (2) is mixed, obtain mixed liquor；
(4) mixed liquor is atomized, protective atmosphere carries out heat treatment, obtains described composite positive pole.
Method the most according to claim 3, it is characterised in that described in step (1), dispersant is molten
In liquid, the concentration of Organic substance dispersant is 20～100g/L；
Preferably, described in step (1), Organic substance dispersant is gamma-butyrolacton, Allyl carbonate, ethylene
Any in alkene ester, ethyl acetate, polyvinylpyrrolidone, Brij-35 or polyvinyl alcohol
A kind of or the combination of at least two；
Preferably, solvent described in step (1) be N-Methyl pyrrolidone, deionized water, dehydrated alcohol,
Any one or the combination of at least two in propanol or isopropanol.
5. according to the method described in claim 3 or 4, it is characterised in that graphite described in step (2)
In alkene dispersion liquid, the concentration of Graphene is 4～20g/L；
Preferably, described in step (2), graphene dispersing solution is prepared via a method which to obtain: by Graphene
Join in dispersant solution, utilize and shear dispersal device dispersion；
Preferably, the rotating speed of described shearing dispersal device is 1000～10000rpm；
Preferably, step (2) described Graphene is prepared into by the method for preparing graphene by using supercritical fluid
Arrive.
6. according to the method one of claim 3-5 Suo Shu, it is characterised in that mixed described in step (3)
Closing the concentration of positive electrode in liquid is 100～1200g/L；
Preferably, positive electrode described in step (3) be cobalt acid lithium, nickel cobalt lithium aluminate, nickle cobalt lithium manganate,
Any one or the combination of at least two in lithium nickelate, LiMn2O4 or lithium-rich manganese base material；
Preferably, be blended in described in step (3) continuously stirred under the conditions of carry out.
7. according to the method one of claim 3-6 Suo Shu, it is characterised in that heat described in step (4)
The temperature processed is 400-1000 DEG C；
Preferably, the time that described in step (4), heat treatment is carried out is 0.05-3min；
Preferably, step (4) described heat treatment is carried out in vertical atmosphere furnace.
8. according to the method one of claim 3-7 Suo Shu, it is characterised in that mist described in step (4)
Change and realized by peristaltic pump and nebulizer；
Preferably, mixed liquor is imported in nebulizer by described peristaltic pump according to the flow velocity of 0.01～10L/min；
Preferably, the droplet maximum particle diameter of described nebulizer ejection is 30～60 μm；
Preferably, described in step (4), protective atmosphere is argon and/or nitrogen atmosphere.
9. according to the method one of claim 3-8 Suo Shu, it is characterised in that described method includes walking as follows
Rapid:
(1) by Organic substance dispersant in solvent, obtaining Organic substance dispersant concentration is 20～100g/L
Dispersant solution；
(2) Graphene is joined in the dispersant solution that step (1) obtains, utilize and shear dispersal device
Disperseing, the rotating speed shearing dispersal device is 1000～10000rpm, and obtaining Graphene concentration is
The graphene dispersing solution of 4～20g/L；
(3) positive electrode is added in the graphene dispersing solution that step (2) obtains and continuously stirred, obtain
Positive electrode concentration is the mixed liquor of 100～1200g/L；
(4) mixed liquor is imported in nebulizer according to the flow velocity of 0.01～10L/min and is atomized by peristaltic pump,
The droplet maximum particle diameter of nebulizer ejection is 30～60 μm, and atomization air flow is downwardly into vertical atmosphere furnace,
Under the conditions of 400～1000 DEG C, heat treatment 0.05～3min, obtains composite positive pole.
10. utilize the lithium ion battery that the composite positive pole described in claim 1 or 2 prepares.
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| 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 |
| CN112635728A (en) * | 2020-12-16 | 2021-04-09 | 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 |
| 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 |
| CN114709404A (en) * | 2022-04-22 | 2022-07-05 | 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 |
| 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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