CN104934608A - Preparation method of in-situ graphene coated lithium ion battery cathode material - Google Patents
Preparation method of in-situ graphene coated lithium ion battery cathode material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 94
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000010406 cathode material Substances 0.000 title abstract description 15
- 238000011065 in-situ storage Methods 0.000 title abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 15
- 239000010405 anode material Substances 0.000 claims description 60
- 238000000498 ball milling Methods 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 22
- 235000012239 silicon dioxide Nutrition 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 18
- 239000010453 quartz Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012159 carrier gas Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 3
- -1 graphene modified lithium Chemical class 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 19
- 239000003708 ampul Substances 0.000 description 15
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical class [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 5
- 229910015645 LiMn Inorganic materials 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000009831 deintercalation Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 229910010710 LiFePO Inorganic materials 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000005536 Jahn Teller effect Effects 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002113 nanodiamond Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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 invention discloses a preparation method of an in-situ graphene coated lithium ion battery cathode material, and mainly relates to the technical field of lithium ion batteries, in particular to a preparation method of a graphene modified lithium battery cathode material. The method aims at solving the technical problems that the lithium battery cathode material is low in electronic conductivity and poor in cycle performance, and the physical graphene doped or carbon material coated lithium ion cathode material in the prior art is poor in coating effect, loose in coating and easy to separate. The method comprises the steps of allowing a carbon source to directly generate graphene on the surface of the lithium battery cathode material by a chemical vapor deposition method, and then allowing the graphene to coat the lithium battery cathode material in situ. The composite graphene is good in coating effect and higher in conductivity.
Description
Technical field
The present invention relates to technical field of lithium ion, relate to the application of highly electron conductive Graphene in anode material for lithium-ion batteries, be related specifically to a kind of preparation method of Graphene in-stiu coating anode material for lithium-ion batteries.
Technical background
Along with the development of science and technology, the development of novel green high efficient energy sources makes rapid progress, and lithium ion battery is high with its operating voltage, energy density is large, and have extended cycle life, charge efficiency is high, security performance is good, the advantages such as adaptive capacity to environment is strong is become to the focus studied now.Lithium ion battery be a kind of rely on lithium ion between a positive electrode and a negative electrode movement carry out the rechargeable battery of work, in charge and discharge process, Li
+come and go between two electrodes and embed and deintercalation: when charging to battery, Li
+from positive pole deintercalation, embed negative pole through electrolyte, negative pole is in rich lithium state; Equally, (use the process of battery) during electric discharge, the lithium ion be embedded in negative pole carbon-coating is deviate from, and move back again positive pole.The lithium ion returning positive pole is more, and discharge capacity is higher, and (lithium ion enters the process of positive electrode embedding, and the process left is deintercalation; Lithium ion enters the process of negative material insertion, and the process left is inserted de-).
Lithium ion battery has been taken as the leading factor with positive electrodes such as LiMn2O4, cobalt acid lithiums since appearance always: LiMn2O4 (LiMn
2o
4) there is the advantages such as raw material resources are abundant, cheap, nontoxic pollution-free, but LiMn2O4 (LiMn
2o
4) there is the capacity attenuation that caused by dissolving and Jahn-Teller effect of Mn i.e. cycle performance difference and the defect such as high-temperature behavior is poor soon, so the cycle performance of LiMn2O4 and high-temperature behavior still need to be further improved.At present, doping and surface modification improve the main path of LiMn2O4 performance.LiFePO4 (LiFePO
4) lattice stability good, the embedding of lithium ion and deviate from the impact of lattice little, there is good invertibity, and have lightweight, energy storage is large, power is large, the life-span is long, self discharge coefficient is little, Acclimation temperature wide ranges, aboundresources, security performance are good, nontoxic environmentally friendly and can be applicable to ask for something and compare the advantages such as exacting terms, LiFePO4 (LiFePO
4) become one of the most promising anode material for lithium-ion batteries, but pure LiFePO4 (LiFePO
4) material exists that cryogenic property is bad, conductivity is poor, energy density is low and the problem such as poor processability, limits its application in anode material for lithium-ion batteries, needs by its modification or carry out doping and improve its conductivity.Traditional material with carbon element is coated, high volence metal ion doping and the means such as metal nanoparticle mixing all can improve LiFePO4 (LiFePO
4) conductivity.But the coated volume energy density that can reduce positive electrode of traditional method of modifying carbon, also can hinder migration and the diffusion of lithium ion.Therefore, in order to improve LiFePO4 (LiFePO
4) high rate performance, overcome carbon coated give LiFePO4 (LiFePO
4) the negative effect that brings of energy density, wish by introducing Graphene to LiFePO4 (LiFePO
4) carry out composite modified.
Graphene is incorporated in lithium ion battery electrode material by people in recent years, the problem such as excessively slow to solve lithium ion mobility, the electronic conductivity of electrode is poor, resistivity increase between high rate charge-discharge bottom electrode and electrolyte.Graphene is the material with carbon element by individual layer or the two-dimentional hexagonal lattice structure of the tightly packed one-tenth of which floor carbon atom, is thin, the hardest nano material in known world.Under normal temperature, its electron mobility is more than 15000cm
2/ Vs, higher than CNT (carbon nano-tube) and crystalline silicon; Resistivity only has an appointment 10
-8Ω m, lower than copper and silver; Conductive coefficient up to 5300W/mK, higher than carbon nano-tube and diamond.Graphene is mainly used in solar cell, transducer, ultracapacitor and various electronic devices etc.Graphene and traditional anode material of lithium battery compound demonstrate some new electrochemical characteristics, and the general electronic conductivity of traditional anode material for lithium-ion batteries is lower: as LiCoO
2, LiMn
2o
4and LiFePO
4, its electronic conductivity is respectively 10
-4, 10
-6with 10
-9s/cm.And graphene conductive is good, mechanical strength is high, therefore utilize the high electronics of Graphene and ionic conductivity and high mechanical strength can significantly improve heavy-current discharge and the cycle performance of material.
Because Graphene specific area is large, mechanical strength is high, have unusual electric conductivity, therefore Graphene is advantageously material modified compared to traditional anode material of lithium battery.Graphene coated anode material of lithium battery is expected to break through the means such as the coated and nano metal ion doping of conventional carbon, realizes the breakthrough of lithium ion cell high-capacity.The preparation method of current Graphene mainly contains mechanical glass method, silicon carbide epitaxy is thought of a way, chemical vapour deposition technique and graphene oxide reducing process etc.
More existing team successfully use anode material for lithium-ion batteries such as Graphene modification LiMn2O4 and LiFePO4 etc. at present, but mostly just Graphene and lithium ion battery positive electrode are carried out physical blending:
Chinese patent literature CN103872287A (publication number) discloses a kind of by Graphene and the coated liFePO of carbon
4after anode material for lithium-ion batteries ball mill carries out ball milling mixing, obtain Graphene/liFePO
4the method of anode composite material of lithium ion battery, but just Graphene and iron phosphate powder have been carried out simple physical blending.Graphene small-sized, be nanometer materials, the dispersion in LiFePO4 is particularly difficult, and covered effect is also bad, coated loose easy disengaging.(Ding Y, Jiang Y, Xu F, the et al.Preparation of nano-structured LiFePO such as the Ding Yanhuai of University Of Xiangtan
4/ graphenecomposites by co-precipitation method [J] .Electrochemistry Communications, 2010,12 (1): 10-13.) use (NH
4)
2fe (SO
4)
26h
2O, NH
4h
2pO
4, the first co-precipitation of LiOH and Graphene, then the method sintered has prepared Graphene/liFePO
4anode material for lithium-ion batteries, but liFePO
4particle is on loose loading graphene sheet layer, makes liFePO
4anode material for lithium-ion batteries electronic conductivity improves by a small margin.Chinese Academy of Sciences's Ningbo material (ZhouX, Wang F, Zhu Y, the et al.Graphene modified LiFePO such as Zhou Xufeng
4cathode materials for high powerlithium ion batteries [J] .J.Mater.Chem., 2011,21 (10): 3353-3358.) having invented one prepares Graphene/liFePO
4the method of anode material for lithium-ion batteries: first use hummer legal system for graphene oxide (GO) aqueous solution, then after being mixed with LiFePO4 by graphene oxide (GO) aqueous solution, spraying dry prepares graphene oxide/liFePO
4compound, finally uses high temperature reduction graphene oxide (GO) to prepare Graphene/liFePO
4anode material for lithium-ion batteries.Although this kind of method makes liFePO
4the electronic conductivity of anode material for lithium-ion batteries effectively improves, but graphene oxide manufacturing cycle is oversize, is unfavorable for producing.The Cui Yongli of China Mining University (Cui Yongli, Xu Kun, Yuan Zheng, etc. Graphene/spinelle LiMn
2o
4nano-composite materials and chemical property [J]. Chinese Journal of Inorganic Chemistry, 2013,29 (1): 50-56.) Graphene/LiMn2O4 nano composite material has been prepared by cryodesiccated method, but LiMn2O4 is just reunited on the surface of graphene sheet layer, and be not that graphene coated is on the surface of LiMn2O4.
The present invention adopts chemical vapour deposition technique (chemical vapor deposition, CVD) at the surperficial direct growth Graphene of anode material of lithium battery, the anode material of lithium battery of the graphene coated obtained.Chemical vapour deposition technique (chemicalvapor deposition, CVD) be that reactive material issues biochemical reaction at quite high temperature, gaseous condition, the solid matter generated is deposited on the solid matrix surface of heating, and then the technology of obtained solid material.Chemical vapour deposition technique preparation technology is simple to operate, is easy to control, with low cost, can prepare high-quality, Graphene that the number of plies is few.Adopt chemical vapor infiltration both can overcome the shortcoming of Graphene easy reunion difficulties in dispersion in coated process at the surperficial direct growth Graphene of anode material of lithium battery anode material of lithium battery, the covered effect of Graphene can also be improved, make coated not easily loosely to come off.
Summary of the invention
Disperse uneven for high temperature sintering after solving simple physical doped graphene existing for the on the low side and prior art of traditional anode material for lithium-ion batteries electronic conductivity and anode material of lithium battery carries out coated occurred graphene powder, sintering covered effect is bad, coated loose easy disengaging, causes the series of technical of the limited grade of electronic conductivity room for promotion.The present invention's Graphene carries out modification to anode material of lithium battery, adopt chemical vapour deposition technique (chemical vapor deposition, CVD) at the surperficial direct growth Graphene of anode material of lithium battery, the anode material of lithium battery of the graphene coated obtained.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of preparation method of Graphene in-stiu coating anode material of lithium battery, be primarily characterized in that by described preparation method: chemical vapour deposition technique (chemical vapor deposition, CVD) is directly at anode material of lithium battery surface in situ coated graphite alkene.The concrete steps of described method comprise:
A. by catalyst, anode material of lithium battery powder and dispersant, after adding ball-milling medium, put into ball mill and carry out ball milling with rotating speed 100 ~ 300r/min, Ball-milling Time is 1 ~ 5h, make that catalyst mixes with anode material of lithium battery powder, uniform particle diameter, obtain presoma.
B. the presoma obtained is placed in drying oven and dries ball-milling medium, obtain the mixed-powder material of dry lithium battery anode material, dispersant and catalyst.
C. the mixture of powders of step B gained is put into reactor, reactor is put into heating furnace, with vacuum pump, reactor is vacuumized, then pass into inert carrier gas, repeated multiple timesly to carry out.
D. heating furnace is risen to uniform temperature, pass into carbon source, carbon source flows in reactor on powder with inert carrier gas, with powdered reaction, and reaction certain hour.
E. close temperature regulating device, carrier gas device, cooling, take out sample.
Described anode material of lithium battery is the combination of one or more in cobalt acid lithium, lithium titanate, LiFePO4, lithium hexafluoro phosphate, LiMn2O4.
Described dispersant is the combination of one or more in acetylene black, polyacrylamide (PAM), polyacrylic acid (PAA), graphite, polyethylene glycol (PEG), glucose, sucrose, and dispersant accounts for 0 ~ 20% of anode material of lithium battery quality.
Described catalyst is the combination of one or more in metallic copper, metallic nickel, metallic iron, metal platinum, metallic cobalt, metal rubidium, metal iridium, metal molybdenum, silicon dioxide, zinc oxide, alundum (Al2O3), magnesium oxide, and catalyst accounts for 0.1% ~ 5% of anode material of lithium battery quality.Described ball-milling medium is zirconia ball, agate ball, stainless steel ball.
Described reaction vessel can be glass container, ceramic vessel, crucible or high quartz container, and described inert carrier gas can be the combination of one or more in helium, nitrogen, argon gas.
Described carbon source is the combination of one or more in methane, ethane, propane, ethanol, methyl alcohol, propyl alcohol, benzene, hexachloro-benzene, ethene, acetylene, sucrose, glucose, polymethyl methacrylate (PMMA), and carbon source accounts for 1% ~ 10% of anode material of lithium battery quality.
The reaction temperature of described heating furnace is 500 ~ 1000 DEG C, and the reaction time is 10 ~ 200min.
The invention has the beneficial effects as follows:
A kind of preparation method of Graphene in-stiu coating anode material of lithium battery, use new preparation method's chemical vapour deposition technique (chemical vapor deposition, CVD) direct in-stiu coating Graphene on anode material of lithium battery, improve researcher by the problems such as Graphene is easily reunited, dispersion effect is poor in basis material, covered effect is bad existing for traditional simple physical blended graphene coated anode material of lithium battery method, anode material of lithium battery electronic conductivity can be significantly improved.Prepare graphene coated anode material of lithium battery simple to operate, experimental period is short, efficiently can prepare graphene coated anode material for lithium-ion batteries fast.The present invention, can also other anode material for lithium-ion batteries of modification except can modified phosphate iron lithium, LiMn2O4, anode material for lithium-ion batteries such as cobalt acid lithium, lithium titanate, lithium hexafluoro phosphate etc., applied widely.Anode material of lithium battery modified for the inventive method is applied to the application that will make lithium ion battery in lithium ion battery more extensive, has great value to the application of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the laser raman figure of graphene-coated lithium iron phosphate positive electrode prepared by the preparation method of a kind of Graphene in-stiu coating of the present invention anode material for lithium-ion batteries.
Fig. 2 is the scanning electron microscope diagram A of the graphene-coated lithium iron phosphate positive electrode of preparation.
Fig. 3 is the transmission electron microscope figure of the graphene-coated lithium iron phosphate positive electrode of preparation.
Fig. 4 is the X-ray diffractogram of the graphene coated manganate cathode material for lithium of preparation.
Fig. 5 is the transmission electron microscope figure of the graphene coated manganate cathode material for lithium of preparation.
Fig. 6 is the scanning electron microscope diagram B of the graphene-coated lithium iron phosphate positive electrode of preparation.
Embodiment
Below by embodiment, and by reference to the accompanying drawings, technical scheme of the present invention is carried out more specifically bright.
Embodiment 1
1. 1.5g SiO 2 powder and the mixing of 30g iron phosphate powder are put into ball mill, agate ball is as ball-milling medium, and put into ball mill and carry out ball milling with rotating speed 300r/min, Ball-milling Time is 5h, obtains presoma.
2. the presoma obtained being placed in drying oven dries to constant weight, obtains the mixed-powder material of LiFePO4 and catalyst.
3. the mixture of powders of step 2 gained is put into quartz ampoule, quartz ampoule is put into heating furnace, with vacuum pump, quartz ampoule is vacuumized, then pass into nitrogen, repeatedly carry out 3 times.
4. the temperature of heating furnace is risen to 650 DEG C, pass into 3mL methane gas, with powdered reaction, generate graphene coated on LiFePO4 surface.
5. after reaction time 50min, close heating furnace, disconnect nitrogen and make it under airtight environment, slowly cool.
6. after being cooled to room temperature, take out sample, the lithium iron phosphate positive material of graphene coated can be obtained, and sample is ground, vacuum drying treatment, compressing tablet, sintering, survey its conductivity by four probe method, obtaining conductivity is 4.2 × 10
-2s/cm, conductivity is greatly improved.Be the laser raman figure of graphene-coated lithium iron phosphate positive electrode, scanning electron microscope diagram and transmission electron microscope figure respectively in accompanying drawing 1 and accompanying drawing 2 and accompanying drawing 3, as can be seen from these figure, Graphene is coated on the surface of LiFePO4 well.
Embodiment 2
1. ball mill is put in the mixing of 1.5 metallic nickel powders, 30g LiMn2O4 powder and 0.9g graphite powder, agate ball is as ball-milling medium, and put into ball mill and carry out ball milling with rotating speed 100r/min, Ball-milling Time is 3h, obtains presoma.
2. the presoma obtained is placed in drying oven to dry to constant weight and obtain, to the mixed-powder material of LiMn2O4, dispersant and catalyst.
3. the mixture of powders of step 2 gained is put into ceramic vessel, quartz ampoule is put into heating furnace, with vacuum pump, quartz ampoule is vacuumized, then pass into nitrogen, repeatedly carry out 3 times.
4. the temperature of heating furnace is risen to 900 DEG C, pass into 2g benzene, with powdered reaction, generate graphene coated on LiMn2O4 surface.
5. after reaction time 50min, close heating furnace, disconnect nitrogen and make it under airtight environment, slowly cool.
6. after being cooled to room temperature, take out sample, the manganate cathode material for lithium of graphene coated can be obtained, and sample is ground, vacuum drying treatment, compressing tablet, sintering, survey its conductivity by four probe method, obtaining conductivity is 4.61 × 10
-4s/cm, conductivity is greatly improved.Accompanying drawing 4 and accompanying drawing 5 are X-ray diffractogram and the transmission electron microscope figure of the graphene coated manganate cathode material for lithium of embodiment 2 method gained.Generate the thin slice of Graphene as can be seen from the picture, and be coated on the surface of LiMn2O4 well.
Embodiment 3
1. ball mill is put in the mixing of 1g metallic copper powder, 30g LiMn2O4 powder and 6g sucrose, zirconia ball is as ball-milling medium, and put into ball mill and carry out ball milling with rotating speed 200r/min, Ball-milling Time is 5h, obtains presoma.
2. the presoma obtained being placed in drying oven dries to constant weight, obtains the mixed-powder material of LiMn2O4, dispersant and catalyst.
3. the mixture of powders of step 2 gained is put into quartz ampoule, quartz ampoule is put into heating furnace, with vacuum pump, quartz ampoule is vacuumized, then pass into argon gas, repeatedly carry out 3 times.
4. the temperature of heating furnace is risen to 1000 DEG C, pass into 3g methane, with powdered reaction, generate graphene coated on LiMn2O4 surface.
5. after reaction time 100min, close heating furnace, disconnect argon gas and make it under airtight environment, slowly cool.
6. after being cooled to room temperature, take out sample, the manganate cathode material for lithium of graphene coated can be obtained, and sample is ground, vacuum drying treatment, compressing tablet, sintering, survey its conductivity by four probe method, obtaining conductivity is 4.03 × 10
-4s/cm, conductivity is greatly improved.
Embodiment 4
1. ball mill is put in 1g metallic nickel, the mixing of metal molybdenum powder, 30g cobalt acid lithium powder and 4g polyacrylic acid (PAA) mixing, agate ball is as ball-milling medium, put into ball mill and carry out ball milling with rotating speed 250r/min, Ball-milling Time is 4h, obtains presoma.
2. the presoma obtained being placed in drying oven dries to constant weight, obtains the mixed-powder material of cobalt acid lithium, dispersant and catalyst.
3. the mixture of powders of step 2 gained is put into ceramic vessel, quartz ampoule is put into heating furnace, with vacuum pump, quartz ampoule is vacuumized, then pass into argon gas, repeatedly carry out 3 times.
4. the temperature of heating furnace is risen to 800 DEG C, pass into 1g ethene, with powdered reaction, generate graphene coated on cobalt acid lithium surface.
5. after reaction time 70min, close heating furnace, disconnect argon gas and make it under airtight environment, slowly cool.
6. after being cooled to room temperature, take out sample, the lithium cobaltate cathode material of graphene coated can be obtained, and sample is ground, vacuum drying treatment, compressing tablet, sintering, survey its conductivity by four probe method, conductivity is 2.6 × 10
-2s/cm, conductivity is greatly improved.
Embodiment 5
1. ball mill is put in 1.8g Zinc oxide powder mixture, 30g cobalt acid lithium powder and the mixing of 1g acetylene black, zirconia ball is as ball-milling medium, and put into ball mill and carry out ball milling with rotating speed 280r/min, Ball-milling Time is 2h, obtains presoma.
2. the presoma obtained being placed in drying oven dries to constant weight, obtains the mixed-powder material of cobalt acid lithium, dispersant and catalyst.
3. the mixture of powders of step 2 gained is put into ceramic vessel, quartz ampoule is put into heating furnace, with vacuum pump, quartz ampoule is vacuumized, then pass into helium, repeatedly carry out 3 times.
4. the temperature of heating furnace is risen to 900 DEG C, pass into 1g benzene, with powdered reaction, generate graphene coated on cobalt acid lithium surface.
5. after reaction time 60min, close heating furnace, disconnect argon gas and make it under airtight environment, slowly cool.
6. after being cooled to room temperature, take out sample, the lithium cobaltate cathode material of graphene coated can be obtained, and sample is ground, vacuum drying treatment, compressing tablet, sintering, survey its conductivity by four probe method, conductivity is 1.8 × 10
-2s/cm, conductivity is greatly improved.
Embodiment 6
1. ball mill is put in the mixing of 2g magnesium oxide powder mixture, 30g iron phosphate powder and 3g glucose, stainless steel ball is as ball-milling medium, and put into ball mill and carry out ball milling with rotating speed 300r/min, Ball-milling Time is 5h, obtains presoma.
2. the presoma obtained being placed in drying oven dries to constant weight, obtains the mixed-powder material of LiFePO4, dispersant and catalyst.
3. the mixture of powders of step 2 gained is put into quartz ampoule, quartz ampoule is put into heating furnace, with vacuum pump, quartz ampoule is vacuumized, then pass into argon gas, repeatedly carry out 3 times.
4. the temperature of heating furnace is risen to 600 DEG C, pass into 1.5g hexachloro-benzene, with powdered reaction, generate graphene coated on LiFePO4 surface.
5. after reaction time 55min, close heating furnace, disconnect argon gas and make it under airtight environment, slowly cool.
6. after being cooled to room temperature, take out sample, the lithium iron phosphate positive material of graphene coated can be obtained, and sample is ground, vacuum drying treatment, compressing tablet, sintering, survey its conductivity by four probe method, conductivity is 4.5 × 10
-2s/cm, conductivity is greatly improved.Accompanying drawing 6 is scanning electron microscope diagrams of graphene-coated lithium iron phosphate positive electrode, and as can be seen from this picture, Graphene is coated on the surface of LiFePO4 well.
The foregoing is only specific embodiments of the invention, but architectural feature of the present invention is not limited only to this, any those skilled in the art is in the field of the invention, and the change done or modification are all encompassed among the scope of the claims of the present invention.
Claims (8)
1. a preparation method for Graphene in-stiu coating anode material for lithium-ion batteries, is characterized in that described method, i.e. chemical vapour deposition technique (chemical vapor deposition, CVD), and the step of its preparation method comprises:
A. by catalyst, anode material of lithium battery powder and dispersant, after adding ball-milling medium, put into ball mill and carry out ball milling with rotating speed 100 ~ 300r/min, Ball-milling Time is 1 ~ 5h, make catalyst mix uniform particle diameter with anode material of lithium battery powder, obtain presoma;
B. the drying oven presoma obtained being placed in 50 ~ 100 DEG C is dried, and obtains dry anode material of lithium battery and the mixed-powder material of catalyst;
C. the mixture of powders of step B gained is put into reactor, reactor is put into heating furnace, with vacuum pump, reactor is vacuumized, then pass into inert carrier gas, repeated multiple timesly to carry out;
D. heating furnace is risen to uniform temperature, add carbon source, flow in reactor on powder with inert carrier gas, with powdered reaction a period of time;
E. close temperature regulating device, carrier gas device, cooling, take out sample.
2. the preparation method of a kind of Graphene in-stiu coating anode material for lithium-ion batteries according to claim 1, is characterized in that: described anode material of lithium battery is the combination of one or more in cobalt acid lithium, lithium titanate, LiFePO4, lithium hexafluoro phosphate, LiMn2O4.
3. the preparation method of a kind of Graphene in-stiu coating anode material for lithium-ion batteries according to claim 1, it is characterized in that: described dispersant is the combination of one or more in acetylene black, polyacrylamide (PAM), polyacrylic acid (PAA), graphite, polyethylene glycol (PEG), glucose, sucrose, and dispersant accounts for 0 ~ 20% of anode material of lithium battery powder quality.
4. the preparation method of a kind of Graphene in-stiu coating anode material for lithium-ion batteries according to claim 1, it is characterized in that: described catalyst is the combination of one or more in metallic copper, metallic nickel, metallic iron, metal platinum, metallic cobalt, metal rubidium, metal iridium, metal molybdenum, silicon dioxide, zinc oxide, alundum (Al2O3), magnesium oxide, catalyst accounts for 0.1% ~ 5% of anode material of lithium battery quality, and ball-milling medium is zirconia ball, agate ball, stainless steel ball.
5. the preparation method of a kind of Graphene in-stiu coating anode material for lithium-ion batteries according to claim 1, it is characterized in that: described reaction vessel can be glass container, ceramic vessel, crucible or high quartz container, described inert carrier gas can be one or more combination in helium, nitrogen, argon gas.
6. the preparation method of a kind of Graphene in-stiu coating anode material for lithium-ion batteries according to claim 1, it is characterized in that: described carbon source is the combination of one or more in methane, ethane, propane, ethanol, methyl alcohol, propyl alcohol, benzene, hexachloro-benzene, ethene, acetylene, sucrose, glucose, polymethyl methacrylate (PMMA), and carbon source accounts for 1% ~ 10% of anode material of lithium battery quality.
7. the preparation method of a kind of Graphene in-stiu coating anode material for lithium-ion batteries according to claim 1, is characterized in that: the heating reaction temperature of described heating furnace is 500-1000 DEG C.
8. the preparation method of a kind of Graphene in-stiu coating anode material for lithium-ion batteries according to claim 1, is characterized in that: the time that described carbon source and anode material of lithium battery react is 10 ~ 200min.
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