CN110048097A - Negative electrode of lithium ion battery silicon/carbon graphite composite material preparation method - Google Patents
Negative electrode of lithium ion battery silicon/carbon graphite composite material preparation method Download PDFInfo
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- CN110048097A CN110048097A CN201910231337.6A CN201910231337A CN110048097A CN 110048097 A CN110048097 A CN 110048097A CN 201910231337 A CN201910231337 A CN 201910231337A CN 110048097 A CN110048097 A CN 110048097A
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- silicon
- carbon
- composite material
- graphite composite
- negative electrode
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 239000010703 silicon Substances 0.000 title claims abstract description 112
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 112
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 84
- 239000010439 graphite Substances 0.000 title claims abstract description 84
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 110
- 239000000463 material Substances 0.000 claims abstract description 42
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 15
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000007790 solid phase Substances 0.000 claims abstract description 13
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 239000007791 liquid phase Substances 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 238000001694 spray drying Methods 0.000 claims abstract description 6
- 239000000320 mechanical mixture Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 62
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 23
- 238000000498 ball milling Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 claims description 14
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 10
- 238000000713 high-energy ball milling Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
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- 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 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011295 pitch Substances 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229910007981 Si-Mg Inorganic materials 0.000 claims description 3
- 229910008316 Si—Mg Inorganic materials 0.000 claims description 3
- 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 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 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 3
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- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 229910021382 natural graphite Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920001690 polydopamine Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910018594 Si-Cu Inorganic materials 0.000 claims description 2
- 229910008465 Si—Cu Inorganic materials 0.000 claims description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229920005990 polystyrene resin Polymers 0.000 claims description 2
- 238000005507 spraying Methods 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229940022682 acetone Drugs 0.000 claims 1
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 claims 1
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 150000002240 furans Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- 239000000243 solution Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 32
- 235000019441 ethanol Nutrition 0.000 description 27
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- 238000012360 testing method Methods 0.000 description 16
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- 239000003595 mist Substances 0.000 description 8
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
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- 230000000630 rising effect Effects 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000011856 silicon-based particle Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
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- 150000003376 silicon Chemical class 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910007933 Si-M Inorganic materials 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
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- 239000002585 base Substances 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
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- 239000011347 resin Substances 0.000 description 1
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- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/362—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention provides a kind of preparation method of negative electrode of lithium ion battery silicon/carbon graphite composite material, comprising steps of obtained silicon source is pre-processed and purified after silicon-containing material is dried；Silicon source is compound using two kinds of different modes progress with organic carbon source, high purity graphite, silicon/carbon graphite composite material is made: silicon source and organic carbon source are subjected to solid phase or the compound obtained presoma of liquid phase, then presoma is placed in high temperature pyrolysis under atmosphere of inert gases and obtains silicon carbon material, silicon carbon material and high purity graphite are subjected to mechanical mixture again, obtain silicon/carbon graphite composite material；Silicon source, organic carbon source, high purity graphite are mixed and added into dispersing agent and be uniformly dispersed, high temperature pyrolysis under atmosphere of inert gases is placed on by spray drying, obtains silicon/carbon graphite composite material.The present invention prepares gained negative electrode material and electric conductivity can be improved and inhibit the volume expansion of silicon, improves the cycle performance of battery, is suitable for large-scale production.
Description
[technical field]
The invention belongs to cell negative electrode material technical field more particularly to a kind of negative electrode of lithium ion battery silicon/carbon graphites
The preparation method of composite material.
[background technique]
Lithium ion battery has that operating voltage is high, specific energy is big, have extended cycle life, pollution-free and memory-less effect etc. is excellent
Point has been widely used in laptop, mobile phone and other portable electronics, and gradually to electric car, satellite with
And the high-power systems field such as large-scale energy-storage battery is expanded.Negative electrode of lithium ion battery mainly uses graphite negative electrodes material, but its
Theoretical specific capacity is low (372mAh/g), and cycle efficieny is relatively low for the first time, is unable to satisfy the needs of high specific energy batteries, and searching has
The negative electrode material of more height ratio capacity is one of the important directions of current Study on Li-ion batteries.At present silicon based anode material because its from
It is the higher theoretical specific capacity of body (3752mAh/g), environmental-friendly and low in cost and be concerned.But silicon based anode material is in reality
Have the defects that poorly conductive and process of intercalation volume expansion, this Volumetric expansion not only result in solid electricity in the application of border
Destruction, the dusting generated repeatedly with silicon electrode for solving matter interfacial film (SEI film), can also make electrode slowly lose electricity with collector and connect
Touching, leads to the raising of electrode material to fall off with irreversible capacity, eventually leads to the reduction of battery whole volume, seriously affect and follow
Ring performance.
Researcher has carried out a large amount of modification to silicon in the prior art, including the second constituent element of incorporation forms Si-M and closes
Golden system, the porous of silicon or nanosizing processing, to reduce the dimension of silicon materials, by prepare nano particle, nano wire or
The materials such as nanotube, to solve silicon bulk effect that may be present in charge and discharge process.In addition, also for example by structure design
Core-shell structure etc. is modified silicon-based anode.But single modified method is difficult to make the chemical property of silicon based anode material full
The requirement of sufficient commercialized development is unfavorable for realizing large-scale preparation and application.
[summary of the invention]
The present invention proposes a kind of preparation method of negative electrode of lithium ion battery silicon/carbon graphite composite material, is changed by a variety of
Property means to silicon based anode material carry out it is composite modified, the negative electrode material haveing excellent performance is prepared, be suitable for large-scale production.
To achieve the goals above, the present invention provides a kind of system of negative electrode of lithium ion battery silicon/carbon graphite composite material
Preparation Method, comprising the following steps:
1) it is pre-processed and is purified after drying silicon-containing material, the silicon source for meeting particle size requirements is made；
2) silicon source is compound using the progress of the following two kinds different modes with organic carbon source, high purity graphite, obtained silicon/
Carbon graphite composite material；
A, the silicon source and the organic carbon source are subjected to solid phase or the compound obtained presoma of liquid phase, then by the forerunner
Body is placed in high temperature pyrolysis under atmosphere of inert gases and obtains silicon carbon material, then the silicon carbon material and the high purity graphite are carried out machine
Tool mixing, obtains the silicon/carbon graphite composite material；
B, the silicon source, the organic carbon source, the high purity graphite are mixed and added into dispersing agent and be uniformly dispersed, by spray
Mist drying is placed on high temperature pyrolysis under atmosphere of inert gases, obtains the silicon/carbon graphite composite material.
In a preferred embodiment, in step 1), the pretreated method include drying, corase grinding, magnetic agitation,
One of mechanical stirring, high-energy ball milling, sand milling are several；The method of the purification includes that pickling, alkali cleaning, washing, alcohol are washed
One of or it is several, wherein being washed for the last time using alcohol in the method for the purification.
In a preferred embodiment, acid used by the pickling is in sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid
One or several kinds, acid concentration used by the pickling are 1M-18M, and the time of the pickling is 10-30h；The alkali cleaning institute
The alkali of use is selected from one of sodium hydroxide, potassium hydroxide, barium hydroxide and ammonium hydroxide or several, used by the alkali cleaning
Alkali concentration is 1M-12M, and the time of the alkali cleaning is 8-20h；Alcohol used by the alcohol is washed is selected from dehydrated alcohol, isopropanol, just
One of butanol is several, and the time that the alcohol is washed is 10-30h.
In a preferred embodiment, the silicon-containing material is thick silicon, silicon copper, silico-aluminum, Si-Mg alloy, aluminium
One of silicon copper, silicon kirsite are several；The organic carbon source is citric acid, pitch, sucrose, glucose, poly- second
Alkene pyrrolidone, Kynoar, polyvinyl alcohol, polythiophene, epoxy resin, phenolic resin, polyacrylonitrile, gathers polyethylene glycol
One of styrene resin, poly-dopamine are several；The high purity graphite is artificial graphite, natural graphite or interphase
One of carbosphere is several.
In a preferred embodiment, in step 2), the inert gas is high-purity argon gas or nitrogen, the high temperature
The method of pyrolysis includes: first to be warming up to 300-500 DEG C of range inside holding 1-24h, is then warming up within the scope of 600-1200 DEG C again
And 1-24h is kept the temperature, it finally cools, wherein heating rate is 2-10 DEG C/min.
In a preferred embodiment, the meso-position radius of the silicon source is having a size of 10-500nm, in the high purity graphite
Position diameter is having a size of 10-18 μm；The silicon/carbon graphite composite material meso-position radius is having a size of 10-22 μm.
In a preferred embodiment, the dispersing agent includes pure water, dehydrated alcohol, acetone, sodium carboxymethylcellulose
One or more of solution, N-Methyl pyrrolidone or tetrahydrofuran, wherein finely dispersed method include solid phase be blended,
Magnetic agitation, ultrasonic disperse, ball milling, churned mechanically one or more.
In a preferred embodiment, the solid phase or the compound method of liquid phase include that solid phase is blended, liquid phase is wrapped in situ
It covers or is spray-dried；The temperature of the spray drying is 120-280 DEG C.
In a preferred embodiment, in step A, the quality of silicon accounts for 70-95%, the quality of carbon in the silicon carbon material
Account for 5-30%；The mass percent that the silicon carbon material and the high purity graphite carry out mechanical mixture is (5-20%): (80-
95%).
In a preferred embodiment, in step B, silicon ingredient in the silicon/carbon graphite composite material, carbon component with
The mass percent of graphite content is (5-20%): (5-20%): (70-80%).
Compared with prior art, the beneficial effects of the present invention are: first by pretreatment by silicon-containing material particle nanometer
Change, the material structural stress that volume expansion generates in charge and discharge process variation can be alleviated, improve the structural stability of material,
And material particle size reduces the diffusion path that can shorten lithium ion, improves the diffusion velocity of lithium ion, improves the big multiplying power of material
Discharge performance；It is compound by carbon coating and graphite again, the carbon material of one layer of high conductivity is coated on silicon particle surface, can be improved
Electric conductivity, while can inhibit the volume expansion of silicon, the cycle performance of battery is improved, and graphite particle is the volume expansion of silicon materials
Buffering matrix is provided, the stability of electrode entirety is further increased, is suitable for large-scale production.
[Detailed description of the invention]
Fig. 1 is XRD diagram of the silicon-containing material after overpickling ball milling in the embodiment of the present invention 7；
Fig. 2 is XRD diagram of the silicon-containing material after sanded treatment in the embodiment of the present invention 7；
Fig. 3 is the SEM figure of the raw material silicon copper used in the embodiment of the present invention；
Fig. 4 schemes for the SEM of silicon/carbon graphite composite material obtained in the embodiment of the present invention 1；
Fig. 5 is the cyclic curve that the button cell assembled in the embodiment of the present invention 8 is tested under 0.1c multiplying power
Figure.
[specific embodiment]
The present invention provides a kind of preparation method of negative electrode of lithium ion battery silicon/carbon graphite composite material, specifically include with
Lower step:
1) it is pre-processed and is purified after drying silicon-containing material, the silicon source for meeting particle size requirements is made；
2) silicon source is compound using the progress of the following two kinds different modes with organic carbon source, high purity graphite, obtained silicon/
Carbon graphite composite material.
A, the silicon source and the organic carbon source are subjected to solid phase or the compound obtained presoma of liquid phase, then by the forerunner
Body is placed in high temperature pyrolysis under atmosphere of inert gases and obtains silicon carbon material, then the silicon carbon material and the high purity graphite are carried out machine
Tool mixing, obtains the silicon/carbon graphite composite material.
B, the silicon source, the organic carbon source, the high purity graphite are mixed and added into dispersing agent and be uniformly dispersed, by spray
Mist drying is placed on high temperature pyrolysis under atmosphere of inert gases, obtains the silicon/carbon graphite composite material.
Specifically, the pretreated method includes drying, corase grinding, magnetic agitation, mechanical stirring, high energy in step 1)
One of ball milling, sand milling are several；The method of the purification includes that pickling, alkali cleaning, washing, alcohol one of are washed or several
Kind, wherein being washed for the last time using alcohol in the method for the purification.
Acid used by the pickling is selected from one of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid or several, the pickling
Used acid concentration is 1M-18M, and the time of the pickling is 10-30h；Alkali used by the alkali cleaning be selected from sodium hydroxide,
One of potassium hydroxide, barium hydroxide and ammonium hydroxide are several, and alkali concentration used by the alkali cleaning is 1M-12M, the alkali
The time washed is 8-20h；Alcohol used by the alcohol is washed is selected from one of dehydrated alcohol, isopropanol, n-butanol or several,
The time that the alcohol is washed is 10-30h.
The silicon-containing material is thick silicon, in silicon copper, silico-aluminum, Si-Mg alloy, Al-Si-Cu alloy, silicon kirsite
It is one or several kinds of；The organic carbon source is citric acid, pitch, sucrose, glucose, polyvinylpyrrolidone, polyethylene glycol, gathers
Vinylidene, polyvinyl alcohol, polythiophene, epoxy resin, phenolic resin, polyacrylonitrile, polystyrene resin, in poly-dopamine
One or several kinds, wherein pitch is one or both of selected from coal tar pitch and petroleum asphalt；The high purity graphite be artificial graphite,
One of natural graphite or carbonaceous mesophase spherules are several.
In step 2), the inert gas is high-purity argon gas or nitrogen, and the method for the high temperature pyrolysis includes: first to heat up
To 300-500 DEG C of range inside holding 1-24h, 1-24h is then warming up within the scope of 600-1200 DEG C and kept the temperature again, finally cooling drop
Temperature, wherein heating rate is 2-10 DEG C/min.
The meso-position radius of the silicon source is having a size of 10-500nm, and the meso-position radius of the high purity graphite is having a size of 10-18 μm；It is described
Silicon/carbon graphite composite material meso-position radius is having a size of 10-22 μm.The dispersing agent includes pure water, dehydrated alcohol, acetone, carboxylic first
One or more of base sodium cellulosate solution, N-Methyl pyrrolidone or tetrahydrofuran, wherein finely dispersed method packet
Include solid phase blending, magnetic agitation, ultrasonic disperse, ball milling, churned mechanically one or more.The solid phase or the compound side of liquid phase
Method includes solid phase blending, liquid phase in-stiu coating or spray drying；The temperature of the spray drying is 120-280 DEG C.
Further, in step A, the quality of silicon accounts for 70-95% in the silicon carbon material, and the quality of carbon accounts for 5-30%；Institute
It states silicon carbon material and the high purity graphite carries out the mass percent of mechanical mixture as (5-20%): (80-95%).In step B,
The mass percent of silicon ingredient, carbon component and graphite content is (5-20%): (5- in the silicon/carbon graphite composite material
20%): (70-80%).
The present invention is described in more detail combined with specific embodiments below, but the present invention is not limited to these Examples.This
Silicon/carbon graphite composite material is prepared in inventive embodiments by being prepared by mixing into slurry with conductive agent, binder etc., applies
Electrode circle piece is struck out after cloth drying, button cell is assembled into glove box, then carry out electric performance test, the matter of a variety of materials
Measuring accounting is silicon/carbon graphite composite material 70%-91%, conductive agent 5%-15%, binder 4%-20% respectively.
Embodiment 1
(1) drying of 500g silicon copper is weighed, the hydrochloric acid 1000g of 2M is added, stirs 12h under magnetic stirring, after standing
Supernatant is poured out, water is added and ethyl alcohol cleans 3 times repeatedly, test solution ph is then added in sodium hydroxide solution if acidity
With extremely neutrality；It is eventually adding dehydrated alcohol 500g (material: the mass ratio of ethyl alcohol is 1:1), adds the agate ball of different-diameter
2500g (ball: the mass ratio of material is 5:1) carries out high-energy ball milling, wherein the agate ball 1500g of diameter 5mm, the agate of diameter 8mm
The agate ball 250g of ball 750g, diameter 1cm, mixing and ball milling time 12h, revolving speed 250r/min, the product drying after collecting ball milling
It is spare, test granularity, pattern or the crystal form of product.
(2) it weighs 53.3g citric acid and is dissolved in 2000ml pure water and solution is made, take products therefrom in above-mentioned steps (1)
200g is added in above-mentioned solution, carries out mist projection granulating after stirring 2h, is loaded into porcelain boat later and is placed in tube furnace in nitrogen gas
It is calcined under atmosphere, temperature is set as rising to 700 DEG C of holding 3h with the heating rate of 2 DEG C/min, takes out and produces after cooled to room temperature
Object is fully ground uniformly.
(3) weighing products therefrom and artificial graphite in above-mentioned steps (2) can be obtained by the mass ratio mixed grinding of 5:95
To silicon/carbon graphite composite material.
(4) using gained silicon/carbon graphite composite material in above-mentioned steps (3) as active material and conductive agent, binder etc.
It is mixed and made into slurry and is assembled into button cell and carry out half electrical testing, wherein active material accounting 91%, conductive agent accounting 5%,
Binder accounting 4%.
Embodiment 2
(1) drying of 500g silicon copper is weighed, the hydrochloric acid 1000g of 2M is added, stirs 12h under magnetic stirring, after standing
Supernatant is poured out, water is added and ethyl alcohol cleans 3 times repeatedly, test solution ph is then added in sodium hydroxide solution if acidity
With extremely neutrality；It is eventually adding dehydrated alcohol 500g (material: the mass ratio of ethyl alcohol is 1:1), adds the agate ball of different-diameter
2500g (ball: the mass ratio of material is 5:1) carries out high-energy ball milling, wherein the agate ball 1500g of diameter 5mm, the agate of diameter 8mm
The agate ball 250g of ball 750g, diameter 1cm, mixing and ball milling time 12h, revolving speed 250r/min, the product drying after collecting ball milling
It is spare.
(2) it weighs 133g polyvinylpyrrolidone and is dissolved in 4000ml pure water and solution is made, take obtained by above-mentioned steps (1)
Product 200g is added in above-mentioned solution, is granulated by spraying after stirring 2h, is loaded into porcelain boat later and is placed in tube furnace in nitrogen
It is calcined under gas atmosphere, temperature is set as rising to 250 DEG C of holding 2h with the heating rate of 2 DEG C/min, then with the heating speed of 2 DEG C/min
Rate rises to 650 DEG C of holding 2h, takes out product after cooled to room temperature and is fully ground.
(3) weighing products therefrom and artificial graphite in above-mentioned steps (2) can be obtained by the mass ratio mixed grinding of 5:95
To silicon/carbon graphite composite material.
(4) using gained silicon/carbon graphite composite material in above-mentioned steps (3) as active material and conductive agent, binder etc.
It is mixed and made into slurry and is assembled into button cell and carry out half electrical testing, wherein active material accounting 91%, conductive agent accounting 5%,
Binder accounting 4%.
Embodiment 3
(1) drying of 500g silicon copper is weighed, the hydrochloric acid 1000g of 2M is added, stirs 12h under magnetic stirring, after standing
Supernatant is poured out, water and ethyl alcohol is added to clean repeatedly 3 times, tests solution ph, if acidity, then sodium hydroxide solution neutralization is added
To neutrality, it is eventually adding dehydrated alcohol 500g (material: the mass ratio of ethyl alcohol is 1:1), adds the agate ball of different-diameter
2500g (ball: the mass ratio of material is 5:1) carries out high-energy ball milling, wherein the agate ball 1500g of diameter 5mm, the agate of diameter 8mm
The agate ball 250g of ball 750g, diameter 1cm, the mixing and ball milling time, revolving speed 250r/min, the product after collecting ball milling was dried for 24 hours
It is spare.
(2) it weighs 53.3g citric acid and is dissolved in 2000ml pure water and solution is made, take products therefrom in above-mentioned steps (1)
200g is added in above-mentioned solution, carries out mist projection granulating after stirring 2h, is loaded into porcelain boat later and is placed in tube furnace in nitrogen gas
It is calcined under atmosphere；Temperature is set as rising to 700 DEG C of holding 3h with the heating rate of 2 DEG C/min, takes out sample after cooled to room temperature
Product are fully ground.
(3) weighing products therefrom and artificial graphite in above-mentioned steps (2) can be obtained by the mass ratio mixed grinding of 5:95
To silicon/carbon graphite composite material.
(4) using gained silicon/carbon graphite composite material in above-mentioned steps (3) as active material and conductive agent, binder etc.
It is mixed and made into slurry and is assembled into button cell and carry out half electrical testing, wherein active material accounting 91%, conductive agent accounting 5%,
Binder accounting 4%.
Embodiment 4
(1) drying of 500g silicon copper is weighed, the hydrochloric acid 1000g of 2M is added, stirs 12h under magnetic stirring, after standing
Supernatant is poured out, water and ethyl alcohol is added to clean repeatedly 3 times, tests solution ph, if acidity, then sodium hydroxide solution neutralization is added
To neutrality, it is eventually adding dehydrated alcohol 500g (material: the mass ratio of ethyl alcohol is 1:1), adds the agate ball of different-diameter
2500g (ball: the mass ratio of material is 5:1) carries out high-energy ball milling, wherein the agate ball 1500g of diameter 5mm, the agate of diameter 8mm
The agate ball 250g of ball 750g, diameter 1cm, the mixing and ball milling time, revolving speed 250r/min, the product after collecting ball milling was dried for 24 hours
It is spare.
(2) it weighs 133g polyvinylpyrrolidone and is dissolved in 4000ml pure water and solution is made, take institute in above-mentioned steps (1)
It obtains product 200g to be added in above-mentioned solution, carries out mist projection granulating after stirring 2h, be loaded into porcelain boat later and be placed in tube furnace
It is calcined under nitrogen atmosphere；Temperature setting rises to 250 DEG C of holding 2h with the heating rate of 2 DEG C/min, then with the heating speed of 2 DEG C/min
Rate rises to 650 DEG C of holding 2h, takes out product after cooled to room temperature and is fully ground.
(3) weighing products therefrom and artificial graphite in above-mentioned steps (2) can be obtained by the mass ratio mixed grinding of 5:95
To silicon/carbon graphite composite material.
(4) using gained silicon/carbon graphite composite material in above-mentioned steps (3) as active material and conductive agent, binder etc.
It is mixed and made into slurry and is assembled into button cell and carry out half electrical testing, wherein active material accounting 91%, conductive agent accounting 5%,
Binder accounting 4%.
Embodiment 5
(1) drying of 500g silicon copper is weighed, the hydrochloric acid 1000g of 2M is added, is stirred for 24 hours, after standing under magnetic stirring
Supernatant is poured out, water and ethyl alcohol is added to clean repeatedly 3 times, tests solution ph, if acidity, then sodium hydroxide solution neutralization is added
To neutrality, it is eventually adding dehydrated alcohol 500g (material: the mass ratio of ethyl alcohol is 1:1), adds the agate ball of different-diameter
2500g (ball: the mass ratio of material is 5:1) carries out high-energy ball milling, wherein the agate ball 1500g of diameter 5mm, the agate of diameter 8mm
The agate ball 250g of ball 750g, diameter 1cm, the mixing and ball milling time, revolving speed 250r/min, the product after collecting ball milling was dried for 24 hours
It is spare.
(2) it weighs 133g polyvinylpyrrolidone and is dissolved in 4000ml pure water and solution is made, take institute in above-mentioned steps (1)
It obtains product 200g to be added in above-mentioned solution, carries out mist projection granulating after stirring 2h, be loaded into porcelain boat later and be placed in tube furnace
It is calcined under nitrogen atmosphere；Temperature setting rises to 250 DEG C of holding 2h with the heating rate of 2 DEG C/min, then with the heating speed of 2 DEG C/min
Rate rises to 650 DEG C of holding 2h, takes out product after cooled to room temperature and is fully ground.
(3) weighing products therefrom and artificial graphite in above-mentioned steps (2) can be obtained by the mass ratio mixed grinding of 5:95
To silicon/carbon graphite composite material.
(4) using gained silicon/carbon graphite composite material in above-mentioned steps (3) as active material and conductive agent, binder etc.
It is mixed and made into slurry and is assembled into button cell and carry out half electrical testing, wherein active material accounting 91%, conductive agent accounting 5%,
Binder accounting 4%.
Embodiment 6
(1) drying of 500g silicon copper is weighed, the hydrochloric acid 1000g of 2M is added, is stirred for 24 hours, after standing under magnetic stirring
Supernatant is poured out, water and ethyl alcohol is added to clean repeatedly 3 times, tests solution ph, if acidity, then sodium hydroxide solution neutralization is added
To neutrality, it is eventually adding dehydrated alcohol 500g (material: the mass ratio of ethyl alcohol is 1:1), adds the agate ball of different-diameter
2500g (ball: the mass ratio of material is 5:1) carries out high-energy ball milling, wherein the agate ball 1500g of diameter 5mm, the agate of diameter 8mm
The agate ball 250g of ball 750g, diameter 1cm, the mixing and ball milling time, revolving speed 250r/min, the product after collecting ball milling was dried for 24 hours
It is spare.
(2) it weighs 11.76g glucose (being 10% calculating by pyrolysis carbon content in core-shell material after sintering) and is added to 667g
Solution is made in pure water, adds above-mentioned steps (1) products therefrom 20g and artificial graphite 168.24g in above-mentioned solution, stirs
Mist projection granulating is carried out after 3h, is loaded into porcelain boat later and is placed in tube furnace and calcines in a nitrogen atmosphere；Temperature setting with 2 DEG C/
The heating rate of min rises to 900 DEG C of holding 3h, takes out product after cooled to room temperature, it is compound that silicon/carbon graphite can be obtained
Material.
(3) using gained silicon/carbon graphite composite material in above-mentioned steps (2) as active material and conductive agent, binder etc.
It is mixed and made into slurry and is assembled into button cell and carry out half electrical testing, wherein active material accounting 91%, conductive agent accounting 5%,
Binder accounting 4%.
Embodiment 7
(1) drying of 500g silicon copper is weighed, the hydrochloric acid 1000g of 2M is added, is stirred for 24 hours, after standing under magnetic stirring
Supernatant is poured out, water and ethyl alcohol is added to clean repeatedly 3 times, tests solution ph, if acidity, then sodium hydroxide solution neutralization is added
To neutrality, it is eventually adding dehydrated alcohol 500g (material: the mass ratio of ethyl alcohol is 1:1), adds the agate ball of different-diameter
2500g (ball: the mass ratio of material is 5:1) carries out high-energy ball milling, wherein the agate ball 1500g of diameter 5mm, the agate of diameter 8mm
The agate ball 250g of ball 750g, diameter 1cm, the mixing and ball milling time, revolving speed 250r/min continued to be sanded, sand after taking-up for 24 hours
Revolving speed 600r/min is ground, time 2h is sanded, the product after being sanded is collected and is dried for standby.
(2) it weighs 133g polyvinylpyrrolidone and is dissolved in 4000ml pure water and solution is made, take institute in above-mentioned steps (1)
It obtains product 200g to be added in above-mentioned solution, carries out mist projection granulating after stirring 2h, be loaded into porcelain boat later and be placed in tube furnace
It is calcined under nitrogen atmosphere；Temperature setting rises to 250 DEG C of holding 2h with the heating rate of 2 DEG C/min, then with the heating speed of 2 DEG C/min
Rate rises to 650 DEG C of holding 2h, takes out product after cooled to room temperature and is fully ground.
(3) weighing products therefrom and artificial graphite in above-mentioned steps (2) can be obtained by the mass ratio mixed grinding of 5:95
To silicon/carbon graphite composite material.
(4) using gained silicon/carbon graphite composite material in above-mentioned steps (3) as active material and conductive agent, binder etc.
It is mixed and made into slurry and is assembled into button cell and carry out half electrical testing, wherein active material accounting 91%, conductive agent accounting 5%,
Binder accounting 4%.
Embodiment 8
(1) drying of 500g silicon copper is weighed, the hydrochloric acid 1000g of 2M is added, is stirred for 24 hours, after standing under magnetic stirring
Supernatant is poured out, water and ethyl alcohol is added to clean repeatedly 3 times, tests solution ph, if acidity, then sodium hydroxide solution neutralization is added
To neutrality, it is eventually adding dehydrated alcohol 500g (material: the mass ratio of ethyl alcohol is 1:1), adds the agate ball of different-diameter
2500g (ball: the mass ratio of material is 5:1) carries out high-energy ball milling, wherein the agate ball 1500g of diameter 5mm, the agate of diameter 8mm
The agate ball 250g of ball 750g, diameter 1cm, the mixing and ball milling time, revolving speed 250r/min continued to be sanded, sand after taking-up for 24 hours
Revolving speed 600r/min is ground, time 2h is sanded, the product after being sanded is collected and is dried for standby.
(2) weigh 30g aluminum sulfate, 65g ammonium formate is dissolved in 300ml water and solution is made, add institute in above-mentioned steps (1)
Product 30g, first magnetic agitation 60min are obtained, 70 DEG C of stirring 2h is again heated to, is centrifuged after sedimentation, repeatedly dried afterwards using alcohol washes
It is dry, it is then added in polyvinylpyrrolidonesolution solution, is spray-dried after stirring 2h, is loaded into porcelain boat later and is placed in tubular type
It is calcined in a nitrogen atmosphere in furnace；Temperature setting rises to 900 DEG C of holding 3h with the heating rate of 2 DEG C/min, naturally cools to room
It is taken out after temperature, finally cleaning carbonized product after centrifugation drying with 10%HCl solution can be obtained silicon/carbon graphite composite material.
(3) using gained silicon/carbon graphite composite material in above-mentioned steps (2) as active material and conductive agent, binder etc.
It is mixed and made into slurry and is assembled into button cell and carry out half electrical testing, wherein active material accounting 91%, conductive agent accounting 5%,
Binder accounting 4%.
At XRD (X-ray diffraction) the respectively product and sand milling to silicon-containing material in embodiment 7 after overpickling ball milling
Product after reason is analyzed, as depicted in figs. 1 and 2.Raw material copper silicon used in the examples is closed using SEM (scanning electron microscope)
Gold carries out morphology analysis, as shown in figure 3, feedstock Particle size is larger in figure, and can receive silicon-containing material particle after pre-processing
Meter Hua, nanometer size effect can alleviate the material structural stress that volume expansion generates in charge and discharge process variation, improve material
The structural stability of material, while the reduction of material particle size can shorten the diffusion path of lithium ion, improve the diffusion speed of lithium ion
Degree, improves the big multiplying power discharging property of material.
Morphology analysis is carried out to silicon obtained in embodiment 1/carbon graphite composite material using SEM (scanning electron microscope), is such as schemed
Shown in 4, morphologically, by the particle accumulation of many Nano grades to the particle for being formed together micron size, silicon particle uniformly divides
It is dispersed in carbon wrapping layer, on the one hand can be improved electric conductivity, on the other hand can inhibit the volume expansion of silicon, while also completely cutting off
Silicon particle is directly contacted with electrolyte, avoids SEI film from generating repeatedly, to improve the cycle performance of material；And graphite particle
Buffering matrix is provided for the volume expansion of silicon materials.
Further, to the silicon of embodiment 1-8 acquisition/carbon graphite composite material assembling button cell in 0.1C multiplying power
Lower carry out charge and discharge cycles, voltage range are 0~2V, and cycle-index is 20 times, and test result is as shown in table 1.
Good cyclical stability is all had by the button cell that embodiment 1-8 is assembled it can be seen from data in table 1,
Wherein, capacity retention ratio is after button cell 20 times circulations of the silicon obtained by embodiment 8/carbon graphite composite material assembling
91.0%.It should be noted that silicon obtained/carbon graphite composite material assembling button cell is in 0.1c multiplying power in embodiment 8
The lower cyclic curve figure tested is as shown in Figure 5.
Table 1
The foregoing is merely illustrative of the preferred embodiments of the present invention, is to combine specific preferred embodiment to institute of the present invention
The further description of work is, and it cannot be said that specific implementation of the invention is confined to these explanations.It is all in spirit of the invention and
Made any modifications, equivalent replacements, and improvements etc., should be included within the scope of the present invention within principle.
Claims (10)
1. a kind of negative electrode of lithium ion battery silicon/carbon graphite composite material preparation method, which is characterized in that including following step
It is rapid:
1) it is pre-processed and is purified after drying silicon-containing material, the silicon source for meeting particle size requirements is made；
2) silicon source and organic carbon source, high purity graphite are subjected to compound, obtained silicon/carbon/stone using the following two kinds different modes
Black composite material；
A, the silicon source and the organic carbon source are subjected to solid phase or the compound obtained presoma of liquid phase, then set the presoma
High temperature pyrolysis obtains silicon carbon material under atmosphere of inert gases, then the silicon carbon material and the high purity graphite are carried out mechanical mix
It closes, obtains the silicon/carbon graphite composite material；
B, the silicon source, the organic carbon source, the high purity graphite are mixed and added into dispersing agent and be uniformly dispersed, by doing by spraying
It is dry to be placed on high temperature pyrolysis under atmosphere of inert gases, obtain the silicon/carbon graphite composite material.
2. negative electrode of lithium ion battery as described in claim 1 silicon/carbon graphite composite material preparation method, feature exist
In in step 1), the pretreated method includes drying, in corase grinding, magnetic agitation, mechanical stirring, high-energy ball milling, sand milling
It is one or several kinds of；The method of the purification includes that pickling, alkali cleaning, washing, alcohol one of are washed or several, wherein described mention
It is washed for the last time using alcohol in pure method.
3. negative electrode of lithium ion battery as claimed in claim 2 silicon/carbon graphite composite material preparation method, feature exist
In acid used by the pickling is selected from one of sulfuric acid, hydrochloric acid, hydrofluoric acid and nitric acid or several, and the pickling is adopted
Acid concentration is 1M-18M, and the time of the pickling is 10-30h；Alkali used by the alkali cleaning is selected from sodium hydroxide, hydrogen-oxygen
Change one of potassium, barium hydroxide and ammonium hydroxide or several, alkali concentration used by the alkali cleaning is 1M-12M, the alkali cleaning
Time is 8-20h；Alcohol used by the alcohol is washed is selected from one of dehydrated alcohol, isopropanol, n-butanol or several, described
The time that alcohol is washed is 10-30h.
4. negative electrode of lithium ion battery as described in claim 1 silicon/carbon graphite composite material preparation method, feature exist
In the silicon-containing material is one of thick silicon, silicon copper, silico-aluminum, Si-Mg alloy, Al-Si-Cu alloy, silicon kirsite
Or it is several；The organic carbon source is citric acid, pitch, sucrose, glucose, polyvinylpyrrolidone, polyethylene glycol, gathers inclined fluorine
One of ethylene, polyvinyl alcohol, polythiophene, epoxy resin, phenolic resin, polyacrylonitrile, polystyrene resin, poly-dopamine
Or it is several；The high purity graphite is one of artificial graphite, natural graphite or carbonaceous mesophase spherules or several.
5. negative electrode of lithium ion battery as described in claim 1 silicon/carbon graphite composite material preparation method, feature exist
In in step 2), the inert gas is high-purity argon gas or nitrogen, and the method for the high temperature pyrolysis includes: first to be warming up to
300-500 DEG C of range inside holding 1-24h, is then warming up within the scope of 600-1200 DEG C again and keeps the temperature 1-24h, finally cooling drop
Temperature, wherein heating rate is 2-10 DEG C/min.
6. negative electrode of lithium ion battery as described in claim 1 silicon/carbon graphite composite material preparation method, feature exist
In the meso-position radius of the silicon source is having a size of 10-500nm, and the meso-position radius of the high purity graphite is having a size of 10-18 μm；The silicon/
The meso-position radius of carbon graphite composite material is having a size of 10-22 μm.
7. negative electrode of lithium ion battery as described in claim 1 silicon/carbon graphite composite material preparation method, feature exist
In the dispersing agent includes pure water, dehydrated alcohol, acetone, carboxymethylcellulose sodium solution, N-Methyl pyrrolidone or tetrahydro
One or more of furans, wherein finely dispersed method includes solid phase blending, magnetic agitation, ultrasonic disperse, ball milling, machinery
The one or more of stirring.
8. negative electrode of lithium ion battery as described in claim 1 silicon/carbon graphite composite material preparation method, feature exist
In the compound method of, the solid phase or liquid phase include solid phase be blended, liquid phase in-stiu coating or spray drying；The spray drying
Temperature be 120-280 DEG C.
9. negative electrode of lithium ion battery as described in claim 1 silicon/carbon graphite composite material preparation method, feature exist
In in step A, the quality of silicon accounts for 70-95% in the silicon carbon material, and the quality of carbon accounts for 5-30%；The silicon carbon material and institute
Stating high purity graphite and carrying out the mass percent of mechanical mixture is (5-20%): (80-95%).
10. negative electrode of lithium ion battery as described in claim 1 silicon/carbon graphite composite material preparation method, feature exist
In in step B, the mass percent of silicon ingredient, carbon component and graphite content is (5- in the silicon/carbon graphite composite material
20%): (5-20%): (70-80%).
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