CN103456926A - Preparation methods of silicon-graphene composite material and lithium ion battery - Google Patents
Preparation methods of silicon-graphene composite material and lithium ion battery Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 36
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- 239000000758 substrate Substances 0.000 claims abstract description 40
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 33
- 239000010703 silicon Substances 0.000 claims abstract description 33
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- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 5
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- 238000001035 drying Methods 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000006258 conductive agent Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 238000005520 cutting process Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000004513 sizing Methods 0.000 claims description 15
- 230000004888 barrier function Effects 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
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- 239000011258 core-shell material Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 5
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 5
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 4
- 206010040844 Skin exfoliation Diseases 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 230000035618 desquamation Effects 0.000 claims description 4
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 230000002045 lasting effect Effects 0.000 abstract 1
- 238000002347 injection Methods 0.000 description 18
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 239000011889 copper foil Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 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 description 9
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
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- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 9
- 238000003475 lamination Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 5
- 239000003595 mist Substances 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910010941 LiFSI Inorganic materials 0.000 description 3
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000004050 hot filament vapor deposition Methods 0.000 description 2
- 238000001182 laser chemical vapour deposition Methods 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000011356 non-aqueous organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011257 shell material Substances 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013528 LiN(SO2 CF3)2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
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- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a preparation method of a silicon-graphene composite material. The preparation method comprises the following steps of putting a substrate into a reaction chamber of a chemical vapor deposition device, heating the substrate to a temperature of 500-1300 DEG C in a protective atmosphere, feeding a gaseous carbon source and a gaseous silicon source into the reaction chamber for a reaction lasting for 1-300min, and carrying out cooling to obtain the silicon-graphene composite material. The preparation method of the silicon-graphene composite material has the simple processes. The invention also provides a preparation method of a lithium ion battery.
Description
Technical field
The present invention relates to a kind of preparation method of silicon-graphene composite material and the preparation method of lithium ion battery.
Background technology
Graphene is as a kind of new carbon, since within 2004, being found, due to its two-dimentional monolayer structure and excellent physical property, as high theoretical specific area, excellent mechanical strength, good pliability and high conductivity etc., two are widely used in lithium ion battery.By silicon materials and Graphene carry out compound can effectively reduce silicon materials expand and contraction process in to the destruction of electrode material, thereby the cycle performance of raising device.
When preparing at present silicon-Graphene and meeting material, first, by the standby graphite oxide of graphite-made, by graphite oxide, prepare graphene oxide, redox graphene prepares Graphene, finally prepared by silicon materials and Graphene blend again.The preparation method of this silicon-graphene composite material is comparatively loaded down with trivial details.
Summary of the invention
Based on this, be necessary to provide the preparation method of silicon-graphene composite material that a kind of technique is comparatively simple and the preparation method of lithium ion battery.
A kind of preparation method of silicon-graphene composite material, comprise the steps:
Substrate is positioned over to the reative cell of chemical vapor depsotition equipment, under the protective gas atmosphere, heating described substrate, to make described substrate temperature be 500 ℃ ~ 1300 ℃; And
Pass into gaseous carbon source and gaseous state silicon source in described reative cell, the cooling silicon-graphene composite material that obtains after reaction 1min ~ 300min.
In embodiment, described protective gas is nitrogen or argon gas therein.
In embodiment, described gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene therein.
In embodiment, described gaseous state silicon source is selected from least one in tetramethylsilane and silicon tetrahydride therein.
In embodiment, the mol ratio in described gaseous carbon source and described gaseous state silicon source is 0.5:1 ~ 6:1 therein.
In embodiment, the preparation method of described silicon-graphene composite material also comprises step therein: described silicon-graphene composite material, from described substrate desquamation, and will be peeled off to the silicon that obtains-graphene composite material and pulverized.
A kind of preparation method of lithium ion battery comprises the following steps:
Provide positive electrode active materials and negative active core-shell material, silicon-graphene composite material prepared by the preparation method that described negative active core-shell material is the described silicon-graphene composite material of claim 1 to 6 any one;
Respectively described positive electrode active materials and described negative active core-shell material are coated on plus plate current-collecting body and negative current collector and prepare positive pole and negative pole; And
By being soaked in electrolyte after described positive pole and negative pole and barrier film assembling, obtain lithium ion battery.
In embodiment, described positive electrode active materials is selected from least one in cobalt acid lithium, LiFePO4 and LiMn2O4 therein.
Therein in embodiment, prepared by following steps by described positive pole: described positive electrode active materials and anodal binding agent, anodal conductive agent are mixed to form to positive electrode in 75 ~ 90:5 ~ 10:5 ~ 15 in mass ratio, described positive electrode and solvent are mixed with to anode sizing agent, then described anode sizing agent is coated on plus plate current-collecting body, drying, rolls film, be made into positive pole after cutting.
Therein in embodiment, prepared by following steps by described negative pole: described negative active core-shell material, negative pole binding agent, cathode conductive agent are mixed to form to negative material in 80 ~ 90:5 ~ 10:5 ~ 10 in mass ratio, described negative material and solvent are mixed with to cathode size, then described cathode size is coated on negative current collector, drying, rolls film, be made into negative pole after cutting.
The preparation method of above-mentioned silicon-graphene composite material and the preparation method of lithium ion battery, utilize chemical vapour deposition technique to prepare silicon-graphene composite material, and technique is comparatively simple, simple to operate and consuming time shorter; Silicon-the graphene composite material of preparation is applied to the cycle performance that lithium ion battery can improve lithium ion battery.
The accompanying drawing explanation
The preparation method's of silicon-graphene composite material that Fig. 1 is an execution mode flow chart;
The preparation method's of the lithium ion battery that Fig. 2 is an execution mode flow chart.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, those skilled in the art can be in the situation that do similar improvement without prejudice to intension of the present invention, so the present invention is not subject to the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the silicon-graphene composite material of an execution mode, comprise the steps:
Step S110, substrate is positioned over to the reative cell of chemical vapor depsotition equipment, under the protective gas atmosphere, it is 500 ℃ ~ 1300 ℃ that heated substrate makes substrate temperature.
Preferably, substrate is selected from a kind of in Copper Foil, iron foil and nickel foil.
Preferably, substrate was first used successively deionized water, ethanol and acetone ultrasonic cleaning post-drying before being positioned over reative cell.
Preferably, chemical vapor depsotition equipment is that hot-filament chemical vapor deposition equipment, radio frequency plasma strengthen chemical vapor depsotition equipment, microwave plasma enhanced chemical vapor depsotition equipment, laser chemical vapor deposition equipment, low pressure chemical vapor deposition equipment or aumospheric pressure cvd equipment.
Preferably, protective gas is nitrogen or argon gas.
Preferably, after substrate is positioned over to reative cell, in reative cell, pass into nitrogen, adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and keep 1 ~ 30min, stop afterwards logical nitrogen, the closure molecule pump, start substrate is heated.
Step S120, maintenance substrate temperature are 500 ℃ ~ 1300 ℃, in reative cell, pass into gaseous carbon source and gaseous state silicon source, the cooling silicon-graphene composite material that obtains after reaction 1min ~ 300min.
Preferably, gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene.
Preferably, gaseous state silicon source is selected from least one in tetramethylsilane and silicon tetrahydride.
Preferably, the mol ratio in gaseous carbon source and gaseous state silicon source is 0.5:1 ~ 6:1.
Preferably, the flow of gaseous carbon source is 50ml/min ~ 300ml/min, and the flow in gaseous state silicon source is 50ml/min 300ml/min.
In this step, carbon source is carried out chemical vapour deposition (CVD) and is generated Graphene, and the silicon source is carried out chemical vapour deposition (CVD) and generated silicon, and the silicon generated is distributed between graphene sheet layer uniformly.
Step S130, by silicon-graphene composite material from substrate desquamation, and will peel off the silicon that obtains-graphene composite material and pulverize.
Preferably, adopt ball mill that silicon-graphene composite material is crushed to silicon-graphene composite material and become micron order or nano level powder.
The preparation method of above-mentioned silicon-graphene composite material, utilize chemical vapour deposition technique to prepare silicon-graphene composite material, and technique is comparatively simple, simple to operate and consuming time shorter; In the silicon-graphene composite material of preparation, silicon is distributed between graphene sheet layer uniformly.
Refer to Fig. 2, the preparation method of the lithium ion battery of an execution mode, comprise the steps:
Step S210, positive electrode active materials and negative active core-shell material, negative active core-shell material are provided is silicon-graphene composite material.
Wherein, the preparation method of silicon-graphene composite material comprises the following steps:
Step S211, substrate is positioned over to the reative cell of chemical vapor depsotition equipment, under the protective gas atmosphere, it is 500 ℃ ~ 1300 ℃ that heated substrate makes substrate temperature.
Preferably, substrate is selected from a kind of in Copper Foil, iron foil and nickel foil.
Preferably, substrate was first used successively deionized water, ethanol and acetone ultrasonic cleaning post-drying before being positioned over reative cell.
Preferably, chemical vapor depsotition equipment is that hot-filament chemical vapor deposition equipment, radio frequency plasma strengthen chemical vapor depsotition equipment, microwave plasma enhanced chemical vapor depsotition equipment, laser chemical vapor deposition equipment, low pressure chemical vapor deposition equipment or aumospheric pressure cvd equipment.
Preferably, protective gas is nitrogen or argon gas.
Preferably, after substrate is positioned over to reative cell, in reative cell, pass into nitrogen, adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and keep 1 ~ 30min, stop afterwards logical nitrogen, the closure molecule pump, start substrate is heated.
Step S212, maintenance substrate temperature are 500 ℃ ~ 1300 ℃, in reative cell, pass into gaseous carbon source and gaseous state silicon source, the cooling silicon-graphene composite material that obtains after reaction 1min ~ 300min.
Preferably, gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene.
Preferably, gaseous state silicon source is selected from least one in tetramethylsilane and silicon tetrahydride.
Preferably, the mol ratio in gaseous carbon source and gaseous state silicon source is 0.5:1 ~ 6:1.
Preferably, the flow of gaseous carbon source is 50ml/min ~ 300ml/min, and the flow in gaseous state silicon source is 50ml/min ~ 300ml/min.
In this step, carbon source is carried out chemical vapour deposition (CVD) and is generated Graphene, and the silicon source is carried out chemical vapour deposition (CVD) and generated silicon, and the silicon generated is distributed between graphene sheet layer uniformly.
Step S213, by silicon-graphene composite material from substrate desquamation, and will peel off the silicon that obtains-graphene composite material and pulverize.
Preferably, adopt ball mill that silicon-graphene composite material is crushed to silicon-graphene composite material and become micron-sized powder.
Preferably, positive electrode active materials is selected from least one in cobalt acid lithium, LiFePO4 and LiMn2O4.
Step S220, respectively positive electrode active materials and negative active core-shell material are coated on plus plate current-collecting body and negative current collector and prepare positive pole and negative pole.
In present embodiment, positive electrode active materials, anodal adhesive, anodal conductive agent are mixed to form to positive electrode in 75 ~ 90:5 ~ 10:5 ~ 15 in mass ratio, positive electrode and solvent are formed to anode sizing agent, afterwards anode sizing agent is coated on to plus plate current-collecting body (aluminium foil) upper, drying, rolls film, be made into positive pole after cutting.Anodal binding agent is Kynoar (PVDF), and anodal conductive agent is acetylene black.Solvent is 1-METHYLPYRROLIDONE (NMP).The viscosity of anode sizing agent is 4000 centipoises ~ 8000 centipoises, is preferably 5500 centipoises ~ 6500 centipoises.In present embodiment, negative electrode active material, negative pole binding agent, cathode conductive agent are mixed to form to negative material in 80 ~ 90:5 ~ 10:5 ~ 10 in mass ratio, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting.The mixture that the negative pole binding agent is butadiene-styrene rubber (SBR) and sodium carboxymethylcellulose (CMC), conductive agent is acetylene black.Solvent is 1-METHYLPYRROLIDONE (NMP).The viscosity of cathode size is 5500 centipoises ~ 6500 centipoises, is preferably 5500 centipoises ~ 6500 centipoises.
Step S230, by being soaked in electrolyte after positive pole and negative pole and barrier film assembling, obtain lithium ion battery.
In present embodiment, electrolyte is that lithium-ion electrolyte salt and non-aqueous organic solvent are formulated.Lithium-ion electrolyte salt is selected from LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2) and LiFSI (LiN (SO
2f)
2) at least one, non-aqueous organic solvent is selected from least one in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate and acetonitrile.The concentration of electrolyte is preferably 1mol/L.
In present embodiment, anode pole piece, barrier film and cathode pole piece stack gradually rear composition battery core, seal battery core with lithium-ion battery shell again, finally by the liquid injection port be arranged on lithium-ion battery shell, inject electrolyte, the sealing liquid injection port can obtain lithium ion battery.
The preparation method of above-mentioned lithium ion battery is comparatively simple, and the cycle performance of the lithium ion battery of preparation is better.
Below in conjunction with specific embodiment, further illustrate.
Embodiment 1
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reative cell, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and, after keeping 30 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 1300 ℃, start to reative cell be filled with methane (flow: 100ml/ minute) and silicon tetrahydride (flow: mist 200ml/min minute), keep temperature-resistant, start to generate silicon/graphene composite material;
(4) after reacting 240 minutes, stop the substrate heating, and be cooled to room temperature, obtain silicon-graphene composite material.
Embodiment 2
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reative cell, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and, after keeping 30 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 1000 ℃, start to reative cell be filled with methane (flow: 100ml/ minute) and silicon tetrahydride (flow: mist 150ml/min minute), keep temperature-resistant, start to generate silicon/graphene composite material;
(4) after reacting 1 minute, stop the substrate heating, and be cooled to room temperature, obtain silicon/graphene composite material.
Embodiment 3
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reative cell, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and, after keeping 20 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 500 ℃, start to reative cell be filled with acetylene (flow: 50ml/ minute) and silicon tetrahydride (flow: mist 300ml/min minute), keep temperature-resistant, start to generate silicon/graphene composite material;
(4) after reacting 300 minutes, stop the substrate heating, and be cooled to room temperature, obtain silicon/graphene composite material.
Embodiment 4
(1) by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate;
(2) substrate is put into to reative cell, is filled with nitrogen, and adopt mechanical pump, lobe pump and molecular pump are evacuated to 10 by reative cell step by step
-3below Pa, and, after keeping 30 minutes, stop filling nitrogen, air to close closes molecular pump, starts heating;
(3) when underlayer temperature reaches 800 ℃, start to reative cell be filled with ethene (flow: 300ml/ minute) and silicon tetrahydride (flow: mist 50ml/min minute), keep temperature-resistant, start to generate silicon/graphene composite material;
(4) after reacting 150 minutes, stop the substrate heating, and be cooled to room temperature, obtain silicon/graphene composite material.
Embodiment 5
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 1, cathode conductive agent acetylene black 80:10:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting; By positive electrode active materials cobalt acid lithium, anodal adhesive Kynoar, anodal conductive agent acetylene black in mass ratio 75:10:15 be mixed to form positive electrode, positive electrode and solvent 1-METHYLPYRROLIDONE are mixed to form to anode sizing agent, afterwards anode sizing agent is coated on to plus plate current-collecting body (aluminium foil) upper, drying, rolls film, be made into positive pole after cutting.
(2) by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, then use battery housing seal battery core, toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is by LiPF subsequently
6be dissolved in dimethyl carbonate and form, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 6
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 2, cathode conductive agent acetylene black 90:5:5 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting; By iron phosphate serving as positive active material, anodal adhesive Kynoar, anodal conductive agent acetylene black in mass ratio 90:5:5 be mixed to form positive electrode, positive electrode and solvent 1-METHYLPYRROLIDONE are mixed to form to anode sizing agent, afterwards anode sizing agent is coated on to plus plate current-collecting body (aluminium foil) upper, drying, rolls film, be made into positive pole after cutting.
(2) by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, then use battery housing seal battery core, toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is by LiBF subsequently
4be dissolved in diethyl carbonate and form, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 7
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 3, cathode conductive agent acetylene black 85:5:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting; By positive electrode active materials LiMn2O4, anodal adhesive Kynoar, anodal conductive agent acetylene black in mass ratio 80:5:15 be mixed to form positive electrode, positive electrode and solvent 1-METHYLPYRROLIDONE are mixed to form to anode sizing agent, afterwards anode sizing agent is coated on to plus plate current-collecting body (aluminium foil) upper, drying, rolls film, be made into positive pole after cutting.
(2) by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is dissolved in propene carbonate and is formed by LiTFSI, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 8
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 4, cathode conductive agent acetylene black 85:7:8 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting; By positive electrode active materials LiMn2O4, anodal adhesive Kynoar, anodal conductive agent acetylene black in mass ratio 85:5:10 be mixed to form positive electrode, positive electrode and solvent 1-METHYLPYRROLIDONE are mixed to form to anode sizing agent, afterwards anode sizing agent is coated on to plus plate current-collecting body (aluminium foil) upper, drying, rolls film, be made into positive pole after cutting.
(2) by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is dissolved in the mixed solvent be mixed to form by ethylene carbonate and acetonitrile and is formed by LiFSI, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 9
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 1, cathode conductive agent acetylene black 85:5:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting.
(2) using the lithium sheet as positive pole, by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, then use battery housing seal battery core, toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is by LiPF subsequently
6be dissolved in dimethyl carbonate and form, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 10
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 2, cathode conductive agent acetylene black 85:5:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting.
(2) using the lithium sheet as positive pole, by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is dissolved in diethyl carbonate and is formed by LiBF4, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 11
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 3, cathode conductive agent acetylene black 85:5:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting.
(2) using the lithium sheet as positive pole, by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is dissolved in propene carbonate and is formed by LiTFSI, the sealing liquid injection port, obtain lithium ion battery.
Embodiment 12
(1) mixture of silicon-graphene composite material, negative pole binding agent butadiene-styrene rubber and the sodium carboxymethylcellulose prepared by embodiment 4, cathode conductive agent acetylene black 85:5:10 in mass ratio are mixed to form negative material, negative material and solvent are formed to cathode size, afterwards cathode size is coated on to negative current collector (Copper Foil) upper, drying, rolls film, be made into negative pole after cutting.
(2) using the lithium sheet as positive pole, by positive pole, barrier film, negative pole in order stack of laminations dress up battery core, use again battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the electrolyte that injects 1mol/L in battery container, electrolyte is dissolved in the mixed solvent be mixed to form by ethylene carbonate and acetonitrile and is formed by LiFSI, the sealing liquid injection port, obtain lithium ion battery.
Refer to table 1, the lithium ion battery that table 1 is depicted as embodiment 9 ~ 12 preparations is discharged and recharged the test data of the stored energy capacitance obtained under the 0.1C electric current.
Table 1
As can be seen from Table 1, the capacity of lithium ion battery prepared by silicon-graphene composite material prepared by the present invention is higher, and the specific capacity conservation rate after 300 times that circulates all is greater than 65%, is up to 80%.
The above embodiment has only expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection range of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the preparation method of a silicon-graphene composite material, is characterized in that, comprises the steps:
Substrate is positioned over to the reative cell of chemical vapor depsotition equipment, under the protective gas atmosphere, heating described substrate, to make described substrate temperature be 500 ℃ ~ 1300 ℃; And
Pass into gaseous carbon source and gaseous state silicon source in described reative cell, the cooling silicon-graphene composite material that obtains after reaction 1min ~ 300min.
2. the preparation method of silicon-graphene composite material according to claim 1, is characterized in that, described protective gas is nitrogen or argon gas.
3. the preparation method of silicon-graphene composite material according to claim 1, is characterized in that, described gaseous carbon source is selected from least one in methane, ethane, ethene and acetylene.
4. the preparation method of silicon-graphene composite material according to claim 1, is characterized in that, described gaseous state silicon source is selected from least one in tetramethylsilane and silicon tetrahydride.
5. the preparation method of silicon-graphene composite material according to claim 1, is characterized in that, the mol ratio in described gaseous carbon source and described gaseous state silicon source is 0.5:1 ~ 6:1.
6. the preparation method of silicon-graphene composite material according to claim 1, it is characterized in that, the preparation method of described silicon-graphene composite material also comprises step: described silicon-graphene composite material, from described substrate desquamation, and will be peeled off to the silicon that obtains-graphene composite material and pulverized.
7. the preparation method of a lithium ion battery, is characterized in that, comprises the following steps:
Provide positive electrode active materials and negative active core-shell material, silicon-graphene composite material prepared by the preparation method that described negative active core-shell material is the described silicon-graphene composite material of claim 1 to 6 any one;
Respectively described positive electrode active materials and described negative active core-shell material are coated on plus plate current-collecting body and negative current collector and prepare positive pole and negative pole; And
By being soaked in electrolyte after described positive pole and negative pole and barrier film assembling, obtain lithium ion battery.
8. the preparation method of lithium ion battery according to claim 7, is characterized in that, described positive electrode active materials is selected from least one in cobalt acid lithium, LiFePO4 and LiMn2O4.
9. the preparation method of lithium ion battery according to claim 7, it is characterized in that, prepared by following steps by described positive pole: described positive electrode active materials and anodal binding agent, anodal conductive agent are mixed to form to positive electrode in 75 ~ 90:5 ~ 10:5 ~ 15 in mass ratio, described positive electrode and solvent are mixed with to anode sizing agent, then described anode sizing agent is coated on plus plate current-collecting body, drying, rolls film, be made into positive pole after cutting.
10. the preparation method of lithium ion battery according to claim 7, it is characterized in that, prepared by following steps by described negative pole: described negative active core-shell material, negative pole binding agent, cathode conductive agent are mixed to form to negative material in 80 ~ 90:5 ~ 10:5 ~ 10 in mass ratio, described negative material and solvent are mixed with to cathode size, then described cathode size is coated on negative current collector, drying, rolls film, be made into negative pole after cutting.
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