CN104766958A - Silicon-carbon composite material and preparation method thereof, and lithium ion battery - Google Patents
Silicon-carbon composite material and preparation method thereof, and lithium ion battery Download PDFInfo
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- CN104766958A CN104766958A CN201410008625.2A CN201410008625A CN104766958A CN 104766958 A CN104766958 A CN 104766958A CN 201410008625 A CN201410008625 A CN 201410008625A CN 104766958 A CN104766958 A CN 104766958A
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- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 239000012530 fluid Substances 0.000 claims abstract description 39
- 239000007833 carbon precursor Substances 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 78
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 44
- 239000000377 silicon dioxide Substances 0.000 claims description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 239000010703 silicon Substances 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000001856 Ethyl cellulose Substances 0.000 claims description 17
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 17
- 229920001249 ethyl cellulose Polymers 0.000 claims description 17
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 17
- 229920000609 methyl cellulose Polymers 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 235000012239 silicon dioxide Nutrition 0.000 claims description 15
- 239000001923 methylcellulose Substances 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 11
- 229910002804 graphite Inorganic materials 0.000 claims description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 abstract description 4
- 239000002210 silicon-based material Substances 0.000 abstract 4
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 235000013312 flour Nutrition 0.000 description 18
- 238000011056 performance test Methods 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000007599 discharging Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000001761 ethyl methyl cellulose Substances 0.000 description 3
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
-
- 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 discloses a silicon-carbon composite material and a preparation method thereof, and a lithium ion battery. The method comprises that: (1) a silicon-based material is placed into an autoclave, wherein a high-pressure environment exists in the autoclave; and a supercritical fluid having the dissolved organic carbon precursor is pumped into the autoclave by using a high pressure pump to obtain a mixture; (2) the autoclave is communicated with a pressure-releasing sealed container, and the mixture enters the pressure-releasing sealed container to obtain an organic carbon precursor-coated silicon-based material composite material; and (3) high temperature carbonization is performed under a non-oxidizing atmosphere to obtain the silicon-carbon composite material. According to the present invention, with the supercritical fluid, the organic carbon precursor is completely dispersed, such that the organic carbon precursor and the silicon-based material are uniformly mixed, the binding force is increased, the volatilizing gas-state supercritical carbon dioxide can be continuously reused after entering the pressure-releasing sealed container, and no impurity is introduced into the organic carbon precursor and silicon-based material mixture so as to further improve the rate capability of the battery.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of Si-C composite material and preparation method thereof, lithium ion battery.
Background technology
In recent years, along with the requirement of the day by day serious of energy environment issues and electronic product lightness, the research of people to lithium ion battery deepens continuously.Traditional lithium ion battery generally includes positive pole, negative pole, barrier film and electrolyte four parts.Common anode material for lithium-ion batteries selects the reactive compound containing lithium usually, and negative material is then selected from carbon-based material.During charging, the electrical potential difference being added in battery the two poles of the earth forces the active material in positive pole to discharge lithium ion, the negative material of intercalated layered structure; During electric discharge, lithium ion is then separate out from the carbon-based negative electrode material of layer structure, and the active material in positive electrode is combined.
Common graphite class negative material has higher cycle efficieny and good cycle performance, has been widely used in the production application of lithium ion battery.But the capacity of the storage lithium of graphite negative electrodes material is lower, and theoretical specific capacity is only 372mAh/g.So the silica-base material that people are are just researching and developing new high power capacity is applied for lithium ion battery negative.
Silicon can partly repeat, and carry out the reaction storing lithium under relatively low pressure condition, silicon can provide very large specific capacity, and silica-base material theoretical specific capacity can reach 4200mAh/g.But in battery charge and discharge process, the embedding of lithium and deviate from the great variety that circulation can cause silicon volume, the serious volumetric expansion of silicon and contraction, can cause the destruction of material structure, material efflorescence, thus cause the sharply decline of cycle performance of lithium ion battery.So people are just making great efforts to reduce this bulk effect to keep the structural intergrity of negative material.
Summary of the invention
Technical problem to be solved by this invention is for above shortcomings in prior art, a kind of Si-C composite material and preparation method thereof is provided, lithium ion battery, adopt shooting flow physical efficiency that organic carbon presoma is fully disperseed in this preparation method, organic carbon precursor and silica-base material are mixed to get evenly and increase adhesion, after making it enter into pressure release container, supercritical carbon dioxide still can continue recycling after evaporating into gaseous state, impurity is not introduced in the mixture of organic carbon precursor and silica-base material, the high rate performance of further raising lithium ion battery.
The technical scheme that solution the technology of the present invention problem adopts is to provide a kind of preparation method of Si-C composite material, comprises the following steps:
(1) silica-base material is put in autoclave, be hyperbaric environment in this autoclave, then with high-pressure pump, the supercritical fluid having dissolved organic carbon precursor is pumped in described autoclave, obtains the mixture of described silica-base material, described organic carbon precursor, described supercritical fluid;
(2) be communicated with the closed container (expanding chamber) of pressure release by described autoclave, described mixture enters into the closed container of described pressure release again, obtains the composite material of the coated described silica-base material of described organic carbon precursor;
(3) by composite material high temperature cabonization under nonoxidizing atmosphere of coated for described organic carbon precursor described silica-base material, Si-C composite material is obtained.
Preferably, the quality of the described organic carbon precursor in described step (1) accounts for 0.01 ~ 10% of described organic carbon precursor and described supercritical fluid gross mass.
Preferably, the particle diameter of described silica-base material is 20 ~ 200nm.
Preferably, the temperature in the described autoclave in described step (1) is-10 ~ 100 DEG C, and pressure is 1 ~ 10MPa, adapts with the pressure and temperature maintained needed for described supercritical fluid.
Preferably, the described silica-base material in described step (1) is silicon, silicon monoxide, the mixture of silicon and silicon monoxide, the mixture of silicon, silicon monoxide and silicon dioxide, the mixture of silicon and silicon dioxide, the one in the mixture of silicon monoxide and silicon dioxide;
Organic carbon precursor is one or more in methylcellulose, ethyl cellulose, polypropylene, polyvinyl alcohol, polyvinyl butyral resin;
Described supercritical fluid is the one in supercritical carbon dioxide, supercritical water, supercritical methanol.
Preferably, the temperature of the described high temperature cabonization in described step (3) is 350 ~ 850 DEG C, and the time of carbonization is 1 ~ 24 hour.
Preferably, the quality of the described silicon in the described Si-C composite material obtained in described step (3) accounts for 50 ~ 90% of described Si-C composite material quality.
Preferably, the described nonoxidizing atmosphere in described step (3) is the mist of one or more gases in nitrogen, argon gas, hydrogen, ammonia, carbon monoxide.
The present invention also provides a kind of Si-C composite material, and it is prepared by above-mentioned method.
The present invention also provides a kind of lithium ion battery, and its negative pole contains above-mentioned Si-C composite material.
Preferably, described negative material also comprises graphite, and the mass ratio of described Si-C composite material and described graphite is (1:15) ~ (1:2).
Supercritical fluid is owing to being be in more than critical temperature and critical pressure, and the fluid between gas and liquid, has double properties and the advantage of gas liquid concurrently:
(1) dissolubility is strong, and density is close to liquid, and larger than gas hundreds of times, because the solubility of material is directly proportional to the density of solvent, therefore supercritical fluid has the solvability close with liquid flux.
(2) diffusion is good, because viscosity is close to gas, and 2 orders of magnitude little of liquid.Diffusion coefficient, between gas and liquid, is 10-100 times of liquid.Have the characteristic that gas is easy to spread and move, mass transfer rate is far away higher than liquid.
(3) be easy to control, at Near The Critical Point, the minor variations of pressure and temperature, can cause the change that fluid density is very large, thus makes solubility that larger change occur.
In the preparation method of the Si-C composite material in the present invention, by supercritical fluid, organic carbon presoma is dissolved, then mix with silica-base material, be communicated with the closed container of pressure release by autoclave again, mix with the direct of silica-base material relative to the organic carbon presoma of prior art, supercritical fluid makes organic carbon presoma obtain abundant dispersion, and it is more even to make organic carbon precursor and silica-base material be mixed to get, after entering into pressure release container, supercritical carbon dioxide still can continue recycling after evaporating into gaseous state, any impurity is not introduced in the mixture of organic carbon precursor and silica-base material, and do not need to remove decentralized medium supercritical fluid specially, in preparation method, the pressure change in the closed container from autoclave to pressure release can increase the adhesion between organic carbon presoma and silica-base material, preparation method well realizes, to the modification with final obtained Si-C composite material, further increasing the high rate performance of lithium ion battery.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) be that the silica flour of 50nm is put in autoclave by particle diameter, be hyperbaric environment in this autoclave, then with high-pressure pump, the Co 2 supercritical fluid of ethyl cellulose dissolved is pumped in described autoclave, wherein, the quality of ethyl cellulose accounts for 1.7% of ethyl cellulose and Co 2 supercritical fluid gross mass.50 DEG C, under the condition of 8MPa, stir 2 hours, obtain the mixture of silica flour, ethyl cellulose, Co 2 supercritical fluid;
(2) be communicated with expanding chamber (i.e. the closed container of pressure release) by described autoclave, described mixture enters into expanding chamber, obtains the composite material of the coated silica flour of ethyl cellulose again;
(3) by the composite material of coated for ethyl cellulose silica flour under an argon atmosphere, at 350 DEG C, carbonization 12 hours, obtains Si-C composite material, and the quality of the silicon in this Si-C composite material accounts for 60% of Si-C composite material quality.In this step, ethyl cellulose carbonization can become carbon.
Gained Si-C composite material is mixed according to mass ratio 80: 10: 10 with conductive agent acetylene black, binding agent PVDF respectively, use NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, evenly be coated on Copper Foil, 100 DEG C of vacuumize 24 hours, obtained experimental cell pole piece.Be to electrode with lithium sheet, electrolyte is the LiPF of 1mol/L
6solution, solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate) (volume ratio 1: 1), barrier film is celgard2400 film, is assembled into CR2025 type button cell in the glove box being full of argon gas atmosphere.
High rate performance test is carried out to this button cell: discharge and recharge is 0.01 ~ 1.5V by voltage, and charging and discharging currents is respectively 0.2C, 1C, each circulation 10 times, wherein, 1C=700mA/g.High rate performance test result shows, discharge and recharge is 0.01 ~ 1.5V by voltage, and under the condition of 0.2C, the specific discharge capacity of battery is 553mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 414mAh/g, and the high rate performance of battery is better.
The present embodiment provides a kind of lithium ion battery, and its negative pole contains the Si-C composite material prepared by above-mentioned preparation method.
In the preparation method of the Si-C composite material in the present embodiment, by supercritical fluid, organic carbon presoma is dissolved, then mix with silica-base material, be communicated with the closed container of pressure release by autoclave again, mix with the direct of silica-base material relative to the organic carbon presoma of prior art, supercritical fluid makes organic carbon presoma obtain abundant dispersion, and it is more even to make organic carbon precursor and silica-base material be mixed to get, after entering into pressure release container, supercritical carbon dioxide still can continue recycling after evaporating into gaseous state, any impurity is not introduced in the mixture of organic carbon precursor and silica-base material, and do not need to remove decentralized medium supercritical fluid specially, in preparation method, the pressure change in the closed container from autoclave to pressure release can increase the adhesion between organic carbon presoma and silica-base material, preparation method well realizes, to the modification with final obtained Si-C composite material, further increasing the high rate performance of lithium ion battery.
Embodiment 2
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) be that the silicon monoxide of 20nm is put in autoclave by particle diameter, be hyperbaric environment in this autoclave, then the Co 2 supercritical fluid of ethyl cellulose dissolved, methylcellulose to be pumped in described autoclave (wherein with high-pressure pump, the mass ratio of ethyl cellulose and methylcellulose is 1:1), wherein, ethyl cellulose and methylcellulose quality and account for 5% of ethyl cellulose, methylcellulose and Co 2 supercritical fluid gross mass.-10 DEG C, under the condition of 6MPa, stir 24 hours, obtain the mixture of silicon monoxide, ethyl cellulose, methylcellulose, Co 2 supercritical fluid;
(2) be communicated with the closed container of pressure release by described autoclave, described mixture enters into the closed container of pressure release again, obtains the composite material of ethyl cellulose and the coated silicon monoxide of methylcellulose;
(3) by the composite material of ethyl cellulose and the coated silicon monoxide of methylcellulose in a hydrogen atmosphere, at 500 DEG C, carbonization 24 hours, obtains Si-C composite material, and the quality of the silicon in this Si-C composite material accounts for 50% of Si-C composite material quality.In this step can there is disproportionated reaction generation silicon and silicon dioxide in silicon monoxide, and ethyl cellulose carbonization can become carbon with methylcellulose simultaneously.
According to the method preparing button cell in embodiment 1, the obtained Si-C composite material of the present embodiment is used to make button cell as negative material, and high rate performance test is carried out to this battery: discharge and recharge by voltage be 0.01 ~ 1.5V, charging and discharging currents is respectively 0.2C, 1C, each circulation 10 times, wherein, 1C=700mA/g.High rate performance test result shows, discharge and recharge is 0.01 ~ 1.5V by voltage, and under the condition of 0.2C, the specific discharge capacity of battery is 550mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 463mAh/g, and the high rate performance of battery is better.
The present embodiment provides a kind of lithium ion battery, and its negative pole contains the Si-C composite material prepared by above-mentioned preparation method.
Embodiment 3
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) by particle diameter be the mixture of the silica flour of 100nm and silicon monoxide (wherein, the mass ratio of silica flour and silicon monoxide is 2:1) put in autoclave, be hyperbaric environment in this autoclave, then with high-pressure pump, the water supercritical fluid of dissolve polyvinyl alcohol is pumped in described autoclave, wherein, the quality of polyvinyl alcohol accounts for 6% of polyvinyl alcohol and water supercritical fluid gross mass.60 DEG C, under the condition of 4MPa, stir 10 hours, obtain the mixture of silica flour, silicon monoxide, polyvinyl alcohol, water supercritical fluid;
(2) be communicated with expanding chamber by described autoclave, described mixture enters into expanding chamber again, obtains the composite material of the coated silica flour of polyvinyl alcohol and silicon monoxide mixture;
(3) by the composite material of coated for polyvinyl alcohol silica flour and silicon monoxide mixture in a nitrogen atmosphere, at 600 DEG C, carbonization 1 hour, obtains Si-C composite material, and the quality of the silicon in this Si-C composite material accounts for 70% of Si-C composite material quality.In this step can there is disproportionated reaction generation silicon and silicon dioxide in silicon monoxide, and polyvinyl alcohol carbonization can become carbon simultaneously.
According to the method preparing button cell in embodiment 1, the obtained Si-C composite material of the present embodiment is used to make button cell as negative material, and high rate performance test is carried out to this battery: discharge and recharge by voltage be 0.01 ~ 1.5V, charging and discharging currents is respectively 0.2C, 1C, each circulation 10 times, wherein, 1C=700mA/g.High rate performance test result shows, discharge and recharge is 0.01 ~ 1.5V by voltage, and under the condition of 0.2C, the specific discharge capacity of battery is 572mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 451mAh/g, and the high rate performance of battery is better.
The present embodiment provides a kind of lithium ion battery, and its negative pole contains the Si-C composite material prepared by above-mentioned preparation method.
Embodiment 4
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) be that the silica flour of 200nm and the mixture of silicon dioxide to be put in autoclave (wherein by particle diameter, the mass ratio of silica flour and silicon dioxide is 1:2), be hyperbaric environment in this autoclave, then with high-pressure pump, polyacrylic for dissolving methyl alcohol supercritical fluid is pumped in described autoclave, wherein, polyacrylic quality accounts for 0.01% of polypropylene and methyl alcohol supercritical fluid gross mass.100 DEG C, under the condition of 2MPa, stir 6 hours, obtain the mixture of silica flour, silicon dioxide, polypropylene, methyl alcohol supercritical fluid;
(2) be communicated with expanding chamber by described autoclave, described mixture enters into expanding chamber again, obtains the composite material of the coated silica flour of polypropylene and silica mixture;
(3) by the composite material of coated for polypropylene silica flour and silica mixture under an argon atmosphere, at 850 DEG C, carbonization 10 hours, obtains Si-C composite material, and the quality of the silicon in this Si-C composite material accounts for 90% of Si-C composite material quality.
According to the method preparing button cell in embodiment 1, the obtained Si-C composite material of the present embodiment is used to make button cell as negative material, and high rate performance test is carried out to this battery: discharge and recharge by voltage be 0.01 ~ 1.5V, charging and discharging currents is respectively 0.2C, 1C, each circulation 10 times, wherein, 1C=700mA/g.High rate performance test result shows, discharge and recharge is 0.01 ~ 1.5V by voltage, and under the condition of 0.2C, the specific discharge capacity of battery is 583mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 472mAh/g, and the high rate performance of battery is better.
The present embodiment provides a kind of lithium ion battery, and its negative pole contains the Si-C composite material prepared by above-mentioned preparation method.
Embodiment 5
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) be the silica flour of 150nm by particle diameter, the mixture of silicon monoxide, silicon dioxide puts in autoclave, be hyperbaric environment in this autoclave, then with high-pressure pump, the Co 2 supercritical fluid of polyethylene dissolving butyral is pumped in described autoclave, wherein, the quality of polyvinyl butyral resin accounts for 10% of polyvinyl butyral resin and Co 2 supercritical fluid gross mass.80 DEG C, under the condition of 1MPa, stir 18 hours, obtain the mixture of silica flour, silicon monoxide, silicon dioxide, polyvinyl butyral resin, Co 2 supercritical fluid;
(2) be communicated with expanding chamber by described autoclave, described mixture enters into expanding chamber again, obtains the composite material of the coated silica flour of polyvinyl butyral resin, silicon monoxide, silica mixture;
(3) by the composite material of coated for polyvinyl butyral resin silica flour, silicon monoxide, silica mixture under an argon atmosphere, at 750 DEG C, carbonization 20 hours, obtains Si-C composite material, and the quality of the silicon in this Si-C composite material accounts for 80% of Si-C composite material quality.
According to the method preparing button cell in embodiment 1, the obtained Si-C composite material of the present embodiment is used to make button cell as negative material, and high rate performance test is carried out to this battery: discharge and recharge by voltage be 0.01 ~ 1.5V, charging and discharging currents is respectively 0.2C, 1C, each circulation 10 times, wherein, 1C=700mA/g.High rate performance test result shows, discharge and recharge is 0.01 ~ 1.5V by voltage, and under the condition of 0.2C, the specific discharge capacity of battery is 542mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 453mAh/g, and the high rate performance of battery is better.
The present embodiment provides a kind of lithium ion battery, and its negative pole contains the Si-C composite material prepared by above-mentioned preparation method.
Embodiment 6
The present embodiment provides a kind of preparation method of Si-C composite material, comprises the following steps:
(1) be that the silicon monoxide of 80nm and the mixture of silicon dioxide are put in autoclave by particle diameter, be hyperbaric environment in this autoclave, then with high-pressure pump, the Co 2 supercritical fluid dissolving methylcellulose is pumped in described autoclave, wherein, the quality of methylcellulose accounts for 2% of methylcellulose and Co 2 supercritical fluid gross mass.20 DEG C, under the condition of 10MPa, stir 1 hour, obtain the mixture of silicon monoxide, silicon dioxide, methylcellulose, Co 2 supercritical fluid;
(2) be communicated with expanding chamber by described autoclave, described mixture enters into expanding chamber again, obtains the composite material of the coated silicon monoxide of methylcellulose and silica mixture;
(3) by the composite material of coated for methylcellulose silicon monoxide and silica mixture in a nitrogen atmosphere, at 700 DEG C, carbonization 18 hours, obtains Si-C composite material, and the quality of the silicon in this Si-C composite material accounts for 5% of Si-C composite material quality.
According to the method preparing button cell in embodiment 1, the obtained Si-C composite material of the present embodiment is used to make button cell as negative material, and high rate performance test is carried out to this battery: discharge and recharge by voltage be 0.01 ~ 1.5V, charging and discharging currents is respectively 0.2C, 1C, each circulation 10 times, wherein, 1C=700mA/g.High rate performance test result shows, discharge and recharge is 0.01 ~ 1.5V by voltage, and under the condition of 0.2C, the specific discharge capacity of battery is 571mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 435mAh/g, and the high rate performance of battery is better.
The present embodiment provides a kind of lithium ion battery, and its negative pole contains the Si-C composite material prepared by above-mentioned preparation method.
Embodiment 7
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises the arbitrary described Si-C composite material of embodiment 1 ~ 6, also comprise graphite, and the mass ratio of Si-C composite material and graphite is 1:15.
According to the method preparing button cell in embodiment 1, the obtained Si-C composite material of the present embodiment is used to make button cell as negative material, and high rate performance test is carried out to this battery: discharge and recharge by voltage be 0.01 ~ 1.5V, charging and discharging currents is respectively 0.2C, 1C, each circulation 10 times, wherein, 1C=700mA/g.High rate performance test result shows, discharge and recharge is 0.01 ~ 1.5V by voltage, and under the condition of 0.2C, the specific discharge capacity of battery is 542mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 453mAh/g, and the high rate performance of battery is better.
Embodiment 8
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises the arbitrary described Si-C composite material of embodiment 1 ~ 6, also comprise graphite, and the mass ratio of Si-C composite material and graphite is 1:5.
According to the method preparing button cell in embodiment 1, the obtained Si-C composite material of the present embodiment is used to make button cell as negative material, and high rate performance test is carried out to this battery: discharge and recharge by voltage be 0.01 ~ 1.5V, charging and discharging currents is respectively 0.2C, 1C, each circulation 10 times, wherein, 1C=700mA/g.High rate performance test result shows, discharge and recharge is 0.01 ~ 1.5V by voltage, and under the condition of 0.2C, the specific discharge capacity of battery is 517mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 404mAh/g, and the high rate performance of battery is better.
Embodiment 9
The present embodiment provides a kind of lithium ion battery, and its negative pole comprises the arbitrary described Si-C composite material of embodiment 1 ~ 6, also comprise graphite, and the mass ratio of Si-C composite material and graphite is 1:2.
According to the method preparing button cell in embodiment 1, the obtained Si-C composite material of the present embodiment is used to make button cell as negative material, and high rate performance test is carried out to this battery: discharge and recharge by voltage be 0.01 ~ 1.5V, charging and discharging currents is respectively 0.2C, 1C, each circulation 10 times, wherein, 1C=700mA/g.High rate performance test result shows, discharge and recharge is 0.01 ~ 1.5V by voltage, and under the condition of 0.2C, the specific discharge capacity of battery is 498mAh/g; Under the condition of 1C, the specific discharge capacity of battery is 426mAh/g, and the high rate performance of battery is better.
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (10)
1. a preparation method for Si-C composite material, is characterized in that, comprises the following steps:
(1) silica-base material is put in autoclave, be hyperbaric environment in this autoclave, then with high-pressure pump, the supercritical fluid having dissolved organic carbon precursor is pumped in described autoclave, obtains the mixture of described silica-base material, described organic carbon precursor, described supercritical fluid;
(2) be communicated with the closed container of pressure release by described autoclave, described mixture enters into the closed container of described pressure release again, obtains the composite material of the coated described silica-base material of described organic carbon precursor;
(3) by composite material high temperature cabonization under nonoxidizing atmosphere of coated for described organic carbon precursor described silica-base material, Si-C composite material is obtained.
2. the preparation method of Si-C composite material according to claim 1, it is characterized in that, the quality of the described organic carbon precursor in described step (1) accounts for 0.01 ~ 10% of described organic carbon precursor and described supercritical fluid gross mass.
3. the preparation method of Si-C composite material according to claim 1, it is characterized in that, the particle diameter of described silica-base material is 20 ~ 200nm.
4. the preparation method of Si-C composite material according to claim 1, it is characterized in that, the temperature in the described autoclave in described step (1) is-10 ~ 100 DEG C, and pressure is 1 ~ 10MPa.
5. the preparation method of Si-C composite material according to claim 1, it is characterized in that, described silica-base material in described step (1) is silicon, silicon monoxide, the mixture of silicon and silicon monoxide, the mixture of silicon, silicon monoxide and silicon dioxide, the mixture of silicon and silicon dioxide, the one in the mixture of silicon monoxide and silicon dioxide;
Organic carbon precursor is one or more in methylcellulose, ethyl cellulose, polypropylene, polyvinyl alcohol, polyvinyl butyral resin;
Described supercritical fluid is the one in supercritical carbon dioxide, supercritical water, supercritical methanol.
6. the preparation method of Si-C composite material according to claim 1, it is characterized in that, the temperature of the described high temperature cabonization in described step (3) is 350 ~ 850 DEG C, and the time of carbonization is 1 ~ 24 hour.
7. the preparation method of Si-C composite material according to claim 1, it is characterized in that, the quality of the described silicon in the described Si-C composite material obtained in described step (3) accounts for 50 ~ 90% of described Si-C composite material quality.
8. a Si-C composite material, is characterized in that, it is prepared by the method described in claim 1 ~ 7 any one.
9. a lithium ion battery, is characterized in that, its negative pole contains Si-C composite material according to claim 8.
10. lithium ion battery according to claim 9, it is characterized in that, described negative material also comprises graphite, and the mass ratio of described Si-C composite material and described graphite is (1:15) ~ (1:2).
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