CN102593418A - Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material - Google Patents
Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material Download PDFInfo
- Publication number
- CN102593418A CN102593418A CN2012100432735A CN201210043273A CN102593418A CN 102593418 A CN102593418 A CN 102593418A CN 2012100432735 A CN2012100432735 A CN 2012100432735A CN 201210043273 A CN201210043273 A CN 201210043273A CN 102593418 A CN102593418 A CN 102593418A
- Authority
- CN
- China
- Prior art keywords
- carbon
- composite material
- silicon
- silicon composite
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002153 silicon-carbon composite material Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 87
- 239000010703 silicon Substances 0.000 claims abstract description 87
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 57
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002131 composite material Substances 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 230000007797 corrosion Effects 0.000 claims abstract description 20
- 238000005260 corrosion Methods 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 82
- 239000011248 coating agent Substances 0.000 claims description 44
- 238000000576 coating method Methods 0.000 claims description 44
- 239000000377 silicon dioxide Substances 0.000 claims description 41
- 235000013312 flour Nutrition 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001694 spray drying Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 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 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 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 5
- 239000008103 glucose Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 210000000481 breast Anatomy 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 86
- 239000011863 silicon-based powder Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 37
- 239000000463 material Substances 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000004087 circulation Effects 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 239000007833 carbon precursor Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- -1 ethyl carbonate ester Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a carbon-silicon composite material, a preparation method of the carbon-silicon composite material and a lithium ion battery containing the carbon-silicon composite material. The preparation method comprises the steps of: directly selecting silicon powder as a raw material, wrapping the silicon powder with a precursor of organic carbon to obtain a porous carbon layer wrapping silicon composite material, and using corrosive liquid to remove partial silicon in the porous carbon layer wrapping silicon composite material by corrosion, so as to obtain the carbon-silicon composite material, wherein a gap exists between a carbon shell and the silicon arranged in the carbon shell. The preparation process is simple. The carbon-silicon composite material prepared by the preparation method disclosed by the invention is good in electrochemical property, and the battery prepared from the carbon-silicon composite material is good in cycling performance.
Description
Technical field
The invention belongs to battery manufacturing technology field, the lithium ion battery that is specifically related to a kind of height ratio capacity carbon-silicon composite material and preparation method thereof and uses this carbon-silicon composite material to prepare.
Background technology
At present; It is negative material that the lithium ion battery of practical application mainly adopts graphitized carbon; The layer structure space that the graphite-based negative material is bigger is that the storage of lithium provides the place, the big characteristic that has determined the low theoretical specific capacity (about 372mAh/g) of this material of this layer structure.Therefore, high power capacity and powerful negative material have very high research and use value.For a long time, silica-based and tin-based material are just owing to its high specific discharge capacity (theoretical specific capacity of silicon and tin is respectively 4200mAh/g and 990mAh/g) becomes research focus, particularly silica-base material.Yet silicium cathode is accompanied by serious volumetric expansion and contraction in the doff lithium process, causes the electroactive material powder of detached on the electrode, finally causes capacity attenuation.For improving the cyclical stability of silica-base material; Developing siliceous alloy and composite material has become the emphasis of people's research; The research thinking generally is that silicon and other inactive metals (like Fe, Al, Cu etc.) are formed alloy (Wen Zhongsheng, Yang Jun, Liu Yu etc.; Used as negative electrode of Li-ion battery silicon-aluminum/carbon composite and preparation method thereof; One Chinese patent application number: CN03116070.0), or silicon materials are evenly spread to form composite materials such as Si-C, Si-TiN (Yang Jun, Wen Zhongsheng, Liu Yu etc., the carbon-silicon composite material of used as negative electrode of Li-ion battery height ratio capacity and preparation method in other activity or the non-active material; One Chinese patent application number: CN02112180.X), these alloys and composite material can improve its cyclical stability to a certain extent.
Though said method has been alleviated the capacity attenuation of silicon-based anode material to a certain extent; But all to be simple physics compound or pyrocarbon coats for its mechanism; All can not fundamentally suppress the bulk effect in the charge and discharge process, through after the circulation repeatedly, capacity will begin again to decay rapidly.
Summary of the invention
Technical problem to be solved by this invention is to the above-mentioned deficiency that exists in the prior art, the lithium ion battery that a kind of carbon-silicon composite material and preparation method thereof is provided and is prepared by this carbon-silicon composite material.This preparation technology is simple, and prepared carbon-silicon composite material can effectively suppress the volumetric expansion of silicium cathode, big, the good cycle of corresponding lithium ion battery specific capacity.
Solving the technical scheme that technical problem of the present invention adopted is a kind of preparation method of carbon-silicon composite material, may further comprise the steps:
(1) mixes: the organic carbon presoma is mixed with silica flour, obtain the mixture of organic carbon presoma and silica flour;
(2) coat:, obtain the composite material that the porous carbon-coating closely coats silicon said mixture high temperature cabonization in inert atmosphere;
(3) corrosion: remove the part silicon in the composite material that described porous carbon-coating closely coats silicon with corrosive liquid corrosion, obtain carbon-silicon composite material, have the space between carbon shell and its inner silicon in the said carbon-silicon composite material.
Preferably, organic carbon presoma and silica flour method of mixing are comprised ball milling, grinding, spray drying are one of any in the said step (1).
More preferably, the mixed method of organic carbon presoma in the said step (1) and silica flour is a spray drying process.The organic carbon presoma is dissolved in and obtains solution in the organic solvent, and the solution with the organic carbon presoma mixes with silica flour again, uses ultrasonic dispersing 5～120 minutes, and spray drying makes carbon dust be evenly distributed on silicon powder surface, forms organic carbon matrix precursor layer.
Preferably; Organic carbon presoma in the said step (1) comprises any one or several kinds the mixture wherein in polyvinyl alcohol, polyvinyl chloride, butadiene-styrene rubber breast, polymethyl methacrylate, polyacrylonitrile, phenolic resins, pitch, glucose, sucrose, the starch, and silica flour is that particle diameter is the silica flour of 0.05～5 μ m; The mass ratio of organic carbon presoma and silica flour is (1: 20)～(40: 10).
Preferably, the mass ratio of organic carbon presoma and silica flour is (1: 10)～(15: 10) in the said step (1).
Preferably, the temperature of the mixture high temperature cabonization in inert atmosphere in the said step (2) is 400～1500 ℃, and carbonization time is 0.1～12 hour.
Preferably, the temperature of the mixture high temperature cabonization in inert atmosphere in the said step (2) is 700～1200 ℃, and carbonization time is 1～5 hour, obtains the composite material that the porous carbon-coating closely coats silicon.
Preferably, the corrosive liquid in the said step (3) is one of any in the following corrosive liquid, wherein,
Corrosive liquid 2 is that 3%～40% hydrofluoric acid solution and mass percentage concentration are that 5%～35% salpeter solution mixes by mass percentage concentration;
Corrosive liquid 3 is the sodium hydroxide solution of 0.1～10mol/L, and one of 0.1～5.5mol/L potassium hydroxide and 0.1～1.5mol/L sodium carbonate liquor are any.
Preferably, the middle porous carbon-coating of said step (3) closely coats the composite material of silicon and the mass ratio of corrosive liquid is (1: 10)～(1: 1000), and the corrosion treatment time is 0.5～100 hour.
More preferably, the middle porous carbon-coating of said step (3) closely coats the composite material of silicon and the mass ratio of corrosive liquid is (1: 10)～(1: 50), and the corrosion treatment time is 2～24 hours.
Said step (2) closely is coated on the silicon porous carbon-coating, in the step (3), removes the part silicon in the composite material that porous carbon-coating in the step (2) closely coats silicon with corrosive liquid corrosion, between carbon and silicon, forms certain gap, makes carbon-silicon composite material.Carbon-silicon composite material obtained by this method is during as the negative pole of lithium ion battery; Under the removal lithium embedded condition of high level, between carbon and silicon, there are enough spaces to hold the lithium of embedding, when lithium takes off embedding; This nucleocapsid structure is stable; Bulk effect when greatly reducing silicon materials as negative material has reduced the powder phenomenon-tion of silicon, has improved the stability of material.
The present invention also provides a kind of carbon-silicon composite material that uses above-mentioned preparation method's preparation.
The present invention also provides a kind of lithium ion battery, and its negative pole contains above-mentioned material, even prepare the negative pole of lithium ion battery with above-mentioned carbon-silicon composite material, is assembled into lithium ion battery again.
Beneficial effect of the present invention: the preparation process of this carbon-silicon composite material is simple, and this preparation method can control the silicone content in the nucleocapsid structure in the carbon-silicon composite material, the space in the adjusting nucleocapsid structure between carbon shell and its inner silicon; This carbon-silicon composite material has certain lithium storage content, and this is because it has used the dispersible carrier of the carbon class material of electrochemical reversible doff lithium stable performance as active material.Composite material discharge and recharge characteristic possess carrier carbon material and silicon class material separately discharge and recharge characteristic and compound characteristics, so possess the high lithium storage content characteristic of silicon class material and the high cyclical stability of carbon class material simultaneously.
The carbon-silicon composite material that use the present invention makes is as the negative pole of lithium ion battery; Can make the specific capacity and the cycle performance of lithium ion battery have marked improvement; By the battery of made of the present invention, first discharge specific capacity is high, and stable; First discharge specific capacity still remains on 650～750mAh/g at 900～1200mAh/g after 105 circulations.
Description of drawings
Fig. 1 is the sketch map that material structure changes in the preparation carbon-silicon composite material process of the embodiment of the invention 4;
The charge-discharge performance resolution chart of the lithium ion battery that Fig. 2 processes for the carbon-silicon composite material of preparation in the embodiment of the invention 6.
Among the figure: 1-silicon; 2-organic carbon precursor layer; 3-porous carbon-coating; 4-porous carbon-coating closely coats the composite material of silicon; The 5-carbon-silicon composite material.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, the present invention is described in further detail below in conjunction with accompanying drawing and embodiment.
Present embodiment provides a kind of preparation method of carbon-silicon composite material, and it may further comprise the steps:
(1) mix: the silica flour that with polyvinyl chloride and particle diameter is 1.5 μ m is 1: 1 a mixed ball milling according to mass ratio, obtains the mixture of polyvinyl chloride and silica flour;
(2) coat: said mixture is transferred in the porcelain boat, under the protection of argon gas, is warmed up to 950 ℃, be incubated 5 hours, take out the cooling back, obtains the composite material that the porous carbon-coating closely coats silicon;
(3) corrosion: the composite material that described porous carbon-coating is closely coated silicon joins in the corrosive liquid; Both mass ratioes are 1: 200, continuous stirring 24 hours, and the part silicon that the porous carbon-coating closely coats in the composite material of silicon is corroded; The suspended matter of gained is filtered; And fully wash with distilled water, oven dry promptly get carbon-silicon composite material, wherein has the space between the silicon of carbon shell and inside.Wherein corrosive liquid is that 3% hydrofluoric acid solution and 24g mass fraction are that 30% hydrogen peroxide solution mixes by the 400ml mass fraction.
The gained carbon-silicon composite material is mixed according to mass ratio with conductive agent acetylene black, binding agent PVDF respectively at 80: 10: 10; With NMP (1-Methyl-2-Pyrrolidone) this mixture is modulated into slurry; Evenly be coated on the Copper Foil, 100 ℃ of vacuumize 24 hours makes Experimental cell and uses pole piece.With the lithium sheet is to electrode; Electrolyte is the LiPF6 solution of 1mol/L; Solvent is EC (ethyl carbonate ester)+DMC (dimethyl carbonate) (volume ratio 1: 1), and barrier film is the celgard2400 film, in being full of the glove box of argon gas atmosphere, is assembled into CR2025 type button cell.
Press the battery of the method made of present embodiment, first discharge specific capacity has reached 1057mAh/g, still remains on 738mAh/g after 105 circulations.
Embodiment 2
Present embodiment provides a kind of preparation method of carbon-silicon composite material, and it may further comprise the steps:
(1) mixes: phenolic resins is dissolved in the mixed solvent of ethanol and distilled water; Obtain the solution of phenolic resins; Add the silica flour of 0.05 μ m in the solution, the mass ratio of phenolic resins and silica flour is 1: 10, ultrasonic dispersion 120 minutes; Obtain the mixture of phenolic resins and silica flour again through spray drying, the organic carbon presoma is evenly distributed on the surface of silicon;
(2) coat: said mixture is transferred in the porcelain boat, under protection of nitrogen gas, is warmed up to 650 ℃, be incubated 6 hours, take out the cooling back, obtains the composite material that the porous carbon-coating closely coats silicon;
(3) corrosion: the composite material that described porous carbon-coating is closely coated silicon joins in the corrosive liquid; Both mass ratioes are 1: 50, continuous stirring 20 hours, and the part silicon that the porous carbon-coating closely coats in the composite material of silicon is corroded; The suspended matter of gained is filtered; And fully wash with distilled water, oven dry promptly get carbon-silicon composite material, wherein has the space between the silicon of carbon shell and inside.Wherein corrosive liquid is that 40% hydrofluoric acid solution and 80g mass fraction are that 5% salpeter solution mixes by the 100ml mass fraction.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1153mAh/g, still remain on 735mAh/g after 105 circulations.
Embodiment 3
Present embodiment provides a kind of preparation method of carbon-silicon composite material, and it may further comprise the steps:
(1) mix: the silica flour that with butadiene-styrene rubber breast and particle diameter is 2.5 μ m is that 4: 1 mixed is ground according to mass ratio, obtains the mixture of butadiene-styrene rubber breast and silica flour;
(2) coat: said mixture is transferred in the porcelain boat, under the protection of argon gas and hydrogen gas mixture, is warmed up to 1100 ℃, be incubated 2 hours, take out the cooling back, obtains the composite material that the porous carbon-coating closely coats silicon;
(3) corrosion: the composite material that described porous carbon-coating is closely coated silicon joins in the corrosive liquid; Both mass ratioes are 1: 10, continuous stirring 13 hours, and the part silicon that the porous carbon-coating closely coats in the composite material of silicon is corroded; The suspended matter of gained is filtered; And fully wash with distilled water, oven dry promptly get carbon-silicon composite material, wherein has the space between the silicon of carbon shell and inside.Wherein corrosive liquid is that 40% hydrofluoric acid solution and 30g mass fraction are that 1% hydrogen peroxide solution mixes by the 100ml mass fraction.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 950mAh/g, still remain on 697mAh/g after 105 circulations.
Embodiment 4
Present embodiment provides a kind of preparation method of carbon-silicon composite material, and it may further comprise the steps:
(1) mixes: sucrose and glucose is soluble in water; Obtain the mixed solution of sucrose and glucose; Add the silica flour of 0.5 μ m in the solution, the mass ratio of sucrose and glucose organic carbon presoma and silica flour is 15: 10, ultrasonic dispersion 40 minutes; Obtain the mixture of organic carbon presoma and silica flour again through spray drying, the organic carbon presoma is evenly distributed on the surface of silicon;
(2) coat: said mixture is transferred in the porcelain boat, under protection of nitrogen gas, is warmed up to 1200 ℃, be incubated 1 hour, take out the cooling back, obtains the composite material that the porous carbon-coating closely coats silicon;
(3) corrosion: the composite material that described porous carbon-coating is closely coated silicon joins in the corrosive liquid; Both mass ratioes are 1: 1000, continuous stirring 60 hours, and the part silicon that the porous carbon-coating closely coats in the composite material of silicon is corroded; The suspended matter of gained is filtered; And fully wash with distilled water, oven dry promptly get carbon-silicon composite material, wherein has the space between the silicon of carbon shell and inside.Wherein corrosive liquid is that 21% hydrofluoric acid solution and 10g mass fraction are that 20% salpeter solution mixes by the 500ml mass fraction.
As shown in Figure 1, organic carbon presoma and silicon form uniform organic carbon precursor layer 2 after using spray-drying process on the surface of silicon 1; This mixture through behind the high-temperature calcination process, forms the porous carbon-coating 3 of tight coating on the surface of silicon under inert atmosphere, promptly form the composite material 4 that the porous carbon-coating closely coats silicon; Again through corrosive liquid corrosion, remove the part silicon in the composite material 4 that the porous carbon-coating closely coats silicon, form the nucleocapsid structure that certain gap is arranged between carbon shell and the silica flour, obtain carbon-silicon composite material 5.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1052mAh/g, still remain on 780mAh/g after 105 circulations.
Embodiment 5
Present embodiment provides a kind of preparation method of carbon-silicon composite material, and it may further comprise the steps:
(1) mix: the silica flour that with polymethyl methacrylate and particle diameter is 1 μ m is 1: 20 mixed grinding according to mass ratio, obtains the mixture of polymethyl methacrylate and silica flour;
(2) coat: said mixture is transferred in the porcelain boat, under the protection of argon gas and hydrogen gas mixture, is warmed up to 1000 ℃, be incubated 2.5 hours, take out the cooling back, obtains the composite material that the porous carbon-coating closely coats silicon;
(3) corrosion: the composite material that described porous carbon-coating is closely coated silicon joins in the corrosive liquid; Both mass ratioes are 1: 20, continuous stirring 13 hours, and the part silicon that the porous carbon-coating closely coats in the composite material of silicon is corroded; The suspended matter of gained is filtered; And fully wash with distilled water, oven dry promptly get carbon-silicon composite material, wherein has the space between the silicon of carbon shell and inside.Wherein corrosive liquid is that 3% hydrofluoric acid solution and 40g mass fraction are that 35% salpeter solution mixes by the 500ml mass fraction.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1138mAh/g, still remain on 704mAh/g after 105 circulations.
Embodiment 6
Present embodiment provides a kind of preparation method of carbon-silicon composite material, and it may further comprise the steps:
(1) mixes: polyvinyl alcohol is dissolved in the mixed solvent of ethanol and water; Obtain the solution of polyvinyl alcohol; Add the silica flour of 5 μ m in the solution, the mass ratio of polyvinyl alcohol and silica flour is 3: 4, ultrasonic dispersion 5 minutes; Obtain the mixture of polyvinyl alcohol and silica flour again through spray drying, the organic carbon presoma is evenly distributed on the surface of silicon;
(2) coat: said mixture is transferred in the porcelain boat, under the protection of argon gas, is warmed up to 400 ℃, be incubated 12 hours, take out the cooling back, obtains the composite material that the porous carbon-coating closely coats silicon;
(3) corrosion: the composite material that described porous carbon-coating is closely coated silicon joins in the corrosive liquid; Both mass ratioes are 1: 40, continuous stirring 50 hours, and the part silicon that the porous carbon-coating closely coats in the composite material of silicon is corroded; The suspended matter of gained is filtered; And fully wash with distilled water, oven dry promptly get carbon-silicon composite material, wherein has the space between the silicon of carbon shell and inside.Wherein corrosive liquid is the sodium hydroxide solution of the 5mol/L of 400ml.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and be as shown in Figure 2; First discharge specific capacity has reached 1149mAh/g, still remains on 781mAh/g after 105 circulations, and the carbon-silicon composite material nucleocapsid structure is described; Under the removal lithium embedded condition of high level, between carbon and silicon, there are enough spaces to hold the lithium of embedding, when lithium takes off embedding; This nucleocapsid structure is stable; Bulk effect when greatly reducing silicon materials as negative material has reduced the powder phenomenon-tion of silicon, has improved the stability of material.
Embodiment 7
Present embodiment provides a kind of preparation method of carbon-silicon composite material, and it may further comprise the steps:
(1) mix: the silica flour that with grape sugar and starch and particle diameter is 2.5 μ m is 3: 1 a mixed ball milling according to mass ratio, obtains the mixture of grape sugar and starch and silica flour;
(2) coat: said mixture is transferred in the porcelain boat, under protection of nitrogen gas, is warmed up to 900 ℃, be incubated 3 hours, take out the cooling back, obtains the composite material that the porous carbon-coating closely coats silicon;
(3) corrosion: the composite material that described porous carbon-coating is closely coated silicon joins in the corrosive liquid; Both mass ratioes are 1: 500, continuous stirring 100 hours, and the part silicon that the porous carbon-coating closely coats in the composite material of silicon is corroded; The suspended matter of gained is filtered; And fully wash with distilled water, oven dry promptly get carbon-silicon composite material, wherein has the space between the silicon of carbon shell and inside.Wherein corrosive liquid is the sodium hydroxide solution of the 0.1mol/L of 300ml.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1094mAh/g, still remain on 699mAh/g after 105 circulations.
Embodiment 8
Present embodiment provides a kind of preparation method of carbon-silicon composite material, and it may further comprise the steps:
(1) mixes: polyacrylonitrile is dissolved in the acetone; Obtain the solution of polyacrylonitrile; Add the silica flour of 0.8 μ m in the solution, the mass ratio of polyacrylonitrile and silica flour is 1: 2, ultrasonic dispersion 62 minutes; Obtain the mixture of polyacrylonitrile and silica flour again through spray drying, the organic carbon presoma is evenly distributed on the surface of silicon;
(2) coat: said mixture is transferred in the porcelain boat, under the protection of argon gas and hydrogen gas mixture, is warmed up to 1500 ℃, be incubated 0.1 hour, take out the cooling back, obtains the composite material that the porous carbon-coating closely coats silicon;
(3) corrosion: the composite material that described porous carbon-coating is closely coated silicon joins in the corrosive liquid; Both mass ratioes are 1: 300, continuous stirring 0.5 hour, and the part silicon that the porous carbon-coating closely coats in the composite material of silicon is corroded; The suspended matter of gained is filtered; And fully wash with distilled water, oven dry promptly get carbon-silicon composite material, wherein has the space between the silicon of carbon shell and inside.Wherein corrosive liquid is that 21% hydrofluoric acid solution and 60g mass fraction are that 15% hydrogen peroxide solution mixes by the 500ml mass fraction.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 1210mAh/g, still remain on 695mAh/g after 105 circulations.
Embodiment 9
Present embodiment provides a kind of preparation method of carbon-silicon composite material, and it may further comprise the steps:
(1) mixes: pitch is dissolved in the acetone, obtains the solution of pitch, the silica flour of adding 3 μ m in the solution; The mass ratio of pitch and silica flour is 2: 1; Ultrasonic dispersion 80 minutes obtains the mixture of pitch and silica flour again through spray drying, the organic carbon presoma is evenly distributed on the surface of silicon;
(2) coat: said mixture is transferred in the porcelain boat, under the protection of argon gas, is warmed up to 700 ℃, be incubated 4 hours, take out the cooling back, obtains the composite material that the porous carbon-coating closely coats silicon;
(3) corrosion: the composite material that described porous carbon-coating is closely coated silicon joins in the corrosive liquid; Both mass ratioes are 1: 25, continuous stirring 2 hours, and the part silicon that the porous carbon-coating closely coats in the composite material of silicon is corroded; The suspended matter of gained is filtered; And fully wash with distilled water, oven dry promptly get carbon-silicon composite material, wherein has the space between the silicon of carbon shell and inside.Wherein corrosive liquid is the sodium hydroxide solution of the 10mol/L of 200ml.
The manufacture method of CR2025 type button cell such as embodiment 1 press the battery of present embodiment method made, and first discharge specific capacity has reached 970mAh/g, still remain on 682mAh/g after 105 circulations.
Among above-mentioned each embodiment, in corrosive liquid with the configuration of hydrofluoric acid solution and hydrogen peroxide solution, the amount ratio of hydrofluoric acid solution and hydrogen peroxide solution be (50: 3)～(10: 3) (ml/g), those skilled in the art can select suitable proportioning according to demand.
Among above-mentioned each embodiment, in corrosive liquid with the preparation of hydrofluoric acid solution and salpeter solution, the amount ratio of hydrofluoric acid solution and salpeter solution be (5: 4)～(50: 1) (ml/g), those skilled in the art can select suitable proportioning according to demand.
Among above-mentioned each embodiment; 0.1 the corrosive liquid of the sodium hydroxide solution of～10mol/L; Also can be replaced, because of these solution are known silicon etch solutions, so those skilled in the art can select according to demand by 0.1～5.5mol/L potassium hydroxide or 0.1～1.5mol/L sodium carbonate liquor.
Present embodiment provides a kind of carbon-silicon composite material, and it is by method for preparing.
Embodiment 11
Present embodiment provides a kind of lithium ion battery, and its negative pole contains above-mentioned carbon-silicon composite material.
Certainly, also should comprise other material known such as positive electrode, collector, element etc. in the lithium ion battery of this enforcement.
It is understandable that above execution mode only is the illustrative embodiments that adopts for principle of the present invention is described, yet the present invention is not limited thereto.For the one of ordinary skilled in the art, under the situation that does not break away from spirit of the present invention and essence, can make various modification and improvement, these modification also are regarded as protection scope of the present invention with improving.
Claims (10)
1. the preparation method of a carbon-silicon composite material is characterized in that, may further comprise the steps:
(1) mixes: the organic carbon presoma is mixed with silica flour, obtain the mixture of organic carbon presoma and silica flour;
(2) coat:, obtain the composite material that the porous carbon-coating closely coats silicon said mixture high temperature cabonization in inert atmosphere;
(3) corrosion: remove the part silicon in the composite material that described porous carbon-coating closely coats silicon with corrosive liquid corrosion, obtain carbon-silicon composite material, have the space between carbon shell and its inner silicon in the said carbon-silicon composite material.
2. the preparation method of carbon-silicon composite material according to claim 1 is characterized in that, organic carbon presoma and silica flour method of mixing is comprised ball milling, grinding, spray drying are one of any in the said step (1).
3. the preparation method of carbon-silicon composite material according to claim 1; It is characterized in that; Organic carbon presoma in the said step (1) comprises any one or several kinds the mixture wherein in polyvinyl alcohol, polyvinyl chloride, butadiene-styrene rubber breast, polymethyl methacrylate, polyacrylonitrile, phenolic resins, pitch, glucose, sucrose, the starch, and silica flour is that particle diameter is the silica flour of 0.05～5 μ m; The mass ratio of organic carbon presoma and silica flour is (1: 20)～(40: 10).
4. the preparation method of carbon-silicon composite material according to claim 3 is characterized in that, the mass ratio of organic carbon presoma and silica flour is (1: 10)～(15: 10) in the said step (1).
5. the preparation method of carbon-silicon composite material according to claim 1 is characterized in that, the corrosive liquid in the said step (3) is one of any in the following corrosive liquid:
Corrosive liquid 1 is that 3%～40% hydrofluoric acid solution and mass percentage concentration are that 1%～30% hydrogen peroxide solution mixes by mass percentage concentration;
Corrosive liquid 2 is that 3%～40% hydrofluoric acid solution and mass percentage concentration are that 5%～35% salpeter solution mixes by mass percentage concentration;
Corrosive liquid 3 is the sodium hydroxide solution of 0.1～10mol/L, and one of 0.1～5.5mol/L potassium hydroxide and 0.1～1.5mol/L sodium carbonate liquor are any.
6. the preparation method of carbon-silicon composite material according to claim 1; It is characterized in that; The middle porous carbon-coating of said step (3) closely coats the composite material of silicon and the mass ratio of corrosive liquid is (1: 10)～(1: 1000), and the corrosion treatment time is 0.5～100 hour.
7. the preparation method of carbon-silicon composite material according to claim 6 is characterized in that, the middle porous carbon-coating of said step (3) closely coats the composite material of silicon and the mass ratio of corrosive liquid is (1: 10)～(1: 50), and the corrosion treatment time is 2～24 hours.
8. the preparation method of carbon-silicon composite material according to claim 1 is characterized in that, the temperature of the mixture high temperature cabonization in inert atmosphere in the said step (2) is 400～1500 ℃, and carbonization time is 0.1～12 hour; The temperature of the mixture high temperature cabonization in inert atmosphere in the preferably said step (2) is 700～1200 ℃, and carbonization time is 1～5 hour.
9. a carbon-silicon composite material is characterized in that, it is by any described method preparation in the claim 1 to 8.
10. a lithium ion battery is characterized in that, its negative pole contains the described carbon-silicon composite material of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100432735A CN102593418A (en) | 2012-02-24 | 2012-02-24 | Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100432735A CN102593418A (en) | 2012-02-24 | 2012-02-24 | Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102593418A true CN102593418A (en) | 2012-07-18 |
Family
ID=46481784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100432735A Pending CN102593418A (en) | 2012-02-24 | 2012-02-24 | Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102593418A (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800851A (en) * | 2012-08-17 | 2012-11-28 | 奇瑞汽车股份有限公司 | Silicon carbon composite material and preparation method thereof, lithium ion battery containing same |
| CN102931409A (en) * | 2012-10-25 | 2013-02-13 | 中国计量学院 | Preparation method of polyaniline/silicon composite with core-shell structure for lithium ion battery cathode |
| CN102983313A (en) * | 2012-12-05 | 2013-03-20 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof, and lithium ion battery |
| CN103107317A (en) * | 2013-01-17 | 2013-05-15 | 奇瑞汽车股份有限公司 | Si-C composite material and preparation method thereof and lithium ion battery containing same |
| CN103236525A (en) * | 2013-05-06 | 2013-08-07 | 奇瑞汽车股份有限公司 | Silicon carbon composite material, preparation method thereof as well as lithium ion battery |
| CN103280564A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Method for preparing carbon-coated aluminum lithium battery negative pole material with core-shell structure and cavity |
| CN103531760A (en) * | 2013-10-28 | 2014-01-22 | 北京化工大学 | Porous silicon carbon composite microsphere with yolk-eggshell structure and preparation method therefor |
| CN103872330A (en) * | 2014-03-19 | 2014-06-18 | 上海交通大学 | Lithium ion battery negative electrode material and preparation method thereof |
| CN103904335A (en) * | 2014-04-21 | 2014-07-02 | 哈尔滨工业大学 | Lithium ion battery negative material structure and preparation method thereof |
| CN104112847A (en) * | 2014-07-03 | 2014-10-22 | 奇瑞汽车股份有限公司 | Silicon-based negative electrode material and method thereof |
| CN104701491A (en) * | 2015-03-31 | 2015-06-10 | 吕铁铮 | Nano-porous silica lithium battery anode material and preparation method and application thereof |
| CN104981925A (en) * | 2013-01-29 | 2015-10-14 | 三洋电机株式会社 | Negative electrode active material for nonaqueous electrolyte secondary batteries, negative electrode for nonaqueous electrolyte secondary batteries using said negative electrode active material, and nonaqueous electrolyte secondary battery using said negative electrode |
| CN106848257A (en) * | 2017-03-26 | 2017-06-13 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon-coated silicon negative electrode material with hollow structure |
| CN107346820A (en) * | 2016-05-06 | 2017-11-14 | 香港城市大学 | A kind of composite negative pole material of three-dimensional porous carbon parcel silicon and preparation method thereof |
| CN107863504A (en) * | 2017-10-13 | 2018-03-30 | 苏州大学 | A kind of preparation method of core shell structure Si-C composite material |
| US9947928B2 (en) | 2013-02-28 | 2018-04-17 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
| CN108199020A (en) * | 2017-12-28 | 2018-06-22 | 中国科学院理化技术研究所 | Carbon-coated silicon anode material with micro-nano hierarchical structure and preparation method and application thereof |
| CN109585785A (en) * | 2018-11-22 | 2019-04-05 | 江苏科技大学 | A method of Si/CNF/C composite material and lithium ion battery negative electrode material are prepared based on waste plastics |
| CN109888228A (en) * | 2019-02-28 | 2019-06-14 | 蜂巢能源科技有限公司 | Negative electrode material of lithium ion battery and preparation method thereof |
| CN110492091A (en) * | 2019-07-01 | 2019-11-22 | 徐州硕祥信息科技有限公司 | A kind of lithium battery production negative electrode material and preparation method thereof |
| WO2020098088A1 (en) * | 2018-11-13 | 2020-05-22 | 东莞市凯金新能源科技股份有限公司 | Silicon-based composite material with hollow/porous structure, and preparation method therefor |
| CN111584846A (en) * | 2020-05-21 | 2020-08-25 | 合肥国轩高科动力能源有限公司 | Silicon-carbon material with hemp ball-like structure and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101944596A (en) * | 2010-07-30 | 2011-01-12 | 中国科学院化学研究所 | Preparation method of silicon and carbon composite microspheres and application thereof |
| CN102208635A (en) * | 2011-05-06 | 2011-10-05 | 奇瑞汽车股份有限公司 | Lithium ion battery cathode material and manufacturing method thereof and lithium ion battery |
-
2012
- 2012-02-24 CN CN2012100432735A patent/CN102593418A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101944596A (en) * | 2010-07-30 | 2011-01-12 | 中国科学院化学研究所 | Preparation method of silicon and carbon composite microspheres and application thereof |
| CN102208635A (en) * | 2011-05-06 | 2011-10-05 | 奇瑞汽车股份有限公司 | Lithium ion battery cathode material and manufacturing method thereof and lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| YA-XIA YIN ET AL: "Electrospray Synthesis of Silicon/Carbon Nanoporous Microspheres as Improved Anode Materials for Lithium-Ion Batteries", 《THE JOURNAL OF PHYSICAL CHEMISTRY C》 * |
Cited By (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102800851A (en) * | 2012-08-17 | 2012-11-28 | 奇瑞汽车股份有限公司 | Silicon carbon composite material and preparation method thereof, lithium ion battery containing same |
| CN102931409A (en) * | 2012-10-25 | 2013-02-13 | 中国计量学院 | Preparation method of polyaniline/silicon composite with core-shell structure for lithium ion battery cathode |
| CN102931409B (en) * | 2012-10-25 | 2015-08-12 | 中国计量学院 | A kind of used as negative electrode of Li-ion battery polyaniline/silicon composite preparation method of nucleocapsid structure |
| CN102983313A (en) * | 2012-12-05 | 2013-03-20 | 奇瑞汽车股份有限公司 | Silicon-carbon composite material and preparation method thereof, and lithium ion battery |
| CN102983313B (en) * | 2012-12-05 | 2016-01-27 | 奇瑞汽车股份有限公司 | Si-C composite material and preparation method thereof, lithium ion battery |
| CN103107317A (en) * | 2013-01-17 | 2013-05-15 | 奇瑞汽车股份有限公司 | Si-C composite material and preparation method thereof and lithium ion battery containing same |
| CN103107317B (en) * | 2013-01-17 | 2016-03-16 | 奇瑞汽车股份有限公司 | A kind of Si-C composite material and preparation method thereof, lithium ion battery containing this material |
| JPWO2014119256A1 (en) * | 2013-01-29 | 2017-01-26 | 三洋電機株式会社 | Negative electrode active material for nonaqueous electrolyte secondary battery, negative electrode for nonaqueous electrolyte secondary battery using the negative electrode active material, and nonaqueous electrolyte secondary battery using the negative electrode |
| CN104981925A (en) * | 2013-01-29 | 2015-10-14 | 三洋电机株式会社 | Negative electrode active material for nonaqueous electrolyte secondary batteries, negative electrode for nonaqueous electrolyte secondary batteries using said negative electrode active material, and nonaqueous electrolyte secondary battery using said negative electrode |
| US9947928B2 (en) | 2013-02-28 | 2018-04-17 | Sanyo Electric Co., Ltd. | Nonaqueous electrolyte secondary battery |
| CN103236525B (en) * | 2013-05-06 | 2015-09-23 | 奇瑞汽车股份有限公司 | A kind of Si-C composite material and preparation method thereof, lithium ion battery |
| CN103236525A (en) * | 2013-05-06 | 2013-08-07 | 奇瑞汽车股份有限公司 | Silicon carbon composite material, preparation method thereof as well as lithium ion battery |
| CN103280564B (en) * | 2013-05-27 | 2015-05-20 | 浙江大学 | Method for preparing carbon-coated aluminum lithium battery negative pole material with core-shell structure and cavity |
| CN103280564A (en) * | 2013-05-27 | 2013-09-04 | 浙江大学 | Method for preparing carbon-coated aluminum lithium battery negative pole material with core-shell structure and cavity |
| CN103531760A (en) * | 2013-10-28 | 2014-01-22 | 北京化工大学 | Porous silicon carbon composite microsphere with yolk-eggshell structure and preparation method therefor |
| CN103872330A (en) * | 2014-03-19 | 2014-06-18 | 上海交通大学 | Lithium ion battery negative electrode material and preparation method thereof |
| CN103904335B (en) * | 2014-04-21 | 2016-02-17 | 哈尔滨工业大学 | A kind of lithium ion battery negative material |
| CN103904335A (en) * | 2014-04-21 | 2014-07-02 | 哈尔滨工业大学 | Lithium ion battery negative material structure and preparation method thereof |
| CN104112847A (en) * | 2014-07-03 | 2014-10-22 | 奇瑞汽车股份有限公司 | Silicon-based negative electrode material and method thereof |
| CN104701491A (en) * | 2015-03-31 | 2015-06-10 | 吕铁铮 | Nano-porous silica lithium battery anode material and preparation method and application thereof |
| CN107346820B (en) * | 2016-05-06 | 2020-08-14 | 香港城市大学 | Composite anode material with silicon coated by three-dimensional porous carbon and preparation method thereof |
| CN107346820A (en) * | 2016-05-06 | 2017-11-14 | 香港城市大学 | A kind of composite negative pole material of three-dimensional porous carbon parcel silicon and preparation method thereof |
| CN106848257A (en) * | 2017-03-26 | 2017-06-13 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon-coated silicon negative electrode material with hollow structure |
| CN106848257B (en) * | 2017-03-26 | 2019-03-29 | 合肥国轩高科动力能源有限公司 | Preparation method of carbon-coated silicon negative electrode material with hollow structure |
| CN107863504A (en) * | 2017-10-13 | 2018-03-30 | 苏州大学 | A kind of preparation method of core shell structure Si-C composite material |
| CN108199020A (en) * | 2017-12-28 | 2018-06-22 | 中国科学院理化技术研究所 | Carbon-coated silicon anode material with micro-nano hierarchical structure and preparation method and application thereof |
| CN108199020B (en) * | 2017-12-28 | 2020-04-10 | 中国科学院理化技术研究所 | Carbon-coated silicon anode material with micro-nano hierarchical structure and preparation method and application thereof |
| WO2020098088A1 (en) * | 2018-11-13 | 2020-05-22 | 东莞市凯金新能源科技股份有限公司 | Silicon-based composite material with hollow/porous structure, and preparation method therefor |
| CN109585785A (en) * | 2018-11-22 | 2019-04-05 | 江苏科技大学 | A method of Si/CNF/C composite material and lithium ion battery negative electrode material are prepared based on waste plastics |
| CN109888228A (en) * | 2019-02-28 | 2019-06-14 | 蜂巢能源科技有限公司 | Negative electrode material of lithium ion battery and preparation method thereof |
| CN110492091A (en) * | 2019-07-01 | 2019-11-22 | 徐州硕祥信息科技有限公司 | A kind of lithium battery production negative electrode material and preparation method thereof |
| CN111584846A (en) * | 2020-05-21 | 2020-08-25 | 合肥国轩高科动力能源有限公司 | Silicon-carbon material with hemp ball-like structure and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102593418A (en) | Carbon-silicon composite material, preparation method thereof, and lithium ion battery containing carbon-silicon composite material | |
| CN102694155B (en) | Silicon-carbon composite material, preparation method thereof and lithium ion battery employing same | |
| CN103107317B (en) | A kind of Si-C composite material and preparation method thereof, lithium ion battery containing this material | |
| CN102769139B (en) | Preparation method of high power capacity lithium ion battery cathode material | |
| CN106784640B (en) | Silicon-based composite negative electrode material for lithium ion battery, preparation method of silicon-based composite negative electrode material and lithium ion battery negative electrode containing silicon-based composite negative electrode material | |
| CN102157731B (en) | Silicon and carbon compound anode material of lithium ion battery and preparation method of silicon and carbon compound anode material | |
| CN102800851A (en) | Silicon carbon composite material and preparation method thereof, lithium ion battery containing same | |
| CN103346303B (en) | A kind of Si-C composite material and preparation method thereof, lithium ion battery | |
| CN103236530B (en) | Si-C composite material and preparation method thereof, lithium ion battery containing this material | |
| CN103337613B (en) | A kind of Si-C composite material and preparation method thereof, lithium ion battery | |
| CN104009210B (en) | A kind of porous silicon/carbon composite material, Preparation method and use | |
| CN103346324B (en) | Lithium ion battery cathode material and its preparation method | |
| CN102403491A (en) | Lithium ion battery silicon-carbon composite negative electrode material and preparation method thereof, and lithium ion battery | |
| CN102522534B (en) | Silicon-carbon composite material with high specific capacity, preparation method of silicon-carbon composite material, lithium ion battery anode material and lithium ion battery | |
| CN102208635A (en) | Lithium ion battery cathode material and manufacturing method thereof and lithium ion battery | |
| CN102447112A (en) | Silicon-carbon composite material, preparation method thereof, negative electrode material containing silicon-carbon composite material and lithium ion battery | |
| CN103346293A (en) | Lithium ion battery cathode material and preparation method thereof as well as lithium ion battery | |
| CN102983317A (en) | Silicon-based composite material and preparation method thereof, silicon-carbon composite material and lithium ion battery | |
| CN104538585B (en) | Hollow porous micron order silicon ball, silicon based anode material and preparation method of lithium ion battery | |
| CN102983313A (en) | Silicon-carbon composite material and preparation method thereof, and lithium ion battery | |
| CN110416533B (en) | Ion battery composite material, preparation method thereof and ion battery | |
| CN107221661A (en) | A kind of preparation method of graphite negative material of lithium ion battery | |
| US20240105941A1 (en) | Negative Electrode Material, Negative Electrode Plate, and Sodium Ion Battery | |
| CN111640916A (en) | Preparation method of lithium ion battery negative electrode material | |
| CN110336035B (en) | Tin dioxide/aluminum oxide doped carbon composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120718 |