CN104064736A - Carbon nanotube/silicon/graphene composite material, preparation method thereof and lithium ion battery - Google Patents
Carbon nanotube/silicon/graphene composite material, preparation method thereof and lithium ion battery Download PDFInfo
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- 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
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a carbon nanotube/silicon/graphene composite material and a preparation method, the method comprises the following steps: heating a substrate to 500-1300 DEG C, then introducing carbon source in a gaseous state into a reaction chamber, keeping temperature, reacting for 1-300 minutes, stopping the introduction of the carbon source in the gaseous state to obtain the carbon nanotube material; then introducing a silicon source in the gaseous state in the reaction chamber, keeping for 1-300 minutes, stopping heating of the substrate and cooling to room temperature to obtain the carbon nanotube/silicon composite material; taking the carbon nanotube/silicon composite material, placing graphene and the carbon nanotube/silicon composite material in absolute ethyl alcohol for ultrasonic reaction, then filtering and drying to obtain the carbon nanotube/silicon/graphene composite material. In the carbon nanotube/silicon/graphene composite material, the prepared silicon carbon composite material is used for a cathode material of a lithium ion battery, and has excellent energy storage performance and cycle performance.
Description
Technical field
The preparation field that the present invention relates to chemical material, relates in particular to a kind of carbon nanometer tube/silicon/graphene composite material and preparation method thereof.The invention still further relates to the application of this Si-C composite material in lithium ion battery.
Background technology
Lithium ion battery is as a kind of novel energy-storing device, and lot of domestic and international scientific research institution and enterprise fall over each other research.Along with the development of various electronic products, the performance of lithium ion battery more and more can not meet the demand of various consumer products.At present the negative material of lithium ion battery is mainly used graphite, and the theoretical capacity of graphite is only up to 372mAh/g, and this has limited the performance of lithium ion battery greatly.
Recently, researcher finds that silicon is as negative material, has very high stored energy capacitance, and the highest theoretical capacity can reach 4200mAh/g, and this is just for the raising of performance of lithium ion battery provides a kind of very effective method.But there is a problem as negative material in silicon, be that silicon change in volume in the process of embedding lithium and de-lithium is larger, this can cause electrode material powdered, make lithium ion battery along with the increase stored energy capacitance of cycle-index declines very fast, thereby shorten the life-span of lithium ion battery, this is a major issue urgently to be resolved hurrily before silicon materials are applied.
Carbon nano-tube has larger draw ratio, and has higher conductivity.Graphene is a kind of two-dimentional monolayer material, has excellent flexibility.So silicon materials and carbon nano-tube, Graphene carry out compound can effectively reduce silicon materials expand and contraction process in destruction to electrode material, thereby improve the cycle performance of device.
Summary of the invention
The object of the invention is to solve the problem and shortage that above-mentioned prior art exists, a kind of carbon nanometer tube/silicon/graphene composite material be provided, when it is applied in lithium ion battery, show excellent energy-storage property and cycle performance.
The technical scheme that the present invention is directed to above-mentioned technical problem and propose is: a kind of preparation method of carbon nanometer tube/silicon/graphene composite material, comprises the steps:
Cleaning dried substrate are put into reative cell, pass into inert gas, make to form inert environments in described reactor, then described reative cell is taken out to press and process 1～30 minute, stop passing into inert gas and stop taking out pressure;
Described substrate is heated to 500～1300 DEG C, then passes into gaseous carbon source to described reative cell, keep temperature-resistant, react after 1～300 minute, stop passing into described gaseous carbon source, obtain carbon nano-tube material;
Then pass into gaseous state silicon source to described reative cell, keep, after 1～300 minute, stopping substrate heating and be cooled to room temperature, obtain carbon nanometer tube/silicon composite material;
Take out described carbon nanometer tube/silicon composite material, Graphene and described carbon nanometer tube/silicon composite material are placed in to absolute ethyl alcohol and carry out ultrasonicly, then filtration drying, obtains carbon nanometer tube/silicon/graphene composite material.
Described substrate is one or more in Copper Foil, iron foil or nickel foil.
Described gaseous carbon sources be a kind of in methane, ethane, ethene and acetylene or or multiple; Described gaseous state silicon source is silicon tetrahydride.
The flow of described gaseous carbon source is 50～400ml/min, and the flow in described gaseous state silicon source is 50～300ml/min.
Take out and press while processing, adopt mechanical pump, lobe pump and molecular pump to take out step by step pressure, the pressure in reative cell is evacuated to 10
-3below Pa.
Described ultrasonic time is 3～5h.
The present invention also comprises the carbon nanometer tube/silicon/graphene composite material that utilizes above-mentioned preparation method to make.
The present invention also comprises lithium ion battery prepared by carbon nanometer tube/silicon/graphene composite material, this lithium ion battery, comprise by positive plate, barrier film, negative plate is the battery core of stacked composition in order, for installing the closed shell of described battery core, and the electrolyte of filling in closed shell, described negative plate comprises collector and is coated in the slurry on this collector, described slurry comprises the negative material that 85:5:10 mixes in mass ratio, play butadiene-styrene rubber and the sodium carboxymethylcellulose of binding agent effect and play the acetylene black of conductive agent effect, described negative material is above-mentioned carbon nanometer tube/silicon/graphene composite material.
Solute in described electrolyte is LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2), LiFSI (LiN (SO
2f)
2) in one; Solvent in described electrolyte is one or more in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, acetonitrile.
Solute in described electrolyte and the volume ratio of solvent are 1:1, and the concentration of described electrolyte is 1mol/L.
Compared with prior art,, there is following advantage: when prepared Si-C composite material serves as lithium ion battery negative material, have excellent energy-storage property and cycle performance in carbon nanometer tube/silicon/graphene composite material of the present invention.And in the preparation process of Si-C composite material, device therefor is simple, operation simple and feasible, consuming time short, can be used for batch production.
Embodiment
Below in conjunction with embodiment, the present invention is given to elaboration further.
The preparation process of carbon nanometer tube/silicon/graphene composite material of the present invention is roughly divided into following steps:
1, by deionized water, ethanol, acetone ultrasonic cleaning post-drying for substrate, again substrate is put into reative cell, pass into inert gas, make to form inert environments in described reactor, adopt mechanical pump, lobe pump and molecular pump to take out step by step pressure, the pressure in reative cell is evacuated to 10
-3below Pa, keep 1～30 minute, stop passing into inert gas and stop bleeding;
2, substrate is heated to 500～1300 DEG C, then passes into reative cell the gaseous carbon source that flow is 50～400ml/min, keep temperature-resistant, react after 1～300 minute, stop passing into gaseous carbon source, obtain carbon nano-tube material;
3, then pass into reative cell the gaseous state silicon source that flow is 50～300ml/min, keep, after 1～300 minute, stopping substrate heating and be cooled to room temperature, obtain carbon nanometer tube/silicon composite material;
Wherein, in above-mentioned steps 2 and step 3, preparation method used is as Low Pressure Chemical Vapor Deposition, but the present invention is not limited to this, also can utilize other chemical deposition to prepare respectively carbon nano-tube material and carbon nanometer tube/silicon composite material, be that hot filament CVD, radio frequency plasma strengthen in chemical vapour deposition technique, microwave plasma enhanced chemical vapour deposition technique, laser chemical vapor deposition method, aumospheric pressure cvd method, specifically can be one or more combination;
4, take out described carbon nanometer tube/silicon composite material, Graphene and described carbon nanometer tube/silicon composite material are placed in to absolute ethyl alcohol, the solubility of carbon nanometer tube/silicon composite material is 1～2mg/ml, the solubility of Graphene is 0.2～1mg/ml, the ultrasonic machine that is 1000W with power carries out ultrasonic 3～5h, then vacuum filtration, then be placed in dry 12 hours of the vacuum drying oven of 60 DEG C, obtain carbon nanometer tube/silicon/graphene composite material; Wherein, brace "/" represents compound;
Wherein, substrate is one or the combination in any in Copper Foil, iron foil or nickel foil; Gaseous carbon sources is one or the combination in any in methane, ethane, ethene and acetylene; Gaseous state silicon source is silicon tetrahydride.
The present invention also comprises the carbon nanometer tube/silicon/graphene composite material making by above-mentioned preparation method.
This carbon nanometer tube/silicon/graphene composite material can be applicable in lithium ion battery, this lithium ion battery comprise by positive plate, barrier film, negative plate in order the stacked battery core forming, for installing the closed shell of described battery core, and filling is at the electrolyte of closed shell, negative plate comprises collector and is coated in the slurry on this collector, and this slurry comprises above-mentioned carbon nanometer tube/silicon/graphene composite material, the butadiene-styrene rubber that plays binding agent effect and the sodium carboxymethylcellulose that 85:5:10 mixes in mass ratio and plays the acetylene black of conductive agent effect.
Wherein, the solute in electrolyte is LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2), LiF SI (LiN (SO
2f)
2) in one; Solvent in electrolyte is one or more in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, acetonitrile.Solute in electrolyte and the volume ratio of solvent are 1:1, and the concentration of described electrolyte is 1mol/L.
Be specifically described with the preparation process of 1～4 pair of carbon nanometer tube/silicon/graphene composite material of the present invention of embodiment below:
Embodiment 1
1, substrate Copper Foil is spent to ionized water, ethanol, acetone ultrasonic cleaning post-drying, again substrate Copper Foil is put into reative cell, pass into nitrogen, make to form nitrogen atmosphere in described reactor, adopt mechanical pump, lobe pump and molecular pump to take out step by step pressure, the pressure in reative cell is evacuated to 10
-3below Pa, keep 1 minute, stop passing into nitrogen and stop bleeding;
2, substrate Copper Foil is heated to 500 DEG C, then passes into reative cell the methane that flow is 50ml/min, keep temperature-resistant, react after 1 minute, stop passing into methane, obtain carbon nano-tube material;
3, then pass into reative cell the silicon tetrahydride that flow is 50ml/min, keep, after 1 minute, stopping substrate Copper Foil heat and be cooled to room temperature, obtain carbon nanometer tube/silicon composite material;
4, take out carbon nanometer tube/silicon composite material, Graphene and carbon nanometer tube/silicon composite material are placed in to absolute ethyl alcohol, the solubility of carbon nanometer tube/silicon composite material is 1mg/ml, the solubility of Graphene is 0.2mg/ml, the ultrasonic machine that is 1000W with power carries out ultrasonic 3h, then vacuum filtration, then be placed in dry 12 hours of the vacuum drying oven of 60 DEG C, obtain carbon nanometer tube/silicon/graphene composite material.
Embodiment 2
1, by substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying for iron foil, again substrate iron foil is put into reative cell, pass into helium, make to form helium atmosphere in described reactor, adopt mechanical pump, lobe pump and molecular pump to take out step by step pressure, the pressure in reative cell is evacuated to 10
-3below Pa, keep 12 minutes, stop passing into helium and stop bleeding;
2, substrate iron foil is heated to 800 DEG C, then passes into reative cell the ethane that flow is 100ml/min, keep temperature-resistant, react after 30 minutes, stop passing into ethane, obtain carbon nano-tube material;
3, then pass into reative cell the silicon tetrahydride that flow is 100ml/min, keep, after 30 minutes, stopping substrate iron foil heat and be cooled to room temperature, obtain carbon nanometer tube/silicon composite material;
4, take out carbon nanometer tube/silicon composite material, Graphene and carbon nanometer tube/silicon composite material are placed in to absolute ethyl alcohol, the solubility of carbon nanometer tube/silicon composite material is 1.2mg/ml, the solubility of Graphene is 0.5mg/ml, the ultrasonic machine that is 1000W with power carries out ultrasonic 4h, then vacuum filtration, then be placed in dry 12 hours of the vacuum drying oven of 60 DEG C, obtain carbon nanometer tube/silicon/graphene composite material.
Embodiment 3
1, by substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying for iron foil, again substrate iron foil is put into reative cell, pass into argon gas, make to form argon gas atmosphere in described reactor, adopt mechanical pump, lobe pump and molecular pump to take out step by step pressure, the pressure in reative cell is evacuated to 10
-3below Pa, keep 15 minutes, stop passing into argon gas and stop bleeding;
2, substrate iron foil is heated to 1000 DEG C, then passes into reative cell the ethene that flow is 200ml/min, keep temperature-resistant, react after 1～300 minute, stop passing into ethene, obtain carbon nano-tube material;
3, then pass into reative cell the silicon tetrahydride that flow is 200ml/min, keep, after 100 minutes, stopping substrate iron foil heat and be cooled to room temperature, obtain carbon nanometer tube/silicon composite material;
4, take out carbon nanometer tube/silicon composite material, Graphene and carbon nanometer tube/silicon composite material are placed in to absolute ethyl alcohol, the solubility of carbon nanometer tube/silicon composite material is 1.8mg/ml, the solubility of Graphene is 0.8mg/ml, the ultrasonic machine that is 1000W with power carries out ultrasonic 3.5h, then vacuum filtration, then be placed in dry 12 hours of the vacuum drying oven of 60 DEG C, obtain carbon nanometer tube/silicon/graphene composite material.
Embodiment 4
1, by substrate deionized water, ethanol, acetone ultrasonic cleaning post-drying for nickel foil, again substrate nickel foil is put into reative cell, pass into helium, make to form helium atmosphere in described reactor, adopt mechanical pump, lobe pump and molecular pump to take out step by step pressure, the pressure in reative cell is evacuated to 10
-3below Pa, keep 30 minutes, stop passing into helium and stop bleeding;
2, substrate nickel foil is heated to 1300 DEG C, then passes into reative cell the acetylene that flow is 400ml/min, keep temperature-resistant, react after 300 minutes, stop passing into acetylene, obtain carbon nano-tube material;
3, then pass into reative cell the silicon tetrahydride that flow is 300ml/min, keep, after 300 minutes, stopping substrate nickel foil heat and be cooled to room temperature, obtain carbon nanometer tube/silicon composite material;
4, take out carbon nanometer tube/silicon composite material, Graphene and carbon nanometer tube/silicon composite material are placed in to absolute ethyl alcohol, the solubility of carbon nanometer tube/silicon composite material is 2mg/ml, the solubility of Graphene is 1mg/ml, the ultrasonic machine that is 1000W with power carries out ultrasonic 5h, then vacuum filtration, then be placed in dry 12 hours of the vacuum drying oven of 60 DEG C, obtain carbon nanometer tube/silicon/graphene composite material.
The preparation of lithium ion battery
With embodiment 5～8, to the carbon nanometer tube/silicon/graphene composite material making in the embodiment of the present invention 1～4, the application in lithium ion battery is specifically described respectively below:
Embodiment 5
1, the ratio that is 85:5:10 according to mass ratio, the hybrid adhesive of carbon nanometer tube/silicon/graphene composite material prepared by embodiment 1, butadiene-styrene rubber and sodium carboxymethylcellulose and conductive agent acetylene black mix, and obtain slurry;
2, above, drying, slicing treatment, make lithium ion cell electrode sheet slurry to be coated in to collector (preferably Copper Foil);
3, using lithium sheet as to electrode, by the electrode slice making in lithium sheet, barrier film, step 2 in order stack of laminations dress up battery core, then use battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the LiPF that injects 1mol/L in battery container
6(solute is LiPF to/dimethyl carbonate
6, solvent is dimethyl carbonate) and electrolyte, sealing liquid injection port, obtains lithium ion battery.
Embodiment 6
1, the ratio that is 85:5:10 according to mass ratio, the hybrid adhesive of carbon nanometer tube/silicon/graphene composite material prepared by embodiment 2, butadiene-styrene rubber and sodium carboxymethylcellulose and conductive agent acetylene black mix, and obtain slurry;
2, above, drying, slicing treatment, make lithium ion cell electrode sheet slurry to be coated in to collector (preferably Copper Foil);
3, using lithium sheet as to electrode, by the electrode slice making in lithium sheet, barrier film, step 2 in order stack of laminations dress up battery core, then use battery housing seal battery core, subsequently toward being arranged on liquid injection port on battery container toward the LiBF that injects 1mol/L in battery container
4(solute is LiBF to/diethyl carbonate electrolyte
4, solvent is diethyl carbonate) and electrolyte, sealing liquid injection port, obtains lithium ion battery.
Embodiment 7
Carbon nanometer tube/silicon/graphene composite material of the present invention also can be applicable in lithium ion battery, and concrete grammar is as follows:
1, the ratio that is 85:5:10 according to mass ratio, the hybrid adhesive of carbon nanometer tube/silicon/graphene composite material prepared by embodiment 1, butadiene-styrene rubber and sodium carboxymethylcellulose and conductive agent acetylene black mix, and obtain slurry;
2, above, drying, slicing treatment, make lithium ion cell electrode sheet slurry to be coated in to collector (preferably Copper Foil);
3, using lithium sheet as to electrode, by the electrode slice making in lithium sheet, barrier film, step 2 in order stack of laminations dress up battery core, use again battery housing seal battery core, toward being arranged on liquid injection port on battery container, toward the LiTFSI/ propene carbonate electrolyte that injects 1mol/L in battery container, (solute is LiTFSI subsequently, solvent is propene carbonate) electrolyte, sealing liquid injection port, obtains lithium ion battery.
Embodiment 8
Carbon nanometer tube/silicon/graphene composite material of the present invention also can be applicable in lithium ion battery, and concrete grammar is as follows:
1, the ratio that is 85:5:10 according to mass ratio, the hybrid adhesive of carbon nanometer tube/silicon/graphene composite material prepared by embodiment 1, butadiene-styrene rubber and sodium carboxymethylcellulose and conductive agent acetylene black mix, and obtain slurry;
2, above, drying, slicing treatment, make lithium ion cell electrode sheet slurry to be coated in to collector (preferably Copper Foil);
3, using lithium sheet as to electrode, by the electrode slice making in lithium sheet, barrier film, step 2 in order stack of laminations dress up battery core, use again battery housing seal battery core, toward being arranged on liquid injection port on battery container, toward the LiFSI/ ethylene carbonate/acetonitrile that injects 1mol/L in battery container, (solute is LiFSI subsequently, solvent is the mixed liquor of ethylene carbonate and acetonitrile) electrolyte, sealing liquid injection port, obtains lithium ion battery.
Table 1 be the lithium ion battery of embodiment 5～8 preparation under 0.1C electric current, the 2nd circle and the 301st that carries out charge-discharge test encloses the stored energy capacitance data that obtain.
Table 1
| Specific capacity (the 2nd circle) mAh/g | Specific capacity (the 301st circle) mAh/g | |
| Embodiment 5 | 2139 | 1834 |
| Embodiment 6 | 2348 | 1982 |
| Embodiment 7 | 1928 | 1681 |
| Embodiment 8 | 1786 | 1578 |
As can be seen from Table 1, the specific capacity that the carbon nanometer tube/silicon/graphene composite material that adopts this method to prepare obtains is higher, all more than 1700mAh/g, and after circulation 300 circles, specific capacity conservation rate all can be more than 80%, be up to 88%, higher than current Silicon Based Anode Materials for Lithium-Ion Batteries than electric capacity conservation rate.This explanation, when Si-C composite material prepared by the present invention serves as lithium ion battery negative material, has excellent energy-storage property and cycle performance.
Foregoing; it is only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to main design of the present invention and spirit; can carry out very easily corresponding flexible or amendment, therefore protection scope of the present invention should be as the criterion with the desired protection range of claims.
Claims (10)
1. a preparation method for carbon nanometer tube/silicon/graphene composite material, is characterized in that, comprises the steps:
Cleaning dried substrate are put into reative cell, pass into inert gas, make to form inert environments in described reactor, then described reative cell is taken out to press and process 1 ~ 30 minute, stop passing into inert gas and stop taking out pressure;
Described substrate is heated to 500 ~ 1300 DEG C, then passes into gaseous carbon source to described reative cell, keep temperature-resistant, react after 1 ~ 300 minute, stop passing into described gaseous carbon source, obtain carbon nano-tube material;
Then pass into gaseous state silicon source to described reative cell, keep, after 1 ~ 300 minute, stopping substrate heating and be cooled to room temperature, obtain carbon nanometer tube/silicon composite material;
Take out described carbon nanometer tube/silicon composite material, Graphene and described carbon nanometer tube/silicon composite material are placed in to absolute ethyl alcohol and carry out ultrasonicly, then filtration drying, obtains carbon nanometer tube/silicon/graphene composite material.
2. preparation method according to claim 1, is characterized in that, described substrate is one or more in Copper Foil, iron foil or nickel foil.
3. preparation method according to claim 1, is characterized in that, described gaseous carbon sources be a kind of in methane, ethane, ethene and acetylene or or multiple; Described gaseous state silicon source is silicon tetrahydride.
4. preparation method according to claim 1, is characterized in that, the flow of described gaseous carbon source is 50 ~ 400ml/min, and the flow in described gaseous state silicon source is 50 ~ 300ml/min.
5. preparation method according to claim 1, is characterized in that, takes out and presses while processing, adopts mechanical pump, lobe pump and molecular pump to take out step by step pressure, and the pressure in reative cell is evacuated to 10
-3below Pa.
6. preparation method according to claim 1, is characterized in that, described ultrasonic time is 3 ~ 5h.
7. carbon nanometer tube/silicon/the graphene composite material that the arbitrary described preparation method of claim 1 to 6 makes.
8. a lithium ion battery, comprise by positive plate, barrier film, negative plate in order the stacked battery core forming, for installing the closed shell of described battery core, and the electrolyte of filling in closed shell, described negative plate comprises collector and is coated in the slurry on this collector, described slurry comprises negative material, the butadiene-styrene rubber that plays binding agent effect and the sodium carboxymethylcellulose that 85:5:10 mixes in mass ratio and plays the acetylene black of conductive agent effect, it is characterized in that, described negative material is carbon nanometer tube/silicon/graphene composite material claimed in claim 7.
9. lithium ion battery according to claim 8, is characterized in that, the solute in described electrolyte is LiPF
6, LiBF
4, LiTFSI (LiN (SO
2cF
3)
2), LiFSI (LiN (SO
2f)
2) in one; Solvent in described electrolyte is one or more in dimethyl carbonate, diethyl carbonate, propene carbonate, ethylene carbonate, acetonitrile.
10. lithium ion battery according to claim 9, is characterized in that, the solute in described electrolyte and the volume ratio of solvent are 1:1, and the concentration of described electrolyte is 1mol/L.
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