CN105576194B - Preparation method of graphene-carbon nanotube aerogel supported nano-silicon composite electrode material - Google Patents
Preparation method of graphene-carbon nanotube aerogel supported nano-silicon composite electrode material Download PDFInfo
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- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 64
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 48
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 48
- 239000007772 electrode material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000004964 aerogel Substances 0.000 title abstract description 25
- 239000002131 composite material Substances 0.000 title abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 121
- 239000006185 dispersion Substances 0.000 claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 26
- 239000010439 graphite Substances 0.000 claims description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 229910021487 silica fume Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000008246 gaseous mixture Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- -1 sodium alkyl sulfonate Chemical class 0.000 claims description 2
- 239000002071 nanotube Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 7
- 238000004108 freeze drying Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 18
- 229910001416 lithium ion Inorganic materials 0.000 description 18
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 239000002048 multi walled nanotube Substances 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 5
- 239000011889 copper foil Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000002210 silicon-based material Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical class OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002409 silicon-based active material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a graphene-carbon nanotube aerogel supported nano-silicon composite electrode material, which comprises the following steps: preparing graphene oxide dispersion liquid, preparing nano silicon and carbon nanotube dispersion liquid respectively, performing ultrasonic dispersion, adding a surfactant into the carbon nanotube dispersion liquid, adding the nano silicon and carbon nanotube dispersion liquid added with the surfactant into a graphene oxide solution, performing ultrasonic dispersion to obtain uniformly mixed dispersion liquid, performing freeze drying, calcining dried powder in a protective atmosphere, and naturally cooling to obtain the graphene-carbon nanotube aerogel supported nano silicon composite electrode material. The prepared composite electrode material has high capacity, high efficiency, good cycle performance and high safety; the method is simple and feasible in process and is suitable for industrial large-scale production.
Description
Technical field：
The present invention relates to the preparation method of lithium ion battery negative material, more particularly to a kind of silicon/carbon/graphite in lithium ion batteries alkene-
Carbon nanotube aerogel supports the preparation method of nano-silicon combination electrode material, belongs to high power capacity, high efficiency lithium ion battery is born
The preparation method of pole material.
Background technology：
Lithium ion battery has that energy density is high, have extended cycle life, self-discharge rate is low, environment friendly and pollution-free and memory-less effect
The advantages that, have been widely used in the portable electric appts such as mobile phone, notebook computer, video camera.In recent years, with electronic
Many emerging technology industries such as automobile, Aero-Space, energy-storage system develop rapidly, also have to high-performance secondary lithium battery
Higher requirement, it is desirable to which lithium ion battery has bigger specific capacity, higher coulombic efficiency, more preferable high rate performance and more
The cycle life of safety.
Graphite is to be commercialized the most frequently used lithium ion battery negative material at present, but its only 372mAh/g theory
Specific capacity is difficult to the requirement for meeting the development such as space flight, military project, electric car.The theoretical specific capacity of silicium cathode material is up to 4200mAh/
G (silicon can at most combine 4.4 lithium ions), turns into present study hotspot.So far, silicium cathode material business not yet
The reason for industry is that silicon has huge Volume Changes in charge and discharge process, and silicon, which gradually crushes, to come off from collector so as to lose
Dead electricity contacts.In addition, silicon is semiconductor, self-conductive is poor, needs during as electrode to add conductive additive.In order to solve silicon
The problem of material is present, the comprehensive silicon system for designing special construction are the most effective approach to solve the above problems.
Graphene sheet layer is flexible, and lamella two sides can be combined with lithium ion.In the case where being acted on without external force, graphenic surface curling
Gauffer, this characteristic can form stable spatial network, can effectively buffer expansion of the silicon electrode in charge and discharge process
Shrink.The high conductivity that graphene has simultaneously can strengthen the electrical contact between silicon electrode and collector.CNT and stone
Black alkene is equally widely used as conductive matrices to promote the electric transmission of electrode, and its pliability and mechanical strength can also buffer silicon
Volume Changes of the material in charge and discharge process.Therefore, the cooperative effect of graphene and CNT can not only be buffered effectively
Enormousness change of the nano-silicon in lithium ion battery charge and discharge process, while lithium ion and electronics can be significantly increased
Transmission speed in electrode material, so as to obtain the lithium ion battery that lithium storage content is high, good cycle and high rate performance are good
Electrode material.
The content of the invention：
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of high power capacity, high efficiency, good cycle,
The preparation method of safe graphene-carbon nano tube aeroge support nano-silicon combination electrode material.
First technical problem to be solved by this invention is by specific surface area is big, the graphite of electric conductivity and good mechanical property
Alkene and CNT are used for composite Nano silicon, while increase nano-silicon conductive is electrical, have effectively buffered the volume effect of nano-silicon
Answer, improve the cycle performance of nano-silicon.
Second technical problem to be solved by this invention is to be combined to obtain using freeze-drying and thermal reduction technology
Graphene, the combination electrode material of carbon nanotube aerogel support nano-silicon of tridimensional network, promote lithium ion in three-dimensional
Migration and diffusion on direction, so as to which the high rate performance of nano-silicon be greatly improved.
3rd technical problem to be solved by this invention is to be mixed to get graphene, CNT gas by ultrasonic physics
Gel supports nano-silicon combination electrode material, and method is simple and easy, is adapted to industrialization large-scale production.
The technical scheme is that：Graphene-carbon nano tube aeroge supports the preparation of nano-silicon combination electrode material
Method, it is comprised the following steps that：
1) preparation of graphite oxide：
Graphite oxide is prepared by modified Hummer methods；
2) preparation of graphene oxide water solution：
Oxidation graphite solid is scattered in deionized water, it is configured to the oxidation stone that mass concentration is 0.1-10.0mg/ml
Black suspension, by the suspension ultrasonic disperse, realize that individual layer is peeled off, obtain uniform and stable graphene oxide dispersion；
3) preparation of graphene-carbon nano tube aeroge support nano-silicon combination electrode material
Mass concentration is prepared respectively as 0.5-5.0mg/ml nano-silicon dispersion liquid and 0.5-5.0mg/ml CNT
Dispersion liquid, nano-silicon and CNT is uniformly dispersed in solution in ultrasonic disperse, added in carbon nano tube dispersion liquid
Surfactant, the dispersion liquid of nano-silicon and addition surfactant CNT is then added to graphene oxide solution
In, the mass ratio of graphite oxide, nano silica fume and CNT is 1:2：(0.02-2), obtained in ultrasonic disperse well mixed
Dispersion liquid, then uniform dispersion liquid is freeze-dried；After being completely dried, by dried powder under protective atmosphere, temperature
Spend and obtain graphene-carbon nano tube aeroge support nano-silicon combination electrode material for 500-1000 DEG C of calcining 1-10h, natural cooling
Material.
The graphite oxide for preparing described in step 1) typically prepares graphite oxide by the Hummer methods of the modification of routine, excellent
Choosing is referring to patent《A kind of method of preparing grapheme through oxidation reduction》(the patent No.:ZL201110372309.X).By XRD,
Raman and FT-IR is characterized, and the graphite oxide degree of oxidation of preparation is high, in aqueous good dispersion.
Supersonic frequency in preferred steps (2) in suspension ultrasonic disperse is 20-80kHz；Ultrasonic time is 0.5-6h.
Ultrasonic disperse makes nano-silicon in preferred steps (3) and CNT is uniformly dispersed in solution and ultrasonic disperse obtains
It is 20-80kHz to the supersonic frequency described in well mixed dispersion liquid；Ultrasonic time is 1-6h；Dispersion liquid in step (3)
The time of freeze-drying is 24-96h.
It is preferred that described CNT is at least one of multi-walled carbon nanotube or single-walled carbon nanotube.
Surfactant described in preferred steps (3) is dodecyl sodium sulfate, neopelex or 16
One kind in alkyl trimethyl ammonium bromide.
Protective atmosphere described in preferred steps (3) be in argon gas, nitrogen, hydrogen, helium or argon hydrogen gaseous mixture at least
It is a kind of.
The addition of surfactant is that the mass ratio of control surface activating agent and CNT is 1 in preferred steps (3):
(1-100)。
The speed of heat temperature raising described in preferred steps (3) is 1-50 DEG C of min-1；The flow velocity of protective atmosphere is 50-
1000ml·min-1。
Beneficial effect：
Unique association of the present invention innovatively being used in combination using graphene and CNT, graphene and CNT
Same effect, the electric conductivity of combination electrode material is greatly improved, is effectively increased connecing for silicon active material and lithium ion
Touch, improve the specific capacity of silicon materials.Secondly, the present invention constructs three-dimensional network aeroge using being freeze-dried and heat-treating technology
Structure, enormousness change of the nano-silicon in lithium ion battery charge and discharge process is effectively fettered, silicon materials has been solved and exists
The bottleneck problem in lithium ion battery applications field, the stable circulation performance of silicon materials is greatly improved.Finally, this novelty
Three-dimensional structure provide abundant lithium ion transport passage, promote lithium ion moving on three-dimensional in charge and discharge process
Move and spread, effectively improve the high rate performance of silicon materials.
Graphene prepared by the present invention, carbon nanotube aerogel support nano-silicon combination electrode material overcome current negative pole
The key issue of Material Field, greatly improve capacity, efficiency, cyclical stability and the safety of lithium ion battery negative material
Property, while technique is simple, preparation efficiency is high, cost is cheap, is easy to industrial mass production.
Brief description of the drawings：
Fig. 1 is the SEM figures that the graphene-carbon nano tube aeroge of embodiment 2 supports nano-silicon combination electrode material；
Fig. 2 is that graphene, carbon nanotube aerogel prepared by embodiment 2 supports nano-silicon combination electrode material in 0.05C
Charge and discharge cycles curve and corresponding coulombic efficiency curve under current density；
Fig. 3 is that graphene, carbon nanotube aerogel prepared by embodiment 2 supports the forthright again of nano-silicon combination electrode material
Can curve；
Embodiment：
Below in conjunction with the accompanying drawings and embodiment is described in further detail to the present invention.
Embodiment 1：
1) preparation of graphite oxide：
After taking 10g (8000 mesh) natural flake graphites to be well mixed with 500ml mass concentrations for 98% sulfuric acid, add
10.0g potassium nitrate, 60g potassium permanganate is rapidly joined in 15 DEG C of water-bath, be well mixed.Then system temperature is increased to 40
DEG C, react 3h, then add 300ml water, while system is warming up to 80 DEG C of reaction 30min, then with 500ml distilled water and
The excessive potassium permanganate of 100ml hydrogen peroxide (30wt%) reduction, centrifuge washing to pH are that 5,40 DEG C of vacuum drying obtain aoxidizing stone
Black solid.
2) preparation of graphene oxide water solution：
Weigh 30mg oxidation graphite solids to be dispersed in 300ml water, be configured to the oxidation stone that mass concentration is 0.1mg/ml
Black suspension, by the suspension frequency be 20kHz under ultrasonic 0.5h, realize individual layer peel off, obtain uniform and stable oxidation stone
Black alkene dispersion liquid.
3) preparation of graphene, carbon nanotube aerogel support nano-silicon combination electrode material：
120ml 0.5mg/ml nano-silicon dispersion liquid and 1.2ml 0.5mg/ml single-walled carbon nanotube point are prepared respectively
Dispersion liquid, 0.6mg dodecyl sodium sulfates are added in carbon nano tube dispersion liquid.In the case where frequency is 20kHz, by two kinds of dispersion liquids point
Not ultrasonic 1h makes nano-silicon and CNT dispersed.Then scattered nano silica fume solution and carbon nano-tube solution are added
Enter into 300ml 0.1mg/ml graphene oxide solution, in the case where frequency is 20kHz, ultrasonic 1h obtains finely dispersed nanometer
Silica flour, graphene oxide and single-walled carbon nanotube mixed dispersion liquid, it is placed on after then three's mixed dispersion liquid is freezed with liquid nitrogen
24h is dried in freeze drier.Finally dried powder is put into tube furnace, with 50mlmin-1Speed be passed through argon
Gas, in 1 DEG C of min-1Heating rate under be warming up to 500 DEG C keep 10h obtain graphene, carbon nanotube aerogel support nanometer
Silicon combination electrode material, natural cooling are taken out after being down to room temperature.
4) battery assembling and test：
By graphene, carbon nanotube aerogel support nano-silicon combination electrode material, acetylene black and PVDF according to mass ratio
For 80：10：10 are dissolved in nmp solvent, are coated uniformly on copper foil, prepare pole piece.In the glove box full of argon gas atmosphere,
Using metal lithium sheet as negative pole, button cell is assembled into 0.01-3V voltage range, at room temperature, under 0.05C current densities
First discharge specific capacity be 2102mAh/g, charge specific capacity 2022mAh/g, after circulation 100 times, specific discharge capacity is
889mAh/g, charge specific capacity 848mAh/g, capability retention 71%.
Embodiment 2：
1) preparation of graphene oxide water solution：
The oxidation graphite solid for weighing the preparation of 30mg embodiments 1 is dispersed in 30ml water, and it is 1mg/ to be configured to mass concentration
Ml graphite oxide suspension, by the suspension frequency be 20kHz under ultrasonic 1h, realize individual layer peel off, obtain uniform and stable
Graphene oxide dispersion.
2) preparation of graphene, carbon nanotube aerogel support nano-silicon combination electrode material：
60ml 1mg/ml nano-silicon dispersion liquid and 5ml 1mg/ml multi-walled carbon nanotube dispersion liquid are prepared respectively,
0.5mg neopelexes are added in carbon nano tube dispersion liquid.In the case where frequency is 30kHz, two kinds of dispersion liquids are surpassed respectively
Sound 2h makes nano-silicon and CNT dispersed.Then scattered nano silica fume solution and carbon nano-tube solution are added to
In 30ml 1mg/ml graphene oxide solution, in the case where frequency is 30kHz, ultrasonic 2h obtains finely dispersed nano silica fume, oxygen
Graphite alkene and multi-walled carbon nanotube mixed dispersion liquid, freeze-drying is placed on after then three's mixed dispersion liquid is freezed with liquid nitrogen
36h is dried in machine.Finally dried powder is put into tube furnace, with 100mlmin-1Speed be passed through nitrogen, 5
℃·min-1Heating rate under be warming up to 600 DEG C keep 6h obtain graphene, carbon nanotube aerogel support nano-silicon it is compound
Electrode material, natural cooling are taken out after being down to room temperature.Graphene-carbon nano tube aeroge support nano-silicon combination electrode material
SEM figures are as shown in Figure 1.
3) battery assembling and test：
By graphene, carbon nanotube aerogel support nano-silicon combination electrode material, acetylene black and PVDF according to mass ratio
For 80：10：10 are dissolved in nmp solvent, are coated uniformly on copper foil, prepare pole piece.In the glove box full of argon gas atmosphere,
Using metal lithium sheet as negative pole.Graphene, the carbon nanotube aerogel of preparation support nano-silicon combination electrode material in 0.05C electric currents
Charge and discharge cycles curve and corresponding coulombic efficiency curve under density are as shown in Fig. 2 prepared graphene, CNT gas
The high rate performance curve of gel support nano-silicon combination electrode material from figure as shown in figure 3, can be seen that：0.01-3V's
It is 1885.823mAh/g in the first discharge specific capacity of 0.05C current densities, charge specific capacity is at room temperature in voltage range
1314.412mAh/g, after circulating 100 times, specific discharge capacity 1470.813mAh/g, charge specific capacity 1429.67mAh/
G, capability retention 108%.In 0.01-3V voltage range, at room temperature, current density rises to 2C from 0.05C, then
Return to 0.05C, the specific capacity under last test 0.02C current densities, the graphene, carbon nanotube aerogel support nano-silicon are answered
Composite electrode material reversible specific capacity under 2C current density is up to 604.009mAh/g, the base when returning to 0.05C low current
Original level is originally may return to, when returning to smaller electric current 0.02C, performance is still highly stable, it can thus be seen that
The combination electrode material has preferable high rate performance.
Embodiment 3：
1) preparation of graphene oxide water solution：
The oxidation graphite solid for weighing the preparation of 30mg embodiments 1 is dispersed in 15ml water, and it is 2mg/ to be configured to mass concentration
Ml graphite oxide suspension, by the suspension frequency be 40kHz under ultrasonic 2h, realize individual layer peel off, obtain uniform and stable
Graphene oxide dispersion.
2) preparation of graphene, carbon nanotube aerogel support nano-silicon combination electrode material：
30ml 2mg/ml nano-silicon dispersion liquid and 7.5ml 2mg/ml single wall, multi-walled carbon nanotube point are prepared respectively
Dispersion liquid, 0.3mg cetyl trimethylammonium bromides are added in carbon nano tube dispersion liquid.In the case where frequency is 40kHz, by two kinds points
Ultrasonic 3h makes nano-silicon and CNT dispersed to dispersion liquid respectively.Then nano silica fume solution and single wall, more wall carbon are received into carbon
Nanotube solution is added in 15ml 2mg/ml graphene oxide solution, and in the case where frequency is 40kHz, ultrasonic 3h is disperseed
Uniform nano silica fume, graphene oxide and single wall, multi-walled carbon nanotube CNT mixed dispersion liquid.Then with liquid nitrogen by three
It is placed on after the freezing of person's mixed dispersion liquid in freeze drier and dries 48h.Finally dried powder is put into tube furnace, with
500ml·min-1Speed be passed through argon hydrogen gaseous mixture, in 20 DEG C of min-1Heating rate under be warming up to 800 DEG C keep 3h obtain
To graphene, carbon nanotube aerogel support nano-silicon combination electrode material, natural cooling is taken out after being down to room temperature.
3) battery assembling and test：
By graphene, carbon nanotube aerogel support nano-silicon combination electrode material, acetylene black and PVDF according to mass ratio
For 80：10：10 are dissolved in nmp solvent, are coated uniformly on copper foil, prepare pole piece.In the glove box full of argon gas atmosphere,
Using metal lithium sheet as negative pole.In 0.01-3V voltage range, at room temperature, in the first discharge specific capacity of 0.05C current densities
For 1345.385mAh/g, charge specific capacity 1117.188mAh/g, after circulating 100 times, specific discharge capacity is
877.511mAh/g, charge specific capacity 857.061mAh/g, capability retention 77%.
Embodiment 4：
1) preparation of graphene oxide water solution：
The oxidation graphite solid for weighing the preparation of 30mg embodiments 1 is dispersed in 6ml water, and it is 5mg/ml to be configured to mass concentration
Graphite oxide suspension, by the suspension frequency be 60kHz under ultrasonic 4h, realize individual layer peel off, obtain uniform and stable
Graphene oxide dispersion.
2) preparation of graphene, carbon nanotube aerogel support nano-silicon combination electrode material：
20ml 3mg/ml nano-silicon dispersion liquid and 10ml 3mg/ml multi-walled carbon nanotube dispersion liquid are prepared respectively,
0.5mg neopelexes are added in carbon nano tube dispersion liquid.In the case where frequency is 60kHz, two kinds of dispersion liquids are surpassed respectively
Sound 4h makes nano-silicon and CNT dispersed.Then scattered nano silica fume solution and multi-walled carbon nanotube solution are added
Enter into 6ml 5mg/ml graphene oxide solution, in the case where frequency is 60kHz, ultrasonic 4h obtains finely dispersed nano-silicon
Powder, graphene oxide and multi-walled carbon nanotube mixed dispersion liquid.Then it is placed on after three's mixed dispersion liquid is freezed with liquid nitrogen cold
72h is dried in lyophilizer.Finally dried powder is put into tube furnace, with 800mlmin-1Speed be passed through helium,
In 30 DEG C of min-1Heating rate under be warming up to 900 DEG C keep 2h obtain graphene, carbon nanotube aerogel support nano-silicon
Combination electrode material, natural cooling are taken out after being down to room temperature.
3) battery assembling and test：
By graphene, carbon nanotube aerogel support nano-silicon combination electrode material, acetylene black and PVDF according to mass ratio
For 80：10：10 are dissolved in nmp solvent, are coated uniformly on copper foil, prepare pole piece.In the glove box full of argon gas atmosphere,
Using metal lithium sheet as negative pole.In 0.01-3V voltage range, at room temperature, in the first discharge specific capacity of 0.05C current densities
For 1404.083mAh/g, charge specific capacity 1030.889mAh/g, after circulating 100 times, specific discharge capacity is
932.035mAh/g, charge specific capacity 904.374mAh/g, capability retention 88%.
Embodiment 5：
1) preparation of graphene oxide water solution：
The oxidation graphite solid for weighing the preparation of 30mg embodiments 1 is dispersed in 3ml water, and it is 10mg/ to be configured to mass concentration
Ml graphite oxide suspension, by the suspension frequency be 80kHz under ultrasonic 6h, realize individual layer peel off, obtain uniform and stable
Graphene oxide dispersion.
2) preparation of graphene, carbon nanotube aerogel support nano-silicon combination electrode material：
12ml 5mg/ml nano-silicon dispersion liquid and 12ml 5mg/ml multi-walled carbon nanotube dispersion liquid are prepared respectively,
0.6mg neopelexes are added in carbon nano tube dispersion liquid.In the case where frequency is 80kHz, two kinds of dispersion liquids are surpassed respectively
Sound 6h makes nano-silicon and CNT dispersed.Then scattered nano silica fume solution and multi-walled carbon nanotube solution are added
Enter into 3ml 10mg/ml graphene oxide solution, in the case where frequency is 80kHz, ultrasonic 6h obtains finely dispersed nano-silicon
Powder, graphene oxide and multi-walled carbon nanotube mixed dispersion liquid.Then it is placed on after three's mixed dispersion liquid is freezed with liquid nitrogen cold
96h is dried in lyophilizer.Finally dried powder is put into tube furnace, with 1000mlmin-1Speed be passed through hydrogen
Gas, in 50 DEG C of min-1Heating rate under be warming up to 1000 DEG C and keep 1h obtain graphene, carbon nanotube aerogel support
Nano-silicon combination electrode material, natural cooling are taken out after being down to room temperature.
3) battery assembling and test：
By graphene, carbon nanotube aerogel support nano-silicon combination electrode material, acetylene black and PVDF according to mass ratio
For 80：10：10 are dissolved in nmp solvent, are coated uniformly on copper foil, prepare pole piece.In the glove box full of argon gas atmosphere,
Using metal lithium sheet as negative pole.In 0.01-3V voltage range, at room temperature, in the first discharge specific capacity of 0.05C current densities
For 1527.639mAh/g, charge specific capacity 846.305mAh/g, after circulating 100 times, specific discharge capacity is
1159.433mAh/g, charge specific capacity 1032.503mAh/g, capability retention 121%.
Claims (8)
1. graphene-carbon nano tube aeroge supports the preparation method of nano-silicon combination electrode material, it is comprised the following steps that：
1) preparation of graphite oxide
Graphite oxide is prepared by modified Hummer methods；
2) preparation of graphene oxide water solution
Oxidation graphite solid is scattered in deionized water, it is configured to the graphite oxide that mass concentration is 0.1-10.0mg/ml and hangs
Turbid, by the suspension ultrasonic disperse, realize that individual layer is peeled off, obtain uniform and stable graphene oxide dispersion；
3) preparation of graphene-carbon nano tube aeroge support nano-silicon combination electrode material
Mass concentration is prepared respectively for 0.5-5.0mg/ml nano-silicon dispersion liquid and 0.5-5.0mg/ml CNT to disperse
Liquid, ultrasonic disperse make nano-silicon and CNT be uniformly dispersed in solution, and surface is added in carbon nano tube dispersion liquid and is lived
Property agent, then by nano-silicon and addition surfactant CNT dispersion liquid be added in graphene oxide solution, aoxidize
The mass ratio of graphite, nano silica fume and CNT is 1:2：(0.02-2), ultrasonic disperse obtain well mixed dispersion liquid, so
Uniform dispersion liquid is freeze-dried afterwards；After being completely dried, by dried powder under protective atmosphere, temperature 500-
1000 DEG C of calcining 1-10h, natural cooling obtain graphene-carbon nano tube aeroge support nano-silicon combination electrode material.
2. preparation method according to claim 1, it is characterised in that：Ultrasound in step (2) in suspension ultrasonic disperse
Frequency is 20-80kHz；Ultrasonic time is 0.5-6h.
3. preparation method according to claim 1, it is characterised in that：Supersonic frequency in step (3) described in ultrasonic disperse
It is 20-80kHz；Ultrasonic time is 1-6h；The time that dispersion liquid is freeze-dried in step (3) is 24-96h.
4. preparation method according to claim 1, it is characterised in that：CNT described in step (3) is more wall carbon
At least one of nanotube or single-walled carbon nanotube.
5. preparation method according to claim 1, it is characterised in that：Surfactant described in step (3) is 12
One kind in sodium alkyl sulfonate, neopelex or cetyl trimethylammonium bromide.
6. preparation method according to claim 1, it is characterised in that：Protective atmosphere described in step (3) is argon gas, nitrogen
At least one of gas, hydrogen, helium or argon hydrogen gaseous mixture.
7. preparation method according to claim 1, it is characterised in that：The addition of surfactant is control in step (3)
The mass ratio of control surface activating agent and CNT is 1:(1-100).
8. preparation method according to claim 1, it is characterised in that：The heating rate of calcining described in step (3) is
1-50℃·min-1；The flow velocity of protective atmosphere is 50-1000mlmin-1。
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