CN107946562A - A kind of graphene/silicon composite material and preparation method thereof, lithium ion battery - Google Patents
A kind of graphene/silicon composite material and preparation method thereof, lithium ion battery Download PDFInfo
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- CN107946562A CN107946562A CN201711115517.5A CN201711115517A CN107946562A CN 107946562 A CN107946562 A CN 107946562A CN 201711115517 A CN201711115517 A CN 201711115517A CN 107946562 A CN107946562 A CN 107946562A
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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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/38—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
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/62—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 present invention relates to a kind of graphene/silicon composite material and preparation method thereof, lithium ion battery, belong to field of lithium ion battery material preparation.The preparation method of the graphene/silicon composite material of the present invention, comprises the following steps：1) silane compound, graphene oxide solution, nitrogen source are reacted into 1~6h in 120~150 DEG C, obtains hydrogel A；The silane compound, graphene oxide, the mass ratio of nitrogen source are 10~30：1~10：1~5；2) hydrogel A is subjected to vacuum freeze drying, obtains material B；3) material B is kept the temperature into 1~6h in 300~400 DEG C under an inert atmosphere, then keep the temperature 1~6h in 800~900 DEG C, cool down to obtain the final product.The graphene/silicon composite material that preparation method of the present invention obtains, tap density and specific surface area significantly improve, in the application prospect that lithium battery preparation field has had.
Description
Technical field
The present invention relates to a kind of graphene/silicon composite material and preparation method thereof, lithium ion battery, belong to lithium ion battery
Field of material preparation.
Background technology
The raising required with market electric car course continuation mileage, it is desirable to which electric automobile, which matches somebody with somebody lithium ion battery, has higher
Energy density to meet market demands, and negative material is the critical material for forming lithium ion battery, the quality of its performance
The energy density, security performance and its service life of lithium ion battery are had an important influence on.Currently on the market lithium used from
Sub- cell negative electrode material is mainly based on graphite type material, but relatively low its lithium ion battery energy density that limits of its gram volume
Improve.And silicon-carbon cathode material is paid attention to the advantages that its gram volume is high, aboundresources be subject to researcher, and it is applied to high ratio
The fields such as energy density lithium ion battery, but high, the conductive sexual deviation of its expansion rate is as its extensive use of restriction.Reduce at present
The expansion measure main method of silicon materials has：1) in silicon materials coated with carbon material, its volume dilatation is reduced；2) prepare
Poroid template, and nano silicon material is embedded in hole, reduce its expansion rate；3) material that expansion rate is high, electric conductivity is strong is coated,
Such as the material such as graphene, carbon nanotubes, to reduce the expansion rate of its silicon materials and its electric conductivity.
Application publication number is a kind of graphene battery of Chinese invention patent of CN 105576242A, using with oxidation
Graphene mixes with nanometer silicon liquid and prepares graphene oxide/nano silicon material, then is heat-treated by high temperature and prepare graphene/nano
Rice silicon composite, although being improved in terms of specific capacity, due to silicon materials and graphene dispersion lack of homogeneity and its
The big coefficient of expansion of silicon materials, its cycle performance not be improved significantly.
Application publication number be CN 106099061A a kind of porous graphene/silicon composite of Chinese invention patent, its system
Preparation Method and lithium ion battery disclose a kind of preparation method of porous graphene/silicon composite, specially by graphite oxide
Aqueous solution, nano silica fume, deionized water, surfactant and the organic solvent mixing of alkene, graphene/silicon is obtained through hydro-thermal reaction
Plural gel；The graphene/silicon plural gel is dried to, is freeze-dried, is heat-treated and to obtain porous graphene/silicon composite material.
The porous graphene that the patented method obtains/silicon composite first discharge specific capacity is high, but its cycle performance is not good enough.
The content of the invention
It is an object of the invention to provide a kind of preparation method of graphene/silicon composite material, the graphite that this method obtains
Alkene/silicon composite can significantly improve the energy density and cycle performance of lithium ion battery.
Second object of the present invention is to provide a kind of graphene/silicon composite material.
Third object of the present invention is to provide a kind of lithium ion battery.
To achieve the above object, the technical solution of the preparation method of graphene/silicon composite material of the present invention is：
A kind of preparation method of graphene/silicon composite material, comprises the following steps：
1) silane compound, graphene oxide solution, nitrogen source are reacted into 1~6h in 120~150 DEG C, obtains hydrogel A；Institute
It is 10~30 to state silane compound, graphene oxide, the mass ratio of nitrogen source:1~10：1~5；
2) hydrogel A is subjected to vacuum freeze drying, obtains material B；
3) material B is kept the temperature into 1~6h in 300~400 DEG C under an inert atmosphere, then keeps the temperature 1~6h in 800~900 DEG C,
Cool down to obtain the final product.
The silane compound, graphene oxide solution, the nitrogen source first ultrasonic disperse before 120~150 DEG C of reactions are uniform.Institute
Stating ultrasonic disperse uniformly makes silane compound, graphene oxide solution, nitrogen source be sufficiently mixed, is dispersed, more individually by nanometer
Silicon materials be entrained in graphene oxide solution disperse evenly, it is stronger with reference to power.
Reaction in step 1) carries out in autoclave.
The silane compound is aqueous silane compound.
Filtered in step 1) after 1~6h of reaction, obtain hydrogel.The hydrogel is block hydrogel.In hydro-thermal reaction bar
Under part, nitrogen source, silane gasification are decomposed, and hydroxyl, the carboxyl with surface of graphene oxide are combined, and are deposited on surface, postcooling,
Obtain hydrogel.Between aqueous silane compound, nitrogen source are doped into graphene oxide by hydro-thermal reaction, and then uniformly by silicon
Compound, nitrogen Uniform Doped are into graphene surface and its interlayer.
The aqueous silane compound is amino silane, any one in alkoxy silane, acyloxy silane, oximino silane
Kind.
Above-mentioned amino silane for 3-aminopropyltriethoxysilane, double [(3- triethoxysilyls) propyl group] amine,
3- TSL 8330s, 3- aminopropyltriethoxies diethoxy silane, 3- aminopropyltriethoxies dimethoxysilane, ammonia second
Base aminopropyl trimethoxysilane, aminoethylaminopropyl triethoxysilane, aminoethylaminopropyl methyl dimethoxysilane, ammonia
Ethylaminopropyl methyldiethoxysilane, aminoethyl aminomethyl triethoxysilane, aminoethyl aminomethyl methyl diethoxy
Silane, three aminopropyl trimethoxysilane of diethylidene, three aminopropyl triethoxysilane of diethylidene, three ammonia third of diethylidene
Ylmethyl dimethoxysilane, three aminopropyltriethoxy diethoxy silane of diethylidene, three aminomethyl methyl diethyl of diethylidene
Any one in oxysilane, diethylaminomethyl triethoxysilane.
Above-mentioned alkoxy silane is 3- ureidopropyltriethoxysilanes, 3- isocyanates propyl trimethoxy silicane, 3-
Isocyanates propyl-triethoxysilicane, trimethoxy silane, triethoxysilane, methyl dimethoxysilane, methyl diethyl
Oxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyl tripropoxy silane, three butoxy silane of methyl,
Methyl three (t-butyl peroxy) silane, dimethylethoxysilane, dimethyldimethoxysil,ne, dimethyl diethoxy silicon
Alkane, propyl trimethoxy silicane, N- butyl trimethoxy silanes, N- butyl triethoxysilane, 1- butyl trimethoxy silanes,
1- butyl triethoxysilane, allyltriethoxysilane, dodecyltrimethoxysilane, dodecyl methyl dimethoxy
Base silane, octadecyl trimethoxysilane, octadecyltriethoxy silane, octadecyl methyl dimethoxysilane, N-
In octyl group trimethoxy silane, N- octyltri-ethoxysilanes, octyl methyl diethoxy silane, cyclohexyltriethyloxysilane
Any one.
Above-mentioned acyloxy silane for four acetoxylsilanes, ethyltriacetoxysilane, methyl triacetoxysilane,
Any one in dimethyl 2 acetoxyl group silane, two-tert-butoxy-diacetoxy silane.
Above-mentioned oximino silane is phenyl three (methyl ethyl ketoxime) silane, four (methyl isobutyl ketoxime) silane, front three
Base (methyl ethyl ketoxime) silane, dimethyl two (methyl ethyl ketoxime) silane, methyl three (methyl isobutyl ketoxime) silicon
Alkane, methyl three (acetoxime) silane, methyl three (methyl ethyl ketoxime) silane, vinyl three (methyl isobutyl ketoxime) silicon
Alkane, methyl ethylene two (cyclohexanone oxime) silane, methyl ethylene two (methyl ethyl ketoxime) silane, three (methyl of vinyl
Ethyl ketone oxime) any one in silane.
The concentration of the graphene oxide solution is 1~10mg/mL.
The nitrogen source is any one in pyrroles, aniline, thiophene, ammonium hydroxide, melamine.The nitrogen source can not only carry
The specific capacity of high material, can also improve the conductivity of material, and then improve the multiplying power and cycle performance of material.
Vacuum freeze drying in step 2) is that 6~48h is kept the temperature under the conditions of 5~50Pa, -60~-20 DEG C.The vacuum
Freeze-drying can improve specific surface area, the imbibition liquid-keeping property of material while material structure is kept.
The speed that 300~400 DEG C are warming up in step 3) is 1~10 DEG C/min.
The speed that 800~900 DEG C are warming up in step 3) is 1~10 DEG C/min.
1~6h is kept the temperature in 800~900 DEG C in step 3), the hydroxyl on graphene oxide composite material surface, carboxyl is departed from this
Body, makes graphene oxide be reduced into graphene.
A kind of graphene/silicon composite material, is made using above-mentioned preparation method.The graphene/silicon composite material is
Porous graphene/silicon composite.The tap density and specific surface area of the graphene/silicon composite material of the present invention significantly improve.
A kind of lithium ion battery, including cathode, anode, membrane and electrolyte, the anode are answered including above-mentioned graphene/silicon
Condensation material.The lithium ion battery of the present invention, the imbibition liquid-keeping property of its anode significantly improve, and liquid-keeping property is up to more than 94%.
The lithium ion battery of the present invention, cycle performance is excellent, and conservation rate is still more than 95% after circulating 500 times.
The preparation method of the graphene/silicon composite material of the present invention, graphene, silane compound, nitrogen source collaboration are used,
Using the high electric conductivity of graphene, big mechanical strength, expansion rate of the silicon materials in charge and discharge process is reduced, is carried using nitrogen source
The specific capacity and conductivity of high material, are equably mixed graphene with silicon materials, nitrogen source using hydro-thermal method, between raising material
Combination power, improve the tap density of material, can be while material structure be kept using freeze-drying, the hole of material
Increase, improve the specific surface area of its material, so as to improve the cycle performance of material.
The graphene/silicon composite material of the present invention, tap density and specific surface area significantly improve, in lithium battery preparation field
With good application prospect.
The lithium ion battery of the present invention, the imbibition liquid-keeping property of its anode significantly improve, and liquid-keeping property is up to more than 94%；
The lithium ion battery of the present invention, cycle performance is excellent, and conservation rate is still more than 95% after circulating 500 times.
Brief description of the drawings
Fig. 1 is that the SEM of 1 gained graphene/silicon composite material of embodiment schemes.
Embodiment
Embodiments of the present invention are described further below in conjunction with the accompanying drawings.
Embodiment 1
The preparation method of the graphene/silicon composite material of the present embodiment, comprises the following steps：
1) preparation of hydrogel
20g 3-aminopropyltriethoxysilane is added to the graphene oxide solution that 1000mL concentration is 5mg/mL
In, after stirring evenly, then add 3g melamine ultrasonic disperses it is uniform after, be transferred in autoclave, in 130 DEG C reaction
3h, is filtered afterwards, obtains block hydrogel A；
2) vacuum freeze drying
Block hydrogel A is positioned in vacuum freeze drier, 20Pa is evacuated down to, vacuum drying chamber cools down afterwards
To -40 DEG C of insulation 24h, then it is warmed to room temperature, by material disintegrating, briquetting, obtains material B；
3) heat-treat
Material B is positioned in tube furnace, under argon gas protection, 350 DEG C of insulations are warming up to the heating rate of 5 DEG C/min
3h, is warming up to 850 DEG C of insulation 3h, Temperature fall is to room temperature afterwards, and crushes, is classified with the heating rate of 5 DEG C/min again afterwards
To obtain the final product.
The graphene/silicon composite material of the present embodiment, is obtained using above-mentioned preparation method.
The lithium ion battery of the present embodiment, including cathode, anode, membrane and electrolyte, anode include above-mentioned graphene/silicon
Composite material.
Embodiment 2
The preparation method of the graphene/silicon composite material of the present embodiment, comprises the following steps：
1) preparation of hydrogel
Three aminopropyl trimethoxysilane of 10g diethylidenes is added to the graphene oxide that 1000mL concentration is 1mg/mL
In solution, after stirring evenly, then add 1g ammonium hydroxide ultrasonic disperses it is uniform after, be transferred in autoclave, and temperature be 120
DEG C reaction 1h, filter afterwards, obtain block hydrogel A；
2) vacuum freeze drying
Block hydrogel A is placed in vacuum freeze drier, is evacuated down to 5Pa, afterwards cool to vacuum drying chamber-
6h is kept the temperature at a temperature of 60 DEG C, is then warming up to room temperature, afterwards by material disintegrating, briquetting, obtains material B；
3) heat-treat
Material B is placed into tube furnace, under argon gas protection, 300 DEG C of insulations are warming up to the heating rate of 1 DEG C/min
1h, is warming up to 800 DEG C of insulation 1h, Temperature fall is to room temperature afterwards, and crushes, is classified with the heating rate of 1 DEG C/min again afterwards
To obtain the final product.
The graphene/silicon composite material of the present embodiment, is obtained using above-mentioned preparation method.
The lithium ion battery of the present embodiment, including cathode, anode, membrane and electrolyte, the anode include above-mentioned graphite
Alkene/silicon composite.
Embodiment 3
The preparation method of the graphene/silicon composite material of the present embodiment, comprises the following steps：
1) preparation of hydrogel
30g phenyl three (methyl ethyl ketoxime) silane is added to the graphene oxide that 1000mL concentration is 10mg/mL
In solution, after stirring evenly, then add 5g pyrroles's ultrasonic disperse it is uniform after, be transferred in autoclave, and temperature be 150
DEG C reaction 6h, filter afterwards, obtain block hydrogel A；
2) vacuum freeze drying
Block hydrogel A is placed into vacuum freeze drier, 50Pa is evacuated down to, vacuum drying chamber cools down afterwards
48h is kept the temperature at a temperature of to -20 DEG C, is finally warming up to room temperature, carries out material disintegrating, material briquetting, obtains material B；
3) heat-treat
Material B is placed into tube furnace, under argon gas protection, 400 DEG C of guarantors are warming up to the heating rate of 10 DEG C/min
Warm 6h, is warming up to 900 DEG C of insulation 6h with the heating rate of 10 DEG C/min again afterwards, afterwards Temperature fall to room temperature, crushes, classification
To obtain the final product.
The graphene/silicon composite material of the present embodiment, is obtained using above-mentioned preparation method.
The lithium ion battery of the present embodiment, including cathode, anode, membrane and electrolyte, the anode include above-mentioned graphite
Alkene/silicon composite.
Embodiment 4
The preparation method of the graphene/silicon composite material of the present embodiment, comprises the following steps：
1) preparation of hydrogel
10g ethyltriacetoxysilanes are added in the graphene oxide solution that 1000mL concentration is 1mg/mL, stirred
Mix uniformly after, then add 1g ammonium hydroxide ultrasonic disperses it is uniform after, be transferred in autoclave, and temperature for 120 DEG C reaction 1h,
Filter afterwards, obtain block hydrogel A；
2) vacuum freeze drying
Block hydrogel A is placed in vacuum freeze drier, is evacuated down to 5Pa, afterwards cool to vacuum drying chamber-
6h is kept the temperature at a temperature of 60 DEG C, is then warming up to room temperature, afterwards by material disintegrating, briquetting, obtains material B；
3) heat-treat
Material B is placed into tube furnace, under argon gas protection, 300 DEG C of insulations are warming up to the heating rate of 1 DEG C/min
1h, is warming up to 800 DEG C of insulation 1h, Temperature fall is to room temperature afterwards, and crushes, is classified with the heating rate of 1 DEG C/min again afterwards
To obtain the final product.
The graphene/silicon composite material of the present embodiment, is obtained using above-mentioned preparation method.
The lithium ion battery of the present embodiment, including cathode, anode, membrane and electrolyte, the anode include above-mentioned graphite
Alkene/silicon composite.
Embodiment 5
The preparation method of the graphene/silicon composite material of the present embodiment, comprises the following steps：
1) preparation of hydrogel
20g 3- ureidopropyltriethoxysilanes are added to the graphene oxide solution that 1000mL concentration is 5mg/mL
In, after stirring evenly, then add 3g melamine ultrasonic disperses it is uniform after, be transferred in autoclave, in 130 DEG C reaction
3h, is filtered afterwards, obtains block hydrogel A；
2) vacuum freeze drying
Block hydrogel A is positioned in vacuum freeze drier, 20Pa is evacuated down to, vacuum drying chamber cools down afterwards
To -40 DEG C of insulation 24h, then it is warmed to room temperature, by material disintegrating, briquetting, obtains material B；
3) heat-treat
Material B is positioned in tube furnace, under argon gas protection, 350 DEG C of insulations are warming up to the heating rate of 5 DEG C/min
3h, is warming up to 850 DEG C of insulation 3h, Temperature fall is to room temperature afterwards, and crushes, is classified with the heating rate of 5 DEG C/min again afterwards
To obtain the final product.
The graphene/silicon composite material of the present embodiment, is obtained using above-mentioned preparation method.
The lithium ion battery of the present embodiment, including cathode, anode, membrane and electrolyte, anode include above-mentioned graphene/silicon
Composite material.
Comparative example
The preparation method of the composite material of this comparative example comprises the following steps：
20g nano-silicons (particle diameter 50nm) are added in the graphene oxide solution that 1000mL concentration is 5mg/mL, stirring
Uniformly after, then add 3g melamine ultrasonic disperses it is uniform after, be transferred in autoclave, and temperature for 130 DEG C reaction
3h, is filtered afterwards, obtains block hydrogel A；Hydrogel A is put into vacuum drying chamber afterwards, vacuum for-
Material, is placed into tube furnace, under an inert atmosphere, and using heating rate as 5 by dry 48h afterwards under 0.08MPa vacuums
DEG C/heating rate of min is warming up to 350 DEG C of insulation 3h, 850 DEG C of insulation 3h are warming up to the heating rate of 5 DEG C/min again afterwards,
Temperature fall is to room temperature afterwards, and crushes, is classified to obtain the final product.
Experimental example 1
SEM tests are carried out to the graphene/silicon composite material of the gained of embodiment 1, it is as shown in Figure 1, real shown in result figure 1
The graphene/silicon composite material for applying the gained of example 1 is in granular form, and particle diameter is between 5~20 μm.
Experimental example 2
According to national standard GB/T _ 245332009《Silicon/carbon/graphite in lithium ion batteries class negative material》Obtained by testing example 1-3
Specific surface area, the tap density of material, as a result as shown in table 1, table 2.
1 embodiment 1-3 of table is compared with the physical and chemical performance of composite material obtained by comparative example
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example |
| Tap density (g/cm3) | 1.21 | 1.19 | 1.18 | 0.94 |
The ratio surface and its pore volume of 2 embodiment 1-3 of table and comparative example gained composite material are compared
Graphene/silicon composite material obtained by embodiment 1-3 in tap density and its compares surface it can be seen from table 1, table 2
Product aspect is better than comparative example, the reason for this is that can uniformly be mixed graphene with silicon materials using hydro-thermal method, between raising material
Combination power, improve the tap density of its material, while can be beneficial to while material structure is kept using freeze-drying
The hole of material increases, so as to improve the specific surface area of its material.
Experimental example 3
Respectively using resulting materials in embodiment 1-3 and comparative example as anode (formula：Composite material：CMC：SBR：SP：
H2O=95:2.5:1.5:1:150), lithium piece uses LiPF as cathode, electrolyte6/ EC+DEC, electrolyte solvent volume ratio EC:
DEC=1: 1, membrane uses the composite membrane of polythene PE, polypropylene PP and poly- second propylene PEP, and button cell, which is assemblied in, is flushed with hydrogen gas
Glove box in carry out, be assembled into button cell A1, A2, A3 and B.Chemical property is surveyed in the blue electricity CT2001A types battery in Wuhan
Carried out on examination instrument, charging/discharging voltage scope control is in 0.005~2.0V, charge-discharge velocity 0.1C.
Button cell A1, A2, A3 and the electrical testing comparative result of buckleing of comparative example see the table below 3.
3 button cell performance of table compares
As can be seen from the above table, its discharge capacity and efficiency is bright first first of the button electricity battery made of embodiment 1-3
It is aobvious to be higher than comparative example, show that the graphene/silicon composite material that the present invention prepares improves silicon materials and stone using hydro-thermal reaction method
Dispersing uniformity between black alkene, the gram volume for improving silicon materials plays, while the material ratio prepared using freeze-drying
Surface is big, further improves the imbibition ability of material.
Experimental example 4
Electrochemical property test：The composite material that Example 1-3 and comparative example are prepared carries out conjunction slurry, coating is prepared
Cathode pole piece, for LiFePO4 as cathode, solvent is EC/DEC/PC (EC:DEC:PC=1:1:1) electrolyte is used as, solute is
LiPF6, 2400 films of Celgard are membrane, prepare 5Ah soft-package batteries C1, C2, C3 and D1 respectively.
The imbibition ability of negative plate and efficiency first, the cycle performance (1.0C/1.0C) of lithium battery are tested afterwards, respectively
As shown in table 4, table 5.Test method is with reference to standard GB/T/T 24533-2009《Silicon/carbon/graphite in lithium ion batteries class negative material》；
At the same time according to discharge capacity of lithium ion battery and quality, the mass energy density of flexible packing lithium ion battery is calculated.
The imbibition ability of 4 negative plate of table
| Project | Rate of liquid aspiration (mL/min) | Protect liquid rate (24h electrolyte contents/0h electrolyte contents) |
| Embodiment 1 | 3.8 | 95.1% |
| Embodiment 2 | 3.6 | 94.3% |
| Embodiment 3 | 3.5 | 94.2% |
| Comparative example | 1.2 | 83.1% |
As shown in Table 4, the imbibition liquid-keeping property of negative electrode is significantly better than that comparative example in embodiment 1-3, analyzes reason
It is：The present invention is combined the silicon-carbon cathode electrode prepared and is had nano level hole using hydro-thermal method and vacuum freeze drying
Hole, improves the imbibition liquid-keeping property of material.
The cycle performance of 5 soft-package battery of table
As shown in Table 5, the cycle performance of soft-package battery is significantly better than that comparative example in embodiment 1-3, and analysis reason is：
Freeze-drying can prepare the big graphene/silicon composite material of specific surface area, which has the big advantage of specific surface area,
The imbibition ability of material can be improved, so as to improve the cycle performance of material；Meanwhile graphene has mechanical strength height, compares table
The big advantage of area, with the expansion in padded coaming charge and discharge process, can improve the cycle performance of material.
Claims (10)
1. a kind of preparation method of graphene/silicon composite material, it is characterised in that comprise the following steps：
1) silane compound, graphene oxide solution, nitrogen source are reacted into 1~6h in 120~150 DEG C, obtains hydrogel A；The silicon
Hydride compounds, graphene oxide, the mass ratio of nitrogen source are 10~30：1~10：1~5；
2) hydrogel A is subjected to vacuum freeze drying, obtains material B；
3) material B is kept the temperature into 1~6h in 300~400 DEG C under an inert atmosphere, 1~6h, cooling is then kept the temperature in 800~900 DEG C
To obtain the final product.
2. the preparation method of graphene/silicon composite material according to claim 1, it is characterised in that the silane chemical combination
Thing is aqueous silane compound.
3. the preparation method of graphene/silicon composite material according to claim 2, it is characterised in that the aqueous silane
Compound is any one in amino silane, alkoxy silane, acyloxy silane, oximino silane.
4. the preparation method of graphene/silicon composite material according to claim 1, it is characterised in that the graphite oxide
The concentration of alkene solution is 1~10mg/mL.
5. the preparation method of graphene/silicon composite material according to claim 1, it is characterised in that the nitrogen source is pyrrole
Cough up, any one in aniline, thiophene, ammonium hydroxide, melamine.
6. the preparation method of graphene/silicon composite material according to claim 1, it is characterised in that true in step 2)
Vacuum freecing-dry is that 6~48h is kept the temperature under the conditions of 5~50Pa, -60~-20 DEG C.
7. the preparation method of graphene/silicon composite material according to claim 1, it is characterised in that heating in step 3)
It is 1~10 DEG C/min to 300~400 DEG C of speed.
8. the preparation method of graphene/silicon composite material according to claim 1, it is characterised in that heating in step 3)
It is 1~10 DEG C/min to 800~900 DEG C of speed.
9. a kind of graphene/silicon composite material, it is characterised in that be made using preparation method as claimed in claim 1.
10. a kind of lithium ion battery, it is characterised in that including cathode, anode, membrane and electrolyte, it is characterised in that described negative
Pole includes graphene/silicon composite material as claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711115517.5A CN107946562B (en) | 2017-11-13 | 2017-11-13 | Graphene/silicon composite material, preparation method thereof and lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711115517.5A CN107946562B (en) | 2017-11-13 | 2017-11-13 | Graphene/silicon composite material, preparation method thereof and lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107946562A true CN107946562A (en) | 2018-04-20 |
| CN107946562B CN107946562B (en) | 2020-04-10 |
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| CN109802175A (en) * | 2019-01-22 | 2019-05-24 | 常州天宇宏图电子有限公司 | A kind of preparation method of sodium-ion battery gel state electrolyte |
| CN109860554A (en) * | 2019-01-29 | 2019-06-07 | 常州讯宛德电子有限公司 | A kind of preparation method of stable structure type lithium battery combination electrode powder body material |
| CN109904415A (en) * | 2019-01-25 | 2019-06-18 | 武汉科技大学 | A kind of nano-silicon-graphene aerogel is composite porous and preparation method thereof |
| CN110459747A (en) * | 2019-08-19 | 2019-11-15 | 齐鲁工业大学 | A kind of graphene-iron titanate-titanium dioxide nanofiber composite material and preparation method and application |
| CN115725199A (en) * | 2021-08-31 | 2023-03-03 | 江苏星源新材料科技有限公司 | Coupling agent composition, ceramic slurry, and battery separator |
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| CN109802175A (en) * | 2019-01-22 | 2019-05-24 | 常州天宇宏图电子有限公司 | A kind of preparation method of sodium-ion battery gel state electrolyte |
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