CN106299375A - A kind of carbon fibre composite of silicon cladding and its preparation method and application - Google Patents
A kind of carbon fibre composite of silicon cladding and its preparation method and application Download PDFInfo
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- CN106299375A CN106299375A CN201610865456.3A CN201610865456A CN106299375A CN 106299375 A CN106299375 A CN 106299375A CN 201610865456 A CN201610865456 A CN 201610865456A CN 106299375 A CN106299375 A CN 106299375A
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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
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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
- H01M4/62—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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses the preparation method of the carbon fibre composite of a kind of silicon cladding, including: configuration silxoane precursors thing solution for later use, native cellulose is immersed in silxoane precursors thing solution, natural drying at room temperature, obtain the natural cellulosic materials of surface deposition silica dioxide gel film；The carbon fibre composite of silicon parcel is obtained again after carbonization and magnesiothermic reduction process.The invention provides the preparation method of the carbon fibre composite of a kind of silicon parcel, through a step impregnation process, at the silica dioxide gel film of native cellulose surface basis weight deposition high silicon content, enormously simplify preparation technology, improve work efficiency, large-scale industrial production can be realized.The carbon fibre composite of the silicon parcel prepared using this method, as the negative material of lithium ion battery, has specific capacity big, and cyclical stability is high, and the advantage such as have extended cycle life.
Description
Technical field
The present invention relates to the preparation field of composite, be specifically related to carbon fibre composite and the system thereof of a kind of silicon parcel
Preparation Method and application.
Background technology
Along with the fast development of science and technology, various electronic equipments and electric automobile have had and have been widely applied, to chemistry
The requirement of power supply is more and more higher.Lithium ion battery is little due to its volume, and specific capacity is high, environmental protection, can repeatedly discharge and recharge etc.
Advantage, has been widely used in electronic equipment.
The negative material of the lithium ion battery of at present commercialization mostly is graphite, but the theoretical specific capacity that graphite is relatively low
(372mAh/g) the further development of high-capacity lithium ion cell, is limited.Research finds, silica-based, tinbase and other alloy materials
The reversible lithium storage capacity of material is much larger than graphite, but due to the bulk effect during lithium ion deintercalation, causes these materials
Cyclical stability is poor, it is impossible to commercialization.So, the bulk effect how reducing these materials has become current lithium ion battery to grind
Hot issue in studying carefully.
In non-graphite system negative material, silicon is owing to having high theoretical specific capacity (4200mAh/g), high stability, peace
Entirely, the advantage such as pollution-free has obtained paying close attention to widely.But during lithium ion deintercalation, volumetric expansion is serious with contraction, can lead
Cause material disintegrating comes off, and specific capacity declines fast, and cyclical stability is poor.It addition, the electric conductivity of silicon is not fine, this strong influence
The cycle performance of silicon cathode material and the application of silica-based anode material lithium ion battery.
At present, researcher solves, by multiple method, the problem that silica-based cathode material exists, including nanorize, thin
Membranization, Composite etc..Material with carbon element has stable chemical property, good conductivity, it addition, material with carbon element is inherently a kind of good
Lithium storage materials, during storage lithium, change in volume is little, can bear certain mechanical stress, and certain delaying is played in the volumetric expansion to silicon
Punching effect and similar to the intercalation potential of silicon compound with silicon after relatively small, therefore, at silica-based composite wood to material capacity loss
Material is studied widely.In recent years, general employing high-energy ball milling method or chemical gaseous phase deposition (CVD) method etc. prepare silicon/carbon
Nano composite material.Although these measures improve the performance of silica-based cathode material the most to some extent, but preparation process is complicated,
Needing expensive instrument and equipment, cost is high so that silica-based anode material and commercial applications there is also certain distance.
As the patent documentation of Publication No. CN103730645A discloses a kind of silicon carbon coated for lithium ion battery
Fiber nano composite material and its preparation method and application, concretely comprises the following steps: with tetramethoxy-silicane as precursor, natural fiber
Element is template and carbon source, first deposits nanometer titanium dioxide silicate gel film through surface sol-gel method on native cellulose surface, then
In noble gas, calcine carbonization obtain coated with silica carbon fiber nanometer composite material, finally use low temperature magnesium reduction process
Reduction obtains silicon cladding carbon fiber nanometer composite material.In this preparation method, by repeating the operation of standing deposition-hydrolysis repeatedly
After, the accuracy controlling to the nanometer titanium dioxide silicate gel film thickness deposited can be realized, to obtain the silicon carbon coated of different silicone content
Fiber nano composite material.When the method yet suffers from following drawback:
1) silicone content, in the silicon for preparing cladding carbon fiber nanometer composite material is too low, causes silicon carbon coated fiber
The specific capacity of nano composite material is the highest, and compared with graphite cathode material, in terms of specific capacity, advantage is little, is unfavorable for improving lithium
The performance of ion battery.
2), complicated process of preparation, it is more difficult to realize large-scale industrial production.
Summary of the invention
The invention provides the preparation method of the carbon fibre composite of a kind of silicon parcel, through a step impregnation process, in sky
So the silica dioxide gel film of cellulose surface quantitative deposition high silicon content, enormously simplify preparation technology, improves work effect
Rate, can realize large-scale industrial production.The carbon fibre composite of the silicon parcel prepared using this method is as lithium-ion electric
The negative material in pond, has specific capacity big, and cyclical stability is high, and the advantage such as have extended cycle life.
The invention discloses the preparation method of the carbon fibre composite of a kind of silicon parcel, specifically comprise the following steps that
(1) configuration silxoane precursors thing solution for later use, immerses in silxoane precursors thing solution by native cellulose, and room temperature is certainly
So it is dried, obtains the natural cellulosic materials of surface deposition silica dioxide gel film；
(2) natural cellulosic materials of step (1) obtains surface deposition silica dioxide gel film is through carbonization and magnesium heat also
The carbon fibre composite of silicon parcel is obtained after the reason of original place.
The present invention is directed to the serious bulk effect that silicon produces when lithium deintercalation, utilize support and the cushioning effect of material with carbon element,
Keep the characteristic of silicon height ratio capacity, and increase its cyclical stability.
In step (1), the solvent needed for configuration silxoane precursors thing solution only needs to dissolve silxoane precursors thing,
As preferably, described silxoane precursors thing is tetraethoxysilane or tetramethoxy-silicane, and solvent is ethanol.
Chemical property is relevant with content and the silicon layer thickness of silicon in composite.And the concentration of silxoane precursors thing solution
Content and the silicon layer thickness of silicon in the composite prepared will be directly affected.As preferably, described silxoane precursors thing is molten
The concentration of liquid is 0.1M～1.2M.Finding through test, the thickness of silicon layer is the thinnest, is unfavorable for improving the specific capacity of composite, too
The special capacity fade of thick composite is fast, poor stability.Therefore, the concentration of silxoane precursors thing solution be further preferably 0.1～
0.6M。
Further, also find through test, when the concentration of silxoane precursors thing solution is 0.3M, the silicon carbon coated of preparation
In fibrous composite, the weight/mass percentage composition of silicon is 25wt%, and thickness is about 40nm.In this composite, the thickness of silicon layer is fitted
In, be on the one hand conducive to the buffering embedding lithium of nano silicon particles to take off enormousness change during lithium, effectively prevent material disintegrating from coming off,
On the other hand, relatively thin silicon layer is conducive to the stress of volume increase generation during transmission silicon embedding lithium.It addition, the carbon of multilayered structure is fine
Dimension mesh substrate also has certain restriction to the cushioning effect of silicon layer.So, prepare with the silxoane precursors thing solution of this concentration
The carbon fibre composite specific capacity obtaining silicon parcel is maximum, and in charge and discharge cycles, stability is preferable.Therefore, most preferably
The concentration of silxoane precursors thing solution is 0.3M.
The material with carbon element used in the present invention derives from native cellulose, and native cellulose is heated in noble gas, when arriving
Reaching 275 DEG C and i.e. start spontaneous carbonization, in the case of anoxia, only a part of carbon and other composition are burnt, when temperature reaches
When 400～500 DEG C, carbonization completes, and the material with carbon element obtained can effectively buffer change in volume serious during silicon removal lithium embedded, and increases
The electric conductivity of material.As preferably, in step (1), described native cellulose includes quantitative filter paper, Cotton Gossypii or cotton.Enter one
Step is preferably quantitative filter paper, and quantitative filter paper is interwoven by many micron order fleeces, and these micron order fibers are by many
Nano-scale fiber binding is interwoven, and has fibrous layer level structure, has the biography of the biggest specific surface area, beneficially electronics
Defeated, improve the electric conductivity of material, the specific capacity of material can be effectively improved.
As preferably, in step (2), described carbonization treatment is carried out under an inert atmosphere, and carburizing temperature is 450～750
DEG C, the time is 5～10h.
As preferably, in step (2), described magnesiothermic reduction processes specifically comprises the processes of:
The carbonized product of the natural cellulosic materials that surface deposits silica dioxide gel film mixes with magnesium powder, 650～
750 DEG C, reduce under inert atmosphere, obtain the carbon fibre composite of described silicon parcel；
The carbonized product of natural cellulosic materials and the mass ratio of magnesium powder of described surface deposition silica dioxide gel film are
1:1～5.
The most preferred:
In step (2), carbonization treatment technique is: the lower 600 DEG C of carbonization 6h of argon shield；Magnesiothermic reduction processes technique: table
The carbonized product of natural cellulosic materials of face deposition silica dioxide gel film and magnesium powder 1:1 in mass ratio mixing, 700 DEG C,
Reduction 6h in argon.
The concrete technology condition that above-mentioned carbonization treatment and magnesiothermic reduction process all finds after lot of experiments, with
The natural cellulosic materials of the surface deposition silica dioxide gel film prepared by the silxoane precursors thing solution of 0.1～0.6M is
The subsequent treatment process joined.Certainly, the silxoane precursors thing solution concentration mated the most with above-mentioned subsequent treatment process is 0.3M.
As preferably, magnesiothermic reduction process after product again through soak with hydrochloric acid, washing, obtain described silicon parcel after drying
Carbon fibre composite.
As preferably, the noble gas that carbonization and magnesiothermic reduction use in processing is high-purity argon gas.
The invention also discloses the carbon fibre composite of the silicon parcel prepared according to above-mentioned method and at lithium ion
Application in battery.
In order to detect the chemical property of the carbon fibre composite that the silicon of preparation wraps up, assemble them into button cell and enter
Row electrochemical property test.Compared with graphite negative electrodes material conventional in current commercial Li-ion batteries, there is bigger specific volume
Amount.
Compared with prior art, the invention have the advantages that
1, the present invention is during the deposition silica dioxide gel film of natural cellulosic materials surface, use only a step leaching
Stain processes, and is achieved that the deposition of high silicon content, and by changing the concentration of precursor solution used, it is possible to achieve to titanium dioxide
In silicate gel film, the regulation and control of silicone content, enormously simplify preparation technology, improve work efficiency, it is simple to realize large-scale industry
Metaplasia is produced.
2, the preparation method in the present invention is simple, low cost, pollution-free.
3, the lithium ion battery that the carbon fibre composite of the silicon parcel prepared using this method assembles as negative material, tool
Having specific capacity big, cyclical stability is high, and the advantage such as have extended cycle life.
Accompanying drawing explanation
Fig. 1 is that the carbon fibre composite of the silicon parcel of embodiment 1 preparation scanning electron microscope under different amplification shines
Sheet；
Fig. 2 is the transmission electron microscope photo of the carbon fibre composite of the silicon parcel of embodiment 1 preparation；
Fig. 3 is the high-resolution-ration transmission electric-lens photo of the carbon fibre composite of the silicon parcel of embodiment 1 preparation；
Fig. 4 is transmission electron microscope and the high power transmission electron microscope photo of nano-tube material prepared by comparative example；
Fig. 5 is constant current charge and discharge cycle performance and the coulombic efficiency curve of battery 1；
Fig. 6 is the battery 1 charge-discharge performance curve under different multiplying；
Fig. 7 is the comparison diagram of the constant current charge-discharge cycle performance curve of battery 1,2；
Fig. 8 is the scanning under different amplification of the carbon fibre composite of the silicon parcel of embodiment 2 preparation and transmission
Electromicroscopic photograph；
Fig. 9 is the scanning under different amplification of the carbon fibre composite of the silicon parcel of embodiment 3 preparation and transmission
Electromicroscopic photograph；
Figure 10 is the scanning under different amplification of the carbon fibre composite of the silicon parcel of embodiment 4 preparation and transmission
Electromicroscopic photograph；
Figure 11 is constant current charge and discharge cycle performance and the coulombic efficiency curve of battery 3；
Figure 12 is the battery 3 charge-discharge performance curve under different multiplying；
Figure 13 is constant current charge and discharge cycle performance and the coulombic efficiency curve of battery 4；
Figure 14 is the battery 4 charge-discharge performance curve under different multiplying；
Figure 15 is constant current charge and discharge cycle performance and the coulombic efficiency curve of battery 5；
Figure 16 is the battery 5 charge-discharge performance curve under different multiplying.
Detailed description of the invention
Embodiment 1:
(1) with ethanol as solvent, configuration concentration is the tetraethoxysilane solution of 0.3M, and be stirred at room temperature 2 little
Time.
(2) laboratory is commonly used quantitative filter paper be immersed in above-mentioned tetraethoxysilane/ethanol solution, naturally dry under room temperature
Dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film.
(3) native cellulose of step (2) obtains surface deposition silica dioxide gel film is under high-purity argon gas is protected 600
DEG C carbonization 6h, obtains the carbon fibre composite of Silica-coated.
(4) carbon fibre composite and the magnesium powder 1:1 in mass ratio of Silica-coated step (3) obtained mixes,
700 DEG C, high-purity argon gas reduces 6h, reduzate soak with hydrochloric acid 8h, then by distilled water and washing with alcohol, be vacuum dried,
Obtain the carbon fibre composite of described silicon parcel.
The stereoscan photograph of the carbon fibre composite of silicon prepared by the present embodiment parcel is as it is shown in figure 1, Fig. 1 a) for putting
The stereoscan photograph of big 10k times, interior accompanying drawing is the photo of material；Fig. 1 b) for amplifying the stereoscan photograph of 50k times.Observe
Fig. 1 is it will be seen that the carbon fibre composite of silicon parcel replicates the filamentary structure of quantitative filter paper, the diameter of fiber well
It is 100～200nm.
The transmission electron microscope photo of the carbon fibre composite of silicon parcel prepared by the present embodiment is as in figure 2 it is shown, be single in figure
The carbon fiber of root silicon parcel.The diameter of fiber about 150nm, the thickness of the silicon layer of fiber surface parcel is 30～50nm, silicon grain
Size be a few nanometer.Fig. 3 is the high-resolution-ration transmission electric-lens photo of the carbon fibre composite of silicon parcel, it can be seen that silicon crystal
(220) crystal face of lattice fringe correspondence silicon.Insert in figure is SEAD image, electronic diffraction collection of illustrative plates display crystal formation
Silicon, (311) and (511) crystal face of 1,2 diffraction rings respectively corresponding silicon.Prove after low temperature magnesiothermic reduction, silicon dioxide success
Be reduced to crystalline silicon.
Comparative example:
Step (3) in embodiment 1 changes into calcining at 600 DEG C in atmosphere 6h, and remaining is the most same as in Example 1.Pass through
Air calcination removes as the native cellulose of template, prepare for Silica Nanotube material, then through magnesiothermic reduction
Obtain nano-tube material.
The transmission electron microscope a) of nano-tube material prepared by comparative example and b), high-resolution-ration transmission electric-lens photo c) and constituency electricity
Sub-diffraction pattern d) as shown in Figure 4, can be clearly apparent the tubular structure of nano-tube material, and the silicon of nano-particle is packed together shape
Become tube wall.From high-resolution-ration transmission electric-lens photo it can be seen that (111) crystal face of crystalline silicon, spread out in 1～3 in SEAD figure
Penetrate (220) of ring correspondence silicon, (422) and (511) crystal face.
Embodiment 2:
(1) with ethanol as solvent, configuration concentration is the tetraethoxysilane solution of 0.1M, and be stirred at room temperature 2 little
Time.
(2) laboratory is commonly used quantitative filter paper be immersed in above-mentioned tetraethoxysilane/ethanol solution, naturally dry under room temperature
Dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film.
(3) native cellulose of step (2) obtains surface deposition silica dioxide gel film is under high-purity argon gas is protected 600
DEG C carbonization 6h, obtains the carbon fibre composite of Silica-coated.
(4) carbon fibre composite and the magnesium powder 1:1 in mass ratio of Silica-coated step (3) obtained mixes,
700 DEG C, high-purity argon gas reduces 6h, reduzate soak with hydrochloric acid 8h, then by distilled water and washing with alcohol, be vacuum dried,
Obtain the carbon fibre composite of described silicon parcel.
The stereoscan photograph of the carbon fibre composite of silicon prepared by the present embodiment parcel as shown in Figure 8, Fig. 8 a) for putting
The stereoscan photograph of big 20k times, interior accompanying drawing is the photo of material；Fig. 8 b) for amplifying the stereoscan photograph of 80k times.From sweeping
Retouch and the carbon fibre composite of silicon parcel be can be observed in electromicroscopic photograph replicate the filamentary structure of quantitative filter paper well, fine
A diameter of the 100～200nm of dimension.
Transmission electron microscope photo such as Fig. 8 c of the carbon fibre composite of silicon parcel prepared by the present embodiment) and d) shown, figure
In be single silicon parcel carbon fiber.The diameter of fiber about 150nm, the thickness of the silicon layer of fiber surface parcel is about 20nm.
Embodiment 3:
(1) with ethanol as solvent, configuration concentration is the tetraethoxysilane solution of 0.6M, and be stirred at room temperature 2 little
Time.
(2) laboratory is commonly used quantitative filter paper be immersed in above-mentioned tetraethoxysilane/ethanol solution, naturally dry under room temperature
Dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film.
(3) native cellulose of step (2) obtains surface deposition silica dioxide gel film is under high-purity argon gas is protected 600
DEG C carbonization 6h, obtains the carbon fibre composite of Silica-coated.
(4) carbon fibre composite and the magnesium powder 1:1 in mass ratio of Silica-coated step (3) obtained mixes,
700 DEG C, high-purity argon gas reduces 6h, reduzate soak with hydrochloric acid 8h, then by distilled water and washing with alcohol, be vacuum dried,
Obtain the carbon fibre composite of described silicon parcel.
The stereoscan photograph of the carbon fibre composite of silicon prepared by the present embodiment parcel is as it is shown in figure 9, Fig. 9 a) for putting
The stereoscan photograph of big 20k times, interior accompanying drawing is the photo of material；Fig. 9 b) for amplifying the stereoscan photograph of 100k times.From sweeping
Retouch and the carbon fibre composite of silicon parcel be can be observed in electromicroscopic photograph replicate the filamentary structure of quantitative filter paper well, fine
A diameter of the 100～200nm of dimension.
Transmission electron microscope photo such as Fig. 9 c of the carbon fibre composite of silicon parcel prepared by the present embodiment) and d) shown, figure
In be single silicon parcel carbon fiber.The diameter of fiber about 150nm, the thickness of the silicon layer of fiber surface parcel is about 50nm.
Embodiment 4:
(1) with ethanol as solvent, configuration concentration is the tetraethoxysilane solution of 1.2M, and be stirred at room temperature 2 little
Time.
(2) laboratory is commonly used quantitative filter paper be immersed in above-mentioned tetraethoxysilane/ethanol solution, naturally dry under room temperature
Dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film.
(3) native cellulose of step (2) obtains surface deposition silica dioxide gel film is under high-purity argon gas is protected 600
DEG C carbonization 6h, obtains the carbon fibre composite of Silica-coated.
(4) carbon fibre composite and the magnesium powder 1:1 in mass ratio of Silica-coated step (3) obtained mixes,
700 DEG C, high-purity argon gas reduces 6h, reduzate soak with hydrochloric acid 8h, then by distilled water and washing with alcohol, be vacuum dried,
Obtain the carbon fibre composite of described silicon parcel.
The stereoscan photograph of the carbon fibre composite of silicon prepared by the present embodiment parcel as shown in Figure 10, Figure 10 a) be
Amplifying the stereoscan photograph of 20k times, interior accompanying drawing is the photo of material；Figure 10 b) for amplifying the stereoscan photograph of 80k times.From
The carbon fibre composite that silicon parcel be can be observed in stereoscan photograph replicates the filamentary structure of quantitative filter paper well,
A diameter of the 100 of fiber～200nm.
Transmission electron microscope photo such as Figure 10 c of the carbon fibre composite of silicon parcel prepared by the present embodiment) and d) shown, figure
In be single silicon parcel carbon fiber.The diameter of fiber about 150nm, the thickness of the silicon layer of fiber surface parcel is about 60nm.
Application examples:
Material a is ground in agate mortar 30min, weighs 40mg and with mass ratio 70:15:15 and superconduction electrical carbon with glue
Knot agent PVDF mixing, furnishing pasty slurry, it is applied in nickel foam, is vacuum dried 12 hours, tabletting.
When the carbon fibre composite that material a is the silicon parcel that embodiment prepares, the lithium ion battery being prepared as
Negative plate is designated as 1；
When material a is the nano-tube material that comparative example prepares, the anode plate for lithium ionic cell being prepared as is designated as
2；
When the carbon fibre composite that material a is the silicon parcel that embodiment 2 prepares, the lithium ion battery being prepared as
Negative plate is designated as 3；
When the carbon fibre composite that material a is the silicon parcel that embodiment 3 prepares, the lithium ion battery being prepared as
Negative plate is designated as 4；
When the carbon fibre composite that material a is the silicon parcel that embodiment 4 prepares, the lithium ion battery being prepared as
Negative plate is designated as 5；
Anode plate for lithium ionic cell 1～5 is assembled in the glove box of full argon respectively with positive plate-lithium sheet respectively,
Obtain CR2025 type button cell 1～5.The electrolyte used is with LiPF6For solute, the ethylene carbonate with volume ratio as 1:1:1
Ester (EC), dimethyl carbonate (DMC) and Ethyl methyl carbonate (EMC) are solvent, and the barrier film of use is Celgard 2300.
The button cell assembled is tested, uses battery system to test battery 1～5 respectively in constant current and difference times
Charge-discharge performance under rate, charge and discharge voltage range is 0.01～3.0V.
Constant current (100mA/g) charge-discharge performance of battery 1 and coulombic efficiency are as it is shown in figure 5, first lap electric discharge is compared
Capacity is 2610.5mAh/g, and first lap charge specific capacity is 1422.7mAh/g, coulombic efficiency 54.5%.After circulation 200 circle, put
Electricity specific capacity still has 729.3mAh/g, and the coulombic efficiency after stablizing is maintained at more than 98%.Silicon parcel prepared by embodiment 1 is described
Carbon fibre composite assemble lithium battery there is bigger specific capacity and preferable cyclical stability.
The battery 1 charge-discharge performance under different multiplying as shown in Figure 6, at 0.1A/g, 0.2A/g, 0.5A/g, 1A/
Circulate ten circles under the electric current density of g, 2A/g, 3A/g successively, finally return 0.1A/g.During 3A/g, specific capacity still has
218.2mAh/g, after returning to 0.1A/g, specific capacity is returned to more than 700mAh/g.
The contrast of the constant current charge-discharge cycle performance of battery 1,2 is as shown in Figure 7.Carbon fiber composite due to silicon parcel
The support of carbon and cushioning effect in material, silicon is difficult to subside in cyclic process, and material is difficult to pulverizing and comes off, so having preferably
Cyclical stability.It can be seen that after circulation 200 circle, the specific capacity of battery 1 still has a 729.3mAh/g, and battery 2
Specific capacity has fallen to 325mAh/g.
As shown in figure 11, first lap electric discharge is compared for constant current (100mA/g) charge-discharge performance of battery 3 and coulombic efficiency
Capacity is 2133.5mAh/g, and first lap charge specific capacity is 1104.3mAh/g, coulombic efficiency 51.8%.After circulation 180 circle, put
Electricity specific capacity still has 630.8mAh/g, and the coulombic efficiency after stablizing is maintained at more than 98%.Silicon parcel prepared by embodiment 2 is described
Carbon fibre composite assemble lithium battery there is bigger specific capacity and preferable cyclical stability.
The battery 3 charge-discharge performance under different multiplying as shown in figure 12,0.1A/g, 0.2A/g, 0.5A/g,
Circulate ten circles under the electric current density of 1A/g, 2A/g, 3A/g successively, finally return and carry out discharge and recharge under 0.1A/g electric current density and follow
Ring.As can be observed from Figure along with the increase of charging and discharging currents density, the specific capacity of battery is gradually reduced, when electric current density is
During 3A/g, specific capacity is 165.5mAh/g, and after returning to 0.1A/g, specific capacity is returned to more than 590mAh/g, and along with circulation time
Number is carried out, and specific capacity is more stable.Illustrate that this composite has preferable high rate performance and cyclical stability.
As shown in figure 13, first lap electric discharge is compared for constant current (100mA/g) charge-discharge performance of battery 4 and coulombic efficiency
Capacity is 3009.3mAh/g, and first lap charge specific capacity is 1505.2mAh/g, coulombic efficiency 50.0%.After circulation 200 circle, put
Electricity specific capacity still has 487.2mAh/g, and the coulombic efficiency after stablizing is maintained at more than 98%.The carbon of the silicon parcel of embodiment 3 preparation
The lithium battery that fibrous composite assembles specific capacity in front 80 circulations has decayed, after 100 times circulate, and the ratio of battery
Example capacity is more stable.
The battery 4 charge-discharge performance under different multiplying as shown in figure 14,0.1A/g, 0.2A/g, 0.5A/g,
Circulate ten circles under the electric current density of 1A/g, 2A/g, 3A/g successively, finally return and carry out discharge and recharge under 0.1A/g electric current density and follow
Ring.As can be observed from Figure along with the increase of charging and discharging currents density, the specific capacity of battery is gradually reduced, when electric current density is
During 3A/g, specific capacity still has 234.9mAh/g, and after electric current density returns to 0.1A/g, specific capacity is returned to more than 630mAh/g.Explanation
This composite has preferable high rate performance and cyclical stability.
As shown in figure 15, first lap electric discharge is compared for constant current (100mA/g) charge-discharge performance of battery 5 and coulombic efficiency
Capacity is 2508.1mAh/g, and first lap charge specific capacity is 1545.3mAh/g, coulombic efficiency 61.6%.After circulation 165 circle, put
Electricity specific capacity still has 635.7mAh/g, and the coulombic efficiency after stablizing is maintained at more than 98%.The carbon of the silicon parcel of embodiment 4 preparation
The lithium battery that fibrous composite assembles special capacity fade in front 80 circulations is very fast, but after 100 times circulate, battery
Rate-capacity is more stable.
The battery 5 charge-discharge performance under different multiplying as shown in figure 16,0.1A/g, 0.2A/g, 0.5A/g,
Circulate ten circles under the electric current density of 1A/g, 2A/g, 3A/g successively, finally return and carry out discharge and recharge under 0.1A/g electric current density and follow
Ring.As can be observed from Figure along with the increase of charging and discharging currents density, the specific capacity of battery is gradually reduced, when electric current density is
During 3A/g, specific capacity is 155.8mAh/g, and after returning to 0.1A/g, specific capacity is returned to 680mAh/g, along with circulation carries out battery ratio
Capacity has been decayed, and after 100 circulations, specific capacity is 520mAh/g.
Claims (10)
1. the preparation method of the carbon fibre composite of a silicon parcel, it is characterised in that specifically comprise the following steps that
(1) configuration silxoane precursors thing solution for later use, immerses in silxoane precursors thing solution by native cellulose, and room temperature is naturally dry
Dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film；
(2) natural cellulosic materials of the surface deposition silica dioxide gel film that step (1) obtains is at carbonization and magnesiothermic reduction
The carbon fibre composite of silicon parcel is obtained after reason.
The preparation method of the carbon fibre composite of silicon the most according to claim 1 parcel, it is characterised in that step (1)
In, described silxoane precursors thing is tetraethoxysilane or tetramethoxy-silicane；
Described silxoane precursors thing solution is with ethanol as solvent；
The concentration of described silxoane precursors thing solution is 0.1～1.2M.
The preparation method of the carbon fibre composite of silicon the most according to claim 2 parcel, it is characterised in that described silicon
Oxygen alkane precursor solution is tetraethoxysilane/ethanol solution, and concentration is 0.1～0.6M.
The preparation method of the carbon fibre composite of silicon the most according to claim 1 parcel, it is characterised in that step (1)
In, described native cellulose includes quantitative filter paper, Cotton Gossypii or cotton.
The preparation method of the carbon fibre composite of silicon the most according to claim 4 parcel, it is characterised in that described sky
So cellulose is quantitative filter paper.
The preparation method of the carbon fibre composite of silicon the most according to claim 1 parcel, it is characterised in that step (2)
In, described carbonization treatment is carried out under an inert atmosphere, and carburizing temperature is 450～750 DEG C, and the time is 5～10h.
The preparation method of the carbon fibre composite of silicon the most according to claim 1 parcel, it is characterised in that step (2)
In, described magnesiothermic reduction processes specifically comprises the processes of:
The carbonized product of the natural cellulosic materials that surface deposits silica dioxide gel film mixes with magnesium powder, 650～750
DEG C, reduce under inert atmosphere, obtain the carbon fibre composite of described silicon parcel；
The described surface deposition carbonized product of natural cellulosic materials of silica dioxide gel film and the mass ratio of magnesium powder be 1:1～
5。
The preparation method of the carbon fibre composite of silicon the most according to claim 7 parcel, it is characterised in that magnesiothermic reduction
Product after process again through soak with hydrochloric acid, washing, obtain the carbon fibre composite of described silicon parcel after drying.
9. the carbon fibre composite of the silicon parcel that prepared by the method as described in claim 1～8 any claim.
10. the carbon fibre composite of silicon as claimed in claim 9 parcel application in lithium ion battery.
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