CN106299375B - A kind of carbon fibre composite and its preparation method and application of silicon cladding - Google Patents
A kind of carbon fibre composite and its preparation method and application of silicon cladding Download PDFInfo
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- CN106299375B CN106299375B CN201610865456.3A CN201610865456A CN106299375B CN 106299375 B CN106299375 B CN 106299375B CN 201610865456 A CN201610865456 A CN 201610865456A CN 106299375 B CN106299375 B CN 106299375B
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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 a kind of preparation methods of the carbon fibre composite of silicon package, it include: configuration silxoane precursors object solution for later use, native cellulose is immersed in silxoane precursors object solution, natural drying at room temperature, obtains the natural cellulosic materials of surface deposition silica dioxide gel film；It is carbonized again and obtains the carbon fibre composite of silicon package with after magnesiothermic reduction processing.The present invention provides a kind of preparation methods of the carbon fibre composite of silicon package, preparation process is enormously simplified in the silica dioxide gel film of native cellulose surface basis weight deposition high silicon content through a step impregnation, it improves work efficiency, it can be achieved that large-scale industrial production.The carbon fibre composite of the silicon package prepared using this method has specific capacity big, cyclical stability is high, the advantages that having extended cycle life as the negative electrode material of lithium ion battery.
Description
Technical field
The present invention relates to the preparation fields of composite material, and in particular to a kind of carbon fibre composite and its system of silicon package
Preparation Method and application.
Background technique
With the fast development of science and technology, various electronic equipments and electric car, which have, to be widely applied, to chemistry
The requirement of power supply is also higher and higher.For lithium ion battery since its is small in size, specific capacity is high, environmentally protective, can repeatedly charge and discharge etc.
Advantage has been widely used in electronic equipment.
The negative electrode material for the lithium ion battery being commercialized at present is mostly graphite, but the lower theoretical specific capacity of graphite
(372mAh/g) limits the further development of high-capacity lithium ion cell.The study found that silicon substrate, 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, leads to these materials
Cyclical stability is poor, can not be commercialized.So the bulk effect for how reducing these materials is ground at current lithium ion battery
Hot issue in studying carefully.
In non-graphite system negative electrode material, silicon is due to high theoretical specific capacity (4200mAh/g), high stability, peace
Entirely, the advantages such as pollution-free have obtained extensive concern.But volume expansion and contraction are serious during lithium ion deintercalation, can lead
Material disintegrating is caused to fall off, specific capacity decline is fast, and cyclical stability is poor.In addition, the electric conductivity of silicon is not this strong influence very well
The application of the cycle performance and silicon substrate anode material lithium ion battery of silicon cathode material.
Currently, researcher solves the problems, such as that silicon substrate cathode material exists by a variety of methods, including nanosizing, thin
Membranization, Composite etc..Carbon material has stable chemical property, good conductivity, in addition, carbon material is inherently a kind of good
Lithium storage materials, volume change is small during storing up lithium, can bear certain mechanical stress, plays certain delay to the volume expansion of silicon
Punching effect and it is similar to the intercalation potential of silicon it is compound with silicon after it is relatively small to material capacity loss, therefore, in silicon substrate composite wood
It is widely studied in material.In recent years, silicon/carbon is generally prepared using high-energy ball milling method or chemical vapor deposition (CVD) method etc.
Nanocomposite.Although these measures all improve the performance of silicon substrate cathode material to some extent, preparation process is complicated,
Expensive instrument and equipment is needed, it is at high cost, so that there is also certain distances for silicon substrate anode material and commercial applications.
As Publication No. CN103730645A patent document in disclose a kind of silicon carbon coated for lithium ion battery
Fiber nanocomposite and its preparation method and application, specific steps are as follows: using tetramethoxy-silicane as precursor, natural fiber
Element is template and carbon source, deposits nanometer titanium dioxide silicate gel film on native cellulose surface through surface sol-gel method first, then
Coated with silica carbon fiber nanometer composite material is obtained through calcining carbonization in inert gas, finally uses low temperature magnesium reduction process
Reduction obtains silicon cladding carbon fiber nanometer composite material.It is multiple by repeating standing deposition-hydrolysis operation in the preparation method
Afterwards, it can be achieved that the accuracy controlling of the nanometer titanium dioxide silicate gel film thickness to deposition, to obtain the silicon carbon coated of different silicone contents
Fiber nanocomposite.When this method still has following drawback:
1) silicone content in silicon cladding carbon fiber nanometer composite material, being prepared is too low, and silicon is caused to coat carbon fiber
The specific capacity of nanocomposite is not high, and compared with graphite cathode material, advantage is little in terms of specific capacity, is unfavorable for improving lithium
The performance of ion battery.
2), preparation process is complicated, it is more difficult to realize large-scale industrial production.
Summary of the invention
The present invention provides a kind of preparation methods of the carbon fibre composite of silicon package, through a step impregnation, in day
The silica dioxide gel film of right cellulose surface quantitative deposition high silicon content, enormously simplifies preparation process, improves work effect
Rate is, it can be achieved that large-scale industrial production.Using the carbon fibre composite of the silicon package of this method preparation as lithium-ion electric
The negative electrode material in pond has specific capacity big, and cyclical stability is high, the advantages that having extended cycle life.
The invention discloses a kind of preparation methods of the carbon fibre composite of silicon package, the specific steps are as follows:
(1) silxoane precursors object solution for later use is configured, native cellulose is immersed in silxoane precursors object solution, room temperature is certainly
It is so dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film；
(2) natural cellulosic materials for the surface deposition silica dioxide gel film that step (1) obtains are through being carbonized with magnesium heat also
The carbon fibre composite of silicon package is obtained after the reason of original place.
The present invention is directed to the serious bulk effect that generates in lithium deintercalation of silicon, using the support and buffer function of carbon material,
The characteristic of silicon height ratio capacity is kept, and increases its cyclical stability.
In step (1), solvent needed for configuring silxoane precursors object solution only needs that silxoane precursors object can be dissolved,
Preferably, the silxoane precursors object is tetraethoxysilane or tetramethoxy-silicane, solvent is ethyl alcohol.
Chemical property is related with the content of silicon in composite material and silicon layer thickness.And the concentration of silxoane precursors object solution
The content and silicon layer thickness of silicon in the composite material being prepared will be directly affected.Preferably, the silxoane precursors object is molten
The concentration of liquid is 0.1M~1.2M.It is found through experiment that the thickness of silicon layer is too thin, it is unfavorable for improving the specific capacity of composite material, too
The special capacity fade of thick composite material is fast, and stability is poor.Therefore, the concentration of silxoane precursors object solution be further preferably 0.1~
0.6M。
Further, it also found through test, when the concentration of silxoane precursors object solution is 0.3M, the silicon carbon coated of preparation
In fibrous composite, the mass percentage of silicon is 25wt%, and thickness is about 40nm.The thickness of silicon layer is suitable in the composite material
In, be on the one hand conducive to buffer enormousness during the embedding lithium of nano silicon particles takes off lithium and change, material disintegrating is effectively prevent to fall off,
On the other hand, volume increases the stress generated when relatively thin silicon layer is conducive to transmit silicon embedding lithium.In addition, the carbon fiber of multilayered structure
Dimension mesh substrate also has certain limitation to the buffer function of silicon layer.So being prepared with the silxoane precursors object solution of the concentration
The carbon fibre composite specific capacity for obtaining silicon package is maximum, and stability is also preferable in charge and discharge cycles.Therefore, most preferably
The concentration of silxoane precursors object solution is 0.3M.
The carbon material used in the present invention derives from native cellulose, and native cellulose heats in inert gas, when arriving
Start spontaneous charing up to 275 DEG C, only a part of carbon and other ingredient burn-ups in the case where anoxic, when temperature reaches
It carbonizes and completes at 400~500 DEG C, obtained carbon material can effectively buffer serious volume change when silicon removal lithium embedded, and increase
The electric conductivity of material.Preferably, the native cellulose includes quantitative filter paper, cotton or cotton in step (1).Into one
Step is preferably quantitative filter paper, and quantitative filter paper is interwoven by many micron order webs, and these micron order fibers are by many
Nano-scale fiber binding is interwoven, and has fibrous layer level structure, has very big specific surface area, is conducive to the biography of electronics
It is defeated, the electric conductivity of material is improved, the specific capacity of material can be effectively improved.
Preferably, the carbonization treatment carries out under an inert atmosphere in step (2), carburizing temperature is 450~750
DEG C, the time is 5~10h.
Preferably, in step (2), the magnesiothermic reduction processing specifically comprises the processes of:
The carbonized product of natural cellulosic materials of surface deposition silica dioxide gel film is mixed with magnesium powder, 650~
750 DEG C, restore under inert atmosphere, obtain the carbon fibre composite of the silicon package；
The surface deposits the carbonized product of natural cellulosic materials of silica dioxide gel film and the mass ratio of magnesium powder is
1:1~5.
Still more preferably:
In step (2), carbonization treatment technique are as follows: argon gas protects lower 600 DEG C of carbonizations 6h；Magnesiothermic reduction treatment process are as follows: table
Face deposit silica dioxide gel film natural cellulosic materials carbonized product and magnesium powder 1:1 in mass ratio mixing, 700 DEG C,
6h is restored in argon gas.
Above-mentioned carbonization treatment and magnesiothermic reduction processing concrete technology condition find after extensive testing, with
The natural cellulosic materials of the surface deposition silica dioxide gel film prepared by the silxoane precursors object solution of 0.1~0.6M are most
The subsequent treatment process matched.It certainly, is 0.3M with above-mentioned subsequent treatment process silxoane precursors object solution concentration the most matched.
Preferably, magnesiothermic reduction treated product again through salt acid soak, washing, it is dry after obtain the silicon package
Carbon fibre composite.
Preferably, the inert gas used in carbonization and magnesiothermic reduction processing is high-purity argon gas.
The invention also discloses the carbon fibre composite wrapped up according to the silicon of above-mentioned method preparation and its in lithium ion
Application in battery.
In order to detect preparation silicon package carbon fibre composite chemical property, assemble them into button cell into
Row electrochemical property test.There is bigger specific volume compared with graphite negative electrodes material common in current commercial Li-ion batteries
Amount.
Compared with prior art, the invention has the following advantages that
1, the present invention uses only a step leaching during natural cellulosic materials surface deposits silica dioxide gel film
Stain processing is achieved that the deposition of high silicon content, and the concentration by changing precursor solution used, may be implemented to titanium dioxide
The regulation of silicone content, enormously simplifies preparation process in silicate gel film, improves work efficiency, and is easy to implement large-scale industry
Metaplasia produces.
2, preparation method is simple in the present invention, inexpensive, pollution-free.
3, the lithium ion battery that the carbon fibre composite of the silicon package prepared using this method is assembled as negative electrode material, tool
Have that specific capacity is big, cyclical stability is high, the advantages that having extended cycle life.
Detailed description of the invention
Fig. 1 is that scanning electron microscope of the carbon fibre composite of silicon package prepared by embodiment 1 under different amplification is shone
Piece；
Fig. 2 is the transmission electron microscope photo of the carbon fibre composite of silicon package prepared by embodiment 1；
Fig. 3 is the high-resolution-ration transmission electric-lens photo of the carbon fibre composite of silicon package prepared by embodiment 1；
Fig. 4 is the transmission electron microscope and high power transmission electron microscope photo of the nano-tube material of comparative example preparation；
Fig. 5 is the constant current charge and discharge cycle performance and coulombic efficiency curve of battery 1；
Fig. 6 is charge-discharge performance curve of the battery 1 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 scanning and transmission of the carbon fibre composite of silicon package prepared by embodiment 2 under different amplification
Electromicroscopic photograph；
Fig. 9 is scanning and transmission of the carbon fibre composite of silicon package prepared by embodiment 3 under different amplification
Electromicroscopic photograph；
Figure 10 is scanning and transmission of the carbon fibre composite of silicon package prepared by embodiment 4 under different amplification
Electromicroscopic photograph；
Figure 11 is the constant current charge and discharge cycle performance and coulombic efficiency curve of battery 3；
Figure 12 is charge-discharge performance curve of the battery 3 under different multiplying；
Figure 13 is the constant current charge and discharge cycle performance and coulombic efficiency curve of battery 4；
Figure 14 is charge-discharge performance curve of the battery 4 under different multiplying；
Figure 15 is the constant current charge and discharge cycle performance and coulombic efficiency curve of battery 5；
Figure 16 is charge-discharge performance curve of the battery 5 under different multiplying.
Specific embodiment
Embodiment 1:
(1) using ethyl alcohol as solvent, configuration concentration is the tetraethoxysilane solution of 0.3M, and is stirred at room temperature 2 small
When.
(2) laboratory is often immersed in above-mentioned tetraethoxysilane/ethanol solution with quantitative filter paper, it is naturally dry at room temperature
It is dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film.
(3) native cellulose for the surface deposition silica dioxide gel film that step (2) obtains is 600 under high-purity argon gas protection
DEG C carbonization 6h, obtain the carbon fibre composite of Silica-coated.
(4) carbon fibre composite for the Silica-coated for obtaining step (3) and magnesium powder 1:1 in mass ratio mixing,
Restore 6h, reduzate salt acid soak 8h in 700 DEG C, high-purity argon gas, then with distilled water and ethanol washing, vacuum drying,
Obtain the carbon fibre composite of the silicon package.
The stereoscan photograph of the carbon fibre composite of silicon package manufactured in the present embodiment is as shown in Figure 1, Fig. 1 a) it is to put
Big 10k times of stereoscan photograph, interior attached drawing are the photo of material；Fig. 1 b) it is the stereoscan photograph for amplifying 50k times.Observation
Fig. 1 can see, and the carbon fibre composite of silicon package replicates the fibrous structure of quantitative filter paper, the diameter of fiber well
For 100~200nm.
The transmission electron microscope photo of the carbon fibre composite of silicon package manufactured in the present embodiment is as shown in Fig. 2, be single in figure
The carbon fiber of root silicon package.The diameter of fiber about 150nm, fiber surface package silicon layer with a thickness of 30~50nm, silicon particle
Size be several nanometers.Fig. 3 is the high-resolution-ration transmission electric-lens photo of the carbon fibre composite of silicon package, it can be seen that silicon crystal
Lattice fringe correspond to (220) crystal face of silicon.What is be inserted into figure is selective electron diffraction image, and electronic diffraction map shows crystal form
Silicon, 1,2 diffraction rings respectively correspond (311) and (511) crystal face of silicon.It proves after low temperature magnesiothermic reduction, silica success
Ground is reduced to crystalline silicon.
Comparative example:
Step (3) in embodiment 1 is changed to calcine 6h at 600 DEG C in air, remaining is same as Example 1.Pass through
Air calcination removes the native cellulose as template, and being prepared is Silica Nanotube material, then through magnesiothermic reduction
Obtain nano-tube material.
Comparative example preparation nano-tube material transmission electron microscope a) and b), high-resolution-ration transmission electric-lens photo c) and constituency electricity
For sub- diffraction pattern d) as shown in figure 4, the tubular structure of nano-tube material can be clearly apparent, the silicon of nano particle is packed together shape
At tube wall.Spread out from high-resolution-ration transmission electric-lens photo it can be seen that (111) crystal face of crystalline silicon, 1~3 in selective electron diffraction figure
It penetrates (220) that ring corresponds to silicon, (422) and (511) crystal face.
Embodiment 2:
(1) using ethyl alcohol as solvent, configuration concentration is the tetraethoxysilane solution of 0.1M, and is stirred at room temperature 2 small
When.
(2) laboratory is often immersed in above-mentioned tetraethoxysilane/ethanol solution with quantitative filter paper, it is naturally dry at room temperature
It is dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film.
(3) native cellulose for the surface deposition silica dioxide gel film that step (2) obtains is 600 under high-purity argon gas protection
DEG C carbonization 6h, obtain the carbon fibre composite of Silica-coated.
(4) carbon fibre composite for the Silica-coated for obtaining step (3) and magnesium powder 1:1 in mass ratio mixing,
Restore 6h, reduzate salt acid soak 8h in 700 DEG C, high-purity argon gas, then with distilled water and ethanol washing, vacuum drying,
Obtain the carbon fibre composite of the silicon package.
The stereoscan photograph of the carbon fibre composite of silicon package manufactured in the present embodiment is as shown in figure 8, Fig. 8 a) it is to put
Big 20k times of stereoscan photograph, interior attached drawing are the photo of material；Fig. 8 b) it is the stereoscan photograph for amplifying 80k times.From sweeping
Retouching can be observed the fibrous structure that the carbon fibre composite that silicon wraps up replicates quantitative filter paper well in electromicroscopic photograph, fine
The diameter of dimension is 100~200nm.
Transmission electron microscope photo such as Fig. 8 c of the carbon fibre composite of silicon package manufactured in the present embodiment) and d) shown, figure
In be single silicon package carbon fiber.The thickness of the diameter of fiber about 150nm, the silicon layer of fiber surface package are about 20nm.
Embodiment 3:
(1) using ethyl alcohol as solvent, configuration concentration is the tetraethoxysilane solution of 0.6M, and is stirred at room temperature 2 small
When.
(2) laboratory is often immersed in above-mentioned tetraethoxysilane/ethanol solution with quantitative filter paper, it is naturally dry at room temperature
It is dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film.
(3) native cellulose for the surface deposition silica dioxide gel film that step (2) obtains is 600 under high-purity argon gas protection
DEG C carbonization 6h, obtain the carbon fibre composite of Silica-coated.
(4) carbon fibre composite for the Silica-coated for obtaining step (3) and magnesium powder 1:1 in mass ratio mixing,
Restore 6h, reduzate salt acid soak 8h in 700 DEG C, high-purity argon gas, then with distilled water and ethanol washing, vacuum drying,
Obtain the carbon fibre composite of the silicon package.
The stereoscan photograph of the carbon fibre composite of silicon package manufactured in the present embodiment is as shown in figure 9, Fig. 9 a) it is to put
Big 20k times of stereoscan photograph, interior attached drawing are the photo of material；Fig. 9 b) it is the stereoscan photograph for amplifying 100k times.From sweeping
Retouching can be observed the fibrous structure that the carbon fibre composite that silicon wraps up replicates quantitative filter paper well in electromicroscopic photograph, fine
The diameter of dimension is 100~200nm.
Transmission electron microscope photo such as Fig. 9 c of the carbon fibre composite of silicon package manufactured in the present embodiment) and d) shown, figure
In be single silicon package carbon fiber.The thickness of the diameter of fiber about 150nm, the silicon layer of fiber surface package are about 50nm.
Embodiment 4:
(1) using ethyl alcohol as solvent, configuration concentration is the tetraethoxysilane solution of 1.2M, and is stirred at room temperature 2 small
When.
(2) laboratory is often immersed in above-mentioned tetraethoxysilane/ethanol solution with quantitative filter paper, it is naturally dry at room temperature
It is dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film.
(3) native cellulose for the surface deposition silica dioxide gel film that step (2) obtains is 600 under high-purity argon gas protection
DEG C carbonization 6h, obtain the carbon fibre composite of Silica-coated.
(4) carbon fibre composite for the Silica-coated for obtaining step (3) and magnesium powder 1:1 in mass ratio mixing,
Restore 6h, reduzate salt acid soak 8h in 700 DEG C, high-purity argon gas, then with distilled water and ethanol washing, vacuum drying,
Obtain the carbon fibre composite of the silicon package.
The stereoscan photograph of the carbon fibre composite of silicon package manufactured in the present embodiment is as shown in Figure 10, Figure 10 a) be
The stereoscan photograph of 20k times of amplification, interior attached drawing are the photo of material；Figure 10 b) it is the stereoscan photograph for amplifying 80k times.From
The carbon fibre composite that silicon package can be observed in stereoscan photograph replicates the fibrous structure of quantitative filter paper well,
The diameter of fiber is 100~200nm.
Transmission electron microscope photo such as Figure 10 c of the carbon fibre composite of silicon package manufactured in the present embodiment) and d) shown, figure
In be single silicon package carbon fiber.The thickness of the diameter of fiber about 150nm, the silicon layer of fiber surface package are about 60nm.
Application examples:
Material a is ground into 30min in the agate mortar, weigh 40mg and with mass ratio 70:15:15 and superconduction electrical carbon and is glued
Agent PVDF mixing is tied, pasty slurry is tuned into, is applied in nickel foam, is dried in vacuo 12 hours, tabletting.
When material a is the carbon fibre composite for the silicon package that embodiment is prepared, the lithium ion battery that is prepared into
Negative electrode tab is denoted as 1；
When material a is the nano-tube material that comparative example is prepared, the anode plate for lithium ionic cell being prepared into is denoted as
2；
When material a is the carbon fibre composite for the silicon package that embodiment 2 is prepared, the lithium ion battery that is prepared into
Negative electrode tab is denoted as 3；
When material a is the carbon fibre composite for the silicon package that embodiment 3 is prepared, the lithium ion battery that is prepared into
Negative electrode tab is denoted as 4；
When material a is the carbon fibre composite for the silicon package that embodiment 4 is prepared, the lithium ion battery that is prepared into
Negative electrode tab is denoted as 5；
Anode plate for lithium ionic cell 1~5 is assembled in the glove box full of argon gas with positive plate-lithium piece respectively respectively,
Obtain CR2025 type button cell 1~5.The electrolyte used is with LiPF6It is the ethylene carbonate of 1:1:1 with volume ratio for solute
Ester (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) are solvent, and the diaphragm used is Celgard 2300.
The button cell of assembling is tested, tests battery 1~5 respectively using battery system in constant current and difference times
Charge-discharge performance under rate, charge and discharge voltage range are 0.01~3.0V.
Constant current (100mA/g) charge-discharge performance and coulombic efficiency of battery 1 ratio as shown in figure 5, first lap discharges
Capacity is 2610.5mAh/g, and first lap charge specific capacity is 1422.7mAh/g, coulombic efficiency 54.5%.After 200 circle of circulation, put
Electric specific capacity still has 729.3mAh/g, and the coulombic efficiency after stablizing is maintained at 98% or more.Illustrate silicon package prepared by embodiment 1
Carbon fibre composite assembling lithium battery have biggish specific capacity and preferable cyclical stability.
Charge-discharge performance of the battery 1 under different multiplying is as shown in fig. 6, in 0.1A/g, 0.2A/g, 0.5A/g, 1A/
G, ten circles are circuited sequentially under the current density of 2A/g, 3A/g, finally returns 0.1A/g.Still there is specific capacity when 3A/g
218.2mAh/g, after returning to 0.1A/g, specific capacity is returned to 700mAh/g or more.
The comparison of the constant current charge-discharge cycle performance of battery 1,2 is as shown in Figure 7.Due to the carbon fiber composite of silicon package
The support and buffer function of carbon, silicon are not easy to collapse in cyclic process in material, and material, which is not easy to crush, to fall off, so having preferable
Cyclical stability.It can be seen from the figure that the specific capacity of battery 1 still has a 729.3mAh/g after 200 circle of circulation, and battery 2
Specific capacity has fallen to 325mAh/g.
Constant current (100mA/g) charge-discharge performance and coulombic efficiency of battery 3 are as shown in figure 11, first lap electric discharge ratio
Capacity is 2133.5mAh/g, and first lap charge specific capacity is 1104.3mAh/g, coulombic efficiency 51.8%.After 180 circle of circulation, put
Electric specific capacity still has 630.8mAh/g, and the coulombic efficiency after stablizing is maintained at 98% or more.Illustrate silicon package prepared by embodiment 2
Carbon fibre composite assembling lithium battery have biggish specific capacity and preferable cyclical stability.
Charge-discharge performance of the battery 3 under different multiplying is as shown in figure 12,0.1A/g, 0.2A/g, 0.5A/g,
Ten circles are circuited sequentially under the current density of 1A/g, 2A/g, 3A/g, are finally returned progress charge and discharge under 0.1A/g current density and are followed
Ring.As can be observed from Figure with the increase of charging and discharging currents density, the specific capacity of battery is gradually reduced, when current density is
Specific capacity is 165.5mAh/g when 3A/g, and after returning to 0.1A/g, specific capacity is returned to 590mAh/g or more, and with circulation time
Number carries out, and specific capacity is more stable.Illustrate that the composite material has preferable high rate performance and cyclical stability.
Constant current (100mA/g) charge-discharge performance and coulombic efficiency of battery 4 are as shown in figure 13, first lap electric discharge ratio
Capacity is 3009.3mAh/g, and first lap charge specific capacity is 1505.2mAh/g, coulombic efficiency 50.0%.After 200 circle of circulation, put
Electric specific capacity still has 487.2mAh/g, and the coulombic efficiency after stablizing is maintained at 98% or more.The carbon of silicon package prepared by embodiment 3
The lithium battery of fibrous composite assembling specific capacity in first 80 times circulations is decayed, after 100 circulations, the ratio of battery
Example capacity is more stable.
Charge-discharge performance of the battery 4 under different multiplying is as shown in figure 14,0.1A/g, 0.2A/g, 0.5A/g,
Ten circles are circuited sequentially under the current density of 1A/g, 2A/g, 3A/g, are finally returned progress charge and discharge under 0.1A/g current density and are followed
Ring.As can be observed from Figure with the increase of charging and discharging currents density, the specific capacity of battery is gradually reduced, when current density is
After specific capacity still has 234.9mAh/g, current density to return to 0.1A/g when 3A/g, specific capacity is returned to 630mAh/g or more.Explanation
The composite material has preferable high rate performance and cyclical stability.
Constant current (100mA/g) charge-discharge performance and coulombic efficiency of battery 5 are as shown in figure 15, first lap electric discharge ratio
Capacity is 2508.1mAh/g, and first lap charge specific capacity is 1545.3mAh/g, coulombic efficiency 61.6%.After 165 circle of circulation, put
Electric specific capacity still has 635.7mAh/g, and the coulombic efficiency after stablizing is maintained at 98% or more.The carbon of silicon package prepared by embodiment 4
The lithium battery of fibrous composite assembling special capacity fade in first 80 times circulations is very fast, but after 100 circulations, battery
Rate-capacity is more stable.
Charge-discharge performance of the battery 5 under different multiplying is as shown in figure 16,0.1A/g, 0.2A/g, 0.5A/g,
Ten circles are circuited sequentially under the current density of 1A/g, 2A/g, 3A/g, are finally returned progress charge and discharge under 0.1A/g current density and are followed
Ring.As can be observed from Figure with the increase of charging and discharging currents density, the specific capacity of battery is gradually reduced, when current density is
Specific capacity is 155.8mAh/g when 3A/g, and after returning to 0.1A/g, specific capacity is returned to 680mAh/g, as circulation carries out battery ratio
Capacity is decayed, after 100 circulations, specific capacity 520mAh/g.
Claims (6)
1. a kind of preparation method for the carbon fibre composite that the silicon applied to lithium ion battery wraps up, which is characterized in that specific
Steps are as follows:
(1) silxoane precursors object solution for later use is configured, native cellulose is immersed in silxoane precursors object solution, room temperature is naturally dry
It is dry, obtain the natural cellulosic materials of surface deposition silica dioxide gel film；
The silxoane precursors object solution, concentration 0.3M；
The silxoane precursors object is tetraethoxysilane or tetramethoxy-silicane；
The silxoane precursors object solution is using ethyl alcohol as solvent
(2) natural cellulosic materials of step (1) obtains surface deposition silica dioxide gel film through carbonization and magnesiothermic reduction at
The carbon fibre composite of silicon package is obtained after reason；
The carbonization treatment technique are as follows: argon gas protects lower 600 DEG C of carbonizations 6h；
The magnesiothermic reduction treatment process are as follows: surface deposit silica dioxide gel film natural cellulosic materials carbonized product and
Magnesium powder 1:1 in mass ratio mixing, restores 6h in 700 DEG C, argon gas；
In the carbon fibre composite of the silicon package, the mass percentage of silicon is 25wt%, the silicon layer of fiber surface package
With a thickness of 30 ~ 50nm.
2. the preparation method for the carbon fibre composite that the silicon according to claim 1 applied to lithium ion battery wraps up,
It is characterized in that, the silxoane precursors object solution is tetraethoxysilane/ethanol solution.
3. the preparation method for the carbon fibre composite that the silicon according to claim 1 applied to lithium ion battery wraps up,
It is characterized in that, the native cellulose includes quantitative filter paper, cotton or cotton in step (1).
4. the preparation method for the carbon fibre composite that the silicon according to claim 3 applied to lithium ion battery wraps up,
It is characterized in that, the native cellulose is quantitative filter paper.
5. the preparation method for the carbon fibre composite that the silicon according to claim 1 applied to lithium ion battery wraps up,
It is characterized in that, magnesiothermic reduction treated product again through salt acid soak, washing, it is dry after obtain the carbon fiber of the silicon package
Tie up composite material.
6. a kind of silicon package applied to lithium ion battery of the method preparation as described in claim 1 ~ 5 any claim
Carbon fibre composite.
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| CN103730645A (en) * | 2014-01-17 | 2014-04-16 | 江苏华盛精化工股份有限公司 | Silicon-coated carbon fiber nano composite material and preparation method and application thereof |
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Address after: 215635 No.10, Qinghai Road, Yangzi River International Chemical Industry Park, Zhangjiagang, Suzhou, Jiangsu Province Co-patentee after: Zhejiang University Patentee after: Jiangsu Huasheng lithium battery materials Co., Ltd Address before: 215635, Qinghai Road, Zhangjiagang International Chemical Industrial Park, Yangzi River, Suzhou, Jiangsu 28, China Co-patentee before: Zhejiang University Patentee before: HSC Corporation |