CN108172781A - A kind of Si-C composite material of Argent grain doping and its preparation method and application - Google Patents
A kind of Si-C composite material of Argent grain doping and its preparation method and application Download PDFInfo
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- CN108172781A CN108172781A CN201711311092.5A CN201711311092A CN108172781A CN 108172781 A CN108172781 A CN 108172781A CN 201711311092 A CN201711311092 A CN 201711311092A CN 108172781 A CN108172781 A CN 108172781A
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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
- H01M4/366—Composites as layered products
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- 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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- 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
- H01M4/626—Metals
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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
Si-C composite material the invention discloses a kind of doping of Argent grain and its preparation method and application, this method includes:Al Si alloying pellets are dispersed in HCl/water solution, dispersion reaction is then centrifuged for, cleans, vacuum drying;Ammonium hydroxide is added to AgNO3In aqueous solution, it is prepared into silver ammino solution, by the powder of gained Porous Silicon structures, ethyl alcohol, silver ammino solution and polyvinylpyrrolidone hybrid reaction, finally centrifuged, cleaning, vacuum drying obtains black powder by black powder by chemical vapour deposition reaction deposited carbon layer, obtains the Si-C composite material of Argent grain doping.Obtained structure has high stability and high conductivity, it can not only effectively solve the problems, such as volume change of the silicon in charge and discharge process, the problem of also improving the intrinsic poorly conductive of silicon simultaneously, battery is suitable for high-energy density energy storage device made of the Ag doping silicon-carbon compound lithium ion negative material prepared using the present invention.
Description
Technical field
The present invention relates to technical field of lithium ion battery negative, and in particular to a kind of silicon-carbon of Argent grain doping is compound
Material and its preparation method and application.
Background technology
As the novel energy-storing technology application scale based on battery technology steeply rises, lithium ion battery plays more next
More important role.Commercial lithium ion battery has been unable to meet high energy portable power, power using graphite as cathode at present
Demand of the fields such as battery and energy-accumulating power station to high-energy density and high power density, silicon possess very high theoretical specific capacity and
Low operating voltage has become the emphasis of lithium ion battery worker research.However, due to bulk effect and poorly conductive
Problem, silicon-based anode does not slowly put into large-scale commercial in use, silicon can generate about 300% volume in process of intercalation
Variation, huge volume change can cause the dusting of silicon electrode to peel off, and make to lose between silicon particle and between silicon and collector
Electrical contact, the specific capacity of electrode drastically decline even entirely ineffective.
There is the defects of above notable in view of silicium cathode, the performance of silicon is improved there has been proposed a large amount of silicon structure.
Silicon nanowires, nano-tube, silicon thin film inhibit the expansion of silicon to have significant effect all on three-dimensional, have the ability to bear to take off
Volume change in process of intercalation repeatedly is without generating powder phenomenon-tion.In addition to the silicon of these structures, it is similarly subjected in silicium cathode
What is studied extensively is to be combined silicon with the carbon of various structures.The addition of carbon can effectively make up asking for the intrinsic poorly conductive of silicon
Topic, and then improve coulombic efficiency.In view of this consideration, people have successfully prepared a large amount of silicon-carbon composite cathode material, carbon-coating
As protective layer and conductive layer for promoting the chemical properties such as the stable circulation performance of silicon cathode lithium ion battery, high rate performance
With obvious action.However, only there is certain limitation in the external electric conductivity for improving silicon, to further play
The new capability of silicon, internal electric conductivity are also badly in need of improving.
Invention content
The present invention provides a kind of Si-C composite material of Argent grain doping and preparation method thereof and is preparing lithium ion battery
It applies in negative material and lithium ion battery, is made first with the commercialized Al-Si alloys of hydrochloric acid solution pickling with internal holes
Then metallic silver particles are made by modified silver mirror reaction, finally with acetylene gas in the porous silicon of hole structure inside porous silicon
Body coats one layer of carbon for carbon source in the porous silicon surface for being doped with Argent grain, silicon-carbon composite cathode material is made, and as work
Property substance assembling battery.
A kind of preparation method of the Si-C composite material of Argent grain doping, includes the following steps:
(1) Al-Si alloying pellets being dispersed in HCl/water solution, dispersion reaction is then centrifuged for, cleans, vacuum drying,
Obtain the powder of Porous Silicon structures;
(2) ammonium hydroxide is added to AgNO3In aqueous solution, silver ammino solution is prepared into, by Porous Silicon structures obtained by step (1)
Powder, ethyl alcohol, silver ammino solution and polyvinylpyrrolidone hybrid reaction, are finally centrifuged, and are cleaned, and vacuum drying obtains
Black powder;
(3) black powder obtained by step (2) is obtained into Argent grain doping by chemical vapour deposition reaction deposited carbon layer
Si-C composite material.
The method of the present invention using HCl/water solution etches Al-Si alloys, obtains the internal porous silicon with porous structure, is
Huge volume change provides space during removal lithium embedded;Using silver ammino solution, by modified silver mirror reaction in porous silicon
Portion's in-situ preparation has the Argent grain of high conductivity, in porous silicon internal build conductive network structure, improves its internal conduction
Property;Carbon-coating is coated in porous silicon surface using acetylene as presoma by way of chemical vapor deposition, on the one hand plays stable knot
Structure, the effect for preventing volume change from structure being caused to be destroyed, on the other hand in porous silicon build up outside conductive network, is conducive to electricity
The transmission of son, so as to improve chemical property.Material carbon content (mass percent) 20-40% obtained in this way, silver
Content (mass percent) 3-5%.The novel uniqueness of this method, obtained structure have high stability and high conductivity,
It can not only effectively solve the problems, such as volume change of the silicon in charge and discharge process, while also improve the intrinsic poorly conductive of silicon
Problem, battery is stored up suitable for high-energy density made of the Ag doping silicon-carbon compound lithium ion negative material prepared using the present invention
It can device.
In step (1), commercialized commercial product can be used in Al-Si alloying pellets.
The mass fraction of HCl/water solution is 10%~30%, further preferably 15%~25%, most preferably 20%.
The condition of described dispersion reaction is:Ultrasound 15 minutes~45 minutes, magnetic agitation 1h~3h, further excellent later
Choosing, ultrasound 20 minutes~40 minutes, magnetic agitation 1.5h~2.5h, most preferably, 30 minutes ultrasonic later, later magnetic agitation
2h。
Cleaning uses deionized water and washes of absolute alcohol for several times.
The vacuum drying condition is:Place 4~8 hours in 70 DEG C~90 DEG C of vacuum drying chamber, further
It is preferred that being placed 5~7 hours in 75 DEG C~85 DEG C of vacuum drying chamber, most preferably, 6 are placed in 80 DEG C of vacuum drying chamber
Hour.
In step (2), a concentration of 0.5mol/L-3mol/L, AgNO of the ammonium hydroxide3A concentration of 0.005- of aqueous solution
0.03mol/L.Further preferably, a concentration of 1mol/L-3mol/L, AgNO of the ammonium hydroxide3A concentration of 0.01- of aqueous solution
0.03mol/L。
The hybrid reaction is to react 16h~32h in 60 DEG C~80 DEG C stirring in water bath, further preferably, 65 DEG C~
75 DEG C of stirring in water bath react 20h~28h, most preferably, in 70 DEG C of stirring in water bath reactions for 24 hours.
In step (3), specifically included by chemical vapour deposition reaction deposited carbon layer:
Black powder is laid in quartz boat, tube furnace is put into and carries out chemical vapour deposition reaction, in Ar protective atmospheres
Under with the speed of 3~8 DEG C/min be warming up to 600 DEG C~800 DEG C, be passed through C2H2Gas, at the same by Ar flows be adjusted to 30sccm~
50sccm keeps 20min~40min, closes C2H2Gas takes out after environment temperature is cooled under Ar protective atmospheres.
Further preferably, black powder is laid in quartz boat, is put into tube furnace and carries out chemical vapour deposition reaction,
700 DEG C are warming up to the speed of 5 DEG C/min under Ar protective atmospheres, is passed through C2H2Gas, while reduce Ar flows to 40sccm, it protects
30min is held, closes C2H2Gas takes out after environment temperature is cooled under Ar protective atmospheres.
The Si-C composite material of Argent grain doping prepared by the preparation method, carbon content (mass percent) exist
20-40%, silver content (mass percent) is in 3-5%.
The Si-C composite material of the Argent grain doping is used in particular for preparing lithium ion battery negative material and be used for
Prepare lithium ion battery.Using the Si-C composite material (powder) of Argent grain doping as active material, according to active material:
super P:CMC:SBR=7:1:1:1 ratio prepares slurry, as cathode assembled battery.
Compared with prior art, the invention has the advantages that:
(1) there is enough inner spaces by porous silicon prepared by pickling Al-Si alloys, can greatly alleviates charge and discharge
Huge volume change in electric process.
(2) doping metals Argent grain can provide inner conductive network for porous silicon inside porous silicon, be conducive to improve
The electric conductivity of composite inner.
(3) on the one hand rock-steady structure is played the role of by carbon-coating made from chemical vapor deposition, to a certain extent
The expansion of silicon is inhibited, on the other hand external conductive network is provided as outer conductive layers, improves outside composite material
Electric conductivity.
(4) lithium ion battery assembled by the use of the Argent grain doping Si-C composite material prepared as cathode significantly improves electricity
Chemical stability and high rate performance.
Description of the drawings
It, below will be to attached drawing needed in the embodiment in order to illustrate more clearly of the technical solution that the present invention is implemented
It is briefly described.
Fig. 1 is the silicon-carbon composite lithium ion battery cathode material of the Argent grain doping according to prepared by embodiment 1 in difference
The stereoscan photograph of preparatory phase, Fig. 1 a are initial Al-Si alloys, and Fig. 1 b are Porous Silicon structures, and Fig. 1 c are mixed for Ag particles
Miscellaneous structure, the Si-C composite material of Argent grain doping of the surface covered with carbon-coating shown in Fig. 1 d;
Fig. 2 is the transmission of the silicon-carbon composite lithium ion battery cathode material of the Argent grain doping according to prepared by embodiment 1
Electron microscopic picture and distribution diagram of element, Fig. 2 a, 2b, 2c are the transmission of the silicon-carbon composite lithium ion battery cathode material of Argent grain doping
Electron microscopic picture, Fig. 2 d are the Si distribution diagram of element of the silicon-carbon composite lithium ion battery cathode material of Argent grain doping, and Fig. 2 e are silver
The C element distribution map of the silicon-carbon composite lithium ion battery cathode material of particle doping, Fig. 2 f are that the silicon-carbon of Argent grain doping is compound
The Ag distribution diagram of element of lithium ion battery negative material;
Fig. 3 is the silicon-carbon composite lithium ion battery cathode material assembling of the Argent grain doping according to prepared by embodiment 1
The cyclic voltammetry curve of battery;
Fig. 4 is the silicon-carbon composite lithium ion battery cathode material assembling of the Argent grain doping according to prepared by embodiment 1
Cycle performance of the battery under different multiplying.
Specific embodiment
With reference to embodiment and attached drawing, the present invention will be described in detail, but the present invention is not limited merely to this.
Embodiment 1
(1) by commercialized Al-Si alloys (1250 mesh, Al/Si=90wt.%:10wt.%, Huzhou, China) it is dispersed in
Mass fraction is in 20% HCl/water solution, and ultrasound 30 minutes, and magnetic agitation 2h is then centrifuged for, with deionized water and anhydrous
Ethyl alcohol cleaning number 3 times, is placed 6 hours in 80 DEG C of vacuum drying chamber;
(2) ammonium hydroxide of a concentration of 1mol/L of 50ml is added to the AgNO of the prepared 0.01mol/L of 50ml3Aqueous solution
In, silver ammino solution is prepared into, by black powder obtained by step (1) and 15ml absolute ethyl alcohols, 100ml silver ammino solutions, 0.3g PVP
(polyvinylpyrrolidone) mixes and carries out 70 DEG C of stirring in water bath for 24 hours, is finally centrifuged, and cleans, and vacuum drying obtains black
Powder;
(3) black powder obtained by step (2) is laid in quartz boat, is put into tube furnace and carries out chemical vapor deposition,
700 DEG C are warming up to the speed of 5 DEG C/min under Ar protective atmospheres, is passed through C2H2Gas, gas flow 30sccm, subtracts simultaneously
Small Ar flows keep 30min, close C to 40sccm2H2Gas takes out after the decline of Ar protective atmospheres warms to room temperature 25 DEG C, obtains
To powder (the i.e. silicon-carbon composite lithium ion battery cathode material of the Si-C composite material of Argent grain doping, also referred to as Argent grain doping
Material).
(4) using the powder obtained by step (3) as active material, according to active material:Super P (conductive carbon black):CMC
(carboxymethyl cellulose):SBR (binding agent, lithium battery is special, butadiene-styrene rubber) mass ratio=7:1:1:1 ratio prepares slurry,
It is uniformly coated on copper foil as negative material, using CR2025 button cells shell, microporous polyethylene and polyacrylic compound
Film is diaphragm (Celgard2325), metal lithium sheet be filler to electrode, foam nickel sheet, be sequentially placed into battery case respectively,
Inject suitable (1M LiPF6, EC/DMC=1:1 volume ratio) electrolyte, then battery case is compressed in full-automatic sealing machine
Sealing, whole process are below completing in the glove box of 0.1ppm full of Ar and water oxygen content.The battery standing assembled
More than 12h.
In embodiment 1, the material of different preparatory phases is observed using scanning electron microscope (SEM).From figure
It can be seen that, initial Al-Si alloys have smooth surface in 1a, after the pickling of HCl solution, have successfully obtained such as figure
Porous Silicon structures shown in 1b.It is adulterated by further Ag particles, obtains structure as illustrated in figure 1 c, CVD (form sediment by chemical gaseous phase
Product) after the packet carbon of surface, obtain the Si-C composite material of Argent grain doping of the surface as shown in Figure 1 d covered with carbon-coating.Into one
Transmission electron microscope (TEM) analysis is carried out to it for step it can be found that Argent grain has successfully been doped into inside porous silicon (such as really
Fig. 2 a, shown in 2b), and it is 10nm or so (as shown in Figure 2 c), Si, C, tri- kinds of elements of Ag to pass through the carbon layers having thicknesses that CVD is coated
Distribution also very uniformly (such as Fig. 2 d, 2e, shown in 2f).Huge body of this unique structure design for generation during removal lithium embedded
Product variation provides enough inner spaces, and limit external expansion, while internal Argent grain and external carbon-coating are big
Improve the problem of silicium cathode material conductivity is poor greatly.The carbon of the lithium ion battery silicon-carbon composite material of thus obtained Ag doping
Content (mass percent) is that 30%, Ag contents (mass percent) are 3%.
In embodiment 1, to use Argent grain adulterate silicon-carbon composite lithium ion battery cathode material assemble battery into
The test of chemical property is gone.In 0.2A g-1Current density under carried out constant current cycle charge-discharge test.Obtained cycle
Number-capacity curve fig. 3, it is shown that the doping of carbon coating and Argent grain to the capacity and electricity of silicon-carbon cathode
Chemical stability has apparent improvement, is particularly doped with after Argent grain, and compared to simple carbon coated, cycle is steady
Qualitative to be greatly improved, capacity is still up to 988.6mAh g after 200 cycles-1, compared with second recycles
Capacity retention ratio is up to 79.6%.In addition to this, also the high rate performance of assembled battery is tested, as shown in figure 4, with
0.1A g-1、0.2A g-1、0.5A g-1、1A g-1、2A g-1Current density charge-discharge test is carried out to it, show respectively
1112,1078,980,855,765mAhg-1Capacity, when current density is reduced to 0.5A g-1When, it still shows to be up to
1053mAhg-1Specific capacity, illustrate have good high rate performance.Excellent chemical property is attributed to the fact that the stabilization of material structure
Property and high electric conductivity, the problem of greatly improving silicon-carbon composite cathode material cyclical stability and poorly conductive.
Embodiment 2
(1) commercialized Al-Si alloys are dispersed in the HCl/water solution that mass fraction is 20%, ultrasound 30 minutes, and
Magnetic agitation 2h, is then centrifuged for, and with deionized water and washes of absolute alcohol number 3 times, it is small that 6 are placed in 80 DEG C of vacuum drying chamber
When;
(2) ammonium hydroxide of a concentration of 2mol/L of 50ml is added to the AgNO of the prepared 0.02mol/L of 50ml3Aqueous solution
In, silver ammino solution is prepared into, by black powder obtained by step (1) and 15ml absolute ethyl alcohols, 100ml silver ammino solutions, 0.3g PVP
It mixes and carries out 70 DEG C of stirring in water bath for 24 hours, finally centrifuged, cleaned, vacuum drying obtains black powder;
(3) black powder obtained by step (2) is laid in quartz boat, is put into tube furnace and carries out chemical vapor deposition,
700 DEG C are warming up to the speed of 5 DEG C/min under Ar protective atmospheres, is passed through C2H2Gas, gas flow 40sccm, subtracts simultaneously
Small Ar flows keep 30min, close C to 40sccm2H2Gas takes out after the decline of Ar protective atmospheres warms to room temperature 25 DEG C.
(4) using the powder obtained by step (3) as active material, according to active material:super P:CMC:SBR mass ratioes
=7:1:1:1 ratio prepares slurry, is uniformly coated on copper foil as negative material, using CR2025 button cells shell,
Microporous polyethylene and polyacrylic composite membrane are diaphragm (Celgard 2325), metal lithium sheet is to fill out to electrode, foam nickel sheet
Object is filled, is sequentially placed into battery case respectively, injects suitable (1M LiPF6, EC/DMC=1:1 volume ratio) electrolyte, then will
Battery case compresses sealing in full-automatic sealing machine, and whole process is in the gloves that 0.1ppm is below full of Ar and water oxygen content
It is completed in case.More than the battery standing 12h assembled.
In example 2, the carbon content of the lithium ion battery silicon-carbon composite material of Ag doping obtained is 40%, Ag contents
It is 4%.
In example 2, to use Argent grain adulterate silicon-carbon composite lithium ion battery cathode material assemble battery into
The test of chemical property is gone.In 0.2A g-1Current density under carried out constant current cycle charge-discharge test.By 200 times
Capacity is still up to 902.6mAh g after cycle-1, capacity retention ratio is up to 80.2% compared with second recycles.In addition to this, also
The high rate performance of assembled battery is tested, with 0.1A g-1、0.2A g-1、0.5A g-1、1A g-1、2A g-1Electricity
Current density carries out charge-discharge test to it, shows 996,953,876,803,702mAhg respectively-1Capacity, when electric current is close
Degree is reduced to 0.5A g-1When, still show up to 975mAhg-1Specific capacity.
Claims (10)
1. a kind of preparation method of the Si-C composite material of Argent grain doping, which is characterized in that include the following steps:
(1) Al-Si alloying pellets are dispersed in HCl/water solution, dispersion reaction is then centrifuged for, cleans, and vacuum drying obtains
The powder of Porous Silicon structures;
(2) ammonium hydroxide is added to AgNO3In aqueous solution, be prepared into silver ammino solution, by the powder of Porous Silicon structures obtained by step (1),
Ethyl alcohol, silver ammino solution and polyvinylpyrrolidone hybrid reaction, are finally centrifuged, and are cleaned, and vacuum drying obtains black powder
End;
(3) black powder obtained by step (2) is obtained into the silicon of Argent grain doping by chemical vapour deposition reaction deposited carbon layer
Carbon composite.
2. the preparation method of the Si-C composite material of Argent grain doping according to claim 1, which is characterized in that step
(1) in, the mass fraction of the HCl/water solution is 10%~30%.
3. the preparation method of the Si-C composite material of Argent grain doping according to claim 1, which is characterized in that step
(1) in, the condition of the dispersion reaction is:Ultrasound 15 minutes~45 minutes, later magnetic agitation 1h~3h.
4. the preparation method of the Si-C composite material of Argent grain doping according to claim 1, which is characterized in that step
(1) in, the vacuum drying condition is:It is placed 4~8 hours in 70 DEG C~90 DEG C of vacuum drying chamber.
5. the preparation method of the Si-C composite material of Argent grain doping according to claim 1, which is characterized in that step
(2) in, a concentration of 0.5mol/L-3mol/L of the ammonium hydroxide, the AgNO3A concentration of 0.005- of aqueous solution
0.03mol/L。
6. the preparation method of the Si-C composite material of Argent grain doping according to claim 1, which is characterized in that step
(2) in, the hybrid reaction is to react 16h~32h in 60 DEG C~80 DEG C stirring in water bath.
7. the preparation method of the Si-C composite material of Argent grain doping according to claim 1, which is characterized in that step
(3) it in, is specifically included by chemical vapour deposition reaction deposited carbon layer:
Black powder is laid in quartz boat, tube furnace is put into and carries out chemical vapour deposition reaction, with 3 under Ar protective atmospheres
The speed of~8 DEG C/min is warming up to 600 DEG C~800 DEG C, is passed through C2H2Gas, at the same by Ar flows be adjusted to 30sccm~
50sccm keeps 20min~40min, closes C2H2Gas takes out after environment temperature is cooled under Ar protective atmospheres.
8. the Si-C composite material adulterated according to Argent grain prepared by claim 1~7 any one of them preparation method.
9. the Si-C composite material of Argent grain doping according to claim 8 is in lithium ion battery negative material is prepared
Using.
10. application of the Si-C composite material of Argent grain doping according to claim 8 in lithium ion battery is prepared.
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