CN103184465B - A kind of electrochemical preparation method of nm-class silicon carbide material - Google Patents
A kind of electrochemical preparation method of nm-class silicon carbide material Download PDFInfo
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Abstract
The invention provides a kind of electrochemical method preparing silicon carbide nanometer line, particle.Its characteristic is: with Si oxide SiO
xthe precursor composite porous material of (0 < X≤2) and carbon is negative electrode, anode is set, is placed in the ionogen comprising metallic compound fused salt, applies voltage between a cathode and an anode, control reaction conditions, at silicon carbide nanometer line, the particle of negative electrode.Its advantage be pollution-free, raw material is easy to get, equipment is cheap, the preparation temperature that is easy to continuous seepage, reduces silicon carbide simultaneously, the production for silicon carbide explores a new way.
Description
Technical field
The present invention relates to a kind of method of electrochemical production silicon carbide nanometer line, particle.
Background technology
The energy, information and material are three large pillars of modern name of the country economy.The wherein basis of material all trades and professions especially.SiC as structural ceramic material, the advantage such as there is hardness high (between corundum and diamond), hot strength is large, creep-resistant property good, stable chemical performance, thermal conductivity are high, thermal expansivity is little, wear resisting property is good.With the parts that SiC micro mist obtains, there is more excellent high temperature strength, wear resistance, be widely used in the industrial circles such as Aeronautics and Astronautics, automobile, machinery, petrochemical industry as structured material.Because silicon carbide micro-powder and many metals and nonmetal oxide have good chemical compatibility, for the preparation of metal matrix, ceramic base and polymer matrix composite, show excellent performance.SiC nanoparticle can launch stronger blue light under certain condition, when its size little to a certain extent time, the transformation of indirect band gap to direct band gap will be there is, once formation direct band gap, then generation significantly changes by its luminosity factor, can be used for preparing superhigh brightness LED and short-wavelength semiconductor laser apparatus.
Whisker reinforcing and toughening is considered to the effective ways solving material at high temperature toughness, and compared with continuous fibre reinforcing and toughening, crystal whisker toughened technique is more easy.Therefore, the demand of various advanced composite material to whisker constantly increases.SiC whisker has low density, high-melting-point, high strength, high-modulus, thermal expansion rate and the good characteristic such as corrosion-resistant.As the excellent toughener of the advanced composite materials such as metal matrix, ceramic base and superpolymer base, the various fields such as machinery, electronics, chemical industry, the energy, aerospace and environmental protection are widely used in.
The preparation method of SiC nanowire mainly contains two kinds, and one is solid material method, namely utilizes carrier gas by carbon containing and siliceous mixing material, forms the synthetic method of SiC in the space separated with reaction material.Bai Chungen etc., at 1400 ~ 1600 DEG C, use Fe, H respectively
3bO
3, NaCl tri-kinds contacts the SiC nanowire length that obtains of matchmaker and reaches 200 μm; Non-metallic catalyst and the metal composite catalyst such as Wang Qibao, raw materials used middle SiO
2content is 57.5%, in 1650 DEG C of synthesizing β-SiC nano wires, and production rate > 30%.Solid-phase synthesis has cheaper starting materials; raw material sources are wide; method is simple; the advantages such as easy handling; be the main method commercially produced, but solid phase method need to grow under the effect of catalyzer and under the protection of mixed gas mostly, more containing impurity such as catalyzer in whisker; purity is not high, and the productive rate of whisker is not high.Another kind is gas-phase reaction method, namely reacts with carbonaceous gas and silicon-containing gas; Or decompose a kind of carbon containing, silicon compound organic gas synthesis SiC nanowire method.Other metals of composite catalyst Cu compound such as Ikeyama, SiCl4 and hydrocarbon reaction obtain the pure SiC nanowire that diameter is greater than 1 μm.Otoishi Shinji etc. are obtained containing the w/o type milk sap of Polycarbosilane with the carbon fiber pulverized, and obtain porous insert thus further, at 1273 ~ 1623 DEG C of these porous inseries of thermal treatment in Ar atmosphere, have β-SiCw to generate on the surface of porous insert and inwall.But it is all not bery desirable as there is the aspect problem such as environmental pollution, Preparation equipment complexity to prepare SiC whisker by gas-phase reaction.
The preparation method of SiC nano particle has a lot, comprises chemical Vapor deposition process (CVD), Laser induced diffusion (LIVCD), plasma (orifice) gas phase synthesi (PCVD method) and laser ablation method etc.But these methods or need special equipment, or complex process, cause manufacturing cost to improve.
Although the preparation method of SiC nanowire, particle has a lot, employing electrochemical method prepares silicon carbide nanometer line, the method for particle yet there are no pertinent literature report.
Summary of the invention
The object of this invention is to provide a kind of pollution-free, raw material is easy to get, equipment is cheap, be easy to continuous product, reduce the SiC nanowire of preparation temperature, the electrochemical method of particle simultaneously.
According to the present invention, one or more in SiC nanowire, SiC nano particle are prepared in employing fused salt electrolysis, it is characterized in that: by Si oxide/carbon composite porous material as negative electrode, anode is set, be placed in the ionogen comprising metallic compound fused salt, apply voltage between a cathode and an anode, carry out electrolysis, obtain one or more in SiC nanowire, SiC nano particle at negative electrode.
Si oxide in the present invention/carbon composite porous material is mixed with the precursor of carbon by Si oxide, is hot pressed into porous material, or mold pressing or mould fill with shaping, then sinter porous material into.
Described Si oxide mixes with the precursor of carbon, and wherein the mol ratio of Siliciumatom and carbon atom is 0.01 ~ 5.
Si oxide/the carbon composite prepared in the present invention is mixed with the precursor of carbon by Si oxide, wherein Si oxide-SiO
x, 0 < X≤2.
The precursor of described carbon comprises: polyvinyl alcohol, furfuryl alcohol, wood sugar, styrene-butadiene rubber(SBR) breast, carboxymethyl cellulose, polymethacrylate, tetrafluoroethylene, polyvinylidene difluoride (PVDF), poly-divinylbenzene, polyacrylonitrile, resol, phenolic resin, epoxy resin, glucose, sucrose, fructose, Mierocrystalline cellulose, starch or pitch etc.
The shape of described silicon oxide powder be spherical, class spherical in one or more, the median size of silicon oxide powder is less than 100nm.
Described Si oxide mixes with the precursor of carbon, dissolved in a solvent by the precursor of carbon, wherein solvent can be deionized water or organic solvent (as ethanol, acetone etc.), the consumption of solvent is 5 to 20 times of the quality of the presoma of carbon, form the solution of the precursor of carbon, Si oxide is dispersed in the solution of the precursor of carbon.
Described Si oxide is dispersed in the solution of the precursor of carbon, it is characterized in that, the dispersing method of employing comprises the method that ultrasonic disperse, high-shear emulsifying homogenizer etc. are easy to nanoparticulate dispersed.
The precursor mixing solutions of described Si oxide and carbon is dry, it is characterized in that, the rate of dryings such as employing microwave drying, lyophilize, spraying dry are fast, the drying means of uniform drying.
In the compound porous block materials process of described sinterable silicon oxide/carbon, the temperature of sintering 600 ~ 1500 DEG C, the atmosphere of sintering is argon gas, and the time of sintering is 1h-2h.
Described Si oxide/carbon cathode is carbonization under 600 ~ 1500 DEG C of argon gas atmosphere by Si oxide and carbon precursor mixture, sinter a step completes.
Described Si oxide/carbon composite porous material, is characterized in that: carbon is coated on the surface of silicon oxide particles.
Described using the cathode collector volume recombination of the compound porous block materials of Si oxide/carbon and conduction as negative electrode, it is characterized in that: porous blocks material becomes negative electrode with conductive cathode collector by mechanical package.
One or more ionogen of ionogen middle finger of described metal-containing compound fused salt.
Apply voltage between a cathode and an anode lower than electrolytical theoretical decomposition voltage.
Electrolysis is carried out at the temperature of 500-1000 DEG C.
The mean diameter of the nanometer powder of described SiC is less than 100 nanometers.
The nanowire diameter of described SiC is less than 100 nanometers.
Tool of the present invention has the following advantages:
The carbon precursor adopted not only provides carbon but also be coated on nano-silica surface as binding agent, is conducive to shaping; Carbonization, sintering once complete, and nano silicon is dispersed in carbon base body uniformly simultaneously, and compared with material prepared by the method for adulterating with micro mist, the matrix material prepared by present patent application is more even.Silicon carbide nanometer line, nanometer silicon carbide particle are prepared in fused salt electrolysis, reduce the preparation temperature of SiC; Abundant raw material source simultaneously, raw material and the equal environmentally safe of preparation process, the nano wire of preparation, nano particle morphology controllable, uniform particle diameter; Device simple, low price; Raw material and product add all in solid form or shift out and be easy to continuous product.
Accompanying drawing explanation
The SiC nanowire of accompanying drawing 1 embodiment 1, particle amplify the SEM figure of 50000 times;
The SiC nano particle of accompanying drawing 2 embodiment 5 amplifies the SEM figure of 50000 times;
The SiC nano material of accompanying drawing 3 embodiment 9 amplifies the SEM figure of 50000 times;
The SiC nano material of accompanying drawing 4 embodiment 10 amplifies the SEM figure of 50000 times;
The SiC nanowire of accompanying drawing 5 embodiment 11 amplifies the SEM figure of 50000 times;
Embodiment
Below will present invention is described further combined with drawings and Examples.These describe just in order to the present invention will be described further, instead of limit the invention.
Embodiment 1
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 0.8: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 900 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 900 DEG C, constant-potential electrolysis is carried out by potentiostat control voltage, bath voltage is 3.0V, and electrolysis time is 8h, is rinsed successively by electrolysate after electrolysis completes with deionized water immersion, dehydrated alcohol, vacuum-drying, obtain product as shown in Figure 1, obtain the mixture of nano particle and a small amount of nano wire, SiC nanowire diameter is about 50nm, be about 500nm, SiC nano-particle diameter is 10-30nm.
Embodiment 2
Nano silicon and the sucrose of certain mass is taken by silicon-carbon mol ratio 0.8: 1, by sucrose dissolved in deionized water, nano silicon is dispersed in the solution of sucrose, drying, obtains the nano grade silica particles of Surface coating sucrose, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 900 DEG C of constant temperature 1h, by the C/SiO of sinter molding
2(sucrose carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 900 DEG C, carry out constant-potential electrolysis by potentiostat control voltage, bath voltage is 3.0V, and electrolysis time is 6h, after electrolysis completes, electrolysate is rinsed with deionized water immersion, dehydrated alcohol successively, vacuum-drying, obtains product, and SiC nano-particle diameter is 30-50nm.
Embodiment 3
Nano silicon and the polyvinyl alcohol of certain mass is taken by silicon-carbon mol ratio 0.8: 1, by polyvinyl alcohol dissolution in dehydrated alcohol, nano silicon is dispersed in polyvinyl alcohol solution, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 900 DEG C of constant temperature 1h, by the C/SiO of sinter molding
2(polyvinyl alcohol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 900 DEG C, carry out constant-potential electrolysis by potentiostat control voltage, bath voltage is 2.6V, and electrolysis time is 10h, after electrolysis completes, electrolysate is rinsed with deionized water immersion, dehydrated alcohol successively, vacuum-drying, obtains nano particle, and SiC nano-particle diameter is 20-50nm.
Embodiment 4
Nano silicon and the polyvinylidene difluoride (PVDF) of certain mass is taken by silicon-carbon mol ratio 0.8: 1, polyvinylidene difluoride (PVDF) is dissolved in N-Methyl pyrrolidone, nano silicon is dispersed in the N-Methyl pyrrolidone solution of polyvinylidene difluoride (PVDF), drying, obtains the nano grade silica particles of Surface coating polyvinylidene difluoride (PVDF), is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 900 DEG C of constant temperature 1h, by the C/SiO of sinter molding
2(polyvinylidene fluoride olefinic carbon/silicon-dioxide small pieces) and conductive cathode collector compound, as negative electrode, using graphite rod as anode, take mass ratio as the melting CaCl of 6: 4
2be ionogen with NaCl, in the environment of argon gas, temperature is 600 DEG C, carry out constant-potential electrolysis by potentiostat control voltage, bath voltage is 3.0V, and electrolysis time is 10h, after electrolysis completes, electrolysate is rinsed with deionized water immersion, dehydrated alcohol successively, vacuum-drying, obtains product, and SiC nano-particle diameter is 20-50nm.
Embodiment 5
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 1: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 900 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound, as negative electrode, using graphite rod as anode, take mass ratio as the melting CaCl of 8: 2
2be ionogen with NaCl, in the environment of argon gas, temperature is 700 DEG C, carry out constant-potential electrolysis by potentiostat control voltage, bath voltage is 3.0V, and electrolysis time is 12h, after electrolysis completes, electrolysate is rinsed with deionized water immersion, dehydrated alcohol successively, vacuum-drying, obtains product as shown in Figure 2, and obtaining nano-particle diameter is 10-50nm.
Embodiment 6
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 1: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 1000 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 950 DEG C, constant-potential electrolysis is carried out by potentiostat control voltage, bath voltage is 3.0V, and electrolysis time is 8h, is rinsed successively by electrolysate after electrolysis completes with deionized water immersion, dehydrated alcohol, vacuum-drying, obtaining nano-particle diameter is 10-50nm.
Embodiment 7
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 1: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 1100 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 1000 DEG C, constant-potential electrolysis is carried out by potentiostat control voltage, bath voltage is 2.0V, and electrolysis time is 8h, is rinsed successively by electrolysate after electrolysis completes with deionized water immersion, dehydrated alcohol, vacuum-drying, obtaining nano-particle diameter is 10-50nm.
Embodiment 8
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 1: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 1200 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 900 DEG C, carry out constant-potential electrolysis by potentiostat control voltage, bath voltage is 2.8V, and electrolysis time is 8h, after electrolysis completes, electrolysate is rinsed with deionized water immersion, dehydrated alcohol successively, vacuum-drying, obtains the mixture of nano particle and a small amount of nano wire, and SiC nano-particle diameter is 10-50nm.
Embodiment 9
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 1: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 1300 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 950 DEG C, carries out constant-potential electrolysis by potentiostat control voltage, bath voltage is 2.4V, electrolysis time is 8h, is rinsed successively by electrolysate, vacuum-drying after electrolysis completes with deionized water immersion, dehydrated alcohol, obtain product as shown in Figure 3, obtain the mixture of nano wire and nano particle, SiC nanowire diameter is 20-100nm, is about several micron.
Embodiment 10
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 1.5: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 1300 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 900 DEG C, carries out constant-potential electrolysis by potentiostat control voltage, and bath voltage is 2.8V, electrolysis time is 12h, rinsed with deionized water immersion, dehydrated alcohol successively by electrolysate after electrolysis completes, vacuum-drying, obtains product as shown in Figure 4, obtaining diameter is 20-100nm, is about several microns bending and ganoid SiC nanowire.
Embodiment 11
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 2: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 1300 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 1000 DEG C, carries out constant-potential electrolysis by potentiostat control voltage, and bath voltage is 3.0V, electrolysis time is 14h, rinsed with deionized water immersion, dehydrated alcohol successively by electrolysate after electrolysis completes, vacuum-drying, obtains product as shown in Figure 5, obtaining diameter is 20-100nm, is about the ganoid SiC nanowire of several microns.
Embodiment 12
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 3: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 1300 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 800 DEG C, carry out constant-potential electrolysis by potentiostat control voltage, bath voltage is 2.0V, and electrolysis time is 17h, after electrolysis completes, electrolysate is rinsed with deionized water immersion, dehydrated alcohol successively, vacuum-drying, obtaining diameter is 20-100nm, is about the SiC nanowire of several microns.
Embodiment 13
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 4: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 1300 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 850 DEG C, carries out constant-potential electrolysis by potentiostat control voltage, and bath voltage is 2.0V, electrolysis time is 20h, rinsed with deionized water immersion, dehydrated alcohol successively by electrolysate after electrolysis completes, vacuum-drying, obtains product as shown in Figure 3, obtaining diameter is 20-100nm, is about the SiC nanowire of 1 micron.
Embodiment 14
Nano silicon and the resol of certain mass is taken by silicon-carbon mol ratio 5: 1, by phenol formaldehyde resin dissolves in dehydrated alcohol, nano silicon is dispersed in the ethanol solution of resol, drying, obtains the nano grade silica particles of Surface coating resol, is compressed to thickness is about 2mm by mechanical pressure at 8MPa, internal diameter is about 10mm, external diameter is about 25mm, under an argon atmosphere 1300 DEG C of constant temperature 1h, by the PFC/SiO of sinter molding
2(resol carbon/silicon-dioxide small pieces) and conductive cathode collector compound as negative electrode, using graphite rod as anode, with melting CaCl
2for ionogen, in the environment of argon gas, temperature is 900 DEG C, carry out constant-potential electrolysis by potentiostat control voltage, bath voltage is 2.0V, and electrolysis time is 24h, after electrolysis completes, electrolysate is rinsed with deionized water immersion, dehydrated alcohol successively, vacuum-drying, obtaining diameter is 20-100nm, the SiC nanowire of long 500nm-1000nm micron.
Claims (13)
1. the electrochemical preparation method of a nm-class silicon carbide material, it is characterized in that: using the cathode collector volume recombination of the compound porous block materials of Si oxide/carbon and conduction as negative electrode, anode is set, be placed in the ionogen comprising metallic compound fused salt, apply the voltage lower than electrolyte decomposition voltage between a cathode and an anode, under argon gas atmosphere, control electrolysis time, obtain the electrolysate of one or more in the nano particle of the nano wire of SiC, SiC at negative electrode; Wherein, the compound porous block materials of described Si oxide/carbon is mixed with the precursor of carbon by silicon oxide powder, and hot repressing, mold pressing or mould fill with shaping porous blocks material, then carries out sintering the compound porous block materials of Si oxide/carbon into; In the compound porous block materials of Si oxide/carbon, the mol ratio of Siliciumatom and carbon atom is 0.01 ~ 5; Described Si oxide is SiO
x, 0 < X≤2.
2. the electrochemical preparation method of nm-class silicon carbide material according to claim 1, it is characterized in that, the precursor of described carbon is one or more in polyvinyl alcohol, furfuryl alcohol, wood sugar, styrene-butadiene rubber(SBR) breast, carboxymethyl cellulose, polymethacrylate, tetrafluoroethylene, polyvinylidene difluoride (PVDF), poly-divinylbenzene, polyacrylonitrile, resol, phenolic resin, epoxy resin, glucose, sucrose, fructose, Mierocrystalline cellulose, starch, pitch.
3. the electrochemical preparation method of nm-class silicon carbide material according to claim 1 and 2, it is characterized in that, the precursor mixing process of described silicon oxide powder and carbon is, the precursor of carbon is dissolved in a solvent, form the solution of the precursor of carbon, then Si oxide is dispersed in the solution of the precursor of carbon; Again by dry for the precursor mixing solutions of described Si oxide and carbon, obtain the precursor mixed powder of dried Si oxide and carbon.
4. the electrochemical preparation method of nm-class silicon carbide material according to claim 3, is characterized in that, the shape of described silicon oxide powder be spherical, class spherical in one or more, the median size of silicon oxide powder is less than 100nm.
5. the electrochemical preparation method of nm-class silicon carbide material according to claim 3, is characterized in that, the dispersing method be dispersed in by silicon oxide powder in the solution of the precursor of carbon is ultrasonic disperse or the method using the dispersion of high-shear emulsifying homogenizer.
6. the electrochemical preparation method of nm-class silicon carbide material according to claim 3, is characterized in that, the drying means of the precursor mixing solutions of Si oxide and carbon is method for microwave drying, freeze-drying method or spray drying process.
7. the electrochemical preparation method of nm-class silicon carbide material according to claim 1, it is characterized in that, in the compound porous block materials process of described sinterable silicon oxide/carbon, the temperature of sintering 600 ~ 1500 DEG C, the atmosphere of sintering is argon gas, and the time of sintering is 1h-2h.
8. the electrochemical preparation method of nm-class silicon carbide material according to claim 6, is characterized in that, the particle that the surface that the compound porous block materials of Si oxide/carbon obtained after sintering is coated on silicon oxide particles by carbon is formed formed.
9. the electrochemical preparation method of nm-class silicon carbide material according to claim 1, is characterized in that, the described complex sintered step of the cathode current collector sintering Si oxide/carbon compound porous block materials process and conduction into completes.
10. the electrochemical preparation method of nm-class silicon carbide material according to claim 1, is characterized in that, the described ionogen comprising metallic compound fused salt refers to one or more ionogen.
The electrochemical preparation method of 11. nm-class silicon carbide materials according to claim 1, is characterized in that, electrolysis is carried out at the temperature of 500-1000 DEG C.
12. want the electrochemical preparation method of the nm-class silicon carbide material described in 1 according to right, it is characterized in that, the mean diameter of the nano wire of described SiC, the nano particle of SiC is less than 100 nanometers.
The electrochemical preparation method of 13. nm-class silicon carbide materials according to claim 1, is characterized in that, the nanowire diameter of described SiC is less than 100 nanometers.
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