CN110854359B - Silicon/carbon composite material and preparation method thereof - Google Patents

Silicon/carbon composite material and preparation method thereof Download PDF

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CN110854359B
CN110854359B CN201810945783.9A CN201810945783A CN110854359B CN 110854359 B CN110854359 B CN 110854359B CN 201810945783 A CN201810945783 A CN 201810945783A CN 110854359 B CN110854359 B CN 110854359B
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silicon
composite material
carbon composite
carbon
carbonate
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CN110854359A (en
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包志豪
黄曦
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Tongji University
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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
    • 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
    • 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
    • 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
    • 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 relates to a silicon/carbon composite material and a preparation method thereof, belonging to the technical field of electrode materials of lithium ion batteries. The process comprises the steps of reacting silicon dioxide raw materials with metal magnesium to generate a product containing magnesium silicide, reacting with carbonate to obtain a product, removing impurities by acid washing, and drying to obtain the silicon/carbon composite material. The invention has the advantages of rich sources of silicon dioxide raw materials, simple process and convenient large-scale production. Compared with the traditional magnesiothermic reduction reaction, the preparation method is easier to obtain the composite material of the silicon nano-particles and carbon with small size (less than 80nm), shows excellent electrochemical performance as the cathode material of the lithium ion battery, and has wide application value.

Description

Silicon/carbon composite material and preparation method thereof
Technical Field
The invention relates to a silicon/carbon composite material and a preparation method thereof, belonging to the technical field of electrode materials of lithium ion batteries.
Background
With the rapid development of portable devices and electric vehicles, the worldwide demand for lithium ion secondary batteries with high specific capacity, long cycle life and high energy density is increasingly urgent. The electrode material is one of the most critical components. In terms of the negative electrode material, the graphite carbon negative electrode material is mainly used, but the capacity is low (372mAh/g), and the lithium intercalation potential is close to that of metallic lithium, so that the lithium precipitation is easy to occur during the rapid charging, and the safety problem is caused. Among other various non-carbon anode materials, silicon has received extensive attention from researchers at the highest theoretical capacity (4200mAh/g) and high safety among existing anode materials.
However, the huge volume expansion (> 300%) of the silicon negative electrode material in the circulation process is easy to cause pulverization of the material, loss of contact with a current collector, poor conductivity of the silicon negative electrode material, and the like, so that the cycle reversible capacity of the battery is reduced and the rate capability of an electrode is improved. In order to overcome the above problems, one of the currently effective methods is to make the material into a nano-size, particularly, to reduce the nano-size of the material to 80nm or less, so that the silicon nanoparticles are not easily broken when used as a negative electrode material, and the utilization rate of the active material is high. However, nano-silicon particles, particularly those having a diameter of less than 80nm, are difficult to prepare on a large scale, thus limiting their wide application.
Document 1, Li, Xuegen, Yuanq He, and Mark T. Swihart, "Surface function activation of silicon nanoparticles produced by laser-driven by HF-HNO 3 etching."Langmuir 20.11(2004):4720-4727, silicon particles with a size of less than 100 nm were prepared by laser pyrolysis of silane, but the yield was 200 mg/hour, which is not easy to scale up. Document 2, Yu, y., Gu, l., Zhu, c., Tsukimoto, s., van Aken, p.a.,&maier, j. (2010) Reversible Storage of Lithium in Silver-Coated Three-Dimensional macromolecular silicon advanced Materials,22(20), 2247-.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a silicon/carbon composite material and a preparation method thereof, the technical process is simple, and a two-step method is adopted to prepare silicon nanoparticles and a carbon composite, namely, silicon dioxide is reacted to obtain a mixture containing magnesium silicide, the generated magnesium silicide is reacted with calcium carbonate, the obtained product is subjected to acid cleaning to remove impurities, and the silicon nanoparticles and the carbon composite is obtained after cleaning and drying. In the process of the traditional magnesiothermic reduction method, magnesium silicide can be generated as a byproduct, and the magnesium silicide has strong reducibility, so that the reaction product magnesium silicide is further reacted with carbonate, and in the generation process, because the magnesium silicide is generated and carbon is synchronously generated, the diffusion of silicon is blocked, and the generated silicon particles are small. Meanwhile, by utilizing the silicon dioxide-containing materials such as diatomite, white carbon black, rice hull ash, glass fiber waste, sand, sandy soil and powder after glass ball milling, the advantages of easy obtainment of the materials and capability of changing waste into valuable are brought.
In order to achieve the above object, the present invention adopts the following technical solutions:
the silicon dioxide raw material and magnesium powder react to generate a mixture containing magnesium silicide, the mixture reacts with carbonate, impurities are removed through acid washing, and the mixture is dried to generate the carbon and silicon composite material. The method specifically comprises the following steps:
(1) mixing a silicon dioxide raw material with magnesium powder, heating and reacting under an inert atmosphere, and cooling to obtain a mixture containing magnesium silicide;
(2) adding carbonate into the mixture prepared in the step (1), uniformly mixing, heating and reacting under an inert atmosphere, and cooling to obtain a reaction product;
(3) and (3) after the reaction in the step (2) is finished, respectively soaking the reaction product into hydrochloric acid and hydrofluoric acid solution to remove impurities, and then separating and drying to prepare the silicon/carbon composite material.
Further, the raw material of the silicon dioxide in the step (1) is one or more of diatomite, white carbon black, rice hull ash, glass fiber waste, sand, sandy soil and powder of ball-milled glass.
Further, the inert atmosphere in the step (1) and the step (2) is pure argon gas or hydrogen-argon gas mixture.
Further, the molar ratio of the silicon dioxide raw material to the magnesium powder in the step (1) is 1: 2.05-1: 6.
further, the heating reaction conditions in the steps (1) and (2) are 500-900 ℃, and the reaction is carried out for 2-10 hours at constant temperature.
Further, the carbonate in the step (2) is one or a mixture of calcium carbonate and magnesium carbonate.
Further, the molar ratio of the carbonate in the step (2) to the silicon dioxide in the step (1) is 0.05: 1-2: 1.
further, the primary particle size of the silicon in the silicon/carbon composite is less than 80 nanometers.
The silicon/carbon composite material prepared by the invention contains silicon nano-particles; the particle size of the silicon particles in the whole silicon/carbon composite material is below 80 nm.
Further, the silicon/carbon composite material prepared by the method is used as a lithium ion battery cathode material, is uniformly mixed with a commercially available Super-P conductive agent and a sodium alginate binder according to a mass ratio of 60:20:20, is coated on a current collector copper foil, is dried in a vacuum box at 60 ℃, is prepared into an electrode plate with the diameter of 1.2cm by a tablet press, and is dried in vacuum at 75 ℃ for 12 hours. Using a metal lithium sheet as a counter electrode, adopting Celgard 2400 as a diaphragm and 1mol/L LiPF 6 + EC + DEC (EC: DEC volume ratio 1:1) containing 10 vol% FEC as electrolyte in a glove box (H) 2 O<1ppm,O 2 <1ppm) is assembled into an experimental battery, an electrochemical performance test is carried out by adopting a blue CT2001A type battery tester, the charge-discharge cut-off voltage is 0.005-1V (vs Li +/Li), the test temperature is 25 ℃, and the test result shows that the first cycle capacity of the composite material can reach 3937.1mAh g -1 The first coulombic efficiency is 78.8 percent, and the material has excellent rate capability of 0.5,1,1.5,2,2.5,3,4A g -1 The specific capacity respectively reaches 3047,2873,2733,2592,2460,2329,2068mAh g under the current density -1 At 1A g -1 The specific capacity of the current density can still reach 1842mAh g after the circulation for 300 weeks -1 。
Compared with the prior art, the invention has the following characteristics:
1) when the silicon/carbon composite material is prepared, compared with a one-step magnesiothermic reduction method, the obtained silicon particles are smaller. Because the silicon material is generated and the carbon material is generated at the same time, the silicon and the carbon material are compounded more uniformly.
2) The adopted silicon dioxide raw materials are low in cost and convenient for large-scale production, the silicon dioxide raw materials have high specific area and limit the growth of silicon particles, and the obtained silicon/carbon composite material used as the lithium ion battery cathode material shows excellent electrochemical cycle stability and rate capability.
Drawings
FIG. 1 is a schematic view of a process flow of a silicon/carbon composite material prepared by the method of the present invention.
FIG. 2 is an XRD of a silicon/carbon composite material prepared according to example 1 of the present invention; wherein the abscissa is angle in degrees (deg.), and the ordinate is intensity in arbitrary units (a.u deg.);
FIG. 3 is a scanning electron microscope spectrum of the silicon/carbon composite material prepared in example 1 of the present invention;
FIG. 4 is a TEM spectrum of the silicon/carbon composite material prepared in example 1 of the present invention, wherein the left and right images are low-magnification and high-magnification TEM images, respectively;
fig. 5 is a graph showing electrochemical cycle performance and coulombic efficiency of the silicon/carbon composite material prepared in example 1 of the present invention.The horizontal coordinate is the cycle number of weeks, and the unit is week; the left ordinate is the specific discharge capacity, in units: milliampere hour gram -1 (mAh g -1 ) The right ordinate is coulombic efficiency in units: percentage (%).
Fig. 6 is an electrochemical rate performance curve of the silicon/carbon composite material prepared in example 1 of the present invention. The horizontal coordinate is the cycle number of weeks, and the unit is week; the left ordinate is the specific discharge capacity, in units: milliampere hour gram -1 (mAh g -1 ) The right ordinate is coulombic efficiency in units: percentage (%).
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1:
the silicon/carbon composite material prepared in this embodiment specifically includes the following steps, as shown in fig. 1:
(1) mixing diatomite and magnesium powder, heating to 700 ℃ under inert atmosphere, preserving heat for 5 hours, and cooling to obtain a mixture containing magnesium silicide.
(2) Adding calcium carbonate into the mixture prepared in the step (1), uniformly mixing, heating to 700 ℃ in an inert atmosphere, preserving heat for 5 hours, and cooling to obtain a reaction product.
(3) And (3) adding sufficient 3mol/l hydrochloric acid and 5 wt% hydrofluoric acid into the reaction product obtained in the step (2), and cleaning and drying to obtain the silicon/carbon composite material.
The mol ratio of the silicon dioxide to the magnesium powder in the diatomite obtained in the step (1) is 1: 4.
The molar ratio of the calcium carbonate in the step (2) to the silicon dioxide in the diatomite in the step (1) is 1: 4.
The inert gas in the step (1) and the step (2) is pure argon or a mixed gas of argon (95 v%) and hydrogen (5 v%).
Fig. 2 shows XRD of the silicon/carbon composite material prepared in this example, which indicates that the silicon/carbon composite material prepared in this example contains silicon nanoparticles;
fig. 3 is a scanning electron microscope image of the silicon/carbon composite material prepared in this example, which shows that the prepared silicon/carbon composite material maintains a good three-dimensional porous structure.
Fig. 4 is a transmission electron micrograph of the silicon/carbon composite material prepared in this example. Fig. 4a is a low resolution transmission electron micrograph, which also confirms that the silicon nanoparticles in the obtained silicon/carbon composite material are distributed on the carbon material, and the distribution is relatively uniform. FIG. 4b is a higher resolution electron micrograph. The distance of the stripes was 0.31nm, demonstrating the presence of silicon particles, and the size of the silicon particles was less than 80 nm.
As shown in FIG. 5 and FIG. 6, when the silicon/carbon composite material prepared in this example is used as the negative electrode material of a lithium ion battery, the specific capacity is still as high as 2873g at a current density of 1A/g -1 After 300 times of circulation, the specific capacity can be kept at 1842mAh g -1 The above. Under the high current density of 4A/g, the specific capacity is as high as 2068mAh g -1 。
Example 2:
the silicon/carbon composite material prepared in the embodiment specifically includes the following steps:
(1) mixing glass fiber and magnesium powder, heating to 500 ℃ in an inert atmosphere, preserving heat for 12 hours, and cooling to obtain a mixture containing magnesium silicide.
(2) Adding calcium carbonate into the mixture prepared in the step (1), uniformly mixing, heating to 900 ℃ in an inert atmosphere, preserving heat for 2 hours, and cooling to obtain a reaction product.
(3) And (3) adding sufficient 3mol/l hydrochloric acid and 5 wt% hydrofluoric acid into the reaction product obtained in the step (2), and cleaning and drying to obtain the silicon/carbon composite material.
The molar ratio of the silicon dioxide to the magnesium powder in the glass fiber in the step (1) is 1: 2.05.
The molar ratio of the calcium carbonate in the step (2) to the silica in the glass fiber in the step (1) is 0.05: 1.
The inert gas in the step (1) and the step (2) is pure argon or a mixed gas of argon (95 v%) and hydrogen (5 v%).
Example 3:
the silicon/carbon composite material prepared in the embodiment specifically includes the following steps:
(1) mixing white carbon black and magnesium powder, heating to 600 ℃ in an inert atmosphere, preserving heat for 6 hours, and cooling to obtain a mixture containing magnesium silicide.
(2) Adding calcium carbonate into the mixture prepared in the step (1), uniformly mixing, heating to 600 ℃ in an inert atmosphere, preserving heat for 12 hours, and cooling to obtain a reaction product.
(3) And (3) adding sufficient 3mol/l hydrochloric acid and 5 wt% hydrofluoric acid into the reaction product obtained in the step (2), and cleaning and drying to obtain the silicon/carbon composite material.
The molar ratio of the silicon dioxide to the magnesium powder in the white carbon black in the step (1) is 1: 6.
The molar ratio of the calcium carbonate in the step (2) to the silica in the white carbon black in the step (1) is 2: 1.
the inert gas in the step (1) and the step (2) is pure argon or a mixed gas of argon (95 v%) and hydrogen (5 v%).
Example 4:
the silicon/carbon composite material prepared in this embodiment specifically includes the following steps:
(1) mixing the rice hull ash and magnesium powder, heating to 500 ℃ in an inert atmosphere, preserving heat for 12 hours, and cooling to obtain a mixture containing magnesium silicide.
(2) Adding calcium carbonate into the mixture prepared in the step (1), uniformly mixing, heating to 900 ℃ in an inert atmosphere, preserving heat for 2 hours, and cooling to obtain a reaction product.
(3) And (3) adding sufficient 3mol/l hydrochloric acid and 5 wt% hydrofluoric acid into the reaction product obtained in the step (2), and cleaning and drying to obtain the silicon/carbon composite material.
The molar ratio of the silicon dioxide to the magnesium powder in the rice hull ash in the step (1) is 1: 4.
The molar ratio of the calcium carbonate in the step (2) to the silicon dioxide in the rice hull ash in the step (1) is 2: 1.
Example 5:
the silicon/carbon composite material prepared in the embodiment specifically includes the following steps:
(1) mixing the fiber solid waste with magnesium powder, heating to 800 ℃ in an inert atmosphere, preserving heat for 4 hours, and cooling to obtain a mixture containing magnesium silicide.
(2) And (2) adding calcium carbonate into the mixture prepared in the step (1), uniformly mixing, heating to 800 ℃ in an inert atmosphere, preserving heat for 4 hours, and cooling to obtain a reaction product.
(3) And (3) adding sufficient 3mol/l hydrochloric acid and 5 wt% hydrofluoric acid into the reaction product obtained in the step (2), and cleaning and drying to obtain the silicon/carbon composite material.
The molar ratio of the silicon dioxide to the magnesium powder in the optical fiber in the step (1) is 1: 4.
The molar ratio of the calcium carbonate in the step (2) to the silica in the optical fiber in the step (1) is 2: 1.
Example 6:
the silicon/carbon composite material prepared in the embodiment specifically includes the following steps:
(1) mixing the powder obtained after ball milling of glass with magnesium powder, heating to 900 ℃ in an inert atmosphere, preserving heat for 2 hours, and cooling to obtain a mixture containing magnesium silicide.
(2) Adding calcium carbonate into the mixture prepared in the step (1), uniformly mixing, heating to 900 ℃ in an inert atmosphere, preserving heat for 2 hours, and cooling to obtain a reaction product.
(3) And (3) adding sufficient 3mol/l hydrochloric acid and 5 wt% hydrofluoric acid into the reaction product obtained in the step (2), and cleaning and drying to obtain the silicon/carbon composite material.
The mol ratio of silicon dioxide to magnesium powder contained in the powder obtained after the glass is ball-milled in the step (1) is 1: 4.
The molar ratio of the calcium carbonate in the step (2) to the silicon dioxide in the powder obtained after the glass is ball-milled in the step (1) is 2: 1.
Example 7:
the silicon/carbon composite material prepared in this embodiment specifically includes the following steps, as shown in fig. 1:
(1) mixing sand and magnesium powder, heating to 700 ℃ in an inert atmosphere, preserving heat for 5 hours, and cooling to obtain a mixture containing magnesium silicide.
(2) Adding magnesium carbonate into the mixture prepared in the step (1), uniformly mixing, heating to 700 ℃ in an inert atmosphere, preserving heat for 5 hours, and cooling to obtain a reaction product.
(3) And (3) adding sufficient 3mol/l hydrochloric acid and 5 wt% hydrofluoric acid into the reaction product obtained in the step (2), and cleaning and drying to obtain the silicon/carbon composite material.
The mole ratio of the silicon dioxide to the magnesium powder in the sand in the step (1) is 1: 4.
The molar ratio of the magnesium carbonate in the step (2) to the silica in the sand in the step (1) is 1: 4.
The inert gas in the step (1) and the step (2) is pure argon or a mixed gas of argon (95 v%) and hydrogen (5 v%).
Example 8:
the silicon/carbon composite material prepared in this embodiment specifically includes the following steps, as shown in fig. 1:
(1) mixing sandy soil and magnesium powder, heating to 700 ℃ in an inert atmosphere, preserving heat for 5 hours, and cooling to obtain a mixture containing magnesium silicide.
(2) And (2) adding a mixture of magnesium carbonate and calcium carbonate into the mixture prepared in the step (1), uniformly mixing, heating to 800 ℃ in an inert atmosphere, keeping the temperature for 5 hours, and cooling to obtain a reaction product.
(3) And (3) adding sufficient 3mol/l hydrochloric acid and 5 wt% hydrofluoric acid into the reaction product obtained in the step (2), and cleaning and drying to obtain the silicon/carbon composite material.
The molar ratio of the silicon dioxide to the magnesium powder in the sandy soil in the step (1) is 1: 4.
The molar ratio of the mixture of magnesium carbonate and calcium carbonate in the step (2) to the silica in the sandy soil in the step (1) is 1: 4.
The inert gas in the step (1) and the step (2) is pure argon or a mixed gas of argon (95 v%) and hydrogen (5 v%).
The above description is only illustrative of the preferred embodiments of the present invention and should not be taken as limiting the scope of the invention in any way. Any changes or modifications of the technical contents disclosed above by a person skilled in the art should be considered as equivalent effective embodiments, and all the changes or modifications should be covered by the technical scope of the present invention.

Claims (9)

1. A preparation method of a silicon/carbon composite material is characterized by comprising the following steps: the method comprises the following steps of reacting a silicon dioxide raw material with magnesium powder to generate a magnesium silicide-containing mixture, reacting the mixture with carbonate, removing impurities through acid washing, and drying to generate the carbon and nano-silicon composite material, wherein the method specifically comprises the following steps:
(1) uniformly mixing a silicon dioxide raw material and magnesium powder, heating and reacting under an inert atmosphere, and cooling to obtain a mixture containing magnesium silicide;
(2) and (2) adding carbonate into the mixture prepared in the step (1), uniformly mixing, heating and reacting in an inert atmosphere, after the reaction is finished, sequentially immersing reaction products into sufficient hydrochloric acid aqueous solution and hydrofluoric acid solution to remove impurities, and then separating and drying to obtain the silicon/carbon composite material.
2. The method for preparing a silicon/carbon composite material according to claim 1, wherein: the silica raw material in the step (1) is one or more of diatomite, white carbon black, rice hull ash, glass fiber waste, sand, sandy soil and powder of ball-milled glass.
3. The method for preparing a silicon/carbon composite material according to claim 1, wherein: the inert atmosphere in the step (1) and the step (2) is pure argon gas or a mixed gas of 5 v% of hydrogen and 95 v% of argon gas.
4. The method for preparing a silicon/carbon composite material according to claim 1, wherein: the carbonate is one or a mixture of calcium carbonate and magnesium carbonate.
5. The method for preparing a silicon/carbon composite material according to claim 1, wherein: the mole ratio of the silicon dioxide to the magnesium powder in the silicon dioxide raw material in the step (1) is 1: 2.05-1: 6.
6. the method for preparing a silicon/carbon composite material according to claim 1, wherein: the heating reaction conditions in the steps (1) and (2) are 500 ℃ and 900 ℃, and the reaction is carried out for 2-12 hours at constant temperature.
7. The method for preparing a silicon/carbon composite material according to claim 1, wherein: the molar ratio of the carbonate in the step (2) to the silica in the silica raw material in the step (1) is 0.05: 1-2:1.
8. A silicon/carbon composite material obtained by the production method according to any one of claims 1 to 7.
9. The silicon/carbon composite material according to claim 8, wherein: the silicon/carbon composite material has silicon nanoparticles uniformly distributed on the carbon material, and the particle size of the silicon is less than 80 nanometers.
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CN111874911A (en) * 2020-07-10 2020-11-03 同济大学 Preparation method of amorphous silicon material
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CN104617275A (en) * 2015-02-11 2015-05-13 武汉科技大学 Method for preparing silicon-carbon compound from silicon-containing biomass as raw material as well as prepared silicon-carbon compound and application thereof
CN105084366A (en) * 2014-05-15 2015-11-25 国家纳米科学中心 Method for preparing nano-sized silicon and silicon/carbon composite material by using silica fume as raw material and application thereof

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CN105084366A (en) * 2014-05-15 2015-11-25 国家纳米科学中心 Method for preparing nano-sized silicon and silicon/carbon composite material by using silica fume as raw material and application thereof
CN104617275A (en) * 2015-02-11 2015-05-13 武汉科技大学 Method for preparing silicon-carbon compound from silicon-containing biomass as raw material as well as prepared silicon-carbon compound and application thereof

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