CN110581270A - Preparation method and application of hollow nano silicon sphere negative electrode material - Google Patents
Preparation method and application of hollow nano silicon sphere negative electrode material Download PDFInfo
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Abstract
The invention relates to a preparation method and application of a hollow nano silicon ball cathode material, which specifically comprises the following steps: s1: mixing hexadecyl ammonium bromide, lauryl sodium sulfate, ammonia water, absolute ethyl alcohol and ultrapure water, and adding tetraethyl orthosilicate for sol-gel reaction to obtain white powder. S2: after the white powder is incubated, the mixture is washed by acid absolute ethyl alcohol, dried and calcined to obtain the hollow silicon dioxide. S3: the hollow silica is fully ground with magnesium powder, sodium chloride, potassium chloride and the like, mixed and calcined to obtain a brown mixture. S4: and cleaning the brown mixture by hydrochloric acid and hydrofluoric acid, and drying to obtain the hollow nano silicon spheres. Tests show that the hollow nano silicon spheres have the capacity of 1200mAh/g after 100 cycles under the current density of 1.0A/g, which is far higher than that of common silicon (only 400mAh/g is left after 100 cycles). The hollow nano silicon spheres can obviously improve the cycling stability of the silicon cathode material.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery cathode materials, and particularly relates to a preparation method of hollow nano silicon spheres and application of the hollow nano silicon spheres in preparation of a lithium ion battery cathode material.
Background
Silicon has a very high reserve on earth and has a wide application in the semiconductor and energy fields. The theoretical capacity of silicon is 4200 mAh.g-1The material is far higher than the traditional graphite cathode, and is expected to become a cathode material of a new-generation lithium ion battery. However, the lithiation process of silicon has large volume expansion, which causes continuous fracture growth of the SEI film, resulting in lower first effect and poorer cycle performance. At present, there are two main methods for improving the performance of silicon cathode materials, one is to coat the surface of silicon, and the other is to design silicon with different microstructures.
Chinese patent application 201910072699.5 discloses a surface double-layer coated silicon cathode material structure, wherein the surface of silicon particles is coated with a silicon nitride layer and a silicon oxide layer in sequence from inside to outside. The silicon material lithium storage expansion can be limited by the silicon nitride layer of the inner layer, and the elastic pinning effect can be achieved by combining the Si-O bond in the silicon oxide layer of the outer layer with the carbon-hydrogen-oxygen structure in the binder to form a chemical bond, so that the cycle stability of the lithium ion battery is improved. Meanwhile, due to the existence of the inner silicon nitride layer, the outer silicon oxide layer only has the function of combining with the binder to form a pinning effect, so that the thickness of the silicon oxide layer can be thinner, excessive irreversible oxide cannot be generated in the lithium storage process, and the first coulomb efficiency of the silicon cathode material cannot be greatly influenced. Therefore, the silicon oxide and silicon nitride double-layer coated silicon negative electrode material structure is expected to simultaneously have high specific capacity, excellent cycling stability and high first coulombic efficiency.
Chinese patent application 201810797037.X discloses a silicon-based negative electrode material, which comprises a plurality of silicon nanoparticles and a binder, wherein the silicon nanoparticles are connected with each other by the binder, the binder comprises citric acid and a macromolecular chain polymer, the citric acid is coated on the surfaces of the silicon nanoparticles, and the macromolecular chain polymer is connected with the citric acid on the surfaces of the silicon nanoparticles. The synergistic effect of macromolecular chain polymer and the double binders of CA is utilized to form a three-dimensional cross-linked structure as the binder of the silicon-based negative electrode material, so that the structural stability of the electrode material is enhanced.
The Chinese patent application 201710856095.0 discloses a novel silicon micro-nano structure preparation technology, which combines metal-induced silicon oxidation and acid-base corrosion, and provides a preparation method of a large-area periodic silicon micro-nano structure array with low cost and high efficiency. The pattern of the silicon micro-nano structure is determined not only by the pattern of the micro-nano structure on the photoetching template, but also by the type of the used corrosive agent. The preparation method is simple in process and low in equipment requirement, and can be used for efficiently preparing periodic silicon micro-nano structure arrays, such as microstructures of silicon micro-nano holes, regular pyramids, inverted pyramids and the like. The method has simple process and low cost, and the prepared large-area silicon micro-nano structure array has wide application prospect in the fields of solar cells, sensors and the like.
In the prior art, a report that the nano silicon spheres with hollow structures are prepared by combining a sol-gel method and a magnesiothermic reduction method so as to effectively improve the cycle performance of a silicon cathode material does not exist.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method and application of a hollow nano silicon sphere negative electrode material.
the invention adopts the following technical scheme: a preparation method of a hollow nano silicon ball cathode material comprises the steps of preparing hollow silicon dioxide by a sol-gel method, and carrying out magnesiothermic reduction on the hollow silicon dioxide to obtain a hollow nano silicon ball.
In a preferred embodiment of the present invention, the preparation method specifically comprises the following steps:
S1: mixing hexadecyl ammonium bromide, lauryl sodium sulfate, ammonia water, absolute ethyl alcohol and water, and adding tetraethyl orthosilicate to perform sol-gel reaction to obtain white powder;
S2: after the obtained white powder is incubated in water, the white powder is washed and dried by acid absolute ethyl alcohol and calcined to obtain hollow silicon dioxide;
S3: fully grinding hollow silicon dioxide, magnesium powder, sodium chloride, potassium chloride and the like, mixing, and calcining to obtain a brown mixture;
S4: and cleaning the brown mixture by hydrochloric acid and hydrofluoric acid, and drying to obtain the hollow nano silicon spheres.
Preferably, the specific operation of S1 is: dissolving cetyl ammonium bromide and lauryl sodium sulfate in a mixed solution of ultrapure water and absolute ethyl alcohol, adding ammonia water, stirring, dropwise adding tetraethyl orthosilicate into the mixed solution, stirring, and performing suction filtration to obtain white powder.
Preferably, in the specific operation of S1, the reaction temperature is 30-35 ℃.
Preferably, in the specific operation of S1, the stirring rate is 500-800 rpm.
Preferably, in the specific operation of S1, the reaction time is 20-30 h.
Preferably, in the specific operation of S1, the mass to volume (g/L) ratio of cetylammonium bromide, sodium dodecylsulfate to water is 1.5-3.5: 1.5-3.5:0.5-2.
Preferably, in the specific operation of S1, the volume ratio of ammonia water, tetraethyl orthosilicate, absolute ethyl alcohol and water is: 0.5-1.5:0.5-1.2: 25-40:35-60.
Preferably, in the specific operation of S1, the concentration of aqueous ammonia is 28 wt%.
Preferably, in the specific operation of S2, the white powder is incubated in ultrapure water.
Preferably, in the specific operation of S2, the incubation temperature is 65-90 ℃.
Preferably, in the specific operation of S2, the incubation time is 24h-72 h.
Preferably, in the specific operation of S2, the mixture is washed in absolute ethyl alcohol, and 0.2-0.5ml of hydrochloric acid is added.
Preferably, in the specific operation of S2, the washing temperature is 60-70 ℃.
Preferably, in the specific operation of S2, the cleaning time is 6-12 h.
Preferably, in the specific operation of S2, the drying temperature is 80 ℃, and the drying time is 12 h.
Preferably, in the specific operation of S2, calcination is performed in air.
Preferably, in the specific operation of S2, the calcination temperature is 450-600 ℃.
Preferably, in the specific operation of S2, the calcination time is 4-8 h.
Preferably, in the specific operation of S3, the mass ratio of the hollow silica, the magnesium powder, the sodium chloride and the potassium chloride is 1:0.8-1.5:5-10: 5-10.
Preferably, in the specific operation of S3, the grinding time is not specifically defined, and the mixture is mixed uniformly.
preferably, in the specific operation of S3, the magnesiothermic reduction reaction is performed under an argon atmosphere.
Preferably, in the specific operation of S3, the temperature of the magnesiothermic reduction reaction is 650-700 ℃.
Preferably, in the specific operation of S3, the heating rate is 1-10 deg.C/min.
Preferably, in the specific operation of S3, the holding time is 2.5-4 h.
Preferably, in the specific operation of S4, the hydrochloric acid concentration is 1-3 mol/L.
Preferably, in the specific operation of S4, the washing time of hydrochloric acid is 5-12 h.
Preferably, in the specific operation of S4, the concentration of hydrofluoric acid is 5 to 10 wt%.
Preferably, in the specific operation of S4, the cleaning time of hydrofluoric acid is 1-3 h.
Preferably, in the specific operation of S4, the drying manner is vacuum drying.
Preferably, in the specific operation of S4, the drying time is 12-24 h.
The invention also protects the application of the hollow nano silicon spheres in the negative electrode material of the lithium ion battery.
Compared with the prior art, the method for preparing the hollow nano silicon spheres by combining the sol-gel method with the magnesiothermic reduction method for the first time provides space for the volume change of the prepared hollow nano silicon spheres in the lithiation process of the silicon material, shortens the lithium ion transmission path, and effectively improves the cycling stability of the silicon.
Drawings
The following is further described with reference to the accompanying drawings:
FIG. 1 is a TEM picture of a hollow silica of example 3;
FIG. 2 is a TEM image of the hollow nano-silica spheres of example 3;
Fig. 3 shows the measurement results of the charge and discharge performance and the cycle performance of the hollow nano-silicon spheres of example 3.
Detailed Description
The following examples are further described below.
Example 1
S1: mixing hexadecyl ammonium bromide, lauryl sodium sulfate, ammonia water, absolute ethyl alcohol and ultrapure water, and adding tetraethyl orthosilicate for sol-gel reaction to obtain white powder.
S2: after the white powder is incubated, the mixture is washed by acid absolute ethyl alcohol, dried and calcined to obtain the hollow silicon dioxide.
S3: the hollow silica is fully ground with magnesium powder, sodium chloride, potassium chloride and the like, mixed and calcined to obtain a brown mixture.
S4: and cleaning the brown mixture by hydrochloric acid and hydrofluoric acid, and drying to obtain the hollow nano silicon spheres.
Wherein, the specific operation of S1 is: dissolving cetyl ammonium bromide and sodium dodecyl sulfate in the mixed solution of ultrapure water and absolute ethyl alcohol, adding ammonia water, and stirring. And dropwise adding tetraethyl orthosilicate into the mixed solution, stirring, carrying out suction filtration to obtain white powder, and carrying out incubation, cleaning, drying and calcining on the obtained white powder to obtain the hollow silicon dioxide.
In the specific operation of S1, the reaction temperature was 35 ℃.
In the specific operation of S1, the stirring rate was 600 rpm.
In the specific operation of S1, the reaction time was 20 hours.
In the specific operation of S1, the mass-to-volume (g/L) ratio of cetylammonium bromide, sodium dodecylsulfate and water was 3:3: 1.
In the specific operation of S1, the volume ratio of ammonia water, tetraethyl orthosilicate, absolute ethyl alcohol and water is as follows: 1.5:1:30:50.
in the specific operation of S1, the concentration of aqueous ammonia was 28% by weight.
In a specific procedure of S2, the white powder was incubated in ultrapure water.
In the specific procedure of S2, the incubation temperature was 80 ℃.
In the specific operation of S2, the incubation time was 36 h.
In the specific operation of S2, the mixture was washed with absolute ethanol, and 0.3ml of hydrochloric acid was added thereto.
In the specific operation of S2, the washing temperature was 60 ℃.
In the specific operation of S2, the washing time was 10 hours.
In the specific operation of S2, the drying temperature is 80 ℃, and the drying time is 12 h.
In the specific operation of S2, calcination was carried out in air.
In the specific operation of S2, the calcination temperature was 550 ℃.
In the specific operation of S2, the calcination time was 6 hours.
The hollow silica obtained in S2 had a particle size of 450 nm.
In the specific operation of S3, the mass ratio of the hollow silica, the magnesium powder, the sodium chloride and the potassium chloride is 1:1:5: 5.
In the specific operation of S3, the grinding time is not specifically defined, and the mixture is mixed uniformly.
In the specific operation of S3, the magnesiothermic reduction reaction was performed under an argon atmosphere.
In the specific operation of S3, the magnesiothermic reduction reaction temperature was 700 ℃.
In the specific operation of S3, the temperature increase rate was 5 ℃/min.
In the specific operation of S3, the incubation time was 3 hours.
In the specific operation of S4, the hydrochloric acid concentration was 1.5 mol/L.
In the specific operation of S4, the washing time with hydrochloric acid was 10 hours.
In the specific operation of S4, the concentration of hydrofluoric acid was 5 wt%.
In the specific operation of S4, the cleaning time of hydrofluoric acid was 1 h.
In the specific operation of S4, the drying method is vacuum drying.
In the specific operation of S4, the drying time was 18 hours.
The particle size of the hollow silicon microsphere obtained in S4 is about 450 nm.
Example 2
The preparation method of the hollow nano silicon ball comprises the following steps
S1: mixing hexadecyl ammonium bromide, lauryl sodium sulfate, ammonia water, absolute ethyl alcohol and ultrapure water, and adding tetraethyl orthosilicate for sol-gel reaction to obtain white powder.
S2: after the white powder is incubated, the mixture is washed by acid absolute ethyl alcohol, dried and calcined to obtain the hollow silicon dioxide.
S3: the hollow silica is fully ground with magnesium powder, sodium chloride, potassium chloride and the like, mixed and calcined to obtain a brown mixture.
S4: and cleaning the brown mixture by hydrochloric acid and hydrofluoric acid, and drying to obtain the hollow nano silicon spheres.
Wherein, the specific operation of S1 is: dissolving cetyl ammonium bromide and sodium dodecyl sulfate in the mixed solution of ultrapure water and absolute ethyl alcohol, adding ammonia water, and stirring. And dropwise adding tetraethyl orthosilicate into the mixed solution, stirring, carrying out suction filtration to obtain white powder, and carrying out incubation, cleaning, drying and calcining on the obtained white powder to obtain the hollow silicon dioxide.
In the specific operation of S1, the reaction temperature was 30 ℃.
In the specific operation of S1, the stirring rate was 500 rpm.
In the specific operation of S1, the reaction time was 24 hours.
In the specific operation of S1, the mass-to-volume (g/L) ratio of cetylammonium bromide, sodium dodecylsulfate and water was 2:2: 1.
In the specific operation of S1, the volume ratio of ammonia water, tetraethyl orthosilicate, absolute ethyl alcohol and water is as follows: 0.5:0.5:25:35.
in the specific operation of S1, the concentration of aqueous ammonia was 28wt%
In a specific procedure of S2, the white powder was incubated in ultrapure water.
In the specific procedure of S2, the incubation temperature was 90 ℃.
in the specific operation of S2, the incubation time was 24 hours.
In the specific operation of S2, the mixture was washed with absolute ethanol, and 0.2ml of hydrochloric acid was added thereto.
In the specific operation of S2, the washing temperature was 60 ℃.
In the specific operation of S2, the washing time was 6 hours.
In the specific operation of S2, the drying temperature is 80 ℃, and the drying time is 12 h.
In the specific operation of S2, calcination was carried out in air.
in the specific operation of S2, the calcination temperature was 500 ℃.
In the specific operation of S2, the calcination time was 8 hours.
The hollow silica obtained in S2 had a particle size of 450 nm.
In the specific operation of S3, the mass ratio of the hollow silica, the magnesium powder, the sodium chloride and the potassium chloride is 1:0.8:5: 5.
In the specific operation of S3, the grinding time is not specifically defined, and the mixture is mixed uniformly.
In the specific operation of S3, the magnesiothermic reduction reaction was performed under an argon atmosphere.
In the specific operation of S3, the magnesiothermic reduction reaction temperature was 700 ℃.
In the specific operation of S3, the temperature increase rate was 3 ℃/min.
In the specific operation of S3, the holding time was 2.5 hours.
In the specific operation of S4, the hydrochloric acid concentration was 1 mol/L.
In the specific operation of S4, the washing time with hydrochloric acid was 12 hours.
In the specific operation of S4, the concentration of hydrofluoric acid was 5 wt%.
In the specific operation of S4, the cleaning time of hydrofluoric acid was 1 h.
In the specific operation of S4, the drying method is vacuum drying.
In the specific operation of S4, the drying time was 12 hours.
The particle size of the hollow silicon microsphere obtained in S4 is about 450 nm.
Embodiment 3
The preparation method of the hollow nano silicon ball comprises the following steps
s1: mixing hexadecyl ammonium bromide, lauryl sodium sulfate, ammonia water, absolute ethyl alcohol and ultrapure water, and adding tetraethyl orthosilicate for sol-gel reaction to obtain white powder.
S2: after the white powder is incubated, the mixture is washed by acid absolute ethyl alcohol, dried and calcined to obtain the hollow silicon dioxide.
S3: the hollow silica is fully ground with magnesium powder, sodium chloride, potassium chloride and the like, mixed and calcined to obtain a brown mixture.
S4: and cleaning the brown mixture by hydrochloric acid and hydrofluoric acid, and drying to obtain the hollow nano silicon spheres.
Wherein, the specific operation of S1 is: dissolving cetyl ammonium bromide and sodium dodecyl sulfate in the mixed solution of ultrapure water and absolute ethyl alcohol, adding ammonia water, and stirring. And dropwise adding tetraethyl orthosilicate into the mixed solution, stirring, carrying out suction filtration to obtain white powder, and carrying out incubation, cleaning, drying and calcining on the obtained white powder to obtain the hollow silicon dioxide.
In the specific operation of S1, the reaction temperature was 35 ℃.
In the specific operation of S1, the stirring rate was 800 rpm.
In the specific operation of S1, the reaction time was 20 hours.
In the specific operation of S1, the mass to volume (g/L) ratio of cetylammonium bromide, sodium dodecylsulfate and water was 1.5:1.5: 1.
In the specific operation of S1, the volume ratio of ammonia water, tetraethyl orthosilicate, absolute ethyl alcohol and water is as follows: 1:1:25:35.
In the specific operation of S1, the concentration of aqueous ammonia was 28% by weight.
In a specific procedure of S2, the white powder was incubated in ultrapure water.
In the specific procedure of S2, the incubation temperature was 80 ℃.
In the specific operation of S2, the incubation time was 48 hours.
In the specific operation of S2, the mixture was washed with absolute ethanol, and 0.3ml of hydrochloric acid was added thereto.
In the specific operation of S2, the washing temperature was 65 ℃.
in the specific operation of S2, the washing time was 12 hours.
In the specific operation of S2, the drying temperature is 80 ℃, and the drying time is 12 h.
In the specific operation of S2, calcination was carried out in air.
In the specific operation of S2, the calcination temperature was 550 ℃.
In the specific operation of S2, the calcination time was 6 hours.
The hollow silica obtained in S2 had a particle size of 450 nm.
in the specific operation of S3, the mass ratio of the hollow silica, the magnesium powder, the sodium chloride and the potassium chloride is 1:1:10: 10.
In the specific operation of S3, the grinding time is not specifically defined, and the mixture is mixed uniformly.
In the specific operation of S3, the magnesiothermic reduction reaction was performed under an argon atmosphere.
In the specific operation of S3, the magnesiothermic reduction reaction temperature was 700 ℃.
In the specific operation of S3, the temperature increase rate was 5 ℃/min.
In the specific operation of S3, the incubation time was 3 hours.
In the specific operation of S4, the hydrochloric acid concentration was 2 mol/L.
In the specific operation of S4, the washing time with hydrochloric acid was 6 hours.
In the specific operation of S4, the concentration of hydrofluoric acid was 10 wt%.
In the specific operation of S4, the cleaning time of hydrofluoric acid was 0.5 h.
In the specific operation of S4, the drying method is vacuum drying.
In the specific operation of S4, the drying time was 12 hours.
The particle size of the hollow silicon microsphere obtained in S4 is about 500 nm.
Fig. 1 is a TEM picture of the hollow silica of example 3, fig. 2 is a TEM picture of the hollow nano silicon spheres of example 3, fig. 3 is a result of detecting charge and discharge performance and cycle performance of the hollow nano silicon spheres of example 3 and common nano silicon, and the result shows that the hollow nano silicon spheres still have a capacity of 1200mAh/g after 100 cycles at a current density of 1.0A/g, which is much higher than that of the common silicon (only 400mAh/g remains after 100 cycles).
The above description is only for the preferred embodiments of the present invention, but the scope of the present invention is not limited thereto, and the modifications or substitutions according to the concept of the present invention should be covered within the scope of the present invention.
Claims (7)
1. A preparation method of a hollow nano silicon ball cathode material is characterized in that hollow silicon dioxide is prepared through a sol-gel method and subjected to magnesiothermic reduction to obtain hollow nano silicon balls.
2. The preparation method according to claim 1, wherein the preparation method specifically comprises the following steps:
S1: mixing hexadecyl ammonium bromide, lauryl sodium sulfate, ammonia water, absolute ethyl alcohol and water, and adding tetraethyl orthosilicate to perform sol-gel reaction to obtain white powder;
S2: after the obtained white powder is incubated in water, the white powder is washed and dried by acid absolute ethyl alcohol and calcined to obtain hollow silicon dioxide;
S3: fully grinding hollow silicon dioxide, magnesium powder, sodium chloride, potassium chloride and the like, mixing, and calcining to obtain a brown mixture;
S4: and cleaning the brown mixture by hydrochloric acid and hydrofluoric acid, and drying to obtain the hollow nano silicon spheres.
3. The preparation method according to claim 2, wherein the specific operation of S1 is: dissolving cetyl ammonium bromide and lauryl sodium sulfate in a mixed solution of ultrapure water and absolute ethyl alcohol, adding ammonia water, stirring, dropwise adding tetraethyl orthosilicate into the mixed solution, stirring, and performing suction filtration to obtain white powder; in the specific operation of S1, the reaction temperature is 30-35 ℃, the stirring speed is 500-800rpm, the reaction time is 20-30h, and the mass-to-volume (g/L) ratio of the hexadecyl ammonium bromide, the lauryl sodium sulfate and the water is 1.5-3.5: 1.5-3.5:0.5-2, wherein the volume ratio of ammonia water, tetraethyl orthosilicate, absolute ethyl alcohol and water is as follows: 0.5-1.5:0.5-1.2: 25-40:35-60, and the concentration of ammonia water is 28 wt%.
4. the method according to claim 2, wherein in the specific operation of S2, the white powder is incubated in ultrapure water at 65-90 ℃ for 24-72 hours, washed in absolute ethanol and added with 0.2-0.5ml of hydrochloric acid at 60-70 ℃ for 6-12 hours; the drying temperature is 80 ℃, and the drying time is 12 h; calcining in air at the temperature of 450 ℃ and 600 ℃ for 4-8 h.
5. the preparation method according to claim 2, wherein in the specific operation of S3, the mass ratio of the hollow silica, magnesium powder, sodium chloride and potassium chloride is 1:0.8-1.5:5-10: 5-10; the grinding time is not specifically specified, and the grinding and grinding processes are uniformly mixed; the magnesium thermal reduction reaction is carried out in the argon atmosphere, the temperature of the magnesium thermal reduction reaction is 650-700 ℃, the heating rate is 1-10 ℃/min, and the heat preservation time is 2.5-4 h.
6. The preparation method according to claim 2, wherein in the specific operation of S4, the hydrochloric acid concentration is 1 to 3mol/L, and the cleaning time of the hydrochloric acid is 5 to 12 hours; the concentration of the hydrofluoric acid is 5-10wt%, and the cleaning time of the hydrofluoric acid is 1-3 h; the drying mode is vacuum drying, and the drying time is 12-24 h.
7. The application of the hollow nano silicon spheres prepared by the preparation method of any one of claims 1 to 6 in lithium ion battery cathode materials.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111232985A (en) * | 2020-01-17 | 2020-06-05 | 昆明理工大学 | Preparation method of micron-sized porous hollow silicon spheres |
| CN111446432A (en) * | 2020-04-20 | 2020-07-24 | 上海交通大学 | Preparation method of nano silicon/carbon composite negative electrode material for lithium ion battery |
| CN113363455A (en) * | 2021-06-04 | 2021-09-07 | 广东工业大学 | Composite two-dimensional micron-sized silicon wafer and preparation method thereof |
| CN113488624A (en) * | 2021-07-08 | 2021-10-08 | 中国恩菲工程技术有限公司 | Silicon-carbon composite material and preparation method and application thereof |
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| CN113488624A (en) * | 2021-07-08 | 2021-10-08 | 中国恩菲工程技术有限公司 | Silicon-carbon composite material and preparation method and application thereof |
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