CN114735704B - Method for synthesizing nano silicon carbide at low temperature - Google Patents
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 50
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000005543 nano-size silicon particle Substances 0.000 title abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 60
- 241000209094 Oryza Species 0.000 claims abstract description 39
- 235000007164 Oryza sativa Nutrition 0.000 claims abstract description 39
- 239000010903 husk Substances 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 39
- 235000009566 rice Nutrition 0.000 claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 27
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000012298 atmosphere Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 239000011780 sodium chloride Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 239000011863 silicon-based powder Substances 0.000 claims abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 8
- 239000001103 potassium chloride Substances 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001291 vacuum drying Methods 0.000 abstract description 4
- 239000002154 agricultural waste Substances 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- FRIKWZARTBPWBN-UHFFFAOYSA-N [Si].O=[Si]=O Chemical compound [Si].O=[Si]=O FRIKWZARTBPWBN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/956—Silicon carbide
- C01B32/963—Preparation from compounds containing silicon
- C01B32/977—Preparation from organic compounds containing silicon
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Abstract
本发明属于材料制备技术领域，具体涉及一种低温合成纳米碳化硅的方法，该方法主要包括：将洁净的稻壳在空气气氛中热处理，将热处理的产物与适量的NaCl、KCl和Mg粉混合，在惰性气氛中还原热处理，产物经酸洗、干燥，制得含微量氧和碳的纳米硅粉；将硅粉与镁粉、碳源混合，在惰性气氛、550～750℃热处理，热处理产物经酸浸泡、清洗、真空干燥，得到纯净的纳米碳化硅材料，产率达到96％以上。本发明以稻壳为主要原料，制得纳米碳化硅材料，实现农业废弃物的循环利用；同时，本发明的制备工艺简单，效率高，合成温度低，成本低廉，可直接用于工业化生产。
The invention belongs to the technical field of material preparation, and specifically relates to a method for low-temperature synthesis of nanometer silicon carbide. The method mainly includes: heat-treating clean rice husk in an air atmosphere, and mixing the heat-treated product with an appropriate amount of NaCl, KCl and Mg powder. , perform reduction heat treatment in an inert atmosphere, and the product is pickled and dried to obtain nano-silica powder containing trace amounts of oxygen and carbon; mix the silicon powder with magnesium powder and carbon source, and heat-treat it in an inert atmosphere at 550-750°C to obtain the heat-treated product After acid soaking, cleaning and vacuum drying, pure nano-silicon carbide material is obtained with a yield of more than 96%. The invention uses rice husk as the main raw material to prepare nano-silicon carbide materials and realizes the recycling of agricultural waste; at the same time, the preparation process of the invention is simple, has high efficiency, low synthesis temperature and low cost, and can be directly used in industrial production.
Description
技术领域Technical field
本发明属于材料制备技术领域，具体涉及一种低温合成纳米碳化硅的方法。The invention belongs to the technical field of material preparation, and specifically relates to a method for synthesizing nanometer silicon carbide at low temperature.
背景技术Background technique
碳化硅具有独特的物理化学性质，例如能带带隙宽、机械强度高、热导率高、耐氧化性及化学稳定性好，应用前景及其广阔。这些独特的理化特性使其在电场发射、电子设备、微波吸收器、催化剂、电容器、传感器和生物探针等方面有广阔的应用前景。纳米碳化硅的制备方法一般采用溶胶-凝胶法、热化学气相反应法和碳热还原法等。溶胶-凝胶法制备纳米碳化硅材料受到很多因素的影响，例如，水解时间、溶液的pH值、热处理温度等，因此无法做到对碳化硅材料的微观结构的精准控制，难以生成结晶良好、纯度高、形状和粒径可控的纳米碳化硅；另外，也很难大规模生产。热化学气相反应法是将反应物加热至气相状态下反应，能耗高，产量低。因此，此方法生产纳米碳化硅成本高。碳热还原法是一种在一定温度下以无机碳为还原剂进行氧化还原反应的方法。碳热还原法制备碳化硅时，反应温度一般要达到1300℃，才可以得到纯度较高的碳化硅；因此，在高温下碳化硅易于生成大晶粒，产物尺寸不易控制。Silicon carbide has unique physical and chemical properties, such as wide energy band gap, high mechanical strength, high thermal conductivity, good oxidation resistance and chemical stability, and its application prospects are extremely broad. These unique physical and chemical properties make it have broad application prospects in electric field emission, electronic equipment, microwave absorbers, catalysts, capacitors, sensors and biological probes. The preparation methods of nanometer silicon carbide generally adopt sol-gel method, thermochemical gas phase reaction method and carbothermal reduction method. The preparation of nanometer silicon carbide materials by the sol-gel method is affected by many factors, such as hydrolysis time, pH value of the solution, heat treatment temperature, etc. Therefore, it is impossible to accurately control the microstructure of silicon carbide materials, and it is difficult to produce well-crystallized, Nano-silicon carbide with high purity, controllable shape and particle size; in addition, it is also difficult to produce on a large scale. The thermochemical gas phase reaction method is to heat the reactants to react in the gas phase state, which has high energy consumption and low yield. Therefore, the cost of producing nano-silicon carbide by this method is high. The carbothermal reduction method is a method that uses inorganic carbon as a reducing agent to perform an oxidation-reduction reaction at a certain temperature. When silicon carbide is prepared by carbothermal reduction, the reaction temperature generally needs to reach 1300°C to obtain silicon carbide with higher purity; therefore, silicon carbide tends to generate large grains at high temperatures, and the product size is difficult to control.
稻壳中含有大量的碳和硅，公开号为CN103803982B的专利文献中公开了直接利用稻壳中的碳和硅合成碳化硅，但是在稻壳碳化后，硅以二氧化硅形式存在，碳与二氧化硅合成碳化硅必须在1400度以上才能合成。公开号为CN109748282B的专利文献公开了以纳米二氧化硅和有机物为原料，碳化后与金属镁粉在密闭容器中加热，低温合成碳化硅，但是需在高压下进行。Rice husk contains a large amount of carbon and silicon. The patent document with publication number CN103803982B discloses the direct use of carbon and silicon in rice husk to synthesize silicon carbide. However, after the rice husk is carbonized, the silicon exists in the form of silicon dioxide, and the carbon and Synthesis of silicon dioxide Silicon carbide must be synthesized at temperatures above 1400 degrees. The patent document with publication number CN109748282B discloses using nano-silica and organic matter as raw materials. After carbonization, it is heated with metal magnesium powder in a closed container to synthesize silicon carbide at low temperature, but it needs to be carried out under high pressure.
有鉴于此，有必要提供一种低温合成纳米碳化硅的方法。In view of this, it is necessary to provide a method for synthesizing nanometer silicon carbide at low temperature.
发明内容Contents of the invention
本发明的目的在于克服传统技术中存在的上述问题，提供一种低温合成纳米碳化硅的方法，通过使用生物质材料制备的超细纳米硅颗粒粉末和氧化石墨烯作为原料，可以增加反应面积以降低碳化硅合成反应的反应，能够低温合成碳化硅。The purpose of the present invention is to overcome the above-mentioned problems existing in traditional technology and provide a method for low-temperature synthesis of nano-silicon carbide. By using ultra-fine nano-silicon particle powder prepared from biomass materials and graphene oxide as raw materials, the reaction area can be increased to Reduce the reaction of silicon carbide synthesis reaction and enable low-temperature synthesis of silicon carbide.
为实现上述技术目的，达到上述技术效果，本发明是通过以下技术方案实现：In order to achieve the above technical objectives and achieve the above technical effects, the present invention is implemented through the following technical solutions:
一种低温合成纳米碳化硅的方法，包括如下步骤：A method for synthesizing nanometer silicon carbide at low temperature, including the following steps:
1)将洁净稻壳在空气气氛中进行恒温热处理，得到含微量碳的稻壳热处理产物；1) The clean rice husk is subjected to constant temperature heat treatment in an air atmosphere to obtain a rice husk heat treatment product containing trace amounts of carbon;
2)将得到的稻壳热处理产物与混合盐、Mg粉混合，在惰性气氛中恒温热处理，得到热处理产物A；2) Mix the obtained rice husk heat treatment product with mixed salt and Mg powder, and perform heat treatment at a constant temperature in an inert atmosphere to obtain heat treatment product A;
3)将得到的热处理产物A在盐酸中连续搅拌3～6h后，经分离、洗涤、真空干燥，得到含微量氧和碳的纳米硅粉；3) The obtained heat treatment product A is continuously stirred in hydrochloric acid for 3 to 6 hours, and then separated, washed, and vacuum dried to obtain nanosilica powder containing trace amounts of oxygen and carbon;
4)将得到的纳米硅粉与碳源混合，球磨一段时间，得到Si/C复合材料；4) Mix the obtained nano-silica powder with a carbon source and ball-mill for a period of time to obtain a Si/C composite material;
5)将得到的Si/C复合材料与Mg粉混合，在惰性气氛中进行恒温热处理，得到热处理产物B；5) Mix the obtained Si/C composite material with Mg powder, and perform constant temperature heat treatment in an inert atmosphere to obtain heat treatment product B;
6)将得到的热处理产物B在盐酸中连续搅拌2～8h，再经分离、洗涤、真空干燥，得到纳米碳化硅。6) The obtained heat-treated product B is continuously stirred in hydrochloric acid for 2 to 8 hours, and then separated, washed, and vacuum dried to obtain nanometer silicon carbide.
进一步地，如上所述低温合成纳米碳化硅的方法，步骤1)中，在空气气氛中的恒温热处理温度为450～600℃，恒温热处理时间为3～7h。Furthermore, in the method of low-temperature synthesis of nanometer silicon carbide as described above, in step 1), the constant temperature heat treatment temperature in the air atmosphere is 450-600°C, and the constant temperature heat treatment time is 3-7 hours.
进一步地，如上所述低温合成纳米碳化硅的方法，步骤2)中，在惰性气氛中的恒温热处理温度为550～750℃，恒温热处理时间为0.5～3h。Further, in the method of low-temperature synthesis of nanometer silicon carbide as described above, in step 2), the constant temperature heat treatment temperature in an inert atmosphere is 550-750°C, and the constant temperature heat treatment time is 0.5-3 hours.
进一步地，如上所述低温合成纳米碳化硅的方法，步骤2)中，混合盐由NaCl和KCl按摩尔比为1:1组成，Mg粉与稻壳热处理产物的质量比1:0.9～1.1，稻壳热处理产物、Mg粉的总质量与混合盐的质量比为1：2.2～2.8。Further, in the method of low-temperature synthesis of nanometer silicon carbide as described above, in step 2), the mixed salt is composed of NaCl and KCl in a molar ratio of 1:1, and the mass ratio of Mg powder to rice husk heat treatment product is 1:0.9~1.1, The mass ratio of the total mass of rice husk heat treatment products, Mg powder and mixed salt is 1:2.2~2.8.
进一步地，如上所述低温合成纳米碳化硅的方法，步骤2)和步骤5)中，Mg粉的粒径为50～300目。Further, in the method of low-temperature synthesis of nanometer silicon carbide as described above, in step 2) and step 5), the particle size of the Mg powder is 50 to 300 mesh.
进一步地，如上所述低温合成纳米碳化硅的方法，步骤3)和步骤6)中，盐酸的浓度为5～15wt％。Further, in the method of low-temperature synthesis of nanometer silicon carbide as described above, in step 3) and step 6), the concentration of hydrochloric acid is 5 to 15 wt%.
进一步地，如上所述低温合成纳米碳化硅的方法，步骤4)中，碳源为氧化石墨烯。Further, in the method for low-temperature synthesis of nanometer silicon carbide as described above, in step 4), the carbon source is graphene oxide.
进一步地，如上所述低温合成纳米碳化硅的方法，步骤4)中，纳米硅粉与碳源按照硅、碳摩尔比为1：1.1～2.0混合。Further, in the method of low-temperature synthesis of nano-silicon carbide as described above, in step 4), nano-silicon powder and carbon source are mixed according to a molar ratio of silicon to carbon of 1:1.1-2.0.
进一步地，如上所述低温合成纳米碳化硅的方法，步骤4)中，纳米硅粉、碳源的总质量与磨球的质量比为1:10～15，球磨机工作条件为：转速为400～450rpm，总球磨时间为10～12h。Further, in the method of low-temperature synthesis of nano silicon carbide as described above, in step 4), the mass ratio of the total mass of nano silicon powder, carbon source and grinding ball is 1:10~15, and the working conditions of the ball mill are: the rotation speed is 400~ 450rpm, the total ball milling time is 10~12h.
进一步地，如上所述低温合成纳米碳化硅的方法，步骤5)中，在惰性气氛中的恒温热处理温度为550～750℃，恒温热处理时间为1～5h。Further, in the method of low-temperature synthesis of nanometer silicon carbide as described above, in step 5), the constant temperature heat treatment temperature in an inert atmosphere is 550-750°C, and the constant temperature heat treatment time is 1-5 hours.
本发明的有益效果是：The beneficial effects of the present invention are:
本发明提供一种低温合成纳米碳化硅的方法，该方法设计科学合理，一方面将农业废弃物稻壳进行“去碳处理”，而后作为碳化硅的硅源，实现农业废弃物的变废为宝；另一方面与现有技术相比，能够在“超低温”下制备具有球形、粒径小于100nm的碳化硅粉末，同时具有较高的产率。The invention provides a method for low-temperature synthesis of nanometer silicon carbide. The method is scientifically and rationally designed. On the one hand, agricultural waste rice husks are "decarbonized" and then used as a silicon source for silicon carbide to realize the conversion of agricultural waste into waste. Bao; on the other hand, compared with the existing technology, it can prepare spherical silicon carbide powder with a particle size less than 100nm at "ultra-low temperature" and at the same time have a higher yield.
当然，实施本发明的任一产品并不一定需要同时达到以上的所有优点。Of course, any product implementing the present invention does not necessarily need to achieve all the above advantages at the same time.
附图说明Description of drawings
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to explain the technical solutions of the embodiments of the present invention more clearly, the drawings needed to describe the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without exerting creative efforts.
图1为本发明实施例1中稻壳还原产物的XRD图；Figure 1 is an XRD pattern of the rice husk reduction product in Example 1 of the present invention;
图2为本发明实施例1中稻壳还原产物的SEM；Figure 2 is an SEM of the rice husk reduction product in Example 1 of the present invention;
图3为本发明实施例1中稻壳还原产物氮气脱附曲线和孔径分布图；Figure 3 is a nitrogen desorption curve and pore size distribution diagram of the rice husk reduction product in Example 1 of the present invention;
图4为本发明实施例1所制备的纳米碳化硅的X射线衍射图；Figure 4 is an X-ray diffraction pattern of nanometer silicon carbide prepared in Example 1 of the present invention;
图5为本发明实施例1所制备的纳米碳化硅的场发射扫描电镜图。Figure 5 is a field emission scanning electron microscope image of nanometer silicon carbide prepared in Example 1 of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
本发明提供一种低温合成纳米碳化硅的方法，发明人在利用稻壳作为制备纳米碳化硅原料的研究过程中，发现直接利用稻壳作为主要碳源和硅源过程中，无法实现低温合成甚至是无法合成纳米碳化硅，发明人通过长期的研究，发现问题出现在利用稻壳作为碳源这个点上，为此，对应设计了对稻壳进行热处理除碳后只作为主要硅源，再与添加的碳源实现低温合成纳米碳化硅的技术方案。The present invention provides a method for low-temperature synthesis of nano-silicon carbide. During the research process of using rice husk as a raw material for preparing nano-silicon carbide, the inventor found that low-temperature synthesis or even low-temperature synthesis cannot be achieved by directly using rice husk as the main carbon source and silicon source. It is impossible to synthesize nano-silicon carbide. Through long-term research, the inventor found that the problem arises in using rice husk as a carbon source. To this end, the corresponding design is to heat-treat the rice husk to remove carbon and then use it as the main silicon source, and then use it with The added carbon source realizes the technical solution of low-temperature synthesis of nanometer silicon carbide.
本发明的具体实施例如下：Specific embodiments of the present invention are as follows:
实施例1Example 1
一种低温合成纳米碳化硅的方法，包括以下步骤：A method for synthesizing nanometer silicon carbide at low temperature, including the following steps:
1)将洁净稻壳在500℃空气气氛下中进行恒温4h，得到稻壳热处理产物；1) The clean rice husk is kept at a constant temperature for 4 hours in an air atmosphere of 500°C to obtain a rice husk heat treatment product;
2)将上述稻壳热处理产物与NaCl和KCl组成的混合盐、Mg粉混合，在750℃、Ar气气氛中进行恒温0.5h热处理，得到热处理产物A。其中NaCl与KCl摩尔比为1:1；Mg粉与稻壳热处理产物的质量比1:1；Mg粉粒径为150目；稻壳热处理产物和Mg粉的总质量与NaCl和KCl混合盐的总质量比为1：2.5；2) Mix the above rice husk heat treatment product with a mixed salt composed of NaCl and KCl and Mg powder, and perform heat treatment at a constant temperature of 750°C in an Ar gas atmosphere for 0.5 hours to obtain heat treatment product A. The molar ratio of NaCl to KCl is 1:1; the mass ratio of Mg powder to rice husk heat treatment product is 1:1; the Mg powder particle size is 150 mesh; the total mass of rice husk heat treatment product and Mg powder and NaCl and KCl mixed salt The total mass ratio is 1:2.5;
3)将得到的热处理产物A置于浓度为15wt％盐酸中连续搅拌3h，随后经洗涤、分离、真空干燥，得到含微量氧和碳的纳米硅粉；3) Place the obtained heat treatment product A in hydrochloric acid with a concentration of 15wt% and stir continuously for 3 hours, followed by washing, separation, and vacuum drying to obtain nanosilica powder containing trace amounts of oxygen and carbon;
4)将得到的纳米硅粉与氧化石墨烯按硅、碳摩尔比1:1.5混合，球磨12h，得到Si/C复合材料；4) Mix the obtained nano-silica powder and graphene oxide at a silicon to carbon molar ratio of 1:1.5, and ball-mill for 12 hours to obtain a Si/C composite material;
5)将得到的Si/C复合材料与Mg粉混合均匀，在700℃、Ar气气氛恒温1.5h，得到热处理产物B；5) Mix the obtained Si/C composite material and Mg powder evenly, and heat it at a constant temperature of 700°C and Ar gas atmosphere for 1.5 hours to obtain heat treatment product B;
6)将得到的热处理产物B在浓度为15wt％盐酸中连续搅拌3h，经洗涤、分离和真空干燥，得到纳米碳化硅粉体。产率(以煅烧后SiO2计算)为96.5％。6) The obtained heat-treated product B was continuously stirred in hydrochloric acid with a concentration of 15wt% for 3 hours, washed, separated and vacuum dried to obtain nanometer silicon carbide powder. The yield (calculated as SiO2 after calcination) is 96.5%.
实施例2：Example 2:
一种低温合成纳米碳化硅的方法，包括以下步骤：A method for synthesizing nanometer silicon carbide at low temperature, including the following steps:
1)将洁净干燥的稻壳置于高温炉中，在450℃空气气氛中，保温时间为7h，得到稻壳热处理产物；1) Place the clean and dry rice husk in a high-temperature furnace in an air atmosphere of 450°C for a holding time of 7 hours to obtain a rice husk heat treatment product;
2)将得到的稻壳热处理产物与NaCl和KCl组成的混合盐、Mg粉混合，在700℃、Ar气气氛中进行恒温1.5h热处理，得到热处理产物A。其中NaCl与KCl摩尔比为1:1；Mg粉与稻壳热处理产物的质量比1:1.1；Mg粉粒径为50目；稻壳热处理产物和Mg粉的总质量与NaCl和KCl混合盐的总质量比为1：2.2；2) Mix the obtained rice husk heat treatment product with a mixed salt composed of NaCl and KCl and Mg powder, and perform heat treatment at a constant temperature of 700°C in an Ar gas atmosphere for 1.5 hours to obtain heat treatment product A. The molar ratio of NaCl to KCl is 1:1; the mass ratio of Mg powder to rice husk heat treatment product is 1:1.1; the Mg powder particle size is 50 mesh; the total mass of rice husk heat treatment product and Mg powder and NaCl and KCl mixed salt The total mass ratio is 1:2.2;
3)将热处理产物A取出，置于浓度为15wt％盐酸中连续搅拌3h，经分离、洗涤、真空干燥，得到含微量氧和碳的纳米硅粉；3) Take out the heat treatment product A, place it in hydrochloric acid with a concentration of 15wt% and stir continuously for 3 hours. After separation, washing and vacuum drying, nano-silica powder containing trace amounts of oxygen and carbon is obtained;
4)将得到的纳米硅粉与氧化石墨烯按硅、碳摩尔比为1：1.3混合，混合物置于密封的球磨罐中，料与磨球的质量比为1:15；球磨机转速为400～450rpm，总球磨时间为10h；4) Mix the obtained nano-silica powder and graphene oxide at a silicon to carbon molar ratio of 1:1.3. The mixture is placed in a sealed ball mill tank. The mass ratio of the material to the grinding balls is 1:15; the ball mill speed is 400~ 450rpm, total ball milling time is 10h;
5)将得到的混合物与150目Mg粉质量比为1:1.1混合，在650℃氩气气氛中进行恒温热处理1h，得到热处理产物B；5) Mix the obtained mixture with 150 mesh Mg powder at a mass ratio of 1:1.1, and perform constant temperature heat treatment in an argon atmosphere at 650°C for 1 hour to obtain heat treatment product B;
6)将得到的热处理产物B置于浓度为15wt％盐酸中连续搅拌4h，再经分离、洗涤、真空干燥，得到纳米碳化硅粉体。产率(以煅烧后SiO2计算)为97.2％。6) The obtained heat-treated product B was placed in hydrochloric acid with a concentration of 15wt% and continuously stirred for 4 hours, and then separated, washed, and vacuum dried to obtain nanometer silicon carbide powder. The yield (calculated as SiO2 after calcination) is 97.2%.
实施例3Example 3
一种低温合成纳米碳化硅的方法，包括以下步骤：A method for synthesizing nanometer silicon carbide at low temperature, including the following steps:
1)将稻壳除杂、清洗、烘干，将得到的洁净稻壳置于马弗炉中，在空气气氛中以5℃/min升温至600℃，进行恒温热处理3h，得到稻壳热处理产物；1) Remove impurities from the rice husk, clean it, and dry it. Place the obtained clean rice husk in a muffle furnace, raise the temperature to 600°C at 5°C/min in an air atmosphere, and perform constant temperature heat treatment for 3 hours to obtain a rice husk heat treatment product. ;
2)将得到的稻壳热处理产物与NaCl和KCl组成的混合盐、Mg粉混合，在550℃、Ar气气氛中进行恒温3h热处理，得到热处理产物A。其中NaCl与KCl摩尔比为1:1；Mg粉与稻壳热处理产物的质量比1:0.9；Mg粉粒径为300目；稻壳热处理产物和Mg粉的总质量与NaCl和KCl混合盐的总质量比为1：2.8；2) Mix the obtained rice husk heat treatment product with a mixed salt composed of NaCl and KCl and Mg powder, and perform heat treatment at a constant temperature of 550°C in an Ar gas atmosphere for 3 hours to obtain heat treatment product A. The molar ratio of NaCl to KCl is 1:1; the mass ratio of Mg powder to rice husk heat treatment product is 1:0.9; the Mg powder particle size is 300 mesh; the total mass of rice husk heat treatment product and Mg powder and NaCl and KCl mixed salt The total mass ratio is 1:2.8;
3)将得到的热处理产物A置于浓度为10wt％盐酸中连续搅拌5h，随后经洗涤、分离、真空干燥，得到含微量氧和碳的纳米硅粉；3) Place the obtained heat treatment product A in hydrochloric acid with a concentration of 10wt% and stir continuously for 5 hours, followed by washing, separation, and vacuum drying to obtain nanosilica powder containing trace amounts of oxygen and carbon;
4)将得到的纳米硅粉与氧化石墨烯按硅、碳摩尔比1:1.5混合，球磨12h，得到Si/C复合材料；4) Mix the obtained nano-silica powder and graphene oxide at a silicon to carbon molar ratio of 1:1.5, and ball-mill for 12 hours to obtain a Si/C composite material;
5)将得到的Si/C复合材料与300目Mg粉混合均匀，在550℃、Ar气气氛恒温5h，得到热处理产物B；5) Mix the obtained Si/C composite material with 300 mesh Mg powder evenly, and heat it at a constant temperature of 550°C and Ar gas atmosphere for 5 hours to obtain heat treatment product B;
6)将得到的热处理产物B在浓度为15wt％盐酸中连续搅拌3h，经洗涤、分离和真空干燥，得到纳米碳化硅粉体。产率(以煅烧后SiO2计算)为97.9％。6) The obtained heat-treated product B was continuously stirred in hydrochloric acid with a concentration of 15wt% for 3 hours, washed, separated and vacuum dried to obtain nanometer silicon carbide powder. The yield (calculated as SiO2 after calcination) is 97.9%.
以上公开的本发明优选实施例只是用于帮助阐述本发明。优选实施例并没有详尽叙述所有的细节，也不限制该发明仅为具体实施方式。显然，根据本说明书的内容，可作很多的修改和变化。本说明书选取并具体描述这些实施例，是为了更好地解释本发明的原理和实际应用，从而使所属技术领域技术人员能很好地理解和利用本发明。本发明仅受权利要求书及其全部范围和等效物的限制。The preferred embodiments of the invention disclosed above are only intended to help illustrate the invention. The preferred embodiments do not describe all details, nor do they limit the invention to specific implementations. Obviously, many modifications and variations are possible in light of the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, so that those skilled in the art can better understand and utilize the present invention. The invention is limited only by the claims and their full scope and equivalents.
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