WO2023115762A1 - 一种感应等离子热解硅烷制备纳米硅粉的方法 - Google Patents

一种感应等离子热解硅烷制备纳米硅粉的方法 Download PDF

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WO2023115762A1
WO2023115762A1 PCT/CN2022/087241 CN2022087241W WO2023115762A1 WO 2023115762 A1 WO2023115762 A1 WO 2023115762A1 CN 2022087241 W CN2022087241 W CN 2022087241W WO 2023115762 A1 WO2023115762 A1 WO 2023115762A1
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gas
silicon powder
silane
temperature
nano
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PCT/CN2022/087241
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English (en)
French (fr)
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秦海青
张振军
唐慧杰
刘文平
雷晓旭
卢安军
肖乐银
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中国有色桂林矿产地质研究院有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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

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  • the invention relates to the technical field of material chemistry, in particular to a method for preparing nano silicon powder by induction plasma pyrolysis of silane.
  • nano silicon powder can effectively improve the capacity and effective service life of lithium-ion batteries, and control the expansion rate of negative electrode materials within an acceptable range.
  • nano silicon powder also has broad application prospects in other fields.
  • nano-silicon powder and diamond are mixed under high pressure to form silicon carbide, which is often used as abrasives, grinding tools, and cutting tools; nano-silicon powder can react with organic matter and be used as a raw material for organosilicon polymer materials.
  • the methods for preparing nano silicon powder include mechanical ball milling method, chemical vapor deposition method, molten salt electrolysis method, plasma evaporation condensation method and so on.
  • the mechanical ball milling method generally uses zirconia as the grinding medium to grind silicon particles with large particle size into silicon powder with a small size.
  • the advantage is that the steps are simple and the cost is relatively low.
  • the obtained silicon powder has high impurity content, and it is difficult to control the particle shape and particle size range, and it is difficult to obtain nano-scale products.
  • the chemical vapor deposition method is to obtain nano silicon powder by heating silane in an atmosphere diluted with high-purity hydrogen until it is decomposed, and then cooled.
  • the size of silicon particles prepared by electrolysis of SiO 2 with anhydrous CaCl 2 as electrolyte by molten salt electrolysis method is not uniform, and it is difficult to control the further growth of silicon particles.
  • the plasma evaporation and condensation method usually uses micron-sized silicon powder as the raw material, uses DC arc plasma as the heat source to vaporize the silicon raw material instantly, and then cools the silicon vapor to prepare nano-silicon powder.
  • the thermal coupling efficiency between the raw material powder and the plasma is low, and it is difficult to guarantee the purity and yield of the product.
  • the present invention provides a method for preparing nano silicon powder by induction plasma pyrolysis of silane.
  • a method for preparing nano-silicon powder by induction plasma pyrolysis of silane comprising the following steps: exciting a working gas in an induction plasma reactor to form a stable high-temperature plasma, mixing gas silane and diluent gas into the high-temperature plasma thermal field, The gas silane decomposes under the joint action of the hot air flow of the high-temperature plasma thermal field and the high-temperature circulating cooling air flow, and the silicon atoms or silicon ions generated by pyrolysis condense into nano-scale spherical silicon powder after cooling; In the collection chamber of the device, after passing through the filter, the nano-silicon powder is deposited on the surface of the filter, and then blows down through the periodic back-blowing airflow to collect the nano-silicon powder.
  • the working gas is passed into the plasma reactor, and a stable high-temperature plasma with a predetermined power is formed after being excited.
  • the compressor is used to feed high-temperature circulating cooling air into the first-level high-temperature cooling area, and the second-level low-temperature cooling area is fed into low-temperature Circulating cooling air flow and nitrogen cooling air flow;
  • the silicon powder cooled by the secondary low-temperature cooling area is carried to the collection chamber by the mixed air flow, the gas passes through the filter in the collection chamber and is partially emptied after treatment, and the remaining gas is recycled as circulating cooling gas, and the nano-silicon powder is collected.
  • the filter blocks and adheres to the surface of the filter, and is blown off by the periodic back-blowing airflow, and the nano-silica powder is collected.
  • the working gas includes central gas and sheath gas.
  • the central gas is argon with a flow rate of 5-100 slpm;
  • the sheath gas is a mixed gas of argon and hydrogen, the flow rate of argon in the sheath gas is 20-250 slpm, and the flow rate of hydrogen in the sheath gas is 0-30 slpm.
  • the beneficial effect of adopting the above further solution is that introducing an appropriate amount of hydrogen into the sheath gas can effectively increase the thermal conductivity of the plasma hot gas flow, thereby improving the heating efficiency of the plasma thermal field.
  • the power of the plasma reactor in step (2) is 15-80kw; the working pressure of the system is 14-17Psig.
  • the beneficial effect of adopting the above-mentioned further solution is that: setting the system working pressure to approximately equal to one atmospheric pressure can reduce the airtightness requirements of the system, and also reduce the possibility of causing fire and explosion hazards when the system has a large leakage .
  • the high-temperature circulating cooling airflow is a mixed gas of nitrogen, argon and hydrogen; the temperature of the high-temperature circulating cooling airflow is 420-650°C, and the flow rate is 1000-3000 slpm
  • the volume ratio of nitrogen, argon and hydrogen in the mixed gas of the high-temperature circulating cooling air flow is: 50% nitrogen, 40% argon, and 10% hydrogen.
  • the low-temperature circulating cooling airflow is a mixed gas of nitrogen, argon and hydrogen; the temperature of the low-temperature circulating cooling airflow is 18-35°C, and the flow rate is 5000-15000 slpm; the flow rate of the nitrogen cooling airflow is 150-450 slpm.
  • the volume ratio of nitrogen, argon and hydrogen in the mixed gas of the low-temperature circulating cooling airflow is: 50% nitrogen, 40% argon, and 10% hydrogen.
  • the beneficial effect of adopting the above-mentioned further solution is that: using relatively cheap nitrogen as the main cooling gas can effectively reduce the production cost; meanwhile, nitrogen has a high specific heat capacity and can effectively improve the cooling efficiency.
  • Using a circulating cooling air flow with a higher temperature (higher than the pyrolysis temperature of silane gas) as the primary cooling can cool silicon atoms or silicon ions to form silicon particles, and at the same time provide energy for a small amount of unreacted silane gas as a supplementary heat source And reaction atmosphere, greatly improve the thermal decomposition rate of silane gas (greater than 99%).
  • the ultra-large flow rate of low-temperature circulating gas is used as the secondary cooling, which can effectively control the further growth of silicon particles generated by the reaction, and as the main cooling method, the temperature of the gas in the system can be controlled within a lower range, which can effectively avoid powder Interference in the cooling process to achieve the purpose of long-term stable operation.
  • the flow rate of the gas silane gas flow is 15-120 slpm; the dilution gas flow is argon, and the flow rate is 50-200 slpm.
  • the beneficial effect of adopting the above-mentioned further scheme is that: using silane as the raw material gas, the molecular level contact between the raw material and the plasma thermal field can be realized, and the thermal coupling efficiency can be improved; The production of micron-sized large particles formed by vaporization.
  • the introduction of the dilute airflow can restrict the flow direction of the silane gas and prevent it from escaping before it is injected into the high-temperature thermal field; at the same time, the dilute airflow can initially dilute the silane gas before injection, which helps to produce nano-silicon powder products with smaller particle sizes .
  • the backflush gas is argon or nitrogen.
  • the beneficial effect of adopting the above further scheme is that the backflushing step can be completed without introducing more kinds of gases by using argon or nitrogen as the backflushing gas, thereby reducing the complexity of the process conditions.
  • the beneficial effect of the present invention is that: the present invention uses silane gas as raw material, induction plasma as main heat source, common electric heating tube as auxiliary heat source, and adopts multi-stage reaction and multi-stage cooling to prepare nano-silicon powder.
  • the method has the advantages of high silane decomposition rate, high safety and continuous production.
  • the invention uses induction plasma as the main heat source, which can realize the centralized heating of the raw material gas under the condition of zero contact between the material and the equipment, without introducing electrode pollution, which helps to improve the purity of the product; it can avoid the sticky powder generated by the reaction during the heating process Covering the surface of the heating device, the heating efficiency is improved, the equipment maintenance cost is reduced, and it is beneficial to industrial continuous production.
  • the invention uses silane gas as a raw material, which can realize the molecular-level contact between the raw material and the plasma hot gas flow, greatly improves the thermal coupling efficiency, and improves the energy utilization rate.
  • silane gas as a raw material can avoid the generation of micron-sized large particles due to incomplete vaporization of coarse silicon powder during production, which is conducive to improving the quality of nano-silicon powder products in terms of particle size.
  • an ordinary electric heating tube is used as an auxiliary heat source, combined with an induction plasma heat source, innovatively introducing a multi-stage reaction and multi-stage cooling mode, giving full play to the advantages of the two heating modes, and greatly improving the pyrolysis of silane gas Rate.
  • the pyrolysis rate of silane can reach more than 99%, which can effectively improve the utilization rate of silane gas, reduce the environmental protection cost of tail gas treatment, and further achieve the purpose of reducing production cost.
  • the working gas is recycled and used as a super-large flow cooling air flow, which can not only effectively control the particle size of the nanoparticles, but also reduce the amount of working gas and save costs.
  • the large flow of working gas can dilute the total concentration of hydrogen and silane in the system to less than 10%, which greatly reduces the possibility of dangerous system leakage in extreme cases.
  • the present invention adopts a feeding probe with a double-layer coaxial tube structure for feeding, and the silane gas is directly injected into the high-temperature plasma thermal field under the argon gas curtain wrapping, which can prevent the silane gas from escaping before entering the plasma thermal field, and can also utilize the argon
  • the preliminary dilution of the silane gas by the gas helps to improve the heating efficiency and reduce the particle size of the nano silicon powder.
  • the present invention adopts a long cylindrical filter group made of porous metal ceramics for gas-solid separation, and uses periodic back-blowing airflow to back-blow the filters one by one, which can achieve higher filtration efficiency and better efficiency than traditional bag collectors. Long service life can realize continuous production for a long time.
  • the average particle size of the nano silicon powder prepared by the invention is adjustable from 30 to 120 nm, and has the characteristics of high purity, narrow distribution, spherical shape, easy dispersion, good fluidity, large specific surface area and high surface activity.
  • the present invention also provides a device for preparing nano-silicon powder by induction plasma pyrolysis of silane, including a plasma generator, a feeding probe, a primary high-temperature cooling zone, a secondary low-temperature cooling zone, a collection chamber, a filter, a compressor, an electric heating Tube, water-cooled heat exchanger, exhaust gas treatment device.
  • the ion generator and the feeding probe are all fixed in the first-level high-temperature cooling area, and the second-level low-temperature cooling area is fixed at the bottom of the first-level high-temperature cooling area;
  • One side of the collection chamber at the bottom of the area communicates; the other side of the collection chamber communicates with the water-cooled heat exchanger;
  • a compressor is arranged between the collection chamber and the water-cooled heat exchanger, and the compressor and water
  • An electric heating pipe is arranged between the cold and heat exchangers;
  • an exhaust gas treatment device is arranged between the compressor and the collection chamber;
  • the surface of the first-level high-temperature cooling area is provided with a high-temperature circulating cooling air inlet;
  • the second-level low-temperature cooling area is provided with a low-temperature circulating cooling air inlet, and the low-temperature circulating cooling air inlet is also provided with nitrogen cooling. air inlet;
  • a powder collection tank is arranged at the bottom of the collection chamber, and a filter is arranged inside the collection chamber.
  • the structure of the feeding probe is a double-layer coaxial tube, the inner tube is a silane gas channel, and the interlayer between the inner and outer tubes is a dilution gas flow channel.
  • the inner tube is a silane gas channel
  • the interlayer between the inner and outer tubes is a dilution gas flow channel.
  • the filter is made of porous cermet, and the shape of the filter is long cylinder.
  • Fig. 1 is the schematic flow diagram of the device structure and method for preparing nano-silicon powder by induction plasma pyrolysis of silane in the present invention
  • the labels in the figure are: 1-induction plasma generator, 2-central gas, 3-sheath gas, 4-feeding probe, 5-silane air flow, 6-dilution air flow, 7-first-level high temperature cooling area, 8-secondary Low-temperature cooling area, 9-high-temperature circulating cooling air inlet, 10-low-temperature circulating cooling air inlet, 11-nitrogen cooling air inlet, 12-collection chamber, 13-filter, 14-powder collection tank, 15 -Compressor, 16-Electric heating tube, 17-Water-cooled heat exchanger, 18-Tail gas treatment device.
  • Fig. 2 is an electron micrograph of the nano-silicon powder sample prepared in Example 1 of the present invention.
  • Fig. 3 is an electron micrograph of a nano-silicon powder sample prepared in Example 2 of the present invention.
  • the purity of silane used in the embodiment of the present invention is 99.9999%, the purity of hydrogen is 99.999%, the purity of argon is 99.999%, and the purity of nitrogen is >99.99%.
  • Preparation process flush the system with argon gas at a flow rate of 300 slpm for 10 minutes, and perform leak detection.
  • the process of leak detection is divided into high-level leak detection and low-pressure leak detection.
  • the passing standards are: when the system is at a high pressure of 18psi, the leak rate is not higher than 5slpm; when the system is at a low pressure of 2psi, the leak rate is not higher than 2slpm.
  • 30 slpm central gas (argon) and sheath gas a mixture of 90 slpm argon and 10 slpm hydrogen
  • Reaction process A total of 30 slpm of silane gas flow is passed into the inner tube feeding the three feeding probes, and a total of 90 slpm of argon gas is passed into the interlayer between the inner and outer tubes as a dilution gas flow.
  • Silane gas is directly injected into the plasma hot gas flow with a core temperature as high as 10,000°C under the wrapping and dilution of argon gas, and is rapidly decomposed into atomic or ion silicon and hydrogen.
  • silicon atoms or ions After passing through the first-level high-temperature cooling zone, silicon atoms or ions are rapidly cooled to form tiny silicon particles.
  • a small amount of undecomposed silane gas is further pyrolyzed in this area to generate tiny silicon particles and hydrogen gas.
  • the mixed gas flow carries the silicon powder into the secondary low-temperature cooling area, and the temperature of the gas and silicon powder drops sharply below 200°C after cooling.
  • the silicon powder generated in the reaction area is carried to the collection chamber by the airflow. Among them, after the gas passes through multiple filters suspended in the collection chamber, part of the gas is incinerated and washed by the tail gas treatment device, and then emptied; The first-level high-temperature cooling area, and the other part passes through the second-level low-temperature cooling area after being cooled by a water-cooled heat exchanger. Nano silicon powder is blocked by the filter and adheres to the surface of the filter. Using argon as the back-blowing air flow, the multiple filters are periodically back-flushed one by one, and the sticky nano-silica powder is blown down to the powder collection tank at the bottom of the collection chamber. The reaction process continued for 8 hours, and a total of 15.8 kg of nano-silicon powder was obtained by on-line replacement of the powder collection tank and collection after shutdown.
  • the nano-silicon powder obtained in this embodiment is light yellow powder, the BET average particle size is 61nm, and the particle shape is spherical or nearly spherical, as shown in FIG. 2 .
  • step 1) 40 slpm of central gas (argon) and sheath gas (a mixture of 120 slpm argon and 15 slpm hydrogen) were introduced into the induction plasma generator. Excite the induction plasma, adjust the system pressure to 14.7psi, and the power of the induction plasma generator 1 to 60kw. Then start the compressor, feed 1700slpm, 450°C high-temperature circulating cooling airflow to the primary high-temperature cooling area, and feed 7500slpm, 30°C low-temperature circulating cooling airflow and 300slpm nitrogen cooling airflow to the secondary low-temperature cooling area.
  • argon central gas
  • sheath gas a mixture of 120 slpm argon and 15 slpm hydrogen
  • step 2) a total of 60 lpm of silane gas flow is fed into the inner tube of the three feeding probes, and a total of 150 slpm of argon gas is fed into the interlayer between the inner and outer tubes as a dilution gas flow.
  • step 3 the reaction process continued for 24 hours, and a total of 86.2 kg of nano-silicon powder was obtained by on-line replacement of the powder collection tank 14 and collection after shutdown.
  • the nano-silicon powder obtained in this embodiment is a dark yellow powder, the BET average particle size is 98nm, and the particle shape is spherical or nearly spherical, as shown in FIG. 3 .

Abstract

本发明公开了一种感应等离子热解硅烷制备纳米硅粉的方法，步骤为：将工作气体在感应等离子反应器中激发形成稳定的高温等离子体，将气体硅烷与稀释气体混合注入高温等离子体热场中，气体硅烷在高温等离子体热场的热气流高温循环冷却气流的共同作用下分解，热解生成的硅原子经过冷却后凝结成纳米尺度的球形硅粉；裹挟硅粉的气流经过滤器过滤，纳米硅粉沉积在过滤器表面，然后通过周期性反吹气流吹落，收集得到纳米硅粉。本发明以硅烷气体作为原料，采用感应等离子体作为主要热源，普通加热管为辅助热源，具有热分解率高、无电极污染、可长时间连续生产的优点。所制备的纳米硅粉纯度高、球形度高、粒度分布窄、流动性好，具备很高的品质。

Description

一种感应等离子热解硅烷制备纳米硅粉的方法 技术领域
本发明涉及材料化学技术领域，具体的说涉及一种感应等离子热解硅烷制备纳米硅粉的方法。
背景技术
随着新能源相关产业的兴起和3C电子产品的普及，人们对锂离子电池提出来更高的要求——更大的体积/质量比能量密度、更快得充放电速率、更高的安全性。硅材料以其约10倍于石墨的能量密度，成为锂离子电池负极材料的有力竞争者。但是硅用作负极材料也有一个相当严重的缺陷，它在嵌锂后会膨胀至原体积的约3倍尺寸，制约了其在该领域的应用。纳米硅粉因其所具备的纳米效应，可以有效的降低这一负面效应。将纳米硅粉表面包碳与石墨混合使用，可有效的提升锂离子电池的容量和有效使用寿命，并将负极材料的膨胀率控制在可接受的范围之内。另外，纳米硅粉在其它领域也有着广泛的应用前景。比如，纳米硅粉与金刚石高压下混合形成碳化硅，常用作磨料、磨具、切削工具；纳米硅粉可与有机物反应，作为有机硅高分子材料的原料。
目前制备纳米硅粉的方法有机械球磨法、化学气相沉积法、熔盐电解法、等离子蒸发冷凝法等。机械球磨法一般以氧化锆为磨介，将粒径大的硅颗粒研磨成较小尺寸的硅粉，优点是步骤简单，成本相对比较低廉。但所得硅粉杂质含量高，颗粒形貌和粒径范围难以控制，且很难获得纳米级产品。化学气相沉积法是通过将硅烷在高纯氢稀释的气氛下加热至分解，然后冷却获得纳米硅粉。但制备过程中涉及高压力高浓度的氢气和硅烷，存在不小的安全隐患。熔盐电解法以无水CaCl 2为电解质电解SiO 2制备的硅颗粒大小不均，且难以控制硅颗粒进一步长大。等离子蒸发冷凝法通常采用微米级硅粉作为原料，利用直流电弧等离子体为热源将硅原料瞬间汽化，然后冷却硅蒸汽制备 纳米硅粉，制备过程中容易引入电极材料汽化后造成的污染，且微米级原料粉末与等离子体的热耦合效率低，难以保证产品的纯度和产率。
因此，提供一种硅烷分解率高、安全性强、可连续生产的感应等离子热解硅烷制备纳米硅粉的方法是本领域技术人员亟需解决的技术问题。
发明内容
有鉴于此，本发明提供了一种感应等离子热解硅烷制备纳米硅粉的方法。
为了实现上述目的，本发明采用如下技术方案：
一种感应等离子热解硅烷制备纳米硅粉的方法，包括以下步骤：将工作气体在感应等离子反应器中激发形成稳定的高温等离子体，将气体硅烷与稀释气体混合注入高温等离子体热场中，气体硅烷在高温等离子体热场的热气流高温循环冷却气流的共同作用下分解，热解生成的硅原子或硅离子经过冷却后凝结成纳米尺度的球形硅粉；裹挟硅粉的气流进入含有过滤器的收集室中，透过过滤器后，纳米硅粉沉积在过滤器表面，然后通过周期性反吹气流吹落，收集得到纳米硅粉。
进一步，上述方法具体包括以下步骤：
(1)利用氩气或氮气对整个热解系统进行冲洗并检漏；
(2)将工作气体通入至等离子反应器中，经激发形成预定功率的稳定的高温等离子体，采用压缩机对一级高温冷却区域通入高温循环冷却气流，二级低温冷却区域通入低温循环冷却气流和氮气冷却气流；
(3)采用送料探针将气体硅烷在稀释气流包裹下注入高温等离子体热场中，硅烷在高温等离子体热场中分解，然后一级高温冷却区域，热解生成的硅原子或硅离子冷却形成微小的硅粉，同时，未分解的硅烷气体会进一步热解并生成硅粉和氢气，硅粉被混合气流携带至二级低温冷却区域，进行进一步冷却；
(4)被二级低温冷却区域冷却的硅粉被混合气流携带至收集室，气体透过收集室的过滤器后部分经处理后排空，剩余气体作为循环冷却气体循环利用，纳米硅粉被过滤器阻挡并粘附在过滤器表面，被周期性反吹气流吹落，收集得到纳米硅粉。
进一步，所述工作气体包括中心气和鞘气。
更进一步，所述中心气为氩气，流量为5～100slpm；所述鞘气为氩气和氢气的混合气体，鞘气中氩气流量为20～250slpm，鞘气中氢气流量0～30slpm。
采用上述进一步方案的有益效果在于：在鞘气中引入适当量的氢气可以有效的提升等离子热气流的热传导率，进而提高等离子热场的加热效率。
进一步，步骤(2)中所述等离子反应器的功率为15～80kw；系统工作压力为14～17Psig。
采用上述进一步方案的有益效果在于：将系统工作压力设定为约等于一个大气压，可以降低对系统的气密性要求，同时也降低了在系统发生较大泄漏时引发起火、爆炸危险的可能性。
进一步，所述高温循环冷却气流为氮气、氩气和氢气混合气体；高温循环冷却气流的温度为420～650℃，流量为1000～3000slpm
更进一步，高温循环冷却气流的混合气体中氮气、氩气和氢气体积比为：氮气50％，氩气40％，氢气10％。
更进一步，所述低温循环冷却气流为氮气、氩气和氢气的混合气体；低温循环冷却气流的温度为18～35℃，流量为5000～15000slpm；所述氮气冷却气流流量为150～450slpm。
更进一步，低温循环冷却气流的混合气体中氮气、氩气和氢气体积比为：氮气50％，氩气40％，氢气10％。
采用上述进一步方案的有益效果在于：采用价格相对低廉的氮气作为主要冷却气体，可以有效的降低制备成本；同时，氮气具有较高的比热容，可 以有效的提升冷却效率。采用较高温度(高于硅烷气体的热解温度)的循环冷却气流作为一级冷却，可以在将硅原子或硅离子冷却生成硅颗粒的同时，作为补充热源为少量未反应的硅烷气体提供能量和反应气氛，极大的提升硅烷气体的热分解率(大于99％)。采用超大流量的低温循环气体作为二级冷却，可有效的控制反应生成的硅颗粒进一步长大，并作为主要冷却手段将系统内的气体温度控制在较低的范围内，可以有效的避免粉体对冷却过程中的干扰，达到长时间稳定运行的目的。
进一步，所述气体硅烷气流流量为15～120slpm；所述稀释气流为氩气，流量为50～200slpm。
采用上述进一步方案的有益效果在于：以硅烷作为原料气体，可以实现原料与等离子热场分子级的接触，提高热耦合效率；同时，可以避免以粗硅粉为原料生产时由于粗硅粉不完全汽化而形成的微米级大颗粒的产生。引入稀释气流可以约束硅烷气体的流向，避免其在注入高温热场之前发生逸散；同时，稀释气流可以将硅烷气体在注入前进行初步稀释，有助于生成更小粒径的纳米硅粉产品。
进一步，所述反吹气体为氩气或氮气。
采用上述进一步方案的有益效果在于：以氩气或氮气作为反吹气体可以在不引入更多种类气体的前提下完成反吹步骤，降低工艺条件的复杂性。
本发明的有益效果在于：本发明以硅烷气体作为原料，以感应等离子体为主要热源，以普通电加热管为辅助热源，采用多级反应和多级冷却的方式制备纳米硅粉。该方法具有硅烷分解率高、安全性强、可连续生产的优点。
本发明采用感应等离子体作为主要热源，可以实现物料与设备零接触的条件下对原料气体进行集中加热，不会引入电极污染，有助于提高产品纯度；可以避免加热过程中反应生成的粉末粘覆在加热器件表面，提高加热效率，降低设备维护成本，有利于工业化连续生产。
本发明以硅烷气体作为原料，可以实现原料与等离子热气流之间分子级的接触，极大的提升热耦合效率，提高能源利用率。同时，以硅烷气体作为原料可以避免以粗硅粉为原料生产时由于粗硅粉不完全汽化而形成的微米级大颗粒的产生，有利于提高纳米硅粉产品在粒度方面的品质。
本发明中以普通电加热管为辅助热源，与感应等离子热源相结合，创新性引入多级反应和多级冷却模式，充分发挥两种加热模式的优势，极大的提升的硅烷气体的热解率。采用本发明所述方法，硅烷的热解率可达99％以上，可以有效的提高硅烷气体的利用率，并降低尾气处理的环保成本，进而达到降低生产成本的目的。
本发明的制备过程中约有90％的工作气体被循环利用，用作超大流量的冷却气流，既可以有效控制纳米颗粒的粒径大小，又可以减少工作气体的用量，节约成本。同时，较大流量的工作气体可以将系统内的氢气和硅烷总浓度稀释至10％以下，极大的降低了极端情况下系统泄漏发生危险的可能性。
本发明采用双层同轴管结构的送料探针进行送料，硅烷气体在氩气气幕包裹下直接注入高温等离子热场，既可以防止硅烷气体在进入等离子热场前逸散，又可以利用氩气对硅烷气体进行初步稀释，有助于提高加热效率和降低纳米硅粉粒度。
本发明采用材质为多孔金属陶瓷的长筒状过滤器组进行气固分离，并用周期性的反吹气流对过滤器逐个反吹，可以达到相较于传统布袋收集器更高的过滤效率和更长的使用周期，可实现长时间连续生产。
本发明所制备的纳米硅粉的平均粒度在30～120nm可调，且具备高纯度、分布窄、球形状、易分散、流动性好、比表面积大和表面活性高的特点。
本发明还提供了上述感应等离子热解硅烷制备纳米硅粉的装置，包括等离子发生器、送料探针、一级高温冷却区域、二级低温冷却区、收集室、过滤器、压缩机、电加热管、水冷热交换器、尾气处理装置。
其中，所述离子发生器和所述送料探针均固定在所述一级高温冷却区域，所述二级低温冷却区域固定在所述一级高温冷却区域的底端；所述二级低温冷却区域的底端收集室的一侧连通；所述收集室的另一侧与水冷热交换器连通；所述收集室和水冷热交换器之间设置有压缩机，所述压缩机和水冷热交换器之间设置有电加热管；所述压缩机和收集室之间设置有尾气处理装置；
所述一级高温冷却区域表面设有高温循环冷却气流进气口；所述二级低温冷却区域设有低温循环冷却气流进气口，且所述低温循环冷却气流进气口还设有氮气冷却气流进气口；
所述收集室的底端设置有收粉罐，所述收集室内部设有过滤器。
进一步，所述送料探针结构为双层同轴管，内管为硅烷气体通道，内外管间的夹层为稀释气流通道。所述送料探针设有3～4根。
进一步，收集室内的过滤器设有10～30根，所述过滤器的材质为多孔金属陶瓷，所述过滤器的形状为长筒型。
附图说明
图1为本发明感应等离子热解硅烷制备纳米硅粉的装置结构和方法流程示意图；
图中标号为：1-感应等离子发生器、2-中心气、3-鞘气、4-送料探针、5-硅烷气流、6-稀释气流、7-一级高温冷却区域、8-二级低温冷却区域、9-高温循环冷却气流进气口、10-低温循环冷却气流进气口、11-氮气冷却气流进气口、12-收集室、13-过滤器、14-收粉罐、15-压缩机、16-电加热管、17-水冷热交换器、18-尾气处理装置。
图2为本发明所述实施实例1所制备纳米硅粉样品的电镜图。
图3为本发明所述实施实例2所制备纳米硅粉样品的电镜图。
具体实施方式
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做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
在本发明实施例中所用硅烷纯度为99.9999％、氢气纯度为99.999％、氩气纯度为99.999％、氮气纯度为＞99.99％。
实施例1
1)准备过程：利用300slpm的流量的氩气对系统进行时长10min的冲洗，并进行检漏。检漏的过程分为高于检漏和低压检漏。通过标准分别为：系统在18psi的高压时，漏率不高于5slpm；系统在2psi的低压时，漏率不高于2slpm。向感应等离子发生器中通入30slpm的中心气(氩气)和鞘气(为90slpm氩气和10slpm氢气的混合气)。激发感应等离子体，调节系统压力至14.5psi，感应等离子发生器功率至40kw。然后启动压缩机，向一级高温冷却区域通入1500slpm、430℃的高温循环冷却气流，向二级低温冷却区域通入6500slpm、28℃的低温循环冷却气流和250slpm的氮气冷却气流。
2)反应过程：向送3个送料探针的内管通入共计30slpm的硅烷气流，内外管间的夹层通入共计90slpm的氩气作为稀释气流。硅烷气体在氩气的包裹和稀释下直接注入核心温度高达10000℃的等离子热气流中，急速分解为原子态或离子态的硅和氢。经过一级高温冷却区域时，硅原子或离子快速冷却形成微小的硅粒。同时，未分解的少量硅烷气体在这一区域进一步热解并生成微小的硅粒和氢气。然后，混合气流携带着硅粉进入二级低温冷却区域，经冷却后气体和硅粉的温度骤降至200℃以下。
3)收集过程：在反应区域生成的硅粉被气流携带至收集室。其中，气体透过收集室内悬挂的多个过滤器后，一部分经过尾气处理装置进行焚烧、洗涤后排空；剩余的气体经压缩机加压后循环利用，一部分经电加热管加热后通入一级高温冷却区域，另一部分经水冷热交换器冷却后通入二级低温冷却 区域。纳米硅粉被过滤器阻挡并粘附在过滤器表面。采用氩气作为反吹气流，周期性对多个过滤器进行逐个反吹，将粘覆的纳米硅粉吹落至收集室底部的收粉罐中。反应过程持续8小时，通过在线更换收粉罐和停机后收集共获得纳米硅粉15.8kg。
本实施实例中所得纳米硅粉为淡黄色粉末，BET平均粒度为61nm，颗粒形貌为球形或近球形，如图2所示。
实施实例2
重复实施实例1，不同的是：
步骤1)中，向感应等离子发生器中通入40slpm的中心气(氩气)和鞘气(为120slpm氩气和15slpm氢气的混合气)。激发感应等离子体，调节系统压力至14.7psi，感应等离子发生器1功率至60kw。然后启动压缩机，向一级高温冷却区域通入1700slpm、450℃的高温循环冷却气流，向二级低温冷却区域通入7500slpm、30℃的低温循环冷却气流和300slpm的氮气冷却气流。
步骤2)中，向送3个送料探针的内管通入共计60lpm的硅烷气流，内外管间的夹层通入共计150slpm的氩气作为稀释气流。
步骤3)中，反应过程持续24小时，通过在线更换收粉罐14和停机后收集共获得纳米硅粉86.2kg。
本实施实例中所得纳米硅粉为暗黄色粉末，BET平均粒度为98nm，颗粒形貌为球形或近球形，如图3所示。
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。

Claims (9)

  1. 一种感应等离子热解硅烷制备纳米硅粉的方法，其特征在于，包括以下步骤：将工作气体在感应等离子反应器中激发形成稳定的高温等离子体，将气体硅烷与稀释气体混合注入高温等离子体热场中，气体硅烷在高温等离子体热场的热气流高温循环冷却气流的共同作用下分解，热解生成的硅原子或硅离子经过冷却后凝结成纳米尺度的球形硅粉；裹挟硅粉的气流进入含有过滤器的收集室中，经过滤器过滤后，纳米硅粉沉积在过滤器表面，然后通过周期性反吹气流吹落，收集得到纳米硅粉。
  2. 根据权利要求1所述一种感应等离子热解硅烷制备纳米硅粉的方法，其特征在于，具体包括以下步骤：
    (1)利用氩气或氮气对整个热解系统进行冲洗并检漏；
    (2)将工作气体通入至等离子反应器中，经激发形成预定功率的稳定的高温等离子体，采用压缩机对一级高温冷却区域通入高温循环冷却气流，二级低温冷却区域通入低温循环冷却气流和氮气冷却气流；
    (3)采用送料探针将气体硅烷在稀释气流包裹下注入高温等离子体热场中，硅烷在高温等离子体热场中分解，然后一级高温冷却区域，热解生成的硅原子或硅离子冷却形成微小的硅粉，同时，未分解的硅烷气体会进一步热解并生成硅粉和氢气，硅粉被混合气流携带至二级低温冷却区域，进行进一步冷却；
    (4)被二级低温冷却区域冷却的硅粉被混合气流携带至收集室，气体透过收集室的过滤器后，纳米硅粉被过滤器阻挡并粘附在过滤器表面，被周期性反吹气流吹落，收集得到纳米硅粉。
  3. 根据权利要求2所述一种感应等离子热解硅烷制备纳米硅粉的方法，其特征在于，所述工作气体包括中心气和鞘气。
  4. 根据权利要求3所述一种感应等离子热解硅烷制备纳米硅粉的方法，其特征在于，所述中心气为氩气，流量为5～100slpm；所述鞘气为氩气和氢气的混合气体，鞘气中氩气流量为20～250slpm，鞘气中氢气流量0～30slpm。
  5. 根据权利要求2所述一种感应等离子热解硅烷制备纳米硅粉的方法，其特征在于，步骤(2)中所述等离子反应器的功率为15～80kw；系统工作压力为14～17Psig。
  6. 根据权利要求2所述一种感应等离子热解硅烷制备纳米硅粉的方法，其特征在于，所述高温循环冷却气流为氮气、氩气和氢气混合气体；高温循环冷却气流的温度为420～650℃，流量为1000～3000slpm
  7. 根据权利要求2所述一种感应等离子热解硅烷制备纳米硅粉的方法，其特征在于，所述低温循环冷却气流为氮气、氩气和氢气的混合气体；低温循环冷却气流的温度为18～35℃，流量为5000～15000slpm；所述氮气冷却气流流量为150～450slpm。
  8. 根据权利要求2所述一种感应等离子热解硅烷制备纳米硅粉的方法，其特征在于，所述气体硅烷气流流量为15～120slpm；所述稀释气流为氩气，流量为50～200slpm。
  9. 根据权利要求2所述一种感应等离子热解硅烷制备纳米硅粉的方法，其特征在于，所述反吹气体为氩气或氮气。
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070172406A1 (en) * 2003-11-19 2007-07-26 Degussa Ag Nanoscale, crystalline silicon powder
CN103936009A (zh) * 2014-04-21 2014-07-23 浙江中宁硅业有限公司 一种硅烷热分解生产纳米级高纯硅粉的装置及方法
CN106185947A (zh) * 2016-07-21 2016-12-07 中国有色桂林矿产地质研究院有限公司 一种纳米硅粉的制备方法
US20160362302A1 (en) * 2013-11-25 2016-12-15 Korea Institute Of Energy Research Apparatus for producing silicon nanoparticle using inductive coupled plasma
CN106698437A (zh) * 2017-01-03 2017-05-24 昆明理工大学 一种利用热等离子法制备球形纳米硅的方法
CN108101061A (zh) * 2017-11-22 2018-06-01 合肥开尔纳米能源科技股份有限公司 纳米硅粉的制备方法
CN114031082A (zh) * 2021-12-22 2022-02-11 中国有色桂林矿产地质研究院有限公司 一种感应等离子热解硅烷制备纳米硅粉的方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07161646A (ja) * 1993-12-13 1995-06-23 Nec Corp 多結晶膜作成方法
CN102153087B (zh) * 2010-12-24 2013-01-23 上海普罗新能源有限公司 双室单联真空循环脱气炉及太阳能级多晶硅的制备
CN102320606B (zh) * 2011-07-20 2012-10-31 河北大学 一种生长纳米晶硅粉体的方法
CN110156022A (zh) * 2019-07-06 2019-08-23 金雪莉 一种宏量制备硅纳米材料的方法及装置
CN111261864A (zh) * 2020-02-10 2020-06-09 马鞍山科达普锐能源科技有限公司 一种锂离子电池用硅碳负极材料及其制备方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070172406A1 (en) * 2003-11-19 2007-07-26 Degussa Ag Nanoscale, crystalline silicon powder
US20160362302A1 (en) * 2013-11-25 2016-12-15 Korea Institute Of Energy Research Apparatus for producing silicon nanoparticle using inductive coupled plasma
CN103936009A (zh) * 2014-04-21 2014-07-23 浙江中宁硅业有限公司 一种硅烷热分解生产纳米级高纯硅粉的装置及方法
CN106185947A (zh) * 2016-07-21 2016-12-07 中国有色桂林矿产地质研究院有限公司 一种纳米硅粉的制备方法
CN106698437A (zh) * 2017-01-03 2017-05-24 昆明理工大学 一种利用热等离子法制备球形纳米硅的方法
CN108101061A (zh) * 2017-11-22 2018-06-01 合肥开尔纳米能源科技股份有限公司 纳米硅粉的制备方法
CN114031082A (zh) * 2021-12-22 2022-02-11 中国有色桂林矿产地质研究院有限公司 一种感应等离子热解硅烷制备纳米硅粉的方法

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