CN109860548B - Preparation method and application of nano silicon material - Google Patents
Preparation method and application of nano silicon material Download PDFInfo
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Abstract
The invention discloses a preparation method of a nano silicon material, which comprises the following steps: (1) grinding the coarse silicon slurry to obtain micron-sized silicon powder slurry; (2) adding a carbon material into the micron-sized silicon powder slurry for grinding to obtain a nanoscale silicon powder slurry; (3) and drying, crushing, sieving and demagnetizing the nano-scale silicon powder slurry to obtain the nano-silicon material. In the preparation method, the carbon material is added as a grinding medium, so that on one hand, the grinding of particles is promoted to be finer; on the other hand, the carbon material replaces the traditional dispersing agent, so that the hard agglomeration phenomenon among the nano silicon particles is effectively avoided, the residual of the dispersing agent is reduced, the conductivity of the material is effectively improved, and the electrochemical performance of the material is further improved.
Description
Technical Field
The invention belongs to the field of preparation of nano powder, and particularly relates to a preparation method of a nano silicon material applied to a lithium ion battery cathode material.
Background
At present, the commercial lithium ion battery cathode material is mainly made of graphite, the theoretical specific capacity is 372mAh/g, the development capacity of 350-360mAh/g in the prior art is close to the theoretical value, and the development potential is limited. In addition, the aim of realizing the specific energy of the single battery more than or equal to 300Wh/kg is clearly provided by the four departments in the scheme for promoting the development action of the automobile power battery industry, and the requirement cannot be met by adopting a graphite cathode, so that the development of a novel cathode material with high specific capacity is particularly critical.
The silicon material has the advantages of high lithium storage capacity (the theoretical specific capacity is 4200mAh/g), low discharge platform, rich storage capacity and the like, and becomes a breakthrough for solving the target of 300 Wh/kg. However, the problems of low first efficiency and poor cyclicity in the charging and discharging process become stumble stones which hinder the industrial application of silicon materials: the silicon material has a larger expansion rate (more than 300%) in the charging and discharging processes, which leads to pulverization of silicon particles and continuous generation and consumption of SEI film, thereby leading to continuous performance attenuation; as a semiconductor material, the electronic conductivity and the ionic conductivity of the material are relatively low, and the material cannot meet the related requirements of a power battery.
In order to solve the above problems, the silicon material is mainly subjected to nanocrystallization, alloying, cladding, and the like. The nano-crystallization is used for preparing a nano-sized silicon material, and is the first step of synthesis and preparation of a silicon-carbon material; the nano silicon with smaller size can greatly reduce the volume expansion rate in the charging and discharging process, improve the expansion resistance of the material and reduce the adverse effect in the charging and discharging process. At present, the methods for preparing the silicon material with the nanometer size mainly comprise a mechanical grinding method, a vapor deposition method, a hydrothermal synthesis method, a sol-gel method, a thermal reduction method and the like. The above methods are superior and inferior, and among them, the mechanical grinding method is favored by many technical developers because of its simple equipment and process, low cost, and easy mass production. However, the process method has the following technical difficulties: the specific surface area of the nano silicon is large, so that the agglomeration phenomenon is serious; in the preparation process, air is frequently contacted, so that nano silicon particles are easily oxidized to generate silicon dioxide, and the activity of silicon is reduced; although the agglomeration problem can be solved by adding auxiliary materials or dispersing agents, other impurities are easily introduced to reduce the material performance; in addition, when the particle size of the nano-silicon is less than or equal to 150nm, the residual organic solvent is easily oxidized or even ignited at normal temperature, so that potential safety hazards are brought to storage of the nano-silicon, and the problem can be solved by oxidation to a certain degree, so that effective regulation and control of the degree of oxidation becomes another bottleneck of synthetic preparation. For example, patent document CN 105655570a discloses a method for refining nano-scale silicon powder material, in which after a dispersing agent is added, nano-scale silicon powder with a particle size of 50-500nm is obtained by high-speed grinding, and this method can realize precise control of particle size, but can prepare uniformly dispersed nano-scale silicon powder, in which the mass ratio of the added dispersing agent is 10% -20%, and related dispersing agents are not removed in the patent, which greatly reduces the performance of the material battery and limits the application of nano-scale preparation. Patent document CN 107311181a discloses a method for preparing high-purity nano silicon particles from industrial silicon silica fume. The method uses collected industrial silicon ash as a raw material, and obtains nano silicon particles with the particle size of 100nm through acid washing, coarse grinding and wet superfine grinding. Although the invention can utilize industrial waste to prepare the nano-silicon, the acid cleaning process introduces hydrogen ions with higher concentration, on one hand, the equipment cost and the environmental pollution are increased for industrial production; on the other hand, the prepared nano silicon material is acidic, and the performance of the material is greatly reduced. Meanwhile, the grinding time of the 100nm nano silicon particles prepared by the method exceeds 30h, the productivity is greatly reduced, and the industrial production is not facilitated.
Therefore, the development of a preparation method of the nano silicon, which has simple process equipment, low cost, suitability for industrial production, controllable oxidation and granularity and good dispersibility, is particularly critical; the development of the technology has a profound influence on the application of the silicon cathode material.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects and shortcomings in the background technology and providing a preparation method of a nano silicon material applied to a lithium ion battery cathode material.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of nano silicon material comprises the following steps:
(1) grinding the coarse silicon slurry to obtain micron-sized silicon powder slurry;
(2) adding a carbon material into the micron-sized silicon powder slurry for grinding to obtain a nanoscale silicon powder slurry;
(3) and drying, crushing, sieving and demagnetizing the nano-scale silicon powder slurry to obtain the nano-silicon material.
In the above preparation method, preferably, in the steps (1) and (2), the grinding process is performed in a protective gas; the protective gas is inert gas, and comprises one of high-purity nitrogen and argon.
In the preparation method, preferably, in the step (2), the carbon material is one or more of graphite, pitch, carbon microspheres, carbon nanotubes, graphene oxide, and carbon fibers; the adding mass of the carbon material is 0.01-10% of the mass of the micron-sized silicon slurry. Still more preferably, the added mass of the carbon material is 0.01-2% of the mass of the micron-sized silicon slurry.
In the above preparation method, preferably, in the steps (1) and (2), a grinding medium is added during the grinding process, and the grinding medium includes one or more of zirconia, titania, silicon nitride, silicon carbide, tungsten carbide, boron nitride, boron carbide and zirconium boride.
In the above preparation method, preferably, in the step (1), the grinding media with different particle sizes are freely matched, the particle size distribution range of the small particle grinding media is 0.1-1.0mm, and the particle size distribution range of the medium particle grinding media is 3-10 mm; the particle size distribution of the large-particle grinding media is 30-100 mm.
In the above preparation method, preferably, in the step (1), the crude silicon slurry is obtained by crushing crude silicon into crude silicon powder, adding the crushed crude silicon powder into a nonaqueous solvent, stirring, and sieving.
In the above preparation method, the non-aqueous solvent is preferably one or more of absolute ethyl alcohol, ethylene glycol, glycerol, isopropanol, butanol, polyethylene glycol, polyvinylpyrrolidone, acetone, cyclohexane, butanone, and benzene; the crude silicon is one or more of industrial polycrystalline silicon blocks, silicon microcrystals and industrial silicon ash; the mass ratio of the coarse silicon powder to the non-aqueous solvent is 1 (0.1-50), and the particle size of the coarse silicon powder is 50-500 um.
In the preparation method, preferably, in the step (1), the grinding time is 2-24h, and the grinding parameter is 500-3000 rpm; the grain size of the micron-sized silicon powder slurry is 1.0-30 um;
in the step (2), the grinding time is 2-10h, and the grinding parameter is 500-3000 rpm; the grain size of the nano-scale silicon powder slurry is 30-500 nm.
In the preparation method, preferably, in the step (3), the drying manner is one of forced air drying, vacuum drying, spray drying and freeze drying; the sieving is carried out by adopting one of an ultrasonic vibrating screen machine or an airflow sieving machine.
As a general inventive concept, the invention also provides an application of the nano silicon material prepared by the preparation method in a lithium ion battery cathode material.
Compared with the prior art, the invention has the advantages that:
(1) in the preparation method, the carbon material is added as a grinding medium, so that on one hand, the grinding of particles is promoted to be finer; on the other hand, the carbon material replaces the traditional dispersing agent, the generation of hard agglomeration phenomenon among the nano silicon particles is effectively avoided, the dispersing agent residue is reduced, and meanwhile, the addition of the carbon material can effectively improve the conductivity of the material.
(2) The preparation method provided by the invention is used for grinding in an oxygen-free environment, so that the surface oxidation degree of the nano particles is ensured to be lower; meanwhile, the echelon grinding is adopted, so that the nano silicon grinding time is greatly reduced, and the productivity is favorably improved.
(3) The preparation method solves the problems of high silica powder oxidation degree, serious agglomeration, large potential safety hazard in storage and the like in the preparation process of the nano-silicon in the prior art, and prepares the nano-silicon with high purity, controllable granularity and safe storage by simple mechanical step grinding.
(4) The silicon material prepared by the preparation method provides a silicon-based composite material precursor with good dispersion effect, high first effect and specific capacity for the application of the silicon material in a battery material, and meanwhile, the preparation method is simple in preparation process, low in cost, wide in raw material source and capable of being applied to the field of battery-grade silicon-carbon materials in a large scale.
In conclusion, the invention obtains the nanoscale silicon powder with controllable oxidation degree and particle size distribution range by simple closed echelon grinding, strictly controlling the oxygen content in the grinding environment, adding the carbon material as a dispersing grinding medium and adjusting the grinding parameters; meanwhile, the addition of the carbon material is beneficial to grinding of the nano silicon and reduction of agglomeration, and can further improve the conductivity of the nano silicon material and improve the electrochemical performance of the material. The method is simple, convenient, efficient, low in cost, easy to realize industrialization and capable of realizing large-scale battery-level application.
Drawings
FIG. 1 is an SEM image of nano-silicon prepared in example 2 of the present invention.
Fig. 2 is an XRD pattern of nano-silicon prepared in example 2 of the present invention.
FIG. 3 is an SEM image of nano-silicon prepared in comparative example 1 of the present invention.
FIG. 4 is an SEM image of nano-silicon prepared in comparative example 2 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the preparation method of the nano silicon material comprises the following steps:
(1) weighing 1kg of industrial silica fume, placing the industrial silica fume in a jaw crusher for crushing for 2h, and then placing the industrial silica fume in ball milling equipment for crushing for 3h to obtain coarse silica fume with the particle size of 50-500 um;
adding 4kg of absolute ethyl alcohol into the obtained coarse silicon powder, stirring at a high speed of 500rpm, and sieving with a 32-mesh sieve to obtain coarse silicon powder slurry;
(2) adding boron nitride balls (the median particle diameters of the boron nitride balls are 0.3mm, 3mm and 50mm, the mass ratio is 3:2:1) into the coarse silicon powder slurry prepared in the step (1), and mixing the boron nitride balls according to the mass ratio of 1: 1, proportioning in a mode;
placing the slurry in a closed high-energy planetary ball mill filled with protective gas (high-purity nitrogen) to grind for 15h (rotating speed 800rpm), and sieving with a 325-mesh sieve to obtain uniformly dispersed micron-sized silicon slurry;
(3) adding 50g of carbon nano tube into the micron-sized silicon powder slurry obtained in the step (2), and stirring at a high speed of 500rpm to obtain uniformly dispersed slurry;
grinding the slurry in a sand mill sealed and filled with protective gas (high-purity nitrogen gas) for 6h (3000rpm) to obtain uniformly dispersed nano-scale silicon powder slurry;
(4) and (4) carrying out vacuum drying, crushing, ultrasonic vibration, screening by using a 325-mesh screen and demagnetizing on the nano silicon slurry obtained in the step (3) to prepare the nano silicon powder with the particle size of 30-100 nm.
Example 2:
the preparation method of the nano silicon material comprises the following steps:
(1) weighing 500g of polycrystalline silicon blocks, placing the polycrystalline silicon blocks in a jaw crusher for crushing for 2 hours, and then placing the crushed polycrystalline silicon blocks in ball milling equipment for crushing for 2 hours to obtain coarse silicon powder with the particle size of 50-500 um;
adding 9kg of isopropanol into the obtained crude silicon powder, stirring at a high speed (500rpm), and sieving with a 32-mesh sieve to obtain crude silicon powder slurry;
(2) adding zirconia balls (the median particle diameters of the zirconia balls are 0.5mm, 5mm and 80mm, the mass ratio is 3:2:1) into the coarse silicon powder slurry prepared in the step (1), and mixing the zirconia balls according to the mass ratio of 1: 1, proportioning in a mode;
placing the slurry in a high-energy planetary ball mill which is sealed and is filled with protective gas (high-purity argon gas) to grind (rotating speed 800rpm) for 10h, and sieving by a 325-mesh sieve to obtain uniformly dispersed micron-sized silicon slurry;
(3) adding 15g of graphene oxide into the micron-sized silicon powder slurry obtained in the step (2), and stirring at a high speed of 200rpm to obtain uniformly dispersed slurry;
grinding the slurry in a closed high-purity argon sand mill at the rotating speed of 3000rpm for 6 hours to obtain uniformly dispersed nano-scale silicon powder slurry;
(4) and (3) preparing the nano silicon slurry obtained in the step (3) into nano silicon powder with the particle size of 30-100nm by freeze drying, crushing, vibrating sieving and demagnetizing, wherein the characteristics are shown in a figure 1 and a figure 2.
Comparative example 1:
the preparation method of the nano-silicon material of the comparative example is different from that of the example 2 only in that the micron-sized silicon slurry obtained after the step (2) is directly placed in an open sand mill to be ground for 6 hours, and the nano-silicon powder with the particle size of 200-300nm is prepared after vacuum drying, crushing, vibrating screening and demagnetizing, and the characterization is shown in fig. 3.
Comparative example 2:
the difference between the preparation method of the nano silicon material of the comparative example and the embodiment 2 is only that the operation mode of the step (3) is different, and the dispersion agent sodium carboxymethyl cellulose is adopted to replace the graphene oxide, and the specific operation mode of the step (3) is as follows: adding 50g of carboxymethyl cellulose sodium serving as a dispersing agent into the nano-scale silicon slurry obtained in the step (2), and stirring at a high speed to obtain uniformly dispersed slurry; then placing the slurry into a closed high-energy planetary ball mill which is filled with protective gas to grind for 6 hours to obtain uniformly dispersed nano-scale silicon powder slurry; the nano-scale silicon powder with the particle size of 100-200nm is prepared by freeze drying, crushing, vibrating sieving and demagnetizing, and the characterization is shown in figure 4.
The SEM characterization comparison shows that compared with the comparative example 2 (FIG. 4), the nano-scale silicon powder prepared in example 2 (FIG. 1) has basically similar dispersibility of silicon powder particles, and has a certain degree of soft agglomeration, and the secondary dispersion of the silicon powder can be realized through ultrasonic treatment at the later stage. In comparative example 1, no dispersant or carbon material (fig. 3) was added, the particle size of the milled nano-silicon powder was coarser to 200-300nm, and the agglomeration and hardening phenomenon existed to affect the re-dispersion of nano-silicon. The silicon powder prepared in example 2 (fig. 2) exhibits a cubic phase structure, which is suitable for use as a negative electrode material; meanwhile, other peak positions do not appear in XRD, and the addition amount of the carbon material is also proved to be small.
Example 3:
the preparation method of the nano silicon material comprises the following steps:
(1) weighing 500g of silicon microcrystal, placing the silicon microcrystal in a jaw crusher for crushing for 2h, and then placing the silicon microcrystal in ball milling equipment for crushing for 3h to obtain coarse silicon powder, wherein the particle diameter of the coarse silicon powder is concentrated in 50-500 um;
adding 5kg of polyvinylpyrrolidone into the prepared coarse silicon powder, and passing through a 32-mesh screen after high-speed stirring (200rpm) to prepare coarse silicon powder slurry;
(2) adding tungsten carbide balls (the median particle diameters of the tungsten carbide balls are 1.0mm, 10mm and 50mm, the mass ratio is 3:2:1) into the coarse silicon powder slurry prepared in the step (1), and mixing the tungsten carbide balls with the coarse silicon powder slurry according to the mass ratio of 1: 1, proportioning in a mode;
grinding the slurry in a sealed cone mill filled with protective gas (argon) at the rotating speed of 2000rpm for 10h, and sieving with a 325-mesh sieve to obtain uniformly dispersed micron-sized silicon slurry;
(3) adding 5g of graphite into the micron-sized silicon powder slurry obtained in the step (2), and stirring at a high speed (the rotating speed is 200rpm) to obtain uniformly dispersed slurry;
putting the slurry into a closed high-energy planetary ball mill filled with protective gas (high-purity nitrogen) and grinding for 3 hours at the rotating speed of 3000rpm to obtain uniformly dispersed nano-scale silicon powder slurry;
(4) and (4) preparing the nano silicon slurry obtained in the step (3) into nano silicon powder with the particle size of 300-400nm through forced air drying, crushing, vibrating sieving and demagnetizing.
Example 4:
the preparation method of the nano silicon material comprises the following steps:
(1) weighing 200kg of industrial silica fume, adding 5kg of N-methyl pyrrolidone, placing the industrial silica fume in a jaw crusher for crushing, placing the crushed industrial silica fume in ball milling equipment for crushing for 3 hours, and sieving the crushed industrial silica fume with a 32-mesh sieve to obtain crude silicon powder slurry, wherein the particle size of the crude silicon is intensively distributed to be 50-500 um;
(2) adding tungsten carbide balls (the median particle diameters of the tungsten carbide balls are 0.5mm, 30mm and 50mm, the mass ratio is 3:2:1) into the coarse silicon powder slurry prepared in the step (1), and mixing the tungsten carbide balls with the coarse silicon powder slurry according to the mass ratio of 1: 1, proportioning in a mode;
grinding the slurry in a tube mill sealed and filled with protective gas (high-purity nitrogen) at the rotating speed of 3000rpm for 8h, and sieving the ground slurry with a 325-mesh sieve to obtain uniformly dispersed micron-sized silicon slurry;
(3) adding 50g of asphalt powder into the micron-sized silicon powder slurry obtained in the step (2), and stirring at a high speed of 200rpm to obtain uniformly dispersed slurry;
grinding the slurry in a closed sand mill filled with protective gas (high-purity nitrogen) at the rotating speed of 3000rpm for 3 hours to obtain uniformly dispersed nano-scale silicon powder slurry;
(4) and (4) preparing the nano silicon slurry obtained in the step (3) into nano silicon powder with the particle size of 200-300nm through vacuum drying, crushing, vibrating sieving and demagnetizing.
The electrochemistry was tested using the following method: mixing nano silicon powder and artificial graphite according to the mass ratio of 1:9 to obtain a negative electrode material, pulping the negative electrode material, a conductive agent and a binder according to the mass ratio of 93:1:6, controlling the solid content of the slurry to be 50%, coating the slurry on a copper foil current collector to obtain a negative electrode plate, and controlling the compaction density of the plate to be 1.5g/cm3(ii) a Using a metallic lithium plate as a counter electrode, 1mol/L LiPF6And the/EC + DMC electrolyte is assembled into a 2032 button cell. The battery adopts an LAND battery test system, the constant current charge and discharge test is carried out at 0.1 ℃, the voltage range is 0.001-1.5V, and the test results are shown in the following table 1:
table 1: preparing a comparative table of the charging parameters from the nano silicon prepared by the invention;
as can be seen from Table 1, in example 2, compared with comparative example 2, the specific charging capacity of the nano-silicon prepared in example 2 reaches 597mAh/g, and the first coulombic efficiency reaches 88.4%, which indicates that the problem of silicon powder agglomeration can be solved by adding a small amount of carbon material, and the problems of material specific capacity and first effect reduction caused by adding a dispersing agent can be solved; compared with the comparative example 1, the comparative example 2 has the advantages that the difference of the charging specific capacity of the nano silicon is larger, and the embodiment 2 mainly performs environmental control to reduce the oxidation degree of the nano silicon, so that the specific capacity of the material is better, and the first effect is higher (the first effect is lower because silicon oxide is generated by oxidation).
An oxygen-nitrogen analyzer ONH-801A is adopted to test the oxygen content in the nano silicon, and a comparison sample is lead oxide (the oxygen content is 9.9%): the prepared nano silicon is subjected to an oxygen content test, and the test results are shown in the following table 2:
table 2: the content of the nano silica prepared by the invention is shown in a comparison table;
| performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 |
| Oxygen content (%) | 9.8541 | 9.2641 | 10.3498 | 10.5276 | 15.6293 | 10.2457 |
Therefore, the nano silicon prepared by the invention can be used as a battery material, and can effectively improve the initial charging specific capacity and the coulombic efficiency of the battery: on one hand, the added carbon medium can relieve the agglomeration effect of the nano silicon to a certain extent and increase the conductivity of the material; on the other hand, the oxygen-free environment is controlled, and the low oxidation degree of the prepared nano silicon powder is ensured.
Claims (8)
1. A preparation method of nano silicon material is characterized by comprising the following steps:
(1) grinding the coarse silicon slurry to obtain micron-sized silicon powder slurry; the grinding time is 2-24h, and the grinding parameter is 500-3000 rpm; the grain size of the micron-sized silicon powder slurry is 1.0-30 um;
(2) adding a carbon material into the micron-sized silicon powder slurry for grinding to obtain a nanoscale silicon powder slurry; wherein the adding mass of the carbon material is 0.01-10% of the mass of the micron-sized silicon slurry; the grinding time is 2-10h, and the grinding parameter is 500-3000 rpm; the grain size of the nano-scale silicon powder slurry is 30-500 nm; in the steps (1) and (2), the grinding process is carried out in a protective gas, and the protective gas is an inert gas;
(3) and drying, crushing, sieving and demagnetizing the nano-scale silicon powder slurry to obtain the nano-silicon material.
2. The method according to claim 1, wherein in the step (2), the carbon material is one or more of graphite, pitch, carbon microspheres, carbon nanotubes, graphene oxide, and carbon fibers.
3. The preparation method according to claim 1, wherein in the steps (1) and (2), grinding media are added in the grinding process, and the grinding media comprise one or more of zirconium oxide, titanium oxide, silicon nitride, silicon carbide, tungsten carbide, boron nitride, boron carbide and zirconium boride.
4. The method according to claim 3, wherein in the step (1), the grinding media are freely selected from grinding media with different particle sizes, the particle size distribution range of the small-particle grinding media is 0.1-1.0mm, the particle size distribution range of the medium-particle grinding media is 3-10mm, and the particle size distribution range of the large-particle grinding media is 30-100 mm.
5. The production method according to any one of claims 1 to 4, wherein in the step (1), the crude silicon slurry is a slurry obtained by crushing crude silicon into crude silicon powder, adding the crushed crude silicon powder to a nonaqueous solvent, stirring the resultant, and sieving the resultant.
6. The method according to claim 5, wherein the non-aqueous solvent is one or more of absolute ethanol, ethylene glycol, glycerol, isopropanol, butanol, polyethylene glycol, polyvinylpyrrolidone, acetone, cyclohexane, methyl ethyl ketone, and benzene; the crude silicon is one or more of industrial polycrystalline silicon blocks, silicon microcrystals and industrial silicon ash; the mass ratio of the coarse silicon powder to the non-aqueous solvent is 1 (0.1-50), and the particle size of the coarse silicon powder is 50-500 um.
7. The method according to any one of claims 1 to 4, wherein in the step (3), the drying is one of air drying, vacuum drying, spray drying and freeze drying; the sieving is carried out by adopting one of an ultrasonic vibrating screen machine or an airflow sieving machine.
8. Application of the nano silicon material prepared by the preparation method of any one of claims 1 to 4 in negative electrode materials of lithium ion batteries.
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| CN110783555A (en) * | 2019-09-16 | 2020-02-11 | 安徽若水化工有限公司 | Nano silicon material with low cost and high yield and preparation method thereof |
| CN112645333B (en) * | 2019-10-11 | 2022-06-10 | 洛阳阿特斯光伏科技有限公司 | Preparation method of nano silicon powder, prepared nano silicon powder and application |
| CN111180719A (en) * | 2020-01-07 | 2020-05-19 | 马鞍山科达普锐能源科技有限公司 | Method for preparing nano silicon by three-stage grinding |
| CN111392731A (en) * | 2020-04-08 | 2020-07-10 | 江苏新效新材料科技有限公司 | Preparation method of nano silica sand mill by taking polyvinylpyrrolidone as dispersing agent |
| CN111446431B (en) * | 2020-04-14 | 2022-12-06 | 南京宁智高新材料研究院有限公司 | Method for enhancing interface contact of silicon-oxygen-carbon cathode material of lithium ion battery through oxygen transfer reaction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531761A (en) * | 2013-10-28 | 2014-01-22 | 上海利物盛企业集团有限公司 | Preparation method for nanometer silicon |
| CN105655569A (en) * | 2016-04-01 | 2016-06-08 | 四川创能新能源材料有限公司 | Preparation method of ultrafine nano-level silicon powder |
| CN106532019A (en) * | 2016-12-31 | 2017-03-22 | 湖北诺邦科技股份有限公司 | Silicon-carbon composite material and preparation method thereof |
| CN107248451A (en) * | 2017-07-28 | 2017-10-13 | 中国科学院电工研究所 | A kind of lithium-ion capacitor of high-energy-density |
| CN108172785A (en) * | 2017-12-22 | 2018-06-15 | 东莞东阳光科研发有限公司 | A kind of carbon/silicon/carbon composite and its preparation method and application |
-
2019
- 2019-01-17 CN CN201910043744.4A patent/CN109860548B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103531761A (en) * | 2013-10-28 | 2014-01-22 | 上海利物盛企业集团有限公司 | Preparation method for nanometer silicon |
| CN105655569A (en) * | 2016-04-01 | 2016-06-08 | 四川创能新能源材料有限公司 | Preparation method of ultrafine nano-level silicon powder |
| CN106532019A (en) * | 2016-12-31 | 2017-03-22 | 湖北诺邦科技股份有限公司 | Silicon-carbon composite material and preparation method thereof |
| CN107248451A (en) * | 2017-07-28 | 2017-10-13 | 中国科学院电工研究所 | A kind of lithium-ion capacitor of high-energy-density |
| CN108172785A (en) * | 2017-12-22 | 2018-06-15 | 东莞东阳光科研发有限公司 | A kind of carbon/silicon/carbon composite and its preparation method and application |
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