CN110642253A - Preparation method for preparing nano reduced silicon through aluminothermic reaction - Google Patents
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Abstract
The invention discloses a preparation method for preparing nano reduced silicon by thermite reaction, which can replace a nano silicon negative electrode material for preparing a battery by a laser method, improve the specific capacity of the battery and reduce the cost. The synthesis step of the nano silicon is mainly divided into two parts. The first part is the reduction of silicon dioxide by aluminum powder; and the second part is to remove impurities except silicon powder through other purification processes. The method can obtain brown yellow silicon powder of dozens of nanometers. The method controls the reaction temperature through molten salt, uses sodium hexafluoroaluminate as a starter to promote the reaction to start and improve the yield, and uses potassium pyrosulfate to remove aluminum oxide. The method has simple implementation equipment and can synthesize the nano silicon powder on a large scale on the basis of not changing production conditions. And the price is cheap, the operation is safe, the by-product and the fused salt are easy to recycle, and the green pollution-free production is realized.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery cathode materials, in particular to a preparation method for preparing nano reduced silicon through thermite reaction.
Background
Currently, the automotive industry is facing a major revolution. The new energy automobile replaces a fuel vehicle to become the choice of the times. The lithium ion battery is one of the best choices of the power battery of the new energy automobile.
The biggest obstacle of new energy automobiles to replace fuel vehicles is that the specific capacity of a power battery is low, so that the mileage of the new energy automobiles is greatly limited.
The scientists have found that when the negative electrode is replaced by silicon of the order of tens of nanometers, the cycle performance and the specific capacity of the battery are greatly improved. However, industrially, the nano-scale silicon powder can be prepared only by the laser vapor deposition method. A disadvantage of this method is that the production speed is limited by the number of instruments. In addition, the smaller the particle size, the lower the yield.
Many scientists develop a new method for preparing the nano-silicon elemental powder by reducing silicon dioxide by a chemical method. Most people adopt magnesium as a reducing agent to reduce a silicon-containing material to obtain silicon elemental powder. For example, magnesium is directly reacted with silica, magnesium is reacted with silicon tetrachloride, and magnesium is reacted with organosilane. The methods can obtain the nano silicon material, and the prepared battery has good performance. But the defect is obvious that magnesium is a material which is easy to spontaneously combust, and many experimental accidents also show that the magnesium has extremely high risk and high price. Compared with the prior art, the aluminum powder can stably exist in the air, has higher molar heat value, is a cheap product which is used in a large amount in the firework and cracker industry, and has much better safety and economy than magnesium. If aluminum can be substituted for magnesium, the process is more amenable to industrialization.
The aluminum-reduced silicon has the biggest disadvantage that the residual alumina after the aluminum-reduced silicon is difficult to remove. There have been many researchers, such as vacuum ball milling aluminum reduction of silicon, and battery assembly with the non-dealuminated product, with a capacity much higher than commercial graphite. And the anhydrous aluminum chloride is used as molten salt for people to remove aluminum oxide while reducing silicon by aluminum, and the method has the defect that the anhydrous aluminum chloride is easy to absorb water in air and decompose into aluminum hydroxide. In addition, the thermite reaction forms large silicon particles at high temperatures, and such silicon powders cannot be used as battery negative electrode materials.
Disclosure of Invention
The invention aims to solve the problems that: the preparation method for preparing the nano reduced silicon through the aluminothermic reaction is provided, the reaction temperature is controlled through molten salt, sodium hexafluoroaluminate is used as a starter to promote the reaction to start and improve the yield, and potassium pyrosulfate is used for removing aluminum oxide. The method has simple implementation equipment and can synthesize the nano silicon powder on a large scale on the basis of not changing production conditions. And the price is cheap, the operation is safe, the by-product and the fused salt are easy to recycle, and the green pollution-free production is realized.
The technical scheme provided by the invention for solving the problems is as follows: a preparation method for preparing nano reduced silicon by thermite reaction comprises the following steps,
(1) uniformly stirring silicon dioxide, aluminum powder, potassium chloride, anhydrous lithium chloride and trisodium hexafluoroaluminate according to the mass percentage of 1.2:1.2:4:3.4:1 at low humidity to obtain a mixture 1;
(2) adding the mixture 1 into a crucible with a cover, heating to 650-900 ℃ in a muffle furnace at a heating rate of 20 ℃/min, and preserving heat for more than 10 hours; naturally cooling to room temperature and taking out to obtain a frit 1;
(3) adding the frit 1 into a hydrochloric acid solution, and reacting at room temperature until no bubbles are generated; filtering to obtain a solid 1;
(4) adding the solid 1 into a container with water, covering a cover, heating to 100-120 ℃, and completely dissolving the molten salt; after standing, sucking out the salt-containing solution on the upper layer, and drying the precipitate to obtain a solid 2;
(5) grinding the solid 2, sieving the ground solid with a 500-mesh sieve, and mixing potassium pyrosulfate powder with the mass of more than 10 times that of the solid 2; putting the mixture into a covered porcelain crucible, heating the mixture to 600 ℃ at the heating rate of 20 ℃/min, and preserving the heat for 30 minutes; naturally cooling and taking out to obtain a frit 2;
(6) adding the frit 2 into a container with water, covering the container with a cover, heating to 100-120 ℃, and completely dissolving the molten salt; after standing, sucking out the salt-containing solution on the upper layer, and drying the precipitate to obtain a solid 3;
(7) adding the solid 3 into excessive 1mol/L hydrofluoric acid, reacting for 5-10 h, and removing the residual silicon dioxide; sucking out the supernatant, washing the precipitate for more than 3 times, and filtering to obtain simple substance silicon;
(8) and (5) drying the simple substance silicon in the step (7) in vacuum at 80 ℃ to obtain a final product.
Preferably, in step (1), in order to ensure a low humidity of 40% or less, a method of pre-oven drying and dehumidifier dehumidification is adopted.
Preferably, the uniform stirring performed in step (1) does not involve high-speed or long-time ball milling, and other mixing methods that may cause oxidation of the aluminum powder.
Preferably, the atmosphere for performing the experiment in the step (2) is air, and the inert gas protection is not needed, but the atmosphere should be covered.
Preferably, the hydrochloric acid in the step (3) should be in excess and maintained at a concentration of 1 mol/L.
Preferably, the reaction is carried out in step (3) with stirring or with heating suitably not exceeding 40 ℃ to accelerate the reaction.
Preferably, in the steps (4) and (6), a proper stirring measure is adopted to accelerate the fusion cake dissolution.
Preferably, in the steps (4) and (6), the solid can be separated by centrifugation, standing or filtration.
Preferably, in the step (7), during the process of removing silicon dioxide by hydrofluoric acid, the temperature must be kept in the room temperature range to prevent the silicon simple substance from being reacted, and ice water centrifugation or semi-permeable membrane filtration can be adopted.
Compared with the prior art, the invention has the advantages that: the invention adopts a fused salt-aluminothermic silicon reduction method to prepare the nano silicon cathode material. According to the Sherle formula, the particle size of the silicon nano-particles prepared by the method is about 20nm, the morphology of the TEM test powder is similar to that of silicon reduced by magnesium, the silicon nano-particles are aggregates of small particles in a solution, and the purity is high. The resulting powder was brown-yellow. The materials used were: silicon dioxide, aluminum powder, potassium chloride, anhydrous lithium chloride, trisodium hexafluoroaluminate, potassium pyrosulfate, hydrogen fluoride and the like have the characteristics of safety and low price. The generated solid waste such as residual potassium chloride, anhydrous lithium chloride, aluminum fluoride, aluminum sulfate and other byproducts is harmless to the environment and is easy to recycle; the generated hydrogen is less in amount and free of pollution; the produced silicon fluoride is easy to dissolve in the water solution, while the impurity removal process of the invention is carried out in water, and alkali can be added into the solution after impurity removal and separation for treatment; the whole process is green and environment-friendly. The required production equipment is widely used, and additional investment equipment is not needed generally; the required atmosphere is air. The invention has the characteristics of low cost, easy production and easy implementation
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is an XRD pattern of the examples.
FIG. 2 is a TEM image of the embodiment.
FIG. 3 is a pictorial diagram of an embodiment.
Detailed Description
The following embodiments are described in detail with reference to the accompanying drawings, so that how to implement the technical features of the present invention to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Example 1
A preparation method for preparing nano reduced silicon by thermite reaction comprises the following steps,
(1) the silicon dioxide, aluminum powder, potassium chloride, anhydrous lithium chloride and trisodium hexafluoroaluminate are uniformly stirred at a humidity of 40% according to a ratio of 1.2g to 4g to 3.4g to 1g to obtain a mixture 1.
(2) The mixture 1 was placed in a covered 30ml crucible and heated to 700 ℃ in a muffle furnace at a heating rate of 20 ℃/min and held for 10 h. Naturally cooling to room temperature, and taking out to obtain the frit 1.
(3) Frit 1 was added to a beaker containing 30ml of 1mol/L hydrochloric acid solution and the reaction was carried out at 100 ℃ with the lid closed until no bubbles were formed. Filtration and drying gave solid 1.
(4) The solid 1 was added to a beaker with water, covered, heated to 100 ℃ and the molten salt was completely dissolved. After standing, the upper salt-containing solution was aspirated, and the precipitate was dried to give solid 2.
(5) The solid 2 was ground, passed through a 500-mesh sieve, and potassium pyrosulfate powder 10 times the mass of the solid 2 was mixed in. Putting the mixture into a covered porcelain crucible, heating to 600 ℃ at the heating rate of 20 ℃/min, and preserving the heat for 30 minutes. Naturally cooling and taking out to obtain the frit 2.
(6) The frit 2 was added to the vessel in the presence of water, the lid was closed, and the molten salt was completely dissolved by heating to 120 ℃. After standing, the upper salt-containing solution was aspirated, and the precipitate was dried to give solid 3.
(7) Adding the solid 3 into 10ml of 1mol/L hydrofluoric acid, and reacting for 6h to remove the residual silicon dioxide. Sucking out supernatant, washing the precipitate for more than 3 times, and filtering to obtain simple substance silicon.
(8) And (5) drying the simple substance silicon in the step (7) at 80 ℃ in vacuum for 5h to obtain a final product.
Further, in step (1), in order to ensure low humidity below 40%, a method of pre-oven drying and dehumidifier dehumidification is adopted.
Further, the uniform stirring performed in the step (1) does not involve high-speed or long-time ball milling, and other mixing methods that may cause oxidation of the aluminum powder.
Further, the atmosphere for performing the experiment in the step (2) is air, and the inert gas protection is not needed, but the atmosphere should be covered.
Further, the hydrochloric acid should be in excess and maintained at a concentration of 1mol/L in the step (3).
Further, in the step (3), the reaction is carried out while stirring or the reaction is suitably heated to not more than 40 ℃ to accelerate the reaction.
Further, in the steps (4) and (6), appropriate stirring measures are taken to accelerate the fusion cakes to dissolve.
Further, in the steps (4) and (6), the solid can be separated by centrifugation, standing or filtration.
Further, in the step (7), during the process of removing silicon dioxide by hydrofluoric acid, the temperature must be kept in the room temperature range to prevent the silicon simple substance from being reacted, and ice water centrifugation or semi-permeable membrane filtration can be adopted.
Example 2
A preparation method for preparing nano reduced silicon by thermite reaction comprises the following steps,
(1) the silicon dioxide, aluminum powder, potassium chloride, anhydrous lithium chloride and trisodium hexafluoroaluminate are uniformly stirred at a humidity of 40% according to a ratio of 1.2g to 4g to 3.4g to 1g to obtain a mixture 1.
(2) The mixture 1 was placed in a covered 30ml crucible and heated to 700 ℃ in a muffle furnace at a heating rate of 20 ℃/min and held for 10 h. Naturally cooling to room temperature, and taking out to obtain the frit 1.
(3) Frit 1 was added to a beaker containing 30ml of 1mol/L hydrochloric acid solution and the reaction was carried out at 100 ℃ with the lid closed until no bubbles were formed. Filtration and drying gave solid 1.
(4) The solid 1 was added to a beaker with water, covered, heated to 120 ℃ and the molten salt was completely dissolved. After standing, the upper salt-containing solution was aspirated, and the precipitate was dried to give solid 2.
(5) The solid 2 was ground, passed through a 500-mesh sieve, and potassium pyrosulfate powder 10 times the mass of the solid 2 was mixed in. Putting the mixture into a covered porcelain crucible, heating to 600 ℃ at the heating rate of 20 ℃/min, and preserving the heat for 30 minutes. Naturally cooling and taking out to obtain the frit 2.
(6) The frit 2 was added to the vessel in the presence of water, the lid was closed, and the molten salt was completely dissolved by heating to 120 ℃. After standing, the upper salt-containing solution was aspirated, and the precipitate was dried to give solid 3.
(7) Adding the solid 3 into 10ml of 1mol/L hydrofluoric acid, and reacting for 10h to remove the residual silicon dioxide. Sucking out supernatant, washing the precipitate for more than 3 times, and filtering to obtain simple substance silicon.
(8) And (5) drying the simple substance silicon in the step (7) at 80 ℃ in vacuum for 5h to obtain a final product.
The foregoing is merely illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the claims. The present invention is not limited to the above embodiments, and the specific structure thereof is allowed to vary. All changes which come within the scope of the invention as defined by the independent claims are intended to be embraced therein.
Claims (9)
1. A preparation method for preparing nano reduced silicon by thermite reaction is characterized in that: the method comprises the following steps of,
(1) uniformly stirring silicon dioxide, aluminum powder, potassium chloride, anhydrous lithium chloride and trisodium hexafluoroaluminate according to the mass percentage of 1.2:1.2:4:3.4:1 at low humidity to obtain a mixture 1;
(2) adding the mixture 1 into a crucible with a cover, heating to 650-900 ℃ in a muffle furnace at a heating rate of 20 ℃/min, and preserving heat for more than 10 hours; naturally cooling to room temperature and taking out to obtain a frit 1;
(3) adding the frit 1 into a hydrochloric acid solution, and reacting at room temperature until no bubbles are generated; filtering to obtain a solid 1;
(4) adding the solid 1 into a container with water, covering a cover, heating to 100-120 ℃, and completely dissolving the molten salt; after standing, sucking out the salt-containing solution on the upper layer, and drying the precipitate to obtain a solid 2;
(5) grinding the solid 2, sieving the ground solid with a 500-mesh sieve, and mixing potassium pyrosulfate powder with the mass of more than 10 times that of the solid 2; putting the mixture into a covered porcelain crucible, heating the mixture to 600 ℃ at the heating rate of 20 ℃/min, and preserving the heat for 30 minutes; naturally cooling and taking out to obtain a frit 2;
(6) adding the frit 2 into a container with water, covering the container with a cover, heating to 100-120 ℃, and completely dissolving the molten salt; after standing, sucking out the salt-containing solution on the upper layer, and drying the precipitate to obtain a solid 3;
(7) adding the solid 3 into excessive 1mol/L hydrofluoric acid, reacting for 5-10 h, and removing the residual silicon dioxide; sucking out the supernatant, washing the precipitate for more than 3 times, and filtering to obtain simple substance silicon;
(8) and (5) drying the simple substance silicon in the step (7) in vacuum at 80 ℃ to obtain a final product.
2. The preparation method of nano reduced silicon by thermite reaction according to claim 1, wherein the preparation method comprises the following steps: in order to ensure the low humidity below 40% in the step (1), a method of drying in an oven and dehumidifying in a dehumidifier is adopted in advance.
3. The preparation method of nano reduced silicon by thermite reaction according to claim 1, wherein the preparation method comprises the following steps: the uniform stirring performed in the step (1) does not involve high-speed or long-time ball milling, and other mixing methods that may cause oxidation of the aluminum powder.
4. The preparation method of nano reduced silicon by thermite reaction according to claim 1, wherein the preparation method comprises the following steps: the atmosphere for carrying out the experiment in the step (2) is air, and inert gas protection is not needed, but the experiment should be covered.
5. The preparation method of nano reduced silicon by thermite reaction according to claim 1, wherein the preparation method comprises the following steps: the hydrochloric acid should be in excess and maintained at a concentration of 1mol/L in said step (3).
6. The preparation method of nano reduced silicon by thermite reaction according to claim 1, wherein the preparation method comprises the following steps: in the step (3), the reaction is carried out under stirring or is properly heated but not more than 40 ℃ so as to accelerate the reaction.
7. The preparation method of nano reduced silicon by thermite reaction according to claim 1, wherein the preparation method comprises the following steps: in the steps (4) and (6), appropriate stirring measures are taken to accelerate the fusion cakes to dissolve.
8. The preparation method of nano reduced silicon by thermite reaction according to claim 1, wherein the preparation method comprises the following steps: in the steps (4) and (6), the solid can be separated by centrifugation, standing or filtration.
9. The preparation method of nano reduced silicon by thermite reaction according to claim 1, wherein the preparation method comprises the following steps: in the step (7), during the process of removing silicon dioxide by hydrofluoric acid, the temperature must be kept in the room temperature range to prevent the silicon simple substance from being reacted, and ice water centrifugation or semi-permeable membrane filtration can be adopted.
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