CN108358206B - Three-dimensional cross-linked structure silicon nano material and preparation method and application thereof - Google Patents
Three-dimensional cross-linked structure silicon nano material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a three-dimensional cross-linked structure silicon nano material and a preparation method and application thereof. A fused salt reduction method is adopted to extract the silicon nano material with the three-dimensional cross-linked structure from silicate minerals, and specifically, magnesium powder or aluminum powder, aluminum chloride and a silicon dioxide precursor derived from natural silicate minerals through hydrothermal acidification treatment are uniformly mixed, and sealed fused salt reduction reaction is carried out in a reaction kettle to prepare the silicon nano material with the three-dimensional cross-linked structure. The method is simple and efficient, is easy to operate, and the prepared silicon particles have the excellent characteristics of high purity, small size, high specific capacity and the like, and have wide application prospects in the energy storage fields of electrode materials of ion batteries and the like.
Description
Technical Field
The invention relates to a three-dimensional cross-linked structure silicon nano material extracted and prepared from natural silicate minerals, a preparation method and application thereof, belonging to the field of inorganic nonmetal nano materials.
Background
The increasing global demand for energy, the heavy use of non-renewable fossil fuels, and the increasing problem of environmental pollution have prompted researchers to explore and utilize more technologies and materials with efficient, low cost, and environmentally friendly energy storage and conversion. In the past few years, lithium ion batteries having good charge-discharge cycle stability have been gradually applied to practical production and life. However, the specific theoretical capacity of carbon material, a commercial lithium battery negative electrode material, has been low to date (0.372Ah g)-1) The demand of human life is increasingly not satisfied. The negative electrode material of the ion battery has a large lifting space. The silicon material has an extremely high theoretical specific capacity (about 4.20Ah g)-1) However, there is a serious problem of volume expansion during charge and discharge cycles, which results in a sharp drop in the lithium insertion/removal capacity, and seriously hinders the popularization and application of silicon negative electrode materials. Meanwhile, the traditional magnesium thermal reaction adopted for synthesizing silicon materials at present needs very high temperature conditions, which results in the generation of byproducts such as magnesium-silicon alloy compounds and the like. At the same time, highThe temperature conditions place high demands on the equipment required for the reduction reaction. In addition, the silicon dioxide raw material adopted by the magnesium thermal reaction is ethyl orthosilicate through the prior art
The method is derived and has high synthesis cost and time cost. Therefore, it is of great significance to develop a method with abundant and cheap raw materials and easily available reaction conditions to prepare the high-performance silicon negative electrode material.
Disclosure of Invention
The invention aims to provide a simple and efficient method for extracting and preparing a silicon negative electrode material from natural silicate minerals, a synthetic product and application thereof.
A preparation method of a three-dimensional cross-linked structure silicon nano material comprises the following steps: uniformly dispersing natural silicate minerals into an acid solution for hydrothermal acidification treatment to obtain a silicon dioxide precursor; and then uniformly mixing the obtained silicon dioxide precursor, metal powder with strong reducibility and low-melting-point salt powder, transferring the mixture into a reaction kettle for carrying out sealed molten salt reduction reaction, and carrying out acid cleaning, purification and drying on a reaction product to obtain the silicon nano material with the three-dimensional cross-linked structure.
The preparation method of the three-dimensional cross-linked structure silicon nano material comprises the following steps: the natural silicate mineral comprises one or more of halloysite, silicalite, kaolinite and montmorillonite; halloysite is preferred.
The preparation method of the three-dimensional cross-linked structure silicon nano material comprises the following steps: the dilute acid solution adopted in the hydrothermal acidification treatment is hydrochloric acid or sulfuric acid.
The preparation method of the three-dimensional cross-linked structure silicon nano material comprises the following steps: uniformly dispersing natural silicate minerals into an acid solution with the molar concentration of 0.5-10 mol/L; the preferable molar concentration of the acid solution is 2-6 mol/L; the natural silicate mineral is uniformly dispersed in the acid solution according to the solid-liquid mass/volume ratio of 1: 50-100 (g/mL).
The preparation method of the three-dimensional cross-linked structure silicon nano material comprises the following steps: uniformly dispersing natural minerals into an acid solution, uniformly stirring, transferring the solution into a reaction kettle, sealing, heating to 80-150 ℃, and reacting for 0.5-10 h; the preferable temperature range is 100-130 ℃, and the time range is 2-5 h.
According to the method, the natural silicate minerals are uniformly dispersed into an acid solution for hydrothermal acidification treatment to obtain a silicon dioxide precursor, and a reaction product is centrifuged, washed and dried at 60 ℃ for 6-8 hours and then used for a subsequent molten salt reduction reaction.
The preparation method of the three-dimensional cross-linked structure silicon nano material comprises the following steps: the metal powder with strong reducibility comprises one or two of magnesium powder and aluminum powder; the low-melting-point salt powder comprises one or two of aluminum chloride powder and magnesium chloride powder.
The role of the strongly reducing metal powder is to reduce the silica in the mineral by its strong reducing properties, acting as a reducing agent. The low melting point salts are used as reactants to participate in reduction reaction on one hand, and provide a reaction system for the reaction on the other hand.
The preparation method of the three-dimensional cross-linked structure silicon nano material comprises the following steps: uniformly mixing a silicon dioxide precursor derived from a natural silicate mineral, metal powder with strong reducibility and low-melting-point salt powder, transferring the mixture into a reaction kettle for sealing, and heating to 210-300 ℃ for reacting for 2-48 hours; the preferable temperature range is 240-260 ℃, and the time range is 8-12 h.
The preparation method of the three-dimensional cross-linked structure silicon nano material comprises the following steps: the mass ratio of the silicon dioxide precursor obtained by the hydrothermal acidification of the natural silicate mineral to the metal powder with strong reducibility is 1: 0.6-0.9, and the mass ratio of the silicon dioxide precursor obtained by the hydrothermal acidification of the natural silicate mineral to the low-melting-point salt powder is 1: 5-10; preferably, the mass ratio of the silicon dioxide precursor obtained by the hydrothermal acidification of the natural silicate mineral to the metal powder with strong reducibility is 1:0.8, and the mass ratio of the silicon dioxide precursor obtained by the hydrothermal acidification of the natural silicate mineral to the low-melting-point salt powder is 1: 8.
According to the invention, the excessive silicon dioxide precursor derived from natural silicate minerals can cause incomplete reaction, and nanoparticles with higher purity cannot be obtained; too much metal powder may cause the reaction system to expand excessively, and in severe cases, may even present a risk of explosion.
The preparation method of the three-dimensional cross-linked structure silicon nano material comprises the following steps: carrying out acid pickling purification on the fused salt through reduction reaction, and selecting 2-4 mol/L hydrochloric acid and 10 wt% hydrofluoric acid to carry out mixed acid pickling at a volume ratio of 2-3: 1; the pickling temperature is 70-90 ℃, the preferred temperature is 80 ℃, and the pickling time is 2-6 h; and then drying for 6-8 h at 60 ℃.
The three-dimensional cross-linked structure silicon nano material is prepared by the method. The three-dimensional cross-linked structure silicon nano material is used as an ion battery cathode material.
Compared with the prior art, the silicon nanomaterial with a three-dimensional cross-linked structure can be synthesized, and the technical scheme of the invention has the following advantages:
1. according to the invention, silicate clay minerals with low cost and quite rich reserves are used as raw materials, the sealed reaction of acid treatment and molten salt reduction is realized in the reaction kettle, the experimental process is simple, the equipment requirement is not high, the operation is safe, the raw material reserves are rich, and the commercial popularization and application of silicon materials are facilitated.
2. The silicon nanomaterial with a three-dimensional cross-linked structure is successfully synthesized by adopting halloysite clay mineral as a raw material, magnesium powder as a reducing agent and aluminum chloride as a molten salt system at a temperature far lower than the traditional magnesiothermic reduction temperature (>650 ℃), such as 250 ℃.
3. The invention researches the influence of the reduction temperature on the phase of the three-dimensional cross-linked silicon nano material, and finds that the silicon product obtained at a lower reduction temperature (such as 200 ℃) has low purity and contains a lot of impurities which are difficult to remove, and the specific details are shown in the embodiment, the comparative example and the attached drawing.
4. When the prepared three-dimensional cross-linked structure silicon nano material is used as a negative electrode active material of a lithium battery, the prepared three-dimensional cross-linked structure silicon nano material has excellent lithium battery performance, and the lithium battery performance is 0.1A g-1、0.5A g-1And 2A g-1The specific capacity after 50, 200 and 500 cycles of cyclic charge and discharge under constant current density is 2.54Ah g-1、1.87Ah g-1And 0.97Ah g-1Has wide prospect in the commercial application of silicon electrode materials.
Drawings
FIG. 1 is an X-ray powder diffraction (XRD) pattern of a halloysite clay mineral used in example 1;
FIG. 2 shows SiO obtained by hydrothermal acid treatment in example 12XRD pattern of (a);
FIG. 3 is an amorphous prepared SiO resulting from hydrothermal acid treatment of example 12A spectrum of (a);
FIG. 4 is an XRD pattern of a three-dimensional cross-linked structure silicon nanomaterial prepared in example 1;
FIG. 5 is an SEM electron microscopic view of the three-dimensional cross-linked structure silicon nanomaterial prepared in example 1;
FIG. 6 is a TEM micrograph of the three-dimensional cross-linked structure silicon nanomaterial prepared in example 1;
fig. 7 is a lithium battery performance diagram of a half-cell assembled by the three-dimensional cross-linked structure silicon nanomaterial prepared in example 1: (a) a capacity-voltage curve chart of the silicon nano electrode material in the charging and discharging process; (b) the silicon nano electrode material is subjected to cyclic charge and discharge under the constant current density of 0.1A/g; (c) multiplying power performance diagram of the silicon nano electrode material; (d) a capacity-voltage curve chart of the silicon nano electrode material in the charge and discharge process under different current densities; (e) the silicon nano electrode material is subjected to cyclic charge and discharge under the constant current density of 0.5A/g; (f) the silicon nano electrode material is subjected to cyclic charge and discharge under the constant current density of 2A/g.
FIG. 8 is an XRD pattern of the product obtained by acid treatment of comparative example 1;
FIG. 9 is an XRD pattern of the product prepared in comparative example 2;
fig. 10 is an XRD pattern of the product prepared in comparative example 3.
Detailed Description
The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.
Example 1
0.5g of halloysite clay mineral is weighed and dispersed into 2mol/L hydrochloric acid solution (40mL), the mixture is transferred into a reaction kettle after being stirred evenly, sealed and placed at 120 ℃ for reaction for 4 hours. And centrifuging and washing the reaction product, drying at 60 ℃ for 6-8 h, weighing 0.2g of the product, 0.8g of magnesium powder and 8g of aluminum chloride powder, uniformly mixing, transferring to a reaction kettle, and reacting at 250 ℃ for 10 h. And (3) pickling the reaction product with a mixture (volume ratio is 2:1) of hydrochloric acid (2mol/L) and hydrofluoric acid (10 wt%) at 80 ℃ for 3h, purifying, drying at 60 ℃ for 6-8 h to obtain a powder sample, and carrying out lithium battery performance test on the prepared sample. The halloysite clay mineral shown in fig. 1 was identified by XRD as a high-purity halloysite phase; the powder product obtained by hydrothermal acid treatment as shown in FIG. 2 is amorphous silicon dioxide; the analysis of the element species and content is carried out by an X-ray energy spectrometer, and it can be seen from FIG. 3 that the elements contained in the product are silicon and oxygen, and the atomic ratio of the silicon oxygen element is 1: 2; the product after being reduced, purified and dried by magnesium powder is identified as a high-purity silicon simple substance by XRD as shown in figure 4; the morphology of the material is analyzed by SEM and TEM, and the morphology of the material can be seen from FIGS. 5 and 6 as a three-dimensional cross-linked nanostructure with a nano-branch size of about 15 nm; the lithium battery performance test is shown in fig. 7.
Example 2
0.7g of halloysite clay mineral is weighed and dispersed into 5mol/L hydrochloric acid solution (40mL), the mixture is transferred into a reaction kettle after being stirred uniformly, sealed and placed at 130 ℃ for reaction for 2 hours. And centrifuging and washing the reaction product, drying at 60 ℃ for 6-8 h, weighing 0.2g of the product, 0.8g of magnesium powder and 8g of aluminum chloride powder, uniformly mixing, transferring to a reaction kettle, and reacting at 250 ℃ for 10 h. After the reaction product is purified by acid washing with a mixture (volume ratio of 2:1) of hydrochloric acid (2mol/L) and hydrofluoric acid (10 wt%) at 80 ℃ for 3 hours, dried and dried at 60 ℃ for 6-8 hours, a powder sample is obtained, and the prepared sample is subjected to a lithium battery performance test, and the performance of the sample is equivalent to that of the material prepared in example 1.
Example 3
0.7g of montmorillonite is weighed and dispersed in 2mol/L sulfuric acid solution (40mL), after being uniformly stirred, the mixture is transferred into a reaction kettle to be sealed and placed at 90 ℃ for reaction for 2 hours. And centrifuging and washing the reaction product, drying at 60 ℃ for 6-8 h, weighing 0.2g of the product, 0.8g of magnesium powder and 8g of aluminum chloride powder, uniformly mixing, transferring to a reaction kettle, and reacting at 210 ℃ for 4 h. And (3) pickling the reaction product with a mixture (volume ratio is 2:1) of hydrochloric acid (2mol/L) and hydrofluoric acid (10 wt%) at 80 ℃ for 3h, purifying, drying at 60 ℃ for 6-8 h to obtain a powder sample, and carrying out lithium battery performance test on the prepared sample. It is found that the material prepared in the embodiment is slightly inferior to the material prepared in the embodiment 1 in purity, size and performance, but also can be significantly superior to the common lithium battery negative electrode active material, and the purpose of the invention is achieved.
Comparative example 1
0.5g of halloysite clay mineral is weighed and dispersed into 2mol/L hydrochloric acid solution (40mL), the mixture is transferred into a reaction kettle after being stirred evenly, sealed and placed at 80 ℃ for reaction for 4 hours. And centrifuging and washing the reaction product, and drying at 60 ℃ for 6-8 h to obtain a powder sample. As shown in FIG. 8, SiO could not be obtained at 80 ℃ condition2A precursor.
Comparative example 2
0.5g of halloysite clay mineral is weighed and dispersed into 2mol/L hydrochloric acid solution (40mL), the mixture is transferred into a reaction kettle after being stirred evenly, sealed and placed at 120 ℃ for reaction for 4 hours. And centrifuging and washing the reaction product, drying at 60 ℃ for 6-8 h, weighing 0.2g of the product, 0.8g of magnesium powder and 8g of aluminum chloride powder, uniformly mixing, transferring to a reaction kettle, and reacting at 200 ℃ for 10 h. And (3) pickling the reaction product with a mixture (volume ratio is 2:1) of hydrochloric acid (2mol/L) and hydrofluoric acid (10 wt%) at 80 ℃ for 3 hours, purifying, drying and drying at 60 ℃ for 6-8 hours to obtain a powder sample. It can be seen from fig. 9 that the resulting silicon product is less pure and contains many impurity phases.
Comparative example 3
0.5g of halloysite clay mineral is weighed and dispersed into 2mol/L hydrochloric acid solution (40mL), the mixture is transferred into a reaction kettle after being stirred uniformly, sealed and placed at 120 ℃ for reaction for 4 hours. And centrifuging and washing the reaction product, drying at 60 ℃ for 6-8 h, weighing 0.2g of the product, 0.8g of magnesium powder and 8g of aluminum chloride powder, uniformly mixing, transferring to a reaction kettle, and reacting at 250 ℃ for 10 h. After the reaction product was acid-washed for 3h with a mixture (volume ratio 2:1) of hydrochloric acid (2mol/L) and hydrofluoric acid (10 wt%) at room temperature (25 ℃), purified, dried and dried at 60 ℃ for 6-8 h, a powder sample was obtained. From FIG. 1In 0, it can be seen that since the acid cleaning purification step is carried out at a relatively low temperature (25 ℃ C.), the silicon product obtained is low in purity and contains Al as a large impurity phase9Si。
Claims (12)
1. A preparation method of a three-dimensional cross-linked structure silicon nano material is characterized by comprising the following steps: uniformly dispersing halloysite into an acid solution for hydrothermal acidification treatment to obtain a silicon dioxide precursor; uniformly mixing the obtained silicon dioxide precursor, metal powder with strong reducibility and low-melting-point salt powder, transferring the mixture into a reaction kettle for sealed molten salt reduction reaction, and heating to 210-250 ℃ for reaction for 2-48 hours; acid washing, purifying and drying the reaction product to obtain the silicon nano material with the three-dimensional cross-linked structure; the metal powder with strong reducibility comprises one or two of magnesium powder and aluminum powder; the low-melting-point salt powder comprises one or two of aluminum chloride powder and magnesium chloride powder.
2. The preparation method according to claim 1, wherein the acid solution used in the hydrothermal acidification treatment is hydrochloric acid or sulfuric acid; the halloysite is uniformly dispersed into an acid solution with the molar concentration of 0.5-10 mol/L; the halloysite is uniformly dispersed in an acid solution according to the solid-liquid mass/volume ratio of 1g to 50-100 mL.
3. The method according to claim 2, wherein the molar concentration of the acid solution is 2 to 6 mol/L.
4. The preparation method according to claim 1, wherein the halloysite is uniformly dispersed in the acid solution, is transferred to a reaction kettle after being uniformly stirred, is sealed, and is heated to 80-150 ℃ for reaction for 0.5-10 h.
5. The method according to claim 4, wherein the temperature is in the range of 100 to 130 ℃ and the time is in the range of 2 to 5 hours.
6. The method according to claim 1, wherein the halloysite-derived silica precursor, the metal powder with strong reducibility and the low-melting-point salt powder are mixed uniformly, transferred to a reaction kettle, sealed, heated to 240-250 ℃ and reacted for 8-12 hours.
7. The method according to claim 1, wherein the mass ratio of the silica precursor obtained by the halloysite hydrothermal acidification treatment to the metal powder having strong reducibility is 1:0.6 to 0.9, and the mass ratio of the silica precursor obtained by the halloysite hydrothermal acidification treatment to the low-melting-point salt powder is 1:5 to 10.
8. The method according to claim 7, wherein the mass ratio of the silica precursor obtained by the hydrothermal acidification of the halloysite to the metal powder having strong reducibility is 1:0.8, and the mass ratio of the silica precursor obtained by the hydrothermal acidification of the halloysite to the powder of the low-melting-point salt is 1: 8.
9. The preparation method of claim 1, wherein the molten salt reduction reaction is performed with acid cleaning and purification by mixing 2-4 mol/L hydrochloric acid and 10 wt% hydrofluoric acid at a volume ratio of 2-3: 1; the pickling temperature is 70-90 ℃, and the pickling time is 2-6 h; and then drying for 6-8 h at 60 ℃.
10. The method according to claim 9, wherein the pickling temperature is 80 ℃.
11. A three-dimensional cross-linked silicon nanomaterial characterized by being produced by the method of any one of claims 1 to 10.
12. Use of the three-dimensionally crosslinked silicon nanomaterial of claim 11 as an ion battery negative electrode material.
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| WO2022246427A1 (en) * | 2021-05-18 | 2022-11-24 | Brigham Young University | Production of electrochemically active silicon from clay minerals |
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