阅读说明：本技术 硅-过渡金属硅化物纳米复合材料及其制备方法与应用 (Silicon-transition metal silicide nano composite material and preparation method and application thereof ) 是由 朱润良 陈情泽 杜静 何宏平 朱建喜 何秋芝 杨奕煊 魏洪燕 于 2019-11-28 设计创作，主要内容包括：本发明设计硅-过渡金属硅化物纳米复合材料领域,公开了硅-过渡金属硅化物纳米复合材料及其制备方法与应用。硅-过渡金属硅化物纳米复合材料的制备方法,包括：将含有前驱体、还原剂以及无机盐的混合物经500～900℃热反应得到；所述前驱体为含过渡金属离子的天然黏土矿物或经过渡金属离子改性后的改性黏土矿物。硅-过渡金属硅化物纳米复合材料,采用上述方法制得。该方法可制得纳米级别的具有较大比表面积的硅-过渡金属硅化物纳米复合材料。硅-过渡金属硅化物纳米复合材料在薄膜涂层、电子元件、热电材料、光伏材料或锂电子电池中具有良好的应用前景。(The invention relates to the field of silicon-transition metal silicide nanocomposite materials, and discloses a silicon-transition metal silicide nanocomposite material and a preparation method and application thereof. The preparation method of the silicon-transition metal silicide nanocomposite comprises the following steps: carrying out a thermal reaction on a mixture containing a precursor, a reducing agent and inorganic salt at 500-900 ℃ to obtain the catalyst; the precursor is natural clay mineral containing transition metal ions or modified clay mineral modified by the transition metal ions. The silicon-transition metal silicide nano composite material is prepared by adopting the method. The method can prepare the nano-scale silicon-transition metal silicide nano composite material with larger specific surface area. The silicon-transition metal silicide nanocomposite has good application prospects in thin film coatings, electronic elements, thermoelectric materials, photovoltaic materials or lithium electronic batteries.)

1. A method for preparing a silicon-transition metal silicide nanocomposite, comprising:

carrying out thermal reaction on a mixture containing a precursor, a reducing agent and inorganic salt at the temperature of 500-900 ℃ to obtain the catalyst; the precursor is natural clay mineral containing transition metal ions or modified clay mineral modified by the transition metal ions.

2. The method for preparing the silicon-transition metal silicide nanocomposite as claimed in claim 1, wherein the mass ratio of the precursor to the inorganic salt is 1:1 to 30; more preferably, the inorganic salt includes at least one of sodium chloride, potassium chloride, lithium chloride, and calcium chloride.

3. The method for preparing a silicon-transition metal silicide nanocomposite as claimed in claim 1 or 2, wherein the reducing agent is a reducing metal; more preferably, the mass ratio of the precursor to the reducing metal is 1: 0.3-6; more preferably, the reducing metal is at least one of magnesium, aluminum, sodium, potassium, and calcium;

preferably, the precursor, the reducing agent and the inorganic salt are all powder which is sieved by a 200-mesh sieve.

4. The method according to claim 3, wherein the transition metal ions in the natural clay mineral are greater than or equal to 5% by mass;

preferably, the natural clay mineral is at least one of oolitic chlorite, manganese chlorite, nickel chlorite, vermiculite, iron sepiolite, nickel sepiolite, iron palygorskite, iron serpentine, hydrobiotite, biotite and nontronite.

5. The method of claim 3, wherein the modified clay mineral is obtained by modifying clay mineral with transition metal ions;

preferably, the modification is by ion exchange or loading;

preferably, the mass ratio of the clay mineral to the transition metal ions is 1: 0.1-3;

more preferably, the clay mineral is at least one of montmorillonite, vermiculite, biotite, muscovite, illite, sepiolite, palygorskite, kaolinite and halloysite;

more preferably, the transition metal ion includes at least one of iron, manganese, cobalt, nickel, copper, titanium, and zirconium.

6. The method of claim 1, wherein the thermal reaction time is 0.5-12 hours.

7. The method of preparing a silicon-transition metal silicide nanocomposite as claimed in claim 1, wherein the method of preparing the modified clay mineral comprises:

mixing and reacting a transition metal ion pillared agent and a clay mineral suspension, and then sequentially performing aging, washing, centrifuging, drying and grinding to obtain the clay mineral suspension;

preferably, the aging process is carried out for 20-30 h at 55-65 ℃;

preferably, the mixing reaction of the transition metal ion pillaring agent and the clay mineral suspension is to drop the transition metal ion pillaring agent into the clay mineral suspension;

more preferably, stirring is continuously carried out in the dropping process, and the temperature of the system is kept at 55-65 ℃.

8. The method for preparing a silicon-transition metal silicide nanocomposite as claimed in any one of claims 4 to 7, wherein the thermal reaction of the mixture containing the precursor, the reducing agent and the inorganic salt further comprises:

sequentially carrying out acid washing, water washing and drying on the cooled thermal reaction product;

preferably, the acid selected in the acid washing process is hydrochloric acid, and the concentration of the hydrochloric acid is 0.5-5 mol/L;

preferably, acid liquor is adopted for acid washing for 2-4 times in the acid washing process, and each time lasts for 2-5 hours;

preferably, the water adopted in the water washing process is ultrapure water;

preferably, the drying process is drying under vacuum environment;

preferably, the drying temperature in the drying process is 50-80 ℃.

9. A silicon-transition metal silicide nanocomposite material, characterized by being produced by the production method as claimed in any one of claims 1 to 8.

10. Use of the silicon-transition metal silicide nanocomposite according to claim 9 in thin film coatings, electronic components, thermoelectric materials, photovoltaic materials or lithium electronic cells.

Technical Field

The invention relates to the field of silicon-transition metal silicide nano composite materials, in particular to a silicon-transition metal silicide nano composite material and a preparation method and application thereof.

Background

The silicon-transition metal silicide nanocomposite has the properties of high melting point, low resistivity, thermal stability, oxidation resistance, magnetism and the like, and is widely applied to various fields such as thin film coatings, electronic components, thermoelectric materials, photovoltaic materials and the like; in addition, the silicon-transition metal silicide nanocomposite has strong sulfur resistance and has potential value in a large amount of catalytic reactions containing sulfides. The traditional preparation methods of the silicon-transition metal silicide nano composite material mainly comprise a chemical vapor deposition method, a mechanical alloying method and a wet chemical method. However, these methods have some disadvantages, such as the use of toxic reagents, high cost, time consuming and the quality of the prepared product to be improved, and are difficult to realize in large-scale production.

In addition, in order to further improve the performance of the nano transition metal silicide in practical application and widen the application of the nano transition metal silicide in the fields of environmental remediation, energy storage and the like, other substances are often required to be compounded. For example, a transition metal silicide and silicon are compounded to prepare a transition metal silicide/silicon nanocomposite, and the hydrophobicity, the semiconductor property, the high lithium ion affinity and the like of the silicon are combined, so that the adsorption/catalysis performance, the lithium storage performance and the like of the material are improved. However, the additional introduction of silicon nanomaterials with difficult preparation and high price not only makes it difficult to realize the uniform and effective compounding of the transition metal silicide and silicon, but also has high preparation cost, which hinders the large-scale preparation and practical application of the transition metal silicide/silicon nanocomposite.

In view of this, the invention is particularly proposed.

Disclosure of Invention

The invention aims to provide a silicon-transition metal silicide nanocomposite and a preparation method thereof, wherein the method is simple and feasible, and the silicon-transition metal silicide nanocomposite with the nanoscale and the larger specific surface area can be prepared.

The invention is realized by the following steps:

in a first aspect, an embodiment of the present invention provides a method for preparing a silicon-transition metal silicide nanocomposite, including:

carrying out thermal reaction on a mixture containing a precursor, a reducing agent and inorganic salt at the temperature of 500-900 ℃ to obtain the catalyst; the precursor is natural clay mineral containing transition metal ions or modified clay mineral modified by transition metal ions.

In an optional embodiment, the mass ratio of the precursor to the inorganic salt is 1:1 to 30; more preferably, the inorganic salt includes at least one of sodium chloride, potassium chloride, lithium chloride, and calcium chloride.

In alternative embodiments, the reducing agent is a reducing metal; more preferably, the mass ratio of the precursor to the reducing metal is 1: 0.3-6; more preferably, the reducing metal is at least one of magnesium, aluminum, sodium, potassium, and calcium.

In an alternative embodiment, the precursor, the reducing agent and the inorganic salt are all powders that are sieved by a 200-mesh sieve.

In an optional embodiment, in the natural clay mineral, the mass ratio of the transition metal ions is greater than or equal to 5%;

preferably, the natural clay mineral is at least one of oolitic chlorite, manganese chlorite, nickel chlorite, vermiculite, iron sepiolite, nickel sepiolite, iron palygorskite, iron serpentine, hydrobiotite, biotite and nontronite.

In an alternative embodiment, the modified clay mineral is obtained by modifying a clay mineral with transition metal ions;

preferably, the mass ratio of the clay mineral to the transition metal ions is 1: 0.1-3;

more preferably, the clay mineral is at least one of montmorillonite, vermiculite, biotite, muscovite, illite, sepiolite, palygorskite, kaolinite and halloysite;

more preferably, the transition metal ion comprises at least one of iron, manganese, cobalt, nickel, copper, titanium, and zirconium.

In an alternative embodiment, the thermal reaction time is 0.5 to 12 hours.

In an alternative embodiment, the method for preparing a modified clay mineral comprises:

mixing and reacting a transition metal ion pillared agent and a clay mineral suspension, and then sequentially performing aging, washing, centrifuging, drying and grinding to obtain the clay mineral suspension;

preferably, the aging process is carried out for 20-30 h at 55-65 ℃;

preferably, the mixing reaction of the transition metal ion pillared agent and the clay mineral suspension is to drop the transition metal ion pillared agent into the clay mineral suspension;

more preferably, stirring is continuously carried out in the dropping process, and the temperature of the system is kept at 55-65 ℃.

In an alternative embodiment, the thermal reaction of the mixture containing the precursor, the reducing agent and the inorganic salt further comprises:

sequentially carrying out acid washing, water washing and drying on the cooled thermal reaction product;

preferably, the acid selected in the acid washing process is hydrochloric acid, and the concentration of the hydrochloric acid is 0.5-5 mol/L;

preferably, acid liquor is adopted for acid washing for 2-4 times in the acid washing process, and each time lasts for 2-5 hours;

preferably, the water adopted in the water washing process is ultrapure water;

preferably, the drying process is drying under vacuum environment;

preferably, the drying temperature in the drying process is 50-80 ℃.

In a second aspect, embodiments of the present invention provide a silicon-transition metal silicide nanocomposite material, which is prepared by the preparation method according to any one of the foregoing embodiments.

In a third aspect, embodiments of the present invention provide the use of a silicon-transition metal silicide nanocomposite material as in the previous embodiments in thin film coatings, electronic components, thermoelectric materials, photovoltaic materials, or lithium electronic cells.

The invention has the following beneficial effects:

the invention relates to a preparation method of the silicon-transition metal silicide nano composite material, because the precursor is selected from natural clay mineral containing transition metal ions or modified clay mineral modified by the transition metal ions, the clay mineral has a special lamellar structure or porous structure, so that the transition metal ion can microscopically contact with silicon at the atomic level no matter the transition metal ion-containing natural clay mineral or the transition metal ion-modified clay mineral, the method is beneficial to the generation of transition metal silicide during the subsequent thermal reaction, so that the microstructure of the substance produced after the subsequent thermal reaction can be basically consistent with the microstructure of clay mineral, so that the prepared silicon-transition metal silicide nano composite material has larger specific surface area. In the reaction process, under the action of a reducing agent, the clay mineral silicon-oxygen tetrahedron is firstly reduced into silicon nanocrystals, the reduction reaction is an exothermic reaction, and the high-activity silicon nanocrystals are combined with transition metals for thermal reaction to generate the silicon-transition metal silicide nano composite material. Because the transition metal silicide and the nano-silicon generated in the reaction process are compounded in situ, the transition metal silicide and the nano-silicon are uniformly distributed and firmly combined. Particularly, in the present invention, inorganic salts are also thermally reacted with the precursor and the reducing agent, and the addition of the inorganic salts absorbs excessive heat released in the reduction reaction to prevent the system temperature from being too high, thereby inhibiting the generation of a high-temperature phase (such as mullite), and on the other hand, acts as a spacer to prevent the generated silicon-transition metal silicide nanocomposite from aggregating and combining into bulk crystals to fail to obtain a nanoscale product.

The silicon-transition metal silicide nano composite material obtained by the design is prepared by the preparation method provided by the invention, so that the specific surface area is high, the particle size belongs to the nano level, and the silicon-transition metal silicide nano composite material can be applied to the fields of thin film coatings, electronic elements, thermoelectric materials, photovoltaic materials or lithium electronic batteries and the like.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is an X-ray diffraction pattern of a silicon-transition metal silicide nanocomposite prepared in example 1;

FIG. 2 is an SEM photograph of a transition metal silicide/silicon nanocomposite obtained in example 1.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The silicon-transition metal silicide nanocomposite provided by the present invention, and the preparation method and application thereof are specifically described below.

The embodiment of the invention provides a preparation method of a silicon-transition metal silicide nano composite material, which comprises the following steps:

carrying out a thermal reaction on a mixture containing a precursor, a reducing agent and inorganic salt at 500-900 ℃ to obtain the catalyst; the precursor is natural clay mineral containing transition metal ions or modified clay mineral modified by transition metal ions.

According to the preparation method provided by the invention, the precursor is a natural clay mineral containing transition metal ions or a modified clay mineral modified by the transition metal ions, the clay mineral has a special lamellar structure or porous structure, so that the clay mineral has a large specific surface area, and no matter the natural clay mineral containing the transition metal ions or the modified clay mineral modified by the transition metal ions, the transition metal ions and silicon can be in atom-level contact microscopically, so that the generation of transition metal silicide in a subsequent thermal reaction is facilitated, the microstructure of the clay mineral can be copied to a certain extent by a substance microstructure produced after the subsequent thermal reaction, and the prepared silicon-transition metal silicide nano composite material has a large specific surface area. The reducing agent reduces the clay mineral silicon-oxygen tetrahedron into silicon nanometer crystal, and the high activity silicon nanometer crystal and transition metal are combined to react thermally to produce the silicon-transition metal silicide nanometer composite material. In the reaction process, the reduction reaction process of the clay mineral silicon-oxygen tetrahedron is an exothermic reaction, which can cause excessive heat release in the reactants and excessive reaction temperature, and further cause high-temperature phases to appear in reaction products. In addition, the clay mineral is selected as the raw material, the raw material is rich in variety, low in price, simple and controllable in preparation process, suitable for large-scale production and high in economic benefit, a new method is provided for preparation of the transition metal silicide and the corresponding nanocomposite, and a new idea is provided for efficient high-value utilization of the clay mineral resource. In the method provided by the invention, because the transition metal silicide and the nano-silicon generated in the reaction process are compounded in situ, the transition metal silicide and the nano-silicon are uniformly distributed and firmly combined.

In the embodiment provided by the invention, if the precursor is a natural clay mineral containing transition metal ions, the natural clay mineral with the mass ratio of the transition metal ions being greater than or equal to 5% is selected to ensure the content of the transition metal ions in the prepared silicon-transition metal silicide nanocomposite. Specifically, the natural clay minerals containing transition metal ions are selected from at least one of oolitic chlorite, manganese chlorite, nickel chlorite, vermiculite, iron sepiolite, nickel sepiolite, iron palygorskite, iron serpentine, hydrobiotite, biotite and nontronite.

In the embodiment provided by the invention, if the precursor is a modified clay mineral modified by transition metal ions. Then the clay mineral is modified by transition metal ions, either by ion exchange or by loading. It should be noted that the term "ion exchange" as used herein is to be understood in a broad sense, i.e., the exchange of ions occurs during the reaction. In the preferred embodiment provided by the invention, the clay mineral is modified mainly by an ion exchange mode, and the ion exchange modification mode is mainly to mix and react the transition metal ion pillared agent and the clay mineral suspension.

In a preferred embodiment of the invention, the precursor is modified montmorillonite, the microscopic result of the montmorillonite is sheet-shaped, the specific surface area is large, and the prepared silicon-transition metal silicide nanocomposite has better quality.

The preparation method of the silicon-transition metal silicide nano composite material provided by the embodiment of the invention specifically comprises the following steps:

preparing a precursor:

in order to ensure full reaction, the transition metal ion pillared agent is added into the clay mineral suspension in a dropwise manner, and the temperature is ensured to be 55-65 ℃ in the dropwise adding process. After the dropwise adding is finished, the temperature is kept at 55-65 ℃ for aging reaction for 20-30 h. And after aging, washing, centrifuging, drying and finally grinding to obtain precursor powder.

Thermal reaction:

and (3) placing the mixture obtained by uniformly mixing the precursor powder, the reducing agent and the inorganic salt in a tubular furnace, and adjusting the temperature of the tubular furnace to be 500-900 ℃ for thermal reaction to obtain a crude product. In order to ensure the sufficient thermal reaction and not waste too much energy, the thermal reaction time is 0.5-12 h. In order to make the mixing more uniform and complete, in a preferred embodiment of the present invention, the precursor powder, the reducing agent and the inorganic salt are all powders that are sieved after passing through a 200-mesh sieve.

Preferably, in embodiments of the present invention the reducing agent is a reducing metal. In the prior art, reducing gas is adopted as a reducing agent, but the reducing gas has the problems of inconvenient operation and potential safety hazards such as explosion and the like, but the reducing agent is adopted to act on reducing metal in the application, so that the problems are solved.

Preferably, in order to ensure that the silicon-oxygen tetrahedron is fully reduced to silicon nanocrystals, the mass ratio of the precursor to the reducing metal in the present invention is 1: 0.3-6. Preferably, the mass ratio of the precursor to the inorganic salt is 1: 1-30, in order to ensure that the content of the inorganic salt is sufficient to fully absorb the heat released by the thermal reaction, but not too much to affect the quality of the product after the thermal reaction.

Preferably, in a preferred embodiment provided by the present invention, the selected inorganic salt includes at least one of sodium chloride, potassium chloride, lithium chloride and calcium chloride. The principle of selecting these inorganic salts is: the melting point of the selected inorganic salt is higher than the reaction set temperature so that the inorganic salt can absorb excessive heat released in the reaction by melting itself, and the selected inorganic salt is stable in properties, is not easily decomposed, and does not participate in the reaction.

Preferably, in a preferred embodiment provided by the present invention, the reducing metal is at least one of magnesium, aluminum, sodium, potassium and calcium. These reducing metals are preferred because they are easily obtained and have a good reducing effect.

Impurity removal process:

and naturally cooling the product after the thermal reaction, and sequentially carrying out acid washing, water washing and drying after cooling to obtain the finished product of the silicon-transition metal silicide nano composite material.

Preferably, in order to ensure good impurity removal effect, the acid selected in the acid washing process is hydrochloric acid, and the concentration of the hydrochloric acid is 0.5-5 mol/L. The hydrochloric acid dissolves the impurities loaded in the pores or the surface of the silicon-transition metal silicide nano composite material.

Preferably, in order to ensure thorough impurity removal, acid liquor is adopted for pickling for 2-4 times in the pickling process, and each time lasts for 2-5 hours.

Preferably, the water used in the water washing process is ultrapure water, and the number of washing times is multiple to ensure sufficient cleaning of impurities.

Preferably, the drying process is performed in a vacuum environment to avoid air from reacting with the silicon-transition metal silicide nanocomposite to affect the product quality.

Preferably, the drying temperature is 50-80 ℃ to ensure rapid drying and prevent the phase change of the silicon-transition metal silicide nanocomposite caused by too high drying temperature.

In order to avoid the deterioration of the product, the prepared silicon-transition metal silicide nano composite material is placed in a brown bottle for storage.

The embodiment of the invention also provides a silicon-transition metal silicide nano composite material which is prepared by the preparation method provided by the embodiment of the invention. Therefore, the silicon-transition metal silicide nano composite material has larger specific surface area and better microscopic appearance.

The features and properties of the present invention are described in further detail below with reference to examples.