阅读说明：本技术 一种偏硅酸锂/镍复合材料的制备方法 (Preparation method of lithium metasilicate/nickel composite material ) 是由 张辉 孙博 陈文革 于 2021-08-04 设计创作，主要内容包括：本发明公开了一种Li-(2)SiO-(3)/Ni复合材料的制备方法,将泡沫镍置于过量无水乙醇超声后洗涤,再置于盐酸中静置后洗涤,得处理后泡沫镍,将LiOH·H-(2)O完全溶解于蒸馏水(去离子水/纯水)后滴加正硅酸四乙酯(TEOS),充分搅拌均匀得到混合溶液,将处理后泡沫镍和混合溶液加入聚四氟乙烯内胆中反应得到样品负载的泡沫镍,对其进行抽滤、洗涤、干燥得到Li-(2)SiO-(3)/Ni复合材料。本发明制备的Li-(2)SiO-(3)微纳结构在泡沫镍上界面结合良好,形态均匀,相纯度高。(The invention discloses Li 2 SiO 3 The preparation method of the/Ni composite material comprises the steps of placing foamed nickel in excessive absolute ethyl alcohol for ultrasonic treatment, washing, placing in hydrochloric acid for standing, washing to obtain treated foamed nickel, and placing LiOH & H 2 Completely dissolving O in distilled water (deionized water/pure water), dropwise adding tetraethyl orthosilicate (TEOS), fully and uniformly stirring to obtain a mixed solution, adding the treated foam nickel and the mixed solution into a polytetrafluoroethylene liner to react to obtain sample-loaded foam nickel, and performing suction filtration, washing and drying on the sample-loaded foam nickel to obtain Li 2 SiO 3 a/Ni composite material. Li prepared by the invention 2 SiO 3 The micro-nano structure has good interface combination on the foam nickel, uniform shape and high phase purity.)

1. Li₂SiO₃The preparation method of the/Ni composite material is characterized by comprising the following steps: the method specifically comprises the following steps:

step 1, processing foam nickel;

step 2, preparing a lithium hydroxide aqueous solution;

step 3, preparing a mixed solution according to the solution obtained in the step 2;

step 4, preparing sample-loaded foamed nickel;

step 5, carrying out suction filtration on the foamed nickel loaded on the sample prepared in the step 4, washing the foamed nickel for 3-5 times by using distilled water and alcohol respectively, and removing impurities in the residual solution to obtain a sample filter cake;

and 6, keeping the temperature of the sample filter cake obtained in the step 5 at 60-80 ℃ and drying for 12-24 h, and removing water molecules and alcohol molecules to obtain the foamed nickel loaded on the dried sample.

2. Li according to claim 1₂SiO₃The preparation method of the/Ni composite material is characterized by comprising the following steps: the specific process of the step 1 is as follows: placing untreated foamed nickel in excessive absolute ethyl alcohol, performing ultrasonic treatment for 20-40 min to remove surface impurities, washing with deionized water for 3 times, then placing in 2-6 mol/L hydrochloric acid to remove NiO and residual ions on the surface of the foamed nickel, sealing and standing a preservative film for 30-60 min, and washing with deionized water for 3 times to obtain the treated foamed nickel.

3. Li according to claim 2₂SiO₃The preparation method of the/Ni composite material is characterized by comprising the following steps: the specific process of the step 2 is as follows: reacting LiOH & H₂Adding O into 70ml of distilled water, magnetically stirring for 30-40 min at the stirring speed of 600-1000 r/min to ensure that LiOH. H₂And completely dissolving the O to obtain a transparent lithium hydroxide aqueous solution.

4. Li according to claim 3₂SiO₃The preparation method of the/Ni composite material is characterized by comprising the following steps: the specific process of the step 3 is as follows: dropping TEOS into the transparent lithium hydroxide aqueous solution prepared in the step 2 within 5-10 minAnd (3) the molar ratio of Li to Si is 1.7-10, and after the dripping is finished, magnetic stirring is continuously carried out, wherein the magnetic stirring speed is 600-1000 r/min, and the stirring time is 30-60 min, so that a uniform mixed solution is obtained.

5. Li according to claim 4₂SiO₃The preparation method of the/Ni composite material is characterized by comprising the following steps: the specific steps of the step 4 are as follows: and (3) adding the processed foamed nickel obtained in the step (1) and the mixed solution obtained in the step (3) into a polytetrafluoroethylene inner container, controlling the volume filling degree of the inner container to be 70-80%, sealing a stainless steel reaction kettle, and reacting at 150-180 ℃ for 10-12 h to obtain the sample-loaded foamed nickel.

Technical Field

The invention belongs to the technical field of preparation of inorganic micro-nano powder, and relates to Li₂SiO₃A preparation method of a/Ni composite material.

Background

The rapid development of economic technology leads to the ever-increasing demand of society for energy, and directly leads to the increasing problems of environmental pollution, energy shortage and the like. Lithium metasilicate (Li)₂SiO₃) Because of the special properties of excellent high-temperature structural stability, mechanical stability, nontoxicity, good tritium solubility, good irradiation performance, good compatibility with other structural materials and the like, the material has new energy, environmental protection and the likeThe material has potential application value in the field, and can be used as a lithium ion battery anode material, a solid tritium value-added material, an environmental material and the like. In addition, the raw material for synthesizing lithium metasilicate has abundant resources, low cost and no pollution to the environment, so that the further research on the lithium metasilicate material is more widely concerned. In addition, Nickel foam (Nickel foam) has a three-dimensional porous structure, and is widely selected as a substrate due to its advantages of high specific surface area, high electronic conductivity, low cost, and easy practical use. In scientific and technical research, a plurality of methods are used for synthesizing lithium metasilicate micro-nano structures on different substrates, such as a solid-state reaction method, a calcination method, a sol-gel method and the like. However, the lithium metasilicate micro-nano structure obtained by the methods is poor in load degree and uneven, and has the inherent defect of insufficient reaction power.

The existing research utilizes a hydrothermal reaction process to synthesize Li on foamed nickel₂SiO₃The micro-nano structure has good load degree and uniform shape, has great breakthrough in scale compared with the process, and realizes the growth of Li on the nickel foam₂SiO₃The micro-nano structure does not fill the blank for regulating the appearance of the foam nickel. Meanwhile, the Li/Si raw material selected by the system is required to be more than 1.7, which does not meet the standard stoichiometric ratio, thereby not only wasting the raw material, but also influencing the load degree of the product. Thus, how to obtain Li by a simple and efficient method₂SiO₃the/Ni composite material is still a problem to be solved urgently by modern scientific and technical research.

Disclosure of Invention

It is an object of the present invention to provide a Li₂SiO₃Preparation method of/Ni composite material and Li prepared by method₂SiO₃The micro-nano structure has good interface combination on the foam nickel, uniform shape and high phase purity.

The technical scheme adopted by the invention is that Li₂SiO₃The preparation method of the/Ni composite material specifically comprises the following steps:

step 1, processing foam nickel;

step 2, preparing a lithium hydroxide aqueous solution;

step 3, preparing a mixed solution according to the solution obtained in the step 2;

step 4, preparing sample-loaded foamed nickel;

step 5, carrying out suction filtration on the foamed nickel loaded on the sample prepared in the step 4, washing the foamed nickel for 3-5 times by using distilled water and alcohol respectively, and removing impurities in the residual solution to obtain a sample filter cake;

and 6, keeping the temperature of the sample filter cake obtained in the step 5 at 60-80 ℃ and drying for 12-24 h, and removing water molecules and alcohol molecules to obtain the foamed nickel loaded on the dried sample.

The invention is also characterized in that:

the specific process of the step 1 is as follows: placing untreated foamed nickel in excessive absolute ethyl alcohol, performing ultrasonic treatment for 20-40 min to remove surface impurities, washing with deionized water for 3 times, then placing in 2-6 mol/L hydrochloric acid to remove NiO and residual ions on the surface of the foamed nickel, sealing and standing a preservative film for 30-60 min, and washing with deionized water for 3 times to obtain the treated foamed nickel.

The specific process of the step 2 is as follows: reacting LiOH & H₂Adding O into 70ml of distilled water, magnetically stirring for 30-40 min at the stirring speed of 600-1000 r/min to ensure that LiOH. H₂And completely dissolving the O to obtain a transparent lithium hydroxide aqueous solution.

The specific process of the step 3 is as follows: and (3) dropwise adding TEOS into the transparent lithium hydroxide aqueous solution prepared in the step (2) within 5-10 min to enable the molar ratio of Li to Si to be 1.7-10, and then continuing to perform magnetic stirring at the magnetic stirring speed of 600-1000 r/min for 30-60 min to obtain a uniform mixed solution.

The specific steps of the step 4 are as follows: and (3) adding the processed foamed nickel obtained in the step (1) and the mixed solution obtained in the step (3) into a polytetrafluoroethylene inner container, controlling the volume filling degree of the inner container to be 70-80%, sealing a stainless steel reaction kettle, and reacting at 150-180 ℃ for 10-12 h to obtain the sample-loaded foamed nickel.

The invention has the beneficial effects that: the invention adopts distilled water (deionized water/pure water) solvent as hydrothermal reaction medium, and has no pollution to environment; by usingThe raw materials of (A) are tetraethyl orthosilicate (TEOS) and lithium hydroxide monohydrate (LiOH. H)₂O), ensuring sufficient reaction power in the later period, and avoiding generating other impurities and harmful substances; the foam nickel is adopted as the conductive substrate, has larger specific surface area and high conductivity, and is easy to regulate and control the form of the lithium metasilicate; by adopting a hydrothermal reaction method and taking a stainless steel reaction kettle as a shell, the device is sealed and safe, does not overflow harmful substances, has low reaction temperature, and is energy-saving and environment-friendly; li on the foam nickel can be realized by adjusting the molar ratio of Li to Si (1.7-10)₂SiO₃Regulating and controlling the appearance of the assembly unit; obtained Li₂SiO₃The interface of the/Ni composite material is well combined, and the shape is uniform.

Drawings

FIG. 1 shows a Li according to the invention₂SiO₃Typical Li prepared by preparation method of/Ni composite material₂SiO₃The overall topography of the/Ni composite material is shown in the figure 1(a), the surface of the composite material is enlarged, and the columnar crystal of the assembly unit is enlarged in the figure 1 (c);

FIG. 2 shows a Li according to the present invention₂SiO₃Typical Li prepared by preparation method of/Ni composite material₂SiO₃XRD phase pattern of the/Ni composite material.

Detailed Description

The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.

The invention relates to Li₂SiO₃A method for preparing a/Ni composite material by reacting LiOH H₂Pouring O into distilled water until LiOH & H₂Completely dissolving O, dropwise adding TEOS, magnetically stirring uniformly to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene inner container, adding the treated foamed nickel, sealing a stainless steel reaction kettle, carrying out hydrothermal reaction to obtain sample-loaded foamed nickel, and carrying out suction filtration, washing and drying on the obtained product to obtain Li₂SiO₃a/Ni composite material. The method comprises the following steps:

step 1, placing untreated foamed nickel in excessive absolute ethyl alcohol, performing ultrasonic treatment for 20-40 min to remove surface impurities, washing with deionized water for 3 times, then placing in 2-6 mol/L hydrochloric acid to remove NiO and residual ions on the surface of the foamed nickel, sealing and standing a preservative film for 30-60 min, and washing with deionized water for 3 times to obtain treated foamed nickel;

step 2, weighing LiOH. H₂O, reaction of LiOH. H₂Adding O into 70ml of distilled water, and magnetically stirring for 30-40 min at the stirring speed of 600-1000 r/min to completely dissolve O to obtain a transparent lithium hydroxide aqueous solution;

step 3, weighing TEOS, dropwise adding the TEOS into the transparent lithium hydroxide aqueous solution prepared in the step S2 within 5-10 min to enable the molar ratio of Li to Si to be 1.7-10, and after dropwise adding is finished, continuing to stir by magnetic force at a speed of 600-1000 r/min for 30-60 min to obtain a uniform mixed solution;

step 4, adding the processed foamed nickel obtained in the step 1 and the mixed solution obtained in the step S3 into a polytetrafluoroethylene inner container, controlling the volume filling degree of the inner container to be 70-80%, sealing a stainless steel reaction kettle, and reacting at 150-180 ℃ for 10-12 hours to obtain sample-loaded foamed nickel;

step 5, carrying out suction filtration on the foamed nickel loaded on the sample prepared in the step 4, washing the foamed nickel for 3-5 times by using distilled water and alcohol respectively, and removing impurities in the residual solution to obtain a sample filter cake;

and 6, drying the foamed nickel and the filter cake obtained in the step 5 at the temperature of 60-80 ℃ for 12-24 hours, and removing water molecules and alcohol molecules to obtain the foamed nickel loaded on the dry sample.

The magnetic stirring method is simple to operate, does not need sealing operation, has low operation requirement on the early stage of reaction, and is convenient for industrial production.

The Li/Si molar ratio is set to be 1.7-10, so that the high purity and high crystallinity of the lithium metasilicate product can be ensured simultaneously.

According to the invention, the hydrothermal reaction temperature is set to be 150-180 ℃ and the reaction time is set to be 10-12 h, so that the loading degree and uniformity of the lithium metasilicate micro-nano structure on the foamed nickel can be regulated and controlled.

The mixed solvent proportion, the hydrothermal reaction temperature, the hydrothermal reaction time and the filling degree in the invention have wide ranges, and have the significance of easy control on the following large-scale production.

In the suction filtration process, the residual solvent in the reaction and unreacted ions adsorbed on the product can be removed by washing distilled water and alcohol, and meanwhile, hard agglomeration in the subsequent drying process can be avoided, and the dispersibility of the product is improved.

The invention can thoroughly remove water and alcohol molecules during washing by slow drying, thereby ensuring the dryness of the product.

The preparation method provided by the invention has the advantages of simple equipment requirement, simple and cheap operation, low raw material price, adjustable and easily-controlled reaction parameter ranges such as raw material proportion and the like, high product yield, controllable shape of the prepared micro-nano structure, uniform load and suitability for large-scale industrial production and commercial popularization.

Example 1

Step 1, placing untreated foamed nickel in excessive absolute ethyl alcohol, performing ultrasonic treatment for 30min to remove surface impurities, washing with deionized water for 3 times, then placing in 2mol/L hydrochloric acid to remove NiO and residual ions on the surface of the foamed nickel, sealing and standing a preservative film for 30min, and washing with deionized water for 3 times to obtain treated foamed nickel;

step 2, weighing LiOH. H₂O, reaction of LiOH. H₂Adding O into 70ml of distilled water, and magnetically stirring for 30min at the stirring speed of 700r/min to completely dissolve the O to obtain a transparent lithium hydroxide aqueous solution;

step 3, weighing TEOS, dropwise adding the TEOS into the transparent lithium hydroxide aqueous solution prepared in the step S within 10min to enable the Li/Si molar ratio to be 1.8, and after dropwise adding is finished, continuing to stir by magnetic force at 700r/min for 30min to obtain a uniform mixed solution;

step 4, adding the processed foamed nickel obtained in the step 1 and the mixed solution obtained in the step S3 into a polytetrafluoroethylene inner container, controlling the volume filling degree of the inner container to be 80%, sealing a stainless steel reaction kettle, and reacting at 180 ℃ for 12 hours to obtain sample-loaded foamed nickel;

step 5, carrying out suction filtration on the sample loaded foamed nickel prepared in the step 4, respectively washing the sample loaded foamed nickel for 3 times by using distilled water and alcohol, and removing impurities in residual solution to obtain a sample filter cake;

and 6, keeping the temperature of the foam nickel filter cake obtained in the step 5 at 60 ℃ and drying for 24h, and removing water molecules and alcohol molecules to obtain the foam nickel loaded on the dry sample.

Example 2

Step 1, placing untreated foamed nickel in excessive absolute ethyl alcohol, performing ultrasonic treatment for 30min to remove surface impurities, washing with deionized water for 3 times, then placing in 2mol/L hydrochloric acid to remove NiO and residual ions on the surface of the foamed nickel, sealing and standing a preservative film for 30min, and washing with deionized water for 3 times to obtain treated foamed nickel;

step 2, weighing LiOH. H₂O, reaction of LiOH. H₂Adding O into 70ml of distilled water, and magnetically stirring for 30min at the stirring speed of 700r/min to completely dissolve the O to obtain a transparent lithium hydroxide aqueous solution;

step 3, weighing TEOS, dropwise adding the TEOS into the transparent lithium hydroxide aqueous solution prepared in the step 2 within 10min to enable the molar ratio of Li to Si to be 2, and after dropwise adding, continuing to stir by magnetic force at 700r/min for 30min to obtain a uniform mixed solution;

step 4, adding the processed foamed nickel obtained in the step 1 and the mixed solution obtained in the step S3 into a polytetrafluoroethylene inner container, controlling the volume filling degree of the inner container to be 80%, sealing a stainless steel reaction kettle, and reacting at 180 ℃ for 12 hours to obtain sample-loaded foamed nickel;

step 5, carrying out suction filtration on the sample loaded foamed nickel prepared in the step 4, respectively washing the sample loaded foamed nickel for 3 times by using distilled water and alcohol, and removing impurities in residual solution to obtain a sample filter cake;

and 6, keeping the temperature of the foam nickel filter cake obtained in the step 5 at 60 ℃ and drying for 24h, and removing water molecules and alcohol molecules to obtain the foam nickel loaded on the dry sample.

Example 3

Step 1, placing untreated foamed nickel in excessive absolute ethyl alcohol, performing ultrasonic treatment for 30min to remove surface impurities, washing with deionized water for 3 times, then placing in 2mol/L hydrochloric acid to remove NiO and residual ions on the surface of the foamed nickel, sealing and standing a preservative film for 30min, and washing with deionized water for 3 times to obtain treated foamed nickel;

step 2, weighing LiOH. H₂O, reaction of LiOH. H₂Adding O into 70ml of distilled water, and magnetically stirring for 30min at the stirring speed of 700r/min to completely dissolve the O to obtain a transparent lithium hydroxide aqueous solution;

step 3, weighing TEOS, dropwise adding the TEOS into the transparent lithium hydroxide aqueous solution prepared in the step 2 within 10min to ensure that the molar ratio of Li to Si is 2.5, and after dropwise adding, continuing to stir by magnetic force at 700r/min for 30min to obtain a uniform mixed solution;

step 4, adding the processed foamed nickel obtained in the step 1 and the mixed solution obtained in the step 3 into a polytetrafluoroethylene inner container, controlling the volume filling degree of the inner container to be 80%, sealing a stainless steel reaction kettle, and reacting at 180 ℃ for 12 hours to obtain sample-loaded foamed nickel;

step 5, carrying out suction filtration on the sample loaded foamed nickel prepared in the step 4, respectively washing the sample loaded foamed nickel for 3 times by using distilled water and alcohol, and removing impurities in residual solution to obtain a sample filter cake;

and 6, keeping the temperature of the foam nickel filter cake obtained in the step 5 at 60 ℃ and drying for 24h, and removing water molecules and alcohol molecules to obtain the foam nickel loaded on the dry sample.

Example 4

Step 1, placing untreated foamed nickel in excessive absolute ethyl alcohol, performing ultrasonic treatment for 30min to remove surface impurities, washing with deionized water for 3 times, then placing in 2mol/L hydrochloric acid to remove NiO and residual ions on the surface of the foamed nickel, sealing and standing a preservative film for 30min, and washing with deionized water for 3 times to obtain treated foamed nickel;

step 2, weighing LiOH. H₂O, reaction of LiOH. H₂Adding O into 70ml of distilled water, and magnetically stirring for 30min at the stirring speed of 700r/min to completely dissolve the O to obtain a transparent lithium hydroxide aqueous solution;

step 3, weighing TEOS, dropwise adding the TEOS into the transparent lithium hydroxide aqueous solution prepared in the step 2 within 10min to enable the molar ratio of Li to Si to be 10, and after dropwise adding, continuing to stir by magnetic force at 700r/min for 30min to obtain a uniform mixed solution;

step 4, adding the processed foamed nickel obtained in the step 1 and the mixed solution obtained in the step 3 into a polytetrafluoroethylene inner container, controlling the volume filling degree of the inner container to be 80%, sealing a stainless steel reaction kettle, and reacting at 180 ℃ for 12 hours to obtain sample-loaded foamed nickel;

step 5, carrying out suction filtration on the sample loaded foamed nickel prepared in the step 4, respectively washing the sample loaded foamed nickel for 3 times by using distilled water and alcohol, and removing impurities in residual solution to obtain a sample filter cake;

and 6, keeping the temperature of the foam nickel filter cake obtained in the step 5 at 60 ℃ and drying for 24h, and removing water molecules and alcohol molecules to obtain the foam nickel loaded on the dry sample.

FIG. 1 shows Li obtained in example 3 of the present invention₂SiO₃The structural morphology of the/Ni composite material is shown in the figure 1(a), which is the overall morphology of the composite material; FIG. 1(b) is a magnified view of the surface of the composite material; FIG. 1(c) is an enlarged view of assembled unit columnar crystals of the composite material. From fig. 1(a) to (c), the composite material has a complete structure and a flat rod-shaped crystal surface, which illustrates that the nickel foam has excellent loading degree, uniform morphology and good interface bonding.

FIG. 2 shows Li obtained in example 3 of the present invention₂SiO₃XRD pattern of the/Ni composite material. No other impurity phases were observed from the XRD pattern, indicating Li₂SiO₃The crystalline phase purity of the/Ni composite material is high, and the peak intensity is high, so that the form uniformity of a sample is further demonstrated.

The invention relates to Li₂SiO₃The preparation method of the/Ni composite material uses the raw materials including distilled water (deionized water/pure water), Nickel foam (Nickel foam), tetraethyl orthosilicate (TEOS) and lithium hydroxide monohydrate (LiOH. H)₂O), avoiding introducing other impurities and harmful substances, and having no pollution to the environment. The method has the advantages of simple equipment requirement, simple and cheap operation, low raw material price, adjustable and easily-controlled reaction parameter ranges such as raw material proportion and the like, uniform product loading degree and good interface combination, and the prepared Li₂SiO₃the/Ni composite material has uniform and controllable shape, and is suitable for large-scale industrial production and commercial popularization.