阅读说明：本技术 一种聚苯胺原位聚合插层五氧化二钒及其制备方法和应用 (Polyaniline in-situ polymerization intercalation vanadium pentoxide and preparation method and application thereof ) 是由 王明珊 张俊 李星 于 2020-08-06 设计创作，主要内容包括：本发明属于电极材料技术领域,本发明提供了一种聚苯胺原位聚合插层五氧化二钒的制备方法,包括以下步骤：将五氧化二钒粉体、水和双氧水混合得到溶液a；将苯胺单体和水混合后使用酸溶液调节pH值,得到溶液b；将溶液a与溶液b混合后进行反应,得到聚苯胺原位聚合插层五氧化二钒。本发明以五氧化二钒粉体为钒源,以苯胺单体原位聚合为插层分子,以双氧水为助溶剂制备得到高比容量、循环稳定性和倍率性能优异的聚苯胺原位聚合插层五氧化二钒。本发明的电极材料在1A·g<Sup>-1</Sup>和5A·g<Sup>-1</Sup>的电流密度下首次放电比容量分别为330～390mAh·g<Sup>-1</Sup>和120～180mAh·g<Sup>-1</Sup>。(The invention belongs to the technical field of electrode materials, and provides a preparation method of polyaniline in-situ polymerization intercalation vanadium pentoxide, which comprises the following steps: mixing vanadium pentoxide powder, water and hydrogen peroxide to obtain a solution a; mixing aniline monomer and water, and adjusting the pH value by using an acid solution to obtain a solution b; and mixing the solution a and the solution b and then reacting to obtain the polyaniline in-situ polymerization intercalation vanadium pentoxide. The polyaniline in-situ polymerization intercalation vanadium pentoxide with high specific capacity, excellent cycle stability and excellent rate performance is prepared by taking vanadium pentoxide powder as a vanadium source, aniline monomer in-situ polymerization as intercalation molecules and hydrogen peroxide as a cosolvent. Electrode material of the present inventionAt 1 A.g ‑1 And 5 A.g ‑1 The specific capacity of the first discharge under the current density is 330-390 mAh.g ‑1 And 120 to 180 mAh.g ‑1 。)

1. A preparation method of polyaniline in-situ polymerization intercalation vanadium pentoxide is characterized by comprising the following steps:

1) mixing vanadium pentoxide powder, water and hydrogen peroxide to obtain a solution a;

2) mixing aniline monomer and water, and adjusting the pH value by using an acid solution to obtain a solution b;

3) and mixing the solution a and the solution b and then reacting to obtain the polyaniline in-situ polymerization intercalation vanadium pentoxide.

2. The preparation method according to claim 1, wherein the ratio of the vanadium pentoxide powder in the step 1) to the water to the hydrogen peroxide is 1-20 mmol: 1-200 mL: 1-20 mL; the mixing time is 1-24 h; the mass fraction of the hydrogen peroxide is 20-40%; the particle size of the vanadium pentoxide powder is 1-50 μm.

3. The preparation method according to claim 1 or 2, wherein the ratio of the aniline monomer and water in step 2) is 0.2 to 4 mmol: 1-300 mL; the pH value is 1-4.

4. The preparation method according to claim 3, wherein the concentration of the acid solution in the step 2) is 0.2-10 mol/L, and the acid solution is hydrochloric acid, sulfuric acid, phosphoric acid, sulfurous acid, acetic acid or citric acid.

5. The preparation method according to claim 4, wherein the reaction temperature in the step 3) is 60-180 ℃ and the reaction time is 1-24 h.

6. The method according to claim 5, wherein the mixing in step 3) is carried out by heating the solution a to a reaction temperature and mixing the solution a with the solution b, and after the reaction is completed, freeze-drying and vacuum-drying are carried out in this order.

7. The preparation method according to claim 6, wherein the freeze drying time is 24-72 hours, the vacuum drying temperature is 60-240 ℃, the vacuum drying time is 1-10 hours, and the vacuum degree is 2-4 KPa.

8. The polyaniline in-situ polymerization intercalation vanadium pentoxide obtained by the preparation method of any one of claims 1 to 7, wherein the thickness of the polyaniline in-situ polymerization intercalation vanadium pentoxide is 10-500 nm, and the mass fraction of polyaniline is 3.0-40%.

9. The use of the polyaniline in-situ polymerized intercalated vanadium pentoxide of claim 8 as an electrode material in metal-ion batteries and metal-ion capacitors.

10. The use according to claim 9, wherein the metal-ion battery is a zinc-ion battery, a lithium-ion battery, a sodium-ion battery, a potassium-ion battery or a magnesium-ion battery, and the metal-ion capacitor is a lithium-ion capacitor or a sodium-ion capacitor.

Technical Field

The invention relates to the technical field of electrode materials, in particular to polyaniline in-situ polymerization intercalation vanadium pentoxide and a preparation method and application thereof.

Background

Rechargeable secondary batteries have been widely used in the fields of wearable devices, electric vehicles, and the like. With the development of society, people have more and more urgent demands for batteries with high specific capacity. However, the theoretical capacity of the lithium iron phosphate serving as the current commercial anode material and the ternary anode material is 160-220 mAh.g^-1And the requirements of people are difficult to meet. Therefore, a high specific capacity of the positive electrode material is urgently required to meet the market demand. The vanadium-based oxide has a high theoretical capacity (300-400 mAh.g)^-1) Is a potential high specific capacity anode material with larger interlayer spacingA two-dimensional channel can be provided for ion de-intercalation; meanwhile, the lithium ion battery anode material has the advantages of low price, easiness in preparation and the like, and is an anode material with a very good application prospect.

However, vanadium pentoxide, as a secondary battery positive electrode material, is still too small in interlayer and unstable in structure during circulation, so that ion diffusion is hindered, capacity attenuation is severe, and circulation stability is reduced. Therefore, the vanadium-based cathode material which is stable in structure, improves the ion diffusion rate, ensures high specific capacity, is stable in long circulation and excellent in rate performance is provided, and has a very good market prospect.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provide polyaniline in-situ polymerization intercalation vanadium pentoxide and a preparation method thereof.

In order to achieve the above object, the present invention provides the following technical solutions:

the invention provides a preparation method of polyaniline in-situ polymerization intercalation vanadium pentoxide, which comprises the following steps:

1) mixing vanadium pentoxide powder, water and hydrogen peroxide to obtain a solution a;

2) mixing aniline monomer and water, and adjusting the pH value by using an acid solution to obtain a solution b;

3) and mixing the solution a and the solution b and then reacting to obtain the polyaniline in-situ polymerization intercalation vanadium pentoxide.

Preferably, the ratio of the vanadium pentoxide powder, water and hydrogen peroxide in the step 1) is 1-20 mmol: 1-200 mL: 1-20 mL; the mixing time is 1-24 h; the mass fraction of the hydrogen peroxide is 20-40%; the particle size of the vanadium pentoxide powder is 1-50 μm.

Preferably, the ratio of the aniline monomer to water in the step 2) is 0.2-4 mmol: 1-300 mL; the pH value is 1-4.

Preferably, the concentration of the acid solution in the step 2) is 0.2-10 mol/L, and the acid solution is hydrochloric acid, sulfuric acid, phosphoric acid, sulfurous acid, acetic acid or citric acid.

Preferably, the reaction temperature in the step 3) is 60-180 ℃, and the reaction time is 1-24 h.

Preferably, in the step 3), the solution a is heated to a reaction temperature and then mixed with the solution b, and after the reaction is finished, freeze drying and vacuum drying are sequentially performed.

Preferably, the freeze drying time is 24-72 hours, the vacuum drying temperature is 60-240 ℃, the vacuum drying time is 1-10 hours, and the vacuum degree is 2-4 KPa.

The invention also provides polyaniline in-situ polymerization intercalation vanadium pentoxide obtained by the preparation method, wherein the thickness of the polyaniline in-situ polymerization intercalation vanadium pentoxide is 10-500 nm, and the mass fraction of polyaniline is 3.0-40%.

The invention also provides application of the polyaniline in-situ polymerization intercalation vanadium pentoxide as an electrode material in a metal ion battery and a metal ion capacitor.

Preferably, the metal ion battery is a zinc ion battery, a lithium ion battery, a sodium ion battery, a potassium ion battery or a magnesium ion battery, and the metal ion capacitor is a lithium ion capacitor or a sodium ion capacitor.

The beneficial effects of the invention include the following:

1) the polyaniline in-situ polymerization intercalation vanadium pentoxide with high specific capacity, excellent cycle stability and excellent rate performance is prepared by taking vanadium pentoxide powder as a vanadium source, aniline monomer in-situ polymerization as intercalation molecules and hydrogen peroxide as a cosolvent.

2) The method has the advantages of simple operation and easy control of reaction conditions, and can increase the interlayer spacing and the internal surface area of the vanadium pentoxide and provide more active sites for the electrochemical storage of metal ions because the aniline monomer is polymerized in situ between the vanadium pentoxide layers and the vanadium pentoxide is intercalated into nanosheets. Meanwhile, the diffusion rate of ions in vanadium pentoxide is enhanced by the conductive polymer polyaniline, the reaction kinetics rate of metal ions in vanadium pentoxide is improved, the interlayer capacitance effect is enhanced, and the reversible capacity and the rate capability of vanadium pentoxide as an electrode material are obviously improved.

Drawings

FIG. 1 is a scanning electron microscope photograph of the polyaniline in-situ polymerized intercalated vanadium pentoxide of example 1;

FIG. 2 is a TEM image of the intercalated vanadium pentoxide by in-situ polymerization of polyaniline in example 1;

FIG. 3 shows that the voltage of the zinc-ion battery made of the polyaniline in-situ polymerization intercalation vanadium pentoxide electrode material of example 1 is 1 A.g^-1A cycle performance curve at current density;

FIG. 4 shows different multiplying powers (0.3, 0.5, 1, 3, 5 A.g) of the zinc-ion battery made of the polyaniline in-situ polymerization intercalation vanadium pentoxide electrode material of example 1^-1) Constant current charge and discharge curve.

Detailed Description

The invention provides a preparation method of polyaniline in-situ polymerization intercalation vanadium pentoxide, which comprises the following steps:

1) mixing vanadium pentoxide powder, water and hydrogen peroxide to obtain a solution a;

2) mixing aniline monomer and water, and adjusting the pH value by using an acid solution to obtain a solution b;

3) and mixing the solution a and the solution b and then reacting to obtain the polyaniline in-situ polymerization intercalation vanadium pentoxide.

The preferred proportion of the vanadium pentoxide powder in the step 1) of the invention to the water and the hydrogen peroxide is 1-20 mmol: 1-200 mL: 1-20 mL, more preferably 5-15 mmol: 50-150 mL: 5-15 mL, more preferably 10-12 mmol: 100-120 mL: 10-12 mL.

The mixing time in the step 1) is preferably 1-24 hours, more preferably 10-20 hours, and even more preferably 15-18 hours; the mass fraction of the hydrogen peroxide is preferably 20-40%, and more preferably 30%; the particle size of the vanadium pentoxide powder is preferably 1-50 μm, more preferably 15-40 μm, and even more preferably 25-30 μm.

Adding vanadium pentoxide powder into water, and then adding hydrogen peroxide; the mixing is preferably carried out under stirring conditions; the water is preferably deionized water.

The method takes the hydrogen peroxide as the cosolvent, and the hydroxyl generated by the decomposition of the hydrogen peroxide acts on the surface of the vanadium pentoxide, so that the solubility of the vanadium pentoxide is improved.

The ratio of the aniline monomer to water in the step 2) is preferably 0.2-4 mmol: 1 to 300mL, more preferably 0.8 to 3 mmol: 50-200 mL, more preferably 2-2.5 mmol: 100-150 mL; the pH value is preferably 1 to 4, and more preferably 2 to 3.

The concentration of the acid solution in the step 2) is preferably 0.2-10 mol/L, more preferably 1.2-7 mol/L, and even more preferably 3-5 mol/L; the acid solution is preferably hydrochloric acid, sulfuric acid, phosphoric acid, sulfurous acid, acetic acid or citric acid.

The reaction temperature in the step 3) of the invention is preferably 60-180 ℃, more preferably 80-150 ℃, and more preferably 100-120 ℃; the reaction time is preferably 1-24 h, more preferably 5-18 h, and even more preferably 10-12 h.

The mixing in the step 3) of the invention is preferably to mix the solution a with the solution b after the solution a is heated to the reaction temperature; after the reaction is finished, cooling, centrifuging, washing, freeze drying and vacuum drying are preferably carried out in sequence.

The reaction in step 3) of the present invention is preferably carried out under oil bath conditions; the solutions a and b are preferably homogeneous solutions.

The cooling in the step 3) of the invention is preferably carried out to room temperature, and the temperature of the freeze drying is less than or equal to-53 ℃; the freeze drying time is preferably 24 to 72 hours, more preferably 30 to 60 hours, and still more preferably 40 to 50 hours; the temperature of the vacuum drying is preferably 60-240 ℃, more preferably 100-200 ℃, and even more preferably 120-180 ℃; the vacuum drying time is preferably 1-10 hours, and further preferably 5-8 hours; the vacuum degree of the vacuum drying is preferably 2-4 KPa, and more preferably 3 KPa.

The invention also provides polyaniline in-situ polymerization intercalation vanadium pentoxide obtained by the preparation method, wherein the thickness of the polyaniline in-situ polymerization intercalation vanadium pentoxide is preferably 10-500 nm, more preferably 50-300 nm, and more preferably 100-200 nm; the mass fraction of the polyaniline is preferably 3.0-40%, more preferably 10-30%, and even more preferably 15-25%.

The invention also provides application of the polyaniline in-situ polymerization intercalation vanadium pentoxide as an electrode material in a metal ion battery and a metal ion capacitor.

The metal ion battery is preferably a zinc ion battery, a lithium ion battery, a sodium ion battery, a potassium ion battery or a magnesium ion battery, and the metal ion capacitor is preferably a lithium ion capacitor or a sodium ion capacitor.

The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.