阅读说明：本技术 基于富钒液的甲胺插层钒氧化物电极材料的制备方法 (Preparation method of methylamine intercalation vanadium oxide electrode material based on vanadium-rich liquid ) 是由 刘涛 潘东 张一敏 刘红 于 2021-01-04 设计创作，主要内容包括：本发明涉及一种基于富钒液的甲胺插层钒氧化物电极材料的制备方法。其技术方案是：按草酸根离子与富钒液中钒离子的摩尔比为(0.5～1)∶1,将草酸二水合物或草酸盐加入富钒液中,搅拌1～3小时,得到溶液I。按铵根离子与所述溶液I中钒离子的摩尔比为(0.5～2)∶1,将铵盐加入所述溶液I中,搅拌1～2小时,得到溶液II。将所述溶液II置于反应釜内,在160～200℃条件下水热反应2～4小时,冷却至室温,固液分离,制得基于富钒液的甲胺插层钒氧化物电极材料。本发明具有制备成本低、制备过程安全环保和制备时间短的特点,所制备的基于富钒液的甲胺插层钒氧化物电极材料应用于水系锌离子电池,在0.1A/g的电流密度下,首次充放电容量为560～570mAh/g。(The invention relates to a preparation method of a methylamine intercalation vanadium oxide electrode material based on a vanadium-rich solution. The technical scheme is as follows: adding oxalic acid dihydrate or oxalate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of (0.5-1) to 1, and stirring for 1-3 hours to obtain a solution I. Adding ammonium salt into the solution I according to the molar ratio of ammonium ions to vanadium ions in the solution I of (0.5-2) to 1, and stirring for 1-2 hours to obtain a solution II. And (3) placing the solution II in a reaction kettle, carrying out hydrothermal reaction for 2-4 hours at 160-200 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the vanadium-rich liquid-based methylamine intercalation vanadium oxide electrode material. The preparation method has the characteristics of low preparation cost, safe and environment-friendly preparation process and short preparation time, and the prepared methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid is applied to a water system zinc ion battery, and the first charge-discharge capacity is 560-570 mAh/g under the current density of 0.1A/g.)

1. A method for preparing methylamine intercalation vanadium oxide electrode material based on vanadium-rich liquid is characterized by comprising the following steps:

step one, adding oxalic acid dihydrate or oxalate into a vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of (0.5-1) to 1, and stirring for 1-3 hours to obtain a solution I;

secondly, adding ammonium salt into the solution I according to the molar ratio of ammonium ions to vanadium ions in the solution I being (0.5-2) to 1, and stirring for 1-2 hours to obtain a solution II;

placing the solution II in a reaction kettle, carrying out hydrothermal reaction for 2-4 hours at 160-200 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain a methylamine intercalation vanadium oxide electrode material based on a vanadium-rich solution;

the vanadium-rich liquid is a product purified and enriched in wet extraction, purification and enrichment, ammonium salt vanadium precipitation and high-temperature calcination of a vanadium-containing substance; the vanadium-rich liquid: the vanadium concentration is 5-50 g/L, the Na concentration is less than or equal to 0.05g/L, the Fe concentration is less than or equal to 0.05g/L, the Al concentration is less than or equal to 0.05g/L, the P concentration is less than or equal to 0.05g/L, and the Si concentration is less than or equal to 0.05 g/L; the pH value is 0.5-8, and the content of pentavalent vanadium in the total vanadium is more than 90 wt%.

2. The method for preparing the methylamine intercalated vanadium oxide electrode material based on vanadium-rich liquid as claimed in claim 1, wherein the purity of the oxalic acid dihydrate is technical grade.

3. The method for preparing a methylamine intercalated vanadium oxide electrode material based on vanadium-rich liquid as claimed in claim 1, wherein the oxalate is one of sodium oxalate, potassium oxalate and ammonium oxalate.

4. The method for preparing methylamine intercalated vanadium oxide electrode material based on vanadium-rich liquid as claimed in claim 1, wherein the ammonium salt is one of ammonium chloride, ammonium sulfate, ammonium carbonate and ammonium bicarbonate.

Technical Field

The present invention belongs to the field of methylamine intercalation vanadium oxide electrode material. In particular to a preparation method of methylamine intercalation vanadium oxide electrode material based on vanadium-rich liquid.

Background

Organically intercalated V⁵⁺/V⁴⁺The mixed valence vanadium oxide electrode material is applied to various secondary ion batteries due to the obvious layered structure, wherein methylamine intercalates vanadium oxide (CH)₃NH₃V₂O₅) Is an organic intercalation V with typical lamellar structure⁵⁺/V⁴⁺The mixed valence vanadium oxide material has higher capacity and can be used as a secondary ion battery anode material.

Current CH₃NH₃V₂O₅Is mainly prepared from V₂O₅The vanadium raw material is prepared under hydrothermal conditions by adding nitrogen-containing and carbon-containing substances.

Li Yangguang et al (LI Y G, LAN Y, WANG X L, et al hydro thermal synthesis and structure of (CH)₃NH₃)₂(V^IVO)₂(V^VO₄)₂:A new layered mixed～valence vanadium oxide incorporated with organic cations[J]Chemical Research in Chinese Universities,2002,18: 252-254) with V₂O₅、NH₄F、CH₃NH₂(CH) was prepared as a reactant by hydrothermal reaction at 160 ℃ for 144 hours₃NH₃)₂V₄O₁₀Layered vanadium mixed valence compounds. Due to the higher price of V₂O₅The added ammonium fluoride is taken as a raw material, the added ammonium fluoride has strong acidity and larger corrosivity after being heated and dissolved, and methylamine belongs to flammable and explosive dangerous articles, so that the preparation method is not economical and unsafe, and the reaction time is too long.

Rongji Chen et al (CHEN R, ZAVALIJ P, WHITTINGHAM, et al. the hydraulic synthesis of the new mangannese and vanadia oxides, NiMnO₃H,MAV₃O₇ and MA_0.75V₄O₁₀·0.67H₂O[J]Journal of Materials Chemistry,1999,9: 93-100.) with V₂O₅Methylamine solution as reactant and reaction liquidThe pH values of (A) and (B) are respectively 4 and 7, and hydrothermal reaction is carried out for 4 days and 5 days at the temperature of 200 ℃ respectively to obtain (CH) with a double sheet structure (double sheet vanadia oxide)₃NH₃)V₃O₇And (CH)₃NH₃)_0.75V₄O₁₀·0.67H₂And O. The reaction is likewise carried out as V₂O₅As raw materials, dangerous chemical reagent-methylamine solution is required to be added, and the reaction time is too long.

Thus, the existing CH₃NH₃V₂O₅The preparation method has the defects of high preparation cost, unsafe preparation process, no environmental protection, overlong preparation time and the like, and the material is not applied to a water system zinc ion battery at present.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and aims to provide a method for preparing a methylamine intercalated vanadium oxide electrode material based on a vanadium-rich liquid, which has low preparation cost, safe and environment-friendly preparation process and short preparation time.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following specific steps:

step one, adding oxalic acid dihydrate or oxalate into the vanadium-rich liquid according to the molar ratio of the oxalate ions to the vanadium ions in the vanadium-rich liquid of (0.5-1) to 1, and stirring for 1-3 hours to obtain a solution I.

And secondly, adding ammonium salt into the solution I according to the molar ratio of ammonium ions to vanadium ions in the solution I of (0.5-2) to 1, and stirring for 1-2 hours to obtain a solution II.

And step three, placing the solution II in a reaction kettle, carrying out hydrothermal reaction for 2-4 hours at 160-200 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the vanadium-rich liquid-based methylamine intercalation vanadium oxide electrode material. The chemical formula of methylamine intercalated vanadium oxide is CH₃NH₃V₂O₅。

The vanadium-rich liquid is a product purified and enriched in wet extraction, purification and enrichment, ammonium salt vanadium precipitation and high-temperature calcination of a vanadium-containing substance; the vanadium-rich liquid: the vanadium concentration is 5-50 g/L, the Na concentration is less than or equal to 0.05g/L, the Fe concentration is less than or equal to 0.05g/L, the Al concentration is less than or equal to 0.05g/L, the P concentration is less than or equal to 0.05g/L, and the Si concentration is less than or equal to 0.05 g/L; the pH value is 0.5-8, and the content of pentavalent vanadium in the total vanadium is more than 90 wt%.

The purity of the oxalic acid dihydrate is industrial grade.

The oxalate is one of sodium oxalate, potassium oxalate and ammonium oxalate.

The ammonium salt is one of ammonium chloride, ammonium sulfate, ammonium carbonate and ammonium bicarbonate.

Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:

the invention replaces V with vanadium-rich liquid which is rich in vanadium and has low content of impurity elements₂O₅As a raw material of the hydrothermal reaction, the preparation cost of the methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid is obviously reduced.

The ammonium salt, oxalic acid dihydrate or oxalate adopted by the invention belongs to conventional chemical reagents, and compared with dangerous chemical reagents such as ammonium fluoride, methylamine and the like, the ammonium salt, oxalic acid dihydrate or oxalate is nonflammable and non-explosive, is convenient to transport and store, and has low corrosivity at high temperature, so that the preparation process is safer and more environment-friendly.

According to the method, the vanadium-rich solution with the pH value of 0.5-8 is used as a raw material, ammonium salt, oxalic acid dihydrate or oxalate is used as a nitrogen-containing and carbon-containing additive, and a methylamine intercalation vanadium oxide electrode material based on the vanadium-rich solution is prepared through hydrothermal reaction for 2-4 hours, so that the preparation time of the material is greatly shortened.

According to the invention, the vanadium-rich solution with low cost is used as a raw material, conventional chemical reagents such as ammonium salt, oxalic acid dihydrate or oxalate are added, and the methylamine intercalation vanadium oxide electrode material based on the vanadium-rich solution is prepared in a short time by a safe and environment-friendly one-step hydrothermal method.

The methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid, which is prepared by the invention, is applied to a water-based zinc ion battery, and the first charge-discharge capacity is 560-570 mAh/g under the current density of 0.1A/g.

Therefore, the method has the characteristics of low preparation cost, safe and environment-friendly preparation process and short preparation time, and the prepared methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid is applied to the first charge-discharge capacity of the water system zinc ion battery.

Drawings

FIG. 1 is an X-ray diffraction pattern of a methylamine intercalation vanadium oxide electrode material based on vanadium-rich liquid prepared by the invention.

Detailed Description

The invention is further described with reference to the following figures and detailed description, without limiting its scope.

A method for preparing methylamine intercalation vanadium oxide electrode material based on vanadium-rich liquid. The preparation method of the embodiment comprises the following steps:

step one, adding oxalic acid dihydrate or oxalate into the vanadium-rich liquid according to the molar ratio of the oxalate ions to the vanadium ions in the vanadium-rich liquid of (0.5-1) to 1, and stirring for 1-3 hours to obtain a solution I.

And secondly, adding ammonium salt into the solution I according to the molar ratio of ammonium ions to vanadium ions in the solution I of (0.5-2) to 1, and stirring for 1-2 hours to obtain a solution II.

And step three, placing the solution II in a reaction kettle, carrying out hydrothermal reaction for 2-4 hours at 160-200 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the vanadium-rich liquid-based methylamine intercalation vanadium oxide electrode material.

The vanadium-rich liquid: the vanadium concentration is 5-50 g/L, the Na concentration is less than or equal to 0.05g/L, the Fe concentration is less than or equal to 0.05g/L, the Al concentration is less than or equal to 0.05g/L, the P concentration is less than or equal to 0.05g/L, and the Si concentration is less than or equal to 0.05 g/L; the pH value is 0.5-8, and the content of pentavalent vanadium in the total vanadium is more than 90 wt%.

The oxalate is one of sodium oxalate, potassium oxalate and ammonium oxalate.

The ammonium salt is one of ammonium chloride, ammonium sulfate, ammonium carbonate and ammonium bicarbonate.

In this embodiment:

the chemical formula of methylamine intercalated vanadium oxide is CH₃NH₃V₂O₅；

The purity of the oxalic acid dihydrate is industrial grade;

the vanadium-rich liquid is a product purified and enriched in wet extraction, purification and enrichment, ammonium salt vanadium precipitation and high-temperature calcination of vanadium-containing substances.

The detailed description is omitted in the embodiments.

Example 1

A method for preparing methylamine intercalation vanadium oxide electrode material based on vanadium-rich liquid. The preparation method comprises the following steps:

step one, adding oxalic acid dihydrate into the vanadium-rich liquid according to the molar ratio of the oxalate ions to the vanadium ions in the vanadium-rich liquid of 0.5: 1, and stirring for 1 hour to obtain a solution I.

And step two, adding ammonium salt into the solution I according to the molar ratio of ammonium ions to vanadium ions in the solution I of 0.5: 1, and stirring for 1 hour to obtain a solution II.

And step three, placing the solution II in a reaction kettle, carrying out hydrothermal reaction for 2 hours at 160 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid.

The vanadium-rich liquid: the vanadium concentration is 5g/L, the Na concentration is 0.01g/L, the Fe concentration is 0.01g/L, the Al concentration is 0.01g/L, the P concentration is 0.01g/L, and the Si concentration is 0.01 g/L; the pH was 0.5 and the pentavalent vanadium content of the total vanadium was 90.05 wt%.

The ammonium salt is ammonium chloride.

The methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid is applied to a water-based zinc ion battery, and the first charge-discharge capacity is 560mAh/g under the current density of 0.1A/g.

Example 2

A method for preparing methylamine intercalation vanadium oxide electrode material based on vanadium-rich liquid. The preparation method comprises the following steps:

step one, adding oxalate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of 0.6: 1, and stirring for 1.5 hours to obtain a solution I.

And step two, adding ammonium salt into the solution I according to the mol ratio of the ammonium ions to the vanadium ions in the solution I of 1: 1, and stirring for 1.4 hours to obtain a solution II.

And step three, placing the solution II in a reaction kettle, carrying out hydrothermal reaction for 2.5 hours at the temperature of 170 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid.

The vanadium-rich liquid: the vanadium concentration is 25g/L, the Na concentration is 0.02g/L, the Fe concentration is 0.02g/L, the Al concentration is 0.03g/L, the P concentration is 0.02g/L, and the Si concentration is 0.02 g/L; the pH was 2 and the pentavalent vanadium content of the total vanadium was 91 wt%.

The oxalate is sodium oxalate.

The ammonium salt is ammonium sulfate.

The methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid is applied to a water-based zinc ion battery, and the first charge-discharge capacity is 563mAh/g under the current density of 0.1A/g.

Example 3

A method for preparing methylamine intercalation vanadium oxide electrode material based on vanadium-rich liquid. The preparation method comprises the following steps:

step one, adding oxalate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of 0.8: 1, and stirring for 2.5 hours to obtain a solution I.

And step two, adding ammonium salt into the solution I according to the mol ratio of the ammonium ions to the vanadium ions in the solution I of 1.5: 1, and stirring for 1.8 hours to obtain a solution II.

And step three, placing the solution II in a reaction kettle, carrying out hydrothermal reaction for 3.5 hours at 180 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid.

The vanadium-rich liquid: the vanadium concentration is 35g/L, the Na concentration is 0.04g/L, the Fe concentration is 0.04g/L, the Al concentration is 0.04g/L, the P concentration is 0.03g/L, and the Si concentration is 0.04 g/L; the pH was 4 and the pentavalent vanadium content of the total vanadium was 92 wt%.

The oxalate is potassium oxalate.

The ammonium salt is ammonium carbonate.

The methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid is applied to a water-based zinc ion battery, and the first charge-discharge capacity is 568mAh/g under the current density of 0.1A/g.

Example 4

A method for preparing methylamine intercalation vanadium oxide electrode material based on vanadium-rich liquid. The preparation method comprises the following steps:

step one, adding oxalate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of 1: 1, and stirring for 3 hours to obtain a solution I.

And step two, adding ammonium salt into the solution I according to the mol ratio of the ammonium ions to the vanadium ions in the solution I of 2: 1, and stirring for 2 hours to obtain a solution II.

And step three, placing the solution II in a reaction kettle, carrying out hydrothermal reaction for 4 hours at the temperature of 200 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid.

The vanadium-rich liquid: the vanadium concentration is 50g/L, the Na concentration is 0.05g/L, the Fe concentration is 0.05g/L, the Al concentration is 0.05g/L, the P concentration is 0.05g/L, and the Si concentration is 0.05 g/L; the pH was 8 and the pentavalent vanadium content of the total vanadium was 94 wt%.

The oxalate is ammonium oxalate.

The ammonium salt is ammonium bicarbonate.

The methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid is applied to a water-based zinc ion battery, and the first charge-discharge capacity is 570mAh/g under the current density of 0.1A/g.

Compared with the prior art, the specific implementation mode has the following positive effects:

in the specific embodiment, V is replaced by vanadium-rich liquid which is rich in vanadium and has low impurity element content₂O₅As a raw material of the hydrothermal reaction, the preparation cost of the methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid is reduced.

The ammonium salt, oxalic acid dihydrate or oxalate adopted by the specific embodiment belongs to conventional chemical reagents, and compared with dangerous chemical reagents such as ammonium fluoride and methylamine, the ammonium salt, oxalic acid dihydrate or oxalate is nonflammable and non-explosive, is convenient to transport and store, and has low corrosivity at high temperature, so that the preparation process is safer and more environment-friendly.

According to the specific embodiment, the methylamine intercalation vanadium oxide electrode material based on the vanadium-rich solution is prepared by taking the vanadium-rich solution with the pH of 0.5-8 as a raw material and taking ammonium salt, oxalic acid dihydrate or oxalate as a nitrogen-containing and carbon-containing additive through hydrothermal reaction for 2-4 hours, so that the preparation time of the material is greatly shortened.

The methylamine intercalation vanadium oxide electrode material based on vanadium-rich liquid prepared by the specific embodiment is shown in the attached drawing: fig. 1 is an X-ray diffraction pattern of a vanadium-rich liquid based methylamine intercalated vanadium oxide electrode material prepared in example 3. As can be seen from fig. 1: diffraction peak and CH of the material₃NH₃V₂O₅The X-ray diffraction peaks of (PDF No. 46-2496) correspond to each other, and have similar crystal structures.

According to the specific embodiment, the vanadium-rich solution with low cost is used as a raw material, conventional chemical reagents such as ammonium salt, oxalic acid dihydrate or oxalate are added, and the methylamine intercalation vanadium oxide electrode material based on the vanadium-rich solution is prepared in a short time by a safe and environment-friendly one-step hydrothermal method.

The methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid prepared by the specific embodiment is applied to a water-based zinc ion battery, and the first charge-discharge capacity is 560-570 mAh/g under the current density of 0.1A/g.

Therefore, the specific embodiment has the characteristics of low preparation cost, safe and environment-friendly preparation process and short preparation time, and the prepared methylamine intercalation vanadium oxide electrode material based on the vanadium-rich liquid is applied to the first charge-discharge capacity of the water-based zinc ion battery and is obviously improved.