CN115000394B - Electrochemical material and preparation method and application thereof - Google Patents

Abstract

The invention relates to the technical field of battery materials, in particular to an electrochemical material and a preparation method and application thereof, wherein the electrochemical material comprises active aluminum oxide, potassium-containing manganese oxide filter material, calcium tungstate and active manganese oxide precipitate, and the weight ratio of the active aluminum oxide to the potassium-containing manganese oxide filter material to the calcium tungstate to the active manganese oxide precipitate is (0.5-1): 5:0.5-0.9:20. in the invention, aluminum ions, calcium ions of calcium tungstate and tungstate ions in the activated alumina are embedded in the crystal lattice of manganese oxide, so that microscopic crystal lattice defects and macroscopic defects are increased. The potassium-containing manganese oxide and the active manganese oxide with amorphous structures are compounded, so that the ordering of the manganese oxide is greatly destroyed, and the distortion of the crystal lattice of the manganese oxide is more serious. The distortion of the crystal lattice not only provides a good channel for the movement of ions, but also provides a structural basis for obtaining larger specific surface area of manganese oxide after crushing.

Description

Electrochemical material and preparation method and application thereof

Technical Field

The present invention relates to the technical field of battery materials, and in particular to an electrochemical material and a preparation method thereof.

Background technique

Manganese dioxide (MnO ₂ ) is an important industrial material and is therefore widely used in the fields of molecular ion sieves, catalysts, and energy storage and conversion systems.

The patent application with application number CN201310546757.6 involves the field of battery material processing, specifically a method for preparing electrolytic manganese dioxide for button-type alkaline zinc/manganese dioxide batteries. The preparation method includes manganese sulfate leaching, neutralization and iron removal, heavy metal impurity removal, electrolysis and post-treatment steps. Manganese oxide ore powder, pyrite ore powder, and industrial sulfuric acid are soaked in the presence of _SO2 to prepare a crude manganese sulfate solution, and then iron is removed by ammonium bicarbonate solution, and heavy metals are removed by barium sulfide. After periodic electrolysis, a manganese dioxide semi-finished product is obtained at the anode, and then after post-treatment, a special electrolytic manganese dioxide is finally obtained. However, its specific surface area value needs to be improved.

Summary of the invention

In view of this, the purpose of the present invention is to provide an electrochemical material and a preparation method and application thereof, so as to solve the problem of low specific surface area of the electrochemical material.

Based on the above purpose, the present invention provides an electrochemical material, including activated alumina, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate, wherein the weight ratio of the activated alumina, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate is 0.5-1:5:0.5-0.9:20.

The present invention also provides a method for preparing the electrochemical material, comprising the following steps:

Step 1: Take the formulated amount of activated alumina, potassium-containing manganese oxide filtrate, and calcium tungstate and add them to the activated manganese oxide precipitate, mix and stir, and then dry;

Step 2: calcine the mixture after drying in step 1 at 880-940° C. for 2-3 hours, and then cool it to obtain the electrochemical material.

The preparation method of the activated alumina is as follows: firstly prepare 105-110g/L of aluminum salt solution, then add alkali of 6 times the molar amount of the aluminum salt, and then stir, precipitate, wash, dry, and treat at 210-250°C to obtain the activated alumina. The aluminum ions in the activated alumina and the calcium ions and tungstate ions of calcium tungstate are embedded in the lattice of manganese oxide, which will cause the distortion of the lattice of manganese oxide, increase the microscopic lattice defects and macroscopic defects, and provide a structural basis for obtaining a larger specific surface area of manganese oxide.

The preparation method of the potassium-containing manganese oxide filtrate is as follows: a potassium permanganate solution with a concentration of 13-13.4 g/L is mixed with a PVA aqueous solution with a concentration of 6.4-6.8 g/L to obtain a mixed solution, and then the mixed solution is heated at a temperature of 260-270°C for 0.5-1h, filtered, and dried to obtain the result. The potassium-containing manganese oxide with an amorphous structure and the active manganese oxide are combined, which greatly destroys the orderliness of the manganese oxide and makes the distortion of the lattice of the manganese oxide more serious. This lattice distortion not only provides a good channel for the movement of ions, but also provides a structural basis for obtaining a larger specific surface area of manganese oxide after crushing.

Preferably, the potassium content in the potassium-containing manganese oxide filtrate is 1-3%.

The preparation method of the active manganese oxide precipitate comprises the following steps:

S1. Put manganese oxide, ferrous sulfide and concentrated sulfuric acid into a reaction tank in a weight ratio of 1:0.2-0.5:2, stir and react for 2-3 hours at a temperature of 85-95°C and a stirring speed of 55-60rpm, then introduce sulfur dioxide gas to react for 1-2 hours, the weight ratio of the molar amount of sulfur dioxide gas introduced to manganese oxide is 0.02-0.03 mol/g, and obtain a manganese sulfate solution;

S2. Dissolve manganese sulfate solution, ammonium sulfate and ammonium persulfate in water at a mass ratio of 0.3-0.5:0.4:1, stir until no precipitation occurs, transfer to a reactor, perform heat preservation reaction, cool, dry and grind to obtain an active manganese oxide precipitate.

Preferably, the temperature of the insulation reaction is 145° C. and the insulation time is 10 h.

Preferably, the drying temperature is 110° C. and the powder is ground to 200 mesh.

The invention also provides application of the electrochemical material in a battery.

Beneficial effects of the present invention: In the present invention, aluminum ions in activated alumina and calcium ions and tungstate ions in calcium tungstate are embedded in the lattice of manganese oxide, which will cause the distortion of the manganese oxide lattice and increase microscopic lattice defects and macroscopic defects. The combination of potassium-containing manganese oxide with an amorphous structure and activated manganese oxide greatly destroys the orderliness of manganese oxide and makes the distortion of the lattice of manganese oxide more serious. This lattice distortion not only provides a good channel for the movement of ions, but also provides a structural basis for obtaining a larger specific surface area of manganese oxide after crushing. The electrochemical material preparation method of the present invention simplifies the production process, has high production process efficiency, a wide source of materials, low cost, is suitable for industrial production, and can be used in the fields of batteries and the like.

Detailed ways

In order to make the objectives, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments.

It should be noted that, unless otherwise defined, the technical terms or scientific terms used in the present invention should be understood by people with ordinary skills in the field to which the present invention belongs. The words "first", "second" and similar words used in the present invention do not indicate any order, quantity or importance, but are only used to distinguish different components. The words "include" or "comprise" and similar words mean that the elements or objects appearing before the word include the elements or objects listed after the word and their equivalents, without excluding other elements or objects.

The present invention relates to an electrochemical material, comprising activated aluminum oxide, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate, wherein the weight ratio of activated aluminum oxide, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate is 0.5-1:5:0.5-0.9:20. Among them, aluminum ions in activated aluminum oxide and calcium ions and tungstate ions of calcium tungstate are embedded in the lattice of manganese oxide, which will cause the distortion of the manganese oxide lattice and increase microscopic lattice defects and macroscopic defects. The composite of potassium-containing manganese oxide with amorphous structure and activated manganese oxide greatly destroys the orderliness of manganese oxide and makes the distortion of the lattice of manganese oxide more serious. This lattice distortion not only provides a good channel for the movement of ions, but also provides a structural basis for obtaining a larger specific surface area of manganese oxide after crushing.

The preparation method of activated alumina is as follows: aluminum salt Al ₂ (SO ₄ ) ₃ is taken to prepare an aqueous solution containing 105-110 g/L of alumina, then NaOH is added in an amount 6 times the molar amount of Al ₂ (SO ₄ ) ₃ , the solution is stirred for 0.5-1 hour, and then the precipitate is washed 2-3 times with distilled water and anhydrous ethanol respectively. First, it is placed in a drying oven for 0.5-1 hour, and then heated to 210-250°C to obtain activated alumina powder and ground to 200 mesh for standby use.

Preparation method of potassium-containing manganese oxide filtrate: Mix potassium permanganate solution and PVA aqueous solution in a mass ratio of 1:2.5-2.8. The concentration of potassium permanganate solution is 13.0-13.4 g/L, and the concentration of PVA aqueous solution is 6.4-6.8 g/L. Heat the mixed solution at a temperature of 260-270°C for 0.5-1 hour. After filtering, take out the potassium-containing active manganese oxide filtrate. Then dry it at 120°C and grind it to 200 mesh for standby use. The potassium content in the potassium-containing manganese oxide filtrate is 1-3%.

Preparation method of active manganese oxide precipitate: put 200 mesh manganese oxide, ferrous sulfide and industrial sulfuric acid into a reaction tank in a weight ratio of 1:0.2-0.5:2. The concentration of H ₂ SO ₄ in concentrated sulfuric acid is 97%. React for 2-3 hours at a temperature of 85-95°C and a stirring speed of 55-60rpm. Then introduce sulfur dioxide SO ₂ gas, the weight ratio of sulfur dioxide SO ₂ gas introduction to manganese oxide is 0.02-0.03 mol/g, the reaction time is 1-2 hours, and a manganese sulfate solution is obtained by leaching. Then weigh the manganese sulfate solution, (NH4) ₂ SO ₄ and (NH ₄ ) ₂ S ₂ O ₈ , the mass ratio of which is 0.3-0.5:0.4:1. Dissolve in 400mL of deionized water, stir until there is no precipitation and impurities in the solution, and then transfer to the reactor. The reactor was placed in an environment of 145° C. for 10 hours, and then naturally cooled to room temperature to obtain active manganese oxide precipitate in the reactor, which was then dried at 110° C. and ground to 200 mesh for later use.

The following is a detailed explanation through specific examples.

Example 1

An electrochemical material consists of activated alumina, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate, wherein the weight ratio of the activated alumina, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate is 0.5:5:0.5:20.

The preparation method of the electrochemical material of this embodiment includes the following steps:

Step 1: Prepare materials according to the weight ratio of activated alumina, potassium manganese oxide filtrate, calcium tungstate and activated manganese oxide of 0.5:5:0.5:20, then add activated alumina, potassium manganese oxide filtrate and calcium tungstate into the activated manganese oxide precipitate, mix and stir for 1.5-2h, and then dry at 110℃.

Step 2: calcine the mixture after drying in step 1 at 900° C. for 2.5 h, and then cool it to obtain the electrochemical material.

The preparation method of activated alumina is as follows: aluminum salt Al ₂ (SO ₄ ) ₃ is prepared into an aqueous solution containing 108/L of aluminum sulfate, then NaOH is added in an amount 6 times the molar amount of Al ₂ (SO ₄ ) ₃ , the solution is stirred for 0.5-1h, and then the precipitate is washed 2-3 times with distilled water and anhydrous ethanol respectively. First, it is placed in a drying oven for 0.5-1h, and then heated to 230°C to obtain activated alumina powder and ground to 200 mesh for standby use.

Preparation method of potassium-containing manganese oxide filtrate: Mix potassium permanganate solution and PVA aqueous solution, wherein the concentration of potassium permanganate solution is 13g/L and the concentration of PVA aqueous solution is 6.4g/L. Heat the mixed solution at 265°C for 0.5-1 hour. After filtering, take out the potassium-containing active manganese oxide filtrate. Then dry it at 120°C and grind it to 200 mesh for standby use. The potassium content in the potassium-containing manganese oxide filtrate is 2%.

Preparation method of active manganese oxide precipitate: put 200 mesh manganese oxide, ferrous sulfide and industrial sulfuric acid into the reaction tank in a weight ratio of 1:0.3:2. Industrial sulfuric acid is concentrated sulfuric acid, and the concentration of H ₂ SO ₄ in concentrated sulfuric acid is 97%. React for 2-3 hours at a temperature of 90°C and a stirring speed of 58rpm. Then introduce sulfur dioxide SO ₂ gas, the weight ratio of sulfur dioxide SO ₂ gas introduction to manganese oxide is 0.025 mol/g, the reaction time is 1.5 hours, and leaching manganese sulfate solution is obtained. Then weigh the manganese sulfate solution, (NH4) ₂ SO ₄ , and (NH ₄ ) ₂ S ₂ O ₈ , and the mass ratio is 0.4:0.4:1. Dissolve in 400mL of deionized water, stir until there is no precipitation and impurities in the solution, and then transfer to the reactor. The reactor was placed in an environment of 145° C. for 10 hours, and then naturally cooled to room temperature to obtain active manganese oxide precipitate in the reactor, which was then dried at 110° C. and ground to 200 mesh for later use.

Example 2

An electrochemical material consists of activated aluminum oxide, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate, wherein the weight ratio of the activated aluminum oxide, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate is 0.7:5:0.7:20.

The preparation method of the electrochemical material of this embodiment includes the following steps:

Step 1: Prepare materials according to the weight ratio of activated alumina, potassium manganese oxide filtrate, calcium tungstate and activated manganese oxide of 0.7:5:0.7:20, then add activated alumina, potassium manganese oxide filtrate and calcium tungstate into the activated manganese oxide precipitate, mix and stir for 1.5-2h, and then dry at 110℃.

Step 2: calcine the mixture after drying in step 1 at 900° C. for 2.5 h, and then cool it to obtain the electrochemical material.

The preparation method of activated alumina is as follows: aluminum salt Al ₂ (SO ₄ ) ₃ is prepared into an aqueous solution containing 108/L of aluminum sulfate, then NaOH is added in an amount 6 times the molar amount of Al ₂ (SO ₄ ) ₃ , the solution is stirred for 0.5-1h, and then the precipitate is washed 2-3 times with distilled water and anhydrous ethanol respectively. First, it is placed in a drying oven for 0.5-1h, and then heated to 230°C to obtain activated alumina powder and ground to 200 mesh for standby use.

Preparation method of potassium-containing manganese oxide filtrate: Mix potassium permanganate solution and PVA aqueous solution, wherein the concentration of potassium permanganate solution is 13.4 g/L and the concentration of PVA aqueous solution is 6.8 g/L. Heat the mixed solution at 265°C for 0.5-1 hour. After filtering, take out the potassium-containing active manganese oxide filtrate. Then dry it at 120°C and grind it to 200 mesh for standby use. The potassium content in the potassium-containing manganese oxide filtrate is 2%.

Preparation method of active manganese oxide precipitate: put 200 mesh manganese oxide, ferrous sulfide and industrial sulfuric acid into the reaction tank in a weight ratio of 1:0.4:2. Industrial sulfuric acid is concentrated sulfuric acid, and the concentration of H ₂ SO ₄ in concentrated sulfuric acid is 97%. React for 2-3 hours at a temperature of 90°C and a stirring speed of 58rpm. Then introduce sulfur dioxide SO ₂ gas, the weight ratio of sulfur dioxide SO ₂ gas introduction to manganese oxide is 0.025 mol/g, the reaction time is 1.5 hours, and leaching manganese sulfate solution is obtained. Then weigh the manganese sulfate solution, (NH4) ₂ SO ₄ , and (NH ₄ ) ₂ S ₂ O ₈ , and the mass ratio is 0.4:0.4:1. Dissolve in 400mL of deionized water, stir until there is no precipitation and impurities in the solution, and then transfer to the reactor. The reactor was placed in an environment of 145° C. for 10 hours, and then naturally cooled to room temperature to obtain active manganese oxide precipitate in the reactor, which was then dried at 110° C. and ground to 200 mesh for later use.

Example 3

An electrochemical material is composed of activated aluminum oxide, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate, wherein the weight ratio of the activated aluminum oxide, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate is 1:5:0.9:20.

The preparation method of the electrochemical material of this embodiment includes the following steps:

Step 1: Prepare materials according to the weight ratio of activated alumina, potassium manganese oxide filtrate, calcium tungstate and activated manganese oxide of 1:5:0.9:20, then add activated alumina, potassium manganese oxide filtrate and calcium tungstate into the activated manganese oxide precipitate, mix and stir for 1.5-2h, and then dry at 110℃.

Step 2: calcine the mixture after drying in step 1 at 900° C. for 2.5 h, and then cool it to obtain the electrochemical material.

The preparation method of activated alumina is as follows: aluminum salt Al ₂ (SO ₄ ) ₃ is prepared into an aqueous solution containing 108/L of aluminum sulfate, then NaOH is added in an amount 6 times the molar amount of Al ₂ (SO ₄ ) ₃ , the solution is stirred for 0.5-1h, and then the precipitate is washed 2-3 times with distilled water and anhydrous ethanol respectively. First, it is placed in a drying oven for 0.5-1h, and then heated to 230°C to obtain activated alumina powder and ground to 200 mesh for standby use.

Preparation method of potassium-containing manganese oxide filtrate: Mix potassium permanganate solution and PVA aqueous solution, wherein the concentration of potassium permanganate solution is 13.2 g/L and the concentration of PVA aqueous solution is 6.6/L. Heat the mixed solution at 265°C for 0.5-1 hour. After filtering, take out the potassium-containing active manganese oxide filtrate. Then dry it at 120°C and grind it to 200 mesh for standby use. The potassium content in the potassium-containing manganese oxide filtrate is 2%.

Preparation method of active manganese oxide precipitate: put 200 mesh manganese oxide, ferrous sulfide and industrial sulfuric acid into the reaction tank in a weight ratio of 1:0.5:2. Industrial sulfuric acid is concentrated sulfuric acid, and the concentration of H ₂ SO ₄ in concentrated sulfuric acid is 97%. React for 2-3 hours at a temperature of 90°C and a stirring speed of 58rpm. Then introduce sulfur dioxide SO ₂ gas, the weight ratio of sulfur dioxide SO ₂ gas introduction to manganese oxide is 0.025 mol/g, the reaction time is 1.5 hours, and leaching manganese sulfate solution is obtained. Then weigh the manganese sulfate solution, (NH4) ₂ SO ₄ , (NH ₄ ) ₂ S ₂ O ₈ , and the mass ratio is 0.4:0.4:1. Dissolve in 400mL deionized water, stir until there is no precipitation and impurities in the solution, and then transfer to the reactor. The reactor was placed in an environment of 145° C. for 10 hours, and then naturally cooled to room temperature to obtain active manganese oxide precipitate in the reactor, which was then dried at 110° C. and ground to 200 mesh for later use.

Example 4

An electrochemical material consists of activated aluminum oxide, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate, wherein the weight ratio of the activated aluminum oxide, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate is 0.4:5:0.4:20.

The preparation method of the electrochemical material of this embodiment includes the following steps:

Step 1: Prepare materials according to the weight ratio of activated alumina, potassium manganese oxide filtrate, calcium tungstate and activated manganese oxide of 0.4:5:0.4:20, then add activated alumina, potassium manganese oxide filtrate and calcium tungstate into the activated manganese oxide precipitate, mix and stir for 1.5-2h, and then dry at 110℃.

Step 2: calcine the mixture after drying in step 1 at 900° C. for 2.5 h, and then cool it to obtain the electrochemical material.

The preparation method of activated alumina is as follows: aluminum salt Al ₂ (SO ₄ ) ₃ is prepared into an aqueous solution containing 108/L of aluminum sulfate, then NaOH is added in an amount 6 times the molar amount of Al ₂ (SO ₄ ) ₃ , the solution is stirred for 0.5-1h, and then the precipitate is washed 2-3 times with distilled water and anhydrous ethanol respectively. First, it is placed in a drying oven for 0.5-1h, and then heated to 230°C to obtain activated alumina powder and ground to 200 mesh for standby use.

Preparation method of potassium-containing manganese oxide filtrate: Mix potassium permanganate solution and PVA aqueous solution, the concentration of potassium permanganate solution is 13.3g/L, and the concentration of PVA aqueous solution is 6.6g/L. Heat the mixed solution at 265°C for 0.5-1 hour. After filtering, take out the potassium-containing active manganese oxide filtrate. Then dry it at 120°C and grind it to 200 mesh for standby use. The potassium content in the potassium-containing manganese oxide filtrate is 2%.

Preparation method of active manganese oxide precipitate: put 200 mesh manganese oxide, ferrous sulfide and industrial sulfuric acid into the reaction tank in a weight ratio of 1:0.3:2. Industrial sulfuric acid is concentrated sulfuric acid, and the concentration of H ₂ SO ₄ in concentrated sulfuric acid is 97%. React for 2-3 hours at a temperature of 90°C and a stirring speed of 58rpm. Then introduce sulfur dioxide SO ₂ gas, the weight ratio of sulfur dioxide SO ₂ gas introduction to manganese oxide is 0.025 mol/g, the reaction time is 1.5 hours, and leaching manganese sulfate solution is obtained. Then weigh the manganese sulfate solution, (NH4) ₂ SO ₄ , and (NH ₄ ) ₂ S ₂ O ₈ , and the mass ratio is 0.4:0.4:1. Dissolve in 400mL of deionized water, stir until there is no precipitation and impurities in the solution, and then transfer to the reactor. The reactor was placed in an environment of 145° C. for 10 hours, and then naturally cooled to room temperature to obtain active manganese oxide precipitate in the reactor, which was then dried at 110° C. and ground to 200 mesh for later use.

Example 5

An electrochemical material consists of activated alumina, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate, wherein the weight ratio of the activated alumina, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate is 1.1:5:1.1:20.

The preparation method of the electrochemical material of this embodiment includes the following steps:

Step 1: Prepare materials according to the weight ratio of activated alumina, potassium manganese oxide filtrate, calcium tungstate and activated manganese oxide of 1.1:5:1.1:20, then add activated alumina, potassium manganese oxide filtrate and calcium tungstate into the activated manganese oxide precipitate, mix and stir for 1.5-2h, and then dry at 110℃.

Step 2: calcine the mixture after drying in step 1 at 900° C. for 2.5 h, and then cool it to obtain the electrochemical material.

The preparation method of activated alumina is as follows: aluminum salt Al ₂ (SO ₄ ) ₃ is prepared into an aqueous solution containing 108/L of aluminum sulfate, then NaOH is added in an amount 6 times the molar amount of Al ₂ (SO ₄ ) ₃ , the solution is stirred for 0.5-1h, and then the precipitate is washed 2-3 times with distilled water and anhydrous ethanol respectively. First, it is placed in a drying oven for 0.5-1h, and then heated to 230°C to obtain activated alumina powder and ground to 200 mesh for standby use.

Preparation method of potassium-containing manganese oxide filtrate: Mix potassium permanganate solution and PVA aqueous solution, wherein the concentration of potassium permanganate solution is 13.1/L and the concentration of PVA aqueous solution is 6.8g/L. Heat the mixed solution at 265°C for 0.5-1 hour. After filtering, take out the potassium-containing active manganese oxide filtrate. Then dry it at 120°C and grind it to 200 mesh for standby use. The potassium content in the potassium-containing manganese oxide filtrate is 2%.

Preparation method of active manganese oxide precipitate: put 200 mesh manganese oxide, ferrous sulfide and industrial sulfuric acid into the reaction tank in a weight ratio of 1:0.5:2. Industrial sulfuric acid is concentrated sulfuric acid, and the concentration of H ₂ SO ₄ in concentrated sulfuric acid is 97%. React for 2-3 hours at a temperature of 90°C and a stirring speed of 58rpm. Then introduce sulfur dioxide SO ₂ gas, the weight ratio of sulfur dioxide SO ₂ gas introduction to manganese oxide is 0.025 mol/g, the reaction time is 1.5 hours, and leaching manganese sulfate solution is obtained. Then weigh the manganese sulfate solution, (NH4) ₂ SO ₄ , (NH ₄ ) ₂ S ₂ O ₈ , and the mass ratio is 0.4:0.4:1. Dissolve in 400mL deionized water, stir until there is no precipitation and impurities in the solution, and then transfer to the reactor. The reactor was placed in an environment of 145° C. for 10 hours, and then naturally cooled to room temperature to obtain active manganese oxide precipitate in the reactor, which was then dried at 110° C. and ground to 200 mesh for later use.

Comparative Example 1

The product prepared by the method for preparing electrolytic manganese dioxide for button-type alkaline zinc/manganese dioxide batteries disclosed in application number CN201310546757.6 has a specific surface area (BET) of 28 m ² /g.

The specific surface area of the products prepared in Examples 1-5 was tested, and the results are shown in Table 1 below.

Table 1

Specific surface area (BET) Example 1 28.9 Example 2 29.5 Example 3 29.3 Example 4 28.4 Example 5 28.5 Comparative Example 1 28

It can be seen from Table 1 that by adopting the preparation method of the present invention, a larger specific surface area can be obtained through reasonable composition and ratio.

Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention (including the claims) is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

The present invention is intended to cover all such substitutions, modifications and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims (5)

1. A method for preparing an electrochemical material, characterized in that it comprises the following steps: Step 1: Take a formula amount of activated alumina, potassium-containing manganese oxide filtrate, and calcium tungstate and add them to the activated manganese oxide precipitate, mix and stir, and then dry; the weight ratio of the activated alumina, potassium-containing manganese oxide filtrate, calcium tungstate and activated manganese oxide precipitate is 0.5-1:5:0.5-0.9:20; Step 2: calcining the mixture after drying in step 1 at 880-940° C. for 2-3 hours, and cooling to obtain an electrochemical material; The preparation method of the activated alumina is as follows: first prepare 105-110 g/L aluminum salt solution, then add 6 times the molar amount of base of the aluminum salt, and then stir, precipitate, wash, dry, and treat at 210-250° C. to obtain the activated alumina; The preparation method of the potassium-containing manganese oxide filtrate is as follows: a potassium permanganate solution with a concentration of 13-13.4 g/L and a PVA aqueous solution with a concentration of 6.4-6.8 g/L are mixed to obtain a mixed solution, and then the mixed solution is heated at a temperature of 260-270° C. for 0.5-1 h, filtered, and dried to obtain the product; The mass percentage of potassium in the potassium-containing manganese oxide filtrate is 1-3%; The preparation method of the active manganese oxide precipitate comprises the following steps: S1. Put manganese oxide, ferrous sulfide and concentrated sulfuric acid into a reaction tank in a weight ratio of 1:0.2-0.5:2, stir and react for 2-3 hours at a temperature of 85-95°C and a stirring speed of 55-60rpm, then introduce sulfur dioxide gas to react for 1-2 hours, the weight ratio of the molar amount of sulfur dioxide gas introduced to manganese oxide is 0.02-0.03 mol/g, and obtain a manganese sulfate solution; S2. Dissolve manganese sulfate solution, ammonium sulfate and ammonium persulfate in water at a mass ratio of 0.3-0.5:0.4:1, stir until no precipitation occurs, transfer to a reactor, perform heat preservation reaction, cool, dry and grind to obtain an active manganese oxide precipitate. 2. The method for preparing the electrochemical material according to claim 1, characterized in that the temperature of the insulation reaction is 145°C and the insulation time is 10 hours. 3. The method for preparing the electrochemical material according to claim 1, characterized in that the drying temperature in S2 is 110°C and the grinding is to 200 mesh. 4. An electrochemical material, characterized in that the electrochemical material is obtained by the preparation method described in any one of claims 1 to 3. 5. Use of the electrochemical material according to claim 4 in a battery.