A negative electrode material for alkaline zinc-manganese batteries, a preparation method thereof, and applications thereof

Abstract

This application relates to the field of alkaline zinc-manganese batteries, and specifically discloses a negative electrode material for alkaline zinc-manganese batteries, a preparation method thereof, and an application. A negative electrode material for alkaline zinc-manganese batteries comprises the following components in parts by weight: 55-65 parts of zinc powder, 0.4-0.8 part of a dispersant, 0.4-0.8 part of a binder, 25-30 parts of an electrolyte, 0.2-2 parts of a corrosion inhibitor, 0.3-2 parts of an anti-passivation agent, 1-3 parts of water, and the anti-passivation agent comprises sodium silicate and zeolite, and the mass ratio of sodium silicate to zeolite is 1:(0.5-1.5); the preparation method comprises the following steps: mixing the zinc powder, the dispersant, and the binder evenly, adding the electrolyte, the corrosion inhibitor, the anti-passivation agent, and water, stirring, and evacuating; the application is: using the negative electrode material for alkaline zinc-manganese batteries as the negative electrode, assembling it with a manganese dioxide positive electrode to obtain an alkaline zinc-manganese battery. This application has the advantage of improving the high-power discharge performance of alkaline zinc-manganese batteries.

Description

Technical Field

[0001] This application relates to the technical field of alkaline zinc-manganese batteries. More specifically, it relates to a negative electrode material for an alkaline zinc-manganese battery, a preparation method thereof, and an application thereof. Background Art

[0002] An alkaline zinc-manganese battery is a primary battery with zinc as the negative electrode, manganese dioxide as the positive electrode, and a potassium hydroxide solution as the electrolyte. Zinc is an amphoteric metal. In an alkaline zinc-manganese battery, the zinc electrode loses electrons and is oxidized and dissolved, generating zincate ions in an alkaline environment. As zinc continues to dissolve, the concentration of zincate ions gradually increases. When the concentration of zincate ions increases to a certain extent, the zinc hydroxide formed by the hydrolysis of zincate ions precipitates as a solid phase and deposits on the surface of the zinc electrode to form a passivation film, which affects the normal dissolution of zinc.

[0003] When the current density of the battery is small, the passivation film is in a loose state, and some zinc can still continue to dissolve, and the zinc electrode can still maintain a certain activity; when the current density increases to a certain value, the passivation film is in a dense state and completely covers the zinc electrode, and the zinc electrode loses its activity and becomes "passive". Therefore, under high-power discharge conditions, the discharge performance of alkaline zinc-manganese batteries is poor. Summary of the Invention

[0004] In order to solve the problem of poor high-power discharge performance of alkaline zinc-manganese batteries, this application provides a negative electrode material for an alkaline zinc-manganese battery, a preparation method thereof, and an application thereof.

[0005] In a first aspect, this application provides a negative electrode material for an alkaline zinc-manganese battery, adopting the following technical solution:

[0006] A negative electrode material for an alkaline zinc-manganese battery, comprising the following components in parts by weight: 55-65 parts of zinc powder, 0.4-0.8 parts of a dispersant, 0.4-0.8 parts of a binder, 25-30 parts of an electrolyte, 0.1-0.4 parts of a corrosion inhibitor, 0.2-2 parts of an anti-passivation agent, and 1-3 parts of water. The anti-passivation agent comprises sodium silicate and zeolite, and the mass ratio of sodium silicate to zeolite is 1:(0.5-1.5).

[0007] By adopting the above technical solution, sodium silicate hydrolyzes to generate hydroxide ions, and the increase in hydroxide ion concentration will inhibit the hydrolysis reaction of zincate ions and delay the formation of the passivation film on the zinc electrode; when the passivation film is formed, the microporous structure of zeolite provides a channel for the movement of reaction particles, and the reaction particles can penetrate the passivation film, enabling the zinc electrode to maintain a certain activity and continue to dissolve. Therefore, the interaction between sodium silicate and zeolite has a synergistic effect in improving the high-power discharge performance of the zinc electrode, resulting in an improvement in the discharge performance of alkaline zinc-manganese batteries in a high-power working environment.

[0008] Preferably, the zeolite is zeolite molecular sieve.

[0009] By adopting the above technical solution, the micropore size of the zeolite molecular sieve is more uniform, and the distribution of reaction particles penetrating the micropores of the zeolite is more uniform, which can reduce the self-discharge phenomenon caused by the concentration difference of reaction particles.

[0010] Preferably, the anti-passivation agent further includes calcium chloride hexahydrate, and the mass ratio of the zeolite to the calcium chloride hexahydrate is 1:(0.5-1.2).

[0011] By adopting the above technical solution, zinc loses electrons and is oxidized to release heat, and calcium chloride hexahydrate absorbs heat and loses its crystal water. The heat released by the oxidation of the zinc electrode is absorbed by calcium chloride hexahydrate, which can inhibit the temperature rise of the battery system, inhibit the reaction rate and reaction degree of the hydrolysis of zincate ions, thereby delaying the formation of the passivation film and improving the high-power discharge performance of the zinc electrode.

[0012] Preferably, the mass ratio of the corrosion inhibitor to the anti-passivation agent is 1:(3-6).

[0013] By adopting the above technical solution, the corrosion inhibitor can reduce the activity of the zinc electrode to achieve the purpose of inhibiting self-corrosion and reducing the gas evolution amount; the anti-passivation agent can increase the activity of the zinc electrode to achieve the purpose of delaying passivation. The ratio of the two is controlled within a certain range, which can alleviate the self-corrosion and passivation of the zinc electrode.

[0014] Preferably, the corrosion inhibitor is sodium dodecylbenzenesulfonate.

[0015] By adopting the above technical solution, sodium dodecylbenzenesulfonate forms an adsorption film on the surface of the zinc electrode to inhibit the self-corrosion of the zinc electrode; at the same time, the formed adsorption film is composed of many interlaced small holes to inhibit the passivation of the zinc electrode.

[0016] Preferably, the particle size range of the zinc powder is 40-150 mesh.

[0017] By adopting the above technical solution, the particle size of the zinc powder is controlled within a certain range, which can inhibit the passivation and self-corrosion of the zinc electrode. If the zinc powder is too coarse, the concentration diffusion of zinc hydroxide is blocked, accelerating passivation; if the zinc powder is too fine, the specific surface area is too large, and the gas evolution amount of self-corrosion is too large.

[0018] In the second aspect, the present application provides a preparation method of a negative electrode material for an alkaline zinc-manganese battery, adopting the following technical solution:

[0019] A preparation method of a negative electrode material for an alkaline zinc-manganese battery includes the following steps: mixing the zinc powder, the dispersant and the binder evenly to obtain a powder material, adding the electrolyte, the corrosion inhibitor, the anti-passivation agent and the water into the powder material, stirring evenly, and evacuating to obtain the negative electrode material for an alkaline zinc-manganese battery.

[0020] By adopting the above technical solution, the preparation method of the negative electrode material for alkaline zinc-manganese batteries is simple and can effectively reduce costs.

[0021] In a third aspect, the present application provides an application of a negative electrode material for alkaline zinc-manganese batteries, adopting the following technical solution: An application of a negative electrode material for alkaline zinc-manganese batteries, using the negative electrode material for alkaline zinc-manganese batteries as the negative electrode and assembling it with a manganese dioxide positive electrode to obtain an alkaline zinc-manganese battery.

[0022] By adopting the above technical solution, due to the addition of an anti-passivation agent in the negative electrode material for alkaline zinc-manganese batteries, the high-power discharge performance of the prepared alkaline zinc-manganese battery is improved. The number of pulse discharges (the first pulse discharges at 1500 mW for 2 s, the second pulse discharges at 650 mW for 28 s, and the pulse repeats 10 times and then stops for 55 min until 1.05 V) can reach 105 times, and the continuous discharge time (under a 3.9 Ω load, down to 0.8 V) can reach 335 min.

[0023] In summary, the present application has the following beneficial effects:

[0024] 1. The present application uses sodium silicate and zeolite as anti-passivation agents for the negative electrode material of alkaline zinc-manganese batteries: The hydroxide ions generated by the hydrolysis of sodium silicate can inhibit the hydrolysis of zincate ions, thereby delaying the formation of the passivation film on the zinc electrode; when the passivation film is formed, the reaction particles can penetrate the passivation film through the microporous structure of the zeolite, keeping the zinc electrode with a certain activity. The interaction between the two can improve the high-power discharge performance of the zinc electrode.

[0025] 2. The present application adds calcium chloride hexahydrate to the anti-passivation agent. Calcium chloride hexahydrate can absorb the heat released by the oxidation of the zinc electrode and remove its own crystal water, thereby inhibiting the temperature rise of the battery system, further inhibiting the hydrolysis of zincate ions, delaying the formation of the passivation film, and improving the high-power discharge performance of the zinc electrode. Specific Embodiments

[0026] The following further elaborates on the present application in conjunction with embodiments.

[0027] Embodiments

[0028] Embodiment 1

[0029] A negative electrode material for alkaline zinc-manganese batteries includes the following components in parts by weight: zinc powder (particle size range of 160 - 200 mesh) 55 parts, Tween 20 0.4 parts, sodium polyacrylate (model QP-3) 0.4 parts, potassium hydroxide solution with a concentration of 35% 25 parts, polyethylene glycol (model PEG600) 0.3 parts, anti-passivation agent 0.3 parts, and water 1 part, wherein the anti-passivation agent includes sodium silicate 0.2 parts and natural zeolite powder (particle size range of 180 - 200 mesh) 0.1 part.

[0030] A preparation method of a negative electrode material for an alkaline zinc-manganese battery, comprising the following steps: putting the weighed zinc powder, Tween 20 and sodium polyacrylate into a V-shaped mixing device, stirring for 30 min to obtain a powder material; transferring all the obtained powder material into a cylindrical stirring tank, adding the weighed potassium hydroxide solution, polyethylene glycol, passivation inhibitor and water into the cylindrical stirring tank, stirring for 40 min, and evacuating to obtain the negative electrode material for the alkaline zinc-manganese battery.

[0031] Example 2

[0032] A negative electrode material for an alkaline zinc-manganese battery, which is different from Example 1 in that: 65 parts of zinc powder, 0.8 part of Tween 20, 0.8 part of sodium polyacrylate, 30 parts of a potassium hydroxide solution with a concentration of 35%, 2 parts of polyethylene glycol, 2 parts of passivation inhibitor, and 3 parts of water, wherein the passivation inhibitor includes 0.8 part of sodium silicate and 1.2 parts of natural zeolite powder.

[0033] Example 3

[0034] A negative electrode material for an alkaline zinc-manganese battery, which is different from Example 1 in that: 60 parts of zinc powder, 0.6 part of Tween 20, 0.6 part of sodium polyacrylate, 28 parts of a potassium hydroxide solution with a concentration of 35%, 1.2 parts of polyethylene glycol, 1.2 parts of passivation inhibitor, and 2 parts of water, wherein the passivation inhibitor includes 0.6 part of sodium silicate and 0.6 part of natural zeolite powder.

[0035] Example 4

[0036] A negative electrode material for an alkaline zinc-manganese battery, which is different from Example 3 in that: NaY type zeolite molecular sieve is used instead of natural zeolite powder.

[0037] Example 5

[0038] A negative electrode material for an alkaline zinc-manganese battery, which is different from Example 4 in that: 1.5 parts of polyethylene glycol, 1.5 parts of passivation inhibitor, including 0.6 part of sodium silicate, 0.6 part of NaY type zeolite molecular sieve and 0.3 part of calcium chloride hexahydrate.

[0039] Example 6

[0040] A negative electrode material for an alkaline zinc-manganese battery, which is different from Example 4 in that: 1.9 parts of polyethylene glycol, 1.9 parts of passivation inhibitor, including 0.6 part of sodium silicate, 0.6 part of NaY type zeolite molecular sieve and 0.7 part of calcium chloride hexahydrate.

[0041] Example 7

[0042] A negative electrode material for an alkaline zinc-manganese battery, which is different from Example 4 in that: 1.7 parts of polyethylene glycol, 1.7 parts of passivation inhibitor, including 0.6 part of sodium silicate, 0.6 part of NaY type zeolite molecular sieve and 0.5 part of calcium chloride hexahydrate.

[0043] Example 8

[0044] A negative electrode material for alkaline zinc-manganese batteries, which is different from Example 7 in that: 0.2 parts of polyethylene glycol.

[0045] Example 9

[0046] A negative electrode material for alkaline zinc-manganese batteries, which is different from Example 7 in that: 0.6 parts of polyethylene glycol.

[0047] Example 10

[0048] A negative electrode material for alkaline zinc-manganese batteries, which is different from Example 7 in that: 0.3 parts of polyethylene glycol.

[0049] Example 11

[0050] A negative electrode material for alkaline zinc-manganese batteries, which is different from Example 10 in that: sodium dodecylbenzenesulfonate is used instead of polyethylene glycol.

[0051] Example 12

[0052] A negative electrode material for alkaline zinc-manganese batteries, which is different from Example 11 in that: the particle size range of zinc powder is 10 - 30 mesh.

[0053] Example 13

[0054] A negative electrode material for alkaline zinc-manganese batteries, which is different from Example 11 in that: the particle size range of zinc powder is 40 - 150 mesh.

[0055] Comparative Example

[0056] Comparative Example 1

[0057] A negative electrode material for alkaline zinc-manganese batteries, which is different from Example 3 in that: it does not include an anti-passivation agent.

[0058] Comparative Example 2

[0059] A negative electrode material for alkaline zinc-manganese batteries, which is different from Example 3 in that: 1.2 parts of anti-passivation agent, all of which are natural zeolite powder.

[0060] Comparative Example 3

[0061] A negative electrode material for alkaline zinc-manganese batteries, which is different from Example 3 in that: 1.2 parts of anti-passivation agent, all of which are sodium silicate.

[0062] Comparative Example 4

[0063] A negative electrode material for alkaline zinc-manganese batteries, which is different from Example 3 in that: 1.2 parts of anti-passivation agent, including 1 part of sodium silicate

[0064] and 0.2 parts of natural zeolite powder.

[0065] Comparative Example 5

[0066] A negative electrode material for alkaline zinc-manganese batteries, which is different from that in Example 3 in that: 1.2 parts of anti-passivation agent, including 0.4 part of sodium silicate and 0.8 part of natural zeolite powder.

[0067] Application Example

[0068] Application Example 1

[0069] An application of a negative electrode material for alkaline zinc-manganese batteries, using the negative electrode material of the alkaline zinc-manganese battery in Example 1 as the negative electrode; electrolytic manganese dioxide, graphite, potassium hydroxide solution with a concentration of 35%, and polyacrylic acid are mixed evenly according to a mass ratio of 90:6:3:0.4, and then tableted and granulated to make a positive electrode ring; the negative electrode and the positive electrode ring are assembled to obtain an alkaline zinc-manganese battery.

[0070] Application Examples 2-13

[0071] An application of a negative electrode material for alkaline zinc-manganese batteries, which is different from Application Example 1 in that: the materials used for the negative electrode are different, as shown in Table 1 specifically.

[0072] Table 1. Negative electrode materials for Application Examples 2-13

[0073] Application Example 2 3 4 5 6 7 Negative Electrode Material Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Application Example 8 9 10 11 12 13 Negative Electrode Material Example 8 Example 9 Example 10 Example 11 Example 12 Example 13

[0074] Application Comparative Example

[0075] Application Comparative Examples 1-5

[0076] An application of a negative electrode material for alkaline zinc-manganese batteries, which is different from Application Example 1 in that: the materials used for the negative electrode are different, as shown in Table 2 specifically.

[0077] Table 2. Negative electrode materials for Application Comparative Examples 1-5

[0078] Application Comparative Example 1 2 3 4 5 Negative Electrode Material Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5

[0079] For the alkaline zinc-manganese batteries of Application Examples 1-13 and Application Comparative Examples 1-5, high-power discharge performance tests are carried out, and the discharge modes are divided into two types: pulse discharge and continuous discharge.

[0080] Pulse discharge mode: The first pulse discharges at 1500 mW for 2 s, the second pulse discharges at 650 mW for 28 s, and this pulse is repeated 10 times and then stops for 55 min. Repeat the above pulse process and stop time until the preset cut-off voltage of 1.05 V, and record the number of pulses from the start of discharge to the cut-off voltage.

[0081] Continuous discharge mode: Continuously discharge the alkaline zinc-manganese battery with a 3.9 Ω load until the preset cut-off voltage of 0.8 V, and record the discharge time.

[0082] The specific results are shown in Table 3.

[0083] Table 3. Discharge Performance Test Results of Alkaline Zinc-Manganese Batteries

[0084] Types of Alkaline Zinc-Manganese Batteries Number of Pulse Discharges (times) Continuous Discharge Time (min) Application Example 1 105 335 Application Example 2 107 341 Application Example 3 108 353 Application Example 4 110 362 Application Example 5 113 369 Application Example 6 115 375 Application Example 7 118 380 Application Example 8 120 384 Application Example 9 123 389 Application Example 10 126 392 Application Example 11 129 395 Application Example 12 127 393 Application Example 13 131 399 Application Comparative Example 1 85 287 Application Comparative Example 2 88 298 Application Comparative Example 3 91 309 Application Comparative Example 4 98 322 Application Comparative Example 5 93 318

[0085] Combined with Application Examples 1-3, it can be seen that adding an anti-passivation agent composed of sodium silicate and natural zeolite powder to the negative electrode material enables the battery to have better high-power discharge performance. When the content of each component in the negative electrode material varies within a certain range, the high-power discharge performance of the battery remains at a certain level. The reason is that the hydroxide ions generated by the hydrolysis of sodium silicate can delay the formation of the passivation film, and the microporous structure of the zeolite enables the passivation film to have channels for the movement of reaction particles, keeping the zinc electrode active and improving the high-power discharge performance of the zinc electrode.

[0086] Combined with Application Example 3 and Application Example 4, it can be seen that among the components of the anti-passivation agent, the effect of zeolite molecular sieve is better than that of natural zeolite powder. The reason is that the micropore size of zeolite molecular sieve is more uniform. When the reaction particles penetrate the passivation film through the microporous structure, the distribution of reaction particles in the micropores is more uniform, thereby reducing the self-discharge phenomenon caused by the concentration difference of reaction particles.

[0087] Combined with Application Example 4 and Application Examples 5-7, it can be seen that adding calcium chloride hexahydrate to the components of the anti-passivation agent can improve the high-efficiency discharge performance of alkaline zinc-manganese batteries. The reason is that the heat released by the oxidation of the zinc electrode is absorbed by calcium chloride hexahydrate, and calcium chloride hexahydrate absorbs heat and loses its own crystal water. The absorption of heat by calcium chloride hexahydrate will inhibit the temperature rise of the battery system, thereby inhibiting the hydrolysis of zincate ions and delaying the formation of the passivation film.

[0088] Combined with Application Example 7 and Application Examples 8-10, it can be seen that the mass ratio of the corrosion inhibitor to the anti-passivation agent will affect the high-power discharge performance of the battery. The reason is that the effects of the corrosion inhibitor and the anti-passivation agent on the activity of the zinc electrode are opposite: the corrosion inhibitor aims to reduce the activity of the zinc electrode, inhibit the self-corrosion of the zinc electrode, reduce the gas evolution amount, and ensure the safe use of the battery; the anti-passivation agent aims to increase the activity of the zinc electrode, delay the passivation of the zinc electrode, and improve the high-power discharge performance of the battery. Therefore, the ratio of the two needs to be controlled within a certain range to achieve the effect of simultaneously alleviating the self-corrosion and passivation of the zinc electrode.

[0089] Combined with Application Example 10 and Application Example 11, it can be seen that the effect of sodium dodecylbenzenesulfonate as a corrosion inhibitor is better than that of polyethylene glycol. The reason is that while sodium dodecylbenzenesulfonate plays a corrosion inhibition role, it can also delay the passivation of the zinc electrode. The adsorption film formed on the surface of the zinc electrode has many small holes. The coating of the adsorption film on the zinc electrode inhibits the self-corrosion of the zinc electrode, and the small holes on the adsorption film provide channels for the movement of reaction particles, delaying the passivation of the zinc electrode.

[0090] From Application Examples 11, 12, and 13, it can be seen that the particle size of zinc powder also affects the high-power discharge performance of the battery. The reason is as follows: If the zinc powder is too coarse, the concentration diffusion of the solid-phase zinc hydroxide generated by the hydrolysis of zincate is hindered, and the passivation film is more likely to form, accelerating the passivation of the zinc electrode; if the zinc powder is too fine, the specific surface area of the zinc powder is too large, there are more active sites for reaction, and the gas evolution amount of self-corrosion is too large.

[0091] From Application Example 3 and Comparative Application Example 1, it can be seen that the high-power discharge performance of the alkaline zinc-manganese battery composed of the negative electrode material without the addition of the anti-passivation agent is significantly reduced. The reason is that the formation of the passivation film on the surface of the zinc electrode cannot be effectively inhibited, so that the passivation film has a greater negative effect on the activity of the zinc electrode.

[0092] From Application Example 3 and Comparative Application Examples 2-3, it can be seen that sodium silicate and zeolite in the anti-passivation agent are both indispensable, and there is a synergistic effect between the two in improving the high-power discharge performance of the zinc electrode. The reason is that sodium silicate acts before the formation of the passivation film to inhibit the formation of the passivation film; zeolite acts after the formation of the passivation film to keep the zinc electrode covered by the passivation film active. The two work together to effectively improve the high-power discharge performance of the alkaline zinc-manganese battery.

[0093] From Application Example 3 and Comparative Application Examples 4-5, it can be seen that the mass ratio of sodium silicate and zeolite affects the high-power discharge performance of the alkaline zinc-manganese battery. The reason is that if there is too little zeolite, there is insufficient channel for the reaction particles to move; if there is too much zeolite, the covering effect of the zeolite particles on the zinc electrode is enhanced, which instead inhibits the activity of the zinc electrode.

[0094] This specific embodiment is only an explanation of the present application, and it does not limit the present application. After reading this specification, those skilled in the art can make modifications that do not contribute creatively to this embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A negative electrode material for an alkaline zinc-manganese battery, characterized in that, It comprises components in the following parts by weight: 55 - 65 parts of zinc powder, 0.4 - 0.8 part of dispersant, 0.4 - 0.8 part of binder, 25 - 30 parts of electrolyte, 0.2 - 2 parts of corrosion inhibitor, 0.3 - 2 parts of anti-passivation agent, and 1 - 3 parts of water. The anti-passivation agent includes sodium silicate, zeolite, and calcium chloride hexahydrate. The mass ratio of the sodium silicate to the zeolite is 1:(0.5 - 1.5), and the mass ratio of the zeolite to the calcium chloride hexahydrate is 1:(0.5 - 1.2). The corrosion inhibitor is sodium dodecylbenzenesulfonate.

2. The negative electrode material for an alkaline zinc-manganese battery according to claim 1, characterized in that, The mass ratio of the corrosion inhibitor to the anti-passivation agent is 1:(3 - 6).

3. The negative electrode material for an alkaline zinc-manganese battery according to claim 1, characterized in that: The particle size range of the zinc powder is 40 - 150 mesh.

4. A preparation method of the negative electrode material for an alkaline zinc-manganese battery according to any one of claims 1-3, characterized in that, It includes the following steps: The zinc powder, the dispersant, and the binder are mixed evenly to obtain a powder material. The electrolyte, the corrosion inhibitor, the anti-passivation agent, and the water are added into the powder material, stirred evenly, and vacuumized to obtain the negative electrode material of the alkaline zinc-manganese battery.

5. An application of the negative electrode material for an alkaline zinc-manganese battery according to any one of claims 1-3, characterized in that, Using the negative electrode material of the alkaline zinc-manganese battery as the negative electrode, it is assembled with a manganese dioxide positive electrode to prepare an alkaline zinc-manganese battery.