Preparation method of a button zinc-air battery

Abstract

The present invention discloses a button-type zinc-air battery, belonging to the technical field of zinc-air batteries. The positive electrode case is coated with an adhesive, and a diffusion paper is pasted on the air holes at the bottom of the positive electrode case. Then, a sealant is applied to the bottom of the positive electrode case. The positive electrode plate is punched into a disc shape and installed in the positive electrode case. One side of the polytetrafluoroethylene breathable membrane is bonded to the bottom of the positive electrode case to form an integrated structure. At the same time, the bottom edge of the negative electrode cover is printed with a sealant and combined with an outward-expanded U-shaped sealing ring. Then, zinc powder is put into the negative electrode cover, and a negative electrode liquid is injected. Then, the negative electrode cover with the negative electrode material and the sealing ring assembly are placed into the positive electrode case. Then, the open end of the positive electrode case is sealed to form an R position and is in contact connection with the insulating rubber ring and the reverse edge of the negative electrode cover. Finally, a sealing sticker is pasted on the air holes of the positive electrode case of the battery. The catalytic layer positive electrode powder is added with a metal oxide catalyst, which can accelerate the speed of the discharge reaction and improve the high-power discharge performance of the zinc-air battery.

Description

Technical Field

[0001] The present invention belongs to the field of zinc-air batteries, and more specifically, particularly relates to a preparation method of a button zinc-air battery. Background Art

[0002] For the current zinc-air battery, its components from outside to inside are: a sealing sticker, a positive electrode case (with air holes), a diffusion paper, a positive electrode plate, a sealing ring, a negative electrode cover, and negative zinc (negative electrode material). And for the positive electrode plate of the current zinc-air battery, from outside to inside are: a polytetrafluoroethylene breathable membrane, a catalytic layer, a conductive nickel mesh, and a separator paper. Then, a sealing glue structure is provided between the battery positive electrode case and the positive electrode plate, so that the positive electrode plate and the battery positive electrode case form an integrated structure. The sealing glue between the battery positive electrode case and the positive electrode plate is a Teflon thermosetting glue.

[0003] However, the catalytic layer is roll-pressed into the positive electrode plate at one time by a rolling press. The porosity of the powder particles inside the catalytic layer is small, and the specific surface area is small, which is not conducive to the high-power discharge reaction of the battery, resulting in poor high-power discharge performance. Summary of the Invention

[0004] The purpose of the present invention is to solve the deficiencies existing in the prior art, and to propose a preparation method of a button zinc-air battery, which can improve the discharge performance of the zinc-air battery.

[0005] To achieve the above purpose, the present invention provides the following technical solutions:

[0006] A preparation method of a button zinc-air battery includes the following steps:

[0007] S1. Preparation of the positive electrode material. Weigh the following raw materials by weight:

[0008] 34 - 38 parts of activated carbon; 8 - 12 parts of conductive carbon; 28 - 32 parts of manganese oxide; 0.01 - 20 parts of catalyst; 25 - 26 parts of polytetrafluoroethylene;

[0009] Add activated carbon, conductive carbon, manganese oxide, and catalyst into a 60°C vacuum furnace for 2 hours to remove moisture before stirring. Then, add activated carbon, conductive carbon, manganese oxide, catalyst, and polytetrafluoroethylene into the stirring container in sequence, and stir evenly under the conditions of an environmental temperature of 15 - 30°C and a humidity of 45 - 70% RH to obtain the positive powder of the catalytic layer;

[0010] Then, press and granulate the positive powder of the catalytic layer with a roller repeatedly; place the polytetrafluoroethylene breathable membrane, the granulated positive powder of the catalytic layer, the conductive nickel mesh, and the separator paper on the rolling press in sequence, and roll them into a positive electrode plate;

[0011] S2. Preparation of the negative electrode material. Weigh the following raw materials by weight:

[0012] 160 - 170 parts of zinc powder; 3 - 4 parts of gelling agent (1); 1 - 2 parts of gelling agent (2); 35 - 39 parts of potassium hydroxide; 5 - 6 parts of zinc oxide; 0.015 - 0.02 parts of indium hydroxide; 35 - 39 parts of pure water;

[0013] a1. Add zinc powder, gelling agent (1), and gelling agent (2) into a stirring container in sequence, and stir evenly under the conditions of an ambient temperature of 15 - 30°C and a humidity of 45 - 70%RH to obtain the negative electrode zinc powder;

[0014] a2. Add zinc oxide and indium hydroxide into deionized water and stir evenly;

[0015] b2. Then add potassium hydroxide to the solution in step a2 and stir for about 2 hours until the materials are dissolved;

[0016] c2. After the solution in step b2 is cooled, adjust the specific gravity to 1.355 - 1.365 g / ml (25°C) to obtain the negative electrode liquid;

[0017] S3. Preparation of the zinc - air button battery:

[0018] Apply an adhesive to the positive electrode case, stick the diffusion paper on the air holes at the bottom of the positive electrode case, then apply a sealant to the bottom of the positive electrode case, punch the positive electrode plate into a round cake, put the positive electrode plate into the positive electrode case, and bond one side of the polytetrafluoroethylene breathable membrane to the bottom of the positive electrode case to form an integrated structure; at the same time, print a sealant on the bottom edge of the negative electrode cover and combine it with an outward - extending U - shaped sealing ring, then put the zinc powder into the negative electrode cover, inject the negative electrode liquid, and then put the negative electrode cover - and - sealing - ring combination containing the negative electrode material into the positive electrode case, and then seal the open end of the positive electrode case to form an R position and make it contact and connect with the insulating rubber ring and the reverse edge of the negative electrode cover. Finally, stick a sealing sticker on the air holes of the positive electrode case of the battery.

[0019] Preferably, the manganese oxide in S1 is chemical manganese dioxide or active manganese dioxide or electrolytic manganese dioxide.

[0020] Preferably, the manganese oxide in S1 is a mixture of two or three of chemical manganese dioxide, active manganese dioxide, and electrolytic manganese dioxide.

[0021] Preferably, the manganese oxide in S1 is a mixture of one, two, or three of chemical manganese dioxide, active manganese dioxide, and electrolytic manganese dioxide and potassium permanganate.

[0022] Preferably, the conductive carbon in S1 is any one of graphite, carbon black, or a mixture of graphite and carbon black.

[0023] Preferably, the catalyst in S1 is a metal oxide, including one, two or a mixture of two or more of iron oxide, titanium oxide, cobalt oxide, aluminum oxide, nickel oxide, calcium oxide, magnesium oxide, and copper oxide.

[0024] Preferably, the gelling agent (1) in S2 is a combination of one of carboxymethyl cellulose and polyacrylic acid, and the gelling agent (2) is a combination of one of sodium carboxymethyl cellulose, sodium polyacrylate, and a cross-linked body of polyacrylic acid and sodium polyacrylate.

[0025] Preferably, the negative electrode cover in S3 is made of a composite metal material, including a nickel layer, a stainless steel layer, a copper layer, and a tin layer arranged in sequence from outside to inside.

[0026] A further solution is that the thickness of the nickel layer is 10 - 30 μm, the thickness of the copper layer is 30 - 50 μm, and the thickness of the tin layer or tin alloy layer or indium layer or indium alloy layer is 0.1 - 2 μm.

[0027] A further solution is that the sealing ring is injection-molded from polyamide resin.

[0028] A further solution is that the positive electrode case is stamped from a stainless steel plate.

[0029] A further solution is that the negative electrode cover is stamped from the above composite metal material.

[0030] Technical effects and advantages of the present invention: A preparation method of a button-type zinc-air battery provided by the present invention, compared with the prior art, adding a metal oxide catalyst to the positive electrode powder of the catalytic layer can accelerate the speed of the discharge reaction, improve the high-power discharge performance of the zinc-air battery, and drying the activated carbon, conductive carbon, manganese oxide, and catalyst in a 60°C vacuum furnace for 2 hours before stirring can remove moisture, enabling the materials to be fully mixed and stirred. And by installing the positive electrode plate into the positive electrode case, the polytetrafluoroethylene breathable membrane is adhered to the bottom of the positive electrode case to form an integrated structure; at the same time, applying a sealant to the bottom edge of the negative electrode cover and combining it with an outward-expanded U-shaped sealing ring ensures that the prepared zinc-air battery has a tightly structured feature. Using a nickel-stainless steel-copper composite sheet negative electrode cover plated with tin or indium, adding indium element and zinc oxide to the negative electrode material can inhibit the generation of hydrogen with elements having a relatively high hydrogen evolution overpotential. Detailed implementation manners

[0031] In order to make the objectives, technical solutions, and advantages of the present invention clearer and more understandable, the following further elaborates on the present invention in combination with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0032] Example 1

[0033] A preparation method of a button zinc-air battery, comprising the following steps:

[0034] 1. Preparation of the positive electrode material, weighing the following raw materials by weight:

[0035] 34-38 parts of activated carbon; 8-12 parts of carbon black; 28-32 parts of electrolytic manganese dioxide; 0.5-1.5 parts of iron oxide; 25-26 parts of polytetrafluoroethylene.

[0036] Before stirring, activated carbon, carbon black, electrolytic manganese dioxide and iron oxide are dried in a 60°C vacuum furnace for 2 hours to remove moisture. Then, activated carbon, carbon black, electrolytic manganese dioxide, iron oxide, and polytetrafluoroethylene are added to the stirring container in sequence, and stirred evenly under the conditions of an ambient temperature of 15-30°C and a humidity of 45-70%RH to obtain the catalytic layer positive electrode powder. Then, the catalytic layer positive electrode powder is granulated by repeatedly pressing tablets with a roller. The polytetrafluoroethylene breathable membrane, the granulated catalytic layer positive electrode powder, the conductive nickel mesh, and the separator paper are placed on the rolling press in sequence and rolled into a positive electrode plate.

[0037] Among them, the carbon black is one of graphite, carbon black or a mixture of graphite and carbon black of conductive carbon, the electrolytic manganese dioxide is one of chemical manganese dioxide, active manganese dioxide or electrolytic manganese dioxide of manganese oxide, and the iron oxide is a metal oxide of a catalyst, including one of iron oxide, titanium oxide, cobalt oxide, aluminum oxide, nickel oxide, calcium oxide, magnesium oxide, copper oxide.

[0038] 2. Preparation of the negative electrode material, weighing the following raw materials by weight:

[0039] 160 parts of zinc powder; 3 parts of carboxymethyl cellulose; 1 part of sodium polyacrylate; 37 parts of potassium hydroxide; 5 parts of zinc oxide; 0.018 part of indium hydroxide; 37 parts of pure water.

[0040] a1. Add zinc powder, carboxymethyl cellulose, and sodium polyacrylate to the stirring container in sequence, and stir evenly under the conditions of an ambient temperature of 15-30°C and a humidity of 45-70%RH to obtain the negative electrode zinc powder.

[0041] a2. Add zinc oxide and indium hydroxide to deionized water and stir evenly;

[0042] b2. Then add potassium hydroxide to step a2 and stir for about 2 hours until the material dissolves;

[0043] c2. After the solution in step b2 cools, adjust the specific gravity to 1.355-1.365 g / ml (25°C) to obtain the negative electrode liquid;

[0044] Among them, the carboxymethyl cellulose is one of the carboxymethyl cellulose and polyacrylic acid of the gelling agent (1), and polyacrylic acid can also be used for substitution. The sodium polyacrylate is one of the sodium carboxymethyl cellulose, sodium polyacrylate, and the cross-linked body of polyacrylic acid and sodium polyacrylate of the gelling agent (2).

[0045] 3. Preparation of the zinc-air button battery

[0046] Apply an adhesive to the positive electrode case, stick the diffusion paper on the air holes at the bottom of the positive electrode case, then apply a sealant to the bottom of the positive electrode case, punch the positive electrode plate into a disc, place the positive electrode plate into the positive electrode case, and bond one side of the polytetrafluoroethylene breathable membrane to the bottom of the positive electrode case to form an integrated structure. At the same time, print a sealant on the bottom edge of the negative electrode cover, combine it with the outward-expanded U-shaped sealing ring, then put zinc powder into the negative electrode cover, inject the negative electrode liquid, and then put the negative electrode cover-sealing ring combination containing the negative electrode material into the positive electrode case. Then seal the open end of the positive electrode case to form an R position, and make contact connection with the insulating rubber ring and the turned-back edge of the negative electrode cover. Then stick a seal sticker on the air holes of the positive electrode case of the battery. The negative electrode cover is made of a composite metal material, including a nickel layer, a stainless steel layer, a copper layer, and a tin layer arranged in sequence from outside to inside.

[0047] Comparative Example 1

[0048] A preparation method of a button-type zinc-air battery includes the following steps:

[0049] 1. Preparation of the positive electrode material: Weigh the following raw materials by weight parts:

[0050] 34 - 38 parts of activated carbon; 8 - 12 parts of carbon black; 28 - 32 parts of electrolytic manganese dioxide; 25 - 26 parts of polytetrafluoroethylene.

[0051] Place the polytetrafluoroethylene breathable membrane, the catalytic layer positive electrode powder, the conductive nickel mesh, and the separator paper on the rolling machine in sequence, and roll them into a positive electrode plate.

[0052] 2. Preparation of the negative electrode material: Weigh the following raw materials by weight parts:

[0053] 160 parts of zinc powder; 3 parts of carboxymethyl cellulose; 1 part of sodium polyacrylate; 37 parts of potassium hydroxide; 5 parts of zinc oxide; 37 parts of pure water.

[0054] a1. Add zinc powder, carboxymethyl cellulose, and sodium polyacrylate into the stirring container in sequence, and stir evenly under the conditions of an environmental temperature of 15 - 30°C and a humidity of 45 - 70%RH to obtain the negative electrode zinc powder.

[0055] a2. Add zinc oxide into deionized water and stir evenly;

[0056] b2. Then add potassium hydroxide to step a2 and stir for about 2 hours until the material is dissolved;

[0057] c2. After the solution in step b2 is cooled, adjust the specific gravity to 1.443 - 1.445 g / ml (25 °C) to obtain the negative electrode solution;

[0058] 3. Preparation of zinc - air button battery

[0059] Apply adhesive to the positive electrode case, stick the diffusion paper on the air holes at the bottom of the positive electrode case, punch the positive electrode plate into round cakes, and place the positive electrode plate into the positive electrode case; at the same time, print sealant on the bottom edge of the negative electrode cover, combine it with the sealing ring, then put zinc powder into the negative electrode cover, inject the negative electrode solution, and then put the negative electrode cover - sealing ring combination containing the negative electrode material into the positive electrode case. Then seal the open end of the positive electrode case to form an R position, and make it contact and connect with the insulating rubber ring and the turned - up edge of the negative electrode cover. Finally, stick a sealing sticker on the air holes of the positive electrode case of the battery.

[0060] The negative electrode cover is made of a composite metal material, including a nickel layer, a stainless - steel layer, and a copper layer arranged in sequence from outside to inside.

[0061] The specific formulation data of three groups of examples according to Example 1 and Comparative Example 1 of the present invention are as follows in the table:

[0062]

[0063]

[0064] It can be seen from Table 1 that the zinc - air button battery of Example 1 of the present invention has no liquid leakage phenomenon, and its discharge performance is significantly improved.

[0065] Finally, it should be noted that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, for those skilled in the art, they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A preparation method of a button zinc-air battery, characterized in that, It includes the following steps: S1. Preparation of the positive electrode material. Weigh the following raw materials by weight parts: 34 - 38 parts of activated carbon; 8 - 12 parts of conductive carbon; 28 - 32 parts of manganese oxide; 0.01 - 20 parts of catalyst; 25 - 26 parts of polytetrafluoroethylene; the catalyst is a metal oxide; Add activated carbon, conductive carbon, manganese oxide and catalyst into a 60°C vacuum furnace and bake for 2 hours to remove moisture before stirring. Then add activated carbon, conductive carbon, manganese oxide, catalyst and polytetrafluoroethylene into the stirring container in sequence, and stir evenly under the conditions of environmental temperature of 15 - 30°C and humidity of 45 - 70%RH to obtain the catalytic layer positive electrode powder; Then, repeatedly press and granulate the catalytic layer positive electrode powder with a rolling mill; place the polytetrafluoroethylene breathable membrane, the granulated catalytic layer positive electrode powder, the conductive nickel mesh and the separator paper on the rolling press in sequence and roll them into a positive electrode plate; S2. Preparation of the negative electrode material. Weigh the following raw materials by weight parts: 160 - 170 parts of zinc powder; 3 - 4 parts of gelling agent (1); 1 - 2 parts of gelling agent (2); 35 - 39 parts of potassium hydroxide; 5 - 6 parts of zinc oxide; 0.015 - 0.02 parts of indium hydroxide; 35 - 39 parts of pure water; a1. Add zinc powder, gelling agent (1) and gelling agent (2) into the stirring container in sequence and stir evenly under the conditions of environmental temperature of 15 - 30°C and humidity of 45 - 70%RH to obtain the negative electrode zinc powder; a2. Add zinc oxide and indium hydroxide into deionized water and stir evenly; b2. Then add potassium hydroxide to step a2 and stir for about 2 hours until the materials are dissolved; c2. After the solution in step b2 cools down, adjust the specific gravity to 1.355 - 1.365 g / ml (25°C) to obtain the negative electrode liquid; S3. Preparation of the zinc - air button battery: Apply adhesive to the positive electrode case, stick the diffusion paper on the air holes at the bottom of the positive electrode case, then apply sealant to the bottom of the positive electrode case. Cut the positive electrode plate into a round cake, put the positive electrode plate into the positive electrode case, and bond one side of the polytetrafluoroethylene breathable membrane with the bottom of the positive electrode case to form an integrated structure; at the same time, print sealant on the bottom edge of the negative electrode cover and combine it with the outward - extending U - shaped sealing ring. Then put the zinc powder into the negative electrode cover, inject the negative electrode liquid, and put the negative electrode cover - and - sealing - ring combination filled with the negative electrode material into the positive electrode case. Then seal the open end of the positive electrode case to form an R position, and make it contact and connect with the insulating rubber ring and the reverse edge of the negative electrode cover. Finally, stick a sealing sticker on the air holes of the positive electrode case of the battery.

2. The preparation method of a button zinc-air battery according to claim 1, wherein: The manganese oxide in S1 is chemical manganese dioxide, active manganese dioxide or electrolytic manganese dioxide.

3. The preparation method of a button zinc-air battery according to claim 1, characterized in that: The manganese oxide in S1 is a mixture of two or three of chemical manganese dioxide, active manganese dioxide and electrolytic manganese dioxide.

4. The preparation method of a button-type zinc-air battery according to claim 1, characterized in that: The manganese oxide in S1 is a mixture of one, two or three of chemical manganese dioxide, active manganese dioxide, electrolytic manganese dioxide and potassium permanganate.

5. The preparation method of a button-type zinc-air battery according to claim 1, characterized in that: The conductive carbon in S1 is any one of graphite, carbon black or a mixture of graphite and carbon black.

6. The preparation method of a button-type zinc-air battery according to claim 1, characterized in that: The catalyst in S1 is a metal oxide, including one, two or a mixture of more than two of iron oxide, titanium oxide, cobalt oxide, aluminum oxide, nickel oxide, calcium oxide, magnesium oxide, and copper oxide.

7. The preparation method of a button-type zinc-air battery according to claim 1, wherein: The gelling agent (1) in S2 is one or a combination of carboxymethyl cellulose and polyacrylic acid, and the gelling agent (2) is one or a combination of sodium carboxymethyl cellulose, sodium polyacrylate, and a cross-linked body of polyacrylic acid and sodium polyacrylate.

8. The preparation method of a button zinc-air battery according to claim 1, characterized in that: The negative electrode cap in S3 is composed of a composite metal material, including a nickel layer, a stainless steel layer, a copper layer, and a tin layer arranged in sequence from outside to inside.

Images