CN110943267A

CN110943267A - Preparation method of flexible zinc-air battery with waste cloth as substrate

Info

Publication number: CN110943267A
Application number: CN201811104275.4A
Authority: CN
Inventors: 詹鸿飞; 江棋明
Original assignee: Fujian Jianou First High School
Current assignee: Fujian Jianou First High School
Priority date: 2018-09-21
Filing date: 2018-09-21
Publication date: 2020-03-31

Abstract

The invention provides a preparation method of a flexible zinc-air battery with waste cloth as a substrate, which comprises the following steps: electrodepositing cobalt hydroxide on a carbon film, performing heat treatment to obtain cobaltosic oxide serving as an anode, plating zinc on chemical copper-plated waste fabric serving as a cathode, using colloid of PVA and potassium hydroxide as a diaphragm and an electrolyte, and then performing plastic packaging by adopting a plastic film to obtain the flexible battery. Compared with the prior art, the invention has the following beneficial effects: the colloid of PVA and potassium hydroxide is used as diaphragm and electrolyte, and no liquid electrolyte is used, so that leakage can be effectively prevented, and the colloid can be tightly attached to the rough surface of the carbon cloth anode, and the conductive efficiency is improved. 2. The electrogalvanizing adopts a special alkaline galvanizing solution galvanizing formula, so that the galvanizing quality is greatly improved. 3. The negative electrode raw material is waste fabric, waste of waste articles can be avoided, and the environment-friendly effect is achieved.

Description

Preparation method of flexible zinc-air battery with waste cloth as substrate

Technical Field

The invention relates to a preparation method of a flexible zinc-air battery with waste cloth as a matrix, belonging to the technical field of energy devices.

Background

With changes in lifestyle and the development of electronic technology, flexible wearable electronic devices are coming into the line of sight of people. The traditional battery can not be bent, and can not meet the requirements of integral lightness, thinness and softness of electronic products. The development of flexible energy storage devices matched with flexible wearable electronic products plays a crucial role in the development of flexible wearable electronic devices.

At present, some small-sized flexible batteries with a certain degree of bending, such as flexible neutral zinc-manganese batteries, soft-package lithium batteries, etc., are available on the market. These batteries all suffer from the drawback of having a low energy density. However, the theoretical energy density of the zinc air battery can reach 1084 Wh/kg, which is 3 to 5 times of that of the lithium ion battery, and the zinc air battery can be used as an ideal flexible battery system.

The colloidal electrolyte is adopted to replace the traditional liquid electrolyte, can be in close contact with the carbon cloth of the battery, improves the efficiency, has certain strength and can provide restoring force after the battery is bent.

The negative electrode of the battery can be galvanized on non-conductive matrixes such as cloth and the like as the negative electrode, so that the flexibility is ensured, waste fabrics can be recycled, the cost is lower than that of other flexible batteries, and the performance is superior to that of other flexible batteries.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to provide a preparation method of a flexible zinc-air battery with waste cloth as a substrate.

The purpose of the invention is realized by the following technical scheme:

the invention provides a preparation method of a flexible zinc-air battery with waste cloth as a substrate, which comprises the following steps: electrodepositing cobalt hydroxide on a carbon film and performing heat treatment to obtain cobaltosic oxide as an anode, using colloid of PVA and potassium hydroxide as a diaphragm and electrolyte, sensitizing waste fabrics by stannous chloride and palladium chloride solution, then chemically plating copper, electrodepositing zinc in a special alkaline zinc plating solution as a cathode, and then performing plastic package by adopting a plastic film with holes to obtain the flexible battery.

Preferably, the preparation method of the cobalt hydroxide electrodeposited on the carbon film specifically adopts the following method:

1. cleaning the carbon film, then carrying out electroplating deposition in a cobalt nitrate aqueous solution with a certain concentration at the temperature of 20-35 ℃, washing the carbon film with clear water, putting the carbon film into a heating furnace, and carrying out heat treatment at a certain temperature.

Preferably, the concentration of the cobalt nitrate is 0.01 to 0.1mol/L.

Preferably, the voltage of the electroplating deposition is 1 to 1.2V, and the deposition time is 5 to 15min.

Preferably, the heat treatment temperature is 200 to 400 ℃, and the heat treatment time is 60 to 180min.

Preferably, the preparation method of the colloid containing potassium hydroxide specifically adopts the following method:

6. adding a certain amount of polyvinyl alcohol powder into a solution of potassium hydroxide with a certain concentration of 10ml, heating and stirring, and then solidifying to form the colloidal electrolyte.

Preferably, the concentration of the potassium hydroxide is 0.05 to 0.15g/ml.

Preferably, the preparation method of the zinc plating on the cloth specifically adopts the following method:

9. and cleaning the waste cloth, soaking the waste cloth in stannous chloride and palladium chloride solutions in sequence for sensitization, and carrying out industrial copper plating. And soaking the obtained copper cloth in a zinc chloride and potassium hydroxide alkali solution, and performing electrochemical galvanization at 25 to 30 ℃.

Preferably, the concentration of the stannous chloride solution is 10 to 15g/L, and 36.5% hydrochloric acid is added, wherein the concentration is 30 to 60mL/L; the concentration of the palladium chloride solution is 0.3 to 0.8g/L, and 36.5% hydrochloric acid is added, wherein the concentration is 15 to 30mL/L.

Preferably, the specially-made alkaline galvanizing solution comprises 80g/L of zinc chloride and 240g/L of potassium hydroxide solution.

Preferably, the current of the electroplating deposition is 0.1 to 0.4A, and the deposition time is 5 to 20min.

Compared with the prior art, the invention has the following beneficial effects:

1. colloid of PVA and potassium hydroxide is used as a diaphragm and electrolyte, and liquid electrolyte is not used, so that liquid leakage can be effectively prevented, and the colloid can be tightly attached to the rough surface of the carbon cloth anode, so that the conductive efficiency is increased. 2. The galvanizing quality is greatly improved by using a special alkaline galvanizing solution galvanizing formula for the galvanizing. 3. The negative electrode raw material is waste fabric, waste of waste articles can be avoided, and the environment-friendly effect is achieved.

The alkaline flexible zinc-air battery prepared by the invention meets the flexibility requirements of bending, folding and the like, and has the advantages of wide raw materials, lower cost, high energy density and simple preparation method.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the invention.

Example 1

The embodiment relates to a preparation method of a flexible zinc-air battery with waste cloth as a matrix, which comprises the following steps:

step one, putting the cleaned 2 cm-5 cm carbon film into a 0.01mol/L cobalt nitrate aqueous solution for electrodeposition, controlling the temperature at 20-35 ℃, taking out the carbon film after electrodeposition voltage is 1V and 10min, rinsing the carbon film with water, drying the carbon film, putting the carbon film into a heating furnace, and performing heat treatment for 2 hours at the temperature of 200 ℃ to obtain a cobaltosic oxide/carbon film;

step two, preparing the colloidal electrolyte: a certain amount of polyvinyl alcohol powder was added to a solution of 0.1g/ml 10ml potassium hydroxide, heated with stirring, and then solidified to form a colloidal electrolyte.

And step three, putting the 2 cm-by-5 cm cloth into a stannous chloride solution with the concentration of 10g/L and containing 40mL/L and 36.5% hydrochloric acid, soaking for 5min, rinsing, putting the cloth into a palladium chloride solution with the concentration of 0.5g/L and containing 20mL/L and 36.5% hydrochloric acid, soaking for 10min, rinsing, and carrying out industrial copper plating. Rinsing, putting into 250ml of alkali solution containing 20g of zinc chloride and 60g of potassium hydroxide, controlling the temperature at 20-35 ℃ to carry out electrodeposition with the current of 0.2A and the deposition time of 20min, and cleaning and drying. To obtain a negative electrode

And step three, laminating and combining a cobaltosic oxide/carbon film anode, a sheet colloidal electrolyte and a zinc cloth cathode, and plastically packaging with a plastic film to obtain the flexible battery.

The invention has many applications, and the above description is only a preferred embodiment of the invention. It should be noted that the above examples are only for illustrating the present invention, and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that various modifications can be made without departing from the principles of the invention and these modifications are to be considered within the scope of the invention.

Claims

1. A preparation method of a flexible zinc-air battery with waste cloth as a substrate is characterized by comprising the following steps: electrodepositing cobalt hydroxide on a carbon film and performing heat treatment to obtain cobaltosic oxide serving as a positive electrode, using colloid of PVA and potassium hydroxide as a diaphragm and an electrolyte, sensitizing waste fabrics by stannous chloride and palladium chloride solutions, then chemically plating copper, electrodepositing zinc in a special alkaline zinc plating solution serving as a negative electrode, and then plastically packaging by adopting a plastic film with holes to obtain the flexible battery.

2. The preparation method of the flexible zinc-air battery with the waste cloth as the matrix according to claim 1, wherein the preparation method of the cobalt hydroxide electrodeposition on the carbon cloth specifically adopts the following method: cleaning the carbon cloth, then carrying out electroplating deposition in 0.01-0.1mol/L cobalt nitrate aqueous solution at 20-35 ℃, washing the carbon cloth with clear water, putting the carbon cloth into a heating furnace, and carrying out heat treatment at a certain temperature.

3. The method for preparing the flexible zinc air battery with the waste cloth as the matrix according to claim 2, wherein the voltage of electroplating deposition is 1 to 1.2V, and the deposition time is 5 to 15min.

4. The method for preparing the flexible zinc-air battery with the waste cloth as the base body according to claim 2 is characterized in that the heat treatment temperature is 200-400 ℃, and the heat treatment time is 60-180min.

5. The method for preparing the flexible zinc-air battery with the waste cloth as the matrix according to claim 1, wherein the method for preparing the colloid containing the potassium hydroxide specifically adopts the following method: adding a certain amount of polyvinyl alcohol into a solution of potassium hydroxide with a certain concentration of 10ml, heating and stirring, and then solidifying to form the colloidal electrolyte.

6. The method for preparing the flexible zinc-air battery with the waste cloth as the matrix according to claim 5, wherein the concentration of the potassium hydroxide is 0.05 to 0.15g/ml.

7. The method for preparing the flexible zinc-air battery with the waste cloth as the matrix according to claim 1, wherein the concentration of a stannous chloride solution in the sensitization process is 10 to 15g/L, and 36.5% hydrochloric acid is added, and the concentration is 30 to 60mL/L.

8. The concentration of the palladium chloride solution is 0.3 to 0.8g/L, and 36.5% hydrochloric acid is added, and the concentration is 15 to 30mL/L.

9. The preparation method of the flexible zinc-air battery with the waste cloth as the base body according to claim 1, wherein the specially-made alkaline zinc plating solution comprises 80g/L zinc chloride and 240g/L potassium hydroxide solution.

10. The method for preparing the flexible zinc air battery by using the waste cloth as the matrix according to claim 1, wherein the current of electroplating deposition is 0.1 to 0.4A, and the deposition time is 5 to 20min.