阅读说明：本技术 一种基于pva/kc-koh复合凝胶电解质的柔性铝空气电池 (Flexible aluminum air battery based on PVA/KC-KOH composite gel electrolyte ) 是由 陈黎 孙雪艳 王成骅 于思乐 赵炜 陈曦 于 2021-05-25 设计创作，主要内容包括：本发明公开了一种基于PVA/KC-KOH复合凝胶电解质的柔性铝空气电池,该柔性铝空气电池从上至下依次由集流体、铝箔金属阳极、PVA/KC-KOH复合凝胶电解质、复合催化剂空气阴极、集流体层叠而成；本发明创造性的将к-卡拉胶应用到电池电解质中,具有大范围可调的固液比例,可以抑制开放性铝空气电池的漏液问题；并且PVA/KC-KOH复合凝胶电解质解决了传统铝空气电池结构在柔性方面的限制,因而,本发明可制备超薄柔性、高导电率的铝空气电池。(The invention discloses a flexible aluminum-air battery based on a PVA/KC-KOH composite gel electrolyte, which is formed by sequentially laminating a current collector, an aluminum foil metal anode, a PVA/KC-KOH composite gel electrolyte, a composite catalyst air cathode and a current collector from top to bottom; the kappa-carrageenan is creatively applied to the battery electrolyte, has a large-range adjustable solid-liquid ratio, and can inhibit the leakage problem of the open aluminum-air battery; and the PVA/KC-KOH composite gel electrolyte solves the limitation of the traditional aluminum-air battery structure in the aspect of flexibility, so that the ultrathin flexible high-conductivity aluminum-air battery can be prepared by the method.)

1. The flexible aluminum-air battery based on the PVA/KC-KOH composite gel electrolyte is characterized by being formed by sequentially stacking a current collector (1), an aluminum foil metal anode (2), the PVA/KC-KOH composite gel electrolyte (3), a composite catalyst air cathode (4) and the current collector (1) from top to bottom.

2. The flexible aluminum-air battery based on PVA/KC-KOH composite gel electrolyte as claimed in claim 1, wherein the preparation method of the PVA/KC-KOH composite gel electrolyte (3) is as follows:

dissolving kappa-carrageenan (KC) and PVA in an aqueous solution, heating to 90-98 ℃ while stirring, and pouring into a film forming mold after uniformly mixing; placing the film forming mould in a freezing environment, and forming a first network by PVA through freeze-thaw cycle to obtain a gel film with the thickness of 0.5-1 mm and uniform thickness; soaking the gel film in potassium hydroxide solution for a certain time until KC passes K⁺And (3) crosslinking to form a second network, namely obtaining the needed PVA/KC-KOH composite gel electrolyte.

3. The flexible aluminum-air cell based on PVA/KC-KOH composite gel electrolyte as claimed in claim 2, wherein the ratio of PVA: the mass ratio of KC is 10: 1-8: 1.

4. The flexible aluminum-air battery based on the PVA/KC-KOH composite gel electrolyte as claimed in claim 2, wherein the freezing temperature is-18 ℃ to-30 ℃, and the flexible aluminum-air battery is unfrozen at room temperature;

5. the flexible aluminum-air battery based on PVA/KC-KOH composite gel electrolyte as claimed in claim 2, wherein the concentration of the potassium hydroxide solution is 1 mol/L-3 mol/L.

6. The flexible aluminum air cell based on PVA/KC-KOH composite gel electrolyte as claimed in claim 2, wherein the ratio of PVA: KC is in a mass ratio of 9:1, the heating temperature is 95 ℃, and the freezing temperature is-20 ℃.

7. The flexible aluminum-air battery based on PVA/KC-KOH composite gel electrolyte as claimed in claim 1, wherein the current collector (1) is made of nickel mesh material.

8. The flexible aluminum-air battery based on the PVA/KC-KOH composite gel electrolyte as claimed in claim 1, wherein the composite catalyst of the composite catalyst air cathode (4) is composed of sulfur-doped graphene, manganese dioxide and conductive carbon black, wherein the sulfur-doped graphene accounts for 5-15% of the mass of the composite catalyst, the manganese dioxide accounts for 10-30% of the mass of the composite catalyst, and the conductive carbon black composite catalyst accounts for 55-85% of the mass of the composite catalyst.

9. The flexible aluminum-air battery based on the PVA/KC-KOH composite gel electrolyte as claimed in claim 8, wherein the sulfur-doped graphene accounts for 5% of the mass of the composite catalyst, and the manganese dioxide accounts for 20% of the mass of the composite catalyst.

10. The flexible aluminum-air battery based on PVA/KC-KOH composite gel electrolyte as claimed in claim 1, wherein the aluminum foil metal anode (2) is composed of aluminum, magnesium, gallium and indium, wherein the aluminum accounts for 98% of the mass fraction of the aluminum foil material.

Technical Field

The invention relates to the field of aluminum-air batteries, in particular to a flexible aluminum-air battery based on a PVA/KC-KOH composite gel electrolyte.

Background

The rapid development of electronic devices puts higher performance demands on energy storage devices, and metal-air batteries have become a focus of attention of researchers in recent years due to their high theoretical energy density. Aluminum-air batteries are a promising safe power source due to their high specific energy, low cost, high recyclability, and environmental benefits. The electronic device is expected to be widely developed in the development of next-generation electronic equipment, such as electric automobiles, wearable portable electronic products and the like. However, energy storage devices are required to be light in weight, high in flexibility and high in safety. However, the high quality, difficult packaging, and rigid flexibility of the conventional aluminum-air battery limit its application in portable, flexible electronic products.

In recent years, considerable progress has been made in the development of high performance flexible energy storage and conversion devices, but there are still many technical challenges, for flexible electronic applications, stable electrochemical performance under repetitive external forces is crucial for flexible metal-air batteries. Much work has been devoted to the search for effective electrode/electrolyte materials and more preferred battery structures to develop flexible power sources with better electrochemical performance for use in flexible electronics.

Disclosure of Invention

Aiming at the limitation of the prior art, the invention provides a flexible aluminum-air battery based on a PVA/KC-KOH composite gel electrolyte, which can realize an all-solid-state aluminum-air battery and fundamentally overcomes the defects of high quality, difficult packaging, difficult bending, easy leakage and flammability of electrolyte and the like of the traditional electrolyte aluminum-air battery.

In order to solve the problems, the invention adopts the following technical scheme:

the flexible aluminum-air battery is formed by sequentially stacking a current collector 1, an aluminum foil metal anode 2, a PVA/KC-KOH composite gel electrolyte 3, a composite catalyst air cathode 4 and a current collector 1 from top to bottom.

The preparation method of the PVA/KC-KOH composite gel electrolyte 3 comprises the following steps:

dissolving kappa-carrageenan (KC) and PVA in an aqueous solution, heating to 90-98 ℃ while stirring, and pouring into a film forming mold after uniformly mixing; the film-forming mould is put into a freezing environment,PVA forms a first network through freeze-thaw cycle to obtain a gel film with uniform thickness of 0.5-1 mm; soaking the gel film in potassium hydroxide solution for a certain time until KC passes K⁺And crosslinking to form a second network, so that the needed PVA/KC-KOH composite gel electrolyte can be obtained.

The PVA/KC-KOH composite gel electrolyte is characterized in that the ratio of PVA: the mass ratio of KC is 10: 1-8: 1.

The freezing temperature is-18 ℃ to-30 ℃, and the thawing is carried out at room temperature;

the concentration of the potassium hydroxide solution is 1 mol/L-3 mol/L.

The current collector 1 is made of a nickel mesh material.

The composite catalyst of the composite catalyst air cathode 4 comprises sulfur-doped graphene, manganese dioxide and conductive carbon black, wherein the sulfur-doped graphene accounts for 5-15% of the mass of the composite catalyst, the manganese dioxide accounts for 10-30% of the mass of the composite catalyst, and the conductive carbon black composite catalyst accounts for 55-85% of the mass of the composite catalyst.

The aluminum foil metal anode 2 is composed of aluminum, magnesium, gallium and indium, wherein the aluminum accounts for 98% of the mass fraction of the aluminum foil material.

Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages.

1. The invention adopts PVA/KC-KOH composite gel electrolyte to replace liquid electrolyte and diaphragm, avoids the leakage of electrolyte and flammability, and makes the aluminum-air battery light in weight, easy to package and strong in flexibility.

2. When the PVA/KC-KOH composite gel electrolyte is used in an aluminum air battery, the reactant deposition of an aluminum metal anode and an electrolyte interface can be stabilized, so that the self-corrosion phenomenon of aluminum in an alkaline electrolyte is inhibited.

3. The invention discloses a flexible aluminum air battery based on a PVA/KC-KOH composite gel electrolyte, which solves the problem that the traditional rigid structure functional equipment cannot meet the actual energy supply requirement of the next generation of flexible wearable electronic devices.

4. The cost of PVA and KC is low, the preparation method of the PVA/KC-KOH composite gel electrolyte is simple, the requirement on required equipment is low, and large-scale industrial preparation can be realized.

Drawings

Fig. 1 is a structural view of a battery of the present invention.

FIG. 2 is a graph of effective voltage and power density of a flexible aluminum-air battery based on a PVA/KC-KOH composite gel electrolyte at 90 ℃ and different current densities.

FIG. 3 is a graph of the discharge performance of a flexible aluminum-air cell based on a PVA/KC-KOH composite gel electrolyte at 90 degrees according to the invention.

Detailed Description

The invention is described in further detail below with reference to the figures and specific examples.

As shown in figure 1, the flexible aluminum-air battery based on the PVA/KC-KOH composite gel electrolyte is formed by sequentially laminating a current collector 1, an aluminum foil metal anode 2, a PVA/KC-KOH composite gel electrolyte 3, a composite catalyst air cathode 4 and a current collector 1 from top to bottom.

As a preferred embodiment of the present invention, the current collector 1 is made of a nickel mesh material.

As a preferred embodiment of the invention, the aluminum foil metal anode 2 is composed of aluminum, magnesium, gallium and indium, wherein the aluminum accounts for 98% of the mass fraction of the aluminum foil material.

The preparation method of the PVA/KC-KOH composite gel electrolyte 3 comprises the following steps:

dissolving kappa-carrageenan (KC) and PVA in an aqueous solution, heating to 90-98 ℃ while stirring, and pouring into a film forming mold after uniformly mixing; placing the film forming mould in a freezing environment, and forming a first network by PVA through freeze-thaw cycle to obtain a gel film with the thickness of 0.5-1 mm and uniform thickness; soaking the gel film in potassium hydroxide solution for a certain time until KC passes K⁺And (3) crosslinking to form a second network, namely obtaining the needed PVA/KC-KOH composite gel electrolyte.

As a preferred embodiment of the present invention, the PVA/KC-KOH composite gel electrolyte, wherein the PVA: KC is in a mass ratio of 10: 1-8: 1, and the more preferable PVA: the mass ratio of KC is 9: 1.

As a preferred embodiment of the invention, the PVA/KC-KOH composite gel electrolyte is heated at 90-98 ℃, and more preferably at 95 ℃.

In a preferred embodiment of the present invention, the PVA/KC-KOH composite gel electrolyte has a freezing temperature of-18 ℃ to-30 ℃, more preferably-20 ℃.

In a preferred embodiment of the present invention, the concentration of the PVA/KC-KOH composite gel electrolyte is 1mol/L to 3mol/L, and more preferably 2 mol/L.

In a preferred embodiment of the present invention, the composite catalyst of the composite catalyst air cathode 4 is composed of sulfur-doped graphene, manganese dioxide and conductive carbon black, wherein the sulfur-doped graphene accounts for 5% to 15% of the mass of the composite catalyst, the manganese dioxide accounts for 10% to 30% of the mass of the composite catalyst, the conductive carbon black composite catalyst accounts for 55% to 85% of the mass of the composite catalyst, more preferably, the sulfur-doped graphene content is 5%, the manganese dioxide content is 15%, and the conductive carbon black content is 80%.

The specific assembly is shown in fig. 1.

The prepared flexible aluminum-air battery based on the PVA/KC-KOH composite gel electrolyte is subjected to discharge test under the bending of 90 degrees, the effective voltage and the power density under different current densities are shown in figure 2, and the power density of the battery can reach 18Mw/cm at most^-2The flexible aluminum-air battery has higher effective working voltage and power density.

As shown in FIG. 3, it is a graph of the discharge performance of the flexible aluminum-air battery based on PVA/KC-KOH composite gel electrolyte at 90 degrees.

The invention has been described in detail in order to provide those skilled in the art with the understanding that the invention is not limited thereto, and that various changes and modifications can be made without departing from the spirit and scope of the invention.