阅读说明：本技术 一种具有液态合金改性阳极的纸基铝空气电池及制备方法 (Paper-based aluminum air battery with liquid alloy modified anode and preparation method ) 是由 高钱 王宏超 于 2020-06-22 设计创作，主要内容包括：本发明公开了一种具有液态合金改性阳极的纸基铝空气电池,由三层结构组成,具体为依次叠加的铝阳极、纸基、空气电极；其中,铝阳极表面负载有液态合金微粒。液态合金微粒由Ga、In、Sn、Bi、Zn中的两种或多种组成,并且在铝空气电池工作温度下为液态。铝阳极表面负载的液态合金微粒可以很好地活化铝阳极,在中性电解液中放电性能良好,放电时间长,可满足小功率市场应用。本发明公开了一种具有液态合金改性阳极的纸基铝空气电池的制备方法。(The invention discloses a paper-based aluminum air battery with a liquid alloy modified anode, which consists of three layers of structures, namely an aluminum anode, a paper base and an air electrode which are sequentially overlapped; wherein, the surface of the aluminum anode is loaded with liquid alloy particles. The liquid alloy fine particles are composed of two or more of Ga, In, Sn, Bi, Zn, and are liquid at the operating temperature of the aluminum-air battery. The liquid alloy particles loaded on the surface of the aluminum anode can well activate the aluminum anode, has good discharge performance in neutral electrolyte and long discharge time, and can meet the application of low-power markets. The invention discloses a preparation method of a paper-based aluminum air battery with a liquid alloy modified anode.)

1. A paper-based aluminum air battery with a liquid alloy modified anode is composed of a three-layer structure, namely an aluminum anode, a paper base and an air electrode which are sequentially overlapped; it is characterized in that the surface of the aluminum anode is loaded with liquid alloy particles.

2. A paper-based aluminum air cell with liquid alloy modified anode as claimed In claim 1, said liquid alloy particles are composed of two or more of Ga, In, Sn, Bi, Zn and are liquid at aluminum air cell operating temperature.

3. The paper-based aluminum air cell with liquid alloy modified anode of claim 1, wherein the liquid alloy particle loading of the aluminum anode surface is not less than 1ug/cm²。

4. A paper-based aluminum air cell with liquid alloy modified anode as claimed in claim 1, the liquid alloy particle size is no greater than 5 um.

5. A paper-based aluminum air cell with liquid alloy modified anode as claimed in claim 1, said aluminum anode thickness is no greater than 2 mm.

6. A paper-based aluminum air cell with liquid alloy modified anode as claimed in claim 1, said paper-based is drop-fed with electrolyte.

7. A paper-based aluminum air cell with liquid alloy modified anode as claimed in claim 1, said paper-based being cellulose paper.

8. A paper-based aluminum air cell with liquid alloy modified anode as claimed in claim 7 wherein said cellulose paper thickness is not less than 0.1 mm.

9. A preparation method of a paper-based aluminum air battery with a liquid alloy modified anode comprises the following steps:

s1, selecting two or more of Ga, In, Sn, Zn and Bi, mixing the two or more of Ga, In, Sn, Zn and Bi according to a ratio, heating the mixture In an inert gas atmosphere at a temperature higher than the melting point of the selected elements by 100 ℃, and keeping the temperature for 1 to 2 hours to prepare a liquid alloy;

s2, alloying the liquid alloy prepared in the step S1 at room temperature for 10-24 h;

s3, mixing the liquid alloy, the surfactant and the solvent according to the weight ratio of 0.01-10 g: 0.01-20 g: mixing 10-100ml, and ultrasonically stirring for 20-40min to obtain liquid alloy particles;

s4, loading liquid alloy particles on the surface of the aluminum anode;

s5, sequentially superposing the aluminum anode loaded with the liquid alloy particles, the paper base and the air electrode to obtain a paper base aluminum air battery, and dropwise adding electrolyte to the paper base layer to realize low-power discharge.

Technical Field

The invention belongs to the field of metal air batteries, relates to a novel cheap green paper-based aluminum air battery, and particularly relates to a paper-based aluminum air battery with a liquid alloy modified anode and a preparation method thereof.

Background

Primary batteries are used as a disposable power source, usually without being recharged or unnecessarily recharged. A wide variety of small power devices (e.g., healthcare biosensors, medical diagnostic assays, wearable electronics, smart packaging, etc.) are currently emerging on the market and occupy a significant market share. Most of these devices are inexpensive and consume only mW or even uW power and are discarded after use, so there is a need for an inexpensive, light, portable and environmentally friendly power source to match.

The metal-air battery adopts different metal materials as the anode, and the air cathode directly utilizes oxygen in the air, so that the metal-air battery has higher energy density. Common anode materials for metal-air batteries include Zn, Mg, Al, Li, Fe, etc. Among them, aluminum element has attracted attention because of its abundant reserves, low price and high energy density. Conventional aluminum-air cells are not suitable for use in low power markets due to the complex fluid and gas management systems involved. In recent years, cellulose paper has been increasingly used in various fields such as lithium ion batteries, fuel cells, supercapacitors, and nanogenerators. In the aluminum air battery, the cellulose paper can automatically convey electrolyte, thereby greatly simplifying a water management system; it is light and flexible, and can improve the energy density and flexibility of the equipment. In addition, the cellulose has low cost and is a renewable green and environment-friendly material.

The paper-based aluminum air battery is concerned by people due to the fact that the paper-based aluminum air battery is high in energy density, low in cost and environment-friendly, at present, research on the paper-based aluminum air battery mainly focuses on optimization research on parameters such as paper thickness, electrolyte type and concentration and cathode side activity, and no people directly conduct surface modification research on an aluminum anode of the aluminum air battery. Meanwhile, the paper-based aluminum air battery manufactured at present generally has the problems of short discharge time, insufficient utilization rate of an aluminum anode, insufficient discharge power of neutral electrolyte and the like.

In recent years, liquid alloys have attracted attention because of their low melting point (i.e., liquid at room temperature), excellent electrical conductivity, and extremely strong ductility, and studies have shown that liquid alloys can activate aluminum alloys at the same time. We report here a new paper-based aluminum air cell with liquid alloy surface activation that can discharge for a long time in neutral electrolyte.

Disclosure of Invention

The invention provides a paper-based aluminum air battery with a liquid alloy modified anode and a preparation method thereof, aiming at the defects of the existing primary paper air battery, and the paper-based aluminum air battery is low in cost, green and environment-friendly.

As one aspect of the invention, the invention provides a paper-based aluminum air battery with a liquid alloy modified anode, which consists of a three-layer structure, specifically, an aluminum anode, a paper base and an air electrode which are sequentially stacked; wherein, the surface of the aluminum anode is loaded with liquid alloy particles. The liquid alloy particles loaded on the surface of the aluminum anode can well activate the aluminum anode, has good discharge performance in neutral electrolyte and long discharge time, and can meet the application of low-power markets.

Preferably, the liquid alloy fine particles are composed of two or more of Ga, In, Sn, Bi, Zn, and are liquid at the operating temperature of the aluminum-air battery.

Preferably, the loading of the liquid alloy particles on the surface of the aluminum anode is not less than 1ug/cm²。

More preferably, the loading amount of the liquid alloy particles on the surface of the aluminum anode is not less than 10ug/cm²。

More preferably, the liquid alloy particles are no larger than 5um in size.

Further, the aluminum anode is aluminum foil.

Further, the aluminum anode has a thickness of not more than 2 mm.

Preferably, the aluminum anode has a thickness of less than 0.5 mm.

More preferably, the aluminum anode 3 has a thickness of 0.2 mm.

Further, electrolyte is dripped on the paper base, and low-power discharge can be realized.

Preferably, the paper substrate is a cellulose paper.

More preferably, the cellulose paper is selected from one or more of cheap paper or paper products with good water absorption such as commercial filter paper, napkin paper, corrugated paper and the like.

More preferably, the cellulose paper has a thickness of not less than 0.1 mm.

More preferably, the cellulose paper has a thickness of 0.5mm to 5 mm.

More preferably, the cellulose paper has a thickness of 1 mm.

As another aspect of the present invention, there is provided a method for preparing a paper-based aluminum air battery having a liquid alloy modified anode, comprising the steps of:

s1, selecting two or more of Ga, In, Sn, Zn and Bi, mixing the two or more of Ga, In, Sn, Zn and Bi according to a ratio, heating the mixture In an inert gas atmosphere at a temperature 100 ℃ higher than the melting point of the selected elements, and keeping the temperature for 1-2 hours to obtain a liquid alloy;

s2, alloying the liquid alloy prepared in the step S1 at room temperature for 10-24 h;

s3, mixing the liquid alloy, the surfactant and the solvent according to the weight ratio of 0.01-10 g: 0.01-20 g: mixing 10-100ml, and ultrasonically stirring for 20-40min to obtain liquid alloy particles;

s4, loading liquid alloy particles on the surface of the aluminum anode;

s5, sequentially superposing the aluminum anode loaded with the liquid alloy particles, the paper base and the air electrode to obtain a paper base aluminum air battery, and dropwise adding electrolyte to the paper base layer to realize low-power discharge.

Compared with the prior art, the invention has the following advantages:

1. compared with the traditional aluminum-air battery, the aluminum-air battery avoids a complex fluid and gas management system, realizes automatic transportation of electrolyte through the capillary action of the cellulose paper, and realizes miniaturization and lightweight of the aluminum-air battery.

2. Compared with the existing paper-based aluminum air battery, the liquid alloy loaded on the surface of the aluminum anode can destroy the aluminum surface oxide film to activate the aluminum anode, has good discharge performance in neutral electrolyte and long discharge time, and can meet the application of low-power markets.

Drawings

FIG. 1 is a schematic structural diagram of a paper-based aluminum air battery with a liquid alloy modified anode according to the present invention;

in the figure:

1-an air electrode; 2-paper base; 3-an aluminum anode; 4-electrolyte.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, but the present invention is not limited thereto.

Referring to fig. 1, the paper-based aluminum air battery with the liquid alloy modified anode is composed of a three-layer structure, specifically, an aluminum anode 3, a paper base 2 and an air electrode 1 which are sequentially stacked; wherein, the surface of the aluminum anode 3 is loaded with liquid alloy particles. The liquid alloy particles loaded on the surface of the aluminum anode can well activate the aluminum anode, has good discharge performance in neutral electrolyte and long discharge time, and can meet the application of low-power markets.

Preferably, the liquid alloy fine particles are composed of two or more of Ga, In, Sn, Bi, Zn, and are liquid at the operating temperature of the aluminum-air battery.

Preferably, the loading amount of the liquid alloy particles on the surface of the aluminum anode 3 is not less than 1ug/cm²。

More preferably, the loading amount of the liquid alloy particles on the surface of the aluminum anode 3 is not less than 10ug/cm²。

More preferably, the liquid alloy particles are no larger than 5um in size.

Further, the aluminum anode is aluminum foil.

Further, the aluminum anode 3 has a thickness of not more than 2 mm.

Preferably, the aluminum anode 3 has a thickness of less than 0.5 mm.

More preferably, the aluminum anode 3 has a thickness of 0.2 mm.

Further, the paper base 2 is dropwise added with the electrolyte 4, and then low-power discharge can be achieved.

Preferably, the paper base 2 is cellulose paper.

More preferably, the cellulose paper is selected from one or more of cheap paper or paper products with good water absorption such as commercial filter paper, napkin paper, corrugated paper and the like.

More preferably, the cellulose paper has a thickness of not less than 0.1 mm.

More preferably, the cellulose paper has a thickness of 0.5mm to 5 mm.

More preferably, the cellulose paper has a thickness of 1 mm.

A preparation method of a paper-based aluminum air battery with a liquid alloy modified anode comprises the following steps:

s1, selecting two or more of Ga, In, Sn, Zn and Bi, mixing the two or more of Ga, In, Sn, Zn and Bi according to a ratio, heating the mixture In an inert gas atmosphere at a temperature 100 ℃ higher than the melting point of the selected elements, and keeping the temperature for 1-2 hours to obtain a liquid alloy;

s2, alloying the liquid alloy prepared in the step S1 at room temperature for 10-24 h;

s3, mixing the liquid alloy, the surfactant and the solvent according to the weight ratio of 0.01-10 g: 0.01-20 g: mixing 10-100ml, and ultrasonically stirring for 20-40min to obtain liquid alloy particles;

s4, loading liquid alloy particles on the surface of the aluminum anode;

s5, sequentially superposing the aluminum anode loaded with the liquid alloy particles, the paper base and the air electrode to obtain a paper base aluminum air battery, and dropwise adding electrolyte to the paper base layer to realize low-power discharge.