CN109494431B - Flexible aluminium air battery of flexible - Google Patents
Flexible aluminium air battery of flexible Download PDFInfo
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- CN109494431B CN109494431B CN201811339778.XA CN201811339778A CN109494431B CN 109494431 B CN109494431 B CN 109494431B CN 201811339778 A CN201811339778 A CN 201811339778A CN 109494431 B CN109494431 B CN 109494431B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
Abstract
A flexible aluminum-air battery capable of being bent is formed by sequentially laminating an aluminum alloy anode, an alkaline hydrogel electrolyte, an air cathode using a composite catalyst and a cathode current collector from inside to outside; the method comprises the steps of firstly clamping the manufactured aluminum alloy anode in the middle, sequentially placing the alkaline hydrogel electrolyte, the air cathode using the composite catalyst and the cathode current collector from the inner side to the outer side, and fixing the alkaline hydrogel electrolyte, the air cathode using the composite catalyst and the cathode current collector by using a clamp, so that the influence on the overall performance of the battery due to interface contact is avoided as much as possible; the invention can prevent surface passivation by clamping the aluminum alloy anode in the middle, and can increase the oxygen adsorption area by connecting one aluminum alloy anode with two air cathodes, thereby improving the oxygen adsorption rate and the redox activity; the bendable flexible aluminum-air battery provided by the invention solves the problem that the traditional rigid structure energy supply equipment cannot meet the actual energy supply requirement of the next generation of flexible wearable electronic devices, and is expected to realize large-scale application.
Description
Technical Field
The invention relates to the technical field of aluminum-air batteries, in particular to a flexible aluminum-air battery.
Background
The flexible electronic product has the advantages of portability, flexibility and wearability, and promotes the development of electronic equipment with different fields and functions. The development of flexible wearable electronic devices has rapidly increased demand for flexible power supplies with high energy density and durability, and flexible energy storage conversion systems have great application prospects in the future market as a novel power supply.
In recent years, relatively good 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, where 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 configurations to develop flexible power sources with better electrochemical performance for flexible electronics powering.
Disclosure of Invention
Aiming at the technical problems existing in the development of the conventional flexible power supply, the invention aims to provide a flexible aluminum-air battery which can meet the requirements of tiny devices and wearable electronic equipment on flexible, ultra-light and ultra-thin energy storage equipment, and can realize the following purposes through the design: firstly, the aluminum electrode is clamped in the middle to prevent surface passivation, and secondly, one aluminum electrode is connected with two air electrodes to increase the oxygen adsorption area, so that the oxygen adsorption rate and the redox activity are improved; the flexible aluminum-air battery has great development value and is expected to realize large-scale application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the flexible aluminum-air battery comprises an aluminum alloy anode (1), an alkaline hydrogel electrolyte (2), an air cathode (3) using a composite catalyst and a cathode current collector (4) which are laminated from inside to outside in sequence.
The aluminum alloy anode material is composed of aluminum, magnesium, gallium and indium, and the mass fraction of each component in the total mass of all materials of the aluminum alloy anode is as follows: 97-99% of aluminum, 0.5-1% of magnesium, 0.1-1.0% of gallium and 0.1-1.0% of indium, preferably 98% of aluminum, 1% of magnesium, 0.4% of gallium and 0.6% of indium.
The alkaline hydrogel electrolyte is formed by mixing a gel polymer and an alkaline electrolyte added with a composite corrosion inhibitor, wherein the mass fraction of the corrosion inhibitor in the alkaline electrolyte is 5-8%, and the content of the corrosion inhibitor is preferably 6%.
The gel polymer is polyvinyl alcohol (PVA) and polyethylene oxide (PEO), wherein the mass ratio of PVA to PEO is 10: 1-5: 1, and preferably 10: 1. The composite corrosion inhibitor is prepared by mixing sodium stannate and casein, wherein the molar mass ratio of the sodium stannate to the casein is 1: 1.
The alkaline electrolyte is NaOH or KOH solution, wherein the molar concentration of the NaOH solution or the KOH solution is 2-4 mol/L, and preferably 4 mol/L.
The composite catalyst of the air cathode (3) using the composite catalyst is composed of sulfur-doped graphene and manganese dioxide, 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, the content of the sulfur-doped graphene is preferably 5%, and the content of the manganese dioxide is preferably 15%.
The cathode current collector is made of a nickel mesh material.
After the electrode material is prepared, an aluminum alloy anode is connected with two air cathodes using composite catalysts through alkaline hydrogel electrolytes on the left side and the right side, a lead is adhered to the surface of the electrode through a conductive adhesive tape, the electrode is connected with the electrolytes, the two outer ends of the lead are tightly bound through the conductive adhesive tape or clamped by a clamp, the electrolyte is ensured to be in good contact with a point-electrode interface, and therefore the influence on the overall performance of a battery due to interface contact is avoided. At the same time, it is ensured that the surface is provided with gaps, and oxygen can enter the catalyst layer in the air electrode.
Compared with the prior art, the invention has the following advantages:
(1) the invention discloses a bendable flexible aluminum-air battery, which solves the problem that the traditional rigid structure energy supply equipment cannot meet the actual energy supply requirement of the next generation of flexible wearable electronic devices.
(2) Through the improvement of the battery structure, the aluminum alloy anode of the designed flexible aluminum air battery is clamped in the middle of the battery, so that the surface passivation of the aluminum anode can be effectively prevented, the electrode activity is enhanced, and the electrochemical performance of the battery is improved.
(3) Through battery structural improvement, the flexible aluminium air battery who designs adopts an aluminium alloy anode to link to each other with two air cathode, and oxygen adsorption area increases one time, and air electrode oxygen adsorption rate and redox activity all have showing and promote.
Drawings
Fig. 1 is a structural view of a bendable flexible aluminum air battery according to the present invention.
Fig. 2 is a performance test chart of the bendable flexible aluminum-air battery of the invention.
Fig. 3 is a graph comparing the discharge performance of the flexible aluminum-air battery of the invention with that of a pure aluminum-air battery.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
As shown in fig. 1, the flexible aluminum-air battery according to the present invention comprises an aluminum alloy anode (1), an alkaline hydrogel electrolyte (2), an air cathode (3) using a composite catalyst, and a cathode current collector (4) laminated in this order from the inside to the outside.
As a preferred embodiment of the present invention, the aluminum alloy anode material is composed of aluminum, magnesium, gallium and indium, and the mass fraction of each component in the total mass of all materials of the aluminum alloy anode is as follows: 97-99% of aluminum, 0.5-1% of magnesium, 0.1-1.0% of gallium and 0.1-1.0% of indium, more preferably 98% of aluminum, 1% of magnesium, 0.4% of gallium and 0.6% of indium.
As a preferred embodiment of the invention, the alkaline hydrogel electrolyte is formed by mixing a gel polymer and an alkaline electrolyte added with a composite corrosion inhibitor, wherein the mass fraction of the corrosion inhibitor in the alkaline electrolyte is 5-8%, and more preferably the content of the corrosion inhibitor is 6%.
According to a preferred embodiment of the invention, the gel polymer is polyvinyl alcohol (PVA) and polyethylene oxide (PEO), wherein the mass ratio of PVA to PEO is 10: 1-5: 1, and preferably 10: 1. The composite corrosion inhibitor is prepared by mixing sodium stannate and casein, wherein the molar mass ratio of the sodium stannate to the casein is 1: 1.
In a preferred embodiment of the present invention, the alkaline electrolyte is a NaOH or KOH solution, wherein the molar concentration of the NaOH or KOH solution is 2 to 4mol/L, and more preferably 4 mol/L.
In a preferred embodiment of the invention, the composite catalyst of the air cathode (3) using the composite catalyst comprises sulfur-doped graphene and manganese dioxide, 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 more preferably, the sulfur-doped graphene accounts for 5% of the mass of the composite catalyst, and the manganese dioxide accounts for 15% of the mass of the composite catalyst.
As a preferred embodiment of the present invention, the cathode current collector is made of a nickel mesh material.
The specific assembly method is shown in figure 1, an aluminum alloy anode 1 is connected with two air cathodes 3 using composite catalysts through alkaline hydrogel electrolytes 2 on the left side and the right side, leads of an external circuit are adhered to the surfaces of the aluminum alloy anode 1 and the air cathodes 3 using the composite catalysts through conductive adhesive tapes, the anode and the cathode are respectively connected with the alkaline hydrogel electrolytes, and the two external ends are tightly bound through the conductive adhesive tapes or clamped by clips, so that the alkaline hydrogel electrolytes are ensured to be in good contact with the interfaces of the anode and the cathode, and the influence on the overall performance of the battery due to interface contact is avoided. At the same time, it is ensured that the surface is provided with gaps, and oxygen can enter the catalyst layer in the air electrode.
The prepared bendable flexible aluminum-air battery is subjected to discharge test under the condition of bending at 90 degrees, effective voltage and power density curves under the conditions of different current densities are shown in figure 2, the discharge current density is increased, the power density of the battery is increased, and the maximum power density can reach 109.8 mW cm-2Compared with the existing aluminum-air battery, the flexible aluminum-air battery has higher effective working voltage and power density.
Fig. 3 is a graph comparing the discharge performance of the flexible aluminum-air cell with pure aluminum-air cell, comparing the overall performance of aluminum-air cells with different anodes. The operating voltage and the anode efficiency of the aluminum-air battery with the Al-Mg-In-Ga electrode were calculated by numerical calculation to be as high as 1.28V and 73.9%, respectively. The anode efficiency and fuel efficiency of Al-Mg-In-Ga are improved compared to pure Al due to the inhibition of hydrogen evolution corrosion and the improvement of electrochemical activity.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above case, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (7)
1. The bendable flexible aluminum-air battery is characterized by comprising an aluminum alloy anode (1), an alkaline hydrogel electrolyte (2), an air cathode (3) using a composite catalyst and a cathode current collector (4) which are laminated from inside to outside in sequence;
the alkaline hydrogel electrolyte (2) is formed by mixing a gel polymer and an alkaline electrolyte added with a composite corrosion inhibitor, wherein the mass fraction of the corrosion inhibitor in the alkaline electrolyte is 5-8%;
the gel polymer is polyvinyl alcohol (PVA) and polyethylene oxide (PEO), wherein the mass ratio of the PVA to the PEO is 10: 1-5: 1;
the composite corrosion inhibitor is prepared by mixing sodium stannate and casein, wherein the molar mass ratio of the sodium stannate to the casein is 1: 1;
the alkaline electrolyte is NaOH solution or KOH solution, wherein the molar concentration of the NaOH solution or the KOH solution is 2-4 mol/L.
2. A bendable flexible aluminum air battery according to claim 1, characterized in that the aluminum alloy anode (1) is made of aluminum, magnesium, gallium and indium, and the mass fraction of each component in the total mass of all materials of the aluminum alloy anode is as follows: 97-99% of aluminum, 0.5-1% of magnesium, 0.1-1.0% of gallium and 0.1-1.0% of indium.
3. The bendable flexible aluminum-air battery according to claim 2, wherein the mass fractions of the components in the total mass of all materials of the aluminum alloy anode are as follows: 98% of aluminum, 1% of magnesium, 0.4% of gallium and 0.6% of indium.
4. The bendable flexible aluminum-air battery according to claim 1, wherein the mass fraction of the corrosion inhibitor in the alkaline electrolyte is 6%, the mass ratio of PVA to PEO is 10:1, and the molar concentration of NaOH solution or KOH solution is 4 mol/L.
5. The bendable flexible aluminum-air battery according to claim 1, wherein the composite catalyst of the air cathode (3) using the composite catalyst comprises sulfur-doped graphene and manganese dioxide, wherein the sulfur-doped graphene accounts for 5-15% of the mass of the composite catalyst, and the manganese dioxide accounts for 10-30% of the mass of the composite catalyst.
6. The bendable flexible aluminum-air battery according to claim 5, wherein the sulfur-doped graphene accounts for 5% of the mass of the composite catalyst, and the manganese dioxide accounts for 15% of the mass of the composite catalyst.
7. A bendable flexible aluminum air battery according to claim 1, characterized in that the cathode current collector (4) is made of nickel mesh material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110247137A (en) * | 2019-06-18 | 2019-09-17 | 哈尔滨工业大学 | A kind of nuclear magnetic resonance original position aluminium-air cell and its discharge test method |
| CN110534749B (en) * | 2019-08-19 | 2020-12-18 | 武汉大学 | Horizontal hydrogel modified air cathode, microbial fuel cell and preparation method |
| CN111342063A (en) * | 2020-03-04 | 2020-06-26 | 西北大学 | Manganese dioxide-loaded nitrogen-sulfur double-doped graphene catalyst for oxygen reduction reaction, and preparation method and application thereof |
| CN112467258A (en) * | 2020-11-25 | 2021-03-09 | 北京航空航天大学 | Preparation method of lithium-air battery based on gel electrolyte-lithium cathode integrated structure |
| CN113517499B (en) * | 2021-05-25 | 2023-01-31 | 西北大学 | Flexible aluminum-air battery based on PVA/KC-KOH composite gel electrolyte |
| CN114005995B (en) * | 2021-11-01 | 2023-11-10 | 天津理工大学 | Preparation method of flexible metal electrode |
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