CN114824328A - Photosensitive low-temperature metal-air battery pack and preparation method thereof - Google Patents
Photosensitive low-temperature metal-air battery pack and preparation method thereof Download PDFInfo
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- CN114824328A CN114824328A CN202210533119.XA CN202210533119A CN114824328A CN 114824328 A CN114824328 A CN 114824328A CN 202210533119 A CN202210533119 A CN 202210533119A CN 114824328 A CN114824328 A CN 114824328A
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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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
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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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
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Hybrid Cells (AREA)
Abstract
The invention is suitable for the field of photosensitive low-temperature metal-air battery packs, and provides a photosensitive low-temperature metal-air battery pack, which comprises: the plurality of photosensitive low-temperature metal-air cells are connected in parallel or in series; the photosensitive low-temperature metal-air battery comprises a photosensitive positive electrode, a diaphragm or solid electrolyte soaked with electrolyte and a metal negative electrode; the photosensitive anode consists of a photo-anode catalyst and an anode current collector; the photo-anode catalyst is a catalyst compounded by metal nanoparticles and a conductive substrate, and the catalyst compounded by the metal nanoparticles and the conductive substrate has full-spectrum absorption response; the selected metal nano particles and the catalyst compounded with the conductive substrate have excellent photo-thermal conversion capability, can catalyze oxygen reduction and precipitation reaction, the composite photocatalytic anode loaded with the metal nano particles can absorb and utilize solar energy, and light energy is converted into electric energy and heat energy through a plasma resonance effect, so that the performance of the battery is improved.
Description
Technical Field
The invention belongs to the field of photosensitive low-temperature metal-air battery packs, and particularly relates to a photosensitive low-temperature metal-air battery pack and a preparation method thereof.
Background
Rechargeable batteries are the core technology of modern energy networks. With the increasing progress of human social activities, various operating conditions of rechargeable batteries are more demanding. Particularly in high latitude, high altitude, deep sea and other environments, low temperature energy storage of rechargeable batteries is a new challenge. Therefore, whether the new battery technology can store energy efficiently at low temperature is highly valued by science and technology personnel.
Among all the new secondary batteries, the metal-air battery has received much attention, has an extremely high energy density, and can continuously supply energy to electronic devices for a long time. The most typical metal-air batteries are nonaqueous lithium-air batteries and aqueous zinc-air batteries. However, the metal-air battery still has the problems of limited battery capacity, poor rate capability, short service life and the like at low temperature, and practical application of the metal-air battery at low temperature is limited, so that further research on the low-temperature metal-air battery is needed.
The performance degradation of metal-air batteries under low temperature conditions is limited by two factors: on one hand, the dynamics of the air anode is sensitive to temperature, and can be reduced along with the reduction of the temperature to cause larger overpotential, so that energy loss is caused; on the other hand, the electrolyte has a high ice point and is easily frozen, which limits ion mobility and wettability of the electrolyte to the electrode, resulting in deterioration of the electrode/electrolyte interface. At present, an effective method for realizing the low-temperature operation of the metal-air battery is not available except for physically heating the external package of the battery; the existing heating technology can increase the weight of the battery pack, seriously reduce the overall energy density of the battery, and need to consume the electric energy of the battery to realize self-heating.
To avoid the above technical problems, it is necessary to provide a photosensitive low-temperature metal-air battery and a method for manufacturing the same to overcome the above-mentioned drawbacks in the prior art.
Disclosure of Invention
The invention aims to provide a photosensitive low-temperature metal-air battery pack and a preparation method thereof, and aims to design the photosensitive low-temperature metal-air battery pack, so that the battery can safely, stably and continuously output energy at low temperature without external heating.
The present invention is thus achieved, a photosensitive low temperature metal air battery comprising:
the plurality of photosensitive low-temperature metal-air cells are connected in parallel or in series; the photosensitive low-temperature metal-air battery comprises a photosensitive positive electrode, a diaphragm or solid electrolyte soaked with electrolyte and a metal negative electrode;
the photosensitive anode consists of a photo-anode catalyst and an anode current collector;
the photo-anode catalyst is a catalyst compounded by metal nanoparticles and a conductive substrate, and the catalyst compounded by the metal nanoparticles and the conductive substrate has full-spectrum absorption response; the catalyst compounded by the selected metal nanoparticles and the conductive substrate has excellent photo-thermal conversion capability and can catalyze oxygen reduction and precipitation reaction.
The preparation method of the catalyst compounded by the metal nano particles and the conductive substrate comprises the following steps;
s1, preparing a carbon nano tube conductive substrate;
s2, growing gold nanoparticles on the surface of the carbon nanotube conductive substrate in the step S1;
in a further technical scheme, the electrolyte is alkaline electrolyte or solid electrolyte.
In a further technical scheme, the metal nanoparticles are gold, silver, metal oxide or composite nanoparticles.
According to a further technical scheme, the conductive substrate comprises carbon nanotubes, graphene and conductive carbon.
According to the further technical scheme, the photosensitive positive electrode is an Au @ CNT positive electrode.
In a further technical scheme, the metal cathode is a zinc plate.
A method for preparing a photosensitive low-temperature metal-air battery pack is characterized in that a photosensitive positive electrode, a diaphragm/solid electrolyte soaked with electrolyte and a metal negative electrode are packaged in a battery mould.
Compared with the prior art, the invention has the following beneficial effects:
(1) the composite photocatalytic anode loaded with the metal nanoparticles can absorb and utilize solar energy, and can convert light energy into electric energy and heat energy through a plasma resonance effect, so that the reaction kinetics of the air anode is promoted, and the performance of the battery is improved;
(2) the composite light anode and the electrolyte are subjected to effective heat transfer, so that the effective implementation of an oxidation-reduction reaction is ensured, and the stable output of energy under a low-temperature condition is realized;
(3) the photosensitive low-temperature metal air battery pack can supply power to electrical appliances for lithium ion batteries with the time length exceeding the equal area in the environment of natural illumination and the temperature of-20 ℃.
The research is not limited to the metal-air battery, but can be applied to other battery systems, and constitutes an important step for the practical application of the all-solid-state photosensitive metal-air battery.
Drawings
FIG. 1 is an Au @ CNT photo-anode transmission electron microscope image in an embodiment of the present invention.
FIG. 2 is a graph of the infrared thermal imaging of the Au @ CNT photo-anode of example 1 of the present invention.
Fig. 3 shows a scene in which the photosensitive zinc-air cell of example 2 of the present invention supplies power to a 5V fan under irradiation of sunlight at-20 ℃.
Fig. 4 shows a scenario where the photosensitive solid-state zinc-air cell of example 3 of the present invention supplies power to an 18V temperature display under-20 degrees celsius sunlight.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention.
Specific implementations of the present invention are described in detail below with reference to specific embodiments.
Preparing an Au @ CNT photo-anode, comprising the following steps of:
s1, weighing 2g of melamine, flatly paving the melamine at the bottom of a porcelain boat, placing carbon paper on the surface of the porcelain boat, then placing a substrate on the carbon paper, and transferring the substrate into a tube furnace;
s2, introducing nitrogen into the tubular furnace for 1 hour, heating to 750 ℃, keeping for 2 hours, and annealing to obtain the carbon nano tube conductive substrate;
and S3, soaking the carbon nano tube conductive substrate in chloroauric acid aqueous solution, adjusting the pH to 7, and illuminating for 20 minutes under a xenon lamp. Taking out the substrate, cleaning the substrate with clear water, and drying to obtain an Au @ CNT conductive substrate, namely an Au @ CNT photo-anode;
the Au @ CNT photo-positive electrode prepared in example 1 of the present invention was characterized.
Referring to fig. 1, fig. 1 is a transmission electron micrograph of Au @ CNT photo-anode prepared in example 1.
As can be seen from FIG. 1, the Au @ CNT photo-anode prepared by the method disclosed by the invention has the advantages that Au nanoparticles are tightly combined with a CNT conductive substrate, so that the synergistic absorption of sunlight is facilitated, and the progress of an oxidation-reduction reaction is promoted. Referring to fig. 2, fig. 2 shows the Au @ CNT photo-anode prepared in example 1 for infrared thermographic detection.
As can be seen from FIG. 2, the Au @ CNT photo-anode can reach 28 ℃ at-30 ℃ of ambient temperature under the sunlight irradiation, which is higher than that of a single Au anode and a CNT anode, and thus the Au @ CNT can synergistically absorb solar energy and effectively convert the solar energy into heat energy.
The preparation method of the photosensitive low-temperature liquid zinc-air battery comprises the following steps:
s1, packaging an Au @ CNT photo-anode, a 6mol/L potassium hydroxide electrolyte membrane and a cathode zinc plate in a battery grinding tool from top to bottom;
s2, placing the battery in sunlight for testing;
the photosensitive zinc-air cell prepared in example 2 of the present invention was tested.
Referring to fig. 3, fig. 3 is a statistical chart of the power supply time of the photosensitive zinc-air cell prepared by the invention for a 5V fan under the irradiation of sunlight at-20 ℃.
As can be seen from FIG. 3, under the sun illumination of the ambient temperature of-20 ℃, the photosensitive zinc-air cell can supply energy to the 5V fan for 175 minutes, which is greater than the 50-minute working time of the zinc-air cell without illumination. The operating time also exceeds the operating time of 1 hour per unit area of a lithium ion battery using lithium iron phosphate as a positive electrode and graphite as a negative electrode.
The preparation method of the photosensitive low-temperature solid zinc-air battery comprises the following steps:
s1, adding polyvinyl alcohol into deionized water according to the ratio of 1:40, heating to 90 ℃, heating for 4 hours until the solid is completely dissolved, and changing the solution back to a transparent solution;
s2, dispersing potassium hydroxide in deionized water, preparing 10mol/L, transferring the solution into the transparent solution, and uniformly stirring to obtain a PVA solution;
s3, pouring the PVA solution on a zinc plate while the PVA solution is hot, and standing for 24 hours at the temperature of minus 20 ℃;
and S4, attaching the Au @ CNT optical anode to the other side of the PVA, and packaging into a battery.
The photosensitive solid-state zinc-air cell prepared in example 3 of the present invention was tested.
Referring to fig. 4, fig. 4 is a statistical chart of the power supply time of the photosensitive zinc-air cell prepared by the invention for a 5V fan under the irradiation of sunlight at-20 ℃.
As can be seen from FIG. 4, under the sun illumination of the ambient temperature of-20 ℃, the photosensitive solid zinc-air cell can supply energy to the 18V display screen for 40 minutes, which is longer than the working time of the solid zinc-air cell without the illumination for 10 minutes. The operating time also exceeded the operating time of a lithium ion battery having lithium iron phosphate as a positive electrode, graphite as a negative electrode, and PEO as a solid electrolyte for 20 minutes per unit area.
Under the background of the era of carbon neutralization and carbon peak, a photosensitive metal-air battery represented by a photosensitive solid zinc-air battery is expected to become an important component for energy storage and energy supply under extreme conditions.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (7)
1. A photosensitive low temperature metal air battery, comprising:
the plurality of photosensitive low-temperature metal-air cells are connected in parallel or in series;
the photosensitive low-temperature metal-air battery comprises a photosensitive positive electrode, a diaphragm or solid electrolyte soaked with electrolyte and a metal negative electrode;
the photosensitive anode consists of a photo-anode catalyst and an anode current collector; the photo-anode catalyst is a catalyst compounded by metal nanoparticles and a conductive substrate.
2. The photosensitive low temperature metal air battery of claim 1, wherein the electrolyte is an alkaline electrolyte or a solid state electrolyte.
3. The photosensitive low temperature metal-air battery of claim 1, wherein the metal nanoparticles are gold, silver, metal oxide or composite nanoparticles.
4. The photosensitive low temperature metal-air battery of claim 1, wherein the conductive substrate comprises carbon nanotubes, graphene, and conductive carbon.
5. The photosensitive low temperature metal air battery of claim 1, wherein the photosensitive positive electrode is an Au @ CNT positive electrode.
6. The photosensitive low temperature metal-air battery of claim 1, wherein the metal negative electrode is a zinc plate.
7. A method of making a photosensitive low temperature metal air battery as claimed in any of claims 1 to 6, wherein the photosensitive positive electrode, the infiltrated electrolyte membrane/solid state electrolyte, and the metal negative electrode are encapsulated in a battery mold.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210533119.XA CN114824328A (en) | 2022-05-12 | 2022-05-12 | Photosensitive low-temperature metal-air battery pack and preparation method thereof |
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| CN202210533119.XA CN114824328A (en) | 2022-05-12 | 2022-05-12 | Photosensitive low-temperature metal-air battery pack and preparation method thereof |
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| JP2013239245A (en) * | 2012-05-11 | 2013-11-28 | Yoshiaki Nagaura | Metal-air battery |
| WO2015045396A1 (en) * | 2013-09-30 | 2015-04-02 | 日本ゼオン株式会社 | Dye-sensitized solar cell and solar cell module |
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2022
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Patent Citations (10)
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| CN102347140A (en) * | 2011-07-20 | 2012-02-08 | 彩虹集团公司 | Preparation method of dye-sensitized solar cell counter electrode |
| KR20130118578A (en) * | 2012-04-20 | 2013-10-30 | 재단법인대구경북과학기술원 | Light sensitized solar cell and method for manufacturing the same |
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