CN110943268A - All-solid-state metal-air battery and preparation method thereof - Google Patents
All-solid-state metal-air battery and preparation method thereof Download PDFInfo
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- CN110943268A CN110943268A CN201811105179.1A CN201811105179A CN110943268A CN 110943268 A CN110943268 A CN 110943268A CN 201811105179 A CN201811105179 A CN 201811105179A CN 110943268 A CN110943268 A CN 110943268A
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- electrolyte
- solid
- air battery
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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
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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
Abstract
The invention provides a solid electrolyte metal-air battery and a preparation method thereof. The battery is a cathode supporting structure, metal sodium is used as an anode material, electrolyte is positioned on the surface of the cathode supporting body, and a porous composite material formed by lanthanum strontium cobalt iron metal oxide LSCF with a perovskite structure and an electrolyte material is used as the cathode supporting body. On one hand, the cathode support body can replace a noble metal catalyst to realize the catalytic action of an air electrode and complete the reaction of the battery, thereby greatly reducing the manufacturing cost of the battery; on the other hand, the electrolyte can provide matrix support for the thinning of the electrolyte, which is beneficial to reducing the resistance of the electrolyte, improving the conductivity and realizing the reaction discharge of the battery at the medium and low temperature of 150-350 ℃.
Description
Technical Field
The invention belongs to the technical field of metal-air batteries, and particularly relates to an all-solid-state metal-air battery and a preparation method thereof.
Background
The metal-air battery is a battery formed by coupling chemically active metal and air electrode through chemical reaction, not only refers to the characteristics of common primary battery, but also refers to some characteristics of fuel battery, so that it has the characteristics of large capacity, high specific energy, low cost and stable discharge.
The metal-air batteries which are researched and developed at present comprise zinc-air batteries, magnesium-air batteries, aluminum-air batteries and lithium-air batteries. But the development of commercial products for metal-air batteries has been hindered by problems and costs such as polarization or instability of the negative electrode, associated corrosion, non-uniform dissolution, safety, practical operability, etc.
Metal-air batteries are classified into liquid metal-air batteries, semi-solid metal-air batteries, and all-solid metal-air batteries according to the difference in electrolyte materials.
Electrolyte materials are currently mainly divided into three major categories: zirconia electrolyte material, ceria electrolyte material, and lanthanum gallate series electrolyte material. YSZ (Y)2O3Doped ZrO2) And SSZ (Sc)2O3Doped ZrO2) Is representative of a zirconia-based electrolyte material, SDC (Sm)2O3Doped CeO2)、YDC(Y2O3Doped CeO2) With GDC (Gd)2O3Doped CeO2) Belongs to cerium oxide electrolyte materials, and the most widely applied lanthanum gallate series electrolyte materials are LSGM (La)xSr1-xGayMg1-yO3). However, these electrolytes have low ionic conductivity at medium and low temperatures.
Disclosure of Invention
In view of the technical current situation of the metal-air battery, the invention provides an all-solid-state metal-air battery which can improve the ionic conductivity of electrolyte and can perform discharge reaction at a medium-low temperature.
The technical scheme adopted by the invention is as follows: an all-solid-state metal-air battery, characterized by: the method is characterized in that metal sodium is used as an anode material, a porous composite material formed by lanthanum strontium cobalt iron metal oxide LSCF with a perovskite structure and an electrolyte material is used as a cathode support, and the electrolyte material is supported by the cathode support.
The porous composite material formed by LSCF and electrolyte material is formed by adding a small amount of electrolyte material into lanthanum strontium cobalt iron metal oxide with a perovskite structure, and is used for enhancing the conduction capability of oxygen ions.
The electrolyte material is not limited, and comprises one or more of SSZ, YSZ, SDC, GDC, YDC, LSGM and the like.
Preferably, an interface modification layer is arranged between the electrolyte material and the anode material and is used for improving the coating wettability of the liquid sodium on the surface of the ceramic electrolyte when the metal sodium is molten into a liquid state in the working state, so that the internal resistance of the battery is further reduced. Preferably, the interface modification layer material is Ag.
Preferably, the electrolyte is formed in a thin film shape on the surface of the support. It is further preferred that the electrolyte thin film is less than 50 μm thick, more preferably less than 25 μm thick.
As a mounting seal, the all-solid-state metal-air battery of the present invention further includes an anode casing for mounting an anode material, and a cathode casing for mounting a cathode material. Preferably, a high temperature insulating material is provided between the anode casing and the cathode casing for sealing the connection between the anode casing and the cathode casing. The high-temperature insulating material is not limited, such as asbestos, etc.
The all-solid-state metal-air battery of the invention takes the metal sodium as the anode material, takes the porous composite material formed by the LSCF and the electrolyte material as the cathode support body, and takes the electrolyte material as the support body, and has the following beneficial effects:
(1) the sodium reserves in nature are abundant, and the overpotential of the sodium-air battery is low;
(2) the porous composite material formed by LSCF and electrolyte material is used as a cathode support body, on one hand, the catalytic action of an air electrode can be realized, and the complete battery reaction is completed, namely O of the cathode2Obtaining electrons under the catalytic action of LSCF to generate O2-Is conducted to the anode through the electrolyte and reacts with the anode material sodium to generate Na2O releases electrons and is conducted to the cathode through an external single path to form a complete battery reaction, so that the porous material LSCF can replace a noble metal catalyst Pt, and the manufacturing cost of the battery is greatly reduced; on the other hand, the porous composite material can be used as a support body of electrolyte, so that the thinning of the electrolyte is realized, the reduction of the resistance of the electrolyte and the improvement of the conductivity are facilitated, and particularly, the ionic conductivity can be improved when a battery reacts at a medium-low temperature, so that the effect of improving the ionic conductivity is realizedThe existing battery is subjected to reaction discharge at the medium-low temperature of 150-350 ℃, particularly at the medium-low temperature of 250-350 ℃, and has the advantages of low cost, firmness, durability, small test internal resistance, stable voltage and the like.
(3) The electrolyte material support LSCF is compounded, and compared with the traditional water-soluble electrolyte or polymer electrolyte metal-air battery, the safety of the solid electrolyte metal-air battery is greatly improved.
The invention also provides a method for preparing the all-solid-state metal-air battery, which comprises the following steps: and forming an electrolyte film layer on the surface of the cathode support body by using methods such as dipping, coating, screen printing and the like, and then sintering to be dense.
Preferably, the cathode support is prepared by sintering, and the specific implementation mode can be as follows: and tabletting the LSCF, the electrolyte material and the NMT-3 mixed powder, and sintering at high temperature to obtain the composite material.
When the interface modification layer Ag is disposed on the surface of the electrolyte material, the interface modification layer Ag is preferably formed on the electrolyte thin layer by a method such as dipping, coating, screen printing, or the like.
Drawings
Fig. 1 is a reaction schematic diagram of an all-solid-state metal-air battery in example 1 of the present invention.
Fig. 2 is a schematic structural diagram of an all-solid-state metal-air battery in embodiment 1 of the present invention after being assembled and sealed.
Fig. 3 is a test curve of OCV at 350 ℃ of the all-solid metal-air battery in example 1 of the present invention.
Detailed Description
The invention will be described in further detail below with reference to the embodiments of the drawing, which are intended to facilitate the understanding of the invention and are not intended to limit the invention in any way.
Example 1:
in this embodiment, in the all-solid-state metal-air battery, the anode material is sodium metal, the electrolyte material is SSZ ceramic material, the porous composite material LSCF/SSZ is used as a cathode support, and the surface of the cathode support is a thin film structure with a thickness of 15 μm. And an anode interface modification film layer Ag is arranged between the electrolyte material and the anode and is used for improving the coating wettability of the liquid metal sodium on the surface of the ceramic electrolyte SSZ in the working state and reducing the internal resistance of the battery.
The reaction principle of the all-solid-state metal-air battery is shown in fig. 1. O of cathode2Obtaining electrons under the catalytic action of LSCF to generate O2-，O2-Is conducted to the anode through the electrolyte and reacts with the anode material sodium to generate Na2O releases electrons and conducts to the cathode through an external single path to form a complete cell reaction.
The preparation method of the all-solid-state metal-air battery comprises the following steps:
(1) sintering to prepare the LSCF/SSZ support body, which comprises the following steps: and tabletting the mixed powder of LSCF, SSZ and NMT-3, sintering at high temperature, and volatilizing NMT-3 to obtain the ceramic sheet with the diameter of 15.8 mm.
(2) And screen printing SSZ electrolyte on an LSCF/SSZ support, sintering to be dense, and then screen printing Ag as electrolyte to face the surface modification of the anode to obtain LSCF (SSZ)/SSZ/Ag.
(3) Assembling and sealing the cathode, the anode and the electrolyte, wherein the method comprises the following steps:
as shown in fig. 2, the cathode housing 2 is used to mount the cathode. The cathode casing 2 is made of 304 stainless steel, and has a structure as shown in fig. 2, and an open hollow cavity 11 is used for the cathode to contact with air. The anode casing 4 is used for mounting an anode material. The cathode casing is made of 304 steel, and is structured as shown in fig. 2, and the metal sodium 7 is installed in the closed hollow cavity 10.
The LSCF (SSZ)/SSZ/Ag prepared as above is arranged between the hollow cavity 10 and the hollow cavity 11, and the LSCF/SSZ support body 5, the electrolyte material 6 and the interface modification film layer 8 are arranged from top to bottom in sequence.
The cathode casing and the anode casing are fixed by screws 10, and the screws 10 are made of ceramic materials and are insulated and non-conductive.
Putting the assembled and sealed battery into a high-temperature furnace, connecting an electrochemical workstation, and checking that all parts are in good contact by using a universal meter; then, the temperature was slowly raised to 350 ℃, so that the heated air was continuously blown into the cathode surface, the temperature was maintained, and the OCV change was recorded by an electrochemical workstation, and as a result, as shown in fig. 3, it was revealed that the OCV was stabilized at 2.2V, which was close to 2.29V of the theoretical OCV, indicating that the battery reached an ideal discharge state.
Example 2:
in this example, the structure of the all-solid-state metal-air battery was the same as that in example 1, except that the electrolyte material was in a thin film structure with a thickness of 8 μm on the surface of the cathode support.
In this example, the preparation method of the all-solid-state metal-air battery was the same as that in example 1.
Putting the assembled and sealed battery into a high-temperature furnace, connecting an electrochemical workstation, and checking that all parts are in good contact by using a universal meter; the temperature was then slowly raised to 300 c to ensure that heated air was continuously blown onto the cathode surface, the temperature was maintained, and OCV changes were recorded using an electrochemical workstation, with results similar to example 1 indicating that the cell reached the desired discharge state.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An all-solid-state metal-air battery, characterized by: the cathode support structure is a porous composite material formed by lanthanum strontium cobalt iron metal oxide LSCF with a perovskite structure and an electrolyte material.
2. The all-solid-state metal-air battery of claim 1, wherein: the electrolyte material is one or more of SSZ, YSZ, SDC, GDC, YDC and LSGM.
3. The all-solid-state metal-air battery of claim 1, wherein: an interface modification layer is arranged between the electrolyte material and the anode material;
preferably, the interface modification layer material is Ag.
4. The all-solid-state metal-air battery of claim 1, wherein: the electrolyte is in a film shape on the surface of the cathode support body;
preferably, the electrolyte thin film has a thickness of 5 μm to 100 μm, more preferably 5 μm to 25 μm, and most preferably 8 μm to 15 μm.
5. The all-solid-state metal-air battery of claim 1, wherein: also comprises an anode shell for installing anode materials and a cathode shell for installing cathode materials.
6. The all-solid-state metal-air battery of claim 1, wherein: a high-temperature insulating material is arranged between the anode casing and the cathode casing and is used for sealing the connecting part between the anode casing and the cathode casing;
preferably, the high temperature insulating material is asbestos.
7. The all-solid-state metal-air battery according to any one of claims 1 to 6, wherein: discharging reaction at 150-350 deg.c.
8. The method for producing an all-solid-state metal-air battery according to any one of claims 1 to 6, characterized by: the method comprises the following steps: an electrolyte SSZ thin film layer is formed on the surface of the cathode support body through dipping, coating or screen printing, and then sintering is carried out to compact the electrolyte SSZ thin film layer.
9. The method of manufacturing an all-solid-state metal-air battery according to claim 8, wherein: the cathode support is prepared by sintering.
10. The method of manufacturing an all-solid-state metal-air battery according to claim 8, wherein: when the interface modification layer Ag is arranged on the surface of the electrolyte material, the interface modification layer Ag is formed on the electrolyte thin layer through dipping, coating or silk-screen printing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811105179.1A CN110943268A (en) | 2018-09-21 | 2018-09-21 | All-solid-state metal-air battery and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811105179.1A CN110943268A (en) | 2018-09-21 | 2018-09-21 | All-solid-state metal-air battery and preparation method thereof |
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| CN110943268A true CN110943268A (en) | 2020-03-31 |
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| CN201811105179.1A Withdrawn CN110943268A (en) | 2018-09-21 | 2018-09-21 | All-solid-state metal-air battery and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115207371A (en) * | 2022-07-21 | 2022-10-18 | 清华大学 | Porous electrode, magnetron sputtering preparation method thereof and solid oxide fuel cell |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610842A (en) * | 2012-03-28 | 2012-07-25 | 南京工业大学 | Medium and high-temperature carbon-air battery |
| JP2014017230A (en) * | 2012-06-12 | 2014-01-30 | Toyota Motor Corp | Porous carbon and metal air battery |
| WO2014042761A2 (en) * | 2012-09-17 | 2014-03-20 | Battelle Memorial Institute | Metal-air battery |
| WO2015169786A1 (en) * | 2014-05-06 | 2015-11-12 | Danmarks Tekniske Universitet | Method for producing and controlling the morphology of metal-oxide nanofiber and/or nanotube catalysts |
| CN205159472U (en) * | 2015-09-23 | 2016-04-13 | 湘潭大学兴湘学院 | Metal -air battery |
-
2018
- 2018-09-21 CN CN201811105179.1A patent/CN110943268A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610842A (en) * | 2012-03-28 | 2012-07-25 | 南京工业大学 | Medium and high-temperature carbon-air battery |
| JP2014017230A (en) * | 2012-06-12 | 2014-01-30 | Toyota Motor Corp | Porous carbon and metal air battery |
| WO2014042761A2 (en) * | 2012-09-17 | 2014-03-20 | Battelle Memorial Institute | Metal-air battery |
| WO2015169786A1 (en) * | 2014-05-06 | 2015-11-12 | Danmarks Tekniske Universitet | Method for producing and controlling the morphology of metal-oxide nanofiber and/or nanotube catalysts |
| CN205159472U (en) * | 2015-09-23 | 2016-04-13 | 湘潭大学兴湘学院 | Metal -air battery |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115207371A (en) * | 2022-07-21 | 2022-10-18 | 清华大学 | Porous electrode, magnetron sputtering preparation method thereof and solid oxide fuel cell |
| CN115207371B (en) * | 2022-07-21 | 2023-06-13 | 清华大学 | Porous electrode, magnetron sputtering preparation method thereof and solid oxide fuel cell |
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