CN113270590A - Air battery anode - Google Patents

Air battery anode Download PDF

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Publication number
CN113270590A
CN113270590A CN202110303753.XA CN202110303753A CN113270590A CN 113270590 A CN113270590 A CN 113270590A CN 202110303753 A CN202110303753 A CN 202110303753A CN 113270590 A CN113270590 A CN 113270590A
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positive electrode
cavity
air battery
air
container
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CN202110303753.XA
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Chinese (zh)
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曹梅君
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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
    • H01M4/94—Non-porous diffusion electrodes, e.g. palladium membranes, ion exchange membranes
    • 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
    • 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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • H01M4/8657—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites layered
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inert Electrodes (AREA)
  • Hybrid Cells (AREA)

Abstract

The invention provides an air battery anode, which comprises an anode container, wherein the anode container comprises an anode container cavity and a cavity opening communicated with the anode container cavity; a waterproof breathable film for closing the cavity opening; the positive electrode body is filled in the positive electrode container cavity and consists of a plurality of thread-shaped positive electrode split bodies; electrolyte filled in the cavity of the positive electrode container and a positive electrode lead wire communicated with the positive electrode body. Compared with the prior art, the invention has the beneficial effects that: the positive electrode is distributed in the cavity in a filiform mode, and air is more easily dispersed in the cavity when the air-cooled generator is used, so that the cost of raw materials is further reduced while the effect is ensured.

Description

Air battery anode
Technical Field
The invention relates to the field of batteries, in particular to an air battery anode.
Background
The positive electrode structure in the air battery is an important component, and the working efficiency of the battery is directly influenced. The existing anode is prepared from a material with a porous structure, and the existing research direction adopts the research and development of the material with the porous structure.
However, when the porous material is used as a positive electrode structure in a catalyst application, simple filling is often adopted, so that gas cannot be sufficiently diffused in the positive electrode prepared from the porous material, the reaction rate is too low, the use of the porous material is correspondingly limited, and the cost consumption for developing a new material is too high.
Disclosure of Invention
In order to solve the technical problem, the invention provides an air battery anode.
The specific technical scheme is as follows:
an air battery positive electrode, characterized by comprising:
the positive electrode container comprises a positive electrode container cavity, and a first cavity opening and a second cavity opening which are communicated with the positive electrode container cavity, wherein the first cavity opening is sealed by a sealing piece comprising a waterproof breathable film, and gas enters the first cavity opening through the waterproof breathable film;
the positive electrode body is filled in the positive electrode container cavity, is composed of a plurality of thread-shaped positive electrode split bodies and can be taken out from the second cavity;
electrolyte filled in the cavity of the positive electrode container;
and
the positive electrode lead wire is communicated with the positive electrode body, and one end of the positive electrode lead wire is arranged outside the positive electrode container cavity;
wherein, the air battery anode takes oxygen and water as raw materials to carry out reduction reaction.
Compared with the prior art, the invention has the beneficial effects that: the positive pole body adopts filiform form distribution in the cavity, and when using, the air is changeed and is dispersed in the cavity, has further reduced raw materials cost when guaranteeing the effect.
Further, the positive electrode sub-bodies of the positive electrode body are separated from each other.
The beneficial effect of adopting the further technical scheme is that: the blockage of the gas channel is avoided, and the diffusion of the reaction gas is more facilitated.
Furthermore, the waterproof breathable film is made of polytetrafluoroethylene.
Further, the air battery anode also comprises an air pump communicated with the waterproof breathable film.
The beneficial effect of adopting the further technical scheme is that: air enters the cavity of the positive electrode container through the air pump, so that the diffusion of the air can be further accelerated, and the reaction rate is improved.
Further, the closed piece comprises a waterproof breathable film arranged at the first cavity and a gas cavity arranged below the waterproof breathable film, and the gas pump is connected with the gas cavity.
Further, the closed piece further comprises a closed piece body, a plurality of through holes are formed in the closed piece body, the waterproof breathable film is arranged at the positions of the through holes, and the through holes are connected with the air pump through pipelines.
Further, the anode split body comprises a conductive substrate and an electrode metal layer covering the conductive substrate, and the electrode metal catalyst layer is made of Ag.
Further, a loaded catalyst layer is further arranged between the conductive substrate and the electrode metal layer, and the loaded catalyst layer is arranged between the conductive substrate and the electrode metal layer, and uses graphitized activated carbon or graphene as a load layer to load one or more of manganese dioxide, simple substance nano silver powder, perovskite type cobalt oxide or platinum.
The beneficial effect of adopting the further technical scheme is that: the catalyst layer is used to accelerate the reaction rate, and the filamentous structure is matched, so that the catalyst is distributed in a positive electrode reaction system in a large specific surface area, and the large specific surface area of the positive electrode main body, namely the larger the surface area of the catalyst, is favorable for forming a solid-liquid-gas three-phase interface, the more the three-phase interface is, the more the oxygen and water are favorable for being reduced into OH-Ions.
Further, the positive electrode split body is of a bent wire-shaped structure.
The beneficial effect of adopting the further technical scheme is that: the surface area of the catalyst can be further increased.
Further, the air battery positive electrode also comprises CO communicated with the waterproof breathable film2-An absorption device.
The beneficial effect of adopting the further technical scheme is that: the carbon dioxide removal container is arranged to prevent carbon dioxide from entering the anode electrolyte to generate carbonate ions, and the carbonate ions can affect the efficiency of the catalyst and poison the catalyst.
Further, the CO is2-The absorption device is filled with alkaline substances.
Further, the air pump is connected to the CO2-The absorption device and the positive electrode container.
Further, the air pump is connected with a driving power supply.
Further, the driving power supply comprises an external power supply.
Further, the driving power supply is an external power supply and an air battery comprising the positive electrode.
Furthermore, the air battery anode also comprises a current collection metal frame which is arranged in the anode container cavity and connected between the anode lead-out wire and the anode body.
The beneficial effect of adopting the further technical scheme is that: the electrons are led out through the current collecting metal frame, so that the conduction rate can be increased.
Furthermore, the material of the current collecting metal frame is Cu.
Drawings
Fig. 1 is a cross-sectional view of a positive electrode of an air battery of example 1;
FIG. 2 is a structural view of a positive electrode of an air battery according to example 1;
FIG. 3 is a structural view of a positive electrode can in example 1;
FIG. 4 is a bottom view of the positive electrode container cavity of FIG. 3;
FIG. 5 is a structural view of a positive electrode can in example 1;
FIG. 6 is a bottom view of the closure of FIG. 5;
FIG. 7 is a structural view of a positive electrode of an air battery according to example 1;
FIG. 8 is a view showing a split structure of the positive electrode;
wherein, the anode-A, the cathode-B, the anode container-1, the anode container cavity-101, the first cavity opening-1011, the second cavity opening-1012, the air pump-2, CO2An absorption device-3, an external power supply-4, an alkaline substance-301, a starting switch-5, an anode body-6, an anode split body-601, an electrolyte-7, an anode lead-out wire-8, a current collection metal frame-9, a sealing piece-10, a waterproof breathable air-permeableMembrane-1001, gas chamber-1002, closure body-1003, through-hole-10031, vent-pipe-1004, current sensor-11.
Detailed Description
The principles and features of this invention are described below in conjunction with the following drawings, which are set forth by way of illustration only and are not intended to limit the scope of the invention.
Example 1
The present embodiment provides an air battery positive electrode a which, as shown in fig. 1,
the method comprises the following steps: the positive electrode container 1, the positive electrode container 1 include positive electrode container cavity 101 and first chamber mouth 1011 and second chamber mouth 1012 with positive electrode container cavity 101 intercommunication, first chamber mouth 1011 adopts closure piece 10 including waterproof ventilated membrane 1001 to seal, and gas gets into chamber mouth 1011 from waterproof ventilated membrane, and positive electrode container cavity 101 is filled with electrolyte 7, and in this embodiment, the material of waterproof ventilated membrane 10 adopts the polytetrafluoroethylene material preparation. The positive electrode body 6 is filled in the positive electrode container cavity 101, the positive electrode body 6 is composed of a plurality of thread-shaped positive electrode split bodies 601, the structures of the positive electrode split bodies are consistent from the second cavity 1012, the positive electrode body 6 is communicated with the positive electrode lead-out wire 8, and one end of the positive electrode lead-out wire 8 is arranged outside the positive electrode container cavity 101;
in this embodiment, the anode a may perform a reduction reaction using oxygen as a raw material, and the specific reaction formula is shown in formula I, on the premise that the basic reaction is satisfied, the anode material and the electrolyte material are not limited, and are all known in the art, and in this embodiment, the electrolyte may be an alkali solution (NaOH, KOH).
The reaction formula carried out at the positive electrode is:
the reaction formula of the positive electrode is as follows:
Figure RE-GDA0003137227500000051
to reduce subsequent assembly procedures, a convenient OH may be employed-Is mounted at the second chamber 1012. The anion exchange membrane 1013 may also be assembled at a later time of use.
In order to further increase the diffusion rate of the gas in the positive electrode container cavity 101, as shown in fig. 2 to fig. 6, the gas pump 2 is an electric gas pump, and is started by using a driving power supply, which may be completely an external power supply, or may be a combination of the external power supply and the internal power supply, in this embodiment, the internal power supply including the negative electrode B and the positive electrode a in this embodiment and the external power supply 4 are used together as the driving power supply for the gas pump 2, in this embodiment, a lithium battery is used as the external power supply 4, and the specific connection method thereof is as follows:
the air pump 2 is respectively connected with an external power supply 4 and a battery containing the positive electrode of the embodiment, a starting switch 5 is arranged on a connection path of the air pump 2 and the external power supply, a current sensor 11 is arranged on a path of the battery containing the positive electrode A of the embodiment, the current sensor 11 is connected with the starting switch 5, and the power required by the air pump 2 is far less than the power supply power of the battery containing the positive electrode of the embodiment.
The negative electrode B and the positive electrode A jointly form an electrochemical reaction by taking metal as a raw material.
In this example, the reaction carried out by the negative electrode B was:
Al-3e→Al3+
Al3++4OH-→AlO2 -+2H2O；
the anode structure and the anode electrolyte are conventionally selected in the art based on the above reaction mechanism.
As shown in fig. 3 to 4, in the present embodiment, the gas is pressed into the positive electrode container cavity 101 by the gas pump 2, specifically, the sealing member 10 is composed of a gas cavity 1002 and a waterproof gas-permeable membrane 1001, the waterproof gas-permeable membrane seals the whole cavity opening, the gas cavity is disposed below the waterproof gas-permeable membrane, a through hole (not shown) is disposed on the outer layer of the gas cavity 1002, and the gas pump 2 is communicated with the gas cavity 102.
Alternatively, as shown in fig. 5 to 6, the closure 10 is composed of a closure body 1003 and a waterproof breathable film 1002, the closure body is provided with a plurality of through holes 10031, the waterproof breathable film is provided at the through holes, and the through holes 10031 and the air pump 2 are communicated with each other by a breathable pipe 1004.
In this embodiment, the anode split bodies 601 are not adhered to each other as much as possible to ensure the dispersion of the reaction gas in the anode container cavity. To be liftedIn this embodiment, as shown in fig. 8, the positive electrode separator 601 has a three-layer structure: comprises a conductive substrate 6011, a supported catalyst layer 6012 and an electrode metal catalyst layer 6013 from inside to outside in sequence, more specifically, the conductive aggregate is made of a high-conductivity material, the electrode metal catalyst layer is mainly made of an Ag material, the supported catalyst layer is made of graphitized activated carbon and supports MnO2And single-substance nano silver powder and the like.
In order to further increase the supported surface area of the supported catalyst and the electrode metal catalyst, the positive electrode separator 601 may have a bent filament structure in the present embodiment.
As shown in FIG. 7, in the present embodiment, the air inlet end of the air pump 2 is connected with the CO2Absorption unit 3 connected, CO2The absorption device 3 is internally provided with alkaline substances 301(NaOH, KOH and the like) so that CO in the gas entering the positive electrode container cavity 101 for reaction is removed firstly2So as to avoid entering into electrolyte to generate carbonate to cause catalyst poisoning.
In order to further increase the conducting speed, in this embodiment, a current collecting metal frame 9 is disposed in the positive electrode container cavity 101, the positive electrode lead wire 8 is connected to the current collecting metal frame 9, and further, the current collecting metal frame 9 is made of Cu.
The method for using the air battery anode comprises the following steps: the external power supply 4 and the air pump 2 are connected, so that air enters the positive electrode container cavity 101 through the air cavity 102, oxygen in the air is dispersed and enters the electrolyte 7 to perform positive electrode reaction, the current sensor 11 senses that the current reaches a preset current, the starting switch is switched off, and the power supply supplies power to the air pump 2.
The devices are all existing equipment and are available in the market.
Comparative example 1
The supported catalyst layer prepared from the same material as in example 1 was coated with Ag to the same thickness as in example 1, and the resultant was directly filled in a positive electrode container shown in FIG. 1 to a total volume of 1dm3The electrolyte and the negative electrode connected to the container were also the same as in example 1.
Example 3
The positive electrode shown in FIG. 1The positive electrode shown in FIG. 2, the positive electrode shown in FIG. 3 and the electrode of comparative example 1 were subjected to discharge voltage test experiments, wherein the negative electrode having the same structure as that of FIG. 1 was the same as that of FIGS. 2 and 7, and the volume of the catalyst in the positive electrode structure was 1dm3And the other conditions are consistent, and the discharge voltage and the peak power after the continuous use for 7 days are counted.
The results are shown in Table 1.
TABLE 1 discharge Voltage test results
Figure RE-GDA0003137227500000071
Figure RE-GDA0003137227500000081
As can be seen from table 1, in example 1, the discharge voltage is significantly higher than that of the conventional filled positive electrode structure battery using the filament shape as the positive electrode host, compared to comparative example 1.
Meanwhile, the research team of the applicant adopts the air pump to further increase the diffusion rate of the gas and plays an important role in further improving the discharge voltage.
And using CO2The absorption device absorbs CO in the air2It can prevent catalyst poisoning, further improve catalytic efficiency, and promote discharge voltage increase.
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, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. An air battery positive electrode, comprising:
the positive electrode container comprises a positive electrode container cavity, and a first cavity opening and a second cavity opening which are communicated with the positive electrode container cavity, wherein the first cavity opening is sealed by a sealing piece comprising a waterproof breathable film, and gas enters the first cavity opening through the waterproof breathable film;
the positive electrode body is filled in the positive electrode container cavity, is composed of a plurality of thread-shaped positive electrode split bodies and can be taken out from the second cavity;
electrolyte filled in the cavity of the positive electrode container;
and
and one end of the positive electrode lead-out wire is arranged outside the positive electrode container cavity.
2. The air battery positive electrode according to claim 1, further comprising an air pump connected to the waterproof breathable film.
3. The air-battery positive electrode according to claim 1 or 2, further comprising CO in communication with the water-resistant breathable film2An absorption device.
4. The air battery positive electrode of claim 3, wherein the air pump is connected to the CO2The absorption device and the positive electrode container.
5. The air battery positive electrode according to any one of claims 1 to 4, wherein the positive electrode separation body comprises a conductive substrate and an electrode metal catalyst layer covering the conductive substrate.
6. The air battery positive electrode according to claim 5, further comprising a supported catalyst layer between the conductive substrate and the electrode metal layer, wherein the supported catalyst layer uses graphitized activated carbon or graphene as a supporting layer and supports one or more of manganese dioxide, elemental nano silver powder, perovskite type cobalt oxide or platinum.
7. The air battery positive electrode according to claim 2, wherein the air pump is connected to a driving power source.
8. The air battery positive electrode according to claim 5, wherein the electrode metal catalyst layer is made of Ag.
9. The air battery positive electrode according to claim 1, further comprising a collector metal frame connected between the positive electrode lead wire and the positive electrode body inside the positive electrode container cavity.
10. The air battery positive electrode according to claim 9, wherein the collector metal frame is made of Cu.
CN202110303753.XA 2021-03-22 2021-03-22 Air battery anode Pending CN113270590A (en)

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CN202110303753.XA CN113270590A (en) 2021-03-22 2021-03-22 Air battery anode

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Country Status (1)

Country Link
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