CN108736019A - Metal fuel battery air electrode and preparation method thereof - Google Patents
Metal fuel battery air electrode and preparation method thereof Download PDFInfo
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- CN108736019A CN108736019A CN201810317587.7A CN201810317587A CN108736019A CN 108736019 A CN108736019 A CN 108736019A CN 201810317587 A CN201810317587 A CN 201810317587A CN 108736019 A CN108736019 A CN 108736019A
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- micropore ceramics
- layer
- current collector
- air electrode
- conductive current
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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
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8882—Heat treatment, e.g. drying, baking
- H01M4/8885—Sintering or firing
- H01M4/8889—Cosintering or cofiring of a catalytic active layer with another type of layer
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
- H01M4/8896—Pressing, rolling, calendering
Abstract
The invention discloses metal fuel battery air electrodes and preparation method thereof, wherein metal fuel battery includes with air electrode：Conductive current collector, micropore ceramics layer, waterproof layer and Catalytic Layer, the micropore ceramics layer are formed on a side surface of the conductive current collector；The waterproof layer is formed on the surface of the micropore ceramics layer；The Catalytic Layer is formed on another side surface of the conductive current collector.Metal fuel battery proposed by the present invention not only has excellent mechanical strength, preferable gas permeability, water proofing property and good electric conductivity with air electrode, also there is higher catalytic activity and gas-selectively, and in use, micropore ceramics layer, waterproof layer and Catalytic Layer it is not easily to fall off, have higher discharge voltage and longer service life.
Description
Technical field
The invention belongs to metal fuel battery fields, in particular to metal fuel battery air electrode and its system
Preparation Method.
Background technology
Currently, the preparation process of metal fuel battery air electrode, using by hydrophobic carbon material acetylene black or catalyst material
Material is mixed in a certain ratio separate roller with PTFE emulsion and is pressed onto certain thickness waterproof layer or Catalytic Layer, the film that then will be suppressed
Layer is pressed into air electrode with conductive current collector, and the pressing process of waterproof layer, catalyst preparation and Catalytic Layer is cumbersome, yield
It is low, a large amount of human and material resources need to be consumed, and the air electrode consistency prepared is poor.Lead to air electrode in use
Occur that carbon falls off, catalyst falls off and electrolyte carbonation phenomenon, to greatly shorten the service life of air electrode.Therefore,
Metal fuel battery air electrode is further improved.
Invention content
The present invention is directed to solve at least some of the technical problems in related technologies.For this purpose, the present invention
One purpose is to propose metal fuel battery air electrode and preparation method thereof.Metal fuel battery proposed by the present invention is used
Air electrode not only has excellent mechanical strength, preferable gas permeability, water proofing property and good electric conductivity, also has higher
Catalytic activity and gas-selectively, and in use, micropore ceramics layer, waterproof layer and Catalytic Layer it is not easily to fall off, have compared with
High discharge voltage and longer service life.
According to the first aspect of the invention, the present invention proposes a kind of metal fuel battery air electrode, including：
Conductive current collector；
Micropore ceramics layer, the micropore ceramics layer are formed on a side surface of the conductive current collector；
Waterproof layer, the waterproof layer are formed on the surface of the micropore ceramics layer；
Catalytic Layer, the Catalytic Layer are formed on another side surface of the conductive current collector.
The metal fuel battery of the above embodiment of the present invention not only has excellent mechanical strength, preferable with air electrode
Gas permeability, water proofing property and good electric conductivity also have higher catalytic activity and gas-selectively, and in use
Micropore ceramics layer, waterproof layer and Catalytic Layer are not easily to fall off, have higher discharge voltage and longer service life.
In addition, metal fuel battery air electrode according to the above embodiment of the present invention can also be with following additional
Technical characteristic：
In some embodiments of the invention, the conductive current collector by be selected from copper, copper nickel plating, nickel, stainless steel nickel plating and
The metal mesh that at least one of nickel alloy is formed.Thus, it is possible to further increase the conduction of metal fuel battery air electrode
Property and corrosion resistance.
In some embodiments of the invention, the metal mesh is oblique pull net, establishment net or punching net.Thus, it is possible into
One step improves the mechanical strength of metal fuel battery air electrode.
In some embodiments of the invention, the Catalytic Layer is formed by the micropore ceramics of supported catalyst, the catalysis
Agent is selected from least one of manganese cobalt, lithium manganese cobalt, Mn oxide, argentum-based catalyzer and perovskite type catalyst.It not only can be with
Further increase the specific surface area, catalytic activity and catalytic selectivity of Catalytic Layer, moreover it is possible to significantly improve metal fuel battery sky
Mechanical strength, gas permeability and the electric conductivity of pneumoelectric pole.
In some embodiments of the invention, the micropore ceramics difference for including in the micropore ceramics layer and the Catalytic Layer
It independently is and is selected from Al2O3、ZnO、ZrO、SiO2、CaO、MgO、TiO2With in SiC at least two high-temperature roasting product.As a result,
The mechanical strength and gas permeability of metal fuel battery air electrode can be further increased, and makes ratio of the Catalytic Layer with bigger
Surface area.
According to the second aspect of the invention, the present invention, which proposes, a kind of preparing above-mentioned metal fuel battery air electrode
Method, including：
(1) conductive current collector is pre-processed；
(2) micropore ceramics are mixed with binder and is coated on the side surface Jing Guo the pretreated conductive current collector
On, drying, to form micropore ceramics layer；
(3) micropore ceramics of supported catalyst are mixed with binder and is coated on by the pretreated conductive afflux
On another side surface of body, drying, to form Catalytic Layer；
(4) conductive current collector obtained to step (3) is pressed and calcination process, to obtain micropore ceramics sky
Pneumoelectric pole；
(5) water-proofing treatment is carried out to the surface of the micropore ceramics layer, to form waterproof layer, and obtains the metal combustion
Expect battery air electrode.
The method for preparing metal fuel battery air electrode of the above embodiment of the present invention is not only simple for process, parameter item
Part is easily controllable and production cost is low, it is easy to accomplish large-scale production, and the metal fuel battery being prepared air electricity
Pole not only has excellent mechanical strength, preferable gas permeability, water proofing property and good electric conductivity, also has higher catalysis
Activity and gas-selectively, and micropore ceramics layer, waterproof layer and Catalytic Layer are not easily to fall off in use, have higher put
Piezoelectric voltage and longer service life.
In some embodiments of the invention, in step (1), the pretreatment is that the conductive current collector is placed in pre- place
It is ultrasonically treated 30-90 minutes in reason liquid, the pretreatment fluid is selected from least one of lye, alcohol and acetone.As a result, may be used
To effectively remove the pollutants such as conductive current collector surface impurity that may be present, greasy dirt.
In some embodiments of the invention, in step (2) and step (3), the micropore ceramics are separately choosing
From Al2O3、ZnO、ZrO、SiO2、CaO、MgO、TiO2With in SiC at least two high temperature sintering product.Thus, it is possible to further
The mechanical strength and gas permeability of metal fuel battery air electrode are improved, and makes specific surface area of the Catalytic Layer with bigger.
In some embodiments of the invention, the binder be separately selected from CMC, HPMC, PEO, PVA and
At least one of PTFE.Thus, it is possible to the bond strength of micropore ceramics layer and Catalytic Layer and conductive current collector is further increased,
Make metal fuel battery air electrode that there is better mechanical performance and gas permeability.
In some embodiments of the invention, in step (2), the mass percent of the micropore ceramics and the binder
For 60-90%.Thus, it is possible to further increase the bond strength of micropore ceramics layer and conductive current collector.
In some embodiments of the invention, the quality percentage of the micropore ceramics of the supported catalyst and the binder
Than for 75-90%.Thus, it is possible to further increase the bond strength of Catalytic Layer and conductive current collector.
In some embodiments of the invention, in step (4), the pressure that the compression moulding uses is 10-100MPa.No
The green body of dimensionally stable only can effectively be prepared, moreover it is possible to further increase micropore ceramics layer and Catalytic Layer and conductive current collector
Bond strength.
In some embodiments of the invention, the calcination process be under the protective atmosphere of argon gas, nitrogen or helium, and
It is warming up to 500-1400 DEG C with the heating rate of 2-20 DEG C/min and maintains 5-20h, then is dropped with the rate of temperature fall of 5-20 DEG C/min
Warm to room temperature completion.It is possible thereby to further increase the efficiency of calcination process, and avoid temperature change too fast so that roasting
Micropore ceramics air electrode internal-external temperature difference is excessive in journey, dry and cracked phenomenon occurs.
In some embodiments of the invention, in step (5), using organic polydimethylsiloxane to the micropore ceramics layer
Surface carry out water-proofing treatment.Thus, it is possible to further increase the waterproof effect of waterproof layer.
Description of the drawings
Fig. 1 is the structural schematic diagram of metal fuel battery air electrode according to an embodiment of the invention.
Fig. 2 is the method flow diagram according to an embodiment of the invention for preparing metal fuel battery air electrode.
Specific implementation mode
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings, wherein from beginning to end
Same or similar label indicates same or similar element or element with the same or similar functions.Below with reference to attached
The embodiment of figure description is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.
According to the first aspect of the invention, the present invention proposes a kind of metal fuel battery air electrode, such as Fig. 1 institutes
Show, including：Conductive current collector 100, micropore ceramics layer 200, waterproof layer 300 and Catalytic Layer 400, wherein 200 shape of micropore ceramics layer
At on a side surface of conductive current collector 100；Waterproof layer 300 is formed on the surface of micropore ceramics layer 200；Catalytic Layer 400
It is formed on 100 another side surface of conductive current collector.
The metal fuel battery of the above embodiment of the present invention not only has excellent mechanical strength, preferable with air electrode
Gas permeability, water proofing property and good electric conductivity also have higher catalytic activity and gas-selectively, and in use
Micropore ceramics layer 200, waterproof layer 300 and Catalytic Layer 400 are not easily to fall off, have higher discharge voltage and it is longer use the longevity
Life.
According to a particular embodiment of the invention, conductive current collector 100 can be by being selected from copper, copper nickel plating, nickel, stainless steel nickel plating
The metal mesh formed at least one of nickel alloy.The present invention can further increase metal combustion by selecting above-mentioned metal mesh
Expect the electric conductivity and corrosion resistance of battery air electrode.
According to a particular embodiment of the invention, metal mesh can be oblique pull net, establishment net or punching net.Thus, it is possible into
One step improves the mechanical strength of metal fuel battery air electrode.
According to a particular embodiment of the invention, Catalytic Layer 400 can be formed by the micropore ceramics of supported catalyst, catalyst
Can be selected from least one of manganese cobalt, lithium manganese cobalt, Mn oxide, argentum-based catalyzer and perovskite type catalyst.The present invention
In by selecting form Catalytic Layer 400 with the micropore ceramics of supported catalyst, can not only further increase the ratio of Catalytic Layer 400
Surface area, catalytic activity and catalytic selectivity, moreover it is possible to significantly improve the mechanical strength of metal fuel battery air electrode, breathe freely
Property and electric conductivity.Preferably, the catalyst can be manganese Co catalysts or perovskite type catalyst, thus, it is possible to further
Improve the catalytic activity and catalytic selectivity of Catalytic Layer 400.
According to a particular embodiment of the invention, the micropore ceramics for including in micropore ceramics layer 200 and Catalytic Layer 400 can divide
It independently is not selected from Al2O3、ZnO、ZrO、SiO2、CaO、MgO、TiO2With in SiC at least two high-temperature roasting product.Hair
A person of good sense has found, the micropore ceramics of mentioned kind using micro- stomata as main phase, and with excellent wear-resistant, high temperature resistant, it is anticorrosive and
The excellent performances such as high rigidity, by selecting above-mentioned micropore ceramics to be used to form micropore ceramics layer 200 in the present invention, and load is urged
It is used to form Catalytic Layer 400 after agent, the mechanical strength of metal fuel battery air electrode can be further increased and breathes freely
Property, and make specific surface area of the Catalytic Layer 400 with bigger.
According to a particular embodiment of the invention, the thickness of micropore ceramics layer 200 can be 0.2-0.5mm, waterproof layer 300
Thickness can be 0.2-0.6mm, and the thickness of Catalytic Layer 400 can be 0.1-0.4mm.Inventor has found, if micropore ceramics layer 200
It is excessively thin, it is unfavorable for enhancing the mechanical strength of metal fuel battery air electrode, is easy to happen mechanical damage in use
Decline with electrode performance；And if micropore ceramics layer 200 is blocked up, although the machine of metal fuel battery air electrode can be significantly improved
Tool intensity, but the diffusion rate of gas can be influenced, and then influence the discharge effect of metal fuel battery；If 300 mistake of waterproof layer
Thin, generated waterproof effect is limited, when the vapor in electrolyte is different with the partial pressure of water vapor in air, is easy to cause
Vapor is diffused to by air electrode in electrolyte from air, or is diffused in air from electrolyte, and then influences electricity
Solving the service life of the concentration and metal fuel battery of liquid further can also influence metal when vapor is spread through air electrode
The gas permeability of fuel cell air electrode, so influence metal fuel battery discharge effect, and if waterproof layer 300 is blocked up,
The diffusion rate of gas can equally be influenced；If Catalytic Layer 400 is excessively thin, the catalytic effect of the generation in hydrogen reduction catalytic process has
Limit, and electrolyte is easy blocking microporous ceramics, influence gas influences oxygen reduction reaction in turn with electrolyte contacts, and works as Catalytic Layer
400 it is blocked up when, can not only influence the diffusion rate of gas, and be easy to cause in preparation process Catalytic Layer 400 occur it is dry and cracked.By
This can be such that metal fires by controlling micropore ceramics layer 200, waterproof layer 300 and Catalytic Layer 400 as above-mentioned thickness in present invention
Expect that battery has excellent mechanical strength, preferable gas permeability, water proofing property and electric conductivity and higher catalysis with air electrode
Activity and gas-selectively, and micropore ceramics layer 200, waterproof layer 300 and Catalytic Layer 400 are not easily to fall off in use, tool
There are higher discharge voltage and longer service life.
According to the second aspect of the invention, the present invention, which proposes, a kind of preparing above-mentioned metal fuel battery air electrode
Method, including：
(1) conductive current collector 100 is pre-processed；(2) micropore ceramics are mixed with binder and is coated on by pre-
On one side surface of the conductive current collector of processing, drying, to form micropore ceramics layer 200；(3) by the micropore of supported catalyst
Ceramics are mixed with binder and are coated on another side surface Jing Guo pretreated conductive current collector, are dried, are urged to be formed
Change layer 400；(4) conductive current collector obtained to step (3) is pressed and calcination process, to obtain micropore ceramics sky
Pneumoelectric pole；(5) water-proofing treatment is carried out to the surface of micropore ceramics layer 200, to form waterproof layer 300, and obtains metal fuel
Battery air electrode.
The method for preparing metal fuel battery air electrode of the above embodiment of the present invention is not only simple for process, parameter item
Part is easily controllable and production cost is low, it is easy to accomplish large-scale production, and the metal fuel battery being prepared air electricity
Pole not only has excellent mechanical strength, preferable gas permeability, water proofing property and good electric conductivity, also has higher catalysis
Activity and gas-selectively, and micropore ceramics layer 200, waterproof layer 300 and Catalytic Layer 400 are not easily to fall off in use, tool
There are higher discharge voltage and longer service life.
The method for preparing metal fuel battery air electrode of the above embodiment of the present invention is carried out in detail below with reference to Fig. 2
Thin description.
S100：It is respectively formed micropore ceramics layer and Catalytic Layer in the both sides of conductive current collector
According to an embodiment of the invention, conductive current collector 100 is pre-processed, and micropore ceramics is mixed with binder
And coated on by pretreated conductive current collector surface, drying, to form micropore ceramics layer 200；By supported catalyst
Micropore ceramics mix and be coated on another side surface Jing Guo pretreated conductive current collector with binder, dry, so as to
Form Catalytic Layer 400.Thus, it is possible to be respectively formed micropore ceramics layer 200 and Catalytic Layer 400 in the both sides of conductive current collector 100.
According to a particular embodiment of the invention, conductive current collector 100 can be placed in pretreatment fluid at ultrasound by pretreatment
Reason is completed for 30-90 minutes, and pretreatment fluid can be selected from least one of lye, alcohol and acetone.Thus, it is possible to effectively go
Except pollutants such as 100 surface of conductive current collector impurity that may be present, greasy dirts.
According to a particular embodiment of the invention, the above-mentioned micropore ceramics for being used to form micropore ceramics layer and supported catalyst
Micropore ceramics can be separately selected from Al2O3、ZnO、ZrO、SiO2、CaO、MgO、TiO2With in SiC at least two height
Warm sintered product.Inventor has found, the micropore ceramics of mentioned kind are using micro- stomata as main phase, and with excellent wear-resistant, resistance to
The excellent performances such as high temperature, anticorrosive and high rigidity, by selecting above-mentioned micropore ceramics to be used to form micropore ceramics layer in the present invention
200 and supported catalyst after be used to form Catalytic Layer 400, metal fuel battery air electrode can be further increased
Mechanical strength and gas permeability, and make specific surface area of the Catalytic Layer 400 with bigger.
According to a particular embodiment of the invention, the micropore ceramics of supported catalyst can be Al2O3、ZnO、ZrO、SiO2、
CaO、MgO、TiO2With in SiC at least two high temperature sintering product.
According to a particular embodiment of the invention, above-mentioned binder can be separately selected from CMC, HPMC, PEO, PVA
At least one of with PTFE.The binder of the above-mentioned type has preferable hydrophobicity or caking property, passes through selection in the present invention
Above-mentioned binder can be not only contributed to the micropore ceramics of micropore ceramics and supported catalyst being coated on and be led by pretreated
The both sides of electrojet body, and the bond strength of micropore ceramics layer 200 and Catalytic Layer 400 and conductive current collector 100 is further increased,
The hydrophobicity of micropore ceramics layer 200 and Catalytic Layer 400 can also be significantly improved, and then metal fuel battery air electrode can be made
With better mechanical performance and gas permeability.
According to a particular embodiment of the invention, the mass percent of micropore ceramics and binder can be 60-90%.Invention
People has found that, when the mass ratio of micropore ceramics and binder is excessive, the addition of binder is very few, micropore ceramics and conductive afflux
The bond strength of body 100 is smaller, is unfavorable for forming micropore ceramics layer 200；And when the mass ratio of micropore ceramics and binder is too small
When, the addition of binder is excessive, not only wastes raw material, also result in belong to fuel cell air electrode mechanical strength and thoroughly
Gas declines.It is as a result, 60-90% by controlling the mass percent of micropore ceramics and binder in the present invention, it not only can be with
The bond strength of micropore ceramics layer 200 and conductive current collector 100 is further increased, metal fuel battery air can also be made electric
It is great to have better mechanical performance and gas permeability.
According to a particular embodiment of the invention, the mass percent of the micropore ceramics of supported catalyst and binder can be
75-90%.The bond strength that Catalytic Layer 400 and conductive current collector 100 can not only be further increased as a result, can also make gold
Belong to fuel cell has better mechanical performance and gas permeability with air electrode.
According to a particular embodiment of the invention, micropore ceramics can be mixed with binder and is coated on by pretreated
On conductive current collector surface, it is placed in vacuum drying oven or air dry oven and carries out 30-180min at 50-150 DEG C, so as to shape
At micropore ceramics layer 200.Thus, it is possible to further increase drying effect and micropore ceramics layer 200 and conductive current collector 100
Bond strength.
According to a particular embodiment of the invention, the micropore ceramics of supported catalyst can be mixed and be coated on binder
By on another side surface of pretreated conductive current collector 100, being placed in vacuum drying oven or air dry oven in 50-150
30-180min is carried out at DEG C, to form Catalytic Layer 400, thus, it is possible to further increase drying effect and Catalytic Layer 400
With the bond strength of conductive current collector 100.
S200：Compression moulding and calcination process
According to an embodiment of the invention, to be formed with the conductive current collector 100 of micropore ceramics layer 200 and Catalytic Layer 400 into
Row compression moulding and calcination process, to obtain micropore ceramics air electrode.By in advance to being formed with micropore pottery in the present invention
The conductive current collector 100 of enamel coating 200 and Catalytic Layer 400 is pressed carries out calcination process again, can effectively be prepared
The green body of dimensionally stable, and it is avoided to occur dry and cracked phenomenon during calcination process, to obtain having excellent machinery strong
The micropore ceramics air electrode of degree.
According to a particular embodiment of the invention, the pressure that compression moulding uses is 10-100MPa.Can not only have as a result,
The green body of dimensionally stable is prepared in effect, moreover it is possible to further increase micropore ceramics layer 200 and Catalytic Layer 400 and conductive current collector
100 bond strength.
According to a particular embodiment of the invention, calcination process can under the protective atmosphere of argon gas, nitrogen or helium, and with
The heating rate of 2-20 DEG C/min is warming up to 500-1400 DEG C and maintains 5-20h, then is cooled down with the rate of temperature fall of 5-20 DEG C/min
It is completed to room temperature.The efficiency of calcination process can not be further increased as a result, and avoids the catalyst quilt in Catalytic Layer 400
Oxidation, moreover it is possible to effectively avoid temperature change too fast so that micropore ceramics air electrode internal-external temperature difference is excessive in roasting process, occur
Dry and cracked phenomenon, and then the bond strength of Catalytic Layer 400 and micropore ceramics layer 200 and conductive current collector 100 can be further increased
And the mechanical strength of micropore ceramics air electrode.
S300：Waterproof layer is formed on the surface of micropore ceramics layer
According to an embodiment of the invention, water-proofing treatment can be carried out to the surface of micropore ceramics layer 200, to form waterproof
Layer 300, and obtain metal fuel battery air electrode.Thus, it is possible to effectively vapor be avoided to expand by air electrode
It dissipates, and then the gas permeability of metal fuel battery air electrode can be further increased.
According to a particular embodiment of the invention, surface of organic polydimethylsiloxane to micropore ceramics layer 200 may be used
Carry out water-proofing treatment.Specifically, the surface that organic polydimethylsiloxane is coated in micropore ceramics layer 200 may be used, in 100-
It is dried to get to waterproof layer under 200 degrees Celsius.Thus, it is possible to further increase the waterproof effect of waterproof layer 300.
Embodiment 1
(1) 5cm × 10cm punching stainless steels is taken to plate nickel screen as conductive current collector, and to conductive afflux in weak caustic solution
Body is pre-processed；
(2) by ZrO2-ZnO-SiO2- CaO micropore ceramics material and binder (CMC and PTFE) by mass percentage 85%
Mixing, wherein binder CMC are 1 with PTFE mass ratioes：2.Water is added to stir evenly, slurry is coated on and is led by pretreated
On one side surface of electrojet body, 8h is dried in 80 DEG C of convection ovens, forms micropore ceramics layer；
(3) load is had to the ZrO of manganese cobalt spinel2-ZnO-SiO2- CaO micropore ceramics press quality percentage with binder CMC
Than 90% mixing, water is added and stirs evenly, slurry is coated on another side surface Jing Guo pretreated conductive current collector, in
6h is dried in 80 DEG C of vacuum drying ovens, forms Catalytic Layer；
(4) conductive current collector that step (3) obtains is subjected to calcination process under 60MPa pressure after compression moulding 10min,
Calcination atmosphere is helium, is that 5 DEG C/min is warming up to 1000 DEG C with heating rate, keeps the temperature 10h, dropped for 10 DEG C/min with rate of temperature fall
It warms to room temperature, obtains micropore ceramics air electrode；
(5) water-proofing treatment is carried out to the surface of micropore ceramics layer using organic polydimethylsiloxane, forms waterproof layer, obtains
Metal fuel battery air electrode.
Embodiment 2
(1) it takes 5cm × 10cm oblique pull nickel screens as conductive current collector, and conductive current collector is carried out in advance in alkaline solution
Processing；
(2) by ZrO2-Al2O3-SiO2- CaO micropore ceramics material is mixed with binder (HPMC and PTFE) in mass ratio 87%
It closes, wherein binder HPMC is 2 with PTFE mass ratioes：3.Water is added to stir evenly, slurry is coated on and is led by pretreated
On one side surface of electrojet body, 8h is dried in 100 DEG C of convection ovens, forms micropore ceramics layer；
(3) load is had to the ZrO of manganese cobalt spinel catalyst2-Al2O3-SiO2- CaO micropore ceramics are pressed with binder HPMC
Mass ratio 85% mixes, and water is added and stirs evenly, and slurry is coated on another side surface Jing Guo pretreated conductive current collector
On, 6h is dried in 100 DEG C of vacuum drying ovens, forms Catalytic Layer；
(4) conductive current collector that step (3) obtains is subjected to calcination process under 60MPa pressure after compression moulding 10min,
Calcination atmosphere is helium, is that 5 DEG C/min is warming up to 1000 DEG C with heating rate, keeps the temperature 10h, dropped for 10 DEG C/min with rate of temperature fall
It warms to room temperature, obtains micropore ceramics air electrode；
(5) water-proofing treatment is carried out to the surface of micropore ceramics layer using organic polydimethylsiloxane, forms waterproof layer, obtains
Metal fuel battery air electrode.
Embodiment 3
(1) 5cm × 10cm punching stainless steels is taken to plate nickel screen as conductive current collector, and to conductive afflux in weak caustic solution
Body is pre-processed；
(2) by ZrO2-Al2O3-TiO2- CaO micropore ceramics material and binder (PVA and PTFE) are by mass percentage
80% mixing, wherein binder PVA are 1 with PTFE mass ratioes：3.Water is added to stir evenly, slurry is coated on by pre-processing
Conductive current collector a side surface on, dry 8h in 80 DEG C of convection ovens, form micropore ceramics layer；
(3) load is had to the ZrO of manganese cobalt spinel catalyst2-Al2O3-TiO2- CaO micropore ceramics are pressed with binder PVA
Mass percent 80% mixes, and water is added and stirs evenly, and slurry is coated on the other side Jing Guo pretreated conductive current collector
On surface, 6h is dried in 80 DEG C of vacuum drying ovens, forms Catalytic Layer；
(4) conductive current collector that step (3) obtains is subjected to calcination process under 60MPa pressure after compression moulding 10min,
Calcination atmosphere is helium, is that 5 DEG C/min is warming up to 1000 DEG C with heating rate, keeps the temperature 10h, dropped for 10 DEG C/min with rate of temperature fall
It warms to room temperature, obtains micropore ceramics air electrode；
(5) water-proofing treatment is carried out to the surface of micropore ceramics layer using organic polydimethylsiloxane, forms waterproof layer, obtains
Metal fuel battery air electrode.
Method that the above embodiment of the present invention 1-3 prepares metal fuel battery air electrode is not only simple for process, is easy to
It accomplishes scale production, and stronger machinery is all had with air electrode using the metal fuel battery that this method is prepared
Intensity, the permeability of stabilization, excellent water proofing property and good electric conductivity, and the larger i.e. catalysis of specific surface area of Catalytic Layer
Active higher and catalyst and collector binding force are stronger.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be any
It can be combined in any suitable manner in a or multiple embodiments or example.In addition, without conflicting with each other, the technology of this field
The feature of different embodiments or examples described in this specification and different embodiments or examples can be combined by personnel
And combination.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (10)
1. a kind of metal fuel battery air electrode, which is characterized in that including：
Conductive current collector；
Micropore ceramics layer, the micropore ceramics layer are formed on a side surface of the conductive current collector；
Waterproof layer, the waterproof layer are formed on the surface of the micropore ceramics layer；
Catalytic Layer, the Catalytic Layer are formed on another side surface of the conductive current collector.
2. metal fuel battery air electrode according to claim 1, which is characterized in that the conductive current collector is by being selected from
The metal mesh that at least one of copper, copper nickel plating, nickel, stainless steel nickel plating and nickel alloy are formed,
Optionally, the metal mesh is oblique pull net, establishment net or punching net.
3. metal fuel battery air electrode according to claim 1, which is characterized in that the Catalytic Layer is by supported catalyst
The micropore ceramics of agent are formed, and the catalyst is to be urged selected from manganese cobalt, lithium manganese cobalt, Mn oxide, argentum-based catalyzer and Ca-Ti ore type
At least one of agent.
4. metal fuel battery air electrode according to claim 3, which is characterized in that the micropore ceramics layer and described
The micropore ceramics for including in Catalytic Layer are separately selected from Al2O3、ZnO、ZrO、SiO2、CaO、MgO、TiO2With in SiC extremely
Few two kinds of high-temperature roasting product.
5. a kind of method preparing any one of claim 1-4 metal fuel battery air electrodes, which is characterized in that
Including：
(1) conductive current collector is pre-processed；
(2) micropore ceramics are mixed with binder and are coated on the side surface Jing Guo the pretreated conductive current collector,
Drying, to form micropore ceramics layer；
(3) micropore ceramics of supported catalyst are mixed with binder and is coated on by the pretreated conductive current collector
On another side surface, drying, to form Catalytic Layer；
(4) conductive current collector obtained to step (3) is pressed and calcination process, to obtain micropore ceramics air electricity
Pole；
(5) water-proofing treatment is carried out to the surface of the micropore ceramics layer, to form waterproof layer, and obtains the metal fuel electricity
Pond air electrode.
6. according to the method described in claim 5, it is characterized in that, in step (1), the pretreatment is by the conductive afflux
Body is placed in pretreatment fluid and is ultrasonically treated 30-90 minutes, and the pretreatment fluid is at least one in lye, alcohol and acetone
Kind.
7. according to the method described in claim 5, it is characterized in that, in step (2) and step (3), the micropore ceramics are distinguished
It independently is and is selected from Al2O3、ZnO、ZrO、SiO2、CaO、MgO、TiO2With in SiC at least two high temperature sintering product,
Optionally, the binder is separately selected from least one of CMC, HPMC, PEO, PVA and PTFE.
8. the method according to the description of claim 7 is characterized in that in step (2), the micropore ceramics and the binder
Mass percent is 60-90%,
In step (3), the mass percent of the micropore ceramics of the supported catalyst and the binder is 75-90%.
9. according to the method described in claim 5, it is characterized in that, in step (4), pressure that the compression moulding uses for
10-100MPa,
Optionally, the calcination process be under the protective atmosphere of argon gas, nitrogen or helium, and with the heating of 2-20 DEG C/min speed
Rate is warming up to 500-1400 DEG C and maintains 5-20h, then is cooled to room temperature completion with the rate of temperature fall of 5-20 DEG C/min.
10. according to the method described in claim 5, it is characterized in that, in step (5), using organic polydimethylsiloxane to institute
The surface for stating micropore ceramics layer carries out water-proofing treatment.
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