CN108346807A - Gas-diffusion electrode, catalyst, preparation method and Catalytic Layer spray preparation method - Google Patents
Gas-diffusion electrode, catalyst, preparation method and Catalytic Layer spray preparation method Download PDFInfo
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- CN108346807A CN108346807A CN201810126733.8A CN201810126733A CN108346807A CN 108346807 A CN108346807 A CN 108346807A CN 201810126733 A CN201810126733 A CN 201810126733A CN 108346807 A CN108346807 A CN 108346807A
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- catalyst
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- diffusion 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
- H01M4/9041—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
- 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
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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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
A kind of catalyst of gas-diffusion electrode is disclosed comprising carrier material and active component；Carrier material is that one or several kinds of mixing in acetylene black, activated carbon and/or carbon black are constituted；Active component is double Cob altporphyrins or double Cob altporphyrin doped precious metal agent scarce metallic compounds；The weight percent of the carrier material is 70 99%, and the weight percent of active material is 1 30%.Due to the predominantly double Cob altporphyrins of active component, so the catalyst of this gas-diffusion electrode has either high redox, material is cost-effective, and the chemical property of the electrode manufactured is good, output current is big, high working potential, discharge life are long.Gas-diffusion electrode, Catalytic Layer spray is also disclosed, and prepares the method for this gas-diffusion electrode, the method for preparing this catalyst, the method for preparing this Catalytic Layer spray.
Description
Technical field
The present invention relates to the technical field of new energy battery more particularly to a kind of gas-diffusion electrode, catalyst, Catalytic Layers
Spray, and prepare the method for this gas-diffusion electrode, the method for preparing this catalyst, prepare this Catalytic Layer spray
Method.
Background technology
Metal battery (i.e. metal-air battery) is using the oxygen in air as positive active material, using metal as negative electrode active
Substance issues a kind of biochemical chemistry for reacting and producing electricl energy using conducting solution as electrolyte in the catalytic action of catalyst
Power supply.
Metal battery has many unique advantages, and fuel is metal material, such as the gold such as aluminium, magnesium, zinc and lithium, sodium
Belong to；Because combust aluminium, magnesium, zinc reserves are very abundant, metal-air battery resource enough can be supplied.Positive active material is in air
Oxygen, battery itself do not have to carry, and the energy size entrained by battery is determined by the amount of negative metal so that this kind of battery
It is practical to reach 350Wh/kg or more (lithium ion battery is 100Wh/kg at present) than energy, there is great performance advantage.Instead
Product after answering can utilize the electric energy of the clean energy resourcies such as wind energy, solar energy, water energy or electric energy areas of well-being to be electrolysed oxygen again
Changing aluminium (or magnesium hydroxide) becomes metal, is then again mounted to metal-air battery electric discharge, drives electric vehicle.It thus can be with
It realizes and concentrates large-scale production, it is possible to reduce pollution reduces discharge, and centrally connected power supply may be implemented, and dispersion uses, will be at
This lower electric energy transfer is used to the high place of the cost of electric energy, and the place that electric energy is easily obtained from the energy is transferred to energy hardly possible
It is used with the place of acquisition.It can really realize the completely new auto Life of pollution-free zero-emission.Realize in the process it is pollution-free, zero
The green energy resource of discharge recycles, and metal-air battery worldwide increasingly draws attention.
Metal-air battery has many advantages, such as that capacity is big, energy is high, safe to use and non-environmental-pollution, has always wide
Application prospect.Gas-diffusion electrode is not only the chief component of metal-air battery, even more restricts the key of its performance
Factor.The activity of electrode directly determines the discharge potential and output power of battery, therefore produces the gas diffusion of high activity
Electrode is the committed step for ensureing metal-air battery performance.
However, at present the catalyst material of common gas-diffusion electrode have the shortcomings that it is respective：
1. metal oxide, for example, MnO2 etc. is used as catalyst, redox active relatively low.
2. precious metal material, for example, the precious metal materials such as Ag, Pt have excellent catalytic performance but the cost of raw material very
It is high.
3. the catalytic performance of rear-earth-doped perofskite type oxide is fine, but price is also higher and manufacture difficulty is higher.
Invention content
To overcome the deficiencies of existing technologies, the technical problem to be solved in the present invention is to provide a kind of gas-diffusion electrodes
Catalyst, with either high redox, material is cost-effective, and the chemical property of the electrode manufactured is good, output current
Greatly, high working potential, discharge life are long.
The technical scheme is that：The catalyst of this gas-diffusion electrode comprising carrier material and active component；
Carrier material is that one or several kinds of mixing in acetylene black, activated carbon and/or carbon black are constituted；
Active component is double Cob altporphyrins or double Cob altporphyrin doped precious metal agent scarce metallic compounds；
The weight percent of the carrier material is 70-99%, and the weight percent of active material is 1-30%.
Due to the predominantly double Cob altporphyrins of active component, so the catalyst of this gas-diffusion electrode has either high redox
Property, material is cost-effective, and the chemical property of the electrode manufactured is good, output current is big, high working potential, discharge life
It is long.
Additionally provide a kind of gas-diffusion electrode containing this catalyst comprising Catalytic Layer, transition zone, afflux are conductive
Net and waterproof ventilative layer；
For wherein afflux conductive mesh in the side or centre of transition zone, afflux conductive mesh is metal material or carbon material,
Wherein metal material is stainless steel, nickel, aluminium, iron, copper or silver-plated in the metal surface；The shape of afflux conductive mesh be it is netted or
Foam-like；Catalytic Layer is made catalysis slurry by catalyst and sprays on transition zone, or by catalyst and carbon black and adhesive
It is sufficiently mixed after being pressed into film and is pressed again with transition zone and current collector layer.
The preparation method of the catalyst of this gas-diffusion electrode is additionally provided, this approach includes the following steps：
(1) carbon support material, active material are mixed and added into deionized water and stirred evenly；
(2) it through high-speed stirred at 10-100 DEG C of constant temperature, then dries through 40-120 DEG C, catalyst powder is ground into after cooling
End.
The preparation method of this gas-diffusion electrode is additionally provided, this approach includes the following steps：
(1) transition zone that the afflux conductive mesh that certain, thickness is 0.1-2mm by size is 0.5-3mm with thickness is cold-pressed；
(2) a face coating thickness of transition zone be 0.005-0.5mm catalysis slurry, through 10-100 DEG C drying and
20-80 DEG C of hot pressing；
(3) another side of the transition zone of step (2) and thickness are cold-pressed into 0.5- for the waterproof ventilative layer of 0.05-0.5mm
The electrode slice of 2mm thickness, and it is fired into gas-diffusion electrode at 30-400 DEG C.
Another preparation method of this gas-diffusion electrode is additionally provided, this approach includes the following steps：
(I) in certain size, the side for the afflux conductive mesh that thickness is 0.1-2mm scratches the transition that thickness is 0.5-3mm
Layer slurry is cold-pressed through 10-100 DEG C of drying and in room temperature；
(II) catalyst pulp is sprayed in the one side of transition zone, coating thickness 0.05-0.5mm, then through 10-100
DEG C drying；
(III) waterproof ventilative layer and electrode that thickness is 0.05-0.5mm are coated to the another of the transition zone of catalyst pulp
The electrode slice of 0.5-2mm thickness is bonded and be pressed on one side, is finally fired into gas-diffusion electrode at 30-400 DEG C.
The preparation method of the Catalytic Layer spray of this gas-diffusion electrode is additionally provided, this approach includes the following steps：
A) catalyst fines, ptfe emulsion, adhesive and deionized water are weighed；Wherein catalyst material weight
Amount degree is 30-50%, and ptfe emulsion weight percent content is 5-30%, deionized water 10-40%；It is viscous
Mixture 30-50%；
B) deionized water is added in catalyst fines and is stirred evenly；
C) other components are added in whipping process, through high-speed stirred at catalyst spraying slurry at 10-100 DEG C.
Description of the drawings
Fig. 1 is the chemical structural drawing of double Cob altporphyrins of catalysts for gas diffusion electrodes according to the present invention.
Fig. 2 is the polarization curve of gas-diffusion electrode according to the present invention.
Specific implementation mode
The catalyst of this gas-diffusion electrode comprising carrier material and active component；
Carrier material is that one or several kinds of mixing in acetylene black, activated carbon and/or carbon black are constituted；
Active component is double Cob altporphyrins (as shown in Figure 1) or double Cob altporphyrin doped precious metal agent scarce metallic compounds；
The weight percent of the carrier material is 70-99%, and the weight percent of active material is 1-30%.
Due to the predominantly double Cob altporphyrins of active component, so the catalyst of this gas-diffusion electrode has either high redox
Property, material is cost-effective, and the chemical property of the electrode manufactured is good, output current is big, high working potential, discharge life
It is long.Fig. 2 is to use double polarization curves of the Cob altporphyrin as the gas-diffusion electrode of catalyst.It can be seen from the figure that is close when electric current
Degree is 160mA/cm2When, single battery voltage 1.1V.It is compared to MnO2, operating voltage improves 20%.
Additionally provide a kind of gas-diffusion electrode of the catalyst containing this gas-diffusion electrode comprising Catalytic Layer,
Transition zone, afflux conductive mesh and waterproof ventilative layer；
For wherein afflux conductive mesh in the side or centre of transition zone, afflux conductive mesh is metal material or carbon material,
Wherein metal material is stainless steel, nickel, aluminium, iron, copper or silver-plated in the metal surface；The shape of afflux conductive mesh be it is netted or
Foam-like；Catalytic Layer is made catalysis slurry by catalyst and sprays on transition zone, or by catalyst and carbon black and adhesive
It is sufficiently mixed after being pressed into film and is pressed again with transition zone and current collector layer.
Preferably, the thickness of the Catalytic Layer is 0.005-0.5mm, and the thickness of the waterproof ventilative layer is 0.05-2mm,
The waterproof ventilative layer is fired into the gas-diffusion electrode of 0.5mm thickness with the transition zone by adhesive at 30-400 DEG C.
The preparation method of the catalyst of this gas-diffusion electrode is additionally provided, this approach includes the following steps：
(1) carbon support material, active material are mixed and added into deionized water and stirred evenly；
(2) it through high-speed stirred at 10-100 DEG C of constant temperature, then dries through 40-120 DEG C, catalyst powder is ground into after cooling
End.
The preparation method of this gas-diffusion electrode is additionally provided, this approach includes the following steps：
(1) transition zone that the afflux conductive mesh that certain, thickness is 0.1-2mm by size is 0.5-3mm with thickness is cold-pressed；
(2) a face coating thickness of transition zone be 0.005-0.5mm catalysis slurry, through 10-100 DEG C drying and
20-80 DEG C of hot pressing；
(3) another side of the transition zone of step (2) and thickness are cold-pressed into 0.5- for the waterproof ventilative layer of 0.05-0.5mm
The electrode slice of 2mm thickness, and it is fired into gas-diffusion electrode at 30-400 DEG C.
Another preparation method of this gas-diffusion electrode is additionally provided, this approach includes the following steps：
(I) in certain size, the side for the afflux conductive mesh that thickness is 0.1-2mm scratches the transition that thickness is 0.5-3mm
Layer slurry is cold-pressed through 10-100 DEG C of drying and in room temperature；
(II) catalyst pulp is sprayed in the one side of transition zone, coating thickness 0.05-0.5mm, then through 10-100
DEG C drying；
(III) by waterproof ventilative layer and electrode that thickness is 0.05-0.5mm (please clear electrode herein refer specifically to above
Which part) electrode slice of 0.5-2mm thickness is bonded and is pressed into, finally gas-diffusion electrode is fired at 30-400 DEG C.
The preparation method of the catalysis spray of this gas-diffusion electrode is additionally provided, this approach includes the following steps：
A) catalyst fines, ptfe emulsion, adhesive and deionized water are weighed；Wherein catalyst material weight
Amount degree is 30-50%, and ptfe emulsion weight percent content is 5-30%, deionized water 10-40%；It is viscous
Mixture 30-50%；
B) deionized water is added in catalyst fines and is stirred evenly；
C) other components are added in whipping process, through high-speed stirred at catalyst spraying slurry at 10-100 DEG C.
Several specific embodiments are given below.
Embodiment 1
A kind of air electrode catalyst, including activated carbon and active component are double Cob altporphyrins.The weight of the activated carbon
Percentage is 90%, and the weight percent of catalyst activity component is 10%.
The preparation method of above-mentioned air electrode catalyst：By the activated carbon (XC-72R of Carbot companies of said ratio
Carbon black) it is put into container with the double Cob altporphyrins of active constituent, and it is slowly added to a small amount of deionized water stirring.In whipping process, by
Ptfe emulsion, adhesive and deionized water is added in step, and mixing liquid is sufficiently stirred dispersion with rotating speed for 4000r/min
1 hour, it is finally made catalyst spraying slurry.Process is dispersed with stirring to carry out under the conditions of 10 DEG C of constant temperature.
Embodiment 2
A kind of air electrode catalyst, including activated carbon and active component are double Cob altporphyrins and AgO.The activated carbon
Weight percent is 70%, and the weight percent of catalyst activity component is 10% double Cob altporphyrins, 20% AgO.
The preparation method of above-mentioned air electrode catalyst：By the activated carbon (BP2000 of Carbot companies of said ratio
Carbon black) it is put into container with the double Cob altporphyrins of active constituent and AgO, and it is slowly added to a small amount of deionized water stirring.In whipping process
In, it is gradually added ptfe emulsion, adhesive and deionized water, mixing liquid is fully stirred with rotating speed for 4000r/min
Dispersion 1 hour is mixed, catalyst spraying slurry is finally made.Process is dispersed with stirring to carry out under the conditions of 20 DEG C of constant temperature.
Embodiment 3
A kind of air electrode catalyst, including activated carbon and active component are double Cob altporphyrins, AgO and NiO.The activity
The weight percent of charcoal is 70%, the weight percent of catalyst activity component be 10% double Cob altporphyrins, 10% AgO and
10% NiO.
The preparation method of above-mentioned air electrode catalyst：By activated carbon (the XC-72 carbon of Carbot companies of said ratio
It is black) it is put into container with the double Cob altporphyrins of active constituent, AgO and NiO, and it is slowly added to a small amount of deionized water stirring.Stirred
Cheng Zhong is gradually added ptfe emulsion, adhesive and deionized water, and mixing liquid is abundant for 4000r/min with rotating speed
It is dispersed with stirring 1 hour, is finally made catalyst spraying slurry.Process is dispersed with stirring to carry out under the conditions of 30 DEG C of constant temperature.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, it is every according to
According to the technical spirit of the present invention to any simple modification, equivalent change and modification made by above example, still belong to the present invention
The protection domain of technical solution.
Claims (7)
1. a kind of catalyst of gas-diffusion electrode, it is characterised in that：It includes carrier material and active component；
Carrier material is that one or several kinds of mixing in acetylene black, activated carbon and/or carbon black are constituted；
Active component is double Cob altporphyrins or double Cob altporphyrin doped precious metal agent scarce metallic compounds；
The weight percent of the carrier material is 70-99%, and the weight percent of active material is 1-30%.
2. a kind of gas-diffusion electrode containing catalyst according to claim 1, it is characterised in that：
It includes Catalytic Layer, transition zone, afflux conductive mesh and waterproof ventilative layer；
For wherein afflux conductive mesh in the side or centre of transition zone, afflux conductive mesh is metal material or carbon material, wherein
Metal material is stainless steel, nickel, aluminium, iron, copper or silver-plated in the metal surface；The shape of afflux conductive mesh is netted or foam
Shape；Catalytic Layer is made catalysis slurry by catalyst and sprays on transition zone, or catalyst and carbon black and adhesive is abundant
Mixing is pressed with transition zone and current collector layer again after being pressed into film.
3. gas-diffusion electrode according to claim 2, it is characterised in that：The thickness of the Catalytic Layer is 0.005-
The thickness of 0.5mm, the waterproof ventilative layer are 0.05-2mm, and the waterproof ventilative layer is existed with the transition zone by adhesive
The gas-diffusion electrode of 0.5mm thickness is hot pressed at 30-400 DEG C.
4. a kind of preparation method of the catalyst of gas-diffusion electrode according to claim 1, it is characterised in that：This method
Include the following steps：
(1) carbon support material, active material are mixed and added into deionized water and stirred evenly；
(2) it through high-speed stirred at 10-100 DEG C of constant temperature, then dries through 40-120 DEG C, catalyst fines is ground into after cooling.
5. a kind of preparation method of gas-diffusion electrode according to claim 3, it is characterised in that：
This approach includes the following steps：
(1) transition zone that the afflux conductive mesh that certain, thickness is 0.1-2mm by size is 0.5-3mm with thickness is cold-pressed；
(2) in the catalysis slurry that a face coating thickness of transition zone is 0.005-0.5mm, through 10-100 DEG C of drying and in 20-80
DEG C hot pressing；
(3) another side of the transition zone of step (2) and thickness are cold-pressed into 0.5-2mm thickness for the waterproof ventilative layer of 0.05-0.5mm
Electrode slice, and be fired into gas-diffusion electrode at 30-400 DEG C.
6. a kind of preparation method of gas-diffusion electrode according to claim 3, it is characterised in that：
This approach includes the following steps：
(I) in certain size, the transition zone that the side blade coating thickness for the afflux conductive mesh that thickness is 0.1-2mm is 0.5-3mm is starched
Material is cold-pressed through 10-100 DEG C of drying and in room temperature；
(II) catalyst pulp, coating thickness 0.05-0.5mm are sprayed in the one side of transition zone, then is dried through 10-100 DEG C
It is dry；
(III) another side of the waterproof ventilative layer that thickness is 0.05-0.5mm and the transition zone for coating catalyst pulp is bonded
And it is pressed into the electrode slice of 0.5-2mm thickness, finally gas-diffusion electrode is fired at 30-400 DEG C.
7. a kind of preparation method of the Catalytic Layer spray of gas-diffusion electrode according to claim 1, it is characterised in that：It should
Method includes the following steps：
A) catalyst fines, ptfe emulsion, adhesive and deionized water are weighed；Wherein catalyst material weight hundred
It is 30-50% to divide than content, and ptfe emulsion weight percent content is 5-30%, deionized water 10-40%；Adhesive
30-50%；
B) deionized water is added in catalyst fines and is stirred evenly；
C) other components are added in whipping process, through high-speed stirred at catalyst spraying slurry at 10-100 DEG C.
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2018
- 2018-02-08 CN CN201810126733.8A patent/CN108346807A/en active Pending
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