CN107369838A - It is a kind of to exempt from hot pressing combination electrode and preparation method thereof for DMFC - Google Patents
It is a kind of to exempt from hot pressing combination electrode and preparation method thereof for DMFC Download PDFInfo
- Publication number
- CN107369838A CN107369838A CN201710485275.2A CN201710485275A CN107369838A CN 107369838 A CN107369838 A CN 107369838A CN 201710485275 A CN201710485275 A CN 201710485275A CN 107369838 A CN107369838 A CN 107369838A
- Authority
- CN
- China
- Prior art keywords
- combination electrode
- substrate
- layer
- hot pressing
- dmfc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- 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
- H01M4/8882—Heat treatment, e.g. drying, baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Composite Materials (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Exempt from hot pressing combination electrode and preparation method thereof for DMFC the invention discloses a kind of.The electrode includes integrated flow field diffusion layer and Catalytic Layer；The integrated flow field diffusion layer includes substrate and packed layer；The substrate is the metallic fiber with porosity gradient or metal powder sintered porous plate in a thickness direction；The packed layer is attached to the less one side of substrate porosity and part space interior；The Catalytic Layer is attached to the surface of packed layer；The present invention is used for the preparation method for exempting from hot pressing combination electrode of DMFC, comprises the following steps：（1）The preparation of substrate；（2）The preparation of packed layer；（3）The preparation of integrated flow field diffusion layer；（4）The preparation of Catalytic Layer；（5）The preparation of combination electrode.The present invention proposes flow field and diffusion layer integration system is standby, eliminates individually processing and flow field preparation technology, simplifies the preparation technology of battery key component membrane electrode, possess the characteristics of efficient, inexpensive.
Description
Technical field
It is especially a kind of to exempt from hot pressing combination electrode for DMFC the present invention relates to fuel cell field
And preparation method thereof.
Background technology
Instantly, energy crisis is increasingly severe, and traditional chemical energy source is present that environmental pollution is big, energy utilization rate is low
Etc. disadvantage, under such a background, fuel cell shows its distinctive advantage：Environmental protection, cleaning, and can be directly by chemical energy
Endlessly it is converted into electric energy.DMFC（DMFC）It is a kind of electric as the fuel of raw material using methanol and oxygen
Pond, have structure is relatively easy, easy to make, energy density is high, fuel is easy to transport and stores and the advantage such as comparatively safe, into
For the focus that each scientific research institution, each major company are studied both at home and abroad nearly ten years.
DMFC structure composition mainly includes end plate, collector plate, flow-field plate and membrane electrode, and membrane electrode is subdivided into spreading
Layer, Catalytic Layer and PEM.In traditional each component process for machining and manufacturing, flow-field plate is needed in metal or stone mostly
It is individually formed on black plate by techniques such as machining, punching presses.For the mainstream machining processes of membrane electrode, diffusion layer is general
Using materials such as the carbon paper of close and distant water process or carbon cloths, microporous layers are prepared on top layer；And or Catalytic Layer is attached in microporous layers,
It is attached on PEM, then the hot pressing under certain temperature and pressure, forms membrane electrode assembly.This flow field and expansion
Scattered layer be manufactured separately and each component of membrane electrode by hot pressing and the processing mode that is formed so that the whole work of DMFC processing and manufacturings
Skill process is complex, and process time is longer, expends more human and material resources and financial resources.In cell assembling processes, flow-field plate
It is again the plate-shaped member being separately separated with membrane electrode, is forced into a certain degree by make-up machinery power, is contacted with this to reduce
Resistance, but this contact resistance still account for larger portion in overall electrical resistance, so as to increase the energy loss of battery.
The content of the invention
In order to solve the problems, such as that each parts machinings of DMFC or preparation technology are lengthy and tedious, so as to simplify processing step, reduce and add
Work manufacturing cost, exempt from hot pressing combination electrode and preparation method thereof for DMFC the invention provides a kind of.
For DMFC, flow field, diffusion layer and Catalytic Layer have strong influence to battery performance.
The present invention's exempts from hot pressing combination electrode first by traditional flow-field plate for being separately separated, being compressed by Automatic manual transmission and diffusion laminated two
For one, integrated flow field diffusion layer is prepared.Integrated flow field diffusion layer is porous, on the basis of three-dimensional structure, spraying catalysis
Layer slurry, forms the Catalytic Layer of high-specific surface area, so as to form flow field-diffusion layer-Catalytic Layer combination electrode, simplifies battery knot
Structure, while significantly reducing parts resistance itself and contact resistance, the management of reactant and product can be preferably carried out, is had
Beneficial to lifting battery performance.
The present invention is achieved through the following technical solutions.
It is a kind of to exempt from hot pressing combination electrode, including integrated flow field diffusion layer and catalysis for DMFC
Layer；
The integrated flow field diffusion layer includes substrate and packed layer；The substrate is to have porosity gradient in a thickness direction
Metallic fiber or metal powder sintered porous plate；The packed layer is attached in the less one side of substrate porosity and part
Portion space；
The Catalytic Layer is attached to the surface of packed layer.
Further, the hot pressing combination electrode of exempting from directly exempts from hot pressing when for DMFC by described
Combination electrode is placed in the ladder hole among the collector plate of DMFC, and Catalytic Layer side is close to exchange
Film.
Further, the thickness of the substrate is 1 ~ 2mm.
Further, the substrate in a thickness direction, has the porosity gradient in 60 ~ 90% ranges.
Further, the material of the metallic fiber or metal dust is preferably copper or stainless steel.
Further, the hot pressing combination electrode of exempting from for DMFC includes anode combination electrode or the moon
Pole combination electrode.
Further, in the anode combination electrode, substrate has hydrophily, and the material of packed layer is conductive black
And perfluorinated sulfonic acid（Nafion）Mixture, the mass ratio of conductive black and perfluorinated sulfonic acid is 20:1~4:1.
Further, in the negative electrode combination electrode, substrate has hydrophobicity, and the material of packed layer is conductive black
And polytetrafluoroethylene (PTFE)（PTFE）Mixture, the mass ratio of conductive black and polytetrafluoroethylene (PTFE) is 10:1~1:1.
Further, the material of the Catalytic Layer is catalyst and perfluorinated sulfonic acid（Nafion）Mixture, and catalyst
Mass ratio with perfluorinated sulfonic acid is 5:1~1:1.
Prepare a kind of method for exempting from hot pressing combination electrode for DMFC described in any of the above-described, tool
Body comprises the following steps：
（1）The preparation of substrate：According to the order of porosity gradual change, by the metallic fiber of different porosities or metal powder sintered more
Orifice plate alignment is overlayed in pressure mould, is placed in heat preservation sintering in sintering furnace, is obtained blocking complex sintered fiber or porous plate, is obtained
To the substrate；
（2）The preparation of packed layer：By solution mixture and the dispersant of filling layer material, be uniformly dispersed after obtain packed layer
Slurry, substrate is placed on heating platform and is heated to the boiling point temperatures above of dispersant, by packed layer slurry uniformly blade coating or
It is sprayed on the less side of substrate porosity, dispersant and solvent volatilization in slurry, the packed layer adhered in substrate；
（3）The preparation of integrated flow field diffusion layer：The substrate for being attached with packed layer is subjected to Heat preservation processing, obtains described one
Fluidized flow field diffusion layer；
（4）The preparation of Catalytic Layer：By the solution mixture for being catalyzed layer material and dispersant, it is uniformly dispersed, obtains Catalytic Layer
Slurry, integrated flow field diffusion layer is positioned on heating platform and is heated to the boiling point temperatures above of dispersant, by Catalytic Layer
Slurry even application dispersant and solvent volatilization in slurry, obtains the Catalytic Layer on packed layer；
（5）The preparation of combination electrode：The integrated flow field diffusion that preparation has Catalytic Layer is placed in vacuum drying chamber and done
Dry processing, obtain described exempting from hot pressing combination electrode for DMFC.
Further, step（1）In, the heat preservation sintering is 300 ~ 500 DEG C of insulations under hydrogen or argon gas protection atmosphere
Sinter 0.5 ~ 2h.
Further, step（1）In, when preparing the substrate of anode combination electrode, to the blocking complex sintered fiber of acquisition
Or porous plate carries out hydrophilic treated, that is, obtain the substrate of anode combination electrode.
Further, step（1）In, when preparing the substrate of negative electrode combination electrode, to the blocking complex sintered fiber of acquisition
Or porous plate carries out hydrophobic treatment, that is, obtain the substrate of negative electrode combination electrode.
Further, step（2）In, the preparation of packed layer slurry, specifically include：Conductive black, dispersant and
Nafion solution is well mixed, and anode packed layer slurry is made；Conductive black, dispersant and PTFE emulsion are well mixed, made
Into negative electrode packed layer slurry；
After dispersant and solvent volatilization, residual conductive carbon black and Nafion form anode filling in the substrate of anode combination electrode
Layer, residual conductive carbon black and PTFE form negative electrode packed layer in the substrate of negative electrode combination electrode；The solvent includes water.
Further, step（3）In, Heat preservation processing is after being incubated 0.5 ~ 1h at 250 ~ 300 DEG C, then heats up
0.5 ~ 1h is incubated to 350 ~ 400 DEG C.
Further, step（2）、（4）In, the dispersant includes isopropanol；The effect of dispersant is packed layer
Material or catalysis layer material are uniformly dispersed, in favor of blade coating or spray process.
Further, step（4）In, after dispersant and solvent volatilization, residual catalyst and Nafion form Catalytic Layer, institute
Catalyst is stated using the general catalyst of DMFC, including Platinum series catalyst.
Packed layer and Catalytic Layer are prepared by the processing mode for scratching or spraying, wherein most of raw material of packed layer
Into the part space interior of substrate, and the equal very little of residue particle diameter of packed layer and Catalytic Layer surface attaching portion, it is
Nano grade, therefore the very thin thickness that packed layer and Catalytic Layer are formed, the thickness for integrally exempting from hot pressing combination electrode remain essentially as
Substrate thickness rank.
Further, step（5）In, the drying process is 1 ~ 2h of boiling point temperatures above drying in dispersant.
Compared with prior art, the invention has the advantages that and beneficial effect：
（1）In the preparation method of the present invention, it is proposed that flow field and diffusion layer integration system are standby, by the metal with porosity gradient
Fiber or metal powder sintered porous plate are as flow field, while the substrate as diffusion layer again, prepare integrated flow field diffusion
Layer, eliminate individually processing or prepare the processing step in flow field, simplify DMFC processing and manufacturing flow；
（2）When exempting from hot pressing combination electrode in DMFC of the present invention, it is placed directly within direct methanol fuel electricity
In ladder hole among the collector plate in pond, and directly compressed with PEM by assembly force, without hot pressing, simplify electricity
The preparation technology of pond key component-membrane electrode, possesses the characteristics of efficient, inexpensive；
（3）The present invention makees using with porosity gradient and the metallic fiber of parent/hydrophobic performance or metal powder sintered porous plate
For electrode basement, the porous plate constant compared to traditional perforated plate and porosity gradient, preferably reactant and product can be entered
Row management.
Brief description of the drawings
Fig. 1 is that the present invention exempts from the assembling schematic diagram that hot pressing combination electrode is used for DMFC；
Fig. 2 is that layer cross section signal is spread in the integrated flow field in embodiment 1 with three blocks of sintered porous plates of porosity gradual change form
Figure；
Fig. 3 is to be equipped with traditional hot pressing electrode with exempting from the battery performance comparison diagram of hot pressing combination electrode in embodiment 1.
Embodiment
To further understand the present invention, technical solution of the present invention is made further specifically below in conjunction with drawings and examples
It is bright, but the invention is not restricted to this.
The present invention is a kind of to exempt from hot pressing combination electrode for DMFC, including integrated flow field diffusion layer and
Catalytic Layer；Integrated flow field diffusion layer includes substrate and packed layer；
Substrate in a thickness direction with porosity gradient metallic fiber or metal powder sintered porous plate, metallic fiber or
The material of metal dust is copper or stainless steel, and the thickness of substrate is 1 ~ 2mm；Substrate in a thickness direction, has 60 ~ 90%
The porosity gradient of range；
Packed layer is attached to the less one side of substrate porosity and part space interior；
Hot pressing combination electrode of exempting from for DMFC includes anode combination electrode or negative electrode combination electrode；Anode is answered
In composite electrode, substrate has a hydrophily, and the material of packed layer is the mixture of conductive black and perfluorinated sulfonic acid, conductive black and
The mass ratio of perfluorinated sulfonic acid is 20:1~4:1；In negative electrode combination electrode, substrate has hydrophobicity, and the material of packed layer is conduction
The mass ratio of the mixture of carbon black and polytetrafluoroethylene (PTFE), conductive black and polytetrafluoroethylene (PTFE) is 10:1~1:1；
Catalytic Layer is attached to the surface of packed layer, and the material of Catalytic Layer is catalyst and the mixture of perfluorinated sulfonic acid, and catalyst
Mass ratio with perfluorinated sulfonic acid is 5:1~1:1.
The hot pressing combination electrode of exempting from of the present invention is used for the assembling schematic diagram of DMFC as shown in figure 1, by electricity
The side in pond is to opposite side, successively including anode end cap 1, anode gel sealing gasket 2-1, anode collector plate 3-1, anode polytetrafluoro
Ethene pad 4-1, PEM 5, negative electrode teflon gasket 4-2, cathode collector plate 3-2, negative electrode silica gel sealing pad 2-2
With cathode end plate 6, exempt from hot pressing combination electrode and be placed directly within the ladder hole among the collector plate of DMFC, its
In, anode combination electrode 7-1 is placed directly within the ladder hole among the anode collector plate 3-1 of DMFC, cloudy
Pole combination electrode 7-2 is placed directly within the ladder hole among the cathode collector plate 3-2 of DMFC, and compound
The Catalytic Layer side of electrode is close to PEM 5.
Embodiment 1
The present embodiment is the integrated flow field diffusion layer with three blocks of sintered porous plates of copper of porosity gradual change form, and its section is illustrated
Figure is as shown in Figure 2.Wherein, three blocks of sintered porous plates of copper include porous plate 8, porous plate 9 and porous plate 10 successively, and three blocks of sintering are more
The porosity of orifice plate is followed successively by 90%, 80% and 70%, forms the porous plate that blocking thickness is 1 mm；Packed layer 11 is attached to porous
The side of plate 10 and its part space interior.
The material of negative electrode packed layer is mass ratio 5:1 conductive black and the mixture of polytetrafluoroethylene (PTFE), anode packed layer
Material be mass ratio 10:1 conductive black and the mixture of perfluorinated sulfonic acid；
The material of Catalytic Layer is mass ratio 3:1 catalyst and the mixture of perfluorinated sulfonic acid, Catalytic Layer adhere to packed layer in fig. 2
11 surface, a kind of exempt from hot pressing combination electrode for DMFC so as to be formed.
The hot pressing combination electrode of exempting from of the present embodiment is assemblied in DMFC with traditional hot pressing electrode,
Enter the test of line output voltage, power density, test result such as Fig. 3 institutes under 4 mol/L methanol concentration, normal temperature and pressure conditionses
Show；From the figure 3, it may be seen that the maximum output voltage and maximum power density of the battery for exempting from the assembling of hot pressing combination electrode of the present embodiment connect
Closely, and the present embodiment exempt from hot pressing combination electrode for flow field and diffusion layer integration, be placed directly within DMFC
Collector plate among ladder hole in, and directly compressed with PEM by assembly force, can be preferably right without hot pressing
Reactant and product are managed.
Embodiment 2
The present embodiment is the integrated flow field diffusion layer with three blocks of sintered porous plates of copper of porosity gradual change form.Wherein, three pieces
The porosity of sintered porous plate is followed successively by 85%, 75% and 65%, forms the porous plate that blocking thickness is 1.5 mm, packed layer attachment
In the side of the porous plate of porosity 65% and its part space interior.
The material of negative electrode packed layer is mass ratio 10:1 conductive black and the mixture of polytetrafluoroethylene (PTFE), anode packed layer
Material be mass ratio 5:1 conductive black and the mixture of perfluorinated sulfonic acid；
The material of Catalytic Layer is mass ratio 1:1 catalyst and the mixture of perfluorinated sulfonic acid, Catalytic Layer are attached to the table of packed layer
Face, a kind of exempt from hot pressing combination electrode for DMFC so as to be formed.
The hot pressing combination electrode of exempting from of the present embodiment is applied to direct methanol fuel cell, is placed directly within direct methanol fuel electricity
In ladder hole among the collector plate in pond, and directly compressed with PEM by assembly force, can be preferably without hot pressing
Reactant and product are managed.
Embodiment 3
The present embodiment is the integrated flow field diffusion layer with two blocks of sintered porous plates of copper of porosity gradual change form.Three blocks of sintering are more
The porosity of orifice plate is followed successively by 80%, 70% and 60%, forms the porous plate that blocking thickness is 2 mm, and packed layer is attached to porosity
The side of 60% porous plate and its part space interior.
The material of negative electrode packed layer is mass ratio 20:1 conductive black and the mixture of polytetrafluoroethylene (PTFE), anode packed layer
Material be mass ratio 1:1 conductive black and the mixture of perfluorinated sulfonic acid；
The material of Catalytic Layer is mass ratio 5:1 catalyst and the mixture of perfluorinated sulfonic acid, Catalytic Layer are attached to the table of packed layer
Face, a kind of exempt from hot pressing combination electrode for DMFC so as to be formed.
The hot pressing combination electrode of exempting from of the present embodiment is applied to direct methanol fuel cell, is placed directly within direct methanol fuel electricity
In ladder hole among the collector plate in pond, and directly compressed with PEM by assembly force, can be preferably without hot pressing
Reactant and product are managed.
Embodiment 4
A kind of preparation method for exempting from hot pressing combination electrode for DMFC, comprise the following steps：
（1）It is prepared by substrate：It is 0.5mm by three pieces of thickness according to the order of porosity gradual change, porosity is respectively 60%, 70%
The sintered porous plate of copper with 80% is alignd overlay in pressure mould successively, and mould is put into the sintering with atmosphere protection
0.5h is incubated at 300 DEG C in stove, obtains blocking compound porous plate；
After blocking compound porous plate is cleaned up, NaOH is immersed in（Concentration is 3mol/L）And K2S2O8（Concentration is 0.2mol/
L）Deionized water solution in 5min, carry out hydrophilic treated, take out, deionized water cleaning, air-dry, obtain anode substrate；
After blocking compound porous plate is cleaned up, NaOH is immersed in（Concentration is 3mol/L）And K2S2O8（Concentration is 0.2mol/
L）Deionized water solution in 5min, take out, deionized water cleaning, air-dry；Then 500 in the resistance furnace with hydrogen shield
2h is incubated at DEG C, is immersed in after taking-up in 0.01mol/L stearic acid ethanol solutions 3 days, carries out hydrophobic treatment, is taken out, acetone is clear
Wash clean, air-dry, obtain cathode substrate；
（2）It is prepared by packed layer：By the Nafion solution of conductive black, isopropanol dispersant and mass fraction 5% according to mass ratio 1：
20：1 uniformly mixing, is made anode slurry；
By the PTFE emulsion of conductive black, isopropanol dispersant and mass fraction 40% according to mass ratio 4：80：1 uniformly mixing, system
Into cathode slurry；
Substrate is placed on heating platform and is heated to 85 DEG C, by slurry even application to the less side of substrate porosity, slurry
In dispersant and solvent volatilization；
After dispersant and solvent volatilization, residual conductive carbon black and Nafion form anode packed layer, negative electrode base in anode substrate
Residual conductive carbon black and PTFE form negative electrode packed layer on bottom；
（3）It is prepared by integrated flow field diffusion layer：By the substrate for being attached with packed layer under hydrogen shield atmosphere, it is incubated at 250 DEG C
0.5h, then be warming up at 350 DEG C and be incubated 0.5h, obtain the flow field diffusion layer of integration；
（4）It is prepared by Catalytic Layer：By the Nafion solution of catalyst, isopropanol and mass fraction 5%, according to mass ratio 1：20：4 is mixed
Close, ink shape slurry is made, integrated flow field diffusion layer is placed on heating platform and is heated to 85 DEG C, by slurry even application
Onto packed layer, the isopropyl alcohol and solvent volatilization in slurry, catalyst and Nafion are left, obtains Catalytic Layer；
（5）It is prepared by combination electrode：The integrated flow field diffusion layer that preparation has Catalytic Layer is put into vacuum drying chamber, at 85 DEG C
1h is dried, respectively obtains anode combination electrode and negative electrode combination electrode.
The hot pressing combination electrode of exempting from prepared is applied to direct methanol fuel cell, is placed directly within DMFC
In ladder hole among collector plate, and directly compressed with PEM by assembly force, can be preferably right without hot pressing
Reactant and product are managed.
Embodiment 5
A kind of preparation method for exempting from hot pressing combination electrode for DMFC, comprise the following steps：
（1）It is prepared by substrate：It is 0.5mm by three pieces of thickness according to the order of porosity gradual change, porosity is respectively 60%, 70%
The sintered porous plate of copper with 80% is alignd overlay in pressure mould successively, and mould is put into the sintering with atmosphere protection
1h is incubated at 400 DEG C in stove, obtains blocking compound porous plate；
After blocking compound porous plate is cleaned up, NaOH is immersed in（Concentration is 1mol/L）And K2S2O8（Concentration is 0.05mol/
L）Deionized water solution in 30min, carry out hydrophilic treated, take out, deionized water cleaning, air-dry, obtain anode substrate；
After blocking compound porous plate is cleaned up, NaOH is immersed in（Concentration is 1mol/L）And K2S2O8（Concentration is 0.05mol/
L）Deionized water solution in 30min, take out, deionized water cleaning, air-dry；Then in the resistance furnace with hydrogen shield
0.5h is incubated at 300 DEG C, is immersed in after taking-up in 0.01mol/L stearic acid ethanol solutions 1 day, carries out hydrophobic treatment, is taken out, third
Ketone cleans up, and air-dries, obtains cathode substrate；
（2）It is prepared by packed layer：By the Nafion solution of conductive black, isopropanol dispersant and mass fraction 5% according to mass ratio 1：
20：2 uniformly mixing, are made anode slurry；
By the PTFE emulsion of conductive black, isopropanol dispersant and mass fraction 40% according to mass ratio 2：40：1 uniformly mixing, system
Into cathode slurry；
Substrate is placed on heating platform and is heated to 85 DEG C, by slurry even application to the less side of substrate porosity, slurry
In dispersant and solvent volatilization；
After dispersant and solvent volatilization, residual conductive carbon black and Nafion form anode packed layer, negative electrode base in anode substrate
Residual conductive carbon black and PTFE form negative electrode packed layer on bottom；
（3）It is prepared by integrated flow field diffusion layer：By the substrate for being attached with packed layer under hydrogen shield atmosphere, it is incubated at 275 DEG C
0.75h, then be warming up at 375 DEG C and be incubated 0.75h, obtain the flow field diffusion layer of integration；
（4）It is prepared by Catalytic Layer：By the Nafion solution of catalyst, isopropanol and mass fraction 5%, according to mass ratio 1：20：8 is mixed
Close, ink shape slurry is made, integrated flow field diffusion layer is placed on heating platform and is heated to 85 DEG C, by slurry even application
Onto packed layer, the isopropyl alcohol and solvent volatilization in slurry, catalyst and Nafion are left, obtains Catalytic Layer；
（5）It is prepared by combination electrode：The integrated flow field diffusion layer that preparation has Catalytic Layer is put into vacuum drying chamber, at 85 DEG C
1h is dried, respectively obtains anode combination electrode and negative electrode combination electrode.
The hot pressing combination electrode of exempting from prepared is applied to direct methanol fuel cell, is placed directly within DMFC
In ladder hole among collector plate, and directly compressed with PEM by assembly force, can be preferably right without hot pressing
Reactant and product are managed.
Embodiment 6
A kind of preparation method for exempting from hot pressing combination electrode for DMFC, comprise the following steps：
（1）It is prepared by substrate：It is 0.5mm by three pieces of thickness according to the order of porosity gradual change, porosity is respectively 60%, 70%
The sintered porous plate of copper with 80% is alignd overlay in pressure mould successively, and mould is put into the sintering with atmosphere protection
2h is incubated at 500 DEG C in stove, obtains blocking compound porous plate；
After blocking compound porous plate is cleaned up, NaOH is immersed in（Concentration is 2mol/L）And K2S2O8（Concentration is 0.1mol/
L）Deionized water solution in 60min, carry out hydrophilic treated, take out, deionized water cleaning, air-dry, obtain anode substrate；
After blocking compound porous plate is cleaned up, NaOH is immersed in（Concentration is 2mol/L）And K2S2O8（Concentration is 0.1mol/
L）Deionized water solution in 60min, take out, deionized water cleaning, air-dry；Then in the resistance furnace with hydrogen shield
1h is incubated at 400 DEG C, is immersed in after taking-up in 0.005mol/L stearic acid ethanol solutions 2 days, carries out hydrophobic treatment, is taken out, third
Ketone cleans up, and air-dries, obtains cathode substrate；
（2）It is prepared by packed layer：By the Nafion solution of conductive black, isopropanol dispersant and mass fraction 5% according to mass ratio 1：
20：5 uniformly mixing, are made anode slurry；
By the PTFE emulsion of conductive black, isopropanol dispersant and mass fraction 40% according to mass ratio 2：40：5 uniformly mixing, system
Into cathode slurry；
Substrate is placed on heating platform and is heated to 85 DEG C, by slurry even application to the less side of substrate porosity, slurry
In dispersant and solvent volatilization；
After dispersant and solvent volatilization, residual conductive carbon black and Nafion form anode packed layer, negative electrode base in anode substrate
Residual conductive carbon black and PTFE form negative electrode packed layer on bottom；
（3）It is prepared by integrated flow field diffusion layer：By the substrate for being attached with packed layer under hydrogen shield atmosphere, it is incubated at 300 DEG C
1h, then be warming up at 400 DEG C and be incubated 1h, obtain the flow field diffusion layer of integration；
（4）It is prepared by Catalytic Layer：By the Nafion solution of catalyst, isopropanol and mass fraction 5%, according to mass ratio 1：20：20 is mixed
Close, ink shape slurry is made, integrated flow field diffusion layer is placed on heating platform and is heated to 85 DEG C, by slurry even application
Onto packed layer, the isopropanol volatilization in slurry, catalyst and Nafion are left, obtains Catalytic Layer；
（5）It is prepared by combination electrode：The integrated flow field diffusion layer that preparation has Catalytic Layer is put into vacuum drying chamber, at 85 DEG C
2h is dried, respectively obtains anode combination electrode and negative electrode combination electrode.
The hot pressing combination electrode of exempting from prepared is applied to direct methanol fuel cell, is placed directly within DMFC
In ladder hole among collector plate, and directly compressed with PEM by assembly force, can be preferably right without hot pressing
Reactant and product are managed.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description
Other various forms of changes or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all the present invention
All any modification, equivalent and improvement made within spirit and principle etc., should be included in the protection of the claims in the present invention
Within the scope of.
Claims (10)
1. a kind of exempt from hot pressing combination electrode for DMFC, it is characterised in that is spread including integrated flow field
Layer and Catalytic Layer；
The integrated flow field diffusion layer includes substrate and packed layer；The substrate is to have porosity gradient in a thickness direction
Metallic fiber or metal powder sintered porous plate；The packed layer is attached in the less one side of substrate porosity and part
Portion space；
The Catalytic Layer is attached to the surface of packed layer；
The hot pressing combination electrode of exempting from for DMFC includes anode combination electrode or negative electrode combination electrode.
A kind of exempt from hot pressing combination electrode for DMFC 2. according to claim 1, it is characterised in that
It is described when exempting from hot pressing combination electrode and being used for DMFC, the hot pressing combination electrode of exempting from directly is placed in direct methanol
In ladder hole among the collector plate of fuel cell, and Catalytic Layer side is close to PEM.
A kind of exempt from hot pressing combination electrode for DMFC 3. according to claim 1, it is characterised in that
The thickness of the substrate is 1 ~ 2mm；The substrate in a thickness direction, has the porosity gradient in 60 ~ 90% ranges；
The material of the metallic fiber or metal dust is copper or stainless steel.
A kind of exempt from hot pressing combination electrode for DMFC 4. according to claim 1, it is characterised in that
In the anode combination electrode, substrate has hydrophily, and the material of packed layer is the mixture of conductive black and perfluorinated sulfonic acid,
The mass ratio of conductive black and perfluorinated sulfonic acid is 20:1~4:1.
A kind of exempt from hot pressing combination electrode for DMFC 5. according to claim 1, it is characterised in that
In the negative electrode combination electrode, substrate has hydrophobicity, and the material of packed layer is the mixing of conductive black and polytetrafluoroethylene (PTFE)
The mass ratio of thing, conductive black and polytetrafluoroethylene (PTFE) is 10:1~1:1.
A kind of exempt from hot pressing combination electrode for DMFC 6. according to claim 1, it is characterised in that
The material of the Catalytic Layer is the mixture of catalyst and perfluorinated sulfonic acid, and the mass ratio of catalyst and perfluorinated sulfonic acid is 5:1~1:
1。
7. prepare a kind of side for exempting from hot pressing combination electrode for DMFC described in any one of claim 1 ~ 6
Method, it is characterised in that specifically comprise the following steps：
（1）The preparation of substrate：According to the order of porosity gradual change, by the metallic fiber of different porosities or metal powder sintered more
Orifice plate alignment is overlayed in pressure mould, is placed in heat preservation sintering in sintering furnace, is obtained blocking complex sintered fiber or porous plate, is obtained
To the substrate；
（2）The preparation of packed layer：By solution mixture and the dispersant of filling layer material, be uniformly dispersed after obtain packed layer
Slurry, substrate is placed on heating platform and is heated to dispersant boiling point temperatures above, by uniformly blade coating or the spray of packed layer slurry
It is coated in the less side of substrate porosity, dispersant and solvent volatilization in slurry, the packed layer adhered in substrate；
（3）The preparation of integrated flow field diffusion layer：The substrate for being attached with packed layer is subjected to Heat preservation processing, obtains described one
Fluidized flow field diffusion layer；
（4）The preparation of Catalytic Layer：By the solution mixture for being catalyzed layer material and dispersant, it is uniformly dispersed, obtains Catalytic Layer
Slurry, integrated flow field diffusion layer is positioned on heating platform and is heated to dispersant boiling point temperatures above, Catalytic Layer is starched
Even application is expected to packed layer, dispersant and solvent volatilization in slurry, obtains the Catalytic Layer；
（5）The preparation of combination electrode：The integrated flow field diffusion that preparation has Catalytic Layer is placed in vacuum drying chamber and done
Dry processing, obtain described exempting from hot pressing combination electrode for DMFC.
8. a kind of preparation method for exempting from hot pressing combination electrode for DMFC according to claim 7,
Characterized in that, step（1）In, the heat preservation sintering is 300 ~ 500 DEG C of heat preservation sinterings 0.5 under hydrogen or argon gas protection atmosphere
~2h；When preparing the substrate of anode combination electrode, hydrophilic treated is carried out to the blocking complex sintered fiber or porous plate of acquisition, i.e.,
Obtain the substrate of anode combination electrode；When preparing the substrate of negative electrode combination electrode, to the blocking complex sintered fiber or more of acquisition
Orifice plate carries out hydrophobic treatment, that is, obtains the substrate of negative electrode combination electrode.
9. a kind of preparation method for exempting from hot pressing combination electrode for DMFC according to claim 7,
Characterized in that, step（3）In, Heat preservation processing is after being incubated 0.5 ~ 1h at 250 ~ 300 DEG C, then it is warming up to 350 ~
0.5 ~ 1h is incubated at 400 DEG C.
10. a kind of preparation method for exempting from hot pressing combination electrode for DMFC according to claim 7,
Characterized in that, step（2）、（4）In, the dispersant includes isopropanol；Step（5）In, the drying process is scattered
The boiling point temperatures above of agent dries 1 ~ 2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710485275.2A CN107369838B (en) | 2017-06-23 | 2017-06-23 | Hot-pressing-free composite electrode for direct methanol fuel cell and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710485275.2A CN107369838B (en) | 2017-06-23 | 2017-06-23 | Hot-pressing-free composite electrode for direct methanol fuel cell and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107369838A true CN107369838A (en) | 2017-11-21 |
| CN107369838B CN107369838B (en) | 2020-09-22 |
Family
ID=60304965
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710485275.2A Active CN107369838B (en) | 2017-06-23 | 2017-06-23 | Hot-pressing-free composite electrode for direct methanol fuel cell and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107369838B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112838234A (en) * | 2019-11-22 | 2021-05-25 | 西部金属材料股份有限公司 | Metal fiber flow field and metal fiber gas diffusion layer integrated sintered bipolar plate |
| EP3958360A1 (en) * | 2020-08-18 | 2022-02-23 | Paul Scherrer Institut | Hybrid structured porous transport electrodes with electrochemically active top-layer |
| CN114540851A (en) * | 2022-02-17 | 2022-05-27 | 武汉理工大学 | Novel anode diffusion layer and proton exchange membrane water electrolytic cell |
| CN114865028A (en) * | 2022-05-05 | 2022-08-05 | 大连理工大学 | Method for adjusting hydrophobicity of integrated membrane electrode of fuel cell and application |
| WO2023006202A1 (en) * | 2021-07-29 | 2023-02-02 | Paul Scherrer Institut | Hybrid structured porous transport electrodes with electrochemically active top-layer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1658422A (en) * | 2005-03-23 | 2005-08-24 | 武汉理工大学 | Gas diffusion layer for fuel cell and its preparation method |
| WO2010107429A1 (en) * | 2009-03-18 | 2010-09-23 | Utc Power Corporation | Fuel cell for moisture management at gas inlets |
| CN102024961A (en) * | 2010-11-29 | 2011-04-20 | 新源动力股份有限公司 | Gaseous diffusion layer of proton exchange membrane fuel cell and preparation method thereof |
| US20160064755A1 (en) * | 2013-04-30 | 2016-03-03 | Aktiengesellschaft | Self-wetting membrane electrode unit and fuel cell having such a unit |
-
2017
- 2017-06-23 CN CN201710485275.2A patent/CN107369838B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1658422A (en) * | 2005-03-23 | 2005-08-24 | 武汉理工大学 | Gas diffusion layer for fuel cell and its preparation method |
| WO2010107429A1 (en) * | 2009-03-18 | 2010-09-23 | Utc Power Corporation | Fuel cell for moisture management at gas inlets |
| CN102024961A (en) * | 2010-11-29 | 2011-04-20 | 新源动力股份有限公司 | Gaseous diffusion layer of proton exchange membrane fuel cell and preparation method thereof |
| US20160064755A1 (en) * | 2013-04-30 | 2016-03-03 | Aktiengesellschaft | Self-wetting membrane electrode unit and fuel cell having such a unit |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112838234A (en) * | 2019-11-22 | 2021-05-25 | 西部金属材料股份有限公司 | Metal fiber flow field and metal fiber gas diffusion layer integrated sintered bipolar plate |
| CN112838234B (en) * | 2019-11-22 | 2022-03-11 | 西部金属材料股份有限公司 | Metal fiber flow field and metal fiber gas diffusion layer integrated sintered bipolar plate |
| EP3958360A1 (en) * | 2020-08-18 | 2022-02-23 | Paul Scherrer Institut | Hybrid structured porous transport electrodes with electrochemically active top-layer |
| WO2023006202A1 (en) * | 2021-07-29 | 2023-02-02 | Paul Scherrer Institut | Hybrid structured porous transport electrodes with electrochemically active top-layer |
| CN114540851A (en) * | 2022-02-17 | 2022-05-27 | 武汉理工大学 | Novel anode diffusion layer and proton exchange membrane water electrolytic cell |
| CN114865028A (en) * | 2022-05-05 | 2022-08-05 | 大连理工大学 | Method for adjusting hydrophobicity of integrated membrane electrode of fuel cell and application |
| CN114865028B (en) * | 2022-05-05 | 2024-04-16 | 大连理工大学 | Method for adjusting hydrophobicity of integrated membrane electrode of fuel cell and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107369838B (en) | 2020-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107369838A (en) | It is a kind of to exempt from hot pressing combination electrode and preparation method thereof for DMFC | |
| CN110148759B (en) | Preparation method of high-current-density-oriented proton exchange membrane fuel cell gas diffusion layer | |
| CN101557001B (en) | Fuel cell film electrode and preparation method thereof | |
| CN106784943A (en) | A kind of membrane electrode of fuel batter with proton exchange film of high power density and preparation method thereof | |
| CN101800321B (en) | Method for preparing membrane electrode for hydrophilicity and hydrophobicity-adjustable proton exchange membrane fuel battery on the basis of catalyst/membrane technology | |
| CN110459774A (en) | A kind of preparation method of fuel cell membrane electrode | |
| CN100515566C (en) | Production method of catalyst coating film | |
| CN1988225A (en) | Gas diffusion layer for proton exchanging film fuel cell and its preparing method | |
| CN100405641C (en) | Electrode production of fuel battery membrane with proton exchange membrane | |
| CN101552342B (en) | Method of compositely manufacturing proton exchange membrane fuel cell bipolar plate and membrane electrode assembly | |
| CN111063925B (en) | Catalyst coated membrane, fuel cell and method of making | |
| CN101000967A (en) | Membrane electrode of protone exchange membrane fuel cell and preparation method thereof | |
| CN102496726B (en) | Preparation method and forming fixture of membrane electrode of proton exchange membrane fuel cell | |
| EP2461401A1 (en) | Gas diffusion layer member for solid polymer fuel cells, and solid polymer fuel cell | |
| CN1330026C (en) | Technique for mfg. two-polar plates of proton exchange film fuel cell | |
| CN106785241A (en) | Metal air battery cathodes and preparation method thereof | |
| CN102104155A (en) | Low-platinum cathode catalyst layer used for fuel cell and application thereof | |
| CN101587953A (en) | The process for hydrophobicizing of a kind of fuel cell porous basic unit | |
| CN102074715B (en) | Double-effect membrane electrode for integrated regenerative fuel cell and preparation method thereof | |
| CN103985888B (en) | The preparation method of ceramic membrane fuel cells connecting material film and electrolytic thin-membrane | |
| CN102522570A (en) | Method for preparing enhanced membrane electrode (MEA) of proton exchange membrane fuel cell (PEMFC) | |
| CN103474683B (en) | Improve membrane electrode assembly of integral type regenerative fuel cell performance and preparation method thereof | |
| KR20080105255A (en) | Method for manufacturing 5-layer mea | |
| CN105161729A (en) | Miniature direct methanol fuel cell membrane electrode and preparation method thereof | |
| CN102723509B (en) | Proton conductors, membrane electrode and preparation thereof is tieed up based on 3 of nanofiber array structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |