CN100555723C - The direct methanol fuel cell method for preparing membrane electrode - Google Patents

The direct methanol fuel cell method for preparing membrane electrode Download PDF

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CN100555723C
CN100555723C CNB2008101122123A CN200810112212A CN100555723C CN 100555723 C CN100555723 C CN 100555723C CN B2008101122123 A CNB2008101122123 A CN B2008101122123A CN 200810112212 A CN200810112212 A CN 200810112212A CN 100555723 C CN100555723 C CN 100555723C
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microporous layers
anode
preparation
catalyst
cathode
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CN101281971A (en
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王新东
王同涛
林才顺
苗睿瑛
薛方勤
方勇
叶锋
李晶晶
王永亮
刘芸
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University of Science and Technology Beijing USTB
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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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention discloses a kind of direct methanol fuel cell membrane electrode preparation method, belong to the direct methanol fuel cell field.It is dielectric film that described membrane electrode adopts proton exchange membrane, anode is a platinum ruthenium C catalyst, negative electrode is the platinum C catalyst, by the supporting layer of supporting layer, microporous layers, Catalytic Layer, proton exchange membrane and the cathode side of anode-side, microporous layers, Catalytic Layer totally seven layers of institute form.The preparation technology of described membrane electrode comprises the preparation at end and preparation and the preparation of Catalytic Layer, the preparation of microporous layers slurry and the preparation and the hot pressing of microporous layers of preliminary treatment, catalyst pulp.The invention has the advantages that: the microporous layers and the supporting layer of the preparation of adopting new technology, has higher porosity, reduced the resistance to mass tranfer of membrane electrode, help improving the interface between microporous layers or Catalytic Layer and the supporting layer, thereby improve the three-phase contact area of catalyst and reactant, improved the output power density of battery.

Description

The direct methanol fuel cell method for preparing membrane electrode
Technical field
The present invention relates to a kind of direct methanol fuel cell preparation methods, belong to direct methanol fuel cell film electrode structure and manufacturing technology field.
Background technology
Direct methanol fuel cell (DMFC) is the Blast Furnace Top Gas Recovery Turbine Unit (TRT) that a kind of chemical energy that will be stored in fuel (methyl alcohol) and the oxidant (oxygen or air) is converted into electric energy, its significant advantage is: fuel (methyl alcohol) source is abundant, with low cost, energy density is higher, the direct charging of fuel when battery operated, need not to reform and handle, simple in structure, response time is short, easy to operate, portable and store, be the desirable power source of portable electric appts, mobile phone, video camera and electric automobile, be considered to most possibly realize business-like application.Membrane electrode is to be arranged in order the superimposed body of the stratiform that constitutes by the supporting layer of anode, microporous layers, catalyst layer, Nafion film, the catalyst layer of negative electrode, microporous layers, supporting layer, be the core component of DMFC and the important place that material Transfer, electrochemical reaction take place, its preparation technology directly has influence on the microstructure and the battery performance of membrane electrode.Though a lot of DMFC method for preparing membrane electrode are used for reference from PEMFC and are come, but one of different with the PEMFC membrane electrode catalyst loading height that are the DMFC membrane electrode, Catalytic Layer is relatively very thick, by the supporting layer of supporting layer, microporous layers, Catalytic Layer, proton exchange membrane and the cathode side of anode-side, microporous layers, Catalytic Layer totally seven layers of institute form.Its preparation technology comprises that mainly slurry preparation, proton exchange membrane are handled, technical processs such as slurry applies, electrode sintering, hot pressing.Direct methanol fuel cell generally adopts the carbon paper of process hydrophobic treatment as supporting layer, and carbon paper is a kind of supporting layer of loose structure, and the aperture is generally about 30um.If directly prepare microporous layers and Catalytic Layer, will cause that the carbon granule (aperture is generally about 30nm) of microporous layers and catalyst granules (aperture is generally about 3nm) are along with slurry gos deep into supporting layer on its surface.It has blocked the hole of supporting layer on the one hand, causes the supporting layer porosity to descend, and has hindered the transmission of methyl alcohol, air and product.On the other hand, cause the waste of catalyst, reduced the utilance of catalyst.
Summary of the invention
The object of the present invention is to provide a kind of direct methanol fuel cell membrane electrode preparation method of more optimizing.This membrane electrode has improved the porosity of supporting layer effectively, promoted fuel, oxidant, product carbon dioxide and water in membrane electrode, to transmit, reduced the resistance to mass tranfer of membrane electrode, help improving the utilance of anode and cathode catalyst, improve the interface between microporous layers or Catalytic Layer and the supporting layer, thereby improved the output power density of battery.
The present invention adopts following proposal to be realized.It is dielectric film that this membrane electrode adopts proton exchange membrane, anode is a platinum ruthenium C catalyst, negative electrode is the platinum C catalyst, supporting layer is a carbon paper, by the supporting layer of supporting layer, microporous layers, Catalytic Layer, proton exchange membrane and the cathode side of anode-side, microporous layers, Catalytic Layer totally seven layers of institute form, it is characterized in that, the microporous layers of membrane electrode and Catalytic Layer are after supporting layer is heated to a certain degree, again microporous layers or Catalytic Layer slurry are sprayed onto on the supporting layer with vaporific form, it is condensed in rapidly on the support layer surface, and the infiltration that reduces slurry forms.
Above-mentioned membrane electrode preparation method comprises following process:
1. the preparation of film and preliminary treatment.The Nafion film is the Nafion115 that U.S. Du Pont company produces, and ionic forms is a proton type.This film needed to carry out preliminary treatment before using, to remove the organic substance and the metal ion on film surface, its processing procedure is as follows: is 5%H with the Nafion film of certain size in volume ratio 2O 2Handle 1 hour to remove the organic substance on striping surface for 80 ℃ in the aqueous solution, then put into 80 ℃ redistilled water and handle 1 hour hydrogen peroxide, use 80 ℃ 0.5molL again with washing film surface -1H 2SO 4The aqueous solution is handled inorganic metal ion, inserts then in 80 ℃ the redistilled water and handles 1 hour H with washing film surface 2SO 4, the Nafion film after handling is placed in the redistilled water standby.
2. the preparation of the preparation of catalyst pulp and anode and cathode Catalytic Layer.Anode selects 20-70wt%PtRu/C or PtRublack catalyst to make raw material, and 2-20wt%Nafion solution is made binding agent, and normal propyl alcohol is made dispersant, is mixed into the anode catalyst layer slurry, is uniformly dispersed with ultrasonic cell disruptor is ultrasonic then; The Catalytic Layer slurry is sprayed on the transfer medium, and airing at normal temperatures.Negative electrode selects 20-70wt%Pt/C or Pt black catalyst to make raw material, and 2-20wt%Nafion solution is made binding agent, and normal propyl alcohol prepares anode and cathode catalysis layer slurry as dispersant, is uniformly dispersed with ultrasonic cell disruptor is ultrasonic; The Catalytic Layer slurry is sprayed on the transfer medium, and airing at normal temperatures.The anode and cathode catalyst loading is 1-4mg/cm 2
3. the preparation of microporous layers slurry.The microporous layers slurry generally adopts Vulcan XC-72 carbon black to make main body.Anode micro porous layer adopts the Nafion of 5-30wt% to make binding agent, and isopropyl alcohol or normal propyl alcohol are made dispersant, are made into microporous layers solution, and the slurry concentration proportioning of Vulcan XC-72 carbon black and pure dispersant is 5-25mg/ml.Cathode micro porous layer adopts the PTFE of 5-30wt% to make binding agent, and isopropyl alcohol or normal propyl alcohol are made dispersant, are made into microporous layers solution, and the slurry concentration proportioning of Vulcan XC-72 carbon black and pure dispersant is 5-25mg/ml.
4. the preparation of anode and cathode microporous layers.Adding thermal spray methods, to prepare microporous layers be that the microporous layers slurry is sprayed onto on the supporting layer after the heating (60-140 ℃) with vaporific form, and condense in rapidly on the support layer surface, forms the microporous layers of porous.
5. hot pressing.The dielectric film both sides that place step 1 to handle well the transfer medium that is loaded with the anode and cathode catalyst, at 6-12MPa pressure, 80-150 ℃ following hot pressing 2-5 minute, hot-forming, obtain catalyst and film composite CCM after taking transfer medium off, the anode and cathode supporting layer that has the anode and cathode microporous layers that again step 4 is obtained is put into the both sides of CCM, at 6-12MPa pressure, 80-150 ℃ following hot pressing 2-5 minute, hot pressing obtains the membrane electrodes of seven unifications.
The carbon carrier carrying capacity of microporous layers carbon black is 1-4mg/cm in the step 3 2, the microporous layers pulp solution that is made into needs ultrasonic to even.
What above-mentioned ultrasonic procedure adopted is ultrasonic cell disruptor.
Compared with prior art, electrode of the present invention, method for preparing membrane electrode and membrane electrode performance have the following advantages:
(1) supporting layer has higher porosity.After supporting layer is heated to a certain degree, the microporous layers slurry is sprayed onto on the supporting layer with vaporific form again, it is condensed in rapidly on the support layer surface, the infiltration that reduces slurry forms.
(2) improved the utilance of anode and cathode catalyst.The improvement in supporting layer and microporous layers porosity and aperture has reduced the resistance to mass tranfer of membrane electrode, help improving the interface between microporous layers or Catalytic Layer and the supporting layer, thereby improve the contact area of catalyst and reactant, improve the output power density of battery, prepared the 34.2mW/cm of membrane electrode from original drop-coating 2Bring up to the 75.61mW/cm of present hot spraying method 2(55 ℃, normal pressure).
Description of drawings
The battery performance test operating condition of embodiment 1 to 4: battery temperature is 55 ℃, 1.5M methanol aqueous solution 2.5ml/min charging, and atmospheric air, flow velocity are 670ml/min.
Fig. 1 is the embodiment of the invention 1 a membrane electrode open circuit voltage performance curve.
Fig. 2 is the embodiment of the invention 1 a membrane electrode power density performance curve.
Fig. 3 is the embodiment of the invention 2 membrane electrode open circuit voltage performance curves.
Fig. 4 is the embodiment of the invention 2 membrane electrode power density performance curves.
Fig. 5 is the embodiment of the invention 3 membrane electrode open circuit voltage performance curves.
Fig. 6 is the embodiment of the invention 3 membrane electrode power density performance curves.
Fig. 7 is the embodiment of the invention 4 membrane electrode open circuit voltage performance curves.
Fig. 8 is the embodiment of the invention 4 membrane electrode power density performance curves.
Fig. 9 is the surface topography map of the embodiment of the invention 5 membrane electrodes.
Figure 10 is the cross section microscopic appearance figure of the embodiment of the invention 5 membrane electrodes.
Embodiment
Embodiment 1
1. the preparation of film and preliminary treatment.The Nafion film is the Nafion115 that U.S. Du Pont company produces, and ionic forms is a proton type.This film needed to carry out preliminary treatment before using: the Nafion film of certain size is 5%H in volume ratio 2O 2Handle 1 hour to remove the organic substance on striping surface for 80 ℃ in the aqueous solution, then put into 80 ℃ redistilled water and handle 1 hour hydrogen peroxide, use 80 ℃ 0.5molL again with washing film surface -1H 2SO 4The aqueous solution is handled inorganic metal ion, inserts then in 80 ℃ the redistilled water and handles 1 hour H with washing film surface 2SO 4, the Nafion film after handling is placed in the redistilled water standby.
2. the preparation of the preparation of catalyst pulp and anode and cathode Catalytic Layer.Anode and negative electrode select PtRu black catalyst and Pt Black catalyst to make raw material respectively, and 2%Nafion solution is made binding agent, and normal propyl alcohol prepares anode and cathode catalysis layer slurry as dispersant, is uniformly dispersed with ultrasonic cell disruptor is ultrasonic; The Catalytic Layer slurry is sprayed on the transfer medium, and airing at normal temperatures.The anode and cathode catalyst loading is 1mg/cm 2
3. the preparation of the preparation of microporous layers slurry and anode and cathode microporous layers.The microporous layers slurry generally adopts Vulcan XC-72 carbon black to make main body, and the slurry concentration proportioning is 5mg/ml.Anode micro porous layer adopts that carrying capacity is 1,2,3mg/cm 2The VulcanXC-72 carbon black, the Nafion of 5wt% makes binding agent, isopropyl alcohol is made dispersant, is made into microporous layers solution, and ultrasonic to evenly.Cathode micro porous layer adopts the PTFE of 20wt% to make binding agent, and isopropyl alcohol is made dispersant, is made into microporous layers solution, and ultrasonic to even.Adding thermal spray methods, to prepare microporous layers be that the microporous layers slurry is sprayed onto on the supporting layer that is heated to 70 ℃ with vaporific form, and condense in rapidly on the support layer surface, forms the microporous layers of porous.
4. hot pressing.The dielectric film both sides that place step 1 to handle well the transfer medium that is loaded with the anode and cathode catalyst, hot-forming 6MPa pressure, 130 ℃ of following hot pressing 5 minutes, obtain CCM after taking transfer medium off.The anode and cathode supporting layer that will have the anode and cathode microporous layers is put into the both sides of CCM, and 6MPa pressure, 130 ℃ of following hot pressing 5 minutes, hot pressing obtained the membrane electrodes of seven unifications.
5. the membrane electrode of doing that will the make battery of packing into, battery temperature remains on 50 ℃.Feed atmospheric air and methanol aqueous solution respectively in anode and cathode, after the low discharging current 10h activation, carry out the test of battery performance.
The performance curve of battery illustrates that anode micro porous layer adopts that carrying capacity is 1,2,3mg/cm as shown in Figure 1 and Figure 2 2The VulcanXC-72 carbon black, the Nafion of 20wt% makes binding agent, the membrane electrode voltage performance of preparation is close, power density is 2mg/cm with the carrying capacity 2The highest.
Embodiment 2
1. the preparation of film and preliminary treatment.The Nafion film is the Nafion115 that U.S. Du Pont company produces, and ionic forms is a proton type.This film needed to carry out preliminary treatment before using: the Nafion film of certain size is 5%H in volume ratio 2O 2Handle 1 hour to remove the organic substance on striping surface for 80 ℃ in the aqueous solution, then put into 80 ℃ redistilled water and handle 1 hour hydrogen peroxide, use 80 ℃ 0.5molL again with washing film surface -1H 2SO 4The aqueous solution is handled inorganic metal ion, inserts then in 80 ℃ the redistilled water and handles 1 hour H with washing film surface 2SO 4, the Nafion film after handling is placed in the redistilled water standby.
2. the preparation of the preparation of catalyst pulp and anode and cathode Catalytic Layer.Anode and negative electrode select 20wt%PtRu/C catalyst and 20wt%Pt/C catalyst to make raw material respectively, and 18%Nafion solution is made binding agent, and normal propyl alcohol prepares anode and cathode catalysis layer slurry as dispersant, are uniformly dispersed with ultrasonic cell disruptor is ultrasonic; The Catalytic Layer slurry is sprayed on the transfer medium, and airing at normal temperatures.The anode and cathode catalyst loading is 4mg/cm 2
3. the preparation of the preparation of microporous layers slurry and anode and cathode microporous layers.The microporous layers slurry generally adopts Vulcan XC-72 carbon black to make main body, and the slurry concentration proportioning is 10mg/ml.It is 2mg/cm that anode micro porous layer adopts carrying capacity 2The VulcanXC-72 carbon black, 10,20, the Nafion of 30wt% makes binding agent, normal propyl alcohol is made dispersant, is made into microporous layers solution, and ultrasonic to evenly.Cathode micro porous layer adopts the PTFE of 20wt% to make binding agent, and normal propyl alcohol is made dispersant, is made into microporous layers solution, and ultrasonic about hundreds of times and form.Adding thermal spray methods, to prepare microporous layers be that the microporous layers slurry is sprayed onto on the supporting layer that is heated to 60 ℃ with vaporific form, and condense in rapidly on the support layer surface, forms the microporous layers of porous.
4. hot pressing.The dielectric film both sides that place step 1 to handle well the transfer medium that is loaded with the anode and cathode catalyst, hot-forming 8MPa pressure, 110 ℃ of following hot pressing 4 minutes, obtain CCM after taking transfer medium off.The anode and cathode supporting layer that will have the anode and cathode microporous layers is put into the both sides of CCM, and 8MPa pressure, 110 ℃ of following hot pressing 4 minutes, hot pressing obtained the membrane electrodes of seven unifications.
5. the membrane electrode of doing that will the make battery of packing into, battery temperature remains on 50 ℃.Feed atmospheric air and methanol aqueous solution respectively in anode and cathode, after the low discharging current 10h activation, carry out the test of battery performance.
The performance curve of battery illustrates that it is 2mg/cm that anode micro porous layer adopts carrying capacity as shown in Figure 3, Figure 4 2The VulcanXC-72 carbon black, 10,20, the Nafion of 30wt% makes binding agent, power density was the highest when the membrane electrode of preparation was made binding agent with 20wt%Nafion.
Embodiment 3
1. the preparation of film and preliminary treatment.The Nafion film is the Nafion115 that U.S. Du Pont company produces, and ionic forms is a proton type.This film needed to carry out preliminary treatment before using: the Nafion film of certain size is 5%H in volume ratio 2O 2Handle 1 hour to remove the organic substance on striping surface for 80 ℃ in the aqueous solution, then put into 80 ℃ redistilled water and handle 1 hour hydrogen peroxide, use 80 ℃ 0.5molL again with washing film surface -1H 2SO 4The aqueous solution is handled inorganic metal ion, inserts then in 80 ℃ the redistilled water and handles 1 hour H with washing film surface 2SO 4, the Nafion film after handling is placed in the redistilled water standby.
2. the preparation of the preparation of catalyst pulp and anode and cathode Catalytic Layer.Anode and negative electrode select 40wt%PtRu/C catalyst and 40wt%Pt/C catalyst to make raw material respectively, and 15%Nafion solution is made binding agent, and normal propyl alcohol prepares anode and cathode catalysis layer slurry as dispersant, are uniformly dispersed with ultrasonic cell disruptor is ultrasonic; The Catalytic Layer slurry is sprayed on the transfer medium, and airing at normal temperatures.The anode and cathode catalyst loading is 2mg/cm 2
3. the preparation of the preparation of microporous layers slurry and anode and cathode microporous layers.The microporous layers slurry generally adopts Vulcan XC-72 carbon black to make main body, and the slurry concentration proportioning is 15m/ml.It is 2mg/cm that anode micro porous layer adopts carrying capacity 2The VulcanXC-72 carbon black, the Nafion of 20wt% makes binding agent, normal propyl alcohol is made dispersant, is made into microporous layers solution, and ultrasonic to evenly.Cathode micro porous layer adopts that carrying capacity is 1,2,3mg/cm 2Vulcan XC-72 carbon black, adopt the PTFE of 5wt% to make binding agent, normal propyl alcohol is made dispersant, is made into microporous layers solution, and ultrasonic to evenly.Adding thermal spray methods, to prepare microporous layers be that the microporous layers slurry is sprayed onto on the supporting layer of heating back (100 ℃) with vaporific form, and condense in rapidly on the support layer surface, forms the microporous layers of porous.
4. hot pressing.The dielectric film both sides that place step 1 to handle well the transfer medium that is loaded with the anode and cathode catalyst, hot-forming 10MPa pressure, 90 ℃ of following hot pressing 3 minutes, obtain CCM after taking transfer medium off.The anode and cathode supporting layer that will have the anode and cathode microporous layers is put into the both sides of CCM, and 10MPa pressure, 90 ℃ of following hot pressing 3 minutes, hot pressing obtain the membrane electrodes of seven unifications.
5. the membrane electrode of doing that will the make battery of packing into, battery temperature remains on 50 ℃.Feed atmospheric air and methanol aqueous solution respectively in anode and cathode, after the low discharging current 10h activation, carry out the test of battery performance.
The performance curve of battery such as Fig. 5, shown in Figure 6 illustrate that cathode micro porous layer adopts that carrying capacity is 1,2,3mg/cm 2Vulcan XC-72 carbon black, adopt the PTFE of 20wt% to make binding agent, power density was the highest when the membrane electrode of preparation was 2mg/cm2 with the carrying capacity, voltage performance is best.
Embodiment 4
1. the preparation of film and preliminary treatment.The Nafion film is the Nafion115 that U.S. Du Pont company produces, and ionic forms is a proton type.This film needed to carry out preliminary treatment before using: the Nafion film of certain size is 5%H in volume ratio 2O 2Handle 1 hour to remove the organic substance on striping surface for 80 ℃ in the aqueous solution, then put into 80 ℃ redistilled water and handle 1 hour hydrogen peroxide, use 80 ℃ 0.5molL again with washing film surface -1H 2SO 4The aqueous solution is handled inorganic metal ion, inserts then in 80 ℃ the redistilled water and handles 1 hour H with washing film surface 2SO 4, the Nafion film after handling is placed in the redistilled water standby.
2. the preparation of the preparation of catalyst pulp and anode and cathode Catalytic Layer.Anode and negative electrode select 60wt%PtRu/C catalyst and 60wt%Pt/C catalyst to make raw material respectively, and 10%Nafion solution is made binding agent, and normal propyl alcohol prepares anode and cathode catalysis layer slurry as dispersant, are uniformly dispersed with ultrasonic cell disruptor is ultrasonic; The Catalytic Layer slurry is sprayed on the transfer medium, and airing at normal temperatures.The anode and cathode catalyst loading is 2mg/cm 2
3. the preparation of the preparation of microporous layers slurry and anode and cathode microporous layers.The microporous layers slurry generally adopts Vulcan XC-72 carbon black to make main body, and the slurry concentration proportioning is 18mg/ml.It is 2mg/cm that anode micro porous layer adopts carrying capacity 2The VulcanXC-72 carbon black, the Nafion of 20wt% makes binding agent, normal propyl alcohol is made dispersant, is made into microporous layers solution, and ultrasonic to evenly.It is 2mg/cm that cathode micro porous layer adopts carrying capacity 2Vulcan XC-72 carbon black, adopt 10,20, the PTFE of 30wt% makes binding agent, normal propyl alcohol is made dispersant, is made into microporous layers solution, and ultrasonic to evenly.Adding thermal spray methods, to prepare microporous layers be that the microporous layers slurry is sprayed onto on the supporting layer after the heating (110 ℃) with vaporific form, and condense in rapidly on the support layer surface, forms the microporous layers of porous.
4. hot pressing.The dielectric film both sides that place step 1 to handle well the transfer medium that is loaded with the anode and cathode catalyst, hot-forming 12MPa pressure, 80 ℃ of following hot pressing 2 minutes, obtain CCM after taking transfer medium off.The anode and cathode supporting layer that will have the anode and cathode microporous layers is put into the both sides of CCM, and 12MPa pressure, 80 ℃ of following hot pressing 2 minutes, hot pressing obtained the membrane electrodes of seven unifications.
5. the membrane electrode of doing that will the make battery of packing into, battery temperature remains on 50 ℃.Feed atmospheric air and methanol aqueous solution respectively in anode and cathode, after the low discharging current 10h activation, carry out the test of battery performance.
The performance curve of battery such as Fig. 7, shown in Figure 8 illustrate that it is 2mg/cm that cathode micro porous layer adopts carrying capacity 2The VulcanXC-72 carbon black, adopt 10,20, the PTFE of 30wt% makes binding agent, performance was best when the membrane electrode of preparation was binding agent with 20wt%PTFE.
Embodiment 5
1. the preparation of film and preliminary treatment.The Nafion film is the Nafion115 that U.S. Du Pont company produces, and ionic forms is a proton type.This film needed to carry out preliminary treatment before using: the Nafion film of certain size is 5%H in volume ratio 2O 2Handle 1 hour to remove the organic substance on striping surface for 80 ℃ in the aqueous solution, then put into 80 ℃ redistilled water and handle 1 hour hydrogen peroxide, use 80 ℃ 0.5molL again with washing film surface -1H 2SO 4The aqueous solution is handled inorganic metal ion, inserts then in 80 ℃ the redistilled water and handles 1 hour H with washing film surface 2SO 4, the Nafion film after handling is placed in the redistilled water standby.
2. the preparation of the preparation of catalyst pulp and anode and cathode Catalytic Layer.Anode and negative electrode select PtRu black catalyst and Pt Black catalyst to make raw material respectively, and 5%Nafion solution is made binding agent, and normal propyl alcohol prepares anode and cathode catalysis layer slurry as dispersant, is uniformly dispersed with ultrasonic cell disruptor is ultrasonic; The Catalytic Layer slurry is sprayed on the transfer medium, and airing at normal temperatures.The anode and cathode catalyst loading is 4mg/cm 2
3. the preparation of the preparation of microporous layers slurry and anode and cathode microporous layers.The microporous layers slurry generally adopts Vulcan XC-72 carbon black to make main body, and the slurry concentration proportioning is 20mg/ml.It is 2mg/cm that anode micro porous layer adopts carrying capacity 2The VulcanXC-72 carbon black, the Nafion of 10wt% makes binding agent, isopropyl alcohol is made dispersant, is made into microporous layers solution, and ultrasonic to evenly.It is 2mg/cm that cathode micro porous layer adopts carrying capacity 2Vulcan XC-72 carbon black, adopt the PTFE of 20wt% to make binding agent, isopropyl alcohol is made dispersant, is made into microporous layers solution, and ultrasonic to evenly.Adding thermal spray methods, to prepare microporous layers be that the microporous layers slurry is sprayed onto on the supporting layer after the heating (130 ℃) with vaporific form, and condense in rapidly on the support layer surface, forms the microporous layers of porous.
4. hot pressing.The dielectric film both sides that place step 1 to handle well the transfer medium that is loaded with the anode and cathode catalyst, hot-forming 8MPa pressure, 110 ℃ of following hot pressing 4 minutes, obtain CCM after taking transfer medium off.The anode and cathode supporting layer that will have the anode and cathode microporous layers is put into the both sides of CCM, and 8MPa pressure, 110 ℃ of following hot pressing 4 minutes, hot pressing obtained membrane electrode.The microstructure (SEM figure) that can obtain membrane electrode is as Fig. 9, shown in Figure 10.

Claims (4)

1, a kind of direct methanol fuel cell method for preparing membrane electrode carries out preliminary treatment to the Nafion film, it is characterized in that, comprises following process:
1) preparation of the preparation of catalyst pulp and cathode and anode Catalytic Layer, select 20-70wt%PtRu/C or PtRu black catalyst to make the anode catalyst layer raw material respectively, 20-70wt%Pt/C or Pt black catalyst are made the cathode catalysis layer raw material, adopt 2-20wt%Nafion solution to make binding agent simultaneously, normal propyl alcohol is made dispersant, is mixed into anode and cathode catalysis layer slurry, ultrasonic then being uniformly dispersed, again the Catalytic Layer slurry is sprayed on the transfer medium, and airing at normal temperatures;
2) the moon, the preparation of sun microporous layers, adopt Vulcan XC-72 carbon black to make main body, anode micro porous layer adopts the Nafion of 5-30wt% to make binding agent, isopropyl alcohol or normal propyl alcohol are made dispersant, be made into the microporous layers pulp solution, cathode micro porous layer adopts the PTFE of 5-30wt% to make binding agent, isopropyl alcohol or normal propyl alcohol are made dispersant, be made into the microporous layers pulp solution, the slurry concentration proportioning of microporous layers Vulcan XC-72 carbon black and pure dispersant is 5-25mg/ml, the microporous layers slurry is sprayed onto on the supporting layer that is heated to after 60-140 ℃ with vaporific form, and condenses in rapidly on the support layer surface, form the microporous layers of porous;
3) carry out hot pressing, the transfer medium that is loaded with the cathode and anode catalyst is placed pretreated Nafion dielectric film both sides, at 6-12MPa pressure, 80-150 ℃ following hot pressing 2-5 minute, hot-forming, obtain catalyst and film composite CCM after taking transfer medium off, the cathode and anode supporting layer that will have the cathode and anode microporous layers is put into the both sides of CCM, and at 6-12MPa pressure, 80-150 ℃ following hot pressing 2-5 minute, hot pressing obtains the membrane electrodes of seven unifications.
2, direct methanol fuel cell method for preparing membrane electrode as claimed in claim 1 is characterized in that step 2) in the carbon carrier carrying capacity of yin, yang microporous layers Vulcan XC-72 carbon black be 1-4mg/cm 2
3, direct methanol fuel cell method for preparing membrane electrode as claimed in claim 1 is characterized in that, to step 2) in the microporous layers pulp solution that is made into carry out ultrasonic to evenly.
4, as claim 1 or 3 described direct methanol fuel cell method for preparing membrane electrode, it is characterized in that ultrasonic employing ultrasonic cell disruptor.
CNB2008101122123A 2008-05-21 2008-05-21 The direct methanol fuel cell method for preparing membrane electrode Expired - Fee Related CN100555723C (en)

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