CN107611452A - A kind of preparation method of the membrane electrode containing three-dimensional hydrophobic cathode catalysis layer - Google Patents
A kind of preparation method of the membrane electrode containing three-dimensional hydrophobic cathode catalysis layer Download PDFInfo
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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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
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Abstract
The invention discloses a kind of preparation method of the membrane electrode containing three-dimensional hydrophobic cathode catalysis layer.Method uses high platinum content catalyst and ultra-thin PEM, by adding three-dimensional structure auxiliary agent and lyophobic dust in cathode catalysis layer, is prepared for the high-performance containing three-dimensional hydrophobic cathode catalysis layer, high power density membrane electrode.Cathode catalysis layer constructs the three-dimensional structure of Catalytic Layer by adding CNT etc. in the present invention, improves catalysis layer porosity and catalyst utilization, the transmittability for improving gas diffusibility and electronics；And the lyophobic dust added can be effectively improved the water management of negative electrode, particularly under high current density, effectively water caused by cathode reaction can discharge, guarantee cathode reaction gas can be diffused into cathode catalysis layer and catalyst reacts with smooth.Preparation method step of the present invention is simple, and feasibility is strong, and practical easy to operate, cost is low；The small volume of membrane electrode, easily light weight, preparation, it is possible to achieve the large-scale production of membrane electrode.
Description
Technical field
The present invention relates to Proton Exchange Membrane Fuel Cells field, and in particular to a kind of film electricity containing three-dimensional hydrophobic cathode catalysis layer
The preparation method of pole.
Background technology
Proton Exchange Membrane Fuel Cells（PEMFC）It is a kind of green energy resource that chemical energy is directly converted into electric energy, it has
Have the advantages that under transformation efficiency high and low temperature quickly to start, be pollution-free, having on portable electric appts and power vehicle extensive
Application prospect.Membrane electrode（MEA）It is the core component of Proton Exchange Membrane Fuel Cells, is urged by anode gas diffusion layer, anode
Change layer, PEM, cathode catalysis layer and cathode gas diffusion layer composition, the performance of membrane electrode and directly decide fuel cell
Performance, prepare high-performance high power density membrane electrode for fuel cell commercialization progress it is significant.
Because the oxidation of the reduction ratio hydrogen of oxygen is much more difficult, generates and discharge in negative electrode plus water, on negative electrode
The diffusion of gas and water, and the discharge of water simultaneously be present.Therefore the structure of cathode catalysis layer and performance are for fuel cell
Performance has highly important influence.
Membrane electrode catalytic layer is the place to chemically react, and the utilization rate and reacting gas of catalyst are in Catalytic Layer
The performance of diffusion couple membrane electrode has a great impact.If catalyst can not be utilized completely, then may result in catalyst
Waste, it is difficult to the performance of membrane electrode is got a promotion.Caused electronics can not be conducted in time in same course of reaction, with
And reacting gas can not diffuse in time in Catalytic Layer with catalyst reaction, also can limited reactions progress.Improve Catalytic Layer
The utilization rate of middle catalyst, to improve in Catalytic Layer the conducting power of electronics and promote diffusion of the reacting gas in Catalytic Layer be very
Significant research work.Reaction generation water in other membrane electrode cathode Catalytic Layer, if caused water is not discharged in time, just
Water logging phenomenon can be produced, causes catalyst activity to reduce, cathode reaction gas diffusion hindered, particularly under high current density,
So that membrane electrode performance is greatly lowered.Membrane electrode cathode water management is also the focus that everybody studies in recent years, to pass through
Effective manner improves negative electrode water management, prevents the generation of water logging phenomenon, improves the performance of membrane electrode.
Chinese patent application 200710125266.9 discloses a kind of " fuel cell membrane electrode and preparation method thereof ", and this is special
Gas diffusion layers in profit include a carbon nano-tube thin-film structure, and the carbon nano-tube thin-film structure includes at least one CNT
Layer, and the CNT in the carbon nanotube layer is arranged of preferred orient in the same direction.The carbon nano-tube film is as microporous layers
A large amount of uniform and regular distribution microcellular structures can be formed, and there is great specific surface area, this structure can be effective
Equably diffusion reaction gas and fuel.The resistivity of the other carbon nano-tube film is low, can effectively conduct electronics.But
The patent application is merely related in microporous layers（Diffusion layer）Middle addition CNT, this kind of thing is added without regard in catalyst layer
Matter.
Chinese patent application 201410358042.2 discloses " fuel cell membrane electrode ", and the gas used in the patent expands
Dissipating layer includes a carbon-fiber film, and the carbon-fiber film includes multiple CNTs and multiple graphite flakes, and the CNT joins end to end
And extension formation one is membranaceous in the same direction, each CNT is surrounded by multiple graphite flakes, and each graphite flake is received with carbon
Shape is at an angle between the outer wall of mitron.This gas diffusion layers increase the specific surface area of carbon-fiber film, improve gas expansion
The ability of the uniform diffusion reaction gas of layer is dissipated, and the resistivity of carbon-fiber film is smaller, improves gas diffusion conduction electronics
Ability, further increase the chemical properties such as the reactivity of fuel cell membrane electrode.The patent application also only pertains only to
Carbon fiber is added in gas diffusion layers, is not related to Catalytic Layer.
Chinese patent application 201310353990.2 discloses " used in proton exchange membrane fuel cell catalyst, its preparation side
Method and Proton Exchange Membrane Fuel Cells ", the catalyst carrier used in the patent are received for activated carbon, CNT and helical form carbon
More than the one or more in mitron, the catalyst prepared can form three-dimensional network-like structure, have continuous reaction
Thing/product transmission channel, proton migrating channels and electronics conduction pathway, not only improve electronic conductivity, can also improve
Mass transfer effect, reduce every polarization loss.Catalytic Layer is prepared using the catalyst using carbon nanotube carrier, tasted in the presence of thin
The problem of water-based and porosity is unadjustable.
Chinese patent application 99112826.5 discloses " thin-layer hydrophobic catalyst electrode, the system of three-in-one membrane electrode assembly
Preparation Method ", the carbon dust that addition lyophobic dust such as PTFE is handled during the patent is proposed toward cathode catalysis layer, add hydrophobicity thing
Be advantageous to form gas passage in electrode catalyst layer after matter, be advantageous to the expansion of reacting gas or product gas in Catalytic Layer
Dissipate.The method that application proposes can play preferable effect, but the carbon dust for preparing PTFE processing is cumbersome, regulates and controls Catalytic Layer
Porosity is also relatively difficult.
Chinese patent application 200810228028.5 discloses " a kind of preparation method of thin hydrophobisation layer ", the patent
It is middle that catalyst and hydrophober are modulated into ink, then spray on resistance to thermal medium, carry out high-temperature roasting and realize hydrophobisation；Roasting
Spray proton conductor polymer again afterwards and realize electrode three-dimensional.Membrane electrode prepared by this method has good hydrophobic duct,
The water logging phenomenon of fuel cell high current density region is avoided, performance is greatly improved.But the patent application, which is design, urges
Change in layer and add lyophobic dust, without the utilization rate that can improve catalyst well.
Chinese patent application 201610717402.2 discloses " the compound Multilayer Film Electrode of hydrophilic/hydrophobic and its preparation side
Method ", patented invention cathode catalysis layer is the three-layer composite structure with hydrophilic gradient, and one layer close to proton membrane is parent
Water modified layer, the side close to gas diffusion layers is hydrophobically modified layer, is unmodified layer among two layers, hydrophilic layer can be in low phase
To playing moisture-keeping function to PEM and Catalytic Layer intermediate ion polymer under humidity, so as to reduce the ionic conduction of membrane electrode
Resistance, and hydrophobic layer reduces the capillary pressure gradient between Catalytic Layer and gas diffusion layers, it is suppressed that under high relative humidity
Water is spread from diffusion layer to Catalytic Layer, and the invention can reach the purpose of water distribution in optimization Catalytic Layer.But prepare compound
Multilayer Film Electrode process is somewhat complicated, also improves the preparation cost of membrane electrode.
Although above-mentioned report, which is recognized, constructs the importance with good hydrophobic cathode catalysis layer, and has done some
Attempt, but these methods still suffer from the weak point of many, the utilization rate of catalyst still needs into one in membrane electrode catalytic layer
Step improves, and the conducting power of electronics needs to continue to improve in Catalytic Layer, the water pipe of the diffusion of reacting gas and negative electrode in Catalytic Layer
Reason still be present, cause membrane electrode of fuel batter with proton exchange film to reach high in the case of low platinum carrying capacity
The impact of performance.So the research for membrane electrode catalytic layer and water management needs further to be improved, especially to membrane electrode cathode
The research of Catalytic Layer.
The content of the invention
In order to solve the defects of existing correlation technique is present and deficiency, the present invention proposes a kind of containing three-dimensional hydrophobic negative electrode
The preparation method of the membrane electrode of Catalytic Layer, the Catalytic Layer have high catalyst utilization, excellent electronic conduction ability, efficiently
Reacting gas diffusivity and product water transmittability.
On the one hand the three-dimensional structure auxiliary agent added in Catalytic Layer of the present invention can construct the three-dimensional structure of Catalytic Layer, improve catalysis
The utilization rate of agent and the diffusion of reacting gas；On the other hand by the three-dimensional structure auxiliary agent added has low resistivity, energy
Enough improve the conducting power of electronics in Catalytic Layer；And the lyophobic dust added in Catalytic Layer can be effectively improved cathode catalysis layer
Water management capabilities, further lifted Catalytic Layer reacting gas diffusivity.It can be used as the cathode catalysis layer of membrane electrode, Neng Gouji
The performance of the earth lifting membrane electrode simultaneously simplifies making step and manufacturing process.
The purpose of the present invention is realized at least through one of following technical scheme.
A kind of preparation method of the membrane electrode containing three-dimensional hydrophobic cathode catalysis layer, comprises the following steps：
（1）PEM is successively pre-processed with deionized water, hydrogen peroxide and sulfuric acid；
（2）Three-dimensional structure auxiliary agent is pre-processed；
（3）Carbon supported platinum catalyst, perfluorinated sulfonic acid polymer, three-dimensional structure auxiliary agent, lyophobic dust and effumability solvent are pressed
10:2-4:0.1-2:0.1-0.5:After 500-1500 mass ratio mixing, black aqueous solution is dispersed into after ultrasonic oscillation,
The black aqueous solution is coated in cathode catalysis layer of the PEM side as membrane electrode again, then by coated proton
Exchange membrane is heat-treated 20-40 minutes at 40-60 DEG C, that is, the cathode catalysis layer containing three dimensional hydrophobic is made；The negative electrode is urged
It is 0.1-0.3mgPtcm to change active component Pt carrying capacity in layer-2；
（4）Carbon supported platinum catalyst, perfluorinated sulfonic acid polymer and effumability solvent are pressed 10:2-4:500-1500 mass ratio mixes
After conjunction, black aqueous solution is dispersed into after ultrasonic oscillation, the solution is coated in through step（3）Proton exchange after processing
The opposite side of film, coated PEM is then heat-treated 20-40 minutes at 40-60 DEG C, the sun of membrane electrode is made
Pole Catalytic Layer；Pt carrying capacity is controlled in 0.05-0.15mgPtcm in the anode catalyst layer-2；
（5）Carbon paper is immersed water delivery processing is carried out in ptfe emulsion；
（6）Carbon dust, ptfe emulsion, effumability solvent are pressed 10:1-3:500-1500 mass ratio mixing, ultrasound
Ripple concussion is dispersed into black aqueous solution, and the solution is coated to the side of the carbon paper by silicic acid anhydride, the total amount of carbon material
Control is in 2.0-4.0 mg cm-2, coated carbon paper is heat-treated 20-40 minutes at 40-60 DEG C, in 300-400 after drying
1-3 hours are calcined at DEG C, cathode gas diffusion layer is made；
（7）Carbon dust, ptfe emulsion and effumability solvent are pressed 10:1-3:500-1500 mass ratio mixing, ultrasound
Ripple concussion is dispersed into black aqueous solution, the solution is coated to the side of the carbon paper by silicic acid anhydride, by coated carbon
Paper is heat-treated 20-40 minutes at 40-60 DEG C, is calcined 1-3 hours after drying at 300-400 DEG C, and anodic gas diffusion is made
Layer；
（8）Will be through（6）With（7）Two gas diffusion layers after processing are fitted in through step respectively（4）Proton after processing
The both sides of exchange membrane, that is, anode and cathode Catalytic Layer, the membrane electrode of gas diffusion layers is made.
In the above method, described PEM is the perfluorinated sulfonic resin film of the micron thickness of thickness 20-100.
In the above method, the effumability solvent is one or more of distilled water, ethanol, isopropanol.
In the above method, the perfluorinated sulfonic acid polymer includes Nafion212 or Nafion211 PEMs.
In the above method, it is fine that the three-dimensional structure auxiliary agent includes CNT, azotized carbon nano pipe, carbon fiber or carbonitride
Dimension；The three-dimensional structure additive dosage is the 1.0%-20.0% of cathode catalysis layer quality.
In the above method, step（2）In, it is described three-dimensional structure auxiliary agent is subjected to pretreatment to comprise the following steps：
Three-dimensional structure auxiliary agent is placed in acetone, 8-12 hours are stirred under normal temperature, are placed on 0.1-2mol L after filtering again-1
Sulfuric acid solution in, under conditions of 50-70 degrees Celsius stir 8-12 hours remove the metal ion that may poison catalyst layer, mistake
Filter and be washed with deionized to neutrality, drying.
In the above method, step（3）In, while three-dimensional structure auxiliary agent is added in cathode catalysis layer, add hydrophobicity
Material, the lyophobic dust include polytetrafluoroethylene (PTFE)（PTFE）Emulsion, Kynoar（PVDF）Emulsion or fluorocarbon resin；Institute
The addition for stating lyophobic dust is the 1-5% of cathode catalysis layer quality.
The present invention compared with prior art, has advantages below：
1. three-dimensional structure auxiliary agent of the present invention and lyophobic dust are direct add in cathode inks with urging
Agent slurry is well mixed, and three-dimensional structure auxiliary agent is added in cathode catalysis layer can construct the three-dimensional structure of Catalytic Layer,
The utilization rate of catalyst is improved, the conducting power of electronics is lifted and promotes the diffusion of reacting gas；And add lyophobic dust can
To effectively improve the water management of negative electrode, water caused by negative electrode is discharged, the active, anti-of cathode catalysis layer catalyst can be ensured
Answer gas is smooth to diffuse to Catalytic Layer, so as to improve the performance of membrane electrode, especially the membrane electrode performance in high current density area；
2. the membrane electrode high-performance prepared by the present invention is embodied in：On the one hand the addition of three-dimensional structure auxiliary agent improves catalyst
Utilization rate, promote the diffusion of reacting gas；On the other hand because three-dimensional structure auxiliary agent has low resistivity, it is possible to increase catalysis
The conducting power of electronics improves the utilization rate of catalyst, promotes the diffusion of gas in layer；In high current density area, have and dredge
Caused water can rapidly be transferred to gas diffusion layers and discharge by water-based cathode catalysis layer, while accelerate reacting gas to expand
It is dissipated in Catalytic Layer and participates in reaction, under the synergy of both three-dimensional structure auxiliary agent and lyophobic dust, reaches and improve film electricity
The purpose of pole output performance；
3. the present invention is simple to operation toward the method for addition three-dimensional structure auxiliary agent and lyophobic dust in cathode catalysis layer, it is not necessary to
By special, cumbersome operating procedure；
4. the monocell performance that membrane electrode of the present invention is assembled is good, under conditions of operating voltage is 0.6-0.7V, electricity
Current density is not added with the membrane electrode of three-dimensional structure auxiliary agent and lyophobic dust apparently higher than cathode catalysis layer；In high current density
Area, the more obvious membrane electrode that three-dimensional structure auxiliary agent and lyophobic dust are not added better than cathode catalysis layer of its performance.
Brief description of the drawings
Fig. 1 be the membrane electrode that is prepared to embodiment 3 of embodiment 1 and blank membrane electrode prepared by comparative example hydrogen-
Air cell temperature is 70 degrees Celsius, and anode and cathode back pressure is 30psi, and the monocell polarization curve under relative humidity is 100% contrasts
Figure；
The blank membrane electrode prepared by membrane electrode and comparative example that Fig. 2 is prepared for embodiment 1 to embodiment 3 is in hydrogen-air
Battery temperature is 70 degrees Celsius, and anode and cathode back pressure is 30psi, and relative humidity is the monocell power density comparison diagram under 100%.
Embodiment
The goal of the invention of the present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, embodiment is not
It can repeat one by one herein, but therefore embodiments of the present invention are not defined in following examples.Unless stated otherwise, it is of the invention
The material and processing method used is the art conventional material and processing method.
Embodiment 1
The first step takes 4cm × 4cm Nafion211 PEMs, is initially positioned in deionized water 80 DEG C and handles 2 hours, so
It is placed in mass percentage concentration afterwards to handle 2 hours for 80 DEG C in 5% hydrogen peroxide, after distilling water washing, in 0.5mol L-1Sulfuric acid
Handled 2 hours at 80 DEG C in solution, then with distilled water washes clean.The Nafion membrane handled well is placed in and prepares membrane electrode
Fixed on mould, active region size is 5cm2, to prevent film contraction distortion during catalyst pulp is sprayed；
CNT is put into acetone by second step, is stirred 10 hours under normal temperature, CNT is placed in into 1mol/L again after filtering
Sulfuric acid solution in, stirred 10 hours under conditions of 60 degrees Celsius, filter and CNT is washed with deionized to neutrality, dry
It is dry；
3rd step presses 10:3:1:0.3:1000 mass ratio weighs the Pt/C catalyst that 4.2 mg Pt contents are 60% respectively
（Johnson Matthey）, 25.2mg perfluorinated sulfonic acid polymer solution（5wt% Nafion, DuPont）, 0.42mg carbon nanometers
Pipe, 2.52mg ptfe emulsions（Mass fraction is 5%）And 0.42g isopropanols, it is dispersed into and urges through ultrasonic oscillation after mixing
Agent slurry, under infrared light irradiation, the side coated in PEM, then it is heat-treated 30 minutes, that is, makes at 50 DEG C
Cathode catalysis layer is obtained, wherein Pt carrying capacity is 0.2 mg cm-1；
4th step presses 10:3:1000 mass ratio weighs the Pt/C catalyst that 2.1mg Pt contents are 60% respectively（Johnson
Matthey）, 12.6mg perfluorinated sulfonic acid polymer solution（5wt% Nafion, DuPont）And 0.21g isopropanols, through super after mixing
Sound wave shock is dispersed into catalyst pulp, under infrared light irradiation, coated in the 4th step spraying complete PEM it is another
Side, then coated PEM is heat-treated 30 minutes at 50 DEG C, the anode catalyst layer of membrane electrode is made, wherein
Pt carrying capacity is 0.1mg cm-1；
TGP-H-60 carbon papers are cut into the cm of 2.5 cm × 2.5 fritter by the 5th step, are placed in acetone and handle 2 hours, with except
Surface organic matter impurity is removed, dries and is soaked 15 minutes after in the ptfe emulsion that mass percentage concentration is 10%, is dried,
Polytetrafluoroethylene (PTFE) is accounted for the 10% of whole carbon paper weight, be calcined 2 hours at 350 DEG C, polytetrafluoroethylene (PTFE) is sintered in carbon paper,
Complete the water delivery processing of carbon paper；
6th step presses 10:2:1000 mass ratio weighs 37.5mg XC-72 carbon dusts, 150mg ptfe emulsions respectively（Matter
It is 5% to measure fraction）And 3.75g aqueous isopropanols, black aqueous solution is dispersed into through ultrasonic oscillation after mixing, the solution is applied
To the side of the carbon paper Jing Guo silicic acid anhydride, coated carbon paper is toasted 30 minutes at 50 DEG C, after drying at 350 DEG C
Roasting 2 hours, gas diffusion layers are made；
Two gas diffusion layers sprayed through the 6th step are fitted in and have sprayed anode and cathode catalysis through the 3rd step by the 7th step respectively
The both sides of the PEM of layer, that is, membrane electrode is made.
Membrane electrode is placed in monocell, is 70 degree in battery temperature, under conditions of anode and cathode humidification completely, activation process
6 hours, electric discharge repeatedly made it fully activate, and battery performance test condition is as follows：Fuel gas is hydrogen, and oxidant is air,
Battery temperature is 70 DEG C, and anode and cathode back pressure is 30psi, and anode and cathode relative humidity is 100%.
Be 70 degree in battery temperature, anode and cathode relative humidity under conditions of 100%, cell polarization curves as shown in figure 1,
When voltage is 0.7V and 0.6V, current density can respectively reach 1000mAcm-2With 1450 mA cm-2.Monocell power is close
Line write music as shown in Fig. 2 maximum power density is 872mWcm-2。
Embodiment 2
Except cathode catalysis layer slurry presses 10:3:1:1000 mass ratio come weigh Pt contents be 60% Pt/C catalyst, perfluor sulphur
Outside acid polymer, CNT and isopropanol（Do not add polytetrafluoroethylene (PTFE)）, other steps are identical with example 1, cell activation side
Formula and method of testing are identical with example 1.Cell polarization curves are as shown in figure 1, when voltage is 0.7V and 0.6V, electric current
Density can respectively reach 800mAcm-2 And 1300mAcm-2.Monocell power density curve is as shown in Fig. 2 maximum power density is
801mWcm-2。
Embodiment 3
Except cathode catalysis layer slurry presses 10:3:0.3:1000 mass ratio come weigh Pt contents be 60% Pt/C catalyst, perfluor
Outside sulfonic acid polymer, ptfe emulsion and isopropanol（Do not add CNT）, other steps are identical with example 1, battery
Activation method and method of testing are identical with example 1.Cell polarization curves are as shown in figure 1, be 0.7V and 0.6V in voltage
When, current density can respectively reach 800mAcm-2 And 1300mAcm-2.Monocell power density curve is as shown in Fig. 2 maximum work
Rate density is 808mWcm-2。
Embodiment 4
Except cathode catalysis layer slurry presses 10:3:0.1:0.3:1000 mass ratio come weigh Pt contents be 60% Pt/C catalyst,
Outside perfluorinated sulfonic acid polymer, CNT, polytetrafluoroethylene (PTFE) and isopropanol, other steps are identical with example 1.
Embodiment 5
Except cathode catalysis layer slurry presses 10:3:2:0.3:1000 mass ratio weighs Pt/C catalyst that Pt contents are 60%, complete
Outside perfluorinated sulfonic acid polymer, CNT, polytetrafluoroethylene (PTFE) and isopropanol, other steps are identical with example 1.
Embodiment 6
Except cathode catalysis layer slurry presses 10:3:1:0.1:1000 mass ratio weighs Pt/C catalyst that Pt contents are 60%, complete
Outside perfluorinated sulfonic acid polymer, CNT, polytetrafluoroethylene (PTFE) and isopropanol, other steps are identical with example 1.
Embodiment 7
Except cathode catalysis layer slurry presses 10:3:1:0.5:1000 mass ratio weighs Pt/C catalyst that Pt contents are 60%, complete
Outside perfluorinated sulfonic acid polymer, CNT, polytetrafluoroethylene (PTFE) and isopropanol, other steps are identical with example 1.
Embodiment 8
Except cathode catalysis layer slurry presses 10:3:1:0.3:1000 mass ratio weighs Pt/C catalyst that Pt contents are 20%, complete
Outside perfluorinated sulfonic acid polymer, CNT, polytetrafluoroethylene (PTFE) and isopropanol, other steps are identical with example 1.
Embodiment 9
Except cathode catalysis layer slurry presses 10:3:1:0.3:1000 mass ratio weighs Pt/C catalyst that Pt contents are 40%, complete
Outside perfluorinated sulfonic acid polymer, CNT, polytetrafluoroethylene (PTFE) and isopropanol, other steps are identical with example 1.
Comparative example
Except cathode catalysis layer slurry presses 10:3:1000 mass ratio come weigh Pt contents be 60% Pt/C catalyst, perfluorinated sulfonic acid
Outside polymer and isopropanol（Do not add CNT and ptfe emulsion）, other steps are identical with example 1.
Cell activation mode and method of testing are identical with example 1.Cell polarization curves as shown in figure 1, be in voltage
During 0.7V and 0.6V, current density can respectively reach 700 mA cm-2 With 1100 mA cm-2.Monocell power density curve is such as
Shown in Fig. 2, maximum power density is 712mW cm-2。
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 (7)
1. a kind of preparation method of the membrane electrode containing three-dimensional hydrophobic cathode catalysis layer, it is characterised in that comprise the following steps：
（1）PEM is successively pre-processed with deionized water, hydrogen peroxide and sulfuric acid；
（2）Three-dimensional structure auxiliary agent is pre-processed；
（3）Carbon supported platinum catalyst, perfluorinated sulfonic acid polymer, three-dimensional structure auxiliary agent, lyophobic dust and effumability solvent are pressed
10:2-4:0.1-2:0.1-0.5:After 500-1500 mass ratio mixing, black aqueous solution is dispersed into after ultrasonic oscillation,
The black aqueous solution is coated in cathode catalysis layer of the PEM side as membrane electrode again, then by coated proton
Exchange membrane is heat-treated 20-40 minutes at 40-60 DEG C, that is, the cathode catalysis layer containing three dimensional hydrophobic is made；The negative electrode is urged
It is 0.1-0.3mgPtcm to change active component Pt carrying capacity in layer-2；
（4）Carbon supported platinum catalyst, perfluorinated sulfonic acid polymer and effumability solvent are pressed 10:2-4:500-1500 mass ratio mixes
After conjunction, black aqueous solution is dispersed into after ultrasonic oscillation, the solution is coated in through step（3）Proton exchange after processing
The opposite side of film, coated PEM is then heat-treated 20-40 minutes at 40-60 DEG C, the sun of membrane electrode is made
Pole Catalytic Layer；Pt carrying capacity is controlled in 0.05-0.15mgPtcm in the anode catalyst layer-2；
（5）Carbon paper is immersed water delivery processing is carried out in ptfe emulsion；
（6）Carbon dust, ptfe emulsion, effumability solvent are pressed 10:1-3:500-1500 mass ratio mixing, ultrasound
Ripple concussion is dispersed into black aqueous solution, and the solution is coated to the side of the carbon paper by silicic acid anhydride, the total amount of carbon material
Control is in 2.0-4.0 mg cm-2, coated carbon paper is heat-treated 20-40 minutes at 40-60 DEG C, in 300-400 after drying
1-3 hours are calcined at DEG C, cathode gas diffusion layer is made；
（7）Carbon dust, ptfe emulsion and effumability solvent are pressed 10:1-3:500-1500 mass ratio mixing, ultrasound
Ripple concussion is dispersed into black aqueous solution, the solution is coated to the side of the carbon paper by silicic acid anhydride, by coated carbon
Paper is heat-treated 20-40 minutes at 40-60 DEG C, is calcined 1-3 hours after drying at 300-400 DEG C, and anodic gas diffusion is made
Layer；
（8）Will be through（6）With（7）Two gas diffusion layers after processing are fitted in through step respectively（4）Proton after processing
The both sides of exchange membrane, that is, anode and cathode Catalytic Layer, the membrane electrode of gas diffusion layers is made.
2. the method for preparing membrane electrode according to claim 1 containing three-dimensional hydrophobic cathode catalysis layer, it is characterised in that institute
The PEM stated is the perfluorinated sulfonic resin film of the micron thickness of thickness 20-100.
3. the method for preparing membrane electrode according to claim 1 containing three-dimensional hydrophobic cathode catalysis layer, it is characterised in that institute
Effumability solvent is stated as one or more of distilled water, ethanol, isopropanol.
4. the method for preparing membrane electrode according to claim 1 containing three-dimensional hydrophobic cathode catalysis layer, it is characterised in that institute
Stating perfluorinated sulfonic acid polymer includes Nafion212 or Nafion211 PEMs.
5. prepared by the membrane electrode according to claim 1 containing three-dimensional hydrophobic cathode catalysis layer, it is characterised in that described three
Tieing up structural promoter includes CNT, azotized carbon nano pipe, carbon fiber or nitridation carbon fiber；The three-dimensional structure additive dosage
For the 1.0%-20.0% of cathode catalysis layer quality.
6. prepared by the membrane electrode according to claim 1 containing three-dimensional hydrophobic cathode catalysis layer, step（2）In, it is described to incite somebody to action
Three-dimensional structure auxiliary agent carries out pretreatment and comprised the following steps：
Three-dimensional structure auxiliary agent is placed in acetone, 8-12 hours are stirred under normal temperature, are placed on 0.1-2mol L after filtering again-1's
In sulfuric acid solution, 8-12 hours are stirred under conditions of 50-70 degrees Celsius, filters and is washed with deionized to neutrality, drying.
7. the method for preparing membrane electrode according to claim 1 containing three-dimensional hydrophobic cathode catalysis layer, it is characterised in that step
Suddenly（3）In, the lyophobic dust includes polytetrafluoroethylene (PTFE)（PTFE）Emulsion, Kynoar（PVDF）Emulsion or fluorine carbon tree
Fat；The addition of the lyophobic dust is the 1-5% of cathode catalysis layer quality.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710699034.8A CN107611452A (en) | 2017-08-15 | 2017-08-15 | A kind of preparation method of the membrane electrode containing three-dimensional hydrophobic cathode catalysis layer |
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Cited By (8)
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| CN109524674A (en) * | 2017-09-19 | 2019-03-26 | 粟青青 | The method for promoting fuel cell membrane electrode cathode catalysis layer performance |
| CN109524676A (en) * | 2018-11-20 | 2019-03-26 | 安徽明天氢能科技股份有限公司 | A kind of fuel cell catalyst layer electrode of three-dimensional and preparation method thereof |
| CN109830696A (en) * | 2019-01-09 | 2019-05-31 | 安徽明天氢能科技股份有限公司 | A kind of fuel cell membrane electrode preparation process |
| CN111203236A (en) * | 2020-01-15 | 2020-05-29 | 清创人和生态工程技术有限公司 | Preparation method and application of cobalt disulfide/carbon fiber composite material |
| CN112002916A (en) * | 2020-09-08 | 2020-11-27 | 广东工业大学 | Transition metal doped anode catalyst and preparation method and application thereof |
| CN113328102A (en) * | 2021-06-28 | 2021-08-31 | 三一汽车制造有限公司 | Electrode, battery and vehicle |
| CN113684458A (en) * | 2021-07-06 | 2021-11-23 | 华南理工大学 | Carbon nanotube with multi-wall disordered structure for proton exchange membrane fuel cell, membrane electrode, preparation method and application |
| CN114068955A (en) * | 2021-10-29 | 2022-02-18 | 浙江天能氢能源科技有限公司 | Fuel cell membrane electrode and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109524674A (en) * | 2017-09-19 | 2019-03-26 | 粟青青 | The method for promoting fuel cell membrane electrode cathode catalysis layer performance |
| CN109524674B (en) * | 2017-09-19 | 2022-06-21 | 粟青青 | Method for improving performance of cathode catalyst layer of membrane electrode of fuel cell |
| CN109524676A (en) * | 2018-11-20 | 2019-03-26 | 安徽明天氢能科技股份有限公司 | A kind of fuel cell catalyst layer electrode of three-dimensional and preparation method thereof |
| CN109830696B (en) * | 2019-01-09 | 2022-03-22 | 安徽明天氢能科技股份有限公司 | Preparation process of fuel cell membrane electrode |
| CN109830696A (en) * | 2019-01-09 | 2019-05-31 | 安徽明天氢能科技股份有限公司 | A kind of fuel cell membrane electrode preparation process |
| CN111203236A (en) * | 2020-01-15 | 2020-05-29 | 清创人和生态工程技术有限公司 | Preparation method and application of cobalt disulfide/carbon fiber composite material |
| CN111203236B (en) * | 2020-01-15 | 2023-04-18 | 清创人和生态工程技术有限公司 | Preparation method and application of cobalt disulfide/carbon fiber composite material |
| CN112002916A (en) * | 2020-09-08 | 2020-11-27 | 广东工业大学 | Transition metal doped anode catalyst and preparation method and application thereof |
| CN113328102A (en) * | 2021-06-28 | 2021-08-31 | 三一汽车制造有限公司 | Electrode, battery and vehicle |
| CN113328102B (en) * | 2021-06-28 | 2023-08-22 | 三一汽车制造有限公司 | Electrode, battery and vehicle |
| CN113684458A (en) * | 2021-07-06 | 2021-11-23 | 华南理工大学 | Carbon nanotube with multi-wall disordered structure for proton exchange membrane fuel cell, membrane electrode, preparation method and application |
| CN113684458B (en) * | 2021-07-06 | 2022-08-12 | 华南理工大学 | Membrane electrode prepared by utilizing multi-wall disordered structure carbon nano tube for proton exchange membrane fuel cell, preparation method and application |
| CN114068955A (en) * | 2021-10-29 | 2022-02-18 | 浙江天能氢能源科技有限公司 | Fuel cell membrane electrode and preparation method thereof |
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