CN108598534A - A kind of fuel cell humidification control water quality proton exchange and preparation method certainly - Google Patents
A kind of fuel cell humidification control water quality proton exchange and preparation method certainly Download PDFInfo
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- CN108598534A CN108598534A CN201810495717.6A CN201810495717A CN108598534A CN 108598534 A CN108598534 A CN 108598534A CN 201810495717 A CN201810495717 A CN 201810495717A CN 108598534 A CN108598534 A CN 108598534A
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- gelatin
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- aerosil
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention proposes that a kind of fuel cell is used from humidification control water quality proton exchange and preparation method, and doughnut is immersed to the polyethylene glycol phase-change material of hot melt, weaves after adsorbing polyethylene glycol, obtains textle layers；Gelatin is scattered in aerosil to be uniformly dispersed, makes gelatin uniform adsorption in the micropore of aerosil, condensation dispersion obtains load gelatin corpuscle；Metal platinum and graphene grinding load are obtained into metal platinum carried fine particles；Metal platinum carried fine particles are added in Nafion solution and are disperseed, it is then immersed in microporous teflon membran, it is dry, obtain the perfluorinated sulfonic acid polymer composite membrane that a microporous teflon membran is network skeleton, then gelatin corpuscle is sprayed by anode surface in film, and attaches textle layers.Proton exchange membrane of the present invention, the purpose of the water balance in film in the components fine adjustment film such as polyethylene glycol, aerosil, have it is good from humidification control water characteristic, it is good from moisturising and humidification management to realize.
Description
Technical field
The present invention relates to field of fuel cell technology, use from humidification control water proton and exchange more particularly to a kind of fuel cell
Film and preparation method.
Background technology
It is surging forward in fuel cell electric vehicle research and development at the international level.Proton Exchange Membrane Fuel Cells (proton
Exchange membrane fuel cell, PEMFC) have high energy transformation ratio, power density height, startup soon and without dirt
The advantages that dye, becomes the one preferred technique of fuel cell electric vehicle.Currently, influencing the commercialized major technique of fuel cell car
Difficult point comes from service life and the cost of fuel cell.Vehicle fuel battery durability is not good enough, main the reason is that vehicle-mounted operating mode is to fuel
The influence of battery.
Proton exchange membrane is the core component of proton exchange fuel cell, it plays two important works in a fuel cell
With first, hydrogen ion channel is provided as electrolyte, second is that polarization response gas is isolated as diaphragm.Proton exchange film properties
Quality directly affects the working performance, cost and application prospect of fuel cell, is the key problem in technology of fuel cell.
The fuel cell water that cathode generates at runtime can be to anode diffusion, and anode hydrone can be moved with proton to cathode
It moves, but the water purification of film both sides transmission is to flow to cathode by anode, as a result causes the dielectric film aquation of anode-side insufficient,
And cathode is compared with excess moisture.The electrochemical reaction of fuel cell is happened at water/gas/proton interface, and excessive water can diluent gas
Reaction density influences reaction efficiency, influences proton exchange membrane proton conductivity, therefore, it is necessary to maintain the abundant aquation of anode, prevents
Only cathode excess moisture.Furthermore the proton exchange membrane that fuel cell uses at present is all almost the production of Du Pont companies of the U.S.
Nafion perfluoro sulfonic acid membranes, Nafion perfluoro sulfonic acid membranes in larger water content have higher proton conductivity, this kind of film
Ionic conductance be strongly dependent on water content, it is relatively low or temperature is higher in water content, when especially temperature is higher than 100 DEG C, electricity
Conductance, which is decreased obviously, can also make film that chemical degradation occur.Therefore, the stabilisation job control and normal pressure of proton exchange membrane are abundant
Aquation be stable operation fuel cell, promoted proton exchange film fuel battery performance and service life key.And carry out film, electrode
And the structure in flow field is improved, and realizes that the reasonable distribution of water and effectively management are the prerequisites of stable operation fuel cell.
Those skilled in the art propose the self-humidification thinking by being internalized by synthetic water in dielectric film.Such as middle promulgated by the State Council
Bright number of patent application 200410061104.X provides a kind of multi-layer nano compound proton exchange membrane with self-moistening function
Preparation method first impregnates proton conductive resin and SiO in polytetrafluoroethylene (PTFE) (PTFE) perforated membrane2Or TiO2Nano-particle
Mixture forms water conservation proton conduction layer, then impregnates proton conductive resin and formed certainly with the mixture of Pt nano particle or nano Pd particle particle
Be humidified proton conduction layer.Chinese invention patent application number 200510018740.9 discloses the proton exchange membrane with water retaining function
The preparation method of fuel cell chip has water conservation in transfer medium surface coating catalyst layer in catalyst layer surface coating
Proton exchange membrane is placed among two transfer mediums coated with inorganic nano-particle, heat by the inorganic nano-particle sublayer of function
Transfer medium is pressed and thrown off, fuel cell chip is obtained, however the introducing of inorganic nano-particle can increase cell resistance, influence
Catalyst is contacted with proton exchange membrane.Although being improved in said program by disperseing nanocatalyst and/or inorganic nano-particle
Proton exchange membrane water-retaining property, however but can not be in adjusting film water balance, water control pipe reason is unsatisfactory.
Chinese invention patent application number 201210557812.7 disclose it is a kind of for Proton Exchange Membrane Fuel Cells from
Humidifying film electrode and preparation method.By by carbon supported platinum catalyst or platinum ruthenium catalyst, perfluor sulfoacid resin solution, have it is hydrophilic
The organic high molecular polymer and inorganic oxide of property mix in water or low boiling point solvent and are ultrasonically formed catalyst pulp,
Catalyst pulp is sprayed on to the side of proton exchange membrane, anode catalyst layer is made, is sprayed in the other side of the proton exchange membrane
Slurry without hydrophilic organic high molecular polymer and inorganic oxide, obtains cathode catalysis layer.However due to film both sides
Hydrophily is different, and film meets solvent and swelling set occurs, and reduces battery performance.It is therefore proposed that one kind can effectively carry out being humidified certainly
The proton exchange membrane that can carry out humidification management simultaneously is of great significance to the raising of fuel cell proton conduction property.
Invention content
In order to keep fuel proton exchange membrane good a kind of fuel cell is proposed from moisturising and humidification management, the present invention
With from control water quality proton exchange and the preparation method of being humidified, the purpose of the water balance in adjusting film is realized, have good from humidification
Control water characteristic.
To solve the above problems, the present invention uses following technical scheme：
A kind of fuel cell humidification control water quality proton exchange certainly, which is characterized in that including：Textle layers, gelatin corpuscle layer, poly- four
Fluoride microporous film is the perfluorinated sulfonic acid polymer composite film of network skeleton, wherein the thickness of the textle layers is 50-100 μ
The thickness of m, the gelatin corpuscle layer are 15-170 μm, and the microporous teflon membran is that the perfluorinated sulfonic acid of network skeleton is poly-
The thickness for closing object composite film is 100-300 μm.
Preferably, the textle layers are made of doughnut, and fiber-loaded have a polyethylene glycol, and the doughnut is superelevation
One kind in molecular weight polyethylene doughnut, hollow carbon fiber, line footpath are 1-5 μm, and specific surface area is 1020-3200 m2g-1, the wherein load capacity of polyethylene glycol is 10%-25%.
Preferably, the gelatin corpuscle layer is made of gelatin uniform adsorption in the micropore of aerosil, wherein
The load capacity of gelatin is 35%-60%, and the grain size of the aerosil particle is 3-8 μm, and aperture is 10-300 nm.
Preferably, the microporous teflon membran be network skeleton perfluorinated sulfonic acid polymer composite membrane, described poly- four
The aperture of fluoride microporous film is 1-3 μm, and thickness is 20-50 μm, and outer wrapping perfluorinated sulfonic acid polymer film, fluosulfonic acid polymerization
Contain metal platinum/graphen particle in object, the wherein grain size of metal platinum/graphen particle is 10-30 nm, the quality of each component
Score is the microporous teflon membran of 30%-40%, the perfluorinated sulfonic acid polymer of 50-60%, the metal Pt microparticles of 6-9%, 1-4%
Graphene.
Preferably, a kind of preparation method of fuel cell from humidification control water quality proton exchange, which is characterized in that specific system
Preparation Method is as follows：
（1）The doughnut is immersed to the polyethylene glycol phase-change material of heating melting, absorption polyethylene glycol takes after 2-10 hours
Go out Temperature fall, obtains the doughnut of load polyethylene glycol, then weave, obtain textle layers；
（2）Gelatin is dissolved in hot water, a concentration of 10%-30% of the gelatin, gelatin hot water is added in aerosil
In solution, impregnates 12-36 hours, make gelatin uniform adsorption in the micropore of aerosil, be warming up to 110-130 DEG C of steaming
Room temperature is cooled to after shampoo part, condensation obtains the aerosil gelatin corpuscle of load gelatin；
（3）The metal platinum of the mass ratio is uniformly mixed with graphene, by mechanical lapping 12-24h, it is negative to obtain metal platinum
Carry particle；
（4）By step（3）Obtained metal platinum carried fine particles are added in Nafion solution, by high-speed stirred and ultrasound point
It dissipates, so that the metal platinum carried fine particles is dispersed in Nafion solution, be then immersed in microporous teflon membran, impregnate
12-24h pulls drying out, obtains the perfluorinated sulfonic acid polymer composite membrane that microporous teflon membran is network skeleton；
（5）By gelatin corpuscle ultrasonic disperse in ethanol solution, gelatin corpuscle dispersion liquid is obtained, in step（4）Described
Perfluorinated sulfonic acid polymer composite membrane sprays gelatin corpuscle by anode surface, and attaches textle layers, obtains handing over from the control water proton that is humidified
Change film.
Preferably, step（1）Described in polyethylene glycol heating temperature be 68-87 DEG C.
Preferably, step（2）The temperature of the hot water is 60-80 DEG C.
Preferably, step（4）In, a concentration of 5-7% of the Nafion solution, the quality of the metal platinum carried fine particles
A concentration of 9-15%, the drying are vacuum drying, and vacuum degree 0.1-3kPa, temperature is 50-75 DEG C.
Preferably, step（5）Described in the mass concentration of gelatin corpuscle be 10-30%, the input speed of the spraying is
50-80ml/min, compressed air pressure are 0.2-0.4 Mpa, and temperature is 70-110 DEG C at nozzle.
In order to keep fuel proton exchange membrane good a kind of fuel cell is proposed from moisturising and humidification management, the present invention
Water quality proton exchange and preparation method are controlled with from humidification.Ultra-high molecular weight polyethylene doughnut, hollow carbon fiber etc. is hollow
Fiber immerses the polyethylene glycol phase-change material of hot melt, weaves after adsorbing polyethylene glycol, obtains textle layers；Gelatin is scattered in
Aerosil is uniformly dispersed, and makes gelatin uniform adsorption in the micropore of aerosil, and condensation dispersion is born
Carry gelatin corpuscle；Metal platinum and graphene grinding load are obtained into metal platinum carried fine particles；Metal platinum carried fine particles are added to
Disperse in Nafion solution, be then immersed in microporous teflon membran, dry, it is network bone to obtain a microporous teflon membran
Then the perfluorinated sulfonic acid polymer composite membrane of frame sprays gelatin corpuscle by anode surface in film, and attaches textle layers and be prepared.
Polyethylene glycol is carried on doughnut in the present invention, and prepares textle layers, makes it have good water imbibition, to change sun
Pole moisture transmission rate, effectively prevent excessive water to be transmitted to cathode；Metal platinum and graphene-supported particle when work, diffuse into
The oxidant and reducing agent gas electrification synthetic water at Pt particles for entering dielectric film, make film keep sufficient hydrated state, and
There is aerosil absorption regulation and control water, while polyethylene glycol, as phase-change material, absorb water solidification when working low temperature, in height
There is fusing tendency, absorbent function enhancing to achieve the purpose that the water balance in fine adjustment film when warm, have good from humidification control
Water characteristic, it is good from moisturising and humidification management to realize.
The present invention proposes that a kind of fuel cell is used from humidification control water quality proton exchange and preparation method, with prior art phase
Than the feature and excellent effect protruded is：
1, metal platinum and graphene grinding load are obtained metal platinum carried fine particles by use of the invention, and metal platinum carried fine particles are added
Enter and disperse into Nafion solution, be then immersed in microporous teflon membran, dry, it is network to obtain microporous teflon membran
Then the perfluorinated sulfonic acid polymer composite membrane of skeleton sprays gelatin corpuscle by anode surface in film, and attaches with good suction
Aqueous textle layers, metal platinum and graphene-supported particle when work, diffuse into the oxidant and reducing agent gas of dielectric film
Body electrification synthetic water at Pt particles makes film keep sufficient hydrated state, and has aerosil absorption regulation and control water, together
When polyethylene glycol as phase-change material, absorb water solidification when working low temperature, and there is fusing tendency, absorbent function to increase at high temperature
By force, achieve the purpose that the water balance in fine adjustment film, have good from humidification control water characteristic.
2, fuel cell provided by the invention is used from humidification control water quality proton exchange, and super high molecular weight doughnut is immersed
The polyethylene glycol phase-change material of hot melt weaves after adsorbing polyethylene glycol, obtains textle layers, polyethylene glycol is carried on hollow
Fiber, and textle layers are prepared, good water imbibition is made it have, to change anode moisture transmission rate, effectively prevent excess
Water is transmitted to cathode.
3, proton exchange membrane prepared by the present invention can be carried out effectively from humidification while can carry out humidification management, preparation
Fuel cell is in low humidity conditions and wider operation temperature area performance better than the proton exchange membrane for directly coating composite nano-granule sublayer
The fuel cell of preparation.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）Ultra-high molecular weight polyethylene doughnut is immersed to the polyethylene glycol phase-change material of heating melting, heating temperature 68
DEG C, absorption polyethylene glycol takes out Temperature fall after 10 hours, obtains the doughnut of load polyethylene glycol, and line footpath is 1-5 μm,
Specific surface area is 2200 m2g-1, wherein the load capacity of polyethylene glycol is 10%%, then is weaved, and it is 100 μm of spinnings to obtain thickness
Tissue layer；
（2）Gelatin is dissolved in hot water, the temperature of hot water is 60-80 DEG C, a concentration of the 30% of the gelatin, by silica gas
Gel is added in gelatin hydrothermal solution, impregnates 12 hours, makes gelatin uniform adsorption in the micropore of aerosil, heats up
It is cooled to room temperature after to 130 DEG C of evaporation moisture content, condensation obtains gelatin uniform adsorption and constituted in the micropore of aerosil
Gelatin corpuscle layer, the wherein load capacity of gelatin is 50%, and the grain size of the aerosil particle is 80 μm, and aperture is
230 nm, thickness are the aerosil gelatin corpuscle layer of 8 μm of load gelatin；
（3）The metal platinum of the mass ratio is uniformly mixed with graphene, by mechanical lapping 18h, obtains metal platinum load
Particle；
（4）By step（3）Obtained metal platinum carried fine particles are added in Nafion solution, by high-speed stirred and ultrasound point
It dissipates, the metal platinum carried fine particles is made to be dispersed in Nafion solution, a concentration of the 6% of the Nafion solution, the gold
The mass concentration for belonging to platinum carried fine particles is 12%, and the drying is vacuum drying, and vacuum degree 1.3kPa, temperature is 5 DEG C, then
Microporous teflon membran is immersed, 12h is impregnated, pulls drying out, it is network that obtain thickness, which be 300 μm of microporous teflon membrans,
The perfluorinated sulfonic acid polymer composite membrane of skeleton, the wherein aperture of microporous teflon membran are 2 μm, and thickness is 45 μm, outsourcing
Perfluorinated sulfonic acid polymer film is wrapped up in, contains metal platinum/graphen particle, wherein metal platinum/graphen particle in perfluorinated sulfonic acid polymer
Grain size be 10-30 nm, the mass fraction of each component be 30%% microporous teflon membran, 60% perfluorinated sulfonic acid polymer,
7% metal Pt microparticles, 3% graphene；
（5）By gelatin corpuscle ultrasonic disperse in ethanol solution, gelatin corpuscle dispersion liquid is obtained, the quality of gelatin corpuscle is dense
Degree is 23%, and the input speed of the spraying is 60ml/min, and compressed air pressure is 0.34 Mpa, and temperature is 100 at nozzle
DEG C, in step（4）The perfluorinated sulfonic acid polymer composite membrane sprays gelatin corpuscle by anode surface, and attaches textle layers, obtains
Water quality proton exchange is controlled to from humidification.
The proton exchange membrane that the present embodiment prepares is placed between catalyst layer and diffusion layer, hot pressing is carried out and obtains film
Electrode and monocell, active area 25cm2, in temperature 60 C, atmospheric hydrogen 300mL/ minutes, 1960mL/ points of atmospheric oxygen
It is tested under the conditions of clock, tests electrolytic cell chemical property using electrochemical workstation, it is as shown in table 1 to obtain data.
Embodiment 2
（1）Super high molecular weight hollow carbon fiber fiber is immersed to the polyethylene glycol phase-change material of heating melting, heating temperature 87
DEG C, absorption polyethylene glycol takes out Temperature fall after 10 hours, obtains the doughnut of load polyethylene glycol, and line footpath is 1 μm, than
Surface area is 3200 m2g-1, wherein the load capacity of polyethylene glycol is 10%, then is weaved, and it is 100 μm of weavings to obtain thickness
Layer；
（2）Gelatin is dissolved in hot water, the temperature of hot water is 60 DEG C, a concentration of the 30% of the gelatin, by aerosil
It is added in gelatin hydrothermal solution, impregnates 12 hours, make gelatin uniform adsorption in the micropore of aerosil, be warming up to
It is cooled to room temperature after 130 DEG C of evaporation moisture content, condensation obtains what gelatin uniform adsorption was constituted in the micropore of aerosil
Gelatin corpuscle layer, the wherein load capacity of gelatin are 35%, and the grain size of the aerosil particle is 6 μm, aperture 200
Nm, thickness are the aerosil gelatin corpuscle layer of 170 μm of load gelatin；
（3）The metal platinum of the mass ratio is uniformly mixed with graphene, for 24 hours by mechanical lapping, obtains metal platinum load
Particle；
（4）By step（3）Obtained metal platinum carried fine particles are added in Nafion solution, by high-speed stirred and ultrasound point
It dissipates, the metal platinum carried fine particles is made to be dispersed in Nafion solution, a concentration of the 7% of the Nafion solution, the gold
The mass concentration for belonging to platinum carried fine particles is 15%, and the drying is vacuum drying, and vacuum degree 0.1kPa, temperature is 75 DEG C, then
Microporous teflon membran is immersed, 12h is impregnated, pulls drying out, it is network that obtain thickness, which be 300 μm of microporous teflon membrans,
The perfluorinated sulfonic acid polymer composite membrane of skeleton, the wherein aperture of microporous teflon membran are 3 μm, and thickness is 20 μm, outsourcing
Perfluorinated sulfonic acid polymer film is wrapped up in, contains metal platinum/graphen particle, wherein metal platinum/graphen particle in perfluorinated sulfonic acid polymer
Grain size be 26nm, the mass fraction of each component be 34% microporous teflon membran, 59% perfluorinated sulfonic acid polymer, 6% gold
Belong to Pt microparticles, 1% graphene；
（5）By gelatin corpuscle ultrasonic disperse in ethanol solution, gelatin corpuscle dispersion liquid is obtained, the quality of gelatin corpuscle is dense
Degree is 23%, and the input speed of the spraying is 64ml/min, and compressed air pressure is 0.3 Mpa, and temperature is 110 DEG C at nozzle,
In step（4）The perfluorinated sulfonic acid polymer composite membrane sprays gelatin corpuscle by anode surface, and attaches textle layers, obtains certainly
Humidification control water quality proton exchange.
The proton exchange membrane that the present embodiment prepares is placed between catalyst layer and diffusion layer, hot pressing is carried out and obtains film
Electrode and monocell, active area 25cm2, in temperature 60 C, atmospheric hydrogen 300mL/ minutes, 1960 mL/ points of atmospheric oxygen
It is tested under the conditions of clock, tests electrolytic cell chemical property using electrochemical workstation, it is as shown in table 1 to obtain data.
Embodiment 3
（1）The doughnut is immersed to the polyethylene glycol phase-change material of heating melting, heating temperature is 68 DEG C, adsorbs poly- second two
After alcohol 2 hours, Temperature fall is taken out, obtains the doughnut of load polyethylene glycol, doughnut is ultra-high molecular weight polyethylene
One kind in doughnut, hollow carbon fiber, line footpath are 5 μm, specific surface area 1020m2g-1, the wherein load of polyethylene glycol
Amount is 25%, then is weaved, and it is 50 μm of textle layers to obtain thickness；
（2）Gelatin is dissolved in hot water, the temperature of hot water is 80 DEG C, a concentration of the 10% of the gelatin, by aerosil
It is added in gelatin hydrothermal solution, impregnates 36 hours, make gelatin uniform adsorption in the micropore of aerosil, be warming up to
It is cooled to room temperature after 110 DEG C of evaporation moisture content, condensation obtains what gelatin uniform adsorption was constituted in the micropore of aerosil
Gelatin corpuscle layer, the wherein load capacity of gelatin are 60%, and the grain size of the aerosil particle is 3 μm, aperture 300
Nm, thickness are the aerosil gelatin corpuscle layer of 15 μm of load gelatin；
（3）The metal platinum of the mass ratio is uniformly mixed with graphene, by mechanical lapping 12h, obtains metal platinum load
Particle；
（4）By step（3）Obtained metal platinum carried fine particles are added in Nafion solution, by high-speed stirred and ultrasound point
It dissipates, the metal platinum carried fine particles is made to be dispersed in Nafion solution, a concentration of the 6% of the Nafion solution, the gold
The mass concentration for belonging to platinum carried fine particles is 9%, and the drying is vacuum drying, and vacuum degree 2.4kPa, temperature is 75 DEG C, then
Microporous teflon membran is immersed, 18h is impregnated, pulls drying out, it is network that obtain thickness, which be 120 μm of microporous teflon membrans,
The perfluorinated sulfonic acid polymer composite membrane of skeleton, the wherein aperture of microporous teflon membran are 2.4 μm, and thickness is 45 μm, outside
It is wrapped in perfluorinated sulfonic acid polymer film, contains metal platinum/graphen particle in perfluorinated sulfonic acid polymer, wherein metal platinum/graphen is micro-
The grain size of grain is 30 nm, and the mass fraction of each component is 40% microporous teflon membran, 50% perfluorinated sulfonic acid polymer, 6%
Metal Pt microparticles, 4% graphene；
（5）By gelatin corpuscle ultrasonic disperse in ethanol solution, gelatin corpuscle dispersion liquid is obtained, the quality of gelatin corpuscle is dense
Degree is 30%, and the input speed of the spraying is 50ml/min, compressed air pressure 0.2Mpa, and temperature is 110 DEG C at nozzle,
In step（4）The perfluorinated sulfonic acid polymer composite membrane sprays gelatin corpuscle by anode surface, and attaches textle layers, obtains certainly
Humidification control water quality proton exchange.
The proton exchange membrane that the present embodiment prepares is placed between catalyst layer and diffusion layer, hot pressing is carried out and obtains film
Electrode and monocell, active area 25cm2, in temperature 60 C, atmospheric hydrogen 300mL/ minutes, 1960 mL/ points of atmospheric oxygen
It is tested under the conditions of clock, tests electrolytic cell chemical property using electrochemical workstation, it is as shown in table 1 to obtain data.
Embodiment 4
（1）Ultra-high molecular weight polyethylene doughnut is immersed to the polyethylene glycol phase-change material of heating melting, heating temperature 84
DEG C, absorption polyethylene glycol takes out Temperature fall after 6 hours, obtains the doughnut of load polyethylene glycol, and line footpath is 4.5 μm, than
Surface area is 1200 m2g-1, wherein the load capacity of polyethylene glycol is 23%, then is weaved, and it is 80 μm of textle layers to obtain thickness；
（2）Gelatin is dissolved in hot water, the temperature of hot water is 75 DEG C, a concentration of the 17% of the gelatin, by aerosil
It is added in gelatin hydrothermal solution, impregnates 24 hours, make gelatin uniform adsorption in the micropore of aerosil, be warming up to
It is cooled to room temperature after 125 DEG C of evaporation moisture content, condensation obtains what gelatin uniform adsorption was constituted in the micropore of aerosil
Gelatin corpuscle layer, the wherein load capacity of gelatin are 30%, and the grain size of the aerosil particle is 5 μm, aperture 230
Nm, thickness are the aerosil gelatin corpuscle layer of 80 μm of load gelatin；
（3）The metal platinum of the mass ratio is uniformly mixed with graphene, by mechanical lapping 12-24h, it is negative to obtain metal platinum
Carry particle；
（4）By step（3）Obtained metal platinum carried fine particles are added in Nafion solution, by high-speed stirred and ultrasound point
It dissipates, the metal platinum carried fine particles is made to be dispersed in Nafion solution, a concentration of the 6% of the Nafion solution, the gold
The mass concentration for belonging to platinum carried fine particles is 13%, and the drying is vacuum drying, and vacuum degree 2kPa, temperature is 50 DEG C, is then soaked
Enter microporous teflon membran, impregnate 18h, pull drying out, it is network bone that obtain thickness, which be 230 μm of microporous teflon membrans,
The perfluorinated sulfonic acid polymer composite membrane of frame, the wherein aperture of microporous teflon membran are 2.5 μm, and thickness is 20 μm, outsourcing
Perfluorinated sulfonic acid polymer film is wrapped up in, contains metal platinum/graphen particle, wherein metal platinum/graphen particle in perfluorinated sulfonic acid polymer
Grain size be 19 nm, the mass fraction of each component is 36% microporous teflon membran, 54% perfluorinated sulfonic acid polymer, 8%
Metal Pt microparticles, 2% graphene；
（5）By gelatin corpuscle ultrasonic disperse in ethanol solution, gelatin corpuscle dispersion liquid is obtained, the quality of gelatin corpuscle is dense
Degree is 23%, and the input speed of the spraying is 65ml/min, and compressed air pressure is 0.35 Mpa, and temperature is 100 at nozzle
DEG C, in step（4）The perfluorinated sulfonic acid polymer composite membrane sprays gelatin corpuscle by anode surface, and attaches textle layers, obtains
Water quality proton exchange is controlled to from humidification.
The proton exchange membrane that the present embodiment prepares is placed in 40w% carbon and carries Pt catalyst layers and polytetrafluoroethylene (PTFE) processing
Between carbon paper diffusion layer afterwards, carries out hot pressing and obtain membrane electrode and monocell, active area 25cm2, in temperature 60 C, normal pressure
Hydrogen 300mL/ minutes, atmospheric oxygen is tested under the conditions of 1960 mL/ minutes, and electrolytic cell is tested using electrochemical workstation
It is as shown in table 1 to obtain data for chemical property.
Embodiment 5
（1）Ultra-high molecular weight polyethylene doughnut is immersed to the polyethylene glycol phase-change material of heating melting, heating temperature 82
DEG C, absorption polyethylene glycol takes out Temperature fall after 9 hours, obtains the doughnut of load polyethylene glycol, and line footpath is 4.5 μm, than
Surface area is 3200 m2g-1, wherein the load capacity of polyethylene glycol is 25%, then is weaved, and it is 50 μm of textle layers to obtain thickness；
（2）Gelatin is dissolved in hot water, the temperature of hot water is 80 DEG C, a concentration of the 28% of the gelatin, by aerosil
It is added in gelatin hydrothermal solution, impregnates 30 hours, make gelatin uniform adsorption in the micropore of aerosil, be warming up to
It is cooled to room temperature after 123 DEG C of evaporation moisture content, condensation obtains what gelatin uniform adsorption was constituted in the micropore of aerosil
Gelatin corpuscle layer, the wherein load capacity of gelatin are 53%, and the grain size of the aerosil particle is 4 μm, aperture 80
Nm, thickness are the aerosil gelatin corpuscle layer of 45 μm of load gelatin；
（3）The metal platinum of the mass ratio is uniformly mixed with graphene, by mechanical lapping 18h, obtains metal platinum load
Particle；
（4）By step（3）Obtained metal platinum carried fine particles are added in Nafion solution, by high-speed stirred and ultrasound point
It dissipates, the metal platinum carried fine particles is made to be dispersed in Nafion solution, a concentration of the 7% of the Nafion solution, the gold
The mass concentration for belonging to platinum carried fine particles is 15%, and the drying is vacuum drying, and vacuum degree 0.4kPa, temperature is 65 DEG C, then
Microporous teflon membran is immersed, dipping for 24 hours, pulls drying out, and it is network that obtain thickness, which be 300 μm of microporous teflon membrans,
The perfluorinated sulfonic acid polymer composite membrane of skeleton, the wherein aperture of microporous teflon membran are 2 μm, and thickness is 50 μm, outsourcing
Perfluorinated sulfonic acid polymer film is wrapped up in, contains metal platinum/graphen particle, wherein metal platinum/graphen particle in perfluorinated sulfonic acid polymer
Grain size be 22 nm, the mass fraction of each component is 35% microporous teflon membran, 54% perfluorinated sulfonic acid polymer, 7%
Metal Pt microparticles, 4% graphene；
（5）By gelatin corpuscle ultrasonic disperse in ethanol solution, gelatin corpuscle dispersion liquid is obtained, the quality of gelatin corpuscle is dense
Degree is 29%, and the input speed of the spraying is 80ml/min, compressed air pressure 0.27Mpa, and temperature is 104 DEG C at nozzle,
In step（4）The perfluorinated sulfonic acid polymer composite membrane sprays gelatin corpuscle by anode surface, and attaches textle layers, obtains certainly
Humidification control water quality proton exchange.
The proton exchange membrane that the present embodiment prepares is placed between catalyst layer and diffusion layer, hot pressing is carried out and obtains film
Electrode and monocell, active area 25cm2, in temperature 60 C, atmospheric hydrogen 300mL/ minutes, 1960 mL/ points of atmospheric oxygen
It is tested under the conditions of clock, tests electrolytic cell chemical property using electrochemical workstation, it is as shown in table 1 to obtain data.
Comparative example 1
Active area is 25cm2Nafion perfluoro sulfonic acid membranes, be used to prepare monocell according to the method described in embodiment 1-5,
It is tested under similarity condition, it is as shown in table 1 to obtain data.
Comparative example 2
（1）Ultra-high molecular weight polyethylene is weaved, it is 100 μm of textle layers to obtain thickness；
（2）Gelatin is dissolved in hot water, the temperature of hot water is 60-80 DEG C, a concentration of the 30% of the gelatin, by silica gas
Gel is added in gelatin hydrothermal solution, impregnates 12 hours, makes gelatin uniform adsorption in the micropore of aerosil, heats up
It is cooled to room temperature after to 130 DEG C of evaporation moisture content, condensation obtains gelatin uniform adsorption and constituted in the micropore of aerosil
Gelatin corpuscle layer, the wherein load capacity of gelatin is 50%, and the grain size of the aerosil particle is 80 μm, and aperture is
230 nm, thickness are the aerosil gelatin corpuscle layer of 80 μm of load gelatin；
（3）The metal platinum of the mass ratio is uniformly mixed with graphene, by mechanical lapping 18h, obtains metal platinum load
Particle；
（4）By step（3）Obtained metal platinum carried fine particles are added in Nafion solution, by high-speed stirred and ultrasound point
It dissipates, the metal platinum carried fine particles is made to be dispersed in Nafion solution, a concentration of the 6% of the Nafion solution, the gold
The mass concentration for belonging to platinum carried fine particles is 12%, and the drying is vacuum drying, and vacuum degree 1.3kPa, temperature is 5 DEG C, then
Microporous teflon membran is immersed, 12h is impregnated, pulls drying out, it is network that obtain thickness, which be 300 μm of microporous teflon membrans,
The perfluorinated sulfonic acid polymer composite membrane of skeleton, the wherein aperture of microporous teflon membran are 2 μm, and thickness is 45 μm, outsourcing
Perfluorinated sulfonic acid polymer film is wrapped up in, contains metal platinum/graphen particle, wherein metal platinum/graphen particle in perfluorinated sulfonic acid polymer
Grain size be 10-30 nm, the mass fraction of each component be 30%% microporous teflon membran, 60% perfluorinated sulfonic acid polymer,
7% metal Pt microparticles, 3% graphene；
（5）By gelatin corpuscle ultrasonic disperse in ethanol solution, gelatin corpuscle dispersion liquid is obtained, the quality of gelatin corpuscle is dense
Degree is 23%, and the input speed of the spraying is 60ml/min, and compressed air pressure is 0.34 Mpa, and temperature is 100 at nozzle
DEG C, in step（4）The perfluorinated sulfonic acid polymer composite membrane sprays gelatin corpuscle by anode surface, and attaches textle layers, obtains
Water quality proton exchange is controlled to from humidification.The solid electrolyte of acquisition is used to prepare monocell according to embodiment 1-5 same methods,
It is tested under the same terms, it is as shown in table 1 to obtain data.
Table 1:
By test, the present invention prepares textle layers by the way that polyethylene glycol is carried on doughnut in film, makes it have good
Good water imbibition effectively prevent excessive water to be transmitted to cathode to change anode moisture transmission rate；Metal platinum is negative with graphene
Particle is carried, when work, the oxidant and reducing agent gas electrification synthetic water at Pt particles of dielectric film is diffused into, film is made to protect
Sufficient hydrated state is held, and has aerosil absorption regulation and control water, while polyethylene glycol is working as phase-change material
Absorb water solidification when low temperature, and there is fusing tendency, absorbent function enhancing to reach the mesh of the water balance in fine adjustment film at high temperature
, have good from humidification control water characteristic.Cell working stability is set to be substantially improved.
Claims (9)
1. a kind of fuel cell is used from humidification control water quality proton exchange, which is characterized in that including：Textle layers, gelatin corpuscle layer,
Microporous teflon membran is the perfluorinated sulfonic acid polymer composite film of network skeleton, wherein the thickness of the textle layers is 50-
100 μm, the thickness of the gelatin corpuscle layer is 15-170 μm, and the microporous teflon membran is the perfluor sulphur of network skeleton
The thickness of acid polymer composite film is 100-300 μm.
2. a kind of fuel cell according to claim 1 is used from humidification control water quality proton exchange, which is characterized in that the spinning
Tissue layer is made of doughnut, and fiber-loaded have a polyethylene glycol, the doughnut be ultra-high molecular weight polyethylene doughnut,
One kind in hollow carbon fiber, line footpath are 1-5 μm, and specific surface area is 1020-3200 m2g-1, the wherein load of polyethylene glycol
Amount is 10%-25%.
3. a kind of fuel cell according to claim 1 is used from humidification control water quality proton exchange, which is characterized in that stated clearly
Glue particulate layer is made of gelatin uniform adsorption in the micropore of aerosil, and wherein the load capacity of gelatin is 35%-60%,
The grain size of the aerosil particle is 3-8 μm, and aperture is 10-300 nm.
4. a kind of fuel cell according to claim 1 is used from humidification control water quality proton exchange, which is characterized in that described poly-
Tetrafluoroethene microporous barrier is the perfluorinated sulfonic acid polymer composite membrane of network skeleton, and the aperture of the microporous teflon membran is 1-
3 μm, thickness is 20-50 μm, and outer wrapping perfluorinated sulfonic acid polymer film, and it is micro- to contain metal platinum/graphen in perfluorinated sulfonic acid polymer
Grain, the wherein grain size of metal platinum/graphen particle are 10-30 nm, and the mass fraction of each component is the polytetrafluoroethyl-ne of 30%-40%
The graphene of alkene microporous barrier, the perfluorinated sulfonic acid polymer of 50-60%, the metal Pt microparticles of 6-9%, 1-4%.
5. a kind of fuel cell as described in any claims of claim 1-4 is used from the preparation side of humidification control water quality proton exchange
Method, which is characterized in that specific preparation method is as follows：
（1）The doughnut is immersed to the polyethylene glycol phase-change material of heating melting, absorption polyethylene glycol takes after 2-10 hours
Go out Temperature fall, obtains the doughnut of load polyethylene glycol, then weave, obtain textle layers；
（2）Gelatin is dissolved in hot water, a concentration of 10%-30% of the gelatin, gelatin hot water is added in aerosil
In solution, impregnates 12-36 hours, make gelatin uniform adsorption in the micropore of aerosil, be warming up to 110-130 DEG C of steaming
Room temperature is cooled to after shampoo part, condensation obtains the aerosil gelatin corpuscle of load gelatin；
（3）The metal platinum of the mass ratio is uniformly mixed with graphene, by mechanical lapping 12-24h, it is negative to obtain metal platinum
Carry particle；
（4）By step（3）Obtained metal platinum carried fine particles are added in Nafion solution, by high-speed stirred and ultrasound point
It dissipates, so that the metal platinum carried fine particles is dispersed in Nafion solution, be then immersed in microporous teflon membran, impregnate
12-24h pulls drying out, obtains the perfluorinated sulfonic acid polymer composite membrane that microporous teflon membran is network skeleton；
（5）By gelatin corpuscle ultrasonic disperse in ethanol solution, gelatin corpuscle dispersion liquid is obtained, in step（4）Described
Perfluorinated sulfonic acid polymer composite membrane sprays gelatin corpuscle by anode surface, and attaches textle layers, obtains handing over from the control water proton that is humidified
Change film.
6. a kind of preparation method of water electrolysis hydrogen production solid electrolyte film according to claim 5, which is characterized in that step
Suddenly（1）Described in polyethylene glycol heating temperature be 68-87 DEG C.
7. a kind of preparation method of water electrolysis hydrogen production solid electrolyte film according to claim 5, which is characterized in that step
Suddenly（2）The temperature of the hot water is 60-80 DEG C.
8. a kind of preparation method of water electrolysis hydrogen production solid electrolyte film according to claim 5, which is characterized in that step
Suddenly（4）In, the mass concentration of a concentration of 5-7% of the Nafion solution, the metal platinum carried fine particles are 9-15%, described dry
Dry is vacuum drying, and vacuum degree 0.1-3kPa, temperature is 50-75 DEG C.
9. a kind of preparation method of water electrolysis hydrogen production solid electrolyte film according to claim 5, which is characterized in that step
Suddenly（5）Described in the mass concentration of gelatin corpuscle be 10-30%, the input speed of the spraying is 50-80ml/min, and compression is empty
Atmospheric pressure is 0.2-0.4 Mpa, and temperature is 70-110 DEG C at nozzle.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109888302A (en) * | 2019-02-25 | 2019-06-14 | 成都新柯力化工科技有限公司 | A kind of method that scale continuously prepares membrane electrode ordering Catalytic Layer |
| GB2582695A (en) * | 2019-01-17 | 2020-09-30 | Johnson Matthey Fuel Cells Ltd | Membrane |
| CN112271301A (en) * | 2020-10-16 | 2021-01-26 | 成都新柯力化工科技有限公司 | Method for preparing fuel cell membrane electrode by inorganic in-situ adhesion |
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| CN114899464A (en) * | 2022-05-30 | 2022-08-12 | 国家电投集团氢能科技发展有限公司 | Microporous membrane and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2582695A (en) * | 2019-01-17 | 2020-09-30 | Johnson Matthey Fuel Cells Ltd | Membrane |
| GB2582695B (en) * | 2019-01-17 | 2021-12-08 | Johnson Matthey Fuel Cells Ltd | Membrane |
| CN109888302A (en) * | 2019-02-25 | 2019-06-14 | 成都新柯力化工科技有限公司 | A kind of method that scale continuously prepares membrane electrode ordering Catalytic Layer |
| CN112271301A (en) * | 2020-10-16 | 2021-01-26 | 成都新柯力化工科技有限公司 | Method for preparing fuel cell membrane electrode by inorganic in-situ adhesion |
| CN113113622A (en) * | 2021-03-16 | 2021-07-13 | 国家电投集团氢能科技发展有限公司 | Fuel cell catalyst layer slurry and preparation method and application thereof |
| CN113097550A (en) * | 2021-04-01 | 2021-07-09 | 广东省科学院生物工程研究所 | Nafion composite membrane for high-temperature low-humidity proton exchange membrane fuel cell and preparation and application thereof |
| CN114220983A (en) * | 2021-12-15 | 2022-03-22 | 南京工业大学 | Modified membrane based on hollow carbon spheres and preparation method and application thereof |
| CN114220983B (en) * | 2021-12-15 | 2024-01-30 | 南京工业大学 | Modified membrane based on hollow carbon spheres and preparation method and application thereof |
| CN114899464A (en) * | 2022-05-30 | 2022-08-12 | 国家电投集团氢能科技发展有限公司 | Microporous membrane and preparation method and application thereof |
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Application publication date: 20180928 |