CN103490081B - Modification perfluorosulfonic acid proton exchange film, its preparation method and direct methanol fuel cell membrane electrode and preparation method thereof - Google Patents
Modification perfluorosulfonic acid proton exchange film, its preparation method and direct methanol fuel cell membrane electrode and preparation method thereof Download PDFInfo
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- CN103490081B CN103490081B CN201310459422.0A CN201310459422A CN103490081B CN 103490081 B CN103490081 B CN 103490081B CN 201310459422 A CN201310459422 A CN 201310459422A CN 103490081 B CN103490081 B CN 103490081B
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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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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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
- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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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
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- 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
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Abstract
The invention provides a kind of modification perfluorosulfonic acid proton exchange film and preparation method thereof, perfluorosulfonic acid proton exchange film under vacuo, is immersed in polybenzimidazoles phosphoric acid lysate by the method; Then the perfluorosulfonic acid proton exchange film after dry immersion, obtains modification perfluorosulfonic acid proton exchange film.The invention provides a kind of direct methanol fuel cell membrane electrode and preparation method thereof, the load of Yin/Yang electrode catalyst layer difference on the gas diffusion layers of Yin/Yang pole, is obtained Yin/Yang pole electrode by the method; Described anode electrode, modification perfluorosulfonic acid proton exchange film mentioned above and cathode electrode are stacked successively, through hot pressing, obtain membrane electrode, described modification perfluorosulfonic acid proton exchange film is adjacent with male/female electrode catalyst layer respectively.The polybenzimidazoles that the present invention is dissolved with phosphoric acid modifies perfluorosulfonic acid proton exchange film, reduces the transmission space of hydroaropic substance, can reduce methanol solution through; Simultaneously the better performances such as proton conductivity of film, is beneficial to and improves battery performance.
Description
Technical field
The present invention relates to field of fuel cell technology, particularly a kind of modification perfluorosulfonic acid proton exchange film, its preparation method and direct methanol fuel cell membrane electrode and preparation method thereof.
Background technology
As a kind of clean and efficient energy transition equipment, in decades, fuel cell obtains the extensive research of people always.Along with energy crisis appears in the whole world, fuel cell is paid close attention to being subject to emphasis especially, and people mainly wish the energy demand by adopting fuel cell to meet the whole world.In various dissimilar fuel cell, direct methanol fuel cell (DMFCs) belongs to Proton Exchange Membrane Fuel Cells, it directly uses methyl alcohol for fuel, oxygen or air are oxidant, operation principle is: at the anode of membrane electrode, electrochemical oxidation reactions is there is in methyl alcohol under the effect of catalyst, generate carbon dioxide, proton and electronics, the proton produced moves to the negative electrode of membrane electrode through the proton exchange membrane of membrane electrode, and at negative electrode and oxygen water generation reaction under the effect of catalyst, electronics is delivered to negative electrode by external circuit, release electric energy simultaneously, can externally do work.Direct methanol fuel cell has the advantages that production process is simple and energy efficiency is higher, therefore be it is believed that it is the clean energy resource being rich in development prospect most.
But, commercial applications direct methanol fuel cell is still faced with many problems, such as, the cathode oxidation caused to negative electrode because of crossover of methanol can make that the activity of cathod catalyst reduces, the crossover of methanol of anode catalyst to the low activity of methanol oxidation and proton exchange membrane is too high.Wherein, crossover of methanol is particularly serious to the problem of negative electrode.Because crossover of methanol can produce mixed potential at negative electrode usually; reduce Energy transmission efficiency; result also in the poisoning of cathod catalyst simultaneously; and methyl alcohol through the utilance that also greatly can reduce fuel; and then reduce the operating efficiency of direct methanol fuel cell; so solving the crossover of methanol problem of proton exchange membrane is the practical key point of direct methanol fuel cell.
At present, perfluorosulfonic acid proton exchange film, as Nafion film, has higher proton conductivity and stability because of it and is widely used in DMFCs the most.It is determined by its special Structure and form that Nafion film has excellent battery performance, in Nafion film, polytetrafluoro skeleton structure assembles formation hydrophobic region due to extremely strong hydrophobic effect, sulfonic acid group is due to strong hydrophilic interaction gathering formation ion cluster, form super hydrophilic region, make to form micro phase separation structure in film.By little angle and wide-angle x-ray diffraction, the micro-structural to Nafion film is studied the people such as Gierke, establishes ion cluster network configuration (cluster-network) model, and as shown in Figure 1, Fig. 1 is the microstructure of hygrometric state Nafion film.As shown in Figure 1, Nafion film is when absorbing water saturation condition, and carbon fluorine main chain forms certain crystalline phase hydrophobic region, containing sulfonic side chain due to hydrophilic and form water core reverse micelle ion cluster.Under moisture-saturated state, the diameter of ion cluster is about 4nm, bunch and bunch between distance be about 5nm, due to swelling action, the ion channel diameter formed between bunch is about 1nm, and hydrone enters into the hydrophilic region in film, thus forms the duct of proton transport.But the crossover of methanol of Nafion film is too high, the commercialization requirement of DMFCs can not be met well.
In order to reduce the methanol permeability of Nafion film, the scientists of various countries conducts extensive research and explores.Such as, adulterate in film organic material and inorganic material, form blend film, reached the object (Li, Q.F., etal., ChemistryofMaterials, 2003, the 15:4896-4915 that reduce crossover of methanol by inorganic material of adulterating in film; Li, X.F., etal., JournalofMembraneScience, 2006,281:1-6), or by with other without leading the polyblend of proton ability, preparation blend film and modification (Cui, Z.M. are carried out to Nafion, etal., JournalofPowerSources, 2007,167:94-99; Jones, D.J.andJ.Roziere, JournalofMembraneScience, 2001,185:41-58).But these methods, due to the material that can not conduct electricity that adulterates, can cause proton conductivity decline, mechanical performance reduction, and make cost increase further.In addition, prior art can also modify the resistance alcohol material of thin layer outside the anode side on Nafion film surface, with reduce methyl alcohol through (Linkous, C.A., etal., IntJHydrogenEnergy, 1998,23:525-529).But this surface modification has blocked the proton of anode catalyst catalysis methanol oxidation generation to the transfer of Nafion film main body, thus makes the proton conductivity of film entirety greatly reduce, is unfavorable for the raising of battery performance.
Summary of the invention
In order to solve above technical problem, the invention provides a kind of modification perfluorosulfonic acid proton exchange film, its preparation method and direct methanol fuel cell membrane electrode and preparation method thereof, the modification perfluorosulfonic acid proton exchange film adopting the inventive method to prepare has excellent alcohol-rejecting ability, can higher proton conductivity be ensured simultaneously, be beneficial to the raising of battery performance.
The invention provides a kind of preparation method of modification perfluorosulfonic acid proton exchange film, comprise the following steps:
Under vacuum, perfluorosulfonic acid proton exchange film is soaked in polybenzimidazoles phosphoric acid lysate, obtain the perfluorosulfonic acid proton exchange film after soaking;
Perfluorosulfonic acid proton exchange film after soaking is carried out drying, obtains modification perfluorosulfonic acid proton exchange film.
Preferably, the preparation method of described polybenzimidazoles phosphoric acid lysate comprises:
Polybenzimidazole membrane is dissolved in phosphoric acid solution, obtains polybenzimidazoles phosphoric acid lysate.
Preferably, the temperature of described dissolving is 100 DEG C ~ 150 DEG C.
Preferably, the time of described immersion is 12h ~ 36h.
Preferably, the temperature of described drying is 60 DEG C ~ 80 DEG C.
The invention provides a kind of modification perfluorosulfonic acid proton exchange film, its preparation method mentioned above obtains.
Compared with prior art, first perfluorosulfonic acid proton exchange film to be immersed in polybenzimidazoles phosphoric acid lysate and to vacuumize by the present invention, then dry soak after perfluorosulfonic acid proton exchange film, obtain modification perfluorosulfonic acid proton exchange film.Polybenzimidazoles (PBI) is a kind of unbodied thermoplastic polymer, have excellent thermal stability and mechanical property, and polybenzimidazole membrane can be used for the fuel cell of middle temperature (100 DEG C ~ 200 DEG C).In the present invention, there is phosphate-doped polybenzimidazoles in polybenzimidazoles phosphoric acid lysate, as being made into phosphate-doped polybenzimidazoles composite membrane, then this composite membrane inherently has the following advantages: (1) has good proton conduction property; (2) there is lower methanol permeability; (3) in conducting process, almost can not need the participation of water, in film, the electrostatic diffusion coefficient of water equals zero approx, and after this just makes to be applied to fuel cell, fuel cell stably can work when not additional moisture.And the polybenzimidazoles that the present invention adopts phosphoric acid to dissolve is to modify perfluorosulfonic acid proton exchange film, modification has been carried out to the hydrophilic transmission channel of film, its action principle is under vacuum, polybenzimidazoles that is hydrophobic, doping phosphoric acid can be filled in the water core reverse micelle ion cluster of perfluorosulfonic acid proton exchange film, reduce the transmission space of hydroaropic substance, thus can reduce well methanol solution through.Further, compared with chemical doping, there is not chemical reaction in said process, and other performances such as the proton conductivity of film can not be affected, thus be beneficial to and improve battery performance.
The invention provides a kind of direct methanol fuel cell membrane electrode, comprise the anode gas diffusion layer, anode catalyst layer, proton exchange membrane, cathode catalyst layer and the cathode gas diffusion layer that set gradually, it is characterized in that, described proton exchange membrane is modification perfluorosulfonic acid proton exchange film mentioned above.
Preferably, in described cathode catalyst layer, cathod catalyst is the black or Pt/C of Pt;
In described anode catalyst layer, anode catalyst is PtRu or PtRu/C.
Preferably, in described cathode catalyst layer, the carrying capacity of cathod catalyst is 4mg/cm
2~ 6mg/cm
2.
The invention provides a kind of preparation method of direct methanol fuel cell membrane electrode, comprise the following steps:
By cathode catalyst layer load on cathode gas diffusion layer, obtain cathode electrode;
By anode catalyst layer load on anode gas diffusion layer, obtain anode electrode;
Described anode electrode, modification perfluorosulfonic acid proton exchange film mentioned above and described cathode electrode are stacked successively, through hot pressing, obtain membrane electrode, described modification perfluorosulfonic acid proton exchange film is adjacent with cathode catalyst layer with described anode catalyst layer.
Compared with prior art, cathode catalyst layer load on cathode gas diffusion layer, is obtained cathode electrode by the present invention; By anode catalyst layer load on anode gas diffusion layer, obtain anode electrode; Described anode electrode, modification perfluorosulfonic acid proton exchange film mentioned above and described cathode electrode are stacked successively, through hot pressing, obtain membrane electrode, described modification perfluorosulfonic acid proton exchange film is adjacent with cathode catalyst layer with described anode catalyst layer.The proton exchange membrane that the present invention is direct methanol fuel cell membrane electrode with modification perfluorosulfonic acid proton exchange film mentioned above, can improve battery performance, be beneficial to commercial applications.
Accompanying drawing explanation
Fig. 1 is the microstructure of hygrometric state Nafion film;
Fig. 2 is the discharge voltage of the direct methanol fuel cell that obtains of embodiment 1 and comparative example 1 when 3M methyl alcohol and power density curve chart;
Fig. 3 is the discharge voltage of the direct methanol fuel cell that obtains of embodiment 1 and comparative example 1 when 10M methyl alcohol and power density curve chart;
Fig. 4 is the open circuit voltage curve figure of direct methanol fuel cell when pure methyl alcohol that embodiment 1 and comparative example 1 obtain;
Fig. 5 is the limiting current density curve chart of direct methanol fuel cell when 2M methyl alcohol that embodiment 1 and comparative example 1 obtain;
Fig. 6 is the discharge voltage of the direct methanol fuel cell that obtains of embodiment 1 and embodiment 2 when 3M methyl alcohol and power density curve chart;
Fig. 7 is the discharge voltage of the direct methanol fuel cell that obtains of embodiment 1 and embodiment 3 when 3M methyl alcohol and power density curve chart.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention provides a kind of preparation method of modification perfluorosulfonic acid proton exchange film, comprise the following steps:
Under vacuum, perfluorosulfonic acid proton exchange film is soaked in polybenzimidazoles phosphoric acid lysate, obtain the perfluorosulfonic acid proton exchange film after soaking;
Perfluorosulfonic acid proton exchange film after soaking is carried out drying, obtains modification perfluorosulfonic acid proton exchange film.
The present invention modifies perfluorosulfonic acid proton exchange film by adopting phosphate-doped polybenzimidazoles, has carried out modification to the hydrophilic transmission channel of film, makes modification perfluorosulfonic acid proton exchange film have excellent alcohol-rejecting ability and good proton conduction property.
First perfluorosulfonic acid proton exchange film is immersed in polybenzoxazole phosphoric acid lysate by the embodiment of the present invention, and vacuumizes a period of time, obtains the perfluorosulfonic acid proton exchange film after soaking.
In the proton exchange membrane of the numerous kinds of exploitation at present, the present invention carries out modification to widely used perfluorosulfonic acid proton exchange film.And Nafion film is a kind of perfluorosulfonic acid proton exchange film be widely used in the most in DMFCs, the present invention preferably carries out modification to Nafion film, the Nafion film of each series that described Nafion film can be well known to those skilled in the art.
The present invention adopts polybenzoxazole phosphoric acid lysate to soak described perfluorosulfonic acid proton exchange film, described polybenzimidazoles phosphoric acid lysate is the polybenzimidazoles that phosphoric acid dissolves, wherein there is phosphate-doped polybenzimidazoles, as being made into phosphate-doped polybenzimidazoles composite membrane, then this composite membrane inherently has the following advantages: (1) has good proton conduction property; (2) there is lower methanol permeability; (3) in conducting process, almost can not need the participation of water, in film, the electrostatic diffusion coefficient of water equals zero approx, and after this just makes to be applied to fuel cell, fuel cell stably can work when not additional moisture.
And the polybenzimidazoles that the present invention adopts phosphoric acid to dissolve is to modify perfluorosulfonic acid proton exchange film, the hydrophilic transmission channel of energy Modified Membrane, its action principle is: under vacuum, polybenzimidazoles that is hydrophobic, doping phosphoric acid can be filled in the water core reverse micelle ion cluster of perfluorosulfonic acid proton exchange film, reduce the transmission space of hydroaropic substance, thus can reduce well methanol solution through.Further, compared with chemical doping, there is not chemical reaction in said process, and other performances such as the proton conductivity of film can not be affected, thus be beneficial to and improve battery performance.
In the present invention, the preparation method of described polybenzimidazoles phosphoric acid lysate preferably includes:
Polybenzimidazole membrane is dissolved in phosphoric acid solution, obtains polybenzimidazoles phosphoric acid lysate.
Polybenzimidazoles (PBI) film is put into phosphoric acid (H by the embodiment of the present invention
3pO
4) in solution, dissolve completely at a certain temperature, obtain lysate.
Polybenzimidazoles is a kind of unbodied thermoplastic polymer, have excellent thermal stability and mechanical property, and polybenzimidazole membrane can be used for the fuel cell of middle temperature (100 DEG C ~ 200 DEG C).The present invention is not particularly limited described polybenzimidazole membrane, adopts commercially available.The present invention is also not particularly limited described phosphoric acid solution, if its concentration can be 85%.Described dissolving can make PBI be dissolved in phosphoric acid solution completely and form solution, and its temperature is preferably 100 DEG C ~ 150 DEG C, is more preferably 110 DEG C ~ 140 DEG C.
Described perfluorosulfonic acid proton exchange film is put into the PBI solution that phosphoric acid dissolves by the present invention, places under vacuum, namely after vacuumizing, soaking, obtains the perfluorosulfonic acid proton exchange film semi-finished product that PBI modifies.Wherein, the time that the time of described immersion namely vacuumizes is preferably 12h ~ 36h, is more preferably 15h ~ 25h.
After obtaining the perfluorosulfonic acid proton exchange film after soaking, the embodiment of the present invention puts it in drying box, dry at a certain temperature, obtains stable modification perfluorosulfonic acid proton exchange film finished product, i.e. PBI-perfluorosulfonic acid proton exchange film finished product.Wherein, the temperature of described drying is preferably 60 DEG C ~ 80 DEG C, is more preferably 65 DEG C ~ 75 DEG C.
Accordingly, the invention provides a kind of modification perfluorosulfonic acid proton exchange film, its preparation method by mentioned earlier obtains.
The preparation method of modification perfluorosulfonic acid proton exchange film provided by the invention is the preparation method of the low crossover of methanol film of a kind of direct methanol fuel cell, the film adopting method of the present invention to prepare has comparatively excellent alcohol-rejecting ability, can reduce methyl alcohol through, thus decrease the waste of cathodic polarization and fuel, improve the energy conversion rate of DMFCs.Further, the proton conductivity of described modification perfluorosulfonic acid proton exchange film is higher, adopts the electrode performance of this film preparation better, is beneficial to the performance improving battery.
In addition, the method is easy and simple to handle, carrying out complicated doping reaction, other performances of film can not be made to be subject to bad impact without the need to adding various organic and inorganic material.
Present invention also offers a kind of direct methanol fuel cell membrane electrode, comprise the anode gas diffusion layer, anode catalyst layer, proton exchange membrane, cathode catalyst layer and the cathode gas diffusion layer that set gradually, wherein, described proton exchange membrane is modification perfluorosulfonic acid proton exchange film mentioned above.
The proton exchange membrane that the present invention is direct methanol fuel cell membrane electrode with modification perfluorosulfonic acid proton exchange film mentioned above, can improve battery performance, be beneficial to commercial applications.
In the present invention, described membrane electrode comprises anode gas diffusion layer, anode catalyst layer, cathode catalyst layer and cathode gas diffusion layer are well known to the skilled person.In described cathode catalyst layer, cathod catalyst is preferably the black or Pt/C of Pt; The carrying capacity of cathod catalyst is preferably 4mg/cm
2~ 6mg/cm
2.In described anode catalyst layer, anode catalyst is preferably PtRu or PtRu/C.
Accordingly, the invention provides a kind of preparation method of direct methanol fuel cell membrane electrode, comprise the following steps:
By cathode catalyst layer load on cathode gas diffusion layer, obtain cathode electrode;
By anode catalyst layer load on anode gas diffusion layer, obtain anode electrode;
Described anode electrode, modification perfluorosulfonic acid proton exchange film mentioned above and described cathode electrode are stacked successively, through hot pressing, obtain membrane electrode, described modification perfluorosulfonic acid proton exchange film is adjacent with cathode catalyst layer with described anode catalyst layer.
The proton exchange membrane that the present invention is direct methanol fuel cell membrane electrode with modification perfluorosulfonic acid proton exchange film mentioned above, adopts the membrane electrode better performances of this film preparation, can improve the performance of battery, be beneficial to commercial applications.
In the present invention, described anode gas diffusion layer, anode catalyst layer, cathode catalyst layer and cathode gas diffusion layer all adopt this area to commonly use.
In one embodiment of the invention, described cathode gas diffusion layer can obtain in accordance with the following methods:
Carbon dust, water, isopropyl alcohol are mixed with polytetrafluoroethylsolution solution, obtains mixture;
By described mixture blade coating on negative electrode carbon paper, form microporous layers;
Calcine after the negative electrode carbon paper drying with microporous layers, obtain cathode gas diffusion layer.
Wherein, proportioning between the raw material such as described carbon dust, water, polytetrafluoroethylene (PTFE) solution and negative electrode carbon paper and raw material all adopts this area conventional.The quality of described carbon dust is relevant with the area of carbon paper, for the area of carbon paper is multiplied by 2; Described water is used for wetting carbon dust, generally adds a small amount of, and the amount empirically added ensures that carbon dust becomes paste in water; Described isopropyl alcohol is used for diluting carbon dust slurries, and because isopropyl alcohol is volatile, the impact of its addition is little.Described water and isopropyl alcohol are equivalent to solvent, and the amount added can empirically, as long as ensure that carbon dust forms paste in a solvent.Described PTFE is key factor, its volume added (V(mL)) be 2.5 quality being multiplied by carbon dust.Described mixing, blade coating, drying and calcining are technological means well known to those skilled in the art, and the present invention is not particularly limited.
Adopt anode carbon paper, be prepared according to above-mentioned method, correspondingly can obtain anode gas diffusion layer.
In one embodiment of the invention, described cathode catalyst layer can obtain in accordance with the following methods:
Cathod catalyst, water, perfluor sulfoacid resin solution are mixed with isopropyl alcohol, obtains mixture;
Described mixture is sprayed, obtains cathode catalyst layer.
Wherein, described cathod catalyst is preferably the black or Pt/C of Pt; The carrying capacity of described cathod catalyst is preferably 4mg/cm
2~ 6mg/cm
2, the quality=carrying capacity × carbon paper area of catalyst; Described perfluor sulfoacid resin solution is preferably Nafion solution.
Adopt anode catalyst, be prepared according to above-mentioned method, correspondingly can obtain anode catalyst layer.Wherein, described anode catalyst is preferably PtRu or PtRu/C.
After obtaining cathode gas diffusion layer, the mixture forming cathode catalyst layer is sprayed on it by the embodiment of the present invention, makes cathode catalyst layer load on described cathode gas diffusion layer, obtains cathode electrode.
Equally, after obtaining anode gas diffusion layer, the mixture forming anode catalyst layer is sprayed on it by the embodiment of the present invention, makes anode catalyst layer load on described anode gas diffusion layer, obtains anode electrode.
Finally, described anode electrode, modification perfluorosulfonic acid proton exchange film mentioned above and described cathode electrode stack by the embodiment of the present invention successively, through hot pressing, obtain membrane electrode, described modification perfluorosulfonic acid proton exchange film is adjacent with cathode catalyst layer with described anode catalyst layer.
Wherein, described hot pressing is technological means well known to those skilled in the art, and temperature is preferably 125 DEG C ~ 135 DEG C; Pressure is preferably 3MPa ~ 5MPa; Time is preferably 120s ~ 180s, is more preferably 150s ~ 170s.
After obtaining membrane electrode, the present invention is arranged in direct methanol fuel cell, at room temperature the performance of test battery.Method of testing is: adopt concentration to be respectively the methanol solution of 3M and 10M, the voltage at 25 DEG C during test battery electric discharge and power density.
Test result shows, the modification perfluorosulfonic acid proton exchange film adopting the inventive method to prepare has excellent alcohol-rejecting ability, can ensure higher proton conductivity simultaneously, be beneficial to the raising of battery performance.
In order to understand the present invention further, below in conjunction with embodiment, modification perfluorosulfonic acid proton exchange film provided by the invention, its preparation method and direct methanol fuel cell membrane electrode and preparation method thereof are specifically described.
Raw materials usedly in following examples be the conventional chemical articles for use buied from the market.Following examples and comparative example PBI film used are the PBI film of Shanghai Sheng Jun plastic cement Science and Technology Ltd.; Nafion film is the Nafion117 film of DuPont; H
3pO
4the concentration of solution is 80% ~ 90%.
Embodiment 1
(1) the PBI film of a slice 200mg is placed on 200mLH
3pO
4in solution, be heated to dissolve completely under the condition of 110 DEG C in temperature, obtain lysate;
The Nafion film of a slice 4cm × 4cm is put into described lysate, places 24h under vacuum, obtain PBI-Nafion film semi-finished product, wherein the doping ratio of PBI is about 1:4;
Described PBI-Nafion film semi-finished product are put into drying box, is dry under the condition of 60 DEG C in temperature, obtains PBI-Nafion film (PBI/Nafion film) finished product.
(2) get the VulcanXC-72R carbon dust of certain mass, and add deionized water and isopropyl alcohol successively wherein, be uniformly dispersed by stirring and ultrasonic making it, then add the PTFE solution that mass fraction is 10%, after being uniformly dispersed, obtain paste mixture;
By finely dispersed paste mixture by hand blade coating to negative electrode carbon paper TGP-H-030(, it contains the PTFE of 20wt%) on, formation carrying capacity is 2mg/cm
2microporous layers;
Be placed in Muffle furnace by under the negative electrode carbon paper natural conditions with microporous layers after drying, be calcine under the condition of 300 DEG C in temperature, after 30min, form cathode gas diffusion layer.
It contains the PTFE of 10wt% to adopt anode carbon paper TGP-H-060(), be prepared according to above-mentioned method, form anode gas diffusion layer.
Take a certain amount of Pt black, and add deionized water wherein successively, concentration be 5% Nafion solution and 20mL isopropyl alcohol, by stir and ultrasonic making it be uniformly dispersed, obtain slurry mixture; V
water=2.5m
catalyst/ 795(mL); V
nafion=3.2m
catalyst/ 795(mL);
Be sprayed on the cathode gas diffusion layer of preparation by finely dispersed slurry mixture spraying instrument, carrying capacity is 5mg/cm
2, obtain cathode electrode.
Take a certain amount of PtRu black, be sprayed on the anode gas diffusion layer of preparation according to above-mentioned method, carrying capacity is 5mg/cm
2, obtain anode electrode.
Described anode electrode, PBI/Nafion film finished product and described cathode electrode are stacked successively, in 130 DEG C, hot pressing 120s under 3MPa in hot press, obtains membrane electrode (by this membrane electrode called after M1).
M1 is arranged in a set of passive direct methanol fuel cell, according to the performance of method of testing test battery mentioned above.Test result as shown in Figures 2 and 3, Fig. 2 is the discharge voltage of the direct methanol fuel cell that obtains of embodiment 1 and comparative example 1 when 3M methyl alcohol and power density curve chart, and Fig. 3 is the discharge voltage of the direct methanol fuel cell that obtains of embodiment 1 and comparative example 1 when 10M methyl alcohol and power density curve chart.In figs. 2 and 3, abscissa is discharge current density, and main ordinate is discharge voltage, and secondary ordinate is power density.As can be seen from Fig. 2 and Fig. 3, when methanol concentration is 3M, the maximum power density adopting the battery of M1 is 25.5mW/cm
2; When methanol concentration is 10M, the maximum power density adopting the battery of M1 is 13.9mW/cm
2.
Pure methyl alcohol and concentration is adopted to be the methanol solution of 2M respectively, the open circuit voltage of the battery that test is provided with M1 at 25 DEG C when discharging and limiting current density.Test result is see Fig. 4 and Fig. 5, Fig. 4 is the open circuit voltage curve figure of direct methanol fuel cell when pure methyl alcohol that embodiment 1 and comparative example 1 obtain, Fig. 5 is the limiting current density curve chart of direct methanol fuel cell when 2M methyl alcohol that embodiment 1 and comparative example 1 obtain.As seen from Figure 4, when adopting pure methanol feeding, crossover of methanol is very serious, and M1 has alcohol-rejecting ability due to PBI-Nafion film, adopts the open circuit voltage of the battery of M1 to reduce amplitude less.As seen from Figure 5, when adopting 2M methanol feeding, the limiting current density adopting the battery of M1 is 24.5mA/cm
2.
From above test result, the modification perfluorosulfonic acid proton exchange film adopting the inventive method to prepare has excellent alcohol-rejecting ability, can ensure proton conductivity simultaneously, be beneficial to battery performance.
Comparative example 1
Adopt Nafion film, according to the method for embodiment 1, prepare membrane electrode (by this membrane electrode called after M4).
Be arranged on by M4 in a set of passive direct methanol fuel cell, according to the performance of method of testing test battery mentioned above, test result as shown in Figures 2 and 3.As can be seen from Fig. 2 and Fig. 3, when methanol concentration is 3M, the maximum power density adopting the battery of M4 is 29.1mW/cm
2; When methanol concentration is 10M, the maximum power density adopting the battery of M1 is 10.5mW/cm
2.
It can thus be appreciated that, use identical electrode composition, when methanol concentration is 3M, because concentration is lower, can there is mass transfer polarization at Dicharged at High Current Desity, M1 is owing to have employed PBI-Nafion film, alcohol-rejecting ability improves, and causes methyl alcohol under-supply, and makes its performance lower than M4; When methanol concentration is 10M, because concentration is higher, crossover of methanol is more, so the performance of M1 and M4 all decreases, but M1 is owing to have employed PBI-Nafion film, and alcohol-rejecting ability improves, and its maximum power density is higher than M4.
According to the method for embodiment 1, adopt pure methyl alcohol and concentration to be the methanol solution of 2M respectively, the open circuit voltage of the battery that test is provided with M4 at 25 DEG C when discharging and limiting current density, test result is see Fig. 4 and Fig. 5.As seen from Figure 4, use identical electrode composition, when adopting pure methanol feeding, crossover of methanol is very serious, adopts the open circuit voltage of the battery of M4 to reduce gradually in time, and always lower than the open circuit voltage of the battery of employing M1.As seen from Figure 5, use identical electrode composition, when adopting 2M methanol feeding, the limiting current density adopting the battery of M4 is 46mA/cm
2.The size of limiting current density can be used to reflect crossover of methanol number, the crossover of methanol being further illustrated M1 by Fig. 5 is less than M4, thus shows that the alcohol-rejecting ability of PBI-Nafion film is improved.
Embodiment 2
Outside " Nafion film is put into described lysate, places 12h under vacuum, obtain PBI-Nafion film semi-finished product " this step, all the other are identical with the method for embodiment 1, prepare membrane electrode (by this membrane electrode called after M2).
M2 is arranged in a set of passive direct methanol fuel cell, according to the performance of method of testing test battery mentioned above.As shown in Figure 6, Fig. 6 is the discharge voltage of the direct methanol fuel cell that obtains of embodiment 1 and embodiment 2 when 3M methyl alcohol and power density curve chart to test result.In figure 6, abscissa is discharge current density, and main ordinate is discharge voltage, and secondary ordinate is power density.
As seen from Figure 6, use identical electrode composition, when methanol concentration is 3M, the maximum power density adopting the battery of M1 is 25.5mW/cm
2, the maximum power density adopting the battery of M2 is 21.6mW/cm
2and the open circuit voltage of M1 is higher than the open circuit voltage of M2, but, when Dicharged at High Current Desity, the performance of M1 is larger than the hydraulic performance decline amplitude of M2, and this causes its methyl alcohol under-supply caused because M1 has higher alcohol-rejecting ability, illustrates the processing time of Nafion film longer, PBI fills comparatively abundant, and alcohol-rejecting ability improves further.
Embodiment 3
Outside " Nafion film is put into described lysate, places 36h under vacuum, obtain PBI-Nafion film semi-finished product " this step, all the other are identical with the method for embodiment 1, prepare membrane electrode (by this membrane electrode called after M3).
M3 is arranged in a set of passive direct methanol fuel cell, according to the performance of method of testing test battery mentioned above.As shown in Figure 7, Fig. 7 is the discharge voltage of the direct methanol fuel cell that obtains of embodiment 1 and embodiment 3 when 3M methyl alcohol and power density curve chart to test result.In the figure 7, abscissa is discharge current density, and main ordinate is discharge voltage, and secondary ordinate is power density.
As seen from Figure 7, use identical electrode composition, when methanol concentration is 3M, the maximum power density adopting the battery of M1 is 25.5mW/cm
2, the maximum power density adopting the battery of M3 is 26.6mW/cm
2, power density is more or less the same, and the open circuit voltage of M1 and M3 is also similar, illustrates the processing time of Nafion film long, and PBI fills and reaches capacity, and alcohol-rejecting ability reaches the highest.
From above embodiment and comparative example, the modification perfluorosulfonic acid proton exchange film adopting the inventive method to prepare has excellent alcohol-rejecting ability, can ensure higher proton conductivity simultaneously, be beneficial to the raising of battery performance.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
Claims (9)
1. a preparation method for modification perfluorosulfonic acid proton exchange film, comprises the following steps:
Under vacuum, perfluorosulfonic acid proton exchange film is soaked in polybenzimidazoles phosphoric acid lysate, obtain the perfluorosulfonic acid proton exchange film after soaking;
Perfluorosulfonic acid proton exchange film after soaking is carried out drying, obtains modification perfluorosulfonic acid proton exchange film;
The preparation method of described polybenzimidazoles phosphoric acid lysate comprises:
Polybenzimidazole membrane is dissolved in phosphoric acid solution, obtains polybenzimidazoles phosphoric acid lysate.
2. the preparation method of modification perfluorosulfonic acid proton exchange film according to claim 1, is characterized in that, the temperature of described dissolving is 100 DEG C ~ 150 DEG C.
3. the preparation method of modification perfluorosulfonic acid proton exchange film according to claim 1, is characterized in that, the time of described immersion is 12h ~ 36h.
4. the preparation method of modification perfluorosulfonic acid proton exchange film according to claim 1, is characterized in that, the temperature of described drying is 60 DEG C ~ 80 DEG C.
5. a modification perfluorosulfonic acid proton exchange film, is characterized in that, is obtained by the preparation method described in any one of Claims 1 to 4.
6. a direct methanol fuel cell membrane electrode, comprise the anode gas diffusion layer, anode catalyst layer, proton exchange membrane, cathode catalyst layer and the cathode gas diffusion layer that set gradually, it is characterized in that, described proton exchange membrane is modification perfluorosulfonic acid proton exchange film according to claim 5.
7. direct methanol fuel cell membrane electrode according to claim 6, is characterized in that, in described cathode catalyst layer, cathod catalyst is the black or Pt/C of Pt;
In described anode catalyst layer, anode catalyst is PtRu or PtRu/C.
8. direct methanol fuel cell membrane electrode according to claim 6, is characterized in that, in described cathode catalyst layer, the carrying capacity of cathod catalyst is 4mg/cm
2~ 6mg/cm
2.
9. a preparation method for direct methanol fuel cell membrane electrode, comprises the following steps:
By cathode catalyst layer load on cathode gas diffusion layer, obtain cathode electrode;
By anode catalyst layer load on anode gas diffusion layer, obtain anode electrode;
Described anode electrode, modification perfluorosulfonic acid proton exchange film according to claim 5 and described cathode electrode are stacked successively, through hot pressing, obtain membrane electrode, described modification perfluorosulfonic acid proton exchange film is adjacent with cathode catalyst layer with described anode catalyst layer.
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