CN101170183B - A carbon nano tube enhanced self-humidied compound proton exchange film and its preparation - Google Patents
A carbon nano tube enhanced self-humidied compound proton exchange film and its preparation Download PDFInfo
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Abstract
The invention relates to a fuel cell, in particular to a self-humidifying combined proton exchange membrane for a strengthening fuel cell based on a carbon nanotube and a preparation method thereof, which comprises the following steps: a solution casting method is utilized to prepare and obtain a strengthened perfluorosulfonic resin membrane of the carbon nanotube, and Pt is introduced into the membrane as self-humidifying catalyst, wherein, Pt can be directly carried on the carbon nanotube or carried on nano SiO2 particle, and the prepared membrane is 10-100 [mu]m thick. The prepared combined membrane thickness and nanotube content can be easily controlled, the manufactured membrane surface is level and smooth, not ventilate, has no short-circuit with good intensity, has better cell performance on self-humidifying operation, and can be safely applied to the fuel cell.
Description
Technical field
The present invention relates to the proton exchange membrane of fuel cell, a kind of specifically self-humidifying composite proton exchange film for fuel cell that strengthens based on carbon nano-tube and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) has high power density, high-energy conversion efficiency, cold-starting, advantages of environment protection, and it will be widely used in fields such as space flight, military affairs, the energy and traffic.Proton exchange membrane (PEM) is one of core building block of PEMFC, it with general chemical power source in the barrier film that uses a great difference is arranged, at first it is not only a kind of diaphragm material, and it still is the substrate of electrolyte (transmission proton) and electrode active material (eelctro-catalyst); In addition, PEM is different from common porous membrane, and it is a kind of selective permeation film of densification.Desirable PEM should have proton conductivity height, low, the sufficiently high mechanical strength of gas permeability, thermal stability and chemical stability, suitable performance and price ratio.
At present, to hinder a key factor of PEMFC commercialization process be proton exchange membrane price and performance are unsatisfactory.The way of dealing with problems has two: the one, and the consumption of minimizing perfluorinated sulfonic resin; The 2nd, the non-fluorine proton exchange membrane material that exploitation is cheap.But perfluorinated sulfonic resin has the incomparable advantage of other material aspect chemical property and the chemical stability at present.So the consumption that reduces perfluorinated sulfonic resin by the thickness that reduces the perfluorinated sulfonic resin film is just very necessary.So not only can save material, reduce cost, and the reduction of film thickness can reduce the internal resistance of cell, thereby improve battery performance.But the reduction of perfluorinated sulfonic resin film thickness can reduce the mechanical strength of film, is unfavorable for the practical application of fuel cell.Therefore need to adopt composite methods to improve the mechanical strength of film.
Simultaneously, that uses at present needs existing of water with Nafion as the perfluorinated sulfonic resin film proton conducting of representative, and its conductivity and its water content are almost linear.And the even aquation of whole proton exchange membrane can prevent the part dehydration of film, or hot localised points, also may avoid because the battery performance that the film dehydration causes descends and the degraded of membrane material.Therefore, keep the water content of proton exchange membrane abundance just very important.
Usually, thereby all use complicated pure water humidification auxiliary system to come humidification fuel and reacting gas humidification PEM among the PEMFC, therefore increased weight, complexity, cost and the in-fighting of battery.Because the water that negative electrode generates can not in time be discharged electrode, cause that easily electrode is not had phenomenon by water logging during big current work.Having one of difficult problem that the PEMFC of outer humidification auxiliary system is applied to be faced with on the electric automobile is that water low temperature freezes.Therefore, explore and simplify or cancellation pure water humidification system, can reduce the complexity of system, improve energy content of battery efficient, reduce the battery cost, have important research meaning and using value.
The water transport mechanism is as follows among the PEMFC: have only negative electrode to generate water in the battery, the proton that anode generates transmits water from anode to negative electrode with the hydrated ion form.The water anode back-diffusion that only relies on negative electrode to generate, it is unbalance to cause water to transmit when high current density is worked, and causes galvanic anode side dehydration drying, and film resistance increases.Therefore, conventional P EMFC relies on humidification reacting gas mode water supply humidification PEM in battery.We know from PEMFC water transport mechanism, if can reduce the thickness of film, just can quicken the back-diffusion that negative electrode generates the water anode, help the operation of battery under the dry gas state.Simultaneously, if in PEM, introduce one deck contain Pt from the humidification layer, cut off electrical conductivity between them at the Nafion layer between humidification layer and electrode, electrocatalytic reaction can not take place in the Pt catalyst in the humidification layer, but can chemical catalysis respectively from the H of anode and negative electrode infiltration
2And O
2Generate water.The common humidification PEM of generation water in the humidification layer and the water from the negative electrode back-diffusion to anode is chosen as SiO if support the carrier of Pt catalyst simultaneously
2Deng the material of possess hydrophilic property, battery can adsorb a certain amount of water when low current density is worked, and can discharge water when high current density is worked, and can realize the PEMFC from the humidification stable operation.In addition, can effectively stop H from the humidification layer
2And O
2To the Catalytic Layer diffusion of yin, yang two electrodes, reduce to improve the service behaviour of battery respectively because the short circuit current that gas permeation causes can reduce cathode electrode polarization overpotential.
Thereby the thickness that reduces proton exchange membrane helps the battery performance of back-diffusion raising fuel cell under the dry gas operation that negative electrode generates the water anode, but the reduction of thickness can make proton exchange film strength and dimensional stability descend, and this just needs to adopt composite methods to improve the mechanical performance of film.This shows that exploitation has and strengthens and the compound proton exchange membrane of self-moistening function is very important for the practical application of PEMFC.
The enhancing proton exchange membrane that is adopted at present all patents, document all is to be support membrane or to be fortifying fibre with the PTFE fiber with the PTFE perforated membrane.
The twentieth century Gore﹠amp nineties; Associated company adopts stretching PTFE perforated membrane to develop enhancing perfluorinated sulfonic resin proton exchange membrane, thickness is 20-40 μ m, it is except having excellent in chemical performance and electrical property, also show the favorable mechanical performance, be widely used in PEMFC now, its commodity are called Gore-Select
TM
In WO Patent 98/51733, at first by hot pressing under 310 ℃ of vacuum states together the PTFE film of the thick Gore company of the perfluorinated sulfonic resin film of the thick sulfuryl fluoride type of 25 μ m and 23-25 μ m, then film hydrolysis in the KOH solution of dimethyl sulfoxide (DMSO) (DMSO), make in the film-SO
2The F group changes into-SO
3 -, be coated with three times 5% perfluor sulfoacid resin solution in the one side of porous PTFE film at last, in 150 ℃ of vacuum drying ovens, make film become as a whole.Obvious this method is too time-consuming, needs several steps just can finish.
Dalian Chemical Physics Research Institute at first soaks the PTFE perforated membrane in Chinese patent CN 1416186A in ethanolic solution, remove the organic substance of porous film surface; On perforated membrane, drip perfluorinated sulfonic resin then with the high boiling organic solvent dissolving; Be put at last in the vacuum drying oven, heating promptly makes perfluorinated sulfonic resin compound proton exchange membrane again.This method prepares the thickness of composite membrane and the immersion amount of perfluorinated sulfonic resin is controlled easily, and the film-strength of making is good, and this method cost is lower.
At European patent EP1, in 139,472, Asahi Glass company introduction a kind of method of using PTFE fiber reinforcement perfluorinated sulfonic resin film.Granulation after the presoma of perfluorinated sulfonic resin and the PTFE powder adopts the hot-stretch method to obtain a kind of thicker basement membrane, and this then basement membrane stretches with support membrane and obtains a kind of thin cationic membrane, and acidifying obtains fiber reinforced film then.But the complex process of this method, PTFE is not the very high fortifying fibre of a kind of intensity in addition, the composite membrane intensity that obtains at last improves smaller.
At present more about the document patent of self-humidifying fuel cell, the realization fuel cell is generally used two kinds of methods from the humidification operation, and a kind of is by designing suitable gas flow field channels, quickening negative electrode and generate the back-diffusion of water anode; Another kind is exactly to introduce metal Pt in proton exchange membrane, relies on the O that infiltrates into PEM
2And H
2Come the humidification battery at Pt catalyst surface chemical catalysis water generation reaction.
At document 1[J.Electrochem.Soc.143 (1996) 3847-3852], document 2[J.Electrochem.Soc, 145 (1998) 1137-114] and document 3 in [J.Phys.Chem.B, 102 (1998) 3129-3137], Japan scholar Watanabe M has reported a kind of self-humidifying method, mainly is the O that relies on from the infiltration of negative and positive the two poles of the earth
2And H
2Pt catalyst surface chemical catalysis water generation reaction in PEM is with negative electrode O
2Reduction reaction generates the two acting in conjunction humidification PEM of water.In PEM, utilize chemical plating to form the catalyst Pt particle (d=1-2nm) of high degree of dispersion, perhaps adopt and contain the casting film again of Pt particle, hydrophilic oxide and Nafion resin as electrolyte, the Pt catalyst particle has high specific area, and chemical catalysis is penetrated into its surperficial O respectively from negative and positive the two poles of the earth
2And H
2Generate water in PEM, when low current density, hydrophilic oxide absorbs water, discharges water when high current density.But the chemical plating Pt complex process of this scheme, the cycle is longer, and the Pt in the composite membrane might form continuous electron channel and cause the internal short-circuit of composite membrane.
In patent [Chinese patent application number: 00110729.1], Dalian Chemical Physics Research Institute adopts Du commercial proton exchange membrane of Pont company such as Nafion 112 and Nafion 115 films to make electrolyte, prepare the Pt/C-Nafion film from the humidification layer in its anode-side, studied Nafion resin content in humidification layer Pt/C-Nafion film to the influence of battery from the humidification effect, and battery carried out scale-up, when having estimated oxygen or air oxidant from the service behaviour of humidification actuating battery.But adopt thick film (Nafion 115), H
2And O
2Infiltration capacity by film is limited, makes whole DeGrain from humidification operation.
In recent years, also there are many research workers to develop and have the proton exchange membrane of enhancing and self-moistening function simultaneously.At first prepare the thinner proton exchange membrane of thickness, and then in film, introduce self-moistening function by the method that strengthens.
In patent [Chinese patent application number: 02122635.0], it serves as to strengthen the enhancing of body from the humidification composite membrane that Dalian Chemical Physics Research Institute utilizes the perfluor sulfoacid resin solution of the supported catalyst that contains Pt to adopt casting method to prepare with organic porous films such as PTFE.This method is simple to operate, and one step of composite membrane finishes, and the thickness of composite membrane is controlled easily with the loading that contains the supported catalyst unit are of Pt.
At document 4[J.Solid-State Lett., 9 (2006) A49-A52] and 5[J.Power Sources, in press] in, the researcher of Dalian Chemical Physics Research Institute is supporter with the porous ptfe film, utilize casting method to obtain the Nafion/PTFE composite membrane, in the both sides of this film and film, introduce Pt/SiO respectively
2Catalyst utilizes Pt catalysis to infiltrate into H in the film from anode and negative electrode respectively
2And O
2Generate the water humidifying proton exchange film.Adopt nonconducting SiO
2Be catalyst carrier, can avoid the internal short-circuit of film.
Because the volume content of PTFE can be led by the apparent in view electricity that influences composite membrane than higher in this class composite membrane, the intensity of PTFE is not very high simultaneously, causes compound film strength raising to be restricted.A kind of fiber doping content is lower, the more obvious method of reinforced effects strengthens proton exchange membrane so be necessary to adopt.Carbon nano-tube has that caliber is little, draw ratio is big, advantages of high strength and become desirable fibre reinforcement, and lower doping content just can significantly improve the mechanical strength of composite material, and the while can reduce the influence to the composite membrane proton conductivity again.Therefore this patent has been foundational development with the carbon nano-tube enhancing and has had an ionic exchange film for fuel cell of self-moistening function.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of fuel cell with the perfluorinated sulfonic resin compound proton exchange membrane of carbon nano-tube enhancing with self-moistening function, this method is simple to operate, the composite membrane of making is airtight, intensity is good, cost is low, not short circuit, and the film surfacing is smooth, battery performance is better, can being applied in the fuel cell of safety go.
For achieving the above object, the technical solution used in the present invention is divided into two parts, comprises the steps: respectively
The carbon nano-tube that adopts is single wall or multi-walled carbon nano-tubes, and diameter is 0.4-100nm, and length is 100nm-50 μ m; Its diameter is preferably 1-50nm, and length is preferably 100nm-5 μ m.The dispersiveness of carbon nano-tube in solvent reaches and the binding ability of Nafion resin in order to improve, and needs at first carry out surface modification to strengthen its hydrophilicity to carbon nano-tube.1.0g CNTs is placed the dense HNO of 100mL
3In, 140 ℃ of backflow 4h to remove the pollutant on surface, after rinsed with deionized water 3 times, add the dense HNO of 100mL
3+ dense H
2SO
4(1: 1, V/V), continue to carry out the surface-functionalized of carbon nano-tube at 140 ℃ of following backflow 4h, cyclic washing is to neutral, and is standby behind 80 ℃ of vacuumize 24h.
Measure the 0.05M H of certain volume
2PtCl
66H
2O mixes in a beaker with 25ml EG and 0.4ml 0.4M NaOH, and 0.200g CNTs is put into above-mentioned mixed solution, ultrasonicly then makes it fully mix.Beaker is put into microwave oven (LG WD700,2450MHz, 700W) middle heating 60s.With the suspension centrifugation that obtains, the precipitation that obtains is used deionized water rinsing repeatedly.Then this is deposited in 80 ℃ of vacuum drying chambers standby behind the dry 12h.The quality percentage composition of Pt is about 0.01-30% among the Pt/CNTs.
Measure the 0.05M H of certain volume
2PtCl
66H
2O mixes in a beaker with 25ml EG and 0.4ml 0.4M NaOH, with 0.200g SiO
2Put into above-mentioned mixed solution, ultrasonic then dispersion makes it fully mix.Beaker is put into microwave oven (LG WD700,2450MHz, 700W) middle heating 60s.With the suspension centrifugation that obtains, the precipitation that obtains is used deionized water rinsing repeatedly.Then this is deposited in 80 ℃ of vacuum drying chambers standby behind the dry 12h.Pt/SiO
2The quality percentage composition of middle Pt is about 0.01-30%.
This membrane structure can be divided into two classes:
The first kind is made up of Pt/CNTs and perfluorinated sulfonic resin: at first be dispersed in by Pt/CNTs and form one deck in the perfluorinated sulfonic resin and have individual layer composite membrane from humidification, enhancement function, compound respectively again one deck perfluorinated sulfonic resin forms the composite membrane with three-decker in the both sides of this tunic then;
Scheme one:
The self-humidifying composite proton exchange film that a kind of carbon nano-tube strengthens is formed the intermediate layer by perfluorinated sulfonic resin with supporting by the carbon nano-tube of metal Pt, and the compound respectively one deck perfluorinated sulfonic resin in its both sides forms the composite membrane with three-decker; The quality percentage composition of Pt/CNTs is 0.5-30% in the intermediate layer, and wherein the quality loading of Pt is 0.01-30wt.% in the Pt/CNTs catalyst.
A. perfluor sulfoacid resin solution is placed on the 30-80 ℃ of hot platform, make solvent evaporates, add a certain amount of high boiling organic solvent then as N, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAC), N-methylpyrrole gastral cavity ketone (NMP) or dimethyl sulfoxide (DMSO) (DMSO) dissolve perfluorinated sulfonic resin again.Add a certain amount of Pt/CNTs, ultrasonic dispersion obtains high boiling solvent-Pt/CNTs-perfluor sulfoacid resin solution.This solution-cast of obtaining in horizontal glass plate casting film frame, is put on the 40-50 ℃ of hot platform, makes the solvent evaporates casting film;
B. glass plate is taken off from hot platform, take out the Pt/CNTs-perfluorinated sulfonic resin individual layer composite membrane of preparation, spray respectively in the both sides of this film then or flood the perfluorinated sulfonic resin layer that a layer thickness is 0.5-10 μ m, dry naturally, obtain three layers of composite membrane.This film is put in the vacuum drying oven, the heating-up temperature scope is 120-200 ℃, 0.5-20h take out the back, prepares by having from humidification and the compound proton exchange membrane that strengthens dual-use function that Pt/CNTs and perfluorinated sulfonic resin are formed, the film thickness that makes is 6-120 μ m.
May further comprise the steps,
(1) heating for dissolving perfluorinated sulfonic resin film in the solvent of low boiling organic alcohols and water is made mass content 1-15% perfluor sulfoacid resin solution;
(2) in the perfluor sulfoacid resin solution of step (1) preparation or business-like perfluor sulfoacid resin solution, add high boiling organic solvent by the mass ratio of perfluor sulfoacid resin solution 1: 5-50 in high boiling organic solvent and the step (1);
(3) add Pt/CNTs in the perfluor sulfoacid resin solution of step (2) preparation, Pt/CNTs accounts for the 0.5%-30% of Pt/CNTs and perfluorinated sulfonic resin gross mass in the formed solution; Ultrasonic dispersion obtains finely dispersed Pt/CNTs-perfluor sulfoacid resin solution;
(4) solution casting that step (3) is prepared is in the glass casting film frame of level, and 40-120 ℃ is heated 1-3h on heating station, and forming thickness is the intermediate layer of 5-100 μ m;
(5) film with step (4) preparation takes out, and sprays respectively in its both sides or floods certain thickness perfluorinated sulfonic resin, and the thickness of each side perfluorinated sulfonic resin is respectively 0.5 μ m-10 μ m;
(6) composite membrane of above-mentioned steps preparation is placed 0.5-20h in 120-200 ℃ the vacuum drying oven, cooling promptly obtains the described three layers of composite membrane being made up of Pt/CNTs and perfluorinated sulfonic resin of claim 1.
Described low boiling organic alcohols solvent is ethanol, methyl alcohol, isopropyl alcohol or propyl alcohol;
Described high boiling organic solvent is N, N-methylformamide, N, N-dimethylacetylamide, N methylpyrrole gastral cavity ketone or dimethyl sulfoxide (DMSO).
Scheme two:
Second class is by Pt/SiO
2, carbon nano-tube and perfluorinated sulfonic resin form, and at first is dispersed in an individual layer composite membrane that obtains having enhancement function in the perfluorinated sulfonic resin by carbon nano-tube, is dispersed with Pt/SiO at the compound respectively again one deck in the both sides of this film then
2Perfluorinated sulfonic resin form composite membrane with three-decker.
The self-humidifying composite proton exchange film that a kind of carbon nano-tube strengthens is formed the intermediate layer by perfluorinated sulfonic resin and carbon nano-tube, and the compound respectively one deck in its both sides contains nanometer SiO
2The Pt/SiO of particles supported Pt
2Perfluorinated sulfonic resin form composite membrane with three-decker; The quality percentage composition of CNTs is 0.5-30%, wherein Pt/SiO in the intermediate layer
2The quality loading of Pt is 0.01-30wt.% in the catalyst.
Described carbon nano-tube is single wall or multi-walled carbon nano-tubes, and its diameter is 0.4-100nm, and length is 100nm-50 μ m, SiO
2Particle diameter be 5nm-500nm.
A. perfluor sulfoacid resin solution is placed on the 30-80 ℃ of hot platform, make solvent evaporates, add a certain amount of high boiling organic solvent then as N, dinethylformamide (DMF), N, N-dimethylacetylamide (DMAC), N-methylpyrrole gastral cavity ketone (NMP) or dimethyl sulfoxide (DMSO) (DMSO) dissolve perfluorinated sulfonic resin again.Add a certain amount of CNTs, ultrasonic dispersion obtains high boiling solvent-CNTs-perfluor sulfoacid resin solution.This solution-cast of obtaining in horizontal glass plate casting film frame, is put on the 40-50 ℃ of hot platform, makes the solvent evaporates casting film;
B. glass plate is taken off from hot platform, take out the CNTs-perfluorinated sulfonic resin individual layer composite membrane of preparation, spray respectively in the both sides of this film then or flood the Pt/SiO that is dispersed with that a layer thickness is 0.5-10 μ m
2The perfluorinated sulfonic resin layer, dry naturally, obtain three layers of composite membrane.This film is put in the vacuum drying oven, and the heating-up temperature scope is 120-200 ℃, takes out behind the 0.5-20h, prepares by Pt/SiO
2, having of forming of carbon nano-tube and perfluorinated sulfonic resin is from humidification and strengthen the compound proton exchange membrane of dual-use function, the film thickness of preparation is 6-120 μ m.
May further comprise the steps,
1) heating for dissolving perfluorinated sulfonic resin film in the solvent of low boiling organic alcohols and water is made the 1-15% perfluor sulfoacid resin solution;
2) in the perfluor sulfoacid resin solution of step 1) preparation or business-like perfluor sulfoacid resin solution, add high boiling organic solvent by the mass ratio of high boiling organic solvent and step 1) perfluor sulfoacid resin solution 1: 5-50;
3) to step 2) preparation perfluor sulfoacid resin solution in add carbon nano-tube; Ultrasonic dispersion obtains finely dispersed CNTs-perfluor sulfoacid resin solution; The 0.5%-30% of carbon nano-tube carbon nano-tube and perfluorinated sulfonic resin gross mass;
4) solution casting that step 3) is prepared is in the glass casting film frame of level, and 40-120 ℃ is heated 1-3h on heating station, and forming thickness is the intermediate layer of 5-100 μ m;
5) film with step 4) preparation takes out, and sprays respectively in its both sides or floods the certain thickness Pt/SiO of being dispersed with
2Perfluorinated sulfonic resin, each side Pt/SiO
2The thickness of-perfluorinated sulfonic resin is respectively 0.5-10 μ m, wherein Pt/SiO in the layer of both sides
2Account for Pt/SiO
21%-30% with the perfluorinated sulfonic resin gross mass; Pt/SiO
2The quality percentage composition of Pt is 0.01%-30% in the catalyst;
6) composite membrane of above-mentioned steps preparation is placed 0.5-20h in 120-200 ℃ the vacuum drying oven, it is described by Pt/SiO that cooling promptly obtains claim 6
2Three layers of composite membrane with the perfluorinated sulfonic resin composition.
Described low boiling organic alcohols solvent is ethanol, methyl alcohol, isopropyl alcohol or propyl alcohol;
Described high boiling organic solvent is N, dinethylformamide, N, N-dimethylacetylamide, N methylpyrrole gastral cavity ketone or dimethyl sulfoxide (DMSO).
To the heat treatment of composite membrane is a committed step in the film-forming process.In perfluorinated sulfonic resin, its similar polytetrafluoroethylene fluorine carbon backbone chain forms certain crystalline phase hydrophobic region; Form phase separation structure with the side chain of hydrophilic sulfonate radical.During aquation, the elastic force between the fluorine carbon backbone chain weakens under being higher than room temperature, forms inverted structure.When heat treatment, merge again between the fluorine carbon backbone chain, form have certain intensity, insoluble structure.Obtain well behaved film, must use high boiling solvent such as dissolved carbon nanotube-perfluorinated sulfonic resins such as DMSO, DMF, DMAC and NMP, high-temperature process film forming again.Therefore, the film-forming temperature of carbon nano-tube-perfluorinated sulfonic resin compound proton exchange membrane (120-200 ℃) between its glass transition temperature and melt temperature.
The method of being introduced in the present invention and the background technology relatively has following advantage:
1. compare with the composite membrane that the PTFE perforated membrane is done supporting layer, the method technological operation of adopting carbon nano-tube to strengthen is simple.
2. compare with adopting the fibre-reinforced method of PTFE, this method technology is simple, and the intensity that strengthens the body carbon nano-tube helps the raising of composite material strength far above the PTFE fiber.
3. owing to strengthen the intensity height of body, can use very low content and significantly improve the mechanical strength of composite membrane, so just can reduce of the reduction of enhancing body to the composite membrane conductivity as far as possible.
4. compare with document 1-3, this method can not cause the internal short-circuit of composite membrane.Catalyst in the composite membrane of this method preparation can not be communicated with the catalyst in the electrode, promptly can not produce the electrochemical catalysis reaction, and only can infiltrate into the interior H of film by chemical catalysis
2And O
2Water generation reaction.
5. the thickness that adopts the present invention's preparation is that the battery performance of perfluorinated sulfonic resin composite membrane when battery has external humidification and no external humidification of 25 μ m all is better than the business-like Nafion of Du Pont company
The battery of NRE-212 (50 μ m) assembling.
For further understanding flesh and blood of the present invention, provide embodiment below and in conjunction with the accompanying drawings the present invention is done detailed description.
Description of drawings
Fig. 1 is the TEM photo of the configuration of surface of the Pt/CNTs in the embodiments of the invention 1;
Fig. 2 is the Pt/CNTs-Nafion composite membrane section SEM photo in the embodiments of the invention 1; Wherein: what the I district represented is the pure Nafion floor of composite membrane both sides; What the II district represented is the Nafion floor that is dispersed with Pt/CNTs, and what small particles was wherein represented is the section of Pt/CNTs.
Fig. 3 be CNTs-Nafion film and Nafion NRE-212 film in Pt/CNTs-Nafion composite membrane in the embodiments of the invention 1 and the comparing embodiment 1 outer humidification battery performance relatively; Operating condition is: 80 ℃ of battery temperatures, and full humidification, operating pressure is 0.2MPa, gas is hydrogen and oxygen.
Fig. 4 be in Pt/CNTs-Nafion composite membrane in the embodiments of the invention 1 and the comparing embodiment 1 CNTs-Nafion film and Nafion NRE-212 film from the humidification battery performance relatively; Operating condition is: 80 ℃ of battery temperatures, and dry gas, operating pressure are 0.2MPa, gas is hydrogen and oxygen.
Fig. 5 is the Pt/SiO in the embodiments of the invention 2
2-Nafion composite membrane section SEM photo; Wherein: that the I district represents is the Pt/SiO that is dispersed with of composite membrane both sides
2The Nafion layer; What the II district represented is the Nafion floor that is dispersed with CNTs, and what small particles was wherein represented is the section of carbon nano-tube.The arrow indication is Pt/SiO among the figure
2
Embodiment
Below by embodiment the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1: get 3g 5.4%Nafion solution and pour in the small beaker, heating with the low boiling point organic solvent volatilization totally adds the analytically pure DMF solution of 3ml then the Nafion resin is dissolved again on 50 ℃ of hot platforms.The employing diameter is that 30nm, length are that the Pt quality percentage composition of the made of carbon nanotubes about 3 μ m is 1% Pt/CNTs as from the humidification catalyst.Get in the Nafion solution after 5mg Pt/CNTs adds the DMF dissolving, ultrasonic dispersion 10min obtains uniform Pt/CNTs-Nafion-DMF solution.Leaving standstill the bubble of driving away in this solution, is 20cm with its impouring area
2Plate glass casting film frame in, the casting film frame is placed on the heating platform of a level.On 50 ℃ hot platform, heat 2h solvent flashing film forming then, the film that obtains is taken out, spray the mixed solution of 0.185g 5.4%Nafion solution and 2g isopropyl alcohol preparation then respectively in its both sides, naturally dry, form the pure Nafion resin bed that thickness is 2.5 μ m respectively in the both sides of original film.The vacuum drying oven that composite membrane is put into 165 ℃ heats the thorough solvent flashing of 90min.Finally obtaining thickness is the Pt/CNTs-Nafion composite membrane of 25 μ m.With this composite membrane at 80 ℃ of 0.5M H
2SO
4Be placed in the deionized water standby in the solution behind the acidifying 1h.
Adopt carbon paper, polytetrafluoroethylene (PTFE) emulsion, XC-72 carbon dust and 20%Pt/C Preparation of Catalyst porous gas diffusive electrode, catalyst loading is 0.30mgPt/cm in the electrode
2Electrode sprays a certain amount of 5%Nafion solution (U.S. Du Pont company) to Catalytic Layer before use, carrying out three-dimensional handles to increase the phase reaction area of electrode, with Nafion solution dilution 2-4 doubly, uniformly spray at the electrode catalyst laminar surface, dry in room temperature, in about 80 ℃, dry by the fire 40min again, promptly finish electrode three-dimensional step.
For guaranteeing that electrode and the effective of proton exchange membrane contact, reduce the contact resistance between electrode and the proton exchange membrane, adopt hot-pressing technique that electrode and proton exchange membrane are bonded together.The preparation method places Pt/CNTs-Nafion composite membrane both sides respectively with two gas-diffusion electrodes, and the Catalytic Layer one side is towards composite membrane.In 160 ℃ of hot pressing, earlier little exerting pressure after water drains in the film, improved pressure again to 1.0MPa in forcing press, and hot pressing 1min takes out rapidly and cools off, and it is three-in-one promptly to make membrane electrode.
The three-in-one both sides of membrane electrode of preparation are added anode and cathode flow field plate respectively, and collector plate and end plate constitute PEMFC monocell, test battery performance on the monocell evaluating apparatus.The operating condition of battery is as follows: battery temperature is 80 ℃, and Hydrogen Vapor Pressure is 0.20MPa, and oxygen pressure is 0.20MPa, and when estimating battery outside during the battery performance under the humidification condition, hydrogen and oxygen is the outer humidifier humidification by 80 ℃ all; When estimating battery at the battery performance under the humidification condition, hydrogen and oxygen are directly sent into battery without outer humidifier.
Comparing embodiment 1: get 3g 5.4%Nafion solution and pour in the small beaker, heating with the low boiling point organic solvent volatilization totally adds the analytically pure DMF solution of 3ml then the Nafion resin is dissolved again on 50 ℃ of hot platforms.Adding the 5mg diameter in Nafion-DMF solution is that 30nm, length are the multi-walled carbon nano-tubes about 3 μ m, and ultrasonic dispersion 10min obtains uniform CNTs-Nafion-DMF solution.Leaving standstill the bubble of driving away in this solution, is 20cm with its impouring area
2Plate glass casting film frame in, the casting film frame is placed on the heating platform of a level.On 50 ℃ hot platform, heat 2h solvent flashing film forming then, the film that obtains is taken out, spray the mixed solution of 0.185g 5.4%Nafion solution and 2g isopropyl alcohol preparation then respectively in its both sides, naturally dry, form the pure Nafion resin bed that thickness is 2.5 μ m respectively in the both sides of original film.The vacuum drying oven that composite membrane is put into 165 ℃ heats the thorough solvent flashing of 90min.Finally obtaining thickness is the CNTs-Nafion composite membrane of 25 μ m.With this composite membrane at 80 ℃ of 0.5M H
2SO
4Be placed in the deionized water standby in the solution behind the acidifying 1h.
Table 1 be Pt/CNTs-Nafion composite membrane in the embodiments of the invention 1 and Nafion NRE-212 film physical and chemical performance relatively.
Embodiment 2: get 3g 5.4%Nafion solution and pour in the small beaker, on 50 ℃ of hot platforms heating low boiling point organic solvent volatilization is clean, add 3ml then and analyze pure DMF solution the Nafion resin is dissolved again.Adding the 5mg diameter in Nafion-DMF solution is that 30nm, length are the multi-walled carbon nano-tubes about 3 μ m, and ultrasonic dispersion 10min obtains uniform CNTs-Nafion-DMF solution.Leaving standstill the bubble of driving away in this solution, is 20cm with its impouring area
2Plate glass casting film frame in, the casting film frame is placed on the heating platform of a level.Heating 2h solvent flashing film forming on 50 ℃ hot platform is taken out the CNTs-Nafion composite membrane that obtains then.Get 1mg Pt/SiO
2Catalyst and 0.185g 5.4%Nafion solution and 2g isopropyl alcohol are mixed with mixed solution, disperse to obtain in 15 minutes homogeneous solution, wherein Pt/SiO in ultrasonator
2The quality percentage composition of Pt is 1% in the catalyst.Use the same method respectively with this Pt/SiO
2Two parts of-Nafion-aqueous isopropanol preparations utilize spray gun with two parts of Pt/SiO
2-Nafion-aqueous isopropanol is sprayed on the both sides of CNTs-Nafion composite membrane respectively, dries naturally, and forming thickness respectively in the both sides of CNTs-Nafion composite membrane is the Pt/SiO that is dispersed with of 2.5 μ m
2The Nafion resin bed.The vacuum drying oven that composite membrane is put into 165 ℃ heats the thorough solvent flashing of 90min.Finally obtain the Pt/SiO that thickness is 25 μ m
2-CNTs-Nafion composite membrane.With this composite membrane at 80 ℃ of 0.5M H
2SO
4Be placed in the deionized water standby in the solution behind the acidifying 1h.
Embodiment 3: get 5g 5.4%Nafion solution and pour in the small beaker, heating with the low boiling point organic solvent volatilization totally adds the analytically pure DMF solution of 5ml then the Nafion resin is dissolved again on 60 ℃ of hot platforms.Adding the 10mg diameter in Nafion-DMF solution is that 10nm, length are the multi-walled carbon nano-tubes about 1 μ m, and ultrasonic dispersion 10min obtains uniform CNTs-Nafion-DMF solution.Leave standstill the bubble of driving away in this solution, in its impouring plate glass casting film frame, the casting film frame is placed on the heating platform of a level.Heating 2h solvent flashing film forming on 50 ℃ hot platform is taken out the CNTs-Nafion composite membrane that obtains then.Get a certain amount of Pt/SiO
2Catalyst and Nafion solution and isopropyl alcohol disperse to obtain in 15 minutes homogeneous solution, wherein Pt/SiO in ultrasonator
2The quality percentage composition of Pt is 1% in the catalyst.The CNTs-Nafion composite membrane of preparation is immersed in the Pt/SiO for preparing
2Take out nature in the-Nafion-aqueous isopropanol behind the certain hour and dry, respectively form a thickness in the both sides of former CNTs-Nafion composite membrane and be the Pt/SiO that is dispersed with about 3 μ m
2The Nafion resin bed.The vacuum drying oven that composite membrane is put into 165 ℃ heats the thorough solvent flashing of 90min.Finally obtain the Pt/SiO that thickness is 30 μ m
2-CNTs-Nafion composite membrane.With this composite membrane at 80 ℃ of 0.5M H
2SO
4Be placed in the deionized water standby in the solution behind the acidifying 1h.
Embodiment 4: get 3g 5.4%Nafion solution and pour in the small beaker, heating with the low boiling point organic solvent volatilization totally adds the analytically pure DMF solution of 3ml then the Nafion resin is dissolved again on 50 ℃ of hot platforms.The employing diameter is that 10nm, length are that the Pt quality percentage composition of the made of carbon nanotubes about 1 μ m is 1% Pt/CNTs as from the humidification catalyst.Get in the Nafion solution after 5mgPt/CNTs adds the DMF dissolving, ultrasonic dispersion 15min obtains uniform Pt/CNTs-Nafion-DMF solution.Leave standstill the bubble of driving away in this solution, in the plate glass casting film frame with the certain area of its impouring, the casting film frame is placed on the heating platform of a level.Heating 2h solvent flashing film forming on 60 ℃ hot platform is taken out the film that obtains then.Get a certain amount of Nafion solution and mix then in ultrasonator ultrasonic dispersion with isopropyl alcohol 20 minutes, the Nafion-isopropyl alcohol mixture that obtains mixing.The Pt/CNTs-Nafion composite membrane of preparation is immersed in the Nafion-aqueous isopropanol for preparing takes out nature behind the certain hour and dry, respectively form a thickness in the both sides of former Pt/CNTs-Nafion composite membrane and be the Nafion resin bed about 3 μ m.The vacuum drying oven that composite membrane is put into 165 ℃ heats the thorough solvent flashing of 90min.Finally obtaining thickness is three layers of composite membrane of Pt/CNTs-Nafion of 30 μ m.With this composite membrane at 80 ℃ of 0.5M H
2SO
4Be placed in the deionized water standby in the solution behind the acidifying 1h.
Embodiment 5: get 30g 1wt.%Nafion solution and pour in the small beaker, heating with the low boiling point organic solvent volatilization totally adds the analytically pure DMF solution of 2ml then the Nafion resin is dissolved again on 50 ℃ of hot platforms.The employing diameter is that 0.5nm, length are that the Pt quality percentage composition of the made of carbon nanotubes about 100nm is 0.01% Pt/CNTs as from the humidification catalyst.Get in the Nafion solution after 1.5mg Pt/CNTs adds the DMF dissolving, ultrasonic dispersion 10min obtains uniform Pt/CNTs-Nafion-DMF solution.Leaving standstill the bubble of driving away in this solution, is 600cm with its impouring area
2Plate glass casting film frame in, the casting film frame is placed on the heating platform of a level.On 50 ℃ hot platform, heat 2h solvent flashing film forming then, obtain the intermediate layer that thickness is 5 μ m, the film that obtains is taken out, spray the mixed solution of 3g 1wt.%Nafion solution and 2g isopropyl alcohol preparation then respectively in its both sides, naturally dry, form the pure Nafion resin bed that thickness is 0.5 μ m respectively in the both sides of original film.The vacuum drying oven that composite membrane is put into 165 ℃ heats the thorough solvent flashing of 90min.Finally obtaining thickness is the Pt/CNTs-Nafion composite membrane of 6 μ m.With this composite membrane at 80 ℃ of 0.5M H
2SO
4Be placed in the deionized water standby in the solution behind the acidifying 1h.
Embodiment 6: get 2g 15wt.%Nafion solution and pour in the small beaker, heating with the low boiling point organic solvent volatilization totally adds the analytically pure DMF solution of 2ml then the Nafion resin is dissolved again on 50 ℃ of hot platforms.The employing diameter is that 100nm, length are that the Pt quality percentage composition of the made of carbon nanotubes about 50 μ m is 30% Pt/CNTs as from the humidification catalyst.Get in the Nafion solution after 90mg Pt/CNTs adds the DMF dissolving, ultrasonic dispersion 30min obtains uniform Pt/CNTs-Nafion-DMF solution.Leaving standstill the bubble of driving away in this solution, is 30cm with its impouring area
2Plate glass casting film frame in, the casting film frame is placed on the heating platform of a level.On 60 ℃ hot platform, heat 1h solvent flashing film forming then, obtain the intermediate layer that thickness is 100 μ m, the film that obtains is taken out, spray the mixed solution of 0.2g 15wt.%Nafion solution and 1g isopropyl alcohol preparation then respectively in its both sides, naturally dry, form the pure Nafion resin bed that thickness is 10 μ m respectively in the both sides of original film.The vacuum drying oven that composite membrane is put into 165 ℃ heats the thorough solvent flashing of 90min.Finally obtaining thickness is the Pt/CNTs-Nafion composite membrane of 120 μ m.With this composite membrane at 80 ℃ of 0.5M H
2SO
4Be placed in the deionized water standby in the solution behind the acidifying 1h.
Embodiment 7: get 10g 1%Nafion solution and pour in the small beaker, on 60 ℃ of hot platforms heating low boiling point organic solvent volatilization is clean, add 2ml then and analyze pure DMF solution the Nafion resin is dissolved again.Adding the 5mg diameter in Nafion-DMF solution is that 0.5nm, length are the multi-walled carbon nano-tubes about 100nm, and ultrasonic dispersion 10min obtains uniform CNTs-Nafion-DMF solution.Leaving standstill the bubble of driving away in this solution, is 200cm with its impouring area
2Plate glass casting film frame in, the casting film frame is placed on the heating platform of a level.Heating 2h solvent flashing film forming on 50 ℃ hot platform obtains the intermediate layer that thickness is 5 μ m then.Get 2mg Pt/SiO
2Catalyst and 1g 1%Nafion solution and 2g isopropyl alcohol are mixed with mixed solution, disperse to obtain in 30 minutes homogeneous solution, wherein Pt/SiO in ultrasonator
2The quality percentage composition of Pt is 0.01% in the catalyst.Use the same method respectively with this Pt/SiO
2Two parts of-Nafion-aqueous isopropanol preparations utilize spray gun with two parts of Pt/SiO
2-Nafion-aqueous isopropanol is sprayed on the both sides of CNTs-Nafion composite membrane respectively, dries naturally, and forming thickness respectively in the both sides of CNTs-Nafion composite membrane is the Pt/SiO that is dispersed with of 0.5 μ m
2The Nafion resin bed.The vacuum drying oven that composite membrane is put into 165 ℃ heats the thorough solvent flashing of 90min.Finally obtain the Pt/SiO that thickness is 6 μ m
2-CNTs-Nafion composite membrane.With this composite membrane at 80 ℃ of 0.5M H
2SO
4Be placed in the deionized water standby in the solution behind the acidifying 1h.
Embodiment 8: get 2g 15wt.%Nafion solution and pour in the small beaker, heating with the low boiling point organic solvent volatilization totally adds the analytically pure DMF solution of 2ml then the Nafion resin is dissolved again on 50 ℃ of hot platforms.Get the 90mg diameter and be 100nm, length and be in the Nafion solution after carbon nano-tube about 50 μ m adds the DMF dissolving, ultrasonic dispersion 30min obtains uniform CNTs-Nafion-DMF solution.Leaving standstill the bubble of driving away in this solution, is 30cm with its impouring area
2Plate glass casting film frame in, the casting film frame is placed on the heating platform of a level.Heating 1h solvent flashing film forming on 60 ℃ hot platform obtains the intermediate layer that thickness is 100 μ m then, and the film that obtains is taken out, and sprays the Pt/SiO of 0.2g 15wt.%Nafion solution and 6mg 30wt.% then respectively in its both sides
2And the mixed solution of 1g isopropyl alcohol preparation, dry naturally, form the pure Nafion resin bed that thickness is 10 μ m respectively in the both sides of original film.The vacuum drying oven that composite membrane is put into 165 ℃ heats the thorough solvent flashing of 90min.Finally obtain the Pt/SiO that thickness is 120 μ m
2-CNTs-Nafion composite membrane.With this composite membrane at 80 ℃ of 0.5M H
2SO
4Be placed in the deionized water standby in the solution behind the acidifying 1h.
Claims (5)
1. the self-humidifying composite proton exchange film that carbon nano-tube strengthens is characterized in that: form the intermediate layer by perfluorinated sulfonic resin with supporting by the carbon nano-tube of metal Pt, the composite membrane that the compound respectively one deck perfluorinated sulfonic resin formation in its both sides has three-decker;
The quality percentage composition of Pt/CNTs is 0.5-30% in the intermediate layer, and wherein the quality loading of Pt is 0.01-30wt.% in the Pt/CNTs catalyst.
2. according to the self-humidifying composite proton exchange film of the described carbon nano-tube enhancing of claim 1, it is characterized in that: described carbon nano-tube is single wall or multi-walled carbon nano-tubes, and its diameter is 0.4-100nm, and length is 100nm-50 μ m.
3. according to the self-humidifying composite proton exchange film of the described carbon nano-tube enhancing of claim 1, it is characterized in that: the thickness in described intermediate layer is 5-100 μ m, and the thickness of both sides perfluorinated sulfonic resin is respectively 0.5-10 μ m.
4. the preparation method of the self-humidifying composite proton exchange film that strengthens of the described carbon nano-tube of a claim 1 is characterized in that: may further comprise the steps,
(1) heating for dissolving perfluorinated sulfonic resin film in the solvent of low boiling organic alcohols and water is made quality percentage composition 1-15% perfluor sulfoacid resin solution;
(2) in the perfluor sulfoacid resin solution of step (1) preparation or business-like perfluor sulfoacid resin solution, add high boiling organic solvent by the mass ratio of perfluor sulfoacid resin solution 1: 5-50 in high boiling organic solvent and the step (1);
(3) add Pt/CNTs in the perfluor sulfoacid resin solution of step (2) preparation, Pt/CNTs accounts for the 0.5%-30% of Pt/CNTs and perfluorinated sulfonic resin gross mass in the formed solution; Ultrasonic dispersion obtains finely dispersed Pt/CNTs-perfluor sulfoacid resin solution;
(4) solution casting that step (3) is prepared is in the glass casting film frame of level, and 40-120 ℃ is heated 1-3h on heating station, and forming thickness is the intermediate layer of 5-100 μ m;
(5) film with step (4) preparation takes out, and sprays respectively in its both sides or floods certain thickness perfluorinated sulfonic resin, and the thickness of each side perfluorinated sulfonic resin is respectively 0.5-10 μ m;
(6) composite membrane of above-mentioned steps preparation is placed 0.5-20h in 120-200 ℃ the vacuum drying oven, cooling promptly obtains the described three layers of composite membrane being made up of Pt/CNTs and perfluorinated sulfonic resin of claim 1.
5. the preparation method of the self-humidifying composite proton exchange film that strengthens according to the described carbon nano-tube of claim 4 is characterized in that:
Described low boiling organic alcohols solvent is ethanol, methyl alcohol, isopropyl alcohol or propyl alcohol;
Described high boiling organic solvent is N, dinethylformamide, N, N-dimethylacetylamide, N methyl pyrrolidone or dimethyl sulfoxide (DMSO).
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| CN102605608B (en) * | 2012-02-11 | 2014-01-08 | 东华大学 | Method for preparing super-hydrophobic conductive cellulose fabrics by CNT (carbon nano tube) finishing technology |
| CN103296297B (en) * | 2013-06-07 | 2015-02-11 | 湖北工程学院 | Preparation method of organic-inorganic composite proton exchange membrane for fuel cell |
| CN105601968B (en) * | 2015-11-19 | 2018-09-21 | 黄河科技学院 | A kind of preparation method of polybenzimidazoles multilayer complex films used for high-temperature fuel cell |
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| CN109065923A (en) * | 2018-07-06 | 2018-12-21 | 华南理工大学 | Add the high-performance high power density membrane electrode and preparation method thereof of hydrophily carbon material preparation having from humidifying capacity |
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| CN110323460B (en) * | 2019-07-03 | 2021-01-19 | 深圳市南科燃料电池有限公司 | Catalyst slurry, preparation method and fuel cell |
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| CN113471496A (en) * | 2021-06-29 | 2021-10-01 | 上海化工研究院有限公司 | High-proton conductivity high-strength perfluorosulfonic acid composite proton exchange membrane and preparation method thereof |
| CN117107295B (en) * | 2023-08-08 | 2024-07-02 | 中瑞国能科技(东莞)有限公司 | Membrane module and preparation method and application thereof |
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