CN102796274A - Composite proton exchange membrane for high temperature-resistant fuel cell and preparation method for composite proton exchange membrane - Google Patents
Composite proton exchange membrane for high temperature-resistant fuel cell and preparation method for composite proton exchange membrane Download PDFInfo
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Abstract
The invention relates to a composite proton exchange membrane and a preparation method thereof, in particular to a composite proton exchange membrane for a high temperature-resistant fuel cell and a preparation method for the composite proton exchange membrane, and belongs to the field of fuel cells. The method comprises the following steps of: preparing polybenzimidazole (PBI) serving as a matrix material and an amphoteric nano particle disperse solution, preparing a composite membrane disperse solution, curtain coating to form the membrane and the like. According to the method, a preparation process is simple and easy to control. Amphoteric nano particles in the composite membrane have high acid absorption capacity and high acid keeping performance, so that the proton exchange membrane has high proton conductivity at high temperature.
Description
Technical field
The present invention relates to a kind of compound proton exchange membrane and preparation method thereof, compound proton exchange membrane of a kind of high temperature resistant fuel cell and preparation method thereof belongs to fuel cell field specifically.
Background technology
PEM (Proton exchange membrane; PEM) be Proton Exchange Membrane Fuel Cells (Proton exchange membrane fuel cell; PEMFC) one of vitals; Its role is: anode and negative electrode are separated in (1), avoid fuel and air (oxygen) directly to mix chemical reaction takes place; (2) proton conduction; (3) electronic body stops the conduction of electronics in film, and electronics flows through external circuit.Usually the PEM used of fuel cell need satisfy following requirement: (1) specific conductivity high (ionic conduction of highly selective but not electronic conduction); (2) chemicalstability (acid and alkali-resistance and resistance of oxidation); (3) thermal stability is good; (4) good mechanical stability (like intensity and toughness etc.); (5) cheap or the like.
At present the commonplace PEM of usefulness is a perfluorinated sulfonic acid type PEM in the world, and wherein the most representative be the Nafion series perfluorinated sulfonic acid type PEM that du pont company is produced.This type film has proton conductivity preferably, good mechanical intensity, and advantages such as excellent in chemical and electrochemical stability can life-time service.But do not reached the performance requriements of PEM well by the film of this material, still exist some shortcomings: the working temperature of (1) film is limited in 70 ℃～90 ℃ scopes; (2) preparation technology's more complicated of Nafion film, technical difficulty is big, causes its cost higher.Therefore, development has high proton conductivity and is extremely important for the business-like process that reduces film cost, promotion fuel cell with proton exchange membrane material cheaply under hot conditions.
Contain ladder-shaper structure in the main chain of polybenzimidazole (PBI), therefore show outstanding thermostability, oxidation-resistance and mechanical stability, obtained widespread use as high performance engineering plastics; PBI doping phosphoric acid system has higher proton conductivity under higher temperature, but the problem of oozing out of phosphoric acid never is well solved.
What need particularly point out here is, among the PBI film after phosphate-doped, because phosphoric acid and PBI can form the hydrogen bond network structure; Proton can transmit in hydrogen bond network, thereby reaches higher proton transport performance (referring to document: Progress in Polymer Science, 2009; 34,449-477), therefore; The amount that keeps doping phosphoric acid among the PBI is the key that guarantees the proton conductivity of film; Bibliographical information is arranged, doping inorganic hygroscopic nanoparticle (SiO in PBI
2, TiO
2), have certain guarantor acid can, thereby improve film than the proton conductivity under the high stable (referring to document: Journal of Membrane Science 2011,369,105-111; Applied Materials&Interfaces 2009,1,1002-1012; Journal of Membrane Science 2009,332,121-128).
Prepared both sexes nanoparticle is the oligopolymer of the silicon after crosslinked among the present invention; Has certain space reticulated structure; What the outside of spheroidal particle distributed is hydrophilic sulfonic acid group; Can improve on the one hand the content of moisture in the film, can rely on its space reticulated structure on the other hand and keep phosphoric acid stable at the film intensive amount, thereby make the proton film keep higher proton conductivity.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high temperature resistant compound proton exchange membrane of PBI of the doping both sexes nanoparticle that is used for fuel cell.
For achieving the above object, the concrete technical scheme of the present invention is, a kind of preparation method of the high temperature resistant compound proton exchange membrane of PBI of the doped with nanometer particle that is used for fuel cell specifically may further comprise the steps:
(1) general step of preparation polybenzimidazole: (referring to document: Journal of Power Sources 2007,168,172-177; Chem. Mater. 2005,17, and 5,328 5333).Concrete preparation process is: in round-bottomed flask, add a certain amount of polyphosphoric acid (CP, content >=85%), 90 ℃, nitrogen atmosphere adding 3 down; The 4-diaminobenzidine stirred one hour under 100 ℃ of temperature, was cooled to 90 ℃; The adding dicarboxylic acid monomer (1,4-terephthalic acid, 2, two (4-carboxyl phenyl) propane, 2 of 2-; Two (4-carboxyl phenyl) HFC-236fas of 2-etc.), 100 ℃ were stirred one hour, adopted the mode that progressively heats up then; Stopped reaction (polyreaction is carried out in nitrogen atmosphere) after respectively reacting 12 hours under 140 ℃, 160 ℃, 180 ℃ respectively; Pour in the deionized water dope into deposition and repetitive scrubbing to neutral after the cooling, place then 120 ℃ dry down, obtain polymkeric substance at last.
(2) preparation polybenzimidazole solution: get polybenzimidazole and be dissolved in the methyl-sulphoxide (DMSO), per 10～20ml methyl-sulphoxide dissolving 1g polybenzimidazole, it is complete to be heated to polymer dissolution, and system becomes brown clear solution.
(3) preparation both sexes nanoparticle sol: in nitrogen atmosphere; THF (THF) solution of sultone slowly is added drop-wise in THF (THF) solution of 3-aminopropyltriethoxywerene werene, and wherein the mol ratio of sultone and 3-aminopropyltriethoxywerene werene is 1:1, and temperature of reaction is controlled between 40-60 ℃; Behind magnetic agitation reaction 1 ~ 3h; Remove the THF in the system with Rotary Evaporators, and use petroleum ether, remove sherwood oil after; The adding mol ratio is that 10 times PH of 3-aminopropyltriethoxywerene werene is zero(ppm) water stirring at room 24h ~ 48h of 2, obtains nanoparticle sol.
(4) preparation is used for adulterated nanoparticle dispersion liquid: get the nanoparticle sol that step (3) obtains and be dissolved in the methyl-sulphoxide (DMSO); Every 10ml methyl-sulphoxide dissolving 1g nanoparticle sol; Place ultrasonic apparatus to make nanoparticle sol then, obtain the nanoparticle sol dispersion liquid at the methyl-sulphoxide homodisperse.
(5) the PBI composite package of preparation doped with nanometer particle: get the DMSO solution of the polybenzimidazole of gained in the step (2) and the nanoparticle sol dispersion liquid of the middle gained of step (4); Mass ratio mixing and the ultra-sonic dispersion of pressing nanoparticle sol and polymkeric substance 1:3 ~ 19 are even; The gained dispersion liquid is poured onto on the clean sheet glass of smooth; Under 60 ~ 80 ℃ temperature, vapor away solvent, be cooled to the room temperature rear demoulding.
(6) gained film in (5) is immersed in 75 ~ 85wt% phosphoric acid solution, takes out behind 48 ~ 72h, dry the phosphoric acid solution on film surface, obtain being used for the compound proton exchange membrane of fuel cell at last, the gauge control of film is between 40～120 microns.
Because the technique scheme utilization, the present invention compared with prior art has advantage:
The present invention is to add the both sexes nanoparticle in the body material through polybenzimidazole (PBI), because the wetting ability of both sexes inorganic nano-particle can be adsorbed more phosphoric acid; And; Phosphoric acid is not easy to be washed out around being attracted to the both sexes inorganic nano-particle, and resulting nano combined proton film is compared with pure PBI phosphoric acid composite package through test; Have proton conductivity preferably, have higher fuel battery performance.
Description of drawings
Fig. 1 is the structural representation of both sexes nanoparticle 3-(N-sulfopropyl) aminopropyl polysilane (PSPAPS);
Fig. 2 is the TGA figure of both sexes nanoparticle, pure PBI film, compound PBI film;
Fig. 3 is the conductivity map after the composite package of doping different ratios both sexes nanoparticle steeps acid;
Fig. 4 is the TEM figure of both sexes nanoparticle;
Pickling after the acid of Fig. 5 position doping both sexes nanoparticle bubble goes out to change comparison diagram;
Fig. 6 is the monocell performance of doping both sexes nanoparticle composite membrane.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described:
Embodiment 1: the preparation of both sexes nanoparticle 3-(N-sulfopropyl) aminopropyl polysilane (PSPAPS) colloidal sol: in nitrogen atmosphere, with 1, THF (THF) solution of 3-propane sultone slowly is added drop-wise in THF (THF) solution of 3-aminopropyltriethoxywerene werene; Wherein 1; The mol ratio of 3-propane sultone and 3-aminopropyltriethoxywerene werene is 1:1, and temperature of reaction is controlled at 50 ℃, and the magnetic agitation reaction is after 1 hour; Remove the THF in the system with Rotary Evaporators; And use petroleum ether, remove sherwood oil after, adding certain proportion (mol ratio is 10 times of 3-aminopropyltriethoxywerene werene) pH value is 2 zero(ppm) water; At room temperature stir 24h, obtain both sexes nanoparticle 3-(N-sulfopropyl) aminopropyl polysilane (PSPAPS) colloidal sol.
Its structure and reaction synoptic diagram are seen Fig. 1: the first step reaction is alkyl azochlorosulfonate to be connected on the amino of 3-aminopropyltriethoxywerene werene formed inner salt among the figure; Add PH and be behind 2 the zero(ppm) water crosslinked, crosslinked product is that the periphery has many sulfonate radical tridimensional networks.
Embodiment 2: the preparation of both sexes nanoparticle 3-(N-sulphur butyl) aminopropyl polysilane (PSPAPS) colloidal sol: in nitrogen atmosphere, with 1, the THF of 4-butane sultone (THF) solution slowly is added drop-wise in THF (THF) solution of 3-aminopropyltriethoxywerene werene; Wherein 1; The mol ratio of 3-propane sultone and 3-aminopropyltriethoxywerene werene is 1:1, and temperature of reaction is controlled at 50 ℃, and the magnetic agitation reaction is after 2 hours; Remove the THF in the system with Rotary Evaporators; And use petroleum ether, remove sherwood oil after, adding certain proportion (mol ratio is 10 times of 3-aminopropyltriethoxywerene werene) pH value is 2 zero(ppm) water; At room temperature stir 36h, obtain both sexes nanoparticle 3-(N-sulphur butyl) aminopropyl polysilane (PSPAPS) colloidal sol.
The preparation of embodiment 3:5% both sexes nanoparticle doped P BI heatproof PEM
(1) get polybenzimidazole (PBI) 0.95g and be dissolved in the 10ml methyl-sulphoxide (DMSO), be heated to polymkeric substance and dissolve fully, system becomes brown clear solution;
(2) in nitrogen atmosphere, will contain 0.01mol 1, the THF of 4-butane sultone (THF) solution slowly is added drop-wise in THF (THF) solution that contains 0.01mol 3-aminopropyltriethoxywerene werene; Temperature of reaction is controlled at 50 ℃; The magnetic agitation reaction was removed the THF in the system with Rotary Evaporators, and is used petroleum ether after 3 hours; After removing sherwood oil; Adding 0.1mol PH is 2 zero(ppm) water, at room temperature stirs 48h, obtains both sexes nanoparticle 3-(N-sulphur butyl) aminopropyl polysilane (PSPAPS) colloidal sol;
(3) get the nanoparticle sol 0.05g that obtains in the step (2) and be dissolved in the 0.5ml methyl-sulphoxide (DMSO), in ultrasonic apparatus, disperseed 30 minutes then, make nanoparticle sol homodisperse in methyl-sulphoxide;
(4) polymers soln of getting step (1) gained mixes with the nanoparticle sol dispersion liquid of gained in the step (3) that also ultra-sonic dispersion is even; The mass ratio of polymkeric substance and nanoparticle sol is 5:95; With mixed dispersion liquid to being poured on the clean smooth sheet glass; Put into loft drier, drying is 48 hours under 80 ℃ of temperature; Put into after the demoulding and take out after the 85wt% phosphoric acid solution soaks 48h, wash the surperficial phosphoric acid solution of film off with thieving paper, obtain final PEM, doping ratio 5%, the thickness of film are 80 microns.
The preparation of embodiment 4:15% nanoparticle doped P BI heatproof PEM
Methyl-sulphoxide (DMSO) the solution 10ml that contains the 0.85g polybenzimidazole adds and contains 0.15g both sexes nanoparticle sol dispersion liquid, and ultra-sonic dispersion was uniformly dispersed it in 30 minutes; The concentration of phosphoric acid solution is 75 wt%, soaks 60h, and all the other operations are all identical with embodiment 3, and the doping ratio of PEM is 15%, and the gauge control of film is at 65 microns.
The preparation of embodiment 5:25% nanoparticle doped P BI heatproof PEM
Methyl-sulphoxide (DMSO) the solution 10ml that contains the 0.75g polybenzimidazole adds and contains 0.25g both sexes nanoparticle sol dispersion liquid, and ultra-sonic dispersion was uniformly dispersed it in 30 minutes; The concentration of phosphoric acid solution is 80wt%, soaks 72h, and all the other operations are all identical with embodiment 3, and the doping ratio of PEM is 25%, and the gauge control of film is at 55 microns.
Embodiment 6:TGA test
The thermotolerance of PBI, both sexes nanoparticle sol and doped P BI is all used thermal analyzer SDT Q600 (U.S. TA company).
The result sees Fig. 2, and the result shows that the both sexes nanoparticle sol just begins to decompose in the time of 150 ℃, and the decomposition temperature of the PBI of PBI and doping 25% both sexes nanoparticle reaches more than 350 ℃.
Embodiment 7: the test of specific conductivity
Adopt the specific conductivity of AC impedence method test membrane, adopt electrochemical workstation (Zahner 1M6EX) to test, exchanging the perturbation amplitude in the test process is 10mV, and range of frequency is 10～1MHz; The body resistance value Rb of film gets Z '-Z " abscissa value that curve medium-high frequency semicircle is corresponding with the low frequency straight-line intersection, if when the not too high or system specific conductivity of test frequency is higher, the high frequency semicircle does not occur, Rb gets the abscissa value of high frequency end points; Calculate the specific conductivity of film under certain temperature according to following calculation formula:
σ=d/Rb?S
Wherein: σ is proton conductivity (S/cm); D is the thickness (cm) of dielectric film; Rb is the body resistance of dielectric film; S is the contact area (cm of electrode and dielectric film
2).
The result sees Fig. 3: along with the rising of temperature, the specific conductivity of film progressively increases, and the high energy of the specific conductivity of the composite package of doping both sexes nanoparticle reaches 1.033 * 10
-1S/cm.
Embodiment 8:
The transmission microscopy test result of both sexes nanoparticle shows: the size distribution of both sexes nanoparticle is even, is about about 10 nanometers, and the result sees Fig. 4.
Embodiment 9: the suction of composite package, the sour rate of suction and dissolution test.
With the composite package of the both sexes nanoparticle of doping different ratios, after 105 ℃ of constant weights, the film of 0.2g placed 50ml zero(ppm) water or 85% phosphoric acid 48h after; Film is taken out, and oven dry is weighed; Triplicate, the adsorptive capacity of calculating water or phosphoric acid, the result sees table 1; From table, can find out: along with the rising of doping ratio, the water cut of film explains that also along with increasing adulterated nanoparticle seed has stronger hydrophilic ability; The content of acid also increases along with the rising of doping ratio in the sour caudacoria of same bubble, explain that nanoparticle and phosphoric acid have affinity preferably, forms hydrogen bond between the two, for the conduction of proton provides passage, and then the proton conductivity of raising film.
Table 1 is the suction and the absorption phosphoric acid performance of doping both sexes nanoparticle composite membrane
After the composite package bubble acid with the both sexes nanoparticle of doping different ratios, the film of 0.2g is placed 50ml zero(ppm) water to certain hour (10min, 20 min30 min, 45 min; 60 min, 120 min) after, film is taken out; Oven dry is weighed, and calculates both sexes nanoparticle seepage discharge; Triplicate, the result sees Fig. 5, as can be seen from the figure along with the raising of nanoparticle doping ratio; The loss ratio of acid is reducing in the film, explains that adulterated nanoparticle has the effect that keeps phosphorus acid content in the film, finally can keep the stable conductivity of proton film.
Embodiment 10: the test of assembling monocell
Adopt carbon to carry platinum as catalyst layer, the charge capacity of platinum is about 0.1mg/cm
2, adopt H
2/ O
2As the two poles of the earth gas, normal pressure, assembling fuel cell, the result sees Fig. 6, under 80 degree, can reach 80mW/cm
2
Claims (3)
1. the compound proton exchange membrane of a high temperature resistant fuel cell is characterized in that: adopt following method preparation:
(1) preparation polybenzimidazole solution: get polybenzimidazole and be dissolved in the methyl-sulphoxide (DMSO), per 10～20ml methyl-sulphoxide dissolving 1g polybenzimidazole, it is complete to be heated to polymer dissolution, and system becomes brown clear solution;
(2) preparation both sexes nanoparticle sol: in nitrogen atmosphere; THF (THF) solution of sultone slowly is added drop-wise in THF (THF) solution of 3-aminopropyltriethoxywerene werene, and wherein the mol ratio of sultone and 3-aminopropyltriethoxywerene werene is 1:1, and temperature of reaction is controlled between 40-60 ℃; Behind magnetic agitation reaction 1 ~ 3h; Remove the THF in the system with Rotary Evaporators, and use petroleum ether, remove sherwood oil after; The adding amount of substance is that 10 times PH of 3-aminopropyltriethoxywerene werene is zero(ppm) water stirring at room 24h ~ 48h of 2, obtains nanoparticle sol;
(3) preparation is used for adulterated nanoparticle dispersion liquid: get the nanoparticle sol that step (3) obtains and be dissolved in the methyl-sulphoxide (DMSO); Every 10ml methyl-sulphoxide dissolving 1g nanoparticle sol; Place ultrasonic apparatus to make nanoparticle sol then, obtain the nanoparticle sol dispersion liquid at the methyl-sulphoxide homodisperse;
(4) the PBI composite package of preparation doped with nanometer particle: get the DMSO solution of the polybenzimidazole of gained in the step (1) and the nanoparticle sol dispersion liquid of the middle gained of step (4); Mass ratio mixing and the ultra-sonic dispersion of pressing nanoparticle sol and polymkeric substance 1:3 ~ 19 are even; The gained dispersion liquid is poured onto on the clean sheet glass of smooth; Vapor away solvent, be cooled to the room temperature rear demoulding;
(5) gained film in the step (4) is immersed in 75 ~ 85wt% phosphoric acid solution, takes out behind 48 ~ 72h, dry the phosphoric acid solution on film surface, obtain being used for the compound proton exchange membrane of fuel cell, the gauge control of film is between 40～120 microns.
2. the compound proton exchange membrane of a kind of high temperature resistant fuel cell as claimed in claim 1, it is characterized in that: the sultone in the said step (2) is 1,3-propane sultone or 1,4-butane sultone.
3. the compound proton exchange membrane of a kind of high temperature resistant fuel cell as claimed in claim 1, it is characterized in that: the solvent that vapors away in the said step (4) is under 60～80 ℃ temperature, to vapor away solvent.
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