CN102796274B - 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, a kind of compound proton exchange membrane and preparation method thereof of high temperature resistant fuel cell, belongs to fuel cell field specifically.
Background technology
Proton exchange membrane (Proton exchange membrane, PEM) be Proton Exchange Membrane Fuel Cells (Proton exchange membrane fuel cell, PEMFC) one of vitals, its role is: (1) comes anode and cathode spacer, avoids fuel and air (oxygen) directly mixing generation chemical reaction; (2) proton conduction; (3) electronic body, stop the conduction of electronics in film, electronics is flowed by external circuit.The proton exchange membrane of usual fuel cell need meet following requirement: (1) specific conductivity high ionic conduction of the highly selective (but not electronic conduction); (2) chemical stability (acid and alkali-resistance and resistance of oxidation); (3) thermal stability is good; (4) good mechanical stability energy (as intensity and toughness etc.); (5) cheap etc.
At present commonplace proton exchange membrane is in the world perfluorosulfonic acid type proton exchange membrane, and wherein most is representational is the Nafion series perfluorosulfonic acid type proton exchange membrane that du pont company produces.This kind of film has good proton conductivity, good mechanical strength, and the advantages such as excellent chemistry and electrochemical stability, can life-time service.But the film made by this material does not reach the performance requriements of proton exchange membrane well, still there are some shortcomings: the working temperature of (1) film is limited within the scope of 70 DEG C ~ 90 DEG C; (2) preparation technology's more complicated of Nafion film, technical difficulty is large, causes its cost higher.Therefore, development has the proton exchange membrane material of high proton conductivity and low cost under the high temperature conditions for reducing film cost, promoting that the business-like process of fuel cell is extremely important.
Containing ladder-shaper structure in the main chain of polybenzimidazole (PBI), therefore show outstanding thermostability, oxidation-resistance and mechanical stability, be widely applied as high performance engineering plastics; PBI doping phosphoric acid system, has higher proton conductivity at a higher temperature, but the problem of oozing out of phosphoric acid is never well solved.
Here it needs to be noted, among PBI film after phosphate-doped, because phosphoric acid and PBI can form hydrogen bond network structure, proton can transmit in hydrogen bond network, thus reaches higher proton transport performance (see document: Progress in Polymer Science, 2009,34,449-477), therefore, keeping the amount of doping phosphoric acid in PBI, is the key of the proton conductivity ensureing film; There is bibliographical information, inorganic hygroscopic of adulterating in PBI nanoparticle (SiO
2, TiO
2), have certain guarantor acid can, thus improve film compared with the proton conductivity under high stable (see document: Journal of Membrane Science 2011,369,105-111; Applied Materials & Interfaces 2009,1,1002-1012; Journal of Membrane Science 2009,332,121-128).
Both sexes nanoparticle prepared in the present invention is the oligopolymer of the silicon after being cross-linked, there is certain space net structure, spheroidal particle outside distribution be hydrophilic sulfonic acid group, the content of moisture in film can be improved on the one hand, its space net structure can be relied on the other hand and maintain phosphoric acid stablizing at film intensive amount, thus make the proton conductivity that proton membrane keeps higher.
Summary of the invention
The object of this invention is to provide a kind of preparation method of the high temperature resistant compound proton exchange membrane of PBI of the doping both sexes nanoparticle 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 for fuel cell, specifically comprises the following steps:
(1) general step of polybenzimidazole is prepared: (see document: Journal of Power Sources 2007,168,172-177; Chem. Mater. 2005,17,5,328 5333).Concrete preparation process is: in round-bottomed flask, add a certain amount of polyphosphoric acid (chemical pure, content >=85%), at 90 DEG C, 3 are added under nitrogen atmosphere, 4-diaminobenzidine, stir one hour at 100 DEG C of temperature, be cooled to 90 DEG C, add dicarboxylic acid monomer (1, 4-terephthalic acid, 2, two (4-carboxyl phenyl) propane of 2-, 2, two (4-carboxyl phenyl) HFC-236fa of 2-etc.), 100 DEG C are stirred one hour, then the mode progressively heated up is adopted, respectively at 140 DEG C, 160 DEG C, respectively stopped reaction (polyreaction is carried out in nitrogen atmosphere) after 12 hours is reacted at 180 DEG C, after cooling, dope is poured into precipitation in deionized water and repetitive scrubbing extremely neutrality, then dry at being placed in 120 DEG C, finally obtain polymkeric substance.
(2) prepare polybenzimidazole solution: get polybenzimidazole and be dissolved in methyl-sulphoxide (DMSO), every 10 ~ 20ml methyl-sulphoxide dissolves 1g polybenzimidazole, and be heated to polymer dissolution complete, system becomes amber transparent solution.
(3) both sexes nanoparticle sol is prepared: in nitrogen atmosphere, tetrahydrofuran (THF) (THF) solution of sultone is slowly added drop-wise in tetrahydrofuran (THF) (THF) solution of APTES, wherein the mol ratio of sultone and APTES is 1:1, temperature of reaction controls between 40-60 DEG C, after magnetic agitation reaction 1 ~ 3h, with the THF in Rotary Evaporators removing system, and by petroleum ether, after removing sherwood oil, to add mol ratio be the PH of 10 times of APTES be 2 distilled water stirring at room temperature 24h ~ 48h, obtain nanoparticle sol.
(4) for the preparation of the nanoparticle dispersion liquid of doping: get the nanoparticle sol obtained in step (3) and be dissolved in methyl-sulphoxide (DMSO), every 10ml methyl-sulphoxide dissolves 1g nanoparticle sol, then being placed in ultrasonic apparatus makes nanoparticle sol dispersed at methyl-sulphoxide, obtains nanoparticle sol dispersion liquid.
(5) the PBI composite membrane of doped with nanometer particle is prepared: get the DMSO solution of the polybenzimidazole of gained in step (2) and the nanoparticle sol dispersion liquid of the middle gained of step (4), by nanoparticle sol and polymkeric substance 1:3 ~ 19 mass ratio mixing and ultrasonic disperse is even, gained dispersion liquid is poured onto on smooth clean sheet glass, evaporation of solvent at the temperature of 60 ~ 80 DEG C, is cooled to room temperature rear demoulding.
(6) be immersed in 75 ~ 85wt% phosphoric acid solution by gained film in (5), take out after 48 ~ 72h, dry the phosphoric acid solution on film surface, finally obtain the compound proton exchange membrane that may be used for fuel cell, the gauge control of film is between 40 ~ 120 microns.
Because technique scheme is used, the present invention compared with prior art has following advantages:
The present invention passes through polybenzimidazole (PBI) for adding both sexes nanoparticle in body material, due to the wetting ability of both sexes inorganic nano-particle, more phosphoric acid can be adsorbed, and, phosphoric acid is attracted to around both sexes inorganic nano-particle and is not easy to be washed out, and the nano combined proton membrane obtained passes through test, compared with pure PBI phosphoric acid composite membrane, there is good proton conductivity, there is higher fuel battery performance.
Accompanying drawing explanation
Fig. 1 is both sexes nanoparticle 3-(N-sulfopropyl) structural representation of 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 compound film bubble acid of doping different ratios both sexes nanoparticle;
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 drawings and Examples, the invention will be further described:
Embodiment 1: both sexes nanoparticle 3-(N-sulfopropyl) preparation of aminopropyl polysilane (PSPAPS) colloidal sol: in nitrogen atmosphere, by 1, tetrahydrofuran (THF) (THF) solution of 3-propane sultone is slowly added drop-wise in tetrahydrofuran (THF) (THF) solution of APTES, wherein 1, the mol ratio of 3-propane sultone and APTES is 1:1, temperature of reaction controls at 50 DEG C, after magnetic agitation reacts 1 hour, with the THF in Rotary Evaporators removing system, and by petroleum ether, after removing sherwood oil, adding certain proportion (mol ratio is 10 times of APTES) pH value is the distilled water of 2, at room temperature stir 24h, obtain both sexes nanoparticle 3-(N-sulfopropyl) aminopropyl polysilane (PSPAPS) colloidal sol.
Its structure and reaction schematic diagram see the reaction of the first step in Fig. 1: figure be alkyl azochlorosulfonate is connected on APTES amino on define inner salt, it is crosslinked after the distilled water of 2 for adding PH, and crosslinked product is peripheral with many sulfonate radical tridimensional networks.
Embodiment 2: both sexes nanoparticle 3-(N-sulphur butyl) preparation of aminopropyl polysilane (PSPAPS) colloidal sol: in nitrogen atmosphere, by 1, tetrahydrofuran (THF) (THF) solution of 4-butane sultone is slowly added drop-wise in tetrahydrofuran (THF) (THF) solution of APTES, wherein 1, the mol ratio of 3-propane sultone and APTES is 1:1, temperature of reaction controls at 50 DEG C, after magnetic agitation reacts 2 hours, with the THF in Rotary Evaporators removing system, and by petroleum ether, after removing sherwood oil, adding certain proportion (mol ratio is 10 times of APTES) pH value is the distilled water of 2, at room temperature stir 36h, obtain both sexes nanoparticle 3-(N-sulphur butyl) aminopropyl polysilane (PSPAPS) colloidal sol.
The preparation of the resistance to temperature proton exchange film of PBI of embodiment 3:5% both sexes nanoparticle doped
(1) get polybenzimidazole (PBI) 0.95g to be dissolved in 10ml methyl-sulphoxide (DMSO), be heated to polymkeric substance and dissolve completely, system becomes amber transparent solution;
(2) in nitrogen atmosphere, will containing 0.01mol 1, tetrahydrofuran (THF) (THF) solution of 4-butane sultone is slowly added drop-wise in tetrahydrofuran (THF) (THF) solution containing 0.01mol APTES, temperature of reaction controls at 50 DEG C, after magnetic agitation reacts 3 hours, with the THF in Rotary Evaporators removing system, and by petroleum ether, after removing sherwood oil, add the distilled water that 0.1mol PH is 2, at room temperature stir 48h, obtain both sexes nanoparticle 3-(N-sulphur butyl) aminopropyl polysilane (PSPAPS) colloidal sol;
(3) getting the nanoparticle sol 0.05g obtained in step (2) is dissolved in 0.5ml methyl-sulphoxide (DMSO), then disperses 30 minutes in ultrasonic apparatus, makes nanoparticle sol dispersed in methyl-sulphoxide;
(4) polymers soln getting step (1) gained and the nanoparticle sol dispersion liquid of gained in step (3) mixs also that ultrasonic disperse is even, the mass ratio of polymkeric substance and nanoparticle sol is 5:95, by mixed dispersion liquid to being poured on totally smooth sheet glass, put into loft drier, drying 48 hours at 80 DEG C of temperature; Put into after the demoulding after 85wt% phosphoric acid solution soaks 48h and take out, wash the phosphoric acid solution on film surface off, obtain final proton exchange membrane, doping ratio 5% with thieving paper, the thickness of film is 80 microns.
The preparation of the resistance to temperature proton exchange film of PBI of embodiment 4:15% nanoparticle doped
Methyl-sulphoxide (DMSO) solution 10ml containing 0.85g polybenzimidazole, add containing 0.15g both sexes nanoparticle sol dispersion liquid, ultrasonic disperse makes it be uniformly dispersed in 30 minutes; The concentration of phosphoric acid solution is 75 wt%, and soak 60h, all the other operations are all identical with embodiment 3, and the doping ratio of proton exchange membrane is 15%, and the gauge control of film is at 65 microns.
The preparation of the resistance to temperature proton exchange film of PBI of embodiment 5:25% nanoparticle doped
Methyl-sulphoxide (DMSO) solution 10ml containing 0.75g polybenzimidazole, add containing 0.25g both sexes nanoparticle sol dispersion liquid, ultrasonic disperse makes it be uniformly dispersed in 30 minutes; ; The concentration of phosphoric acid solution is 80wt%, and soak 72h, all the other operations are all identical with embodiment 3, and the doping ratio of proton exchange membrane is 25%, and the gauge control of film is at 55 microns.
Embodiment 6:TGA tests
The thermotolerance of the PBI of PBI, both sexes nanoparticle sol and doping all uses thermal analyzer SDT Q600 (TA company of the U.S.).
The results are shown in Figure 2, result shows, both sexes nanoparticle sol just starts to decompose 150 DEG C time, and the decomposition temperature of the PBI of PBI and doping 25% both sexes nanoparticle reaches more than 350 DEG C.
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 perturbation amplitude in test process is 10mV, and range of frequency is 10 ~ 1MHz; The bulk resistance value Rb of film gets Z '-Z " abscissa value that curve medium-high frequency semicircle is corresponding with low frequency straight-line intersection, if when test frequency is not too high or system specific conductivity is higher, high frequency semicircle does not occur, Rb gets the abscissa value of high frequency end points; The specific conductivity of film at certain temperature is calculated according to calculation formula below:
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 results are shown in Figure 3: along with the rising of temperature, the specific conductivity of film progressively increases, and the most high energy of the specific conductivity of the composite membrane of doping both sexes nanoparticle reaches 1.033 × 10
-1s/cm.
Embodiment 8:
The transmission microscopy test result display of both sexes nanoparticle: the even particle size distribution of both sexes nanoparticle, is about 10 ran, the results are shown in Figure 4.
Embodiment 9: the water suction of composite membrane, inhale sour rate and dissolution test.
By the composite membrane of the both sexes nanoparticle of doping different ratios, after 105 DEG C of constant weights, after the film of 0.2g being placed in 50ml distilled water or 85% phosphoric acid 48h, film is taken out, dry, weigh, in triplicate, calculate the adsorptive capacity of water or phosphoric acid, the results are shown in Table 1, as can be seen from the table: along with the rising of doping ratio, the water content of film, also along with increasing, illustrates that the nanoparticle seed of doping has stronger hydrophilic ability; In same bubble acid caudacoria, the content of acid also increases along with the rising of doping ratio, illustrates that nanoparticle and phosphoric acid have good affinity, forms hydrogen bond therebetween, for the conduction of proton provides passage, and then improve the proton conductivity of film.
The water suction that table 1 is doping both sexes nanoparticle composite membrane and the acid energy of Phosphate Sorption
After the compound film bubble acid of the both sexes nanoparticle of doping different ratios, the film of 0.2g is placed in 50ml distilled water to certain hour (10min, 20 min30 min, 45 min, 60 min, 120 min) after, film is taken out, dries, weigh, calculate both sexes nanoparticle seepage discharge, in triplicate, the results are shown in Figure 5, as can be seen from the figure along with the raising of nanoparticle doped ratio, the loss ratio of acid in film, in reduction, illustrates that the nanoparticle of doping has the effect keeping phosphorus acid content in film, finally can keep the stable conductivity of proton membrane.
Embodiment 10: assembling monocell test
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 results are shown in Figure 6, can reach 80mW/cm under 80 degree
2.
Claims (3)
1. a compound proton exchange membrane for high temperature resistant fuel cell, is characterized in that: adopt and prepare with the following method:
(1) prepare polybenzimidazole solution: get polybenzimidazole and be dissolved in methyl-sulphoxide (DMSO), every 10 ~ 20ml methyl-sulphoxide dissolves 1g polybenzimidazole, and be heated to polymer dissolution complete, system becomes amber transparent solution;
(2) both sexes nanoparticle sol is prepared: in nitrogen atmosphere, tetrahydrofuran (THF) (THF) solution of sultone is slowly added drop-wise in tetrahydrofuran (THF) (THF) solution of APTES, wherein the mol ratio of sultone and APTES is 1:1, temperature of reaction controls between 40-60 DEG C, after magnetic agitation reaction 1 ~ 3h, with the THF in Rotary Evaporators removing system, and by petroleum ether, after removing sherwood oil, to add amount of substance be the pH of 10 times of APTES be 2 distilled water stirring at room temperature 24h ~ 48h, obtain nanoparticle sol,
(3) for the preparation of the nanoparticle dispersion liquid of doping: get the nanoparticle sol obtained in step (2) and be dissolved in methyl-sulphoxide (DMSO), every 10ml methyl-sulphoxide dissolves 1g nanoparticle sol, then being placed in ultrasonic apparatus makes nanoparticle sol dispersed at methyl-sulphoxide, obtains nanoparticle sol dispersion liquid;
(4) the PBI composite membrane of doped with nanometer particle is prepared: get the DMSO solution of the polybenzimidazole of gained in step (1) and the nanoparticle sol dispersion liquid of the middle gained of step (3), by nanoparticle sol and polymkeric substance 1:3 mass ratio mixing and ultrasonic disperse is even, gained dispersion liquid is poured onto on smooth clean sheet glass, evaporation of solvent, is cooled to room temperature rear demoulding;
(5) be immersed in 75 ~ 85wt% phosphoric acid solution by gained film in step (4), take out after 48 ~ 72h, dry the phosphoric acid solution on film surface, obtain the compound proton exchange membrane for 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, is characterized in that: the sultone in described step (2) is PS or Isosorbide-5-Nitrae-butane sultone.
3. the compound proton exchange membrane of a kind of high temperature resistant fuel cell as claimed in claim 1, is characterized in that: the evaporation of solvent in described step (4) is evaporation of solvent at the temperature of 60 ~ 80 DEG C.
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| CN103570960B (en) * | 2013-07-19 | 2016-01-27 | 常州大学 | A kind of preparation method of the compound proton exchange membrane for high temperature resistant fuel cell |
| CN103700874B (en) * | 2013-12-23 | 2018-01-16 | 湖北工业大学 | A kind of in-situ modified polybenzimidazoles PEM of inorganic nano-particle and preparation method thereof |
| CN106887623A (en) * | 2015-12-16 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of membrane electrode used for high-temperature fuel cell and its preparation and application |
| CN106894162B (en) * | 2015-12-18 | 2020-03-10 | 中国科学院大连化学物理研究所 | Composite fiber membrane and preparation and application thereof |
| CN105680079B (en) * | 2016-04-19 | 2018-03-09 | 合肥工业大学 | A kind of preparation method of lamellar composite PEM for fuel cell |
| CN106084776B (en) * | 2016-07-08 | 2018-08-24 | 上海电力学院 | A kind of high intensity high heat conductive insulating composite membrane and preparation method thereof |
| CN106410247A (en) * | 2016-12-07 | 2017-02-15 | 黄河科技学院 | Polybenzimidazole phosphoric acid high-temperature proton exchange membrane with high phosphoric acid adsorbing capability and preparation method thereof |
| CN108649257B (en) * | 2018-04-03 | 2020-12-18 | 福建永同丰超低能耗建筑研究院有限公司 | High-temperature proton exchange membrane and preparation method thereof |
| CN109575346B (en) * | 2018-12-22 | 2021-03-16 | 大连大学 | Preparation method of flexible conductive material of high-temperature-resistant substrate |
| CN109580418A (en) * | 2019-01-20 | 2019-04-05 | 王忠良 | Harmful heavy metal detection method in a kind of cosmetics |
| CN117126403B (en) * | 2023-10-26 | 2024-01-02 | 山东富源新材料股份有限公司 | Synthesis method of methyl MQ silicon resin |
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