CN101148537A - Nano-level zirconium-salt dispersion modified polyphenyl ether composite proton exchanging film material - Google Patents
Nano-level zirconium-salt dispersion modified polyphenyl ether composite proton exchanging film material Download PDFInfo
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- CN101148537A CN101148537A CNA2007100373134A CN200710037313A CN101148537A CN 101148537 A CN101148537 A CN 101148537A CN A2007100373134 A CNA2007100373134 A CN A2007100373134A CN 200710037313 A CN200710037313 A CN 200710037313A CN 101148537 A CN101148537 A CN 101148537A
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Abstract
The present invention discloses one kind of nanometer zirconium salt modified polyphenylene oxide composite proton exchange film material, which consists of modified polyphenylene oxide, imidazole or benzimidazole, and nanometer level zirconium salt. The modified polyphenylene oxide has the chemical structure as shown, characteristic viscosity of 0.50-0.80 dl/g and ion exchange capacity of 2.0-4.0 meq/g; and the nanometer level zirconium salt is zirconium phosphate or zirconium citrate. The nanometer zirconium salt modified polyphenylene oxide composite proton exchange film material has ion exchange capacity of 1.9-5.0 meq/g, thickness of 60-200 microns, excellent mechanical performance, high heat stability, low cost, high operation temperature and high conductivity. It may be applied in proton exchange film fuel cell and redox fluid flow cell.
Description
Technical field
The present invention relates to a kind of functional polymer composites, particularly a kind of nano-level zirconium-salt dispersive modified polyphenyl ether composite proton exchanging film material can be used for the proton exchange membrane in Proton Exchange Membrane Fuel Cells, the redox flow batteries.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) removes the general characteristic with fuel cell, and as not being subjected to the restriction of carnot's working cycle, energy conversion efficiency is high, start fast but also have room temperature simultaneously, no electrolyte loss, water is easily discharged, life-span is long, outstanding features such as specific power and energy height.Therefore, not only can be used for building and disperse the power station, also be suitable for especially as removable propulsion source.Future with the hydrogen energy era of hydrogen as main energy carrier, the family power source that it is still best.Proton exchange membrane is that the core of PEMFC is formed, provide passage in the fuel battery inside proton exchange membrane for the migration and the conveying of proton, make proton arrive negative electrode from anode through film, constitute the loop with the transfer transport of external circuit, provide electric current to the external world, therefore the performance of proton exchange membrane plays crucial effects to fuel cell performance, and its quality directly influences the work-ing life of battery.
Concerning Proton Exchange Membrane Fuel Cells, proton exchange membrane is not only a kind of diaphragm material, or the substrate of ionogen and electrode active material (eelctro-catalyst); But also should have low-permeability to reactant gases to avoid penetration phenomenon.Therefore, the proton exchange membrane that is used for Proton Exchange Membrane Fuel Cells should meet the following conditions: (1) gas permeability is low, to play the effect that intercepts fuel and oxygenant; (2) proton conductivity height; (3) good chemistry and electrochemical stability is as the acid and alkali-resistance scale resistance, to guarantee the working life of battery; (4) Heat stability is good impacts to bear the uneven heat that is in operation; (5) have certain physical strength, workability is good; (6) suitable cost performance.
For many years, people have studied various films and have been used for Proton Exchange Membrane Fuel Cells.Once adopted resol sulfonic acid type film, polystyrolsulfon acid type film, polytrifluorostyrene sulfonic acid type film etc. several, what application was more now is the perfluoro sulfonic acid membrane of DuPont and Dow Chemical Company exploitation, and its primary structure is to connect sulfonic acid group (SO by ehter bond on the skeleton of tetrafluoroethylene
3H), excellent chemical stability and low resistance make it become preferred material.But still there are some shortcomings in perfluoro sulfonic acid membrane:
(1) making is difficult, cost is high, and the synthetic and sulfonation procedure of perfluor material is loaded down with trivial details, costs an arm and a leg the Treatment for Reuse difficulty;
(2) to the temperature requirement height, be generally 70-90 ℃, surpass 100 ℃ because water content sharply reduces, and conductivity descends rapidly, hindered by suitable raising working temperature and improved an electrode reaction speed and a difficult problem that overcomes poisoning of catalyst;
(3) some hydrocarbon polymer, as methyl alcohol, rate of permeation is higher.
Proton exchange membrane has determined the temperature profile of Proton Exchange Membrane Fuel Cells.In allowed band, working temperature has very remarkable influence to the PEMFC performance: along with the rising of temperature, under the same current density condition, the operating voltage of fuel cell increases thereupon, that is to say that the power of fuel cell increases.In addition, along with the rising of temperature, can accelerate the diffusion of reactant gases to catalyst layer, to the motion of negative electrode and the discharge of resultant water, these all can play a positive role to the raising of battery performance accelerating proton from anode.But because the restriction of the used macromolecular material of perfluoro sulfonic acid membrane, when temperature surpassed 100 ℃, moisture evaporation in the film caused the proton conduction performance sharply to descend, so the use temperature of proton exchange film fuel cell electric piling is all about 80 ℃.In order to guarantee the works better of high power fuel cell, to have to battery energy-producing 50% is used for cooled fuel cell systems, the heat that is produced to remove so just greatly reduces the specific power of fuel cell.
In addition, Proton Exchange Membrane Fuel Cells has high requirement to the purity of fuel gas.Often contain a spot of carbon monoxide (being generally about 1%) in the fuel reforming gas, and CO very easily makes poisoning of catalyst among the PEMFC, under higher current density condition, even the CO of several ppm content, also can cause the serious decline of battery performance.And the tolerance of the impure fuel of fuel cell and working temperature are closely related, and temperature raises, and tolerance improves.Temperature is higher than 120 ℃ just can obviously reduce the CO intoxicating phenomenon.
Therefore,, improve the use temperature of the used macromolecular material of proton exchange membrane, improve the use temperature of fuel cell pile, become the bottleneck problem that improves the Proton Exchange Membrane Fuel Cells specific power for accelerating to realize the business-like speed of Proton Exchange Membrane Fuel Cells.
The polyphenylene oxide base polymer is a kind of engineering plastics of excellent performance, and second-order transition temperature is the highest in thermoplastics, water-absorbent is minimum, receives publicity with its good thermotolerance and mechanical property.The homogeneous phase sulfonated poly (phenylene oxide) has good mechanical property, the thermostability height, and have the selection separation function.Document J.Mem.Sci.225,63-76 (2003) have reported the proton exchange membrane of sulfonated poly (phenylene oxide) preparation, and loading capacity (IEC) can reach 0.4217meq or g.Chinese patent 99809604.0＜the be used for blend membranes based on sulfonated poly (phenylene oxide) of the polymer electrochemical cells of improvement in performance 〉, introduced the homogeneous blend of sulfonated poly (phenylene oxide) and poly(vinylidene fluoride), but these proton exchange membrane all are the low-cost surrogates as Nafion class film, are still in routine work temperature (＜100 ℃) to use down.
Document Chem.Rev.104,4637-4678 (2004) have reported that imidazoles is by hydrogen bond action generation proton room and proton between-NH base and N or the O.With the water ratio, obviously improve (boiling point is 257 ℃) as the imidazoles temperature stability of cloth Leinster alkali, can be used in fuel cell and the secondary cell, and can solve the infiltration of humidification water and than evaporation of water problem under the elevated operating temperature.Document J.Am.Chem.Soc.126,15644-15645 (2004) has reported 2,4,5-three flumizoles and Nafion blend film can be worked under 120 ℃ of temperature, have also alleviated the carbon monoxide poisoning problem of platinum electrode when keeping high conductivity, but owing to be fluorochemical, price is still high.
Zirconium phosphate or citric acid zirconium have water absorbability, adding nano level zirconium phosphate or nano level citric acid zirconium can improve the water retention property of film in the proton exchange membrane, make proton exchange membrane to move under comparatively high temps, reaction kinetics is improved, thereby improves the energy density of fuel cell; The improvement of water retention property has also reduced humidification requirement, has simplified water management.Document Electrochem.Solid State Lett.4, A31-A34 (2001) has reported the proton exchange membrane with nano level zirconium phosphate modification Nafion, moves under 150 ℃, dry oxygenant condition, and is functional.But with Nafion is substrate, and price remains key issue.
Redox flow batteries (RFB-Redox Flow Battery) is that a kind of redox couple that utilizes in the electrolytic solution that flows is as the electric energy accumulator of electrochemical reaction active substance.Active substance is the ion that is present in the different oxidation state in the electrolytic solution, and electrolytic solution and battery are placed apart, does not have normal self-discharge and the electrolytic solution spoilage problems that exists of common batteries.But behind the battery life-time service, membranous resistance increases, and ion selectivity reduces, to battery discharge and recharge and battery performance has detrimentally affect.Therefore, the good proton exchange membrane that is used for RFB should meet the following conditions: (1) chemistry and electrochemical stability under Working environment; (2) physical strength under working conditions and stability; (3) ionic conductance height; (4) suitable cost performance.
Summary of the invention
The purpose of this invention is to provide a kind of is matrix with the Noryl, the composite proton exchange membrane material of doping imidazoles or benzoglyoxaline and nano-level zirconium-salt, this material has higher proton conductivity, mechanical property is good, Heat stability is good, can under comparatively high temps (120 ℃-200 ℃), be used for Proton Exchange Membrane Fuel Cells, also can be used for redox flow batteries simultaneously.
A kind of nano-level zirconium-salt dispersive of the present invention modified polyphenyl ether composite proton exchanging film material is composed as follows:
Noryl is 20-78wt%, and imidazoles or benzoglyoxaline are 7-47wt%, and nano-level zirconium-salt is 15-33wt%;
Wherein, Noryl has following chemical structure:
R in the formula
1And R
2Be selected from H, SO respectively
3H, SO
3M, SO
2R
3Or SO
2N (R
3)
2, R wherein
3Be selected from C
1-C
4Alkyl or aryl, M is selected from Li
+, Na
+, K
+, Mg
2+, Ca
2+Or NH
4 +R
1And R
2In have at least one not to be H; N is the integer of 70-5000; Its intrinsic viscosity is that 0.50-0.80dl/g, loading capacity are 2.0-4.0meq/g; Nano-level zirconium-salt is nano level zirconium phosphate or nano level citric acid zirconium;
A kind of loading capacity of nano-level zirconium-salt dispersive modified polyphenyl ether composite proton exchanging film material is 1.9-5.0meq/g, and thickness is 60-200 μ m.
The preparation method of a kind of nano-level zirconium-salt dispersive of the present invention modified polyphenyl ether composite proton exchanging film material is as follows:
Noryl is dissolved in the organic solvent, forms the solution of 5-20wt%; Add imidazoles or benzoglyoxaline then, wherein imidazoles or benzoglyoxaline are 8.9-236wt% with the ratio of Noryl, after ultrasonic vibration 0.5-5 under the frequency 20-60kHz hour, be poured on the clean plane, the scraper curtain coating, curtain coating solution was placed in the container that high pure nitrogen flows down 12-24 hour vacuum-drying 24-48 hour again; Be immersed in the 3-80wt% zirconium oxychloride solution 2-12 hour then, take out drip washing, put into 5-55wt% phosphoric acid or 7-80wt% citric acid solution again 6-24 hour, the drip washing drying, place the hydrochloric acid soln of volume ratio 1/23-1/10 to be converted to proton form, washing is to remove unnecessary acid in deionized water, and drying obtains a kind of nano-level zirconium-salt dispersive modified polyphenyl ether composite proton exchanging film material.
The Noryl that the present invention uses has following chemical structure:
R in the formula
1And R
2Be selected from H, SO respectively
3H, SO
3M, SO
2R
3Or SO
2N (R
3)
2, R wherein
3Be selected from C
1～C
4Alkyl or aryl, M is selected from Li
+, Na
+, K
+, Mg
2+, Ca
2+Or NH
4 +R
1And R
2In have at least one not to be H; N is the integer of 70-5000; Its intrinsic viscosity is that 0.50-0.80dl/g, loading capacity are about 2.0-4.0meq/g.
The organic solvent that the present invention uses is selected from N, dinethylformamide, N,N-dimethylacetamide or N-N-methyl-2-2-pyrrolidone N-.
A kind of nano-level zirconium-salt dispersive of the present invention modified polyphenyl ether composite proton exchanging film material is owing to added imidazoles or benzoglyoxaline in modified polyphenyl ether, reduced dependence to water, simultaneously, in the fenestra road, reach the nano-level zirconium-salt that the film surface forms, improved the water retention property of film; And imidazoles or benzoglyoxaline obviously improve (boiling point is 257 ℃) than water temp is stable, and zirconium phosphate or citric acid zirconium fusing point are higher, have improved the thermostability of material, make proton exchange membrane to move under comparatively high temps.
The loading capacity of a kind of nano-level zirconium-salt dispersive of the present invention modified polyphenyl ether composite proton exchanging film material is 1.9-5.0meq/g, and thickness is 60-200 μ m.Compare with perfluoro sulfonic acid membrane such as Nafion, when reducing cost, more can under comparatively high temps, (120-200 ℃) be used for Proton Exchange Membrane Fuel Cells, also can be used for redox flow batteries simultaneously.160 ℃, relative humidity (RH) 15% o'clock, the proton conductivity of the Nafion117 film that DuPont company produces is 7.3 * 10
-6S/cm, a kind of nano-level zirconium-salt dispersive Noryl compound proton exchange membrane then is 1.01 * 10 under the similarity condition
-4-2.40 * 10
-2S/cm.
Description of drawings
The nano level zirconium phosphate dispersive Noryl-imidazoles compound proton exchange membrane specific conductivity that Fig. 1 obtains for embodiment 1 and the graph of a relation of temperature.
The electron scanning micrograph of nano level zirconium phosphate dispersive Noryl-imidazoles compound proton exchange membrane that Fig. 2 obtains for embodiment 2.
The electron scanning micrograph of nano level zirconium phosphate dispersive Noryl-benzoglyoxaline compound proton exchange membrane that Fig. 3 obtains for embodiment 3.
The electron scanning micrograph of nano level citric acid zirconium dispersive Noryl-imidazoles compound proton exchange membrane that Fig. 4 obtains for embodiment 5.
The electron scanning micrograph of nano level citric acid zirconium dispersive Noryl-benzoglyoxaline compound proton exchange membrane that Fig. 5 obtains for embodiment 7.
Embodiment
Following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
With 0.49g Noryl (R
1, R
2=SO
3Na) be dissolved in 5.2mL N, form the solution of 10wt% in the N-N,N-DIMETHYLACETAMIDE, add 0.30g imidazoles (imidazoles and Noryl two components by weight are 40: 60), ultrasonic vibration is 2 hours under frequency 40kHz, be poured over clean plane (on the 7cm * 7cm), the scraper curtain coating was placed on curtain coating solution in the container that high pure nitrogen flows down 24 hours, and vacuum-drying is 48 hours again; Be immersed in the 24wt% zirconium oxychloride solution 4 hours then, take out drip washing, put into the 10wt% phosphoric acid solution again 12 hours, the drip washing drying, placing volume ratio is that 1/11 hydrochloric acid soln is converted to proton form, unnecessary acid is removed in washing in deionized water, drying obtains little Huang, translucent Noryl-imidazoles-zirconium phosphate composite proton exchange membrane material, and the thickness of film is 115 μ m, 160 ℃, during relative humidity 15%, proton conductivity is 1.21 * 10
-2S/cm.The nano level zirconium phosphate dispersive Noryl-imidazoles compound proton exchange membrane specific conductivity that Fig. 1 obtains for embodiment 1 and the graph of a relation of temperature, the Nafion film is produced by DuPont company among the figure, model is Nafion117,160 ℃, during relative humidity 15%, the proton conductivity of Nafion117 film is 7.3 * 10
-6S/cm, the specific conductivity of nano level zirconium phosphate dispersive Noryl-imidazoles compound proton exchange membrane is than the specific conductivity height of Nafion117 film as seen from the figure, and both specific conductivity differ and can reach 3 orders of magnitude in the time of 160 ℃.
Embodiment 2
With 0.40g Noryl (R
1=H
+, R
2=SO
3H) be dissolved in 4.2mL N, form the solution of 10wt% in the dinethylformamide, add 0.133g imidazoles (imidazoles and Noryl two components by weight are 25: 75), ultrasonic vibration is 1 hour under frequency 20kHz, be poured over clean plane (on the 5cm * 5cm), the scraper curtain coating was placed on curtain coating solution in the container that high pure nitrogen flows down 12 hours, and vacuum-drying is 36 hours again; Be immersed in the 15wt% zirconium oxychloride solution 10 hours then, take out drip washing, put into the 10wt% phosphoric acid solution again 24 hours, the drip washing drying, obtain little Huang, translucent nano level zirconium phosphate dispersive Noryl-imidazoles composite proton exchange membrane material, the thickness of film is 106 μ m, 160 ℃, during relative humidity 15%, proton conductivity is 2.40 * 10
-2S/cm.The electron scanning micrograph of nano level zirconium phosphate dispersive Noryl-imidazoles compound proton exchange membrane that Fig. 2 obtains for embodiment 2, amplified 20,000 times, top white point is the zirconium phosphate that forms on the film surface, the size of zirconium phosphate particles is in nanometer range as can be seen from Figure, because zirconium phosphate formation condition surperficial at film and in the duct is the same, can infers that the zirconium phosphate particles of producing also is nano level in the duct, and be many same particulate coacervates.
Embodiment 3
With 0.31g Noryl (R
1=H
+, R
2=SO
2N (CH
3)
2) be dissolved in 6.4mL N, form the solution of 5wt% in the dinethylformamide, add 0.31g benzoglyoxaline (benzoglyoxaline and Noryl two components by weight are 50: 50), ultrasonic vibration is 5 hours under frequency 40kHz, be poured over clean plane (on the 7cm * 7cm), the scraper curtain coating was placed on curtain coating solution in the container that high pure nitrogen flows down 12 hours, and vacuum-drying is 36 hours again; Be immersed in the 6wt% zirconium oxychloride solution 6 hours then, take out drip washing, put into the 23wt% phosphoric acid solution again 12 hours, the drip washing drying, placing volume ratio is that 1/10 hydrochloric acid soln is converted to proton form, unnecessary acid is removed in washing in deionized water, drying obtains little Huang, translucent nano level zirconium phosphate dispersive Noryl-benzoglyoxaline compound proton exchange membrane, and the thickness of film is 110 μ m, 200 ℃, during relative humidity 15%, proton conductivity is 6.14 * 10
-3S/cm.The electron scanning micrograph of nano level zirconium phosphate dispersive Noryl-benzoglyoxaline compound proton exchange membrane that Fig. 3 obtains for embodiment 3 has amplified 20,000 times, and the size of zirconium phosphate particles is a nano level as can be seen from Figure.
Embodiment 4
Adopt the identical method of embodiment 1, different is that solvent for use is the N-N-methyl-2-2-pyrrolidone N-, obtain little Huang, translucent nano level zirconium phosphate dispersive Noryl-imidazoles compound proton exchange membrane, the thickness of film is 120 μ m, 160 ℃, during relative humidity 15%, proton conductivity is 9.07 * 10
-3S/cm.
Embodiment 5
Adopt the identical method of embodiment 1, different is that phosphoric acid solution is changed to citric acid solution, obtain little Huang, translucent nano level citric acid zirconium dispersive Noryl-imidazoles compound proton exchange membrane, the thickness of film is 117 μ m, 120 ℃, during relative humidity 15%, proton conductivity is 5.44 * 10
-4S/cm.The electron scanning micrograph of nano level citric acid zirconium dispersive Noryl-imidazoles compound proton exchange membrane that Fig. 4 obtains for embodiment 5 has amplified 27,000 times, and citric acid zirconium particulate size is a nano level as can be seen from Figure.
Embodiment 6
Adopt the identical method of embodiment 2, different is that phosphoric acid solution is changed to citric acid solution, obtain little Huang, translucent nano level citric acid zirconium dispersive Noryl-imidazoles compound proton exchange membrane, the thickness of film is 110 μ m, 140 ℃, during relative humidity 15%, proton conductivity is 1.08 * 10
-3S/cm.
Embodiment 7
Adopt the identical method of embodiment 3, different is that phosphoric acid solution is changed to citric acid solution, obtain little Huang, translucent nano level citric acid zirconium dispersive Noryl-benzoglyoxaline compound proton exchange membrane, the thickness of film is 115 μ m, 180 ℃, during relative humidity 15%, proton conductivity is 9.55 * 10
-4S/cm.The electron scanning micrograph of nano level citric acid zirconium dispersive Noryl-benzoglyoxaline compound proton exchange membrane that Fig. 5 obtains for embodiment 7 has amplified 20,000 times, and citric acid zirconium particulate size is a nano level as can be seen from Figure.
Embodiment 8
Adopt the identical method of embodiment 4, different is that phosphoric acid solution is changed to citric acid solution, obtain little Huang, translucent nano level citric acid zirconium dispersive Noryl-imidazoles compound proton exchange membrane, the thickness of film is 127 μ m, 200 ℃, during relative humidity 15%, proton conductivity is 1.01 * 10
-4S/cm.
Claims (1)
1. a nano-level zirconium-salt dispersive modified polyphenyl ether composite proton exchanging film material is characterized in that its composition
As follows:
Noryl is 20-78wt%, and imidazoles or benzoglyoxaline are 7-47wt%, and nano-level zirconium-salt is 15-33wt%, and wherein Noryl has following chemical structure:
R in the formula
1And R
2Be selected from H, SO respectively
3H, SO
3M, SO
2R
3Or SO
2N (R
3)
2, R wherein
3Be selected from C
1-C
4Alkyl or aryl, M is selected from Li
+, Na
+, K
+, Mg
2+, Ca
2+Or NH
4 +R
1And R
2In have at least one not to be H; N is the integer of 70-5000; Its intrinsic viscosity is that 0.50-0.80dl/g, loading capacity are about 2.0-4.0meq/g; Nano-level zirconium-salt is nano level zirconium phosphate or nano level citric acid zirconium; A kind of loading capacity of nano-level zirconium-salt dispersive modified polyphenyl ether composite proton exchanging film material is 1.9-5.0meq/g, and thickness is 60-200 μ m.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011044778A1 (en) * | 2009-10-16 | 2011-04-21 | 中国科学院大连化学物理研究所 | Aromatic polymer ion exchange membrane and its complex membrane and its application for acidic electrolyte flow energy storage battery |
| CN103094587A (en) * | 2013-01-21 | 2013-05-08 | 常州大学 | Preparation method of high-temperature resistant sulfonated polyimide-zirconium phosphate proton exchange composite membrane |
| CN108306036A (en) * | 2018-02-11 | 2018-07-20 | 温州市赢创新材料技术有限公司 | A kind of polyalcohol intercalation basic zirconium phosphate proton exchange membrane and preparation method thereof |
| CN108417869A (en) * | 2018-03-06 | 2018-08-17 | 查公祥 | A kind of bromination is fitted into polyphenylene oxide proton membrane and preparation method thereof |
| CN108598536A (en) * | 2018-04-27 | 2018-09-28 | 芜湖天科生物科技有限公司 | A kind of heat-resisting proton exchange membrane and preparation method thereof |
-
2007
- 2007-02-08 CN CNA2007100373134A patent/CN101148537A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011044778A1 (en) * | 2009-10-16 | 2011-04-21 | 中国科学院大连化学物理研究所 | Aromatic polymer ion exchange membrane and its complex membrane and its application for acidic electrolyte flow energy storage battery |
| US9276282B2 (en) | 2009-10-16 | 2016-03-01 | Dalian Rongke Power Co., Ltd. | Aromatic polymer ion exchange membranes, its composite membrane, and its application in acidic electrolyte flow battery |
| CN103094587A (en) * | 2013-01-21 | 2013-05-08 | 常州大学 | Preparation method of high-temperature resistant sulfonated polyimide-zirconium phosphate proton exchange composite membrane |
| CN103094587B (en) * | 2013-01-21 | 2015-04-22 | 常州大学 | Preparation method of high-temperature resistant sulfonated polyimide-zirconium phosphate proton exchange composite membrane |
| CN108306036A (en) * | 2018-02-11 | 2018-07-20 | 温州市赢创新材料技术有限公司 | A kind of polyalcohol intercalation basic zirconium phosphate proton exchange membrane and preparation method thereof |
| CN108417869A (en) * | 2018-03-06 | 2018-08-17 | 查公祥 | A kind of bromination is fitted into polyphenylene oxide proton membrane and preparation method thereof |
| CN108598536A (en) * | 2018-04-27 | 2018-09-28 | 芜湖天科生物科技有限公司 | A kind of heat-resisting proton exchange membrane and preparation method thereof |
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