CN101733010B - Doped double cross-linking reinforced perfluorinated proton exchange membrane and preparation method thereof - Google Patents
Doped double cross-linking reinforced perfluorinated proton exchange membrane and preparation method thereof Download PDFInfo
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- CN101733010B CN101733010B CN2009102311358A CN200910231135A CN101733010B CN 101733010 B CN101733010 B CN 101733010B CN 2009102311358 A CN2009102311358 A CN 2009102311358A CN 200910231135 A CN200910231135 A CN 200910231135A CN 101733010 B CN101733010 B CN 101733010B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a doped acylamino cross-linking reinforced perfluorinated proton exchange membrane belonging to the field of functional polymer composites. The perfluorinated proton exchange membrane has an acylamino cross-linking structure and a physical bonding network structure, wherein the acylamino cross-linking structure is formed by using perfluorinated sulfonic acid resin as a film-forming resin, adding an auxiliary proton transfer substance and carrying out across-linking reaction on the auxiliary proton transfer substance and a cross-linking agent; and the physical bonding network structure is formed by adding the high-price metal compound and an acid group with the acylamino cross-linking structure. With the two cross-linking network structures, the perfluorinated proton exchange membrane achieves the effect of improving the mechanical property, the stability, the air tightness and other performances.
Description
Technical field
The invention belongs to field of functional polymer composites, relate to a kind of ionic exchange film for fuel cell, particularly a kind of dual cross-linked perfluorinated sulfonic acid proton exchange film that adds high-valency metal compound and auxiliary proton conductive substance.
Background technology
Proton Exchange Membrane Fuel Cells is a kind ofly directly chemical energy to be converted into the TRT of electric energy by electrochemical means, is considered to the cleaning of 21 century first-selection, generation technology efficiently.(proton exchange membrane PEM) is Proton Exchange Membrane Fuel Cells (proton exchange membrane fuel cell, critical material PEMFC) to PEM.
Present employed perfluorinated sulfonic acid PEM has good proton-conducting and chemical stability under (80 ℃) and the higher humidity at a lower temperature.But they also have a lot of defectives:, poor chemical stability not high as poor dimensional stability, mechanical strength etc.Film water absorption rate and size of causing because of suction under different humidity expand also different, and when film during at different operating mode down conversion, the size of film also will so change.So repeatedly, finally cause PEM generation mechanical damage.In addition, the reaction of the positive pole of fuel cell usually produces the material that a large amount of hydroxyl free radicals and hydrogen peroxide etc. have strong oxidizing property, and non-fluorin radical on these materials meeting attack film-forming resin molecules causes film generation chemical degradation and damaged, foaming.At last, when the operating temperature of perfluorinated sulfonic acid exchange membrane is higher than 90 ℃,, thereby the efficient of fuel cell is descended greatly owing to the rapid dehydration of film causes the proton-conducting of film sharply to descend.But high operating temperature can improve the anti-carbon monoxide of fuel-cell catalyst greatly.Be exactly that existing perfluoro sulfonic acid membrane all has certain hydrogen or methanol permeability in addition, especially in DMFC, methanol permeability is very big, and this becomes fatal problem.Therefore, how to improve the proton conduction efficient under perfluorinated sulfonic acid proton exchange film strength, dimensional stability and the high temperature, the permeability of reduction working media etc. and become the key subjects that fuel cell industries faces.
U.S. Pat 7259208 discloses and has contained triazine ring cross-linked structure perfluoro sulfonic acid membrane, has excellent mechanical intensity and dimensional stability equally, but makes inevitably in the method for this patent disclosure and exist a large amount of unreacted crosslinked groups in the cross linking membrane.In the operation of fuel cells environment, these unreacted crosslinked groups will be degraded by free radical, thus the life-span of having reduced film.
U.S. Pat 6733914 discloses the perfluor sulfonyl fluorine type film that will melt extrude and has soaked in ammoniacal liquor, thereby forms the PEM of sulfimide cross-linked structure, and so the perfluoro sulfonic acid membrane of handling has excellent mechanical intensity and dimensional stability.But the resulting film of the method for utilizing this patent does not have the good high-temperature proton conductivity.
For solving the high temperature proton conduction behavior of perfluoro sulfonic acid membrane, the auxiliary proton conductive substance that will much have the high-temp water-preserving ability joins in the perfluorinated sulfonic acid exchange membrane.Selected auxiliary proton conductive substance must have following performance: (1) particle has water holding capacity preferably, and higher dehydration temperature is just arranged; (2) has intermiscibility preferably with proton exchange resins; (3) particle has certain proton conductivity; (4) be easy to obtain littler nanometer particle; (5) structural stability of particle is good, does not follow tangible structural change in suction, dehydration; (6) help keeping or improving the mechanical strength or the physical size stability of PEM.The auxiliary proton conductive substance particle that adopts is SiO normally
2, TiO
2, Zr (HPO
4)
2Or ZrO
2Particle, heteropoly acid or solid acid particle, zeolite family mineral particle, stratotype clay mineral such as montmorillonite and intercalation clay mineral thereof etc.
For example Chinese patent 200810138704.x discloses a kind of crosslinked enhancing and adds by the perfluoro sulfonic acid membrane of assisting proton conductive substance, owing to added auxiliary proton conductive substance in cross linking membrane, makes the high temperature proton conducting ability of film improve greatly.
But crosslinked enhancing film in the past often only adopts chemical bonding crosslinked, and its degree of cross linking is little, can't increase substantially the character of film on mechanical performance.
The perfluorinated sulfonic acid ionic membrane that is used for fuel cell need meet the demands: stable, high conductivity, high mechanical properties.Generally speaking, when ion-exchange capacity raise, the equivalent value of (per) fluoropolymer descends, and (equivalent value EW value reduced, ion exchange capacity IEC=1000/EW), film strength also reduces simultaneously, and the also rising thereupon of the gas permeability of film, and this will produce very fuel cell and seriously influence.Therefore, preparation has the macroion exchange capacity, has favorable mechanical mechanical strength and air-tightness, and the film with good stable is fuel cell, and especially the fuel cell that uses on delivery vehicles such as automobile is able to practical key.
Summary of the invention
At the deficiencies in the prior art, the inventor after having paid a large amount of creative works, thereby has finished the present invention through further investigation.
The objective of the invention is, provide a kind of and have than high proton conductivity with than the perfluoro sulfonic acid membrane of the dual cross-linked structure of doping of high-mechanical property.
The dual intercrossed enhanced full fluorin PEM of described doping provided by the invention, it is characterized in that: this film is film forming matter with the perfluorinated sulfonic resin, add auxiliary proton conductive substance, carry out cross-linking reaction with crosslinking agent under certain condition and form the amide groups cross-linked structure, the acidic-group that adds high-valency metal compound and amide groups cross-linked structure simultaneously forms the physical bond network structure.
The thickness of the dual crosslinked enhancing film of described adulterated full fluorin sulfonic acid is 1～300 μ m, is preferably 5～100 μ m, more preferably 10～30 μ m.
Described perfluorinated sulfonic resin is by tetrafluoroethene, and one or more copolymerization in the described perfluor olefinic functionality of general formula (A) monomer form:
CF
2＝CFO[CF
2CF(CF
3)]
fO(CF
2)
gSO
2F
F=0 or 1; The integer of g=2～4 (A)
This copolyreaction is the common practise in the organic chemistry field of polymer technology, as long as clear and definite comonomer specifically, then to those skilled in the art, select suitable copolyreaction condition according to prior art with may be obvious that, as temperature, time, solvent, initator etc., thereby obtain perfluorinated ion exchange resin of the present invention.
Amide groups cross-linked structure in the described dual cross-linked network is to form by the sulfuryl fluoride group on the perfluorinated sulfonic resin and ammonia, hydrazine or diamines, and its structure is suc as formula (II) or (III):
Wherein, a=1 or 2, R are methylene or perfluor methylene, and n is 0～5 integer.
Wherein, described auxiliary proton conductive substance comprises one or more in the following material:
(1) oxide: TiO for example
2, Sb
2O
5, ZrO
2, MoO
3, Ta
2O
5Or HfO
2
(2) phosphate: BPO for example
4, Zr
dH
3-2dPO
4(wherein d=0～1.5), Ti (HPO
4)
2, HSbP
2O
8, HSb
3P
2O
14Or H
5Sb
5P
2O
20
(3) heteropoly acid: H for example
3PW
12O
40, H
3SiW
12O
40, HxWO
3, HSbWO
6, H
3PMo
12O
40, H
2Sb
4O
11, HTaWO
6, HNbO
3, HTiNbO
5, HTiTaO
5, HSbTeO
6, H
5Ti
4O
9, HSbO
3Or H
2MoO
4
Preferably, described auxiliary proton conductive substance is: SiO
2, ZrO
2, TiO
2, BPO
4, Zr
3(PO
4)
4, Zr (HPO
4)
2, H
3PW
12O
40, CsHSO
4, CsH
2PO
4, H-modenite, H-montmorillonite, HZr
2(PO
4)
3, Zr
3(PO
4)
4, Ce (HPO
4)
2, Ti (HPO
4)
2Or Zr
2H (P
3O
10)
2In one or more.
The mass ratio of described auxiliary proton conductive substance and perfluorinated ion exchange resin is 0.5～50: 100, is preferably 1～40: 100, and 5-30 more preferably: 100, most preferably be 10-20: 100; Its particle diameter is 0.001～5 μ m, is preferably 0.01～4 μ m, and more preferably 0.5～3 μ m most preferably is 1～2 μ m.
The metallic element of described high-valency metal compound can be one of following element or combination: W, Ir, Y, Mn, Ru, V, Zn or La element.These element compounds account for perfluorinated ion exchange resin quality 0.001～5%, be preferably 0.1～4%, more preferably 0.5～3%, most preferably be 1～2%.
Described high-valency metal compound can be selected from a kind of or combination double salt in nitrate, sulfate, carbonate, phosphate or the acetate of the highest price attitude of these metallic elements and middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitogen-contained crown ether and nitrogen heterocyclic ring, EDTA (ethylenediamine tetra-acetic acid), DMF (N, dinethylformamide) or DMSO (dimethyl sulfoxide (DMSO)) complex compound of middle valence state.
Described high-valency metal compound can be selected from the highest price attitude of these metallic elements and the hydroxide of middle valence state.Described metal ion compound with high valence state is selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state.Described oxide with perovskite structure comprises but is not only following Compound C e
xTi
(1-x)O
2(x=0.25～0.4), Ca0.6La
0.27TiO
3, La
(1-y)Ce
yMnO
3(y=0.1～0.4) or La
0.7Ce
0.15Ca
0.15MnO
3
Described high-valency metal compound can load on the auxiliary proton conductive substance.The method for preparing this support structures can be sol-gel process, ion-exchange, chemical precipitation method, hydro-thermal method and hydrolytic precipitation method.For example use the process of gel-sol method as follows: with a certain amount of SiO
2Join in the cerium ammonium nitrate solution, stir adding citric acid down, continuation is stirred to spend the night and can be obtained above-mentioned CeO
2The SiO of load
2Particle.
The present invention also provides the preparation method of described ionic membrane, and step is as follows:
(1) perfluor sulfonyl fluororesin and auxiliary proton conductive substance are mixed, to melt extrude or the hot forming mode makes film;
(2) film that step (1) is made soaks down in 0 ℃～150 ℃ in the solution of crosslinking agent;
(3) film that step (2) is prepared is under the displacement reaction effect of heating or acid, alkali, part sulfuryl fluoride group and crosslinking agent formation cross-linked structure;
(4) with the basic hydrolysis of film process, the acidification step of step (3) preparation, make the crosslinked enhancing film of adulterated full fluorin sulfonic acid.
Also can behind (4) film forming hydrolysis acidification, film be immersed in the solution of high-valency metal compound.
Form formula (II) or (III) method of cross-linked structure be: utilize sulfuryl fluoride type resin and crosslinking agent ammonia, hydrazine, organic diamine or can obtain through the substance reaction that chemical treatment discharges ammonia, hydrazine, organic diamine.
Described organic diamine is C
1～C
5Alkyl or perfluor C
1～C
5Alkyl diamine, described organic or inorganic acid hydrochlorate, urea or the guanidine that can include but not limited to ammonia, hydrazine, organic diamine through the material that chemical treatment discharges ammonia, hydrazine, organic diamine.
The dual intercrossed enhanced full fluorin PEM of doping of the present invention has Mechanics of Machinery intensity and the air-tightness that exceeds the imagination, film also has amazing chemical stability simultaneously, this may be to come to have formed two kinds of cross-linked networks in the film, and wherein the formed network cross-linked degree of high-valency metal compound and acid ion cation exchange groups is much higher than only simple chemical bonding cross-linking network.In addition, the high-valency metal compound that is added easily with the acid amides cross-linked structure forms chelation structure, thereby further strengthened the performance of this dual cross-linked structure, the chemical substance Penetration Signature of film particularly, make the free radical of strong oxidizing property to diffuse into film by infiltration, the chemical stability of corresponding film is also improved greatly.
The specific embodiment
Present invention is described and explain for more detailed clearly; followingly many embodiment of the present invention are provided; but it will be understood by those skilled in the art that these embodiments only are used to exemplify, but not spirit of the present invention and claimed scope are limited.
Embodiment 1:
With formula
, EW=700 perfluor sulfonyl fluororesin and perovskite structure La
0.7Ce
0.15Ca
0.15MnO
3(account for resin quality 2%) mixed (wherein the phosphate mass content is 10%) with phosphoric acid one hydrogen zirconium powder body (diameter is 0.5 μ m) down at 210 ℃ and extruded by extruder, and extruding thickness is 50 μ m.Cut the above-mentioned extruded film of 10cm * 10cm, be immersed in perfluoro caprylic acid amine/dimethyl sulfoxide (DMSO) of 50 ℃ 5 hours, place 200 ℃ to handle 3 hours down film after the taking-up.It is that 25% NaOH was placed 8 hours down in 80 ℃ that the film of heating is placed mass concentration, and then be placed on mass concentration be in 5% the sulfuric acid in 80 ℃ place 3 hours down after, be washed till neutrality, obtain cross linking membrane.
Embodiment 2:
With formula
, the perfluor sulfonyl fluororesin of EW=1100 and zinc hydroxide (account for resin quality 2%) pass through extruder, mixing (wherein the phosphate mass content is 20%) with basic zirconium phosphate powder (diameter is 0.1 μ m) down at 250 ℃ extrudes, extruding thickness is 30 μ m, cut the above-mentioned extruded film of 10cm * 10cm, be immersed in 80 ℃ NH
4In the DMF solution of Cl 5 hours.Then the film that soaks is placed triethylamine 2 hours under 200 ℃, get crosslinked film.It is that 15% potassium hydroxide was placed 8 hours down in 80 ℃ that film is placed mass concentration, and then be placed on mass concentration be in 10% the nitric acid in 60 ℃ place 1 hour down after, be washed till neutrality, the crosslinked enhancing film of adulterated full fluorin sulfonic acid.
Embodiment 3:
With formula
Perfluor sulfonyl fluororesin and Zirconium powder (diameter is 0.05 μ m) mix (wherein the zirconia mass content is 5%), hot pressing film forming then, film thickness is 80 μ m.Cut the above-mentioned extruded film of 10cm * 10cm, be immersed in 90 ℃ the dimethylacetylamide aqueous mixtures of urea 5 hours.Place 100 ℃ to decompose 3 hours film after the taking-up, be warmed up to 170 ℃ again and kept 1.5 hours.It is that 10% NaOH was placed 8 hours down in 80 ℃ that the film of heating is placed mass concentration, and then be placed on mass concentration be in 15% the hydrochloric acid in 90 ℃ place 3 hours down after, be washed till neutrality, then this film be immersed in the nitric acid ruthenium solution, get the crosslinked enhancing film of adulterated full fluorin sulfonic acid.
Embodiment 4:
With formula
, EW=800 the perfluor sulfonyl fluororesin mix by extruder, mix (wherein the titanium dioxide mass content is 25%) with titanium dioxide powder (diameter is 2 μ m) down at 170 ℃ and extrude, extruding thickness is 120 μ m.Cut the above-mentioned extruded film of 10cm * 10cm, be immersed in 80 ℃ NH
3The dimethyl formamide aqueous mixtures in 3 hours.After the taking-up film is placed the nmp solution of ethylenediamine to soak and be warmed up to 160 ℃ and kept 1.5 hours, it is that 25% NaOH was in 80 ℃ of following hydrolysis 8 hours that this film is placed mass concentration, and then be placed on mass concentration be in 5% the sulfuric acid in 80 ℃ place 3 hours down after, be washed till neutrality, then this is immersed in acetylacetone,2,4-pentanedione-Y (III) complex solution, gets the crosslinked enhancing film of adulterated full fluorin sulfonic acid.
Embodiment 5:
With structure
The perfluor sulfonyl fluororesin of EW=900 mixes by extruder, at 250 ℃ of following and Ce (HPO
4)
2Powder (diameter is 0.005 μ m) mixes (wherein this powder quality content is 8%) to be extruded, and extruding thickness is 60 μ m.Cut the above-mentioned extruded film of 10cm * 10cm, be immersed in 80 ℃ the hydrazine 3 hours, place 110 ℃ to decompose 5 hours film after the taking-up.It is that 25% NaOH was in 80 ℃ of following hydrolysis 8 hours that film after decomposing is placed mass concentration, and then be placed on mass concentration be in 5% the sulfuric acid in 80 ℃ place 3 hours down after, be washed till neutrality, then this film be immersed in the EDTA-Ru solution, get the crosslinked enhancing film of adulterated full fluorin sulfonic acid.
Embodiment 6:
With repetitive be
, EW=820 fluoropolymer resin, repetitive is:
, the perfluor sulfonyl fluororesin resin of EW=750 and carbonic acid vanadium (account for total resin quality 1.3%) mix by extruder, at 210 ℃ down and H
5Sb
5P
2O
20Powder (diameter is 10 μ m) mixes (H wherein
5Sb
5P
2O
20Mass content is 1%) mix and extrude, extruding thickness is 60 μ m.Cut the above-mentioned extruded film of 10cm * 10cm, be immersed in 100 ℃ the guanidine hydrochloride ethylene glycol solution 8 hours.Place 155 ℃ to assign 5 hours film after the taking-up, it is that 13% NaOH was in 100 ℃ of following hydrolysis 16 hours that the film of heating is placed mass concentration, and then be placed on mass concentration be in 10% the sulfuric acid in 100 ℃ place 3 hours after, be washed till neutrality, the crosslinked enhancing film of adulterated full fluorin sulfonic acid.
Comparative example:
With formula
, EW=700 the perfluor sulfonyl fluororesin by extruder, mix (wherein the phosphate mass content is 10%) with phosphoric acid one hydrogen zirconium powder body (diameter is 0.5 μ) down at 210 ℃ and extrude, extruding thickness is 50 μ m.Cut the above-mentioned extruded film of 10cm * 10cm, be immersed in 50 ℃ the perfluoro caprylic acid amine dimethyl sulfoxide (DMSO) 5 hours, place 200 ℃ to assign 3 hours film after the taking-up.It is that 25% NaOH was placed 8 hours down in 80 ℃ that the film of heating is placed mass concentration, and then be placed on mass concentration be in 5% the sulfuric acid in 80 ℃ place 3 hours down after, be washed till neutrality and obtain cross linking membrane.
Embodiment 7
Performance to various films characterizes, and the results are shown in Table 1.As can be seen from Table 1, performances such as the hot strength of the compound-modified fiber reinforcement doping cross-linking of high-valency metal perfluorinated ion-exchange membrane, hydrogen permeate electric current all are better than the ionic membrane of simple doping cross-linking, and the raising and the improvement of highly significant are especially arranged aspect gas barrier
The various films of table 1 characterize
Claims (8)
1. doping double cross networking network full fluorin proton exchange film, it is characterized in that: this film with perfluorinated sulfonic resin as film-forming resin, add auxiliary proton conductive substance, carry out cross-linking reaction with crosslinking agent under certain condition and form the amide groups cross-linked structure, the acidic-group that adds high-valency metal compound and amide groups cross-linked structure simultaneously forms the physical bond network structure;
The metallic element of wherein said high-valency metal compound is selected from down one of column element or combination: W, Ir, Y, Mn, Ru, V, Zn or La element; And
Described high-valency metal compound is selected from the highest price attitude of these metallic elements and cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitrogen heterocyclic ring, EDTA, DMF or the DMSO complex compound of middle valence state;
Or be selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state.
2. exchange membrane as claimed in claim 1 is characterized in that: described amide groups cross-linked structure have formula (II) or (III) shown in structure:
Wherein, a=1 or 2, R are methylene or perfluor methylene, and n is 0～5 integer.
3. as each described exchange membrane of claim 1-2, it is characterized in that: described auxiliary proton conductive substance is selected from: SiO
2, ZrO
2, TiO
2, BPO
4, Zr
3(PO
4)
4, Zr (HPO
4)
2, H
3PW
12O
40, CsHSO
4, CsH
2PO
4, H-modenite, H-montmorillonite, HZr
2(PO
4)
3, Ce (HPO
4)
2, Ti (HPO
4)
2Or Zr
2H (P
3O
10)
2In one or more.
4. exchange membrane as claimed in claim 3 is characterized in that: described high-valency metal is compound loaded on auxiliary proton conductive substance.
5. exchange membrane as claimed in claim 1 is characterized in that: described high-valency metal compound is selected from the highest price attitude of these metallic elements and cyclodextrin, crown ether, acetylacetone,2,4-pentanedione, nitrogen heterocyclic ring, EDTA, DMF or the DMSO complex compound of middle valence state.
6. exchange membrane as claimed in claim 5 is characterized in that: described nitrogen heterocyclic ring is a nitogen-contained crown ether.
7. exchange membrane as claimed in claim 1 is characterized in that: described high-valency metal compound is selected from the highest price attitude of these metallic elements and the oxide with perovskite structure of middle valence state.
8. exchange membrane as claimed in claim 7 is characterized in that: described oxide with perovskite structure is Ca
0.6La
0.27TiO
3, La
(1-y)Ce
yMnO
3Or La
0.7Ce
0.15Ca
0.15MnO
3, y=0.1～0.4 wherein.
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| WO2011156934A1 (en) * | 2010-06-18 | 2011-12-22 | 山东东岳神舟新材料有限公司 | Proton exchange membrane, its preparing method and use |
| CN102008905B (en) * | 2010-06-18 | 2013-09-25 | 山东华夏神舟新材料有限公司 | Proton exchange film as well as preparation method and application thereof |
| CN102019147B (en) * | 2010-06-18 | 2013-09-25 | 山东华夏神舟新材料有限公司 | Proton exchange membrane as well as preparation method and application thereof |
| US9539568B2 (en) * | 2011-04-07 | 2017-01-10 | Solvay Specialty Polymers Italy S.P.A. | Process for the preparation of cross-linked fluorinated polymers |
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| CN101376717A (en) * | 2008-08-15 | 2009-03-04 | 黑龙江大学 | Preparation of nano inorganic doped perfluorosulfonated compound film |
| CN101383404A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院大连化学物理研究所 | Fluorine/hydrocarbon composite ion exchange film and preparation thereof |
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| US6059943A (en) * | 1997-07-30 | 2000-05-09 | Lynntech, Inc. | Composite membrane suitable for use in electrochemical devices |
| US6733914B1 (en) * | 2000-02-18 | 2004-05-11 | Ion Power, Inc. | Fuel cell membranes |
| CN101023550A (en) * | 2004-09-20 | 2007-08-22 | 3M创新有限公司 | Fuel cell durability |
| CN101383404A (en) * | 2007-09-05 | 2009-03-11 | 中国科学院大连化学物理研究所 | Fluorine/hydrocarbon composite ion exchange film and preparation thereof |
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| CN101376717A (en) * | 2008-08-15 | 2009-03-04 | 黑龙江大学 | Preparation of nano inorganic doped perfluorosulfonated compound film |
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