CN108493469A - A kind of cross-linking type high temperature proton exchange film and preparation method thereof - Google Patents
A kind of cross-linking type high temperature proton exchange film and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of cross-linking type high temperature proton exchange films and preparation method thereof; specifically; polybenzimidazoles type compound A contains hydroxy functional group or hydroxyl with another and is combined as raw material by the alkaline polymer B and organic molecule crosslinking agent C that blocking group is protected; wherein, the molar ratio nA of the A and B:NB=1:The molar ratio nA of 0.01 99.99, A and C:NC=1:0.01‑2.00.The present invention also provides the preparation methods of the cross-linking type high temperature proton exchange film.The high temperature proton exchange film of the present invention has both high-quality electron conductivity, high mechanical properties, high thermal stability, high antioxidative stabilizer and low swelling ratio, is highly suitable for Proton Exchange Membrane Fuel Cells.
Description
Technical field
The invention belongs to field of fuel cell technology, and in particular to a kind of cross-linking type high temperature proton exchange film and its preparation side
Method.
Background technology
Fuel cell is the power generator that the chemical energy of fuel is converted directly into electric energy by electrochemical reaction.Due to combustion
Expect battery with efficient, energy density is big, power is big, power-on time is long, long lifespan, reliability are high, noise is low and does not generate
Noxious emission etc., it is considered to be the novel power supply in the world that faces the future.In the fuel cell of numerous kinds, proton exchange membrane
Fuel cell (proton exchange membrane fuel cell, PEMFC) is high with its energy density, room temperature startup is fast,
Environmental-friendly, the advantages that noiseless and infra-red radiation are small, is as most practical and commercial value fuel cell.Proton exchange membrane
The application of fuel cell is divided into three classes：Portable, the fixed and vehicles.Portable proton exchange film fuel battery is mainly
For charging of mobile devices, application prospect is consumer electronics and military product；Fixed Proton Exchange Membrane Fuel Cells is applied to enterprise
Industry data center backup power supply, distributing base station power, unmanned miniature thermoelectric power source and watt million grades of power large-scale electric generating stations, are current masters
The application field wanted；In addition, Proton Exchange Membrane Fuel Cells can also be used as automobile power source, ship power supply, unmanned electromechanical source etc.,
The advantages that by its energy conservation and environmental protection, is of increasing concern, is the most promising application field of Proton Exchange Membrane Fuel Cells.It passes
The PEMFC of system since its operating temperature is low (be less than 100 DEG C, generally at 60-90 DEG C), lead to it there are fuel utilization efficiencies it is low,
The problems such as environmental resistance is poor, hydro-thermal complex management.Therefore, the operating temperature of fuel cell is improved, high temperature proton exchange is developed
Membrane cell (high temperature proton exchange membrane fuel cell, HT-PEMFC) is
As a kind of inevitable development trend.And high temperature proton exchange film (HT-PEM) is the core of HT-PEMFC, is to realize height
The key point of temperature operation.
Currently, widely used high temperature proton exchange film is the proton exchange membrane of PBI (polybenzimidazoles) type, which supports by the arm
Miscellaneous inorganic phosphate is used together.Although the film is using than wide, its disadvantage is also apparent：(a) inorganic phosphate holds
It is easy to run off；The proton conductivity that the loss of phosphoric acid causes proton exchange membrane drastically declines, so as to cause under battery performance
Drop, shortens the job stability and service life of battery.(b) lance between the proton conductivity of film and the mechanical strength of film
Shield；In order to improve the proton conductivity of film, the adsorbance of inorganic phosphate in film can be generally improved, but with the suction of inorganic phosphate
The mechanical strength of the increase of attached amount, film can reduce rapidly, and seriously affect proton exchange membrane dimensional stability and service life.Cause
This can only consider the proton conductivity of film and the mechanical strength of film in actual use.For the film of PBI types
These existing problems, we have developed the proton exchange (number of patent application 201710084102.X) of organic composite type high temperature,
The proton exchange of the organic composite type high temperature has following apparent advantage compared to PBI films：(a) cost declines to a great extent；(b) film
Proton conductivity greatly improves；(c) bleed rate of inorganic phosphate is reduced.But the proton exchange of organic composite type high temperature
It also needs to further increase in mechanical strength and thermal stability and antioxidative stabilizer etc..
In conclusion this field still lacks one kind, to have both high-quality electron conductivity, high mechanical properties, low swelling ratio, high fever steady
Qualitative, high anti-oxidation stability, low-phosphorous acid bleed rate have the high temperature proton exchange film in long-time stable service life again simultaneously.
Invention content
It is an object of the invention to provide one kind having both high-quality electron conductivity, high mechanical properties, low swelling ratio, high heat stability
Property, high anti-oxidation stability, it is low-phosphorous acid bleed rate simultaneously again with the long-time stable service life high temperature proton exchange film.
The first aspect of the present invention provides a kind of cross-linking type high temperature proton exchange film, and the high temperature proton exchange film is
By polybenzimidazoles type compound A, containing the alkaline polymer B that hydroxy functional group or hydroxyl are protected by blocking group, with
And organic molecule crosslinking agent C is combined as raw material；Wherein, the molar ratio nA of the A and B:NB=1:0.01-
The molar ratio nA of 99.99, A and C:NC=1:0.01-2.00.
In another preferred example, the organic molecule crosslinking agent C is selected from the group：
In another preferred example, the alkaline polymer B is the polymer with structure shown in formula I：
Wherein, the D rings are -1 to 3 yuan of alkylidene-OR of H atom quilt at least one ring3Substituted 5-12 members are nitrogenous
Heteroaryl；
R3It is selected from the group：H, Ac (acetyl group), PhCO (benzoyl), ClCH2CO (chloracetyl), Bn (benzyl), THP
(dihydropyran), TMS (Me3Si, trimethyl silicon substrate), TES (Et3Si, triethyl group silicon substrate), TBS (t-Butyldimethylsilyl),
TIPS (triisopropylsilyl), TBDPS (tert-butyl diphenyl silicon substrate)；
N=2-10000.
In another preferred example, the polybenzimidazoles Type of Collective object A is selected from the group：
Wherein, n=2-10000, p=0,1,2 or 3；
R is selected from the group：Nothing, O, S, NH, C (O), S (O)2, it is unsubstituted or halogenated C1-C6 alkylidenes, unsubstituted or halogenated
C2-C6 alkenylenes；
R1It is selected from the group：
In another preferred example, the polybenzimidazoles type compound A is selected from the group：
Wherein, R1Described in as defined above, n=2-10000, p=0,1,2 or 3；Preferably, p=1 or 2.
In another preferred example, the alkaline polymer B is selected from the group：
Wherein, n=2-10000；
R3It is selected from the group：H, Ac (acetyl group), PhCO (benzoyl), ClCH2CO (chloracetyl), Bn (benzyl), THP
(dihydropyran), TMS (Me3Si, trimethyl silicon substrate), TES (Et3Si, triethyl group silicon substrate), TBS (t-Butyldimethylsilyl),
TIPS (triisopropylsilyl), TBDPS (tert-butyl diphenyl silicon substrate).
In another preferred example, the molar ratio nA of the A and B:NB=1：0.1~25, and the molar ratio nA of A and C:nC
=1:0.02-2.00.
In another preferred example, the molar ratio nA of the A and the C:NC=1:0.1-2.0.
In another preferred example, the tensile strength of organic high temperature proton exchange film is more than 98MPa.
In another preferred example, the thickness of organic high temperature proton exchange film is 15~45 microns.
In another preferred example, organic high temperature proton exchange film TgIt is 245~290 DEG C.
The second aspect of the present invention additionally provides a kind of cross-linking type high temperature proton exchange film as described in relation to the first aspect and prepares
The preparation method of method, the high temperature proton exchange film is as follows：
Offer polybenzimidazoles type compound A contains hydroxy functional group with another or hydroxyl is protected by blocking group
The alkaline polymer B of shield；
Under the protection of inert gas, the mixture of the two is dissolved in organic solvent, heating stirring is made into mixed solution；
Organic molecule crosslinking agent C is added into the mixed solution, stirs evenly；Preferably, organic small in addition
Before molecule cross-link agent C, the mixed solution is cooled to room temperature (20-40 DEG C)；It is filtered to remove insoluble matter, obtains mixing filter
Liquid；
The mixing filtrate is de-gassed；
Make the mixing filtrate film forming being de-gassed, obtains cross-linking type high temperature proton exchange film.
In another preferred example, it is small that the stirring 1~10 of the mixed solution after the organic molecule crosslinking agent C will be added
When；Preferably, it stirs 1~3 hour.
In another preferred example, polybenzimidazoles type compound A with containing hydroxy functional group or hydroxyl by protecting group
The molar ratio of the alkaline polymer B of group's protection is 1:0.1~25 and/or polybenzimidazoles type compound A with organic small point
The molar ratio of sub- crosslinking agent C is 1:0.02-2.0.
In another preferred example, the organic solvent is highly polar organic solvent, is more preferably selected from the group：DMSO (two
Methyl sulfoxide), DMF (n,N-Dimethylformamide), DMAC (n,N-dimethylacetamide) or NMP (N-Methyl pyrrolidone),
Or combinations thereof.
In another preferred example, the solid content of the mixed solution is 1-40wt%；Preferably, 1-30wt%.
In another preferred example, the film forming includes：Film and drying on glass plate or plastic film form crosslinking
Type high temperature proton exchange film.
In another preferred example, the coating method is the tape casting.
In another preferred example, the drying includes：After carrying out preliminarily dried at 70-90 DEG C, it is warming up to 100-140
Second step drying is carried out at DEG C, is then warming up to 140-300 DEG C and is carried out third step drying.
In another preferred example, the preliminarily dried carries out 1~3 hour, the progress 0.5~2 hour and the third
Step is dry to be carried out 0.5~2 hour.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment)
It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist
This no longer tires out one by one states.
Description of the drawings
Fig. 1 is m-PBI and poly- [(6- hydroxymethyls) -2- vinylpyridines] and bis- [(the oxiranyl methoxies of 1,3-
Base) benzene (molar ratio 1：0.2：0.2) the DSC test charts of composite membrane (embodiment 1).
Fig. 2 is Py-O-PBI and poly- [(2- hydroxymethyls) -4-vinylpridine] and 2 [(4- chloromethyls) phenoxy group] first
Hexadecyl ethylene oxide (molar ratio 1:0.4:0.3) the DSC test charts of composite membrane (embodiment 2).
The comparison diagram that Fig. 3 varies with temperature for the proton conductivity of cross-linking type high temperature proton exchange film of the present invention and PBI films.
Fig. 4 is the proton of the organic composite type high temperature proton exchange film and PBI films of number of patent application 201710084102.X
The comparison diagram that conductivity varies with temperature, in figure, the number of each curve is the embodiment number in above-mentioned number of patent application.
The comparison diagram that Fig. 5 varies with temperature for the swelling ratio of cross-linking type high temperature proton exchange film of the present invention and PBI films.
Fig. 6 is the swelling of the organic composite type high temperature proton exchange film and PBI films of number of patent application 201710084102.X
The comparison diagram that rate varies with temperature, in figure, the number of each curve is the embodiment number in above-mentioned number of patent application.
Fig. 7 is No. 6 films (embodiment 6) of cross-linking type high temperature proton exchange film of the present invention and in patent 201710084102.X 13
The job stability test chart of number film (embodiment 13) and PBI films assembling monocell.
Specific implementation mode
The present inventor passes through long-term and in-depth study has been surprisingly found that, using polybenzimidazoles Type of Collective object A and other one
Kind of the alkaline polymer B protected by blocking group containing hydroxy functional group or hydroxyl is added organic after wiring solution-forming
Small molecule crosslinking agent C pours into a mould film forming after being uniformly mixed, after drying, can obtain with high proton conductivity, height again
The high temperature proton exchange film of mechanical strength, high thermal stability, high antioxidative stabilizer and low swelling ratio, therefore be very suitable for
It is used as the proton exchange membrane of high temperature proton conductive membrane cell.Based on above-mentioned discovery, inventor completes the present invention.
Cross-linking type high temperature proton exchange film
The present invention provides a kind of cross-linking type high temperature proton exchange film, the high temperature proton exchange film is by polyphenyl and miaow
Azoles type compound A with another contain alkaline polymer B that hydroxy functional group or hydroxyl are protected by blocking group and
Organic molecule crosslinking agent C is combined as raw material, wherein the molar ratio nA of the A and B:NB=1:0.01-99.99,
The molar ratio nA of A and C:NC=1:0.01-2.00.
In another preferred example, the polybenzimidazoles Type of Collective object A is selected from the group：
Wherein, n=2-10000；
R is selected from the group：Nothing, O, S, NH, C (O), S (O)2, it is unsubstituted or halogenated C1-C6 alkylidenes, unsubstituted or halogenated
C2-C6 alkenylenes；
R1It is selected from the group：
In another preferred example, the polybenzimidazoles type compound A is selected from the group：
Wherein R1It is defined as described above.
In another preferred example, the alkaline polymer protected by blocking group containing hydroxy functional group or hydroxyl
B is selected from the group：
Wherein, n=2-10000.
R3It is selected from the group：H, Ac (acetyl group), PhCO (benzoyl), ClCH2CO (chloracetyl), Bn (benzyl), THP
(dihydropyran), TMS (Me3Si, trimethyl silicon substrate), TES (Et3Si, triethyl group silicon substrate), TBS (t-Butyldimethylsilyl),
TIPS (triisopropylsilyl), TBDPS (tert-butyl diphenyl silicon substrate).
In another preferred example, the organic molecule crosslinking agent C is selected from the group：
In another preferred example, the molar ratio nA of the A and B:NB=1：The molar ratio nA of 0.1~25, A and C:NC=
1:0.02-1.0 0。
Cross-linking type high temperature proton exchange film preparation method
The present invention also provides a kind of cross-linking type high temperature proton exchange film preparation methods, which is characterized in that described
High temperature proton exchange film preparation method it is as follows：
Offer polybenzimidazoles type compound A contains hydroxy functional group with another or hydroxyl is protected by blocking group
The alkaline polymer B of shield；
Under the protection of inert gas, the mixture of the two is dissolved in organic solvent, heating stirring is made into centainly to be contained admittedly
The mixed solution of amount；
Mixed solution is cooled to room temperature, and organic molecule crosslinking agent C is added, and is stirred two hours, is stirred evenly；
It is filtered to remove insoluble matter, obtains mixing filtrate；
The mixing filtrate is de-gassed；
Make the mixing filtrate film forming being de-gassed, obtains cross-linking type high temperature proton exchange film.
In another preferred example, polybenzimidazoles type compound A with containing hydroxy functional group or hydroxyl by protecting group
The molar ratio of the alkaline polymer B of group's protection is 1：0.1~25, polybenzimidazoles type compound A are handed over organic molecule
The molar ratio for joining agent C is 1:0.02-1.0.
In another preferred example, the organic solvent is highly polar organic solvent, is more preferably selected from the group：DMSO (two
Methyl sulfoxide), DMF (n,N-Dimethylformamide), DMAC (n,N-dimethylacetamide) or NMP (N-Methyl pyrrolidone),
Or combinations thereof.
In another preferred example, the solid content of matched solution is 1-40wt%.
In another preferred example, the film forming includes：Film and drying on glass plate or plastic film form crosslinking
Type high temperature proton exchange film.
In another preferred example, the coating method is the tape casting.
In another preferred example, the drying includes：After carrying out preliminarily dried at 70-90 DEG C, it is warming up to 100-140
Second step drying is carried out at DEG C, is then warming up to 160-300 DEG C and is carried out third step drying.
Main advantages of the present invention include
The cross-linking type high temperature proton exchange film of the present invention is handed over the high temperature proton that traditional PBI films and our fronts are researched and developed
It changes film to compare, has the following advantages：
(1) traditional PBI films are compared, membrane swelling ratio of the invention reduces；
(2) traditional PBI films are compared, mold conductivity of the invention further increases；
(3) traditional PBI films are compared, film tool intensity of the invention further increases；
(4) traditional PBI films are compared, membrane stability of the invention and antioxidative stabilizer improve；
Therefore, cross-linking type high temperature proton exchange film using the present invention will have higher mechanical strength, higher proton
Conductivity, lower swelling ratio, more high operational stability and durability are conducive to the commercialization hair for pushing high-temperature fuel cell
Exhibition.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are weight percent and weight
Number.
Embodiment 1
M-PBI and poly- [(6- hydroxymethyls) -2- vinylpyridines] and bis- [(oxiranyl methoxyl group) benzene of 1,3-
(molar ratio 1:0.2:0.2) preparation of composite membrane：
According to 1:0.2:0.2 molar ratio weighs dry m-PBI (616.7mg, 2mmol) and poly- [(6- hydroxyl first
Base) -2- vinylpyridines] (60.0mg, 0.4mmol).Under the protection of nitrogen, the mixture of the two is dissolved in dry DMSO
In (dimethyl sulfoxide (DMSO), 12.857g), heating stirring is made into the solution that solid content is 5%, is cooled to room temperature, and it is bis- that 1,3- is added
[(oxiranyl methoxyl group) benzene (88.9mg, 0.4mmol) is stirred 2 hours, is filtered after stirring evenly, and filters off insoluble matter, filter
Liquid is cast to after degassing process on the glass plate of 10cm × 10cm, and it is small to be then put into convection oven at 80 DEG C dry two
When, it then further heats up to a dry hour at 120 DEG C, is finally warming up to one hour of 160 DEG C of dryings to get to crosslinking
Type high temperature proton exchange film.The thickness of the film is 22 μm (microns), and DSC tests show its glass transition temperature Tg=248 DEG C
(as shown in Figure 1), Mechanics Performance Testing show that its tensile strength is 145MPa.
Embodiment 2
Py-O-PBI and poly- [(2- hydroxymethyls) -4-vinylpridine] and 2 [(4- chloromethyls) phenoxy group] methyl rings
Oxidative ethane (molar ratio 1:0.4:0.3) preparation of composite membrane：
According to 1:0.4:0.3 molar ratio weighs dry Py-O-PBI (710.8mg, 2mmol) and poly- [(2- hydroxyl first
Base) -4-vinylpridine] (108.1mg, 0.8mmol).Under the protection of nitrogen, the mixture of the two is dissolved in dry DMF
In (n,N-Dimethylformamide 19.654g), heating stirring is made into the solution that solid content is 4%, is cooled to room temperature, and is added 2
[(4- chloromethyls) phenoxy group] methyl oxirane (119.2mg, 0.6mmol) is stirred 2 hours, is filtered after stirring evenly, and is filtered off
Insoluble matter, filtrate are cast to after degassing process on the glass plate of 10cm × 10cm, are then put into convection oven at 80 DEG C
Lower drying two hours then further heats up to a dry hour at 120 DEG C, is finally warming up to one hour of 180 DEG C of dryings,
Obtain cross-linking type high temperature proton exchange film.The thickness of the film is 24 μm (microns), and DSC tests show its glass transition temperature
Tg=257 DEG C (as shown in Figure 2), Mechanics Performance Testing show that its tensile strength is 138MPa.
Embodiment 3
F6- PBI (rubs with poly- [(6- trimethylsiloxy groups methyl) -2- vinylpyridines] and 1,4- bis- (chloromethyl) benzene
That ratio 1:0.6:0.4) preparation of composite membrane：
According to 1:0.6:0.4 molar ratio weighs dry F6- PBI (1069.0mg, 2mmol) and poly- [(6- trimethyls
Silica ylmethyl) -2- vinylpyridines] (266.4mg, 1.2mmol).Under the protection of nitrogen, the mixture of the two is dissolved in
In dry NMP (N-Methyl pyrrolidone 15.747g), heating stirring is made into the solution that solid content is 8%, is cooled to room temperature,
Isosorbide-5-Nitrae-two (chloromethyl) benzene (140.0mg, 0.8mmol) is added, stirs 2 hours, is filtered after stirring evenly, filters off insoluble matter, filter
Liquid is cast to after degassing process on the glass plate of 10cm × 10cm, and it is small to be then put into convection oven at 80 DEG C dry two
When, it then further heats up to a dry hour at 120 DEG C, is finally warming up to one hour of 220 DEG C of dryings to get to crosslinking
Type high temperature proton exchange film.The thickness of the film is 30 μm (microns), and DSC tests show its glass transition temperature Tg=280 DEG C,
Mechanics Performance Testing shows that its tensile strength is 135MPa.
Embodiment 4
SO2- PBI and poly- [(2- acetoxy-methyls) -4-vinylpridine] and 1,4- bis- (bromomethyl) benzene (molar ratio
1:0.8:0.5) preparation of composite membrane：
According to 1:0.8:0.5 molar ratio weighs dry SO2- PBI (987.1mg, 2mmol) and poly- [(2- acetyl oxygen
Ylmethyl) -4-vinylpridine] (283.2mg, 1.6mmol).Under the protection of nitrogen, the mixture of the two is dissolved in drying
DMAC (n,N-dimethylacetamide, 7.198g) in, heating stirring be made into solid content be 15% solution, be cooled to room temperature,
Isosorbide-5-Nitrae-two (bromomethyl) benzene (264.0mg, 1.0mmol) is added, stirs 2 hours, is filtered after stirring evenly, filters off insoluble matter, filter
Liquid is cast to after degassing process on the glass plate of 10cm × 10cm, and it is small to be then put into convection oven at 80 DEG C dry two
When, it then further heats up to a dry hour at 120 DEG C, is finally warming up to one hour of 250 DEG C of dryings to get to crosslinking
Type high temperature proton exchange film.The thickness of the film is 33 μm (microns), and DSC tests show its glass transition temperature Tg=277 DEG C,
Mechanics Performance Testing shows that its tensile strength is 129MPa.
Embodiment 5
Poly- [2,2 '-[4 ", 4 " '-sub- (diphenyl methane)] -5,5 '-bibenzimidaz sigmale] and poly- [(5- hydroxymethyls) -2-
Vinylpyridine] and bis- [(oxiranyl methoxyl group) benzene (molar ratios 1 of 1,3-:5:0.5) preparation of composite membrane：
According to 1:5:0.5 molar ratio weighs dry poly- [2,2 '-[4 ", 4 " '-sub- (diphenyl methane)] -5,5 '-connection
Benzimidazole] (398.2mg, 1mmol) and poly- [(5- hydroxymethyls) -2- vinylpyridines] (675.6mg, 5mmol).In nitrogen
Protection under, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 9.644g), heating stirring is made into
Solid content be 10% solution, be cooled to room temperature, be added 1,3- it is bis- [(oxiranyl methoxyl group) benzene (111.1mg,
0.5mmol), stir 2 hours, filtered after stirring evenly, filter off insoluble matter, filtrate be cast to after degassing process 10cm ×
It on the glass plate of 10cm, is then put into convection oven at 80 DEG C two hours dry, then further heats up to doing at 120 DEG C
A dry hour is finally warming up to one hour of 170 DEG C of dryings to get to cross-linking type high temperature proton exchange film.The thickness of the film
For 35 μm (microns), DSC tests show its glass transition temperature Tg=289 DEG C, Mechanics Performance Testing shows its tensile strength
For 123MPa.
Embodiment 6
Poly- [2,2 '-(metaphenylene) -5,5 '-two (benzimidazolyl) ketone] and poly- [(4- tertiary butyl dimethyl Sis Ji Jia
Base) -1- vinyl pyrazoles] and 2 [(4- bromomethyls) phenoxy group] methyl oxirane (molar ratios 1:6:0.6) system of composite membrane
It is standby：
According to 1:6:0.6 molar ratio weighs dry poly- [2,2 '-(metaphenylene) -5,5 '-two (benzimidazolyls)
Ketone] (168.1mg, 0.5mmol) and poly- [(4- tertiary butyl dimethyl Sis ylmethyl) -1- vinyl pyrazoles] (715.2mg,
3mmol).Under the protection of nitrogen, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 6.472g)
In, heating stirring is made into the solution that solid content is 12%, is cooled to room temperature, and 2 [(4- bromomethyls) phenoxy group] methyl epoxies are added
Ethane (72.9mg, 0.3mmol) is stirred 2 hours, is filtered after stirring evenly, and filters off insoluble matter, and filtrate is flowed after degassing process
Prolong onto the glass plate of 10cm × 10cm, is then put into convection oven drying two hours at 80 DEG C, then further heats up
A dry hour to 120 DEG C is finally warming up to one hour of 240 DEG C of dryings to get to cross-linking type high temperature proton exchange film.
The thickness of the film is 22 μm (microns), and DSC tests show its glass transition temperature Tg=286 DEG C, Mechanics Performance Testing is shown
Its tensile strength is 119MPa.
Embodiment 7
Poly- [2,2 '-(metaphenylene) -5,5 '-two (benzimidazolyl) methane] and poly- [(4- hydroxymethyls) -1- vinyl
Pyrazoles] and 2 [(2- bromomethyls) phenoxy group] methyl oxirane (molar ratios 1:7:0.5) preparation of composite membrane：
According to 1:7:0.5 molar ratio weighs dry poly- [2,2 '-(metaphenylene) -5,5 '-two (benzimidazolyls)
Methane] (161.1mg, 0.5mmol) and poly- [(4- hydroxymethyls) -1- vinyl pyrazoles] (434.6mg, 3.5mmol).In nitrogen
Protection under, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 11.317g), heating stirring
It is made into the solution that solid content is 5%, is cooled to room temperature, 2 [(2- bromomethyls) phenoxy group] methyl oxiranes of addition (60.8mg,
0.25mmol), stir 2 hours, filtered after stirring evenly, filter off insoluble matter, filtrate be cast to after degassing process 10cm ×
It on the glass plate of 10cm, is then put into convection oven at 80 DEG C two hours dry, then further heats up to doing at 120 DEG C
A dry hour is finally warming up to one hour of 170 DEG C of dryings to get to cross-linking type high temperature proton exchange film.The thickness of the film
For 20 μm (microns), DSC tests show its glass transition temperature Tg=278 DEG C, Mechanics Performance Testing shows its tensile strength
For 125MPa.
Embodiment 8
Poly- [2,2 '-(metaphenylene) -5,5 '-two (benzimidazolyl) thioether] and poly- [(2- hydroxymethyls) -1- vinyl
Imidazoles] and 2,2- bis- [(4- (oxiranyl methoxyl group) phenyl] propane (molar ratio 1:8:0.8) preparation of composite membrane：
According to 1:8:0.8 molar ratio weighs dry poly- [2,2 '-(metaphenylene) -5,5 '-two (benzimidazolyls)
Thioether] (170.1mg, 0.5mmol) and poly- [(2- hydroxymethyls) -1- vinyl pyrazoles] (496.7mg, 4mmol).In nitrogen
Under protection, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 7.668g), heating stirring, which is made into, to be contained
Gu amount is 8% solution, it is cooled to room temperature, addition 2,2- bis- [(4- (oxiranyl methoxyl group) phenyl] propane (136.2mg,
0.4mmol), it stirs 2 hours, stirs evenly filtering, filter off insoluble matter, filtrate is cast to 10cm × 10cm after degassing process
Glass plate on, be then put into convection oven at 80 DEG C two hours dry, then further heat up at 120 DEG C dry one
A hour is finally warming up to one hour of 160 DEG C of dryings to get to cross-linking type high temperature proton exchange film.The thickness of the film is 21 μ
M (micron), DSC test show its glass transition temperature Tg=267 DEG C, Mechanics Performance Testing shows that its tensile strength is
119MPa。
Embodiment 9
Poly- [2,6- [4 ', 4 "-sub- (diphenyl methane)]-benzo diimidazole] with poly- [(2- hydroxymethyls) -5- vinyl is phonetic
Pyridine] and 4,4 '-bis- [(oxiranyl methoxyl group) diphenyl-methane (molar ratios 1:10:0.6) preparation of composite membrane：
According to 1:10:0.6 molar ratio weighs dry poly- two miaow of [2,6- [4 ', 4 "-sub- (diphenyl methane)]-benzo
Azoles] (161.2mg, 0.5mmol) and poly- [(2- hydroxymethyls) -5- vinyl pyrimidines] (756.0mg, 5mmol).In the guarantor of nitrogen
Under shield, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 17.427g), heating stirring, which is made into, to be contained
Gu amount is 5% solution, it is cooled to room temperature, is added 4,4 '-bis- [(oxiranyl methoxyl group) diphenyl-methane (93.7mg,
0.3mmol), stir 2 hours, filtered after stirring evenly, filter off insoluble matter, filtrate be cast to after degassing process 10cm ×
It on the glass plate of 10cm, is then put into convection oven at 80 DEG C two hours dry, then further heats up to doing at 120 DEG C
A dry hour is finally warming up to one hour of 165 DEG C of dryings to get to cross-linking type high temperature proton exchange film.The thickness of the film
For 21 μm (microns), DSC tests show its glass transition temperature Tg=279 DEG C, Mechanics Performance Testing shows its tensile strength
For 117MPa.
Embodiment 10
Poly- [2,2 '-(2 ", 6 "-sub-pyridyl group) -5,5 '-two (benzimidazolyl) sulfones] and poly- [(N- hydroxymethyls) -2- second
Alkenyl imidazoles] and 3,3 ', 5,5 '-tetramethyls -4,4 '-bis- [(oxiranyl methoxyl group) biphenyl (molar ratio 1:12:0.7)
The preparation of composite membrane：
According to 1:12:0.7 molar ratio weighs dry poly- [2,2 '-(2 ", 6 "-sub-pyridyl groups) -5,5 '-two (benzos
Imidazole radicals) sulfone] (186.6mg, 0.5mmol) and poly- [(N- hydroxymethyls) -2- vinyl imidazoles] (745.0mg, 6mmol).
Under the protection of nitrogen, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 17.700g), heating is stirred
It mixes and is made into the solution that solid content is 5%, be cooled to room temperature, 3,3 ', 5,5 '-tetramethyl -4,4 '-bis- [(oxiranyl first are added
Oxygroup) biphenyl (124.1mg, 0.35mmol), stirs 2 hours, is filtered after stirring evenly, filter off insoluble matter, filtrate is by degassing
Be cast on the glass plate of 10cm × 10cm after processing, be then put into convection oven at 80 DEG C it is two hours dry, then into
One step is warming up at 120 DEG C a dry hour, is finally warming up to one hour of 160 DEG C of dryings to get to cross-linking type high temperature matter
Proton exchange.The thickness of the film is 36 μm (microns), and DSC tests show its glass transition temperature Tg=269 DEG C, mechanical property
Test shows that its tensile strength is 118MPa.
Embodiment 11
ABPBI and poly- [(N- hydroxymethyls) -4- vinyl imidazoles] and 4,4 '-bis- [(oxiranyl methoxyl groups) two
Phenylmethane (molar ratio 1:14:0.5) preparation of composite membrane：
According to 1:14:0.5 molar ratio weighs dry ABPBI (58.1mg, 0.5mmol) and poly- [(N- hydroxyl first
Base) -4- vinyl imidazoles] (869.2mg, 7mmol).Under the protection of nitrogen, the mixture of the two is dissolved in dry DMAC
In (n,N-dimethylacetamide, 22.254g), heating stirring is made into the solution that solid content is 4%, is cooled to room temperature, and is added 4,
It is 4 '-bis- that [(oxiranyl methoxyl group) diphenyl-methane (78.1mg, 0.25mmol) is stirred 2 hours, is filtered after stirring evenly, and is filtered
It goes insoluble matter, filtrate to be cast on the glass plate of 10cm × 10cm after degassing process, is then put into convection oven 80
It is two hours dry at DEG C, it then further heats up to a dry hour at 120 DEG C, it is one small to be finally warming up to 160 DEG C of dryings
When to get to cross-linking type high temperature proton exchange film.The thickness of the film is 30 μm (microns), and DSC tests show its glass transition
Temperature Tg=272 DEG C, Mechanics Performance Testing shows that its tensile strength is 110MPa.
Embodiment 12
Poly- [2,2 '-[4 ", 4 " '-sub- (methyldiphenyl phosphine oxide)] -5,5 '-two (benzimidazole) ethers] and poly- [(2- vinyl
Benzimidazole -1-) methanol] and bis- [(oxiranyl methoxyl group) benzene (molar ratios 1 of 4,4-:9:1.0) preparation of composite membrane：
According to 1:9:1 molar ratio weighs dry poly- [2,2 '-[4 ", 4 " '-sub- (methyldiphenyl phosphine oxide)] -5,5 '-two
(benzimidazole) ether] (462.4mg, 1mmol) and poly- [(2- vinyl benzimidazoles -1-) methanol] (1567.8mg, 9mmol).
Under the protection of nitrogen, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 26.972g), is heated
Stirring be made into solid content be 7% solution, be cooled to room temperature, be added 4,4- it is bis- [(oxiranyl methoxyl group) benzene (222.2mg,
1mmol), it stirs 2 hours, is filtered after stirring evenly, filter off insoluble matter, filtrate is cast to 10cm × 10cm after degassing process
Glass plate on, be then put into convection oven at 80 DEG C two hours dry, then further heat up at 120 DEG C dry one
A hour is finally warming up to one hour of 160 DEG C of dryings to get to cross-linking type high temperature proton exchange film.The thickness of the film is 45 μ
M (micron), DSC test show its glass transition temperature Tg=265 DEG C, Mechanics Performance Testing shows that its tensile strength is
125MPa。
Embodiment 13
Poly- [2,2 '-(metaphenylene) -5,5 '-two (benzimidazolyl) thioether] and poly- [(1- vinyl -1H-1,2,3- three
Nitrogen azoles -4-) methanol] and 2 [(2- chloromethyls) phenoxy group] methyl oxirane (molar ratios 1:8:1) preparation of composite membrane：
According to 1:8:1 molar ratio weighs dry poly- [2,2 '-(metaphenylene) -5,5 '-two (benzimidazolyl) sulphur
Ether] (340.1mg, 1mmol) and poly- [(1- vinyl -1H-1,2,3- triazoles -4-) methanol] (1001.0mg, 8mmol).
Under the protection of nitrogen, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 15.421g), heating is stirred
It mixes and is made into the solution that solid content is 8%, be cooled to room temperature, 2 [(2- chloromethyls) phenoxy group] methyl oxiranes are added
(198.6mg, 1mmol) is stirred 2 hours, is filtered after stirring evenly, filter off insoluble matter, and filtrate is cast to after degassing process
On the glass plate of 10cm × 10cm, drying two hours at 80 DEG C are then put into convection oven, are then further heated up to 120
A dry hour at DEG C is finally warming up to one hour of 160 DEG C of dryings to get to cross-linking type high temperature proton exchange film.The film
Thickness be 39 μm (microns), DSC tests show its glass transition temperature Tg=271 DEG C, Mechanics Performance Testing shows its drawing
It is 124MPa to stretch intensity.
Embodiment 14
Poly- [2,2 '-[4 ", 4 " '-sub- (diphenyl methane)] -5,5 '-bibenzimidaz sigmale] and poly- [(5- vinyl -1H-1,
2,4- triazoles -1-) methanol] and pentaglycol 2 two (oxiranyl methyl) ether (molar ratio 1:5:1) compound
The preparation of film：
According to 1:5:1 molar ratio weighs dry poly- [2,2 '-[4 ", 4 " '-sub- (diphenyl methane)] -5,5 '-biphenyl
And imidazoles] (398.2mg, 1mmol) and poly- [(5- vinyl -1H-1,2,4- triazoles -1-) methanol] (625.6mg, 5mmol).
Under the protection of nitrogen, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 9.214g), heating is stirred
It mixes and is made into the solution that solid content is 10%, be cooled to room temperature, 2,2- dimethyl propylenes glycol, two (oxiranyl methyl) ether is added
(216.3mg, 1mmol) is stirred 2 hours, is stirred evenly filtering, filters off insoluble matter, and filtrate is cast to after degassing process
On the glass plate of 10cm × 10cm, drying two hours at 80 DEG C are then put into convection oven, are then further heated up to 120
A dry hour at DEG C is finally warming up to one hour of 160 DEG C of dryings to get to cross-linking type high temperature proton exchange film.The film
Thickness be 43 μm (microns), DSC tests show its glass transition temperature Tg=259 DEG C, Mechanics Performance Testing shows its drawing
It is 121MPa to stretch intensity.
Embodiment 15
S-PBI and poly- [(1- vinyl -1H-1,2,4- triazoles -5-) methanol] and trimethoxy [(3- (oxa- rings third
Ylmethoxy) propyl] silane (molar ratio 1：16：2) preparation of composite membrane：
According to 1：16：2 molar ratio weighs dry S-PBI (208.1mg, 0.5mmol) and poly- [(1- vinyl -1H-
1,2,4- triazoles -5-) methanol] (1001mg, 8mmol).Under the protection of nitrogen, the mixture of the two is dissolved in dry
In DMAC (n,N-dimethylacetamide, 3.627g), heating stirring is made into the solution that solid content is 25%, is cooled to room temperature, adds
Enter trimethoxy [(3- (oxiranyl methoxyl group) propyl] silane (236.3mg, 1mmol), stirs 2 hours, after stirring evenly
Filtering filters off insoluble matter, and filtrate is cast to after degassing process on the glass plate of 10cm × 10cm, is then put into convection oven
In dry two hours at 80 DEG C, then further heat up to a dry hour at 120 DEG C, be finally warming up to 160 DEG C of dryings
One hour is to get to cross-linking type high temperature proton exchange film.The thickness of the film is 28 μm (microns), and DSC tests show its glass
Change transition temperature Tg=255 DEG C, Mechanics Performance Testing shows that its tensile strength is 107MPa.
Embodiment 16
Py-PBI and poly- [(1- ethylene -2- (triethyl group silica ylmethyl) benzimidazole] and [(4- chloromethyls) phenyl]
Ethyl trimethoxy silane (molar ratio 1:20:1) preparation of composite membrane：
According to 1:20:1 molar ratio weighs dry Py-PBI (154.6mg, 0.5mmol) and poly- [(1- ethylene -2-
(triethyl group silica ylmethyl) benzimidazole] (2884.6mg, 10mmol).It is under the protection of nitrogen, the mixture of the two is molten
In dry DMF (n,N-Dimethylformamide 27.353g), heating stirring is made into the solution that solid content is 10%, is cooled to
[(4- chloromethyls) phenyl] ethyl trimethoxy silane (137.4mg, 0.5mmol) is added in room temperature, stirs 2 hours, stirs evenly
After filter, filter off insoluble matter, filtrate is cast to after the degassing process on the glass plate of 10cm × 10cm, is then put into air blast
It is two hours dry at 80 DEG C in baking oven, it then further heats up to a dry hour at 120 DEG C, is finally warming up to 260 DEG C
A dry hour is to get to cross-linking type high temperature proton exchange film.The thickness of the film is 35 μm (microns), and DSC tests show it
Glass transition temperature Tg=261 DEG C, Mechanics Performance Testing shows that its tensile strength is 109MPa.
Embodiment 17
O-PBI and poly- [(1- (benzyloxymethyl) -2- vinyl benzimidazole] and two (oxygen of pentaglycol 2
Heterocycle hydroxypropyl methyl) ether (molar ratio 1:18:1) preparation of composite membrane：
According to 1:18:1 molar ratio weighs dry O-PBI (200.2mg, 0.5mmol) and poly- [(1- (benzyloxy first
Base) -2- vinyl benzimidazole] (2378.9mg, 9mmol).Under the protection of nitrogen, the mixture of the two is dissolved in dry
In DMF (n,N-Dimethylformamide 23.211g), heating stirring is made into the solution that solid content is 10%, is cooled to room temperature, and is added
2,2- dimethyl propylene glycol two (oxiranyl methyl) ethers (108.2mg, 0.5mmol) stir 2 hours, mistake after stirring evenly
Filter, filters off insoluble matter, and filtrate is cast on the glass plate of 10cm × 10cm after degassing process, is then put into convection oven
It is two hours dry at 80 DEG C, it then further heats up to a dry hour at 120 DEG C, is finally warming up to 280 DEG C of dryings one
A hour is to get to cross-linking type high temperature proton exchange film.The thickness of the film is 36 μm (microns), and DSC tests show its vitrifying
Tg=265 DEG C of transition temperature, Mechanics Performance Testing show that its tensile strength is 118MPa.
Embodiment 18
OO-PBI and poly- [(1- (chloroacetoxymethyl) -2- vinyl benzimidazole] and [(4- (the oxa- rings of 2,2- bis-
Propylmethoxy) phenyl] propane (molar ratio 1:6:0.3) preparation of composite membrane：
According to 1：6:0.3 molar ratio weighs dry OO-PBI (246.8mg, 0.5mmol) and poly- [(1- (chloracetyls
Oxygroup methyl) -2- vinyl benzimidazole] (752.0mg, 3mmol).Under the protection of nitrogen, the mixture of the two is dissolved in
In dry NMP (N-Methyl pyrrolidone 98.885g), heating stirring is made into the solution that solid content is 1%, is cooled to room temperature,
Addition 2,2- bis- [(4- (oxiranyl methoxyl group) phenyl] propane (51.1mg, 0.15mmol), stirs 2 hours, stirs evenly
After filter, filter off insoluble matter, filtrate is cast to after degassing process on the glass plate of 10cm × 10cm, is then put into air blast baking
It is two hours dry at 80 DEG C in case, it then further heats up to a dry hour at 120 DEG C, is finally warming up to 240 DEG C and does
A dry hour is to get to cross-linking type high temperature proton exchange film.The thickness of the film is 20 μm (microns), and DSC tests show its glass
Glass transition temperature Tg=262 DEG C, Mechanics Performance Testing shows that its tensile strength is 125MPa.
Embodiment 19
OSO2- PBI and poly- [(1- ethylene -2- methylols) benzimidazole] and 1,4- bis- [(oxiranyl methoxyl groups)
Benzene (molar ratio 1:1:0.5) preparation of composite membrane：
According to 1:1:0.5 molar ratio weighs dry OSO2- PBI (928.2mg, 2mmol) and poly- [(1- ethylene -2-
Methylol) benzimidazole] (348.4.2mg, 2mmol).Under the protection of nitrogen, the mixture of the two is dissolved in dry DMAC
In (n,N-dimethylacetamide, 24.255g), heating stirring is made into the solution that solid content is 5%, is cooled to room temperature, and is added 1,
4- it is bis- [(oxiranyl methoxyl group) benzene (222.2mg, 1mmol), stir 2 hours, filtered after stirring evenly, filter off insoluble matter,
Filtrate is cast to after degassing process on the glass plate of 10cm × 10cm, is then put into convection oven at 80 DEG C dry two
Hour, it then further heats up to a dry hour at 120 DEG C, is finally warming up to one hour of 160 DEG C of dryings to get to friendship
Connection type high temperature proton exchange film.The thickness of the film is 32 μm (microns), and DSC tests show its glass transition temperature Tg=288
DEG C, Mechanics Performance Testing shows that its tensile strength is 148MPa.
Embodiment 20
P-PBI and poly- [(1- vinyl -1H-1,2,4- triazoles -3-) methanol] and 1,3- bis- (chloromethyl) benzene (mole
Than 1:2:1) preparation of composite membrane：
According to 1:2:0.1 molar ratio weighs dry p-PBI (308.4mg, 1mmol) and poly- [(1- vinyl -1H-
1,2,4- triazoles -3-) methanol] (250.1mg, 2mmol).Under the protection of nitrogen, the mixture of the two is dissolved in dry
In DMAC (n,N-dimethylacetamide, 8.749g), heating stirring is made into the solution that solid content is 6%, is cooled to room temperature, and is added
1,3- bis- (chloromethyl) benzene (175.0mg, 1mmol) is stirred 2 hours, is filtered after stirring evenly, and filters off insoluble matter, and filtrate is passed through
It is cast on the glass plate of 10cm × 10cm after degassing process, is then put into convection oven drying two hours at 80 DEG C, connects
It and further heats up to a dry hour at 120 DEG C, be finally warming up to one hour of 160 DEG C of dryings to get compound to being crosslinked
Type high temperature proton exchange film.The thickness of the film is 18 μm (microns), and DSC tests show its glass transition temperature Tg=279 DEG C,
Mechanics Performance Testing shows that its tensile strength is 145MPa.
Embodiment 21
Poly- [2,2 '-(2 ", 5 "-Asia pyrazine) -5,5 '-bibenzimidaz sigmales] and poly- [(1- vinyl -3- (trimethylsiloxy groups
Methyl) -1H-1,2,4- triazoles)] and 2 [(4- chloromethyls) phenoxy group] methyl oxirane (molar ratios 1:8:0.8) compound
The preparation of film：
According to 1:8:0.8 molar ratio weighs dry poly- [2,2 '-(2 ", 5 "-sub- pyrazine) -5,5 '-bibenzimidaz sigmales]
(310.3mg, 1mmol) and poly- [(1- vinyl -3- (trimethylsiloxy group methyl) -1H-1,2,4- triazoles)] (864.8mg,
8mmol).Under the protection of nitrogen, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 6.659g)
In, heating stirring is made into the solution that solid content is 15%, is cooled to room temperature, and 2 [(4- chloromethyls) phenoxy group] methyl epoxies are added
Ethane (194.5mg, 0.8mmol) is stirred 2 hours, is filtered after stirring evenly, and filters off insoluble matter, filtrate is after degassing process
It is cast on the glass plate of 10 × 10cm, is then put into convection oven drying two hours at 80 DEG C, then further heats up
A dry hour to 120 DEG C is finally warming up to one hour of 200 DEG C of dryings to get to cross-linking type high temperature proton exchange film.
The thickness of the film is 30 μm (microns), and DSC tests show its glass transition temperature Tg=263 DEG C, Mechanics Performance Testing is shown
Its tensile strength is 99MPa.
Embodiment 22
Poly- [2,2 '-(metaphenylene) -5,5 '-two (benzimidazolyl) sulfone] and poly- [N- (trimethylsiloxy group methyl) -2-
Vinyl imidazole] and [(4- chloromethyls) phenyl] ethyl trimethoxy silane (molar ratio 1:4:0.4) preparation of composite membrane：
According to 1:4:0.4 molar ratio weighs dry poly- [2,2 '-(metaphenylene) -5,5 '-two (benzimidazolyls)
Sulfone] (372.1mg, 1mmol) and poly- [N- (trimethylsiloxy group methyl) -2- vinyl imidazoles] (758.3mg, 4mmol).In nitrogen
Under the protection of gas, the mixture of the two is dissolved in dry DMAC (n,N-dimethylacetamide, 21.99g), heating stirring is matched
The solution for being 5% at solid content, is cooled to room temperature, addition [(4- chloromethyls) phenyl] ethyl trimethoxy silane (109.9mg,
0.4mmol), stir 2 hours, filtered after stirring evenly, filter off insoluble matter, filtrate be cast to after degassing process 10cm ×
It on the glass plate of 10cm, is then put into convection oven at 80 DEG C two hours dry, then further heats up to doing at 120 DEG C
A dry hour is finally warming up to one hour of 260 DEG C of dryings to get to compound high temperature proton exchange film.The thickness of the film
For 35 μm (microns), DSC tests show its glass transition temperature Tg=245 DEG C, Mechanics Performance Testing shows its tensile strength
For 132MPa.
Testing example：
Mechanical property (tensile strength) is tested
It is tested by INSTRON-5566 universal material testers, test result is shown in each embodiment.
Proton conductivity is tested
With 740 devices of Membrane Test System, No. 6 films in PBI films and the application are tested using two-probe method
(embodiment 6), No. 7 films (embodiment 7), No. 14 films (embodiment 14), No. 19 films (embodiment 19), No. 20 films (embodiment 20),
The proton conductivity test of No. 22 films (embodiment 22).
Test method：
(1) pre-treatment is tested：
Under the conditions of 60 DEG C, each group film is immersed in 85% phosphoric acid, drying is taken out after impregnating 48 hours, it is to be measured.
(2) official testing (test equipment Membrane Test System 740)：
1. sample to be tested film is cut out 1cm × 3cm shapes；
2. there is the GDE of Pt/C catalyst with conduction adhesive tape on two electrode holder sheet metals, it is each a piece of up and down, and will cut
Good film to be measured is among GDE, clamping device；
3. connecting the power supply of MTS 740, the fixture equipped with film to be measured is put into the test chamber of the present apparatus.
4. opening this instrument test program, the pipeline that gas cylinder is connected with instrument is connected.Adjust N2Loine pressure is extremely
0.5MPa, H2Loine pressure checks that indicator light instruction is normal in program, and check chem workstation and 740 behaviour to 0.4MPa
Make the connection of cavity；
5. membrane sample starts test, it should first be passed through N2To exclude the indoor air of chamber, purging speed is purging 10min
500sccm/min, in instrument operational process, after temperature and humidity (relative humidity 2%) reach the value of setting and stablize, i.e.,
It can start to test.
6. automatically obtaining impedance spectra using MTS740 programs, electric resistance value R is obtained by spectrogram.
7. data processing：Conductivity is calculated by ρ=L/ (Rs × A).
L:Film thickness；
Rs:The film resistance that impedance spectrum is read
A:Tested area
8. at the end of test, it is necessary to use N2Purging 15min to exclude the steam in instrument, last bolt down procedure and instrument
Power supply.
As a result as shown in Figure 3.The results show that the conductivity of each conductive film of the application is significantly higher than control group PBI
And organic composite type high temperature proton exchange film (number of patent application 201710084102.X, the Proton conducting developed before us
Rate test result is same the application of test method shown in Fig. 4, and each embodiment number is in the patent application in wherein Fig. 4
Embodiment number).
Swelling ratio is tested
PBI films are measured respectively and No. 6, No. 14, No. 19, No. 20 and No. 22 films (are respectively embodiment 6, embodiment 14, implement
Prepared film in example 19 and 20 embodiment 22 of embodiment) swelling ratio.PBI films and No. 6, No. 14, No. 19 and 20, No. 22 films
(respectively film prepared in embodiment 6, embodiment 14, embodiment 19,20 and embodiment 22) swelling ratio test experiments：
1. each group film to be measured to be cut into the shape of 5cm × 5cm；
2. measuring the thickness of each film to be measured with thickness gauge；
3. calculating the initial volume (cubature formula=length × width x thickness degree) of each group film to be measured；
4. each group film is immersed in 85% phosphoric acid, phosphoric acid is heated to test temperature, after film absorption phosphoric acid saturation
It takes out, dries；
5. measuring the length of each group film again；
6. calculating the volume after each group membrane swelling；
7. calculating swelling ratio (calculation formula is as follows)
Test result is as shown in Figure 5, the results show that at up to 200 DEG C, the conduction in each embodiment of the application
The swelling ratio of film (can be less than 30%) below 50% in the preferred embodiment of part, well below PBI films and patent
(test result is as shown in Figure 6, and test method is the same as this Shen for organic composite type high temperature proton exchange film in 201710084102.X
Please；Wherein, each embodiment number in Fig. 6 is that embodiment is numbered in patent 201710084102.X), illustrate the conduction of the application
Film has lower swelling ratio.
The job stability of monocell is tested
No. 13 single electricity of films (embodiment 13) assembling in PBI films and No. 6 films (embodiment 6) and patent 201710084102.X
The job stability in pond is tested：
1. film process before test：
A. under the conditions of 60 DEG C, each group film is immersed in 85% phosphoric acid, drying is taken out after impregnating 48 hours, it is to be measured；
B., film to be measured is cut into the size of 6.5cm × 6.5cm；
It is prepared by 2.MEA (membrane electrode)；
A) it is the GDL of 29BC to use SIGRACET company models, is cut into 5 × 5cm sizes, and standard is done for catalyst spraying
It is standby；
B) catalyst spraying is carried out in GDL stomata layers, cathod catalyst loading is 2mg/cm2, anode catalyst supports
Amount is 3mg/cm2, prepare GDE；
C) film to be measured is placed on centre, places the cathode and anode of GDE respectively up and down, puts into sandwich structure, then carry out
Hot pressing (hot pressing condition is 135 DEG C, 10MPa, 2min), obtains MEA；
3. battery assembles：
The MEA being prepared is assembled in monocell model.
4. monocell is tested：
Test equipment:Fuel Cell Test System 850e
Monocell and test equipment are connected, according to the parameter of setting：Anode：500 ml/min of hydrogen；Cathode：It is empty
1500 ml/min of gas；Test temperature：160℃；Relative humidity：2%, constant scan voltage 0.7v. instrument under test conditions
The data of automatic recording current density.Test results are shown in figure 7.
Test result is as shown in Figure 7, from test result as can be seen that 13 in PBI films and patent 201710084102.X
The monocell of number film assembling after test more than 600 hours it is seen that apparent performance declines, and No. 6 film (embodiment 6) groups
The performance of the monocell of dress is very stable always, does not significantly decrease, and illustrates that the monocell of the conductive film preparation of the application obtains
Better stability.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document
It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can
To be made various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims
It encloses.
Claims (10)
1. a kind of cross-linking type high temperature proton exchange film, which is characterized in that the high temperature proton exchange film is by (a) polyphenyl and miaow
Azoles type compound A (b) contains the alkaline polymer B by hydroxyl protection base protection or unprotected hydroxy functional group, and
(c) organic molecule crosslinking agent C is compounded to form；Wherein, the molar ratio nA of the A and B:NB=1:0.01-99.99, A with
The molar ratio nA of C:NC=1:0.01-2.00.
2. cross-linking type high temperature proton exchange film as described in claim 1, which is characterized in that the organic molecule crosslinking agent
C is selected from the group：
3. cross-linking type high temperature proton exchange film as described in claim 1, which is characterized in that the alkaline polymer B be with
The polymer of structure shown in formula I：
Wherein, the D rings are -1 to 3 yuan of alkylidene-OR of H atom quilt at least one ring3Substituted 5-12 membered nitrogen-containing heteroaryls
Base；
R3It is selected from the group：H, Ac (acetyl group), PhCO (benzoyl), ClCH2CO (chloracetyl), Bn (benzyl), THP (dihydros
Pyrans), TMS (Me3Si, trimethyl silicon substrate), TES (Et3Si, triethyl group silicon substrate), TBS (t-Butyldimethylsilyl), TIPS
(triisopropylsilyl), TBDPS (tert-butyl diphenyl silicon substrate)；
N=2-10000.
4. cross-linking type high temperature proton exchange film as described in claim 1, which is characterized in that the polybenzimidazoles Type of Collective
Object A is selected from the group：
Wherein, n=2-10000, p=0,1,2 or 3；
R is selected from the group：Nothing, O, S, NH, C (O), S (O)2, unsubstituted or halogenated C1-C6 alkylidenes, unsubstituted or halogenated C2-
C6 alkenylenes；
R1It is selected from the group：
5. cross-linking type high temperature proton exchange film as described in claim 1, which is characterized in that the polybenzimidazoles type chemical combination
Object A is selected from the group：
Wherein, R1Definition as claimed in claim 4, n=2-10000, p=0,1,2 or 3；Preferably, p=1 or 2.
6. cross-linking type high temperature proton exchange film as described in claim 1, which is characterized in that the alkaline polymer B is selected from
The following group：
Wherein, n=2-10000；
R3It is selected from the group：H, Ac (acetyl group), PhCO (benzoyl), ClCH2CO (chloracetyl), Bn (benzyl), THP (dihydros
Pyrans), TMS (Me3Si, trimethyl silicon substrate), TES (Et3Si, triethyl group silicon substrate), TBS (t-Butyldimethylsilyl), TIPS
(triisopropylsilyl), TBDPS (tert-butyl diphenyl silicon substrate).
7. cross-linking type high temperature proton exchange film as described in claim 1, which is characterized in that the molar ratio nA of the A and B:
NB=1：0.1~25, and the molar ratio nA of A and C:NC=1:0.02-2.00.
8. cross-linking type high temperature proton exchange film preparation method as described in claim 1, which is characterized in that the high temperature proton
The preparation method of exchange membrane is as follows：
The alkaline polymerization that polybenzimidazoles type compound A is provided and is protected by blocking group containing hydroxy functional group or hydroxyl
Object B；
Under the protection of inert gas, the mixture of the two is dissolved in organic solvent, heating stirring is made into mixed solution；
Organic molecule crosslinking agent C is added into the mixed solution, stirs evenly；Preferably, it is crosslinked in organic molecule
Before agent C, the mixed solution is cooled to room temperature (20-40 DEG C)；
It is filtered to remove insoluble matter, obtains mixing filtrate；
The mixing filtrate is de-gassed；
Make the mixing filtrate film forming being de-gassed, obtains cross-linking type high temperature proton exchange film.
9. preparation method as claimed in claim 8, which is characterized in that polybenzimidazoles type compound A with contain hydroxyl official
The molar ratio for the alkaline polymer B that energy group or hydroxyl are protected by blocking group is 1:0.1~25 and/or polybenzimidazoles
The molar ratio of type compound A and organic molecule crosslinking agent C is 1:0.02-2.0.
10. preparation method as claimed in claim 8, which is characterized in that the organic solvent is highly polar organic solvent, more
It is selected from the group goodly：DMSO (dimethyl sulfoxide (DMSO)), DMF (n,N-Dimethylformamide), DMAC (n,N-dimethylacetamide), or
NMP (N-Methyl pyrrolidone), or combinations thereof.
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| CN113299959A (en) * | 2021-06-04 | 2021-08-24 | 中国科学院化学研究所 | Composite proton exchange membrane and preparation method and application thereof |
| CN117276611A (en) * | 2023-11-22 | 2023-12-22 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
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| CN103555248A (en) * | 2013-11-07 | 2014-02-05 | 包兰珍 | Modified epoxy resin adhesive and preparation method thereof |
| CN104151587A (en) * | 2013-05-15 | 2014-11-19 | 北京化工大学 | Preparation of novel covalent cross-linking polybenzimidazole proton exchange membrane |
| CN106803598A (en) * | 2017-02-16 | 2017-06-06 | 中国科学院上海有机化学研究所 | A kind of organic composite type high temperature proton exchange film and preparation method thereof |
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| CN104151587A (en) * | 2013-05-15 | 2014-11-19 | 北京化工大学 | Preparation of novel covalent cross-linking polybenzimidazole proton exchange membrane |
| CN103358372A (en) * | 2013-07-17 | 2013-10-23 | 中南林业科技大学 | In-situ generation method of phosphorus-containing benzimidazole derivative modifier in timber |
| CN103555248A (en) * | 2013-11-07 | 2014-02-05 | 包兰珍 | Modified epoxy resin adhesive and preparation method thereof |
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| CN113299959A (en) * | 2021-06-04 | 2021-08-24 | 中国科学院化学研究所 | Composite proton exchange membrane and preparation method and application thereof |
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| CN117276611A (en) * | 2023-11-22 | 2023-12-22 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
| CN117276611B (en) * | 2023-11-22 | 2024-02-23 | 佛山科学技术学院 | Preparation method of nano hollow polybenzimidazole composite membrane |
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