CN102299351B - Polybenzimidazole polymer ion exchange membrane, and preparation and application thereof - Google Patents

Polybenzimidazole polymer ion exchange membrane, and preparation and application thereof Download PDF

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CN102299351B
CN102299351B CN201010210135.2A CN201010210135A CN102299351B CN 102299351 B CN102299351 B CN 102299351B CN 201010210135 A CN201010210135 A CN 201010210135A CN 102299351 B CN102299351 B CN 102299351B
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李先锋
张华民
麦振声
史丁秦
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Dalian Rongke Power Co Ltd
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Abstract

The invention relates to a polybenzimidazole polymer ion exchange membrane, and preparation and application thereof. The invention further relates to an acid electrolyte redox energy storage battery including the polymer ion exchange membrane in the invention. The preparation condition of the polybenzimidazole polymer ion exchange membrane including a pyridine group is moderate. The preparation process is simple. The batch production is facilitated. The prepared polybenzimidazole polymer ion exchange membrane including the pyridine group has good mechanical strength and simultaneously has good toughness. The polybenzimidazole polymer ion exchange membrane has good proton conduction performance and excellent penetration insulation performance of positive and negative ions in the acid electrolyte redox energy storage battery.

Description

Polybenzimidazole polymer ion exchange membrane and preparation thereof and application
Technical field
The present invention relates to a kind of polybenzimidazoles class amberplex containing pyridine groups and preparation method thereof, the particularly application of this polybenzimidazoles class amberplex containing pyridine groups in vanadium redox battery.
Background technology
Liquid-flow energy storage battery with acidic electrolyte is a kind of electrochemical energy storage new technology, have that energy conversion efficiency is high, system is flexible, capacitance of storage is large, addressing is free, can deep discharge etc. advantage, be one of one preferred technique of extensive high-efficiency energy-storage technology.Vanadium redox battery (VRB) is a kind of as liquid-flow energy storage battery with acidic electrolyte, vanadium ion electrolyte due to both positive and negative polarity employing different valence state, therefore avoided the electrolyte both positive and negative polarity electrolyte contamination problem that string brings mutually, and the advantage such as battery has capacity and power is separate, long service life, easy to operate and maintenance, being considered to has one of prospect and representational a kind of energy-storage battery most in liquid-flow energy storage battery with acidic electrolyte.
Amberplex is the important component part of vanadium cell, and it plays and intercepts positive and negative electrode electrolyte, and the effect of proton transport passage is provided.The proton-conducting of amberplex, chemical stability and ion selectivity etc. directly affect chemical property and the useful life of vanadium cell; Therefore require film to there is lower active material permeability (having higher selectivity) and lower surface resistance (having higher ionic conductance), also should there is good chemical stability and lower cost simultaneously.The Nafion film that the main membrane material using is mainly du pont company's exploitation both at home and abroad now, Nafion film has excellent performance at aspects such as chemical property and useful lifes, but be applied to exist ion selectivity low in vanadium redox battery, the shortcoming such as expensive, thus limited the industrial applications of this film.Therefore, exploitation has high selectivity, high stability and amberplex is most important cheaply.
Polybenzimidazoles base polymer is to take the polymer that benzimidazole is main repetitive, owing to there being the fragrant heterocycle of conjugation in strand, keep the hexahedral arrangement architecture of polymer fragrance, thereby there is excellent thermal stability, chemical stability and mechanical property.Polybenzimidazoles can form with strong acid hydridization a kind of doping system of soda acid, and possesses good ionic conduction ability.(J.Mater.Chem.，1999，9，3045-3049)。Vanadium redox battery adopts the sulfuric acid solution of different valence state vanadium ion as electrolyte, thereby what sulfuric acid adulterated can play proton conducting as vanadium redox battery barrier film containing imidazoles polymer film.At present, the polybenzimidazole resin that on market, commercialization contains glyoxaline structure is for gathering [2,2 '-(m-phenylene)-5,5 '-bisbenzimidazole].This resin exists that infusibility melts, unmanageable defect, and film forming procedure is had relatively high expectations to experimental provision, and operating condition is comparatively harsh.And, film prepared by poly-[2,2 '-(m-phenylene)-5, the 5 '-bisbenzimidazole] of full aromatic structure, nitrogen that can be protonated is less, and resistance is larger.Therefore, angle from flow battery practical application, develop targetedly and there is excellent dissolution and processing characteristics and the high polybenzimidazoles base polymer of inhaling acid energy, can under relatively mild condition, prepare amberplex, obtain amberplex with low cost, there is superperformance in vanadium redox battery.
Summary of the invention
The object of the present invention is to provide a kind of liquid-flow energy storage battery with acidic electrolyte that is applicable to, there is polybenzimidazoles class amberplex of good ionic conductivity and filming performance and preparation method thereof.The present invention is based on pyridine groups in acid containing the high suction of N group, the construction unit that contains pyridine by introducing, improves the ionic conductivity of polybenzimidazoles.The present invention utilizes bisgallic acid and the biphenyl tetramine of different structure, by nucleophilic condensation polymerization, obtains.In reaction system, wherein a kind of structure of bisgallic acid is the diacid that contains pyridine groups, by adjusting this sour content, obtains having the polybenzimidazoles base polymer of different pyridine structures unit, and this base polymer has good film forming.In liquid flow energy storage battery, have a good application prospect.
For achieving the above object, the technical solution used in the present invention is:
, described polymer architecture general formula is as follows,
Figure BSA00000157424300021
Polymer is random copolymer, and wherein m and n are respectively the molar content of different structure unit, 0 < n≤0.8, and 0.2≤m < 1, m+n=1, the weight average molecular weight of this base polymer is between 5000-800000;
R 1represent one of following structure:
Figure BSA00000157424300022
R wherein 1design feature is: pyridine groups, as alkalescent group, can, by protonated, more be conducive to the transmission of proton under acid condition.Therefore the introducing of R1 structure can improve the proton conductivity of amberplex, reduces the internal resistance of battery, and then improves the voltage efficiency of battery.
R 2represent one of following structure:
Figure BSA00000157424300023
Wherein: R 3and R 4be respectively a kind of in hydrogen atom, C1-C4 saturated alkane group or the unsaturated alkane group of C2-C4, R 3and R 4it can be identical or different group.
R in this invention 2design feature be diphenyl ether structure, the existence of ehter bond can improve the dissolubility of polymer, further improves the processing characteristics of film.
The preparation of described amberplex:
(1) phosphorus pentoxide is dissolved in polyphosphoric acids, heats up and form settled solution; Wherein the mass ratio of phosphorus pentoxide and polyphosphoric acids was between 1: 5～1: 20;
(2) in the solution of step (1), add containing R 1the diacid of group and containing R 2the diacid of group and biphenyl tetramine; Be heated to 190-220 ℃, reaction 3-30 hour, pours solution in alkali lye into, finally controls solution for neutral, filters, by the solid polymer water boil obtaining, and filters, by the solid polymer oven dry obtaining; Monomer R in reaction system wherein 1the diacid of group and R 2the diacid of group and the biphenyl tetramine gross mass percentage composition in polyphosphoric acids solvent is between 2%-15%; And containing R 1the diacid of group and containing R 2total mole dosage sum of the diacid of group is identical with biphenyl tetramine;
(3) the polybenzimidazoles base polymer containing pyridine groups of drying is dissolved in one or more solvents of NMP, DMF, DMAC, DMSO at 60-100 ℃, the concentration of solution is controlled at 2-15wt%, by the polymer solution direct pouring obtaining on glass plate or corrosion resistant plate, at 60～100 ℃ more than dry 5h, then 80～150 ℃ of above film forming of vacuumize 1h, the thickness of film is between 10～200 μ m.
In polymer, the content of pyridine ring can contain R by control 1the diacid of group with containing R 2the ratio of the diacid mole dosage of group realizes.0 < R 1the diacid mole of group/containing R 2diacid mole≤4 of group;
Described containing R 1the diacid structural of group is one of following structure:
Figure BSA00000157424300031
Containing R 2the diacid of group is one of following structure:
Figure BSA00000157424300032
Described amberplex can be used in liquid-flow energy storage battery with acidic electrolyte.
Before application, can will prepare containing immerse in sulfuric acid or phosphoric acid solution>=1h of the Polybenzimidazole polymer ion exchange membrane of pyridine groups; The concentration of sulfuric acid or phosphoric acid solution is at 1～16mol L -1between.
The invention still further relates to amberplex prepared by the above-mentioned copolymer application in liquid-flow energy storage battery with acidic electrolyte.Liquid-flow energy storage battery with acidic electrolyte comprises: all-vanadium liquid flow energy storage battery, siderochrome liquid flow energy storage battery, zinc bromine liquid flow energy storage battery, vanadium bromine liquid flow energy storage battery, the redox flow batteries that vanadium Cerium liquid flow energy storage battery etc. contains acidic electrolyte bath.Useful result of the present invention is:
(1) preparation condition of the polybenzimidazole polymer containing pyridine groups that the present invention synthesizes is gentle, and the polymer of reaction preparation contains more activation N group, is conducive to improve the hydrophily of film and the proton-conducting of film.
(2) in this reaction, can control by controlling the content of different structure bisgallic acid monomer the content of pyridine structure unit in polymer.
(3) polymer by this reaction preparation has good dissolubility and filming performance.
(4) this is invented prepared amberplex and has good thermal stability and mechanical performance.
(5) containing the polybenzimidazoles class amberplex of pyridine groups, be applied to vanadium redox battery and there is good proton conduction property and excellent obstruct vanadium ion permeance property.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the polymer of embodiment 2 preparations.
Fig. 2 is the stress-strain diagram of the polymer film of embodiment 2 preparations.
Fig. 3 is the polymer thermogravimetric analysis curve of embodiment 2 preparations.
Fig. 4 is the contact angle data of embodiment 1 and embodiment 4 prepared films.
Fig. 5 is that the whole vanadium oxide reduction battery of ion exchange polymer film of embodiment 2 preparation is at 80mAcm -2time charging and discharging curve.
Embodiment
The following examples are to further illustrate of the present invention, rather than limit the scope of the invention.
Embodiment 1
3.4 grams of phosphorus pentoxides are dissolved in 34 grams of polyphosphoric acids, join in the there-necked flask of 500ml, heat up to stir and form after settled solution, then add 6mmol biphenyl tetramine, 6mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling, pours in the sodium hydroxide solution that contains 5%.After placing 24 hours, fully wash with water, until solution is neutral.Filter, dry.The polymer of preparation is dissolved in to the solution of preparing 4wt% in DMSO, solution-cast, to glass plate, is bulldozed with casting film cutter.Dry after 20 hours at 80 ℃, film is taken off from glass plate.Dry polymer film soaking at room temperature is processed to 5h in 4M sulfuric acid, and obtaining thickness is the polybenzimidazoles amberplex of the not pyridine structure contained unit of about 35 μ m.
Embodiment 2
3.4 grams of phosphorus pentoxides are dissolved in 34 grams of polyphosphoric acids, join in the there-necked flask of 500ml, heating up to stir forms after settled solution, then adds 6mmol biphenyl tetramine, 1.2mmol 2,6-cinchomeronic acid, 4.8mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling, pours in the sodium hydroxide solution that contains 5%.After placing 24 hours, fully wash with water, until solution is neutral.Filter, dry.The polymer of preparation is dissolved in to the solution of preparing 4wt% in DMSO, solution-cast, to glass plate, is bulldozed with casting film cutter.Dry after 20 hours at 80 ℃, film is taken off from glass plate.Dry polymer film soaking at room temperature is processed to 5h in 4M sulfuric acid, and obtaining thickness is the polybenzimidazoles amberplex containing 20wt% pyridine structure unit of about 35 μ m.Fig. 1 is the infrared figure for preparing polymer, has confirmed the structure of prepared polymer.The stress-strain diagram of film is as Fig. 2, and the hot strength of film is 90MPa, and modulus of elasticity is 3GPa, has shown good mechanical performance.Fig. 3 is the polymer thermogravimetric analysis curve of preparation, and as can be seen from the figure this polymer is in about 530 ℃ of thermal degradations that main chain occurs, and this polymer shows good thermal stability.
Embodiment 3
With embodiment 2, difference is with it, replaces sulfuric acid film soaking at room temperature is processed 3 days with 6M phosphoric acid, takes out and dry to obtain the polybenzimidazoles amberplex that thickness is 40 μ m.
Embodiment 4
3.6 grams of phosphorus pentoxides are dissolved in 36 grams of polyphosphoric acids, join in the there-necked flask of 500ml, heating up to stir forms after settled solution, then adds 6mmol biphenyl tetramine, 2.4mmol 2,6-cinchomeronic acid, 3.6mmol4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling, pours in the sodium hydroxide solution that contains 5wt%.After placing 24 hours, fully wash with water, until solution is neutral.Filter, dry.The polymer of preparation is dissolved in to the solution of preparing 4wt% in DMSO, solution-cast, to glass plate, is bulldozed with casting film cutter.Dry after 20 hours at 80 ℃, film is taken off from glass plate.Dry polymer film soaking at room temperature is processed to 5h in 4M sulfuric acid, and obtaining thickness is the polybenzimidazoles amberplex containing 40wt% pyridine structure unit of about 35 μ m.Fig. 4 has provided the contact angle of the polybenzimidazole membrane of the prepared film of embodiment 4 and the prepared pyridine structure contained unit not of embodiment 1.The contact angle that does not wherein contain the polybenzimidazole membrane of pyridine groups is 92.82 °, and (Fig. 4 a), the contact angle that contains the polybenzimidazole polymer film of 40% pyridine structure unit is 55.77 ° (Fig. 4 b), the introducing of pyridine structure unit is described, has greatly improved the hydrophily of film.
Embodiment 5
With embodiment 4, difference is with it, replaces sulfuric acid film soaking at room temperature is processed 3 days with 6M phosphoric acid, takes out and dry that to obtain thickness be the amberplex that 40 μ m Han oxadiazoles and triazole are gathered aryl.
Embodiment 6
3.6 grams of phosphorus pentoxides are dissolved in 36 grams of polyphosphoric acids, join in the there-necked flask of 500ml, heating up to stir forms after settled solution, then adds 6mmol biphenyl tetramine, 3mmol 2,6-cinchomeronic acid, 3mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling, pours in the sodium hydroxide solution that contains 5%.After placing 24 hours, fully wash with water, until solution is neutral.Filter, dry.The polymer of preparation is dissolved in to the solution of preparing 4wt% in DMSO, solution-cast, to glass plate, is bulldozed with casting film cutter.Dry after 20 hours at 80 ℃, film is taken off from glass plate.Dry polymer film soaking at room temperature is processed to 5h in 4M sulfuric acid, and obtaining thickness is the polybenzimidazoles amberplex containing 50wt% pyridine structure unit of about 35 μ m.
Embodiment 7
3.4 grams of phosphorus pentoxides are dissolved in 34 grams of polyphosphoric acids, join in the there-necked flask of 500ml, heating up to stir forms after settled solution, then adds 6mmol biphenyl tetramine, 1.2mmol 3,5-cinchomeronic acid, 4.8mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling, pours in the sodium hydroxide solution that contains 5%.After placing 24 hours, fully wash with water, until solution is neutral.Filter, dry.The polymer of preparation is dissolved in to the solution of preparing 4wt% in DMSO, solution-cast, to glass plate, is bulldozed with casting film cutter.Dry after 20 hours at 80 ℃, film is taken off from glass plate.Dry polymer film soaking at room temperature is processed to 5h in 4M sulfuric acid, obtain thickness and be about 35 μ m containing 20wt%3, the polybenzimidazoles amberplex of 5-disubstituted pyridines construction unit.
Embodiment 8
3.6 grams of phosphorus pentoxides are dissolved in 36 grams of polyphosphoric acids, join in the there-necked flask of 500ml, heating up to stir forms after settled solution, then adds 6mmol biphenyl tetramine, 2.4mmol 3,5-cinchomeronic acid, 3.6mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling, pours in the sodium hydroxide solution that contains 5wt%.After placing 24 hours, fully wash with water, until solution is neutral.Filter, dry.The polymer of preparation is dissolved in to the solution of preparing 4wt% in DMSO, solution-cast, to glass plate, is bulldozed with casting film cutter.Dry after 20 hours at 80 ℃, film is taken off from glass plate.Dry polymer film soaking at room temperature is processed to 5h in 4M sulfuric acid, obtain thickness and be about 35 μ m containing 40wt%3, the polybenzimidazoles amberplex of 5-disubstituted pyridines construction unit.
Embodiment 9
3.4 grams of phosphorus pentoxides are dissolved in 34 grams of polyphosphoric acids, join in the there-necked flask of 500ml, heating up to stir forms after settled solution, then adds 6mmol biphenyl tetramine, 1.2mmol 2,5-cinchomeronic acid, 4.8mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling, pours in the sodium hydroxide solution that contains 5%.After placing 24 hours, fully wash with water, until solution is neutral.Filter, dry.The polymer of preparation is dissolved in to the solution of preparing 4wt% in DMSO, solution-cast, to glass plate, is bulldozed with casting film cutter.Dry after 20 hours at 80 ℃, film is taken off from glass plate.Dry polymer film soaking at room temperature is processed to 5h in 4M sulfuric acid, obtain thickness and be about 35 μ m containing 20wt%2, the polybenzimidazoles amberplex of 5-disubstituted pyridines construction unit.
Embodiment 10
3.6 grams of phosphorus pentoxides are dissolved in 36 grams of polyphosphoric acids, join in the there-necked flask of 500ml, heating up to stir forms after settled solution, then adds 6mmol biphenyl tetramine, 2.4mmol 2,5-cinchomeronic acid, 3.6mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling, pours in the sodium hydroxide solution that contains 5wt%.After placing 24 hours, fully wash with water, until solution is neutral.Filter, dry.The polymer of preparation is dissolved in to the solution of preparing 4wt% in DMSO, solution-cast, to glass plate, is bulldozed with casting film cutter.Dry after 20 hours at 80 ℃, film is taken off from glass plate.Dry polymer film soaking at room temperature is processed to 5h in 4M sulfuric acid, obtain thickness and be about 35 μ m containing 40wt%2, the polybenzimidazoles amberplex of 5-disubstituted pyridines construction unit.
Embodiment 11
3.4 grams of phosphorus pentoxides are dissolved in 34 grams of polyphosphoric acids, join in the there-necked flask of 500ml, heating up to stir forms after settled solution, then add 6mmol biphenyl tetramine, 1.2mmol 2,6-cinchomeronic acid, and 4.8mmol 4,4 '-dicarboxyl-3,3 '-dimethyl diphenyl ether, stirs and is warming up to 200 degree, reacts after 20 hours, cooling, pours in the sodium hydroxide solution that contains 5%.After placing 24 hours, fully wash with water, until solution is neutral.Filter, dry.The polymer of preparation is dissolved in to the solution of preparing 4wt% in DMSO, solution-cast, to glass plate, is bulldozed with casting film cutter.Dry after 20 hours at 80 ℃, film is taken off from glass plate.Dry polymer film soaking at room temperature is processed to 5h in 4M sulfuric acid, and obtaining thickness is the polybenzimidazoles amberplex containing 20wt% pyridine structure unit of about 35 μ m.
Embodiment 12
By in embodiment 1 not containing in the polybenzimidazoles amberplex of pyridine groups and embodiment 2 containing the polybenzimidazoles amberplex assembling vanadium redox battery of pyridine groups, activated carbon-fiber felt is Catalytic Layer, graphite cake is bipolar plates, and film effective area is 9cm -2, current density is 80mAcm -2, in electrolyte, vanadium ion concentration is 1.50mol L -1, H 2sO 4concentration is 3mol L -1.
The battery that utilizes embodiment 1 not assemble containing the polybenzimidazoles amberplex of pyridine groups, current efficiency is 99.2%, and voltage efficiency is 80.6%, and energy efficiency is 80.2%.The current efficiency 99.3% that contains the amberplex assembled battery of pyridine groups in embodiment 2, voltage efficiency is 86.2%, energy efficiency is 85.6%.Compare with the polybenzimidazoles that does not contain pyridine ring, containing cell voltage efficiency and the energy efficiency of the amberplex assembling of pyridine ring be significantly improved (having risen 5 percentage points), illustrate that the introducing of pyridine ring effectively raises the ionic conductivity of film, reduced the internal resistance of cell, thereby voltage efficiency is significantly improved.Battery charging and discharging curve is shown in Fig. 5, in figure charging interval and discharge time substantially suitable, discharge quite mild, show that the vanadium permeability of film is quite low.
Relatively: will in above-described embodiment 1, containing the polybenzimidazoles amberplex of pyridine groups, not change Nafion 115 films of E.I.Du Pont Company's production into, other conditions are constant.Battery current efficiency is 94.8%, and voltage efficiency is 88.9%, and energy efficiency is 84.5%.Compare with business-like Nafion, the polybenzimidazoles amberplex containing pyridine groups of preparation is under the suitable prerequisite of energy efficiency, and current efficiency significantly improves (improving 5 percentage points).Polybenzimidazoles base polymer is described, has effectively reduced vanadium ion and interpenetrated the cross pollution causing, improved the current efficiency of battery.

Claims (5)

1. the application of Polybenzimidazole polymer ion exchange membrane in flow battery, is characterized in that: described ion exchange polymer film is for liquid-flow energy storage battery with acidic electrolyte, and polymer architecture general formula is as follows,
Figure FDA0000383252290000011
Polymer is random copolymer, and wherein m and n are respectively the molar content of different structure unit, 0 < n≤0.8, and 0.2≤m < 1, m+n=1, the weight average molecular weight of this polymer is between 5000-800000;
R 1represent one of following structure:
R 2represent one of following structure:
Figure FDA0000383252290000013
Wherein: R 3and R 4be respectively a kind of in hydrogen atom, C1-C4 saturated alkane group or the unsaturated alkane group of C2-C4, R 3and R 4it can be identical or different group;
Described film adopts following process to be prepared,
(1) phosphorus pentoxide is dissolved in polyphosphoric acids, heats up and form settled solution; Wherein the mass ratio of phosphorus pentoxide and polyphosphoric acids is between 1:5～1:20;
(2) in the solution of step (1), add containing R 1the diacid of group and containing R 2the diacid of group and biphenyl tetramine; Be heated to 190-220 ℃, reaction 3-30 hour, pours solution in alkali lye into, finally controls solution for neutral, filters, by the solid polymer water boil obtaining, and filters, by the solid polymer oven dry obtaining; Wherein in reaction system, contain R 1the diacid of group and containing R 2the diacid of group and the biphenyl tetramine gross mass percentage composition in polyphosphoric acids solvent is between 2%-15%; And containing R 1the diacid of group and containing R 2total mole dosage sum of the diacid of group is identical with biphenyl tetramine;
(3) the polybenzimidazoles base polymer containing pyridine groups of drying is dissolved in one or more solvents of NMP, DMF, DMAC, DMSO at 60-100 ℃, the concentration of solution is controlled at 2-15wt%, by the polymer solution direct pouring obtaining on glass plate or corrosion resistant plate, at 60～100 ℃ more than dry 5h, then 80～150 ℃ of above film forming of vacuumize 1h, the thickness of film is between 10～200 μ m.
2. application according to claim 1, is characterized in that: in polymer, the content of pyridine ring can contain R by control<sub TranNum="201">1</sub>the diacid of group with containing R<sub TranNum="202">2</sub>the ratio of the mole dosage of the diacid of group realizes; 0<containing R<sub TranNum="203">1</sub>the diacid mole of group/containing R<sub TranNum="204">2</sub>diacid mole≤4 of group.
3. application according to claim 2, is characterized in that: described containing R 1the diacid structural of group is one of following structure:
Figure FDA0000383252290000021
Containing R 2the diacid of group is one of following structure:
Figure FDA0000383252290000022
Wherein: R 3and R 4be respectively a kind of in hydrogen atom, C1-C4 saturated alkane group or the unsaturated alkane group of C2-C4, R 3and R 4it can be identical or different group.
4. application according to claim 1, is characterized in that: before application, can will prepare containing immerse in sulfuric acid or phosphoric acid solution >=1h of the Polybenzimidazole polymer ion exchange membrane of pyridine groups.
5. application according to claim 4, is characterized in that: the concentration of sulfuric acid or phosphoric acid solution is at 1～16mol L -1between.
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