CN102299351A - 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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CN102299351A
CN102299351A CN2010102101352A CN201010210135A CN102299351A CN 102299351 A CN102299351 A CN 102299351A CN 2010102101352 A CN2010102101352 A CN 2010102101352A CN 201010210135 A CN201010210135 A CN 201010210135A CN 102299351 A CN102299351 A CN 102299351A
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diacid
solution
polymer
amberplex
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CN102299351B (en
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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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Dalian Institute of Chemical Physics of CAS
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

Polybenzimidazoles base polymer amberplex and preparation thereof and application
Technical field
The present invention relates to a kind of polybenzimidazoles class amberplex that contains the pyridine group and preparation method thereof, particularly this contains the application of polybenzimidazoles class amberplex in vanadium redox battery of pyridine group.
Background technology
Liquid-flow energy storage battery with acidic electrolyte is a kind of electrochemical energy storage new technology, but has the energy conversion efficiency height, advantages such as system design is flexible, capacitance of storage is big, the free deep discharge of addressing, is 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, because both positive and negative polarity adopts the vanadium ion electrolyte of different valence state, therefore the electrolyte contamination problem of having avoided the mutual string of electrolyte both positive and negative polarity to bring, and 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 the 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 influence the chemical property and the useful life of vanadium cell; Therefore require film to have lower active material permeability (higher selectivity is promptly arranged) and lower face resistance (higher ionic conductance is promptly arranged), also should have better chemical stability and lower cost simultaneously.The Nafion film that the main both at home and abroad now membrane material that uses mainly is the du pont company exploitation, the Nafion film has excellent performance at aspects such as chemical property and useful lifes, but be applied to exist in the vanadium redox battery ion selectivity low, shortcoming such as cost an arm and a leg, thus limited the industrial applications of this film.Therefore, exploitation has high selectivity, high stability and amberplex is most important cheaply.
The polybenzimidazoles base polymer is to be the polymer of main repetitive with benzimidazole, owing in strand, there is the fragrant heterocycle of conjugation, keep the hexahedral arrangement architecture of polymer fragrance, thereby had excellent thermal stability, chemical stability and mechanical property.Polybenzimidazoles can form a kind of doping system of soda acid with strong acid hydridization, 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 sulfuric acid mixes contains the imidazoles polymer film and can play proton conducting as the vanadium redox battery barrier film.At present, the polybenzimidazole resin that commercialization contains glyoxaline structure on the market is poly-[2,2 '-(-phenylene)-5,5 '-bisbenzimidazole].This resin exists that infusibility melts, unmanageable defective, and film forming procedure is had relatively high expectations to experimental provision, and operating condition is comparatively harsh.And, the film of poly-[2,2 '-(-phenylene)-5,5 '-bisbenzimidazole] preparation of full aromatic structure, nitrogen that can be protonated is less, and resistance is bigger.Therefore, from the flow battery angle of practical application, develop targetedly and have 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, that in vanadium redox battery, have superperformance.
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, have polybenzimidazoles class amberplex of good ionic conductivity and filming performance and preparation method thereof.The present invention is based on the pyridine group in contain the high suction acidity of N group, contain the construction unit of pyridine by introducing, improve the ionic conductivity of polybenzimidazoles.The present invention utilizes the bisgallic acid and the biphenyl tetramine of different structure, obtains by nucleophilic condensation polymerization.In the reaction system wherein a kind of structure of bisgallic acid be the diacid that contains the pyridine group, by adjusting this sour content, obtain having the polybenzimidazoles base polymer of different pyridine structures unit, 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:
A kind of polybenzimidazoles base polymer amberplex, described polymer architecture general formula is as follows,
Polymer is a random copolymer, and wherein m and n are respectively the molar content of different structure unit, 0＜n≤0.8,0.2≤m＜1, and m+n=1, the weight average molecular weight of this base polymer is between 5000-800000;
R 1Represent one of following structure:
R wherein 1Design feature is: the pyridine group can more be helped the transmission of proton as the alkalescent group by protonated 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:
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 the 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 the polyphosphoric acids, heating up forms settled solution; Wherein the mass ratio of phosphorus pentoxide and polyphosphoric acids was between 1: 5～1: 20;
(2) adding contains R in the solution of step (1) 1The diacid of group and contain R 2The diacid of group and biphenyl tetramine; Heat temperature raising reacted 3-30 hour to 190-220 ℃, and solution is poured in the alkali lye, finally controlled solution for neutral, filtered, with the solid polymer that obtains water boil, filters, the solid polymer that obtains is dried; Monomer R in the reaction system wherein 1The diacid of group and R 2The diacid of group and the biphenyl tetramine gross mass percentage composition in the polyphosphoric acids solvent is between 2%-15%; And contain R 1The diacid of group and contain R 2Total mole dosage sum of the diacid of group is identical with the biphenyl tetramine;
(3) the polybenzimidazoles base polymer that contains the pyridine group that will dry is dissolved under 60-100 ℃ in one or more solvents of NMP, DMF, DMAC, DMSO, the concentration of solution is controlled at 2-15wt%, with the polymer solution direct pouring that obtains on glass plate or corrosion resistant plate, more than dry 5h under 60～100 ℃, 80～150 ℃ of above film forming of vacuumize 1h then, the thickness of film is between 10～200 μ m.
The content of pyridine ring can contain R by control in the polymer 1The diacid of group with contain R 2The ratio of the diacid mole dosage of group realizes.0＜R 1The diacid mole of group/contain R 2Diacid mole≤4 of group;
The described R that contains 1The diacid structural of group is one of following structure:
Figure BSA00000157424300031
Contain R 2The diacid of group is one of following structure:
Figure BSA00000157424300032
Described amberplex can be used in the liquid-flow energy storage battery with acidic electrolyte.
Before the application, can immerse in sulfuric acid or the phosphoric acid solution 〉=1h preparing the polybenzimidazoles base polymer amberplex that contains the pyridine group; The concentration of sulfuric acid or phosphoric acid solution is at 1～16mol L -1Between.
The invention still further relates to the application of amberplex in liquid-flow energy storage battery with acidic electrolyte of above-mentioned copolymer.Liquid-flow energy storage battery with acidic electrolyte comprises: all-vanadium liquid flow energy storage battery, siderochrome liquid flow energy storage battery, and zinc bromine liquid flow energy storage battery, vanadium bromine liquid flow energy storage battery, vanadium Cerium liquid flow energy storage battery etc. contains the redox flow batteries of acidic electrolyte bath.Useful result of the present invention is:
The preparation condition gentleness of the polybenzimidazole polymer that contains the pyridine group that (1) the present invention synthesizes, the polymer of prepared in reaction contain more activation N group, help improving the hydrophily of film and the proton-conducting of film.
(2) can be in this reaction by the content of pyridine structure unit in the content control polymer of control different structure bisgallic acid monomer.
(3) polymer by this prepared in reaction has fine solubility and filming performance.
(4) the prepared amberplex of this invention has good thermal stability and mechanical performance.
(5) the polybenzimidazoles class amberplex that contains the pyridine group is applied to vanadium redox battery and has good proton conduction performance and excellent obstruct vanadium ion permeance property.
Description of drawings
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 -2The time charging and discharging curve.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
3.4 gram phosphorus pentoxides are dissolved in the 34 gram polyphosphoric acids, join in the there-necked flask of 500ml, after the stirring that heats up forms settled solution, add 6mmol biphenyl tetramine then, 6mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling is poured into and is contained in 5% the sodium hydroxide solution.After placing 24 hours, fully wash with water, be neutral up to solution.Filter oven dry.The polymer of preparation is dissolved in the solution for preparing 4wt% among the DMSO, to glass plate, pushes away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtaining thickness is the polybenzimidazoles amberplex of the not pyridine structure contained unit of about 35 μ m.
Embodiment 2
3.4 gram phosphorus pentoxides are dissolved in the 34 gram polyphosphoric acids, join in the there-necked flask of 500ml, after the stirring that heats up forms settled solution, add 6mmol biphenyl tetramine then, 1.2mmol 2, the 6-cinchomeronic acid, 4.8mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling is poured into and is contained in 5% the sodium hydroxide solution.After placing 24 hours, fully wash with water, be neutral up to solution.Filter oven dry.The polymer of preparation is dissolved in the solution for preparing 4wt% among the DMSO, to glass plate, pushes away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtaining thickness is the polybenzimidazoles amberplex that contains 20wt% pyridine structure unit of about 35 μ m.Fig. 1 is the infrared figure of preparation polymer, has confirmed the structure of prepared polymer.The stress-strain diagram of film such as Fig. 2, the hot strength of film is 90MPa, modulus of elasticity is 3GPa, has shown the favorable 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 takes place, and this polymer shows good thermal stability.
Embodiment 3
With embodiment 2, difference is with it, replaces sulfuric acid with 6M phosphoric acid the film soaking at room temperature was handled 3 days, takes out and dry to obtain the polybenzimidazoles amberplex that thickness is 40 μ m.
Embodiment 4
3.6 gram phosphorus pentoxides are dissolved in the 36 gram polyphosphoric acids, join in the there-necked flask of 500ml, after the stirring that heats up forms settled solution, add 6mmol biphenyl tetramine then, 2.4mmol 2, the 6-cinchomeronic acid, 3.6mmol4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling is poured in the sodium hydroxide solution that contains 5wt%.After placing 24 hours, fully wash with water, be neutral up to solution.Filter oven dry.The polymer of preparation is dissolved in the solution for preparing 4wt% among the DMSO, to glass plate, pushes away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtaining thickness is the polybenzimidazoles amberplex that contains 40wt% pyridine structure unit of about 35 μ m.Fig. 4 has provided the contact angle of the polybenzimidazole membrane of the prepared pyridine structure contained unit not of the prepared film of embodiment 4 and embodiment 1.The contact angle that does not wherein contain the polybenzimidazole membrane of pyridine group 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 improved the hydrophily of film greatly.
Embodiment 5
With embodiment 4, difference is with it, replaces sulfuric acid with 6M phosphoric acid the film soaking at room temperature was handled 3 days, and taking-up and oven dry obtain the amberplex that thickness is 40 μ m De Han oxadiazoles and the poly-aryl of triazole.
Embodiment 6
3.6 gram phosphorus pentoxides are dissolved in the 36 gram polyphosphoric acids, join in the there-necked flask of 500ml, after the stirring that heats up forms settled solution, add 6mmol biphenyl tetramine then, 3mmol 2, the 6-cinchomeronic acid, 3mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling is poured into and is contained in 5% the sodium hydroxide solution.After placing 24 hours, fully wash with water, be neutral up to solution.Filter oven dry.The polymer of preparation is dissolved in the solution for preparing 4wt% among the DMSO, to glass plate, pushes away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtaining thickness is the polybenzimidazoles amberplex that contains 50wt% pyridine structure unit of about 35 μ m.
Embodiment 7
3.4 gram phosphorus pentoxides are dissolved in the 34 gram polyphosphoric acids, join in the there-necked flask of 500ml, after the stirring that heats up forms settled solution, add 6mmol biphenyl tetramine then, 1.2mmol 3, the 5-cinchomeronic acid, 4.8mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling is poured into and is contained in 5% the sodium hydroxide solution.After placing 24 hours, fully wash with water, be neutral up to solution.Filter oven dry.The polymer of preparation is dissolved in the solution for preparing 4wt% among the DMSO, to glass plate, pushes away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtaining thickness is the 20wt%3 that contains of about 35 μ m, the polybenzimidazoles amberplex of 5-disubstituted pyridines construction unit.
Embodiment 8
3.6 gram phosphorus pentoxides are dissolved in the 36 gram polyphosphoric acids, join in the there-necked flask of 500ml, after the stirring that heats up forms settled solution, add 6mmol biphenyl tetramine then, 2.4mmol 3, the 5-cinchomeronic acid, 3.6mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling is poured in the sodium hydroxide solution that contains 5wt%.After placing 24 hours, fully wash with water, be neutral up to solution.Filter oven dry.The polymer of preparation is dissolved in the solution for preparing 4wt% among the DMSO, to glass plate, pushes away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtaining thickness is the 40wt%3 that contains of about 35 μ m, the polybenzimidazoles amberplex of 5-disubstituted pyridines construction unit.
Embodiment 9
3.4 gram phosphorus pentoxides are dissolved in the 34 gram polyphosphoric acids, join in the there-necked flask of 500ml, after the stirring that heats up forms settled solution, add 6mmol biphenyl tetramine then, 1.2mmol 2, the 5-cinchomeronic acid, 4.8mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling is poured into and is contained in 5% the sodium hydroxide solution.After placing 24 hours, fully wash with water, be neutral up to solution.Filter oven dry.The polymer of preparation is dissolved in the solution for preparing 4wt% among the DMSO, to glass plate, pushes away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtaining thickness is the 20wt%2 that contains of about 35 μ m, the polybenzimidazoles amberplex of 5-disubstituted pyridines construction unit.
Embodiment 10
3.6 gram phosphorus pentoxides are dissolved in the 36 gram polyphosphoric acids, join in the there-necked flask of 500ml, after the stirring that heats up forms settled solution, add 6mmol biphenyl tetramine then, 2.4mmol 2, the 5-cinchomeronic acid, 3.6mmol 4,4 '-dicarboxyl diphenyl ether, stirring is warming up to 200 degree, react after 20 hours, cooling is poured in the sodium hydroxide solution that contains 5wt%.After placing 24 hours, fully wash with water, be neutral up to solution.Filter oven dry.The polymer of preparation is dissolved in the solution for preparing 4wt% among the DMSO, to glass plate, pushes away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtaining thickness is the 40wt%2 that contains of about 35 μ m, the polybenzimidazoles amberplex of 5-disubstituted pyridines construction unit.
Embodiment 11
3.4 gram phosphorus pentoxides are dissolved in the 34 gram polyphosphoric acids, join in the there-necked flask of 500ml, after the stirring that heats up forms settled solution, add 6mmol biphenyl tetramine then, 1.2mmol 2, the 6-cinchomeronic acid, 4.8mmol 4,4 '-dicarboxyl-3,3 '-dimethyl diphenyl ether stirs and is warming up to 200 degree, reacts after 20 hours, cooling is poured into and is contained in 5% the sodium hydroxide solution.After placing 24 hours, fully wash with water, be neutral up to solution.Filter oven dry.The polymer of preparation is dissolved in the solution for preparing 4wt% among the DMSO, to glass plate, pushes away flat solution-cast with the casting film cutter.After under 80 ℃ dry 20 hours, film is taken off from glass plate.Dry polymer film soaking at room temperature is handled 5h in 4M sulfuric acid, obtaining thickness is the polybenzimidazoles amberplex that contains 20wt% pyridine structure unit of about 35 μ m.
Embodiment 12
The polybenzimidazoles amberplex assembling vanadium redox battery that contains the pyridine group among the polybenzimidazoles amberplex of pyridine group and the embodiment 2 will do not contained among the embodiment 1, activated carbon-fiber felt is a Catalytic Layer, graphite cake is a bipolar plates, and the film effective area is 9cm -2, current density is 80mAcm -2, vanadium ion concentration is 1.50mol L in the electrolyte -1, H 2SO 4Concentration is 3mol L -1
Utilize embodiment 1 not contain the battery of the polybenzimidazoles amberplex assembling of pyridine group, 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 group among the embodiment 2, voltage efficiency are 86.2%, and energy efficiency is 85.6%.Compare with the polybenzimidazoles that does not contain pyridine ring, cell voltage efficient and the energy efficiency that contains 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, reduce the internal resistance of cell, thereby made voltage efficiency be significantly improved.The battery charging and discharging curve is seen Fig. 5, among the figure charging interval and discharge time suitable substantially, it is quite mild to discharge, and shows that the vanadium permeability of film is quite low.
Relatively: change the polybenzimidazoles amberplex that does not contain the pyridine group in the foregoing description 1 into Nafion 115 films that E.I.Du Pont Company produces, other conditions are constant.Battery current efficient is 94.8%, and voltage efficiency is 88.9%, and energy efficiency is 84.5%.Compare with business-like Nafion, the polybenzimidazoles amberplex that contains the pyridine group of preparation is under the suitable prerequisite of energy efficiency, and current efficiency significantly improves (improving 5 percentage points).The polybenzimidazoles base polymer is described, has reduced vanadium ion effectively and interpenetrated the cross pollution that causes, improved the current efficiency of battery.

Claims (7)

1. polybenzimidazoles base polymer amberplex, it is characterized in that: described polymer architecture general formula is as follows,
Figure FSA00000157424200011
Polymer is a random copolymer, and wherein m and n are respectively the molar content of different structure unit, 0＜n≤0.8,0.2≤m＜1, and m+n=1, the weight average molecular weight of this base polymer is between 5000-800000;
R 1Represent one of following structure:
Figure FSA00000157424200012
R 2Represent one of following structure:
Figure FSA00000157424200013
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.
2. the preparation method of the described amberplex of claim 1 is characterized in that: adopt following process to be prepared,
(1) phosphorus pentoxide is dissolved in the polyphosphoric acids, heating up forms settled solution; Wherein the mass ratio of phosphorus pentoxide and polyphosphoric acids was between 1: 5～1: 20;
(2) adding contains R in the solution of step (1) 1The diacid of group and contain R 2The diacid of group and biphenyl tetramine; Heat temperature raising reacted 3-30 hour to 190-220 ℃, and solution is poured in the alkali lye, finally controlled solution for neutral, filtered, with the solid polymer that obtains water boil, filters, the solid polymer that obtains is dried; Monomer R in the reaction system wherein 1The diacid of group and R 2The diacid of group and the biphenyl tetramine gross mass percentage composition in the polyphosphoric acids solvent is between 2%-15%; And contain R 1The diacid of group and contain R 2The mole dosage sum of the diacid of group is identical with the biphenyl tetramine;
(3) the polybenzimidazoles base polymer that contains the pyridine group that will dry is dissolved under 60-100 ℃ in one or more solvents of NMP, DMF, DMAC, DMSO, the concentration of solution is controlled at 2-15wt%, with the polymer solution direct pouring that obtains on glass plate or corrosion resistant plate, more than dry 5h under 60～100 ℃, 80～150 ℃ of above film forming of vacuumize 1h then, the thickness of film is between 10～200 μ m.
3. the preparation method of amberplex according to claim 2, it is characterized in that: the content of pyridine ring can contain R by control in the polymer 1The diacid of group with contain R 2The ratio of the diacid mole dosage of group realizes; 0＜R 1The diacid mole of group/contain R 2Diacid mole≤4 of group.
4. the preparation method of amberplex according to claim 2 is characterized in that: the described R of containing 1The diacid structural of group be following structure it～:
Figure FSA00000157424200021
Contain R 2The diacid of group is one of following structure:
Figure FSA00000157424200022
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.
5. the application of the described amberplex of claim 1 in flow battery is characterized in that: the described amberplex of claim 1 is used for liquid-flow energy storage battery with acidic electrolyte.
6. application according to claim 5 is characterized in that: before the application, can immerse in sulfuric acid or the phosphoric acid solution 〉=1h preparing the polybenzimidazoles base polymer amberplex that contains the pyridine group.
7. application according to claim 6 is characterized in that: the concentration of sulfuric acid or phosphoric acid solution is at 1～16mol L -1Between.
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CN108649256A (en) * 2018-05-12 2018-10-12 中国科学院山西煤炭化学研究所 The preparation method and application of sulfonate polybenzimidazole proton exchange membrane
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