CN106750441A - A kind of poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film and preparation method thereof - Google Patents

A kind of poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film and preparation method thereof Download PDF

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CN106750441A
CN106750441A CN201611116453.6A CN201611116453A CN106750441A CN 106750441 A CN106750441 A CN 106750441A CN 201611116453 A CN201611116453 A CN 201611116453A CN 106750441 A CN106750441 A CN 106750441A
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ionic liquid
high temperature
proton exchange
triazole
polybenzimidazoles
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CN106750441B (en
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于书淳
张燕燕
何春霞
郭会娟
李慧
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Zhangjiagang Institute of industrial technology, Dalian Institute of Chemical Physics, China Academy of Sciences
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Huanghe Science and Technology College
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
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    • H01—ELECTRIC ELEMENTS
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
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    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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    • H01—ELECTRIC ELEMENTS
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    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
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    • C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses the poly- triazole ionic liquid of a kind of cross-linking type/polybenzimidazoles high temperature proton exchange film and preparation method thereof, described cross linking membrane is with polybenzimidazoles as polymer backbone, with triazole ionic liquid base polyethylene as crosslinking agent, cross-linking type high temperature proton exchange film is formed by self-crosslinking.The poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film proposed by the present invention has preferable Proton conducting ability and excellent dimensional stability under not humidification conditions, be prevented effectively from polybenzimidazoles/phosphoric acid type high temp film phosphoric acid be lost in the electrical conductivity that causes it is unstable the shortcomings of, there is electrical conductivity and low-permeable higher.The poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film proposed by the present invention can be applied in high temperature proton exchange film fuel cell, direct alcohol fuel cell, electrochemical sensor or other electrochemical appliances.

Description

A kind of poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film And preparation method thereof
Technical field
The invention belongs to fuel cell material technical field, and in particular to a kind of poly- triazole ionic liquid of cross-linking type/poly- Benzimidazole high temperature proton exchange film and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells（PEMFC）It is a kind of efficient, cleaning, environment-friendly TRT, is electronic vapour The ideal power source of car, can act also as the Military Powers or compact power etc. such as dispersion power station, submarine and spacecraft, with very Wide application prospect.But now widely used is perfluor type sulfonic acid membrane cell with Nafion as representative, but The proton conducting ability of this kind of PEM is influenceed greatly by water content in film and temperature, and alcohol-rejecting ability is poor, the work of PEMFC Make temperature no more than 80 DEG C.Because PEMFC is limited by operating temperature so that it faces CO tolerances in practical application The problems such as difference, hydro-thermal difficult management of system.Therefore PEMFC running temperatures are brought up to more than 100 DEG C, just can be efficiently against The above mentioned problem of traditional Nafion bases PEMFC, the fuel cell of this type（FC）Normally referred to as high temperature proton exchange film combustion Material battery（HT-PEMFC）, it is an important developing direction of PEMFC technologies.
HT-PEMFC systems have the following advantages：1）Electrochemical reaction speed is improved, and effectively reduces electrochemical cathode polarization Overpotential, it is allowed to reduce catalyst load amount, it is allowed to use non-platinum catalyst；2）Humidification requirements reduction to reacting gas；3）Electricity Pool inner water is managed with gas phase in the presence of hydro-thermal is simplified；Additionally, HT-PEMFC simplifies FC cooling systems to a certain extent.In view of HT-PEMFC tempting development prospect, has carried out the development of HT-PEMFC critical materials extensively both at home and abroad, including high temperature proton is handed over Change film, catalyst and carrier etc., and achieve preferable PRELIMINARY RESULTS, wherein high temperature proton exchange film be research focus it One.
At present polybenzimidazoles is concentrated mainly on for the research of HT-PEMFC PEMs（PBI）On, it is in 1959 Year is reported first in United States Patent (USP), and Hoechst Celanese companies of the U.S. introduce PBI film products to the market within 1988.Such as The present, PBI as polymer-based material the most outstanding in engineering thermoplasties, in the high temperature proton exchange as HT-PEMFC Film aspect shows huge validity and feasibility.But PBI types membrane material is in hot operation（T≥150℃）, meeting can not Degrade with avoiding.Furthermore, phosphoric acid losing issue is also one of bottleneck of influence PBI type high temp film commercial applications, therefore, The conduction of phosphoric acid can be replaced by the ionic liquid of other conducting hydrogen ions, so as to solve the problems, such as that phosphoric acid is lost in.
In sum, obtain at present such PEM polymeric substrates easily by free radical attack and degrade, phosphoric acid It is lost in the problem such as serious and restricts its commercialized application, by will be built in film using ionic liquid conducting hydrogen ions, in film Cross-linked structure, can effectively avoid the losing issue of phosphoric acid, lift the service life of film, and improve the dimensional stability of film.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide the poly- triazole ionic liquid/polyphenyl of cross-linking type simultaneously Imidazoles high temperature proton exchange film and preparation method thereof, by with triazole ionic liquid base polyethylene as crosslinking agent, by certainly Cross-linking type high temperature proton exchange film is cross-linked to form, so that the dimensional stability of polybenzimidazoles high temperature proton exchange film is improved, and It is prevented effectively from phosphoric acid and is lost in the electrical conductivity loss for bringing.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of preparation method of the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film, including following step Suddenly：
（1）0.2 ~ 1 g polybenzimidazoles is dissolved in 10 ~ 20 mL high boiling solvents, after stirring and dissolving, triazole is added Ionic liquid base polyethylene, stirring are until dissolving；Wherein, the addition of triazole ionic liquid base polyethylene be polyphenyl simultaneously The 50% ~ 150% of imidazoles quality；
（2）Solution is put into oil bath again, is stirred at 50 ~ 100 DEG C, react 12 ~ 48 h；
（3）Solution is poured into casting film plate, solvent is evaporated at 60 ~ 80 DEG C, the high temperature proton exchange film that will be obtained carefully is taken off Under, immersion is dried after washing in ethanol, obtains the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange Film.
Preferably, step（1）Described in triazole ionic liquid base polyethylene intermediate ion liquid selected by sun from Son be 1H-1,2,4- triazole cations, structure is C2H4N3 +；Anion is CH3SO3 -、CF3SO3 -、H2PO4 -In one kind or Various mixtures.
Preferably, step（1）Described in triazole ionic liquid base polyethylene preparation method, including following step Suddenly：
（1）1- vinyl -1 of 0.5 ~ 2 mol/L is prepared, 2,4- triazole chloroformic solutions are poured into there-necked flask, in 50 ~ 80 Stirring is extremely dissolved at DEG C；
（2）Pyrovinic acid, trifluoromethane sulfonic acid, one or more of phosphoric acid of mixture are added dropwise over, 1- vinyl -1 is added, 2,4- triazoles are 1 with the mol ratio of acid:1.5~1:3；
（3）Solution is put in heating stirring in oil bath, reaction temperature is 50 ~ 80 DEG C, after 2 ~ 4 h of reaction, by solution pour into from In sub- water, washing, suction filtration removes many spent acid and solvent, is washed with ethanol for several times and dried, and obtains white flock powder；
（4）The white powder that will be obtained weighs 0.2 ~ 1.2 g, adds 5 ~ 15 mL high boiling solvents, stirring and dissolving；
（5）Chain initiator azodiisobutyronitrile will be added in solution, the wherein mass content of chain initiator is high boiling solvent 20~50%；
（6）After by solution stirring and dissolving, it is put into oil bath, reacts 30 ~ 60 h, reaction temperature is 50 ~ 80 DEG C；
（7）After reaction terminates, solution is poured into ethanol, obtain White Flocculus, dried after being washed with ethanol, obtain triazole Class ionic liquid base polyethylene.
Preferably, the high boiling solvent is DMA or 1-METHYLPYRROLIDONE.
The poly- triazole ionic liquid of the cross-linking type/polybenzimidazoles high temperature proton exchange obtained using above-mentioned preparation method Film.
The poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film and its preparation side that the present invention is provided Method, has the advantages that compared with prior art：
1. the present invention is respectively adopted polybenzimidazoles for polymer backbone, is crosslinking with triazole ionic liquid base polyethylene Agent, uniform by structure of composite membrane obtained in self-crosslinking, it is adaptable to anhydrous system, the high temperature proton of 120 ~ 200 DEG C of operating temperature Exchange film fuel battery.
2. the present invention uses polybenzimidazoles/polyethylene triazole cross-linked structure, after can effectively reducing film immersion phosphoric acid It is swelling, the conduction of phosphoric acid is replaced using ionic liquid conducting hydrogen ions, be prevented effectively from the loss of phosphoric acid, improve high temperature proton and hand over Change the stable conductivity of film.
3. the triazol radical ionic liquid in crosslinking agent of the present invention, can efficiently proton conducting so that hand over Connection film has electrical conductivity higher.
Brief description of the drawings
Fig. 1 is the poly- triazole ionic liquid of cross-linking type obtained in embodiment 1/polybenzimidazoles high temperature proton exchange film Electrical conductivity variation with temperature figure；
Fig. 2 is the battery of the poly- triazole ionic liquid of cross-linking type obtained in embodiment 2/polybenzimidazoles high temperature proton exchange film Polarization curve.
Specific embodiment
Polybenzimidazoles used in example below（PBI, CAS 25928-81-8）Purchased from FuMA-Tech companies；Diformazan Yl acetamide（DMAC, CAS: 127-19-5）, 1-METHYLPYRROLIDONE（NMP, CAS: 872-50-4）Purchased from Tianjin great Mao Chemical reagents corporation；1- vinyl -1,2,4- triazoles（CAS: 2764-83-2）Purchased from Shanghai Yuan Ye bio tech ltd； Azodiisobutyronitrile（AIBN, CAS: 78-67-1）Purchased from Tianjin great Mao chemical reagents corporations；Phosphoric acid is purchased from Shanghai Aladdin Biochemical technology limited company；Pyrovinic acid（CAS: 75-75-2）, trifluoromethane sulfonic acid（CAS: 1493-13-61）It is purchased from Tianjin great Mao chemical reagents corporations.
Embodiment 1
A kind of preparation method of the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film, by following step It is rapid to prepare：
（1）1- vinyl -1 of 0.5 mol/L is prepared, 2,4- triazole chloroformic solutions are poured into there-necked flask, at 50 DEG C Stirring is extremely dissolved；
（2）Phosphoric acid is added dropwise over, 1- vinyl -1,2,4- triazoles are 1 with the mol ratio of phosphoric acid:1.5；
（3）Solution is put in heating stirring in oil bath, reaction temperature is 50 DEG C, after 4 h of reaction, solution is poured into deionized water In, washing, suction filtration removes many spent acid and solvent, is washed with ethanol for several times and dried, and obtains white flock powder；
（4）The white powder that will be obtained weighs 0.2 g, adds 10 mL dimethylacetylamides, stirring and dissolving；
（5）Chain initiator azodiisobutyronitrile will be added in solution, the wherein mass content of chain initiator is dimethylacetylamide 50%；
（6）After by solution stirring and dissolving, it is put into oil bath, reacts 40 h, reaction temperature is 50 DEG C；
（7）After reaction terminates, solution is poured into ethanol, obtain White Flocculus, dried after being washed with ethanol, obtain C2H4N3 +- H2PO4Ionic liquid base polyethylene；
（8）Then, 1 g polybenzimidazoles is dissolved in 20 mL 1-METHYLPYRROLIDONEs, after stirring and dissolving, adds C2H4N3 +- H2PO4Ionic liquid base polyethylene, stirring are until dissolving；Wherein, C2H4N3 +- H2PO4The addition of ionic liquid base polyethylene Measure is the 50% of polybenzimidazoles quality；
（9）Solution is put into oil bath again, is stirred at 80 DEG C, react 12 h；
（10）Solution is poured into casting film plate, solvent is evaporated at 80 DEG C, the high temperature proton exchange film that will be obtained carefully is taken off, Immersion in ethanol, is dried after washing, obtains the poly- triazole ionic liquid of type/polybenzimidazoles high temperature proton exchange film.
The poly- triazole ionic liquid of cross-linking type obtained in embodiment 1/polybenzimidazoles high temperature proton exchange film, tests conductance Rate variation with temperature figure.By the poly- triazole ionic liquid of cross-linking type obtained in embodiment 1/polybenzimidazoles high temperature proton exchange Film and its preparation be cut into size be 40 mm × 10 mm rectangular sheet, then by the poly- triazole of cross-linking type obtained in embodiment 1 from Sub- liquid/polybenzimidazoles high temperature proton exchange film and its preparation are placed in electrical conductivity fixture, and fixture is put in into vacuum drying chamber In, 3 h are kept at 90 DEG C, then temperature rises to 170 DEG C from 90 DEG C, the electrical conductivity of lower film is tested every 10 DEG C, as a result As shown in Figure 1.
It will be seen from figure 1 that the poly- triazole ionic liquid of cross-linking type obtained in embodiment 1/polybenzimidazoles high temperature proton At 150 DEG C, anhydrous condition is issued to 32 mS/cm, and electrical conductivity meets high temperature proton exchange for exchange membrane and its preparation electrical conductivity The need for membrane cell, illustrate that prepared cross linking membrane has electrical conductivity higher.
Embodiment 2
A kind of preparation method of the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film, by following step It is rapid to prepare：
（1）1- vinyl -1 of 2mol/L is prepared, 2,4- triazole chloroformic solutions are poured into there-necked flask, in stirring at 80 DEG C To dissolving；
（2）Trifluoromethane sulfonic acid is added dropwise over, 1- vinyl -1 is added, 2,4- triazoles are with the mol ratio of trifluoromethane sulfonic acid 1:1.3；
（3）Solution is put in heating stirring in oil bath, reaction temperature is 80 DEG C, after 2 h of reaction, solution is poured into deionized water In, washing, suction filtration removes many spent acid and solvent, is washed for several times with ethanol, and dries, and obtains white flock powder；
（4）The white powder that will be obtained weighs 1 g, adds 15 mLN- methyl pyrrolidones, stirring and dissolving；
（5）Chain initiator azodiisobutyronitrile will be added in solution, the wherein mass content of chain initiator is N- crassitudes The 48% of ketone；
（6）After by solution stirring and dissolving, it is put into oil bath, reacts 60 h, reaction temperature is 80 DEG C；
（7）After reaction terminates, solution is poured into ethanol, obtain White Flocculus, dried after being washed with ethanol, obtain C2H4N3 +- CF3SO3 -Ionic liquid base polyethylene；
（8）Then, 0.5 g polybenzimidazoles is dissolved in 10 mLN- methyl pyrrolidones, after stirring and dissolving, adds C2H4N3 +- CF3SO3 -Ionic liquid base polyethylene, stirring are until dissolving；Wherein, C2H4N3 +- CF3SO3 -Ionic liquid base polyethylene Addition is the 120% of polybenzimidazoles quality；
（9）Solution is put into oil bath again, is stirred at 70 DEG C, react 48 h；
（10）Solution is poured into casting film plate, solvent is evaporated at 60 DEG C, the high temperature proton exchange film that will be obtained carefully is taken off, Immersion in ethanol, is dried after washing, obtains the poly- triazole ionic liquid of type/polybenzimidazoles high temperature proton exchange film.
The poly- triazole ionic liquid of cross-linking type obtained in embodiment 2/polybenzimidazoles high temperature proton exchange film, in monocell The battery performance tested on evaluating apparatus under its different temperatures.Wherein, GND uses carbon（C）Carry nickel（Ni）Catalyst with It is applied to after PBI solution is well mixed on carbon paper and is obtained（Using the preparation method disclosed in patent CN02127802.4）, Ni accounts for The mass percent of C/Ni catalyst is that the mass ratio of 40%, C/Ni and PBI is 1：1；Anode uses carbon（C）Carry platinum（Pt） Catalyst is applied on carbon paper after being well mixed with PBI solution and is obtained（Using the preparation side disclosed in patent CN02127802.4 Method）, the mass percent that Pt accounts for C/ Pt catalyst is 70%, and Pt carrying capacity is 0.5 mg/cm in positive pole2；Battery operating environment point It is not set as：Battery temperature is 150 DEG C；Hydrogen and oxygen gas flow rate are respectively 50 mL/min, 100 mL/min, and gas is without increasing Wet, pressure is 0.05 MPa, and test result is as shown in Figure 2.
Figure it is seen that the poly- triazole ionic liquid of cross-linking type obtained in embodiment 2/polybenzimidazoles high temperature proton The high-temperature fuel cell of exchange membrane assembling, battery has excellent discharge performance, and maximum power density is up to 600 mW/cm2。
Embodiment 3
A kind of preparation method of the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film, by following step It is rapid to prepare：
（1）1- vinyl -1 of 1.5 mol/L is prepared, 2,4- triazole chloroformic solutions are poured into there-necked flask, at 80 DEG C Stirring is extremely dissolved；
（2）Pyrovinic acid is added dropwise over, vinyl -1 is added, 2,4- triazoles are 1 with the mol ratio of pyrovinic acid:1.4；
（3）Solution is put in heating stirring in oil bath, reaction temperature is 80 DEG C, after 2 h of reaction, solution is poured into deionized water In, washing, suction filtration removes many spent acid and solvent, is washed with ethanol for several times and dried, and obtains white flock powder；
（4）The white powder that will be obtained weighs 0.8 g, adds 15 mL dimethylacetylamides, stirring and dissolving；
（5）Chain initiator azodiisobutyronitrile will be added in solution, the wherein mass content of chain initiator is dimethylacetylamide 48%；
（6）After by solution stirring and dissolving, it is put into oil bath, reacts 60 h, reaction temperature is 80 DEG C；
（7）After reaction terminates, solution is poured into ethanol, obtain White Flocculus, dried after being washed with ethanol, obtain C2H4N3 +- CH3SO3 -Ionic liquid base polyethylene；
（8）Then, 0.2 g polybenzimidazoles is dissolved in 10 mLN- methyl pyrrolidones, after stirring and dissolving, adds C2H4N3 +- CH3SO3 -Ionic liquid base polyethylene, stirring are until dissolving；Wherein, C2H4N3 +- CH3SO3 -Ionic liquid base polyethylene Addition is the 80% of polybenzimidazoles quality；
（9）Solution is put into oil bath again, is stirred at 70 DEG C, react 48 h；
（10）Solution is poured into casting film plate, solvent is evaporated at 60 DEG C, the high temperature proton exchange film that will be obtained carefully is taken off, Immersion in ethanol, is dried after washing, obtains the poly- triazole ionic liquid of type/polybenzimidazoles high temperature proton exchange film.
The above, specific embodiment only of the invention, but protection scope of the present invention is not limited thereto, ability Other modifications or equivalent that domain those of ordinary skill is made to technical scheme, without departing from skill of the present invention The spirit and scope of art scheme, all should cover in the middle of scope of the presently claimed invention.

Claims (5)

1. a kind of preparation method of the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film, its feature exists In comprising the following steps：
（1）0.2 ~ 1 g polybenzimidazoles is dissolved in 10 ~ 20 mL high boiling solvents, after stirring and dissolving, triazole is added Ionic liquid base polyethylene, stirring are until dissolving；Wherein, the addition of triazole ionic liquid base polyethylene be polyphenyl simultaneously The 50% ~ 150% of imidazoles quality；
（2）Solution is put into oil bath again, is stirred at 50 ~ 100 DEG C, react 12 ~ 48 h；
（3）Solution is poured into casting film plate, solvent is evaporated at 60 ~ 80 DEG C, the high temperature proton exchange film that will be obtained carefully is taken off Under, immersion is dried after washing in ethanol；Obtain the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange Film.
2. the system of the poly- triazole ionic liquid of cross-linking type according to claim 1/polybenzimidazoles high temperature proton exchange film Preparation Method, it is characterised in that：Step（1）Described in triazole ionic liquid base polyethylene intermediate ion liquid selected by sun Ion is 1H-1,2,4- triazole cations, and structure is C2H4N3 +；Anion is CH3SO3 -、CF3SO3 -、H2PO4 -In one kind Or various mixtures.
3. the system of the poly- triazole ionic liquid of cross-linking type according to claim 1/polybenzimidazoles high temperature proton exchange film Preparation Method, it is characterised in that：Step（1）Described in triazole ionic liquid base polyethylene preparation method, it is including following Step：
（1）Vinyl -1 of 0.5 ~ 2 mol/L is prepared, 2,4- triazole chloroformic solutions are poured into there-necked flask, in 50 ~ 80 DEG C Lower stirring is extremely dissolved；
（2）Pyrovinic acid, trifluoromethane sulfonic acid, one or more of phosphoric acid of mixture are added dropwise over, additional proportion is：Ethene Base -1,2,4- triazoles are 1 with the mol ratio of acid:1.5~1:3；
（3）Solution is put in heating stirring in oil bath, reaction temperature is 50 ~ 80 DEG C, after 2 ~ 4 h of reaction, by solution pour into from In sub- water, washing, suction filtration removes many spent acid and solvent, is washed with ethanol for several times and dried, and obtains white flock powder；
（4）The white powder that will be obtained weighs 0.2 ~ 1.2 g, adds 5 ~ 15 mL high boiling solvents, stirring and dissolving；
（5）Chain initiator azodiisobutyronitrile will be added in solution, the wherein mass content of chain initiator is high boiling solvent 20~50%；
（6）After by solution stirring and dissolving, it is put into oil bath, reacts 30 ~ 60 h, reaction temperature is 50 ~ 80 DEG C；
（7）After reaction terminates, solution is poured into ethanol, obtain White Flocculus, after being washed with ethanol, dried, obtain three nitrogen Azole ionic liquid base polyethylene.
4. the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film according to claim 1 and 3 Preparation method, it is characterised in that：The high boiling solvent is DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
5. the poly- triazole ionic liquid of a kind of cross-linking type/polybenzimidazoles high temperature proton exchange film, it is characterised in that：The crosslinking The poly- triazole ionic liquid of type/polybenzimidazoles high temperature proton exchange film is by any one of Claims 1-4 claim institute What the method stated was prepared.
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