CN106750441B - 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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CN106750441B
CN106750441B CN201611116453.6A CN201611116453A CN106750441B CN 106750441 B CN106750441 B CN 106750441B CN 201611116453 A CN201611116453 A CN 201611116453A CN 106750441 B CN106750441 B CN 106750441B
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ionic liquid
high temperature
proton exchange
triazole
polybenzimidazoles
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CN106750441A (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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Zhangjiagang Institute Of Industrial Technology Dalian Institute Of Chemical Physics China Academy Of Sciences
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Abstract

The invention discloses the poly- triazole ionic liquid of a kind of cross-linking type/polybenzimidazoles high temperature proton exchange films and preparation method thereof, the cross linking membrane is using polybenzimidazoles as polymer backbone, using 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, the advantages that the disadvantages of conductivity caused by effectively avoiding polybenzimidazoles/phosphoric acid type high temp film phosphoric acid from being lost is unstable, conductivity with higher and low-permeable.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 fields, 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 technique
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of efficient, cleaning, environmental-friendly power generator, is electronic vapour The ideal power source of vehicle can also be used as the Military Powers or portable power etc. such as dispersion power station, submarine and spacecraft, have very Wide application prospect.However now widely used is perfluor type sulfonic acid membrane cell using Nafion as representative, but The proton conducting ability of this kind of proton exchange membrane is influenced very big 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.Since PEMFC is limited by operating temperature, so that it faces CO tolerance in practical application The problems such as difference, the hydro-thermal difficult management of system.Therefore PEMFC running temperature is increased to 100 DEG C or more, it can be efficiently against The above problem of traditional Nafion base PEMFC, the fuel cell (FC) of this type are normally referred to as high temperature proton exchange film combustion Expect battery (HT-PEMFC), is an important developing direction of PEMFC technology.
HT-PEMFC system has the following advantages: 1) electrochemical reaction speed improves, and effectively reduces electrochemical cathode polarization Overpotential allows to reduce catalyst load amount, allow using non-platinum catalyst；2) humidification requirements of reaction gas are reduced；3) electric Pool inner water exists with gas phase simplifies hydro-thermal management；In addition, HT-PEMFC simplifies FC cooling system to a certain extent.In view of HT-PEMFC tempting development prospect has carried out the development of HT-PEMFC critical material 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 hot spot it One.
The research of HT-PEMFC proton exchange membrane is concentrated mainly on polybenzimidazoles (PBI) at present, it is in 1959 Year is reported for the first time in United States Patent (USP), and Hoechst Celanese company, the U.S. introduces PBI film product to the market within 1988.Such as The present, PBI is as polymer-based material the most outstanding in engineering thermoplasties, in the high temperature proton exchange for being used as HT-PEMFC Huge validity and feasibility are shown in terms of film.But PBI type membrane material (T >=150 DEG C) in hot operation, meeting can not It degrades with avoiding.Furthermore phosphoric acid losing issue is also one of the bottleneck for influencing PBI type high temp film commercial applications, for this purpose, It can be by the ionic liquid of other conducting hydrogen ions, to replace the conduction of phosphoric acid, to solve the problems, such as that phosphoric acid is lost.
It is easy to be attacked and degraded, phosphoric acid by free radical in conclusion obtaining such proton exchange membrane polymeric substrates at present It is lost the problems such as serious and restricts its commercialized application, by using ionic liquid conducting hydrogen ions in film, being constructed in film Cross-linked structure can effectively avoid the losing issue of phosphoric acid, promote the service life of film, and improve the dimensional stability of film.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide the poly- triazole ionic liquid/polyphenyl of cross-linking type simultaneously Imidazoles high temperature proton exchange film and preparation method thereof, by using triazole ionic liquid base polyethylene as crosslinking agent, by from It is cross-linked to form cross-linking type high temperature proton exchange film, so that the dimensional stability of polybenzimidazoles high temperature proton exchange film is improved, and Phosphoric acid is effectively avoided to be lost the loss of bring conductivity.
To achieve the goals above, the technical solution adopted by the present invention are as follows:
A kind of preparation method of the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film, including with Lower step:
(1) 0.2 ~ 1 g polybenzimidazoles is dissolved in 10 ~ 20 mL high boiling solvents, after stirring and dissolving, three nitrogen is added Azole ionic liquid base polyethylene, stirring is until dissolution；Wherein, the additional amount of triazole ionic liquid base polyethylene is poly- The 50% ~ 150% of benzimidazole 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, is evaporated solvent at 60 ~ 80 DEG C, obtained high temperature proton exchange film is careful It takes off, impregnates drying after washing in ethanol, obtain the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange Film.
Preferably, sun selected by triazole ionic liquid base polyethylene intermediate ion liquid as described in step (1) from Son is 1H-1,2,4- triazoles cation, structure C2H4N3 +；Anion is CH3SO3 -、CF3SO3 -、H2PO4 -One of or A variety of mixtures.
Preferably, the preparation method of triazole ionic liquid base polyethylene as described in step (1), including following step It is rapid:
(1) 1- vinyl -1,2 of 0.5 ~ 2 mol/L is prepared, 4- triazole chloroformic solution pours into three-necked flask, in 50 Stirring is extremely dissolved at ~ 80 DEG C；
(2) one or more mixtures of methane sulfonic acid, trifluoromethane sulfonic acid, phosphoric acid are added dropwise, 1- ethylene is added The molar ratio of base -1,2,4- triazole and acid is 1:1.5 ~ 1:3；
(3) solution is put in heating stirring in oil bath, reaction temperature is 50 ~ 80 DEG C, and after reacting 2 ~ 4 h, solution is poured into It in deionized water, washs, filters, remove extra acid and solvent, it is for several times and dry with ethanol washing, obtain white flock powder；
(4) obtained white powder is weighed into 0.2 ~ 1.2 g, 5 ~ 15 mL high boiling solvents, stirring and dissolving is added；
(5) chain initiator azodiisobutyronitrile will be added in solution, wherein the mass content of chain initiator is that higher boiling is molten The 20 ~ 50% of agent；
(6) it by after solution stirring and dissolving, is put into oil bath, reacts 30 ~ 60 h, reaction temperature is 50 ~ 80 DEG C；
(7) after reaction, solution is poured into ethyl alcohol, obtains White Flocculus, with drying after ethanol washing, obtain three Nitrogen azole ionic liquid base polyethylene.
Preferably, the high boiling solvent is n,N-dimethylacetamide or N-Methyl pyrrolidone.
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 provided by the invention and its preparation side Method has the advantages that compared with prior art
It is to hand over triazole ionic liquid base polyethylene 1. it is polymer backbone that polybenzimidazoles, which is respectively adopted, in the present invention Join agent, the structure of composite membrane as made from self-crosslinking is uniform, is suitable for anhydrous system, 120 ~ 200 DEG C of operating temperature of high temperature matter Proton exchange film fuel cell.
2. the present invention uses polybenzimidazoles/polyethylene triazole cross-linked structure, after film immersion phosphoric acid can be effectively reduced Swelling, the conduction of phosphoric acid is replaced using ionic liquid conducting hydrogen ions, effectively avoids the loss of phosphoric acid, high temperature proton is improved and hands 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 handing over Join film conductivity with higher.
Detailed description of the invention
Fig. 1 is the poly- triazole ionic liquid of cross-linking type made from embodiment 1/polybenzimidazoles high temperature proton exchange film Conductivity variation with temperature figure；
Fig. 2 is the poly- triazole ionic liquid of cross-linking type made from embodiment 2/polybenzimidazoles high temperature proton exchange film Cell polarization curves figure.
Specific embodiment
Polybenzimidazoles (PBI, CAS 25928-81-8) used is purchased from FuMA-Tech company in following example；Diformazan Yl acetamide (DMAC, CAS:127-19-5), N-Methyl pyrrolidone (NMP, CAS:872-50-4) are purchased from Tianjin great Mao Chemical reagents corporation；1- vinyl -1,2,4- triazole (CAS:2764-83-2) is purchased from Shanghai Yuan Ye Biotechnology Co., Ltd； Azodiisobutyronitrile (AIBN, CAS:78-67-1) is purchased from Tianjin great Mao chemical reagents corporation；Phosphoric acid is purchased from Shanghai Aladdin Biochemical technology limited liability company；Methane sulfonic acid (CAS:75-75-2), trifluoromethane sulfonic acid (CAS:1493-13-61) are purchased from Tianjin great Mao chemical reagents corporation.
Embodiment 1
A kind of preparation method of the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film, by with Lower step preparation:
(1) 1- vinyl -1,2 of 0.5 mol/L is prepared, 4- triazole chloroformic solution pours into three-necked flask, in 50 Stirring is extremely dissolved at DEG C；
(2) it is added dropwise phosphoric acid, the molar ratio of 1- vinyl -1,2,4- triazole and phosphoric acid is 1:1.5；
(3) solution is put in heating stirring in oil bath, reaction temperature is 50 DEG C, after reacting 4 h, by solution pour into from It in sub- water, washs, filters, remove extra acid and solvent, it is for several times and dry with ethanol washing, obtain white flock powder；
(4) obtained white powder is weighed into 0.2 g, 10 mL dimethyl acetamides, stirring and dissolving is added；
(5) chain initiator azodiisobutyronitrile will be added in solution, wherein the mass content of chain initiator is dimethyl second The 50% of amide；
(6) it by after solution stirring and dissolving, is put into oil bath, reacts 40 h, reaction temperature is 50 DEG C；
(7) after reaction, solution is poured into ethyl alcohol, obtains White Flocculus, with drying after ethanol washing, obtained C2H4N3 +- H2PO4Ionic liquid base polyethylene；
(8) then, 1 g polybenzimidazoles is dissolved in 20 mL N-Methyl pyrrolidones, after stirring and dissolving, is added C2H4N3 +- H2PO4Ionic liquid base polyethylene, stirring is until dissolution；Wherein, C2H4N3 +- H2PO4Ionic liquid base polyethylene Additional amount be polybenzimidazoles quality 50%；
(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, is evaporated solvent at 80 DEG C, obtained high temperature proton exchange film is carefully taken off Under, it impregnates in ethanol, it is dry after washing, obtain the poly- triazole ionic liquid of type/polybenzimidazoles high temperature proton exchange film.
The poly- triazole ionic liquid of cross-linking type made from 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 made from embodiment 1/polybenzimidazoles high temperature proton exchange Film and its preparation be cut into the rectangular sheet having a size of the mm of 40 mm × 10, then by the poly- triazole of cross-linking type made from embodiment 1 from Sub- liquid/polybenzimidazoles high temperature proton exchange film and its preparation are placed in conductivity fixture, and fixture is put in vacuum oven In, 3 h are kept at 90 DEG C, then temperature rises to 170 DEG C from 90 DEG C, the 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 made from embodiment 1/polybenzimidazoles high temperature proton Exchange membrane and its preparation conductivity reach 32 mS/cm, conductivity meets high temperature proton exchange at 150 DEG C under anhydrous condition The needs of membrane cell illustrate prepared cross linking membrane conductivity with 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 with Lower step preparation:
(1) 1- vinyl -1,2 of 2mol/L is prepared, 4- triazole chloroformic solution pours into three-necked flask, at 80 DEG C Stirring is extremely dissolved；
(2) trifluoromethane sulfonic acid is added dropwise, 1- vinyl -1,2, mole of 4- triazole and trifluoromethane sulfonic acid is added Than for 1:1.3；
(3) solution is put in heating stirring in oil bath, reaction temperature is 80 DEG C, after reacting 2 h, by solution pour into from It in sub- water, washs, filters, remove extra acid and solvent, for several times with ethanol washing, and it is dry, obtain white flock powder；
(4) obtained white powder is weighed into 1 g, 15 mLN- methyl pyrrolidones, stirring and dissolving is added；
(5) chain initiator azodiisobutyronitrile will be added in solution, wherein the mass content of chain initiator is N- methyl pyrrole The 48% of pyrrolidone；
(6) it by after solution stirring and dissolving, is put into oil bath, reacts 60 h, reaction temperature is 80 DEG C；
(7) after reaction, solution is poured into ethyl alcohol, obtains White Flocculus, with drying after ethanol washing, obtained C2H4N3 +- CF3SO3 -Ionic liquid base polyethylene；
(8) then, 0.5 g polybenzimidazoles is dissolved in 10 mLN- methyl pyrrolidones, after stirring and dissolving, is added C2H4N3 +- CF3SO3 -Ionic liquid base polyethylene, stirring is until dissolution；Wherein, C2H4N3 +- CF3SO3 -The poly- second of ionic liquid base The additional amount of alkene 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, is evaporated solvent at 60 DEG C, obtained high temperature proton exchange film is carefully taken off Under, it impregnates in ethanol, it is dry after washing, obtain the poly- triazole ionic liquid of type/polybenzimidazoles high temperature proton exchange film.
The poly- triazole ionic liquid of cross-linking type made from embodiment 2/polybenzimidazoles high temperature proton exchange film, in monocell The battery performance under its different temperatures is tested on evaluating apparatus.Wherein, battery cathode using carbon (C) carry nickel (Ni) catalyst with PBI solution, which is applied to after mixing on carbon paper, to be made (using preparation method disclosed in patent CN02127802.4), and Ni is accounted for The mass ratio that the mass percent of C/Ni catalyst is 40%, C/Ni and PBI is 1:1；Anode carries platinum (Pt) using carbon (C) Catalyst and PBI solution are applied on carbon paper after mixing and are made (using 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 anode2；Battery operating environment point It does not set are as follows: 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 results are shown in figure 2.
Figure it is seen that the poly- triazole ionic liquid of cross-linking type made from embodiment 2/polybenzimidazoles high temperature proton The high-temperature fuel cell of exchange membrane assembling, battery have 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 with Lower step preparation:
(1) 1- vinyl -1,2 of 1.5 mol/L is prepared, 4- triazole chloroformic solution pours into three-necked flask, in 80 Stirring is extremely dissolved at DEG C；
(2) it is added dropwise methane sulfonic acid, is added vinyl -1,2, the molar ratio of 4- triazole and methane sulfonic acid is 1:1.4；
(3) solution is put in heating stirring in oil bath, reaction temperature is 80 DEG C, after reacting 2 h, by solution pour into from It in sub- water, washs, filters, remove extra acid and solvent, it is for several times and dry with ethanol washing, obtain white flock powder；
(4) obtained white powder is weighed into 0.8 g, 15 mL dimethyl acetamides, stirring and dissolving is added；
(5) chain initiator azodiisobutyronitrile will be added in solution, wherein the mass content of chain initiator is dimethyl second The 48% of amide；
(6) it by after solution stirring and dissolving, is put into oil bath, reacts 60 h, reaction temperature is 80 DEG C；
(7) after reaction, solution is poured into ethyl alcohol, obtains White Flocculus, with drying after ethanol washing, obtained C2H4N3 +- CH3SO3 -Ionic liquid base polyethylene；
(8) then, 0.2 g polybenzimidazoles is dissolved in 10 mLN- methyl pyrrolidones, after stirring and dissolving, is added C2H4N3 +- CH3SO3 -Ionic liquid base polyethylene, stirring is until dissolution；Wherein, C2H4N3 +- CH3SO3 -The poly- second of ionic liquid base The additional amount of alkene 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, is evaporated solvent at 60 DEG C, obtained high temperature proton exchange film is carefully taken off Under, it impregnates in ethanol, it is dry after washing, obtain the poly- triazole ionic liquid of type/polybenzimidazoles high temperature proton exchange film.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, ability Other modifications or equivalent replacement that domain those of ordinary skill makes technical solution of the present invention, without departing from skill of the present invention The spirit and scope of art scheme, are intended to be within the scope of the claims of the 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, feature exist 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 is until dissolution；Wherein, the additional amount 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, is evaporated solvent at 60 ~ 80 DEG C, obtained high temperature proton exchange film is carefully taken off Under, it impregnates dry 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/polybenzimidazoles high temperature proton exchange film according to claim 1 Preparation Method, it is characterised in that: sun selected by triazole ionic liquid base polyethylene intermediate ion liquid as described in step (1) Ion is 1H-1,2,4- triazoles cation, structure C2H4N3 +；Anion is CH3SO3 -、CF3SO3 -、H2PO4 -One of Or a variety of mixture.
3. the system of the poly- triazole ionic liquid of cross-linking type/polybenzimidazoles high temperature proton exchange film according to claim 1 Preparation Method, it is characterised in that: the preparation method of triazole ionic liquid base polyethylene as described in step (1), including it is following Step:
(1) vinyl -1,2 of 0.5 ~ 2 mol/L is prepared, 4- triazole chloroformic solution pours into three-necked flask, in 50 ~ 80 DEG C Lower stirring is extremely dissolved；
(2) one or more mixtures of methane sulfonic acid, trifluoromethane sulfonic acid, phosphoric acid, additional proportion are as follows: ethylene is added dropwise The molar ratio of base -1,2,4- triazole and acid is 1:1.5 ~ 1:3；
(3) solution is put in heating stirring in oil bath, reaction temperature is 50 ~ 80 DEG C, after reacting 2 ~ 4 h, by solution pour into from It in sub- water, washs, filters, remove extra acid and solvent, it is for several times and dry with ethanol washing, obtain white flock powder；
(4) obtained white powder is weighed into 0.2 ~ 1.2 g, 5 ~ 15 mL high boiling solvents, stirring and dissolving is added；
(5) chain initiator azodiisobutyronitrile will be added in solution, wherein the mass content of chain initiator is high boiling solvent 20~50%；
(6) it by after solution stirring and dissolving, is put into oil bath, reacts 30 ~ 60 h, reaction temperature is 50 ~ 80 DEG C；
(7) after reaction, solution is poured into ethyl alcohol, obtains White Flocculus, it is dry after ethanol washing, 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 or 3 Preparation method, it is characterised in that: the high boiling solvent is n,N-dimethylacetamide or N-Methyl pyrrolidone.
5. a kind of poly- triazole ionic liquid 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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