CN106147197A - A kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane and preparation method thereof - Google Patents
A kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane and preparation method thereof, belonging to fuel cell material technical field, described anion exchange membrane is made up of the poly ion liquid with structural formula I therein that is doped in of the quaternized polyphenylene oxide anion exchange membrane of the N-methyl imidazoles with following constitutional repeating unit II of 99 weight % and 1 weight %:Wherein n is the integer not less than 1, and the carbon number of straight chained alkyl is 5 12；Wherein x is the integer not less than 0；Y is the integer not less than 0, and is 0 during x, y difference.The method technique of the present invention is simple, low cost.Prepared many conduction site polyphenyl ether anion exchange membrane has the advantage such as high proton conductivity and Heat stability is good, and application prospect is extensive, is particularly well-suited to anion-exchange membrane fuel cells and is suitable for.
Description
Technical field
The present invention relates to a kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane and preparation method thereof, belong to
In fuel cell material technical field, particularly anion exchange technical field of membrane.
Background technology
Fuel cell is a kind of efficient, energy conversion apparatus of cleaning.In recent years, polymer-membrane fuel battery has obtained extensively
General application, the polymeric film as critical material serves conclusive effect to performance and the life-span of fuel cell.Its
In be typically the Nafion membrane of E.I.Du Pont Company the most, it has excellent conductivity, high mechanical properties and chemical stability,
It it is the object of researcher reference.But using PEM as the polymer-membrane fuel battery of electrolyte exist a series of not
Foot: under (1) acid condition, needs the dependence noble metal such as platinum, gold as catalyst, adds the cost of fuel cell；(2) acid
Under the conditions of, the easy CO of catalyst is poisoned, and seriously reduces fuel battery performance；(3) fuel is identical with proton conduction orientation, easily causes
Electric pole short circuit.
In order to overcome disadvantage mentioned above, anion exchange membrane is considered the alternative material of PEM.Anion exchange
In the basic conditions, the stability of catalyst is high for film, therefore can use the non-noble metallic materials such as ferrum, cobalt, nickel as catalyst, and
And the reduction kinetics of oxygen of the catalyst under the conditions of alkalescence is better than acid condition.But the limitation due to anion exchange membrane itself
Property, commercial level to be reached, also need to improve the ionic conductance of anion exchange membrane, alkaline stability and mechanical performance energetically.
Research finds, increases conduction site and can be effectively improved the conductivity of anion exchange membrane.Increase conduction site
Method has following two: a kind of method is by glycerol polymerization, and the ionic group containing multiple conduction sites is grafted to polymerization
On thing skeleton；Another kind of method is directly to be doped in polymer by the ionic liquid that can conduct hydroxide ion.Wherein
Two kinds of methods are the simplest directly.
Polyphenylene oxide (PPO) is the high-strength engineering plastic developed by General Corporation, has prominent electrical insulating property and water-fast
Property, higher thermostability, simple in construction, be beneficial to the most qualitatively and quantitatively research side chain or dopant ion liquid to anion exchange membrane
The impact of energy.
The object of study of present stage ionic liquid is mostly independent conductive group, and three imidazoles benzene of a unit exist three
Individual conductive group, individual unit three imidazoles benzene just can increase substantially ionic conductance in theory.Additionally, three imidazoles benzene can also
Keep higher stability in the basic conditions.
Therefore, the ionic liquid of three imidazoles benzene is mixed in the anion exchange membrane of polyphenylene oxide, it becomes possible to improve anion
The ionic conductance of exchange membrane and stability.
Summary of the invention
An object of the present invention is to provide a kind of dye cell many conduction sites polyphenyl ether anion exchange membrane, makes
It has high ion conductivity and higher stability.
The above-mentioned purpose of the present invention reaches by the following technical programs:
A kind of fuel cell many conduction sites polyphenyl ether anion exchange membrane, it is characterised in that: described anion is handed over
Change film by the quaternized polyphenylene oxide anion exchange of the N-methyl imidazoles with following constitutional repeating unit II of 98-99 weight %
The poly ion liquid with structural formula I therein that is doped in of film and 1-2 weight % forms:
Wherein n is the integer not less than 1, and the carbon number of straight chained alkyl is 5-12；
Wherein x is the integer not less than 0；Y is the integer not less than 0, and is 0 during x, y difference.
Preferably, in described construction unit II, x:y=7:3.
Preferably, described structural formula I is poly-1,3,5-tri-(3-amyl group-1-imidazoles), poly-1,3,5-tri-(3-octyl group-1-miaows
Azoles) or poly-1,3,5-tri-(3-dodecyl-1-imidazoles) benzene ionic liquid.
It is a further object to provide the preparation method of above-mentioned many conduction sites polyphenyl ether anion exchange membrane.
The above-mentioned purpose of the present invention reaches by the following technical programs:
A kind of fuel cell preparation method of many conduction sites polyphenyl ether anion exchange membrane, comprises the steps:
(1) synthesis of polyphenylene oxide (PPO) N-methyl imidazole skeleton
Polyphenylene oxide is joined in reaction unit, under nitrogen atmosphere, be heated to 40-60 DEG C, after polyphenylene oxide is completely dissolved,
Add benzoyl peroxide (PPO) and N-bromo-succinimide (NBS), temperature is raised to 70-90 DEG C, after reacting 3-5 hour,
Reduce the temperature to room temperature, reactant solution steamed color at 40-80 DEG C of backspin and becomes brown color, then precipitate in methanol,
Obtain faint yellow solid, with dichloromethane faint yellow solid is dissolved, rotation is steamed, precipitation, repeats this operation, obtains pure faint yellow
Bromide PPO (BPPO), dry, be dissolved in DMF solution, until completely dissolved, add N-Methylimidazole., reaction, by bromo
Site is the most quaternized, obtains the polyphenylene oxide that N-methyl imidazoles is quaternized；
(2) preparation of poly-three imidazoles benzene ionic liquids
The preparation of () 1,3,5-tri-(1-imidazoles) benzene:
By 1,3,5-tribromo-benzenes, imidazoles, potassium carbonate and copper sulfate add in container, be passed through nitrogen, temperature is raised to 170-
190 DEG C, reacting 8-16 hour, product temperatur is down to room temperature afterwards, is washed with deionized, and filters, and collects upper strata solid, will be thick
Product dichloromethane extracts, after collected organic layer, and rotary evaporation, obtain 1,3,5-tri-(1-imidazoles) benzene；
The preparation of () poly-three imidazoles benzene ionic liquids:
By 1,3,5-tri-(1-imidazoles) benzene is dissolved in DMF (DMF) solution in 80-120 DEG C, adds halogen
For alkane, react 6-18 hour, obtain yellow solid, filter and be placed in baking oven drying, obtain poly-three imidazoles benzene ionic liquids；
(3) conduct the preparation of site polyphenyl ether anion exchange membrane more
Weigh step 2 products therefrom, add in step (1) products therefrom of equivalent, ultrasonic 0.5 hour and to stir 0.5 little
Time, end product is poured in ultra-flat surface ware, be placed in 60 DEG C of drying in baking oven, obtain pale yellow transparent film, then film is soaked
Steep in 1mol/L NaOH solution two days, obtain final anion exchange membrane.
Preferably, described in described step (1), repetitive operation is 3 times.
Preferably, halogenated alkane described in described step (2) is dibromo pentane, two bromooctanes or dibromo-dodecane.
Preferably, poly-three imidazoles benzene ionic liquids described in described step (2) are poly-1,3,5-tri-(3-amyl group-1-miaows
Azoles), poly-1,3,5-tri-(3-octyl group-1-imidazoles) or poly-1,3,5-tri-(3-dodecyl-1-imidazoles) benzene ionic liquid.
Preferably, the amount of step (1) products therefrom described in described step (3) reduces half.
The present invention compared with prior art has an obvious advantage:
1, the preparation technology of film is simple.Poly ion liquid is directly doped to polyphenylene oxide (PPO) anion exchange membrane skeleton
In, simplify the synthesis step of film.
2, the ionic conductance of film is high.The present invention, in addition to the conductivity of film self, introduces ternary poly ion liquid, each
Unit can conduct three hydroxide ions, greatly strengthen the ionic conductance of film.
3, the good stability of the dimension of film.Pure polyphenylene oxide (PPO) skeleton anion exchange film water absorbs and expansion rate is too high, easily
Fragmentation in test process.And after adding ternary poly ion liquid, tested caudacoria and can also keep relative fullness.
Below by the drawings and specific embodiments, the present invention is described in detail.It should be understood that described reality
Execute example and only relate to the preferred embodiments of the invention, in the case of without departing from the spirit and scope of the present invention, various compositions and containing
The changes and improvements of amount are all possible.
Accompanying drawing explanation
Fig. 1 is 1 that the present invention synthesizes, the nuclear magnetic resoance spectrum of 3,5-tri-(1-imidazoles) benzene, H2Correspond to benzene ring hydrogen, H1、
H3、H4Correspond to three hydrogen on imidazole ring respectively.
Fig. 2 is that the nuclear-magnetism of poly-1,3,5-tri-(3-pentyl-1-imidazoles) the benzene ionic liquid (PTPIB) that the present invention synthesizes is total to
Shake spectrum, wherein H1For benzene ring hydrogen, H2、H3、H4It is respectively three hydrogen on imidazole ring, H5、H6It is respectively and nitrogen on imidazole ring
The hydrogen on two carbon being connected, H7For other hydrogen on dodecyl chain.
Fig. 3 is that the nuclear-magnetism of poly-1,3,5-tri-(3-octyl-1-imidazoles) the benzene ionic liquid (PTOIB) that the present invention synthesizes is total to
Shake spectrum, wherein H1For benzene ring hydrogen, H2、H3、H4It is respectively three hydrogen on imidazole ring, H5、H6It is respectively and nitrogen on imidazole ring
The hydrogen on two carbon being connected, H7For other hydrogen on dodecyl chain.
Fig. 4 is the nuclear-magnetism of poly-1,3,5-tri-(3-dodecyl-1-imidazoles) the benzene ionic liquid (PTDIB) that the present invention synthesizes
Figure, wherein H1For benzene ring hydrogen, H2、H3、H4It is respectively three hydrogen on imidazole ring, H5、H6It is respectively and nitrogen phase on imidazole ring
Hydrogen on two carbon even, H7For other hydrogen on dodecyl chain.
Fig. 5 is the polyphenylene oxide N-methyl imidazole anion exchange membrane that the present invention synthesizes: the polyphenyl that N-methyl imidazoles is quaternized
The nuclear magnetic resoance spectrum of ether, wherein H1For the hydrogen on the methyl that connects on phenyl ring, H2For the hydrogen on the methyl that connects on quaternary ammonium salt, H3For benzene
The hydrogen of the methylene connected on ring, H4, H5For benzene ring hydrogen.
Fig. 6 is that the ionic conductance of the polyphenylene oxide N-methyl imidazole anion exchange membrane 1-4 that the present invention synthesizes becomes with temperature
The graph of a relation changed.
Detailed description of the invention
Comparative examples 1
1, the preparation of polyphenylene oxide (PPO) N-methyl imidazole skeleton:
Commercially available for 0.3g polyphenylene oxide is joined equipped with in the 100mL there-necked flask of agitator, condensing tube and airway, nitrogen
Under atmosphere, it is heated to 50 DEG C, after polyphenylene oxide is completely dissolved, adds the commercially available benzoyl peroxide of 4.64g (PPO) and 0.232g city
Sell N-bromo-succinimide (NBS), oil bath pan temperature is raised to 80 DEG C, after reacting 4 hours, reduce the temperature to room temperature, will be anti-
Answering thing solution to forward rotation to and steam in bottle, at 60 DEG C, rotation is steamed and is become brown color to solution colour, then precipitates in methanol, obtains light
Yellow solid, with commercially available dichloromethane faint yellow solid is dissolved, rotation is steamed, precipitation, repeats this operation 3 times, obtains pure yellowish
The bromide PPO (BPPO) of color, in an oven 60 DEG C of drying, the BPPO being dried by 0.25g is dissolved in the commercially available DMF solution of 15mL,
Until completely dissolved, add 207 μ L commercially available N-Methylimidazole., react 12 hours, by the most quaternized for bromo site, obtain formylmerphalan
The polyphenylene oxide that base imidazoles is quaternized.
As it is shown in figure 5, be the nuclear magnetic resoance spectrum of polyphenylene oxide trimethylamine film, wherein, H1For the hydrogen on the methyl that connects on phenyl ring,
H2For the hydrogen on the methyl that connects on quaternary ammonium salt, H3The hydrogen of the methylene for connecting on phenyl ring, H4, H5For benzene ring hydrogen.
2, the preparation of polyphenyl ether anion exchange membrane:
Step 1 products therefrom is poured in ultra-flat surface ware, is placed in 60 DEG C of drying in baking oven, obtains pale yellow transparent film,
Then film is soaked in 1mol/L NaOH solution two days, obtains final fuel cell polyphenyl ether anion exchange membrane
1, the thickness of film is measured with micrometer caliper.Polyphenyl ether anion exchange membrane is control sample, does not adds poly ion liquid.
Embodiment 1
1, the preparation of polyphenylene oxide (PPO) N-methyl imidazole skeleton:
Commercially available for 0.3g polyphenylene oxide is joined equipped with in the 100mL there-necked flask of agitator, condensing tube and airway, nitrogen
Under atmosphere, it is heated to 50 DEG C, after polyphenylene oxide is completely dissolved, adds the commercially available benzoyl peroxide of 4.64g (PPO) and 0.232g city
Sell N-bromo-succinimide (NBS), oil bath pan temperature is raised to 80 DEG C, after reacting 4 hours, reduce the temperature to room temperature, will be anti-
Answering thing solution to forward rotation to and steam in bottle, at 60 DEG C, rotation is steamed and is become brown color to solution colour, then precipitates in methanol, obtains light
Yellow solid, with commercially available dichloromethane faint yellow solid is dissolved, rotation is steamed, precipitation, repeats this operation 3 times, obtains pure yellowish
The bromide PPO (BPPO) of color, in an oven 60 DEG C of drying, the BPPO being dried by 0.25g is dissolved in the commercially available DMF solution of 15mL,
Until completely dissolved, add 207 μ L commercially available N-Methylimidazole., react 12 hours, by the most quaternized for bromo site, obtain formylmerphalan
The polyphenylene oxide that base imidazoles is quaternized, its nuclear magnetic resoance spectrum is as shown in Figure 5.
2, the preparation of poly-1,3,5-tri-(3-amyl group-1-imidazoles) benzene ionic liquid (PTPIB):
(1), the preparation of 1,3,5-tri-(1-imidazoles) benzene:
By commercially available for 2.52g 1,3,5-tribromo-benzenes, 5.44g commercial imidazole, the commercially available potassium carbonate of 4.42g, 0.05g commercial sulfuric acid copper
Joining in 100mL there-necked flask, be passed through nitrogen, temperature is raised to 180 DEG C, react 12 hours, then product temperatur is down to room temperature,
With 30mL deionized water wash five times, filter, collect upper strata solid, commercially available for crude product 30mL dichloromethane is extracted 5 times, receive
After collection organic layer, rotary evaporation obtains 1,3,5-tri-(1-imidazoles) benzene.
As it is shown in figure 1, be the nuclear magnetic resoance spectrum of 1,3,5-tri-(1-imidazoles) benzene, wherein, H1Correspond to benzene ring hydrogen, H2、
H3、H4Correspond to three hydrogen on imidazole ring respectively.
(2), the preparation of poly-1,3,5-tri-(3-amyl group-1-imidazoles) benzene ionic liquid (PTPIB):
Commercially available for 0.15g 1,3,5-tri-(1-imidazoles) benzene is dissolved in the commercially available N,N-dimethylformamide of 15mL (DMF) in 100 DEG C
In solution, add the commercially available dibromo pentane of 0.375g, react 12 hours, obtain yellow solid, filter and be placed in 60 DEG C of baking ovens baking
Dry, obtain poly-1,3,5-tri-(3-pentyl-1-imidazoles) benzene ionic liquid (PTPIB).
As in figure 2 it is shown, be the nuclear magnetic resoance spectrum of poly-1,3,5-tri-(3-pentyl-1-imidazoles) benzene ionic liquid (PTPIB),
Wherein, H1For benzene ring hydrogen, H2、H3、H4It is respectively three hydrogen on imidazole ring, H5、H6It is to be connected with nitrogen on imidazole ring respectively
Two carbon on hydrogen, H7For other hydrogen on dodecyl chain.
3, the preparation of many conduction sites polyphenyl ether anion exchange membrane:
Weigh step 2 products therefrom 0.003g, add in step 1 products therefrom of equivalent, ultrasonic 0.5 hour and stir
0.5 hour, end product is poured in ultra-flat surface ware, be placed in 60 DEG C of drying in baking oven, obtain pale yellow transparent film, then will
Film is soaked in 1mol/L NaOH solution two days, obtains final fuel cell many conduction sites polyphenyl ether aniones and hands over
Change film 2, measure the thickness of film with micrometer caliper.
Embodiment 2
1, the preparation of polyphenylene oxide (PPO) N-methyl imidazole skeleton:
Commercially available for 0.3g polyphenylene oxide is joined equipped with in the 100mL there-necked flask of agitator, condensing tube and airway, nitrogen
Under atmosphere, it is heated to 50 DEG C, after polyphenylene oxide is completely dissolved, adds the commercially available benzoyl peroxide of 4.64g (PPO) and 0.232g city
Sell N-bromo-succinimide (NBS), after oil bath pan temperature being raised to 80 DEG C of reactions 4 hours, reduce the temperature to room temperature, will reaction
Thing solution forwards rotation to and steams in bottle, and 60 DEG C of rotations are steamed and become brown color to solution, then precipitate in methanol, obtain faint yellow solid,
Faint yellow solid is dissolved with commercially available dichloromethane, revolves steaming, precipitation, repeat this operation 3 times, obtain pure flaxen bromo and gather
Phenylate (BPPO), in an oven 60 DEG C of drying, the BPPO being dried by 0.25g is dissolved in the commercially available DMF solution of 15mL, waits to be completely dissolved
After, add 207 μ L commercially available N-Methylimidazole., react 12 hours, by the most quaternized for bromo site, obtain N-methyl imidazoles quaternary ammonium
The polyphenylene oxide changed；
2, the preparation of poly-1,3,5-tri-(3-octyl group-1-imidazoles) benzene ionic liquid (PTOIB):
(1), the preparation of 1,3,5-tri-(1-imidazoles) benzene:
By commercially available for 2.52g 1,3,5-tribromo-benzenes, 5.44g commercial imidazole, the commercially available potassium carbonate of 4.42g, 0.05g commercial sulfuric acid copper
Joining in 100mL there-necked flask, be passed through nitrogen, temperature is raised to 180 DEG C, react 12 hours, then product temperatur is down to room temperature,
With 30mL deionized water wash five times, filter, collect upper strata solid, commercially available for crude product 30mL dichloromethane is extracted 5 times, receive
After collection organic layer, rotary evaporation obtains 1,3,5-tri-(1-imidazoles) benzene.
(2), the preparation of poly-1,3,5-tri-(3-octyl group-1-imidazoles) benzene ionic liquid (PTOIB):
Commercially available for 0.15g 1,3,5-tri-(1-imidazoles) benzene is dissolved in the commercially available N,N-dimethylformamide of 15mL (DMF) in 100 DEG C
In solution, add commercially available two bromooctanes of 0.443g, react 12 hours, obtain yellow solid, filter and be placed in 60 DEG C of baking ovens baking
Dry, obtain poly-1,3,5-tri-(3-octyl group-1-imidazoles) benzene ionic liquid (PTOIB).
As it is shown on figure 3, poly-1,3,5-tri-(3-octyl-1-imidazoles) the benzene ionic liquid (PTOIB) synthesized for the present invention
Nuclear magnetic resoance spectrum, wherein H1For benzene ring hydrogen, H2、H3、H4It is respectively three hydrogen on imidazole ring, H5、H6It is respectively and miaow
The hydrogen on two carbon that on azoles ring, nitrogen is connected, H7For other hydrogen on dodecyl chain.
3, the preparation of many conduction sites polyphenyl ether anion exchange membrane:
Weigh step 2 products therefrom 0.0038g, add in step 1 products therefrom of equivalent, ultrasonic 0.5 hour and stir
0.5 hour, end product is poured in ultra-flat surface ware, be placed in 60 DEG C of drying in baking oven, obtain pale yellow transparent film, then will
Film is soaked in 1mol/L NaOH solution two days, obtains final fuel cell many conduction sites polyphenyl ether aniones and hands over
Change film 3, measure the thickness of film with micrometer caliper.
Embodiment 3
1, the preparation of polyphenylene oxide (PPO) N-methyl imidazole skeleton:
Commercially available for 0.3g polyphenylene oxide is joined equipped with in the 100mL there-necked flask of agitator, condensing tube and airway, nitrogen
Under atmosphere, it is heated to 50 DEG C, after polyphenylene oxide is completely dissolved, adds the commercially available benzoyl peroxide of 4.64g (PPO) and 0.232g city
Sell N-bromo-succinimide (NBS), after oil bath pan temperature being raised to 80 DEG C of reactions 4 hours, reduce the temperature to room temperature, will reaction
Thing solution forwards rotation to and steams in bottle, and it is brown color that 60 DEG C of rotations are steamed to solution, then precipitates in methanol, obtains faint yellow solid, uses
Faint yellow solid is dissolved by commercially available dichloromethane, rotation is steamed, precipitation, repeats this operation 3 times, obtains pure flaxen bromo polyphenyl
Ether (BPPO), in an oven 60 DEG C of drying, the BPPO being dried by 0.25g is dissolved in the commercially available DMF solution of 15mL, waits to be completely dissolved
After, add 207 μ L commercially available N-Methylimidazole., react 12 hours, by the most quaternized for bromo site, obtain N-methyl imidazoles quaternary ammonium
The polyphenylene oxide changed；
2, the preparation of poly-1,3,5-tri-(3-octyl group-1-imidazoles) benzene ionic liquid (PTOIB):
(1), the preparation of 1,3,5-tri-(1-imidazoles) benzene:
By commercially available for 2.52g 1,3,5-tribromo-benzenes, 5.44g commercial imidazole, the commercially available potassium carbonate of 4.42g, 0.05g commercial sulfuric acid copper
Joining in 100mL there-necked flask, be passed through nitrogen, temperature is raised to 180 DEG C, react 12 hours, then product temperatur is down to room temperature,
With 30mL deionized water wash five times, filter, collect upper strata solid, commercially available for crude product 30mL dichloromethane is extracted 5 times, receive
After collection organic layer, rotary evaporation obtains end product.
(2), the preparation of poly-1,3,5-tri-(3-dodecyl-1-imidazoles) benzene ionic liquid (PTDIB):
Commercially available for 0.15g 1,3,5-tri-(1-imidazoles) benzene is dissolved in the commercially available N,N-dimethylformamide of 15mL (DMF) in 100 DEG C
In solution, add the commercially available dibromo-dodecane of 0.535g, react 12 hours, obtain yellow solid, filter and be placed in 60 DEG C of baking ovens
Dry, obtain poly-1,3,5-tri-(3-dodecyl-1-imidazoles) benzene ionic liquid (PTDIB).
As shown in Figure 4, for poly-1,3,5-tri-(3-dodecyl-1-imidazoles) benzene ionic liquid of present invention synthesis
(PTDIB) nuclear-magnetism figure, wherein H1For benzene ring hydrogen, H2、H3、H4It is respectively three hydrogen on imidazole ring, H5、H6Be respectively with
The hydrogen on two carbon that on imidazole ring, nitrogen is connected, H7For other hydrogen on dodecyl chain.
3, the preparation of many conduction sites polyphenyl ether anion exchange membrane:
Weigh step 2 products therefrom 0.0049g, add in step 1 products therefrom of equivalent, ultrasonic 0.5 hour and stir
0.5 hour, end product is poured in ultra-flat surface ware, be placed in 60 DEG C of drying in baking oven, obtain pale yellow transparent film, then will
Film is soaked in 1mol/L NaOH solution two days, obtains final fuel cell many conduction sites polyphenyl ether aniones and hands over
Change film 4, measure the thickness of film with micrometer caliper.
The amount adding step 1 products therefrom in described step 3 can reduce half.
The present invention utilizes the tape casting that film is carried out poly ion liquid doping treatment, obtain conducting more site polyphenyl ether cloudy from
Proton exchange, its preparation technology is simple, low cost.Prepared many conduction site polyphenyl ether anion exchange membrane has high-quality
The advantages such as sub-conductivity and Heat stability is good, uniformly (120～150 μm), ionic liquid doping is 1% to thickness, application prospect
Extensively, it is particularly well-suited to anion-exchange membrane fuel cells be suitable for.
Performance test:
Use electrochemistry AC impedence method, under saturation water environment, from 30 DEG C to 80 DEG C of test comparison embodiments 1 and embodiments
1-3 gained fuel cell with the ionic conductances conducting site polyphenyl ether anion exchange membrane 1-4 more, its result such as Fig. 6 institute
Show.
As shown in Figure 6, the fuel cell for present invention synthesis conducts site polyphenyl ether anion exchange membrane 1-4 with more
(i.e. the present invention synthesis polyphenylene oxide N-methyl imidazole anion exchange membrane and be separately added into poly-1,3,5-tri-(3-pentyl-1-
Imidazoles) benzene ionic liquid (PTPIB), poly-1,3,5-tri-(3-octyl-1-imidazoles) benzene ionic liquid (PTOIB), poly-1,3,5-
Three (3-dodecyl-1-imidazoles) benzene ionic liquid (PTDIB) anion exchange membrane afterwards) ionic conductance and variations in temperature
Graph of a relation.
Being explained in detail embodiments of the invention above, all embodiments are under premised on technical solution of the present invention
Implement, give detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to above-mentioned
Embodiment.
Claims (9)
1. fuel cell many conduction sites polyphenyl ether anion exchange membrane, it is characterised in that: described anion exchange
Film is by the quaternized polyphenylene oxide anion exchange membrane of the N-methyl imidazoles with following constitutional repeating unit II of 98-99 weight %
The poly ion liquid composition with structural formula I therein that is doped in 1-2 weight %:
Wherein n is the integer not less than 1, and the carbon number of straight chained alkyl is 5-12；
Wherein x is the integer not less than 0；Y is the integer not less than 0, and is 0 during x, y difference.
Fuel cell the most according to claim 1 many conduction sites polyphenyl ether anion exchange membrane, it is characterised in that:
In described constitutional repeating unit II, x:y=7:3.
Fuel cell the most according to claim 2 many conduction sites polyphenyl ether anion exchange membrane, it is characterised in that:
Described structural formula I is poly-1,3,5-tri-(3-amyl group-1-imidazoles), poly-1,3,5-tri-(3-octyl group-1-imidazoles) or poly-1,3,5-tri-
(3-dodecyl-1-imidazoles) benzene ionic liquid.
4. a fuel cell preparation method for many conduction sites polyphenyl ether anion exchange membrane, comprises the steps:
(1) synthesis of polyphenylene oxide N-methyl imidazole skeleton
Polyphenylene oxide is joined in reaction unit, under nitrogen atmosphere, be heated to 40-60 DEG C, after polyphenylene oxide is completely dissolved, add
Benzoyl peroxide and N-bromo-succinimide, be raised to 70-90 DEG C by temperature, after reacting 3-5 hour, reduces the temperature to room
Temperature, steams solution colour by reactant solution at 40-80 DEG C of backspin and becomes brown color, then precipitates in methanol, obtains yellowish
Color solid, dissolves faint yellow solid with dichloromethane, revolves steaming, precipitation, repeat this operation, obtain pure flaxen bromo and gather
Phenylate, dries, is dissolved in DMF solution, until completely dissolved, adds N-Methylimidazole., and reaction, by complete for bromo site quaternary ammonium
Change, obtain the polyphenylene oxide that N-methyl imidazoles is quaternized；
(2) preparation of poly-three imidazoles benzene ionic liquids
The preparation of () 1,3,5-tri-(1-imidazoles) benzene:
By 1,3,5-tribromo-benzenes, imidazoles, potassium carbonate and copper sulfate add in container, be passed through nitrogen, temperature is raised to 170-190
DEG C, reacting 8-16 hour, product temperatur is down to room temperature afterwards, is washed with deionized, and filters, and collects upper strata solid, will slightly produce
Thing dichloromethane extracts, after collected organic layer, and rotary evaporation, obtain 1,3,5-tri-(1-imidazoles) benzene；
The preparation of () poly-three imidazoles benzene ionic liquids:
By 1,3,5-tri-(1-imidazoles) benzene is dissolved in DMF solution in 80-120 DEG C, adds halogenated alkane, instead
Answer 6-18 hour, obtain yellow solid, filter and be placed in baking oven drying, obtain poly-three imidazoles benzene ionic liquids；
(3) conduct the preparation of site polyphenyl ether anion exchange membrane more
Weigh step (2) products therefrom, add in step (1) products therefrom of equivalent, ultrasonic agitation, end product is poured into super
In flat surface plate, it is placed in baking oven drying, obtains pale yellow transparent film, then film is soaked in NaOH solution, obtain final
Anion exchange membrane.
The fuel cell the most according to claim 4 preparation method of many conduction sites polyphenyl ether anion exchange membrane,
It is characterized in that: the time of ultrasonic agitation described in described step (3) is 0.5 hour, and described drying temperature is 60 DEG C, described
The concentration of NaOH solution is 1mol/L, and described soak time is two days.
The fuel cell the most according to claim 4 preparation method of many conduction sites polyphenyl ether anion exchange membrane,
It is characterized in that: repetitive operation described in described step (1) is 3 times.
The fuel cell the most according to claim 4 preparation method of many conduction sites polyphenyl ether anion exchange membrane,
It is characterized in that: halogenated alkane dibromo pentane, two bromooctanes or dibromo-dodecane described in described step (2).
The fuel cell the most according to claim 4 preparation method of many conduction sites polyphenyl ether anion exchange membrane,
It is characterized in that: poly-three imidazoles benzene ionic liquids described in described step (2) are poly-1,3,5-tri-(3-amyl group-1-imidazoles), gather
1,3,5-tri-(3-octyl group-1-imidazoles) or poly-1,3,5-tri-(3-dodecyl-1-imidazoles) benzene ionic liquid.
The fuel cell the most according to claim 4 preparation method of many conduction sites polyphenyl ether anion exchange membrane,
It is characterized in that: the addition of step (1) products therefrom described in described step (3) reduces half.
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