CN106832369A - Fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film and preparation method thereof - Google Patents
Fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film and preparation method thereof, belongs to polymer chemistry and Proton Exchange Membrane Fuel Cells field.The PEM includes by weight percentage：85~95% sulfonated poly aryl ether ketone sulfones and 5~15% ionic liquids；Described sulfonated poly aryl ether ketone sulfone and ionic liquid, structural formula is respectively as shown in formula I and formula II.The present invention also provides the preparation method of a kind of fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film.Sulfonated poly aryl ether ketone sulfone of the invention is 0.067S/cm~0.08S/cm with proton conductivity of the ionic liquid compoiste proton exchange film at 80 DEG C, and the Inorganic whisker type proton exchange film thickness is 50~80 μm.
Description
Technical field
The invention belongs to polymer chemistry and Proton Exchange Membrane Fuel Cells field, and in particular to a kind of fuel cell sulphur
Change PAEK sulfone and ionic liquid compoiste proton exchange film and preparation method thereof.
Background technology
PEM (PEM) is " heart " of Proton Exchange Membrane Fuel Cells (PEMFC), in general electrochmical power source
Barrier film is different, and it can not only isolate fuel and oxidant, prevent them from directly reacting, and play the work of electrolyte
With.
The Chinese patent of Publication No. CN104659395A, disclose a kind of used in proton exchange membrane fuel cell it is organic-nothing
Machine compound proton exchange membrane and preparation method thereof, the PEM is by functional polymer (such as poly- second of the side chain with N- heterocycles
Alkene pyrrolidone), heteropoly acid and skeleton polymer (such as Kynoar, polyether sulfone, polysulfones, PPSU) composition, organic-nothing
Machine compound proton exchange membrane can reach 10 in the proton conductivity of room temperature-2S/cm.Due to the Organic-inorganic composite proton conductive membrane
Proton conductivity it is relatively low, so as to influence the stability and service life of conducting film.
The content of the invention
The invention aims to provide a kind of fuel cell sulfonated poly aryl ether ketone sulfone and the compound matter of ionic liquid
Proton exchange and preparation method thereof, the composite membrane has proton conductivity and preferable thermal stability higher, and has
Good dimensional stability and mechanical performance, meanwhile, preparation method process is simple, the low cost.
Present invention firstly provides a kind of fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film,
The PEM includes following component by weight percentage：
Sulfonated poly aryl ether ketone sulfone：85~95%；
Ionic liquid：5~15%；
Described sulfonated poly aryl ether ketone sulfone and ionic liquid, structural formula is respectively as shown in formula I and formula II：
Formula I
Formula II
In formula I, m, n are number of repeat unit, m, n be >=1 integer.
The present invention also provides a kind of fuel cell sulfonated poly aryl ether ketone sulfone with ionic liquid compoiste proton exchange film
Preparation method, including it is as follows：
Step one：Sulfonated poly aryl ether ketone sulfone and ionic liquid are dissolved in solvent respectively, then mix both, mixed
Close solution；
Step 2：Mixed solution that step one is obtained is stirred 24~48 hours, obtains into film liquid, described into film liquid
Sulfonated poly aryl ether ketone sulfone and ionic liquid percentage by weight are (85~95%)：(5~15%)；
Step 3：Stream film forming is prolonged using the tape casting into film liquid by what step 2 was obtained, that is, is obtained fuel cell sulfonation and is gathered
Aryl ether ketone sulfone and ionic liquid compoiste proton exchange film.
Preferably, described sulfonated poly aryl ether ketone sulfone preparation method is：Under nitrogen protection, a is added in there-necked flask
Mol 4,4 '-difluoro benzophenone, (1-a) mol 4,4 '-sulfonation difluorodiphenyl sulfone, b mol bisphenol A monomers add after being well mixed
Enter salt forming agent, water entrainer and solvent, 120~140 DEG C of band water release water entrainer after flowing back 4~5 hours, and temperature rises to 160~175
DEG C, continue to react 4~6 hours, obtain sulfonated poly aryl ether ketone sulfone, wherein a=0.01~0.09, b=0.01~0.09.
Preferably, described solvent is DMF, DMA, 1-METHYLPYRROLIDONE
Or the one kind in dimethyl sulfoxide (DMSO).
Preferably, described water entrainer is toluene.
Preferably, the preparation method of described ionic liquid, including：
1- methylimidazoles and halogenated alkane are reacted 3 days at 60-65 DEG C, again with toluene wash-out, by product in 65-
Dried under 75 DEG C of vacuum conditions, obtain villaumite imidazole ion liquid, by above-mentioned villaumite imidazole ion liquid and double (fluoroform sulphurs
Acid) acid imide lithium salts is that solvent carries out anion exchange under agitation with water, stirring one day, stratification takes organic phase
Drying is ionic liquid in vacuum drying oven.
Preferably, described halogenated alkane is 1- chloroethanes.
Preferably, described 1- methylimidazoles and the mol ratio of halogenated alkane are 1：1.
Preferably, described villaumite imidazole ion liquid and the mol ratio of double (TFMS) acid imide lithium salts are 1：
1。
Beneficial effects of the present invention
Present invention firstly provides a kind of fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film,
The PEM includes by weight percentage：85~95% sulfonated poly aryl ether ketone sulfones and 5~15% ionic liquids：The proton is handed over
Changing in film can serve as the donor and acceptor of proton due to nitrogen-atoms, and can both receive proton can also provide proton, with sulfonic acid
New proton transmitting channel can be formed between group, then solving film dehydration under low humidity or high temperature causes proton conductivity
The problem of decline, test result indicate that：Sulfonated poly aryl ether ketone sulfone of the invention is with ionic liquid compoiste proton exchange film 80
DEG C when proton conductivity be 0.067S/cm~0.08S/cm, the Inorganic whisker type proton exchange film thickness be 50~80 μ
m。
The present invention also provides a kind of fuel cell sulfonated poly aryl ether ketone sulfone with ionic liquid compoiste proton exchange film
Preparation method, the method is to prepare sulfonated poly aryl ether ketone sulfone using solution polycondensation reaction, recycles solution blended process to prepare sulfonation
PAEK sulfone and ionic liquid compoiste proton exchange film, the method that the present invention prepares compoiste proton exchange film are simple, raw
Cycle is short is produced, raw material is easy to get, sulfonated poly aryl ether ketone sulfone is less than perfluoro sulfonic acid membrane with ionic liquid compoiste proton exchange film cost,
Still there is conductibility higher in high temperature, fuel cell field is can be applied to.
Brief description of the drawings
Fig. 1 is that sulfonated poly aryl ether ketone sulfone prepared by the embodiment of the present invention 2 is red with ionic liquid compoiste proton exchange film
External spectrum figure.
Specific embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are described with reference to embodiment, but
It is it should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention rather than to patent requirements of the present invention
Limitation.
Present invention firstly provides a kind of fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film,
The PEM includes following component by weight percentage：
Sulfonated poly aryl ether ketone sulfone：85~95%；
Ionic liquid：5~15%；
Described sulfonated poly aryl ether ketone sulfone and ionic liquid, structural formula is respectively as shown in formula I and formula II：
Formula I
Formula II
In formula I, m, n are number of repeat unit, m, n be >=1 integer.
The present invention also provides a kind of fuel cell sulfonated poly aryl ether ketone sulfone with ionic liquid compoiste proton exchange film
Preparation method, including it is as follows：
Step one：Sulfonated poly aryl ether ketone sulfone and ionic liquid are dissolved in solvent respectively, then mix both, mixed
Solution is closed, described solvent is preferably DMA (DMAc)；
Step 2：Mixed solution that step one is obtained is stirred 24~48 hours, obtains into film liquid, described into film liquid
Sulfonated poly aryl ether ketone sulfone and ionic liquid percentage by weight are (85~95%)：(5~15%)；
Step 3：Stream film forming is prolonged using the tape casting into film liquid by what step 2 was obtained, will be into film liquid in glass culture dish
Or prolong stream film forming on plate glass, and it is then placed in insulating box, dried 24 hours at 70 DEG C, dried 12 hours at 120 DEG C,
Room temperature is naturally cooled to, the demoulding in water obtains fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid composite type proton
Exchange membrane.
Sulfonated poly aryl ether ketone sulfone preparation method of the present invention is：Under nitrogen protection, a mol are added in there-necked flask
4,4 '-difluoro benzophenone, (1-a) mol 4,4 '-sulfonation difluorodiphenyl sulfone, b mol bisphenol A monomers are added into after being well mixed
Salt agent, water entrainer and solvent, 120~140 DEG C of band water release water entrainer after flowing back 4~5 hours, and temperature rises to 160~175 DEG C,
Continue to react 4~6 hours, discharge in cold water, soak 24~48 hours, distilled water is boiled 5~8 times, and dry for standby in baking oven is obtained
To sulfonated poly aryl ether ketone sulfone, wherein a=0.01~0.09, b=0.01~0.09.Described salt forming agent is preferably Carbon Dioxide
Potassium, water entrainer is preferably toluene, and solvent is preferably the high boiling solvent of more than 150 DEG C of boiling point, including but not limited to N, N- diformazans
Base formamide (DMF), DMAC N,N' dimethyl acetamide (DMAc), 1-METHYLPYRROLIDONE (NMP) or dimethyl sulfoxide (DMSO) (DMSO).Tool
The course of reaction of body is as follows：
According to the present invention, the preparation method of described ionic liquid is preferably included：
1- methylimidazoles and halogenated alkane are reacted 3 days at 60-65 DEG C, impure ionic liquid, again with toluene is generated
Wash-out, removes unreacted material, and product is dried the unnecessary toluene of removal under 65-75 DEG C of vacuum condition, obtains villaumite
Imidazole ion liquid, is that solvent is being stirred with water by above-mentioned villaumite imidazole ion liquid and double (TFMS) acid imide lithium salts
Under the conditions of carry out anion exchange, stir one day, stratification, take organic phase and dried at 60-70 DEG C in the vacuum drying oven and be
Ionic liquid.
According to the present invention, described halogenated alkane is preferably 1- chloroethanes.
According to the present invention, described 1- methylimidazoles and the mol ratio of halogenated alkane are preferably 1：1；Described villaumite imidazoles
The mol ratio of ionic liquid and double (TFMS) acid imide lithium salts is preferably 1：1.
Further detailed description is done to the present invention with reference to embodiment.
Embodiment 1
1mol 1- methylimidazoles and 1mol halogenated alkanes are reacted 3 days at 60 DEG C, impure ionic liquid is generated, then
Eluted with toluene, remove unreacted material, product is dried the unnecessary toluene of removal under 70 DEG C of vacuum conditions, obtain chlorine
Salt imidazole ion liquid, be with water by above-mentioned 1mol villaumites imidazole ion liquid and double (TFMS) the acid imide lithium salts of 1mol
Solvent carries out anion exchange under agitation, stirs one day, stratification, takes organic phase and is dried at 65 DEG C in the vacuum drying oven
It is dry to be ionic liquid.
Embodiment 2
(1) 0.95g sulfonated poly aryl ether ketones sulfone and 0.05g ionic liquids are dissolved in DMAC N,N' dimethyl acetamide (DMAc) respectively
In, the sulfonated poly aryl ether ketone sulfolane solution that concentration is 10% and the ionic liquid solution that concentration is 10% are respectively obtained, then will be upper
Two kinds of solution mixing are stated, mixed solution is obtained；
(2) mixed solution for obtaining step (1) is stirred 24 hours, obtains into film liquid, each active principle into film liquid
Percentage by weight is：
Sulfonated poly aryl ether ketone sulfone：95%；
Ionic liquid：5%；
(3) prolong stream film forming on glass culture dish into film liquid by what step (2) was obtained, be then placed in insulating box, 70
Dried 24 hours at DEG C, dried 12 hours at 120 DEG C, naturally cool to 25 DEG C, the demoulding in water obtains fuel cell use
Sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film.
By above-mentioned fuel cell with sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film 1M H2SO4It is molten
Soaked in liquid 24 hours, then soaked 24 hours in deionized water, period repeatedly changes water flushing, to wash away the H of residual2SO4,
Soak standby in deionized water by pretreated sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film.
Tested at 80 DEG C, the sulfonated poly aryl ether ketone sulfone is 0.067S/cm, thickness with the electrical conductivity of ionic liquid compoiste proton exchange film
It is 63 μm to spend, and Young's modulus at room temperature is 1648.2Mpa.Sulfonated poly aryl ether ketone sulfone and ionic liquid that embodiment 2 is obtained
As shown in figure 1, a represents sulfonated poly aryl ether ketone sulfone in figure, b represents sulfonated polyether for the infrared spectrogram of compoiste proton exchange film
Ketone sulfone and ionic liquid compoiste proton exchange film, it will be seen from figure 1 that embodiment has successfully synthesized sulfonated poly aryl ether ketone sulfone
With ionic liquid compoiste proton exchange film.
Embodiment 3
(1) 0.9g sulfonated poly aryl ether ketones sulfone and 0.1g ionic liquids are dissolved in DMAC N,N' dimethyl acetamide (DMAc) respectively
In, the sulfonated poly aryl ether ketone sulfolane solution that concentration is 10% and the ionic liquid solution that concentration is 10% are respectively obtained, then will be upper
Two kinds of solution mixing are stated, mixed solution is obtained；
(2) mixed solution for obtaining step (1) is stirred 24 hours, obtains into film liquid, each active principle into film liquid
Percentage by weight is：
Sulfonated poly aryl ether ketone sulfone：90%；
Ionic liquid：10%；
(3) prolong stream film forming on glass culture dish into film liquid by what step (2) was obtained, be then placed in insulating box, 70
Dried 24 hours at DEG C, dried 12 hours at 120 DEG C, naturally cool to 25 DEG C, the demoulding in water obtains fuel cell use
Sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film.
Gained sulfonated poly aryl ether ketone sulfone is pre-processed with ionic liquid compoiste proton exchange film according to the method for embodiment 2,
Tested at 80 DEG C, the sulfonated poly aryl ether ketone sulfone is 0.072S/cm, film with the electrical conductivity of ionic liquid compoiste proton exchange film
Thickness is 58 μm, and Young's modulus at room temperature is 1631.66Mpa.
Embodiment 4
(1) 0.85g sulfonated poly aryl ether ketones sulfone and 0.15g ionic liquids are dissolved in DMAC N,N' dimethyl acetamide (DMAc) respectively
In, the sulfonated poly aryl ether ketone sulfolane solution that concentration is 10% and the ionic liquid solution that concentration is 10% are respectively obtained, then will be upper
Two kinds of solution mixing are stated, mixed solution is obtained；
(2) mixed solution for obtaining step (1) is stirred 24 hours, obtains into film liquid, each active principle into film liquid
Percentage by weight is：
Sulfonated poly aryl ether ketone sulfone：85%；
Ionic liquid：15%；
(3) prolong stream film forming on glass culture dish into film liquid by what step (2) was obtained, be then placed in insulating box, 70
Dried 24 hours at DEG C, dried 12 hours at 120 DEG C, naturally cool to 25 DEG C, the demoulding in water obtains fuel cell use
Sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film.
Gained sulfonated poly aryl ether ketone sulfone is pre-processed with ionic liquid compoiste proton exchange film according to the method for embodiment 2,
Tested at 80 DEG C, the sulfonated poly aryl ether ketone sulfone is 0.08S/cm, film with the electrical conductivity of ionic liquid compoiste proton exchange film
Thickness is 75 μm, and Young's modulus at room temperature is 1613.18Mpa.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept, it is noted that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (9)
1. a kind of fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film, it is characterised in that the matter
Proton exchange includes following component by weight percentage：
Sulfonated poly aryl ether ketone sulfone：85~95%；
Ionic liquid：5~15%；
Described sulfonated poly aryl ether ketone sulfone and ionic liquid, structural formula is respectively as shown in formula I and formula II：
In formula I, m, n are number of repeat unit, m, n be >=1 integer.
2. a kind of fuel cell according to claim 1 is exchanged with sulfonated poly aryl ether ketone sulfone with ionic liquid composite type proton
The preparation method of film, it is characterised in that including as follows：
Step one：Sulfonated poly aryl ether ketone sulfone and ionic liquid are dissolved in solvent respectively, then mix both, obtain mixing molten
Liquid；
Step 2：Mixed solution that step one is obtained is stirred 24~48 hours, obtains into film liquid, described into sulfonation in film liquid
PAEK sulfone and ionic liquid percentage by weight are (85~95%)：(5~15%)；
Step 3：Stream film forming is prolonged using the tape casting into film liquid by what step 2 was obtained, that is, obtains fuel cell sulfonated polyether
Ketone sulfone and ionic liquid compoiste proton exchange film.
3. a kind of fuel cell according to claim 2 is exchanged with sulfonated poly aryl ether ketone sulfone with ionic liquid composite type proton
The preparation method of film, it is characterised in that described sulfonated poly aryl ether ketone sulfone preparation method is：Under nitrogen protection, in there-necked flask
A mol 4 are added, 4 '-difluoro benzophenone, (1-a) mol 4,4 '-sulfonation difluorodiphenyl sulfone, b mol bisphenol A monomers, mixing is equal
Salt forming agent, water entrainer and solvent, 120~140 DEG C of band water is added to release water entrainer after flowing back 4~5 hours after even, temperature rises to
160~175 DEG C, continue to react 4~6 hours, obtain sulfonated poly aryl ether ketone sulfone, wherein a=0.01~0.09, b=0.01~
0.09。
4. a kind of fuel cell according to claim 3 is exchanged with sulfonated poly aryl ether ketone sulfone with ionic liquid composite type proton
The preparation method of film, it is characterised in that described solvent is DMF, DMA, N- methyl
One kind in pyrrolidones or dimethyl sulfoxide (DMSO).
5. a kind of fuel cell according to claim 2 is exchanged with sulfonated poly aryl ether ketone sulfone with ionic liquid composite type proton
The preparation method of film, it is characterised in that described water entrainer is toluene.
6. a kind of fuel cell according to claim 2 is exchanged with sulfonated poly aryl ether ketone sulfone with ionic liquid composite type proton
The preparation method of film, it is characterised in that the preparation method of described ionic liquid, including：
1- methylimidazoles and halogenated alkane are reacted 3 days at 60-65 DEG C, again with toluene wash-out, by product at 65-75 DEG C
Dried under vacuum condition, obtain villaumite imidazole ion liquid, by above-mentioned villaumite imidazole ion liquid and double (TFMS) acyls
Imines lithium salts carries out anion exchange under agitation by solvent of water, stirs one day, and stratification takes organic phase in vacuum
Drying is ionic liquid in baking oven.
7. a kind of fuel cell according to claim 6 is exchanged with sulfonated poly aryl ether ketone sulfone with ionic liquid composite type proton
The preparation method of film, it is characterised in that described halogenated alkane is 1- chloroethanes.
8. a kind of fuel cell according to claim 6 is exchanged with sulfonated poly aryl ether ketone sulfone with ionic liquid composite type proton
The preparation method of film, it is characterised in that described 1- methylimidazoles and the mol ratio of halogenated alkane are 1：1.
9. a kind of fuel cell according to claim 6 is exchanged with sulfonated poly aryl ether ketone sulfone with ionic liquid composite type proton
The preparation method of film, it is characterised in that described villaumite imidazole ion liquid rubs with double (TFMS) acid imide lithium salts
You are than being 1：1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710102133.3A CN106832369A (en) | 2017-02-24 | 2017-02-24 | Fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710102133.3A CN106832369A (en) | 2017-02-24 | 2017-02-24 | Fuel cell sulfonated poly aryl ether ketone sulfone and ionic liquid compoiste proton exchange film and preparation method thereof |
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| Publication Number | Publication Date |
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| CN106832369A true CN106832369A (en) | 2017-06-13 |
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| CN107722275A (en) * | 2017-09-20 | 2018-02-23 | 长春工业大学 | New side chain sulfonated poly aryl ether ketone sulfone PEM and preparation method thereof |
| CN110862533A (en) * | 2019-11-25 | 2020-03-06 | 九江天赐高新材料有限公司 | Preparation method of polyion liquid for lithium battery polymer solid electrolyte |
| CN111313067A (en) * | 2018-12-11 | 2020-06-19 | 中国科学院大连化学物理研究所 | Composite alkaline electrolyte membrane based on ionic liquid and having electrostatic effect, and preparation and application thereof |
| CN112133946A (en) * | 2020-09-18 | 2020-12-25 | 长春工业大学 | Carboxyl-containing sulfonated polyaryletherketone sulfone/loaded phosphotungstic acid-ionic liquid metal organic framework composite membrane and preparation method thereof |
| CN112290068A (en) * | 2020-09-21 | 2021-01-29 | 长春工业大学 | Two quaternary ammonium side chain type anion exchange membranes for fuel cell and preparation method thereof |
| CN115403804A (en) * | 2022-09-11 | 2022-11-29 | 长春工业大学 | Na 7 H 2 LaW 10 O 36 Preparation method of sulfonated polyaryletherketone sulfone composite proton exchange membrane |
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| CN107722275A (en) * | 2017-09-20 | 2018-02-23 | 长春工业大学 | New side chain sulfonated poly aryl ether ketone sulfone PEM and preparation method thereof |
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| CN112133946A (en) * | 2020-09-18 | 2020-12-25 | 长春工业大学 | Carboxyl-containing sulfonated polyaryletherketone sulfone/loaded phosphotungstic acid-ionic liquid metal organic framework composite membrane and preparation method thereof |
| CN112290068A (en) * | 2020-09-21 | 2021-01-29 | 长春工业大学 | Two quaternary ammonium side chain type anion exchange membranes for fuel cell and preparation method thereof |
| CN115403804A (en) * | 2022-09-11 | 2022-11-29 | 长春工业大学 | Na 7 H 2 LaW 10 O 36 Preparation method of sulfonated polyaryletherketone sulfone composite proton exchange membrane |
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