CN107540861A - A kind of PEM with low swelling and high alcohol-rejecting ability and preparation method thereof - Google Patents

A kind of PEM with low swelling and high alcohol-rejecting ability and preparation method thereof Download PDF

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Publication number
CN107540861A
CN107540861A CN201710755693.9A CN201710755693A CN107540861A CN 107540861 A CN107540861 A CN 107540861A CN 201710755693 A CN201710755693 A CN 201710755693A CN 107540861 A CN107540861 A CN 107540861A
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pem
ether
ketone
sulfonated polyether
low swelling
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程寒松
张运丰
刘旭坡
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China University of Geosciences
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China University of Geosciences
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polyethers (AREA)

Abstract

The invention discloses a kind of PEM with low swelling and high alcohol-rejecting ability, the film forming raw material of the PEM is sulfonated polyether-ether-ketone, brominated polyphenylether and diamine base class crosslinking agent.The invention also discloses a kind of preparation method and application of the PEM with low swelling and high alcohol-rejecting ability.The present invention is reacted using the benzyl bromide a-bromotoluene of brominated polyphenylether and the amido of diamine base class crosslinking agent, it is thermally treated resulting in cross-linked structure, linear sulfonated polyether-ether-ketone is fixed using cross-linked network, semi-interpenetrating polymer network PEM is made, solve the swelling serious problems of highly sulfonated polyether-ether-ketone, while reduce the methanol crossover of film；The PEM of acquisition can be widely applied in high concentration DMFC, have higher-energy output；It is moreover, raw materials used cheap, simple and easy into mould step, it is easy to accomplish commercial applications.

Description

A kind of PEM with low swelling and high alcohol-rejecting ability and preparation method thereof
Technical field
The present invention relates to Proton Exchange Membrane Fuel Cells technical field, has low swelling and height in particular to one kind PEM of alcohol-rejecting ability and preparation method thereof.
Background technology
DMFC is a kind of device that chemical energy is directly converted into electric energy, has the spy efficiently and cleaned Point, meet the requirement of sustainable development, therefore by common concern both domestic and external.Commercialized full fluorin proton exchange film Nafion Serious Methanol permeation problems be present in series membranes, in DMFC running, serious methanol crossover meeting Reduce the service efficiency of fuel and cause cathode catalyst to be poisoned so that fuel cell can only be in methanol concentration less than 5mol/L's Under the conditions of work, reduce the energy density of fuel cell.Therefore, novel proton exchange membranes are found and substitutes Nafion, solved straight The Methanol permeation problems of methanol fuel cell are connect, turn into current study hotspot.
Sulfonated polyether-ether-ketone is a kind of proton cheap, heat endurance is good, mechanical performance is high and alcohol-rejecting ability is excellent Exchange membrane, there is the application potential for substituting Nafion.However, the electrical conductivity of sulfonated polyether-ether-ketone film, methanol crossover and mechanicalness Energy waits and depends on its sulfonation degree, and the proton conductivity compared with low sulfonation degree sulfonated polyether-ether-ketone film is relatively low, can not meet direct methanol Requirement of the fuel to battery conductive performance；Highly sulfonated can make PEM have high-quality electron conductivity, but can cause molten The problem of swollen and methanol crossover is serious, limit the practical application of sulfonated polyether-ether-ketone.
Brominated polyphenylether is a kind of industrial products, has cheap, high hydrophobic, high mechanical properties and good filming Advantage, there are many applications in PEM field.The reactivity of benzyl bromide a-bromotoluene in brominated polyphenylether molecule is very high, can with it is more Kind group, such as amido etc., reacts, can form three-dimensional net structure.Semi-interpenetrating network polymer structure is that one kind will Linear polymer chain is extended through in another Space network of polymer structure, superior low due to Space network of polymer structure Swelling behavior, high the shortcomings that being swelled of purely linear polymer separators can be effectively improved.
The content of the invention
In view of this, the embodiment provides a kind of benzyl bromide a-bromotoluene using brominated polyphenylether and diamine base class to be crosslinked The amido reaction of agent, is thermally treated resulting in cross-linked structure, linear sulfonated polyether-ether-ketone is consolidated using cross-linked structure It is fixed, and then reduce water absorption and swelling, at the same reduce methanol permeability have low swelling and high alcohol-rejecting ability PEM and Its preparation method.
Embodiments of the invention provide a kind of PEM with low swelling and high alcohol-rejecting ability, the proton exchange The film forming raw material of film is sulfonated polyether-ether-ketone, brominated polyphenylether and diamine base class crosslinking agent.
Further, the sulfonate radical of sulfonated polyether-ether-ketone, the benzyl bromide a-bromotoluene of brominated polyphenylether and diamine base in the film forming raw material The mol ratio of the amido of class crosslinking agent can make PEM have good film forming.
Further, the sulfonation degree of the sulfonated polyether-ether-ketone is changed by adjusting sulfonation temperature and sulfonation time, described The sulfonation degree of sulfonated polyether-ether-ketone is 50-80%.
Further, the Benzylphosphonium Bromide degree of the brominated polyphenylether is 50-60%.
Further, the diamine base class crosslinking agent is the fats containing two amidos, the aromatics containing two amidos Or the condensed ring quasi-molecule containing two amidos.
A kind of preparation method of the PEM with low swelling and high alcohol-rejecting ability, comprises the following steps：
S1. sulfonated polyether-ether-ketone is prepared；
S2. it is sulfonated polyether-ether-ketone prepared by step S1 is in situ with diamine base class crosslinking agent as matrix, brominated polyphenylether Heat cross-linking obtains cross-linked structure, and the cross-linked structure fixes sulfonated polyether-ether-ketone, that is, obtains having low swelling and height The PEM of alcohol-rejecting ability.
Further, in the step S1, the preparation method of sulfonated polyether-ether-ketone is：Polyether-ether-ketone particle and the concentrated sulfuric acid are added Enter into flask, mechanical agitation 6 hours at 30 DEG C, then heat to 50 DEG C, react 3 hours, reaction product is poured into frozen water In, it is multiple with milli-Q water, until solution ph is neutrality, product is dried in vacuo 24 hours at 80 DEG C, obtained required Sulfonated polyether-ether-ketone.
Further, the specific method of the step S2 is：
S2.1. brominated polyphenylether and diamine base class crosslinking agent are dissolved in 1-METHYLPYRROLIDONE, magnetic agitation 12h, Obtain homogeneous solution；
S2.2. sulfonated polyether-ether-ketone is dissolved in 1-METHYLPYRROLIDONE；
S2.3. the solution obtained step S2.1 and step S2.2 mixes, and stirs 2h, ultrasonic de-soak 15min, is cast into Film, 24h is dried in 80 DEG C of baking ovens, then 2h is dried in vacuo at 100 DEG C, the benzyl bromide a-bromotoluene and diamine base class for making brominated polyphenylether are handed over The amido of connection agent reacts, and is fixed the cross-linked structure of sulfonated polyether-ether-ketone；
S2.4. demoulding in water, and immerse in sulfuric acid solution and be acidified, with milli-Q water to neutrality, that is, obtain having low molten The PEM of swollen and high alcohol-rejecting ability.
A kind of application with low swelling and high alcohol-rejecting ability PEM, the PEM can apply to height Concentration DMFC, methanol concentration used are up to 20mol/L.
Compared with prior art, the invention has the advantages that：Utilize the benzyl bromide a-bromotoluene and diamine base of brominated polyphenylether The amido reaction of class crosslinking agent, is thermally treated resulting in cross-linked structure, and linear sulfonated polyether-ether-ketone is carried out using cross-linked network It is fixed, by linear sulfonated polyether-ether-ketone macromolecular chain run through with brominated polyphenylether and the reaction of diamine base class crosslinking agent generate three Tie up in network structure, successfully prepare semi-interpenetrating polymer network PEM, pass through the diamine base class from different structure Crosslinking agent, prepare the direct methanol fuel that the PEM with low swelling and high alcohol-rejecting ability is applied to high methanol concentration In battery, solve the swelling serious problems of highly sulfonated polyether-ether-ketone, while reduce the methanol crossover of film；The matter of acquisition Proton exchange can be widely applied in high concentration DMFC, have higher-energy output；Moreover, raw materials used valency Lattice are cheap, simple and easy into mould step, it is easy to accomplish commercial applications.
Brief description of the drawings
Fig. 1 is an a kind of flow of the preparation method of the PEM with low swelling and high alcohol-rejecting ability of the present invention Figure.
Fig. 2 is a kind of PEM with low swelling and high alcohol-rejecting ability of the present invention in room temperature, 1-20mol/L methanol DMFC polarization curve under concentration.
Fig. 3 is a kind of PEM with low swelling and high alcohol-rejecting ability of the present invention in 30-60 DEG C, 5mol/L methanol DMFC polarization curve under concentration.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to embodiment party of the present invention Formula is further described.
The embodiment provides a kind of PEM with low swelling and high alcohol-rejecting ability, the proton is handed over The film forming raw material for changing film is sulfonated polyether-ether-ketone, brominated polyphenylether and diamine base class crosslinking agent.
The amine of the sulfonate radical of sulfonated polyether-ether-ketone, the benzyl bromide a-bromotoluene of brominated polyphenylether and diamine base class crosslinking agent in film forming raw material The mol ratio of base is arranged to make PEM have good film forming, in one embodiment, the sulfonate radical of polyether-ether-ketone, The mol ratio of the benzyl bromide a-bromotoluene of brominated polyphenylether and the amido of crosslinking agent is arranged to 5：1：0.75, ensureing the condition of film forming Under, the material rate can adjust.
The sulfonation degree of sulfonated polyether-ether-ketone is changed by adjusting sulfonation temperature and sulfonation time, the sulfonated polyether-ether-ketone Sulfonation degree be 50-80%.
The Benzylphosphonium Bromide degree of brominated polyphenylether is 50-60%.
Diamine base class crosslinking agent is the fats containing two amidos, the aromatics containing two amidos or contains two amine The condensed ring quasi-molecule of base.
It refer to Fig. 1, a kind of preparation method of the PEM with low swelling and high alcohol-rejecting ability, including following step Suddenly：
S1. sulfonated polyether-ether-ketone is prepared；
The preparation method of sulfonated polyether-ether-ketone is：20g polyether-ether-ketones particle and the concentrated sulfuric acids of 200mL 95% are added to In 500mL three-necked flasks, mechanical agitation is used in course of reaction, is stirred 6 hours at 30 DEG C, then heats to 50 DEG C, reaction 3 Hour, reaction product is poured into a large amount of frozen water, it is multiple with milli-Q water, until solution ph is neutrality, by product 80 It is dried in vacuo 24 hours at DEG C, obtains required sulfonated polyether-ether-ketone.
The sulfonation degree that sulfonated polyether-ether-ketone is obtained by nuclear magnetic resonance method is 69.5%.
S2. it is sulfonated polyether-ether-ketone prepared by step S1 is in situ with diamine base class crosslinking agent as matrix, brominated polyphenylether Heat cross-linking obtains cross-linked structure, and the cross-linked structure fixes sulfonated polyether-ether-ketone, that is, obtains having low swelling and height The PEM of alcohol-rejecting ability.
Specific method is：
S2.1. brominated polyphenylether and diamine base class crosslinking agent are dissolved in 1-METHYLPYRROLIDONE, magnetic agitation 12h, Obtain homogeneous solution；
S2.2. sulfonated polyether-ether-ketone is dissolved in 1-METHYLPYRROLIDONE；
S2.3. the solution obtained step S2.1 and step S2.2 mixes, and stirs 2h, ultrasonic de-soak 15min, is cast into Film, 24h is dried in 80 DEG C of baking ovens, then 2h is dried in vacuo at 100 DEG C, the benzyl bromide a-bromotoluene and diamine base class for making brominated polyphenylether are handed over The amido of connection agent reacts, and is fixed the cross-linked structure of sulfonated polyether-ether-ketone；
S2.4. demoulding in water, and immerse in 1mol/L sulfuric acid solutions and be acidified, with milli-Q water to neutrality, that is, had There is the PEM of low swelling and high alcohol-rejecting ability.
The present invention runs through linear sulfonated polyether-ether-ketone macromolecular chain to react with brominated polyphenylether and diamine base class crosslinking agent Generate in three-dimensional net structure, successfully prepare semi-interpenetrating polymer network PEM.
In one embodiment, the fats containing two amidos are preferably butanediamine, octamethylenediamine or 2,2'- (ethylene dioxy) Double (ethamine) etc.；The aromatics containing two amidos are preferably p-phenylenediamine, m-phenylene diamine (MPD) or 2,4- diamino benzene sulfonic acids Deng；The condensed ring quasi-molecule containing two amidos is preferably double (4- aminophenyls) fluorenes of 9,9- or 9,9- double (4- aminophenyls) Fluorenes -2,7- disulfonic acid etc..
From 2,4- diamino benzene sulfonic acids as diamine base class crosslinking agent, the performance for obtaining PEM is as shown in table 1.
The performance of 1 PEM of the present invention of table
Sample Area swelling/% (60 DEG C) Methanol permeability/cm2s-1(30℃)
SPEEK films Go to sticks and staves 12.79×10-7
PEM of the present invention 47.71 4.88×10-7
The present invention effectively reduces the water absorption and swelling and methanol crossover of sulfonated polyether-ether-ketone film as seen from Table 1.
A kind of application with low swelling and high alcohol-rejecting ability PEM, the PEM can apply to highly concentrated DMFC is spent, methanol concentration used is up to 20mol/L, close to pure methanol concentration (24.8mol/L).
Performance of direct methanol fuel cells is tested：Filled using Scribner Associates Inc.805e battery testings Put, effective electrode area 5cm2, positive pole and cathode catalyst carrying capacity are respectively 2mg/cm2PtRu/C (40%Pt and 20% ) and 2mg/cm Ru2Pt/C (40%Pt).Methanol concentration used is 1mol/L, 2mol/L, 5mol/L, 10mol/ in test process L, 15mol/L and 20mol/L, methanol solution flow velocity are 1mL/min, oxygen gas flow rate 100mL/min.Matter made from the present embodiment Proton exchange can be run in high concentration methanol solution, and methanol concentration is up to 20mol/L, close to pure methanol concentration (24.8mol/ L).At room temperature, there is highest energy output, maximum power density is 5.9mW cm in 5mol/L methanol solutions-2, such as accompanying drawing 2 It is shown；Run in 60 DEG C, 5mol/L methanol solutions, maximum power density is 17.6mW cm-2, as shown in Figure 3.
The present invention is reacted using the benzyl bromide a-bromotoluene of brominated polyphenylether and the amido of diamine base class crosslinking agent, is thermally treated resulting in crosslinking Network structure, linear sulfonated polyether-ether-ketone is fixed using cross-linked network, linear sulfonated polyether-ether-ketone macromolecular chain is passed through Wear with brominated polyphenylether and the reaction of diamine base class crosslinking agent generate in three-dimensional net structure, successfully prepare Semi-IPN polymerization Thing network PEM, by the diamine base class crosslinking agent from different structure, prepare with low swelling and high alcohol-resistant performance The PEM of energy is applied in the DMFC of high methanol concentration, solves the molten of highly sulfonated polyether-ether-ketone Swollen serious problems, while reduce the methanol crossover of film；The PEM of acquisition can be widely applied to the direct first of high concentration In alcohol fuel battery, there is higher-energy output；It is moreover, raw materials used cheap, simple and easy into mould step, it is easy to accomplish Commercial applications.
In the case where not conflicting, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.

Claims (9)

  1. A kind of 1. PEM with low swelling and high alcohol-rejecting ability, it is characterised in that the film forming of the PEM Raw material is sulfonated polyether-ether-ketone, brominated polyphenylether and diamine base class crosslinking agent.
  2. 2. it is according to claim 1 with it is low swelling and high alcohol-rejecting ability PEM, it is characterised in that it is described into The mol ratio of the amido of the sulfonate radical of sulfonated polyether-ether-ketone, the benzyl bromide a-bromotoluene of brominated polyphenylether and diamine base class crosslinking agent in film raw material It is arranged to make PEM that there is good film forming.
  3. 3. the PEM according to claim 1 with low swelling and high alcohol-rejecting ability, it is characterised in that the sulphur The sulfonation degree for changing polyether-ether-ketone is changed by adjusting sulfonation temperature and sulfonation time, and the sulfonation degree of the sulfonated polyether-ether-ketone is 50-80%.
  4. 4. the PEM according to claim 1 with low swelling and high alcohol-rejecting ability, it is characterised in that the bromine The Benzylphosphonium Bromide degree for changing polyphenylene oxide is 50-60%.
  5. 5. the PEM according to claim 1 with low swelling and high alcohol-rejecting ability, it is characterised in that described double Amido class crosslinking agent is the fats containing two amidos, the aromatics containing two amidos or the condensed ring class containing two amidos Molecule.
  6. 6. a kind of preparation method of the PEM with low swelling and high alcohol-rejecting ability, it is characterised in that including following step Suddenly：
    S1. sulfonated polyether-ether-ketone is prepared；
    S2. handed over sulfonated polyether-ether-ketone prepared by step S1 as matrix, brominated polyphenylether with diamine base class crosslinking agent in-situ heat Connection obtains cross-linked structure, and the cross-linked structure fixes sulfonated polyether-ether-ketone, that is, obtains having low swelling and high resistant alcohol The PEM of performance.
  7. 7. the membrane preparation method of the proton exchange according to claim 6 with low swelling and high alcohol-rejecting ability, its feature It is, in the step S1, the preparation method of sulfonated polyether-ether-ketone is：Polyether-ether-ketone particle and the concentrated sulfuric acid are added to flask In, mechanical agitation 6 hours at 30 DEG C, 50 DEG C are then heated to, react 3 hours, reaction product is poured into frozen water, use is ultrapure Water washing is multiple, until solution ph is neutrality, product is dried in vacuo 24 hours at 80 DEG C, obtains required sulfonated polyether ether Ketone.
  8. 8. the proton exchange membrane preparation method according to claim 6 with low swelling and high alcohol-rejecting ability, its feature exist In the specific method of the step S2 is：
    S2.1. brominated polyphenylether and diamine base class crosslinking agent are dissolved in 1-METHYLPYRROLIDONE, magnetic agitation 12h, obtained Homogeneous solution；
    S2.2. sulfonated polyether-ether-ketone is dissolved in 1-METHYLPYRROLIDONE；
    S2.3. the solution obtained step S2.1 and step S2.2 mixes, and stirs 2h, ultrasonic de-soak 15min, casting film, 24h is dried in 80 DEG C of baking ovens, then 2h is dried in vacuo at 100 DEG C, makes the benzyl bromide a-bromotoluene and diamine base class crosslinking agent of brominated polyphenylether Amido react, be fixed the cross-linked structure of sulfonated polyether-ether-ketone；
    S2.4. demoulding in water, and immerse in sulfuric acid solution and be acidified, with milli-Q water to neutrality, that is, obtain having low swelling and The PEM of high alcohol-rejecting ability.
  9. 9. a kind of application with low swelling and high alcohol-rejecting ability PEM, it is characterised in that the PEM can To be up to 20mol/L applied to high concentration DMFC, methanol concentration used.
CN201710755693.9A 2017-08-29 2017-08-29 A kind of PEM with low swelling and high alcohol-rejecting ability and preparation method thereof Pending CN107540861A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103724643A (en) * 2013-12-31 2014-04-16 华北电力大学 Semi-ipn (interpenetrating polymer network) proton exchange membrane and preparation method thereof
CN106887628A (en) * 2017-01-13 2017-06-23 杭州聚力氢能科技有限公司 Polyamide/sulfonated polyether-ether-ketone compound proton exchange membrane

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103724643A (en) * 2013-12-31 2014-04-16 华北电力大学 Semi-ipn (interpenetrating polymer network) proton exchange membrane and preparation method thereof
CN106887628A (en) * 2017-01-13 2017-06-23 杭州聚力氢能科技有限公司 Polyamide/sulfonated polyether-ether-ketone compound proton exchange membrane

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHUNLIU FANG, ET AL.: "Preparation of semi-interpenetrating polymer networks with adjustable mesh", 《POLYMER》 *
方勇等: "直接甲醇燃料电池用聚合物质子交换膜的研究进展", 《高分子学报》 *

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Application publication date: 20180105