CN103490080B - Nano yttrium oxide and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives and preparation method thereof - Google Patents

Nano yttrium oxide and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives and preparation method thereof Download PDF

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CN103490080B
CN103490080B CN201310432549.3A CN201310432549A CN103490080B CN 103490080 B CN103490080 B CN 103490080B CN 201310432549 A CN201310432549 A CN 201310432549A CN 103490080 B CN103490080 B CN 103490080B
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polyphenylene sulfide
yttrium oxide
sulfonated polyphenylene
proton exchange
exchange membrane
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CN103490080A (en
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郭强
李夏
钱君质
毕宸洋
张天骄
陈新新
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University of Shanghai for Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/02—Polythioethers; Polythioether-ethers
    • 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

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Abstract

The present invention relates to a kind of nano yttrium oxide and polyphosphazene derivatives binary doped modified Sulfonated Polyphenylene Sulfide SPPS proton exchange membrane and preparation method thereof.The composition of this proton exchange membrane and mass percent are: sulfonation degree is the Sulfonated Polyphenylene Sulfide of 57% ~ 80%: 75% ~ 99%; The binary doped phase of nano yttrium oxide and polyphosphazene derivatives composition: 1% ~ 25%; Wherein nano yttrium oxide and polyphosphazene derivatives mol ratio are 1:(1 ~ 4).The present invention adopts the SPPS of medium sulfonation degree as basis material, and to overcome highly sulfonated SPPS, to there is water absorption rate too high, the shortcoming of composite membrane less stable, and ensure that composite membrane has certain water absorption rate; By nano-scale rare earth metal oxide yttrium and the binary doped mode of polyphosphazene derivatives, make SPPS matrix and this dopant material that soda acid directly occur and adopt, to improve the combination property of composite membrane.

Description

Nano yttrium oxide and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives and preparation method thereof
Technical field
The present invention relates to a kind of binary doped modified Sulfonated Polyphenylene Sulfide SPPS proton exchange membrane and preparation method thereof, particularly a kind of nano yttrium oxide and polyphosphazene derivatives binary doped modified Sulfonated Polyphenylene Sulfide SPPS proton exchange membrane and preparation method thereof.
Background technology
Sulfonated Polyphenylene Sulfide (SPPS) material becomes the research emphasis of Proton Exchange Membrane for DMFC owing to having high mechanical properties, preferably thermal stability and chemical stability.With sulfonated reagent as concentrated sulfuric acid p-poly-phenyl thioether (PPS) carries out sulfonation, sulfonic acid group is incorporated on PPS main chain, due to sulfonic group aqueous favoring and the existence of the hydrophobic phase of phenyl ring, carbon-sulfur bond etc. on polymer backbone, SPPS material can be made to have certain proton conductivity, and lower synthesis cost, good mechanical strength and the excellent thermal stability of SPPS material can meet the requirement of fuel cell to proton exchange membrane.But the sulfonation degree of this kind of material (DS) directly can affect the performance of proton exchange membrane each side, the SPPS proton exchange membrane of low DS has good mechanical strength, alcohol-rejecting ability and thermal stability, but due to the negligible amounts of sulfonic acid group, two-phase laminated flow is not obvious, its proton conductivity is not ideal enough, hinders fuel cell chemical looping reaction.And though the SPPS proton exchange membrane of high DS has higher proton conductivity, its mechanical strength reduce, water absorption rate and swellbility is too high, at high temperature SPPS can degrade in methyl alcohol, have a strong impact on the stability of film and the life-span of fuel cell.Because sulfonation degree exists conflicting effect to proton exchange membrane material performance, on the conceptual design of SPPS proton exchange membrane, usually need to consider the mode of SPPS sulfonation degree and modification, can not attend to one thing and lose sight of another.
Polyphosphazene is alternately arranged as main chain backbone, the class novel organic-inorganic polymer that is side chain with different organic groups with nitrogen phosphorus atoms list double bond.Polyphosphazene derivatives replaces diversity due to the superior compliance of its main chain and side base, promises to be the material of new class for modification direct methanol fuel cell.
Summary of the invention
An object of the present invention is to provide a kind of nano yttrium oxide and polyphosphazene derivatives binary doped modified Sulfonated Polyphenylene Sulfide SPPS proton exchange membrane
Two of object of the present invention is the preparation method providing this proton exchange membrane
A kind of nano yttrium oxide and the binary doped modified sulfonation degree polyphenylene sulfide proton exchange membrane of polyphosphazene derivatives, is characterized in that the composition of this proton exchange membrane and mass percentage are:
Sulfonated Polyphenylene Sulfide 75%-99%,
Binary doped phase 1% ~ 25%;
The structural formula of described Sulfonated Polyphenylene Sulfide is: ;
Described binary doped mutually for yittrium oxide and polyphosphazene are by 1:(1 ~ 4) the mixture of mixed in molar ratio;
Described polyphosphazene derivatives structural formula is:
。
The above-mentioned sulfonation degree being Sulfonated Polyphenylene Sulfide is 57% ~ 80%.
The particle diameter of above-mentioned yttria particles is 40 ~ 70nm.
A kind of method preparing above-mentioned nano yttrium oxide and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives; it is characterized in that the concrete steps of the method are: by Sulfonated Polyphenylene Sulfide, to be binary dopedly scattered in mutually in casting solution; be mixed with the preparation liquid that solid concentration is 5% ~ 25%, ultrasonic process makes Sulfonated Polyphenylene Sulfide can be uniformly dispersed in mutually in casting solution with binary doped; Then by preparation liquid casting film-forming, after drying, cooling, carry out taking off film, namely obtain nano yttrium oxide and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives.
Above-mentioned casting solution is: DMF DMF, DMA DMAC or dimethyl sulfoxide (DMSO) DMSO.
Sulfonation degree is sulfonic acid group number contained by 100 repetitives every in Sulfonated Polyphenylene Sulfide.
The advantage of binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of the present invention and preparation method thereof is:
1. adopt the SPPS of medium sulfonation degree as basis material, to overcome highly sulfonated SPPS, to there is water absorption rate too high, the shortcoming of composite membrane less stable, and ensure that composite membrane has certain water absorption rate;
2., by nano-scale rare earth metal oxide yttrium and the binary doped mode of polyphosphazene derivatives, make SPPS matrix and this dopant material directly acid-base reaction occur, to improve the combination property of composite membrane.
Embodiment
Embodiment one: compositing formula and the preparation technology of the present embodiment are as follows:
1. compositing formula
(1). composite membrane basis material: DS is the SPPS material of 70.2%, and mass percent is 90%.
(2). binary doped phase: nanometer Y 2o 3and polyphosphazene derivatives, mass percent is 10%, wherein Y 2o 3with the sub-liquid mole of polyphosphazene derivatives than being 1:1.
2.DS is the synthesis of the SPPS material of 70.2%: join in the there-necked flask of 1L by 20g pps powder, the 800ml concentrated sulfuric acid, mechanic whirl-nett reaction 4h under 60 ° of C, after question response liquid is cooled to room temperature, by reactant liquor by glass funnel, pour in the mixture of ice and water of 4.5L, after cooling, with a large amount of deionized water rinsing 5 times, then use the deionized water hold over night of 4.5L, then use deionized water rinse 3 times, filter out the SPPS solid of white, by product vacuumize 24h under 110 ° of C.
3. the preliminary treatment of material: by the SPPS material dry 24h under 100 ° of C after shredding, and nano yttrium oxide dry 48h under 90 ° of C after grinding.
4. the preparation of composite membrane: take 1.3802gSPPS, 0.0195gY 2o 3be placed in ground beaker, pipette 10mlDMF with pipette again to add in above-mentioned port grinding bottle, after sealing, stir 24h, then add 0.0125g polyphosphazene derivatives, continue to stir 2h, ultrasonic 1h again, gets 6.6ml preparation liquid and waters and cast from 10cm × 6cm glass plate, and glass plate is dry 20h under 50 ° of C first, then after the dry 4h of 120 ° of C, take out from baking oven, naturally cool to after room temperature until it, pour a small amount of deionized water on a glass into and carry out taking off film.
The water absorption rate of pure SPPS film under 30 ° of C is 48.32%, and methanol permeability is 1.0 × 10 -6cm 2/ s, proton conductivity is 1.03 × 10 -3s/cm; The water absorption rate of this composite membrane is 46.22%, and methanol permeability is 8.3 × 10 -7cm 2/ s, proton conductivity is 2.1 × 10 -2s/cm.
Embodiment two: compositing formula and the preparation technology of the present embodiment are as follows:
1. compositing formula
(1). composite membrane basis material: DS is the SPPS material of 72.4%, and mass percent is 90%.
(2). binary doped phase: nanometer Y 2o 3and polyphosphazene derivatives, mass percent is 10%, wherein Y 2o 3be 1:2 with polyphosphazene derivatives mol ratio.
2.DS is the synthesis of the SPPS material of 72.4%: join in the there-necked flask of 1L by 20g pps powder, the 800ml concentrated sulfuric acid, mechanic whirl-nett reaction 4h under 70 ° of C, after question response liquid is cooled to room temperature, by reactant liquor by glass funnel, pour in the mixture of ice and water of 4.5L, after cooling, with a large amount of deionized water rinsing 5 times, then use the deionized water hold over night of 4.5L, then use deionized water rinse 3 times, filter out the SPPS solid of white, by product vacuumize 24h under 110 ° of C.
3. the preliminary treatment of material: by the SPPS material dry 24h under 100 ° of C after shredding, and by the nano yttrium oxide dry 48h under 90 ° of C after grinding.
4. the preparation of composite membrane: take 1.3791gSPPS, 0.0164gY 2o 3be placed in ground beaker, pipette 10mlDMAC with pipette again to add in above-mentioned port grinding bottle, after sealing, stir 24h, then add 0.0131g polyphosphazene derivatives, continue to stir 2h, ultrasonic 1h again, gets 6.6ml preparation liquid and waters and cast from 10cm × 6cm glass plate, and glass plate is dry 20h under 50 ° of C first, then after the dry 4h of 120 ° of C, take out from baking oven, naturally cool to after room temperature until it, pour a small amount of deionized water on a glass into and carry out taking off film.
The water absorption rate of pure SPPS film under 30 ° of C is 48.32%, and methanol permeability is 1.0 × 10 -6cm 2/ s, proton conductivity is 1.03 × 10 -3s/cm; The water absorption rate of this composite membrane is 44.12%, and methanol permeability is 8.3 × 10 -7cm 2/ s, proton conductivity is 3.1 × 10 -2s/cm.
Embodiment three: compositing formula and the preparation technology of the present embodiment are as follows:
1. compositing formula
(1). composite membrane basis material: DS is the SPPS material of 74.8%, and mass percent is 90%.
(2). binary doped phase: nanometer Y 2o 3and polyphosphazene derivatives, mass percent is 10%, wherein Y 2o 3and polyphosphazene derivatives mol ratio is 1:3.
2.DS is the synthesis of the SPPS material of 74.8%: join in the there-necked flask of 1L by 20g pps powder, the 800ml concentrated sulfuric acid, mechanic whirl-nett reaction 7h under 75 ° of C, after question response liquid is cooled to room temperature, by reactant liquor by glass funnel, pour in the mixture of ice and water of 4.5L, after cooling, with a large amount of deionized water rinsing 5 times, then use the deionized water hold over night of 4.5L, then use deionized water rinse 3 times, filter out the SPPS solid of white, by product vacuumize 24h under 110 ° of C.
3. the preliminary treatment of material: by the SPPS material dry 24h under 100 ° of C after shredding, and by the nano yttrium oxide dry 48h under 80 ° of C after grinding.
4. the preparation of composite membrane: take 1.3682gSPPS, 0.0132gY 2o 3be placed in ground beaker, pipette 10mlDMSO with pipette again to add in above-mentioned port grinding bottle, after sealing, stir 24h, then add 0.0121g polyphosphazene derivatives, continue to stir 2h, ultrasonic 1h again, gets 6.6ml preparation liquid and waters and cast from 10cm × 6cm glass plate, and glass plate is dry 20h under 50 ° of C first, then after the dry 4h of 120 ° of C, take out from baking oven, naturally cool to after room temperature until it, pour a small amount of deionized water on a glass into and carry out taking off film.
The water absorption rate of pure SPPS film under 30 ° of C is 48.32%, and methanol permeability is 1.0 × 10 -6cm 2/ s, proton conductivity is 1.03 × 10 -3s/cm; The water absorption rate of this composite membrane is 40.98%, and methanol permeability is 7.9 × 10 -7cm 2/ s, proton conductivity is 3.9 × 10 -2s/cm.
Embodiment four: compositing formula and the preparation technology of the present embodiment are as follows:
1. compositing formula
(1). composite membrane basis material: DS is the SPPS material of 79.6%, and mass percent is 90%.
(2). binary doped phase: nanometer Y 2o 3and polyphosphazene derivatives, mass percent is 10%, wherein Y 2o 3and polyphosphazene derivatives body mol ratio is 1:4.
2.DS is the synthesis of the SPPS material of 79.6%: join in the there-necked flask of 1L by 20g pps powder, the 800ml concentrated sulfuric acid, mechanic whirl-nett reaction 8h under 80 ° of C, after question response liquid is cooled to room temperature, by reactant liquor by glass funnel, pour in the mixture of ice and water of 4.5L, after cooling, with a large amount of deionized water rinsing 5 times, then use the deionized water hold over night of 4.5L, then use deionized water rinse 3 times, filter out the SPPS solid of white, by product vacuumize 24h under 110 ° of C.
3. the preliminary treatment of material: by the SPPS material dry 24h under 100 ° of C after shredding, and by the nano yttrium oxide dry 48h under 80 ° of C after grinding.
4. the preparation of composite membrane: take 1.3579gSPPS, 0.0121gY 2o 3be placed in ground beaker, pipette 10mlDMSO with pipette again to add in above-mentioned port grinding bottle, after sealing, stir 24h, then add 0.0138g polyphosphazene derivatives, continue to stir 2h, ultrasonic 1h again, gets 6.6ml preparation liquid and waters and cast from 10cm × 6cm glass plate, and glass plate is dry 20h under 50 ° of C first, then after the dry 4h of 120 ° of C, take out from baking oven, naturally cool to after room temperature until it, pour a small amount of deionized water on a glass into and carry out taking off film.
The water absorption rate of pure SPPS film under 30 ° of C is 48.32%, and methanol permeability is 1.0 × 10 -6cm 2/ s, proton conductivity is 1.03 × 10 -3s/cm; The water absorption rate of this composite membrane is 38.97%, and methanol permeability is 6.9 × 10 -7cm 2/ s, proton conductivity is 4.7 × 10 -2s/cm.

Claims (5)

1. nano yttrium oxide and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives, is characterized in that the composition of this proton exchange membrane and mass percentage are:
Sulfonated Polyphenylene Sulfide 75%-99%,
Binary doped phase 1% ~ 25%;
The structural formula of described Sulfonated Polyphenylene Sulfide is: ;
Described binary doped mutually for nano yttrium oxide and polyphosphazene derivatives are by 1:(1 ~ 4) the mixture of mixed in molar ratio;
Described polyphosphazene derivatives structural formula is:
。
2. to go the nano yttrium oxide described in 1 and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives according to right, it is characterized in that the sulfonation degree of described Sulfonated Polyphenylene Sulfide is 57% ~ 80%.
3. nano yttrium oxide according to claim 1 and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives, is characterized in that the particle diameter of described nano yttrium oxide particle is 40 ~ 70nm.
4. prepare the method for nano yttrium oxide according to claim 1,2 or 3 and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives for one kind; it is characterized in that the concrete steps of the method are: by Sulfonated Polyphenylene Sulfide, to be binary dopedly scattered in mutually in casting solution; be mixed with the preparation liquid that solid concentration is 5% ~ 25%, ultrasonic process makes Sulfonated Polyphenylene Sulfide can be uniformly dispersed in mutually in casting solution with binary doped; Then by preparation liquid casting film-forming, after drying, cooling, carry out taking off film, namely obtain nano yttrium oxide and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives.
5. method according to claim 4, is characterized in that described casting solution is: DMF DMF, DMA DMAC or dimethyl sulfoxide (DMSO) DMSO.
CN201310432549.3A 2013-09-23 2013-09-23 Nano yttrium oxide and the binary doped modified Sulfonated Polyphenylene Sulfide proton exchange membrane of polyphosphazene derivatives and preparation method thereof Expired - Fee Related CN103490080B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101071873A (en) * 2007-06-06 2007-11-14 武汉理工大学 Polymer supershort fiber reinforced fuel cell proton exchange membrane and its preparing method
CN101960057A (en) * 2008-03-12 2011-01-26 松下电器产业株式会社 Fiber manufacturing method, fiber manufacturing apparatus and proton-exchange membrane fuel cell

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US20060261304A1 (en) * 2004-11-05 2006-11-23 Aspen Aerogels, Inc. Thermal management of electronic devices

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101071873A (en) * 2007-06-06 2007-11-14 武汉理工大学 Polymer supershort fiber reinforced fuel cell proton exchange membrane and its preparing method
CN101960057A (en) * 2008-03-12 2011-01-26 松下电器产业株式会社 Fiber manufacturing method, fiber manufacturing apparatus and proton-exchange membrane fuel cell

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