CN107591550A - PEM, preparation method and solid polymer fuel cell - Google Patents

PEM, preparation method and solid polymer fuel cell Download PDF

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Publication number
CN107591550A
CN107591550A CN201610522355.6A CN201610522355A CN107591550A CN 107591550 A CN107591550 A CN 107591550A CN 201610522355 A CN201610522355 A CN 201610522355A CN 107591550 A CN107591550 A CN 107591550A
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pem
decker
molecular sieve
silicon
containing sulfonic
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邵芳可
胡元帅
陈桥
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Toray Advanced Materials Research Laboratories China Co Ltd
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Toray Advanced Materials Research Laboratories China Co Ltd
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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

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Abstract

Polymer electrolyte fuel cell the invention discloses a kind of PEM with three-decker and preparation method thereof and containing the PEM.The PEM with three-decker is the film of three-decker, and in described three-decker, intermediate layer is the blended layer of thing containing sulfonic polymeric and silicon-based mesoporous molecular sieve, and both sides layer is the homosphere of the thing containing sulfonic polymeric.Excellent proton-conducting under the conditions of PEM provided by the invention with three-decker carries with low humidification, relatively low hot water swellbility.

Description

PEM, preparation method and solid polymer fuel cell
Technical field
The present invention relates to a kind of PEM with three-decker, and preparation method thereof and use the matter The solid polymer fuel cell of proton exchange.
Background technology
Fuel cell be by by electrochemical reaction oxygenated fuel, such as：Hydrogen or methanol, so as to produce electricity The electric organ of energy.Attracted attention in recent years as clean energy resource supply source.Particularly solid polymer type fires Expect battery, due to as little as about 100 DEG C of operating temperature, and there is higher energy density, it is therefore contemplated that can It is widely used in the TRT of the moving bodys such as small-scale decentralized power generating equipment and automobile, ship. In addition, the power supply as small-sized movable instrument, portable instrument also attracts attention.
Fuel electrode (anode), oxygen electrode (negative electrode) and the knot for being placed in two interelectrode PEMs Structure is referred to as membrane electrode assembly (abbreviation MEA), then forms monocell with barrier film parcel membrane electrode assembly.Again One complete fuel cell is synthesized by single battery group.
So far, perfluorinated sulfonic acid based polymer Nafion (registration mark) (E.I.Du Pont Company's system) is widely used As PEM.Nafion is very expensive because of its complicated manufacturing process, and fuel crossover rate be present The problem of high.In addition, there is also lose the mechanical strength of film, physical durability due to swelling-contraction The problem of such.Nafion softening point is low, it is impossible to uses at high temperature, using rear waste treatment and again Recycle difficult.In addition, the excellent hydrocarbon system proton of cheap and film properties as alternative Nafion is handed over The exploitation for changing membrane material has enlivened.
But these PEMs are used for solid polymer fuel cell, all existing needs to improve high temperature Under low humidified condition the problem of proton-conducting.In addition, these PEMs are in fuel cell work Undergo during high humidification-low humidification-height humidifies that there is also the problem of dimensional stability deficiency when making repeatedly. Dimensional stability deficiency is mainly manifested in the state that PEM works in high temperature and water, and film tends to In notable water absorption and swelling, when humidity change is small, film starts to shrink at from solvent swelling state.Due to PEM The change of size, apply stress in the joint of membrane-electrode assembly so that be very easy to film and electrode occur In the possibility that joint is peeled off or film is damaged, and the significantly swelling contraction that film be present may cause film Intensity reduction and the problem of cause film destroyed.
To solve these problems, being introduced into porous resin to contain in sulfonic polymer in patent document 1 improves Film strength and water absorption and swelling degree, but used PEM is similar to traditional material, still suffers from Proton conductivity is relatively low under low humidity, and leaves and need solve the problems, such as heat endurance.Patent document 2 is by alkali Property polymer poly pyrrole throat be combined PEM, by the azacyclo- of poly- pyrrole throat main chain and contain sulfonic group Polymer forms soda acid crosslinking to reduce the water absorption and swelling degree of PEM.It is not easy to solve poly- pyrrole throat The problem of dissolving, it is blended by the way that poly- pyrrole throat pre-polymer solution and thing containing sulfonic polymeric are dissolved, then is led to The method realization blending that reaction improves poly- pyrrole throat molecular weight is crossed, step is relatively complicated.And without solve because Be crosslinked certainty caused by sulfonic group consume, so as to cause PEM proton conductivity decline the problem of. Patent document 3 passes through the ultrashort fine reduction PEM of composition polymer in containing sulfonic polymer Water absorption and swelling degree, the problem of influenceing the proton conductivity of PEM there is also ultrashort fine introducing.
On the other hand, some inorganic material are also introduced into is modified to PEM.Patent document 4 Hollow mesoporous silica microsphere is incorporated into containing manufactured PEM in sulfonic polymer, in Empty mesoporous silicon dioxide micro-sphere plays water suction, the effect of water.But its water absorption and swelling degree is still higher, Do not improve, when water absorption rate is relatively low, the swellbility of film is just than relatively low, but now proton conductivity must for it So receive bad influence.
Also have to be crosslinked and introduce the method for improving PEM dimensional stability.Patent document 5 utilizes inorganic Silicon dioxide granule is crosslinked as crosslinking agent to the polyether-ether-ketone of Direct Sulfonation to be gathered to improve Direct Sulfonation The swellability of ether ether ketone, still, crosslinking cause its proton conductivity to decline, it is necessary to introduce other protons Conductor.Patent document 6 improves the water absorption and swelling of sulfonate polybenzimidazole by being crosslinked, but its is necessary Introducing heteropoly acid, which is doped, can just obtain higher proton conductivity.In actual use, PEM Proton conductivity can be reduced with the loss of heteropoly acid, lose generating capacity.
Prior art literature
Patent document 1：United States Patent (USP)：US6242135
Patent document 2：Chinese patent CN103087337A
Patent document 3：Chinese patent CN101071873A
Patent document 4：Chinese patent CN103474680A
Patent document 5：Chinese patent CN101188301A
Patent document 6：Chinese patent CN104151587A.
The content of the invention
The problem of the present invention is that solve deficiency more than of the prior art, it is an object of the present invention to provide Under a kind of low humidified condition with excellent proton conductivity and higher temperature low water absorption and swelling degree with The PEM of three-decker, the practicality that may achieve excellent mechanical strength and physical durability are excellent PEM.The proton exchange with three-decker is prepared it is a further object of the present invention to provide a kind of The method of film.In addition, the purpose of the present invention is also to provide a kind of proton friendship using this with three-decker Change the solid polymer fuel cell of film.
The PEM with three-decker of the present invention is specifically described below.
The present invention provides a kind of PEM with three-decker, in described three-decker, centre Layer is thing containing sulfonic polymeric A and silicon-based mesoporous molecular sieve B blended layer, and both sides layer is to gather containing sulfonic group Compound A homosphere.
The present invention is by further investigation, using silicon-based mesoporous molecular sieve B as additive, and containing sulfonic group Polymer A carries out blending film forming, and resulting film is as PEM in use, being protected in water absorption rate Hold in the case of being basically unchanged, the size deformation ratio of PEM can be can be effectively reduced, i.e., containing sulfonic acid Based polyalcohol A and silicon-based mesoporous molecular sieve B blend film has relatively low water absorption and swelling degree, and silicon substrate Mesopore molecular sieve B, because it has silicon and oxygen element, deleterious effect will not be produced to fuel cell. But silicon-based mesoporous molecular sieve B addition, the proton conductivity of PEM can be also reduced sometimes. By analyzing the microstructure of blend film, discovery is primarily present following two problems.First, silicon Base mesopore molecular sieve B, when its size, form and/or incorrect addition, can be broken as inorganic particle Macromolecule higher order structure when the bad A of thing containing sulfonic polymeric is separately as PEM, so as to destroy sulphur The proton transmitting channel that acidic group cluster is formed；In addition, silicon-based mesoporous molecular sieve B and thing containing sulfonic polymeric Blend film made of A, makes film become out-of-flatness sometimes, shows as the big situation of surface roughness, this Be because inorganic mesopore molecular sieve in film forming because proportion is higher, it is intended to assemble in the side of film, Either film than it is relatively thin when, mesopore molecular sieve is not completely embedded.(the Ra when its surface roughness is higher More than 0.02), now, by PEM and anode, during negative electrode component film electrode assemblie, patch be present Conjunction property generating efficiency that is bad and influenceing membrane electrode assembly.Therefore the present invention will contain sulfonic polymeric thing A with Intermediate layer of the silicon-based mesoporous molecular sieve B blends as PEM, play supporting and to improve size steady Qualitatively act on, both sides layer is the A of thing containing sulfonic polymeric homosphere.Contain sulfonic acid in the homosphere of both sides Based polyalcohol A in film forming, can guide the A of thing containing sulfonic polymeric in intermediate layer as far as possible more in addition During silicon-based mesoporous molecular sieve B, the higher order structure of its own is kept, so as to retain proton transmitting channel, is made PEM with three-decker with higher water suction dimensional stability while, it is also higher Proton conductivity.In addition, when both sides layer is homosphere, moreover it is possible to be effectively reduced the table of PEM Surface roughness, it is set preferably to be bonded electrode when being applied to polymer electrolyte fuel cell, carry The overall generating efficiency of high fuel cell.In the present invention, there is the surface of the PEM of three-decker Roughness can be by surface roughometer (Ling Hua systems society manufactures, trade name Vertscan2.0) in 5 times of mesh Measured under mirror, the surface roughness Ra of the PEM with three-decker of the invention is less than 0.015.
The PEM with three-decker of the present invention, the A of thing containing sulfonic polymeric in preferably each layer A part of segment extend into the structure of other layers.The A of thing containing sulfonic polymeric is punctured into each layer, favorably In keeping continuous proton transmitting channel, so that the PEM with three-decker is reducing suction With higher proton conductivity while water swelling degree.
Generating efficiency when in solid fuel cell is applied in order to improve PEM, in the electricity used In the case that solution material is constant, it is necessary to reduce the proton resistance of film by reducing the thickness of film as far as possible Rate, therefore the more Bao Yuehao, but simultaneously in order to obtain the mechanical strength of durable film that PEM is done, There must be certain thickness, the preferred gross thickness of the PEM of three-decker provided by the invention is 5~200 μm, intermediate layer thickness is 3~198 μm, and outer layer thickness is 1~20 μm；Further preferred proton exchange The gross thickness of film is 5~50 μm, and intermediate layer thickness is 3~48 μm, and outer layer thickness is 1~10 μm；Especially Preferable gross thickness is 10~30 μm, and intermediate layer thickness is 5~28 μm, and outer layer thickness is 1~5 μm.
When the ratio done in view of PEM is relatively thin, if silicon-based mesoporous molecular sieve B particle diameter is larger, Defect easily is introduced in intermediate layer, is unfavorable for forming proton transmitting channel；It is in addition, thick in order to obtain surface The small PEM of rugosity, using big particle diameter silicon-based mesoporous molecular sieve B when, must increase outer layer homogeneous The thickness of layer, it can make to have the swellbility of the PEM of three-decker to become big.And when silicon-based mesoporous point When son sieve particle diameter is too small, its mesoporous average pore size formed is difficult to do greatly.Therefore the silicon substrate of the present invention Mesopore molecular sieve B average grain diameter is preferably 20~1000nm, more preferably 50~800nm.
In view of the A of thing containing sulfonic polymeric enter silicon-based mesoporous molecular sieve B it is mesoporous middle when, silicon substrate be situated between Porous molecular sieve B is stronger to the A of thing containing sulfonic polymeric cage effect, has the proton exchange of three-decker Film can also reach lower water absorption and swelling degree, but the silicon-based mesoporous molecular sieve B of large aperture can compare and be difficult to Ordered structure is formed, is also easier to make duct cave in, it is advantageous to silicon-based mesoporous molecular sieve B average hole Footpath is 2~50nm, more preferably 5~20nm.
Silicon-based mesoporous molecular sieve B has a various structures, and the present invention is in order that described thing containing sulfonic polymeric A enter through it is mesoporous, currently preferred silicon-based mesoporous molecular sieve B be with mesoporous submicron order Powder body material, specific surface area is big, and mesopore orbit is regular, has powerful adsorption function.The present invention Preferable silicon-based mesoporous molecular sieve B can be enumerated as MCM-41, MCM-48, MCM-50, SBA-1, SBA-3, SBA-15 or SBA-16 one kind therein, wherein most preferably SBA-15, because it has than table Area is big, and the distribution of homogeneous channel diameter, average pore size is larger, generally 5-30nm, wall thickness and hydro-thermal The advantages that stability is very high, the A of thing containing sulfonic polymeric can be easier to enter its mesopore orbit, be advantageous to Form the organic/inorganic inierpeneirating network structure that polymer molecule beam and silicon-based mesoporous molecular sieve are formed.Polymer After being passed out of hole, hold with the polymer being wrapped in outside particle and be integrated, make outside hole in polymer and hole Polymer interconnects, and promotes molecular sieve particle to be coupled effect with the interface of polymeric matrix, thus can carry For larger support, and the A of thing containing sulfonic polymeric is not influenceed and forms proton conducting channel.
In intermediate layer of the present invention, silicon-based mesoporous molecular sieve B mass is preferably thing containing sulfonic polymeric The 0.1~30% of A mass, more preferably 0.5%~15%.Within the range, can not reduce or The overall proton conductivity of film is reduced less, while greatly reduces the water absorption and swelling degree of PEM.When Silicon-based mesoporous molecular sieve B is beyond above-mentioned content, both situations less than 0.1%, silicon-based mesoporous molecular sieve B Deficiency, water absorption and swelling degree can not reduce；On the other hand, in the situation more than 30%, silicon-based mesoporous molecule Sieve B becomes superfluous, can have a strong impact on the A of thing containing sulfonic polymeric higher order structure, influence sulfonic group shape Into cluster, cause to have the PEM entirety proton conductivity of three-decker to reduce.
In order to preferably provide support, the water absorption and swelling degree of PEM is reduced, the present invention is preferably described 20~100% in silicon-based mesoporous molecular sieve B are bonded with the A of thing containing sulfonic polymeric by sulphur amido bond.That is, The present invention has carried out aminofunctional to used silicon-based mesoporous molecular sieve B therein 20~100% and repaiied Decorations, then the sulfonic group in the silicon-based mesoporous molecular sieve B and the A of thing containing sulfonic polymeric for passing through aminofunctional Chemical bonding is formed, obtains cross-linked structure.But the formation of cross-linked structure will necessarily consume part sulfonic acid Base, and then influence proton conductivity.The present invention is according to silicon-based mesoporous molecular sieve B in sulfonic polymeric thing A Content, by controlling the silicon-based mesoporous molecular sieve B of aminofunctional to account for all silicon-based mesoporous molecular sieve B 20~100%, efficiently control the degree of cross linking so that the PEM with three-decker is with relatively low While water absorption and swelling is spent, there is higher proton conductivity.
The silicon-based mesoporous molecular sieve B of aminofunctional used in the present invention can use direct synthesis technique Or post synthesis method.Direct synthesis technique needs to add amino silicone in silicon-based mesoporous molecular sieve B preparation process Alkane coupling agent, when amino silicane coupling agent addition is higher, it is not easy to obtain the meso-hole structure of long-range order, Therefore the present invention preferably post synthesis method obtains the silicon-based mesoporous molecular sieve B of aminofunctional.Post synthesis method is Coupling reaction is carried out using the silicone hydroxyl of amino silicane coupling agent and silicon-based mesoporous molecular sieve B surface, so as to Amido functional group is grafted onto inside and outside silicon-based mesoporous molecular sieve B ducts.Described amino silicane coupling agent Gamma-aminopropyl-triethoxy-silane, γ-aminopropyltrimethoxysilane, phenylaminomethyl three can be included Methoxy silane, phenylaminomethyl triethoxysilane, aminoethyl aminoethylaminopropyl trimethoxy silane, Polyamino alkyltrialkoxysilaneand, N- β (aminoethyl)-γ-aminopropyltrimethoxysilane, N- β (ammonia second Base)-γ-aminopropyl dimethoxy silane ,-β (aminoethyl)-gamma-aminopropyl-triethoxy-silane or N- β (ammonia second Base)-γ-aminopropyl diethoxy silane.Wherein preferably by gamma-aminopropyl-triethoxy-silane or γ-aminopropyl Trimethoxy silane is modified to silicon-based mesoporous molecular sieve B.
As the A of thing containing sulfonic polymeric used in the present invention, do not limit, as long as proton can be had concurrently Power generation characteristics and the polymer of chemical stability can, for example can polymerize containing sulfonic perfluor system Thing and containing any of sulfonic hydrocarbon system polymer.Herein, so-called perfluor based polymer, representing should Most or all polymer being replaced by fluorine atoms of the hydrogen of alkyl and/or alkylidene in polymer. In this manual, the hydrogen more than 85% of the alkyl in polymer and/or alkylidene is replaced by fluorine atoms Polymer is defined as perfluor based polymer.The generation with sulfonic perfluor based polymer as the present invention Table example, Nafion (registration mark) (E.I.Du Pont Company's system), Flemion (registration mark) (Asahi Glass company can be enumerated System) and the commercially available product such as Aciplex (registration mark) (Asahi Kasei Corporation's system).As an example, these have sulfonic acid The structure of the perfluor based polymer of base can be represented with following formula N1.But used in the present invention complete Fluorine system polymer is not limited to this.
(in formula (N1), n1, n2 separately represent natural number, and k1 and k2 are separately represented 0~5 integer.)
There is sulfonic perfluor based polymer the problems such as very expensive, fuel infiltration is big be present for these, therefore, It is steady from mechanical strength, physical durability, chemistry as the A of thing containing sulfonic polymeric used in the present invention The viewpoint such as qualitative is set out, with aromatic rings and with sulfonic hydrocarbon system polymer more preferably in main chain. Aromatic rings can not only include hydrocarbon system aromatic rings, can also include hetero-aromatic ring etc..In addition, also include fat Race's unit is formed together with aromatic unit can have alkane with sulfonic polymer, aromatic unit The hydrocarbon system such as base, alkoxy, haloalkyl, aromatic series base, allyloxy base, halogen radical, nitro, cyanogen The arbitrary non-hydrocarbon system substituent such as base, amino, carboxyl, phosphonate group or hydroxyl.
As the concrete example of the polymer in main chain with aromatic rings, can enumerate has sulfone linkage in strand Polysulfones, the polyether sulfone containing ehter bond and sulfone linkage, the polyether-ketone containing ehter bond and ketonic bond, polyphenylene oxide, poly- virtue Support ether based polymer, poly arylidene thio-ester, polyphenylene sulfide, PPSS, polyparaphenylene, polyarylene, poly- Arone, polyarylene phosphine oxide, polybenzoxazole, polybenzimidazoles, polybenzothiozole, aromatic polyamide, The polymer such as polyimides, PEI or polyimide sulfones.
In addition, as the A of thing containing sulfonic polymeric used in the present invention, under the low humidified condition of raising From the viewpoint of proton-conducting and/or power generation characteristics, preferably comprise more than one containing sulfonic parent Water-based segments A 1 and more than one block copolymer without sulfonic hydrophobic chain segment A2.
In the present invention, segment refers to the part-structure in block copolymer, represent by a kind of repeat unit or What the combination of a variety of repeat units was formed, the part of number-average molecular weight more than 2000.
As the A of thing containing sulfonic polymeric used in the present invention, further preferably：Containing more than one Containing sulfonic hydrophilic segment A1, without sulfonic hydrophobic chain segment A2 and the above-mentioned segment of connection it Between attachment position block copolymer.So-called attachment position, it is defined as connection and contains sulfonic parent Water-based segments A 1 and without the position between sulfonic hydrophobic chain segment A2, the position have with containing sulphur The hydrophilic segment A1 of acidic group, without the different chemical constitutions of sulfonic hydrophobic chain segment A2.Because The attachment position can suppress the randomization as caused by ether exchange reaction, segment cut-out, side reaction Meanwhile connect different segments.The A of thing containing sulfonic polymeric of the present invention block polymer is excellent The bridging agent specific example as attachment position of choosing include but is not limited to decafluorobiphenyl, phenyl-hexafluoride, 4,4 '-difluorodiphenyl base sulfone or 2,6- difluorobenzonitriles etc..
As the A of thing containing sulfonic polymeric used in the present invention block copolymer, being will be of more than two kinds Segment incompatible with each other, i.e., containing sulfonic hydrophilic segment A1 and be free of sulfonic hydrophobic chain Section A2 is connected by attachment position, so as to be formed obtained by a polymer chain.In block copolymer In, by being interacted by the repulsion between chemically distinct segment and caused short distance, it is separated Into nanometer farmland or micron farmland comprising each segment, by grown as caused by segment covalent bond each other away from From the effect of interaction, so as to which each farmland configures in which can keep specific order.Include each segment nanometer farmland Or micron farmland farmland set and caused higher structure, be referred to as receiving phase separation structure or microphase-separated Structure, conducted for the proton of polyelectrolyte membrane, the space configuration of the proton conduction segment in film, Receive phase separation structure or micro phase separation structure becomes important.Herein, so-called farmland, represented one In bar or a plurality of polymer chain, block that similar segment aggegation forms.
The A of thing containing sulfonic polymeric used in the present invention block copolymer, containing sulfonic hydrophily chain Section A1 and without polymer higher structure be used as in sulfonic hydrophobic chain segment A2, control and receive phase separation Structure or micro phase separation structure, so as to realize durability, physical durability and the excellent matter of chemistry Sub- conductibility, high proton-conducting can also be particularly realized under low humidified condition.
By the chemical constitution of the A of thing containing the sulfonic polymeric block copolymer that suitably selects to use in invention, Segment chain length, molecular weight, ion exchange capacity etc., PEM can be controlled within the specific limits Processability, farmland size, crystallinity/amorphism, mechanical strength, proton-conducting, dimensional stability etc. are all Characteristic.
There is the effect of high proton-conducting in order to realize the present invention in the case of low humidification, containing sulfonic group Polymer A block copolymer is wherein containing sulfonic hydrophilic segment A1 much further preferably under The repeat unit shown in formula Q1 is stated,
In above-mentioned formula Q1, Z1Represent ketone group, sulfuryl, direct key ,-PO (R1)-(wherein, R1To have Machine base group) ,-(CF2)f- (integer that wherein, f is 1~5) or-C (CF3)2- in one kind；Z2Represent O Or S；M represents the one of hydrogen, metal cation, ammonium cation or the alkyl with 1~20 carbon atom Kind；M1 represents 1~4 integer；Ar1Represent the divalent organic group containing aromatic rings.
It is preferably chemically stable in order to further increase the proton-conducting under low humidified condition, due to inhaling Electronic effect and introduce segment therein with peracidity and by highdensity sulfonic group.So above-mentioned formula Q1 is preferably the repeat unit shown in following formula Q2,
In above-mentioned formula Q2, M represents hydrogen, metal cation or ammonium cation；Ar2Selected from following formulas At least one of X-1~X-4 repeat units,
In general formula X -1, Z3For one kind in ketone group, sulfuryl or direct key.
It is preferably chemically stable and due to strong intermolecular solidifying as without sulfonic hydrophobic chain segment A2 Collect power and show crystalline component units, can so obtain mechanical strength, dimensional stability and physics The block copolymer of excellent durability.
Sulfonic hydrophobic chain segment is more preferably free of by the A of thing containing sulfonic polymeric used in the present invention A2 contains the repeat unit described in following formula Q3 and/or Q4,
In formula Q3, phenyl ring can be arbitrarily substituted, but be free from sulfonic group.Z4For electron-withdrawing group； Z5For electron-withdrawing group, O or S,
In formula Q4, Z6With Z7For the divalent organic base containing aromatic ring, it can be two or more that they are each Group, but it is free from sulfonic group.A and b is each independently 1 or 2.
Formula Q3 repeat unit is due to electron-withdrawing group Z4Effect and chemical stability is excellent, and And mechanical strength and water-resistance can be improved when forming block copolymer, therefore reinforcing three-dimensional network can be formed, Realize excellent physical durability.Electron-withdrawing group Z4Specific example include-CO- ,-(CF2)n3- (its In, n3 be 1~5 integer) ,-C (CF3)2-、-SO2- or-PO (R1)-(wherein, R1For organic group) Deng.In view of chemical stability and cost, wherein, Z4More preferably-CO- or-SO2-, it is contemplated that thing Durability is managed, is most preferably-CO-.
In formula Q3, Z5For electron-withdrawing group when, specific example is included such as-CO- ,-(CF2)n4- (its In, n4 be 1~5 integer) ,-C (CF3)2-、-SO2- or-PO (R1)-(wherein, R1For organic group) Deng.But consider cost and physical durability, Z5More preferably-O- or-S-, it is most preferably-O-.
In view of physical durability and chemical stability, the component units with formula Q3 are without sulfonic group Hydrophobic chain segment A2 in ratio it is more big better, preferably 25% mole or more, further preferably It is still more preferably 75 moles of % or more for 50 moles of % or more, most preferably 90 moles of % Or more.
It is readily obtained in view of raw material, the component units of the formula Q3 more preferably have following formula Q3-1 group Into unit.In view of mechanical strength, dimensional stability, and the physical durability as caused by crystallinity, More preferably there are following formula Q3-2 component units.
As Z in formula Q46With Z7Shown preferable organic group, more preferably Z6For phenylene, Z7 For at least one of following formula X-3, X-5, X-6 and X-7.The organic group can be by beyond sulfonic group Group substitutes, and still, from the point of view of crystallinity is assigned, more preferably organic group is unsubstituted.Z6With Z7More preferably phenylene, most preferably to phenylene.
The preferred example of component units with formula Q4 includes but is not limited to following formula Q4-1 to Q4-6 etc. Component units, and the component units with formula Q4 can suitably select according to crystallinity and mechanical strength. In view of crystallinity and manufacturing cost, more preferably Q4-1, Q4-2, Q4-5 in the component units with formula Q4 Or Q4-6, most preferably formula Q4-1 or Q4-6.
Formula Q4-1 to Q4-6 is represented with contraposition, but may include other combinations when it has crystallinity Position, such as ortho position or meta.However, considering from crystallinity, preferably align.
Containing sulfonic hydrophilic segment A1, the number-average molecular weight without sulfonic hydrophobic chain segment A2, It is relevant with phase separation structure, considered based on the balance of the proton-conducting under low humidification and physical durability, More preferably more than 0.5 ten thousand, and then preferably more than 10,000, most preferably more than 1.5 ten thousand.It is in addition, more excellent Select less than 50,000, and then preferably less than 40,000, more preferably less than 30,000.
It is existing include containing sulfonic hydrophilic segment A1, without sulfonic hydrophobic chain segment A2 and The block copolymer at the attachment position between segment is connected, in polymerization, due to needing solvent soluble Limited in such synthesis, therefore it is required that all segments have dissolubility.But there is deliquescent chain Often crystallinity is bad for section, often leads to the cohesive force that polymer lacks strand, thus tough after film forming Property deficiency so that film has huge water absorption and swelling, and/or can not reach sufficient mechanical strength.This In block copolymer of the invention preferably containing sulfonic polymer A, without sulfonic hydrophobic chain segment A2 is crystalline segment.Therefore prepare it is above-mentioned without sulfonic hydrophobic chain segment A2 to be crystalline During the film of the block copolymer containing sulfonic polymer A of segment, it can utilize at least without sulfonic acid The A of thing containing the sulfonic polymeric precursors dissolving of protection group has been imported in the hydrophobic chain segment A2 of base in a solvent It is filmed, at least a portion of the protection group contained in film is deprotected to manufacture.Block Compared with random copolymer, have is become copolymer by foring the crystallization of the polymer on farmland and processability Bad tendency, it is advantageous to import protection group at least in without sulfonic hydrophobic chain segment A2 to come Processability is improved, for containing sulfonic hydrophilic segment A1, it is also preferred that being led when processability becomes bad Enter protection group.
As the specific example of the protection group used in the present invention, can include general in organic synthesis The protection group used, the protection group refer to premised on it can be removed in the stage below, temporarily import Substituent, be the high functional group of protection reactivity, it is become to react inactive group, and It can be deprotected after reaction, functional groups originally are able to the group recovered.It is anti-as such protection Should, such as document (Theodora W.Greene, Protective Groups in Organic are recorded in detail Synthesis, America, John Wiley＆Sons, Inc, 1981) in it is preferable to use.Introduce protection The stage of base, can be since monomer stage, can also be from the oligomer stage or since polymer stage. As the concrete example for enumerating protection reaction, it can include and ketone position is carried out what is protected/be deprotected with ketal Method.It can include in addition, carry out what is protected/be deprotected between sulfonic group and soluble ester derivant Method.The tert-butyl group is imported in aromatic rings as soluble base and carries out de- tert-butylation with acid and is protected Method of shield/deprotection etc..But from the viewpoint of the dissolubility to common solvent is improved, due to three-dimensional position The reason for resistance, fatty group are particularly the fatty group containing annulus preferably as protection group.From anti- Ying Xing, set out the reasons why stability, ketone position is preferably become into the method that ketal protect/be deprotected. In the present invention, can specifically enumerate send as an envoy to the monomer with ketone group in presence of an acid catalyst with dihydric alcohol The method of reaction.For example, by making 4,4 '-dihydroxy benaophenonel with dihydric alcohol in aliphatic or aromatic series Manufacture is reacted in solvent in the presence of the acid catalysts such as hydrogen bromide.Wherein, the dihydric alcohol is carbon atom The fatty alcohol of number 1~20.Its modification method be make ketone precursor compound such as 4,4 '-dihydroxy benaophenonel with Dihydric alcohol reacts in the presence of alkyl N-butyl and solid catalyst.
In the present invention, at least a portion at the ketone position protected to ketal is deprotected the side to form ketone position Method, have no particular limits.Above-mentioned deprotection reaction, can under not homogeneous or homogeneous phase condition in water and Carried out in the presence of acid, from mechanical strength, physical durability, from the viewpoint of solvent resistance, more preferably The method that acid treatment is carried out after film is shaped to.Specifically, by by the film immersion of shaping in hydrochloric acid or It in aqueous sulfuric acid, can be deprotected, to the concentration of acid, the temperature of the aqueous solution, can be fitted Work as selection.Relative to the weight ratio of the necessary acidic aqueous solution of polymer, preferably 1~100 times, but A greater amount of water can be used.Acid catalyst preferably uses under 0.1~50% weight concentration that water be present. But as the condition of deprotection, this is not limited to, sour gas, organic acid, heat treatment can be used Etc. being deprotected.
Explanation exemplified below contains sulfonic hydrophilic segment A1, without sulfonic hydrophobic chain segment A2 and the specific synthesis by the intersegmental each more than one block copolymer of joins linked up of all chains Method.But the invention is not limited in this.In addition, the block copolymer of the present invention, can pass through synthesis The block copolymer precursor containing protection group after, at least a portion of protection group for making to contain in precursor is carried out Deprotection manufacture.As the present invention block copolymer and block copolymer precursor manufacture method it is specific Example, it can include：
Method a:Make two ends that there is repeat unit and/or importing represented by-OM bases and above-mentioned formula Q1 Repeat unit represented by the above-mentioned formula Q1 of blocking group has containing sulfonic acid based compound and two ends Repeat unit represented by-OM bases and above-mentioned formula Q3 and/or Q4 and/or the above-mentioned of blocking group is imported Repeat unit represented by formula Q3 and/or Q4 does not contain sulfonic acid based compound, alternately poly- by bridging agent Close and manufacture block copolymer.
Method b：Make two ends that there is Component units and/or importing represented by-OM bases and above-mentioned formula Q1 Repeat unit represented by the above-mentioned formula Q1 of blocking group has containing sulfonic acid based compound and two ends There is repeat unit represented by-OM bases and above-mentioned formula formula Q3 and/or Q4 and/or imported blocking group Repeat unit represented by above-mentioned formula Q3 and/or Q4 does not contain sulfonic acid based compound, by bridging agent without Rule polymerize and manufacture block copolymer.
Wherein, the O of-OM bases represents oxygen, and M represents hydrogen, metal cation, ammonium cation.It is wherein golden Belong to cation preferred Na, K, Li.
The bridging agent can be decafluorobiphenyl, phenyl-hexafluoride, 4,4 '-difluorodiphenyl base sulfone or 2,6- difluoros Benzonitrile etc..
In addition, it can be more easy to obtain sequential like phase separation structure from the block copolymer obtained by alternating polymerization Consider, most preferred method a.
The A of thing containing sulfonic polymeric used in the present invention being achieved in that molecular weight, passes through polystyrene The weight average molecular weight of calibration, it is 0.1 ten thousand~5,000,000, preferably 20,000~700,000.If less than 0.1 ten thousand, then Crackle etc. occurs in PEM after shaping, and mechanical strength, physical durability, solvent resistance may Can be insufficient.On the other hand, if it exceeds 5,000,000, then dissolubility becomes insufficient, and solution glues in addition Degree uprises, and processability becomes the problems such as bad.
The method that explanation prepares the PEM of three-decker of the present invention below.Include following step Suddenly：
(1) will contain sulfonic polymeric thing A or the A of thing containing sulfonic polymeric precursors dissolving obtain in organic solvent it is molten Liquid 1, liquid film is made on base material with solution 1, is dried 10 minutes~4 hours at 40~100 DEG C, shape Into the first tunic.
(2) use and contain the A of block polymer containing sulfonic group or the A precursors of thing containing sulfonic polymeric, silicon-based mesoporous molecule B solution 2 is sieved, second layer liquid film is made on the first tunic, is dried 10 minutes at 40~100 DEG C ~4 hours, form the second tunic；
(3) third layer liquid film is formed on the second tunic with solution 1, it is small to dry 10 minutes~4 at 40~100 DEG C When, obtain three-decker film.
(4) film obtained in acid treatment step (3) is used, finally gives the PEM with three-decker.
In the method for the PEM of described preparation three-decker, the A precursors of thing containing sulfonic polymeric are In order to solve the A of thing containing sulfonic polymeric synthesis and the solubility problem before film, in synthesis, containing sulfonic acid The polymer for introducing protection group in based polyalcohol A and obtaining.During acid treatment after film forming, containing sulphur Protection group in acid-based polymer A precursors can be removed, so as to become the A of thing containing sulfonic polymeric.
As the organic solvent used in film forming, as long as sulfonic polymeric thing A can will be contained or containing sulphur Acid-based polymer A precursors dissolve, then removable solvent.It can be very good the solvent used Such as DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, METHYLPYRROLIDONE, dimethyl are sub- The aprotic polars such as sulfone, sulfolane, 1,3- dimethyl -2- imidazolidinones or HMPA are molten Agent.It can also be the mixed solvent of above solvent.In addition, in order to further improve thing containing sulfonic polymeric A or its precursor dissolubility, the grade crown ether of 18- crown ethers -6 is preferably added in a solvent.
As it was previously stated, in the method for the PEM of the preparation three-decker of the present invention, silicon-based mesoporous point Son sieve B average grain diameter is preferably 20~1000nm, more preferably 50~800nm.It is silicon-based mesoporous Molecular sieve B average pore size is preferably 2~50nm, more preferably 5~20nm.Preferable silicon substrate is situated between Porous molecular sieve B can be enumerated as MCM-41, MCM-48, MCM-50, SBA-1, SBA-3, SBA-15 Or SBA-16 one kind therein, wherein most preferably SBA-15.
In the method for the PEM of described preparation three-decker, the silicon-based mesoporous molecule in solution 2 B mass is preferably the A mass of thing containing sulfonic polymeric 0.1~30% is sieved, more preferably 0.5%~15%.
In the method for the PEM of described preparation three-decker, in order to reach lower hot water swelling Degree, preferably described silicon-based mesoporous molecular sieve B wherein 20~100% is by aminofunctional, also, for work Change amino and sulfonic reaction, form sulphur amido bond, the solution 2 adds before the second tunic is made Enter N, N '-dicarbapentaborane imidazoles.In order to be completely consumed amino and not remain small molecular weight impurity, further It is preferred that N, N ' mole ratio of the mole of-dicarbapentaborane imidazoles and amino is 1：1.
The solid content of polymer solution during present invention shaping does not limit.But from being easy to be molded and be molded The performance of film afterwards considers, preferable solid content is the weight % of 10 weight %~30.In addition, after dissolving To polymer solution 1 can carry out natural filtration or pressure filtration etc., it is different present in solution to remove Thing, this is preferable method for obtaining tough formed body.There is no special limit to filter material used herein Fixed, glass filter or metallic filter are all suitable.
The preparation method of PEM of the present invention with three-decker, to containing sulfonic polymeric The molten of silicon-based mesoporous molecular sieve B formation compositions is added in thing A or the A precursor solutions of thing containing sulfonic polymeric During liquid 2, in order to enable the A of thing containing sulfonic polymeric or the A of thing containing sulfonic polymeric precursors smoothly In the hole for entering through mesopore molecular sieve B, preferably using vacuum and ultrasonic technology.The side of ultrasonic wave one Face can eliminate air remaining in mesopore orbit, on the other hand can be dispersed by silicon-based mesoporous molecular sieve B Solution 2 in.
The preparation method of PEM of the present invention with three-decker, sulfonic acid is contained to described Based polyalcohol A and its preferred embodiment are as previously described.
The preparation method of PEM of the present invention with three-decker, the preparation of the liquid film Method does not limit, as specific example, can include rod painting, spraying, slit die coating, cutter painting, Vapour cutter painting cloth, brushing, intaglio plate coating, silk-screen printing, ink jet printing, scraper plate add roller etc., but not office It is limited to these.
The preparation method of PEM of the present invention with three-decker, preferably drying condition are The drying 10 minutes~1 hour of (1) 40~60 DEG C of step, the drying 10 minutes~1 hour of (2) 40~60 DEG C of step, The drying 10 minutes~1 hour of (3) 40~60 DEG C of step, then in 60 DEG C~100 DEG C dryings 1 hour~3 hours. Under preferable drying condition, the moiety segments of the thing containing sulfonic polymeric in each tunic can intert into other In layer, and mesopore molecular sieve will not enter homosphere substantially due to the relation of viscosity.
The preparation method of PEM of the present invention with three-decker, by controlling liquid film thick Degree realizes preferable thickness as previously described with solution solid content.Matter provided by the invention with three-decker Proton exchange has larger proton exchange capacity 0.75-2.68meq/g, high proton conductivity 1.3~7.5mS/cm.After wherein by optimizing thing containing sulfonic polymeric A and silicon-based mesoporous molecular sieve B, very To when can reach that water absorption and swelling degree is below 5% in 80 DEG C of hot water, proton conductivity remains at 6mS/cm More than.The surface roughness Ra of PEM with three-decker is less than 0.015, can be with catalyst And the fitting that electrode is splendid.
The present invention also provides a kind of solid polymer fuel cell, has three-decker containing described above PEM.
The present invention's has three-decker PEM widely used, such as the medical of artificial skin On the way, filtration applications, chlorine resistance is counter to be impregnated with film plasma exchanger resin purposes, electrochemical applications, humidification membrane, Antifog film and electrostatic prevention film etc..Wherein it is more preferably used for various electrochemical applications.As electrochemistry Purposes, the solid polymer fuel electricity for example containing this with three-decker PEM can be included Pond, redox cell, apparatus for electrolyzing or chloric alkali electrolysis device etc., wherein being most preferably to contain to be somebody's turn to do Solid polymer fuel cell with three-decker PEM.The solid polymer fuel cell Can be as the power supply source of the substitute of one-level battery or secondary battery and the fixed hair of portable apparatus Electrical equipment, including mobile phone, personal computer, PDA, TV, radio, music player, trip Gaming machine or earphone etc.；Various industrial robots；Power equipment, including wireless dust collector；Toy； And moving body, including vehicle, ship and electric car.
Specific embodiment
Embodiment is given below, and the invention will be further described, provides the purpose of these embodiments herein only It is that the present invention will be described, and does not lie in and the scope of the present invention is defined.In addition, measurement is each The condition of kind property is as follows：
(1) ion exchange capacity (IEC)
The ion exchange capacity (meq/ grams) of per unit gram is calculated by acid-base titration.Titration method passes through following (i) described in~(iv).Measure is carried out 3 times, takes its average value.
(i) carry out proton exchange and wipe the moisture on the film surface of the PEM fully washed with pure water After dry, it is dried in vacuo 12 hours at 100 DEG C, weighs weight.
(ii) 5wt% aqueous sodium persulfate solution 50mL are added in PEM, 12 hours is stood and goes forward side by side Row ion exchange.
(iii) 0.01mol/L sodium hydrate aqueous solutions are used, titrate the sulfuric acid of generation.Utilize commercially available phenolphthalein Solution 0.1w/v% will become the point of light violet magenta as terminal as indicator.
(iv) ion exchange capacity is asked by following formula.
Ion exchange capacity (IEC) (meq/g)=[concentration (mmol/mL) Х dripping quantities of sodium hydrate aqueous solution (mL) dry weight (g) of]/sample.
(2) proton conductivity
Film sample is impregnated in 25 DEG C of pure water 24 hours, is then in 80 DEG C and relative humidity Kept for 30 minutes in 25~95% constant temperature and humidity cabinet, recycle fixed potential AC impedence method measurement proton Conductivity.Use the electrochemical measurement system (Solartron 1287 manufactured by Solartron companies Electrochemical Interface and Solartron 1255B Frequency Response Analyzxer) make For measurement apparatus, current potential impedance measurement is fixed by two-terminal method, obtains proton conductivity.Exchange Amplitude is set to 50 millivolts.Test sample is 10 mm wides, 50 millimeters of long films.Measured material is by phenol Urea formaldehyde manufactures, and the part of measurement is to unclamp.Electrode uses platinum sheet (thick 100 microns, 2 sheets).Will Electrode is placed on the front and rear side of sample thin film with 10 millimeters of electrode spacing, makes parallel to each other and thin with sample The longitudinal direction of film is orthogonal.
(3) hot water swellbility
The hot water swellbility of PEM is assessed by measuring size changing rate in 80 DEG C of hot water.Will PEM is cut into 5 centimeters of wide squares, and a night is stood in 25 DEG C, the room of 55% humidity, Measurement long (L1) and width (H1), impregnate 24 hours in 25 DEG C of water, then dipping 2 is small in 80 DEG C of hot water When again rapidly with the length (L2) of vernier caliper measurement wet film and wide (H2).By (L2-L1)/L1*100% and (H2-H1) average value for the numerical value that/H1*100% is calculated is heat-resisting water swelling degree.
(4) surface roughness (Ra)
Surface roughness can pass through surface roughometer (Ling Hua systems society manufactures, trade name Vertscan2.0) With the double interferometric methods of white light, tested under 5 times of eyepieces and there is instrument to be calculated automatically.
(5) average grain diameter
Inorganic particulate is disperseed in ethanol, after sample preparation, utilizes Japanese JEOL ESEMs JSM-6700 Test, its average grain diameter is counted under × 10000 times of amplifications.Its diameter of inorganic spherical particle statistics, it is non- Its maximum draw ratio of inorganic spherical particle measurement.
(6) average pore size
Using U.S.'s Micromeritics companies specific surface area and lacunarity analysis instrument ASAP2020 in 77K The N2 adsorption-desorption isothermals of lower test sample.18 are dried before sample test under 120 DEG C of condition of high vacuum degree Hour, then tested under liquid nitrogen temperature, the average pore size of sample is calculated with BET methods.
The Nafion solution (5wt%) used in following examples, N, N ' purchase of-dicarbapentaborane imidazoles is certainly Sigma-Aldrich Reagent Companies.METHYLPYRROLIDONE is bought from traditional Chinese medicines reagent Co., Ltd.Dioxy SiClx nano-particle is purchased from Zhoushan Of Zhejiang Province Putuo Sheng Xing nano materials development corporation, Ltd., model SS1. 13X micro porous molecular sieves are purchased from Shanghai Hengye Chemical Co., Ltd., name of an article HYD10A, are ground to micron order. Silicon-based mesoporous molecular sieve MCM-41, MCM-48 and SBA-15 (b) are purchased from the limited public affairs of Shanghai brilliance chemical industry Department, the name of an article NZ-HM41-003, NZ-HM48-001 and NZ-SBA15-001b；SBA-15 (a), SBA-15 (c) is according to document (DY Zhao, Triblock copolymer syntheses of mesoporous 50 to of silica with periodic 300 angstrom pores, Science, 1998,279,548-552) self-control Obtain.Aminofunctional MCM-41, aminofunctional SBA15 according to document (McKittrick MW, Toward single-site functional materials preparation of amine-functionalized surfaces exhibiting site-isolated behavior.Chem Mater,2003,15(5):1132–1139) Self-control obtains, and amino content is respectively 1.32mmol/g and 2.57mmol/g.Table 1 lists used institute There is the physical property situation of silicon-based mesoporous molecular sieve.Group block copolymer containing sulfonic acid b1, b2 (contain following formula G1 Represent hydrophilic segment containing sulfonic group and containing following formula G2 represent be free of sulfonic hydrophobicity The G1 segments number-average molecular weight contained in segment, wherein b1 is that 20000, G2 segment number-average molecular weights are Contain G1 segment number-average molecular weights in 12000, b2,12000) G2 segment number-average molecular weights are according to special Sharp CN103814062 self-controls obtain.Group block copolymer containing sulfonic acid b1, b2 are things containing sulfonic polymeric B1 ', b2 ' (containing following formula G1 ' hydrophilic segments containing sulfonic group represented and contain following formula G2 ' tables That shows is free of sulfonic hydrophobic chain segment) precursor, film is being made in group block copolymer containing sulfonic acid b1, b2 Afterwards, by acidification, ketal protected group is removed, becomes thing containing sulfonic polymeric b1 ', b2 '.
The positive integer that M represents Na in formula G1, G1 ' or K, n5 are 15~40.
In formula G2, G2 ', n6 represents 15~40 positive integer.
The b3 of group block copolymer containing sulfonic acid (containing following formula G3 represent hydrophilic segment containing sulfonic group with Containing following formula G4 represent be free of sulfonic hydrophobic chain segment) according to patent CN103998527 oneself System obtains.
In formula G3 and G4, n6 represents 10~40 positive integer.
The b4 of group block copolymer containing sulfonic acid (as shown in following formula G5) according to patent CN103998527 from System obtains.
The inorganic particulate of table 1 collects
Embodiment 1
By 20g group block copolymers containing sulfonic acid b1 be dissolved in 80g METHYLPYRROLIDONEs (NMP) from And obtain the clear solution that solid content is 20 weight %.Obtained clear solution is used into glass fiber filter Device carries out pressure filtration, obtains solution 1.30g solution 1 is taken, wherein containing group block copolymer containing sulfonic acid B1 about 6g, 0.9g MCM-41 are added thereto, ultrasonic disperse 30 minutes, obtain solution 2.Will be molten The cast coat of liquid 1 (50 μm of thickness of liquid film) is in PET base material, after being dried 0.5 hour at 50 DEG C, Form the first tunic.By on the first tunic of the cast coat of solution 2 (200 μm of thickness of liquid film) after the drying, After being dried 1 hour at 60 DEG C, the second tunic is formed.Solution 1 is continued into cast coat (thickness of liquid film 50 μm) on the second tunic after the drying, dried 1 hour at 60 DEG C, then 3 are dried at 100 DEG C Hour.What is finally given there is three-decker film to be impregnated 24 hours in 10 weight % aqueous sulfuric acids, After carrying out proton exchange, deprotection reaction, fully washed with substantial amounts of pure water, so as to obtain that there are three layers PEM F1, the F1 performance of structure is as shown in table 2.
Embodiment 2
By 20g group block copolymers containing sulfonic acid b1 be dissolved in 80g METHYLPYRROLIDONEs (NMP) from And obtain the clear solution that solid content is 20 weight %.Obtained clear solution is used into glass fiber filter Device carries out pressure filtration, obtains solution 1.30g solution 1 is taken, wherein containing group block copolymer containing sulfonic acid B1 about 6g, 0.9g MCM-41 are added thereto, ultrasonic disperse 30 minutes, obtain solution 2.Will be molten The cast coat of liquid 1 (50 μm of thickness of liquid film) is in PET base material, after being dried 4 hours at 100 DEG C, shape Into the first tunic.By on the first tunic of the cast coat of solution 2 (200 μm of thickness of liquid film) after the drying, After being dried 4 hours at 100 DEG C, the second tunic is formed.Solution 1 is continued into cast coat (thickness of liquid film 50 μm) on the second tunic after the drying, dried 4 hours at 100 DEG C.What is finally given has three layers Structural membrane impregnates 24 hours in 10 weight % aqueous sulfuric acids, carries out proton exchange, deprotection reaction Afterwards, fully washed with substantial amounts of pure water, so as to obtain the PEM F2, F2 with three-decker Performance is as shown in table 2.
Embodiment 3
Except by the species of silicon-based mesoporous molecular sieve and dosage be changed into 0.9g MCM-48 obtain solution 2 it Outside, operate similarly to Example 1 to manufacture the performance of PEM F3, F3 with three-decker such as Shown in table 2.
Embodiment 4
Except by the species of silicon-based mesoporous molecular sieve and dosage be changed into 0.9g SBA-15 (a) obtain solution 2 it Outside, operate similarly to Example 1 to manufacture the performance of PEM F4, F4 with three-decker such as Shown in table 2.
Embodiment 5
Except by the species of silicon-based mesoporous molecular sieve and dosage be changed into 0.9g SBA-15 (b) obtain solution 2 it Outside, operate similarly to Example 1 to manufacture the performance of PEM F5, F5 with three-decker such as Shown in table 2.
Embodiment 6
Except by the species of silicon-based mesoporous molecular sieve and dosage be changed into 0.9g SBA-15 (c) obtain solution 2 it Outside, operate similarly to Example 1 to manufacture the performance of PEM F6, F6 with three-decker such as Shown in table 2.
Embodiment 7
Except by the species of silicon-based mesoporous molecular sieve and dosage be changed into 1.8g SBA-15 (c) obtain solution 2 it Outside, operate similarly to Example 1 to manufacture the performance of PEM F7, F7 with three-decker such as Table 2
Embodiment 8
Except by the species of silicon-based mesoporous molecular sieve and dosage be changed into 0.6g SBA-15 (c) obtain solution 2 it Outside, operate similarly to Example 1 to manufacture the performance of PEM F8, F8 with three-decker such as Shown in table 2.
Embodiment 9
Except by the species of silicon-based mesoporous molecular sieve and dosage be changed into 0.3g SBA-15 (c) obtain solution 2 it Outside, operate similarly to Example 1 to manufacture the PEM F9 with three-decker.F9 performance is such as Shown in table 2.
Embodiment 10
Except by the species of silicon-based mesoporous molecular sieve and dosage be changed into 0.03g SBA-15 (c) obtain solution 2 it Outside, operate similarly to Example 1 to manufacture the performance of PEM F10, F10 with three-decker As shown in table 2.
Embodiment 11
Except the species of silicon-based mesoporous molecular sieve and dosage are changed into 1.2g amination SBA-15 (c), then 0.46g N, N '-dicarbapentaborane imidazoles are added thereto to obtain outside solution 2, are operated similarly to Example 1 It is as shown in table 2 to manufacture the performance of PEM F11, F11 with three-decker.
Embodiment 12
Except the species of silicon-based mesoporous molecular sieve and dosage are changed into 0.3g amination SBA-15 (c), then 0.15g N, N '-dicarbapentaborane imidazoles is added thereto to obtain outside solution 2.Operate similarly to Example 1 To manufacture the PEM F12 with three-decker.F12 performance is as shown in table 1.
Embodiment 13
Except the species of silicon-based mesoporous molecular sieve and dosage are changed into 0.03g amination SBA-15 (c), then 0.02g N, N '-dicarbapentaborane imidazoles are added thereto to obtain outside solution 2, are operated similarly to Example 1 It is as shown in table 2 to manufacture the performance of PEM F13, F13 with three-decker.
Embodiment 14
Except the species of silicon-based mesoporous molecular sieve and dosage are changed into 0.24g SBA-15 (c) and 0.06g amino Change SBA-15 (c), then add 0.03g N, N '-dicarbapentaborane imidazoles thereto and obtain outside solution 2, with Embodiment 1 is equally operated to manufacture the performance such as table 2 of PEM F14, F14 with three-decker It is shown.
Embodiment 15
Except the species of silicon-based mesoporous molecular sieve and dosage are changed into 0.24g MCM-41 and 0.06g amino Change MCM-41, then add 0.03g N, N '-dicarbapentaborane imidazoles thereto and obtain outside solution 2, with Embodiment 1 is equally operated to manufacture the PEM F15 with three-decker.F15 performance such as table 2 It is shown.
Embodiment 16
Outside the b1 of group block copolymer containing sulfonic acid being replaced with the b2 of group block copolymer containing sulfonic acid, and by silicon substrate The species and dosage of mesopore molecular sieve are changed into 0.24g SBA-15 (c) and 0.06g amination SBA-15 (c), so Add 0.03g N, N '-dicarbapentaborane imidazoles thereto afterwards and obtain solution 2, operate similarly to Example 1 to make The performance for making PEM F16, F16 with three-decker is as shown in table 2.
Embodiment 17
Outside the b1 of group block copolymer containing sulfonic acid being replaced with the b2 of group block copolymer containing sulfonic acid, and by silicon substrate The species and dosage of mesopore molecular sieve are changed into 0.18g SBA-15 (c) and 0.12g amination SBA-15 (c), Then 0.06g N, N '-dicarbapentaborane imidazoles are added thereto and obtains solution 2, and operation similarly to Example 1 comes PEM F17, F17 of the manufacture with three-decker performance are as shown in table 2.
Embodiment 18
Outside the b1 of group block copolymer containing sulfonic acid being replaced with the b2 of group block copolymer containing sulfonic acid, and by silicon substrate The species and dosage of mesopore molecular sieve are changed into 0.06g SBA-15 (c) and 0.24g amination SBA-15 (c), Then 0.12g N, N '-dicarbapentaborane imidazoles are added thereto and obtains solution 2, are then grasped similarly to Example 1 Make to manufacture the PEM F18 with three-decker.F18 performance is as shown in table 2.
Embodiment 19
Outside the b1 of group block copolymer containing sulfonic acid being replaced with the b3 of group block copolymer containing sulfonic acid, and by silicon substrate The species and dosage of mesopore molecular sieve are changed into 0.24g SBA-15 (c) and obtain solution 2, similarly to Example 1 Operation is as shown in table 2 to manufacture the performance of PEM F19, F19 with three-decker.
Embodiment 20
Replaced with the b3 of group block copolymer containing sulfonic acid outside b1 containing sulfonic group, and by silicon-based mesoporous molecular sieve Species and dosage be changed into 0.24g amination SBA-15 (c), then add thereto 0.12g N, N '- Dicarbapentaborane imidazoles obtains solution 2, operates handed over to manufacture the proton with three-decker similarly to Example 1 The performance for changing film F20, F20 is as shown in table 2.
Embodiment 21
Outside the b1 of group block copolymer containing sulfonic acid being replaced with the b3 of group block copolymer containing sulfonic acid, and by silicon substrate The species and dosage of mesopore molecular sieve are changed into 0.06g SBA-15 (c) and 0.24g amination SBA-15 (c), so Add 0.12g N, N '-dicarbapentaborane imidazoles thereto afterwards and obtain solution 2, operate similarly to Example 1 to make The performance for making PEM F21, F21 with three-decker is as shown in table 2.
Embodiment 22
Outside the b1 of group block copolymer containing sulfonic acid being replaced with the b4 of group block copolymer containing sulfonic acid, and by silicon substrate The species and dosage of mesopore molecular sieve are changed into 0.06g SBA-15 (c) and 0.24g amination SBA-15 (b), Then 0.12g N, N '-dicarbapentaborane imidazoles are added thereto and obtains solution 2, and operation similarly to Example 1 comes PEM F22, F22 of the manufacture with three-decker performance are as shown in table 1.
Embodiment 23
Replaced with Nafion solution in embodiment 1 outside solution 1, and take 30g nafion solution, Xiang Zhong Add the 0.015g SBA-15 (c) and 0.06g amination SBA-15 (c) of silicon-based mesoporous molecular sieve, Ran Houxiang Wherein add 0.12g N, N '-dicarbapentaborane imidazoles and obtain solution 2, operate similarly to Example 1 to manufacture tool There are the PEM F23, F23 of three-decker performance as shown in table 2.
Comparative example 1
By the 1 direct cast coat of solution (300 μm of thickness of liquid film) in embodiment 1 in PET base material, After being dried 1 hour at 60 DEG C, then dried 3 hours at 100 DEG C, the single layer structure film finally given Impregnate 24 hours in 10 weight % aqueous sulfuric acids, after carrying out proton exchange, deprotection reaction, use Substantial amounts of pure water fully washs, so as to obtain the PEM F1 ', F1 ' of single layer structure performance such as table Shown in 2.
Comparative example 2
By the 1 direct cast coat of solution (300 μm of thickness of liquid film) in embodiment 16 in PET base material, After being dried 1 hour at 60 DEG C, then dried 3 hours at 100 DEG C, the single layer structure film finally given Impregnate 24 hours in 10 weight % aqueous sulfuric acids, after carrying out proton exchange, deprotection reaction, use Substantial amounts of pure water fully washs, so as to obtain the PEM F2 ', F2 ' of single layer structure performance such as table Shown in 2.
Comparative example 3
By the 1 direct cast coat of solution (300 μm of thickness of liquid film) in embodiment 19 in PET base material, After being dried 1 hour at 60 DEG C, then dried 3 hours at 100 DEG C, the single layer structure film finally given Impregnate 24 hours in 10 weight % aqueous sulfuric acids, after carrying out proton exchange, deprotection reaction, use Substantial amounts of pure water fully washs, so as to obtain the PEM F3 ', F3 ' of single layer structure performance such as table Shown in 2.
Comparative example 4
By the 1 direct cast coat of solution (300 μm of thickness of liquid film) in embodiment 22 in PET base material, After being dried 1 hour at 60 DEG C, then dried 3 hours at 100 DEG C, the single layer structure film finally given Impregnate 24 hours in 10 weight % aqueous sulfuric acids, after carrying out proton exchange, deprotection reaction, use Substantial amounts of pure water fully washs, so as to obtain the PEM F4 ', F4 ' of single layer structure performance such as table Shown in 2.
Comparative example 5
By the 1 direct cast coat of solution (300 μm of thickness of liquid film) in embodiment 23 in PET base material, After being dried 1 hour at 60 DEG C, then dried 3 hours at 100 DEG C, the single layer structure film finally given Impregnate 24 hours in 10 weight % aqueous sulfuric acids, after carrying out proton exchange, deprotection reaction, use Substantial amounts of pure water fully washs, so as to obtain the PEM F5 ', F5 ' of single layer structure performance such as table Shown in 2.
Comparative example 6
Solution 2 in embodiment 1 (is contained relative to the weight %'s of the b1 of block polymer containing sulfonic group 30 MCM-41).Direct cast coat (300 μm of thickness of liquid film) dries 1 in PET base material at 60 DEG C After hour, then dried 3 hours at 100 DEG C, the single layer structure film finally given is in 10 weight % sulfuric acid Impregnate 24 hours in the aqueous solution, after carrying out proton exchange, deprotection reaction, fully washed with substantial amounts of pure water Wash, it is as shown in table 2 so as to obtain the PEM F6 ', F6 ' of single layer structure performance.
Comparative example 7
Solution 2 in embodiment 14 (is contained relative to the weight %'s of the b1 of block polymer containing sulfonic group 30 SBA-15(c).Direct cast coat (300 μm of thickness of liquid film) dries 1 in PET base material at 60 DEG C After hour, then dried 3 hours at 100 DEG C, the single layer structure film finally given is in 10 weight % sulfuric acid Impregnate 24 hours in the aqueous solution, after carrying out proton exchange, deprotection reaction, fully washed with substantial amounts of pure water Wash, it is as shown in table 2 so as to obtain the PEM F7 ', F7 ' of single layer structure performance.
Comparative example 8
By the solution 2 in embodiment 18, direct cast coat (300 μm of thickness of liquid film) in PET base material, After being dried 1 hour at 60 DEG C, then dried 3 hours at 100 DEG C, the single layer structure film finally given Impregnate 24 hours in 10 weight % aqueous sulfuric acids, after carrying out proton exchange, deprotection reaction, use Substantial amounts of pure water fully washs, so as to obtain the PEM F8 ', F8 ' of single layer structure performance such as table Shown in 2.
Comparative example 9
It is same with embodiment 1 in addition to the species of inorganic particulate and dosage are changed into 0.9g nano silicons Sample operation is as shown in table 2 to manufacture the performance of PEM F9 ', F9 ' with three-decker.
Comparative example 10
In addition to the species of inorganic particulate and dosage are changed into 0.9g 13X micro porous molecular sieves, with embodiment 1 Same operation is as shown in table 2 to manufacture the performance of PEM F10 ', F10 ' with three-decker.
Table 2
According to table 2, individual layer PEM (comparative example 1~5) is made compared to identical thing containing sulfonic polymeric, The water absorption and swelling degree of the PEM with three-decker containing silicon-based mesoporous molecular sieve substantially reduces .(compare compared to the PEM with three-decker of nano silicon and micro porous molecular sieve Example 9~10), the water absorption and swelling degree drop of the PEM with three-decker containing silicon-based mesoporous molecular sieve It is low to become apparent from and maintain higher proton conductivity, because the hole that silicon-based mesoporous molecular sieve has is big Small suitable, thing containing sulfonic polymeric can be entered in hole, form cage effect, molten so as to be absorbed water to it It is swollen to cause to limit, while part thing containing sulfonic polymeric can pass through silicon-based mesoporous molecular sieve, proton transport Passage can retain, therefore possess higher proton conductivity.Compared to comprising only silicon-based mesoporous molecular sieve Single layer structure PEM (comparative example 6~8), the PEM with three-decker is with lower Surface roughness, and there is higher proton conductivity, because the thing containing sulfonic polymeric of both sides The silicon-based mesoporous molecular sieve that efficiently solves of homogeneous layer formed in intermediate layer uneven, induce simultaneously Intermediate layer forms more proton transmitting channels.When shape between thing containing sulfonic polymeric and mesopore molecular sieve After being bonded into sulphur amido bond, water absorption and swelling limitation of the silicon-based mesoporous molecular sieve to the thing containing sulfonic polymeric is brighter It is aobvious so that PEM water absorption and swelling degree becomes smaller, and embodiment 17 and embodiment 18 are by preferred Thing containing sulfonic polymeric and silicon-based mesoporous molecular sieve, and control mesopore molecular sieve and amination mesopore molecular sieve Ratio, so as to control sulphur amido bond be bonded degree, obtain optimal combination property：Higher matter Sub- conductivity, relatively low swelling and relatively low surface roughness.

Claims (21)

  1. A kind of 1. PEM with three-decker, it is characterised in that：In three-decker, intermediate layer is containing sulfonic acid Based polyalcohol A and silicon-based mesoporous molecular sieve B blended layer, both sides layer are the A of thing containing sulfonic polymeric homogeneous Layer.
  2. A kind of 2. PEM with three-decker according to claim 1, it is characterised in that：The silicon Base mesopore molecular sieve B average grain diameters are 20~1000nm, and average pore size is 2~50nm.
  3. A kind of 3. PEM with three-decker according to claim 2, it is characterised in that：Described Silicon-based mesoporous molecular sieve B is SBA-15.
  4. A kind of 4. PEM with three-decker according to claim 1, it is characterised in that：Described In intermediate layer, silicon-based mesoporous molecular sieve B mass is the 0.1~30% of the A mass of thing containing sulfonic polymeric.
  5. A kind of 5. PEM with three-decker according to claim 1, it is characterised in that：The silicon 20~100% in base mesopore molecular sieve B are bonded with the A of thing containing sulfonic polymeric by sulphur amido bond.
  6. A kind of 6. PEM with three-decker according to claim 1, it is characterised in that：Described The A of thing containing sulfonic polymeric be containing it is more than one containing sulfonic hydrophilic segment A1 and it is more than one not Block copolymer containing sulfonic hydrophobic chain segment A2.
  7. A kind of 7. PEM with three-decker according to claim 6, it is characterised in that：Described Contain the repeat unit shown in following formula Q1 containing sulfonic hydrophilic segment A1,
    In formula Q1, Z1Represent ketone group, sulfuryl, direct key ,-PO (R1)-,-(CF2)f- or-C (CF3)2- In one kind, wherein, R1 is organic radicals, and f is 1~5 integer；Z2Represent O or S；M expressions hydrogen, One kind of metal cation, ammonium cation or the alkyl with 1~20 carbon atom；M1 represent 1~4 it is whole Number；Ar1Represent the divalent organic group containing aromatic rings.
  8. A kind of 8. PEM with three-decker according to claim 7, it is characterised in that：It is described logical Repeat unit shown in formula Q1 is the repeat unit shown in following formula Q2,
    In formula Q2, M represents hydrogen, metal cation or ammonium cation；Ar2Selected from following general formula Xs -1~X-4 At least one of repeat unit,
    In general formula X -1, Z3For one kind in ketone group, sulfuryl or direct key.
  9. A kind of 9. PEM with three-decker according to claim 6, it is characterised in that：It is described not Contain the repeat unit shown in following formula Q3 and/or Q4 containing sulfonic hydrophobic chain segment A2；
    Wherein, in formula Q3, phenyl ring can be arbitrarily substituted, but be free from sulfonic group；Z4For electron-withdrawing base Group；Z5For electron-withdrawing group, O or S,
    In formula Q4, Z6With Z7For the divalent organic base containing aromatic ring, but sulfonic group is free from, a and b is each It independently is 1 or 2.
  10. A kind of 10. PEM with three-decker according to claim 9, it is characterised in that：It is described Z4For-CO- or-SO2-, Z5For-O- or-S-, Z6For phenylene, Z7For following formula X-3, X-5, X-6 At least one of with X-7,
  11. 11. a kind of preparation method of the PEM according to any one of claims 1 to 10 with three-decker, It is characterized in that：Comprise the steps of：
    (1) sulfonic polymeric thing A or the dissolving of the A of thing containing sulfonic polymeric precursors will be contained in organic solvent Solution 1 is obtained, liquid film is made on base material with solution 1,10 minutes~4 are dried at 40~100 DEG C Hour, form the first tunic；
    (2) with containing the A of thing containing sulfonic polymeric or the A precursors of thing containing sulfonic polymeric and silicon-based mesoporous Molecular sieve B solution 2, is made second layer liquid film on the first tunic, in 40~100 DEG C of dryings 10 minutes~4 hours, form the second tunic；
    (3) third layer liquid film is formed on the second tunic with solution 1, is dried 10 minutes at 40~100 DEG C ~4 hours, obtain three-decker film；
    (4) film obtained in acid treatment step (3) is used, finally gives PEM.
  12. 12. a kind of preparation method of PEM with three-decker according to claim 11, its feature It is：Described silicon-based mesoporous molecular sieve B average grain diameters are 20~1000nm, and average pore size is 2~50nm.
  13. 13. a kind of preparation method of PEM with three-decker according to claim 12, its feature It is：Described silicon-based mesoporous molecular sieve B is SBA-15.
  14. 14. a kind of preparation method of PEM with three-decker according to claim 11, its feature It is：Silicon-based mesoporous molecular sieve B mass in the solution 2 is the A matter of thing containing sulfonic polymeric in solution 2 The 0.1~30% of amount.
  15. 15. a kind of preparation method of PEM with three-decker according to claim 11, its feature It is：Silicon-based mesoporous molecular sieve B in the solution 2 has 20~100% by aminofunctional, and solution 2 In contain N, N '-dicarbapentaborane imidazoles.
  16. 16. a kind of preparation method of PEM with three-decker according to claim 11, its feature It is：The described A of thing containing sulfonic polymeric be containing it is more than one containing sulfonic hydrophilic segment A1 and The more than one block copolymer without sulfonic hydrophobic chain segment A2.
  17. 17. a kind of preparation method of PEM with three-decker according to claim 16, its feature It is：The described repeat unit contained containing sulfonic hydrophilic segment A1 shown in following formula Q1,
    In formula Q1, Z1Represent ketone group, sulfuryl, direct key ,-PO (R1)-,-(CF2)f- or-C (CF3)2- In one kind, wherein, R1 is organic radicals, and f is 1~5 integer；Z2Represent O or S；M expressions hydrogen, One kind of metal cation, ammonium cation or the alkyl with 1~20 carbon atom；M1 represent 1~4 it is whole Number；Ar1Represent the divalent organic group containing aromatic rings.
  18. 18. a kind of preparation method of PEM with three-decker according to claim 16, its feature It is：Repeat unit shown in the formula Q1 is the repeat unit shown in following formula Q2,
    In formula Q2, M represents hydrogen, metal cation or ammonium cation；Ar2Selected from following general formula Xs -1~X-4 At least one of repeat unit,
    In general formula X -1, Z3For one kind in ketone group, sulfuryl or direct key.
  19. 19. a kind of preparation method of PEM with three-decker according to claim 16, its feature It is：The repetition contained without sulfonic hydrophobic chain segment A2 shown in following formula Q3 and/or Q4 Unit；
    In formula Q3, phenyl ring can be arbitrarily substituted, but be free from sulfonic group；Z4For electron-withdrawing group；Z5 For electron-withdrawing group, O or S,
    In formula Q4, Z6With Z7For the divalent organic base containing aromatic ring, but sulfonic group is free from, a and b is each It independently is 1 or 2.
  20. 20. a kind of preparation method of PEM with three-decker according to claim 19, its feature It is：Described Z4For-CO- or-SO2-, Z5For-O- or-S-, Z6For phenylene, Z7For following formula X-3, At least one of X-5, X-6 and X-7,
  21. A kind of 21. solid polymer fuel cell, it is characterised in that：Contain any tool described in claim 1~10 There is the PEM of three-decker.
CN201610522355.6A 2016-07-05 2016-07-05 PEM, preparation method and solid polymer fuel cell Pending CN107591550A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251446A (en) * 2018-08-24 2019-01-22 海信（山东）空调有限公司 A kind of high water absorption is low to be swollen anti-condensation thin-film material and its preparation method and application
CN109873189A (en) * 2019-03-22 2019-06-11 四川东为氢源科技有限公司 Proton exchange membrane and preparation method thereof
CN111653810A (en) * 2020-05-29 2020-09-11 西安工程大学 PVA-based molecular sieve composite proton exchange membrane and preparation method thereof
CN112969661A (en) * 2018-11-29 2021-06-15 庄信万丰股份有限公司 Method for modifying the surface of molecular sieves with aminosilanes

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1861667A (en) * 2006-06-09 2006-11-15 清华大学 Preparation process of composite hydrogen type proton exchaning membrane for fuel cell
US20070092777A1 (en) * 2005-10-26 2007-04-26 Aruna Zhamu Self-humidifying proton exchange membrane, membrane-electrode assembly, and fuel cell
CN101938002A (en) * 2010-07-23 2011-01-05 北京化工大学 Nafion/sulfonated SiO2 molecular sieve composite proton exchange membrane and preparation method thereof
CN103814062A (en) * 2011-09-20 2014-05-21 东丽先端材料研究开发（中国）有限公司 Sulfonic acid group-containing polymer, sulfonic acid group-containing aromatic compound and method of making same, as well as polymer electrolyte material, polymer electrolyte molded product and solid polymer fuel cell using same
CN105355939A (en) * 2015-11-26 2016-02-24 辽宁科技大学 Proton exchange membrane for fuel cell and preparation method of proton exchange membrane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070092777A1 (en) * 2005-10-26 2007-04-26 Aruna Zhamu Self-humidifying proton exchange membrane, membrane-electrode assembly, and fuel cell
CN1861667A (en) * 2006-06-09 2006-11-15 清华大学 Preparation process of composite hydrogen type proton exchaning membrane for fuel cell
CN101938002A (en) * 2010-07-23 2011-01-05 北京化工大学 Nafion/sulfonated SiO2 molecular sieve composite proton exchange membrane and preparation method thereof
CN103814062A (en) * 2011-09-20 2014-05-21 东丽先端材料研究开发（中国）有限公司 Sulfonic acid group-containing polymer, sulfonic acid group-containing aromatic compound and method of making same, as well as polymer electrolyte material, polymer electrolyte molded product and solid polymer fuel cell using same
CN105355939A (en) * 2015-11-26 2016-02-24 辽宁科技大学 Proton exchange membrane for fuel cell and preparation method of proton exchange membrane

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251446A (en) * 2018-08-24 2019-01-22 海信（山东）空调有限公司 A kind of high water absorption is low to be swollen anti-condensation thin-film material and its preparation method and application
CN112969661A (en) * 2018-11-29 2021-06-15 庄信万丰股份有限公司 Method for modifying the surface of molecular sieves with aminosilanes
CN112969661B (en) * 2018-11-29 2023-11-28 庄信万丰股份有限公司 Method for modifying the surface of molecular sieves with aminosilanes
CN109873189A (en) * 2019-03-22 2019-06-11 四川东为氢源科技有限公司 Proton exchange membrane and preparation method thereof
CN109873189B (en) * 2019-03-22 2020-08-11 四川东为氢源科技有限公司 Proton exchange membrane and preparation method thereof
CN111653810A (en) * 2020-05-29 2020-09-11 西安工程大学 PVA-based molecular sieve composite proton exchange membrane and preparation method thereof

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