CN101789516A - Free-standing sandwich structure composite proton conducting film and preparation method thereof - Google Patents
Free-standing sandwich structure composite proton conducting film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a free-standing sandwich structure composite proton conducting film and a preparation method thereof in the technical field of a fuel cell. A sandwich structure is formed by an upper organic proton conducting film layer, a lower organic proton conducting film layer and a middle inorganic proton conducting film layer, wherein, the inorganic proton conducting film layer is metallic oxide or phosphorus-containing metallic oxide with proton conducting capacity, and the organic proton conducting film layer is polymer with the proton conducting capacity. The problems of no flexibility of the inorganic proton conducting film layer and high methanol permeability of the organic proton conducting film layer are overcome, and the free-standing sandwich structure composite proton conducting film with proton conducting capacity and very low methanol permeability is obtained, so as to solve technical problems in the prior art.
Description
Technical field
What the present invention relates to is the material in a kind of fuel cell technology field and preparation method thereof, specifically is a kind of free-standing sandwich structure composite proton conducting film and preparation method thereof.
Background technology
Polymer dielectric film (as
Film) has high proton conductivity and good chemical stability, be widely used in low-temperature fuel cell (PEFCs and DMFCs).Yet the distortion that water adsorbs and desorption causes takes place in polymer proton conductive film easily, makes fuel (particularly methyl alcohol) pass dielectric film, causes chemical short, and contaminated electrode causes the power output of fuel cell significantly to reduce.With respect to polymer dielectric film, inorganic proton conducting film preparation technology is simple, cost is low, and therefore the distortion that does not have water absorption, desorption to cause is expected to become substituting of polymer dielectric film.But, comprise that sol-gel glass is (as SiO
2, P
2O
5-SiO
2), heteropoly acid is (as H
3PW
12O
4029H
2O) and solid acid (as CsH
2PO
4) the inorganic proton conducting film that waits, pliability is poor, thickness is big, when the battery proton film that acts as a fuel is used, and poor processability, and the internal resistance power loss is big.
Through the prior art literature search is found, people such as Colomer deliver " Nanoporous Anatase Thin Films as Fast Proton-ConductingMaterials " (as the nano-pore anatase film of fast proton electric conducting material) on " Advanced Materiels " (advanced material was rolled up the 371st page of 3 phase in 2006 the 18th), reported nano-pore titanium dioxide anatase proton conductive film.Yet this film can not self-supporting, in fuel cell, realize separating the proton film function of fuel and oxidant, and this proton conductive membrane must be supported on the specific porous substrate, has increased membrane electrode and has prepared complexity, and its application is restricted.Therefore, prepare a kind of ultra-thin, pliable and tough, the self-supporting proton conductive membrane is extremely important.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of free-standing sandwich structure composite proton conducting film and preparation method thereof is provided, suppress methanol permeation effectively by inorganic film being arranged at pars intermedia, the organic film of both sides then provides enough mechanical strength and pliability up and down.This sandwich composite construction has high dimensional stability and thermal endurance.Ultra-thin, pliable and tough, free-standing sandwich structure organic/inorganic/organic composite proton conducting film that the present invention makes have proton conductivity and low-down methanol permeability simultaneously.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of free-standing sandwich structure composite proton conducting film, constitute sandwich structure by last organic electronic conduction rete, following organic electronic conduction rete and middle inorganic proton conductive film layer.
Described inorganic proton conductive film layer is meant the metal oxide or the phosphorous metal oxide of proton conductive ability.For example, SiO
2, TiO
2, ZrO
2, Al
2O
3, SiO
2-P
2O
5, TiO
2-P
2O
5, ZrO
2-P
2O
5And Al
2O
3-P
2O
5In one or more make.
Described organic electronic conduction rete is the polymer with proton conductive ability.For example, Polyetherimide (PEI), polyvinyl alcohol (PVA), perfluorinated sulfonic acid (PSA) etc.The present invention prepares gained composite proton electric conducting material and has proton conductive ability, and remarkable low methanol permeability.This proton conducting material can be used for fields such as fuel cell, electrochemical sensor, super capacitor.
The present invention relates to the preparation method of above-mentioned free-standing sandwich structure composite proton conducting film, may further comprise the steps:
Step 1: preparation sacrifice layer solution, adopt coating processes, on substrate, form sacrifice layer.
Described substrate is silicon chip, sheet glass, plastic plate, metallic plate or ceramic wafer.
Described sacrifice layer solution, the 0.1～50wt% solution that is dissolved in the water or forms in the organic solvent for organic polymer.For example, poly-(p styrene sulfonic acid) (PSS) is dissolved in deionized water, and preparation gathers the aqueous solution of (p styrene sulfonic acid); Polyvinylphenol (PHS) is dissolved in the ethanol, the ethanolic solution of preparation polyvinylphenol; The liposoluble of polyvinyl acetate base prepares the acetone soln of polyvinyl acetate base fat in acetone; Polymethyl methacrylate (PMMA) is dissolved in the acetylacetone,2,4-pentanedione, the acetylacetone,2,4-pentanedione solution of preparation polymethyl methacrylate; Polystyrene is dissolved in the chloroform, the chloroformic solution of preparation polystyrene etc.
Step 2: prepare organic electronic conduction polymer solution, adopt coating processes, on sacrifice layer, form organic proton conductive layer.
Described organic electronic conduction polymer solution is for having the 0.01～50wt% solution that forms in the water-soluble or organic solvent of proton conductive ability organic polymer.For example, Polyetherimide is dissolved in the chloroform, the chloroform soln of preparation Polyetherimide; (PCGF is Aldrich) with polymine (PEI, Aldrich) mixed solution in chloroform for the polymer of formaldehyde and (chloromethyl) oxirane and 2-methylphenol; (PVA) is soluble in water for polyvinyl alcohol, obtains the aqueous solution of polyvinyl alcohol (PVA); Perfluorinated sulfonic acid (PSA) is dissolved in the pure water, obtains the alcohol solution of perfluorinated sulfonic acid (PSA) etc.
Described organic electronic conduction layer is for having proton conductive ability organic film, for example, and Polyetherimide (PEI), polyvinyl alcohol (PVA), perfluorinated sulfonic acid (PSA) etc.
Step 3: preparation inorganic proton conduction colloidal sol, adopt coating processes, on organic electronic conduction layer, form the inorganic proton conductive layer.
Described inorganic proton conduction colloidal sol, preparation in the following manner:
Metal oxide precursor, deionized water, organic solvent, inorganic acid aqueous solution and additive through being mixed and made into colloidal sol, are added phosphoric acid then in colloidal sol, after stirring, obtain mixed sols.
The mol ratio of described metal oxide precursor, deionized water, organic solvent, inorganic acid, additive is: 1: 1～8: 1～100: 0～0.1: 0～5.
Described metal oxide precursor refers to the compound of metal alkoxide or metal alkoxide.
Described metal alkoxide can be a metal alkoxide or form metallic alkoxide compound (as ZrCl by being dissolved in appropriate solvent
4, Si (OCN)
4Deng), for example: methyl silicate, four titanium butoxide, four titanium propanolates, zirconium-n-propylate, tetrabutyl zirconate, aluminium butoxide, five butoxy niobiums, four butoxy tin; Methyltrimethoxy silane or diethyl diethoxy silane.Can use one or more combination.
Described organic solvent is meant: a kind of or its combination in methyl alcohol, ethanol or the propyl alcohol;
Described inorganic acid is meant: a kind of or its combination in hydrochloric acid, sulfuric acid, the acetic acid;
Described phosphoric acid is with P
2O
5Convert P
2O
5With the molar percentage of metal alkoxide be 0～50%: 100%～50%;
Described additive is meant: surfactant (HO (CH2CH2O) 10C16H33) (SIGMA-ALDRICH), block copolymer
F127 (BASF), acetylacetone,2,4-pentanedione, and other organic substance (starch, glucose etc.).
Step 4: prepare organic electronic conduction polymer solution, adopt coating processes, on sacrifice layer, form organic proton conductive layer.
Described organic electronic conduction polymer solution is for having the 0.01-50wt% solution that forms in the water-soluble or organic solvent of proton conductive ability organic polymer.For example, Polyetherimide is dissolved in the chloroform, the chloroform soln of preparation Polyetherimide; (PCGF is Aldrich) with polymine (PEI, Aldrich) mixed solution in chloroform for the polymer of formaldehyde and (chloromethyl) oxirane and 2-methylphenol; (PVA) is soluble in water for polyvinyl alcohol, obtains the aqueous solution of polyvinyl alcohol (PVA); Perfluorinated sulfonic acid (PSA) is dissolved in the pure water, obtains the alcohol solution of perfluorinated sulfonic acid (PSA) etc.
Step 5: substrate is immersed in the solvent, and organic sacrificing layer dissolves and is removed, and composite proton conducting film separates with substrate, obtains free-standing sandwich structure composite proton conducting film.
Described solvent, the liquid that can dissolve for sacrifice layer.For example, water, ethanol, acetone, chloroform equal solvent.
Coating processes described in the above-mentioned steps, in following two kinds any:
A) spin-coating: substrate is placed on the whirler, then with drips of solution in substrate surface, start whirler, making the spin-coating motor speed reach 100 changes-10000 rev/mins, and keeps 5 seconds-10 minutes; Optimum condition is-6000 rev/mins of 1000 commentaries on classics, keeps 30 seconds-3 minutes.Form membrane structure on the substrate.
B) lift and film: substrate is immersed in the solution, lift out substrate with the speed of 0.1-100 cm per minute from liquid, preferred pull rate is the 1-20 cm per minute.Form membrane structure on the substrate.
The present invention prepares gained composite proton electric conducting material and has proton conductive ability and significantly being lower than
The methanol permeability of film.This proton conducting material can be used for fields such as fuel cell, electrochemical sensor, super capacitor.
Description of drawings
Fig. 1 is a structural representation of the present invention.
Fig. 2 is embodiment 1 optical photograph.
Fig. 3 is that embodiment 1 proton conductivity and humidity concern schematic diagram.
Fig. 4 is embodiment 1 methanol concentration and time of penetration relation.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed execution mode and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
Step 1: preparation sacrifice layer.(PSS Aldrich) is dissolved in deionized water, the PSS aqueous solution of preparation 5wt% will to gather (p styrene sulfonic acid).Substrate is placed on the whirler, with 3000 rev/mins, kept 1 minute, rotation applies the PSS sacrifice layer.
Step 2: preparation organic layer.(PCGF, Aldrich) (PEI Aldrich) mixes preparation 1wt% solution with 1: 1 mass ratio to the polymer of formaldehyde and (chloromethyl) oxirane and 2-methylphenol in chloroform with polymine.With 3000 rev/mins, kept 1 minute, rotation applies the PEI/PCGF organic layer on the substrate that step 1 obtains.
Step 3: preparation inorganic layer.With tetraethoxysilance: normal propyl alcohol: water: hydrochloric acid: C
16H
33(OC
2H
4)
10OH (CEO, Aldrich)=1: 11.4: 5: ratio preparation (CEO) SiO of 0.004: 0.1
2Colloidal sol.With 3000 rev/mins, kept 1 minute, rotation applies the SiO that contains surfactant
2Layer is on the substrate that step 2 obtains.
Step 4: preparation organic layer.Class coating material and technology are with step 2.
Step 5: substrate is immersed in the water, dissolve sacrifice layer.Separate with substrate, obtain free-standing sandwich structure (PEI/PCGF)/(CEO) SiO
2/ (PEI/PCGF) proton conductive membrane.
Embodiment 2:
Step 1: preparation sacrifice layer.PSS is dissolved in deionized water, the PSS aqueous solution of preparation 20wt%.Substrate is placed on the whirler, with 10000 rev/mins, kept 1 minute, rotation applies the PSS sacrifice layer.
Step 2: preparation organic layer.PCGF mixes in chloroform with 1: 1 mass ratio with PEI, preparation 50wt% solution.Start whirler, apply the PEI/PCGF organic layer on the substrate that step 1 obtains.
Step 3: preparation inorganic layer.At first with tetraethoxysilane, deionized water, hydrochloric acid according to 1: 4: 4 * 10
-3Mol ratio was room temperature strong agitation 30 minutes.Then according to 5%P
2O
5-95%SiO
2Molar percentage, in solution, slowly add phosphoric acid, stirred 20 minutes.The colloidal sol for preparing is dripped on the substrate of step 2, with 1000 rev/mins, kept 1 minute, rotation applies and obtains phosphorus silicic acid layer.
Step 4: preparation organic layer.Class coating material and technology are with step 2.
Step 5: substrate is immersed in the water, dissolve sacrifice layer.Separate with substrate, obtain free-standing sandwich structure (PEI/PCGF)/P
2O
5SiO
2/ (PEI/PCGF) proton conductive membrane.
Free-standing sandwich structure (the PEI/PCGF)/P that obtains
2O
5SiO
2/ (PEI/PCGF) performance of proton conductive membrane is similar to Example 1.
Embodiment 3:
Step 1: preparation sacrifice layer.PSS is dissolved in deionized water, the PSS aqueous solution of preparation 0.1wt%.Substrate is placed on the whirler,, kept 5 minutes, start whirler, apply the PSS sacrifice layer with 100 rev/mins.
Step 2: preparation organic layer.PCGF mixes in chloroform with 1: 1 mass ratio with PEI, preparation 0.1wt% solution.Start whirler, with 1000 rev/mins, kept 1 minute, rotation applies the PEI/PCGF organic layer on the substrate that step 1 obtains.
Step 3: preparation inorganic layer.With zirconium-n-butylate: acetylacetone,2,4-pentanedione: water: propyl alcohol: surfactant
F127 (BASFCorporation)=1: 5: 5: 20: 0.01 ratio preparation colloidal sol.In proportion zirconium-n-butylate is diluted in the butanols, adds acetylacetone,2,4-pentanedione and water, at stirring at room 1h; Surfactant
F127 is dissolved in the butanols of 5 times of volumes, at stirring at room 1h; With above-mentioned two kinds of solution mixing, room temperature continuous stirring 2h, colloidal sol transparent until obtaining, clarification.The colloidal sol for preparing is dripped on the substrate of step 2, with 10000 rev/mins, kept 10 minutes, rotation applies (F127) ZrO that contains surfactant
2Layer.
Step 4: preparation organic layer.Class coating material and technology are with step 2.
Step 5: substrate is immersed in the water, dissolve sacrifice layer.Separate with substrate, obtain free-standing sandwich structure (PEI/PCGF)/(F127) ZrO
2/ (PEI/PCGF) proton conductive membrane.
Free-standing sandwich structure (PEI/PCGF)/(F127) ZrO that obtains
2/ (PEI/PCGF) performance of proton conductive membrane is similar to Example 1.
Embodiment 4:
Step 1: preparation sacrifice layer.PSS is dissolved in deionized water, the PSS aqueous solution of preparation 5wt%.Substrate is placed on the whirler, with 1000 rev/mins, kept 1 minute, rotation applies the PSS sacrifice layer.
Step 2: preparation organic layer.Use polymine (PEI), with 3000 rev/mins, kept 1 minute, rotation applies the PEI organic layer on the substrate that step 1 obtains.
Step 3: preparation inorganic layer.With tetraethoxysilance: normal propyl alcohol: water: hydrochloric acid: C
16H
33(OC
2H
4)
10OH (CEO, Aldrich)=1: 11.4: 5: ratio preparation (CEO) SiO of 0.004: 0.1
2Colloidal sol.With 1000 rev/mins, kept 1 minute, rotation applies the SiO that contains surfactant
2Layer is on the substrate that step 2 obtains.
Step 4: preparation organic layer.Class coating material and technology are with step 2.
Step 5: substrate is immersed in the water, dissolve sacrifice layer.Separate with substrate, obtain free-standing sandwich structure PEI/ (CEO) SiO
2/ PEI proton conductive membrane.
Free-standing sandwich structure PEI/ (CEO) SiO that obtains
2The performance of/PEI proton conductive membrane is similar to Example 1.
Embodiment 5
Step 1: preparation sacrifice layer.(PHS Aldrich) in the ethanol, prepares 30wt% solution with polyvinylphenol.Speed with 100 cm per minute lifts out substrate from liquid, lift to apply the PHS sacrifice layer.
Step 2: preparation organic layer.Polyvinyl alcohol (PVA, Aldrich) soluble in water, the preparation 5wt% aqueous solution.Speed with 0.1 cm per minute lifts out substrate from liquid, lift on the substrate that is coated on step 1 acquisition.
Step 3: preparation inorganic layer.According to isopropyl titanate: propyl alcohol: the ratio preparation colloidal sol of surfactant=1: 20: 0.1.In proportion isopropyl titanate is diluted in the propyl alcohol; The while surfactant
F127 is dissolved in the propyl alcohol of 5 times of volumes, at stirring at room 1h.With above-mentioned two kinds of solution mixing, room temperature continuous stirring 2h, colloidal sol transparent until obtaining, clarification.The colloidal sol for preparing is dripped on the substrate of step 2, from liquid, lift out substrate, lift and apply (F127) TiO that contains surfactant with the speed of 0.1 cm per minute
2Layer.
Step 4: preparation organic layer.Class coating material and technology are with step 2.
Step 5: substrate is immersed in the alcohol, dissolve sacrifice layer.Separate with substrate, obtain free-standing sandwich structure PVA/ (F127) TiO
2/ PVA composite proton conducting film.
Free-standing sandwich structure PVA/ (F127) TiO that obtains
2The performance of/PVA composite proton conducting film is similar to Example 1.
Step 1: preparation sacrifice layer.PHS is dissolved in the ethanol preparation 0.01wt% solution.Substrate is immersed in the solution, from liquid, lift out substrate, lift and apply the PHS sacrifice layer with the speed of 100 cm per minute.
Step 2: preparation organic layer.(PVA) is soluble in water for polyvinyl alcohol, the preparation 0.01wt% aqueous solution.Speed with 100 cm per minute lifts out substrate from liquid, lift on the substrate that is coated on step 1 acquisition.
Step 3: preparation inorganic layer.With tetraethoxysilance: normal propyl alcohol: water: hydrochloric acid: CEO=1: 11.4: 5: 0.004: 0.1 ratio preparation SiO
2Colloidal sol.Speed with 10 cm per minute lifts out substrate from liquid, lift to apply the SiO that contains surfactant
2Layer.
Step 4: preparation organic layer.PVA is soluble in water, preparation 0.01wt% solution.Speed with 100 cm per minute lifts out substrate from liquid, lift on the substrate that is coated on step 3 acquisition.
Step 5: substrate is immersed in the ethanol, dissolve sacrifice layer.Separate with substrate, obtain free-standing sandwich structure PVA/SiO
2/ PVA composite proton conducting film.
Obtain free-standing sandwich structure PVA/SiO
2The performance of/PVA composite proton conducting film is similar to Example 1.
Step 1: preparation sacrifice layer.PSS is dissolved in deionized water, the PSS aqueous solution of preparation 5wt%.Substrate is placed on the whirler, with 1000 rev/mins, kept 1 minute, rotation applies the PSS sacrifice layer.
Step 2: preparation organic conductive layers.PCGF mixes in chloroform with 1: 1 mass ratio with PEI, preparation 1wt% solution.With 1000 rev/mins, kept 1 minute, rotation applies the PEI/PCGF organic layer on the substrate that step 1 obtains.
Step 3: preparation inorganic conductive layer.At first with tetraethoxysilane, deionized water, hydrochloric acid according to 1: 4: 4 * 10
-3Mol ratio was room temperature strong agitation 30 minutes.Then according to 5%P
2O
5-95%SiO
2Molar percentage, in solution, slowly add phosphoric acid, stirred 20 minutes.With 1000 rev/mins, kept 1 minute, rotation applies and obtains phosphorus silicic acid layer.
Step 4: preparation organic conductive layers.(PSA Dupont) is dissolved in the pure water perfluorinated sulfonic acid, preparation 5wt% solution.With 1000 rev/mins, kept 1 minute, rotation is coated on the substrate of step 3 acquisition.
Step 5: substrate is immersed in the water, dissolve sacrifice layer.Separate with substrate, obtain free-standing sandwich structure (PEI/PCGF)/P
2O
5SiO
2/ PSA composite proton conducting film.
Obtain free-standing sandwich structure (PEI/PCGF)/P
2O
5SiO
2The performance of/PSA composite proton conducting film is similar to Example 1.
Embodiment 8
Step 1: preparation sacrifice layer.PHS is dissolved in the ethanol preparation 5wt% solution.Substrate is placed on the whirler, with 1000 rev/mins, kept 1 minute, rotation applies the PHS sacrifice layer.
Step 2: preparation organic conductive layers.The preparation organic layer.PVA is soluble in water, preparation 5wt% solution.With 1000 rev/mins, kept 1 minute, rotation is coated on the substrate of step 1 acquisition.
Step 3: preparation inorganic conductive layer.With tetrabutyl zirconate: acetylacetone,2,4-pentanedione: water: propyl alcohol=1: 5: 5: 20: 0.01 ratio preparation colloidal sol.In proportion zirconium-n-butylate is diluted in the butanols, adds acetylacetone,2,4-pentanedione and water, at stirring at room 1h, then according to 5%P
2O
5-95% ZrO
2Molar percentage, in solution, slowly add phosphoric acid, stirred 20 minutes.With 1000 rev/mins, kept 1 minute, rotation applies the zirconium phosphate layer that contains surfactant.
Step 4: preparation organic conductive layers.(PSA Dupont) is dissolved in the pure water perfluorinated sulfonic acid, preparation 10wt% solution.With 1000 rev/mins, kept 1 minute, rotation is coated on the substrate of step 3 acquisition.
Step 5: substrate is immersed in the propyl alcohol, dissolve sacrifice layer.Separate with substrate, obtain free-standing sandwich structure PVA/P
2O
5ZrO
2/ PSA organic composite proton conducting film.
The free-standing sandwich structure PVA/P that obtains
2O
5ZrO
2The performance of/PSA composite proton conducting film is similar to Example 1.
Step 1: preparation sacrifice layer.PSS is dissolved in deionized water, the PSS aqueous solution of preparation 50wt%.Substrate is placed on the whirler, with 10000 rev/mins, kept 1 minute, rotation applies the PSS sacrifice layer.
Step 2: prepare organic electronic conduction layer.PCGF mixes in chloroform with 1: 1 mass ratio with PEI.With 10000 rev/mins, kept 1 minute, rotation applies the PEI/PCGF organic layer on the substrate that step 1 obtains.
Step 3: preparation inorganic proton conductive layer.According to four titanium propanolates: propyl alcohol: the ratio preparation colloidal sol of surfactant=1: 20: 0.1.In proportion isopropyl titanate is diluted in the propyl alcohol; The while surfactant
F127 is dissolved in the propyl alcohol of 5 times of volumes, at stirring at room 1h.With above-mentioned two kinds of solution mixing, room temperature continuous stirring 2h, then according to 5%P
2O
5-95%TiO
2Molar percentage, in solution, slowly add phosphoric acid, stirred 20 minutes., with 10000 rev/mins, keeping 1 minute, rotation applies the phosphoric acid titanium layer that contains surfactant.
Step 4: preparation organic conductive layers.(PSA Dupont) is dissolved in the pure water perfluorinated sulfonic acid, preparation 10wt% solution.With 1000 rev/mins, kept 1 minute, rotation is coated on the substrate of step 3 acquisition.
Step 5: substrate is immersed in the water, dissolve sacrifice layer.Separate with substrate, obtain free-standing sandwich structure (PEI/PCGF)/(F127) P
2O
5TiO
2/ (PSA) organic composite proton conducting film.
Free-standing sandwich structure (PEI/PCGF)/(F127) P that obtains
2O
5TiO
2/ (PSA) performance of composite proton conducting film is similar to Example 1.
The embodiment performance test:
Use digital camera (DSC-W50, Sony) optical photograph of acquisition sample.The proton conductivity test sample preparation: sputter gold electrode on sample, the lead that connects sample is the Au lead.(alternating voltage is 10mV to conductivity for SI-1260, Solartron) test, and test is carried out in climatic chamber with the impedance spectrometer.The mensuration of methanol permeability adopts two Room methods, and (GC-2010 SHIMADZU) measures the methanol concentration that takes out in the sample to gas chromatograph.
As shown in Figure 1, be the foregoing description 1 preparation gained composite proton conducting film structural representation, this composite proton conducting film comprises: inorganic proton conductive film layer 1 and organic electronic conduction rete 2 compositions that are covered in its upper and lower surface respectively.
Shown in Fig. 2 a, composite proton conducting film floats in water; Shown in Fig. 2 b, 600 nanometer thickness composite proton conducting films are supported on the becket.Fig. 2 a and Fig. 2 b demonstrate composite proton conducting film and have good pliability and mechanical strength.
Measure the proton conductivity of the sandwich structure composite membrane for preparing according to embodiment 1 with electric impedance analyzer.As shown in Figure 3, for the proton conductivity of film with the humidity variation diagram.The proton conductivity of film is to the variation sensitivity of humidity, under 80 degree conditions, and 40%～90%RH humidity measurement scope, the proton conductivity of film increases with humidity and improves, and the raising degree is near 2 orders of magnitude.
The cell electrolyte that acts as a fuel, one of them important parameter is a methanol permeability.As shown in Figure 4, pass through the methanol concentration of sandwich structure composite membrane and the relation of time of penetration for infiltration.According to this figure, calculate methanol permeability and be about 1.07 * 10
-8Cm
2/ S, this numeric ratio
2 * 10 of film
-6Cm
2Low approximately two orders of magnitude of/S methanol permeability.In composite membrane, the inorganic silicon dioxide layer has hindered methanol crossover, thereby significantly reduces methanol permeability, and organic layer then provides the pliability and the mechanical strength of composite membrane.
The foregoing description is by dissolving sacrifice layer method, obtain the sandwich structure composite proton conducting film of self-supporting, it is poor to overcome inorganic proton conductive film layer pliability, the high problem of organic electronic conduction rete methanol permeability, obtain to have simultaneously the free-standing sandwich structure composite proton conducting film of proton conductivity and low-down methanol permeability, thereby solve a prior art difficult problem.This sandwich structure composite proton conducting film can be applicable to fields such as fuel cell, transducer and ultracapacitor.
Claims (10)
1. free-standing sandwich structure composite proton conducting film, it is characterized in that, constitute sandwich structure by last organic electronic conduction rete, following organic electronic conduction rete and middle inorganic proton conductive film layer, wherein: the inorganic proton conductive film layer is metal oxide or the phosphorous metal oxide that the proton conductive ability is arranged; Organic electronic conduction rete is the polymer with proton conductive ability.
2. free-standing sandwich structure composite proton conducting film according to claim 1 is characterized in that, described inorganic proton conductive film layer is SiO
2, TiO
2, ZrO
2, Al
2O
3, SiO
2-P
2O
5, TiO
2-P
2O
5, ZrO
2-P
2O
5, Al
2O
3-P
2O
5In one or more compositions.
3. free-standing sandwich structure composite proton conducting film according to claim 1 is characterized in that, described organic electronic conduction rete is Polyetherimide, polyvinyl alcohol or perfluorinated sulfonic acid.
4. the preparation method of a free-standing sandwich structure composite proton conducting film according to claim 1 is characterized in that, may further comprise the steps:
Step 1: preparation sacrifice layer solution, adopt coating processes, on substrate, form sacrifice layer;
Step 2: prepare organic electronic conduction polymer solution, adopt coating processes, on sacrifice layer, form organic proton conductive layer;
Step 3: preparation inorganic proton conduction colloidal sol, adopt coating processes, on organic electronic conduction layer, form the inorganic proton conductive layer;
Step 4: prepare organic electronic conduction polymer solution, adopt coating processes, on the inorganic proton conductive layer, form organic proton conductive layer;
Step 5: substrate is immersed in the dissolving sacrifice layer solvent, and organic sacrificing layer dissolves and is removed, and composite proton conducting film separates with substrate, makes free-standing composite proton conducting film.
5. the preparation method of free-standing sandwich structure composite proton conducting film according to claim 4 is characterized in that, the described substrate of step 1 is silicon chip, sheet glass, plastic plate, metallic plate or ceramic wafer.
6. the preparation method of free-standing sandwich structure composite proton conducting film according to claim 4 is characterized in that, the described sacrifice layer solution of step 1 is the 0.01-50wt% solution that organic polymer is dissolved in the water or forms in the organic solvent.
7. the preparation method of free-standing sandwich structure composite proton conducting film according to claim 4, it is characterized in that the described organic electronic conduction polymer solution of step 2 and step 4 is to have the 0.01-50wt% solution that forms in the water-soluble or organic solvent of proton conductive ability organic polymer; Described organic electronic conduction layer is for having proton conductive ability organic film.
8. the preparation method of free-standing sandwich structure composite proton conducting film according to claim 4 is characterized in that, the inorganic proton conduction colloidal sol described in the step 3, and preparation in the following manner:
Metal oxide precursor, deionized water, organic solvent, inorganic acid aqueous solution and additive through being mixed and made into colloidal sol, are added phosphoric acid then in colloidal sol, after stirring, obtain mixed sols.
9. the preparation method of free-standing sandwich structure composite proton conducting film according to claim 8, it is characterized in that the mol ratio of described metal oxide precursor, deionized water, organic solvent, inorganic acid, additive is: 1: 1～8: 1～100: 0～0.1: 0～5.
10. the preparation method of free-standing sandwich structure composite proton conducting film according to claim 4 is characterized in that, described coating processes, in following two kinds any:
A) spin-coating: substrate is placed on the whirler, then with drips of solution in substrate surface, start whirler, making the spin-coating motor speed reach 100 changes-10000 rev/mins, and keeps 5 seconds 10 minutes.
B) lift and film: substrate is immersed in the solution, from liquid, lift out substrate with the speed of 0.1-100 cm per minute.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109383087A (en) * | 2018-11-23 | 2019-02-26 | 华中科技大学 | A method of preparing multilayer self-supporting carbon film |
| CN112510235A (en) * | 2020-12-03 | 2021-03-16 | 东华大学 | Polyvinyl alcohol-bacterial cellulose trimmings structure type alkaline anion exchange membrane, preparation and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354532A (en) * | 2001-09-17 | 2002-06-19 | 中国科学院长春应用化学研究所 | Preparation method of compound electrolyte film formed by making low methyl alcohol penetrate proton conductor |
| US6416898B1 (en) * | 1999-03-31 | 2002-07-09 | Kabushiki Kaisha Toshiba | Fuel cell comprising an inorganic glass layer |
| US20070015022A1 (en) * | 2005-07-12 | 2007-01-18 | Samsung Sdi Co., Ltd. | Ion conductive composite membrane using inorganic conductor and method of manufacturing the same |
| JP2007109657A (en) * | 2005-10-14 | 2007-04-26 | Gm Global Technology Operations Inc | Multi-layered polymeric electrolyte membrane for fuel cell |
| US20080261098A1 (en) * | 2007-04-20 | 2008-10-23 | General Electric Company | Proton-conducting membranes for electrochemical devices, and related articles and processes |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6416898B1 (en) * | 1999-03-31 | 2002-07-09 | Kabushiki Kaisha Toshiba | Fuel cell comprising an inorganic glass layer |
| CN1354532A (en) * | 2001-09-17 | 2002-06-19 | 中国科学院长春应用化学研究所 | Preparation method of compound electrolyte film formed by making low methyl alcohol penetrate proton conductor |
| US20070015022A1 (en) * | 2005-07-12 | 2007-01-18 | Samsung Sdi Co., Ltd. | Ion conductive composite membrane using inorganic conductor and method of manufacturing the same |
| JP2007109657A (en) * | 2005-10-14 | 2007-04-26 | Gm Global Technology Operations Inc | Multi-layered polymeric electrolyte membrane for fuel cell |
| US20080261098A1 (en) * | 2007-04-20 | 2008-10-23 | General Electric Company | Proton-conducting membranes for electrochemical devices, and related articles and processes |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109383087A (en) * | 2018-11-23 | 2019-02-26 | 华中科技大学 | A method of preparing multilayer self-supporting carbon film |
| CN109383087B (en) * | 2018-11-23 | 2019-10-25 | 华中科技大学 | A method of preparing multilayer self-supporting carbon film |
| CN112510235A (en) * | 2020-12-03 | 2021-03-16 | 东华大学 | Polyvinyl alcohol-bacterial cellulose trimmings structure type alkaline anion exchange membrane, preparation and application |
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| CN101789516B (en) | 2012-09-05 |
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