CN101789278B - Free-standing composite proton conducting film and preparation method thereof - Google Patents
Free-standing composite proton conducting film and preparation method thereof Download PDFInfo
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- CN101789278B CN101789278B CN201010126399XA CN201010126399A CN101789278B CN 101789278 B CN101789278 B CN 101789278B CN 201010126399X A CN201010126399X A CN 201010126399XA CN 201010126399 A CN201010126399 A CN 201010126399A CN 101789278 B CN101789278 B CN 101789278B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 52
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- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 70
- 239000000243 solution Substances 0.000 claims description 36
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 23
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 23
- 239000004697 Polyetherimide Substances 0.000 claims description 21
- 229920001601 polyetherimide Polymers 0.000 claims description 21
- 238000000576 coating method Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
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- 239000003960 organic solvent Substances 0.000 claims description 9
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- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
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- 238000000034 method Methods 0.000 claims description 5
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- 238000004528 spin coating Methods 0.000 claims description 4
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- 239000012528 membrane Substances 0.000 description 14
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- 239000004094 surface-active agent Substances 0.000 description 13
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- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
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- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
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- 229910052905 tridymite Inorganic materials 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
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- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- JOXCDOKKASTCHR-UHFFFAOYSA-N [Si](O)(O)(O)O.[P] Chemical compound [Si](O)(O)(O)O.[P] JOXCDOKKASTCHR-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
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- 238000010276 construction Methods 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
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- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical class CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a free-standing composite proton conducting film and a preparation method thereof in the technical field of a fuel cell. The free-standing composite proton conducting film is formed by overlapping an organic proton conducting film layer and an 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 free-standing composite proton conducting film is obtained by dissolving a sacrificial layer, 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 composite proton conducting film with proton conducting capacity and very low methanol permeability is obtained, so as to solve the 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 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 composite proton conducting film and preparation method thereof is provided, suppress methanol permeation by inorganic film, organic film then provides enough mechanical strength and pliability.This composite construction has high dimensional stability and thermal endurance.The present invention obtains the organic/inorganic composite proton conducting film of self-supporting by dissolving sacrifice layer method.Ultra-thin, pliable and tough, self-supporting organic/inorganic 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 composite proton conducting film, overlapped by organic electronic conduction rete and inorganic proton conductive film layer and form, wherein: the 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
5, Al
2O
3-P
2O
5In one or more make; 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 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 0.01-50wt% solution that is dissolved in the water or forms in the organic solvent for organic polymer.For example, poly-(p styrene sulfonic acid) is dissolved in deionized water, the aqueous solution of preparation poly-(p styrene sulfonic acid); Polyvinylphenol 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 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: adopt in the following dual mode any one to prepare free-standing composite proton conducting film:
A) preparation inorganic proton conduction colloidal sol adopts coating processes, forms the inorganic proton conductive layer on organic electronic conduction layer; Substrate is immersed in the solvent, and organic sacrificing layer dissolves and is removed, and composite proton conducting film separates with substrate, makes free-standing composite proton conducting film;
B) substrate is immersed in the solvent, organic sacrificing layer dissolves and is removed, and composite proton conducting film separates with substrate, preparation inorganic proton conduction colloidal sol, adopt coating processes then, on organic electronic conduction layer, form the inorganic proton conductive layer, make free-standing composite proton conducting film.
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: substrate is immersed in the solvent, and organic sacrificing layer dissolves and is removed, and composite proton conducting film separates with substrate, makes free-standing composite proton conducting film.
Described solvent is for dissolving the liquid of 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.
Can change step 2 and step 3 sequencing.(seeing embodiment 6 and embodiment 7)
The present invention obtains the composite proton conducting film of self-supporting by dissolving sacrifice layer method.Adopt proton conductive rete structure of the present invention and preparation method, can overcome the inorganic proton conductive film layer and not have pliability, the high problem of organic electronic conduction rete methanol permeability, obtain to have simultaneously the free-standing composite proton conducting film of proton conductive ability and low-down methanol permeability, thereby solve a prior art difficult problem.This composite membrane can be applicable to 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.
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: substrate is immersed in the water, dissolve sacrifice layer.Separate with substrate, obtain self-supporting (PEI/PCGF)/(CEO) SiO
2Proton conductive membrane.
Embodiment 2:
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: 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: substrate is immersed in the water, dissolve sacrifice layer.Separate with substrate, obtain self-supporting (PEI/PCGF)/P
2O
5SiO
2Proton conductive membrane.
Self-supporting (the PEI/PCGF)/P that obtains
2O
5SiO
2The 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, with 100 rev/mins, kept 5 minutes, rotation starts whirler, applies the PSS sacrifice layer.
Step 2: preparation organic layer.PEI is dissolved in the chloroform, preparation 0.01wt% solution.Start whirler, with 100 rev/mins, kept 1 minute, rotation applies the PEI 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: substrate is immersed in the water, dissolve sacrifice layer.Separate with substrate, obtain self-supporting PEI/ (F127) ZrO
2Proton conductive membrane.
Self-supporting PEI/ (F127) ZrO that obtains
2The performance of proton conductive membrane is similar to Example 1.
Embodiment 4:
Step 1: preparation sacrifice layer.Polymethyl methacrylate (PMMA) is dissolved in the acetylacetone,2,4-pentanedione, preparation 10wt% solution.Start whirler, with 3000 rev/mins, kept 1 minute, rotation applies the PMMA sacrifice layer.
Step 2: 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 applies the PSA 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: substrate is immersed in the carrene, dissolve sacrifice layer.Separate with substrate, obtain self-supporting PSA/ (CEO) SiO
2Composite proton conducting film.
Self-supporting PSA/ (CEO) SiO that obtains
2The performance of proton conductive membrane is similar to Example 1.
Step 1: preparation sacrifice layer.(PHS Aldrich) is dissolved in the ethanol, preparation 0.01wt% solution with polyvinylphenol.Speed with 100 cm per minute lifts out substrate from liquid, lift coating polyethylene base phenol sacrifice layer.
Step 2: preparation organic layer.Polyvinyl alcohol (PVA, Aldrich) soluble in water, the preparation 5wt% 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.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: substrate is immersed in the alcohol, dissolve sacrifice layer.Separate with substrate, obtain self-supporting PVA/ (F127) TiO
2Composite proton conducting film.
Self-supporting PVA/ (F127) TiO that obtains
2The performance of composite proton conducting film is similar to Example 1.
Step 1: preparation sacrifice layer.Polymethyl methacrylate (PMMA) is dissolved in the acetylacetone,2,4-pentanedione, preparation 30wt% solution.Speed with 10 cm per minute lifts out substrate from liquid, lift to apply the PMMA sacrifice layer.
Step 2: 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 1 obtains.
Step 3: preparation organic layer.(PVA) is soluble in water for polyvinyl alcohol, 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 2 acquisition.
Step 4: substrate is immersed in the carrene, dissolve sacrifice layer.Separate with substrate, obtain self-supporting (CEO) SiO
2/ PVA composite proton conducting film.
Self-supporting (CEO) SiO that obtains
2The performance of/PVA composite proton conducting film is similar to Example 1.
Step 1: preparation sacrifice layer.Polymethyl methacrylate (PMMA) is dissolved in the acetylacetone,2,4-pentanedione, preparation 30wt% solution.Speed with 100 cm per minute lifts out substrate from liquid, lift to apply the PMMA sacrifice layer.
Step 2: 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) SiO2 colloidal sol of 0.004: 0.1.With 1000 rev/mins, kept 1 minute, the rotation coating contains the SiO2 layer of surfactant on the substrate that step 2 obtains.
Step 3: 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 2 acquisition.
Step 4: substrate is immersed in the carrene, dissolve sacrifice layer.Separate with substrate, obtain self-supporting (CEO) SiO
2/ PSA composite proton conducting film.
Self-supporting (CEO) SiO that obtains
2The performance of/PSA composite proton conducting film is similar to Example 1.
Step 1: preparation sacrifice layer.PHS is dissolved in the ethanol preparation 10wt% solution.Substrate is immersed in the solution, from liquid, lift out substrate, lift and apply the PHS sacrifice layer with the speed of 10 cm per minute.
Step 2: preparation organic layer.PVA is soluble in water, the preparation 5wt% aqueous solution.Speed with 10 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 5wt% solution.Speed with 10 cm per minute lifts out substrate from liquid, lift on the substrate that is coated on step 3 acquisition.
Step 5: 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 6: substrate is immersed in the ethanol, dissolve sacrifice layer.Separate with substrate, obtain self-supporting PVA/ (CEO) SiO
2/ PVA/ (CEO) SiO
2Composite proton conducting film.
Obtain self-supporting PVA/ (CEO) SiO
2/ PVA/ (CEO) SiO
2The 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: organic electronic conduction rete and inorganic proton conductive film layer are formed.
As shown in Figure 2, be (PEI/PCGF)/(CEO) SiO according to embodiment 1 preparation
2The optical photograph of composite proton conducting film.Thickness is that the composite proton conducting film of 500 nanometers is supported on the becket, shows good pliability and mechanical strength.
Measure (PEI/PCGF)/(CEO) SiO for preparing according to embodiment 1 with electric impedance analyzer
2The proton conductivity of film.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.
The cell electrolyte that acts as a fuel, one of them important parameter is a methanol permeability.The methanol permeability that is somebody's turn to do (PEI/PCGF)/(CEO) SiO2 film is about 1.66 * 10-8cm2/S.This numeric ratio
Low approximately two orders of magnitude of 2 * 10-6cm2/S methanol permeability of film.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.
Claims (8)
1. the preparation method of a free-standing composite proton conducting film, this free-standing composite proton conducting film is overlapped by organic electronic conduction rete and inorganic proton conductive film layer and forms, and wherein: the inorganic proton conductive film layer is the phosphorous metal oxide that the proton conductive ability is arranged; Organic electronic conduction rete is the polymer with proton conductive ability, it is characterized in that, said method comprising the steps of:
Step 1: preparation sacrifice layer solution, adopt coating processes, on substrate, form organic sacrificing layer;
Step 2: prepare organic electronic conduction polymer solution, adopt coating processes, on organic sacrificing layer, form organic proton conductive layer;
Step 3: adopt in the following dual mode any one to prepare free-standing composite proton conducting film:
A) preparation inorganic proton conduction colloidal sol adopts coating processes, forms the inorganic proton conductive layer on organic electronic conduction layer; Substrate is immersed in the solvent, and organic sacrificing layer dissolves and is removed, and composite proton conducting film separates with substrate, makes free-standing composite proton conducting film;
B) substrate is immersed in the solvent, organic sacrificing layer dissolves and is removed, and organic electronic conduction layer separates with substrate, preparation inorganic proton conduction colloidal sol, adopt coating processes then, on organic electronic conduction layer, form the inorganic proton conductive layer, make free-standing composite proton conducting film.
2. the preparation method of free-standing 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.
3. the preparation method of free-standing composite proton conducting film according to claim 1 is characterized in that, the substrate described in the step 1 is silicon chip, sheet glass, plastic plate, metallic plate or ceramic wafer.
4. the preparation method of free-standing composite proton conducting film according to claim 1 is characterized in that, the solution of sacrifice layer described in the step 1 is 0.01～50wt% solution that organic polymer is dissolved in the water or forms in the organic solvent.
5. the preparation method of free-standing composite proton conducting film according to claim 1, it is characterized in that the organic electronic conduction polymer solution described in the step 2 is to have the 0.01～50wt% solution that forms in the water-soluble or organic solvent of proton conductive ability organic polymer.
6. the preparation method of free-standing composite proton conducting film according to claim 1, it is characterized in that, inorganic proton conduction colloidal sol described in the step 3, in the following manner the preparation: with metal oxide precursor, deionized water, organic solvent, inorganic acid aqueous solution and additive through being mixed and made into colloidal sol, in colloidal sol, add phosphoric acid then, after brute force stirs, obtain mixed sols.
7. the preparation method of free-standing composite proton conducting film according to claim 6, 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.
8. the preparation method of free-standing composite proton conducting film according to claim 1, it is characterized in that, coating processes described in the step 1 is meant: 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.
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