CN1265478C - Modified proton exchanging film of direct alcohol fuel battery and preparing method thereof - Google Patents

Modified proton exchanging film of direct alcohol fuel battery and preparing method thereof Download PDF

Info

Publication number
CN1265478C
CN1265478C CNB200410027559XA CN200410027559A CN1265478C CN 1265478 C CN1265478 C CN 1265478C CN B200410027559X A CNB200410027559X A CN B200410027559XA CN 200410027559 A CN200410027559 A CN 200410027559A CN 1265478 C CN1265478 C CN 1265478C
Authority
CN
China
Prior art keywords
proton exchange
membrane
alcohol
film
fuel battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB200410027559XA
Other languages
Chinese (zh)
Other versions
CN1585153A (en
Inventor
沈培康
宋洪峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sun Yat Sen University
National Sun Yat Sen University
Original Assignee
National Sun Yat Sen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Sun Yat Sen University filed Critical National Sun Yat Sen University
Priority to CNB200410027559XA priority Critical patent/CN1265478C/en
Publication of CN1585153A publication Critical patent/CN1585153A/en
Application granted granted Critical
Publication of CN1265478C publication Critical patent/CN1265478C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • 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

Landscapes

  • Fuel Cell (AREA)

Abstract

The present invention discloses a modified proton exchange membrane for direct alcohol fuel batteries and a method for preparing the modified proton exchange membrane. The preparing method is realized by that commercial sulfonated resin is used as raw material, inorganic nanometer material is added, and a membrane forming method, such as a casing method, a rolling method, a slurry plating method or a cement dipping method, etc., is adopted to prepare the proton exchange membrane. The proton exchange membrane of the present invention has a favorable proton conductive property and a favorable alcohol resisting property, and the price of the present invention is lower than that of a commercial Nafion membrane. Sulfonated resin is used as a substrate, and inorganic nanometer material is doped for modification. Under the precondition of not influencing the proton conductive property of the membrane, the penetration rate of alcohol molecules in the membrane is reduced, and the alcohol resisting property of membrane material is enhanced.

Description

Modified proton exchange film of direct alcohol fuel battery and preparation method thereof
Technical field
The present invention relates to a kind of preparation method of modified proton exchange film of direct alcohol fuel battery;
The invention still further relates to the modified proton exchange film of the direct alcohol fuel battery that described method prepares.
Background technology
Fuel cell be a kind of directly that chemical energy is efficient by electrochemical reaction, change the device of low-voltage DC into to environmental friendliness, have and be not subjected to Carnot cycle restriction, energy conversion efficiency advantages of higher.Proton Exchange Membrane Fuel Cells wherein (PEMFC) except advantage with general fuel cell, but also have such as outstanding advantages such as no burn into high-energy-density, low operating temperature cold-startings, therefore caused that countries in the world extensively pay attention to.
Directly be with the liquid alcohol Proton Exchange Membrane Fuel Cells of fuel be commonly referred to as direct alcohol fuel battery (Direct alcohol fuel cell, DAFC).Its outstanding advantage be alcohol rich and easy to get, the low price in source, be easy to carry about with one and store.Compare with general hydrogen-oxygen proton exchange membrane fuel cell simultaneously, directly alcohol fuel battery also has volumetric specific energy height, simple in structure, easy to operate, advantage such as cost is lower.Therefore, the directly extremely favor of industrial circle of alcohol fuel battery can be used as the electrical source of power of family's Compact Power Plant, portable electronic appliances power source and motor vehicle etc. in the last few years, had boundless application prospect and huge market.
Proton exchange membrane is the core of direct alcohol fuel battery.At present, the perfluoro sulfonic acid membrane such as the Nafion film that extensively adopt in hydrogen oxygen fuel cell when directly being used in alcohol fuel battery, exist serious pure phenomenon of osmosis.The alcohol molecule can see through proton exchange membrane and arrive negative electrode, and cathod catalyst is poisoned, and reduces the utilance of pure fuel, causes the loss of fuel; Also can cause the increase significantly of oxygen electrode polarization on the other hand, thereby reduce the overall performance of battery, and shortened the useful life of DAFC system.Therefore, reducing the permeability that alcohol sees through proton exchange membrane, prepare that the pure ability of resistance is good, high-performance, proton exchange membrane material cheaply, is the important topic of the direct alcohol fuel battery of exploitation high-performance.
Patent WO99/29763 discloses a kind of sulfonated polyether-ether-ketone (PEEK) proton exchange membrane and preparation technology thereof.It is compared with perfluoro sulfonic acid membrane, hinders pure ability preferably though have, and still exists complicated process of preparation, the more high defective of material price production cost more expensive, film, thereby restricts it in the directly application in alcohol fuel battery field.
People such as Yoon reduce methyl alcohol penetrate by the method for modifying dielectric film, and promptly the method by sputter deposits layer of metal Pd on Nafion film surface, but because Nafion film smooth surface, Pd is little at Nafion film surface adhesion force, comes off easily.Therefore must carry out etch processes to Nafion film surface earlier.And it has also reduced proton conductivity when reducing methanol crossover, and cell integrated performance is also had bad influence [J.of Power Sources, 2002,106:215-223].
People such as Aric ò adopt vinyl-tetrafluoroethene to do base material, by the electron beam radiation, and concurrent grafting, and then carry out crosslinked and sulfonation process, make vinyl-tetrafluoroethene substrate grafting film.Though when reducing methanol crossover, kept certain conductivity and battery performance, this method apparatus expensive, operation are too complicated, operate too loaded down with trivial details [J.of Power Sources, 2003,123:107-115].
People such as Li adopt casting film after PVA and the phosphotungstic acid blend, the film that obtains has the pure effect of tangible resistance, but during long-term work because the loss of phosphorus, unstable properties when causing it to be applied to direct methanol fuel cell, can not long-term work [Materials Letters, 2003,57:1406-1410].
People such as Dimitrova adopt Nafion solution and aerosil and phosphomolybdic acid blend, casting film then, and alcohol-resistant performance increases, but its thermal stability under the DAFC condition of work bad [SolidState Ionics, 2002,150:115-122].
Summary of the invention
One object of the present invention is the shortcoming at prior art, and a kind of modified proton exchange film of direct alcohol fuel battery is provided.This film has good proton conduction performance and alcohol-rejecting ability, and price is lower than the price of commercially available Nafion film, it promptly is substrate with the sulfate resin, carry out modification by the doping inorganic nano material, under the prerequisite of the proton conduction performance that does not influence film, reduce the permeability of pure molecule in film, improve the alcohol-rejecting ability of membrane material.
Another object of the present invention provides the preparation method of the modified proton exchange film of this direct alcohol fuel battery.
Preparation method of the present invention is to be raw material with commercially available sulfate resin, and adds inorganic nano material, prepares the modified proton exchange film of direct alcohol fuel battery by film build methods such as The tape casting, rolling process, coating method or cement-dipping methods.
The preparation method of the modified proton exchange film of direct alcohol fuel battery of the present invention may further comprise the steps:
The first step, sulfate resin and solvent are that 0.5-8Mpa, temperature are to dissolve in 200-650 ℃ the autoclave in pressure under inert gas shielding, make Polymer Solution;
Second step, under agitation add inorganic nano material, Ludox, additive to described Polymer Solution, sonicated mixes it in supersonic generator;
The 3rd step, use The tape casting, this mixed liquor is tiled in curtain coating on polytetrafluoroethylene or the substrate of glass, vacuumize at room temperature is complete to solvent evaporation, under 60 ℃ of condition of normal pressure dry 60-120 minute then; Promptly obtain proton exchange membrane.
In above-mentioned the 3rd step, also can adopt processes such as rolling process, coating method or cement-dipping method to obtain proton exchange membrane.
The percentage by weight of each component is:
Sulfate resin 20-95%
Inorganic nano material 1-60%
Ludox 1-40%
Additive 0.1-10%
The solvent surplus
Described sulfate resin is meant perfluorinated sulfonic acid polymer or has one or more mixtures in the sulfonated polymer of aromatic ring structure.
Described inorganic nano material is meant that particle size is the WO of 1-100nm 3, SiO 2, TiO 2, MoO 2, V 2O 5In one or more mixtures.
Ludox is acidic silicasol or alkaline silica sol;
Additive is surfactant, nano material dispersant or crosslinking agent;
Solvent is water, methyl alcohol, alcohol or dimethyl sulfoxide (DMSO).
The present invention uses the alcohol-rejecting ability of the modified proton exchange film of the direct alcohol fuel battery of barrier film diffusion cell studies.This barrier film diffusion cell is made up of two continuous aquariums, film is clipped between two Room of barrier film diffusion cell the alcohol (1mol/l) of packing in the single pond (A)+sulfuric acid (0.5mol/l) mixed solution; Add sulfuric acid (0.5mol/l) solution in another single pond (B), the determining alcohol variation utilizes and is obtained by its pure oxidation peak current of cyclic voltammetry in single pond (B).The quantity of methyl alcohol that is penetrated into single pond (B) in the more identical time is the pure permeability of comparative film qualitatively.
Compared with the prior art, the present invention has following beneficial effect:
(1) modified proton exchange film of the direct alcohol fuel battery of invention preparation has good proton conduction performance, and its conductivity can reach 10 -1Scm -1The order of magnitude;
(2) modified proton exchange film of the direct alcohol fuel battery of the present invention preparation has good alcohol-rejecting ability, and the methanol permeation rate Nafion1135 film of comparing can reduce methanol permeability more than 50%;
(3) to prepare the method for modified proton exchange film of direct alcohol fuel battery simple in the present invention, and the cost of film is lower than the Nafion film, is easy to industrialization.Can be widely used in fuel cell field, especially require proton exchange membrane to have the direct alcohol fuel battery field of higher alcohol-rejecting ability.
Description of drawings
The WO that Fig. 1 makes for embodiment 1 3The SEM shape appearance figure of/perfluorinated sulfonic acid composite membrane;
The alcohol-rejecting ability comparison diagram of the modified proton exchange film of the direct alcohol fuel battery that Fig. 2 makes for embodiment 3.
Embodiment
Embodiment 1:
Adopt the base material of perfluorinated sulfonic resin as composite membrane; use the solvent of high boiling organic solvent DMF as perfluorinated sulfonic resin; under nitrogen protection, in autoclave, be pressurized to 5Mpa, and be heated to 300 ℃ and dissolve that to obtain perfluor sulfoacid resin solution stand-by.Press WO 3: perfluorinated sulfonic resin=3: 97 (mass ratio) batching.Adding nano-scale in perfluor sulfoacid resin solution is the WO of 4nm 3Nano material, the strong agitation while adding obtains composite membrane solution, and ultrasonic dispersion in supersonic generator is till mixing.Adopt the The tape casting film forming then, be about to this mixed liquor and be tiled in curtain coating on the polytetrafluoroethyldisk disk, film thickness monitoring is at 50 μ m, vacuumize at room temperature is complete to solvent evaporation, under 60 ℃ of condition of normal pressure dry 90 minutes then, dried composite membrane passed through hydrogen peroxide solution, deionized water, the 0.5mol/lH of 3wt% respectively 2SO 4Solution, deionized water are standby after boiling and handling in 1 hour.Fig. 1 is the WO that makes 3/ perfluorinated sulfonic resin composite membrane pattern, surface distributed is smooth evenly, is translucent.
Embodiment 2:
Adopt the base material of perfluorinated sulfonic resin as composite membrane; use the solvent of high boiling organic solvent DMF as perfluorinated sulfonic resin; under nitrogen protection, in autoclave, be pressurized to 5Mpa, and be heated to 300 ℃ and dissolve that to obtain perfluor sulfoacid resin solution stand-by.Press TiO 2: Ludox: perfluorinated sulfonic resin=5: 5: 90 (mass ratio) batching.Adding nano-scale in perfluor sulfoacid resin solution is the nano-TiO of 6nm 2And Ludox, the strong agitation while adding obtains composite membrane solution, and ultrasonic dispersion in supersonic generator is till mixing.Adopt the The tape casting film forming then, be about to this mixed liquor and be tiled in curtain coating on the polytetrafluoroethyldisk disk, film thickness monitoring is at 50 μ m, vacuumize at room temperature is complete to solvent evaporation, under 60 ℃ of condition of normal pressure dry 90 minutes then, dried composite membrane passed through hydrogen peroxide solution, deionized water, the 0.5mol/lH of 3wt% respectively 2SO 4Solution, deionized water are standby after boiling and handling in 1 hour.The Nano silica sol that makes/perfluorinated sulfonic resin composite membrane surfacing, even, transparent.
Embodiment 3:
Press MoO 2: Ludox: half perfluorosulfonic acid resin=5: 15: 80 (mass ratio) batching.Adding nano-scale in half perfluorosulfonic acid resin solution is the nanometer MoO of 8nm 2And Ludox, the strong agitation while adding obtains composite membrane solution, and ultrasonic dispersion in supersonic generator is till mixing.Adopt the The tape casting film forming then, be about to this mixed liquor and be tiled in curtain coating on the polytetrafluoroethyldisk disk, film thickness monitoring is at 50 μ m, vacuumize at room temperature is complete to solvent evaporation, under 60 ℃ of condition of normal pressure dry 90 minutes then, dried composite membrane passed through hydrogen peroxide solution, deionized water, the 0.5mol/l H of 3wt% respectively 2SO 4Solution, deionized water are standby after boiling and handling in 1 hour.The resistance methyl alcohol performance of this film as shown in Figure 2.Curve a is the penetration curve of Nafion1135 film, and b is the pure penetration curve with the film of the present invention's preparation.

Claims (2)

1, a kind of preparation method of modified proton exchange film of direct alcohol fuel battery is characterized in that comprising the steps:
The first step, sulfate resin and solvent are that 0.5-8Mpa, temperature are to dissolve in 200-650 ℃ the autoclave in pressure under inert gas shielding, make Polymer Solution;
Second step, under agitation add inorganic nano material, Ludox, additive to described Polymer Solution, sonicated mixes it in supersonic generator;
The 3rd step, use The tape casting, this mixed liquor is tiled in curtain coating on polytetrafluoroethylene or the substrate of glass, vacuumize at room temperature is complete to solvent evaporation, under 60 ℃ of condition of normal pressure dry 60-120 minute then; Promptly obtain proton exchange membrane;
Above-mentioned each components based on weight percentage consumption is as follows:
Sulfate resin 20-95%
Inorganic nano material 1-60%
Ludox 1-40%
Additive 0.1-10%
The solvent surplus
Sulfate resin is meant perfluorinated sulfonic acid polymer or has one or more mixtures in the sulfonated polymer of aromatic ring structure; Inorganic nano material is meant that particle size is the WO of 1-100nm 3, SiO 2, TiO 2, MoO 2, V 2O 5In one or more mixtures; Ludox is acidic silicasol or alkaline silica sol; Additive is surfactant, nano material dispersant or crosslinking agent; Solvent is water, methyl alcohol, alcohol or dimethyl sulfoxide (DMSO).
2, the modified proton exchange film of the direct alcohol fuel battery that obtains of the described preparation method of claim 1.
CNB200410027559XA 2004-06-11 2004-06-11 Modified proton exchanging film of direct alcohol fuel battery and preparing method thereof Expired - Fee Related CN1265478C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB200410027559XA CN1265478C (en) 2004-06-11 2004-06-11 Modified proton exchanging film of direct alcohol fuel battery and preparing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB200410027559XA CN1265478C (en) 2004-06-11 2004-06-11 Modified proton exchanging film of direct alcohol fuel battery and preparing method thereof

Publications (2)

Publication Number Publication Date
CN1585153A CN1585153A (en) 2005-02-23
CN1265478C true CN1265478C (en) 2006-07-19

Family

ID=34601400

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB200410027559XA Expired - Fee Related CN1265478C (en) 2004-06-11 2004-06-11 Modified proton exchanging film of direct alcohol fuel battery and preparing method thereof

Country Status (1)

Country Link
CN (1) CN1265478C (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1312788C (en) * 2005-09-30 2007-04-25 清华大学 Proton exchange composite membrane for all vanadium redox flow battery and its preparing method
CN100441616C (en) * 2006-12-08 2008-12-10 中山大学 Alcohol-rejecting proton exchange film for alcohol fuel cell and its preparation method
CN101440167B (en) * 2007-11-19 2012-07-04 中国石油大学(北京) Preparation of SiO2/organic polymer composite proton exchange membrane
CN103904344B (en) * 2014-04-23 2016-02-10 北京九谷超微科技有限公司 A kind of proton exchange membrane and preparation method thereof
CN111326775B (en) * 2018-12-17 2021-07-27 中国科学院大连化学物理研究所 Membrane electrode based on ultrathin membrane direct methanol fuel cell and preparation method thereof
CN112481657B (en) * 2020-11-16 2021-10-26 山东东岳高分子材料有限公司 Fluoride ion exchange membrane for alkali chloride electrolysis having impurity tolerance

Also Published As

Publication number Publication date
CN1585153A (en) 2005-02-23

Similar Documents

Publication Publication Date Title
CN110256913B (en) Preparation method of antioxidant, water-retaining agent, mixture and modified fuel cell membrane electrode
CN100345332C (en) Process for preparing proton exchange film full cell chips with water retaining function
CN108878993A (en) A method of slowing down proton exchange membrane electrochemical degradation
CN1725536A (en) Self-moist proton exchange film and its preparation method
CA2614876A1 (en) Electrolyte membrane for polymer electrolyte fuel cell, process for its production and membrane-electrode assembly for polymer electrolyte fuel cell
CN102569855A (en) Electrolyte membrane and fuel cell employing it
Kumar et al. Polypyrrole and polyaniline-based membranes for fuel cell devices: A review
CN116646574A (en) Polymer modified composite proton exchange membrane, preparation method thereof and fuel cell
Nishihara et al. Proton-conductive nano zeolite-PVA composite film as a new water-absorbing electrolyte for water electrolysis
CN1265478C (en) Modified proton exchanging film of direct alcohol fuel battery and preparing method thereof
CN101488572B (en) Ionic exchange film for fuel cell and preparation thereof
CN102838777A (en) Recovery method of sulfonated polyether ether ketone (SPEEK) / polyaniline (PANI) / propylene glycol monomethyl acetate (PMA) composite proton exchange membrane
CN101733021B (en) Perfluoro ion exchange membrane with interpenetrating network structure and preparation method thereof
CN111525167B (en) Preparation method of perfluorosulfonic acid resin/modified lignin composite ion exchange membrane
CN111129557B (en) Phosphoric acid modified polybenzimidazole proton exchange membrane and preparation method thereof
CN100452501C (en) Modified alcohol-barrier proton exchange film based on hydrophilic area surface and its production
JP2007109634A (en) Membrane for proton conductive fuel cell capable of operating under nonaqueous and high temperature condition and its manufacturing method
CN1677732A (en) Organic-inorganic compoiste proton exchange film and preparing method
CN102002167A (en) Proton exchange membrane applied to direct methanol fuel cell and preparation method thereof
CN1264597C (en) Inhibiting alcohol proton exchanging film and its preparation process
CN1803921A (en) Intermediate temperature proton electro-conductive film material based on sulphonated polystyrene resin hollow nano-microsphere
CN100479242C (en) Production of composite proton exchange-film of water-retaining component uniform dispersion
CN1263179C (en) Process for preparing proton composite exchange membrane for high temperature proton exchange membrane fuel battery
CN1195337C (en) Self-humidifying solid electrolyte composite membrane and manufacturing process thereof
CN101794888B (en) Ion exchange membrane of interpenetrating network structure and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C17 Cessation of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20060719