CN1411085A - Proton exchange film and its preparation method - Google Patents
Proton exchange film and its preparation method Download PDFInfo
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- CN1411085A CN1411085A CN01133538A CN01133538A CN1411085A CN 1411085 A CN1411085 A CN 1411085A CN 01133538 A CN01133538 A CN 01133538A CN 01133538 A CN01133538 A CN 01133538A CN 1411085 A CN1411085 A CN 1411085A
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- film
- proton exchange
- micropore
- preparation
- exchange membrane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
This invention discloses a proton exchange film and its preparation method. The film is made of a ceramic thin film with thickness of h is less than or equal to 1mm and distributed with several microholes on it with the diameter n is less than or equal to 2mm, distributed on the whole thin film and fully filled with high conductivity electrolyte. Diameter of hole n is better is nanometer degree. The preparation method is as follow: first to prepare ordered microholes on the metal film with thickness in h is less than or equal to 1mm to be oxidated to ceramic film by electrochemical or other ways, then to fill with high conductivity electrolyte. The above mentioned metal film is better A1 film with the advantage of easy filming, low cost solving the problem of catalyst poisoning by increasing operation temperature of the proton exchange film.
Description
Technical field
The invention belongs to the amberplex technical field, be specifically related to a kind of proton exchange membrane, it is particularly useful for fuel cell.
Background technology
Preparing high efficiency amberplex is one of core technology of fuel cell.The used exchange membrane of Proton Exchange Membrane Fuel Cells (PEMEC) adopts many (entirely) perfluorinated sulfonic acid polymer Nafion series membranes mostly at present.But there is following shortcoming in the Nafion series membranes:
(1) film forming difficulty, cost height.The Nafion series membranes is a (per) fluoropolymer, and structure is also complicated.The sulfonation of perfluor material and synthetic all unusual difficulties, and the hydrolysis in the film forming procedure and sulfonation make polymer sex change, degraded easily, makes the film forming difficulty to cause cost higher.
(2) to some hydrocarbon conducting.Because the design feature of high polymer and the technology path characteristics in the building-up process make that unavoidably existence is empty in the film of making, the hydrocarbon that some performance is suitable can directly pass the cavity; Reduce the utilization ratio of raw material.
(3) catalyst poisoning.There is the anthracemia problem in the employed anode catalyst of Nafion.
These shortcomings make Proton Exchange Membrane Fuel Cells realize that the scale commodity production is restricted.See " Proton-conducting polymer electrolyte membranes based onhydrocarbon polymers " (Prog.Polym.Sci.25 (2000), 1463-1502) with " Hybrid Nafion-inorganic membrane with potential applications forpolymer electrolyte fuel cells " (Journal of ElectroanalyticalChemistry, 489 (2000), 101-105).
Summary of the invention
The object of the present invention is to provide a kind of proton exchange membrane that can overcome above-mentioned defective.This proton exchange membrane has the film forming of being easy to, characteristics that cost is low, and can solve the catalyst poisoning problem.The present invention also provides the method for preparing this proton exchange membrane.
For achieving the above object, this proton exchange membrane is made of the ceramic membrane of a thickness h≤1mm, is distributed with some micropores on this ceramic membrane in order, its aperture n≤2mm, micropore spreads all over whole ceramic membrane, is filled with the electrolyte of high conductivity in the micropore of described ceramic membrane.
The preparation method of above-mentioned proton exchange membrane is:
(1) the orderly micropore of preparation on thickness h≤1mm metallic film;
(2) with electrochemical method or alternate manner with the surface or all be oxidized to pottery;
(3) electrolyte of filling high conductivity in the micropore of ceramic membrane.
The best aluminium film of above-mentioned metallic film.
" in order micropore " of indication of the present invention be meant the hole pipeline straight, perpendicular to the micropore on fenestra surface.Micropore pipeline in traditional microporous barrier is tortuous, three-dimensional random distribution, and this makes the distance of diffusate wherein extend significantly.In order to improve permeation flux, can adopt the microporous barrier of thinner thickness, or adopt bigger osmotic drive power, but this all can increase the ability that sees through of non-intended particle.In order the hole pipeline in the microporous barrier straight, perpendicular to the fenestra surface, guarantee that micropore distributes and the uniformity of film properties in film, make it improve permeation flux under prerequisite not losing optionally.At present, adopt anode oxidation method, can produce aperture 5-200nm, density reaches 10
11Individual/cm
2Orderly microporous barrier, and very even.With above-mentioned orderly micropore ceramics film as skeleton, filling electrolyte in micropore can make the dielectric film in the fuel cell, does not so just need the independent film forming of electrolyte, can select the inorganic or organic bath of high conductivity as required, as various super acids.Like this, the inventive method has solved the problem of Nafion film forming difficulty dexterously, and is convenient to realize the large-scale industrial production of proton exchange membrane, reduces manufacturing cost significantly.
When micropore size of the present invention reaches nanometer scale, behind the filling electrolyte, residual porosity pipe diameter in the microporous barrier is a nanometer scale in order, and it also should be ordering, also should there be the effect of capillary pressure in this ordering nanotube capillaries, therefore can increases substantially permeation flux, in addition, the nanometer micropore of ordering also may bring a lot of special catalysis, characterization of adsorptions to microporous barrier itself and the catalyst that adheres to, and improves the catalytic efficiency of electrode.
According to the study, as the working temperature of proton exchange membrane being brought up to the 130 ℃ of poisoning problems that can eliminate the carbon monoxide of catalyst.But after temperature was higher than 90 ℃, the water content of Nafion series membranes reduced fast with the rising of temperature, its conductivity is also descended fast, thereby be difficult to improve its working temperature.But the present invention can solve the poisoning problem of catalyst by the working temperature that improves dielectric film itself.
Embodiment
Select the metallic aluminium film of thickness h=100um for use, use laser on whole film, to punch, aperture n=0.1mm, will make the hole pipeline straight, perpendicular to the fenestra surface, use anode oxidation method that the micropore aluminium film surface is oxidized to ceramic membrane then, refill 20%H
2SO
4Ludox.Present embodiment also can use other oxidizing process that the porous aluminium surface oxidation is become ceramic membrane, or fills the electrolyte of other high conductivity.
Aperture n is preferably nanometer scale, i.e. n≤1um, best results of the present invention at this moment.The present invention can use existing the whole bag of tricks to punch on metallic film, as laser drilling method or electrochemical etching method etc.Also can adopt existing the whole bag of tricks that the microporous metal membrane surface oxidation is become ceramic membrane, as anode oxidation method, air oxidation process etc.
Proton exchange membrane provided by the invention as a kind of new material, also has broad application prospects in fields such as electrochemistry, environmental protection, separation, microelectronics.As can be used as dielectric film in battery operation, electrolysis industry, the water treatment electrochemical method; Diffusion barrier in the membrane technology, barrier film of microelectronic component such as ultracapacitor or the like.
Claims (5)
1. proton exchange membrane, it is characterized in that it is made of the ceramic membrane of a thickness h≤1mm, on this ceramic membrane, be distributed with some micropores in order, its aperture n≤2mm, micropore spreads all over whole ceramic membrane, is filled with the electrolyte of high conductivity in the micropore of described ceramic membrane.
2. proton exchange membrane according to claim 1 is characterized in that: described aperture n≤1um.
3. proton exchange membrane according to claim 1 and 2 is characterized in that: the micropore on the described ceramic membrane is for evenly distributing.
4. the preparation method of proton exchange membrane according to claim 1 and 2 is characterized in that:
(1) the orderly micropore of preparation on thickness h≤1mm metallic film;
(2) with above-mentioned metallic film surface or all be oxidized to ceramic membrane;
(3) electrolyte of filling high conductivity in the micropore of ceramic membrane.
5. proton exchange membrane according to claim 4 is characterized in that: described metallic film is the aluminium film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011335386A CN1205684C (en) | 2001-10-08 | 2001-10-08 | Proton exchange film and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011335386A CN1205684C (en) | 2001-10-08 | 2001-10-08 | Proton exchange film and its preparation method |
Publications (2)
| Publication Number | Publication Date |
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| CN1411085A true CN1411085A (en) | 2003-04-16 |
| CN1205684C CN1205684C (en) | 2005-06-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011335386A Expired - Fee Related CN1205684C (en) | 2001-10-08 | 2001-10-08 | Proton exchange film and its preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105624759A (en) * | 2015-12-30 | 2016-06-01 | 苏州容电储能科技有限公司 | Ceramic membrane with capillary structure and super dehumidifying and wetting performance and preparation method thereof |
| CN107289722A (en) * | 2017-06-12 | 2017-10-24 | 青岛海尔股份有限公司 | A kind of depository dish and the refrigerator with it |
| CN114204086A (en) * | 2021-11-29 | 2022-03-18 | 镇江春环密封件集团有限公司 | Formula and process of novel acid fuel cell composite membrane |
-
2001
- 2001-10-08 CN CNB011335386A patent/CN1205684C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105624759A (en) * | 2015-12-30 | 2016-06-01 | 苏州容电储能科技有限公司 | Ceramic membrane with capillary structure and super dehumidifying and wetting performance and preparation method thereof |
| CN105624759B (en) * | 2015-12-30 | 2018-02-16 | 苏州容电储能科技有限公司 | Ceramic membrane with capillary structure and super dehumidifier wetting property and preparation method thereof |
| CN107289722A (en) * | 2017-06-12 | 2017-10-24 | 青岛海尔股份有限公司 | A kind of depository dish and the refrigerator with it |
| CN114204086A (en) * | 2021-11-29 | 2022-03-18 | 镇江春环密封件集团有限公司 | Formula and process of novel acid fuel cell composite membrane |
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| Publication number | Publication date |
|---|---|
| CN1205684C (en) | 2005-06-08 |
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