CN101626084A - Method for preparing membrane electrode by CCM - Google Patents
Method for preparing membrane electrode by CCM Download PDFInfo
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- CN101626084A CN101626084A CN200910184058A CN200910184058A CN101626084A CN 101626084 A CN101626084 A CN 101626084A CN 200910184058 A CN200910184058 A CN 200910184058A CN 200910184058 A CN200910184058 A CN 200910184058A CN 101626084 A CN101626084 A CN 101626084A
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention relates to an improvement of a method for preparing the membrane electrode of a proton exchange membrane fuel cell by screen printing, characterized in that a solvent is paved on a non-deformation flat heat carrier before complete volatilization during the membrane preparation, and then a catalyst layer is sprayed or screen-printed. The invention well solves the following two technical challenges: the membrane is difficult to flatten and fix, and expansion is easy to occur when spraying catalyst; therefore, not only the occurrence of difficult flattening and fixing of the membrane can be completely avoided, but also, the catalyst layer is sprayed evenly, as the membrane is flat when spraying catalyst; in addtion, the one-time pass percentage of catalyst spraying is improved to above 95%, and the uniformity of the membrane electrode is excellent.
Description
Technical field
The present invention is the improvement that silk screen printing is prepared membrane electrode of fuel batter with proton exchange film CCM preparation method, particularly the applicant is formerly applied for a patent 200710025554.7 further improvement.
Background technology
Membrane electrode (MEA) is one of core component of Proton Exchange Membrane Fuel Cells, is the electrochemical reaction zone takes place.Membrane electrode preparation at present mainly contains two kinds of methods: a kind of for catalyst by modes such as spraying, wire mark, blade coatings, impose on the carbon paper that hydrophobisation handles, prepare gas-diffusion electrode (GDE), make up with proton exchange membrane (for example Nafion film) hot pressing then; Another kind of for catalyst by modes such as spraying, wire mark, blade coating are coated with, impose on and obtain CCM on the proton exchange membrane, be covered with gas diffusion layers then, make up with diffusion layer.Prepare membrane electrode with GDE and compare, CCM prepares the membrane electrode method can not carry out hot pressing, thus the damage of avoiding film to cause because of hot pressing, and and catalyst contacts closely with proton exchange membrane, helps electrochemical reaction and generates water wetting to film.
The CCM method prepares membrane electrode, mainly contains two kinds of direct method and transfer printings at present.Transfer printing such as Chinese patent CN1560949, CN1862855 is described, earlier catalyst pulp is coated to the transfer medium surface, forms Catalytic Layer after solvent is removed in heating, by hot pressing Catalytic Layer is transferred on the proton exchange membrane then.This method technology more complicated, preparation cost is higher, and Catalytic Layer is difficult to control with contacting of film during the hot pressing transfer printing, and film and transfer medium engagement edge are stressed irregular, cause the damage of film easily; In transfer process,, make the part catalyst be bonded on the transfer medium in addition, cause catalyst utilization to descend because transfer printing is incomplete.Transfer medium hot pressing repeatedly in addition, easily destroyed and can not reuse, increased manufacturing cost.Direct method is dispersant as described in the Chinese patent CN1477724 with low boiling, low viscosity alcohol, and higher boiling point, high viscosity alcohol prepare catalyst pulp for stabilizer, directly are coated on the treated proton exchange membrane then.It is simple that direct method has technology, but the proton exchange membrane that catalyst pulp applies is very thin flexible membrane, thickness as thin as a wafer for example Nafion212, Nafion211 thickness only be 50 and 25 microns, be difficult to smooth fixingly, cause the fixing very difficult of film when applying.Prior art adopts usually film is tiled on the planar substrates, adopts artificial brushing method then, the manual brushing catalyst, and efficient is very low.Silk screen printing can realize the coating to slurry, and more manually being coated with carried catalyst has higher production efficiency, but in the screen printing process because print roller needs to roll back and forth, therefore requiring to be filmed must firm fixation.Existing screen process press adopts fixedly printed material body of air draught usually, by numerous wind inlets on the substrate printed material body is sucked on the base station surface, moves for preventing that film is in press stressed, and enough negative pressure air draughts must be arranged.Yet big air draught easily causes film generation crape as thin as a wafer to fold existing out-of-flatness; In addition, film runs into water, swelling can take place the ethanol equal solvent, and contains alcohols solvent usually in the configuration catalyst pulp, can cause the swelling set of film when wire mark.The film out-of-flatness not only causes being coated with the inhomogeneous of carried catalyst layer on film, and first-time qualification rate is the highest about 80%, influence assembling pile performance, and the membrane electrode poor repeatability of preparation, be difficult to obtain the membrane electrode of uniformity, cause assembling pile performance heterogeneity.Above-mentioned reason objectively is difficult to adopt silk screen seal coating catalyst.The smooth of above-mentioned film fixed, and become a big obstacle of restriction CCM method efficient production membrane electrode, also is to cause membrane electrode to be difficult to a major reason of commercial applications.
The applicant formerly applies for a patent 200710025554.7 silk screen printing CCM and prepares the membrane electrode of fuel batter with proton exchange film method, proposes to adopt the air draught of the dull and stereotyped carrier negative pressure of micropore to fix.More directly adopt the screen process press base station, though solved the deficiency that macropore air draught film crape folding is difficult to pave, solvent causes film swelling defective still to exist in the catalyst pulp, fails to be overcome, and the micropore substrate makes that the required power of fan of air draught is higher, has increased to be coated with the carried catalyst energy consumption.Above-mentioned deficiency still has is worth improved place.
Summary of the invention
The object of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of and not only can high efficiency be coated with carried catalyst, and can guarantee film smooth firmly pave fixing, the heart and avoid the CCM of film swelling during catalyst to prepare the method for membrane electrode at wire mark or spraying.
The object of the invention realizes, the main improvement is when wire mark or spraying Catalytic Layer, not volatilization fully of solvent at the preparation film, it is paved in the constant temperature substrate, and carry out silk screen printing or spraying immediately, thus film can smoothly be fixed, eliminated the swelling of film again, make spraying or during the wire mark catalyst film can not be moved, shrink, guaranteed film smooth when being coated with carried catalyst.Specifically, CCM of the present invention prepares the method for membrane electrode, is included in and is coated with the carried catalyst layer on the film, and oven dry removes solvent, and solvent does not volatilize just to be tiled in fully when it is characterized in that making film does not have the dull and stereotyped heat carrier of distortion, spraying or silk screen printing catalyst layer.
The present invention makes film and prior art is basic identical, for go up cast or spraying electrolyte solution at polymer-based counterdie (for example polytetrafluoroethylene), for example solution such as proton-conducting polymer, perfluor based polyalcohol, benzimidazole-based polymer, ketone group polymer, ester group polymer, amido polymer, imide polymer are treated promptly to get proton exchange membrane after the solvent evaporates.The inventive method is behind cast or spraying electrolyte solution, solvent is volatilization fully not, for example solvent is 30-95wt% in the film, when more preferably solvent is 75-85wt% (solvent is coated with to carry at catalyst at least and finishes not yet volatilization fully), being about to wet film paves on flat base, utilize the natural adsorptivity of wet film to make film obtain smooth fixing, simultaneously owing to be wet film, when wire mark or spraying Catalytic Layer, swelling can not take place, thereby it is smooth effectively fixing that film is obtained, and solved the difficult fixing two big defectives that reach easy swelling of prior art film.
Dull and stereotyped carrier of the present invention has no special requirements, if enough evenness are arranged and meet water and/or smooth plates that solvent can not deform all can, for example glass, metallic plate, solvent is not had the plastic plate of swelling, polyformaldehyde plate etc. for example.The flat plate heat carrier, the one, cold and hot variation causes distortion in the film-forming process, the 2nd, also help the volatilization of follow-up Catalytic Layer solvent, its temperature roughly requires temperature similar with system film and solvent flashing, and for example 60-125 ℃, more preferably 85-105 ℃.The flat plate heat carrier can be that for example Electric radiant Heating Film of electric heating is set on dull and stereotyped carrier, also can be carrier to be positioned in the baking oven heat, and takes out band temperature shop film.The present invention is a kind of better to be according to the film size, and preparation can improve wire mark or spraying production efficiency so suitably greater than the dull and stereotyped carrier baking oven of film.
CCM of the present invention prepares the method for membrane electrode, with respect to prior art, because employing solvent when the system film volatilizees fully just to be tiled in and does not have on the dull and stereotyped heat carrier of distortion, better having solved when being coated with carried catalyst film is difficult to smooth fixing and swelling two big technical barriers take place, it is fixing not only can to avoid film to be difficult to tiling fully, and chance water or alcohols solvent swelling set problem, can adapt to silk screen printing or spraying continuous high-efficient industrialized mass production thereby reach, and because film is smooth when being coated with carried catalyst, it is even to be coated with the carried catalyst layer, be coated with shoe catalyst first-time qualification rate and can bring up to more than 95%, gained membrane electrode performance homogeneity is better.
Below in conjunction with two specific embodiments; the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention to conceive whole technical schemes down; therefore should not be construed as the technical scheme qualification total to the present invention, some are In the view of the technical staff, and the unsubstantiality that does not depart from the present invention's design increases and/or change; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection range of the present invention.
Embodiment
Embodiment 1: adopt for example long and wide proton exchange membrane that is 10.5 centimetres of CN200510046177.6 method preparation, dried 2.5 hours down at 80～100 ℃, obtain the wet film (weight-loss method is differentiated solvent 75wt%) that solvent does not volatilize as yet fully.Then directly with wet film, being placed on by shifting out temperature in the baking oven is on 85-105 ℃ the glass plate, 0.5 centimetre of part is respectively arranged around the film, be not printed on catalyst with the covering of article such as adhesive tape, be put in screen process press loading floor (being placed with thermal insulation board), (Catalytic Layer is 40% the carbon supported platinum catalyst and the electrolyte solution that contains Nafion5% of du pont company production by platiniferous to the wire mark Catalytic Layer, evenly mix in 3: 1 ratios of mass ratio, add aqueous isopropanol and be mixed with 20wt% concentration solution, prepared Chinese ink shape catalyst liquid is made in concussion in ultrasonic wave).Treat solvent evaporates in the Catalytic Layer, take off film and weigh, look gain in weight decision and whether replenish printing (weight difference of weighing for twice is the weight of coating catalyst and Nafion), extremely required catalytic amount; Bone dry is not simultaneously scribbled the semi-finished product of Catalytic Layer, repeat above-mentioned print steps, at semi-finished product film another side printed catalyst layer.At last with satisfactory be coated with the film that is loaded with catalyst be put in 80-100 ℃ down baking remove solvent.Boiled 0.5～3 hour with 0.1～5mol/L sulfuric acid solution respectively again, composite membrane is converted into the hydrogen ion type, boil with 3% hydrogen peroxide again and removed organic impurities in 1 hour, clean up and just obtain operable CCM film.
Embodiment 2: wire mark is coated with the carried catalyst method, makes to be coated with carried catalyst into, all the other are the same substantially.
To those skilled in the art; under this patent design and specific embodiment enlightenment; some distortion that can directly derive or associate from this patent disclosure and general knowledge; those of ordinary skills will recognize also can adopt additive method; or the substituting of known technology commonly used in the prior art; and the mutual various combination between feature; for example hold the change of film flat board; perhaps adopt the flat board of band heater; or the like unsubstantiality change, can be employed equally, can both realize and basic identical function of the foregoing description and effect; launch for example no longer one by one to describe in detail, all belong to this patent protection range.
Claims (8)
1, CCM prepares the method for membrane electrode, is included in and is coated with the carried catalyst layer on the film, and oven dry removes solvent, and solvent does not volatilize just to be tiled in fully when it is characterized in that making film does not have the dull and stereotyped heat carrier of distortion, spraying or silk screen printing catalyst layer.
2, the method for preparing membrane electrode according to the described CCM of claim 1, when it is characterized in that spreading film in the film solvent be 30-95wt%.
3, the method for preparing membrane electrode according to the described CCM of claim 2, when it is characterized in that spreading film in the film solvent be 75-85wt%.
4, the method for preparing membrane electrode according to the described CCM of claim 1 is characterized in that dull and stereotyped heat carrier temperature is 60-125 ℃.
5, the method for preparing membrane electrode according to the described CCM of claim 4 is characterized in that dull and stereotyped heat carrier temperature is 85-105 ℃.
6, the method for preparing membrane electrode according to claim 1,2,3,4 or 5 described CCM is characterized in that dull and stereotyped heat carrier is glass, metallic plate.
7, the method for preparing membrane electrode according to the described CCM of claim 6 is characterized in that dull and stereotyped heat carrier is not for being with heater.
8, the method for preparing membrane electrode according to the described CCM of claim 7 is characterized in that dull and stereotyped heat carrier is heated by baking oven.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910184058A CN101626084A (en) | 2009-08-12 | 2009-08-12 | Method for preparing membrane electrode by CCM |
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| CN200910184058A CN101626084A (en) | 2009-08-12 | 2009-08-12 | Method for preparing membrane electrode by CCM |
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| CN101626084A true CN101626084A (en) | 2010-01-13 |
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| CN200910184058A Pending CN101626084A (en) | 2009-08-12 | 2009-08-12 | Method for preparing membrane electrode by CCM |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102088092A (en) * | 2011-01-10 | 2011-06-08 | 北京科技大学 | Preparation method for three-dimensional network structure membrane electrode for direct methanol fuel cell |
| CN104181219A (en) * | 2014-08-29 | 2014-12-03 | 武汉理工大学 | Formaldehyde gas sensor |
| CN108767297A (en) * | 2018-05-25 | 2018-11-06 | 上海交通大学 | A kind of preparation method of fuel cell membrane electrode |
| CN109326808A (en) * | 2018-09-20 | 2019-02-12 | 宝应县润华静电涂装工程有限公司 | It is a kind of to prevent the corrugated film of Surface modification of proton exchange membrane |
| CN110676494A (en) * | 2019-09-24 | 2020-01-10 | 东莞市魔方新能源科技有限公司 | Preparation method of membrane electrode, membrane electrode and proton exchange membrane fuel cell |
| CN111785932A (en) * | 2020-09-07 | 2020-10-16 | 苏州清陶新能源科技有限公司 | Preparation method of positive electrode of lithium ion battery |
-
2009
- 2009-08-12 CN CN200910184058A patent/CN101626084A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102088092A (en) * | 2011-01-10 | 2011-06-08 | 北京科技大学 | Preparation method for three-dimensional network structure membrane electrode for direct methanol fuel cell |
| CN102088092B (en) * | 2011-01-10 | 2013-04-03 | 北京科技大学 | Preparation method for three-dimensional network structure membrane electrode for direct methanol fuel cell |
| CN104181219A (en) * | 2014-08-29 | 2014-12-03 | 武汉理工大学 | Formaldehyde gas sensor |
| CN108767297A (en) * | 2018-05-25 | 2018-11-06 | 上海交通大学 | A kind of preparation method of fuel cell membrane electrode |
| CN108767297B (en) * | 2018-05-25 | 2021-11-23 | 上海交通大学 | Preparation method of fuel cell membrane electrode |
| CN109326808A (en) * | 2018-09-20 | 2019-02-12 | 宝应县润华静电涂装工程有限公司 | It is a kind of to prevent the corrugated film of Surface modification of proton exchange membrane |
| CN110676494A (en) * | 2019-09-24 | 2020-01-10 | 东莞市魔方新能源科技有限公司 | Preparation method of membrane electrode, membrane electrode and proton exchange membrane fuel cell |
| CN110676494B (en) * | 2019-09-24 | 2023-08-08 | 魔方氢能源科技(江苏)有限公司 | Membrane electrode preparation method, membrane electrode and proton exchange membrane fuel cell |
| CN111785932A (en) * | 2020-09-07 | 2020-10-16 | 苏州清陶新能源科技有限公司 | Preparation method of positive electrode of lithium ion battery |
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Application publication date: 20100113 |