CN1661838A - Method for preparing self-humidifying membrane electrode in fuel cell - Google Patents
Method for preparing self-humidifying membrane electrode in fuel cell Download PDFInfo
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- CN1661838A CN1661838A CN2005100165630A CN200510016563A CN1661838A CN 1661838 A CN1661838 A CN 1661838A CN 2005100165630 A CN2005100165630 A CN 2005100165630A CN 200510016563 A CN200510016563 A CN 200510016563A CN 1661838 A CN1661838 A CN 1661838A
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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
Abstract
Carbon paper, carbon cloth, carbon felt, porous thin slice of foam nickel or foam titanium are as electroconductive carrier. Carbon carried catalyst and admixture of hydrophobic latex containing fluoropolymer and hole expansion agent are coated on the electroconductive carrier. Content of catalyst metal contained on carbon carried catalyst on electroconductive carrier is 0.02 - 3 mg / cm2, and content of fluoropolymer on electroconductive carrier is 0.1-2 cm2. Then, following operations are carried out for electroconductive carrier: hot pressing the carrier for 1-5 minutes under l-7MPa, at 100-200 deg.C; after agglomeration at 300-500 deg.C, admixture of carbon carried catalyst and ionic polymer solution is coated on the carrier; faced to a piece of ion exchange membrane, two pieces of dried carrier clip the membrane; membrane electrode is made by hot pressing clipped membrane for 1-5 minutes under l-7MPa, at 100-160 deg.C.
Description
Technical field
The invention belongs to the preparation method of self-humidifying membrane electrode in fuel cell.
Background technology
Manufacturing about membrane electrode, E. La Moni etc. has described a kind of general manufacture method among the Chinese patent CN98109696.4: after active carbon or other conduction charcoal and ptfe emulsion are mixed, be coated on carrier carbon paper or charcoal cloth or other conductive carrier, be coated with the mixture that one deck contains catalyst, ptfe emulsion, ionomer solution after the heat treatment again, clamp an ionic polymer membranes with two such carriers then, form polymer membrane electrode through hot pressing, hereinafter to be referred as MEA.
Other method has wire mark method, electrodeposition process, spraying process, sputtering method, chemical deposition or the like.Such patent or document can be referring to 1, wire mark method: Int.J.Hydrogen.Energy.vol 23, No.1 pp1045-1048,1998; 2, pre-deposition method: P.Millet, J ofApplied electrochemistry 25 (1995) 233-239; 3, electrodeposition process: US508414 and US6258239; 4, sputtering method: Electrochimica Acta.1997.42 (10) 1587-1593.
But the fuel cell of the membrane electrode of these articles and patent description and design thus all is to adopt the mode of outer humidification to move, need extra humidifying equipment, can not realize membrane electrode from humidification, also promptly under the situation that does not have extra humidifying equipment, can not stable operation.
The development of fuel cell generally speaking is the direction towards simple, efficient, safety, environmental protection.If wherein solved fuel cell membrane electrode from the humidification problem, simplified apparatus requirement greatly.
Wang Cheng etc. have set forth a kind of manufacture method of self-humidifying membrane electrode in " preparation of novel self-humidifying membrane electrode and fuel battery performance one SCI thereof; Vol 24; No 1; 140-142 in January, 2003 " literary composition; promptly on carbon paper, apply the mixture of layer of active carbon and polytetrafluoroethylene; spray one deck again and contain the mixture of the perfluor sulfoacid resin solution of charcoal carried catalyst, a kind of commodity Nafion by name; handle the back and form membrane electrode, can obtain effect from humidification with the amberplex that a kind of commodity are called the Nafion112 film.Its stability of just not touching upon.
Rope advances equality and mix film forming with silicon dioxide mutually with organic polymer in " novelly exempting from humidifying composite proton exchange film-composite material journal based on inorganic matter; Vol 21; No in February, 1 2004 " literary composition, by silicon dioxide being cross-linked to form a kind of comparatively stable proton exchange membrane, be still waiting just that it exempts from humidification effect and stability by actual verification.
Above invention and document are owing to be difficult to the Gradient distribution of structure catalyst, hydrophobic resin, hydrophilic resin simultaneously, also promptly be difficult to guarantee three unobstructed passages: electron channel, proton and fluid passage, gas passage, thus be difficult to realize the stable operation of self-humidifying fuel cell.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of self-humidifying membrane electrode in fuel cell.
Self-humidifying membrane electrode is defined as: fuel cell does not need additionally to increase humidifying equipment in running, the water that membrane electrode self produces turns back to anode from negative electrode under osmosis, finish the aquation of reacting gas and proton, unnecessary water is then discharged with tail gas, thereby reaches the water balance of fuel battery inside.
The ideal polymer membrane electrode has following performance 1) contact of good interface to be to obtain low internal resistance; 2) loose structure is to help mass transfer but not limiting factor; 3) big electrode-ion exchange polymer film (hereinafter to be referred as: PEM) contact area is to provide sufficient electro-chemical activity area; 4) catalyst deposit is in ion exchange polymer film, and contiguous place forms skim on the film surface.In other words: good membrane electrode must have three unobstructed passages: electron channel, proton and fluid passage, gas passage.And these passages are all constructed to a hundreds of micrometer range several, if three passages have one not smooth, under the certain prerequisite of catalyst activity, the efficient of fuel cell all will be had a greatly reduced quality.What can assert is, in catalytic reaction process, because constantly consume fuel and oxygen, constantly form product such as water and carbon dioxide etc. again, so it is uneven that the gas-liquid of whole membrane electrode layer distributes, if the structure of membrane electrode can not adapt to this situation, that just be easy to cause local catalyst by water logging do not have, phenomenons such as product can not arranged or reactant can not advance, film mummification, cause battery performance to become bad.The data demonstration, if can form the Gradient distribution of hydrophobic layer and hydrophilic layer, and the Gradient distribution of catalyst, so just can under the situation of less catalyst, obtain higher battery performance.
The invention provides a kind of fairly simple method, can realize the Gradient distribution of hydrophobic layer and hydrophilic layer and the Gradient distribution of catalyst layer simultaneously, can realize fuel cell from humidification stable operation.
The present invention adopt with hydrophobic polymer and ionomer respectively with catalyst mix, be coated in succession on the conductive carrier, compound with ionic polymer membranes again, form polymer membrane electrode.This membrane electrode can obtain the Gradient distribution of catalyst, hydrophobic resin, hydrophilic resin, thus the realization membrane electrode in service of fuel cell from humidification.
The difference of this method and preceding method is that this method realizes the Gradient distribution of hydrophobic layer and hydrophilic layer and the Gradient distribution of catalyst layer simultaneously under simple prerequisite.Promptly on the interface of the hydrophobic layer that mainly contains polytetrafluoroethylene and charcoal carried catalyst and the hydrophilic layer of main ion-containing polymer and charcoal carried catalyst, catalyst concentration is the highest, concentration before and after it then reduces successively, in addition, because the diffusion and the infiltration of polytetrafluoroethylene and ionomer, cause them also to form certain Gradient distribution, it is more wherein to contain the amount of polytetrafluoroethylene away from a side of proton exchange membrane, the amount of ion-containing polymer is less, and in a side that contacts proton exchange membrane, ionomer content height then, polytetrafluoroethylene content is low, this result can be so that the proton that anode tap produces reaches negative electrode by more and more wideer hydrophilic channel and proton exchange membrane, makes the water that generates gas passage can not stopped up by more and more wideer hydrophobic channel the time simultaneously.In addition, because the charcoal carried catalyst that is coated on the carbon paper closely contacts with carbon paper, again because the pure active carbon of electric transmission resistance ratios of the active carbon of year metal is little, so total internal resistance of cell little than the active carbon that does not carry metal again.The discharge capability of battery is just improved like this, simultaneously, because three passages are all comparatively unimpeded, so negative electrode and anode all are not easy not had by water logging, the water that battery produces is enough kept the needs of proton transfer again, like this with regard to relatively easily realized fuel cell from humidification, keep certainly.
The present invention with carbon paper, charcoal cloth, charcoal felt, porous foam metal sheet nickel foam or titanium foam porous thin slice as conductive carrier, the mixture that will contain charcoal carried catalyst and hydrophobicity fluoropolymer emulsion and expanding agent is coated on the conductive carrier, the method that applies can be knife coating or spraying process, wherein: the content of catalyst metals on conductive carrier contained in the charcoal carried catalyst is: 0.02～3 milligram/square centimeter, and the content of fluoropolymer on the metallic conductivity carrier: 0.1～2 milligram/square centimeter; With carrier under 100～200 ℃ of temperature, hot pressing is 1～5 minute under 1～7Mpa pressure, behind 300～500 ℃ of sintering, be coated with the mixture that contains charcoal carried catalyst and ionomer solution again, wherein the contained content of catalyst metals on carrier is in the charcoal carried catalyst: 0.05～3 milligram/square centimeter, the content of polymer on carrier is in the ionomer solution: 0.5～2 milligram/square centimeter, after the room temperature mummification, get two such conductive carrier, clamping a thickness is: 45～250 microns amberplex, the catalyst layer of conductive carrier is towards amberplex, then at 100～160 ℃, hot pressing is 1～5 minute under 1～7Mpa pressure, makes membrane electrode.
In the superincumbent description, hydrophobic treatment is all made to help generating the discharge of water in the conductive carrier surface.
The charcoal carried catalyst is based on the active carbon of specific area more than 100 meters squared per gram, adopt the whole bag of tricks such as liquid phase method, vapour phase processes, solid phase method, metallic catalyst such as Pt, Rh, Pd, Au, Ag, Os, Ir, Ru are deposited on the surface of active carbon with the nano-grade size size, generate nm-class catalyst.In hydrogen oxygen fuel cell, be major catalyst mainly with platinum, be doped with a little other metal such as Ru, Ir etc. to obtain comprehensive performance.
Above-mentioned hydrophobicity fluoropolymer is a polytetrafluoroethylene (PTFE).
Above-mentioned ionomer solution mainly is meant the fluoride ion polymer solution, and ionic polymer membranes mainly is meant the fluoride ion polymer film, and typically Nafion solution and the Nafion film of producing as E.I.Du Pont Company also has a lot of similar products like certainly.
Material such as solvent, tackifier, pore creating material etc. of in the manufacture process of electrode, also adding other, what these materials had can make processing more convenient, what have can produce bigger active surface, their addition is decided according to concrete electrode, but in final electrode, these materials all are non-existent.
Can find out that from above-mentioned explanation the electrode that the present invention touched upon, its catalyst are divided into the coating of two steps, wherein a part is mixed mutually with lyophobic dust, and another part mixes mutually with hydroaropic substance.Catalyst is the content difference in these two parts, can construct different catalyst concn gradients, thereby obtains different effects.
Embodiment
Embodiment 1: with the charcoal carried catalyst of containing metal platinum and PTFE weight resin percentage composition is 10 emulsion 0.08ml, and after secondary water 5ml, expanding agent 100mg mixed, ultrasonic dispersion 20 minutes was pulpous state, and this slurry is coated in 7 * 7cm with knife coating
2Hydrophobic carbon paper on, wherein the content of metal platinum is: 0.4 milligram/square centimeter, behind the airing, handled 3 minutes down 5MPa pressure and 100 ℃, place 350 ℃ of hot-airs of Muffle furnace to handle then 1 hour; Get charcoal carried catalyst and 1ml weight percentage again and be after 5 Nafion ionomer solution mixes, ultrasonic dispersion 20 minutes, be pulpous state, be coated in this slurry on the charcoal carried catalyst layer of process formation with knife coating, wherein the content of metal platinum is: 0.4 milligram/square centimeter, make cathode catalysis layer.Adopt and use the same method, just change wherein each platinum content into 0.35 milligram/square centimeter, other is constant, makes anode catalyst layer.These two carried catalyst carbon papers are clamped a Nafion112 film, and about 45 microns of thickness, catalyst layer be towards the Nafion film, and hot pressing 5 minutes under 135 ℃, 1MPa pressure then promptly forms membrane electrode.Load onto this membrane electrode in graphite pole plate battery case, under 70 ℃, working pressure is 1.8 atmospheric common hydrogen and 2.4 atmospheric common oxygen, without humidifying device, moves this battery, can obtain maximum discharge power: 0.65W/cm
2At discharge current density is 0.75A/cm
2Situation under one week of intermittent discharge, can keep voltage is near the 0.5V.
Comparative example 1: adopt the platinum content same with embodiment one, just catalyst all is placed in hydrophily ionomer one deck, and in hydrophobicity one deck, replaces the charcoal carried catalyst with the 60mg active carbon, under same condition, move, find that maximum discharge power can only reach 0.54W/cm
2, and promptly begin to descend less than battery performance operation two hours, can not stable operation.
Embodiment 2: with the charcoal carried catalyst of containing metal platinum and PTFE weight resin percentage composition is 10 emulsion 0.05ml, and after secondary water 5ml, pore creating material 50mg mixed, ultrasonic dispersion 20 minutes was pulpous state, and this slurry is sprayed on 7 * 7cm
2Hydrophobic carbon paper on, wherein the content of metal platinum is: 0.35 milligram/square centimeter, behind the airing, handled 3 minutes down 5MPa pressure and 135 ℃, place 300 ℃ of hot-airs of Muffle furnace to handle then 1 hour; Get charcoal carried catalyst and 0.5ml weight percentage again and be after 5 Nafion ionomer solution mixes, ultrasonic dispersion 20 minutes, be pulpous state, this slurry is used on the charcoal carried catalyst layer that is sprayed on process formation, wherein the content of metal platinum is: 0.25 milligram/square centimeter, make cathode catalysis layer.Adopt and use the same method, just change wherein each platinum content into 0.02 milligram/square centimeter, other is constant, makes anode catalyst layer.These two carried catalyst carbon papers are clamped a Nafion115 film, and about 170 microns of thickness, catalyst layer be towards the Nafion film, and hot pressing 1 minute under 135 ℃, 7MPa pressure then promptly forms membrane electrode.Load onto this membrane electrode in graphite pole plate battery case, under 70 ℃, working pressure is 1.8 atmospheric common hydrogen and 2.4 atmospheric common oxygen, without humidifying device, moves this battery, can obtain maximum discharge power: 0.35W/cm
2At discharge current density is 0.30A/cm
2Situation under one week of intermittent discharge, can keep voltage is near the 0.5V.
Comparative example 2: adopt the platinum content same with embodiment two, just catalyst all is placed in hydrophily ionomer one deck, and in hydrophobicity one deck, replaces the charcoal carried catalyst with the 60mg active carbon, under same condition, move, find that maximum discharge power can only reach 0.25W/cm
2, and promptly begin to descend less than battery performance operation two hours, can not stable operation.
Embodiment 3: be 10 emulsion 1ml with the charcoal carried catalyst of containing metal platinum and ruthenium and PTFE weight resin percentage composition, after secondary water 10ml, pore creating material 200mg mix, ultrasonic dispersion 20 minutes, be pulpous state, this slurry is coated in knife coating on 7 * 7 square centimeters the hydrophobic charcoal cloth, wherein the content of metal platinum is: 2 milligrams/square centimeter, ruthenium content: 1 milligram/square centimeter, behind the airing, 5MPa pressure and 135 ℃ of following processing 3 minutes, place 500 ℃ of hot-airs of Muffle furnace to handle then 1 hour; Get charcoal carried catalyst and 2ml weight percentage again and be after 5 Nafion ionomer solution mixes, ultrasonic dispersion 20 minutes, be pulpous state, be coated in this slurry on the charcoal carried catalyst layer of process formation with knife coating, wherein the content of metal platinum is: 2 milligrams/square centimeter, ruthenium content: 1 milligram/square centimeter, make cathode catalysis layer.Adopt and use the same method, just change wherein each platinum content into 0.35 milligram/square centimeter, other is constant, makes anode catalyst layer.These two carried catalyst carbon papers are clamped a Nafion117 film, and thick about 220 microns, catalyst layer is towards the Nafion film, and hot pressing 3 minutes under 160 ℃, 5MPa pressure then promptly forms membrane electrode.Load onto this membrane electrode in graphite pole plate battery case, under 70 ℃, working pressure is 1.8 atmospheric common hydrogen and 2.4 atmospheric common oxygen, without humidifying device, moves this battery, can obtain maximum discharge power: 0.58W/cm
2At discharge current density is 0.8A/cm
2Situation under one week of intermittent discharge, can keep voltage is near the 0.5V.
Should be noted that, under the premise without departing from the spirit of the present invention, the common researcher of the industry promptly can adopt other any charcoal supported metal catalyst to comprise that composite catalyst comes the platinum catalyst in the alternate embodiment, as long as can as embodiment, construct the concentration gradient of a catalyst, hydrophobic polymer, hydrophobic polymer, just can obtain the performance higher than the membrane electrode that does not have this Gradient distribution.Also can be with the polytetrafluoroethylene in other the fluoropolymer alternate embodiment, come Nafion film in the alternate embodiment with other ionic polymer membranes, used coating process is not to be best yet among the embodiment, by means of the modern high technology coating apparatus, should be issued to same performance on lower platinum content basis.
Claims (4)
1, a kind of preparation method of self-humidifying membrane electrode in fuel cell, with carbon paper, these conductivity porous thin slices of charcoal cloth are as conductive carrier, to contain charcoal carried catalyst and hydrophobicity fluoropolymer emulsion and expanding agent, tackifier, the mixture of water is coated on the conductive carrier, wherein: the content of catalyst metals on conductive carrier contained in the charcoal carried catalyst is: 0.02～3 milligram/square centimeter, the content of fluoropolymer on carrier: 0.1～2 milligram/square centimeter, with the hot pressing under 100～200 ℃ of temperature of this carrier, behind 300～500 ℃ of sintering, be coated with the mixture that contains charcoal carried catalyst and ionomer solution again, wherein the contained content of catalyst metals on carrier is 0.05～3 milligram/square centimeter in the charcoal carried catalyst of back adding, the content of dry state ionomer on carrier is 0.5～2 milligram/square centimeter, after the room temperature mummification, get two such conductive carrier, clamp the perfluoroethylene proton exchange membrane of an amberplex such as commodity Nafion by name, the thickness of amberplex is 45～250 microns, the catalyst layer of conductive carrier becomes membrane electrode 100～160 ℃ of hot pressings then towards amberplex.
2, the preparation method of a kind of self-humidifying membrane electrode in fuel cell as claimed in claim 1, it is characterized in that the charcoal carried catalyst is that charcoal platinum catalyst or charcoal carry the platinum ruthenium catalyst, it is based on active carbon, metal platinum and ruthenium are loaded on the surface of active carbon, form catalyst with very big active surface area.
3, the preparation method of a kind of self-humidifying membrane electrode in fuel cell as claimed in claim 1 is characterized in that described hydrophobic fluoropolymer mainly is meant polytetrafluoroethylene, fluorinated ethylene-propylene copolymer (FEP), polytrifluorochloroethylene and similar fluoropolymer.
4, the preparation method of a kind of self-humidifying membrane electrode in fuel cell as claimed in claim 1, it is characterized in that described ionomer and amberplex mainly be meant at room temperature be solid-state, have the ion-exchange gene, fluorine-containing macromolecule homopolymers or copolymer, wherein have at least a monomeric unit partly or all fluoridize; Polymer contains a lot of side chains, and its end is acidic group, base or salt group.
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| CNB2005100165630A CN1303709C (en) | 2005-02-01 | 2005-02-01 | Method for preparing self-humidifying membrane electrode in fuel cell |
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| CN1303709C CN1303709C (en) | 2007-03-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101577342B (en) * | 2009-06-08 | 2011-08-17 | 清华大学 | Fuel cell with humidification zone of single cell |
| CN107037107A (en) * | 2015-12-08 | 2017-08-11 | 恩德莱斯和豪瑟尔分析仪表两合公司 | Potentiometric sensor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09265992A (en) * | 1996-03-29 | 1997-10-07 | Mazda Motor Corp | Electrode structure for fuel cell |
| CN1181585C (en) * | 2002-06-19 | 2004-12-22 | 中国科学院大连化学物理研究所 | Process for preparing self-humidifying composite proton exchange film for fuel cell |
-
2005
- 2005-02-01 CN CNB2005100165630A patent/CN1303709C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101577342B (en) * | 2009-06-08 | 2011-08-17 | 清华大学 | Fuel cell with humidification zone of single cell |
| CN107037107A (en) * | 2015-12-08 | 2017-08-11 | 恩德莱斯和豪瑟尔分析仪表两合公司 | Potentiometric sensor |
| CN107037107B (en) * | 2015-12-08 | 2020-10-16 | 恩德莱斯和豪瑟尔分析仪表两合公司 | Electric potential sensor |
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| CN1303709C (en) | 2007-03-07 |
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