CN1274046C - Method for producing proton exchange film fuel cell core module - Google Patents

Method for producing proton exchange film fuel cell core module Download PDF

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Publication number
CN1274046C
CN1274046C CNB2004100609444A CN200410060944A CN1274046C CN 1274046 C CN1274046 C CN 1274046C CN B2004100609444 A CNB2004100609444 A CN B2004100609444A CN 200410060944 A CN200410060944 A CN 200410060944A CN 1274046 C CN1274046 C CN 1274046C
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sulfonic acid
proton exchange
exchange membrane
acid type
anionic polymer
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CN1588680A (en
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潘牧
唐浩林
宛朝辉
袁润章
谢春华
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Wuhan University of Science and Engineering WUSE
Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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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

The present invention provides a method for manufacturing core assemblies of proton exchange membrane fuel batteries, which is characterized in that precursor salt of catalysts is chemically reduced in water solution of sulfonic acid type negative ion polymers with the capability of proton conduction to obtain nanometer catalyst particles modified by ions, and then, a coating method, an ink-jet printing method or a transfer printing method is adopted to transfer the nanometer catalyst particles modified by ions onto a proton exchange membrane, or the nanometer catalyst particles modified by ions are thoroughly mixed with ethylene glycol and then are transferred onto a proton exchange membrane through a coating method or a transfer printing method, or positive ion polymers are arranged on the surface of a proton exchange membrane firstly through electrostatic self-assembly, and then, the proton exchange membrane treated by the positive ion polymers is submerged into hydrolytic solution of the nanometer catalyst particles modified by ions to assemble the nanometer catalyst particles modified by ions through self-assembly. As a result, a core assembly for proton exchange membrane fuel batteries is obtained. The surfaces of the catalyst particles of the assembly are modified by sulfonic acid type negative ion polymers, so that the assembly has a favorable capability of proton conduction.

Description

The manufacture method of one proton exchange membrane fuel cell core module
Technical field
The present invention relates to the manufacture method of a proton exchange membrane fuel cell core module, be characterized in that the nanocatalyst particle surface in the Catalytic Layer has been modified the sulfonated anionics polymer with proton conductivity.
Background technology
In today that global energy crisis and environment go from bad to worse, improve resource utilization, reduce the important topic that environmental pollution has become scientific research.Fuel cell technology has become one of focus of international new and high technology competition as a kind of energy technology of cleaning.(Catalyst coated membrane CCM) is the core component of Proton Exchange Membrane Fuel Cells (PEMFC) to the fuel cell core component, is made up of proton exchange membrane and the Catalytic Layer that is coated on the film both sides.In some early stage at home and abroad patents or other report, the combination of film and Catalytic Layer generally be with catalyst-coated on gas-diffusion electrode (as porous carbon paper, carbon cloth), form with proton exchange membrane hot pressing then, therefore this assembly be also referred to as in early days membrane electrode (membraneelectrode assembly, MEA).Along with the development of PEMFC technology, it is found that Catalytic Layer is coated to the assembly that forms on the proton exchange membrane and has better Catalytic Layer uniformity and gas-liquid-proton phase reaction passage, can on lower catalyst loading, reach better output performance.Therefore CCM also becomes one of the main flow trend of current PE MFC and advanced field.In CCM, because proton film the selection of material is more fixing, the perfluoro sulfonic acid membrane that generally adopts main chain all to fluoridize, the very high but stable performance of its cost, so the structure of Catalytic Layer is depended in the improvement of the Cost And Performance of CCM to a great extent.
US2004124091 has described the method that a kind of preparation prepares CCM continuously, proton exchange membrane one side is aggregated the covering of thing back of the body counterdie in their invention, opposite side adopts the method printing Pt/C catalyst of silk screen printing and the ink that ion exchange resin forms, after super-dry, remove polymer back of the body counterdie, adopt the printing Catalytic Layer that uses the same method at the opposite side of proton exchange membrane.US2004086632 has described a kind of proton exchange membrane of heating earlier to making the film surface softening more than the vitrification point, and the method that adopts air blast to blow is then transferred to the method that the proton exchange membrane surface forms CCM with the catalyst of fluid bed mixing and the mixture of ion exchange resin.US6749892 has described a kind of method of electric arc sputter that adopts catalyst metals or carbon supported catalyst has been splashed to the method that the proton exchange membrane surface forms CCM.
Can think, existing CCM typical case manufacture method be earlier preparation Pt/C catalyst, Pt/C catalyst and proton conductive resin (as Nafion) mixed to transfer on proton exchange membrane or the gas-diffusion electrode form then, because the proton conductive resin of physical mixed is difficult for contacting closely with catalyst, and a large amount of Pt catalyst is isolated in the micropore of porous carbon black, the inefficiency away from the necessary proton of catalytic reaction, electronics and gas three-phase passage, its utilance only is 10%～20%[Electrochim.Acta, 2001,46,1657; J Mater.Res., 2004,19,2279]; Directly transfer to CCM on the proton exchange membrane for catalyst metals, because the very high surface activity of nano metal particles, generally to reunite or the form of film exists, this has just reduced the surface activity area of catalyst to catalyst.
Summary of the invention
The new manufacture method that the purpose of this invention is to provide a proton exchange membrane fuel cell core module, this manufacture method is in the electrochemical reaction zone of fuel cell Catalytic Layer, the surface that is catalyst granules makes up more perfect proton conduction passage, make Catalytic Layer have the original position conducting power, thereby reduce Catalytic Layer because the ohmic polarization that proton conduction does not freely produce.
The manufacture method step of core components of PEMFC of the present invention is:
The 1st step: the nanocatalyst particle dispersion that preparation sulfonic acid type anionic polymer is modified: get the Nafion resin; or sulfonated polystyrene-polyethylene or butylene-polystyrene; or sulfonation trifluorostyrene sulfonic acid-based polymer is dissolved in the deionized water; add catalyst metals Pt or/and Pd or/and the presoma salt of Ru; adding boiling point is lower than 120 ℃ alcohols reducing agent and fully mixes; regulate more than the pH value to 7 with NaOH; under nitrogen protection, be heated to 70～95 ℃; backflow mixed solution to the presoma reactant salt of catalyst metals finishes; obtain the dispersion liquid that the nanocatalyst particle surface is modified with the sulfonic acid type anionic polymer; its reaction condition: the mol ratio of sulfonic acid-based polymer monomer and catalyst precursor ion is 1: 0.5-15; water is 1 with the mass ratio of alcohol in the mixed solution: 0.7-10, the presoma salt of described catalyst metals Pt is H 2PtCl 6, the presoma salt of catalyst metals Pd is PdCl 3, the presoma salt of catalyst metals Ru is RuCl 3, alloy catalyst is the mixture of the presoma salt of alloying element by alloy dosage ratio;
The 2nd step: the finishing that step 1 is obtained has the dispersion liquid purification of the nanocatalyst particle of sulfonic acid type anionic polymer to separate: the nanocatalyst particle that isolated pure sulfonic acid type anionic polymer is modified directly is brushed on the proton exchange membrane; The nanocatalyst particle that perhaps adopts ethylene glycol to regulate the modification of sulfonic acid type anionic polymer becomes the ink shape, and inkjet printing is on proton exchange membrane; The nanocatalyst particle that perhaps adopts ethylene glycol to regulate the modification of sulfonic acid type anionic polymer becomes the ink shape, adopts the method for inkjet printing or brushing to transfer on the polytetrafluoroethylene film ink, and hot pressing is transferred on the proton exchange membrane then; Perhaps earlier at proton exchange membrane surface self assembly cationic polymer, then it was immersed in the sulfonic acid type anionic polymer nanocatalyst particle dispersion that step 1 obtains 24-48 hour, obtain core components of PEMFC.
Described sulfonic acid-based polymer is the side chain of band sulfonate group, and do not contain in the polymer in the aqueous solution can other group of ionization anionic polymer, can be perfluorinated sulfonic resin, sulfonation trifluorostyrene, polymethyl-benzene base sulfonic acid siloxanes, sulfonated polyether-ether-ketone, sulfonated polystyrene-polyethylene and ethylene copolymers, sulfonated polystyrene-polyethylene/butylene-polystyrene.
Described boiling point is lower than 120 ℃ alcohols reducing agent and is meant in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol any.
It is to adopt pellicle to filter out Na that the purification of the nanocatalyst particle dispersion that described sulfonic acid type anionic polymer is modified separates +, Cl -Foreign ion.
The method for purifying and separating of the nanocatalyst particle dispersion that described sulfonic acid type anionic polymer is modified is to add H 2SO 4Regulate the pH value less than 1, and centrifugation goes out the nanocatalyst that pure sulfonic acid type anionic polymer is modified.
The purification of the nanocatalyst particle dispersion that described sulfonic acid type anionic polymer is modified separates: adopt the phase transfer of chloroform non-polar solven to go out the nanocatalyst that pure sulfonic acid type anionic polymer is modified.
Described method at proton exchange membrane surface self assembly cationic polymer is: with proton exchange membrane successively at the H of 5wt% 2O 2, deionized water, 1mol/L H 2SO 4, and deionized water in respectively soak 30 minutes after, the PDDA solution of putting into 0.05mol/L soaked 1～3 hour, then at the H of 1mol/L 2SO 4, respectively soaked the proton exchange membrane that promptly obtains having assembled cationic polymer 30 minutes in the deionized water.
Compare with existing P t/C fuel cell core component, therefore the core component that the present invention obtains has good proton conductivity because catalyst granules has been modified the sulfonic acid type anionic polymer, and the ohmic polarization that the proton conduction resistance of Catalytic Layer forms is very little; Compare to the fuel cell core component on the proton exchange membrane with existing P t sputter or chemical deposition, core component of the present invention since the catalyst granules finishing by the sulfonic acid type anionic polymer, catalyst granules exists with the form of high degree of dispersion rather than reunion, therefore has good catalytic performance.
Embodiment
Following embodiment further specifies of the present invention.
Embodiment 1
The Nafion solution 1mL that gets 5wt% adds in the 70mL deionized water, and adding 10mL concentration under the mechanical agitation condition is the H of 15g/L 2PtCl 2Solution adds the 60mL absolute ethyl alcohol behind the 5min, continuing to stir 10 minutes pH values with the NaOH regulation system is 12, sealed reaction vessel and logical N 2Protection, heating reaction solution reflux at 84 ℃ and obtained the nanocatalyst particle dispersion that the sulfonic acid type anionic polymer is modified in 10 minutes, and the zeta of dispersion liquid is-18mV that grain diameter is 1.9 ± 0.2nm.The pH value that constantly drips NaOH maintenance system in the reflux course is 12.
With proton exchange membrane successively at the H of 5wt% 2O 2, deionized water, 1mol/L H 2SO 4, respectively soak 30 minutes in the deionized water after, the PDDA solution (PDDA) of putting into 0.05mol/L soaked 2 hours, then at the H of 1mol/L 2SO 4, respectively soak 30 minutes in the deionized water after, obtain having assembled the cationic proton exchange membrane of PDDA, with static self assembly in the nanocatalyst particle dispersion of this proton exchange membrane immersion sulfonic acid type anionic polymer modification 36 hours, obtain thin layer used in proton exchange membrane fuel cell core component.
Embodiment 2
Sulfonated polystyrene-the polyethylene or the butylene-polystyrene solution 3mL that get 3wt% add in the 210mL deionized water, and adding 24mL concentration under the mechanical agitation condition is the H of 15g/L 2PtCl 2Solution adds the 240mL isopropyl alcohol behind the 5min, continues to stir 10 minutes, and be 9 with the pH value of NaOH regulation system, sealed reaction vessel also leads to N 2Protection, heating reaction solution reflux at 93 ℃ and obtained the nanometer Pt catalyst granules dispersion liquid that the sulfonic acid type anionic polymer is modified in 16 minutes, and the zeta of dispersion liquid is-14mV that grain diameter is 2.3 ± 0.2nm.The pH value that constantly drips NaOH maintenance system in the reflux course is 9.The H that adds 0.5mol/L in the nanocatalyst particle dispersion 2SO 4Regulating the pH value is 0.5 also centrifugation, adds washed with de-ionized water, centrifugation in the nanocatalyst that isolated sulfonic acid type anionic polymer is modified.Cleaning process repeats 3 times and obtains the nanocatalyst that pure sulfonic acid type anionic polymer is modified, and the nanocatalyst that adopts ethylene glycol to regulate the modification of sulfonic acid type anionic polymer becomes the ink shape, and the ink inkjet printing of modulation is to polytetrafluoroethylene film.
With proton exchange membrane successively at the H of 5wt% 2O 2, deionized water, 1mol/L H 2SO 4, respectively soak 30 minutes in the deionized water after, Catalytic Layer is transferred on the proton exchange membrane 2Mpa, 130 ℃ of hot pressing 5 minutes with the polytetrafluoroethylene film of having printed catalyst ink then, obtain thin layer used in proton exchange membrane fuel cell core component.
Embodiment 3
The sulfonation trifluorostyrene solution 3mL that gets 3wt% adds in the 210mL deionized water, and adding 12mL concentration under the mechanical agitation condition is the H of 15g/L 2PtCl 2Solution and 12mL concentration are the RuCl of 2g/L 3Solution adds the 240mL isopropyl alcohol behind the 5min, continues to stir 10 minutes, and be 11 with the pH value of NaOH regulation system, sealed reaction vessel also leads to N 2Protection, heating reaction solution reflux at 93 ℃ and obtained the nanocatalyst particle dispersion that the sulfonic acid type anionic polymer is modified in 16 minutes, and the zeta of dispersion liquid is-14mV that grain diameter is 4.3 ± 0.3nm.The pH value that constantly drips NaOH maintenance system in the reflux course is 11.Adopt the phase transfer of chloroform non-polar solven to go out the nanocatalyst that pure sulfonic acid type anionic polymer is modified, add ethanol in the nanocatalyst that isolated sulfonic acid type anionic polymer is modified and clean the nanocatalyst that obtains pure sulfonic acid type anionic polymer modification for 3 times, the nanocatalyst that adopts ethylene glycol to regulate the modification of sulfonic acid type anionic polymer becomes the ink shape, and the ink inkjet printing of modulation is to polytetrafluoroethylene film.
With proton exchange membrane successively at the H of 5wt% 2O 2, deionized water, 1mol/L H 2SO 4, respectively soak 30 minutes in the deionized water after, Catalytic Layer is transferred on the proton exchange membrane 2Mpa, 130 ℃ of hot pressing 5 minutes with the polytetrafluoroethylene film of having printed catalyst ink then, obtain thin layer used in proton exchange membrane fuel cell core component.

Claims (6)

1, the manufacture method of a proton exchange membrane fuel cell core module is characterized in that making step is:
The 1st step: the nanocatalyst particle dispersion that preparation sulfonic acid type anionic polymer is modified: get the Nafion resin; or sulfonated polystyrene-polyethylene or butylene-polystyrene; or sulfonation trifluorostyrene sulfonic acid-based polymer is dissolved in the deionized water; add catalyst metals Pt or/and Pd or/and the presoma salt of Ru; adding boiling point is lower than 120 ℃ alcohols reducing agent and fully mixes; regulate more than the pH value to 7 with NaOH; under nitrogen protection, be heated to 70～95 ℃; backflow mixed solution to the presoma reactant salt of catalyst metals finishes; obtain the dispersion liquid that the nanocatalyst particle surface is modified with the sulfonic acid type anionic polymer; its reaction condition: the mol ratio of sulfonic acid-based polymer monomer and catalyst precursor ion is 1: 0.5-15; water is 1 with the mass ratio of alcohol in the mixed solution: 0.7-10, the presoma salt of described catalyst metals Pt is H 2PtCl 6, the presoma salt of catalyst metals Pd is PdCl 3, the presoma salt of catalyst metals Ru is RuCl 3, alloy catalyst is the mixture of the presoma salt of alloying element by alloy dosage ratio;
The 2nd step: the finishing that step 1 is obtained has the nanocatalyst particle dispersion purification of sulfonic acid type anionic polymer to separate: the nanocatalyst particle that isolated pure sulfonic acid type anionic polymer is modified directly is brushed on the proton exchange membrane; The nanocatalyst particle that perhaps adopts ethylene glycol to regulate the modification of sulfonic acid type anionic polymer becomes the ink shape, and inkjet printing is on proton exchange membrane; The nanocatalyst particle that perhaps adopts ethylene glycol to regulate the modification of sulfonic acid type anionic polymer becomes the ink shape, adopts the method for inkjet printing or brushing to transfer on the polytetrafluoroethylene film ink, and hot pressing is transferred on the proton exchange membrane then; Perhaps earlier at proton exchange membrane surface self assembly cationic polymer, then it was immersed in the nanocatalyst particle dispersion that sulfonic acid type anionic polymer that step 1 obtains modifies 24-48 hour, obtain core components of PEMFC.
2, manufacture method as claimed in claim 1 is characterized in that described boiling point is lower than 120 ℃ alcohols reducing agent and is meant in methyl alcohol, ethanol, propyl alcohol and the isopropyl alcohol any.
3, manufacture method as claimed in claim 1, the purification separation that it is characterized in that the nanocatalyst particle dispersion of described sulfonic acid type anionic polymer is to adopt pellicle to filter out Na +, Cl -Foreign ion.
4, manufacture method as claimed in claim 1 is characterized in that the method for purifying and separating of the nanocatalyst particle dispersion that described sulfonic acid type anionic polymer is modified is, adds H 2SO 4Regulate the pH value less than 1, and centrifugation goes out the nanocatalyst that pure sulfonic acid type anionic polymer is modified.
5, manufacture method as claimed in claim 1 is characterized in that the purification separation of the nanocatalyst particle dispersion that described sulfonic acid type anionic polymer is modified is: adopt the phase transfer of chloroform non-polar solven to go out the nanocatalyst that pure sulfonic acid type anionic polymer is modified.
6, manufacture method as claimed in claim 1 is characterized in that described method at proton exchange membrane surface self assembly cationic polymer is: with proton exchange membrane successively at the H of 5wt% 2O 2, deionized water, 1mol/L H 2SO 4, and deionized water in respectively soak 30 minutes after, the PDDA solution of putting into 0.05mol/L soaked 1～3 hour, then at the H of 1mol/L 2SO 4, respectively soaked the proton exchange membrane that promptly obtains having assembled cationic polymer 30 minutes in the deionized water.
CNB2004100609444A 2004-10-11 2004-10-11 Method for producing proton exchange film fuel cell core module Expired - Fee Related CN1274046C (en)

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Publication number Priority date Publication date Assignee Title
CN100392897C (en) * 2006-03-23 2008-06-04 武汉理工大学 Method for preparing film electrode for hydrophilic and hydrophobic adjustable proton exchange film fuel cell
CN100392896C (en) * 2006-03-23 2008-06-04 武汉理工大学 Mehtod for preparing core assembly for proton exchange membrane fuel cell with adjustable hydrophilicity and hydrophobicity
KR100846478B1 (en) * 2006-05-16 2008-07-17 삼성에스디아이 주식회사 Supported Catalyst, manufacturing method thereof, and fuel cell using the same
KR101011014B1 (en) * 2008-06-13 2011-01-26 한국타이어 주식회사 Process for preparing separator material for a fuel cell having high electrical conductivity, separator for a fuel cell and feul cell
KR102162703B1 (en) * 2017-09-20 2020-10-07 주식회사 엘지화학 Method for carrier for electrode catalyst, precursor of carrier for electrode catalyst and carrier for electrode catalyst comprising the same
CN110323477A (en) * 2019-04-19 2019-10-11 武汉理工大学 A kind of hydrogen reduction Catalytic Layer and preparation method thereof based on poly ion liquid as proton conductor
KR20210028824A (en) * 2019-09-05 2021-03-15 현대자동차주식회사 Polymer Electrolyte Membrane for Fuel Cell and Method for Manufacturing The Same
CN112421056B (en) * 2020-11-18 2022-05-27 江苏耀扬新能源科技有限公司 Novel fuel cell membrane electrode and preparation method thereof

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