CN1185737C - Method of preparing membrane electrode using recasted perfluro sulfonic acid proton exchange film - Google Patents
Method of preparing membrane electrode using recasted perfluro sulfonic acid proton exchange film Download PDFInfo
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- CN1185737C CN1185737C CNB011368179A CN01136817A CN1185737C CN 1185737 C CN1185737 C CN 1185737C CN B011368179 A CNB011368179 A CN B011368179A CN 01136817 A CN01136817 A CN 01136817A CN 1185737 C CN1185737 C CN 1185737C
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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
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- 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
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Abstract
The present invention relates to a method for preparing membrane electrodes by using recast perfluoro-sulfoacid proton exchange membranes, which comprises the steps that perfluoro-sulfoacid substances are put into a water solution of an organic polar solvent with low boiling point and are heated to be dissolved in a sealed reaction vessel; a perfluoro-sulfoacid solution is heated to be dried; an organic solvent with high boiling point is added to dissolve dried perfluoro-sulfoacid substances, and then, the organic solvent is kept in a dryer for 24 hours to prepare membrane preparing liquid; after the membrane preparing liquid and a mold are heated, the membrane preparing liquid is cast into the mold and then is heated and dried in vacuum to form membranes; the membrane preparing liquid is coated on the surface of a catalyst layer of a porous gas diffusion electrode, and then is heated and dried after being aired; two porous gas diffusion electrodes are respectively put on both sides of a recast perfluoro-sulfoacid proton exchange membrane, and the catalyst layers of the electrodes face to the proton exchange membrane and are hot-pressed by a pressing machine. The method has the advantages of simple preparing technology, no requirement for complicated devices, and convenient and rapid operation.
Description
Technical field
The present invention relates to the recycling method of the proton exchange membrane in the proton exchanging film fuel battery, the recovery that relates in particular to a kind of perfluorinated sulfonic acid proton film prepares the Proton Exchange Membrane Fuel Cells method.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) has high power density, high-energy conversion efficiency, and cold-starting, advantages of environment protection, it will be widely used in fields such as space flight, military affairs, the energy and traffic.The electrode of PEMFC is a porous gas diffusive electrode, makes eelctro-catalyst with pure Pt, Pt/C or Pt-Ru/C etc., and electrolyte is a solid polymer proton exchange membrane.Proton exchange membrane (PEM) is one of core building block of PEMFC, it with general chemical power source in the barrier film that uses a great difference is arranged, at first it is not a kind of diaphragm material, and it still is the substrate of electrolyte (transmission proton) and electrode active material (eelctro-catalyst); In addition, PEM still is a kind of selective permeation film of densification, and is different from common porous membrane.Desirable PEM should have the proton conductivity height, gas permeability is low, sufficiently high mechanical strength, thermal stability and chemical stability, suitable performance and price ratio.Up to now, adopted the perfluorinated sulfonic acid proton exchange membrane among the PEMFC mostly, it has good battery performance and useful life, but the shortcoming of perfluoro sulfonic acid membrane has been to use fluorochemical, and experienced loaded down with trivial details synthesis step, therefore cost an arm and a leg (about 700 dollars every square metre).If can be, be prepared into perfluorinated sulfonic acid solution or casting film again, the use cost that all will save the perfluorinated sulfonic acid material to the recycling of perfluorinated sulfonic acid proton exchange membrane.
At present to prepare the perfluorinated sulfonic acid solution patent documentation relevant with perfluoro sulfonic acid membrane comparatively rare with the perfluoro sulfonic acid membrane recycling:
At EP Patent 0,066,369 and US Patent 4,433, in 082, the solution that adopts water and organic solvent (comprising methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, 2-butanols and acetylene etc.) 250-300 ℃ with pulverous perfluorinated sulfonic resin vibration heating 18 hours and dissolve, be mainly used in reverse osmosis, ultrafiltration and common salt electrolytic industry with the non-support membrane of this formulations prepared from solutions.This method more than 250 ℃ and under the condition of vibration is being dissolved perfluorinated sulfonic resin, and the non-support membrane of making is not applied to Proton Exchange Membrane Fuel Cells.
At US Patent 5,242,764 and US Patent 5,318, in 863, employing spraying perfluor sulfoacid resin solution on porous gas diffusive electrode prepares dielectric film, sprays the Nafion solution of some on two electrodes respectively, 80 ℃ of oven dry make it form film, and it is three-in-one that two electrodes are hot pressed into membrane electrode.The dielectric film compactness of this battery is bad, can only work under normal temperature, normal pressure and the gas flow condition near stoichiometric proportion, can't be applied to powerful electric power system.
Summary of the invention
The objective of the invention is to propose a kind of method of preparing membrane electrode using recasted perfluro sulfonic acid proton exchange film, preparation technology is simple for this method, and no complex device requirement is easy to operate, quick.
The technical scheme that the present invention is adopted for achieving the above object comprises the steps:
(1) the perfluorinated sulfonic acid proton exchange membrane is inserted methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol or/and in the aqueous solution of 2-butanols, heating for dissolving in closed reactor, heating for dissolving temperature are 180-240 ℃;
(2) perfluorinated sulfonic acid solution is heated to drying for 80-100 ℃;
(3) add N, dinethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO) or 1-Methyl-2-Pyrrolidone dissolve the dry thing of perfluorinated sulfonic acid, leave standstill to be no less than 24 hours in drier, make preparation liquid;
(4) preparation liquid and mould are heated to 40-60 ℃, preparation liquid is poured in the mould, 120-200 ℃ of vacuum and heating drying film forming;
(5) preparation liquid is sprayed on the Catalytic Layer surface of porous gas diffusive electrode, the oven dry of heating after drying;
(6) two porous gas diffusive electrodes are placed the both sides that cast the perfluorinated sulfonic acid proton exchange membrane more respectively, the Catalytic Layer of electrode is towards proton exchange membrane, hot pressing in forcing press, and hot pressing condition is: pressure 2Mpa, temperature 110-140 ℃, time 1-3 minute.
Wherein the described porous gas diffusive electrode of step (5) is that carbon paper, ptfe emulsion, carbon dust and 20% platinum/C catalyst is prepared from.
Be sprayed on catalyst surface after wherein the described preparation liquid of step (5) dilutes 2-4 times, and in 70-90 ℃ of baking 30-50 minute.
In sum:
The present invention can carry out recycling to perfluoro sulfonic acid membrane and prepare perfluorinated sulfonic acid solution and perfluoro sulfonic acid membrane, can save the use cost of proton exchange membrane, will promote the commercial applications of PEMFC.
In the perfluorinated sulfonic acid solution because of preparation mainly is volatile organic solvent, can be used for spraying or directly being added on pole catalyze layer to increase the phase reaction area of catalyst in the electrode, improves the utilance of catalyst.
The present invention makes perfluorinated sulfonic acid solution can be used for preparation enhancing composite membrane, also can repair the micropore in the perfluoro sulfonic acid membrane.
The present invention is film forming in high boiling solvent, lower boiling organic solvent and water are driven away fully, the big shortcoming of film fragility when both having overcome film forming, also improved the compactness of film, the perfluoro sulfonic acid membrane of preparation can be applied to Proton Exchange Membrane Fuel Cells once more, the composite membrane of direct methanol fuel cell and multilayer.
The present invention adopts and adds high boiling solvent film forming, in perfluorinated sulfonic resin quality one regularly, and can be by adding thickness and the area that the high boiling solvent volume comes controlling diaphragm.
The present invention adopts solution-casting from perfluorinated sulfonic acid formulations prepared from solutions perfluorinated sulfonic acid proton exchange membrane, and preparation technology is simple, and no complex device requirement is easy to operate, quick.Technology of the present invention has high value of practical, is easy to produce in batches perfluorinated sulfonic acid solution and perfluoro sulfonic acid membrane.
The patented method of being introduced in the present invention and the background technology relatively has following advantage:
1, the present invention can perfluoro sulfonic acid membrane carries out recycling and prepares perfluorinated sulfonic acid solution and perfluoro sulfonic acid membrane.Compare with EP Patent 0,066,369, the temperature that the present invention prepares perfluorinated sulfonic acid solution decreases, and Zhi Bei perfluoro sulfonic acid membrane compactness is good in addition, can directly apply to PEMFC.
2, with document US Patent 5,242,764 and US Patent 5,318,863 compare, and the perfluoro sulfonic acid membrane compactness of this method preparation is good, can under high temperature (80 ℃) and high pressure (0.5MPa) condition, work, fail safe is reliable, can be applied to powerful electric power system, and its battery operated performance significantly improves.
3, adopt the present invention to prepare the Nafion film assembling PEMFC that casts Nafion film and the business-like 50 μ m of Du Pont company again of thickness 60 μ m, their battery performance is comparatively near (see figure 5).
In conjunction with the accompanying drawings the present invention is described in detail with embodiment below.
Description of drawings
Fig. 1 is the battery polarization test curve of embodiment 1;
Fig. 2 is the battery polarization test curve of embodiment 2;
Fig. 3 is the battery polarization test curve of embodiment 3;
Fig. 4 is the battery polarization test curve of embodiment 4;
Fig. 5 is the battery polarization test curve of embodiment 5;
Fig. 6 compares for the performance of the present invention and commercialization Proton Exchange Membrane Fuel Cells.
Embodiment
Embodiment 1: the corner material that will reclaim perfluorinated sulfonic acid Nafion film carries out preliminary treatment, to remove the organic substance and the impurity metal ion on surface, at first uses 3-5%H
2O
2Under 80 ℃, boiled 1 hour, and, used the H of 0.5M more then with redistilled water flushing three times
2SO
4Boiled under 80 ℃ 1 hour, and boiled three times in 80 ℃ with redistilled water more afterwards, each 30 minutes, pretreated Nafion film was dried in 80 ℃ baking oven.The dried Nafion film that takes by weighing certain mass is placed in the reactor, before placing film is shredded, the aqueous solution (ethanol and water volume ratio are 1: 1) that adds absolute ethyl alcohol then, tightly react kettle cover well, again reactor was placed in 200 ℃ the baking oven molten sample 20 hours, cool to room temperature takes out, and promptly makes perfluorinated sulfonic acid Nafion solution; The Nafion solution that takes out certain volume places beaker, on 100 ℃ electric hot plate, organic solvent and water are driven away fully, thin film appears until beaker bottom, add a certain amount of N again, dinethylformamide, stirring is dissolved fully until beaker bottom film thing, places the ultrasonic wave vibration to remove bubble in 10 minutes, leaves standstill 24 hours in placing drier; Before the system film preparation liquid and mould all be placed on 50 ℃ the heating plate and heat, after waiting to be heated evenly, preparation liquid is poured in the mould, after treating the whole evaporation membranes dry tack frees of solvent, mould is placed in the vacuum drying oven, 120 ℃ of drying and forming-films of vacuum 12 hours, cool to room temperature takes out, put in the redistilled water film is taken out from mould, promptly make and cast perfluorinated sulfonic acid Nafion film (film thickness 60 μ m) again.Pretreated film be positioned in the redistilled water retain standby.
Adopt carbon paper, polytetrafluoroethylene (PTFE) emulsion, XC-72 carbon dust and 20%Pt/C Preparation of Catalyst porous gas diffusive electrode, catalyst loading is 0.40mg Ptcm in the electrode
2Electrode carries out three-dimensional and handles to increase the phase reaction area of electrode before use to the preparation liquid of the above-mentioned preparation of Catalytic Layer spraying one deck, dries in room temperature, dries by the fire 40min again in about 80 ℃, promptly finishes electrode three-dimensional step.
For guaranteeing that electrode and the effective of proton exchange membrane contact, reduce the contact resistance between electrode and the proton exchange membrane, adopt hot-pressing technique that electrode and proton exchange membrane are bonded together.The preparation method places two gas-diffusion electrodes respectively to cast Nafion film both sides again, and the Catalytic Layer one side is towards proton exchange membrane.In 130 ℃ of hot pressing, earlier little exerting pressure after water drains in the film, improved pressure again to 2MPa in forcing press, and hot pressing 2min takes out rapidly and cools off for little pressurization, and it is three-in-one promptly to make membrane electrode.
With the three-in-one PEMFC that is assembled into of membrane electrode of preparation, test battery performance on the monocell evaluating apparatus.The test battery polarization curve is seen accompanying drawing 1.The operating condition of battery is as follows: battery temperature is 80 ℃, and Hydrogen Vapor Pressure is 0.30MPa, and oxygen pressure is 0.50MPa, and hydrogen and oxygen is the outer humidifier humidification by 90 ℃ all.
Embodiment 2: adopt embodiment 1 method to prepare perfluorinated sulfonic acid Nafion solution and cast perfluorinated sulfonic acid Nafion film again and membrane electrode three-in-one.Solvent becomes methyl alcohol, normal propyl alcohol and water (volume ratio of methyl alcohol, normal propyl alcohol and water is 1: 1: 1), reactor was placed in 240 ℃ the baking oven molten sample 20 hours, high boiling solvent adopts dimethyl sulfoxide (DMSO), 160 ℃ of film-forming temperatures, it is 80 μ m that perfluorinated sulfonic acid Nafion film thickness is cast in preparation again, and it is three-in-one to adopt this film hot pressing to prepare membrane electrode.With the PEMFC of assembling, test battery performance on the monocell evaluating apparatus.The test battery polarization curve is seen accompanying drawing 2.The operating condition of battery is with embodiment 1.
Embodiment 3: adopt embodiment 1 method to prepare perfluorinated sulfonic acid Nafion solution and cast perfluorinated sulfonic acid Nafion film again and membrane electrode three-in-one.Solvent becomes ethanol, isopropyl alcohol and water (volume ratio of ethanol, isopropyl alcohol and water is 1: 2: 1), reactor was placed in 180 ℃ the baking oven molten sample 20 hours, high boiling solvent adopts 1-Methyl-2-Pyrrolidone, 160 ℃ of film-forming temperatures, it is 200 μ m that perfluorinated sulfonic acid Nafion film thickness is cast in preparation again, and it is three-in-one to adopt this film hot pressing to prepare membrane electrode.With the PEMFC of assembling, test battery performance on the monocell evaluating apparatus.Test to such an extent that the battery polarization curve is seen accompanying drawing 3.The operating condition of battery is with embodiment 1.
Embodiment 4: adopt embodiment 1 method to prepare perfluorinated sulfonic acid Nafion solution, to cast perfluorinated sulfonic acid Nafion film and membrane electrode more three-in-one.Solvent becomes methyl alcohol, ethanol, (volume ratio of methyl alcohol, ethanol, 2-fourth alcohol and water is 1: 2: 2 to 2-fourth alcohol and water: 1), reactor was placed in 180 ℃ the baking oven molten sample 20 hours, the Nafion solution that takes out certain volume adopts spraying method that electrode is carried out three-dimensional and handles, take out the perfluorinated sulfonic acid of the casting again Nafion film of the Nafion formulations prepared from solutions 60 μ m of certain volume, high boiling solvent adopts N, the N-dimethylacetylamide, 120 ℃ of film-forming temperatures, it is three-in-one to adopt this film hot pressing to prepare membrane electrode.With the PEMFC of assembling, test battery performance on the monocell evaluating apparatus.Test to such an extent that the battery polarization curve is seen accompanying drawing 4.The operating condition of battery is with embodiment 1.
Embodiment 5: adopt embodiment 1 method to prepare perfluorinated sulfonic acid Nafion solution and cast perfluorinated sulfonic acid Nafion film again and membrane electrode three-in-one.Solvent becomes ethanol, n-butanol and water (volume ratio of ethanol, isopropyl alcohol and water is 1: 1: 1), reactor was placed in 180 ℃ the baking oven molten sample 18 hours, high boiling solvent adopts N, dinethylformamide, 200 ℃ of film-forming temperatures, it is 90 μ m that perfluorinated sulfonic acid Nafion film thickness is cast in preparation again, and it is three-in-one to adopt this film hot pressing to prepare membrane electrode.With the PEMFC of assembling, test battery performance on the monocell evaluating apparatus.Test to such an extent that the battery polarization curve is seen accompanying drawing 5.The operating condition of battery is with embodiment 1.
Claims (3)
1, a kind of method of preparing membrane electrode using recasted perfluro sulfonic acid proton exchange film, it comprises the steps:
(1) the perfluorinated sulfonic acid proton exchange membrane is inserted methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol or/and in the aqueous solution of 2-butanols, heating for dissolving in closed reactor, heating for dissolving temperature are 180-240 ℃;
(2) perfluorinated sulfonic acid solution is heated to drying for 80-100 ℃;
(3) add N, dinethylformamide, N, N-dimethylacetylamide, dimethyl sulfoxide (DMSO) or 1-Methyl-2-Pyrrolidone dissolve the dry thing of perfluorinated sulfonic acid, leave standstill to be no less than 24 hours in drier, make preparation liquid;
(4) preparation liquid and mould are heated to 40-60 ℃, preparation liquid is poured in the mould, 120-200 ℃ of vacuum and heating drying film forming;
(5) preparation liquid is sprayed on the Catalytic Layer surface of porous gas diffusive electrode, heats after drying to 70-90 ℃ of baking 30-50 minute;
(6) two porous gas diffusive electrodes are placed the both sides that cast the perfluorinated sulfonic acid proton exchange membrane more respectively, the Catalytic Layer of electrode is towards proton exchange membrane, hot pressing in forcing press, and hot pressing condition is: pressure 2Mpa, temperature 110-140 ℃, time 1-3 minute.
2, the method for preparing membrane electrode using recasted perfluro sulfonic acid proton exchange film as claimed in claim 1 is characterized in that, the described porous gas diffusive electrode of step (5) is that carbon paper, ptfe emulsion, carbon dust and 20% platinum/C catalyst is prepared from.
3, the method for preparing membrane electrode using recasted perfluro sulfonic acid proton exchange film as claimed in claim 1 is characterized in that, is sprayed on catalyst surface after the described preparation liquid of step (5) dilutes 2-4 times.
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| CNB011368179A CN1185737C (en) | 2001-10-24 | 2001-10-24 | Method of preparing membrane electrode using recasted perfluro sulfonic acid proton exchange film |
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| CNB011368179A CN1185737C (en) | 2001-10-24 | 2001-10-24 | Method of preparing membrane electrode using recasted perfluro sulfonic acid proton exchange film |
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| CN1414652A CN1414652A (en) | 2003-04-30 |
| CN1185737C true CN1185737C (en) | 2005-01-19 |
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Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602005020790D1 (en) * | 2004-07-01 | 2010-06-02 | Umicore Ag & Co Kg | LAMINATION PROCESS FOR THE MANUFACTURE OF INTEGRATED MEMBRANE ELECTRODE MODULES |
| US9647274B2 (en) | 2008-01-11 | 2017-05-09 | GM Global Technology Operations LLC | Method of making a proton exchange membrane using a gas diffusion electrode as a substrate |
| US9419286B2 (en) | 2011-01-13 | 2016-08-16 | GM Global Technology Operations LLC | Wet lamination process for reducing mud cracking in fuel cell components |
| US9780399B2 (en) | 2008-01-11 | 2017-10-03 | GM Global Technology Operations LLC | Electrode assembly with integrated reinforcement layer |
| US9722269B2 (en) | 2008-01-11 | 2017-08-01 | GM Global Technology Operations LLC | Reinforced electrode assembly |
| CN101640274B (en) * | 2008-07-28 | 2011-04-13 | 上海蓝蔚科技发展有限公司 | Exhausting method during die closing in manufacturing membrane electrode of fuel battery |
| CN101759865B (en) * | 2008-11-14 | 2012-07-04 | 山东东岳高分子材料有限公司 | Method for preparing perfluor sulphonic acid proton exchange membranes by liquid surface tape casting method |
| US9012346B2 (en) | 2010-11-04 | 2015-04-21 | GM Global Technology Operations LLC | Wet lamination process for reducing mud cracking in fuel cell components |
| CN110112447B (en) * | 2019-05-09 | 2022-08-02 | 朝阳华鼎储能技术有限公司 | Multi-layer composite proton exchange membrane containing perfluorinated sulfonic acid resin and preparation method thereof |
| CN110066421A (en) * | 2019-05-09 | 2019-07-30 | 朝阳华鼎储能技术有限公司 | A kind of perfluorinated sulfonic resin recovery method of waste and old diaphragm |
| CN111116979A (en) * | 2019-12-09 | 2020-05-08 | 一汽解放汽车有限公司 | Recycling method of perfluorosulfonic acid proton exchange membrane, recycled product and application of recycled product |
| CN111077202B (en) * | 2019-12-31 | 2022-10-11 | 深圳市普晟传感技术有限公司 | Preparation method of selective formaldehyde membrane electrode assembly |
| CN111740124A (en) * | 2020-08-04 | 2020-10-02 | 无锡威孚高科技集团股份有限公司 | Processing method for improving microstructure of catalyst layer of proton exchange membrane fuel cell |
| CN114654755B (en) * | 2022-04-22 | 2024-05-10 | 天宫氢能材料科技(东莞)有限公司 | Production equipment and production method of perfluorosulfonic acid proton membrane |
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