CN1206760C - Preparation of non-carried catalyst electrode of polymer electrolyte film fuel cells - Google Patents
Preparation of non-carried catalyst electrode of polymer electrolyte film fuel cells Download PDFInfo
- Publication number
- CN1206760C CN1206760C CNB031187730A CN03118773A CN1206760C CN 1206760 C CN1206760 C CN 1206760C CN B031187730 A CNB031187730 A CN B031187730A CN 03118773 A CN03118773 A CN 03118773A CN 1206760 C CN1206760 C CN 1206760C
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- Prior art keywords
- catalyst
- polymer dielectric
- polymer electrolyte
- solution
- manufacture method
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- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000000446 fuel Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000005518 polymer electrolyte Substances 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- -1 poly tetrafluoroethylene Polymers 0.000 claims description 7
- 229940058401 polytetrafluoroethylene Drugs 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229920005601 base polymer Polymers 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000001603 reducing effect Effects 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052799 carbon Inorganic materials 0.000 abstract description 11
- 239000012528 membrane Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 239000012018 catalyst precursor Substances 0.000 abstract 3
- 239000002245 particle Substances 0.000 abstract 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 229910002849 PtRu Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000003460 sulfonic acids Chemical class 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
Classifications
-
- 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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- Inert Electrodes (AREA)
Abstract
本发明公开了一种聚合物电解质膜燃料电池无担载催化剂电极的制作方法。该方法将催化剂前体与聚合物电解质一起配成溶液；将此溶液涂于聚合物电解质膜或碳纸等基底的表面；再将基底表面涂层中的催化剂前体还原成金属。此方法将无担载催化剂的制备与电极的制作结合在一起，催化剂前体在聚合物电解质的保护下被还原成金属，可防止纳米尺寸的催化剂颗粒发生团聚和烧结，获得高度分散的催化剂；同时这种条件下产生的催化剂颗粒与聚合物电解质混合均匀，可获得最充分的接触。本方法操作简单，制作成本低，适合大规模工业化生产。
The invention discloses a method for preparing a catalyst-free electrode of a polymer electrolyte membrane fuel cell. In the method, the catalyst precursor and the polymer electrolyte are formulated into a solution; the solution is coated on the surface of a substrate such as a polymer electrolyte membrane or carbon paper; and then the catalyst precursor in the surface coating of the substrate is reduced to metal. This method combines the preparation of unsupported catalysts with the fabrication of electrodes. The catalyst precursors are reduced to metals under the protection of polymer electrolytes, which can prevent the agglomeration and sintering of nano-sized catalyst particles and obtain highly dispersed catalysts; At the same time, the catalyst particles produced under this condition are evenly mixed with the polymer electrolyte to obtain the most sufficient contact. The method is simple in operation, low in production cost and suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of polymer dielectric film fuel cell does not have the manufacture method of catalyst-loaded electrode.
Background technology
Polymer dielectric film fuel cell (polymer electrolyte membrane fuel cell, PEMFC) but have energy density and advantages such as power density is big, the low room temperature startup of working temperature, be considered to the optimal power supply of electric motor car and mobile electronic device.The core component of PEMFC is that (membrane electrode assembly, MEA), the quality of its structure is directly connected to the performance of battery to membrane electrode assembly.For the big electric current output of utilance, acquisition that improves catalyst, the electrode layer among the MEA should be thin as far as possible.Yet can obtain the PEMFC of enough big power output (as direct methanol fuel cell for need greater catalytic agent carrying capacity, direct methanol fuel cell, DMFC), reduce electrode layers thickness and have contradiction to a certain extent with the raising catalyst loading.
The catalyst that PEMFC uses normally is supported on platinum and the alloy thereof on the high-ratio surface charcoal.There are some researches show (L.Liu, et al, Electrochimica Acta, 1998,43,3657), if the catalyst that DMFC uses charcoal to carry, when catalyst loading is higher than 0.5mg/cm
2The time battery performance can't continue to improve; Do not have catalyst-loaded SC service ceiling and then can reach 8mg/cm
2In recent years, no catalyst-loaded quilt adopts more and more in the report of high-performance DMFC.
High dispersive no catalyst-loaded difficulty relatively in preparation, and in use take place easily to reunite and sintering.Make and do not have the key technology that catalyst-loaded electrode is acquisition high-performance DMFC efficiently.
Summary of the invention
The present invention is directed to the problems referred to above, propose the manufacture method that a kind of polymer dielectric film fuel cell does not have catalyst-loaded electrode.This method is simple to operate, and cost of manufacture is low, thereby suitable large-scale industrial production.
Technical scheme provided by the invention is: a kind of polymer dielectric film fuel cell does not have the manufacture method of catalyst-loaded electrode, and preparation earlier contains polymer dielectric and catalyst precarsor (as H
2PtCl
6, RuCl
3) solution; This kind solution is applied to substrate surface; After treating solvent evaporates, the catalyst precarsor in the substrate surface coating is reduced into metal.
Above-mentioned polymer dielectric is the strong-acid type polymer dielectric, or the strong base polymer dielectric; The solvent of above-mentioned solution is a water, or lower alcohol, or the mixture of lower alcohol and water (also can be the solvent of other solubilized catalyst precarsor and polymer dielectric); Above-mentioned substrate is heat-resisting chemically inert polymer film (as poly tetrafluoroethylene), or the polymer dielectric film of assemble use, or the diffusion layer material (as carbon paper) of assemble use; The above-mentioned method that catalyst precarsor in the substrate surface coating is reduced into metal is under the temperature that is no more than the polymer dielectric decomposition temperature, with substrate heat treatment under nitrogen atmosphere, make the catalyst precarsor in the substrate surface coating be reduced into metal: or substrate immersed contain in the concentrated solution of strong reductant, make the catalyst precarsor in the substrate surface coating be reduced into metal.
Advantage of the present invention is: making that will not have catalyst-loaded preparation and electrode combines, catalyst precarsor is reduced into metal under the protection of polymer dielectric, the catalyst granules that can prevent nano-scale takes place to reunite and sintering, obtains the catalyst of high degree of dispersion; Catalyst granules and the polymer dielectric that produces under this condition mixes simultaneously, can obtain the contact of fullest.These characteristics all are very beneficial for improving battery performance.Method provided by the invention is simple to operate, and cost of manufacture is low, thereby suitable large-scale industrial production.
Description of drawings
Fig. 1 is that no catalyst-loaded electrode of the present invention is made flow chart;
Fig. 2 supports the scanning electron micrograph of PtRu electrode surface for the nothing that makes with the present invention;
Fig. 3 supports the scanning electron micrograph of PtRu electrode section for the nothing that makes with the present invention;
Fig. 4 supports the X-ray diffraction spectrum that Pt and nothing support the PtRu electrode for the nothing that makes with the present invention.
Embodiment
Referring to Fig. 1, supporting the PtRu electrode with the making nothing is example, with H
2PtCl
6With RuCl
3(raw material A) is dissolved in ethanol or water, adds the ethanolic solution of an amount of perfluorinated sulfonic acid type polymer dielectric or polyvinyl pyridine quaternary ammonium type polymer dielectric (raw material B), and the ratio of Pt and Ru and polymer dielectric is regulated as required; According to the catalyst loading needs, this solution of certain volume is applied to poly tetrafluoroethylene or carbon paper surface (the ink coating surface that carbon paper is made into acetylene black and ptfe emulsion in advance, make its surfacing), poly tetrafluoroethylene or carbon paper place on the heating plate to promote solvent evaporates during operation; With the above-mentioned poly tetrafluoroethylene of catalyst precarsor and polymer dielectric or the NaBH that carbon paper immerses 2mol/L of scribbling
4Or N
2H
4The aqueous solution in, or 120 ℃ down with hydrogen reducings 1 hours, required nothing support the PtRu catalyst electrode.
Above-mentioned etoh solvent or water also can replace with the solvent of other solubilized catalyst precarsor and polymer dielectric.
The nothing that covers the carbon paper surface that adopts said method to make supports the surface and the section pattern of PtRu electrode and sees Fig. 2, Fig. 3, and catalyst layer surface is more smooth, thickness 10 μ m (every square centimeter contains 4mgPt+2mgRu) only.
Fig. 4 supports the X-ray diffraction spectrum that Pt (Fig. 4 c) and nothing support PtRu (Fig. 4 d) electrode with the nothing that covers the carbon paper surface that said method makes.Fig. 4 a, b are respectively perfluorinated sulfonic acid polymer dielectric film and the carbon paper X-ray diffraction spectrum of (surface coverage contains the diffusion layer of acetylene black and polytetrafluoroethylene) as reference object.The * peak is corresponding to the crystalline phase of fluorocarbon chain, from the polytetrafluoroethylene in perfluorinated sulfonic acid polymer dielectric film or the carbon paper among the figure; The # peak is from the graphite phase of carbon paper.Can calculate corresponding nothing according to the halfwidth of Scherrer formula Pt (220) diffraction maximum from Fig. 4 c, d supports the granularity that Pt catalyst and nothing support PtRu catalyst (the electrolytical content of perfluorinated sulfonic acid polymer is 15wt% in the electrode) and is respectively 6.1nm and 3.5nm.
Claims (5)
1. a polymer dielectric film fuel cell does not have the manufacture method of catalyst-loaded electrode, it is characterized in that: preparation contains the solution of polymer dielectric and catalyst precarsor; This kind solution is applied to substrate surface; After treating solvent evaporates, with the catalyst precarsor NaBH in the substrate surface coating
4Or N
2H
4The aqueous solution or hydrogen reducing become metal.
2. manufacture method according to claim 1 is characterized in that: above-mentioned polymer dielectric is the strong-acid type polymer dielectric, or the strong base polymer dielectric.
3. manufacture method according to claim 1 and 2 is characterized in that: the solvent of above-mentioned solution is a water, or lower alcohol, or the mixture of lower alcohol and water.
4. manufacture method according to claim 1 and 2 is characterized in that: above-mentioned substrate is a poly tetrafluoroethylene, or the polymer dielectric film of assemble use, or the diffusion layer material of assemble use.
5. manufacture method according to claim 1 and 2, it is characterized in that: the above-mentioned method that catalyst precarsor in the substrate surface coating is reduced into metal makes the catalyst precarsor in the substrate surface coating be reduced into metal under the temperature that is no more than the polymer dielectric decomposition temperature, with substrate heat treatment under nitrogen atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031187730A CN1206760C (en) | 2003-03-14 | 2003-03-14 | Preparation of non-carried catalyst electrode of polymer electrolyte film fuel cells |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031187730A CN1206760C (en) | 2003-03-14 | 2003-03-14 | Preparation of non-carried catalyst electrode of polymer electrolyte film fuel cells |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1440085A CN1440085A (en) | 2003-09-03 |
| CN1206760C true CN1206760C (en) | 2005-06-15 |
Family
ID=27797205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031187730A Expired - Fee Related CN1206760C (en) | 2003-03-14 | 2003-03-14 | Preparation of non-carried catalyst electrode of polymer electrolyte film fuel cells |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1206760C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326032A (en) * | 2013-05-30 | 2013-09-25 | 上海交通大学 | Method for preparing platinum gradient-distribution catalyst layer structure of proton exchange membrane fuel cell |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7981571B2 (en) | 2004-07-13 | 2011-07-19 | Panasonic Corporation | Polymer electrolyte fuel cell |
| JP5298405B2 (en) * | 2006-04-14 | 2013-09-25 | トヨタ自動車株式会社 | Manufacturing method of membrane electrode assembly for fuel cell |
| CN105372308B (en) * | 2015-12-09 | 2018-04-24 | 广东南海普锐斯科技有限公司 | A kind of low noble metal dosage formaldehyde sensor membrane electrode assembly and preparation method thereof |
| CN105845946B (en) * | 2016-05-10 | 2018-08-10 | 湖南科技大学 | A kind of gas-diffusion electrode and its manufacturing method of the in-situ deposition metal nano catalyst on carbon paper |
| CN107634232B (en) * | 2017-09-18 | 2020-06-05 | 大连交通大学 | Preparation method of membrane electrode for hydrophobic proton exchange membrane fuel cell |
| CN109103472B (en) * | 2018-07-27 | 2021-06-22 | 武汉理工新能源有限公司 | High oxygen transmission fuel cell catalyst layer, membrane electrode assembly and fuel cell |
-
2003
- 2003-03-14 CN CNB031187730A patent/CN1206760C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103326032A (en) * | 2013-05-30 | 2013-09-25 | 上海交通大学 | Method for preparing platinum gradient-distribution catalyst layer structure of proton exchange membrane fuel cell |
| CN103326032B (en) * | 2013-05-30 | 2015-07-15 | 上海交通大学 | Method for preparing platinum gradient-distribution catalyst layer structure of proton exchange membrane fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1440085A (en) | 2003-09-03 |
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