CN85102225A - Method for manufacturing thin waterproof gas diffusion electrode - Google Patents
Method for manufacturing thin waterproof gas diffusion electrode Download PDFInfo
- Publication number
- CN85102225A CN85102225A CN85102225.1A CN85102225A CN85102225A CN 85102225 A CN85102225 A CN 85102225A CN 85102225 A CN85102225 A CN 85102225A CN 85102225 A CN85102225 A CN 85102225A
- Authority
- CN
- China
- Prior art keywords
- solution
- catalyst
- aqueous solution
- flocculate
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000009792 diffusion process Methods 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000012528 membrane Substances 0.000 claims abstract description 7
- 238000004078 waterproofing Methods 0.000 claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- 239000000084 colloidal system Substances 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 claims description 3
- 238000005189 flocculation Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims 3
- 239000002184 metal Substances 0.000 claims 3
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000010422 painting Methods 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000007650 screen-printing Methods 0.000 claims 1
- 239000004809 Teflon Substances 0.000 abstract 1
- 229920006362 Teflon® Polymers 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000010345 tape casting Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000007767 bonding agent Substances 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HDEPFLVKWKPGFZ-UHFFFAOYSA-N Cl(=O)(=O)O.[Pt] Chemical compound Cl(=O)(=O)O.[Pt] HDEPFLVKWKPGFZ-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 238000007443 liposuction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000006228 supernatant Substances 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
Landscapes
- Inert Electrodes (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The present invention belongs to a method for manufacturing a thin waterproof gas diffusion electrode used in an electrochemical device. According to the method, the catalyst is directly prepared into a colloidal state in an aqueous solution so as to ensure high dispersibility. The colloidal solution of catalyst is added with high polymer emulsion as adhesive and water-proofing agent. After mixing uniformly, adjusting the pH value of the solution to 1-4 to flocculate the solution. A small amount of acid is added to the flocs to make them strongly acidic (pH < 1) to ensure good conductivity of the subsequently formed electrodes. The flocs are screen printed or doctor-blading coated onto a porous teflon membrane. Extracting with acetone to remove the residual surfactant.
Description
The invention belongs in the electrochemical device, particularly the manufacture method of the thin type waterproof gas diffused electrode that uses in electrochemical gas sensor and the metal-air cell.
In many electrochemical devices, need to use the water proof type gas-diffusion electrode.This class electrode in the past is made up of Catalytic Layer, conductive supporting member and watertight composition three parts mostly.Much more general with catalyst fines in addition the water proofing property high polymer make the bonding agent coated on conductive supporting member, porous waterproof membrane in addition again, co-sintered forms.Usually skewness in Catalytic Layer influences the consistency of its performance owing to catalyst fines and high polymer bonding agent.The patent GB 1,549,469 of U.S. united Technologies Corporation and US 4,043,933 have proposed one and have improved one's methods.At first catalyst fines is made aqueous solution suspended substance, and mix with the polymer emulsion of making bonding agent, regulator solution PH makes it flocculation then.The flocculate coated on conductive supporting member, is made electrode behind the sintering, can improve the gas-diffusion electrode that the consistency of electrode performance is used for some electrochemical sensor like this,, how to make catalyst with simple noble metal because of the need background current is little.Require the catalyst capacity value little, Catalytic Layer will approach, and without conductive supporting member.The common decentralization of noble metal catalyst for preparing with straightforward procedure is not enough, and particularly gold because it is very easily coalescent, is difficult to obtain the powder of high degree of dispersion, thereby Catalytic Layer is difficult to approach the very difficult minimizing of catalyst capacity value.The sintering process of this external electrode is complex process not only, but also influences activity of such catalysts to a certain extent.
Purpose of the present invention is born in that to make a kind of catalyst capacity value little, and catalyst and water proofing property bonding agent are evenly distributed in the Catalytic Layer, the chemical property high conformity, and without sintering,, without the thin type waterproof gas diffused electrode of conductive supporting member.
The invention is characterized at first noble metal catalyst is directly made the colloid form in the aqueous solution to have the dispersiveness of height to guarantee it.For example aqueous solution of chloraurate is made the colloid that reducing agent just can make gold with natrium citricum.The water proofing property high polymer that adds amount of calculation in solution is made bonding agent, and the weight ratio that for example adds ptfe emulsion itself and catalyst is after mixing to 4: 6 at 1: 9, to use H
2SO
4Regulator solution PH makes to produce flocculation.Drip small amount of acid in the flocculate, make into highly acid, have good electrical conductivity to guarantee the electrode that makes subsequently.Said flocculate coated on ptfe porous membrane (thickness 0.1-0.4mm aperture 0.1-60 μ m), is become an equal skim.Do the back and use the acetone extracting,, heat again and remove acetone to remove the surfactant of bringing into by ptfe emulsion, thin type waterproof gas diffused electrode.Wherein the capacity value of catalyst is 5～10 milligrams/centimetre
2
Waterproof gas diffused electrode made in accordance with the present invention, Catalytic Layer itself promptly has good electrical conductivity, thereby can save conductive supporting member.Said waterproof gas diffused electrode has enough water proofing properties and very high electro-chemical activity after the acetone extracting, therefore need not sintering again.
The aqueous solution of noble metal salts such as platinum chloric acid, iridous chloride, ruthenium trichloride makes colloidal platinum, colloid iridium, colloid ruthenium through reduction, and just can make with platinum, iridium or ruthenium according to method of the present invention is the waterproof gas diffused electrode of catalyst again.
Embodiments of the invention are as follows:
Get gold chloride 1 gram, be dissolved in 500 ml distilled waters, add the aqueous solution of 20 milligrams of gelatin, be heated to and boil.In addition 1% sodium citrate aqueous solution is heated to for 500 milliliters and boils.The two mixes rapidly.Under strong agitation, continue boiling 15 minutes, promptly obtain the colloid of gold.Be cooled to room temperature, in the colloidal solution of gold, add 160 milligrams of the ptfe emulsions of 60% concentration.Strong agitation makes it to mix.H with 30%
2SO
4Regulator solution PH is 1～4.Place a night, make it to flocculate fully.Inclining supernatant liquor, takes out flocculate.In said flocculate, drip small amount of H
2SO
4, make into highly acid (PH＜1).Said flocculate is become an even thin layer with stainless steel scraper coated under the infrared lamp irradiation on porous polytetrafluoroethyl-ne film.The electrode that coats is used the acetone extracting in the liposuction device, remove remaining surfactant.Electrode is taken out, under infrared lamp, dry.
According to the electrode that method of the present invention is made, Catalytic Layer is thin, and the catalyst capacity value is little, and the electrode activity height without sintering, without conductive supporting member, and has the low and simple advantage of technology of cost.
Claims (8)
1, a kind of manufacture method of water proof type gas-diffusion electrode.It is characterized in that electrode catalyst is the aqueous solution colloid with the metal of chemical method preparation.The waterproof polymer emulsion that in said aqueous solution colloid, adds amount of calculation.After mixing, regulator solution PH makes formation catalyst/high polymer flocculate.Said flocculate coated on ptfe porous membrane, is formed an even thin layer.Do the back and use the acetone extracting, remove remaining surfactant, acetone is removed in heating again.
2, the metal water solution colloid of said electrode catalyst is characterized in that the collaurum that aqueous solution of chloraurate makes with the natrium citricum reduction in the claim 1.
3, the metal water solution colloid of said electrode catalyst is characterized in that the colloidal platinum that chloroplatinic acid aqueous solution makes with the natrium citricum reduction in the claim 1.
4, said water proofing property high polymer is a polytetrafluoroethylene in the claim 1.The addition of said water proofing property high polymer is 1: 9 to 4: 6 with the ratio of catalyst weight.
5, claim requires the flocculation process described in 1, and the adjusting of its PH is to use 30%H
2SO
4The aqueous solution is adjusted to 1～4 with solution PH.
6, said flocculate adding small amount of acid makes into highly acid (PH＜1), has enough conductivity to guarantee the electrode of painting subsequently in the claim 1.
7, in the claim 6 said add after the acid flocculate with silk screen printing or with the scraper coated on ptfe porous membrane.
8, said ptfe porous membrane is that its thickness of perforated membrane without sintering is 0.1～0.4 millimeter in the claim 7, and its average pore size is 0.1～60 micron.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85102225A CN1020993C (en) | 1985-04-01 | 1985-04-01 | Process for thin type waterproof gas diffused electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85102225A CN1020993C (en) | 1985-04-01 | 1985-04-01 | Process for thin type waterproof gas diffused electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85102225A true CN85102225A (en) | 1986-09-24 |
| CN1020993C CN1020993C (en) | 1993-05-26 |
Family
ID=4792349
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN85102225A Expired - Fee Related CN1020993C (en) | 1985-04-01 | 1985-04-01 | Process for thin type waterproof gas diffused electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1020993C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100472209C (en) * | 2000-09-13 | 2009-03-25 | 中国科学院长春应用化学研究所 | Process for preparing full-fluorine sulfornic ions exchange membrane electrode |
| WO2012151820A1 (en) * | 2011-05-06 | 2012-11-15 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit baseboard made therefrom and production method thereof |
| CN105745533A (en) * | 2013-11-20 | 2016-07-06 | 株式会社电装 | Gas sensor |
| CN110261449A (en) * | 2019-05-15 | 2019-09-20 | 嘉兴鸿明传感科技有限公司 | A kind of preparation method and catalysis electrode of gas sensor catalysis electrode |
| CN111073034A (en) * | 2018-10-22 | 2020-04-28 | 中昊晨光化工研究院有限公司 | Method for continuously extracting and recovering polytetrafluoroethylene dispersion resin |
-
1985
- 1985-04-01 CN CN85102225A patent/CN1020993C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100472209C (en) * | 2000-09-13 | 2009-03-25 | 中国科学院长春应用化学研究所 | Process for preparing full-fluorine sulfornic ions exchange membrane electrode |
| WO2012151820A1 (en) * | 2011-05-06 | 2012-11-15 | 广东生益科技股份有限公司 | Composite material, high-frequency circuit baseboard made therefrom and production method thereof |
| US10194528B2 (en) | 2011-05-06 | 2019-01-29 | Guangdong Shengyi Sci. Tech Co., Ltd. | Composite material, high-frequency circuit baseboard made therefrom and production method thereof |
| CN105745533A (en) * | 2013-11-20 | 2016-07-06 | 株式会社电装 | Gas sensor |
| CN105745533B (en) * | 2013-11-20 | 2018-10-26 | 株式会社电装 | Gas sensor |
| CN111073034A (en) * | 2018-10-22 | 2020-04-28 | 中昊晨光化工研究院有限公司 | Method for continuously extracting and recovering polytetrafluoroethylene dispersion resin |
| CN110261449A (en) * | 2019-05-15 | 2019-09-20 | 嘉兴鸿明传感科技有限公司 | A kind of preparation method and catalysis electrode of gas sensor catalysis electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1020993C (en) | 1993-05-26 |
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Legal Events
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model |