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US5084144A Expired / Lapsed US ⏱️ 0.0 years remaining

High utilization supported catalytic metal-containing gas-diffusion electrode, process for making it, and cells utilizing it

Assignee: Physical Sciences Inc
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Filing: 1990-07-31
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Granted: 1992-01-28
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Expires: 2010-07-31
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Abstract

Abstract Gas-diffusion electrodes (GDE's) suitable for use with a solid polymer electrolyte (s.p.e.), particularly in s.p.e. fuel cells, which GDE's provide unusually highly efficient use of noble or precious electrocatalytic metals, are obtained by starting with a GDE which is essentially fully fabricated except for electrocatalytic metal treatment and s.p.e. treatment, e.g. a carbon GDE having a gas-permeable hydrophobic face and a particulate carbon-containing catalytic face. This untreated GDE is treated by a. impregnating an s.p.e. solutuion into the catalytic face until the solution penetrates part way into the cross-section of the GDE, especially into the carbon particulate or other support material, but not as far as the hydrophobic, gas permeable face, b. inserting the thus-treated GDE and a counterelectrode into a plating bath containing, for example, M+, M++, and/or M+++ ions, where M is a metal of Group VIII or I-B of the Periodic Table, and c. applying an interrupted current (periodically interrupted or a single, long pulse <2 minutes in duration) to the thus-treated GDE, so that metal particles<10 nm (<100A) in average particle size deposit on the particulate support material (e.g. high surface are carbon) of the catalytic face, but essentially only on sites where the support material is already in contact with the previously-deposited s.p.e. Because the deposited metal particles are in contact with an ionic pathway (through the s.p.e.) and an electronic pathway (through the support material), virtually every deposited metal particle is effective in catalyzing the electro-oxidation or electro-reduction of a reactant gas supplied to the gas-permeable hydrophobic face of the GDE during cell operation. s.p.e. fuel cells of this invention provide good performance with GDE loadings of 0.05-4.0 mg/cm2 of catalytic metal, a performance comparable to cells with GDE loadings of about 0.5 mg/cm2 of the same metal.

Inventors

  • 👤 N. R. K. Vilambi Reddy
  • 👤 Everett B. Anderson
  • 👤 Earl J. Taylor

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-29 17:25
CPC Classifications
H; H01; H01M; H01M4/00; H01M4/86; H01M4/88; H01M4/8803; H01M4/8807; H01M4/8663; H01M4/8668; H01M4/8825; H01M4/8853; H01M4/90; H01M4/92; H01M4/925; H01M4/926; H01M8/00; H01M8/08; H01M8/10; H01M8/1004; H01M2300/00; H01M2300/0017; H01M2300/0065; H01M2300/0082; H01M8/1007; H01M8/1009; Y; Y02; Y02E; Y02E60/00; Y02E60/30; Y02E60/50; Y02P; Y02P70/00; Y02P70/50; Y10; Y10S; Y10S205/00; Y10S205/917

Claims Analysis

Total Claims: 21
Claim 1
Independent Claim 266 words
A process for increasing the electrocatalytic activity of a gas-diffusion electrode having a gas-permeable face, and opposite thereto, a catalyzable face comprising a support material, said gas-diffusion electrode being substantially free of catalytic metal on the surface of said support material, said method comprising: a. impregnating into the catalyzable face of the gas-diffusion electrode a solution comprising an ion-exchange polymer, until said solution has wetted the catalyzable face of the gas-diffusion electrode and has penetrated part way into the cross-section of the untreated gas-diffusion electrode, thereby depositing ion-exchange polymer in contact with the support material, said gas-diffusion electrode, prior to this impregnating step, being substantially free of noble or precious catalytic metal on the surface of the support material and also substantially free of ion-exchange polymer, b. inserting the thus-treated gas-diffusion electrode resulting from said step a., along with a counterelectrode, into a plating bath containing ions, said ions including ions which contain a noble or precious catalytic metal in oxidized form, c. applying direct current to the said ion-exchange polymer-treated gas-diffusion electrode and the counterelectrode, and interrupting the direct current so that noble or precious catalytic metal particles not larger than about 10 nanometers in average particle size deposit on the support material of the catalyzable face of said treated gas diffusion electrode wherein a resulting loading of the catalytic metal particles is less than 4 mg per geometric square centimeter of catalyzable face, the depositing of these catalytic metal particles on the support material of the catalyzable face taking place essentially only on sites where support material is in contact with previously-deposited ion-exchange polymer.
Claim 2
Dependent Claim 266 words
A process for increasing the electrocatalytic activity of a gas-diffusion electrode having a gas-permeable face, and opposite thereto, a catalyzable face comprising a support material, said gas-diffusion electrode being substantially free of catalytic metal on the surface of said support material, said method comprising: a. impregnating into the catalyzable face of the gas-diffusion electrode a solution comprising an ion-exchange polymer, until said solution has wetted the catalyzable face of the gas-diffusion electrode and has penetrated part way into the cross-section of the untreated gas-diffusion electrode, thereby depositing ion-exchange polymer in contact with the support material, said gas-diffusion electrode, prior to this impregnating step, being substantially free of noble or precious catalytic metal on the surface of the support material and also substantially free of ion-exchange polymer, b. inserting the thus-treated gas-diffusion electrode resulting from said step a., along with a counterelectrode, into a plating bath containing ions, said ions including ions which contain a noble or precious catalytic metal in oxidized form, c. applying direct current to the said ion-exchange polymer-treated gas-diffusion electrode and the counterelectrode, and interrupting the direct current so that noble or precious catalytic metal particles not larger than about 10 nanometers in average particle size deposit on the support material of the catalyzable face of said treated gas diffusion electrode wherein a resulting loading of the catalytic metal particles is less than 4 mg per geometric square centimeter of catalyzable face, the depositing of these catalytic metal particles on the support material of the catalyzable face taking place essentially only on sites where support material is in contact with previously-deposited ion-exchange polymer.
Claim 3
Dependent Claim 33 words
A process according to claim 1 wherein the support material comprises particles or fibers or sintered particles or fibers comprising carbon or a non-noble, non-precious metal or an electrically-conductive or semi-conducting inorganic compound.
Claim 4
Dependent Claim 30 words
A process according to claim 1, wherein said solution comprises a fluorinated cation-exchange polymer dissolved in a polar liquid organic solvent or a polar liquid organic solvent mixed with water.
Claim 5
Dependent Claim 43 words
A process according to claim 3 wherein, in said step a, the untreated gas-diffusion electrode is floated on the surface of said solution such that the catalyzable face of the untreated gas-diffusion electrode is in face-to-face contact with the surface of the solution.
Claim 6
Dependent Claim 45 words
A process according to claim 3 wherein, in said step a, said solution comprises 0.1 to 50% by weight of fluorinated cation-exchange polymer, based on the weight of the solution, said solvent having a boiling point at atmospheric pressure not greater than about 150° C.
Claim 7
Dependent Claim 53 words
A process according to claim 5 wherein, during or subsequent to the completion of said step a but prior to said step b the polar liquid organic solvent is evaporated from the thus-treated gas-diffusion electrode so that the deposits of ion-exchange polymer in contact with the support material become substantially immobilized, solidified material.
Claim 8
Dependent Claim 75 words
A process according to claim 1 wherein the support material comprises particles or fibers or sintered particles or fibers comprising carbon or an electrically conducting or semiconducting oxide of a non-noble, non-precious transition metal, and the catalytic metal deposited on the support material consists essentially of a particulate metal of Group VIII or Group I-B of the Periodic Table of the Elements, the particles of said particulate metal averaging less than 5 nanometers in size.
Claim 9
Dependent Claim 41 words
A process according to claim 1 wherein the ion-exchange polymer is a cation exchange polymer, and the plating bath of said step b contains cations of a metal of Group VIII or Group I-B of the Periodic Table of the Elements.
Claim 10
Dependent Claim 34 words
A process according to claim wherein the loading of catalytic metal on the support material resulting from said step c is about 0.01 to about 2.0 mg per geometric square centimeter of catalyzable face.
Claim 11
Dependent Claim 23 words
A process according to claim 9 wherein said loading is about 0.03 to about 1.0 mg per geometric square centimeter of catalyzable face.
Claim 12
Dependent Claim 40 words
A process according to claim 1, wherein the pulsed direct current of said step c thus interrupted, is selected to produce adherent deposits of catalytic metal and particles of catalytic metal which are smaller on the average than 10 nanometers.
Claim 13
Dependent Claim 39 words
A process according to claim 11 wherein the thus-interrupted direct current is governed by a wave form selected such that the peak current density is at least about 5 mA/cm 2 and the on-time is less than 5 minutes.
Claim 14
Dependent Claim 31 words
A process according to claim 12, wherein the wave form is selected such that the peak current is about 10-100 mA/cm 2 and the on-time is 0.1 to about 2 minutes.
Claim 15
Dependent Claim 77 words
A process according to claim 1, wherein the ion-exchange polymer is a solid polymer obtained by polymerizing an unsaturated monomer of the formula Z--CF(R.sub.f)CF(R.sub.f)O[CR.sub.f CF.sub.2 O].sub.n CR.sub.f ═CFR.sub.f (I) or Z[CF(R.sub.f)].sub.m CR.sub.f ═CFR.sub.f (II) wherein Z is an ionic or ionizable group, the R f radicals, which are the same or different, are F, fluoroalkyl, perfluoroalkyl, or Cl, n is a number ranging from 0 to 10, and m is a number ranging from 1 to 10.
Claim 16
Dependent Claim 35 words
A process according to claim 14, wherein Z is an acidic group selected from --SC 3 H, --COOH, --PO 3 H 2 , --P(R f )O 2 H, --B(R f )OH, and --B(OR f )OH.
Claim 17
Dependent Claim 25 words
A process according to claim 14, wherein said unsaturated monomer is co-polymerized with a second unsaturated monomer of the formula CFR f =CFR f .
Claim 18
Dependent Claim 42 words
A treated, fully catalyzed, gas-diffusion electrode made by the process of claim 1 and having a loading of catalytic metal on the support material resulting from said step c. which is less than 4 mg per geometric square centimeter of catalyzable face.
Claim 19
Dependent Claim 45 words
An electrochemical cell comprising a cathode, an anode, and an electrolyte comprising a solid polymer electrolyte comprising an ion-exchange polymer or a liquid electrolyte, wherein either the cathode or the anode or both is or are a gas-diffusion electrode or the electrodes of claim 17.
Claim 20
Dependent Claim 73 words
A fuel cell comprising a cathode, an anode, means for providing a flow of fuel to the anode, means for providing air or oxygen to the cathode, and an electrolyte comprising a cation-exchange polymer or an aqueous solution of an acid for providing an ionic pathway between the cathode and the anode, wherein the anode comprises or the anode and the cathode comprise a gas-diffusion electrode mode by the process of claim 17.
Claim 21
Dependent Claim 37 words
A process according to claim 1, wherein said gas-diffusion electrode which is impregnated in said impregnating step has a gas-permeable face comprising a hydrophobic polymer and an opposite face comprising a particulate or fibrous electrically conductive material.

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1995-01-27 1995-07-29 1996-01-28 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1999-01-27 1999-07-29 2000-01-28 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 2003-01-27 2003-07-29 2004-01-28 $7700.00 Window Closed / Lapsed

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