Composite polymer electrolytes for proton exchange membrane fuel cells

• US 7,008,971 B2
• Filed: 08/19/2003
• Issued: 03/07/2006
• Est. Priority Date: 08/13/2002
• Status: Expired due to Fees

• Current Assignee: Hoku Corp.
• Original Assignee: Hoku Scientific, Inc.
• Inventors: Taft, Karl Milton III, Kurano, Matthew Robert, Mada Kannan, Arunachala Nadar
• Primary Examiner(s): Bell, Bruce F.
• Application Number:
  US10/644,227
• Publication Number:
  US 20040048129A1
• Time in Patent Office: 931 Days
• Field of Search: 429/30, 429/33, 204/296, 524/445, 524/186, 524/431, 524/236, 521/27, 423/331, 423/327.1, 423/332
• US Class Current: 521/27
• CPC Class Codes: B01D 67/0079 Manufacture of membranes comprising organic and inorganic components
• CPC Class Codes: B01D 67/00793 Dispersing a component, e.g. as particles or powder, in another component
• CPC Class Codes: B01D 69/141 Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
• CPC Class Codes: B01D 69/14111 with nanoscale dispersed material, e.g. nanoparticles
• CPC Class Codes: B01D 71/024 Oxides
• CPC Class Codes: B01D 71/027 Silicium oxide
• CPC Class Codes: B01D 71/028 Molecular sieves carbon B01D71/021
• CPC Class Codes: B01D 71/0281 Zeolites
• CPC Class Codes: B01D 71/52 Polyethers
• CPC Class Codes: B01D 71/5222 Polyetherketone, polyetheretherketone, or polyaryletherketone
• CPC Class Codes: C08J 2383/02 Polysilicates
• CPC Class Codes: C08J 5/22 Films, membranes or diaphragms
• CPC Class Codes: C08K 3/346 Clay
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01M 2300/0068 inorganic
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 2300/0091 in the form of mixtures
• CPC Class Codes: H01M 8/0289 Means for holding the electrolyte solid polymer electrolytes H01M8/1018
• CPC Class Codes: H01M 8/1007 with both reactants being gaseous or vaporised H01M8/12 takes precedence
• CPC Class Codes: H01M 8/1016 characterised by the electrolyte material H01M8/12 takes precedence
• CPC Class Codes: Y02E 60/50 : Fuel cells

Abstract

Thin films of inexpensive composite polymer electrolyte membranes containing inorganic cation exchange materials including various clay based fillers are fabricated by solution casting. The membranes exhibit higher ion exchange capacity, proton conductivity and/or lower gas crossover. In general, the composite membranes exhibit excellent physicochemical properties and superior fuel cell performance in hydrogen oxygen fuel cells.

Claims

1. A method of fabricating a composite electrolyte for use in an electrochemical fuel cell, comprising:

(i) applying onto a surface of a substrate a viscous liquid composition of (a) an inorganic cation exchange material, (b) silica-based material, (c) a polymer-based material, and (d) a solvent-dispersant;

(ii) spreading the viscous liquid composition to form a uniform thickness layer on the substrate; and

(iii) allowing the solvent to evaporate from the viscous liquid composition to yield the composite electrolyte, wherein the inorganic cation exchange material comprises about 0.1 wt % to about 99 wt % of the composite electrolyte.

2. The method of claim 1, wherein the silica-based material comprises about 0.1 wt % to about 70 wt %, and the polymer-based material comprises about 0.1 wt % to 99.9 wt % of the composite electrolyte.

3. The method of claim 1 wherein step (ii) includes drawing the viscous liquid composition through a doctor blade assembly.

4. The method of claim 1 wherein step (iii) includes heating the viscous liquid composition.

5. The method of claim 1 wherein the inorganic cation exchange material comprises about 0.1 wt % to about 30 wt %, the silica-based material comprises about 0.1 wt % to about 15 wt %, and the polymer-based material comprises about 40 wt % to 99 wt % of the composite electrolyte.

6. The method of claim 1 wherein the inorganic cation exchange material is selected from the group consisting of clay, zeolite, hydrous oxide, inorganic and salt.

7. The method of claim 6 wherein the clay includes an aluminosilicate-based exchange material selected from the group consisting of montmorillonite, kaolinite, vermiculite, smectite, hectorite, mica, bentonite, nontronite, beidellite, volkonskoite, saponite, magadite, kenyaite, zeolite, alumina, and rutile.

8. The method of claim 6, wherein the clay is modified to make it more compatible with organic matrices, a clay modification including exfoliation which helps to separate platelets of inorganic substance.

9. The method of claim 6, wherein the clay includes a modified montmorillonite consisting of montmorillonite treated with a modifier material selected from a group consisting of aminododecanoic acid, trimethyl stearate ammonium, octadecylamine, and methyl dihydroxy hydrogenated tallow ammonium.

10. The method of claim 1 wherein the polymer-based material has a linear, branched, or netted morphology.

11. The method of claim 1 wherein the polymer-based material includes one of acrylonitrile/butadiene/stryene rubber (ABS), styrene butadiene/acrylate/acetate polymer blends, epoxides, polypropylene, polycarbonate, polystyrene, polyethylene, polyaryl ethers, and polysulfones.

12. The method of claim 1 wherein the solvent-dispersant comprises water, N-methyl pyrrolidinone, dimethyl sulfoxide, dimethyl acidimide, and dimethylformamide.

13. The method of claim 1 wherein the inorganic cation exchange material, the silica-based material and the polymer-based material comprise 90 wt % or more of the solids content of the composite electrolyte.

14. The method of claim 1 wherein the composite electrolyte when measured in the substantially dried state consists essentially of the inorganic cation exchange material, the silica-based material and the polymer-based material.

15. The method of claim 1 wherein the composite electrolyte has a proton conductivity of about 0.05 S/cm or higher.