Ion conducting hybrid membranes

• US 10,170,813 B2
• Filed: 05/06/2016
• Issued: 01/01/2019
• Est. Priority Date: 03/06/2014
• Status: Active Grant

• Current Assignee: Asahi Kasei Kabushiki Kaisha (Asahi Kasei Corporation), International Business Machines Corporation
• Original Assignee: Asahi Kasei Kabushiki Kaisha (Asahi Kasei Corporation), International Business Machines Corporation
• Inventors: Aetukuri, Naga Phani B., Hart, Mark W., Kim, Ho-Cheol, Kitajima, Shintaro, Krupp, Leslie E., McCloskey, Bryan D., Miller, Robert D., Scott, John Campbell, Wilcke, Winfried
• Primary Examiner(s): Marks, Jacob B
• Application Number:
  US15/148,676
• Publication Number:
  US 20160254560A1
• Time in Patent Office: 970 Days
• CPC Class Codes: C08J 5/22 Films, membranes or diaphragms
• CPC Class Codes: H01M 10/056 characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
• CPC Class Codes: H01M 12/02 Details of electrodes H01M4/00; of non-active parts H01M50/00
• CPC Class Codes: H01M 12/08 composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• CPC Class Codes: H01M 2300/0065 Solid electrolytes
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: H01M 8/1048 Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
• CPC Class Codes: H01M 8/1076 Micromachining techniques, e.g. masking, etching steps or photolithography
• CPC Class Codes: Y02E 60/10 Energy storage using batteries
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A method includes dispensing ion-conducting particles on a substrate comprising an adhesive to which the ion-conducting particles adhere; overcoating the ion conducting particles with a polymer; removing the substrate and the adhesive from the ion conducting particles; and removing a polymer overburden on the ion conducting particles to form a device that includes: (i) the polymer or a derivative thereof, and (ii) ion-conducting particles. At least a portion of the ion-conducting particles extend through the polymer or its derivative.

Claims

1. A method, comprising:

dispensing ion-conducting particles on a substrate comprising an adhesive to which the ion-conducting particles adhere, wherein the ion-conducting particles conduct ions chosen from Li, Na, and combinations thereof;

overcoating the ion conducting particles with a polymer;

removing the substrate and the adhesive from the ion conducting particles; and

removing a polymer overburden on the ion conducting particles to form a device that includes;

(i) the polymer or a derivative thereof, and (ii) ion-conducting particles, wherein at least a portion of the ion-conducting particles extend through the polymer or its derivative.

2. The method of claim 1, wherein the removable substrate has at least a portion in contact with the particles, and wherein the adhesive on the substrate is either water soluble or soluble in an organic solvent.

3. The method of claim 1, wherein the substrate is removed by mechanical, thermal and/or photochemical means.

4. The method of claim 1, wherein the polymer or its derivative is insoluble in one or more polar solvents.

5. The method of claim 1, wherein at least a portion of the ion conducting particles have a first exposed surface projecting from a first side of the polymer and a second exposed surface projecting from an opposed second side of the polymer, and wherein the exposed surfaces are free of the polymer.

6. The method of claim 1, wherein an aqueous solvent, an organic solvent, or a mixture thereof, is applied to remove the adhesive layer.

7. The method of claim 1, wherein the polymer overburden is removed by oxygen reactive ion etching, ion milling, or a combination thereof.

8. A method, comprising:

(a) dispensing metal oxide lithium ion-conducting particles on an adhesive layer;

(b) overcoating the ion conducting particles with a layer of a polymer selected from cyclo-olefins, poly-para-xylylenes, and benzocyclobutenes;

(c) removing a polymer overburden on the ion conducting particles to form a lithium ion conducting membrane, wherein at least a portion of the ion conducting particles in the membrane have a first exposed surface projecting from a first side of the layer of the polymer and a second exposed surface projecting from an opposed second side of the layer of the polymer, wherein the exposed surfaces are free of the polymer; and

(d) removing the adhesive layer from the ion conducting particles.

9. The method of claim 8, wherein the membrane has a lithium ion conductivity greater than about 10^-5 S/cm.

10. The method of claim 8, wherein the polymer layer is annealed prior to step (d).

11. The method of claim 8, wherein an aqueous solvent, an organic solvent, or a mixture thereof, is applied to remove the adhesive layer.

12. The method of claim 8, wherein the polymer overburden is removed by oxygen reactive ion etching, ion milling, or a combination thereof.