Ion conducting hybrid membranes

• US 10,770,769 B2
• Filed: 12/04/2018
• Issued: 09/08/2020
• Est. Priority Date: 03/06/2014
• Status: Active Grant

• Current Assignee: Asahi Kasei Kabushiki Kaisha, International Business Machines Corporation
• Original Assignee: 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:
  US16/209,894
• Publication Number:
  US 20190109359A1
• Time in Patent Office: 644 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 device, comprising:

a membrane comprising a polymer that is;

(i) impermeable to oxygen, and (ii) insoluble in at least one polar solvent; and

Li ion conducting particles in the membrane, wherein at least a portion of the particles have a first exposed surface projecting from a first side of the membrane and a second exposed surface projecting from an opposed second side of the membrane, wherein the exposed surfaces of the conducting particles are substantially free of the polymer, and wherein the thickness of the membrane is 15 μ

m to 100 μ

m.

2. The device of claim 1, wherein the thickness of the membrane is 15 μ

m to 65 μ

m.

3. The device of claim 1, wherein the thickness of the membrane is 15 μ

m to 30 μ

m.

4. The device of claim 1, wherein the membrane is impermeable to water and carbon dioxide.

5. The device of claim 1, wherein the polymer is chosen from cyclo-olefin polymers, poly-para-xylylenes, benzocyclobutenes, olefin addition polymers and copolymers, ring opening metathesis polymers and reduced forms thereof, acyclic diene metathesis polymers and reduced forms thereof, fluorocarbon addition polymers, fluoroether polymers, ring opened cyclobutyl fluoroethers, polyarylenes, polyarylene ethers, polybenzoazoles, polysiloxanes, silsequioxanes, polycarbosilanes, and mixtures and combinations thereof.

6. The device of claim 1, wherein the metal oxide lithium ion conducting particles comprise at least one of:

Li₃La_2/3-xTiO₃ or Li_xLa₃M₂O₁₂, wherein M=Zr, Nb, Ta, Sb, or Bi;

or Li_2-2xZn_1-xGe(OS)₄or LiM₂(PO₄)₃, wherein M=Ge, Ti, Hf, or Zr; and

mixtures and combinations thereof.

7. A lithium oxygen battery, comprising:

an anode;

a porous cathode;

an electrolyte; and

a membrane between the anode and the cathode, wherein the membrane comprises a polymer matrix and Li ion conducting particles in the matrix, wherein a majority of the particles have a first exposed surface projecting from a first side of the membrane and a second exposed surface projecting from an opposed second side of the membrane, wherein the exposed surfaces of the conducting particles are substantially free of the polymer forming the polymer matrix, and wherein the thickness of the membrane is 15 μ

m to 100 μ

m.

8. The battery of claim 7, wherein the thickness of the membrane is 15 μ

m to 65 μ

m.

9. The battery of claim 7, wherein the thickness of the membrane is 15 μ

m to 30 μ

m.

10. The battery of claim 7, wherein the membrane is impermeable to water and carbon dioxide.

11. The battery of claim 7, wherein the polymer matrix is chosen from cyclo-olefin polymers, poly-para-xylylenes, benzocyclobutenes, olefin addition polymers and copolymers, ring opening metathesis polymers and reduced forms thereof, acyclic diene metathesis polymers and reduced forms thereof, fluorocarbon addition polymers, fluoroether polymers, ring opened cyclobutyl fluoroethers, polyarylenes, polyarylene ethers, polybenzoazoles, polysiloxanes, silsequioxanes, polycarbosilanes, and mixtures and combinations thereof.

12. The battery of claim 7, wherein the metal oxide lithium ion conducting particles comprise at least one of:

Li₃La_2/3-xTiO₃ or Li_xLa₃M₂O₁₂, wherein M=Zr, Nb, Ta, Sb, or Bi;

or Li_2-2xZn_1-xGe(OS)₄or LiM₂(PO₄)₃, wherein M=Ge, Ti, Hf, or Zr; and

mixtures and combinations thereof.

13. The battery of claim 7, wherein the lithium ion conducting particles are embedded as a single layer in the polymer matrix.

14. The battery of claim 7, wherein the battery has a lithium ion conductivity greater than about 10⁻

5 S/cm.

15. The battery of claim 7, wherein the electrolyte is aqueous.

16. The battery of claim 7, wherein the electrolyte comprises a polar solvent.

17. The battery of claim 7, wherein the battery comprises:

a first electrolyte on a first side of the membrane; and

a second electrolyte on a second side of the membrane, wherein the second electrolyte is different from the first electrolyte, and the second side of the membrane is opposite the first side of the membrane.

18. The battery of claim 7, wherein the porous cathode is chosen from carbon, metals, metal oxides, and mixtures and combinations thereof.