Method for producing a waterproof and ion-conducting flexible membrane

Patent metadata

Field	Value
Publication number	US-9972817-B2
Application number	US-201515536238-A
Country	US
Kind code	B2
Filing date	Dec 14, 2015
Priority date	Dec 17, 2014
Publication date	May 15, 2018
Grant date	May 15, 2018

Abstract

A method for producing a waterproof and ion-conducting flexible membrane intended for protecting a metal electrode. It comprises a synthesis by electrically assisted extrusion of compact fibers forming an ion-conducting fiber array comprising a first material. The fiber array defines a first surface and a second surface opposite the first surface. Subsequently, the fiber array is impregnated with a polymer of a second material, to form a metal electrode protection membrane. The fiber array forms paths for conducting ions between the first surface and the second surface and through the second material. The first surface is intended to be in contact with the metal electrode.

First claim

The invention claimed is:

1. A method for producing a waterproof and ion-conducting flexible membrane for protecting a metal electrode comprising:
synthesizing, by electrically assisted extrusion, sealant fibers forming a fiber array of ion-conducting fibers comprising at least one first material, the fiber array defining a first surface and a second surface opposite the first surface;
impregnating the fiber array with a polymer of a second material, to form a metal electrode protection membrane, the fiber array forming ion conduction paths between the first and second surfaces and through the polymer of the second material, the first surface being in contact with the metal electrode.

2. The method according to claim 1 , wherein the fiber array impregnation further comprises:
removing the polymer on a surface of the membrane such that the first surface of the fiber array is devoid of polymer.

3. The method according to claim 1 , wherein the first material is present in the form of inorganic particles, the method further comprises:
performing spark plasma sintering of the fiber array prior to impregnating the fiber array to ensure a connection of inorganic particles of sealant fibers in the fiber array.

4. The method according to claim 1 , wherein, after the electrically assisted extrusion of sealant fibers, the method further comprises:
depositing, on the ion-conducting fiber array, a third material chosen from among the group constituted of a photo-activated polymerization polymer, an electrically activated polymerization polymer.

5. The method according to claim 1 , wherein the electrically assisted extrusion of sealant fibers further comprises:
extruding the sealant fibers by using at least one nozzle with a chosen diameter comprising several material inlets for synthesizing a sealant fiber with a chosen dimension, and
controlling the dosage and arrangement of materials composing the sealant fibers by using various material inlets of the nozzle.

6. The method according to claim 1 , wherein the method further comprises:
performing electrically assisted extrusion and impregnation on the surface of a metal negative electrode of a metal-air battery.

7. A waterproof and ion-conducting flexible membrane for protecting a metal electrode comprising:
a fiber array comprising sealant and ion-conducting fibers comprising at least one first material, the fiber array defining a first surface and a second surface opposite the first surface;
a second material comprising a polymer impregnating the fiber array and thus forming a metal electrode protection membrane, the fiber array forming ion conduction paths between the first and second surfaces and through the polymer of the second material, the first surface being in contact with the metal electrode.

8. The membrane according to claim 7 , wherein the fiber array comprises sealant fibers comprising:
a central part comprising ion-conducting particles of the first material, and
a peripheral part surrounding the central part comprising a sealant polymer.

9. The membrane according to claim 7 , wherein the fiber array comprises sealant fibers comprising:
a central part comprising a fourth material, which is organic, comprising a polymer, and
a central envelope surrounding the central part, comprising ion-conducting particles of the first material, and
a peripheral part surrounding the central envelope, comprising a sealant polymer.

10. The membrane according to claim 7 , wherein the fiber array comprises sealant fibers comprising:
a central part comprising ion-conducting particles of the first material, and
a central envelope surrounding the central part, comprising a fourth material, which is organic, comprising a polymer, and
a peripheral part surrounding the central envelope, comprising a sealant polymer.

11. The membrane according to claim 7 , wherein the first surface has a physicochemical affinity with an outer surface of the metal electrode, said physicochemical affinity ensuring permanent contact between the first surface and the outer surface of the metal electrode.

12. The membrane according to claim 7 , wherein the first material may be chosen from among the group of inorganic compounds constituted of lithium aluminum titanium phosphate (LATP), Li1.4Al0.4Ti1.6(PO4)3 Li1.2Al0.2Ti1.8(PO4)3, LiTi2(PO4)3, lithium titanium phosphate (LTP), Na3Si2Zr1.88Y0.12PO12, Na3Si2 Zr2PO12 or beta-Al2O3 and the second material may be a fluorinated polymer.

13. The membrane according to claim 7 , wherein the membrane has a thickness of between one micron and one hundred microns.

14. A battery comprising at least one electrochemical cell comprising:
a metal negative electrode immersed in a liquid electrolyte solution;
a waterproof and ion-conducting flexible membrane for protecting a metal electrode comprising:
a fiber array comprising sealant and ion-conducting fibers comprising at least one first material, the fiber array defining a first surface and a second surface opposite the first surface;
a second material comprising a polymer impregnating the fiber array and thus forming a metal electrode protection membrane, the fiber array forming ion conduction paths between the first and second surfaces and through the polymer of the second material, the first surface being in contact with the metal electrode,
the waterproof and ion-conducting flexible membrane surrounding the negative electrode in the electrolyte solution.

Assignees

• Electricite De France

Inventors

• Stevens Philippe
• Toussaint Gwenaelle
• Lancel Gilles
• Laberty-Robert Christel
• Bregiroux Damien
• Sanchez Clement

Classifications

• H01M50/406

  Moulding; Embossing; Cutting · CPC title

• H01M4/8605

  Porous electrodes · CPC title

• H01M4/90

  Selection of catalytic material · CPC title

• H01M8/1041

  Polymer electrolyte composites, mixtures or blends · CPC title

• C04B35/634

  Polymers (C04B35/636 takes precedence) · CPC title