Layered double hydroxide film and composite material containing layered double hydroxide

Patent metadata

Field	Value
Publication number	US-10370250-B2
Application number	US-201715607765-A
Country	US
Kind code	B2
Filing date	May 30, 2017
Priority date	Dec 17, 2014
Publication date	Aug 6, 2019
Grant date	Aug 6, 2019

Abstract

Provided is a layered double hydroxide membrane containing a layered double hydroxide represented by the formula: M 2+ 1-x M 3+ x (OH) 2 A n− x/n .mH 2 O (where M 2+ represents a divalent cation, M 3+ represents a trivalent cation, A n− represents an n-valent anion, n is an integer of 1 or more, and x is 0.1 to 0.4), the layered double hydroxide membrane having water impermeability. The layered double hydroxide membrane includes a dense layer having water impermeability, and a non-flat surface structure that is rich in voids and/or protrusions and disposed on at least one side of the dense layer. The present invention provides an LDH membrane suitable for use as a solid electrolyte separator for a battery, the LDH membrane including a dense layer having water impermeability, and a specific structure disposed on at least one side of the dense layer and suitable for reducing the interfacial resistance between the LDH membrane and an electrolytic solution.

First claim

What is claimed is:

1. A layered double hydroxide membrane comprising a layered double hydroxide represented by the formula: M 2+ 1-x M 3+ x (OH) 2 A n− x/n .mH 2 O (where M 2+ represents a divalent cation, M 3+ represents a trivalent cation, A n− represents an n-valent anion, n is an integer of 1 or more, x is 0.1 to 0.4, and m is 0 or more), the layered double hydroxide membrane having water impermeability, wherein
the layered double hydroxide membrane comprises a dense layer having water impermeability, and a non-flat surface structure that is rich in voids and/or protrusions and disposed on at least one side of the dense layer.

2. The layered double hydroxide membrane according to claim 1 , wherein the non-flat surface structure comprises acicular particles protruding from the dense layer in a direction away from the dense layer.

3. The layered double hydroxide membrane according to claim 2 , wherein the acicular particles each have a cross-sectional diameter of 0.01 to 0.5 μm and a height of 0.5 to 3.0 μm.

4. The layered double hydroxide membrane according to claim 1 , wherein the non-flat surface structure comprises open-porous coarse particles that are rich in voids.

5. The layered double hydroxide membrane according to claim 4 , wherein the open-porous coarse particles comprise agglomerates of acicular or platy particles, the acicular or platy particles entangling each other to form voids.

6. The layered double hydroxide membrane according to claim 4 , wherein the open-porous coarse particles each have a diameter of 0.5 to 30 μm as measured in a direction parallel to the dense layer and a height of 0.5 to 30 μm.

7. The layered double hydroxide membrane according to claim 1 , wherein the layered double hydroxide contained in the dense layer is an agglomeration of platy particles, and the platy particles are oriented in such a manner that the tabular faces of the platy particles are substantially perpendicular to or oblique to the surface of the dense layer.

8. The layered double hydroxide membrane according to claim 1 , wherein in the general formula, M 2+ comprises Mg 2+ , M 3+ comprises Al 3+ , and A n− comprises Off and/or CO 3 2− .

9. The layered double hydroxide membrane according to claim 1 , having a thickness of not more than 100 μm.

10. A layered-double-hydroxide-containing composite material comprising a porous substrate and the layered double hydroxide membrane according to claim 1 , the layered double hydroxide membrane being disposed on at least one surface of the porous substrate.

11. The layered-double-hydroxide-containing composite material according to claim 10 , wherein the porous substrate is composed of at least one selected from the group consisting of ceramics, metals and polymers.

12. The layered-double-hydroxide-containing composite material according to claim 11 , wherein the porous substrate is composed of a ceramic, and the ceramic is at least one selected from the group consisting of alumina, zirconia, titania, magnesia, spinel, calcia, cordierite, zeolite, mullite, ferrite, zinc oxide, and silicon carbide.

13. The layered-double-hydroxide-containing composite material according to claim 10 , wherein the porous substrate has an average pore diameter of 0.001 to 1.5 μm.

14. The layered-double-hydroxide-containing composite material according to claim 10 , wherein the surface of the porous substrate has a porosity of 10 to 60%.

15. A battery comprising a separator comprising the layered double hydroxide membrane according to claim 1 .

16. A battery comprising a separator comprising the layered-double-hydroxide-containing composite material according to claim 10 .

Assignees

• Ngk Insulators Ltd

Inventors

• Yamamoto Sho
• FUJISAKI Megumi
• Yokoyama Shohei
• Yamada Naohito

Classifications

• H01M50/434

  Ceramics · CPC title

• H01M50/491

  Porosity · CPC title

• H01M50/489

  Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties · CPC title

• C04B35/453

  based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates · CPC title

• C04B35/565

  based on silicon carbide · CPC title