Layered-double-hydroxide-oriented film and method for producing same

Patent metadata

Field	Value
Publication number	US-9793529-B2
Application number	US-201514814620-A
Country	US
Kind code	B2
Filing date	Jul 31, 2015
Priority date	Dec 27, 2013
Publication date	Oct 17, 2017
Grant date	Oct 17, 2017

Abstract

Provided is a layered double hydroxide oriented membrane in which layered double hydroxide plate-like particles are highly oriented in the approximately perpendicular direction and which is also suitable for densification. The layered double hydroxide oriented membrane of the present invention is composed of a layered double hydroxide represented by the general formula: M 2+ 1-x M 3+ x (OH) 2 A n− x/n .mH 2 O wherein M 2+ is a divalent cation, M 3+ is a trivalent cation, A n− is an anion having a valency of n, n is an integer of 1 or greater, x is 0.1 to 0.4, and m is 0 or greater, wherein when a surface of the oriented membrane is measured by X-ray diffractometry, a peak of a (003) plane is not substantially detected or is detected to be smaller than a peak of a (012) plane.

First claim

What is claimed is:

1. A battery including a separator comprising a layered double hydroxide oriented membrane composed of a layered double hydroxide represented by the following general formula:
M 2+ 1-x M 3+ x (OH) 2 A n− x/n .m H 2 O
wherein M 2+ is a divalent cation, M 3+ is a trivalent cation, A n− is an anion having a valency of n, n is an integer of 1 or greater, x is 0.1 to 0.4, and m is 0 or greater,
wherein when a surface of the oriented membrane is measured by X-ray diffractometry, a peak of a (003) plane is detected to be smaller than a peak of a (012) plane,
wherein the layered double hydroxide oriented membrane is formed on a polymer substrate, and
wherein the layered double hydroxide oriented membrane has a thickness of 5 μm or less.

2. The battery according to claim 1 , wherein in the general formula, at least M 2+ comprises Mg 2+ , M 3+ comprises Al 3+ , and A n− comprises OH − and/or CO 3 2− .

3. The battery according to claim 1 , wherein the surface of the oriented membrane has a porosity of 20% or less.

4. The battery according to claim 1 , wherein the surface of the oriented membrane has a porosity of 10% or less.

5. The battery according to claim 1 , wherein the peak of the (003) plane is less than ½ the peak of the (012) plane in intensity.

6. A method for producing a layered double hydroxide oriented membrane, comprising the steps of:
providing a polymer substrate of which a surface is anionized;
immersing the polymer substrate in an aqueous raw material solution comprising magnesium ions (Mg 2+ ) and aluminum ions (Al 3+ ) in a total concentration of 0.20 mol/L to 0.40 mol/L and comprising urea; and
subjecting the polymer substrate to a hydrothermal treatment in the aqueous raw material solution to form the layered double hydroxide oriented membrane on the polymer substrate,
wherein the layered double hydroxide is represented by the following general formula:
M 2+ 1-x M 3+ x (OH) 2 A n− x/n .m H 2 O

wherein M 2+ is a divalent cation, M 3+ is a trivalent cation, A n− is an anion having a valency of n, n is an integer of 1 or greater, x is 0.1 to 0.4, and m is 0 or greater,
wherein when the surface of the oriented membrane is measured by X-ray diffractometry, a peak of a (003) plane is detected to be smaller than a peak of a (012) plane, and
wherein the layered double hydroxide oriented membrane has a thickness of 5 μm or less.

7. The method according to claim 6 , wherein the anionization is performed by imparting at least one selected from the group consisting of SO 3 − , OH − , and CO 2 − to the surface of the polymer substrate.

8. The method according to claim 6 , wherein the polymer substrate of which the surface is anionized is a polymer substrate of which a surface is sulfonated.

9. The method according to claim 8 , wherein the sulfonated polymer substrate is an aromatic polymer substrate, which is sulfonated such that when a surface of the aromatic polymer substrate is analyzed by an attenuated total reflection (ATR) technique of Fourier transform infrared spectroscopy (FT-IR), a value T 1601 /T 1127 is 0.920 or greater wherein the value T 1601 /T 1127 is obtained by dividing T 1601 , which is a value of transmittance at 1601 cm −1 derived from phenyl group CC stretching vibration, by T 1127 , which is a value of transmittance at 1127 cm −1 derived from a sulfonic acid group, of a transmission spectrum.

10. The method according to claim 8 , wherein the step of providing a polymer substrate of which a surface is sulfonated is performed by providing a polymer substrate capable of being sulfonated, and immersing the polymer substrate in at least one selected from the group consisting of sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, and sulfuric anhydride.

11. The method according to claim 6 , wherein the total concentration of magnesium ions and aluminum ions is 0.24 mol/L to 0.28 mol/L.

12. The method according to claim 8 , wherein the hydrothermal treatment is performed in a closed vessel at a temperature of 60° C. to 150° C.

13. The method according to claim 6 , wherein magnesium nitrate and aluminum nitrate are dissolved in the aqueous raw material solution, whereby the aqueous raw material solution comprises nitrate ions in addition to magnesium ions and aluminum ions.

14. The method according to claim 13 , wherein a molar ratio of the urea to the nitrate ions (NO 3 − ) in the aqueous raw material solution is 4 to 5.

15. The method according to claim 6 , wherein the polymer substrate is composed of at least one selected from the group consisting of polystyrene, polyethersulfone, epoxy resin, and polyphenylene sulfide.

Assignees

• Ngk Insulators Ltd

Inventors

• FUJISAKI Megumi
• Saito Naomi
• Yamada Naohito

Classifications

• H01M12/06

  with one metallic and one gaseous electrode · CPC title

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title

• C01P2002/22

  layered hydroxide-type, e.g. of the hydrotalcite-type · CPC title

• C01F7/162 Primary

  Magnesium aluminates · CPC title

• H01M8/1016

  characterised by the electrolyte material (H01M8/12 takes precedence) · CPC title