# US 10,370,250 B2 · Layered double hydroxide film and composite material containing layered double hydroxide

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- Number: US 10,370,250 B2
- Document ID: US10370250B2
- Status: Granted
- Kind: B2
- Application number: 15/607,765
- Filed: 2017-05-30
- Published: 2017-09-14
- Granted: 2019-08-06
- Earliest claimed: 2014-12-17
- Assignees: NGK Insulators, Ltd.
- Applicants: Ngk Insulators, Ltd.
- Inventors: Sho Yamamoto; Megumi Fujisaki; Shohei Yokoyama; Naohito Yamada
- Web page: https://patentgrep.com/patent/US10370250B2

## CPC

- C01B 13/14: Methods for preparing oxides or hydroxides in general (particular individual oxides or hydroxides, see the relevant groups of subclasses C01B - C01G or C25B, according to the element combined with the oxygen or hydroxy group)
- C01F 7/785: Hydrotalcite
- C04B 35/04: based on magnesium oxide
- C04B 35/057: based on calcium oxide
- C04B 35/111: Fine ceramics
- C04B 35/185: Mullite {3Al2O3-2SiO2}
- C04B 35/195: Alkaline earth aluminosilicates, e.g. cordierite {or anorthite}
- C04B 35/26: based on ferrites
- C04B 35/443: Magnesium aluminate spinel
- C04B 35/453: based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
- C04B 35/46: based on titanium oxides or titanates (containing also zirconium or hafnium oxides, zirconates or hafnates C04B35/49)
- C04B 35/486: Fine ceramics
- C04B 35/565: based on silicon carbide
- H01M 50/403: Manufacturing processes of separators, membranes or diaphragms
- H01M 50/434: Ceramics
- H01M 50/44: Fibrous material
- H01M 50/449: having a layered structure
- H01M 50/489: Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M 50/491: Porosity
- C01P 2002/22: layered hydroxide-type, e.g. of the hydrotalcite-type
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C04B 2235/3225: Yttrium oxide or oxide-forming salts thereof
- C04B 2235/6021: Extrusion moulding
- C04B 2235/6567: Treatment time
- H01M 8/083: Alkaline fuel cells
- H01M 8/1016: characterised by the electrolyte material (H01M8/12 takes precedence)
- H01M 12/06: with one metallic and one gaseous electrode
- H01M 12/08: composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
- H01M 2300/0014: Alkaline electrolytes
- Y02E 60/10: Energy storage using batteries
- Y02E 60/50: Fuel cells
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01F: COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides or polysulfides of magnesium, calcium, strontium, or barium C01B17/42; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia or cyanogen containing nitrogen and non-metals and optionally metals C01B21/082; amides or imides of silicon C01B21/087}; metal {imides or} amides C01B21/092, {C01B21/0923}; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20; {double sulfates of magnesium with sodium or potassium C01D5/12; with other alkali metals C01D15/00, C01D17/00})
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Provided is a layered double hydroxide membrane containing a layered double hydroxide represented by the formula: M2+1-xM3+x(OH)2An−x/n.mH2O (where M2+ represents a divalent cation, M3+ represents a trivalent cation, An− 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.

## Claims

### Claim 1

A layered double hydroxide membrane comprising a layered double hydroxide represented by the formula: M2+1-xM3+x(OH)2An−x/n.mH2O (where M2+ represents a divalent cation, M3+ represents a trivalent cation, An− 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.

### Claim 2 (depends on 1)

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.

### Claim 3 (depends on 2)

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.

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 4)

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.

### Claim 6 (depends on 4)

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.

### Claim 7 (depends on 1)

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.

### Claim 8 (depends on 1)

The layered double hydroxide membrane according to claim 1, wherein in the general formula, M2+ comprises Mg2+, M3+ comprises Al3+, and An− comprises Off and/or CO32−.

### Claim 9 (depends on 1)

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

### Claim 10 (depends on 1)

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.

### Claim 11 (depends on 10)

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.

### Claim 12 (depends on 11)

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.

### Claim 13 (depends on 10)

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.

### Claim 14 (depends on 10)

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%.

### Claim 15 (depends on 1)

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

### Claim 16 (depends on 10)

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