# US 2014/0197351 A1 · Lithium-ion-conducting materials

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- Number: US 2014/0197351 A1
- Document ID: US20140197351A1
- Status: Published application
- Kind: A1
- Application number: 13/742,989
- Filed: 2013-01-16
- Published: 2014-07-17
- Earliest claimed: 2013-01-16
- Assignees: Ceramatec, Inc.
- Inventors: Shekar Balagopal; Roeger Marc Flinders; Spencer Jackman
- Web page: https://patentgrep.com/patent/US20140197351A1

## CPC

- C04B 35/447: based on phosphates {, e.g. hydroxyapatite}
- C04B 35/19: Alkali metal aluminosilicates, e.g. spodumene
- C04B 35/6261: {Milling}
- H01M 10/052: Li-accumulators
- H01M 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- C04B 2235/3203: Lithium oxide or oxide-forming salts thereof
- C04B 2235/3217: Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B 2235/3232: Titanium oxides or titanates, e.g. rutile or anatase
- C04B 2235/3244: Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B 2235/34: Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B 2235/3418: Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
- C04B 2235/77: Density
- C04B 2235/96: Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- H01M 10/0562: Solid materials
- H01M 2300/0071: Oxides
- Y02E 60/10: Energy storage using batteries
- 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
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Lithium-ion-conducting ceramic materials are disclosed having characteristics of high lithium-ion conductivity at low temperatures, good current efficiency, and stability in water and corrosive media under static and electrochemical conditions. Some general formulas for the lithium-ion-conducting materials include MI1+x+z-δMIIIxMIVayMIVb2-x-yMVzP3-zO12 and MI1+x+4z-δMIIIxMIVayMIVb2-x-y-zP3O12, wherein MI comprises Li, Na, or mixtures thereof; 0.05<x<0.5, 0.05<y<2, 0≦z<3, and 0≦δ<0.5; MIII comprises Al, Hf, Sc, Y, La, or mixtures thereof; MIVa comprises Zr, Ge, Sn, or mixtures thereof; MIVb comprises Ti; and MV comprises Si, Ge, Sn, or mixtures thereof. In some cases, the lithium-ion conducting materials are formed through a process in which the materials' powdered precursors are milled after being calcined and before being sintered. The milling process may include using milling media of multiple sizes.

## Claims

### Claim 1

A lithium ion conducting ceramic material having the general formulation:
MI1+x+z-δMIIIxMIVayMIVb2-x-yMVzP3-zO12
wherein MI comprises Li, Na, or a mixture thereof;
wherein 0.05<x<0.5, 0.05<y<2, 0≦z<3, 0≦δ<0.5;
wherein MIII comprises Al, Hf, Sc, Y, La, or mixtures thereof;
wherein MIVa comprises Zr, Ge, Sn, or mixtures thereof;
wherein MIVb comprises Ti; and
wherein MV comprises Si, Ge, Sn, or mixtures thereof.

### Claim 2 (depends on 1)

The lithium ion conducting ceramic material according to claim 1, wherein 0<z<3.

### Claim 3 (depends on 1)

The lithium ion conducting ceramic material according to claim 1, wherein 0<δ<0.5.

### Claim 4 (depends on 1)

The lithium ion conducting ceramic material according to claim 1, wherein MI comprises Li.

### Claim 5 (depends on 1)

The lithium ion conducting ceramic material of claim 1, wherein MIII comprises Al.

### Claim 6 (depends on 1)

The lithium ion conducting ceramic material of claim 1, wherein MIVa comprises Zr.

### Claim 7 (depends on 1)

The lithium ion conducting ceramic material of claim 1, wherein MV comprises Si.

### Claim 8 (depends on 1)

The lithium ion conducting ceramic material of claim 1, wherein MI comprises Li, wherein MIII comprises Al, wherein MIVa comprises Zr, and wherein MV comprises Si.

### Claim 9

A lithium ion conducting ceramic material having the general formulation:
MI1+x+4z-δMIIIxMIVayMIVb2-x-y-zP3O12
wherein MI comprises Li, Na, or mixtures thereof;
wherein 0.05<x<0.5, 0.05<y<2, 0≦z<3, 0≦δ<0.5;
wherein MIII comprises Al, Hf, Sc, Y, La, or mixtures thereof;
wherein MIVa comprises Zr, Ge, Sn, or mixtures thereof; and
wherein MIVb comprises Ti.

### Claim 10 (depends on 8)

The lithium ion conducting ceramic material according to claim 8, wherein 0<z<3.

### Claim 11 (depends on 8)

The lithium ion conducting ceramic material according to claim 8, wherein 0<δ<0.5.

### Claim 12 (depends on 1)

The lithium ion conducting ceramic material of claim 1, wherein 0.05≦x≦0.45.

### Claim 13 (depends on 1)

The lithium ion conducting ceramic material of claim 1, wherein 0.05≦y≦0.4.

### Claim 14 (depends on 1)

The lithium ion conducting ceramic material of claim 1, wherein MI comprises Li.

### Claim 15 (depends on 1)

The lithium ion conducting ceramic material of claim 1, wherein MIII comprises Al.

### Claim 16 (depends on 1)

The lithium ion conducting ceramic material of claim 1, wherein the material is substantially devoid of MIVa.

### Claim 17

A lithium ion conducting ceramic material having the general formulation selected from (i)
MI1+x+z-δMIIIxMIVayMIVb2-x-yMVzP3-zO12
and (ii)
MI1+x+4z-δMIIIxMIVayMIVb2-x-y-zP3O12,
wherein MI comprises Li, Na, or mixtures thereof;
wherein 0.05<x<0.5, 0.05<y<2, 0≦z<3, 0≦δ<0.5;
wherein MIII comprises Al, Hf, Sc, Y, La, or mixtures thereof;
wherein MIVa comprises Zr, Ge, Sn, or mixtures thereof;
wherein MIVb comprises Ti;
MV comprises Si, Ge, Sn, or mixtures thereof; and
wherein the lithium ion conducting ceramic material is hermetic to helium gas.

### Claim 18 (depends on 17)

The lithium ion conducting ceramic material of claim 17, wherein the ceramic material is produced through a process in which powdered precursors of the material are milled for over 80 hours, after being calcined and before being sintered.

### Claim 19 (depends on 18)

The lithium ion conducting ceramic material of claim 18, wherein the milling process includes using a first size of milling media and a second size of milling media that is large than the first size of milling media.

### Claim 20 (depends on 19)

The lithium ion conducting ceramic material of claim 19, wherein the first size of milling media comprises a diameter between about 3 mm and about 7 mm in diameter.

### Claim 21 (depends on 19)

The lithium ion conducting ceramic material of claim 19, wherein the second size of milling media comprises a diameter between about 8 mm and about 12 mm in diameter.

### Claim 22

A lithium ion conducting ceramic material having the general formulation:
MI1+x+4z-δMIIIxMIVayMIVb2-x-y-zP3O12
wherein MI comprises Li;
wherein 0≦x≦0.5, 0≦y≦2, 0≦z≦3, 0≦δ≦1;
wherein MIII comprises Al, Hf, Sc, Y, La, or mixtures thereof;
wherein MIVa comprises Zr, Ge, Sn, or mixtures thereof; and
wherein MIVb comprises Ti.

### Claim 23

A lithium ion conducting ceramic material having the general formulation:
MI1+x+4α-βMIIIxMIVayMIVb2-x-y-αMVzP3-zO12
wherein MI comprises Li;
wherein 0.05≦x≦0.5, 0.05≦y≦2, 0≦z≦1, 0.05≦α≦0.5, 0≦β≦1;
wherein MIII comprises Al, Hf, Sc, Y, La, or mixtures thereof;
wherein MIVa comprises Zr, Ge, Sn, or mixtures thereof; and
wherein MIVb comprises Ti.