# US 12,191,443 B2 · Argyrodites doped with thiophilic metals

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- Number: US 12,191,443 B2
- Document ID: US12191443B2
- Status: Granted
- Kind: B2
- Application number: 16/947,793
- Filed: 2020-08-17
- Published: 2021-02-18
- Granted: 2025-01-07
- Earliest claimed: 2019-08-16
- Assignees: Blue Current, Inc.
- Applicants: Blue Current, Inc.
- Inventors: Benjamin Rupert
- Web page: https://patentgrep.com/patent/US12191443B2

## CPC

- H01M 10/0562: Solid materials
- C01B 25/14: Sulfur, selenium, or tellurium compounds of phosphorus
- C01D 15/00: Lithium compounds
- C01G 3/006: {Compounds containing copper, with or without oxygen or hydrogen, and containing two or more other elements}
- H01M 4/5815: {Sulfides}
- H01M 10/052: Li-accumulators
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/76: by a space-group or by other symmetry indications
- C01P 2002/77: by unit-cell parameters, atom positions or structure diagrams
- C01P 2006/40: Electric properties
- H01M 2300/002: Inorganic electrolyte
- H01M 2300/0082: Organic polymers
- H01M 2300/0091: in the form of mixtures
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01D: COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides C01B17/22; 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 and cyanogen, containing nitrogen and other non-metals C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; phosphides 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; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; 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 cyanamide C01C3/16; thiocyanates C01C3/20)
- 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 herein are solid materials that are ionically conductive and electrochemically stable. Embodiments of the solid materials are argyrodite-type compositions that have high ionic conductivity. The compositions include small amounts of thiophilic metals, whose binary sulfides do not react with water to hydrogen sulfide (H2S). As such, H2S release is minimized or eliminated. Also provided are methods of fabricating the materials and batteries and battery components containing the materials.

## Claims

### Claim 1

A composition comprising:
an alkali metal argyrodite sulfide-based halogen-containing ion conductor doped with a thiophilic metal,
wherein the thiophilic metal is selected from manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), mercury (Hg), molybdenum (Mo), and combinations thereof, wherein the ratio of thiophilic metal atoms to sulfur atoms in the alkali metal argyrodite sulfide-based ion conductor is between 1:120 and 1:20.

### Claim 2 (depends on 1)

The composition of claim 1, wherein the alkali metal is lithium (Li), sodium (Na) or potassium (K).

### Claim 3 (depends on 1)

The composition of claim 1, wherein the alkali metal is lithium.

### Claim 4 (depends on 1)

The composition of claim 1, wherein the alkali metal argyrodite sulfide-based ion conductor is given by the formula:
A7−x-(z*y)MzyPS6−xHalx
wherein
A is the alkali metal;
M is the thiophilic metal;
Hal is selected from chlorine (Cl), bromine (Br), and iodine (I);
z is the oxidation state of the metal;
0<x≤2; and
0<y<(7−x)/z.

### Claim 5 (depends on 4)

The composition of claim 4, wherein z>+1.

### Claim 6 (depends on 4)

The composition of claim 4, wherein z=+2.

### Claim 7 (depends on 4)

The composition of claim 4, wherein 1≤x≤1.6.

### Claim 8 (depends on 4)

The composition of claim 4, wherein 0.1≤y≤2−x.

### Claim 9 (depends on 1)

The composition of claim 1, wherein the alkali metal argyrodite sulfide-based ion conductor is given by the formula: A7−x+n-(z*y)MzyPS6−xHalx+n
wherein
A is the alkali metal;
M is the thiophilic metal;
Hal is selected from chlorine (Cl), bromine (Br), and iodine (I);
z is the oxidation state of the metal;
0.05≤n≤0.9
−3.0x+1.8≤n≤−3.0x+5.7
0≤y<(7−x)/z; and
0<x≤2.

### Claim 10 (depends on 9)

The composition of claim 9, wherein z>+1.

### Claim 11 (depends on 9)

The composition of claim 9, wherein z=+2.

### Claim 12 (depends on 1)

The composition of claim 1, wherein the alkali metal argyrodite sulfide-based ion conductor is single phase material.

### Claim 13 (depends on 1)

The composition of claim 1, wherein the argyrodite is Li5.8Cu0.1PS5Cl or Li5.4Cu0.1PS4.6Cl1.4.

### Claim 14 (depends on 1)

A composition comprising:
a composite film of particles comprising an argyrodite according to claim 1 in a polymer.