# US 12,218,315 B2 · Barium-doped composite electrode materials for fluoride-ion electrochemical cells

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- Number: US 12,218,315 B2
- Document ID: US12218315B2
- Status: Granted
- Kind: B2
- Application number: 17/395,087
- Filed: 2021-08-05
- Published: 2021-11-25
- Granted: 2025-02-04
- Earliest claimed: 2016-12-15
- Assignees: Honda Motor Co., Ltd.; California Institute of Technology
- Applicants: Honda Motor Co., Ltd.; California Institute of Technology
- Inventors: Nam Hawn Chou; Kaoru Omichi; Ryan McKenney; Qingmin Xu; Christopher Brooks; Simon C. Jones; Isabelle M. Darolles; Hongjin Tan
- Web page: https://patentgrep.com/patent/US12218315B2

## CPC

- H01M 10/36: Accumulators not provided for in groups H01M10/05-H01M10/34
- C01F 17/265: Fluorides
- C01F 17/30: Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 (C01F17/247 - C01F17/294 take precedence)
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/366: {as layered products}
- H01M 10/054: Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C01F 11/22: Fluorides
- C01P 2002/54: one element only
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/03: obtained by SEM
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/80: Particles consisting of a mixture of two or more inorganic phases
- C01P 2006/40: Electric properties
- H01M 4/38: of elements or alloys
- H01M 2300/0034: Fluorinated solvents
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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})
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- 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

The present disclosure relates to a method of making core-shell and yolk-shell nanoparticles, and to electrodes comprising the same. The core-shell and yolk-shell nanoparticles and electrodes comprising them are suitable for use in electrochemical cells, such as fluoride shuttle batteries. The shell may protect the metal core from oxidation, including in an electrochemical cell. In some embodiments, an electrochemically active structure includes a dimensionally changeable active material forming a particle that expands or contracts upon reaction with or release of fluoride ions. One or more particles are at least partially surrounded with a fluoride-conducting encapsulant and optionally one or more voids are formed between the active material and the encapsulant using sacrificial layers or selective etching. The fluoride-conducting encapsulant may comprise one or more metals. When the electrochemically active structures are used in secondary batteries, the presence of voids can accommodate dimensional changes of the active material.

## Claims

### Claim 1

An electrode comprising:
a core comprising copper nanoparticles, and
a fluoride-containing shell at least partially surrounding the core,
wherein the fluoride-containing shell comprises a fluoride of barium and lanthanum, and wherein an empirical formula of the fluoride-containing shell comprises BaxLa1−x, wherein x is from about 0.03 to about 0.15.

### Claim 2 (depends on 1)

The electrode of claim 1, wherein the fluoride-containing shell is directly attached to the core.

### Claim 3 (depends on 1)

The electrode of claim 1, wherein the fluoride-containing shell is spaced from the core so as to define a void space therebetween.

### Claim 4 (depends on 1)

The electrode of claim 1, wherein x is about 0.03.

### Claim 5 (depends on 1)

A fluoride shuttle battery comprising the electrode of claim 1 and a liquid electrolyte.

### Claim 6 (depends on 5)

The fluoride shuttle battery of claim 5, wherein the liquid electrolyte comprises a fluoride salt and a solvent.

### Claim 7 (depends on 5)

The fluoride shuttle battery of claim 5, wherein the liquid electrolyte comprises a fluoride salt, a polymer, and an organic liquid.