# US 10,374,252 B2 · Fluoride ion battery and method for producing fluoride ion battery

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- Number: US 10,374,252 B2
- Document ID: US10374252B2
- Status: Granted
- Kind: B2
- Application number: 15/708,643
- Filed: 2017-09-19
- Published: 2018-05-10
- Granted: 2019-08-06
- Earliest claimed: 2016-11-08
- Assignees: Toyota Jidosha Kabushiki Kaisha
- Applicants: Toyota Jidosha Kabushiki Kaisha
- Inventors: Hidenori Miki
- Web page: https://patentgrep.com/patent/US10374252B2

## CPC

- H01M 10/0562: Solid materials
- C01F 17/0031
- H01M 4/0447: {of complete cells or cells stacks}
- H01M 4/38: of elements or alloys
- H01M 4/582: {Halogenides}
- H01M 4/583: Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/5835: {Comprising fluorine or fluoride salts}
- H01M 4/661: {Metal or alloys, e.g. alloy coatings (H01M4/669 take precedence)}
- H01M 10/05: Accumulators with non-aqueous electrolyte (H01M10/39 takes precedence)
- C01P 2006/40: Electric properties
- H01M 2300/008: Halides
- 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})
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

A fluoride ion battery in which an occurrence of a short circuit is suppressed achieves the object by providing a fluoride ion battery including: an electrode layer that includes a first metal element or a carbon element and has capability of fluorination and defluorination; a solid electrolyte layer containing a solid electrolyte material, the solid electrolyte material including a second metal element with lower fluorination potential and defluorination potential than the potentials of the first metal element or the carbon element; and an anode current collector, in this order; and an anode active material layer being not present between the solid electrolyte layer and the anode current collector; and at least one of the solid electrolyte layer and the anode current collector includes a simple substance of Pb, Sn, In, Bi, or Sb, or an alloy containing one or more of these metal elements.

## Claims

### Claim 1

A fluoride ion battery comprising:
an electrode layer that includes a first metal element or a carbon element and has capability of fluorination and defluorination;
a solid electrolyte layer containing a solid electrolyte material, the solid electrolyte material including a second metal element with lower fluorination potential and defluorination potential than the potentials of the first metal element or the carbon element; and
an anode current collector, in this order; and
an anode active material layer being not present between the solid electrolyte layer and the anode current collector; and
the anode current collector includes a simple substance of Pb, Sn, In, Bi, or Sb, or an alloy containing one or more of these metal elements; and wherein the anode current collector is directly disposed on a surface of the solid electrolyte layer.

### Claim 2 (depends on 1)

The fluoride ion battery according to claim 1, further comprising a bipolar structure in which a plurality of the electrode layers and the solid electrolyte layers are alternately disposed.

### Claim 3 (depends on 2)

The fluoride ion battery according to claim 2, wherein the electrode layer includes a simple substance of Pb, Sn, In, Bi, or Sb, or an alloy containing one or more of these metal elements.

### Claim 4 (depends on 1)

The fluoride ion battery according to claim 1, wherein the solid electrolyte layer includes a simple substance of Pb, Sn, In, Bi, or Sb, or an alloy containing one or more of these metal elements.

### Claim 5 (depends on 1)

The fluoride ion battery according to claim 1, wherein the second metal element is at least one kind of La, Ba, Pb, Sn, Ca and Ce.

### Claim 6 (depends on 1)

The fluoride ion battery according to claim 1, wherein the solid electrolyte material is at least one kind of La1-xBaxF3-x in which 0≤x≤2, Pb2-xSnxF4 in which 0≤x≤2, Ca2-xBaxF4 in which 0≤x≤2, and Ce1-xBaxF3-x in which 0≤x≤2.

### Claim 7

A fluoride ion battery comprising:
an electrode layer that includes a first metal element or a carbon element and has capability of fluorination and defluorination;
a solid electrolyte layer containing a solid electrolyte material, the solid electrolyte material including a second metal element with lower fluorination potential and defluorination potential than the potentials of the first metal element or the carbon element; and
an anode current collector, in this order; and
a fluoride layer containing a fluoride of the first metal element or the carbon element on a surface, that is the anode current collector side, of the electrode layer; and
an anode active material layer containing a simple substance of the second metal element on a surface, that is the anode current collector side, of the solid electrolyte layer, and
the anode current collector includes a simple substance of Pb, Sn, In, Bi, or Sb, or an alloy containing one or more of these metal elements; and wherein the anode current collector is directly disposed on a surface of the solid electrolyte layer prior to charging the battery.

### Claim 8 (depends on 7)

The fluoride ion battery according to claim 7, further comprising a bipolar structure in which a plurality of the electrode layers and the solid electrolyte layers are alternately disposed.

### Claim 9 (depends on 8)

The fluoride ion battery according to claim 8, wherein the electrode layer includes a simple substance of Pb, Sn, In, Bi, or Sb, or an alloy containing one or more of these metal elements.

### Claim 10 (depends on 7)

The fluoride ion battery according to claim 7, wherein the solid electrolyte layer includes a simple substance of Pb, Sn, In, Bi, or Sb, or an alloy containing one or more of these metal elements.

### Claim 11 (depends on 7)

The fluoride ion battery according to claim 7, wherein the second metal element is at least one kind of La, Ba, Pb, Sn, Ca and Ce.

### Claim 12 (depends on 7)

The fluoride ion battery according to claim 7, wherein the solid electrolyte material is at least one kind of La1-xBaxF3-x in which 0≤x≤2, Pb2-xSnxF4 in which 0≤x≤2, Ca2-xBaxF4 in which 0≤x≤2, and Ce1-xBaxF3-x in which 0≤x≤2.

### Claim 13 (depends on 1)

A method for producing the fluoride ion battery of claim 1, the method comprising:
a laminated body forming step of forming a laminated body including an electrode layer that includes a first metal element or a carbon element and has capability of fluorination and defluorination; a solid electrolyte layer including a solid electrolyte material, the solid electrolyte material including a second metal element with lower fluorination potential and defluorination potential than the potentials of the first metal element or the carbon element; and an anode current collector, in this order; and an anode active material layer being not present between the solid electrolyte layer and the anode current collector; and
the anode current collector includes a simple substance of Pb, Sn, In, Bi, or Sb, or an alloy containing one or more of these metal elements.

### Claim 14 (depends on 13)

The method according to claim 13, further comprising a charging step of charging the laminated body, forming a fluoride layer containing a fluoride of the first metal element or the carbon element on a surface, that is the anode current collector side, of the electrode layer, and forming an anode active material layer containing a simple substance of the second metal element on a surface, that is the anode current collector side, of the solid electrolyte layer, of the solid electrolyte layer.