# US 2014/0154575 A1 · Cyanometallate cathode battery and method for fabrication

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- Number: US 2014/0154575 A1
- Document ID: US20140154575A1
- Status: Published application
- Kind: A1
- Application number: 14/174,171
- Filed: 2014-02-06
- Published: 2014-06-05
- Earliest claimed: 2012-03-28
- Assignees: Sharp Laboratories of America, Inc.
- Applicants: Sharp Laboratories of America, Inc.
- Inventors: Yuhao Lu; Long Wang; Jong-Jan Lee
- Web page: https://patentgrep.com/patent/US20140154575A1

## CPC

- H01M 4/134: Electrodes based on metals, Si or alloys
- B01J 6/008: {Pyrolysis reactions (of hydrocarbons C10G9/00)}
- C01B 17/02: Preparation of sulfur; Purification
- C01B 19/02: Elemental selenium or tellurium
- C01B 25/003: {Phosphorus}
- C01B 32/00: Carbon; Compounds thereof (C01B21/00, C01B23/00 take precedence; percarbonates C01B15/10; carbon black C09C1/48)
- C01B 33/021: Preparation (chemical coating from the vapour phase C23C16/00)
- C01C 3/12: Simple or complex iron cyanides
- C01D 1/02: Oxides
- C01D 15/02: Oxides; Hydroxides
- H01M 4/04: Processes of manufacture in general
- H01M 4/0404: {by coating on electrode collectors}
- H01M 4/0416: {involving impregnation with a solution, dispersion, paste or dry powder (H01M4/0438 takes precedence)}
- H01M 4/0452: {from solutions}
- H01M 4/0471: {involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis}
- H01M 4/049: {Manufacturing of an active layer by chemical means}
- H01M 4/0495: {Chemical alloying}
- H01M 4/0497: {Chemical precipitation}
- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M 4/136: Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/1395: of electrodes based on metals, Si or alloys
- H01M 4/1397: of 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 4/38: of elements or alloys
- H01M 4/381: {Alkaline or alkaline earth metals elements (H01M4/40 takes precedence)}
- H01M 4/382: {Lithium (H01M4/405 takes precedence)}
- H01M 4/387: {Tin or alloys based on tin}
- H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 4/56: of lead
- H01M 4/58: of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M 4/5815: {Sulfides}
- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01M 4/587: for inserting or intercalating light metals
- H01M 4/60: of organic compounds
- H01M 4/623: {fluorinated polymers}
- H01M 4/628: {Inhibitors, e.g. gassing inhibitors, corrosion inhibitors}
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/054: Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
- H01M 10/056: characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M 10/0565: Polymeric materials, e.g. gel-type or solid-type
- H02J 7/70: characterised by the mechanical construction
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/77: by unit-cell parameters, atom positions or structure diagrams
- C01P 2002/88: by thermal analysis data, e.g. TGA, DTA, DSC
- H01M 10/052: Li-accumulators
- H01M 50/414: Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M 50/426: Fluorocarbon polymers
- H01M 2004/027: {Negative electrodes}
- Y02E 60/10: Energy storage using batteries
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- Y10T 29/49108: Electric battery cell making
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01C: AMMONIA; CYANOGEN; COMPOUNDS THEREOF ({metal hydrides, monoborane, diborane or addition complexes thereof C01B6/00}; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; azides C01B21/08; {compounds other than ammonia or cyanogen, containing nitrogen, non-metals and optionally metals C01B21/082}; metal imides or amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; compounds containing silicon C01B33/00; compounds containing boron C01B35/00)
- 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)
- H02J: ELECTRIC POWER NETWORKS; CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION

## Abstract

A method is provided for fabricating a cyanometallate cathode battery. The method provides a cathode of AXM1YM2Z(CN)N.MH2O, where “A” is selected from a first group of metals, and where M1 and M2 are transition metals. The method provides an anode and a metal ion-permeable membrane separating the anode from the cathode. A third electrode is also provided including “B” metal ions selected from the first group of metals. Typically, the first group of metals includes alkali and alkaline metals. The method intercalates “B” metal ions from the third electrode to the anode, the cathode, or both the anode and cathode to form a completely fabricated battery. In one aspect, a solid electrolyte interface (SEI) layer including the “B” metal ions overlies a surface of the anode, the cathode, or both the anode and cathode. A cyanometallate cathode battery is also provided.

## Claims

### Claim 1

A method for fabricating a cyanometallate cathode battery, the method comprising:
providing a cathode of AXM1YM2Z(CN)N.MH2O;
where “A” is selected from a first group of metals;
where M1 and M2 are transition metals;
where x is less than or equal to 2;
where Y is less than or equal to 1;
where Z is less than or equal to 1;
where N is less than or equal to 6;
where M is less than or equal to 20;
providing an anode;
proving a metal ion-permeable membrane separating the anode from the cathode;
providing a third electrode including “B” metal ions selected from the first group of metals;
intercalating “B” metal ions from the third electrode to an electrode selected from a group consisting of the anode, the cathode, and both the anode and cathode; and,
forming a completely fabricated battery.

### Claim 2 (depends on 1)

The method of claim 1 further comprising:
forming a solid electrolyte interface (SEI) layer including the “B” metal ions overlying a surface selected from a group consisting of the anode, the cathode, and both the anode and cathode.

### Claim 3 (depends on 1)

The method of claim 1 further comprising:
subsequent to forming the completely fabricated battery, discharging the battery in response to creating a battery external voltage potential between the cathode and the anode; and,
forming a cathode of BDAX′M1YM2Z(CN)N.MH2O;
where D>0; and,
where X′ is less than or equal to X.

### Claim 4 (depends on 1)

The method of claim 1 further comprising:
subsequent to forming the completely fabricated battery, charging the battery in response to creating a battery external voltage potential between the anode and the cathode; and,
forming an anode including intercalated “B” metal ions.

### Claim 5 (depends on 1)

The method of claim 1 wherein where the first group of metals is selected from a group consisting of alkali metals, alkaline earth metals, and combinations thereof.

### Claim 6 (depends on 5)

The method of claim 5 wherein the first group of metals is selected from a group of metals consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rh), cesium (Cs), calcium (Ca), and in (Mg).

### Claim 7 (depends on 1)

The method of claim 1 wherein M1 and M2 are each independently derived, as selected from a group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper Cu), zinc (Zn), Ca, and Mg.

### Claim 8 (depends on 1)

The method of claim 1 further comprising:
subsequent to intercalating “B” metal ions from the third electrode to the selected electrode, removing the third electrode.

### Claim 9 (depends on 1)

The method of claim 1 further comprising:
immersing the third electrode and the anode in an electrolyte; and,
creating a battery external voltage potential between the anode and the third electrode; and,
wherein intercalating “B” metal ions from the third electrode to the selected electrode includes intercalating “B” metal ions into the anode.

### Claim 10 (depends on 1)

The method of claim 1 further comprising:
immersing the third electrode and the cathode in an electrolyte;
creating a battery external voltage potential between the cathode and the third electrode;
wherein intercalating “B” metal ions from the third electrode to the selected electrode includes intercalating “B” metal ions into the cathode.

### Claim 11 (depends on 1)

The method of claim 1 further comprising:
immersing the third electrode and the cathode in an electrolyte;
creating a battery external voltage potential between the cathode and the third electrode;
wherein intercalating “B” metal ions from the third electrode to the selected electrode includes intercalating “B” metal ions into the cathode;
immersing the anode and cathode in an electrolyte;
creating a battery external voltage potential between the anode and the cathode; and,
deintercalating “B” metal ions from the cathode and intercalating the “B” metal ions into the anode.

### Claim 12

The method of claim further comprising:
forming an immediate, low resistance contact between the anode and the third electrode;
immersing the anode and cathode in an electrolyte;
creating a battery external voltage potential between the cathode and the anode; and,
wherein intercalating “B” metal ions from the third electrode to the selected electrode includes intercalating “B” metal ions from the anode into the cathode.

### Claim 13 (depends on 1)

The method of claim 1 wherein providing the anode includes providing an anode made from a material selected from a group consisting of carbon (C), silicon (Si), antimony (Sb), lead (Ph), tin (Sn), and phosphorus (P).

### Claim 14

A cyanometallate cathode battery, the battery comprising:
an electrolyte;
a cathode of AX′M1YM2Z(CN)N.MH2O in a battery charged state;
where “A” is selected from a first group of metals;
where M1 and M2 are transition metals;
where X′ is less than or equal to 2;
where Y is less than or equal to 1;
where Z is less than or equal to 1;
where N is less than or equal to 6;
where M is less than or equal to 20;
an anode including “B” metal ions, selected from the first group of metals, in the battery charged state;
a metal ion-permeable membrane separating the anode from the cathode; and,
wherein the cathode is BDAX′M1YM2Z(CN)N.MH2O in a battery discharged state, where D>0.

### Claim 15 (depends on 14)

The battery of claim 14 wherein where the first group of metals is selected from a group consisting of alkali metals, alkaline earth metals, and combinations thereof.

### Claim 16 (depends on 15)

The battery of claim 15 wherein the first group of metals is selected from a group of metals consisting of lithium (Li), sodium (Na), potassium (K), rubidium (Rh), cesium (Cs), calcium (Ca), and magnesium (Mg).

### Claim 17 (depends on 14)

The battery of claim 14 wherein M1 and M2 are each independently derived, as selected from a group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper Cu), zinc (Zn), Ca, and Mg.

### Claim 18 (depends on 14)

The battery of claim 14 further comprising:
a solid electrolyte interface (SEI) layer including the “B” metal ions overlying a surface selected from a group consisting of the anode, the cathode, and both the anode and cathode.

### Claim 19 (depends on 14)

The battery of claim 14 wherein the anode includes a material selected from a group consisting of carbon (C), silicon (Si), antimony (Sb), lead (Ph), tin (Sn), and phosphorus (P).