# US 5,700,598 A · Method for preparing mixed amorphous vanadium oxides and their use as electrodes in reachargeable lithium cells

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- Number: US 5,700,598 A
- Document ID: US5700598A
- Status: Granted
- Kind: A
- Application number: 08/678,210
- Filed: 1996-07-11
- Granted: 1997-12-23
- Earliest claimed: 1996-07-11
- Assignees: Bell Communications Research, Inc.
- Inventors: Sophie Denis; Francois Orsini; Jean-Marie Tarascon; Marcel Touboul
- Web page: https://patentgrep.com/patent/US5700598A

## CPC

- 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)
- C01G 31/00: Compounds of vanadium
- C01P 2002/02: Amorphous compounds
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2006/12: Surface area
- C01P 2006/40: Electric properties
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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

A method for preparing an amorphous ternary lithiated vanadium metal oxide of the formula Li.sub.x M.sub.y V.sub.z O.sub.(x+5z+ny)/2, where M is a metal, 0<x.ltoreq.3, 0<y.ltoreq.3, 1.ltoreq.z.ltoreq.4, and n=2 or 3, comprising the steps of creating an aqueous solution of at least one metavanadate salt selected from the group consisting of NH.sub.4 VO.sub.3 and NaVO.sub.3, and a nitrate salt of the formula M(NO.sub.3).sub.n containing a large excess of a lithium salt; heating the solution; adding a sufficient amount of a base to obtain a suitable pH; and precipitating the amorphous lithiated vanadium metal oxide. A rechargeable lithiated intercalation battery cell comprising a positive electrode, a negative electrode, and an electrolyte, wherein the active material of the negative electrode is an amorphous ternary lithiated vanadium metal oxide of the formula Li.sub.x M.sub.y V.sub.z O.sub.(x+5z+ny)/2 or an amorphous binary non-lithiated vanadium metal oxide of the formula M.sub.y V.sub.z O.sub.(5z+ny)/2, prepared according to the methods of the present invention.

## Claims

### Claim 1

A method for preparing an amorphous ternary lithiated vanadium metal oxide of the formula Li.sub.x M.sub.y V.sub.z O.sub.(x+5z+ny)/2, where M is a metal, 0<x.ltoreq.3, 0<y.ltoreq.3, 1.ltoreq.z.ltoreq.4, and n=2 or 3
characterized in that
a) an aqueous solution is prepared of
1) at least one metavanadate salt selected from the group consisting of NH.sub.4 VO.sub.3 and NaVO.sub.3,
2) a nitrate salt of the formula M(NO.sub.3).sub.n, where M is said metal, and
3) an excess of a lithium salt;
b) the resulting solution is heated; and
c) a sufficient amount of a base is added to the heated solution to obtain a pH suitable for precipitating the amorphous lithiated vanadium metal oxide.

### Claim 2 (depends on 1)

A method according to claim 1
characterized in that said aqueous solution is prepared by mixing
a) a first aqueous solution comprising said metavanadate salt; and
b) a second aqueous solution comprising said nitrate and lithium salts.

### Claim 3 (depends on 1)

A method according to claim 1 wherein said base is selected from the group consisting of ammonia, amines, alkali hydroxides, alkaline earth hydroxides, alkali salts of alcohols, and alkali salts of carboxylic acids.

### Claim 4 (depends on 1)

A method according to claim 1 wherein said base is added in the form of an aqueous solution of said base.

### Claim 5 (depends on 1)

A method according to claim 1 wherein said lithium salt is selected from the group consisting of LiNO.sub.3, LiOH, LiOH.cndot.H.sub.2 O, and Li.sub.2 CO.sub.3.

### Claim 6 (depends on 1)

A method according to claim 1 wherein said heating comprises heating the solution to a temperature in the range of about 80.degree. C. to 95.degree. C.

### Claim 7 (depends on 1)

A method according to claim 1 wherein said metal is at least one metal selected from the group consisting of manganese, cobalt, iron, copper, cadmium, nickel, chromium, indium, aluminum, and magnesium.

### Claim 8

A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and an non-aqueous electrolyte
characterized in that said active positive electrode material is an amorphous vanadium metal oxide selected from the group consisting of:
a) ternary lithiated vanadium metal oxides of the formula Li.sub.x M.sub.y V.sub.z O.sub.(x+5z+ny)/2, where M is a metal, 0<x.ltoreq.3, 0<y.ltoreq.3, 1.ltoreq.z.ltoreq.4, and n=2 or 3; and
b) binary non-lithiated vanadium metal oxides of the formula M.sub.y V.sub.z O.sub.(5z+ny)/2, where M is a metal, 0<y.ltoreq.3, 1.ltoreq.z.ltoreq.4, and n=2 or 3.

### Claim 9 (depends on 1)

A non-aqueous secondary battery cell comprising an active negative electrode material an active positive electrode material, and a non-aqueous electrolyte
characterized in that said active positive electrode material is an amorphous vanadium metal oxide consisting of a ternary lithiated vanadium metal oxide of the formula Li.sub.x M.sub.y V.sub.z O.sub.(x+5z+ny)/2, where M is a metal, 0<x.ltoreq.3, 0<y.ltoreq.3, 1.ltoreq.z.ltoreq.4, and n=2 or 3 and prepared by a process according to claim 1.

### Claim 10 (depends on 8)

A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and a non-aqueous electrolyte
characterized in that said active positive electrode material is a binary non-lithiated vanadium metal oxide of the formulaM.sub.y V.sub.z O.sub.(5z+ny)/2, where M is a metal, 0<y.ltoreq.3, 1.ltoreq.z.ltoreq.4, and n=2 or 3 and prepared by a process according to claim 8.

### Claim 11

A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and an non-aqueous electrolyte
characterized in that said active negative electrode material is an amorphous vanadium metal oxide selected from the group consisting of:
a) ternary lithiated vanadium metal oxides of the formula Li.sub.x M.sub.y V.sub.z O.sub.(x+5z+ny)/2, where M is a metal, 0<x.ltoreq.3, 0<y.ltoreq.3, 1.ltoreq.z.ltoreq.4, and n=2 or 3; and
b) binary non-lithiated vanadium metal oxides of the formula M.sub.y V.sub.z O.sub.(5z+ny)/2, where M is a metal, 0<y.ltoreq.3, 1.ltoreq.z.ltoreq.4, and n=2 or 3.

### Claim 12 (depends on 1)

A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and a non-aqueous electrolyte
characterized in that said active negative electrode material is a ternary lithiated vanadium metal oxide of the formula Li.sub.x M.sub.y V.sub.z O.sub.(x+5z+ny)/2, where M is a metal, 0<x.ltoreq.3, 0<y.ltoreq.3, 1.ltoreq.z.ltoreq.4, and n=2 or 3 and prepared by a process according to claim 1.

### Claim 13 (depends on 8)

A non-aqueous secondary battery cell comprising an active negative electrode material, an active positive electrode material, and a non-aqueous electrolyte
characterized in that said active negative electrode material is a binary non-lithiated vanadium metal oxide of the formula M.sub.y V.sub.z O.sub.(5z+ny)/2, where M is a metal, 0<y.ltoreq.3, 1.ltoreq.z.ltoreq.4, and n=2 or 3 and prepared by a process according to claim 8.