# US 2019/0245205 A1 · High voltage lithium ion positive electrode material

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- Number: US 2019/0245205 A1
- Document ID: US20190245205A1
- Status: Published application
- Kind: A1
- Application number: 16/201,212
- Filed: 2018-11-27
- Published: 2019-08-08
- Earliest claimed: 2013-12-04
- Assignees: The Government of the United States, as represented by the Secretary of the Army
- Applicants: Government of the United States, as represented by the Secretary of the Army
- Inventors: Jan L. Allen; Joshua L. Allen; Samuel A. Delp, III; Jeffrey B. Wolfenstine; T. Richard Jow
- Web page: https://patentgrep.com/patent/US20190245205A1

## CPC

- H01M 4/5825: {Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines}
- H01G 11/46: Metal oxides
- H01G 11/50: specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 2004/021: {Physical characteristics, e.g. porosity, surface area}
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

A positive electrode material having a nominal stoichiometry Li1+y/2Co1−x−y−z−dSizFexMyM′d(PO4)1+y/2 where M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La and/or Ga, M′ is a divalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca and/or Mg, y is within a range of 0<y≤0.10 and x is within a range of 0≤x≤0.2. The use of double compositional modification to LiCoPO4 increases the discharge capacity from ˜100 mAh/g to about 130 mAh/g while retaining the discharge capacity retention of the singly Fe-substituted LiCoPO4. Additional compositional modification to include Si increases the cycle life and greatly improved the coulombic efficiency to between 97-100% at a C/3 cycle rate.

## Claims

### Claim at position 1

1-20. (canceled)

### Claim 21

A lithium-ion battery, the battery comprising:
a positive electrode, comprising a compound of formula Li1+y/2Co1−x−y−z−dSizFexMyM′d(PO4) wherein,
M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La, and/or Ga;
M′ is a divalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca, and/or Mg;
y is within a range of 0<y≤0.10;
x is within a range of 0<x≤0.20;
z is within a range of 0≤z≤0.10; and
d is within a range of 0≤d≤0.20;
the positive electrode material having an initial capacity of at least 120 mAhg−1; and
a negative electrode; and
an electrolyte.

### Claim 22 (depends on 21)

The battery of claim 21, wherein z=0, y is within the range of 0.02≤y<0.08 and xis within the range of 0.05<x≤0.15 and M=Cr.

### Claim 23 (depends on 21)

The battery of claim 21, wherein y is within the range of 0.04≤y<0.06 and x is within the range of 0.08≤x≤0.12.

### Claim 24 (depends on 21)

The battery of claim 21, wherein z=0.

### Claim 25 (depends on 21)

The battery of claim 21, wherein d=0.

### Claim 26 (depends on 21)

The battery of claim 21, wherein y=0.05 and x=0.10.

### Claim 27 (depends on 21)

The battery of claim 21, wherein 0<z≤0.10.

### Claim 28 (depends on 21)

The battery of claim 21, wherein 0<d≤0.20.

### Claim 29 (depends on 21)

The battery of claim 21, wherein x is within the range of 0.08≤x≤0.12.

### Claim 29

A lithium-ion battery, the battery comprising:
a positive electrode, comprising a compound of formula Li1+y/2Co1−x−y−z−dSizFexMyM′d(PO4) wherein,
M is a trivalent cation selected from at least one of Cr, Ti, Al, Mn, Ni, V, Sc, La, and/or Ga;
M′ is a covalent cation selected from at least one of Mn, Ni, Zn, Sr, Cu, Ca, and/or Mg;
y is within a range of 0<y≤0.10;
x is within a range of 0<x≤0.20;
z is within a range of 0≤z≤0.10; and
d is within a range of 0≤d≤0.20;
the positive electrode material having a capacity of at least 100 mAhg−1 after 500 cycles; and
a negative electrode; and
an electrolyte.

### Claim 30 (depends on 21)

The battery of claim 21, wherein y is 0.02≤y<0.08.

### Claim 30 (depends on 21)

The battery of claim 21, wherein z=0, y is within the range of 0.02≤y<0.08 and xis within the range of 0.05≤x≤0.15 and M=Cr.

### Claim 31 (depends on 29)

The battery of claim 29, wherein y is within the range of 0.04≤y<0.06 and x is within the range of 0.08≤x≤0.12.

### Claim 32 (depends on 29)

The battery of claim 29, wherein z=0.

### Claim 33 (depends on 29)

The battery of claim 29, wherein d=0.

### Claim 34 (depends on 29)

The battery of claim 29, wherein y=0.05 and x=0.10.

### Claim 35 (depends on 29)

The battery of claim 29, wherein 0<z≤0.10.

### Claim 36 (depends on 29)

The battery of claim 29, wherein 0<d≤0.20.

### Claim 37 (depends on 29)

The battery of claim 29, wherein x is within the range of 0.08≤x≤0.12.

### Claim 38 (depends on 29)

The battery of claim 29, wherein y is 0.02≤y<0.08.

### Claim 39 (depends on 29)

The battery of claim 29, wherein the positive electrode has a coulombic efficiency between 97-100% at a C/3 cycle rate.

### Claim 40 (depends on 29)

The battery of claim 29, wherein the positive electrode material has an initial capacity of at least 125 mAhg−1.