# US 5,702,844 A · Nickel electrode for an alkaline storage cell

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- Number: US 5,702,844 A
- Document ID: US5702844A
- Status: Granted
- Kind: A
- Application number: 08/609,388
- Filed: 1996-03-01
- Granted: 1997-12-30
- Earliest claimed: 1995-03-03
- Assignees: Saft
- Inventors: Patrick Bernard; Andre Lecerf; Stephane Senyarich; Claudette Audry
- Web page: https://patentgrep.com/patent/US5702844A

## CPC

- H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/1391: of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
- H01M 4/32: Nickel oxide or hydroxide electrodes
- H01M 4/52: of nickel, cobalt or iron
- H01M 4/762: {Porous or perforated metallic containers}
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The present invention concerns a nickel electrode comprising a nickel-based hydroxide which satisfies at least one of the following criteria: an intensity ratio of the ›103! line to the ›200! line in the X-ray diffraction diagram of 1.05.+-.0.10; a coherence length L of 13.+-.3 nm, a ratio of the sum of the surface areas of the peaks at 3687.+-.10 cm.sup.-1 and 3600.+-.10 cm.sup.-1 to the surface area of the peak at 3580.+-.10 cm.sup.-1 of the Raman spectrum of 0.11.+-.0.03; a ratio of the surface area of the peak at 511.+-.10 cm.sup.-1 to the surface area of the peak at 460.+-.10 cm.sup.-1 in the Raman spectrum of 1.1.+-.0.1.

## Claims

### Claim 1

A nickel electrode with a non-sintered support for a storage cell containing an alkaline electrolyte, the electrode comprising a porous three-dimensional conductive structure and an electrochemically active material containing particles of a nickel-based hydroxide with a .beta. crystallographic structure, wherein said hydroxide satisfies at least one of the following criteria:
an intensity ratio of the (103) line to the (200) line in an X-ray diffraction diagram generated under Cu(K.sub..alpha.) radiation conditions of the hydroxide of 1.05.+-.0.10;
a coherence length L of 13.+-.3 nm, said coherence length L having the formula: ##EQU3## where .PHI..sub.›100! is the crystallite size calculated from the mid-height width of the (100) line and .PHI..sub.›001! is the crystallite size calculated from the mid-height width of the (001) line of the X-ray diffraction diagram of said hydroxide;
a ratio of the sum of the surface areas of the peaks at 3687.+-.10 cm.sup.-1 and 3600.+-.10 cm.sup.-1 to the surface area of the peak at 3580.+-.10 cm.sup.-1 in the Raman spectrum of said hydroxide of 0.11.+-.0.03;
a ratio of the surface area of the peak at 511.+-.10 cm.sup.-1 to the surface area of the peak at 460.+-.10 cm.sup.-1 in the Raman spectrum of said hydroxide of 1.1.+-.0.1.

### Claim 2 (depends on 1)

An electrode according to claim 1, in which said hydroxide satisfies at least two of said criteria.

### Claim 3 (depends on 1)

An electrode according to claim 1, in which said nickel-based hydroxide contains at least one syncrystallized hydroxide of a metal selected from cobalt, cadmium, zinc, calcium, and magnesium.

### Claim 4

An electrode according to any one of the preceding claims, in which said hydroxide is mainly composed of a nickel hydroxide and contains at least a proportion by weight P, as a % of said hydroxide, of a syncrystallized cobalt hydroxide, said hydroxide further satisfying the following criterion:
a ratio Q of the intensity of the peak at 511.+-.10 cm.sup.-1 to the intensity of the peak at 460.+-.10 cm.sup.-1 in the Raman spectrum of said hydroxide which is such that:
Q=xP+y where x=0.24.+-.0.02 and y.gtoreq.0.7.

### Claim 5

A storage cell comprising an alkaline electrolyte and a nickel electrode with a non-sintered support, wherein said electrode comprises a porous three-dimensional conductive structure and an electrochemically active material containing particles of a nickel-based hydroxide with a .beta. crystallographic structure, wherein said hydroxide satisfies at least one of the following criteria:
an intensity ratio of the (103) line to the (200) line in an X-ray diffraction diagram generated under Cu(K.sub..alpha.) radiation conditions of the hydroxide of 1.05.+-.0.10;
a coherence length L of 13.+-.3 nm, said coherence length L, having the formula: ##EQU4## where .PHI..sub.›100! is the crystallite size calculated from the mid-height width of the (100) line and .PHI..sub.›001! is the crystallite size calculated from the mid-height width of the (001) line of the X-ray diffraction diagram of said hydroxide;
a ratio of the sum of the surface areas of the peaks at 3687.+-.10 cm.sup.-1 and 3600.+-.10 cm.sup.-1 to the surface area of the peak at 3580.+-.10 cm.sup.-1 in the Raman spectrum of said hydroxide of 0.11.+-.0.03;
a ratio of the surface area of the peak at 511.+-.10 cm.sup.-1 to the surface area of the peak at 460.+-.10 cm.sup.-1 in the Raman spectrum of said hydroxide of 1.1.+-.0.1.

### Claim 6 (depends on 5)

The storage cell according to claim 5, in which said hydroxide satisfies at least two of said criteria.

### Claim 7 (depends on 5)

The storage cell according to claim 5, in which said hydroxide contains at least one syncrystallized hydroxide of a metal selected from cobalt, cadmium, zinc, calcium, and magnesium.

### Claim 8 (depends on 5)

The storage cell according to claim 5, in which said hydroxide is mainly composed of a nickel hydroxide and contains at least a proportion by weight P, as a % of said hydroxide, of a syncrystallized cobalt hydroxide, said hydroxide further satisfying the following criterion:
a ratio Q of the intensity of the peak at 511.+-.10 cm.sup.-1 to the intensity of the peak at 460.+-.10 cm.sup.-1 in the Raman spectrum of said hydroxide which is such that:
Q=xP+y where x=0.24.+-.0.02 and y.gtoreq.0.7.

### Claim 9

A battery of storage cells wherein each storage cell comprises an alkaline electrolyte and a nickel electrode with a non-sintered support, each of said nickel electrode comprising a porous three-dimensional conductive structure and an electrochemically active material containing particles of a nickel-based hydroxide with a .beta. crystallographic structure, wherein said hydroxide satisfies at least one of the following criteria:
an intensity ratio of the (103) line to the (200) line in an X-ray diffraction diagram generated under Cu(K.sub..alpha.) radiation conditions of the hydroxide of 1.05.+-.0.10;
a coherence length L of 13.+-.3 nm, said coherence length L, having the formula: ##EQU5## where .PHI..sub.›100! is the crystallite size calculated from the mid-height width of the (100) line and .PHI..sub.›001! is the crystallite size calculated from the mid-height width of the (001) line of the X-ray diffraction diagram of said hydroxide;
a ratio of the sum of the surface areas of the peaks at 3687.+-.10 cm.sup.-1 and 3600.+-.10 cm.sup.-1 to the surface area of the peak at 3580.+-.10 cm.sup.-1 in the Raman spectrum of said hydroxide of 0.11.+-.0.03;
a ratio of the surface area of the peak at 511.+-.10 cm.sup.-1 to the surface area of the peak at 460.+-.10 cm.sup.-1 in the Raman spectrum of said hydroxide of 1.1.+-.0.1.

### Claim 10 (depends on 9)

The battery according to claim 9, in which said hydroxide satisfies at least two of said criteria.

### Claim 11 (depends on 9)

The battery according to claim 9, in which said nickel-based hydroxide contains at least one syncrystallized hydroxide of a metal selected from cobalt, cadmium, zinc, calcium and magnesium.

### Claim 12 (depends on 9)

The battery according to claim 9, in which said hydroxide is mainly composed of a nickel hydroxide and contains at least a proportion by weight P, as a % of said hydroxide, of a syncrystallized cobalt hydroxide, said hydroxide further satisfying the following criterion:
a ratio Q of the intensity of the peak at 511.+-.10 cm.sup.-1 to the intensity of the peak at 460.+-.10 cm.sup.-1 on the Raman spectrum of said hydroxide which is such that:
Q=xP+y where x=0.24.+-.0.02 and y.gtoreq.0.7.