Lithium nickel containing composite oxide and manufacturing method thereof, and nonaqueous-electrolyte secondary battery

Patent metadata

Field	Value
Publication number	US-10777815-B2
Application number	US-201615766104-A
Country	US
Kind code	B2
Filing date	Oct 11, 2016
Priority date	Oct 9, 2015
Publication date	Sep 15, 2020
Grant date	Sep 15, 2020

Abstract

A cathode active material that is able to improve storage characteristics without deteriorating charging and discharging capacity is provided. By mixing lithium nickel containing composite oxide particles comprising a layered rock-salt type crystal structure, a lithium compound, and an alkali metal compound; calcining the mixed powder at a temperature range of 800° C. to 1000° C.; washing and removing alkali metal other than lithium; mixing washed calcined particles with a lithium compound again; calcining the mixture in an oxidizing atmosphere at a temperature range of 600° C. to 800° C., lithium nickel containing composite oxide comprising a layered rock-salt type crystal structure and a peak intensity ratio of (003) plane with respect to (104) plane of 1.2 or more that are obtained by X-ray powder diffraction using Cu-Kα ray as an X-ray source is obtained.

First claim

The invention claimed is:

1. A lithium nickel containing composite oxide mainly containing nickel as a transition metal,
the lithium nickel containing composite oxide having a layered rock-salt type crystal structure,
wherein the lithium nickel containing composite oxide is composed of primary particles that do not have grain boundaries;
wherein the average primary particle size is 2.0 μm or more and the BET specific surface area is 0.35 m 2 /g or less;
wherein a peak intensity ratio of (003) plane with respect to (104) plane that are obtained by X-ray powder diffraction using Cu-Kα ray as an X-ray source is 1.2 or more; and
wherein a peak intensity relationship between (006) plane, (102) plane, and (101) plane that are obtained by X-ray powder diffraction using Cu-Kα ray as an X-ray source satisfies [(006)+(102)]/(101)≤0.6.

2. A lithium nickel containing composite oxide according to claim 1 , wherein a lithium occupancy at 3 a site in the layered rock-salt type crystal structure obtained by Rietvelt analysis is 96% or more.

3. A lithium nickel containing composite oxide according to claim 1 , wherein the lithium nickel containing composite oxide contains cobalt, and/or aluminum as an added element.

4. A lithium nickel containing composite oxide according to claim 1 , wherein the lithium nickel containing composite oxide has a composition expressed by a general formula: Li 1+u Ni x Co y Al z O 2 , where −0.03≤u≤0.10, x+y+z=1, 0.50≤x≤1.00, 0≤y≤0.50, 0≤z≤0.10.

5. A manufacturing method of lithium nickel containing composite oxide, comprising steps of:
a mixing process wherein lithium nickel containing composite oxide particles that have a layered rock-salt type crystal structure and mainly contains nickel as a transition metal; a lithium compound; and an alkali metal compound are mixed to obtain mixed powder,
a first calcination process wherein the mixed powder is calcined at a temperature range of 800° C. to 1000° C. to obtain calcined particles,
a washing process wherein alkali metal other than the lithium is removed by washing the calcined particles, and
a second calcination process wherein the washed calcined particles is mixed with a lithium compound to obtain a mixture of these and the mixture is calcined in an oxidizing atmosphere at a temperature range of 600° C. to 800° C. to obtain lithium nickel containing composite oxide that has a layered rock-salt type crystal structure and has a peak intensity ratio of (003) plane with respect to (104) plane that are obtained by X-ray powder diffraction using Cu-Kα ray as an X-ray source of 1.2 or more.

6. A manufacturing method of lithium nickel containing composite oxide according to claim 5 , wherein, in the mixing process, the alkali metal compound is mixed in the mixing process so that a ratio of an amount of substance of the alkali metal compound with respect to a sum of an amount of substance of metal elements excluding lithium that form the lithium nickel containing composite oxide particles and the amount of substance of the alkali metal compound becomes to be within a range of 0.55 to 0.99.

7. A manufacturing method of lithium nickel containing composite oxide according to claim 5 , wherein chloride, carbonate, sulfate, or a mixture of these containing one or more alkali metal that is selected at least from among Li, Na, and K as the alkali metal compound is used in the mixing process.

8. A manufacturing method of lithium nickel containing composite oxide according to claim 5 , wherein the lithium compounds is mixed in the mixing process so that a ratio of the amount of substance of Li in the lithium compounds with respect to an amount of substance of metal elements excluding lithium that form the lithium nickel containing composite oxide particles to be within a range of 0 to 0.30.

9. A manufacturing method of lithium nickel containing composite oxide according to claim 5 , wherein a calcination time in the first calcination process is set to 10 hours or less.

10. A manufacturing method of lithium nickel containing composite oxide according to claim 5 , wherein a calcination time in the second calcination process is set to be within a range of 1 hour to 20 hours.

11. A manufacturing method of lithium nickel containing composite oxide according to claim 5 , wherein an eventually-obtained lithium nickel containing composite oxide is adjusted to have a composition that is expressed by a general formula: Li 1+u Ni x Co y Al z O 2 , where −0.03≤u≤0.10, x+y+z=1, 0.50≤x≤1.00, 0≤y≤0.50, 0≤z≤0.10.

12. A nonaqueous-electrolyte secondary battery comprising a cathode, anode, separator, and nonaqueous-electrolyte, and a lithium nickel containing composite oxide according to claim 1 is used as a cathode material of the cathode.

Assignees

• Sumitomo Metal Mining Co
• Univ Shinshu

Inventors

• Kanada Satoshi
• Teshima Katsuya
• Zettsu Nobuyuki
• Kimijima Takeshi

Classifications

• C01P2002/74

  by peak-intensities or a ratio thereof only · CPC title

• C01P2004/03

  obtained by SEM · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M4/1391

  of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title

• H01M4/131

  Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx · CPC title