Cathode active material for non-aqueous electrolyte rechargeable battery and manufacturing method for same, and non-aqueous electrolyte rechargeable battery

Patent metadata

Field	Value
Publication number	US-9786913-B2
Application number	US-201414907005-A
Country	US
Kind code	B2
Filing date	Jul 22, 2014
Priority date	Jul 24, 2013
Publication date	Oct 10, 2017
Grant date	Oct 10, 2017

Abstract

To provide a cathode active material for a non-aqueous electrode rechargeable battery, with which it is possible to improve input/output characteristics, particularly by reducing resistance in a low SOC state in which DCIR increases, and to provide a manufacturing method for same. The cathode active material includes layered hexagonal crystal lithium nickel manganese composite oxide particles represented by the general formula (A): Li 1+u Ni x Mn y Co z M t O 2 (where 0≦u≦0.20, x+y+z+t=1, 0.30≦x ≦0.70, 0.10≦y≦0.55, 0≦z≦0.40, 0≦t≦0.10, and M is one or more elements selected from Al, Ti, V, Cr, Zr, Nb, Mo, and W), and further including Na, Mg, Ca and SO 4 , in which the total amount of Na, Mg and Ca is 0.01 to 0.1 mass %, the amount of SO 4 is 0.1 to 1.0 mass %, and the ratio of the integrated intensity of the diffraction peak on plane (003) to that on plane (104) obtained by powder X-ray diffraction measurement using CuKα rays is 1.20 or greater.

First claim

What is claimed is:

1. Cathode active material for a non-aqueous electrolyte rechargeable battery comprising:
layered hexagonal crystal lithium nickel manganese composite oxide particles that are expressed by the general formula (A): Li 1+u Ni x Mn y Co z M t O 2 (where 0≦u≦0.20, x+y+z+t=1, 0.30≦x≦0.70, 0.10≦y≦0.55, 0≦z≦0.40, 0≦t≦0.10, and M is selected from one or more elements selected from among Al, Ti, V, Cr, Zr, Nb, Mo, and W); and further includes Na, Mg, Ca and SO 4 ; and wherein
the total amount of Na, Mg and Ca included is 0.01% by mass to 0.1% by mass, and the amount of SO 4 included is 0.1% by mass to 1.0% by mass;
sodium ions, magnesium ions and calcium ions are dissolved in Li sites; and
the ratio of the integrated intensity of the diffraction peak on plane (003) with respect to the integrated intensity of the diffraction peak on plane (104) that were obtained by power X-ray diffraction measurement that uses CuKα rays is 1.20 or greater wherein
a crystallization process for obtaining nickel manganese composite hydroxide particles that include secondary particles that are formed from an aggregation of plural primary particles, and are expressed by the general formula (B):: Ni x Mn y Co z M t (OH) 2+α (where x+y+z+t=1, 0.30≦x≦0.70, 0.10≦y≦0.55, 0≦z≦0.40, 0≦t≦0.10, 0≦α≦0.5, and M is at least one element that is selected from among Al, Ti, V, Cr, Zr, Nb, Mo, and W), and further includes Na, Mg, Ca and SO 4 , with the total amount of Na, Mg and Ca included being 0.01% by mass to 0.1% by mass, and the amount of SO 4 included being 0.1% by mass to 1.0% by mass;
a mixing process for obtaining a lithium mixture by mixing a lithium compound into the nickel manganese composite hydroxide particles that were obtained in the crystallization process so that the ratio of the number of atoms of Li with respect to the number of atoms of Ni, Mn, Co and M is 1:0.95 to 1.20; and
a calcination process for obtaining lithium nickel manganese composite oxide particles by performing calcination of the lithium mixture in an oxidizing atmosphere and at a calcination temperature of 850° C. to 1000° C., with T ave1 being the average temperature during the temperature rise from 650° C. to the calcination temperature, t 1 being the amount of time for the temperature to rise from 650° C. to the calcination temperature, T ave2 being the average temperature while the temperature is maintained at the calcination temperature, and t 2 being the amount of time that the temperature is maintained at the calcination temperature, and wherein a crystal growth index (G 1 ) that is defined by an Equation (a)
Crystal growth index: G 1 = T ave1 × t 1 1/2   (a)

is controlled so as to be 550° C.·h 1/2 to 1000° C.·h 1/2 , and a crystal growth index (G 2 ) that is defined by an Equation (b)
Crystal growth index: G 2 = T ave2 × t 2 1/12   (b)

is controlled so as to be 1500° C.·h 1/2 to 3500° C.·h 1/2 .

2. The cathode active material for a non-aqueous electrolyte rechargeable battery according to claim 1 , wherein the crystallite size that is found from the diffraction peak on plane (003) is 80 nm to 200 nm.

3. The cathode active material for a non-aqueous electrolyte rechargeable battery according to claim 1 , wherein the average particle size is 3μm to 20μm.

4. A manufacturing method for a cathode active material for a non-aqueous electrolyte rechargeable battery that comprises layered hexagonal crystal lithium nickel manganese composite oxide particles that are expressed by the general formula (A): Li 1+u Ni x Mn y Co z M t O 2 (where 0≦u≦0.20, x+y+z+t=1, 0.30≦x≦0.70, 0.10≦y≦0.55, 0≦z≦0.40, 0≦t≦0.10, and M is selected from one or more elements selected from among Al, Ti, V, Cr, Zr, Nb, Mo, and W); and further includes Na, Mg, Ca and SO 4 ; comprising:
a crystallization process for obtaining nickel manganese composite hydroxide particles that include secondary particles that are formed from an aggregation of plural primary particles, and are expressed by the general formula (B):: Ni x Mn y Co z M t (OH) 2+α (where x+y+z+t =1, 0.30≦x≦0.70, 0.10≦y≦0.55, 0≦z≦0.40, 0≦t≦0.10, 0≦α≦0.5, and M is at least one element that is selected from among Al, Ti, V, Cr, Zr, Nb, Mo, and W), and further includes Na, Mg, Ca and SO 4 , with the total amount of Na, Mg and Ca included being 0.01% by mass to 0.1% by mass, and the amount of SO 4 included being 0.1% by mass to 1.0% by mass;
a mixing process for obtaining a lithium mixture by mixing a lithium compound into the nickel manganese composite hydroxide particles that were obtained in the crystallization process so that the ratio of the number of atoms of Li with respect to the number of atoms of Ni, Mn, Co and M is 1:0.95 to 1.20; and
a calcination process for obtaining lithium nickel manganese composite oxide particles by performing calcination of the lithium mixture in an oxidizing atmosphere and at a calcination temperature of 850° C. to 1000° C., with T ave1 being the average temperature during the temperature rise from 650° C. to the calcination temperature, t ave2 being the amount of time for the temperature to rise from 650° C. to the calcination temperature, t ave2 being the average temperature while the temperature is maintained at the calcination temperature, and t 2 being the amount of time that the temperature is maintained at the calcination temperature, and wherein a crystal growth index (G 1 ) that is defined by an Equation (a)
Crystal growth index: G 1 =T ave1 ×t 1 1/2   (a)

is controlled so as to be 550° C.·h 1/2 to 1000° C.·h 1/2 , and a crystal growth index (G 2 ) that is defined by an Equation (b)
Crystal growth index: G 2 =T ave2 ×t 2 1/2   (b)

is controlled so as to be 1500° C.·h 1/2 to 3500° C.·h 1/2 .

5. The manufacturing method for a cathode active material for a non-aqueous electrolyte rechargeable battery according to claim 4 , wherein
the crystallization process is a process for crystallizing the nickel manganese composite hydroxide particles by obtaining a reaction aqueous solution by mixing together a mixed aqueous solution in which Ni, Mn, Co and M are included so that the composition ratios are expressed by the general formula (B), an ammonium-ion donor and sodium hydroxide, and controlling the temperature of the reaction aqueous solution to be 35° C. or greater, and the pH value to be 10.5 to 12.0 at a standard liquid temperature of 25° C.; and
where of the metal elements of the mixed aqueous solution, at least nickel sulfate and manganese sulfate are used as the nickel source and manganese source.

6. The manufacturing method for a cathode active material for a non-aqueous electrolyte rechargeable battery according to claim 4 , wherein the mixed aqueous solution further includes 10 mg/L to 50 mg/L of Mg, and/or 10 mg/L to 30 mg/L of Ca.

7. The manufacturing method for a cathode active material for a non-aqueous electrolyte rechargeable battery according to claim 4 , wherein in the calcination process the amount of time for raising the temperature from 650° C. to the calcination temperature is 0.5 hours to 1.8 hours, and the amount of time that the temperature is maintained at the calcination temperature is 4 hours to 15 hours.

8. The manufacturing method for a cathode active material for a non-aqueous electrolyte rechargeable battery according to claim 4 , wherein in the calcination process, the amount of time from after the temperature reaches 650° C. to the end of calcination is 5 hours to 15 hours.

9. The manufacturing method for a cathode active material for a non-aqueous electrolyte rechargeable battery according to claim 4 , wherein the oxygen concentration in the oxidizing atmosphere is 18% by v

Assignees

• Sumitomo Metal Mining Co

Inventors

• Inoue Katsuya
• Toya Hiroyuki

Classifications

• C01P2006/40

  Electric properties · CPC title

• C01P2002/50

  Solid solutions · CPC title

• C01P2004/61

  Micrometer sized, i.e. from 1-100 micrometer · CPC title

• C01P2002/60

  Compounds characterised by their crystallite size · CPC title

• H01M4/525 Primary

  of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy · CPC title