# US 10,312,513 B2 · Lithium composite metallic oxide and production process for the same

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- Number: US 10,312,513 B2
- Document ID: US10312513B2
- Status: Granted
- Kind: B2
- Application number: 15/309,859
- Filed: 2015-04-07
- Published: 2017-05-25
- Granted: 2019-06-04
- Earliest claimed: 2014-05-13
- Assignees: Kabushiki Kaisha Toyota Jidoshokki
- Applicants: Kabushiki Kaisha Toyota Jidoshokki
- Inventors: Tsukasa Sugie; Dai Matsushiro; Masanori Harata
- Web page: https://patentgrep.com/patent/US10312513B2

## CPC

- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- C01G 53/502: containing lithium and cobalt
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/84: one phase coated with the other
- C01P 2006/40: Electric properties
- Y02E 60/10: Energy storage using batteries
- Y02T 10/70: Energy storage systems for electromobility, e.g. 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
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## Abstract

A lithium composite metallic oxide expressed by: LiaNibCocMndDeOf (where 0.2≤“a”≤1.5, “b”+“c”+“d”+“e”=1, 0<“e”<1, “D” is at least one of the following elements: Fe, Cr, Cu, Zn, Ca, Mg, Zr, S, Si, Na, K, Al, Ti, P, Ga, Ge, V, Mo, Nb, W, La, Hf and Rf, and 1.7≤“f”≤2.1), and including: a high manganese portion, which is made of a metallic oxide including Ni, Co and Mn at least and of which the composition ratio between Ni, Co and Mn is expressed by Ni:Co:Mn=g:h:i (note that “g”+“h”+“i”=1, 0<“g”<1, 0<“h”<“c”, and “d”<“i”<1), in a superficial layer thereof; and a metallic oxidation portion in an outermost superficial layer of the high manganese portion.

## Claims

### Claim 1

A lithium composite metallic oxide expressed by a general formula, LiaNibCocMndDeOf where 0.2≤“a”≤1.5, “b”+“c”+“d”+“e”=1, 0<“e”<1,“D” is at least one element selected from the group consisting of Fe, Cr, Cu, Zn, Ca, Mg, Zr, S, Si, Na, K, Al, Ti, P, Ga, Ge, V, Mo, Nb, W, La, Hf, and Rf, and 1.7≤“f”≤2.1;
the lithium composite metallic oxide comprising:
a high manganese portion, which is made of a metallic oxide including Ni, Co and Mn at least and of which the composition ratio between Ni, Co and Mn is expressed by Ni:Co:Mn=g:h:i where “g”+“h”+“i”=1, 0<“g”<1, 0<“h”<“c”, and “d”<“i”<1, in a superficial layer thereof; and
a metallic oxidation portion in an outermost superficial layer of the high manganese portion,
the metallic oxidation portion is expressed by a formula LiqM2O3+r, where 0<“q”<1, 0≤“r”<1, M is a metal selected from the group consisting of Ni, Co and Mn, and
the composition of the metallic oxidation portion is different from the composition of the high manganese portion;
the lithium composite metallic oxide further comprising:
a first-composition portion expressed by a general formula, Lia1Nib1Coc1Mnd1De1 Of1 where 0.2≤“a1”≤1.5, “b1”+“c1”+“d1”+“e1”=1, 0<“e1”<1, “D” is at least one element selected from the group consisting of Fe, Cr, Cu, Zn, Ca, Mg, Zr, S, Si, Na, K, Al, Ti, P, Ga, Ge, V, Mo, Nb, W, La, Hf and Rf, and 1.7≤“f1”≤2.1; and
a second-composition portion expressed by a general formula, Lia2Nib2Coc2Mnd2De2Of2where 0.2≤“a2”≤1.5, “b2”+“c2”+“d2”+“e2”=1, 0<“e2”<1, “D” is at least one element selected from the group consisting of Fe, Cr, Cu, Zn, Ca, Mg, Zr, S, Si, Na, K, Al, Ti, P, Ga, Ge, V, Mo, Nb, W, La, Hf and Rf, and 1.7≤“f2”≤2.1 where at least any of the following is satisfied: “c2”<“c1”; or “d2”>“d1”.

### Claim 2 (depends on 1)

The lithium composite metallic oxide as set forth in claim 1, wherein the metallic oxidation portion includes a crystal.

### Claim 3 (depends on 1)

The lithium composite metallic oxide as set forth in claim 1, wherein the second-composition portion satisfies both of the following: “d2”>“d1”;
and “e2”<“e1”.

### Claim 4 (depends on 1)

A production process for the lithium composite metallic oxide as set forth in claim 1, the production process comprising any of following Treatments 1 through 5 carried out to a material expressed by a general formula, LiaNibCocMndDeOf (where 0.2≤“a”≤1.5, “b”+“c”+“d”+“e”=1, 0<“e”<1, “D” is at least one element selected from the group consisting of Fe, Cr, Cu, Zn, Ca, Mg, Zr, S, Si, Na, K, Al, Ti, P, Ga, Ge, V, Mo, Nb, W, La, Hf and Rf, and 1.7≤“f”≤2.1):
(Treatment 1) comprising the steps of:
1-1) readying an acidic metallic salt aqueous solution;
1-2) mixing the acidic metallic salt aqueous solution with the aforementioned material;
1-3) mixing a liquid obtained at said step 1-2) with an ammonium-phosphate salt aqueous solution; and
1-4) isolating the lithium composite metallic oxide from another liquid obtained at said step 1-3);
(Treatment 2) comprising the steps of:
2-1) readying an ammonium-phosphate salt aqueous solution;
2-2) mixing the ammonium-phosphate salt aqueous solution with the aforementioned material;
2-3) mixing a liquid obtained at said step 2-2) with an acidic metallic salt aqueous solution; and
2-4) isolating the lithium composite metallic oxide from another liquid obtained at said step 2-3);
(Treatment 3) comprising the steps of:
3-1) readying an aqueous solution of an ammonium-phosphate salt, or an aqueous solution of a metallic salt and an ammonium-phosphate salt;
3-2) mixing the aqueous solution with the aforementioned material; and
3-3) isolating the lithium composite metallic oxide from a liquid obtained at said step 3-2);
(Treatment 4) comprising the steps of:
4-1) readying an acidic metallic salt aqueous solution, and an ammonium-phosphate salt aqueous solution, respectively;
4-2) mixing water with the aforementioned material;
4-3) mixing a liquid obtained at said step 4-2), said acidic metallic salt aqueous solution, and said ammonium-phosphate salt aqueous solution each other; and
4-4) isolating the lithium composite metallic oxide from another liquid obtained at said step 4-3); or
(Treatment 5) comprising the steps of:
5-1) readying a metallic phosphate salt aqueous solution, or a metallic polyphosphate salt aqueous solution;
5-2) mixing the aqueous solution with the aforementioned material; and
5-3) isolating the lithium composite metallic oxide from a liquid obtained at said step 5-2).

### Claim 5 (depends on 1)

A lithium-ion secondary battery comprising the lithium composite metallic oxide as set forth in claim 1.