# US 11,309,543 B2 · Electrode active composition with reduced amount of cobalt

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- Number: US 11,309,543 B2
- Document ID: US11309543B2
- Status: Granted
- Kind: B2
- Application number: 16/516,249
- Filed: 2019-07-18
- Published: 2021-01-21
- Granted: 2022-04-19
- Earliest claimed: 2019-07-18
- Assignees: Guangxi Nowphene Energy Storage Technologies Co., Ltd; Boston Global Technologies, LLC
- Applicants: Guiqing Huang; Boshan Mo; Youde Mo
- Inventors: Guiqing Huang; Boshan Mo; Youde Mo
- Web page: https://patentgrep.com/patent/US11309543B2

## CPC

- C01G 53/82: Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
- H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
- C01G 53/50: of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
- H01M 4/364: {as mixtures}
- 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
- C01P 2002/52: containing elements as dopants
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2004/03: obtained by SEM
- C01P 2004/84: one phase coated with the other
- H01M 2004/028: {Positive electrodes}
- Y02E 60/10: Energy storage using batteries
- 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)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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

## Abstract

The present invention provides an electrode active composition represented by formula (I). Li1+xMnaNibO2+x.LiyCoyO2y.D*C (I), wherein x>0, 0<y<0.1, a+b=1, 1.2≤a/b≤3.0; and D and C are optional dopants and coating agents that contain no cobalt element. The active compositions of Formula (I) exhibit electrochemical properties comparable to those with a higher cobalt amount, such as NCM523 electrode material (LiNi0.5Co0.2Mn0.3O2).

## Claims

### Claim 1

An electrode active composition represented by formula (I)
Li1+xMnaNibO2+x.LiyCoyO2yD*C (I)
wherein x>0, 0<y<0.1, a+b=1, and 1.2≤a/b≤3.3;
wherein D is one or more dopants that contain(s) no Cobalt (Co) element, and D may be present or absent (i.e. optional) in formula (I); and
wherein C is one or more coating agents that contain(s) no Cobalt element, and C may be present or absent (i.e. optional) in formula (I).

### Claim 2 (depends on 1)

The electrode active composition according to claim 1, wherein YL≤y<YH, and wherein YL and YH are selected from 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019, 0.02, 0.021, 0.022, 0.023, 0.024, 0.025, 0.026, 0.027, 0.028, 0.029, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, 0.07, 0.071, 0.072, 0.073, 0.074, 0.075, 0.076, 0.077, 0.078, 0.079, 0.08, 0.081, 0.082, 0.083, 0.084, 0.085, 0.086, 0.087, 0.088, 0.089, 0.09, 0.091, 0.092, 0.093, 0.094, 0.095, 0.096, 0.097, 0.098, and 0.099, providing that YL≤YH.

### Claim 3 (depends on 1)

The electrode active composition according to claim 1, wherein 0.01≤y≤0.07.

### Claim 4 (depends on 1)

The electrode active composition according to claim 1, wherein YL≤y≤YH, and wherein YL and YH are selected from 0.01, 0.015, 0.02, 0.025, 0.03, 0.035, 0.04, 0.045, 0.05, 0.055, 0.06, 0.065, and 0.07, providing that YL≤YH.

### Claim 5 (depends on 1)

The electrode active composition according to claim 1, wherein YL≤y≤YH, and wherein YL and YH are selected from 0.023, 0.03, 0.034, 0.045, and 0.046, providing that YL≤YH.

### Claim 6 (depends on 1)

The electrode active composition according to claim 1, wherein y is 0.023, 0.03, 0.034, 0.045, or 0.046.

### Claim 7 (depends on 1)

The electrode active composition according to claim 1, wherein XL≤x≤XH, and wherein XL and XH are selected from 0.1, 0.15, 0.2, 0.28, 0.3, 0.35, 0.375, 0.4, 0.43, 0.45, 0.5, 0.55, and 0.6, providing that XL≤XH.

### Claim 8 (depends on 1)

The electrode active composition according to claim 1, wherein XL≤x≤XH, and wherein XL and XH are selected from 0.28, 0.375, 0.4, and 0.43, providing that XL≤XH.

### Claim 9 (depends on 1)

The electrode active composition according to claim 1, wherein (a/b)L≤a/b≤(a/b)H, and wherein (a/b)L and (a/b)H are selected from 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.05, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, and 3.3, providing that (a/b)L≤(a/b)H.

### Claim 10 (depends on 1)

The electrode active composition according to claim 1, wherein (a/b)L≤a/b≤(a/b)H, and wherein (a/b)L and (a/b)H are selected from 1.7, 2.05, 2.2, and 2.5, providing that (a/b)L≤(a/b)H.

### Claim 11 (depends on 1)

The electrode active composition according to claim 1, wherein D and C are independently of each other selected from M(0-0.1) oxides, M(0-0.1) fluorides, salts of M(0-0.1) with the conjugate base of an inorganic acid, or any combination thereof, wherein M is selected from Li, Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, Mo, W, and V.

### Claim 12 (depends on 1)

The electrode active composition according to claim 1, wherein D and C are independently of each other selected, by stoichiometry, from the group consisting of Al2O3, MgO, Cr2O3, SnO2, SrO2, ZnO, Nb2O5, ZrO2, TiO2, FeO, Fe3O4, AlF3, BF3, FeF3, CaF2, MgF2, B2O3, B2O5, LiF, SrF2, SnF2, ZnF2, CuF2, MnF2, NiF2, LiB3O5, Li3BO3, LiBO2, Li3B7O12, LiAlO2, Li2SiO3, Li8SiO6, LiPO3, Li3PO4, LiTi2(PO4)3, Li4Ti5O12, LiNbO3, Li3NbO4, Li2ZrO3, Li3TaO3, LiCr3O8, LiVO3, Li2MoO4, Li2Mo2O7, Li2TiO3, Li2WO4, LiTa3O8, Li4GeO4, LiFePO4, and Fe2P2O7.

### Claim 13 (depends on 1)

The electrode active composition according to claim 1, wherein D is selected from the group consisting of Li0.045Ti0.021O0.063, Sn0.01O0.02, Li0.03V0.03O0.09, and Li0.1Mo0.05O0.2.

### Claim 14 (depends on 1)

The electrode active composition according to claim 1, wherein C is selected from the group consisting of Al0.039F0.12, Al0.0039O0.058, Al0.03F0.09, Al0.05F0.15, Ca0.03F0.06 Ca0.05F0.1, Li0.01V0.01O0.03, Li0.03(PO4)0.01, Li0.03Al0.03O0.06, Li0.03Mo0.03O0.12, Li0.03Nb0.03O0.09, Li0.03V0.03O0.09, Li0.06W0.03O0.12, Li0.05Al0.05O0.1, Li0.05Nb0.05O0.10, Li0.05B0.05O0.15, Li0.05W0.05O0.2, Li0.03(PO4)0.02, Li0.06W0.03O0.12, Li0.08W0.04O0.16, Li0.09B0.03O0.09, Li0.15(PO4)0.05, Li0.15B0.05O0.1, Li0.15B0.05O0.15, Li0.1Mo0.05O0.2, Mg0.03F0.06, Mg0.05F00.1, Zn0.05O0.05, Zn0.07O0.07, Zr0.03O0.06, and Zn0.05O0.1.

### Claim 15 (depends on 1)

The electrode active composition according to claim 1, wherein D*C is selected from the group consisting of:
Li0.045Ti0.021O0.063*Al0.039O0.058,
Li0.045Ti0.021O0.063*Al0.039F0.12,
Sn0.01O0.02*Al0.039O0.058,
Sn0.01O0.02*Al0.039F0.12,
Sn0.01O0.02*Li0.01V0.01O0.03,
Li0.03V0.03O0.09*Zn0.07O0.07,
Li0.03V0.03O0.09*Li0.05Al0.05O0.1,
Li0.03V0.03O0.09*Al0.05F0.15,
Li0.03V0.03O0.09*Ca0.05F0.1,
Li0.1Mo0.05O0.2*Ca0.03F0.06,
Li0.1Mo0.05O0.2*Li0.03(PO4)0.01,
Li0.1Mo0.05O0.2*Li0.03V0.03O0.09,
Li0.1Mo0.05O0.2*Al0.03F0.09,
Li0.1Mo0.05O0.2*Zn0.05O0.05, and
Li0.1Mo0.05O0.2*Li0.03Al0.03O0.06.

### Claim 16 (depends on 1)

The electrode active composition according to claim 1, which is selected from the group consisting of:
Li1.43Mn0.715Ni0.285O2.43.Li0.046Co0.046O0.092,
Li1.43Mn0.715Ni0.285O2.43.Li0.046Co0.046O0.092.Li0.045Ti0.021O0.063,
Li1.43Mn0.715Ni0.285O2.43.Li0.046Co0.046O0.092.Li0.045Ti0.021O0.063*Al0.039O0.058,
Li1.43Mn0.715Ni0.285O2.43.Li0.046Co0.046O0.092.Li0.045Ti0.021O0.063*Al0.039F0.12,
Li1.4Mn0.715Ni0.285O2.4.Li0.034Co0.034O0.068.Sn0.01O0.02,
Li1.4Mn0.715Ni0.285O2.4.Li0.034Co0.034O0.068.Sn0.01O0.02*Al0.039O0.058,
Li1.4Mn0.715Ni0.285O2.4.Li0.034Co0.034O0.068.Sn0.01O0.02*Al0.039F0.12,
Li1.4Mn0.715Ni0.285O2.4.Li0.034Co0.034O0.068.Sn0.01O0.02*Li0.01V0.01O0.03,
Li1.40Mn0.688Ni0.312O2.40.Li0.045Co0.045O0.09.Li0.03V0.03O0.09,
Li1.40Mn0.688Ni0.312O2.40.Li0.045Co0.045O0.09.Li0.03V0.03O0.09*Zn0.07O0.07,
Li1.40Mn0.688Ni0.312O2.40.Li0.045Co0.045O0.09.Li0.03V0.03O0.09*Li0.05Al0.05O0.1,
Li1.40Mn0.688Ni0.312O2.40.Li0.03Co0.03O0.06.Li0.03V0.03O0.09*Al0.05F0.15,
Li1.40Mn0.688Ni0.312O2.40.Li0.03Co0.03O0.06.Li0.03V0.03O0.09*Ca0.05F0.1,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Ca0.05F0.1,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Li0.06(PO4)0.02,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Li0.05V0.05O0.15,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Al0.05F0.15,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Zn0.05O0.05,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Li0.05Al0.05O0.1,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Li0.15B0.05O0.1,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Li0.05Nb0.05O0.15,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Li0.1Mo0.05O0.2,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Zr0.05O0.1,
Li1.375Mn0.688Ni0.312O2.375.Li0.03Co0.03O0.06*Li0.05W0.05O0.2,
Li1.375Mn0.63Ni0.372O2.375.Li0.03Co0.03O0.06*Li0.1Mo0.05O0.2*Ca0.03F0.06,
Li1.375Mn0.63Ni0.312O2.375.Li0.03Co0.03O0.06*Li0.1Mo0.05O0.2*Li0.03(PO4)0.01,
Li1.375Mn0.63Ni0.37O2.375.Li0.03Co0.03O0.06*Li0.1Mo0.05O0.2*Li0.03V0.03O0.09,
Li1.375Mn0.63Ni0.37O2.375.Li0.03Co0.03O0.06*Li0.1Mo0.05O0.2*Zn0.05O0.05,
Li1.375Mn0.63Ni0.37O2.375.Li0.03Co0.03O0.06*Li0.1Mo0.05O0.2*Li0.03Al0.03O0.06,
Li1.375Mn0.63Ni0.37O2.375.Li0.023Co0.023O0.046*Mg0.05F0.1,
Li1.375Mn0.63Ni0.37O2.375.Li0.023Co0.023O0.046*Li0.15B0.05O0.15,
Li1.375Mn0.63Ni0.37O2.375.Li0.023Co0.023O0.046*Li0.05Nb0.05O0.10,
Li1.375Mn0.63Ni0.37O2.375.Li0.023Co0.023O0.046*Li0.1Mo0.05O0.20,
Li1.375Mn0.63Ni0.37O2.375.Li0.023Co0.023O0.046*Zr0.03O0.06,
Li1.375Mn0.63Ni0.37O2.375.Li0.023Co0.023O0.046*Li0.08W0.04O0.16,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Ca0.05F0.10,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Li0.15(PO4)0.15,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Li0.05V0.05O0.15,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Al0.03F0.09,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Zn0.05O0.05,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Li0.03Al0.03O0.06,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Mg0.03F0.06,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Li0.09B0.03O0.09,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Li0.03Nb0.03O0.12,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Zr0.03O0.06,
Li1.375Mn0.672Ni0.328O2.375.Li0.03Co0.03O0.06*Li0.06W0.03O0.12,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Ca0.03F0.06,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Li0.03(PO4)0.01,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Li0.03V0.03O0.09,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Al0.03F0.09,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Zn0.05O0.05,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Li0.03Al0.03O0.06,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Mg0.03F0.06,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Li0.09B0.03O0.09,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Li0.03Nb0.03O0.09,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Li0.03Mo0.03O0.12,
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Zr0.03O0.03, and
Li1.28Mn0.63Ni0.37O2.28.Li0.03Co0.03O0.06*Li0.06W0.03O0.12.

### Claim 17 (depends on 1)

The electrode active composition according to claim 1, which is selected from the group consisting of:
Li1.43Mn0.715Ni0.285O2.43.Li0.046Co0.046O0.092,
Li1.43Mn0.715Ni0.285O2.43.Li0.046Co0.046O0.092.Li0.045Ti0.021O0.063,
Li1.43Mn0.715Ni0.285O2.43.Li0.046Co0.046O0.092.Li0.045Ti0.021O0.063*Al0.039O0.058,
Li1.43Mn0.715Ni0.285O2.43.Li0.046Co0.046O0.092.Li0.045Ti0.021O0.063*Al0.039F0.12,
Li1.4Mn0.715Ni0.285O2.4.Li0.034Co0.034O0.068.Sn0.01O0.02,
Li1.4Mn0.715Ni0.285O2.4.Li0.034Co0.034O0.068.Sn0.01O0.02*Al0.039O0.058,
Li1.4Mn0.715Ni0.285O2.4.Li0.034Co0.034O0.068.Sn0.01O0.02*Al0.039F0.12, and
Li1.4Mn0.715Ni0.285O2.4.Li0.034Co0.034O0.068.Sn0.01O0.02*Li0.01V0.01O0.03.

### Claim 18 (depends on 1)

The electrode active composition according to claim 1, which exhibits a specific discharge capacity of:
at least about 215 mAh/g at a discharge rate of 0.1C when discharged from 4.8V to 2.0V;
at least about 195 mAh/g at a discharge rate of 0.2C when discharged from 4.6V to 2.0V after the first cycle at 0.1C rate and between 4.8V and 2.0V;
at least about 185 mAh/g at a discharge rate of 0.2C when discharged from 4.45V to 2.0V after the first cycle at 0.1C rate and between 4.8V and 2.0V; or
at least about 180 mAh/g at a discharge rate of 0.2C when discharged from 4.35V to 2.0V after the first cycle at 0.1C rate and between 4.8V and 2.0V.

### Claim 19 (depends on 1)

A battery comprising the electrode active composition according to claim 1.