# US 9,040,203 B2 · Lithium battery

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- Number: US 9,040,203 B2
- Document ID: US9040203B2
- Status: Granted
- Kind: B2
- Application number: 13/830,446
- Filed: 2013-03-14
- Published: 2014-07-17
- Granted: 2015-05-26
- Earliest claimed: 2013-01-16
- Assignees: Samsung SDI Co., Ltd.
- Applicants: Samsung SDI Co., Ltd.
- Inventors: Myung-Hoon Kim; Man-Seok Han; Seung-Wan Kim; Jung-Yeon Won; Ha-Na Yoo
- Web page: https://patentgrep.com/patent/US9040203B2

## CPC

- H01M 10/0569: characterised by the solvents
- H01M 4/386: {Silicon or alloys based on silicon}
- H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence)
- H01M 10/052: Li-accumulators
- H01M 10/0567: characterised by the additives
- 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
- H01M 2300/0034: Fluorinated solvents
- H01M 2300/004: Three solvents
- 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
- 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 battery including: a positive electrode including an overlithiated lithium transition metal oxide having a layered structure; a negative electrode including a silicon-based negative active material; and an electrolyte between the positive electrode and the negative electrode, the electrolyte including an electrolytic solution including a fluorinated ether solvent in an amount of 3 vol % or more based on the total volume of the electrolytic solution.

## Claims

### Claim 1

A lithium battery comprising:
a positive electrode comprising an overlithiated transition metal oxide having a layered structure;
a negative electrode comprising a silicon-based negative active material; and
an electrolyte between the positive electrode and the negative electrode, the electrolyte comprising an electrolytic solution comprising a fluorinated ether solvent in an amount of 3 vol % or more based on the total volume of the electrolytic solution,
wherein the overlithiated transition metal oxide comprises a compound represented by Formula 1 below:
xLi2MO3-(1-x)LiM′O2, <Formula 1>
wherein 0<x<1, M is at least one metal selected from Period 4 transition metals and Period 5 transition metals having a mean oxidation number of +4, and M′ is at least one metal selected from Period 4 transition metals and Period 5 transition metals having a mean oxidation number of +3.

### Claim 2 (depends on 1)

The lithium battery of claim 1, wherein the fluorinated ether solvent comprises at least one compound represented by Formulae 4 to 6 below:
Rf1-O—Rf2 <Formula 4>
Rf1-O—R <Formula 5>
Rf1-O —(R′—O)n—Rf2 <Formula 6>
wherein Rf1 and Rf2 are each independently a linear or branched C1 to C12 fluoroalkyl group having at least one hydrogen atom substituted with a fluoro group, R is a linear or branched C1 to C12 alkyl group, R′ is a linear or branched C1 to C5 alkylene group, and n is an integer of 1 to 5.

### Claim 3 (depends on 2)

The lithium battery of claim 2, wherein Rf1 or Rf2 are each independently a fluoroalkyl group selected from the group consisting of HCF2—, CF3—, HCF2CF2—, CH3CF2—, CF3CH2—, CF3CF2—, (CF3)2CH—, HCF2CF2CH2—, CF3CH2CH2—, HCF2CF2CF2CH2—, HCF2CF2CF2CF2CH2—, CF3CF2CH2—, CF3CFHCF2CH2—, HCF2CF(CF3)CH2—, and CF3CF2CH2CH2—.

### Claim 4 (depends on 2)

The lithium battery of claim 2, wherein R is an alkyl group selected from the group consisting of —CH3, —C2H5, —C3H7, and —CH(CH3)CH3.

### Claim 5 (depends on 2)

The lithium battery of claim 2, wherein R′ is an alkylene group selected from the group consisting of —CH2—, —CH2CH2—, and —CH2CH2CH2—.

### Claim 6 (depends on 1)

The lithium battery of claim 1, wherein the fluorinated ether solvent is selected from the group consisting of HCF2CF2CH2OCF2CF2H, HCF2CF2CH2OCF2CH3, CF3CF2CH2OCF2CF2H, CF3CF2CH2OCF2H, HCF2CF2OCH2CF3, HCF2CF2CH2OCF2CFHCF3, CF3CF2CH2OCF2CFHCF3, HCF2CF2CH2OCH2CFHCF3, CF3CF2CH2OCH2CFHCF3, HCF2CF2CH2OCH3, and combinations thereof.

### Claim 7 (depends on 1)

The lithium battery of claim 1, wherein the electrolytic solution comprises the fluorinated ether solvent in an amount of about 3 to about 70 vol % based on the total volume of the electrolytic solution.

### Claim 8 (depends on 1)

The lithium battery of claim 1, wherein the electrolytic solution comprises the fluorinated ether solvent in an amount of about 10 vol % or more based on the total volume of the electrolytic solution.

### Claim 9 (depends on 1)

The lithium battery of claim 1, wherein the electrolyte further comprises an additive selected from the group consisting of tris(trimethylsilyl) phosphate (TMSPa), lithium difluorooxalatoborate (LiFOB), vinylcarbonate (VC), propanesultone (PS), succinitrile (SN), LiBF4, a silane compound, a silazane compound, and combinations thereof.

### Claim 10 (depends on 9)

The lithium battery of claim 9, wherein each of the silane compound and the silazane compound has a functional group capable of forming of a siloxane bond.

### Claim 11 (depends on 10)

The lithium battery of claim 10, wherein the functional group is selected from the group consisting of acryl, amino, epoxy, methoxy, and vinyl.

### Claim 12 (depends on 9)

The lithium battery of claim 9, wherein the electrolytic solution comprises the additive in an amount in a range of about 0.01 to about 10 wt % based on the total weight of the electrolytic solution.

### Claim 13 (depends on 1)

The lithium battery of claim 1, wherein the electrolytic solution further comprises a carbonate-based compound, an ester-based compound, an ether-based compound, a ketone-based compound, an alcohol-based compound, an aprotic solvent, or a combination thereof.

### Claim 14 (depends on 13)

The lithium battery of claim 13, wherein the carbonate-based compound comprises a chain carbonate compound and a fluoro carbonate compound.

### Claim 15 (depends on 14)

The lithium battery of claim 14, wherein the fluoro carbonate compound is present in an amount from about 1 to about 30 vol % based on the total volume of the electrolytic solution.

### Claim 16 (depends on 1)

The lithium battery of claim 1, wherein the overlithiated transition metal oxide comprises at least one compound represented by Formulae 2 to 5 below:
xLi2Mn03-(1-x)LiNiaCobMncO2, <Formula 2>
wherein 0<x<1, 0<a<1, 0<b<1, 0<c<1, and a+b+c=1;
xLi2MO3-yLiM'O2-zLi1+dMn 2-dO4, <Formula 3>
wherein x+y+z=1, 0<x<1, 0<y<1, 0<z<1, and 0<d<0.33, M is at least one metal selected from Period 4 transition metals and Period 5 transition metals having a mean oxidation number of +4, M′ is at least one metal selected from Period 4 transition metals and Period 5 transition metals having a mean oxidation number of +3, and M″ is at least one metal selected from Period 4 transition metals and Period 5 transition metals having a combined mean oxidation number of +3 or +4;
Li[LixMey]O2+d, <Formula 4>
wherein x+y=1, 0<x<1, 0≦d≦0.1, and Me is at least one metal selected from the group consisting of Mn, V, Cr, Fe, Co, Ni, Zr, Re, Al, B, Ge, Ru, Sn, Ti, Nb, Mo, and Pt; and
Li[LixNiaCobMnc]O2+d, <Formula 5>
wherein x+a+b+c=1, 0<x<1, 0<a<1, 0<b<1, 0<c<1, and 0≦d≦0.1.

### Claim 17 (depends on 1)

The lithium battery of claim 1, wherein the silicon-based negative active material comprises a material selected from the group consisting of Si, SiOx(O<x<2), Si—Z alloy, and combinations thereof, wherein Z is alkali metal, alkali earth metal, a Group 11 element, a Group 12 element, a Group 13 element, a Group 14 element, a Group 15 element, a Group 16 element, a transition metal, a rare earth element, or a combination thereof, and is not Si.

### Claim 18 (depends on 1)

The lithium battery of claim 1, wherein the silicon-based negative active material has a nano-structure having a dimension of at least one region thereof being less than about 500 nm.

### Claim 19 (depends on 18)

The lithium battery of claim 18, wherein the nano-structure has a structure selected from the group consisting of nanoparticle, nanopowder, nanowire, nanorod, nanofiber, nanocrystal, nanodot, nanoribbon and combinations thereof.