Nonaqueous electrolyte compositions comprising a fluorinated solvent and a 2-furanone

1. An electrolyte composition consisting of:

a) a fluorinated solvent, wherein the fluorinated solvent is a fluorinated acyclic carboxylic acid ester represented by Formula (I)

R 1 —COO—R 2   (I)

wherein

i) R 1 is H, an alkyl group, or a fluoroalkyl group;

ii) R 2 is an alkyl group or a fluoroalkyl group;

iii) either or both of R 1 and R 2 comprises fluorine; and

iv) R 1 and R 2 , taken as a pair, comprise at least two carbon atoms but not more than seven carbon atoms;

b) a carbonate co-solvent, wherein said carbonate co-solvent is ethylene carbonate;

c) at least one γ-lactone, wherein the γ-lactone comprises 2(5H)-furanone;

d) at least one electrolyte salt; and

optionally one or more selected from:

e) a cyclic sulfate represented by Formula (II)

wherein each Q is independently a hydrogen or an optionally fluorinated vinyl, allyl, acetylenic, propargyl, or C 1 -C 3 alkyl group;

f) at least one component selected from:

i) a borate salt represented by Formula (III):

LiBF (4−2p) (C 2 O 4 ) p   (III)

wherein p is 0, 1, or 2; and/or

ii) an oxalate salt represented by Formula (IV):

LiPF (6−2q) (C 2 O 4 ) q   (IV)

wherein q is 1, 2, or 3; and

g) an HF scavenger, wherein the HF scavenger comprises silanes, silazanes, epoxides, amines, aziridines, salts of carbonic acid, B 2 O 5 , and ZnO; and

h) a gas-reduction additive, wherein gas-reduction additive comprises halobenzenes, haloalkylbenzenes; 1,3-propane sultone; succinic anhydride; ethynyl sulfonyl benzene; 2-sulfobenzoic acid cyclic anhydride; divinyl sulfone; triphenylphosphate (TPP); diphenyl monobutyl phosphate (DMP); 2,3-dichloro-1,4-naphthoquinone; 1,2-naphthoquinone; 2,3-dibromo-1,4-naphthoquinone; 3-bromo-I,2-naphthoquinone; 2-acetylfuran; 2-acetyl-5-methylfuran; 2-methyl imidazole1-(phenylsulfonyl)pyrrole; 2,3-benzofuran; fluoro-cyclotriphosphazenes; benzotriazole; anisole; diethylphosphonate; fluoroalkyl-substituted dioxolanes, trimethylene borate; diethylene glycol diacetate; triethylene glycol dimethacrylate; triglycol diacetate; 1,2-ethanedisulfonic anhydride; 1,3-propanedisulfonic anhydride; 2,2,7,7-tetraoxide 1,2,7-oxadithiepane; 3-methyl-, 2,2,5,5-tetraoxide 1,2,5-oxadithiolane; hexamethoxycyclotriphosphazene; 4,5-dimethyl-4,5-difluoro-1,3-dioxolan-2-one; 2-ethoxy-2,4,4,6,6-pentafluoro-2,2,4,4,6,6-hexahydro-1,3,5,2,4,6-triazatriphosphorine; 2,2,4,4,6-pentafluoro-2,2,4,4,6,6-hexahydro-6-methoxy-1,3,5,2,4,6-triazatriphosphorine; 4,5-Difluoro-1,3-dioxolan-2-one; 1,4-bis(ethenylsulfonyl)-butane; bis(vinylsulfonyl)-methane; 1,3-bis(ethenylsulfonyl)-propane; 1,2-bis(ethenylsulfonyl)-ethane, and 1,1′-[oxybis(methylenesulfonyl)]bis-ethene;

wherein the electrolyte composition is free from other solvents not listed as one of the a) or b) components;

wherein the electrolyte composition comprises from 0.1 to 5 wt % of the γ-lactone based on the total weight of the electrolyte composition;

wherein the electrolyte composition comprises from 5 to 95 wt % of the fluorinated solvent based on the total weight of the electrolyte composition; and

wherein the electrolyte composition comprises from 0.5 to 95 wt % of the carbonate co-solvent based on the total weight of the electrolyte composition.

2. The electrolyte composition of claim 1 , wherein the fluorinated acyclic carboxylic acid ester is CH 3 —COO—CH 2 CF 2 H, CH 3 CH 2 —COO CH 2 CF 2 H, F 2 CHCH 2 —COO—CH 3 , F 2 CHCH 2 —COO—CH 2 CH 3 , CH 3 —COO—CH 2 CH 2 CF 2 H, CH 3 CH 2 —COO—CH 2 CH 2 CF 2 H, F 2 CHCH 2 CH 2 —COO—CH 2 CH 3 , CH 3 —COO—CH 2 CF 3 , CH 3 CH 2 —COO—CH 2 CF 2 H, H—COO—CH 2 CF 2 H, H—COO—CH 2 CF 3 , or mixtures thereof.

3. The electrolyte composition of claim 1 , wherein the fluorinated acyclic carboxylic acid ester comprises 2,2-difluoroethyl acetate.

4. The electrolyte composition of claim 1 , wherein the cyclic sulfate comprises ethylene sulfate.

5. The electrolyte composition of claim 1 , wherein the borate salt comprises lithium bis(oxalato)borate.

6. The electrolyte composition of claim 1 , wherein the oxalate salt comprises lithium tris(oxalato)phosphate.

7. An electrochemical cell comprising:

(a) a housing;

(b) an anode and a cathode disposed in the housing and in ionically conductive contact with one another;

(c) the electrolyte composition of claim 1 disposed in the housing and providing an ionically conductive pathway between the anode and the cathode; and

(d) a porous separator between the anode and the cathode.

8. The electrochemical cell of claim 7 , wherein the electrochemical cell is a lithium ion battery.

9. The electrochemical cell of claim 8 , wherein the anode comprises an anode active material, and the anode active material is lithium titanate, graphite, lithium alloys, silicon, or combinations thereof.

10. The electrochemical cell of claim 8 , wherein the cathode comprises a cathode active material exhibiting greater than 30 mAh/g capacity in the potential range greater than 4.6 V versus a Li/Li + reference electrode, or a cathode active material which is charged to a potential greater than or equal to 4.1 V versus a Li/Li + reference electrode.

11. The electrochemical cell of claim 8 , wherein the cathode comprises a cathode active material, and the cathode active material comprises

Li a Ni b Mn c Co d R e O 2-f Z f ,

wherein:

R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, a rare earth element, or a combination thereof;

Z is F, S, P, or a combination thereof; and

0.8≤a≤1.2, 0.1≤b≤0.9, 0.0≤c≤0.7, 0.05≤d≤0.4, 0≤e≤0.2; wherein the sum of b+c+d+e is about 1; and 0≤f≤0.08;

or comprises a composite material represented by the structure of Formula:

x (Li 2−w A 1−v Q w+v O 3−e )·(1− x )(Li y Mn 2−z M 2 O 4−d )

wherein:

x is about 0 to about 0.1;

A comprises one or more of Mn or Ti;

Q comprises one or more of Al, Ca, Co, Cr, Cu, Fe, Ga, Mg, Nb, Ni, Ti, V, Zn, Zr or Y;

e is 0 to about 0.3;

v is 0 to about 0.5;

w is 0 to about 0.6;

M comprises one or more of Al, Ca, Co, Cr, Cu, Fe, Ga, Li, Mg, Mn, Nb, Ni, Si, Ti, V, Zn, Zr or Y;

d is 0 to about 0.5;

y is about 0 to about 1;

z is about 0.3 to about 1; and

wherein the Li y Mn 2−z M 2 O 4−d component has a spinel structure and the Li 2-w Q w+v A 1−v O 3−e component has a layered structure;

or comprises:

Li a A 1−b ,R b D 2 ,

wherein:

A is Ni, Co, Mn, or a combination thereof;

R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, a rare earth element, or a combination thereof;

D is O, F, S, P, or a combination thereof; and

0.90≤a≤1.8 and 0≤b≤0.5;

or comprises:

Li a A 1−x R x DO 4−f Z f ,

wherein:

A is Fe, Mn, Ni, Co, V, or a combination thereof;

R is Al, Ni, Co, Mn, Cr, Fe, Mg, Sr, V, Zr, Ti, a rare earth element, or a combination thereof;

D is P, S, Si, or a combination thereof;

Z is F, Cl, S, or a combination thereof;

8≤a≤2.2;

0≤x≤0.3; and

0≤f≤0.1.

12. An electronic device, transportation device, or telecommunications device, comprising an electrochemical cell according to claim 7 .

13. The electrolyte composition of claim 1 , wherein the halobenzene is selected from the group consisting of fluorobenzene, chlorobenzene, bromobenzene, and iodobenzene.

14. The electrolyte composition of claim 1 , wherein the fluoro-cyclotriphosphazenes is selected from the group consisting of 2,4,6-trifluoro-2-phenoxy-4,6-dipropoxy-cyclotriphosphazene, and 2,4,6-trifluoro-2-(3-(trifluoromethyl)phenoxy)-6-ethoxy-cyclotriphosphazene.

15. The electrolyte composition of claim 1 , wherein the fluoroalkyl-substituted dioxolane is selected from the group consisting of 2-trifluoromethyldioxolane, and 2,2-bistrifluoromethyl-1,3-dioxolane.

16. A method comprising:

forming an electrolyte composition consisting of:

a) a fluorinated solvent, wherein the fluorinated solvent is a fluorinated acyclic carboxylic acid ester represented by Formula (I)

R 1 —COO—R 2   (I)

wherein

i) R 1 is H, an alkyl group, or a fluoroalkyl group;

ii) R 2 is an alkyl group or a fluoroalkyl group;

iii) either or both of R 1 and R 2 comprises fluorine; and

iv) R 1 and R 2 , taken as a pair, comprise at least two carbon atoms but not more than seven carbon atoms;

b) a carbonate co-solvent, wherein said carbonate co-solvent is ethylene carbonate;

c) at least one γ-lactone, wherein the γ-lactone comprises 2(5H)-furanone;

d) at least one electrolyte salt; and

optionally one or more selected from:

e) a cyclic sulfate represented by Formula (II)

wherein each Q is independently a hydrogen or an optionally fluorinated vinyl, allyl, acetylenic, propargyl, or C 1 -C 3 alkyl group;

f) at least one component selected from:

i) a borate salt represented by Formula (III):

LiBF (4−2p) (C 2 O 4 ) p   (III)

wherein p is 0, 1, or 2; and/or

ii) an oxalate salt represented by Formula (IV):

LiPF (6−2q) (C 2 O 4 ) q   (IV)

wherein q is 1, 2, or 3; and

g) an HF scavenger, wherein the HF scavenger comprises silanes, silazanes, epoxides, amines, aziridines, salts of carbonic acid, B 2 O 5 , and ZnO;

h) a gas-reduction additive, wherein gas-reduction additive comprises halobenzenes, haloalkylbenzenes; 1,3-propane sultone; succinic anhydride; ethynyl sulfonyl benzene; 2-sulfobenzoic acid cyclic anhydride; divinyl sulfone; triphenylphosphate (TPP); diphenyl monobutyl phosphate (DMP); 2,3-dichloro-1,4-naphthoquinone; 1,2-naphthoquinone; 2,3-dibromo-1,4-naphthoquinone; 3-bromo-I,2-naphthoquinone; 2-acetylfuran; 2-acetyl-5-methylfuran; 2-methyl imidazole1-(phenylsulfonyl)pyrrole; 2,3-benzofuran; fluoro-cyclotriphosphazenes; benzotriazole; anisole; diethylphosphonate; fluoroalkyl-substituted dioxolanes, trimethylene borate; diethylene glycol diacetate; triethylene glycol dimethacrylate; triglycol diacetate; 1,2-ethanedisulfonic anhydride; 1,3-propanedisulfonic anhydride; 2,2,7,7-tetraoxide 1,2,7-oxadithiepane; 3-methyl-, 2,2,5,5-tetraoxide 1,2,5-oxadithiolane; hexamethoxycyclotriphosphazene; 4,5-dimethyl-4,5-difluoro-1,3-dioxolan-2-one; 2-ethoxy-2,4,4,6,6-pentafluoro-2,2,4,4,6,6-hexahydro-1,3,5,2,4,6-triazatriphosphorine; 2,2,4,4,6-pentafluoro-2,2,4,4,6,6-hexahydro-6-methoxy-1,3,5,2,4,6-triazatriphosphorine; 4,5-Difluoro-1,3-dioxolan-2-one; 1,4-bis(ethenylsulfonyl)-butane; bis(vinylsulfonyl)-methane; 1,3-bis(ethenylsulfonyl)-propane; 1,2-bis(ethenylsulfonyl)-ethane, and 1,1′-[oxybis(methylenesulfonyl)]bis-ethene;

wherein the electrolyte composition is free from other solvents not listed as one of the a) or b) components;

wherein the electrolyte composition comprises from 0.1 to 5 wt % of the γ-lactone;

wherein the electrolyte composition comprises from 5 to 95 wt % of the fluorinated solvent; and

wherein the electrolyte composition comprises from 0.5 to 95 wt % of the carbonate co-solvent based on the total weight of the electrolyte composition.

17. The method of claim 16 , wherein the halobenzene is selected from the group consisting of fluorobenzene, chlorobenzene, bromobenzene, and iodobenzene.

18. The method of claim 16 , wherein the fluoro-cyclotriphosphazenes is selected from the group consisting of 2,4,6-trifluoro-2-phenoxy-4,6-dipropoxy-cyclotriphosphazene, and 2,4,6-trifluoro-2-(3-(trifluoromethyl)phenoxy)-6-ethoxy-cyclotriphosphazene.

19. The method of claim 16 , wherein the fluoroalkyl-substituted dioxolane is selected from the group consisting of 2-trifluoromethyldioxolane, and 2,2-bistrifluoromethyl-1,3-dioxolane.