A lithium cobalt oxide secondary battery comprising a fluorinated electrolyte and a positive electrode material for high voltage applications

Patent metadata

Field	Value
Publication number	US-2021135291-A1
Application number	US-201917051322-A
Country	US
Kind code	A1
Filing date	May 2, 2019
Priority date	May 4, 2018
Publication date	May 6, 2021
Grant date	—

Abstract

A liquid electrolyte lithium secondary battery cell comprising: a positive electrode including a powderous positive active material having the following chemical formula: Li 1−x (Co 1-a-b-c Ni a Mn b M″ c ) 1−x O 2 with −0.01≤x≤0.01, 0.00≤a≤0.09, 0.01≤b≤0.05, and 0.00≤c≤0.03 wherein M″ is either one or more metals of the group consisting of Al, Mg, Ti and Zr; and an electrolyte composition comprising at least one cyclic carbonate; at least one fluorinated acyclic carboxylic acid ester; at least one electrolyte salt; at least one lithium compound selected from lithium phosphates compounds, lithium boron compounds, lithium sulfonates compounds and mixtures thereof; at least one cyclic sulfur compound; and optionally at least one cyclic carboxylic acid anhydride.

First claim

1 - 24 . (canceled)

25 . A liquid electrolyte lithium secondary battery cell having an operating voltage superior or equal to 4.4 V, comprising:
a positive electrode including a powderous positive active material represented by the following chemical formula:
Li 1−x (Co 1-a-b-c Ni a Mn b M″ c ) 1+x O 2 with −0.01 ≤x≤ 0.01, 0.00 ≤a≤ 0.09, 0.01 ≤b≤ 0.05, and 0.00 ≤c≤ 0.03,

wherein M″ is one or more metals selected from the group consisting of Al, Mg, Ti and Zr; and
an electrolyte composition comprising:
1) from 5.0% to 17.0% of a non-fluorinated cyclic carbonate, and from 0.5% to 10% of a fluorinated cyclic carbonate,
2) from 70.0% to 95.0% of a fluorinated acyclic carboxylic acid ester,
3) at least one electrolyte salt,
4) from 0.10% to 5.0% of a lithium boron compound,
5) from 0.20% to 10.0% of a cyclic sulfur compound, and
6) optionally at least one cyclic carboxylic acid anhydride,

all percentages being expressed by weight relative to the total weight of the electrolyte composition.

26 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the non-fluorinated cyclic carbonate of the electrolyte composition is of formula (I) or (II)

wherein R 1 to R 6 are independently selected from hydrogen, C 1 to C 3 -alkyl, C 2 to C 3 -alkenyl, or C 2 to C 3 -alkynyl groups.

27 . The liquid electrolyte lithium secondary battery cell according to claim 26 , wherein the non-fluorinated cyclic carbonate of the electrolyte composition is selected from the group consisting of ethylene carbonate, propylene carbonate, vinylene carbonate, ethyl propyl vinylene carbonate, vinyl ethylene carbonate, dimethylvinylene carbonate, and mixtures thereof.

28 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the fluorinated cyclic carbonate of the electrolyte composition is of formula (I) or (II)

wherein at least one of R 1 to R 6 is fluorine or a C 1 to C 3 -fluoroalkyl, C 2 to C 3 -fluoroalkenyl, C 2 to C 3 -fluoroalkynyl group.

29 . The liquid electrolyte lithium secondary battery cell according to claim 28 , wherein the fluorinated cyclic carbonate of the electrolyte composition is selected from the group consisting of 4-fluoro-1,3-dioxolan-2-one; 4-fluoro-4-methyl-1,3-dioxolan-2-one; 4-fluoro-5-methyl-1,3-dioxolan-2-one; 4-fluoro-4,5-dimethyl-1,3-dioxolan-2-one; 4,5-difluoro-1,3-dioxolan-2-one; 4,5-difluoro-4-methyl-1,3-dioxolan-2-one; 4,5-difluoro-4,5-dimethyl-1,3-dioxolan-2-one; 4,4-difluoro-1,3-dioxolan-2-one; 4,4,5-trifluoro-1,3-dioxolan-2-one; 4,4,5,5-tetrafluoro-1,3-dioxolan-2-one; and mixtures thereof; being preferably 4-fluoro-1,3-dioxolan-2-one.

30 . The liquid electrolyte lithium secondary battery cell according to claim 28 , wherein the fluorinated cyclic carbonate is present in the electrolyte composition in an amount ranging from 0.5% to 10%, by weight relative to the total weight of the electrolyte composition.

31 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the fluorinated acyclic carboxylic acid ester of the electrolyte composition is represented by the formula:
R 1 —COO—R 2
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.

32 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the fluorinated acyclic carboxylic acid ester of the electrolyte composition is selected from the group consisting of 2,2-difluoroethyl acetate, 2,2,2-trifluoroethyl acetate, 2,2-difluoroethyl propionate, 3,3-difluoropropyl acetate, 3,3-difluoropropyl propionate, methyl 3,3-difluoropropanoate, ethyl 3,3-difluoropropanoate, ethyl 4,4-difluorobutanoate, difluoroethyl formate, trifluoroethyl formate, and mixtures thereof, preferably selected from the group consisting of 2,2-difluoroethyl acetate, 2,2-difluoroethyl propionate, 2,2,2-trifluoroethyl acetate, 2,2-difluoroethyl formate and mixtures thereof.

33 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the electrolyte salt of the electrolyte composition is a lithium salt.

34 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the electrolyte salt is present in the electrolyte composition in an amount ranging from 5% to 20%, by weight relative to the total weight of the electrolyte composition.

35 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein said lithium boron compound of the electrolyte composition is selected from the group consisting of lithium tetrafluoroborate, lithium bis(oxalato)borate, lithium difluoro(oxalato)borate, Li 2 B 12 F 12-x H x , wherein x is an integer ranging from 0 to 8.

36 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the lithium boron compound is present in the electrolyte composition in an amount ranging from 0.2% to 4%, by weight relative to the total weight of the electrolyte composition.

37 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the cyclic sulfur compound of the electrolyte composition is represented by the formula:

wherein Y is oxygen or denotes an HCA group; wherein each A is independently hydrogen or an optionally fluorinated ethenyl, allyl, ethynyl, propargyl, or C 1 -C 3 alkyl group; and n is 0 or 1.

38 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the cyclic sulfur compound of the electrolyte composition is selected from the group consisting of 1,3,2-dioxathiolane-2,2-dioxide, 1,3,2-dioxathiolane-4-ethynyl-2,2-dioxide, 1,3,2-dioxathiolane-4-ethenyl-2,2-dioxide, 1,3,2-dioxathiolane-4,5-diethenyl-2,2-dioxide, 1,3,2-dioxathiolane-4-methyl-2,2-dioxide, 1,3,2-dioxathiolane-4,5-dimethyl-2,2-dioxide; 1,3,2-dioxathiane-2,2-dioxide, 1,3,2-dioxathiane-4-ethynyl-2,2-dioxide, 1,3,2-dioxathiane-5-ethynyl-2,2-dioxide, 1,3,2-dioxathiane-4-ethenyl-2,2-dioxide, 1,3,2-dioxathiane-5-ethenyl-2,2-dioxide, 1,3,2-dioxathiane-4,5-diethenyl-2,2-dioxide, 1,3,2-dioxathiane-4,6-diethenyl-2,2-dioxide, 1,3,2-dioxathiane-4,5,6-triethenyl-2,2-dioxide, 1,3,2-dioxathiane-4-methyl-2,2-dioxide, 1,3,2-dioxathiane-5-methyl-2,2-dioxide, 1,3,2-dioxathiane-4,5-dimethyl-2,2-dioxide, dioxathiane-4,6-dimethyl-2,2-dioxide, dioxathiane-4,5,6-trimethyl-2,2-dioxide; 1,3-propane sultone, 3-fluoro-1,3-propane sultone, 4-fluoro-1,3-propane sultone, 5-fluoro-1,3-propane sultone, 1,4-butane sultone, 3-fluoro-1,4-butane sultone, 4-fluoro-1,4-butane sultone, 5-fluoro-1,4-butane sultone, 6-fluoro-1,4-butane sultone and mixtures thereof.

39 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the cyclic sulfur compound is present in the electrolyte composition in an amount ranging from 0.3% to 7%, by weight relative to the total weight of the electrolyte composition.

40 . The liquid electrolyte lithium secondary battery cell according to claim 25 , wherein the cyclic carboxylic acid anhydride of the electrolyte composition is represented by one of th

Assignees

• Umicore Nv
• Solvay

Inventors

• Kim Jeong-Rae
• Lee Jong-Ju
• Bridel Jean-Sébastien
• Won Ji-Hye
• Choi Moon-Hyung
• Oh Mi-Soon
• Lee Hyuncheol
• Hough Lawrence Alan
• Kim Hae-Young

Classifications

• 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

• H01M10/0569 Primary

  characterised by the solvents · CPC title

• H01M4/505

  of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy · CPC title

• H01M10/0567

  characterised by the additives · CPC title

• H01M2300/004

  Three solvents · CPC title