Bis(phenyl) methanedisulfonate-based additive and lithium secondary battery comprising the same

Patent metadata

Field	Value
Publication number	US-11038202-B2
Application number	US-201816049963-A
Country	US
Kind code	B2
Filing date	Jul 31, 2018
Priority date	Aug 16, 2017
Publication date	Jun 15, 2021
Grant date	Jun 15, 2021

Abstract

An electrolyte includes: a lithium salt; a non-aqueous solvent; and a disulfonate compound represented by Formula 1:wherein, in Formula 1, R1 and R2 are each independently a fluorine, a cyano group, a nitro group, or a methyl group substituted with at least one fluorine,R11 to R14 are each independently a hydrogen, a deuterium, a fluorine, a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C2-C10 alkenyl group, or a substituted or unsubstituted C2-C10 alkynyl group,a1 and a2 are each independently an integer of 1 to 5,a11 and a12 are each independently an integer of 0 to 4, anda sum of a1 and a11 is 5, and a sum of a2 and a12 is 5.

First claim

What is claimed is:

1. A lithium secondary battery comprising:
a positive electrode,
a negative electrode, and
an electrolyte disposed between the positive electrode and the negative electrode,
wherein the electrolyte comprises:
a lithium salt;
a non-aqueous solvent; and
about 0.1 weight percent or greater to less than about 3 weight percent of a disulfonate compound represented by Formula 1, each of which is based on a total weight of the electrolyte,
and the positive electrode comprises a positive active material represented by Formula 2:

wherein, in Formula 1,
R 1 and R 2 are each independently a cyano group or a nitro group,
R 11 to R 14 are each independently a hydrogen, a deuterium, a fluorine, a hydroxyl group, a cyano group, a nitro group, a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 2 -C 10 alkenyl group, or a substituted or unsubstituted C 2 -C 10 alkynyl group,
a1 and a2 are each independently an integer of 1 to 5,
a11 and a12 are each independently an integer of 0 to 4, and
a sum of a1 and a11 is 5, and a sum of a2 and a12 is 5;
Formula 2
Li x Ni y M 1−y O 2−z A z

wherein, in Formula 2, 0.9≤x≤1.2, 0.1≤y≤0.98, 0≤z<0.2,
M includes Al, Mg, Mn, Co, Fe, Cr, V, Ti, Cu, B, Ca, Zn, Zr, Nb, Mo, Sr, Sb, W, Bi, or a combination thereof; and
A is an element having an oxidation number of −1, −2 or −3.

2. The lithium secondary battery of claim 1 , wherein the disulfonate compound represented by Formula 1 is present in an amount of about 1 weight percent to about 2 weight percent.

3. The lithium secondary battery of claim 1 ,
wherein R 1 and R 2 are each independently a cyano group.

4. The lithium secondary battery of claim 1 , wherein R 11 to R 14 are each independently a hydrogen, a substituted or unsubstituted C 1 -C 10 alkyl group, or a substituted or unsubstituted C 2 -C 10 alkenyl group.

5. The lithium secondary battery of claim 1 , wherein a1 and a2 are each independently 1, 2, or 5.

6. The lithium secondary battery of claim 1 , wherein the lithium salt comprises lithium difluoro(oxalato)borate, lithium bis(oxalato)borate, lithium difluoro bis(oxalato)phosphate, LiBF 4 , LiPF 6 , LiCF 3 SO 3 , (CF 3 SO 2 ) 2 NLi, (FSO 2 ) 2 NLi, or a combination thereof.

7. The lithium secondary battery of claim 1 , wherein the non-aqueous solvent comprises dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, or a combination thereof.

8. The lithium secondary battery of claim 1 , wherein the non-aqueous solvent further includes fluoroethylene carbonate.

9. The lithium secondary battery of claim 1 , wherein the positive active material is represented by Formula 3 or Formula 4:
Formula 3
LiNi y′ CO 1−y′−z′ Mn z′ O 2
Formula 4
LiNi y′ Co 1−y′−z′ Mn z′ O 2
wherein, in Formula 3 and 4, 0.9≤x′≤1.2, 0.8≤y′≤0.98, 0<z′<0.1, and 0<1−y′−z′<0.2.

10. The lithium secondary battery of claim 1 , wherein the positive electrode comprises LiNi 0.80 Co 0.15 Mn 0.05 O 2 , LiNi 0.85 Co 0.1 Mn 0.05 O 2 , LiNi 0.88 Co 0.08 Mn 0.04 O 2 , LiNi 0.88 Co 0.08 Al 0.04 O 2 , Li 1.02 Ni 0.80 Co 0.15 Mn 0.05 O 2 , Li 1.02 Ni 0085 Co 0.10 Mn 0005 O 2 , Li 1.02 Ni 0.88 Co 00.8 Mn 00.4 O 2 , or a combination thereof.

11. The lithium secondary battery of claim 1 , wherein the lithium secondary battery has a capacity retention of about 80% or greater and a direct current internal resistance increase rate of less than about 150% after 300 charge/discharge cycles at a temperature of about 45° C.

12. The lithium secondary battery of claim 1 , wherein the lithium secondary battery has a cell energy density of about 500 watt hours per liter or greater.

13. The lithium secondary battery of claim 1 , further comprising a carbonate including a carbon-carbon single bond, a carbonate including a carbon-carbon double bond, a carbonate including a carbon-carbon triple bond, a carboxylic anhydride including a carbon-carbon double bond, a carboxylic anhydride including a carbon-carbon triple bond, or a combination thereof.

14. The lithium secondary battery of claim 1 , further comprising a vinylene carbonate, a vinyl ethylene carbonate, a maleic anhydride, a succinic anhydride, or a combination thereof.

15. The lithium secondary battery of claim 1 , further comprising a phosphorus-containing compound, a sulfur-containing compound other than the disulfonate compound represented by Formula 1, or a combination thereof, wherein the phosphorus-containing compound, the sulfur-containing compound other than the disulfonate compound represented by Formula 1, or the combination thereof is present in an amount of about 0.1 weight percent to about 2 weight percent, based on a total weight of the electrolyte.

16. The lithium secondary battery of claim 15 , wherein the phosphorus-containing compound comprises a phosphine compound, a phosphite compound, or a combination thereof.

17. The lithium secondary battery of claim 1 , wherein the negative electrode comprises a negative active material comprising a metal or a metalloid alloyable with lithium, a carbonaceous negative active material, or a combination thereof.

18. The lithium secondary battery of claim 17 , wherein the negative active material comprising a metalloid alloyable with lithium comprises silicon, a silicon-carbon composite material, SiO a′ , wherein 0<a′<2, or a combination thereof.

19. The lithium secondary battery of claim 1 ,
wherein the negative electrode comprises a negative active material comprising a silicon-carbon composite that includes silicon particles, and
wherein the silicon particles have an average particle diameter of about 200 nanometers or less.

20. The lithium secondary battery of claim 19 , wherein the silicon-carbon composite includes graphite to provide the negative electrode with a capacity of 600 milliampere hours per gram (mAh/g) to about 2000 mAh/g.

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Koh Myongchun
• Kang Yoonsok
• Park Eunha
• Seo Jinah

Classifications

• H01M2300/0034

  Fluorinated solvents · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M10/0567 Primary

  characterised by the additives · CPC title

• H01M4/505

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