Electrolyte for lithium secondary battery and lithium secondary battery using the same

Patent metadata

Field	Value
Publication number	US-10388990-B2
Application number	US-201715724698-A
Country	US
Kind code	B2
Filing date	Oct 4, 2017
Priority date	Aug 30, 2013
Publication date	Aug 20, 2019
Grant date	Aug 20, 2019

Abstract

An electrolyte for a lithium secondary battery, the electrolyte including: a lithium salt; a non-aqueous organic solvent; and a piperazine derivative represented by Formula 1 having an oxidation potential lower than an oxidation potential of the non-aqueous organic solvent by about 2 V to about 4 V:

wherein, in Formula 1, X, Y, and R 1 to R 4 are defined in the specification.

First claim

What is claimed is:

1. A lithium secondary battery comprising:
a cathode comprising a cathode active material,
an anode comprising an anode active material, and
a non-aqueous liquid electrolyte comprising:
a lithium salt;
a non-aqueous organic solvent;
a piperazine derivative additive represented by Formula 1 having an oxidation potential lower than an oxidation potential of the non-aqueous organic solvent by about 2 V to about 4 V:

wherein, in Formula 1,
at least one of X and Y is selected from a C 1 -C 60 alkyl group, a C 1 -C 60 aminoalkyl group, a C 1 -C 60 thioalkyl group, a C 1 -C 60 hydroxyalkyl group, a C 1 -C 60 alkylnitrile group, and a substituted or unsubstituted C 6 -C 60 aryl group, and the unselected rest of X and Y is a hydrogen atom;
R 1 to R 4 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an azido group, an amino group, an amido group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a thiol group, —C(═O)—H, a substituted or unsubstituted C 1 -C 60 alkyl group, a substituted or unsubstituted C 1 -C 60 alkoxy group, a substituted or unsubstituted C 1 -C 60 heteroalkyl group, a substituted or unsubstituted C 2 -C 60 alkenyl group, a substituted or unsubstituted C 2 -C 60 alkynyl group, a substituted or unsubstituted C 3 -C 10 cycloalkyl group, a substituted or unsubstituted C 3 -C 10 heterocycloalkyl group, a substituted or unsubstituted C 2 -C 10 cycloalkenyl group, a substituted or unsubstituted C 2 -C 10 heterocycloalkenyl group, a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, a substituted or unsubstituted C 2 -C 60 heteroaryl group, -(Q 1 ) r -(Q 2 ) s , —N(Q 3 )(Q 4 )(Q 5 ), —P(═O)(Q 6 )(Q 7 ), and —P(Q 8 )(Q 9 )(Q 10 )(Q 11 );
wherein at least one of R 11 to R 14 and at least one of R 21 to R 30 are optionally linked to each other to form a substituted or unsubstituted, saturated or unsaturated ring;
Q 1 is at least one selected from —O—, —S—, —C(═O)—, a substituted or unsubstituted C 1 -C 60 alkylene group, a substituted or unsubstituted C 2 -C 60 alkenylene group, a substituted or unsubstituted C 3 -C 10 cycloalkylene group, a substituted or unsubstituted C 3 -C 10 heterocycloalkylene group, a substituted or unsubstituted C 2 -C 10 cycloalkenylene group, a substituted or unsubstituted C 2 -C 10 heterocycloalkenylene group, a substituted or unsubstituted C 6 -C 60 arylene group, and a substituted or unsubstituted C 2 -C 60 heteroarylene group;
Q 2 to Q 11 are each independently selected from a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an azido group, an amino group, an amido group, an amid ino group, a hydrazine group, a hydrazone group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a thiol group, a substituted or unsubstituted C 1 -C 60 alkyl group, a substituted or unsubstituted C 1 -C 60 alkoxy group, a substituted or unsubstituted C 1 -C 60 heteroalkyl group, a substituted or unsubstituted C 2 -C 60 alkenyl group, a substituted or unsubstituted C 2 -C 60 alkynyl group, a substituted or unsubstituted C 1 -C 60 alkoxy group, a substituted or unsubstituted C 3 -C 10 cycloalkyl group, a substituted or unsubstituted C 3 -C 10 heterocycloalkyl group, a substituted or unsubstituted C 2 -C 10 cycloalkenyl group, a substituted or unsubstituted C 2 -C 10 heterocycloalkenyl group, a substituted or unsubstituted C 6 -C 60 aryl group, a substituted or unsubstituted C 6 -C 60 aryloxy group, and a substituted or unsubstituted C 2 -C 60 heteroaryl group; and
r and s are each independently an integer from 1 to 5, wherein,
when r is 2 or greater, groups Q 1 are each identical to or different from each other, and
when s is 2 or greater, groups Q 2 are each identical to or different from each other,
wherein the lithium secondary battery further comprises a film disposed between the cathode and the electrolyte, wherein the film comprises at least a part of the additive.

2. The lithium secondary battery of claim 1 , wherein R 1 to R 4 in Formula 1 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an azido group, an amino group, an amido group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a thiol group, —C(═O)—H, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, a n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, and -(Q 1 ) r -(Q 2 ) s , wherein
Q 1 is selected from —O—, —S—, —C(═O)—, a C 1 -C 10 alkylene group, a C 6 -C 14 arylene group, and a C 2 -C 14 heteroarylene group;
Q 2 is selected from a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an azido group, an amino group, an amido group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a thiol group, —C(═O)—H, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-a butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, and a C 1 -C 10 alkoxy group, and
r and s are each independently an integer from 1 to 5 wherein,
when r is 2 or greater, groups Q 1 are each identical to or different from each other, and
when s is 2 or greater, groups Q 2 are each identical to or different from each other.

3. The lithium secondary battery of claim 1 , wherein R 1 to R 4 in Formula 1 are each independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an azido group, an amino group, an amido group, an amidino group, a hydrazine group, a hydrazone group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a thiol group, —C(═O)—H, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group,

Assignees

• Samsung Electronics Co Ltd

Inventors

• Kang Yoon-Sok
• Mun Jun-Young
• Park Min-Sik
• Yoon Jae-Gu

Classifications

• H01M10/052 Primary

  Li-accumulators · CPC title

• H01M4/485

  of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) · CPC title

• H01M10/0567 Primary

  characterised by the additives · CPC title

• Y02T10/7011

  Cross-Sectional Technologies · mapped topic

• Y02E60/10

  Energy storage using batteries · CPC title