Polymer electrolyte, method of preparing the polymer electrolyte, and lithium metal battery including the same

Patent metadata

Field	Value
Publication number	US-10862164-B2
Application number	US-201715624226-A
Country	US
Kind code	B2
Filing date	Jun 15, 2017
Priority date	Jun 24, 2016
Publication date	Dec 8, 2020
Grant date	Dec 8, 2020

Abstract

A polymer electrolyte including a polymerization product of a polymer having an unsaturated functional group at a terminal thereof and a fluoroalkylene chain, and an ion-conductive polymer having an unsaturated functional group at a terminal thereof, wherein the ion-conductive polymer having an unsaturated functional group at a terminal thereof is a polymer represented by Formula 1 or Formula 2, and the polymer having an unsaturated functional group at a terminal thereof and a fluoroalkylene chain is a compound represented by Formula 3, wherein Formulae 1 to 3 are the same as represented in the detailed description of the specification.

First claim

What is claimed is:

1. A polymer electrolyte comprising a polymerization product of:
a polymer comprising an unsaturated functional group at a terminal thereof and a fluoroalkylene chain, and
an ion-conductive polymer comprising an unsaturated functional group at a terminal thereof,
wherein the polymer having an unsaturated functional group at a terminal thereof and a fluoroalkylene chain is a compound represented by Formula 3:

wherein, in Formula 3,
L 1 and L 3 are each independently a bond or —C(═O)O—R—NH—, wherein R is a divalent, trivalent or tetravalent group and selected from a C1-C20 aliphatic hydrocarbon group, a C5-C40 cycloaliphatic group, a C5-C40 cycloaliphatic urethane group, a C6-C40 aryl group, and a C2-C40 heteroaryl group,
A 1 and A 2 are each independently a bond or a divalent, trivalent or tetravalent bonding group,
L 2 is a fluoropolyalkylene oxide chain or a perfluoropolyalkylene oxide chain,
R 1 and R 2 are each independently a hydrogen or a C1-C5 alkyl group, and
n and m are each independently an integer from 1 to 3;
wherein the ion-conductive polymer comprising an unsaturated functional group at a terminal thereof is a polymer represented by Formula 1 or Formula 2,

wherein, in Formula 1,
R 1 and R 2 are each independently a hydrogen or a C1-C5 alkyl group, and L is one selected from groups represented by Formula 1a,

wherein, in Formula 1a,
R 1 is a C1-C5 alkylene group,
R 2 and R 3 are each independently a C1-C5 alkyl group,
a is an integer from 1 to 10,
k is an integer from 1 to 10,
l is an integer from 1 to 10,
n is an integer from 1 to 10, and
* denotes a binding site to a neighboring atom;

wherein, in Formula 2,
R 1 is a hydrogen or a C1-C5 alkyl group, and
L′ is one selected from groups represented by Formula 2a,

wherein, in Formula 2a,
a is an integer from 1 to 10,
R 1 is a C1-C5 alkylene group,
R 0 and R 2 to R 6 are each independently a C1-C10 alkyl group, a C6-C10 aryl group, or a C1-C10 heteroaryl group,
k is an integer from 1 to 10,
l is an integer from 1 to 10, and
* denotes a binding site to a neighboring atom;

wherein the polymerization product is a compound represented by Formula 8 or a compound represented by Formula 9,

wherein, in Formula 8,
l is an integer from 1 to 10,
m is an integer from 1 to 10,
each n is an integer from 1 to 10,
R 1 and R are independently hydrogen or a C1-C5 alkyl group,

is a group represented by the following formula,

wherein, in the above formula,
L1 and L3 are each independently a bond or —C(═O)O—R—NH—, wherein R is a divalent, trivalent or tetravalent group, and selected from a C1-C20 aliphatic hydrocarbon group, a C5-C40 cycloaliphatic group, a C5-C40 cycloaliphatic urethane group, a C6-C40 aryl group, and a C2-C40 heteroaryl group,
A1 and A2 are each independently a bond or a divalent, trivalent or tetravalent bonding group,
L2 is a fluoropolyalkylene oxide chain or a perfluoropolyalkylene oxide chain,

is L, wherein L is one selected from groups represented by Formula 1a,

wherein, in Formula 1a,
R1 is a C1-05 alkylene group,
R2 and R3 are each independently a C1-C5 alkyl group,
a is an integer from 1 to 10,
k is an integer from 1 to 10,
l is an integer from 1 to 10,
n is an integer from 1 to 10, and
* denotes a binding site to a neighboring atom;

wherein, in Formula 9,

is the same as in Formula 8, and

is L′, wherein L′ is one selected from groups represented by Formula 2a,

wherein, in Formula 2a,
a is an integer from 1 to 10,
R1 is a C1-C5 alkylene group,
R0 and R2 to R6 are each independently a C1-C10 alkyl group, a C6-C10 aryl group, or a C1-C10 heteroaryl group,
k is an integer from 1 to 10,
l is an integer from 1 to 10, and
* denotes a binding site to a neighboring atom.

2. The polymer electrolyte of claim 1 , wherein an amount of the ion-conductive polymer having an unsaturated functional group at a terminal thereof is from about 0.1 part to about 50 parts by weight based on 100 parts by weight of the polymer having an unsaturated functional group at a terminal thereof and a fluoroalkylene chain.

3. The polymer electrolyte of claim 1 , wherein L 2 in Formula 3 is a group represented by Formula 3a:
—(CF 2 O) p (CF 2 CF 2 O) q (CFYO) r (CF 2 CFYO) s —(CF 2 (CF 2 ) z CF 2 O) t —  Formula 3a

wherein, in Formula 3a,
Y is a C1-C5 perfluoroalkyl group or a C1-C5 perfluoroalkyloxygroup,
z is 1 or 2, and
p, q, r, s, and t are each independently selected from 0 and a positive integer such that the weight average molecular weight of L 2 is about 500 to about 4,000 grams per mole.

4. The polymer electrolyte of claim 1 , wherein L 2 in Formula 3 is a group represented by Formula 3b:
—(CF 2 O) p (CF 2 CF 2 O) q —  Formula 3b

wherein, in Formula 3b,
p and q are each independently selected from 0 and a positive integer such that the weight average molecular weight of L 2 is about 500 to 4,000 grams per mole.

5. The polymer electrolyte of claim 1 , wherein A 1 and A 2 in Formula 3 are each a group represented by the following formula:

* denotes a binding site to a neighboring atom.

6. The polymer electrolyte of claim 1 , wherein the compound represented by Formula 3 is a compound represented by Formula 4 or Formula 5:

wherein, in Formula 4, R 1 , R 2 , A 1 , n, m, L 2 , and A 2 are the same as in Formula 3, and

in Formula 5, R 1 , R 2 , Al n, m, L 2 , and A 2 are the same as in Formula 3, and
R is a

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Lee Myungjin
• Kim Kihyun
• Yu Taehwan
• Chang Wonseok

Classifications

• C08F222/1065

  of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates · CPC title

• C08G65/007

  containing fluorine · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• C08J2327/12

  containing fluorine atoms · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title