Composite membrane, anode structure including the composite membrane, lithium battery including the anode structure, and method of preparing the composite membrane

Patent metadata

Field	Value
Publication number	US-10930913-B2
Application number	US-201816152948-A
Country	US
Kind code	B2
Filing date	Oct 5, 2018
Priority date	Jan 9, 2018
Publication date	Feb 23, 2021
Grant date	Feb 23, 2021

Abstract

A composite membrane comprising an organic film layer; and a plurality of ion conductive inorganic particles disposed in the organic film layer, wherein the organic film layer comprises a crosslinked copolymer, and the crosslinked copolymer comprises a fluorine-containing first repeating unit and at least one repeating unit selected from a fluorine-free second repeating unit and a fluorine-free third repeating unit.

First claim

What is claimed is:

1. A composite membrane comprising
an organic film layer; and
a plurality of ion conductive inorganic particles disposed in the organic film layer,
wherein the organic film layer comprises a crosslinked copolymer, and
the crosslinked copolymer comprises a fluorine-containing first repeating unit and at least one repeating unit selected from a fluorine-free second repeating unit and a fluorine-free third repeating unit.

2. The composite membrane of claim 1 , wherein the fluorine-containing first repeating unit is represented by one or more of Formulae 1 to 3:

wherein, in Formulae 1 to 3,
A 1 , A 2 , A 3 , and A 4 are each independently a covalent bond, —C(═O)—O—, —C(═O)—, or a C1 to C5 linear or branched alkylene group,
R 1 and R 2 are each independently a C1 to C10 linear or branched alkylene group; -(—R a —O—) k - wherein k is an integer from 2 to 100 and R a is a C2 to C10 alkylene group; a C6 to C10 cycloalkylene group; a C6 to C10 arylene group; or a C2 to C10 heteroarylene group,
R 1 and R 2 are each substituted with at least one fluorine atom,
X 1 and X 2 are each independently a covalent bond, —NH—C(═O)—, —CH 2 CH(OH)—, —CF 2 CF(OH)—, —O—, or —S—, and
a1, a2, and b are each a mole fraction and satisfy the conditions of 0≤a1<1, 0<a2≤1, 0≤b<1, and 0<a1+a2+b<1.

3. The composite membrane of claim 1 , wherein the fluorine-free second repeating unit is represented by one or more of Formulae 4 to 7:

wherein, in Formulae 4 to 7,
A 5 , A 6 , A 7 , and A 8 are each independently a covalent bond, —C(═O)—O—, —C(═O)—, or a C1 to C5 linear or branched alkylene group,
R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , and R 10 are each independently a C1 to C10 linear or branched alkylene group; -(—R a —O—) k - wherein k is an integer of 2 to 100 and R a is a C2 to C10 alkylene group; a C6 to C10 cycloalkylene group; a C6 to C10 arylene group; or a C2 to C10 heteroarylene group,
Y 1 is a hydrogen atom, —OH, or —SH,
X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , and X 9 are each independently a covalent bond, —NH—C(═O)—, —CH 2 CH(OH)—, —CF 2 CF(OH)—, —O—, or —S—, and
c, d, e, and f are each a mole fraction and satisfy the conditions of 0≤c<1, 0≤d<1, 0≤e<1, 0≤f<1, and 0<c+d+e+f<1.

4. The composite membrane of claim 1 , wherein the fluorine-free third repeating unit is represented by one or more of Formulae 8 to 13:

wherein, in Formulae 8 to 13,
A 9 , A 10 , A 11 , A 12 , and A 13 are each independently a covalent bond, —O—, —C(═O)—O—, —C(═O)—, or a C1 to C5 linear or branched alkylene group,
R 11 , R 12 , R 13 , and R 14 are each independently a covalent bond, a C1 to C10 linear or branched alkylene group; -(—R a —O—) k - wherein k is an integer of 2 to 100 and R a is a C2 to C10 alkylene group; a C6 to C10 cycloalkylene group; a C6 to C10 arylene group; or a C2 to C10 heteroarylene group,
CY1 is a C2 to C20 heterocycloalkylene group substituted or unsubstituted; a C5 to C20 cycloalkylene group substituted or unsubstituted; a C6 to C20 arylene group substituted or unsubstituted; or a C2 to C20 heteroarylene group substituted or unsubstituted;
X 10 , X 11 , X 12 , X 13 , and X 14 are each independently be a covalent bond, —NH—C(═O)—, —CH 2 CH(OH)—, —CF 2 CF(OH)—, —O—, or —S—, and
g, h, i, j, k, and L are each a mole fraction and satisfy the conditions of 0≤g<1, 0≤h<1, 0≤i<1, 0≤j<1, 0≤k<1, 0≤l<1, and 0<g+h+i+j+k+l<1.

5. The composite membrane of claim 4 , wherein CY1 in Formulae 11 to 13 is represented by one of Formulae 14 or 16, and CY1 in Formulae 8 to 10 is represented by one of Formulae 15 or 17:

wherein, in Formulae 14 to 17,
each R 15 is the same or different, and is independently a hydrogen atom or a C1 to C10 linear or branched alkyl group,
each R 27 is the same or different, and is independently a hydrogen atom, or a C1 to C10 linear or branched alkyl group, and
Y 2 , Y 3 , and Y 4 are each independently C, N, or P,
with the proviso that when Y 2 , Y 3 , and Y 4 are each independently N or P, Y 2 , Y 3 , and Y 4 are not connected to R 15 , R 27 , or other linking group,
m is 0 to 10,
n is 0 to 9,
q is 0 to 4, and
r is 0 to 3.

6. The composite membrane of claim 1 , wherein an amount of the fluorine-containing first repeating unit is, based on a total weight of the crosslinked copolymer, in a range of about 1 weight percent to about 50 weight percent, and a sum of an amount of the fluorine-free second repeating unit and an amount of the fluorine-free third repeating unit is, based on the total weight of the crosslinked copolymer, in a range of about 50 weight percent to about 99 weight percent.

7. The composite membrane of claim 1 , wherein the crosslinked copolymer comprises a polymerization product of polymerizable fluoro-containing monomer and a polymerizable fluorine-free monomer, or
a polymerization product of a polymerizable fluoro-containing monomer, a polymerizable fluorine-free monomer, and a polythiol compound comprising three or four thiol groups.

8. The composite membrane of claim 1 , wherein the crosslinked copolymer comprises
a polymerization product of at least one polyfunctional fluorine-free monomer selected from a polyfunctional acrylic monomer, a polyfunctional vinyl monomer, and a polyfunctional isocyanate monomer, and at least one polyfunctional fluoro-containing monomer selected from a polyfunctional fluoro-containing acrylic monomer, a polyfunctional fluoro-containing vinyl monomer, a polyfunctional fluoro-containing isocyanate monomer, and a polyfunctional fluoro-containing epoxide monomer, or
a polymerization product of a polythiol compound comprising three or four thiol groups, at least one polyfunctional fluorine-free monomer selected from a polyfunctional acrylic monomer, a polyfunctional vinyl monomer, and a polyfunctional isocyanate monomer, and at least one polyfunctional fluoro-containing monomer selected from a polyfunctional fluoro-containing acrylic monomer, a polyfunctional fluoro-containing vinyl monomer, a polyfunctional fluoro-containing isocyanate monomer, and a polyfunctional fluoro-containing epoxide monomer.

9. The composite membrane of claim 8 , wherein the polyfunctional fluoro-containing monomer is represented by one or more of Formulae 14 to 18:

wherein, in Formulae 14 to 18,
A 1 , A 2 , A 3 , and A 4 are each independently a covalent bond, —C(═O)—O—, —C(═O)—, or a C1 to C5 linear or branched alkylene group,
B 1 , B 2 , B 3 , and B 4 are each independently a covalent bond or a C1 to C5 linear or branched alkylene group,
R 1 and R 2 are each independently a C1 to C10 linear or branched alkylene group; -(—R a —O—) k — wherein k is an integer from 2 to 100 and R a is a C2 to C10 alkylene group a C6 to C10 cycloalkylene group; a C6 to C10 arylene group; or a C2 to C10 heteroarylene group, and R 1 and R 2 are each substituted with at least one fluorine atom, X 1a and X 2a are each independently —O— or —S—, and
Z 1 and Z 2 are each independently a hydrogen atom, a C1 t

Assignees

• Samsung Electronics Co Ltd

Inventors

• Choi Wonsung
• Choi Kyounghwan
• Lee Myungjin
• Sugimoto Toshinori
• Kitajima Shintaro

Classifications

• H01M50/443

  Particulate material · CPC title

• H01M50/494

  Tensile strength · CPC title

• H01M50/489

  Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties · CPC title

• H01M50/414

  Synthetic resins, e.g. thermoplastics or thermosetting resins · CPC title

• H01M50/403

  Manufacturing processes of separators, membranes or diaphragms · CPC title