Electrolyte, method of preparing the electrolyte, and lithium secondary battery comprising the electrolyte

Patent metadata

Field	Value
Publication number	US-10468718-B2
Application number	US-201514855657-A
Country	US
Kind code	B2
Filing date	Sep 16, 2015
Priority date	Sep 19, 2014
Publication date	Nov 5, 2019
Grant date	Nov 5, 2019

Abstract

An electrolyte including a copolymer including (i) an ion-conductive domain including an ion-conductive segment of the copolymer, wherein the ion-conductive segment includes a plurality of ion-conductive units, and (ii) a structural domain including a structural segment of the copolymer, wherein the structural segment includes a plurality of structural units, wherein the ion-conductive domain and the structural domain are covalently linked, and a polymer network phase coupled to the ion-conductive domain.

First claim

What is claimed is:

1. An electrolyte comprising
a copolymer comprising
(i) an ion-conductive domain comprising an ion-conductive segment of the copolymer, wherein the ion-conductive segment comprises a plurality of ion-conductive units, and
(ii) a structural domain comprising a structural segment of the copolymer, wherein the structural segment comprises a plurality of structural units, wherein the ion-conductive domain and the structural domain are covalently linked, and

a polymer network phase, which is physically coupled to, included in, and completely surrounded by the ion-conductive domain of the copolymer,
wherein the polymer network phase comprises a polymerization product of at least one polymerizable reactive group-including compound selected from a multi-functional monomer with a polymerizable reactive group, an inorganic particle with a polymerizable reactive group, and an ionic liquid with a polymerizable reactive group,
wherein the polymerizable reactive group of the inorganic particle is at least one selected from a functional group comprising an ethylenically unsaturated bond, an epoxy group, and an aldehyde group.

2. The electrolyte of claim 1 , wherein the copolymer is a block copolymer.

3. The electrolyte of claim 1 , wherein the polymerizable group of the multi-functional monomer and the ionic liquid is at least one selected from a functional group comprising an ethylenically unsaturated bond, a hydroxyl group, an amino group, an amide group, an epoxy group, a carboxyl group, and an aldehyde group.

4. The electrolyte of claim 1 , wherein the polymerizable group-including compound comprises at least one selected from a lithium ion-conductive moiety and a hydrophilic moiety.

5. The electrolyte of claim 1 , wherein the multi-functional monomer with a polymerizable reactive group is at least one selected from a C5-C30 (meth)acrylate ester comprising at least two carbon-carbon double bonds, a poly(C3-C30 (meth)acrylate ester) comprising at least two carbon-carbon double bonds, a C4-C30 aliphatic compound comprising at least two carbon-carbon double bonds, and a C4-C30 aromatic compound comprising at least two carbon-carbon double bonds.

6. The electrolyte of claim 1 , wherein the multi-functional monomer with a polymerizable reactive group is at least one selected from polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, 1,4-butadiene, 1,6-hexadiene, allyl acrylate, acrylated cinnamate, isoprene, butadiene, chloroprene, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, ethylene glycol (meth)acrylate, 1,2-propylene glycol (meth)acrylate, 1,3-propylene glycol (meth)acrylate, acrylic acid, methacrylic acid, 2-(meth)acryloyloxy acetic acid, 3-(meth)acryloyloxy propionic acid, 4-(meth)acryloyloxy butyric acid, itaconic acid, maleic acid, 2-isocyanatoethyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 4-isocyanatobutyl (meth)acrylate, (meth)acrylamide, N-vinylpyrrolidone, ethylene dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylol propane trimethacrylate, trimethylol propane triacrylate, 1,3-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and N-vinyl caprolactam.

7. The electrolyte of claim 1 , wherein an amount of the multi-functional monomer with a polymerizable reactive group is in a range of about 5 parts to about 50 parts by weight based on 100 parts by weight of the copolymer.

8. The electrolyte of claim 1 , wherein an amount of the inorganic particles with a polymerizable reactive group is in a range of about 1 part to about 40 parts by weight based on 100 parts by weight of the copolymer.

9. The electrolyte of claim 1 , wherein an amount of the ionic liquid with a polymerizable reactive group is in a range of about 5 parts to about 40 parts by weight based on 100 parts by weight of the copolymer.

10. The electrolyte of claim 1 , wherein the ion-conductive units of the ion-conductive segment of the copolymer are not crosslinked.

11. The electrolyte of claim 1 , wherein the ion-conductive segment of the copolymer comprising a plurality of ion-conductive repeating units is derived from at least one selected from polyethylene oxide, polypropylene oxide, polymethylmethacrylate, polyethylmethacrylate, polydimethylsiloxane, polyacrylic acid, polymethacrylic acid, polymethylacrylate, polyethylacrylate, poly-2-ethylhexyl acrylate, polybutyl methacrylate, poly-2-ethylhexylmethacrylate, polydecylacrylate, polyethylene vinyl acetate, polyimide, polyamine, polyamide, polyalkyl carbonate, polynitrile, polyphosphazine, polyolefin, and polydiene.

12. The electrolyte of claim 1 , further comprising at least one type of inorganic particles selected from SiO 2 , TiO 2 , ZnO, Al 2 O 3 , BaTiO 3 , cage-structured silsesquioxane, and a metal-organic framework.

13. The electrolyte of claim 1 , wherein the inorganic particles with a polymerizable reactive group are at least one type of particles selected from silsesquioxane with a polymerizable reactive group, SiO 2 with a polymerizable reactive group, TiO 2 with a polymerizable reactive group, ZnO with a polymerizable reactive group, Al 2 O 3 with a polymerizable reactive group, BaTiO 3 with a polymerizable reactive group, and a metal-organic framework with a polymerizable reactive group.

14. The electrolyte of claim 1 , wherein the polymer network phase comprises a reaction product of:
i) at least one polymerizable reactive group-including compound selected from a multi-functional monomer with a polymerizable reactive group, an inorganic particle with a polymerizable reactive group, and an ionic liquid with a polymerizable reactive group, and
ii) at least one monofunctional monomer selected from a monofunctional acrylate monomer and a monofunctional methacrylate monomer.

15. The electrolyte of claim 14 , wherein the monofunctional monomer is at least one selected from butyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate, decylacrylate, ethylene vinyl acetate, ethylene glycol monoacrylate, ethylene glycol monomethacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, 2,2,2-trifluoroethyl acrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1,1,1,3,3,3-hexafluoro isopropyl acrylate, 1,1,1,3,3,3-hexafluoro isopropyl methacrylate, 2,2,3,3,4,4,4-heptafluorobutyl acrylate, 2,2,3,3,4,4,4-heptafluorobutyl methacrylate, 2,2,3,3,4,4,5,5-octafluoropentyl acrylate, 2,2,3,3,4,4,5,5-octafluoropentyl methacrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl acrylate, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl methacrylate, 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate, and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl methacrylate.

16. The electrolyte of claim 14 , wherein an amount of the monofunctional monomer is in a range of about 0.1 part to about 50 parts by weight based on 100 parts by weight of the copolymer.

17. The electrolyte of claim 1 , further comprising at least one ionic liquid selected from compounds each comprising:
i) a cation of at least one selected from an ammonium cation, a pyrrolidinium cation, a pyridinium cation, a pyrimidinium cation, an imidazolium cation, a piperidinium cation, a pyrazolium cation, an oxazolium cation, a pyridazinium cation, a phosphonium cation, a sulfonium cation, and a triazolium cation, and
ii) a

Assignees

• Samsung Electronics Co Ltd

Inventors

• Lee Yonggun
• Yang Yooseong
• Choi Hongsoo
• Lee Jenam
• Chang Wonseok

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0565 Primary

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M2300/0082

  Organic polymers · CPC title

• H01M10/0525

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

• Y02E60/10

  Energy storage using batteries · CPC title