Solid state electrolyte for lithium secondary battery

Patent metadata

Field	Value
Publication number	US-2017194663-A1
Application number	US-201614998411-A
Country	US
Kind code	A1
Filing date	Jan 4, 2016
Priority date	Jan 4, 2016
Publication date	Jul 6, 2017
Grant date	—

Abstract

Provided is a solid state electrolyte composition for a rechargeable lithium battery. The electrolyte composition comprises a lithium ion-conducting polymer matrix or binder and lithium ion-conducting inorganic species that is dispersed in or chemically bonded by the polymer matrix or binder, wherein the lithium ion-conducting inorganic species is selected from Li 2 CO 3 , Li 2 O, Li 2 C 2 O 4 , LiOH, LiX, ROCO 2 Li, HCOLi, ROLi, (ROCO 2 Li) 2 , (CH 2 OCO 2 Li) 2 , Li 2 S, Li x SO y , or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, x=0-1, y=1-4; and wherein the polymer matrix or binder is in an amount from 1% to 99% by volume of the electrolyte composition. Also provided are a process for producing this solid state electrolyte and a lithium secondary battery containing such a solid state electrolyte.

First claim

1 . A solid state electrolyte composition for a rechargeable lithium battery, said electrolyte composition comprising a lithium ion-conducting polymer matrix or binder and lithium ion-conducting inorganic species that is dispersed in or chemically bonded by said polymer matrix or binder, wherein said lithium ion-conducting inorganic species is selected from Li 2 CO 3 , Li 2 O, Li 2 C 2 O 4 , LiOH, LiX, ROCO 2 Li, HCOLi, ROLi, (ROCO 2 Li) 2 , (CH 2 OCO 2 Li) 2 , Li 2 S, Li x SO y , or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, x=0-1, y=1-4; and wherein the polymer matrix or binder is in an amount from 1% to 99% by volume of the electrolyte composition.

2 . The solid state electrolyte composition of claim 1 , wherein said polymer matrix or binder comprises a sulfonated polymer, a mixture of a sulfonated polymer and an electron-conducting polymer, a mixture of a sulfonated polymer and an electronically non-conducting polymer, or a mixture of an electron-conducting polymer and a lithium ion-conducting polymer.

3 . The solid state electrolyte composition of claim 1 , wherein said polymer matrix or binder is selected from sulfonated polyaniline, sulfonated polypyrrole, sulfonated polythiophene, sulfonated polyfuran, or a combination thereof.

4 . A solid state electrolyte composition for a rechargeable lithium battery, said electrolyte composition comprising a lithium ion-conducting polymer matrix or binder selected from a sulfonated polymer and a lithium ion-conducting inorganic species that is dispersed in or chemically bonded by said polymer matrix or binder, wherein said lithium ion-conducting inorganic species contains a lithium salt selected from lithium perchlorate, LiClO 4 , lithium hexafluorophosphate, LiPF 6 , lithium borofluoride, LiBF 4 , lithium hexafluoroarsenide, LiAsF 6 , lithium trifluoro-metasulfonate, LiCF 3 SO 3 , bis-trifluoromethyl sulfonylimide lithium, LiN(CF 3 SO 2 ) 2 , lithium bis(oxalato)borate, LiBOB, lithium oxalyldifluoroborate, LiBF 2 C 2 O 4 , lithium oxalyldifluoroborate, LiBF 2 C 2 O 4 , lithium nitrate, LiNO 3 , Li-Fluoroalkyl-Phosphates, LiPF 3 (CF 2 CF 3 ) 3 , lithium bisperfluoro-ethysulfonylimide, LiBETI, lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide, LiTFSI, an ionic liquid-based lithium salt, or a combination thereof; and wherein the polymer matrix or binder is in an amount from 1% to 99% by volume of the electrolyte composition.

5 . The solid state electrolyte composition of claim 2 , wherein said sulfonated polymer is selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetra-fluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene, sulfonated perfluoroethylene-propylene copolymer, sulfonated ethylene-chlorotrifluoroethylene copolymer, sulfonated polyvinylidenefluoride, sulfonated copolymers of polyvinylidenefluoride with hexafluoropropene and tetrafluoroethylene, sulfonated copolymers of ethylene and tetrafluoroethylene, polybenzimidazole, and chemical derivatives, copolymers, and blends thereof.

6 . The solid state electrolyte composition of claim 4 , wherein said sulfonated polymer is selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetra-fluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene, sulfonated perfluoroethylene-propylene copolymer, sulfonated ethylene-chlorotrifluoroethylene copolymer, sulfonated polyvinylidenefluoride, sulfonated copolymers of polyvinylidenefluoride with hexafluoropropene and tetrafluoroethylene, sulfonated copolymers of ethylene and tetrafluoroethylene, polybenzimidazole, and chemical derivatives, copolymers, and blends thereof

7 . The solid state electrolyte composition of claim 1 , wherein said polymer matrix or binder comprises a mixture of an electron-conducting polymer and a lithium ion-conducting polymer; said lithium ion-conducting polymer is selected from the group consisting of poly(perfluoro sulfonic acid), sulfonated polytetrafluoroethylene, sulfonated perfluoroalkoxy derivatives of polytetra-fluoroethylene, sulfonated polysulfone, sulfonated poly(ether ketone), sulfonated poly (ether ether ketone), sulfonated polystyrene, sulfonated polyimide, sulfonated styrene-butadiene copolymers, sulfonated poly chloro-trifluoroethylene, sulfonated perfluoroethylene-propylene copolymer, sulfonated ethylene-chlorotrifluoroethylene copolymer, sulfonated polyvinylidenefluoride, sulfonated copolymers of polyvinylidenefluoride with hexafluoropropene and tetrafluoroethylene, sulfonated copolymers of ethylene and tetrafluoroethylene, polybenzimidazole, and chemical derivatives, copolymers, and blends thereof, wherein the electron-conducting polymer-to-lithium ion-conducting polymer weight ratio is from 1/99 to 99/1.

8 . The solid state electrolyte composition of claim 1 , wherein said polymer matrix or binder comprises a mixture of a lithium ion-conducting polymer and an electron-conducting polymer and wherein said electron-conducting polymer is selected from the group consisting of polyaniline, polypyrrole, polythiophene, polyfuran, bi-cyclic polymers, derivatives thereof, and combinations thereof.

9 . The solid state electrolyte composition of claim 1 , wherein said polymer matrix or binder contains a lithium ion-conducting polymer selected from poly(ethylene oxide) (PEO), Polypropylene oxide (PPO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride) (PVdF), Poly bis-methoxy ethoxyethoxide-phosphazenex, Polyvinyl chloride, Polydimethylsiloxane, and poly(vinylidene fluoride)-hexafluoropropylene (PVDF-HFP), a derivative thereof, or a combination thereof, or a mixture thereof with a sulfonated polymer.

10 . The solid state electrolyte composition of claim 1 , wherein said polymer matrix further contains particles of a filler dispersed therein.

11 . The solid state electrolyte composition of claim 8 , wherein said filler is selected from a metal oxide, metal carbide, metal nitride, metal boride, metal dichalcogenide, or a combination thereof.

12 . The solid state electrolyte composition of claim 8 , wherein said filler is selected from an oxide, dichalcogenide, trichalcogenide, sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, vanadium, chromium, cobalt, manganese, iron, or nickel in a nanowire, nano-disc, nano-ribbon, or nano platelet form.

13 . The solid state electrolyte composition of claim 8 , wherein said filler is selected from nano discs, nano platelets, or nano sheets of an inorganic material selected from: (a) bismuth selenide or bismuth telluride, (b) transition metal dichalcogenide or trichalcogenide, (c) sulfide, selenide, or telluride of niobium, zirconium, molybdenum, hafnium, tantalum, tungsten, titanium, cobalt, manganese, iron, nickel, or a transition metal; (d) boron nitride, or (e) a combination thereof; wherein said discs, platelets, or sheets have a thickness less than 100 nm.

14 . The solid state electrolyte composition of claim 1 , wherein said lithium ion-conducting species has a room temperature ion conductivity no less than 10 −4 S

Assignees

• Zhamu Aruna
• Jang Bor Z

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01M2300/0068

  inorganic · CPC title

• H01M10/056 Primary

  characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M4/38

  of elements or alloys · CPC title

• H01M2220/20

  Batteries in motive systems, e.g. vehicle, ship, plane · CPC title