Hybrid Solid State Electrolyte for Lithium Secondary Battery

Patent metadata

Field	Value
Publication number	US-2018166759-A1
Application number	US-201615375508-A
Country	US
Kind code	A1
Filing date	Dec 12, 2016
Priority date	Dec 12, 2016
Publication date	Jun 14, 2018
Grant date	—

Abstract

Provided is a solid state electrolyte for a rechargeable lithium battery, comprising a lithium ion-conducting polymer matrix or binder and a lithium ion-conducting inorganic species dispersed in or chemically bonded by the polymer matrix or binder, wherein the lithium ion-conducting inorganic species is selected from a mixture of a sodium-conducting species or sodium salt and a lithium-conducting species or lithium salt 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 mixture of a lithium ion-conducting polymer matrix or binder, a lithium ion-conducting inorganic species or lithium salt, and a sodium ion-conducting species or sodium salt, wherein said lithium ion-conducting inorganic species or lithium salt and said sodium ion-conducting species or sodium salt are 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 weight of the electrolyte composition and a weight ratio between said lithium ion-conducting inorganic species or lithium salt and said sodium ion-conducting species or sodium salt is from 1/99 to 99/1.

2 . The solid state electrolyte composition of claim 1 , wherein said sodium-conducting species or sodium salt is selected from Na 2 CO 3 , Na 2 O, Na 2 C 2 O 4 , NaOH, NaX, ROCO 2 Na, HCONa, RONa, (ROCO 2 Na) 2 , (CH 2 OCO 2 Na) 2 , Na 2 S, Na x SO y , NaClO 4 , NaPF 6 , NaF 4 , NaAsF 6 , NaCF 3 SO 3 , NaN(CF 3 SO 2 ) 2 , sodium bis(oxalato)borate, NaBOB, NaBF 2 C 2 O 4 , NaBF 2 C 2 O 4 , NaNO 3 , NaPF 3 (CF 2 CF 3 ) 3 , sodium bisperfluoro-ethysulfonylimide, NaBETI, sodium bis(trifluoromethanesulphonyl)imide, sodium bis(fluorosulphonyl)imide, sodium trifluoromethanesulfonimide, NaTFSI, an ionic liquid-based sodium salt, or a combination thereof; wherein X=F, Cl, I, or Br, R=a hydrocarbon group, x=0-1, y=1-4.

3 . 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.

4 . 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.

5 . A solid state electrolyte composition for a rechargeable lithium battery, said electrolyte composition comprising (A) a lithium ion-conducting polymer matrix or binder selected from a sulfonated polymer, (B) a lithium ion-conducting inorganic species or lithium salt, and (C) a sodium ion-conducting species or sodium salt, wherein said lithium ion-conducting inorganic species or lithium salt and said sodium ion-conducting species or sodium salt are dispersed in or chemically bonded by said polymer matrix or binder, wherein said lithium ion-conducting inorganic species is 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 weight of the electrolyte composition and a weight ratio between said lithium ion-conducting inorganic species or lithium salt and said sodium ion-conducting species or sodium salt is from 1/99 to 99/1

6 . The solid state electrolyte composition of claim 5 , wherein said sodium ion-conducting species or sodium salt is selected from Na 2 CO 3 , Na 2 O, Na 2 C 2 O 4 , NaOH, NaX, ROCO 2 Na, HCONa, RONa, (ROCO 2 Na) 2 , (CH 2 OCO 2 Na) 2 , Na 2 S, Na x SO y , NaClO 4 , NaPF 6 , NaF 4 , NaAsF 6 , NaCF 3 SO 3 , NaN(CF 3 SO 2 ) 2 , sodium bis(oxalato)borate, NaBOB, NaBF 2 C 2 O 4 , NaBF 2 C 2 O 4 , NaNO 3 , NaPF 3 (CF 2 CF 3 ) 3 , sodium bisperfluoro-ethysulfonylimide, NaBETI, sodium bis(trifluoromethanesulphonyl)imide, sodium bis(fluorosulphonyl)imide, sodium trifluoromethanesulfonimide, NaTFSI, an ionic liquid-based sodium salt, or a combination thereof; wherein X=F, Cl, I, or Br, R=a hydrocarbon group, x=0-1, y=1-4.

7 . The solid state electrolyte composition of claim 3 , 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.

8 . The solid state electrolyte composition of claim 5 , 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

9 . 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.

10 . 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, polyf

Assignees

• Nanotek Instruments Inc

Inventors

• Zhamu Aruna
• Jang Bor Z

Classifications

• H01M10/056 Primary

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

• H01M10/052

  Li-accumulators · CPC title

• H01M2300/0071

  Oxides · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title

• H01M4/38

  of elements or alloys · CPC title