Process for producing non-flammable quasi-solid electrolyte and electrolyte-separator for lithium battery applications

Patent metadata

Field	Value
Publication number	US-9601805-B2
Application number	US-201313987396-A
Country	US
Kind code	B2
Filing date	Jul 22, 2013
Priority date	Jul 22, 2013
Publication date	Mar 21, 2017
Grant date	Mar 21, 2017

Abstract

A process for producing a separator-electrolyte layer for use in a lithium battery, comprising: (a) providing a porous separator; (b) providing a quasi-solid electrolyte containing a lithium salt dissolved in a first liquid solvent up to a first concentration no less than 3 M; and (c) coating or impregnating the separator with the electrolyte to obtain the separator-electrolyte layer with a final concentration≧the first concentration so that the electrolyte exhibits a vapor pressure less than 0.01 kPa when measured at 20° C., a vapor pressure less than 60% of that of the first liquid solvent alone, a flash point at least 20 degrees Celsius higher than a flash point of the first liquid solvent alone, a flash point higher than 150° C., or no detectable flash point. A battery using such a separator-electrolyte is non-flammable and safe, has a long cycle life, high capacity, and high energy density.

First claim

The invention claimed is:

1. A process for producing a separator-electrolyte layer for use in a lithium battery, said process comprising:
(a) providing a porous thin-film separator, wherein said porous thin-film separator has a thickness of less than 500 μm and has pores that allow for lithium ion migration;
(b) providing a non-flammable quasi-solid electrolyte containing a lithium salt dissolved in a first liquid solvent at a first concentration greater than 7 M (mole/L); and
(c) coating or impregnating said porous thin-film separator with said non-flammable quasi-solid electrolyte to obtain said separator-electrolyte layer with a final lithium salt concentration equal to or greater than said first concentration, wherein the ions of the lithium salt retain or capture molecules of the first liquid solvent to a degree that results in supersaturation of the non-flammable quasi-solid electrolyte without precipitation or crystallization of said lithium salt so that said non-flammable quasi-solid electrolyte exhibits a vapor pressure of less than 0.01 kPa when measured at 20° C., a vapor pressure of less than 60% of the vapor pressure of said first liquid solvent alone, a flash point of at least 20° C. higher than a flash point of said first liquid solvent alone, a flash point higher than 150° C., or no detectable flash point.

2. The process of claim 1 , wherein said final lithium salt concentration is greater than 8.5 M.

3. The process of claim 1 , wherein said step (c) comprises removing a portion of said first liquid solvent so that the final lithium salt concentration is greater than said first concentration.

4. The process of claim 1 , wherein said electrolyte has a lithium ion transference number greater than 0.4.

5. The process of claim 1 , wherein said electrolyte has a lithium ion transference number greater than 0.6.

6. The process of claim 1 , wherein said electrolyte has a lithium ion transference number greater than 0.7.

7. The process of claim 1 , wherein said first liquid solvent is selected from the group consisting of 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, sulfolane, ethylene carbonate (EC), dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), gamma-butyrolactone (γ-BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene, methyl acetate (MA), fluoroethylene carbonate (FEC), vinylene carbonate (VC), allyl ethyl carbonate (AEC), a hydrofluoroether, a room-temperature ionic liquid solvent, and combinations thereof.

8. The process of claim 7 , wherein said room-temperature ionic liquid solvent has a cation selected from tetraalkylammonium, di-, tri-, or tetra-alkylimidazolium, alkylpyridinium, dialkyl-pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, trialkylsulfonium, or a combination thereof.

9. The process of claim 7 , wherein said room-temperature ionic liquid solvent has an anion selected from BF 4 − , B(CN) 4 − , CH 3 BF 3 − , CH 2 CHBF 3 − , CF 3 BF 3 − , C 2 F 5 BF 3 − , n-C 3 F 7 BF 3 − , n-C 4 F 9 BF 3 − , PF 6 − , CF 3 CO 2 − , CF 3 SO 3 − , N(SO 2 CF 3 ) 2 − , N(COCF 3 )(SO 2 CF 3 ) − , N(SO 2 F) 2 − , N(CN) 2 − , C(CN) 3 − , SCN − , SeCN − , CuCl 2 − , AlCl 4 − , F(HF) 2.3 − , or a combination thereof.

10. The process of claim 1 , wherein said lithium salt 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, lithium bisperfluoro-ethysulfonylimide (LiBETI), lithium bis(trifluoromethanesulphonyl)imide, lithium bis(fluorosulphonyl)imide, lithium trifluoromethanesulfonimide (LiTFSI), an ionic liquid lithium salt, or a combination thereof.

11. The process of claim 1 , wherein said electrolyte contains a mixture of an organic liquid solvent and an ionic liquid solvent.

12. The process of claim 11 , wherein said ionic liquid solvent is selected from a room temperature ionic liquid having a cation selected from tetraalkylammonium, di-, tri-, or tetra-alkylimidazolium, alkylpyridinium, dialkyl-pyrrolidinium, dialkylpiperidinium, tetraalkylphosphonium, trialkylsulfonium, or a combination thereof.

13. The process of claim 11 , wherein said ionic liquid solvent is selected from a room temperature ionic liquid having an anion selected from BF 4 − , B(CN) 4 − , CH 3 BF 3 − , CH 2 CHBF 3 − , CF 3 BF 3 − , C 2 F 5 BF 3 − , n-C 3 F 7 BF 3 − , n-C 4 F 9 BF 3 − , PF 6 − , CF 3 CO 2 − , CF 3 SO 3 − , N(SO 2 CF 3 ) 2 − , N(COCF 3 )(SO 2 CF 3 ) − , N(SO 2 F) 2 − , N(CN) 2 − , C(CN) 3 − , SCN − , SeCN − , CuCl 2 − , AlCl 4 − , F(HF) 2.3 − , or a combination thereof.

14. The process of claim 1 , wherein said electrolyte contains a mixture of an organic liquid solvent and an ionic liquid solvent and an ionic liquid solvent-to-organic liquid solvent weight ratio is greater than 1/1.

15. The process of claim 1 , said process being a roll-to-roll process wherein step (a) entails continuously or intermittently feeding said porous thin-film separator from a feeder roller and step (c) entails collecting said separator-electrolyte layer on a winding roller.

16. The process of claim 1 , said process being a roll-to-roll process wherein step (a) entails continuously or intermittently feeding a porous thin-film separator sheet from a feeder roller, step (b) entails depositing said non-flammable quasi-solid electrolyte onto one or two primary surface(s) of said porous thin-film separator sheet or impregnating pores of said porous thin-film separator sheet with said non-flammable quasi-solid electrolyte to form said separator-electrolyte layer, and step (c) entails collecting said separator-electrolyte layer on a winding roller.

17. The process of claim 16 , wherein step (b) entails spraying and depositing said lithium salt and said first liquid solvent concurrently or sequentially onto one or two primary surface(s) of said porous thin-filmed separator sheet to form said separator-electrolyte layer.

18. The process of claim 16 , wherein step (b) includes a further step of removing a portion of said first liquid solvent to increase a lithium salt concentration of the non-flammable quasi-solid electrolyte.

19. The process of claim 1 , wherein said first liquid solvent contains a mixture of a volatile organic solvent and an ionic liquid or a less volatile organic solvent.

20. The process of claim 19 , wherein said volatile organic solvent contains an ether-type solvent selected from 1,3-dioxolane (DOL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethylether (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), diethylene glycol dibutyl ether (DEGDBE), 2-ethoxyethyl ether (EEE), sulfone, or sulfolane.

21. The process of claim 1 , wherein said porous thin-film separator is selected from a porous polymer film, a porous mat, fabric, paper made of polymer or glass fibers, or a combination thereof.

22. A process for producing

Assignees

• He Hui
• Jang Bor Z
• Wang Yanbo
• Zhamu Aruna
• Nanotek Instruments Inc

Inventors

• He Hui
• Jang Bor Z
• Wang Yanbo
• Zhamu Aruna

Classifications

• H01M2/162

  Electricity · mapped topic

• H01M10/0568

  characterised by the solutes · CPC title

• H01M10/0566 Primary

  Liquid materials · CPC title

• H01M2/145

  Electricity · mapped topic

• H01M2300/0028

  characterised by the solvent · CPC title