Solid electrolyte interphase (sei) application on anode of fluoride ion/shuttle batteries

Patent metadata

Field	Value
Publication number	US-2020185776-A1
Application number	US-201916702327-A
Country	US
Kind code	A1
Filing date	Dec 3, 2019
Priority date	Dec 5, 2018
Publication date	Jun 11, 2020
Grant date	—

Abstract

The present disclosure is directed to fluoride (F) ion batteries and F shuttle batteries comprising an anode with a solid electrolyte interphase (SEI) layer, a cathode comprising a core shell structure, and a liquid fluoride battery electrolyte. According to some aspects, the components therein enable discharge and recharge at room-temperature.

First claim

What is claimed is:

1 . A fluoride ion battery comprising:
a liquid electrolyte comprising fluoride ions; an anode containing an alkali earth metal, a rare earth metal, or combinations thereof, and having an outer solid electrolyte interphase layer in contact with the electrolyte; and a cathode containing:
a core-shell particle having a transition metal core and a shell at least partially surrounding the transition metal core, the shell in contact with the electrolyte, or
a metal nanostructure core including at least one dimension that is less than or equal to 20 nm, and a shell at least partially surrounding the core.

2 . The fluoride ion battery of claim 1 , wherein the liquid electrolyte comprises bis(2-methoxyethyl) ether, bis(2,2,2-trifluoroethyl) ether, N,N,N-trimethyl-N-neopentylammonium fluoride, N,N-dimethyl-N,N-dineopentylammonium fluoride, propionitrile, or combinations thereof.

3 . The fluoride ion battery of claim 1 , wherein the alkali earth metal is calcium, and the rare earth metal is selected from cerium and lanthanum.

4 . The fluoride ion battery of claim 1 , wherein the transition metal core comprises bismuth, lead, copper, or combinations thereof.

5 . The fluoride ion battery of claim 1 , wherein the outer solid electrolyte interphase layer is covalently attached to the anode, the outer solid electrolyte interphase layer comprising CF 3 (CF 2 ) 5 CH 2 , CF 3 (CF 2 ) 2 CH 2 , para-tert-butylphenyl, para-methoxyphenyl, para-(dimethylamino) phenyl, para-nitrophenyl, para-trifluoromethylphenyl, or combinations thereof.

6 . The fluoride ion battery of claim 1 , wherein the outer solid electrolyte interphase layer comprises 1H, 1H,2H,2H-perfluorooctyltriethoxysilane; 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene; 4-tert-butylbenzene diazonium salt; 4-methoxybenzene diazonium salt; 4-(dimethylamino)benzene diazonium salt; 4-nitrobenzene diazonium salt; 4-trifluoromethylbenzene diazonium salt, or combinations thereof.

7 . The fluoride ion battery of claim 6 , wherein the outer solid electrolyte interphase layer is a film on the anode, and the 4-tert-butylbenzenediazonium salt; 4-methoxybenzene diazonium salt; 4-(dimethylamino)benzene diazonium salt; 4-nitrobenzene diazonium salt; 4-trifluoromethyl benzene diazonium salt, or combinations thereof further comprise a salt counter anion comprising BF 4 − , F − , Cl − , PF 6 − , CF 3 SO 3 − , [(CF 3 SO 2 ) 2 N]−, or a combination thereof.

8 . The fluoride ion battery of claim 1 , wherein the transition metal core comprises copper and the shell comprises LaF 3 .

9 . The fluoride ion battery of claim 1 , wherein the shell comprises a thickness from about 2 nm to about 5 nm.

10 . The fluoride ion battery of claim 1 , wherein the transition metal core has at least one dimension less than or equal to about 20 nm.

11 . A method of making a fluoride ion battery, said method comprising:
providing a liquid electrolyte comprising an additive; providing a working electrode comprising an alkali earth metal, a rare earth metal, or combinations thereof in contact with the electrolyte; providing a counter electrode in contact with the electrolyte; varying the voltage potential between the working electrode and the counter electrode between a first potential and a second potential for a number of cycles until the additive forms an outer solid electrolyte interphase layer on the working electrode, the second potential being higher than the first potential.

12 . The method of claim 11 , wherein the liquid electrolyte comprises bis(2-methoxyethyl) ether, bis(2,2,2-trifluoroethyl) ether, N,N,N-trimethyl-N-neopentylammonium fluoride, propionitrile, N,N-dimethyl-N,N-dineopentylammonium fluoride, or combinations thereof.

13 . The method of claim 11 , wherein the first potential is about −0.8V and the second potential is about +0.7 V vs Li + /Li, the number of cycles is up to five, and the additive comprises 1H, 1H,2H,2H-perfluorooctyltriethoxy-silane, 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene, or combinations thereof.

14 . The method of claim 11 , wherein the first potential is about −1.0V and the second potential is about +0.8 V vs. Li + /Li, the number of cycles is up to 20, and the additive is selected from the group consisting of 4-tert-butylbenzene diazonium salt; 4-methoxybenzenediazonium salt; 4-(dimethylamino)benzene diazonium salt; 4-nitrobenzene diazonium salt; 4-trifluoromethylbenzene diazonium salt, variants thereof, or combinations thereof.

15 . The method of claim 11 , wherein the working electrode comprises calcium, cerium, lanthanum, or combinations thereof.

16 . A method of making a cathode for a fluoride ion battery, the method comprising:
providing a solid transition metal; treating the solid transition metal with lanthanum and fluorine to form a LaF 3 shell at least partially surrounding the solid transition metal.

17 . The method of claim 16 , wherein the treating comprises dispersing the solid transition metal in an aqueous solution of hydrazine hydrate and contacting the solid transition metal with an aqueous solution of lanthanum ions and fluoride ions.

18 . The method of claim 17 , wherein the aqueous solution of lanthanum ions and fluoride ions comprises lanthanum nitrate hexahydrate and sodium fluoride.

19 . The method of claim 16 , wherein the treating comprises radio frequency sputtering of LaF 3 onto the solid transition metal.

20 . The method of claim 16 , wherein the solid transition metal comprises bismuth, lead, copper, or combinations thereof.

Assignees

• Honda Motor Co Ltd
• California Inst Of Techn

Inventors

• Xu Qingmin
• Brooks Christopher J
• Omichi Kaoru
• Jones Simon
• Davis Victoria
• Munoz Stephen
• Kim Jeongmin
• Billings Keith
• Miller Iii Thomas
• Grubbs Robert H
• Wolf William

Classifications

• Y02P70/50

  Manufacturing or production processes characterised by the final manufactured product · CPC title

• H01M2300/0037

  Mixture of solvents · CPC title

• H01M2300/0034

  Fluorinated solvents · CPC title

• H01M10/0568

  characterised by the solutes · CPC title

• H01M10/05 Primary

  Accumulators with non-aqueous electrolyte (H01M10/39 takes precedence) · CPC title