Redox mediators for metal-sulfur batteries

Patent metadata

Field	Value
Publication number	US-2017222226-A1
Application number	US-201515502479-A
Country	US
Kind code	A1
Filing date	Aug 11, 2015
Priority date	Aug 11, 2014
Publication date	Aug 3, 2017
Grant date	—

Abstract

Metal-sulfur energy storage devices also comprising new redox mediator compounds are described.

First claim

What is claimed is:

1 . An energy storage device comprising:
an anode; a cathode comprising:
a metal sulfide M x S y , wherein M is a metal, subscript x is from 0 to 2 and y is from 1 to 8,
a redox mediator having a redox potential suitable for reducing or oxidizing M x S y , and
an electrolyte,
a membrane separator between the anode and the cathode; and a current collector in electrical contact with the anode and cathode.

2 . The energy storage device of claim 1 , wherein the anode comprises lithium.

3 . The energy storage device of claim 1 , wherein the metal M is selected from the group consisting of an alkali metal, an alkali earth metal, and a transition metal.

4 . The energy storage device of claim 1 , wherein the metal M is lithium.

5 . The energy storage device of claim 1 , wherein the metal sulfide comprises at least one of Li 2 S 8 and Li 2 S 6 .

6 . The energy storage device of claim 1 , wherein the redox mediator is a polycyclic aromatic hydrocarbon redox mediator.

7 . The energy storage device of claim 1 , wherein the redox mediator is a perylene bisimide (PBI) or a benzoperyleneimide (BPI).

8 . The energy storage device of claim 1 , wherein
the redox mediator is a compound of Formula I:

wherein
each R 1 and R 2 is independently selected from the group consisting of halogen, C 1-20 alkyl, C 1-20 haloalkyl, C 1-20 alkoxy, C 1-20 heteroalkyl, C 3-20 carbocycle, C 3-20 heterocycle, C 6-20 aryl, C 5-20 heteroaryl, —N(R 3 )(R 4 ), —OR 3 , —C(O)R 3 , —C(O)OR 3 , —OC(O)R 3 , —C(O)N(R 3 )(R 4 ), —N(R 3 )C(O)R 4 , —N(R 3 )C(O)N(R 4 )(R 5 ), —OC(O)N(R 4 )(R 5 ), —N(R 3 )C(O)OR 4 , —SR 3 , —S(O)R 3 , —S(O) 2 R 3 , —N 3 , —B(OR 3 ) 2 , and —SeR 3 ;
alternatively, two R 1 or R 2 groups on adjacent ring atoms can be combined to form —O(CH 2 CH 2 ) m O—, wherein subscript m is an integer from 3 to 10;
each R 3 , R 4 and R 5 is independently selected from the group consisting of H and C 1-20 alkyl; and
each subscript n is from 1 to 5.

9 . The energy storage device of claim 1 , wherein
the redox mediator is a compound of Formula II:

wherein
each R 1 is independently selected from the group consisting of halogen, C 1-20 alkyl, C 1-20 haloalkyl, C 1-20 alkoxy, C 1-20 heteroalkyl, C 3-20 carbocycle, C 3-20 heterocycle, C 6-20 aryl, C 5-20 heteroaryl, —N(R 3 )(R 4 ), —OR 3 , —C(O)R 3 , —C(O)OR 3 , —OC(O)R 3 , —C(O)N(R 3 )(R 4 ), —N(R 3 )C(O)R 4 , —N(R 3 )C(O)N(R 4 )(R 5 ), —OC(O)N(R 4 )(R 5 ), —N(R 3 )C(O)OR 4 , —SR 3 , —S(O)R 3 , —S(O) 2 R 3 , —N 3 , —B(OR 3 ) 2 , and —SeR 3 ;
alternatively, two R 1 groups on adjacent ring atoms can be combined to form —O(CH 2 CH 2 ) m O—, wherein subscript m is an integer from 3 to 10;
each R 3 , R 4 and R 5 is independently selected from the group consisting of H and C 1-20 alkyl; and
subscript n is from 1 to 5.

10 . The energy storage device of claim 1 , wherein
the electrolyte comprises a metal salt.

11 . The energy storage device of claim 10 , wherein
the cation of the metal salt is selected from the group consisting of lithium and sodium; and the anion of the metal salt is selected from the group consisting of bis(trifluoromethyl)sulfonimide, trifluoromethylsulfonate, fluorosulfonimide, perchlorate, tetrafluoroborate, hexafluorophosphate, nitrate, fluoride, chloride, bromide, and iodide.

12 . The energy storage device of claim 1 , wherein
the electrolyte comprises at least one of diglyme, PGMEA, dimethoxyethane, triglyme, tetraglyme, dioxolane, THF, propylene carbonate, dimethylcarbonate, ethylene carbonate, ethyl methyl sulfone (EMS), propyl methyl sulfone (PMS), water, poly(ethylene oxide) and copolymers thereof, dimethylsulfoxide, N-methylpyrrolidinone, and acetonitrile.

13 . The energy storage device of claim 1 , wherein the cathode further comprises a conductive additive.

14 . The energy storage device of claim 13 , wherein the conductive additive comprises carbon.

15 . The energy storage device of claim 1 , wherein the current collector comprises at least one of carbon cloth, carbon felt, carbon paper, carbon particles, carbon nanomaterial, metal chalcogenide, metal, and metal oxide.

16 . The energy storage device of claim 1 , comprising:
the anode comprising lithium; the cathode comprising:
Li 2 S 8 ,
the redox mediator having the structure:

diglyme,
lithium bis(trifluoromethyl)sulfonimide, and
lithium nitrate;

the membrane separator; and
the current collector.

17 . The energy storage device of claim 1 , comprising:
the anode comprising lithium; the cathode comprising:
Li 2 S 8 ,
the redox mediator having the structure:

and
diglyme, lithium bis(trifluoromethyl)sulfonimide, and lithium nitrate;
the membrane separator; and
the current collector.

18 . A compound of Formula I:

wherein
each R 1 and R 2 is independently selected from the group consisting of halogen, C 1-20 alkyl, C 1-20 haloalkyl, C 1-20 alkoxy, C 1-20 heteroalkyl, C 3-20 carbocycle, C 3-20 heterocycle, C 6-20 aryl, C 5-20 heteroaryl, —N(R 3 )(R 4 ), —OR 3 , —C(O)R 3 , —C(O)OR 3 , —OC(O)R 3 , —C(O)N(R 3 )(R 4 ), —N(R 3 )C(O)R 4 , —N(R 3 )C(O)N(R 4 )(R 5 ), —OC(O)N(R 4 )(R 5 ), —N(R 3 )C(O)OR 4 , —SR 3 , —S(O)R 3 , —S(O) 2 R 3 , —N 3 , —B(OR 3 ) 2 , and —SeR 3 ;
alternatively, two R 1 or R 2 groups on adjacent ring atoms can be combined to form —O(CH 2 CH 2 ) m O—, wherein subscript m is an integer from 3 to 10;
each R 3 , R 4 and R 5 is independently selected from the group consisting of H and C 1-20 alkyl; and
each subscript n is from 1 to 5.

19 . The compound of claim 18 , wherein
each R 1 and R 2 is —O—(CH 2 CH 2 O) 2 CH 3 ; and each subscript n is 3.

20 . The compound of claim 18 , having the structure:

21 . A compound of Formula II:

wherein
each R 1 is independently selected from the group consisting of halogen, C 1-20 alkyl, C 1-20 haloalkyl, C 1-20 alkoxy, C 1-20 heteroalkyl, C 3-20 carbocycle, C 3-20 heterocycle, C 6-20 aryl, C 5-20 heteroaryl, —N(R 3 )(R 4 ), —OR 3 , —C(O)R 3 , —C(O)OR 3 , —OC(O)R 3 , —C(O)N(R 3 )(R 4 ), —N(R 3 )C(O)R 4 , —N(R 3 )C(O)N(R 4 )(R 5 ), —OC(O)N(R 4 )(R 5 ), —N(R 3 )C(O)OR 4 , —SR 3 , —S(O)R 3 , —S(O) 2 R 3 , —N 3 , —B(OR 3 ) 2 , and —SeR 3 ;
alternatively, two R 1 groups on adjacent ring atoms can be combined to form —O(CH 2 CH 2 ) m O—, wherein subscript m is an integer from 3 to 10;
each R 3 , R 4 and R 5 is independently selected from the group consisting of H and C 1-20 alkyl; and
subscript n is from 1 to 5.

Assignees

• Univ California
• The Massachusetts Inst Of Tech

Inventors

• Helms Brett A
• Frischmann Peter D
• Chiang Yet-Ming
• Fan Frank Y
• Doris Sean E
• Gerber Laura C H

Classifications

• C07D471/06

  Peri-condensed systems · CPC title

• H01M2300/0028

  characterised by the solvent · CPC title

• H01M4/5815

  Sulfides · CPC title

• H01M4/62 Primary

  Selection of inactive substances as ingredients for active masses, e.g. binders, fillers · CPC title

• H01M4/382

  Lithium (H01M4/405 takes precedence) · CPC title