IP Library Granted Patent US 11,955,636
Granted Patent B2
US 11,955,636 · App. 17/477,828 · Granted Apr 9, 2024

Rechargeable lithium sulfur and/or selenium battery

Inventors: Matthew Li (Chicago, IL); Khalil Amine (Oakbrook, IL); Jun Lu (Naperville, IL)
Assignee: UCHICAGO ARGONNE, LLC
H01M4/5815H01M10/0525H01M10/0569H01M2004/027H01M2004/028H01M4/133H01M4/134H01M4/625H01M4/661H01M2300/0028
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Quick Facts
Patent No.
US 11,955,636
App. No.
17/477,828
Granted
Apr 9, 2024
Kind
B2
Abstract

An electrochemical device includes a cathode comprising a first cathode component of lithium and Se x S y ; and a second cathode component of an alkali metal and/or alkaline earth metal sulfur and/or selenide, different from the first cathode component; an initial discharge product of a polyselenide and/or polysulfide anion charge compensated by an alkali metal and/or alkaline earth metal cation; an anode; a porous separator; and a non-aqueous electrolyte with one or more lithium salts, and one or more solvents; wherein the electrochemical device is a lithium sulfur and/or lithium selenide battery.

Claims (29)

1. An electrochemical device comprising:

a cathode comprising:

a first cathode component comprising lithium and Se x S y , wherein x+y=1, 0≤x≤1, and 0≤y≤1; and

a second cathode component comprising sodium sulfide, sodium selenide, or a mixture thereof;

an anode;

a porous separator; and

a non-aqueous electrolyte comprising one or more lithium salts, and one or more aprotic solvents;

wherein:

the electrochemical device is a lithium sulfur and/or lithium selenide battery.

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

3. The electrochemical device of claim 1 , wherein the anode is lithium free.

4. The electrochemical device of claim 1 which is an as-prepared device.

5. The electrochemical device of claim 1 further comprising an initial discharge product comprising a polyselenide and/or polysulfide anion compensated by an alkali metal and/or alkaline earth metal cation.

6. The electrochemical device of claim 1 , wherein the lithium salt comprises a lithium alkyl fluorophosphate; a lithium alkyl fluoroborate; lithium 4,5-dicyano-2-(trifluoromethyl)imidazole; lithium 4,5-dicyano-2-methylimidazole; trilithium 2,2′, 2″-tris(trifluoromethyl)benzotris(imidazolate); LiN(CN) 2 ; Li[SO 3 CF 3 ]; Li[CF 3 CO 2 ]; Li[C 2 F 5 CO 2 ]; Li[CH 3 SO 3 ]; Li[N(SO 2 CF 3 ) 2 ]; Li[N(SO 2 F) 2 ]; Li[C(CF 3 SO 2 ) 3 ]; Li[N(SO 2 C 2 F 5 ) 2 ]; LiClO 4 ; LiBF 4 ; LiAlCl 4 ; LiPF 6 ; Li 2 SO 4 ; LiOH; Li[BF 2 (C 2 O 4 )]; Li[B(C 2 O 4 ) 2 ]; Li[PF 2 (C 2 O 4 ) 2 ]; Li[PF 4 (C 2 O 4 )]; LiAsF 6 ; LiSbF 6 ; LiNO 3 ; Li 2 (B 12 X 12 -pHp); Li 2 (B 10 X 10 -pHp); or a mixture of any two or more thereof, wherein X is independently at each occurrence F, Cl, Br, or I, p is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and p′ is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

7. The electrochemical device of claim 1 , wherein the lithium salt comprises Li[N(SO 2 CF 3 ) 2 ], LiNO 3 , or a mixture thereof.

8. The electrochemical device of claim 1 , wherein a ratio of the first cathode component to the second cathode component is from 80 to 10.

9. The electrochemical device of claim 1 , wherein a ratio of lithium to sodium is from 80 to 10.

10. The electrochemical device of claim 1 , wherein the aprotic solvent comprises an ether.

11. The electrochemical device of claim 10 , wherein the ether is dimethoxyethane (DME), 1,3 dioxolane (DOL), diethylene glycol dimethyl ether (DEGDME), triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether (TEGDME), or a mixture of any two or more thereof.

12. The electrochemical device of claim 1 , wherein the cathode, prior to a first discharge charge cycle, is free of polysulfide anion, polyselenide anion, elemental sulfur, and elemental selenium.

13. The electrochemical device of claim 1 which is configured to, after a first charge cycle, comprise elemental sulfur.

14. The electrochemical device of claim 1 , wherein the anode comprises lithium, lithiated carbon, lithiated tin, lithiated silicon, sodium, sodiated carbon, sodiated tin, sodiated silicon, potassium, potassiated carbon, potassiated tin, potassiated silicon, magnesium, magnesiated carbon, magnesiated tin, magnesiated silicon, zinc, zincated carbon, zincated tin, zincated silicon, or a mixture of any two or more thereof.

15. The electrochemical device of claim 1 , wherein the anode further comprises a current collector, a conductive carbon material, a binder, or any combination thereof.

16. The electrochemical device of claim 1 , wherein the porous separator comprises a glass fiber material, a carbon fiber material, polyethylene, solid state membranes, or a combination of any two or more thereof.

17. The electrochemical device of claim 1 , wherein the cathode further comprises:

a current collector comprising copper, stainless steel, or titanium; and

a conductive carbon material comprising synthetic graphite, natural graphite, expanded graphite, graphene, reduced graphene oxide, a metal-organic framework, amorphous carbon, hard carbon, soft carbon, carbon black, acetylene black, carbon spheres, mesocarbon microbeads (MCMB), mesoporous carbon, porous carbon matrix, carbon nanofiber, carbon aerogel, single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanotube arrays, or a mixture of any two or more thereof.

18. A process of charging the electrochemical device of claim 1 , the process comprising: applying a first charging current to the electrochemical device in an as-assembled, uncharged state to form polysulfide and/or polyselenide anions within the electrolyte.

19. The process of claim 18 , wherein upon further application of the first charging current, elemental sulfur is formed.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 10, 2023
From: AMINE, KHALIL
To: UCHICAGO ARGONNE, LLC
Reel/Frame 065522/0171 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 10, 2023
From: LI, MATTHEW
To: UCHICAGO ARGONNE, LLC
Reel/Frame 065538/0482 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 10, 2023
From: LU, JUN
To: UCHICAGO ARGONNE, LLC
Reel/Frame 065538/0550 →
CONFIRMATORY LICENSE Recorded Apr 19, 2022
From: UCHICAGO ARGONNE, LLC
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 059637/0894 →
Continuity (2)
Provisional Application 63082520 · Sep 24, 2020
Related Publication 20220123312A1 · Apr 21, 2022