IP Library Granted Patent US 10,892,524
Granted Patent B2
US 10,892,524 · App. 16/089,587 · Granted Jan 12, 2021

Electrolyte for rechargeable electrochemical cell

Inventors: George W. Adamson (Edison, NJ); Sara S. Bowers (Edison, NJ); Francis W. Richey (Brooklyn, NY)
Assignee: Eos Energy Storage, LLC
H01M10/365H01M2300/00H01M2300/0005H01M2300/0091
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Quick Facts
Patent No.
US 10,892,524
App. No.
16/089,587
Granted
Jan 12, 2021
Kind
B2
Abstract

The present invention provides an aqueous electrolyte for use in rechargeable zinc-halide storage batteries that possesses improved stability and durability and improves zinc-halide battery performance (e.g., energy efficiency, Coulombic efficiency, and/or the like). One aspect of the present invention provides an electrolyte for use in a secondary zinc bromine electrochemical cell comprising from about 30 wt % to about 40 wt % of ZnBr 2 by weight of the electrolyte; from about 5 wt % to about 15 wt % of KBr; from about 5 wt % to about 15 wt % of KCl; and one or more quaternary ammonium agents, wherein the electrolyte comprises from about 0.5 wt % to about 10 wt % of the one or more quaternary ammonium agents.

Claims (67)

1. An electrolyte for use in a secondary static zinc halide electrochemical cell comprising:

from about 30.00 wt % to about 50.00 wt % of ZnBr 2 ;

from about 22.50 wt % to about 40.00 wt % of H 2 O;

from about 3.00 wt % to about 9.50 wt % of KBr;

from about 7.75 wt % to about 14.00 wt % of KCl;

from about 0.25 wt % to about 2.25 wt % of MPEG 2K; and

from about 0.075 wt % to about 1.25 wt % of MPEG 1K.

2. The electrolyte of claim 1 , further comprising

at least two different quaternary ammonium agents, wherein the at least two different quaternary ammonium agents are of a formula N + (R A )(R B ) 3 X − , wherein R A is a C 1-6 alkyl, R B is a C 1-6 alkyl, and X − is Br − or Cl − ; and

wherein an aggregate concentration of the at least two different quaternary ammonium agents is from about 3.50 wt % to about 20.00 wt %.

3. The electrolyte of claim 2 , wherein one of the at least two different quaternary ammonium agents is tetraethylammonium bromide, and the tetraethylammonium bromide has a concentration of from about 0.35 wt % to about 3.75 wt %.

4. The electrolyte of claim 2 , wherein one of the at least two different quaternary ammonium agents is triethylmethylammonium chloride, and the triethylmethylammonium chloride has a concentration of from about 3.50 wt % to about 15.0 wt %.

5. The electrolyte of claim 1 , further comprising a quaternary ammonium agent of trimethylpropylammonium bromide, and the trimethylpropylammonium bromide has a concentration of from about 0.25 wt % to about 0.75 wt %.

6. The electrolyte of claim 1 , further comprising from about 0.35 wt % to about 2.75 wt % of a glycol, wherein the glycol is selected from ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, hexalene glycol, or any combination thereof.

7. The electrolyte of claim 1 , further comprising from about 2.00 wt % to about 4.00 wt % of a glyme, wherein the glyme is selected from monoglyme, diglyme, triglyme, tetraglyme, pentaglyme, hexaglyme, or any combination thereof.

8. An electrolyte for use in a secondary static zinc halide electrochemical cell comprising:

from about 30.00 wt % to about 50.00 wt % of ZnBr 2 ;

from about 22.50 wt % to about 40.00 wt % of H 2 O;

from about 3.00 wt % to about 9.50 wt % of KBr;

from about 7.75 wt % to about 14.00 wt % of KCl;

from about 0.25 wt % to about 2.25 wt % of MPEG 2K;

from about 0.075 wt % to about 1.25 wt % of MPEG 1K; and

from about 0.50 wt % to about 3.50 wt % of a first quaternary ammonium agent,

wherein the first quaternary ammonium agent is selected from a tetra-C 1-6 alkyl ammonium chloride or a tetra-C 1-6 alkyl ammonium bromide.

9. The electrolyte of claim 8 , wherein the first quaternary ammonium agent is selected from tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, or tetrabutylammonium bromide.

10. The electrolyte of claim 8 , further comprising a second quaternary ammonium agent wherein the second quaternary ammonium agent has a formula N + (R A )(R B ) 3 X − , wherein R A is a C 1-6 alkyl, R B is a C 1-6 alkyl different from R A , and X − is Br − or Cl − ; and

wherein a concentration of the second quaternary ammonium agent is from about 3.50 wt % to about 15.00 wt %.

11. The electrolyte of claim 10 , wherein the second quaternary ammonium agent is selected from a chloride or bromide of trimethylethylammonium, trimethyl propylammonium, trimethylbutylammonium, triethylmethylammonium, triethylpropylammonium, triethylbutylammonium, tripropylmethylammonium, tripropylethylammonium, or tripropylbutylammonium.

12. The electrolyte of claim 10 , further comprising a third quaternary ammonium agent, wherein the third quaternary ammonium agent has a formula N + (R A )(R B ) 3 X − , wherein R A is a C 1-6 alkyl, R B is a C 1-6 alkyl different from R A , and X − is Br − or Cl − ;

the third quaternary ammonium agent is different than the second quaternary ammonium agent; and

wherein a concentration of the third quaternary ammonium agent is from about 0.25 wt % to about 0.85 wt %.

13. The electrolyte of claim 12 , wherein the third quaternary ammonium agent is selected from a chloride or bromide of trimethylethylammonium, trimethyl propylammonium, trimethylbutylammonium, triethylmethylammonium, triethylpropylammonium, triethylbutylammonium, tripropylmethylammonium, tripropylethylammonium, or tripropylbutylammonium.

14. The electrolyte of claim 8 , further comprising from about 0.35 wt % to about 2.75 wt % of a glycol, wherein the glycol is selected from ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, hexalene glycol, or any combination thereof.

15. The electrolyte of claim 8 , further comprising from about 2.00 wt % to about 4.00 wt % of a glyme, wherein the glyme is selected from monoglyme, diglyme, triglyme, tetraglyme, pentaglyme, hexaglyme, or any combination thereof.

16. An electrolyte for use in a secondary static zinc halide electrochemical cell comprising:

from about 30.00 wt % to about 50.00 wt % of ZnBr 2 ;

from about 22.50 wt % to about 40.00 wt % of H 2 O;

from about 3.00 wt % to about 9.50 wt % of KBr;

from about 7.75 wt % to about 14.00 wt % of KCl;

from about 0.25 wt % to about 2.25 wt % of MPEG 2K;

from about 0.075 wt % to about 1.25 wt % of MPEG 1K; and

one or more quaternary ammonium agents, wherein each quaternary ammonium agent is independently selected from a quaternary ammonium agent having a formula N + (R A )(R B ) 3 X − , wherein R A is a C 1-6 alkyl, R B is a C 1-6 alkyl, and X − is Br − or Cl − , and

wherein the one or more quaternary ammonium agents has an aggregate concentration of from about 3.50 wt % to about 20.00 wt %.

17. The electrolyte of claim 16 , wherein the one or more quaternary ammonium agents comprises a first quaternary ammonium agent with a concentration from about 0.50 wt % to about 3.50 wt %, wherein the first quaternary ammonium agent is selected from a tetra-C 1-6 alkyl ammonium chloride or a tetra-C 1-6 alkyl ammonium bromide.

18. The electrolyte of claim 17 , wherein the first quaternary ammonium agent is selected from tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, or tetrabutylammonium bromide.

19. The electrolyte of claim 17 , wherein the one or more quaternary ammonium agents further comprising a second quaternary ammonium agent wherein the second quaternary ammonium agent has a formula N+(R A )(R B ) 3 X − , wherein R A is a C 1-6 alkyl, R B is a C 1-6 alkyl different from R A , and X − is Br − or Cl − ; and wherein a concentration of the second quaternary ammonium agent is from about 3.50 wt % to about 15.00 wt %.

20. The electrolyte of claim 19 , wherein the second quaternary ammonium agent is selected from a chloride or bromide of trimethylethylammonium, trimethyl propylammonium, trimethylbutylammonium, triethylmethylammonium, triethylpropylammonium, triethylbutylammonium, tripropylmethylammonium, tripropylethylammonium, or tripropylbutylammonium.

21. The electrolyte of claim 20 , wherein the second quaternary ammonium agent is triethylmethylammonium chloride or triethylmethylammonium bromide.

22. The electrolyte of claim 19 , wherein the one or more quaternary ammonium agents further comprising a third quaternary ammonium agent, wherein the third quaternary ammonium agent has a formula N + (R A )(R B ) 3 X − , wherein R A is a C 1-6 alkyl, R B is a C 1-6 alkyl different from R A , and X − is Br − or Cl − ;

the third quaternary ammonium agent is different than the second quaternary ammonium agent; and

wherein a concentration of the third quaternary ammonium agent is from about 0.25 wt % to about 0.85 wt %.

23. The electrolyte of claim 22 , wherein the third quaternary ammonium agent is selected from a chloride or bromide of trimethylethylammonium, trimethylpropylammonium, trimethylbutylammonium, triethylmethylammonium, triethylpropylammonium, triethylbutylammonium, tripropylmethylammonium, tripropylethylammonium, or tripropylbutylammonium.

24. The electrolyte of claim 16 , further comprising from about 0.35 wt % to about 2.75 wt % of a glycol, wherein the glycol is selected from ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, hexalene glycol, or any combination thereof.

25. The electrolyte of claim 16 , further comprising from about 2.00 wt % to about 4.00 wt % of a glyme, wherein the glyme is selected from monoglyme, diglyme, triglyme, tetraglyme, pentaglyme, hexaglyme, or any combination thereof.

26. An electrolyte for use in a secondary static zinc halide electrochemical cell comprising:

from about 30.00 wt % to about 50.00 wt % of ZnBr 2 ;

from about 22.50 wt % to about 40.00 wt % of H 2 O;

from about 3.00 wt % to about 9.50 wt % of KBr;

from about 7.75 wt % to about 14.00 wt % of KCl;

from about 0.25 wt % to about 2.25 wt % of MPEG 2K;

from about 0.075 wt % to about 1.25 wt % of MPEG 1K;

from about 3.50 wt % to about 15.00 wt % of a chloride or a bromide of triethylmethylammonium; and

from about 0.50 wt % to about 3.50 wt % of a chloride or a bromide of tetra-C 1-6 alkyl ammonium.

27. The electrolyte of claim 26 , further comprising from about 0.25 wt % to about 0.75 wt % of a quaternary ammonium agent having a formula N + (R A )(R B ) 3 X − , wherein R A is a C 1-6 alkyl, R B is a C 1-6 alkyl different from R A , and X − is Br − or Cl − ; and the quaternary ammonium agent is not a chloride or bromide of triethylmethylammonium;

wherein the quaternary ammonium agent is selected from a chloride or a bromide of trimethylethvlammonium, trimethylpropylammonium, trimethylbutylammonium, triethylpropylammonium, triethylbutylammonium, tripropylmethylammonium, tripropylethylammonium, or tripropylbutylammonium.

28. The electrolyte of claim 26 , further comprising from about 0.35 wt % to about 2.75 wt % of neopentyl glycol.

29. The electrolyte of claim 26 , further comprising from about 2.00 wt % to about 4.00 wt % of tetraglyme.

Assignments (10)
SECURITY INTEREST Recorded Nov 27, 2024
From: EOS ENERGY TECHNOLOGY HOLDINGS, LLC; EOS ENERGY STORAGE LLC
To: CITIBANK, N.A., AS COLLATERAL AGENT
Reel/Frame 069458/0388 →
TERMINATION AND RELEASE OF PATENT SECURITY AGREEMENT Recorded Jun 24, 2024
From: ACP POST OAK CREDIT I LLC
To: EOS ENERGY STORAGE LLC; EOS ENERGY TECHNOLOGY HOLDINGS, LLC
Reel/Frame 067823/0035 →
SECURITY INTEREST Recorded Jun 24, 2024
From: EOS ENERGY TECHNOLOGY HOLDINGS, LLC; EOS ENERGY STORAGE LLC
To: CCM DENALI DEBT HOLDINGS, LP, AS COLLATERAL AGENT
Reel/Frame 067823/0430 →
CORRECTIVE ASSIGNMENT TO CORRECT THE COVER SHEET US PATENT NO. 7369440 SHOULD HAVE BEEN 7396440 PREVIOUSLY RECORDED ON REEL 048752 FRAME 0864. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY INTEREST. Recorded Jun 15, 2023
From: EOS ENERGY STORAGE, LLC
To: ALTENERGY STORAGE BRIDGE, LLC
Reel/Frame 064021/0102 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Aug 12, 2022
From: EOS ENERGY STORAGE LLC
To: EOS ENERGY TECHNOLOGY HOLDINGS, LLC
Reel/Frame 061161/0750 →
SECURITY INTEREST Recorded Aug 3, 2022
From: EOS ENERGY STORAGE LLC; EOS ENERGY TECHNOLOGY HOLDINGS LLC
To: ACP POST OAK CREDIT I LLC
Reel/Frame 061056/0282 →
RELEASE OF SECURITY INTEREST Recorded May 25, 2022
From: ALTENERGY STORAGE BRIDGE LLC
To: EOS ENERGY STORAGE LLC
Reel/Frame 060178/0097 →
SECURITY INTEREST Recorded Apr 1, 2019
From: EOS ENERGY STORAGE, LLC
To: ALTENERGY STORAGE BRIDGE, LLC
Reel/Frame 048752/0864 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 5, 2019
From: ADAMSON, GEORGE W.; BOWERS, SARA S.
To: EOS ENERGY STORAGE, LLC
Reel/Frame 048235/0581 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 5, 2019
From: RICHEY, FRANCIS W.
To: EOS ENERGY STORAGE, LLC
Reel/Frame 048235/0656 →
Continuity (2)
Continuation In Part 15083558 · Mar 29, 2016
Related Publication 20190131662A1 · May 2, 2019