US2019198881A1PendingUtilityA1

Electrolyte for rechargeable electrochemical cell

67
Assignee: EOS ENERGY STORAGE LLCPriority: Oct 6, 2014Filed: Mar 5, 2019Published: Jun 27, 2019
Est. expiryOct 6, 2034(~8.2 yrs left)· nominal 20-yr term from priority
Inventors:George W. AdamsonSara S. BowersFrancis W. Richey
H01M 12/085H01M 4/364H01M 4/76H01M 4/583H01M 10/0418H01M 4/663H01M 10/365H01M 10/0463H01M 10/056H01M 4/0473H01M 2004/029H01M 4/60H01M 10/38H01M 4/667H01M 2300/0002H01M 8/184H01M 4/661H01M 50/553H01M 50/562H01M 2/30H01M 2/1673H01M 2/1613H01M 50/543H01M 50/44H01M 50/46H01M 50/431Y02P70/50Y02E60/50Y02E60/10H01M 10/044
67
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Claims

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. 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 ZnBr2 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

exact text as granted — not AI-modified
What is claimed is: 
     
         1 . An electrolyte for use in a secondary static zinc halide electrochemical cell comprising:
 an aggregate concentration of from about 2.0 wt % to about 15.0 wt % of one or more quaternary ammonium agents, wherein the one or more quaternary ammonium agents comprises at least cetyltrimethylammonium chloride or cetyltrimethylammonium bromide.   
     
     
         2 . The electrolyte of  claim 1 , further comprising from about 0.2 wt % to about 1.2 wt % of the cetyltrimethylammonium chloride or cetyltrimethylammonium bromide, and at least one additional quaternary ammonium agent. 
     
     
         3 . The electrolyte of  claim 2 , further comprising an alkyl substituted pyridinium chloride or an alkyl substituted pyridinium bromide. 
     
     
         4 . The electrolyte of  claim 3 , further comprising from about 1.8 wt % to about 7.5 wt % of the alkyl substituted pyridinium chloride or the alkyl substituted pyridinium bromide. 
     
     
         5 . The electrolyte of  claim 4 , further comprising from about 2.0 wt % to about 6.0 wt % of the alkyl substituted pyridinium chloride or the alkyl substituted pyridinium bromide. 
     
     
         6 . The electrolyte of  claim 5 , further comprising from about 2.0 wt % to about 6.0 wt % of alkyl substituted pyridinium bromide, wherein the alkyl substituted pyridinium bromide is selected from 1-ethyl-2-methylpyridinium bromide, 1-ethyl-3-methylpyridinium bromide, or 1-ethyl-4-methylpyridinium bromide. 
     
     
         7 . The electrolyte of  claim 6 , further comprising from about 0.05 wt % to about 0.2 wt % of 1,1-dioctadecyl-4-4′bypyridinium chloride or from about 0.05 wt % to about 0.2 wt % of 1,1-dioctadecyl-4-4′bypyridinium bromide. 
     
     
         8 . The electrolyte of  claim 6 , further comprising from about 25 wt % to about 40 wt % of ZnBr 2 . 
     
     
         9 . The electrolyte of  claim 8 , further comprising from about 25 wt % to about 45 wt % of water. 
     
     
         10 . The electrolyte of  claim 9 , further comprising from about 1 wt % to about 5 wt % of KBr. 
     
     
         11 . The electrolyte of  claim 10 , further comprising from about 5 wt % to about 15 wt % of KCl. 
     
     
         12 . The electrolyte of  claim 11 , further comprising from about 0.5 wt % to about 2.5 wt % of an ether selected from DME-PEG, dimethyl ether, or any combination thereof. 
     
     
         13 . The electrolyte according to  claim 12 , wherein the ether is DME-PEG, and the DME-PEG has an average molecular weight of from about 350 amu to about 3000 amu. 
     
     
         14 . The electrolyte according to  claim 13 , wherein the DME-PEG has an average molecular weight of from about 750 amu to about 2500 amu. 
     
     
         15 . The electrolyte according to  claim 14 , wherein the ether is DME-PEG, and the electrolyte comprises from about 0.1 wt % to about 0.5 wt % of DME-PEG having an average molecular weight of from about 750 amu to about 1250 amu. 
     
     
         16 . The electrolyte according to  claim 14 , wherein the ether is DME-PEG, and the electrolyte comprises from about 1.0 wt % to about 2.0 wt % of DME-PEG having an average molecular weight of from about 1750 amu to about 2250 amu. 
     
     
         17 . The electrolyte of  claim 2 , further comprising from about 2 wt % to about 6 wt % of the tetraethylammonium chloride or tetraethylammonium bromide. 
     
     
         18 . The electrolyte of  claim 17 , further comprising from about 2 wt % to about 6 wt % of the tetraethylammonium bromide. 
     
     
         19 . The electrolyte of  claim 18 , further comprising N-ethyl-N-methylmorpholinium chloride or N-ethyl-N-methylmorpholinium bromide. 
     
     
         20 . The electrolyte of  claim 19 , further comprising from about 0.5 wt % to about 2.0 wt % of the N-ethyl-N-methylmorpholinium chloride or N-ethyl-N-methylmorpholinium bromide. 
     
     
         21 . The electrolyte of  claim 20 , further comprising from about 25 wt % to about 40 wt % of ZnBr 2 . 
     
     
         22 . The electrolyte of  claim 21 , further comprising from about 25 wt % to about 45 wt % of water. 
     
     
         23 . The electrolyte of  claim 22 , further comprising from about 2 wt % to about 10 wt % of KBr. 
     
     
         24 . The electrolyte of  claim 23 , further comprising from about 5 wt % to about 15 wt % of KCl. 
     
     
         25 . The electrolyte of  claim 24 , further comprising from about 0.5 wt % to about 2.5 wt % of an ether selected from DME-PEG, dimethyl ether, or any combination thereof. 
     
     
         26 . The electrolyte according to  claim 25 , wherein the ether is DME-PEG, and the DME-PEG has an average molecular weight of from about 350 amu to about 3000 amu. 
     
     
         27 . The electrolyte according to  claim 25 , wherein the DME-PEG has an average molecular weight of from about 750 amu to about 2500 amu. 
     
     
         28 . The electrolyte according to  claim 27 , wherein the ether is DME-PEG, and the electrolyte comprises from about 0.1 wt % to about 0.5 wt % of DME-PEG having an average molecular weight of from about 750 amu to about 1250 amu. 
     
     
         29 . The electrolyte according to  claim 27 , wherein the ether is DME-PEG, and the electrolyte comprises from about 1.0 wt % to about 2.0 wt % of DME-PEG having an average molecular weight of from about 1750 amu to about 2250 amu. 
     
     
         30 . An electrolyte for use in a secondary zinc bromine electrochemical cell comprising:
 from about 25 wt % to about 40 wt % of ZnBr 2 ;   from about 25 wt % to about 45 wt % of water; and   one or more quaternary ammonium agents,   wherein the electrolyte has an aggregate concentration of from about 2.0 wt % to about 15.0 wt % of the one or more quaternary ammonium agents, and wherein the one or more quaternary ammonium agents comprises at least   cetyltrimethylammonium bromide, and   an alkyl substituted pyridinium bromide, wherein the alkyl substituted pyridinium bromide is selected from 1-ethyl-2-methylpyridinium bromide, 1-ethyl-3-methylpyridinium bromide, or 1-ethyl-4-methylpyridinium bromide.   
     
     
         31 . The electrolyte of  claim 30 , further comprising from about 0.2 wt % to about 1.2 wt % of cetyltrimethylammonium bromide and from about 1.8 wt % to about 7.5 wt % of the alkyl substituted pyridinium bromide. 
     
     
         32 . The electrolyte of  claim 31 , further comprising from about 0.05 wt % to about 0.2 wt % of 1,1-dioctadecyl-4-4′bypyridinium chloride or from about 0.05 wt % to about 0.2 wt % of 1,1-dioctadecyl-4-4′bypyridinium bromide. 
     
     
         33 . The electrolyte of  claim 32 , further comprising from about 1 wt % to about 5 wt % of KBr. 
     
     
         34 . The electrolyte of  claim 33 , further comprising from about 5 wt % to about 15 wt % of KCl. 
     
     
         35 . The electrolyte of  claim 34 , further comprising from about 0.1 wt % to about 0.5 wt % of DME-PEG having an average molecular weight of from about 750 amu to about 1250 amu. 
     
     
         36 . The electrolyte of  claim 35 , further comprising from about 1.0 wt % to about 2.0 wt % of DME-PEG having an average molecular weight of from about 1750 amu to about 2250 amu. 
     
     
         37 . The electrolyte of  claim 36 , further comprising an acid, or the conjugate base of an acid, selected from acetic acid, nitric acid, and citric acid. 
     
     
         38 . The electrolyte of  claim 37 , further comprising from about 0.1 wt % to about 1.0 wt % of glacial acetic acid or from about 0.1 wt % to about 1.0 wt % of HBr. 
     
     
         39 . An electrolyte for use in a secondary zinc bromine electrochemical cell comprising:
 from about 25 wt % to about 40 wt % of ZnBr 2 ;   from about 25 wt % to about 45 wt % of water; and   one or more quaternary ammonium agents,   wherein the electrolyte has an aggregate concentration of from about 2.0 wt % to about 15.0 wt % of the one or more quaternary ammonium agents, and wherein the one or more quaternary ammonium agents comprises at least   cetyltrimethylammonium bromide, and   tetraethylammonium bromide.   
     
     
         40 . The electrolyte of  claim 38 , further comprising from about 0.2 wt % to about 1.2 wt % of cetyltrimethylammonium bromide and from about 2.0 wt % to about 6.0 wt % of the tetraethylammonium bromide. 
     
     
         41 . The electrolyte of  claim 40 , wherein the electrolyte further comprises from about 0.5 wt % to about 2.0 wt % of the N-ethyl-N-methylmorpholinium chloride or N-ethyl-N-methylmorpholinium bromide. 
     
     
         42 . The electrolyte of  claim 41 , further comprising from about 1 wt % to about 5 wt % of KBr. 
     
     
         43 . The electrolyte of  claim 42 , further comprising from about 5 wt % to about 15 wt % of KCl. 
     
     
         44 . The electrolyte of  claim 43 , further comprising from about 0.1 wt % to about 0.5 wt % of DME-PEG having an average molecular weight of from about 750 amu to about 1250 amu. 
     
     
         45 . The electrolyte of  claim 44 , further comprising from about 1.0 wt % to about 2.0 wt % of DME-PEG having an average molecular weight of from about 1750 amu to about 2250 amu. 
     
     
         46 . The electrolyte of  claim 45 , further comprising an acid, or the conjugate base of an acid, selected from acetic acid, nitric acid, and citric acid. 
     
     
         47 . The electrolyte of  claim 46 , further comprising from about 0.1 wt % to about 1.0 wt % of glacial acetic acid or from about 0.1 wt % to about 1.0 wt % of HBr. 
     
     
         48 . The electrolyte of  claim 47 , further comprising from about 1.0 wt % to about 5 wt % of a glyme, wherein the glyme is selected from diglyme, triglyme, or tetraglyme. 
     
     
         49 . An electrolyte for use in a secondary zinc bromine electrochemical cell comprising:
 from about 1.0 wt % to about 5 wt % of alkyl ammonium chloride;   from about 25 wt % to about 40 wt % of ZnBr 2 ;   from about 25 wt % to about 45 wt % of water; and   
     
     
         50 . The electrolyte of  claim 49 , wherein the tetra-alkyl ammonium chloride is selected from triethylmethylammonium chloride, trimethylpropylammonium chloride, butyltrimethyl ammonium chloride, tetraethylammonium chloride, trimethylethylammonium chloride, or any combination thereof. 
     
     
         51 . The electrolyte of  claim 50 , wherein the tetra-alkylammonium chloride is triethylmethylammonium chloride 
     
     
         52 . The electrolyte of  claim 49 , further comprising cetyltrimethylammonium bromide or cetyltrimethylammonium chloride. 
     
     
         53 . The electrolyte of  claim 49 , further comprising tetraethylammonium bromide or tetraethylammonium chloride. 
     
     
         54 . The electrolyte of  claim 49 , further comprising from about 0.2 wt % to about 1.2 wt % of cetyltrimethylammonium bromide and from about 1.5 wt % to about 5.0 wt % of the tetraethylammonium bromide. 
     
     
         55 . The electrolyte of  claim 54 , wherein the electrolyte further comprises from about 0.5 wt % to about 2.0 wt % of the N-ethyl-N-methylmorpholinium chloride or N-ethyl-N-methylmorpholinium bromide. 
     
     
         56 . The electrolyte of  claim 55 , further comprising from about 2.5 wt % to about 7.5 wt % of KBr. 
     
     
         57 . The electrolyte of  claim 56 , further comprising from about 5 wt % to about 15 wt % of KCl. 
     
     
         58 . The electrolyte of  claim 58 , further comprising from about 0.1 wt % to about 0.5 wt % of DME-PEG having an average molecular weight of from about 750 amu to about 1250 amu. 
     
     
         59 . The electrolyte of  claim 44 , further comprising from about 1.0 wt % to about 2.0 wt % of DME-PEG having an average molecular weight of from about 1750 amu to about 2250 amu. 
     
     
         60 . The electrolyte of  claim 45 , further comprising an acid, or the conjugate base of an acid, selected from acetic acid, nitric acid, and citric acid. 
     
     
         61 . The electrolyte of  claim 46 , further comprising from about 0.1 wt % to about 1.0 wt % of glacial acetic acid or from about 0.1 wt % to about 1.0 wt % of HBr.

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