Patent US4068046A successfully refreshed from Google Patents.
US4068046A
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Metal halogen electrochemical cell
Assignee: ExxonMobil Technology and Engineering Co
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Filing: 1977-04-29
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Granted: 1978-01-10
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Expires: 1997-04-29
Abstract
Abstract An improved aqueous metal-halogen electrochemical cell, particularly a zinc bromide cell, contains a water soluble tetraorgano-substituted ammonium salt in the electrolyte which forms a substantially water insoluble liquid complex with cathodic halogen thereby reducing self-discharge of the cell. Particularly preferred as the ammonium salt is N-ethyl, N-methyl morpholinium bromide.
Inventors
- 👤 Daniel J. Eustace
- 👤 Paul A. Malachesky
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 21:46
CPC Classifications
H; H01; H01M; H01M10/00; H01M10/36; H01M10/365; Y; Y02; Y02E; Y02E60/00; Y02E60/10
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
180 words
In an electrochemical cell having a metal anode selected from the group consisting of zinc and cadmium; a bromine cathode; and, an aqueous electrolyte containing a metal bromide, the metal bromide having the same metal as the metal of the anode, the improvement comprising: a bromine complexing agent in said aqueous metal bromide electrolyte consisting solely of a tetraorgano substituted ammonium salt, which salt is soluble in water and forms a substantially water immiscible liquid bromine complex at temperatures in the range of about 10° C to about 60° C and wherein the tetraorgano substituted ammonium salt is selected from asymmetric quaternary ammonium compounds having the formula: ##STR15##wherein the dangling valences of nitrogen indicates that the nitrogen is an endocyclic nitrogen atom connected to carbon atoms, thereby forming a ring structure selected from saturated five-membered ring structure and a saturated six-membered ring structure including an additional heteroatom and wherein X - is a halide selected from chloride and bromide, and R 1 and R 2 are selected from alkyl groups and haloalkyl groups of from 1 to 8 carbon atoms.
Claim 2
Dependent Claim
180 words
In an electrochemical cell having a metal anode selected from the group consisting of zinc and cadmium; a bromine cathode; and, an aqueous electrolyte containing a metal bromide, the metal bromide having the same metal as the metal of the anode, the improvement comprising: a bromine complexing agent in said aqueous metal bromide electrolyte consisting solely of a tetraorgano substituted ammonium salt, which salt is soluble in water and forms a substantially water immiscible liquid bromine complex at temperatures in the range of about 10° C to about 60° C and wherein the tetraorgano substituted ammonium salt is selected from asymmetric quaternary ammonium compounds having the formula: ##STR15##wherein the dangling valences of nitrogen indicates that the nitrogen is an endocyclic nitrogen atom connected to carbon atoms, thereby forming a ring structure selected from saturated five-membered ring structure and a saturated six-membered ring structure including an additional heteroatom and wherein X - is a halide selected from chloride and bromide, and R 1 and R 2 are selected from alkyl groups and haloalkyl groups of from 1 to 8 carbon atoms.
Claim 3
Dependent Claim
11 words
The cell of claim 1 wherein the anode metal is zinc.
Claim 4
Dependent Claim
11 words
The cell of claim 1 wherein the anode metal is cadmium.
Claim 5
Dependent Claim
13 words
The cell of claim 1 wherein the halide, X - , is bromide.
Claim 6
Dependent Claim
96 words
The cell of claim 1 wherein the asymmetrical quaternary ammonium compound is selected from piperidinium, pyrrolidinium and morpholinium salts represented by the formulas: ##STR16##wherein R 1 is a methyl group and R 2 is selected from alkyl groups and haloalkyl groups having from 1 to 8 carbon atoms, R 3 is independently at each occurrence selected from hydrogen and alkyl groups having from 1 to 4 carbon atoms, and when R 3 is hydrogen at each location R 2 is different from R 1 ; and, X - is a halide selected from chloride and bromide.
Claim 7
Dependent Claim
47 words
The cell of claim 5 wherein the quaternary ammonium compound is a morpholinium salt having the formula: ##STR17##wherein R 1 is a methyl group and wherein R 2 is selected from the group consisting of alkyl groups having from 2 to 8 carbon atoms and chloromethyl group.
Claim 8
Dependent Claim
14 words
The cell of claim 5 wherein the quaternary ammonium compound is a pyrrolidinium bromide.
Claim 9
Dependent Claim
14 words
The cell of claim 5 wherein the quaternary ammonium compound is a piperidinium bromide.
Claim 10
Dependent Claim
15 words
The cell of claim 6 wherein the quaternary ammonium compound is N-ethyl, N-methyl morpholinium bromide.
Claim 11
Dependent Claim
15 words
The cell of claim 6 wherein the quaternary ammonium compound is N-chloromethyl, N-methyl morpholinium bromide.
Claim 12
Dependent Claim
14 words
The cell of claim 7 wherein the pyrrolidinium bromide is N-ethyl, N-methyl pyrrolidinium bromide.
Claim 13
Dependent Claim
14 words
The cell of claim 7 wherein the pyrrolidinium bromide is N-chloromethyl, N-methyl pyrrolidinium bromide.
Claim 14
Dependent Claim
14 words
The cell of claim 8 wherein the piperidinium bromide is N-ethyl, N-methyl piperidinium bromide.
Claim 15
Dependent Claim
179 words
An aqueous metal halogen secondary battery including a plurality of electrochemical cells, said electrochemical cells comprising a metal anode selected from the group consisting of zinc and cadmium; an inert counterelectrode; and aqueous electrolyte, said aqueous electrolyte consisting essentially of an aqueous metal bromide solution in which the metal is the same as the metal of the anode and a cathodically active bromine complex which complex is a liquid at temperatures in the range of about 10° C to about 60° C and substantially water immiscible, said bromine complex being formed solely between bromine and a water soluble, asymmetric quaternary ammonium bromide having the general formula: ##STR18##wherein the dangling valences of the nitrogen indicate that the nitrogen is part of an endocyclic structure selected from five-membered structures and six-membered structures containing only carbon and hydrogen and another heteroatom and wherein R 1 is selected from alkyl groups having from 1 to 8 carbon atoms and R 2 is selected from alkyl groups and haloalkyl substituted groups having from 1 to 8 carbon atoms but different from R 1 .
Claim 16
Dependent Claim
179 words
An aqueous metal halogen secondary battery including a plurality of electrochemical cells, said electrochemical cells comprising a metal anode selected from the group consisting of zinc and cadmium; an inert counterelectrode; and aqueous electrolyte, said aqueous electrolyte consisting essentially of an aqueous metal bromide solution in which the metal is the same as the metal of the anode and a cathodically active bromine complex which complex is a liquid at temperatures in the range of about 10° C to about 60° C and substantially water immiscible, said bromine complex being formed solely between bromine and a water soluble, asymmetric quaternary ammonium bromide having the general formula: ##STR18##wherein the dangling valences of the nitrogen indicate that the nitrogen is part of an endocyclic structure selected from five-membered structures and six-membered structures containing only carbon and hydrogen and another heteroatom and wherein R 1 is selected from alkyl groups having from 1 to 8 carbon atoms and R 2 is selected from alkyl groups and haloalkyl substituted groups having from 1 to 8 carbon atoms but different from R 1 .
Claim 17
Dependent Claim
11 words
The battery of claim 14 wherein the metal anode is zinc.
Claim 18
Dependent Claim
15 words
The battery of claim 15 wherein the aqueous electrolyte is a solution of zinc bromide.
Claim 19
Dependent Claim
36 words
The battery of claim 16 wherein the quaternary ammonium compound is an asymmetric morpholinium compound having the general formula: ##STR19##wherein R 2 is an alkyl radical having from 2 to 8 carbon atoms or chloromethyl groups.
Claim 20
Dependent Claim
36 words
The battery of claim 16 wherein the quaternary ammonium compound is an asymmetric pyrrolidinium compound having the general formula: ##STR20##wherein R 2 is an alkyl radical having from 2 to 8 carbon atoms or chloromethyl groups.
Claim 21
Dependent Claim
36 words
The battery of claim 16 wherein the quaternary ammonium compound is an asymmetric piperidinium compound having the formula: ##STR21##wherein R 2 is an alkyl radical having from 2 to 8 carbon atoms or a chloromethyl group.
Claim 22
Dependent Claim
132 words
An aqueous zinc bromide cell comprising a zinc anode; an inert electrode; and, an aqueous zinc bromine electrolyte containing a cathodically active bromine complex consisting solely of bromine and a water soluble asymmetric quaternary ammonium bromide having the general formula: ##STR22##wherein the dangling valences of nitrogen indicate that the nitrogen is an endocyclic nitrogen atom connected to carbon atoms, thereby forming a ring structure selected from saturated five-membered ring structures and a saturated six-membered ring structure including an additonal heteroatom and wherein R 1 and R 2 are selected from alkyl groups and haloalkyl groups of from 1 to 8 carbon atoms, said quaternary ammonium bromide being capable of forming a substantially water immiscible complex with bromine which complex is a liquid at temperatures ranging from about 10° to about 60° C.
Claim 23
Dependent Claim
132 words
An aqueous zinc bromide cell comprising a zinc anode; an inert electrode; and, an aqueous zinc bromine electrolyte containing a cathodically active bromine complex consisting solely of bromine and a water soluble asymmetric quaternary ammonium bromide having the general formula: ##STR22##wherein the dangling valences of nitrogen indicate that the nitrogen is an endocyclic nitrogen atom connected to carbon atoms, thereby forming a ring structure selected from saturated five-membered ring structures and a saturated six-membered ring structure including an additonal heteroatom and wherein R 1 and R 2 are selected from alkyl groups and haloalkyl groups of from 1 to 8 carbon atoms, said quaternary ammonium bromide being capable of forming a substantially water immiscible complex with bromine which complex is a liquid at temperatures ranging from about 10° to about 60° C.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-01-09 | 1981-07-11 | 1982-01-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-01-09 | 1985-07-11 | 1986-01-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-01-09 | 1989-07-11 | 1990-01-10 | $7700.00 | Window Closed / Lapsed |