US2014170511A1PendingUtilityA1
Flow Battery And Regeneration System With Improved Safety
Est. expiryAug 19, 2032(~6.1 yrs left)· nominal 20-yr term from priority
Inventors:Yuriy Vyacheslalovovich Tolmachev
H01M 8/0656H01M 8/22H01M 8/188H01M 8/20H01M 8/08Y02E60/50
42
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Claims
Abstract
A method for producing electric power and regenerating an aqueous multi-electron oxidant (AMO) and a reducer in an energy storage cycle is provided. A discharge system includes a discharge unit, an acidification reactor, and a neutralization reactor. The acidification reactor converts an oxidant fluid including the AMO into an acidic oxidant fluid. The discharge unit generates electric power and a discharge fluid by transferring electrons from a positive electrode of an electrolyte-electrode assembly (EEA) to the AMO and from a reducer to a negative electrode of the EEA. The neutralization reactor neutralizes the discharge fluid to produce a neutral discharge fluid. The regeneration system splits an alkaline discharge fluid into a reducer and an intermediate oxidant in a splitting-disproportionation reactor and releases the reducer and a base, while producing the AMO by disproportionating the intermediate oxidant. The regenerated AMO and reducer are supplied to the discharge unit for power generation.
Claims
exact text as granted — not AI-modifiedI claim:
1 . A method for producing electric power from an aqueous multi-electron oxidant and a reducer and for simultaneously generating a discharge fluid, said method comprising:
providing a discharge system comprising one or more forms of a reducer fluid, one or more forms of an oxidant fluid, a discharge unit, and an acidification reactor, said discharge unit comprising an electrolytic cell stack, said electrolytic cell stack comprising a plurality of electrolytic cells, wherein each of said electrolytic cells comprises an electrolyte-electrode assembly; and facilitating discharge of said discharge unit for producing said electric power from a neutral oxidant fluid comprising one or more forms of said aqueous multi-electron oxidant, and from said reducer fluid comprising one or more forms of said reducer, said facilitation of said discharge comprising:
lowering pH of said neutral oxidant fluid in said acidification reactor for generating an acidic oxidant fluid;
transferring electrons from a positive electrode of said electrolyte-electrode assembly to said aqueous multi-electron oxidant in said acidic oxidant fluid; and
transferring electrons from said reducer fluid to a negative electrode of said electrolyte-electrode assembly to produce said electric power in an external electric circuit operably connected to terminals of said discharge unit and to generate an acidic discharge fluid on consumption of said acidic oxidant fluid and said reducer fluid.
2 . The method of claim 1 , further comprising optionally neutralizing said acidic discharge fluid in a neutralization reactor of said discharge system to produce a neutral discharge fluid.
3 . The method of claim 1 , wherein said aqueous multi-electron oxidant comprises one or more of halogens, halogen oxides, halogen oxoanions, and salts and acids of said halogen oxoanions.
4 . The method of claim 3 , wherein said halogen oxoanions comprise one or more of hypochlorite, chlorite, chlorate, perchlorate, hypobromite, bromite, perbromate, hypoiodite, iodite, iodate, and periodate.
5 . The method of claim 3 , wherein one of said halogen oxoanions is bromate.
6 . The method of claim 1 , wherein said acidic oxidant fluid comprises water, said one or more forms of said aqueous multi-electron oxidant, an extra acid, and one or more of a plurality of counter cations.
7 . The method of claim 6 , wherein said extra acid is one or more of a phosphoric acid, a 3-(N-morpholino)propanesulfonic acid, a 3-(N-morpholino)ethanesulfonic acid, a methanesulfonic acid, a triflic acid, a substituted sulfonic acid, a substituted phosphonic acid, a perchloric acid, a sulfuric acid, a molecule comprising sulfonic moieties and phosphonic moieties, and an acid with a pKa<2.
8 . The method of claim 6 , wherein said counter cations comprise alkali metal cations, alkali earth metal cations, and organic cations.
9 . The method of claim 6 , wherein one of said counter cations is lithium.
10 . The method of claim 6 , wherein one of said counter cations is sodium.
11 . The method of claim 1 , further comprising maintaining stability of said acidic oxidant fluid by performing an ignition regime in said discharge system at low acid concentrations in said acidic oxidant fluid.
12 . The method of claim 1 , wherein concentration of said one or more forms of said aqueous multi-electron oxidant in one or more of said neutral oxidant fluid and said acidic oxidant fluid supplied to said discharge unit is above one of 1M, 2M, 5M, and 10M.
13 . The method of claim 1 , wherein concentration of acidic protons in said acidic oxidant fluid supplied to said discharge unit is below one of 0.1M, 0.5M, 1M, 2M, 5M, and 10M.
14 . The method of claim 1 , wherein concentration of acidic protons in said acidic oxidant fluid stored in said discharge system is below one of 0.1M, 0.5M, 1M, 2M, and 5M.
15 . The method of claim 1 , wherein said transfer of said electrons from said positive electrode of said electrolyte-electrode assembly to said aqueous multi-electron oxidant in said acidic oxidant fluid is performed at a high current density and at low flow rates in an ignition mode of operation of said discharge system.
16 . The method of claim 1 , wherein said acidic discharge fluid comprises one or more of water, a halide, a hydroxonium cation, an extra acid, and one or more counter cations.
17 . The method of claim 1 , wherein said reducer is hydrogen.
18 . The method of claim 1 , wherein said reducer is selected from a group consisting of ammonia, hydrazine, hydroxylamine, phosphine, methane, a hydrocarbon, an alcohol, an aldehyde, a carbohydrate, a hydride, an oxide, a sulfide, an organic compound, an inorganic compound, and any combination thereof, with one of each other, water, and another solvent.
19 . The method of claim 1 , wherein said generation of said acidic oxidant fluid from said neutral oxidant fluid is performed in said acidification reactor via an electric field driven orthogonal ion migration across laminar flow process.
20 . The method of claim 1 , wherein said generation of said acidic oxidant fluid from said neutral oxidant fluid is performed in said acidification reactor by one or more of an ion exchange on solids, an ion exchange in liquids, electrolysis, and adding an extra acid to said neutral oxidant fluid during said discharge of said discharge unit.
21 . The method of claim 1 , wherein said discharge is facilitated on said positive electrode of said electrolyte-electrode assembly by one or more of electrocatalysis, a solution-phase chemical reaction, a solution-phase comproportionation, a solution-phase redox catalysis, a solution-phase redox mediator, an acid-base catalysis, and any combination thereof.
22 . The method of claim 1 , wherein said discharge is facilitated via a solution-phase comproportionation of said aqueous multi-electron oxidant with a final product of a reduction of said aqueous multi-electron oxidant.
23 . The method of claim 22 , wherein said solution-phase comproportionation is pH-dependent and said discharge is facilitated in a presence of an acid.
24 . The method of claim 1 , further comprising regenerating a certain amount of an intermediate oxidant and said reducer in said discharge unit from said acidic discharge fluid by applying an electric current of a polarity opposite to a polarity of electric current through said discharge unit during said discharge.
25 . A discharge system comprising:
one or more forms of an oxidant fluid comprising one or more forms of an aqueous multi-electron oxidant; one or more forms of a reducer fluid comprising one or more forms of a reducer; a discharge unit comprising an electrolytic cell stack, said electrolytic cell stack comprising a plurality of electrolytic cells, wherein each of said electrolytic cells comprises an electrolyte-electrode assembly; an acidification reactor operably connected to said discharge unit, said acidification reactor configured to lower pH of a neutral oxidant fluid for generating an acidic oxidant fluid; and said discharge unit configured to produce said electric power from said acidic oxidant fluid and from said reducer fluid by:
transferring electrons from a positive electrode of said electrolyte-electrode assembly to said aqueous multi-electron oxidant in said acidic oxidant fluid; and
transferring electrons from said reducer fluid to a negative electrode of said electrolyte-electrode assembly to produce said electric power in an external electric circuit operably connected to terminals of said discharge unit and to generate an acidic discharge fluid on consumption of said acidic oxidant fluid and said reducer fluid.
26 . The discharge system of claim 25 , further optionally comprising a neutralization reactor configured to neutralize said acidic discharge fluid to produce a neutral discharge fluid.
27 . The discharge system of claim 26 , wherein said acidification reactor and said neutralization reactor are functionally combined as an orthogonal ion migration across laminar flow reactor.
28 . The discharge system of claim 27 , wherein said orthogonal ion migration across laminar flow reactor comprises flow cell assemblies, end plates, and bipolar plates, wherein each of said flow cell assemblies of said orthogonal ion migration across laminar flow reactor comprises:
ion exchange membranes comprising a positive side ion exchange membrane and a negative side ion exchange membrane positioned parallel to each other; a positive electrode layer and a negative electrode layer flanking outer surfaces of said ion exchange membranes, wherein said positive electrode layer is configured for a hydrogen oxidation reaction and said negative electrode layer is configured for a hydrogen evolution reaction; an intermembrane flow field comprising a plurality of flow channels, said intermembrane flow field interposed between said ion exchange membranes; and porous diffusion layers flanking said outer surfaces of said ion exchange membranes and in electric contact with one of said bipolar plates and said end plates.
29 . The discharge system of claim 25 configured to operate in an electric partial recharge mode for facilitating regenerative breaking when said discharge system powers an electric vehicle, wherein said reducer is produced on said negative electrode of said electrolyte-electrode assembly and an intermediate oxidant is produced on said positive electrode of said electrolyte-electrode assembly during said electric partial recharge mode.
30 . A method for regenerating an aqueous multi-electron oxidant and a reducer in stoichiometric amounts from one or more forms of a neutral discharge fluid using external power, said method comprising:
converting said neutral discharge fluid into an alkaline discharge fluid by using one or more of an externally supplied base and a base produced in a splitting-disproportionation reactor configured for one of an aqueous multi-electron oxidant-on-negative electrode mode of operation, a no-aqueous multi-electron oxidant-on-negative electrode mode of operation, and a combination thereof; splitting said alkaline discharge fluid into a reducer and an intermediate oxidant in said splitting-disproportionation reactor, wherein said intermediate oxidant is converted into one or more forms of said aqueous multi-electron oxidant via disproportionation of said intermediate oxidant with said base, and wherein said splitting releases a stoichiometric amount of said reducer and said base in said splitting-disproportionation reactor; and continuing said splitting and said disproportionation in said splitting-disproportionation reactor in one of a batch mode of operation, a cyclic flow mode of operation, a cascade flow mode of operation, and a combination thereof until a desired degree of conversion of a discharge product of said aqueous multi-electron oxidant into said one or more forms of said aqueous multi-electron oxidant is achieved.
31 . The method of claim 30 , wherein said splitting is performed by:
electrolyzing said alkaline discharge fluid into said reducer and said intermediate oxidant in said splitting-disproportionation reactor configured as an electrolysis-disproportionation reactor, wherein said intermediate oxidant produced at one or more positive electrodes of said electrolysis-disproportionation reactor is converted into said one or more forms of said aqueous multi-electron oxidant via said disproportionation of said intermediate oxidant produced at said one or more positive electrodes with said base, wherein said electrolysis releases said stoichiometric amount of said reducer and said base at said one or more negative electrodes of said electrolysis-disproportionation reactor; and continuing said electrolysis and said disproportionation in said electrolysis-disproportionation reactor in said one of said batch mode of operation, said cyclic flow mode of operation, said cascade flow mode of operation, and a combination thereof until a desired degree of conversion of said discharge product of said aqueous multi-electron oxidant into said one or more forms of said aqueous multi-electron oxidant is achieved.
32 . The method of claim 30 , wherein said discharge fluid comprises one or more of water, a halide, a hydroxonium cation, a buffer, and one or more counter cations.
33 . The method of claim 30 , further comprising optimizing and stabilizing pH of said alkaline discharge fluid in said splitting-disproportionation reactor using a buffer present in said one or more forms of said discharge fluid to facilitate said disproportionation of said intermediate oxidant into said one or more forms of said aqueous multi-electron oxidant.
34 . The method of claim 33 , wherein said pH of said alkaline discharge fluid is one of between 6 and 10 and between 4 and 9.
35 . The method of claim 33 , wherein said buffer is configured to maintain said pH of said alkaline discharge fluid at one of between 6 and 10 and between 4 and 9.
36 . The method of claim 33 , wherein a base component of said buffer is selected from a group comprising a hydroxide ion, hydrogen phosphate, a phosphate ester, a substituted phosphonate, alkylphosphonate, arylphosphonate, a deprotonated form of one or more of Good's buffers, an amine, a nitrogen heterocycle, and any combination thereof.
37 . The method of claim 33 , wherein a cationic component of said buffer comprises a cation of lithium.
38 . The method of claim 33 , wherein a cationic component of said buffer comprises a cation of sodium.
39 . The method of claim 33 , wherein an anionic component of said buffer comprises one or more of ω-(N-morpholino)alkanesulfonate, 2-(N-morpholino)ethanesulfonate, 3-(N-morpholino)propanesulfonate, and 4-(N-morpholino)butanesulfonate.
40 . The method of claim 33 , wherein an anionic component of said buffer is one or more of ω-(N-morpholino)alkanesulfonate, 2-(N-morpholino)ethanesulfonate, 3-(N-morpholino)propanesulfonate, and 4-(N-morpholino)butanesulfonate, and wherein a cationic component of said buffer is lithium.
41 . The method of claim 33 , wherein an anionic component of said buffer comprises one or more of an alkylphosphonate and an arylphosphonate.
42 . The method of claim 33 , wherein an anionic component of said buffer comprises one or more of an alkylphosphonate and an arylphosphonate, and wherein a cationic component of said buffer is lithium.
43 . The method of claim 33 , wherein a base component of said buffer is monohydrogen phosphate, and wherein a cationic component of said buffer is sodium.
44 . The method of claim 30 , wherein said splitting of said alkaline discharge fluid into said reducer and said intermediate oxidant in said splitting-disproportionation reactor is performed via one of electrolysis, photolysis, photoelectrolysis, radiolysis, thermolysis, and any combination thereof.
45 . The method of claim 44 , wherein said photolysis and said photoelectrolysis of said alkaline discharge fluid is performed in one of a presence and an absence of a light adsorbing facilitator, a semiconductor, a catalyst, and any combination thereof.
46 . A regeneration system comprising:
a splitting-disproportionation reactor configured to convert a neutral discharge fluid into an alkaline discharge fluid by using one or more of an externally supplied base and a base produced in said splitting-disproportionation reactor; said splitting-disproportionation reactor further configured to split said alkaline discharge fluid into a reducer and an intermediate oxidant, wherein said splitting releases a stoichiometric amount of said reducer and said base in said splitting-disproportionation reactor; said splitting-disproportionation reactor further configured to convert said intermediate oxidant into one or more forms of an aqueous multi-electron oxidant via disproportionation of said intermediate oxidant with said base; and said splitting-disproportionation reactor further configured to continue said splitting and said disproportionation in one of a batch mode of operation, a cyclic flow mode of operation, a cascade flow mode of operation, and any combination thereof, until a desired degree of conversion of a discharge product of said aqueous multi-electron oxidant into said one or more forms of said aqueous multi-electron oxidant is achieved.
47 . The regeneration system of claim 46 , further optionally comprising a concentrating reactor configured to produce a concentrated solution of a neutral oxidant fluid comprising a salt form of said aqueous multi-electron oxidant.
48 . The regeneration system of claim 46 , further comprising one or more separation reactors configured to separate gases from liquids during a regeneration process.
49 . The regeneration system of claim 46 , wherein said splitting-disproportionation reactor is further configured for an aqueous multi-electron oxidant-on-negative electrode mode of operation using a multilayer structure on a negative electrode side of said splitting-disproportionation reactor.
50 . The regeneration system of claim 49 , wherein said multilayer structure on said negative electrode side of said splitting-disproportionation reactor is configured to minimize reduction of a regenerated aqueous multi-electron oxidant in a regenerated oxidant fluid on said negative electrode side while facilitating hydrogen evolution and an increase in pH of said regenerated oxidant fluid.
51 . The regeneration system of claim 46 , wherein said splitting-disproportionation reactor is further configured for a no-aqueous multi-electron oxidant-on-negative electrode mode of operation by transferring a base produced on one or more negative electrodes of said splitting-disproportionation reactor to a regenerated oxidant fluid produced at one or more positive electrodes of said splitting-disproportionation reactor and comprising said one or more forms of said aqueous multi-electron oxidant and said intermediate oxidant.
52 . A regeneration system comprising:
an electrolysis-disproportionation reactor configured to convert a neutral discharge fluid into an alkaline discharge fluid by using one or more of an externally supplied base and a base produced at one or more negative electrodes of said electrolysis-disproportionation reactor in one of an aqueous multi-electron oxidant-on-negative electrode mode of operation, a no-aqueous multi-electron oxidant-on-negative electrode mode of operation, and a combination thereof; said electrolysis-disproportionation reactor further configured to split said alkaline discharge fluid into a reducer and an intermediate oxidant via electrolysis, wherein said electrolysis releases a stoichiometric amount of said reducer and said base at said one or more negative electrodes of said electrolysis-disproportionation reactor; said electrolysis-disproportionation reactor further configured to convert said intermediate oxidant produced at one or more positive electrodes of said electrolysis-disproportionation reactor into one or more forms of an aqueous multi-electron oxidant via disproportionation of said intermediate oxidant produced at said one or more positive electrodes with said base; and said electrolysis-disproportionation reactor further configured to continue said electrolysis and said disproportionation in one of a batch mode of operation, a cyclic flow mode of operation, a cascade flow mode of operation, and any combination thereof, until a desired degree of conversion of a discharge product of said aqueous multi-electron oxidant into said one or more forms of said aqueous multi-electron oxidant is achieved.
53 . A method for producing electric power and regenerating an aqueous multi-electron oxidant and a reducer in an energy storage cycle, said method comprising:
providing a discharge system comprising one or more forms of a reducer fluid, one or more forms of an oxidant fluid, a discharge unit, an acidification reactor, and optionally a neutralization reactor, said discharge unit comprising an electrolytic cell stack, said electrolytic cell stack comprising a plurality of electrolytic cells, wherein each of said electrolytic cells comprises an electrolyte-electrode assembly; facilitating discharge of said discharge unit for producing said electric power from a neutral oxidant fluid comprising one or more forms of said aqueous multi-electron oxidant, and from said reducer fluid comprising one or more forms of said reducer, said facilitation of said discharge comprising:
lowering pH of said neutral oxidant fluid in said acidification reactor for generating an acidic oxidant fluid;
transferring electrons from a positive electrode of said electrolyte-electrode assembly to said aqueous multi-electron oxidant in said acidic oxidant fluid; and
transferring electrons from said reducer fluid to a negative electrode of said electrolyte-electrode assembly to produce said electric power in an external electric circuit operably connected to terminals of said discharge unit and to generate an acidic discharge fluid on consumption of said acidic oxidant fluid and said reducer fluid;
optionally neutralizing said acidic discharge fluid in said neutralization reactor of said discharge system to produce a neutral discharge fluid; regenerating said one or more forms of oxidant fluid comprising said aqueous multi-electron oxidant and said reducer fluid comprising said reducer in stoichiometric amounts from one or more forms of said neutral discharge fluid in a regeneration system using external power, said regeneration comprising:
converting said neutral discharge fluid into an alkaline discharge fluid by using one or more of an externally supplied base and a base produced in a splitting-disproportionation reactor configured for one of an aqueous multi-electron oxidant-on-negative electrode mode of operation, a no-aqueous multi-electron oxidant-on-negative electrode mode of operation, and a combination thereof;
splitting said alkaline discharge fluid into a reducer and an intermediate oxidant in said splitting-disproportionation reactor, wherein said intermediate oxidant is converted into one or more forms of said aqueous multi-electron oxidant via disproportionation of said intermediate oxidant with said base, and wherein said splitting releases a stoichiometric amount of said reducer and said base in said splitting-disproportionation reactor; and
continuing said splitting and said disproportionation in said splitting-disproportionation reactor in one of a batch mode of operation, a cyclic flow mode of operation, a cascade flow mode of operation, and a combination thereof, until a desired degree of conversion of a discharge product of said aqueous multi-electron oxidant into said one or more forms of said aqueous multi-electron oxidant is achieved; and
supplying said regenerated one or more forms of said oxidant fluid comprising said aqueous multi-electron oxidant and said regenerated reducer fluid comprising said reducer to said discharge system for said facilitation of said discharge of said discharge unit.
54 . The method of claim 53 , wherein said aqueous multi-electron oxidant comprises one or more of halogens, halogen oxides, halogen oxoanions, and salts and acids of said halogen oxoanions.
55 . The method of claim 54 , wherein said halogen oxoanions comprise one or more of hypochlorite, chlorite, chlorate, perchlorate, hypobromite, bromite, perbromate, hypoiodite, iodite, iodate, and periodate.
56 . The method of claim 54 , wherein one of said halogen oxoanions is bromate.
57 . The method of claim 53 , wherein said acidic oxidant fluid comprises water, said one or more forms of said aqueous multi-electron oxidant, optionally an extra acid, and one or more of a plurality of counter cations.
58 . The method of claim 57 , wherein said counter cations comprise alkali metal cations, alkali earth metal cations, and organic cations.
59 . The method of claim 57 , wherein one of said counter cations is lithium.
60 . The method of claim 57 , wherein one of said counter cations is sodium.
61 . The method of claim 53 , wherein concentration of said one or more forms of said aqueous multi-electron oxidant in one or more of said neutral oxidant fluid and said acidic oxidant fluid supplied to said discharge unit of said discharge system is above one of 1M, 2M, 5M, and 10M.
62 . The method of claim 53 , wherein concentration of acidic protons in said acidic oxidant fluid supplied to said discharge unit of said discharge system is below one of 0.1M, 0.5M, 1M, 2M, 5M, and 10M.
63 . The method of claim 53 , wherein concentration of acidic protons in said acidic oxidant fluid stored in said discharge system is below one of 0.1 M, 0.5 M, 1 M, 2 M, and 5 M.
64 . The method of claim 53 , wherein said transfer of said electrons from said positive electrode of said electrolyte-electrode assembly of said discharge system to said aqueous multi-electron oxidant in said acidic oxidant fluid is performed at a high current density and at low flow rates in an ignition mode of operation of said discharge system.
65 . The method of claim 64 , wherein a limiting current of said transfer of said electrons from said positive electrode of said electrolyte-electrode assembly to said aqueous multi-electron oxidant in said acidic oxidant fluid in an ignition regime is limited by one of a mass transport of said aqueous multi-electron oxidant, a mass transport of acidic protons, and a rate of comproportionation.
66 . The method of claim 53 , wherein said acidic discharge fluid comprises one or more of water, a halide, a hydroxonium cation, an extra acid, and one or more counter cations.
67 . The method of claim 53 , wherein said reducer is hydrogen.
68 . The method of claim 53 , wherein said reducer is selected from a group consisting of ammonia, hydrazine, hydroxylamine, phosphine, methane, a hydrocarbon, an alcohol, an aldehyde, a carbohydrate, a hydride, an oxide, a sulfide, an organic compound, an inorganic compound, and any combination thereof, with one of each other, water, and another solvent.
69 . The method of claim 53 , wherein said generation of said acidic oxidant fluid from said neutral oxidant fluid is performed in said acidification reactor of said discharge system via an electric field driven orthogonal ion migration across laminar flow process.
70 . The method of claim 53 , wherein said generation of said acidic oxidant fluid from said neutral oxidant fluid is performed in said acidification reactor of said discharge system via one or more of an ion exchange on solids, an ion exchange in liquids, electrolysis, and adding an extra acid to said neutral oxidant fluid during said discharge of said discharge unit of said discharge system.
71 . The method of claim 53 , wherein said discharge is facilitated on said positive electrode of said electrolyte-electrode assembly by one or more of electrocatalysis, a solution-phase chemical reaction, a solution-phase comproportionation, a solution-phase redox catalysis, a solution-phase redox mediator, an acid-base catalysis, and any combination thereof.
72 . The method of claim 53 , wherein said discharge is facilitated via a solution-phase comproportionation of said aqueous multi-electron oxidant with a final product of a reduction of said aqueous multi-electron oxidant.
73 . The method of claim 72 , wherein said solution-phase comproportionation is pH-dependent and said discharge is facilitated in a presence of an acid.
74 . The method of claim 53 , further comprising optimizing and stabilizing pH of said acidic oxidant fluid in said splitting-disproportionation reactor of said regeneration system using an extra acid present in said acidic oxidant fluid to facilitate comproportionation of said aqueous multi-electron oxidant with a final product of a reduction of said aqueous multi-electron oxidant into said intermediate oxidant.
75 . The method of claim 74 , wherein said extra acid is one or more of a phosphoric acid, a 3-(N-morpholino)propanesulfonic acid, a 3-(N-morpholino)ethanesulfonic acid, another ω-(N-morpholino)propanesulfonic acid, a methanesulfonic acid, triflic acid, a substituted sulfonic acid, a substituted phosphonic acid, a perchloric acid, a sulfuric acid, a molecule comprising sulfonic moieties and phosphonic acid moieties, and an acid with a pKa<2.
76 . The method of claim 53 , wherein said pH of said acidic discharge fluid is below one of 0, 1, 2, and 3.
77 . The method of claim 53 , wherein concentration of acidic protons in said acidic discharge fluid is below one of 0.1M, 0.5M, 1M, 2M, 5M, and 10M.
78 . The method of claim 53 , wherein said splitting of said alkaline discharge fluid into said reducer and said intermediate oxidant in said splitting-disproportionation reactor of said regeneration system is performed via one of electrolysis, photolysis, photoelectrolysis, radiolysis, thermolysis, and any combination thereof.
79 . The method of claim 78 , wherein said photolysis and said photoelectrolysis of said alkaline discharge fluid is performed in one of a presence and an absence of a light adsorbing facilitator, a semiconductor, a catalyst, and any combination thereof.
80 . The method of claim 53 , wherein said splitting-disproportionation reactor of said regeneration system is configured as an electrolysis-disproportionation reactor for said aqueous multi-electron oxidant-on-negative electrode mode of operation using a multilayer structure on a negative electrode side of said electrolysis-disproportionation reactor.
81 . The method of claim 80 , wherein said multilayer structure on said negative electrode side of said electrolysis-disproportionation reactor is configured to minimize reduction of a regenerated aqueous multi-electron oxidant in a regenerated oxidant fluid on said negative electrode side while facilitating hydrogen evolution and an increase in pH of said regenerated oxidant fluid.
82 . The method of claim 53 , wherein said splitting-disproportionation reactor of said regeneration system is configured as an electrolysis-disproportionation reactor for said no-aqueous multi-electron oxidant-on-negative electrode mode of operation by transferring a base produced on one or more negative electrodes of said electrolysis-disproportionation reactor to a regenerated oxidant fluid produced at one or more positive electrodes of said electrolysis-disproportionation reactor and comprising said one or more forms of said aqueous multi-electron oxidant and said intermediate oxidant.
83 . The method of claim 53 , wherein said acidification reactor and said neutralization reactor of said discharge system are functionally combined as an orthogonal ion migration across laminar flow reactor.
84 . A method for producing electric power and regenerating hydrogen and an oxidant fluid comprising lithium bromate in an energy storage cycle, said method comprising:
providing a discharge system comprising a discharge unit, an acidification reactor, and optionally a neutralization reactor, said discharge system comprising a neutral oxidant fluid comprising said lithium bromate, one or more forms of a buffer, and said hydrogen, wherein concentration of said lithium bromate dissolved in said neutral oxidant fluid is above one of 1M, 2M, 5M, and 10M; converting said neutral oxidant fluid into an acidic oxidant fluid in said acidification reactor, wherein concentration of acidic protons in said acidic oxidant fluid is below one of 0.1M, 0.5M, 1M, 2M, 5M, and 10M; facilitating discharge of said discharge unit for producing said electric power from said acidic oxidant fluid and from said hydrogen and generating an acidic discharge fluid on consumption of said acidic oxidant fluid and said hydrogen, wherein said discharge is facilitated via a pH-dependent solution-phase comproportionation of bromate with bromide formed via electroreduction of an intermediate bromine; optionally neutralizing said acidic discharge fluid in said neutralization reactor of said discharge system to produce one or more forms of a neutral discharge fluid; regenerating said hydrogen and one or more forms of said oxidant fluid comprising said lithium bromate in stoichiometric amounts from one or more forms of said neutral discharge fluid in a regeneration system using external power, said regeneration comprising:
splitting said one or more forms of said neutral discharge fluid into stoichiometric amounts of bromine, hydrogen, and a base form of said buffer using said external power in a splitting-disproportionation reactor, and producing said lithium bromate via disproportionation of said bromine with said base form of said buffer, wherein said splitting is performed via one or more of electrolysis, photolysis, photoelectrolysis, radiolysis, and thermolysis, and wherein said disproportionation of said bromine is facilitated by a buffer capable of maintaining a solution pH between 4 and 9; and
continuing said splitting and said disproportionation in said splitting-disproportionation reactor in one of a no-aqueous multi-electron oxidant-on-negative electrode mode of operation and an aqueous multi-electron oxidant-on-negative electrode mode of operation in one of a plurality of modes, until a desired degree of conversion of said bromide into said bromate is achieved; and
supplying said regenerated one or more forms of said oxidant fluid comprising said bromate and said regenerated hydrogen to said discharge system for subsequent generation of electric power on demand.
85 . The method of claim 84 , wherein said modes comprise a batch mode, a cyclic flow mode, a cascade flow mode, and any combination thereof.
86 . The method of claim 84 , wherein a cationic component of said buffer is lithium, and wherein an anionic component of said buffer is one or more of ω-(N-morpholino)alkanesulfonate, 3-(N-morpholino)methanesulfonate, 3-(N-morpholino)ethanesulfonate, 3-(N-morpholino)propanesulfonate, 3-(N-morpholino)butanesulfonate, methylphosphonate, an alkylphosphonate, an arylphosphonate, and a molecule comprising phosphonate moieties and sulfonate moieties.
87 . The method of claim 84 , wherein a cationic component of said buffer is sodium, and wherein an anionic component of said buffer is one or more of ω-(N-morpholino)alkanesulfonate, methylphosphonate, 3-(N-morpholino)ethanesulfonate, 3-(N-morpholino)propanesulfonate, an alkylphosphonate, an arylphosphonate, and a molecule comprising phosphonate moieties and sulfonate moieties.
88 . The method of claim 84 , wherein said discharge system further comprises a deprotionated form of an extra acid.
89 . The method of claim 88 , wherein said extra acid comprises one or more of bromic acid, sulfuric acid, perchloric acid, triflic acid, a sulfonic acid, molecules comprising phosphonate moieties and sulfonate moieties, and an acid with a pKa≦2.
90 . The method of claim 84 , wherein said base form of said buffer is one or more of ω-(N-morpholino)alkanesulfonate, 2-(N-morpholino)ethanesulfonate, 3-(N-morpholino)propanesulfonate, 4-(N-morpholino)butanesulfonate, a phosphoric acid derivative, an alkylphosphonate, an arylphosphonate, a molecule comprising phosphonate moieties and sulfonate moieties, an amine, a nitrogen heterocycle, and a base with a pKa between 4 and 9.
91 . The method of claim 84 , wherein one or more forms of said acidic oxidant fluid comprises said lithium bromate, water, one or more forms of a buffer, and optionally one or more forms of an extra acid,
92 . The method of claim 84 , wherein said buffer is in an acid form during said discharge with a pH≦4, and wherein said acid form of said buffer comprises one or more of a phosphoric acid derivative, a phosphoric acid ester, one or more substituted phosphonic acids, one or more 2-(N-morpholino) alkanesulfonic acids, molecules comprising both phosphonate and sulfonate moieties, and buffers capable of maintaining pH between 4 and 9.
93 . A system for producing electric power and regenerating an aqueous multi-electron oxidant and a reducer in an energy storage cycle, said system comprising:
a discharge system comprising:
a neutral oxidant fluid comprising one or more forms of said aqueous multi-electron oxidant;
a reducer fluid comprising one or more forms of said reducer;
a discharge unit comprising an electrolytic cell stack, said electrolytic cell stack comprising a plurality of electrolytic cells, wherein each of said electrolytic cells comprises an electrolyte-electrode assembly;
an acidification reactor operably connected to said discharge unit, said acidification reactor configured to lower pH of said neutral oxidant fluid for generating an acidic oxidant fluid; and
said discharge unit configured to produce said electric power from said acidic oxidant fluid and from said reducer fluid by performing:
transferring electrons from a positive electrode of said electrolyte-electrode assembly to said aqueous multi-electron oxidant in said acidic oxidant fluid; and
transferring electrons from said reducer fluid to a negative electrode of said electrolyte-electrode assembly to produce said electric power in an external electric circuit operably connected to terminals of said discharge unit and to generate an acidic discharge fluid on consumption of said acidic oxidant fluid and said reducer fluid; and
a regeneration system comprising:
an splitting-disproportionation reactor configured to convert a neutral discharge fluid into an alkaline discharge fluid by using one or more of an externally supplied base and a base produced in said splitting-disproportionation reactor configured for one of an aqueous multi-electron oxidant-on-negative electrode mode of operation, a no-aqueous multi-electron oxidant-on-negative electrode mode of operation, and a combination thereof;
said splitting-disproportionation reactor configured to split said alkaline discharge fluid into a reducer and an intermediate oxidant via one of electrolysis, photoelectrolysis, photolysis, thermolysis, and radiolysis, wherein said splitting also releases stoichiometric amounts of said reducer and said base in said splitting-disproportionation reactor;
said splitting-disproportionation reactor configured to convert said intermediate oxidant produced in said splitting-disproportionation reactor into one or more forms of said aqueous multi-electron oxidant via disproportionation of said intermediate oxidant with said base; and
said splitting-disproportionation reactor configured to continue said splitting and said disproportionation in one of a batch mode of operation, a cyclic flow mode of operation, a cascade flow mode of operation, and a combination thereof, until a desired degree of conversion of a discharge product of said aqueous multi-electron oxidant into one or more forms of said aqueous multi-electron oxidant is achieved.
94 . The system of claim 93 , wherein said discharge system further optionally comprises a neutralization reactor operably connected to said discharge unit, wherein said neutralization reactor is configured to raise pH of said acidic discharge fluid for generating one or more forms of said neutral discharge fluid.
95 . The system of claim 94 , wherein said acidification reactor and said neutralization reactor of said discharge system are functionally combined as an orthogonal ion migration across laminar flow reactor.
96 . The system of claim 95 , wherein said orthogonal ion migration across laminar flow reactor comprises flow cell assemblies, end plates, and bipolar plates, wherein each of said flow cell assemblies of said orthogonal ion migration across laminar flow reactor comprises:
ion exchange membranes comprising a positive side ion exchange membrane and a negative side ion exchange membrane positioned parallel to each other; a positive electrode layer and a negative electrode layer flanking outer surfaces of said ion exchange membranes, wherein said positive electrode layer is configured for a hydrogen oxidation reaction and said negative electrode layer is configured for a hydrogen evolution reaction; an intermembrane flow field comprising a plurality of flow channels, said intermembrane flow field interposed between said ion exchange membranes; and porous diffusion layers flanking said outer surfaces of said ion exchange membranes and in electric contact with one of said bipolar plates and said end plates.
97 . The system of claim 93 , wherein said discharge system is configured to operate in an electric partial recharge mode for facilitating regenerative breaking when said discharge system powers an electric vehicle, wherein said reducer is produced on said negative electrode of said electrolyte-electrode assembly and an intermediate oxidant is produced on said positive electrode of said electrolyte-electrode assembly during said electric partial recharge mode.
98 . The system of claim 93 , wherein said regeneration system further optionally comprises a concentrating reactor configured to produce a concentrated solution of a neutral oxidant fluid comprising a salt form of said aqueous multi-electron oxidant.
99 . The system of claim 93 , wherein said regeneration system further comprises one or more separation reactors configured to separate gases from liquids during a regeneration process.
100 . The system of claim 93 , wherein said splitting-disproportionation reactor of said regeneration system is further configured for an aqueous multi-electron oxidant-on-negative electrode mode of operation using a multilayer structure on a negative electrode side of said splitting-disproportionation reactor.
101 . The system of claim 100 , wherein said multilayer structure on said negative electrode side of said splitting-disproportionation reactor is configured to minimize reduction of a regenerated aqueous multi-electron oxidant in a regenerated oxidant fluid on said negative electrode side while facilitating hydrogen evolution and an increase in pH of said regenerated oxidant fluid.
102 . The system of claim 93 , wherein said splitting-disproportionation reactor is further configured for a no-aqueous multi-electron oxidant-on-negative electrode mode of operation by transferring a base produced on one or more negative electrodes of said splitting-disproportionation reactor to a regenerated oxidant fluid at one or more positive electrodes of said splitting-disproportionation reactor and comprising said one or more forms of said aqueous multi-electron oxidant and said intermediate oxidant.Join the waitlist — get patent alerts
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