Patent Application
20240006644
Energy storage technologies are playing an increasingly important role in electric power grids; at a most basic level, these energy storage assets provide smoothing to better match generation and demand on a grid. The services performed by energy storage devices are beneficial to electric power grids across multiple time scales, from milliseconds to years. Today, energy storage technologies exist that can support timescales from milliseconds to hours, but there is a need for long and ultralong (collectively, >8 h) energy storage systems. Of benefit are potentially low-cost rechargeable battery chemistries that can enable long duration large scale energy storage.
Systems, methods, and device of the various embodiments may support energy storage devices in which electrochemical oxidation and reduction of one or more redox-active oxyanions occurs during charging and/or discharging of the energy storage device.
Various embodiments may include an energy storage device, comprising: at least one electrode configured such that electrochemical oxidation and reduction of one or more redox-active oxyanions occurs during charging and/or discharging of the energy storage device.
Various embodiments may include an energy storage device, comprising: negative electrode materials comprising sulfate and sulfite; and positive electrode materials comprising oxygen, wherein the energy storage device is configured to be rechargeable.
Various embodiments include halogen oxyanion-based electrodes and related batteries and systems. Various embodiments include electrochemical electrode reactions comprising halogen oxyanions. Various embodiments may include an electrode in an electrochemical device comprising an electrode reaction, or redox reaction, of a halogenated oxyanion species.
Various embodiments include reversible Cl(III)/Cl(IV) electrodes, processes for making reversible Cl(III)/Cl(IV) electrodes, and batteries and battery systems including reversible Cl(III)/Cl(IV) electrodes. Various embodiments may include a direct reversible Cl(III)/Cl(IV) cathode, for example coupled with ClO2 storage, in a battery and/or battery system. Various embodiments may include an indirect Cl(III)/Cl(IV) electrode, for example without ClO2 storage, in a battery and/or battery system. Such indirect Cl(III)/Cl(IV) electrode may be, for example, based on a 3-Chemical Chlorine Dioxide Reaction.
A first example implementation may include an alkaline electrolyte with a polysulfide electrode and NaClO2 electrode. Such an example has been observed to have an open circuit voltage (OCV) of 1.50 volts (V). A second example implementation may include an alkaline electrolyte with an iron electrode and NaClO2 electrode. Such an example is calculated to have an OCV of 1.84V. A third example implementation may include a neutral electrolyte with an iron electrode and NaClO2 electrode. Such an example is calculated to have an OCV of 1.39V. A fourth example implementation may include an acidic electrolyte with a hydrogen electrode and NaClO2 electrode. Such an example is calculated to have an OCV of 1.27V.
Various embodiments may include an electrochemical system, comprising: a first electrode; and a second electrode, wherein the electrochemical system stores energy and/or discharges energy by an electrode reaction of a halogenated oxyanion species. In some embodiments, the storing of energy and/or the discharging of energy by the electrode reaction of the halogenated oxyanion species comprises storing energy and discharging energy by a reversable electrode reaction between a chlorine containing ion and chlorine dioxide. In some embodiments, the chlorine containing ion comprises a salt. In some embodiments, the salt is an alkali metal salt. In some embodiments, the electrochemical system comprises a storage battery. In some embodiments, the system may further comprise a current collector comprising a metal or metal compound. In some embodiments, the current collector comprises carbon. In some embodiments, the system is a bulk energy storage system is a long duration energy storage (LODES) system.
Various embodiments may include a method, comprising: storing and/or discharging energy by an electrode reaction of a halogenated oxyanion species. In some embodiments, storing and/or discharging energy by an electrode reaction of a halogenated oxyanion species comprises storing and/or discharging energy by a reversable electrode reaction between a chlorine containing ion and chlorine dioxide. In some embodiments, the chlorine containing ion comprises a salt. In some embodiments, the salt is an alkali metal salt. In some embodiments, the storing and/or discharging are performed as part of operating a battery in a bulk energy storage system. In some embodiments, the bulk energy storage system is a long duration energy storage (LODES) system.
Various embodiments may include an energy storage device, comprising: negative electrode materials; and positive electrode materials comprising chlorine dioxide and chlorite, wherein the energy storage device is configured to be rechargeable.
The accompanying drawings, which are incorporated herein and constitute part of this specification, illustrate example embodiments of the claims, and together with the general description given above and the detailed description given below, serve to explain the features of the claims.
Embodiments will be described in detail with reference to the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. References made to particular examples and implementations are for illustrative purposes and are not intended to limit the scope of the claims. The following description of the embodiments of the disclosure is not intended to limit the disclosure to these embodiments but rather to enable a person skilled in the art to make and use this disclosure. Unless otherwise noted, the accompanying drawings are not drawn to scale.
As used herein unless specified otherwise, the recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value within a range is incorporated into the specification as if it were individually recited herein.
The following examples are provided to illustrate various embodiments of the present systems and methods of the present disclosure. These examples are for illustrative purposes, may be prophetic, and should not be viewed as limiting, and do not otherwise limit the scope of the present disclosure.
It is noted that there is no requirement to provide or address the theory underlying the novel and groundbreaking processes, materials, performance or other beneficial features and properties that are the subject of, or associated with, embodiments of the present disclosure. Nevertheless, various theories are provided in this specification to further advance the art in this area. The theories put forth in this specification, and unless expressly stated otherwise, in no way limit, restrict or narrow the scope of protection to be afforded the claimed invention. These theories may not be required to utilize the present disclosure. It is further understood that the present disclosure may lead to new, and heretofore unknown theories to explain the function-features of embodiments of the methods, articles, materials, devices, and system of the present disclosure, and such later developed theories shall not limit the scope of protection afforded the present disclosure.
The various embodiments of systems, equipment, techniques, methods, activities, and operations set forth in this specification may be used for various other activities and in other fields in addition to those set forth herein. Additionally, these embodiments, for example, may be used with other equipment or activities that may be developed in the future and with existing equipment or activities which may be modified, in-part, based on the teachings of this specification. Further, the various embodiments and examples set forth in this specification may be used with each other, in whole or in part, and in different and various combinations. Thus, for example, the configurations provided in the various embodiments of this specification may be used with each other. Thus, the configurations provided in the various embodiments of this specification may be used with each other. For example, the components of an embodiment having A, A′ and B and the components of an embodiment having A″, C and D can be used with each other in various combination, e.g., A, C, D, and A. A″ C and D, etc., in accordance with the teaching of this Specification. The scope of protection afforded the present disclosure should not be limited to a particular embodiment, configuration or arrangement that is set forth in a particular embodiment, example, or in an embodiment in a particular figure.
As used herein, unless stated otherwise, room temperature is 25° C. And, standard temperature and pressure is 25° C. and 1 atmosphere. Unless expressly stated otherwise all tests, test results, physical properties, and values that are temperature dependent, pressure dependent, or both, are provided at standard ambient temperature and pressure.
Embodiments of the present disclosure include apparatuses, systems, and methods for long-duration, and ultra-long-duration energy storage. Herein, “long duration” and/or “ultra-long duration” may refer to periods of energy storage of 8 hours or longer, such as periods of energy storage of 8 hours, periods of energy storage ranging from 8 hours to 20 hours, periods of energy storage of 20 hours, periods of energy storage ranging from 20 hours to 24 hours, periods of energy storage of 24 hours, periods of energy storage ranging from 24 hours to a week, periods of energy storage ranging from a week to a year (e.g., such as from several days to several weeks to several months), etc. In other words, “long duration” and/or “ultra-long duration” energy storage devices or systems may refer to energy storage devices or systems that may be configured to store energy over time spans of days, weeks, or seasons. For example, the energy storage devices or systems may be configured to store energy generated by solar cells during the summer months, when sunshine is plentiful and solar power generation exceeds power grid requirements, and discharge the stored energy during the winter months, when sunshine may be insufficient to satisfy power grid requirements.
Other embodiments include backup power for telecommunications, data centers, electronic devices, transportation signals, medical facilities, or buildings. The duration of power delivery from the battery may range from a few minutes to a few hours. The durations of energy storage and/or power delivery described herein are provided merely as examples and are not intended to be limiting.
Various embodiments provide systems for ultra-long (days, weeks, months, years) energy storage based upon electrochemical oxidation and reduction of oxyanions that include, but are not limited to, electrochemical reactions of aqueous solutions of nitrogen, sulfur, and phosphorus oxyanions. The present systems have advantages in cost, scalability, and safety compared to existing energy storage technologies.
Existing electrochemical energy storage technologies have a high cost of energy capacity (S/kWh), making it economically infeasible to scale them to durations greater than 8 hours. This high cost is largely attributed to the use of expensive raw materials as energy storage media. The presently described system offers ultra-low cost electrochemical energy storage by utilizing abundant oxyanion chemical feedstocks for energy storage.
Various embodiments may include chemical reactants for such an electrochemical energy storage system, supporting materials, such as electrolytes and additives, and/or components of an electrochemical cell or energy storage system. Various embodiments may include the electrochemical cell and its design, as well as auxiliary subsystems aiding in the function of the energy storage system. Various embodiments may include a system comprising the electrochemical cell and subsystems aiding in its function, including but not limited to, subsystems delivering and removing gaseous reactants, subsystems delivering and removing liquid reactants, subsystems providing for interconnection of the energy storage system with electricity inputs and outputs, thermal management subsystems, and/or subsystems providing for electrical or mechanical control of the system, including but not limited to battery management systems (sometimes referred to as BMSs). Various embodiments may also include systems comprising said energy storage system and a source of electricity, including but not limited to a source of renewable electricity.
As used herein the term “redox” may refer to a reduction-oxidation reaction in which a reduction process and an oxidation process occur at the same time. During redox, one reactant loses an electron, thereby being oxidized (i.e., entering an oxidation state) and the other reactant gains an electron, thereby being reduced (i.e., entering a reduction state). Redox-active species may be species changing oxidation state (e.g., undergoing reduction or undergoing oxidation) in a reduction-oxidation reaction.
Various embodiments include electrodes, electrochemical couples, batteries, and energy storage systems comprising redox-active oxyanions, including without limitation nitrate (NO32−), nitrite (NO22−), sulfate (SO42−), sulfite (SO32−), hyposulfite (SO22−), phosphate (PO43−), phosphite (PO33−), hypophosphite (PO23−), and the like, or combinations thereof. In some embodiments, the redox-active oxyanions may include more highly oxidized or more highly reduced species such as, peroxodisulfate (S2O82−), ammonia (NH3), ammonium (NH4+), or sulfides such as S2− or HS2. In some embodiments, the redox-active oxyanions may include chlorite (ClO2−), chlorate (ClO3−), chlorine dioxide (ClO2), hypochlorite (ClO−), and the like, or combinations thereof. In some embodiments, the operation of the energy storage system comprises reversible reduction/oxidation (redox) of one or more of the oxyanion species. In some embodiments, the source of the redox-active species is a salt, including but not limited to a sodium salt, such as sodium nitrate, sodium nitrite, sodium sulfate, sodium sulfite, analogous potassium salts, or an ammonium salt such as ammonium nitrate or ammonium sulfate.
In various embodiments, provided are energy storage devices such as electrochemical cells (e.g., batteries) that include an anode, a cathode, and an aqueous electrolyte in which the redox-active oxyanions may be dissolved. The redox-active oxyanions may be considered to be an electrode active material of either the anode or the cathode, depending on the configuration of the battery.
In some embodiments an energy storage system comprises an electrochemical cell (e.g., battery) or stack or electrochemical cells in which aqueous electrolyte solutions comprising oxyanion compounds are stationary (that is, not pumped). In other embodiments, the aqueous electrolyte solutions are pumped or otherwise moved through the electrochemical stack. In some embodiments, the batteries may operate using a gaseous reactant, such as air, oxygen, or ammonia. As used herein, the term “air” may refer to a general mixture of gases making up an atmosphere, such as Earth's atmosphere (e.g., largely nitrogen, oxygen, and other elements) or other atmospheres (e.g., extraterrestrial atmospheres, selected atmospheres, etc.). In some embodiments, gaseous reactants are passively delivered to the electrochemical cells (that is, are not pumped or otherwise forced under pressure), whereas in other embodiments, said gaseous reactants are pumped or otherwise moved to or within the electrochemical cell. In some embodiments, reduction and oxidation of the gaseous reactant is conducted at a single electrode (also referred to as a bi-functional electrode). In other embodiments, reduction and oxidation of the gaseous reactant are carried out at separate electrodes. In particular embodiments, a gas-diffusion layer (GDL) electrode is used for reduction of the gaseous reactant, and/or a gas-evolution electrode is used for oxidation of the gaseous reactant. In one particular embodiment, the gaseous reactant is oxygen, and the GDL electrode is an oxygen reduction reaction (ORR) electrode, and the gas-evolution electrode is an oxygen evolution (OER) electrode.
Existing scientific literature teaches that sulfite oxidation on graphite is electrolytically irreversible. In contrast, the present inventors surprisingly found that the oxidation of sulfite to sulfate in alkaline solution (e.g., pH=13) occurs reversibly at about +0.6 V vs SHE (standard hydrogen electrode) at room temperature, while the oxygen evolution reaction (OER) occurs at about +1.4 V vs SHE. Various embodiments may include a rechargeable sulfate-oxygen, or sulfate-air, battery comprising sulfate and sulfite as the negative electrode materials and oxygen and/or air, as the positive electrode materials. In some embodiments, such a sulfate-oxygen, or sulfate-air, battery may have an open-cell voltage or operating voltage of about 0.8 V.
In some embodiments, provided are energy storage devices, such as electrochemical cells (e.g., batteries) that include stationary electrolytes (e.g., the electrolytes are not pumped or otherwise circulated during operation of the battery). In other embodiments, provided are energy storage devices that include a circulated electrolyte. For example, a volume of the electrolyte may be circulated between an electrochemical cell or stack of electrochemical cells and an electrolyte reservoir. In some embodiments, a gaseous reactant, such as air, oxygen, or ammonia, may be provided to an electrochemical cell. In some embodiments, gaseous reactants are passively delivered to the electrochemical cell (that is, are not pumped or otherwise injected), whereas in other embodiments, the gaseous reactants are pumped or otherwise provided to or circulated within the electrochemical cell. In some embodiments, reduction and oxidation of the gaseous reactant is conducted at a single electrode (also referred to as a bi-functional electrode). In other embodiments, reduction and oxidation of the gaseous reactant are carried out at separate electrodes. In particular embodiments, a gas-diffusion layer (GDL) electrode is used for reduction of the gaseous reactant, and/or a gas-evolution electrode is used for oxidation of the gaseous reactant. In one particular embodiment, the gaseous reactant is oxygen, and the GDL is an oxygen reduction reaction (ORR) electrode, and the gas-evolution electrode is an oxygen evolution reaction (OER) electrode.
In various embodiments, an electrode, electrochemical cell, battery, and/or energy storage system may be configured such that electrochemical oxidation and reduction of one or more redox-active oxyanions occurs during charging and/or discharging of the energy storage device. In some embodiments, the electrode, electrochemical cell, battery, and/or energy storage system may be configured such that electrochemical conversions between nitrate, nitrite, and/or ammonia occur during charging and/or discharging. In some embodiments, an electrode may include an aqueous solution of sodium nitrate, potassium nitrate, lithium nitrate, magnesium nitrate, calcium nitrate, calcium ammonium nitrate, sodium nitrite, potassium nitrite, lithium nitrite, or mixtures thereof. In some embodiments, the electrode, electrochemical cell, battery, and/or energy storage system may be configured such that electrochemical conversions between sulfate, sulfite, hyposulfite, thiosulfate, dithionite, and/or hydrogen sulfide occur during charging and/or discharging of the energy storage device. In some embodiments, an electrode may include an aqueous solution of an aqueous solution of sodium sulfate, potassium sulfate, magnesium sulfate, ammonium sulfate, sodium sulfite, potassium sulfite, or mixtures thereof. In some embodiments, the electrode, electrochemical cell, battery, and/or energy storage system may be configured such that electrochemical conversions between phosphate, phosphite, and hypophosphite occur during charging and/or discharging of the energy storage device. In some embodiments, an electrode may include an aqueous solution of sodium phosphate, potassium phosphate, disodium hydrogen phosphite, diammonium hydrogen phosphite, or mixtures thereof.
In various embodiments, an electrode, electrochemical cell, battery, and/or energy storage system may comprise one or more biomolecules, enzymes, and/or microorganisms which aid the reduction or oxidization of one or more redox-active species of the electrode, the electrochemical cell, the battery, and/or the energy storage system. As used herein “microorganisms” (also referred to as microbes) refers to microbial organisms, such as bacteria, protozoa, algae, viruses, etc. According to such embodiments, the redox-active species of may include any electrode-active compound serving as a positive or negative electrode, and which stores charge by undergoing changes in oxidation state. Such electrode-active compounds may comprise a solid, liquid, or gas.
Solid electrode-active compounds may comprise intercalation compounds in which the insertion or removal of an ion is accommodated by a change in the valence state of the host, non-limiting examples of which include lithium, sodium, or proton insertion cathodes and anodes used in lithium-ion, sodium-ion, nickel metal hydride, and Zn—MnO2 alkaline cells. Solid electrode-active compounds may comprise compounds undergoing a phase change upon incorporating a working ion, non-limiting examples of which include the oxidation of zinc metal to zincate, oxidation of iron to iron hydroxide (Fe(OH)2), iron oxyhydroxide (FeOOH), or iron oxide (e.g., Fe3O4 or Fe2O3).
Liquid electrode-active compounds may comprise neat or dissolved salts, including nitrogen, sulfur, and phosphorus oxyanions, ammonium, ammonia, and sulfide, as described elsewhere herein. Liquid electrode-active compounds may also include molecular species dissolved in a liquid solvent, such as ammonia, nitrogen, oxygen, chlorine, or bromine dissolved in a nonpolar solvent, or used in the form of a liquid condensed phase including liquid ammonia, liquid nitrogen, liquid oxygen, liquid chlorine, and the like.
Gaseous electrode-active compounds may include molecular species such as ammonia, nitrogen, chlorine, and oxygen in gaseous form.
In various embodiments, the oxidation or reduction of any of the aforementioned electrode-active compounds (e.g., the solid, liquid, and/or gaseous electrode-active compounds discussed above) may be aided (e.g., facilitated, catalyzed, otherwise improved, etc.) by biomolecules, enzymes, and/or microorganisms (e.g., bacteria, etc.).
In some embodiments, the electrode, the electrochemical cell, the battery, and/or the energy storage system may comprise one or more biomolecules, enzymes, microorganisms, or any combination thereof. In certain embodiments, the biomolecules, enzymes, and/or microorganisms (e.g., bacteria, etc.) may serve to catalyze the reduction or oxidation of redox-active oxyanions or other species, or to reduce or oxidize said oxyanions or redox-active species by, for example, carrying out electron transfer reactions. As a non-limiting example, sulfate-reducing and nitrate-reducing bacteria are known and may be used to facilitate or promote the reduction of sulfate to sulfite or hyposulfite, or of nitrate to nitrite. In some embodiments, the microorganisms used are selected from those present and active in environmental or natural denitrification processes, including those where nitrates and nitrates may be reduced to gaseous nitrogen species. In other embodiments, the microorganisms used are selected from those present and active in the natural sulfur cycle.
In various embodiments, the microorganisms used are selected from those tolerant of the chemical and electrochemical operating conditions of the battery. As a non-limiting example of such selection, bioelectrochemical reduction of nitrate has been observed to depend on whether sulphate is simultaneously present, and on the value of the electrical potential. For example, in the absence of sulphate, Shinella-like and Alicycliphilus-like bacteria may be exclusively found on carbon felt cathodes, while Ochrobactrum-like and Sinorhizobium-like bacteria may be found on the cathodes irrespective of sulphate presence and over a range of cathode potentials. As another example of selection of microorganisms for the purposes of the disclosure, aerobic nitrate reduction, defined as reduction in the presence of atmospheric oxygen, is preferably conducted by certain soil bacteria in the genera Pseudomonas, Aeromonas, and Moraxella. In some embodiments, said microorganisms may be anaerobic, and in other embodiments, said microorganisms may be aerobic.
Accordingly, the preferred bacteria for oxyanion reduction in some embodiments of the disclosure may be selected depending on atmospheric conditions, electrolyte composition, pH, and/or the operating electrical potential of a battery. In various embodiments, said redox reactions may be carried out in acidic solution, near neutral or neutral pH solution, or alkaline (basic) solution. In some embodiments, the pH may be between 7 and 14, and the microorganisms used to facilitate reduction or oxidation may selected, or genetically evolved, to be tolerant of high pH environments.
In some embodiments, the electrodes, electrochemical cells, batteries, or energy storage systems of the present disclosure comprise microorganisms from the group comprising sulphate-reducing bacteria (SRB). SRB are anaerobic microorganisms that are known to play an important role in both the sulfur and carbon cycles. In various embodiments, SRB may be present in the electrodes, electrochemical cells, batteries, or energy storage systems of the present disclosure to facilitate redox processes of the redox-active electrodes in accordance with various embodiments. For example, SRBs may include individually, or in combinations, Archaeoglobus fulgidus DSM 4304, Caldivirga maquilingensis IC-167, Desulfotomaculum reducens MI-1, Desulfovibrio vulgaris subsp. vulgaris strain Hildenborough, Desulfovibrio vulgaris subsp. vulgaris DP4, Desulfovibrio desulfuricans G20, Desulfotalea psychrophila LSv54, Synthrophobacter fumaroxidans MPOB, or the like.
In some embodiments, the anode and/or cathode may comprise a dispersed metal, including but not limited to nanoparticles of iron. In certain embodiments, the efficacy of the microorganism(s) in promoting reduction or oxidation is improved by the presence of dispersed metal. For example, it has been found that the microbial reduction of nitrate is enhanced in the presence of nanoparticulate iron.
Certain embodiments of the disclosure comprise a rechargeable battery wherein charging or partial charging, including the reduction of self-discharge, is accomplished by microorganisms that reduce one or more oxidized discharge products of the battery. For example, in embodiments where discharge of the battery is accommodated by the oxidation of one or more of the herein described redox-active species, charging of the battery may be accomplished by microorganisms which reduce said redox active species.
The cathode 20 may be a bifunctional cathode operable as an oxygen reduction reaction (ORR) electrode during discharging and operable as an oxygen evolution reaction (OER) electrode during charging. The cathode 20 may include a cathode catalyst layer 22 disposed on a current collector 24. The current collector 24 may comprise graphite, glassy carbon, disordered carbon, graphene, graphene oxide, carbon nanofibers, carbon nanotubes, and/or other fullerenic carbons. The cathode catalyst layer 22 may include one or more catalysts such as Cu, Ag, Pt, Ti, Fe, Ru, a Cu/Ni alloy, combinations thereof, or the like, for example.
The electrolyte 50 may be an aqueous electrolyte comprising redox-active oxyanions, including, without limitation, nitrate (NO32−), nitrite (NO22−), sulfate (SO42−), sulfite (SO32−), hyposulfite (SO22−), phosphate (PO43−), phosphite (PO33−), hypophosphite (PO23−), and the like, or combinations thereof. In some embodiments the redox-active oxyanions may include more highly oxidized or more highly reduced species such as, peroxodisulfate (S2O82−), ammonia (NH3), ammonium (NH4+), or sulfides such as S2− or HS2. In some embodiments, the redox-active oxyanions may include chlorite (ClO2-), chlorate (ClO3−), chlorine dioxide (ClO2), hypochlorite (ClO−), and the like, or combinations thereof. A source of the redox-active species may be a salt, including but not limited to, a sodium salt, such as sodium nitrate, sodium nitrite, sodium sulfate, sodium sulfite, analogous potassium salts, or an ammonium salt such as ammonium nitrate or ammonium sulfate.
Referring to
Referring to
Referring to
Nitrates (NO3−) are the most oxidized class of nitrogen compounds. Nitrate compounds, such as sodium nitrate and potassium nitrate, are used widely in the fertilizer industry. They are readily soluble in water and demonstrate high chemical stability. Nitrates can undergo a two-electron reduction to become nitrites (NO2—). Nitrites possess many similar traits as nitrates in terms of cost, solubility, and stability. Nitrites can undergo an additional six-electron reduction to become ammonia (NH3). A variety of electrocatalysts can be used to perform reversible electrochemical conversions between these species in aqueous solutions.
As shown below, half reaction 1 occurs at the anode 10, with NO3— being generated during discharging and NO2— being generated during charging, and half reaction 2 occurs at the cathode 20, with oxygen being reduced during discharging (OH— generation and O2 consumption) and with oxygen being evolved during charging (H2O and O2 generation), with the sum of reaction 1 and reaction 2 being net reaction 3:
NO3
2OH−(aq)↔H2O(I)+½O2(g)+2e−; and Reaction 2:
NO3
The charge process (energy storing) drives net reaction 3 to the right, creating nitrite (NO2—) and oxygen. The discharge process is the oxidation of nitrite to create nitrate (NO3—). The standard reduction potential of reaction 1 above is 0.01 V, while that of reaction 2 is 1.23 V. These two half reactions sum to the overall cell reaction 3, with a standard potential of 1.22 V.
The following Table 1 includes oxyanion electrode reactions and corresponding battery components that may be used in various embodiments to store and discharge power in electrochemical cells of the present disclosure.
As shown in Table 1, in some embodiments, ammonia may be oxidized during discharging of an electrochemical cell to generate nitrates and/or nitrites, which may be reduced during charging of the cell to generate ammonia. Similar oxidation and reduction reactions of sulfur species may also occur during charging and discharging of an electrochemical cell.
The following Table 2 includes other electrode reactions that may be used to store and discharge power in electrochemical cells of the present disclosure.
According to various embodiments, the energy capacity of a battery can be increased at a low marginal cost, which enables energy storage for long durations. Electrochemical energy is stored in a concentrated aqueous solution (containing dissolved oxyanion and hydroxide species) and air (containing molecular oxygen). In some embodiments, the aqueous solution may comprise or consist of water and a low-cost chemical feedstock. Therefore, the anode energy capacity can be increased at a low cost by increasing the volume of this low-cost solution. Meanwhile, the air cathode has an indefinite supply of oxygen. The scalability of energy capacity allows the energy storage device to deliver power for long durations (>8 hrs) at a low system cost.
Another advantage of the present disclosure is its limited potential for self-discharge. The aqueous electrolyte may include of a mixture of oxyanions at various oxidation states. Due to the stability of these species, all of these species can remain in the electrolyte simultaneously without undergoing self-discharge reactions. The system can remain in a charged state for long periods of time, on the order of weeks, months, and years. This facilitates smoothing the seasonal and inter-year variability of abundant but non-dispatchable energy sources such as wind, solar, or hydroelectric power. However, the present disclosure is not restricted to use over long durations and may be used over any charge or discharge duration to which a storage battery may be applied.
As the present disclosure can use common chemical feedstocks as energy storage media, it provides for greater operational flexibility than other energy storage technologies. For example, nitrites or ammonia (charged state species) may be generated by the intended energy storing process, or they may be sourced from any other available sources. Furthermore, the ammonia (or other storage chemical) synthesized by the energy storing processes, can be either used as a fuel for the electricity producing step or it may be used in other chemical processes or sold as a commodity chemical. Ammonia is most commonly produced today by the Haber-Bosch process, a thermochemical transformation which has been practiced on an industrial scale since the early twentieth century. Thus, the present technology provides advantages in flexible operation.
The theoretical volumetric energy density of the various embodiments of the present disclosure is also attractive. Consider the non-limiting case of a battery with an aqueous nitrate solution anode and air cathode. The charge storing capacity of concentrated aqueous sodium nitrate solution (10 M) is 214 Wh/L. This volumetric density is within the range of lithium ion technologies (100-200 Wh/L) and significantly higher than that of pumped hydro (0.25-1 Wh/L), the incumbent long duration storage technology.
Another advantage of the present disclosure may be improved safety. The electrolytes of various embodiments do not require flammable organic solvents. For example, aqueous electrolyte solutions including oxyanions pose limited fire risk, as compared to conventional electrolytes.
Various embodiments may provide devices and/or methods for use in bulk energy storage systems, such as long duration energy storage (LODES) systems, short duration energy storage (SDES) systems, etc. As an example, various embodiments may provide batteries for bulk energy storage systems, such as batteries for LODES systems, batteries for SDES systems, and/or batteries for systems needing power delivery for any time period. Renewable power sources are becoming more prevalent and cost effective. However, many renewable power sources face an intermittency problem that is hindering renewable power source adoption. The impact of the intermittent tendencies of renewable power sources may be mitigated by pairing renewable power sources with bulk energy storage systems, such as LODES systems, SDES systems, etc. To support the adoption of combined power generation, transmission, and storage systems (e.g., a power plant having a renewable power generation source paired with a bulk energy storage system and transmission facilities at any of the power plant and/or the bulk energy storage system) devices and methods to support the design and operation of such combined power generation, transmission, and storage systems, such as the various embodiment devices and methods described herein, are needed.
A combined power generation, transmission, and storage system may be a power plant including one or more power generation sources (e.g., one or more renewable power generation sources, one or more non-renewable power generations sources, combinations of renewable and non-renewable power generation sources, etc.), one or more transmission facilities, and one or more bulk energy storage systems. Transmission facilities at any of the power plant and/or the bulk energy storage systems may be co-optimized with the power generation and storage system or may impose constraints on the power generation and storage system design and operation. The combined power generation, transmission, and storage systems may be configured to meet various output goals, under various design and operating constraints.
As one example of operation of the power plant 350, the LODES system 304 may be used to reshape and “firm” the power produced by the wind farm 302. In one such example, the wind farm 302 may have a peak generation output (capacity) of 260 megawatts (MW) and a capacity factor (CF) of 41%. The LODES system 304 may have a power rating (capacity) of 106 MW, a rated duration (energy/power ratio) of 150 hours (h), and an energy rating of 15,900 megawatt hours (MWh). In another such example, the wind farm 302 may have a peak generation output (capacity) of 300 MW and a capacity factor (CF) of 41%. The LODES system 304 may have a power rating of 106 MW, a rated duration (energy/power ratio) of 200 h and an energy rating of 21,200 MWh. In another such example, the wind farm 302 may have a peak generation output (capacity) of 176 MW and a capacity factor (CF) of 53%. The LODES system 304 may have a power rating (capacity) of 88 MW, a rated duration (energy/power ratio) of 150 h and an energy rating of 13,200 MWh. In another such example, the wind farm 302 may have a peak generation output (capacity) of 277 MW and a capacity factor (CF) of 41%. The LODES system 304 may have a power rating (capacity) of 97 MW, a rated duration (energy/power ratio) of 50 h and an energy rating of 4,850 MWh. In another such example, the wind farm 302 may have a peak generation output (capacity) of 315 MW and a capacity factor (CF) of 41%. The LODES system 304 may have a power rating (capacity) of 110 MW, a rated duration (energy/power ratio) of 25 h and an energy rating of 2,750 MWh.
As one example of operation of the power plant 450, the LODES system 304 may be used to reshape and “firm” the power produced by the PV farm 402. In one such example, the PV farm 402 may have a peak generation output (capacity) of 490 MW and a capacity factor (CF) of 24%. The LODES system 304 may have a power rating (capacity) of 340 MW, a rated duration (energy/power ratio) of 150 h and an energy rating of 51,000 MWh. In another such example, the PV farm 402 may have a peak generation output (capacity) of 680 MW and a capacity factor (CF) of 24%. The LODES system 304 may have a power rating (capacity) of 410 MW, a rated duration (energy/power ratio) of 200 h, and an energy rating of 82,000 MWh. In another such example, the PV farm 402 may have a peak generation output (capacity) of 330 MW and a capacity factor (CF) of 31%. The LODES system 304 may have a power rating (capacity) of 215 MW, a rated duration (energy/power ratio) of 150 h, and an energy rating of 32,250 MWh. In another such example, the PV farm 402 may have a peak generation output (capacity) of 510 MW and a capacity factor (CF) of 24%. The LODES system 304 may have a power rating (capacity) of 380 MW, a rated duration (energy/power ratio) of 50 h, and an energy rating of 19,000 MWh. In another such example, the PV farm 402 may have a peak generation output (capacity) of 630 MW and a capacity factor (CF) of 24%. The LODES system 304 may have a power rating (capacity) of 380 MW, a rated duration (energy/power ratio) of 25 h, and an energy rating of 9,500 MWh.
As one example of operation of the power plant 500, the LODES system 304 may be used to reshape and “firm” the power produced by the wind farm 302 and the PV farm 402. In one such example, the wind farm 302 may have a peak generation output (capacity) of 126 MW and a capacity factor (CF) of 41% and the PV farm 402 may have a peak generation output (capacity) of 126 MW and a capacity factor (CF) of 24%. The LODES system 304 may have a power rating (capacity) of 63 MW, a rated duration (energy/power ratio) of 150 h, and an energy rating of 9,450 MWh. In another such example, the wind farm 302 may have a peak generation output (capacity) of 170 MW and a capacity factor (CF) of 41% and the PV farm 402 may have a peak generation output (capacity) of 110 MW and a capacity factor (CF) of 24%. The LODES system 304 may have a power rating (capacity) of 57 MW, a rated duration (energy/power ratio) of 200 h, and an energy rating of 11,400 MWh. In another such example, the wind farm 302 may have a peak generation output (capacity) of 105 MW and a capacity factor (CF) of 51% and the PV farm 402 may have a peak generation output (capacity) of 70 MW and a capacity factor (CF) of 31 The LODES system 304 may have a power rating (capacity) of 61 MW, a rated duration (energy/power ratio) of 150 h, and an energy rating of 9,150 MWh. In another such example, the wind farm 302 may have a peak generation output (capacity) of 135 MW and a capacity factor (CF) of 41% and the PV farm 402 may have a peak generation output (capacity) of 90 MW and a capacity factor (CF) of 24%. The LODES system 304 may have a power rating (capacity) of 68 MW, a rated duration (energy/power ratio) of 50 h, and an energy rating of 3,400 MWh. In another such example, the wind farm 302 may have a peak generation output (capacity) of 144 MW and a capacity factor (CF) of 41% and the PV farm 402 may have a peak generation output (capacity) of 96 MW and a capacity factor (CF) of 24%. The LODES system 304 may have a power rating (capacity) of 72 MW, a rated duration (energy/power ratio) of 25 h, and an energy rating of 1,800 MWh.
Together the LODES system 304 and the transmission facilities 306 may constitute a power plant 600. As an example, the power plant 600 may be situated downstream of a transmission constraint, close to electrical consumption. In such an example downstream situated power plant 600, the LODES system 304 may have a duration of 24 h to 500 h and may undergo one or more full discharges a year to support peak electrical consumptions at times when the transmission capacity is not sufficient to serve customers. Additionally in such an example downstream situated power plant 600, the LODES system 304 may undergo several shallow discharges (daily or at higher frequency) to arbiter the difference between nighttime and daytime electricity prices and reduce the overall cost of electrical service to customer. As a further example, the power plant 600 may be situated upstream of a transmission constraint, close to electrical generation. In such an example upstream situated power plant 600, the LODES system 304 may have a duration of 24 h to 500 h and may undergo one or more full charges a year to absorb excess generation at times when the transmission capacity is not sufficient to distribute the electricity to customers. Additionally in such an example upstream situated power plant 600, the LODES system 304 may undergo several shallow charges and discharges (daily or at higher frequency) to arbiter the difference between nighttime and daytime electricity prices and maximize the value of the output of the generation facilities.
Together, the LODES system 304 and transmission facilities 306 may constitute a power plant 700. As an example, the power plant 700 may be situated close to electrical consumption, i.e., close to the C&I customer 702, such as between the grid 308 and the C&I customer 702. In such an example, the LODES system 304 may have a duration of 24 h to 500 h and may buy electricity from the markets and thereby charge the LODES system 304 at times when the electricity is cheaper. The LODES system 304 may then discharge to provide the C&I customer 702 with electricity at times when the market price is expensive, therefore offsetting the market purchases of the C&I customer 702. As an alternative configuration, rather than being situated between the grid 308 and the C&I customer 702, the power plant 700 may be situated between a renewable source, such as a PV farm, wind farm, etc., and the transmission facilities 306 may connect to the renewable source. In such an alternative example, the LODES system 304 may have a duration of 24 h to 500 h, and the LODES system 304 may charge at times when renewable output may be available. The LODES system 304 may then discharge to provide the C&I customer 702 with renewable generated electricity so as to cover a portion, or the entirety, of the C&I customer 702 electricity needs.
The LODES system 304 may output stored power to the transmission facilities 306. The transmission facilities 306 may output power received from one or both of the wind farm 302 and LODES system 304 to the C&I customer 702. Together the wind farm 302, the LODES system 304, and the transmission facilities 306 may constitute a power plant 800 that may be a combined power generation, transmission, and storage system. The power generated by the wind farm 302 may be directly fed to the C&I customer 702 through the transmission facilities 306, or may be first stored in the LODES system 304. In certain cases, the power supplied to the C&I customer 702 may come entirely from the wind farm 302, entirely from the LODES system 304, or from a combination of the wind farm 302 and the LODES system 304. The LODES system 304 may be used to reshape the electricity generated by the wind farm 302 to match the consumption pattern of the C&I customer 702. In one such example, the LODES system 304 may have a duration of 24 h to 500 h and may charge when renewable generation by the wind farm 302 exceeds the C&I customer 702 load. The LODES system 304 may then discharge when renewable generation by the wind farm 302 falls short of C&I customer 702 load so as to provide the C&I customer 702 with a firm renewable profile that offsets a fraction, or all of, the C&I customer 702 electrical consumption.
In certain cases the power supplied to the C&I customer 702 may come entirely from the PV farm 402, entirely from the wind farm 302, entirely from the LODES system 304, entirely from the thermal power plant 902, or from any combination of the PV farm 402, the wind farm 302, the LODES system 304, and/or the thermal power plant 902. As examples, the LODES system 304 of the power plant 900 may have a duration of 24 h to 500 h. As a specific example, the C&I customer 702 load may have a peak of 100 MW, the LODES system 304 may have a power rating of 14 MW and duration of 150 h, natural gas may cost $6/million British thermal units (MMBTU), and the renewable penetration may be 58%. As another specific example, the C&I customer 702 load may have a peak of 100 MW, the LODES system 304 may have a power rating of 25 MW and duration of 150 h, natural gas may cost $8/MMBTU, and the renewable penetration may be 65%.
Having described above certain aspects of energy storage systems, devices, and components including aqueous oxyanion electrolytes, attention is now specifically directed to description of aspects of halogen oxyanion-based electrodes and related batteries and systems. For the sake of clear and efficient description, aspects of the energy storage systems, devices, and components described above are not necessarily repeated in the description of halogen oxyanion-based electrodes and related batteries and systems described below. However, unless otherwise specified or made clear from the context, it shall be understood that various aspects of the energy storage systems, devices, and components described above may be combined with the halogen oxyanion-based electrodes and related batteries and systems described below. For example, unless a contrary intent is explicitly indicated or is clear from the context, any one or more of the various, different halogen oxyanion-based electrodes and related batteries and systems described below may be uses as part of bulk energy storage systems, such as LODES systems, SDES systems, systems needing power delivery for any time period, etc., such as the examples described above with respect to
In some embodiments, an electrochemical cell includes a negative electrode, a positive electrode, an electrolyte, and a separator disposed between the positive electrode and the negative electrode (for example as shown in
In some embodiments, a plurality of electrochemical cells (or batteries) 1000 in
Various embodiments include halogen oxyanion based electrodes and related batteries and systems. Various embodiments include electrochemical electrode reactions comprising halogen oxyanions. Various embodiments may include an electrode in an electrochemical device comprising an electrode reaction, or redox reaction, of a halogenated oxyanion species.
Various embodiments include reversible Cl(III)/Cl(IV) electrodes, processes for making reversible Cl(III)/Cl(IV) electrodes, and batteries and battery systems including reversible Cl(III)/Cl(IV) electrodes. Various embodiments may include a direct reversible Cl(III)/Cl(IV) cathode, for example coupled with ClO2 storage, in a battery and/or battery system. Various embodiments may include an indirect Cl(III)/Cl(IV) electrode, for example without ClO2 storage, in a battery and/or battery system. Such indirect Cl(III)/Cl(IV) electrode may be, for example, based on a 3-Chemical Chlorine Dioxide Reaction.
A first example implementation may include an alkaline electrolyte with a polysulfide electrode and NaClO2 electrode. Such an example has been observed to have an open circuit voltage (OCV) of 1.50 volts (V). A second example implementation may include an alkaline electrolyte with an iron electrode and NaClO2 electrode. Such an example is calculated to have an OCV of 1.84V. A third example implementation may include a neutral electrolyte with an iron electrode and NaClO2 electrode. Such an example is calculated to have an OCV of 1.39V. A fourth example implementation may include an acidic electrolyte with a hydrogen electrode and NaClO2 electrode. Such an example is calculated to have an OCV of 1.27V.
Various embodiments may include an electrode in an electrochemical device comprising an electrode reaction, or redox reaction, of a halogenated oxyanion species. Various embodiments may include certain chemical species involved in said redox reactions, one or more of which may be a halogenated oxyanion. The reactant or product of said redox reaction may comprise an ionic or electrically neutral chemical species. In some embodiments, the electrochemical device is a storage battery, which may include batteries of the primary type, which is understood to mean that the battery is provided in a charged or partially charged state and discharged once, or may be batteries of secondary type, which is understood to mean rechargeable batteries which may be recharged or partially recharged at least once before being discharged again. In some embodiments, said redox reaction may comprise oxidation of said halogenated oxyanion species. In other embodiments, said redox reaction may comprise reduction of said halogenated oxyanion species. In some embodiments, said redox reaction may comprise the reversible oxidation and reduction of said chemical species. In various embodiments, the current collector at which said redox reaction occurs may be selected to allow such highly reversible reaction, by which it is meant that the overpotential for oxidation or reduction is relatively small. Such current collectors may comprise various metals or metal compounds as described herein, and preferably, may comprise carbon. Said electrode may comprise the positive electrode or the negative electrode of said electrochemical device. In some embodiments, the halogen may be chlorine or bromine.
In addition to chemical compositions used in said redox reactions, electrodes, and electrochemical devices, various embodiments may include materials used in said electrochemical devices, the design of said devices, and systems and methods of use of said devices and systems.
An example of the redox reactions of the various embodiments is the electrochemical reaction between chlorine (III) oxyanion (ClO2-) and chlorine (IV) dioxide (ClO2), which in some embodiments may be carried out in an aqueous electrolyte. The chlorine (III) oxyanion (i.e., chlorite containing compound) may be provided in the form of a chlorite salt, including but not limited to HClO2, LiClO2, NaClO2, KClO2, RbClO2, and CsClO2, which may dissociate at least partially in the electrolyte used. Such reversible halogenated oxyanion electrodes may be operated in acidic, neutral, or alkaline aqueous electrolytes.
In acidic electrolyte, the electrode half-cell reaction may be:
ClO2+H++e−⇔HClO2E0=1.277VvsSHE (Eq. 1)
In neutral or alkaline electrolyte, the electrode half-cell reaction may be:
ClO2(aq)+e−⇔ClO2−E0=0.954VvsSHE (Eq. 2)
The solubility of NaClO2 in water is substantial, being:
8.4mol_NaClO2/L_H2O at 25degC; and 4.3mol_NaClO2/L_H2O at 17degC.
Accordingly, in use as an electrochemical battery, an aqueous electrolyte may have a substantial concentration of ClO2 or HClO2, resulting in a desirably high storage capacity or energy density.
According to the above electrode half-cell reactions, ClO2, chlorine dioxide, may be the product of the oxidation reaction. The solubility of ClO2 in water is relatively low, being 0.12 mol_ClO2/L_H2O at 20 degC. The boiling point of ClO2 at 1 atmosphere pressure is about 11 degC, and said boiling point increases with the applied pressure. The freezing point of ClO2 is about −68 degC. In some embodiments, at least a portion of the chlorine dioxide produced by electrochemical oxidation is present within or as a phase separate and distinct from the aqueous electrolyte. Said phase may be a liquid phase, or a solid phase. In some embodiments, the operating temperature of the battery is low enough, and the pressure to which the reactants are subjected is high enough, so that at least some of the chlorine dioxide produced is present as a separate phase. In some embodiments, the electrochemical device is sealed, and is under internal pressure during at least some of its state-of-charge range.
In some embodiments, the current collector for the reversible Cl(III)/Cl(IV) electrode comprises a carbon-based material, a metal or metal alloy, or an electronically conductive compound. Said carbon-based material may comprise glassy carbon, disordered carbon, graphite, carbon black, activated carbon, carbon fiber, carbon nanotubes, heteroatom doped carbon nanotube, graphene, heteroatom doped graphene, graphene oxide, or other carbonaceous material. In certain embodiments, the carbon-based current collector comprises the form of a carbon plate, carbon felt, carbon foam, reticulated carbon, carbon cloth, carbon paper, or other form. Said metal or metal alloy may comprise iron, carbon steel, stainless steel, titanium, nickel, copper, silver, platinum, palladium, or other metal. Said electronically conductive compounds may comprise metal carbides, metal sulfides, metal nitrides, metal oxides, or alloys of such compounds.
In certain embodiments, the reversible Cl(III)/Cl(IV) electrode contains oxygen evolution inhibitors or suppressants. In certain embodiments, the reversible Cl(III)/Cl(IV) electrode contains electrocatalysts including but not limited to, noble metals and alloys, noble metal oxides, transition metals and alloys, transition metal oxides, and the like. In certain embodiments, the reversible Cl(III)/Cl(IV) electrode is a gas diffusion electrode containing hydrophobic polymers such as PTFE, FEP, polyethylene, polypropylene, or a combination thereof.
In some embodiments, the current collector is in the form of solid plate, perforated plate, felt, foam, wool, mesh, or other form. In some embodiments, the current collector is a conductive substrate coated by one or more of the preceding electrode or catalyst materials.
Reversible Cl(III)/Cl(IV) Electrode
The oxidation reaction from chlorite (ClO2-) to chlorine dioxide (ClO2), and the reduction reaction back to chlorite, is surprisingly found to be highly reversible with low overpotential in either direction, and in acidic or alkaline electrolyte, as shown in the following examples.
Three-electrode cyclic voltammetry was conducted at room temperature (about 23° C. in this context) using a glassy carbon working electrode, a platinum counter electrode, and an Ag/AgCl reference electrode (3M NaCl). The electrolyte contained 10 mM NaClO2 dissolved in reverse osmosis deionized (RODI) water, and 1M KOH, producing pH≈14. A polypropylene laboratory cell was used. The working electrode potential was swept from −1.2V to 1.0V (with respect to Ag/AgCl) at a rate of 100 mV/sec and the current was recorded. An example of the results is shown in
Three-electrode cyclic voltammetry was conducted at room temperature (about 23° C. in this context) using a glassy carbon working electrode, a platinum counter electrode, and an Ag/AgCl reference electrode (3M NaCl). The electrolyte contained 10 mM NaClO2 dissolved in reverse osmosis deionized (RODI) water, and 9 mM H2SO4, producing pH 2. A polypropylene laboratory cell was used. The working electrode potential was swept from −0.6V to 1.4V (with respect to Ag/AgCl) at a rate of 100 mV/sec and the current was recorded. An example of the results is shown in
Thus, as may be appreciated from the results of Example 1 and Example 2 above, the Cl(III)/Cl(IV) redox reaction is shown to be highly reversible in both acidic and alkaline solution.
Direct Reversible Cl(III)/Cl(IV) Electrode (with ClO2 Storage)
Depending on the temperature and pressure, chlorine dioxide can be stored in the form of a gas, liquid, liquid solution, solid, or a combination thereof. A chlorite bearing compound, including for example NaClO2, NaBrO2, KClO2, or KBrO2, may be stored as a dissolved solution. In some embodiments, the chlorite bearing compound and chlorine dioxide may be stored in the same enclosure. In some embodiments, the chlorite containing compound and chlorine dioxide may each be stored in separate enclosure. In certain embodiments, chlorine dioxide may be stored at a temperature ≤11° C. In certain embodiments, the reversible Cl(III)/Cl(IV) electrode may include a chlorite stabilizer. In certain embodiments, the reversible Cl(III)/Cl(IV) electrode may contain a chlorine dioxide stabilizer. Such stabilizers may reduce or eliminate decomposition of chlorine dioxide to other compounds, or decrease the self-discharge rate of the battery. In certain embodiments, the reversible Cl(III)/Cl(IV) electrode may be used in a tank cell configuration where the active species are contained within the cell embodiment. In certain embodiments, the reversible Cl(III)/Cl(IV) electrode may be in a flow cell configuration where the active species are pumped to the cell from an external storage vessel. In some embodiments as a storage battery, during charge, Cl(III) is oxidized to Cl(IV), and the electrical energy is stored in the form of chlorine dioxide. During discharge, Cl(IV) is reduced to Cl(III), and the electrical energy is released to the external circuit.
An Iron-Chlorine Dioxide Battery
A Cl(III)/Cl(IV) electrode, such as any one or more of the Cl(III)/Cl(IV) electrode described above, may be used as a reversible electrode. As described in greater detail below, embodiments of the reversible Cl(III)/Cl(IV) electrode include: direct reversible Cl(III)/Cl(IV) cathode (with ClO2 storage) and indirect Cl(III)/Cl(IV) electrode (without ClO2 storage) (based on 3-Chemical Chlorine Dioxide Reaction).
The above-described Cl(III)/Cl(IV) electrode may be used as a positive electrode in a battery. It may be paired with various negative electrodes, including but not limited to the following combinations: polysulfide negative electrode NaClO2 alkaline electrolyte battery (OCV=1.50V, empirical); iron negative electrode NaClO2 alkaline electrolyte battery (OCV=1.84V, calculated); iron negative electrode NaClO2 neutral electrolyte battery (OCV=1.39V, calculated); hydrogen negative electrode NaClO2 acidic electrolyte battery (OCV=1.27V, calculated). Several of these examples are described in greater detail below.
More generally, the negative electrode may include a metal or alloy, including but not limited to a first-row transition metal (e.g., titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, or zinc), tin, cadmium, lead, magnesium, calcium, aluminum lithium, sodium, potassium, rubidium, or cesium. The negative electrode may have a half-cell reaction, especially in alkaline electrolyte, that comprises the formation of an oxide, hydroxide, or other metal salt during oxidation, corresponding to discharge of the battery. The metal salt may be soluble in the electrolyte in some instances. In other instances, the metal salt may remain in solid form and may be at least partially attached to the metal or alloy. Upon charging, the metal salt may be reduced to a metal or alloy.
The negative electrode may also have, especially in acidic electrolyte, a half-cell reaction comprising dissolution of the metal as metal ions or complexes in the electrolyte upon discharge of said battery. Upon charging, the metal ions or complexes may be reduced to the metal or alloy.
In some embodiments, the negative electrode comprises sulfur. Sulfur negative electrodes may comprise sulfur in any of its oxidation states including elemental sulfur and various polysulfides including S2−, S22−, S32−, S42−, and S52−. For example, such polysulfides may be prepared by dissolving in aqueous solution any one or more of the compounds Na2S, Na2S2, Na2S3, Na2S4, or Na2S5. The electrolyte may be alkaline, to avoid the formation of H2S gas. In a particular embodiment, the electrolyte is alkaline and the polysulfide is cycled between the limits S22− to S42−. A battery cell using S22−/S42− as the negative electrode redox reaction and ClO2−/ClO2 as the positive electrode redox reaction may have an open circuit voltage of about 1.50 V.
In some embodiments, the oxidation or reduction of a positive or negative electrode may be facilitated or assisted by a redox mediator compound.
As an example of such a battery, consider an iron-chlorine dioxide battery, the operation of which is shownin
Another configuration for an iron-chlorine dioxide battery may comprise an acidic electrolyte of pH<7. In such instances, the oxidation of the iron electrode upon discharge of the battery may comprise its dissolution as ferrous ion: Fe0=Fe2++2e−. During charging, dissolved iron ions may be reduced at the negative electrode, in the reverse of this reaction.
According to these embodiments, the starting state of the battery may be charged or partially charged, in which case there is at least some metallic iron or an iron alloy at the negative electrode and at least some chlorine dioxide at the positive electrode. This starting state may be achieved by assembling the battery using metallic iron and chlorine dioxide as components. Additionally, or alternatively, the starting state may be achieved by carrying out an initial electrochemical reaction that forms ClO2 within the cell, regardless of whether the iron-comprising negative electrode undergoes reduction to metallic iron. This initial electrochemical reaction is also herein referred to as “formation” or a “formation cycle” or “formation reaction,” and has the characteristics that a reduction “side reaction” occurs at the negative electrode so that oxidation can occur at the positive electrode. This side reaction may produce a reaction product that is a gas, liquid, or solid, and which may not thereafter substantially participate in the charge-discharge reactions of the battery.
An example of such a formation cycle is shown in
During the formation reaction, a source of chlorite ions is for forming chlorine dioxide may include a chlorite compound, such as an alkali chlorite (e.g., NaClO2). As shown in
ClO2 has limited solubility in aqueous solution, and has a density of 1.64 g/cm3 that is higher than that of typical aqueous electrolytes. The density of ClO2 may also be lower than that of certain electrolytes such as the “water-in-salt” type of electrolyte, wherein there is a higher concentration of the electrolyte salt than the water solvent. Accordingly, as shown in
In some embodiments, an electrolyte with a high salt concentration is used. While many typical aqueous electrolytes may have a salt concentration of about 1 M, or even less, in some instances the salt concentration may exceed 1 M, or even 5 M or 10 M. Electrolytes with a salt concentration that exceeds the solvent concentration are sometimes referred to as “water in salt” electrolytes, to contrast with typical electrolytes in which the salt is dissolved in water. Without being bound by any particular scientific interpretation, the use of a highly concentrated electrolyte may allow the Cl(III)/Cl(IV) reaction, or the ClO2−/ClO2 reaction, to be conducted with a decreased rate of competing parasitic or “side” reactions such as the oxygen evolution reaction (OER).
As shown in
Indirect Cl(III)/Cl(IV) Electrode without ClO2 Storage, and Batteries and Systems Thereof.
Various embodiments relate to an electrode, electrochemical device, or system in which the ClO2 to ClO2− electrochemical reduction reaction is utilized, while the reactant ClO2 is produced as needed to supply the reaction rather than being stored as ClO2. Such a system has the advantage of not needing to store or manage a reservoir of ClO2, which is known to be an unstable chemical under certain conditions. The design and operation of such a system is shown in
Chlorine dioxide may be produced using the chemical reaction: 2NaClO2+HOCl+HCl→2ClO2+2NaCl+H2O. Chlorite to chlorine dioxide conversion of 95-98% is possible via this reaction. In various embodiments, a different reaction, 2NaClO2+NaOCl+NaCl→2ClO2+NaCl+2NaOH, is used to produce ClO2 for the electrode reaction of an electrochemical battery. In such a battery, the ClO2 is electrochemically reduced to chlorite, ClO2−. In instances in which the chlorite/chlorine dioxide reaction comprises the positive electrode reaction, the reduction of chlorine dioxide to chlorite corresponds to the discharge reaction of the battery.
During discharge (
The relative amounts of the solution in the ClO2 vessel 1204 circulated to the electrochemical cell and the NaClO+NaCl storage vessel 1208 may be varied, but generally maintains the NaCl and/or NaOH concentrations and solution volumes in the respective storage vessels.
Referring now to
In certain embodiments, the pH of the solution in the ClO2 vessel 1204 is optimized for ClO2 generation and short term storage. In some embodiments, the pH of the solution in the NaClO2 storage vessel 1206 is optimized for stable NaClO2 storage. In some embodiments, the pH of the solution in the NaClO+NaCl storage vessel 1208 is optimized for stable NaClO storage.
In some embodiments, the indirect Cl(III)/Cl(IV) electrode includes a monofunctional ClO2 reducing electrode and a chlorine generation electrode. In certain embodiments, the chlorine generation electrode contains materials known for use in chloralkali anodes. In some embodiments, the indirect Cl(III)/Cl(IV) electrode includes a bifunctional electrode for both ClO2 reduction process and the chlorine generation process. In certain embodiments, the pH of the solution in the ClO2 vessel is lower than 7. In certain embodiments, the pH of the solution in the NaClO+NaCl is higher than 7.
In some embodiments, the battery is a flow battery, in which the electrochemical cell and one or more of the vessels shown in
Reversible Chlorite/Chlorine Dioxide Anion Redox Couple
Decarbonization of global electricity production will require significant amounts of power storage to be deployed. This creates challenges in terms of both the availability and the scaling of mining and extraction of critical metals such as Li, Co, Ni, V, or Sb, depending on the elemental requirements of the storage technology being used. For battery chemistries that do meet cost and scalability criteria, additional criteria such as energy efficiency (typically represented by coulombic and voltaic efficiency), durability (cycle and calendar life), operating temperature, and safety, come into consideration. However, the ranked importance of such criteria may be unique to each application. There exists a continuing need for new redox couples for rechargeable batteries that can meet current and future needs.
The aqueous chlorine dioxide/chlorite (ClO2/ClO2−) redox couple has exceptional electrochemical reversibility using catalyst-free, low-cost carbon electrodes. The large crustal abundance of chlorine, which is the highest amongst halogens and is greater than that of nitrogen, makes chlorine attractive as the basis for low-cost, large-scale storage. In particular, the chlorite ion is widely available at low cost when sourced from sodium chlorite (NaClO2). Furthermore, since oxidation to chlorine dioxide occurs at a standard potential of 0.954V vs SHE, the ClO2/ClO2− redox couple is attractive as a positive electrode that can be paired with a wide range of possible negative electrodes, which include low-cost candidates such as Zn or Fe metal electrodes, or S in the form of dissolved polysulfide species. The following Table 3 summarizes the theoretical equilibrium cell voltages of rechargeable batteries using chlorine oxyanion electrochemical couples (e.g., Cl(III)/Cl(IV) couples) as the positive electrode in neutral and alkaline electrolytes.
As indicated in Table 3, an alkaline Zn/ClO2 battery can have a 2.15V equilibrium cell voltage, which ranks amongst the highest of aqueous battery systems. As used herein, the term the “chemical cost of storage energy” is defined as the estimated cost of starting electrode materials and electrolyte divided by stored energy and is used as a metric that represents the minimum cost of any battery system in U.S. dollars per kilowatt hour (thus, chemical cost of storage is represented symbolically herein as “$X/kWh”, where X is the value), and shall be understood to be based on 2022 U.S. dollars. The ClO2/ClO2− based battery chemistries described herein, assuming the use of NaClO2 as a starting material, have estimated chemical costs of $3/kWh-$10/kWh. This estimated chemical cost range compares favorably to comparable estimates of Li-ion chemistries ($20/kWh-$30/kWh), vanadium redox flow batteries (˜$100/kWh), and iron-air batteries ($1.3/kWh). Rechargeable Zn/ClO2 cells are described herein as an example of this chemistry.
While the electrochemical oxidation of chlorite to chlorine dioxide is the basis for significant commercial production of ClO2, an industrial chemical most widely used for disinfection, the reverse reaction (electrochemical reduction to ClO2−) has not been extensively studied. Without wishing to be bound by theory, it is believed that the reaction ClO2-↔ClO2+e− is highly reversible, since only electron transfer is required, rather than atomic bond breaking or formation (e.g., as in chlorine oxidation 2Cl−↔H Cl2+2e−). Simple electron transfer is advantageously used for several transition metal cations used as redox-active battery electrodes in aqueous solution (e.g., Fe(II)/Fe(III), V(II)/V(III), V(IV)/V(V), Cr(II)/Cr(III), Ce(III)/Ce(IV), etc.), particularly in flow batteries.
Referring to
A pH shift is seen for the oxygen evolution reaction (OER), which occurs at a lower potential (at ˜0.9V vs Ag/AgCl) in the alkaline CV curve than in the neutral or acidic condition in
Referring to
Referring to
As a storage electrode, ClO2 may be stored in either a gaseous or liquid phase. The currently described experiments span the boiling point of ClO2, which is 11° C. at one atmosphere pressure. These experiments confirm that the reaction has good electrochemical reversibility both above and below the boiling point of ClO2, as described in greater detail below. Indeed, the separation in potential between oxidation and reduction peaks, as well as the magnitude of the peak currents, are nearly the same between 5° C. and 20° C. For practical application in battery systems, storage as a condensed phase is desirable for higher energy density and ease of containment. Note that liquid ClO2 is immiscible with aqueous electrolytes and has a higher density of 1.64 g/cm3. These features facilitate the storage of ClO2 as a separate liquid phase, without resorting to high pressures and facilitates the use density-based separation, as described in greater detail below.
To demonstrate use of the ClO2−/ClO2 couple in a full cell, Zn—ClO2 cells were prepared and tested while operating with near-neutral electrolyte at temperature of 0.5±0.5° C., where any ClO2 phase produced is liquid. The Zn—ClO2 couple has the highest theoretical equilibrium cell voltage of the anode-cathode combinations considered above, 1.72V (Table 3), which is about 0.5V higher than that of several well-known aqueous rechargeable chemistries such the Fe—Ni “Edison” battery (1.4V), Ni—Cd battery (1.2 V), vanadium redox flow battery (1.26V), and the all-Fe redox battery (1.2V). In alkaline media, when Zn metal and NaClO2 (dissolved in the electrolyte) are used as the starting materials, it is necessary to perform a first charging step to produce ClO2, at the negative electrode, during which hydrogen evolution occurs at the positive electrode, according to the negative electrode half-cell charging reaction (Reaction 4), the positive electrode half-cell charging reaction (Reaction 5), and the full cell charging reaction (Reaction 6):
2H2O+2e−↔H2+2OH−; Reaction 4:
2ClO2−↔2ClO2+2e−; and Reaction 5:
2H2O+2ClO2
With ClO2 formed, the cell is in the fully charged state with Zn and ClO2 present at negative and positive electrodes, respectively, and may be operated reversibly, with the negative electrode half-cell discharging reaction (Reaction 7), the positive electrode half-cell discharging reaction (Reaction 8), and the full cell charging reaction (Reaction 9):
Zn+2OH−↔Zn(OH)2+2e−; Reaction 7:
2ClO2+2e−↔2ClO2−; and Reaction 8:
Zn+2OH−+2ClO2↔Zn(OH)2+2ClO2
Assuming a balanced cell with equal capacity at the negative and positive electrodes, an alkaline electrolyte containing NaClO2 as the sole source of working chlorite ions, and assuming that the ClO2 formed upon charge is present as a pure liquid, the theoretical energy density is calculatable. This energy density is primarily limited by the solubility of NaClO2 in the electrolyte, which was independently determined to be 2 M and 3 M at 0° C. and 20° C., respectively. The corresponding calculated energy density values are 77 Wh/L and 106 Wh/L, and the estimated chemical cost of stored energy (cost of Zn and electrolyte components divided by the stored energy) is 7.3$/kWh. This estimated chemical cost is significantly lower than estimates for Li-ion, Ni—Cd and NiMH batteries ($30/kWh-80$/kWh) as well as estimates for vanadium redox flow batteries (100$/kWh) and is comparable to estimates for primary Zn/MnO2 and high temperature rechargeable Na/NiCl2 batteries.
Referring to
Initial full-cell experiments conducted in three-electrode beaker-type cells led to the flat cell design as shown, which was used to obtain the results below. Two likely parasitic reactions were recognized in the initial full-cell experiments conducted in three-electrode beaker-type cells, and the cell design was adapted to reduce such reactions. Without wishing to be bound by theory, one such parasitic reaction is believed to be the reaction that occurs between Zn metal and ClO2−, forming solid Zn(OH)2 and water. The constructed full cell included a zinc sheet negative electrode and vitreous carbon foam positive electrode, separated by a Nafion™ 117 membrane (available from The Chemours Company of Wilmington, Delaware, United States) that was pre-soaked in an NaOH solution to provide Na+ ion conductivity, while significantly blocking the crossover of chlorite ions, thereby mitigating this side reaction.
Again without wishing to be bound by theory, a second parasitic reaction is believed to be the disproportionation reaction ClO2+H2O↔ClO2−+ClO3−+2H+. To reduce the likelihood of this reaction, the ClO2 may be exsolved as a separate liquid phase, taking advantage of its low solubility in water, thus reducing contact. Additionally, or alternatively, separating ClO2 from water may include providing a separate, immiscible, organic phase in which the ClO2 is soluble, as an accumulator phase. This approach decreases energy density but has the advantage of lowering the vapor pressure of ClO2. Several organic liquids having significant solubility for ClO2 are known; here a synthetic saturated hydrocarbon solvent was selected with a similar range of carbon number to that of Diesel fuel, a ClO2 solubility of about 4 g/L, and that segregates as a surface layer on the aqueous electrolyte due to its lower density (
The open-circuit voltage (OCV) of the cell was 1.7V, close to the theoretical value, after charging to 10% state-of-charge (SOC). Reversible cycling was observed, with a coulombic efficiency of 92-96% over the first 50 cycles. By comparison, beaker-type cells without either the Nafion membrane or the organic solvent accumulator exhibited a coulombic efficiency of less than 50%.
For the flat cells, after about 50 cycles, a step change in charge voltage emerged at a high SOC. A similar feature is seen in the plot of cathode-reference potential vs. capacity in
These loss mechanisms may be further mitigated by improvements in cell design, including implementation in half-flow or flow-battery designs. Treating the cell in
According to various embodiments, the ClO2−/ClO2 electrochemical reaction is shown to be highly reversible in acidic, near-neutral, and alkaline electrolytes while using low-cost carbon electrodes. Its equilibrium potential (0.954 V vs SHE) is pH-independent and facilitates high aqueous cell voltages of 1.38-2.15 V when used as a positive electrode in conjunction with negative electrodes such as Zn, Fe, or S electrodes. This anion redox couple may facilitate production of low-cost aqueous rechargeable batteries, free or substantially free of resource-constrained metals. The rapid reaction kinetics and stability of the ClO2 phase at low temperatures also suggests that chlorite-based batteries may be favorable for applications in cold environments.
The foregoing method descriptions are provided merely as illustrative examples and are not intended to require or imply that the steps of the various embodiments must be performed in the order presented. As will be appreciated by one of skill in the art the order of steps in the foregoing embodiments may be performed in any order. Words such as “thereafter,” “then,” “next,” etc. are not necessarily intended to limit the order of the steps; these words may be used to guide the reader through the description of the methods. Further, any reference to claim elements in the singular, for example, using the articles “a,” “an” or “the” is not to be construed as limiting the element to the singular.
Various examples are provided below to illustrate aspects of the various embodiments. Example 1. An electrode which performs electrochemical oxidation and reduction of oxyanions. Example 2. The electrode of example 1 which performs electrochemical conversions between nitrate, nitrite, and ammonia, the electrode comprising an aqueous solution of sodium nitrate, potassium nitrate, lithium nitrate, magnesium nitrate, calcium nitrate, calcium ammonium nitrate, sodium nitrite, potassium nitrite, lithium nitrite, or mixtures thereof. Example 3. The electrode of example 1 which performs electrochemical conversions between sulfate, sulfite, hyposulfite, thiosulfate, dithionite, and hydrogen sulfide, the electrode comprising an aqueous solution of sodium sulfate, potassium sulfate, magnesium sulfate, ammonium sulfate, sodium sulfite, potassium sulfite, or mixtures thereof. Example 4. The electrode of example 1 which performs electrochemical conversions between phosphate, phosphite, and hypophosphite, the electrode comprising an aqueous solution of sodium phosphate, potassium phosphate, disodium hydrogen phosphite, diammonium hydrogen phosphite, or mixtures thereof. Example 5. An energy storage device in which: the device charges with electrical energy by an electrochemical process; the device releases electrical energy by an electrochemical process; and one or more electrodes are as described by examples 2, 3, or 4, wherein an electrochemical reaction of oxyanions occurs. Example 6. The device in example 5 wherein the cathode uses atmospheric oxygen and is comprised either of: a single bifunctional electrode with performs both oxidation and reduction of atmospheric oxygen; or a dual electrode cathode, with distinct electrodes to perform oxidation and reduction of atmospheric oxygen. Example 7. The device in example 5 wherein the cathode comprises of iron (III)/iron (II) cations, molecular chlorine/chloride, molecular bromine/bromide, and/or manganese (II) oxide/manganese (II) hydroxide. Example 8. The device in example 5 wherein both the anode and cathode comprise aqueous solutions of oxyanions, separated by an ion-exchange membrane. Example 9. The device in example 5 wherein reduction of oxyanions is performed by microbial activity. Example 10. The device in example 5 wherein the energy storage media is cycled in a flow battery. Example 11. A bulk energy storage system, comprising at least one energy storage device of any of examples 5-10; and/or at least one energy storage device having an electrode of any of examples 1-4. Example 12. The bulk energy storage system of example 11, wherein the bulk energy storage system is a long or ultra-long duration energy storage system.
Example A1. An energy storage device, comprising: at least one electrode configured such that electrochemical oxidation and reduction of one or more redox-active oxyanions occurs during charging and/or discharging of the energy storage device. Example A2. The energy storage device of example A1, wherein at least one of the one or more redox-active oxyanions comprise nitrate (NO32−), nitrite (NO22−), sulfate (SO42−), sulfite (SO32−), hyposulfite (SO22−), phosphate (PO43−), phosphite (PO33−), hypophosphite (PO23−), peroxodisulfate (S2O82−), ammonia (NH3), ammonium (NH4+), S2−, HS2, chlorite (ClO2−), chlorate (ClO3−), chlorine dioxide (ClO2), or hypochlorite (ClO−). Example A3. The energy storage device of example A1, wherein the energy storage device is configured such that electrochemical conversions between nitrate, nitrite, and/or ammonia occur during charging and/or discharging of the energy storage device. Example A4. The energy storage device of example A3, wherein the electrode comprises an aqueous solution of sodium nitrate, potassium nitrate, lithium nitrate, magnesium nitrate, calcium nitrate, calcium ammonium nitrate, sodium nitrite, potassium nitrite, lithium nitrite, or mixtures thereof. Example A5. The energy storage device of example A1, wherein the energy storage device is configured such that electrochemical conversions between sulfate, sulfite, hyposulfite, thiosulfate, dithionite, and/or hydrogen sulfide occur during charging and/or discharging of the energy storage device. Example A6. The energy storage device of example A5, wherein the electrode comprises an aqueous solution of an aqueous solution of sodium sulfate, potassium sulfate, magnesium sulfate, ammonium sulfate, sodium sulfite, potassium sulfite, or mixtures thereof. Example A7. The energy storage device of example A1, wherein the energy storage device is configured such that electrochemical conversions between phosphate, phosphite, and hypophosphite occur during charging and/or discharging of the energy storage device. Example A8. The energy storage device of example A1, wherein the electrode comprises an aqueous solution of sodium phosphate, potassium phosphate, disodium hydrogen phosphite, diammonium hydrogen phosphite, or mixtures thereof. Example A9. The energy storage device of example A1, wherein the one or more redox-active oxyanions comprise nitrate and/or nitrite anions. Example A10. The energy storage device of any of examples A1-A9, wherein the electrode comprises a bifunctional air electrode configured to perform oxygen reduction reactions and oxygen evolution reactions. Example A11. The energy storage device of any of examples A1-A9, wherein the electrode comprises a dual electrode configuration comprising: an oxygen reduction reaction (ORR) electrode; and an oxygen evolution reaction (OER) electrode separate from the ORR electrode. Example A12. The energy storage device of any of examples A1-A11, wherein the electrode is a cathode that comprises a cathode active material selected from iron (III)/iron (II) cations, molecular chlorine/chloride, molecular bromine/bromide, manganese (II) oxide/manganese (II) hydroxide, or any combination thereof. Example A13. The energy storage device of any of examples A1-A12, comprising: an anode; and a cathode, wherein the anode and/or the cathode are the electrode according to examples A1-A12 and both the anode and the cathode comprise aqueous solutions of oxyanions; and an ion exchange membrane disposed between the anode and the cathode. Example A14. The energy storage device of any of examples A1-A13, further comprising: one or more biomolecules, one or more enzymes, and/or one or more microorganisms disposed within the energy storage device, wherein the one or more biomolecules, the one or more enzymes, and/or the one or more microorganisms aid in oxidation and/or reduction of the one or more redox-active oxyanions during charging and/or discharging of the energy storage device. Example A15. The energy storage device of example A14, wherein the one or more biomolecules, one or more enzymes, and/or one or more microorganisms disposed within the energy storage device are at least one microorganism. Example A16. The energy storage device of example A15, wherein the at least one microorganism is a bacteria. Example A17. The energy storage device of example A16, wherein the bacteria is a sulphate-reducing bateria. Example A18. The energy storage device of any of examples A1-A17, wherein the energy storage device is a flow battery. Example A19. An energy storage device, comprising: negative electrode materials comprising sulfate and sulfite; and positive electrode materials comprising oxygen, wherein the energy storage device is configured to be rechargeable. Example A20. A bulk energy storage system, comprising one or more energy storage devices of any of examples A1-A19. Example A21. The bulk energy storage system of example A20, wherein the bulk energy storage system is a long or ultra-long duration energy storage system.
Example B1. 1. An electrochemical system, comprising: a first electrode; and a second electrode, wherein the electrochemical system stores energy and/or discharges energy by an electrode reaction of a halogenated oxyanion species. Example B2. The electrochemical system of example B1, wherein the storing of energy and/or the discharging of energy by the electrode reaction of the halogenated oxyanion species comprises storing energy and discharging energy by a reversable electrode reaction between a chlorine containing ion and chlorine dioxide. Example B3. The electrochemical system of example B2, wherein the chlorine containing ion comprises a salt. Example B4. The electrochemical system of example B3, wherein the salt is an alkali metal salt. Example B5. The electrochemical system of any of examples B1-B4, wherein the electrochemical system comprises a storage battery. Example B6. The electrochemical system of any of examples B1-B5, further comprising a current collector comprising a metal or metal compound. Example B7. The electrochemical system of example B6, wherein the current collector comprises carbon. Example B8. The electrochemical system of any of examples B1-B7, wherein the system is a bulk energy storage system is a long duration energy storage (LODES) system. Example B9. A method of operating an electrochemical system, the method comprising: storing and/or discharging energy by an electrode reaction of a halogenated oxyanion species. Example B10. The method of example B9, wherein storing and/or discharging energy by an electrode reaction of a halogenated oxyanion species comprises storing and/or discharging energy by a reversable electrode reaction between a chlorine containing ion and chlorine dioxide. Example B11. The method of example B10, wherein the chlorine containing ion comprises a salt. Example B12. The method of example B11, wherein the salt is an alkali metal salt. Example B13. The method of any of examples B9-B12, wherein the storing and/or discharging are performed as part of operating a battery in a bulk energy storage system. Example B14. The method of example B13, wherein the bulk energy storage system is a long duration energy storage (LODES) system. Example B15. An energy storage device, comprising: negative electrode materials; and positive electrode materials comprising chlorine dioxide and chlorite, wherein the energy storage device is configured to be rechargeable. Example B16. The energy storage device of example B15, further comprising an electrolyte, wherein the negative electrode materials comprise carbon, zinc, iron, or sulfur. Example 17. A bulk energy storage system, comprising one or more energy storage devices of any of examples B15-B16. Example B18. The bulk energy storage system of example B17, wherein the bulk energy storage system is a long or ultra-long duration energy storage system.
The preceding description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the described embodiment. Further, any step of any embodiment described herein can be used in any other embodiment. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the following claims and the principles and novel features disclosed herein.
This application claims the benefit of priority to U.S. Provisional Patent Application No. 63/381,099, filed Oct. 26, 2022, and to U.S. Provisional Patent Application No. 63/363,020, filed Apr. 14, 2022, and is a continuation-in-part of, and claims priority to, U.S. patent application Ser. No. 18/049,957, filed Oct. 26, 2022, which claims the benefit of priority to U.S. Provisional Patent Application No. 63/273,746, filed Oct. 29, 2021, the entire contents of which are hereby incorporated by reference for all purposes.
| Number | Date | Country | |
|---|---|---|---|
| 63381099 | Oct 2022 | US | |
| 63363020 | Apr 2022 | US | |
| 63273746 | Oct 2021 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 18049957 | Oct 2022 | US |
| Child | 18300970 | US |
