Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M12/00—Hybrid cells; Manufacture thereof
  • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/368—Liquid depolarisers

Definitions

• a first example implementation may include an alkaline electrolyte with a polysulfide electrode and NaClO 2 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 NaClO 2 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 NaClO 2 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 NaClO 2 electrode. Such an example is calculated to have an OCV of 1.27V.
• FIGS.1-4 are schematic views of electrochemical energy storage devices, according to various embodiments of the present disclosure.
• FIGS.5A and 5B are schematic views showing discharging and charging of an energy storage device of FIG.1, according to various embodiments of the present disclosure.
• FIGS.6A and 6B are schematic views showing discharging and charging of an energy storage device of FIG.2, according to various embodiments of the present disclosure.
• FIGS.7-15 illustrate various example systems in which one or more aspects of the various embodiments may be used as part of bulk energy storage systems.
• FIG.16 is a schematic representation of an electrochemical cell, according to various embodiments of the present disclosure.
• FIG.24A is a graph showing cyclic voltammetry (CV) of cells including 10mM NaClO 2 on a glassy carbon electrode (GCE, 3mm dia.) at a scan rate of 100 mV/sec.
• FIG.24B is a graph showing CV for 10mM NaClO 2 on a glassy carbon electrode (GCE, 3mm dia.) in 1M NaCl electrolyte at different scan rates.
• FIG.24C is a graph showing a Randles – Sevcik analysis based on data from FIG.24B.
• 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.
• sulfite to sulfate in alkaline solution 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.
• OER oxygen evolution reaction
• 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.
• such a sulfate-oxygen, or sulfate-air, battery may have an open-cell voltage or operating voltage of about 0.8 V.
• the oxidation or reduction of any of the aforementioned electrode-active compounds may be aided (e.g., facilitated, catalyzed, otherwise improved, etc.) by biomolecules, enzymes, and/or microorganisms (e.g., bacteria, etc.).
• 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.
• 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.
• 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.
• a sodium salt such as sodium nitrate, sodium nitrite, sodium sulfate, sodium sulfite, analogous potassium salts
• an ammonium salt such as ammonium nitrate or ammonium sulfate.
• 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.
• Reaction 1 NO 3 - (aq) + H 2 O (l) + 2e- ⁇ -> NO 2 - (aq) + 2OH- (aq) ;
• Reaction 2 2OH-(aq) ⁇ -> H2O(l) + 1 ⁇ 2 O 2 (g) + 2e-;
• Reaction 3 NO 3 -(aq) ⁇ -> NO 2 -(a)
• 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.
• 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.
• 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.
• 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.
• 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.
• FIG.8 illustrates an example system in which one or more aspects of the various embodiments may be used as part of bulk energy storage system.
• the LODES system 304 may have a duration of 24h to 500h 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.
• FIG.11 illustrates an example system in which one or more aspects of the various embodiments may be used as part of bulk energy storage system.
• the LODES system 304 may have a duration of 24h to 500h, 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.
• FIG.12 illustrates an example system in which one or more aspects of the various embodiments may be used as part of bulk energy storage system. While FIG.12 is discussed in relation to an example LODES system 304, the durations of energy storage and/or power delivery described with reference to FIG.12 are provided merely as examples and are not intended to limit the scope of the invention or claims.
• the LODES system 304 may be part of a power plant 900 that is used to integrate large amounts of renewable generation in microgrids and harmonize the output of renewable generation by, for example a PV farm 402 and wind farm 302, with existing thermal generation by, for example a thermal power plant 902 (e.g., a gas plant, a coal plant, a diesel generator set, etc., or a combination of thermal generation methods), while renewable generation and thermal generation supply the C&I customer 702 load at high availability.
• a thermal power plant 902 e.g., a gas plant, a coal plant, a diesel generator set, etc., or a combination of thermal generation methods
• Microgrids such as the microgrid constituted by the power plant 900 and the thermal power plant 902, may provide availability that is 90% or higher.
• the LODES system 304 may have durations of 24h to 500h and round-trip efficiencies of greater than 40%. In one such example, the LODES system 304 may have a duration of 150 hours and support customer electrical consumption for up to a week of renewable under-generation. The LODES system 304 may also support customer electrical consumption during intra-day under-generation events, augmenting the capabilities of the SDES system 1102. Further, the SDES system 1102 may supply customers during intra-day under-generation events and provide power conditioning and quality services such as voltage control and frequency regulation. [00108] 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.
• 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 (ClO 2 -) and chlorine (IV) dioxide (ClO 2 ), which in some embodiments may be carried out in an aqueous electrolyte.
• the solubility of NaClO 2 in water is substantial, being: 8.4mol_NaClO 2 /L_H 2 O at 25degC; and 4.3mol_NaClO 2 /L_H 2 O at 17degC.
• Example 1 Cl(III)/Cl(IV) redox reaction in alkaline solution
• Three-electrode cyclic voltammetry was conducted at room temperature (about 23 ⁇ -> 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 NaClO 2 dissolved in reverse osmosis deionized (RODI) water, and 1M KOH, producing pH ⁇ 14.
• RODI reverse osmosis deionized
• 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.
• 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 ClO 2 storage)
• 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 NaClO 2 , NaBrO 2 , KClO 2 , or KBrO 2 , may be stored as a dissolved solution.
• the chlorite bearing compound and chlorine dioxide may be stored in the same enclosure.
• the chlorite containing compound and chlorine dioxide may each be stored in separate enclosure.
• chlorine dioxide may be stored at a temperature ⁇ 11 ⁇ ->.
• the reversible Cl(III)/Cl(IV) electrode may include a chlorite stabilizer.
• 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.
• 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.
• the starting state may be achieved by carrying out an initial electrochemical reaction that forms ClO 2 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.
• FIG. 4 An example of such a formation cycle is shown in Figure 4, where the initial state of the battery has metallic iron at the negative electrode.
• a source of chlorite ions is for forming chlorine dioxide may include a chlorite compound, such as an alkali chlorite (e.g., NaClO 2 ).
• the battery is a flow battery, in which the electrochemical cell and one or more of the vessels shown in FIGS.23A-C are physically separated and are connected to other components of the system by flow channels or pipes.
• the electrochemical cell and the vessels or tanks are partially or completely integrated into the same device, forming separate chambers within an assembly or ⁇ device.
• relay controlled valves and pumps are placed in the battery system to control flow between said cell and vessels or tanks.
• the aqueous chlorine dioxide/chlorite (ClO 2 /ClO 2 -) 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.
• the chlorite ion is widely available at low cost when sourced from sodium chlorite (NaClO 2 ).
• NaClO 2 sodium chlorite
• the ClO 2 /ClO 2 - 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.
• FIG.24B is a graph showing CV for 10mM NaClO 2 on a glassy carbon electrode (GCE, 3mm dia.) in 1M NaCl electrolyte at different scan rates.
• FIG.24C is a graph showing a Randles-Sevcik analysis based on data from FIG.10B. All CV experiments were performed at room temperature (19°C +/- 1°C) using an Ag/AgCl (3M NaCl) reference electrode and a platinum wire counter electrode. ⁇ [00166] Referring to FIG.24A, CV curves were taken at the same temperature and sweep rate for acidic, near neutral, and alkaline solutions spanning pH 2 to 14. The supporting electrolyte in the alkaline solution was 1M KOH (about pH 14).
• Reaction 4 2H2O + 2e- ⁇ -> H2 + 2OH-
• Reaction 5 2ClO 2 - ⁇ -> 2ClO 2 + 2e-
• Reaction 6 2H2O + 2ClO 2 - ⁇ -> H2 + 2OH- + 2ClO 2 .
• FIGS.13A and 13B the results obtained from a representative Zn-ClO 2 full cell tested at 0.5°C ⁇ 0.5°C, plotted as cell voltage vs capacity for a capacity-limited cycling regimen wherein galvanostatic charging at a current density of 5 mA/cm 2 up to a capacity limit of 10 mAh was performed, followed by discharging to a voltage limit of 0.8V.
• the positive electrolyte included a 1.5 mL volume of 1.95 mol/L NaClO 2 solution, on top of which floated 6 mL of a hydrocarbon solvent in which ClO 2 is soluble.
• loss of ClO 2 /ClO 2 - may be attributable to any one or more of incomplete blocking of chlorite crossover to the Zn electrode, partial disproportionation of ClO 2 in the electrolyte, or possible leakage of ClO 2 from the cell.
• 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 ⁇ FIGS.26A-26C as the power-generating stack of a flow battery, the ClO 2 product could be stored in a tank and circulated to the positive electrode.
• 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 both the anode and cathode comprise aqueous solutions of oxyanions, separated by an ion-exchange membrane.

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• 2023
  • 2023-04-14 WO PCT/US2023/018696 patent/WO2023201068A1/en not_active Ceased
  • 2023-04-14 EP EP23789023.1A patent/EP4508699A4/de active Pending

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