WO1990003666A1 - Etat de charge d'une pile redox - Google Patents

Etat de charge d'une pile redox Download PDF

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Publication number
WO1990003666A1
WO1990003666A1 PCT/AU1989/000252 AU8900252W WO9003666A1 WO 1990003666 A1 WO1990003666 A1 WO 1990003666A1 AU 8900252 W AU8900252 W AU 8900252W WO 9003666 A1 WO9003666 A1 WO 9003666A1
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Prior art keywords
positive
negative
electrolyte
redox flow
flow cell
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PCT/AU1989/000252
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English (en)
Inventor
Maria Skyllas-Kazacos
Barry George Maddern
Michael Kazacos
Jaqui Joy
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Unisearch Limited
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Publication of WO1990003666A1 publication Critical patent/WO1990003666A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04746—Pressure; Flow
    • H01M8/04753—Pressure; Flow of fuel cell reactants
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04313—Processes for controlling fuel cells or fuel cell systems characterised by the detection or assessment of variables; characterised by the detection or assessment of failure or abnormal function
    • H01M8/0432—Temperature; Ambient temperature
    • H01M8/04365—Temperature; Ambient temperature of other components of a fuel cell or fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04701—Temperature
    • H01M8/04708—Temperature of fuel cell reactants
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04858—Electric variables
    • H01M8/04865—Voltage
    • H01M8/0488—Voltage of fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04858—Electric variables
    • H01M8/04895—Current
    • H01M8/0491—Current of fuel cell stacks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04298—Processes for controlling fuel cells or fuel cell systems
    • H01M8/04694—Processes for controlling fuel cells or fuel cell systems characterised by variables to be controlled
    • H01M8/04858—Electric variables
    • H01M8/04949—Electric variables other electric variables, e.g. resistance or impedance
    • H01M8/04953—Electric variables other electric variables, e.g. resistance or impedance of auxiliary devices, e.g. batteries, capacitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/184—Regeneration by electrochemical means
    • H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
    • H01M8/04194—Concentration measuring cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • This invention relates to a method of determining the state of charge of a redox flow cell through which positive and negative electrolytes flow, a method of providing a selected discharge voltage/current from a redox flow cell through which positive and negative electrolytes flow, a method of providing a selected charge voltage/current from a redox flow cell through which positive and negative electrolytes flow, a redox flow cell system in which the state of charge can be determined, a redox flow cell system for providing a selected discharge voltage/current from a redox flow cell through which positive and negative electrolytes flow and a redox flow cell system having a redox flow cell through which positive and negative electrolytes flow, which cell is adaptable to require a selected charge voltage/current.
  • redox flow cells have many advantages over conventional batteries, they do have a particular disadvantage in that energy is lost as a result of pumping the positive and negative electrolytes through the respective half-cells.
  • the minimum flow rate per cell required is referred to as the stoichiometric flow rate.
  • Another object is to provide a method of providing a selected discharge voltage/current from a redox flow cell through which positive and negative electrolytes flow.
  • Another object is to provide a method of providing a selected charge voltage/current from a redox flow cell through which positive and negative electrolytes flow.
  • Yet another object is to provide a redox flow cell system in which the state of charge can be determined.
  • a further object is to provide a redox flow cell system for providing a selected discharge voltage/current from a redox flow cell through which positive and negative electrolytes flow.
  • Yet a further object is to provide a redox flow cell system having a redox flow cell through which positive and negative electrolytes flow, which cell is adaptable to require a selected charge voltage/current.
  • a method of determining the state of charge of a redox flow cell through which positive and negative electrolytes flow the redox flow cell having:
  • a method of providing a selected discharge voltage/current from a redox flow cell through which positive and negative electrolytes flow the redox flow cell having:
  • a third embodiment of this invention there is provided a method of providing a selected charge voltage/current from a redox flow cell through which positive and negative electrolytes flow, the redox flow cell having:
  • the methods of the first, second and third embodiments can include:
  • the methods of the first and second embodiments further include the step of determining the state of charge of the cell or a parameter related thereto from the characteristic(s).
  • the change in the flow rates of the positive and negative electrolytes is determined from the state of charge of the cell.
  • the methods of the invention can include measuring characteristics of the positive and/or negative electrolytes related to the state of charge of the cell by:
  • A. (1) measuring inlet and outlet open circuit redox flow cell voltages between the positive and negative electrolytes of the redox flow cell and determining the difference therebetween;
  • X and Y is an ion selected from ions such as Cr, Fe, Mn, Ni, Al, Mo, Ru, La, Ti, Pb, etc. measuring the absorption of a charged or discharged X m+ /X n+
  • negative electrolyte is a function of concentration of X m+ /X n+ posit1ve electrolyte and/or Y a+ /Y b+ ;
  • a redox flow cell having:
  • a redox flow cell system for providing a selected discharge voltage/current from a redox flow cell through which positive and negative electrolytes flow, which-system comprises:
  • a positive electrolyte pump means for transporting positive electrolyte between the positive compartment and the positive electrolyte pump, operatively associated with the positive compartment and the positive electrolyte pump;
  • adjusting means for adjusting pumping speeds of the positive and negative electrolyte pumps and thereby change flow rates of the positive and negative electrolytes through the positive and negative compartments respectively, in accordance with the determined change(s) in the flow rates of the positive and negative electrolytes, whereby the cell provides the selected discharge voltage/current, which adjusting means is operatively associated with the means to determine and the positive and negative electrolyte pumps.
  • a redox flow cell system having a redox flow cell through which positive and negative electrolytes flow, which cell is adaptable to require a selected charge voltage/current, which system comprises:
  • a redox flow cell having:
  • adjusting means for adjusting pumping speeds of the positive and negative electrolyte pumps and thereby change flow rates of the positive and negative electrolytes through the positive and negative compartments respectively, in accordance with the determined change in the flow rates of the positive and negative electrolytes, whereby the cell requires the selected charge voltage/current, which adjusting means is operatively associated with the means to determine and the positive and negative electrolyte pumps.
  • the systems of the fourth, fifth and sixth embodiments can include: (i) Means to measure a characteristic(s) of the positive electrolyte entering the redox flow cell and leaving the redox flow cell; or (ii) Means to measure a characteristic(s) of the negative electrolyte entering the redox flow cell and leaving the redox flow cell; or
  • the positive electrolyte is recirculated to the positive compartment via the means for transporting oositive electrolyte by the positive electrolyte pump.
  • the negative electrolyte is recirculated to the negative compartment via the means for transporting negative electrolyte by the negative electrolyte pump.
  • the means to measure in the apparatus of the invention can be means to measure the following characteristics of the positive and/or negative electrolytes as follows:
  • A. means to measure inlet and outlet open circuit redox flow cell voltages between the positive and negative electrolytes of the redox flow cell and determining the difference therebetween;
  • electrolyte means to measure the absorption of a charged or discharged negative V 2+ /V 3+ electrolyte at a selected
  • the positive compartments of the first to fourth embodiments each include a positive electrode and the negative compartments of the first to fourth embodiments each include a negative electrode.
  • the positive and negative electrodes can be any shape desired. It is preferred that the positive and negative electrodes are rectangular-plate shaped.
  • the positive and negative electrodes can be carbon or graphite felt, mat, plate, rod, knit, fibre, and cloth; carbon impregnated teflon; carbon impregnated polyethylene; carbon impregnated polypropylene; carbon
  • the positive electrode can also be carbon or graphite felt, mat, plate, rod, knit, fibre, and cloth, carbon impregnated teflon, carbon impregnated polyethylene, carbon impregnated polypropylene, carbon impregnated polystyrene, carbon impregnated polyvinylchloride and carbon impregnated polyvinylidenechloride, impregnated with and/or coated with Au, Mn, Pt, Ir, Ru, Os, Re, Rh, Sb, Te, Pb and/or Ag.
  • the negative electrode can also be carbon and graphite felt, mat, plate, rod, knit, fibre, and cloth, carbon impregnated teflon, carbon impregnated
  • Other types of caroon electrodes can also be used.
  • the positive and negative electrodes can also De non carbon electrodes such as platinised Ti; platinised Ru; platinised
  • a dimensionally stabilized anode (DSA - Ti or Ti alloy core, coated at least partially with titanium dioxide which coating is coated in turn with a noble metal coating selected from the group consisting of Pt, Pd, Os, Rh,
  • Ru, Ir and alloys thereof is a suitable positive electrode or V 2 O 5 coated Pb or Ti.
  • the Dositive anolytes and the negative catholytes in the case of an all-vanadium cell for example, comprise an electrolyte which is typically an aqueous solution which includes at least one of the following H 2 SO 4 , trifluoromethanesulphonic acid, Na 2 SO 4 , K 2 SO 4 , H 3 PO 4 ,
  • arylsulphonic acid such as p-toluenesulphonic acid, benzenesulphonic acid, naphthalenesulphonic acid, C 1 -C 8 alkylsulphonic acid such as
  • methylsulphonic acid and ethylsulphonic acid, acetic acid or mixtures thereof in a concentration of from 0.01M to 6.0M. It is especially preferred to use H 2 SO 4 in a concentration of from 0.25M to 4.5M, more preferably 0.5M to 4M.
  • the electrolyte typically has vanadium ions in sufficient concentration for high discharge capacity in the discharge cell, for example, 0.25M to 3.5M, preferably 1M to 3M, and more preferably 1.5M to 2.5M are typical in the charge and discharge cells of the invention.
  • the vanadium ions in the electrolyte can oe prepared by dissolving an oxide, sulphate, phosphate, nitrate, halide or other salt or complex of vanadium which is soluble in the electrolyte. It is especially preferable to dissolve vanadyl sulphate in 0.5M to 3.5M H 2 SO 4 or
  • the electrolyte is typically stirred or agitated preferably with a mechanical stirrer.
  • a cell used in a system of the invention typically cells of the "memorane-type", that is each type of cell employs a membrane rather than a diaphragm to separate a positive compartment from a negative compartment.
  • the membrane employed is typically sheet-like and can transport electrolyte ions whilst at the same time being hydraulically-impermeable in contrast to a diaphragm (typically asbestos) which allows restricted electrolyte transfer between compartments.
  • the ionically conducting separator can be a microporous separator or a membrane fabricated from a polymer based on perfluorocarboxylic acids or a proton exchange polymer such as sulphonated polystyrene, sulphonated polyethylene or a substantially fluorinated sulpnonic acid polymer such as Nafion (Trade Mark) or membranes of Flemion (Trade Mark) or Selemion (Trade Mark) material as manufactured by Asahi Glass Company.
  • Discharging and charging a cell are typically conducted in sealed air tight cells and can be conducted under an inert atmosphere such as nitrogen, argon, helium or neon or mixtures thereof although an inert atmosphere can be avoided in a sealed system.
  • an inert atmosphere such as nitrogen, argon, helium or neon or mixtures thereof although an inert atmosphere can be avoided in a sealed system.
  • All-vanadium redox cells can be operated over a broad temperature range, e.g. -5°C to 99°C but are typically operated in the temperature range 0°C to 40°C.
  • the redox flow cell includes monopolar and bipolar type cells.
  • a bipolar cell typically includes a plurality of positive compartments eacn having a positive electrode therein and a plurality of negative
  • a bipolar cell is typically of tne flat plate- or filter press-type.
  • the electrolyte storage vessels may also oe equipped with liquid level detectors which will detect any changes to the electrolyte levels resulting from evaporation or water decomposition during charging.
  • valves open and allow water to be delivered by gravity from a separate holding tank into the electrolyte storage tanks. When the desired level is once more established the valves are automatically closed.
  • the electrolyte storage vessels may also be equipped with temperature sensors to ensure that the solution temperature does not exceed 40°C at which point the V(V) solution would be in danger of decomposing and precipitating. If the temperature reaches 40°C, the solution charging is ceased and the system is allowed to discharge to approximately 80%
  • a heat-exchanger may be incorporated in the catholyte flow loop to prevent excessive heating of solutions.
  • the present invention describes methods and apparatuses for
  • state-of-charge of the flow cell can be monitored by utilizing two electrodes, one in each type of half-cell, and measuring the open circuit voltage therebetween.
  • the monitoring device is connected nydraulically but not electrically in the cell stack.
  • a open-circuit voltmeter is placed both before and after the cell stack to monitor the state-of-charge of the electrolytes as they enter and leave the positive and negative compartments. The difference between the open-circuit voltage before and after the positive and negative compartments is a measure of the 7.
  • ⁇ E cell should be 0.12 volts when the solutions are fully charged
  • the all-vanadium redox flow cell can include an open-circuit cell which is hydraulically connected but not electrically connected to the cell stack.
  • the anolyte and catholyte flow through each half-cell and the open-circuit voltage of the system can be continuously monitored and used to include state-of-charge of system as well as to regulate charging and discharging between tne desired limits e.g. 10% to 90% state-of-charge, by control system.
  • the open-circuit cell voltage can be used as an indication of the system state-of-charge it must be assumed that the two half-cells are at the same state-of-charge i.e. the system is balanced. If the electrolytes were to become unbalanced, however, it would not be possible to determine the imbalance from the open-circuit voltage, nor would the state-of-charge be accurately indicated by E oc . Ideally, therefore, each of the 1/2-cell electrolyte potentials should be monitored so that the system balance can be measured together with the state-of-charge.
  • an inert metal indicator electrode could be utilized.
  • Electrolyte conductivity can also be used to continuously monitor state of charge and regulate charging and discharging between desired limits. Since electrolyte conductivity varies linearly with the
  • Conductivity varies linearly with SOC however, so for a particular conversion per pass, a constant value of ⁇ (conductivity) between inlet and outlet positive and/or negative electrolyte would be set to control the pump flow rates.
  • the positive electrolyte conductivity increases by approximately 11 ms/cm for each 107. increase in SOC for the range 0 to 907. SOC, as shown in Figure 13. Thus, by measuring the conductivity of the positive
  • This ⁇ (conductivity) value is independent of the solution state-of-cnarge and would be a much simpler pump control method than the ⁇ E oc approach described previously.
  • Temperature compensation can readily be performed by using temperature probes and conductivity meters or circuitry capable of correcting for temperature variations.
  • Fig. 1 depicts schematically a redox flow cell system for providing a selected discharge voltage/current from a redox flow cell through which positive and negative electrolytes flow;
  • Fig. 2 depicts schematically an alternative redox flow cell system for providing a selected discharge voltage/current from a redox flow cell through which positive and negative electrolytes flow;
  • Fig. 3 depicts schematically a non-linear circuit for recirculation control of the positive and negative electrolytes
  • Fig. 4 depicts schematically an alternative non-linear circuit for recirculation control of the positive and negative electrolytes
  • Fig. 5 depicts schematically a cross section of an electrolyte absorption probe in a pipe
  • Fig. 6 depicts schematically a front view'of the electrolyte absorption probe of Fig. 5;
  • Fig. 7 depicts schematically another alternative redox flow cell system for providing a selected discharge voltage/current from a redox flow cell through which positive and negative electrolytes flow;
  • Fig. 8 is a plot of ⁇ E cell calculated for different value of SOC, x and fraction conversion y;
  • Fig. 9 is a plot of solution ootential of V 2+ /V 3+ and
  • Fig. 10 depicts cell voltage as a function of % state-of-cnarge for an al l-vanadi um cel l employi ng a Sel emion membrane and 1 .5M VOSO 4 i n 2M
  • Fig. 11 depicts a calibration curve for 1.0M V(IV)/V(V) half cell
  • Fig. 12 depicts a calibration curve for 1.0M V(II)/V(III) half cell
  • Fig. 13a depicts a plot of conductivity of 2M V + 2M H 2 SO 4
  • Fig. 13b depicts a plot of conductivity of negative vanadium cell electrolyte as a function of state-of-charge (2M V in 3M H 2 SO 4 ).
  • Fig. 13c depicts a plot of conductivity of a positive electrolyte ( 2M V in 3M H 2 SO 4 ) as a function of state-of-charge.
  • Fig. 14 depicts a plot of UV-visible spectra for 2 M positive electrolytes at different states-of-charge. Curves 1-10 correspond to state-of-charge values of 1.0, 0.95, 0.90, 0.80, 0.60, 0.40, 0.20, 0.10, 0.05 and 0 respectively.
  • Fig. 15a depicts a plot of UV-visible spectra for 2 molar negative electrolysis at different states-of-charge. Curves 1-4 correspond to state-of-charge values 1,0. 0.95,09 and 0.8 respectively.
  • Fig. 15b depicts a plot of UV-visible spectra for 2 molar negative electrolytes at different states-of-charge. Curves 5-7 correspond to state-of-charge values of 0.6, 0.4, and 0.2 respectively.
  • Fig. 15c depicts a plot of UV-visible spectra for 2 molar negative electrolytes at different states-of-charge. Curves 8-10 correspond to state-of-charge values 0.1, 0.5 and 0 respectively.
  • Fig. 16 depicts a plot of aosorbance of 2 molar negative electrolyte at 750 nm as a function of state-of-charge.
  • Fig. 17 depicts a plot of absorbance of 2 molar negative electrolyte as a function of state-of-cnarge.
  • Curve 1 corresponds to absorbance at the minimum in spectrum at 450-500 nm
  • curve 2 is apsorpance at 700-850 nm mi ni mum.
  • a redox flow cell system 100 for providing a selected discharge voltage/current from redox flow cell 101 through which positive and negative electrolytes flow.
  • the positive electrolyte consists of 0.25M to 2.5M pentavalent/tetravalent vanadium ions in 0.25M - 5M H 2 SO 4 .
  • the negative electrolyte consists of 0.25M to 2.5M
  • Cell 101 has a negative compartment 102 having negative electrode 114 disposed therein, positive compartment 103 having positive electrode 115 disposed therein and ionically conducting separator 104 generally a Selemion CMV membrane. Negative electrode 114 and positive electrode 115 are electrically coupled via means to charge/discharge 116. Separator 104 is operatively disposed between compartments 102 and 103 to provide ionic communication between positive electrolyte in the positive compartment 103 and negative electrolyte in compartment 102.
  • System 100 includes positive electrolyte storage/flowthrough reservoir 105 and negative electrolyte
  • Positive electrolyte pump 1 is connected to pipe 107 to recirculate positive electrolyte between positive compartment 103 and storage reservoir 105 via pipes 107 and 107A.
  • Negative electrolyte pump 2 is connected to pipe 108 to recirculate negative electrolyte between negative compartment 102 and storage reservoir 106 via pipes 108 and 108A.
  • Electrolyte voltage probes 110 and 111 (which can be Hg/Hg 2 SO 4 electrode for example) are placed sealably through apertures (not snown) in pipes 108A and 107A respectively and are connected electrically to voltmeter 109 via wires 118 and 119.
  • Voltmeter 109 measures the open circuit voltage between inlet positive electrolyte flowing via pipe 107A into comoartment 103 and inlet negative electrolyte fowing via pipe 108A into negative comoartment 102.
  • an inlet open-circuit cell containing a membrane and electrodes which can be graphite plates, glassy carbon, platinum or other noble metals for example can be placed in line in pipes 108A and 107A.
  • the membrane acts as an ionic conductor between the electrolytes in pipes 108A and 107A and the electrodes are connected to voltmeter 109 to measure the potential difference between the electrolytes in pipes 108A and 107A which
  • Electrolyte voltage probes 112 and 113 are placed in apertures (not shown) in pipes 107 and 108 respectively and are connected electrically to voltmeter 117 via wires 120 and 121 respectively.
  • Voltmeter 117 measures the open circuit voltage between outlet positive electrolyte flowing via pipe 107 into reservoir 105 and outlet negative electrolyte via pipe 108 into reservoir 106.
  • an outlet open-circuit cell containing a membrane and electrodes which can be graphite plates, glassy carbon, platinum or other noble metals, for example, can be placed in line in pipes 107 and 108.
  • the membrane acts as an ionic conductor between the electrolytes in pipes 107 and 108 and the electrodes are connected to voltmeter 117 which measures the potential difference between the electrolytes in pipes 107 and 108 which corresponds to the open circuit voltage between the outgoing electrolytes.
  • Adjusting means 122 is connected electrically to voltmeters 109 and 117 via wires 123 and 124 to receive output signals corresponding to the open circuit voltage measured by voltmeters 109 and 117 via wires 123 and 124. Adjusting means 122 is connected electrically to pumps 1 and 2 via wires 125 and 126 respectively.
  • pump 1 recirculates pentavalent/tetravalent vanadium ions through positive compartment 103 and through reservoir 105 via pipes 107 and 107A.
  • Pump 2 recirculates di vaient/trivalent vanadium ions tnrougn negative comoartment 102 and through reservoir 106 via pipes 108 and 108A.
  • Electrical energy is withdrawn from cell 101 by loading an external circuit in the means to charge/discharge 116.
  • the incoming open circuit voltage between the incoming negative electrolyte flowing through pipe 108A and the incoming positive electrolyte flowing through pipe 107A is measured by voltmeter 109 which determines the voltage difference measured by electrolyte voltage probes 110 and 111.
  • the outgoing open circuit voltage between the outgoing negative electrolyte flowing through pipe 108 and the outgoing positive electrolyte flowing through pipe 107 is measured by voltmeter 117 which determines the voltage difference between voltage probes 112 and 113.
  • Output signals corresponding to the incoming open circuit voltage and the outgoing open circuit voltage are sent to adjusting means 122 via wires 123 and 124 respectively.
  • recirculation control of the positive and negative electrolytes is shown in block diagrammatic form in Fig. 3.
  • Separate electrically controlled pumps 1 and 2 for conveyi ng positi ve and negati ve el ectrolytes through compartments 103 and 102 respectively, are energised by common line 12 from a power control unit 13 responding to digital pump commands on line 14 generated from computing block 15 and converted to analogue command signals on line 40 by D/A converter 16.
  • the pumping flow rate is automatically adjusted to produce a selected differential open circuit voltage
  • ⁇ E oc cell value dependent upon three factors, (1) the state of cnarge of the electrolyte, (2) the state of the cell charge, and (3) the current drain thereon.
  • Factor (1) is represented in the drawing by signal " ⁇ E oc measured” 34 applied on input line 17 to one side of a second computing block 18.
  • Output line 27 from computing block 18 is applied as input to computing block 15.
  • the otner input 19 to computing block 18 is derived from a ROM 20 whicn by a look-up table for a selected value of by" 35, ano corrected for temperature, determines on the output line 19 what the state-of-charge of the positive and negative electrolytes should be.
  • the internal table of the ROM 20 is addressed on input line 21 by the state of charge of the cells derived through a look-up table in a second ROM 22 which in turn is addressed by the open circuit cell voltage "Eoc i measured" 28 via input line 29 and the actual temperature "Temp. T” 30 via line 31.
  • the signal line 21 is applied as a first input to a computing block 23 which also receives on input line 24 an indication of the current drain on the batteries as an input "IC/ d measured" 32 and on a third input 25 a signal "manual constant C" 33 which provides manual control to modify the pump response to current drain.
  • An output F s is applied on output line 26 to a second input to the computing block 15 thereby to derive a pump command on line 14 which correlates the three factors (1), (2) and (3) referred to above.
  • FIG. 4 An alternative non-linear circuit for adjusting means 122 is shown in Fig. 4 where like designating numerals are applied to like componentry of Fig. 3.
  • a linear controller 27 generates pump commands on output line 14 based upon the error differential between the measured ⁇ E oc 34 and a value of ⁇ E oc calculated 19 from the state of charge of the cell.
  • the control parameters 36, 37 and a manually set constant 38, 39 are also inputs to the control strategy incorporated in the linear controller 27.
  • the states of charge of the positive and negative electrolytes and what those charges should be, are derived through ROM's 20 and 22 in a similar manner to that previously described in connection with Fig. 3.
  • a redox flow cell system 200 for providing a selected discnarge voltage/current from redox flow cell 201 through which positive and negative electrolytes flow.
  • Cell 201 has a negative compartment 202 having negative electrode 214 di sposed therein, positive compartment 203 having positive electrode 215 disposed therein and ionically conducting separator 204 generally a Selemion CMV membrane. Negative electrode 214 and positive electrode 215 are electrically coupled via means to charge/discharge 216. Separator 204 is operatively disposed between compartments 202 and 203 to provide ionic communication between positive electrolyte in the positive compartment 203 and negative
  • System 200 includes positive electrolyte storage/flowthrough reservoir 205 and negative electrolyte
  • Positive electrolyte pump 1 is connected to pipe 207 to recirculate positive electrolyte between positive compartment 203 and storage reservoir 205 via pipes 207 and 207A.
  • Negative electrolyte pump 2 is connected to pipe 208 to recirculate negative electrolyte between negative compartment 202 and storage
  • V 2+ /V 3+ negative electrolyte absorption probe 210 is placed sealably through an aperture (not shown) in pipe 208A and is connected electrically to voltmeter 209 via wire 218.
  • Meter 209 measures a voltage or current from probe 210 related to the absorption of incoming V 2+ /V 3+ negative electrolyte at about 750nm.
  • V 2+ /V 3+ negative absorption probe 212 is placed through an aperture
  • Adjusting means 222 is connected electrically to
  • Adjusting means 222 is connected electrically to pumps 1 and 2 via wires 225 and 226 respectively.
  • pump 1 recirculates pentavalent/tetravalent vanadium ions through positive compartment 203 and through reservoir 205 via pipes 207 and 207A.
  • Pump 2 recirculates divalent/trivalent vanadium ions through negative compartment 202 and through reservoir 206 via pipes 208 and 208A.
  • Electrical energy is withdrawn from cell 201 by loading an external circuit in the means to charge/discharge 216.
  • the incoming absorption of V 2+ /V 3+ incoming negative electrolyte flowing tnrough pipe 208A is measured by probe 210 and an output signal related thereto is determined as an incoming voltage by voltmeter 209.
  • Fig. 5 depicts a cross sectional section of a pipe 600 having a V 2+ /V 3+ negative absorption probe 210 inserted through an aperture 602 in pipe 600.
  • Probe 210 has an outer casing 603 which has a transverse aperture 604 extending from side 605 through to side 606 of probe 210.
  • An apsorption system 607 is located within casing 603 about aperture 604.
  • System 607 has an array of infrared light emitting diodes 608 which emit infrared light of about 750nm and an array of silicon diode detectors 609 which are located opposite diodes 608 to detect light emitted therefrom.
  • Diodes 608 are housed in compartment 610 which has a window 611 opposite detectors 609 and detectors 509 are housed in compartment 612 which has a window 613 opposite diodes 608. Hence light emitted by diodes 608 can pass through windows 611 and 613 and be detected by detectors 609. Diodes 608 are connected electrically to power supply 614 via wires 615.
  • Detectors 609 can be connected electrically to voltmeter 209 depicted in Fig. 2 via wires 218.
  • Fig. 5 depicts a front view of probe 210 which clearly shows aperture 604 extending from side 605.
  • diodes 608 are powered by power supply 614 to emit light of about 750nm which passes through windows 611 and 613 and is detected by detectors 609. A portion of V 2+ /V 3+ negative electrolyte 601 which is flowing through pipe 600 passes through aperture 604. Output signals related to the absorption of V 2+ /V 3+ negative electrolyte
  • a redox flow cell system 500 for providing a selected discharge voltage/current from redox flow cell 501 through which positive anc negative electrolytes flow.
  • the positive electrolyte consists of 0.25M to 2.5M pentavalent/tetravalent vanadium ions in 0.25M - 5M H 2 SO 4 .
  • the negative electrolyte consists of 0.25M to 2.5M
  • Cell 501 has a negative compartment 502 having negative electrode 514 disposed therein.
  • positive compartment 503 having positive electrode 515 disposed therein and ionically conducting separator 504 generally a Selemion CMV memorane.
  • Negative electrode 514 and positive electrode 515 are electrically coupled via means to charge/discharge 516.
  • Separator 504 is operatively disposed between compartments 502 and 503 to provide ionic communication between positive electrolyte in the positive compartment 503 and negative
  • System 500 includes positive electrolyte storage/flowthrough reservoir 505 and negative electrolyte
  • Positive electrolyte pump 1 is connected to pipe 507 to recirculate positive electrolyte between positive compartment 503 and storage reservoir 505 via pipes 507 and 507A.
  • Negative electrolyte pump 2 is connected to pipe 508 to recirculate negative electrolyte between negative compartment 502 and storage
  • Meter 509 measures a voltage or current from probe 510 related to the conductivity of incoming V 2+ /V 3+ negative electrolyte.
  • electrolyte conductivity probe 511 is placed sealably through an aperture (not shown) in pipe 508A and is connected electrically to conductivity meter 509A via wire 519.
  • Meter 509A measures a voltage or current from probe 519 related to the conductivity of incoming V 4+ /V 5+ positive electrolyte.
  • V 2+ /V 3+ negative conductivity meter probe 512 is placed through an aperture (not shown) in pipe 508 and is connected electrically to conductivity meter 517 via wire 520.
  • Meter 517 measures a voltage or current from probe 512 related to the conductivity of outgoing V 2 +/V 3+ negative electrolyte.
  • V 4+ /V 5+ positive conductivity meter probe 512A is oiaced through an aperture (not shown) in pipe 508 and is connected electrically to conductivity meter 517A via wire 521.
  • Meter 517A measares a voltage or current from probe 512A related to the conductivity of outgoing V 4+ /V 5+ positive electrolyte. Adjusting means 522 is
  • conductivity meters 509, 509A, 517 and 517A vi a wires 523, 523A , 524 and 524A respectively to recei ve output si gnals corresponding to the voltage or current measured by conductivity meters
  • Adjusting means 522 is connected electrically to pumps 1 and 2 via wires 525 and 526 respectively.
  • electrolyte rebalance one can employ oxalic acid additions from reservoir 527 via line 528 to positive electrolyte storage/flowthrough reservoir 505 periodically, e.g. if system capacity drops by 10% or if +ve & -ve side out of balance by e.g. 10% add stoichiometric amount of oxalic acid to +ve electrolyte+
  • the positive electrolyte in reservoir 505 can be agitated by bubbling N 2 through to assist reaction and allow escape of CO 2 through vents. After several hours of reaction battery 501 can be reused and system capacity will gradually be restored - see Fig. 18. In the case of experiments which led to the results shown in Fig. 18 when excess oxalic acid was added only a slight increase in capacity is observed. If required amount is added capacity is restored.
  • the chemical reductant can also be KHC 2 O 4 .H 2 O, K 2 C 2 O 4 ,
  • Other chemical reductants can be used.
  • a reducing organic water-soluble compound such as a reducing organic water-soluble mercapto group-containing compound including SH-containing water-soluble lower alcohols (including SH-containing C 1 -C 1 2 primary, secondary and tertiary alkyl alcohols), SH-containing C 1 -C 12 primary, secondary and tertiary alkyl carboxylic acids, SH-containing C 1 -C 12 primary, secondary and tertiary alkyl amines and salts thereof,
  • SH-containing water-soluble lower alcohols including SH-containing C 1 -C 1 2 primary, secondary and tertiary alkyl alcohols
  • SH-containing C 1 -C 12 primary, secondary and tertiary alkyl carboxylic acids SH-containing C 1 -C 12 primary, secondary and tertiary alkyl amines and salts thereof
  • SH-containing C 1 -C 1 2 primary, secondary and tertiary alkyl amine acids and di- or tripeptides such as 2-mercaptoethylamine hydrochloride,
  • Reductants such as (NH 4 ) 2 C 2 O 4 NH 4 HC 2 O 4 .H 2 O, SO 2 ,
  • (NH 4 ) 2 SO 6 and H 2 are particularly advantageous as reductants since at least some of the reaction product is gaseous permitting higher concentrations of vanadium ions to be prepared and reducing further treatment of electrolyte to remove unwanted products.
  • pump 1 recirculates pentavalent/tetravalent vanadium ions througn positive compartment 503 and througn reservoir 505 via pipes 507 and 507A.
  • Pumo 2 recirculates divalent/trivalent vanadium ions through negative compartment 502 and through reservoir 506 via pipes 508 and 508A.
  • Electrical energy is withdrawn from cell 501 by loading an external circuit in the means to charge/discharge 516.
  • the incoming conductivity of V 2+ /V 3+ incoming negative electrolyte flowing through pipe 508A is measured by probe 510 and an output signal related thereto is determined by conductivity meter .
  • the incoming conductivity of V 4+ /V 5+ incoming positive electrolyte flowing through pipe 507A is measured by probe 511 and an output signal related thereto is determined by conductivity meter 509A.
  • the outgoing conductivity of V 2+ /V 3+ outgoing negative electrolyte flowing through pipe 508 is measured by probe 512 and an output signal related thereto is determined by
  • conductivity meter 517 The outgoing conductivity of V 4+ /V 5+ outgoing positive electrolyte flowing through pipe 507 is measured by probe 512A and an output signal related thereto is determined by conductivity meter
  • conductivities and the determined outgoing conductivities are transmitted to adjusting means 522 via wires 523, 523A, 524 and 524A respectively.
  • Adjusting means 522 determines the difference between the conductivities of the incoming and outgoing negative electrolytes and the difference between the conductivities of the incoming and outgoing positive electrolytes and adjusts the pump speeds of pumps 2 and 1, so that cell 501 outputs a selected discharge voltage.
  • Two analogous circuits to that shown in Fig. 3 or to that shown in Fig. 4 can be utilized, one for controlling pump 1 and one for controlling pump 2; except that ⁇ E oc is replaced by the difference between the
  • Fig. 9 demonstrates that the solution potentials of V 2+ /V 3+ in
  • H 2 SO 4 and V 4+ /V 5+ in H 2 SO 4 changes only slightly over a wide
  • E E° - cell cell
  • Fig. 10 shows the results of experiments in which the open-circuit voltage of an all-vanadium redox cell employing Selemion CMV membrane, as a function of the system's state-of-charge.
  • the results in this diagram demonstrates the feasibility of utilizing open-circuit voltage to monitor state-of-charge of the cell and thus control the charging and discharging processes between the required limits e.g. 10% to 90% state-of-charge.
  • Figs. 11 and 12 show the potentials of the positive and negative
  • Figs. 13a - 13c show the linear variation in the conductivities of both the positive (V 4+ /V 5+ ) and negative (V 2+ /V 3+ ) electrolytes of the vanadium redox cell as a function of state-of-charge.
  • the results in this diagram show that by simply measuring the conductivity of each solution with a standard probe, a simple meter can be calibrated to indicate solution state-of-charge directly for each half-cell electrolyte.
  • V 4+ (blue) - V 5+ (yellow) a spectrophotometric method could also be
  • Figure 14 shows a series of
  • curve 2 is absorbance at 700-850 nm minimum.
  • a simple detector can thus be employed to monitor the absorption by the solution of
  • the present invention discloses a method and apparatus which provide the necessary solution flowrate for a selected discharge voltage/current from a redox flow cell particularly an all-vanadium redox flow cell.
  • the method and apparatus are particularly useful in practical applications since a redox flow cell can be operated with minimum pumping energy so as to provide the required constant current and/or voltage output over a given period of time.
  • a redox flow cell can be operated so as to provide variable current and/or voltage output so as to meet demand requirements.
  • the latter method and apparatus are particularly useful in practical applications since a redox flow cell can be operated so that it requires a constant current and/or voltage input over a given period of time.
  • a redox flow cell can be operated with a variable current and/or voltage input under which conditions considerable pumping energy can be saved by adjusting the pump flow rates to the minimum required for the current involved and the SOC of the system.

Abstract

La présente invention se rapporte à un système de pile redox à flux électrolytique (100) dont l'état de charge peut être déterminé. Le système (100) comprend une pile redox à flux électrolytique (101) comportant un compartiment négatif (102), un compartiment positif (103) et un séparateur ionoconducteur (104) disposé opérationnellement entre le compartiment positif et le compartiment négatif et en contact avec des électrolytes positif et négatif dans les compartiments (103 et 102) pour assurer une communication ionique entre eux; une pompe à électrolyte positif (1); des organes (107, 105 et 107A) servant à transporter l'électrolyte positif entre le compartiment positif (103) et la pompe à électrolyte positif (1) et associés opérationnellement au compartiment positif (103) et à la pompe à électrolyte positif (1); une pompe à électrolyte négatif (2); des organes (108, 106 et 108A) servant à transporter l'électrolyte négatif entre le compartiment négatif (102) et la pompe à électrolyte négatif (2) et associés opérationnellement au compartiment négatif (102) et à la pompe à électrolyte négatif (2); des organes (110, 111 et 109) servant à mesurer une ou plusieurs caractéristiques des électrolytes positif et/ou négatif se rapportant à l'état de charge de la pile et associés opérationnellement aux électrolytes positif et/ou négatif; ainsi qu'un organe (122) permettant de déterminer l'état de charge de la pile à partir de ladite caractéristique ou desdites caractéristiques et associé opérationnellement aux organes de mesure (110, 111 et 109). La présente invention se rapporte également à un procédé permettant de déterminer l'état de charge d'une pile redox à flux électrolytique, à un procédé servant à fournir une tension/un courant de décharge sélectionné depuis une pile redox à flux électrolytique, à un procédé servant à fournir une tension/un courant de charge sélectionné depuis une pile redox à flux électrolytique, à un système de pile redox à flux électrolytique servant à fournir une tension/un courant de décharge sélectionné depuis une pile redox à flux électrolytique, ainsi qu'un système de pile redox à flux électrolytique comprenant une pile redox à flux électrolytique qui est adaptable de façon à nécessiter une tension/un courant de charge sélectionné.
PCT/AU1989/000252 1988-09-23 1989-06-09 Etat de charge d'une pile redox WO1990003666A1 (fr)

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