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  • 专利说明
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    • 专利摘要:
    Redox battery with immiscible electrolytes. The present invention relates to a redox battery (10) comprising a first and a second electrode (2, 3) separated, respectively by a first and a second electrolyte (4, 5) which are immiscible and which comprise redox active species. In this way this redox battery (10) can work without the need to use a selective ion exchange membrane, or any other type of physical separator such as ceramic membranes, or porous polymer membranes. This redox battery can operate in dynamic mode (redox flow battery), or in static mode. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2633601A1
    申请号:ES201630327
    申请日:2016-03-21
    公开日:2017-09-22
    发明作者:Paula NAVALPOTRO MOLINA；Marc Arlen ANDERSON；Jesús PALMA DEL VAL；Rebeca MARCILLA GARCÍA
    申请人:Fund Imdea Energia；Fundacion Imdea Energia；
    IPC主号:
    专利说明:

    REDOX BATTERY WITH INMISCIBLE ELECTROLYTES
    D E S C R I P C I O N
    5 OBJECT OF THE INVENTION
    The present invention is within the field of electric energy accumulators.
    More specifically, the object of the present invention is a redox battery with immiscible electrolytes that can work in dynamic mode (redox flow battery), or in static mode. Therefore, the present redox battery does not require a selective ion exchange membrane, or any other type of physical separator such as ceramic membranes, or porous polymeric membranes to separate the electrolytes.
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    BACKGROUND OF THE INVENTION
    Redox batteries are electrochemical energy storage devices that are based on the potential difference between two redox pairs. This potential difference determines the voltage of said battery. Usually the redox pairs are found in the active material of the electrodes but sometimes these redox pairs are dissolved in two liquid electrolytes that are separated by a selective ion exchange membrane and form two separate compartments. Through the reduction-oxidation of these species in their respective electrodes, electricity is stored.
    25
    Usually, these redox batteries are redox flow batteries, that is to say, each electrolyte flows, or circulates, through its corresponding compartment of the redox flow battery which has an inlet port and an outlet port of its respective electrolyte.
    30 More specifically, redox flow batteries, circulate the two electrolytes from two external tanks through each of the two compartments of the redox flow battery, enabling the decoupling of the energy and power they can supply. In this way, the energy depends on the size of the tanks that contain each electrolyte, while the power depends on the specific design of the battery.
    In a secondary, or reversible, redox-flow battery, dissolved redox species oxidize at the negative electrode (anode) and are reduced at the positive electrode (cathode) during the discharge of the battery. During the recharge of the battery the opposite process occurs regenerating the original species.
    5
    The most common configuration of the flow battery comprises a first and a second electrode in contact with a first and a second electrolyte each of which contains the redox active species. The first electrode is in contact with a redox active species of the first electrolyte and the second electrode is in contact with another redox active species of the second electrolyte. Both electrodes have connection terminals that can be connected to each other by a connection cable with an electric charge through which electrons flow. The active species of the electrolyte can be dissolved or suspended, such as vanadium, iron, zinc or other metal salts and more recently organic molecules.
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    In this configuration, the redox active species that are in contact with the anode and with the cathode are separated by a selective ion exchange membrane that serves both to keep the electrolytes separated and to allow the flow of ions from one compartment to another to Maintain electrical neutrality during operation. These 20 membranes are expensive, approximately 30% of the total cost of the battery, their ability to separate the electrolytes is not perfect, and their durability is limited, their replacement being necessary regularly with the consequent increase in maintenance costs.
    Currently, there are some developments in which the flow batteries allow the system to operate without the need to include a selective ion exchange membrane because liquid electrolytes are pumped with a constant flow in the laminar regime. Due to the laminar flow of the electrolytes they are kept separate and a physical separator between the two electrolytes is not necessary to avoid mixing. However, the design of a battery where laminar flow is forced can only be achieved through the implementation of microfluldica concepts. These concepts limit both the design and the
    battery size and therefore also limit its range of applications. This is because the amount of energy stored as! as its electrical power are several orders of magnitude lower than those of a conventional flow battery operating with the ionic exchange selective membrane.
    DESCRIPTION OF THE INVENTION
    The present invention consists of a redox battery for the accumulation of energy in a receptacle, or cell, which comprises in a first internal wall a first electrode and in 5 a second internal wall, facing the first internal wall, a second electrode. Preferably and not limitatively, both walls, and therefore the first and second electrodes, have a horizontal parallel projection.
    Additionally, said receptacle comprises a first liquid electrolyte in contact with the first electrode and a second liquid electrolyte in contact with the second electrode and with the first liquid electrolyte.
    It should be noted that in the present invention, "electrolyte" means a liquid medium consisting of a solvent containing dissolved free ions that behave like an electric conductive medium, and which additionally contains an active redox species that oxidizes and reduces during operation of the redox battery.
    More specifically, this redox battery can work in dynamic mode, referred to as redox flow battery, or in static mode, referred to as redox static battery. In dynamic mode the electrolytes are stored in external tanks and are flowed through at least one surface of their corresponding electrode, and in static mode the electrolytes do not flow, but are confined inside the redox battery.
    The first and the second electrolyte are immiscible with each other, so that by contacting they form two phases separated by an interface. The electrolyte separation therefore takes place spontaneously and the selective ion exchange membrane or any other type of physical separator such as ceramic membranes or porous polymer membranes is not necessary. From now on all these membranes or separators will be referred to as non-limiting as membrane.
    30
    The present invention by not requiring the use of membrane reduces the costs of fabrication, initial investment and operation and maintenance compared to conventional redox flow batteries that do require said membrane, which is usually a selective ion exchange membrane.
    Additionally, the redox battery of the present invention is very versatile, that is, it covers a wide range of applications, since the two electrolytes can be aqueous, or one of them aqueous and the other non-aqueous, or even the two electrolytes can be non-aqueous Specifically, this redox battery provides advantages in terms of the nominal voltage since 5, if at least one of the electrolytes is based on a non-aqueous solvent, it has greater electrochemical stability than the aqueous one. This allows electrochemical reactions of the active species to more positive or more negative potentials without the electrolyte degrading. This increase in the nominal voltage is associated with the consequent increase in energy density (E = QV) and the power (P = IV) of the battery. In addition, the
    The fact of having a wide range of solvents and redox species means that the chances of obtaining redox batteries with better performance are greatly increased.
    Another advantage of the present invention is that organic redox active species such as quinones, quinoxalines, viologens, pyridine carboxylates, methylphthalimides, methoxybenzenes,
    15 phenothiazines, nitroxides (radical TEMPO) are cheap, abundant and environmentally friendly, improving the sustainability of the redox batteries hitherto known that depend primarily on redox pairs based on metal centers as in the case of vanadium that is toxic, expensive and with limited solubility.
    20 In addition to being able to work in dynamic mode (redox flow battery) and in static mode, the present invention is fully scalable and its design is not subject to fluid dynamic requirements of laminar flow. That is, it is not necessary to pump the liquid electrolyte with a constant flow in the laminar regime to be able to operate without a membrane, but the separation of the two electrolytes occurs spontaneously due to their immiscibility.
    Additionally, in the present invention redox battery is understood as a secondary or rechargeable electrochemical cell, whose electrochemical reactions are electrically reversible, that is, it allows electric charge and discharge by changing the polarity of the electrodes.
    30 This redox battery can be assembled and connected fluidically and / or electrically in series and / or in parallel with other redox batteries to obtain a stackable redox battery whose voltage, energy and / or power values are suitable for the application in which use
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    Therefore, a first aspect of the invention relates to a redox battery with a receptacle comprising in a first internal wall a first electrode and in a second internal wall a second electrode, characterized in that:
    • the first and second electrodes are, preferably facing each other and horizontally parallel,
    • the receptacle comprises a first electrolyte in contact with the first electrode and a second electrolyte in contact with the second electrode and with the first electrolyte, and
    • electrolytes are immiscible and comprise redox active species.
    The electrolytes of the redox battery of the present invention are based on aqueous or non-aqueous solvents. Aqueous electrolytes are solutions of acids, bases or salts in water. While non-aqueous electrolytes can be salt solutions in organic solvents or ionic liquids. More specifically, organic solvents are polar organic (both protic and aprotic) and / or non-polar solvents. Ionic liquids are understood as any molten salt composed of cations and anions that are in a liquid state at temperatures below 100 ° C and preferably at room temperature. Ionic liquids are those compounds that are not limited to imidazolium, pyrrolidinium, quaternary ammonium, sulphonium or phosphonium cations and halide anions, borates, phosphates, imides, amides, triflates, etc.
    In a preferred embodiment, the two immiscible electrolytes are based on aqueous solvents.
    Another preferred embodiment relates to a redox battery, where one electrolyte is based on an aqueous solvent and the other electrolyte is based on a non-aqueous solvent.
    Another preferred embodiment relates to a redox battery, where both immiscible electrolytes are based on non-aqueous solvents.
    It should be noted that in the present invention, redox active species may be organic or inorganic redox active species.
    Redox organic species are any organic species that has reversible redox reactions and remains dissolved in the electrolyte when its oxidation state changes. Therefore, the redox species cannot suffer decomposition or degradation, nor form solids or gaseous species.
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    Preferably, the organic active species are from the family of quinones such as benzoquinones, naphthaquinones, anthraquinones. Other preferred organic active species are viologens, quinoxalines, pyridines, carboxylates, diols, ketones, phenols, methylphthalimides, methoxybenzenes, phenothiazines, nitroxides such as TEMPO.
    10
    Preferably, inorganic redox active species are based on the different oxidation states of metals such as Ru, Fe, U, V, Cr, Ni, Mn, Cu and Co.
    Preferably, the redox battery receptacle comprises a first pair of hydraulic connectors 15 with a first and a second connector adjacent to the first inner wall and a second pair of hydraulic connectors with a third and a fourth connector adjacent to the second inner wall respectively intended to connect a first and a second storage and distribution unit to store and distribute respectively the first and second liquid electrolyte inside the receptacle.
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    More specifically, said first and second electrolyte storage and distribution unit respectively comprise at least a first and a second tank linked with at least one first and a second pump.
    25 The first tank is linked to the first pair of hydraulic connectors and contains the first liquid electrolyte. This first liquid electrolyte is driven inwards through the first pump that is connected to the first connector and returns to the first tank through the second connector.
    30 The second tank is linked to the second pair of hydraulic connectors and contains the second liquid electrolyte. This second liquid electrolyte is driven inwards through the second pump that is connected to the third connector and returns to the second tank through the fourth connector.
    Thus, by connecting the receptacle of the battery to said first and second tank, and driving the electrolytes into it, the redox battery behaves like a redox flow battery.
    Additionally, the first tank comprises a first sensor to detect if the second electrolyte reaches the first tank and / or the second tank comprises a second sensor to detect if the first electrolyte reaches the second tank. Due to the thermodynamic properties of the electrolytes, the separation of these in both tanks occurs spontaneously, so that by means of a transfer unit, linked to both tanks, 10 the electrolyte that is not in the appropriate tank is transferred to its tank corresponding, without replacing the entire electrolyte or stopping the operation of the redox flow battery.
    In a second aspect of the invention it refers to the use of the redox battery described above as an energy storage device.
    DESCRIPTION OF THE DRAWINGS
    To complement the description that is being made and in order to help a better understanding of the characteristics of the invention, according to a preferred example of practical realization of the same, a set of said description is accompanied, as an integral part of said description. Drawings where the following has been illustrated and not limited to:
    Figure 1.- Shows a schematic view of a preferred embodiment of the redox battery of the present invention.
    Figure 2.- Shows a graph of the cyclic voltameters of a first and a second electrolyte
    TO.
    Figure 3.- Shows a graph of the polarization curve in discharge of the redox battery with electrolytes A from an initial state of charge of 35%.
    Figure 4.- Shows a graph of the discharge profile of the redox battery with electrolytes A for different discharge currents.
    Figure 5.- Shows a graph of the charge / discharge cycles at a constant intensity of 5 0.05mA / cm2 of the redox battery with electrolytes A.
    Figure 6.- It shows a graph of the evolution of the retention of the capacity of the redox battery with electrolytes A and its coulombic efficiency against the number of charge and discharge cycles.
    10
    Figure 7.- Shows a graph of the cyclic voltameters of a first and a second electrolyte
    B.
    Figure 8.- Shows a graph of the discharge profile of the redox battery with B electrolytes for 15 different discharge currents.
    Figure 9.- It shows a graph of the evolution of the retention of the redox battery capacity with B electrolytes and its coulombic efficiency against the number of charge and discharge cycles.
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    Figure 10.- Shows a graph of the cyclic voltameter of a first and second electrolyte
    C.
    Figure 11.- It shows a graph of the discharge profile of the redox battery with C 25 electrolytes for different discharge currents.
    Figure 12.- It shows a graph of the evolution of the retention of the capacity of the redox battery with C electrolytes and its coulombic efficiency against the number of charge and discharge cycles.
    30
    Figure 13.- Shows a graph of the voltametrlas clclicas of the first and second electrolyte
    D.
    Figure 14.- Shows a graph of the discharge profile of the redox battery with D electrolytes for a discharge current of 0.2 mA / cm2.
    PREFERRED EMBODIMENT OF THE INVENTION
    5
    In a preferred embodiment of the present invention, as shown schematically in Figure 1, the redox battery (10) comprises a receptacle (1) or cell, consisting of a first and a second electrode (2,3 ) positioned parallel and horizontally facing each other and acting as current collectors. These 10 electrodes (2,3) are separated by a first and a second electrolyte (4,5) that are immiscible with each other at room temperature, so that two phases are formed spontaneously separated by an interface (IB).
    Preferably, the electrolytes (4,5) are stored in a first and a second tank (6,7) and 15 are pumped by a first and a second pump (8,9) into the receptacle (1). Both the tanks (6,7) and the pumps (8,9) are connected to the receptacle (1) by means of hydraulic connectors, not shown. Thus, the connection between the tanks (6,7), the pumps (8,9) and the receptacle (1) form a first feedback circuit of the first electrolyte (4) and a second feedback circuit of the second electrolyte (5) where the 20 electrolytes (4,5) are always kept separate.
    Preferably, and not limitatively, the electrodes (2,3) comprise carbonaceous materials such as graphites, active carbons or carbon felts.
    25 It should be noted that in the preferred embodiments of the invention to facilitate its understanding, the first electrode (2) has been defined, not limited to, as an anolyte, that is, as the electrolyte where the reduction reaction of the redox active species occurs , and the second electrode (3) as a catholyte as the electrolyte where oxidation of the redox active species occurs during the redox battery charge (10).
    30
    EXAMPLE 1: In one embodiment, preferably, the electrolytes (4,5) are a first and a second liquid electrolyte A comprising two redox pairs of the quinonic type. More specifically, the first liquid electrolyte A comprises parabenzoquinone (pBQ) dissolved in an ionic liquid and the second liquid electrolyte A comprises hydroquinone (H2Q) dissolved in
    an aqueous solvent.
    More specifically, electrolytes A are prepared at room temperature by the following mixture of components:
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    • first liquid electrolyte A, or anolyte A: 20 mM Parabenzoquinone (pBQ) in 1-butyl- 1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide (PYR14TFSI),
    • Second liquid electrolyte A, or catholyte A: 20 mM Hydroquinone (H2Q) in 0.1M HCl acid medium in water.
    10
    During the redox battery charging (10) the following half-reactions occur:
    In the first electrolyte liquid A parabenzoquinone is reduced to its diameter.
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    image 1
    While in the second electrolyte liquid A hydroquinone is oxidized to parabenzoquinone.
    image2
    Reverse reactions take place during the download process.
    This preferred embodiment has the advantage that the active species are very similar in the two phases only by varying the oxidation state of parabenzoquinone, present in both phases. Therefore, if any species migrated from one phase to another (known in English as "crossover"), there would be no contamination of the electrolyte and it would be possible to regenerate the electrolyte 5 by applying an electric current to force the oxidation or reduction of the active species. If the active species were different, the "crossover" would cause a mixture of electrolytes whose regeneration would require much more complex chemical separation operations.
    10 The behavior of these half-reactions is independently assessed by means of a cyclic voltameter of each of the liquid electrolytes A, represented in Figure 2. More specifically, Figure 2 describes a first voltameter (to the left of Figure 2) corresponding to the of the first liquid electrolyte A comprising parabenzoquinone (pBQ) dissolved in a non-aqueous ionic liquid type electrolyte and a second voltameter (at
    15 right of the figure) corresponding to that of the second liquid electrolyte A comprising hydroquinone (H2Q) dissolved in an aqueous electrolyte.
    This cyclic voltameter has been performed in a three electrode electrochemical cell at a scanning speed of 10 mV / s using a glass carbon electrode as the electrode
    20 work, a platinum mesh as a counter electrode and a reference electrode (silver wire in the anolyte and Ag / AgCl in the catholyte). This figure 2 shows the redox behavior of each of the two liquid electrolytes A, the reversibility of the half-reactions and their redox potential.
    25 In the present embodiment, different types of experiments have been carried out for the characterization of the redox battery (10):
    Polarization test on discharge
    30 It consists of once the redox battery (10) is charged, different discharge current intensities are applied for short periods of time and the evolution of the redox battery potential (10) is recorded.
    In this preferred embodiment, discharge currents from 0 (open circuit) to 0.9mA / cm2 were applied through the electrodes (2.3), obtaining discharge voltages of 1.1 V-0.6 V, represented in Figure 3, and that It depends on the current density.
    5 Battery discharge tests at different discharge currents
    Once the battery is charged by a pre-charge stage, the discharge tests consist of applying a constant discharge current between the electrodes (2,3) until the redox battery (10) is completely discharged, reaching a potential of 0V. The discharge capacity of the battery as! Is calculated from the 10 discharge curve. As your download potential. Figure 4 shows the capacity of the redox battery (10) for different discharge currents, starting from a state of charge of 35%.
    Cyclability Assays
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    It consists of several consecutive cycles of constant current charge and discharge of the redox battery (10) as shown in Figure 5. This test allows to evaluate the reversibility of the battery and determine some characteristic parameters such as capacity retention and coulombic efficiency with the number of cycles as shown in Figure 20 6.
    EXAMPLE 2: In another embodiment, preferably the electrolytes (4,5) are a first and a second liquid electrolyte B which are formed by:
    • first electrolyte B liquid or anolyte B: 20 mM Parabenzoquinone (pBQ) in 1-butyl-125 methylpyrrolidinium bis (trifluoromethanesulfonyl) imide (PYR14TFSI),
    • Second liquid electrolyte B or catholyte B: 20 mM TEMPO in 0.1M NaCl neutral aqueous medium.
    During the redox battery charge (10) the following half-reactions occur:
    In the first liquid electrolyte B, parabenzoquinone is reduced to its size:
    image3
    While in the second illiquid electrolyte B the TEMPO radical oxidizes to its cation.
    image4
    5
    Reverse reactions take place during the download process
    The electrochemical behavior of each of the liquid electrolytes B is independently evaluated by the technique of cyclic voltameter shown in Figure 7. 10 More specifically, Figure 3 represents a first voltameter (to the left of the figure) corresponding to that of the first liquid electrolyte B comprising parabenzoquinone (pBQ) dissolved in a non-aqueous ionic liquid type electrolyte, and a second voltameter (to the right of the figure) corresponding to that of the second electrolyte B comprising the TEMPO molecule dissolved in a liquid electrolyte aqueous.
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    This cyclic voltameter has been performed in a three electrode electrochemical cell at a scanning speed of 10 mV / s using a glass carbon electrode as a working electrode, a platinum mesh as a counter electrode and a reference electrode (silver wire in the anolyte and Ag / AgCl in the catholyte). This figure 7 shows the redox behavior of each of the two liquid electrolytes B, the reversibility of the half-reactions and their redox potential.
    In the present embodiment, different types of experiments have been carried out for the characterization of this redox battery (10):
    Battery discharge tests at different discharge currents
    5
    Once the battery is charged through a pre-charge stage, the discharge tests consist of applying a constant discharge current between the electrodes (2,3) until the redox battery (10) is completely discharged to a potential of 0V. The discharge capacity of the battery and its discharge potential are calculated from the discharge curve. 10 Figure 8 shows the capacity of the redox battery (10) for different discharge currents, starting from a state of charge of 5%.
    Cyclability Assays
    15 It consists of doing several consecutive cycles of constant current charge / discharge of the redox battery (10), which allows to evaluate the evolution of capacity and efficiency with the number of cycles as shown in Figure 9.
    EXAMPLE 3: In another preferred embodiment, the electrolytes (4,5) are a first and a second Kquido C electrolyte which are formed by:
    • first liquid electrolyte C, or anolyte C: 20 mM Parabenzoquinone (pBQ) in 2- butanone with 0.1 M TBAPF6 as support salt.
    • second electrolyte Kquido C, or catholyte C: 20 mM Hydroquinone (H2Q) 0.1M HCl acid medium in water.
    25
    During the redox battery charge (10) the following half-reactions occur:
    In the first liquid electrolyte C, parabenzoquinone is reduced to its size:
    5
    image5
    While in the second illiquid electrolyte C the hydroquinone is oxidized to parabenzoquinone.
    image6
    Reverse reactions take place during the download process.
    This preferred embodiment of redox battery (10) with liquid electrolytes C has the advantage that the non-aqueous phase is based on an ordinary organic solvent with respect to liquid electrolytes A and B using an ionic liquid.
    The electrochemical behavior of each of the liquid electrolytes C is independently evaluated by the technique of cyclic voltameter shown in figure 10. 15 More specifically, this figure 10 shows a first voltameter (to the left of the figure) corresponding to that of the first liquid electrolyte C comprising parabenzoquinone (pBQ) dissolved in an organic non-aqueous electrolyte (butanone) and a second voltameter (to the right of the figure) which is that of the second liquid electrolyte C comprising hydroquinone (H2Q) dissolved in an aqueous liquid electrolyte.
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    This cyclic voltameter has been performed in a three electrode electrochemical cell at a scanning speed of 10 mV / s using a glass carbon electrode as a working electrode, a platinum mesh as a counter electrode and a reference electrode (silver wire in the anolyte and Ag / AgCl in the catholyte). This figure 10 shows the reversibility of the 25 semi-reactions and their redox potential.
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    In the present embodiment, different types of experiments have been carried out for the characterization of the redox battery (10):
    Battery discharge tests at different discharge currents
    Once the battery is charged through a pre-charge stage, the discharge tests consist of applying a constant discharge current between the electrodes (2,3) until the redox battery (10) is completely discharged to a potential of 0V. The discharge capacity of the battery and its discharge potential are calculated from the discharge curve. Figure 11 shows the capacity of the redox battery (10) for different discharge currents, starting from a state of charge of 35%.
    Cyclability Assays
    It consists of several consecutive cycles of charge / discharge at constant current of the redox battery (10), which allows to evaluate the evolution of capacity and efficiency with the number of cycles as shown in Figure 12.
    EXAMPLE 4: In another preferred embodiment the electrolytes (4,5) are a first and a second Kquido D electrolyte that are formed by:
    • first electrolyte Kquido D or anolyte D: 0.1 M Parabenzoquinone (pBQ) in propylene carbonate (PC) with 0.1 M TBAPF6 as a support salt,
    • Second liquid electrolyte D or catholyte D: 0.1 M Hydroquinone (H2Q) 0.1M HCl acid medium in water.
    During the redox battery charge (10) the following half-reactions occur:
    In the first Kquido D electrolyte, parabenzoquinone is reduced to its dianion:
    image7
    While in the second illiquid electrolyte D hydroquinone is oxidized to parabenzoquinone:
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    image8
    Reverse reactions take place during the download process.
    This preferred embodiment has the advantage of using in the non-aqueous phase an ordinary organic solvent and a higher concentration of active species in the two phases with respect to the previous embodiments.
    The electrochemical behavior of each of the liquid electrolytes D is evaluated independently by the technique of cyclic voltameter shown in Figure 13. More specifically, this figure 13 shows a first voltameter (to the left of the figure) corresponding to that of the first Liquid electrolyte D comprising parabenzoquinone (pBQ) dissolved in an organic non-aqueous electrolyte (propylene carbonate). The second voltameter (to the right of the figure) is that of the second liquid electrolyte D which comprises hydroquinone (H2Q) dissolved in an aqueous liquid electrolyte.
    This cyclic voltameter has been performed in a three electrode electrochemical cell at a scanning speed of 10 mV / s using a glass carbon electrode as the electrode
    work, a platinum mesh as a counter electrode and a reference electrode (silver wire in the anolyte and Ag / AgCl in the catholyte). This figure 7 shows the redox behavior of each of the two liquid electrolytes D, the reversibility of the half-reactions and their redox potential.
    5
    In the present embodiment different types of experiments have been carried out for the characterization of the redox battery (10):
    Battery discharge tests at different discharge currents
    10
    Once the battery is charged by a pre-charge stage, the discharge tests consist of applying a constant discharge current to the electrodes (2,3) until the redox battery (10) is completely discharged to a potential of 0V. The discharge capacity of the battery and its discharge potential are calculated from the discharge curve. 15 Figure 14 shows the capacity of the redox battery (10) for a discharge current of 0.2 mA / cm2, based on a state of charge of 5%.
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    权利要求:
    Claims (18)
    [1]
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    R E I V I N D I C A C I O N E S
    1. Redox battery (10) with a receptacle (1) comprising in a first internal wall a first electrode (2) and in a second internal wall a second electrode (3), characterized in that:
    • the first and second electrodes (2,3) face each other and in parallel,
    • the receptacle (1) comprises a first electrolyte (4) in contact with the first electrode (2) and a second electrolyte (5) in contact with the second electrode (3) and with the first electrolyte (4), and
    • electrolytes (4,5) are immiscible and comprise redox active species.
    [2]
    2. Redox battery (10) according to claim 1, wherein the two electrolytes (4,5) are based on an aqueous solvent.
    [3]
    3. Redox battery (10) according to claim 1, wherein the first electrolyte (4) is based on an aqueous solvent and the second electrolyte (5) is based on a non-aqueous solvent.
    [4]
    4. Redox battery (10) according to claim 1, wherein the second electrolyte (5) is based on an aqueous solvent and the first electrolyte (4) is based on a non-aqueous solvent.
    [5]
    5. Redox battery (10) according to claim 1, wherein both electrolytes (4,5) are based on a non-aqueous solvent.
    [6]
    6. Redox battery (10) according to any of claims 1 to 5, wherein the electrolytes
    (4.5) comprise the same redox active species.
    [7]
    7. Redox battery (10) according to any of claims 1 to 5, wherein the electrolytes
    (4.5) comprise different redox active species.
    [8]
    8. Redox battery (10) according to any one of claims 1 to 7, wherein the species
    redox active are organic or inorganic redox active species.
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    [9]
    9. Redox battery (10) according to claim 8, wherein the organic redox active species are selected from benzoquinones, naphthaquinones, anthraquinones, viologens, quinoxalines, pyridines, carboxylates, diols, ketones, phenols, methylphthalimides, methoxybenzenes, phenothiazines, nitroxidoses, nitroxidoses TEMPO.
    [10]
    10. Redox battery (10) according to claim 9, wherein the organic redox active species is parabenzoquinone.
    [11]
    11. Redox battery (10) according to claim 1, characterized in that the redox battery (10) does not comprise a selective ion exchange membrane or any other type of physical separator such as ceramic membranes, or porous polymeric membranes to separate electrolytes (4 ,5).
    [12]
    12. Redox battery (10) according to claim 1, characterized in that the receptacle (1) comprises a first pair of hydraulic connectors adjacent to the first inner wall and a second pair of hydraulic connectors adjacent to the second inner wall respectively intended for connect a first and a second storage and distribution unit to store and distribute respectively the first and second electrolyte (4,5) inside the receptacle (1).
    [13]
    13. Redox battery (10), according to claim 12, characterized in that the first and second storage and distribution unit respectively comprise at least a first tank (6) and a second tank (7) linked with at least a first pump (8) and a second pump (9) that allow the first and second electrolyte (4,5) to be pushed into the redox battery (10) and return to the tanks (6,7) to behave like a battery redox flow
    [14]
    14. Redox battery (10), according to claim 13, characterized in that the first tank (6) comprises a first sensor to detect if the second electrolyte (5) reaches the first tank (6).
    [15]
    15. Redox battery (10) according to claims 13 or 14, characterized in that the second tank (7) comprises a second sensor to detect if the first electrolyte (4) reaches the second tank (7).
    16. Redox battery (10) according to claims 14 or 15, characterized in that it comprises
    a transfer unit, linked to both tanks (6.7), which transfers the electrolyte that is not in its tank (6.7) to its corresponding tank (6.7).
    [17]
    17. Redox battery (10) according to claim 1, characterized in that the first and second
    10 electrode (2,3) have a horizontal parallel projection.
    [18]
    18. Redox battery (10), according to any one of the preceding claims, characterized in that several redox batteries (10) can be assembled and connected fluidically and / or electrically in series and / or in parallel to obtain a battery
    15 stackable redox whose voltage, energy and / or power values are suitable for the
    application in which it is used.
    [19]
    19. Use of the redox battery (10) according to claims 1 to 18 as an energy storage device.
    twenty
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    WO2021209585A1|2020-04-17|2021-10-21|Fundación Imdea Energía|Redox flow battery with immiscible electrolyte and flow through electrode|
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