WO2015019973A1 - Batterie à flux redox - Google Patents

Batterie à flux redox Download PDF

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Publication number
WO2015019973A1
WO2015019973A1 PCT/JP2014/070423 JP2014070423W WO2015019973A1 WO 2015019973 A1 WO2015019973 A1 WO 2015019973A1 JP 2014070423 W JP2014070423 W JP 2014070423W WO 2015019973 A1 WO2015019973 A1 WO 2015019973A1
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Prior art keywords
ion
ions
electrode electrolyte
positive electrode
divalent
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PCT/JP2014/070423
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English (en)
Japanese (ja)
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宏一 加來
雍容 董
慶 花房
良潤 關根
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住友電気工業株式会社
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Publication of WO2015019973A1 publication Critical patent/WO2015019973A1/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
    • H01M8/18—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
    • H01M2300/0011—Sulfuric acid-based
    • 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

  • the present invention relates to a redox flow battery.
  • the present invention relates to a redox flow battery that can suppress the generation of precipitates and has a high energy density.
  • RF battery redox flow battery
  • MW class megawatt class
  • long life long life
  • the RF battery performs charge and discharge by supplying a positive electrode electrolyte and a negative electrode electrolyte to battery cells in which a diaphragm is interposed between the positive electrode and the negative electrode, respectively.
  • a solution containing, as an active material, a metal ion whose valence changes by oxidation and reduction is typically used.
  • Typical examples are Fe-Cr RF batteries using iron (Fe) ions as the positive electrode active material and chromium (Cr) ions as the negative electrode active material, and V-based RF batteries using vanadium (V) ions as the active materials of both electrodes ( Paragraph 0003 of the specification of Patent Document 1).
  • Patent Document 1 as an RF battery capable of obtaining a higher electromotive force than a conventional V-type RF battery, manganese (Mn) ions are used as a positive electrode active material and titanium (Ti) ions are used as a negative electrode active material.
  • An RF battery is disclosed.
  • Patent Document 1 by containing together titanium ions in the positive electrode electrolyte solution, it is possible to suppress the generation of precipitates such as manganese oxide (MnO 2), it can be performed stably reaction of Mn 2+ / Mn 3+ Is disclosed.
  • MnO 2 manganese oxide
  • the generation of precipitates can be suppressed as described above by containing titanium ions in the positive electrode electrolyte.
  • the titanium ions in the positive electrode electrolyte basically do not function as a positive electrode active material and do not contribute to charge / discharge. Therefore, when the total concentration of metal ions in the positive electrode electrolyte is constant, the ratio of the active material in the positive electrode electrolyte is relatively decreased due to the inclusion of titanium ions, and the energy density is lowered. Further, for example, in order to use an electrolytic solution with a small proportion of the active material as a redox flow battery having a long capacity, it is necessary to use a large amount of the electrolytic solution. Then, the capacity of the tank increases, the size of the entire RF battery system due to the increase in the tank (enlargement of the installation space), the increase in the electrolyte cost, and the like are caused.
  • one of the objects of the present invention is to provide a redox flow battery that can suppress the generation of precipitates and has a high energy density.
  • the redox flow battery performs charge and discharge by supplying a positive electrode electrolyte and a negative electrode electrolyte to a battery cell including a positive electrode, a negative electrode, and a diaphragm interposed between the two electrodes.
  • the positive electrode electrolyte contains manganese ions and reactive metal ions.
  • the negative electrode electrolyte contains at least one metal ion selected from titanium ions, chromium ions, and zinc ions.
  • the reactive metal ion is at least one selected from vanadium ion, chromium ion, iron ion, cobalt ion, copper ion, molybdenum ion, ruthenium ion, palladium ion, silver ion, tungsten ion, mercury ion and cerium ion. .
  • the redox flow battery of the present invention can suppress the generation of precipitates and has a high energy density.
  • the redox flow battery according to the embodiment performs charge and discharge by supplying a positive electrode electrolyte and a negative electrode electrolyte to a battery cell including a positive electrode, a negative electrode, and a diaphragm interposed between the two electrodes.
  • the positive electrode electrolyte contains manganese ions and reactive metal ions.
  • the negative electrode electrolyte contains at least one metal ion selected from titanium ions, chromium ions, and zinc (Zn) ions.
  • the reactive metal ions include vanadium ions, chromium ions, iron (Fe) ions, cobalt (Co) ions, copper (Cu) ions, molybdenum (Mo) ions, ruthenium (Ru) ions, palladium (Pd) ions, silver It is at least one selected from (Ag) ions, tungsten (W) ions, mercury (Hg) ions, and cerium (Ce) ions.
  • the said reactive metal ion means what has a function as a positive electrode active material, and the function which suppresses precipitation of a deposit.
  • the RF battery of the embodiment uses manganese ions contained in the positive electrode electrolyte as the positive electrode active material, (1) the electromotive force can be increased as compared with a conventional V-type RF battery, (2) Since manganese ions are water-soluble metal ions, the electrolytic solution can be made into an aqueous solution and excellent in manufacturability. (3) Manganese ions are relatively inexpensive and preferable from the viewpoint of resource supply. Play.
  • the specific metal ion (reactive metal ion) contained in the positive electrode electrolyte also functions as the positive electrode active material, so that the ratio of the active material in the electrolyte can be increased.
  • the RF battery of the embodiment has a higher energy density than an RF battery including a positive electrode electrolyte that includes manganese ions and titanium ions and does not include the reactive metal ions.
  • the RF battery of the embodiment can suppress the generation of precipitates, even when the state of charge is increased, an increase in cell resistance due to the precipitates can be suppressed, and the cell resistance is low.
  • the RF battery of the embodiment has excellent battery characteristics.
  • the RF battery of the embodiment can reduce the size of the tank, the installation space, the cost of the electrolyte, and the like.
  • the positive electrode electrolyte further contains added metal ions.
  • the additive metal ions include aluminum (Al) ions, cadmium (Cd) ions, indium (In) ions, tin (Sn) ions, antimony (Sb) ions, iridium (Ir) ions, gold (Au) ions, lead ( Pb), at least one selected from bismuth (Bi) and magnesium (Mg) ions.
  • the said additive metal ion means what has a function which does not function as an active material substantially, but suppresses precipitation of a deposit.
  • the above-mentioned specific metal ions are present together with manganese ions in the positive electrode electrolyte, thereby suppressing the generation of precipitates such as manganese oxides.
  • the additive metal ions can suppress the generation of precipitates even if the content of the added metal ions is very small.
  • the said form can suppress generation
  • the said form can suppress the fall of the ratio of the active material in electrolyte solution by reducing content of an addition metal ion, and can have a high energy density.
  • the concentration of the reactive metal ions in the positive electrode electrolytic solution (total concentration in the case of plural) is 0.001 M or more and 5 M or less can be given.
  • M shown as a unit of concentration means volume molar concentration, that is, mol / L (mol / liter).
  • the said form contains a reactive metal ion in the above-mentioned specific range, (1) It can utilize a reactive metal ion favorably as an active material, and can have a high energy density, (2) Precipitate (3) Even when the electrolytic solution is an aqueous acid solution, it can be dissolved satisfactorily, and the electrolytic solution is excellent in manufacturability.
  • the concentration of the additive metal ions in the positive electrode electrolyte is 0.001M or more and 1M or less.
  • concentration of the additive metal ions in the positive electrode electrolyte is 0.001M or more and 1M or less.
  • the generation of precipitates can be effectively suppressed by containing the added metal ions in the specific range described above.
  • the RF battery of the embodiment there is a form in which at least one of the manganese ion concentration in the positive electrode electrolyte and the metal ion concentration in the negative electrode electrolyte is 0.3 M or more and 5 M or less. .
  • the metal ions contained in the negative electrode electrolyte are plural kinds, the total concentration is used.
  • the said form contains the metal ion which functions as an active material of each pole in the above-mentioned specific range, (i) It can fully contain the metal element which performs a valence change reaction, and can have a high energy density. (Ii) Even when the electrolytic solution is an aqueous acid solution, it can be dissolved satisfactorily, and the electrolytic solution is excellent in manufacturability.
  • the negative electrode electrolyte contains titanium ions as the metal ions, the concentration of the manganese ions in the positive electrode electrolyte, and the concentration of the titanium ions in the negative electrode electrolyte.
  • the form whose at least one is 0.3M or more and 5M or less is mentioned.
  • the manganese ion concentration and the titanium ion concentration satisfy a specific range, whereby a Mn—Ti RF battery having a high energy density can be obtained. Further, as described in the above-described embodiment (5) ( The effect of ii) is also achieved.
  • the reactive metal ion may have a form satisfying at least one of the following (A) to (L).
  • the vanadium ion is a divalent vanadium ion, a trivalent vanadium ion, a tetravalent vanadium ion, or a pentavalent vanadium ion.
  • the chromium ion is a divalent chromium ion, 3
  • the iron ion is at least one of a divalent iron ion and a trivalent iron ion
  • the cobalt ion is at least one of a divalent cobalt ion and a trivalent cobalt ion.
  • the copper ion is at least one of a monovalent copper ion and a divalent copper ion.
  • the molybdenum ion. Is at least one of a tetravalent molybdenum ion, a pentavalent molybdenum ion, and a hexavalent molybdenum ion.
  • the mu ion is at least one of a divalent ruthenium ion, a trivalent ruthenium ion, and a tetravalent ruthenium ion.
  • the palladium ion is at least one of a divalent palladium ion and a tetravalent palladium ion.
  • the silver ion is at least one of a monovalent silver ion and a divalent silver ion.
  • the tungsten ion is at least a tetravalent tungsten ion, a pentavalent tungsten ion, and a hexavalent tungsten ion.
  • the mercury ion is at least one of monovalent mercury ion and divalent mercury ion.
  • the cerium ion is at least one of trivalent cerium ion and tetravalent cerium ion. is there
  • the metal ions having the respective valences listed above function as a positive electrode active material and exhibit the effect of suppressing precipitates. Therefore, the above form has high energy density and can suppress the generation of precipitates.
  • the negative electrode electrolyte may further include a manganese ion.
  • both the positive electrode electrolyte and the negative electrode electrolyte contain manganese ions. That is, in the above form, at least one ionic species existing in the electrolyte solution of both electrodes overlaps. Therefore, for example, even when the manganese ions of the positive electrode move to the negative electrode over time, it is easy to avoid a decrease in battery capacity due to the reduction of the positive electrode active material by moving the manganese ions of the negative electrode to the positive electrode.
  • the negative electrode electrolyte may further include manganese ions and the reactive metal ions.
  • both the positive electrode electrolyte and the negative electrode electrolyte contain manganese ions and reactive metal ions. That is, in the above embodiment, both of the electrolyte solutions of both electrodes include a plurality of ion species, and a plurality of ion species existing in the electrolyte solution of both electrodes overlap.
  • the negative electrode electrolyte when the positive electrode electrolyte contains the above-described additive metal ions, the negative electrode electrolyte further contains manganese ions, the reactive metal ions, and the additive metal ions.
  • the form to include is mentioned.
  • both the positive electrode electrolyte and the negative electrode electrolyte contain manganese ions, reactive metal ions, and additive metal ions.
  • both the electrolytes of both electrodes contain a plurality of ionic species, and the plurality of ionic species existing in the electrolytes of both electrodes overlap. Therefore, as in the above-described form (9), the above-described form is (i) it is easy to avoid a decrease in battery capacity due to the reduction of the active material over time, and (ii) the liquid is changed over time with charge / discharge. Even if there is a variation in the amount of electrolyte solution in both electrodes due to the transfer, it is easy to correct, and (iii) the electrolyte solution is excellent in productivity.
  • the above embodiment has the same effects as the above embodiments (8) to (10). Specifically, the said form can suppress the reduction
  • the additional metal ion satisfies at least one of the following (a) to (j).
  • the aluminum ion is a monovalent aluminum ion, a divalent aluminum ion, or a trivalent aluminum ion.
  • the cadmium ion is a monovalent cadmium ion or a divalent cadmium ion.
  • the indium ion is at least one of monovalent indium ion, divalent indium ion, and trivalent indium ion.
  • the tin ion is divalent tin ion and tetravalent.
  • the antimony ion is a trivalent antimony ion and at least one of a pentavalent antimony ion
  • the iridium ion is a monovalent iridium ion or a divalent iridium ion Trivalent iridium ion, tetravalent iridium ion, pentavalent iri
  • the gold ion is a monovalent gold ion, a divalent gold ion, a trivalent gold ion, a tetravalent gold ion, or a pentavalent gold ion.
  • the lead ion is at least one of a divalent lead ion and a tetravalent lead ion
  • the bismuth ion is at least a trivalent bismuth ion and a pentavalent bismuth ion
  • the magnesium ion is at least one of a monovalent magnesium ion and a divalent magnesium ion
  • the above-described form contains the added metal ions having the respective valences in addition to the reactive metal ions, thereby generating precipitates. Can be more effectively suppressed.
  • the manganese ion is at least one of a divalent manganese ion and a trivalent manganese ion
  • the negative electrode electrolyte contains titanium ions as the metal ions.
  • the form whose titanium ion is at least one of a trivalent titanium ion and a tetravalent titanium ion is mentioned.
  • the listed manganese ions function as a positive electrode active material in the positive electrode electrolyte, and the listed titanium ions function as a negative electrode active material.
  • An Mn—Ti based RF battery can be constructed.
  • manganese ions of each listed valence are also contained in the negative electrode electrolyte, the same effect as in the above embodiments (8) to (10), that is, the battery capacity due to at least the reduction of the positive electrode active material over time Can be suppressed.
  • the concentration of manganese ions in the positive electrode electrolyte, the type / concentration of metal ions (negative electrode active material) in the negative electrode electrolyte, the type of acid / acid concentration, and the reactivity of the electrolyte in each electrode The type / concentration of the metal ions / additional metal ions, the amount of the electrolyte, the material / size of the electrode, the material of the diaphragm, and the like can be appropriately changed.
  • an additional metal ion can be added to the electrolyte solution of at least one of the electrodes.
  • FIG. 1 shows an example of ionic species contained in the electrolytic solution.
  • a solid line arrow means charging
  • a broken line arrow means discharging.
  • the redox flow battery (RF battery) 1 of the embodiment typically includes a power generation unit 300 (for example, a solar power generator, a wind power generator, and the like, via an AC / DC converter 200, a transformer facility 210, and the like. General power plant etc.) and a power system or a customer (power system / customer 400) are connected and charged using the power generation unit 300 as a power supply source, and discharged using the power system / customer 400 as a power supply target.
  • a circulation mechanism for circulating the electrolyte in the RF battery 1 is constructed.
  • the RF battery 1 includes a positive electrode cell 102 containing a positive electrode 104, a negative electrode cell 103 containing a negative electrode 105, and a diaphragm 101 that separates the cells 102 and 103 and transmits predetermined ions. Is a main component.
  • a positive electrode electrolyte tank 106 is connected to the positive electrode cell 102 via conduits 108 and 110.
  • a negative electrode electrolyte tank 107 is connected to the negative electrode cell 103 via conduits 109 and 111.
  • the conduits 108 and 109 are provided with pumps 112 and 113 for circulating the electrolyte solution of each electrode.
  • the RF battery 1 uses the conduits 108 to 111 and the pumps 112 and 113 to the positive electrode cell 102 (positive electrode 104) and the negative electrode cell 103 (negative electrode 105), respectively.
  • the electrolyte solution is circulated and supplied, and charging / discharging is performed in accordance with the valence change reaction of the metal ion that becomes the active material in the electrolyte solution of each electrode.
  • the RF battery 1 typically uses a form called a cell stack including a plurality of battery cells 100.
  • the cells 102 and 103 include a bipolar plate (not shown) in which the positive electrode 104 is disposed on one surface and the negative electrode 105 is disposed on the other surface, a supply hole for supplying an electrolytic solution, and an exhaust for discharging the electrolytic solution.
  • a configuration using a cell frame having a liquid hole and having a frame (not shown) formed on the outer periphery of the bipolar plate is representative.
  • the liquid supply hole and the drainage hole constitute an electrolyte flow path, and the flow path is connected to conduits 108-111.
  • the cell stack is configured by repeatedly stacking a cell frame, a positive electrode 104, a diaphragm 101, a negative electrode 105, a cell frame,.
  • As the basic configuration of the RF battery system a known configuration can be appropriately used.
  • the positive electrode electrolyte contains manganese ions
  • the negative electrode electrolyte contains at least one metal ion selected from titanium ions, chromium ions, and zinc ions.
  • a reactive metal ion is contained as a specific metal ion which has a some function further in positive electrode electrolyte solution.
  • Manganese ions have at least one valence ion in the positive electrode electrolyte.
  • a divalent manganese ion and a trivalent manganese ion can be mentioned.
  • tetravalent manganese may be contained. This tetravalent manganese is considered to be MnO 2 .
  • this MnO 2 is not a solid precipitate but exists in a stable state as dissolved in the electrolyte, and is reduced to Mn 2+ by a two-electron reaction (Mn 4+ + 2e ⁇ ⁇ Mn 2+ ) during discharge. In other words, it can be discharged to act as an active material and be used repeatedly, which may contribute to an increase in battery capacity. Therefore, the presence of a slight amount (about 10% or less of the total amount (mol) of manganese ions) of tetravalent manganese is allowed in the positive electrode electrolyte.
  • Examples of the manganese ion concentration (hereinafter referred to as Mn content) in the positive electrode electrolyte include 0.3M or more and 5M or less. When it is 0.3 M or more, a sufficient energy density (for example, about 10 kWh / m 3 ) as a large-capacity storage battery can be obtained. Since the energy density is increased as the Mn content is higher, the Mn content can be set to 0.5 M or more, and more preferably 1.0 M or more. In the RF battery 1 according to the embodiment, by containing the reactive metal ions described later in the positive electrode electrolyte, even if the concentration of manganese ions is increased, the generation of precipitates can be suppressed, and the manganese ions can be stabilized. Be present. However, considering the solubility in a solvent, the Mn content is easily 5M or less, more preferably 2M or less, and the productivity of the electrolytic solution is excellent.
  • the positive electrode electrolyte solution with which RF battery 1 of embodiment is equipped contains a reactive metal ion further.
  • This reactive metal ion functions as a positive electrode active material, and also functions as an inhibitor for the generation of precipitates such as manganese oxide.
  • the specific reactive metal ion is at least one selected from vanadium ion, chromium ion, iron ion, cobalt ion, copper ion, molybdenum ion, ruthenium ion, palladium ion, silver ion, tungsten ion, mercury ion and cerium ion. Is mentioned.
  • Each reactive metal ion has at least one valence ion in the positive electrode electrolyte.
  • vanadium ions include divalent vanadium ions, trivalent vanadium ions, tetravalent vanadium ions, and pentavalent vanadium ions.
  • chromium ions include divalent chromium ions, trivalent chromium ions, tetravalent chromium ions, and hexavalent chromium ions.
  • the iron ion includes a divalent iron ion and a trivalent iron ion.
  • cobalt ions include divalent cobalt ions and trivalent cobalt ions.
  • the copper ion includes a monovalent copper ion and a divalent copper ion.
  • Examples of (F) molybdenum ions include tetravalent molybdenum ions, pentavalent molybdenum ions, and hexavalent molybdenum ions.
  • (G) Ruthenium ions include divalent ruthenium ions, trivalent ruthenium ions, and tetravalent ruthenium ions.
  • Examples of (H) palladium ions include divalent palladium ions and tetravalent palladium ions.
  • (I) Silver ions include monovalent silver ions and divalent silver ions.
  • Examples of tungsten ions include tetravalent tungsten ions, pentavalent tungsten ions, and hexavalent tungsten ions.
  • Examples of (K) mercury ions include monovalent mercury ions and divalent mercury ions.
  • Examples of (L) cerium ions include trivalent cerium ions and tetravalent cerium ions. There may be other valences than those listed. In some cases, ions of the same element but different in valence are included. Furthermore, the case where these elements exist as a metal (solid) in addition to ions is allowed.
  • each metal ion listed as a reactive metal ion is a lower potential or a higher potential than that of manganese ions. For this reason, these metal ions are contained together with manganese ions in the positive electrode electrolyte solution, so that the valence change reaction is sequentially performed substantially in accordance with the potential and functions as a positive electrode active material.
  • any of a form containing a single type of reactive metal ion and a form containing a plurality of types of reactive metal ions can be used.
  • the vanadium ions when vanadium ions are included as reactive metal ions, the vanadium ions have a track record as an active material for conventional V-type RF batteries, so that the reliability of the battery can be improved.
  • the concentration of the reactive metal ions in the positive electrode electrolyte (the total concentration when plural kinds of reactive metal ions are included) is, for example, 0.001M or more and 5M or less.
  • concentration when plural kinds of reactive metal ions are included is, for example, 0.001M or more and 5M or less.
  • reactive metal ions can be effectively used as a positive electrode active material together with manganese ions, and the ratio of the positive electrode active material in the positive electrode electrolyte can be increased. Therefore, the RF battery 1 having a high energy density can be obtained.
  • production of a precipitate can be suppressed even if the positive electrode electrolyte solution does not contain a titanium ion as it is 0.001M or more.
  • the concentration of the reactive metal ion in the positive electrode electrolyte is 5M or less, and more preferably 2M or less, which is excellent in the productivity of the electrolyte.
  • the electrolytic solution is an aqueous acid solution
  • the generation of precipitates can be suppressed by increasing the acid concentration to some extent, as will be described later.
  • increasing the acid concentration causes a decrease in the solubility of the metal ions.
  • the RF battery 1 of the embodiment can suppress the generation of precipitates by containing reactive metal ions, it is not necessary to excessively increase the acid concentration, and the metal ion concentration should be within a practical range. it can. Either the same or different manganese ion concentration and reactive metal ion concentration can be used.
  • the positive electrode electrolyte solution with which the RF battery 1 of embodiment is equipped can contain further the ion which has an inhibitory effect with respect to generation
  • ions include at least one selected from aluminum ions, cadmium ions, indium ions, tin ions, antimony ions, iridium ions, gold ions, lead ions, bismuth ions, and magnesium ions.
  • Each metal ion has at least one valence ion in the positive electrode electrolyte.
  • (a) aluminum ions include monovalent aluminum ions, divalent aluminum ions, and trivalent aluminum ions.
  • Cadmium ions include monovalent cadmium ions and divalent cadmium ions.
  • Indium ions include monovalent indium ions, divalent indium ions, and trivalent indium ions.
  • D As for a tin ion, a bivalent tin ion and a tetravalent tin ion are mentioned.
  • Antimony ions include trivalent antimony ions and pentavalent antimony ions.
  • iridium ions include monovalent iridium ions, divalent iridium ions, trivalent iridium ions, tetravalent iridium ions, pentavalent iridium ions, and hexavalent iridium ions.
  • Gold ions include monovalent gold ions, divalent gold ions, trivalent gold ions, tetravalent gold ions, and pentavalent gold ions.
  • Lead ions include divalent lead ions and tetravalent lead ions.
  • Bismuth ions include trivalent bismuth ions and pentavalent bismuth ions.
  • Magnesium ions include monovalent magnesium ions and divalent magnesium ions. There may be other valences than those listed. In some cases, ions of the same element but different in valence are included. Furthermore, the case where these elements exist as a metal (solid) in addition to ions is allowed.
  • Each metal ion enumerated as an additive metal ion is effective in suppressing the generation of the above-mentioned precipitates, even if it is in a trace amount, and therefore suppresses a decrease in the ratio of the active material accompanying the inclusion of the additive metal ion in the electrolyte. easy.
  • Each of the metal ions listed above mainly functions as an inhibitor of the generation of the precipitate, and does not substantially function as an active material. However, some ionic species may function as an active material (for example, lead ions). When the added metal ion also functions as a positive electrode active material, the energy density can be further increased.
  • any of a form containing a single kind of added metal ion and a form containing a plurality of kinds of added metal ions can be used.
  • the concentration of the added metal ions in the positive electrode electrolyte (the total concentration when plural kinds of added metal ions are included) is, for example, 0.001M or more and 1M or less.
  • production of a precipitate can be effectively suppressed with a reactive metal ion as it is 0.001M or more.
  • the concentration of the added metal ions is expected to increase the effect of suppressing the precipitate as the concentration increases, it can be 0.005M or more, and further 0.01M or more.
  • the concentration of the added metal ion is preferably 0.8M or less, more preferably 0.5M or less.
  • the negative electrode electrolyte with which the RF battery 1 of embodiment is equipped contains at least 1 type of metal ion selected from a titanium ion, chromium ion, and zinc ion as a negative electrode active material. Any of these metal ions can be combined with manganese ions as the positive electrode active material to form a redox pair having a high electromotive force.
  • Each metal ion used as the negative electrode active material has at least one valence ion in the negative electrode electrolyte.
  • ions of the same element and different valences are included.
  • these elements exist as a metal (solid) in addition to ions is allowed.
  • a form containing a single kind of metal ion or a form containing a plurality of kinds of metal ions can be used.
  • an electromotive force of about 1.4 V can be obtained in a Mn—Ti RF battery containing titanium ions as the negative electrode active material.
  • titanium ions when titanium ions are included as the negative electrode active material, titanium ions move over time due to repeated charge and discharge and mixed into the positive electrode electrolyte from the negative electrode electrolyte. It can function as an inhibitor for the generation of precipitates.
  • the titanium ion in the negative electrode electrolyte contains at least one valence ion. For example, a trivalent titanium ion and a tetravalent titanium ion can be mentioned.
  • the negative electrode electrolyte can increase the utilization rate of metal ions and improve the energy density.
  • Examples of the concentration of each metal ion listed as the negative electrode active material include 0.3 M or more and 5 M or less. When it is 0.3 M or more, a sufficient energy density (for example, about 10 kWh / m 3 ) as a large-capacity storage battery can be obtained. Since the energy density increases as the concentration of the metal ion in the negative electrode electrolyte increases, it can be set to 0.5 M or more, and further 1.0 M or more. However, considering the solubility in the solvent, the concentration of the metal ion in the negative electrode electrolyte is easily 5M or less, more preferably 2M or less, and the productivity of the electrolyte is excellent.
  • a Mn—Ti RF battery having a high energy density as described above when titanium ions are contained as a negative electrode active material in the range of 0.3M to 5M, a Mn—Ti RF battery having a high energy density as described above can be obtained.
  • the total form of the concentration of manganese ions that mainly function as a positive electrode active material and the concentration of reactive metal ions in the positive electrode electrolyte and the concentration of metal ions that mainly function as the negative electrode active material in the negative electrode electrolyte are the same, Any of the different forms can be used.
  • the negative electrode electrolyte solution can contain at least one of the above-mentioned ionic species of added metal ions. That is, at least one of the positive electrode electrolyte and the negative electrode electrolyte can be in a form containing an additive metal ion.
  • the negative electrode electrolyte contains at least one kind of added metal ion, (1) the battery reactivity of the metal ion functioning as the negative electrode active material can be increased (the reaction rate can be increased), and (2) depending on the ionic species, the active material (3) the generation of hydrogen accompanying water decomposition can be suppressed.
  • the negative electrode electrolyte solution can include the above-described metal ions such as titanium ions serving as a negative electrode active material, and can have the following form.
  • A A form containing manganese ions.
  • B A form containing at least one of the same ionic species as the reactive metal ion contained in the positive electrode electrolyte.
  • C A form in which at least one of the same ionic species is included when the positive electrode electrolyte contains at least one of the ionic species of the additive metal ions listed above.
  • D A form satisfying two of the above forms (a) to (c) (for example, form (a) + form (b)).
  • E A form satisfying all of the above forms (a) to (c).
  • any of the above forms (a) to (e) at least one ionic species contained in the positive electrode electrolyte and the negative electrode electrolyte overlaps. Therefore, these forms are (i) easy to avoid a decrease in battery capacity due to a decrease in active material over time, (ii) easy to correct variations in the amount of electrolyte in both electrodes due to liquid transfer, (iii) There are effects that it is easy to suppress a change in concentration caused by the movement of metal ions to the counter electrode, and (iv) it is easy to produce an electrolyte solution. For example, in the form (a), it is easy to suppress at least a decrease with time of the positive electrode active material.
  • the negative electrode electrolyte contains chromium ions and manganese ions and the reactive metal ions of the positive electrode electrolyte are chromium ions
  • all ionic species can match.
  • the concentration of the metal ion overlapping in the electrolyte solution of both electrodes can be used either in a different form in both electrodes or in an equal form in both electrodes.
  • the valence of the metal ions overlapping in the electrolyte solution of both electrodes either a different form in both electrodes or an equal form in both electrodes can be used.
  • the negative electrode electrolyte contains titanium ions and manganese ions (a), the negative electrode electrolyte contains titanium ions, manganese ions, and reactive metal ions of the same ionic species contained in the positive electrode electrolyte.
  • Form (d) (form (a) + form (b)), form in which the negative electrode electrolyte contains titanium ions, manganese ions, and reactive metal ions and added metal ions of the same ionic species contained in the positive electrode electrolyte ( e).
  • the reactive metal ion contained in the electrolyte solution of both electrodes is vanadium ion
  • the vanadium ion in the electrolyte solution of each electrode can function as a positive electrode active material and a negative electrode active material.
  • the concentration of manganese ions in the negative electrode electrolyte is, for example, 0.3 M or more and 5 M or less. If it is this concentration range, it will be easy to melt
  • the negative electrode electrolyte contains manganese ions, for example, divalent manganese ions and trivalent manganese ions can be mentioned.
  • reactive metal ions or additive metal ions are included in the electrolyte solution of both electrodes, at least one ion species of each electrode can include different ions.
  • An aqueous solution (electrolytic solution) of an acid prepared using sulfuric acid or sulfate includes, for example, sulfate anion (SO 4 2 ⁇ ).
  • the generation of precipitates such as manganese oxide can be suppressed to some extent by increasing the acid concentration.
  • an electrolytic solution containing metal ions capable of suppressing the generation of precipitates such as reactive metal ions the generation of precipitates may be suppressed even if the acid concentration in the electrolytic solution is lowered to some extent.
  • an aqueous solution prepared using a known acid or a known salt in addition to sulfuric acid or a sulfate can be used.
  • the materials of the positive electrode 104 and the negative electrode 105 include those mainly composed of carbon fiber, for example, non-woven fabric (carbon felt) and paper.
  • carbon felt non-woven fabric
  • the electrolyte oxygen gas is hardly generated even when the oxygen generation potential is reached during charging, (2) the surface area is large, (3) the electrolyte It has the effect of being excellent in the distribution of Known electrodes can be used.
  • an ion exchange membrane such as a cation exchange membrane or an anion exchange membrane can be mentioned.
  • the ion exchange membrane has the effects of (1) excellent separation between the metal ions of the positive electrode active material and the metal ions of the negative electrode active material, and (2) excellent permeability of H + ions (charge carriers inside the battery). Yes, it can be suitably used for the diaphragm 101.
  • a known diaphragm can be used.
  • Test Example 1 A positive electrode electrolyte containing manganese ions and a negative electrode electrolyte containing titanium ions were prepared, the RF battery system shown in FIG. 1 was constructed, and after charging, the deposition state was examined.
  • Sample No. containing only manganese ions as the positive electrode active material was used.
  • Sample No. 1-100 containing manganese ions and vanadium ions (reactive metal ions) as positive electrode active materials. 1-1 were prepared.
  • the positive electrode electrolyte 1-1 was prepared using manganese sulfate, vanadium oxosulfate, and sulfuric acid (in this case, an aqueous solution).
  • the produced positive electrode electrolyte has a manganese ion (divalent) concentration of 0.5 M, a vanadium ion (tetravalent) concentration of 0.5 M, and a sulfate ion concentration (the total concentration in the electrolyte, which is shown as the total concentration in the table) The same applies to the following test examples.) Is 4.0M.
  • Sample No. A positive electrode electrolyte of 1-100 was prepared using manganese sulfate and sulfuric acid (here, an aqueous solution).
  • the prepared positive electrode electrolyte has a manganese ion (divalent) concentration of 0.5M and a sulfate ion concentration (total concentration) of 3.5M.
  • the negative electrode electrolyte was prepared using titanium sulfate and sulfuric acid (in this case, an aqueous solution).
  • the produced negative electrode electrolyte has a titanium ion (tetravalent) concentration of 1.0 M and a sulfate ion concentration (total concentration) of 4.0 M.
  • a small cell having an electrode reaction area of 9 cm 2 was produced. Carbon felt was used for each electrode, and an ion exchange membrane was used for the diaphragm.
  • a ⁇ h Charging current (A) x Charging time (h)
  • Theoretical electricity of one-electron reaction (A ⁇ h) electrolyte volume (L) ⁇ manganese ion concentration (mol / L) ⁇ Faraday constant: 96,485 (A ⁇ second / mol) ⁇ 1 (electron) / 3600
  • sample No. 1 containing only manganese ions in the positive electrode electrolyte was obtained.
  • a brown substance solid
  • This brown material was analyzed and found to be MnO 2 . From this, sample no. It can be seen that in 1-100, precipitates are generated when the state of charge is increased.
  • Sample No. In 1-1 substantially no deposits as described above were found on the inner wall of the tank of the positive electrode electrolyte. From this, it was confirmed that the generation of precipitates such as MnO 2 can be suppressed by adding metal ions such as vanadium ions in addition to manganese ions to the positive electrode electrolyte.
  • Test Example 2 A positive electrode electrolyte containing manganese ions and a negative electrode electrolyte containing titanium ions were prepared, the RF battery system shown in FIG. 1 was constructed, and after charging, the state of charge (SOC) was examined.
  • SOC state of charge
  • sample no. 2-1 is a positive electrode electrolyte solution having a composition of manganese ion (divalent) concentration of 0.5M, vanadium ion (tetravalent) concentration of 0.5M, and sulfate ion concentration (total concentration) of 4.0M. Prepared.
  • Sample No. In No. 2-100 an electrolytic solution having a composition of a manganese ion (divalent) concentration of 0.5 M and a sulfate ion concentration (total concentration) of 3.5 M was prepared as a positive electrode electrolytic solution.
  • an electrolyte solution having a composition of a negative electrode electrolyte having a titanium ion (tetravalent) concentration of 1.0 M and a sulfate ion concentration (total concentration) of 4.0 M was prepared.
  • 9 ml of the positive electrode electrolyte and 30 ml of the negative electrode electrolyte were prepared.
  • a small cell having an electrode reaction area of 9 cm 2 was prepared and charged using the prepared electrolyte.
  • the charging conditions were a constant current of 630 mA (a constant current with a current density of 70 mA / cm 2 ), and a charge termination voltage of 2.0V.
  • SOC,% of manganese ions at the end of this charge was examined. The results are shown in Table 1. Further, after the end of charging, the amount of precipitates (here, MnO 2 ) present in the tank or the like was visually examined. The results are shown in Table 1.
  • sample No. 1 containing only manganese ions in the positive electrode electrolyte was used.
  • Sample No. 2 contains metal ions such as vanadium ions in addition to manganese ions in the positive electrode electrolyte.
  • SOC state of charge
  • One of the reasons for the improved state of charge is that of sample no.
  • manganese ions could be sufficiently utilized as an active material because generation of precipitates such as MnO 2 could be suppressed by metal ions such as vanadium ions.
  • Test Example 3 A positive electrode electrolyte containing manganese ions and a negative electrode electrolyte containing titanium ions were prepared, the RF battery system shown in FIG. 1 was constructed, and the battery characteristics were examined by charging and discharging.
  • positive electrode electrolyte and the negative electrode electrolyte those having the same ion species and concentration as those in Test Example 1 were used. That is, sample no. 3-1.
  • a positive electrode electrolyte an electrolyte having a composition of manganese ion (divalent) concentration of 0.5M, vanadium ion (tetravalent) concentration of 0.5M, and sulfate ion concentration (total concentration) of 4.0M Prepared.
  • Sample No. No. 3-100 prepared a positive electrode electrolyte having a composition of manganese ion (divalent) concentration of 0.5M and sulfate ion concentration (total concentration) of 3.5M.
  • sample No. Sample No. 3 further containing titanium ions in the positive electrode electrolyte of 3-100. 3-110 was prepared.
  • Sample No. The 3-110 positive electrode electrolyte has a manganese ion (divalent) concentration of 0.5M, a titanium ion (tetravalent) concentration of 0.5M, and a sulfate ion concentration (total concentration) of 4.0M. did.
  • an electrolyte solution having a composition of a negative electrode electrolyte having a titanium ion (tetravalent) concentration of 1.0 M and a sulfate ion concentration (total concentration) of 4.0 M was prepared.
  • 6 ml of electrolyte solution for each electrode was prepared.
  • a small cell having an electrode reaction area of 9 cm 2 was prepared, and a charge / discharge cycle test was performed using the prepared electrolyte.
  • the charging / discharging conditions are a constant current of 630 mA (constant current of 70 mA / cm 2 current density), a charging side switching voltage (voltage switching from charging to discharging) is 1.5 V, and a discharging side switching voltage (from discharging to charging).
  • the voltage to be switched) was 0 V, and the number of cycles was 3.
  • current efficiency (%) and discharge capacity (Ah / L) were examined.
  • the current efficiency (%) was obtained by (discharge time / charge time) ⁇ 100 for each cycle.
  • Table 2 shows the average of the current efficiency at the second cycle and the current efficiency at the third cycle.
  • discharge time (s) discharge time (s) ⁇ current value (A) / 3600) / electrolyte volume (L) was determined for each cycle.
  • Table 2 shows the average of the discharge capacity at the second cycle and the discharge capacity at the third cycle.
  • sample No. 1 containing only manganese ions in the positive electrode electrolyte was used.
  • sample No. 3 containing metal ions such as vanadium ions in addition to manganese ions in the positive electrode electrolyte. 3-1, it can be seen that the current efficiency and the discharge capacity are high.
  • One of the reasons for the improvement in current efficiency and discharge capacity is that of sample no.
  • 3-1 it is considered that manganese ions could be sufficiently used as an active material because generation of precipitates such as MnO 2 could be suppressed by metal ions such as vanadium ions.
  • sample Nos. Containing metal ions such as vanadium ions In Sample 3-1, Sample No.
  • Test Example 4 A positive electrode electrolyte containing manganese ions and a negative electrode electrolyte containing titanium ions and manganese ions were prepared, the RF battery system shown in FIG. 1 was constructed, and the battery characteristics were examined by charging and discharging.
  • the positive electrode electrolyte and the negative electrode electrolyte were prepared using sulfate and sulfuric acid as in Test Example 1.
  • Sample No. 4-1 is an electrolyte having a composition of a manganese ion (divalent) concentration of 0.5 M, a vanadium ion (tetravalent) concentration of 0.5 M, and a sulfate ion concentration (total concentration) of 4.0 M as a positive electrode electrolyte. 6 ml was prepared.
  • the negative electrode electrolyte 12 ml of an electrolyte having a composition of titanium ion (tetravalent) concentration of 0.5M, manganese ion (divalent) concentration of 0.5M, and sulfate ion concentration (total concentration) of 4.0M was prepared.
  • Sample No. 4-2 is a positive electrode electrolyte having a manganese ion (divalent) concentration of 0.5M, a vanadium ion (trivalent) concentration of 0.25M, a vanadium ion (tetravalent) concentration of 0.25M, and a sulfate ion concentration
  • An electrolyte solution having a composition with a total concentration of 4.0M was prepared.
  • the negative electrode electrolyte has a titanium ion (tetravalent) concentration of 0.5M, a manganese ion (divalent) concentration of 0.5M, a vanadium ion (trivalent) concentration of 0.25M, and a vanadium ion (tetravalent) concentration of 0.
  • An electrolyte solution having a composition of .25M and a sulfate ion concentration (total concentration) of 4.5M was prepared.
  • Test Example 5 A positive electrode electrolyte containing manganese ions and a negative electrode electrolyte containing titanium ions were prepared, the RF battery system shown in FIG. 1 was constructed, and the battery characteristics were examined by charging and discharging.
  • sample no. 5-1 uses manganese sulfate, sulfuric acid, and iron (II) sulfate as the positive electrode electrolyte, the manganese ion (divalent) concentration is 0.5M, the sulfate ion concentration (total concentration) is 4.0M, Fe ions ( An electrolytic solution having a composition having a divalent concentration of 0.5M was prepared.
  • 5-4 uses manganese sulfate, sulfuric acid, and disodium molybdate as the positive electrode electrolyte, the manganese ion (divalent) concentration is 0.5M, the sulfate ion concentration (total concentration) is 3.5M, and Mo ions (6 An electrolytic solution having a composition having a (valence) concentration of 0.07M was prepared. Sample No. In No. 5-5, an electrolyte solution having a composition in which manganese sulfate and sulfuric acid were used as the positive electrode electrolyte solution and the manganese ion (divalent) concentration was 0.5M and the sulfate ion concentration (total concentration) was 3.5M was prepared.
  • an electrolyte solution having a composition of a negative electrode electrolyte having a titanium ion (tetravalent) concentration of 1.0 M and a sulfate ion concentration (total concentration) of 4.0 M was prepared.
  • 6 ml of electrolyte solution for each electrode was prepared.
  • a small cell having an electrode reaction area of 9 cm 2 was prepared, and a charge / discharge cycle test was performed using the prepared electrolyte.
  • the charging / discharging conditions are a constant current of 630 mA (constant current of 70 mA / cm 2 current density), a charging side switching voltage (voltage to switch from charging to discharging) is 1.8 V, and a discharging side switching voltage (from discharging to charging).
  • the voltage to be switched) was 0 V, and the number of cycles was 3.
  • the discharge capacity (Ah / L) was examined.
  • Table 4 shows the average of the discharge capacity at the second cycle and the discharge capacity at the third cycle.
  • the redox flow battery of the present invention has a large capacity for the purpose of stabilizing fluctuations in power generation output, storing power when surplus generated power, load leveling, etc., for power generation of natural energy such as solar power generation and wind power generation. It can utilize suitably for this storage battery.
  • the redox flow battery of the present invention can be suitably used as a large-capacity storage battery that is provided in a general power plant and is used for the purpose of instantaneous voltage drop / power failure countermeasures and load leveling.

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Abstract

La présente invention concerne une batterie à flux redox capable de supprimer la précipitation de précipités ayant une densité d'énergie élevée. La batterie à flux redox fournit un électrolyte d'électrode positive et un électrolyte d'électrode négative à une cellule de batterie et charge et décharge celle-ci, ladite cellule de batterie comprenant une électrode positive, une électrode négative, et un diaphragme intercalé entre les deux électrodes. L'électrolyte d'électrode positive contient des ions de manganèse, des ions de titane, et des ions métalliques réactifs. L'électrolyte d'électrode négative contient au moins un type d'ion métallique choisi parmi des ions de titane, des ions de chrome, et des ions de zinc. Les ions métalliques réactifs sont au moins un type choisi parmi des ions de vanadium, des ions de chrome, des ions de fer, des ions de cobalt, des ions de cuivre, des ions de molybdène, des ions de ruthénium, des ions de palladium, des ions d'argent, des ions de tungstène, des ions de mercure, et des ions de cérium.
PCT/JP2014/070423 2013-08-07 2014-08-04 Batterie à flux redox WO2015019973A1 (fr)

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CN113767491A (zh) * 2019-02-28 2021-12-07 Ip2Ipo创新有限公司 氧化还原液流电池
CN113270648A (zh) * 2021-05-24 2021-08-17 中国科学技术大学 金属离子诱导的水系锌锰二次电池

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