WO2012117594A1 - Batterie de stockage électrique - Google Patents

Batterie de stockage électrique Download PDF

Info

Publication number
WO2012117594A1
WO2012117594A1 PCT/JP2011/070367 JP2011070367W WO2012117594A1 WO 2012117594 A1 WO2012117594 A1 WO 2012117594A1 JP 2011070367 W JP2011070367 W JP 2011070367W WO 2012117594 A1 WO2012117594 A1 WO 2012117594A1
Authority
WO
WIPO (PCT)
Prior art keywords
complex
aqueous solution
mol
electrode electrolyte
positive electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/070367
Other languages
English (en)
Japanese (ja)
Inventor
嵐 黄
洋成 出口
昭介 山之内
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissin Electric Co Ltd
Original Assignee
Nissin Electric Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissin Electric Co Ltd filed Critical Nissin Electric Co Ltd
Publication of WO2012117594A1 publication Critical patent/WO2012117594A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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 power storage battery such as a redox flow battery.
  • Patent Document 1 and Non-Patent Document 1 describe a configuration (electromotive force) in which hydrochloric acid (solvent is water) is used as the electrolyte, the positive electrode electrolyte is an aqueous hydrochloric acid solution of iron chloride, and the negative electrode electrolyte is an aqueous hydrochloric acid solution of chromium chloride. Is about 1.0V).
  • Patent Documents 2 and 3 and Non-Patent Document 2 sulfuric acid (solvent is water) is used as the electrolyte, and the positive and negative electrolytes are vanadium sulfate aqueous solutions (electromotive force is about 1.4 V). )
  • Patent Document 4 discloses a configuration in which hydrochloric acid (solvent is water) is used as an electrolyte, a positive electrode electrolyte is a Mn-pyrophosphate aqueous hydrochloric acid solution, and a negative electrode electrolyte is a Cr-phosphoric acid hydrochloric acid aqueous solution (electromotive force is About 1.8V) has been proposed.
  • Non-Patent Documents 3 to 5 propose a configuration in which the negative electrode electrolyte is an aqueous solution of a Cr-EDTA (ethylenediaminetetraacetic acid) complex.
  • the above Cr-EDTA complex can satisfactorily perform a redox reaction under conditions of pH 3-8.
  • the positive electrode electrolyte in each of these structures is strongly acidic, and therefore there are still difficulties in handling and selection of battery container materials.
  • Non-Patent Document 6 sodium acetate (solvent is water) is used as the electrolyte, the negative electrode electrolyte is a sodium acetate aqueous solution of Cr—EDTA complex, and the positive electrode electrolyte is a sodium acetate aqueous solution of Cr—EDTA complex. And a configuration in which the positive electrode electrolyte is a sodium acetate aqueous solution of Fe-EDTA complex (electromotive force is about 1.4 V) are proposed.
  • JP-A-8-78042 (published March 22, 1996) US 6,143,443 (Date of Patent; Nov. 7, 2000) US 6,562,514 B1 (Date of Patent; May 13, 2003) JP 57-9073 (published January 18, 1982)
  • Non-Patent Document 6 allows the redox reaction of the negative electrode side active material Cr-EDTA complex to be carried out satisfactorily on the negative electrode side under the conditions of pH 3-8.
  • Cr compound ions cannot be dissolved in water and self-discharged, so that the charge / discharge cycle characteristics (reversibility) are inferior, and the Coulomb efficiency (50% or less) and It is inferior in energy efficiency and is not suitable as a power storage battery to be used repeatedly.
  • the positive electrode electrolyte is an aqueous sodium acetate solution of Fe-EDTA complex, the ions of the Fe compound cannot be dissolved in water and precipitate on the positive electrode side under the conditions of pH 3-8.
  • transition metals generally used in redox flow type batteries are used.
  • the oxide or hydroxide becomes insoluble in water and precipitates under conditions of pH 3-8.
  • the region in which transition metal ions can be dissolved in water is extremely narrow (the ions can be dissolved in water under strongly acidic conditions, but the ions are water under conditions of pH 3-8. Can not be dissolved in).
  • the present inventor has intensively studied to find a suitable active material on the positive electrode side. That is, the inventors have eagerly searched for a compound containing a metal that can change its valence in an ionic state without causing the oxide or hydroxide to be insoluble in water under the conditions of pH 3-8.
  • Mn is determined from the potential-pH diagram that oxides (MnO 2 and Mn 2 O 3 ) generated by charging and discharging are insoluble in water and precipitate, By doing so, it was found that the valence can be changed in an ionic state without the oxide or hydroxide being insoluble in water under the conditions of pH 3-8.
  • the valence may change in an ionic state without the oxide or hydroxide being insoluble in water under pH 3-8 conditions. I found out that I can do it. Further, by using an aqueous solution containing the chelate (Mn complex or Fe complex having a structure similar to that of the Cr-EDTA complex) as a positive electrode electrolyte, the handling property is excellent, and charge / discharge cycle characteristics (reversibility) As a result, it was confirmed that a power storage battery excellent in various performances such as energy efficiency and coulomb efficiency was obtained, and the present invention was completed.
  • the present inventor diligently studied to find a more suitable active material on the negative electrode side. That is, since the redox reaction can be performed particularly well on the negative electrode side of the Cr-EDTA complex, the Cr complex having a chelate other than EDTA as a ligand within the pH range of 3 to 8 is eagerly searched. The inventors have intensively studied the use of these complexes alone and the combined use with Cr-EDTA complexes. As a result, several Cr complexes (having a chelate other than EDTA as a ligand) were found as inexpensive and suitable active materials.
  • Non-Patent Document 5 describes a Cr (III) complex having cyclohexane-1,2-diaminetetraacetic acid (CyDTA) or diethylenetriaminepentaacetic acid (DTPA) as a ligand, these complexes are It is expensive and not practical.
  • the present invention has been made in view of the above problems, and its main purpose is that the pH of the positive electrode electrolyte and the negative electrode electrolyte is in the range of 3 to 8, which is excellent in handleability and charge / discharge.
  • An object of the present invention is to provide a power storage battery excellent in various performances such as cycle characteristics (reversibility), energy efficiency, and Coulomb efficiency.
  • the power storage battery according to the present invention has an aminopolycarboxylic acid in which the pH of the positive electrode electrolyte and the negative electrode electrolyte is in the range of 3 to 8, and the positive electrode electrolyte is Mn and / or Fe. It is an aqueous solution containing an acid chelate.
  • Mn has a relatively high electromotive force
  • a high-output power storage battery of about 1.85 V can be provided.
  • Fe has a relatively high electromotive force
  • a high-output power storage battery of about 1.3 to 1.4 V can be provided.
  • the Mn and / or Fe aminopolycarboxylic acid chelate used as the active material on the positive electrode side does not produce oxides or hydroxides within a pH range of 3 to 8, and therefore charge / discharge cycle characteristics (reversibility) ) Is excellent, energy efficiency and coulomb efficiency are excellent, and it can withstand the use of thousands of cycles, and therefore has excellent performance as a power storage battery that is used repeatedly.
  • the positive electrode electrolyte is Mn-EDTA complex, Mn-EGTA complex, Mn-HIDA complex, Mn-DTPA complex, Mn-EDTA-OH complex, Fe-EGTA complex, Fe-HIDA complex. More preferably, it is an aqueous solution containing at least one complex selected from the group consisting of a complex, an Fe-DTPA complex, and an Fe-EDTA-OH complex. Further, the positive electrode electrolyte is an Mn-EDTA complex or an Mn-DTPA complex.
  • an aqueous solution containing a plurality of complexes selected from the group consisting of Mn-EDTA-OH complexes, or the positive electrode electrolyte is composed of an Fe-EGTA complex, an Fe-HIDA complex, and an Fe-DTPA complex. More preferably, the aqueous solution contains a plurality of complexes selected from the group consisting of:
  • the total concentration of the Mn complex and the Fe complex in the aqueous solution is more preferably 0.1 mol / L or more and 1.0 mol / L or less.
  • the negative electrode electrolyte is at least selected from the group consisting of a Cr—EDTA complex, a Cr—EGTA complex, a Cr—EDTA—OH complex, a Cr—NTA complex, and a Cr—DTPA complex.
  • An aqueous solution containing one complex is more preferable.
  • the positive electrode electrolyte and the negative electrode electrolyte are more preferably an aqueous solution containing a Mn-EDTA complex and a Cr-EDTA complex.
  • the power storage battery according to the present invention is more preferably a redox flow battery.
  • the concentration of the Mn-EDTA complex in the aqueous solution is set to a relatively high concentration (1.0 mol / L or less). Therefore, the energy density of the power storage battery can be increased.
  • the positive electrode electrolyte and the negative electrode electrolyte are aqueous solutions containing a Mn-EDTA complex and a Cr-EDTA complex (so-called premix method)
  • the capacity of the power storage battery (Various performances) can be kept constant for a longer period of time, so that the maintenance of the power storage battery becomes easier.
  • Cr-EGTA complex, Cr-EDTA-OH complex, Cr-NTA complex, Cr-DTPA complex, and Cr-EDTA complex used as the active material on the negative electrode side are oxidized within the pH range of 3 to 8 on the negative electrode side. No charge or hydroxide is generated, so the charge / discharge cycle characteristics (reversibility) are good, the energy efficiency and coulomb efficiency are excellent, and it can withstand thousands of cycles. As an excellent performance. Furthermore, since the positive electrode electrolyte and the negative electrode electrolyte are not strongly acidic, they are excellent in handleability and increase the degree of freedom in selecting the battery container material.
  • the positive electrode electrolyte and the negative electrode electrolyte are strongly acidic, there are restrictions on the selection of materials that can be used as battery containers (for example, hydrolyzed plastic cannot be used), Since the positive electrode electrolyte and the negative electrode electrolyte are not strongly acidic, general-purpose plastics and relatively inexpensive metals such as Sn, Al, Ti, Cu, Fe, and Ni can be used. Therefore, according to said structure, while being excellent in handleability, the power storage battery excellent in various performances, such as charging / discharging cycling characteristics (reversibility), energy efficiency, and Coulomb efficiency, can be provided comparatively cheaply. .
  • the concentration of the Cr complex in the aqueous solution is more preferably 0.1 mol / L or more and 1.0 mol / L or less.
  • the power storage battery according to the present invention is more preferably a redox flow battery.
  • the power storage battery of the present invention it is possible to provide a power storage battery that is excellent in handleability and excellent in various performances such as charge / discharge cycle characteristics (reversibility), energy efficiency, and coulomb efficiency at a relatively low cost. There is an effect that can be.
  • the power storage battery according to the present invention is easy to mass-produce (industrialize) at a relatively low cost as compared with the conventional power storage battery.
  • the power storage battery according to the present invention has a configuration in which the pH of the positive electrode electrolyte and the negative electrode electrolyte is in the range of 3 to 8, and the positive electrode electrolyte is an aqueous solution containing an aminopolycarboxylic acid chelate of Mn and / or Fe. It is.
  • the pH of the positive electrode electrolyte and the negative electrode electrolyte is in the range of 3 to 8
  • the negative electrode electrolyte is a Cr—EGTA complex, a Cr—EDTA—OH complex, a Cr—NTA complex.
  • an aqueous solution containing at least one complex selected from the group consisting of Cr-DTPA complexes is aqueous solution containing at least one complex selected from the group consisting of Cr-DTPA complexes.
  • Mn aminopolycarboxylic acid chelate refers to a Mn complex (organometallic complex) using aminopolycarboxylic acid as a chelating agent.
  • Fe aminopolycarboxylic acid chelate refers to an Fe complex (organometallic complex) using aminopolycarboxylic acid as a chelating agent.
  • pH 3 to 8 means that the pH is 3 or more and 8 or less.
  • EDTA (sometimes described as “EDTA (4H)”) refers to ethylenediaminetetraacetic acid.
  • EGTA refers to O, O′-bis (2-aminoethyl) ethylene glycol-N, N, N ′, N′-tetraacetic acid.
  • EDTA-OH refers to N- (2-hydroxyethyl) ethylenediamine-N, N ′, N′-triacetic acid.
  • HIDA refers to N- (2-hydroxyethyl) iminodiacetic acid.
  • DTPA refers to diethylenetriaminepentaacetic acid.
  • NTA refers to nitrilotriacetic acid.
  • Mn-EDTA complex refers to a Mn complex having EDTA as a chelating agent as a ligand. The same applies to other ligands, Fe, and Cr.
  • a redox flow battery is taken as an example of the power storage battery.
  • the present invention is not limited to this, and can be implemented in a mode in which various modifications are added within the range described.
  • the redox flow battery 1 mainly includes a charge / discharge cell (battery container) 2, a positive electrode electrolyte tank 3, and a negative electrode electrolyte tank 4.
  • the inside of the charge / discharge cell 2 is partitioned into a positive electrode side cell 2a and a negative electrode side cell 2b by a diaphragm 11 made of, for example, an ion exchange membrane.
  • the charge / discharge cell 2 may be provided with a temperature control device that keeps the temperature constant.
  • the positive electrode side cell 2a accommodates a current collector plate 12 such as a glassy carbon plate and a positive electrode 13 made of, for example, carbon felt.
  • the negative electrode side cell 2b accommodates a current collector plate 14 such as a glassy carbon plate and a negative electrode 15 made of, for example, carbon felt.
  • the positive electrode 13 is impregnated with a positive electrode electrolyte
  • the negative electrode 15 is impregnated with a negative electrode electrolyte. Since the positive electrode electrolyte and the negative electrode electrolyte are not strongly acidic and poor in corrosivity, they are excellent in handleability.
  • the current collecting plates 12 and 14 are electrically connected to the charging / discharging device 10.
  • the positive electrode 13 performs a reduction reaction and receives electrons
  • the negative electrode 15 performs an oxidation reaction and emits electrons.
  • the current collecting plate 12 receives electrons from the charging / discharging device 10 and supplies them to the positive electrode 13, and the current collecting plate 14 collects electrons emitted from the negative electrode 15 and collects them in the charging / discharging device 10. It comes to supply.
  • the positive electrode 13 performs an oxidation reaction and emits electrons
  • the negative electrode 15 performs a reduction reaction and receives electrons.
  • the current collector 12 collects the electrons emitted from the positive electrode 13 and supplies them to the charging / discharging device 10.
  • the current collector 14 receives the electrons from the charging / discharging device 10 and supplies them to the negative electrode 15. It comes to supply.
  • the positive electrode electrolyte tank 3 is a tank for storing the positive electrode electrolyte, and is connected to the positive electrode side cell 2a. That is, the positive electrode electrolyte tank 3 supplies the positive electrode electrolyte to the positive electrode 13 in the positive electrode side cell 2a through the supply pipe 3a, and the positive electrode electrolyte that has passed through the positive electrode 13 passes through the recovery pipe 3b. It comes to collect.
  • the positive electrode electrolyte is circulated by a pump 5 provided in the supply pipe 3a.
  • the supply amount of the positive electrode electrolyte per unit time to the positive electrode side cell 2a at the time of charge / discharge and the capacity of the positive electrode electrolyte tank 3 depend on the size of the charge / discharge cell 2, the capacity required for the redox flow battery 1 and the like. There is no particular limitation.
  • the negative electrode electrolyte tank 4 is a tank for storing the negative electrode electrolyte, and is connected to the negative electrode side cell 2b. That is, the negative electrode electrolyte tank 4 supplies the negative electrode electrolyte to the negative electrode 15 in the negative electrode side cell 2b through the supply pipe 4a, and the negative electrode electrolyte that has passed through the negative electrode 15 passes through the recovery pipe 4b. It comes to collect.
  • the negative electrode electrolyte is circulated by a pump 6 provided in the supply pipe 4a.
  • the supply amount of the negative electrode electrolyte per unit time to the negative electrode side cell 2b during charge / discharge and the capacity of the negative electrode electrolyte tank 4 depend on the size of the charge / discharge cell 2 and the capacity required of the redox flow battery 1 and the like. There is no particular limitation.
  • the electrolyte in the charge / discharge cell 2 can be exchanged. Therefore, in the redox flow battery 1 according to the present embodiment, a long-time (so-called large-capacity battery). ) Charging and discharging are possible.
  • the charge / discharge cell 2, the positive electrode electrolyte tank 3 and the negative electrode electrolyte tank 4 are supplied with an inert gas such as nitrogen gas from a gas supply device (not shown) through an inert gas supply pipe 7. Thereby, the positive electrode electrolyte and the negative electrode electrolyte are shielded from oxygen in the atmosphere.
  • the inert gas supplied from the inert gas supply pipe 7 is exhausted to the outside through the exhaust pipe 8.
  • the front end of the exhaust pipe 8 is sealed with a water-sealed pipe 9 to prevent backflow of the atmosphere and keep the air pressure in the charge / discharge cell 2, the positive electrode electrolyte tank 3 and the negative electrode electrolyte tank 4 constant. ing.
  • the inert gas supply pipe 7 may supply an inert gas to the gas phase portion of the charge / discharge cell 2 and the positive electrode electrolyte tank 3 and the negative electrode electrolyte tank 4. And you may come to supply by bubbling in a negative electrode electrolyte solution.
  • the material of each constituent member constituting the redox flow battery 1 Great freedom of choice. That is, if the positive electrode electrolyte and the negative electrode electrolyte are strongly acidic, there are restrictions on the selection of materials that can be used as battery containers (for example, plastics that are hydrolyzed cannot be used), Since the positive electrode electrolyte and the negative electrode electrolyte are not strongly acidic, specific examples of the material of the charge / discharge cell 2 include, for example, general-purpose plastics and relatively, such as Sn, Al, Ti, Cu, Fe, and Ni. An inexpensive metal can be used.
  • each constituent member constituting the redox flow type battery 1 has an appropriate mechanical strength sufficient to maintain the apparatus, and may be made of a material that is not corroded by the positive electrode electrolyte and the negative electrode electrolyte.
  • the material is not limited to the above exemplified materials.
  • the negative electrode electrolyte has a pH in the range of 3 to 8, more preferably in the range of 4 to 7, and can perform a good redox reaction under the conditions of pH 3 to 8 (charged in the ionic state).
  • the aqueous solution may contain an active material on the negative electrode side (which changes in number).
  • Specific examples of the negative electrode electrolyte include an aqueous solution containing a Cr-EDTA complex, an aqueous solution containing a Cr-EGTA complex, an aqueous solution containing a Cr-EDTA-OH complex, an aqueous solution containing a Cr-NTA complex, and Cr-DTPA.
  • an aqueous solution comprising an aqueous solution comprising at least one selected complex, Cr-EDTA complex, Aqueous solution containing a plurality of complex selected from the group consisting of r-EGTA complex, and Cr-EDTA-OH complex is particularly preferred.
  • the positive electrode electrolyte is an aqueous solution containing a Mn-EDTA complex
  • an aqueous solution containing a Cr-EDTA complex is most preferable.
  • the negative electrode electrolyte When the negative electrode electrolyte is an aqueous solution containing, for example, a Cr-EDTA complex, the complex becomes a Cr (II) -EDTA complex in a charged state, and becomes a Cr (III) -EDTA complex that emits electrons in a discharged state.
  • the negative electrode electrolyte may further contain a known electrolyte such as sodium acetate, a sodium salt of EDTA, or NaCl in addition to the complex.
  • the preparation method of a negative electrode electrolyte solution can employ
  • the water used for the negative electrode electrolyte is sufficient if it has a purity equivalent to or higher than that of distilled water.
  • an aqueous solution containing an aminopolycarboxylic acid chelate of Cr and Fe is used in order to make the formation of the chelate, that is, a complex more completely. More preferably, the mixture is heated to reflux for about 4 to 18 hours. When the reflux operation is not performed, there is a possibility that Cr or the like is deposited or that the power storage battery using the aqueous solution cannot be charged. In addition, what is necessary is just to set reflux time suitably according to the kind of ligand. Further, the reflux operation may be performed in several steps.
  • the positive electrode electrolyte has a pH in the range of 3 to 8, more preferably in the range of 4 to 7, and can perform a good redox reaction under the conditions of pH 3 to 8 (charged in an ionic state).
  • the active material on the positive electrode side (which changes in number), that is, the positive electrode electrolyte may be an aqueous solution containing an aminopolycarboxylic acid chelate of Mn and / or Fe.
  • the positive electrode electrolyte may further contain a known electrolyte such as sodium acetate, a sodium salt of EDTA, NaCl, in addition to the complex.
  • a known electrolyte such as sodium acetate, a sodium salt of EDTA, NaCl
  • the preparation method of positive electrode electrolyte solution can employ
  • the water used for the positive electrode electrolyte is sufficient if it has a purity equivalent to or higher than that of distilled water.
  • aminopolycarboxylic acid constituting the aminopolycarboxylic acid chelate of Mn and / or Fe include, for example, nitrilotriacetic acid ⁇ NTA (Nitrilotriacetic acid); N (CH 2 COOH) 3 ⁇ and salts thereof , Ethylenediaminetetraacetic acid ⁇ EDTA (Ethylene Diamine Tetraacetic acid); (CH 2 COOH) 2 NCH 2 CH 2 N (CH 2 COOH) 2 ⁇ and salts thereof, diethylenetriaminepentaacetic acid ⁇ DTPA (Diethylene Triamine Pentaacetic acid); (CH 2 COOH) 2 NCH 2 CH 2 N (CH 2 COOH) CH 2 CH 2 N (CH 2 COOH) 2 ⁇ and salts thereof, triethylene tetramine hexaacetic acid ⁇ TTHA (triethylene tetraamine Hexaacetic acid) ; (CH 2 COOH) 2 NCH 2 CH 2 N (CH 2 COOH)
  • aminopolycarboxylic acids that serve as ligands
  • EDTA and its salts EGTA and its salts, HIDA and its salts, DTPA and its salts, EDTA-OH and its salts are more preferred.
  • EDTA and its salt, DTPA and its salt, EDTA-OH and its salt are more preferred, and in the case of Fe complex, EGTA and its salt, HIDA and its salt, DTPA and its salt are more preferred.
  • the negative electrode electrolyte is an aqueous solution containing a Cr complex
  • aminopolycarboxylic acids, EDTA and salts thereof are particularly preferable, and ethylenediaminetetraacetic acid / tetrasodium salt (EDTA (4Na)) is most preferable.
  • the Mn aminopolycarboxylic acid chelate is particularly preferably an Mn ethylenediaminetetraacetic acid chelate, that is, a Mn-EDTA complex.
  • the redox flow battery 1 using an aqueous solution containing an Mn complex and / or an Fe complex as a positive electrode electrolyte has an excellent charge / discharge reaction rate.
  • a method for preparing an Mn aminopolycarboxylic acid chelate using an inorganic compound of Mn and an aminopolycarboxylic acid as starting materials is not particularly limited, and a known chelating method can be employed.
  • the Mn complex can be produced by using MnSO 4 as a starting material (raw material) and coordinating aminopolycarboxylic acid as a ligand. That is, the method for preparing Mn aminopolycarboxylic acid chelate is not particularly limited.
  • the aqueous solution containing the Mn aminopolycarboxylic acid chelate may be heated to reflux for several hours, if necessary.
  • the inorganic compound of Mn may be a water-soluble compound (solubility of 0.2 mol / L or more) suitable for chelation.
  • a known chelating method can be employed for preparing an Fe aminopolycarboxylic acid chelate using an Fe inorganic compound and an aminopolycarboxylic acid as starting materials.
  • the positive electrode electrolyte is an aqueous solution containing Mn complex and / or Fe complex
  • the total concentration of Mn complex and Fe complex is 0.1 mol / L or more and 1.0 mol / L or less, preferably Is 0.2 mol / L or more and 1.0 mol / L or less, more preferably 0.4 mol / L or more and 0.8 mol / L or less, and still more preferably about 0.6 mol / L. .
  • the positive electrode electrolyte is an aqueous solution containing, for example, a Mn-EDTA complex
  • the complex becomes a Mn (III) -EDTA complex that has released electrons in a charged state, and becomes a Mn (II) -EDTA complex in a discharged state.
  • the positive electrode electrolyte is an aqueous solution containing a Mn complex, since Mn has a relatively high electromotive force, a high-power redox flow battery of 1.85 V or more can be provided.
  • a redox flow battery having a high output of about 1.3 to 1.4 V can be provided.
  • the positive electrode electrolyte is an aqueous solution containing a Mn-EDTA complex
  • EDTA and its salt are particularly preferable, and ethylenediaminetetraacetic acid / tetrasodium salt (EDTA (4Na)) is most preferable.
  • EDTA (4Na) ethylenediaminetetraacetic acid / tetrasodium salt
  • the redox flow battery 1 using an aqueous solution containing a Cr complex as the negative electrode electrolyte has an excellent charge / discharge reaction rate.
  • a method for preparing a Cr complex using a Cr inorganic compound and a chelate as a starting material is not particularly limited, and a known chelation method can be employed. That is, the method for preparing the Cr complex is not particularly limited.
  • the Cr inorganic compound may be a water-soluble compound (solubility of 0.2 mol / L or more) suitable for chelation.
  • the redox flow battery has higher energy efficiency and better charge / discharge cycle characteristics (reversibility) when the coulomb efficiency is higher.
  • the Coulomb efficiency is preferably 65% or more, and more preferably 80% or more.
  • the energy efficiency is preferably 40% or more, and more preferably 60% or more.
  • the charge / discharge cycle characteristics (reversibility) are preferably 90% or more practically.
  • the voltage efficiency is preferably 60% or more practically, and more preferably 75% or more.
  • the utilization factor of the electrolytic solution is preferably 28% or more, and more preferably 55% or more.
  • the cell resistance is preferably in the range of 2 ⁇ to 4 ⁇ for practical use.
  • the charge yield is preferably in the range of 90% to 100% practically.
  • the discharge yield is preferably 80% or more practically.
  • the redox flow battery 1 uses an aqueous solution containing an aminopolycarboxylic acid chelate of Mn and / or Fe as a positive electrode electrolyte and having a pH in the range of 3 to 8, and / or Since the negative electrode electrolyte has a pH in the range of 3 to 8 and an aqueous solution containing the above exemplified Cr complex is used, the Coulomb efficiency can be made 65% or more, more preferably 80% or more. Further, the energy efficiency can be 40% or more, more preferably 60% or more. Furthermore, the charge / discharge cycle characteristics (reversibility) can be 90% or more. Further, the voltage efficiency can be 60% or more, more preferably 75% or more.
  • the utilization factor of the electrolytic solution can be 28% or more, more preferably 75% or more.
  • the cell resistance can be in the range of 2 ⁇ to 4 ⁇ .
  • the charge yield can be in the range of 90% to 100%.
  • the discharge yield can be 80% or more.
  • the redox flow battery 1 since the redox flow battery 1 according to the present embodiment can withstand the use of several thousand cycles, it can be suitably used as a power storage battery.
  • specific calculation methods for various performances charge / discharge cycle characteristics (reversibility), coulomb efficiency, voltage efficiency, energy efficiency, and electrolyte utilization), and cell resistance, charge yield, and discharge yield A typical calculation method will be described in a later embodiment.
  • the diaphragm 11 which partitions the inside of the charge / discharge cell 2 into the positive electrode side cell 2a and the negative electrode side cell 2b can be separated to some extent so as not to mix the positive electrode electrolyte and the negative electrode electrolyte, Since the performance is not 100%, it is impossible to completely block the passage of the active material (the active material is mixed together). Therefore, when the redox flow battery 1 is used for a long period of time, so-called cross contamination occurs, the positive electrode side active material gradually moves to the negative electrode side, the negative electrode side active material gradually moves to the positive electrode side, A state close to equilibrium will be reached. That is, the composition of the positive electrode electrolyte and the composition of the negative electrode electrolyte are close to each other.
  • the amount (concentration) of the active material on the positive electrode side present on the positive electrode side and the amount (concentration) of the active material on the negative electrode side present on the negative electrode side are reduced, and the capabilities (various performances) of the redox flow battery 1 are reduced. ) May decrease over time.
  • the amount (concentration) of the active material on the positive electrode side existing on the positive electrode side, and on the negative electrode side are present.
  • a method of maintaining the amount (concentration) of the active material on the negative electrode side can also be adopted.
  • the positive electrode electrolyte and the negative electrode electrolyte may be composed of aqueous solutions having different compositions (so-called two-component type), and the above amount ( In order to maintain the (concentration), the two electrolytes may be mixed to form an aqueous solution (so-called premix system) having the same composition. Practically, a premix type electrolyte is more preferable. Since the ability (various performances) of the redox flow battery 1 can be kept constant for a longer period of time by using the premix type electrolytic solution, the maintenance of the redox flow battery 1 becomes easier.
  • the ratio of the active material containing the active material on the positive electrode side to the aqueous solution containing the active material on the negative electrode side in the above equilibrium state What is necessary is just to mix so that it may become.
  • a positive electrode electrolyte and a negative electrode electrolyte are included, for example, a Mn-EDTA complex and a Cr-EDTA complex so that both active materials (Mn, Cr) have a ratio in the above-described equilibrium state. It can be an aqueous solution.
  • the redox flow battery 1 uses an aqueous solution containing an aminopolycarboxylic acid chelate of Mn and / or Fe as a positive electrode electrolyte and having a pH in the range of 3 to 8, and as a negative electrode electrolyte.
  • An aqueous solution having a pH in the range of 3 to 8 is used.
  • an aqueous solution containing, for example, a Cr-EDTA complex is used as the negative electrode electrolyte, or an aqueous solution having the same composition as each other (for example, containing a Mn-EDTA complex and a Cr-EDTA complex).
  • the Mn (III) -EDTA complex is not reduced by the Cr (II) -EDTA complex on the negative electrode side. That is, Mn does not precipitate as a metal (or compound) insoluble in water on the negative electrode side. Therefore, the aqueous solution can be used as a premix type electrolyte.
  • the above-described various Mn complexes, Fe complexes, and Cr complexes can be used in appropriate combination depending on various desired performances.
  • an aqueous solution containing these Mn complexes, Fe complexes, and Cr complexes (including a plurality of complexes) is used as a premix type electrolytic solution
  • an aqueous solution containing one type of complex is used as a premix type electrolytic solution.
  • an aqueous solution was prepared by the following method so as to be a so-called premix system. That is, first, 0.08 mol (40.0 g) of CrK (SO 4 ) 2 ⁇ 12H 2 O was added to 40 ml of distilled water and dissolved. Subsequently, 0.09 mol (26.3 g) of EDTA (4H) and 0.18 mol (7.2 g) of NaOH were added to the aqueous solution little by little and dissolved. The resulting aqueous solution was heated to reflux for 4 hours.
  • a charge / discharge test of a redox flow battery having the configuration shown in FIG. 1 was performed.
  • the redox flow battery used for the charge / discharge test is a small-scale battery for testing.
  • GFA5 manufactured by SGL, which is a kind of carbon felt
  • the electrode area was 10 cm 2 .
  • Nafion 112 made by Daw which is a kind of ion exchange membrane
  • SG carbon thickness 0.6 mm
  • Showa Denko KK which is a kind of glassy carbon plate, was used as the current collector plate.
  • a glass syringe (with the piston removed from the syringe) was used, and the positive electrode side and negative electrode side capacities (electrolytic solution capacities) in the state where the positive electrode, negative electrode, diaphragm, and current collector were loaded.
  • the volume was adjusted to 5 ml.
  • a glass syringe having a capacity of 10 ml (a piston having been omitted from a syringe having a capacity of 10 ml) was used.
  • Silicone tubes were used as various pipes such as a supply pipe, a recovery pipe, an inert gas supply pipe, and an exhaust pipe.
  • a micro tube pump MP-1000 manufactured by Tokyo Science Instrument Co., Ltd. was used as the pump.
  • the charging / discharging battery test system PFX200 by Kikusui Electronics Industry Co., Ltd. was used as a charging / discharging apparatus.
  • the conditions for the charge / discharge test were that both charging and discharging were performed at a constant current of 100 mA, the charge end voltage was set to 2.2V, and the discharge end voltage was set to 0.8V. And charging / discharging was repeated 3 times (3 cycles).
  • nitrogen gas is supplied from an inert gas supply pipe to expel oxygen from the gas phase portion of the charge / discharge cell and the positive and negative electrolyte tanks. Expelled dissolved oxygen inside.
  • the “charge / discharge cycle characteristics (reversibility)” is obtained by calculating the coulomb amount b during discharge in the second cycle charge / discharge and the coulomb amount e during discharge in the third cycle charge / discharge. b) ⁇ 100 ”(%). And the case where the calculated numerical value is 80% or more was evaluated as “ ⁇ ” (repetitive charge / discharge is possible), and the case where it is less than 80% was evaluated as “x” (repetitive charge / discharge is not possible).
  • the “voltage efficiency” is obtained by calculating an average terminal voltage a at the time of charging in the second cycle charge / discharge and an average terminal voltage b at the time of discharging in the second cycle charging / discharging by the equation “(b / a)”. * 100 "(%).
  • the above “utilization rate of the electrolytic solution” is obtained by multiplying the amount (mole number) of the active material of the electrolytic solution supplied to the positive electrode side or the negative electrode side by the Faraday constant (96500 coulomb / mol) to obtain the coulomb amount c.
  • the coulomb amount d at the time of discharge in the charge / discharge of the cycle was obtained and calculated using the formula “(d / c) ⁇ 100” (%). If there is a difference between the amount of the active material of the electrolyte supplied to the positive electrode side and the amount of the active material of the electrolyte supplied to the negative electrode side in the so-called two-component system, the smaller amount is selected. It was decided to adopt and calculate.
  • a negative electrode electrolyte was prepared by the following method. That is, first, 0.08 mol (40.0 g) of CrK (SO 4 ) 2 ⁇ 12H 2 O was added to 30 ml of distilled water and dissolved. Subsequently, 0.09 mol (26.3 g) of EDTA (4H) and 0.18 mol (7.2 g) of NaOH were added to the aqueous solution little by little and dissolved. The resulting aqueous solution was heated to reflux for 4 hours. During the reflux operation, 32 ml of NaOH aqueous solution having a concentration of 5.0 mol / L was added little by little. And after cooling aqueous solution, 0.2 mol (27.2g) sodium acetate trihydrate was added and dissolved.
  • distilled water was added so that the total amount became 200 ml, and then diluted sulfuric acid having a concentration of 2.5 mol / L was added dropwise to adjust the pH to 5.7.
  • an aqueous solution having a Cr-EDTA complex concentration of 0.4 mol / L was prepared and used as a negative electrode electrolyte.
  • a positive electrode electrolyte was prepared by the following method. That is, first, 0.08 mol (13.5 g) of MnSO 4 .H 2 O was added to 140 ml of distilled water and dissolved. Subsequently, 0.08 mol (33.3 g) of EDTA.tetrasodium salt.dihydrate (EDTA (4Na) .2H 2 O) was added to this aqueous solution and dissolved, and then 0.2 mol. (16.4 g) of anhydrous sodium acetate was added and dissolved.
  • distilled water was added so that the total amount became 200 ml, and then the pH was adjusted to 6.6 by dropwise addition of a 1.0 mol / L sodium acetate aqueous solution.
  • an aqueous solution having a concentration of Mn-EDTA complex of 0.4 mol / L was prepared and used as a positive electrode electrolyte.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using the positive electrode electrolyte and the negative electrode electrolyte.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 50 mA, the charge end voltage was set to 2.0V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolytic force is 1.85 V
  • charge / discharge cycle characteristics (reversibility) is “ ⁇ ”
  • Coulomb efficiency is 75%
  • voltage efficiency is 85%
  • energy efficiency is 64%.
  • Ultraviolet efficiency of electrolytic solution was 55%. Therefore, it turned out that it can be used conveniently as a power storage battery.
  • aqueous solutions were prepared by the following method so as to be a so-called one-component type. That is, in the same manner as in Example 2, an aqueous solution having a Cr-EDTA complex concentration of 0.4 mol / L and a pH of 5.7 was prepared. Next, after adding anhydrous sodium acetate and distilled water to the aqueous solution so that the concentration of Cr-EDTA complex is 0.1 mol / L and the concentration of sodium acetate is 1.0 mol / L, the concentration is The pH was adjusted to 5.5 by dropwise addition of 2.5 mol / L dilute sulfuric acid. As a result, a one-part electrolyte solution having a Cr-EDTA complex concentration of 0.1 mol / L was prepared.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using the above electrolytic solution.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 50 mA, the charge end voltage was set to 2.4V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolytic force is 2.05 V
  • charge / discharge cycle characteristics (reversibility) is “ ⁇ ”
  • coulomb efficiency is 50%
  • voltage efficiency is 60%
  • energy efficiency is 30%.
  • the “utilization rate of the electrolytic solution” was 10%, which proved unsuitable as a power storage battery.
  • a positive electrode electrolyte was prepared by the following method. That is, first, 0.08 mol (22.2 g) of FeSO 4 .7H 2 O was added to 120 ml of distilled water and dissolved. Subsequently, 0.08 mol (29.8 g) of EDTA ⁇ disodium salt ⁇ dihydrate (EDTA (2Na) ⁇ 2H 2 O) was added to this aqueous solution and dissolved, and then 0.2 mol (16.4 g) of anhydrous sodium acetate was added and dissolved.
  • 0.08 mol (22.2 g) of FeSO 4 .7H 2 O was added to 120 ml of distilled water and dissolved. Subsequently, 0.08 mol (29.8 g) of EDTA ⁇ disodium salt ⁇ dihydrate (EDTA (2Na) ⁇ 2H 2 O) was added to this aqueous solution and dissolved, and then 0.2 mol (16.4 g) of anhydrous sodium acetate was added and
  • distilled water was added so that the total amount became 200 ml, and then an aqueous solution of sodium acetate having a concentration of 1.0 mol / L was added dropwise to adjust the pH to 4.5.
  • an aqueous solution having a concentration of Fe-EDTA complex of 0.4 mol / L was prepared and used as a positive electrode electrolyte.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using both the above electrolytes.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 50 mA, the charge end voltage was set to 1.6V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolytic force is 1.25 V
  • charge / discharge cycle characteristics (reversibility) is “x”
  • coulomb efficiency is 65%
  • voltage efficiency is 90%
  • energy efficiency is 59%.
  • the “utilization rate of the electrolytic solution” was 25%, which proved unsuitable as a power storage battery.
  • Example 3 In the same manner as in Example 2, an aqueous solution (pH: 5.7) having a Cr-EDTA complex concentration of 0.4 mol / L was prepared. On the other hand, an aqueous solution (pH 4.5) having a concentration of Fe-EDTA complex of 0.4 mol / L was prepared in the same manner as in Comparative Example 2. Then, by mixing the two aqueous solutions at a ratio of 1: 1, a premix type electrolytic solution in which the concentration of the Cr-EDTA complex is 0.2 mol / L and the concentration of the Fe-EDTA complex is 0.2 mol / L. A liquid was prepared.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using the above electrolytic solution. As a result, the battery was charged with a constant current of 50 mA and the charge end voltage could be set to 1.3 V, but could not be discharged. Therefore, it turned out that it is unsuitable as a power storage battery.
  • Example 4 In the same manner as in Example 2, an aqueous solution (pH: 5.7) having a Cr-EDTA complex concentration of 0.4 mol / L was prepared as a negative electrode electrolyte.
  • a positive electrode electrolyte was prepared by the following method. That is, 0.08 mol (22.2 g) of FeSO 4 .7H 2 O was added to 90 ml of distilled water and dissolved, and then 80 ml of diluted sulfuric acid having a concentration of 2.5 mol / L was added. Next, the aqueous solution was diluted with distilled water to prepare an aqueous solution having a FeSO 4 concentration of 0.4 mol / L, which was used as a positive electrode electrolyte.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using both the above electrolytes. As a result, the battery was charged with a constant current of 50 mA and the charge end voltage could be set to 1.3 V, but could not be discharged. Therefore, it turned out that it is unsuitable as a power storage battery.
  • Example 5 In the same manner as in Example 2, an aqueous solution (pH: 5.7) having a Cr-EDTA complex concentration of 0.4 mol / L was prepared as a negative electrode electrolyte.
  • a positive electrode electrolyte was prepared by the following method. That is, 0.2 mol (20.6 g) of NaBr was added and dissolved in 140 ml of distilled water, and then 0.2 mol (16.4 g) of anhydrous sodium acetate was added and dissolved. Then, distilled water was added so that the total amount was 200 ml. As a result, an aqueous solution having a NaBr concentration of 1.0 mol / L was prepared and used as a positive electrode electrolyte.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using both the above electrolytes.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 50 mA, the charge end voltage was set to 2.3V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolytic force is 2.20 V
  • charge / discharge cycle characteristics (reversibility) is “ ⁇ ”
  • Coulomb efficiency is 55%
  • voltage efficiency is 70%
  • energy efficiency is 39%.
  • the “utilization rate of the electrolytic solution” was 15%, which proved unsuitable as a power storage battery.
  • aqueous solution having a Cr-EDTA complex concentration of 0.4 mol / L was prepared as a negative electrode electrolyte.
  • a positive electrode electrolyte was prepared by the following method. That is, 0.2 mol (42.0 g) of tetraethylammonium bromide (N (C 2 H 5 ) 4 + ⁇ Br ⁇ ) was added to 130 ml of distilled water and dissolved, and then 0.2 mol (16. 4 g) anhydrous sodium acetate was added and dissolved. Then, distilled water was added so that the total amount was 200 ml. As a result, an aqueous solution having a tetraethylammonium bromide concentration of 1.0 mol / L was prepared and used as a positive electrode electrolyte.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using both the above electrolytes.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 50 mA, the charge end voltage was set to 2.4V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolytic force is 2.15 V
  • charge / discharge cycle characteristics (reversibility) is “x”
  • coulomb efficiency is 40%
  • voltage efficiency is 80%
  • energy efficiency is 32%.
  • the “utilization rate of the electrolytic solution” was 10%, which proved unsuitable as a power storage battery.
  • Example 7 In the same manner as in Example 1, 140 ml of an aqueous solution (pH: 5.7) having a Cr-EDTA complex concentration of 0.57 mol / L was prepared. Next, the aqueous solution was diluted with distilled water so that the concentration of the Cr—EDTA complex was 0.4 mol / L, and 0.2 mol (20.6 g) of NaBr was added and dissolved. As a result, a one-component electrolyte solution having a Cr-EDTA complex concentration of 0.4 mol / L and a NaBr concentration of 1.0 mol / L was prepared.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using the above electrolytic solution.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 50 mA, the charge end voltage was set to 2.3V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolytic force is 2.20 V
  • charge / discharge cycle characteristics (reversibility) is “ ⁇ ”
  • Coulomb efficiency is 45%
  • voltage efficiency is 90%
  • energy efficiency is 41%.
  • the “utilization rate of the electrolytic solution” was 15%, which proved unsuitable as a power storage battery.
  • Example 3 As the positive electrode electrolyte and the negative electrode electrolyte, an aqueous solution was prepared by the following method so as to be a so-called premix system. That is, first, in the same manner as in Example 1, 140 ml (pH: 5.7) of an aqueous solution having a Cr-EDTA complex concentration of 0.57 mol / L was prepared. Next, 0.1 mol (16.9 g) of MnSO 4 .H 2 O was added to the prepared aqueous solution and dissolved. Subsequently, 0.1 mol (41.6 g) of EDTA.tetrasodium salt.dihydrate (EDTA (4Na) .2H 2 O) was added and dissolved in this aqueous solution.
  • EDTA EDTA.tetrasodium salt.dihydrate
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using the aqueous solution as a premix type electrolyte.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 100 mA, the charge end voltage was set to 2.2V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • Example 4 As the positive electrode electrolyte and the negative electrode electrolyte, an aqueous solution was prepared by the following method so as to be a so-called premix system. That is, first, in the same manner as in Example 1, 105 ml of an aqueous solution (pH: 5.7) having a Cr-EDTA complex concentration of 0.57 mol / L was prepared. Next, 0.2 mol (33.8 g) of MnSO 4 .H 2 O was added to the prepared aqueous solution and dissolved. Subsequently, 0.2 mol (83.2 g) of EDTA.tetrasodium salt.dihydrate (EDTA (4Na) .2H 2 O) was added and dissolved in this aqueous solution.
  • EDTA EDTA.tetrasodium salt.dihydrate
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using the aqueous solution as a premix type electrolyte.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 100 mA, the charge end voltage was set to 2.2V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolytic force is 2.0 V
  • charge / discharge cycle characteristics (reversibility) is “ ⁇ ”
  • Coulomb efficiency is 76%
  • voltage efficiency is 70%
  • energy efficiency is 53%.
  • Ultraviolet intensity of electrolytic solution was 82%. Therefore, it turned out that it can be used conveniently as a power storage battery.
  • Example 5 As the positive electrode electrolyte and the negative electrode electrolyte, an aqueous solution was prepared by the following method so as to be a so-called premix system. That is, in the same manner as in Example 3, an aqueous solution having a Mn-EDTA complex concentration of 0.4 mol / L and a Cr-EDTA complex concentration of 0.32 mol / L was prepared. Thereafter, dilute sulfuric acid having a concentration of 2.5 mol / L was dropped into this aqueous solution to adjust the pH to 3.0, thereby preparing a premix type electrolyte.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using the above electrolytic solution.
  • the charge / discharge test was conducted under the condition that both charging and discharging were performed at a constant current of 100 mA, the charge end voltage was set to 2.4V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolyte As a result, “electromotive force” is 2.0 V, “charge / discharge cycle characteristics (reversibility)” is “ ⁇ ”, “Coulomb efficiency” is 66%, “voltage efficiency” is 64%, and “energy efficiency” is 42%. “Utilization rate of electrolyte” was 29%. Therefore, it turned out that it can be used conveniently as a power storage battery.
  • Example 6 A premix type electrolyte was prepared by performing the same operation as in Example 5 except that the pH was adjusted to 4.5.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using the above electrolytic solution.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 100 mA, the charge end voltage was set to 2.2V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolytic solution As a result, “electromotive force” is 2.0 V, “charge / discharge cycle characteristics (reversibility)” is “ ⁇ ”, “Coulomb efficiency” is 74%, “voltage efficiency” is 70%, and “energy efficiency” is 52%.
  • the “utilization rate of the electrolytic solution” was 39%. Therefore, it turned out that it can be used conveniently as a power storage battery.
  • Example 7 As the positive electrode electrolyte and the negative electrode electrolyte, an aqueous solution was prepared by the following method so as to be a so-called premix system. That is, in the same manner as in Example 3, an aqueous solution having a Mn-EDTA complex concentration of 0.4 mol / L and a Cr-EDTA complex concentration of 0.32 mol / L was prepared. Thereafter, an aqueous NaOH solution having a concentration of 5.0 mol / L was dropped into this aqueous solution to adjust the pH to 6.0, thereby preparing a premix type electrolyte.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using the above electrolytic solution.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 100 mA, the charge end voltage was set to 2.2V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolytic solution As a result, “electromotive force” is 2.0 V, “charge / discharge cycle characteristics (reversibility)” is “ ⁇ ”, “Coulomb efficiency” is 74%, “voltage efficiency” is 74%, and “energy efficiency” is 55%.
  • the “utilization rate of the electrolytic solution” was 60%. Therefore, it turned out that it can be used conveniently as a power storage battery.
  • Example 8 A premix type electrolyte was prepared by performing the same operation as in Example 7 except that the pH was adjusted to 8.0.
  • the charge / discharge test of the redox flow battery used in Example 1 was performed using the above electrolytic solution.
  • the conditions of the charge / discharge test were that charging and discharging were both performed at a constant current of 100 mA, the charge end voltage was set to 2.3V, and the discharge end voltage was set to 0.8V.
  • the other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • electrolytic force is 2.0 V
  • charge / discharge cycle characteristics (reversibility) is “ ⁇ ”
  • Coulomb efficiency is 70%
  • voltage efficiency is 68%
  • energy efficiency is 48%.
  • Ultraviolet intensity of electrolytic solution was 43%. Therefore, it turned out that it can be used conveniently as a power storage battery.
  • ⁇ Positive Electrolyte Solution a, a ′> In 90 ml of distilled water, 0.012 mol (4.56 g) of EGTA and 0.048 mol (1.92 g) of NaOH were added little by little and dissolved. Subsequently, 0.012 mol (3.34 g) of FeSO 4 .7H 2 O was added and dissolved in this aqueous solution, and then 0.24 mol (14.04 g) of NaCl was added and dissolved.
  • distilled water was added so that the total amount became 120 ml, and then diluted sulfuric acid having a concentration of 2.5 mol / L was added dropwise to adjust the pH to 5.7.
  • an aqueous solution having a concentration of Fe-EGTA complex of 0.1 mol / L was prepared and used as a positive electrode electrolyte a.
  • EGTA, NaOH, FeSO 4 .7H 2 O and NaCl were dissolved in distilled water to obtain an aqueous solution, and then the aqueous solution was heated to reflux for 4 hours and cooled. Subsequently, distilled water was added so that the total amount became 120 ml, and then dilute sulfuric acid having a concentration of 2.5 mol / L was added dropwise to adjust the pH to 5.7. As a result, an aqueous solution having a concentration of Fe-EGTA complex of 0.1 mol / L was prepared and used as a positive electrode electrolyte a ′.
  • distilled water was added so that the total amount was 20 ml, and then dilute sulfuric acid having a concentration of 2.5 mol / L was added dropwise to adjust the pH to 5.7.
  • an aqueous solution having a concentration of Fe-HIDA complex of 0.1 mol / L was prepared and used as a positive electrode electrolyte b.
  • ⁇ Cathode electrolyte c> In 90 ml of distilled water, 0.012 mol (4.72 g) of DTPA and 0.06 mol (2.4 g) of NaOH were added little by little and dissolved. Subsequently, 0.012 mol (3.34 g) of FeSO 4 .7H 2 O was added and dissolved in this aqueous solution, and then 0.24 mol (14.04 g) of NaCl was added and dissolved.
  • distilled water was added so that the total amount became 120 ml, and then diluted sulfuric acid having a concentration of 2.5 mol / L was added dropwise to adjust the pH to 5.7.
  • an aqueous solution having a concentration of Fe-DTPA complex of 0.1 mol / L was prepared and used as a positive electrode electrolyte c.
  • ⁇ Cathode electrolyte d> In 90 ml of distilled water, 0.012 mol (4.72 g) of DTPA and 0.06 mol (2.4 g) of NaOH were added little by little and dissolved. Subsequently, 0.012 mol (2.03 g) of MnSO 4 .H 2 O was added and dissolved in this aqueous solution, and then 0.24 mol (14.04 g) of NaCl was added and dissolved.
  • distilled water was added so that the total amount became 120 ml, and then diluted sulfuric acid having a concentration of 2.5 mol / L was added dropwise to adjust the pH to 5.7.
  • an aqueous solution having a concentration of Mn-DTPA complex of 0.1 mol / L was prepared and used as a positive electrode electrolyte d.
  • distilled water was added so that the total amount became 120 ml, and then diluted sulfuric acid having a concentration of 2.5 mol / L was added dropwise to adjust the pH to 5.7.
  • an aqueous solution having a Mn-EDTA-OH complex concentration of 0.1 mol / L was prepared, and used as a positive electrode electrolyte e.
  • distilled water was added so that the total amount became 120 ml, and then diluted sulfuric acid having a concentration of 2.5 mol / L was added dropwise to adjust the pH to 5.7.
  • an aqueous solution having a Mn-EDTA-OH complex concentration of 0.1 mol / L was prepared, and used as a positive electrode electrolyte f.
  • aqueous solution was heated and refluxed for 4 hours to be cooled. Thereafter, dilute sulfuric acid having a concentration of 2.5 mol / L was added dropwise to adjust the pH to 5.7. As a result, an aqueous solution having a concentration of Mn-EDTA complex of 0.1 mol / L was prepared and used as a positive electrode electrolyte g.
  • aqueous solution was heated and refluxed for 4 hours to be cooled. Thereafter, dilute sulfuric acid having a concentration of 2.5 mol / L was added dropwise to adjust the pH to 5.7. As a result, an aqueous solution having a concentration of Mn-EDTA complex of 0.4 mol / L was prepared and used as a positive electrode electrolyte g ′.
  • distilled water is added to the above aqueous solution so that the total amount becomes 560 ml, and 1.12 mol (65.45 g) NaCl is added and dissolved, and then dilute sulfuric acid having a concentration of 2.5 mol / L. Was added dropwise to adjust the pH to 5.7.
  • an aqueous solution having a Cr-EDTA complex concentration of 0.1 mol / L was prepared and used as negative electrode electrolyte C.
  • Example 1 The charging / discharging test of the redox flow type battery used in Example 1 was done using the positive electrode electrolyte and the negative electrode electrolyte in combination.
  • a diaphragm a CMS membrane manufactured by Astom Co., Ltd., which is a kind of ion exchange membrane, was used instead of Nafion 112 manufactured by Daw.
  • the conditions of the charge / discharge test were that both charging and discharging were performed at a constant current of 100 mA (charging current and discharging current), and the final discharge voltage was set to 0.8V. Further, the end-of-charge voltage was set at 1.6 V when the positive electrode electrolyte contained an Fe complex, and at 2.2 V when the positive electrode electrolyte contained an Mn complex. The other conditions in the charge / discharge test were set to be the same as the conditions of the charge / discharge test in Example 1.
  • the charging time refers to the time from the start of charging to the end of charge voltage
  • the discharging time refers to the time from the start of discharging to the end of discharge voltage.
  • F is the Faraday constant (96500 coulombs / mol).
  • Examples 9 to 17 are examples using the negative electrode electrolyte C as the negative electrode electrolyte
  • Examples 17 to 24 are examples using the positive electrode electrolyte g ′ as the positive electrode electrolyte.
  • these redox flow batteries can be suitably used as power storage batteries.
  • the upper horizontal line indicates the value of “Coulomb efficiency” of the redox flow battery in Example 1
  • the lower horizontal line indicates the redox in Example 1.
  • the value of “cell resistance” of the flow type battery is shown. Since the superiority or inferiority of the performance of the redox flow type battery is mainly determined by “Coulomb efficiency” and “cell resistance”, the redox flow type battery in which the value of “Coulomb efficiency” is located above the horizontal line, and The redox flow battery in which the value of “cell resistance” is located below the horizontal line can be determined to be a redox flow battery superior to the redox flow battery in Example 1.
  • the power storage battery of the present invention it is possible to provide a power storage battery that is excellent in handleability and excellent in various performances such as charge / discharge cycle characteristics (reversibility), energy efficiency, and coulomb efficiency at a relatively low cost. There is an effect that can be.
  • the power storage battery according to the present invention can be widely used not only in power companies but also in various industries that require power storage.
  • Redox flow battery power storage battery
  • Charge / discharge cell battery container
  • Positive electrode side cell 2b
  • Negative electrode side cell 3
  • Positive electrode electrolyte tank 4
  • Negative electrode electrolyte tank 10
  • Separator 12 Current collector plate 13
  • Positive electrode 14 Current collector plate 15

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Fuel Cell (AREA)

Abstract

L'invention concerne une batterie à flux redox (1) qui comprend principalement un élément de chargement-déchargement (2), une cuve de solution électrolytique d'électrode positive (3) et une cuve de solution électrolytique d'électrode négative (4). L'intérieur de l'élément de chargement-déchargement (2) est divisé en un élément du côté électrode positive (à savoir, un élément côté électrode positive) (2a) et un élément du côté d'électrode négative (à savoir un élément côté électrode négative) (2b) par un film de séparation (11) comprenant un film d'échange d'ions ou analogue. Dans l'élément côté électrode positive (2a) sont reçues une plaque collectrice de courant (12), telle qu'une plaque de carbone amorphe, et une électrode positive (13) comprenant un feutre à base de carbone ou analogue. Une solution aqueuse contenant un complexe Mn-EDTA et ayant une valeur de pH de 3-8 est introduite dans l'électrode positive (13) en provenance de la cuve de solution électrolytique d'électrode positive (3) par l'intermédiaire d'un conduit de distribution (3a). De cette manière, il devient possible de proposer une batterie à flux redox (1) ayant d'excellentes propriétés de manipulation et d'excellentes propriétés diverses, y compris des propriétés de cycle de chargement-déchargement, de rendement énergétique et de rendement coulombique, à un coût relativement bas.
PCT/JP2011/070367 2011-03-02 2011-09-07 Batterie de stockage électrique Ceased WO2012117594A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
PCT/JP2011/054798 WO2012117543A1 (fr) 2011-03-02 2011-03-02 Accumulateur électrique
JPPCT/JP2011/054798 2011-03-02

Publications (1)

Publication Number Publication Date
WO2012117594A1 true WO2012117594A1 (fr) 2012-09-07

Family

ID=46757503

Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/JP2011/054798 Ceased WO2012117543A1 (fr) 2011-03-02 2011-03-02 Accumulateur électrique
PCT/JP2011/070367 Ceased WO2012117594A1 (fr) 2011-03-02 2011-09-07 Batterie de stockage électrique

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/054798 Ceased WO2012117543A1 (fr) 2011-03-02 2011-03-02 Accumulateur électrique

Country Status (1)

Country Link
WO (2) WO2012117543A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015019973A1 (fr) * 2013-08-07 2015-02-12 住友電気工業株式会社 Batterie à flux redox
JPWO2014102898A1 (ja) * 2012-12-25 2017-01-12 日新電機株式会社 電力貯蔵電池及びその製造方法
CN107134582A (zh) * 2017-06-05 2017-09-05 上海骐杰碳素材料有限公司 一种高活性电极材料及其改性方法
WO2019036633A1 (fr) * 2017-08-17 2019-02-21 The Trustees Of Columbia University In The City Of New York Batteries à flux redox et composés pour application de batterie
WO2020191330A1 (fr) 2019-03-20 2020-09-24 The Regents Of The University Of Colorado, A Body Corporate Dispositifs de stockage électrochimiques comportant des métaux chélatés
CN114243073A (zh) * 2021-12-09 2022-03-25 大连博融新材料有限公司 一种低温下稳定运行和存储的盐酸电解液、其制备方法及应用

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9768463B2 (en) 2012-07-27 2017-09-19 Lockheed Martin Advanced Energy Storage, Llc Aqueous redox flow batteries comprising metal ligand coordination compounds
US9865893B2 (en) 2012-07-27 2018-01-09 Lockheed Martin Advanced Energy Storage, Llc Electrochemical energy storage systems and methods featuring optimal membrane systems
US9559374B2 (en) * 2012-07-27 2017-01-31 Lockheed Martin Advanced Energy Storage, Llc Electrochemical energy storage systems and methods featuring large negative half-cell potentials
US9899694B2 (en) 2012-07-27 2018-02-20 Lockheed Martin Advanced Energy Storage, Llc Electrochemical energy storage systems and methods featuring high open circuit potential
JP6065349B2 (ja) * 2012-12-25 2017-01-25 日新電機株式会社 電力貯蔵電池及びその製造方法
CN105009343B (zh) 2013-03-21 2017-04-26 日新电机株式会社 蓄电池
CN105493329B (zh) * 2013-08-26 2017-03-01 一般社团法人新能源支援机构 电力能量的输送系统
JP6308366B2 (ja) * 2014-07-25 2018-04-11 住友電気工業株式会社 電解液循環型電池
JP2025517802A (ja) * 2022-05-27 2025-06-10 グリーン エナジー ストレージ エッセ．エッレ．エッレ． レドックスフロー電池
CN114899466B (zh) * 2022-06-21 2023-02-21 中山大学 一种锰铁液流电池及其制造方法
CN120709391B (zh) * 2025-08-27 2025-11-11 杭州德海艾科能源科技有限公司 一种尖晶石纳米纤维复合石墨毡电极及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5642970A (en) * 1979-09-14 1981-04-21 Agency Of Ind Science & Technol Redox battery
JPS579073A (en) * 1980-06-17 1982-01-18 Agency Of Ind Science & Technol Bedox battery
JPS579072A (en) * 1980-06-17 1982-01-18 Agency Of Ind Science & Technol Redox battery
JPS611270U (ja) * 1984-06-11 1986-01-07 住友電気工業株式会社 電池
JPS6122574A (ja) * 1984-07-09 1986-01-31 Sumitomo Electric Ind Ltd 電池
JPS6215770A (ja) * 1985-07-11 1987-01-24 Yamaguchi Univ レドックス二次電池
JP2009231230A (ja) * 2008-03-25 2009-10-08 Kurita Water Ind Ltd 微生物発電方法および装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3959234B2 (ja) * 2000-12-26 2007-08-15 日本化学工業株式会社 変性バナジウム化合物、その製造方法、レドックスフロー型電池用電解液組成物及びレドックスフロー型電池用電解液の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5642970A (en) * 1979-09-14 1981-04-21 Agency Of Ind Science & Technol Redox battery
JPS579073A (en) * 1980-06-17 1982-01-18 Agency Of Ind Science & Technol Bedox battery
JPS579072A (en) * 1980-06-17 1982-01-18 Agency Of Ind Science & Technol Redox battery
JPS611270U (ja) * 1984-06-11 1986-01-07 住友電気工業株式会社 電池
JPS6122574A (ja) * 1984-07-09 1986-01-31 Sumitomo Electric Ind Ltd 電池
JPS6215770A (ja) * 1985-07-11 1987-01-24 Yamaguchi Univ レドックス二次電池
JP2009231230A (ja) * 2008-03-25 2009-10-08 Kurita Water Ind Ltd 微生物発電方法および装置

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
C.-H. BAE ET AL.: "Chromium redox couples for application to redox flow batteries", ELECTROCHIMICA ACTA, vol. 48, 2002, pages 279 - 287 *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2014102898A1 (ja) * 2012-12-25 2017-01-12 日新電機株式会社 電力貯蔵電池及びその製造方法
WO2015019973A1 (fr) * 2013-08-07 2015-02-12 住友電気工業株式会社 Batterie à flux redox
CN107134582B (zh) * 2017-06-05 2021-04-06 上海骐杰碳素材料有限公司 一种高活性电极材料及其改性方法
CN107134582A (zh) * 2017-06-05 2017-09-05 上海骐杰碳素材料有限公司 一种高活性电极材料及其改性方法
WO2019036633A1 (fr) * 2017-08-17 2019-02-21 The Trustees Of Columbia University In The City Of New York Batteries à flux redox et composés pour application de batterie
CN111066109A (zh) * 2017-08-17 2020-04-24 纽约市哥伦比亚大学理事会 用于电池应用的氧化还原液流电池和化合物
US11289729B2 (en) 2017-08-17 2022-03-29 The Trustees Of Columbia University In The City Of New York Redox flow batteries and compounds for battery application
WO2020191330A1 (fr) 2019-03-20 2020-09-24 The Regents Of The University Of Colorado, A Body Corporate Dispositifs de stockage électrochimiques comportant des métaux chélatés
CN113853523A (zh) * 2019-03-20 2021-12-28 科罗拉多大学董事会 包括螯合金属的电化学储存装置
EP3942313A4 (fr) * 2019-03-20 2024-05-15 The Regents Of The University Of Colorado Dispositifs de stockage électrochimiques comportant des métaux chélatés
CN113853523B (zh) * 2019-03-20 2024-06-07 科罗拉多大学董事会 包括螯合金属的电化学储存装置
CN114243073A (zh) * 2021-12-09 2022-03-25 大连博融新材料有限公司 一种低温下稳定运行和存储的盐酸电解液、其制备方法及应用
CN114243073B (zh) * 2021-12-09 2023-11-28 大连融科储能集团股份有限公司 一种低温下稳定运行和存储的盐酸电解液、其制备方法及应用

Also Published As

Publication number Publication date
WO2012117543A1 (fr) 2012-09-07

Similar Documents

Publication Publication Date Title
WO2012117543A1 (fr) Accumulateur électrique
US8481192B2 (en) Redox flow battery
CN104995767B (zh) 包含金属配体配位化合物的含水氧化还原液流电池
JP5768933B2 (ja) 電力貯蔵電池
CN101326672B (zh) 具有双功能电解质的电池
US9960445B2 (en) Redox flow battery that uses complexes of cobalt and iron with amino-alcohol ligands in alkaline electrolytes to store electrical energy
CN118016944B (zh) 一种水系铁铈液流电池
JPH0864223A (ja) バナジウム系レドックスフロー型電池の電解液
JP2018537838A (ja) 再生燃料電池
CN102844925A (zh) 电解质组合物
KR20150046075A (ko) 높은 개방 회로 전위를 특징으로 하는 전기화학적 시스템
WO2014001787A1 (fr) Utilisation de batterie d'oxydoréduction pour polyoxométallate
JP6349414B2 (ja) レドックスフロー電池用正極電解質の製造方法およびレドックスフロー電池
JP6621584B2 (ja) レドックスフロー電池用電解液およびレドックスフロー電池
CN113067025A (zh) 一种碱性锌铁液流电池电解液在线恢复方法
CN106030884A (zh) 氧化还原液流电池
WO2013118277A1 (fr) Batterie de stockage d'énergie
JP5874833B2 (ja) 電力貯蔵電池及びその製造方法
CN105009343B (zh) 蓄电池
CN110100343A (zh) 氧化还原液流电池
CN102856573A (zh) 一种锌钒液流储能电池
CN117352799A (zh) 一种锰螯合物的正极电解液及液流电池
JP2020107415A (ja) レドックスフロー電池
JP2016536775A (ja) 化学流動電池の運転方法
CN104716385A (zh) 一种钒锰混合液流电池

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11859953

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11859953

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP