WO2023120446A1 - Matériau actif à base d'anthraquinone - Google Patents

Matériau actif à base d'anthraquinone Download PDF

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Publication number
WO2023120446A1
WO2023120446A1 PCT/JP2022/046564 JP2022046564W WO2023120446A1 WO 2023120446 A1 WO2023120446 A1 WO 2023120446A1 JP 2022046564 W JP2022046564 W JP 2022046564W WO 2023120446 A1 WO2023120446 A1 WO 2023120446A1
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WIPO (PCT)
Prior art keywords
active material
anthraquinone
redox flow
compound
flow battery
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PCT/JP2022/046564
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English (en)
Japanese (ja)
Inventor
航一郎 平山
敏康 木薮
靖 森田
剛志 村田
彩 伊藤
茂満 岡田
Original Assignee
三菱重工業株式会社
学校法人 名古屋電気学園
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Application filed by 三菱重工業株式会社, 学校法人 名古屋電気学園 filed Critical 三菱重工業株式会社
Publication of WO2023120446A1 publication Critical patent/WO2023120446A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
    • 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
    • H01M8/02—Details
    • 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
    • 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 disclosure relates to anthraquinone-class active materials for redox flow batteries.
  • This application claims priority based on Japanese Patent Application No. 2021-208049 filed with the Japan Patent Office on December 22, 2021, the content of which is incorporated herein.
  • the redox flow battery is suitable for storing large amounts of electric power because the amount of electric power stored can be freely designed according to the capacity of the electrolyte tank.
  • a redox flow battery is composed of a cell that charges and discharges and an electrolyte tank that stores electric power, and is characterized in that charging and discharging are performed by circulating the electrolyte with a pump.
  • Patent Document 1 describes a redox flow battery using anthraquinone or naphthoquinone as a negative electrode active material, and exemplifies many anthraquinones having a sulfo group.
  • Patent Document 2 describes a redox flow battery that uses, as an active material, a composition containing a coordination compound in which a redox non-innocent ligand is coordinated to a metal center, although the active material itself is not an active material.
  • Non-Patent Documents 1 and 2 also describe compounds in which various functional groups and elements are bonded to the 1- to 8-positions of anthraquinone.
  • Non-Patent Documents 1 and 2 describe compounds in which various functional groups and elements are bonded to the 1- to 8-positions of anthraquinone.
  • the overvoltage (resistance) of the redox flow battery increases, resulting in a decrease in energy efficiency.
  • At least one embodiment of the present disclosure aims to provide an anthraquinone-class active material capable of reducing the overvoltage of a redox flow battery.
  • the anthraquinone-based active material according to the present disclosure is an anthraquinone-based active material for a redox flow battery containing a compound represented by the following chemical formula, At least one of R 2 , R 3 , R 6 and R 7 is a hydroxyl group or an alkoxy group.
  • FIG. 4 is a graph showing measurement results of overvoltage of a redox flow battery using a compound of each example and each comparative example as an anthraquinone class active material for a negative electrode.
  • the active material of the present disclosure is an active material that dissolves in the electrolytic solution on the negative electrode side of the redox flow battery in a discharged state, and contains a compound represented by the following chemical formula (1).
  • this compound When this compound is used as an active material on the negative electrode side of a redox flow battery, this compound and a reductant in which the oxygen atoms double-bonded at the 9- and 10-positions of the anthraquinone skeleton are converted to hydroxyl groups by oxidation-reduction reaction.
  • At least one of R 2 , R 3 , R 6 and R 7 among R 1 to R 8 respectively bonded to positions 1 to 8 of the anthraquinone skeleton is a hydroxyl group or an alkoxy group (-OR).
  • the R attached to the oxygen atom in the alkoxy group has 1 to 6 carbon atoms, and when it has 4 to 6 carbon atoms, it has a linear or branched structure. Bonds between carbon atoms constituting R are not limited to single bonds, and may include double bonds or triple bonds. Also, R may contain an ether bond.
  • At least one of the carbons constituting R has a halogen or an arbitrary functional group, such as a sulfone group, an amino group, a nitro group, a carboxyl group, a phosphoryl group, a thiol group, an alkyl ester, etc., instead of hydrogen. may be combined.
  • R 2 , R 3 , R 6 , and R 7 may be a hydroxyl group or an alkoxy group, and which functional groups are bound and how many are bound.
  • a compound having a structure in which one of R 2 and R 6 is a hydroxyl group and the other is an alkoxy group may be used as the negative electrode active material of the redox flow battery.
  • the overvoltage of the redox flow battery is extremely small. found to have a tendency. Therefore, by using a compound having such a structure as an active material, the overvoltage of the redox flow battery can be reduced.
  • a compound having a structure in which each of R 2 , R 3 , R 6 and R 7 is either a hydroxyl group or an alkoxy group may be used as a negative electrode active material for a redox flow battery.
  • a compound having a structure in which one of R 2 and R 6 is a hydroxyl group and the other is an alkoxy group is used in a redox flow battery.
  • At least one of R 2 , R 3 , R 6 and R The effect of reducing the overvoltage is observed when compared with a compound that does not have a structure in which one is a hydroxyl group or an alkoxy group. Therefore, by using a compound having such a structure as an active material, the overvoltage of the redox flow battery can be reduced.
  • the alkoxy group bonded to at least one of R 2 , R 3 , R 6 and R 7 may be O(CH 2 ) n COOH (n is a natural number of 1 to 6) having a carboxyl group.
  • n is a natural number of 1 to 6
  • the solubility of the negative electrode in the electrolytic solution can be improved.
  • a hydroxyl group is bonded to the 1-, 4-, 5- or 8-position of the anthraquinone skeleton, the possibility of forming the above-described six-membered ring structure with potassium ions in the electrolyte. Therefore, it is preferable that no hydroxyl groups are bonded to the 1-, 4-, 5- or 8-positions of the anthraquinone skeleton, and functional groups other than hydroxyl groups and alkoxy groups, or hydrogen or halogen atoms are bonded to these positions. preferably.
  • Example 1 (2,6-dihydroxyanthraquinone (2,6-DHAQ)) is available from Tokyo Chemical Industry Co., Ltd. under product code A1894.
  • the compound of Example 2 (2,6-bis(3′-carboxypropyloxy)-9,10-anthraquinone) is available from Tokyo Chemical Industry Co., Ltd. under product code D5764.
  • the compound of Example 3 was synthesized by the procedure represented by the following chemical reaction formula (2).
  • the outline of the synthesis is that from 2,6-DHAQ as a starting material, an intermediate substance having an alkoxy group in which the hydrogen of one hydroxyl group is replaced with ethyl butanoate is synthesized, and from this intermediate substance, the compound of Example 3 is obtained. synthesized.
  • 2,3,6,7-tetrahydroxyanthraquinone which is the compound of Example 4, is obtained by the first step of the following chemical reaction formula (3) and the following chemical reaction formula (4 ) and the third step of the following chemical reaction formula (5).
  • the precipitate was filtered by suction, washed with 160 mL of ethanol and 320 mL of distilled water, and then vacuum-dried at 60° C. for 5 hours to obtain 22.3 g of a white solid (chemical reaction formula (3 ) yield of 75%).
  • Example 5 The compound of Example 5 is synthesized from the first step of chemical reaction formula (6) below and the second step of chemical reaction formula (7) below.
  • a 1 L eggplant flask was charged with 8.13 g (29.9 mmol) of 2,3,6,7-THAQ and 400 mL of DMF. 18.26 g (217 mmol) of potassium ethoxide was added thereto, and the temperature was raised to 65° C. while stirring. After that, 42.1 g (305 mmol) of potassium carbonate and 43.8 mL (306 mmol) of ethyl 4-bromobutanoate were added and stirred at 95° C. for 24 hours.
  • Example 6 was synthesized by the procedure represented by the following chemical reaction formula (8). An outline of this synthesis is as follows. 2,3,6,7-THAQ as starting material gave an intermediate mixture having an alkoxy group in which two hydroxyl hydrogens were replaced by ethyl butanoate, from which the mixture of Example 6 was obtained. be done.
  • the compound of Comparative Example 1 (1,3,5,7-tetrahydroxyanthraquinone (1,3,5,7-THAQ)) was synthesized by the procedure represented by the following chemical reaction formula (9). 3.00 g (19.5 mmol) of 3,5-dihydroxybenzoic acid (available from Tokyo Kasei Kogyo Co., Ltd.) and 39 mL of concentrated sulfuric acid were placed in a 100 mL eggplant flask and stirred at 120° C. for 2 hours. After allowing to cool, the reaction solution was poured into a 300 mL beaker containing 100 g of ice, centrifuged, the supernatant was removed by decantation, and the residue was diluted with 100 mL of distilled water and suction filtered. The filtrate was washed with distilled water and vacuum dried at 75° C. for 2 hours to obtain 2.15 g of the desired product (yield 81%).
  • the compound of Comparative Example 2 is synthesized from the compound of Comparative Example 1 as a starting material through the first step of chemical reaction formula (10) below and the second step of chemical reaction formula (11) below.
  • a 100 mL eggplant flask was charged with 500 mg (1.84 mmol) of 1,3,5,7-THAQ and 25 mL of DMF. 1.23 g (14.6 mmol) of potassium ethoxide was added thereto and stirred for 20 minutes. After that, 2.87 g (20.8 mmol) of potassium carbonate and 2.63 mL (18.3 mmol) of ethyl 4-bromobutanoate were added and stirred at 95° C. for 20 hours.
  • a positive electrode electrolyte was prepared by dissolving 2.53 g (6.00 mmol) of potassium ferrocyanide trihydrate in a 1.0 mol/L potassium hydroxide aqueous solution and diluting the solution to 30 mL.
  • the negative electrode electrolyte is prepared by dissolving the compounds or mixtures of Examples 1 to 6 and Comparative Examples 1 and 2 in the amounts shown in Table 1 in a 1.0 mol / L potassium hydroxide aqueous solution and diluting to 25 mL. prepared.
  • the redox flow battery used for the measurement was manufactured by the inventors of the present disclosure.
  • This redox flow battery has a configuration in which a cell on the positive electrode side and a cell on the negative electrode side are separated by an ion exchange membrane (Nafion (registered trademark), NR-212).
  • Each cell has a meandering flow path of 21 mm ⁇ 21 mm as a flow path through which the electrolytic solution flows.
  • Each cell is provided with a carbon paper porous electrode (20 mm ⁇ 20 mm).
  • a charge/discharge device (ACD-01, Asuka Denshi Co., Ltd.) is electrically connected with a cable to a current collector (a carbon separator manufactured by the inventors of the present disclosure using a conductive carbon resin) provided in each cell,
  • the battery was charged to 50% of the theoretical capacity by constant current constant voltage charging with a current value of 400 mA (current density of 100 mA/cm 2 ), an upper limit voltage of 1.4 V, and a cutoff current density of 2 mA/cm 2 .
  • the battery was charged at a current density of 33 mA/cm 2 , and the voltage obtained 1 minute after the energization was used as the charging voltage.
  • the absolute value of the difference between the open circuit voltage (OCV) at a depth of charge (SOC) of 50% and the charging voltage was defined as the overvoltage during charging.
  • the discharge voltage the voltage after 1 minute from the energization was defined as the discharge voltage
  • the difference from the OCV was defined as the overvoltage during discharge.
  • the average of the overvoltage during charging and the overvoltage during discharging was taken as the overvoltage during charging and discharging.
  • FIG. 1 shows the measurement results of the overvoltage.
  • the compounds of Comparative Examples 1 and 2 in which hydroxyl groups are bonded to the 1- and 5-positions of the anthraquinone skeleton
  • the compounds of Examples 1 to 3 in which either a hydroxyl group or an alkoxy group is bonded to the 2- and 6-positions of the anthraquinone skeleton and the compounds of Examples 4 to 6, in which hydroxyl groups or alkoxy groups were bonded to the 2-, 3-, 6-, and 7-positions of the anthraquinone skeleton, were found to have low overvoltages.
  • the overvoltage of the redox flow battery can be reduced by using a compound in which a hydroxyl group or an alkoxy group is bonded to the 2-, 3-, 6- or 7-position of the anthraquinone skeleton as the negative electrode active material of the redox flow battery. It can be said that Compounds in which either a hydroxyl group or an alkoxy group is bonded to the 2- and 6-positions of the anthraquinone skeleton are preferred over compounds in which either a hydroxyl group or an alkoxy group is bonded to the 2-, 3-, 6-, and 7-positions of the anthraquinone skeleton. It can also be said that the effect is greater.
  • An anthraquinone-based active material comprising a compound represented by the following chemical formula, At least one of R 2 , R 3 , R 6 and R 7 is a hydroxyl group or an alkoxy group.
  • the active material of the present disclosure a hydroxyl group or an alkoxy group is bonded to the 2-, 3-, 6- or 7-position of the anthraquinone skeleton, so that the coordination to the potassium ion is the former
  • the overvoltage of the redox flow battery can be reduced as compared with the case of using the active material with the former structure, since it is considered to be weaker than the coordination with the active material of the former structure.
  • An anthraquinone active material is the anthraquinone active material of [1], One of R2 or R6 is a hydroxyl group and the other is an alkoxy group.
  • An anthraquinone active material is the anthraquinone active material of [1] or [2],
  • Each of R 2 , R 3 , R 6 and R 7 is either a hydroxyl group or an alkoxy group.
  • the compound having the structure [2] when used as the active material of the redox flow battery, the compound having this structure is more effective than the active material of the redox flow battery. Although the effect of lowering overvoltage is slightly inferior, the effect of lowering overvoltage can be seen as compared with the compound that does not have the structure of [1]. Therefore, by using a compound having such a structure as an active material, the overvoltage of the redox flow battery can be reduced.
  • An anthraquinone active material is the anthraquinone active material according to any one of [1] to [3], At least one of the alkoxy groups is O(CH 2 ) n COOH (n is a natural number from 1 to 6).
  • An anthraquinone-based active material is the anthraquinone-based active material according to any one of [1] to [4], R 1 , R 4 , R 5 and R 8 are functional groups other than hydroxyl and alkoxy groups, hydrogen, or halogen.
  • the active material is not strongly coordinated with potassium ions, so the overvoltage of the redox flow battery can be reduced.

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Abstract

Ce matériau actif à base d'anthraquinone pour une batterie redox contient un composé représenté par la formule chimique ci-jointe, au moins un groupe parmi R2, R3, R6 et R7 représentant un groupe hydroxyle ou un groupe alcoxy.
PCT/JP2022/046564 2021-12-22 2022-12-19 Matériau actif à base d'anthraquinone WO2023120446A1 (fr)

Applications Claiming Priority (2)

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JP2021-208049 2021-12-22
JP2021208049A JP2023092820A (ja) 2021-12-22 2021-12-22 アントラキノン類活物質

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WO2023120446A1 true WO2023120446A1 (fr) 2023-06-29

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019516781A (ja) * 2016-04-07 2019-06-20 ツェーエムブルー プロイェクト アーゲー スルホン化芳香族化合物
WO2019157437A1 (fr) * 2018-02-09 2019-08-15 President And Fellows Of Harvard College Quinones ayant une haute capacité de rétention destinées à être utilisées en tant qu'électrolytes dans des batteries à flux redox aqueux

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019516781A (ja) * 2016-04-07 2019-06-20 ツェーエムブルー プロイェクト アーゲー スルホン化芳香族化合物
WO2019157437A1 (fr) * 2018-02-09 2019-08-15 President And Fellows Of Harvard College Quinones ayant une haute capacité de rétention destinées à être utilisées en tant qu'électrolytes dans des batteries à flux redox aqueux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RUAN WENQING, MAO JIATAO, CHEN QING: "Redox flow batteries toward more soluble anthraquinone derivatives", CURRENT OPINION IN ELECTROCHEMISTRY, vol. 29, 1 October 2021 (2021-10-01), pages 100748, XP093073662, ISSN: 2451-9103, DOI: 10.1016/j.coelec.2021.100748 *

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