WO2023026972A1 - 水溶液系二次電池用電極、及び水溶液系二次電池 - Google Patents

水溶液系二次電池用電極、及び水溶液系二次電池 Download PDF

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WO2023026972A1
WO2023026972A1 PCT/JP2022/031338 JP2022031338W WO2023026972A1 WO 2023026972 A1 WO2023026972 A1 WO 2023026972A1 JP 2022031338 W JP2022031338 W JP 2022031338W WO 2023026972 A1 WO2023026972 A1 WO 2023026972A1
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electrode
aqueous
secondary battery
active material
moo
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French (fr)
Japanese (ja)
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創 荒井
篤憲 池澤
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Tokyo Institute of Technology NUC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to electrodes for aqueous solution secondary batteries and aqueous solution secondary batteries.
  • Lithium-ion secondary batteries which are currently the most widely used secondary batteries (storage batteries), have an insertion-desorption type electrode material in the positive electrode and negative electrode that allows lithium ions to enter and exit while maintaining the crystal structure. It is an excellent secondary battery having reversibility and charge/discharge efficiency (see Patent Document 1).
  • lithium-ion secondary batteries consist of a positive electrode with extremely strong oxidizing power and a negative electrode with extremely strong reducing power, and the electrolyte mainly composed of organic solvents is flammable, so there are safety issues. For this reason, it is necessary to provide a protection circuit or the like in order to ensure safety, which increases the cost. Therefore, for large-scale applications such as storage of renewable energy, secondary batteries that emphasize safety rather than the electromotive force or energy density based on the oxidizing power of the positive electrode and the reducing power of the negative electrode are desirable. That is, there is a demand for a safe and inexpensive aqueous secondary battery to replace the lithium ion secondary battery.
  • Base metals such as zinc and hydrogen storage alloys typified by LaNi 5 have been proposed for electrodes for conventional aqueous secondary batteries. is still in its infancy.
  • An object of the present invention is to provide an electrode for an aqueous solution secondary battery and an aqueous solution secondary battery having good proton insertion/extraction characteristics.
  • An aqueous solution secondary battery electrode is an aqueous solution secondary battery electrode capable of intercalating and deintercalating protons, comprising: a current collector; and a mixture layer, wherein the mixture layer contains an active material capable of intercalating and deintercalating protons, and the active material comprises a metal oxide, a metal oxoacid, a metal fluoride, and a metal oxyfluoride. It is at least one selected from the group consisting of
  • the crystal structure of the active material is at least selected from the group consisting of a layered structure, a spinel structure, an inverse spinel structure, an olivine structure, a rutile structure, and an anatase structure. It may be one type.
  • the active material may be at least one selected from the group consisting of molybdenum oxide and tungsten oxide.
  • the active material may be at least one selected from the group consisting of MoO 3 , WO 3 , LiV 3 O 8 and Mn 2 O 4 .
  • the MoO 3 is H x MoO 3 (where x is 0 to 0.0). 53 or less) composition range.
  • the MoO 3 is H x MoO 3 (where x is 1.52 or more 2) composition range.
  • the current collector may be made of a carbon material.
  • An aqueous secondary battery includes a positive electrode, a negative electrode, and an aqueous electrolyte, wherein at least one of the positive electrode and the negative electrode is the aqueous secondary battery electrode described above. Become.
  • the electrolyte is at least one selected from the group consisting of an aqueous sulfuric acid solution, an aqueous nitric acid solution, an aqueous hydrochloric acid solution, an aqueous potassium hydroxide solution, an aqueous potassium nitrate solution, an aqueous potassium sulfate solution, and an aqueous potassium chloride solution. good too.
  • an electrode for an aqueous solution secondary battery and an aqueous solution secondary battery having good proton insertion/extraction characteristics.
  • FIG. 1 is a cross-sectional view showing a configuration example of an electrode for an aqueous solution secondary battery according to an embodiment
  • FIG. 1 is a schematic diagram showing a configuration example of an aqueous secondary battery according to an embodiment
  • FIG. 4 is the result of cyclic voltammogram measurement of the MoO 3 mixture electrode according to Example 1.
  • FIG. 4 is the result of cyclic voltammogram measurement of the MoO 3 mixture electrode according to Example 1.
  • FIG. 4 is a graph showing charge-discharge characteristics of the MoO 3 mixture electrode of Example 1 in red1/ox1.
  • 4 is a graph showing charge-discharge characteristics of the MoO 3 mixture electrode of Example 1 in red1/ox1.
  • FIG. 4 is a graph showing charge-discharge characteristics of the MoO 3 mixture electrode of Example 1 in red3/ox3.
  • 4 is a graph showing charge-discharge characteristics of the MoO 3 mixture electrode of Example 1 in red3/ox3.
  • 4 is a graph showing charge-discharge characteristics of an aqueous secondary battery formed using the MoO 3 mixture electrode according to Example 2.
  • FIG. 4 is a graph showing charge-discharge characteristics of an aqueous secondary battery formed using the MoO 3 mixture electrode according to Example 2.
  • FIG. 10 is a measurement result of a cyclic voltammogram of the WO 3 mixture electrode according to Example 3.
  • FIG. 10 is a graph showing charge-discharge characteristics of a WO3 mixture electrode according to Example 3.
  • FIG. 10 shows the measurement results of cyclic voltammograms of the LiV 3 O 8 mixture electrode according to Example 4.
  • FIG. 10 is a graph showing charge-discharge characteristics of the LiV 3 O 8 mixture electrode according to Example 4.
  • FIG. 10 is a measurement result of a cyclic voltammogram of the Mn 2 O 4 mixture electrode according to Example 5.
  • FIG. 1 is a cross-sectional view showing a configuration example of an electrode for an aqueous secondary battery according to an embodiment.
  • an electrode 1 for an aqueous solution secondary battery (hereinafter also simply referred to as electrode 1) according to the present embodiment includes a current collector 11 and an aggregate formed on the current collector 11. and an agent layer 12 .
  • the electrode 1 according to the present embodiment is an electrode for an aqueous secondary battery capable of intercalating/deintercalating protons.
  • the current collector 11 has a function of holding the mixture layer 12 and supplying and recovering electric charges to and from the mixture layer 12 .
  • the current collector 11 can be configured using a highly conductive metal foil or metal plate.
  • aluminum an alloy containing aluminum as a main component, nickel, titanium, copper, or the like can be used.
  • a carbon material graphite may be used as the current collector 11 .
  • hydrogen embrittlement deterioration of the current collector due to generation of hydrogen, which is a side reaction can be suppressed.
  • the mixture layer 12 is formed on the current collector 11 and contains an active material capable of intercalating and deintercalating protons.
  • the active material can be composed of at least one selected from the group consisting of metal oxides, metal oxoacids, metal fluorides, and metal oxyfluorides.
  • the crystal structure of the active material may be at least one selected from the group consisting of a layered structure, a spinel structure, an inverse spinel structure, an olivine structure, a rutile structure, and an anatase structure.
  • the active material is TiO2 , V2O5 , VO2 , V6O13 , LiV3O8 , Mn2O4 , MoO3 , WO3 , CrO3 , Cr2O5 , CrO 2 , K2MnO4 , BaFeO4 , FeBO3 , FePO4 , LiCoO2 , LiNiO2 , LiCuO2 , Fe2 ( SO4 ) 3 , FeF3 , MnF3 , FeOF, and LiFeSO4F is preferably at least one of
  • the active material is preferably at least one selected from the group consisting of molybdenum oxide and tungsten oxide. Further, in this embodiment, the active material is more preferably at least one selected from the group consisting of MoO 3 , WO 3 , LiV 3 O 8 and Mn 2 O 4 .
  • the active material used for the mixture layer 12 is not limited to the active materials described above, and active materials other than these may be used. Moreover, the active material used for the mixture layer 12 can be appropriately selected according to the polarity of the electrode 1 . Further, the active material used for the material mixture layer 12 can be pulverized using a ball mill or the like to obtain a fine powder having a high surface area, thereby enhancing reactivity.
  • the mixture layer 12 may contain a binder.
  • Carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), or the like may be used as the binder.
  • the ratio of the binder to the active material can be, for example, 1% by mass or more and 20% by mass or less, preferably 3% by mass or more and 10% by mass or less, and more preferably 4% by mass or more and 6% by mass or less.
  • the mixture layer 12 may contain a conductive material.
  • the conductive material is a material that forms an electron conduction path in the mixture layer 12, and for example, carbon black such as acetylene black, graphite, or the like can be used.
  • carbon black such as acetylene black, graphite, or the like
  • hydrogen may be generated due to a side reaction. In this case, it is preferable to configure the mixture layer 12 without adding a conductive material.
  • a method for manufacturing an electrode according to this embodiment will be described.
  • a slurry is formed. Specifically, an active material, a binder, and a solvent (a conductive material may be added as necessary) are mixed and kneaded.
  • solvents examples include 2-propanol, water, N-methyl-2-pyrrolidone (NMP), and the like.
  • NMP N-methyl-2-pyrrolidone
  • the kneaded slurry is applied onto the current collector 11 and dried. After that, by pressing the mixture layer 12 formed on the current collector 11, the electrode 1 according to the present embodiment can be manufactured.
  • FIG. 2 is a schematic diagram showing a configuration example of the aqueous secondary battery according to the present embodiment.
  • the aqueous secondary battery 20 includes a positive electrode 21 , a negative electrode 22 and an electrolyte 23 .
  • a positive electrode 21 , a negative electrode 22 , and an electrolyte 23 are housed in a battery housing 24 .
  • a positive lead-out electrode 26 is attached to the positive electrode 21 .
  • the positive lead-out electrode 26 is arranged so as to be exposed to the outside of the battery housing 24 .
  • a negative lead electrode 27 is attached to the negative electrode 22 .
  • the negative lead-out electrode 27 is arranged so as to be exposed to the outside of the battery housing 24 .
  • the positive lead-out electrode 26 and the negative lead-out electrode 27 are connected to a load 28 via lead wires.
  • protons move between the positive electrode 21 and the negative electrode 22, and protons are intercalated and deintercalated between the positive electrode 21 and the negative electrode 22 to charge and discharge.
  • protons are detached from the positive electrode 21 , the detached protons move from the positive electrode 21 to the negative electrode 22 in the electrolyte 23 , and are inserted into the negative electrode 22 .
  • an electrolyte with high ionic conductivity as the electrolyte 23 .
  • the aqueous solution used for the electrolyte 23 at least one selected from the group consisting of an aqueous sulfuric acid solution, an aqueous nitric acid solution, an aqueous hydrochloric acid solution, an aqueous potassium hydroxide solution, an aqueous potassium nitrate solution, an aqueous potassium sulfate solution, and an aqueous potassium chloride solution can be used.
  • the positive electrode 21 and the negative electrode 22 may be configured using the electrodes according to the present embodiment described above.
  • the electrodes may be formed using different active materials, the electrode having a higher potential relative to the reference electrode may be used as the positive electrode 21 , and the electrode having a lower potential relative to the reference electrode may be used as the negative electrode 22 .
  • the potential with respect to the reference electrode varies depending on the active material used. In this embodiment, it is preferable to select a combination of active materials such that the potential difference between the positive electrode 21 and the negative electrode 22 is large.
  • the positive electrode 21 and the negative electrode 22 may be formed using MoO 3 .
  • the MoO 3 used for the positive electrode 21 operates within the composition range of H x MoO 3 (where x is a value of 0 or more and 0.53 or less).
  • MoO 3 used for the negative electrode 22 operates within a composition range of H x MoO 3 (where x is a value of 1.52 or more and 2 or less).
  • the formal valence of the central metal of the active material of the negative electrode 22 is preferably trivalent to heptavalent on the expensive side. For this reason, it is preferable to use an electrode using a metal oxide as the negative electrode in this embodiment mode.
  • molybdenum oxides (3 to 6 valences of molybdenum) typified by MoO3
  • tungsten oxides (3 to 6 valences of tungsten) typified by WO3
  • permanganese typified by K2MnO4 acid salts (5-7 valences of manganese)
  • perferrates 4-6 valences of iron
  • vanadates 3-5 valences of vanadium typified by LiV3O8 value
  • the mixture layer contains an active material capable of intercalating/deintercalating protons
  • the active material is a metal oxide, a metal oxoacid, a metal fluoride, or a metal oxyfluor. It is configured using at least one selected from the group consisting of olides.
  • Such an active material is a material capable of intercalating and deintercalating protons during charging and discharging, and has good proton intercalation and deintercalation properties. Therefore, according to the present invention, it is possible to provide an electrode for an aqueous solution secondary battery and an aqueous solution secondary battery having good proton insertion/extraction characteristics.
  • the aqueous secondary battery using the electrode according to the present embodiment can ensure safety because the electrolyte is nonflammable, and has a long life, high efficiency, and is inexpensive. It can be suitably used for large-scale secondary batteries that store renewable energy.
  • protons are used as mobile ions to move between the positive electrode and the negative electrode. Therefore, protons can move at high speed in the aqueous electrolyte.
  • protons since protons have a small ionic radius, they can accelerate diffusion within the electrode. Therefore, extremely high output characteristics (rate characteristics) can be realized.
  • Example 1 An electrode containing MoO3 as Example 1 was fabricated.
  • MoO 3 manufactured by Kanto Kagaku Co., Ltd.
  • carbon black manufactured by Denka Co., Ltd.
  • polyvinylidene fluoride manufactured by Kureha Corporation
  • MoO 3 , carbon black, and polyvinylidene fluoride were mixed and dispersed in N-methylpyrrolidone (manufactured by Kanto Kagaku Co., Ltd.) to prepare a slurry.
  • the proportions of MoO 3 , carbon black, and polyvinylidene fluoride at this time were 85 mass % MoO 3 , 10 mass % carbon black, and 5 mass % polyvinylidene fluoride.
  • the prepared slurry was applied to a graphite sheet as a current collector, heated and dried at 80° C. for 12 hours to form a mixture layer, and an electrode according to Example 1 was prepared.
  • Example 1 Samples according to Example 1 were evaluated using the following methods.
  • a three-electrode half cell (test cell) was constructed using the electrode (MoO 3 ) according to Example 1 as a working electrode, and a cyclic voltammogram was measured.
  • a glass container was used as the test cell.
  • An aqueous sulfuric acid solution (manufactured by Nacalai Tesque, Inc.) with a weight concentration of 50% was used as the electrolyte (electrolytic solution).
  • a silver-silver chloride electrode immersed in a potassium chloride saturated solution was used as a reference electrode. All potentials below are with respect to this reference electrode.
  • a Pt mesh was used as the counter electrode.
  • Example 1 a test cell of a type in which the working electrode is fixed to the bottom was used. By using such a test cell, the area of the working electrode can be defined more strictly using the packing. Also, the potential scanning speed of the cyclic voltammogram was set to 10 mV/s.
  • FIG. 3 and 4 are measurement results of cyclic voltammograms of the electrode (MoO 3 ) according to Example 1.
  • FIG. 3 shows the case where the potential is scanned down to ⁇ 0.5V
  • FIG. 4 shows the case where the potential is scanned down to 0.05V.
  • red3/ox3 charge/discharge characteristics of the MoO 3 mixture electrode in red3/ox3
  • an anion exchange membrane manufactured by Tokuyama Corporation
  • red3/ox3 yielded a reversible capacity of 90 mAhg ⁇ 1 for the electrode after charge-discharge conditioning.
  • 98% reversible capacity was exhibited at 100mAg ⁇ 1 (corresponding to 1C).
  • Example 2 An aqueous secondary battery (tetrapolar cell) was produced using the electrode produced in Example 1.
  • a glass container was used for the quadrupole cell (full cell).
  • An aqueous sulfuric acid solution (manufactured by Nacalai Tesque, Inc.) with a weight concentration of 50% was used as the electrolyte (electrolytic solution).
  • a silver-silver chloride electrode immersed in a potassium chloride saturated solution was used as a reference electrode.
  • a Pt mesh (for conditioning) was used as the counter electrode.
  • the MoO3 mixture electrodes prepared in Example 1 were used for the positive and negative electrodes.
  • the electrode holder and the packing are used to sandwich the mixture electrode. This makes it possible to strictly define the exposed area of the mixture electrode.
  • FIG. 9 and 10 are graphs showing charge-discharge characteristics of aqueous secondary batteries formed using MoO 3 mixture electrodes.
  • FIG. 9 shows the cell voltage
  • FIG. 10 shows the potential of each electrode.
  • Example 2 the weight of the active material of the positive electrode and the negative electrode was the same, so the negative electrode can emit protons of up to 90 mAhg ⁇ 1 while the potential is almost constant ( ⁇ 0.26 V), and the positive electrode has a potential of 0. It can accept 63 mAhg ⁇ 1 protons when going from 0.35V to 0.20V.
  • a battery capacity of 63 mAhg ⁇ 1 per positive electrode can be obtained when the cell voltage changes from 0.61 V to 0.46 V. rice field.
  • an average discharge voltage of 0.58 V and a discharge capacity of 66 mAhg ⁇ 1 per positive electrode were obtained.
  • Example 2 the remaining protons can be received by making the weight of the positive electrode a little heavier, so it is thought that the battery capacity can be increased.
  • the rate characteristics of the positive electrode and the negative electrode are relatively uniform, so the rate characteristics of the full cell can be expected.
  • Example 3 As Example 3, an electrode containing WO 3 was produced. First, WO 3 (manufactured by Kanto Kagaku Co., Ltd.) was prepared as an active material, carbon black (manufactured by Denka Co., Ltd.) as a conductive material (conductive auxiliary agent), and polyvinylidene fluoride (manufactured by Kureha Corporation) as a binder. Then, WO 3 , carbon black, and polyvinylidene fluoride were mixed and dispersed in N-methylpyrrolidone (manufactured by Kanto Kagaku Co., Ltd.) to prepare a slurry.
  • N-methylpyrrolidone manufactured by Kanto Kagaku Co., Ltd.
  • the proportions of WO 3 , carbon black, and polyvinylidene fluoride at this time were 85% by mass of WO 3 , 10% by mass of carbon black, and 5% by mass of polyvinylidene fluoride.
  • the prepared slurry was applied to a graphite sheet as a current collector, heated and dried at 80° C. for 12 hours to form a mixture layer, and an electrode according to Example 3 was prepared.
  • Samples according to Example 3 were evaluated using the following methods.
  • a three-electrode half cell (test cell) was constructed using the electrode (WO 3 ) according to Example 3 as a working electrode, and a cyclic voltammogram was measured.
  • a glass container was used as the test cell.
  • An aqueous sulfuric acid solution (manufactured by Nacalai Tesque, Inc.) with a weight concentration of 50% was used as the electrolyte (electrolytic solution).
  • a silver-silver chloride electrode immersed in a potassium chloride saturated solution was used as a reference electrode. All potentials below are with respect to this reference electrode.
  • a Pt mesh was used as the counter electrode.
  • Example 3 a test cell of a type in which the working electrode is fixed to the bottom was used. By using such a test cell, the area of the working electrode can be defined more strictly using the packing. Also, the potential scanning speed of the cyclic voltammogram was set to 10 mV/s.
  • FIG. 11 shows measurement results of cyclic voltammograms of the electrode (WO 3 ) according to Example 3.
  • FIG. 12 is a graph showing charge-discharge characteristics of the electrode (WO 3 ) according to Example 3.
  • FIG. From the results shown in FIGS. 11 and 12, the WO 3 mixture electrode had a reversible capacity of 63 mAhg ⁇ 1 after the charge/discharge conditioning. Also, the WO 3 mixture electrode operated in the composition range of H x WO 3 (x 0-0.55).
  • Example 4 As Example 4, an electrode containing LiV 3 O 8 was produced. First, an equimolar mixture of Li 2 CO 3 and V 2 O 5 was baked in air at 680° C. for 12 hours to synthesize LiV 3 O 8 as an active material. Next, this LiV 3 O 8 is mixed with carbon black (manufactured by Denka Co., Ltd.) as a conductive material (conductive auxiliary agent) and polyvinylidene fluoride (manufactured by Kureha Co., Ltd.) as a binder, and then N-methylpyrrolidone. (manufactured by Kanto Kagaku Co., Ltd.) to prepare a slurry.
  • carbon black manufactured by Denka Co., Ltd.
  • polyvinylidene fluoride manufactured by Kureha Co., Ltd.
  • N-methylpyrrolidone manufactured by Kanto Kagaku Co., Ltd.
  • the proportions of LiV 3 O 8 , carbon black, and polyvinylidene fluoride at this time were 85 mass % LiV 3 O 8 , 10 mass % carbon black, and 5 mass % polyvinylidene fluoride.
  • the produced slurry was applied to a graphite sheet as a current collector, heated and dried at 80° C. for 12 hours to form a mixture layer, and an electrode according to Example 4 was produced.
  • Samples according to Example 4 were evaluated using the following methods.
  • a three-electrode half cell (test cell) was constructed using the electrode (LiV 3 O 8 ) according to Example 4 as a working electrode, and a cyclic voltammogram was measured.
  • a glass container was used as the test cell.
  • An aqueous sulfuric acid solution (manufactured by Nacalai Tesque, Inc.) with a weight concentration of 50% was used as the electrolyte (electrolytic solution).
  • a silver-silver chloride electrode immersed in a potassium chloride saturated solution was used as a reference electrode. All potentials below are with respect to this reference electrode.
  • a Pt mesh was used as the counter electrode.
  • Example 4 a test cell of a type in which the working electrode is fixed to the bottom was used. By using such a test cell, the area of the working electrode can be defined more strictly using the packing. Also, the potential scanning speed of the cyclic voltammogram was set to 10 mV/s.
  • FIG. 13 shows measurement results of cyclic voltammograms of the electrode (LiV 3 O 8 ) according to Example 4.
  • FIG. 14 is a graph showing charge-discharge characteristics of the electrode (LiV 3 O 8 ) according to Example 4.
  • the MoO3 mixture electrode prepared in Example 1 is used as the negative electrode, and the LiV3O8 mixture electrode prepared in Example 4 is used as the positive electrode.
  • an aqueous secondary battery can be formed.
  • Example 5 As Example 5, an electrode containing Mn 2 O 4 was produced. First, LiMn 2 O 4 having a spinel structure was acid-treated to synthesize Mn 2 O 4 as an active material. LiMn 2 O 4 was synthesized by calcining a powder obtained by mixing Li 2 CO 3 and MnO at a molar ratio of 1:4 in air at 800° C. for 8 hours and then in air at 900° C. for 8 hours. Subsequently, Mn 2 O 4 was synthesized by acid-treating LiMn 2 O 4 in a 5 wt % aqueous sulfuric acid solution for 1 hour. This Mn 2 O 4 had a defective spinel structure in which lithium was removed from LiMn 2 O 4 .
  • this Mn 2 O 4 is mixed with carbon black (manufactured by Denka Co., Ltd.) as a conductive material (conductive auxiliary agent) and polyvinylidene fluoride (manufactured by Kureha Co., Ltd.) as a binder, and N-methylpyrrolidone ( manufactured by Kanto Kagaku Co., Ltd.) to prepare a slurry.
  • the proportions of Mn 2 O 4 , carbon black, and polyvinylidene fluoride at this time were 85% by mass for Mn 2 O 4 , 10% by mass for carbon black, and 5% by mass for polyvinylidene fluoride.
  • the prepared slurry is applied to a graphite sheet as a current collector, heated and dried at 80° C. for 12 hours to form a mixture layer, and a cation exchange membrane Nafion (manufactured by Sigma-Aldrich) is further applied to the surface.
  • An electrode according to Example 5 was produced by coating.
  • Samples according to Example 5 were evaluated using the following methods.
  • a three-electrode half cell (test cell) was constructed using the electrode (Mn 2 O 4 ) according to Example 5 as a working electrode, and a cyclic voltammogram was measured.
  • a glass container was used as the test cell.
  • An aqueous sulfuric acid solution (manufactured by Nacalai Tesque, Inc.) with a weight concentration of 50% was used as the electrolyte (electrolytic solution).
  • a silver-silver chloride electrode immersed in a potassium chloride saturated solution was used as a reference electrode. All potentials below are with respect to this reference electrode.
  • a Pt mesh was used as the counter electrode.
  • Example 5 a test cell of a type in which the working electrode was fixed to the bottom was used. By using such a test cell, the area of the working electrode can be defined more strictly using the packing. Also, the potential scanning speed of the cyclic voltammogram was set to 10 mV/s.
  • FIG. 15 shows measurement results of cyclic voltammograms of the electrode (Mn 2 O 4 ) according to Example 5.
  • FIG. 15 From the results shown in FIG. 15, it was confirmed that the Mn 2 O 4 mixture electrode reversibly charges and discharges in a potential range of 0.3 V to 0.4 V higher than that of the LiV 3 O 8 mixture electrode.
  • the MoO3 mixture electrode prepared in Example 1 is used as the negative electrode, and the Mn2O4 mixture electrode prepared in Example 5 is used as the positive electrode.
  • an aqueous secondary battery can be formed.
  • the present invention has been described in accordance with the above embodiments, but the present invention is not limited only to the configurations of the above embodiments, and is applicable within the scope of the invention of the claims of the present application. Needless to say, it includes various modifications, modifications, and combinations that can be made by a trader.

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  • Battery Electrode And Active Subsutance (AREA)
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CN116731700A (zh) * 2023-06-07 2023-09-12 深圳技术大学 一种光致变色凝胶及其制备方法与应用

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JP2011249238A (ja) * 2010-05-28 2011-12-08 National Institute Of Advanced Industrial & Technology プロトンを挿入種とする蓄電デバイス

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JP2011249238A (ja) * 2010-05-28 2011-12-08 National Institute Of Advanced Industrial & Technology プロトンを挿入種とする蓄電デバイス

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GUO HAOCHENG, GOONETILLEKE DAMIAN, SHARMA NEERAJ, REN WENHAO, SU ZHEN, RAWAL ADITYA, ZHAO CHUAN: "Two-Phase Electrochemical Proton Transport and Storage in α-MoO3 for Proton Batteries", CELL REPORTS PHYSICAL SCIENCE, vol. 1, no. 10, 1 October 2020 (2020-10-01), pages 100225, XP093038984, ISSN: 2666-3864, DOI: 10.1016/j.xcrp.2020.100225 *

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