WO2023012993A1 - プロトン伝導型二次電池用ペースト式電極およびこれを備えるプロトン伝導型二次電池 - Google Patents

プロトン伝導型二次電池用ペースト式電極およびこれを備えるプロトン伝導型二次電池 Download PDF

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WO2023012993A1
WO2023012993A1 PCT/JP2021/029209 JP2021029209W WO2023012993A1 WO 2023012993 A1 WO2023012993 A1 WO 2023012993A1 JP 2021029209 W JP2021029209 W JP 2021029209W WO 2023012993 A1 WO2023012993 A1 WO 2023012993A1
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Prior art keywords
paste
type electrode
proton
active material
negative electrode
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English (en)
French (fr)
Japanese (ja)
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クーシャン ヤン
泰平 大内
浩 福永
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Kawasaki Motors Ltd
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Kawasaki Motors Ltd
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Priority to CN202180101271.4A priority Critical patent/CN117795703A/zh
Priority to JP2023539506A priority patent/JP7751644B2/ja
Priority to PCT/JP2021/029209 priority patent/WO2023012993A1/ja
Priority to US18/294,740 priority patent/US20240347692A1/en
Publication of WO2023012993A1 publication Critical patent/WO2023012993A1/ja
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 a paste-type electrode for a proton-conducting secondary battery and a proton-conducting secondary battery having the same.
  • Alkali metals with small electrochemical equivalents, such as lithium are particularly useful as constituent materials for batteries.
  • lithium By using lithium, it is possible to obtain more energy per unit weight than nickel and cadmium, which have been used in the past.
  • effective charge-discharge cycles have been an important development issue. Repeated charging and discharging gradually creates lithium "dendrites" on the surface of the lithium metal electrode, and these eventually grow to the extent that they touch the positive electrode, causing an internal short circuit in the battery, and after relatively few cycles The battery may become unusable.
  • silicon-based negative electrodes are generally produced by dry compression molding an active material mixture containing a conductive binder.
  • the dry compression molding method it is difficult to adjust the electrode thickness to a specified value.
  • a large amount of processing waste is generated in the manufacturing process, and if it adheres to the electrode surface, it may cause an internal short circuit. Therefore, the dry compression molding method is not suitable for mass production of proton-conducting secondary batteries.
  • the dry compression method cannot be applied when the substrate to which the active material is fixed is a metal foil or when the electrode material contains a combustible material.
  • An object of the present invention is to provide a negative electrode suitable for mass production of proton-conducting secondary batteries and applicable to various forms of proton-conducting secondary batteries, in order to solve the above problems.
  • a paste-type electrode for a proton-conduction secondary battery is a paste-type electrode used as a negative electrode for a proton-conduction secondary battery, comprising: an active material powder containing a Group 14 element as a main component; a binder; a substrate coated with a mixture containing the active material powder and the binder; Prepare.
  • the paste-type electrode manufactured by a wet manufacturing method can easily adjust the thickness of the electrode to a specified value, and the generation of processing waste in the manufacturing process is suppressed, so this paste-type electrode It becomes easy to mass-produce a proton-conducting secondary battery. Further, as will be described in detail later, it was confirmed that even if a negative electrode configured as a paste-type electrode was used, practically satisfactory charge/discharge performance as a proton type secondary battery could be obtained.
  • a proton-conducting secondary battery according to the present invention comprises a negative electrode comprising the paste-type electrode described above, a positive electrode including a positive electrode active material capable of absorbing and releasing hydrogen; a non-aqueous electrolyte interposed between the positive electrode and the negative electrode; Prepare.
  • FIG. 1 is a cross-sectional view schematically showing a test cell for testing characteristics of a negative electrode according to an example of the present invention
  • FIG. 4 is a graph showing charge-discharge cycle test results for a test cell having a negative electrode according to an example of the present invention
  • FIG. 5 is a graph showing charge-discharge cycle test results for a test cell having a negative electrode according to another example of the present invention
  • the electrode used in the proton-conducting secondary battery according to the present embodiment is a paste-type electrode used as the negative electrode of the proton-conducting secondary battery, and comprises an active material powder containing a Group 14 element as a main component and a binder. and a substrate coated with a mixture containing the active material powder and the binder.
  • a paste-type electrode manufactured by a wet manufacturing method makes it easy to adjust the thickness of the electrode to a specified value and suppresses the generation of processing waste in the manufacturing process. This facilitates mass production of secondary batteries. Further, as will be described in detail later, it was confirmed that even if a negative electrode configured as a paste-type electrode was used, practically satisfactory charge/discharge performance as a proton type secondary battery could be obtained.
  • the proton-conducting secondary battery according to the present embodiment includes, in addition to the negative electrode described above, a positive electrode containing a positive electrode active material capable of absorbing and releasing hydrogen, and a non-aqueous electrolyte interposed between the positive electrode and the negative electrode. and This proton-conducting secondary battery further includes a separator interposed between the negative electrode and the positive electrode and permeable to protons.
  • the proton-conducting secondary battery according to the present embodiment includes a positive electrode containing a positive electrode active material capable of absorbing and releasing hydrogen, a negative electrode containing a negative electrode active material capable of absorbing and releasing hydrogen, and the compounds exemplified above. and an electrolytic solution consisting of
  • proton-conducting secondary battery in this specification differs from conventional batteries using metal hydride in many respects, such as not using an aqueous electrolyte.
  • This new type of proton-conducting secondary battery works like conventional batteries by circulating hydrogen between the negative and positive electrodes. This results in the formation of hydrides of one or more elements at the negative electrode during charging. This hydride is a reversible product, producing both protons and electrons as part of the active material of the negative electrode during discharge.
  • negative electrode refers to the electrode on the side containing a substance that electrochemically receives electrons during charging
  • positive electrode refers to the electrode that electrochemically releases electrons during charging. Refers to the pole on the side containing matter.
  • a reaction that occurs at the negative electrode of the proton-conducting secondary battery is represented by the following half-reaction formula. M, which is the negative electrode active material in this formula, will be described later.
  • a reaction occurring at the positive electrode corresponding to the above reaction is represented by the following half-reaction formula.
  • M C in this formula is a metal element in the positive electrode active material M C (OH) 2 .
  • the positive electrode active material is, for example, a transition metal hydroxide.
  • the positive electrode active material may be, for example, a nickel hydroxide or a nickel-containing composite hydroxide containing nickel and other transition metals. More specifically, the positive electrode active material is represented by, for example, Ni (1-xy) CoxZny (OH) 2 (where 0 ⁇ x ⁇ 0.1, 0 ⁇ y ⁇ 0.1). It may be a compound that is
  • the negative electrode active material is a Group 14 element or a compound composed of a plurality of Group 14 elements that can absorb hydrogen electrochemically generated in the electrolyte during charging and can easily release the absorbed hydrogen during discharging. or an alloy.
  • Specific examples of the negative electrode active material include silicon, carbon, silicon carbide (C x Si 1-x ), and silicon germanium alloy (Si x Ge 1-x ).
  • the negative electrode active material preferably contains silicon alone, a compound containing silicon, or a combination thereof, since a high charge/discharge capacity can be obtained.
  • the content of silicon element in the negative electrode active material is not particularly limited, but may be 80% by weight or more, 85% by weight or more, or even 90% by weight or more.
  • the crystal state of the negative electrode active material is not particularly limited, and may be single crystal, polycrystal, nanocrystal (microcrystal), amorphous, or a combination thereof.
  • One or both of the negative electrode active material and the positive electrode active material may be in powder or granular form.
  • the particles can be held together by a binder and layered onto a current collector in the formation of a negative or positive electrode.
  • the binder can be any binder known in the art suitable for use in forming a negative electrode, a positive electrode, or both, and suitable for proton conduction.
  • binders used to form the negative electrode include, but are not limited to, polymeric binder materials.
  • specific examples of the material of the binder include elastomer materials, more specifically, styrene-butadiene (SB), styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer.
  • SB styrene-butadiene
  • SBS styrene-butadiene-styrene block copolymer
  • SEBS styrene-isoprene-styrene block copolymer
  • binder examples include polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), Teflon-modified acetylene black (TAB-2), styrene-butadiene binder material, or carboxymethyl cellulose (CMC). including but not limited to.
  • PTFE polytetrafluoroethylene
  • PVA polyvinyl alcohol
  • TAB-2 Teflon-modified acetylene black
  • CMC carboxymethyl cellulose
  • One or both of the positive electrode and the negative electrode may further contain one or more additives contained in the active material.
  • the additive is, for example, a conductive material.
  • This conductive material is preferably conductive carbon.
  • Examples of conductive carbon include graphitic carbon such as graphite, carbon nanotubes, and graphitized coke.
  • Still other examples of conductive carbons include non-graphitizing carbons that are amorphous or amorphous, such as petroleum coke and carbon black.
  • the conductive material is contained in the positive electrode or negative electrode, for example, in the range of 0.1 wt% to 20 wt%.
  • the negative electrode is a paste type electrode as described above. That is, the active material of the negative electrode is mixed with a binder and optionally a conductive material in an appropriate solvent to form a paste-like mixture (slurry), and the slurry is coated on the current collector (substrate). and drying to evaporate part or all of the solvent to form a layer of active material on the surface of the current collector.
  • the positive electrode can be formed by any method known in the art.
  • the active material of the positive electrode is mixed with a binder and optionally a conductive material in a suitable solvent to form a slurry, the slurry is coated on a current collector and dried.
  • a layer of active material can be formed on the surface of the current collector by evaporating some or all of the solvent.
  • the current collector may be mesh-like, foil-like, or any other suitable form.
  • the current collector can be made of materials such as aluminum-based metals such as aluminum alloys, nickel or nickel alloys, steels such as stainless steel, copper or copper alloys.
  • the current collector may be, for example, sheet-like, and may be foil, solid substrate, porous substrate, grid, foam, or other forms known in the art.
  • the current collector can be any suitable electronically conductive and selectively impermeable or substantially impermeable material, including copper, stainless steel, titanium, or carbon paper/film, non- Perforated metal foil, aluminum foil, clad material containing nickel and aluminum, clad material containing copper and aluminum, nickel plated steel, nickel plated copper, nickel plated aluminum, gold, silver, or any suitable combination thereof good.
  • the non-aqueous electrolyte includes, for example, an ionic liquid.
  • the ionic liquid contained in the electrolytic solution may contain, for example, an aprotic liquid and one or more acids as proton sources added to the aprotic liquid.
  • the aprotic liquid can be any compound that is suitable for composition in the electrolyte and that cannot adversely react with other compounds in the battery. Examples of compounds that make up an aprotic liquid include ammonium or phosphonium compounds, optionally wherein the ammonium or phosphonium is one or more linear, branched or cyclic substituted or non-substituted nitrogen or phosphorus-bonded Contains substituted alkyl groups.
  • Aprotic compounds are e.g. ammonium or phosphonium containing linear, branched or cyclic, substituted or unsubstituted alkyls attached to one or more linear, positively charged nitrogen or phosphorus atoms. It may be a compound. Nitrogen or phosphorus may be members of a 5- or 6-membered ring structure that may have one or more pendant groups extending from the central ring. As a specific example, the ammonium ion may be an imidazolium ion and the phosphonium ion may be a pyrrolidinium ion.
  • Ammonium or phosphonium includes 1 or 2 linear or cyclic, substituted or unsubstituted alkyls having 1 to 6 carbon atoms.
  • the alkyl contains 2-6 carbons.
  • Alkyl substituents may be, for example, nitrogen, oxygen, or sulfur.
  • aprotic compounds for use as electrolytes include 1-butyl-3-methylimidazolium (BMIM), 1-ethyl-3-methylimidazolium (EMIM), 1,3-dimethylimidazolium , 1,2,3-trimethylimidazolium, tris(hydroxyethyl)methylammonium, 1,2,4-trimethylpyrazolium, or combinations thereof.
  • BMIM 1-butyl-3-methylimidazolium
  • EMIM 1-ethyl-3-methylimidazolium
  • 1,3-dimethylimidazolium 1,2,3-trimethylimidazolium
  • tris(hydroxyethyl)methylammonium 1,2,4-trimethylpyrazolium, or combinations thereof.
  • the aprotic compound optionally contains one or more anions in combination with the aprotic compound.
  • anions include methide, nitrate, carboxylate, imide, halide, borate, phosphate, phosphinate, phosphonate, sulfonate, sulfate, carbonate and aluminate, but , but not limited to.
  • anions include carboxylates such as acetates, hydrogen, alkyl, or phosphates such as fluorophosphates, phosphinates such as alkyl phosphinates.
  • aprotic compounds examples include 1-butyl-3-methylimidazolium (BMIM), 1-ethyl-3-methylimidazolium (EMIM), 1,3-dimethylimdiazolium, 1,2 acetate, sulfonate, or borate salts of ,3-trimethylimidazolium, tris(hydroxyethyl)methylammonium, 1,2,4-trimethylpyrazolium, or combinations thereof; not.
  • Specific examples of such compounds include diethylmethylammonium trifluoromethanesulfonate (DEMA/TfO), 1-ethyl-3-methylimidazolium acetate (EMIM/AC), or 1-butyl-3-methylimidazolium.
  • DEMA/TfO diethylmethylammonium trifluoromethanesulfonate
  • EMIM/AC 1-ethyl-3-methylimidazolium acetate
  • EMIM/AC 1-butyl-3-methylimidazol
  • a salt may be added as a pH buffer to the ionic liquid of the electrolytic solution, if necessary.
  • the added salt may be an organic salt or an inorganic salt.
  • organic salts include potassium or sodium citrate, potassium or sodium oxalate
  • inorganic salts include potassium or sodium phosphate, carbonate, or sulfate, which are is not limited to
  • the acid dissociation constant (pKa) in aqueous solutions of these salt additives may range from 1-14. Said pKa value of the salt may be lower than 7, even lower than 3, or even lower than 1.5.
  • the proton-conducting secondary battery may have a separator interposed between the negative electrode and the positive electrode.
  • the separator can be permeable to hydrogen ions so as to acceptably or not unacceptably restrict ion transfer between the negative and positive electrodes.
  • Materials such as nylon, polyester, polyvinyl chloride, glass fiber, and cotton can be used as separators, but are not limited to these.
  • the separator can be polyethylene or polypropylene.
  • the separator may be a proton exchange membrane that selectively allows only protons to pass through.
  • the proton exchange membrane may be a proton-conducting (proton-permeable) polymeric material.
  • proton exchange membranes include, more specifically, perfluorosulfonic acid (PFSA), PFSA-PTFE composite, sulfonated polysulfone, sulfonated hydrocarbon, sulfonated polyetheretherketone (s- PEEK, sulfonated polyether ether-ketone), sulfonated polyimide, sulfonated polyetherimide, sulfonated poly(2,6-dimethyl-1,4-phenylene ether), composite membrane (PFSA-silica), sulfonated polystyrene, sulfone sulfonated phenylenes, sulfonated poly(arylene sulphone), sulfonated poly(arylene ether ketone), poly(
  • the ionic liquid used as the negative electrode, positive electrode, separator, and electrolyte is housed in the exterior body.
  • the outer body may be, for example, a metal or polymeric can, or a laminated film such as a heat-sealable aluminum foil such as an aluminized polypropylene film.
  • the electrochemical cells provided herein may be of any known form, such as button cells, pouch cells, cylindrical cells, prismatic cells, and the like.
  • the current collector and/or substrate may include one or more tabs to allow electron transfer from the current collector to the exterior of the battery and to connect the current collector to a device such as a circuit.
  • the tab can be formed of any suitable electrically conductive material (eg, nickel, aluminum, or other metal) and connected to the current collector, eg, by welding.
  • first example negative electrode silicon powder (manufactured by Japan NER Co., Ltd.) as an active material, carbon nanotubes (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a conductive material, and polyethylene oxide (manufactured by Meisei Chemical Industry Co., Ltd.) as a binder at a ratio of 22:65:13.
  • the size of the negative electrode is 10 mm ⁇ 15 mm (thickness 0.092 mm).
  • the test battery was designed with negative electrode capacity regulation.
  • the manufacturing process of the negative electrode of the first embodiment will be described in detail.
  • Polycrystalline silicon powder was used as silicon, which is an active material.
  • This silicon powder and carbon nanotubes were placed in a beaker and stirred several times.
  • An aqueous polyethylene oxide solution and an appropriate amount of ethanol were added to the mixed powder, and the mixture was stirred at room temperature for 1 hour with a stirrer.
  • a paste-like negative electrode mixture was produced.
  • a nickel foam manufactured by Sumitomo Electric Industries, Ltd.
  • This substrate was impregnated with the paste-like negative electrode mixture, and the protruding paste was scraped off.
  • the electrode in this state was dried in a dryer at 70° C. for 20 minutes.
  • the dried electrode body was compressed at 40 MPa with a hydraulic press to complete the first example negative electrode for the test battery.
  • the thickness of the completed electrodes was 0.15-0.18 mm.
  • EMIM/AC purity >95%) containing 3.33 m of acetic acid was used as the electrolyte.
  • a 210 ⁇ m thick sulfonated polyethylene/polypropylene film manufactured by Nihon Vilene Co., Ltd. was used as the separator.
  • FIG. 1 shows the structure of the test cell C used in this charge/discharge test.
  • This test cell C has a frame 1 made of polypropylene, in which an electrode group consisting of a positive electrode 3, a separator 5, and a negative electrode 7 is placed in a Ni plate 9, a Ni block 11, and a Ni foam (cushion). material) 13 and stored.
  • the frame 1 was covered with a positive electrode terminal plate 15 and a negative electrode terminal plate 17 , which were further covered with an insulating plate 19 made of polypropylene, and fixed with a hexagonal screw 21 and a nut 23 . After injecting the electrolytic solution from the upper screw hole 25, a hexagonal screw 27 was attached to form a sealed test cell C.
  • first test cell the test cell including the negative electrode of the first example will be referred to as "first test cell”.
  • the discharge capacity was 2700 mAh with respect to the charge capacity of 12000 mAh, and the coulombic efficiency was 23%. Rose. As shown by this test result, it was confirmed that the proton absorption-desorption reaction was repeated without problems in the paste-type negative electrode using polycrystalline silicon as an active material.
  • second negative electrode the negative electrode according to Example 2 (hereinafter referred to as "second negative electrode") was prepared with the exception that 1.0 g of amorphous silicon powder (manufactured by Cenate, Norway) was used as the silicon powder as the active material. It was produced in the same procedure as the negative electrode of the first example.
  • a test cell was prepared in the same manner as described above, except that the negative electrode of Example 2 was used as the negative electrode. This test cell is called a "second test cell”.
  • a charge/discharge cycle test was performed on the second test cell under the following charge/discharge conditions.
  • the discharge was performed by multi-stage discharge in which the discharge rate was gradually lowered.
  • the charging/discharging conditions described below are the same as the charging/discharging conditions for the first test cell described above, except for the charging conditions for the first cycle.
  • the discharge capacity was 2120 mAh with respect to the charge capacity of 12000 mAh, and the coulombic efficiency was about 18%. increased to %. As shown by this test result, it was confirmed that the proton absorption-desorption reaction was repeated without any problem even in the paste-type negative electrode using amorphous silicon as an active material.
  • the paste-type electrode manufactured by the wet manufacturing method has practically no problem in charging and discharging performance, and it is easy to adjust the thickness of the electrode to a specified value, and in addition, the processing waste is not generated in the manufacturing process. Since the generation is suppressed, mass production of proton-conducting secondary batteries having this paste-type electrode is facilitated.

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PCT/JP2021/029209 2021-08-05 2021-08-05 プロトン伝導型二次電池用ペースト式電極およびこれを備えるプロトン伝導型二次電池 Ceased WO2023012993A1 (ja)

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CN202180101271.4A CN117795703A (zh) 2021-08-05 2021-08-05 质子传导型二次电池用糊式电极及具备该糊式电极的质子传导型二次电池
JP2023539506A JP7751644B2 (ja) 2021-08-05 2021-08-05 プロトン伝導型二次電池用ペースト式電極およびこれを備えるプロトン伝導型二次電池
PCT/JP2021/029209 WO2023012993A1 (ja) 2021-08-05 2021-08-05 プロトン伝導型二次電池用ペースト式電極およびこれを備えるプロトン伝導型二次電池
US18/294,740 US20240347692A1 (en) 2021-08-05 2021-08-05 Paste-type electrode for proton conductive secondary battery and proton conductive secondary battery provided with same

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Citations (3)

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