WO2018123487A1 - Matériau actif d'électrode positive pour batterie potassium-ion, électrode positive pour batterie potassium-ion et batterie potassium-ion - Google Patents

Matériau actif d'électrode positive pour batterie potassium-ion, électrode positive pour batterie potassium-ion et batterie potassium-ion Download PDF

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WO2018123487A1
WO2018123487A1 PCT/JP2017/043860 JP2017043860W WO2018123487A1 WO 2018123487 A1 WO2018123487 A1 WO 2018123487A1 JP 2017043860 W JP2017043860 W JP 2017043860W WO 2018123487 A1 WO2018123487 A1 WO 2018123487A1
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positive electrode
potassium
potassium ion
active material
ion battery
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PCT/JP2017/043860
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English (en)
Japanese (ja)
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慎一 駒場
久保田　圭
▲暁▼非 別
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学校法人東京理科大学
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • C01C3/12—Simple or complex iron cyanides
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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 positive electrode active material for a potassium ion battery, a positive electrode for a potassium ion battery, and a potassium ion battery.
  • non-aqueous electrolyte secondary batteries that use a non-aqueous electrolyte as a secondary battery with a high energy density, for example, charge and discharge by moving lithium ions between the positive electrode and the negative electrode are widely used. Yes.
  • a lithium transition metal composite oxide having a layered structure such as lithium nickelate (LiNiO 2 ) or lithium cobaltate (LiCoO 2 ) is generally used as a positive electrode, and lithium is occluded as a negative electrode.
  • carbon materials that can be released, lithium metal, lithium alloys, and the like are used (see, for example, JP-A-2003-151549).
  • a positive electrode of a non-aqueous electrolyte secondary battery those described in JP-T-2015-515081 are known.
  • Lithium ion secondary batteries that can achieve high energy density at a high voltage have been mainly used so far as secondary batteries that can be charged and discharged, but lithium has a relatively limited amount of resources. And expensive. In addition, resources are unevenly distributed in South America, and Japan relies entirely on imports from overseas. Therefore, in order to reduce the cost of the battery and provide a stable supply, a sodium ion secondary battery replacing the lithium ion secondary battery is currently being developed. However, since the atomic weight is larger than that of lithium, the standard electrode potential is about 0.33 V higher than that of lithium, and the cell voltage is lowered, there is a problem that it is difficult to increase the capacity.
  • the electrode active material which comprises a potassium ion secondary battery especially a positive electrode active material must become a supply source of potassium ion, it needs to be a potassium compound which contains potassium as a structural element.
  • a positive electrode active material for a potassium ion secondary battery for example, a material composed of crystal K 0.3 MnO 2 having a layered rock salt structure (Christoph Vaalma, et al., Journal of The Electrochemical Society, 163 (7), A1295-A1299 (2016)) and Prussian blue material crystals (see Ali Eftekhari, Journal of Power Souces, 126, 221-228 (2004)) are known.
  • Problems to be solved by the present invention include a positive electrode active material for a potassium ion battery from which a potassium ion battery having a high energy density is obtained, and a positive electrode for a potassium ion battery containing the positive electrode active material for a potassium ion battery, or the potassium It is providing the potassium ion battery provided with the positive electrode for ion batteries.
  • a positive electrode active material for a potassium ion battery comprising a compound represented by the following formula (1).
  • m represents a number from 0.5 to 2
  • x represents a number from 0.5 to 1.5
  • y represents a number from 0.5 to 1.5
  • z represents 0 or a positive number.
  • a positive electrode for a potassium ion battery comprising the positive electrode active material for a potassium ion battery according to ⁇ 1>.
  • a potassium ion battery comprising the positive electrode for a potassium ion battery according to ⁇ 2>.
  • a positive electrode active material for a potassium ion battery from which a potassium ion battery having a high energy density is obtained, and a positive electrode for a potassium ion battery comprising the positive electrode active material for a potassium ion battery, or the positive electrode for a potassium ion battery can be provided.
  • the positive electrode active material for a potassium ion battery includes a compound represented by the following formula (1).
  • m represents a number from 0.5 to 2
  • x represents a number from 0.5 to 1.5
  • y represents a number from 0.5 to 1.5
  • the positive electrode active material for potassium ion batteries which concerns on this embodiment is used suitably as a positive electrode active material for potassium ion secondary batteries.
  • lithium has a relatively limited amount of resources and is expensive. Also, resources are unevenly distributed in South America. For example, in Japan, the entire amount depends on imports from overseas.
  • potassium is abundant in seawater and the earth's crust, so it becomes a stable resource and can be reduced in cost. Specifically, global lithium production in 2012 is 34,970 t in terms of pure content, and potassium production is 27,146 t in terms of pure content.
  • lithium ion batteries lithium forms an alloy with many metals such as aluminum, so it was necessary to use expensive copper for the negative electrode substrate. Alternatively, inexpensive aluminum can be used for the negative electrode substrate, which is a great cost reduction advantage.
  • the electrode active material which comprises a potassium ion secondary battery especially a positive electrode active material must become a supply source of potassium ion, it needs to be a potassium compound which contains potassium as a structural element.
  • a positive electrode active material for potassium ion batteries are known, but no positive electrode active material for potassium ion batteries has been found that can provide a sufficient output for practical use.
  • the positive electrode active material for a potassium ion battery has an energy density by using a compound represented by the above formula (1), that is, a hexacyano metal acid potassium salt having Fe and Mn as a central metal.
  • a high potassium ion battery is obtained.
  • the positive electrode active material for potassium ion batteries which concerns on this embodiment uses the compound represented by said Formula (1), and in addition to the above, charging / discharging capacity is high, it is high output, and charging / discharging is repeated.
  • a potassium ion battery in which the charge / discharge capacity is hardly deteriorated can be obtained.
  • Fe and Mn are presumed to be divalent or trivalent, and the potassium ion in the compound represented by the formula (1) is increased when the valence is increased. Estimated to be released.
  • the compound represented by the formula (1) is added to the total mass of the positive electrode active material for a potassium ion battery from the viewpoint of output and charge / discharge capacity in the potassium ion battery.
  • the positive electrode active material for a potassium ion battery according to this embodiment may include a compound in which potassium of the compound represented by the formula (1) is replaced with lithium or sodium as an impurity.
  • M in the formula (1) is preferably 1.0 or more and 2.0 or less, more preferably 1.2 or more and 2.0 or less, from the viewpoint of energy density in the potassium ion battery. It is particularly preferably 5 or more and 2.0 or less. Further, from the viewpoint of synthesis, it is preferably 1.2 or more and 2.0 or less, and particularly preferably 1.5 or more and 2.0 or less.
  • X in the formula (1) is preferably 0.7 or more and 1.3 or less, more preferably 0.8 or more and 1.2 or less, from the viewpoint of energy density in the potassium ion battery. It is especially preferable that it is 85 or more and 1.15 or less.
  • Y in the formula (1) is preferably 0.7 or more and 1.3 or less, more preferably 0.8 or more and 1.2 or less, from the viewpoint of energy density in the potassium ion battery. It is especially preferable that it is 85 or more and 1.15 or less.
  • x / y in the formula (1) is preferably 0.5 or more and 1.5 or less, more preferably 0.7 or more and 1.3 or less, from the viewpoint of energy density in the potassium ion battery.
  • the compound represented by the formula (1) preferably has at least one structure selected from the group consisting of a hexacyanoiron structure and a hexacyanomanganese structure.
  • Z in the formula (1) represents the amount of water of hydration, preferably crystallization water, and is not particularly limited as long as it is 0 or a positive number, but is 0 from the viewpoint of energy density and charge / discharge capacity in a potassium ion battery. It is preferably 10 or less, more preferably 0 or more and 5 or less, still more preferably 0 or more and 2 or less, and particularly preferably 0 or more and 1 or less.
  • K 2 FeMn ( CN) 6 ⁇ zH 2 O K 2 Fe 0.5 Mn 1.5 (CN) 6 ⁇ zH 2 O, K 2 Fe 1 .5 Mn 0.5 (CN) 6 ⁇ zH 2 O, K 0.5 FeMn (CN) 6 ⁇ zH 2 O, K 1.0 FeMn (CN) 6 ⁇ zH 2 O, K 1.5 FeMn (CN ) 6 ⁇ zH 2 O, K 1.88 Fe 1.00 Mn 1.08 (CN) 6 ⁇ 0.62H 2 O , and the like.
  • z represents 0 or a positive number, and is preferably 0 or more and 2 or less.
  • the shape of the positive electrode active material for a potassium ion battery according to the present embodiment is not particularly limited, and may be any desired shape, but is a particulate positive electrode active material from the viewpoint of dispersibility during positive electrode formation. It is preferable.
  • the shape of the positive electrode active material for a potassium ion battery according to this embodiment is particulate, the arithmetic average particle size of the positive electrode active material for a potassium ion battery according to this embodiment is from the viewpoint of dispersibility and positive electrode durability.
  • the thickness is preferably 10 nm to 200 ⁇ m, more preferably 50 nm to 100 ⁇ m, still more preferably 75 nm to 75 ⁇ m, and particularly preferably 100 nm to 50 ⁇ m.
  • the method for measuring the arithmetic average particle diameter in the present embodiment is preferably, for example, using HORIBA Laser Scattering Particle Size Distribution Analyzer LA-950 manufactured by Horiba, Ltd., with dispersion medium: water, and laser wavelengths used: 650 nm and 405 nm. Can be measured.
  • the positive electrode active material inside a positive electrode can be measured using a solvent etc. or physically separating.
  • a liquid phase method is mentioned. Specifically, for example, it can be produced by reacting K 4 Fe (CN) 6 (potassium ferrocyanide), MnCl 2 , and KCl in a predetermined amount in an aqueous solution.
  • the positive electrode for potassium ion batteries according to the present embodiment includes the positive electrode active material for potassium ion batteries according to the present embodiment.
  • the positive electrode for a potassium ion battery according to this embodiment may contain a compound other than the positive electrode active material for a potassium ion battery according to this embodiment.
  • the well-known additive used for preparation of the positive electrode of a battery can be used. Specifically, a conductive assistant, a binder, a current collector, and the like can be given.
  • the positive electrode for a potassium ion battery according to the present embodiment preferably includes the positive electrode active material for a potassium ion battery, a conductive additive, and a binder according to the present embodiment from the viewpoint of durability and moldability. .
  • the positive electrode for potassium ion batteries which concerns on this embodiment is 10 masses of compounds represented by said Formula (1) with respect to the total mass of the positive electrode for potassium ion batteries from a viewpoint of the output in a potassium ion battery, and charging / discharging capacity.
  • % Preferably 20% by mass or more, more preferably 50% by mass or more, and particularly preferably 70% by mass or more.
  • the positive electrode active material for a potassium ion battery according to this embodiment may be formed into a desired shape and used as it is as the positive electrode, but the positive electrode rate characteristics (output)
  • the positive electrode for potassium ion batteries which concerns on this embodiment further contains a conductive support agent.
  • Preferred examples of the conductive aid used in the present embodiment include carbons such as carbon blacks, graphites, carbon nanotubes (CNT), and vapor grown carbon fibers (VGCF). Examples of carbon blacks include acetylene black, oil furnace, and ketjen black.
  • conductive support agent chosen from the group which consists of acetylene black and Ketjen black from an electroconductive viewpoint, and it is more preferable that they are acetylene black or Ketjen black.
  • a conductive support agent may be used individually by 1 type, or may use 2 or more types together.
  • the mixing ratio of the positive electrode active material and the conductive auxiliary agent is not particularly limited, but the content of the conductive auxiliary agent in the positive electrode is 1% by mass to 80% by mass with respect to the total mass of the positive electrode active material contained in the positive electrode. It is preferably 2% by mass to 60% by mass, more preferably 5% by mass to 50% by mass, and particularly preferably 5% by mass to 25% by mass. Within the above range, a higher output positive electrode is obtained, and the durability of the positive electrode is excellent.
  • the positive electrode active material can be mixed with the conductive auxiliary agent in an inert gas atmosphere to increase the electric conductivity of the positive electrode.
  • an inert gas nitrogen gas, argon gas, or the like can be used, and argon gas can be preferably used.
  • pulverization and dispersion treatment such as a dry ball mill or a bead mill to which a small amount of a dispersion medium such as water is added may be performed. By performing the pulverization / dispersion treatment, the adhesion and dispersibility between the conductive additive and the positive electrode active material can be increased, and the electrode density can be increased.
  • the positive electrode for potassium ion batteries which concerns on this embodiment further contains a binder from a viewpoint of a moldability.
  • the binder is not particularly limited, and known binders can be used, and examples thereof include polymer compounds such as fluororesins, polyolefin resins, rubber-like polymers, polyamide resins, polyimide resins (polyamideimide, etc.). And cellulose ether are preferred.
  • binders include polyvinylidene fluoride (PVDF), vinylidene fluoride-hexafluoropropylene fluororubber (VDF-HFP fluororubber), vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene fluororubber ( VDF-HFP-TFE fluorine rubber), polyethylene, aromatic polyamide, cellulose, styrene-butadiene rubber, isoprene rubber, butadiene rubber, ethylene-propylene rubber, styrene-butadiene-styrene block copolymer, its hydrogenated product, styrene -Ethylene-butadiene-styrene copolymer, styrene-isoprene-styrene block copolymer, hydrogenated product thereof, syndiotactic-1,2-polybutadiene, ethylene-vinyl acetate cop
  • the specific gravity of the compound used as the binder is preferably greater than 1.2 g / cm 3 .
  • the weight average molecular weight of the binder is preferably 1,000 or more, more preferably 5,000 or more, and 10,000 or more. More preferably. There is no particular upper limit, but it is preferably 2 million or less.
  • a binder may be used individually by 1 type, or may use 2 or more types together.
  • the mixing ratio of the positive electrode active material and the binder is not particularly limited, but the content of the binder in the positive electrode is 0.5% by mass to 30% by mass with respect to the total mass of the positive electrode active material contained in the positive electrode. %, More preferably 1% by mass to 20% by mass, and still more preferably 2% by mass to 15% by mass. It is excellent in a moldability and durability as it is the said range.
  • the method for producing the positive electrode including the positive electrode active material, the conductive auxiliary agent, and the binder is not particularly limited.
  • the positive electrode active material, the conductive auxiliary agent, and the binder are mixed and subjected to pressure molding.
  • the method of preparing the slurry mentioned later and forming a positive electrode may be sufficient.
  • the positive electrode for a potassium ion battery according to this embodiment may further include a current collector.
  • the current collector include a foil, a mesh, an expanded grid (expanded metal), a punched metal, and the like using a conductive material such as nickel, aluminum, and stainless steel (SUS).
  • the mesh opening, wire diameter, number of meshes, etc. are not particularly limited, and conventionally known ones can be used.
  • the shape of the current collector is not particularly limited, and may be selected according to a desired shape of the positive electrode. For example, foil shape, plate shape, etc. are mentioned.
  • the method for forming the positive electrode on the current collector is not particularly limited, but a positive electrode active material slurry is prepared by mixing a positive electrode active material, a conductive additive, a binder, an organic solvent or water, and a current collector.
  • Examples of the method of coating are shown in FIG.
  • Examples of the organic solvent include amines such as N, N-dimethylaminopropylamine and diethyltriamine; ethers such as ethylene oxide and tetrahydrofuran; ketones such as methyl ethyl ketone; esters such as methyl acetate; dimethylacetamide and N-methyl- Examples include aprotic polar solvents such as 2-pyrrolidone.
  • the prepared slurry is applied, for example, on a current collector, dried, pressed, and fixed to produce a positive electrode.
  • Examples of the method of coating the slurry on the current collector include a slit die coating method, a screen coating method, a curtain coating method, a knife coating method, a gravure coating method, and an electrostatic spray method.
  • the potassium ion battery according to the present embodiment includes the positive electrode for a potassium ion battery according to the present embodiment. Moreover, the potassium ion battery which concerns on this embodiment can be used suitably as a potassium ion secondary battery.
  • the potassium ion battery according to the present embodiment preferably includes the positive electrode for potassium ion battery, the negative electrode, and the electrolyte according to the present embodiment.
  • the negative electrode used in the present embodiment only needs to contain a negative electrode active material.
  • a negative electrode active material, a current collector and a negative electrode active material layer formed on the surface of the current collector are used.
  • the negative electrode active material layer includes a negative electrode active material and a binder.
  • the electrical power collector mentioned above in the positive electrode can be used suitably.
  • size of a negative electrode According to the shape and magnitude
  • the negative electrode active material examples include carbon materials such as natural graphite, artificial graphite, coke, hard carbon, carbon black, pyrolytic carbon, carbon fiber, and fired organic polymer compound.
  • the shape of the carbon material may be, for example, a flake shape such as natural graphite, a spherical shape such as mesocarbon microbeads, a fibrous shape such as graphitized carbon fiber, or a particulate aggregate.
  • the carbon material may play a role as a conductive additive.
  • graphite or hard carbon is preferable, and graphite is more preferable.
  • potassium metal can also be used suitably as a negative electrode active material.
  • the negative electrode the negative electrode described in International Publication No. 2016/059907 can also be suitably used.
  • the graphite in the present embodiment refers to a graphite-based carbon material.
  • the graphite-based carbon material include natural graphite, artificial graphite, and expanded graphite.
  • natural graphite for example, scaly graphite, massive graphite and the like can be used.
  • artificial graphite for example, massive graphite, vapor-grown graphite, flaky graphite, fibrous graphite and the like can be used.
  • flaky graphite and lump graphite are preferable for reasons such as high packing density. Two or more types of graphite may be used in combination.
  • the average particle diameter of graphite is preferably 30 ⁇ m, more preferably 15 ⁇ m, further preferably 10 ⁇ m, more preferably 0.5 ⁇ m, more preferably 1 ⁇ m, and even more preferably 2 ⁇ m as the upper limit.
  • the average particle diameter of graphite is a value measured by an electron microscope observation method.
  • the hard carbon in the present embodiment is a carbon material that does not graphitize even when heat-treated at a high temperature of 2,000 ° C. or higher, and is also called non-graphitizable carbon.
  • hard carbon carbon fiber obtained by carbonizing an infusible yarn, which is an intermediate product in the production process of carbon fiber, at about 1,000 ° C to 1,400 ° C, and an organic compound after air oxidation at about 150 ° C to 300 ° C Examples thereof include carbon materials carbonized at about 1,000 ° C. to 1,400 ° C.
  • the method for producing hard carbon is not particularly limited, and hard carbon produced by a conventionally known method can be used. There are no particular restrictions on the average particle size, true density, and (002) plane spacing of the hard carbon, and it can be carried out by selecting preferred ones as appropriate.
  • a negative electrode active material may be used individually by 1 type, or may use 2 or more types together.
  • the content of the negative electrode active material in the negative electrode active material layer is not particularly limited, but is preferably 80 to 95% by mass.
  • both an electrolytic solution and a solid electrolyte can be used.
  • the electrolyte solution is not particularly limited as long as it has a potassium salt as a main electrolyte.
  • the potassium salt include KClO 4 , KPF 6 , KNO 3 , KOH, KCl, K 2 SO 4 , and K 2 S in the case of an aqueous electrolyte. These potassium salts can be used alone or in combination of two or more.
  • an electrolyte for example, KPF 6 , KBF 4 , CF 3 SO 3 K, KAsF 6 , KB (C 6 H 5 ) 4 , CH 3 SO 3 K, KN (SO 2 CF 3 ) 2 , KN (SO 2 C 2 F 5 ) 2 , KC (SO 2 CF 3 ) 3 , KN (SO 3 CF 3 ) 2, etc.
  • an electrolysis containing propylene carbonate PC
  • dissolved in the solvent etc. can be used as electrolyte solution.
  • KPF 6 is preferable.
  • propylene carbonate ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate, vinylene carbonate, fluoroethylene carbonate, 4-trifluoromethyl-1,3-dioxolane-2- ON, carbonates such as 1,2-di (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyldifluoro Ethers such as methyl ether, tetrahydrofuran and 2-methyltetrahydrofuran; Esters such as methyl formate, methyl acetate and ⁇ -butyrolactone; Nitriles such as acetonitrile and butyronitrile Amides such as N, N-dimethylformamide and N, N-di
  • the solvent of the electrolytic solution may be used singly or as a mixture of two or more, but it is preferable to use a mixture of two or more.
  • at least one solvent selected from the group consisting of propylene carbonate, ethylene carbonate and diethyl carbonate is preferable, and at least two mixed solvents selected from the group consisting of propylene carbonate, ethylene carbonate and diethyl carbonate are more preferable.
  • the concentration of the potassium salt in the electrolytic solution is not particularly limited, but is preferably 0.1 mol / L or more and 2 mol / L or less, and more preferably 0.5 mol / L or more and 1.5 mol / L or less. preferable.
  • a known solid electrolyte can be used.
  • an organic solid electrolyte such as a polyethylene oxide polymer compound, a polymer compound containing at least one of a polyorganosiloxane chain or a polyoxyalkylene chain can be used.
  • maintained the nonaqueous electrolyte solution to the high molecular compound can also be used.
  • the potassium ion battery according to this embodiment preferably further includes a separator.
  • a separator plays the role which isolates a positive electrode and a negative electrode physically, and prevents an internal short circuit.
  • the separator is made of a porous material, and the voids are impregnated with an electrolyte, and have ion permeability (particularly at least potassium ion permeability) in order to ensure a battery reaction.
  • a nonwoven fabric other than a resin porous film can be used as the separator.
  • the separator may be formed of only a porous membrane layer or a non-woven fabric layer, or may be formed of a laminate of a plurality of layers having different compositions and forms. Examples of the laminate include a laminate having a plurality of resin porous layers having different compositions, and a laminate having a porous membrane layer and a nonwoven fabric layer.
  • the material of the separator can be selected in consideration of the operating temperature of the battery, the composition of the electrolyte, and the like.
  • the resin contained in the fibers forming the porous film and the nonwoven fabric include polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymer; polyphenylene sulfide resins such as polyphenylene sulfide and polyphenylene sulfide ketone; and aromatic polyamide resins (aramid).
  • polyamide resins such as resins
  • polyimide resins One of these resins may be used alone, or two or more thereof may be used in combination.
  • the fibers forming the nonwoven fabric may be inorganic fibers such as glass fibers.
  • the separator is preferably a separator containing at least one material selected from the group consisting of glass, polyolefin resin, polyamide resin, and polyphenylene sulfide resin. Among these, a glass filter is more preferable as the separator.
  • the separator may include an inorganic filler. Examples of the inorganic filler include ceramics (silica, alumina, zeolite, titania, etc.), talc, mica, wollastonite and the like.
  • the inorganic filler is preferably particulate or fibrous.
  • the content of the inorganic filler in the separator is preferably 10% by mass to 90% by mass, and more preferably 20% by mass to 80% by mass.
  • the shape and size of the separator are not particularly limited, and may be appropriately selected according to a desired battery shape and the like.
  • the potassium ion battery according to the present embodiment various known materials used in conventional lithium ion batteries and sodium ion batteries are used for elements such as battery cases, spacers, gaskets, leaf springs, and other structural materials. There are no particular restrictions. What is necessary is just to assemble the potassium ion battery which concerns on this embodiment according to a well-known method using the said battery element.
  • the shape of the battery is not particularly limited, and various shapes and sizes such as a cylindrical shape, a square shape, and a coin shape can be appropriately employed.
  • FIG. 1 is a schematic diagram illustrating an example of a potassium ion battery 10 according to the present embodiment.
  • a potassium ion battery 10 shown in FIG. 1 is a coin-type battery, and in order from the negative electrode side, a battery case 12 on the negative electrode side, a gasket 14, a negative electrode 16, a separator 18, and a positive electrode (positive electrode) for a potassium ion battery according to this embodiment. 20, the spacer 22, the leaf spring 24, and the battery case 26 on the positive electrode side are stacked, and the battery case 12 and the battery case 26 are fitted together.
  • the separator 18 is impregnated with an electrolytic solution (not shown).
  • solution B was slowly added dropwise at a rate of 40 mL / hour or less while stirring at a speed of 500 rpm (rotation per minute). As soon as it was dropped, a precipitate was formed. After completion of the dropwise addition, the liquid temperature was kept at 60 ° C., and stirring was performed for 4 hours at a speed of 500 rpm while bubbling nitrogen gas. Thereafter, the reaction solution was centrifuged (MX-301 manufactured by Tommy Seiko Co., Ltd., 8,000 rpm to 10,000 rpm) to obtain a mixture of an alkali metal salt of hexacyano acid metal and ACl.
  • the resulting mixture was washed with 1 L of deionized water, and centrifuged (8,000 rpm to 10,000 rpm) several times to obtain a metal potassium hexacyanoate containing a small amount of water.
  • the obtained alkali metal salt of hexacyano acid metal containing a small amount of water was dried at 80 ° C. for 12 hours using a constant temperature dryer to obtain an alkali metal salt of hexacyano acid metal.
  • the alkali metal salt of each hexacyano acid metal obtained above was measured by elemental analysis and X-ray diffraction structure analysis, respectively, and the chemical structure was specified.
  • Each of the obtained alkali metal salts of hexacyano acid metal was used to prepare positive electrodes.
  • the shape of the positive electrode not including the aluminum foil was a cylindrical shape having a diameter of 10 mm and a thickness of 0.03 mm to 0.04 mm.
  • the mass of the positive electrode not containing the aluminum foil was 3 mg to 5 mg.
  • the amount of the electrolyte used was an amount sufficient to fill the separator with the electrolyte (0.15 mL to 0.3 mL).
  • the electrolytic solution was prepared using KPF 6 manufactured by Tokyo Chemical Industry Co., Ltd., ethylene carbonate manufactured by Kishida Chemical Co., and diethyl carbonate manufactured by Kishida Chemical Co., Ltd.
  • the charge / discharge conditions were measured at room temperature (25 ° C.) with the charge / discharge current density set to the constant current mode. Using the obtained positive electrode, the current density was set to 30 mA / g, and the charge voltage was constant current charged to 4.5V. After charging, constant current discharge was repeated until the charge voltage was 4.5V and the end-of-discharge voltage was 2.0V.
  • the charge / discharge conditions were measured at room temperature (25 ° C.) with the charge / discharge current density set to the constant current mode. Using the obtained positive electrode, the current density was set to 30 mA / g, and constant current charging was performed up to a charging voltage of 4.0V. After charging, constant current discharging was repeated until the charging voltage was 4.0 V and the final discharge voltage was 2.0 V.
  • the charge / discharge conditions were measured at room temperature (25 ° C.) with the charge / discharge current density set to the constant current mode. Using the obtained positive electrode, the current density was set to 30 mA / g, and constant current charging was performed up to a charging voltage of 4.8V. After charging, constant current discharge was repeated until the charge voltage was 4.8 V and the end-of-discharge voltage was 2.0 V.
  • the energy density in Table 1 was calculated from the average working potential x discharge capacity.
  • FIGS. 2 to 4 show charge / discharge profiles up to the third cycle in the case of using an alkali metal salt of each hexacyano metal acid.
  • FIG. 5 shows a charge / discharge profile at the second cycle when an alkali metal salt of each hexacyano metal acid is used.
  • the vertical axis of the charge / discharge profiles in FIGS. 2 to 5 represents the potential (Voltage, unit: V (V vs. A / V) based on the standard unipolar potential of the alkali metal of the alkali metal salt of each hexacyano metal acid used. A + )), and the horizontal axis represents capacity (capacity, unit: mAh / g). Further, FIG.
  • FIG. 6 is a diagram showing a change in discharge capacity over the course of the cycle.
  • the vertical axis of FIG. 6 represents the discharge capacity (Discharge Capacity, unit: mAh / g), and the horizontal axis represents the cycle number (Cycle Number).
  • a potassium ion battery having a high energy density was obtained by using the positive electrode active material for a potassium ion battery according to this embodiment.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • the amount of the electrolyte used was an amount sufficient to fill the separator with the electrolyte (0.15 mL to 0.3 mL).
  • the electrolytic solution was prepared using KPF 6 manufactured by Tokyo Chemical Industry Co., Ltd., ethylene carbonate manufactured by Kishida Chemical Co., and diethyl carbonate manufactured by Kishida Chemical Co., Ltd.
  • the charge / discharge conditions were measured at room temperature (25 ° C.) with the charge / discharge current density set to the constant current mode. Using the obtained positive electrode, the current density was set to 30 mA / g, and the charge voltage was constant current charged to 4.5V. After charging, constant current discharge was repeated until the charge voltage was 4.5V and the end-of-discharge voltage was 2.0V.
  • the coulombic efficiency in Table 2 is calculated from the initial charge capacity / initial discharge capacity ⁇ 100, the energy density is calculated from the average operating potential ⁇ discharge capacity, and the average potential is a value obtained by integrating the measured voltage by the discharge capacity / It was calculated from the discharge capacity.
  • FIG. 7 to 11 show charge / discharge profiles in the first cycle when potassium salts of hexacyano metal acids are used.
  • FIG. 12 shows a diagram in which charge / discharge profiles of one cycle in the case where potassium salts of hexacyano metal acids are used are combined into one figure. 7 to 12, the vertical axis represents the potential (Voltage, unit: V (V vs. K / K + )) based on the standard unipolar potential of potassium, and the horizontal axis represents the capacity ( Capacity, unit: mAh / g). Further, FIG.
  • FIG. 13 is a diagram showing a change in discharge capacity over the course of a cycle when K—Mn [Fe (CN) 6 ] or K—Fe [Fe (CN) 6 ] is used.
  • the vertical axis in FIG. 13 represents the discharge capacity (Discharge Capacity, unit: mAh / g), and the horizontal axis represents the cycle number (Cycle Number).
  • a potassium ion battery having a high energy density was obtained by using the positive electrode active material for a potassium ion battery according to this embodiment.

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Abstract

Cette invention concerne un matériau actif d'électrode positive pour une batterie potassium-ion, contenant un composé représenté par la formule (1). Dans la formule (1), m représente un nombre allant de 0,5 à 2, x représente un nombre allant de 0,5 à 1,5, y représente un nombre allant de 0,5 à 1,5, et z représente zéro ou un nombre positif. L'invention concerne en outre une électrode positive pour une batterie potassium-ion contenant le matériau actif d'électrode positive pour batterie potassium-ion selon le présent mode de réalisation, ou une batterie potassium-ion pourvue de l'électrode positive pour une batterie potassium-ion Formule (1) : KmFexMny(CN)6•zH2O
PCT/JP2017/043860 2016-12-26 2017-12-06 Matériau actif d'électrode positive pour batterie potassium-ion, électrode positive pour batterie potassium-ion et batterie potassium-ion WO2018123487A1 (fr)

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WO2021111497A1 (fr) * 2019-12-02 2021-06-10 日本電信電話株式会社 Batterie secondaire au potassium et son procédé de fabrication
CN113161603A (zh) * 2021-04-07 2021-07-23 北京航空航天大学 一种新型钾离子电池及其制备方法
WO2022270561A1 (fr) * 2021-06-23 2022-12-29 セントラル硝子株式会社 Solution électrolytique non aqueuse, batterie sodium-ion non aqueuse, batterie potassium-ion non aqueuse, procédé de fabrication de batterie sodium-ion non aqueuse, et procédé de fabrication de batterie potassium-ion non aqueuse
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US20220158254A1 (en) 2019-03-19 2022-05-19 The University Of Tokyo Aqueous electrolyte solution for energy storage devices and energy storage device comprising this aqueous electrolyte solution
CN112645354B (zh) * 2020-12-21 2022-07-15 电子科技大学 表面改性钠锰铁基普鲁士蓝材料及其制备方法和应用
JP7457817B2 (ja) * 2021-04-29 2024-03-28 寧徳時代新能源科技股▲分▼有限公司 コア－シェル構造を有するプルシアンブルー類似体、その製造方法、および、それを含むナトリウムイオン二次電池

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WO2022270561A1 (fr) * 2021-06-23 2022-12-29 セントラル硝子株式会社 Solution électrolytique non aqueuse, batterie sodium-ion non aqueuse, batterie potassium-ion non aqueuse, procédé de fabrication de batterie sodium-ion non aqueuse, et procédé de fabrication de batterie potassium-ion non aqueuse
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