WO2011129419A1 - Oxyde métallique composite, matériau actif d'électrode positive, électrode positive et pile secondaire au sodium - Google Patents

Oxyde métallique composite, matériau actif d'électrode positive, électrode positive et pile secondaire au sodium Download PDF

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WO2011129419A1
WO2011129419A1 PCT/JP2011/059321 JP2011059321W WO2011129419A1 WO 2011129419 A1 WO2011129419 A1 WO 2011129419A1 JP 2011059321 W JP2011059321 W JP 2011059321W WO 2011129419 A1 WO2011129419 A1 WO 2011129419A1
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metal oxide
composite metal
positive electrode
secondary battery
sodium secondary
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PCT/JP2011/059321
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English (en)
Japanese (ja)
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舞子 坂
哲理 中山
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住友化学株式会社
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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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1228—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [MnO2]n-, e.g. LiMnO2, Li[MxMn1-x]O2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/0018—Mixed oxides or hydroxides
    • C01G49/0072—Mixed oxides or hydroxides containing manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
    • 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
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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 composite metal oxide and a sodium secondary battery using this as a positive electrode active material.
  • the composite metal oxide is used as an electrode active material for a secondary battery.
  • lithium secondary batteries have already been put into practical use as small power sources for mobile phones and laptop computers, and further, power sources for automobiles such as electric vehicles and hybrid vehicles, or power sources for distributed power storage, etc. It is being considered as a large power source. Therefore, the demand for lithium secondary batteries is expected to increase.
  • the material constituting the electrode of the lithium secondary battery contains a large amount of lithium, which is a rare metal element, and there is a concern about the shortage of supply of lithium in response to the increase in demand for large power sources.
  • a sodium secondary battery has been studied as a secondary battery that can solve the above supply concerns.
  • Patent Document 1 discloses firing a raw material having a composition ratio of Na, Mn and Co (Na: Mn: Co) of 0.7: 0.5: 0.5.
  • the Na deficient positive electrode active material obtained in this way is specifically described.
  • ⁇ -NaFeO 2 which is a complex oxide of Fe and Na, which is an abundant element as a resource, is specifically described in Patent Document 2 as a positive electrode active material for a nonaqueous electrolyte secondary battery. It is known that the (104) plane spacing is 2.20 mm.
  • the object of the present invention is to reduce the content of expensive rare metal elements such as Li and Co, and to provide a sodium secondary battery that contains Fe, which is an element rich in resources, and has a high energy density. It is to provide a metal oxide. Means for Solving the Problems The present invention provides the following.
  • ⁇ 4> A positive electrode active material containing the composite metal oxide according to any one of ⁇ 1> to ⁇ 3>.
  • ⁇ 5> A positive electrode containing the positive electrode active material of ⁇ 4>.
  • ⁇ 6> A sodium secondary battery having the positive electrode of ⁇ 5>.
  • ⁇ 7> The sodium secondary battery according to ⁇ 6>, further including a separator.
  • FIG. 1 shows an X-ray diffraction pattern of the composite metal oxide 1.
  • FIG. 2 shows an X-ray diffraction pattern in the composite metal oxide 2.
  • FIG. 3 shows an X-ray diffraction pattern in the composite metal oxide 3.
  • FIG. 4 shows an X-ray diffraction pattern in the composite metal oxide 5.
  • FIG. 5 shows an X-ray diffraction pattern in the composite metal oxide 6.
  • FIG. 6 shows an X-ray diffraction pattern in the composite metal oxide 7.
  • the composite metal oxide is ⁇ -NaFeO. 2
  • the (104) plane spacing is not less than 2.16 angstroms and less than 2.18 angstroms, and is represented by the following formula (1): Na (Fe x Ni y Mn 1-xy ) O 2 (1) (Here, x is 0.1 or more and 0.6 or less, and y is more than 0 and less than 0.9.) When x exceeds 0.6, the discharge capacity becomes small. When x is less than 0.1, single-phase ⁇ -NaFeO 2 The type crystal structure is difficult to obtain and the energy density is lowered.
  • x is preferably 0.2 or more, and more preferably 0.4 or less in order to increase the discharge capacity.
  • the composite metal oxide may have an impurity phase such as NiO and an impurity compound, but single-phase ⁇ -NaFeO. 2 It is preferably composed of a type crystal structure. Crystal structure of composite metal oxide and ⁇ -NaFeO 2 The interplanar spacing of the (104) plane of the type crystal structure can be determined by powder X-ray diffraction measurement.
  • the interplanar spacing of the (104) plane of the type crystal structure is preferably 2.163 angstroms or more and 2.175 angstroms or less, more preferably 2.171 angstroms or more and 2.175 angstroms or less.
  • the BET specific surface area of the composite metal oxide is 0.1 to 5 m. 2 / G, and this tends to increase the energy density.
  • the BET specific surface area is more preferably 0.3 m 2 / G or more, and even more preferably 0.5 m 2 / G or more.
  • the BET specific surface area is more preferably 4.5 m. 2 / G or less, even more preferably 4 m 2 / G or less.
  • Part of M (wherein M is one or more elements selected from the group consisting of Fe, Ni and Mn) contained in the composite metal oxide may be replaced with a metal element other than M. .
  • the battery characteristics of the sodium secondary battery may be improved by the replacement.
  • metals other than M Li, K, Ag, Mg, Ca, Sr, Ba, Al, Ga, In, Ti, V, Cr, Co, Cu, Zn, Sc, Y, Nb, Mo, La, Ce, Examples thereof include metal elements such as Pr, Nd, Sm, Eu, Gd, Tb, Ho, Er, Tm, Yb, and Lu.
  • Method for producing composite metal oxide The composite metal oxide can be produced by firing a raw material having a composition that can be a composite metal oxide.
  • Examples of the raw material include a mixture of metal-containing compounds.
  • By firing the mixture single-phase ⁇ -NaFeO 2
  • a composite metal oxide composed of a type crystal structure can be produced.
  • the metal-containing compounds containing the corresponding metal elements are weighed so as to have a predetermined composition, and they are mixed to obtain a mixture.
  • a composite metal oxide can be manufactured by baking the obtained mixture.
  • Each of the raw materials is weighed so that the molar ratio of Na: Mn: Fe: Ni is 1: 0.3: 0.4: 0.3, they are mixed, and the resulting mixture is fired.
  • the metal-containing compounds include oxides or compounds that can be converted to oxides at high temperatures such as hydroxides, carbonates, nitrates, halides, or oxalates.
  • the sodium compound examples include one or more compounds selected from the group consisting of sodium hydroxide, sodium chloride, sodium nitrate, sodium peroxide, sodium sulfate, sodium bicarbonate, sodium oxalate and sodium carbonate.
  • the compound may be a hydrate.
  • sodium carbonate is preferable because of its low hygroscopicity, and from the viewpoint of manufacturing cost, sodium hydroxide is preferable because of its high reactivity at low temperatures. If sodium hydroxide is used, it can be fired at a relatively low firing temperature.
  • MnO 2 manganese compound
  • the iron compound is Fe 3 O 4 Ni is preferred as the nickel compound. 2 O 3 Is preferred. These compounds may be hydrates.
  • a mixture of metal-containing compounds can also be obtained by mixing a metal-containing compound obtained by the following coprecipitation method and a sodium compound.
  • a metal-containing compound obtained by the following coprecipitation method e.g., a sodium compound.
  • compounds of Mn, Fe and Ni compounds such as chloride, nitrate, acetate, formate, oxalate or sulfate are dissolved in water to obtain a mixed aqueous solution.
  • a precipitate containing a metal-containing compound can be obtained.
  • chloride or sulfate is preferable.
  • the precipitant include LiOH (lithium hydroxide), NaOH (sodium hydroxide), KOH (potassium hydroxide), Li 2 CO 3 (Lithium carbonate), Na 2 CO 3 (Sodium carbonate), K 2 CO 3 (Potassium carbonate), (NH 4 ) 2 CO 3 (Ammonium carbonate) and (NH 2 ) 2
  • examples thereof include compounds selected from the group consisting of CO (urea).
  • the precipitating agent may be one or more of the compounds described above, may be one or more hydrates of the compounds described above, and a compound and a hydrate may be used in combination.
  • These precipitating agents are preferably aqueous precipitant solutions.
  • the aqueous precipitant solution is obtained by dissolving the precipitant in water.
  • the concentration of the precipitating agent in the aqueous precipitant solution is about 0.5 to 10 mol / liter, preferably about 1 to 8 mol / liter.
  • the precipitating agent is preferably KOH or NaOH.
  • the aqueous precipitant solution is preferably an aqueous KOH solution or an aqueous NaOH solution.
  • Aqueous ammonia can also be mentioned as the precipitant aqueous solution.
  • Ammonia water and a precipitant aqueous solution may be used in combination.
  • Examples of the method of bringing the mixed aqueous solution into contact with the precipitant include a method of adding a precipitant (including a precipitant aqueous solution) to the mixed aqueous solution, a method of adding the mixed aqueous solution to the precipitant aqueous solution, and a mixed aqueous solution of water. And a method of adding a precipitant (including a precipitant aqueous solution). These additions are preferably accompanied by stirring.
  • a method of adding a mixed aqueous solution to a precipitant aqueous solution is preferable.
  • the pH tends to decrease as the mixed aqueous solution is added to the precipitant aqueous solution. It is preferable to add the mixed aqueous solution while adjusting the pH to be 9 or more, preferably 10 or more.
  • This adjustment can be performed by adding a precipitant aqueous solution.
  • the atmosphere at the time of contact is preferably nitrogen or argon in order to suppress impurity generation.
  • a precipitate can be obtained by the above contact. This precipitate contains a metal-containing compound. After bringing the mixed aqueous solution into contact with the precipitating agent, a slurry containing a precipitate is usually obtained, and the precipitate may be recovered by solid-liquid separation.
  • Solid-liquid separation may be performed by any method. From the viewpoint of operability, solid-liquid separation such as filtration is preferable. A method of volatilizing the liquid by heating such as spray drying may be used. The collected precipitate may be washed and dried. The precipitate obtained after the solid-liquid separation may have an excessive component of the precipitant attached thereto, and the component can be reduced by washing.
  • the cleaning liquid used for cleaning is preferably water, and may be a water-soluble organic solvent such as alcohol or acetone. Examples of drying include heat drying, air drying, and vacuum drying. Heat drying is usually performed at 50 to 300 ° C., preferably about 100 to 200 ° C. Washing and drying may be performed twice or more. Examples of the mixing method include dry mixing and wet mixing.
  • the mixing device examples include a stirring and mixing device, a V-type mixer, a W-type mixer, a ribbon mixer, a drum mixer, and a ball mill.
  • the firing temperature depends on the type of sodium compound used, and is usually about 400 to 1200 ° C., preferably about 500 to 1000 ° C.
  • the time for holding at the firing temperature is usually 0.1 to 20 hours, preferably 0.5 to 10 hours.
  • the rate of temperature rise to the firing temperature is usually 50 to 400 ° C./hour, and the rate of temperature fall from the firing temperature to room temperature is usually 10 to 400 ° C./hour.
  • the firing atmosphere include air, oxygen, nitrogen, argon, or a mixed gas thereof.
  • Air is preferable from the viewpoint of ease of atmosphere control, and oxygen, nitrogen, argon, or a mixed gas thereof is preferable from the viewpoint of stability of the sample after firing.
  • a halide such as fluoride or chloride
  • the halide may play a role as a reaction accelerator (flux). Examples of the flux include NaF and MnF.
  • the obtained composite metal oxide may be optionally pulverized using an industrially commonly used apparatus such as a ball mill, a jet mill, a vibration mill, You may wash and classify. By these operations, the particle size of the composite metal oxide may be adjusted.
  • Firing may be performed twice or more.
  • a surface treatment such as coating the particle surface of the composite metal oxide with an inorganic substance containing Si, Al, Ti, Y or the like may be performed.
  • you may heat-process after said surface treatment.
  • the BET specific surface area of the powder after the heat treatment may vary from the BET specific surface area of the composite metal oxide.
  • the composite metal oxide can be used as a positive electrode active material.
  • the positive electrode active material contains a composite metal oxide. If a composite metal oxide is used for the positive electrode active material of a sodium secondary battery, the resulting sodium secondary battery has a higher energy density than the conventional one.
  • Positive electrode and manufacturing method thereof The positive electrode contains a positive electrode active material.
  • the positive electrode can be produced by supporting a positive electrode mixture containing a positive electrode active material, a conductive material and a binder on a positive electrode current collector.
  • the conductive material include carbon materials such as natural graphite, artificial graphite, cokes, and carbon black.
  • a thermoplastic resin is mentioned as a binder.
  • thermoplastic resins include polyvinylidene fluoride (hereinafter sometimes referred to as PVDF), polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), tetrafluoroethylene and hexafluoropropylene.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • Fluorine resins such as vinylidene fluoride copolymers, propylene hexafluoride / vinylidene fluoride copolymers, tetrafluoroethylene / perfluorovinyl ether copolymers; and polyolefin resins such as polyethylene and polypropylene . Two or more of these may be used.
  • the positive electrode current collector include Al, Ni, and stainless steel.
  • Al is preferable from the viewpoint of being easily processed into a thin film and inexpensive.
  • the method of supporting the positive electrode mixture on the positive electrode current collector include a pressure molding method; a positive electrode mixture paste is obtained by further using an organic solvent, and the paste is applied to the positive electrode current collector and dried. Then, a method of fixing the positive electrode mixture to the current collector by pressing the obtained sheet is obtained.
  • the positive electrode mixture paste contains a positive electrode active material, a conductive material, a binder, and an organic solvent.
  • organic solvents include amine solvents such as N, N-dimethylaminopropylamine and diethylenetriamine; ether solvents such as tetrahydrofuran; ketone solvents such as methyl ethyl ketone; ester solvents such as methyl acetate; dimethylacetamide, N- Examples thereof include amide solvents such as methyl-2-pyrrolidone (hereinafter sometimes referred to as NMP).
  • NMP amide solvents such as methyl-2-pyrrolidone
  • Examples of the method of applying the positive electrode mixture to the positive electrode 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. As described above, the positive electrode can be manufactured.
  • Sodium secondary battery A sodium secondary battery usually has a separator.
  • the sodium secondary battery stores an electrode group obtained by laminating a positive electrode, a separator, a negative electrode, and a separator in this order, or laminating and winding in a battery case such as a battery can. It can be manufactured by injecting an electrolytic solution containing an electrolyte and an organic solvent into the case.
  • the sodium secondary battery for example, a positive electrode, a solid electrolyte, a negative electrode and a solid electrolyte are laminated in this order, or an electrode group obtained by laminating and winding is used as a battery can. It can be housed in a battery case and manufactured.
  • a cross section when the electrode group is cut perpendicularly to the axis of winding or a cross section when the electrode group is cut parallel to the stacking direction has a circle, an ellipse, a rectangle, and a corner.
  • the shape which becomes such a rectangle etc. is mentioned.
  • Examples of the shape of the battery include a paper shape, a coin shape, a cylindrical shape, and a square shape.
  • Sodium secondary battery-negative electrode The negative electrode can be doped with sodium ions and dedope at a lower potential than the positive electrode.
  • the negative electrode include an electrode in which a negative electrode mixture containing a negative electrode material is supported on a negative electrode current collector, or an electrode made of a negative electrode material alone.
  • the negative electrode material may be a carbon material, a chalcogen compound (oxide, sulfide, etc.), a nitride, a metal or an alloy, which can be doped with sodium ions at a lower potential than that of the positive electrode and can be undoped. Possible materials are listed. These negative electrode materials may be mixed. Specific examples of the negative electrode material are shown below.
  • the carbon material specifically, in graphite such as natural graphite and artificial graphite, coke, carbon black, pyrolytic carbon, carbon fiber, polymer fired body, etc., at a lower potential than the positive electrode, Examples include materials that can be doped with sodium ions and can be dedope.
  • These carbon materials, oxides, sulfides, and nitrides may be used in combination, and may be crystalline or amorphous. These carbon materials, oxides, sulfides and nitrides are mainly carried on the negative electrode current collector and used as the negative electrode.
  • the metal include sodium metal, silicon metal, and tin metal.
  • alloys include sodium alloys such as Na—Al, Na—Ni, Na—Si; silicon alloys such as Si—Zn; Sn—Mn, Sn—Co, Sn—Ni, Sn—Cu, Sn—La, etc. Tin alloy; Cu 2 Sb, La 3 Ni 2 Sn 7 And alloys thereof.
  • the negative electrode mixture may contain a binder as necessary.
  • a thermoplastic resin is mentioned as a binder.
  • Specific examples of the thermoplastic resin include PVDF, thermoplastic polyimide, carboxymethyl cellulose, polyethylene, and polypropylene.
  • the electrolytic solution does not contain the later-described ethylene carbonate and the negative electrode mixture contains polyethylene carbonate, the cycle characteristics and large current discharge characteristics of the obtained battery may be improved.
  • the negative electrode current collector include Cu, Ni, stainless steel, and Al. From the viewpoint that it is difficult to make an alloy with sodium and it is easy to process into a thin film, Cu or Al is preferable.
  • the method of supporting the negative electrode mixture on the negative electrode current collector is the same as the method of forming the positive electrode; pressure molding; obtaining a negative electrode mixture paste by further using an organic solvent and the like, and applying the paste to the negative electrode current collector And drying to obtain a sheet, and pressing the obtained sheet to fix the negative electrode mixture to the current collector.
  • Sodium secondary battery separator examples of the material for the separator include polyolefin resins such as polyethylene and polypropylene, fluororesins, and nitrogen-containing aromatic polymers.
  • Examples of the shape of the separator include shapes such as a porous film, a nonwoven fabric, and a woven fabric. A single-layer or multi-layer separator using two or more of these materials may be used.
  • the separator examples include those described in JP 2000-30686 A, JP 10-324758 A, and the like.
  • the thickness of the separator is preferably thin as long as the mechanical strength is maintained from the viewpoint of increasing the volume energy density of the battery and reducing the internal resistance.
  • the thickness of the separator is preferably about 5 to 200 ⁇ m, more preferably about 5 to 40 ⁇ m.
  • the separator preferably has a porous film containing a thermoplastic resin.
  • the secondary battery preferably has a function of shutting down the current when the abnormal current flows in the battery due to a short circuit between the positive electrode and the negative electrode, etc., and preventing the excessive current from flowing (shuts down). .
  • the secondary battery is preferably shut down at the lowest possible temperature when the normal operating temperature is exceeded.
  • the shutdown is performed by closing the micropores of the porous film. Furthermore, even after the shutdown, even if the temperature in the battery rises to a certain high temperature, the separator can maintain the shutdown state without breaking the film due to the temperature, in other words, it has high heat resistance. preferable.
  • a separator having a laminated porous film in which a heat-resistant porous layer containing a heat-resistant resin and a porous film containing a thermoplastic resin are laminated with each other it is possible to further prevent thermal film breakage of the secondary battery Become.
  • the heat resistant porous layer may be laminated on both surfaces of the porous film.
  • a separator having a laminated porous film in which a heat resistant porous layer containing a heat resistant resin and a porous film containing a thermoplastic resin are laminated will be described.
  • the thickness of this separator is usually 40 ⁇ m or less, preferably 20 ⁇ m or less.
  • the value of A / B is preferably 0.1 to 1.
  • this separator preferably has an air permeability of 50 to 300 seconds / 100 cc, more preferably 50 to 200 seconds / 100 cc, as measured by the Gurley method.
  • the separator has a porosity of usually 30 to 80% by volume, preferably 40 to 70% by volume.
  • the heat resistant porous layer contains a heat resistant resin.
  • the heat-resistant porous layer is preferably a thin heat-resistant porous layer having a thickness of 1 to 10 ⁇ m, more preferably 1 to 5 ⁇ m, particularly 1 to 4 ⁇ m.
  • the heat-resistant porous layer has fine pores, and the size (diameter) of the pores is usually 3 ⁇ m or less, preferably 1 ⁇ m or less. Furthermore, the heat resistant porous layer can also contain a filler described later.
  • the heat resistant resin contained in the heat resistant porous layer include polyamide, polyimide, polyamideimide, polycarbonate, polyacetal, polysulfone, polyphenylene sulfide, polyetheretherketone, aromatic polyester, polyethersulfone and polyetherimide, In order to further improve the heat resistance, polyamide, polyimide, polyamideimide, polyethersulfone, and polyetherimide are preferable, and polyamide, polyimide, and polyamideimide are more preferable.
  • the heat-resistant resin is a nitrogen-containing aromatic polymer such as aromatic polyamide (para-oriented aromatic polyamide, meta-oriented aromatic polyamide), aromatic polyimide, aromatic polyamideimide, and particularly preferably aromatic.
  • aromatic polyamide particularly preferably para-oriented aromatic polyamide (hereinafter sometimes referred to as para-aramid).
  • para-aramid polyamide, particularly preferably para-oriented aromatic polyamide
  • the heat resistant resin also include poly-4-methylpentene-1 and cyclic olefin polymers.
  • the thermal film breaking temperature is about 400 ° C. at the maximum.
  • the thermal film breaking temperature is about 250 ° C. at the maximum.
  • the thermal film breaking temperature is about 300 ° C. at the maximum.
  • Para-aramid is obtained by polycondensation of a para-oriented aromatic diamine and a para-oriented aromatic dicarboxylic acid halide, and the amide bond is in the para position of the aromatic ring or an oriented position equivalent thereto (for example, 4,4 in biphenylene).
  • para-aramid is para-aramide having a para-orientation type or a structure according to para-orientation type, specifically, poly (paraphenylene terephthalamide), poly (parabenzamide), poly (4,4′-benzanilide terephthalate) Amide), poly (paraphenylene-4,4′-biphenylenedicarboxylic acid amide), poly (paraphenylene-2,6-naphthalenedicarboxylic acid amide), poly (2-chloro-paraphenylene terephthalamide), paraphenylene terephthalamide / 2,6-dichloroparaphenylene terephthalamide copolymer.
  • the aromatic polyimide is preferably a wholly aromatic polyimide produced by condensation polymerization of an aromatic dianhydride and an aromatic diamine.
  • the dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid And dianhydride, 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane, and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride.
  • diamine examples include oxydianiline, paraphenylenediamine, benzophenonediamine, 3,3′-methylenedianiline, 3,3′-diaminobenzophenone, 3,3′-diaminodiphenylsulfone, and 1,5-naphthalenediamine.
  • a polyimide soluble in a solvent can be preferably used.
  • An example of such a polyimide is a polyimide that is a condensation polymer of 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride and an aromatic diamine.
  • Aromatic polyamideimides include those obtained from condensation polymerization of aromatic dicarboxylic acids and aromatic diisocyanates, and those obtained from condensation polymerization of aromatic dianhydrides and aromatic diisocyanates.
  • Specific examples of the aromatic dicarboxylic acid include isophthalic acid and terephthalic acid.
  • Specific examples of the aromatic dianhydride include trimellitic anhydride.
  • Specific examples of the aromatic diisocyanate include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, orthotolylene diisocyanate, and m-xylene diisocyanate.
  • the heat resistant porous layer may contain a filler.
  • the filler is selected from organic powder, inorganic powder, or a mixture thereof.
  • the average particle diameter of the particles constituting the filler is preferably 0.01 to 1 ⁇ m.
  • Examples of the shape of the filler include a substantially spherical shape, a plate shape, a column shape, a needle shape, a whisker shape, and a fiber shape. Since it is easy to form uniform holes, a substantially spherical shape is preferable.
  • organic powder as the filler examples include, for example, styrene, vinyl ketone, acrylonitrile, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate, glycidyl acrylate, methyl acrylate and the like alone or in combination of two or more types; polytetrafluoroethylene, Fluorocarbon resins such as tetrafluoroethylene-6-fluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer and polyvinylidene fluoride; Melamine resin; urea resin; polyolefin; polymethacrylate; Is mentioned.
  • An organic powder may be used independently and can also be used in mixture of 2 or more types. From the viewpoint of chemical stability, polytetrafluoroethylene powder is preferred.
  • the inorganic powder as the filler include powders made of inorganic substances such as metal oxides, metal nitrides, metal carbides, metal hydroxides, carbonates, sulfates, specifically, alumina, silica, The powder which consists of titanium dioxide, calcium carbonate, etc. is mentioned.
  • An inorganic powder may be used independently and can also be used in mixture of 2 or more types. From the viewpoint of chemical stability, alumina powder is preferred.
  • the filler is more preferably an alumina powder, the filler is an alumina powder, and even more preferably, some or all of the particles constituting the alumina powder are substantially spherical.
  • the filler content in the heat-resistant porous layer depends on the specific gravity of the filler material.
  • the weight ratio of the filler is usually 20 to 95 parts by weight, preferably 30 to 90 parts by weight with respect to 100 parts by weight of the total weight of the heat resistant porous layer.
  • the weight ratio of the filler can be appropriately set depending on the specific gravity of the filler material.
  • the porous film in laminated porous film contains a thermoplastic resin.
  • the thickness of the porous film is usually 3 to 30 ⁇ m, preferably 3 to 20 ⁇ m. Similar to the heat resistant porous layer, the porous film has fine pores, and the pore size is usually 3 ⁇ m or less, preferably 1 ⁇ m or less.
  • the porosity of the porous film is usually 30 to 80% by volume, preferably 40 to 70% by volume.
  • the thermoplastic resin contained in the porous film include those that soften at 80 to 180 ° C. Those that do not dissolve in the electrolyte in the secondary battery can be selected.
  • thermoplastic resin examples include polyolefins such as polyethylene and polypropylene, and thermoplastic polyurethane. A mixture of two or more of these may be used.
  • the thermoplastic resin in the porous film is preferably polyethylene.
  • polyethylene include polyethylene such as low-density polyethylene, high-density polyethylene, and linear polyethylene, and also includes ultra-high molecular weight polyethylene.
  • the thermoplastic resin preferably contains ultrahigh molecular weight polyethylene.
  • the thermoplastic resin preferably contains a wax made of polyolefin having a low molecular weight (weight average molecular weight of 10,000 or less).
  • Sodium secondary battery-electrolyte or solid electrolyte The electrolytic solution contains an electrolyte and an organic solvent. Examples of electrolytes in the electrolyte include NaClO 4 , NaPF 6 , NaAsF 6 , NaSbF 6 , NaBF 4 , NaCF 3 SO 3 NaN (SO 2 CF 3 ) 2 , Lower aliphatic carboxylic acid sodium salt, NaAlCl 4 Is mentioned. A mixture of two or more of these may be used.
  • the electrolyte is NaPF 6 , NaAsF 6 , NaSbF 6 , NaBF 4 , NaCF 3 SO 3 And NaN (SO 2 CF 3 ) 2 It is preferable to contain at least one fluorine-containing sodium salt selected from the group consisting of Examples of the organic solvent in the electrolytic solution include propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, isopropyl methyl carbonate, vinylene carbonate, 4-trifluoromethyl-1,3-dioxolan-2-one, 1, Carbonates such as 2-di (methoxycarbonyloxy) ethane; 1,2-dimethoxyethane, 1,3-dimethoxypropane, pentafluoropropyl methyl ether, 2,2,3,3-tetrafluoropropyl difluoromethyl ether, tetrahydrofuran Ethers such as 2-methyltetrahydrofuran; esters
  • a solid electrolyte may be used instead of the electrolytic solution.
  • the solid electrolyte include a polymer solid electrolyte such as a polymer containing at least one selected from a polyethylene oxide polymer, a polyorganosiloxane chain, and a polyoxyalkylene chain.
  • a so-called gel type electrolyte in which an electrolyte is held in a polymer can also be used.
  • solid electrolyte for example, Na 2 S-SiS 2 , Na 2 S-GeS 2 , Na 2 SP 2 S 5 , Na 2 SB 2 S 3 , Na 2 S-SiS 2 -Na 3 PO 4 , Na 2 S-SiS 2 -Na 2 SO 4 Sulfide-containing electrolyte such as NaZr 2 (PO 4 ) 3
  • Inorganic solid electrolytes such as NASICON type electrolytes are also included.
  • the solid electrolyte may serve as a separator, and in that case, a separator may not be required.
  • the sodium secondary battery of the present invention has a high energy density, it is a small battery, automobile, motorcycle, electric chair, forklift, train, airplane, ship, which is a power source for small equipment such as a mobile phone, portable audio, and laptop computer.
  • Suitable for medium- and large-sized batteries that are mobile batteries such as power supplies for transportation equipment such as spacecraft and submarines; power supplies for machinery such as cultivators; outdoor power supplies for camping applications; outdoor / indoor power supplies for vending machines, etc. It is.
  • the sodium secondary battery of the present invention uses abundant and inexpensive raw materials, so it can be used in outdoor / indoor power sources for factories, houses, etc .; solar battery chargers, wind power generators, etc.
  • Load leveling power supply for various power generations Installation power supply for low-temperature environments such as refrigerated / refrigerated warehouses and extremely cold areas; Installation power supply for high-temperature environments such as deserts; Installation power supply for space environments such as space stations; It is suitable as a middle- or large-sized battery that is a type battery.
  • Powder X-ray diffraction measurement The measurement was performed under the following conditions unless otherwise specified using a powder X-ray diffraction measurement device RINT2500TTR manufactured by Rigaku Corporation.
  • the mixed metal oxide and acetylene black are sufficiently mixed in an agate mortar, and N-methyl-2-pyrrolidone (NMP: manufactured by Tokyo Kasei Kogyo Co., Ltd.) is added to this mixture, and PVDF is further added to continue to be uniform.
  • NMP N-methyl-2-pyrrolidone
  • the mixture was mixed in an agate mortar to obtain a positive electrode mixture paste.
  • the positive electrode mixture paste was applied to an aluminum foil having a thickness of 40 ⁇ m, which is a current collector, with a thickness of 100 ⁇ m using an applicator.
  • the coated current collector was put in a dryer and dried while removing NMP to obtain an electrode sheet.
  • This electrode sheet was punched to a diameter of 1.5 cm with an electrode punching machine, and then pressed with a hand press to obtain a positive electrode.
  • a battery was prepared by combining the polypropylene porous film (thickness 20 ⁇ m) and metallic sodium (manufactured by Aldrich) as the negative electrode. The battery was assembled in a glove box in an argon atmosphere.
  • 44.88 g of potassium hydroxide was added to 300 ml of distilled water and dissolved by stirring to prepare an aqueous potassium hydroxide solution (precipitant aqueous solution).
  • the face spacing of the (104) plane of this ⁇ -NaFeO 2 type crystal structure was 2.175 mm.
  • the molar ratio of Na: Fe: Ni: Mn was 1: 0.5: 0.23: 0.27. .
  • 0.5 g of the composite metal oxide 2 was weighed and dried at 150 ° C. in a nitrogen stream for 15 minutes, and then the BET specific surface area of the composite metal oxide 2 was measured using a Micromerex Flowsorb II 2300. It was 1 m 2 / g.
  • the precipitate and sodium carbonate were weighed so that the molar ratio of Fe: Na was 0.4: 1, and these were dry-mixed using an agate mortar to obtain a mixture.
  • the mixture was placed in an alumina firing vessel and held in an air atmosphere at 900 ° C. for 4 hours using an electric furnace, whereby the mixture was fired and cooled to room temperature to obtain a composite metal oxide 3.
  • (2) Evaluation of composite metal oxide As a result of powder X-ray diffraction measurement of composite metal oxide 3, the crystal structure of composite metal oxide 3 belongs to the ⁇ -NaFeO 2 type crystal structure, and the impurity phase is It was not observed and was found to be a single phase (FIG. 3).
  • the face spacing of the (104) plane of this ⁇ -NaFeO 2 type crystal structure was 2.171 mm.
  • the molar ratio of Na: Fe: Ni: Mn was 1: 0.4: 0.3: 0.3. . 0.5 g of the composite metal oxide 3 was weighed and dried at 150 ° C. in a nitrogen stream for 15 minutes, and then the BET specific surface area of the composite metal oxide 3 was measured using a Micrometrix Flowsorb II2300. 0.2 m 2 / g.
  • the face spacing of the (104) plane of this ⁇ -NaFeO 2 type crystal structure was 2.170 mm.
  • the composition of the composite metal oxide 4 was analyzed by ICP (high frequency inductively coupled plasma) emission analysis, the molar ratio of Na: Fe: Ni: Mn was 1: 0.33: 0.34: 0.33. .
  • the BET specific surface area of the composite metal oxide 4 was measured using a Micromerex Flowsorb II2300. 0.6 m 2 / g.
  • the face spacing of the (104) plane of this ⁇ -NaFeO 2 type crystal structure was 2.173 mm.
  • the molar ratio of Na: Fe: Ni: Mn was 1: 0.4: 0.3: 0.3. . 0.5 g of the composite metal oxide 7 was weighed and dried in a nitrogen stream at 150 ° C. for 15 minutes, and then the BET specific surface area of the composite metal oxide 7 was measured using a Micromerex Flowsorb II2300. 0.2 m 2 / g.
  • a porous film was fixed on a PET film having a thickness of 100 ⁇ m, and the coating slurry was applied onto the porous film with a bar coater manufactured by Tester Sangyo Co., Ltd. While the PET film and the coated porous film are integrated, they are immersed in poor solvent water to deposit a para-aramid porous film (heat-resistant porous layer), and then the solvent is dried to peel off the PET film. Thus, a laminated porous film in which the heat-resistant porous layer was laminated on the porous film was obtained. The thickness of the laminated porous film was 16 ⁇ m, and the thickness of the para-aramid porous film (heat resistant porous layer) was 4 ⁇ m.
  • the laminated porous film had an air permeability of 180 seconds / 100 cc and a porosity of 50%.
  • SEM scanning electron microscope
  • a relatively small fine hole of about 0.03 to 0.06 ⁇ m and a relatively large fine of about 0.1 to 1 ⁇ m were observed. It was found to have pores.
  • the laminated porous film was evaluated by the following (A) to (C).
  • (A) Thickness measurement The thickness of the laminated porous film and the thickness of the porous film were measured in accordance with JIS standards (K7130-1992).
  • the thickness of the heat resistant porous layer a value obtained by subtracting the thickness of the porous film from the thickness of the laminated porous film was used.
  • B Measurement of air permeability by Gurley method The air permeability of the laminated porous film was measured with a digital timer type Gurley type densometer manufactured by Yasuda Seiki Seisakusho, based on JIS P8117.
  • C Porosity A sample of the obtained laminated porous film was cut into a square having a side length of 10 cm, and the weight W (g) and the thickness D (cm) were measured.
  • Porosity (volume%) 100 ⁇ ⁇ 1 ⁇ (W1 / true specific gravity 1 + W2 / true specific gravity 2 + ⁇ + Wn / true specific gravity n) / (10 ⁇ 10 ⁇ D) ⁇
  • the laminated porous film as obtained by the manufacture example is used as a separator, the sodium secondary battery which can prevent a thermal membrane breakage can be obtained.
  • a composite metal oxide using Fe and abundant resources in an optimal range can be provided by suppressing the use amount of rare metal elements Li and Co. If the composite metal oxide of the present invention is used as an electrode active material, a sodium secondary battery having a high energy density can be provided.
  • the present invention is extremely useful industrially.

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Abstract

La présente invention concerne : un oxyde métallique composite ; un matériau actif d'électrode positive ; une électrode positive ; et une pile secondaire au sodium. L'oxyde métallique composite présent une structure cristalline de type α-NaFeO2, ainsi qu'un espacement entre les faces (104) d'au moins 2,16 angströms et de moins de 2,18 angströms, et répond à la formule (1) : Na(FexNiyMn1-x-y)O2 (où x représente une valeur numérique comprise entre 0,1 et 0,6 inclus ; et y représente une valeur numérique comprise entre 0 et 0,9 exclu). Le matériau actif d'électrode positive comprend l'oxyde métallique composite. L'électrode positive comprend le matériau actif d'électrode positive. La pile secondaire au sodium inclut l'électrode positive.
PCT/JP2011/059321 2010-04-16 2011-04-08 Oxyde métallique composite, matériau actif d'électrode positive, électrode positive et pile secondaire au sodium WO2011129419A1 (fr)

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JP2015176662A (ja) * 2014-03-13 2015-10-05 国立研究開発法人産業技術総合研究所 ナトリウムイオン二次電池用正極活物質
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CN110521035A (zh) * 2017-03-29 2019-11-29 住友化学株式会社 钠二次电池用电极活性物质、钠二次电池用电极、钠二次电池和复合金属氧化物的制造方法
US10978708B2 (en) 2014-01-09 2021-04-13 Faradion Limited Doped nickelate compounds
CN116082653A (zh) * 2022-12-30 2023-05-09 江苏大学 一种具有过氧化物酶活性MOFs的制备方法及对猪德尔塔冠状病毒的酶联免疫检测应用

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GB2503897A (en) * 2012-07-10 2014-01-15 Faradion Ltd Nickel doped compound for use as an electrode material in energy storage devices
WO2014081786A1 (fr) * 2012-11-21 2014-05-30 3M Innovative Properties Company Compositions d'anode pour batteries au sodium-ion et procédés de fabrication de celles-ci
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JP2013175311A (ja) * 2012-02-23 2013-09-05 National Institute Of Advanced Industrial & Technology ナトリウム二次電池正極材料、該ナトリウム二次電池用正極材料の製造方法、該ナトリウム二次電池用正極材料を用いるナトリウム二次電池用電極、該ナトリウム二次電池用電極を備える非水系ナトリウム二次電池、及び該非水系ナトリウム二次電池を用いる電気機器
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JP2015176662A (ja) * 2014-03-13 2015-10-05 国立研究開発法人産業技術総合研究所 ナトリウムイオン二次電池用正極活物質
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CN110461769A (zh) * 2017-03-29 2019-11-15 住友化学株式会社 复合金属氧化物、正极活性物质、正极、钠二次电池以及复合金属氧化物的制造方法
CN110521035A (zh) * 2017-03-29 2019-11-29 住友化学株式会社 钠二次电池用电极活性物质、钠二次电池用电极、钠二次电池和复合金属氧化物的制造方法
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CN110461769B (zh) * 2017-03-29 2022-03-01 住友化学株式会社 复合金属氧化物、正极活性物质、正极、钠二次电池以及复合金属氧化物的制造方法
CN110521035B (zh) * 2017-03-29 2022-08-23 住友化学株式会社 钠二次电池用电极活性物质、钠二次电池用电极、钠二次电池和复合金属氧化物的制造方法
CN116082653A (zh) * 2022-12-30 2023-05-09 江苏大学 一种具有过氧化物酶活性MOFs的制备方法及对猪德尔塔冠状病毒的酶联免疫检测应用
CN116082653B (zh) * 2022-12-30 2024-05-10 江苏大学 一种具有过氧化物酶活性MOFs的制备方法及对猪德尔塔冠状病毒的酶联免疫检测应用

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