WO2013024739A1 - Matériau actif pour batterie secondaire à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux, et procédé de fabrication d'un matériau actif pour une batterie secondaire à électrolyte non aqueux - Google Patents

Matériau actif pour batterie secondaire à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux, et procédé de fabrication d'un matériau actif pour une batterie secondaire à électrolyte non aqueux Download PDF

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WO2013024739A1
WO2013024739A1 PCT/JP2012/070040 JP2012070040W WO2013024739A1 WO 2013024739 A1 WO2013024739 A1 WO 2013024739A1 JP 2012070040 W JP2012070040 W JP 2012070040W WO 2013024739 A1 WO2013024739 A1 WO 2013024739A1
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transition metal
silicide
electrolyte secondary
active material
lithium
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PCT/JP2012/070040
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English (en)
Japanese (ja)
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正信 竹内
柳田　勝功
喜田　佳典
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三洋電機株式会社
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    • 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
    • H01M4/362—Composites
    • 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
    • H01M4/48—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
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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
    • H01M10/052—Li-accumulators
    • 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
    • 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 non-aqueous electrolyte secondary battery active material, a non-aqueous electrolyte secondary battery, and a method for producing a non-aqueous electrolyte secondary battery active material.
  • Patent Document 1 in order to obtain high output characteristics, a composite material of metal, oxide, nitride, carbide, boride or silicide and graphite or amorphous carbon is used as a conductive agent of the positive electrode active material. It has been proposed to use.
  • the main object of the present invention is to provide a non-aqueous electrolyte secondary battery active material capable of realizing a non-aqueous electrolyte secondary battery having high output characteristics.
  • the active material for a non-aqueous electrolyte secondary battery according to the present invention is obtained by sintering a transition metal silicide on the surface of lithium-containing transition metal composite oxide particles.
  • the non-aqueous electrolyte secondary battery according to the present invention includes a non-aqueous electrolyte secondary battery electrode having an active material layer containing the non-aqueous electrolyte secondary battery active material according to the present invention.
  • an active material for a non-aqueous electrolyte secondary battery is obtained by sintering a transition metal silicide on the surface of the lithium-containing transition metal composite oxide particles.
  • nonaqueous electrolyte secondary battery active material capable of realizing a nonaqueous electrolyte secondary battery having high output characteristics.
  • FIG. 1 is a schematic cross-sectional view of a nonaqueous electrolyte secondary battery according to an embodiment of the present invention.
  • FIG. 2 is a schematic view of a three-electrode test cell produced in Examples 1 to 4 and Comparative Examples 1 to 5.
  • FIG. 3 is a scanning electron micrograph of the positive electrode active material produced in Example 1.
  • the nonaqueous electrolyte secondary battery 1 includes a battery container 17.
  • the battery case 17 is a cylindrical shape.
  • the shape of the battery container is not limited to a cylindrical shape.
  • the shape of the battery container may be, for example, a flat shape.
  • an electrode body 10 impregnated with a nonaqueous electrolyte is accommodated.
  • non-aqueous electrolyte for example, a known non-aqueous electrolyte can be used.
  • the nonaqueous electrolyte solvent include cyclic carbonates, chain carbonates, and mixed solvents of cyclic carbonates and chain carbonates.
  • Specific examples of the cyclic carbonate include ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate, and the like.
  • Specific examples of the chain carbonate include dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate and the like.
  • a chain carbonate and a mixed solvent of a cyclic carbonate and a chain carbonate are preferably used as a non-aqueous solvent having a low viscosity and a low melting point and a high lithium ion conductivity.
  • the mixing ratio of cyclic carbonate to chain carbonate should be in the range of 2: 8 to 5: 5 by volume ratio. Is preferred.
  • An ionic liquid can also be used as a non-aqueous solvent for the non-aqueous electrolyte.
  • the cation species and anion species of the ionic liquid are not particularly limited. From the viewpoint of low viscosity, electrochemical stability, and hydrophobicity, for example, a pyridinium cation, an imidazolium cation, or a quaternary ammonium cation is preferably used as the cation.
  • an ionic liquid containing a fluorine-containing imide anion is preferably used as the anion.
  • a known lithium salt can be used as the solute of the nonaqueous electrolyte.
  • the lithium salt preferably used as the solute of the nonaqueous electrolyte include a lithium salt containing at least one element selected from the group consisting of P, B, F, O, S, N, and Cl.
  • Specific examples of such a lithium salt include, for example, LiPF 6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 , LiN (CF 3 SO 2 ) (C 4 F 9 SO 2 ), LiC (C 2 F 5 SO 2 ) 3 , LiAsF 6 , LiClO 4 and the like.
  • LiPF 6 is more preferably used as the solute of the nonaqueous electrolyte from the viewpoint of improving the high rate charge / discharge characteristics and durability.
  • the non-aqueous electrolyte may contain a kind of solute or may contain a plurality of kinds of solutes.
  • the electrode body 10 is formed by winding a negative electrode 11, a positive electrode 12, and a separator 13 disposed between the negative electrode 11 and the positive electrode 12.
  • the separator 13 is not particularly limited as long as it can suppress a short circuit due to contact between the positive electrode 12 and the negative electrode 11 and is impregnated with a non-aqueous electrolyte to obtain lithium ion conductivity.
  • Separator 13 can be constituted by a porous film made of resin, for example.
  • resin porous membrane include, for example, polypropylene and polyethylene porous membranes, and laminates of polypropylene porous membranes and polyethylene porous membranes.
  • the negative electrode 11 has a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector.
  • the negative electrode current collector can be composed of, for example, a foil made of a metal such as Cu or an alloy containing a metal such as Cu.
  • the negative electrode active material layer may contain a binder or a conductive agent in addition to the negative electrode active material.
  • the negative electrode active material is not particularly limited as long as it can reversibly occlude and release lithium.
  • Examples of the negative electrode active material include a carbon material, a material alloyed with lithium, and a metal oxide such as tin oxide.
  • Examples of the material to be alloyed with lithium include one or more metals selected from the group consisting of silicon, germanium, tin and aluminum, or one or more metals selected from the group consisting of silicon, germanium, tin and aluminum. What consists of an alloy containing is mentioned.
  • the carbon material examples include natural graphite, artificial graphite, mesophase pitch-based carbon fiber (MCF), mesocarbon microbead (MCMB), coke, hard carbon, fullerene, and carbon nanotube. From the viewpoint of improving the high rate charge / discharge characteristics, it is preferable to use a carbon material obtained by coating a graphite material with low crystalline carbon as the negative electrode active material.
  • the positive electrode 12 includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector.
  • the positive electrode current collector can be made of, for example, a metal such as Al or an alloy containing a metal such as Al.
  • the positive electrode active material layer includes a positive electrode active material.
  • the positive electrode active material layer may contain an appropriate material such as a binder and a conductive agent in addition to the positive electrode active material.
  • a binder preferably used include, for example, polyvinylidene fluoride.
  • a conductive agent preferably used include carbon materials such as graphite.
  • the positive electrode active material is formed by sintering a transition metal silicide on the surface of lithium-containing transition metal composite oxide particles. Therefore, excellent output characteristics can be obtained.
  • the following reasons can be considered as this reason. That is, since the transition metal silicide having electron conductivity is sintered on the surface of the lithium-containing transition metal composite oxide particles, the lithium-containing transition metal is also charged / discharged during which the positive electrode active material expands and contracts. The state in which the composite oxide particles and the transition metal silicide are in contact can be maintained. Therefore, it is considered that the transition metal silicide functions suitably during charge and discharge, and as a result, excellent output characteristics can be obtained.
  • transition metal silicide is simply added to the positive electrode active material. However, in that case, excellent output characteristics cannot be obtained. This is because transition metal silicide lacks flexibility and cannot be deformed following the expansion and contraction behavior of lithium-containing transition metal composite oxide particles during charge and discharge. This is considered to be because the state in contact with the transition metal silicide cannot be suitably maintained during charging and discharging.
  • transition metal borides, transition metal carbides and the like can be cited as materials having electronic conductivity.
  • excellent output characteristics can be realized by using a transition metal silicide as in this embodiment.
  • the following reasons can be considered as this reason. That is, when the boride is sintered, an oxide film is formed on the surface, so that the electron conductivity is lowered. As a result, it is considered that the output characteristics are not as excellent as when the transition metal silicide is used. Even with a transition metal silicide, an oxide film may be formed during sintering, but the oxide film formed on the surface of the transition metal silicide is considered to be very thin. Transition metal carbides do not have excellent oxidation resistance, so transition metal carbides are oxidatively decomposed during sintering, so it is considered that excellent output characteristics cannot be obtained as much as transition metal silicides are used. It is done.
  • the kind of lithium-containing transition metal composite oxide particles is not particularly limited.
  • the lithium-containing transition metal composite oxide particles preferably used include a lithium-containing transition having a layered structure represented by the general formula LiMeO 2 (where Me is at least one selected from the group consisting of Ni, Co and Mn).
  • a lithium-containing transition metal composite oxide having a spinel structure represented by the general formula LiMe 2 O 4 (Me is at least one selected from the group consisting of Fe, Ni, Co, and Mn).
  • Specific examples of the lithium-containing transition metal composite oxide particles preferably used include LiCoO 2 , LiNiO 2 , LiNi 0.3 Co 0.3 Mn 0.3 O 2 , LiFePO 4 , LiMn 2 O 4 and the like.
  • the general formula Li a (Ni b Co c Mn d) lithium-containing transition metal composite oxide particles represented by O 2 is also preferably used.
  • the volume change associated with the charge / discharge reaction tends to increase.
  • the technique of sintering the transition metal silicide on the surface of the lithium-containing transition metal composite oxide particles as in the present embodiment is suitable when applied to a positive electrode active material having a large volume change associated with the charge / discharge reaction.
  • b / d is 1.4 or more.
  • the technique of sintering the transition metal silicide on the surface of the lithium-containing transition metal composite oxide particles as in this embodiment is applied to a positive electrode active material having a low Co content and a low electron conductivity. Is preferred. Therefore, c is preferably 0.45 or less.
  • the lithium-containing transition metal composite oxide particles further include at least one selected from the group consisting of aluminum, titanium, chromium, vanadium, iron, copper, zinc, niobium, molybdenum, zirconium, tin, tungsten, sodium, and potassium. May be included.
  • the preferred transition metal silicide used for example, tungsten silicide, zirconium silicide, such ZrSi 2, titanium silicide such as TiSi 2, niobium silicide, such NbSi 2, silicide such as TaSi 2, such as WSi 2 tantalum, chromium silicide such as CrSi 2, include molybdenum silicide, etc., such as MoSi 2.
  • one type of transition metal silicide may be used, or a plurality of types of transition metal silicides may be mixed and used.
  • the content of the transition metal silicide in the positive electrode active material is not particularly limited, but is preferably 0.1 mol% or more and 5 mol% or less, and more preferably 0.5 mol% or more and 2 mol% or less. . If the content of the transition metal silicide in the positive electrode active material is too low, the effect of improving the output characteristics may be too small. On the other hand, if the content of the transition metal silicide in the positive electrode active material is too high, the proportion of the lithium-containing transition metal composite oxide particles in the positive electrode active material becomes too high, and the energy density of the positive electrode may become too low.
  • the transition metal silicide may cover the entire surface of the lithium-containing transition metal composite oxide particles, or may cover only a part thereof.
  • the coverage of the transition metal silicide on the surface of the lithium-containing transition metal composite oxide particles may be less than 10%.
  • lithium-containing transition metal composite oxide particles having a layered structure represented by the general formula LiMeO 2 (where Me is at least one selected from the group consisting of Ni, Co, and Mn) are used, transition is performed.
  • the metal silicide at least one selected from the group consisting of tungsten silicide, zirconium silicide and titanium silicide is preferably used, and at least one of tungsten silicide and zirconium silicide is more preferably used.
  • the active material for a nonaqueous electrolyte secondary battery (positive electrode active material) of the present embodiment can be produced by sintering a transition metal silicide on the surface of lithium-containing transition metal composite oxide particles.
  • the positive electrode active material of this embodiment can be produced by sintering a transition metal silicide on the surface of lithium-containing transition metal composite oxide particles.
  • the atmosphere in which the lithium transition metal composite oxide particles and the transition metal silicide are sintered may be, for example, an air atmosphere.
  • the lithium transition metal composite oxide particles and the transition metal silicide are sintered at a temperature at which at least a part of the structure of the transition metal silicide before sintering is maintained even after the sintering.
  • the lithium transition metal composite oxide particles and the transition metal silicide are sintered at a temperature not higher than the oxidative decomposition start temperature of the transition metal silicide. Therefore, when molybdenum silicide is used as the transition metal silicide, it is preferable to sinter at less than 400 ° C. When titanium silicide is used as the transition metal silicide, it is preferable to sinter at less than 500 ° C. When niobium silicide is used as the transition metal silicide, sintering is preferably performed at less than 650 ° C. When tungsten silicide is used as the transition metal silicide, it is preferable to sinter at less than 700 ° C.
  • sintering is preferably performed at less than 800 ° C.
  • tantalum silicide is used as the transition metal silicide, it is preferable to sinter at less than 900 ° C.
  • chromium silicide is used as the transition metal silicide, sintering is preferably performed at less than 1050 ° C.
  • transition metal silicide after sintering maintains the crystal structure before sintering can be confirmed using an X-ray diffraction (XRD) method or the like.
  • the transition metal silicide particles used for the sintering are used. It is preferable to appropriately adjust the diameter, sintering time, etc. so that at least a part of the structure of the transition metal silicide before sintering is maintained even after sintering.
  • the sintering temperature of the lithium transition metal composite oxide particles and the transition metal silicide is too low, the sintering of the lithium transition metal composite oxide particles and the transition metal silicide does not proceed sufficiently, and the transition metal silicide is The lithium transition metal composite oxide particles may not be firmly held on the surface. For this reason, it is preferable that sintering temperature is 300 degreeC or more, and it is more preferable that it is 500 degreeC or more.
  • the reason why the sintering of the lithium transition metal composite oxide particles and the transition metal silicide proceeds favorably even at a low temperature is that lithium contained in the lithium transition metal composite oxide particles functions as a sintering accelerator. it is conceivable that.
  • lithium-containing transition metal composite oxide particles it is preferable to use particles having a layered structure represented by a general formula LiMeO 2 (where Me is at least one selected from the group consisting of Ni, Co and Mn). .
  • the transition metal silicide at least one selected from the group consisting of molybdenum silicide, titanium silicide, niobium silicide, tungsten silicide, zirconium silicide, tantalum silicide, and chromium silicide can be used. Among them, it is preferable to use at least one selected from the group consisting of titanium silicide, niobium silicide, tungsten silicide, zirconium silicide, tantalum silicide, and chromium silicide having a high oxidative decomposition starting temperature. This is because when the transition metal silicide having a high oxidative decomposition starting temperature is used, the sintering temperature can be increased, and thus the transition metal silicide can be strongly sintered.
  • zirconium silicide and tungsten silicide it is more preferable to use at least one of zirconium silicide and tungsten silicide, and it is more preferable to use zirconium silicide.
  • the reason why excellent output characteristics can be obtained when at least one of zirconium silicide and tungsten silicide is used is as follows. That is, the compound produced by the interdiffusion of elements between the lithium transition metal composite oxide particles and the transition metal silicide functions as a catalyst, and the activity of the reaction between the lithium-containing transition metal compound and lithium ions. It is considered that excellent output characteristics can be obtained because of the reduction in the activation energy.
  • the lithium transition metal composite oxide particles are usually mixed with a lithium source such as lithium carbonate and lithium hydroxide and a transition metal source such as transition metal hydroxide at a predetermined ratio, and oxidized and fired at about 800 to 900 ° C. Can be obtained.
  • a transition metal silicide is added at this firing stage, the transition metal silicide is oxidatively decomposed, and the transition metal silicide diffuses into the lithium-containing transition metal oxide particles, so that the conductivity of the transition metal silicide is increased. Lost. For this reason, in order to sinter the transition metal silicide on the surface of the lithium-containing transition metal oxide particles, it is desirable to mix both and then fire at the above temperature range.
  • nonaqueous electrolyte secondary battery according to the present invention will be specifically described with reference to examples.
  • the nonaqueous electrolyte secondary battery of the present invention is not limited to the following examples, and can be implemented with appropriate modifications within a range not changing the gist thereof.
  • Li 2 CO 3 and Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 obtained by the coprecipitation method are mixed at a predetermined ratio, and these are fired in the air to form a layered structure.
  • LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles were prepared. The average particle size of primary particles of this particle was about 1 ⁇ m, and the average particle size of secondary particles was about 10 ⁇ m.
  • the LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles and the WSi 2 particles having an average particle diameter of 3 ⁇ m are in a molar ratio of 99: 1.
  • WSi 2 particles were adhered to the surface of LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles.
  • baked 1 hour at 600 ° C. in air to prepare a positive electrode active material WSi 2 is formed by baking on the surface of LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles.
  • a positive electrode active material, an artificial graphite as a conductive agent, and an N-methyl-2-pyrrolidone solution in which polyvinylidene fluoride as a binder is dissolved are mixed in a mass ratio of the positive electrode active material, the conductive agent, and the binder.
  • a slurry was applied onto a positive electrode current collector made of an aluminum foil, dried, rolled with a rolling roller, and an aluminum current collecting tab was attached thereto to complete a positive electrode.
  • FIG. 3 shows a scanning electron micrograph of the positive electrode active material produced in Example 1.
  • the light-colored particles are WSi 2 particles.
  • Example 1 A positive electrode was produced in the same manner as in Example 1 except that WSi 2 was not added and not fired, and a three-electrode test cell 20 was produced.
  • Comparative Example 2 Similarly to Example 1, using a mechanofusion manufactured by Hosokawa Micron Co., Ltd., LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles and WSi 2 particles having an average particle diameter of 3 ⁇ m were in a molar ratio of 99: 1. WSi 2 particles were adhered to the surface of LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles. However, in Comparative Example 2, the firing of the LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles and the WSi 2 particles was not performed. Otherwise, a positive electrode was produced in the same manner as in Example 1, and a three-electrode test cell 20 was produced.
  • Example 2 A positive electrode was produced in the same manner as in Example 1 except that ZrSi 2 having an average particle diameter of 2 ⁇ m was used as a transition metal silicide, and a three-electrode test cell 20 was produced. Also in Example 2, when the crystal structure of the positive electrode active material was confirmed using XRD, it was confirmed that the structure of ZrSi 2 before firing was maintained in the transition metal silicide after firing.
  • Example 3 A positive electrode was prepared in the same manner as in Example 2 except that firing of LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles and ZrSi 2 particles was not performed, and a three-electrode test cell 20 was made.
  • Example 3 A positive electrode was produced in the same manner as in Example 1 except that TiSi 2 having an average particle diameter of 1 ⁇ m was used as a transition metal silicide, and a three-electrode test cell 20 was produced. Also in Example 3, when the crystal structure of the positive electrode active material was confirmed using XRD, it was confirmed that the structure of TiSi 2 before firing was maintained even in the transition metal silicide after firing.
  • Example 4 A positive electrode was produced in the same manner as in Example 3 except that firing of LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles and TiSi 2 particles was not performed, and a three-electrode test cell 20 was made.
  • the three-electrode test cell was charged at a constant current of up to 4.5 V (vs. Li / Li + ) at a current density of 2.0 mA / cm 2 at 25 ° C., and then the current density was 0.025 mA. Constant current-constant voltage charging was performed, maintaining a constant potential of 4.5 V (vs. Li / Li + ) until reaching / cm 2 .
  • the three-electrode test cell was stored at 60 ° C. for 10 days, it was discharged at 10.0 mA / cm 2 at 25 ° C., and the average discharge operating potential at that time was measured as the average discharge operating position after storage.
  • Example 4 A positive electrode was produced in the same manner as in Example 1 except that the firing temperature of LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles and WSi 2 particles was 500 ° C. A cell 20 was produced. Also in Example 4, when the crystal structure of the positive electrode active material was confirmed using XRD, it was confirmed that the structure of WSi 2 before firing was maintained even in the transition metal silicide after firing.
  • Comparative Example 5 A positive electrode was produced in the same manner as in Example 1 except that the firing temperature of LiNi 0.5 Co 0.2 Mn 0.3 O 2 particles and WSi 2 particles was 700 ° C. A cell 20 was produced. Also in Comparative Example 5, when the crystal structure of the positive electrode active material was confirmed using XRD, no peak derived from WSi 2 crystals was observed after firing, and WSi 2 was oxidized and decomposed. Was suggested.
  • Li 2 CO 3 and Ni 0.45 Co 0.30 Mn 0.25 (OH) 2 obtained by the coprecipitation method are mixed at a predetermined ratio, and these are fired in the air to form a layered structure.
  • LiNi 0.45 Co 0.30 Mn 0.25 O 2 particles were prepared. The average particle size of primary particles of this particle was about 1 ⁇ m, and the average particle size of secondary particles was about 10 ⁇ m.
  • the LiNi 0.45 Co 0.30 Mn 0.25 O 2 particles and the ZrSi 2 particles having an average particle diameter of 2 ⁇ m are set to a molar ratio of 99: 1.
  • ZrSi 2 particles were adhered to the surface of LiNi 0.45 Co 0.30 Mn 0.25 O 2 particles.
  • baked 1 hour at 600 ° C. in air the surface of LiNi 0.45 Co 0.30 Mn 0.25 O 2 particles ZrSi 2 particles to prepare a positive electrode active material made by firing.
  • Li 2 CO 3 and Ni 0.55 Co 0.25 Mn 0.20 (OH) 2 obtained by the coprecipitation method are mixed at a predetermined ratio, and these are fired in the air, thereby forming a layered structure.
  • LiNi 0.55 Co 0.25 Mn 0.20 O 2 particles were prepared. The average particle size of primary particles of this particle was about 1 ⁇ m, and the average particle size of secondary particles was about 10 ⁇ m.
  • the LiNi 0.55 Co 0.25 Mn 0.20 O 2 particles and the ZrSi 2 particles having an average particle diameter of 2 ⁇ m are set to a molar ratio of 99: 1.
  • ZrSi 2 particles were adhered to the surface of LiNi 0.55 Co 0.25 Mn 0.20 O 2 particles.
  • baked 1 hour at 600 ° C. in air the surface of LiNi 0.55 Co 0.25 Mn 0.20 O 2 particles ZrSi 2 particles to prepare a positive electrode active material made by firing.
  • Example 6 A positive electrode was prepared in the same manner as in Example 1 except that the ZrSi 2 particles were not adhered to the surface of the LiNi 0.50 Co 0.20 Mn 0.30 O 2 particles and were not fired. An electrode type test cell 20 was produced.
  • Example 7 A positive electrode was prepared in the same manner as in Example 5 except that the ZrSi 2 particles were not adhered to the surface of the LiNi 0.45 Co 0.30 Mn 0.25 O 2 particles and were not fired. An electrode type test cell 20 was produced.
  • Example 8 A positive electrode was prepared in the same manner as in Example 6 except that the ZrSi 2 particles were not attached to the surface of the LiNi 0.55 Co 0.25 Mn 0.20 O 2 particles and were not fired. An electrode type test cell 20 was produced.

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  • Organic Chemistry (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un matériau actif pour une batterie secondaire à électrolyte non aqueux qui permet la réalisation d'une batterie secondaire à électrolyte non aqueux ayant des caractéristiques de sortie élevées. Le matériau actif pour batterie secondaire à électrolyte non aqueux est formé en frittant un siliciure de métal de transition à la surface de particules d'oxyde composite de métal de transition contenant du lithium.
PCT/JP2012/070040 2011-08-16 2012-08-07 Matériau actif pour batterie secondaire à électrolyte non aqueux, batterie secondaire à électrolyte non aqueux, et procédé de fabrication d'un matériau actif pour une batterie secondaire à électrolyte non aqueux WO2013024739A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011177828 2011-08-16
JP2011-177828 2011-08-16
JP2012075662 2012-03-29
JP2012-075662 2012-03-29

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WO2013024739A1 true WO2013024739A1 (fr) 2013-02-21

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Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2017073682A1 (fr) * 2015-10-28 2017-05-04 住友金属鉱山株式会社 Matériau actif d'électrode positive pour pile rechargeable à électrolyte non aqueux, procédé de production dudit matériau et pile rechargeable à électrolyte non aqueux
CN108039466A (zh) * 2017-12-05 2018-05-15 合肥国轩高科动力能源有限公司 一种硅化钛包覆磷酸铁锂复合材料的制备方法
US20180301748A1 (en) * 2017-04-13 2018-10-18 Nichia Corporation Positive electrode material for nonaqueous secondary batteries, and nonaqueous secondary batteries using same
US11811052B2 (en) 2018-03-29 2023-11-07 Sumitomo Metal Mining Co., Ltd. Positive electrode active material for non-aqueous electrolyte secondary battery

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JP2009105017A (ja) * 2007-10-25 2009-05-14 Sanyo Electric Co Ltd 非水電解質二次電池
JP2009176597A (ja) * 2008-01-25 2009-08-06 Panasonic Corp 非水電解質二次電池
JP2011070789A (ja) * 2008-09-26 2011-04-07 Sanyo Electric Co Ltd 非水電解質二次電池
JP2011076797A (ja) * 2009-09-29 2011-04-14 Sanyo Electric Co Ltd 非水電解質二次電池

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JPH08222219A (ja) * 1995-02-14 1996-08-30 Yuasa Corp 非水電解質電池
JP2008235153A (ja) * 2007-03-23 2008-10-02 Sanyo Electric Co Ltd 非水電解質二次電池
JP2009105017A (ja) * 2007-10-25 2009-05-14 Sanyo Electric Co Ltd 非水電解質二次電池
JP2009176597A (ja) * 2008-01-25 2009-08-06 Panasonic Corp 非水電解質二次電池
JP2011070789A (ja) * 2008-09-26 2011-04-07 Sanyo Electric Co Ltd 非水電解質二次電池
JP2011076797A (ja) * 2009-09-29 2011-04-14 Sanyo Electric Co Ltd 非水電解質二次電池

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017073682A1 (fr) * 2015-10-28 2017-05-04 住友金属鉱山株式会社 Matériau actif d'électrode positive pour pile rechargeable à électrolyte non aqueux, procédé de production dudit matériau et pile rechargeable à électrolyte non aqueux
JP2017084628A (ja) * 2015-10-28 2017-05-18 住友金属鉱山株式会社 非水系電解質二次電池用正極活物質とその製造方法、及び非水系電解質二次電池
US11063257B2 (en) 2015-10-28 2021-07-13 Sumitomo Metal Mining Co., Ltd. Positive electrode active material for nonaqueous electrolyte secondary batteries, production method thereof, and nonaqueous electrolyte secondary battery
US20180301748A1 (en) * 2017-04-13 2018-10-18 Nichia Corporation Positive electrode material for nonaqueous secondary batteries, and nonaqueous secondary batteries using same
US10741876B2 (en) 2017-04-13 2020-08-11 Nichia Corporation Positive electrode material for noaqueous secondary batteries, and nonaqueous secondary batteries using same
CN108039466A (zh) * 2017-12-05 2018-05-15 合肥国轩高科动力能源有限公司 一种硅化钛包覆磷酸铁锂复合材料的制备方法
CN108039466B (zh) * 2017-12-05 2020-07-17 合肥国轩高科动力能源有限公司 一种硅化钛包覆磷酸铁锂复合材料的制备方法
US11811052B2 (en) 2018-03-29 2023-11-07 Sumitomo Metal Mining Co., Ltd. Positive electrode active material for non-aqueous electrolyte secondary battery

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