WO2012085994A1 - Electrode for lithium ion secondary battery, and lithium ion secondary battery - Google Patents

Electrode for lithium ion secondary battery, and lithium ion secondary battery Download PDF

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Publication number
WO2012085994A1
WO2012085994A1 PCT/JP2010/072873 JP2010072873W WO2012085994A1 WO 2012085994 A1 WO2012085994 A1 WO 2012085994A1 JP 2010072873 W JP2010072873 W JP 2010072873W WO 2012085994 A1 WO2012085994 A1 WO 2012085994A1
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Prior art keywords
electrode
lithium ion
ion secondary
secondary battery
oxide particles
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PCT/JP2010/072873
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French (fr)
Japanese (ja)
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澤木　裕子
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株式会社日立製作所
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Priority to PCT/JP2010/072873 priority Critical patent/WO2012085994A1/en
Priority to KR1020110091741A priority patent/KR20120069531A/en
Priority to US13/229,576 priority patent/US20120156558A1/en
Priority to CN201110276997XA priority patent/CN102544439A/en
Publication of WO2012085994A1 publication Critical patent/WO2012085994A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 lithium ion secondary battery having good load characteristics and an electrode that can constitute the lithium ion secondary battery.
  • Lithium ion secondary batteries are being rapidly developed as batteries for use in portable electronic devices and hybrid vehicles.
  • a carbon material is mainly used as the negative electrode active material, and metal oxides, metal sulfides, various polymers, and the like are used as the positive electrode active material.
  • lithium composite oxides such as lithium cobaltate, lithium nickelate, and lithium manganate can be used as a positive electrode active material for lithium ion secondary batteries because they can realize high energy density and high voltage batteries. It has been.
  • the lithium ion conduction inside the battery is It is conceivable to respond to this by increasing the nature.
  • the lithium ion secondary battery the following are mainly involved in lithium ion conductivity.
  • Patent Document 1 proposes a technique for reducing the internal resistance of a battery by lowering the interface resistance between the positive electrode active material and the electrolytic solution by covering the surface of the positive electrode active material with a layer containing phosphorus.
  • Patent Document 2 discloses that the addition of 4-fluoro-1,3-dioxolan-2-one as an additive to the electrolytic solution improves the lithium ion conductivity in the electrolytic solution, A technique for improving the ionic conductivity of SEI (Solid (Electrolyte Interface) coating has been proposed.
  • SEI Solid (Electrolyte Interface) coating
  • Patent Documents 3 to 5 propose a technique for containing oxide particles in the active material layer (mixture layer) of the positive electrode and the negative electrode. It is described that the lithium ion conductivity of the SEI film can be improved. According to these methods, it is considered that there is a possibility that the desolvation reaction energy can also be reduced by improving the SEI film.
  • This invention is made
  • the objective is to provide the lithium ion secondary battery which has a favorable load characteristic, and the electrode which can comprise this lithium ion secondary battery. .
  • the electrode for a lithium ion secondary battery of the present invention that can achieve the above object is for a lithium ion secondary battery having an electrode mixture layer containing oxide particles, active material particles capable of occluding and releasing Li, and a resin binder.
  • the lithium ion secondary battery of the present invention has a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, and the positive electrode and / or the negative electrode is an electrode for a lithium ion secondary battery according to the present invention. It is characterized by being.
  • the present invention it is possible to provide a lithium ion secondary battery having good load characteristics and an electrode that can constitute the lithium ion secondary battery.
  • FIG. 2 is a powder X-ray diffraction spectrum of oxide particles used in the negative electrode for the lithium ion secondary battery of Example 1.
  • An electrode for a lithium ion secondary battery of the present invention (hereinafter sometimes simply referred to as “electrode”) has an electrode mixture layer containing active material particles capable of occluding and releasing Li, oxide particles, and a resin binder.
  • the electrode mixture layer has a structure formed on one side or both sides of the current collector, for example.
  • the electrode of the present invention is used for a positive electrode or a negative electrode of a lithium ion secondary battery.
  • the oxide particles contained in the electrode mixture layer according to the electrode of the present invention are fine and have low crystallinity.
  • the diffusion polarization of lithium ions is reduced by the influence of the element (metal element) contained in the oxide particles.
  • the interface resistance between this electrode (the active material contained therein) and the non-aqueous electrolyte is reduced. Can be lowered.
  • load characteristics can be improved by these actions of the oxide particles.
  • the non-aqueous electrolyte contained in the battery is smoothly introduced into the electrode mixture layer due to the surface polarity of the oxide particles. Therefore, for example, even if the electrode mixture layer is thickened, the effective reaction area of the active material of the electrode can be maintained well, and the charge / discharge cycle characteristics of the battery can be improved.
  • the oxide particles have an average primary particle size of 20 nm or less, preferably 10 nm or less. With such fine oxide particles, the effect of improving the load characteristics of the battery is satisfactorily exhibited. Even if the size of the oxide particles is large, when the crystallinity is low, for example, there is a certain effect in reducing the interface resistance between the electrode and the non-aqueous electrolyte. However, in this case, since large particles having insulating properties are present in the electrode mixture layer, the DC electric resistance increases as a whole of the electrode mixture layer, and the load of the battery using this electrode is increased. Effective improvement of characteristics cannot be expected.
  • the average particle diameter of the primary particles of the oxide particles is 1 nm or more, and preferably 1.5 nm or more.
  • the average particle diameter of the primary particles of the oxide particles referred to in this specification is the particle diameter (when the particles are spherical) or the length of 300 primary particles of the oxide particles observed with a transmission electron microscope (TEM). This is an average value obtained by determining the diameter of the axial length (when the particles have a shape other than a sphere) and dividing the total value of these particle diameters by the number (300).
  • the average particle size of the primary particles may be obtained by a small angle X-ray scattering method.
  • action which improves the load characteristic of the said battery will be exhibited favorably.
  • the crystallinity of the oxide particles is high, in the case of the fine form as described above, the load characteristics of the battery having the electrode using the same are not impaired, but the electrode and the non-aqueous electrolyte The effect of reducing the interfacial resistance is small, and a large improvement in the load characteristics of the battery cannot be expected.
  • the oxide particles preferably have a specific surface area measured by nitrogen gas adsorption of 30 m 2 / g or more, more preferably 100 m 2 / g or more, and 500 m 2 / g or less. Preferably there is.
  • the specific surface area of the oxide particles is as described above, the effect of increasing the load characteristics of the battery is further improved. This is because, if the oxide particles have a low crystallinity and a large surface area as described above, for example, many dangling bonds remain on the outermost surface. This is probably because the dissociation of lithium is promoted and the diffusion polarization of lithium ions is further reduced.
  • the specific surface area of the oxide particles referred to in the present specification is a specific surface area of the surface of the oxide particles and the fine pores, which is obtained by measuring and calculating the surface area using the BET equation, which is a theoretical formula of multimolecular layer adsorption. .
  • BET equation which is a theoretical formula of multimolecular layer adsorption.
  • measurement was performed up to a relative pressure of 0.99 with respect to the saturated vapor pressure, and the BET specific surface area was obtained. Value.
  • the saturated vapor pressure is the pressure at the start of measurement
  • the dead volume is an actual measurement value
  • the pre-measurement drying conditions are 80 ° C. for 2 hours in a nitrogen gas flow.
  • oxide constituting the oxide particles for example, since an oxide having lower crystallinity is easily obtained, at least selected from the group consisting of Si, Zr, Al, Ce, Mg, Ti, Ba and Sr. An oxide containing one kind of element can be given.
  • the oxide may be a substitute for another element containing an element other than each of the above elements.
  • Good For example, one obtained by substituting a part of Zr in the ZrO y with Y may be used.
  • an oxide in which a part of Ti in TiBaO 3 is substituted with Sr can be used.
  • the oxide particles for example, only one kind of particles composed of these oxides may be used, or two or more kinds may be used in combination.
  • any synthesis method may be adopted as long as it is a method capable of obtaining oxide particles having low crystallinity.
  • the heating temperature It is preferable to employ a synthesis method by oxidation treatment in an aqueous solution such as hydrothermal treatment (hydrothermal synthesis method) at a low temperature.
  • the raw material contains an element (an element other than oxygen) constituting the oxide particles because it needs to be dissolved in water.
  • an element an element other than oxygen
  • water-soluble salts examples include sulfates, nitrates, and chlorides containing elements that constitute oxide particles.
  • the aqueous solution of the raw material (water-soluble salt) as described above is neutralized by introducing an alkaline aqueous solution such as an aqueous solution of an alkali metal hydroxide such as ammonia water or sodium hydroxide. And a precipitate is obtained by a coprecipitation method, and then this is oxidized in an aqueous solution.
  • an alkaline aqueous solution such as an aqueous solution of an alkali metal hydroxide such as ammonia water or sodium hydroxide.
  • a precipitate is obtained by a coprecipitation method, and then this is oxidized in an aqueous solution.
  • a hydrothermal treatment method in which heat treatment is performed under pressure, or the like can be applied.
  • the oxidizing agent may remain as an impurity, care must be taken when selecting it.
  • oxidation by bubbling may be performed at the same time as the coprecipitation. After the suspension containing the generated precipitate is washed well, the precipitate is taken out of the solution by filtration and dried. To obtain oxide particles.
  • the suspension obtained by the coprecipitation method (the aqueous solution containing the precipitate) is heated in a sealed container to heat-treat under pressure, and then the suspension is thoroughly washed.
  • the precipitate is removed by filtration and dried to obtain oxide particles.
  • the SiO x , ZrO 2 ⁇ nH 2 O, AlOOH, Al (OH) 3 , MgO a ⁇ mH 2 O, etc. are obtained by obtaining a glassy precipitate by hydrothermal treatment, and then taking it out and drying it. It is preferable to obtain oxide particles through this.
  • the suspension in the hydrothermal treatment method preferably has a pH of 4 to 11 by adjusting the amount of the alkaline aqueous solution to be added, and the target oxide is precipitated within such a range. What is necessary is just to select pH to obtain.
  • a glassy precipitate is obtained by hydrothermal treatment, for example, in the case of SiO x , ZrO 2 .nH 2 O, AlOOH, Al (OH) 3 , MgO a ⁇ mH 2 O, etc.
  • the pH of the suspension is more preferably from 4 to 7 in a weakly acidic to neutral range.
  • the pH after adding the alkaline aqueous solution to the raw material aqueous solution is the same as the pH in the suspension in the hydrothermal treatment method. .
  • the heating temperature in the hydrothermal treatment method is preferably 60 ° C. or higher, and is preferably 200 ° C. or lower. Note that it is more preferable to select a heating temperature that is low enough to prevent excessive crystallization of the oxide particles. Specifically, the heating temperature is more preferably 80 ° C. or higher, more preferably 150 ° C. or lower, and still more preferably 120 ° C. or lower.
  • the heating time in the hydrothermal treatment method is preferably 1 hour or longer from the viewpoint of suppressing the formation of particles that are insufficiently oxidized and dehydrated.
  • the heating time in the hydrothermal treatment method is preferably 40 hours or less, and more preferably 6 hours or less.
  • the electrode of the present invention from the viewpoint of ensuring the above-mentioned effects by using the oxide particles satisfactorily, when the total of the oxide particles and the active material particles contained in the electrode mixture layer is 100% by mass
  • the ratio of the oxide particles is 0.1% by mass or more, preferably 0.5% by mass or more.
  • the content of the oxide particles in the electrode mixture layer is excessively large, an insulating material is present in a large amount in the electrode mixture layer, and the direct current resistance of the electrode is increased. The load characteristic of the battery using the electrode is lowered. Therefore, when the total of the oxide particles and the active material particles contained in the electrode mixture layer is 100% by mass, the ratio of the oxide particles is 10% by mass or less, preferably 5% by mass or less.
  • the active material particles include active material particles used for a negative electrode of a conventionally known lithium ion secondary battery, that is, Li. Active material particles that can be occluded and released can be used. Specific examples of such active material particles include, for example, graphite (natural graphite; artificial graphite obtained by graphitizing graphitized carbon such as pyrolytic carbons, MCMB, and carbon fiber at 2800 ° C.
  • heat Carbon materials such as decomposed carbons, cokes, glassy carbons, fired organic polymer compounds, mesocarbon microbeads, carbon fibers and activated carbon; metals that can be alloyed with lithium (Si, Sn, etc.), and these And other particles containing a metal (such as an alloy).
  • these active material particles may be used alone or in combination of two or more.
  • the active material particles include active material particles used for a positive electrode of a conventionally known lithium ion secondary battery, that is, Active material particles capable of occluding and releasing Li can be used.
  • Active material particles capable of occluding and releasing Li
  • Specific examples of such active material particles are represented by, for example, Li 1 + c M 1 O 2 ( ⁇ 0.1 ⁇ c ⁇ 0.1, M 1 : Co, Ni, Mn, Al, Mg, etc.).
  • Lithium-containing transition metal oxide having a layered structure LiMn 2 O 4 and a spinel-structured lithium manganese oxide obtained by substituting some of its elements with other elements, LiM 2 PO 4 (M 2 : Co, Ni, Mn, Fe, etc. It is possible to use particles such as olivine type compounds represented by Specific examples of the lithium-containing transition metal oxide having a layered structure include LiCoO 2 and LiNi 1-d Co d e Al e O 2 (0.1 ⁇ d ⁇ 0.3, 0.01 ⁇ e ⁇ 0.
  • Electrode of the present invention is used as a positive electrode for a lithium ion secondary battery, these active material particles may be used alone or in combination of two or more.
  • the active material particles when the electrode of the present invention is a negative electrode for a lithium ion secondary battery and the active material particles when the electrode is a positive electrode for a lithium ion secondary battery are measured by the same method as the oxide particles.
  • the average particle diameter of the primary particles is preferably 50 nm or more, more preferably 500 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the resin binder according to the electrode mixture layer of the electrode of the present invention is used in a conventionally known positive electrode mixture layer related to a positive electrode for a lithium ion secondary battery and a negative electrode mixture layer related to a negative electrode.
  • the same resin binder can be used.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • SBR styrene butadiene rubber
  • CMC carboxymethyl cellulose
  • the electrode mixture layer according to the electrode of the present invention may contain a conductive auxiliary as necessary.
  • conductive aids include, for example, graphite such as natural graphite (eg, flaky graphite) and artificial graphite; carbon such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. Black; carbon fiber; and the like.
  • the composition of each component in the electrode mixture layer is, for example, 85 to 99% by mass of active material particles, and a resin binder. Is preferably 1.0 to 10% by mass. In the case where a conductive auxiliary is used, the amount of the conductive auxiliary in the electrode mixture layer is preferably 0.5 to 10% by mass.
  • the thickness of the electrode mixture layer (negative electrode mixture layer) (when the electrode mixture layer is formed on one side or both sides of the current collector, the thickness per side of the current collector) is 30 to 150 ⁇ m. It is preferable.
  • the current collector can be made of copper or nickel foil, punched metal, net, expanded metal, etc. Copper foil is used.
  • the thickness of the current collector is preferably 5 to 30 ⁇ m.
  • the composition of each component in the electrode mixture layer is, for example, 75 to 95% by mass of active material particles, and a resin binder. Is preferably 2 to 15% by mass, and the conductive auxiliary is preferably 2 to 15% by mass.
  • the thickness of the electrode mixture layer (positive electrode mixture layer) is the single side of the current collector. The thickness is preferably 30 to 180 ⁇ m.
  • the electrode of the present invention When the electrode of the present invention is used as a positive electrode for a lithium ion secondary battery having a current collector, an aluminum foil, punching metal, net, expanded metal, or the like can be used as the current collector. Is used.
  • the thickness of the current collector is preferably 10 to 30 ⁇ m.
  • the electrode of the present invention includes, for example, an electrode mixture containing the oxide particles, active material particles and resin binder, and optionally a conductive auxiliary agent, such as N-methyl-2-pyrrolidone (NMP).
  • An electrode mixture-containing composition prepared by dispersing in a solvent such as organic solvent or water is applied to one side or both sides of the current collector, dried, and subjected to press treatment as necessary. It can be manufactured through a process.
  • the electrode mixture The dispersed particle diameter of the oxide particles in the layer is preferably 300 nm or less.
  • the dispersed particle diameter of the oxide particles referred to here is determined by observing the cross section of the electrode with a scanning electron microscope (SEM), and the oxide particles (the oxide particles dispersed in the state of primary particles and the secondary particles). It is a value obtained by measuring the diameter of the largest particle of 100 particles (including oxide particles that are aggregated and dispersed in a state).
  • the oxide particles are dispersed in the same solvent as the solvent used for the electrode mixture-containing composition to prepare an oxide particle dispersion.
  • This oxide particle dispersion preferably does not contain an organic substance such as a resin binder or a dispersant.
  • a known disperser suitable for the preparation of the nanoparticle dispersion such as a ball mill, nanomill, picomill, paint shaker, or dissolver can be used.
  • the dispersion conditions of the oxide particle dispersion and the concentration (solid content concentration) of the oxide particles in the oxide particle dispersion are such that the dispersed particle diameter of the oxide particles is 300 nm in the electrode mixture layer to be formed later. What is necessary is just to select the conditions and solid content concentration which become the following. Specifically, the solid content concentration of the oxide particle dispersion is 5 to 50 in consideration of, for example, an electrode mixture-containing composition later and easy handling such as dispersion stability. It is preferable to set it as the mass%.
  • the dispersion time is 5 minutes to 2 minutes. It is preferable to set it to about time.
  • the active material particles and the resin binder, and further, if necessary, a conductive auxiliary agent and a solvent are added to and mixed with the oxide particle dispersion prepared as described above to prepare an electrode mixture-containing composition.
  • the active material particles, the resin binder, and the conductive auxiliary are previously dispersed in a solvent to prepare a dispersion (the resin binder may be dissolved in the solvent).
  • An electrode mixture-containing composition may be prepared by mixing with a particle dispersion.
  • a disperser using a dispersion medium such as zirconia beads can be used. Since there is a possibility of damaging the active material particles, it is more preferable to use a medialess disperser.
  • the medialess disperser include general-purpose dispersers such as a hybrid mixer, a nanomizer, and a jet mill.
  • an electrode mixture layer is formed using the electrode mixture-containing composition prepared as described above, and the electrodes subjected to press treatment as necessary are connected to terminals in the battery according to a conventional method.
  • the lead part for doing can be formed.
  • the lithium ion secondary battery of the present invention (hereinafter sometimes simply referred to as “battery”) includes a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, and at least one of the positive electrode and the negative electrode is the lithium of the present invention. Any other configuration and structure may be used as long as it is an electrode for an ion secondary battery, and various configurations and structures employed in conventionally known lithium ion secondary batteries can be applied.
  • only one of the positive electrode and the negative electrode may be the electrode of the present invention, and both the positive electrode and the negative electrode may be the electrode of the present invention.
  • a positive electrode having the same configuration as the electrode (positive electrode) of the present invention can be used as the positive electrode except that the oxide particles are not contained.
  • the negative electrode having the same configuration as the electrode (negative electrode) of the present invention may be used except that the oxide particles are not included. it can.
  • the separator according to the battery of the present invention has a property (that is, a shutdown function) that the pores are blocked at 80 ° C. or higher (more preferably 100 ° C. or higher) and 170 ° C. or lower (more preferably 150 ° C. or lower).
  • separators used in ordinary lithium ion secondary batteries for example, microporous membranes made of polyolefin such as polyethylene (PE) and polypropylene (PP) can be used.
  • the microporous film constituting the separator may be, for example, one using only PE or one using PP, or a laminate of a PE microporous film and a PP microporous film. There may be.
  • the thickness of the separator is preferably 10 to 30 ⁇ m, for example.
  • the positive electrode, the negative electrode, and the separator are formed in the form of a laminated electrode body in which a separator is interposed between the positive electrode and the negative electrode, or a wound electrode body in which the separator is wound in a spiral shape. It can be used for the battery of the invention.
  • nonaqueous electrolytic solution examples include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propionate, ethylene carbonate, propylene carbonate, butylene carbonate, gamma-butyrolactone, ethylene glycol sulfite, 1,2- dimethoxyethane, 1,3-dioxolane, tetrahydrofuran, 2-methyl - tetrahydrofuran, organic solvents such as diethyl ether, for example, LiClO 4, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ⁇ 2), LiN (R f OSO 2 ) 2 [wherein R f is a fluoroal
  • the concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.5 to 1.5 mol / l, particularly 0.9 to 1.25 mol / l.
  • vinylene carbonates, 1,3-propane sultone, diphenyl disulfide, cyclohexyl benzene, biphenyl, fluorobenzene, t for the purpose of improving safety, charge / discharge cycleability, and high-temperature storage properties of these electrolytes -Additives such as butylbenzene can be added as appropriate.
  • Examples of the form of the lithium ion secondary battery of the present invention include a cylindrical shape (such as a square cylindrical shape or a cylindrical shape) using a steel can or an aluminum can as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
  • the lithium ion secondary battery of the present invention has excellent load characteristics and charge / discharge cycle characteristics, and conventionally known lithium ion secondary batteries are applied, including applications in which such characteristics are particularly required. It can be used for the same applications as various applications.
  • Example 1 ⁇ Synthesis of zirconia particles> First, chlorinated zirconium oxide octahydrate was dissolved in water to prepare an aqueous 8 mass% zirconium salt solution. Next, the zirconium salt aqueous solution was added dropwise to a 1.4 mass% ammonia aqueous solution while stirring to produce a precipitate containing zirconium oxide hydrate particles. The suspension containing this precipitate was aged at room temperature for 21 hours.
  • the suspension was charged in an autoclave, heated to 100 ° C. over 1 hour, then hydrothermally treated at 100 ° C. for 7 hours, cooled to room temperature over 10 hours, and then aged at room temperature for 36 hours. I let you.
  • the powder X-ray diffraction spectrum of the zirconium oxide hydrate particles is shown in FIG.
  • required by the said method is 2.1 nm
  • suction is 433 m ⁇ 2 >. / G.
  • ⁇ Preparation of negative electrode mixture-containing composition The zirconium oxide hydrate particles in an amount of 20% by mass were added to water and mixed with a paint shaker for 1 hour using ⁇ 0.3 mm zirconia beads to prepare an aqueous dispersion of zirconium oxide hydrate particles. .
  • the dispersion particle diameter of the zirconium oxide hydrate particles in this dispersion was 116 nm.
  • Scale-like graphite manufactured by Hitachi Chemical Co., Ltd., average particle diameter of primary particle diameter: about 450 ⁇ m
  • CMC 1 part by mass are dispersed in water: 100 parts by mass.
  • a prepared dispersion was prepared. To this dispersion: 100 parts by mass, the above-mentioned aqueous dispersion of zirconium oxide hydrate particles: 2.5 parts by mass was added, and the mixture was mixed for about 15 minutes using a paint shaker without using beads for dispersion.
  • a negative electrode mixture-containing composition containing 1% by mass of zirconium oxide hydrate particles in a total of 100% by mass of zirconia and zirconium oxide hydrate particles was prepared.
  • the negative electrode mixture-containing composition is applied to one side of a copper foil having a thickness of 8 ⁇ m as a current collector using an applicator, dried, pressed, cut into a size of 35 ⁇ 35 mm, and the negative electrode Was made.
  • the thickness of the negative electrode mixture layer of the obtained negative electrode was 63 ⁇ m.
  • the positive electrode and the negative electrode are laminated via a separator (PE microporous film having a thickness of 16 ⁇ m) and inserted into a laminate film exterior, and a non-aqueous electrolyte (volume ratio of ethylene carbonate and diethyl carbonate) After injecting LiPF 6 at a concentration of 1.2 M into a 3: 7 mixed solvent, the laminate film outer package was sealed to prepare a test cell.
  • a separator PE microporous film having a thickness of 16 ⁇ m
  • a non-aqueous electrolyte volume ratio of ethylene carbonate and diethyl carbonate
  • Example 2 Cerium chloride heptahydrate was dissolved in water to prepare a 3.0% by mass aqueous cerium chloride solution.
  • the aqueous solution of cerium chloride and the aqueous solution of sodium hydroxide having the same number of bases are used as the alkaline solution.
  • the aqueous solution of cerium chloride is added dropwise to precipitate the hydroxide, and then the suspension.
  • the pH of was adjusted to 8. Thereafter, the suspension was aged at room temperature for about 12 hours, then the pH was adjusted again to 8 and subjected to hydrothermal treatment at 180 ° C. for 5 hours in the same manner as in Example 1, and further in the same manner as in Example 1.
  • the average particle diameter of the primary particles determined by the above method is 2.2 nm, and the specific surface area (BET specific surface area) determined by nitrogen gas adsorption is 220 m 2 / g. there were.
  • a negative electrode was prepared in the same manner as in Example 1 except that this cerium oxide particle was used in place of the zirconium oxide hydrate particles, and a test cell (lithium) was prepared in the same manner as in Example 1 except that this negative electrode was used.
  • An ion secondary battery was produced.
  • Example 3 Aluminum chloride was dissolved in water to prepare 4.0 mass% aluminum chloride aqueous solution.
  • the aqueous solution of aluminum chloride and the aqueous solution of sodium hydroxide having the same base number are used as the alkaline solution, and the aqueous solution of aluminum chloride is added dropwise to precipitate the hydroxide while stirring the solution at room temperature.
  • the pH of the was adjusted to 5.
  • a hydrothermal treatment was performed at 90 ° C. for 36 hours in the same manner as in Example 1 to obtain an aluminum gel. After washing with water in the same manner as in Example 1, filtration and drying were performed.
  • aluminum hydroxide [Al (OH) 3 ] particles were obtained.
  • required by the said method is 8.2 nm
  • suction is 85 m ⁇ 2 > / g. Met.
  • a negative electrode was prepared in the same manner as in Example 1 except that this aluminum hydroxide particle was used in place of the zirconium oxide hydrate particles, and a test cell (in the same manner as in Example 1 except that this negative electrode was used) Lithium ion secondary battery) was produced.
  • Comparative Example 1 A negative electrode was prepared in the same manner as in Example 1 except that zirconium oxide hydrate particles were not used, and a test cell (lithium ion secondary battery) was prepared in the same manner as in Example 1 except that this negative electrode was used. Produced.
  • Comparative Example 2 Scale-like graphite and hydrated zirconium oxide were the same as in Example 1 except that the dispersion containing scale-like graphite and the like: 100 parts by mass and the aqueous dispersion of zirconium oxide hydrate particles: 43 parts by mass were added. A negative electrode mixture-containing composition containing 15% by mass of zirconium oxide hydrate particles in a total of 100% by mass with product particles was prepared.
  • a negative electrode was produced in the same manner as in Example 1 except that this negative electrode mixture-containing composition was used, and a test cell (lithium ion secondary battery) was produced in the same manner as in Example 1 except that this negative electrode was used. did.
  • Example 3 Zirconium oxide hydrate particles synthesized in the same manner as in Example 1 were heat-treated in air at 600 ° C. for 2 hours to obtain zirconium oxide particles.
  • required by the said method was 25 nm, and the specific surface area (BET specific surface area) calculated
  • a negative electrode was prepared in the same manner as in Example 1 except that this zirconium oxide particle was used in place of the zirconium oxide hydrate particles, and a test cell (lithium) was prepared in the same manner as in Example 1 except that this negative electrode was used.
  • An ion secondary battery was produced.
  • required by the said method is 274 nm, and the specific surface area (BET specific surface area) calculated
  • a negative electrode was prepared in the same manner as in Example 1 except that this aluminum oxide particle was used in place of the zirconium oxide hydrate particles, and a test cell (lithium) was prepared in the same manner as in Example 1 except that this negative electrode was used.
  • An ion secondary battery was produced.
  • the load characteristics and charge / discharge cycle characteristics of the test cells of the examples and comparative examples were evaluated by the following methods.
  • each test cell was charged under the same conditions as described above, and then discharged at a 5 C current ground until the voltage became 2.5 V to obtain a 5 C discharge capacity. And about each test cell, the value which remove
  • Tables 1 and 2 show the composition of the oxide particles used in the test cells of Examples and Comparative Examples, and Table 3 shows the evaluation results.
  • “Ratio” in Table 2 means the ratio of oxide particles in 100% by mass of the total of active material particles and oxide particles.
  • test cells of Examples 1 to 3 each having a negative electrode containing an appropriate amount of oxide particles having an appropriate primary particle average particle size and low crystallinity are as follows. Compared with the test cell of Comparative Example 1 having a negative electrode containing no oxide particles, the load characteristics and charge / discharge cycle characteristics are excellent.
  • the test cell of Comparative Example 2 using a negative electrode having too much amount of oxide particles has the effect of lowering the electronic conductivity due to the mixing of insulating particles as well as the effect of containing oxide particles. Although the load characteristic does not deteriorate, the improvement effect is inferior to that of the test cell of the example. Further, the test cells of Comparative Examples 3 and 4 have a negative electrode containing oxide particles having a high average particle size of primary particles and high crystallinity, and of these, the particle size is relatively small. The test cell of Comparative Example 3 using oxide particles has the same load characteristics as the test cell of Comparative Example 1 not using oxide particles, and Comparative Example 4 using coarser oxide particles. These test cells have inferior load characteristics as compared with the test cell of Comparative Example 1, and none of the test cells can be expected to significantly improve load characteristics.

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Abstract

[Problem] To provide: a lithium ion secondary battery which has good load characteristics; and an electrode which is capable of constituting the lithium ion secondary battery. [Solution] The above-mentioned problem is solved by an electrode for lithium ion secondary battery, which has an electrode mixture layer that contains oxide particles, active material particles capable of absorbing and desorbing Li and a resin binder, and wherein: the oxide particles have an average particle diameter of primary particles of 1-20 nm, and the oxide particles do not have a peak within the range of 2θ = 20-70˚ or have a half width of the highest intensity peak of 1.5˚ or more in a powder X-ray diffraction spectrum; and the ratio of oxide particles is 0.1-10% by mass when the total of the active material particles and the oxide particles is taken as 100% by mass. The above-mentioned problem is also solved by a lithium ion secondary battery which comprises the above-described electrode as a positive electrode and/or a negative electrode.

Description

リチウムイオン二次電池用電極およびリチウムイオン二次電池Lithium ion secondary battery electrode and lithium ion secondary battery
　本発明は、良好な負荷特性を有するリチウムイオン二次電池と、該リチウムイオン二次電池を構成し得る電極に関するものである。 The present invention relates to a lithium ion secondary battery having good load characteristics and an electrode that can constitute the lithium ion secondary battery.
　リチウムイオン二次電池は、携帯用電子機器やハイブリッド自動車などに用いるための電池として、急速に開発が進められている。このようなリチウムイオン二次電池では、負極活物質には主に炭素材料が用いられ、正極活物質には、金属酸化物、金属硫化物、各種ポリマーなどが用いられている。特に、コバルト酸リチウム、ニッケル酸リチウム、マンガン酸リチウムなどのリチウム複合酸化物は、高エネルギー密度で高電圧の電池を実現できることから、現在、リチウムイオン二次電池の正極活物質として一般的に用いられている。 Lithium ion secondary batteries are being rapidly developed as batteries for use in portable electronic devices and hybrid vehicles. In such a lithium ion secondary battery, a carbon material is mainly used as the negative electrode active material, and metal oxides, metal sulfides, various polymers, and the like are used as the positive electrode active material. In particular, lithium composite oxides such as lithium cobaltate, lithium nickelate, and lithium manganate can be used as a positive electrode active material for lithium ion secondary batteries because they can realize high energy density and high voltage batteries. It has been.
　また、現在では、使用機器の高機能化などに伴って、例えば、電池の負荷特性向上が求められているが、前記のような汎用の活物質を用いる場合には、電池内部のリチウムイオン伝導性を高めることで、これに対応することが考えられる。リチウムイオン二次電池において、リチウムイオン伝導性に関与するものとしては、主に以下のものが挙げられる。 In addition, at present, improvement of the load characteristics of the battery is demanded along with the enhancement of the function of the device used. However, when the general-purpose active material as described above is used, the lithium ion conduction inside the battery is It is conceivable to respond to this by increasing the nature. In the lithium ion secondary battery, the following are mainly involved in lithium ion conductivity.
（１）負極活物質と非水電解液との界面。
（２）正極活物質と非水電解液との界面。
（３）非水電解液中のリチウムイオンの拡散。
（４）リチウムイオンの脱溶媒和反応エネルギー。
（５）正負極の活物質内部でのリチウムイオンの拡散。 (1) An interface between the negative electrode active material and the non-aqueous electrolyte.
(2) Interface between the positive electrode active material and the non-aqueous electrolyte.
(3) Diffusion of lithium ions in the non-aqueous electrolyte.
(4) Desolvation reaction energy of lithium ions.
(5) Diffusion of lithium ions inside the active material of the positive and negative electrodes.
　これらのうち、（５）活物質内部でのリチウムイオンの拡散は、単一の結晶構造内であれば十分に速く、高負荷での放電にも対応し得ることが分かっている。その一方で、（１）～（４）については、種々の改善に向けた検討が行われている。 Among these, it has been found that (5) the diffusion of lithium ions inside the active material is sufficiently fast if it is within a single crystal structure and can cope with discharge under high load. On the other hand, (1) to (4) are being studied for various improvements.
　例えば、特許文献１には、正極活物質表面を、リンを含む層で被覆することにより、正極活物質と電解液との界面抵抗を下げ、電池の内部抵抗を低減する技術が提案されている。また、特許文献２には、電解液中に４－フルオロ－１，３－ジオキソラン－２－オンを添加剤として加えることにより、電解液中のリチウムイオン伝導度の向上を図ると共に、負極表面のＳＥＩ（Ｓｏｌｉｄ Ｅｌｅｃｔｒｏｌｙｔｅ Ｉｎｔｅｒｆａｃｅ）皮膜のイオン伝導性を高める技術が提案されている。 For example, Patent Document 1 proposes a technique for reducing the internal resistance of a battery by lowering the interface resistance between the positive electrode active material and the electrolytic solution by covering the surface of the positive electrode active material with a layer containing phosphorus. . Patent Document 2 discloses that the addition of 4-fluoro-1,3-dioxolan-2-one as an additive to the electrolytic solution improves the lithium ion conductivity in the electrolytic solution, A technique for improving the ionic conductivity of SEI (Solid （Electrolyte Interface) coating has been proposed.
　更に、特許文献３～５には、正極や負極の活物質層（合剤層）中に酸化物粒子を含有させる技術が提案されており、特許文献５には、これにより、電極表面に形成されるＳＥＩ皮膜のリチウムイオン伝導度を向上させることができる旨記載されている。なお、これらの方法によれば、ＳＥＩ皮膜の改善によって脱溶媒和反応エネルギーも減少させることができる可能性があると考えられる。 Further, Patent Documents 3 to 5 propose a technique for containing oxide particles in the active material layer (mixture layer) of the positive electrode and the negative electrode. It is described that the lithium ion conductivity of the SEI film can be improved. According to these methods, it is considered that there is a possibility that the desolvation reaction energy can also be reduced by improving the SEI film.
特開２０１０－１１８１７９号公報JP 2010-118179 A 特開２００７－１８８８６１号公報JP 2007-188861 A 特開平１０－２５５８４２号公報JP-A-10-255842 特開２００４－２００１７６号公報JP 2004-200196 A 特開２００７－３０５５４５号公報JP 2007-305545 A
　本発明は、前記事情に鑑みてなされたものであり、その目的は、良好な負荷特性を有するリチウムイオン二次電池と、該リチウムイオン二次電池を構成し得る電極とを提供することにある。 This invention is made | formed in view of the said situation, The objective is to provide the lithium ion secondary battery which has a favorable load characteristic, and the electrode which can comprise this lithium ion secondary battery. .
　前記目的を達成し得た本発明のリチウムイオン二次電池用電極は、酸化物粒子、Ｌｉを吸蔵放出可能な活物質粒子および樹脂製バインダを含む電極合剤層を有するリチウムイオン二次電池用電極であって、前記酸化物粒子は、一次粒子の平均粒子径が１～２０ｎｍであり、粉末Ｘ線回折スペクトルにおける２θ＝２０～７０°の範囲内において、ピークを有していないか、または最も強度の大きなピークの半値幅が１．５°以上であり、前記活物質粒子と前記酸化物粒子の合計を１００質量％としたとき、前記酸化物粒子の割合が０．１～１０質量％であることを特徴とするものである。 The electrode for a lithium ion secondary battery of the present invention that can achieve the above object is for a lithium ion secondary battery having an electrode mixture layer containing oxide particles, active material particles capable of occluding and releasing Li, and a resin binder. In the electrode, the oxide particles have an average primary particle diameter of 1 to 20 nm and do not have a peak within a range of 2θ = 20 to 70 ° in a powder X-ray diffraction spectrum, or When the full width at half maximum of the strongest peak is 1.5 ° or more and the total of the active material particles and the oxide particles is 100% by mass, the ratio of the oxide particles is 0.1 to 10% by mass. It is characterized by being.
　また、本発明のリチウムイオン二次電池は、正極、負極、非水電解液およびセパレータを有しており、前記正極および／または前記負極が、本発明に記載のリチウムイオン二次電池用電極であることを特徴とするものである。 The lithium ion secondary battery of the present invention has a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, and the positive electrode and / or the negative electrode is an electrode for a lithium ion secondary battery according to the present invention. It is characterized by being.
　本発明によれば、良好な負荷特性を有するリチウムイオン二次電池と、該リチウムイオン二次電池を構成し得る電極とを提供することができる。 According to the present invention, it is possible to provide a lithium ion secondary battery having good load characteristics and an electrode that can constitute the lithium ion secondary battery.
実施例１のリチウムイオン二次電池に係る負極に用いた酸化物粒子の粉末Ｘ線回折スペクトルである。2 is a powder X-ray diffraction spectrum of oxide particles used in the negative electrode for the lithium ion secondary battery of Example 1. FIG.
　本発明のリチウムイオン二次電池用電極（以下、単に「電極」という場合がある）は、Ｌｉを吸蔵放出可能な活物質粒子、酸化物粒子および樹脂製バインダを含む電極合剤層を有するものであり、この電極合剤層が、例えば、集電体の片面または両面に形成された構造を有している。本発明の電極は、リチウムイオン二次電池の正極または負極に使用される。 An electrode for a lithium ion secondary battery of the present invention (hereinafter sometimes simply referred to as “electrode”) has an electrode mixture layer containing active material particles capable of occluding and releasing Li, oxide particles, and a resin binder. The electrode mixture layer has a structure formed on one side or both sides of the current collector, for example. The electrode of the present invention is used for a positive electrode or a negative electrode of a lithium ion secondary battery.
　本発明の電極に係る電極合剤層に含有させる前記酸化物粒子は、微細かつ結晶性の低いものである。 The oxide particles contained in the electrode mixture layer according to the electrode of the present invention are fine and have low crystallinity.
　本発明の電極において、前記酸化物粒子を使用することで、この酸化物粒子に含まれる元素（金属元素）の影響によってリチウムイオンの拡散分極が低減される。また、添加した酸化物粒子によって電極の活物質の表面物性が変化するため、この電極を用いた電池において、この電極（そこに含まれる活物質）と非水電解液との間の界面抵抗を下げることができる。本発明の電極を用いた電池（本発明のリチウムイオン二次電池）では、前記酸化物粒子によるこれらの作用によって、負荷特性向上を図ることができる。 In the electrode of the present invention, by using the oxide particles, the diffusion polarization of lithium ions is reduced by the influence of the element (metal element) contained in the oxide particles. In addition, since the surface physical properties of the active material of the electrode change due to the added oxide particles, in the battery using this electrode, the interface resistance between this electrode (the active material contained therein) and the non-aqueous electrolyte is reduced. Can be lowered. In a battery using the electrode of the present invention (lithium ion secondary battery of the present invention), load characteristics can be improved by these actions of the oxide particles.
　また、本発明の電極では、前記酸化物粒子の表面極性により、電池の有する非水電解液の電極合剤層への導入がスムーズとなる。そのため、例えば、電極合剤層を厚くしても、電極の活物質の有効反応面積を良好に維持することができ、電池の充放電サイクル特性を高めることもできる。 Moreover, in the electrode of the present invention, the non-aqueous electrolyte contained in the battery is smoothly introduced into the electrode mixture layer due to the surface polarity of the oxide particles. Therefore, for example, even if the electrode mixture layer is thickened, the effective reaction area of the active material of the electrode can be maintained well, and the charge / discharge cycle characteristics of the battery can be improved.
　前記酸化物粒子は、一次粒子の平均粒子径が２０ｎｍ以下、好ましくは１０ｎｍ以下である。このような微細な酸化物粒子であれば、前記の電池の負荷特性を高める作用が良好に発揮される。酸化物粒子のサイズが大きくても、結晶性が低い場合には、例えば、電極と非水電解液との間の界面抵抗の低減については一定の効果がある。しかし、この場合、絶縁性を有するサイズの大きな粒子が電極合剤層中に存在することになるため、電極合剤層全体として直流電気抵抗が上昇してしまい、この電極を用いた電池の負荷特性の効果的な向上が見込めない。 The oxide particles have an average primary particle size of 20 nm or less, preferably 10 nm or less. With such fine oxide particles, the effect of improving the load characteristics of the battery is satisfactorily exhibited. Even if the size of the oxide particles is large, when the crystallinity is low, for example, there is a certain effect in reducing the interface resistance between the electrode and the non-aqueous electrolyte. However, in this case, since large particles having insulating properties are present in the electrode mixture layer, the DC electric resistance increases as a whole of the electrode mixture layer, and the load of the battery using this electrode is increased. Effective improvement of characteristics cannot be expected.
　ただし、あまりにサイズの小さな前記酸化物粒子の場合には、製造が困難であり、また、取り扱い性が低下する。よって、前記酸化物粒子の一次粒子の平均粒子径は、１ｎｍ以上であり、１．５ｎｍ以上であることが好ましい。 However, in the case of the oxide particles having a too small size, the production is difficult and the handleability is lowered. Therefore, the average particle diameter of the primary particles of the oxide particles is 1 nm or more, and preferably 1.5 nm or more.
　なお、本明細書でいう酸化物粒子の一次粒子の平均粒子径は、透過型電子顕微鏡（ＴＥＭ）観察した酸化物粒子の一次粒子３００個について、粒子の直径（粒子が球形の場合）または長軸長さの径（粒子が球形以外の形状の場合）を求め、これらの粒子径の合計値を個数（３００個）で除して求められる平均値である。ただし、酸化物粒子のサイズがあまりに微細で、前記の方法による測定が難しい場合には、小角Ｘ線散乱法により、一次粒子の平均粒子径を求めればよい。 In addition, the average particle diameter of the primary particles of the oxide particles referred to in this specification is the particle diameter (when the particles are spherical) or the length of 300 primary particles of the oxide particles observed with a transmission electron microscope (TEM). This is an average value obtained by determining the diameter of the axial length (when the particles have a shape other than a sphere) and dividing the total value of these particle diameters by the number (300). However, when the size of the oxide particles is too fine and measurement by the above method is difficult, the average particle size of the primary particles may be obtained by a small angle X-ray scattering method.
　また、前記酸化物粒子は、粉末Ｘ線回折スペクトルにおける２θ＝２０～７０°の範囲内において、ピークを有していないか、または最も強度の大きなピークの半値幅が１．５°以上である。このように結晶性の低い酸化物粒子であれば、前記の電池の負荷特性を高める作用が良好に発揮される。酸化物粒子の結晶性が高くても、前記のような微細な形態の場合には、これを用いた電極を有する電池の負荷特性が損なわれることはないが、電極と非水電解液との間の界面抵抗を低減する作用が小さく、電池の負荷特性の大きな向上は見込めない。 The oxide particles do not have a peak within the range of 2θ = 20 to 70 ° in the powder X-ray diffraction spectrum, or the half-width of the peak with the highest intensity is 1.5 ° or more. . Thus, if it is an oxide particle with low crystallinity, the effect | action which improves the load characteristic of the said battery will be exhibited favorably. Even if the crystallinity of the oxide particles is high, in the case of the fine form as described above, the load characteristics of the battery having the electrode using the same are not impaired, but the electrode and the non-aqueous electrolyte The effect of reducing the interfacial resistance is small, and a large improvement in the load characteristics of the battery cannot be expected.
　更に、前記酸化物粒子は、窒素ガス吸着により測定される比表面積が、３０ｍ２／ｇ以上であることが好ましく、１００ｍ２／ｇ以上であることがより好ましく、また、５００ｍ２／ｇ以下であることが好ましい。前記酸化物粒子の比表面積が前記のような値の場合には、電池の負荷特性を高める作用がより向上する。これは、結晶性が低く、かつ比表面積が前記のような大きな構造の酸化物粒子であれば、例えば、最表面に未結合手が多く残存するため、これらによって非水電解液中のリチウムイオンの解離が促され、リチウムイオンの拡散分極がより低減するためであると考えられる。 Further, the oxide particles preferably have a specific surface area measured by nitrogen gas adsorption of 30 m 2 / g or more, more preferably 100 m 2 / g or more, and 500 m 2 / g or less. Preferably there is. When the specific surface area of the oxide particles is as described above, the effect of increasing the load characteristics of the battery is further improved. This is because, if the oxide particles have a low crystallinity and a large surface area as described above, for example, many dangling bonds remain on the outermost surface. This is probably because the dissociation of lithium is promoted and the diffusion polarization of lithium ions is further reduced.
　本明細書でいう酸化物粒子の比表面積は、多分子層吸着の理論式であるＢＥＴ式を用いて、表面積を測定、計算したもので、酸化物粒子の表面と微細孔の比表面積である。具体的には、日本ベル社製の自動比表面積／細孔分布測定装置（装置型番：ＢＥＬＳＯＲＰ－ｍｉｎｉ）を用い、飽和蒸気圧に対する相対圧０．９９まで測定を行い、ＢＥＴ比表面積として得た値である。また、飽和蒸気圧は測定開始時圧力を用い、死容積は実測値とし、測定前乾燥条件は、窒素ガスフロー中８０℃で２時間とする。 The specific surface area of the oxide particles referred to in the present specification is a specific surface area of the surface of the oxide particles and the fine pores, which is obtained by measuring and calculating the surface area using the BET equation, which is a theoretical formula of multimolecular layer adsorption. . Specifically, using an automatic specific surface area / pore distribution measuring device (apparatus model number: BELSORP-mini) manufactured by Nippon Bell Co., Ltd., measurement was performed up to a relative pressure of 0.99 with respect to the saturated vapor pressure, and the BET specific surface area was obtained. Value. The saturated vapor pressure is the pressure at the start of measurement, the dead volume is an actual measurement value, and the pre-measurement drying conditions are 80 ° C. for 2 hours in a nitrogen gas flow.
　酸化物粒子を構成する酸化物としては、例えば、より結晶性の低い酸化物が得られやすいことから、Ｓｉ、Ｚｒ、Ａｌ、Ｃｅ、Ｍｇ、Ｔｉ、ＢａおよびＳｒよりなる群から選択される少なくとも１種の元素を含む酸化物が挙げられる。このような酸化物の具体例としては、例えば、ＳｉＯｘ（ｘ＝１．７～２．５）、ＺｒＯｙ（ｙ＝１．８～２．２）、ＺｒＯ２・ｎＨ２Ｏ（ｎ＝０．５～１０）、ＡｌＯＯＨ、Ａｌ（ＯＨ）３、ＣｅＯ２、ＭｇＯｚ（ｚ＝０．８～１．２）、ＭｇＯａ・ｍＨ２Ｏ（ａ＝０．８～１．２、ｍ＝０．５～１０）、ＴｉＯｂ（ｂ＝１．５～２）、ＢａＴｉＯ３、ＳｒＯ、ＳｒＴｉＯ３、Ｂａ２Ｏ３などが挙げられる。また、前記の各酸化物について、それぞれの結合を壊すことなく金属元素サイトに置換され得る元素であれば、酸化物は、前記の各元素以外の元素を含有する他元素置換体であってもよい。例えば、前記ＺｒＯｙにおけるＺｒの一部をＹで置換したものなどが挙げられる。また、ＴｉＢａＯ３におけるＴｉの一部をＳｒで置換した酸化物などを用いることもできる。酸化物粒子には、例えば、これらの酸化物により構成される粒子の１種のみを使用してもよく、２種以上を併用してもよい。 As the oxide constituting the oxide particles, for example, since an oxide having lower crystallinity is easily obtained, at least selected from the group consisting of Si, Zr, Al, Ce, Mg, Ti, Ba and Sr. An oxide containing one kind of element can be given. Specific examples of such oxides include, for example, SiO x (x = 1.7 to 2.5), ZrO y (y = 1.8 to 2.2), ZrO 2 .nH 2 O (n = 0.5-10), AlOOH, Al (OH) 3 , CeO 2 , MgO z (z = 0.8 to 1.2), MgO a · mH 2 O (a = 0.8 to 1.2, m = 0.5-10), TiO b (b = 1.5-2), BaTiO 3 , SrO, SrTiO 3 , Ba 2 O 3 and the like. In addition, for each of the above oxides, if the element can be replaced with a metal element site without breaking each bond, the oxide may be a substitute for another element containing an element other than each of the above elements. Good. For example, one obtained by substituting a part of Zr in the ZrO y with Y may be used. Alternatively, an oxide in which a part of Ti in TiBaO 3 is substituted with Sr can be used. For the oxide particles, for example, only one kind of particles composed of these oxides may be used, or two or more kinds may be used in combination.
　前記酸化物粒子の合成方法には、結晶性の低い酸化物粒子を得ることが可能な方法であれば、いずれの合成方法を採用しても構わない。しかし、結晶性の低さと一次粒子のサイズの小ささとを両立させることは技術的に困難であり、このような構造および形態を有する酸化物粒子を合成するには、沈殿析出法、加熱温度を低温度とした水熱処理（水熱合成法）などの水溶液中酸化処理による合成方法を採用することが好ましい。 As the method for synthesizing the oxide particles, any synthesis method may be adopted as long as it is a method capable of obtaining oxide particles having low crystallinity. However, it is technically difficult to achieve both the low crystallinity and the small size of the primary particles. In order to synthesize oxide particles having such a structure and form, the precipitation method, the heating temperature It is preferable to employ a synthesis method by oxidation treatment in an aqueous solution such as hydrothermal treatment (hydrothermal synthesis method) at a low temperature.
　前記の水溶液中酸化処理による合成方法で前記酸化物粒子を合成する場合、その原料としては、水に溶解させる必要があることから、酸化物粒子を構成する元素（酸素以外の元素）を含有する水溶性の塩を使用することが好ましい。このような水溶性の塩としては、例えば、酸化物粒子を構成する元素を含む硫酸塩、硝酸塩、塩化物などが挙げられる。 When the oxide particles are synthesized by the synthesis method by oxidation treatment in an aqueous solution, the raw material contains an element (an element other than oxygen) constituting the oxide particles because it needs to be dissolved in water. It is preferable to use water-soluble salts. Examples of such water-soluble salts include sulfates, nitrates, and chlorides containing elements that constitute oxide particles.
　水溶液中酸化処理による合成方法では、前記のような原料（水溶性の塩）の水溶液に、アンモニア水、水酸化ナトリウムなどのアルカリ金属の水酸化物の水溶液などのアルカリ水溶液を投入して中和させ、共沈法にて沈殿物を得た後、これを水溶液中で酸化処理を行う。水溶液中酸化処理としては、攪拌しながら酸素、または、空気などの酸素を含むガスをバブリングして酸化させる方法や、加圧下で熱処理を行う水熱処理法などが適用出来る。別途酸化剤を添加して酸化させる方法もあるが、酸化剤が不純物として残存する場合があるため、使用する際には選定に注意が必要である。沈殿析出法の場合、バブリングによる酸化を共沈時に同時に行ってもよく、生成した沈殿物を含む懸濁液をよく洗浄した後、この沈殿物を液中から濾過などにより取り出し、乾燥するなどして酸化物粒子を得る。 In the synthesis method by oxidation treatment in an aqueous solution, the aqueous solution of the raw material (water-soluble salt) as described above is neutralized by introducing an alkaline aqueous solution such as an aqueous solution of an alkali metal hydroxide such as ammonia water or sodium hydroxide. And a precipitate is obtained by a coprecipitation method, and then this is oxidized in an aqueous solution. As the oxidation treatment in an aqueous solution, a method in which oxygen or a gas containing oxygen such as air is oxidized while being stirred, a hydrothermal treatment method in which heat treatment is performed under pressure, or the like can be applied. There is another method of oxidizing by adding an oxidizing agent. However, since the oxidizing agent may remain as an impurity, care must be taken when selecting it. In the case of the precipitation method, oxidation by bubbling may be performed at the same time as the coprecipitation. After the suspension containing the generated precipitate is washed well, the precipitate is taken out of the solution by filtration and dried. To obtain oxide particles.
　水熱処理法の場合、共沈法により得られた懸濁液（前記沈殿物を含む水溶液）を密閉容器中で加熱することにより、加圧下で熱処理し、その後に懸濁液をよく洗浄してから濾過して沈殿物を取り出し、これを乾燥するなどして酸化物粒子を得る。特に、前記のＳｉＯｘ、ＺｒＯ２・ｎＨ２Ｏ、ＡｌＯＯＨ、Ａｌ（ＯＨ）３、ＭｇＯａ・ｍＨ２Ｏなどは、水熱処理によってガラス質沈殿を得た後、これを取り出し、乾燥する工程を経て酸化物粒子を得ることが好ましい。 In the case of the hydrothermal treatment method, the suspension obtained by the coprecipitation method (the aqueous solution containing the precipitate) is heated in a sealed container to heat-treat under pressure, and then the suspension is thoroughly washed. The precipitate is removed by filtration and dried to obtain oxide particles. In particular, the SiO x , ZrO 2 · nH 2 O, AlOOH, Al (OH) 3 , MgO a · mH 2 O, etc. are obtained by obtaining a glassy precipitate by hydrothermal treatment, and then taking it out and drying it. It is preferable to obtain oxide particles through this.
　水熱処理法における前記懸濁液は、添加するアルカリ水溶液の量を調節することにより、そのｐＨを４～１１とすることが好ましく、このような範囲の中で、目的とする酸化物が析出し得るｐＨを選択すればよい。なお、例えば、前記のＳｉＯｘ、ＺｒＯ２・ｎＨ２Ｏ、ＡｌＯＯＨ、Ａｌ（ＯＨ）３、ＭｇＯａ・ｍＨ２Ｏなどの場合のように、水熱処理によってガラス質沈殿が得られるものの場合には、懸濁液のｐＨを４～７の弱酸性から中性域とすることがより好ましい。また、前記の沈殿析出法により酸化物粒子を合成する場合にも、原料の水溶液にアルカリ水溶液を投入後のｐＨを、水熱処理法における前記懸濁液における前記のｐＨと同様とすることが好ましい。 The suspension in the hydrothermal treatment method preferably has a pH of 4 to 11 by adjusting the amount of the alkaline aqueous solution to be added, and the target oxide is precipitated within such a range. What is necessary is just to select pH to obtain. In the case where a glassy precipitate is obtained by hydrothermal treatment, for example, in the case of SiO x , ZrO 2 .nH 2 O, AlOOH, Al (OH) 3 , MgO a · mH 2 O, etc. The pH of the suspension is more preferably from 4 to 7 in a weakly acidic to neutral range. Also, when the oxide particles are synthesized by the precipitation method, it is preferable that the pH after adding the alkaline aqueous solution to the raw material aqueous solution is the same as the pH in the suspension in the hydrothermal treatment method. .
　水熱処理法における加熱温度は、６０℃以上とすることが好ましく、また、２００℃以下とすることが好ましい。なお、加熱温度は、酸化物粒子に過度な結晶化が起こらない程度に低い温度を選択することがより好ましい。具体的には、加熱温度を、８０℃以上とすることがより好ましく、また、１５０℃以下とすることがより好ましく、１２０℃以下とすることが更に好ましい。 The heating temperature in the hydrothermal treatment method is preferably 60 ° C. or higher, and is preferably 200 ° C. or lower. Note that it is more preferable to select a heating temperature that is low enough to prevent excessive crystallization of the oxide particles. Specifically, the heating temperature is more preferably 80 ° C. or higher, more preferably 150 ° C. or lower, and still more preferably 120 ° C. or lower.
　また、水熱処理法における加熱時間は、酸化脱水が不十分な粒子の形成を抑制する観点から、１時間以上とすることが好ましい。ただし、水熱処理法を採用する場合において、加熱時間は、長くし過ぎても、合成される酸化物粒子の特性にあまり影響はないが、前記懸濁液のｐＨと加熱温度とによって決定される飽和反応状態に到達した後には、酸化物粒子の状態が変化しなくなる。よって、水熱処理法における加熱時間は、４０時間以下とすることが好ましく、６時間以下とすることがより好ましい。 In addition, the heating time in the hydrothermal treatment method is preferably 1 hour or longer from the viewpoint of suppressing the formation of particles that are insufficiently oxidized and dehydrated. However, in the case of adopting the hydrothermal treatment method, even if the heating time is too long, there is not much influence on the characteristics of the synthesized oxide particles, but it is determined by the pH of the suspension and the heating temperature. After reaching the saturated reaction state, the state of the oxide particles does not change. Therefore, the heating time in the hydrothermal treatment method is preferably 40 hours or less, and more preferably 6 hours or less.
　本発明の電極においては、前記酸化物粒子の使用による前記の効果を良好に確保する観点から、電極合剤層の含有する前記酸化物粒子と活物質粒子との合計を１００質量％としたとき、前記酸化物粒子の割合を、０．１質量％以上、好ましくは０．５質量％以上とする。ただし、電極合剤層中の前記酸化物粒子の含有量が多くなり過ぎると、絶縁性の物質が電極合剤層中に多量に存在することになって電極の直流抵抗が増大し、却ってこの電極を用いた電池の負荷特性が低下する。よって、電極合剤層の含有する前記酸化物粒子と活物質粒子との合計を１００質量％としたとき、前記酸化物粒子の割合は、１０質量％以下、好ましくは５質量％以下とする。 In the electrode of the present invention, from the viewpoint of ensuring the above-mentioned effects by using the oxide particles satisfactorily, when the total of the oxide particles and the active material particles contained in the electrode mixture layer is 100% by mass The ratio of the oxide particles is 0.1% by mass or more, preferably 0.5% by mass or more. However, if the content of the oxide particles in the electrode mixture layer is excessively large, an insulating material is present in a large amount in the electrode mixture layer, and the direct current resistance of the electrode is increased. The load characteristic of the battery using the electrode is lowered. Therefore, when the total of the oxide particles and the active material particles contained in the electrode mixture layer is 100% by mass, the ratio of the oxide particles is 10% by mass or less, preferably 5% by mass or less.
　本発明の電極がリチウムイオン二次電池用負極として使用される場合、活物質粒子には、従来から知られているリチウムイオン二次電池の負極に使用されている活物質粒子、すなわち、Ｌｉを吸蔵放出可能な活物質の粒子を用いることができる。このような活物質粒子の具体例としては、例えば、黒鉛（天然黒鉛；熱分解炭素類、ＭＣＭＢ、炭素繊維などの易黒鉛化炭素を２８００℃以上で黒鉛化処理した人造黒鉛；など）、熱分解炭素類、コークス類、ガラス状炭素類、有機高分子化合物の焼成体、メソカーボンマイクロビーズ、炭素繊維、活性炭などの炭素材料；リチウムと合金化可能な金属（Ｓｉ、Ｓｎなど）や、これらの金属を含む材料（合金など）；などの粒子が挙げられる。本発明の電極をリチウムイオン二次電池用負極とする場合、これらの活物質粒子は、１種のみを使用してもよく、２種以上を併用してもよい。 When the electrode of the present invention is used as a negative electrode for a lithium ion secondary battery, the active material particles include active material particles used for a negative electrode of a conventionally known lithium ion secondary battery, that is, Li. Active material particles that can be occluded and released can be used. Specific examples of such active material particles include, for example, graphite (natural graphite; artificial graphite obtained by graphitizing graphitized carbon such as pyrolytic carbons, MCMB, and carbon fiber at 2800 ° C. or higher), heat Carbon materials such as decomposed carbons, cokes, glassy carbons, fired organic polymer compounds, mesocarbon microbeads, carbon fibers and activated carbon; metals that can be alloyed with lithium (Si, Sn, etc.), and these And other particles containing a metal (such as an alloy). When the electrode of the present invention is used as a negative electrode for a lithium ion secondary battery, these active material particles may be used alone or in combination of two or more.
　また、本発明の電極がリチウムイオン二次電池用正極として使用される場合、活物質粒子には、従来から知られているリチウムイオン二次電池の正極に使用されている活物質粒子、すなわち、Ｌｉを吸蔵放出可能な活物質の粒子を用いることができる。このような活物質粒子の具体例としては、例えば、Ｌｉ１＋ｃＭ１Ｏ２（－０．１＜ｃ＜０．１、Ｍ１：Ｃｏ、Ｎｉ、Ｍｎ、Ａｌ、Ｍｇなど）で表される層状構造のリチウム含有遷移金属酸化物、ＬｉＭｎ２Ｏ４やその元素の一部を他元素で置換したスピネル構造のリチウムマンガン酸化物、ＬｉＭ２ＰＯ４（Ｍ２：Ｃｏ、Ｎｉ、Ｍｎ、Ｆｅなど）で表されるオリビン型化合物などの粒子を用いることが可能である。前記層状構造のリチウム含有遷移金属酸化物の具体例としては、ＬｉＣｏＯ２やＬｉＮｉ１－ｄＣｏｄ－ｅＡｌｅＯ２（０．１≦ｄ≦０．３、０．０１≦ｅ≦０．２）などの他、少なくともＣｏ、ＮｉおよびＭｎを含む酸化物（ＬｉＭｎ１／３Ｎｉ１／３Ｃｏ１／３Ｏ２、ＬｉＭｎ５／１２Ｎｉ５／１２Ｃｏ１／６Ｏ２、ＬｉＭｎ３／５Ｎｉ１／５Ｃｏ１／５Ｏ２など）などを例示することができる。本発明の電極をリチウムイオン二次電池用正極とする場合、これらの活物質粒子は、１種のみを使用してもよく、２種以上を併用してもよい。 In addition, when the electrode of the present invention is used as a positive electrode for a lithium ion secondary battery, the active material particles include active material particles used for a positive electrode of a conventionally known lithium ion secondary battery, that is, Active material particles capable of occluding and releasing Li can be used. Specific examples of such active material particles are represented by, for example, Li 1 + c M 1 O 2 (−0.1 <c <0.1, M 1 : Co, Ni, Mn, Al, Mg, etc.). Lithium-containing transition metal oxide having a layered structure, LiMn 2 O 4 and a spinel-structured lithium manganese oxide obtained by substituting some of its elements with other elements, LiM 2 PO 4 (M 2 : Co, Ni, Mn, Fe, etc. It is possible to use particles such as olivine type compounds represented by Specific examples of the lithium-containing transition metal oxide having a layered structure include LiCoO 2 and LiNi 1-d Co d e Al e O 2 (0.1 ≦ d ≦ 0.3, 0.01 ≦ e ≦ 0. 2) and other oxides containing at least Co, Ni and Mn (LiMn 1/3 Ni 1/3 Co 1/3 O 2 , LiMn 5/12 Ni 5/12 Co 1/6 O 2 , LiMn 3 / 5 Ni 1/5 Co 1/5 O 2 etc.). When the electrode of the present invention is used as a positive electrode for a lithium ion secondary battery, these active material particles may be used alone or in combination of two or more.
　なお、本発明の電極をリチウムイオン二次電池用負極とする場合の前記活物質粒子や、リチウムイオン二次電池用正極とする場合の前記活物質粒子は、前記酸化物粒子と同じ方法で測定される一次粒子の平均粒子径が、５０ｎｍ以上であることが好ましく、また、５００μｍ以下であることが好ましく、１０μｍ以下であることがより好ましい。 The active material particles when the electrode of the present invention is a negative electrode for a lithium ion secondary battery and the active material particles when the electrode is a positive electrode for a lithium ion secondary battery are measured by the same method as the oxide particles. The average particle diameter of the primary particles is preferably 50 nm or more, more preferably 500 μm or less, and even more preferably 10 μm or less.
　本発明の電極の電極合剤層に係る樹脂製バインダには、従来から知られているリチウムイオン二次電池用の正極に係る正極合剤層や、負極に係る負極合剤層で使用されている樹脂製バインダと同じものが使用できる。具体的には、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）、スチレンブタジエンゴム（ＳＢＲ）、カルボキシメチルセルロース（ＣＭＣ）などが好ましいものとして挙げられる。 The resin binder according to the electrode mixture layer of the electrode of the present invention is used in a conventionally known positive electrode mixture layer related to a positive electrode for a lithium ion secondary battery and a negative electrode mixture layer related to a negative electrode. The same resin binder can be used. Specifically, for example, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), styrene butadiene rubber (SBR), carboxymethyl cellulose (CMC) and the like are preferable.
　また、本発明の電極に係る電極合剤層には、必要に応じて導電性助剤を含有させることもできる。導電性助剤の具体例としては、例えば、天然黒鉛（鱗片状黒鉛など）、人造黒鉛などの黒鉛；アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラックなどのカ－ボンブラック；炭素繊維；などが挙げられる。 In addition, the electrode mixture layer according to the electrode of the present invention may contain a conductive auxiliary as necessary. Specific examples of conductive aids include, for example, graphite such as natural graphite (eg, flaky graphite) and artificial graphite; carbon such as acetylene black, ketjen black, channel black, furnace black, lamp black, and thermal black. Black; carbon fiber; and the like.
　本発明の電極をリチウムイオン二次電池用負極とする場合、電極合剤層（負極合剤層）における各成分の組成としては、例えば、活物質粒子を８５～９９質量％とし、樹脂製バインダを１．０～１０質量％とすることが好ましい。また、導電性助剤を用いる場合には、電極合剤層中における導電性助剤の量を０．５～１０質量％とすることが好ましい。そして、電極合剤層（負極合剤層）の厚み（集電体の片面または両面に電極合剤層を形成する場合には、集電体の片面あたりの厚み）は、３０～１５０μｍとすることが好ましい。 When the electrode of the present invention is a negative electrode for a lithium ion secondary battery, the composition of each component in the electrode mixture layer (negative electrode mixture layer) is, for example, 85 to 99% by mass of active material particles, and a resin binder. Is preferably 1.0 to 10% by mass. In the case where a conductive auxiliary is used, the amount of the conductive auxiliary in the electrode mixture layer is preferably 0.5 to 10% by mass. The thickness of the electrode mixture layer (negative electrode mixture layer) (when the electrode mixture layer is formed on one side or both sides of the current collector, the thickness per side of the current collector) is 30 to 150 μm. It is preferable.
　本発明の電極を、集電体を有するリチウムイオン二次電池用負極とする場合、集電体には、銅製やニッケル製の箔、パンチングメタル、網、エキスパンドメタルなどを用い得るが、通常、銅箔が用いられる。集電体の厚みは、５～３０μｍであることが好ましい。 When the electrode of the present invention is used as a negative electrode for a lithium ion secondary battery having a current collector, the current collector can be made of copper or nickel foil, punched metal, net, expanded metal, etc. Copper foil is used. The thickness of the current collector is preferably 5 to 30 μm.
　本発明の電極をリチウムイオン二次電池用正極とする場合、電極合剤層（正極合剤層）における各成分の組成としては、例えば、活物質粒子を７５～９５質量％とし、樹脂製バインダを２～１５質量％とし、導電性助剤を２～１５質量％とすることが好ましい。そして、電極合剤層（正極合剤層）の厚み（集電体の片面または両面に電極合剤層を形成する場合には、集電体の片面あたりの厚み）は、集電体の片面あたり、３０～１８０μｍとすることが好ましい。 When the electrode of the present invention is used as a positive electrode for a lithium ion secondary battery, the composition of each component in the electrode mixture layer (positive electrode mixture layer) is, for example, 75 to 95% by mass of active material particles, and a resin binder. Is preferably 2 to 15% by mass, and the conductive auxiliary is preferably 2 to 15% by mass. And the thickness of the electrode mixture layer (positive electrode mixture layer) (when the electrode mixture layer is formed on one side or both sides of the current collector, the thickness per side of the current collector) is the single side of the current collector. The thickness is preferably 30 to 180 μm.
　本発明の電極を、集電体を有するリチウムイオン二次電池用正極とする場合、集電体には、アルミニウム製の箔、パンチングメタル、網、エキスパンドメタルなどを用い得るが、通常、アルミニウム箔が用いられる。集電体の厚みは、１０～３０μｍであることが好ましい。 When the electrode of the present invention is used as a positive electrode for a lithium ion secondary battery having a current collector, an aluminum foil, punching metal, net, expanded metal, or the like can be used as the current collector. Is used. The thickness of the current collector is preferably 10 to 30 μm.
　本発明の電極は、例えば、前記酸化物粒子、活物質粒子および樹脂製バインダ、更には必要に応じて導電性助剤を含有する電極合剤を、Ｎ－メチル－２－ピロリドン（ＮＭＰ）などの有機溶剤や水といった溶剤に分散させて調製した電極合剤含有組成物（ペースト、スラリーなど）を、集電体の片面または両面などに塗布して乾燥し、必要に応じてプレス処理を施す工程を経て製造することができる。 The electrode of the present invention includes, for example, an electrode mixture containing the oxide particles, active material particles and resin binder, and optionally a conductive auxiliary agent, such as N-methyl-2-pyrrolidone (NMP). An electrode mixture-containing composition (paste, slurry, etc.) prepared by dispersing in a solvent such as organic solvent or water is applied to one side or both sides of the current collector, dried, and subjected to press treatment as necessary. It can be manufactured through a process.
　なお、前記酸化物粒子による前記の効果をより良好に確保する観点から、電極合剤層中においては、前記酸化物粒子の凝集が抑制されていることが好ましく、具体的には、電極合剤層中における前記酸化物粒子の分散粒子径は、３００ｎｍ以下であることが好ましい。ここでいう前記酸化物粒子の分散粒子径は、電極の断面を走査型電子顕微鏡（ＳＥＭ）で観察し、酸化物粒子（一次粒子の状態で分散している酸化物粒子、および二次粒子の状態で凝集しつつ分散している酸化物粒子を含む）１００個のうちの最も大きい粒子の直径を測定して得られる値である。 In addition, from the viewpoint of ensuring better the above-described effect by the oxide particles, it is preferable that aggregation of the oxide particles is suppressed in the electrode mixture layer. Specifically, the electrode mixture The dispersed particle diameter of the oxide particles in the layer is preferably 300 nm or less. The dispersed particle diameter of the oxide particles referred to here is determined by observing the cross section of the electrode with a scanning electron microscope (SEM), and the oxide particles (the oxide particles dispersed in the state of primary particles and the secondary particles). It is a value obtained by measuring the diameter of the largest particle of 100 particles (including oxide particles that are aggregated and dispersed in a state).
　このように、電極合剤層中での前記酸化物粒子の凝集を抑制するには、下記の方法によって調製された電極合剤含有組成物を用いて電極合剤層を形成することが好ましい。まず、前記酸化物粒子を、電極合剤含有組成物に使用する溶剤と同じ溶剤中に分散させて、酸化物粒子分散体を調製する。この酸化物粒子分散体には、樹脂製バインダや分散剤などの有機物は含有させないことが好ましい。 Thus, in order to suppress aggregation of the oxide particles in the electrode mixture layer, it is preferable to form the electrode mixture layer using the electrode mixture-containing composition prepared by the following method. First, the oxide particles are dispersed in the same solvent as the solvent used for the electrode mixture-containing composition to prepare an oxide particle dispersion. This oxide particle dispersion preferably does not contain an organic substance such as a resin binder or a dispersant.
　酸化物粒子分散体の調製には、ボールミル、ナノミル、ピコミル、ペイントシェーカー、ディゾルバーなどのナノ粒子分散体の調製に好適な公知の分散機を用いることができる。 For the preparation of the oxide particle dispersion, a known disperser suitable for the preparation of the nanoparticle dispersion such as a ball mill, nanomill, picomill, paint shaker, or dissolver can be used.
　酸化物粒子分散体の分散条件や、酸化物粒子分散体における前記酸化物粒子の濃度（固形分濃度）は、後に形成される電極合剤層中において、前記酸化物粒子の分散粒子径が３００ｎｍ以下となるような条件、固形分濃度を選択すればよい。具体的には、酸化物粒子分散体の固形分濃度は、例えば、後に電極合剤含有組成物とすることや、分散安定性など、取り扱いが容易であることなども考慮して、５～５０質量％とすることが好ましい。また、酸化物粒子分散体の分散条件としては、例えば、ペイントシェーカーを使用し、ジルコニアビーズを用いて、前記の固形分濃度の酸化物粒子分散体を調製する場合、分散時間を５分～２時間程度とすることが好ましい。 The dispersion conditions of the oxide particle dispersion and the concentration (solid content concentration) of the oxide particles in the oxide particle dispersion are such that the dispersed particle diameter of the oxide particles is 300 nm in the electrode mixture layer to be formed later. What is necessary is just to select the conditions and solid content concentration which become the following. Specifically, the solid content concentration of the oxide particle dispersion is 5 to 50 in consideration of, for example, an electrode mixture-containing composition later and easy handling such as dispersion stability. It is preferable to set it as the mass%. In addition, as a dispersion condition of the oxide particle dispersion, for example, when the oxide particle dispersion having the above-mentioned solid content concentration is prepared using a paint shaker and zirconia beads, the dispersion time is 5 minutes to 2 minutes. It is preferable to set it to about time.
　前記のように調製した酸化物粒子分散体に、活物質粒子および樹脂製バインダ、更には、必要に応じて導電性助剤や溶剤を加えて混合し、電極合剤含有組成物を調製する。なお、活物質粒子および樹脂製バインダ、導電性助剤は、あらかじめ溶剤に分散させて分散液（樹脂製バインダは溶剤に溶解していてもよい）を調製しておき、この分散液と酸化物粒子分散体とを混合して電極合剤含有組成物を調製してもよい。 The active material particles and the resin binder, and further, if necessary, a conductive auxiliary agent and a solvent are added to and mixed with the oxide particle dispersion prepared as described above to prepare an electrode mixture-containing composition. The active material particles, the resin binder, and the conductive auxiliary are previously dispersed in a solvent to prepare a dispersion (the resin binder may be dissolved in the solvent). An electrode mixture-containing composition may be prepared by mixing with a particle dispersion.
　酸化物粒子分散体と、活物質粒子や樹脂製バインダ、導電性助剤などとを混合する際には、ジルコニアビーズなどの分散メディアを使用する分散機を使用することもできるが、分散メディアが活物質粒子にダメージを与える虞があることから、メディアレス分散機を使用することがより好ましい。メディアレス分散機としては、例えば、ハイブリッドミキサー、ナノマイザー、ジェットミルなどの汎用の分散機が挙げられる。 When mixing the oxide particle dispersion with the active material particles, the resin binder, the conductive auxiliary agent, etc., a disperser using a dispersion medium such as zirconia beads can be used. Since there is a possibility of damaging the active material particles, it is more preferable to use a medialess disperser. Examples of the medialess disperser include general-purpose dispersers such as a hybrid mixer, a nanomizer, and a jet mill.
　例えば前記のようにして調製された電極合剤含有組成物を使用して電極合剤層を形成し、更に必要に応じてプレス処理を施した電極には、常法に従って電池内の端子と接続するためのリード部を形成することができる。 For example, an electrode mixture layer is formed using the electrode mixture-containing composition prepared as described above, and the electrodes subjected to press treatment as necessary are connected to terminals in the battery according to a conventional method. The lead part for doing can be formed.
　本発明のリチウムイオン二次電池（以下、単に「電池」という場合がある）は、正極、負極、非水電解液およびセパレータを備えており、正極および負極のうちの少なくとも一方が本発明のリチウムイオン二次電池用電極であればよく、その他の構成および構造については特に制限されず、従来から知られているリチウムイオン二次電池で採用されている各種構成および構造を適用することができる。 The lithium ion secondary battery of the present invention (hereinafter sometimes simply referred to as “battery”) includes a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator, and at least one of the positive electrode and the negative electrode is the lithium of the present invention. Any other configuration and structure may be used as long as it is an electrode for an ion secondary battery, and various configurations and structures employed in conventionally known lithium ion secondary batteries can be applied.
　本発明の電池は、正極および負極のいずれか一方のみが本発明の電極であればよく、正極および負極の両方が本発明の電極であってもよい。本発明の電池に係る負極のみが本発明の電極である場合、正極には、前記酸化物粒子を含有しない以外は、本発明の電極（正極）と同じ構成の正極を使用することができる。また、本発明の電池に係る正極のみが本発明の電極である場合、負極には、前記酸化物粒子を含有しない以外は、本発明の電極（負極）と同じ構成の負極を使用することができる。 In the battery of the present invention, only one of the positive electrode and the negative electrode may be the electrode of the present invention, and both the positive electrode and the negative electrode may be the electrode of the present invention. When only the negative electrode according to the battery of the present invention is the electrode of the present invention, a positive electrode having the same configuration as the electrode (positive electrode) of the present invention can be used as the positive electrode except that the oxide particles are not contained. In addition, when only the positive electrode according to the battery of the present invention is the electrode of the present invention, the negative electrode having the same configuration as the electrode (negative electrode) of the present invention may be used except that the oxide particles are not included. it can.
　本発明の電池に係るセパレータは、８０℃以上（より好ましくは１００℃以上）１７０℃以下（より好ましくは１５０℃以下）において、その孔が閉塞する性質（すなわちシャットダウン機能）を有していることが好ましく、通常のリチウムイオン二次電池などで使用されているセパレータ、例えば、ポリエチレン（ＰＥ）やポリプロピレン（ＰＰ）などのポリオレフィン製の微多孔膜を用いることができる。セパレータを構成する微多孔膜は、例えば、ＰＥのみを使用したものやＰＰのみを使用したものであってもよく、また、ＰＥ製の微多孔膜とＰＰ製の微多孔膜との積層体であってもよい。セパレータの厚みは、例えば、１０～３０μｍであることが好ましい。 The separator according to the battery of the present invention has a property (that is, a shutdown function) that the pores are blocked at 80 ° C. or higher (more preferably 100 ° C. or higher) and 170 ° C. or lower (more preferably 150 ° C. or lower). Preferably, separators used in ordinary lithium ion secondary batteries, for example, microporous membranes made of polyolefin such as polyethylene (PE) and polypropylene (PP) can be used. The microporous film constituting the separator may be, for example, one using only PE or one using PP, or a laminate of a PE microporous film and a PP microporous film. There may be. The thickness of the separator is preferably 10 to 30 μm, for example.
　前記の正極と前記の負極と前記のセパレータとは、正極と負極との間にセパレータを介在させて重ねた積層電極体や、更にこれを渦巻状に巻回した巻回電極体の形態で本発明の電池に使用することができる。 The positive electrode, the negative electrode, and the separator are formed in the form of a laminated electrode body in which a separator is interposed between the positive electrode and the negative electrode, or a wound electrode body in which the separator is wound in a spiral shape. It can be used for the battery of the invention.
　本発明の電池に係る非水電解液には、例えば、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート、プロピオン酸メチル、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート、ガンマーブチロラクトン、エチレングリコールサルファイト、１，２－ジメトキシエタン、１，３－ジオキソラン、テトラヒドロフラン、２－メチル－テトラヒドロフラン、ジエチルエーテルなどの有機溶媒に、例えば、ＬｉＣｌＯ４、ＬｉＰＦ６、ＬｉＢＦ４、ＬｉＡｓＦ６、ＬｉＳｂＦ６、ＬｉＣＦ３ＳＯ３、ＬｉＣＦ３ＣＯ２、Ｌｉ２Ｃ２Ｆ４（ＳＯ３）２、ＬｉＮ（ＣＦ３ＳＯ２）２、ＬｉＣ（ＣＦ３ＳＯ２）３、ＬｉＣｎＦ２ｎ＋１ＳＯ３（ｎ≧２）、ＬｉＮ（ＲｆＯＳＯ２）２［ここでＲｆはフルオロアルキル基］などのリチウム塩から選ばれる少なくとも一種を溶解させることによって調製したものが使用される。このリチウム塩の非水電解液中の濃度としては、０．５～１．５ ｍｏｌ／ｌ、特に０．９～１．２５ ｍｏｌ／ｌが好ましい。また、これらの電解液に安全性や充放電サイクル性、高温貯蔵性といった特性を向上させる目的で、ビニレンカーボネート類、１，３－プロパンサルトン、ジフェニルジスルフィド、シクロヘキシルベンゼン、ビフェニル、フルオロベンゼン、ｔ－ブチルベンゼンなどの添加剤を適宜加えることもできる。 Examples of the nonaqueous electrolytic solution according to the battery of the present invention include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, methyl propionate, ethylene carbonate, propylene carbonate, butylene carbonate, gamma-butyrolactone, ethylene glycol sulfite, 1,2- dimethoxyethane, 1,3-dioxolane, tetrahydrofuran, 2-methyl - tetrahydrofuran, organic solvents such as diethyl ether, for example, LiClO 4, LiPF 6, LiBF 4, LiAsF 6, LiSbF 6, LiCF 3 SO 3, LiCF 3 CO 2 , Li 2 C 2 F 4 (SO 3 ) 2 , LiN (CF 3 SO 2 ) 2 , LiC (CF 3 SO 2 ) 3 , LiC n F 2n + 1 SO 3 (n ≧ 2), LiN (R f OSO 2 ) 2 [wherein R f is a fluoroalkyl group] or the like prepared by dissolving at least one selected from lithium salts is used. The concentration of the lithium salt in the non-aqueous electrolyte is preferably 0.5 to 1.5 mol / l, particularly 0.9 to 1.25 mol / l. In addition, vinylene carbonates, 1,3-propane sultone, diphenyl disulfide, cyclohexyl benzene, biphenyl, fluorobenzene, t for the purpose of improving safety, charge / discharge cycleability, and high-temperature storage properties of these electrolytes -Additives such as butylbenzene can be added as appropriate.
　本発明のリチウムイオン二次電池の形態としては、スチール缶やアルミニウム缶などを外装缶として使用した筒形（角筒形や円筒形など）などが挙げられる。また、金属を蒸着したラミネートフィルムを外装体としたソフトパッケージ電池とすることもできる。 Examples of the form of the lithium ion secondary battery of the present invention include a cylindrical shape (such as a square cylindrical shape or a cylindrical shape) using a steel can or an aluminum can as an outer can. Moreover, it can also be set as the soft package battery which used the laminated film which vapor-deposited the metal as an exterior body.
　本発明のリチウムイオン二次電池は、優れた負荷特性や充放電サイクル特性を有しており、こうした特性が特に求められる用途をはじめとして、従来から知られているリチウムイオン二次電池が適用されている各種用途と同じ用途に用いることができる。 The lithium ion secondary battery of the present invention has excellent load characteristics and charge / discharge cycle characteristics, and conventionally known lithium ion secondary batteries are applied, including applications in which such characteristics are particularly required. It can be used for the same applications as various applications.
　以下、実施例に基づいて本発明を詳細に述べる。ただし、下記実施例は、本発明を制限するものではない。 Hereinafter, the present invention will be described in detail based on examples. However, the following examples do not limit the present invention.
実施例１
＜ジルコニア粒子の合成＞
　まず、塩化酸化ジルコニウム八水和物を水に溶解させて、８質量％濃度のジルコニウム塩水溶液を調製した。次に、１．４質量％濃度のアンモニア水溶液に、前記ジルコニウム塩水溶液を滴下しつつ攪拌して、酸化ジルコニウム水和物粒子を含む沈殿物を生成させた。この沈殿物を含む懸濁液を室温で２１時間熟成させた。 Example 1
<Synthesis of zirconia particles>
First, chlorinated zirconium oxide octahydrate was dissolved in water to prepare an aqueous 8 mass% zirconium salt solution. Next, the zirconium salt aqueous solution was added dropwise to a 1.4 mass% ammonia aqueous solution while stirring to produce a precipitate containing zirconium oxide hydrate particles. The suspension containing this precipitate was aged at room temperature for 21 hours.
　続いて、前記懸濁液をオートクレーブに仕込み、１時間かけて１００℃にまで昇温し、その後１００℃で７時間水熱処理を施し、１０時間かけて室温まで冷却した後、室温で３６時間熟成させた。 Subsequently, the suspension was charged in an autoclave, heated to 100 ° C. over 1 hour, then hydrothermally treated at 100 ° C. for 7 hours, cooled to room temperature over 10 hours, and then aged at room temperature for 36 hours. I let you.
　次に、水熱処理後の沈殿物から未反応物や不純物を除去するために超音波洗浄器を用いて水洗し、その後に濾過を行って沈殿物を回収し、これを空気中６０℃で６時間乾燥した。乾燥後のものを乳鉢で軽く解砕して、酸化ジルコニウム水和物粒子（ＺｒＯ２・５Ｈ２Ｏ）を得た。 Next, in order to remove unreacted substances and impurities from the precipitate after hydrothermal treatment, it is washed with water using an ultrasonic cleaner, followed by filtration to recover the precipitate. Dry for hours. The dried product was lightly crushed with a mortar to obtain zirconium oxide hydrate particles (ZrO 2 .5H 2 O).
　前記の酸化ジルコニウム水和物粒子の粉末Ｘ線回折スペクトルを図１に示す。図１から明らかなように、この酸化ジルコニウム水和物粒子は、粉末Ｘ線回折スペクトルにおける２θ＝２０～７０°の範囲内において、非常にブロードな回折強度変化を示すが、明瞭な回折線ピークは観測されず、結晶性を判別できないアモルファス構造であることが判明した。 The powder X-ray diffraction spectrum of the zirconium oxide hydrate particles is shown in FIG. As is apparent from FIG. 1, the zirconium oxide hydrate particles show a very broad diffraction intensity change in the range of 2θ = 20 to 70 ° in the powder X-ray diffraction spectrum, but have a clear diffraction line peak. Was not observed, and was found to be an amorphous structure whose crystallinity could not be distinguished.
　また、前記の酸化ジルコニウム水和物粒子のＴＥＭ写真から、前記の方法によって求めた一次粒子の平均粒子径は２．１ｎｍであり、窒素ガス吸着により求めた比表面積（ＢＥＴ比表面積）は４３３ｍ２／ｇであった。 Moreover, from the TEM photograph of the said zirconium oxide hydrate particle | grains, the average particle diameter of the primary particle calculated | required by the said method is 2.1 nm, and the specific surface area (BET specific surface area) calculated | required by nitrogen gas adsorption | suction is 433 m < 2 >. / G.
＜負極合剤含有組成物の調製＞
　２０質量％となる量の前記酸化ジルコニウム水和物粒子を水に加え、φ０．３ｍｍのジルコニアビーズを用いてペイントシェーカーで１時間混合して、酸化ジルコニウム水和物粒子の水分散体を調製した。この分散体における酸化ジルコニウム水和物粒子の分散粒子径は１１６ｎｍであった。 <Preparation of negative electrode mixture-containing composition>
The zirconium oxide hydrate particles in an amount of 20% by mass were added to water and mixed with a paint shaker for 1 hour using φ0.3 mm zirconia beads to prepare an aqueous dispersion of zirconium oxide hydrate particles. . The dispersion particle diameter of the zirconium oxide hydrate particles in this dispersion was 116 nm.
　鱗片状黒鉛（日立化成工業社製、一次粒子径の平均粒子径：約４５０μｍ）：９８質量部、アセチレンブラック：１質量部、およびＣＭＣ：１質量部を、水：１００質量部に分散させて調製した分散体を調製した。この分散体：１００質量部に、前記の酸化ジルコニウム水和物粒子の水分散体：２．５質量部を加え、分散用のビーズを用いずにペイントシェーカーで約１５分間混合し、鱗片状黒鉛と酸化ジルコニウム水和物粒子との合計１００質量％中、酸化ジルコニウム水和物粒子を１質量％の量で含有する負極合剤含有組成物を調製した。 Scale-like graphite (manufactured by Hitachi Chemical Co., Ltd., average particle diameter of primary particle diameter: about 450 μm): 98 parts by mass, acetylene black: 1 part by mass, and CMC: 1 part by mass are dispersed in water: 100 parts by mass. A prepared dispersion was prepared. To this dispersion: 100 parts by mass, the above-mentioned aqueous dispersion of zirconium oxide hydrate particles: 2.5 parts by mass was added, and the mixture was mixed for about 15 minutes using a paint shaker without using beads for dispersion. A negative electrode mixture-containing composition containing 1% by mass of zirconium oxide hydrate particles in a total of 100% by mass of zirconia and zirconium oxide hydrate particles was prepared.
＜リチウムイオン二次電池（テストセル）の作製＞
　前記の負極合剤含有組成物を、集電体となる厚みが８μｍの銅箔の片面にアプリケーターを用いて塗布して乾燥し、プレス処理した後、３５×３５ｍｍのサイズにカットして、負極を作製した。得られた負極の負極合剤層の厚みは６３μｍであった。 <Production of lithium ion secondary battery (test cell)>
The negative electrode mixture-containing composition is applied to one side of a copper foil having a thickness of 8 μm as a current collector using an applicator, dried, pressed, cut into a size of 35 × 35 mm, and the negative electrode Was made. The thickness of the negative electrode mixture layer of the obtained negative electrode was 63 μm.
　また、スピネルマンガン（ＬｉＭｎ２Ｏ４、一次粒子の平均粒子径：約１５μｍ）：９３質量部、アセチレンブラック：３．５質量部、ＰＶＤＦ：３．２質量部およびポリビニルピロリドン：０．３質量部を、ＮＭＰに分散させて正極合剤含有組成物を調製し、これを集電体となる厚みが１５μｍのアルミニウム箔の片面に、活物質であるスピネルマンガンの量が２０ｍｇ／ｃｍ２となるようにアプリケーターを用いて塗布して乾燥し、プレス処理した後、３０×３０ｍｍのサイズにカットして、正極を作製した。得られた正極の正極合剤層の厚みは８０μｍであった。 Spinel manganese (LiMn 2 O 4 , average particle diameter of primary particles: about 15 μm): 93 parts by mass, acetylene black: 3.5 parts by mass, PVDF: 3.2 parts by mass, and polyvinylpyrrolidone: 0.3 parts by mass Is dispersed in NMP to prepare a positive electrode mixture-containing composition, and the amount of spinel manganese as an active material is 20 mg / cm 2 on one side of an aluminum foil having a thickness of 15 μm that serves as a current collector. After applying and drying using an applicator, and press-processing, it cut | disconnected to the size of 30x30 mm, and produced the positive electrode. The thickness of the positive electrode mixture layer of the obtained positive electrode was 80 μm.
　前記の正極と前記の負極とを、セパレータ（厚みが１６μｍのＰＥ製微多孔膜）を介して積層してラミネートフィルム外装体内に挿入し、非水電解液（エチレンカーボネートとジエチルカーボネートとの体積比３：７の混合溶媒に、ＬｉＰＦ６を１．２Ｍの濃度で溶解した溶液）を注入した後にラミネートフィルム外装体を封止して、テストセルを作製した。 The positive electrode and the negative electrode are laminated via a separator (PE microporous film having a thickness of 16 μm) and inserted into a laminate film exterior, and a non-aqueous electrolyte (volume ratio of ethylene carbonate and diethyl carbonate) After injecting LiPF 6 at a concentration of 1.2 M into a 3: 7 mixed solvent, the laminate film outer package was sealed to prepare a test cell.
実施例２
　塩化セリウム七水和物を水に溶解させて３．０質量％濃度の塩化セリウム水溶液を調製した。アルカリ溶液として前記塩化セリウム水溶液と等塩基数の水酸化ナトリウム水溶液を用い、これを室温で攪拌しながら、ここに前記塩化セリウム水溶液を滴下して水酸化物を沈殿させた後、この懸濁液のｐＨを８に調整した。その後、この懸濁液を室温で約１２時間熟成させた後、ｐＨを８に再度調整し、実施例１と同様にして１８０℃で５時間の水熱処理を施し、更に実施例１と同様にして水洗後、濾過および乾燥することで、酸化セリウム（ＣｅＯ２）粒子を得た。 Example 2
Cerium chloride heptahydrate was dissolved in water to prepare a 3.0% by mass aqueous cerium chloride solution. The aqueous solution of cerium chloride and the aqueous solution of sodium hydroxide having the same number of bases are used as the alkaline solution. While stirring the solution at room temperature, the aqueous solution of cerium chloride is added dropwise to precipitate the hydroxide, and then the suspension. The pH of was adjusted to 8. Thereafter, the suspension was aged at room temperature for about 12 hours, then the pH was adjusted again to 8 and subjected to hydrothermal treatment at 180 ° C. for 5 hours in the same manner as in Example 1, and further in the same manner as in Example 1. After washing with water, filtration and drying were performed to obtain cerium oxide (CeO 2 ) particles.
　この酸化セリウム粒子について、粉末Ｘ線回折スペクトルを測定した結果、２θ＝２０～７０°の範囲内において、非常にブロードなピークを有しており、このピークの半値幅は１．７５°であった。 As a result of measuring the powder X-ray diffraction spectrum of this cerium oxide particle, it has a very broad peak in the range of 2θ = 20 to 70 °, and the half-value width of this peak is 1.75 °. It was.
　また、前記の酸化セリウム粒子のＴＥＭ写真から、前記の方法によって求めた一次粒子の平均粒子径は２．２ｎｍであり、窒素ガス吸着により求めた比表面積（ＢＥＴ比表面積）は２２０ｍ２／ｇであった。 Moreover, from the TEM photograph of the cerium oxide particles, the average particle diameter of the primary particles determined by the above method is 2.2 nm, and the specific surface area (BET specific surface area) determined by nitrogen gas adsorption is 220 m 2 / g. there were.
　酸化ジルコニウム水和物粒子に代えて、この酸化セリウム粒子を用いた以外は、実施例１と同様にして負極を作製し、この負極を用いた以外は実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 A negative electrode was prepared in the same manner as in Example 1 except that this cerium oxide particle was used in place of the zirconium oxide hydrate particles, and a test cell (lithium) was prepared in the same manner as in Example 1 except that this negative electrode was used. An ion secondary battery) was produced.
実施例３
　塩化アルミニウムを水に溶解させて４．０質量％濃度の塩化アルミニウム水溶液を調製した。アルカリ溶液として前記塩化アルミニウム水溶液と等塩基数の水酸化ナトリウム水溶液を用い、これを室温で攪拌しながら、ここに前記塩化アルミニウム水溶液を滴下して水酸化物を沈殿させた後、この懸濁液のｐＨを５に調整した。その後、この懸濁液を熟成させることなく、実施例１と同様にして９０℃で３６時間の水熱処理を施してアルミニウムゲルを得、更に実施例１と同様にして水洗後、濾過および乾燥することで、水酸化アルミニウム［Ａｌ（ＯＨ）３］粒子を得た。 Example 3
Aluminum chloride was dissolved in water to prepare 4.0 mass% aluminum chloride aqueous solution. The aqueous solution of aluminum chloride and the aqueous solution of sodium hydroxide having the same base number are used as the alkaline solution, and the aqueous solution of aluminum chloride is added dropwise to precipitate the hydroxide while stirring the solution at room temperature. The pH of the was adjusted to 5. Then, without aging this suspension, a hydrothermal treatment was performed at 90 ° C. for 36 hours in the same manner as in Example 1 to obtain an aluminum gel. After washing with water in the same manner as in Example 1, filtration and drying were performed. Thus, aluminum hydroxide [Al (OH) 3 ] particles were obtained.
　この水酸化アルミニウム粒子について、粉末Ｘ線回折スペクトルを測定した結果、２θ＝２０～７０°の範囲内において、非常にブロードなピークを有しており、このピークの半値幅は約９．５°で、何らかの構造を持つことを示すピークが見られるものの、結晶性を同定できないアモルファス構造に近い低結晶体であることが判明した。 As a result of measuring the powder X-ray diffraction spectrum of this aluminum hydroxide particle, it has a very broad peak in the range of 2θ = 20 to 70 °, and the half width of this peak is about 9.5 °. Thus, although a peak indicating that it has some structure is seen, it has been found that it is a low crystalline substance close to an amorphous structure in which the crystallinity cannot be identified.
　また、前記の水酸化アルミニウム粒子のＴＥＭ写真から、前記の方法によって求めた一次粒子の平均粒子径は８．２ｎｍであり、窒素ガス吸着により求めた比表面積（ＢＥＴ比表面積）は８５ｍ２／ｇであった。 Moreover, from the TEM photograph of the said aluminum hydroxide particle, the average particle diameter of the primary particle calculated | required by the said method is 8.2 nm, and the specific surface area (BET specific surface area) calculated | required by nitrogen gas adsorption | suction is 85 m < 2 > / g. Met.
　酸化ジルコニウム水和物粒子に代えて、この水酸化アルミニウム粒子を用いた以外は、実施例１と同様にして負極を作製し、この負極を用いた以外は実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 A negative electrode was prepared in the same manner as in Example 1 except that this aluminum hydroxide particle was used in place of the zirconium oxide hydrate particles, and a test cell (in the same manner as in Example 1 except that this negative electrode was used) Lithium ion secondary battery) was produced.
比較例１
　酸化ジルコニウム水和物粒子を使用しなかった以外は、実施例１と同様にして負極を作製し、この負極を用いた以外は実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 Comparative Example 1
A negative electrode was prepared in the same manner as in Example 1 except that zirconium oxide hydrate particles were not used, and a test cell (lithium ion secondary battery) was prepared in the same manner as in Example 1 except that this negative electrode was used. Produced.
比較例２
　鱗片状黒鉛などを含む分散体：１００質量部に、酸化ジルコニウム水和物粒子の水分散体：４３質量部を加えた以外は、実施例１と同様にして、鱗片状黒鉛と酸化ジルコニウム水和物粒子との合計１００質量％中、酸化ジルコニウム水和物粒子を１５質量％の量で含有する負極合剤含有組成物を調製した。 Comparative Example 2
Scale-like graphite and hydrated zirconium oxide were the same as in Example 1 except that the dispersion containing scale-like graphite and the like: 100 parts by mass and the aqueous dispersion of zirconium oxide hydrate particles: 43 parts by mass were added. A negative electrode mixture-containing composition containing 15% by mass of zirconium oxide hydrate particles in a total of 100% by mass with product particles was prepared.
　この負極合剤含有組成物を用いた以外は、実施例１と同様にして負極を作製し、この負極を用いた以外は実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 A negative electrode was produced in the same manner as in Example 1 except that this negative electrode mixture-containing composition was used, and a test cell (lithium ion secondary battery) was produced in the same manner as in Example 1 except that this negative electrode was used. did.
比較例３
　実施例１と同様にして合成した酸化ジルコニウム水和物粒子を、空気中６００℃で２時間の加熱処理を行い、酸化ジルコニウム粒子を得た。この酸化ジルコニウム粒子について、粉末Ｘ線回折スペクトルを測定した結果、２θ＝２０～７０°の範囲内において、単斜晶と正方晶の酸化ジルコニウムの混合物であることを示すピークが観測され、そのうち、最も強度の大きなピークの半値幅は０．７°であった。 Comparative Example 3
Zirconium oxide hydrate particles synthesized in the same manner as in Example 1 were heat-treated in air at 600 ° C. for 2 hours to obtain zirconium oxide particles. As a result of measuring the powder X-ray diffraction spectrum of the zirconium oxide particles, a peak indicating a mixture of monoclinic and tetragonal zirconium oxide was observed within the range of 2θ = 20 to 70 °, of which The full width at half maximum of the strongest peak was 0.7 °.
　また、前記の酸化アルミニウム粒子のＴＥＭ写真から、前記の方法によって求めた一次粒子の平均粒子径は２５ｎｍであり、窒素ガス吸着により求めた比表面積（ＢＥＴ比表面積）は２３ｍ２／ｇであった。 Moreover, from the TEM photograph of the said aluminum oxide particle, the average particle diameter of the primary particle calculated | required by the said method was 25 nm, and the specific surface area (BET specific surface area) calculated | required by nitrogen gas adsorption was 23 m < 2 > / g. .
　酸化ジルコニウム水和物粒子に代えて、この酸化ジルコニウム粒子を用いた以外は、実施例１と同様にして負極を作製し、この負極を用いた以外は実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 A negative electrode was prepared in the same manner as in Example 1 except that this zirconium oxide particle was used in place of the zirconium oxide hydrate particles, and a test cell (lithium) was prepared in the same manner as in Example 1 except that this negative electrode was used. An ion secondary battery) was produced.
比較例４
　実施例３と同様にして合成した水酸化アルミニウム粒子を、空気中１２００℃で４時間の加熱処理を行い、酸化アルミニウム粒子を得た。この酸化アルミニウム粒子について、粉末Ｘ線回折スペクトルを測定した結果、２θ＝２０～７０°の範囲内において、α－アルミナを示すピークが観測され、このピークの半値幅は０．２８°であった。 Comparative Example 4
Aluminum hydroxide particles synthesized in the same manner as in Example 3 were heat-treated in air at 1200 ° C. for 4 hours to obtain aluminum oxide particles. As a result of measuring the powder X-ray diffraction spectrum of the aluminum oxide particles, a peak indicating α-alumina was observed within the range of 2θ = 20 to 70 °, and the half-value width of this peak was 0.28 °. .
　また、前記の酸化アルミニウム粒子のＴＥＭ写真から、前記の方法によって求めた一次粒子の平均粒子径は２７４ｎｍであり、窒素ガス吸着により求めた比表面積（ＢＥＴ比表面積）は９．６ｍ２／ｇであった。 Moreover, from the TEM photograph of the said aluminum oxide particle, the average particle diameter of the primary particle calculated | required by the said method is 274 nm, and the specific surface area (BET specific surface area) calculated | required by nitrogen gas adsorption is 9.6 m < 2 > / g. there were.
　酸化ジルコニウム水和物粒子に代えて、この酸化アルミニウム粒子を用いた以外は、実施例１と同様にして負極を作製し、この負極を用いた以外は実施例１と同様にしてテストセル（リチウムイオン二次電池）を作製した。 A negative electrode was prepared in the same manner as in Example 1 except that this aluminum oxide particle was used in place of the zirconium oxide hydrate particles, and a test cell (lithium) was prepared in the same manner as in Example 1 except that this negative electrode was used. An ion secondary battery) was produced.
　実施例および比較例のテストセルについて、以下の方法で負荷特性および充放電サイクル特性を評価した。 The load characteristics and charge / discharge cycle characteristics of the test cells of the examples and comparative examples were evaluated by the following methods.
＜負荷特性＞
　実施例および比較例のテストセルについて、１Ｃの電流値で電圧が４．２Ｖになるまで定電流充電を行い、続いて、４．２Ｖで定電圧充電を行った。なお、定電流充電および定電圧充電の総充電時間は２時間とした。その後、各テストセルを０．２Ｃの電流値で電圧が２．５Ｖになるまで放電させて、０．２Ｃ放電容量を求めた。 <Load characteristics>
About the test cell of the Example and the comparative example, the constant current charge was performed until the voltage became 4.2V at the current value of 1C, and then the constant voltage charge was performed at 4.2V. The total charging time for constant current charging and constant voltage charging was 2 hours. Thereafter, each test cell was discharged at a current value of 0.2 C until the voltage reached 2.5 V, and a 0.2 C discharge capacity was obtained.
　また、各テストセルについて、前記と同じ条件で充電を行った後、５Ｃの電流地で電圧が２．５Ｖになるまで放電させて、５Ｃ放電容量を求めた。そして、各テストセルについて、５Ｃ放電容量を０．２Ｃ放電容量で除した値を百分率で表して、容量維持率を求めた。この容量維持率が大きいほど、テストセルの負荷特性が良好であるといえる。 In addition, each test cell was charged under the same conditions as described above, and then discharged at a 5 C current ground until the voltage became 2.5 V to obtain a 5 C discharge capacity. And about each test cell, the value which remove | divided 5C discharge capacity by 0.2C discharge capacity was represented by the percentage, and the capacity | capacitance maintenance factor was calculated | required. It can be said that the larger the capacity retention rate, the better the load characteristics of the test cell.
＜充放電サイクル特性＞
　実施例および比較例のテストセルについて、１Ｃの電流値で電圧が４．２Ｖになるまで定電流充電を行い、続いて、４．２Ｖで定電圧充電を行った。なお、定電流充電および定電圧充電の総充電時間は２時間とした。その後、各テストセルを１Ｃの電流値で電圧が２．５Ｖになるまで放電させた。この定電圧充電－定電流充電－放電の一連の操作を１サイクルとして、１００サイクルの充放電を行った。そして、１００サイクル目の放電容量を１０サイクル目の放電容量で除した値を百分率で表して、容量維持率を求めた。この容量維持率が大きいほど、テストセルの充放電サイクル特性が良好であるといえる。 <Charge / discharge cycle characteristics>
About the test cell of the Example and the comparative example, the constant current charge was performed until the voltage became 4.2V at the current value of 1C, and then the constant voltage charge was performed at 4.2V. The total charging time for constant current charging and constant voltage charging was 2 hours. Thereafter, each test cell was discharged at a current value of 1 C until the voltage reached 2.5V. A series of operations of constant voltage charging-constant current charging-discharging was defined as one cycle, and charging / discharging for 100 cycles was performed. Then, a value obtained by dividing the discharge capacity at the 100th cycle by the discharge capacity at the 10th cycle was expressed as a percentage to obtain the capacity maintenance rate. It can be said that the larger the capacity retention rate, the better the charge / discharge cycle characteristics of the test cell.
　実施例および比較例のテストセルに使用した酸化物粒子の構成を表１および表２に示し、前記の各評価結果を表３に示す。 Tables 1 and 2 show the composition of the oxide particles used in the test cells of Examples and Comparative Examples, and Table 3 shows the evaluation results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１における「半値幅」は、酸化物粒子の粉末Ｘ線回折スペクトルにおける２θ＝２０～７０°の範囲内に存在する最も強度の大きなピークの半値幅を意味している。 “Half-width” in Table 1 means the half-width of the highest intensity peak present in the range of 2θ = 20 to 70 ° in the powder X-ray diffraction spectrum of the oxide particles.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２における「割合」は、活物質粒子と酸化物粒子との合計１００質量％中における酸化物粒子の割合を意味している。 “Ratio” in Table 2 means the ratio of oxide particles in 100% by mass of the total of active material particles and oxide particles.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１～表３から明らかなように、一次粒子の平均粒子径が適正であり、かつ結晶性の低い酸化物粒子を、適正な量で含有する負極を有する実施例１～３のテストセルは、酸化物粒子を含有しない負極を有する比較例１のテストセルに比べて、負荷特性および充放電サイクル特性が優れている。 As is apparent from Tables 1 to 3, the test cells of Examples 1 to 3 each having a negative electrode containing an appropriate amount of oxide particles having an appropriate primary particle average particle size and low crystallinity are as follows. Compared with the test cell of Comparative Example 1 having a negative electrode containing no oxide particles, the load characteristics and charge / discharge cycle characteristics are excellent.
　一方、酸化物粒子の量が多すぎる負極を用いた比較例２のテストセルは、酸化物粒子を含有させたことによる効果と共に、絶縁性の粒子を混合したことによる電子伝導性の低下の影響が現れ、負荷特性は悪化しないものの、実施例のテストセルに比べて、その向上効果が劣っている。また、比較例３、４のテストセルは、一次粒子径の平均粒子径が大きく、かつ結晶性の高い酸化物粒子を含有する負極を有しているが、このうち、比較的粒子径の小さな酸化物粒子を使用した比較例３のテストセルは、酸化物粒子を用いていない比較例１のテストセルと負荷特性が同程度であり、また、より粗大な酸化物粒子を使用した比較例４のテストセルは、比較例１のテストセルよりも負荷特性が劣っており、いずれも負荷特性の大幅な向上が見込めない。 On the other hand, the test cell of Comparative Example 2 using a negative electrode having too much amount of oxide particles has the effect of lowering the electronic conductivity due to the mixing of insulating particles as well as the effect of containing oxide particles. Although the load characteristic does not deteriorate, the improvement effect is inferior to that of the test cell of the example. Further, the test cells of Comparative Examples 3 and 4 have a negative electrode containing oxide particles having a high average particle size of primary particles and high crystallinity, and of these, the particle size is relatively small. The test cell of Comparative Example 3 using oxide particles has the same load characteristics as the test cell of Comparative Example 1 not using oxide particles, and Comparative Example 4 using coarser oxide particles. These test cells have inferior load characteristics as compared with the test cell of Comparative Example 1, and none of the test cells can be expected to significantly improve load characteristics.

Claims (9)

  1. 　酸化物粒子、Ｌｉを吸蔵放出可能な活物質粒子および樹脂製バインダを含む電極合剤層を有するリチウムイオン二次電池用電極であって、
    　前記酸化物粒子は、一次粒子の平均粒子径が１～２０ｎｍであり、粉末Ｘ線回折スペクトルにおける２θ＝２０～７０°の範囲内において、ピークを有していないか、または最も強度の大きなピークの半値幅が１．５°以上であり、
    　前記活物質粒子と前記酸化物粒子の合計を１００質量％としたとき、前記酸化物粒子の割合が０．１～１０質量％であることを特徴とするリチウムイオン二次電池用電極。     An electrode for a lithium ion secondary battery having an electrode mixture layer containing oxide particles, active material particles capable of occluding and releasing Li, and a resin binder,
    The oxide particles have an average primary particle diameter of 1 to 20 nm and have no peak or the highest intensity peak in the range of 2θ = 20 to 70 ° in the powder X-ray diffraction spectrum. The half-value width is 1.5 ° or more,
    An electrode for a lithium ion secondary battery, wherein the ratio of the oxide particles is 0.1 to 10% by mass when the total of the active material particles and the oxide particles is 100% by mass.
  2. 　酸化物粒子の窒素ガス吸着により求められる比表面積が、３０～５００ｍ２／ｇである請求項１に記載のリチウムイオン二次電池用電極。 The electrode for a lithium ion secondary battery according to claim 1, wherein the specific surface area determined by nitrogen gas adsorption of the oxide particles is 30 to 500 m 2 / g.
  3. 　電極合剤層内における酸化物粒子の分散粒子径が、３００ｎｍ以下である請求項１または２に記載のリチウムイオン二次電池用電極。 The electrode for a lithium ion secondary battery according to claim 1 or 2, wherein the dispersed particle diameter of the oxide particles in the electrode mixture layer is 300 nm or less.
  4. 　酸化物粒子は、Ｓｉ、Ｚｒ、Ａｌ、Ｃｅ、Ｍｇ、Ｔｉ、ＢａおよびＳｒよりなる群から選択される少なくとも１種の元素を含む酸化物の粒子である請求項１～３のいずれかに記載のリチウムイオン二次電池用電極。 The oxide particles are oxide particles containing at least one element selected from the group consisting of Si, Zr, Al, Ce, Mg, Ti, Ba and Sr. Of lithium ion secondary battery.
  5. 　酸化物粒子が、ＺｒＯ２・ｎＨ２Ｏ（ｎ＝０．５～１０）、ＣｅＯ２またはＡｌ（ＯＨ）３の粒子である請求項４に記載のリチウムイオン二次電池用電極。 The electrode for a lithium ion secondary battery according to claim 4, wherein the oxide particles are particles of ZrO 2 · nH 2 O (n = 0.5 to 10), CeO 2 or Al (OH) 3 .
  6. 　酸化物粒子は、水溶液中酸化処理により得られたものである請求項１～５のいずれかに記載のリチウムイオン二次電池用電極。 The electrode for a lithium ion secondary battery according to any one of claims 1 to 5, wherein the oxide particles are obtained by an oxidation treatment in an aqueous solution.
  7. 　水溶液中酸化処理が水熱処理である請求項６に記載のリチウムイオン二次電池用電極。 The electrode for a lithium ion secondary battery according to claim 6, wherein the oxidation treatment in an aqueous solution is a hydrothermal treatment.
  8. 　酸化物粒子は、ｐＨ４～１１の懸濁液中で６０～２００℃の水熱処理により得られたものである請求項７に記載のリチウムイオン二次電池用電極。 The electrode for a lithium ion secondary battery according to claim 7, wherein the oxide particles are obtained by hydrothermal treatment at 60 to 200 ° C in a suspension having a pH of 4 to 11.
  9. 　正極、負極、非水電解液およびセパレータを有するリチウムイオン二次電池であって、
    　前記正極および／または前記負極が、請求項１～８のいずれかに記載のリチウムイオン二次電池用電極であることを特徴とするリチウムイオン二次電池。     A lithium ion secondary battery having a positive electrode, a negative electrode, a non-aqueous electrolyte, and a separator,
    A lithium ion secondary battery, wherein the positive electrode and / or the negative electrode is an electrode for a lithium ion secondary battery according to any one of claims 1 to 8.
PCT/JP2010/072873 2010-12-20 2010-12-20 Electrode for lithium ion secondary battery, and lithium ion secondary battery WO2012085994A1 (en)

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JP2003206475A (en) * 2001-09-26 2003-07-22 Hitachi Maxell Ltd Nonmagnetic platy particle, method for producing the same and abrasive, polishing material and polishing liquid using the particle
JP2005285545A (en) * 2004-03-30 2005-10-13 Ngk Insulators Ltd Lithium secondary battery
JP2010272511A (en) * 2009-04-24 2010-12-02 Dainippon Printing Co Ltd Electrode plate for nonaqueous electrolyte solution secondary battery, method for manufacturing electrode plate for nonaqueous electrolyte solution secondary battery, and nonaqueous electrolyte solution secondary battery

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002141069A (en) * 2000-08-21 2002-05-17 Samsung Sdi Co Ltd Electrode for lithium secondary battery and lithium secondary battery
JP2003109599A (en) * 2000-12-27 2003-04-11 Toshiba Corp Positive electrode active material, and nonaqueous electrolyte secondary battery using the same
JP2003206475A (en) * 2001-09-26 2003-07-22 Hitachi Maxell Ltd Nonmagnetic platy particle, method for producing the same and abrasive, polishing material and polishing liquid using the particle
JP2005285545A (en) * 2004-03-30 2005-10-13 Ngk Insulators Ltd Lithium secondary battery
JP2010272511A (en) * 2009-04-24 2010-12-02 Dainippon Printing Co Ltd Electrode plate for nonaqueous electrolyte solution secondary battery, method for manufacturing electrode plate for nonaqueous electrolyte solution secondary battery, and nonaqueous electrolyte solution secondary battery

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