WO2013099279A1 - Electrode négative pour batteries secondaires à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux comprenant l'électrode négative pour batteries secondaires à électrolyte non aqueux - Google Patents

Electrode négative pour batteries secondaires à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux comprenant l'électrode négative pour batteries secondaires à électrolyte non aqueux Download PDF

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WO2013099279A1
WO2013099279A1 PCT/JP2012/008420 JP2012008420W WO2013099279A1 WO 2013099279 A1 WO2013099279 A1 WO 2013099279A1 JP 2012008420 W JP2012008420 W JP 2012008420W WO 2013099279 A1 WO2013099279 A1 WO 2013099279A1
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active material
negative electrode
electrolyte secondary
secondary battery
potential
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PCT/JP2012/008420
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English (en)
Japanese (ja)
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名倉　健祐
尚士 細川
暢宏 平野
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パナソニック株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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 nonaqueous electrolyte secondary battery having a negative electrode for a nonaqueous electrolyte secondary battery and a negative electrode for a nonaqueous electrolyte secondary battery.
  • non-aqueous electrolyte secondary batteries represented by lithium ion secondary batteries as driving power sources for portable electronic devices such as mobile phones, notebook computers and digital cameras, hybrid vehicles, and electric vehicles has been increasing. .
  • the lithium ion secondary battery includes, for example, a lithium-containing composite oxide as a positive electrode active material, and includes, for example, graphite as a negative electrode active material.
  • Patent Document 1 proposes a technique including Li 4 Ti 5 O 12 in addition to graphite as a negative electrode active material. Specifically, Patent Document 1 discloses a first layer containing a negative electrode active material made of graphite and formed on a negative electrode current collector, and Li 4 Ti 5 O 12 formed on the first layer. A lithium ion secondary battery including a negative electrode having a second layer containing a negative electrode active material is described.
  • the operating potential of Li 4 Ti 5 O 12 is higher than the lithium deposition potential.
  • an object of the present invention is to provide cycle characteristics in a nonaqueous electrolyte secondary battery including a negative electrode for a nonaqueous electrolyte secondary battery having a negative electrode active material layer including a first active material and a second active material. It is to prevent the decrease of.
  • a negative electrode for a nonaqueous electrolyte secondary battery includes a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector. Includes a first active material and a second active material, the first active material occludes and releases lithium ions at a first potential, and the second active material is a first active material. At a first potential close to the first potential and a second potential higher than the first potential, lithium ions are absorbed and released, and the first potential and the second activity of the second active material are absorbed.
  • the difference between the second potential of the material is 0.1 V or more, and the second active material at the second potential with respect to the first electrochemical capacitance C1 at the first potential of the second active material.
  • the capacity ratio C2 / C1 of the second electrochemical capacity C2 is 3.3 or less.
  • non-aqueous electrolyte secondary battery having the negative electrode for non-aqueous electrolyte secondary battery and the negative electrode for non-aqueous electrolyte secondary battery according to the present invention, high lithium ion acceptability can be ensured in a low temperature environment. For this reason, it is possible to prevent lithium from being deposited on the surface of the negative electrode during high rate charging in a low temperature environment, and to prevent deterioration of cycle characteristics.
  • the capacitance ratio C2 / C1 of the second electrochemical capacitance C2 at the second potential of the second active material to the first electrochemical capacitance C1 at the first potential of the second active material is 3.3 or less.
  • the inventors of the present application have found that the above problem can be solved (preventing deterioration of cycle characteristics) by making the above.
  • the inventors of the present application consider that the above-described problem can be solved because the second active material can have a sufficient electrochemical capacity at the first potential.
  • the negative electrode for a non-aqueous electrolyte secondary battery includes a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector.
  • the negative electrode active material layer includes a first active material and a second active material.
  • the first active material occludes and releases lithium ions at a first potential.
  • the second active material occludes and releases lithium ions at a first potential close to the first potential of the first active material and at a second potential higher than the first potential.
  • the “first potential” and the “second potential” are average values of relatively flat potential regions that occlude and release lithium ions, respectively, more specifically, unit capacitance. This is the average value of the potential region where the potential change ⁇ V per (1 mAh / g) is 0.01 V or less.
  • the difference between the first potential of the second active material and the second potential of the second active material is 0.1 V or more. If the difference between the first potential and the second potential is less than 0.1 V, sufficient lithium ion acceptability may not be obtained.
  • the difference between the first potential and the second potential is preferably 0.2 V or more, and more preferably 0.5 V or more. However, if the difference between the first potential and the second potential is too large, the charge / discharge control of the battery becomes complicated, so the difference is preferably 1.8 V or less, and is 1.6 V or less. Is more preferable.
  • the capacitance ratio C2 / C1 of the second electrochemical capacitor C2 at the second potential of the second active material to the first electrochemical capacitor C1 at the first potential of the second active material is 3.3. It is as follows.
  • the first potential of the second active material is a potential close to the first potential of the first active material.
  • the difference between the first potential of the second active material and the first potential of the first active material is preferably 0 V or more and 0.07 V or less.
  • the difference is 0.03V or more and 0.05V or less.
  • the negative electrode active material layer includes, for example, a first layer formed on the negative electrode current collector and including the first active material, and a second layer formed on the first layer and including the second active material. And have.
  • the thickness ratio T1 / T2 of the first layer thickness T1 to the second layer thickness T2 is preferably 0.33 or more and 75 or less.
  • T1 / T2 is smaller than 0.33, the amount of the second active material that reacts with lithium ions at the second potential increases, and thus the energy density of the entire negative electrode decreases.
  • T1 / T2 is larger than 75, the amount of the second active material having excellent input / output characteristics is reduced, so that the acceptability of lithium ions in the whole negative electrode is lowered.
  • the total thickness T1 + T2 of the first layer thickness T1 and the second layer thickness T2 is preferably 40 ⁇ m or more and 300 ⁇ m or less, and more preferably 45 ⁇ m or more and 100 ⁇ m or less.
  • the negative electrode active material layer is, for example, a single layer formed on the negative electrode current collector and including the first active material and the second active material.
  • the weight ratio of the weight W2 of the second active material to the total weight W1 + W2 of the weight W1 of the first active material and the weight W2 of the second active material is preferably 5% or more and 25% or less. .
  • the weight ratio is less than 5%, the amount of the second active material having excellent input / output characteristics is reduced, so that the acceptability of lithium ions in the whole negative electrode is lowered.
  • the weight ratio is larger than 30%, the amount of the second active material that reacts with lithium ions at the second potential increases, and thus the energy density of the entire negative electrode decreases.
  • the first potential of the first active material is preferably less than 0.7 V with respect to Li / Li + .
  • the first potential of the first active material is 0.7 V or more with respect to Li / Li + , the energy density of the battery is lowered.
  • the second potential of the second active material is preferably 0.2 V or more and 3.0 V or less with respect to Li / Li + .
  • the second potential is smaller than 0.2 V with respect to Li / Li + , the lithium ion acceptability is lowered.
  • the second potential is larger than 3.0 V with respect to Li / Li + , the energy density of the battery is lowered.
  • the first potential is less than 0.7 V with respect to Li / Li + ” means an operating potential of less than 0.7 V.
  • the second potential is 0.2 V or more and 3.0 V or less with respect to Li / Li + ” means an operating potential of 0.2 V or more and 3.0 V or less.
  • the first active material is preferably made of a carbon material having a graphite structure.
  • Examples of the carbon material having a graphite structure include natural graphite, artificial graphite, and graphitized mesophase microspheres.
  • the specific surface area of the carbon material having a graphite structure is preferably 0.5 m 2 / g or more and 20 m 2 / g or less, and more preferably 1.0 m 2 / g or more and 10 m 2 / g or less.
  • the specific surface area can be determined by the BET method.
  • a diffraction image of a carbon material having a graphite structure measured by a wide angle X-ray diffraction method has a peak attributed to the (101) plane and a peak attributed to the (100) plane.
  • the ratio of the peak intensity I (101) attributed to the (101) plane to the intensity I (100) attributed to the (100) plane is 0.01 ⁇ I (101) / I (100) ⁇ 0. .25 and more preferably 0.08 ⁇ I (101) / I (100) ⁇ 0.20.
  • the peak intensity means the peak height.
  • the average particle diameter of the carbon material particles having a graphite structure is preferably 8 ⁇ m or more and 25 ⁇ m or less, and more preferably 10 ⁇ m or more and 20 ⁇ m or less.
  • the “average particle size” is the particle size at which the relative particle amount is 50% in the particle size distribution (the particle size distribution indicating the relative particle amount with respect to the particle size) using the volume standard as the reference of the relative particle amount, that is, the middle This means the diameter (Median diameter), so-called D50.
  • the particle size distribution can be measured by, for example, a laser diffraction type particle size distribution measuring apparatus. *
  • the second active material is preferably made of an oxide containing lithium and a transition metal.
  • the second active material is made of lithium-deficient lithium titanate Li x Ti y O z having a spinel crystal structure (see Examples 1 to 10 and 22 to 26 described later).
  • Lithium titanate having a spinel crystal structure has a second potential lower than that of an oxide containing a transition metal other than titanium.
  • lithium titanate having a spinel crystal structure is difficult to inhibit the occlusion and release of lithium ions by the carbon material.
  • lithium titanate has a high acceptability of lithium ions and can easily reduce the diffusion resistance of the negative electrode.
  • lithium titanate does not have electrical conductivity and has higher thermal stability than carbon materials. For this reason, even if an internal short circuit of the battery occurs, current does not flow rapidly, and heat generation is suppressed.
  • the specific surface area of lithium-deficient lithium titanate having a spinel crystal structure is preferably 0.5 m 2 / g or more and 10 m 2 / g or less, and 2.5 m 2 / g or more and 4.5 m 2. / G or less is more preferable.
  • the specific surface area can be determined by the BET method.
  • the average particle diameter of lithium deficient lithium titanate particles having a spinel crystal structure is preferably 0.8 ⁇ m or more and 30 ⁇ m or less, and more preferably 1 ⁇ m or more and 20 ⁇ m or less.
  • the “average particle diameter” means a particle diameter at which the relative particle amount is 50% in the particle size distribution using the volume basis as a reference for the relative particle amount.
  • the particle size distribution can be measured by, for example, a laser diffraction type particle size distribution measuring apparatus.
  • the second active material is preferably made of an oxide containing lithium, a transition metal, and the element M.
  • Element M is an element group consisting of magnesium, calcium, strontium, barium, sodium, manganese, aluminum, zirconium, niobium, boron, nickel, vanadium, iron, cobalt, copper, zinc, molybdenum, tungsten, bismuth, gallium and rare earth elements. It is preferable that at least one element selected from is included.
  • the second active material has a spinel crystal structure, and is an oxide Li x M w Ti y O z containing lithium, titanium, and element M (see Examples 11 to 15 and 27 to 31 described later). ) Or Li x Ti y M w O z (see Examples 16 to 21, 32 to 37 described later).
  • Mg Mg, Ca
  • M Sr, Ba
  • M Al, Zr
  • the second active material is preferably made of an oxide containing a transition metal (hereinafter referred to as “transition metal oxide”).
  • the transition metal oxide preferably has a layered crystal structure, or a spinel-type, olivine-type, NASICON-type, or perovskite-type crystal structure.
  • the transition metal preferably includes at least one transition metal selected from the transition metal group consisting of titanium, vanadium, iron, cobalt, copper, molybdenum, tungsten, manganese, niobium, and nickel.
  • the second active material is preferably made of an oxide containing a metal.
  • the metal includes at least one metal selected from the metal group consisting of boron (metalloid), silicon (metalloid), tin (base metal), zinc (base metal), bismuth (base metal) and lithium (alkali metal). Is preferred.
  • the negative electrode current collector is preferably made of copper foil, copper alloy foil or nickel foil.
  • the thickness of the negative electrode current collector is, for example, 5 ⁇ m or more and 30 ⁇ m or less, but is not particularly limited.
  • the negative electrode active material layer may contain a binder in addition to the first active material and the second active material.
  • the negative electrode active material layer can include 0.5 to 10 parts by weight of a binder per 100 parts by weight of the first active material.
  • the binder is preferably made of an acrylic resin, a fluororesin or a diene rubber.
  • acrylic resin include polyacrylic acid, polymethacrylic acid, sodium salt of polyacrylic acid, sodium salt of polymethacrylic acid, and acrylic acid-ethylene copolymer.
  • the fluororesin include polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and vinylidene fluoride-hexafluoropropylene copolymer.
  • the diene rubber include styrene-butadiene copolymer (SBR).
  • the negative electrode active material layer may contain a thickener in addition to the first active material and the second active material.
  • the negative electrode active material layer can include 0.1 to 5 parts by weight of a thickener per 100 parts by weight of the first active material.
  • the thickener is preferably made of a water-soluble polymer compound such as polyethylene oxide or a cellulose derivative.
  • Cellulose derivatives include carboxymethyl cellulose (CMC), methyl cellulose (MC) and cellulose acetate phthalate (CAP).
  • the capacity ratio C2 / C1 of the second electrochemical capacity C2 to the first electrochemical capacity C1 is 3.3 or less. Therefore, it is possible to prevent lithium from being deposited on the surface of the negative electrode during high rate charging in a low temperature environment, and to prevent deterioration of cycle characteristics.
  • the first active material is made of a carbon material having a graphite structure (more specifically, artificial graphite).
  • the second active material is made of lithium deficient lithium titanate having a spinel crystal structure or an oxide having a spinel crystal structure and containing lithium, titanium, and element M.
  • the capacity ratio C2 / C1 can be reduced to 3.3 or less (3 to 3.3).
  • the acceptability of the high lithium ion in a low-temperature environment is securable. For this reason, it is possible to prevent lithium from being deposited on the surface of the negative electrode during high rate charging in a low temperature environment, and to prevent deterioration of cycle characteristics.
  • the negative electrode active material layer includes the first active material and the second active material
  • the defect of the first active material and the defect of the second active material can be compensated for each other.
  • the first active material has a low first potential with respect to Li / Li + and can easily obtain a high capacity.
  • the acceptability of lithium ions is low.
  • the second active material has a high second potential with respect to Li / Li + and a high acceptability of lithium ions.
  • a non-aqueous electrolyte secondary battery according to the present invention is interposed between a negative electrode for a non-aqueous electrolyte secondary battery according to the present invention (hereinafter sometimes simply referred to as “negative electrode”), a positive electrode, and a positive electrode and a negative electrode.
  • An insulating film having lithium ion permeability and an electrolyte layer having lithium ion conductivity interposed between a positive electrode and a negative electrode are provided.
  • the positive electrode has a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
  • the positive electrode active material layer includes a third active material that absorbs and releases lithium ions at a first potential.
  • the first potential of the third active material is preferably higher than the second potential of the second active material.
  • the third active material is made of an oxide containing, for example, lithium and a transition metal.
  • the transition metal contained in the third active material is preferably different from the transition metal contained in the second active material.
  • the third active material is made of, for example, lithium cobaltate, lithium nickelate, or lithium manganate, but is not limited thereto.
  • the electrolyte layer having lithium ion conductivity includes a non-aqueous solvent and a lithium salt that dissolves in the non-aqueous solvent.
  • non-aqueous solvent examples include ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). It is not limited to. Among the listed non-aqueous solvents, one kind may be used alone, or two or more kinds may be used in combination.
  • lithium salt examples include LiBF 4 , LiPF 6 , LiAlCl 4 , LiCl, and lithium imide salt.
  • one type may be used alone, or two or more types may be used in combination.
  • the electrolyte layer having lithium ion conductivity has a viscosity of 1 cP [mPa ⁇ s] or more and 3 cP [mPa].
  • -It is preferable to use the nonaqueous electrolyte solution which is below s].
  • a separator having an air permeability of 5 seconds to 300 seconds is preferably used as the insulating film having lithium ion permeability. The viscosity can be measured with a cone-plate rotary viscometer at a measurement temperature of 20 ° C.
  • the second active material is composed of lithium titanate
  • titanate unlike titanate, the crystal structure of the lithium titanate does not expand and contract during charge / discharge, and therefore the non-aqueous electrolyte does not easily flow in the battery. Therefore, a non-aqueous electrolyte and a separator having the above physical properties are used. Thereby, the fluidity
  • the second layer is not only the second active material.
  • a fourth active material may be further included.
  • the second layer can include 30 parts by weight or less (for example, 5 parts by weight or more and 20 parts by weight or less) of the fourth active material per 100 parts by weight of the second active material.
  • a 4th active material consists of a carbon material which has electroconductivity.
  • the carbon material having conductivity for example, natural graphite, artificial graphite, graphitized mesophase microsphere, carbon black, carbon fiber, or carbon nanotube can be used.
  • the second layer can impart conductivity to the second layer.
  • the negative electrode active material layer has a first layer containing a first active material and a second layer containing a second active material will be described below.
  • Example 1> (Preparation of negative electrode) (I) First layer 3 kg of artificial graphite (average particle size 10 ⁇ m, BET specific surface area 3 m 2 / g) as the first active material, and BM-400B (solid content 40 wt. % Of modified styrene-butadiene rubber dispersion (200 g) and 50 g of carboxymethyl cellulose (CMC) as a thickener together with an appropriate amount of water, and agitated in a double-arm kneader, the first negative electrode mixture paste was prepared.
  • artificial graphite average particle size 10 ⁇ m, BET specific surface area 3 m 2 / g
  • BM-400B solid content 40 wt. % Of modified styrene-butadiene rubber dispersion (200 g) and 50 g of carboxymethyl cellulose (CMC) as a thickener together with an appropriate amount of water, and agitated in a double-arm kneader,
  • the first negative electrode mixture paste was applied to both surfaces (front and back surfaces) of a negative electrode current collector made of a copper foil having a thickness of 10 ⁇ m, dried, and rolled to a total thickness of 50 ⁇ m.
  • the first layer was formed on the surface of the negative electrode current collector, and the first layer was formed on the back surface of the negative electrode current collector.
  • the thickness T1 of the first layer was 20 ⁇ m, and the density of the first layer was 1.3 g / cm 3 .
  • Second layer Lithium-deficient lithium titanate having a spinel crystal structure as the second active material Li 3.97 Ti 5 O 12 , average particle size 1 ⁇ m, BET specific surface area 3 m 2 / g) 2 kg, 200 g of artificial graphite (average particle size 10 ⁇ m) as the fourth active material, and 200 g of BM-400B (modified styrene-butadiene rubber dispersion having a solid content of 40 wt%) manufactured by Nippon Zeon Co., Ltd.
  • CMC carboxymethyl cellulose
  • the negative electrode current collector, the first layer formed on the negative electrode current collector and including the first active material, and the second active material formed on the first layer A negative electrode plate provided with a negative electrode active material layer having a second layer was obtained.
  • the obtained negative electrode plate was cut into a width and a length that could be inserted into a cylindrical 18650 battery case to obtain a negative electrode.
  • the first potential at which the first active material made of artificial graphite occludes and releases lithium ions is 0.05V. In other words, the first potential of the first active material is 0.05 V with respect to Li / Li + .
  • the second potential at which the second active material made of lithium-deficient lithium titanate having a spinel crystal structure occludes and releases lithium ions is 1.5V. In other words, the second potential of the second active material is 1.5 V with respect to Li / Li + . Therefore, the difference between the first potential of the first active material and the second potential of the second active material is 1.45V.
  • a positive electrode plate including a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector was obtained.
  • the obtained positive electrode plate was cut into a width and a length that can be inserted into a cylindrical 18650 battery case to obtain a positive electrode.
  • the first potential at which the third active material made of lithium cobaltate occludes and releases lithium ions is 3.8V.
  • the first potential (3.8V) of the third active material is higher than the second potential (1.5V) of the second active material.
  • a positive electrode lead made of aluminum was attached to the positive electrode current collector, and a negative electrode lead made of nickel was attached to the negative electrode current collector.
  • the positive electrode and the negative electrode were wound through a separator (A089, manufactured by Celgard Co., Ltd.), which is a polyethylene microporous film having a thickness of 20 ⁇ m, to form a cylindrical electrode group.
  • the negative electrode lead is welded to the bottom of a nickel-plated iron-made cylindrical 18650 battery case (inner diameter: 18 mm), and the positive electrode lead is welded to a sealing body having a safety valve. Housed inside.
  • An insulating plate was disposed at the upper end of the electrode group, while an insulating plate was disposed at the lower end of the electrode group.
  • 5.5 g of non-aqueous electrolyte was injected into the battery case.
  • the opening edge part of the battery case was caulked to the peripheral part of the sealing board via the gasket. In this manner, a cylindrical nonaqueous electrolyte secondary battery having an inner diameter of 18 mm, a height of 65 mm, and a design capacity of 1300 mAh was produced.
  • Example 2 In (preparation of negative electrode), the nonaqueous electrolyte secondary battery was manufactured in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were 300 ⁇ m and 4 ⁇ m, respectively. Produced.
  • Example 3 In (preparation of negative electrode), the nonaqueous electrolyte secondary battery was manufactured in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were 200 ⁇ m and 4 ⁇ m, respectively. Produced.
  • Example 4 In (preparation of negative electrode), the nonaqueous electrolyte secondary battery was manufactured in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were 100 ⁇ m and 4 ⁇ m, respectively. Produced.
  • Example 5 In (preparation of negative electrode), a nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were 40 ⁇ m and 4 ⁇ m, respectively. Produced.
  • Example 6 A nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were set to 30 ⁇ m and 10 ⁇ m, respectively (preparation of the negative electrode). Produced.
  • Example 7 In (preparation of negative electrode), the nonaqueous electrolyte secondary battery was fabricated in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were 50 ⁇ m and 20 ⁇ m, respectively. Produced.
  • Example 8 A nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were 150 ⁇ m and 150 ⁇ m, respectively, in (Preparation of negative electrode). Produced.
  • Example 9 In (Preparation of negative electrode), the nonaqueous electrolyte secondary battery was fabricated in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were 20 ⁇ m and 50 ⁇ m, respectively. Produced.
  • Example 10 In (preparation of negative electrode), the nonaqueous electrolyte secondary battery was fabricated in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were 10 ⁇ m and 30 ⁇ m, respectively. Produced.
  • Example 11 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing Mg in addition to Li and Ti (Li 3.97) A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 4 except that Mg 0.03 Ti 5 O 12 ) was used.
  • Example 12 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing Ca in addition to Li and Ti (Li 3.97). A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 4 except that Ca 0.03 Ti 5 O 12 ) was used.
  • Example 13 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing Sr in addition to Li and Ti (Li 3.97) A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 4 except that Sr 0.03 Ti 5 O 12 ) was used.
  • Example 14 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing Ba in addition to Li and Ti (Li 3.97) A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 4 except that Ba 0.03 Ti 5 O 12 ) was used.
  • Example 15 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing Na in addition to Li and Ti (Li 3.97) A nonaqueous electrolyte secondary battery was produced in the same manner as in Example 4 except that Na 0.03 Ti 5 O 12 ) was used.
  • Example 16 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing Mn in addition to Li and Ti (Li 4 Ti 4 .95 Mn 0.05 O 12 ) was used to produce a nonaqueous electrolyte secondary battery in the same manner as in Example 4.
  • Example 17 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing Al in addition to Li and Ti (Li 4 Ti 4 .95 Al 0.05 O 12 ) was used to produce a nonaqueous electrolyte secondary battery in the same manner as in Example 4.
  • Example 18 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing Zr in addition to Li and Ti (Li 4 Ti 4 .95 Zr 0.05 O 12 ) was used to produce a nonaqueous electrolyte secondary battery in the same manner as in Example 4.
  • Example 19 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing Nb in addition to Li and Ti (Li 4 Ti 4 .95 Nb 0.05 O 12 ) was used to produce a nonaqueous electrolyte secondary battery in the same manner as in Example 4.
  • Example 20 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing B in addition to Li and Ti (Li 4 Ti 4 .95 B 0.05 O 12 ) was used to produce a nonaqueous electrolyte secondary battery in the same manner as in Example 4.
  • Example 21 (Preparation of negative electrode) As a second active material, instead of Li 3.97 Ti 5 O 12 , an oxide having a spinel crystal structure and containing Ni in addition to Li and Ti (Li 4 Ti 4 .95 Ni 0.05 O 12 ) was used to produce a nonaqueous electrolyte secondary battery in the same manner as in Example 4.
  • Example 1 A nonaqueous electrolyte secondary battery was prepared in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were 5 ⁇ m and 30 ⁇ m, respectively, in (Preparation of negative electrode). Produced.
  • Example 2 In (Preparation of negative electrode), the nonaqueous electrolyte secondary battery was fabricated in the same manner as in Example 1 except that the thickness T1 of the first layer and the thickness T2 of the second layer were 300 ⁇ m and 2 ⁇ m, respectively. Produced.
  • the first electrochemical capacitance C1 at the first potential of the second active material and the second electrochemical capacitance C2 at the second potential of the second active material were measured.
  • the measurement of the first electrochemical capacity C1 and the second electrochemical capacity C2 is as follows.
  • a cell for electrochemical capacity measurement was prepared.
  • the production of the cell is as follows. 90 parts by weight of the second active material and 10 parts by weight of a binder composed of PVdF were mixed with NMP to obtain a mixture.
  • the obtained mixture was applied on a current collector made of copper having a thickness of 10 ⁇ m.
  • the coated current collector was dried in vacuum at 60 ° C. for 30 minutes, then cut to a size of 15 mm in width and 20 mm in length, and further dried in vacuum at 150 ° C. for 14 hours to obtain an electrode. .
  • the thickness of the obtained electrode was 120 ⁇ m to 190 ⁇ m.
  • the counter electrode was obtained by crimping a metal sheet made of lithium on a plate made of stainless steel. A polyethylene porous film was used as the separator.
  • the electrolytic solution was prepared by dissolving LiPF 6 to a concentration of 1.0 mol / L in a solvent in which EC and DMC were mixed so that the volume ratio of EC to DMC was 3: 7.
  • a cell was prepared using an electrode, a counter electrode, a separator, and an electrolytic solution.
  • Charging / discharging of the fabricated cell was repeated between 0V-3V voltage region at a current density of 0.17 mA / cm 2 . Thereby, the first electrochemical capacitance C1 and the second electrochemical capacitance C2 were measured.
  • the ratio C2 / C1 of the second electrochemical capacity C2 to the first electrochemical capacity C1 was determined as a capacity ratio.
  • the second active material is made of a material having low conductivity
  • a conductive agent for example, acetylene black
  • the first electrochemical capacitance C1 and the second electrochemical capacitance C2 were derived by subtracting the electrochemical capacitance of the mixed conductive agent from the measured electrochemical capacitance.
  • the ratio T1 / T2 of the thickness T1 of the first layer to the thickness T2 of the second layer was determined as the thickness ratio.
  • ⁇ Capacity maintenance rate> The battery was stored for 7 days in a 45 ° C. environment after two charge-in / discharge cycles. Thereafter, charging and discharging were performed under the following conditions in an environment of 0 ° C. (under a low temperature environment), and an initial discharge capacity was obtained.
  • Constant current charging Charging current value 1C / end-of-charge voltage 4.1V
  • Constant current discharge discharge current value 1C / end-of-discharge voltage 2.5V
  • the ratio of the discharge capacity after 100 charges / discharges to the initial discharge capacity was determined as the capacity maintenance rate.
  • Capacity maintenance ratio (%) discharge capacity after 100 charge / discharge cycles / initial discharge capacity ⁇ 100
  • the material of the first active material and the first potential, the material of the second active material, the first potential and the second potential, the capacitance ratio, the thickness are shown in Table 1 below.
  • the capacity ratio C2 / C1 of Comparative Example 4 is 3.4, which is larger than 3.3, and the capacity maintenance rate of Comparative Example 4 is low.
  • the capacity ratio C2 / C1 of Examples 1 to 21 is 3.3 or less, and the capacity retention rate of Examples 1 to 21 is high.
  • the capacity ratio C2 / C1 needs to be 3.3 or less.
  • the thickness ratio T1 / T2 of Comparative Example 1 is 0.17, which is smaller than 0.33, and the capacity retention rate of Comparative Example 1 is low.
  • the thickness ratio T1 / T2 of Comparative Example 2 is 150, which is larger than 75, and the capacity retention rate of Comparative Example 2 is low.
  • the thickness ratio T1 / T2 of Examples 1 to 21 is 0.33 or more and 75 or less, and the capacity retention rate of Examples 1 to 21 is high.
  • the thickness ratio T1 / T2 is preferably 0.33 or more and 75 or less.
  • the negative electrode active material layer is a single layer including the first active material and the second active material will be described below.
  • Example 22 (Preparation of negative electrode) Artificial graphite (average particle size 10 ⁇ m, BET specific surface area 3 m 2 / g) 2.7 kg as the first active material, and lithium deficient lithium titanate (Li 3 having a spinel crystal structure as the second active material) .97 Ti 5 O 12 , average particle size 1 ⁇ m, BET specific surface area 3 m 2 / g) 0.3 kg, and BM-400B manufactured by Nippon Zeon Co., Ltd.
  • a negative electrode mixture paste (modified styrene-butadiene rubber having a solid content of 40% by weight) 200 g and 50 g of carboxymethyl cellulose (CMC) as a thickener were stirred together with an appropriate amount of water in a double-arm kneader to prepare a negative electrode mixture paste.
  • the obtained negative electrode mixture paste was applied to both surfaces of a negative electrode current collector made of a copper foil having a thickness of 10 ⁇ m, dried, and rolled to a total thickness of 140 ⁇ m. In this way, a negative electrode active material layer was formed on the surface of the negative electrode current collector, and a negative electrode active material layer was formed on the back surface of the negative electrode current collector.
  • the weight W1 of the first active material was 2.7 kg
  • the weight W2 of the second active material was 0.3 kg.
  • the density of the negative electrode active material layer was 1.5 g / cm 3 .
  • a negative electrode plate including a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector and including the first active material and the second active material was obtained.
  • the obtained negative electrode plate was cut into a width and a length that could be inserted into a cylindrical 18650 battery case to obtain a negative electrode.
  • a positive electrode was prepared in the same manner as in Example 1 (Preparation of positive electrode).
  • a nonaqueous electrolytic solution was prepared in the same manner as in Example 1 (Preparation of nonaqueous electrolytic solution).
  • a non-aqueous electrolyte secondary battery was produced in the same manner as in Example 1 (Production of non-aqueous electrolyte secondary battery).
  • Example 23 In (Preparation of negative electrode), the non-aqueous electrolyte was the same as in Example 22, except that the weight W1 of the first active material and the weight W2 of the second active material were 2.85 kg and 0.15 kg, respectively. A secondary battery was produced.
  • Example 24 The nonaqueous electrolyte was the same as in Example 22 except that the weight W1 of the first active material and the weight W2 of the second active material were set to 2.55 kg and 0.45 kg, respectively, in (Preparation of negative electrode). A secondary battery was produced.
  • Example 25 In (Preparation of negative electrode), the non-aqueous electrolyte was the same as in Example 22 except that the weight W1 of the first active material and the weight W2 of the second active material were 2.40 kg and 0.60 kg, respectively. A secondary battery was produced.
  • Example 26 In (Preparation of negative electrode), the non-aqueous electrolyte was the same as in Example 22 except that the weight W1 of the first active material and the weight W2 of the second active material were 2.25 kg and 0.75 kg, respectively. A secondary battery was produced.
  • Example 27 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 3.97 Mg 0.03 Ti 5 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 28 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 3.97 Ca 0.03 Ti 5 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 29 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 3.97 Sr 0.03 Ti 5 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 30 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 3.97 Ba 0.03 Ti 5 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 31 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 3.97 Na 0.03 Ti 5 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 32 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 4 Ti 4.95 Mn 0.05 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 33 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 4 Ti 4.95 Al 0.05 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 34 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 4 Ti 4.95 Zr 0.05 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 35 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 4 Ti 4.95 Nb 0.05 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 36 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 4 Ti 4.95 B 0.05 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 37 In (a negative electrode produced), as a second active material, instead of Li 3.97 Ti 5 O 12, except for the use of Li 4 Ti 4.95 Ni 0.05 O 12, similarly to Example 22 A non-aqueous electrolyte secondary battery was prepared.
  • Example 5 The non-aqueous electrolyte was the same as in Example 22 except that the weight W1 of the first active material and the weight W2 of the second active material were 2.94 kg and 0.06 kg, respectively, in (Preparation of negative electrode). A secondary battery was produced.
  • Example 6 The non-aqueous electrolyte was the same as in Example 22 except that the weight W1 of the first active material and the weight W2 of the second active material were 2.10 kg and 0.90 kg, respectively, in (Preparation of negative electrode). A secondary battery was produced.
  • ⁇ Capacity ratio> The first electrochemical capacitance C1 at the first potential of the second active material and the second electrochemical capacitance C2 at the second potential of the second active material were measured. The measurement of the first electrochemical capacity C1 and the second electrochemical capacity C2 is as described above (see ⁇ capacity ratio> in Examples 1 to 21 and Comparative Examples 1 to 4).
  • the ratio C2 / C1 of the second electrochemical capacity C2 to the first electrochemical capacity C1 was determined as a capacity ratio.
  • ⁇ Weight ratio> The ratio of the weight W2 of the second active material to the total weight W1 + W2 of the weight W1 of the first active material and the weight W2 of the second active material was determined as a weight ratio.
  • Weight ratio (%) W2 ⁇ (W1 + W2) ⁇ 100 ⁇ Capacity maintenance rate>
  • the battery was stored for 7 days in a 45 ° C. environment after two charge-in / discharge cycles. Thereafter, charging and discharging were performed under the following conditions in an environment of 0 ° C., and the initial discharge capacity was determined.
  • Constant current charging Charging current value 1C / end-of-charge voltage 4.1V
  • Constant current discharge discharge current value 1C / end-of-discharge voltage 2.5V
  • the ratio of the discharge capacity after 100 charges / discharges to the initial discharge capacity was determined as the capacity maintenance rate.
  • Capacity maintenance ratio (%) discharge capacity after 100 charge / discharge cycles / initial discharge capacity ⁇ 100
  • the material of the first active material and the first potential, the material of the second active material, the first potential and the second potential, the capacitance ratio, the weight are shown in Table 2 below.
  • the capacity ratio C2 / C1 of Comparative Example 7 is 3.4, which is larger than 3.3, and the capacity maintenance rate of Comparative Example 4 is low.
  • the capacity ratio C2 / C1 of Examples 22 to 37 is 3.3 or less, and the capacity retention rate of Examples 22 to 37 is high.
  • the capacity ratio C2 / C1 needs to be 3.3 or less.
  • the weight ratio of Comparative Example 5 is 2%, which is smaller than 5%, and the capacity maintenance rate of Comparative Example 5 is low.
  • the weight ratio of Comparative Example 6 is 30%, which is larger than 25%, and the capacity retention rate of Comparative Example 6 is low.
  • the weight ratio of Examples 22 to 37 is 5% or more and 25% or less, and the capacity retention rate of Examples 22 to 37 is high. As can be seen from the results in Table 2, the weight ratio is preferably 5% or more and 25% or less.
  • the present invention can prevent the cycle characteristics from being deteriorated during high-rate charging in a low temperature environment.
  • the application of the nonaqueous electrolyte secondary battery having the negative electrode for a nonaqueous electrolyte secondary battery according to the present invention is suitable for applications requiring high input / output characteristics in a low temperature environment, but is not particularly limited.
  • the nonaqueous electrolyte secondary battery having the negative electrode for a nonaqueous electrolyte secondary battery according to the present invention can be used as a driving power source for portable electronic devices, hybrid vehicles, electric vehicles, electric tools, and the like.

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Abstract

L'invention concerne une électrode négative pour batteries secondaires à électrolyte non aqueux comprenant un collecteur d'électrode négative et une couche de matériau actif d'électrode négative. La couche de matériau actif d'électrode négative contient un premier matériau actif et un second matériau actif. Le premier matériau actif absorbe et désorbe des ions de lithium à un premier potentiel. Le second matériau actif absorbe et désorbe des ions de lithium à un premier potentiel qui est proche du premier potentiel du premier matériau actif et un second potentiel qui est plus élevé que le premier potentiel. La différence entre le premier potentiel du second matériau actif et le second potentiel du second matériau actif est 0,1 V ou plus. Le rapport de capacité de la seconde capacité électrochimique (C2) du second matériau actif au second potentiel par rapport à la première capacité électrochimique (C1) du second matériau actif au premier potentiel, à savoir C2/C1, est de 3,3 ou moins.
PCT/JP2012/008420 2011-12-28 2012-12-28 Electrode négative pour batteries secondaires à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux comprenant l'électrode négative pour batteries secondaires à électrolyte non aqueux WO2013099279A1 (fr)

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JPWO2019054330A1 (ja) * 2017-09-13 2020-10-29 国立研究開発法人産業技術総合研究所 スピネル型ナトリウムチタン酸化物
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WO2023181949A1 (fr) * 2022-03-25 2023-09-28 パナソニックＩｐマネジメント株式会社 Électrode négative pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux
CN115064669A (zh) * 2022-06-10 2022-09-16 贵州黔材科技发展有限公司 一种锶掺杂钛酸锂材料及其制备方法和应用
WO2023240595A1 (fr) * 2022-06-17 2023-12-21 宁德时代新能源科技股份有限公司 Plaque d'électrode négative et son procédé de fabrication, ensemble électrode et batterie secondaire

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