WO2018020670A1 - Batterie à électrolyte non aqueux et bloc-batterie - Google Patents

Batterie à électrolyte non aqueux et bloc-batterie Download PDF

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WO2018020670A1
WO2018020670A1 PCT/JP2016/072385 JP2016072385W WO2018020670A1 WO 2018020670 A1 WO2018020670 A1 WO 2018020670A1 JP 2016072385 W JP2016072385 W JP 2016072385W WO 2018020670 A1 WO2018020670 A1 WO 2018020670A1
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positive electrode
active material
battery
negative electrode
electrode active
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PCT/JP2016/072385
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English (en)
Japanese (ja)
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大 山本
圭吾 保科
諒 原
高見　則雄
康宏 原田
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株式会社 東芝
東芝インフラシステムズ株式会社
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Priority to JP2018530307A priority Critical patent/JP6699908B2/ja
Priority to PCT/JP2016/072385 priority patent/WO2018020670A1/fr
Publication of WO2018020670A1 publication Critical patent/WO2018020670A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00—Compounds of niobium
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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

  • Embodiments of the present invention relate to a nonaqueous electrolyte battery and a battery pack.
  • non-aqueous electrolyte batteries batteries that are charged and discharged by moving lithium ions between the negative electrode and the positive electrode are actively studied as high energy density batteries.
  • Non-aqueous electrolyte batteries are expected to be used not only as power sources for small electronic devices, but also as medium- and large-sized power sources for in-vehicle and stationary applications. In such medium and large-sized applications, life characteristics and high safety are desired. In addition, high input / output performance may be required.
  • a non-aqueous electrolyte battery using spinel type lithium titanate as a negative electrode As a non-aqueous electrolyte battery having life characteristics and high safety, a non-aqueous electrolyte battery using spinel type lithium titanate as a negative electrode is known.
  • spinel type lithium titanate has a high lithium storage / release potential of about 1.55 V (vs. Li / Li + )
  • a nonaqueous electrolyte battery using spinel type lithium titanate as a negative electrode active material has a high battery voltage. I can't get it.
  • spinel type lithium titanate shows a flat charge / discharge curve in the lithium occlusion / release potential range, and therefore, the change in potential due to the change in charge state is small.
  • lithium sodium titanium composite oxides such as Li 2 Na 2 Ti 6 O 14 can occlude and release lithium at a low potential among titanium oxides, and the operating potential is 1.25 V (vs. Li / Li + )
  • a non-aqueous electrolyte battery containing Li 2 Na 2 Ti 6 O 14 as a negative electrode active material has a problem in battery performance at high temperatures.
  • an object is to provide a non-aqueous electrolyte battery having high input / output performance and excellent high-temperature durability, and a battery pack including the non-aqueous electrolyte battery.
  • a non-aqueous electrolyte battery including a positive electrode, a negative electrode, and a non-aqueous electrolyte is provided.
  • M1 is one or more elements selected from the group consisting of Cs, K, Sr, Ba and Ca
  • M2 is Zr, Al, Sn, V, Ta,
  • the positive electrode includes a positive electrode active material and a Na component.
  • a battery pack is provided.
  • the battery pack includes the nonaqueous electrolyte battery according to the embodiment.
  • Sectional drawing which cut
  • the expanded sectional view of the A section of FIG. The partial notch perspective view of the nonaqueous electrolyte battery of the 2nd example which concerns on 1st Embodiment.
  • the expanded sectional view of the B section of FIG. The exploded perspective view of an example battery pack concerning a 2nd embodiment.
  • the block diagram which shows the electric circuit of the battery pack shown in FIG.
  • the perspective view which shows the assembled battery containing the nonaqueous electrolyte battery which concerns on 1st Embodiment.
  • a nonaqueous electrolyte battery including a negative electrode, a positive electrode, and a nonaqueous electrolyte is provided.
  • M1 is one or more elements selected from the group consisting of Cs, K, Sr, Ba and Ca
  • M2 is Zr, Al, Sn, V, Ta, Mo, W,
  • One or more elements selected from the group consisting of Fe, Co and Mn (preferably one selected from the group consisting of Sn, V, Ta, Mo, W, Fe, Co and Mn Or two or more elements), 0 ⁇ v ⁇ 2, 0 ⁇ x ⁇ 2, 0 ⁇ y ⁇ 2, 0 ⁇ z ⁇ 3, and ⁇ 0.5 ⁇ ⁇ ⁇ 0.5.
  • the positive electrode contains a positive electrode active material and a Na component.
  • the reaction potential (also referred to as lithium storage / release potential) of the orthorhombic Na-containing niobium titanium composite oxide represented by the general formula (1) is in the range of 1.0 to 1.5 V (vs. Li / Li + ). is there. Therefore, the reaction potential of the negative electrode including the negative electrode active material containing the oxide can be lower than the reaction potential of the negative electrode including spinel type lithium titanate as the negative electrode active material. Therefore, since the operating voltage of the nonaqueous electrolyte battery when the same positive electrode active material is used can be increased, the input / output performance of the nonaqueous electrolyte battery can be improved and the energy density can be improved.
  • a nonaqueous electrolyte battery including a negative electrode including a negative electrode active material including an orthorhombic Na-containing niobium titanium composite oxide represented by the general formula (1)
  • the nonaqueous electrolyte is decomposed.
  • Decomposition products such as hydrofluoric acid (HF) may be formed.
  • HF hydrofluoric acid
  • Na ions can be eluted from the negative electrode during high temperature operation of the battery.
  • Na ions diffuse in the non-aqueous electrolyte, it is inevitable that the Na ion concentration in the vicinity of the negative electrode becomes high and the distribution of Na ion concentration is biased. As a result, battery deterioration during high temperature operation is accelerated.
  • the present inventors include a Na component in the positive electrode, so that deterioration in battery performance during high-temperature operation is suppressed and high-temperature durability is improved without impairing input / output performance. I found out. It is presumed that this is because the presence of the Na component in the positive electrode reduces the uneven distribution of Na ion concentration in the non-aqueous electrolyte.
  • the negative electrode includes a negative electrode current collector and a negative electrode active material-containing layer.
  • the negative electrode active material-containing layer includes a negative electrode active material, and includes a conductive agent and a binder as necessary.
  • the negative electrode active material-containing layer is formed on one side or both sides of the negative electrode current collector.
  • the negative electrode active material contains orthorhombic Na-containing niobium titanium composite oxide particles represented by the general formula (1).
  • the general formula (1) will be described.
  • the atomic ratio v changes within the range of 0 ⁇ v ⁇ 2 depending on the state of charge of the orthorhombic Na-containing niobium titanium composite oxide.
  • y represents the amount of Nb and Na. By substituting a part of Na with Nb, the energy density of the battery increases, so y becomes a value smaller than 2. Since the discharge capacity can be increased when the oxide contains Na and Nb, y is preferably a value larger than 0. A more preferable range of y is 0.1 ⁇ y ⁇ 0.8.
  • the atomic ratio x of the element M1 is 0 ⁇ x ⁇ 2.
  • the atomic ratio of x is limited to the above range
  • the addition of the element M1 can suppress the change in the crystal structure of the active material accompanying charge / discharge and improve the battery life characteristics. This is because the discharge capacity may decrease with the increase.
  • the atomic ratio z of the element M2 is 0 ⁇ z ⁇ 3.
  • the reason why the atomic ratio of z is limited to the above range is that the target crystal structure is obtained.
  • An orthorhombic Na-containing niobium titanium composite oxide having an atomic ratio z within this range can exhibit better rate characteristics. The reason why ⁇ is set to ⁇ 0.5 ⁇ ⁇ ⁇ 0.5 will be described.
  • ⁇ is a value that varies depending on the ratio of lithium and each metal component, and ⁇ 0.5 ⁇ ⁇ ⁇ 0.5 represents a range in which the crystal structure is maintained.
  • An orthorhombic Na-containing niobium titanium composite oxide having an atomic ratio ⁇ within this range can exhibit better rate characteristics and better cycle characteristics.
  • M2 is at least one selected from the group consisting of Zr, Al, Sn, V, Ta, Mo, W, Fe, Co, and Mn.
  • the orthorhombic Na-containing niobium titanium composite oxide can realize more excellent cycle characteristics by containing Zr.
  • the orthorhombic Na-containing niobium titanium composite oxide can realize better rate characteristics by containing Sn. V and Ta can exhibit the same physical and chemical properties as Nb.
  • the orthorhombic Na-containing niobium titanium composite oxide can realize more excellent rate characteristics by containing Mo.
  • the orthorhombic Na-containing niobium titanium composite oxide can realize more excellent rate characteristics when it contains W.
  • the orthorhombic Na-containing niobium titanium composite oxide can realize more excellent cycle characteristics by including Fe.
  • the orthorhombic Na-containing niobium titanium composite oxide can realize more excellent cycle characteristics by containing Co.
  • the orthorhombic Na-containing niobium titanium composite oxide can realize more excellent cycle characteristics by containing Mn.
  • the orthorhombic Na-containing niobium titanium composite oxide can realize better rate characteristics by containing Al.
  • M2 preferably contains one or more elements selected from the group consisting of Sn, V, Ta, Mo, W, Fe, Co, and Mn. More preferably, M2 contains at least one selected from the group consisting of Al, Zr, Sn and V.
  • the particle surface may be coated with a carbon material layer.
  • a compound containing Na may adhere to at least a part of the particle surface.
  • the orthorhombic Na-containing niobium titanium composite oxide particles represented by the general formula (1) are either single primary particles, secondary particles in which primary particles are aggregated, or particles in which primary particles and secondary particles are mixed. May be.
  • the average particle size is desirably in the range of 3 ⁇ m to 20 ⁇ m.
  • the orthorhombic Na-containing niobium titanium composite oxide particles represented by the general formula (1) can be synthesized by, for example, a solid phase method.
  • the negative electrode active material includes other types of negative electrode active materials (second negative electrode). Active material).
  • Examples of the second negative electrode active material include spinel type crystal structure titanium-containing oxide, anatase type crystal structure titanium-containing oxide, rutile type crystal structure titanium-containing oxide, bronze type crystal structure titanium-containing oxide At least one selected from the group consisting of a titanium-containing oxide having a ramsdellite type crystal structure, a niobium titanium-containing oxide having a monoclinic crystal structure, and Ti and P, V, Sn, Cu, Ni, Nb and Fe Metal complex oxides containing elements, sulfides, lithium nitrides, amorphous tin oxides such as SnB 0.4 P 0.6 O 3.1 , tin silicon oxides such as SnSiO 3 , eg WO 3 Such as tungsten oxide.
  • the type of the second negative electrode active material can be one type or two or more types.
  • An example of the spinel type titanium-containing oxide is a spinel type lithium titanium composite oxide.
  • Examples of the spinel-type lithium titanium composite oxide include Li 4 + x Ti 5 O 12 (x varies in the range of 0 ⁇ x ⁇ 3 due to charge / discharge reaction).
  • Examples of the ramsdellite-type titanium-containing oxide include Li 2 + y Ti 3 O 7 (y changes within a range of ⁇ 1 ⁇ y ⁇ 3 due to charge / discharge reaction).
  • composition of anatase-type, rutile-type, and bronze-type titanium-containing oxides can be represented by TiO 2 .
  • Examples of the metal composite oxide containing Ti and at least one element selected from the group consisting of P, V, Sn, Cu, Ni, Nb, and Fe include TiO 2 —P 2 O 5 , TiO 2. —V 2 O 5 , TiO 2 —P 2 O 5 —SnO 2 , TiO 2 —P 2 O 5 —MeO (Me is at least one element selected from the group consisting of Cu, Ni and Fe) And so on.
  • This metal composite oxide has a low crystallinity and preferably has a microstructure in which a crystal phase and an amorphous phase coexist or exist as an amorphous phase alone. With such a microstructure, cycle performance can be greatly improved.
  • the sulfide examples include titanium sulfide such as TiS 2 , molybdenum sulfide such as MoS 2, and iron sulfide such as FeS, FeS 2 , and Li x FeS 2 (0 ⁇ x ⁇ 2).
  • lithium nitride examples include lithium cobalt nitride (for example, Li x Co y N, where 0 ⁇ x ⁇ 4 and 0 ⁇ y ⁇ 0.5).
  • the monoclinic niobium titanium-containing oxide represented by the general formula Li x Ti 1-y M3 y Nb 2-z M4 z O 7 + ⁇ , M3 comprises Zr, Si, Sn, Fe, Co, Mn, and Ni A compound in which M4 is at least one selected from the group consisting of V, Nb, Ta, Mo, W and Bi, and 0 ⁇ x ⁇ 5, 0 ⁇ y. ⁇ 1, 0 ⁇ z ⁇ 2, ⁇ 0.3 ⁇ ⁇ ⁇ 0.3.
  • the ratio of the first negative electrode active material in the negative electrode active material is preferably in the range of 70% by mass to 100% by mass. This is because if the proportion of the first negative electrode active material in the negative electrode active material is less than 70% by mass, the high-temperature durability performance may not be improved even if the Na component is contained in the positive electrode. A more preferable range is 80% by mass or more and 100% by mass or less.
  • the measurement method of the crystal structure, composition and mixing ratio of the negative electrode active material is as follows. First, in order to grasp the crystal state of the active material, the lithium ion is separated from the active material to be measured.
  • the orthorhombic Na-containing niobium titanium composite oxide contains lithium which does not participate in charge / discharge in the structure. Therefore, the “state where lithium ions are released” as used herein means a state where lithium involved in charge / discharge is released.
  • the active material to be measured is contained in the negative electrode, the battery is completely discharged. For example, the nonaqueous electrolyte battery is discharged at 1 C until the battery voltage reaches 1.0V. However, lithium ions remaining in the active material may exist even when the battery is discharged.
  • the battery in such a state is disassembled in a glove box filled with argon.
  • the electrode containing the active material to be measured is taken out from the decomposed battery.
  • the electrode is washed with a suitable solvent.
  • a suitable solvent for example, ethyl methyl carbonate may be used. If the cleaning is insufficient, an impurity phase such as lithium carbonate or lithium fluoride may be mixed under the influence of lithium ions remaining in the electrode. In that case, it is preferable to use an airtight container in which the measurement atmosphere can be performed in an inert gas.
  • the negative electrode active material-containing layer is peeled off from the negative electrode current collector using a spatula or the like to obtain a powdery negative electrode active material-containing layer.
  • the crystal structure of the negative electrode active material is identified by powder X-ray analysis measurement. The measurement is performed in a measurement range where 2 ⁇ is 10 to 90 ° using CuK ⁇ rays as a radiation source. By this measurement, an X-ray diffraction pattern of the compound contained in the selected particle can be obtained.
  • an apparatus for powder X-ray diffraction measurement SmartLab manufactured by Rigaku is used.
  • the measurement conditions are as follows: Cu target; 45 kV, 200 mA; Solar slit: 5 ° for both incidence and reception; Step width: 0.02 deg; Scan rate: 20 deg / min; Semiconductor detector: D / teX Ultra 250; Sample Plate holder: Flat glass sample plate holder (thickness 0.5 mm); Measurement range: 10 ° ⁇ 2 ⁇ ⁇ 90 °.
  • an X-ray diffraction pattern belonging to the orthorhombic type is obtained by X-ray diffraction measurement. I can confirm that.
  • X-ray diffraction (XRD) measurement of the electrode is performed by cutting the electrode to be measured as much as the area of the holder of the wide-angle X-ray diffractometer and directly attaching it to a glass holder for measurement. Can do.
  • XRD is measured in advance according to the type of the electrode current collector, and it is grasped at which position the peak derived from the current collector appears.
  • the presence or absence of a peak of a mixture such as a conductive agent or a binder is also grasped in advance.
  • the electrode may be physically peeled off, but is easily peeled off when ultrasonic waves are applied in a solvent.
  • wide-angle X-ray diffraction measurement of the active material can be performed.
  • the mixed state of the active material is judged by whether or not peaks attributed to a plurality of crystal structures appear.
  • the negative electrode active material-containing layer is observed with a scanning electron microscope (SEM). Sampling of the sample should be performed in an inert atmosphere such as argon or nitrogen while avoiding exposure to the air.
  • the particle size distribution of the selected particles is selected to be as wide as possible.
  • the type and composition of the constituent elements of the active material are specified by energy dispersive X-ray spectroscopy (Energy Dispersive X-ray Spectroscopy; EDX).
  • EDX Energy Dispersive X-ray Spectroscopy
  • grain can be specified.
  • the same operation is performed on each of the plurality of active material particles, and the mixed state of the active material particles is determined. Subsequently, the negative electrode active material-containing layer is weighed.
  • the weighed powder is dissolved in hydrochloric acid and diluted with ion-exchanged water, and then the content of metal is calculated by inductively coupled plasma emission spectroscopy (ICP-AES).
  • ICP-AES inductively coupled plasma emission spectroscopy
  • the mass ratio is estimated from the content ratio of elements unique to each active material.
  • the ratio between the intrinsic element and the active material mass is determined from the composition of the constituent elements determined by energy dispersive X-ray spectroscopy.
  • the XPS spectrum measurement method is as follows.
  • the nonaqueous electrolyte battery is discharged at 1 C until the battery voltage reaches 1.0 V, disassembled in a glove box in an inert atmosphere, and the negative electrode is taken out.
  • the negative electrode is washed with ethyl methyl carbonate and then vacuum dried. After drying, the negative electrode active material-containing layer is peeled off from the negative electrode current collector using a spatula or the like to obtain a powdery negative electrode active material-containing layer as a measurement sample.
  • the measurement sample is mounted on the stage of an X-ray photoelectron spectroscopy (XPS) apparatus under an inert atmosphere.
  • XPS X-ray photoelectron spectroscopy
  • the measurement sample mounted on the XPS stage is introduced into the XPS measurement apparatus while maintaining an inert atmosphere.
  • survey scan measurement qualification analysis
  • narrow scan scan of the element of interest state measurement
  • the XPS spectrum obtained by such measurement is appropriately fitted.
  • the conductive agent has an effect of improving current collecting performance and suppressing contact resistance between the active material and the current collector.
  • Examples of the conductive agent include carbonaceous materials such as acetylene black, carbon black, graphite, carbon nanofiber, and carbon nanotube. These carbonaceous materials may be used alone or a plurality of carbonaceous materials may be used.
  • the binder has an action of binding the active material, the conductive agent, and the current collector.
  • the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluorine-based rubber, styrene butadiene rubber, an acrylic resin or a copolymer thereof, polyacrylic acid, polyacrylonitrile, and the like.
  • the type of the binder can be one type or two or more types.
  • the compounding ratio of the negative electrode active material, the conductive agent and the binder is such that the negative electrode active material is 70% by mass to 96% by mass, the negative electrode conductive agent is 2% by mass to 28% by mass, and the binder is 2% by mass to 28% by mass. It is preferable that it is the range of the mass% or less. If the conductive agent is less than 2% by mass, the current collecting performance of the negative electrode active material-containing layer may be reduced, and the large current characteristics of the nonaqueous electrolyte battery may be reduced. On the other hand, if the binder is less than 2% by mass, the binding property between the negative electrode active material-containing layer and the negative electrode current collector is lowered, and the cycle characteristics may be lowered. On the other hand, from the viewpoint of increasing the capacity, the conductive agent and the binder are each preferably 28% by mass or less.
  • the negative electrode active material-containing layer may contain a compound containing Na.
  • Examples of the Na-containing compound include those described later.
  • the negative electrode current collector is preferably formed from an aluminum foil or an aluminum alloy foil.
  • the aluminum alloy desirably contains one or more elements selected from Mg, Ti, Zn, Mn, Fe, Cu, and Si.
  • the negative electrode can be produced, for example, by the following method. First, a negative electrode active material, a conductive agent, and a binder are suspended in a solvent to prepare a slurry. This slurry is applied to one or both sides of the negative electrode current collector and dried to form a negative electrode active material-containing layer. Then press. Alternatively, the negative electrode active material, the conductive agent, and the binder can be formed into a pellet and used as the negative electrode active material-containing layer.
  • the positive electrode includes a positive electrode current collector and a positive electrode active material-containing layer.
  • a positive electrode active material content layer contains a positive electrode active material and Na component, and further contains a electrically conductive agent and a binder as needed.
  • the positive electrode active material-containing layer is formed on one side or both sides of the positive electrode current collector.
  • the Na component only needs to contain Na, and may be any of those having solubility, dispersion or compatibility in the nonaqueous electrolyte, those insoluble in the nonaqueous electrolyte, and those precipitated in the nonaqueous electrolyte. .
  • the Na component preferably contains one or more of Na ions and Na-containing compounds (Na-containing compounds). Thereby, since the uniformity of distribution of Na component in a nonaqueous electrolyte becomes high, high temperature durability can be improved more.
  • Na-containing compounds examples include NaF, Na 2 SO 4 , Na 2 CO 3 , and Na 4 P 2 O 7 .
  • the kind of Na containing compound can be made into 1 type, or 2 or more types. According to these compounds, it is possible to suppress deterioration of the positive electrode and the negative electrode when the battery is operated at a high temperature.
  • the content of Na component in the positive electrode is desirably 0.01% by mass or more and 1% by mass or less. If the content is less than mass%, the effect of protecting the positive electrode cannot be obtained. On the other hand, when the content exceeds 1% by mass, the properties of the positive electrode active material are deteriorated. A more preferable range is 0.05% by mass or more and 0.5% by mass or less.
  • the amount of Na component in the positive electrode can be determined by the following method.
  • the nonaqueous electrolyte battery is discharged at 1 C until the battery voltage reaches 1.0 V, disassembled in a glove box in an inert atmosphere, and the positive electrode is taken out.
  • the positive electrode is washed with ethyl methyl carbonate and then vacuum dried.
  • powder is collected as a measurement sample and weighed.
  • the obtained powder is dissolved with hydrochloric acid, diluted with ion-exchanged water, and the content of metal is calculated by inductively coupled plasma emission spectroscopy (ICP-AES).
  • ICP-AES inductively coupled plasma emission spectroscopy
  • the nonaqueous electrolyte adhering to the positive electrode is removed by washing the positive electrode with ethyl methyl carbonate, when the Na component is eluted from the positive electrode into the nonaqueous electrolyte, the eluted Na component contains the Na component in the positive electrode. Not included in the quantity.
  • the Na component is present on the surface of the positive electrode active material particles.
  • the surface of the positive electrode active material particle is an interface for insertion / extraction of Li (lithium or lithium ion), and the presence of Na component on the particle surface effectively affects the influence of HF in the nonaqueous electrolyte and eluted Na. Can be suppressed.
  • the Na component is present on the surface of the positive electrode active material particles.
  • the nonaqueous electrolyte battery is discharged at 1 C until the battery voltage reaches 1.0V. Then, it disassembles in the glove box of inert atmosphere and takes out a positive electrode.
  • the positive electrode is washed with dimethyl carbonate and then vacuum dried.
  • the cleaned positive electrode is observed with a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • positive electrode active material particles are confirmed, and the vicinity of the active material particles is observed by electron energy loss spectroscopy (Electron Energy Loss Spectroscopy; EELS) to confirm that the Na component is present around the active material particles.
  • EELS electron Energy Loss Spectroscopy
  • the covering state and the covering amount of the Na component may be in any state.
  • the form of the Na-containing compound in the Na component can be determined by X-ray photoelectron spectroscopy (XPS) measurement.
  • XPS X-ray photoelectron spectroscopy
  • the disassembly of the nonaqueous electrolyte battery and the cleaning and drying of the positive electrode are as described above.
  • powder is collected as a measurement sample from the positive electrode active material-containing layer on the current collector and weighed.
  • the measurement sample is mounted on an XPS stage under an inert atmosphere.
  • the measurement sample mounted on the XPS stage is introduced into the XPS measurement apparatus while maintaining an inert atmosphere.
  • survey scan measurement qualifieditative analysis
  • narrow scan scan of the element of interest state measurement
  • the composition of the Na-containing compound is determined by appropriately fitting the XPS spectrum obtained by the measurement as described above.
  • a Na-containing compound is added to the positive electrode
  • a Na-containing compound is added to the nonaqueous electrolyte or the negative electrode
  • a negative electrode active material for example, the Na component is eluted from the orthorhombic Na-containing niobium titanium composite oxide particles represented by the general formula (1) into the non-aqueous electrolyte and the positive electrode contains the Na component. What was mentioned as what can be contained in a positive electrode and a nonaqueous electrolyte can be used for a Na containing compound.
  • the orthorhombic Na-containing niobium titanium composite oxide particles represented by the general formula (1) mainly have a range of 1.0 V (vs. Li / Li + ) to 1.5 V (vs. Li / Li + ).
  • Li ions can be inserted and desorbed.
  • Na ions can be eluted from the oxide particles into the non-aqueous electrolyte.
  • An example of a method for eluting Na ions will be described below.
  • Na in the negative electrode can be eluted into the non-aqueous electrolyte by aging at a high temperature for a desired time.
  • the positive electrode By impregnating the positive electrode with a nonaqueous electrolyte containing Na ions, the positive electrode can contain the Na component.
  • the elution amount of Na ions can be controlled by, for example, the overcharge state or overdischarge state of the nonaqueous electrolyte battery, the aging temperature, and the aging time. From the viewpoint of battery safety, aging is preferably performed in an overdischarged state. By limiting the operating voltage range of the nonaqueous electrolyte battery to a range different from the voltage at the time of aging, further elution of Na ions can be prevented.
  • the positive electrode active material is not particularly limited as long as it can occlude and release lithium or lithium ions.
  • the positive electrode active material include manganese dioxide (MnO 2 ), iron oxide, copper oxide, nickel oxide, lithium nickel composite oxide (for example, Li x NiO 2 , 0 ⁇ x ⁇ 1), lithium cobalt composite oxide ( For example, Li x CoO 2 , 0 ⁇ x ⁇ 1), lithium nickel cobalt composite oxide (for example, Li x Ni 1-y Co y O 2 , 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), lithium manganese cobalt Complex oxide (for example, Li x Mn y Co 1-y O 2 , 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1), lithium nickel cobalt manganese complex oxide (for example, Li x Ni 1-yz Co y Mn z O 2 , 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, 0 ⁇ z ⁇ 1), lithium nickel cobalt aluminum composite
  • a positive electrode active material containing a lithium manganese composite oxide having a spinel crystal structure is preferable.
  • Five non-aqueous electrolyte batteries including the positive electrode including the positive electrode active material and the negative electrode including the negative electrode active material including the orthorhombic Na-containing niobium titanium composite oxide particles represented by the general formula (1) are connected in series. This is because the assembled battery connected to is excellent in voltage compatibility with the lead acid battery.
  • spinel type lithium titanate is used as the negative electrode active material instead of the negative electrode active material containing the orthorhombic Na-containing niobium titanium composite oxide particles represented by the general formula (1), the voltage compatibility with the lead storage battery is achieved.
  • the number of batteries required to obtain a high assembled battery is 6. Therefore, according to the battery of the first embodiment, it is possible to realize an assembled battery excellent in voltage compatibility with a lead storage battery with a small number of single cells, so that the capacity per unit volume and the unit weight of the assembled battery Capacity can be improved.
  • the spinel-type lithium manganese composite oxide is preferably represented by Li x Mn 2-y A y O 4 .
  • A is one or more elements selected from the group consisting of Al, Mg, Ti, Cr, Fe, Co, and Zn.
  • the atomic ratios x and y satisfy 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 2.
  • a spinel type lithium manganese composite oxide may be used alone, or a plurality of compounds may be used in combination.
  • examples of other compounds LiMeO 2 (Me is one or more elements selected Ni, from the group consisting of Co and Mn), LiMn 1-x- y Fe x A y PO 4 (A is Mg, One or more elements selected from the group consisting of Ca, Al, Ti, Zn and Zr, 0.1 ⁇ x ⁇ 0.35, 0.03 ⁇ y ⁇ 0.1 are included.
  • the proportion of the spinel-type lithium manganese composite oxide in the positive electrode active material is desirably in the range of 50% by mass to 100% by mass.
  • Preferred positive electrode active materials other than spinel type lithium manganese composite oxide include lithium cobalt composite oxide, lithium nickel cobalt composite oxide, lithium manganese cobalt composite oxide, lithium nickel cobalt manganese composite oxide, and lithium phosphorylation having an olivine structure. Things.
  • the positive electrode active material contains a spinel type lithium manganese composite oxide and a lithium cobalt composite oxide, it is desirable that the positive electrode satisfies the following formula (2).
  • W Mn represents the mass ppm of Mn per unit mass of the positive electrode active material-containing layer
  • W Co represents the mass ppm of Co per unit mass of the positive electrode active material-containing layer
  • the mass ratio (W Co / W Mn ) When the mass ratio (W Co / W Mn ) is larger than 0, that is, Co is contained in the positive electrode layer, the effect of Na contained in the positive electrode is promoted, and the high temperature durability is improved. Further, by setting the mass ratio (W Co / W Mn ) to 0.3 or less, the Co component is prevented from reacting with Na contained in the positive electrode, and the positive electrode itself is prevented from being deteriorated in a high-temperature cycle.
  • a more preferable range of the mass ratio (W Co / W Mn ) is 0.03 ⁇ W Co / W Mn ⁇ 0.25.
  • the mass ratio (W Co / W Mn ) can be obtained by the same method as in the case of the Na component content. That is, the nonaqueous electrolyte battery is discharged at 1 C until the battery voltage reaches 1.0 V, disassembled in a glove box in an inert atmosphere, and the positive electrode is taken out. The positive electrode is washed with ethyl methyl carbonate and then vacuum dried. Using a spatula or the like from the positive electrode active material-containing layer on the current collector, powder is collected as a measurement sample and weighed.
  • the obtained powder was dissolved in hydrochloric acid, diluted with ion-exchanged water, and then the contents (mass ppm) of Mn and Co were calculated by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). To do.
  • ICP-AES Inductively Coupled Plasma Atomic Emission Spectroscopy
  • Examples of the conductive agent include carbonaceous materials such as acetylene black, carbon black, graphite, carbon nanofiber, and carbon nanotube. These carbonaceous materials may be used alone or a plurality of carbonaceous materials may be used.
  • the binder has an action of binding the active material, the conductive agent, and the current collector.
  • the binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), and fluorine-based rubber, styrene butadiene rubber, an acrylic resin or a copolymer thereof, polyacrylic acid, polyacrylonitrile, and the like.
  • the type of the binder can be one type or two or more types.
  • the mixing ratio of the positive electrode active material, the conductive agent, and the binder is preferably 80% by mass to 95% by mass, 3% by mass to 18% by mass, and 2% by mass to 17% by mass. .
  • the conductive agent can exhibit the above-described effects by adjusting the amount to 3% by mass or more. By making the amount of the conductive agent 18% by mass or less, the decomposition of the nonaqueous electrolyte on the surface of the conductive agent under high temperature storage can be reduced. Sufficient electrode strength can be obtained by setting the binder to an amount of 2% by mass or more. By setting the binder to an amount of 17% by mass or less, the amount of the binder, which is an insulating material in the positive electrode, can be reduced, and the internal resistance can be reduced.
  • the positive electrode current collector is preferably formed from an aluminum foil or an aluminum alloy foil.
  • the aluminum alloy desirably contains one or more elements selected from Mg, Ti, Zn, Mn, Fe, Cu, and Si.
  • the positive electrode can be produced, for example, by the following method. First, a positive electrode active material, a conductive agent, and a binder are suspended in a solvent to prepare a slurry. This slurry is applied to one or both sides of the current collector and dried to form a positive electrode active material-containing layer. Then press. Alternatively, the positive electrode active material, the conductive agent, and the binder can be formed into a pellet and used as the positive electrode active material-containing layer.
  • Nonaqueous electrolyte As the non-aqueous electrolyte, for example, a liquid non-aqueous electrolyte or a gel-like non-aqueous electrolyte can be used.
  • the liquid non-aqueous electrolyte includes an organic solvent and an electrolyte dissolved in the organic solvent.
  • the gel-like nonaqueous electrolyte is prepared, for example, by combining a liquid nonaqueous electrolyte and a polymer material.
  • electrolytes examples include lithium salts such as LiClO 4 , LiPF 6 , LiBF 4 , LiAsF 6 , LiCF 3 SO 3 , and LiN (CF 3 SO 2 ) 2 . These electrolytes can be used alone or in combination of two or more.
  • the electrolyte preferably contains LiPF 6.
  • the concentration of the electrolyte in the nonaqueous electrolyte is preferably in the range of 0.5 mol / L to 2.5 mol / L.
  • the organic solvent is not particularly limited as long as the electrolyte can be dissolved.
  • organic solvents include propylene carbonate (PC), ethylene carbonate (EC), cyclic carbonates such as vinylene carbonate; Carbonates; cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), dioxolane (DOX); chain ethers such as dimethoxyethane (DME) and dietoethane (DEE); acetonitrile (AN) and sulfolane (SL). These organic solvents can be used alone or in combination of two or more.
  • PC propylene carbonate
  • EC ethylene carbonate
  • cyclic carbonates such as vinylene carbonate
  • Carbonates cyclic ethers such as tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), dioxolane (DOX); chain ethers such as dimethoxyethane
  • Examples of more preferable organic solvents include two or more selected from the group consisting of propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), and methyl ethyl carbonate (MEC).
  • PC propylene carbonate
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • MEC methyl ethyl carbonate
  • an organic solvent containing ethylene carbonate so that the content of ethylene carbonate in the nonaqueous electrolyte is 10% by mass or more and 30% by mass or less.
  • the content of ethylene carbonate in the non-aqueous electrolyte is 10% by mass or more, a film that promotes lithium ion insertion / desorption is easily formed on the surface of the negative electrode active material.
  • content of ethylene carbonate 30 mass% or less the viscosity increase of a nonaqueous electrolyte is suppressed, and since the melting point of ethylene carbonate is near normal temperature, the fall of low-temperature input-output performance can be suppressed.
  • the non-aqueous electrolyte can contain an additive.
  • the additive is preferably one that does not inhibit the effect of Na in the nonaqueous electrolyte, and lithium salt is particularly preferred.
  • examples of such additives include LiN (CF 3 SO 2 ) 2 , LiN (SO 2 C 2 F 5 ) 2 , LiN (SO 2 F) 2 , LiPF 2 O 2 , LiPFO 3 H, LiB (C 2 O 4 ) 2 , LiF 2 BC 2 O 4 , LiBF 2 (OCOOC (CF 3 ) 2 , an imide salt containing a sulfonyl group in the molecular structure (R1-S ( ⁇ O) 2 -R2), and a phosphoryl group
  • the imide salt (R3-P (—R5) ( ⁇ O) —R4) can be selected from the group consisting of one or more additives, including a sulfonyl group.
  • R1 is an imide group
  • R2 is a fluoro group or a hydrocarbon group containing a fluoro group, where the hydrocarbon group may be cyclic or chain-like and unsaturated.
  • R3 is an imide group
  • R4 and R5 are a fluoro group or a hydrocarbon group containing a fluoro group. It may be a chain or may contain an unsaturated bond.
  • the non-aqueous electrolyte may contain a Na component.
  • the Na component only needs to contain Na, and may be any of those having solubility, dispersion or compatibility in the nonaqueous electrolyte, those insoluble in the nonaqueous electrolyte, and those precipitated in the nonaqueous electrolyte.
  • the Na component preferably contains one or more of Na ions and Na-containing compounds (Na-containing compounds).
  • a preferable Na component contains Na ions.
  • Na-containing compounds examples include NaPF 6 , NaBF 4 , NaClO 4 , NaAsF 6 , NaCF 3 SO 3 , NaN (C 2 F 5 SO 2 ) 2 , NaC (CF 3 SO 2 ) 3 , NaN (CF 3 SO 2 ) 2 , NaN (SO 2 C 2 F 5 ) 2 , NaN (SO 2 F) 2 , NaPFO 3 H, NaB (C 2 O 4 ) 2 , NaF 2 BC 2 O 4 , NaBF 2 (OCOOC (CF 3 ) 2
  • the type of the Na-containing compound can be one type or two or more types.
  • the nonaqueous electrolyte includes cations such as Li ions (Li + ), and may include the following as anions.
  • anions include F ⁇ , OH ⁇ , SO 3 2 ⁇ , PO 4 3 ⁇ , PF 6 ⁇ , BF 4 ⁇ , ClO 4 ⁇ , AsF 6 ⁇ , CF 3 SO 3 ⁇ , N (C 2 F 5 SO 2 ) 2 ⁇ , C (CF 3 SO 2 ) 3 ⁇ , N (CF 3 SO 2 ) 2 ⁇ , N (SO 2 C 2 F 5 ) 2 ⁇ , N (SO 2 F) 2 ⁇ , PF 2 O 2 -, PFO 3 H -, B (C 2 O 4) 2 -, F 2 BC 2 O 4 -, BF 2 (OCOOC (CF 3) 2 -. kind of anion that contains the one or more kinds Can be.
  • the amount of Na component in the nonaqueous electrolyte can be determined by the following method.
  • the nonaqueous electrolyte battery is discharged at 1 C until the battery voltage reaches 1.0 V, and disassembled in a glove box in an inert atmosphere.
  • the nonaqueous electrolyte contained in the battery and electrode group is extracted.
  • the non-aqueous electrolyte is a liquid non-aqueous electrolyte
  • the non-aqueous electrolyte is filtered using a filter paper corresponding to Class 5 C specified in JIS P 3801 [filter paper (for chemical analysis)] to remove the solid content. And weigh.
  • the obtained electrolytic solution is dissolved in hydrochloric acid, diluted with ion-exchanged water, and then the amount of sodium contained is calculated by inductively coupled plasma emission spectroscopy.
  • a nonaqueous electrolyte battery includes a separator disposed between a positive electrode and a negative electrode, an exterior member that accommodates the positive electrode, the negative electrode, the separator, and the nonaqueous electrolyte, and an energization that is drawn out of the exterior member.
  • a positive electrode terminal and a negative electrode terminal can be further provided.
  • the separator for example, a porous film formed from a material such as polyethylene, polypropylene, polyethylene terephthalate, cellulose, and polyvinylidene fluoride (PVdF), a synthetic resin nonwoven fabric, or the like can be used. Furthermore, the separator which apply
  • Exterior material As the exterior member, a laminated film bag-like container or a metal container is used.
  • Examples of the shape include a flat type, a square type, a cylindrical type, a coin type, a button type, a sheet type, and a laminated type.
  • a large battery mounted on a two-wheel to four-wheel automobile or the like may be used.
  • the laminate film a multilayer film in which a metal layer is interposed between resin films is used.
  • the metal layer is preferably an aluminum foil or an aluminum alloy foil for weight reduction.
  • a polymer material such as polypropylene (PP), polyethylene (PE), nylon, and polyethylene terephthalate (PET) can be used.
  • the laminate film can be formed into the shape of an exterior member by sealing by heat sealing.
  • the laminate film preferably has a thickness of 0.2 mm or less.
  • the metal container can be formed from aluminum or an aluminum alloy.
  • the aluminum alloy preferably contains elements such as magnesium, zinc and silicon.
  • the content of transition metals such as iron, copper, nickel and chromium is preferably 100 ppm or less. Thereby, it becomes possible to dramatically improve long-term reliability and heat dissipation in a high temperature environment.
  • the metal container preferably has a thickness of 0.5 mm or less, and more preferably has a thickness of 0.2 mm or less.
  • the positive electrode terminal is electrically connected to the positive electrode.
  • the positive electrode terminal is formed of a material that is electrically stable and has electrical conductivity in a range where the potential with respect to the lithium ion metal is 3.0 V or more and 4.5 V or less. It is preferably formed from aluminum or an aluminum alloy containing one or more elements selected from the group consisting of Mg, Ti, Zn, Mn, Fe, Cu and Si.
  • the positive electrode terminal is preferably formed of the same material as the positive electrode current collector in order to reduce contact resistance with the positive electrode current collector.
  • the negative terminal is electrically connected to the negative electrode.
  • the negative electrode terminal is formed of a material that is electrically stable and has electrical conductivity in a range where the potential with respect to the lithium ion metal is 1.0 V or more and 3.0 V or less. It is preferably formed from aluminum or an aluminum alloy containing one or more elements selected from the group consisting of Mg, Ti, Zn, Mn, Fe, Cu and Si.
  • the negative electrode terminal is preferably formed from the same material as the negative electrode current collector in order to reduce the contact resistance with the negative electrode current collector.
  • FIGS. 1 is a cross-sectional view of a flat type nonaqueous electrolyte battery according to the first embodiment
  • FIG. 2 is an enlarged cross-sectional view of a portion A in FIG.
  • the flat wound electrode group 1 is housed in a bag-shaped exterior member 2 made of a laminate film having a metal layer interposed between two resin films.
  • the flat wound electrode group 1 is formed by winding a laminate of the negative electrode 3, the separator 4, the positive electrode 5, and the separator 4 in this order from the outside in a spiral shape and press-molding.
  • the outermost negative electrode 3 has a configuration in which a negative electrode active material-containing layer 3b containing a negative electrode active material is formed on one surface on the inner surface side of a negative electrode current collector 3a.
  • the negative electrode active material-containing layer 3b is formed on both surfaces of the current collector 3a.
  • the positive electrode 5 is configured by forming positive electrode active material-containing layers 5b on both surfaces of a positive electrode current collector 5a.
  • the negative electrode terminal 6 is connected to the negative electrode current collector 3 a of the outermost negative electrode 3, and the positive electrode terminal 7 is connected to the positive electrode current collector 5 a of the inner positive electrode 5.
  • the negative electrode terminal 6 and the positive electrode terminal 7 are extended to the outside from the opening of the bag-shaped exterior member 2.
  • the liquid nonaqueous electrolyte is injected from the opening of the bag-shaped exterior member 2.
  • the wound electrode group 1 and the liquid nonaqueous electrolyte are completely sealed by heat-sealing the opening of the bag-shaped exterior member 2 with the negative electrode terminal 6 and the positive electrode terminal 7 interposed therebetween.
  • the nonaqueous electrolyte battery according to the first embodiment is not limited to the configuration shown in FIGS. 1 and 2 described above, and can be configured as shown in FIGS. 3 and 4, for example.
  • FIG. 3 is a partially cutaway perspective view schematically showing another flat type nonaqueous electrolyte battery according to the first embodiment
  • FIG. 4 is an enlarged sectional view of a portion B in FIG.
  • the laminated electrode group 11 is housed in an exterior member 12 made of a laminate film in which a metal layer is interposed between two resin films. As shown in FIG. 4, the stacked electrode group 11 has a structure in which positive electrodes 13 and negative electrodes 14 are alternately stacked with separators 15 interposed therebetween.
  • positive electrodes 13 each of which includes a current collector 13 a and a positive electrode active material-containing layer 13 b supported on both surfaces of the current collector 13 a.
  • One side of the current collector 14 a of each negative electrode 14 protrudes from the positive electrode 13.
  • the protruding current collector 14 a is electrically connected to the strip-like negative electrode terminal 16.
  • the tip of the strip-shaped negative electrode terminal 16 is drawn out from the exterior member 12 to the outside.
  • the current collector 13a of the positive electrode 13 protrudes from the negative electrode 14 on the side opposite to the protruding side of the current collector 14a.
  • the current collector 13 a protruding from the negative electrode 14 is electrically connected to the belt-like positive electrode terminal 17.
  • the tip of the strip-like positive electrode terminal 17 is located on the opposite side of the negative electrode terminal 16 and is drawn out from the side of the exterior member 12 to the outside.
  • Examples of the shape of the battery include a flat type, a square type, a cylindrical type, a coin type, a button type, a sheet type, and a laminated type.
  • a large battery mounted on a two-wheel to four-wheel automobile or the like may be used.
  • the general formula (1) Li 2 + v Na 2-y M1 x Ti 6-y-z Nb y M2 z O 14 + ⁇ orthorhombic represented by Akiragata Na-containing niobium titanium Since the negative electrode including the composite oxide particles and the positive electrode including the Na component are provided, a nonaqueous electrolyte battery having high energy density and excellent high-temperature durability can be realized.
  • a battery pack is provided. This battery pack includes the nonaqueous electrolyte battery according to the first embodiment.
  • the battery pack according to the second embodiment can also include a plurality of nonaqueous electrolyte batteries.
  • the plurality of nonaqueous electrolyte batteries can be electrically connected in series, or can be electrically connected in parallel.
  • a plurality of nonaqueous electrolyte batteries can be connected in a combination of series and parallel.
  • the battery pack according to the second embodiment can include five first nonaqueous electrolyte batteries. These non-aqueous electrolyte batteries can be connected in series. Moreover, the non-aqueous electrolyte battery connected in series can comprise an assembled battery. That is, the battery pack according to the second embodiment can include an assembled battery.
  • the battery pack according to the second embodiment can include a plurality of assembled batteries.
  • the plurality of assembled batteries can be connected in series, parallel, or a combination of series and parallel.
  • the battery pack of the embodiment will be described in detail with reference to FIG. 5 and FIG.
  • the flat battery shown in FIG. 1 can be used for the unit cell.
  • a plurality of unit cells 21 composed of the flat type nonaqueous electrolyte battery shown in FIG. 1 are laminated so that the negative electrode terminal 6 and the positive electrode terminal 7 extending to the outside are aligned in the same direction.
  • the assembled battery 23 is configured by fastening. These unit cells 21 are electrically connected to each other in series as shown in FIG.
  • the printed wiring board 24 is arranged to face the side surface of the unit cell 21 from which the negative electrode terminal 6 and the positive electrode terminal 7 extend. As shown in FIG. 6, the printed wiring board 24 is mounted with a thermistor 25, a protection circuit 26, and a terminal 27 for energizing external devices. An insulating plate (not shown) is attached to the surface of the protection circuit board 24 facing the assembled battery 23 in order to avoid unnecessary connection with the wiring of the assembled battery 23.
  • the positive electrode side lead 28 is connected to the positive electrode terminal 7 located in the lowermost layer of the assembled battery 23, and the tip thereof is inserted into the positive electrode side connector 29 of the printed wiring board 24 and electrically connected thereto.
  • the negative electrode side lead 30 is connected to the negative electrode terminal 6 located in the uppermost layer of the assembled battery 23, and the tip thereof is inserted into the negative electrode side connector 31 of the printed wiring board 24 and electrically connected thereto.
  • These connectors 29 and 31 are connected to the protection circuit 26 through wirings 32 and 33 formed on the printed wiring board 24.
  • the thermistor 25 detects the temperature of the unit cell 21, and the detection signal is transmitted to the protection circuit 26.
  • the protection circuit 26 can cut off the plus side wiring 34a and the minus side wiring 34b between the protection circuit 26 and the energization terminal 27 to the external device under a predetermined condition.
  • the predetermined condition is, for example, when the temperature detected by the thermistor 25 is equal to or higher than a predetermined temperature.
  • the predetermined condition is when the overcharge, overdischarge, overcurrent, etc. of the cell 21 are detected. This detection of overcharge or the like is performed for each single cell 21 or the entire single cell 21.
  • the battery voltage may be detected, or the positive electrode potential or the negative electrode potential may be detected.
  • a lithium electrode used as a reference electrode is inserted into each unit cell 21.
  • a wiring 35 for voltage detection is connected to each single cell 21, and a detection signal is transmitted to the protection circuit 26 through these wirings 35.
  • Protective sheets 36 made of rubber or resin are disposed on the three side surfaces of the assembled battery 23 excluding the side surfaces from which the positive electrode terminal 7 and the negative electrode terminal 6 protrude.
  • the assembled battery 23 is stored in a storage container 37 together with each protective sheet 36 and the printed wiring board 24. That is, the protective sheet 36 is disposed on each of the inner side surface in the long side direction and the inner side surface in the short side direction of the storage container 37, and the printed wiring board 24 is disposed on the inner side surface on the opposite side in the short side direction.
  • the assembled battery 23 is located in a space surrounded by the protective sheet 36 and the printed wiring board 24.
  • the lid 38 is attached to the upper surface of the storage container 37.
  • a heat shrink tape may be used for fixing the assembled battery 23.
  • protective sheets are arranged on both side surfaces of the assembled battery, the heat shrinkable tube is circulated, and then the heat shrinkable tube is thermally contracted to bind the assembled battery.
  • 5 and 6 show a configuration in which the cells 21 are connected in series, but in order to increase the battery capacity, they may be connected in parallel.
  • the assembled battery packs can be connected in series or in parallel.
  • the mode of the battery pack is appropriately changed depending on the application.
  • the use of the battery pack those in which cycle characteristics with large current characteristics are desired are preferable.
  • Specific examples include vehicles, for example, two-wheel to four-wheel hybrid electric vehicles, two-wheel to four-wheel electric vehicles, on-board vehicles such as assist bicycles, and trains.
  • the vehicle-mounted one is suitable.
  • FIG. 7 shows an assembled battery in which a plurality of the nonaqueous electrolyte batteries of the first embodiment are connected in series.
  • the assembled battery 23 shown in FIG. 7 includes a plurality of (for example, five) square nonaqueous electrolyte batteries 21 as unit cells.
  • a metal container is used for the exterior member of the rectangular nonaqueous electrolyte battery 21.
  • the positive electrode terminal 7 of the battery 21 (nonaqueous electrolyte battery A) and the negative electrode terminal 6 of the battery 21 (nonaqueous electrolyte battery B) located adjacent thereto are electrically connected by leads 40.
  • the positive electrode terminal 7 of the battery 21 (nonaqueous electrolyte battery B) and the negative electrode terminal 6 of the battery 21 (nonaqueous electrolyte battery C) located adjacent thereto are electrically connected by leads 40.
  • the five batteries 21 are connected in series.
  • the positive terminal 7 of the battery 21 positioned at one end (left side in FIG. 7) of the series of batteries 21 connected in series is electrically connected to the external positive terminal 41 for energization.
  • the negative electrode terminal 6 of the battery 21 located at the other end (right side in FIG. 7) of this row is electrically connected to the external negative electrode terminal 42 for energization.
  • An assembled battery in which five nonaqueous electrolyte batteries of the first embodiment are connected in series can exhibit an average operating voltage of 12V to 14V.
  • the average operating voltage within this range is about the same as the average operating voltage of a 12V battery pack including a lead storage battery. Therefore, an assembled battery capable of exhibiting such an average operating voltage can assist input / output of the lead storage battery when used in parallel with a 12V system assembled battery including the lead storage battery. Thereby, the charge by the overdischarge and excessive current which cause deterioration of a lead storage battery can be prevented. Therefore, the assembled battery in which the five nonaqueous electrolyte batteries of the first embodiment are connected in series can exhibit excellent voltage compatibility with the assembled battery including the lead storage battery. In particular, voltage compatibility can be further improved by including a lithium manganese composite oxide having a spinel crystal structure in the positive electrode active material of the nonaqueous electrolyte battery of the first embodiment.
  • the non-aqueous electrolyte battery of the first embodiment since the non-aqueous electrolyte battery of the first embodiment is included, a battery pack having high energy density and excellent high-temperature durability can be provided.
  • Example 1 the nonaqueous electrolyte battery of Example 1 was produced by the following procedure.
  • a powder of a spinel type lithium manganese complex oxide LiAl 0.1 Mn 1.9 O 4 was prepared as a positive electrode active material. 89.9% by mass: 5% by mass: 5% by mass of this composite oxide, acetylene black as a conductive agent, polyvinylidene fluoride (PVdF) as a binder, and sodium carbonate Na 2 CO 3
  • NMP N-methylpyrrolidone
  • the prepared slurry was applied to both surfaces of a current collector made of an aluminum foil having a thickness of 15 ⁇ m.
  • the coating amount per unit area was 95 g / m 2 .
  • the coating film was dried and subjected to pressing.
  • a positive electrode having an electrode density (not including the current collector) of 2.7 g / cm 3 was produced.
  • niobium hydroxide (V): As raw materials, and titanium oxide TiO 2, and lithium carbonate Li 2 CO 3, sodium carbonate Na 2 CO 3, niobium hydroxide (V): were prepared and Nb (OH) 5. These raw materials were mixed so that the molar ratio of Li: Na: Ti: Nb in the mixture was 2: 1.7: 5.7: 0.3. Prior to mixing, the raw material was thoroughly pulverized. The mixed raw material was heat-treated at 900 ° C. for 3 hours in an air atmosphere. Thus, a powder of Na-containing niobium titanium composite oxide particles having an orthorhombic crystal structure was obtained as a negative electrode active material.
  • the reaction potential (lithium occlusion / release potential) of the Na-containing niobium titanium composite oxide particles having an orthorhombic crystal structure was 1.0 to 1.5 V (vs. Li / Li + ).
  • the average particle diameter of the Na-containing niobium titanium composite oxide particles having an orthorhombic crystal structure was 10 ⁇ m.
  • the prepared slurry was applied to both surfaces of a current collector made of an aluminum foil having a thickness of 15 ⁇ m.
  • the coating amount per unit area was 100 g / m 2 .
  • the coating film was dried and subjected to pressing.
  • a negative electrode having an electrode density (not including the current collector) of 2.3 g / cm 3 was produced.
  • the positive electrode prepared earlier, one separator, the negative electrode prepared earlier, and another separator were laminated in this order to obtain a laminate.
  • This laminate was wound in a spiral. This was heated and pressed at 90 ° C. to produce a flat electrode group having a width of 30 mm and a thickness of 3.0 mm.
  • the obtained electrode group was housed in a pack made of a laminate film and vacuum dried at 80 ° C. for 24 hours.
  • the laminate film was constituted by forming a polypropylene layer on both sides of an aluminum foil having a thickness of 40 ⁇ m, and the total thickness was 0.1 mm.
  • a liquid nonaqueous electrolyte was injected into the laminate film pack containing the electrode group as described above. Thereafter, the pack was completely sealed by heat sealing.
  • a nonaqueous electrolyte battery having the structure shown in FIGS. 3 and 4 described above, having a width of 35 mm, a thickness of 3.2 mm, and a height of 65 mm was manufactured.
  • the capacity of the nonaqueous electrolyte battery was 300 mAh.
  • the battery voltage was 2.7 V when the SOC (State of charge) was 50%.
  • the nominal capacity of the nonaqueous electrolyte battery is assumed to be SOC 100%.
  • Example 2 A nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that the Na component content in the positive electrode was changed as shown in Table 1 below.
  • Example 6 to 8 A nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that the type of Na-containing compound added to the positive electrode was changed as shown in Table 1 below.
  • Example 9 A nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that the composition of the orthorhombic Na-containing niobium titanium composite oxide particles was changed as shown in Table 1. The battery voltage when the SOC was 50% was 2.67V.
  • Example 10 90% by mass of orthorhombic Na-containing niobium titanium composite oxide particles synthesized in the same manner as in Example 1, lithium titanate having a spinel crystal structure (Li 4 Ti 5 O 12 , reaction potential (lithium occlusion / release potential) Is a nonaqueous electrolyte in the same manner as in Example 1 except that 1.55 V (vs. Li / Li + ) and an average particle diameter of 1.5 ⁇ m mixed with 10% by mass are used as the negative electrode active material.
  • a battery was manufactured.
  • Example 11 As a positive electrode active material, a powder of spinel type lithium manganese complex oxide LiAl 0.1 Mn 1.9 O 4 was prepared.
  • This composite oxide, acetylene black as a conductive agent, and polyvinylidene fluoride (PVdF) as a binder are mixed at a mixing ratio of 90% by mass: 5% by mass: 5% by mass with N-methyl as a solvent. Poured into pyrrolidone (NMP) and mixed. Next, the mixture thus obtained was dispersed using a rotation and revolution mixer to prepare a slurry. Next, the prepared slurry was applied to both surfaces of a current collector made of an aluminum foil having a thickness of 15 ⁇ m. The coating amount per unit area was 95 g / m 2 . Next, the coating film was dried and subjected to pressing. Thus, a positive electrode having an electrode density (not including the current collector) of 2.7 g / cm 3 was produced.
  • PC Propylene carbonate
  • EMC ethyl methyl carbonate
  • Example 12 As a positive electrode active material, a powder of spinel type lithium manganese complex oxide LiAl 0.1 Mn 1.9 O 4 was prepared. This composite oxide, acetylene black as a conductive agent, and polyvinylidene fluoride (PVdF) as a binder are mixed at a mixing ratio of 90% by mass: 5% by mass: 5% by mass with N-methyl as a solvent. Poured into pyrrolidone (NMP) and mixed. Next, the mixture thus obtained was dispersed using a rotation and revolution mixer to prepare a slurry. Next, the prepared slurry was applied to both surfaces of a current collector made of an aluminum foil having a thickness of 15 ⁇ m.
  • PVdF polyvinylidene fluoride
  • the coating amount per unit area was 95 g / m 2 .
  • the coating film was dried and subjected to pressing.
  • a positive electrode having an electrode density (not including the current collector) of 2.7 g / cm 3 was produced.
  • a non-aqueous electrolyte battery was assembled in the same manner as in Example 1 except that the obtained positive electrode was used, and then charged and discharged to confirm the discharge capacity. Thereafter, the battery was discharged at a 1C rate until the battery voltage became 0.8 V, and the battery was overdischarged. Thereafter, the overdischarged nonaqueous electrolyte battery was left in an environment of 70 ° C. for 12 hours. After being allowed to stand, the battery was charged again, and then the discharge capacity was confirmed.
  • Example 13 a powder of a spinel type lithium manganese complex oxide LiAl 0.1 Mn 1.9 O 4 was prepared as a positive electrode active material.
  • This composite oxide, acetylene black as a conductive agent, polyvinylidene fluoride (PVdF) as a binder, and sodium carbonate Na 2 CO 3 are 89.995% by mass: 5% by mass: 5% by mass:
  • NMP N-methylpyrrolidone
  • the mixture thus obtained was dispersed using a rotation and revolution mixer to prepare a slurry.
  • the prepared slurry was applied to both surfaces of a current collector made of an aluminum foil having a thickness of 15 ⁇ m.
  • the coating amount per unit area was 95 g / m 2 .
  • the coating film was dried and subjected to pressing.
  • a positive electrode having an electrode density (not including the current collector) of 2.7 g / cm 3 was produced.
  • a nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that the obtained positive electrode was used.
  • Example 14 a powder of a spinel type lithium manganese complex oxide LiAl 0.1 Mn 1.9 O 4 was prepared as a positive electrode active material. 87% by mass: 5% by mass: 5% by mass: 3% by mass of this composite oxide, acetylene black as a conductive agent, polyvinylidene fluoride (PVdF) as a binder, and sodium carbonate Na 2 CO 3
  • NMP N-methylpyrrolidone
  • the mixture thus obtained was dispersed using a rotation and revolution mixer to prepare a slurry.
  • the prepared slurry was applied to both surfaces of a current collector made of an aluminum foil having a thickness of 15 ⁇ m.
  • the coating amount per unit area was 95 g / m 2 .
  • the coating film was dried and subjected to pressing.
  • a positive electrode having an electrode density (not including the current collector) of 2.7 g / cm 3 was produced.
  • a nonaqueous electrolyte battery was produced in the same manner as in Example 1 except that the obtained positive electrode was used.
  • Example 15 First, spinel-type lithium manganese composite oxide LiAl 0.1 Mn 1.9 O 4 powder and lithium cobalt composite oxide LiCoO 2 powder were prepared as positive electrode active materials.
  • Example 16 First, spinel-type lithium manganese composite oxide LiAl 0.1 Mn 1.9 O 4 powder and lithium cobalt composite oxide LiCoO 2 powder were prepared as positive electrode active materials.
  • Example 3 Except for using orthorhombic Na-containing niobium titanium composite oxide particles as the negative electrode active material, Li 2 SrTi 6 O 14 (average particle size is 10 ⁇ m) having an orthorhombic crystal structure is the same as in Example 1. Thus, a non-aqueous electrolyte battery was manufactured. The battery voltage when the SOC was 50% was 2.6V.
  • Example 4 Example 1 except that Li 2 Na 2 Ti 6 O 14 (average particle size is 10 ⁇ m) having an orthorhombic crystal structure is used instead of the orthorhombic Na-containing niobium titanium composite oxide particles as the negative electrode active material. A nonaqueous electrolyte battery was manufactured in the same manner as described above. The battery voltage when the SOC was 50% was 2.7V.
  • the Na component was present on the surface of the positive electrode active material particles. It was confirmed that it was present on the surface of the particles.
  • Tables 1 and 3 show the mass ratios (W Co / W Mn ) measured by the above-described methods for the nonaqueous electrolyte batteries of Examples and Comparative Examples.
  • the nonaqueous electrolyte battery was repeatedly charged and discharged in a 50 ° C. environment to measure cycle characteristics. The battery was charged at 1C rate until it was fully charged. Thereafter, the battery was left for 30 minutes, and discharged at a 1C rate until the battery voltage became 1.2V. The battery was left for 30 minutes and charged again. After repeating the above charging and discharging 50 times, the battery voltage was charged again at a 0.2 C rate until the battery voltage was fully charged. Thereafter, the nonaqueous electrolyte battery was discharged at a 0.2 C rate until the battery voltage became 1.2V. A value obtained by dividing the discharge capacity at this time by the initial discharge capacity was defined as a high-temperature cycle characteristic. The results are shown in Tables 2 and 3.
  • the nonaqueous electrolyte batteries of Examples 1 to 14 exhibited higher output than Comparative Examples 1 to 4 while realizing excellent high temperature durability.
  • the non-aqueous electrolyte batteries of Examples 1 to 14 include the orthorhombic Na-containing niobium titanium composite oxide represented by the general formula (1), so that the positive electrode has a high battery voltage and contains the Na component.
  • the comparison between Comparative Examples 1 to 4 and Example 1 shows that the battery capacity and the operating voltage of the battery increased due to the decrease in the reaction potential of the negative electrode, and the energy density increased.
  • the comparison between Examples 1 to 5, 13, and 14 shows that high temperature durability is improved when an appropriate amount of Na component is present in the positive electrode.
  • Comparison of Examples 1 to 5 shows that the high temperature durability is further improved by setting the content of the Na component to 0.05 mass% or more and 0.5 mass% or less.
  • Example 15 Furthermore, from the results of Examples 15 and 16, it can be seen that good results can also be obtained by including a certain amount of Co component together with Na in the positive electrode. From the comparison between Example 15 and Example 16, it can be seen that when the Co component satisfies the formula (2), the energy density is increased by the high battery voltage, and the high-temperature durability is simultaneously improved.
  • the non-aqueous electrolyte battery of the general formula (1) oblique represented by Li 2 + v Na 2-y M1 x Ti 6-y-z Nb y M2 z O 14 + ⁇ according to at least one of the embodiments and examples described above Since the negative electrode containing the tetragonal Na-containing niobium titanium composite oxide particles and the positive electrode containing the Na component are included, the input / output performance and the high temperature durability can be made excellent.

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Abstract

Selon la présente invention, une batterie à électrolyte non aqueux comprenant une électrode positive, une électrode négative et un électrolyte non aqueux est fournie. L'électrode négative contient une substance active d'électrode négative comprenant des particules d'oxyde composite de niobium-titane contenant du Na cristallin rhombique représentées par la formule générale (1) Li 2 + v Na 2-y M1 x Ti 6-y-z Nb y M2 z O 14 + δ Dans la formule générale (1), M1 représente un ou plusieurs éléments choisis dans le groupe constitué par Cs, K, Sr, Ba et Ca, M2 représente un ou plusieurs éléments choisis dans le groupe constitué par Zr, Al, Sn, V, Ta, Mo, W, Fe, Co et Mn, 0 ≤ v < 2, 0 ≤ x < 2, 0 < y < 2, 0 ≤ z < 3, et -0,5 ≤ δ ≤ 0,5. L'électrode positive contient une substance active d'électrode positive et une composante Na.
PCT/JP2016/072385 2016-07-29 2016-07-29 Batterie à électrolyte non aqueux et bloc-batterie WO2018020670A1 (fr)

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CN111837261A (zh) * 2018-03-30 2020-10-27 株式会社东芝 电极组、电池及电池包
JP2021048009A (ja) * 2019-09-17 2021-03-25 株式会社東芝 電極、二次電池、電池パック、及び車両

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JP2016100077A (ja) * 2014-11-18 2016-05-30 日本電信電話株式会社 ナトリウム二次電池
WO2016084200A1 (fr) * 2014-11-27 2016-06-02 株式会社 東芝 Matériau actif pour batteries, batterie à électrolyte non aqueux, batterie assemblée, bloc-batterie et automobile

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Cited By (3)

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CN111837261A (zh) * 2018-03-30 2020-10-27 株式会社东芝 电极组、电池及电池包
CN111837261B (zh) * 2018-03-30 2023-08-01 株式会社东芝 电极组、电池及电池包
JP2021048009A (ja) * 2019-09-17 2021-03-25 株式会社東芝 電極、二次電池、電池パック、及び車両

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