WO2015156400A1 - Électrode positive destinée à un dispositif électrique et dispositif électrique utilisant celle-ci - Google Patents

Électrode positive destinée à un dispositif électrique et dispositif électrique utilisant celle-ci Download PDF

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WO2015156400A1
WO2015156400A1 PCT/JP2015/061284 JP2015061284W WO2015156400A1 WO 2015156400 A1 WO2015156400 A1 WO 2015156400A1 JP 2015061284 W JP2015061284 W JP 2015061284W WO 2015156400 A1 WO2015156400 A1 WO 2015156400A1
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positive electrode
active material
electrode active
battery
composite oxide
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Japanese (ja)
Inventor
和幸 坂本
博文 安田
奈穂子 西村
英則 村田
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Nissan Motor Co Ltd
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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
    • H01M4/36—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • 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 positive electrode for an electric device and an electric device using the same.
  • a nonaqueous electrolyte secondary battery generally includes a positive electrode obtained by applying a positive electrode active material or the like to a current collector, and a negative electrode obtained by applying a negative electrode active material or the like to a current collector. It has the structure connected through the electrolyte layer holding electrolyte gel. Then, when ions such as lithium ions are occluded / released in the electrode active material, a charge / discharge reaction of the battery occurs.
  • non-aqueous electrolyte secondary batteries with a low environmental load are being used not only for portable devices, but also for power supply devices for electric vehicles such as hybrid vehicles (HEV), electric vehicles (EV), and fuel cell vehicles. .
  • HEV hybrid vehicles
  • EV electric vehicles
  • fuel cell vehicles fuel cell vehicles.
  • Non-aqueous electrolyte secondary batteries intended for application to electric vehicles are required to have high output and high capacity.
  • a positive electrode active material used for a positive electrode of a non-aqueous electrolyte secondary battery for an electric vehicle a lithium-cobalt composite oxide that is a layered composite oxide can obtain a high voltage of 4V and has a high energy density. Since it has, it has already been widely put into practical use.
  • cobalt which is a raw material, is scarce in terms of resources and is expensive, there is anxiety in terms of supply of raw materials, considering the possibility that demand will increase significantly in the future. In addition, the price of cobalt raw materials may rise. Therefore, a composite oxide having a low cobalt content is desired.
  • the lithium nickel composite oxide has a layered structure like the lithium cobalt composite oxide, is cheaper than the lithium cobalt composite oxide, and is comparable to the lithium cobalt composite oxide in theoretical discharge capacity. From such a viewpoint, the lithium nickel composite oxide is expected to be able to constitute a practical large-capacity battery.
  • lithium nickel composite oxide such as a lithium nickel composite oxide as a positive electrode active material
  • the composite Charging / discharging is performed by desorption / insertion of lithium ions into the oxide.
  • Japanese Patent Application Laid-Open No. 2011-54334 discloses a lithium transition metal composite oxide having a layered crystal structure that can insert and release lithium ions and contains manganese and nickel as a positive electrode active material, and manganese.
  • a technique using a lithium transition metal composite oxide having a spinel crystal structure is disclosed.
  • the technique described in Japanese Patent Application Laid-Open No. 2011-54334 discloses that the composition ratio of nickel to the transition metal element other than lithium in the lithium transition metal composite oxide having the layered crystal structure is 50% or more by molar ratio. The above problems are solved.
  • the present invention can reduce the internal resistance of a battery in an electric device such as a lithium ion secondary battery, and thus can suppress a decrease in battery capacity accompanying the progress of a charge / discharge cycle (that is, cycle durability can be improved). )
  • the purpose is to provide means.
  • the present inventors have accumulated earnest research.
  • the lithium transition metal composite oxide containing manganese and nickel and having a layered crystal structure capable of inserting and releasing lithium ions is used as the positive electrode active material, and the crystallite size of the lithium transition metal composite oxide is in the range of 900 mm or more. It has been found that the above-mentioned problems can be solved by controlling the present invention, and the present invention has been completed.
  • a positive electrode for an electric device in which a positive electrode active material layer is formed on the surface of a positive electrode current collector.
  • the positive electrode active material layer includes manganese and nickel and a lithium transition metal composite oxide having a layered crystal structure capable of inserting and removing lithium ions as a positive electrode active material.
  • the lithium transition metal composite oxide is characterized in that the crystallite size is 900 mm or more.
  • FIG. 3 is a schematic cross-sectional view illustrating a basic configuration of a non-aqueous electrolyte lithium ion secondary battery that is not a flat type (stacked type) bipolar type, which is an embodiment of the electric device, and is a cross-sectional view taken along the line AA illustrated in FIG. FIG. It is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of an electric device
  • a positive electrode for an electric device in which a positive electrode active material layer is formed on a surface of a positive electrode current collector, the positive electrode active material layer containing manganese and nickel and containing lithium ions
  • a positive electrode for an electrical device comprising a lithium transition metal composite oxide having a layered crystal structure capable of insertion / extraction as a positive electrode active material, wherein the lithium transition metal composite oxide has a crystallite size of 900 mm or more.
  • the positive electrode active material used for the positive electrode for an electrical device essentially contains a lithium transition metal composite oxide having a layered crystal structure containing manganese and nickel and capable of inserting and releasing lithium ions.
  • a lithium transition metal composite oxide having a layered crystal structure containing manganese and nickel and capable of inserting and releasing lithium ions.
  • the composition of the lithium transition metal composite oxide conventionally known knowledge can be referred to as appropriate.
  • a lithium-nickel-manganese-cobalt composite oxide (hereinafter also simply referred to as “NMC composite oxide”) includes a lithium atomic layer and a transition metal (Mn, Ni And Co are arranged in an orderly manner) It has a layered crystal structure in which atomic layers are alternately stacked via oxygen atomic layers, one Li atom is included per one atom of transition metal M, and the amount of Li that can be taken out is spinel system
  • the lithium manganese oxide is doubled, that is, the supply capacity is doubled, and a high capacity can be obtained.
  • it since it has higher thermal stability than LiNiO 2 , it is particularly advantageous among the nickel-based composite oxides used as the positive electrode active material.
  • the NMC composite oxide includes a composite oxide in which a part of the transition metal element is substituted with another metal element.
  • Other elements in that case include Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, Fe, B, Ga, In, Si, Mo, Y, Sn, V, Cu , Ag, Zn, etc., preferably Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, Cr, more preferably Ti, Zr, P, Al, Mg, From the viewpoint of improving cycle characteristics, Ti, Zr, Al, Mg, and Cr are more preferable.
  • a represents the atomic ratio of Li
  • b represents the atomic ratio of Ni
  • c represents the atomic ratio of Mn
  • d represents the atomic ratio of Co
  • x represents the atomic ratio of M. Represents. From the viewpoint of cycle characteristics, it is preferable that 0.4 ⁇ b ⁇ 0.6 in the general formula (1).
  • the composition of each element can be measured by, for example, inductively coupled plasma (ICP) emission spectrometry.
  • ICP inductively coupled plasma
  • Ni nickel
  • Co cobalt
  • Mn manganese
  • Ti or the like partially replaces the transition metal in the crystal lattice. From the viewpoint of cycle characteristics, it is preferable that a part of the transition element is substituted with another metal element, and it is particularly preferable that 0 ⁇ x ⁇ 0.3 in the general formula (1). Since at least one selected from the group consisting of Ti, Zr, Nb, W, P, Al, Mg, V, Ca, Sr, and Cr is dissolved, the crystal structure is stabilized. It is considered that the battery capacity can be prevented from decreasing even if the above is repeated, and that excellent cycle characteristics can be realized.
  • the present inventors charge and discharge the above-mentioned charge and discharge when the metal composition of nickel, manganese and cobalt is not uniform, for example, LiNi 0.5 Mn 0.3 Co 0.2 O 2. It has been found that the influence of strain / cracking of the complex oxide at the time increases. This is presumably because the stress applied to the inside of the particles during expansion and contraction is distorted and cracks are more likely to occur in the composite oxide due to the non-uniform metal composition. Therefore, for example, a complex oxide having a rich Ni abundance ratio (for example, LiNi 0.8 Mn 0.1 Co 0.1 O 2 ) or a complex oxide having a uniform ratio of Ni, Mn, and Co.
  • a complex oxide having a rich Ni abundance ratio for example, LiNi 0.8 Mn 0.1 Co 0.1 O 2
  • a complex oxide having a uniform ratio of Ni, Mn, and Co for example, LiNi 0.8 Mn 0.1 Co 0.1 O 2
  • the lithium transition metal composite oxide according to this embodiment usually has a secondary particle structure in which primary particles are aggregated.
  • the average particle diameter (D1) of the primary particles is preferably 0.20 to 0.6 ⁇ m, more preferably 0.25 to 0.5 ⁇ m.
  • the average particle diameter (D2) of the secondary particles is preferably 5 to 20 ⁇ m, more preferably 5 to 15 ⁇ m.
  • the ratio value (D2 / D1) is preferably greater than 11, more preferably 15 to 50, and even more preferably 25 to 40.
  • the primary particles constituting the lithium transition metal composite oxide usually have a hexagonal crystal structure having a layered structure, but the size of the crystallite has a correlation with the size of D1. Yes.
  • crystallite means the largest group that can be regarded as a single crystal, and can be measured by a method of refining the crystal structure parameters from the diffraction intensity obtained by powder X-ray diffraction measurement or the like.
  • the lithium transition metal composite oxide according to the present embodiment is characterized by its crystallite size value, specifically 900 mm or more, preferably 950 mm or more. By setting it as such a structure, decay
  • the upper limit of the crystallite size is not particularly limited, but is preferably 1 ⁇ m or less, more preferably 0.55 ⁇ m or less, and further preferably 0.4 ⁇ m or less.
  • the values measured by the method described in the column of Examples described later are adopted as the values of D1, D2 and crystallite size in the lithium transition metal composite oxide.
  • the BET specific surface area of the lithium transition metal composite oxide according to this embodiment is preferably 0.1 to 1.0 m 2 / g, more preferably 0.3 to 1.0 m 2 / g, and particularly preferably 0.3 to 0.7 m 2 / g.
  • the specific surface area of the active material is in such a range, the reaction area of the active material is ensured and the internal resistance of the battery is reduced, so that the occurrence of polarization during the electrode reaction can be minimized.
  • the half width of the diffraction peak on the (003) plane obtained by powder X-ray diffraction measurement is preferably 0.115 or less, more preferably 0.103. It is as follows. Depending on the composition of the lithium transition metal composite oxide, such a configuration makes it possible to control the crystallite size to the above-described preferable value, and ultimately contributes to the expression of the effects of the present invention. It will be. Such crystallinity parameters can be controlled by the raw material, composition, firing conditions, and the like.
  • the lithium transition metal composite oxide such as the NMC composite oxide according to this embodiment can be prepared by selecting various known methods such as a coprecipitation method and a spray drying method.
  • the coprecipitation method is preferably used because the complex oxide according to this embodiment is easy to prepare.
  • a method for synthesizing the NMC composite oxide for example, a nickel-cobalt-manganese composite oxide is manufactured by a coprecipitation method as in the method described in JP2011-105588A, and then nickel-cobalt It can be obtained by mixing and firing a manganese composite oxide and a lithium compound. This will be specifically described below.
  • the raw material compound of the composite oxide for example, Ni compound, Mn compound and Co compound is dissolved in an appropriate solvent such as water so as to have a desired composition of the active material.
  • the Ni compound, Mn compound, and Co compound include sulfates, nitrates, carbonates, acetates, oxalates, oxides, hydroxides, and halides of the metal elements.
  • Specific examples of the Ni compound, Mn compound, and Co compound include, but are not limited to, nickel sulfate, cobalt sulfate, manganese sulfate, nickel acetate, cobalt acetate, and manganese acetate.
  • Ti, Zr, Nb as a metal element that substitutes a part of the layered lithium metal composite oxide constituting the active material so as to have a desired active material composition.
  • W, P, Al, Mg, V, Ca, Sr, and a compound containing at least one metal element such as Cr may be further mixed.
  • the coprecipitation reaction can be performed by neutralization and precipitation reaction using the above raw material compound and an alkaline solution.
  • the metal composite hydroxide and metal composite carbonate containing the metal contained in the said raw material compound are obtained.
  • the alkaline solution for example, an aqueous solution of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia or the like can be used, but sodium hydroxide, sodium carbonate or a mixed solution thereof is preferably used for the neutralization reaction. .
  • an aqueous ammonia solution or an ammonium salt is preferably used for the complex reaction.
  • the addition amount of the alkaline solution used for the neutralization reaction may be an equivalent ratio of 1.0 with respect to the neutralized content of all the metal salts contained, but it is preferable to add the alkali excess together for pH adjustment.
  • the addition amount of the aqueous ammonia solution or ammonium salt used for the complex reaction is preferably such that the ammonia concentration in the reaction solution is in the range of 0.01 to 2.00 mol / l.
  • the pH of the reaction solution is preferably controlled in the range of 10.0 to 13.0.
  • the reaction temperature is preferably 30 ° C. or higher, more preferably 30 to 60 ° C.
  • the composite hydroxide obtained by the coprecipitation reaction is then preferably suction filtered, washed with water and dried.
  • the particle size of the composite hydroxide can be controlled by adjusting the conditions (stirring time, alkali concentration, etc.) for carrying out the coprecipitation reaction, which is the secondary electrode of the positive electrode active material finally obtained. It affects the average particle size (D2) of the particles.
  • the nickel-cobalt-manganese composite hydroxide is mixed with a lithium compound and fired to obtain a lithium-nickel-manganese-cobalt composite oxide.
  • the Li compound include lithium hydroxide or a hydrate thereof, lithium peroxide, lithium nitrate, and lithium carbonate.
  • the firing treatment may be performed in one stage, but is preferably performed in two stages (temporary firing and main firing).
  • a composite oxide can be obtained efficiently by two-stage firing.
  • the pre-baking conditions are not particularly limited, and differ depending on the lithium raw material, so that it is difficult to uniquely define them.
  • the firing temperature and firing time during firing are particularly important. It is possible to control D1 and the crystallite size by adjusting based on the tendency. That is, when the firing time is increased, D1 and the crystallite size increase. Further, when the firing temperature is increased, D1 and the crystallite size are increased.
  • the temperature rising rate is preferably 1 to 20 ° C./min from room temperature.
  • the atmosphere is preferably in air or in an oxygen atmosphere.
  • the pre-baking temperature is preferably 500 to 900 ° C., more preferably 600 to 800 ° C., further preferably 650. ⁇ 750 ° C.
  • the pre-baking time is preferably 0.5 to 10 hours, more preferably 4 to 6 hours.
  • the conditions for the main firing are not particularly limited, but the rate of temperature rise is preferably from room temperature to 1 to 20 ° C./min.
  • the atmosphere is preferably in air or in an oxygen atmosphere.
  • the firing temperature is preferably 800 to 1200 ° C., more preferably 850 to 1100 ° C., and further preferably 900 to 1050. ° C.
  • the pre-baking time is preferably 1 to 20 hours, more preferably 8 to 12 hours.
  • a method of previously mixing with nickel, cobalt, manganate Any means such as a method of adding nickel, cobalt and manganate simultaneously, a method of adding to the reaction solution during the reaction, a method of adding to the nickel-cobalt-manganese composite oxide together with the Li compound may be used.
  • the composite oxide of the present invention can be produced by appropriately adjusting the reaction conditions such as the pH of the reaction solution, the reaction temperature, the reaction concentration, the addition rate, and the stirring time.
  • the positive electrode for electrical devices which concerns on this form may contain the other positive electrode active material which plays the role of an active material in a positive electrode.
  • examples of such other positive electrode active materials include spinel-based manganese positive electrode active material (LiMn 2 O 4 ), LiCoO 2 , LiNiO 2, and those in which a part of these transition metals is substituted with other elements, etc.
  • examples thereof include lithium-transition metal composite oxides, lithium-transition metal phosphate compounds, and lithium-transition metal sulfate compounds.
  • the content of the lithium transition metal composite oxide according to the first embodiment of the present invention described above is 80 to 100% by weight with respect to 100% by weight of the material that can function as the positive electrode active material contained in the positive electrode active material layer. Preferably, it is 95 to 100% by weight, more preferably 100% by weight.
  • the spinel manganese positive electrode active material (LiMn 2 O 4 ) is further included as the positive electrode active material.
  • the positive electrode active material layer may contain other additives such as a conductive additive, a binder, an electrolyte (polymer matrix, ion conductive polymer, electrolyte, etc.), and a lithium salt to enhance ionic conductivity as necessary.
  • a conductive additive such as aluminum silicate, aluminum silicate, magnesium silicate, magnesium silicate, magnesium silicate, magnesium silicate, magnesium silicate, magnesium silicate, magnesium silicate, magnesium, magnesium, magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium magnesium
  • the content of a material that can function as a positive electrode active material is preferably 85 to 99.5% by weight.
  • binder Although it does not specifically limit as a binder used for a positive electrode active material layer, for example, the following materials are mentioned. Polyethylene, polypropylene, polyethylene terephthalate (PET), polyether nitrile, polyacrylonitrile, polyimide, polyamide, cellulose, carboxymethyl cellulose (CMC) and its salts, ethylene-vinyl acetate copolymer, polyvinyl chloride, styrene-butadiene rubber (SBR) ), Isoprene rubber, butadiene rubber, ethylene / propylene rubber, ethylene / propylene / diene copolymer, styrene / butadiene / styrene block copolymer and hydrogenated product thereof, styrene / isoprene / styrene block copolymer and hydrogenated product thereof.
  • Thermoplastic polymers such as products, polyvinylidene fluoride (P
  • the amount of the binder contained in the positive electrode active material layer is not particularly limited as long as it is an amount capable of binding the active material, but preferably 0.5 to 15% by weight with respect to the active material layer. More preferably, it is 1 to 10% by weight.
  • the positive electrode active material layer further contains other additives such as a conductive additive, an electrolyte (polymer matrix, ion conductive polymer, electrolytic solution, etc.), and a lithium salt for improving ion conductivity, as necessary.
  • the conductive assistant means an additive blended to improve the conductivity of the positive electrode active material layer or the negative electrode active material layer.
  • the conductive aid include carbon materials such as carbon black such as ketjen black and acetylene black, and carbon fibers.
  • electrolyte salt examples include Li (C 2 F 5 SO 2 ) 2 N, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , LiCF 3 SO 3 and the like.
  • Examples of the ion conductive polymer include polyethylene oxide (PEO) and polypropylene oxide (PPO) polymers.
  • the compounding ratio of the components contained in the positive electrode active material layer and the negative electrode active material layer described later is not particularly limited.
  • the blending ratio can be adjusted by appropriately referring to known knowledge about lithium ion secondary batteries.
  • the thickness of each active material layer is not particularly limited, and conventionally known knowledge about the battery can be appropriately referred to. As an example, the thickness of each active material layer is about 2 to 100 ⁇ m.
  • the positive electrode for an electric device usually, a slurry containing a positive electrode active material is applied to the surface of a current collector, subjected to a drying treatment as necessary, and the obtained coating film is applied in the stacking direction. It is produced by pressing.
  • the positive electrode for an electric device has an increase rate of the BET specific surface area of the positive electrode active material layer before and after the pressure press at the time of production (the value before the pressure press is 100%).
  • the relative value of the increment of the value after pressure pressing is preferably less than 60%, more preferably 55% or less, and even more preferably 50% or less.
  • an electric device having a power generation element including the positive electrode described above, a negative electrode having a negative electrode active material layer formed on the surface of a negative electrode current collector, and a separator. .
  • a lithium ion secondary battery will be described as a preferred embodiment of the electric device, but is not limited to the following embodiment.
  • the same elements are denoted by the same reference numerals, and redundant description is omitted.
  • the dimensional ratios in the drawings are exaggerated for convenience of explanation, and may be different from the actual ratios.
  • FIG. 1 is a schematic cross-sectional view schematically showing a basic configuration of a non-aqueous electrolyte lithium ion secondary battery (hereinafter also simply referred to as “stacked battery”) that is not a flat type (stacked type) bipolar type
  • FIG. 3 is a schematic cross-sectional view along the line AA shown in FIG. 2 described later.
  • the stacked battery 10 of the present embodiment has a structure in which a substantially rectangular power generation element 21 in which a charge / discharge reaction actually proceeds is sealed inside a battery exterior material 29 that is an exterior body.
  • the power generation element 21 has a configuration in which a positive electrode, a separator 17, and a negative electrode are stacked.
  • the separator 17 contains a nonaqueous electrolyte (for example, a liquid electrolyte).
  • the positive electrode has a structure in which the positive electrode active material layers 15 are disposed on both surfaces of the positive electrode current collector 12.
  • the negative electrode has a structure in which the negative electrode active material layer 13 is disposed on both surfaces of the negative electrode current collector 11.
  • the negative electrode, the electrolyte layer, and the positive electrode are laminated in this order so that one positive electrode active material layer 15 and the negative electrode active material layer 13 adjacent thereto face each other with a separator 17 therebetween.
  • the adjacent positive electrode, electrolyte layer, and negative electrode constitute one unit cell layer 19. Therefore, it can be said that the stacked battery 10 shown in FIG. 1 has a configuration in which a plurality of single battery layers 19 are stacked and electrically connected in parallel.
  • the negative electrode active material layer 13 is arrange
  • the arrangement of the positive electrode and the negative electrode is reversed from that in FIG. 1 so that the outermost positive electrode current collector is positioned on both outermost layers of the power generation element 21, A positive electrode active material layer may be disposed.
  • the positive electrode current collector 12 and the negative electrode current collector 11 are each provided with a positive electrode current collector plate (tab) 27 and a negative electrode current collector plate (tab) 25 that are electrically connected to the respective electrodes (positive electrode and negative electrode). It has the structure led out of the battery exterior material 29 so that it may be pinched
  • the positive electrode current collector 27 and the negative electrode current collector 25 are ultrasonically welded to the positive electrode current collector 12 and the negative electrode current collector 11 of each electrode, respectively, via a positive electrode lead and a negative electrode lead (not shown) as necessary. Or resistance welding or the like.
  • FIG. 1 shows a flat battery (stacked battery) that is not a bipolar battery, but a positive electrode active material layer that is electrically coupled to one surface of the current collector and the opposite side of the current collector.
  • a bipolar battery including a bipolar electrode having a negative electrode active material layer electrically coupled to the surface.
  • one current collector also serves as a positive electrode current collector and a negative electrode current collector.
  • the negative electrode active material layer contains an active material, and other additives such as a conductive additive, a binder, an electrolyte (polymer matrix, ion conductive polymer, electrolyte, etc.), and a lithium salt to enhance ionic conductivity as necessary.
  • a conductive additive such as a conductive additive, a binder, an electrolyte (polymer matrix, ion conductive polymer, electrolyte, etc.), and a lithium salt to enhance ionic conductivity as necessary.
  • An agent is further included.
  • Other additives such as conductive assistants, binders, electrolytes (polymer matrix, ion conductive polymers, electrolytes, etc.) and lithium salts for improving ion conductivity are those described in the above positive electrode active material layer column. It is the same.
  • the negative electrode active material layer preferably contains at least an aqueous binder.
  • a water-based binder has a high binding power.
  • it is easy to procure water as a raw material and since steam is generated at the time of drying, the capital investment in the production line can be greatly suppressed, and the environmental load can be reduced. There is.
  • the water-based binder refers to a binder using water as a solvent or a dispersion medium, and specifically includes a thermoplastic resin, a polymer having rubber elasticity, a water-soluble polymer, or a mixture thereof.
  • the binder using water as a dispersion medium refers to a polymer that includes all expressed as latex or emulsion and is emulsified or suspended in water.
  • kind a polymer latex that is emulsion-polymerized in a system that self-emulsifies.
  • water-based binders include styrene polymers (styrene-butadiene rubber, styrene-vinyl acetate copolymer, styrene-acrylic copolymer, etc.), acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, ) Acrylic polymers (polyethyl acrylate, polyethyl methacrylate, polypropyl acrylate, polymethyl methacrylate (methyl methacrylate rubber), polypropyl methacrylate, polyisopropyl acrylate, polyisopropyl methacrylate, polybutyl acrylate, polybutyl methacrylate, polyhexyl acrylate , Polyhexyl methacrylate, polyethylhexyl acrylate, polyethylhexyl methacrylate, polylauryl acrylate, polylauryl meta Acrylate, etc.), polytyren
  • the aqueous binder may contain at least one rubber binder selected from the group consisting of styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, and methyl methacrylate rubber from the viewpoint of binding properties. preferable. Furthermore, it is preferable that the water-based binder contains styrene-butadiene rubber because of good binding properties.
  • Water-soluble polymers suitable for use in combination with styrene-butadiene rubber include polyvinyl alcohol and modified products thereof, starch and modified products thereof, cellulose derivatives (such as carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and salts thereof), polyvinyl Examples include pyrrolidone, polyacrylic acid (salt), or polyethylene glycol. Among them, it is preferable to combine styrene-butadiene rubber and carboxymethyl cellulose (salt) as a binder.
  • the content of the aqueous binder is preferably 80 to 100% by weight, preferably 90 to 100% by weight, and preferably 100% by weight.
  • the negative electrode active material examples include carbon materials such as graphite (graphite), soft carbon, and hard carbon, lithium-transition metal composite oxides (for example, Li 4 Ti 5 O 12 ), metal materials, lithium alloy negative electrode materials, and the like. Is mentioned. In some cases, two or more negative electrode active materials may be used in combination. Preferably, from the viewpoint of capacity and output characteristics, a carbon material or a lithium-transition metal composite oxide is used as the negative electrode active material. Of course, negative electrode active materials other than those described above may be used.
  • the average particle diameter of the negative electrode active material is not particularly limited, but is preferably 1 to 100 ⁇ m, more preferably 1 to 20 ⁇ m from the viewpoint of increasing the output.
  • the separator has a function of holding an electrolyte and ensuring lithium ion conductivity between the positive electrode and the negative electrode, and a function as a partition wall between the positive electrode and the negative electrode.
  • separator examples include a separator made of a porous sheet made of a polymer or fiber that absorbs and holds the electrolyte and a nonwoven fabric separator.
  • a microporous (microporous film) can be used as the separator of the porous sheet made of polymer or fiber.
  • the porous sheet made of the polymer or fiber include polyolefins such as polyethylene (PE) and polypropylene (PP); a laminate in which a plurality of these are laminated (for example, three layers of PP / PE / PP) And a microporous (microporous membrane) separator made of a hydrocarbon resin such as polyimide, aramid, polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), glass fiber, and the like.
  • PE polyethylene
  • PP polypropylene
  • a microporous (microporous membrane) separator made of a hydrocarbon resin such as polyimide, aramid, polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), glass fiber, and the like.
  • the thickness of the microporous (microporous membrane) separator cannot be uniquely defined because it varies depending on the intended use. For example, in applications such as secondary batteries for driving motors such as electric vehicles (EV), hybrid electric vehicles (HEV), and fuel cell vehicles (FCV), it is 4 to 60 ⁇ m in a single layer or multiple layers. Is desirable.
  • the fine pore diameter of the microporous (microporous membrane) separator is desirably 1 ⁇ m or less (usually a pore diameter of about several tens of nm).
  • nonwoven fabric separator cotton, rayon, acetate, nylon, polyester; polyolefins such as PP and PE; conventionally known ones such as polyimide and aramid are used alone or in combination.
  • the bulk density of the nonwoven fabric is not particularly limited as long as sufficient battery characteristics can be obtained by the impregnated polymer gel electrolyte.
  • the thickness of the nonwoven fabric separator may be the same as that of the electrolyte layer, and is preferably 5 to 200 ⁇ m, particularly preferably 10 to 100 ⁇ m.
  • the separator includes an electrolyte.
  • the electrolyte is not particularly limited as long as it can exhibit such a function, but a liquid electrolyte or a gel polymer electrolyte is used.
  • a gel polymer electrolyte By using the gel polymer electrolyte, the distance between the electrodes is stabilized, the occurrence of polarization is suppressed, and the durability (cycle characteristics) is improved.
  • the liquid electrolyte functions as a lithium ion carrier.
  • the liquid electrolyte constituting the electrolytic solution layer has a form in which a lithium salt as a supporting salt is dissolved in an organic solvent as a plasticizer.
  • organic solvent include carbonates such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate.
  • EC ethylene carbonate
  • PC propylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • ethyl methyl carbonate ethyl methyl carbonate.
  • Li (CF 3 SO 2) 2 N Li (C 2 F 5 SO 2) 2 N, LiPF 6, LiBF 4, LiClO 4, LiAsF 6, LiTaF such 6, LiCF 3 SO 3
  • a compound that can be added to the active material layer of the electrode can be similarly employed.
  • the liquid electrolyte may further contain additives other than the components described above.
  • additives include, for example, vinylene carbonate, methyl vinylene carbonate, dimethyl vinylene carbonate, phenyl vinylene carbonate, diphenyl vinylene carbonate, ethyl vinylene carbonate, diethyl vinylene carbonate, vinyl ethylene carbonate, 1,2-divinyl ethylene.
  • the liquid electrolyte includes a cyclic sulfonic acid ester as an additive.
  • a cyclic sulfonic acid ester include 1,3-propane sultone, 1,3-propene sultone, methylenemethane disulfonic acid ester, and the like, and those described in JP 2010-219011 are also used.
  • the cyclic sulfonate ester attacks the predetermined lithium transition metal composite oxide described above to deteriorate its performance and increase the reaction resistance.
  • the liquid electrolyte contains a cyclic sulfonic acid ester as an additive (in addition, the spinel manganese positive electrode active material (LiMn 2 O 4 ) described above is used in combination with the predetermined lithium transition metal composite oxide of the present application).
  • the spinel manganese positive electrode active material (LiMn 2 O 4 ) described above is used in combination with the predetermined lithium transition metal composite oxide of the present application. The effect of suppressing the increase in the internal resistance of the battery can be further exhibited.
  • the gel polymer electrolyte has a configuration in which the above liquid electrolyte is injected into a matrix polymer (host polymer) made of an ion conductive polymer.
  • a gel polymer electrolyte as the electrolyte is superior in that the fluidity of the electrolyte is lost and the ion conductivity between the layers is easily cut off.
  • ion conductive polymer used as the matrix polymer (host polymer) examples include polyethylene oxide (PEO), polypropylene oxide (PPO), polyethylene glycol (PEG), polyacrylonitrile (PAN), polyvinylidene fluoride-hexafluoropropylene ( PVdF-HEP), poly (methyl methacrylate (PMMA), and copolymers thereof.
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PEG polyethylene glycol
  • PAN polyacrylonitrile
  • PVdF-HEP polyvinylidene fluoride-hexafluoropropylene
  • PMMA methyl methacrylate
  • the matrix polymer of gel electrolyte can express excellent mechanical strength by forming a crosslinked structure.
  • thermal polymerization, ultraviolet polymerization, radiation polymerization, electron beam polymerization, etc. are performed on a polymerizable polymer (for example, PEO or PPO) for forming a polymer electrolyte using an appropriate polymerization initiator.
  • a polymerization treatment may be performed.
  • the separator is preferably a separator in which a heat-resistant insulating layer is laminated on a porous substrate (a separator with a heat-resistant insulating layer).
  • the heat-resistant insulating layer is a ceramic layer containing inorganic particles and a binder.
  • a highly heat-resistant separator having a melting point or a heat softening point of 150 ° C. or higher, preferably 200 ° C. or higher is used.
  • the separator is less likely to curl in the battery manufacturing process due to the effect of suppressing thermal shrinkage and high mechanical strength.
  • the inorganic particles in the heat resistant insulating layer contribute to the mechanical strength and heat shrinkage suppressing effect of the heat resistant insulating layer.
  • the material used as the inorganic particles is not particularly limited. Examples thereof include silicon, aluminum, zirconium, titanium oxides (SiO 2 , Al 2 O 3 , ZrO 2 , TiO 2 ), hydroxides and nitrides, and composites thereof. These inorganic particles may be derived from mineral resources such as boehmite, zeolite, apatite, kaolin, mullite, spinel, olivine and mica, or may be artificially produced. Moreover, only 1 type may be used individually for these inorganic particles, and 2 or more types may be used together. Of these, silica (SiO 2 ) or alumina (Al 2 O 3 ) is preferably used, and alumina (Al 2 O 3 ) is more preferably used from the viewpoint of cost.
  • the basis weight of the heat-resistant particles is not particularly limited, but is preferably 5 to 15 g / m 2 . If it is this range, sufficient ion conductivity will be acquired and it is preferable at the point which maintains heat resistant strength.
  • the binder in the heat-resistant insulating layer has a role of adhering the inorganic particles and the inorganic particles to the resin porous substrate layer. With the binder, the heat-resistant insulating layer is stably formed, and peeling between the porous substrate layer and the heat-resistant insulating layer is prevented.
  • the binder used for the heat-resistant insulating layer is not particularly limited.
  • a compound such as butadiene rubber, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl fluoride (PVF), or methyl acrylate can be used as the binder.
  • PVDF polyvinylidene fluoride
  • PTFE polytetrafluoroethylene
  • PVF polyvinyl fluoride
  • methyl acrylate methyl acrylate
  • PVDF polyvinylidene fluoride
  • these compounds only 1 type may be used independently and 2 or more types may be used together.
  • the binder content in the heat resistant insulating layer is preferably 2 to 20% by weight with respect to 100% by weight of the heat resistant insulating layer.
  • the binder content is 2% by weight or more, the peel strength between the heat-resistant insulating layer and the porous substrate layer can be increased, and the vibration resistance of the separator can be improved.
  • the binder content is 20% by weight or less, the gaps between the inorganic particles are appropriately maintained, so that sufficient lithium ion conductivity can be ensured.
  • the thermal contraction rate of the separator with a heat-resistant insulating layer is preferably 10% or less for both MD and TD after holding for 1 hour at 150 ° C. and 2 gf / cm 2 .
  • examples of the metal include aluminum, nickel, iron, stainless steel, titanium, copper, and other alloys.
  • a clad material of nickel and aluminum, a clad material of copper and aluminum, or a plating material of a combination of these metals can be preferably used.
  • covered on the metal surface may be sufficient.
  • aluminum, stainless steel, and copper are preferable from the viewpoints of electronic conductivity and battery operating potential.
  • the size of the current collector is determined according to the intended use of the battery. For example, if it is used for a large battery that requires a high energy density, a current collector having a large area is used. There is no particular limitation on the thickness of the current collector.
  • the thickness of the current collector is usually about 1 to 100 ⁇ m.
  • the material which comprises a current collector plate (25, 27) is not restrict
  • a constituent material of the current collector plate for example, metal materials such as aluminum, copper, titanium, nickel, stainless steel (SUS), and alloys thereof are preferable. From the viewpoint of light weight, corrosion resistance, and high conductivity, aluminum and copper are more preferable, and aluminum is particularly preferable.
  • the same material may be used for the positive electrode current collecting plate 27 and the negative electrode current collecting plate 25, and different materials may be used.
  • the battery outer case 29 a known metal can case can be used, and a bag-like case using a laminate film containing aluminum that can cover the power generation element can be used.
  • a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used as the laminate film, but the laminate film is not limited thereto.
  • a laminate film is desirable from the viewpoint that it is excellent in high output and cooling performance, and can be suitably used for a battery for large equipment for EV and HEV.
  • the exterior body is more preferably an aluminate laminate.
  • FIG. 2 is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of the secondary battery.
  • the flat lithium ion secondary battery 50 has a rectangular flat shape, and a positive electrode tab 58 and a negative electrode tab 59 for taking out electric power are drawn out from both sides thereof.
  • the power generation element 57 is encased by the battery outer packaging material 52 of the lithium ion secondary battery 50, and the periphery thereof is heat-sealed. The power generation element 57 is sealed with the positive electrode tab 58 and the negative electrode tab 59 pulled out to the outside.
  • the power generation element 57 corresponds to the power generation element 21 of the lithium ion secondary battery 10 shown in FIG. 1 described above.
  • the power generation element 57 is formed by laminating a plurality of single battery layers (single cells) 19 including a positive electrode (positive electrode active material layer) 15, an electrolyte layer 17, and a negative electrode (negative electrode active material layer) 13.
  • the lithium ion secondary battery is not limited to a stacked flat shape.
  • the wound lithium ion secondary battery may have a cylindrical shape, or may have a shape that is a flattened rectangular shape by deforming such a cylindrical shape.
  • a laminate film may be used for the exterior material, and the conventional cylindrical can (metal can) may be used, for example, It does not restrict
  • the power generation element is covered with an aluminum laminate film. With this configuration, weight reduction can be achieved.
  • the tabs 58 and 59 shown in FIG. 2 are not particularly limited.
  • the positive electrode tab 58 and the negative electrode tab 59 may be drawn out from the same side, or the positive electrode tab 58 and the negative electrode tab 59 may be divided into a plurality of parts and taken out from each side, as shown in FIG. It is not limited to.
  • a terminal may be formed using a cylindrical can (metal can).
  • the battery storage space is about 170L. Since auxiliary devices such as cells and charge / discharge control devices are stored in this space, the storage efficiency of a normal cell is about 50%. The efficiency of loading cells into this space is a factor that governs the cruising range of electric vehicles. If the size of the single cell is reduced, the loading efficiency is impaired, so that the cruising distance cannot be secured.
  • the battery structure in which the power generation element is covered with the exterior body is preferably large.
  • the length of the short side of the laminated cell battery is preferably 100 mm or more. Such a large battery can be used for vehicle applications.
  • the length of the short side of the laminated cell battery refers to the side having the shortest length.
  • the upper limit of the short side length is not particularly limited, but is usually 400 mm or less.
  • volume energy density and rated discharge capacity In a general electric vehicle, a travel distance (cruising range) by a single charge is 100 km. Considering such a cruising distance, the volume energy density of the battery is preferably 157 Wh / L or more, and the rated capacity is preferably 20 Wh or more.
  • the ratio of the battery area (projected area of the battery including the battery outer package) to the rated capacity is 5 cm 2 / Ah or more, and the rated capacity is 3 Ah or more.
  • the battery area per unit capacity is large, the problem of deterioration of battery characteristics (cycle characteristics) due to the collapse of the crystal structure accompanying the progress of the charge / discharge cycle is more likely to become apparent.
  • the nonaqueous electrolyte secondary battery according to the present embodiment is a battery having a large size as described above from the viewpoint that the merit due to the expression of the effects of the present invention is greater.
  • the aspect ratio of the rectangular electrode is preferably 1 to 3, and more preferably 1 to 2.
  • the electrode aspect ratio is defined as the aspect ratio of the rectangular positive electrode active material layer.
  • the assembled battery is configured by connecting a plurality of batteries. Specifically, at least two or more are used, and are configured by serialization, parallelization, or both. Capacitance and voltage can be freely adjusted by paralleling in series.
  • a small assembled battery that can be attached and detached by connecting a plurality of batteries in series or in parallel. Then, a plurality of small assembled batteries that can be attached and detached are connected in series or in parallel to provide a large capacity and large capacity suitable for vehicle drive power supplies and auxiliary power supplies that require high volume energy density and high volume output density.
  • An assembled battery having an output can also be formed. How many batteries are connected to make an assembled battery, and how many small assembled batteries are stacked to make a large-capacity assembled battery depends on the battery capacity of the mounted vehicle (electric vehicle) It may be determined according to the output.
  • the nonaqueous electrolyte secondary battery of the present invention maintains a discharge capacity even when used for a long period of time, and has good cycle characteristics. Furthermore, the volume energy density is high. Vehicle applications such as electric vehicles, hybrid electric vehicles, fuel cell vehicles, and hybrid fuel cell vehicles require higher capacity, larger size, and longer life than electric and portable electronic devices. . Therefore, the nonaqueous electrolyte secondary battery can be suitably used as a vehicle power source, for example, a vehicle driving power source or an auxiliary power source.
  • a battery or an assembled battery formed by combining a plurality of these batteries can be mounted on the vehicle.
  • a plug-in hybrid electric vehicle having a long EV mileage or an electric vehicle having a long charge mileage can be formed by mounting such a battery.
  • a car a hybrid car, a fuel cell car, an electric car (four-wheeled vehicles (passenger cars, trucks, buses, commercial vehicles, light cars, etc.) This is because it can be used for motorcycles (including motorcycles) and tricycles) to provide a long-life and highly reliable automobile.
  • the application is not limited to automobiles.
  • it can be applied to various power sources for moving vehicles such as other vehicles, for example, trains, and power sources for mounting such as uninterruptible power supplies. It is also possible to use as.
  • NMC composite oxide (LiNi 0.80 Mn 0.10 Co 0.10 O 2) was prepared. At this time, the firing temperature and firing time during firing (temporary firing and main firing) were adjusted so that the crystallite size of the obtained NMC composite oxide was 900 mm. The crystallite diameter was measured by the Rietveld method in which the crystallite diameter was calculated from the diffraction peak intensity obtained by powder X-ray diffraction measurement.
  • the half width from the peak of the (003) plane was measured by powder X-ray diffraction measurement and found to be 0.11.
  • an X-ray diffractometer manufactured by Rigaku
  • Analysis was performed using Fundamental ⁇ Parameter.
  • analysis was performed using analysis software Topas Version 3.
  • the crystal structure is attributed to the hexagonal crystal in the space group R-3m, with Li at the 3a site, M at the 3b site (Ni, Co, Mn, Al, etc.), excess Li content x, and O at the 6c site.
  • the crystallite diameter (Gauss) and crystal distortion (Gauss) were calculated
  • required on the assumption that it was occupied. It is assumed that the isotropic temperature factor (Beq) is 1, and refinement is performed to Rwp ⁇ 10.0 and GOF ⁇ 1.3. As a refinement procedure, Beq 1 is fixed, and each variable does not change in a state where the z coordinate of oxygen, the seat occupancy, the crystallite diameter (Gauss), and the bond distance between each site are variables. Repeated until.
  • the BET specific surface areas of the positive electrode active material layer before and after compression molding with a roll press machine are 0.93 cm 2 / g and 1.50 cm 2 / g, respectively, and the BET ratio of the positive electrode active material layer before and after compression molding
  • the increase rate of the surface area was 59%.
  • AMS8000 type fully automatic powder specific surface area measuring device manufactured by Okura Riken is used to measure the BET specific surface area. Nitrogen is used as the adsorbed gas and helium is used as the carrier gas. Went.
  • the powder sample is heated and deaerated with a mixed gas at a temperature of 150 ° C., then cooled to liquid nitrogen temperature to adsorb the nitrogen / helium mixed gas, and then heated to room temperature with water.
  • the adsorbed nitrogen gas was desorbed, the amount was detected by a heat conduction detector, and the specific surface area of the sample was calculated from this.
  • This negative electrode active material slurry was applied to a copper foil serving as a negative electrode current collector, dried at 120 ° C. for 3 minutes, and then compression molded with a roll press to form a negative electrode active material layer (length 225 mm, width 205 mm, thickness 60 ⁇ m). Negative electrodes having both sides of the negative electrode current collector were prepared. At this time, the basis weight of the amount of the negative electrode active material was 9 mg / cm 2 and the density was 1.5 g / cm 3 .
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • Example 2 (1) In the preparation of the NMC composite oxide, the prepared NMC composite oxide (LiNi 0.80 Mn 0.10 Co 0.10 O 2 ) is fired so as to have a crystallite size of 950 ⁇ Except for adjusting the firing temperature and firing time during firing), an NMC composite oxide, a positive electrode containing this as a positive electrode active material, and a laminate battery were produced in the same manner as in Example 1 described above.
  • Example 1 (1) In the preparation of the NMC composite oxide, the prepared NMC composite oxide (LiNi 0.80 Mn 0.10 Co 0.10 O 2 ) is fired so as to have a crystallite size of 860 ⁇ The NMC composite oxide was prepared by the same method as in Example 1 except that the firing temperature and firing time were adjusted and no cyclic sulfonic acid ester was added as an additive to the electrolyte. A positive electrode including a positive electrode active material and a laminate battery were produced.
  • the rate of increase in the internal resistance of the battery is suppressed to a low value as compared with Comparative Examples 1 and 2.
  • the positive electrode according to the present invention is used in an electric device, thereby preventing a decrease in capacity accompanying the progress of a charge / discharge cycle and providing an electric device such as a lithium ion secondary battery excellent in cycle durability. It becomes possible to do.

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Abstract

Le problème décrit par la présente invention est de fournir un moyen par lequel une résistance interne de batterie peut être réduite et la réduction de capacité de la batterie accompagnant la progression d'un cycle de charge/décharge peut être inhibée (c.-à-d. une durabilité de cycle peut être améliorée), dans un dispositif électrique tel qu'une batterie secondaire au lithium-ion. La solution selon l'invention concerne une électrode positive destinée à un dispositif électrique, obtenue par la formation d'une couche de matériau actif d'électrode positive sur la surface d'un collecteur d'électrode positive. Dans la couche de matériau actif d'électrode positive, un oxyde composite de lithium et de métal de transition, qui comprend du manganèse et du nickel et qui présente une structure cristalline multicouches susceptible d'absorber et de libérer des ions lithium, est incorporé en tant que matériau actif d'électrode positive. La taille des cristallites de l'oxyde composite de lithium et de métal de transition est au moins de 900 Å.
PCT/JP2015/061284 2014-04-11 2015-04-10 Électrode positive destinée à un dispositif électrique et dispositif électrique utilisant celle-ci Ceased WO2015156400A1 (fr)

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JP7183814B2 (ja) * 2019-01-24 2022-12-06 住友金属鉱山株式会社 ニッケルマンガンコバルト含有複合水酸化物およびその製造方法、リチウムイオン二次電池用正極活物質およびその製造方法、並びに、リチウムイオン二次電池
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WO2017082083A1 (fr) * 2015-11-10 2017-05-18 Ｎｅｃエナジーデバイス株式会社 Batterie rechargeable lithium-ion et son procédé de fabrication
WO2017169417A1 (fr) * 2016-03-31 2017-10-05 オートモーティブエナジーサプライ株式会社 Batterie rechargeable au lithium-ion
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JP2023512077A (ja) * 2020-01-31 2023-03-23 アセンド・パフォーマンス・マテリアルズ・オペレーションズ・リミテッド・ライアビリティ・カンパニー 電解液
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