WO2014142281A1 - Électrode positive pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux l'utilisant - Google Patents

Électrode positive pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux l'utilisant Download PDF

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WO2014142281A1
WO2014142281A1 PCT/JP2014/056796 JP2014056796W WO2014142281A1 WO 2014142281 A1 WO2014142281 A1 WO 2014142281A1 JP 2014056796 W JP2014056796 W JP 2014056796W WO 2014142281 A1 WO2014142281 A1 WO 2014142281A1
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positive electrode
active material
secondary battery
composite oxide
electrolyte secondary
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PCT/JP2014/056796
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English (en)
Japanese (ja)
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健児 小原
新田　芳明
聡 市川
狩野　巌大郎
学 西嶋
嶋村　修
文洋 川村
康介 萩山
井深　重夫
加世田　学
真規 末永
珠生 平井
高谷　真弘
邦治 野元
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日産自動車株式会社
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Priority to JP2015505582A priority Critical patent/JP6070823B2/ja
Publication of WO2014142281A1 publication Critical patent/WO2014142281A1/fr

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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • H01M4/50—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
    • 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 a non-aqueous electrolyte secondary battery and a non-aqueous electrolyte secondary battery 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, which is a layered composite oxide, can obtain a high voltage of 4V and has a high energy density.
  • cobalt which is a raw material
  • there is anxiety in terms of supply of raw materials considering the possibility that demand will increase significantly in the future.
  • the price of cobalt raw materials may rise. Therefore, a composite oxide having a low cobalt content is desired.
  • a spinel-based lithium manganese composite oxide (LiMn 2 O 4 ; also referred to as “LMO” in the present specification) has a spinel structure and functions as a 4V-class positive electrode material with a composition with ⁇ -MnO 2 . Since the spinel-type lithium manganese composite oxide has a three-dimensional host structure different from the layered structure such as that of LiCoO 2 or the like, most of the theoretical capacity can be used and is expected to have excellent cycle characteristics. .
  • lithium ion secondary batteries using spinel-based lithium manganese composite oxide as the positive electrode material cannot avoid the capacity degradation that gradually decreases in capacity due to repeated charge and discharge. There was a big problem left.
  • the present invention provides a large-capacity, large-area non-aqueous electrolyte secondary battery containing a spinel-based lithium manganese composite oxide as a positive electrode active material, from the composite oxide resulting from an increase in Joule heat during charge / discharge.
  • An object of the present invention is to provide means capable of suppressing elution of Mn and improving cycle characteristics.
  • the present inventors have accumulated earnest research.
  • the lithium nickel composite oxide is used in combination with the spinel lithium manganese composite oxide as the positive electrode active material, and the ratio of the discharge depth (DOD) corresponding to the positive electrode potential in a specific range is set to the total discharge depth (total).
  • DOD discharge depth
  • total total discharge depth
  • 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 non-aqueous water has a rated capacity of 3 Ah or more.
  • a positive electrode for a non-aqueous electrolyte secondary battery used for an electrolyte secondary battery is provided. This positive electrode has a positive electrode current collector and a positive electrode active material layer formed on the surface of the positive electrode current collector and containing a spinel-based lithium manganese composite oxide and a lithium-nickel-based composite oxide.
  • the depth of discharge (DOD) corresponding to the positive electrode potential (versus lithium oxidation-reduction potential) in the range of 3.93 to 4.03 V is the total depth of discharge (total DOD) of 100 corresponding to the range of the cell voltage of 3 to 4.25 V. It is characterized in that it is 25% or less with respect to%.
  • FIG. 1 is a schematic cross-sectional view showing a basic configuration of a non-aqueous electrolyte lithium ion secondary battery that is not a flat (stacked) bipolar type, which is an embodiment of a nonaqueous electrolyte lithium ion secondary battery.
  • the spinel lithium manganese composite oxide is used as the positive electrode active material (curve a shown in FIG. 2)
  • the mixture of the spinel lithium manganese composite oxide and the lithium nickel composite oxide (mixing ratio) as the positive electrode active material 70:30 (% by weight)) (curve b shown in FIG. 2) and a graph showing a discharge curve for each (graphite is used as the negative electrode active material).
  • FIG. 3 is an enlarged graph showing a region (region X shown in FIG.
  • 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.
  • a positive electrode for a nonaqueous electrolyte secondary battery used for a secondary battery comprising a positive electrode current collector and a surface of the positive electrode current collector, comprising a spinel-based lithium manganese composite oxide and a lithium-nickel-based composite oxide
  • a positive electrode active material layer containing a positive electrode active material, and a discharge depth (DOD) corresponding to a positive electrode potential (with respect to lithium oxidation-reduction potential) of 3.93 to 4.03 V is a cell voltage of 3 to 4.25 V
  • a positive electrode for a nonaqueous electrolyte secondary battery that is 25% or less with respect to 100% of the total depth of discharge (total DOD) corresponding to the range.
  • the discharge profile is changed by using a lithium nickel composite oxide together.
  • the discharge profile in the region corresponding to the positive electrode potential range (Mn elution region) where Mn elution from the spinel-type lithium manganese composite oxide is likely to occur changes, and the accumulated time that passes through this Mn elution region during charging and discharging is reduced. can do.
  • Mn elution region the positive electrode potential range
  • nonaqueous electrolyte lithium ion secondary battery will be described as a preferred embodiment of a nonaqueous electrolyte secondary battery to which the positive electrode according to the present embodiment is applied, but is not limited only 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 (stacked) bipolar type.
  • 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 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 plate 27 and the negative electrode current collector plate 25 are ultrasonically welded to the positive electrode current collector 11 and the negative electrode current collector 12 of each electrode via a positive electrode lead and a negative electrode lead (not shown), respectively, 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 positive electrode has a positive electrode current collector and a positive electrode active material layer formed on the surface of the positive electrode current collector.
  • a metal is preferably used.
  • 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 positive electrode active material layer includes a positive electrode active material.
  • the positive electrode active material essentially includes a spinel-based lithium manganese composite oxide and a lithium-nickel-based composite oxide.
  • the ratio of the total amount of spinel-based lithium manganese composite oxide and lithium-nickel-based composite oxide in the total amount of 100% by weight of the positive electrode active material contained in the positive electrode active material layer is preferably 50% by weight or more, and more It is preferably 70% by weight or more, more preferably 85% by weight or more, still more preferably 90% by weight or more, particularly preferably 95% by weight or more, and most preferably 100% by weight.
  • Spinel-based lithium manganese composite oxide is a composite oxide that typically has a composition of LiMn 2 O 4 and has a spinel structure and essentially contains lithium and manganese.
  • conventionally known knowledge such as JP-A-2000-77071 can be referred to as appropriate.
  • Spinel-based lithium manganese composite oxide has a structure of secondary particles formed by agglomerating primary particles.
  • the average particle diameter (average secondary particle diameter) of the secondary particles is preferably 5 to 50 ⁇ m, more preferably 7 to 20 ⁇ m.
  • the average secondary particle diameter is measured by a laser diffraction method.
  • lithium nickel complex oxide is not specifically limited as long as it is a complex oxide containing lithium and nickel.
  • a typical example of a composite oxide containing lithium and nickel is lithium nickel composite oxide (LiNiO 2 ).
  • a composite oxide in which some of the nickel atoms of the lithium nickel composite oxide are substituted with other metal atoms is more preferable.
  • NMC composite lithium-nickel-manganese-cobalt composite oxide
  • oxide (Also referred to as “oxide”) has a layered crystal structure in which a lithium atomic layer and a transition metal (Mn, Ni, and Co are arranged in order) are alternately stacked via an oxygen atomic layer.
  • a lithium atomic layer Li atomic layer
  • a transition metal Mn, Ni, and Co are arranged in order
  • One Li atom is contained per atom, and the amount of Li that can be taken out is twice that of the spinel-type lithium manganese oxide, that is, the supply capacity is doubled, so that a high capacity can be obtained.
  • LiNiO 2 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 Co
  • d represents the atomic ratio of Mn
  • 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 nickel composite oxide also has a secondary particle structure in which primary particles are aggregated.
  • the average primary particle size (average primary particle size) is preferably 0.9 ⁇ m or less, more preferably 0.20 to 0.6 ⁇ m, and even more preferably 0.25 to 0.5 ⁇ m.
  • the average particle diameter of the secondary particles (average secondary particle diameter) is preferably 5 to 20 ⁇ m, more preferably 5 to 15 ⁇ m.
  • the value of these ratios (average secondary particle size / average primary particle size) is preferably greater than 11, more preferably 15 to 50, and even more preferably 25 to 40.
  • the primary particles constituting the lithium nickel composite oxide usually have a hexagonal crystal structure having a layered structure, but the size of the crystallite is correlated with the size of the average primary particle size.
  • 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.
  • crystallite diameter Preferably it is 1 micrometer or less, More preferably, it is 0.55 micrometer or less, More preferably, it is 0.4 micrometer or less.
  • the value of the crystallite diameter in the positive electrode active material particles is measured by the Rietveld method in which the crystallite diameter is calculated from the diffraction peak intensity obtained by powder X-ray diffraction measurement.
  • the tap density of the lithium nickel composite oxide is preferably 2.3 g / cm 3 , more preferably 2.4 to 2.9 g / cm 3 .
  • the BET specific surface area of the lithium nickel composite oxide is preferably 0.1 to 1.0 m 2 / g, more preferably 0.3 to 1.0 m 2 / g, and particularly preferably 0.00. 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 diffraction peak intensity ratio ((003) / (104)) is the diffraction peak on the (104) plane and the diffraction peak on the (003) plane obtained by powder X-ray diffraction measurement. It is preferably 1.28 or more, more preferably 1.35 to 2.1.
  • the diffraction peak integrated intensity ratio ((003) / (104)) is preferably 1.08 or more, more preferably 1.10 to 1.45.
  • Ni 3+ is easily reduced to Ni 2+, and because substantially equal to the Ni 2+ ion radius (0.83 ⁇ ) is Li + ion radius (0.90 ⁇ ), Ni to Li + defect occurring during active material synthesized 2+ tends to be mixed.
  • Ni 2+ is mixed into the Li + site, a locally electrochemically inactive structure is formed and Li + diffusion is prevented. For this reason, when an active material with low crystallinity is used. Battery charge / discharge capacity may decrease and durability may decrease.
  • the above definition is used as an index of the crystallinity.
  • the ratio of the intensity of diffraction peaks of the (003) plane and the (104) plane and the ratio of the integrated intensity of the diffraction peaks by crystal structure analysis using X-ray diffraction. was used.
  • these parameters satisfy the above-mentioned rules, defects in the crystal are reduced, and a decrease in battery charge / discharge capacity and a decrease in durability can be suppressed.
  • Such crystallinity parameters can be controlled by the raw material, composition, firing conditions, and the like.
  • the lithium nickel composite oxide such as NMC composite oxide can be prepared by selecting various known methods such as coprecipitation method and spray drying method.
  • the coprecipitation method is preferably used because the complex oxide according to this embodiment is easy to prepare.
  • 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 (D50 (A)) 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 factors for controlling the average primary particle size and crystallite size are particularly important as the firing temperature and firing time during firing (temporary firing and main firing in the case of two stages). By adjusting based on the following tendency, the average primary particle diameter and crystallite diameter can be controlled. That is, when the firing time is lengthened, the average primary particle diameter and crystallite diameter increase. Further, when the firing temperature is increased, the average primary particle size and 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 lithium nickel composite oxide can be produced by appropriately adjusting the reaction conditions such as pH of the reaction solution, reaction temperature, reaction concentration, addition rate, and stirring time.
  • One of the characteristics of the positive electrode for a non-aqueous electrolyte secondary battery according to this embodiment is that the discharge depth (DOD) corresponding to a positive electrode potential (with respect to lithium redox potential) of 3.93 to 4.03 V has a cell voltage of 3
  • the total discharge depth (total DOD) corresponding to the range of ⁇ 4.25 V is 25% or less with respect to 100%.
  • FIG. 2 shows a case where only a spinel lithium manganese composite oxide is used as the positive electrode active material (curve a shown in FIG.
  • FIG. 3 is an enlarged graph showing a region (region X shown in FIG. 2) where the depth of discharge (DOD) is 40 to 90% in the discharge curve shown in FIG.
  • the curve b has a steeper slope when passing through the region corresponding to the cell voltage of 3.85 to 3.95 V than the curve a.
  • the cell voltage of 3.85 to 3.95 V corresponds to the positive electrode potential (vs. lithium oxidation-reduction potential) of 3.93 to 4.03 V.
  • Mn elution is likely to occur (see the graph and table shown in FIG. 4; quoted from Journal of Power Sources, 136 (2004), pp. 115-121).
  • the curve a and the curve b have different slopes of the discharge curve, so that the cell voltages corresponding to the positive electrode potential (versus lithium oxidation-reduction potential) in the range of 3.93 to 4.03 V are 3.85 to 3.3.
  • the DOD corresponding to the range of 95V is reduced to 25% for curve b, compared with 33% for curve a, based on 100% total DOD (corresponding to cell voltage 3.0 to 4.25V). ing.
  • the present inventors have surprisingly found that when a lithium nickel composite oxide is used in combination with a spinel lithium manganese composite oxide, a decrease in charge / discharge cycle characteristics is remarkably suppressed. . And in the battery which concerns on such this form, it confirmed that the integration time which passes Mn elution area at the time of charging / discharging was reduced, and came to complete this invention.
  • the discharge depth (DOD) corresponding to the positive electrode potential (versus lithium redox potential) in the range of 3.93 to 4.03 V is Two types of positive electrodes essential to the positive electrode active material layer may be used as long as the total depth of discharge (total DOD) corresponding to the voltage range of 3 to 4.25 V is 100% or less.
  • total DOD total depth of discharge
  • FIG. 5 is a graph comparing the reduction effect of the Mn elution region when two different types of lithium nickel composite oxides are used in combination with the spinel lithium manganese composite oxide. As shown in FIG.
  • the positive electrode according to the present embodiment as a preferred embodiment of the mixing ratio of the two types of positive electrode active materials included in the positive electrode active material layer, inclusion in the positive electrode active material layer of spinel-based lithium manganese composite oxide Nickel when the ratio is A [wt%], the content ratio of the lithium nickel composite oxide in the positive electrode active material layer is B [wt%], and the valence of lithium atoms in the lithium nickel composite oxide is 1.
  • the valence of an atom is x, the following formula 1:
  • the value of B ⁇ x / (A + B) is more preferably 0.24 or more, and further preferably 0.35 or more.
  • the positive electrode active material layer is used to increase the conductivity, as necessary, a conductive additive, a binder, an electrolyte (polymer matrix, ion conductive polymer, electrolyte, etc.), and ion conductivity. It further includes other additives such as lithium salts.
  • a material that can function as an active material in the positive electrode active material layer and the negative electrode active material layer described later 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 auxiliary agent include carbon materials such as carbon black such as ketjen black and acetylene black, graphite, and carbon fiber.
  • 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 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 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. For the same reason, in the non-aqueous electrolyte secondary battery according to this embodiment, the negative electrode active material preferably includes graphite (graphite), and the negative electrode active material preferably includes graphite as a main component.
  • 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.
  • two or more negative electrode active materials may be used in combination.
  • the negative electrode active material is mainly composed of graphite” means that the proportion of graphite in the negative electrode active material is 50% by weight or more.
  • the proportion of graphite in the negative electrode active material is more preferably 70% by weight or more, still more preferably 85% by weight or more, still more preferably 90% by weight or more, and particularly preferably 95% by weight or more. And most preferably 100% by weight.
  • the cell voltage is determined as the difference between the potential difference of the positive electrode active material and the potential difference of the positive electrode active material.
  • a negative electrode active material other than graphite the cell voltage may be in a range different from the examples described later. Nevertheless, as described above, a predetermined positive electrode potential of 3.93 to 4.03 V is used.
  • the range of (redox potential against lithium) is a range in which Mn elution is particularly noticeable
  • the ratio of the DOD corresponding to this range to the total DOD is set to a value equal to or less than the predetermined upper limit value.
  • 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 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 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 carbonate.
  • vinylene carbonate, methyl vinylene carbonate, and vinyl ethylene carbonate are preferable, and vinylene carbonate and vinyl ethylene carbonate are more preferable.
  • These cyclic carbonates may be used alone or in combination of two or more.
  • 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 a 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 .
  • 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. 6 is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of the secondary battery.
  • a flat laminated battery having a structure in which the power generation element is enclosed in a battery outer package made of a laminate film containing aluminum.
  • 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 composed of 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. 6 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 nonaqueous electrolyte secondary battery according to this embodiment is a flat laminated battery, and the ratio of the battery area to the rated capacity (projected area of the battery including the battery outer package) is 5 cm 2 / It is Ah or more and the rated capacity is 3 Ah or more.
  • 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 (1) LiNi 0.80 Mn 0.10 Co 0.10 O 2 ; hereinafter also referred to as “NMC composite oxide (1)”
  • the average secondary particle diameter of the obtained NMC composite oxide (1) was 10 ⁇ m.
  • NMC composite oxide (2) LiNi 0.50 Mn 0.30 Co 0.20 O having a molar ratio of nickel, manganese, and cobalt of 50:30:20 is used. 2 ; hereinafter, also referred to as “NMC composite oxide (2)”).
  • NMC composite oxide (2) the average secondary particle diameter of the obtained NMC composite oxide (2) was 10 ⁇ m.
  • a positive electrode active material layer having a rectangular planar shape was produced by compression molding with a roll press. Similarly, a positive electrode active material layer was formed on the back surface to produce a positive electrode in which a positive electrode active material layer was formed on both surfaces of a positive electrode current collector (aluminum foil). In addition, the single-sided coating amount of the positive electrode active material layer was 17 mg / cm 2 (excluding the foil). In this way, 11 types of positive electrodes having different compositions of the positive electrode active material were produced as shown in Table 1 below (numbers are% by weight).
  • each positive electrode was set to one of ⁇ 1 to ⁇ 3 described in Table 2 below.
  • L1 and L2 shown in Table 2 are the vertical and horizontal lengths of the planar rectangular shape of the positive electrode active material layer (L1 ⁇ L2), and D is the area per electrode.
  • a negative electrode active material layer was formed on the back surface to prepare a negative electrode in which a negative electrode active material layer was formed on both sides of a negative electrode current collector (copper foil).
  • the coating amount of the negative electrode active material layer was adjusted so that the A / C ratio was 1.20 with the positive electrode facing when the test cell described later was prepared (the negative electrode active material
  • the single-side coating amount of the material layer was 5.2 to 8.6 mg / cm 2 (excluding the foil)).
  • three types of negative electrodes having different compositions of the negative electrode active material layer were produced as shown in Table 3 below (numbers are% by weight).
  • test cell (I) The positive electrode produced in the above (3) and the negative electrode produced in the above (4) are selected as shown in Table 4 below, the electrode area is selected from ⁇ 1 or ⁇ 2, and the separator (thickness 25 ⁇ m) , Celgard # 2500 (manufactured by Polypore Co., Ltd.) were alternately stacked (positive electrode 3 layers, negative electrode 4 layers) to produce a power generation element.
  • the obtained power generation element was placed in a bag made of an aluminum laminate sheet as an exterior, and an electrolytic solution was injected.
  • an additive was added to 100% by weight of a solution obtained by dissolving 1.0M LiPF 6 in a 3: 7 (EC: DEC volume ratio) mixed solvent of ethylene carbonate (EC) and diethyl carbonate (DEC). What added 1 mass% of vinylene carbonate which was was used.
  • the injection amount of the electrolytic solution was an amount that is 1.40 times the total pore volume (calculated by calculation) of the positive electrode active material layer, the negative electrode active material layer, and the separator.
  • the opening of the aluminum laminate sheet bag was sealed so that the current extraction tabs connected to both electrodes were led out, and a test cell that was a laminated lithium ion secondary battery was completed. .
  • Table 4 shows the rated capacity (cell capacity) (Ah) and the ratio of the battery area to the rated capacity (capacity area ratio) (cm 2 / Ah) of each test cell obtained.
  • the positive electrode prepared in the above (3) and the negative electrode prepared in the above (4) are selected as shown in Table 4 below, and the electrode area is set as ⁇ 3, and the layers are laminated through the separator in the same manner as described above. Then, after attaching the current take-out tab, it was wound up and sealed in an outer can, and the electrolyte was injected and sealed.
  • Table 4 below shows the rated capacity (cell capacity) (Ah) and the ratio of the battery area to the rated capacity (capacity area ratio) (cm 2 / Ah) of each test cell obtained.
  • the rated capacity of the battery was determined as follows.
  • the rated capacity of the test battery is left to stand for about 10 hours after injecting the electrolytic solution, and the initial charge is performed. Thereafter, the temperature is measured by the following procedures 1 to 5 at a temperature of 25 ° C. and a voltage range of 3.0 V to 4.15 V.
  • Procedure 1 After reaching 4.15V by constant current charging at 0.2C, pause for 5 minutes.
  • Procedure 2 After Procedure 1, charge for 1.5 hours with constant voltage charging and rest for 5 minutes.
  • Procedure 3 After reaching 3.0 V by constant current discharge of 0.2 C, discharge at constant voltage discharge for 2 hours, and then rest for 10 seconds.
  • Procedure 4 After reaching 4.1 V by constant current charging at 0.2 C, charge for 2.5 hours by constant voltage charging, and then rest for 10 seconds.
  • Procedure 5 After reaching 3.0V by constant current discharge of 0.2 C, discharge at constant voltage discharge for 2 hours, and then stop for 10 seconds.
  • the discharge capacity (CCCV discharge capacity) in the discharge from the constant current discharge to the constant voltage discharge in the procedure 5 is defined as the rated capacity.
  • the depth of discharge [%] at .95 V the depth of discharge [%] at a cell voltage of 3.85 V was determined, and the ratio of the obtained depth of discharge depth to the total discharge depth (total DOD) of 100% was calculated.
  • the results are shown in Table 4 below.
  • test cell (II) The separator (thickness 25 ⁇ m, Celgard # 2500, manufactured by Polypore) with the positive electrode (C11) in which the excellent effect was confirmed in (6) and the negative electrode prepared in (4) above, with an electrode area of ⁇ 2.
  • a power generation element having a large number of layers was produced by alternately laminating through the layers.
  • the positive electrode 20 layer + the negative electrode 21 layer was used in Example 8
  • the positive electrode 30 layer + the negative electrode 31 layer was used in Example 9
  • the positive electrode 40 layer + the negative electrode 41 layer was used in Example 10.
  • three types of test cells flat plate (flat) laminate battery) were produced in the same manner as in (5) above.
  • Table 4 shows the rated capacity (cell capacity) (Ah) and the ratio of the battery area to the rated capacity (capacity area ratio) (cm 2 / Ah) of each test cell obtained.
  • the ratio of the discharge depth width corresponding to the cell voltage of 3.85 to 3.95 V in the discharge curve to the total discharge depth (total DOD) of 100% is calculated.
  • a cycle test was performed, and the capacity retention rate after 300 cycles was calculated. The results are shown in Table 5 below.

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Abstract

La présente invention vise à fournir un moyen pour réaliser des améliorations dans des caractéristiques de cycle et pour supprimer une dissolution de Mn à partir d'un oxyde composite comme résultat d'une augmentation de l'effet Joule durant une charge/décharge dans une batterie secondaire à électrolyte non aqueux de grande échelle à capacité élevée qui comprend un oxyde composite de spinelle-lithium-manganèse en tant que matériau actif d'électrode positive. A cet effet, l'invention concerne une électrode positive pour une batterie secondaire à électrolyte non aqueux qui est utilisée dans une batterie secondaire à électrolyte non aqueux qui possède une capacité nominale supérieure ou égale à 3 Ah et qui possède un rapport de surface de batterie (surface projetée de la batterie comprenant un boîtier de batterie) sur la capacité nominale supérieur ou égal à 5 cm2/Ah. L'électrode positive comprend un collecteur d'électrode positive et une couche de matériau actif d'électrode positive qui est formée sur le collecteur d'électrode positive et qui comprend un matériau actif d'électrode positive comprenant un oxyde composite de spinelle-lithium-manganèse et un oxyde composite de lithium-nickel. La profondeur de décharge (DOD) pour la plage de potentiel d'électrode positive (potentiel d'oxydation-réduction par rapport au lithium) de 3,93 V à 4,03 V est inférieure à 25 % d'une profondeur totale de décharge (DOD totale) de 100 % pour la plage de tension de cellule de 3 V à 4,25 V.
PCT/JP2014/056796 2013-03-15 2014-03-13 Électrode positive pour batterie secondaire à électrolyte non aqueux, et batterie secondaire à électrolyte non aqueux l'utilisant WO2014142281A1 (fr)

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Cited By (10)

* Cited by examiner, † Cited by third party
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JPWO2018155713A1 (ja) * 2017-02-27 2020-04-23 日立化成株式会社 エネルギーデバイス電極用樹脂、エネルギーデバイス電極形成用組成物、エネルギーデバイス電極及びエネルギーデバイス
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CN109428083B (zh) * 2017-08-28 2021-10-12 远景Aesc日本有限公司 锂离子二次电池用正极及锂离子二次电池
US20190067691A1 (en) * 2017-08-28 2019-02-28 Automotive Energy Supply Corporation Positive Electrode for Lithium Ion Secondary Battery, and Lithium Ion Secondary Battery
JP2020072091A (ja) * 2018-11-02 2020-05-07 三星エスディアイ株式会社Samsung SDI Co., Ltd. リチウム二次電池用正極活物質、その製造方法およびこれを含むリチウム二次電池
JP7022730B2 (ja) 2018-11-02 2022-02-18 三星エスディアイ株式会社 リチウム二次電池用正極活物質、その製造方法およびこれを含むリチウム二次電池
US11515521B2 (en) 2018-11-02 2022-11-29 Samsung Sdi Co., Ltd. Positive active material for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same
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CN113169304B (zh) * 2018-11-30 2023-09-19 株式会社村田制作所 二次电池
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WO2023050038A1 (fr) * 2021-09-28 2023-04-06 宁德新能源科技有限公司 Dispositif électrochimique et dispositif électronique

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