WO2014142280A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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Publication number
WO2014142280A1
WO2014142280A1 PCT/JP2014/056795 JP2014056795W WO2014142280A1 WO 2014142280 A1 WO2014142280 A1 WO 2014142280A1 JP 2014056795 W JP2014056795 W JP 2014056795W WO 2014142280 A1 WO2014142280 A1 WO 2014142280A1
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Prior art keywords
active material
positive electrode
electrode active
secondary battery
battery
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PCT/JP2014/056795
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English (en)
Japanese (ja)
Inventor
狩野　巌大郎
新田　芳明
聡 市川
井深　重夫
健児 小原
真規 末永
高谷　真弘
邦治 野元
珠生 平井
加世田　学
学 西嶋
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日産自動車株式会社
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Priority to JP2015505581A priority Critical patent/JP6070822B2/ja
Publication of WO2014142280A1 publication Critical patent/WO2014142280A1/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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery.
  • a nonaqueous electrolyte secondary battery generally includes a positive electrode in which a positive electrode active material or the like is applied to a current collector, and a negative electrode in which a negative electrode active material or the like is applied to a current collector. It has the structure connected through the electrolyte layer holding electrolyte gel. Then, ions such as lithium ions are occluded / released in the electrode active material, thereby causing a charge / discharge reaction of the battery.
  • 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.
  • Lithium manganese composite oxide (LiMn 2 O 4 ) has a spinel structure and functions as a 4V-class positive electrode material between the composition and ⁇ -MnO 2 . Since the spinel structure lithium manganese composite oxide has a three-dimensional host structure different from the layered structure of LiCoO 2 and the like, most of the theoretical capacity can be used, and excellent cycle characteristics are expected. Yes.
  • lithium ion secondary batteries using lithium manganese composite oxide as a positive electrode material cannot avoid capacity deterioration that gradually decreases in capacity due to repeated charge and discharge, which is great for practical use. The problem remained.
  • Japanese Patent Application Laid-Open No. 2000-77071 discloses a lithium material having a predetermined specific surface area as a positive electrode material in addition to a lithium manganese composite oxide.
  • a technique of further using a nickel-based composite oxide LiNiO 2 , Li 2 NiO 2 , LiNi 2 O 4 , Li 2 Ni 2 O 4 , LiNi 1-x MxO 2, etc. is disclosed. According to Japanese Patent Application Laid-Open No.
  • the technique related to Japanese Patent Laid-Open No. 2000-77071 does not take into account the required performance of a large battery for an electric vehicle. According to the study by the present inventors, it has been found that even if the technique proposed in the conventional consumer use is applied as it is to a large battery for an electric vehicle, sufficient battery performance is not exhibited. More specifically, a large battery for an electric vehicle requires a high output and a large capacity secondary battery. However, the secondary battery disclosed in Japanese Patent Application Laid-Open No. 2000-77071 is under a high output condition. It has been found that the resistance change with the progress of the depth of discharge is large and the amount of electricity that can be taken out decreases at the end of the discharge.
  • the present invention is assumed to be used particularly at a high output among large-sized nonaqueous electrolyte secondary batteries that can be used for driving electric vehicles and the like (internal resistance is 10 m ⁇ / Ah (SOC 50%) or less). It is an object of the present invention to provide means for suppressing a change in resistance accompanying the depth of discharge and improving discharge rate characteristics in a small battery.
  • the present inventors have accumulated earnest research.
  • the positive electrode active material including the spinel-based manganese positive electrode active material and the lithium nickel-based composite oxide
  • the above-described problem is solved by setting the mixing ratio of the lithium nickel-based composite oxide within a specific range. I found.
  • 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 non-aqueous electrolyte secondary battery. It is a perspective view showing the appearance of a flat lithium ion secondary battery which is a typical embodiment of a nonaqueous electrolyte secondary battery.
  • a positive electrode in which a positive electrode active material layer containing a positive electrode active material is formed on the surface of a positive electrode current collector, and a negative electrode active material layer containing a negative electrode active material on the surface of the negative electrode current collector are provided.
  • a power generation element including a formed negative electrode and a separator; wherein the positive electrode active material includes a spinel-based manganese positive electrode active material and a lithium nickel-based composite oxide; and the positive electrode active material is 100% by weight.
  • a non-aqueous electrolyte secondary battery is provided in which the mixing ratio of the lithium nickel-based composite oxide is 30% by weight or more and the internal resistance is 10 m ⁇ / Ah or less (SOC 50%).
  • the lithium nickel-based composite oxide sufficiently contributes to the discharge even at the end of discharge, it is possible to suppress a change in resistance associated with the depth of discharge and improve the amount of electricity that can be taken out at the end of discharge.
  • a non-aqueous electrolyte secondary battery having excellent discharge rate characteristics can be provided, particularly in a large non-aqueous electrolyte secondary battery having a small internal resistance of 10 m ⁇ / Ah (SOC 50%) or less.
  • FIG. 1 is a schematic cross-sectional view schematically showing an outline of a stacked battery as an embodiment of the battery of the present invention.
  • the flat type (stacked type) lithium ion secondary battery shown in FIG. 1 will be described in detail as an example, but the technical scope of the present invention is only such a form. Not limited to.
  • 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.
  • 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 so that they are 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 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 positive electrode according to the present invention has a configuration in which a positive electrode active material layer containing a positive electrode active material is formed on the surface of a positive electrode current collector.
  • the positive electrode current collector is made of a conductive material.
  • the conductive material is not particularly limited as long as it has conductivity, and conventionally known materials such as metals and conductive polymers can be appropriately used. Specifically, at least one selected from the group consisting of Fe, Cr, Ni, Mn, Ti, Mo, V, Nb, Al, Cu, Ag, Au, Pt and carbon, for example, two or more
  • the current collector material such as stainless steel made of the above alloy can be preferably used.
  • a Ni / Al clad material, a Cu / Al clad material, or a plating material obtained by combining these current collector materials can be preferably used.
  • the current collector may be a current collector in which the surface of a metal (excluding Al) as the current collector material is coated with Al as the other current collector material. Moreover, you may use the electrical power collector which bonded together the metal foil which is two or more said electrical power collector materials depending on the case.
  • the thickness of the positive electrode current collector is not particularly limited, but is usually 1 to 100 ⁇ m, preferably about 1 to 50 ⁇ m.
  • the weight per unit area of the positive electrode is preferably 30 mg / cm 2 or less, and preferably 25 mg / cm 2 or less, from the viewpoint of suppressing a rapid decrease in battery discharge rate characteristics. Is more preferable.
  • the lower limit of the basis weight of the electrode is not particularly defined from the viewpoint of the battery discharge rate characteristics, but is more preferably 10 mg / cm 2 or more from the viewpoint of the electrode preparation process or the battery energy density. Further, the basis weight on both surfaces of the electrode may be the same or different, but is more preferably the same.
  • the packing density of the positive electrode is 2.5 to 3.5 g / cm 3 from the viewpoint of suppressing a rapid decrease in battery discharge rate characteristics in the case of a large current. More preferably, it is set to ⁇ 3.3 g / cm 3 .
  • the positive electrode according to the present invention it is preferable to satisfy at least one of the preferable range of the basis weight and the preferable range of the packing density, and more preferable to satisfy both the preferable range of the basis weight and the preferable range of the packing density. .
  • the positive electrode active material includes a spinel manganese positive electrode active material and a lithium nickel composite oxide.
  • the spinel manganese positive electrode active material is not particularly limited, and a conventional lithium manganese composite oxide having a spinel structure is used.
  • the composition of the lithium nickel composite oxide according to the present invention is not specifically limited as long as it is composed of a composite oxide containing lithium and nickel.
  • a typical example of a composite oxide containing lithium and nickel is lithium nickel-based composite oxide (LiNiO 2 ).
  • a composite oxide in which a part of nickel atoms of a lithium nickel composite oxide is substituted with another metal atom is more preferable.
  • a preferable example is a lithium-nickel-manganese-cobalt composite oxide (hereinafter simply referred to as “NMC”). Or a lithium-nickel-cobalt-aluminum composite oxide.
  • the NMC composite oxide has a layered crystal structure in which a lithium atomic layer and a transition metal (Mn, Ni, and Co are arranged in an orderly manner) atomic layers are alternately stacked via an oxygen atomic layer.
  • a lithium atomic layer and a transition metal (Mn, Ni, and Co are arranged in an orderly manner
  • One Li atom is contained per atom, and the amount of Li that can be taken out is twice that of the spinel-based lithium manganese oxide, 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 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.
  • the lithium-nickel-based composite oxide since the theoretical discharge capacity is high, preferably the general formula (1): Li a Ni b M c Co d O 2 (
  • a represents the atomic ratio of Li
  • b represents the atomic ratio of Ni
  • c represents the atomic ratio of M
  • d represents the atomic ratio of Co.
  • 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
  • Ni nickel
  • Co cobalt
  • Mn manganese
  • Ti and the like partially replace the transition metal in the crystal lattice.
  • a part of the transition element is substituted with another metal element, and it is particularly preferable that 0 ⁇ c ⁇ 0.5 in the general formula (1). Since at least one selected from the group consisting of Mn, Al, Ti, Zr, Nb, W, P, Mg, V, Ca, Sr and Cr is dissolved, the crystal structure is stabilized. It is considered that even when charging and discharging are repeated, a decrease in battery capacity can be prevented and excellent cycle characteristics can be realized.
  • the inventors of the present application have non-uniform metal compositions of nickel, manganese, and cobalt, such as LiNi 0.5 Mn 0.3 Co 0.2 O 2. It was found that the influence of strain / cracking of the composite oxide at the time of charge / discharge is increased. 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.
  • the lithium nickel composite oxide according to the present invention 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 composite oxide of the present invention is easy to prepare.
  • nickel-manganese-cobalt composite hydroxide after producing a nickel-manganese-cobalt composite hydroxide by a coprecipitation method as in the method described in JP2011-105588A, nickel-manganese-cobalt composite hydroxide; It can be obtained by mixing and baking with a lithium compound.
  • the raw material compound of the lithium nickel composite oxide of the present invention for example, Ni compound, Co compound, Mn compound or Al compound is dissolved in an appropriate solvent such as water so as to have a desired active material composition.
  • the Ni compound, Co compound, Mn compound, and Al compound include sulfates, nitrates, carbonates, acetates, oxalates, oxides, hydroxides, and halides of the metal elements.
  • Specific examples of Ni compounds, Mn compounds, and Co compounds include, but are not limited to, nickel sulfate, cobalt sulfate, manganese sulfate, aluminum sulfate, nickel acetate, cobalt acetate, manganese acetate, and aluminum acetate.
  • Ti, Zr as a metal element that substitutes a part of the layered lithium metal composite oxide constituting the active material so that the composition of the desired active material can be obtained.
  • Nb, 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.
  • a nickel-manganese-cobalt composite hydroxide, or a nickel-cobalt-aluminum composite hydroxide is mixed with a lithium compound and fired to obtain a lithium-nickel-manganese-cobalt composite hydroxide or lithium-nickel.
  • a cobalt-aluminum composite hydroxide can be obtained.
  • the Li compound include lithium hydroxide or a hydrate thereof, lithium peroxide, lithium nitrate, and lithium carbonate.
  • the firing treatment 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, 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 700 to 1000 ° C., more preferably 650 to 750 ° C.
  • the firing time is preferably 3 to 20 hours, and 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 700 to 1000 ° C., more preferably 850 to 1100 ° C.
  • the firing time is preferably 3 to 20 hours, and more preferably 8 to 12 hours.
  • the method includes, in advance, nickel, cobalt, manganate or aluminum Method of mixing, method of adding simultaneously with nickel, cobalt, manganate or aluminumate, method of adding to reaction solution during reaction, nickel-cobalt-manganese composite hydroxide or nickel-cobalt-aluminum together with Li compound Any means such as a method of adding to the composite hydroxide 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, the stirring output, and the stirring rate.
  • the present inventors are proceeding with studies to solve the above problems in a non-aqueous electrolyte secondary battery having an internal resistance of 10 m ⁇ / Ah or less (SOC 50%), which is assumed to be used under high output conditions. It was.
  • the internal resistance of the battery is one of indexes indicating its input / output performance.
  • the internal resistance of a large secondary battery used in an automobile or the like is as small as possible within a designable range.
  • the inventors of the present invention have assumed that the non-aqueous electrolyte secondary battery targeted by the present invention is a battery whose internal resistance is 10 m ⁇ / Ah (SOC 50%) or less as a battery expected to be used under high output conditions. We decided to proceed with the investigation.
  • the inventors have found that excellent discharge rate characteristics can be obtained by setting the mixing ratio of the lithium nickel composite oxide to 100% by weight of the positive electrode active material to 30% by weight or more.
  • the positive electrode active material according to the present invention may be composed of only two types of active materials of a spinel-based manganese positive electrode active material and a lithium nickel-based composite oxide, and other positive electrode active materials as long as the effects of the present invention are not impaired. May be included.
  • the mixing ratio of the lithium nickel composite oxide with respect to 100% by weight of the positive electrode active material is 30% by weight. This means that the weight ratio of the lithium nickel composite oxide and the spinel manganese positive electrode active material is 30:70.
  • the mixing ratio of the lithium nickel composite oxide to 100% by weight of the positive electrode active material is preferably 30 to 90% by weight, more preferably 50 to 80% by weight. As described above, when the mixing ratio of the lithium nickel composite oxide is less than 30% by weight, particularly in a secondary battery having an internal resistance of 10 m ⁇ / Ah or less (SOC 50%), the lithium nickel composite is at the end of discharge. The reaction ratio of the oxide is increased, and the discharge rate characteristics are deteriorated.
  • the positive electrode active material layer of the present invention includes a positive electrode material having a core portion containing the lithium nickel composite oxide and a shell portion containing a lithium metal composite oxide different from the lithium nickel composite oxide. But you can.
  • a core-shell structure further improves the cycle characteristics of the nonaqueous electrolyte secondary battery.
  • the present inventors set a hypothesis that Ni may be deactivated in the particle surface layer portion and may not substantially contribute to charge / discharge.
  • Such a core-shell type positive electrode active material can be produced by the method described in Japanese Patent Application Laid-Open No. 2007-213866.
  • primary particles are aggregated to form secondary particles.
  • the porosity of the secondary particles is preferably 2 to less than 10% from the viewpoint of cycle characteristics and volume energy density.
  • the porosity refers to the area ratio of the void portion to the sum of the area of the primary particle and the area of the void portion in the cross section of the secondary particle.
  • the average particle size of the positive electrode active material is not particularly limited, but is preferably 6 to 11 ⁇ m, more preferably 7 to 10 ⁇ m in terms of secondary particle size from the viewpoint of increasing output.
  • the average particle diameter of the primary particles is 0.4 to 0.65 ⁇ m, more preferably 0.45 to 0.55 ⁇ m.
  • the “particle diameter” in the present specification means the maximum distance L among the distances between any two points on the particle outline.
  • the average particle diameter the average particle diameter of particles observed in several to several tens of fields using an observation means such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). A value calculated as a value is adopted.
  • the positive electrode active material of the present invention preferably has a specific surface area of 0.30 to 1.0 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 electrode reaction can be minimized.
  • the occurrence of polarization causes side reactions such as decomposition of the electrolytic solution and oxidative decomposition of the surface of the electrode material. Therefore, it is preferable to minimize the occurrence of polarization.
  • the specific surface area is 0.30 to 0.7 m 2 / g.
  • the lithium nickel composite oxide of the present invention has (1) a true density of 4.40 to 4.80 g / cm 3 , or (2) a specific surface area of 0.30 to 1.0 m 2 / g. It is preferable to satisfy at least one of the above, and it is more preferable to satisfy both (1) and (2).
  • the positive electrode active material content in the positive electrode active material layer is preferably 85 to 99.5% by weight.
  • the positive electrode active material layer according to the present invention is provided with a conductive additive, a binder, an electrolyte (such as a polymer matrix, an ion conductive polymer, an electrolytic solution) and an ion conductivity as necessary. It further includes other additives such as lithium salts.
  • 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 conductive assistant means an additive blended to improve the conductivity of the positive electrode active material layer or the negative electrode active material layer.
  • Examples of the conductive assistant include carbon materials such as carbon black such as ketjen black and acetylene black, graphite, and carbon fiber.
  • Examples of the electrolyte salt (lithium salt) include Li (C 2 F 5 SO 2 ) 2 N, Li (CF 3 SO 2 ) 2 N, LiPF 6 , LiBF 4 , LiClO 4 , LiAsF 6 , and LiCF 3 SO 3. It is done.
  • 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 according to the present invention has a configuration in which a negative electrode active material layer containing a negative electrode active material is formed on the surface of a negative electrode current collector.
  • the negative electrode current collector is composed of a conductive material.
  • 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 methacrylate Such as tacrylate
  • 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.
  • Examples of the form of the separator 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.
  • the liquid electrolyte may further contain additives other than the components described above. Specific examples of such compounds 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 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 .
  • 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.
  • the laminate film for example, a laminate film having a three-layer structure in which PP, aluminum, and nylon are laminated in this order can be used.
  • 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 aluminum laminate because the group pressure applied to the power generation element applied from the outside can be easily adjusted and can be easily adjusted to a desired electrolyte layer thickness.
  • 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 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. 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 negative electrode active material layer is preferably rectangular, and the length of the short side of the rectangle is preferably 100 mm or more.
  • the length of the short side of the negative electrode active material layer refers to the side having the shortest length among the electrodes.
  • the upper limit of the length of the short side of the battery structure is not particularly limited, but is usually 250 mm or less.
  • the nonaqueous electrolyte secondary battery according to the present embodiment is a battery that is enlarged as described above, together with the merit due to the manifestation of the effects of the present invention. Further, as the non-aqueous electrolyte secondary battery according to this embodiment, it is more preferable that it is a large-sized lithium ion secondary battery for automobiles, together with the merit due to the manifestation of the effects of the present invention.
  • the size of the battery can be specified by the volume energy density, the single cell rated capacity, and the like.
  • a travel distance (cruising range) by one charge is 100 km, which is a market requirement.
  • the single cell rated capacity is preferably 20 Wh or more
  • the volume energy density of the battery is preferably 153 Wh / L or more.
  • the volume energy density and the rated discharge capacity are measured by the methods described in the following examples.
  • 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. Setting the aspect ratio in such a range is preferable because the gas generated during charging can be discharged uniformly in the surface direction.
  • 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.
  • Example 1 Preparation of positive electrode active material Sodium hydroxide and ammonia are continuously supplied to an aqueous solution (1.0 mol / L) in which nickel sulfate, cobalt sulfate, and manganese sulfate are dissolved so as to have a pH of 11.0.
  • a metal composite hydroxide formed by solid solution with a molar ratio of nickel, cobalt and manganese of 50:20:30 was prepared by the method.
  • the metal composite oxide and lithium carbonate were weighed so that the ratio of the total number of moles of metals other than Li (Ni, Co, Mn) to the number of moles of Li was 1: 1, and then mixed sufficiently.
  • the temperature was raised at a temperature rate of 5 ° C./min, pre-baked at 900 ° C. for 2 hours in an air atmosphere, then heated at a rate of temperature increase of 3 ° C./min, finally baked at 920 ° C. for 10 hours, and cooled to room temperature.
  • a lithium nickel composite oxide having a chemical composition of LiNi 0.50 Mn 0.30 Co 0.20 O 2 was obtained.
  • the lithium nickel composite oxide (LiNi 0.50 Mn 0.30 Co 0.20 O 2 ) had an average primary particle size of 0.5 ⁇ m and an average secondary particle size of 10.0 ⁇ m.
  • the spinel lithium manganate having the chemical composition LiMn 2 O 4 was obtained by baking at 20 ° C. for 20 hours.
  • the average secondary particle diameter of the spinel lithium manganate (LiMn 2 O 4 ) was 10.0 ⁇ m.
  • lithium nickel composite oxide LiNi 0.50 Mn 0.30 Co 0.20 O 2
  • lithium spinel manganate LiMn 2 O 4
  • This slurry was applied to both surfaces of a copper foil (thickness 10 ⁇ m) serving as a negative electrode current collector, and the coating amount per unit area was 1 for each AC ratio (negative electrode charge capacity / positive electrode charge capacity). .2 was set. After sufficiently drying, the electrode thickness was adjusted using a roll press so that the electrode mixture filling density was 1.4 g / cm 3, and a negative electrode having negative electrode active material layers on both sides was produced.
  • Electrolytic Solution A solution was prepared by dissolving 1.0M LiPF 6 in a mixed solvent (volume ratio of 1: 1) of ethylene carbonate (EC) and dimethyl carbonate (DMC). Vinylene carbonate was added thereto in an amount corresponding to 2% by weight with respect to the weight of the electrolytic solution to obtain an electrolytic solution.
  • 1.0 M LiPF 6 means that the lithium salt (LiPF 6 ) concentration in the mixture of the mixed solvent and the lithium salt is 1.0 M.
  • the positive electrode produced in (1) above is a square with a side of 20 cm
  • the negative electrode produced in (2) above is a square with a side of 20.5 cm
  • a separator polyethylene / polypropylene microporous film, thickness 25 ⁇ m
  • both ends are negative electrodes
  • a separator is interposed between the positive electrode and the negative electrode. It was.
  • Parallel cells were stacked by connecting the tabs of each layer.
  • the obtained power generation element was put in an aluminum laminate outer package, the electrolyte prepared in (1) above was injected, and vacuum sealed to prepare a full cell for evaluation.
  • the projected area of the battery including the full cell aluminum laminate outer package obtained was 484 cm 2 .
  • Examples 2-5, Comparative Examples 1-2 In preparation of the positive electrode active material described in Example 1, the mixing ratio of lithium nickel-based composite oxide (LiNi 0.50 Mn 0.30 Co 0.20 O 2 ) and lithium spinel manganate (LiMn 2 O 4 ) A full cell for evaluation was produced in the same manner as in Example 1 except that a positive electrode active material produced by changing the composition as described in Table 1 was used.
  • Examples 6 to 7, Comparative Example 3 In the preparation of the lithium nickel-based composite oxide described in Example 1, the preparation conditions were changed by the coprecipitation method so that the molar ratio of nickel, cobalt, and manganese was 1/3: 1/3: 1/3. Further, a positive electrode active material prepared according to a mixing ratio of lithium nickel-based composite oxide (LiNi 1/3 Mn 1/3 Co 1/3 O 2 ) and lithium spinel manganate (LiMn 2 O 4 ) described in Table 1 Each full cell for evaluation was produced in the same manner as in Example 1 except that was used.
  • Examples 8 to 9, Comparative Example 4 In the preparation of the lithium nickel-based composite oxide described in Example 1, the preparation conditions were changed by a coprecipitation method so that the molar ratio of nickel, cobalt, and manganese was 80:10:10. Except that a positive electrode active material prepared according to a mixing ratio of lithium nickel-based composite oxide (LiNi 0.8 Mn 0.1 Co 0.1 O 2 ) and spinel lithium manganate (LiMn 2 O 4 ) was used. Each evaluation full cell was produced in the same manner as in Example 1.
  • Examples 10 to 11, Comparative Example 5 In the preparation of the lithium nickel-based composite oxide described in Example 1, the preparation conditions were changed by a coprecipitation method so that the molar ratio of nickel, cobalt, and manganese was 60:20:20. Except that a positive electrode active material prepared according to a mixing ratio of lithium nickel-based composite oxide (LiNi 0.6 Mn 0.2 Co 0.2 O 2 ) and lithium spinel manganate (LiMn 2 O 4 ) was used. Each evaluation full cell was produced in the same manner as in Example 1.
  • Examples 12 to 13, Comparative Example 6 In the production of the lithium nickel composite oxide described in Example 1, aluminum sulfate is used instead of manganese sulfate so that the molar ratio of nickel, cobalt, and aluminum is 80:10:10 by coprecipitation. The preparation conditions were changed, and further according to the mixing ratio of lithium nickel-based composite oxide (LiNi 0.8 Co 0.1 Al 0.1 O 2 ) and spinel lithium manganate (LiMn 2 O 4 ) listed in Table 1 Each evaluation full cell was produced like Example 1 except having used the produced positive electrode active material.
  • Example 14 to 17 In the production of the positive electrode described in Example 1, a full cell for each evaluation was produced in the same manner as in Example 1 except that the basis weight (one side) of the positive electrode was changed according to the description in Table 2.
  • Examples 18 to 21 In the production of the positive electrode described in Example 1, each evaluation full cell was produced in the same manner as in Example 1, except that the packing density of the positive electrode was changed according to the description in Table 3.
  • the results of Examples 1 to 5 and Comparative Examples 1 and 2 are shown in FIG. 3-1, and the results of Examples 6 to 7 and Comparative Example 3 are shown in FIG. 3-2.
  • the results of Examples 8 to 9 and Comparative Example 4 are shown in FIG. 3-3, the results of Examples 10 to 11 and Comparative Example 5 are shown in FIG. 3-4, and the results of Examples 12 to 13 and Comparative Example 6 are shown in FIG.
  • the results of Examples 1 and 14 to 17 are shown in FIG. 4, and the results of Examples 1 and 18 to 21 are shown in FIG.
  • the 4.15V full charge state is SOC 100%
  • the 3V full discharge state is SOC 0%
  • the state in which the capacity of 20% from the full discharge state is charged is SOC 20%
  • the full discharge state is 50%.
  • the state in which the capacity is charged is defined as SOC 50%.
  • the rated capacity is about 10 hours after injecting the electrolyte for the test battery, and the battery is initially charged after the battery voltage becomes 2.0 V or higher. Thereafter, the measurement is performed by the following procedures 1 to 4 at a temperature of 25 ° C. and a voltage range of 3.0 V to 4.15 V.
  • Procedure 1 After reaching 4.15 V by constant current charging at 0.2 C amp, charge for 1.5 hours by constant voltage charging and rest for 5 minutes.
  • Procedure 2 After reaching 3.0 V by constant current discharge of 0.2 C amp, pause for 5 minutes.
  • Procedure 3 After reaching 4.15 V by constant current charging at 1 C amp, charge for 2.5 hours by constant voltage charging, and then rest for 5 minutes.
  • Procedure 4 Discharge until reaching 3.0V by constant current discharge of 0.2C ampere.
  • the discharge capacity obtained from the constant current discharge in step 4 is the rated capacity.
  • Table 1 shows the rated discharge capacity (Ah) and the ratio of the battery area to the rated capacity (cm 2 / Ah) of each full cell measured as described above.

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Abstract

La présente invention vise à fournir un moyen qui est apte à supprimer des changements de résistance associés à la profondeur de décharge et à améliorer des caractéristiques de taux de décharge dans une batterie qui est particulièrement destinée à une utilisation à débit élevé (avec une résistance interne aussi petite que 10 mΩ/Ah (état de charge (SOC) 50 %) ou moins) parmi des batteries secondaires à électrolyte non aqueux de grande taille aptes à être utilisées pour commander des véhicules électriques, par exemple. A cet effet, l'invention concerne une batterie secondaire à électrolyte non aqueux qui comprend un élément de génération d'énergie comprenant : une électrode positive dans laquelle une couche de matériau actif d'électrode positive comprenant un matériau actif d'électrode positive est formée sur la surface d'un collecteur de charge d'électrode positive ; une électrode négative dans laquelle une couche de matériau actif d'électrode négative comprenant un matériau actif d'électrode négative est formée sur la surface d'un collecteur de charge d'électrode négative ; et un séparateur. Dans cette batterie secondaire : le matériau actif d'électrode positive comprend un matériau actif d'électrode positive au manganèse de type spinelle et un oxyde complexe de lithium-nickel ; le taux de mélange dudit oxyde complexe de lithium-nickel sur 100 % en poids dudit matériau actif d'électrode positive et de 30 % en poids ou supérieur ; et la résistance interne est de 10 mΩ/Ah ou moins (SOC 50 %).
PCT/JP2014/056795 2013-03-15 2014-03-13 Batterie secondaire à électrolyte non aqueux WO2014142280A1 (fr)

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US11331692B2 (en) 2017-12-15 2022-05-17 Corning Incorporated Methods for treating a substrate and method for making articles comprising bonded sheets
US11535553B2 (en) 2016-08-31 2022-12-27 Corning Incorporated Articles of controllably bonded sheets and methods for making same
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