WO2023090333A1 - 非水電解質蓄電素子 - Google Patents

非水電解質蓄電素子 Download PDF

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WO2023090333A1
WO2023090333A1 PCT/JP2022/042462 JP2022042462W WO2023090333A1 WO 2023090333 A1 WO2023090333 A1 WO 2023090333A1 JP 2022042462 W JP2022042462 W JP 2022042462W WO 2023090333 A1 WO2023090333 A1 WO 2023090333A1
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aqueous electrolyte
negative electrode
transition metal
positive electrode
less
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English (en)
French (fr)
Japanese (ja)
Inventor
健太 上平
勇人 山川
健太 中井
喬 金子
大聖 関口
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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Priority to US18/711,183 priority Critical patent/US20250006916A1/en
Priority to EP22895614.0A priority patent/EP4439760A4/en
Priority to JP2023562355A priority patent/JPWO2023090333A1/ja
Priority to CN202280077010.8A priority patent/CN118369801A/zh
Publication of WO2023090333A1 publication Critical patent/WO2023090333A1/ja
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
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    • 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
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
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    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/42—Powders or particles, e.g. composition thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
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    • 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
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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 non-aqueous electrolyte storage elements.
  • Non-aqueous electrolyte secondary batteries typified by lithium-ion secondary batteries
  • a non-aqueous electrolyte secondary battery generally has a pair of electrodes electrically isolated by a separator and a non-aqueous electrolyte interposed between the electrodes, and transfers charge transport ions between the electrodes. It is configured to charge and discharge by performing.
  • Capacitors such as lithium ion capacitors and electric double layer capacitors are also widely used as non-aqueous electrolyte storage elements other than non-aqueous electrolyte secondary batteries.
  • An object of the present invention is to provide a non-aqueous electrolyte storage element that has a low initial resistance and suppresses an increase in resistance after charge-discharge cycles.
  • a non-aqueous electrolyte storage element includes a positive electrode containing a lithium transition metal composite oxide containing nickel element and manganese element, and a negative electrode containing solid graphite, and the porosity of the solid graphite is is 2% or less, and the content of the nickel element with respect to the transition metal element in the lithium-transition metal composite oxide is 40 mol% or more.
  • a non-aqueous electrolyte storage element includes a positive electrode containing a lithium transition metal composite oxide containing nickel element and manganese element, and a negative electrode containing solid graphite.
  • the porosity is 2% or less, and the content of the manganese element with respect to the transition metal element in the lithium-transition metal composite oxide is 30 mol % or less.
  • non-aqueous electrolyte storage element having a low initial resistance and a suppressed increase in resistance after charge-discharge cycles.
  • FIG. 1 is a see-through perspective view showing one embodiment of a non-aqueous electrolyte storage element.
  • FIG. 2 is a schematic diagram showing an embodiment of a power storage device configured by assembling a plurality of non-aqueous electrolyte power storage elements.
  • a non-aqueous electrolyte storage element (A) includes a positive electrode containing a lithium transition metal composite oxide containing nickel element and manganese element, and a negative electrode containing solid graphite, The porosity of the solid graphite is 2% or less, and the content of the nickel element with respect to the transition metal element in the lithium-transition metal composite oxide is 40 mol % or more.
  • the non-aqueous electrolyte storage element (A) described in [1] above has a low initial resistance and suppresses an increase in resistance after charge-discharge cycles. Although the reason for this is not clear, the following reasons are presumed.
  • a lithium-transition metal composite oxide (a) containing a nickel element and a manganese element and having a nickel element content of 40 mol% or more with respect to the transition metal element has high electron conductivity.
  • the non-aqueous electrolyte storage element (A) containing the substance (a) in the positive electrode has a low initial resistance.
  • the lithium-transition metal composite oxide (a) which has a high nickel element content, is prone to particle cracking during charge-discharge cycles, and the electrical contact between the particles is reduced, resulting in a decrease in the resistance after charge-discharge cycles. increase is likely to occur.
  • solid graphite with a porosity of 2% or less undergoes less volume change due to expansion and contraction during charge and discharge than hollow graphite with a porosity of more than 2%. Therefore, when the positive electrode containing the lithium-transition metal composite oxide (a) and the negative electrode containing solid graphite are combined, the pressure on the positive electrode due to the expansion of the negative electrode is suppressed, and the lithium-transition metal composite oxide (a) is suppressed.
  • Solid in solid graphite means that the inside of graphite particles is packed and voids are not substantially present. More specifically, the term “solid” refers to the area ratio of voids in the particle to the area of the entire particle ( porosity) is 2% or less.
  • the "area ratio (porosity) of voids in the particles relative to the area of the entire particles" in the graphite particles can be determined by the following procedure. (1) Preparation of measurement sample A negative electrode to be measured is fixed with a thermosetting resin. A cross-section polisher is used to expose the cross section of the negative electrode fixed with the resin, and a sample for measurement is prepared. A negative electrode to be measured is prepared by the following procedure.
  • the negative electrode can be prepared before assembling the non-aqueous electrolyte storage element, it is used as it is.
  • the non-aqueous electrolyte storage element is discharged at a constant current of 0.1 C to the discharge end voltage in normal use to be in a discharged state.
  • the discharged non-aqueous electrolyte storage element is disassembled, the negative electrode is taken out, and components (electrolyte, etc.) adhering to the negative electrode are thoroughly washed with dimethyl carbonate, and then dried under reduced pressure at room temperature for 24 hours.
  • the work from disassembling the non-aqueous electrolyte storage element to preparing the negative electrode to be measured is performed in a dry air atmosphere with a dew point of -40°C or less.
  • the term “during normal use” refers to the case where the non-aqueous electrolyte storage element is used under the charging/discharging conditions recommended or specified for the non-aqueous electrolyte storage element.
  • a charger is prepared for the non-aqueous electrolyte storage device, it refers to the case where the charger is applied to use the non-aqueous electrolyte storage device.
  • the SEM image shall be a secondary electron image.
  • the acceleration voltage is 15 kV.
  • the observation magnification is set so that the number of graphite particles appearing in one field of view is 3 or more and 15 or less.
  • the obtained SEM image is saved as an image file.
  • various conditions such as spot diameter, working distance, irradiation current, brightness, and focus are appropriately set so that the outline of the graphite particles becomes clear.
  • the image of the first graphite particle which is the same as before, is subjected to binarization processing using a density of 10% as a threshold value.
  • the outer edge of the graphite particle is determined by the binarization process, and the area inside the outer edge is calculated to obtain the "area S0 of the entire particle".
  • the ratio of S1 to S0 S1/S0
  • S1 and S0 calculated above
  • the "area ratio R1 of voids in the particle with respect to the area of the whole particle" in the first graphite particle is calculated. do.
  • the images of the second and subsequent graphite particles among the cut-out graphite particles are also subjected to the above-described binarization process, and the area S1 and the area S0 are calculated.
  • image editing and image analysis may be used instead of the scanning electron microscope used for "acquisition of SEM image", image editing software used for "cutting out the outline of graphite particles”, and image analysis software used for "binarization processing", equivalent to these Devices and software capable of measurement.
  • Graphite refers to a carbon material having an average lattice spacing (d 002 ) of the (002) plane of 0.33 nm or more and less than 0.34 nm as determined by X-ray diffraction before charging/discharging or in a discharged state.
  • the “discharged state” of the carbon material means a state in which the carbon material, which is the negative electrode active material, is discharged such that lithium ions that can be inserted/extracted are sufficiently released during charge/discharge.
  • the open circuit voltage is 0.7 V or higher.
  • the content of the manganese element relative to the transition metal element in the lithium-transition metal composite oxide (a) is 30 mol% or less. is preferred.
  • the non-aqueous electrolyte storage element according to [2] above has a lower initial resistance.
  • a nonaqueous electrolyte storage element (B) includes a positive electrode containing a lithium transition metal composite oxide containing nickel element and manganese element, and a negative electrode containing solid graphite.
  • the porosity of the solid graphite is 2% or less
  • the content of the manganese element with respect to the transition metal element in the lithium-transition metal composite oxide is 30 mol % or less.
  • the non-aqueous electrolyte storage element (B) described in [3] above has a low initial resistance and suppresses an increase in resistance after charge-discharge cycles. Although the reason for this is not clear, the following reasons are presumed. Lithium-transition metal composite oxide (b) containing nickel element and manganese element and having a manganese element content of 30 mol% or less relative to the transition metal element is also the same as lithium-transition metal composite oxide (a) described above. Although the initial resistance can be lowered, particle cracking is likely to occur during charge/discharge cycles.
  • the negative electrode further includes a binder, and the solid It is preferable that the graphite have an average particle size of 4 ⁇ m or more.
  • the graphite have an average particle size of 4 ⁇ m or more.
  • contact points between solid graphite particles can be reduced compared to the case of using solid graphite with an average particle size of less than the above lower limit.
  • the amount of binder required to maintain contact between graphite particles can be reduced. That is, even if the content of the binder in the negative electrode is relatively small, the contact between solid graphite particles is enhanced.
  • the solid graphite particles are kept in sufficient contact even after repeated charging and discharging. resistance increase tends to be more suppressed. Furthermore, not only the contact between the solid graphite particles in the negative electrode increases, but also the contact between the negative electrode substrate and the solid graphite increases, so that the solid graphite is detached from the negative electrode during the manufacturing process. There are also advantages such as difficulty and high productivity.
  • Average particle size is based on JIS-Z-8825 (2013), based on the particle size distribution measured by a laser diffraction / scattering method for a diluted solution in which particles are diluted with a solvent, JIS-Z-8819 -2 (2001) means a value at which the volume-based integrated distribution calculated according to 50%.
  • the solid graphite to be measured is used for the measurement as it is when the solid graphite before manufacturing the negative electrode can be prepared.
  • the negative electrode When preparing from the non-aqueous electrolyte storage element after assembly, the negative electrode in a discharged state by the procedure of measuring the "area ratio (porosity) of voids in the particles with respect to the area of the whole particles" A step of collecting graphite and immersing it in dimethyl carbonate for 5 minutes is repeated twice to sufficiently remove the non-aqueous electrolyte, and the solid graphite is dried under reduced pressure at room temperature for 24 hours for measurement.
  • the solid graphite has an average particle size of 7 ⁇ m. It is preferable that it is above. In the non-aqueous electrolyte storage element according to [5] having such a negative electrode, the above effects can be exhibited more effectively.
  • a non-aqueous electrolyte storage device, a storage device, a method for manufacturing a non-aqueous electrolyte storage device, and other embodiments according to one embodiment of the present invention will be described in detail. Note that the name of each component (each component) used in each embodiment may be different from the name of each component (each component) used in the background art.
  • a non-aqueous electrolyte storage element includes an electrode body having a positive electrode, a negative electrode and a separator, a non-aqueous electrolyte, the electrode body and the non-aqueous electrolyte and a container that houses the
  • the electrode body is usually a laminated type in which a plurality of positive electrodes and a plurality of negative electrodes are laminated with separators interposed therebetween, or a wound type in which positive electrodes and negative electrodes are laminated with separators interposed and wound.
  • the non-aqueous electrolyte exists in a state contained in the positive electrode, the negative electrode and the separator.
  • a non-aqueous electrolyte secondary battery hereinafter also simply referred to as "secondary battery" will be described.
  • the positive electrode has a positive electrode base material and a positive electrode active material layer disposed directly on the positive electrode base material or via an intermediate layer.
  • a positive electrode base material has electroconductivity. Whether or not a material has "conductivity" is determined using a volume resistivity of 10 7 ⁇ cm as a threshold measured according to JIS-H-0505 (1975).
  • the material for the positive electrode substrate metals such as aluminum, titanium, tantalum and stainless steel, or alloys thereof are used. Among these, aluminum or an aluminum alloy is preferable from the viewpoint of potential resistance, high conductivity, and cost.
  • the positive electrode substrate include foil, deposited film, mesh, porous material, and the like, and foil is preferable from the viewpoint of cost. Therefore, aluminum foil or aluminum alloy foil is preferable as the positive electrode substrate. Examples of aluminum or aluminum alloy include A1085, A3003, A1N30, etc. defined in JIS-H-4000 (2014) or JIS-H-4160 (2006).
  • the average thickness of the positive electrode substrate is preferably 3 ⁇ m or more and 50 ⁇ m or less, more preferably 5 ⁇ m or more and 40 ⁇ m or less, even more preferably 8 ⁇ m or more and 30 ⁇ m or less, and particularly preferably 10 ⁇ m or more and 25 ⁇ m or less.
  • the intermediate layer is a layer arranged between the positive electrode substrate and the positive electrode active material layer.
  • the intermediate layer contains a conductive agent such as carbon particles to reduce the contact resistance between the positive electrode substrate and the positive electrode active material layer.
  • the composition of the intermediate layer is not particularly limited, and includes, for example, a binder and a conductive agent.
  • the positive electrode active material layer contains a positive electrode active material.
  • the positive electrode active material layer contains arbitrary components such as a conductive agent, a binder (binding agent), a thickener, a filler, etc., as required.
  • the positive electrode active material contains a lithium transition metal composite oxide.
  • the lithium-transition metal composite oxide preferably has a layered ⁇ -NaFeO 2 type crystal structure.
  • the lithium-transition metal composite oxide (a) contains a nickel element and a manganese element as the lithium-transition metal composite oxide, and the content of the nickel element relative to the transition metal element is 40 mol % or more. can be used.
  • the content of the nickel element relative to the transition metal element in the lithium-transition metal composite oxide (a) is preferably 45 mol% or more, more preferably 50 mol% or more.
  • the initial resistance of the non-aqueous electrolyte storage element can be lowered by setting the nickel element content to the above lower limit or more.
  • the content of the nickel element with respect to the transition metal element in the lithium-transition metal composite oxide (a) is preferably 70 mol% or less, more preferably 60 mol% or less, further preferably less than 60 mol%, and 55 mol% or less. is more preferable in some cases.
  • the content of the nickel element with respect to the transition metal element in the lithium-transition metal composite oxide (a) can be at least one of the lower limits described above and not more than any of the upper limits described above.
  • the content of the manganese element relative to the transition metal element in the lithium-transition metal composite oxide (a) is preferably 5 mol% or more and 30 mol% or less, more preferably 10 mol% or more and 25 mol% or less, and 15 mol% or more and 20 mol%. % or less is more preferable.
  • the initial resistance of the non-aqueous electrolyte storage element can be further lowered.
  • the content C Ni of the nickel element relative to the transition metal element in the lithium-transition metal composite oxide (a) is greater than the content C Mn of the manganese element.
  • the relationship between C Ni and C Mn preferably satisfies 1.0 ⁇ C Ni /C Mn ⁇ 3.5, more preferably 1.2 ⁇ C Ni /C Mn ⁇ 3.0, It is more preferable to satisfy 1.5 ⁇ C Ni /C Mn ⁇ 2.5.
  • C Ni is preferably greater than C Mn by 20 mol % or more.
  • the value obtained by subtracting C Mn from C Ni is preferably 35 mol % or less, more preferably 30 mol % or less, still more preferably 25 mol % or less.
  • the lithium-transition metal composite oxide (a) preferably further contains a cobalt element.
  • the content of the cobalt element relative to the transition metal element in the lithium-transition metal composite oxide (a) is preferably 1 mol% or more and 30 mol% or less, more preferably 5 mol% or more and 25 mol% or less, and 10 mol% or more and 20 mol%. % or less is more preferable.
  • the cobalt element content within the above range, the initial resistance of the non-aqueous electrolyte storage element can be further reduced.
  • the content C Ni of the nickel element relative to the transition metal element in the lithium-transition metal composite oxide (a) is greater than the content C Co of the cobalt element.
  • C Ni and C Co preferably satisfies 1.0 ⁇ C Ni /C Co ⁇ 2.0, more preferably 1.0 ⁇ C Ni /C Co ⁇ 1.5, It is more preferable to satisfy 1.1 ⁇ C Ni /C Co ⁇ 1.3.
  • C Ni is preferably at least 5 mol % greater than C Co .
  • the value obtained by subtracting C Co from C Ni is preferably 30 mol % or less, more preferably 20 mol % or less (for example, 12 mol % or less, typically 10 mol % or less).
  • the lithium-transition metal composite oxide (a) may further contain other transition metal elements other than the nickel element, the manganese element, and the cobalt element, and typical metal elements other than the lithium element (eg, aluminum element, etc.).
  • the total content of the nickel element, the manganese element and the cobalt element relative to the transition metal element in the lithium-transition metal composite oxide (a) is preferably 90 mol% or more, more preferably 99 mol% or more, and 100 mol%.
  • the total content of the nickel element, the manganese element and the cobalt element with respect to the metal elements other than the lithium element in the lithium-transition metal composite oxide (a) is preferably 90 mol% or more, more preferably 99 mol% or more, and 100 mol. %.
  • the lithium-transition metal composite oxide (b) contains nickel element and manganese element as the lithium-transition metal composite oxide, and the content of manganese element relative to the transition metal element is 30 mol % or less.
  • the manganese element content relative to the transition metal element in the lithium-transition metal composite oxide (b) is preferably 25 mol % or less, more preferably 20 mol % or less.
  • the initial resistance of the non-aqueous electrolyte storage element can be lowered by setting the content of the manganese element to the above upper limit or less.
  • the manganese element content relative to the transition metal element in the lithium-transition metal composite oxide (b) is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 15 mol % or more.
  • the content of the manganese element relative to the transition metal element in the lithium-transition metal composite oxide (b) can be at least one of the lower limits described above and not more than any of the upper limits described above.
  • the content of the nickel element relative to the transition metal element in the lithium-transition metal composite oxide (b) is preferably 40 mol% or more and 70 mol% or less, more preferably 45 mol% or more and 60 mol% or less, and 50 mol% or more and 60 mol%. % is more preferred, and 55 mol % or less is even more preferred in some cases.
  • the content C Ni of the nickel element relative to the transition metal element in the lithium-transition metal composite oxide (b) is greater than the content C Mn of the manganese element.
  • the relationship between C Ni and C Mn preferably satisfies 1.0 ⁇ C Ni /C Mn ⁇ 3.5, more preferably 1.2 ⁇ C Ni /C Mn ⁇ 3.0, It is more preferable to satisfy 1.5 ⁇ C Ni /C Mn ⁇ 2.5.
  • C Ni is preferably greater than C Mn by 20 mol % or more.
  • the value obtained by subtracting C Mn from C Ni is preferably 35 mol % or less, more preferably 30 mol % or less, still more preferably 25 mol % or less.
  • the lithium-transition metal composite oxide (b) preferably further contains a cobalt element.
  • the content C Co of the cobalt element relative to the transition metal element in the lithium-transition metal composite oxide (b) is greater than the content C Mn of the manganese element.
  • the relationship between C Co and C Mn preferably satisfies 1.0 ⁇ C Co /C Mn ⁇ 3.0, more preferably 1.0 ⁇ C Co /C Mn ⁇ 2.5, It is more preferable to satisfy 1.1 ⁇ C Co /C Mn ⁇ 2.0.
  • C Co is preferably at least 10 mol % greater than C Mn .
  • the value obtained by subtracting C Mn from C Co is preferably 30 mol % or less, more preferably 20 mol % or less, and even more preferably 15 mol % or less.
  • the lithium-transition metal composite oxide (b) may further contain transition metal elements other than nickel, manganese, and cobalt, and typical metal elements other than lithium (for example, aluminum).
  • the content of the cobalt element relative to the transition metal element in the lithium-transition metal composite oxide (b), the total content of the nickel element, the manganese element and the cobalt element relative to the transition metal element, and the nickel element and manganese element relative to the metal elements excluding the lithium element and cobalt elements can be in the same range as these contents in the lithium-transition metal composite oxide (a).
  • a compound represented by the following formula 1 may be used as the lithium transition metal composite oxide.
  • Me is a transition metal element containing Ni and Mn. 0 ⁇ 1.
  • ⁇ in Formula 1 may be 0 or more and 0.5 or less, 0 or more and 0.3 or less, or 0 or more and 0.1 or less.
  • Me preferably further contains Co in addition to Ni and Mn.
  • the content (composition ratio) of each of Ni, Mn, Co, etc. relative to Me is the preferred content of each transition metal element in the lithium-transition metal composite oxide (a) and the lithium-transition metal composite oxide (b) described above. can be adopted.
  • Me may further contain transition metal elements other than Mn, Ni and Co.
  • the composition ratio of the lithium-transition metal composite oxide refers to the composition ratio before charging/discharging or when fully discharged by the following method.
  • the non-aqueous electrolyte storage element is discharged at a constant current of 0.05C to the lower limit voltage for normal use.
  • the non-aqueous electrolyte storage element in this state was disassembled, the positive electrode was taken out, and a half-cell with metal Li as the counter electrode was assembled. Constant current discharge is carried out until Li/Li + to adjust the positive electrode to a fully discharged state. Dismantle again and take out the positive electrode.
  • the components (electrolyte, etc.) adhering to the taken-out positive electrode are thoroughly washed, dried under reduced pressure at room temperature for 24 hours, and then the lithium-transition metal composite oxide of the positive electrode active material is collected.
  • the collected lithium-transition metal composite oxide is subjected to measurement.
  • the work from dismantling the non-aqueous electrolyte storage element to collecting the lithium transition metal composite oxide for measurement is performed in an argon atmosphere with a dew point of -60°C or less.
  • the surface of the lithium-transition metal composite oxide may be coated with another material.
  • Other materials for covering the surface include compounds containing aluminum element, tungsten element, boron element, and the like.
  • the content of the lithium transition metal composite oxide in the positive electrode active material layer is preferably 50% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 98% by mass or less, and further 80% by mass or more and 95% by mass or less. preferable.
  • the positive electrode active material may further contain a positive electrode active material other than the lithium-transition metal composite oxide.
  • a positive electrode active material other positive electrode active materials, conventionally known various positive electrode active materials can be used.
  • the content of the lithium-transition metal composite oxide with respect to all positive electrode active materials contained in the positive electrode active material layer is preferably 90% by mass or more, more preferably 99% by mass or more.
  • the content of all positive electrode active materials in the positive electrode active material layer is preferably 50% by mass or more and 99% by mass or less, more preferably 70% by mass or more and 98% by mass or less, and even more preferably 80% by mass or more and 95% by mass or less.
  • the positive electrode active material is usually particles (powder).
  • the average particle size of the positive electrode active material is preferably, for example, 0.1 ⁇ m or more and 20 ⁇ m or less. By making the average particle size of the positive electrode active material equal to or more than the above lower limit, manufacturing or handling of the positive electrode active material becomes easy. By setting the average particle size of the positive electrode active material to the above upper limit or less, the electron conductivity of the positive electrode active material layer is improved. Note that when a composite of a positive electrode active material and another material is used, the average particle size of the composite is taken as the average particle size of the positive electrode active material.
  • Pulverizers, classifiers, etc. are used to obtain powder with a predetermined particle size.
  • Pulverization methods include, for example, methods using a mortar, ball mill, sand mill, vibrating ball mill, planetary ball mill, jet mill, counter jet mill, whirling jet mill, or sieve.
  • wet pulverization in which water or an organic solvent such as hexane is allowed to coexist can also be used.
  • a sieve, an air classifier, or the like is used as necessary, both dry and wet.
  • the conductive agent is not particularly limited as long as it is a conductive material.
  • Examples of such conductive agents include carbonaceous materials, metals, and conductive ceramics.
  • Carbonaceous materials include graphite, non-graphitic carbon, graphene-based carbon, and the like.
  • Examples of non-graphitic carbon include carbon nanofiber, pitch-based carbon fiber, and carbon black.
  • Examples of carbon black include furnace black, acetylene black, and ketjen black.
  • Graphene-based carbon includes graphene, carbon nanotube (CNT), fullerene, and the like.
  • the shape of the conductive agent may be powdery, fibrous, or the like.
  • As the conductive agent one type of these materials may be used alone, or two or more types may be mixed and used. Also, these materials may be combined for use.
  • a composite material of carbon black and CNT may be used.
  • carbon black is preferable from the viewpoint of electron conductivity and coatability
  • acetylene black is particularly preferable
  • the content of the conductive agent in the positive electrode active material layer is preferably 1% by mass or more and 10% by mass or less, more preferably 3% by mass or more and 9% by mass or less.
  • Binders include, for example, fluorine resins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), thermoplastic resins such as polyethylene, polypropylene, polyacryl, and polyimide; ethylene-propylene-diene rubber (EPDM), sulfone Elastomers such as modified EPDM, styrene-butadiene rubber (SBR) and fluororubber; polysaccharide polymers and the like.
  • fluorine resins polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.
  • thermoplastic resins such as polyethylene, polypropylene, polyacryl, and polyimide
  • EPDM ethylene-propylene-diene rubber
  • SBR styrene-butadiene rubber
  • fluororubber polysaccharide polymers and the like.
  • the content of the binder in the positive electrode active material layer is preferably 1% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 9% by mass or less.
  • thickeners examples include polysaccharide polymers such as carboxymethylcellulose (CMC) and methylcellulose.
  • CMC carboxymethylcellulose
  • methylcellulose examples include polysaccharide polymers such as carboxymethylcellulose (CMC) and methylcellulose.
  • the functional group may be previously deactivated by methylation or the like.
  • the filler is not particularly limited.
  • Fillers include polyolefins such as polypropylene and polyethylene, inorganic oxides such as silicon dioxide, alumina, titanium dioxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide and aluminosilicate, magnesium hydroxide, calcium hydroxide, hydroxide Hydroxides such as aluminum, carbonates such as calcium carbonate, sparingly soluble ionic crystals such as calcium fluoride, barium fluoride, and barium sulfate, nitrides such as aluminum nitride and silicon nitride, talc, montmorillonite, boehmite, zeolite, Mineral resource-derived substances such as apatite, kaolin, mullite, spinel, olivine, sericite, bentonite, and mica, or artificial products thereof may be used.
  • the positive electrode active material layer contains typical nonmetallic elements such as B, N, P, F, Cl, Br, and I, Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, Ba, and the like.
  • typical metal elements, transition metal elements such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Nb, W are used as positive electrode active materials, conductive agents, binders, thickeners, fillers It may be contained as a component other than
  • the mass per unit area of the positive electrode active material layer is preferably 4 mg/cm 2 or more and 12 mg/cm 2 or less, more preferably 5 mg/cm 2 or more and 8 mg/cm 2 or less.
  • the mass per unit area of the positive electrode active material layer refers to the mass per unit area of one positive electrode active material layer.
  • the “mass per unit area of the positive electrode active material layer” is the positive electrode active material layer on one side. It is the mass per unit area of the material layer.
  • the negative electrode has a negative electrode base material and a negative electrode active material layer disposed directly on the negative electrode base material or via an intermediate layer.
  • the structure of the intermediate layer is not particularly limited, and can be selected from, for example, the structures exemplified for the positive electrode.
  • the negative electrode base material has conductivity.
  • materials for the negative electrode substrate metals such as copper, nickel, stainless steel, nickel-plated steel, alloys thereof, carbonaceous materials, and the like are used. Among these, copper or a copper alloy is preferred.
  • negative electrode substrates include foils, deposited films, meshes, porous materials, and the like, and foils are preferred from the viewpoint of cost. Therefore, copper foil or copper alloy foil is preferable as the negative electrode substrate.
  • Examples of copper foil include rolled copper foil and electrolytic copper foil.
  • the average thickness of the negative electrode substrate is preferably 2 ⁇ m or more and 35 ⁇ m or less, more preferably 3 ⁇ m or more and 30 ⁇ m or less, even more preferably 4 ⁇ m or more and 25 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 20 ⁇ m or less.
  • the negative electrode active material layer contains a negative electrode active material.
  • the negative electrode active material layer contains arbitrary components such as a conductive agent, a binder, a thickener, a filler, etc., as required.
  • Optional components such as conductive agents, binders, thickeners, and fillers can be selected from the materials exemplified for the positive electrode.
  • the negative electrode active material layer contains typical nonmetallic elements such as B, N, P, F, Cl, Br, and I, Li, Na, Mg, Al, K, Ca, Zn, Ga, Ge, Sn, Sr, Ba, and the like. and transition metal elements such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Zr, Ta, Hf, Nb, and W are used as negative electrode active materials, conductive agents, binders, and thickeners. You may contain as a component other than a sticky agent and a filler.
  • the negative electrode active material contains solid graphite. By including solid graphite in the negative electrode active material, it is possible to suppress an increase in resistance after charge-discharge cycles.
  • the area ratio (porosity) of voids in the particles to the area of the entire particles in the cross section of the solid graphite observed in the above SEM image is 2% or less, more preferably 1% or less, and 0.5% or less. is more preferred. In some embodiments, the area ratio (porosity) of solid graphite may be 0.3% or less, or 0.1% or less. The lower limit of this area ratio (void ratio) may be 0%. In some embodiments, the area ratio (porosity) of solid graphite may be 0.03% or more, or 0.3% or more.
  • the solid graphite may be natural graphite or artificial graphite, but natural graphite is preferable.
  • the solid graphite is natural graphite (solid natural graphite)
  • the initial resistance of the non-aqueous electrolyte storage element can be made lower, and an increase in resistance after charge/discharge cycles can be suppressed.
  • Natural graphite is a general term for graphite obtained from natural resources.
  • the shape of the solid natural graphite is not particularly limited, and examples thereof include flaky graphite, massive graphite (flaky graphite), earthy graphite, and the like.
  • the solid natural graphite may be spheroidized natural graphite particles obtained by spheroidizing flake natural graphite or the like.
  • the natural graphite may have four peaks in the diffraction angle 2 ⁇ range of 40° to 50° in an X-ray diffraction pattern using CuK ⁇ rays measured before charging/discharging or in a discharged state.
  • the ratio of the peak intensity derived from the (012) plane to the peak intensity derived from the (100) plane is preferably 0.3 or more, more preferably 0.4 or more.
  • the peak intensity ratio ((012)/(100)) is preferably 0.6 or less.
  • the (100) plane is derived from the hexagonal crystal structure
  • the (012) plane is derived from the rhombohedral crystal structure.
  • the average particle diameter of solid graphite is preferably 1 ⁇ m or more and 25 ⁇ m or less, more preferably 4 ⁇ m or more and 20 ⁇ m or less, and even more preferably 5 ⁇ m or more and 15 ⁇ m or less.
  • the lower limit of the average particle size of solid graphite is more preferably 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, or 9 ⁇ m.
  • the average particle size of the solid graphite is at least the above lower limit, the contact of the solid graphite with the negative electrode substrate and the contact between the particles of the solid graphite are enhanced, and as a result, after charge-discharge cycles, An increase in resistance is further suppressed, and productivity and the like are enhanced.
  • a pulverizer, a classifier, or the like is used to obtain solid graphite with a predetermined particle size.
  • the pulverization method and classification method can be selected from, for example, the methods exemplified for the positive electrode.
  • Solid graphite may be particles with pores on the surface.
  • the porosity of the solid graphite is preferably 5% or more and 20% or less, more preferably 9% or more and 15% or less.
  • a sufficient surface area can be secured, and charge/discharge performance can be improved.
  • the porosity of the solid graphite is equal to or less than the above upper limit, the particles become dense, and the energy density can be increased.
  • "Porosity” is a value indicating the ratio of pores (pores), and is a value based on the total pore volume measured by the BJH method.
  • solid graphite when solid graphite can be prepared before manufacturing the negative electrode, it is directly subjected to the measurement of the total pore volume.
  • the negative electrode When preparing from the non-aqueous electrolyte storage element after assembly, the negative electrode in a discharged state by the procedure of measuring the "area ratio (porosity) of voids in the particles with respect to the area of the whole particles" By repeating the process of collecting graphite and immersing it in dimethyl carbonate for 5 minutes twice, the non-aqueous electrolyte is sufficiently removed, and the solid graphite is dried under reduced pressure at room temperature for 24 hours for the measurement of the total pore volume. provide.
  • the porosity (%) is obtained by the following formula 2.
  • Porosity (%) V/ ⁇ V+(1/D) ⁇ ...2
  • the measurement of the total pore volume by the BJH method does not measure the volume of voids in the particles that are closed from the outside. It is an index different from the area ratio (porosity) of voids in the particles with respect to the area of .
  • the content of solid graphite in the negative electrode active material layer is preferably 60% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 98% by mass or less, and is 95% by mass or more, 97% by mass or more, or 98% by mass or more. is more preferred in some cases.
  • the negative electrode active material may contain other negative electrode active materials other than solid graphite.
  • Other negative electrode active materials include hollow graphite (graphite other than solid graphite, graphite in which the area ratio of voids in particles to the area of the entire particle in the cross section of the graphite observed in the SEM image is more than 2%). and other conventionally known various negative electrode active materials can be used.
  • the content of solid graphite in all negative electrode active materials contained in the negative electrode active material layer is preferably 90% by mass or more, more preferably 99% by mass or more, and may be substantially 100% by mass. .
  • the volume change of the negative electrode active material layer due to the expansion and contraction of the negative electrode active material due to charging and discharging is particularly sufficiently suppressed, and the resistance after charging and discharging cycles is reduced. Increase can be suppressed more.
  • the content of all negative electrode active materials in the negative electrode active material layer is preferably 60% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 98% by mass or less.
  • the content of all negative electrode active materials in the negative electrode active material layer may be 95% by mass or more, 97% by mass or more, or 98% by mass or more.
  • the content of the binder in the negative electrode active material layer is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 6% by mass or less.
  • the content of the binder in the negative electrode active material layer may be 3% by mass or less, 2% by mass or less, or 1.5% by mass or less (for example, 1.2% by mass or less).
  • the content of the thickener in the negative electrode active material layer is preferably 0.3% by mass or more and 4% by mass or less, more preferably 0.5% by mass or more and 2% by mass or less.
  • the mass per unit area of the negative electrode active material layer is preferably 2.5 mg/cm 2 or more and 6 mg/cm 2 or less, more preferably 3 mg/cm 2 or more and 5 mg/cm 2 or less.
  • the mass per unit area of the negative electrode active material layer refers to the mass per unit area of one negative electrode active material layer.
  • the “mass per unit area of the negative electrode active material layer” is the negative electrode active material layer on one surface. It is the mass per unit area of the material layer.
  • the separator can be appropriately selected from known separators.
  • a separator consisting of only a substrate layer, a separator having a heat-resistant layer containing heat-resistant particles and a binder formed on one or both surfaces of a substrate layer, or the like can be used.
  • Examples of the shape of the base layer of the separator include woven fabric, nonwoven fabric, and porous resin film. Among these shapes, a porous resin film is preferred from the viewpoint of strength, and a non-woven fabric is preferred from the viewpoint of non-aqueous electrolyte retention.
  • polyolefins such as polyethylene and polypropylene are preferable from the viewpoint of shutdown function, and polyimide, aramid, and the like are preferable from the viewpoint of oxidative decomposition resistance.
  • a material obtained by combining these resins may be used as the base material layer of the separator.
  • the heat-resistant particles contained in the heat-resistant layer preferably have a mass loss of 5% or less when the temperature is raised from room temperature to 500 ° C. in an air atmosphere of 1 atm, and the mass loss when the temperature is raised from room temperature to 800 ° C. is more preferably 5% or less.
  • An inorganic compound can be mentioned as a material whose mass reduction is less than or equal to a predetermined value. Examples of inorganic compounds include oxides such as iron oxide, silicon oxide, aluminum oxide, titanium oxide, zirconium oxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide, and aluminosilicate; nitrides such as aluminum nitride and silicon nitride.
  • carbonates such as calcium carbonate
  • sulfates such as barium sulfate
  • sparingly soluble ionic crystals such as calcium fluoride, barium fluoride, and barium titanate
  • covalent crystals such as silicon and diamond
  • Mineral resource-derived substances such as zeolite, apatite, kaolin, mullite, spinel, olivine, sericite, bentonite, and mica, or artificial products thereof.
  • the inorganic compound a single substance or a composite of these substances may be used alone, or two or more of them may be mixed and used.
  • silicon oxide, aluminum oxide, or aluminosilicate is preferable from the viewpoint of the safety of the electric storage device.
  • the porosity of the separator is preferably 80% by volume or less from the viewpoint of strength, and preferably 20% by volume or more from the viewpoint of discharge performance.
  • the "porosity” is a volume-based value and means a value measured with a mercury porosimeter.
  • a polymer gel composed of a polymer and a non-aqueous electrolyte may be used as the separator.
  • examples of polymers include polyacrylonitrile, polyethylene oxide, polypropylene oxide, polymethyl methacrylate, polyvinyl acetate, polyvinylpyrrolidone, polyvinylidene fluoride, and the like.
  • the use of polymer gel has the effect of suppressing liquid leakage.
  • a polymer gel may be used in combination with the porous resin film or non-woven fabric as described above.
  • Non-aqueous electrolyte The non-aqueous electrolyte can be appropriately selected from known non-aqueous electrolytes. A non-aqueous electrolyte may be used as the non-aqueous electrolyte.
  • the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in this non-aqueous solvent.
  • the non-aqueous solvent can be appropriately selected from known non-aqueous solvents.
  • Non-aqueous solvents include cyclic carbonates, chain carbonates, carboxylic acid esters, phosphoric acid esters, sulfonic acid esters, ethers, amides, nitriles and the like.
  • the non-aqueous solvent those in which some of the hydrogen atoms contained in these compounds are substituted with halogen atoms may be used.
  • Cyclic carbonates include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), vinylethylene carbonate (VEC), chloroethylene carbonate, fluoroethylene carbonate (FEC), and difluoroethylene carbonate. (DFEC), styrene carbonate, 1-phenylvinylene carbonate, 1,2-diphenylvinylene carbonate and the like. Among these, EC is preferred.
  • chain carbonates examples include diethyl carbonate (DEC), dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), diphenyl carbonate, trifluoroethylmethyl carbonate, bis(trifluoroethyl) carbonate, and the like. Among these, EMC is preferred.
  • the non-aqueous solvent it is preferable to use a cyclic carbonate or a chain carbonate, and it is more preferable to use a combination of a cyclic carbonate and a chain carbonate.
  • a cyclic carbonate it is possible to promote the dissociation of the electrolyte salt and improve the ionic conductivity of the non-aqueous electrolyte.
  • a chain carbonate By using a chain carbonate, the viscosity of the non-aqueous electrolyte can be kept low.
  • the volume ratio of the cyclic carbonate to the chain carbonate is preferably in the range of, for example, 5:95 to 50:50.
  • electrolyte salt it is usually possible to appropriately select and use it from known lithium salts.
  • Lithium salts include inorganic lithium salts such as LiPF 6 , LiPO 2 F 2 , LiBF 4 , LiClO 4 and LiN(SO 2 F) 2 , lithium bis(oxalate) borate (LiBOB), lithium difluorooxalate borate (LiFOB).
  • lithium oxalate salts such as lithium bis ( oxalate) difluorophosphate (LiFOP), LiSO3CF3 , LiN( SO2CF3 ) 2 , LiN ( SO2C2F5 ) 2 , LiN( SO2CF3 ) (SO 2 C 4 F 9 ), LiC(SO 2 CF 3 ) 3 , LiC(SO 2 C 2 F 5 ) 3 and other lithium salts having halogenated hydrocarbon groups.
  • inorganic lithium salts are preferred, and LiPF 6 is more preferred.
  • the content of the electrolyte salt in the non-aqueous electrolyte is preferably 0.1 mol/dm 3 or more and 2.5 mol/dm 3 or less, more preferably 0.3 mol/dm 3 or more and 2.0 mol/dm at 20° C. and 1 atm. 3 or less, more preferably 0.5 mol/dm 3 or more and 1.7 mol/dm 3 or less, and particularly preferably 0.7 mol/dm 3 or more and 1.5 mol/dm 3 or less.
  • the non-aqueous electrolyte may contain additives in addition to the non-aqueous solvent and electrolyte salt.
  • additives include aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, and dibenzofuran; 2-fluorobiphenyl, Partial halides of the above aromatic compounds such as o-cyclohexylfluorobenzene and p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroanisole, 3,5-difluoroanisole, etc.
  • the content of the additive contained in the nonaqueous electrolyte is preferably 0.01% by mass or more and 10% by mass or less, and 0.1% by mass or more and 7% by mass or less with respect to the total mass of the nonaqueous electrolyte. More preferably, it is 0.2% by mass or more and 5% by mass or less, and particularly preferably 0.3% by mass or more and 3% by mass or less.
  • a solid electrolyte may be used as the non-aqueous electrolyte, or a non-aqueous electrolyte and a solid electrolyte may be used together.
  • the solid electrolyte can be selected from any material that has lithium ion conductivity and is solid at room temperature (for example, 15°C to 25°C).
  • Examples of solid electrolytes include sulfide solid electrolytes, oxide solid electrolytes, nitride solid electrolytes, polymer solid electrolytes, and the like.
  • Examples of sulfide solid electrolytes include Li 2 SP 2 S 5 , LiI-Li 2 SP 2 S 5 and Li 10 Ge-P 2 S 12 .
  • the shape of the non-aqueous electrolyte storage element of the present embodiment is not particularly limited, and examples thereof include cylindrical batteries, square batteries, flat batteries, coin batteries, button batteries, and the like.
  • Fig. 1 shows a non-aqueous electrolyte storage element 1 as an example of a square battery.
  • An electrode body 2 having a positive electrode and a negative electrode wound with a separator sandwiched therebetween is housed in a rectangular container 3 .
  • the positive electrode is electrically connected to the positive electrode terminal 4 via a positive electrode lead 41 .
  • the negative electrode is electrically connected to the negative terminal 5 via a negative lead 51 .
  • the non-aqueous electrolyte storage element of the present embodiment is a power source for automobiles such as electric vehicles (EV), hybrid vehicles (HEV), and plug-in hybrid vehicles (PHEV), power sources for electronic devices such as personal computers and communication terminals, or electric power It can be installed in a storage power source or the like as a power storage unit (battery module) configured by assembling a plurality of non-aqueous electrolyte power storage elements.
  • the technology of the present invention may be applied to at least one non-aqueous electrolyte storage element included in the storage unit.
  • FIG. 2 shows an example of a power storage device 30 in which a power storage unit 20 in which two or more electrically connected non-aqueous electrolyte power storage elements 1 are assembled is further assembled.
  • the power storage device 30 includes a bus bar (not shown) electrically connecting two or more non-aqueous electrolyte power storage elements 1, a bus bar (not shown) electrically connecting two or more power storage units 20, and the like. good too.
  • the power storage unit 20 or the power storage device 30 may include a state monitoring device (not shown) that monitors the state of one or more non-aqueous electrolyte power storage elements.
  • the method for manufacturing the non-aqueous electrolyte storage element of the present embodiment can be appropriately selected from known methods.
  • the manufacturing method includes, for example, preparing an electrode body, preparing a non-aqueous electrolyte, and housing the electrode body and the non-aqueous electrolyte in a container.
  • Preparing the electrode body includes preparing a positive electrode and a negative electrode, and forming the electrode body by laminating or winding the positive electrode and the negative electrode with a separator interposed therebetween.
  • Containing the non-aqueous electrolyte in the container can be appropriately selected from known methods.
  • the non-aqueous electrolyte may be injected through an inlet formed in the container, and then the inlet may be sealed.
  • non-aqueous electrolyte storage device of the present invention is not limited to the above embodiments, and various modifications may be made without departing from the gist of the present invention.
  • the configuration of another embodiment can be added to the configuration of one embodiment, and part of the configuration of one embodiment can be replaced with the configuration of another embodiment or a known technique.
  • some of the configurations of certain embodiments can be deleted.
  • well-known techniques can be added to the configuration of a certain embodiment.
  • the nonaqueous electrolyte storage element is used as a chargeable/dischargeable nonaqueous electrolyte secondary battery (lithium ion secondary battery). etc. are optional.
  • the present invention can also be applied to various secondary batteries.
  • the electrode body in which the positive electrode and the negative electrode are laminated with a separator interposed therebetween has been described, but the electrode body does not have to have a separator.
  • the positive electrode and the negative electrode may be in direct contact with each other in a state in which a layer having no conductivity is formed on the active material layer of the positive electrode or the negative electrode.
  • Example 1 (Preparation of positive electrode) LiNi 0.50 Co 0.35 Mn 0.15 O 2 as a positive electrode active material, acetylene black (AB) as a conductive agent, polyvinylidene fluoride (PVDF) as a binder, and N-methylpyrrolidone (NMP) as a dispersion medium were used for positive electrode synthesis.
  • agent paste was prepared.
  • the mass ratio of the positive electrode active material, AB and PVDF was 93:3.5:3.5 (in terms of solid content).
  • the positive electrode material mixture paste was applied to both surfaces of an aluminum foil serving as a positive electrode base material so that the coating weight of the solid content was 7.0 mg/cm 2 and dried. After that, roll pressing was performed to obtain a positive electrode.
  • Non-aqueous electrolyte LiPF 6 was dissolved at a concentration of 1.2 mol/dm 3 in a solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 30:70 to obtain a non-aqueous electrolyte.
  • a wound electrode body was obtained using the positive electrode, the negative electrode, and the separator.
  • the electrode body was placed in a container, a non-aqueous electrolyte was injected, and the container was sealed to obtain a non-aqueous electrolyte storage element (secondary battery) of Example 1.
  • Non-aqueous electrolyte storage elements of Comparative Examples 1 and 2 and Reference Example 1 were obtained in the same manner as in Example 1, except that the positive electrode active material and the negative electrode active material shown in Table 1 were used.
  • the hollow natural graphite in Table 1 had a porosity of 3%, a porosity of 7.5%, and an average particle size of 9.1 ⁇ m.
  • Table 1 shows the initial resistance of the non-aqueous electrolyte storage element having LiNi 0.33 Co 0.33 Mn 0.33 O 2 as the positive electrode active material among the non-aqueous electrolyte storage elements using the same negative electrode active material as a reference (100%).
  • the initial resistance (relative value) of the non-aqueous electrolyte storage element is shown. That is, the initial resistance of Example 1 indicates a relative value based on the initial resistance of Comparative Example 1, and the initial resistance of Reference Example 1 indicates a relative value based on the initial resistance of Comparative Example 2.
  • the positive electrode active material contains nickel element and manganese element, and the content of nickel element relative to the transition metal element is 40 mol% or more, or manganese It can be seen that the initial resistance of the non-aqueous electrolyte storage element is low when the lithium-transition gold electrode composite oxide having an element content of 30 mol % or less is used.
  • Example 2 (Preparation of positive electrode) LiNi 0.50 Co 0.35 Mn 0.15 O 2 as a positive electrode active material, acetylene black (AB) as a conductive agent, polyvinylidene fluoride (PVDF) as a binder, and N-methylpyrrolidone (NMP) as a dispersion medium were used for positive electrode synthesis. agent paste was prepared. The mass ratio of the positive electrode active material, AB and PVDF was 93:3.5:3.5 (in terms of solid content). A positive electrode material mixture paste was applied to both surfaces of an aluminum foil serving as a positive electrode substrate and dried. After that, roll pressing was performed to obtain a positive electrode.
  • AB acetylene black
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • Non-aqueous electrolyte LiPF 6 was dissolved at a concentration of 1.2 mol/dm 3 in a solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 30:70 to obtain a non-aqueous electrolyte.
  • a wound electrode body was obtained using the positive electrode, the negative electrode, and the separator.
  • the electrode body was placed in a container, a non-aqueous electrolyte was injected, and the container was sealed to obtain a non-aqueous electrolyte storage element (secondary battery) of Example 2.
  • Non-aqueous electrolyte storage elements of Comparative Examples 3 to 5 were obtained in the same manner as in Example 2, except that the positive electrode active material and negative electrode active material shown in Table 2 were used.
  • the hollow natural graphite in Table 2 had a porosity of 3%, a porosity of 7.5%, and an average particle size of 9.1 ⁇ m.
  • constant current charging was performed at a charging current of 8 C to an amount of electricity equivalent to 80% of the initial discharge capacity, and the non-aqueous electrolyte storage element was adjusted to an SOC of 80%.
  • constant current discharge was carried out at a discharge current of 8 C to an amount of electricity equivalent to 60% of the initial discharge capacity, and the non-aqueous electrolyte storage element was adjusted to an SOC of 20%.
  • constant-current charging was performed with an amount of electricity equivalent to 60% of the initial discharge capacity without providing a rest period, and the non-aqueous electrolyte storage element was adjusted to an SOC of 80%.
  • the resistance increase rate (%) of each non-aqueous electrolyte storage element was obtained from the initial resistance and the resistance after charge-discharge cycles, and the resistance increase suppression rate (%) of each non-aqueous electrolyte storage element of Example 2 and Comparative Example 4 was calculated. asked.
  • x is the resistance increase rate of the non-aqueous electrolyte storage element X (Comparative Example 3 or Comparative Example 5) in which the negative electrode active material is hollow graphite.
  • y is the resistance increase rate of the non-aqueous electrolyte storage element Y (Example 2 or Comparative Example 4), which differs from the non-aqueous electrolyte storage element X only in that the negative electrode active material is solid graphite.
  • the non-aqueous electrolyte storage element X is the non-aqueous electrolyte storage element of Comparative Example 3
  • the non-aqueous electrolyte storage element Y is the non-aqueous electrolyte storage element of Example 3.
  • Table 2 shows the obtained resistance increase suppression rate (%) of each of the non-aqueous electrolyte storage elements of Example 2 and Comparative Example 4.
  • the positive electrode active material contains nickel element and manganese element, and the content of nickel element with respect to the transition metal element is 40 mol% or more, or manganese It can be seen that when a lithium-transition gold electrode composite oxide having an element content of 30 mol % or less is used, an increase in resistance after charge-discharge cycles can be suppressed by using solid graphite as the negative electrode active material.
  • Comparative Examples 4 and 5 it contains nickel element and manganese element, and the content of nickel element with respect to the transition metal element is 40 mol% or more, or the content of manganese element is 30 mol% or less.
  • Example 3 (Preparation of positive electrode) LiNi 0.45 Co 0.35 Mn 0.20 O 2 as a positive electrode active material, acetylene black (AB) as a conductive agent, polyvinylidene fluoride (PVDF) as a binder, and N-methylpyrrolidone (NMP) as a dispersion medium were used for positive electrode synthesis.
  • agent paste was prepared.
  • the mass ratio of the positive electrode active material, AB and PVDF was 93:3.5:3.5 (in terms of solid content).
  • the positive electrode material mixture paste was applied to both surfaces of an aluminum foil serving as a positive electrode substrate so that the coating weight of the solid content was 7.1 mg/cm 2 and dried. After that, roll pressing was performed to obtain a positive electrode.
  • Non-aqueous electrolyte LiPF 6 was dissolved at a concentration of 1.2 mol/dm 3 in a solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 30:70 to obtain a non-aqueous electrolyte.
  • a wound electrode body was obtained using the positive electrode, the negative electrode, and the separator.
  • the electrode body was placed in a container, a non-aqueous electrolyte was injected, and the container was sealed to obtain a non-aqueous electrolyte storage element (secondary battery) of Example 3.
  • Comparative Example 6 A non-aqueous electrolyte storage element of Comparative Example 6 was obtained in the same manner as in Example 3, except that the negative electrode active material shown in Table 3 was used.
  • the hollow natural graphite in Table 3 had a porosity of 3%, a porosity of 7.5%, and an average particle size of 9.1 ⁇ m.
  • the non-aqueous electrolyte storage element of Example 3 can also suppress an increase in resistance after charge-discharge cycles, as in the case of the non-aqueous electrolyte storage element of Example 2 above.
  • Example 4 (Preparation of positive electrode) LiNi 0.45 Co 0.35 Mn 0.20 O 2 as a positive electrode active material, acetylene black (AB) as a conductive agent, polyvinylidene fluoride (PVDF) as a binder, and N-methylpyrrolidone (NMP) as a dispersion medium were used for positive electrode synthesis.
  • agent paste was prepared.
  • the mass ratio of the positive electrode active material, AB and PVDF was 93:3.5:3.5 (in terms of solid content).
  • the positive electrode material mixture paste was applied to both surfaces of an aluminum foil serving as a positive electrode substrate so that the coating weight of the solid content was 6.6 mg/cm 2 and dried. After that, roll pressing was performed to obtain a positive electrode.
  • Non-aqueous electrolyte LiPF 6 was dissolved at a concentration of 1.2 mol/dm 3 in a solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 30:70 to obtain a non-aqueous electrolyte.
  • a wound electrode body was obtained using the positive electrode, the negative electrode, and the separator.
  • the electrode body was placed in a container, a non-aqueous electrolyte was injected, and the container was sealed to obtain a non-aqueous electrolyte storage element (secondary battery) of Example 4.
  • Nonaqueous electrolyte storage elements of Comparative Examples 7 to 9 were obtained in the same manner as in Example 4, except that the positive electrode active material and negative electrode active material shown in Table 4 were used.
  • the natural hollow graphite in Table 4 had a porosity of 3%, a porosity of 7.5%, and an average particle size of 9.1 ⁇ m.
  • constant current charging was performed at a charging current of 8 C to an amount of electricity equivalent to 85% of the initial discharge capacity, thereby adjusting the SOC of the non-aqueous electrolyte storage element to 85%.
  • constant current discharge was carried out at a discharge current of 8 C to an amount of electricity equivalent to 70% of the initial discharge capacity, and the non-aqueous electrolyte storage element was adjusted to an SOC of 15%.
  • constant-current charging was performed with an amount of electricity equivalent to 70% of the initial discharge capacity without providing a rest period, and the nonaqueous electrolyte storage element was adjusted to an SOC of 85%.
  • the resistance increase rate (%) was determined, and the resistance increase suppression rate (%) in each of the non-aqueous electrolyte storage elements of Example 4 and Comparative Example 8 was determined.
  • the non-aqueous electrolyte storage element of Example 4 can also suppress an increase in resistance after charge/discharge cycles, similarly to the non-aqueous electrolyte storage elements of Examples 2 and 3 above.
  • the charge-discharge cycle tests in the examples and comparative examples in Table 4 have a large difference in SOC between charge and discharge, and such a comparison It can be seen that in the case of charge-discharge cycles under extremely severe conditions, the effect of suppressing the increase in resistance after charge-discharge cycles by using solid graphite as a negative electrode active material is remarkably produced.
  • a negative electrode mixture paste was prepared using solid natural graphite as a negative electrode active material, styrene-butadiene rubber (SBR) as a binder, carboxymethyl cellulose (CMC) as a thickener, and water as a dispersion medium. The mass ratio of graphite, SBR and CMC was 98:1:1 (in terms of solid content).
  • a negative electrode mixture paste was applied to the surface of a copper foil as a negative electrode substrate and dried. Thereafter, roll pressing was performed to obtain a negative electrode in which a negative electrode active material layer was laminated on one surface of the negative electrode substrate.
  • various solid natural graphites having average particle diameters shown in Table 5
  • the present invention can be applied to electronic devices such as personal computers and communication terminals, non-aqueous electrolyte storage elements used as power sources for automobiles and the like.
  • Nonaqueous electrolyte storage element 1 Nonaqueous electrolyte storage element 2 Electrode body 3 Container 4 Positive electrode terminal 41 Positive electrode lead 5 Negative electrode terminal 51 Negative electrode lead 20 Storage unit 30 Storage device

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