WO2021015194A1 - 蓄電素子 - Google Patents

蓄電素子 Download PDF

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Publication number
WO2021015194A1
WO2021015194A1 PCT/JP2020/028239 JP2020028239W WO2021015194A1 WO 2021015194 A1 WO2021015194 A1 WO 2021015194A1 JP 2020028239 W JP2020028239 W JP 2020028239W WO 2021015194 A1 WO2021015194 A1 WO 2021015194A1
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Prior art keywords
negative electrode
graphite particles
active material
electrode active
material layer
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PCT/JP2020/028239
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English (en)
French (fr)
Japanese (ja)
Inventor
謙太 尾木
慧 熊林
明彦 宮崎
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GS Yuasa International Ltd
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GS Yuasa International Ltd
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Priority to CN202080052614.8A priority Critical patent/CN114144906A/zh
Priority to JP2021534044A priority patent/JPWO2021015194A1/ja
Priority to EP20843065.2A priority patent/EP3975286A4/en
Priority to US17/597,560 priority patent/US12381223B2/en
Publication of WO2021015194A1 publication Critical patent/WO2021015194A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025121606A priority patent/JP2025157454A/ja
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01G11/42—Powders or particles, e.g. composition thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • 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
    • 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
    • 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
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
    • H01M50/103—Primary casings; Jackets or wrappings characterised by their shape or physical structure prismatic or rectangular
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • 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
    • H01G11/04—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
    • 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
    • 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 power storage element.
  • Non-aqueous electrolyte secondary batteries represented by lithium-ion non-aqueous electrolyte secondary batteries are widely used in electronic devices such as personal computers and communication terminals, automobiles, etc. due to their high energy density.
  • the non-aqueous electrolyte secondary battery generally includes an electrode body having a pair of electrodes electrically separated by a separator, and a non-aqueous electrolyte interposed between the electrodes, and transfers ions between the two electrodes. It is configured to charge and discharge by doing so.
  • capacitors such as lithium ion capacitors and electric double layer capacitors are also widely used as power storage elements other than non-aqueous electrolyte secondary batteries.
  • a carbon material such as graphite having a large charge / discharge capacity is used as the negative electrode active material of the power storage element for the purpose of increasing the energy density of the power storage element and improving the charge / discharge efficiency (patented). Reference 1).
  • the present invention has been made based on the above circumstances, and when graphite is used as the negative electrode active material, the negative electrode active material layer has no or little pressure applied to the negative electrode active material layer.
  • An object of the present invention is to provide a power storage element including a negative electrode having a high discharge capacity per volume.
  • One aspect of the present invention made to solve the above problems includes a negative electrode having a negative electrode base material and a negative electrode active material layer directly or indirectly laminated on at least one surface of the negative electrode base material.
  • a power storage element including a negative electrode having a high discharge capacity per volume of the negative electrode active material layer even when there is no pressure applied to the negative electrode active material layer or when the pressure is small. can be obtained.
  • FIG. 1 is an external perspective view showing a power storage element according to an embodiment of the present invention.
  • FIG. 2 is a schematic view showing a power storage device configured by assembling a plurality of power storage elements according to an embodiment of the present invention.
  • FIG. 3 is a graph showing the relationship between the content ratio of solid graphite particles in Examples and Comparative Examples and the discharge capacity per volume of the negative electrode active material layer.
  • FIG. 4 is a graph showing the relationship between the content ratio of solid graphite particles in Examples and Comparative Examples and the expansion coefficient of the negative electrode active material at the time of initial charging.
  • the power storage element includes a negative electrode having a negative electrode base material and a negative electrode active material layer directly or indirectly laminated on at least one surface of the negative electrode base material, and the negative electrode active material layer
  • the negative electrode active material contains a negative electrode active material
  • the negative electrode active material contains hollow graphite particles having a median diameter D1 and solid graphite particles having a median diameter D2 smaller than the hollow graphite particles.
  • the power storage element contains hollow graphite particles having a median diameter D1 as a negative electrode active material and solid graphite particles having a median diameter D2 smaller than the hollow graphite particles, whereby the hollow graphite particles and the solid graphite particles are contained.
  • the discharge capacity per volume of the negative electrode active material layer when unpressed is higher than that containing any of the above alone, and the synergistic effect of the hollow graphite particles and the solid graphite particles can be obtained. Therefore, it is possible to obtain a power storage element having a negative electrode having an excellent discharge capacity per volume of the negative electrode active material layer without increasing the density by a high-pressure press.
  • the content ratio of the hollow graphite particles to the total content of the hollow graphite particles and the solid graphite particles is 80% by mass or less.
  • the discharge capacity per volume of the negative electrode active material layer can be further increased.
  • the negative electrode active material layer is not substantially pressed. According to such a configuration, it is possible to increase the discharge capacity per volume of the negative electrode active material layer while suppressing inconveniences (for example, expansion of the negative electrode that occurs during initial charging) that may occur by pressing the negative electrode active material layer.
  • the density of the negative electrode active material layer is 1.30 g / cm 3 or more and 1.55 g / cm 3 or less.
  • the application effect of this configuration is more preferably applied to a power storage element in which the density of the negative electrode active material layer containing hollow graphite particles and solid graphite particles as the negative electrode active material is 1.30 g / cm 3 or more and 1.55 g / cm 3 or less. Can be demonstrated.
  • the median diameter of the solid graphite particles is 4 ⁇ m or less.
  • the above-mentioned performance improving effect for example, the effect of increasing the discharge capacity per volume of the negative electrode active material layer when not pressed
  • the output of the power storage element can be further improved.
  • the aspect ratio of the solid graphite particles is 1 or more and 5 or less.
  • the above-mentioned performance improving effect for example, the effect of increasing the discharge capacity per volume of the negative electrode active material layer when not pressed
  • the above-mentioned performance improving effect can be better exhibited.
  • each component (each component) used in each embodiment may be different from the name of each component (each component) used in the background technology.
  • the power storage element includes a positive electrode, a negative electrode, and a non-aqueous electrolyte.
  • the positive electrode and the negative electrode usually form an electrode body laminated or wound via a separator.
  • the electrode body is housed in a container, and the container is filled with a non-aqueous electrolyte.
  • the non-aqueous electrolyte is interposed between the positive electrode and the negative electrode.
  • a non-aqueous electrolyte secondary battery will be described.
  • the negative electrode includes a negative electrode base material and a negative electrode active material layer that is directly or indirectly laminated on at least one surface of the negative electrode base material.
  • the negative electrode may include an intermediate layer arranged between the negative electrode base material and the negative electrode active material layer.
  • the negative electrode base material has conductivity.
  • metals such as copper, nickel, stainless steel, nickel-plated steel, or alloys thereof are used. Among these, copper or a copper alloy is preferable.
  • the negative electrode base material include foils and vapor-deposited films, and foils are preferable from the viewpoint of cost. Therefore, a copper foil or a copper alloy foil is preferable as the negative electrode base material.
  • the copper foil include rolled copper foil, electrolytic copper foil and the like.
  • conductive means that the volume resistivity is measured according to JIS-H0505 (1975) is not more than 1 ⁇ 10 7 ⁇ ⁇ cm, and “non-conductive” are means that the volume resistivity is 1 ⁇ 10 7 ⁇ ⁇ cm greater.
  • the average thickness of the negative electrode base material is preferably 2 ⁇ m or more and 35 ⁇ m or less, more preferably 3 ⁇ m or more and 30 ⁇ m or less, further preferably 4 ⁇ m or more and 25 ⁇ m or less, and particularly preferably 5 ⁇ m or more and 20 ⁇ m or less.
  • the "average thickness of the base material” means a value obtained by dividing the punching mass when a base material having a predetermined area is punched by the true density of the base material and the punched area.
  • the negative electrode active material layer is arranged along at least one surface of the negative electrode base material, either directly or via an intermediate layer.
  • the negative electrode active material layer contains a negative electrode active material.
  • the negative electrode active material disclosed here contains hollow graphite particles having a median diameter D1 and solid graphite particles having a median diameter D2 smaller than the hollow graphite particles.
  • graphite is a carbon substance having an average lattice spacing d (002) of (002) planes measured by X-ray diffraction before charging / discharging or in a discharged state of less than 0.34 nm. ..
  • solid means that the inside of the particle is clogged and there is virtually no void. More specifically, in the present specification, “solid” means a particle with respect to the total area of the particle in the cross section of the particle observed in the SEM image obtained by using a scanning electron microscope (SEM). It means that the area ratio excluding the voids inside is 95% or more. In a preferred embodiment, the area ratio of the solid graphite particles can be 97% or higher (eg, 99% or higher). The term “hollow” means that the area ratio of the total area of the particles excluding voids in the particles is less than 95% in the cross section of the particles observed in the SEM image obtained by using SEM. In a preferred embodiment, the area ratio of the hollow graphite particles can be 92% or less (eg 90% or less).
  • the area ratio R of the graphite particles excluding the voids in the particles with respect to the total area of the particles can be determined by the following procedure.
  • (1) Preparation of sample for measurement The powder of graphite particles to be measured is fixed with a thermosetting resin.
  • a cross section is exposed by using a cross section polisher to prepare a sample for measurement.
  • (2) Acquisition of SEM image JSM-7001F (manufactured by JEOL Ltd.) is used as a scanning electron microscope to acquire the SEM image.
  • the SEM image shall be an observation of 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, focus, etc. are appropriately set so that the outline of the graphite particles becomes clear.
  • Cutout of contour of graphite particles Using the image cropping function of the image editing software Adobe Photoshop Elements 11, the contour of graphite particles is cut out from the acquired SEM image. This contour cropping is performed by selecting the outside of the contour of the active material particles using the quick selection tool and editing the non-graphite particles to a black background.
  • Binarization processing For the image of the first graphite particles among the cut out graphite particles, use the image analysis software PopImaging 6.00 and set the threshold value to a concentration 20% smaller than the concentration that maximizes the intensity. And perform binarization processing. By the binarization process, the area on the low concentration side is calculated to obtain "area S1 excluding voids in the particles". Then, the same image of the first graphite particles as before is subjected to a binarization process with a density of 10 as a threshold value.
  • the outer edge of the graphite particles is determined by the binarization treatment, and the area inside the outer edge is calculated to obtain "the total area S0 of the particles".
  • S1 S1 / S0
  • area ratio R1 excluding voids in the particles to the total area of the particles in the first graphite particle. Is calculated.
  • the image of the second and subsequent graphite particles among the cut out graphite particles is also subjected to the above binarization treatment to calculate the area S1 and the area S0, respectively. Based on the calculated areas S1, S0, the area ratios R2, R3, ... Of the respective graphite particles are calculated.
  • the median diameter D1 of the hollow graphite particles may be larger than the median diameter D2 of the solid graphite particles (that is, D1> D2), and is not particularly limited. It is appropriate that D1 is, for example, 4 ⁇ m or more, and is usually 5 ⁇ m or more, typically 6 ⁇ m or more. D1 is preferably 7 ⁇ m or more, more preferably 7.5 ⁇ m or more. In some embodiments, D1 may be 8 ⁇ m or greater and 10 ⁇ m or greater (eg, 12 ⁇ m or greater). Further, as the hollow graphite particles, those having a D1 of 20 ⁇ m or less can be preferably adopted from the viewpoint of increasing the discharge capacity per volume of the negative electrode active material layer when not pressed.
  • D1 is preferably 18 ⁇ m or less, more preferably 16 ⁇ m or less. In some embodiments, D1 may be 14 ⁇ m or less, or 12 ⁇ m or less (eg, 10 ⁇ m or less).
  • the technique disclosed herein can be preferably carried out in an embodiment in which the median diameter D1 of the hollow graphite particles is 4 ⁇ m or more and 20 ⁇ m or less (further, 6 ⁇ m or more and 16 ⁇ m or less, particularly 8 ⁇ m or more and 14 ⁇ m or less).
  • the median diameter D2 of the solid graphite particles may be smaller than D1 and is not particularly limited. From the viewpoint of increasing the discharge capacity per volume of the negative electrode active material layer when not pressed, those having a D2 of less than 8 ⁇ m can be preferably adopted as the solid graphite particles.
  • D2 is preferably 6 ⁇ m or less, more preferably 4 ⁇ m or less. In some embodiments, D2 may be 3.6 ⁇ m or less, or 3.4 ⁇ m or less (eg, 3.2 ⁇ m or less).
  • D2 is usually 0.5 ⁇ m or more, preferably 1 ⁇ m or more, more preferably 1.5 ⁇ m or more, and further preferably 2 ⁇ m or more.
  • it may be solid graphite particles having D2 of 2.5 ⁇ m or more (for example, 2.8 ⁇ m or more).
  • solid graphite particles having a D2 of 0.5 ⁇ m or more and less than 8 ⁇ m are preferable, and solid graphite particles having a D2 of 1.5 ⁇ m or more and 5 ⁇ m or less are more preferable, and 2 ⁇ m or more and 4 ⁇ m. The following are particularly preferred.
  • the relationship between D1 and D2 satisfies 1 ⁇ (D1 / D2) ⁇ 10.
  • the relationship between D1 and D2 is 1.5 ⁇ (D1 / D2) ⁇ 8, more preferably 1.8 ⁇ (D1 / D2) ⁇ 6, and even more preferably 2 ⁇ .
  • (D1 / D2) ⁇ 5.2 particularly preferably 2.5 ⁇ (D1 / D2) ⁇ 4.8.
  • it may be, for example, (D1 / D2) ⁇ 4, typically (D1 / D2) ⁇ 3.5 (eg, (D1 / D2) ⁇ 3).
  • the value obtained by subtracting D2 from D1 is preferably 2 ⁇ m or more, and more preferably 4 ⁇ m or more. Further, D1-D2 is preferably 18 ⁇ m or less, more preferably 15 ⁇ m or less, and further preferably 12 ⁇ m or less. For example, D1-D2 may be 10 ⁇ m or less, or 6 ⁇ m or less.
  • the “median diameter” means a value (D50) in which the volume-based integrated distribution calculated in accordance with JIS-Z8819-2 (2001) is 50%.
  • the measured value can be obtained by the following method.
  • a laser diffraction type particle size distribution measuring device (“SALD-2200” manufactured by Shimadzu Corporation) is used as a measuring device, and a Wing SALD-2200 is used as a measurement control software.
  • a scattering type measurement mode is adopted, and a wet cell in which a dispersion liquid in which a measurement sample is dispersed in a dispersion solvent circulates is irradiated with laser light to obtain a scattered light distribution from the measurement sample. Then, the scattered light distribution is approximated by a lognormal distribution, and the particle diameter corresponding to a cumulative degree of 50% is defined as the median diameter (D50).
  • the aspect ratio As1 of the hollow graphite particles disclosed herein is not particularly limited. Usually, hollow graphite particles having an aspect ratio of As1 or more are used. It is appropriate that the aspect ratio As1 is 1.1 or more, for example, 1.2 or more. In some embodiments, the aspect ratio As1 may be 1.4 or greater. Further, the aspect ratio As1 of the hollow graphite particles is preferably about 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.0 or less (for example, 1. 8 or less). In some embodiments, the aspect ratio As1 may be 1.5 or less, or 1.3 or less. By setting the aspect ratio As1 of the hollow graphite particles to the above range, it is possible to more effectively increase the discharge capacity per volume of the negative electrode active material layer when not pressed.
  • the aspect ratio As2 of the solid graphite particles disclosed here is not particularly limited, but the lower limit thereof is 1.0, preferably 1.2. From the viewpoint of improving the filling property of the negative electrode active material, solid graphite particles having an aspect ratio of As2 of 1.5 or more can be preferably adopted as the solid graphite particles in the negative electrode active material layer of the above embodiment.
  • the aspect ratio As2 of the solid graphite particles is preferably, for example, 2 or more, and typically may be 2.5 or more.
  • the upper limit of the aspect ratio As2 of the solid graphite particles is 5.0, preferably 4.5.
  • graphite particles having an aspect ratio of As2 of 4.0 or less are preferable, those having an aspect ratio of 3.5 or less are more preferable, and those having an aspect ratio of 3.2 or less (for example, 3.0 or less) are particularly preferable.
  • the aspect ratio As2 of the solid graphite particles By setting the aspect ratio As2 of the solid graphite particles to the above range, the discharge capacity per volume of the negative electrode active material layer when not pressed can be more effectively increased.
  • the graphite particles are close to spherical or spindle-shaped and current concentration is unlikely to occur, non-uniform expansion of the negative electrode can be suppressed.
  • the aspect ratio As2 of the solid graphite particles is larger than the aspect ratio As1 of the hollow graphite particles. It is preferable that the relationship between As1 and As2 satisfies 1 ⁇ (As2 / As1) ⁇ 5.
  • the technique disclosed herein is preferably carried out, for example, in an embodiment in which the relationship between As1 and As2 is 1.2 ⁇ (As2 / As1) ⁇ 4, more preferably 1.5 ⁇ (As2 / As1) ⁇ 3. Can be done.
  • the value obtained by subtracting As1 from As2 (that is, As2-As1) is preferably 0.5 or more, and more preferably 1 or more.
  • As2-As1 is preferably 3 or less, more preferably 2.5 or less, and further preferably 2 or less.
  • the "aspect ratio” means the longest diameter A of the particles and the longest in the direction perpendicular to the diameter A in the cross section of the particles observed in the SEM image obtained by using a scanning electron microscope. It means the A / B value which is the ratio with the diameter B.
  • the aspect ratio can be determined as follows. (1) Preparation of measurement sample A measurement sample with an exposed cross section used for determining the area ratio R1 described above is used. (2) Acquisition of SEM image JSM-7001F (manufactured by JEOL Ltd.) is used as a scanning electron microscope to acquire the SEM image. The SEM image shall be an observation of 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 100 or more and 1000 or less.
  • the obtained SEM image is saved as an image file.
  • various conditions such as spot diameter, working distance, irradiation current, brightness, focus, etc. are appropriately set so that the outline of the graphite particles becomes clear.
  • (3) Determination of aspect ratio 100 graphite particles are randomly selected from the acquired SEM images, and the longest diameter A of the graphite particles and the longest diameter B in the direction perpendicular to the diameter A are measured for each. Then, the A / B value is calculated.
  • the aspect ratio of the graphite particles is determined by calculating the average value of all the calculated A / B values.
  • Type of graphite particles As each of the hollow graphite particles and the solid graphite particles, those having an appropriate median diameter and shape can be appropriately selected and used from among various known graphite particles. Examples of such known graphite particles include natural graphite particles and artificial graphite particles.
  • natural graphite is a general term for graphite obtained from natural minerals
  • artificial graphite is a general term for artificially produced graphite.
  • graphite particles that can be preferably used as hollow graphite particles include natural graphite particles.
  • natural graphite particles have high crystallinity and can effectively contribute to the improvement of the discharge capacity per volume of the negative electrode active material layer of the power storage element.
  • the natural graphite particles include scaly graphite, lump graphite (scaly graphite), and earthy graphite.
  • the hollow graphite particles can be flat scaly natural graphite particles or spheroidized natural graphite particles obtained by spheroidizing the scaly graphite.
  • the solid graphite particles natural graphite particles having a smaller median diameter than the hollow graphite particles may be used, or artificial graphite particles may be used.
  • the solid graphite particles have no cavities inside and are filled in the gaps between the hollow graphite particles, thereby contributing to an increase in the bulk density (coating density when not pressed) of the negative electrode active material layer. obtain.
  • the hollow graphite particles and the solid graphite particles may be composite particles in which the graphite particles and particles made of another material (for example, another carbon material or Si compound) are bonded and composited. It may be non-composite particles that are not composited.
  • the hollow graphite particles and the solid graphite particles disclosed herein can be preferably used in the form of non-composite particles in which the graphite particles and particles made of other materials are not bonded.
  • the hollow graphite particles and the solid graphite particles may be graphite particles having a surface coated (for example, amorphous carbon coat).
  • the hollow graphite particles and the solid graphite particles can be selected so that the R value (R1) of the hollow graphite particles is smaller than the R value (R2) of the solid graphite particles (R1 ⁇ . R2).
  • the "R value” is the ratio of the peak intensity of D-band to the peak intensity of G-band in the Raman spectrum (I G1) (I D1) (I D1 / I G1).
  • the relationship between the R value (R2) of the solid graphite particles and the R value (R1) of the hollow graphite particles is 1 ⁇ (R2 / R1) ⁇ 4, more preferably.
  • the R value (R1) of the hollow graphite particles is generally less than 0.25 (for example, 0.05 or more and less than 0.25), preferably 0.23 or less (for example, 0.1 or more and 0. 23 or less), more preferably 0.22 or less (for example, 0.12 or more and 0.22 or less), still more preferably 0.21 or less.
  • the R1 of the hollow graphite particles may be 0.20 or less, or 0.18 or less.
  • the R value (R2) of the solid graphite particles can be approximately 0.25 or more (for example, 0.25 or more and 0.8 or less), for example, 0.28 or more (for example, 0.28 or more and 0.7 or less). ), Typically 0.3 or more (for example, 0.3 or more and 0.6 or less).
  • the R2 of the solid graphite particles may be 0.5 or less, or 0.4 or less.
  • the "Raman spectrum” is obtained by performing Raman spectroscopic measurement using "HR Revolution” manufactured by Horiba Seisakusho Co., Ltd. under the conditions of a wavelength of 532 nm (YAG laser), a grating of 600 g / mm, and a measurement magnification of 100 times. Specifically, first, subjected to Raman spectroscopic measurement in the range of 200cm -1 ⁇ 4000cm -1, the obtained data, based intensity minimum at 4000 cm -1, the maximum intensity in the measurement range ( For example, the strength of the G band) is standardized.
  • the hollow graphite particles and the solid graphite particles may be spherical or non-spherical, for example.
  • the non-spherical shape include a spindle shape (for example, an elliptical shape and an oval shape), a scaly shape, and a plate shape.
  • the solid graphite particles those having a spindle shape can be particularly preferably adopted.
  • the hollow graphite particles and the solid graphite particles may have irregularities on the surface.
  • the hollow graphite particles and the solid graphite particles may include particles in which a plurality of graphite particles are agglomerated.
  • the content ratio of the hollow graphite particles to the total content of the hollow graphite particles and the solid graphite particles is not particularly limited.
  • the upper limit of the content ratio is preferably 90% by mass, preferably 80% by mass, and even more preferably 75% by mass.
  • the lower limit of the content ratio of the hollow graphite particles is preferably 10% by mass, preferably 20% by mass, and more preferably 30% by mass (for example, 40% by mass).
  • the content ratio of the hollow graphite particles to the total content of the hollow graphite particles and the solid graphite particles is 10% by mass or more and 80% by mass or less (further, 25% by mass or more and 65% by mass).
  • the discharge capacity per volume of the negative electrode active material layer can be further increased.
  • the negative electrode active material layer disclosed herein contains graphite particles other than the hollow graphite particles and the solid graphite particles (hereinafter, referred to as a third graphite particle) as long as the effects of the present invention are not impaired. You may be.
  • the third graphite particles it can be appropriately selected and used from various known graphite particles.
  • the shape of the third graphite particles is not particularly limited, but it is preferably a shape close to a spherical shape or a spindle shape having an aspect ratio of 2 or more and 5 or less.
  • the total mass of the hollow graphite particles and the solid graphite particles out of the total mass of the graphite particles contained in the negative electrode active material layer is 70% by mass or more. , Preferably 80% by mass or more, more preferably 90% by mass or more. Among them, a power storage element in which 100% by mass of the graphite particles contained in the negative electrode active material layer is the hollow graphite particles and the solid graphite particles is preferable.
  • the negative electrode active material layer disclosed herein is a carbonaceous active material other than the hollow graphite particles, the solid graphite particles, and the third graphite particles (hereinafter, non-graphitized) as long as the effects of the present invention are not impaired. It may contain (referred to as graphite active material).
  • Examples of the non-graphitizable carbonaceous active material include non-graphitizable carbon and easily graphitizable carbon.
  • graphite-resistant carbon means that the average lattice spacing d (002) of the (002) plane measured by the X-ray diffraction method before charging / discharging or in the discharged state is 0.36 nm or more and 0.42 nm or less. Refers to the carbon material of.
  • the “graphitizable carbon” refers to a carbon material having d (002) of 0.34 nm or more and less than 0.36 nm.
  • the total mass of the hollow graphite particles and the solid graphite particles in the total mass of the carbonaceous active material contained in the negative electrode active material layer shall be 70% by mass or more.
  • a power storage element in which 100% by mass of the carbonaceous active material contained in the negative electrode active material layer is the hollow graphite particles and the solid graphite particles is preferable.
  • the negative electrode active material layer disclosed herein may contain a negative electrode active material made of a material other than the carbonaceous active material (hereinafter, referred to as a non-carbonic active material) as long as the effects of the present invention are not impaired. ..
  • non-carbon active materials include semimetals such as Si, metals such as Sn, oxides of these metals, and composites of these metals and carbon materials.
  • the content of the non-carbon active material is preferably, for example, 30% by mass or less, preferably 20% by mass or less, more preferably 20% by mass or less, based on the total mass of the negative electrode active material contained in the negative electrode active material layer. It is 10% by mass or less.
  • the technique disclosed herein can be preferably carried out in an embodiment in which the total proportion of the carbonaceous active material in the total mass of the negative electrode active material contained in the negative electrode active material layer is larger than 90% by mass.
  • the proportion of the carbonaceous active material is more preferably 95% by mass or more, further preferably 98% by mass or more, and particularly preferably 99% by mass or more.
  • a power storage element in which 100% by mass of the negative electrode active material contained in the negative electrode active material layer is a carbonaceous active material is preferable.
  • the negative electrode active material layer disclosed herein contains optional components such as a conductive agent, a binder (binder), a thickener, and a filler, if necessary.
  • the hollow graphite particles and the solid graphite particles also have conductivity, and examples of the conductive agent include carbonaceous materials, metals, and conductive ceramics.
  • the carbonaceous material include graphitized carbon, non-graphitized carbon, graphene-based carbon and the like.
  • Examples of non-graphitized carbon include carbon nanofibers, pitch-based carbon fibers, and carbon black.
  • Examples of carbon black include furnace black, acetylene black, and ketjen black.
  • Examples of graphene-based carbon include graphene, carbon nanotubes (CNT), and fullerenes.
  • Examples of the shape of the conductive material include powder and fibrous. As the conductive agent, one of these materials may be used alone, or two or more of these materials may be mixed and used.
  • the ratio of the conductive agent to the entire negative electrode active material layer can be about 8.0% by mass or less, and usually about 5.0% by mass or less (for example, 1). It is preferably 0.0% by mass or less).
  • the technique disclosed herein can be preferably carried out in a manner in which the negative electrode active material layer does not contain the above-mentioned conductive agent.
  • binder examples include fluororesins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), thermoplastic resins such as polyethylene, polypropylene, polyacryl, and polyimide; ethylene-propylene-diene rubber (EPDM), sulfone.
  • EPDM ethylene-propylene-diene rubber
  • elastomers such as chemicalized EPDM, styrene-butadiene rubber (SBR), and fluororubber; and polysaccharide polymers.
  • the content of the binder in the negative electrode active material layer is preferably 1% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 9% by mass or less. By setting the content of the binder in the above range, the negative electrode active material particles can be stably held.
  • the thickener examples include polysaccharide polymers such as carboxymethyl cellulose (CMC) and methyl cellulose.
  • CMC carboxymethyl cellulose
  • methyl cellulose examples include polysaccharide polymers such as carboxymethyl cellulose (CMC) and methyl cellulose.
  • this functional group may be inactivated by methylation or the like in advance.
  • the filler is not particularly limited.
  • the main components of the filler are polyolefins such as polypropylene and polyethylene, inorganic oxides such as silicon dioxide, aluminum oxide, titanium dioxide, calcium oxide, strontium oxide, barium oxide, magnesium oxide and aluminosilicate, magnesium hydroxide and hydroxide.
  • Hydroxides such as calcium and aluminum hydroxide, carbonates such as calcium carbonate, sparingly soluble ion crystals such as calcium fluoride, barium fluoride and barium sulfate, nitrides such as aluminum nitride and silicon nitride, talc and montmorillonite, Examples include mineral resource-derived substances such as boehmite, zeolite, apatite, kaolin, mulite, spinel, olivine, cericite, bentonite, and mica, or man-made products thereof.
  • mineral resource-derived substances such as boehmite, zeolite, apatite, kaolin, mulite, spinel, olivine, cericite, bentonite, and mica, or man-made products thereof.
  • the proportion of the filler in the entire negative electrode active material layer can be about 8.0% by mass or less, and usually about 5.0% by mass or less (for example, 1.0). It is preferably mass% or less).
  • the technique disclosed herein can be preferably carried out in a manner in which the negative electrode active material layer does not contain the above filler.
  • a "main component" means a component having the highest content, for example, a component contained in an amount of 50% by mass or more with respect to the total mass.
  • the negative electrode active material layer disclosed here is not substantially pressed.
  • the residual stress of the press may increase the expansion of the negative electrode during initial charging. Since the negative electrode active material layer containing hollow graphite particles and solid graphite particles is not substantially pressed as the negative electrode active material, the negative electrode active material is hardly stressed by the time the electrode body is formed. .. Therefore, the residual stress is small in the graphite particles themselves, and the non-uniform expansion of the negative electrode due to the release of the residual stress can be suppressed. Therefore, the expansion of the negative electrode that occurs during the initial charging can be suppressed.
  • substantially not pressed means a pressure (line) of 10 kgf / mm or more with respect to the negative electrode active material layer by an apparatus intended to apply pressure to a work such as a roll press machine at the time of manufacturing. It means that the process of applying pressure) has not been performed. That is, in other steps such as winding up the negative electrode, the one in which a slight pressure is applied to the negative electrode active material layer is also included in “substantially not pressed”. Further, “substantially not pressed” includes that a step of applying a pressure (linear pressure) of less than 10 kgf / mm is performed.
  • the density of the negative electrode active material layer is not particularly limited, the lower limit is preferably 1.30 g / cm 3, more preferably 1.35 g / cm 3, more preferably 1.40 g / cm 3.
  • the upper limit of the density of the negative electrode active material layer 1.55 g / cm 3 is preferable, and 1.50 g / cm 3 is more preferable.
  • the density of the negative electrode active material layer may be 1.48 g / cm 3 or less, or 1.45 g / cm 3 or less.
  • the power storage element expands relatively uniformly to maintain a negative electrode active material layer having a high filling rate of the graphite particles, and as a result, suppresses the expansion of the negative electrode that occurs during initial charging. It is speculated that it can be done.
  • Q2 / Q1 which is the ratio of the surface roughness Q1 of the region where the negative electrode active material layer is laminated to the surface roughness Q2 of the region where the negative electrode active material layer is not laminated on the negative electrode base material.
  • the lower limit of 0.90 is preferable, 0.92 is more preferable, and 0.94 is further preferable.
  • the pressure applied to the negative electrode base material the surface roughness of the region where the negative electrode active material layer is formed increases, so that Q2 / Q1 becomes smaller.
  • the negative electrode base material includes a region in which the negative electrode active material layer is arranged and a region in which the negative electrode active material layer is not arranged (so-called exposed region of the negative electrode base material).
  • the pressure applied to the negative electrode active material layer is no or small. Therefore, the residual stress is small in the graphite particles themselves, and the non-uniform expansion of the negative electrode due to the release of the residual stress can be suppressed. In this way, even if the graphite particles expand, the expansion is relatively uniform, so that the negative electrode active material layer having a high filling rate of the graphite particles is maintained, and as a result, the expansion of the negative electrode that occurs during initial charging is suppressed.
  • the upper limit of the surface roughness ratio (Q2 / Q1) is usually 1. In some embodiments, the surface roughness ratio (Q2 / Q1) may be 0.99 or less, or 0.98 or less.
  • surface roughness refers to the center line roughness Ra of the surface of the base material (for the region where the active material layer is formed, the surface after removing the active material layer), JIS-B0601 (2013). Means the value measured with a laser microscope according to.
  • the intermediate layer is a coating layer on the surface of the negative electrode base material, and contains conductive particles such as carbon particles to reduce the contact resistance between the negative electrode base material and the negative electrode active material layer.
  • the composition of the intermediate layer is not particularly limited, and can be formed by, for example, a composition containing a resin binder and conductive particles. The technique disclosed herein can be preferably carried out in an embodiment without the intermediate layer.
  • the positive electrode has a positive electrode base material and a positive electrode active material layer.
  • the positive electrode active material layer contains a positive electrode active material.
  • the positive electrode active material layer is laminated directly or via an intermediate layer along at least one surface of the positive electrode base material.
  • the positive electrode base material has conductivity.
  • metals such as aluminum, titanium, tantalum, and stainless steel or alloys thereof are used.
  • aluminum and aluminum alloys are preferable from the viewpoint of balance of potential resistance, high conductivity and cost.
  • examples of the form of the positive electrode base material include foils and thin-film deposition films, and foils are preferable from the viewpoint of cost. That is, an aluminum foil is preferable as the positive electrode base material.
  • Examples of aluminum or aluminum alloy include A1085 and A3003 specified in JIS-H4000 (2014).
  • the positive electrode active material layer is formed from a so-called positive electrode mixture containing a positive electrode active material. Further, the positive electrode mixture forming the positive electrode active material layer contains optional components such as a conductive agent, a binder, a thickener, and a filler, if necessary.
  • the positive electrode active material for example, a known positive electrode active material can be appropriately selected.
  • the positive electrode active material for a lithium ion secondary battery a material capable of occluding and releasing lithium ions is usually used.
  • the positive electrode active material include a lithium transition metal composite oxide having an ⁇ -NaFeO type 2 crystal structure, a lithium transition metal oxide having a spinel type crystal structure, a polyanion compound, a chalcogen compound, sulfur and the like.
  • the lithium transition metal composite oxide having an ⁇ -NaFeO type 2 crystal structure include Li [Li x Ni 1-x ] O 2 (0 ⁇ x ⁇ 0.5) and Li [Li x Ni ⁇ Co (1-).
  • Examples of the lithium transition metal oxide having a spinel-type crystal structure include Li x Mn 2 O 4 and Li x Ni ⁇ Mn (2- ⁇ ) O 4 .
  • Examples of the polyanion compound include LiFePO 4 , LiMnPO 4 , LiNiPO 4 , LiCoPO 4 , Li 3 V 2 (PO 4 ) 3 , Li 2 MnSiO 4 , Li 2 CoPO 4 F and the like.
  • the chalcogen compound include titanium disulfide, molybdenum disulfide, molybdenum dioxide and the like.
  • the atoms or polyanions in these materials may be partially substituted with atoms or anion species consisting of other elements. The surface of these materials may be coated with other materials.
  • the positive electrode active material layer one of these materials may be used alone, or two or more of these materials may be mixed and used. In the positive electrode active material layer, one of these compounds may be used alone, or two or more of these compounds may be mixed and used.
  • the content of the positive electrode active material in the positive electrode active material layer is not particularly limited, but the lower limit thereof is preferably 50% by mass, more preferably 80% by mass, and even more preferably 90% by mass. On the other hand, as the upper limit of this content, 99% by mass is preferable, and 98% by mass is more preferable.
  • the conductive agent is not particularly limited as long as it is a conductive material.
  • a conductive agent can be selected from the materials exemplified in the negative electrode.
  • the ratio of the conductive agent to the entire positive electrode active material layer can be about 1.0% by mass or more and 20% by mass or less, and usually about 2.0% by mass or more and 15% by mass or less. (For example, 3.0% by mass or more and 6.0% by mass or less) is preferable.
  • binder examples include fluororesins (polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), etc.), thermoplastic resins such as polyethylene, polypropylene, and polyimide; ethylene-propylene-diene rubber (EPDM), sulfonated EPDM, and styrene. Elastomers such as butadiene rubber (SBR) and fluororubber; polysaccharide polymers and the like can be mentioned.
  • the proportion of the binder in the entire positive electrode active material layer can be about 0.50% by mass or more and 15% by mass or less, and usually about 1.0% by mass or more and 10% by mass or less (for example). It is preferably 1.5% by mass or more and 3.0% by mass or less).
  • the thickener examples include polysaccharide polymers such as carboxymethyl cellulose (CMC) and methyl cellulose.
  • CMC carboxymethyl cellulose
  • the proportion of the thickener in the entire positive electrode active material layer can be about 8% by mass or less, and usually about 5.0% by mass or less (for example, 1.0% by mass or less). ) Is preferable.
  • the technique disclosed herein can be preferably carried out in a manner in which the positive electrode active material layer does not contain the thickener.
  • the filler can be selected from the materials exemplified in the negative electrode.
  • the proportion of the filler in the entire positive electrode active material layer can be about 8.0% by mass or less, and usually about 5.0% by mass or less (for example, 1.0% by mass or less). It is preferable to do so.
  • the technique disclosed herein can be preferably carried out in a manner in which the positive electrode active material layer does not contain the above filler.
  • the intermediate layer is a coating layer on the surface of the positive electrode base material, and contains conductive particles such as carbon particles to reduce the contact resistance between the positive electrode base material and the positive electrode active material layer.
  • the structure of the intermediate layer is not particularly limited, and can be formed by, for example, a composition containing a resin binder and conductive particles. The technique disclosed herein can be preferably carried out in an embodiment without the intermediate layer.
  • separator for example, a woven fabric, a non-woven fabric, a porous resin film or the like is used. Among these, a porous resin film is preferable from the viewpoint of strength, and a non-woven fabric is preferable from the viewpoint of liquid retention of a non-aqueous electrolyte.
  • polyolefins such as polyethylene and polypropylene are preferable from the viewpoint of strength, and polyimide and aramid are preferable from the viewpoint of oxidative decomposition resistance. Moreover, you may combine these resins.
  • An inorganic layer may be laminated between the separator and the electrode (usually the positive electrode).
  • This inorganic layer is a porous layer also called a heat-resistant layer or the like.
  • a separator having an inorganic layer formed on one surface or both surfaces of the porous resin film can also be used.
  • the inorganic layer is usually composed of inorganic particles and a binder, and may contain other components.
  • Non-aqueous electrolyte As the non-aqueous electrolyte, a known non-aqueous electrolyte usually used for a general non-aqueous electrolyte secondary battery (storage element) can be used.
  • the non-aqueous electrolyte contains a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
  • the non-aqueous electrolyte may be a solid electrolyte or the like.
  • non-aqueous solvent a known non-aqueous solvent usually used as a non-aqueous solvent for a general non-aqueous electrolyte for a power storage element can be used.
  • the non-aqueous solvent include cyclic carbonate, chain carbonate, ester, ether, amide, sulfonamide, lactone, nitrile and the like. Among these, it is preferable to use at least cyclic carbonate or chain carbonate, and it is more preferable to use cyclic carbonate and chain carbonate in combination.
  • the volume ratio of the cyclic carbonate to the chain carbonate is not particularly limited, but may be, for example, 5:95 to 50:50. preferable.
  • cyclic carbonate examples include ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylene carbonate (VC), vinyl ethylene carbonate (VEC), chloroethylene carbonate, fluoroethylene carbonate (FEC), and difluoroethylene.
  • EC ethylene carbonate
  • PC propylene carbonate
  • BC butylene carbonate
  • VC vinylene carbonate
  • VEC vinyl ethylene carbonate
  • FEC fluoroethylene carbonate
  • difluoroethylene examples thereof include carbonate (DFEC), styrene carbonate, catechol carbonate, 1-phenylvinylene carbonate, 1,2-diphenylvinylene carbonate, and among these, EC is preferable.
  • chain carbonate examples include diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diphenyl carbonate and the like, and among these, EMC is preferable.
  • electrolyte salt a known electrolyte salt usually used as an electrolyte salt of a general non-aqueous electrolyte for a power storage element can be used.
  • electrolyte salt examples include lithium salt, sodium salt, potassium salt, magnesium salt, onium salt and the like, but lithium salt is preferable.
  • lithium salt examples include inorganic lithium salts such as LiPF 6 , LiPO 2 F 2 , LiBF 4 , LiClO 4 , LiN (SO 2 F) 2 , LiSO 3 CF 3 , LiN (SO 2 CF 3 ) 2 , and LiN (SO).
  • 2 C 2 F 5 ) 2 LiN (SO 2 CF 3 ) (SO 2 C 4 F 9 ), LiC (SO 2 CF 3 ) 3 , LiC (SO 2 C 2 F 5 ) 3 hydrogen is replaced with fluorine
  • examples thereof include a lithium salt having a sulfur group. Among these, an inorganic lithium salt is preferable, and LiPF 6 is more preferable.
  • the lower limit of the concentration of the electrolyte salt in the nonaqueous electrolyte is preferably 0.1 mol / dm 3, more preferably 0.3 mol / dm 3, more preferably 0.5mol / dm 3, 0.7mol / dm 3 Is particularly preferable.
  • the upper limit is not particularly limited, but is preferably 2.5 mol / dm 3, more preferably 2.0 mol / dm 3, more preferably 1.5 mol / dm 3.
  • non-aqueous electrolyte a room temperature molten salt, an ionic liquid, or the like can also be used.
  • the shape of the power storage element of the present embodiment is not particularly limited, and examples thereof include a cylindrical battery, a laminated film type battery, a square battery, a flat type battery, a coin type battery, and a button type battery.
  • FIG. 1 shows a power storage element 1 (non-aqueous electrolyte power storage element) as an example of a square battery.
  • the figure is a perspective view of the inside of the case.
  • the electrode body 2 having the positive electrode and the negative electrode wound around the separator is housed in the square case 3.
  • the positive electrode is electrically connected to the positive electrode terminal 4 via the positive electrode lead 4'.
  • the negative electrode is electrically connected to the negative electrode terminal 5 via the negative electrode lead 5'.
  • the power storage element includes a negative electrode having a high discharge capacity per volume of the negative electrode active material layer even when there is no pressure applied to the negative electrode active material layer or when graphite is used as the negative electrode active material. Obtainable.
  • the method for manufacturing the power 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 accommodating the electrode body and the non-aqueous electrolyte in a container.
  • Preparing the electrode body includes preparing a positive electrode body and a negative electrode body, and forming the electrode body by laminating or winding the positive electrode body and the negative electrode body via a separator.
  • the negative electrode activity containing hollow graphite particles having a median diameter D1 and solid graphite particles having a median diameter D2 smaller than the hollow graphite particles.
  • a negative electrode active material layer containing a negative electrode active material containing hollow graphite particles and solid graphite particles is applied to at least one surface of the negative electrode base material. Laminate along. Specifically, for example, the negative electrode active material layer is laminated by applying a negative electrode mixture to the negative electrode base material and drying it. After the above drying, pressing may be performed in the direction of the average thickness of the negative electrode active material layer.
  • the pressure (linear pressure) at the time of pressing is not particularly limited, but from the viewpoint of suppressing the expansion of the negative electrode that occurs during the initial charging, it is appropriate to be approximately 25 kgf / mm or less, preferably 20 kgf / mm or less. , More preferably 16 kgf / mm or less, still more preferably 12 kgf / mm or less.
  • the negative electrode active material layer is not pressed before laminating the negative electrode and the positive electrode. That is, the negative electrode active material layer is arranged on the negative electrode base material in a "substantially unpressed" state.
  • a known method can be appropriately selected.
  • the non-aqueous electrolyte solution may be injected from the injection port formed in the container, and then the injection port may be sealed. Details of each of the other elements constituting the power storage element obtained by the manufacturing method are as described above.
  • the power storage element of the present invention is not limited to the above embodiment, and various modifications may be made without departing from the gist of the present invention.
  • the configuration of one embodiment can be added to the configuration of another embodiment, and a part of the configuration of one embodiment can be replaced with the configuration of another embodiment or a well-known technique.
  • some of the configurations of certain embodiments can be deleted.
  • a well-known technique can be added to the configuration of a certain embodiment.
  • the mode in which the power storage element is a non-aqueous electrolyte secondary battery has been mainly described, but other power storage elements may be used.
  • Examples of other power storage elements include capacitors (electric double layer capacitors, lithium ion capacitors) and the like.
  • Examples of the non-aqueous electrolyte secondary battery include a lithium ion non-aqueous electrolyte secondary battery.
  • the present invention can also be realized as a power storage device including a plurality of the above power storage elements.
  • an assembled battery can be constructed by using one or more power storage elements (cells) of the present invention, and a power storage device can be further configured by using the assembled battery.
  • the power storage device can be used as a power source for automobiles such as electric vehicles (EV), hybrid electric vehicles (HEV), and plug-in hybrid vehicles (PHEV). Further, the power storage device can be used for various power supply devices such as an engine starting power supply device, an auxiliary power supply device, and an uninterruptible power supply (UPS).
  • UPS uninterruptible power supply
  • 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 power storage elements 1 are assembled is further assembled.
  • the power storage device 30 may include a bus bar (not shown) that electrically connects two or more power storage elements 1 and a bus bar (not shown) that electrically connects two or more power storage units 20.
  • the power storage unit 20 or the power storage device 30 may include a condition monitoring device (not shown) that monitors the state of one or more power storage elements.
  • Example 1 to 8 and Comparative Examples 1 to 3 (Negative electrode) It contains water as a negative electrode active material having the composition shown in Table 1 (content ratio to the total content of solid graphite particles and hollow graphite particles), styrene-butadiene rubber as a binder, and carboxymethyl cellulose as a thickener. Was used as a dispersion medium to prepare a negative electrode mixture paste. The ratio of the negative electrode active material, the binder, and the thickener was 97.8: 1.0: 1.2 in terms of mass ratio.
  • the negative electrode mixture paste is applied to both sides of a negative electrode base material (surface roughness 0.86 ⁇ m) made of copper foil having a thickness of 8 ⁇ m and dried to form a negative electrode active material layer, and Examples 1 to 8 are formed.
  • the negative electrode of Comparative Example 3 was obtained from Comparative Example 1.
  • Table 1 shows the physical characteristics of the negative electrode active material.
  • the coating amount of the negative electrode mixture (the dispersion medium evaporated from the negative electrode mixture paste) per unit area on one side after drying was set to 1.0 g / 100 cm 2 . Further, in Examples 1 to 8 and Comparative Examples 1 to 3, the press was performed using a roll press machine so that the pressure (linear pressure) was less than 5 kgf / mm.
  • the positive electrode contains LiNi 0.6 Mn 0.2 Co 0.2 O 2 as a positive electrode active material, polyvinylidene fluoride (PVDF) as a binder, and acetylene black as a conductive agent, and N-methyl-.
  • a positive electrode mixture paste using 2-pyrrolidone (NMP) as a dispersion medium was prepared. The ratio of the positive electrode active material, the binder, and the conductive agent was 94.5: 4: 1.5 in terms of mass ratio.
  • the positive electrode mixture paste was applied to both sides of a positive electrode base material made of an aluminum foil having a thickness of 15 ⁇ m, pressed, and dried to form a positive electrode active material layer.
  • the coating amount of the positive electrode mixture (the dispersion medium evaporated from the positive electrode mixture paste) per unit area on one side after drying was set to 1.7 g / 100 cm 2 .
  • a non-aqueous electrolyte was obtained by dissolving dm 3 ). Then, the positive electrode and the negative electrode were laminated via a separator made of a polyethylene microporous membrane to prepare an electrode body. This electrode body was housed in a square electric tank can made of aluminum, and a positive electrode terminal and a negative electrode terminal were attached. After injecting the non-aqueous electrolyte into the inside of this container (square electric tank can), the container was sealed to obtain a power storage element of Examples and Comparative Examples.
  • the area ratio R of the graphite particles excluding the voids in the particles was calculated by the above method.
  • the aspect ratio of the graphite particles was determined by the method described above.
  • Charging Li absorbing reaction: lower limit voltage 10mV the current density 2 mA / cm 2, charge termination current density 0.04 mA / cm 2 and the constant current constant voltage (CCCV) charge-discharge (Li elimination reaction): Up Constant current (CC) discharge with a voltage of 2.0 V and a current density of 2 mA / cm 2.
  • the amount of expansion of the negative electrode active material during initial charging is calculated by subtracting the "average thickness of the negative electrode active material layer before charging and discharging" from the "average thickness of the negative electrode active material layer during initial charging” calculated by the following method. After the calculation, the expansion rate of the negative electrode active material at the time of initial charging was determined.
  • (1) Measurement of average thickness of negative electrode active material layer before charging / discharging Ten samples with an area of 2 cm x 1 cm of the negative electrode before manufacturing the power storage element were prepared as measurement samples, and a high-precision digital micrometer manufactured by Mitutoyo Co., Ltd. was prepared. The thickness of each negative electrode was measured using a meter.
  • the thickness of the negative electrode is measured at 5 points for each negative electrode, and the thickness of the negative electrode base material is subtracted from the average value by 8 ⁇ m to obtain the thickness of the negative electrode active material layer before charging and discharging of one negative electrode. It was measured. By calculating the average value of the thickness of the negative electrode active material layer before charging / discharging measured with 10 negative electrodes, the average thickness ( ⁇ m) of the negative electrode active material layer before charging / discharging was obtained. (2) Measurement of the average thickness of the negative electrode active material layer during initial charging The average thickness of the negative electrode active material layer during initial charging is measured in a glove box filled with argon having a dew point value of -60 ° C or less.
  • Expansion rate of the negative electrode active material during initial charging For each of Examples 1 to 8 and Comparative Examples 1 to 3, the negative electrode activity before charging and discharging is determined from the average thickness of the negative electrode active material layer during initial charging. After calculating the expansion amount of the negative electrode active material at the time of initial charging by subtracting the average thickness of the material layer, it is divided by the average thickness of the negative electrode active material layer before charging / discharging to obtain the negative electrode active material at the time of initial charging. The expansion rate (%) was calculated.
  • Table 1 shows the evaluation results of the negative electrodes of Examples 1 to 8 and Comparative Examples 1 to 3. Further, with respect to Examples 1 to 5 and Comparative Examples 1 to 2 using solid graphite particles having a median diameter of 3 ⁇ m and hollow graphite particles having a median diameter of 8 ⁇ m, solid graphite particles and hollow graphite are shown in FIG. The relationship between the content ratio (mass%) of the hollow graphite particles to the total content of the particles and the discharge capacity per volume (mAh / cm 3 ) of the negative electrode active material layer when unpressed is shown, and FIG. 4 shows the solid graphite. The relationship between the content ratio (mass%) of the hollow graphite particles to the total content of the particles and the hollow graphite particles and the expansion rate (%) of the negative electrode active material at the time of initial charging is shown.
  • the energy storage elements of Examples 1 to 5 in which the hollow graphite particles and the solid graphite particles having a smaller median diameter are used in combination are the hollow graphite.
  • the discharge capacity per volume of the negative electrode active material layer when not pressed was increased.
  • the power storage elements of Examples 1 to 5 are shown by the broken lines in FIGS. 3 from Comparative Example 2 in which the hollow graphite particles are used alone and Comparative Example 1 in which the solid graphite particles are used alone.
  • the discharge capacity per volume of the negative electrode active material layer when not pressed was increased.
  • the discharge capacities per volume of the negative electrode active material layer when not pressed were 360 mAh / cm 3 , 436 mAh, respectively. since it is / cm 3, in the third embodiment of the hollow graphite particles and solid graphite particles were mixed at 50:50, the volume of the negative electrode active material layer when not pressing the approximate expression shown by the broken line in FIG. 3
  • the discharge capacity per volume of the negative electrode active material layer when not pressed in Example 3 is 459 mAh / cm 3 , which is higher than expected.
  • Comparative Example 3 in which the hollow graphite particles and the solid graphite particles having a larger median diameter were used in combination, the negative electrode active material layer in the unpressed state was compared with Examples 1 to 8.
  • the discharge capacity per volume was inferior. From these results, by using hollow graphite particles and solid graphite particles having a smaller median diameter in combination, a power storage element with a large discharge capacity per volume of the negative electrode active material layer when unpressed was realized. I was able to confirm that I could get it.
  • the power storage element including the negative electrode containing the hollow graphite particles in which the negative electrode active material has a median diameter D1 and the solid graphite particles having a median diameter D2 smaller than the hollow graphite particles is unpressed. It was shown that the discharge capacity per volume of the negative electrode active material layer was high.
  • the present invention is suitably used as a power storage element such as a non-aqueous electrolyte secondary battery used as a power source for personal computers, electronic devices such as communication terminals, automobiles, and the like.

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023090333A1 (ja) * 2021-11-22 2023-05-25 株式会社Ｇｓユアサ 非水電解質蓄電素子

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004134175A (ja) * 2002-10-09 2004-04-30 Matsushita Electric Ind Co Ltd 電池用電極及びそれを用いた電池
JP2005222933A (ja) 2004-01-05 2005-08-18 Showa Denko Kk リチウム電池用負極材及びリチウム電池
JP2011048992A (ja) * 2009-08-26 2011-03-10 Sekisui Chem Co Ltd 炭素材料、電極材料及びリチウムイオン二次電池負極材料
JP2014179291A (ja) * 2013-03-15 2014-09-25 Sumitomo Osaka Cement Co Ltd 電極材料及び電極並びにリチウムイオン電池
JP2014212030A (ja) * 2013-04-18 2014-11-13 Jsr株式会社 蓄電デバイス用電極およびその製造方法、ならびに蓄電デバイス
WO2018066110A1 (en) * 2016-10-06 2018-04-12 Nec Corporation Spacer Included Electrodes Structure and Its Application for High Energy Density and Fast Chargeable Lithium Ion Batteries
WO2018138865A1 (en) * 2017-01-27 2018-08-02 Nec Corporation Silicone ball containing electrode and lithium ion battery including the same

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4666876B2 (ja) 2001-09-26 2011-04-06 Ｊｆｅケミカル株式会社 複合黒鉛質材料およびその製造方法、ならびにリチウムイオン二次電池用負極材料およびリチウムイオン二次電池
US7052803B2 (en) 2002-07-31 2006-05-30 Matsushita Electric Industrial Co., Ltd. Lithium rechargeable battery
JP4252846B2 (ja) 2002-07-31 2009-04-08 パナソニック株式会社 リチウム二次電池
JP4104561B2 (ja) 2003-01-29 2008-06-18 Ｊｆｅケミカル株式会社 リチウムイオン二次電池用負極材料、負極およびリチウムイオン二次電池
JP5081375B2 (ja) 2004-02-12 2012-11-28 三菱化学株式会社 リチウム二次電池用負極材料及びその製造方法、並びにそれを用いたリチウム二次電池用負極及びリチウム二次電池
US20070128518A1 (en) 2004-02-12 2007-06-07 Mitsubishi Chemical Corporation Negative electrode material for lithium secondary battery, method for producing same, negative electrode for lithium secondary battery using same, and lithium secondary battery
JP3958781B2 (ja) * 2005-07-04 2007-08-15 昭和電工株式会社 リチウム二次電池用負極、負極組成物の製造方法、及びリチウム二次電池
JP4665930B2 (ja) * 2007-03-29 2011-04-06 Ｔｄｋ株式会社 アノード及びリチウムイオン二次電池
JP2009026514A (ja) 2007-07-18 2009-02-05 Panasonic Corp 非水電解質二次電池
JP5563743B2 (ja) 2008-03-28 2014-07-30 日立化成株式会社 リチウムイオン二次電池負極用炭素材料、それを用いたリチウムイオン二次電池用負極合剤及びリチウムイオン二次電池
JP5322804B2 (ja) 2009-06-25 2013-10-23 Ｊｆｅケミカル株式会社 リチウムイオン二次電池用負極材料、リチウムイオン二次電池負極およびリチウムイオン二次電池
JP5473886B2 (ja) 2010-12-21 2014-04-16 Ｊｆｅケミカル株式会社 リチウムイオン二次電池用負極材料、リチウムイオン二次電池負極およびリチウムイオン二次電池
CN103328378B (zh) 2011-10-06 2014-12-17 昭和电工株式会社 石墨材料、其制造方法、电池电极用碳材料和电池
JP6040022B2 (ja) 2012-03-02 2016-12-07 Ｊｆｅケミカル株式会社 リチウムイオン二次電池用負極材料、リチウムイオン二次電池用負極およびリチウムイオン二次電池
DE112013003030T5 (de) 2012-06-29 2015-04-09 Showa Denko K.K. Kohlenstoffmaterial, kohlenstoffhaltiges Material für Batterieelektrode, und Batterie
CN104521038B (zh) 2012-08-06 2017-08-22 昭和电工株式会社 锂离子二次电池用负极材料
JP5737347B2 (ja) 2013-08-21 2015-06-17 日立化成株式会社 リチウムイオン二次電池負極用炭素材料、それを用いたリチウムイオン二次電池用負極合剤及びリチウムイオン二次電池
JP2015164127A (ja) 2014-01-31 2015-09-10 三菱化学株式会社 非水系二次電池負極用炭素材、非水系二次電池用負極及び非水系二次電池
US10418629B2 (en) * 2014-03-25 2019-09-17 Tosoh Corporation Composite active material for lithium ion secondary batteries and method for producing same
US20180183061A1 (en) * 2016-12-23 2018-06-28 3M Innovative Properties Company Graphitic materials and methods of making same

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004134175A (ja) * 2002-10-09 2004-04-30 Matsushita Electric Ind Co Ltd 電池用電極及びそれを用いた電池
JP2005222933A (ja) 2004-01-05 2005-08-18 Showa Denko Kk リチウム電池用負極材及びリチウム電池
JP2011048992A (ja) * 2009-08-26 2011-03-10 Sekisui Chem Co Ltd 炭素材料、電極材料及びリチウムイオン二次電池負極材料
JP2014179291A (ja) * 2013-03-15 2014-09-25 Sumitomo Osaka Cement Co Ltd 電極材料及び電極並びにリチウムイオン電池
JP2014212030A (ja) * 2013-04-18 2014-11-13 Jsr株式会社 蓄電デバイス用電極およびその製造方法、ならびに蓄電デバイス
WO2018066110A1 (en) * 2016-10-06 2018-04-12 Nec Corporation Spacer Included Electrodes Structure and Its Application for High Energy Density and Fast Chargeable Lithium Ion Batteries
WO2018138865A1 (en) * 2017-01-27 2018-08-02 Nec Corporation Silicone ball containing electrode and lithium ion battery including the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP3975286A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023090333A1 (ja) * 2021-11-22 2023-05-25 株式会社Ｇｓユアサ 非水電解質蓄電素子

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