WO2023013269A1 - 負極及び蓄電素子 - Google Patents
負極及び蓄電素子 Download PDFInfo
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- WO2023013269A1 WO2023013269A1 PCT/JP2022/024787 JP2022024787W WO2023013269A1 WO 2023013269 A1 WO2023013269 A1 WO 2023013269A1 JP 2022024787 W JP2022024787 W JP 2022024787W WO 2023013269 A1 WO2023013269 A1 WO 2023013269A1
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- Prior art keywords
- negative electrode
- active material
- electrode active
- graphite
- material layer
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- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
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- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- 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
- 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
- H01M4/58—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
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- 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 negative electrode and a storage element.
- Non-aqueous electrolyte secondary batteries typified by lithium-ion secondary batteries
- Non-aqueous electrolyte secondary batteries are widely used in electronic devices such as personal computers, communication terminals, and automobiles due to their high energy density.
- capacitors such as lithium ion capacitors and electric double layer capacitors, and storage elements using electrolytes other than non-aqueous electrolytes are also widely used.
- a storage element generally includes an electrode body in which a positive electrode containing a positive electrode active material and a negative electrode containing a negative electrode active material are superimposed with a separator interposed therebetween. Such an electrode assembly is housed in a container together with an electrolyte to form a storage element. Carbon materials such as graphite are widely used as negative electrode active materials (see Patent Documents 1 and 2).
- Electrical storage elements are required to have various performances according to the usage environment. For example, in a power storage device that is expected to be used in a low temperature environment, it is desired that it can exhibit high input performance even in a low temperature environment.
- An object of the present invention is to provide a negative electrode that can improve the input performance of a storage element in a low-temperature environment, and a storage element having such a negative electrode.
- a negative electrode according to one aspect of the present invention has a negative electrode active material layer containing solid graphite, the average circularity of the solid graphite is 0.7 or less, and the negative electrode active material layer further contains carbon fine particles. It is a negative electrode for the electric storage element to contain.
- a power storage element according to another aspect of the present invention is a power storage element including the negative electrode according to one aspect of the present invention.
- a negative electrode that can improve the input performance of a power storage element in a low-temperature environment, and a power storage element having such a negative electrode.
- FIG. 1 is a see-through perspective view showing one embodiment of a power storage device.
- FIG. 2 is a schematic diagram showing an embodiment of a power storage device configured by assembling a plurality of power storage elements.
- a negative electrode according to one aspect of the present invention has a negative electrode active material layer containing solid graphite, the average circularity of the solid graphite is 0.7 or less, and the negative electrode active material layer further contains carbon fine particles. It is a negative electrode for the electric storage element to contain.
- the negative electrode according to one aspect of the present invention can improve the input performance of the storage element in a low temperature environment. Although the reason for this is not clear, the following reason is presumed. In the case of solid graphite, since electrolyte such as electrolytic solution is hardly impregnated inside the particles, the contact area with the electrolyte is small, so side reactions and film formation during charging and discharging are difficult to occur, and from this point, the reaction resistance increases. input performance can be improved. However, since solid graphite tends to have a low average circularity due to its manufacturing process, the negative electrode active material layer containing solid graphite has a high filling rate.
- the negative electrode active material layer containing solid graphite generally has small voids that can hold the electrolyte, and as a result, the supply of charge transport ions tends to be insufficient. Especially in a low-temperature environment, when the filling rate of the negative electrode active material layer is high, the supply shortage of charge-transporting ions becomes conspicuous.
- the negative electrode active material layer further contains carbon microparticles, and the carbon microparticles form a structural structure. can increase As described above, according to the negative electrode according to one aspect of the present invention, since solid graphite is used, side reactions and film formation are reduced, and the electrolyte is sufficiently retained by containing carbon fine particles. It is considered that the charge transport ions are sufficiently supplied by the presence of the ions, so that the input performance of the storage element can be improved in a low-temperature environment.
- 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. In a preferred embodiment, the area ratio of voids in solid graphite may be 1% 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 of the negative electrode fixed with resin is exposed using a cross-section polisher (trade name) by ion milling to prepare a sample for measurement.
- a negative electrode to be measured is prepared by the following procedure.
- the electric storage element is discharged at a constant current of 0.1 C to the final discharge voltage in normal use, and is in a discharged state.
- This discharged electric storage element is disassembled, the negative electrode is taken out, thoroughly washed with dimethyl carbonate, and then dried under reduced pressure at room temperature.
- the work from dismantling the 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.
- JSM-7001F manufactured by JEOL Ltd.
- the SEM image shall be a secondary electron image.
- the acceleration voltage is 15 kV.
- the observation magnification is set to such a magnification 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 "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.
- the area ratios R2, R3, . (5) Determination of void area ratio By calculating the average value of all void area ratios R1, R2, R3, .
- 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 intercalated and deintercalated are sufficiently released during charging and discharging.
- the open circuit voltage is 0.7 V or higher.
- the "average circularity" of solid graphite is the average of the circularities of any three solid graphite particles.
- the circularity of each particle is measured by image analysis based on SEM images of solid graphite.
- An SEM image of solid graphite is obtained according to the procedure (1) and (2) for determining the "area ratio of voids in the particle to the area of the entire particle (porosity)" in the graphite particle.
- the image analysis is performed using the image analysis software PopImaging 6.00 described in the procedure for determining the "area ratio (porosity) of voids in the particles with respect to the area of the entire particles" in the graphite particles described above.
- By image analysis the area of all three arbitrary solid graphite particles and the peripheral length of the particles are measured from the SEM image.
- the circularity of each particle of solid graphite is calculated by the following formula, and the average value is defined as the "average circularity" of solid graphite.
- Circularity (4 ⁇ ⁇ area of entire particle) /
- Carbon fine particles refer to carbon particles with an average primary particle diameter of 500 nm or less.
- the “average primary particle size” is the average value of the particle sizes of arbitrary 50 primary particles observed in the SEM image of the carbon fine particles.
- the primary particles are particles for which grain boundaries are not observed in appearance in the SEM image.
- the particle diameter of primary particles is determined as follows. The shortest diameter that passes through the center of the minimum circumscribed circle of the primary particles is defined as the shortest diameter, and the diameter that passes through the center and is perpendicular to the shortest diameter is defined as the longer diameter. Let the average value of a long diameter and a short diameter be a primary particle diameter. When there are two or more shortest diameters, the longest perpendicular diameter is taken as the shortest diameter.
- the average particle size of the solid graphite is preferably 8 ⁇ m or less.
- 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 the value (median diameter) at which the volume-based cumulative distribution calculated according to 50%.
- the average particle size based on the above measurement is the particle size of each particle of solid graphite, which is measured by extracting 100 particles from the SEM image of solid graphite, avoiding extremely large particles and extremely small particles. It has been confirmed that it almost matches the average value of The particle size of each solid graphite particle based on the measurement from this SEM image is determined as follows.
- An SEM image of solid graphite is obtained according to the procedure (1) and (2) for determining the "area ratio of voids in the particle to the area of the entire particle (porosity)" in the graphite particle.
- the shortest diameter that passes through the center of the minimum circumscribed circle of each particle of solid graphite is defined as the minor axis, and the diameter that passes through the center and is perpendicular to the minor axis is defined as the major axis.
- the average value of the major axis and the minor axis is taken as the particle size of each particle of solid graphite.
- the longest perpendicular diameter is taken as the shortest diameter.
- the ratio of the average pore size of the negative electrode active material layer to the average particle size of the solid graphite is preferably less than 0.14. As the content of carbon fine particles in the negative electrode active material layer increases, the pores of the negative electrode active material layer become smaller. This indicates that the content of carbon fine particles in the substance layer is large. Therefore, when the ratio of the average pore size of the negative electrode active material layer to the average particle size of the solid graphite is less than 0.14, the effect of enhancing the retention of the electrolyte in the negative electrode active material layer by the carbon fine particles is particularly sufficiently exhibited. , the input performance of the storage element can be further enhanced in a low-temperature environment.
- the "average pore diameter" of the negative electrode active material layer is a value obtained by the following method based on the pore distribution measured by a mercury porosimeter. "AutoPore 9600” is used as a measuring device, and the contact angle of mercury is set at 130° and the surface tension is set at 484 mN/m. The range of pore diameters to be measured is from 20 ⁇ m to 0.0055 ⁇ m, and the pore volume in this range is measured. Assuming that the pores are cylindrical, the volume V of the pores and the surface area A of the pores are expressed by the following equations.
- H pore depth (equivalent to the height of the cylinder)
- a sample of the negative electrode active material layer to be measured is prepared according to the procedure (1) for determining the "area ratio of voids in the particles to the area of the entire particles (void ratio)" in the graphite particles.
- a power storage element according to another aspect of the present invention includes the negative electrode according to one aspect of the present invention. Since the power storage device includes the negative electrode according to one aspect of the present invention, it has high input performance in a low-temperature environment.
- 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 negative electrode according to one embodiment of the present invention has a negative electrode substrate and a negative electrode active material layer disposed on the negative electrode substrate directly or via an intermediate layer.
- the said negative electrode is a negative electrode used for electrical storage elements, such as a secondary battery.
- a negative 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).
- 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.
- the negative electrode substrate include foil, deposited film, mesh, porous material, and the like, and foil is preferable 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 "average thickness" of the negative electrode substrate and the later-described positive electrode substrate refers to a value obtained by dividing the punched mass when a substrate having a predetermined area is punched out by the true density and the punched area of the substrate.
- the intermediate layer is a layer arranged between the negative electrode substrate and the negative electrode active material layer.
- the intermediate layer reduces the contact resistance between the negative electrode substrate and the negative electrode active material layer by containing a conductive agent such as carbon particles.
- the composition of the intermediate layer is not particularly limited, and includes, for example, a binder and a conductive agent.
- the negative electrode active material layer contains solid graphite and carbon fine particles.
- the negative electrode active material layer optionally contains optional components such as a negative electrode active material other than solid graphite, a conductive agent other than carbon fine particles, a binder, a thickener, and a filler.
- Solid graphite is a component that functions as a negative electrode active material. By including solid graphite in the negative electrode active material layer of the negative electrode, side reactions and film formation during charging and discharging can be suppressed, and as a result, the input performance of the storage element in a low temperature environment can be enhanced.
- the solid graphite may be solid natural graphite or solid artificial graphite, but is preferably solid natural graphite.
- the use of solid natural graphite tends to improve the input performance of the storage element in a low-temperature environment. Although the details are unknown, it is presumed that this is due to the fact that solid natural graphite has a higher crystallinity than solid artificial graphite.
- 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 a 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, for example, preferably 1 ⁇ m or more and 30 ⁇ m or less, more preferably 2 ⁇ m or more and 10 ⁇ m or less, and even more preferably 3 ⁇ m or more and 8 ⁇ m or less.
- the average particle diameter of the solid graphite is, for example, preferably 1 ⁇ m or more and 30 ⁇ m or less, more preferably 2 ⁇ m or more and 10 ⁇ m or less, and even more preferably 3 ⁇ m or more and 8 ⁇ m or less.
- a crusher, a classifier, etc. are used to obtain solid graphite 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 classification method a sieve, an air classifier, or the like is used as necessary, both dry and wet.
- the upper limit of the average circularity of solid graphite is 0.7, preferably 0.6, and more preferably 0.5.
- the average circularity of the solid graphite is equal to or less than the above upper limit, the contact area between the solid graphite particles tends to increase, and the electron conductivity of the negative electrode active material layer tends to improve.
- the voids in the negative electrode active material layer that can hold the electrolyte become small, so the negative electrode active material layer needs to contain fine carbon particles.
- the lower limit of the average circularity of solid graphite is preferably 0.2, more preferably 0.3, and still more preferably 0.4.
- the average circularity of solid graphite may be equal to or greater than any of the above lower limits and equal to or less than any of the above upper limits.
- the average circularity of solid graphite can be adjusted by the type of negative electrode active material and manufacturing method.
- the average primary particle size of solid graphite is usually over 500 nm, preferably 1 ⁇ m or more.
- the BET specific surface area of solid graphite is preferably 1 m 2 /g or more and 15 m 2 /g or less, more preferably 3 m 2 /g or more and 10 m 2 /g or less. When the BET specific surface area of the solid graphite is within the above range, particularly good charge/discharge performance can be exhibited.
- 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 even more preferably 95% by mass or more in some cases.
- the negative electrode active material layer may contain a negative electrode active material other than solid graphite.
- Other negative electrode active materials include , for example, metal Li; metals or metalloids such as Si and Sn; metal oxides or metalloid oxides such as Si oxide, Ti oxide and Sn oxide; Titanium-containing oxides such as 12 , LiTiO 2 and TiNb 2 O 7 ; polyphosphate compounds; silicon carbide; graphite other than solid graphite, carbon such as non-graphitizable carbon (easily graphitizable carbon or non-graphitizable carbon) materials and the like.
- the content of solid graphite in all negative electrode active materials is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 99% by mass or more, and even more preferably 99.9% by mass or more. 100% by mass is particularly preferred.
- the negative electrode active material consists essentially of solid graphite, it is possible to further improve the input performance of the storage element in a low-temperature environment.
- the content of the negative electrode active material 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 even more preferably 95% by mass or more in some cases.
- the carbon fine particles are components that enhance the retention of the electrolyte in the negative electrode active material layer. Carbon microparticles can also function as a conductive agent. Carbon fine particles usually form a structural structure in which primary particles are aggregated.
- Carbon black such as furnace black, acetylene black, and ketjen black is preferably used as the fine carbon particles.
- One or two or more kinds of carbon fine particles can be used.
- the average primary particle diameter of the carbon microparticles is preferably 1 nm or more and 500 nm or less, more preferably 5 nm or more and 200 nm or less, and even more preferably 10 nm or more and 100 nm or less.
- the BET specific surface area of the fine carbon particles is preferably 20 m 2 /g or more and 150 m 2 /g or less, more preferably 30 m 2 /g or more and 100 m 2 /g or less.
- the BET specific surface area of the carbon fine particles is within the above range, the ability of the negative electrode active material layer to retain the electrolyte can be further enhanced.
- the content of the carbon fine particles in the negative electrode active material layer is, for example, preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 2% by mass or less.
- the content of the carbon fine particles is, for example, preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 2% by mass or less.
- the negative electrode active material layer may further contain a conductive agent other than carbon fine particles.
- Other conductive agents are not particularly limited as long as they are conductive materials. Examples of such conductive agents include carbonaceous materials other than fine carbon particles, metals, and conductive ceramics. Examples of carbonaceous materials other than carbon fine particles include carbon nanofibers, pitch-based carbon fibers, graphene, carbon nanotubes (CNT), fullerenes, and the like. Since the negative electrode active material layer of the negative electrode contains solid graphite and carbon fine particles, it usually has sufficient electron conductivity. Therefore, in one embodiment of the present invention, the negative electrode active material layer may not contain any conductive agent other than the carbon fine particles.
- 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 negative electrode active material layer is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 5% by mass or less, and further 0.5% by mass or more and 2% by mass or less. preferable. By setting the content of the binder within the above range, the negative electrode active material can be stably retained.
- thickeners examples include polysaccharide polymers such as carboxymethylcellulose (CMC) and methylcellulose. When the thickener has a functional group that reacts with lithium or the like, the functional group may be previously deactivated by methylation or the like.
- the content of the thickener in the negative electrode active material layer is preferably 0.1% by mass or more and 5% by mass or less, more preferably 0.5% by mass or more and 2% by mass or less.
- 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 content of the filler in the negative electrode active material layer is, for example, 0.1% by mass or more and 5% by mass or less.
- the content of the filler in the negative electrode active material layer may be 1% by mass or less, 0.1% by mass or less, or 0% by mass.
- 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, carbon fine particles, other conductive You may contain as a component other than an agent, a binder, a thickener, and a filler.
- 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.
- 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, carbon fine particles, other
- the average pore diameter of the negative electrode active material layer is preferably 0.3 ⁇ m or more and 2 ⁇ m or less, more preferably 0.5 ⁇ m or more and 1.5 ⁇ m or less, and even more preferably 0.7 ⁇ m or more and 1.1 ⁇ m or less.
- the average pore diameter of the negative electrode active material layer is within the above range, the electron conductivity, electrolyte retention, etc. of the negative electrode active material layer are optimized in a well-balanced manner.
- the ratio of the average pore diameter of the negative electrode active material layer to the average particle diameter of the solid graphite may be, for example, 0.2 or less, but is preferably less than 0.14. , 0.13 or less.
- the ratio of the average pore size of the negative electrode active material layer to the average particle size of solid graphite is preferably 0.05 or more, more preferably 0.07 or more, and even more preferably 0.09 or more.
- the ratio of the average pore diameter of the negative electrode active material layer to the average particle diameter of the solid graphite can be within the range between any of the above lower limits and any of the above upper limits.
- the negative electrode can be produced, for example, by applying the negative electrode mixture paste directly or via an intermediate layer to the negative electrode base material and drying it. After drying, pressing or the like may be performed as necessary.
- the negative electrode mixture paste contains solid graphite, fine carbon particles, and optional components such as a binder, which constitute the negative electrode active material layer.
- the negative electrode mixture paste usually further contains a dispersion medium.
- a power storage device includes an electrode assembly having a positive electrode, a negative electrode, and a separator, an electrolyte, and a container that accommodates the electrode assembly and the electrolyte.
- 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 electrolyte exists in a state impregnated with the positive electrode, the negative electrode and the separator.
- a non-aqueous electrolyte secondary battery (hereinafter also simply referred to as a "secondary battery") using a non-aqueous electrolyte as an electrolyte will be described as an example of the storage element.
- 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.
- the structure of the intermediate layer is not particularly limited, and can be selected from, for example, the structures exemplified for the negative electrode.
- the positive electrode base material has conductivity.
- metals such as aluminum, titanium, tantalum and stainless steel, or alloys thereof are used.
- 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.
- aluminum or aluminum alloys 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 positive electrode active material layer contains a positive electrode active material.
- the positive electrode active material layer contains optional components such as a conductive agent, a binder, a thickener, a filler, etc., as required.
- Optional components such as a conductive agent, a binder, a thickener, and a filler can be selected from the materials exemplified for the negative electrode.
- Carbon fine particles such as graphite and carbon black can also be used as the conductive agent for the positive electrode active material layer.
- the positive electrode active material can be appropriately selected from known positive electrode active materials.
- a positive electrode active material for lithium ion secondary batteries a material capable of intercalating and deintercalating lithium ions is usually used.
- positive electrode active materials include lithium-transition metal composite oxides having an ⁇ -NaFeO 2 type crystal structure, lithium-transition metal composite oxides having a spinel-type crystal structure, polyanion compounds, chalcogen compounds, and sulfur.
- lithium transition metal composite oxides having an ⁇ -NaFeO 2 type crystal structure examples include Li[Li x Ni (1-x) ]O 2 (0 ⁇ x ⁇ 0.5), Li[Li x Ni ⁇ Co ( 1-x- ⁇ ) ]O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ 1, 0 ⁇ 1-x- ⁇ ), Li[Li x Co (1-x) ]O 2 (0 ⁇ x ⁇ 0.5), Li[Li x Ni ⁇ Mn (1-x- ⁇ ) ]O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ 1, 0 ⁇ 1-x- ⁇ ), Li[Li x Ni ⁇ Mn ⁇ Co (1-x- ⁇ - ⁇ ) ]O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ , 0 ⁇ , 0.5 ⁇ + ⁇ 1, 0 ⁇ 1-x- ⁇ - ⁇ ), Li[Li x Ni ⁇ Co ⁇ Al (1-x- ⁇ - ⁇ ) ]O 2 (0 ⁇ x ⁇ 0.5, 0 ⁇ , 0 ⁇ , 0.5 ⁇ + ⁇ 1, 0 ⁇ 1-x-
- lithium transition metal composite oxides having a spinel crystal structure examples include Li x Mn 2 O 4 and Li x Ni ⁇ Mn (2- ⁇ ) O 4 .
- polyanion compounds include LiFePO4 , LiMnPO4 , LiNiPO4 , LiCoPO4 , Li3V2 ( PO4 ) 3 , Li2MnSiO4 , Li2CoPO4F and the like.
- chalcogen compounds include titanium disulfide, molybdenum disulfide, and molybdenum dioxide.
- the atoms or polyanions in these materials may be partially substituted with atoms or anionic species of other elements. These materials may be coated with other materials on their surfaces. In the positive electrode active material layer, one kind of these materials may be used alone, or two or more kinds may be mixed and used.
- 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.
- the content of the positive electrode active material 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 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 positive electrode can be produced, for example, by applying the positive electrode mixture paste directly or via an intermediate layer to the positive electrode base material and drying it. After drying, pressing or the like may be performed as necessary.
- the positive electrode mixture paste contains the positive electrode active material and optional components such as a conductive agent and a binder, which constitute the positive electrode active material layer.
- the positive electrode mixture paste usually further contains a dispersion medium.
- the negative electrode provided in the secondary battery is the negative electrode described above as the negative electrode according to one embodiment of the present invention.
- 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 retention of a non-aqueous electrolyte.
- 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 halogens 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.
- the electrolyte salt can be appropriately selected from known electrolyte salts.
- electrolyte salts include lithium salts, sodium salts, potassium salts, magnesium salts, onium salts and the like. Among these, lithium salts are preferred.
- 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 a halogenated hydrocarbon group.
- inorganic lithium salts are preferred, and LiPF6 is more preferred.
- the content of the electrolyte salt in the non-aqueous electrolyte is preferably 0.1 mol/dm3 or more and 2.5 mol/dm3 or less, and 0.3 mol/ dm3 or more and 2.0 mol/dm3 or less at 20°C and 1 atm. It is more preferably 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 non-aqueous 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 non-aqueous 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 ion conductivity, such as lithium, sodium, and calcium, and is solid at room temperature (for example, 15°C to 25°C).
- Examples of solid electrolytes include sulfide solid electrolytes, oxide solid electrolytes, oxynitride 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 , Li 10 Ge—P 2 S 12 and the like.
- the shape of the electric storage element of this embodiment is not particularly limited, and examples thereof include cylindrical batteries, rectangular batteries, flat batteries, coin batteries, button batteries, and the like.
- Fig. 1 shows a power 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 power storage device 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 power sources for power storage.
- EV electric vehicles
- HEV hybrid vehicles
- PHEV plug-in hybrid vehicles
- power sources for electronic devices such as personal computers and communication terminals
- power sources for power storage
- it can be mounted as a power storage unit (battery module) configured by assembling a plurality of power storage elements 1 .
- the technology of the present invention may be applied to at least one power storage element included in the power storage unit.
- FIG. 2 shows an example of a power storage device 30 in which power storage units 20 in which two or more electrically connected power storage elements 1 are assembled are further assembled.
- the power storage device 30 may include a bus bar (not shown) electrically connecting two or more power storage elements 1, a bus bar (not shown) electrically connecting two or more power storage units 20, and the like. good.
- the power storage unit 20 or power storage device 30 may include a state monitoring device (not shown) that monitors the state of one or more power storage elements.
- a method for manufacturing the electric storage device of the present embodiment can be appropriately selected from known methods.
- the manufacturing method includes, for example, preparing an electrode body, preparing an electrolyte, and housing the electrode body and the 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 electrolyte in the container can be appropriately selected from known methods.
- the non-aqueous electrolytic solution may be injected through an injection port formed in the container, and then the injection port may be sealed.
- the electric storage device of the present invention is not limited to the above-described 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 storage element is used as a chargeable/dischargeable non-aqueous electrolyte secondary battery (for example, a lithium ion secondary battery), but the type, shape, size, capacity, etc. of the storage element are arbitrary. .
- the present invention can also be applied to capacitors such as various secondary batteries, electric double layer capacitors, and lithium ion capacitors.
- the electric storage element of the present invention can also be applied to an electric storage element whose electrolyte is an electrolyte other than a non-aqueous electrolyte, that is, an electric storage element whose electrolyte contains water.
- 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 negative electrode) Solid natural graphite (average particle size (a): 7.7 ⁇ m, BET specific surface area: 6 m 2 /g) as negative electrode active material, carbon black (CB: BET specific surface area: 60 m 2 /g) as carbon fine particles, binder: A negative electrode mixture paste was prepared by mixing styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC) as a thickener, and water as a dispersion medium. The mass ratio of solid natural graphite, CB, SBR and CMC was 97:1:1:1 (in terms of solid content).
- SBR styrene-butadiene rubber
- CMC carboxymethyl cellulose
- a negative electrode mixture paste was applied to both surfaces of a copper foil as a negative electrode substrate and dried to form an unpressed negative electrode active material layer. Thereafter, the unpressed negative electrode active material layer was roll-pressed to obtain a negative electrode.
- the porosity of the solid natural graphite in the negative electrode active material layer of the negative electrode obtained by the method described above was 0.5%, and the average circularity was 0.52.
- the average pore diameter (b) of the negative electrode active material layer is 1.03 ⁇ m, and the ratio (b/a) of the average pore diameter (b) of the negative electrode active material layer to the average particle diameter (a) of solid graphite is was 0.13.
- An electrolyte was prepared by dissolving LiPF 6 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.
- An electrode assembly was produced by laminating the above positive electrode and the above negative electrode with a separator interposed therebetween. A polyolefin microporous film was used as the separator. The electrode assembly was placed in a container, and the electrolyte was injected into the container.
- Comparative Examples 1 to 4 Energy storage elements of Comparative Examples 1 to 4 were obtained in the same manner as in Example 1, except that the type of negative electrode active material and the presence or absence of carbon fine particles (CB) were as shown in Table 1. When the carbon fine particles were not used, the mass ratio of the negative electrode active material, SBR and CMC was 98:1:1 (in terms of solid content).
- Table 1 shows the porosity and average circularity of natural graphite measured in the negative electrode active material layer of the negative electrode of each comparative example, the average pore diameter (b) of the negative electrode active material layer, and the negative electrode active material. The ratio (b/a) of the average pore diameter (b) of the negative electrode active material layer to the average particle diameter (a) is also shown.
- the power storage element of Example 1 has higher input performance in a low temperature environment than the power storage elements of Comparative Examples 1 to 4. From the comparison between Comparative Examples 2 and 3, when the negative electrode active material is hollow graphite, the effect of improving the input performance due to the carbon fine particles is slight. , it can be seen that when the negative electrode active material is solid graphite, the input performance is remarkably enhanced by the carbon fine particles. Also, from a comparison of Comparative Examples 1 and 2, etc., it can be confirmed that the input performance of the storage element tends to be improved by using a negative electrode active material (graphite) having a small average particle size.
- a negative electrode active material graphite
- the present invention can be applied to personal computers, electronic devices such as communication terminals, and electric storage elements used as power sources for automobiles and the like.
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Abstract
Description
黒鉛粒子における「粒子全体の面積に対する粒子内の空隙の面積率(空隙率)」は、以下の手順で決定することができる。
(1)測定用試料の準備
測定対象とする負極を熱硬化性の樹脂で固定する。樹脂で固定された負極について、イオンミリング法によりクロスセクション・ポリッシャ(商品名)を用いて断面を露出させ、測定用試料を作製する。なお、測定対象とする負極は、下記の手順により準備する。蓄電素子を、0.1Cの電流で、通常使用時の放電終止電圧まで定電流放電し、放電された状態とする。この放電された状態の蓄電素子を解体し、負極を取り出して、ジメチルカーボネートにより十分に洗浄した後、室温にて減圧乾燥を行う。蓄電素子の解体から測定対象とする負極の準備までの作業は、露点-40℃以下の乾燥空気雰囲気中で行う。
(2)SEM像の取得
SEM像の取得には、走査型電子顕微鏡としてJSM-7001F(日本電子株式会社製)を用いる。SEM像は、二次電子像を観察するものとする。加速電圧は、15kVとする。観察倍率は、一視野に現れる黒鉛粒子が3個以上15個以内となる倍率に設定する。得られたSEM像は、画像ファイルとして保存する。その他、スポット径、ワーキングディスタンス、照射電流、輝度、フォーカス等の諸条件は、黒鉛粒子の輪郭が明瞭になるように適宜設定する。
(3)黒鉛粒子の輪郭の切り抜き
画像編集ソフトAdobe Photoshop Elements 11の画像切り抜き機能を用いて、取得したSEM像から黒鉛粒子の輪郭を切り抜く。この輪郭の切り抜きは、クイック選択ツールを用いて黒鉛粒子の輪郭より外側を選択し、黒鉛粒子以外を黒背景へと編集して行う。このとき、輪郭を切り抜くことができた黒鉛粒子が3個未満であった場合は、再度、SEM像を取得し、輪郭を切り抜くことができた黒鉛粒子が3個以上になるまで行う。
(4)二値化処理
切り抜いた黒鉛粒子のうち1つ目の黒鉛粒子の画像について、画像解析ソフトPopImaging 6.00を用い、強度が最大となる濃度から20%分小さい濃度を閾値に設定して二値化処理を行う。二値化処理により、濃度の高い側の面積を算出することで「粒子内の空隙の面積S1」とする。
ついで、先ほどと同じ1つ目の黒鉛粒子の画像について、濃度10%を閾値として二値化処理を行う。二値化処理により、黒鉛粒子の外縁を決定し、当該外縁の内側の面積を算出することで、「粒子全体の面積S0」とする。
上記算出したS1及びS0を用いて、S0に対するS1の比(S1/S0)を算出することにより、1つ目の黒鉛粒子における「粒子全体の面積に対する粒子内の空隙の面積率R1」を算出する。
切り抜いた黒鉛粒子のうち2つ目以降の黒鉛粒子の画像についても、それぞれ、上記の二値化処理を行い、面積S1、面積S0を算出する。この算出した面積S1、面積S0に基づいて、それぞれの黒鉛粒子の空隙の面積率R2、R3、・・・を算出する。
(5)空隙の面積率の決定
二値化処理により算出した全ての空隙の面積率R1、R2、R3、・・・の平均値を算出することにより、「粒子全体の面積に対する粒子内の空隙の面積率(空隙率)」を決定する。
なお、上記「SEM像の取得」に用いる走査型電子顕微鏡、「黒鉛粒子の輪郭の切り抜き」に用いる画像編集ソフト、及び「二値化処理」に用いる画像解析ソフトに代えて、これらと同等の測定、画像編集及び画像解析が可能な装置及びソフトウェア等を用いてもよい。
円形度=(4π×粒子全体の面積)/(粒子の外周長)2
V=π×(d/2)2×H
A=π×d×H
d:細孔径、H:細孔の深さ(円筒の高さに相当)
なお、表面積の計算において、円筒の両底面に相当する面の面積は無視することができる。上記2つの式から、d=4V/Aの式が導かれる。従って、平均細孔径dは、全細孔の表面積Aと全細孔体積Vの値を用いて、d=4V/Aの式から算出することができる。測定に供する負極活物質層の試料は、上記した黒鉛粒子における「粒子全体の面積に対する粒子内の空隙の面積率(空隙率)」を決定する手順の(1)に準じて準備する。
本発明の一実施形態に係る負極は、負極基材と、当該負極基材に直接又は中間層を介して配される負極活物質層とを有する。当該負極は、二次電池等の蓄電素子に用いられる負極である。
負極基材の材質としては、銅、ニッケル、ステンレス鋼、ニッケルメッキ鋼等の金属又はこれらの合金、炭素質材料等が用いられる。これらの中でも銅又は銅合金が好ましい。負極基材としては、箔、蒸着膜、メッシュ、多孔質材料等が挙げられ、コストの観点から箔が好ましい。したがって、負極基材としては銅箔又は銅合金箔が好ましい。銅箔の例としては、圧延銅箔、電解銅箔等が挙げられる。
本発明の一実施形態に係る蓄電素子は、正極、負極及びセパレータを有する電極体と、電解質と、上記電極体及び電解質を収容する容器と、を備える。電極体は、通常、複数の正極及び複数の負極がセパレータを介して積層された積層型、又は、正極及び負極がセパレータを介して積層された状態で巻回された巻回型である。電解質は、正極、負極及びセパレータに含浸した状態で存在する。蓄電素子の一例として、電解質として非水電解質が用いられた非水電解質二次電池(以下、単に「二次電池」ともいう。)について説明する。
正極は、正極基材と、当該正極基材に直接又は中間層を介して配される正極活物質層とを有する。中間層の構成は特に限定されず、例えば上記負極で例示した構成から選択することができる。
当該二次電池に備わる負極は、本発明の一実施形態に係る負極として上記した負極である。
セパレータは、公知のセパレータの中から適宜選択できる。セパレータとして、例えば、基材層のみからなるセパレータ、基材層の一方の面又は双方の面に耐熱粒子とバインダとを含む耐熱層が形成されたセパレータ等を使用することができる。セパレータの基材層の形状としては、例えば、織布、不織布、多孔質樹脂フィルム等が挙げられる。これらの形状の中でも、強度の観点から多孔質樹脂フィルムが好ましく、非水電解質の保持性の観点から不織布が好ましい。セパレータの基材層の材料としては、シャットダウン機能の観点から例えばポリエチレン、ポリプロピレン等のポリオレフィンが好ましく、耐酸化分解性の観点から例えばポリイミドやアラミド等が好ましい。セパレータの基材層として、これらの樹脂を複合した材料を用いてもよい。
非水電解質としては、公知の非水電解質の中から適宜選択できる。非水電解質には、非水電解液を用いてもよい。非水電解液は、非水溶媒と、この非水溶媒に溶解されている電解質塩とを含む。
本実施形態の蓄電素子は、電気自動車(EV)、ハイブリッド自動車(HEV)、プラグインハイブリッド自動車(PHEV)等の自動車用電源、パーソナルコンピュータ、通信端末等の電子機器用電源、又は電力貯蔵用電源等に、複数の蓄電素子1を集合して構成した蓄電ユニット(バッテリーモジュール)として搭載することができる。この場合、蓄電ユニットに含まれる少なくとも1つの蓄電素子に対して、本発明の技術が適用されていればよい。
本実施形態の蓄電素子の製造方法は、公知の方法から適宜選択できる。当該製造方法は、例えば、電極体を準備することと、電解質を準備することと、電極体及び電解質を容器に収容することと、を備える。電極体を準備することは、正極及び負極を準備することと、セパレータを介して正極及び負極を積層又は巻回することにより電極体を形成することとを備える。
尚、本発明の蓄電素子は、上記実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加えてもよい。例えば、ある実施形態の構成に他の実施形態の構成を追加することができ、また、ある実施形態の構成の一部を他の実施形態の構成又は周知技術に置き換えることができる。さらに、ある実施形態の構成の一部を削除することができる。また、ある実施形態の構成に対して周知技術を付加することができる。
(負極の作製)
負極活物質である中実天然黒鉛(平均粒径(a)7.7μm、BET比表面積6m2/g)、炭素微粒子であるカーボンブラック(CB、BET比表面積60m2/g)、バインダであるスチレン-ブタジエンゴム(SBR)、増粘剤であるカルボキシメチルセルロース(CMC)、及び分散媒である水を混合して負極合剤ペーストを調製した。なお、中実天然黒鉛、CB、SBR及びCMCの質量比率は97:1:1:1(固形分換算)とした。負極基材としての銅箔の両面に負極合剤ペーストを塗布及び乾燥し、未プレスの負極活物質層を形成した。その後、未プレスの負極活物質層に対してロールプレスを行い、負極を得た。上記した方法で求めた得られた負極の負極活物質層中の中実天然黒鉛の空隙率は0.5%、平均円形度は0.52であった。また、負極活物質層の平均細孔径(b)は1.03μmであり、中実黒鉛の平均粒径(a)に対する負極活物質層の平均細孔径(b)の比(b/a)は0.13であった。
(正極の作製)
正極活物質であるLiNi1/3Co1/3Mn1/3O2、導電剤であるアセチレンブラック(AB)、バインダであるポリフッ化ビニリデン(PVDF)及び分散媒であるN-メチルピロリドン(NMP)を用いて正極合剤ペーストを調製した。なお、正極活物質、AB及びPVDFの質量比率は93:4:3(固形分換算)とした。正極基材としてのアルミニウム箔の両面に正極合剤ペーストを塗布し、乾燥した。その後、ロールプレスを行い、正極を得た。
(電解質の調製)
エチレンカーボネート及びエチルメチルカーボネートを体積比率30:70で混合した溶媒に、1.2mol/dm3の濃度でLiPF6を溶解させ、電解質を調製した。
(蓄電素子の作製)
セパレータを介して、上記正極と上記負極とを積層することにより電極体を作製した。なお、上記セパレータには、ポリオレフィン製微多孔膜を用いた。上記電極体を容器に収納し、内部に上記電解質を注入した後、封口し、実施例1の蓄電素子(非水電解質二次電池)を得た。
負極活物質の種類及び炭素微粒子(CB)の有無を表1の通りとしたこと以外は実施例1と同様にして、比較例1から4の各蓄電素子を得た。なお、炭素微粒子を用いない場合、負極活物質、SBR及びCMCの質量比率は98:1:1(固形分換算)とした。また、表1には、各比較例の負極の負極活物質層において測定した天然黒鉛の空隙率、及び平均円形度、並びに、負極活物質層の平均細孔径(b)、及び負極活物質の平均粒径(a)に対する負極活物質層の平均細孔径(b)の比(b/a)をあわせて示す。
得られた各蓄電素子について、25℃の温度環境下、充電電流1.0Cで4.1Vまで定電流充電した後、4.1Vで定電圧充電した。充電の終了条件は、総充電時間が3時間となるまでとした。10分間の休止を設けた後に、放電電流1.0Cで2.5Vまで定電流放電を行い、10分間の休止を設けた。これらの充電及び放電の工程を1サイクルとして、2サイクルを実施した。
その後、25℃の温度環境下にて、充電電流1.0Cで定電流充電を行い、充電状態(SOC)を50%にした。-30℃の恒温槽に4時間保管した後、0.2C、0.5C、又は1.0Cの定電流で、それぞれ10秒間充電した。各充電終了後には、0.05Cの電流で定電流放電を行い、SOCを50%にした。各充電における電流と充電開始10秒後の電圧との関係から、充電開始10秒後の電圧が4.1Vとなるときの電流(A0)を算出し、電圧(4.1V)と電流(A0)との積(4.1×A0)を求め、入力とした。比較例1の蓄電素子の入力を100%とした場合の各蓄電素子の入力の相対値(%)を求めた。結果を表1に示す。
2 電極体
3 容器
4 正極端子
41 正極リード
5 負極端子
51 負極リード
20 蓄電ユニット
30 蓄電装置
Claims (5)
- 中実黒鉛を含有する負極活物質層を有し、
上記中実黒鉛の平均円形度が0.7以下であり、
上記負極活物質層が炭素微粒子をさらに含有する蓄電素子用の負極。 - 上記中実黒鉛の平均粒径が8μm以下である請求項1に記載の負極。
- 上記中実黒鉛の平均粒径に対する上記負極活物質層の平均細孔径の比が0.14未満である請求項1又は請求項2に記載の負極。
- 請求項1又は請求項2に記載の負極を備える蓄電素子。
- 請求項3に記載の負極を備える蓄電素子。
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Citations (5)
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JP2000226206A (ja) * | 1999-02-04 | 2000-08-15 | Kansai Coke & Chem Co Ltd | 黒鉛粒子組成物およびそれを用いた塗布体の製造法 |
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 |
JP2015165510A (ja) * | 2015-05-18 | 2015-09-17 | 日立化成株式会社 | 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 |
JP2017069039A (ja) | 2015-09-30 | 2017-04-06 | 株式会社Gsユアサ | 蓄電素子用負極及び蓄電素子 |
WO2017221895A1 (ja) * | 2016-06-23 | 2017-12-28 | 昭和電工株式会社 | 黒鉛材およびそれを用いた二次電池用電極 |
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JP2000226206A (ja) * | 1999-02-04 | 2000-08-15 | Kansai Coke & Chem Co Ltd | 黒鉛粒子組成物およびそれを用いた塗布体の製造法 |
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 |
JP2015165510A (ja) * | 2015-05-18 | 2015-09-17 | 日立化成株式会社 | 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 |
JP2017069039A (ja) | 2015-09-30 | 2017-04-06 | 株式会社Gsユアサ | 蓄電素子用負極及び蓄電素子 |
WO2017221895A1 (ja) * | 2016-06-23 | 2017-12-28 | 昭和電工株式会社 | 黒鉛材およびそれを用いた二次電池用電極 |
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