WO2022130763A1 - 蓄電装置 - Google Patents
蓄電装置 Download PDFInfo
- Publication number
- WO2022130763A1 WO2022130763A1 PCT/JP2021/038044 JP2021038044W WO2022130763A1 WO 2022130763 A1 WO2022130763 A1 WO 2022130763A1 JP 2021038044 W JP2021038044 W JP 2021038044W WO 2022130763 A1 WO2022130763 A1 WO 2022130763A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- active material
- material layer
- negative electrode
- current collector
- positive electrode
- Prior art date
Links
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- 239000011149 active material Substances 0.000 claims description 90
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
-
- 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
- H01G11/66—Current collectors
- H01G11/70—Current collectors characterised by their structure
-
- 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
- H01G11/78—Cases; Housings; Encapsulations; Mountings
- H01G11/82—Fixing or assembling a capacitive element in a housing, e.g. mounting electrodes, current collectors or terminals in containers or encapsulations
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- 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
- H01M50/183—Sealing members
- H01M50/186—Sealing members characterised by the disposition of the sealing members
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/66—Current collectors
- H01G11/68—Current collectors characterised by their material
-
- 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
- H01M2004/029—Bipolar 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a power storage device.
- Patent Document 1 discloses a flat type power storage device configured by stacking a plurality of individually manufactured power storage cells in series.
- the storage cell has a positive electrode having a positive electrode active material layer formed in the center of one side of the resin collector and a negative electrode active material layer formed in the center of one side of the resin collector. It includes a negative electrode arranged so that the layer faces the positive electrode active material layer of the positive electrode, and a separator arranged between the positive electrode and the negative electrode.
- the storage cell is arranged on the outer peripheral portion of the resin current collector, and has a sealing portion that tightly seals between adjacent resin current collectors in the stacking direction.
- the sealing portion maintains a gap between the resin current collectors to prevent a short circuit between the resin current collectors, and tightly seals the space between the resin current collectors to form a closed space for accommodating the electrolyte.
- a method of increasing the capacity of a laminated storage cell in which a plurality of positive electrodes and negative electrodes are laminated via a separator a method of increasing the area of the active material layer can be considered.
- the capacity of the storage cell can be increased while maintaining the flat shape of the storage cell.
- the portion of the current collector to which the active material layer is adhered expands and contracts with the expansion and contraction of the active material layer during charging and discharging of the storage cell, local deformation is repeated at the non-adhered portion. Specifically, the unbonded portion is bent or bent due to the expansion of the active material layer, and the bent portion or the bent portion is stretched due to the contraction of the active material layer.
- the amount of expansion of the active material layer during charging and discharging increases as the area of the active material layer increases, and the active material layer expands.
- the amount of deformation of the unbonded portion due to shrinkage also increases.
- the load acting on the unbonded portion increases due to the expansion and contraction of the active material layer, and wrinkles and tears are likely to occur in the unbonded portion.
- the power storage device that solves the above problems has a first electrode having a first active material layer formed on the first surface of the first current collector, and a second active material layer on the first surface of the second current collector.
- a second electrode formed so that the second active material layer faces the first active material layer of the first electrode, and the first active material layer and the second active material layer.
- the spacer is provided with a separator arranged between the first collectors and a spacer arranged between the first surfaces of the first current collector and the second collector, and the spacers are the first active material layer and the said.
- the first electrode and the second electrode are arranged so as to surround the periphery of the second active material layer and are adhered to the first surfaces of the first current collector and the second current collector.
- a closed space is formed between the layers, and the first active material layer has a rectangular shape when viewed from the stacking direction, and the spacer on the first surface of the first current collector is adhered to the first active material layer.
- the non-existent region a region in which the first active material layer is formed and a region in which the first active material layer is not formed are provided, and the long side of the first active material layer in the plan view is provided.
- the length is L1
- the length between the spacer and the first active material layer, and the length in the direction parallel to the long side of the first active material layer is L2, the ratio (L2).
- / L1 is a power storage device having 0.02 or less, and at least one corner of the first active material layer has an arc-shaped chamfered shape, and the curvature of the portion having the maximum curvature at the corner is The radius is 5 mm or more.
- the present inventors When the area of the active material layer having a rectangular shape in a plan view is increased, the present inventors have formed a non-adhered portion in which the spacer in the current collector is not adhered and the active material layer is not formed. It was found that the wrinkles and tears that occur are concentrated near the tips of the corners of the active material layer.
- the corner portion of the first active material layer having a rectangular shape in a plan view at the first electrode is chamfered in an arc shape.
- the concentration of stress on the tip of the corner of the first active material layer is relaxed, so that the corner of the first active material layer becomes the first current collector.
- the stress transmitted to the unbonded portion is widely dispersed. As a result, the maximum strain generated in the unbonded portion of the first current collector when the first active material layer is expanded can be reduced, and wrinkles and tears generated in the unbonded portion can be suppressed.
- At least one corner portion of the first active material layer has an arc shape that is convex outward. According to the above configuration, since the protruding corner portion is not formed, it is possible to suppress the stress of expansion of the first active material layer from being concentrated on a part of the corner portion. Therefore, the effect of suppressing wrinkles and tears that occur in the unbonded portion of the first current collector can be obtained more remarkably. Further, as compared with the shape in which the corners are chamfered with C, the amount of decrease in the area of the first active material layer due to the chamfering of the corners can be suppressed to be small, and the decrease in the capacity of the first electrode can be suppressed.
- the radius of curvature is preferably 10 mm or more. According to the above configuration, the maximum strain generated in the unbonded portion of the first current collector can be further reduced.
- the radius of curvature is preferably 30 mm or less.
- the first current collector is preferably a copper foil, and the first active material layer preferably contains a carbon-based active material.
- the configuration in which the first active material layer containing a carbon-based active material having a large expansion rate during charging and discharging and the copper foil are combined is the first current collector due to the expansion and contraction of the first active material layer during charging and discharging. Wrinkles and tears are especially likely to occur. Therefore, the above-mentioned effect can be obtained more remarkably by forming the corner portion of the first active material layer into a specific shape.
- a closed space is formed by a member that seals between adjacent current collectors, wrinkles and tears of the current collector that occur when the area of the active material layer is increased are prevented. Can be suppressed.
- Sectional drawing of the power storage device Top view of the negative electrode.
- a graph showing the results of a simulation test. (A) is an elliptical arc-shaped corner portion, (b) is a corner portion having a shape in which a plurality of curved portions are directly connected, and (c) is a shape in which a plurality of curved portions are connected via a straight line portion. Corner.
- the power storage device 10 shown in FIG. 1 is a power storage module used for batteries of various vehicles such as forklifts, hybrid vehicles, and electric vehicles.
- the power storage device 10 is, for example, a secondary battery such as a nickel hydrogen secondary battery or a lithium ion secondary battery.
- the power storage device 10 may be an electric double layer capacitor. In this embodiment, a case where the power storage device 10 is a lithium ion secondary battery is illustrated.
- the power storage device 10 includes a cell stack 30 (laminated body) in which a plurality of power storage cells 20 are stacked (stacked) in the stacking direction.
- the stacking direction of the plurality of storage cells 20 is simply referred to as a stacking direction.
- Each storage cell 20 includes a positive electrode 21, a negative electrode 22, a separator 23, and a spacer 24.
- the positive electrode 21 includes a positive electrode current collector 21a and a positive electrode active material layer 21b provided on the first surface 21a1 of the positive electrode current collector 21a.
- the positive electrode active material layer 21b is formed in the central portion of the first surface 21a1 of the positive electrode current collector 21a in a plan view (hereinafter, simply referred to as a plan view) viewed from the stacking direction.
- the peripheral edge of the first surface 21a1 of the positive electrode current collector 21a in a plan view is a positive electrode uncoated portion 21c in which the positive electrode active material layer 21b is not provided.
- the positive electrode uncoated portion 21c is arranged so as to surround the periphery of the positive electrode active material layer 21b in a plan view.
- the negative electrode 22 includes a negative electrode current collector 22a and a negative electrode active material layer 22b provided on the first surface 22a1 of the negative electrode current collector 22a.
- the negative electrode active material layer 22b is formed in the central portion of the first surface 22a1 of the negative electrode current collector 22a.
- the peripheral edge of the first surface 22a1 of the negative electrode current collector 22a in a plan view is a negative electrode uncoated portion 22c in which the negative electrode active material layer 22b is not provided.
- the negative electrode uncoated portion 22c is arranged so as to surround the periphery of the negative electrode active material layer 22b in a plan view.
- the positive electrode 21 and the negative electrode 22 are arranged so that the positive electrode active material layer 21b and the negative electrode active material layer 22b face each other in the stacking direction. That is, the opposite directions of the positive electrode 21 and the negative electrode 22 coincide with the stacking direction.
- the negative electrode active material layer 22b is formed to have the same size as the positive electrode active material layer 21b, or is formed one size larger than the positive electrode active material layer 21b. When the negative electrode active material layer 22b is formed one size larger than the positive electrode active material layer 21b, the entire forming region of the positive electrode active material layer 21b is located in the forming region of the negative electrode active material layer 22b in a plan view. ing.
- the positive electrode current collector 21a has a second surface 21a2 which is a surface opposite to the first surface 21a1.
- the positive electrode 21 is an electrode having a monopolar structure in which neither the positive electrode active material layer 21b nor the negative electrode active material layer 22b is formed on the second surface 21a2 of the positive electrode current collector 21a.
- the negative electrode current collector 22a has a second surface 22a2 which is a surface opposite to the first surface 22a1.
- the negative electrode 22 is an electrode having a monopolar structure in which neither the positive electrode active material layer 21b nor the negative electrode active material layer 22b is formed on the second surface 22a2 of the negative electrode current collector 22a.
- the separator 23 is a member arranged between the positive electrode 21 and the negative electrode 22 and allowing a charge carrier such as lithium ion to pass through while separating the positive electrode 21 and the negative electrode 22 to prevent a short circuit due to contact between the two electrodes. ..
- the separator 23 is, for example, a porous sheet or a non-woven fabric containing a polymer that absorbs and retains an electrolyte.
- Examples of the material constituting the separator 23 include polyolefins such as polypropylene and polyethylene, polyester and the like.
- the separator 23 may have a single-layer structure or a multi-layer structure.
- the multilayer structure may have, for example, an adhesive layer, a ceramic layer as a heat-resistant layer, and the like.
- the spacer 24 is between the first surface 21a1 of the positive electrode current collector 21a of the positive electrode 21 and the first surface 22a1 of the negative electrode current collector 22a of the negative electrode 22 and more than the positive electrode active material layer 21b and the negative electrode active material layer 22b. It is arranged on the outer peripheral side and is adhered to both the positive electrode current collector 21a and the negative electrode current collector 22a.
- the spacer 24 maintains a distance between the positive electrode current collector 21a and the negative electrode current collector 22a to prevent a short circuit between the current collectors and tightly seals the current collectors.
- the spacer 24 extends along the peripheral edges of the positive electrode current collector 21a and the negative electrode current collector 22a in a plan view, and is formed in a frame shape surrounding the positive electrode current collector 21a and the negative electrode current collector 22a. ing. The spacer 24 is arranged between the positive electrode uncoated portion 21c on the first surface 21a1 of the positive electrode current collector 21a and the negative electrode uncoated portion 22c on the first surface 22a1 of the negative electrode current collector 22a.
- Examples of the material constituting the spacer 24 include various resins such as polyethylene (PE), modified polyethylene (modified PE), polystyrene (PS), polypropylene (PP), modified polypropylene (modified PP), ABS resin, and AS resin. Materials are mentioned.
- the separator 23 and the electrolyte are housed in the closed space S.
- the peripheral portion of the separator 23 is in a state of being buried in the spacer 24.
- Examples of the electrolyte include a liquid electrolyte and a polymer gel electrolyte containing an electrolyte held in a polymer matrix.
- Examples of the liquid electrolyte include a liquid electrolyte containing a non-aqueous solvent and an electrolyte salt dissolved in the non-aqueous solvent.
- the electrolyte salt known lithium salts such as LiClO4, LiAsF6, LiPF6, LiBF4, LiCF3SO3, LiN (FSO2) 2, and LiN (CF3SO2) 2 can be used.
- the non-aqueous solvent known solvents such as cyclic carbonates, cyclic esters, chain carbonates, chain esters, ethers and the like can be used. In addition, you may use two or more kinds of these known solvent materials in combination.
- the spacer 24 can suppress the leakage of the electrolyte contained in the closed space S to the outside by sealing the closed space S between the positive electrode 21 and the negative electrode 22. Further, the spacer 24 can suppress the intrusion of moisture from the outside of the power storage device 10 into the closed space S. Further, the spacer 24 can suppress the gas generated from the positive electrode 21 or the negative electrode 22 from leaking to the outside of the power storage device 10 due to, for example, a charge / discharge reaction.
- FIG. 2 shows the arrangement of the negative electrode active material layer 22b and the spacer 24 on the first surface 22a1 of the negative electrode current collector 22a, and the plan view shape of the negative electrode active material layer 22b and the spacer 24.
- the negative electrode active material layer 22b has a rectangular shape in a plan view and is formed in the central portion of the first surface 22a1 of the negative electrode current collector 22a.
- the outer peripheral portion of the first surface 22a1 of the negative electrode current collector 22a where the negative electrode active material layer 22b is not provided is the negative electrode uncoated portion 22c.
- the spacer 24 has a rectangular frame shape in a plan view in which the inner and outer peripheral edges are rectangular, and is adhered to the negative electrode uncoated portion 22c on the first surface 22a1 of the negative electrode current collector 22a.
- the rectangular inner peripheral edge of the spacer 24 is formed larger than the rectangular negative electrode active material layer 22b, and the negative electrode is not adhered to the negative electrode uncoated portion 22c of the negative electrode current collector 22a.
- the adhesive portion 22c1 is formed. In other words, in the region where the spacer 24 is not adhered on the first surface 22a1 of the negative electrode current collector 22a, a region where the negative electrode active material layer 22b is formed and a region where the negative electrode active material layer 22b is not formed. Is provided, and the region where the negative electrode active material layer 22b is not formed becomes the negative electrode unbonded portion 22c1.
- the negative electrode unbonded portion 22c1 has a rectangular frame shape in a plan view in which the inner peripheral edge and the outer peripheral edge are rectangular.
- the length of the long side of the negative electrode active material layer 22b in a plan view is L1, and the length between the spacer 24 and the negative electrode active material layer 22b is parallel to the long side of the negative electrode active material layer 22b.
- the length in the direction is the width L2 of the negative electrode unbonded portion 22c1.
- the ratio (L2 / L1) of the width L2 of the negative electrode unbonded portion 22c1 to the length L1 of the long side of the negative electrode active material layer 22b is 0.02 or less, preferably 0.01 or less.
- the ratio (L2 / L1) is, for example, 0.002 or more.
- the ratio of the formation range of the negative electrode active material layer 22b to the first surface 22a1 of the negative electrode current collector 22a is large, and the formation range of the negative electrode unbonded portion 22c1 is the negative electrode active material layer. It means that it is relatively small with respect to the formation range of 22b. More specifically, first, after the area of the first surface 22a1 of the negative electrode current collector 22a is set based on the application of the power storage device 10 such as the mounting space, the frame shape is used to secure the sealing property of the sealed space S. The area to which the spacer 24 of the above is adhered is set.
- the formation range of the negative electrode non-adhesive portion 22c1 and the negative electrode active material layer 22b is set for the region located inside the region to which the spacer 24 is adhered on the first surface 22a1 of the negative electrode current collector 22a.
- the battery capacity (negative electrode) while securing the negative electrode unbonded portion 22c1 on the first surface 22a1 of the negative electrode current collector 22a so that the surplus space for receiving the gas generated during charging / discharging is formed in the closed space S.
- the formation range of the negative electrode active material layer 22b is set so as to increase the capacity) as much as possible.
- the length L1 of the long side of the negative electrode active material layer 22b is preferably 800 mm or more, more preferably 1000 mm or more.
- the length L1 of the long side is preferably 2500 mm or less, more preferably 1600 mm or less.
- the width L2 of the negative electrode non-adhesive portion 22c1 is preferably 3 mm or more, and more preferably 5 mm or more.
- the width L2 of the negative electrode non-adhesive portion 22c1 is, for example, 30 mm or less.
- the arrangement of the positive electrode active material layer 21b and the spacer 24 on the first surface 21a1 of the positive electrode current collector 21a and the plan-view shape of the positive electrode active material layer 21b and the spacer 24 are the same as the configuration of the negative electrode 22 described above. Is.
- the positive electrode active material layer 21b has a rectangular shape in a plan view and is adhered to the central portion of the first surface 21a1 of the positive electrode current collector 21a.
- the outer peripheral portion of the first surface 21a1 of the positive electrode current collector 21a where the positive electrode active material layer 21b is not provided is the positive electrode uncoated portion 21c.
- the positive electrode uncoated portion 21c is formed with a positive electrode unbonded portion 21c1 (not shown) to which the spacer 24 is not adhered.
- Each side constituting the rectangular inner peripheral edge of the spacer 24 is parallel to the opposite side in the positive electrode active material layer 21b. Therefore, the positive electrode non-adhesive portion 21c1 has a rectangular frame shape in a plan view in which the inner peripheral edge and the outer peripheral edge are rectangular.
- the length of the long side of the positive electrode active material layer 21b in a plan view is L1
- the length between the spacer 24 and the positive electrode active material layer 21b is the length between the positive electrode active material layer 21b and the positive electrode active material layer 21b.
- the length in the direction parallel to the long side of the positive electrode is defined as the width L2 of the positive electrode non-bonded portion 21c1.
- the positive electrode active material layer 21b may be formed to have the same size as the negative electrode active material layer 22b, or may be formed to be one size smaller than the negative electrode active material layer 22b. It is assumed that the positive electrode active material layer 21b is formed to have the same size as the negative electrode active material layer 22b.
- the ratio (L2 / L1) of the width L2 of the positive electrode non-adhesive portion 21c1 to the length L1 of the long side of the positive electrode active material layer 21b is 0.02 or less, preferably 0.01 or less.
- the ratio (L2 / L1) is, for example, 0.002 or more.
- the length L1 of the long side of the positive electrode active material layer 21b is preferably 800 mm or more, and more preferably 1000 mm or more.
- the length L1 of the long side is preferably 2500 mm or less, more preferably 1600 mm or less.
- the width L2 of the positive electrode non-adhesive portion 21c1 is preferably 3 mm or more, and more preferably 5 mm or more.
- the width L2 of the positive electrode non-adhesive portion 21c1 is, for example, 30 mm or less.
- the positive electrode active material layer 21b is formed to be one size smaller than the negative electrode active material layer 22b.
- the length L1 of the long side of the positive electrode active material layer 21b is shorter than the length L1 of the long side of the negative electrode active material layer 22b.
- the width L2 of the positive electrode non-adhesive portion 21c1 becomes longer than the width L2 of the negative electrode non-adhesive portion 22c1 according to the shortened length L1 of the long side of the positive electrode active material layer 21b.
- the positive electrode active material layer 21b and the negative electrode active material layer 22b are equivalent in each range of the length L1 of the long side of the positive electrode active material layer 21b, the width L2 of the positive electrode unbonded portion 21c1, and the ratio (L2 / L1).
- the length L1 of the long side of the positive electrode active material layer 21b is shifted according to the shortened length. Specifically, the range of the length L1 of the long side of the positive electrode active material layer 21b shifts in the direction of taking a small value, and the width L2 of the positive electrode non-adhesive portion 21c1 shifts in the direction of taking a large value.
- the range of (L2 / L1) shifts in the direction of taking a large value.
- the positive electrode active material layer 21b and the negative electrode active material layer 22b which have a rectangular shape in a plan view, each have four corner portions C.
- Each corner portion C is formed in a chamfered shape in an arc shape.
- the arc-shaped chamfered shape of the corner portion C may be formed by chamfering the corner portion C in an arc shape after forming the active material layer on the current collector, and the active material layer may be formed on the current collector.
- the corner portion C may be formed so as to have an arc shape when the corner portion C is formed.
- the chamfered shape includes, for example, an arc shape having a constant curvature, an elliptical arc shape having a gradual change in curvature, and a plurality of curved portions consisting of an arc or an elliptical arc directly or via a straight line portion.
- the shape connected by is mentioned.
- Examples of the arc shape include an arc shape that is convex outward and an arc shape that is convex inward.
- FIG. 2 as an example, an arcuate corner portion C that is convex outward is shown.
- Examples of the elliptical arc shape include an elliptical arc shape that is convex outward and an elliptical arc shape that is convex inward.
- FIG. 4A illustrates an elliptical arc-shaped corner portion C that is convex outward.
- FIG. 4B shows a corner portion C having a shape in which two arcs X1 and X2 that are convex outward are connected as an example of a shape in which a plurality of curved portions are connected.
- the number of the curved portions to be connected is not particularly limited.
- the length of each arc or elliptical arc constituting the plurality of curved portions and the curvature of each arc or elliptical arc may be the same, or may be partially or completely different. Further, a part of the curved portion may have an arc shape that is convex inward.
- FIG. 4C shows a corner portion C having a shape in which two outwardly convex arcs X1 and X2 are connected by one straight line Y1 as an example of a shape in which a plurality of curved portions are connected via a straight line portion. Is shown.
- the straight line Y1 is a tangent line at the connection point P1 of the arc X1 with the straight line Y1 and a tangent line at the connection point P2 with the straight line Y1 of the arc X2.
- each arc or elliptical arc constituting the shape connecting a plurality of arcs or elliptical arcs, and the curvature of each arc or elliptical arc may be the same, or may be partially or completely different.
- the straight line connecting the arcs or elliptical arcs is not limited to the tangents at the connection points of the arcs or elliptical arcs.
- the shape in which a plurality of curved portions are connected directly or via a straight portion includes a plurality of curved portions including a curved portion connected to the long side of the active material layer provided with the corner portion C and a curved portion connected to the short side. It is preferable that the shape is directly connected or connected via a straight portion. Further, the shape in which a plurality of curved portions are connected directly or via a straight portion is preferably a shape in which the corner portions protruding to the outer peripheral side are not formed.
- the radius of curvature of the portion having the maximum curvature at the arc-shaped corner portion C is 5 mm or more, preferably 10 mm or more.
- the radius of curvature is preferably 30 mm or less, more preferably 20 mm or less.
- the formation range A1 of the corner C in the direction parallel to the long side of the active material layer in which the corner C is provided which is the formation range of the corner C having a chamfered arc shape, is preferably 5 mm or more. More preferably, it is 10 mm or more.
- the formation range A1 is, for example, 30 mm or less.
- the formation range A2 of the corner portion C in the direction parallel to the short side of the active material layer provided with the corner portion C is preferably 5 mm or more, more preferably 10 mm or more.
- the formation range A2 is, for example, 30 mm or less.
- the formation range of the corner portion C is, for example, a range in which the central angle ⁇ of the arc is 30 degrees or more and 90 degrees or less, and the central angle ⁇ is 90. It is preferably in the range of degrees.
- each corner portion C of the negative electrode active material layer 22b may be the same or different as long as each of the above numerical values is satisfied.
- the shapes of the corner portions C of the positive electrode active material layer 21b may all be the same or different as long as the above numerical values are satisfied.
- the negative electrode 22, the negative electrode current collector 22a, and the negative electrode active material layer 22b correspond to the first electrode, the first current collector, and the first active material layer, respectively.
- the negative electrode non-adhesive portion 22c1 corresponds to a region where the first active material layer is not formed in the region where the spacer on the first surface of the first current collector is not adhered.
- the positive electrode 21, the positive electrode current collector 21a, and the positive electrode active material layer 21b correspond to the second electrode, the second current collector, and the second active material layer, respectively.
- the plurality of storage cells 20 are in direct contact with each other so that the second surface 21a2 of the positive electrode current collector 21a and the second surface 22a2 of the negative electrode current collector 22a are in electrical contact with each other.
- it has an indirectly superposed structure.
- a plurality of storage cells 20 constituting the cell stack 30 are connected in series.
- the two storage cells 20 adjacent to each other in the stacking direction provide a pseudo bipolar electrode 25 in which the positive electrode current collector 21a and the negative electrode current collector 22a in contact with each other are regarded as one current collector. It is formed.
- the pseudo bipolar electrode 25 includes a current collector having a structure in which a positive electrode current collector 21a and a negative electrode current collector 22a are superposed, and a positive electrode active material layer 21b formed on one surface of the current collector. It includes a negative electrode active material layer 22b formed on the other side surface.
- the power storage device 10 includes a pair of energizing bodies composed of a positive electrode energizing plate 40 and a negative electrode energizing plate 50 arranged so as to sandwich the cell stack 30 in the stacking direction of the cell stack 30.
- the positive electrode energizing plate 40 and the negative electrode energizing plate 50 are each made of a material having excellent conductivity.
- the positive electrode energizing plate 40 is electrically connected to the second surface 21a2 of the positive electrode current collector 21a of the positive electrode 21 arranged on the outermost side at one end in the stacking direction.
- the negative electrode energizing plate 50 is electrically connected to the second surface 22a2 of the negative electrode current collector 22a of the negative electrode 22 arranged on the outermost side at the other end in the stacking direction.
- the power storage device 10 is charged and discharged through the terminals provided on the positive electrode energizing plate 40 and the negative electrode energizing plate 50, respectively.
- the material constituting the positive electrode current-carrying plate 40 for example, the same material as the material constituting the positive electrode current collector 21a can be used.
- the positive electrode current-carrying plate 40 may be made of a metal plate thicker than the positive electrode current collector 21a used for the cell stack 30.
- the material constituting the negative electrode current collector plate 50 for example, the same material as the material constituting the negative electrode current collector 22a can be used.
- the negative electrode current-carrying plate 50 may be made of a metal plate thicker than the negative electrode current collector 22a used for the cell stack 30.
- the positive electrode collector 21a and the negative electrode current collector 22a are chemically inert electricity for continuing to flow current through the positive electrode active material layer 21b and the negative electrode active material layer 22b during discharging or charging of the lithium ion secondary battery. It is a conductor.
- the positive electrode current collector 21a and the negative electrode current collector 22a are foil-shaped.
- the thicknesses of the foil-shaped positive electrode current collector 21a and the negative electrode current collector 22a are independently, for example, 1 ⁇ m or more and 100 ⁇ m or less, preferably 10 ⁇ m or more and 60 ⁇ m or less.
- a metal material, a conductive resin material, a conductive inorganic material, or the like can be used as the material constituting the positive electrode current collector 21a and the negative electrode current collector 22a.
- Examples of the metal material include copper, aluminum, nickel, titanium, and stainless steel.
- Examples of the conductive resin material include a conductive polymer material and a resin obtained by adding a conductive filler to a non-conductive polymer material as needed.
- One or both of the positive electrode current collector 21a and the negative electrode current collector 22a may include a plurality of layers including one or more layers including the above-mentioned metal material or conductive resin material.
- the surfaces of one or both of the positive electrode current collector 21a and the negative electrode current collector 22a may be coated with a known protective layer.
- the surfaces of one or both of the positive electrode current collector 21a and the negative electrode current collector 22a may be surface-treated by a known method such as plating. Examples of the surface treatment include chromate treatment and phosphoric acid chromate treatment.
- the positive electrode current collector 21a and the negative electrode current collector 22a there is a case where the positive electrode current collector 21a is made of aluminum foil and the negative electrode current collector 22a is made of copper foil.
- the positive electrode active material layer 21b contains a positive electrode active material that can occlude and release charge carriers such as lithium ions.
- a positive electrode active material for example, a lithium composite metal oxide having a layered rock salt structure, a metal oxide having a spinel structure, a polyanionic compound, or the like, which can be used as a positive electrode active material for a lithium ion secondary battery may be adopted. .. Further, two or more kinds of positive electrode active materials may be used in combination.
- the positive electrode active material layer 21b contains olivine-type lithium iron phosphate (LiFePO4) as a polyanionic compound.
- the negative electrode active material layer 22b can be used without particular limitation as long as it is a simple substance, an alloy, or a compound capable of occluding and releasing charge carriers such as lithium ions.
- examples of the negative electrode active material include Li, a carbon-based active material, a metal compound, an element that can be alloyed with lithium, or a compound thereof.
- examples of the carbon-based active material include natural graphite, artificial graphite, hard carbon (non-graphitizable carbon), soft carbon (easy graphitizable carbon) and the like.
- artificial graphite include highly oriented graphite, mesocarbon microbeads and the like.
- Examples of the element that can be alloyed with lithium include silicon (silicon) and tin.
- the negative electrode active material layer 22b contains a carbon-based active material.
- the positive electrode active material layer 21b and the negative electrode active material layer 22b are conductive aids, binders, and electrolytes (polymer matrix, ions) for increasing electrical conductivity as needed, respectively. It may further contain a conductive polymer, a liquid electrolyte, etc.), an electrolyte supporting salt (lithium salt) for enhancing ionic conductivity, and the like.
- the components contained in the active material layer, the compounding ratio of the components, and the thickness of the active material layer are not particularly limited, and conventionally known findings regarding a lithium ion secondary battery can be appropriately referred to.
- the conductive auxiliary agent is added to increase the conductivity of the positive electrode 21 or the negative electrode 22.
- the conductive auxiliary agent include acetylene black, carbon black, graphite and the like.
- the binder include fluororesins such as polyvinylidene fluoride, polytetrafluoroethylene and fluororubber, thermoplastic resins such as polypropylene and polyethylene, imide-based resins such as polyimide and polyamideimide, and alkoxysilyl group-containing resins.
- acrylic resins such as polyacrylic acid and polymethacrylic acid
- arginates such as styrene-butadiene rubber
- carboxymethyl cellulose sodium alginate, and ammonium alginate
- water-soluble cellulose ester cross-linking products water-soluble cellulose ester cross-linking products
- starch-acrylic acid graft polymers starch-acrylic acid graft polymers.
- these binders can be used alone or in combination.
- the solvent or dispersion medium for example, water, N-methyl-2-pyrrolidone and the like are used.
- the thickness and basis weight of the active material layer are not particularly limited, and conventionally known knowledge about a lithium ion secondary battery can be appropriately referred to. However, from the viewpoint of increasing the energy density of the storage cell 20, it is preferable to increase the thickness and the basis weight of the active material layer.
- the thickness of the positive electrode active material layer 21b is, for example, 100 ⁇ m or more and 400 ⁇ m or less, and preferably 200 ⁇ m or more.
- the basis weight of the positive electrode active material layer 21b is, for example, 40 mg / cm2 or more and 80 mg / cm2 or less, and preferably 50 mg / cm2 or more.
- the thickness of the negative electrode active material layer 22b is 100 ⁇ m or more and 400 ⁇ m or less, and preferably 200 ⁇ m or more.
- the basis weight of the negative electrode active material layer 22b is, for example, 20 mg / cm2 or more and 40 mg / cm2 or less, and preferably 25 mg / cm2 or more.
- Examples of the method for forming the active material layer on the surfaces of the positive electrode current collector 21a and the negative electrode current collector 22a include conventionally known methods such as a roll coating method.
- the heat-resistant layer may be provided on the surface of the active material layer.
- the power storage device 10 of the present embodiment is provided with a spacer 24 that forms a closed space S between the positive electrode 21 and the negative electrode 22, and the outer peripheral portion of the first surface 22a1 of the negative electrode current collector 22a is fixed by the spacer 24. Has been done. Further, on the first surface 22a1 of the negative electrode current collector 22a, a portion where the negative electrode active material layer 22b is formed and a portion where the spacer 24 is adhered to the formation range of the negative electrode active material layer 22b bonded to the central portion. The negative electrode unbonded portion 22c1 located between and is significantly smaller.
- the negative electrode active material layer 22b greatly expands in the plane direction during charging and discharging, while the negative electrode unbonded portion 22c1 which is a portion deformed with the negative electrode active material layer 22b is small. Therefore, the negative electrode unbonded portion 22c1 is greatly deformed as the negative electrode active material layer 22b expands and contracts. As a result, the load acting on the negative electrode non-adhesive portion 22c1 becomes large due to the expansion and contraction of the negative electrode active material layer 22b, and wrinkles and tears are likely to occur in the negative electrode non-adhesive portion 22c1.
- the expansion stress of the negative electrode active material layer 22b when the negative electrode active material layer 22b expands is concentrated on one point at the tip of the corner portion C. Therefore, a large load is locally applied to the negative electrode unbonded portion 22c1 located near the tip of the corner portion C, and the largest strain is generated in the portion.
- the corner portion C of the negative electrode active material layer 22b is formed in an arc-shaped chamfered shape.
- the concentration of stress on the tip of the corner portion C of the negative electrode active material layer 22b is relaxed, and the stress transmitted from the corner portion C to the negative electrode unbonded portion 22c1 is widely dispersed.
- the maximum strain generated in the negative electrode unbonded portion 22c1 when the negative electrode active material layer 22b is expanded can be reduced, and wrinkles and tears generated in the negative electrode unbonded portion 22c1 can be suppressed.
- the positive electrode 21 is similarly configured, and wrinkles and tears that occur in the positive electrode non-adhesive portion 21c1 can be suppressed by the same mechanism.
- the electrodes of models 1 to 4 used in this simulation are negative electrodes using a copper foil as a current collector and a carbon-based active material as an active material, and the detailed configuration thereof is as shown in Table 1. be.
- the corners of the active material layer were arcuate, and the electrode angle R (radius of curvature) of the arcuate corners was changed to 0,5,10,15,20,25,30 mm.
- the width L2 of the unbonded portion of the current collector was set to 8 mm, and the forming range of the arcuate corner portion was set to a range in which the central angle ⁇ was 90 degrees. Then, assuming that the expansion rate of the active material layer in the plane direction with one charge / discharge is 9%, the maximum foil strain in one charge / discharge was obtained. The results are shown in the graph of FIG.
- copper foils are often used in thinner thicknesses. Further, from the viewpoint of suppressing pinholes, the copper foil is often used with a thickness of 10 ⁇ m or more. Therefore, the effect of sufficiently suppressing the maximum strain was obtained in models 1 and 4 using a thin copper foil with a thickness of 6 ⁇ m, which is the same effect when a current collector made of another material is used. Suggests that
- the power storage device 10 includes a positive electrode 21 having a positive electrode current collector 21a and a positive electrode active material layer 21b, a negative electrode 22 having a negative electrode current collector 22a and a negative electrode active material layer 22b, and a positive electrode active material layer 21b and a negative electrode activity.
- a separator 23 arranged between the material layer 22b and a spacer 24 arranged between the positive electrode 21 and the negative electrode 22 are provided.
- the spacer 24 is arranged so as to surround the periphery of the positive electrode active material layer 21b and the negative electrode active material layer 22b, and is adhered to the first surfaces of the positive electrode current collector 21a and the negative electrode current collector 22a to form the positive electrode 21.
- a closed space is formed between the negative electrode 22 and the negative electrode 22.
- the negative electrode active material layer 22b has a rectangular shape in a plan view when viewed from the stacking direction. In the region where the spacer 24 is not adhered on the first surface 22a1 of the negative electrode current collector 22a, a region where the negative electrode active material layer 22b is formed and a negative electrode unbonded portion 22c1 where the negative electrode active material layer 22b is not formed. And are provided.
- the ratio (L2 / L1) of the width L2 of the negative electrode unbonded portion 22c1 to the length L1 of the long side of the negative electrode active material layer 22b in a plan view is 0.02 or less.
- the corner portion C of the negative electrode active material layer 22b has a chamfered shape in an arc shape, and the radius of curvature of the portion having the maximum curvature in the corner portion C is 5 mm or more.
- the maximum strain generated in the negative electrode non-adhesive portion 22c1 when the negative electrode active material layer 22b is expanded can be reduced, and wrinkles and tears in the negative electrode non-adhesive portion 22c1 can be suppressed.
- the corner portion C of the negative electrode active material layer 22b has an arc shape that is convex outward. According to the above configuration, since the protruding corner portion is not formed, it is possible to suppress the stress of expansion of the negative electrode active material layer 22b from concentrating on a part of the corner portion C. Therefore, the effect of the above (1) can be obtained more remarkably. Further, as compared with the shape in which the corner portion C is chamfered, the amount of decrease in the area of the negative electrode active material layer 22b due to the chamfering of the corner portion C can be suppressed to be small, and the capacity decrease of the negative electrode 22 can be suppressed.
- the corner portion C has an arc shape
- the effect of suppressing the concentration of expansion stress of the negative electrode active material layer 22b can be greatly obtained as compared with the case where the corner portion C has an elliptical arc shape.
- the corner portion C is formed into an elliptical arc shape, it is possible to suppress the decrease in the area of the negative electrode active material layer 22b due to chamfering the corner portion C to be smaller than in the case where the corner portion C is formed into an arc shape. ..
- the arcuate corner portion C is matched with the length in the direction parallel to the long side, which is the direction in which the amount of expansion is large.
- the formation range of is set. In this case, if the arcuate corner portion C having a constant curvature is adopted, the formation range A1 of the corner portion C in the direction parallel to the long side and the formation range A2 of the corner portion C in the direction parallel to the short side are equal. Therefore, the formation range A2 of the corner portion C in the direction parallel to the short side becomes larger than necessary.
- the formation of the corner portion C in the direction parallel to the long side is formed.
- the formation range A2 of the corner portion C in the direction parallel to the short side can be made smaller than the range A1. Therefore, the amount of decrease in the area of the negative electrode active material layer 22b due to chamfering the corner portion C can be suppressed to a small amount.
- the effect of (2) is the same for the positive electrode 21.
- the radius of curvature of the corner portion C is 10 mm or more. According to the above configuration, the maximum strain generated in the positive electrode non-adhesive portion 21c1 and the negative electrode non-adhesive portion 22c1 can be further reduced.
- the radius of curvature of the corner portion C is 30 mm or less.
- the effect of reducing the maximum strain generated in the positive electrode non-adhesive portion 21c1 and the negative electrode non-adhesive portion 22c1 by increasing the radius of curvature of the corner portion C converges when the radius of curvature exceeds 30 mm. Therefore, according to the above configuration, it is possible to suppress a decrease in capacity of the positive electrode 21 and the negative electrode 22 due to the arc-shaped corner portion C being formed larger than necessary and the areas of the positive electrode active material layer 21b and the negative electrode active material layer 22b being reduced. ..
- the negative electrode current collector 22a is a copper foil, and the negative electrode active material layer 22b contains a carbon-based active material.
- the configuration in which the negative electrode active material layer 22b containing a carbon-based active material having a large expansion rate during charging and discharging and the copper foil is combined is the negative electrode current collector 22a due to the expansion and contraction of the negative electrode active material layer 22b during charging and discharging. Wrinkles and tears are especially likely to occur. Therefore, the effect of the above (1) can be obtained more remarkably.
- the positive electrode 21, the negative electrode 22, and the separator 23 have a structure in which the separator 23 is repeatedly laminated, and the second surface 21a2 on the opposite side of the first surface 21a1 in the positive electrode current collector 21a and the negative electrode current collector 22a.
- the second surface 22a2 on the opposite side of the first surface 22a1 is in contact with the second surface 22a2.
- this embodiment can be changed and carried out as follows.
- the present embodiment and the following modified examples can be implemented in combination with each other within a technically consistent range.
- all four corners C of the negative electrode active material layer 22b are formed in an arcuate shape, but at least one corner C of the negative electrode active material layer 22b is chamfered in an arc shape. Any shape may be used. When the plurality of corner portions C are chamfered in an arc shape, the shapes may be the same, or some or all of them may be different.
- the configuration of the positive electrode 21 is not limited to the configuration of the above embodiment.
- the shape of the positive electrode active material layer 21b, the ratio of the width L2 of the positive electrode unbonded portion 21c1 to the length L1 of the long side of the positive electrode active material layer 21b, and the shape of the corner portion C of the positive electrode active material layer 21b are the above-described embodiments.
- the configuration is not limited to this, and a conventionally known configuration can be applied. In this case, the negative electrode 22 becomes the first electrode.
- a conductive layer in close contact with the positive electrode current collector 21a may be arranged.
- the conductive layer include a layer containing carbon such as acetylene black or graphite, and a layer having a hardness lower than that of the positive electrode current collector 21a such as a plating layer containing Au or the like.
- a similar conductive layer may be arranged between the negative electrode current-carrying plate 50 and the negative electrode current collector 22a.
- the number of storage cells 20 constituting the power storage device 10 is not particularly limited.
- the number of storage cells 20 constituting the power storage device 10 may be 1.
- the positive electrode active material layer 21b or the negative electrode active material layer 22b may be provided on the second surface 21a2 of the positive electrode current collector 21a. Further, the positive electrode active material layer 21b or the negative electrode active material layer 22b may be provided on the second surface 22a2 of the negative electrode current collector 22a.
- the electrode may be a bipolar electrode using a bimetal or the like and having a positive electrode current collector 21a and a negative electrode current collector 22a as one current collector.
- the second surface 21a2 of the positive electrode current collector 21a which is the contact portion between the storage cells 20 adjacent to each other in the stacking direction, and the second surface 22a2 of the negative electrode current collector 22a may be adhered to each other. ..
- a method of adhering the second surface 21a2 of the positive electrode current collector 21a and the second surface 22a2 of the negative electrode current collector 22a for example, a method using a conductive adhesive can be mentioned.
- the positive electrode, the negative electrode, and the separator are repeatedly laminated, and the second surface on the opposite side of the first surface of the positive electrode current collector and the negative electrode current collector are described.
- the current collector in contact with a second surface on the opposite side of the first surface.
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Abstract
Description
上記構成によれば、突出した角部分が形成されないことにより、第1活物質層の膨張の応力が角部の一部に集中することを抑制できる。そのため、第1集電体の未接着部に生じる皺及び破れを抑制できる効果がより顕著に得られる。また、角部をC面取りした形状と比較して、角部を面取りすることによる第1活物質層の面積の減少量を小さく抑えることができ、第1電極の容量低下を抑制できる。
上記構成によれば、第1集電体の未接着部に生じる最大ひずみを更に小さくできる。
前記曲率半径は、30mm以下であることが好ましい。
充放電時の膨張率の大きい炭素系の活物質を含む第1活物質層と、銅箔とを組み合わせた構成は、充放電時における第1活物質層の膨張収縮により、第1集電体に皺や破れが特に生じやすい。そのため、第1活物質層の角部を特定形状とすることによる上記の効果がより顕著に得られる。
図1に示す蓄電装置10は、例えば、フォークリフト、ハイブリッド自動車、電気自動車等の各種車両のバッテリに用いられる蓄電モジュールである。蓄電装置10は、例えば、ニッケル水素二次電池又はリチウムイオン二次電池等の二次電池である。蓄電装置10は、電気二重層キャパシタであってもよい。本実施形態では、蓄電装置10がリチウムイオン二次電池である場合を例示する。
正極活物質層21bが負極活物質層22bと同等の大きさに形成されているとする。この場合、正極活物質層21bの長辺の長さL1に対する正極未接着部21c1の幅L2の比率(L2/L1)は、0.02以下であり、好ましくは0.01以下である。また、当該比率(L2/L1)は、例えば、0.002以上である。正極活物質層21bの長辺の長さL1は、好ましくは800mm以上であり、より好ましくは1000mm以上である。また、長辺の長さL1は、好ましくは2500mm以下であり、より好ましくは1600mm以下である。正極未接着部21c1の幅L2は、好ましくは3mm以上であり、より好ましくは5mm以上である。正極未接着部21c1の幅L2は、例えば、30mm以下である。なお、正極活物質層21bの平面視形状が正方形である場合、正方形の対向する二組の辺のいずれか一方を長辺とみなす。
楕円弧状としては、例えば、外側に凸となる楕円弧状、内側に凸となる楕円弧状が挙げられる。図4(a)に、外側に凸となる楕円弧状の角部Cを図示する。
<正極集電体及び負極集電体>
正極集電体21a及び負極集電体22aは、リチウムイオン二次電池の放電又は充電の間、正極活物質層21b及び負極活物質層22bに電流を流し続けるための化学的に不活性な電気伝導体である。正極集電体21a及び負極集電体22aは、箔状である。箔状の正極集電体21a及び負極集電体22aの厚さはそれぞれ独立して、例えば、1μm以上100μm以下であり、好ましくは10μm以上60μm以下である。正極集電体21a及び負極集電体22aを構成する材料としては、例えば、金属材料、導電性樹脂材料、導電性無機材料等を用いることができる。
正極活物質層21bは、リチウムイオン等の電荷担体を吸蔵及び放出し得る正極活物質を含む。正極活物質としては、例えば、層状岩塩構造を有するリチウム複合金属酸化物、スピネル構造の金属酸化物、ポリアニオン系化合物など、リチウムイオン二次電池の正極活物質として使用可能なものを採用すればよい。また、2種以上の正極活物質を併用してもよい。本実施形態において、正極活物質層21bはポリアニオン系化合物としてのオリビン型リン酸鉄リチウム(LiFePO4)を含む。
結着剤としては、例えば、ポリフッ化ビニリデン、ポリテトラフルオロエチレン、フッ素ゴム等の含フッ素樹脂、ポリプロピレン、ポリエチレン等の熱可塑性樹脂、ポリイミド及びポリアミドイミド等のイミド系樹脂、アルコキシシリル基含有樹脂、ポリアクリル酸やポリメタクリル酸等のアクリル系樹脂、スチレン-ブタジエンゴム、カルボキシメチルセルロース、アルギン酸ナトリウム、アルギン酸アンモニウム等のアルギン酸塩、水溶性セルロースエステル架橋体、及びデンプン-アクリル酸グラフト重合体等を例示することができる。これらの結着剤は、単独で又は複数で用いられ得る。溶媒又は分散媒には、例えば、水、N-メチル-2-ピロリドン等が用いられる。
正極21又は負極22の熱安定性を向上させるために、活物質層の表面に上記の耐熱層を設けてもよい。
本実施形態の蓄電装置10は、正極21と負極22との間に密閉空間Sを形成するスペーサ24が設けられており、負極集電体22aの第1面22a1の外周部分がスペーサ24により固定されている。また、負極集電体22aの第1面22a1において、中央部に接着される負極活物質層22bの形成範囲に対して、負極活物質層22bが形成される部分とスペーサ24が接着される部分との間に位置する負極未接着部22c1が大幅に小さくなっている。
(1)蓄電装置10は、正極集電体21a及び正極活物質層21bを有する正極21と、負極集電体22a及び負極活物質層22bを有する負極22と、正極活物質層21bと負極活物質層22bとの間に配置されたセパレータ23と、正極21と負極22との間に配置されるスペーサ24とを備える。スペーサ24は、正極活物質層21b及び負極活物質層22bの周囲を囲むように配置されるとともに、正極集電体21a及び負極集電体22aの各第1面に接着されることにより正極21と負極22との間に密閉空間を形成する。負極活物質層22bは、積層方向から見た平面視の形状が矩形状である。負極集電体22aの第1面22a1におけるスペーサ24が接着されていない領域には、負極活物質層22bが形成されている領域と、負極活物質層22bが形成されていない負極未接着部22c1とが設けられている。平面視における負極活物質層22bの長辺の長さL1に対する負極未接着部22c1の幅L2の比率(L2/L1)が0.02以下である。負極活物質層22bの角部Cは、弧状に面取りされた形状であり、角部Cにおける曲率が最大の部分の曲率半径は、5mm以上である。
上記構成によれば、突出した角部分が形成されないことにより、負極活物質層22bの膨張の応力が角部Cの一部に集中することを抑制できる。そのため、上記(1)の効果がより顕著に得られる。また、角部CをC面取りした形状と比較して、角部Cを面取りすることによる負極活物質層22bの面積の減少量を小さく抑えることができ、負極22の容量低下を抑制できる。
上記構成によれば、正極未接着部21c1及び負極未接着部22c1に生じる最大ひずみを更に小さくできる。
角部Cの曲率半径を大きくすることにより、正極未接着部21c1及び負極未接着部22c1に生じる最大ひずみを小さくする効果は、曲率半径30mmを超えると収束する。したがって、上記構成によれば、弧状の角部Cを必要以上に大きく形成されて正極活物質層21b及び負極活物質層22bの面積が小さくなることによる正極21及び負極22の容量低下を抑制できる。
充放電時の膨張率の大きい炭素系の活物質を含む負極活物質層22bと、銅箔とを組み合わせた構成は、充放電時における負極活物質層22bの膨張収縮により、負極集電体22aに皺や破れが特に生じやすい。そのため、上記(1)の効果がより顕著に得られる。
○上記実施形態では、負極活物質層22bの4個の角部Cを全て弧状に面取りされた形状に形成していたが、負極活物質層22bの少なくとも一つの角部Cが弧状に面取りされた形状であればよい。なお、複数の角部Cを弧状に面取りされた形状とする場合、それらの形状は、それぞれ同じであってもよいし、一部又は全てが異なっていてもよい。
○正極通電板40と正極集電体21aとの間に、両部材間の導電接触を良好にするために、正極集電体21aに密着する導電層を配置してもよい。導電層としては、例えば、アセチレンブラック又はグラファイト等のカーボンを含む層、Au等を含むメッキ層などの正極集電体21aよりも低い硬度を有する層が挙げられる。また、負極通電板50と負極集電体22aとの間に同様の導電層を配置してもよい。
〇正極集電体21aの第2面21a2に、正極活物質層21b又は負極活物質層22bが設けられていてもよい。また、負極集電体22aの第2面22a2に、正極活物質層21b又は負極活物質層22bが設けられていてもよい。
○セルスタック30において、積層方向に隣接する蓄電セル20同士の接触部分である正極集電体21aの第2面21a2と負極集電体22aの第2面22a2とを接着させた構成としてもよい。正極集電体21aの第2面21a2と負極集電体22aの第2面22a2とを接着する方法としては、例えば、導電性を有する接着剤を用いる方法が挙げられる。
(イ)前記正極と、前記負極と、前記セパレータとが繰り返し積層された構造を有し、前記正極集電体における前記第1面の反対側の第2面と、前記負極集電体における前記第1面の反対側の第2面とが接触している前記蓄電装置。
S…密閉空間
10…蓄電装置
20…蓄電セル
21…正極
21a…正極集電体
21b…正極活物質層
21c1…正極未接着部
22…負極
22a…負極集電体
22b…負極活物質層
22c1…負極未接着部
23…セパレータ
24…スペーサ
30…セルスタック
40…正極通電板
50…負極通電板。
Claims (5)
- 第1集電体の第1面に第1活物質層が形成された第1電極と、
第2集電体の第1面に第2活物質層が形成されてなり、前記第2活物質層が前記第1電極の前記第1活物質層と対向するように配置された第2電極と、
前記第1活物質層と前記第2活物質層との間に配置されたセパレータと、
前記第1集電体及び前記第2集電体の各第1面の間に配置されるスペーサとを備え、
前記スペーサは、前記第1活物質層及び前記第2活物質層の周囲を囲むように配置されるとともに、前記第1集電体及び前記第2集電体の各第1面に接着されることにより前記第1電極と前記第2電極との間に密閉空間を形成し、
前記第1活物質層は、積層方向から見た平面視の形状が矩形状であり、
前記第1集電体の前記第1面における前記スペーサが接着されていない領域には、前記第1活物質層が形成されている領域と、前記第1活物質層が形成されていない領域とが設けられ、
前記平面視における前記第1活物質層の長辺の長さをL1とし、前記スペーサと前記第1活物質層との間の長さであって、前記第1活物質層の長辺と平行な方向の長さをL2としたとき、比率(L2/L1)が0.02以下である蓄電装置であって、
前記第1活物質層の少なくとも一つの角部は、弧状に面取りされた形状であり、当該角部における曲率が最大の部分の曲率半径は、5mm以上であることを特徴とする蓄電装置。 - 前記第1活物質層の少なくとも一つの角部は、外側に凸となる弧状である請求項1に記載の蓄電装置。
- 前記曲率半径は、10mm以上である請求項1又は請求項2に記載の蓄電装置。
- 前記曲率半径は、30mm以下である請求項1~3のいずれか一項に記載の蓄電装置。
- 前記第1集電体は、銅箔であり、前記第1活物質層は、炭素系の活物質を含む請求項1~4のいずれか一項に記載の蓄電装置。
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JP2012221608A (ja) * | 2011-04-05 | 2012-11-12 | Toyota Motor Corp | 電池 |
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JP2014175247A (ja) * | 2013-03-12 | 2014-09-22 | Sanyo Electric Co Ltd | 電池 |
JP2019192590A (ja) * | 2018-04-27 | 2019-10-31 | 株式会社豊田自動織機 | 蓄電モジュールの製造方法及び蓄電モジュール |
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JP2014175247A (ja) * | 2013-03-12 | 2014-09-22 | Sanyo Electric Co Ltd | 電池 |
JP2019192590A (ja) * | 2018-04-27 | 2019-10-31 | 株式会社豊田自動織機 | 蓄電モジュールの製造方法及び蓄電モジュール |
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