WO2022230933A1 - 電気化学デバイスおよびその製造方法 - Google Patents
電気化学デバイスおよびその製造方法 Download PDFInfo
- Publication number
- WO2022230933A1 WO2022230933A1 PCT/JP2022/019064 JP2022019064W WO2022230933A1 WO 2022230933 A1 WO2022230933 A1 WO 2022230933A1 JP 2022019064 W JP2022019064 W JP 2022019064W WO 2022230933 A1 WO2022230933 A1 WO 2022230933A1
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- WO
- WIPO (PCT)
- Prior art keywords
- electrode
- region
- collector foil
- current collector
- lead terminal
- Prior art date
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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
- H01M10/04—Construction or manufacture in general
- H01M10/0431—Cells with wound or folded electrodes
-
- 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
- H01G11/74—Terminals, e.g. extensions of current collectors
-
- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/004—Details
- H01G9/008—Terminals
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
-
- 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
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
-
- 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
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/543—Terminals
- H01M50/552—Terminals characterised by their shape
- H01M50/559—Terminals adapted for cells having curved cross-section, e.g. round, elliptic or button cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
-
- 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
- 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
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to an electrochemical device and its manufacturing method.
- An electrochemical device comprises a pair of electrodes and an electrolytic solution, and at least one of the pair of electrodes contains an active material capable of adsorbing and desorbing ions.
- a separator is interposed between the pair of electrodes.
- An electric double layer capacitor which is an example of an electrochemical device, has a longer life than a secondary battery, can be rapidly charged, and has excellent output characteristics, and is widely used as a backup power source.
- Patent Document 1 proposes covering the negative electrode terminal with a protective tape in order to suppress the deposition of lithium on the negative electrode terminal during pre-doping in a lithium ion capacitor.
- the strength of the electrodes decreases, making it easier for the electrodes to be damaged or short-circuited due to external impact or the like.
- the impact resistance will be improved by attaching a protective tape to the terminal connection portion to which a load is particularly likely to be applied.
- a good adhesion state cannot be obtained between the electrode and the protective tape, resulting in insufficient impact strength.
- one aspect of the present invention provides a first electrode, a second electrode, a separator interposed between the first electrode and the second electrode, an electrolytic solution, the first electrode and the second electrode.
- a lead terminal electrically connected to at least one electrode of two electrodes, and a protective tape covering the lead terminal, wherein the at least one electrode is composed of a current collector foil and a joint provided on the current collector foil. and a material layer, wherein the current collector foil has a first region covered with the material mixture layer and a second region not covered with the material mixture layer and exposing the surface of the current collector foil.
- the protective tape includes a base material layer and an adhesive layer, and the protective tape is adhered to the lead terminal provided in the second region of the current collector foil and adheres to the second region. and bonded to at least a portion of the third region not covered with the lead terminals.
- an electrochemical device comprising a first electrode, a second electrode, a separator interposed between the first electrode and the second electrode, and an electrolytic solution.
- a manufacturing method comprising a step of preparing an electrode including a current collector foil and a mixture layer provided on the current collector foil as at least one of the first electrode and the second electrode.
- the current collecting foil of the at least one electrode has a first region covered with the mixture layer and a second region not covered with the mixture layer and exposing the surface of the current collecting foil.
- a step of electrically connecting a lead terminal to the second region of the current collecting foil disposing a protective tape so as to cover at least a portion of the lead terminal; and a step of adhering a protective tape to the one electrode in at least a portion of a third region that is part of the second region and is not covered with the lead terminal; Later, it further includes the step of pressing the third region of the one electrode through the protective tape.
- FIG. 1A is a layout diagram showing an example of electrodes used in an electrochemical device according to one embodiment of the present invention.
- FIG. 1B is a cross-sectional view showing an example of electrodes used in an electrochemical device according to one embodiment of the present invention.
- FIG. 2 is a partially cutaway perspective view of an electrochemical device according to an embodiment of the present invention.
- An electrochemical device comprises a first electrode, a second electrode, a separator interposed between the first electrode and the second electrode, an electrolytic solution, a lead terminal, and a lead terminal. and a protective tape for covering.
- At least one of the first electrode and the second electrode may be a polarizable electrode.
- a polarizable electrode may comprise an active material capable of adsorbing and desorbing ions.
- An electrochemical device develops capacity by adsorbing ions to an active material on at least one electrode side.
- a non-faradaic current flows when ions are desorbed from the active material.
- the electrochemical device may be an electric double layer capacitor (EDLC) in which an electric double layer is formed by adsorbing ions to the active material. good.
- EDLC electric double layer capacitor
- the electrochemical device is a lithium ion capacitor (LIC) that develops capacity by adsorption or desorption of lithium ions on one electrode side, good too.
- LIC lithium ion capacitor
- a negative electrode used in lithium ion secondary batteries may be used as the non-polarizable electrode.
- a lead terminal is electrically connected to one of the first electrode and the second electrode (either a polarizable electrode or a non-polarizable electrode). Similarly, another lead terminal can be electrically connected to the other electrode of the first electrode and the second electrode.
- the electrochemical device is provided with a protective tape covering lead terminals on at least one electrode.
- One electrode includes a collector foil and a mixture layer provided on the collector foil.
- the first electrode may be a positive electrode or a negative electrode.
- the first electrode may be a polarizable electrode or a non-polarizable electrode.
- the collector foil has a first region covered with the mixture layer and a second region not covered with the mixture layer, where the surface of the collector foil is exposed.
- a lead terminal is attached to the second region.
- the protective tape covers the lead terminals attached to the second area.
- the protective tape also covers at least part of the third region in the longitudinal direction of the current collector foil (the direction perpendicular to the winding axis when the first electrode and the second electrode constitute a wound electrode group). ing.
- the protective tape may be arranged to straddle the mixture layer beyond the third region between the lead terminal and the mixture layer.
- the protective tape includes a base layer and an adhesive layer.
- the protective tape is adhered to lead terminals provided in the second region of the current collector foil via an adhesive layer, and is also adhered to at least a portion of the third region via an adhesive layer. Thereby, the adhesion between the protective tape and the first electrode is strengthened, and the impact resistance can be improved.
- the width W2 of the second region in the longitudinal direction of the current collector foil is preferably 5000 ⁇ m or more in terms of sufficiently firm adhesion between the protective tape and the first electrode.
- the thickness of the mixture layer is preferably thicker than the thickness of the protective tape in order to achieve a high capacity. Further, from the viewpoint of realizing a high capacity, it is preferable that the area of the third region, which is not used for attachment to the lead terminals, among the second regions where the current collecting foil is exposed is as small as possible. On the other hand, a step is formed at the boundary between the third region where the current collector foil is exposed and the lead terminal and at the boundary between the third region and the mixture layer. The thicker the mixture layer, the higher the step at the boundary between the third region and the mixture layer. Further, the narrower the width of the third region in the longitudinal direction of the current collector foil, the greater the ratio of the height of the step to the width of the third region (the distance between the lead terminal and the mixture layer).
- the protective tape can be strongly adhered to the third region even when the step is increased and/or the height ratio of the step is increased in order to increase the capacity. You may pressurize a 3rd area
- the second area may be pressurized through the protective tape during or after the protective tape is adhered.
- the protective tape By applying pressure to the second area through the protective tape, the protective tape can be firmly adhered to the lead terminals, and the protective tape can be firmly adhered to the collector foil in the third area.
- the pressurization pressure when pressurizing the second region or the third region is preferably 4 N/cm 2 or more, more preferably 6 N/cm 2 or more. Pressurization may be performed, for example, by a roll press.
- the pressure (linear pressure) when pressurizing by a roll press is preferably 2 N/cm or more, more preferably 4 N/cm or more.
- the average thickness of the adhesive layer interposed between the current collector foil and the base layer in the third region is formed thicker than the average thickness of the adhesive layer interposed between the lead terminals and the base layer in the second region.
- the protective tape may be provided on both sides of the current collector foil.
- the second region on the other surface (the back surface of the one surface) may have an overlapping portion with the second region on the one surface. good.
- each of the protective tapes provided on both sides extends from the first electrode in the lateral direction of the current collector foil (the first electrode and the second electrode constitute the wound electrode group). If so, it may protrude in the direction parallel to the winding axis). In this case, protective tapes provided on both sides may be adhered to each other at the projecting portion. Thereby, the adhesion between the protective tape and the first electrode can be made stronger, and the impact resistance can be further improved.
- the material of the base layer and adhesive layer of the protective tape is not particularly limited, but the base layer may contain polypropylene (PP) in order to suppress deterioration of the base layer due to the electrolytic solution.
- PP polypropylene
- a lactone compound such as ⁇ -butyrolactone (GBL) can be used as a solvent for the electrolyte used in electrochemical devices because of its low viscosity.
- GBL ⁇ -butyrolactone
- an electrolytic solution containing a lactone compound if a protective tape containing polyethylene terephthalate (PET), which is commonly used in the base layer, is used, the affinity between PET and the lactone compound is high. It dissolves in the liquid, and deterioration of the base material layer may progress.
- PET polyethylene terephthalate
- a masking tape containing polypropylene in a base layer is difficult to dissolve in a lactone compound, so that deterioration of the base layer can be suppressed.
- the base material layer a compound whose Hildebrand solubility parameter (SP value) is sufficiently different from the SP value of the lactone compound can be used.
- ⁇ -butyrolactone (GBL) which is a lactone compound, has an SP value of 12.6 [(cal/cm) 1/2 ] and is easily dissolved in PET, which has an SP value of 10.7, and has an SP value of 8.0. is difficult to dissolve with PP.
- the SP value of the material constituting the base layer is preferably 2.5 or more, and 3.0 or more, away from the SP value of the lactone compound. more preferably.
- the SP value of the material forming the base layer may be 10.0 or less, or 9.0 or less.
- the protective tape is used as the lead terminal. and the current collector foil in the third region, impact resistance can be improved, and breakage of the current collector foil can be suppressed.
- the collector foil may be an etched foil. Etched foils are weaker than non-etched foils and are easily broken by external impact or the like. However, by adhering the protective tape to the lead terminals and to the collector foil in the third region, impact resistance can be improved, and breakage of the collector foil can be suppressed.
- FIG. 1 shows an example of electrodes used in the electrochemical device of the embodiment of the present invention.
- FIG. 1A is a layout diagram schematically showing a state before winding of a first electrode 2 used in a wound-type electrochemical device.
- the X direction is the longitudinal direction of the first electrode and perpendicular to the winding axis
- the Y direction is the lateral direction of the first electrode and parallel to the winding axis.
- FIG. 1B is a cross-sectional view taken along line X 1 -X 2 of FIG. 1A.
- 1A and 1B emphatically show the connecting portion with the lead terminal, which is the main part of the present invention, and the scale of each component in the drawings does not necessarily correspond to the scale of each component in the actual electrode. It does not match.
- the first electrode 2 includes a collector foil 20 and a mixture layer (active material layer) 21 provided on the collector foil 20 .
- the current collector foil 20 is covered with the mixture layer 21 in the first region 20A, while the surface of the current collector foil is exposed without being covered with the mixture layer 21 in the second region 20B.
- the mixture layer 21 is formed on both sides of the current collector foil 20 so as to cover the entire surface of the current collector foil 20 except for the second region 20B (the region not hatched in FIG. 1A).
- the current collector foil 20 has a first principal surface 20X and a second principal surface 20Y opposite to the first principal surface.
- the second region 20B is provided on both the first main surface 20X and the second main surface 20Y.
- the second region 20B on the first main surface 20X is arranged so as to overlap the second region 20B on the second main surface 20Y when viewed from the normal direction of the first main surface 20X.
- a lead terminal 5a is attached to the second region 20B on the first main surface 20X, and the first electrode 2 and the lead terminal 5a are electrically connected.
- the third area 20C which is part of the second area 20B and is not covered with the lead terminal 5a.
- the surface of the collector foil 20 is exposed even after the lead terminals 5a are attached.
- a step S1 is formed at the boundary between the lead terminal 5a and the third region 20C by the side end surface of the lead terminal 5a.
- a step S2 is formed by the side end face of the mixture layer 21 at the boundary between the mixture layer 21 and the third region 20C.
- the thickness of the lead terminal 5a in the area where the lead terminal 5a is attached in the second area 20B is preferably 450 ⁇ m or less, more preferably 350 ⁇ m or less or 300 ⁇ m or less.
- the lead terminal 5a for example, one having a columnar first portion and a second portion continuous with the first portion and flatter than the first portion may be used, but the lead terminal 5a is not limited to this.
- the lead terminal 5a includes a round bar portion 52 as a first portion, and a flat portion 53 as a second portion that is continuous with the round bar portion 52 and formed flatter than the round bar portion 52. , provided.
- one end of a cylindrical metal member is flattened by pressing to form the second portion (flat portion 53), and the other end that is not pressed forms the first portion (round bar portion 52). can do.
- the lead terminal 5 a further includes a CP wire (copper-coated steel wire) 51 that connects with the round bar portion 52 .
- the CP line 51 is used for electrical connection with an external circuit.
- the flat portion 53 overlaps the current collector foil 20 in the second region 20B.
- Current collector foil 20 has through-holes 22 communicating between first main surface 20X and second main surface 20Y in a region within second region 20B overlapping flat portion 53 .
- a needle-like protruding portion is formed at a predetermined position of the flat portion 53 so as to protrude from the flat portion 53 and the through hole 22 penetrates both. is formed.
- the lead terminal 5a is attached to the first electrode 2 by crimping the protruding portion that is inserted through the through hole 22 along the second main surface 20Y.
- An opening communicating with the second main surface 20Y may be formed.
- the thickness of the flat portion 53 is preferably 450 ⁇ m or less, more preferably 350 ⁇ m or less or 300 ⁇ m or less, in order to maintain a high capacity and a good adhesion state between the protective tape 24a and the first electrode 2. .
- a pair of protective tapes 24a and 24b cover the second regions 20B provided on the first main surface 20X and the second main surface 20Y.
- the protective tape 24a includes a base material layer 25a and an adhesive layer 26a.
- the protective tape 24b includes a base layer 25b and an adhesive layer 26b.
- the protective tape 24a provided on the first main surface 20X covers the lead terminal 5a (flat portion 53), covers the third region 20C, and also covers the third region 20C and the mixture layer. 21 and part of the mixture layer 21 is covered.
- the protective tape 24a is adhered to the lead terminal 5a via the adhesive layer 26a, and is also adhered to the current collector foil 20 in the third region 20C.
- the third region 20C is located between the step S1 formed by the lead terminal 5a and the step S2 formed by the mixture layer 21. Since the third region 20 ⁇ /b>C is sandwiched and recessed, it is difficult to achieve a strong bonding state in the third region 20 ⁇ /b>C by a normal bonding method. In order to obtain a strong adhesion state, it is preferable to apply pressure to the third region 20C during or after adhesion of the protective tape 24a. Pressurization can be performed by pressing at least the third region 20C from both sides of the first main surface 20X and the second main surface 20Y. The entire second region 20B including the third region 20C may be pressed.
- the applied pressure is preferably 4 N/cm 2 or more, more preferably 6 N/cm 2 or more. Pressing may be performed by a roll press.
- the linear pressure when pressurized by a roll press is preferably 2 N/cm or more, more preferably 4 N/cm or more.
- the entire second region 20B When the entire second region 20B is pressed, part of the adhesive layer existing on the adhesive surface of the protective tape 24a with the lead terminal 5a (flat portion 53) is removed from the collector foil 20 in the third region 20C. can flow to the adhesive side of the As a result, the portion of the protective tape 24a extending obliquely to the first main surface 20X of the current collector foil 20 above the current collector foil 20 in the third region 20C can also contribute to adhesion, increasing the bonding area. Further, the average thickness T3 of the adhesive layer interposed between the current collector foil 20 and the base material layer in the third region 20C is thicker than the average thickness T2 of the adhesive layer interposed between the lead terminal 5a and the base material layer. can be formed.
- the thickness ratio T3/T2 can be, for example, 1.01 or more, or 1.05 or more.
- the width W3 of the third region 20C sandwiched between the lead terminal 5a and the mixture layer 21 is preferably 2000 ⁇ m or less.
- the width W3 of the third region is preferably 1000 ⁇ m or more, more preferably 1200 ⁇ m or more, in order to firmly bond the protective tape to the first electrode in the third region 20C.
- a ratio of the thickness of the mixture layer to the width W3 of the third region in the longitudinal direction of the current collector foil is preferably 0.02 or more and 0.08 or less, more preferably 0.04 or more and 0.06 or less.
- Each of the protective tapes 24 a and 24 b has a portion 27 protruding from the first electrode 2 in the lateral direction of the current collector foil 20 .
- the protruding portions 27 of the protective tapes 24a and 24b protrude to the same side in the short direction, and the protruding portions 27 overlap each other when viewed from the normal direction of the first main surface 20X.
- Protective tapes 24 a and 24 b are adhered to the projecting portion 27 . Thereby, the adhesion between the protective tapes 24a and 24b and the first electrode 2 becomes stronger, and the impact resistance is further improved.
- FIG. 2 is a partially cutaway perspective view of an electrochemical device according to an embodiment of the present invention.
- the electrochemical device 10 in FIG. 2 is an electric double layer capacitor and includes a wound capacitor element 1.
- the capacitor element 1 is configured by winding a sheet-like first electrode 2 and a sheet-like second electrode 3 with a separator 4 interposed therebetween.
- the first electrode 2 and the second electrode 3 each have a first current collector and a second current collector made of metal, and a first active layer and a second active layer supported on the surface thereof, and adsorb ions. And the capacity is expressed by desorption.
- the first active layer and the second active layer contain, for example, porous carbon particles.
- a first lead wire 5a and a second lead wire 5b are connected to the first electrode 2 and the second electrode 3, respectively, as lead members (lead terminals).
- Capacitor element 1 is housed in a cylindrical exterior case 6 together with an electrolytic solution (not shown).
- the material of the exterior case 6 may be any metal such as aluminum, stainless steel, copper, iron, brass, or the like.
- the opening of the exterior case 6 is sealed with a sealing member 7 .
- the lead wires 5 a and 5 b are led out to the outside so as to pass through the sealing member 7 .
- a rubber material such as butyl rubber, for example, is used for the sealing member 7 .
- a method for manufacturing an electrochemical device is the method for manufacturing an electrochemical device described above.
- the manufacturing method includes a step of preparing an electrode including a collector foil and a mixture layer provided on the collector foil as one of the first electrode and the second electrode.
- the current collector foil of one electrode to be prepared has a first region covered with the mixture layer and a second region not covered with the mixture layer and exposing the surface of the current collector foil.
- the manufacturing method comprises a step (i) of electrically connecting the lead terminal to the second region of the current collector foil, placing a protective tape so as to cover at least a part of the lead terminal, and covering at least a part of the surface of the lead terminal.
- the step (ii) of adhering the protective tape to the one electrode in at least part of the third region that is part of the second region and is not covered with the lead terminal, and at the time of adhering the protective tape or It further includes a step (iii) of pressing the third region of one electrode through a protective tape after bonding.
- the applied pressure in step (iii) is preferably 4 N/cm 2 or more, more preferably 6 N/cm 2 or more. Pressing in step (iii) may be performed using rolls. In that case, the pressure (linear pressure) in pressurization is preferably 2 N/cm or more, more preferably 4 N/cm or more.
- One of the electrodes obtained in step (iii) is laminated with the other electrode via a separator to obtain a laminate.
- the laminate may be a wound body in which one electrode and the other electrode are wound with a separator interposed therebetween.
- the laminate is housed in an exterior case, and an electrolytic solution is injected into the exterior case. An electrochemical device can then be manufactured by sealing the outer case.
- an electrode including an active layer containing an active material and a current collector supporting the active layer is used as a polarizable electrode.
- the active material includes, for example, porous carbon particles.
- the active layer contains porous carbon particles as an active material as an essential component, and may contain a binder, a conductive agent and the like as optional components.
- Porous carbon particles can be produced, for example, by heat-treating a raw material to carbonize it, and then activating the resulting carbide to make it porous.
- the carbide may be crushed and granulated before the activation treatment.
- the porous carbon particles obtained by the activation treatment may be pulverized. After the pulverization treatment, a classification treatment may be performed. Examples of the activation treatment include gas activation using a gas such as water vapor, and chemical activation using an alkali such as potassium hydroxide.
- Raw materials include, for example, wood, coconut shells, pulp waste liquid, coal or coal-based pitch obtained by thermal decomposition thereof, heavy oil or petroleum-based pitch obtained by thermal decomposition thereof, phenolic resin, petroleum-based coke, coal-based coke etc. Among them, petroleum-based coke and coal-based coke are preferred as raw materials.
- the porous carbon particles may be pulverized.
- pulverization for example, a ball mill, jet mill, or the like is used.
- Fine porous carbon particles are obtained by the above pulverization treatment, and the average particle size (D50) is, for example, 1 ⁇ m or more and 4 ⁇ m or less.
- the average particle diameter (D50) means the particle diameter (median diameter) at which the volume integrated value is 50% in the volume-based particle size distribution measured by the laser diffraction/scattering method.
- the pore distribution and particle size distribution of the porous carbon particles can be adjusted by the raw material, the heat treatment temperature, the activation temperature in gas activation, the degree of pulverization, and the like. Also, two types of porous carbon particles made from different raw materials may be mixed to adjust the pore size distribution and particle size distribution of the porous carbon particles.
- the average particle size and particle size distribution of porous carbon particles are measured by a laser diffraction/scattering method. As a measuring device, for example, a laser diffraction/scattering particle size distribution measuring device “MT3300EXII” manufactured by Microtrack Co., Ltd. is used.
- binder for example, resin materials such as polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), and styrene-butadiene rubber (SBR) are used. Carbon black such as acetylene black is used as the conductive agent, for example.
- PTFE polytetrafluoroethylene
- CMC carboxymethyl cellulose
- SBR styrene-butadiene rubber
- Carbon black such as acetylene black is used as the conductive agent, for example.
- the electrode is produced by applying a slurry containing porous carbon particles, a binder and/or a conductive agent, and a dispersion medium to the surface of a current collector, drying the coating film, and rolling it to activate it. Obtained by forming layers.
- Metal foil such as aluminum foil is used for the current collector, for example.
- an electrode containing the porous carbon particles can be used for at least one of the first electrode and the second electrode.
- the electrochemical device is a lithium ion capacitor (LIC)
- an electrode containing the above porous carbon particles is used as one of the first electrode and the second electrode (positive electrode), and the other of the first electrode and the second electrode (negative electrode) is used.
- a negative electrode that is used in a lithium ion secondary battery can be used for this.
- a negative electrode used in a lithium ion secondary battery includes, for example, a negative electrode active material (such as graphite) capable of intercalating and deintercalating lithium ions.
- the electrolytic solution contains a solvent (non-aqueous solvent) and an ionic substance. Ionic substances are dissolved in a solvent and include cations and anions.
- the ionic substance may include, for example, a low melting point compound (ionic liquid) that can exist as a liquid at around room temperature.
- the concentration of the ionic substance in the electrolytic solution is, for example, 0.5 mol/L or more and 2.0 mol/L.
- the solvent preferably has a high boiling point.
- the solvent may contain a lactone compound. Lactone compounds include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone and the like.
- the lactone compound preferably contains ⁇ -butyrolactone (GBL) because it has a low viscosity even at low temperatures, is electrochemically stable in the voltage range of the device, and emits a small amount of gas.
- the solvent may contain other solvents than the lactone compound.
- Other solvents include, for example, chain carboxylic acid esters such as methyl propionate, chain carbonic acid esters such as diethyl carbonate, cyclic carbonic acid esters such as propylene carbonate, and polyhydric alcohols such as ethylene glycol and propylene glycol.
- cyclic sulfones such as sulfolane, amides such as N-methylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, ethers such as 1,4-dioxane, ketones such as methyl ethyl ketone, formaldehyde, etc. can be used.
- the ratio of the lactone compound to the entire solvent may be, for example, 50% by volume or more and 85% by volume or less.
- the solvent may contain acetonitrile.
- Ionic substances include, for example, organic salts.
- An organic salt is a salt in which at least one of the anion and cation contains an organic substance.
- Examples of organic salts whose cations include organic substances include quaternary ammonium salts.
- Organic salts in which the anion (or both ions) contain an organic substance include, for example, trimethylamine maleate, triethylamine borodisalicylate, ethyldimethylamine phthalate, mono-1,2,3,4-tetramethylimidazolinium phthalate, phthalate acid mono 1,3-dimethyl-2-ethylimidazolinium;
- the anion preferably contains an anion of a fluorine-containing acid from the viewpoint of improving withstand voltage characteristics.
- Anions of fluorine-containing acids include, for example, BF 4 - and/or PF 6 - .
- the organic salt preferably contains, for example, a tetraalkylammonium cation and a fluorine-containing acid anion. Specific examples include diethyldimethylammonium tetrafluoroborate (DEDMABF 4 ), triethylmethylammonium tetrafluoroborate (TEMABF 4 ), and the like.
- the ionic material includes lithium salts.
- Lithium salts are preferably salts having fluorine-containing anions.
- salts having fluorine-containing anions at least one selected from the group consisting of LiBF 4 , LiPF 6 and lithium bis(fluorosulfonyl)imide (LiN(SO 2 F) 2 ) is more preferable.
- LiN( SO2F)2 is also referred to as LiFSI or LFSI.
- salts having a fluorine-containing anion LFSI is less likely to produce by-products and has excellent stability.
- a separator is interposed between the first electrode and the second electrode.
- the separator has ion permeability and has a role of physically separating a pair of electrodes to prevent a short circuit.
- the form of the separator is not particularly limited, and may be, for example, a non-woven fabric, a woven fabric, or a microporous film.
- a wound-type electrochemical device has been described, but the scope of application of the present invention is not limited to the above, and can also be applied to devices with other structures, such as stacked-type electrochemical devices.
- the electrochemical device according to the present invention is suitable for applications requiring large capacity and excellent impact resistance.
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Abstract
Description
本発明の一実施形態に係る電気化学デバイスは、第1電極と、第2電極と、第1電極と第2電極との間に介在するセパレータと、電解液と、リード端子と、リード端子を覆う保護テープと、を備える。
図1Aは、巻回型の電気化学デバイスに用いられる第1電極2の巻回前の状態を模式的に示すレイアウト図である。図1Aにおいて、X方向が第1電極の長手方向であって巻回軸に垂直な方向であり、Y方向が第1電極の短手方向であって巻回軸に平行な方向である。図1Bは図1AのX1-X2線における断面図である。なお、図1Aおよび図1Bでは、本発明の要部であるリード端子との接続部を強調して示しており、図面における各構成要素の縮尺は、実際の電極における各構成要素の縮尺と必ずしも一致しない。
本発明の一実施形態に係る電気化学デバイスの製造方法は、上述した電気化学デバイスの製造方法である。製造方法は、第1電極および前記第2電極の一方の電極として、集電箔と、集電箔に設けられる合剤層と、を備えた電極を準備する工程を有する。準備される一方の電極の集電箔は、合剤層に覆われた第1領域と、合剤層で覆われず集電箔の表面が露出する第2領域と、を有する。
電気化学デバイスの第1電極および第2電極としては、例えば、活物質を含む活性層と、活性層を担持する集電体と、を備えた電極が、分極性電極として用いられる。活物質は、例えば、多孔質炭素粒子を含む。活性層は、活物質である多孔質炭素粒子を必須成分として含み、結着剤、導電剤等を任意成分として含み得る。
多孔質炭素粒子の平均粒径および粒度分布は、レーザ回折/散乱法により測定される。測定装置には、例えば、マイクロトラック社製のレーザ回折/散乱式粒子径分布測定装置「MT3300EXII」が用いられる。
電解液は、溶媒(非水溶媒)と、イオン性物質と、を含む。イオン性物質は、溶媒中に溶解しており、カチオンと、アニオンと、を含む。イオン性物質は、例えば常温付近で液体として存在し得る、低融点の化合物(イオン性液体)を含んでいてもよい。電解液中のイオン性物質の濃度は、例えば、0.5mol/L以上、2.0mol/Lである。
第1電極と第2電極の間には、セパレータが介在している。セパレータは、イオン透過性を有し、一対の電極を物理的に離間させて短絡を防止する役割を有する。セパレータの形態は特に限定されず、例えば、不織布または織布であってもよいし、微多孔フィルムであってもよい。
Claims (11)
- 第1電極と、
第2電極と、
前記第1電極と前記第2電極との間に介在するセパレータと、
電解液と、
前記第1電極および前記第2電極の少なくとも一方の電極に電気的に接続されるリード端子と、
前記リード端子を覆う保護テープと、を備え、
前記少なくとも一方の電極は、集電箔と、前記集電箔に設けられる合剤層と、を備え、
前記集電箔は、前記合剤層に覆われた第1領域と、前記合剤層で覆われず前記集電箔の表面が露出する第2領域と、を有し、
前記保護テープは、基材層と、粘着層と、を備え、
前記保護テープは、前記集電箔の前記第2領域に設けられた前記リード端子と接着されるとともに、前記第2領域の一部であって前記リード端子で覆われていない第3領域の少なくとも一部と接着されている、電気化学デバイス。 - 前記リード端子は、柱状の第1部分と、前記第1部分に連続する前記第1部分よりも扁平な第2部分と、を有し、
前記第2部分が前記集電箔の前記第2領域に固定され、
前記第2部分の厚みは、450μm以下である、請求項1に記載の電気化学デバイス。 - 前記リード端子の前記第2部分の少なくとも一部は、前記第2領域において前記集電箔と重ねられ、
前記集電箔は、前記第2部分の少なくとも一部と重ねられる領域に貫通孔を有し、
前記リード端子は、前記第2部分から突出して前記貫通孔を挿通する突起部分をさらに有し、前記突起部分が前記貫通孔を介して前記集電箔にかしめられている、請求項2に記載の電気化学デバイス。 - 前記集電箔の長手方向において、前記第2領域の幅は5000μm以上である、請求項1~3のいずれか1項に記載の電気化学デバイス。
- 前記集電箔の長手方向において、前記リード端子と前記合剤層との間に挟まれた前記第3領域の幅は2000μm以下である、請求項1~4のいずれか1項に記載の電気化学デバイス。
- 前記保護テープは、前記集電箔の両面に設けられ、
前記保護テープは、前記一方の電極から前記集電箔の短手方向に突出し、突出部分において前記両面に設けられた前記保護テープ同士が接着されている、請求項1~5のいずれか1項に記載の電気化学デバイス。 - 前記第3領域において前記集電箔と前記基材層との間に介在する前記粘着層の平均厚みは、前記リード端子と前記基材層の間に介在する前記粘着層の平均厚みよりも厚い、請求項1~6のいずれか1項に記載の電気化学デバイス。
- 前記一方の電極は、分極性電極である、請求項1~7のいずれか1項に記載の電気化学デバイス。
- 前記第1電極および前記第2電極の両方が、分極性電極である、請求項8に記載の電気化学デバイス。
- 前記電解液は、ラクトン化合物を含み、
前記保護テープの基材層は、ポリプロピレンを含む、請求項1~9のいずれか1項に記載の電気化学デバイス。 - 第1電極と、第2電極と、前記第1電極と前記第2電極との間に介在するセパレータと、電解液と、を備える電気化学デバイスの製造方法であって、
前記第1電極および前記第2電極の少なくとも一方の電極として、集電箔と、前記集電箔に設けられる合剤層と、を備えた電極を準備する工程を有し、
前記少なくとも一方の電極の前記集電箔は、前記合剤層に覆われた第1領域と、前記合剤層で覆われず前記集電箔の表面が露出する第2領域と、を有し、
前記集電箔の前記第2領域にリード端子を電気的に接続する工程と、
前記リード端子の少なくとも一部を覆うように保護テープを配置し、前記リード端子の表面の少なくとも一部、および、前記第2領域の一部であって前記リード端子で覆われていない第3領域の少なくとも一部において、保護テープを前記一方の電極に接着させる工程と、
前記保護テープの接着時または接着後に、前記一方の電極の前記第3領域を前記保護テープを介して加圧する工程と、をさらに有する、電気化学デバイスの製造方法。
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JPH04109551A (ja) * | 1990-08-29 | 1992-04-10 | Sony Corp | 非水電解液二次電池 |
JP2009059487A (ja) * | 2007-08-30 | 2009-03-19 | Panasonic Corp | 非水系二次電池 |
JP2009152029A (ja) * | 2007-12-20 | 2009-07-09 | Panasonic Corp | 非水電解液一次電池 |
JP2017183539A (ja) * | 2016-03-30 | 2017-10-05 | 太陽誘電株式会社 | 電気化学デバイス |
JP2017216160A (ja) * | 2016-05-31 | 2017-12-07 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池 |
JP2018067595A (ja) * | 2016-10-18 | 2018-04-26 | 太陽誘電株式会社 | 電気化学デバイス |
WO2019044168A1 (ja) * | 2017-08-31 | 2019-03-07 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池 |
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JPH04109551A (ja) * | 1990-08-29 | 1992-04-10 | Sony Corp | 非水電解液二次電池 |
JP2009059487A (ja) * | 2007-08-30 | 2009-03-19 | Panasonic Corp | 非水系二次電池 |
JP2009152029A (ja) * | 2007-12-20 | 2009-07-09 | Panasonic Corp | 非水電解液一次電池 |
JP2017183539A (ja) * | 2016-03-30 | 2017-10-05 | 太陽誘電株式会社 | 電気化学デバイス |
JP2017216160A (ja) * | 2016-05-31 | 2017-12-07 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池 |
JP2018067595A (ja) * | 2016-10-18 | 2018-04-26 | 太陽誘電株式会社 | 電気化学デバイス |
WO2019044168A1 (ja) * | 2017-08-31 | 2019-03-07 | パナソニックIpマネジメント株式会社 | 非水電解質二次電池 |
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