JP2013182925A - Electrochemical cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrochemical cell capable of suppressing internal resistance, ensuring excellent electric capacitance, and suppressing short-circuit, by a simple structure.SOLUTION: A hybrid capacitor 1 includes a positive electrode 2, a negative electrode 3 oppositely disposed to the positive electrode 2 and an electrolyte 6 in which the positive electrode 2 and the negative electrode 3 are immersed. The positive electrode 2 and/or the negative electrode 3 is formed in a rectangular shape equipped with short sides and long sides, and a penetrating portion 10 for penetrating in the thickness direction of the positive electrode 2 and/or the negative electrode 3. All longitudinal direction one side end portions a of the penetrating portions 10 are formed so as to face at least one side B, C, D except for a vertical direction lower end side A of the positive electrode and/or the negative electrode 3. The longitudinal length of the penetrating portion 10 is made to be less than the short side length of the positive electrode 2 and/or the negative electrode 3, and the penetrating portion 10 is formed so as to dispose the one side end portion a facing one side on the vertical direction upper side in regard to the other side end portion b which does not face the one side.

Description

  The present invention relates to an electrochemical cell, and more particularly to an electrochemical cell used for an electrochemical capacitor, a secondary battery and the like.

  2. Description of the Related Art Conventionally, studies and development of secondary batteries such as lithium ion batteries, electrochemical capacitors such as electric double layer capacitors and hybrid capacitors have been underway as power storage devices mounted on hybrid vehicles and fuel cell vehicles.

  Such an electricity storage device generally includes a positive electrode, a negative electrode, a separator interposed between these electrodes, a cell tank containing an electrode and a separator and filled with an electrolyte so as to immerse them, and have. In each electrode, the energy stored by the electric double layer and / or the oxidation-reduction reaction is discharged, so that the storage device is charged and discharged.

In such an electricity storage device, as an electrolytic solution, for example, an organic electrolytic solution in which a lithium salt such as lithium hexafluorophosphate (LiPF ₆ ) is dissolved in an organic solvent such as ethylene carbonate (C ₃ H ₄ O ₃ ). Is used. However, such an organic electrolyte may be oxidized and decomposed during charging to generate a gas (for example, CO ₂ ). When the gas is generated, the gas stays in the cell of the electricity storage device and may improve the internal resistance, thereby causing a decrease in output characteristics.

  In order to solve such a problem, for example, a positive electrode, a negative electrode disposed opposite to the positive electrode, and an electrolyte solution in which the positive electrode and the negative electrode are immersed are provided, A region where a current collecting tab (a region where the coating layer of the current collector is not formed) is provided in the entire region in the width direction orthogonal to the longitudinal direction, and a coating layer of the positive electrode and / or the negative electrode is formed The thickness direction of the positive electrode and / or negative electrode is substantially the same as the long side length of the coating layer along the direction in which the current flows, specifically, along the longitudinal direction of the positive electrode and / or negative electrode. An electrochemical cell having a penetrating portion that penetrates has been proposed (see, for example, Patent Document 1).

  According to such an electrochemical cell, the gas generated by the oxidative decomposition of the electrolytic solution can be removed by the penetrating portion, so that the internal resistance can be reduced and the output characteristics can be improved.

JP 2011-066324 A

  On the other hand, in such an electrochemical cell, gas tends to move along the penetrating portion. Therefore, if the penetrating portion is formed to have substantially the same length as the long side length of the coating layer as described above, the penetrating portion is formed. There is a problem in that the gas stays in the middle of the longitudinal direction of the part, thereby inhibiting the movement of ions and increasing the internal resistance.

  In addition, when the penetrating portion is formed to have substantially the same length as the long side length of the coating layer as described above, the effective area of the positive electrode and / or the negative electrode is reduced, which may cause a decrease in electric capacity. Furthermore, charging / discharging locally may cause a short circuit due to dendrite.

  On the other hand, Patent Document 1 also discloses a penetrating portion that is formed intermittently, that is, a perforated penetrating portion. When the penetrating portion is formed in this way, the penetrating portion in the longitudinal direction is a positive electrode. In addition, there is a problem that the gas does not stay at the end (one side) of the negative electrode and the movement of ions is hindered due to the gas retention and the internal resistance increases.

  An object of the present invention is to provide an electrochemical cell capable of suppressing internal resistance with a simple configuration, ensuring an excellent electric capacity, and suppressing a short circuit.

  In order to achieve the above object, an electrochemical cell of the present invention includes a positive electrode, a negative electrode disposed to face the positive electrode, and an electrolyte in which the positive electrode and the negative electrode are immersed, and the positive electrode and / or Alternatively, the negative electrode is formed in a rectangular shape having a short side and a long side, and includes a penetrating portion penetrating in the thickness direction, and one end portion in the longitudinal direction of all the penetrating portions is the positive electrode and / Or is formed so as to face at least one side excluding the lower end in the vertical direction of the negative electrode, and the longitudinal length of the penetrating portion is less than the short side length, and the penetrating portion is the one side The one side end portion facing the side is formed so as to be arranged vertically above the other side end portion not facing the one side.

  Further, in the electrochemical cell of the present invention, the through portion is provided in both the positive electrode and the negative electrode, and the projection surface projected in the facing direction of the positive electrode and the negative electrode is provided in the positive electrode. It is preferable that the penetration portion and the penetration portion provided in the negative electrode do not overlap each other.

  Moreover, in the electrochemical cell of the present invention, the penetrating portion is disposed on each of one side in the horizontal direction and the other side in the horizontal direction of the positive electrode and / or the negative electrode, and is disposed on the one side in the horizontal direction. It is preferable that the other end in the longitudinal direction of the penetrating part and the other end in the other longitudinal direction of the penetrating part arranged on the other side in the horizontal direction do not oppose each other along the horizontal direction.

  In the electrochemical cell of the present invention, the one end in the longitudinal direction of all the penetrating parts is formed to face at least one side excluding the lower end in the vertical direction of the positive electrode and / or the negative electrode, and the length in the longitudinal direction is Further, the length of the positive electrode and / or the negative electrode is less than the short side length, and the one side end portion of the penetrating portion facing one side is disposed vertically above the other side end portion not facing the one side. The

  Therefore, in the electrochemical cell of the present invention, gas (bubbles) generated by oxidative decomposition of the electrolytic solution moves along the penetrating portion by buoyancy and desorbs at one end portion in the longitudinal direction. Moreover, in the electrochemical cell of this invention, since a penetration part is as short as less than the short side length of a positive electrode and / or a negative electrode, gas is efficiently desorbed, without staying in the middle of the longitudinal direction of a penetration part.

  As a result, in the electrochemical cell of the present invention, it is possible to suppress the gas from staying in the penetrating portion. As a result, it is possible to suppress the inhibition of ion movement, and thus it is possible to suppress the increase in internal resistance.

  Further, in the electrochemical cell of the present invention, since the penetrating portion is less than the short side length of the positive electrode and / or the negative electrode, a sufficient effective area of the positive electrode and / or the negative electrode can be ensured, and the electric capacity is reduced. Since it can suppress and local charge / discharge can be suppressed, the short circuit by a dendrite can be suppressed.

It is a schematic block diagram of the hybrid capacitor which shows one Embodiment of the electrochemical cell of this invention. FIG. 1 is a front view of an embodiment of a positive electrode and a negative electrode used in the hybrid capacitor shown in FIG. 1 (a configuration in which one end in the longitudinal direction of the through portion faces one horizontal end or the other horizontal end of the positive electrode and / or negative electrode). It is. Other embodiment of the positive electrode and the negative electrode used in the hybrid capacitor shown in FIG. 1 (when the positive electrode and the negative electrode are opposed to each other, on the projection surface projected in the facing direction, (A) is a front view separately showing a positive electrode and a negative electrode, and (b) is a facing direction of the positive electrode and the negative electrode. FIG. Other embodiment of the positive electrode and negative electrode used in the hybrid capacitor shown in FIG. 1 (longitudinal direction other side end portion of the penetrating portion arranged on one side in the horizontal direction and longitudinal direction of penetrating portion arranged on the other side in the horizontal direction It is a front view of the other side edge part which does not oppose along a horizontal direction. Other embodiments of the positive electrode and the negative electrode used in the hybrid capacitor shown in FIG. 1 (one end in the longitudinal direction of the through portion is on the upper end in the vertical direction, one end in the horizontal direction, or the other end in the horizontal direction of the positive electrode and / or the negative electrode) FIG. FIG. 6 is a front view of another embodiment of the positive electrode and the negative electrode used in the hybrid capacitor shown in FIG. 1 (a configuration in which one end portion in the longitudinal direction of the through portion faces the upper end side in the vertical direction of the positive electrode and / or the negative electrode).

  FIG. 1 is a schematic configuration diagram of a hybrid capacitor showing an embodiment of an electrochemical cell of the present invention.

  In FIG. 1, a hybrid capacitor 1 includes a positive electrode 2, a negative electrode 3 disposed opposite to the positive electrode 2 with a gap, a separator 4 interposed between the positive electrode 2 and the negative electrode 3, a positive electrode 2, a negative electrode 3, the cell tank 5 which accommodates the separator 4 and the capture | acquisition member 7 (after-mentioned) provided as needed, and the electrolyte solution 6 stored by the cell tank 5 and in which the positive electrode 2, the negative electrode 3, and the separator 4 are immersed are provided. . The hybrid capacitor 1 is a battery cell employed on a lab scale, and industrially a hybrid capacitor 1 that is appropriately scaled up by a known technique is employed.

  The positive electrode 2 contains a positive electrode material (polarizable carbon material) made of polarizable carbon. For example, an electrode sheet made of a mixture obtained by blending a positive electrode material, a conductive agent, and a polymer binder is formed into a predetermined shape. After forming into details (described later in detail), it is formed by drying as necessary.

  The positive electrode material is obtained by, for example, activating a carbon material.

  Examples of the carbon material include soft carbon and hard carbon.

With soft carbon, for example, by heat treatment in an inert atmosphere, the hexagonal network surface composed of carbon atoms tends to form a relatively regular laminated structure (graphite structure) than the hexagonal network surface of hard carbon. A general term for carbon. Specifically, when heat-treated in an inert atmosphere at 2000 to 3000 ° C., preferably 2500 ° C., the (002) plane average plane distance d ₀₀₂ is 3.40 mm or less, preferably 3.35 to It is a general term for carbon that forms a crystal structure of 3.40%.

  Specific soft carbons include, for example, pitches such as petroleum pitches, coal pitches, and mesophase pitches, and graphites such as petroleum needle cokes, coal needle cokes, anthracene, polyvinyl chloride, polyacrylonitrile, etc. Thermally decomposed products such as chemical coke. These can be used alone or in combination of two or more.

Also, hard carbon, for example, in an inert atmosphere, when it is heat treated at 2500 ° C., is a general term for carbon to form a crystal structure of greater than 3.40Å average spacing _{d 002} of (002) plane.

  Specific hard carbons include, for example, phenol resins, melamine resins, urea resins, furan resins, epoxy resins, alkyd resins, unsaturated polyester resins, diallyl phthalate resins, furfural resins, resorcinol resins, silicone resins, xylene resins, urethanes. Thermosetting resin such as resin, for example, carbon black such as thermal black, furnace black, lamp black, channel black, acetylene black, for example, non-graphitizable coke such as flue coke and gilsonite coke Examples include coke, for example, plant raw materials such as palm, wood flour, and the like, for example, pyrolysates such as glassy carbon.

  These can be used alone or in combination. Of these, soft carbon is preferable.

As the activation treatment, for example, alkaline activation treatment using potassium hydroxide (KOH), sodium hydroxide (NaOH), lithium hydroxide (LiOH), cesium hydroxide (CsOH), rubidium hydroxide (RbOH) or the like as an activator. For example, chemical activation treatment using zinc chloride (ZnCl ₂ ), phosphoric acid (H ₃ PO ₄ ) or the like as an activator, for example, gas activation treatment using carbon dioxide (CO ₂ ), air or the like as an activator, for example, Examples include steam activation treatment using steam (H ₂ O) as an activator. Among these, Preferably, an alkali activation process is mentioned, More preferably, the alkali activation process (KOH activation process) which uses potassium hydroxide (KOH) as an activator is mentioned.

  In the activation treatment, for example, in the case of KOH activation treatment, the carbon material is pre-fired at 500 to 800 ° C., for example, and then fired together with KOH at 700 to 1000 ° C. in a nitrogen atmosphere. The amount of KOH used is, for example, 0.5 to 5 parts by weight with respect to 1 part by weight of the carbon material.

In the hybrid capacitor using the positive electrode material obtained by the activation process as the positive electrode 2, for example, the potential of the positive electrode 2 is 4.23 V vs. A relatively large irreversible capacity can be developed in the positive electrode 2 in a charge / discharge cycle of Li / Li ⁺ or more. Therefore, in the discharge process, the positive electrode can be discharged to a lower potential. As a result, the electric capacity of the positive electrode 2 can be increased.

  A positive electrode material is mix | blended so that the weight ratio of solid content may become a ratio of 70 to 99 weight% with respect to the mixture whole quantity, for example.

  Examples of the conductive agent include carbon black, ketjen black, and acetylene black. These can be used alone or in combination of two or more.

  Moreover, a electrically conductive agent is mix | blended so that the weight ratio of solid content may be a ratio of 0-20 weight% with respect to the mixture whole quantity, for example. That is, the conductive agent may or may not be blended.

  Examples of the polymer binder include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), fluoroolefin copolymer crosslinked polymer, fluoroolefin vinyl ether copolymer crosslinked polymer, carboxymethyl cellulose, polyvinyl pyrrolidone, polyvinyl alcohol, and polyacryl. An acid etc. are mentioned. These can be used alone or in combination of two or more. Of these, PVdF is preferable.

  Moreover, a polymer binder is mix | blended so that the weight ratio of solid content may become a ratio of 1-20 weight% with respect to the mixture whole quantity, for example.

  And in order to form the positive electrode 2, the mixture which mix | blended positive electrode material, the electrically conductive agent, and the polymer binder is stirred in a solvent, and a slurry (solid content: 10 to 60 weight%) is obtained. Next, the slurry is applied to the surface of the positive electrode side current collector 8a to form the positive electrode side coating layer 9a, and then subjected to pressure stretching using, for example, a roll press to obtain an electrode sheet. Next, after the electrode sheet is cut into a predetermined shape (details will be described later), it is further dried if necessary. Thereby, the positive electrode 2 is obtained.

  Examples of the solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone (NMP) and dimethylformamide (DMF), for example, protic polar solvents such as ethanol, methanol, propanol, butanol, and water, for example, Low polar solvents such as toluene, xylene, isophorone, methyl ethyl ketone, ethyl acetate, methyl acetate, dimethyl phthalate and the like can be mentioned. Among these, Preferably, an aprotic polar solvent is mentioned, More preferably, N-methyl-2-pyrrolidone (NMP) is mentioned.

  Examples of the positive electrode side current collector 8a include metal foils such as aluminum foil, copper foil, stainless steel foil, and nickel foil.

  Although the thickness of the positive electrode side current collector 8a varies depending on the scale of the hybrid capacitor 1, it is, for example, 10 to 50 μm on the lab scale, and the thickness of the positive electrode side coating layer 9a is, for example, 10 to 140 μm. The thickness of the positive electrode 2 (the total thickness of the positive electrode side current collector 8a and the positive electrode side coating layer 9a) is, for example, 30 to 150 μm.

  The negative electrode 3 is an electrode that reversibly stores and releases lithium ions, and includes a negative electrode material that can reversibly store and release lithium ions.

  More specifically, the negative electrode 3 is formed, for example, by forming an electrode sheet made of a mixture obtained by blending a negative electrode material and a polymer binder into a predetermined shape (described later in detail), and then drying as necessary. It is formed by.

  The negative electrode material is not particularly limited, and examples thereof include the hard carbon described above, the soft carbon described above, and graphite.

  Examples of graphite include pyrolytic products of condensed polycyclic hydrocarbon compounds such as natural graphite, artificial graphite, graphitized mesophase carbon microspheres, graphitized mesophase carbon fibers, graphite whiskers, graphitized carbon fibers, pitch, and coke. A graphite-type carbon material is mentioned.

  These can be used alone or in combination of two or more. Further, graphite is preferably used in the form of powder (for example, having an average particle size of 25 μm or less).

  And the above negative electrode materials are mix | blended so that the weight ratio of solid content may become a ratio of 80 to 99 weight% with respect to the mixture whole quantity, for example.

  Examples of the polymer binder include the polymer binder described above, and preferably PVdF. Moreover, a polymer binder is mix | blended so that the weight ratio of solid content may become a ratio of 1 to 10 weight% with respect to the mixture whole quantity, for example.

  Moreover, in manufacture of a negative electrode, a electrically conductive agent can also be mix | blended as needed.

  Examples of the conductive agent include the above-described conductive agents. Moreover, a electrically conductive agent is mix | blended so that the weight ratio of solid content may be a ratio of 0-20 weight% with respect to the mixture whole quantity, for example.

  In order to form the negative electrode 3, for example, first, a mixture containing the negative electrode material and the polymer binder is stirred in a solvent to obtain a slurry (solid content: 10 to 60% by weight). Next, the slurry is applied to the surface of the negative electrode side current collector 8b to form the negative electrode side coating layer 9b, and then subjected to pressure stretching using, for example, a roll press to obtain an electrode sheet. Next, after the electrode sheet is cut into a predetermined shape (details will be described later), it is further dried if necessary. Thereby, the negative electrode 3 is obtained.

  Examples of the solvent include the above-mentioned solvents, preferably an aprotic polar solvent, and more preferably N-methyl-2-pyrrolidone (NMP).

  Moreover, as the negative electrode side current collector 8b, for example, the metal foil described above can be used.

  Although the thickness of the negative electrode side current collector 8b varies depending on the scale of the hybrid capacitor 1, it is 10 to 50 μm, for example, on the lab scale, and the thickness of the negative electrode side coating layer 9b is, for example, 5 to 60 μm. The thickness of the negative electrode 3 (total thickness of the negative electrode side current collector 8b and the negative electrode side coating layer 9b) is, for example, 15 to 70 μm.

  Examples of the separator 4 include separators made of inorganic fibers such as glass fibers, ceramic fibers, and whiskers, natural fibers such as cellulose, and organic fibers such as polyolefin and polyester.

  Further, the thickness and size of the separator 4 vary depending on the scale of the hybrid capacitor 1, but in the lab scale, the thickness is, for example, 15 to 150 μm, and the size is, for example, rectangular. The length in the longitudinal direction is, for example, 55 to 115 mm, and the length orthogonal to the longitudinal direction (width direction) is, for example, 50 to 100 mm.

  The cell tank 5 is a known container that seals the positive electrode 2, the negative electrode 3, the separator 4, and the electrolytic solution 6, and includes a known check valve 12 at the upper part in the vertical direction.

  The electrolytic solution 6 contains an organic solvent containing a lithium salt. Specifically, for example, the electrolytic solution 6 is prepared by dissolving a lithium salt in an organic solvent.

The lithium salt has an anion component containing halogen. For example, LiClO ₄ , LiCF ₃ SO ₃ , LiC (SO ₂ CF ₃ ) ₃ , LiC ₄ F ₉ SO ₃ , LiC ₈ F ₁₇ SO ₃ , LiB [C _{6 H 3 (CF 3) 2} -3,5] 4, LiB (C 6 F 5) 4, LiB [C 6 H 4 (CF 3) -4] 4, LiBF 4, LiPF 6, LiAsF 6, LiSbF 6 , LiCF ₃ CO ₂ , LiN (CF ₃ SO ₂ ) _{2 and the} like. In the above formula, [C ₆ H ₃ (CF ₃ ) ₂ -3, 5] is in the 3rd and 5th positions of the phenyl group, and [C ₆ H ₄ (CF ₃ ) -4] is in the 4th position of the phenyl group. Each of which is substituted with —CF ₃ . These can be used alone or in combination of two or more.

  Examples of the organic solvent include propylene carbonate, propylene carbonate derivatives, ethylene carbonate, ethylene carbonate derivatives, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, γ-butyrolactone, 1,3-dioxolane, dimethyl sulfoxide (DMSO), Sulfolane, formamide, dimethylformamide (DMF), dimethylacetamide (DMA), dioxolane, phosphoric acid triester, maleic anhydride, succinic anhydride, phthalic anhydride, 1,3-propane sultone, 4,5-dihydropyran derivative, Nitrobenzene, 1,3-dioxane, 1,4-dioxane, 3-methyl-2-oxazolidinone, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyl Tetrahydrofuran, tetrahydrofuran derivatives, sydnone compounds, acetonitrile, nitromethane, alkoxy ethane, and toluene. These can be used alone or in combination of two or more.

  In order to prepare the electrolytic solution 6, for example, the concentration of the lithium salt is, for example, 0.5 to 5 mol / L, preferably 1 to 3 mol / L. The lithium salt is dissolved in an organic solvent so that the amount is, for example, 50 ppm or less, preferably 10 ppm or less.

  2 shows an embodiment of a positive electrode and a negative electrode used in the hybrid capacitor shown in FIG. 1 (a configuration in which one end in the longitudinal direction of the through portion faces one end in the horizontal direction or the other end in the horizontal direction of the positive and / or negative electrode. Is a front view.

  In the hybrid capacitor 1, the positive electrode 2 and / or the negative electrode 3 are formed in a rectangular shape (substantially rectangular plate shape) having a short side and a long side.

  The ratio of the length of the short side to the long side of the positive electrode 2 and / or the negative electrode 3 is, for example, 40% to 90%, preferably 55% with respect to the long side length of 100%. ~ 85%.

  More specifically, in this hybrid capacitor 1, the positive electrode 2 has a rectangular positive electrode side coating layer 9a laminated on one surface of a positive electrode side current collector 8a formed in a substantially rectangular shape when viewed from the front. (See FIG. 1), it is formed in a rectangular shape.

  Although the size of the positive electrode side current collector 8a varies depending on the scale of the hybrid capacitor 1, for example, the length in the longitudinal direction is, for example, 46 to 97 mm, preferably 67 to 97 mm, and the length in the width direction is, for example, 41 to 41 mm. 73 mm, preferably 53 to 73 mm.

  Such a positive electrode 2 is provided with a positive electrode side current collecting tab 11a only at one end portion in the width direction on a part of one side, specifically, on one side in the longitudinal direction.

  The positive electrode side current collecting tab 11a is a metal foil having a substantially rectangular shape in front view formed so as to protrude along the longitudinal direction at one end portion in the width direction of one side of the positive electrode 2, The positive electrode side current collector 8a is formed integrally with the positive electrode side current collector 8a so as to be continuous from the positive electrode side current collector 8a.

  The size of the positive electrode side current collecting tab 11a varies depending on the scale of the hybrid capacitor 1. For example, the length in the longitudinal direction is, for example, 12 to 39 mm, preferably 22 to 39 mm, and the length in the width direction is, for example, 21 mm. For example, it is less than 73 mm, preferably 37 mm or less.

  Moreover, the width direction length of the positive electrode side current collection tab 11a is 28% or more with respect to the width direction length of the positive electrode 2, for example, less than 100%, Preferably, it is 50% or less.

  Further, the negative electrode 3 is formed in a rectangular shape by laminating a rectangular negative electrode side coating layer 9b on one surface of the negative electrode side current collector 8b formed in a substantially rectangular shape in front view (see FIG. 1). Is formed.

  Although the size of the negative electrode side current collector 8b varies depending on the scale of the hybrid capacitor 1, for example, the length in the longitudinal direction is, for example, 50 to 105 mm, preferably 75 to 105 mm, and the length in the width direction is, for example, 45 to 45 mm. 80 mm, preferably 60 to 80 mm.

  Such a negative electrode 3 is provided with a negative electrode side current collecting tab 11b only on a part of one side thereof, specifically, on one side in the longitudinal direction, only at one end in the width direction.

  The negative electrode side current collecting tab 11b is a metal foil having a substantially rectangular shape in front view formed so as to protrude along the longitudinal direction at one end portion in the width direction of one side of the negative electrode 3, The negative electrode side current collector 8b is formed integrally with the negative electrode side current collector 8b so as to continue from the negative electrode side current collector 8b.

  The size of the negative electrode side current collecting tab 11b varies depending on the scale of the hybrid capacitor 1. For example, the length in the longitudinal direction is, for example, 10 to 44 m, preferably 20 to 44 mm, and the length in the width direction is, for example, 25 mm. For example, it is less than 80 mm, preferably 40 mm or less.

  Moreover, the width direction length of the negative electrode side current collection tab 11b is 31% or more with respect to the width direction length of the negative electrode 3, for example, is less than 100%, Preferably, it is 50% or less.

  In the hybrid capacitor 1, the positive electrode 2 and / or the negative electrode 3 include a through portion 10 that penetrates the thickness direction thereof.

  More specifically, in this hybrid capacitor 1, the coating layer 9 (positive electrode side coating layer) of either or both of the positive electrode 2 obtained above and the negative electrode 3 obtained above. 9a and / or the negative electrode side coating layer 9b) penetrates the thickness direction of the coating layer 9 and the current collector 8 (positive electrode side current collector 8a and / or negative electrode side current collector 8b). A penetrating portion 10 is formed. Preferably, the penetration part 10 is formed in both the positive electrode 2 and the negative electrode 3.

  The shape of the penetrating portion 10 is not particularly limited, and examples thereof include a linear shape, for example, a curved shape such as an S shape and a J shape, and preferably a linear shape.

  Such a penetrating portion 10 has a length in the longitudinal direction (when the penetrating portion 10 has a curved shape or the like, the longitudinal direction of a line connecting one end and the other end; the same applies hereinafter). It is formed in a slit shape less than the short side length.

  The length in the longitudinal direction of the penetrating portion 10 is not particularly limited as long as it is less than the short side length of the positive electrode 2 and / or the negative electrode 3, but for example, 20 to the short side length of the positive electrode 2 and / or the negative electrode 3 -95%, preferably 30-90%.

  Further, in the positive electrode 2 and / or the negative electrode 3, one end a in the longitudinal direction of all the through portions 10 faces at least one side excluding the vertical lower end side A of the positive electrode 2 and / or the negative electrode 3.

  That is, in this hybrid capacitor 1, the short sides of the positive electrode 2 and / or the negative electrode 3 are the vertical lower end side A and the vertical upper end side B, and the long sides are the horizontal one end side C and the horizontal other end side. The positive electrode 2 and / or the negative electrode 3 are arranged so as to be D.

  And the longitudinal direction one side edge part a of the penetration part 10 is at least one side except the vertical direction lower end side A, ie, the vertical direction upper end side B, the horizontal direction one end side C, and the horizontal direction other end side D. It faces.

  More specifically, in FIG. 2, the penetrating part 10 includes a positive electrode 2 and / or a negative electrode 3 on one side in the horizontal direction (one side in the horizontal direction C) and the other side in the horizontal direction (on the other side D in the horizontal direction). In each of the above, a plurality (10 each) are arranged in parallel to each other.

  And the longitudinal direction one side edge part a of the penetration part 10 arrange | positioned at the horizontal direction one side (horizontal direction one side C side) has faced the horizontal direction one side C. Moreover, the longitudinal direction one side edge part a of the penetration part 10 arrange | positioned at the horizontal direction other side (horizontal direction other side D side) has faced the horizontal direction other side D.

  Moreover, the longitudinal direction other side edge part b of these penetration parts 10 is arrange | positioned in the horizontal direction center vicinity of the positive electrode 2 and / or the negative electrode 3, and the longitudinal direction one side edge part a of all the penetration parts 10 is one side. It is arrange | positioned in the orthogonal | vertical direction upper direction with respect to the longitudinal direction other side edge part b which does not face.

  That is, all the penetrating portions 10 have the other end b in the longitudinal direction at the lowermost end in the vertical direction, and are always directed upward in the vertical direction from the other end b in the longitudinal direction toward the one end a in the longitudinal direction. It is formed so as to extend (raise).

  In particular, when the penetrating portion 10 is linear, the penetrating portion 10 forms a predetermined angle θ with respect to a straight line (see a virtual line) parallel to the vertical lower end side A of the positive electrode 2 and / or the negative electrode 3. Formed.

  The angle θ formed by the penetrating part 10 with respect to the straight line parallel to the lower end side A in the vertical direction is, for example, 0 ° <θ ≦ 90 °, preferably 20 ° <θ ≦ 90, as a right angle or an acute angle. It is in the range of °.

  Note that the number and size of the through portions 10 vary depending on the scale of the hybrid capacitor 1 and are appropriately set according to the purpose and application.

  Further, when a plurality of through portions 10 are formed, the interval between the through portions 10 (the interval in the direction orthogonal to the direction in which the through portions 10 extend) varies depending on the scale of the hybrid capacitor 1 and is appropriately determined according to the purpose and application. Is set.

  Further, the penetrating portion 10 is preferably formed uniformly in the entire region of the positive electrode 2 and / or the negative electrode 3 where the coating layer 9 is formed.

  In the embodiment shown in FIG. 2, the penetrating portion 10 includes both the positive electrode 2 and the negative electrode 3 on one side in the horizontal direction (the one side C in the horizontal direction) and the other side in the horizontal direction (the other side D in the horizontal direction). In each of the above, a plurality (10 in each) are arranged so as to be parallel to each other, but the position where the penetrating portion 10 is formed is not limited to the above. For example, the circumference of the positive electrode 2 and the negative electrode 3 is further increased. The penetration part 10 can be arrange | positioned in the vicinity of an edge (refer broken line of FIG. 2).

  Such a slit-like through portion 10 is not particularly limited, and is formed, for example, by cutting the positive electrode 2 and / or the negative electrode 3 with a metal blade so as to penetrate the thickness direction thereof.

  Thus, by forming the penetration part 10 in the positive electrode 2 and / or the negative electrode 3, the gas generated by the oxidative decomposition of the electrolytic solution 6 can be removed via the penetration part 10.

  That is, in this hybrid capacitor 1, for example, the hybrid capacitor 1 is formed as a laminate cell by a known method and then charged, and then the laminate cell is opened once, thereby charging (particularly, the first charge). It is possible to remove the generated gas.

  Specifically, for example, the positive electrode 2, the negative electrode 3, and the separator 4 described above are laminated, and the obtained laminate is accommodated in a cell tank 5 (for example, an aluminum laminate film). Thereafter, the electrolytic solution 6 is injected into the cell tank 5 to form the hybrid capacitor 1 as a laminate cell.

  In this method, the obtained hybrid capacitor 1 is charged one or more times (several to several hundred times) (precycle) before being shipped as a product, and the electrolytic solution 6 is oxidatively decomposed to produce gas. Is generated. Next, the laminate cell of the hybrid capacitor 1 is once opened, the gas is removed through the through portion 10, and then the laminate cell is sealed again.

  Thereby, the gas generated by the oxidative decomposition of the electrolytic solution 6 can be satisfactorily removed from the hybrid capacitor 1 by the through portion 10.

  Furthermore, in this hybrid capacitor 1, for example, a gas collecting part (not shown) is formed so as to communicate with the hybrid capacitor 1, and gas generated during charging is removed from the hybrid capacitor 1 together with the gas collecting part. You can also

  That is, in this method, for example, the above-described hybrid capacitor 1 is formed, and a gas collection unit that communicates with the interior thereof is provided via the check valve 12. Next, before shipping the hybrid capacitor 1 as a product, the hybrid capacitor 1 is charged one or more times (several to several hundred times) (precycle), and the electrolytic solution 6 is oxidatively decomposed to generate gas. Is introduced from the check valve 12 to the gas collecting part through the through part 10 formed in the positive electrode 2 and / or the negative electrode 3. And in this method, while separating the gas collection part from which the gas was collected from the hybrid capacitor 1, the separated part is sealed again.

  Thereby, the gas generated by the oxidative decomposition of the electrolytic solution 6 can be easily and reliably removed by the penetrating part 10 and the gas collecting part (not shown).

  Further, in such a hybrid capacitor 1, not only the gas generated in the above precycle but also the gas generated by the oxidative decomposition of the electrolyte 6 due to continuous use, for example, reversely passes through the through portion 10. It can be continuously removed from the stop valve 12.

  Thus, by forming the penetration part 10 in the positive electrode 2 and / or the negative electrode 3, the gas generated by the oxidative decomposition of the electrolytic solution 6 can be removed via the penetration part 10.

  Therefore, according to such a hybrid capacitor 1, the energy density can be maintained satisfactorily, and the internal resistance can be reduced. As a result, the output characteristics can be improved.

  And in this hybrid capacitor 1, the longitudinal direction one side edge part a of all the penetration parts 10 is at least one side except the vertical direction lower end side A of the positive electrode 2 and / or the negative electrode 3 (side B, side C, FIG. Side D), the length in the longitudinal direction is less than the short side length of the positive electrode 2 and / or the negative electrode 3, and one end portion of the penetrating portion 10 facing the one side described above a is arrange | positioned perpendicularly with respect to the other side edge part b which does not face the one side.

  Therefore, in this hybrid capacitor 1, the gas (bubbles) generated by the oxidative decomposition of the electrolytic solution 6 moves along the penetrating portion 10 by buoyancy, and is desorbed at one end portion a in the longitudinal direction. Further, in this hybrid capacitor 1, since the through portion 10 is as short as the short side length of the positive electrode 2 and / or the negative electrode 3, the gas is efficiently desorbed without staying in the middle of the through portion 10 in the longitudinal direction.

  As a result, in this hybrid capacitor 1, it is possible to suppress the gas from staying in the penetrating portion 10, and as a result, it is possible to suppress the inhibition of ion movement, thereby suppressing the increase in internal resistance.

  Moreover, in this hybrid capacitor 1, since the penetration part 10 is less than the short side length of the positive electrode 2 and / or the negative electrode 3, the effective area of the positive electrode 2 and / or the negative electrode 3 can fully be ensured, and electric capacity Can be suppressed, and local charging / discharging can be suppressed, so that a short circuit caused by dendrite can be suppressed.

In the hybrid capacitor 1, the potential of the positive electrode 2 is preferably 4.23 V vs Li / Li ⁺ or more.

In order to set the potential of the positive electrode 2 to 4.23 V vs Li / Li ⁺ or higher, for example, when soft carbon and / or hard carbon is used for the negative electrode 3, the cell voltage is applied at 3 V or higher.

If the potential of the positive electrode 2 is 4.23 V vs Li / Li ⁺ or more, the energy density of the hybrid capacitor 1 can be improved.

On the other hand, in this hybrid capacitor 1, when the potential of the positive electrode 2 is set to a high potential of 4.23 V vs Li / Li ⁺ or higher, the anion contained in the electrolyte 6 is caused by the irreversible capacity of the positive electrode 2. (e.g., PF ₆ contained in LiPF ₆ ^-, etc.) negative active inhibitor derived from in some cases be generated.

  The process in which the negative electrode activity inhibitor is generated, for example, the process in which HF is generated due to the development of the irreversible capacity of the positive electrode 2 is presumed as follows.

First, when the above-described predetermined voltage (that is, 4.23 V vs Li / Li ⁺ or more) is applied to the positive electrode 2 and the negative electrode 3, in the electrolytic solution 6, for example, from moisture and organic substances contained in the positive electrode 2 and the electrolytic solution 6. As shown in the following formulas (1) and (2), protons (H ⁺ ) are generated.
(1) 2H ₂ O → O ₂ + 4H ⁺ + 4e ⁻
(2) R−H → R + H ⁺ + e ⁻ (R is an alkyl group)
Then, the generated protons, anion contained in the electrolytic solution 6 (for example, PF ₆ contained in LiPF ₆ ^-, etc.) and react, HF is generated (see the following formula (3)).
(3) PF ₆ ⁻ + H ⁺ → PF ₅ + HF
A negative electrode activity-inhibiting substance such as HF may reduce the electric capacity of the negative electrode 3 and reduce the energy density of the hybrid capacitor 1.

  Therefore, in this hybrid capacitor 1, it is preferable to capture a negative electrode activity inhibiting substance derived from an anion contained in the electrolytic solution 6 between the positive electrode 2 and the negative electrode 3 and at least one of the positive electrode 2 and the negative electrode 3. The scavenger to be contained is included.

  By including a capture agent in the hybrid capacitor 1, for example, even if a negative electrode activity inhibitor is generated due to the irreversible capacity of the positive electrode 2, the negative electrode activity inhibitor can be captured by the capture agent.

Examples of the scavenger include alkali metal carbonates such as lithium carbonate (Li ₂ CO ₃ ), sodium carbonate (Na ₂ CO ₃ ), and potassium carbonate (K ₂ CO ₃ ). These can be used alone or in combination of two or more. Of these, lithium carbonate is preferable.

  More specifically, for example, when the capture agent is contained (arranged) between the positive electrode 2 and the negative electrode 3, the capture agent is preferably formed as the capture member 7.

  The capturing member 7 is, for example, a sheet obtained by press-stretching a capturing agent for capturing a negative electrode activity inhibitor and a polymer binder.

  Examples of the polymer binder include the above-described polymer binder, and preferably PTFE.

  And in order to form the capture | acquisition member 7, for example, first, a capture | acquisition agent and a polymer binder are used, for example, the mixture ratio of capture | acquisition agent: polymer binder is 20: 80-98: 2 in the weight ratio of solid content, Preferably, it mix | blends so that it may become 50: 50-90: 10, and prepares a mixture. Next, the mixture is pressurized and stretched using, for example, a roll press to obtain a capturing agent-containing sheet.

  Then, the scavenger-containing sheet is punched into a predetermined shape (for example, a rectangular shape) and then dried as necessary. Thereby, the capture member 7 is obtained.

  In this hybrid capacitor 1, for example, as shown in FIG. 1, as the separator 4, a separator 4a disposed on the positive electrode 2 side and a separator 4b disposed on the negative electrode 3 side are provided, and these separators 4a and 4b are provided. The capturing member 7 is provided between the two.

  By providing the capture member 7, for example, even if a negative electrode activity inhibitor is generated due to the irreversible capacity of the positive electrode 2, the negative electrode activity inhibitor can be captured by the capture member 7. Moreover, such a capture | acquisition member 7 can serve as a separator as a capture agent containing separator.

  In the hybrid capacitor 1, for example, the above carbonate can be disposed between the separator 4 a and the separator 4 b as a capturing agent without forming the capturing member 7.

  In order to arrange the carbonate between the separator 4a and the separator 4b, for example, powdery carbonate is added to one surface of the separator 4a or the separator 4b, and the surface and the surface of the other separator 4a (4b) are added. And sandwich the carbonate.

  In the hybrid capacitor 1, the carbonate may be coated on the surface of the positive electrode 2 and / or the negative electrode 3.

  In order to coat the carbonate on the surface of the positive electrode 2 and / or the negative electrode 3, for example, a mixture containing carbonate and a binder is stirred and mixed in a solvent, and then applied onto the positive electrode 2 and / or the negative electrode 3 After that, it is dried.

  Examples of the binder include the polymer binder described above.

  Examples of the solvent include the above-mentioned solvents, preferably NMP (N-methyl-2-pyrrolidone) and water.

  Furthermore, in this hybrid capacitor 1, lithium foil can also be used as a scavenger.

  As the lithium foil, a known lithium foil can be used. For example, the lithium foil is formed in a circular shape or a rectangular shape.

  The lithium foil is preferably formed so that the surface area thereof is substantially the same as or larger than the surface areas of the positive electrode 2 and the negative electrode 3. When the surface area of the lithium foil is such an area, the negative electrode activity inhibiting substance (for example, HF) can be efficiently captured.

  Furthermore, the thickness is 0.01-0.1 mm, for example, Preferably, it is 0.01-0.05 mm.

  The lithium foil has a plurality of holes in the thickness direction. By forming such a hole, the electrolytic solution 6 can pass between the separator 4a and the separator 4b, and can be charged and discharged.

  The lithium foil may be any lithium metal. For example, lithium powder or paste-like lithium may be provided as a scavenger.

  In addition to the lithium metal described above, the negative electrode activity inhibitor can also be captured by including in the cell tank 5 a compound having a Si—N bond (for example, perhydropolysilazane, methylpolysilazane, etc.). In this case, the negative electrode activity inhibiting substance is captured and stabilized by the compound having a Si—N bond.

  When the scavenger is contained in the positive electrode 2 and / or the negative electrode 3, the scavenger is used as a material component of the positive electrode 2 and / or the negative electrode 3, for example.

  That is, in such a case, a scavenger (for example, carbonate, lithium powder, etc.) is blended with the positive electrode material or the negative electrode material in the manufacturing process of the positive electrode 2 and / or the negative electrode 3. Thereby, the scavenger is contained in the positive electrode 2 and / or the negative electrode 3.

Then, such scavenger (catching member 7), to the irreversible capacity 1mAh expressed in the positive electrode 2, preferably in a ratio of ^{2 × 10 -5 mol~175 × 10 -5} mol.

  When the amount of the scavenger is within such a range, a further excellent energy density can be expressed.

For example, referring to the above formulas (1) to (3), 1 mol of HF is generated with the flow of 1 mol of electrons. In other words, the irreversible capacity expressed in positive electrode 2 and Q (mAh), a Faraday constant 96500 (C / mol) Then, the amount _{M HF} of HF generated in the hybrid capacitor _1, M HF = 3.6 × Q × F ⁻¹ (mol).

In the case of using the _Li 2 CO ₃ as a scavenger, as shown in the following formula (4), HF is (reacts with _Li 2 CO ₃₎ is trapped in _Li 2 CO _3, LiF and _H 2 CO ₃ is generated.
(4) Li ₂ CO ₃ + 2HF → 2LiF + H ₂ CO ₃
As shown in the above formula (4), 0.5 mol of Li ₂ CO ₃ is required to capture 1 mol of HF. More specifically, the required amount M _Li2CO3 of Li ₂ CO ₃ is M _Li2CO3 = 0.5M _HF = 1.8 × Q × F ⁻¹ (mol). When F = 96500 is substituted, M _Li2CO3 = 2 × 10 ⁻⁵ × Q (mol). That is, when Li ₂ CO ₃ is contained 2 × 10 ⁻⁵ × Qmol or more with respect to the irreversible capacity Q (mAh), HF can be sufficiently captured. As a result, since a decrease in energy density due to the negative electrode activity inhibitor (HF) can be suppressed, a further excellent energy density can be expressed.

  FIG. 3 shows another embodiment of the positive electrode and the negative electrode used in the hybrid capacitor shown in FIG. 1 (when the positive electrode and the negative electrode are opposed to each other, the through-hole provided in the positive electrode is projected in the facing direction. And a through-hole provided in the negative electrode is a front view of a form in which they do not overlap each other.

  In the embodiment shown in FIG. 2, the penetrating portion 10 is formed in the same manner with respect to each of the positive electrode 2 and the negative electrode 3, but when the positive electrode 2 and the positive electrode 3 are arranged to face each other (see FIG. 1), On the projection surface projected in the opposing direction of the positive electrode 2 and the negative electrode 3, the through portion 10 of the positive electrode 2 and the through portion 10 of the negative electrode 3 overlap.

  In such a case, the positive electrode 2 and / or the negative electrode 3 may be damaged (eg, torn), and the electric capacity of the hybrid capacitor 1 may be reduced.

  Therefore, for example, as shown in FIG. 3, in the projection surface projected in the opposing direction of the positive electrode 2 and the negative electrode 3, the penetration part 10 provided in the positive electrode 2 and the penetration part 10 provided in the negative electrode 3 are mutually connected. The positive electrode 2 and the negative electrode 3 can be provided with a through portion 10 so as not to overlap.

  More specifically, in FIG. 3A, the penetrating portion 10 includes a horizontal one side (horizontal one side C side) and a horizontal other side (horizontal other side D) of both the positive electrode 2 and the negative electrode 3. In each of the two sides, a plurality (ten each) are arranged in parallel with each other.

  Further, the penetrating portion 10 formed in the positive electrode 2 and the penetrating portion 10 formed in the negative electrode 3 are formed in the same pattern.

  And in such a positive electrode 2 and the negative electrode 3, as FIG.3 (b) is referred, the penetration part 10 of the positive electrode 2 and the penetration part 10 of the negative electrode 3 have arrange | positioned the positive electrode 2 and the negative electrode 3 facing each other. Sometimes, they are arranged so as not to overlap each other on the projection plane projected in the opposite direction.

  That is, the penetration part 10 of the negative electrode 3 is arranged in a bowl shape between the penetration parts 10 adjacent to each other of the positive electrode 2.

  According to such a hybrid capacitor 1, damage to the positive electrode 2 and / or the negative electrode 3 can be suppressed, and a decrease in electric capacity of the hybrid capacitor 1 can be suppressed.

  4 shows another embodiment of the positive electrode and the negative electrode used in the hybrid capacitor shown in FIG. 1 (the other end portion in the longitudinal direction of the penetrating portion arranged on one side in the horizontal direction and the penetrating member arranged on the other side in the horizontal direction. It is a front view of the longitudinal direction other side edge part of a part which does not oppose along a horizontal direction.

  In the embodiment shown in FIG. 2, the penetrating part 10 is formed so as to be symmetric with respect to the horizontal center line of the positive electrode 2 and / or the negative electrode 3, and the other longitudinal direction of the penetrating part 10 on one side in the horizontal direction. The side end b and the other end b in the longitudinal direction of the penetrating part 10 on the other side in the horizontal direction are arranged so as to face each other along the horizontal direction.

  In such a case, the longitudinal direction other side end portion b of the penetrating portion 10 on the one side in the horizontal direction and the longitudinal direction other side end portion b of the penetrating portion 10 on the other side in the horizontal direction are close to each other. , The positive electrode 2 and / or the negative electrode 3 may be damaged (eg, torn).

  Therefore, for example, as shown in FIG. 4, the other end b in the longitudinal direction of the penetrating part 10 formed on one side in the horizontal direction and the other end in the longitudinal direction of the penetrating part 10 formed on the other side in the horizontal direction. It can arrange | position so that b may not oppose along a horizontal direction.

  More specifically, in FIG. 4, the penetrating portion 10 is disposed on each of the one side in the horizontal direction and the other side in the horizontal direction of the positive electrode 2 and / or the negative electrode 3. And the penetration part 10 arrange | positioned at the horizontal direction one side and the penetration part 10 arrange | positioned at the other horizontal direction side are formed asymmetrically with respect to the horizontal direction center line of the positive electrode 2 and / or the negative electrode 3. The other end b in the longitudinal direction of the penetrating part 10 on the one side in the horizontal direction and the other end b in the longitudinal direction of the penetrating part 10 on the other side in the horizontal direction are arranged so as not to face each other in the horizontal direction. ing.

  That is, in the positive electrode 2 and / or the negative electrode 3, the other end b in the longitudinal direction of the penetrating portion 10 on one side in the horizontal direction and the other end b in the longitudinal direction of the penetrating portion 10 on the other side in the horizontal direction are provided. Are relatively spaced apart.

  In such a hybrid capacitor 1, damage to the positive electrode 2 and / or the negative electrode 3 can be suppressed.

  FIG. 5 shows another embodiment of the positive electrode and the negative electrode used in the hybrid capacitor shown in FIG. 1 (the one end on the longitudinal side of the penetrating portion is the upper end in the vertical direction, one end in the horizontal direction, or the horizontal direction of the negative electrode) FIG. 6 shows another embodiment of the positive electrode and the negative electrode used in the hybrid capacitor shown in FIG. 1 (the one end on the longitudinal side of the through portion is the vertical of the positive electrode and / or the negative electrode). It is a front view of a form facing the upper end side in the direction.

  In the above description, the short side of the positive electrode 2 and / or the negative electrode 3 is the vertical lower end side A and the vertical upper end side B. For example, as shown in FIG. The sides can also be the vertical lower end side A and the vertical upper end side B.

  Further, in the above description, the one end a in the longitudinal direction of the penetrating part 10 faces either one of the two horizontal sides C or the other horizontal side D of the positive electrode 2 and / or the negative electrode 3. For example, as shown in FIG. 5, one end side “a” in the longitudinal direction of the penetrating portion 10 is any one of the three sides of the vertical upper end side B, the horizontal one end side C, and the horizontal other end side D. It can also be brought to.

  Specifically, in the embodiment shown in FIG. 5, the long sides of the positive electrode 2 and the negative electrode 3 formed in a rectangular shape are the lower end side A in the vertical direction and the upper end side B in the vertical direction, and the short side is one end in the horizontal direction. It is set as the side C and the other end D in the horizontal direction.

  And in such embodiment, the penetration part 10 is the horizontal direction one side (the horizontal direction one side C side) of the positive electrode 2 and / or the negative electrode 3, the horizontal direction other side (the horizontal direction other side D side), In addition, a plurality of them are arranged in parallel with each other in the vicinity of the center in the horizontal direction.

  And the longitudinal direction one side edge part a of the penetration part 10 arrange | positioned at the horizontal direction one side (horizontal direction one side C side) has faced the horizontal direction one side C, and these penetration parts 10 are perpendicular | vertical. It is formed so as to form a predetermined angle θ with respect to a straight line parallel to the direction lower end side A.

  Moreover, the longitudinal direction one side edge part a of the penetration part 10 arrange | positioned at the horizontal direction other side (horizontal direction other side D side) has faced the horizontal direction other side D, These penetration parts 10 are It is formed to form a predetermined angle θ with respect to a straight line parallel to the vertical lower end side A.

  Furthermore, the longitudinal direction one side edge part a of the penetration part 10 arrange | positioned in the horizontal direction center vicinity has faced the vertical direction upper end side B, and these penetration parts 10 are a straight line parallel to the vertical direction lower end side A. It is formed so as to form a right angle (90 °).

  Furthermore, as described above, when the long sides of the positive electrode 2 and the negative electrode 3 formed in a rectangular shape are the lower end side A in the vertical direction and the upper end side B in the vertical direction, for example, as shown in FIG. The one end part a in the longitudinal direction of the penetrating part 10 can also face the upper end side B in the vertical direction.

  More specifically, in this embodiment, the current collecting tab 11 is formed over the entire length of one side C of the positive electrode 2 and / or the negative electrode 3 in the horizontal direction, and all the through portions 10 extend along the horizontal direction. Are arranged at equal intervals, and one end portion a in the longitudinal direction thereof faces the upper end side B in the vertical direction and is formed to form a right angle (90 °) with respect to a straight line parallel to the lower end side A in the vertical direction. .

  Also in the hybrid capacitor 1 obtained using the positive electrode 2 and / or the negative electrode 3 shown in FIG. 5 or FIG. 6, the longitudinal direction one side end a of all the through portions 10 is the lower end in the vertical direction of the positive electrode 2 and / or the negative electrode 3. It is formed so as to face at least one side (side B, side C, side D in FIG. 2) excluding side A, and its longitudinal length is less than the short side length of positive electrode 2 and / or negative electrode 3 Furthermore, the one side end a facing the one side of the penetrating portion 10 is arranged vertically above the other side end b not facing the one side.

  Therefore, in this hybrid capacitor 1, the gas (bubbles) generated by the oxidative decomposition of the electrolytic solution 6 moves along the penetrating portion 10 by buoyancy, and is desorbed at one end portion a in the longitudinal direction. Further, in this hybrid capacitor 1, since the through portion 10 is as short as the short side length of the positive electrode 2 and / or the negative electrode 3, the gas is efficiently desorbed without staying in the middle of the through portion 10 in the longitudinal direction.

  As a result, in this hybrid capacitor 1, it is possible to suppress the gas from staying in the penetrating portion 10, and as a result, it is possible to suppress the inhibition of ion movement, thereby suppressing the increase in internal resistance.

  Moreover, in this hybrid capacitor 1, since the penetration part 10 is less than the short side length of the positive electrode 2 and / or the negative electrode 3, the effective area of the positive electrode 2 and / or the negative electrode 3 can fully be ensured, and electric capacity Can be suppressed, and local charging / discharging can be suppressed, so that a short circuit caused by dendrite can be suppressed.

  In the above description, the current collecting tab 11 is provided on the positive electrode 2 and / or the negative electrode 3. However, depending on the purpose and application, the hybrid may be provided without providing the current collecting tab 11 on the positive electrode 2 and / or the negative electrode 3. The capacitor 1 can also be formed.

  As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, A various change is possible within the range of a claim description. For example, the hybrid capacitor 1 can be changed to an electric double layer capacitor or a lithium ion battery.

  For example, in the case of an electric double layer capacitor, for example, activated carbon is used as a material for the negative electrode and the negative electrode.

On the other hand, in the case of a lithium ion battery, various oxides and sulfides are used as the positive electrode material instead of the material used for the positive electrode 2 described above. For example, manganese dioxide (MnO ₂ ), lithium manganese composite Oxides (eg, LiMn ₂ O ₄ , LiMnO _2, etc.), lithium nickel composite oxides (eg, LiNiO _2, etc.), lithium cobalt composite oxides (eg, LiCoO _2, etc.), lithium nickel cobalt composite oxides, lithium manganese Cobalt composite oxide, vanadium oxide (for example, V ₂ O ₅ etc.) and the like are used. Organic materials such as conductive polymer materials and disulfide polymer materials can also be used.

  And the electrochemical cell of this invention can be used suitably as various industrial products, such as memory backup power supplies, such as a drive battery mounted in a motor vehicle (hybrid vehicle etc.), a notebook personal computer, a mobile phone, etc., for example.

DESCRIPTION OF SYMBOLS 1 Hybrid capacitor 2 Positive electrode 3 Negative electrode 4 Separator 5 Cell tank 6 Electrolyte 7 Capturing member 8a Positive electrode side collector 8b Negative electrode side collector 9a Positive electrode side coating layer 9b Negative electrode side coating layer 10 Penetration part 11a Positive electrode side current collector Tab 11b Negative electrode side current collection tab

Claims (3)

A positive electrode;
A negative electrode disposed opposite to the positive electrode;
An electrolyte solution in which the positive electrode and the negative electrode are immersed,
The positive electrode and / or the negative electrode is formed in a rectangular shape having a short side and a long side, and includes a penetrating portion that penetrates the thickness direction thereof.
One end of each penetrating portion in the longitudinal direction is formed so as to face at least one side excluding the lower end in the vertical direction of the positive electrode and / or the negative electrode, and the longitudinal length of the penetrating portion is Less than the short side length, and
The penetrating part is formed such that the one side end facing the one side is arranged vertically above the other side end not facing the one side. Chemical cell. The penetrating portion is provided in both the positive electrode and the negative electrode;
2. The projection surface projected in the opposing direction of the positive electrode and the negative electrode, wherein the through part provided in the positive electrode and the through part provided in the negative electrode do not overlap each other. The electrochemical cell according to 1. The penetrating portion is disposed on each of the one side in the horizontal direction and the other side in the horizontal direction of the positive electrode and / or the negative electrode;
The longitudinal direction other side end portion of the penetrating portion disposed on the one horizontal side;
The longitudinal direction other side end of the penetrating portion arranged on the other side in the horizontal direction,
The electrochemical cell according to claim 1, wherein the electrochemical cell is not opposed along the horizontal direction.

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