WO2013183326A1 - Dispositif électrochimique - Google Patents

Dispositif électrochimique Download PDF

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Publication number
WO2013183326A1
WO2013183326A1 PCT/JP2013/055951 JP2013055951W WO2013183326A1 WO 2013183326 A1 WO2013183326 A1 WO 2013183326A1 JP 2013055951 W JP2013055951 W JP 2013055951W WO 2013183326 A1 WO2013183326 A1 WO 2013183326A1
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WO
WIPO (PCT)
Prior art keywords
sheet
electrode
electrode sheet
lid
electrochemical device
Prior art date
Application number
PCT/JP2013/055951
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English (en)
Japanese (ja)
Inventor
響太郎 真野
直人 萩原
Original Assignee
太陽誘電株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2012220863A external-priority patent/JP2014075204A/ja
Application filed by 太陽誘電株式会社 filed Critical 太陽誘電株式会社
Priority to US14/406,049 priority Critical patent/US20150155540A1/en
Priority to CN201380030147.9A priority patent/CN104380411A/zh
Priority to KR1020147032091A priority patent/KR20150002833A/ko
Publication of WO2013183326A1 publication Critical patent/WO2013183326A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0436—Small-sized flat cells or batteries for portable equipment
    • 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
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/78—Cases; Housings; Encapsulations; Mountings
    • 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
    • H01M10/0463—Cells or batteries with horizontal or inclined electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • This invention relates to the electrochemical device which enclosed the electrical storage element which can be charged / discharged.
  • surface mountable electrochemical devices such as electric double layer capacitors and lithium ion batteries are used as power sources suitable for memory backup applications. It has been.
  • This electrochemical device generally includes an insulating case having a recess in the upper surface opening, a conductive lid in which the recess in the case is closed in a watertight and airtight manner, a chargeable / dischargeable storage element enclosed in the closed recess, and An electrolyte, a positive electrode terminal and a negative electrode terminal provided on the mounting surface of the case, a positive electrode wiring for electrically connecting the positive electrode terminal and the positive electrode side of the energy storage device, and the negative electrode terminal and the negative electrode side of the energy storage device And a negative electrode wiring for electrically connecting the two (refer to Patent Document 1).
  • the power storage element includes a first electrode sheet having a predetermined size made of an active material, a second electrode sheet having a predetermined size made of an active material, and a separate sheet having a predetermined size made of an ion permeable sheet.
  • the sheet and the second electrode sheet are stacked in this order. Since a separate sheet having an outer dimension slightly larger than the outer dimensions of both electrode sheets is used, the outer peripheral portion of the separate sheet slightly protrudes outward from both electrode sheets.
  • the materials of the first electrode sheet and the second electrode sheet may be the same or different depending on the type of electrochemical device.
  • the separate sheet has a role of preventing a short circuit between the first electrode sheet and the second electrode sheet, a role of holding the electrolytic solution between the opposing surfaces of the first electrode sheet and the second electrode sheet, and a retained electrolysis Since it plays a role of allowing ion movement in the liquid, a fiber-based porous sheet having a thickness suitable for these roles is generally used.
  • Patent Document 2 describes a separator for an electric double layer capacitor comprising a porous sheet having a high density layer having a porosity of about 20 to 50% and a low density layer having a porosity of about 50 to 80%.
  • the electrolytic solution is mainly impregnated in the first electrode sheet, the second electrode sheet and the separate sheet, and the electrolytic solution does not flow greatly in the charge and discharge process,
  • the electrolyte solution impregnated in the portion sandwiched between the two electrode sheets of the separate sheet is drawn into both electrode sheets. There may be a phenomenon in which the amount of electrolyte in the portion is very small but decreases.
  • the portion sandwiched between the two electrode sheets of the separate sheet is the portion of the electrolyte sheet corresponding to the portion drawn into the two electrode sheets from the portion of the separate sheet that protrudes outward. Try to pull in.
  • the thickness of the portion of the separate sheet that protrudes outward from both electrode sheets is the same as the thickness of the portion sandwiched between the electrode sheets, and the liquid absorption is the same, so it protrudes outward from both electrode sheets. It is difficult to immediately draw the electrolytic solution from the exposed portion to the portion sandwiched between both electrode sheets.
  • the amount of electrolyte impregnated in the portion projecting outward from both electrode sheets is very small, and when the above phenomenon occurs frequently, the electrolysis of the portion sandwiched between the two electrode sheets of the separate sheet The decrease in the amount of liquid cannot be eliminated, and the accumulation of the phenomenon causes a decrease in charge / discharge characteristics.
  • liquid absorption corresponds to the water absorption speed according to the Bayrec method specified in JIS-L-1907. Further, in [Description of Embodiments] in the specification, mm / 10 min is used as a unit of the “liquid absorption”.
  • An object of the present invention is to provide an electrochemical device capable of quickly and surely eliminating the phenomenon of a decrease in the amount of electrolyte frequently occurring in a portion sandwiched between both electrode sheets of a separate sheet. .
  • an electrochemical device includes a case, a lid, and a power storage element.
  • the case has an opening recess.
  • the lid is coupled to the opening side of the case and forms a closed portion with the recess.
  • the power storage element includes a first electrode sheet, a second electrode sheet, and a porous separate sheet.
  • the first electrode sheet has a first main surface and a first edge surface formed around the first main surface.
  • the second electrode sheet has a second main surface facing the first main surface, and a second edge surface formed around the second main surface.
  • the separate sheet is interposed between the first main surface and the second main surface.
  • the power storage element is enclosed in the closed portion and configured to be chargeable / dischargeable.
  • the separate sheet has a first portion, a second portion, and a third portion.
  • the first portion is disposed between the first electrode sheet and the second electrode sheet.
  • the second portion projects outward from the first electrode sheet and the second electrode sheet, and is not in contact with the lid.
  • the third portion is provided on at least a part of the second portion, and is in contact with at least one of the first edge surface and the second edge surface.
  • the electrolyte solution impregnated in the first portion sandwiched between the two electrode sheets of the separate sheet is brought into both electrode sheets.
  • the electrolyte impregnated in the second portion is absorbed.
  • the first part is immediately drawn in accordance with the liquidity difference, and the electrolyte is replenished immediately to the first part.
  • the second portion is impregnated with a considerable amount of the electrolytic solution, even if the phenomenon occurs frequently, the first portion is immediately replenished with the electrolytic solution.
  • the phenomenon of a decrease in the amount of electrolyte frequently occurs in the portion sandwiched between the two electrode sheets of the separate sheet the phenomenon can be quickly and reliably eliminated, and the charge / discharge characteristics can be reduced by the accumulation of the phenomenon Can also be avoided.
  • the electrolyte solution impregnated in the first part is applied to both electrode sheets.
  • the phenomenon that the amount of the electrolytic solution in the first portion is reduced due to the drawing can be suppressed by the electrolyte replenishing action from the third portion to the electrode sheet.
  • the outer peripheral portion (second portion) of the separate sheet is configured to be in non-contact with the lid, when the case and the lid are joined, the electrolyte overflows and the case and the lid It is possible to effectively prevent the electrolyte from being contaminated and to ensure the productivity of the electrochemical device.
  • FIG. 1 is an external perspective view of an electrochemical device according to a first embodiment of the present invention.
  • FIG. 2 is an enlarged cross-sectional view taken along line S11-S11 of the electrochemical device shown in FIG. It is an enlarged top view of the case shown in FIG.
  • FIG. 3 is a perspective view showing a configuration before arrangement of the electric storage element shown in FIG. 2. It is a figure for demonstrating the arrangement method (arrangement
  • (A) is a principal part schematic sectional drawing of the electrical storage element in the electrochemical device shown in FIG.
  • (B) is a principal part schematic sectional drawing of the electrical storage element in the electrochemical device which concerns on a comparative example. It is an external appearance perspective view of the electrochemical device which concerns on the 2nd Embodiment of this invention. It is an external appearance perspective view of the electrochemical device which concerns on the 3rd Embodiment of this invention. It is a perspective view which shows the structure before arrangement
  • FIGS. 1 and 2 show an electrochemical device according to a first embodiment of the present invention.
  • the electrochemical device 100 illustrated in FIGS. 1 and 2 includes a case 11, a lid 12, a power storage element 13, a positive electrode terminal 14, a negative electrode terminal 15, a positive electrode wiring 16, and a negative electrode wiring 17.
  • the case 11 is made of an insulating material such as alumina, and is formed in a rectangular parallelepiped shape having a predetermined length, width, and height.
  • the upper surface of the case 11 is formed with a concave portion 11a having an opening having a rectangular top view and a predetermined depth. That is, the case 11 has an opening of the recess 11a on its upper surface, and its lower surface is used as a mounting surface. Further, at the four corners when the case 11 is viewed from above, cutouts 11b whose top view outlines form approximately 1 ⁇ 4 circle are formed in the vertical direction.
  • the case 11 is provided with a positive electrode terminal 14, a negative electrode terminal 15, a positive electrode wiring 16, and a negative electrode wiring 17, as well as a coupling ring 18 and a current collecting film 19.
  • the positive electrode terminal 14 is made of a conductive material such as gold, and is formed to have an L-shaped cross section extending from the center to the lower surface of one end surface in the length direction of the case 11 and having a predetermined width.
  • the negative electrode terminal 15 is made of a conductive material such as gold, has an L-shaped cross section extending from the center of the other end surface in the length direction of the case 11 to the lower surface, and has substantially the same width as the positive electrode terminal 14. Is formed.
  • an adhesion auxiliary layer (for example, a tungsten film and a nickel film arranged in order from the case side) is formed on the side surface and the lower surface of the case 11 in advance to increase the adhesion of the positive electrode terminal 14 and the negative electrode terminal 15 to the lower surface. It is good to leave.
  • the positive electrode wiring 16 is made of a conductive material such as tungsten, and is formed inside the case 11 so as to reach the lower surface of the current collecting film 19 from the center of one end surface in the length direction of the case 11. Specifically, as shown in FIG. 3, the positive electrode wiring 16 includes a portion (not shown) having substantially the same width as the positive electrode terminal 14, a total of three strip portions 16 a extending inward from the portion, and each strip portion. A total of three columnar portions 16 b extending from the end of 16 a toward the current collecting film 19 are provided.
  • the positions of the columnar portions 16b are different on the bottom surface 11a1 of the recess 11a of the case 11, and the upper surface of each columnar portion 16b is exposed at the bottom surface 11a1 of the recess 11a.
  • the portion of the positive electrode wiring 16 exposed from one end surface in the length direction of the case 11 is electrically connected to the side surface portion of the positive electrode terminal 14.
  • the negative electrode wiring 17 is made of a conductive material such as tungsten, and a part of the negative electrode wiring 17 is formed inside the case 11 so as to reach the upper surface of the case 11 from the center of the other end surface in the length direction of the case 11, and the other part is the case. 11 are formed on the side surface and the upper surface.
  • the negative electrode wiring 17 has a portion (not indicated by reference numeral) having substantially the same width as the negative electrode terminal 15 and positioned in the case 11, and extends outward from the portion and positioned in the case 11.
  • the portion of the negative electrode wiring 17 exposed from the other end surface in the length direction of the case 11 is electrically connected to the side surface portion of the negative electrode terminal 15, and each fan-shaped portion existing on the upper surface of the case 11 of the negative electrode wiring 17.
  • 17 c is electrically connected to the lower surface of the coupling ring 18.
  • the coupling ring 18 (coupling member) is made of a conductive material such as Kovar (iron-nickel-cobalt alloy), and is formed to have a rectangular shape with a top view outline slightly smaller than the top view outline of the case 11. Yes. Further, the top view outline of the inner hole 18 a of the coupling ring 18 substantially matches the top view outline of the recess 11 a of the case 11. Since the coupling ring 18 is coupled to the upper surface of the case 11 via a bonding material so that the inner hole 18a is aligned with the concave portion 11a, the inner hole 18a is substantially indented by cooperation with the concave portion 11a. Will be composed.
  • a bonding material for example, a brazing material such as a gold-copper alloy, due to the material of the case 11 or the like.
  • a bonding auxiliary layer for example, a tungsten film and a nickel film sequentially arranged from the upper surface side in order
  • a bonding auxiliary layer on the upper surface of the case 11 is previously provided on the upper surface of the case 11 to increase the bonding force of the bonding ring 18 to the upper surface. It is good to form.
  • the coupling ring 18 is made of a material having low corrosion resistance to the electrolytic solution, a corrosion-resistant film for enhancing the corrosion resistance to the electrolytic solution (for example, a nickel film and a gold film arranged in order from the surface side, It is preferable to form a surface of the coupling ring 18 (at least the upper and lower surfaces and the inner surface of the inner hole 18a).
  • the current collecting film 19 is made of a conductive material such as aluminum, and is formed on the bottom surface 11a1 of the recess 11a of the case 11 with a top view contour slightly smaller than the top view contour of the bottom surface. Further, the current collecting film 19 formed on the bottom surface 11 a 1 of the recess 11 a of the case 11 is electrically connected to the exposed portion of each columnar portion 16 b of the positive electrode wiring 16.
  • a conductive auxiliary layer for example, a nickel film and a gold film are sequentially formed from the surface side of the projecting portion to enhance the electrical conduction between the exposed portions of the columnar portions 16b and the current collecting film 19. It is advisable to form a line on the surface of the exposed portion in advance.
  • the lid 12 is coupled to the opening side of the case 11 and forms a closed portion (cell) between the lid 12 and the recess 11a.
  • the lid 12 is made of a conductive material such as Kovar (iron-nickel-cobalt alloy), preferably a clad material having a nickel film on the upper and lower surfaces of the Kovar base material, a clad material having a nickel film on the lower surface of the Kovar base material, These nickel films are made of a clad material obtained by changing the nickel film into a metal film such as platinum, silver, gold, or palladium, and are formed in a rectangular shape having a top view outline that substantially matches the top view outline of the coupling ring 18.
  • the central portion of the lid 12 that is raised in a rectangular shape is shown as the lid 12, but a flat plate may be used as the lid 12.
  • the lid 12 is configured so that the outer peripheral portion of the lower surface thereof is electrically connected to the upper surface of the coupling ring 18 after the electric storage element 13 is disposed inside the recess 11 a (including the inner hole 18 a of the coupling ring 18) of the case 11.
  • each recess 11a (including the inner hole 18a of the coupling ring 18) of the case 11 is closed in a watertight and airtight manner.
  • a direct bonding method such as seam welding or laser welding can be used, or an indirect bonding method with a conductive bonding material can be used.
  • the coupling ring 18 is not limited to being configured independently of the case 11 and the lid 12, and may be provided integrally with the case 11 or the lid 12. Alternatively, the coupling ring 18 may be omitted if necessary, and the lid 12 may be coupled directly to the case 11.
  • the power storage element 13 includes a rectangular first electrode sheet 13a, a rectangular second electrode sheet 13b, and a rectangular separate sheet 131c interposed between the electrode sheets 13a and 13b. Yes.
  • the first electrode sheet 13a and the second electrode sheet 13b have a top view outline smaller than the top view outline of the recess 11a of the case 11, and the separate sheet 131c is slightly larger than the top view outlines of both the electrode sheets 13a and 13b.
  • the top view outline is slightly smaller than the top view outline of the recess 11 a of the case 11.
  • the first electrode sheet 13a and the second electrode sheet 13b are made of an active material such as activated carbon or PAS (polyacenic semiconductor), and the separate sheet 131c is a fiber-based porous sheet mainly made of glass fiber, cellulose fiber, plastic fiber, or the like. Consists of. Incidentally, the materials of the first electrode sheet 13 a and the second electrode sheet 13 b may be the same or different depending on the type of the electrochemical device 100.
  • the first electrode sheet 13a includes a main surface 13a1 (first main surface) in contact with the separate sheet 131c, an outer surface 13a2, and an edge surface 13a3 (first edge surface) formed around the main surface 13a1.
  • the edge surface 13a3 is formed adjacent to the main surface 13a1 between the main surface 13a1 and the outer surface 13a2.
  • the edge surface 13a3 is a flat or curved tapered surface formed by cutting out the periphery of the main surface 13a1.
  • the second electrode sheet 13b includes a main surface 13b1 (second main surface) in contact with the separate sheet 131c, an outer surface 13b2, and an edge surface 13b3 (second edge surface) formed around the main surface 13b1. ).
  • the edge surface 13b3 is formed adjacent to the main surface 13b1 between the main surface 13b1 and the outer surface 13b2.
  • the edge surface 13b3 is configured by a flat or curved tapered surface formed by cutting out the periphery of the main surface 13b1.
  • the separate sheet 131c has a first portion 13c1 disposed (sandwiched) between the electrode sheets 13a and 13b, and a second portion 13c2 projecting outward from the electrode sheets 13a and 13b.
  • the first portion 13c1 and the second portion 13c2 are formed continuously with each other.
  • the second portion 13c2 is configured to have a lower liquid absorption than the first portion 13c1, and in the following description, the “first portion” is also referred to as a “high liquid absorption portion”.
  • the “part” is also referred to as a “low liquid absorption part”.
  • the separate sheet 131c further includes a third portion 13c3.
  • the third portion 13c3 is provided in at least a part of the second portion 13c2, and in the present embodiment, the third portion 13c3 is provided in a surface region near the second electrode sheet 13b of the second portion 13c2.
  • the third portion 13c3 is in contact with at least a part of the edge surface 13b3 of the second electrode sheet 13b.
  • the “third portion” is also referred to as “contact portion”.
  • the thickness (maximum thickness) Tc2 of the low liquid absorbency portion 13c2 is larger than the thickness Tc1 of the high liquid absorbency portion 13c1, and for example, the thickness ratio Tc1 / Tc2 is in the range of 0.3 to 0.8. is there.
  • the high liquid absorbency portion 13c1 is made up of a crushed central portion of the separate sheet base material RM13c shown in FIG. 4, and the low liquid absorbency portion 13c2 is pressed by the separate sheet base material RM13c. It consists of an outer part that is not crushed.
  • the thickness Tc2 of the low liquid absorbency portion 13c2 of the separate sheet 131c is formed to be a predetermined distance away from the lid 12 inside the container 10. That is, the low liquid absorbency portion 13 c 2 is formed with a thickness that is not in contact with the lid 12 inside the container 10.
  • the electrolytic solution prevents the weldability from being intruded. Productivity can be ensured.
  • the uppermost surface (surface on the lid 12 side) of the separation sheet 131c is lower than the interface between the coupling ring 18 and the lid 12 (located on the case 11 side).
  • First and second electrode sheets 13a and 13b and a separate sheet 131c are configured.
  • the low liquid absorption part 13c2 is formed smaller than the total thickness of the first electrode sheet 13a and the second electrode sheet 13b.
  • the thickness of the low liquid absorption portion 13c2 is not limited to this, and the thickness of the outer peripheral portion (low liquid absorption 13c2) of the separate sheet 131c is not in contact with the lid 12 when the electric storage element 13 is incorporated into the container 10. Good.
  • the electricity storage element 13 is enclosed together with an electrolyte solution (not shown) inside the recess 11a (including the inner hole 18a of the coupling ring 18) closed by the lid 12.
  • an electrolytic solution a known electrolytic solution, that is, a solution in which an electrolyte salt is dissolved in a solvent, or an ionic liquid not using a solvent can be appropriately used.
  • the former electrolytic solution includes a chain sulfone, a cyclic sulfone, a chain carbonate, a cyclic carbonate, a chain ester, a cyclic ester, a nitrile, etc., a lithium ion, a quaternary ammonium ion, an imidazolium.
  • examples include those containing cations such as ions and anions such as BF4, PF6, and TFSA.
  • electrolyte solution examples include those containing cations such as imidazolium ions, pyridinium ions, and quaternary ammonium ions, and containing anions such as BF4, PF6, and TFSA.
  • the lower surface of the first electrode sheet 13a of the electricity storage element 13 is electrically connected to the upper surface of the current collecting film 19 through the conductive adhesive layer 20, and the upper surface of the second electrode sheet 13b. Is electrically connected to the lower surface of the lid 12 through the conductive adhesive layer 21.
  • the conductive adhesive layers 20 and 21 are a cured product of a conductive adhesive, and the conductive adhesive is preferably a thermosetting adhesive containing conductive particles, for example, an epoxy containing graphite particles. A system adhesive can be used.
  • FIG. 4 schematically shows a configuration before the storage element 13 is arranged, in which 13a is a first electrode sheet, 13b is a second electrode sheet 13b, and RM 13c is a separate sheet base material.
  • 13a is a first electrode sheet
  • 13b is a second electrode sheet 13b
  • RM 13c is a separate sheet base material.
  • the illustration of the edge surfaces 13a3 and 13b3 of the electrode sheets 13a and 13b is omitted.
  • the first electrode sheet 13a has a predetermined length La and width Wa
  • the second electrode sheet 13b has substantially the same length Lb and width Wb as the first electrode sheet 13a.
  • the materials of the first electrode sheet 13 a and the second electrode sheet 13 b are as described above, and the thickness of each may be the same or different depending on the type of the electrochemical device 100.
  • the separate sheet base material RM13c has a predetermined length Lc, a width Wc and a thickness Tc, a predetermined porosity and a liquid absorption (average value), and has a hardness (which can be crushed by both electrode sheets 13a and 13b). Softness).
  • the length Lc of the separate sheet base material RM13c is preferably about 20 to 40% longer than the lengths La and Lb of both electrode sheets 13a and 13b, and the width Wc is preferably larger than the widths Wa and Wb of both electrode sheets 13a and 13b. Is about 20-40% wider.
  • the material of the separate sheet base material RM13c is the same as the material of the separate sheet 131c described above.
  • an uncured conductive adhesive is applied to the surface of the current collector film 19, and the lower surface of the first electrode sheet 13a is applied to the conductive adhesive.
  • the first electrode sheet 13a is injected and impregnated with an electrolytic solution after the conductive adhesive is cured by relatively pressing and adhering (see step ST1).
  • a separate sheet base material RM13c is placed on the upper surface 13a1 of the first electrode sheet 13a, and an electrolyte is injected and impregnated into the separate sheet base material RM13c (see step ST2).
  • the same uncured conductive adhesive as described above was applied to the lower surface of the lid 12, and the upper surface of the second electrode sheet 13b was relatively pressed against and adhered to the conductive adhesive.
  • the electrolytic solution is injected into the second electrode sheet 13b and impregnated.
  • the outer peripheral portion of the lower surface of the lid 12 is overlaid on the upper surface of the coupling ring 18, and at the same time, the lower surface 13b1 of the second electrode sheet 13b is pressed against the upper surface of the separate sheet 131c (see step ST3).
  • the lid 12 is then coupled to the coupling ring 18.
  • each recess 11a (including the inner hole 18a of the coupling ring 18) of the case 11 when the use polarity is determined in advance in the first electrode sheet 13a and the second electrode sheet 13b constituting the power storage element 13.
  • the first electrode sheet 13a on the positive electrode side is the current collecting film 19.
  • the second electrode sheet 13 b on the negative electrode side faces the lower surface of the lid 12.
  • step ST3 the central portion of the separate sheet base material RM13c is crushed by the upper surface of the first electrode sheet 13a and the lower surface of the second electrode sheet 13b, and the crushed portion has a high liquid absorbency of thickness Tc1.
  • Part (first part) 13c1 see FIG. 2. Since the outer peripheral portion of the separate sheet base material RM13c is not crushed, the portion that is not crushed becomes a low liquid absorbency portion (second portion) 13c2 having a thickness (maximum thickness) Tc2 (see FIG. 2). ), The thickness (maximum thickness) Tc2 is not different from the thickness Tc of the separate sheet base material RM13c.
  • the contact portion 13c3 of the separate sheet 131c is in contact with the edge surface 13b3 of the second electrode sheet 13b.
  • the contact portion 13c3 is connected to the first electrode sheet 13a. May be in contact with the edge surface 13a3, or the contact portions 13c3 may be formed on both sides of the low liquid absorption portion 13c2 so as to contact the edge surfaces 13a3 and 13b3 of the electrode sheets 13a and 13b, respectively.
  • the form of the contact portion 13c3 can be appropriately set according to the initial shape of the separate sheet 131c, the shape and size of both electrode sheets 13a and 13b, the amount of crushing of the separate sheet 131c by both electrode sheets 13a and 13b, and the like.
  • the formation of the edge surface 13a3 of the first electrode sheet 13a is omitted, or the size of the second electrode sheet 13b ( Wb and Lb) are made smaller than the size (Wa and La) of the first electrode sheet 13a, or the taper angle of the edge surface 13b3 of the second electrode sheet 13b is made to be the taper angle of the edge surface 13a3 of the first electrode sheet 13a. It is possible to adopt an appropriate method such as forming it more loosely.
  • the liquid absorption (average value) with respect to the electrolyte sheet (in this case, the solvent is cyclic sulfolane, the cation is TEMA, and the anion is BF4) as the separate sheet base material RM13c is 85 mm.
  • a separate sheet 131c having a thickness ratio Tc1 / Tc2 of 0.5 between the thickness Tc1 of the high liquid absorption portion 13c1 and the thickness (maximum thickness) Tc2 of the low liquid absorption portion 13c2 is used.
  • the porosity of the high liquid absorption part 13c1 is about 70%
  • the low liquid absorption part 13c2 is about 84%
  • the liquid absorption (average value) of the high liquid absorption part 13c1 is 16 mm / 10 min.
  • the liquid absorption (average value) of the low liquid absorption part 13c2 was 10.5 mm / 10 min.
  • the porosity (about 70%) of the high liquid absorbency portion 13c1 formed by the previous crushing is the porosity (85%) of the separate sheet base material RM13c, and the void of the low liquid absorbency portion 13c2.
  • the reason why it does not drop significantly compared to the rate (about 84%) is that a separate sheet base material RM13c having a high porosity is used.
  • a separation sheet base material RM13c having a porosity of 85 to 95% is used, when the thickness ratio Tc1 / Tc2 is 0.5, the high liquid absorption portion 13c1 has 70 to 90%. % Porosity can be secured.
  • the porosity of the high liquid absorbency portion 13c1 is within the range of the thickness ratio Tc1 / Tc2 of 0.3 to 0.8. It has also been confirmed that the porosity of the separate sheet base material RM13c and the porosity of the low liquid absorption portion 13c2 do not decrease significantly.
  • the liquid absorbency (average value: 16 mm / 10 min) of the high liquid absorbency portion 13c1 formed by the previous crushing is the liquid absorbency (average value: 10 mm / 10 min) of the separate sheet base material RM13c, and low
  • the reason why the liquid absorption degree of the liquid absorption part 13c2 is greatly improved compared to the liquid absorption degree (average value: 10.5 mm / 10 min) is that the cross-sectional diameter of the void in the separate sheet base material RM13c is reduced by the previous crushing. is there.
  • the liquid absorbency of the high liquid absorbency portion 13c1 can be obtained when the thickness ratio Tc1 / Tc2 is in the range of 0.3 to 0.8.
  • the liquid absorption of the separate sheet base material RM13c and the liquid absorption of the low liquid absorption portion 13c2 are greatly improved.
  • the electrolytic solution is mainly impregnated in the first electrode sheet 13a, the second electrode sheet 13b, and the separate sheet 131c. Since the separate sheet 131c has a low liquid absorption part 13c2 that projects outward from both electrode sheets 13a and 13b and has a thickness greater than that of the high liquid absorption part 13c1, the low liquid absorption part 13c2. Is impregnated with a considerable amount of electrolyte.
  • the electrolyte solution impregnated in the first electrode sheet 13a, the second electrode sheet 13b, and the separate sheet 131c does not flow greatly in the charge / discharge process, but decomposes into the electrolyte solution in both the electrode sheets 13a and 13b in the process.
  • the electrolytic solution impregnated in the portion sandwiched between both electrode sheets 13a and 13b (high liquid absorption portion 13c1) of the separate sheet 131c is drawn into both electrode sheets 13a and 13b. This may cause a phenomenon that the amount of the electrolytic solution in the portion decreases although it is very small (see the up and down solid arrows in FIG. 2).
  • the electrochemical device 100 Even if such a phenomenon occurs, according to the electrochemical device 100, the electrolyte solution impregnated in the low liquid absorption part 13c2 is immediately drawn into the high liquid absorption part 13c1 according to the liquid absorption difference, The electrolytic solution replenishment to the high liquid absorption portion 13c1 is immediately performed (refer to the solid line arrow in FIG. 2). Further, since the low liquid absorption portion 13c2 is impregnated with a considerable amount of the electrolytic solution, even if the phenomenon occurs frequently, the high liquid absorption portion 13c1 is immediately replenished with the electrolytic solution.
  • the contact portion (third portion) 13c3 provided on a part of the surface of the low liquid absorption portion 13c2 is in contact with the edge surface 13b3 of the second electrode sheet 13b, the electrolysis in the second electrode sheet 13b is performed.
  • the drawing of the electrolyte accompanying the decomposition or deterioration of the liquid is not limited to the first through the contact portion 13c3 from the low liquid absorbency portion 13c2. This is done directly on the route to the two-electrode sheet 13b (see broken line arrow in FIG. 2).
  • the phenomenon in which the electrolyte solution impregnated in the high liquid absorption portion 13c1 is drawn into the second electrode sheet 13b and the amount of the electrolytic solution in the high liquid absorption portion 13c1 is reduced is referred to as the low liquid absorption portion 13c2 and the contact. It can suppress by the electrolyte replenishment effect
  • the electrical conduction between the positive and negative electrodes is maintained and the increase in internal resistance is prevented. can do.
  • a change in characteristics due to the use of an electrochemical device can be suppressed, and production conditions with stable yield and lifetime can be determined.
  • FIG. 6A shows a main part of the power storage element of the electrochemical device shown in FIG.
  • FIG. 6B shows a power storage device according to a comparative example, in which a portion disposed between both electrode sheets 13a and 13b and a portion protruding outward from both electrode sheets 13a and 13b have substantially the same thickness.
  • seat 130c is shown.
  • the production yield decreases. This is because if the total amount of the electrolytic solution exceeds the amount that can be held by the separator 130c, the electrolytic solution overflows when the lid 12 is closed, or the electrolytic solution intervenes on the joint surface with the lid 12 to cause a sealing failure. It is. Therefore, the decrease in yield becomes more apparent as the amount of electrolyte increases.
  • the tolerance in the injection process of the electrolytic solution is ⁇ 0.05 mg
  • the tolerance center must be set to around 1.45 mg, and the life characteristics vary. become. Therefore, in the comparative example, it is difficult to determine production conditions with stable yield and lifetime, and a design change is required to lower the capacity density.
  • the separator 131c according to the present embodiment has a high liquid absorbency part (first part) 13c1 and a low liquid absorbency part (second part) 13c2, so that it is more electrolytic than the separator 130c according to the comparative example. This is because the amount of liquid that can be retained is large.
  • the separator 131c according to this embodiment has a contact portion (third portion) 13c3 that contacts the edge surface 13c3 of the second electrode sheet 13b in a part of the low liquid absorption portion 13c3. This is because the electrolytic solution can be supplied from the contact portion 13c3 to the electrode sheet 13b, and the decrease in the liquid amount in the high liquid absorption portion 13c1 can be reduced as compared with the comparative example.
  • the internal resistance R is stable when the amount of the electrolyte is 1.6 mg or more. For this reason, for example, if the tolerance in the step of injecting the electrolytic solution is ⁇ 0.05 mg, the tolerance center can be set to around 1.65 mg, thereby realizing stable productivity and life characteristics. Therefore, according to the present embodiment, it is possible to determine production conditions that are stable in both yield and lifetime.
  • the outer peripheral portion (second portion 13c2) of the separate sheet 131c is configured to be in non-contact with the lid 12, so that the electrolyte overflow and the case 11 as described above Contamination of the electrolyte between the lid 12 (when the coupling ring 18 is provided, between the coupling ring 18 and the lid 12) can be effectively prevented, and thus the productivity of the electrochemical device 100 can be reduced. Can be secured.
  • FIG. 7 shows an electrochemical device according to a second embodiment of the present invention.
  • the configuration of the separate sheet 132c is different from that of the first embodiment.
  • configurations different from those of the first embodiment will be mainly described, and configurations similar to those of the above-described embodiment will be denoted by the same reference numerals, and description thereof will be omitted or simplified.
  • the separate sheet 132c of this embodiment includes a high liquid absorbency portion (first portion) 13c1 disposed on both electrode sheets 13a and 13b, and a low liquid absorbency portion protruding outward from both electrode sheets 13a and 13b ( (Second portion) 13c2 and a contact portion (third portion) 13c3 provided in a surface region near the first electrode sheet 13a of the low liquid absorbency portion 13c2.
  • the contact portion 13c3 is configured to contact at least part of the edge portion 13a3 of the first electrode sheet 13a.
  • the contact portion (third portion) 13c3 provided on a part of the surface of the low liquid absorption portion 13c2 is in contact with the edge surface 13a3 of the first electrode sheet 13a, the first electrode sheet
  • the drawing of the electrolytic solution due to the decomposition or deterioration of the electrolytic solution in 13a causes the contact portion 13c3 from the low liquid absorption portion 13c2 to the contact portion 13c3. This is performed directly on the route to the first electrode sheet 13a (see the broken line arrow in FIG. 7).
  • the phenomenon in which the electrolyte solution impregnated in the high liquid absorption portion 13c1 is drawn into the first electrode sheet 13a and the amount of the electrolytic solution in the high liquid absorption portion 13c1 is reduced is referred to as the low liquid absorption portion 13c2 and the contact. It can suppress by the electrolyte solution replenishment effect
  • the formation of the edge surface 13b3 of the second electrode sheet 13b is omitted, or the size of the second electrode sheet 13b ( Wb and Lb) are made larger than the size (Wa and La) of the first electrode sheet 13a, or the taper angle of the edge surface 13a3 of the first electrode sheet 13a is made to be the taper angle of the edge surface 13b3 of the second electrode sheet 13b.
  • An appropriate method may be employed such as forming it more loosely.
  • the low liquid absorbency portion 13c2 of the separate sheet 132c has a thickness that is separated from the lid 12 by a predetermined distance inside the container 10, that is, is not relative to the lid 12. It is formed with a thickness that makes contact.
  • the electrolyte impregnated in the outer peripheral portion (low liquid absorption portion 13 c 2) of the separate sheet 132 c overflows to the outside of the case 11, thereby reducing the assembling property.
  • 11 and the lid 12 in the case where the coupling ring 18 is provided, between the coupling ring 18 and the lid 12), the electrolytic solution can be prevented from impeding weldability and the electrochemical device 200. Productivity can be ensured.
  • FIG. 8 shows an electrochemical device according to a third embodiment of the present invention.
  • the configuration of the separate sheet 133c is different from that of the first embodiment.
  • configurations different from those of the first embodiment will be mainly described, and configurations similar to those of the above-described embodiment will be denoted by the same reference numerals, and description thereof will be omitted or simplified.
  • the separate sheet 133c of the present embodiment includes a high liquid absorbency portion (first portion) 13c1 disposed on both electrode sheets 13a and 13b, and a low liquid absorbency portion protruding outward from both electrode sheets 13a and 13b ( (Second portion) 13c2 and contact portions (third portion) 13c3 provided in the surface region near the first electrode sheet 13a and the surface region near the second electrode sheet 13b of the low liquid absorption portion 13c2.
  • Each contact part 13c3 is comprised so that at least one part of the edge parts 13a3 and 13b3 of each of the 1st and 2nd electrode sheets 13a and 13b may be contact
  • contact portions (third portions) 13c3 provided on a part of each surface of the low liquid absorbency portion 13c2 are provided on the edge surfaces 13a3 and 13b3 of the first and second electrode sheets 13a and 13b, respectively. Since the electrodes are in contact with each other, the electrolyte solution in the first and second electrode sheets 13a and 13b is decomposed, deteriorated, or the like, so that the electrolyte solution is drawn from the high liquid absorption portion 13c1 to the first and second electrode sheets 13a. In addition to the route of 13b and 13b, it is performed directly on the route from the low liquid absorption portion 13c2 to the first and second electrode sheets 13a and 13b via the respective contact portions 13c3 (see the broken arrow in FIG.
  • the low liquid absorbency portion 13c2 of the separate sheet 133c has a thickness that is separated from the lid 12 by a predetermined distance inside the container 10, that is, is not relative to the lid 12. It is formed with a thickness that makes contact.
  • the electrolyte impregnated in the outer peripheral portion (low liquid absorption portion 13c2) of the separate sheet 133c overflows to the outside of the case 11 and the assemblability is reduced.
  • the electrolytic solution prevents the weldability from being deteriorated. Productivity can be ensured.
  • FIG. 9 and 10 show a fourth embodiment of the present invention.
  • FIG. 9 is an exploded perspective view of a power storage element
  • FIG. 10 is an exploded perspective view of an electrochemical device.
  • the electrochemical device of the present embodiment has the same configuration as the electrochemical device 300 described in the third embodiment, but the separate sheet 133c ′ of the electricity storage element 13 is a high liquid absorption portion (first portion) 13c1 ′. And a low liquid-absorbing part (second part) 13c2 ′ and a contact part (third part 13c3 ′).
  • the other structure is the same as that of the first and third embodiments. Therefore, the description is omitted.
  • a separate sheet 133c 'shown in FIG. 9 is obtained by press-working a separate sheet base material RM13c and previously shaping a high liquid absorption part 13c1' and a low liquid absorption part 13c2 '.
  • an upper die having the same shape as the upper surface 13a1 of the first electrode sheet 13a and a lower die having the same shape as the lower surface 13b1 of the second electrode sheet 13b are used, and the central portion of the separate sheet base material RM13c is pressed and pressed with both dies.
  • a high liquid absorption part 13c1 ′ having a thickness Tc1 ′ is formed.
  • the uncrushed portion becomes a low liquid absorption portion 13c2 'having a thickness (maximum thickness) Tc2'.
  • the thickness Tc1 'of the high liquid absorption portion 13c1' and the thickness Tc2 'of the low liquid absorption portion 13c2' are not particularly limited and can be set to appropriate thicknesses.
  • the separate sheet base material RM13c has a hardness (softness) that can be crushed, but if the elastic force of the separate sheet base material RM13c is strong, The thickness Tc1 ′ of the liquid absorption portion 13c1 ′ may increase after being crushed. In such a case, when the high liquid absorbency portion 13c1 ′ is formed by pressing, heat necessary for plasticity is simultaneously applied, and the thickness Tc1 ′ of the high liquid absorbency portion 13c1 ′ is obtained by cooling after crushing. It is good to be able to maintain.
  • an uncured conductive adhesive is applied to the surface of the current collector film 19, and the lower surface of the first electrode sheet 13a is applied to the conductive adhesive.
  • the first electrode sheet 13a is injected and impregnated with an electrolytic solution after the conductive adhesive is cured by relatively pressing and adhering (see step ST11).
  • the upper surface 13a1 of the first electrode sheet 13a is placed so that the lower surface of the high liquid absorption portion 13c1 ′ of the separate sheet 13c ′ is aligned with each other, and the electrolytic solution is injected and impregnated into the separate sheet 133c ′. (See step ST12).
  • the same uncured conductive adhesive as described above was applied to the lower surface of the lid 12, and the upper surface of the second electrode sheet 13b was relatively pressed against and adhered to the conductive adhesive.
  • the electrolytic solution is injected into the second electrode sheet 13b and impregnated.
  • the outer peripheral portion of the lower surface of the lid 12 is overlaid on the upper surface of the coupling ring 18, and at the same time, the lower surface 13b1 of the second electrode sheet 13b is aligned with the upper surface of the high liquid absorption portion 13c1 ′ of the separate sheet 133c ′. Place (see step ST13).
  • the lid 12 is then coupled to the coupling ring 18.
  • each recess 11a (including the inner hole 18a of the coupling ring 18) of the case 11 when the use polarity is determined in advance in the first electrode sheet 13a and the second electrode sheet 13b constituting the power storage element 13.
  • the first electrode sheet 13a on the positive electrode side is the current collecting film 19.
  • the second electrode sheet 13 b on the negative electrode side faces the lower surface of the lid 12.
  • the cross-sectional shape of the separate sheet 133c ′ after the storage element 13 is arranged is the same as the cross-sectional shape of the separate sheet 133c shown in FIG. 8, and the porosity and liquid absorption of the separate sheet 133c ′ are also shown in FIG. It is the same as the porosity and liquid absorption of the separate sheet 133c.
  • ⁇ Effect obtained by electrochemical device (fourth embodiment)> According to the electrochemical device, the same effect as in the first and third embodiments described above can be obtained.
  • a depression exists on the lower surface side of the high liquid absorption portion 13c1 ′ of the separate sheet 133c ′, and the lower surface shape thereof matches the upper surface shape of the first electrode sheet 13a. Since the depression is present on the upper surface side of the degree portion 13c1 ′ and the shape of the upper surface is aligned with the shape of the lower surface of the second electrode sheet 13b, the high absorption of the separate sheet 133c ′ is formed on the upper surface of the first electrode sheet 13a.
  • both can be aligned easily and accurately, and the upper surface of the second electrode sheet 13b is placed on the upper surface of the high liquid absorbency portion 13c1 ′ of the separate sheet 133c ′. In the process of mounting, both can be aligned easily and accurately.
  • the outer peripheral portion (second portion 13c2) of the separate sheet 133c ' is configured to be in non-contact with the lid 12. Therefore, as in the first embodiment, the electrolyte overflows and the electrolyte is contaminated between the case 11 and the lid 12 (between the coupling ring 18 and the lid 12 when the coupling ring 18 is provided). Can be effectively prevented, and the productivity of the electrochemical device can be ensured.
  • the edge surfaces 13a3 and 13b3 of the electrode sheet with which the contact portion 13c3 of the separate sheet contacts are formed between the main surfaces 13a1 and 13b1 and the outer surfaces 13a2 and 13b2 of the electrode sheet.
  • the edge surface may be any surface as long as it is formed around the main surfaces 13a1 and 13b1, and for example, the outer surfaces 13a2 and 13b2 may be applied to the edge surfaces.
  • the contact portion 13c3 of the separate sheet is not limited to the example configured to continuously contact the entire region of the edge surface of the electrode sheet, and may be only to contact at least a part of the edge surface.
  • the contact part 13c3 is not restricted to the example continuously formed along the circumference
  • the separate sheet 133c ′ is configured in the shape of the separate sheet 133c described in the third embodiment has been described, but instead of this, the first and second embodiments are described. You may comprise by the shape of the separate sheet
  • Electrochemical device 11 Case 11a ... Recess 12 ... Lid 13 ... Power storage element 13a ... 1st electrode sheet 13b ... 2nd electrode sheet 131c, 132c, 133c, 13c '... Separate sheet 13c1, 13c1' ... High liquid absorption part 13c2, 13c2 '... Low liquid absorption part 13c3, 13c3' ... Contact part

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

Le but de la présente invention est de fournir un dispositif électrochimique qui est apte à éliminer rapidement et sûrement un phénomène de diminution de solution électrolytique dans une partie d'une couche de séparation, ladite partie étant prise en sandwich entre deux couches d'électrode, même si le phénomène se produit fréquemment. Un dispositif électrochimique (100) comporte d'un élément de stockage d'électricité (13) qui est configuré à partir d'une première couche d'électrode (13a), d'une seconde couche d'électrode (13b) et d'une couche de séparation (131c) qui est interposée entre les couches d'électrode (13a, 13b). La couche de séparation (131c) comprend : une première partie (une partie à haute absorption de liquide) (13c1) qui est prise en sandwich entre les couches d'électrode (13a, 13b) ; une seconde partie (une partie à faible absorption de liquide) (13c2) qui fait saillie des couches d'électrode (13a, 13b), tout en étant hors de contact avec un couvercle (12) ; et une troisième partie (une partie de contact) (13c3) qui est en contact avec une surface de bord (13b3) de la seconde couche d'électrode (13b).
PCT/JP2013/055951 2012-06-08 2013-03-05 Dispositif électrochimique WO2013183326A1 (fr)

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US14/406,049 US20150155540A1 (en) 2012-06-08 2013-03-05 Electrochemical device
CN201380030147.9A CN104380411A (zh) 2012-06-08 2013-03-05 电化学器件
KR1020147032091A KR20150002833A (ko) 2012-06-08 2013-03-05 전기 화학 디바이스

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JP2012-130400 2012-06-08
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JP2012201150 2012-09-13
JP2012-220863 2012-10-03
JP2012220863A JP2014075204A (ja) 2012-09-13 2012-10-03 電気化学デバイス

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9318275B2 (en) 2012-09-13 2016-04-19 Taiyo Yuden Co., Ltd. Electrochemical device

Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2001244156A (ja) * 2000-02-29 2001-09-07 Ngk Insulators Ltd 電気化学キャパシタ
JP2004227959A (ja) * 2003-01-23 2004-08-12 Sii Micro Parts Ltd 非水電解質電池および電気二重層キャパシタ
JP2005277064A (ja) * 2004-03-24 2005-10-06 Tdk Corp 電極の製造方法及び電極、並びに、電気化学デバイスの製造方法及び電気化学デバイス
JP2012069508A (ja) * 2010-08-27 2012-04-05 Seiko Instruments Inc 電気化学セル
JP5076034B1 (ja) * 2012-06-08 2012-11-21 太陽誘電株式会社 電気化学デバイス

Patent Citations (5)

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Publication number Priority date Publication date Assignee Title
JP2001244156A (ja) * 2000-02-29 2001-09-07 Ngk Insulators Ltd 電気化学キャパシタ
JP2004227959A (ja) * 2003-01-23 2004-08-12 Sii Micro Parts Ltd 非水電解質電池および電気二重層キャパシタ
JP2005277064A (ja) * 2004-03-24 2005-10-06 Tdk Corp 電極の製造方法及び電極、並びに、電気化学デバイスの製造方法及び電気化学デバイス
JP2012069508A (ja) * 2010-08-27 2012-04-05 Seiko Instruments Inc 電気化学セル
JP5076034B1 (ja) * 2012-06-08 2012-11-21 太陽誘電株式会社 電気化学デバイス

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9318275B2 (en) 2012-09-13 2016-04-19 Taiyo Yuden Co., Ltd. Electrochemical device

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