JP4824279B2 - Electrochemical cell - Google Patents
Electrochemical cell Download PDFInfo
- Publication number
- JP4824279B2 JP4824279B2 JP2004021673A JP2004021673A JP4824279B2 JP 4824279 B2 JP4824279 B2 JP 4824279B2 JP 2004021673 A JP2004021673 A JP 2004021673A JP 2004021673 A JP2004021673 A JP 2004021673A JP 4824279 B2 JP4824279 B2 JP 4824279B2
- Authority
- JP
- Japan
- Prior art keywords
- conductive pattern
- electrochemical cell
- case
- positive electrode
- outer case
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
- 238000003466 welding Methods 0.000 claims abstract description 29
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 19
- 238000007789 sealing Methods 0.000 claims description 45
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- 238000007747 plating Methods 0.000 claims description 15
- 239000006229 carbon black Substances 0.000 claims description 5
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 230000002093 peripheral effect Effects 0.000 claims 2
- 239000000919 ceramic Substances 0.000 abstract description 21
- 230000007797 corrosion Effects 0.000 abstract description 15
- 238000005260 corrosion Methods 0.000 abstract description 15
- 239000004020 conductor Substances 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003575 carbonaceous material Substances 0.000 abstract description 6
- 230000006866 deterioration Effects 0.000 abstract description 5
- 239000007769 metal material Substances 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 abstract 1
- 239000008188 pellet Substances 0.000 description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005219 brazing Methods 0.000 description 9
- 239000011149 active material Substances 0.000 description 5
- 229910000833 kovar Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- -1 or Zr Inorganic materials 0.000 description 4
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- 229920003026 Acene Polymers 0.000 description 1
- 229910017944 Ag—Cu Inorganic materials 0.000 description 1
- 229910018871 CoO 2 Inorganic materials 0.000 description 1
- 229910010199 LiAl Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Secondary Cells (AREA)
Abstract
Description
本発明は、非水電解質電池又は電気二重層原理を利用した電気二重層キャパシタ等の発電もしくは蓄電機能を有する表面実装可能なチップ型の電気化学セルに関するものである。 The present invention relates to a surface-mountable chip-type electrochemical cell having a power generation or storage function such as a non-aqueous electrolyte battery or an electric double layer capacitor utilizing the electric double layer principle.
非水電解質電池や電気二重層キャパシタ等の電気化学セルは、従来、時計機能や半導体メモリのバックアップ電源として、またマイクロコンピュータやICメモリ等からなる電子装置の予備電源やソーラ時計の制御回路やモーター駆動用の電源などとして使用されており、近年は電気自動車の電源やエネルギー変換・貯蔵システムの補助蓄電ユニットなどとしても検討されている。 Electrochemical cells such as non-aqueous electrolyte batteries and electric double layer capacitors have conventionally been used as backup power sources for clock functions and semiconductor memories, as well as backup power sources for electronic devices such as microcomputers and IC memories, control circuits for solar clocks, and motors. It is used as a power source for driving. In recent years, it has been studied as a power source for electric vehicles and an auxiliary power storage unit for an energy conversion / storage system.
機器の小型化、軽量化、高機能化による部品の高密度実装化に伴い、その電源としての電気化学セルに対しても、ますます小型、薄型化の要望がされている。 With the high density mounting of parts due to the miniaturization, weight reduction, and high functionality of equipment, there is a demand for smaller and thinner electrochemical cells as power sources.
図4のように、従来のコイン型やボタン型などの電気化学セルではセルの外装を構成する金属製ケース401と金属製フタ402が外部回路に電気的接続するための外部端子を兼ね、かつ上下に配置されているために回路基板上に実装を行う時、基板回路上の同一平面に正、負極の接続を、リードタブ端子A403、リードタブ端子B404をケースにあらかじめ溶接しておきハンダ付けを行う必要があった。そのため、これらのリードタブ端子等の部品点数が多く製造工数の増加という点でコストアップとなり、電気化学セル本体及び基板上に、端子のスペースを設ける必要があり小型化が困難という問題があった。 As shown in FIG. 4, in a conventional electrochemical cell such as a coin type or a button type, a metal case 401 and a metal lid 402 constituting the exterior of the cell also serve as external terminals for electrical connection to an external circuit, and When mounting on the circuit board because it is arranged vertically, the positive and negative electrodes are connected to the same plane on the board circuit, and the lead tab terminal A403 and lead tab terminal B404 are welded to the case in advance and soldered. There was a need. For this reason, the number of parts such as the lead tab terminals is large and the number of manufacturing steps increases, resulting in an increase in cost, and it is necessary to provide a space for the terminals on the electrochemical cell main body and the substrate, which makes it difficult to reduce the size.
これを解決すべく、耐熱性,耐磨耗性,絶縁性,機械的強度に優れるアルミナ製のセラミックスケースを小型化し、各電極をケース内から外側にかけてタングステンの導電性材料として一般的にパターンを形成している。リードタブ端子が無く軽薄短小のセラミックスケースを半導体素子や水晶振動子等の電子部品用として使用されている。(例えば特許文献1参照)
また、表面実装タイプの電気二重層キャパシタ素子を収納する外装体の構造として絶縁性のリング状外枠にその開口部を閉塞するように金属端子板にろう材を介して密着させ、該ろう材を介して外枠と金属端子板とが対向する部位にレーザー光線を照射することにより該外枠と端子板とを接合する検討もされている。また、上記の構成において熱膨張係数及び熱伝導率がアルミナと近似しているNi或いはステンレスを金属端子板に使用し熱による歪が生じ難い例も検討されている。(例えば特許文献2参照)
Further, as a structure of an exterior body for housing a surface-mount type electric double layer capacitor element, the insulating ring-shaped outer frame is closely attached to a metal terminal plate through a brazing material so as to close the opening, and the brazing material There is also a study of joining the outer frame and the terminal plate by irradiating a laser beam to a portion where the outer frame and the metal terminal plate are opposed to each other. In addition, an example in which Ni or stainless steel whose thermal expansion coefficient and thermal conductivity are close to those of alumina in the above configuration is used for a metal terminal plate and distortion due to heat hardly occurs is also being studied. (For example, see Patent Document 2)
しかし、上記特許文献1における構成では、電気化学セル内部の集電体に高電圧がかかるため正極集電体のアノード腐食が発生しタングステンが溶解し電池特性の劣化が見られる。 However, in the configuration in Patent Document 1, a high voltage is applied to the current collector inside the electrochemical cell, so that anode corrosion of the positive electrode current collector occurs, tungsten is dissolved, and battery characteristics are deteriorated.
また、導電性配線パターン材料とセラミックスを同時に1300℃以上で焼成しセラミックスケースを得るため導電性材料は、高融点の材料を用いないと蒸発凝集され導電性機能を保持することが困難であった。 In addition, since the conductive wiring pattern material and the ceramic are simultaneously fired at 1300 ° C. or more to obtain a ceramic case, the conductive material is evaporated and aggregated and it is difficult to maintain the conductive function unless a high melting point material is used. .
上記特許文献2における構成では、電池内の有効スペースはコイン型に比べて大きく取れるものの、外装ケースを兼ねる金属端子板が上下に配置されているため外部回路との電気的接続のために、リードタブ端子が必要であるという問題があった。金属端子Niを使用した場合でも、レーザー光線を照射することにより発熱し、Niの熱膨張係数が約13×10-6/℃とセラミックス4.0×10-6/℃と差が大きいため、熱膨張と収縮による封口部に歪が発生し密閉性の高い封口が得られず内部抵抗、容量値、長期信頼性が十分に得られないという問題もあった。 In the configuration in Patent Document 2, although the effective space in the battery can be made larger than that of the coin type, the lead terminal is used for electrical connection with an external circuit because the metal terminal plates also serving as the outer case are arranged vertically. There was a problem that a terminal was necessary. Even when the metal terminal Ni is used, heat is generated by irradiation with a laser beam, and the thermal expansion coefficient of Ni is about 13 × 10 −6 / ° C. and the difference between ceramics 4.0 × 10 −6 / ° C. There is also a problem that distortion occurs in the sealing portion due to expansion and contraction, and a sealing with high sealing performance cannot be obtained, and internal resistance, capacitance value, and long-term reliability cannot be sufficiently obtained.
非水電解質電池および電気二重層キャパシタは、外装ケースに封口板を接着し封口する方法としては、接着剤を用いる方法、ろう接法、圧接法及び融接法等がある。 Nonaqueous electrolyte batteries and electric double layer capacitors include a method using an adhesive, a brazing method, a pressure welding method, a fusion welding method, and the like as a method for adhering a sealing plate to an outer case.
しかし、非水電解質電池および電気二重層キャパシタは内部に電解液を含み高電圧が集電体にかかるため、正極、負極集電体のアノード、カソード腐食或いは長期信頼性を得るため密閉性の高い封口が必要とされ、電池特性及び封口特性を満足させるため、封止方法の選定に困難を有していた。 However, since non-aqueous electrolyte batteries and electric double layer capacitors contain an electrolytic solution inside and a high voltage is applied to the current collector, the anode of the positive and negative current collectors, cathode corrosion, or high sealing properties to obtain long-term reliability Since sealing is required and battery characteristics and sealing characteristics are satisfied, selection of a sealing method has been difficult.
たとえば、外装ケース縁部に接着剤、ろう材またはハンダ材等の接合剤を、載せ封口板で挟み、この封口板を接着剤の硬化温度で加熱、或いはろう材またはハンダ材の融点以上で加熱することにより封口した場合、外装ケース中の電解液が加熱されると外装ケース外に揮発し、電池特性の容量低下及び十分な封口をすることができなかった。 For example, a bonding agent such as an adhesive, brazing material, or soldering material is sandwiched between mounting sealing plates on the outer case edge, and this sealing plate is heated at the curing temperature of the adhesive, or heated above the melting point of the brazing material or soldering material. In this case, when the electrolyte in the outer case was heated, it volatilized outside the outer case, and the capacity of the battery characteristics was not reduced and sufficient sealing could not be performed.
本発明に係る電気化学セルは、正極及び負極からなる一対の電極と、非水電解質と、前記電極を分離するセパレータと、前記正極と前記負極と前記電解質と前記セパレータとを収納するセラミックス又はガラス製の外装ケースと、封口板とを有し、前記外装ケースには集電体として作用する導電性パターンが形成されており、前記導電性パターンが金属材料、炭素材料又は導電性セラミックス材料のうちのいずれか一種類を用いる。 The electrochemical cell according to the present invention includes a pair of electrodes composed of a positive electrode and a negative electrode, a nonaqueous electrolyte, a separator separating the electrodes, ceramics or glass containing the positive electrode, the negative electrode, the electrolyte, and the separator. A conductive pattern that acts as a current collector, and the conductive pattern is a metal material, a carbon material, or a conductive ceramic material. Any one of these is used.
本発明に係る電気化学セルは、前記導電性パターンが1300℃以上の融点を有しかつ周期表のIVa族元素、Va族元素、VIII族元素のうちの少なくとも1種類の元素を含む材料からなる。 The electrochemical cell according to the present invention is made of a material in which the conductive pattern has a melting point of 1300 ° C. or higher and contains at least one element selected from the group IVa, Va, and VIII elements of the periodic table. .
また、本発明に係る電気化学セルは、前記導電性パターンがMoを0.5wt%以上含む材料からなる。 In the electrochemical cell according to the present invention, the conductive pattern is made of a material containing 0.5 wt% or more of Mo.
本発明に係る電気化学セルは、前記導電性パターンが、黒鉛、カーボンブラックまたはガラス状カーボンのうち少なくとも一種類を含む炭素材料からなる。 In the electrochemical cell according to the present invention, the conductive pattern is made of a carbon material containing at least one of graphite, carbon black, and glassy carbon.
また、本発明に係る電気化学セルは、前記導電性パターンが導電性セラミックスを含んでいる。 In the electrochemical cell according to the present invention, the conductive pattern includes conductive ceramics.
さらに好ましくは本発明に係る電気化学セルは、前記導電性パターンの表面に、NiまたはAuのメッキが形成されている。 More preferably, in the electrochemical cell according to the present invention, Ni or Au plating is formed on the surface of the conductive pattern.
また、本発明に係る電気化学セルは、封口板は金属もしくは合金からなり、前記封口板の表面には、ろう材がめっき法又は印刷を用いた厚膜法で形成されており、抵抗溶接により前記外装ケースに前記封口板が接合されている。 In the electrochemical cell according to the present invention, the sealing plate is made of a metal or an alloy, and the brazing material is formed on the surface of the sealing plate by a thick film method using a plating method or printing. The sealing plate is joined to the exterior case.
本発明に係る電気化学セルでは、外装ケースに正極集電体を兼ねる導電性のパターンが形成され、導電性材料は、金属材料、炭素材料または導電性セラミックスを用いたことにより、充電又は過放電時による正極集電体の腐食に起因するセルの容量低下や内部抵抗増加等の性能劣化が極めて小さく、抵抗溶接によりセル封口の溶接時に封口板熱膨張及び収縮による歪が発生しないので漏液がなく外部水分浸入によるセルの性能劣化が極めて小さい従来にない信頼性のある電気化学セルを実現できる。 In the electrochemical cell according to the present invention, a conductive pattern also serving as a positive electrode current collector is formed on the outer case, and the conductive material is charged or overdischarged by using a metal material, a carbon material or a conductive ceramic. Performance degradation such as cell capacity reduction and internal resistance increase due to corrosion of the positive electrode current collector due to time is extremely small, and leakage due to thermal expansion and contraction of the sealing plate does not occur when welding the cell seal by resistance welding. In addition, an unprecedented reliable electrochemical cell in which the performance degradation of the cell due to external moisture intrusion is extremely small can be realized.
また、負極、正極の外部回路との接続のための接続リードを導電性のパターン配線とすることにより外装ケース底面に接続端子を直接パターン形成できる構造としたことにより容易でタブ端子等の取付けが不要であり小型、薄型化かつ高容量のセルが得られる等、優れた電気化学セルを実現できる。 In addition, the connection lead for connecting to the external circuit of the negative electrode and the positive electrode is made of conductive pattern wiring so that the connection terminal can be directly patterned on the bottom surface of the outer case, so that tab terminals can be easily attached. An excellent electrochemical cell can be realized such that it is unnecessary and a small, thin and high capacity cell can be obtained.
本発明に係る電気化学セルの断面図を図1に示す。 A cross-sectional view of an electrochemical cell according to the present invention is shown in FIG.
負極集電体を兼ねる封口板101は、結晶粒径の均一化及び粒界腐食に起因するカソード腐食が起こりにくいコバールからなる。コバールは、セラミックス又はガラス製の外装ケース102と同等の熱膨張係数2〜11×10-6/℃(0〜300℃)を有するため、封口板にコバールを用いると抵抗溶接時の封口部歪が緩和され信頼性の高い封口が可能になり、漏液或いは外部水分の浸入を妨げることができる。 The sealing plate 101 that also serves as the negative electrode current collector is made of Kovar that is less susceptible to cathode corrosion due to uniform crystal grain size and intergranular corrosion. Since Kovar has a thermal expansion coefficient of 2 to 11 × 10 −6 / ° C. (0 to 300 ° C.) equivalent to the ceramic or glass outer case 102, if Kovar is used for the sealing plate, the distortion of the sealing portion during resistance welding Is relaxed and a highly reliable sealing becomes possible, and leakage or external moisture intrusion can be prevented.
さらに抵抗溶接を行うため封口板101にNiメッキ105を施す。また外装ケース接合部には、Au或いはNi等からなるメタライズ層111を形成し、封口板との溶接を行う。Niメッキの代わりにAu、Wメッキを用いても好ましい。また、Niメッキ105の上にろう材106を形成すると抵抗溶接の密着性を高めることができる。 Further, Ni plating 105 is applied to the sealing plate 101 for resistance welding. Further, a metallized layer 111 made of Au, Ni, or the like is formed at the exterior case joint, and welding with the sealing plate is performed. It is also preferable to use Au or W plating instead of Ni plating. Further, if the brazing material 106 is formed on the Ni plating 105, the adhesion of resistance welding can be improved.
図1の外装ケース102は、ガラス、セラミックスまたはセラミックスガラス等の耐熱材料が好ましく、封口板101と熱膨張係数の近いものが望ましい。 1 is preferably a heat-resistant material such as glass, ceramics, or ceramic glass, and preferably has a thermal expansion coefficient close to that of the sealing plate 101.
外装ケース102にセラミックスを用いた場合は、強度及び絶縁性が高いため薄型化が容易であり好ましい。セラミックスの中でもアルミナが強度、熱膨張の面で優れている。 The use of ceramics for the outer case 102 is preferable because it is easy to reduce the thickness because of high strength and insulation. Among ceramics, alumina is excellent in terms of strength and thermal expansion.
導電性接着剤109を介して、外装ケース102の内側底面に形成された導電性パタ−ンA112と正極ペレット107を接着した。また導電性パターンA112は、正極集電体として作用する。導電性パターンA112は、外装ケース壁面を貫通し接続端子A103に電気的に接続している。
負極集電体との配線は、外装ケース上面部から、側面の内部に貫通させた導電性パターンB113により、接続端子B104に電気的に接続した。正極及び負極と外部回路との接続のため、導電性パターンを外装ケースにメッキ或いは焼付けにより形成する。導電性パターンは、外装ケース底面、側面に形成可能である。このため、タブ端子等の取付けが不要となり、小型、薄型化が可能となる。
The conductive pattern A 112 and the positive electrode pellet 107 formed on the inner bottom surface of the outer case 102 were bonded via the conductive adhesive 10 9. The conductive pattern A112 functions as a positive electrode current collector. The conductive pattern A112 penetrates the outer case wall surface and is electrically connected to the connection terminal A103.
The wiring with the negative electrode current collector was electrically connected to the connection terminal B104 through the conductive pattern B113 penetrating from the upper surface of the outer case into the inside of the side surface. In order to connect the positive and negative electrodes to an external circuit, a conductive pattern is formed on the outer case by plating or baking. The conductive pattern can be formed on the bottom and side surfaces of the outer case. For this reason, it is not necessary to attach a tab terminal or the like, and the size and thickness can be reduced.
また、導電性パターンが施しているセラミックスケースは、セラミックグリーンシート積層し焼成することにより作られている。導電性材料をグリーンシートに塗布することで、セラミックスケースの焼成と導電性パターンの焼き付けが同時に行われる。
グリーンシートは1300℃以上で焼成される。このため、導電性材料の融点は1300℃以上必要であり、かつ電気化学セルとした時に、アノード腐食を起こさない導電性材料であることが必要である。例えば金属では、Ta,Nb,Ti,Hf,Zr等の弁作用金属、又はMoを0.5wt%以上含むステンレス等の合金であれば良い。また、炭素材料では天然黒鉛、人造黒鉛等の黒鉛、カーボンブラック或いはガラス状カーボン等が良い。導電性セラミックスとしては、SiC、TiC、TiB2、WC、WO2、ZrN、NbSi2、またはTaSi2がアノード腐食に優れ、複合セラミックスとしてはAl2O3-SiC、Al2O3−TiB2、AlN−TiN(TiC)、Si3N4−TiC(TiN)等が好ましい。その導電性材料製の導電性パターン上にNi、又はAuのメッキを被覆することも好ましい。
Moreover, the ceramic case to which the conductive pattern is given is made by laminating and firing ceramic green sheets. By applying the conductive material to the green sheet, firing of the ceramic case and baking of the conductive pattern are performed simultaneously.
The green sheet is fired at 1300 ° C. or higher. For this reason, the melting point of the conductive material is required to be 1300 ° C. or higher, and it is necessary to be a conductive material that does not cause anodic corrosion when an electrochemical cell is formed. For example, the metal may be a valve action metal such as Ta, Nb, Ti, Hf, or Zr, or an alloy such as stainless steel containing 0.5 wt% or more of Mo. As the carbon material, graphite such as natural graphite and artificial graphite, carbon black, glassy carbon, and the like are preferable. As the conductive ceramic, SiC, TiC, TiB 2, WC, WO 2, ZrN, NbSi 2, or TaSi 2 is excellent in the anode corrosion, as the composite ceramic Al 2 O 3 -SiC, Al 2 O 3 -TiB 2 AlN—TiN (TiC), Si 3 N 4 —TiC (TiN), and the like are preferable. It is also preferable to coat Ni or Au plating on the conductive pattern made of the conductive material.
正極ペレット107、負極ペレット108の活物質は炭素を導電性フィラーとする導電性接着剤109で接着した。集電体と正極ペレット107、負極ペレット108は必ずしも接着する必要はなく集電体上に正極ペレット107、負極ペレット108を載置し電気的接続がなされていれば良い。 The active materials of the positive electrode pellet 107 and the negative electrode pellet 108 were bonded with a conductive adhesive 109 using carbon as a conductive filler. The current collector, the positive electrode pellet 107, and the negative electrode pellet 108 are not necessarily bonded, and it is sufficient that the positive electrode pellet 107 and the negative electrode pellet 108 are placed on the current collector and electrically connected.
また、抵抗溶接の密着性を良くするため図2に示すように、外装ケース202へ金属製リング210を設けても良い。外装ケース202と熱膨張係数が同等である金属製リング210を利用することにより、抵抗溶接時の封口部歪がなくなり安定した溶接を行うこともできるが、金属製リング210と正極ペレット206の活物質が接近してしまいショートし易くなる。また、金属製リング210があると薄型化、小型化が困難なため図1のように金属製リングがないものが好ましい。 Further, in order to improve the adhesion of resistance welding, a metal ring 210 may be provided on the outer case 202 as shown in FIG. By using the metal ring 210 having the same thermal expansion coefficient as that of the outer case 202, it is possible to eliminate the sealing portion distortion at the time of resistance welding and perform stable welding. However, the metal ring 210 and the positive electrode pellet 206 can be activated. Substances approach and become short-circuited easily. Further, since it is difficult to reduce the thickness and size of the metal ring 210, it is preferable to have no metal ring as shown in FIG.
電気化学セルの発電素子として非水電解質電池を構成する場合には、正極ペレット107の活物質として、TiS2、MoS2、NbSe3等の金属カルコゲン化物や、MnO2、MoO3、V2O5、LixCoO2、LixNiO2、LixMn2O4等の金属酸化物、ポリアニリン、ポリピロール、ポリパラフェニレン、ポリアセン等の導電性高分子、およびグラファイト層間化合物等のリチウムイオン及びアニオンを吸蔵放出可能な各種の物質を用いることができる。 When a nonaqueous electrolyte battery is configured as a power generation element of an electrochemical cell, a metal chalcogenide such as TiS 2 , MoS 2 , NbSe 3 , MnO 2 , MoO 3 , V 2 O is used as an active material of the positive electrode pellet 107. 5, Li x CoO 2, Li x NiO 2, Li x Mn 2 O metal oxides such as 4, polyaniline, polypyrrole, polyparaphenylene, conductive polymers such as polyacene, and lithium ions and anions such as graphite intercalation compound Various substances capable of occluding and releasing can be used.
また、負極ペレット108の活物質としては特に限定されないが、SiO、WO2、WO3、SnO、LiAl、Liまたは炭素材料等各種物質を用いることができる。 The active material of the negative electrode pellet 108 is not particularly limited, and various materials such as SiO, WO 2 , WO 3 , SnO, LiAl, Li, or a carbon material can be used.
電気化学セルが電気二重層キャパシタの場合には、正負極ペレットの活物質に活性炭或いは活性炭繊維を用いることができる。 When the electrochemical cell is an electric double layer capacitor, activated carbon or activated carbon fiber can be used as the active material of the positive and negative electrode pellets.
使用するセパレータ110は非水電解質への溶解や化学反応劣化がなく耐熱性のある不織布であることが好ましい。たとえば、ポリオレフィンのマイクロポーラスフィルム等のセパレータにおいては、非水電解液への溶解や腐食劣化等に対して安定であるが、抵抗溶接法を利用したシーム溶接時の熱で圧延方向に収縮してしまうため、内部ショートを起こしやすくなる等の問題があり耐熱性が不十分である。耐熱性のある樹脂PPS、PEEKまたはガラス繊維を用いたセパレータの場合、収縮がなく良好であった。また、セラミックスの多孔質体を用いることも良い。 The separator 110 to be used is preferably a non-woven fabric that is heat resistant and does not dissolve in non-aqueous electrolytes or deteriorate in chemical reaction. For example, a separator such as a polyolefin microporous film is stable against dissolution in a non-aqueous electrolyte or corrosion deterioration, but shrinks in the rolling direction by heat during seam welding using a resistance welding method. Therefore, there is a problem that an internal short circuit is likely to occur, and the heat resistance is insufficient. In the case of a separator using heat-resistant resin PPS, PEEK or glass fiber, there was no shrinkage and it was good. It is also possible to use a ceramic porous body.
電解液は非水溶媒としてプロピレンカーボネイト、ブチレンカーボネイト、スルホラン、γ-ブチロラクトン、エチレンカーボネイト、アセトニトリル、ジメトキシエタン、メチルフォルメイト等の単独或いは適宣混合した有機溶媒に六フッ化リン酸リチウム、ホウフッ化リチウム、トリフルオロメタンスルホン酸リチウム、リチウムパーフルオロエチルスルホニルイミド、(C2H5)4PBF4、(C3H7)4PBF4、(CH3)(C2H5)3NBF4、(C2H5)4NBF4、(C2H5)4PPF6、(C2H5)4PCF3SO4、(C2H5)4NPF6等を0.1〜3.0モル溶解したものを用いることができる。 The electrolyte is a non-aqueous solvent such as propylene carbonate, butylene carbonate, sulfolane, γ-butyrolactone, ethylene carbonate, acetonitrile, dimethoxyethane, methyl formate, or an organic solvent such as lithium hexafluorophosphate or borofluoride. Lithium, lithium trifluoromethanesulfonate, lithium perfluoroethylsulfonylimide, (C 2 H 5 ) 4 PBF 4 , (C 3 H 7 ) 4 PBF 4 , (CH 3 ) (C 2 H 5 ) 3 NBF 4 , ( 0.1 to 3.0 mol of C 2 H 5 ) 4 NBF 4 , (C 2 H 5 ) 4 PPF 6 , (C 2 H 5 ) 4 PCF 3 SO 4 , (C 2 H 5 ) 4 NPF 6 and the like. A dissolved one can be used.
外装ケース内部に正極ペレット107及び負極ペレット108、セパレータ110、電解液を収納し、封口板101で蓋をした後、抵抗溶接の原理を利用したパラレルシーム溶接機により、二辺に対向するローラー型の電極を加圧し、電流を流すことで封口板101と外装ケース102をスポット溶接し仮止めしたあと2辺ずつ溶接を行った。この方法により信頼性の高い封口が得られた。 Roller type facing the two sides by parallel seam welding machine using the principle of resistance welding after housing positive electrode pellet 107 and negative electrode pellet 108, separator 110, electrolyte solution inside the outer case, capping with sealing plate 101 The sealing plate 101 and the outer case 102 were spot welded and temporarily fixed by applying pressure and applying current, and then welding was performed two sides at a time. By this method, a highly reliable seal was obtained.
電気化学セルの内部に材料がある場合の溶接においては、抵抗溶接法を利用したシーム溶接が特に好ましい。レーザー等の溶接では外装ケース102中の各材料が封口板101を押上げ外装ケース102の溶接部と封口板101が離れてしまい適切な溶接を得ることができない。それに対しシーム溶接は、電極のローラー型が封口板101を加圧することにより外装ケース102の溶接部と封口板101が密着し信頼性の高い封口が得られる。 In welding where there is a material inside the electrochemical cell, seam welding using resistance welding is particularly preferred. In welding by laser or the like, each material in the outer case 102 pushes up the sealing plate 101 and the welded portion of the outer case 102 is separated from the sealing plate 101, so that appropriate welding cannot be obtained. On the other hand, in the seam welding, when the electrode roller type pressurizes the sealing plate 101, the welded portion of the outer case 102 and the sealing plate 101 are brought into close contact with each other, and a highly reliable sealing is obtained.
本発明の非水電解質電池および電気二重層キャパシタの形状は基本的に自由である。従来の図4に示したかしめ封口による電気二重層キャパシタの形状はほぼ円形に限定される。そのため、角型状がほとんどである他の電子部品と同一の基板上に並べようとすると、デットスペースができ無駄であった。本発明の非水電解質電池および電気二重層キャパシタは角型の設計も可能で、端子等の突起物がないため、小型化及び効率的に基板上に配置することができ、上記のように構成された非水電解質電池および電気二重層キャパシタは、アノード腐食が起こりにくい信頼性の優れた電気化学セルを構成するようになる。 The shapes of the nonaqueous electrolyte battery and the electric double layer capacitor of the present invention are basically free. The shape of the electric double layer capacitor with the caulking seal shown in FIG. 4 is limited to a substantially circular shape. For this reason, when trying to arrange them on the same substrate as other electronic components having almost square shapes, dead space is wasted. The non-aqueous electrolyte battery and the electric double layer capacitor of the present invention can be designed in a square shape, and since there are no protrusions such as terminals, they can be reduced in size and efficiently placed on the substrate, and are configured as described above. The nonaqueous electrolyte battery and the electric double layer capacitor thus formed constitute a highly reliable electrochemical cell in which anodic corrosion hardly occurs.
(実施例1)
実施例1として、熱膨張係数6.8×10-6/℃(0〜300℃)を有するアルミナ製の外装ケース(幅7mm×奥行5mm×高さ0.9mm)を用いた。導電性材料としてカーボンブラックを使用し導電性パターンを形成し、導電性パターン上にNiメッキで被覆した。
外装ケースの底面に導電性接着剤109を塗布後、リチウム含有マンガン酸化物を用いた正極ペレット107(幅5mm×奥行3.2mm×高さ0.3mm)を接着し、その上にガラス繊維不織布を用いたセパレータ110(幅5.3mm×奥行3. 5mm×高さ0.1mm)を載置し正極ユニットとした。また、コバール合金からなる封口板101(幅6.5mm×奥行4.5mm×高さ0.1mm)にNiメッキ105、更にろう材としてAg-Cuを施した。この封口板にシリコン酸化物SiOを活物質とする負極ペレット108(幅5mm×奥行3mm×高さ0.1mm)に炭素を導電性フィラーとした導電性接着剤109で接着し、リチウム(幅5mm×奥行3.2mm×高さ0.1mm)を貼り付け、負極ユニットとした。正極ユニット及び負極ユニットのそれぞれにプロピレンカーボネート(PC)とエチレンカーボネート(EC)とジメトキシエタン(DME)の1:1:2の混合溶媒に支持塩として1Mの濃度の過塩素酸リチウム(LiClO4)を溶解した電解液を注入した後に、正極ユニットと負極ユニットを一体化し、シーム溶接機により溶接電極のローラー型にて封口板周縁部を加圧しながら溶接封止を行い、非水電解質電池を作成した。
Example 1
As Example 1, an alumina outer case (width 7 mm × depth 5 mm × height 0.9 mm) having a thermal expansion coefficient of 6.8 × 10 −6 / ° C. (0 to 300 ° C.) was used. A conductive pattern was formed using carbon black as the conductive material, and the conductive pattern was covered with Ni plating.
After applying the conductive adhesive 109 to the bottom of the outer case, a positive electrode pellet 107 (width 5 mm × depth 3.2 mm × height 0.3 mm) using lithium-containing manganese oxide is adhered, and a glass fiber nonwoven fabric is used thereon. The separator 110 (width 5.3 mm × depth 3.5 mm × height 0.1 mm) was placed to form a positive electrode unit. A sealing plate 101 made of Kovar alloy (width 6.5 mm × depth 4.5 mm × height 0.1 mm) was subjected to Ni plating 105 and Ag—Cu as a brazing material. This sealing plate was bonded to a negative electrode pellet 108 (width 5 mm × depth 3 mm × height 0.1 mm) using silicon oxide SiO as an active material with a conductive adhesive 109 using carbon as a conductive filler, and lithium (width 5 mm × A depth of 3.2 mm × height of 0.1 mm) was pasted to make a negative electrode unit. In each of the positive electrode unit and the negative electrode unit, 1M lithium perchlorate (LiClO4) as a supporting salt was added to a 1: 1: 2 mixed solvent of propylene carbonate (PC), ethylene carbonate (EC), and dimethoxyethane (DME). After injecting the dissolved electrolyte, the positive electrode unit and the negative electrode unit were integrated, and a seam welder was used to weld and seal the periphery of the sealing plate with the roller type of the welding electrode, thereby creating a nonaqueous electrolyte battery. .
(比較例1)
伝導性パターンを形成する導電性材質をカーボンブラックからWに変更した以外は同様に非水電解質電池を作成したものを比較例1とする。
(Comparative Example 1)
A non-aqueous electrolyte battery was prepared as Comparative Example 1 except that the conductive material for forming the conductive pattern was changed from carbon black to W.
以上のようにして作製した非水電解質電池を、約1週間室温でエージングした後、充放電テストを行い充放電容量の確認をした。また、これらの非水電解質電池に3.3Vの電圧を印加しながら100日間60℃で保存した後の容量を測定し、初期容量からの容量劣化率及びその時の内部抵抗の測定、外観を検査した結果を第1表に示した。 The non-aqueous electrolyte battery produced as described above was aged at room temperature for about 1 week, and then a charge / discharge test was performed to confirm the charge / discharge capacity. In addition, the capacity after being stored at 60 ° C. for 100 days while applying a voltage of 3.3 V to these nonaqueous electrolyte batteries is measured, and the capacity deterioration rate from the initial capacity and the internal resistance at that time are measured and the appearance is inspected. The results are shown in Table 1.
実施例2として熱膨張係数6.8×10-6/℃(0〜300℃)であるアルミナ製の外装ケース202(幅5mm×奥行3.2mm×高さ0.6mm)を用い、導電性パターンとして導電性セラミックスTiCを使用しその上にNiメッキAuメッキされた全底面に、炭素を導電性フィラーとした導電性接着剤208を塗布後、正極活物質として活性炭を用いた正極ペレット206(幅3.8mm×奥行2.0mm×高さ0.15mm)を接着し、その上にガラス繊維不織布を用いたセパレータ209(幅3.9mm×奥行2.1mm×高さ0.05mm)を載置し正極ユニットとした。また、コバール合金からなる負極集電体を兼ねる封口板201(幅4.5mm×奥行2.7mm×高さ0.1mm)にNiメッキ205を施した。この封口板に活性炭を用いた負極ペレット207(幅3.8mm×奥行2.0mm×高さ0.15mm)を導電性接着剤208で接着し負極ユニットとした。正極ユニット及び負極ユニットをそれぞれに、プロピレンカーボネイトの溶媒に支持塩として1Mの濃度(C2H5)4NBF4を溶解した電解液を注入した後に、正極ユニットと負極ユニットを一体化し、パラレルシーム溶接機により溶接電極のローラー型にて封口板周縁部を加圧しながら溶接封止を行い、電気二重層キャパシタを作成した。
As Example 2, an alumina outer case 202 (width 5 mm × depth 3.2 mm × height 0.6 mm) having a thermal expansion coefficient of 6.8 × 10 −6 / ° C. (0 to 300 ° C.) was used as a conductive pattern. A conductive adhesive 208 using carbon as a conductive filler is applied to the entire bottom surface of the conductive ceramic TiC and Ni-plated Au plated thereon, and then a positive electrode pellet 206 (width 3.8 mm) using activated carbon as a positive electrode active material. mm × depth 2.0 mm × height 0.15 mm) and a separator 209 (width 3.9 mm × depth 2.1 mm × height 0.05 mm) using a glass fiber nonwoven fabric was placed thereon to form a positive electrode unit. Further, Ni plating 205 was applied to a sealing plate 201 (width 4.5 mm × depth 2.7 mm × height 0.1 mm) that also serves as a negative electrode current collector made of Kovar alloy. A negative electrode pellet 207 (width 3.8 mm × depth 2.0 mm × height 0.15 mm) using activated carbon was adhered to the sealing plate with a conductive adhesive 208 to form a negative electrode unit. Each of the positive electrode unit and the negative electrode unit was injected with an electrolyte solution in which a 1M concentration (C 2 H 5 ) 4 NBF 4 was dissolved as a supporting salt in a propylene carbonate solvent, and then the positive electrode unit and the negative electrode unit were integrated to form a parallel seam. An electric double layer capacitor was produced by performing welding sealing while pressurizing the periphery of the sealing plate with a roller type of a welding electrode by a welding machine.
(比較例2)
導電性パターンの材質をTiCからWに変更した以外は同様に電気二重層キャパシタを作成したものを比較例2とした。
(Comparative Example 2)
Comparative Example 2 was obtained by similarly producing an electric double layer capacitor except that the material of the conductive pattern was changed from TiC to W.
以上のようにして作製した実施例と比較例を充放電テストを行い充放電容量の確認をした。また、70℃の雰囲気中で2.5V以上の電圧を印加しながら1000時間保存した後の容量を測定し、初期容量からの容量劣化率及びその時の内部抵抗の測定、外観を検査した結果を第1表に示した。 The charge / discharge test was conducted by confirming the charge / discharge capacity by carrying out charge / discharge tests on the examples and comparative examples produced as described above. In addition, the capacity after storage for 1000 hours while applying a voltage of 2.5 V or higher in an atmosphere at 70 ° C. was measured, and the capacity deterioration rate from the initial capacity and the internal resistance at that time were measured and the results of the appearance inspection were performed. It is shown in Table 1.
第1表の結果から実施例1と比較例1を比較すると比較例1では容量劣化、内部抵抗増大及び漏液がみられ電気化学セルを分解し正極集電体をSEMにて観察したところ孔食が確認された。一方、実施例1では腐食が見られなかった。また、実施例2と比較例2において、比較例2では容量劣化が大きく内部抵抗の著しい増加が見られた。しかし、実施例2では容量劣化や内部抵抗の増加は殆ど見られず優れていることが解る。比較例2の電気化学セルを分解し正極集電体をSEMにて観察したところ孔食が確認された。しかし、実施例2では腐食が見られなかった。 Comparing Example 1 and Comparative Example 1 based on the results in Table 1, in Comparative Example 1, capacity degradation, increased internal resistance and leakage were observed, the electrochemical cell was disassembled, and the positive electrode current collector was observed by SEM. The food was confirmed. On the other hand, no corrosion was observed in Example 1. Further, in Example 2 and Comparative Example 2, in Comparative Example 2, the capacity was greatly deteriorated and the internal resistance was significantly increased. However, it can be seen that Example 2 is excellent with almost no capacity deterioration or increase in internal resistance. When the electrochemical cell of Comparative Example 2 was disassembled and the positive electrode current collector was observed by SEM, pitting corrosion was confirmed. However, no corrosion was observed in Example 2.
101 封口板
102 外装ケース
103 接続端子A
104 接続端子B
105 Niメッキ
106 ろう材
107 正極ペレット
108 負極ペレット
109 導電性接着剤
110 セパレータ
111 メタライズ層
112 導電性パターンA
113 導電性パターンBOLE_LINK3
201 封口板
202 外装ケース
203 接続端子OLE_LINK3A
204 接続端子B
205 Niメッキ
206 正極ペレット
207 負極ペレット
208 導電性接着剤
209 セパレータ
210 金属製リング
211 メタライズ層
212 導電性パターンA
213 導電性パターンB
301 封口板
302 外装ケース
303 接続端子
401 金属製ケ−ス
402 金属製フタ
403 リードタブ端子A
404 リードタブ端子B
101 Sealing plate 102 Exterior case 103 Connection terminal A
104 Connection terminal B
105 Ni plating 106 Brazing material 107 Positive electrode pellet 108 Negative electrode pellet 109 Conductive adhesive 110 Separator 111 Metallized layer 112 Conductive pattern A
113 Conductive pattern BOLE_LINK3
201 Sealing plate 202 Exterior case 203 Connection terminal OLE_LINK3A
204 Connection terminal B
205 Ni plating 206 Positive electrode pellet 207 Negative electrode pellet 208 Conductive adhesive 209 Separator 210 Metal ring 211 Metallized layer 212 Conductive pattern A
213 Conductive pattern B
301 Sealing plate 302 Exterior case 303 Connection terminal 401 Metal case 402 Metal lid
403 Lead tab terminal A
404 Lead tab terminal B
Claims (3)
前記外装ケースは、前記外装ケースの外側の底面から側面に直接パターン形成された接続端子Aと、前記外装ケースの内側の底面から前記外装ケースの壁面を貫通して前記外装ケースの外側の側面に直接パターン形成された前記導電性パターンAと、前記外装ケースの外側の底面から側面に延設された接続端子Bと、前記外装ケースの側面の内部を前記外装ケースの上面部から前記外装ケースの底面まで貫通している導電性パターンBとを備え、
前記導電性パターンA及び前記導電性パターンBの材料は、カーボンブラック又はTiCであり、
前記導電性パターンAは、前記正極及び前記接続端子Aと電気的に接続され、
前記導電性パターンBは、前記封口板及び、前記接続端子Bと電気的に接続され、
前記封口板の周縁部は、前記外装ケースの縁部の外周より小さく、かつ、前記外装ケースの縁部の内周より大きいことを特徴とする電気化学セル。 A positive electrode, a negative electrode, a nonaqueous electrolyte, a separator that separates the positive electrode and the negative electrode, the positive electrode, the negative electrode, the nonaqueous electrolyte, and the separator are housed, a sealing plate, and a resistor An electrochemical cell comprising an outer case sealed by welding,
The exterior case includes a connection terminal A that is directly patterned on the side surface from the bottom surface on the outside of the exterior case, and a wall surface of the exterior case from the bottom surface on the inside of the exterior case to the outer side surface of the exterior case. The conductive pattern A directly patterned, the connection terminal B extending from the outer bottom surface of the outer case to the side surface, and the inside of the side surface of the outer case from the upper surface portion of the outer case to the outer case With conductive pattern B penetrating to the bottom,
The material of the conductive pattern A and the conductive pattern B is carbon black or TiC,
The conductive pattern A is electrically connected to the positive electrode and the connection terminal A,
The conductive pattern B is electrically connected to the sealing plate and the connection terminal B,
The electrochemical cell according to claim 1, wherein a peripheral edge of the sealing plate is smaller than an outer periphery of an edge of the outer case and larger than an inner periphery of the edge of the outer case.
前記金属製リングの外周は、前記外装ケースの縁部の外周より小さく、かつ、前記外装ケースの縁部の内周より大きく、
前記封口板の周縁部の外周は、前記金属製リングの外周より小さく、かつ、前記金属製リングの内周より大きいことを特徴とする請求項1に記載の電気化学セル。 A metal ring is provided between the outer case and the sealing plate,
The outer periphery of the metal ring is smaller than the outer periphery of the edge of the outer case, and larger than the inner periphery of the edge of the outer case,
The outer periphery of the peripheral portion of the sealing plate is smaller than the outer circumference of the metal ring, and The electrochemical cell according to claim 1, wherein the greater than the inner circumference of the metal ring.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004021673A JP4824279B2 (en) | 2004-01-29 | 2004-01-29 | Electrochemical cell |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004021673A JP4824279B2 (en) | 2004-01-29 | 2004-01-29 | Electrochemical cell |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011170478A Division JP5341960B2 (en) | 2011-08-03 | 2011-08-03 | Electrochemical cell |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2005216668A JP2005216668A (en) | 2005-08-11 |
JP4824279B2 true JP4824279B2 (en) | 2011-11-30 |
Family
ID=34905233
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2004021673A Expired - Fee Related JP4824279B2 (en) | 2004-01-29 | 2004-01-29 | Electrochemical cell |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4824279B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011258566A (en) * | 2011-08-03 | 2011-12-22 | Seiko Instruments Inc | Electrochemical cell |
US11830672B2 (en) | 2016-11-23 | 2023-11-28 | KYOCERA AVX Components Corporation | Ultracapacitor for use in a solder reflow process |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5466065B2 (en) * | 2010-03-29 | 2014-04-09 | セイコーインスツル株式会社 | Method for producing electrochemical element |
JP5777001B2 (en) * | 2010-08-23 | 2015-09-09 | セイコーインスツル株式会社 | Electronic component, electronic device, and method of manufacturing electronic component |
CN106128796A (en) * | 2016-06-08 | 2016-11-16 | 湖南耐普恩科技有限公司 | A kind of ultracapacitor, current collector of super capacitor and processing method thereof |
JP6897682B2 (en) * | 2016-08-02 | 2021-07-07 | 日本ゼオン株式会社 | Solar cell module |
CN111477796B (en) * | 2020-04-30 | 2023-12-08 | 惠州市恒泰科技股份有限公司 | Button cell and preparation method thereof |
CN113937395A (en) * | 2021-09-30 | 2022-01-14 | 新余赣锋电子有限公司 | Button cell |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5780658A (en) * | 1980-11-08 | 1982-05-20 | Hitachi Maxell Ltd | Thin battery |
JPH04170089A (en) * | 1990-11-02 | 1992-06-17 | Kawasaki Steel Corp | Ceramic circuit board |
JP2898877B2 (en) * | 1994-02-14 | 1999-06-02 | 株式会社東芝 | Aluminum nitride sintered body having conductive metallized layer and method of manufacturing the same |
JPH08181449A (en) * | 1994-12-22 | 1996-07-12 | Hitachi Ltd | Connecting electrode of electronic circuit board and manufacture thereof |
JPH08339943A (en) * | 1995-06-09 | 1996-12-24 | Mitsubishi Materials Corp | Structure and method for sealing electronic element |
JP3959220B2 (en) * | 2000-02-04 | 2007-08-15 | 株式会社エスアイアイ・マイクロパーツ | Non-aqueous electrolytic battery for surface mounting and electric double layer capacitor for surface mounting |
JP2002246499A (en) * | 2001-02-21 | 2002-08-30 | Kyocera Corp | Package for accommodating semiconductor device |
JP2003264250A (en) * | 2002-03-07 | 2003-09-19 | Sumitomo Electric Wintec Inc | Packaging metal tape |
JP2005158678A (en) * | 2003-10-30 | 2005-06-16 | Kyocera Corp | Battery case, battery and manufacturing method therefor |
JP2005135726A (en) * | 2003-10-30 | 2005-05-26 | Kyocera Corp | Case for battery, and battery |
-
2004
- 2004-01-29 JP JP2004021673A patent/JP4824279B2/en not_active Expired - Fee Related
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011258566A (en) * | 2011-08-03 | 2011-12-22 | Seiko Instruments Inc | Electrochemical cell |
US11830672B2 (en) | 2016-11-23 | 2023-11-28 | KYOCERA AVX Components Corporation | Ultracapacitor for use in a solder reflow process |
Also Published As
Publication number | Publication date |
---|---|
JP2005216668A (en) | 2005-08-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4550519B2 (en) | Electrochemical cell and method for producing the same | |
US6445566B2 (en) | Power source element | |
JP4527366B2 (en) | Method for producing electrochemical cell | |
JP4817778B2 (en) | Battery case and battery, and electric double layer capacitor case and electric double layer capacitor | |
JP2006049289A (en) | Case for battery, battery, case for electric double layer capacitor, and electric double layer capacitor | |
JP4845388B2 (en) | Electrochemical cell | |
JP5588539B2 (en) | Electrochemical cell | |
JP4824279B2 (en) | Electrochemical cell | |
JP4149349B2 (en) | Secondary battery and manufacturing method thereof | |
JP4671651B2 (en) | Battery case and battery, and electric double layer capacitor case and electric double layer capacitor | |
US8553392B2 (en) | Electronic component, electronic device, and manufacturing method for the electronic component | |
JP5341960B2 (en) | Electrochemical cell | |
JP2005183373A (en) | Battery case, manufacturing method thereof and battery, electric double-layer capacitor case and manufacturing method thereof, and electric double-layer capacitor | |
JP4762074B2 (en) | Container, battery or electric double layer capacitor using the same, and electronic device | |
US20170179446A1 (en) | Package for electrochemical cell, and electrochemical cell | |
JP5813821B2 (en) | Electrochemical cell | |
JP5032636B2 (en) | Electrochemical cell and method for producing the same | |
JP4976623B2 (en) | Reflow solderable electrochemical cell | |
JP6489544B2 (en) | Electrochemical cell | |
JP6362063B2 (en) | Electrochemical cell | |
JP4671652B2 (en) | Battery case and battery | |
JP2005209640A (en) | Battery housing and battery, and housing for battery and electric double-layer capacitor and electric double-layer capacitor | |
JP4694826B2 (en) | Electrochemical cell and method for producing the same | |
JP2006216645A (en) | Electrochemical cell and its manufacturing method | |
JP6308578B2 (en) | Electrochemical cell |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20061227 |
|
A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20071116 |
|
RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20091105 |
|
RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20091112 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100702 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100907 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20101105 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20110510 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20110803 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20110812 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20110906 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20110908 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4824279 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140916 Year of fee payment: 3 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |