TW201230102A - Electrode for power storage device, method of manufacturing the same and connection method thereof - Google Patents

Electrode for power storage device, method of manufacturing the same and connection method thereof Download PDF

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Publication number
TW201230102A
TW201230102A TW100121005A TW100121005A TW201230102A TW 201230102 A TW201230102 A TW 201230102A TW 100121005 A TW100121005 A TW 100121005A TW 100121005 A TW100121005 A TW 100121005A TW 201230102 A TW201230102 A TW 201230102A
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TW
Taiwan
Prior art keywords
layer
electrode
plating
storage device
alloy
Prior art date
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TW100121005A
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English (en)
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TWI528396B (zh
Inventor
Katsuji Nakamura
Kaichi Tsuruta
Yuji Ozaki
Shigeaki Watarai
Hidenori Takagi
Yutaka Ohori
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Senju Metal Industry Co
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Publication of TW201230102A publication Critical patent/TW201230102A/zh
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Publication of TWI528396B publication Critical patent/TWI528396B/zh

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/48—Coating with alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/22—Electroplating: Baths therefor from solutions of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H01B1/023—Alloys based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/32—Filling or coating with impervious material
    • 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
    • H01G11/04—Hybrid capacitors
    • H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/66—Current collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/502—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49117—Conductor or circuit manufacturing
    • Y10T29/49124—On flat or curved insulated base, e.g., printed circuit, etc.
    • Y10T29/49147—Assembling terminal to base

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Connection Of Batteries Or Terminals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemically Coating (AREA)

Description

201230102 六、發明說明： 【發明所屬之技術領域】 从本發:月係關於電雙層電容器 '鐘離子電容器及二次電 池等的可蓄積電能的蓄電穿 接續方^ ㈣電極、其製造方法以及其 【先前技術】 經離子電容器’被期待代替 了 管黽雙層電容器及二次電 池。該鐘離子電容器，係藉 用稱為負極離子吸藏的物 理見象，顯著地提升蓄電效率 电双早的電谷益。現在，電雙層電 係用於列車、建機等的大型機器的電池馬達所產生 =蓄t，而今後期待藉由小型化，亦可使用於汽車的 燃料電池等的蓄電。 鐘離子電容器，具有非對稱電極構造。藉此，相較於 電雙層電容器，具有電壓較古相較於 ，电壓季乂阿，相較於二次電池具有内部 電阻低，可以短時間進 ^ * 兄狡電，因充放電的的惡化少且 產品哥命長等的長處。但是， 鋰離子電谷器，有能密度低 的缺點。於電容器有捲繞型 β 疋土电谷益、積層型電容器等’均 具有陽極及陰極的兩個電極。 具有鐘離子電容器的兩個電極，係分別以不同種類的 金屬所構成’例如，於陽極的導線電極使用Μ等，於陰極 的導線電極使用Cu等。要求夬沾喊带At η古 女 > 大的放電月b時，以並聯連接續 使用，要求高電壓時以串聯使用。 ;先刖的積層型的鋰離子電容器，電雙層電容器及 201230102 -: 人電池等的導線電極的接續方法，有使用羯狀的導線電 極’以超音波等的點焊接接合的方法（專利文獻1}，對導 線電極以按押狀態接觸的旋轉體接續之方法(專利文獻 2)，將狀的導電電極明絲等鎖緊的方法等。 [先行技術文獻] [專利文獻] [專利文獻1]日本特開2000_9〇9〇7號公報 [專利文獻2]日本特開2〇〇5_2〇9735號公報 【發明内容】 [發明所欲解決的課題] 然而’專利文獻1所述以點焊接之電極的接續方法， …、如A1電極與A1電極之接續或電極與電極之接 、-、=聯接續），以同-種類金屬的電極相互接合之接合強 度门仁如A1電極與Cu電極的接續(串聯接續），以異種 金屬的接合則接合強度低，缺乏接續可靠度。 此外，於專利文獻2所述的旋轉體的電極的接續方法 =以鎖螺絲之電極接續方法，由於接觸面積小，而該接觸 的電阻值會變高，而產生很大的電壓降。 ^產生如此之因接續電阻的電壓降，則供給於負載的電 氣機器等的電壓會較蓄電裝置的電壓少。 b因此，本發明係為解決上述課題而完成者，以提供可 ，升異種金屬的電極的接合強度’相較於先前的點焊接或 ★螺絲之接合’可使接觸面積變大，降低接合處的電阻值， 201230102 不會使蓄電裝置的電壓減少而女 搞㈣… 地供給的蓄電裝置用電 極、其製造方法以及其接續方法。 电 [用以解決課題的手段] 本發明者們’發現只要可將蓄電裝置的導線電極 ：將導線電極的全面接續，故可使導線電極的接 二又變同’以及以導線電極全面接續’則接續處的面積 擴大’可降低接續處的電阻值下降而完成本發明。 關於本發明的蓄電裝置用電極，其特徵在於：在 組成的陽極電極上以鍍敷形成以層或Zn合金層
Sn層或Sn合金層。 增、 在關於本發明的蓄電裝晉用 I电裝置用電極，係於A1所組成的陽 玉電二上讀敷形成Zn層或Zn合金層^層、如層或 11…層。藉此’可於Sn層或如合金層上與A1的 金屬所組成的陰極電極桿接。 但 蓄電裝置的陽極的導線電極(以下稱為「ai陽極 主要使用A1’但是A1無法以—般的銲錫焊接。Ai用的銲 =知有Sn-15質量.及^3〇質量仏#，該等辉錫， 係：由_用與A1焊接者，以A1陽極電極相互的接續 的c有：^但疋’以该等銲錫’焊接A1陽極電極與陰極 的Cu電極(以下稱為「Cu陰極電極」），則在高溫高渴声 下出現Sn-Zn輝錫中的Zn離子向Cu中移動的克肯道空； 山加如⑴⑷的現象，而降低銲錫接合強度。特別是 在電雙層電容器、鐘離子電容器及二次電池，由於 覆充放電’故容易發熱。此外，Sn_Zn銲錫容易氧化而降 201230102 低導電性。因此，AI陽極電極與Cu陰極電極上焊材使用 Sn-Zn銲錫直接接合並不佳。 此外彳考慮藉由在A1陽極電極上披覆可與Cu陰極 電極焊接的金屬。但是，與Cu陰極電極焊接性良好^或 Sn合金，相對於Sn的標準電極電位為ΐ38ν，μ的標準 電極電位H 1 662V’ # A1與Gu的標準電極電位差有 1.524V，故無法直接在Αι上鍍Sn或鍍如合金。 於本發明，藉由將A1陽極電極上被覆Zn層或Zn合金 層，可與A1陽極電極形成密著性良好的Zn或&合金膜。 然後，在該膜上形成Sn層或銲錫（Sn合金層），可得與a 陰極電極焊接性良好的A丨陽極電極。 由於披覆在A1陽極電極上的Zn層或Zn合金層的坡 膜。係以鍍敷法形成。於鍍敷法，通常鍍敷Zn單體之情形 為多，惟鍍Zn合金之一例的Zn_6~16%Ni的Zn_Ni合金鍍 敷可以與Zn相同的鋅酸鹽浴鍍形成錢敷。此外，可以鍵敷 法形成的其他Zn合金鍍敷，有Zn —Fe鍍敷或211_“鍍敷等。 由於鍍敷表面保持Zn鍍敷，在後步驟的Sn層或sn合 金層的鍍敷形成困難，故將Ni鏟敷作為Sn層或Sn合金層 的底層披覆於Zn鍍敷上為佳。藉由在Zn鍍敷上設置Ni 層’可提升Sn層或Sn合金層的密著性。此外，於Zn層與 Sn層之間的n i層，可作用作為物理性阻障。即N丨層可防 止起因於披覆在A1陽極電極上的Zn向Cu陰極電極移動而 產生克肯道空洞而降低階合強度。 本發明的Zn層或Zn合金層、Sn層或Sn合金層，可 201230102 1由電链形成，亦可藉由無電電鐵形成。藉由如此之锻敷 :不僅可將所有的步驟統一為鍍敷，而且可得膜厚精度 “的畜電裝置用電極。此外’由於可將膜厚很薄地形成， 故導線的彎曲性良好。然而，將本發明的蓄電裝置用電極 的Sn層或Sn合金層以鍍敷法形成時，sn或“合金層薄 而不容易焊接，故使用含脂㈣錫焊接為佳。&層或％ 合金層’係以含脂銲錫等使含接容易地進行為目的而披覆。 此外，關於本發明的蓄電裝置用電極的製造方法，其 特徵在於：包含：將A1所組成的陽極電極的表面以有機溶 劑脫脂的脫脂步驟；以該脫脂步驟脫脂的陽極電極的表面 以㈣液钕刻的钱刻步驟；在以該钕刻步驟姓刻之陽極電 極的表面，以鋅酸鹽液开彡& 7你^叙 孤履沿成Zn鍍敷的Zn鍍敷步驟；在以 該Zn鍍敷步驟形成的Zn鍍敷上表面上，以^鍛敷液形成 h鍍敷的Ni鍍敷步驟；及以該Ni鍍敷步驟形成Ni鍍敷 的表面上，以Sn鍍敷液形成Sn鍍敷的如鍍步驟。 此外，關於本發明的蓄電裝置用電極的接續方法，其 特徵在於HUSn或銲錫，將於AI所組成的電極上以鑛 敷形成zn層或Zn合金層、Ni層、Sn層或如合金層的陽 極電極’與Cu所組成的陰極電極，接續者。 [發明效果] 根據關於本發明的蓄電裝置用電極，據其製造方法以 及其接續方法，由於可與A〗所組成的陽極電極與幻的異 種金屬所組成的陰極電極焊接，故可提升陽極電極與陰極 電極的接合強度。此外，相較於先前的點祥或以鎖螺絲的 201230102 接合，接觸面積大，接合處的電阻值變低，可減低蓄電妒 置因接續電阻的電壓降。結果，可不使蓄電裝置的電壓減 少而可有效地提供負載。 【實施方式】 以下參照設圖面說明關於電雙層電容器、鋰離子電容 器及一次電池等的關於本發明之蓄電裝置。 [蓄電裝置100的構成例] 首先，說明關於本發明的蓄電裝置i00的構成例。如 圖1所示，蓄電裝置100,係以⑽組成的陽極導線電極 (以下料「A1陽極電極1〇J ) ; A1的異種金屬的Cu所組 成的陰極導線電極(以下稱為「Cu陰極電極3〇」以及分 離器由40所構成。 於A1陽極電極1G及Cu陰極電極3()，分別設有延在 於一端的接續端子部1Qa、3Ga。接續端子部iQa 3〇a係 以：聯接續蓄電裝i丨時，將接續端子部.與接續端 子部30a接續’以並聯接續蓄電裝置1〇〇日夺，將端子部… 與接續端子部3Ga接續。此外，接續端子部1()a、3()a，係 不與畜電裝置1GQ串聯或並聯接續，而成為外部的接續端 子者。 、 :接續端子部10a形成有鍍敷層2〇。鍍敷層2〇係為 只端子部l〇a與接續端子部3〇a容易且確實地接續者。 [鍍數層20的構成例] 如圖2所示’鍍敷層20，係以於A1所組成的接續端 201230102 子部10a上以鍍敷形成z 盾21 Nl層22、Sn層23。再 者，Zn層21亦可為Zn合金屏 θ 層23亦可為Sn合金層。 例如’所謂Zn合金層，係指z 和Zn-Nx合金、Zn_Fe合 合金等，所謂Sn合金層係指 隻 ^ 唆 9 Sn Bl 合金、Sn-Ag 合金、Sn-Cu 合金等。
Zn 層 21、Ni 層 22 及 Sn M 9<ί & 曰23的厚度’會對A!陽極 電極10與Cu陰極電極3〇沾飞▲由 ^ η 的可#度造成影響。由於Zn層 21的厚度在0. 01 // m以下，難 $ a ^ 下難以形成形成在Zn層21上的 Νι層22’Zn層21的厚度左n 予度在〇.15"m以上，A1的接續端子 部10a與Zn層21的密著性合變姜， a k差 而戎部分會有剝離之 情形。Zn層21的厚度以〇 〇5_〇1"m為佳。 此外Μ敷Zn層21時’為提升與M的接續端子部 10 a的密著性，以驗浴龙技 ,,, -佳，例如將ΖηΟ、Ζπ、NaOH等以 水溶解之辞酸鹽浴，及對钫拉缺碰、,、 對該鋅鲅鹽洽，添加NaCN等的氰化 物的氰化物浴為佳。由协丨v拉缺瞒v、 田於以鋅酸鹽浴以及氰化物浴的鍍 敷，接續端子部…的A1的表面容易氧化而以1次不太有 效果’故需要處理2次以上。 Νι層22，係若該Ni層22的厚度過薄，則失去以層 21。Sn層23之間的阻障效果，相反地過厚，則焊接時該 Νι層22與Cu陰極電極3〇反應形成Cu3Sn以及—等的 金屬間化合物。由於CU3Sn及CueSn5等的金屬間化合物硬 脆而不適用於電極。因此，Ni層22的厚度以1〜3# m為佳， 以2-3从m更佳。
Sn層23 ’當該sn層23的厚度過薄，則Ni層22的 201230102 而與Cu陰極電極3〇焊接性變差 極電極Π的f曲加工等，該Sn 八：厚則在A1陽 此％層23的厚产以5 i 。刀办易被破壞。因 [蓄電裝置1 〇 〇的接續例] 接著’說明蓄電裝置1〇〇的 蓄雷駐@… 曰7接續例。如圖3所示’將 畜電裝置100串聯接續時，將接 qn , 貝和于# 1 〇a與接續端子 4 30a經由鍍敷層2〇 杆妫Μ接續。銲錫50,雖難與接 續知子部l〇a的A1焊接 9n六日 彳一 Lu的接續端子部30a與鍍層 20谷易焊接。並且， 了為3鉛銲錫，亦可由 M-Ag-Cu或Sn — Zn所構成的無鉛銲錫。 藉此，可經由錢覆層20將A1陽極電極1〇與&陰極 電極30焊接，故可提升A1陽極電極1〇與cu陰極電極⑽ 的接合強度。此外，相較於先前的點焊或鎖螺絲的接合， 接續端子部IGa與接續端子部3Ga的接地面積大，接合部 (接續端子部l〇a及接續端子部3〇a接合之部分）的電阻值 變低，故可減低減蓄電裝置100的接續電阻的電壓降。結 果，可不使蓄電裝置100的電壓減少而有效地提供負載。 再者，於本實施的形態，說明以Cu組成的陰極電極， 惟並非限定於此，本發明可適用於A1的異種金屬的陰極電 極0 [實施例1] 其次’說明形成於關於本發明之蓄電裝置1〇〇的A1陽 極電極10之鍍敷層20的製造方法。鍍敷層20係以如下 1〜5的順序製造。 10 201230102 < 1.脫脂步驟〉 將長度70mm、寬50mm、厚度0. 2mm的大小的接續端子 部1 〇a ’使用有機溶劑進行浸潰脫脂。 < 2 ·钮刻步驟〉 將脫脂的接續端子部1 水洗’鹼性蝕刻後，浸潰於 酸溶液（姓刻液）將表面粗化。藉由該步驟可使Ai所組成的 接續端子部1 〇a與Zn層21的密著性良好。 <3. Zn鍍敷步驟> 將钮刻處理的接續端子部10 a，浸潰於以水溶解ZnO、 Zn、NaOH等的鋅酸鹽浴，形成Zn鍍（Zn層21)。 為沖去附著於Zn鍍敷的接續端子部1 〇a的鋅酸鹽液而 水洗之後，將該接續端子部1 〇a浸潰於硝酸，將鋅酸鹽（zn 等）剝離。 再度，將接續端子部1 〇a浸潰於鋅酸鹽浴，形成Zn鍍 敷’水洗後’浸潰於硝酸，將鋅酸鹽（Zn等）剝離。 再者’取代上述Zn鍍敷形成Zn-Ni合金鍍敷時，於辞 酸鹽浴使用添加ZnCh、NiCh等的鋅酸鹽浴。 〈4. Ni鍍敷步驟〉 將形成Zn鍍敷的接續端子部1 〇a，浸潰於以水溶解 · 6ib0、NaH2P〇2等的無電電鍍Ni鍍敷浴3〇〇秒左右 形成Ni鍍敷（Ni層22)，水洗之。再者，Ni鍍敷，並非限 定於無電電鍍’亦可為電鍍。 <5. Sn鍍步驟〉 將形成Ni鍍敷的接續端子部丨〇a，浸潰於以水溶解化 201230102 —SO3. 3Hz〇、Sn、Na〇H2等的鹼性酸性“鍍浴中浸2〇分 鐘左右，形成Sn鍍敷（sn層23)，水洗之。之後，藉由乾 燥，完成鍍敷層20。 〜5製造的鍍敷層20，以螢光χ射線膜 ，Zn層21的厚度為〇 〇5"m，Ni層 ’ Sn層23的厚度為7# m。 將以上述步驟1 厚計測定膜厚的結果 22的厚度為1.5#πι [實施例2] 將具有實施例1所形成的鍍敷層20的A1陽極電極 10，與Cu陰極電極30以含脂銲錫焊接。含脂銲錫使用 RMA08(千住金屬工業股份公司製），以銲搶的搶尖溫度為 300°C ’焊接時間1〇秒的條件，焊接。 作為比較例1 ’形成將A1陽極電極與Cu陰極電極以 Sn-1 5質量％Zri所構成的線銲錫直接銲接者。然而，於該焊 接，先塗助焊劑再進行。 作為比較例2，形成將A1陽極電極與Cu陰極電極以 超音波之點焊接續者。 於表1表示實施例1、比較例1及2之A1陽極電極與 Cu陰極電極的接合強度之測定結果。然而，該接合強度係 遵照JIS H8630及JIS C6481 ’以密著強度試驗器測定（試 料數N = 5)。此外，亦測定將試料加速氧化後的接合強度。 該氧化加速條件係將試料放入氣氛溫度85°C、濕度85%的 恆溫槽24小時，對該試料，流通每1秒反覆0N/0FF的1〇〇A 的電流。 [表1 ] 12 201230102 --_ 接合強度（Kg/cm) 氧化加迷前 氧化加速後 差 實施例1 5. 9 4. 5 1.4 比較例1 5.3 3. 8 1.5 比較例2 2. 9 —---------- 0. 71 2. 19 如表1所示，氧化加速前的接合強度，於實施例1為 5. 9kg/cm、比較例 1 為 5· 3kg/cm、比較例 2 為 2. 9kg/cm。 由此可知實施例1的接合強度較比較例1及2提升。 氧化加速後的接合強度，於實施例1為4. 5kg/cm、比 較例1為3. 8kg/cm、比較例2為〇. 71kg/cm。由此可知， 實施例1即使是氧化加速之後，接合強度亦較比較例1及 2提升。 氧化加速前的接合強度與氧化加速後的接合強度的 差’於實施例1為1. 4kg/cm、比較例1為1· 5kg/cm、比較 例2為2. 19kg/cm。由此可知，實施例1的氧化加速前的 接合強度與氧化加速後的接合強度的差距較比較例丨及2 小，而提升了接合可靠度。 其次，將實施例1、比較例1及2的鹽霧環境試驗的 結果（由試驗開始120小時後及600小時後的A1陽極電極 與Cu陰極電極的狀態）示於表2。然而，該環境試驗係遵 照 JIS C0024 〇 13 201230102
\ 鹽霧試驗之結果例 120h 後 600h 後 實施例1 .* < .....-V-...: · :tt^ 孔蝕：無 白粉：無 孔蝕：無 白粉：少量 比較例Ί 1 4» 5 * 孔触：有 白粉：無 孔蝕：有 白粉：大量 比較例2 1— 样 ula-in ,υηιη r · .嫌 *___......mimr-i------*-------- ::巧？ ::、·;:·- V 孔蝕：無 白粉：有 孔蝕：無 白粉：大量 201230102 如表2所示，由試驗開始12 0小時後，實施例1並沒 有發生孔蝕及白粉，6 0 0小時後的實施例1產生少量的白 粉。此外’由試驗開始12 0小時後的比較例1出現孔蝕， 600小時後的比較例1出現大量的白粉。此外，由試驗開 始1 20小時後的比較例2出現白粉，600小時後的比較例2 出現大里白粉。如此地發生孔钱或產生大量的白粉，會降 低蓄電裝置用電極的導電性及強度。 如此地，實施例1即使在鹽霧環境，亦沒有發生孔蝕， 只會產生不會對導電性及強度造成影響的程度的少量白 粉。即’可知實施例1的導電性良好，作為蓄電裝置有可 靠度。此外，比較例1及2，在鹽霧環境導電性變差，缺 乏作為蓄電裝置的可靠度。 [實施例3] 以實施例1、比較例丨及2的Α1陽極電極與Cu陰極 電極製作接合樣品，將該製作的接合樣品的電阻值及電壓 值以微歐姆錶使用凱爾文夾以四線法測定。其測定條件係 將實施例1、比較例i以及2的試料放入氣氛溫度85t、 濕度85%的恆溫槽内，對該試料流通每j秒反覆⑽/〇ff的 100A的電流。 圖4係表示縱軸為接合樣品的電阻值（# Ώ)，橫軸為 100Α的電流的〇N/〇FF反覆次數（χ1〇〇〇)時的接合樣品的電 :值的特性例的說明圖。如4所示，實施例i的接合樣 的電阻值係以菱形表示，初期是400 # Ω，QN/OFF24000 次之後是440 # Ω，〇N/〇FF48〇〇〇次之後是45〇y ◦， 15 201230102 ON/OFF75000 次之後是 450 μ Ω，ON/OFF120000 次之後是 4 7 0 " Ω。比較例1的接合樣品的電阻值係以四角表示，初 期是 33〇β Ω ，ON/OFF24000 次之後是 360 # Ω ， ON/OFF48000 次之後是 400 //Ω，ON/OFF75000 次之後是 5 00 y Ω，ON/OFF120000次之後是600 μ Ω。比較例2的接 合樣品的電阻值係以三角表示，初期是575 // Ω ， ON/OFF24000 次之後是 60〇βΩ，ON/OFF48000 次之後是 600 /ζ Ω ’ ON/OFF75000 次之後是 670 " Ω，ON/OFF1 20000 次之後是750 // Ω。 由此，ΟΝ/OFF反覆次數120000次後的實施例1的電 阻值’與比較例1及2的電阻值相比只有6〜8成的電阻值。 因此’於實施例1可減低約60〜80%的電氣損耗。 此外，實施例1的接合樣品的電阻值，由初期開始 ON/OFF1 2 0000次之後只有70/ζ Ω程度的變化，與此相比， 比較例1的接合樣品的電阻值變化2 7 0 // Ω，比較例2的 接合樣品的電阻值變化1 7 5 /ζ Ω。即，實施例1的可靠度 較比較例1及2提升。 圖5係表示縱軸為接合樣品的電壓值（V)，橫軸為1〇〇A 的電流的ΟΝ/OFF反覆次數（χίοοο)時的接合樣品的電壓值 的特性例的說明圖。如圖5所示’實施例1的接合樣品的 電壓值，係以菱形表示，由初期至〇N/〇FF1 20000次後為維 持0. 2V。比較例1的接合樣品的電壓值係以四角表示，初 期是 0. 2V ’ ON/OFF24000 次之後是 0. 2V，ON/OFF480 00 次 之後是 0. 3V，ON/OFF750 00 次之後是 0.4V，ON/OFF12000 0 16 201230102 次之後是0· 5V。比較例2的接合樣品的電壓值係以三角表 示’初期是 0_ 7V，ON/OFF24000 次之後是 〇. 7V，ON/OFF48000 次之後是 0.8V’ON/OFF75000 次之後是 〇.8V，ON/OFF1 20000 次之後是0. 8V。 由此’實施例1即使是0N/0FF1 20000次之後，接合樣 品的電壓值並沒有變化，可靠度較比較例1及2提升。 [實施例4] 以實施例1、比較例1及2的A1陽極電極與Cu陰極 電極製作接合樣品’將該製作的接合樣品的溫度以K型熱 電偶測定。測定條件’與實施例3所示的測定條件相同， 將實施例1、比較例1及2的試料放入氣氛溫度85°C、濕 度85%恆溫槽内，流對該試料流通每1秒反覆ΟΝ/OFF的 1 00A的電流。 圖6係表示縱軸為接合樣品的溫度（°c )，橫軸為1 〇 〇 A 的電流的ΟΝ/OFF反覆次回數（X1 〇〇〇)時的接合樣品的溫度 的特性例的說明圖。如圖6所示，實施例1的接合樣品的 溫度係以菱形表示，初期是85. 55。(：，ON/OFF24000次之後 是 85. 55°C，ON/OFF48000 次之後是 85. 55°C，ON/OFF75000 次之後是 85.77°C，ON/OFF1 20000 次之後是 85.77°C。比 較例1的接合樣品的溫度係以四角表示，初期是84. 22°C， ON/OFF24000 次之後是 84.28°C，ON/OFF48000 次之後是 85.11°C，ON/OFF75000 次之後是 87.9°C，ON/OFF1 20000 次之後是90. 52°C。比較例2的接合樣品的溫度係以三角 表示，初期是96.3°C，ON/OFF24QOO次之後是96.89°C， 17 201230102 ON/OFF48000 次之後是 96.06°C，ON/OFF75000 次之後是 97. 3°C，ON/OFF1 20000次之後是97. 3。(：。該等溫度變化係 起因於接合樣品的電阻值變化，而使焦耳熱變化。 由此’實施例1即使是〇N/〇FF反覆次數120000次後’ 接合樣品的溫度幾乎不會變化（其理由是由於圖4所示接 合樣品的電阻值低。），可靠度較比較例〗及2提升。 如此地，關於本發明的蓄電裝置丨〇〇，係於A1陽極電 極10上以鍍敷形成Zn層21、Ni層22、Sn層23。藉此， 可以Sn層23與A1的異種金屬的Cu組成的以陰極電極 30焊接。結果，可A1陽極電極1〇與&陰極電極3〇的接 合強度。 ^卜，畜冤裝置100,與以先前的銲接的接合（比較例 1)或以超音波的點焊（比較例2)及鎖螺絲的接合相比，由 於接續端子部10a與接續端子部3〇a的接觸面積大，而接 合部的電阻值變低，故可減低因f電1置1()()的㈣電阻 :電壓降。結果，可不使蓄電裝£⑽的電壓減少 地提供負載。 [產業上的利用可能性] 本發明的蓄電裝置，並非限定為箱形者，亦 圓筒型的電雙層電容器、鋰離子 、用、 蓄電裝置。 …及二次電池等的 【圖式簡單說明】 1 〇 〇的構成例的立 圖1係表示關於本發明的蓄電裝置 18 201230102 剖面圖。
圖6係表示接合樣品的溫度的特性例的說明圖 圖2係表示鍍層20的構成例的 圖3係表示蓄電裝置ι〇〇的接 【主要元件符號說明】 10〜Α1陽極電極； 10a、30a〜接續端子部； 20~鍍層； 21~Zn 層； 22〜Ni層； 2 3 ~ S η 層； 30~Cu陰極電極； 40〜分離器； 50~銲錫； 100〜蓄電裝置。 19

Claims (1)

  1. 201230102 七、申請專利範圍： 在A1所組成的 Ni層、Sn層或 1. 一種蓄電裝置用電極，其特徵在於 陽極電極上以鍍敷形成Zn層或Zn合金層 Sn合金層。 2_如申凊專利範園1項所述的蓄電裝 „ 瑕·置用電極，立φ 上述陽極電極係於A1上形成Zn層赤7 ^ T 層上形成Sn層 -X Zn合金屏，# μ、七 Zn層或Zn合金層上形成Ni層，於 曰於上見 "、上迷n . 或Sn合金層。 其 其 其 3_如申請專利第1或2項所述的 辑电裝置用電極 中上述Zn層或Zn合金層具有〇 〇5〜n 1 . u · 1 V «1的厚度。 4.如申請專利第1或2項所述的蓄電裝置用電極 中上述Ni層具有1〜3ym的厚度。 5·如申請專利第1或2項所述的蓄電裝置用電極 中上述Sn層或Sn合金層具有5~15ym的厚度。 法’其特徵在於具有： 以有機溶劑脫脂的脫 6. —種蓄電裝置用電極的製造方 將A1所組成的陽極電極的表面 脂步驟； 以上述脫脂步冑脫脂的上述陽極電極的表面以姓刻液 #刻的钱刻步驟； 在以上述蝕刻步驟蝕刻之上述陽極電極的表面，以鋅 酸鹽液形成Zn鐘敷的Zn錢敷步驟； 在以上述Zn鐘敷步驟形成的Zn鍍敷上表面上，以Ni 鍵敷液形成Ni鍍敷的鑛敷步驟；及 以上述Ni鍍敷步驟形成Ni鍍敷的表面上，以如鍍敷 20 201230102 液形成Sn鍍敷的Sn鍍步驟。 7. —種蓄電裝置用電極的接續方法，其特徵在於：使 用Sn或銲錫，將於A1所組成的電極上以鍍敷形成Zn層或 Zn合金層、Ni層、Sn層或Sn合金層的陽極電極，與Cu 所組成的陰極電極接續。 ；；! 21
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