TWI528396B - Electrode for storage device, method for manufacturing the same, and method of connection thereof - Google Patents

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

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Publication number
TWI528396B
TWI528396B TW100121005A TW100121005A TWI528396B TW I528396 B TWI528396 B TW I528396B TW 100121005 A TW100121005 A TW 100121005A TW 100121005 A TW100121005 A TW 100121005A TW I528396 B TWI528396 B TW I528396B
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TW
Taiwan
Prior art keywords
layer
plating
electrode
storage device
anode electrode
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TW100121005A
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English (en)
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TW201230102A (en
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 OR LIGHT-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 OR LIGHT-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 OR LIGHT-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
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    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
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    • 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
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    • 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
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    • 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
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    • 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

Description

蓄電裝置用電極、其製造方法以及其接續方法
本發明係關於電雙層電容器、鋰離子電容器及二次電池等的可蓄積電能的蓄電裝置用電極、其製造方法以及其接續方法。
鋰離子電容器，被期待代替電雙層電容器及二次電池。該鋰離子電容器，係藉由利用稱為負極離子吸藏的物理現象，顯著地提升蓄電效率的電容器。現在，電雙層電容器，係用於列車、建機等的大型機器的電池馬達所產生的電的蓄電，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。
鋰離子電容器，具有非對稱電極構造。藉此，相較於電雙層電容器，具有電壓較高，相較於二次電池具有內部電阻低，可以短時間進行充放電，因充放電的的惡化少且產品壽命長等的長處。但是，鋰離子電容器，有能密度低的缺點。於電容器有捲繞型電容器、積層型電容器等，均具有陽極及陰極的兩個電極。
具有鋰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Al等，於陰極的導線電極使用Cu等。要求大的放電能時，以並聯連接續使用，要求高電壓時以串聯使用。
用於先前的積層型的鋰離子電容器，電雙層電容器及二次電池等的導線電極的接續方法，有使用箔狀的導線電極，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)，將箔狀的導電電極以螺絲等鎖緊的方法等。
[先行技術文獻]
[專利文獻]
[專利文獻1]日本特開2000-90907號公報
[專利文獻2]日本特開2005-209735號公報
然而，專利文獻1所述以點焊接之電極的接續方法，雖然如Al電極與Al電極之接續或Cu電極與Cu電極之接續(並聯接續)，以同一種類金屬的電極相互接合之接合強度高，但如Al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或以鎖螺絲之電極接續方法，由於接觸面積小，而該接觸處的電阻值會變高，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。
因此，本發明係為解決上述課題而完成者，以提供可提升異種金屬的電極的接合強度，相較於先前的點焊接或鎖螺絲之接合，可使接觸面積變大，降低接合處的電阻值，不會使蓄電裝置的電壓減少而有效地供給的蓄電裝置用電極、其製造方法以及其接續方法。
本發明者們，發現只要可將蓄電裝置的導線電極以銲錫接續，可將導線電極的全面接續，故可使導線電極的接合強度變高，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Al所組成的陽極電極上以鍍敷形成Zn層或Zn合金層、Ni層、Sn層或Sn合金層。
在關於本發明的蓄電裝置用電極，係於Al所組成的陽極電極上以鍍敷形成Zn層或Zn合金層、Ni層、Sn層或Sn合金層。藉此，可於Sn層或Sn合金層上與Al的異種金屬所組成的陰極電極焊接。
蓄電裝置的陽極的導線電極(以下稱為「Al陽極電極」)主要使用Al，但是Al無法以一般的銲錫焊接。Al用的銲錫已知有Sn-15質量%Zn及Sn-30質量%Zn等，該等銲錫，係藉由Zn的作用與Al焊接者，以Al陽極電極相互的接續不會有問題。但是，以該等銲錫，焊接Al陽極電極與陰極的Cu電極(以下稱為「Cu陰極電極」)，則在高溫高濕度下出現Sn-Zn銲錫中的Zn離子向Cu中移動的克肯道空洞(Kirkendall Void)的現象，而降低銲錫接合強度。特別是在電雙層電容器、鋰離子電容器及二次電池，由於會被反覆充放電，故容易發熱。此外，Sn-Zn銲錫容易氧化而降低導電性。因此，Al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，可考慮藉由在Al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Sn或Sn合金，相對於Sn的標準電極電位為-0.138V，Al的標準電極電位為-1.1662V，而Al與Cu的標準電極電位差有1.524V，故無法直接在Al上鍍Sn或鍍Sn合金。
於本發明，藉由將Al陽極電極上披覆Zn層或Zn合金層，可與Al陽極電極形成密著性良好的Zn或Zn合金膜。然後，在該膜上形成Sn層或銲錫(Sn合金層)，可得與Cu陰極電極焊接性良好的Al陽極電極。
由於披覆在Al陽極電極上的Zn層或Zn合金層的披膜。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鍍敷。此外，可以鍍敷法形成的其他Zn合金鍍敷，有Zn-Fe鍍敷或Zn-Al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鍍敷作為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Ni層，可作用作為物理性阻障。即Ni層可防止起因於披覆在Al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，可藉由電鍍形成，亦可藉由無電電鍍形成。藉由如此之鍍敷法，不僅可將所有的步驟統一為鍍敷，而且可得膜厚精度很高的蓄電裝置用電極。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Sn合金層薄而不容易焊接，故使用含脂的銲錫焊接為佳。Sn層或Sn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Al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蝕刻液蝕刻的蝕刻步驟；在以該蝕刻步驟蝕刻之陽極電極的表面，以鋅酸鹽液形成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Ni鍍敷液形成Ni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Sn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：使用Sn或銲錫，將於Al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，接續者。
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Al所組成的陽極電極與Al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，相較於先前的點焊或以鎖螺絲的接合，接觸面積大，接合處的電阻值變低，可減低蓄電裝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。
以下參照設圖面說明關於電雙層電容器、鋰離子電容器及二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100的構成例。如圖1所示，蓄電裝置100，係以Al所組成的陽極導線電極(以下稱為「Al陽極電極10」)；Al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30」)；以及分離器由40所構成。
於Al陽極電極10及Cu陰極電極30，分別設有延在於一端的接續端子部10a、30a。接續端子部10a、30a係以串聯接續蓄電裝置100時，將接續端子部10a與接續端子部30a接續，以並聯接續蓄電裝置100時，將端子部10a與接續端子部30a接續。此外，接續端子部10a、30a，係不與蓄電裝置100串聯或並聯接續，而成為外部的接續端子者。
於接續端子部10a形成有鍍敷層20。鍍敷層20係為使接續端子部10a與接續端子部30a容易且確實地接續者。
[鍍敷層20的構成例]
如圖2所示，鍍敷層20，係以於Al所組成的接續端子部10a上以鍍敷形成Zn層21、Ni層22、Sn層23。再者，Zn層21亦可為Zn合金層，Sn層23亦可為Sn合金層。例如，所謂Zn合金層，係指Zn-Ni合金、Zn-Fe合金、Zn-Al合金等，所謂Sn合金層係指Sn-Bi合金、Sn-Ag合金、Sn-Cu合金等。
Zn層21、Ni層22及Sn層23的厚度，會對Al陽極電極10與Cu陰極電極30的可靠度造成影響。由於Zn層21的厚度在0.01μm以下，難以形成形成在Zn層21上的Ni層22，Zn層21的厚度在0.15μm以上，Al的接續端子部10a與Zn層21的密著性會變差，而該部分會有剝離之情形。Zn層21的厚度以0.05-0.1μm為佳。
此外，鍍敷Zn層21時，為提升與Al的接續端子部10a的密著性，以鹼浴為佳，例如將ZnO、Zn、NaOH等以水溶解之鋅酸鹽浴，及對該鋅酸鹽浴，添加NaCN等的氰化物的氰化物浴為佳。由於以鋅酸鹽浴以及氰化物浴的鍍敷，接續端子部10a的Al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。
Ni層22，係若該Ni層22的厚度過薄，則失去Zn層21與Sn層23之間的阻障效果，相反地過厚，則焊接時該Ni層22與Cu陰極電極30反應形成Cu3Sn以及Cu6Sn5等的金屬間化合物。由於Cu3Sn及Cu6Sn5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1~3μm為佳，以2-3μm更佳。
Sn層23，當該Sn層23的厚度過薄，則Ni層22的Ni氧化而與Cu陰極電極30焊接性變差，過厚則在Al陽極電極10的彎曲加工等，該Sn層23部分容易被破壞。因此Sn層23的厚度以5~15μm為佳。
[蓄電裝置100的接續例]
接著，說明蓄電裝置100的接續例。如圖3所示，將蓄電裝置100串聯接續時，將接續端子部10a與接續端子部30a經由鍍敷層20及銲錫50接續。銲錫50，雖難與接續端子部10a的Al焊接，但Cu的接續端子部30a與鍍層20容易焊接。並且，銲錫50，可為含鉛銲錫，亦可由Sn-Ag-Cu或Sn-Zn所構成的無鉛銲錫。
藉此，可經由鍍覆層20將Al陽極電極10與Cu陰極電極30焊接，故可提升Al陽極電極10與Cu陰極電極30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10a與接續端子部30a的接地面積大，接合部(接續端子部10a及接續端子部30a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Al的異種金屬的陰極電極。
[實施例1]
其次，說明形成於關於本發明之蓄電裝置100的Al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。
<1.脫脂步驟>
將長度70mm、寬50mm、厚度0.2mm的大小的接續端子部10a，使用有機溶劑進行浸漬脫脂。
<2.蝕刻步驟>
將脫脂的接續端子部10a水洗，鹼性蝕刻後，浸漬於酸溶液(蝕刻液)將表面粗化。藉由該步驟可使Al所組成的接續端子部10a與Zn層21的密著性良好。
<3.Zn鍍敷步驟>
將蝕刻處理的接續端子部10a，浸漬於以水溶解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10a的鋅酸鹽液而水洗之後，將該接續端子部10a浸漬於硝酸，將鋅酸鹽(Zn等)剝離。
再度，將接續端子部10a浸漬於鋅酸鹽浴，形成Zn鍍敷，水洗後，浸漬於硝酸，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，於鋅酸鹽浴使用添加ZnCl2、NiCl2等的鋅酸鹽浴。
<4.Ni鍍敷步驟>
將形成Zn鍍敷的接續端子部10a，浸漬於以水溶解NiSO4‧6H2O、NaH2PO2等的無電電鍍Ni鍍敷浴300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10a，浸漬於以水溶解化Na2SO3‧3H2O、Sn、NaOH2等的鹼性酸性Sn鍍浴中浸20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。
將以上述步驟1~5製造的鍍敷層20，以螢光X射線膜厚計測定膜厚的結果，Zn層21的厚度為0.05μm，Ni層22的厚度為1.5μm，Sn層23的厚度為7μm。
[實施例2]
將具有實施例1所形成的鍍敷層20的Al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)，以銲槍的槍尖溫度為300℃，焊接時間10秒的條件，焊接。
作為比較例1，形成將Al陽極電極與Cu陰極電極以Sn-15質量%Zn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Al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Al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℃、濕度85%的恆溫槽24小時，對該試料，流通每1秒反覆ON/OFF的100A的電流。
[表1]
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0.71kg/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1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Al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。
[表2]
如表2所示，由試驗開始120小時後，實施例1並沒有發生孔蝕及白粉，600小時後的實施例1產生少量的白粉。此外，由試驗開始120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120小時後的比較例2出現白粉，600小時後的比較例2出現大量白粉。如此地發生孔蝕或產生大量的白粉，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1及2的Al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1以及2的試料放入氣氛溫度85℃、濕度85%的恆溫槽內，對該試料流通每1秒反覆ON/OFF的100A的電流。
圖4係表示縱軸為接合樣品的電阻值(μΩ)，橫軸為100A的電流的ON/OFF反覆次數(×1000)時的接合樣品的電阻值的特性例的說明圖。如圖4所示，實施例1的接合樣品的電阻值係以菱形表示，初期是400μΩ，ON/OFF24000次之後是440μΩ，ON/OFF48000次之後是450μΩ，ON/OFF75000次之後是450μΩ，ON/OFF120000次之後是470μΩ。比較例1的接合樣品的電阻值係以四角表示，初期是330μΩ，ON/OFF24000次之後是360μΩ，ON/OFF48000次之後是400μΩ，ON/OFF75000次之後是500μΩ，ON/OFF120000次之後是600μΩ。比較例2的接合樣品的電阻值係以三角表示，初期是575μΩ，ON/OFF24000次之後是600μΩ，ON/OFF48000次之後是600μΩ，ON/OFF75000次之後是670μΩ，ON/OFF120000次之後是750μΩ。
由此，ON/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/OFF120000次之後只有70μΩ程度的變化，與此相比，比較例1的接合樣品的電阻值變化270μΩ，比較例2的接合樣品的電阻值變化175μΩ。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100A的電流的ON/OFF反覆次數(×1000)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ON/OFF120000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/OFF48000次之後是0.3V，ON/OFF75000次之後是0.4V，ON/OFF120000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0.7V，ON/OFF48000次之後是0.8V，ON/OFF75000次之後是0.8V，ON/OFF120000次之後是0.8V。
由此，實施例1即使是ON/OFF120000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Al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℃、濕度85%恆溫槽內，流對該試料流通每1秒反覆ON/OFF的100A的電流。
圖6係表示縱軸為接合樣品的溫度(℃)，橫軸為100A的電流的ON/OFF反覆次回數(×1000)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℃，ON/OFF48000次之後是85.55℃，ON/OFF75000次之後是85.77℃，ON/OFF120000次之後是85.77℃。比較例1的接合樣品的溫度係以四角表示，初期是84.22℃，ON/OFF24000次之後是84.28℃，ON/OFF48000次之後是85.11℃，ON/OFF75000次之後是87.9℃，ON/OFF120000次之後是90.52℃。比較例2的接合樣品的溫度係以三角表示，初期是96.3℃，ON/OFF24000次之後是96.89℃，ON/OFF48000次之後是96.06℃，ON/OFF75000次之後是97.3℃，ON/OFF120000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ON/OFF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1及2提升。
如此地，關於本發明的蓄電裝置100，係於Al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Al的異種金屬的Cu組成的Cu陰極電極30焊接。結果，可Al陽極電極10與Cu陰極電極30的接合強度。
此外，蓄電裝置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30a的接觸面積大，而接合部的電阻值變低，故可減低因蓄電裝置100的接續電阻之電壓降。結果，可不使蓄電裝置100的電壓減少而有效地提供負載。
[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，亦可適用於圓筒型的電雙層電容器、鋰離子電容器以及二次電池等的蓄電裝置。
10．．．Al陽極電極
10a、30a．．．接續端子部
20．．．鍍層
21．．．Zn層
22．．．Ni層
23．．．Sn層
30．．．Cu陰極電極
40．．．分離器
50．．．銲錫
100．．．蓄電裝置
圖1係表示關於本發明的蓄電裝置100的構成例的立體圖。
圖2係表示鍍層20的構成例的剖面圖。
圖3係表示蓄電裝置100的接續例的立體圖。
圖4係表示接合樣品的電阻值的特性例的說明圖。
圖5係表示接合樣品的電壓值的特性例的說明圖。
圖6係表示接合樣品的溫度的特性例的說明圖。
10a．．．接續端子部
20．．．鍍層
21．．．Zn層
22．．．Ni層
23．．．Sn層

Claims (7)

  1. 一種蓄電裝置用電極，為用於蓄電裝置的Al陽極電極，上述蓄電裝置包括Al所組成的陽極電極及和該Al為異種金屬的陰極電極而可將以負荷驅動用的馬達產生的電能在短時間充放電，其特徵在於：上述Al陽極電極具有：Zn層或Zn合金層，以鍍敷形成於延在於一端的接續端子部的Al上，並以鋅酸鹽處理；Ni層，以鍍敷形成於上述Zn層或Zn合金層上；以及Sn層或Sn合金層，以鍍敷形成於上述Ni層上。
  2. 如申請專利範圍1項所述的蓄電裝置用電極，其中對於以上述Al陽極電極與Cu所組成的陰極電極製作的接合樣品，在氣氛溫度85℃、濕度85%、100A的電流，反覆12萬次的ON/OFF，以四線法測定在其前後的上述接合樣品的電阻值時，上述接合樣品具有相對於初期的電阻值的增加的分量為70μΩ以下的特性。
  3. 如申請專利第1項所述的蓄電裝置用電極，其中上述Zn層或Zn合金層具有0.05~0.1μm的厚度。
  4. 如申請專利第1項所述的蓄電裝置用電極，其中上述Ni層具有1~3μm的厚度。
  5. 如申請專利第1項所述的蓄電裝置用電極，其中上述Sn層或Sn合金層具有5~15μm的厚度。
  6. 一種蓄電裝置用電極的製造方法，為用於蓄電裝置 的Al陽極電極的製造方法，上述蓄電裝置包括Al所組成的陽極電極及和該Al為異種金屬的陰極電極而可將以負荷驅動用的馬達產生的電能在短時間充放電，其特徵在於具有：脫脂步驟，將成為延在於Al陽極電極的一端的接續端子部的表面，以有機溶劑脫脂；蝕刻步驟，將以上述脫脂步驟脫脂的上述陽極電極的表面，以蝕刻液蝕刻；Zn鍍敷步驟，反覆以下的處理2次：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鍍敷後，藉由硝酸剝離鋅酸鹽；Ni鍍敷步驟，在以上述Zn鍍敷步驟形成的Zn鍍敷上表面上，以Ni鍍敷液形成Ni鍍敷；及Sn鍍敷步驟，以上述Ni鍍敷步驟形成Ni鍍敷的表面上，以Sn鍍敷液形成Sn鍍敷。
  7. 一種蓄電裝置用電極的接續方法，為用於蓄電裝置的Al陽極電極的接續方法，上述蓄電裝置包括Al所組成的陽極電極及和該Al為異種金屬的陰極電極而可將以負荷驅動用的馬達產生的電能在短時間充放電，其特徵在於：使用銲錫，將Al陽極電極與Cu所組成的陰極電極以焊接接續，其中上述Al陽極電極具有：Zn層或Zn合金層，藉由反覆2次以下的處理的Zn鍍敷步驟而形成：在延在於一端的接續端子部的Al上，以鋅酸鹽液形成Zn鍍敷後，藉由硝酸剝離鋅酸鹽； Ni層，以鍍敷形成於上述Zn層或Zn合金層上；以及Sn層或Sn合金層，以鍍敷形成於上述Ni層上。
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