WO2012102160A1 - 電池端子用接続板および電池端子用接続板の製造方法 - Google Patents
電池端子用接続板および電池端子用接続板の製造方法 Download PDFInfo
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- WO2012102160A1 WO2012102160A1 PCT/JP2012/051046 JP2012051046W WO2012102160A1 WO 2012102160 A1 WO2012102160 A1 WO 2012102160A1 JP 2012051046 W JP2012051046 W JP 2012051046W WO 2012102160 A1 WO2012102160 A1 WO 2012102160A1
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- embedded
- metal
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- hole portion
- hole
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R11/00—Individual connecting elements providing two or more spaced connecting locations for conductive members which are, or may be, thereby interconnected, e.g. end pieces for wires or cables supported by the wire or cable and having means for facilitating electrical connection to some other wire, terminal, or conductive member, blocks of binding posts
- H01R11/11—End pieces or tapping pieces for wires, supported by the wire and for facilitating electrical connection to some other wire, terminal or conductive member
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/507—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing comprising an arrangement of two or more busbars within a container structure, e.g. busbar modules
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/514—Methods for interconnecting adjacent batteries or cells
- H01M50/516—Methods for interconnecting adjacent batteries or cells by welding, soldering or brazing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M50/521—Interconnectors for connecting terminals of adjacent batteries; Interconnectors for connecting cells outside a battery casing characterised by the material
- H01M50/522—Inorganic material
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- 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
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- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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- 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
- Y10T29/49204—Contact or terminal manufacturing
- Y10T29/49224—Contact or terminal manufacturing with coating
Definitions
- the present invention relates to a battery terminal connection plate and a battery terminal connection plate manufacturing method, and more particularly, to a battery terminal connection plate including a first member and a second member and a battery terminal connection plate manufacturing method.
- a battery terminal connection plate including a first member and a second member is known.
- Such a battery terminal connection plate is disclosed in, for example, Japanese Patent Application Laid-Open No. 2002-358945.
- JP-A-2002-358945 discloses a plate-like Al material (first member) including a hole portion into which an external terminal member made of Cu is inserted, and an inner peripheral surface of the Al material hole portion by interference fit.
- positioned in is disclosed.
- the outer peripheral surface of the member is joined by welding.
- connection structure for a lithium secondary cell disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 2002-358945, an annular Cu material (second member) is used as an inner peripheral surface of an Al material (first member) hole. Even if it is arranged by interference fit, when heat is applied to the connection structure, the inner diameter of the hole of the Al material may become larger than the outer diameter of the annular Cu material due to thermal expansion. . In this case, there exists a problem that Cu material may remove
- the present invention has been made to solve the above-described problems, and one object of the present invention is for a battery terminal capable of suppressing the first member and the second member from being separated from each other. It is providing the manufacturing method of a connection board and a connection board for battery terminals.
- a battery terminal connection plate includes a first hole into which a first battery terminal made of a first metal is inserted and an embedded hole, and is made of the same metal as the first metal.
- the first member includes a second hole portion into which a second battery terminal made of a second metal different from the first metal is inserted, and includes a base material made of the same metal as the second metal.
- a second member embedded in the embedded hole portion, and an interface between the embedded hole portion of the first member and the second member is made of an intermetallic compound including at least one of the first metal and the second metal. An intermetallic compound layer is formed.
- the first metal and the second metal is included in the interface between the embedded hole of the first member and the second member.
- the first member and the second member can be joined by the intermetallic compound layer made of the intermetallic compound. Therefore, the second member is simply attached to the first member.
- the bonding strength between the first member and the second member can be increased more than when the first member is embedded. Thereby, it can suppress that a 2nd member remove
- the first terminal made of the same metal as the first metal includes the first hole portion into which the first battery terminal made of the first metal is inserted.
- the first battery terminal and the first member can be joined with a common first metal, and the second battery terminal and the base material of the second member can be joined with a common second metal. it can. Thereby, both the electrical resistance in the joining position of the 1st battery terminal and the 1st member and the electrical resistance in the joining position of the 2nd battery terminal and the substrate of the 2nd member can be made small.
- the first metal is either Al or Cu
- the second metal is either Al or Cu
- the intermetallic compound layer preferably, contains at least Al. If comprised in this way, the joint strength of a 1st member and a 2nd member can be improved with the intermetallic compound containing Al at least.
- the second member is disposed on the surface of the base material and at least at the interface with the first member, and the first metal and the second metal.
- the intermetallic compound of the intermetallic compound layer further includes a coating layer made of a third metal different from that of the first metal and the second member than the intermetallic compound made of the first metal and the second metal. And is made of either the first metal or the second metal and the third metal. If comprised in this way, the joining strength of a 1st member and a 2nd member is given by the intermetallic compound layer comprised from the intermetallic compound which consists of either a 1st metal or a 2nd metal, and a 3rd metal. It can be made even larger.
- the base material of the 1st metal which comprises a 1st member, and the base material of a 2nd member is arrange
- an intermetallic compound having a bonding strength smaller than the intermetallic compound composed of the first metal and the second metal and having either the first metal or the second metal and the third metal is formed in the intermetallic compound layer. The formation can be suppressed.
- the joining strength between the first member and the second member can be further increased, it is possible to effectively suppress the second member from being detached from the first member.
- the third metal is made of a metal that has a higher ionization tendency than either the first metal or the second metal and a lower ionization tendency than either the first metal or the second metal. If comprised in this way, when the 1st metal which comprises a 1st member, and the 2nd metal which comprises the base material of a 2nd member are in direct contact, whichever of a 1st metal or a 2nd metal with a large ionization tendency is large? Even if one of them is corroded (galvanic corrosion), the ionization tendency is greater than either the first metal or the second metal, and the ionization tendency is greater than either the first metal or the second metal.
- the first metal is either Al or Cu
- the second metal is The other metal is Al or Cu
- the third metal is Ni
- the intermetallic compound of the intermetallic compound layer is made of Al and Ni. If comprised in this way, the joint strength of a 1st member and a 2nd member can be further enlarged according to the intermetallic compound layer comprised from the intermetallic compound which consists of Al and Ni.
- the coating layer made of Ni on the surface of the base material and at least at the interface with the first member, it is possible to suppress the reaction between Al and Cu, and there is an ionization tendency. Corrosion of large Al can be suppressed.
- the first member and the second member are made of a rectangular plate material having long sides and short sides extending in the same direction in plan view, and the length of the second member.
- the side and the short side are shorter than the long side and the short side of the first member, respectively.
- the embedded hole portion of the first member has a circular shape when seen in a plan view
- the second member is a cylinder having the second hole portion. It has a shape. According to this configuration, compared with the case where the plate-like second member is embedded (press-fitted) into the rectangular embedded hole, the second hole is applied to the embedded hole with the force applied to the second member evenly. Since the two members can be embedded (press-fit), uniform and high bonding strength can be obtained in the entire bonding portion between the embedded hole and the second member.
- the second member has a truncated cone shape having a second hole portion
- the embedded hole portion of the first member is a cone of the second member. It has a shape corresponding to a trapezoidal shape.
- the second hole is applied to the embedded hole with the force applied to the second member evenly. Since the two members can be embedded (press-fit), uniform and high bonding strength can be obtained in the entire bonding portion between the embedded hole and the second member.
- the opening width of the embedded hole portion of the first member is configured to change from one surface of the first member to the other surface.
- the second member can be more easily embedded in the embedded hole than in the case where the opening width of the embedded hole is substantially constant from one surface of the first member to the other surface.
- the embedded second member can be more difficult to be removed from the embedded hole.
- the opening width of the embedding hole portion of the first member is configured to gradually decrease from one surface of the first member toward the other surface. If comprised in this way, a 2nd member can be easily embedded to an embedding hole part from the one surface of the 1st member with the largest opening width of an embedding hole part. Moreover, it can suppress effectively that the embedded 2nd member remove
- the opening width of the embedded hole portion of the first member is substantially equal to the thickness direction of the first member from the one surface and the other surface of the first member. It is comprised so that it may become small toward the center. If comprised in this way, it can suppress that a 2nd member moves to the thickness direction by latching the embedded 2nd member in the approximate center of the inner surface of an embedding hole part. Thereby, it can suppress effectively that a 2nd member remove
- the embedded hole portion of the first member has a substantially circular shape when viewed in plan, and the second member has a cylindrical shape.
- a threaded portion is formed on the outer surface in contact with the embedded hole portion of the second member, and the threaded portion of the second member is screwed into the inner surface of the embedded hole portion of the first member. Is embedded as such. If comprised in this way, compared with the case where a 2nd member is simply embedded in the embedding hole part of a 1st member, a 2nd member can be embedded more firmly in the embedding hole part of a 1st member. Thereby, since the joint strength between the first member and the second member can be further increased, it is possible to more effectively suppress the second member from being detached from the first member.
- the manufacturing method of the battery terminal connection plate includes a first hole portion into which the first battery terminal made of the first metal is inserted, and a base material made of the second metal different from the first metal.
- a step of providing in the first member made of the same metal as the first metal, a step of embedding the second member in the embedded hole portion of the first member, and a second metal A step of providing the second member with a second hole into which the second battery terminal made of the same metal is inserted, and diffusion annealing, so that the interface between the buried hole of the first member and the second member is Forming an intermetallic compound layer made of an intermetallic compound containing at least one of the first metal and the second metal.
- the first metal and the second metal are formed at the interface between the buried hole portion of the first member and the second member by diffusion annealing.
- the second battery terminal and the base member of the second member can be joined with a common second metal.
- the step of providing the second hole portion in the second member is performed after the step of embedding the second member in the embedded hole portion of the first member. Is called.
- the first member is formed on at least the outer surface of the base material of the second member before the step of embedding the second member in the embedding hole of the first member.
- the method further includes the step of forming a coating layer on at least the outer surface of the substrate by plating with a third metal different from the first metal and the second metal, and the step of forming the intermetallic compound layer is diffusion annealed.
- the bonding strength between the first member and the second member is larger than the intermetallic compound composed of the first metal and the second metal, and either the first metal or the second metal and the third metal Forming an intermetallic compound layer composed of an intermetallic compound formed at the interface between the embedding hole of the first member and the outer surface of the second member. If comprised in this way, the joint strength of a 1st member and a 2nd member can further be enlarged with the intermetallic compound which consists of either a 1st metal or a 2nd metal, and a 3rd metal.
- a metal comprising a step of forming a coating layer made of the third metal on at least the outer surface of the base material, and an intermetallic compound made of either the first metal or the second metal and the third metal Forming the intermetallic compound layer at the interface between the embedding hole of the first member and the outer surface of the second member, thereby forming the first metal constituting the first member and the base material of the second member It is possible to suppress the reaction with the second metal. Thereby, an intermetallic compound having a bonding strength smaller than the intermetallic compound composed of the first metal and the second metal and having either the first metal or the second metal and the third metal is formed in the intermetallic compound layer. The formation can be suppressed. As a result, since the joining strength between the first member and the second member can be further increased, it is possible to effectively suppress the second member from being detached from the first member.
- the second member in the step of embedding the second member in the embedded hole portion of the first member, the second member is disposed above the embedded hole portion of the first member. In this state, by applying pressure to the second member from above, the step of pressing the second member into the embedded hole of the first member is included. With this configuration, the second member can be easily embedded in the embedded hole.
- the step of providing the first hole portion and the embedded hole portion in the first member is such that the embedded hole portion is substantially circular in plan view.
- the step of providing the embedded hole portion in the first member, and the step of embedding the second member in the embedded hole portion of the first member has a cylindrical shape and has a thread portion formed on the outer surface.
- a step of embedding the second member in the embedding hole portion of the first member by screwing the inner surface of the embedding hole portion of the first member while rotating the member is included.
- a 2nd member can be embedded more firmly in the embedding hole part of a 1st member. Therefore, since the joint strength between the first member and the second member can be further increased, it is possible to more effectively suppress the second member from being detached from the first member.
- the method further includes the step of preparing a second member having a columnar shape having the first diameter, and the first hole and the embedded hole are provided with the first hole and the embedded hole.
- the step of providing the first member includes a step of forming the embedded hole portion of the first member into a circular shape having a second diameter smaller than the first diameter of the second member, and the second hole is formed in the embedded hole portion of the first member.
- the step of embedding the member includes a step of press-fitting the second member into the embedding hole of the first member.
- the second member is firmly embedded in the embedded hole portion of the first member by press-fitting the second member into the embedded hole portion having the second diameter smaller than the first diameter of the second member. be able to.
- the joint strength between the first member and the second member can be further increased, it is possible to more effectively suppress the second member from being detached from the first member.
- the second member can be press-fitted into the embedding hole with the force applied to the second member evenly.
- uniform and high bonding strength can be obtained over the entire bonding portion between the embedded hole and the second member.
- the step of forming the embedding hole portion of the first member in a circular shape having the second diameter is formed so that the second diameter is smaller than the first diameter by 0.2 mm or more and 1.0 mm or less.
- the process of carrying out If comprised in this way, a 2nd member can be more firmly embedded to the embedding hole part of a 1st member by making a 2nd diameter only 0.2 mm or more smaller than a 1st diameter. Further, by making the second diameter smaller by 1.0 mm or less than the first diameter, the second member is excessively enlarged, so that the second member can be embedded in the embedded hole portion of the first member. It can suppress becoming difficult.
- the second member having a truncated cone shape having one surface having a third diameter and the other surface having a fourth diameter smaller than the third diameter.
- the step of providing the first hole and the embedded hole in the first member includes a step of providing the embedded hole of the first member with a fifth diameter smaller than the third diameter of the one surface of the second member.
- the second member is press-fitted into the embedded hole portion having the fifth diameter smaller than the third diameter of the one surface of the second member, so that the first member is more firmly inserted into the embedded hole portion of the first member.
- Two members can be embedded. Thereby, since the joint strength between the first member and the second member can be further increased, it is possible to more effectively suppress the second member from being detached from the first member. Further, by pressing the second member into the embedding hole portion of the first member from the other surface side of the second member, compared with the case of pressing from the one surface side having a third diameter larger than the fourth diameter of the other surface. Thus, the second member can be more easily press-fitted into the embedded hole portion of the first member.
- the second member can be prevented from being detached from the first member, and the first member and the second member are loosened due to loose bonding between the first member and the second member.
- An increase in electrical resistance at the interface with the second member can be suppressed.
- FIG. 3 is a cross-sectional view taken along line 800-800 in FIG.
- FIG. 8 is a cross-sectional view taken along line 810-810 in FIG. It is the expanded sectional view which showed the joining state of Al member and embedding member by 1st Embodiment of this invention.
- FIG. 8 is a cross-sectional view taken along line 820-820 in FIG.
- FIG. 8 is a sectional view taken along line 830-830 in FIG.
- FIG. 12 is a cross-sectional view taken along line 840-840 in FIG. It is sectional drawing for demonstrating the manufacturing process of the bus-bar by 4th Embodiment of this invention.
- the lithium-ion battery connector 100 is a large battery system used for an electric vehicle (EV), a hybrid vehicle (HEV), a hybrid electric vehicle, a residential power storage system, and the like. As shown in FIG. 1, the lithium ion battery connector 100 is configured by electrically connecting a plurality of lithium ion batteries 1 by a plurality of bus bars 2.
- the bus bar 2 is an example of the “battery terminal connection plate” in the present invention.
- the lithium ion battery 1 includes a positive electrode side terminal 1a made of Al and a negative electrode side terminal 1b made of Cu. Both the positive electrode side terminal 1a and the negative electrode side terminal 1b have a cylindrical portion having a diameter L1 of about 4.8 mm and extending in the Z direction.
- the positive electrode side terminal 1a is an example of the “first battery terminal” in the present invention
- the negative electrode side terminal 1b is an example of the “second battery terminal” in the present invention.
- Al is an example of the “first metal” in the present invention
- Cu is an example of the “second metal” in the present invention.
- each positive electrode side terminal 1a in the three lithium ion batteries 1 and each negative electrode side terminal 1b in the three lithium ion batteries 1 adjacent on one side are electrically connected by one bus bar 2. .
- each negative electrode side terminal 1b in the three lithium ion batteries 1 and each positive electrode side terminal 1a in the three lithium ion batteries 1 adjacent on the other side are electrically connected by one bus bar 2. .
- the three lithium ion batteries 1 are connected in parallel, and each of the three lithium ion batteries 1 connected in parallel is connected in series.
- the bus bar 2 has a long side extending in the X direction and a short side extending in the Y direction, and is formed of a plate-like member formed in a rectangular shape when viewed from above (Z1 side).
- the bus bar 2 includes an Al member 3 made of the same metal (Al) as the positive electrode side terminal 1 a and an embedded member 4.
- the bus bar 2 has a width W1 of about 50 mm in the direction orthogonal to the X direction (Y direction) and a thickness t1 of about 3 mm in the thickness direction (Z direction).
- the Al member 3 and the embedded member 4 are examples of the “first member” and the “second member” in the present invention, respectively.
- the Al member 3 has a long side extending in the X direction and a short side extending in the Y direction, and is made of a plate-like member formed in a rectangular shape when viewed from above (Z1 side).
- the Al member 3 is formed with three holes 30 into which the positive terminals 1a of the lithium ion battery 1 are inserted, and an embedded hole 31 into which the embedded member 4 is press-fitted.
- the three holes 30 are arranged at substantially equal intervals in the X direction at a substantially central portion in the Y direction of the Al member 3. As shown in FIG. 3, the hole 30 is configured to penetrate the Al member 3 in the thickness direction (Z direction) and has a diameter L2 of about 5 mm.
- the hole 30 is an example of the “first hole” in the present invention.
- the embedded hole portion 31 is formed so that the center in the Y direction is located approximately at the center in the Y direction of the Al member 3. Further, the embedded hole portion 31 is provided only around the hole portion 42 described later into which the negative electrode side terminal 1b is inserted. That is, as viewed from above (Z1 side), the area of the region where the embedded hole 31 is formed is configured to be smaller than the area other than the embedded hole 31 of the Al member 3.
- the opening end 31a of the embedded hole 31 on the upper surface 3a side of the Al member 3 is formed in a rectangular shape when viewed in plan (from the upper side (Z1 side)), and the lower surface 3b of the Al member 3
- the open end 31b of the embedded hole 31 on the side is formed in a rectangular shape substantially the same as the open end 31a of the embedded hole 31 when viewed in plan (from the lower side (Z2 side)).
- the embedded hole 31 has an opening width W2 in the Y direction, and the opening width W2 extends along the thickness direction (Z direction) from the opening end 31a to the opening end 31b. It is configured to have a uniform width.
- the upper surface 3a and the lower surface 3b are examples of the “one surface” and the “other surface” in the present invention, respectively.
- the embedded member 4 is press-fitted into the embedded hole portion 31 of the Al member 3 along the inner side surface 31 c of the embedded hole portion 31.
- the embedded member 4 has a long side extending in the X direction and a short side extending in the Y direction, and has a plate shape formed in a rectangular shape when viewed from above (Z1 side). It consists of members.
- the long side of the embedded member 4 is formed so as to extend in the same direction (X direction) as the long side of the Al member 3 (bus bar 2), and is shorter than the long side of the Al member 3. It is configured.
- the short side of the embedded member 4 is formed to extend in the same direction (Y direction) as the short side of the Al member 3 and is configured to be shorter than the short side of the Al member 3. Yes. Further, as viewed from above, the area of the region where the embedded hole 31 is formed is configured to be smaller than the area of the Al member 3, so that the volume of the Al member 3 (the volume occupied by Al) is The volume of the embedded member 4 (the volume occupied by Cu) is larger.
- the embedding member 4 is composed of a base material 40 made of the same metal (Cu) as the negative electrode side terminal 1b and a Ni plating layer 41 made of Ni.
- the Ni plating layer 41 is an example of the “coating layer” in the present invention, and Ni is an example of the “third metal” in the present invention.
- three holes 42 into which the negative electrode side terminals 1b of the lithium ion battery 1 are respectively inserted are formed in the base material 40.
- the three hole portions 42 are arranged at substantially equal intervals in the X direction at a substantially central portion in the Y direction of the base material 40.
- the hole 42 is configured to penetrate the base material 40 in the thickness direction (Z direction), and the diameter L2 (about 5 mm) of the hole 30 of the Al member 3. Have substantially the same diameter.
- the hole 42 is an example of the “second hole” in the present invention.
- the Ni plating layer 41 of the embedded member 4 is formed on substantially the entire surface of the base material 40 on the upper surface 40a, the lower surface 40b, and the outer surface 40c. That is, the Ni plating layer 41 is formed on the outer surface 40 c of the base material 40 located at the interface with the inner surface 31 c of the Al member 3. Thus, the Ni plating layer 41 is configured to suppress the reaction between Cu constituting the base material 40 and Al constituting the Al member 3. On the other hand, the Ni plating layer 41 is not formed on the inner peripheral surface of the hole 42 of the base material 40.
- the Ni plating layer 41 has a thickness t2 of about 3 ⁇ m or more and about 10 ⁇ m or less.
- the upper surface 4 a and the lower surface 4 b of the embedded member 4 are configured to be substantially flush with the upper surface 3 a and the lower surface 3 b of the Al member 3, respectively, in a state where the embedded member 4 is embedded in the embedded hole 31. Yes.
- the interface between the inner side surface 31 c of the embedded hole portion 31 and the Ni plating layer 41 formed on the outer side surface 40 c of the base member 40 of the embedded member 4 is The intermetallic compound layer 5 is formed.
- This intermetallic compound layer 5 is mainly composed of an Al—Ni intermetallic compound formed by a reaction between Al constituting the Al member 3 and Ni constituting the Ni plating layer 41. Specifically, the Al constituting the Al member 3 and the Ni constituting the Ni plating layer 41 are chemically bonded at a predetermined ratio so as to form a fixed crystal structure, whereby the embedded hole 31 is formed.
- An intermetallic compound layer 5 mainly made of an Al—Ni intermetallic compound is formed at the interface between the inner side surface 31 c of the metal and the Ni plating layer 41 of the embedded member 4.
- the Al member 3 and the embedded member 4 are joined by the chemical bond between Al and Ni.
- the Al—Ni intermetallic compound of the intermetallic compound layer 5 is more Al than the Al—Cu intermetallic compound formed by the reaction of Al of the Al member 3 and Cu of the base material 40 of the embedded member 4. The bonding strength between the member 3 and the embedded member 4 is increased.
- the intermetallic compound layer 5 has a thickness t3 of about 1 ⁇ m to about 5 ⁇ m.
- Ni in the Ni plating layer 41 has a smaller ionization tendency than Al in the Al member 3, but has a larger ionization tendency than Cu in the base material 40 of the embedded member 4.
- the positive electrode side terminal 1a inserted in the hole 30 and the Al member 3 are joined to each other through a welded portion 6 made of Al formed by laser welding.
- the positive electrode side terminal 1a and the hole 30 of the Al member 3 are joined together by the same metal (Al).
- the welded portion 6 is formed to have a thickness of about 0.1 mm between the diameter L1 (about 4.8 mm) of the positive electrode side terminal 1a and the diameter L2 (about 5 mm) of the hole portion 30.
- the welded portion 6 is provided up to the vicinity of the center in the Z direction in the hole portion 30.
- the negative electrode side terminal 1b inserted into the hole 42 and the base material 40 of the embedded member 4 are joined to each other via a welded portion 7 made of Cu formed by laser welding. Yes.
- the negative electrode side terminal 1b and the base material 40 of the embedding member 4 are mutually joined by the same metal (Cu).
- the welded portion 7 is formed to have a thickness of about 0.1 mm between the diameter L1 (about 4.8 mm) of the negative electrode side terminal 1b and the diameter L2 (about 5 mm) of the hole portion 42. .
- the welded portion 7 is provided up to the vicinity of the center of the hole portion 42 in the Z direction.
- an Al plate (not shown) having a thickness t1 (see FIGS. 3 and 4) of about 3 mm and made of Al is prepared. 2 and 3, three holes 30 having a diameter L2 of about 5 mm (see FIG. 3) at a predetermined position substantially in the center in the width direction (Y direction) of the Al plate, and Y A buried hole portion 31 having an opening width W2 in the direction is formed. Thereby, the Al member 3 is formed.
- a base material 40 having a thickness t1 of about 3 mm and made of Cu is prepared. Then, a plating process is performed on the surface of the substrate 40 using Ni. Thereby, the Ni plating layer 41 having a thickness t2 of about 3 ⁇ m or more and about 10 ⁇ m or less is formed on the upper surface 40a, the lower surface 40b, and the outer surface 40c of the substrate 40. As a result, the embedded member 4 in which the hole 42 is not formed is formed.
- the embedded member 4 is formed to be slightly larger than the opening width W2 of the opening end 31a (31b) of the embedded hole 31 in the Y direction.
- the embedded member 4 is placed on the upper surface 3 a of the Al member 3 so as to cover the embedded hole 31 of the Al member 3 when viewed in plan (viewed from the upper side (Z1 side)). Deploy. Then, using the press machine 101, the embedded member 4 is pressed from above (Z1 side). As a result, as shown in FIG. 4, the embedded member 4 is embedded in the embedded hole 31 so that the upper surface 4a and the lower surface 4b of the embedded member 4 are substantially flush with the upper surface 3a and the lower surface 3b of the Al member 3, respectively. Press fit.
- the embedded member 4 formed slightly larger than the opening width W2 of the opening end 31a (31b) of the embedded hole 31 is embedded in the embedded hole 31 in a compressed state. Thereby, it is suppressed that the embedding member 4 remove
- the positive electrode side terminal 1 a of the lithium ion battery 1 is inserted into each of the three holes 30 of the Al member 3.
- laser welding is performed using a laser beam having a wavelength of about 1064 nm emitted from a laser welder (not shown).
- the positive electrode side terminal 1a and the Al member 3 are joined mutually.
- the negative electrode side terminal 1 b of the lithium ion battery 1 is inserted into each of the three hole portions 42 of the embedded member 4.
- laser welding is performed using a laser beam having a wavelength of about 1064 nm.
- a welded portion 7 made of Cu is formed, and the negative electrode side terminal 1 b and the embedded member 4 are joined to each other.
- the positive terminal 1a of the three lithium ion batteries 1 and the negative terminal 1b of the three lithium ion batteries 1 are electrically connected.
- each of the three lithium ion batteries 1 is connected in series using a plurality of bus bars 2 as a unit. In this way, the lithium ion battery connector 100 shown in FIG. 1 is manufactured.
- the embedded member 4 is simply more than the case where the embedded member 4 is embedded in the Al member 3. Further, the bonding strength between the Al member 3 and the embedded member 4 can be further increased.
- the Al member 3 is provided with the three holes 30 into which the positive electrode side terminals 1a of the lithium ion battery 1 are respectively inserted, and the base member 40 of the embedded member 4 is provided with
- the positive electrode side terminal 1a and the Al member 3 can be joined with common Al, and the negative electrode side terminal 1b.
- the base material 40 of the embedding member 4 can be joined with common Cu.
- the Ni plating layer 41 is formed on the upper surface 40a, the lower surface 40b, and the outer surface 40c of the base material 40, thereby embedding Al constituting the Al member 3. It can suppress that Cu which comprises the base material 40 of the member 4 reacts. As a result, it is possible to suppress the formation of an Al—Cu intermetallic compound composed of Al and Cu and having a bonding strength lower than that of the Al—Ni intermetallic compound in the intermetallic compound layer 5. As a result, the bonding strength between the Al member 3 and the embedded member 4 can be further increased.
- Ni plating layer 41 can prevent the base material 40 made of Cu from corroding in a normal environment (such as in the air).
- the upper surface 4a and the lower surface 4b of the embedded member 4 are placed on the upper surface 3a and the lower surface 3b of the Al member 3 with the embedded member 4 embedded in the embedded hole portion 31, respectively. Since the embedded member 4 does not protrude from the embedded hole portion 31 of the Al member 3, the embedded member 4 is detached from the Al member 3 due to the protruding embedded member 4 portion. (Peeling) can be suppressed. Moreover, since the embedded member 4 is embedded in the embedded hole portion 31 of the Al member 3 so as to be substantially flush with each other, the embedded member 4 is positioned over the entire embedded hole portion 31 of the Al member 3. The intermetallic compound layer 5 can be formed over the entire embedded hole 31 of the Al member 3. As a result, sufficient bonding strength between the Al member 3 and the embedded member 4 can be ensured, so that the embedded member 4 can be further prevented from being unexpectedly separated from the Al member 3.
- the long side of the embedded member 4 extends in the same direction (X direction) as the long side of the Al member 3 (bus bar 2), and from the long side of the Al member 3
- the short side of the embedded member 4 extends in the same direction (Y direction) as the short side of the Al member 3 and is shorter than the short side of the Al member 3.
- the embedded member 4 can be easily embedded in the embedded hole 31 of the Al member 3, and the long side of the embedded member 4 can be sufficiently secured.
- the hole 42 can be easily formed at an appropriate position.
- the three hole portions 42 are arranged at substantially the same center in the Y direction of the base material 40 so as to be arranged at substantially equal intervals in the X direction.
- a plurality of lithium ion batteries 1 having the negative electrode side terminal 1 b can be connected to the battery 2. Further, by forming the three hole portions 42 along the direction in which the long side of the embedded member 4 extends (X direction), compared to the case of forming the three hole portions 42 in the direction in which the short side extends (Y direction). Thus, the three holes 42 can be easily formed.
- the volume of the embedded member 4 (the volume occupied by Cu) is configured to be smaller than the volume of the Al member 3 (the volume occupied by Al), so that the volume of the embedded member 4 is smaller than that of Al. Even when the embedded member 4 is configured using Cu having a large specific gravity (density), the weight of the bus bar 2 excessively increases because the volume of the embedded member 4 is smaller than the volume of the Al member 3 made of Al. This can be suppressed.
- the Ni plating layer 41 of the embedding member 4 is formed on substantially the entire surface of the upper surface 40a, the lower surface 40b, and the outer surface 40c of the substrate 40, thereby forming the substrate.
- the base material 40 is prevented from corroding from the exposed portions of the upper surface 40a and the lower surface 40b that are not covered. it can.
- the Ni plating layer 41 is formed on substantially the entire outer surface 40 c of the base material 40, Al— over the substantially entire outer surface 40 c of the base material 40 disposed in the embedded hole 31 of the Al member 3.
- An intermetallic compound layer 5 mainly composed of Ni intermetallic compounds can be formed. As a result, a sufficient bonding strength between the Al member 3 and the embedded member 4 can be ensured, so that the embedded member 4 can be effectively prevented from peeling off from the Al member 3 unexpectedly.
- the Ni plating layer 41 has the thickness t2 of about 3 ⁇ m or more and about 10 ⁇ m or less, so that the thickness t2 of the Ni plating layer 41 is about 3 ⁇ m or more, so that the Al member 3 and Cu of the base material 40 can be sufficiently prevented from reacting with each other. Further, by setting the thickness t2 of the Ni plating layer 41 to about 10 ⁇ m or less, it is possible to suppress an increase in the time required to form the Ni plating layer 41.
- the embedding member 4 is press-fitted into the embedding hole 31, and then the three holes 42 are formed in the embedding member 4, whereby the three holes 42 are formed in the embedding member 4.
- the shapes (diameters, etc.) of the three hole portions 42 change. Can be prevented.
- the embedding member 4 is disposed on the upper surface 3a of the Al member 3 so as to cover the embedding hole 31 of the Al member 3, and then the embedding member is used using the press 101. By pressing 4 from above and press-fitting the embedded member 4 into the embedded hole 31, the embedded member 4 can be easily embedded in the embedded hole 31.
- the embedded member 4 including the base material 40 made of Cu is embedded in the embedded hole portion 31 of the Al member 3 made of Al, and Al
- the first member made of Cu is made of a base made of Al.
- the bus bar 2 can be manufactured at low cost.
- the opening width of the embedded hole portion 231 of the Al member 203 in the bus bar 202 gradually decreases from the upper surface 3a to the lower surface 3b of the Al member 203.
- the bus bar 202 is an example of the “battery terminal connection plate” in the present invention
- the Al member 203 is an example of the “first member” in the present invention.
- the embedded hole portion 231 of the Al member 203 in the bus bar 202 according to the second embodiment of the present invention gradually decreases in opening width from the upper surface 3 a to the lower surface 3 b of the Al member 203 in the Y direction. It is comprised so that it may become.
- the opening width W3 at the opening end 231a on the upper surface 3a side of the embedded hole 231 is the largest among the opening widths of the embedded hole 231, while the opening width W4 at the opening end 231b on the lower surface 3b side is The opening width of the embedded hole 231 is configured to be the smallest.
- the inner side surface 231c of the embedded hole 231 is formed so as to be gradually inclined toward the center of the embedded hole 231 from the open end 231a toward the open end 231b.
- the embedded member 204 is press-fitted into the embedded hole portion 231 of the Al member 203 along the inclined inner surface 231c of the embedded hole portion 231.
- the embedding member 204 is configured to be deformed so as to conform to the shape of the embedding hole 231 when being pressed into the embedding hole 231. That is, the outer surface 240c of the base member 240 of the embedding member 204 is located on the center side of the embedding member 204 from the end of the upper surface 40a toward the end of the lower surface 40b along the inner surface 231c of the embedding hole 231. It is formed so as to be gradually inclined.
- the embedded member 204 is an example of the “second member” in the present invention.
- the Ni plating layer 41 is formed on the upper surface 40a, the lower surface 40b, and the outer surface 240c of the base member 240 of the embedded member 204. Further, the interface between the inner side surface 231c of the embedding hole 231 and the Ni plating layer 41 formed on the outer side surface 240c of the base member 240 of the embedding member 204 is mainly composed of an Al—Ni intermetallic compound. An intermetallic compound layer 5 is formed.
- the other structure of 2nd Embodiment of this invention is the same as that of the said 1st Embodiment.
- the opening width of the embedded hole 231 of the Al member 203 is formed so as to gradually decrease from the upper surface 3a to the lower surface 3b of the Al member 203. Except for this point, the second embodiment is the same as the first embodiment.
- the intermetallic compound layer 5 made of an Al—Ni intermetallic compound, it is possible to effectively prevent the embedded member 204 from coming off the Al member 203.
- the bonding strength between the Al member 203 and the embedded member 204 can be increased, the electrical connection at the interface between the Al member 203 and the embedded member 204 is caused by loosening of the bonding between the Al member 203 and the embedded member 204. An increase in resistance can be suppressed.
- the embedded hole portion 231 of the Al member 203 is configured such that the opening width gradually decreases from the upper surface 3a to the lower surface 3b of the Al member 203 in the Y direction.
- the embedding member 204 can be easily embedded into the embedding hole 231 from the opening end 231a. Moreover, it can suppress effectively that the embedded embedding member 204 remove
- the remaining effects of the second embodiment are similar to those of the aforementioned first embodiment.
- the opening width of the embedded hole portion 331 of the Al member 303 in the bus bar 302 is gradually increased from the opening ends 331a and 331b toward the central portion 331d of the embedded hole portion 331. The case where it becomes smaller will be described.
- the bus bar 302 is an example of the “battery terminal connection plate” in the present invention
- the Al member 303 is an example of the “first member” in the present invention.
- the embedded hole portion 331 of the Al member 303 in the bus bar 302 of the third embodiment of the present invention has a central portion 331d of the embedded hole portion 331 from the upper surface 3a and the lower surface 3b of the Al member 303 in the Y direction.
- the opening width W6 in the central portion 331d of the embedded hole portion 331 is configured to be the smallest among the opening widths of the embedded hole portion 331. Furthermore, the inner side surface 331c of the embedded hole 331 is formed so as to be gradually inclined toward the center of the embedded hole 331 from the opening ends 331a and 331b toward the central part 331d.
- the embedded member 304 is press-fitted into the embedded hole 331 of the Al member 303 so as to follow the inclined inner surface 331c of the embedded hole 331.
- the embedding member 304 is configured to be deformed so as to conform to the shape of the embedding hole 331 when being pressed into the embedding hole 331.
- the outer surface 340c of the base member 340 of the embedding member 304 is located approximately at the center in the thickness direction (Z direction) from the end of the upper surface 40a and the end of the lower surface 40b along the inner surface 331c of the embedding hole 331. It is formed so as to gradually incline toward the center side of the embedded member 304.
- the embedded member 304 is an example of the “second member” in the present invention.
- the Ni plating layer 41 is formed on the upper surface 40a, the lower surface 40b, and the outer surface 340c of the base member 340 of the embedded member 304.
- the interface between the inner side surface 331c of the embedded hole 331 and the Ni plating layer 41 formed on the outer side surface 340c of the base member 340 of the embedded member 304 is mainly composed of an Al—Ni intermetallic compound.
- An intermetallic compound layer 5 is formed.
- the opening width of the embedded hole portion 331 of the Al member 303 is changed from the upper surface 3a and the lower surface 3b of the Al member 303 toward the central portion 331d of the embedded hole portion 331.
- the first embodiment is the same as the first embodiment except that it is formed so as to gradually become smaller.
- the intermetallic compound layer 5 made of an Al—Ni intermetallic compound, it is possible to effectively prevent the embedded member 304 from coming off the Al member 303.
- the bonding strength between the Al member 303 and the embedded member 304 can be increased, the electrical connection at the interface between the Al member 303 and the embedded member 304 is caused by loosening of the bonding between the Al member 303 and the embedded member 304. An increase in resistance can be suppressed.
- the opening width of the embedded hole portion 331 of the Al member 303 gradually increases from the upper surface 3a of the Al member 303 toward the central portion 331d of the embedded hole portion 331 in the Y direction.
- the embedded embedded member 304 is locked to the central portion 331d of the inner side surface 331c of the embedded hole portion 331.
- the remaining effects of the third embodiment are similar to those of the aforementioned first embodiment.
- three embedded hole portions 431 are formed at a predetermined interval in the X direction. Further, as shown in FIG. 12, the embedded hole 431 is formed in a circular shape having a diameter D1 when seen in a plan view. In addition, three embedded holes 431 are provided so as to correspond to the three holes 42 (see FIG. 11) into which the negative electrode side terminal 1b is inserted.
- a cylindrical embedding member 404 having the hole portion 42 is embedded by press-fitting.
- An Ni plating layer 41 is formed on the upper surface 40a, the lower surface 40b, and the outer surface 440c of the base member 440 of the embedded member 404.
- the interface between the inner side surface 431c of the embedded hole portion 431 and the Ni plating layer 41 formed on the outer side surface 440c of the base member 440 of the embedded member 404 is mainly composed of an Al—Ni intermetallic compound.
- An intermetallic compound layer 5 is formed.
- an Al plate (not shown) is prepared. Then, as shown in FIG. 11, three holes 30 and a diameter D2 (see FIG. 13) slightly smaller than the diameter D1 (see FIG. 12) at a predetermined position substantially in the center in the width direction (Y direction) of the Al plate. Three embedded holes 431 having a reference) are formed. Thereby, the Al member 403 is formed. Further, as shown in FIG. 13, three columnar base materials 440 having a diameter D3 and made of Cu are prepared. Then, a plating process is performed on the surface of the base material 440 using Ni. Thereby, the Ni plating layer 41 is formed on the upper surface 40a, the lower surface 40b, and the outer surface 440c of the base material 440.
- a columnar embedded member 404 having a diameter D3 is formed. Thereafter, the hole 42 is formed in the embedded member 404.
- the diameter D2 and the diameter D3 are examples of the “second diameter” and the “first diameter” in the present invention, respectively.
- the diameter D2 of the embedded hole 431 is formed to be smaller than the diameter D3 of the embedded member 404 by 0.2 mm or more and 1.0 mm or less.
- the press member 101 is used to press-fit the embedded members 404 in which the hole portions 42 are formed into the three embedded hole portions 431 of the Al member 403, respectively.
- the embedded member 404 having a diameter D3 larger by 0.2 mm or more and 1.0 mm or less than the diameter D2 of the embedded hole 431 is embedded in the embedded hole 431, whereby the embedded hole 431 is expanded.
- the diameter of the embedded hole 431 becomes a diameter D1 (see FIG. 12) slightly larger than the diameter D2.
- an intermetallic compound layer 5 (see FIG. 12) mainly composed of an Al—Ni intermetallic compound at the interface between the Ni plating layer 41 and the inner side surface 431c. Thereby, the bus bar 402 shown in FIG. 11 is manufactured.
- an Al—Ni metal is formed at the interface between the inner surface 431 c of the embedded hole 431 of the Al member 403 and the Ni plating layer 41 formed on the outer surface 440 c of the embedded member 404.
- the intermetallic compound layer 5 made of an intermetallic compound, it is possible to effectively suppress the embedded member 404 from coming off the Al member 403.
- the bonding strength between the Al member 403 and the embedded member 404 can be increased, the electrical connection at the interface between the Al member 403 and the embedded member 404 is caused by loosening of the bonding between the Al member 403 and the embedded member 404. An increase in resistance can be suppressed.
- the embedded hole portion 431 has a circular shape when seen in a plan view, and the embedded member 404 has a cylindrical shape having the hole portion 42, so that the rectangular embedded hole is formed.
- the embedding member 404 can be press-fitted into the embedding hole portion 431 with a force applied to the embedding member 404 evenly. A uniform and large joint strength can be obtained in the entire joint portion with the member 404.
- the diameter D2 of the embedding hole 431 is formed to be smaller than the diameter D3 of the embedding member 404 by 0.2 mm or more and 1.0 mm or less.
- the embedded member 404 can be more firmly embedded in the embedded hole 431 of the Al member 403 by embedding the embedded member 404 in the embedded hole 431 having a diameter D2 that is as small as 0.2 mm or more.
- the opening end 531a on the upper surface 3a side is formed in a circular shape having a diameter D4
- An opening end 531b on the lower surface 3b side is formed in a circular shape having a diameter D5 smaller than the diameter D4.
- the inner side surface 531c of the embedded hole 531 is formed so as to be gradually inclined from the opening end 531a toward the opening end 531b.
- a truncated cone-shaped embedded member 504 having a hole 42 is embedded in the embedded hole 531 of the Al member 503 by press-fitting. That is, the embedded member 504 is formed in a truncated cone shape in which the upper surface 504a has a circular shape with a diameter D4 and the lower surface 504b has a circular shape with a diameter D5 smaller than the diameter D4. As a result, the embedding hole 531 is formed to have a shape corresponding to the frustoconical embedding member 504.
- the upper surface 504a and the lower surface 504b are examples of the “one surface” and the “other surface” in the present invention, respectively.
- the remaining structure of the first modification of the fourth embodiment of the present invention is similar to that of the aforementioned fourth embodiment.
- a base material 540 made of Cu and having a truncated cone shape is prepared. Specifically, the upper surface 504a (Z1 side surface) of the substrate 540 is formed in a circular shape having a diameter D6 larger than the diameter D4 (see FIG. 14), and the lower surface 504b (Z2 side surface) is formed. , Formed in a circular shape having a diameter D7 that is smaller by about 0.2 mm than the diameter D6. The diameter D7 is larger than the diameter D5 (see FIG. 14).
- the base material 540 is configured so that the diameter gradually decreases from the Z1 side toward the Z2 side.
- the frustoconical embedded member 504 is formed on the surface of the frustoconical base material 540 by plating using Ni. Thereafter, the hole 42 is formed in the embedded member 504.
- the diameter D2, the diameter D6, and the diameter D7 are examples of the “fifth diameter”, “third diameter”, and “fourth diameter” of the present invention, respectively.
- the diameter D2 of the embedding hole 531 is made smaller by 0.2 mm or more and 1.0 mm or less than the diameter D6 of the upper surface 504a of the embedding member 504.
- the diameter D2 of the embedded hole 531 is formed to be slightly smaller than the diameter D7 of the lower surface 504b of the embedded member 504.
- the embedded member 504 is disposed on the upper surface 3a of the Al member 503 so that the lower surface 504b of the embedded member 504 and the embedded hole 531 of the Al member 503 face each other. Then, the embedded member 504 is press-fitted into the embedded hole portion 531 of the Al member 503 from the lower surface 504 b side of the embedded member 504. At this time, the embedded member 504 is embedded in the embedded hole 531 from the lower surface 504b side having a diameter D7 slightly larger than the diameter D2 of the embedded hole 531, whereby the embedded hole 531 is expanded. As a result, in the embedded hole portion 531, the opening end 531a on the upper surface 3a side has a diameter D4 (see FIG.
- the opening end 531b on the lower surface 3b side of the embedded hole 531 is formed in a circular shape having a diameter D5 smaller than the diameter D4 of the opening end 531a on the upper surface 3a side.
- the diameter D7 of the lower surface 504b is obtained.
- the embedding member 504 can be press-fitted into the embedding hole 531 of the Al member 503 more easily.
- the remaining effects of the first modification of the fourth embodiment of the present invention are similar to those of the aforementioned fourth embodiment.
- Example 1 a columnar embedded member 404 (see FIG. 13) having a diameter D3 of 10.0 mm was used as Example 1 corresponding to the fourth embodiment.
- Example 2 the truncated cone-shaped embedding member in which the upper surface 504a has a diameter D6 of 10.0 mm and the lower surface 504b has a diameter D7 of 9.8 mm. 504 (see FIG. 15) was used.
- Example 1 the Al member 403 having the embedded hole portions 431 having different diameters D2 was used. Specifically, four Al members 403 having embedded hole portions 431 each having a diameter D2 of 9.95 mm, 9.90 mm, 9.80 mm, and 9.70 mm were used. In Example 2, the Al member 503 having the embedded hole portion 531 having a diameter D2 of 9.70 mm was used. The thicknesses t1 of the embedded members 404 and 504 and the Al members 403 and 503 were both 3 mm.
- Example 2 the embedded members of Examples 1 and 2 were respectively press-fitted into the corresponding embedded holes of the Al member.
- the embedded member 504 was press-fitted into the embedded hole portion 531 of the Al member 503 from the lower surface 504 b side of the embedded member 504.
- diffusion annealing was performed by maintaining the temperature at 500 ° C. for 3 minutes in a non-oxidizing atmosphere. Thereby, the bus bars of Examples 1 and 2 were prepared.
- Example 1 From the measurement result of the shear load shown in FIG. 16, in Example 1, the shear load is increased by increasing the difference (D3-D2) between the diameter D2 of the embedded hole 431 and the diameter D3 of the embedded member 404. I understood. In Example 1, when (D3-D2) was 0.2 mm or more, the shear load was 1 kN or more. Accordingly, it is considered that the bonding strength between the Al member 403 and the embedded member 404 can be sufficiently increased by setting (D3-D2) to 0.2 mm or more.
- Example 2 when the diameter D2 of the embedded hole portion was 9.70 mm, the shear load in Example 2 was larger than that in Example 1. This is probably because the frustoconical-shaped embedding member 504 of Example 2 was press-fitted into the embedding hole 531 from the side of the lower surface 504b having a small diameter, so that the embedding member 504 was easily pressed into the embedding hole 531. Thus, since the embedded member 504 is press-fitted into the embedded hole portion 531 in a state where the outer side surface 540c of the embedded member 504 and the inner side surface 531c of the embedded hole portion 531 are in close contact with each other, the outer surface 540c of the embedded member 504 The intermetallic compound layer 5 (see FIG.
- the difference between the diameter D2 of the embedding hole 531 and the diameter D6 of the upper surface 504a of the embedding member 504 (D6-D2) is set to 0.2 mm or more, thereby embedding the Al member 503 and the embedding member 504. It is considered that the bonding strength with the member 504 can be sufficiently increased.
- bus bar 602 (Second Modification of Fourth Embodiment) Next, with reference to FIG. 17 and FIG. 18, a second modification of the fourth embodiment of the present invention will be described.
- the bus bar 602 is an example of the “battery terminal connection plate” in the present invention.
- the Al member 603 and the embedded member 604 are examples of the “first member” and the “second member” of the present invention, respectively.
- a screw thread and a thread groove are alternately positioned in the Z direction.
- a portion 631e is formed. That is, the embedded hole 631 is formed as a female screw.
- the embedded member 604 having a cylindrical shape is screwed into the embedded hole portion 631 of the Al member 603.
- the base material 640 embedding member 604 is formed as a male screw.
- the embedded member 604 formed as a male screw is screwed into the embedded hole portion 631 formed as a female screw, whereby the embedded member 604 is embedded in the embedded hole portion 631.
- the Ni plating layer 41 is formed on the upper surface 40a, the lower surface 40b, and the outer surface 640c of the base member 640 of the embedded member 604.
- the interface between the inner side surface 631c of the embedded hole 631 and the Ni plating layer 41 formed on the outer side surface 640c of the base member 640 of the embedded member 604 is mainly composed of an Al—Ni intermetallic compound.
- An intermetallic compound layer 5 is formed.
- an Al member 603 having the same configuration as that of the Al member 403 (see FIG. 11) of the fourth embodiment is prepared.
- the inner surface 631c of the embedded hole 631 is not formed with a screw portion 631e (see FIG. 17) formed of a screw thread and a screw groove.
- a base material 640 which is made of Cu and has a screw portion 640d in which threads and screw grooves are alternately positioned in the Z direction on the outer side surface 640c and in which a hole portion 42 is formed. Then, a plating process is performed on the surface of the base material 640 using Ni. Thereby, the Ni plating layer 41 is formed on the upper surface 40a, the lower surface 40b, and the outer surface 640c of the base material 640. As a result, the embedded member 604 is formed.
- the embedded member 604 is disposed on the upper surface 3a of the Al member 603 from above (Z1 side) so as to cover the embedded hole 631 of the Al member 603 in plan view. Thereafter, the embedded member 604 is pressed from above (Z1 side) while rotating the embedded member 604 using the jig 102. As a result, as shown in FIG. 17, the embedded member 604 is screwed into the embedded hole 631. At this time, the embedding member 604 is screwed into the embedding hole 631 while the inner surface 631c of the embedding hole 631 is formed with the screw portion 631e corresponding to the screw portion 640d of the outer surface 640c of the embedding member 604. The embedding member 604 is screwed into the embedding hole 631 with respect to each of the three embedding holes 631.
- the remaining manufacturing process of the second modification of the fourth embodiment of the present invention is the same as that of the fourth embodiment.
- the intermetallic compound layer 5 made of an Al—Ni intermetallic compound at the interface the detachment of the embedded member 604 from the Al member 603 can be effectively suppressed.
- the bonding strength between the Al member 603 and the embedded member 604 can be increased, the electrical connection at the interface between the Al member 603 and the embedded member 604 is caused by loosening of the bonding between the Al member 603 and the embedded member 604. An increase in resistance can be suppressed.
- the embedded member 604 formed as a male screw is screwed into the embedded hole portion 631 formed as a female screw, so that the embedded member 604 is embedded in the embedded hole.
- the embedded member 604 can be embedded in the embedded hole 631 more firmly than when the embedded member 604 is embedded in the embedded hole 631 of the Al member 603.
- the joint strength between the Al member 603 and the embedded member 604 can be further increased, it is possible to more effectively suppress the embedded member 604 from being detached from the Al member 603.
- the threaded portion 631e formed of a screw thread and a thread groove is not formed on the inner surface 631c of the buried hole portion 631 before the buried member 604 is buried.
- a screw portion 631 e is formed on the inner side surface 631 c of the embedding hole 631, so that the embedding member 604 is screwed into the embedding hole 631 in advance.
- the Al member 603 and the embedded member 604 can be more closely attached to each other, so that the Al member 603 and the embedded member 604 can be bonded more firmly.
- the remaining effects of the second modification of the fourth embodiment are similar to those of the aforementioned first embodiment.
- the bus bar 702 is an example of the “battery terminal connection plate” in the present invention.
- the embedded member 704 is an example of the “second member” in the present invention.
- the first embodiment described above is provided on the surface of the base material 40 of the embedding member 704 (on the upper surface 40 a, on the lower surface 40 b and on the outer surface 40 c). Unlike the form, the Ni plating layer is not formed. Thereby, the inner side surface 31c of the embedding hole 31 and the outer side surface 40c of the base member 40 of the embedding member 704 are configured to be in direct contact with each other. Further, the upper surface 40 a and the lower surface 40 b of the embedded member 704 are configured to be substantially flush with the upper surface 3 a and the lower surface 3 b of the Al member 3, respectively, while being embedded in the embedded hole portion 31.
- an intermetallic compound layer 705 is formed at the interface between the inner surface 31 c of the embedded hole portion 31 and the outer surface 40 c of the base member 40 of the embedded member 704. ing.
- This intermetallic compound layer 705 is mainly composed of an Al—Cu intermetallic compound formed by a reaction between Al constituting the Al member 3 and Cu constituting the base member 40.
- the intermetallic compound layer 705 has a thickness t4 of about 1 ⁇ m or more and about 5 ⁇ m or less.
- the remaining structure of the fifth embodiment of the present invention is similar to that of the aforementioned first embodiment.
- the inner surface of the embedded hole 31 is not subjected to the plating process using Ni on the surface of the base material 40 of the embedded member 704 and the diffusion annealing. Similar to the first embodiment except that an intermetallic compound layer 705 made of an Al—Cu intermetallic compound is formed at the interface between the side surface 31c and the outer surface 40c of the base member 40 of the embedded member 704. It is.
- a metal made of an Al—Cu intermetallic compound is formed at the interface between the inner side surface 31c of the embedded hole portion 31 of the Al member 3 and the outer side surface 40c of the base member 40 of the embedded member 704.
- the intermetallic compound layer 705 it is possible to effectively suppress the embedded member 704 from coming off the Al member 3. Further, since the bonding strength between the Al member 3 and the embedded member 704 can be increased, the electrical connection at the interface between the Al member 3 and the embedded member 704 is caused by loosening of the bonding between the Al member 3 and the embedded member 704. An increase in resistance can be suppressed.
- the fifth embodiment as described above, it is not necessary to perform the plating process using Ni on the surface of the base member 40 of the embedded member 704, so that the manufacturing process of the bus bar 702 can be simplified.
- the remaining effects of the fifth embodiment are similar to those of the aforementioned first embodiment.
- Cu holes 31 (231, 331, 431, 531, 631) of the Al member 3 (203, 303, 403, 503, 603) made of Al are formed in Cu.
- the example which comprised so that it might become larger than the area (area which Cu occupies) of the embedding member was shown, this invention is not limited to this.
- the second member including the base material composed of Al to be embedded in the embedding hole portion of the first member composed of Cu, the area occupied by Cu is more than the area occupied by Al. You may comprise so that it may become large. Thereby, since the area
- the embedded member 4 is formed by forming the Ni plating layer 41 (coating layer) made of Ni on the surface of the base material 40 (240, 340, 440, 540, 640).
- the present invention is not limited to this.
- a coating layer made of a Ni alloy containing Ni may be formed on the surface of the substrate, or a coating layer made of a metal other than Ni may be formed on the surface of the substrate.
- the metal constituting the coating layer is preferably a metal that has a smaller ionization tendency than Al and a larger ionization tendency than Cu, such as Zn.
- it consists of a metal which improves the corrosion resistance of the base material which consists of Cu.
- it is not necessary to form a coating layer on the surface of a base material by a plating process, and you may form a coating layer on the surface of a base material by another method.
- a clad material having a Cu layer (base material) and a Ni layer (coating layer) formed by joining a plate material made of Cu and a plate material made of Ni by applying pressure may be used as an embedded member. Good.
- the upper surface 40a, the lower surface 40b and the outer surface 40c (240c, 340c, 440c, 540c, 640c) of the base material 40 (240, 340, 440, 540, 640) are used.
- the example which formed Ni plating layer 41 (coating layer) which consists of Ni was shown in this, this invention is not limited to this.
- the coating layer may be formed only on the outer surface of the substrate without being formed on the upper surface and the lower surface of the substrate. Thereby, it is possible to reduce the usage-amount of Ni.
- the present invention is not limited to this. Absent.
- a screw portion may be formed in advance on the inner surface of the embedding hole before the embedding member is embedded. As a result, the embedded member can be easily embedded in the embedded hole.
- the width W1 of the bus bar 2 (202, 302, 402, 502, 602, 702) is about 50 mm and the thickness t1 is about 3 mm is shown.
- the present invention is not limited to this.
- the width and thickness of the bus bar are not particularly limited.
- the width of the bus bar is preferably about 10 mm to about 200 mm, and the thickness of the bus bar is preferably about 1 mm to about 4 mm.
- the example in which the Ni plating layer 41 is not provided on the inner peripheral surface of the hole portion 42 into which the negative electrode side terminal 1b of the lithium ion battery 1 is inserted has been described.
- a Ni plating layer may also be provided on the inner peripheral surface of the hole into which the negative electrode side terminal of the lithium ion battery is inserted.
- the manufacturing process in this case is a manufacturing process in which a hole is formed in the embedded member in advance, a plating process is performed with Ni, and finally, the embedded member is embedded in the embedded hole of the Al member.
- the embedded member 4 (204, 304, 404, 504, 704) is replaced with the Al member 3 (203, 303, 403, 503), and in the second modification of the fourth embodiment, the embedded member 604 is screwed into the embedded hole 631 of the Al member 603.
- the embedded member may be embedded in the embedded hole portion of the Al member by a method other than press fitting or screwing.
- the embedded member may be embedded in the embedded hole portion of the Al member by shrink fitting. In shrink fitting, first, the Al member is heated under a temperature condition higher than the temperature at the time of diffusion annealing (about 200 ° C.
- the embedded member is embedded (shrink-fitted) in the embedded hole portion by cooling to a temperature condition of about 200 ° C. or higher and about 500 ° C. or lower. Thereafter, diffusion annealing is performed under a temperature condition of about 200 ° C. or more and about 500 ° C. or less. These series of steps are performed in a non-oxidizing atmosphere or a reducing atmosphere. Other manufacturing processes when adopting shrink fitting are the same as those in the first embodiment.
Abstract
Description
まず、図1~図7を参照して、本発明の第1実施形態によるリチウムイオン電池接続体100の構造について説明する。
次に、図9を参照して、本発明の第2実施形態について説明する。この第2実施形態では、上記第1実施形態とは異なり、バスバー202におけるAl部材203の埋め込み穴部231の開口幅が、Al部材203の上面3aから下面3bに向かって徐々に小さくなる場合について説明する。なお、バスバー202は、本発明の「電池端子用接続板」の一例であり、Al部材203は、本発明の「第1部材」の一例である。
次に、図10を参照して、本発明の第3実施形態について説明する。この第3実施形態では、上記第1実施形態とは異なり、バスバー302におけるAl部材303の埋め込み穴部331の開口幅が、開口端331aおよび331bから埋め込み穴部331の中央部331dに向かって徐々に小さくなる場合について説明する。なお、バスバー302は、本発明の「電池端子用接続板」の一例であり、Al部材303は、本発明の「第1部材」の一例である。
次に、図11~図13を参照して、本発明の第4実施形態について説明する。この第4実施形態によるバスバー402では、上記第1実施形態とは異なり、Al部材403の円形状の埋め込み穴部431に円柱状の埋め込み部材404が圧入される場合について説明する。なお、バスバー402、Al部材403および埋め込み部材404は、それぞれ、本発明の「電池端子用接続板」、「第1部材」および「第2部材」の一例である。
次に、図14および図15を参照して、本発明の第4実施形態の第1変形例について説明する。この第4実施形態の第1変形例によるバスバー502では、上記第4実施形態とは異なり、Al部材503の埋め込み穴部531に円錐台形状に形成された埋め込み部材504が圧入される場合について説明する。なお、バスバー502、Al部材503および埋め込み部材504は、それぞれ、本発明の「電池端子用接続板」、「第1部材」および「第2部材」の一例である。
次に、図13~図16を参照して、本発明の第4実施形態および第4実施形態の第1変形例の効果を確認するために行ったせん断荷重の確認実験について説明する。
次に、図17および図18を参照して、本発明の第4実施形態の第2変形例について説明する。この第4実施形態の第2変形例によるバスバー602では、上記第4実施形態とは異なり、Al部材603の埋め込み穴部631に埋め込み部材604が螺合している場合について説明する。なお、バスバー602は、本発明の「電池端子用接続板」の一例である。また、Al部材603および埋め込み部材604は、それぞれ、本発明の「第1部材」および「第2部材」の一例である。
次に、図19および図20を参照して、本発明の第5実施形態について説明する。この第5実施形態では、上記第1実施形態とは異なり、バスバー702における埋め込み部材704の基材40の表面上にNiメッキ層が形成されていない場合について説明する。なお、バスバー702は、本発明の「電池端子用接続板」の一例である。また、埋め込み部材704は、本発明の「第2部材」の一例である。
Claims (20)
- 第1金属からなる第1電池端子(1a)が挿入される第1穴部(30)と、埋め込み穴部(31、231、331、431、531、631)とを含み、前記第1金属と同一の金属からなる第1部材(3、203、303、403、503、603)と、
前記第1金属とは異なる第2金属からなる第2電池端子(1b)が挿入される第2穴部(42)を有するとともに、前記第2金属と同一の金属からなる基材(40、240、340、440、540、640)を含み、前記第1部材の埋め込み穴部に埋め込まれた第2部材(4、204、304、404、504、604、704)とを備え、
前記第1部材の埋め込み穴部と前記第2部材との界面には、前記第1金属および前記第2金属の少なくともいずれか一方を含む金属間化合物からなる金属間化合物層(5、705)が形成されている、電池端子用接続板(2、202、302、402、502、602、702)。 - 前記第1金属は、AlまたはCuのいずれか一方であり、
前記第2金属は、AlまたはCuのいずれか他方であり、
前記金属間化合物層の金属間化合物は、少なくともAlを含む、請求項1に記載の電池端子用接続板。 - 前記第2部材は、前記基材の表面上で、かつ、少なくとも前記第1部材との界面に配置されるとともに、前記第1金属および前記第2金属とは異なる第3金属からなる被覆層(41)をさらに含み、
前記金属間化合物層の金属間化合物は、前記第1金属と前記第2金属とからなる金属間化合物よりも前記第1部材と前記第2部材との接合強度が大きく、かつ、前記第1金属または前記第2金属のいずれか一方と前記第3金属とからなる、請求項1に記載の電池端子用接続板。 - 前記第3金属は、前記第1金属または前記第2金属のいずれか一方よりもイオン化傾向が大きく、前記第1金属または前記第2金属のいずれか他方よりもイオン化傾向が小さい金属からなる、請求項3に記載の電池端子用接続板。
- 前記第1金属は、AlまたはCuのいずれか一方であり、
前記第2金属は、AlまたはCuのいずれか他方であり、
前記第3金属は、Niであり、
前記金属間化合物層の金属間化合物は、AlとNiとからなる、請求項4に記載の電池端子用接続板。 - 前記第1部材および前記第2部材は、平面視において同一方向に長辺および短辺が延びる矩形状の板材からなり、
前記第2部材の長辺および短辺は、それぞれ、前記第1部材の長辺および短辺よりも短い、請求項1に記載の電池端子用接続板。 - 前記第1部材の埋め込み穴部は、平面的に見て円形状を有しており、
前記第2部材は、前記第2穴部を有する円柱形状を有している、請求項1に記載の電池端子用接続板。 - 前記第2部材は、前記第2穴部を有する円錐台形状を有しており、
前記第1部材の埋め込み穴部は、前記第2部材の円錐台形状に対応する形状を有している、請求項1に記載の電池端子用接続板。 - 前記第1部材の埋め込み穴部の開口幅は、前記第1部材の一方表面(3a)から他方表面(3b)に向かって変化するように構成されている、請求項1に記載の電池端子用接続板。
- 前記第1部材の埋め込み穴部の開口幅は、前記第1部材の前記一方表面から前記他方表面に向かって徐々に小さくなるように構成されている、請求項9に記載の電池端子用接続板。
- 前記第1部材の埋め込み穴部の開口幅は、前記第1部材の前記一方表面および前記他方表面から前記第1部材の厚み方向における略中央に向かって小さくなるように構成されている、請求項9に記載の電池端子用接続板。
- 前記第1部材の埋め込み穴部は、平面的に見て略円形状を有しており、
前記第2部材は、円筒形状を有しているとともに、前記第2部材の前記埋め込み穴部に接する外側面(640c)にはねじ部(640d)が形成されており、
前記第2部材は、前記第2部材のねじ部が前記第1部材の埋め込み穴部の内側面(631c)に螺合するように埋め込まれている、請求項1に記載の電池端子用接続板。 - 第1金属からなる第1電池端子(1a)が挿入される第1穴部(30)と、前記第1金属とは異なる第2金属からなる基材(40、240、340、440、540、640)を含む第2部材(4、204、304、404、504、604、704)が埋め込まれる埋め込み穴部(31、231、331、431、531、631)とを、前記第1金属と同一の金属からなる第1部材(3、203、303、403、503、603)に設ける工程と、
前記第1部材の埋め込み穴部に前記第2部材を埋め込む工程と、
前記第2金属と同一の金属からなる第2電池端子(1b)が挿入される第2穴部(42)を前記第2部材に設ける工程と、
拡散焼鈍することによって、前記第1部材の埋め込み穴部と前記第2部材との界面に、前記第1金属および前記第2金属の少なくともいずれか一方を含む金属間化合物からなる金属間化合物層(5、705)を形成する工程とを備える、電池端子用接続板(2、202、302、402、502、602、702)の製造方法。 - 前記第2穴部を前記第2部材に設ける工程は、前記第1部材の埋め込み穴部に前記第2部材を埋め込む工程よりも後に行われる、請求項13に記載の電池端子用接続板の製造方法。
- 前記第1部材の埋め込み穴部に前記第2部材を埋め込む工程よりも前に、前記第2部材の基材の少なくとも外側面(40c、240c、340c、440c、540c、640c)に前記第1金属および前記第2金属とは異なる第3金属によってめっき処理することによって、前記基材の少なくとも外側面上に被覆層(41)を形成する工程をさらに備え、
前記金属間化合物層を形成する工程は、拡散焼鈍することによって、前記第1金属と前記第2金属とからなる金属間化合物よりも前記第1部材と前記第2部材との接合強度が大きく、かつ、前記第1金属または前記第2金属のいずれか一方と前記第3金属とからなる金属間化合物により構成される前記金属間化合物層を、前記第1部材の埋め込み穴部と前記第2部材の外側面との界面に形成する工程を含む、請求項13に記載の電池端子用接続板の製造方法。 - 前記第1部材の埋め込み穴部に前記第2部材を埋め込む工程は、前記第2部材を前記第1部材の埋め込み穴部の上方に配置した状態で前記第2部材に上方から圧力を加えることによって、前記第1部材の埋め込み穴部に前記第2部材を圧入する工程を含む、請求項13に記載の電池端子用接続板の製造方法。
- 前記第1穴部と前記埋め込み穴部とを前記第1部材に設ける工程は、平面的に見て前記埋め込み穴部が略円形状になるように、前記埋め込み穴部を前記第1部材に設ける工程を含み、
前記第1部材の埋め込み穴部に前記第2部材を埋め込む工程は、円筒形状を有するとともに、外側面にねじ部(640d)が形成された前記第2部材を回転させながら前記第1部材の埋め込み穴部の内側面(631c)に螺合させることによって、前記第1部材の埋め込み穴部に前記第2部材を埋め込む工程を含む、請求項13に記載の電池端子用接続板の製造方法。 - 第1直径を有する円柱形状を有する前記第2部材を準備する工程をさらに備え、
前記第1穴部と前記埋め込み穴部とを前記第1部材に設ける工程は、前記第1部材の埋め込み穴部を、前記第2部材の第1直径よりも小さな第2直径を有する円形状に形成する工程を含み、
前記第1部材の埋め込み穴部に前記第2部材を埋め込む工程は、前記第1部材の埋め込み穴部に前記第2部材を圧入する工程を含む、請求項13に記載の電池端子用接続板の製造方法。 - 前記第1部材の埋め込み穴部を前記第2直径を有する円形状に形成する工程は、前記第2直径を前記第1直径よりも0.2mm以上1.0mm以下だけ小さくなるように形成する工程を有する、請求項18に記載の電池端子用接続板の製造方法。
- 一方面(504a)が第3直径を有するとともに、他方面(504b)が前記第3直径よりも小さな第4直径を有する円錐台形状の前記第2部材を準備する工程をさらに備え、
前記第1穴部と前記埋め込み穴部とを前記第1部材に設ける工程は、前記第1部材の埋め込み穴部を、前記第2部材の一方面の第3直径よりも小さな第5直径を有する円状に形成する工程を含み、
前記第1部材の埋め込み穴部に前記第2部材を埋め込む工程は、前記第2部材の他方面側から、前記第1部材の埋め込み穴部に前記第2部材を圧入する工程を含む、請求項13に記載の電池端子用接続板の製造方法。
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Also Published As
Publication number | Publication date |
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CN103098261B (zh) | 2014-04-02 |
KR101287734B1 (ko) | 2013-07-19 |
US20130309919A1 (en) | 2013-11-21 |
JP5037745B2 (ja) | 2012-10-03 |
KR20130016423A (ko) | 2013-02-14 |
CN103098261A (zh) | 2013-05-08 |
JPWO2012102160A1 (ja) | 2014-06-30 |
US9350007B2 (en) | 2016-05-24 |
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