WO2017002420A1 - Conducteur, et dispositif de stockage de puissance - Google Patents

Conducteur, et dispositif de stockage de puissance Download PDF

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Publication number
WO2017002420A1
WO2017002420A1 PCT/JP2016/061053 JP2016061053W WO2017002420A1 WO 2017002420 A1 WO2017002420 A1 WO 2017002420A1 JP 2016061053 W JP2016061053 W JP 2016061053W WO 2017002420 A1 WO2017002420 A1 WO 2017002420A1
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WO
WIPO (PCT)
Prior art keywords
lead conductor
resin layer
sample
less
power storage
Prior art date
Application number
PCT/JP2016/061053
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English (en)
Japanese (ja)
Inventor
美里 草刈
鉄也 桑原
西川　太一郎
圭太郎 宮澤
木谷　昌幸
Original Assignee
住友電気工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 住友電気工業株式会社 filed Critical 住友電気工業株式会社
Priority to CN201680030956.3A priority Critical patent/CN107683541B/zh
Priority to KR1020177034133A priority patent/KR102550477B1/ko
Publication of WO2017002420A1 publication Critical patent/WO2017002420A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • H01M50/178—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells for pouch or flexible bag cells
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/74—Terminals, e.g. extensions of current collectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/172—Arrangements of electric connectors penetrating the casing
    • H01M50/174—Arrangements of electric connectors penetrating the casing adapted for the shape of the cells
    • 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
    • H01M50/10—Primary casings; Jackets or wrappings
    • H01M50/183—Sealing members
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/534—Electrode connections inside a battery casing characterised by the material of the leads or tabs
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/547—Terminals characterised by the disposition of the terminals on the cells
    • H01M50/55—Terminals characterised by the disposition of the terminals on the cells on the same side of the cell
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/552—Terminals characterised by their shape
    • H01M50/553—Terminals adapted for prismatic, pouch or rectangular cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/543—Terminals
    • H01M50/562—Terminals characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • 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

Definitions

  • the present invention relates to a lead conductor used in a power storage device such as a nonaqueous electrolyte battery, and a power storage device.
  • the present invention relates to a lead conductor that is thin and thin and hardly breaks.
  • Lithium ion secondary batteries are used as power sources for portable electronic / electrical devices such as mobile phones such as smartphones and notebook personal computers, and small electronic / electrical devices (hereinafter sometimes referred to as portable devices).
  • portable devices small electronic / electrical devices
  • a typical lithium-ion secondary battery for use as a power source for portable devices has a configuration in which a battery element is housed in a bag-like container and lead conductors are arranged from the inside to the outside of the container (Patent Document 1). 1 and 2).
  • the lead conductor is mainly made of a metal strip that transfers power between the battery and an external member.
  • pure aluminum is used for the positive lead conductor
  • pure nickel or pure nickel-plated pure copper is used for the negative lead conductor.
  • the above-mentioned bag-shaped container is typically provided with a metal layer. In order to insulate the metal layer from the metal lead conductor, the two are joined via a resin layer. The container is sealed through this resin layer. A lead conductor with resin in which a resin layer is formed on a metal strip is also used.
  • lead conductors used for power storage devices such as lithium ion secondary batteries are not easily broken even if they are thin and narrow.
  • lithium ion secondary batteries and the like used for power supplies of portable devices are required to increase battery capacity (energy density) while being thin and small, and lead conductors are also thicker than before. It is desired to reduce the thickness and the width.
  • lead conductors made of pure metals such as pure aluminum and pure nickel and having a thin and narrow width, for example, a thickness of 0.1 mm or less and a width of 10 mm or less, are assembled in a manufacturing process or in portable devices. There is a risk of breaking.
  • the lead conductor may be bent into a predetermined shape and connected to a member such as a circuit board provided in portable devices.
  • a member such as a circuit board provided in portable devices.
  • the portable device can be stored even when the casing of the portable device is thin or small. If the bending radius is reduced, such as right-angle bending or double folding, the storage capacity of the lead conductor can be further reduced.
  • thin and narrow pure metal lead conductors have a small breaking load, so if they are bent with a small bending radius so that they can be stored in a thin housing, etc., they may break and fall during transport before assembly. There is a possibility of breaking even if an impact such as doing is applied.
  • the lead conductor provided in the power storage device is used for power transfer, it is also desired that the lead conductor is excellent in conductivity.
  • the lead conductor which concerns on 1 aspect of this invention is used for an electric power storage device provided with a positive electrode, a negative electrode, electrolyte solution, and the container which accommodates these.
  • This lead conductor is composed of an aluminum alloy containing 0.005 mass% or more and 2.2 mass% or less of Fe.
  • the tensile strength of this lead conductor is 100 MPa or more and 220 MPa or less.
  • the conductivity of the lead conductor is 50% IACS or more.
  • a power storage device includes the above lead conductor.
  • the above lead conductors are not easily broken even if they are thin and narrow. In the above power storage device, the lead conductor is not easily broken.
  • FIG. 2 is a cross-sectional view of the nonaqueous electrolyte battery of the embodiment taken along the line (II)-(II) shown in FIG.
  • the inventors of the present invention say that a thin and thin lead conductor is not easily broken by bending or impact if it is made of a metal having a specific composition and the tensile strength and conductivity satisfy a specific range. Obtained knowledge.
  • the present invention is based on the above findings. First, the contents of the embodiment of the present invention will be listed and described.
  • the lead conductor which concerns on 1 aspect of this invention is used for an electric power storage device provided with a positive electrode, a negative electrode, electrolyte solution, and the container which accommodates these.
  • This lead conductor is composed of an aluminum alloy containing 0.005 mass% or more and 2.2 mass% or less of Fe.
  • the tensile strength of this lead conductor is 100 MPa or more and 220 MPa or less.
  • the conductivity of the lead conductor is 50% IACS or more.
  • the above lead conductor has a tensile strength that satisfies a specific range, is high in strength but is not too high (not too hard), and is excellent in toughness (for example, elongation at break).
  • Such a lead conductor having high strength and high toughness is thin and thin, for example, with a resistance to bending or impact (for example, 0.1 mm or less) even if the thickness is 0.1 mm or less and the width is 10 mm or less. 2% proof stress), and it is difficult to break even if a predetermined bending is performed or an impact is applied.
  • the lead conductor is not easily broken even when subjected to an impact while being bent into a predetermined shape.
  • the above lead conductor has a specific conductivity and is excellent in conductivity.
  • the strength can be increased by increasing the content of the additive element in the constituent metal of the lead conductor or by sufficiently working and hardening it by plastic working at a high workability.
  • excessive addition of additive elements, excessive strain introduction due to work hardening, and the like cause a decrease in conductivity.
  • Said lead conductor is excellent in electroconductivity, when content of an additive element is adjusted in the range with which the electrical conductivity satisfy
  • non-aqueous electrolyte batteries such as lithium ion secondary batteries used for power sources of portable devices and other power storage devices It can utilize suitably as a structural member.
  • the above lead conductor is excellent in resistance to the electrolytic solution when it is assembled in a power storage device by containing Fe in a specific range.
  • the presence of a resin layer between the lead conductor and the container of the power storage device is also expected to make it difficult to elute the constituent components of the lead conductor and contribute to improvement in resistance to the electrolytic solution.
  • the lead conductor can be suitably used as a constituent member of a power storage device such as a nonaqueous electrolyte battery.
  • the 0.2% proof stress satisfies a specific range, the proof stress is sufficiently high, and even if it is thin and thin, it is difficult to break.
  • the above-mentioned form is thin and narrow, it is not too thin or too narrow, and is difficult to break. Moreover, since the said form is thin and thin, it can respond to the request
  • the diffusion resistance value is 5 ⁇ 10 5 ⁇ ⁇ cm ⁇ 2 or more.
  • the diffusion resistance value is measured as follows. A sample in which a part of the lead conductor is covered with a predetermined resin is used as a sample, and the formation position of the resin and the counter electrode in the sample are brought into contact with the electrolyte used in the power storage device, and the electrolyte is maintained at 60 ° C. Maintain for 1 week. After one week, the AC impedance spectrum of the sample is measured, and the resistance value of the sample is obtained based on the measured AC impedance spectrum. The obtained resistance value is defined as a diffusion resistance value. In a lead conductor with a resin having a coating resin layer to be described later, the diffusion resistance value may be measured by regarding the coating resin layer as the predetermined resin.
  • the diffusion resistance value is high even if the above-described form is in contact with a high-temperature electrolyte solution for a long time via the predetermined resin, it can be said that the constituent elements of the lead conductor are difficult to elute into the electrolyte solution over time. Therefore, the above-mentioned form is not easily broken even if it is thin and narrow, and is excellent in resistance to the electrolytic solution.
  • the surface treatment part has fine unevenness and excellent adhesion to the resin layer, and the lead conductor and the resin layer are difficult to peel off even if the resin layer formation area in the lead conductor is bent or shocked .
  • the above-described form is not easily broken even if it is thin and thin, and the above-mentioned diffusion resistance value is further enhanced in that the resin layer is in close contact, and the resistance to the electrolytic solution is superior.
  • the aluminum alloy contains 0.005% by mass in total of one or more elements selected from Mg, Mn, Ni, Zr, Ag, Cu, Si, Cr, and Zn.
  • the form containing 1 mass% or less is mentioned above.
  • the above-mentioned form contains the above-listed elements in a specific range, so that the strength tends to be higher and the fracture is difficult to occur while having high conductivity.
  • the aluminum alloy contains at least one of Ti of 0.01% by mass to 0.05% by mass and B of 0.001% by mass to 0.02% by mass. A form is mentioned.
  • Both Ti and B have the effect of making the crystal of the aluminum alloy fine during casting.
  • Ti and B are contained in a specific range, so that the constituent metal of the lead conductor can be an aluminum alloy having a fine crystal structure, and the strength tends to be higher and breakage is easily caused. It is hard to do.
  • the lead conductor includes a coating resin layer bonded to a fixed region of the lead conductor with the container, and the coating resin layer has a multilayer structure made of different resins.
  • the form whose total thickness is 20 micrometers or more and 300 micrometers or less is mentioned.
  • the coating resin layer is interposed between the lead conductor and the container of the power storage device and functions as an insulator. If the coating resin layer has a multilayer structure, it can contain resins of various materials, particularly resins having excellent adhesion. Even if the coating resin layer has a multi-layer structure, a thin lead conductor with a resin can be obtained as long as the thickness thereof is within the specific range described above. Therefore, the said form can ensure insulation with a container and contributes to thickness reduction of an electric power storage device. When this coating resin layer is provided in the surface treatment portion of (5) above, it is preferable because of excellent adhesion to the lead conductor as described above.
  • a power storage device includes the lead conductor according to any one of (1) to (8) above.
  • the lead conductor provided in the above power storage device is thin and thin, the lead conductor is not easily broken when it is bent during the manufacturing process or when it is subjected to an impact by dropping it at any time. Therefore, when the power storage device is used as a power source for portable equipment, it is possible to reduce a decrease in yield due to breakage of the lead conductor or to maintain the lead conductor having excellent conductivity for a long period of time. , Can exchange power with the outside.
  • the lead conductor 1 (FIGS. 1 and 2) of the embodiment is a conductive member used in a power storage device (nonaqueous electrolyte battery 10 in FIG. 1), and includes a positive electrode 14 and a negative electrode 15 (see FIG. 1) housed in a container 11. 2) and an external member (not shown) are electrically connected to be used for power transfer.
  • the lead conductor 1 is typically a rectangular metal strip, and is used in a state where the resin layer is in contact with, preferably in close contact with, at least a fixed region of the surface with the container 11.
  • the resin layer is at least one of a coating resin layer 22 described later, an inner resin layer 112 (FIG. 2) provided in the container 11 itself, and a bonding resin layer (not shown) separately bonded between the lead conductor 1 and the container 11. (Hereinafter, simply referred to as a resin layer).
  • the lead conductor 1 of the embodiment is that it is made of an aluminum alloy having a specific composition containing Fe in a specific range.
  • the composition of this aluminum alloy will be described first, and then the characteristics and structure of the lead conductor 1 will be described.
  • the aluminum alloy constituting the lead conductor 1 of the embodiment is Fe—0.005 mass% to 2.2 mass%, with the balance being Al (aluminum) and an Al—Fe alloy that is an inevitable impurity.
  • the aluminum alloy which comprises the lead conductor 1 of embodiment contains Fe in the above-mentioned specific range, and is selected from Mg, Mn, Ni, Zr, Ag, Cu, Si, Cr, and Zn
  • specific elements elements
  • An Al-Fe alloy containing 0.005% or more of Fe has high tensile strength and 0.2% proof stress and is excellent in strength and proof strength. For example, softening treatment is performed after plastic working to improve toughness and electrical conductivity. High strength can be maintained even when increased. In this case, such an Al—Fe-based alloy can have high strength, high toughness, and high conductivity. Even if the lead conductor 1 composed of such an Al—Fe alloy is thin and thin, it is difficult to break when subjected to predetermined bending or impact.
  • Such an Al—Fe-based alloy tends to have higher strength as the Fe content is higher.
  • such an Al—Fe-based alloy has an Fe content of 0.01% or more, more preferably 0.1% or more, 0.5% or more, 0.7% or more, 0.9% or more, 0.8% or more. It can be over 9%.
  • Such an Al—Fe-based alloy can suppress a decrease in conductivity and toughness by containing Fe in a range of 2.2% or less. If the Fe content is too large, the electrical conductivity and toughness are liable to decrease, so that it can be made 2% or less, further 1.8% or less, 1.5% or less, or 1.2% or less. Further, by containing Fe in a specific range, the amount that the constituent components of the aluminum alloy can be eluted into the electrolytic solution can be sufficiently reduced. In the lead conductor 1 attached to the power storage device, if the resin layer is in close contact with at least a part of the surface, it is considered that the above-described elution amount can be easily reduced.
  • the aluminum alloy constituting the lead conductor 1 of the embodiment is likely to have high strength when it contains the above-mentioned specific element in a specific range in addition to Fe.
  • Mg has a large effect in improving the strength, although the decrease in conductivity is somewhat large, and the strength can be further improved by containing it together with Si.
  • Mn, Ni, Zr, and Cr have a large decrease in electrical conductivity, the effect of improving the strength is high.
  • Ag and Zn have little decrease in electrical conductivity and have a certain degree of strength improvement effect.
  • Cu has little decrease in conductivity and can improve strength. Either a form containing only one kind of these elements or a form containing two or more kinds can be used.
  • Such an aluminum alloy has high strength and hardly breaks when the total content of the specific elements is 0.005% or more.
  • the greater the total content, the higher the strength, and the lower limit can be 0.01% or more, further 0.05% or more, 0.1% or more.
  • the total content of the specific element is 1% or less, such an aluminum alloy is excellent in conductivity by reducing the decrease in conductivity.
  • the constituent components of the lead conductor 1 are eluted in the electrolytic solution, there is a possibility that the positive electrode 14 and the negative electrode 15 are short-circuited or the characteristics of the power storage device are deteriorated due to the eluted components.
  • the total content is 1% or less, the elution of the constituent components can be sufficiently reduced.
  • the upper limit of the total content can be 0.9% or less, further 0.8% or less, or 0.7% or less.
  • Examples of the content of each element include the following. Mg 0.005% to 0.4%, further 0.01% to 0.3%, Mn 0.005% to 0.8%, further 0.01% to 0.7% Cu 0.005 % Or more and 0.9% or less, further 0.01% or more and 0.7% or less, Si 0.005% or more and 0.4% or less, and further 0.01% or more and 0.3% or less Cr 0.005% or more. 8% or less, further 0.01% or more and 0.7% or less Ni, Zr, Ag, Zn Total 0.005% or more and 0.2% or less, and further 0.005% or more and 0.15% or less
  • the inventors of the present invention configured a two-electrode electrochemical cell of a working electrode made of aluminum alloy or pure aluminum having various compositions and a counter electrode made of platinum, and both electrodes were immersed in an electrolyte solution to obtain a predetermined voltage.
  • the amount of current that flows when sapphire was measured was measured.
  • the amount of current when the aluminum alloy contains Fe in the above-described specific range for example, the Fe content is 1.05%
  • the lead conductor 1 of the embodiment defines the Fe content and the types and contents of the additive elements listed above.
  • Ti and B are examples of Ti and B in addition to Fe or in addition to Fe and the specific element described above.
  • Ti and B have an effect of making the crystal of the aluminum alloy fine at the time of casting, and the strength is enhanced if it has a fine crystal structure.
  • the form containing B may be sufficient, the refinement
  • crystallization is more easily acquired as it is the form containing Ti and also the form containing both Ti and B.
  • An aluminum alloy is more likely to obtain a crystal refinement effect as the content of Ti or B is larger, but if it is too much, the conductivity is lowered. Moreover, it is thought that the refinement
  • the fine crystal structure described above can be cited.
  • the average crystal grain size may be 1 ⁇ m or more and 50 ⁇ m or less, 2 ⁇ m or more and 40 ⁇ m or less, and further 30 ⁇ m or less.
  • the lead conductor 1 has such a fine crystal structure, the lead conductor 1 is excellent in strength and is not easily broken even if it is thin and thin, and the electrolyte does not easily penetrate into the lead conductor 1. It is expected that the amount of the constituent component eluted into the electrolytic solution is reduced and the resistance to the electrolytic solution is easily increased.
  • the crystal grain size may be controlled to a predetermined size by adjusting the content of the above-described additive elements, the conditions of plastic working in the manufacturing process, the heat treatment conditions, and the like.
  • the lead conductor 1 of the embodiment is characterized in that the tensile strength is 100 MPa or more and 220 MPa or less. Since the lead conductor 1 has a sufficiently high tensile strength, it is difficult to break even if it is thin and narrow. Since the higher the tensile strength, the better the strength and the more difficult it is to break, the lower limit of the tensile strength can be over 110 MPa, 115 MPa or more, further 120 MPa or more, 125 MPa or more. Since the lead conductor 1 is not too high in tensile strength, the electrical conductivity is reduced due to strain introduced during plastic working, and the electrical conductivity is excellent, and the toughness such as elongation is also excellent. Therefore, the lead conductor 1 can have a tensile strength of 210 MPa or less, further 200 MPa or less, and 190 MPa or less.
  • the lead conductor 1 of the embodiment has high tensile strength and typically excellent strength, and it is difficult to break even if it is thin and narrow. Specifically, a lead conductor 1 having a 0.2% proof stress satisfying 40 MPa or more can be mentioned. The lead conductor 1 has a tendency that the higher the yield strength, the more difficult it is to break, and the 0.2% yield strength can be set to 45 MPa or more, further 50 MPa or more, 55 MPa or more. When the 0.2% proof stress is too high, the tensile strength tends to be too high, and there is a concern about the above-described decrease in conductivity and toughness. The upper limit of 0.2% proof stress is about 100 MPa or less.
  • the lead conductor 1 of the embodiment is excellent in strength such as tensile strength and proof stress, and is typically excellent in toughness such as elongation, and it is difficult to break even if it is thin and narrow.
  • the lead conductor 1 satisfying a breaking elongation of 5% or more can be mentioned.
  • the lead conductor 1 tends to be more difficult to break as the elongation is higher, and the elongation at break can be 6% or more, further 7% or more, or 8% or more.
  • the upper limit of breaking elongation is about 40% or less.
  • the lead conductor 1 of the embodiment is excellent in strength and toughness, and is also excellent in conductivity, and has a conductivity satisfying 50% IACS or more.
  • the lead conductor 1 preferably has higher electrical conductivity, and the electrical conductivity can be 51% IACS or higher, further 52% IACS or higher, or 53% IACS or higher.
  • the size (thickness, width, length) of the lead conductor 1 of the embodiment can be selected as appropriate.
  • the lead conductor 1 having a small thickness and a narrow width can be suitably used as a constituent member of a power storage device for which a reduction in thickness and size is desired.
  • Examples of the thin and narrow lead conductor 1 include those having a thickness of 0.03 mm to 0.1 mm and a width of 1 mm to 10 mm.
  • the length of the lead conductor 1 may be adjusted by appropriately cutting before assembling to the power storage device.
  • the lead conductor 1 has a thickness of 0.03 mm or more, it is difficult to break even if the width is as thin as about 1 mm.
  • the lead conductor 1 can have a thickness of 0.035 mm or more, and further 0.04 mm or more. If the lead conductor 1 has a thickness of 0.1 mm or less, it can contribute to the reduction in thickness and size of the power storage device.
  • the lead conductor 1 can have a thickness of 0.08 mm or less, further 0.07 mm or less, and 0.05 mm or less.
  • the width of the lead conductor 1 is 1 mm or more, it is difficult to break even if the thickness is as thin as about 0.03 mm.
  • the width can be 2 mm or more, and further 3 mm or more. If the width
  • the lead conductor 1 can have a width of 9 mm or less, further 8 mm or less, or 7 mm or less.
  • the lead conductor 1 of the embodiment is also excellent in resistance to the electrolyte solution, and the constituent components of the lead conductor 1 are difficult to elute into the electrolyte solution.
  • the lead conductor 1 has a higher diffusion resistance value, so that the amount of the above constituent components eluted into the electrolyte solution is smaller and the resistance to the electrolyte solution is better, and the diffusion resistance value is 6 ⁇ 10 5 ⁇ ⁇ cm ⁇ 2 or more, Furthermore, it is preferable to satisfy 7 ⁇ 10 5 ⁇ ⁇ cm ⁇ 2 or more and 7.5 ⁇ 10 5 ⁇ ⁇ cm ⁇ 2 or more.
  • the lead conductor 1 preferably includes a specific surface treatment portion described later in a contact region with the resin layer.
  • the lead conductor 1 of embodiment is provided with the surface treatment part by which the below-mentioned surface treatment was given to the fixed area
  • region with the container 11 at least on the surface of at least one part of the surface Preferably both surfaces of a front and back, a resin layer Adhesion can be improved.
  • the contact area of the lead conductor 1 with the electrolytic solution in the container 11 in the lead conductor 1 is reduced due to the closely adhered resin layer, and the components of the lead conductor 1 can be reduced from being eluted into the electrolytic solution.
  • a lead conductor 1 has a high diffusion resistance value.
  • the sealed state of the container 11 of the power storage device can be maintained satisfactorily, leakage of the electrolyte solution to the outside of the container 11, and intrusion of moisture from the outside into the container 11 Can be prevented.
  • Form in which the surface treatment part is provided only in the fixed region with the container 11 on the surface of the lead conductor 1 (form in which surface treatment is performed only in the fixed area), and form in which the surface treatment part is provided on the entire front and back surfaces of the lead conductor 1
  • Surface treatment is applied to the end surface / side surface connecting the back surface
  • the surface treatment portion is provided on the entire outer surface of the lead conductor 1 (surface treatment is applied to all of the end surface / side surface connecting the front and back surfaces and the front and back surfaces.
  • Examples of the surface treatment include chemical conversion treatment, boehmite treatment, alumite treatment, etching, blast treatment, and brush polishing.
  • As the conditions for each treatment known conditions that have been applied to conventional lead conductors can be used.
  • the lead conductor 1 when the lead conductor 1 includes a surface treatment portion to which one type selected from chemical conversion treatment, boehmite treatment, alumite treatment, and etching is applied, it is more excellent in adhesion to the resin layer, depending on the treatment conditions. It tends to be the lead conductor 1.
  • the lead conductor 1 includes a surface treatment portion subjected to chemical conversion treatment or etching, the adhesion with the resin layer is further improved. By being superior in the adhesion between the lead conductor 1 and the resin layer, it is possible to reduce the elution amount of the constituent components, increase the diffusion resistance value, maintain a good sealing state, and the like.
  • the surface roughness of this surface treatment part 0.1 micrometer or more and 0.5 micrometer or less are mentioned by arithmetic mean roughness Ra, for example.
  • Covering resin layer As an example of the lead conductor 1 of the embodiment, a coating bonded to a fixed region between the main body of the lead conductor 1 made of an aluminum alloy having the above-described specific composition and the container 11 in the main body of the lead conductor 1 A lead conductor with resin 20 including the resin layer 22 is exemplified.
  • the covering resin layer 22 functions as an insulator between the main body of the lead conductor 1 and the metal layer 110 when the container 11 of the power storage device includes the metal layer 110.
  • known manufacturing conditions for lead conductors with resin can be used for the coating resin layer 22.
  • thermoplastic polyolefin A typical example of the constituent material of the coating resin layer 22 is thermoplastic polyolefin. Specifically, polyethylene, acid-modified polyethylene, polypropylene, ethylene vinyl acetate copolymer, acid-modified polypropylene (for example, maleic anhydride-modified polypropylene), ionic polymers such as ionomer, maleic acid-modified polyolefin (for example, maleic acid-modified polyolefin) Low density polyethylene), or mixtures thereof.
  • ionomer examples include those obtained by crosslinking a copolymer such as ethylene and methacrylic acid with a metal ion such as Na, Mg, K, Ca, or Zr, a metal complex, or a cation such as an ammonium salt.
  • a metal ion such as Na, Mg, K, Ca, or Zr
  • a metal complex such as an ammonium salt.
  • the covering resin layer 22 can be a single layer structure or a multilayer structure made of resins having different components and cross-linked states.
  • the coating resin layer 22 having a multilayer structure include a two-layer structure including an adhesive layer and a surface layer.
  • the adhesive layer includes the above-described thermoplastic polyolefin
  • the surface layer includes the above-described thermoplastic polyolefin cross-linked (for example, the same resin as the constituent resin of the adhesive layer and cross-linked).
  • both the adhesion between the main body of the lead conductor 1 and the coating resin layer 22 and the adhesion between the container 11 and the coating resin layer 22 can be selected by selecting a component, a crosslinked state, and the like. Can be enhanced. As a result, even if the portion having the coating resin layer 22 in the lead conductor 20 with resin is bent or subjected to an impact, the container 11 and the coating resin layer 22 are disposed between the main body of the lead conductor 1 and the coating resin layer 22. The covering resin layer 22 is difficult to peel off.
  • the power storage device including such a lead conductor 20 with resin can reduce the amount of elution into the electrolyte in the constituent components of the main body of the lead conductor 1 by the coating resin layer 22 that is in close contact with the main body of the lead conductor 1.
  • the sealed state of the container 11 can be maintained satisfactorily.
  • the surface treatment portion includes the coating resin layer 22 because the adhesion of the coating resin layer 22 is more excellent.
  • the coating resin layer 22 is thick to some extent, the coating resin layer 22 is not easily damaged when the lead conductor 20 with resin is bent or subjected to an impact, and conversely, the coating resin layer 22 is not too thick. Thus, the lead conductor 20 with resin can be thinned.
  • the thickness of the coating resin layer 22 is, for example, 20 ⁇ m or more and 300 ⁇ m or less, and can be 30 ⁇ m or more and 290 ⁇ m or less, 40 ⁇ m or more and 280 ⁇ m or less, and 50 ⁇ m or more and 200 ⁇ m or less.
  • This thickness is the thickness of the coating resin layer 22 provided on one surface of the main body of the lead conductor 1 when the coating resin layer 22 is provided on the front and back surfaces of the main body of the lead conductor 1, and the coating resin layer provided on one surface. If 22 is a multilayer structure, the total thickness is used.
  • the lead conductor 1 of embodiment and the lead conductor 20 with resin can be utilized for any of the positive electrode of a power storage device, and a negative electrode, it is suitable for the lead conductor for positive electrodes.
  • the lead conductor 1 having the above-mentioned specific composition and having high strength and excellent conductivity, and the lead conductor 1 also excellent in elongation are prepared by preparing an aluminum alloy having a specific composition, and plasticity such as rolling. Manufactured by processing and heat treatment. Examples of the material used for plastic working include a continuous cast material, a billet cast material, and an extruded material obtained by extruding a continuous cast rolled material.
  • the heat treatment includes softening treatment, and plastic processing can be performed before and after the softening treatment.
  • Examples of the lead conductor 1 include soft materials and 1 ⁇ 2 hard materials.
  • the 1 ⁇ 2 hard material can be manufactured by performing plastic processing to some extent after the softening treatment, or by performing a softening treatment to such an extent that the strength does not decrease too much after the plastic working. At least the heat treatment conditions and the degree of plastic working are adjusted so that the tensile strength and the electrical conductivity satisfy the specific ranges described above.
  • the lead conductor 20 with a resin including the coating resin layer 22 is preferably manufactured by, for example, the following manufacturing method (A) or (B) because the adhesiveness of the coating resin layer 22 is excellent.
  • the details of the surface treatment refer to the section of the surface treatment section described above.
  • the details of the coating resin layer 22 may be referred to the section of the coating resin layer 22 described above.
  • Hot rolling or cold rolling is performed by adjusting the rolling reduction so as to obtain a rolled sheet having a desired thickness (which may be the thickness of the lead conductor 1).
  • a desired thickness which may be the thickness of the lead conductor 1.
  • the crystal can be made finer, and even when heat treatment is performed at an appropriate time, the lead conductor 1 having a fine crystal structure can be easily obtained.
  • Intermediate heat treatment can be performed during rolling. When the intermediate heat treatment is performed, the plastic workability can be improved.
  • Heat treatment such as softening treatment can be performed by either continuous treatment performed continuously on a long material or batch treatment performed while the material is sealed in a heating container such as an atmospheric furnace.
  • Examples of the continuous treatment include a direct energization method, an indirect energization method, and a furnace method.
  • Control parameters such as holding temperature, holding time, material supply speed, current value, furnace temperature, and the like are adjusted in accordance with the continuous processing method so that the tensile strength and the electrical conductivity become desired values.
  • the conditions for softening treatment by batch treatment include, for example, a holding temperature of 250 ° C. to 500 ° C., a holding time of 0.5 hours to 6 hours, and an atmosphere having a low oxygen content.
  • a low oxygen atmosphere can suppress the formation of an oxide film.
  • Specific atmospheres include an air atmosphere and a non-oxidizing atmosphere.
  • the non-oxidizing atmosphere include a reduced pressure atmosphere (vacuum atmosphere), an inert gas atmosphere such as nitrogen and argon, and a reducing gas atmosphere containing hydrogen and carbon dioxide gas.
  • the produced aluminum alloy plate having a predetermined thickness is cut according to a predetermined width of the lead conductor 1 to form a strip.
  • the cross-sectional area of the wide thin plate is large to some extent, so that it is difficult to break and is easy to handle.
  • this wide thin plate is cut into, for example, a width of 10 mm or less to form a narrow strip, the cross-sectional area is reduced.
  • this thin and narrow strip is made of the aluminum alloy having the specific composition described above, and the tensile strength and the electrical conductivity satisfy a specific range, so that the breaking load is large and it is difficult to break.
  • this thin and narrow strip (an example of the lead conductor 1 of the embodiment) is not easily broken and easy to handle in the manufacturing process of the lead conductor 1 itself, and is bent or shocked in the manufacturing process of the power storage device. It is difficult to break even if it is received. If the strip is long, it may be appropriately cut to a predetermined length.
  • the power storage device electrically connects a positive electrode, a negative electrode, an electrolyte, a container that stores these, a positive electrode and an external member, and a negative electrode and an external member.
  • One lead conductor In the power storage device of the embodiment, one or two of the two lead conductors are the lead conductor 1 of the above-described embodiment (there may be a lead conductor 20 with resin).
  • Each lead conductor is arranged from the inside to the outside of the container, and a positive electrode or a negative electrode is connected to one end side, and an external member such as a circuit board is connected to the other end side by soldering or the like.
  • a fixing area with the container is provided.
  • a resin layer (at least one of the above-described coating resin layer 22, inner resin layer 112, and bonding resin layer) is interposed between the lead conductor fixing region and the container.
  • the power storage device of the embodiment include a non-aqueous electrolyte battery using a non-aqueous electrolyte, an electric double layer capacitor, and an aqueous electrolyte battery using water as a main solvent of the electrolyte.
  • Known techniques can be applied to the basic configuration of the nonaqueous electrolyte battery, the electric double layer capacitor, the aqueous electrolyte battery, the material of each component, and the like.
  • the nonaqueous electrolyte battery 10 includes a positive electrode 14, a negative electrode 15, a separator 13 impregnated with an electrolytic solution (here, a nonaqueous electrolytic solution), a bag-like container 11 that houses these battery elements, and a container 11. And two lead conductors 20 with resin fixed to each other.
  • At least one of the lead conductors 20 with resin includes a main body of the lead conductor 1 made of an aluminum alloy having the specific composition described above, and a coating resin layer 22 bonded to the front and back surfaces of the main body of the lead conductor 1.
  • the negative electrode lead conductor for example, one made of pure nickel, pure copper, pure nickel-plated pure copper, or the like can be used.
  • the covering resin layer 22 shown in FIG. 2 has a double structure including an adhesive layer 220 in contact with the main body of the lead conductor 1 and a surface layer 222 in contact with the inner surface of the container 11.
  • the positive electrode 14 and the negative electrode 15 of the nonaqueous electrolyte battery 10 are typically an active material layer composed of a powder molded body containing an active material, etc., and are a current collector 16 and a current collector composed of metal foil. 17 is formed on each.
  • the current collector 16 (or current collector 17) and the main body of the lead conductor 1 are connected by, for example, a lead wire 19 (FIG. 2).
  • a lead wire 19 As the positive electrode and the negative electrode of the electric double layer capacitor, solid activated carbon is exemplified.
  • the container 11 is typically provided with a metal layer and a resin layer.
  • the container 11 of FIG. 2 shows the example comprised from the double-sided multilayer film provided with the inner side resin layer 112, the metal layer 110, and the outer side resin layer 114 in order from the inner side.
  • the container 11 is sealed by heat-sealing the peripheral portion of the double-sided multilayer film, and is formed into a bag shape as shown in FIG.
  • the inner resin layer 112 of the container 11 and the covering resin layer 22 (here, the surface layer 222) of the lead conductor 20 with resin are heat-sealed, thereby providing the lead conductor with resin. 20 is fixed to the container 11 and the container 11 is sealed.
  • the strip material of each sample was manufactured as follows. A raw material having a composition shown in Table 1 (remainder Al and inevitable impurities) is prepared, and an aluminum alloy plate having a thickness of 0.05 mm is manufactured by the following steps. Each obtained aluminum alloy plate is cut into a width of 5 mm or a width of 4 mm to obtain a narrow strip. Continuous casting or billet ⁇ conform extrusion ⁇ cold rolling ⁇ softening treatment
  • the aluminum alloy of each sample is as follows. Sample No. 1-1-No. 1-6, 1-101, 1-102 Al—Fe alloy sample no. 2-1. 2-5 Al—Fe—Mg alloy Sample No. 3-1. 3-16, 1-301, 1-302 Al—Fe—Mg + ⁇ -based alloy Sample No. 4-1. 4-12, 1-401, 1-402 Al—Fe—Cu + ⁇ -based alloy ⁇ is one or more elements selected from Mn, Ni, Zr, Ag, Cr, and Zn. ⁇ is one or more elements selected from Mg, Si, Cr, and Zn.
  • a softening treatment (final heat treatment in this test) is performed after rolling.
  • Table 2 shows the conditions for softening treatment (softening temperature, atmosphere).
  • the softening treatment is batch processing (bright softening)
  • the holding time of the softening temperature is adjusted mainly using tensile strength as an index
  • continuous processing continuous softening
  • Control parameters such as material supply speed, current value, and furnace temperature were adjusted according to the continuous processing method.
  • Sample No. No softening treatment is performed on 1-302 and 1-402.
  • a tensile test (room temperature) was performed using a strip of 5 mm width among the strips of each sample prepared, and tensile strength (MPa), 0.2% proof stress (MPa), and elongation at break (%) were examined. . The results are shown in Table 2. The tensile test is performed based on JIS Z 2241 (2011).
  • the electrical conductivity (IACS%) was examined by a four-terminal method using a strip having a width of 5 mm among the strips of each prepared sample. The results are shown in Table 2.
  • the bending test is performed as follows. As shown in FIG. 3, the sample S (strip) having a distance L between the scores of 30 mm is folded into two (see black arrows). Bending is performed so that the distance C between the ends of the sample S adjacent by folding is equal to twice the thickness of the sample S (0.05 mm in this example). Open the sample S folded in two and return it to its original position (see white arrow). This series of operations of folding and returning is considered as one time, and the number of times until it breaks is examined. It can be said that it is hard to break, so that there are many times.
  • the impact test is performed as follows. As shown in FIG. 4, a weight w is attached to the tip of a sample S having a distance L between the scores of 1 m (the left figure in FIG. 4), and after lifting the weight w upward by 1 m (the middle figure in FIG. 4), free fall (Right figure in FIG. 4). The weight (kg) of the maximum weight w at which the sample S does not break by this operation was measured, and the product value obtained by multiplying the weight by the gravitational acceleration (9.8 m / s 2 ) and the drop distance 1 m was divided by the drop distance. Impact resistance is evaluated by the magnitude of the value (J / m or (N ⁇ m) / m). It can be said that the larger the impact value, the better the impact resistance and the more difficult it is to break.
  • 1-1-No. 1-6, No. 1 2-1. 2-5, No. 2 3-1. 3-16, no. 4-1. 4-12 (hereinafter sometimes referred to collectively as a sample group having a specific composition) has a tensile strength of 100 MPa to 220 MPa, a conductivity of 50% IACS or higher, high strength and conductivity It turns out that it is excellent.
  • Sample No. 1-1-No. 1-6 has a tensile strength of 100 MPa or more and many samples of 115 MPa or more.
  • the tensile strength and conductivity can be increased by adjusting the softening conditions, but the elongation is low and the material is easily broken.
  • 1-301 has low conductivity.
  • Sample No. with too much Fe It can be seen that 1-401 has low elongation and is easy to break.
  • Sample No. It can be seen that if the softening treatment is not performed as in 1-302 and 1-402 and the tensile strength is too high (in this case, more than 220 MPa), it is likely to break.
  • a thin and narrow strip having a thickness of 0.1 mm or less and a width of 10 mm or less is bent with a bending radius equal to or less than the thickness of the sample, but is further repeatedly bent.
  • each sample group having a specific composition has a number of folding times of 3 or more. Except for 4-8, it is 4 times or more and it can be seen that it is difficult to break.
  • a lead conductor provided in a power storage device such as a lithium ion secondary battery is bent into a predetermined shape and fixed to an external member, an operation for opening the bent portion is performed in the subsequent manufacturing process. There is usually no such thing.
  • each sample group having a specific composition has high tensile strength and also excellent elongation in addition to satisfying a specific range of tensile strength. It is done. Specifically, all the sample groups having a specific composition have a 0.2% proof stress of 40 MPa or more. Except for 1-3, there are many samples having a 0.2% yield strength of 50 MPa or more and a 0.2% yield strength of 60 MPa or more. In any sample group having a specific composition, the elongation at break is 5% or more, most of the samples are 6% or more, and some samples are 10% or more.
  • each sample group having a specific composition has a fine crystal structure, in particular, a sample containing at least one of Ti and B in a specific range has a finer crystal structure. It is conceivable that When the crystal grain size was examined by observing a cross section of a sample group having a specific composition with an optical microscope, all the samples had an average crystal grain size of 50 ⁇ m or less. Samples containing Ti and B were finer crystals. there were. The average crystal grain size is determined by a cutting method in accordance with JIS G 0551 (steel-crystal grain size microscopic test method, 2005).
  • Test Example 2 Sample No. produced in Test Example 1 Simulated samples of lead conductors with resin were prepared using strips made of 1-1, 2-1, 3-1, 4-1 aluminum alloy, and the diffusion resistance value and the bonding strength of the resin were examined.
  • a simulated sample of the lead conductor with resin was prepared as follows.
  • An aluminum alloy plate (thickness 0.05 mm) having the composition shown in Table 3 (thickness Al and inevitable impurities) was cut into a width of 10 mm and a length of 45 mm to produce a thin and narrow strip, and the surface treatment shown in Table 4 The resin is bonded after applying or without surface treatment.
  • the sample subjected to the surface treatment is subjected to the surface treatment on the entire front and back surfaces of the strip (the entire front and back surfaces are the surface treatment portion), and the end surface and side surfaces of the strip are not subjected to the surface treatment.
  • the details of the surface treatment shown in Table 4 are as follows.
  • the chemical conversion treatments I, III, and IV are chemical conversion treatments using commercially available chemical conversion treatment solutions capable of forming ionomers, and the average thickness of chemical film formation is the values shown in Table 4 (10 nm, 30 nm, 300 nm).
  • the immersion time of the chemical conversion treatment solution is adjusted.
  • Chemical conversion treatment II is a chromate treatment using a commercially available treatment solution.
  • the roughening I and II are etching treatments using a commercially available alkaline etching solution, and the etching time is adjusted so that the average pit depth becomes the values shown in Table 4 (1 ⁇ m, 0.5 ⁇ m).
  • Boehmite I and II are boehmite treatments using 95 ° C.
  • Alumite I and II are anodized using an aqueous sulfuric acid solution, and the treatment time is adjusted so that the average thickness of the alumite layer is 0.5 ⁇ m.
  • sealing treatment is not performed after anodization, and in anodized II, sealing treatment is performed after anodization.
  • -Blasting is a blasting process performed under the conditions shown in Table 4 (shot material: # 120 alumina particles, pressure: 0.3 MPa) using a commercially available pneumatic blasting apparatus.
  • Each sample No. 1 subjected to the above surface treatment was used. 1-21, 1-22, no. 1-24-No. 1-26, no. 2-21, 22-2, no. 3-21, 3-22, no. 4-21 and 4-22, and sample No. Resin is bonded to the front and back surfaces of the 1-23 strip.
  • a double-structure resin film including an adhesive layer (thickness 25 ⁇ m) made of acid-modified polypropylene and a surface layer obtained by crosslinking acid-modified polypropylene is used. Two resin films are used for each sample so as to sandwich the front and back surfaces of the strip of each sample. The thickness of the surface layer for each resin film used in each sample is adjusted so that the total thickness of the adhesive layer and the surface layer becomes “resin thickness” in Table 4.
  • the band material is sandwiched between two resin films, and the resin film is bonded to the front and back surfaces of the band material by hot pressing.
  • the joining conditions are heating temperature: 260 ° C., pressure: 0.2 MPa, and heating time: 10 seconds.
  • a simulated sample of a lead conductor with resin in which a part of the strip is exposed from the resin is obtained.
  • a region on one edge side where the lead wire is connected in the strip (10 mm in the region on the upper edge side in FIG. 5 ⁇ 10 mm in length) is exposed from the resin film.
  • Each resin film is 25 mm ⁇ length 45 mm.
  • the regions on both sides of the strip are exposed from the resin film (regions on the left and right sides in FIG. 7).
  • Each resin film is 5 mm ⁇ length 60 mm.
  • an electrochemical measurement cell 300 is constructed using a simulated sample SS1 including a strip S1 simulating a main body of a lead conductor and a resin layer S22, a counter electrode 302, and an electrolytic solution 304. After the simulated sample SS1 is immersed in the liquid 304 for a predetermined time, a diffusion resistance value is calculated using an AC impedance spectrum (see also Patent Document 1). The results are shown in Table 4.
  • the counter electrode 302 is a wire rod (diameter 0.5 mm ⁇ length 50 mm) made of pure aluminum containing 99.999% by mass of Al.
  • the electrolytic solution 304 is used as an electrolytic solution for a lithium ion secondary battery.
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • V / V% means volume ratio.
  • lead wires are connected to the simulated sample SS1 and the counter electrode 302, respectively, and both lead wires are further connected to the AC impedance spectrum measuring device 310.
  • Each simulated sample SS1 is immersed in the electrolytic solution 304, and the counter electrode 302 is immersed in the electrolytic solution 304. In this way, the electrochemical measurement cell 300 is constructed.
  • the above-described electrochemical measurement cell 300 is inserted into a thermostatic bath (not shown), the temperature of the electrolytic solution 304 is maintained at 60 ° C., and this immersion state is maintained for one week (1 W, 168 hours). After one week, the AC impedance spectrum of each simulated sample SS1 is measured in the electrolyte solution 304, and the diffusion resistance value is calculated from the measured AC impedance spectrum.
  • the diffusion resistance value (Warburg impedance) is calculated using analysis by simulation using the equivalent circuit shown in FIG. When the diffusion resistance value is W, the equivalent circuit has a charge transfer resistance Rp in series with the diffusion resistance value W, a capacitance C in parallel with the diffusion resistance value W and the charge transfer resistance Rp, and a series connection with the parallel circuit.
  • the electrolyte resistance Rs is calculated using analysis by simulation using the equivalent circuit shown in FIG. When the diffusion resistance value is W, the equivalent circuit has a charge transfer resistance Rp in series with the diffusion resistance value W, a capacitance C in parallel with the diffusion resistance value
  • the measurement conditions for the AC impedance spectrum are: amplitude: 25 mV, measurement frequency range: 100 kHz to 100 mHz.
  • the number of AC impedance spectrum measurement points is 10 points from 100 kHz to 10 kHz, and 60 points in total.
  • Each data of the AC impedance spectrum at each measurement frequency is reproduced by simulation using the above-described equivalent circuit, and each parameter of the equivalent circuit shown in FIG. 6 is estimated.
  • the diffusion resistance value is calculated using the result of this simulation.
  • AC impedance spectrum can be automatically measured and analyzed using commercially available AC impedance spectrum measuring apparatus, AC impedance spectrum measuring software, and analysis software.
  • AC impedance spectrum measuring apparatus AC impedance spectrum measuring software
  • analysis software For example, VersaSTAT4-400 + VersaSTAT LC (Princeton Applied Research) can be used as the measurement device, VersaStudio (Princeton Applied Research) can be used as the measurement software, and Zview (Scribner Associates Inc.) can be used as the analysis software.
  • the electrolytic solution As the electrolytic solution, the same one as used for measuring the diffusion resistance value (electrolytic solution manufactured by Kishida Chemical Co., Ltd.) is used.
  • the simulated sample SS2 is taken out from the electrolyte, and one resin film S22a and the strip S1 are cut as shown in the left diagram of FIG. Then, it is divided into two (divided piece S1s, divided piece S1l, film piece la, film piece sa).
  • the simulated sample SS2 is divided so that the length of the other divided piece S1l is sufficiently longer than the length of the one divided piece S1s.
  • the divided pieces S1l and divided pieces S1s that are divided are joined to the other resin film S22b. As shown in the right figure of FIG. 8, this other resin film S22b is folded back so that the short divided piece S1s is separated from the long divided piece S1l.
  • the long split piece S1l and the short split piece S1s are gripped by a commercially available tensile tester (not shown), and the split pieces S1l and the split pieces S1s are separated from each other as shown by the black arrows in the right diagram of FIG. Pull up and down in the right figure of 8).
  • sample no. 1-21, 1-22, 2-21, 22-22, 3-21, 3-22, 4-21, 4-22 (hereinafter sometimes collectively referred to as a sample group for specific processing)
  • the diffusion resistance value is 5 ⁇ 10 5 ⁇ / cm 2 or more, and many samples are 10 ⁇ 10 5 ⁇ / cm 2 or more.
  • the specific treatment sample group has a peel strength after 2.5 W of 2.5 N or more, many samples are 3 N or more, further 4 N or more, and many samples are 5 N or more. It turns out that it is hard to peel. From this, it is considered that one of the reasons why the diffusion resistance value is large is that the resin layer is in close contact without being peeled off, and the contact area with the electrolytic solution in the strip of each sample can be reduced.
  • strip material of a specially treated sample group with a large diffusion resistance value is used as the lead conductor of a power storage device, it can be expected that the constituent components of the strip material can be reduced from leaching into the electrolyte, and that it is also excellent in resistance to the electrolyte. Is done. Moreover, it can be said that the lead conductor excellent also in the tolerance with respect to such electrolyte solution is obtained by selecting an appropriate surface treatment method and process conditions.
  • the present invention is not limited to these exemplifications, but is defined by the scope of the claims, and is intended to include all modifications within the scope and meaning equivalent to the scope of the claims.
  • the composition of the aluminum alloys of Test Examples 1 and 2 the width and thickness of the strip, the surface treatment method, the treatment conditions, the material and thickness of the coating resin layer, and the like can be changed as appropriate.

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  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
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  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
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  • Connection Of Batteries Or Terminals (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
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Abstract

L'invention concerne un conducteur qui est mis en œuvre dans un dispositif de stockage de puissance équipé d'une électrode positive, d'une électrode négative, d'un électrolyte et d'un réceptacle admettant ceux-ci. Ce conducteur est configuré par un alliage d'aluminium comprenant 0,005% en masse ou plus à 2,2% en masse ou moins d'un Fe, et présente une résistance à la traction supérieure ou égale à 100MPa et inférieure ou égale à 220MPa, et une conductivité supérieure ou égale à 50% IACS.
PCT/JP2016/061053 2015-06-30 2016-04-05 Conducteur, et dispositif de stockage de puissance WO2017002420A1 (fr)

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