CN111133612B - Electrode for electric storage device, and method for manufacturing electrode for electric storage device - Google Patents

Electrode for electric storage device, and method for manufacturing electrode for electric storage device Download PDF

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Publication number
CN111133612B
CN111133612B CN201880061165.6A CN201880061165A CN111133612B CN 111133612 B CN111133612 B CN 111133612B CN 201880061165 A CN201880061165 A CN 201880061165A CN 111133612 B CN111133612 B CN 111133612B
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electrode
storage device
collector plate
lead
electric storage
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CN111133612A (en
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井户贵彦
守屋茂树
前田伸也
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Ibiden Co Ltd
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Ibiden Co Ltd
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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
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/533—Electrode connections inside a battery casing characterised by the shape 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • 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
    • H01M50/531—Electrode connections inside a battery casing
    • H01M50/536—Electrode connections inside a battery casing characterised by the method of fixing the leads to the electrodes, e.g. by welding
    • 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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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Connection Of Batteries Or Terminals (AREA)

Abstract

The present invention provides an electrode for an electric storage device, which can ensure high connection reliability and high strength even if a collector plate provided with an electrode part containing silicon as an active material is used. The electrode for an electric storage device according to the present invention is an electrode for an electric storage device comprising a collector plate having a main body portion and a lead-out portion, the electrode portion being disposed in the main body portion of the collector plate, and the lead-out portion being connected to the lead-out portion of the collector plate, wherein the lead-out portion and the main body portion are formed of a homogeneous stainless steel; the stainless steel is an austenitic stainless steel including a martensitic structure; the electrode portion contains silicon as an active material.

Description

Electrode for electric storage device, and method for manufacturing electrode for electric storage device
Technical Field
The present invention relates to an electrode for an electric storage device, and a method for manufacturing an electrode for an electric storage device.
Background
Power storage devices using metals having a high tendency to be ionized by lithium are used in many fields because they can store large amounts of energy.
As a method for manufacturing such an electric storage device, patent document 1 discloses a method for manufacturing an electric storage device including: a positive electrode formed on a positive electrode current collector having a through hole, a negative electrode formed on a negative electrode current collector having a through hole, and a nonaqueous electrolyte solution containing a lithium salt, the positive electrode including, as a positive electrode active material, a carbonaceous material having a layered structure capable of intercalating and deintercalating anions, the negative electrode including, as a negative electrode active material, a carbonaceous material having a layered structure capable of intercalating and deintercalating lithium ions, the manufacturing method comprising the steps of: a battery cell manufacturing step of disposing a laminate in which the positive electrode and the negative electrode are laminated with a separator interposed therebetween and a lithium ion supply source in a battery cell for an electric storage device, and injecting the nonaqueous electrolyte; a charge/discharge step of charging/discharging between the positive electrode and the lithium ion supply source; and an occlusion step of causing electrochemical contact between the negative electrode and the lithium ion supply source to occlude lithium ions in the negative electrode.
In the method for manufacturing the power storage device described in patent document 1, metallic lithium is used as a lithium ion supply source. The lithium ion supply source is used to charge and discharge between the positive electrode and the lithium ion supply source, and further to make electrochemical contact between the negative electrode and the lithium ion supply source, thereby trapping lithium ions in the negative electrode.
When a power storage device is manufactured by the method described in patent document 1, metallic lithium as a lithium ion supply source remains in the power storage device.
The metallic lithium contained in the lithium ion supply source is a flammable hazardous material. Therefore, it is preferable that metallic lithium not remain in the power storage device.
Patent document 2 describes the use of a carbonaceous material doped with lithium ions as such a lithium ion supply source.
That is, it is described therein that a carbonaceous material is fixed to a current collector plate, and lithium ions are occluded between layers of the carbonaceous material by intercalation, and the carbonaceous material is used as a lithium-containing electrode.
By using such a lithium ion-containing electrode, charge and discharge can be performed between the positive electrode and the lithium ion supply source without using lithium metal, and further electrochemical contact can be performed between the negative electrode and the lithium ion supply source, thereby trapping lithium ions in the negative electrode.
However, in the case where lithium ions are occluded in a carbonaceous material by intercalation, the occlusion amount of lithium ions has a theoretical upper limit value of 372mAh/g, and the upper limit value cannot be exceeded. Therefore, materials capable of occluding more lithium ions than carbonaceous materials have been studied.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open publication No. 2014-211950
Patent document 2: japanese patent laid-open publication 2016-103609
Disclosure of Invention
Problems to be solved by the invention
Silicon is known as a substance capable of alloying with lithium ions and capable of occluding lithium ions. In the case of occluding lithium ions with silicon, it is theoretically considered that lithium ions of 4000mAh/g or more can be occluded.
That is, when silicon is used to store lithium ions, the storage device can have a high capacity because of a large amount of stored and released lithium ions per unit volume.
However, there is a problem in that the expansion and contraction of the active material itself increases when lithium ions are released by occlusion.
Therefore, when silicon is fixed to a collector plate to be used as an electrode, there is a problem in that the collector plate is significantly deformed and the collector plate is warped or wrinkled. Since there is such a problem, in the case of using silicon as an active material, there is a problem that the current collector plate is deformed in the power storage device and connection reliability is lowered.
The purpose of the present invention is to provide an electrode for an electric storage device, which can ensure high connection reliability and high strength even when a collector plate having an electrode portion containing silicon as an active material is used, a method for manufacturing the same, and an electric storage device using the electrode for an electric storage device.
Means for solving the problems
(1) The electrode for an electric storage device according to the present invention is an electrode for an electric storage device comprising a collector plate having a main body and a lead-out portion, the electrode portion being disposed in the main body of the collector plate, and the lead being connected to the lead-out portion of the collector plate,
the lead-out portion and the main body portion are formed of a homogeneous stainless steel,
the stainless steel is an austenitic stainless steel comprising a martensitic structure,
the electrode portion contains silicon as an active material.
In the electrode for an electric storage device of the present invention, the collector plate is formed of austenitic stainless steel including a martensitic structure.
The hardness of the martensitic structure is high. Therefore, when the current collector plate is made of austenitic stainless steel including a martensitic structure, the current collector plate can be made hard and have high strength. Therefore, the current collector plate is easily prevented from being warped or wrinkled.
Therefore, even when the metal ions are occluded in the active material of the electrode portion or the metal ions occluded in the active material of the electrode portion are released to change the volume of the active material, warpage or wrinkles of the current collector plate are easily prevented.
In the electrode for an electric storage device of the present invention, the lead portion connected to the lead wire and the main body portion are formed of a homogeneous stainless steel.
That is, when connecting the lead and the current collector plate, the connection is performed by a method that does not heat and does not denature the current collector plate.
Therefore, the strength of the lead portion connected to the lead is sufficiently enhanced, and the function of the collector plate is not easily lowered.
The electrode for a power storage device according to the present invention is preferably the following.
(2) In the electrode for an electric storage device according to the present invention, it is preferable that the martensitic structure is dispersed in the austenitic structure in an island-like manner in a cross section of the collector plate cut in the thickness direction.
The martensite structure is dispersed in the austenite structure in an island shape, which can be said to be more than the content (mass) of the martensite structure.
Since the austenite structure is chemically stable, the current collector plate thus constituted is less likely to corrode or dissolve out.
(3) In the electrode for a power storage device of the present invention, the elastic modulus of the lead wire is preferably smaller than that of the collector plate.
When the elastic modulus of the lead is smaller than that of the collector plate, the lead absorbs external force or vibration when receiving the external force or vibration. Therefore, a strong force is not easily applied to the connection portion between the lead and the current collector plate, and the connection portion between the lead and the current collector plate is not easily broken.
(4) In the electrode for an electric storage device of the present invention, the lead wire preferably contains at least one selected from the group consisting of nickel, copper, aluminum, and brass.
These substances have high electrical conductivity and are excellent materials for the lead wires.
In addition, these substances can be firmly connected to stainless steel by ultrasonic welding. Therefore, the connection strength between the lead and the current collector plate can be sufficiently improved.
(5) In the electrode for an electric storage device of the present invention, the above-mentioned lead may be plated with at least one selected from the group consisting of nickel, gold, silver, zinc and chromium.
These materials can be firmly connected to stainless steel by ultrasonic welding. Therefore, the connection strength between the current collector and the lead coated with these substances can be sufficiently improved.
In addition, a material having a low elastic modulus can be used as the core material of the lead, and the elastic modulus of the entire lead can be reduced.
(6) In the electrode for a power storage device of the present invention, the active material preferably contains only silicon.
Silicon may occlude metal ions by alloying with the metal ions.
Therefore, for example, a larger amount of metal ions can be occluded than a substance in which metal ions are occluded by intercalation such as carbon. In particular, if lithium ions are used, 4000mAh/g or more can be occluded.
Therefore, the capacitance can be sufficiently increased.
When silicon is occluded with a large amount of metal ions or a large amount of metal ions are released from silicon in this manner, the volume of silicon as an active material is significantly changed. When the volume of silicon changes in this way, the collector plate tends to buckle or warp.
However, in the electrode for an electric storage device according to the present invention, the collector plate is formed of austenitic stainless steel including a martensitic structure. Therefore, even when the volume of silicon is changed, the current collector plate is less likely to warp or buckle.
(7) The electrode for an electric storage device of the present invention can be used as a metal ion supply electrode for supplying metal ions to an electrolyte.
The electrode for an electric storage device of the present invention can be used not only as a positive electrode or a negative electrode of an electric storage device but also as a metal ion supply electrode.
(8) The power storage device of the present invention is characterized by comprising the electrode for a power storage device of the present invention.
Therefore, in the power storage device of the present invention, the collector plate of the electrode for the power storage device is less likely to wrinkle or warp.
(9) The method for manufacturing an electrode for an electric storage device according to the present invention is a method for manufacturing an electrode for an electric storage device comprising a collector plate having a main body portion and a lead portion, the electrode portion being disposed on the main body portion of the collector plate, and the lead portion being connected to the lead portion of the collector plate,
the manufacturing method comprises an ultrasonic connection step of connecting the lead-out portion and the lead by ultrasonic welding,
the current collector plate is formed of austenitic stainless steel including a martensitic structure,
the electrode portion contains silicon as an active material.
In the method for manufacturing an electrode for an electric storage device of the present invention, a collector plate and a lead are connected by ultrasonic welding.
When a part of the current collector plate or a part of the lead is melted by heat such as resistance welding to connect the current collector plate and the lead, the stainless steel forming the current collector plate is denatured by heat. When such denaturation occurs, there is a problem that partial thermal deformation occurs and the function of the collector plate is lowered.
On the other hand, ultrasonic welding is a method capable of connecting metals to each other without generating heat. Therefore, when ultrasonic welding is used, the current collecting plate can be connected to the lead without causing denaturation of the current collecting plate. Therefore, the strength of the lead portion connected to the lead is sufficiently enhanced, and the function of the collector plate is not easily lowered.
ADVANTAGEOUS EFFECTS OF INVENTION
In the electrode for an electric storage device of the present invention, the lead portion connected to the lead wire and the main body portion are formed of a homogeneous stainless steel.
That is, when the lead is connected to the current collector plate, the current collector plate is not denatured.
Therefore, partial thermal deformation is less likely to occur, the strength of the lead portion connected to the lead is sufficiently enhanced, and the function of the collector plate is less likely to be lowered.
Drawings
Fig. 1 is a cross-sectional view schematically showing an example of an electrode for a power storage device according to the present invention.
Fig. 2 is a cross-sectional view schematically showing an example of a cross section of a collector plate in the electrode for an electric storage device according to the present invention, which is cut in the thickness direction.
Detailed Description
The electrode for a power storage device according to the present invention will be described below with reference to the drawings, but the electrode for a power storage device according to the present invention is not limited to the following description.
Fig. 1 is a cross-sectional view schematically showing an example of an electrode for a power storage device according to the present invention.
As shown in fig. 1, electrode 10 for a power storage device includes collector plate 20, electrode portions 30 formed on both surfaces of collector plate 20, and lead wires 40 connected to end portions of collector plate 20.
The lead portion 21 and the main body portion 22 are formed of a homogeneous stainless steel.
The stainless steel forming the current collector plate 20 is an austenitic stainless steel including a martensitic structure.
In addition, the electrode portion 30 contains silicon as an active material.
In the electrode 10 for an electric storage device, the collector plate 20 is formed of austenitic stainless steel including a martensitic structure.
The hardness of the martensitic structure is high. Therefore, when collector plate 20 is made of austenitic stainless steel including a martensitic structure, collector plate 20 can be made hard and have high strength. Therefore, the current collector plate 20 is easily prevented from being warped or wrinkled.
Therefore, even when metal ions are occluded in the active material of the electrode portion 30 or the volume of the active material is changed by being released from the metal ions occluded in the active material of the electrode portion, warpage or wrinkles of the current collector plate 20 are easily prevented.
In the electrode 10 for an electric storage device, the lead portion 21 and the main body portion 22 are formed of a homogeneous stainless steel.
As will be described in detail later, when the lead wire 40 is connected to the collector plate 20, the collector plate 20 is not denatured.
Therefore, partial thermal deformation is less likely to occur, and the main body 22 has sufficient strength.
In the electrode 10 for an electric storage device, it is preferable that the martensitic structure is dispersed in the austenitic structure in an island shape in a cross section of the collector plate 20 cut in the thickness direction.
The state in which the martensite structure is dispersed in the austenite structure in an island shape will be described below with reference to the drawings.
Fig. 2 is a cross-sectional view schematically showing an example of a cross section of a collector plate in the electrode for an electric storage device according to the present invention, which is cut in the thickness direction.
In fig. 2, reference numeral 26 denotes a martensitic structure, and reference numeral 27 denotes an austenitic structure.
As shown in fig. 2, the term "state in which the martensite structure is dispersed in the austenite structure in an island form" in this specification means that the martensite structure 26 is present in the austenite structure in a plaque form without being biased.
The martensite structure is dispersed in the austenite structure in an island shape, which can be said to be more than the content (mass) of the martensite structure.
Since the austenite structure is chemically stable, the current collector plate thus constituted is less likely to corrode or dissolve out.
The presence of the martensite structure and the austenite structure can be analyzed by electron back scattering diffraction pattern measurement (EBSD method) under the following conditions.
(conditions of EBSD method)
< analysis device >
EF-SEM: JSM-7000F/EBSDD manufactured by Japanese electronics Co., ltd.): TSL Solution
< analysis conditions >
The range is as follows: 14X 36 μm
Step size: 0.05 μm/step
Measurement points: 233376
Multiplying power: 5000 times
The phases are as follows: gamma-iron, alpha-iron
In the present specification, the term "the lead portion and the main body portion are formed of a homogeneous stainless steel" means that the structure constituting the lead portion and the main body portion is a continuous structure, and the following results are obtained by measurement by the EBSD method.
That is, "the lead-out portion and the main body portion are formed of homogenous stainless steel" means the following cases:
the structure constituting the lead portion 21 and the main body portion 22 is a continuous structure, there is no interface therebetween, and the area of the martensitic structure in the cross section where the lead portion 21 is cut in the thickness direction is 5 to 20% of the entire cross section, and the area of the martensitic structure in the cross section where the main body portion 22 is cut in the thickness direction is 5 to 20% of the entire cross section.
The area of the martensitic structure in the cross section of the lead portion 21 cut in the thickness direction is preferably 5 to 20% of the entire cross section.
The area of the martensitic structure in the cross section of the main body 22 cut in the thickness direction is preferably 5 to 20% of the entire cross section.
When the area of the martensitic structure of the cross section of the lead portion 21 cut in the thickness direction and the area of the martensitic structure of the cross section of the main body portion 22 cut in the thickness direction are within the above ranges, the current collector plate is less likely to corrode and has high strength.
When the area occupied by the martensitic structure in the cross section is less than 5%, the strength-improving effect of the collector plate due to the martensitic structure is not easily obtained.
When the area occupied by the martensitic structure in the cross section is larger than 20%, the martensitic structure is easily exposed on the surface, and the martensitic structure is continuously involved in the martensitic structure existing in the inside, so that the entire collector plate is easily corroded. Further, since the proportion of the martensitic structure increases, the toughness of the collector plate tends to be lowered, and as a result, the collector plate tends to be broken.
In the electrode 10 for an electric storage device, the thickness of the collector plate 20 is preferably 5 to 50 μm.
When the thickness of the collector plate is less than 5 μm, the collector plate is easily broken because the thickness is too thin.
When the thickness of the collector plate is greater than 50 μm, the size of the power storage device using the electrode for the power storage device including the collector plate having such a thickness tends to increase because the thickness is excessively large.
The tensile strength of collector plate 20 is not particularly limited, but is preferably 300 to 1500MPa.
In the electrode 10 for an electric storage device, the elastic modulus of the lead wire 40 is preferably smaller than that of the collector plate 20.
When the elastic modulus of the lead wire 40 is smaller than that of the current collector plate 20, the lead wire 40 absorbs external force or vibration when receiving the external force or vibration. Therefore, a strong force is not easily applied to the connection portion between the lead 40 and the collector plate 20, and the connection portion between the lead 40 and the collector plate 20 is not easily broken.
In the electrode 10 for a power storage device, the elastic modulus of the lead 40 is preferably 50 to 150GPa.
In the electrode 10 for a power storage device, the elastic modulus of the collector plate 20 is preferably 150 to 250GPa.
In addition, in the electrode 10 for an electric storage device, the vickers hardness of the collector plate 20 is preferably 300 to 500.
In the electrode 10 for an electric storage device, the lead 40 preferably contains at least one selected from the group consisting of nickel, copper, aluminum, and brass.
These substances have high electrical conductivity and are excellent materials for the lead wires.
In addition, these substances can be firmly connected to stainless steel by ultrasonic welding. Therefore, the connection strength between the lead and the current collector plate can be sufficiently improved.
In the electrode 10 for an electric storage device, the lead 40 may be plated with at least one selected from the group consisting of nickel, gold, silver, zinc, and chromium.
These materials can be firmly connected to stainless steel by ultrasonic welding. Therefore, the connection strength between the current collector and the lead coated with these substances can be sufficiently improved.
In addition, a material having a low elastic modulus can be used as the core material of the lead, and the elastic modulus of the entire lead can be reduced.
The cross-sectional shape of the lead is not particularly limited. Any shape such as a circular shape, a rectangular shape, a plate shape, etc. may be used.
In the electrode 10 for an electric storage device, the electrode portion 30 preferably contains an active material and a binder.
The active material may contain silicon, carbon, or the like.
The average particle diameter of the active material is not particularly limited, and is preferably 1 to 10. Mu.m.
When the average particle diameter of the active material is 1 μm or more, the average particle diameter of the active material can be easily adjusted.
When the average particle diameter of the active material is 10 μm or less, the specific surface area is sufficiently increased, and thus the time required for doping can be shortened.
In the electrode 10 for an electric storage device, the active material of the electrode portion 30 preferably contains only silicon.
Silicon may occlude metal ions by alloying with the metal ions.
Therefore, for example, a larger amount of metal ions can be occluded than a substance in which metal ions are occluded by intercalation such as carbon. In particular, if lithium ions are used, 4000mAh/g or more can be occluded.
Therefore, when the active material contains only silicon, the capacitance can be sufficiently increased.
When silicon occludes a large amount of metal ions or releases a large amount of metal ions from silicon as described above, the volume of silicon as an active material significantly changes. When the volume of silicon changes in this way, the collector plate tends to buckle or warp.
However, in the electrode for an electric storage device according to the present invention, the collector plate is formed of austenitic stainless steel including a martensitic structure. Therefore, even when the volume of silicon is changed, the current collector plate is less likely to warp or buckle.
The material of the binder of the electrode portion 30 is not particularly limited, and examples thereof include polyimide resin, polyamideimide resin, and the like. Among these, polyimide resins are preferable.
Polyimide resins are heat-resistant and strong compounds. Therefore, when the active material is bonded by the binder made of the polyimide resin, the electrode portion 30 can be made less likely to be peeled off from the collector plate 20 even if the volume of the active material changes due to occlusion and release of metal ions.
The weight ratio of the active material to the binder in the electrode portion 30 is preferably the active material: binder = 70: 30-90: 10.
in addition, a conductive auxiliary agent may be contained in the adhesive of the electrode portion 30.
The material of the conductive additive is not particularly limited, and examples thereof include carbon black, carbon fibers, carbon nanotubes, and the like. Among these, carbon black is preferably contained.
When the binder contains the conductive additive, the conductivity of the electrode 10 for the power storage device can be improved. Therefore, current can be efficiently collected.
In particular, the conductivity can be ensured when the carbon black is small. Therefore, when carbon black is a conductive additive, the conductivity of the electrode 10 for an electric storage device can be further improved.
In the case where the conductive additive contains carbon black, the average particle diameter thereof is preferably 3 to 500nm.
In the electrode portion 30, the weight proportion of the conductive additive in the binder is preferably 20 to 50%.
In the electrode 10 for a power storage device, the thickness of the electrode portion 30 is not particularly limited, and is preferably 5 to 50 μm.
When the thickness of the electrode portion is less than 5 μm, the amount of the active material is reduced as compared with the collector plate, and therefore the capacitance is liable to be reduced.
When the thickness of the electrode portion is greater than 50 μm, the size of the power storage device manufactured using the electrode for the power storage device increases. In addition, the moving distance of the metal ions in the electrode portion becomes long, and it takes time to charge and discharge.
The surface density of the electrode portion 30 on one surface is not particularly limited, but is preferably 0.1 to 10mg/cm 2 。
The electrode for an electric storage device of the present invention can be used as a positive electrode, a negative electrode, or a metal ion supply electrode for doping metal ions in an electrolyte solution of the electric storage device.
Next, a method for manufacturing an electrode for a power storage device according to the present invention will be described.
The method for manufacturing an electrode for an electric storage device according to the present invention is a method for manufacturing an electrode for an electric storage device including a collector plate including a main body portion and a lead portion, the electrode portion being disposed on the collector plate, and an electrode portion connected to the collector plate, and a lead wire, wherein the method for manufacturing an electrode for an electric storage device includes an ultrasonic connection step of connecting the collector plate and the lead wire by ultrasonic welding.
The method is characterized in that the current collector plate is made of austenitic stainless steel including a martensitic structure, and the electrode portion includes silicon as an active material.
An example of a method for producing an electrode for a power storage device according to the present invention will be described in detail below.
(1) Manufacturing process of collector plate
First, a metal plate made of austenitic stainless steel is prepared.
Next, the metal plate is subjected to an expansion process to produce a collector plate. By this expansion process, a part of the austenite structure is denatured into a martensite structure.
The stretching is preferably performed such that the thickness is 60 to 80% of the original thickness.
Thus, a current collector plate made of austenitic stainless steel including a martensitic structure can be produced.
(2) Active material slurry preparation process
Silicon and a binder are mixed to prepare an active material slurry.
The weight ratio of the active material to the binder is not particularly limited, and is preferably as follows: binder = 70: 30-90: 10.
The binder is not particularly limited, and examples thereof include polyimide resin precursors, polyamideimide resin precursors, and the like. Among these, polyimide resin precursors are preferred.
From the viewpoint of coatability, the viscosity of the active material slurry is preferably 1 to 10pa·s. The viscosity of the slurry was measured using a type B viscometer at 1 to 10 rpm.
By adjusting the ratio of active material to binder, the viscosity of the active material slurry can be adjusted. The viscosity may be adjusted by a thickener or the like as needed.
(3) Coating process of active material slurry
The active material slurry is coated on the current collector plate.
The amount of the active material slurry to be coated is not particularly limited, but is preferably 0.1 to 10mg/cm after heat drying 2 。
(4) Pressing process
Next, the collector plate coated with the active material slurry is subjected to press working.
The pressing pressure is not particularly limited, and is sufficient as long as the active material can be pressed flat.
(5) Heating process
Next, the current collector plate coated with the active material slurry is heated to cure the binder contained in the active material slurry.
The heating conditions are preferably determined according to the kind of binder used.
In the case where the binder is a polyimide resin precursor, the heating temperature is preferably 250 to 350 ℃. The atmosphere at the time of heating is preferably an inert atmosphere such as a nitrogen atmosphere.
(6) Ultrasonic welding process
Then, the current collector plate and the lead wire are connected by ultrasonic welding.
When a part of the current collector plate or a part of the lead is melted by heat such as resistance welding to connect the current collector plate and the lead, the stainless steel forming the current collector plate is denatured by heat. When such denaturation occurs, there is a problem in that the function of the collector plate is lowered.
On the other hand, ultrasonic welding is a method capable of connecting metals to each other without generating heat. Therefore, when ultrasonic welding is used, the current collecting plate can be connected to the lead without causing denaturation of the current collecting plate. Therefore, thermal deformation does not occur, the strength of the lead-out portion is sufficiently enhanced, and the function of the collector plate is not easily lowered.
The time period for connecting the current collector plate and the lead wire by ultrasonic welding may be before the active material is placed on the current collector plate.
The ultrasonic welding may be performed using, for example, an ultrasonic welding machine (2000 xea40:0.8 manufactured by Branson corporation, emerson corporation, japan) under conditions of an output of 100 to 500W, a welding time of 50 to 500 milliseconds, and a pressure of an ultrasonic horn of 5 to 25 MPa.
Since the preferred structure of the lead has already been described, the description thereof is omitted.
Next, a power storage device using the electrode for a power storage device of the present invention will be described.
The power storage device using the electrode for a power storage device of the present invention is also a power storage device of the present invention.
The electric storage device of the present invention is composed of
A positive electrode,
A negative electrode,
A separator for separating the positive electrode and the negative electrode,
Power storage case accommodating the positive electrode, the negative electrode, and the separator
An electrolyte sealed in the power storage case,
the positive electrode or the negative electrode may be the electrode for a power storage device of the present invention.
In the power storage device of the present invention, the lead wire of the electrode for a power storage device of the present invention may be used for connection to another electrode or may be used for connection to another electrical component.
In the above-described power storage device according to the present invention, the negative electrode is preferably the electrode for a power storage device according to the present invention.
The following describes an electric storage device of the present invention in which the negative electrode is an electrode for an electric storage device of the present invention.
The negative electrode is the electrode for a power storage device according to the present invention.
That is, the negative electrode is an electrode for an electric storage device, the electrode including a collector plate including a main body and a lead-out portion, the electrode being disposed in the main body of the collector plate, and the lead being connected to the lead-out portion of the collector plate, wherein
The lead-out portion and the main body portion are formed of a homogenous stainless steel,
the stainless steel is an austenitic stainless steel including a martensitic structure,
the electrode portion contains silicon as an active material.
In the following description, the collector plate and silicon of the electrode for an electric storage device according to the present invention are also referred to as a negative electrode collector plate and a negative electrode active material, respectively.
In the electrode for a power storage device of the present invention, the positive electrode is preferably composed of a positive electrode collector plate and a positive electrode active material provided in the positive electrode collector plate.
The positive electrode collector plate is not particularly limited, but preferably contains aluminum, nickel, copper, silver, or an alloy thereof.
The positive electrode active material is not particularly limited, and examples thereof include: liMnO 2 、Li x Mn 2 O 4 (0<x<2)、Li 2 MnO 3 、Li x Mn 1.5 Ni 0.5 O 4 (0<x<2) And lithium manganate having a layered structure or lithium manganate having a spinel structure; liCoO 2 、LiNiO 2 Or a material obtained by replacing a part of these transition metals with other metals; liNi 1/3 Co 1/3 Mn 1/3 O 2 Lithium transition metal oxides of not more than half of the specific transition metals; among these lithium transition metal oxides, those obtained by excess of Li over the stoichiometric composition; liFePO 4 And substances having an olivine structure; etc.
In addition, a material obtained by partially replacing these metal oxides with aluminum, iron, phosphorus, titanium, silicon, lead, tin, indium, bismuth, silver, barium, calcium, mercury, palladium, platinum, tellurium, zirconium, zinc, lanthanum, or the like can be used. Li is particularly preferred α Ni β Co γ Al δ O 2 (1.ltoreq.α.ltoreq.2, β+γ+δ=1, β.ltoreq.0.7, γ.ltoreq.0.2) or Li α Ni β Co γ Mn δ O 2 (1≦α≦1.2、β+γ+δ＝1、β≧0.6、γ≦0.2)。
The positive electrode active material may be used alone or in combination of 2 or more.
In the above-described power storage device of the invention, the separator is not particularly limited, and a porous film or nonwoven fabric of polypropylene, polyethylene or the like may be used. Further, as the separator, a member formed by stacking them may be used. Polyimide, polyamide imide, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, and glass fibers having high heat resistance can be used. In addition, a fabric separator in which these fibers are bundled into a thread form and made into a fabric may be used.
In the above-described power storage device according to the present invention, the electrolyte solution is not particularly limited, and a solution in which a metal salt as an electrolyte is dissolved in a solvent may be used.
Examples of the solvent include cyclic carbonates such as Propylene Carbonate (PC), ethylene Carbonate (EC), butylene Carbonate (BC), and Vinylene Carbonate (VC), chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), and dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate, and ethyl propionate, γ -lactones such as γ -butyrolactone, chain ethers such as 1, 2-Diethoxyethane (DEE), ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran, and 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, acetamide, dimethylformamide, acetonitrile, propionitrile, nitromethane, ethylmonoglyme, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, diethyl ether, 1, 3-sulfolane, and aprotic fluorinated solvents such as benzyl pyrrolidone.
These solvents may be used singly or in combination of 2 or more.
The metal salt is not particularly limited, and lithium salts, sodium salts, calcium salts, magnesium salts, and the like can be used.
When a lithium salt is used as the metal salt, liPF can be used as the lithium salt 6 、LiAsF 6 、LiAlCl 4 、LiClO 4 、LiBF 4 、LiSbF 6 、LiCF 3 SO 3 、LiC 4 F 9 CO 3 、LiC(CF 3 SO 2 ) 2 、LiN(CF 3 SO 2 ) 2 、LiN(C 2 F 5 SO 2 ) 2 、LiB 10 Cl 10 Lithium lower aliphatic carboxylate, lithium borochloride, lithium tetraphenyl borate, liBr, liI, liSCN, liCl, imides, and the like.
These metal salts may be used singly or in combination of 2 or more.
The electrolyte concentration of the electrolyte solution is not particularly limited, but is preferably 0.5 to 1.5mol/L.
When the electrolyte concentration is less than 0.5mol/L, it is difficult to obtain sufficient conductivity of the electrolyte.
When the electrolyte concentration is more than 1.5mol/L, the density and viscosity of the electrolyte tend to increase.
An example of a method of manufacturing a power storage device according to the present invention of this embodiment will be described.
First, a negative electrode collector plate provided with a negative electrode active material, a positive electrode collector plate provided with a positive electrode active material, and a separator are prepared.
Then, a separator is interposed between the negative electrode collector plate and the positive electrode collector plate so that the negative electrode collector plate and the positive electrode collector plate do not contact each other, and the negative electrode collector plate and the positive electrode collector plate are laminated to form a laminate. At this time, the lead portions of the negative electrode collector plates are arranged so as to be exposed from the laminate.
Next, the lead-out portion of the negative electrode collector plate was connected to a lead by ultrasonic welding. Since the connection is performed by ultrasonic welding, the lead portion is not denatured by heat, and is a uniform structure.
The negative electrode current collector plate is made of austenitic stainless steel having a martensitic structure, and the portions thereof connected to the lead wires can be connected to each other by ultrasonic welding without being denatured.
The positive electrode collector plate is also electrically connected to the lead. The method for electrically connecting the positive electrode collector plate and the lead is not particularly limited, and connection may be performed by resistance welding or ultrasonic welding, for example.
Next, the laminate is housed in a power storage case, and an electrolyte solution in which an electrolyte is dissolved is sealed together, whereby the power storage device of the present invention can be manufactured.
Next, another embodiment of the power storage device of the invention will be described.
The electric storage device of the present invention is composed of
A positive electrode,
A negative electrode,
A separator for separating the positive electrode and the negative electrode,
A metal ion supply electrode for doping a metal ion in the positive electrode and/or the negative electrode, a power storage case accommodating the positive electrode, the negative electrode, the separator, and the metal ion supply electrode, and an electrolyte sealed in the power storage case,
the positive electrode, the negative electrode, or the metal ion supply electrode may be the electrode for a power storage device of the present invention.
The case where the electrode for a power storage device according to the present invention is used as a metal ion supply electrode will be described below.
When the electrode for a power storage device of the present invention is used as the metal ion supply electrode, it is necessary to dope the electrode for a power storage device of the present invention with metal ions.
First, a method of doping metal ions in the electrode for an electric storage device according to the present invention will be described.
(1) Organic electrolyte coating process
First, an organic electrolyte is applied to the electrode portion of the collector plate in the electrode for an electric storage device of the present invention.
The organic electrolytic solution is not particularly limited, and a solution obtained by dissolving a metal salt as an electrolyte in an organic solvent can be used.
Examples of the organic solvent include cyclic carbonates such as Propylene Carbonate (PC), ethylene Carbonate (EC), butylene Carbonate (BC) and Vinylene Carbonate (VC), chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methylethyl carbonate (EMC) and dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate, γ -lactones such as γ -butyrolactone, chain ethers such as 1, 2-Diethoxyethane (DEE) and ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, acetamide, dimethylformamide, acetonitrile, propionitrile, nitromethane, ethylmonoglyme, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidone, propylene carbonate derivatives, tetrahydrofuran derivatives, diethyl ether, 1, 3-sulfolane, and aprotic fluorinated solvents such as benzyl lactone and benzyl ether.
These organic solvents may be used alone or in combination of 2 or more.
In the case of using lithium as the metal ion source, the organic electrolytic solution preferably has lithium ion conductivity.
(2) Heating process
Next, the electrode portion coated with the organic electrolyte is brought into contact with a metal ion source, and heated to dope metal ions.
The metal ion source is not particularly limited, and examples thereof include lithium, sodium, magnesium, calcium, and the like. Among these, lithium is preferable.
The heating conditions are not particularly limited, and heating at 250 to 300℃for 10 to 120 minutes is preferable.
(3) Drying process
The doped electrode for the electric storage device is washed with a solvent and then naturally dried, thereby completing doping. As the solvent, DMC (dimethyl carbonate) or the like can be suitably used.
The doping method is not limited to such a method of contacting with the metal ion source, and other methods may be used. For example, the metal ion source and the electrode for the power storage device may be electrically doped by being connected to external circuits, respectively.
The electrode for a power storage device of the present invention is produced by connecting the lead portion of the collector plate and the lead by ultrasonic welding, and doping may be performed before ultrasonic welding or after ultrasonic welding.
When the electrode for an electric storage device of the present invention is used as the metal ion supply electrode, the positive electrode in the electric storage device of the present invention is preferably configured as follows.
That is, the positive electrode is preferably composed of a positive electrode collector plate and a positive electrode active material provided in the positive electrode collector plate.
The positive electrode collector plate is not particularly limited, but preferably contains aluminum, nickel, copper, silver, or an alloy thereof.
The positive electrode active material is not particularly limited, and examples thereof include: liMnO 2 、Li x Mn 2 O 4 (0<x<2)、Li 2 MnO 3 、Li x Mn 1.5 Ni 0.5 O 4 (0<x<2) And lithium manganate having a layered structure or lithium manganate having a spinel structure; liCoO 2 、LiNiO 2 Or a material obtained by replacing a part of these transition metals with other metals; liNi 1/3 Co 1/3 Mn 1/3 O 2 Lithium transition metal oxides of not more than half of the specific transition metals; among these lithium transition metal oxides, those obtained by excess of Li over the stoichiometric composition; liFePO 4 And substances having an olivine structure; etc.
In addition, a material obtained by partially replacing these metal oxides with aluminum, iron, phosphorus, titanium, silicon, lead, tin, indium, bismuth, silver, barium, calcium, mercury, palladium, platinum, tellurium, zirconium, zinc, lanthanum, or the like can be used. Li is particularly preferred α Ni β Co γ Al δ O 2 (1.ltoreq.α.ltoreq.2, β+γ+δ=1, β.ltoreq.0.7, γ.ltoreq.0.2) or Li α Ni β Co γ Mn δ O 2 (1≦α≦1.2、β+γ+δ＝1、β≧0.6、γ≦0.2)。
The positive electrode active material may be used alone or in combination of 2 or more.
When the electrode for an electric storage device of the present invention is used as the metal ion supply electrode, the negative electrode in the electric storage device of the present invention is preferably configured as follows.
That is, the negative electrode preferably includes a negative electrode collector plate, and the electrode portion provided in the negative electrode collector plate includes a negative electrode active material.
The negative electrode collector plate is not particularly limited, but preferably contains aluminum, nickel, copper, silver, an alloy thereof, and the like.
The negative electrode active material is not particularly limited, and preferably contains silicon, silicon monoxide, silicon dioxide, carbon, or the like.
When the electrode for an electric storage device of the present invention is used as the metal ion supply electrode, the separator in the electric storage device of the present invention is not particularly limited, and a porous film or nonwoven fabric of polypropylene, polyethylene or the like may be used. Further, as the separator, a member formed by stacking them may be used. Polyimide, polyamide imide, polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), cellulose, and glass fibers having high heat resistance can be used. In addition, a fabric separator in which these fibers are bundled into a thread form and made into a fabric may be used.
When the electrode for an electric storage device of the present invention is used as the metal ion supply electrode, the electrolyte solution in the electric storage device of the present invention is not particularly limited, and a solution in which a metal salt as an electrolyte is dissolved in a solvent may be used.
Examples of the solvent include cyclic carbonates such as Propylene Carbonate (PC), ethylene Carbonate (EC), butylene Carbonate (BC), and Vinylene Carbonate (VC), chain carbonates such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), and dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate, and ethyl propionate, γ -lactones such as γ -butyrolactone, chain ethers such as 1, 2-Diethoxyethane (DEE), ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran, and 2-methyltetrahydrofuran, dimethyl sulfoxide, 1, 3-dioxolane, formamide, acetamide, dimethylformamide, acetonitrile, propionitrile, nitromethane, ethylmonoglyme, phosphotriester, trimethoxymethane, dioxolane derivatives, sulfolane, methyl sulfolane, 1, 3-dimethyl-2-imidazolidinone, 3-methyl-2-oxazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, diethyl ether, 1, 3-sulfolane, and aprotic fluorinated solvents such as benzyl pyrrolidone.
These solvents may be used singly or in combination of 2 or more.
The metal salt is not particularly limited, and lithium salts, sodium salts, calcium salts, magnesium salts, and the like can be used.
When a lithium salt is used as the metal salt, liPF can be used as the lithium salt 6 、LiAsF 6 、LiAlCl 4 、LiClO 4 、LiBF 4 、LiSbF 6 、LiCF 3 SO 3 、LiC 4 F 9 CO 3 、LiC(CF 3 SO 2 ) 2 、LiN(CF 3 SO 2 ) 2 、LiN(C 2 F 5 SO 2 ) 2 、LiB 10 Cl 10 Lithium lower aliphatic carboxylate, lithium borochloride, lithium tetraphenyl borate, liBr, liI, liSCN, liCl, imides, and the like.
These metal salts may be used singly or in combination of 2 or more.
The electrolyte concentration of the electrolyte solution is not particularly limited, but is preferably 0.5 to 1.5mol/L.
When the electrolyte concentration is less than 0.5mol/L, it is difficult to obtain sufficient conductivity of the electrolyte.
When the electrolyte concentration is more than 1.5mol/L, the density and viscosity of the electrolyte tend to increase.
An example of a method of manufacturing a power storage device according to the present invention of this embodiment will be described.
First, a positive electrode, a negative electrode, and a separator were prepared.
Next, a separator is interposed between the positive electrode and the negative electrode so that the positive electrode and the negative electrode do not contact, and the positive electrode and the negative electrode are laminated to form a laminate.
Separately therefrom, the electrode for a power storage device of the present invention doped with metal ions, that is, the metal ion supply electrode is prepared separately. The lead portion of the metal ion supply electrode and the lead wire formed of nickel-plated copper are connected by ultrasonic welding.
Next, the metal ion supply electrode is arranged outside the laminate, and the metal ion supply electrode and the electrolyte are housed in the power storage case together and sealed in an electrolyte solution in which the electrolyte is dissolved, whereby the power storage device of the present invention can be manufactured.
In addition, by connecting the metal ion supply electrode to the positive electrode or the negative electrode by an external circuit, it is possible to supply the metal ions necessary for charge and discharge to the positive electrode or the negative electrode.
Industrial applicability
The electrode for an electric storage device of the present invention can be suitably used as a positive electrode, a negative electrode, or a metal ion supply electrode for doping metal ions of an electric storage device.
Description of symbols
10. Electrode for electric storage device
20. Current collecting plate
21. Extraction part
22. Main body part
26. Martensitic structure
27. Austenitic structure
30. Electrode part
40. Lead wire

Claims (9)

1. An electrode for an electric storage device comprising a collector plate comprising a main body and a lead-out portion, an electrode portion disposed on the main body of the collector plate, and a lead connected to the lead-out portion of the collector plate,
the lead-out portion and the main body portion are formed of homogenous stainless steel,
the stainless steel is an austenitic stainless steel comprising a martensitic structure,
the electrode portion contains silicon as an active material,
the area of the martensitic structure in the cross section of the lead-out portion cut in the thickness direction is 5-20% of the whole cross section,
the area of the martensitic structure in the cross section of the main body section cut in the thickness direction is 5-20% of the whole cross section.
2. The electrode for an electric storage device according to claim 1, wherein in a cross section of the collector plate cut in a thickness direction, a martensitic structure is dispersed in an austenitic structure in an island shape.
3. The electrode for an electric storage device according to claim 1 or 2, wherein an elastic modulus of the lead is smaller than an elastic modulus of the collector plate.
4. The electrode for an electric storage device according to claim 1 or 2, wherein the lead contains at least one selected from the group consisting of nickel, copper, aluminum, and brass.
5. The electrode for an electric storage device according to claim 1 or 2, wherein the lead is plated with at least one selected from the group consisting of nickel, gold, silver, zinc, and chromium.
6. The electrode for an electric storage device according to claim 1 or 2, wherein the active material contains only silicon.
7. The electrode for an electric storage device according to claim 1 or 2, wherein the electrode for an electric storage device is a metal ion supply electrode that supplies metal ions to an electrolyte.
8. An electric storage device comprising the electrode for an electric storage device according to any one of claims 1 to 7.
9. A method for manufacturing an electrode for an electric storage device, comprising a collector plate comprising a main body portion and a lead-out portion, an electrode portion disposed on the main body portion of the collector plate, and a lead connected to the lead-out portion of the collector plate,
the manufacturing method comprises an ultrasonic connection step of connecting the lead-out portion and the lead by ultrasonic welding,
the current collector plate is formed of austenitic stainless steel including a martensitic structure,
the electrode portion contains silicon as an active material,
the area of the martensitic structure in the cross section of the lead-out portion cut in the thickness direction is 5-20% of the whole cross section,
the area of the martensitic structure in the cross section of the main body section cut in the thickness direction is 5-20% of the whole cross section.
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