WO2022202311A1 - 円筒形非水電解質二次電池 - Google Patents
円筒形非水電解質二次電池 Download PDFInfo
- Publication number
- WO2022202311A1 WO2022202311A1 PCT/JP2022/010201 JP2022010201W WO2022202311A1 WO 2022202311 A1 WO2022202311 A1 WO 2022202311A1 JP 2022010201 W JP2022010201 W JP 2022010201W WO 2022202311 A1 WO2022202311 A1 WO 2022202311A1
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- WIPO (PCT)
- Prior art keywords
- insulating plate
- secondary battery
- aqueous electrolyte
- electrolyte secondary
- negative electrode
- Prior art date
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Images
Classifications
-
- 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
- H01M50/147—Lids or covers
- H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
- H01M50/167—Lids or covers characterised by the methods of assembling casings with lids by crimping
-
- 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
- H01M10/04—Construction or manufacture in general
- H01M10/0422—Cells or battery with cylindrical casing
-
- 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
- H01M10/058—Construction or manufacture
- H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
-
- 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
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/107—Primary casings; Jackets or wrappings characterised by their shape or physical structure having curved cross-section, e.g. round or elliptic
-
- 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
- H01M50/147—Lids or covers
- H01M50/148—Lids or covers characterised by their shape
- H01M50/152—Lids or covers characterised by their shape for cells having curved cross-section, e.g. round or elliptic
-
- 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
- H01M50/147—Lids or covers
- H01M50/166—Lids or covers characterised by the methods of assembling casings with lids
- H01M50/171—Lids or covers characterised by the methods of assembling casings with lids using adhesives or sealing agents
-
- 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
- H01M50/186—Sealing members characterised by the disposition of the 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
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/586—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries inside the batteries, e.g. incorrect connections of electrodes
-
- 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
- H01M50/572—Means for preventing undesired use or discharge
- H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
- H01M50/59—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries characterised by the protection means
- H01M50/593—Spacers; Insulating plates
-
- 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 disclosure relates to cylindrical non-aqueous electrolyte secondary batteries.
- a secondary battery may generate gas due to repeated charging and discharging, and has a mechanism that discharges the gas when the pressure inside the battery exceeds a predetermined value.
- secondary batteries are required to have durability that can withstand impacts from the outside.
- the plane compressive strength of the upper insulating plate placed on the electrode body and the opening ratio of the through holes provided in the upper insulating plate are set to specific ranges to improve the safety of the secondary battery. is disclosed.
- An object of the present disclosure is to provide a cylindrical non-aqueous electrolyte secondary battery with high capacity and improved safety.
- a cylindrical non-aqueous electrolyte secondary battery includes an outer can having a cylindrical shape with a bottom and a grooved portion in an opening, an electrode body and a non-aqueous electrolyte housed in the outer can, and an opening.
- the part includes a sealing body crimped and fixed between the grooved part and the open end, and an upper insulating plate inserted between the electrode body and the sealing body, the upper insulating plate extending from the inner diameter of the grooved part a disk-shaped first insulating plate having a small diameter and a ring-shaped second insulating plate disposed under the first insulating plate, the first insulating plate having higher heat resistance than the second insulating plate. characterized by
- cylindrical non-aqueous electrolyte secondary battery According to the cylindrical non-aqueous electrolyte secondary battery according to the present disclosure, both battery capacity and safety can be achieved.
- FIG. 1 is a vertical cross-sectional view of a cylindrical non-aqueous electrolyte secondary battery that is an example of an embodiment
- FIG. FIG. 4 is a perspective view showing an exploded state of an upper insulating plate in one example of the embodiment
- FIG. 1 is a vertical cross-sectional view of a secondary battery 10 that is an example of an embodiment.
- an electrode body 14 and a non-aqueous electrolyte (not shown) are housed in an outer can 15 .
- the sealing member 16 side will be referred to as "upper” and the bottom side of the outer can 15 will be referred to as "lower”.
- the electrode body 14 has a wound structure in which the positive electrode 11 and the negative electrode 12 are wound with the separator 13 interposed therebetween.
- the positive electrode 11 has a strip-shaped positive electrode current collector and positive electrode mixture layers formed on both sides of the positive electrode current collector.
- the positive electrode current collector for example, a foil of a metal such as aluminum, a film in which the metal is arranged on the surface layer, or the like is used.
- the positive electrode mixture layer is formed, for example, after applying a positive electrode mixture slurry containing a positive electrode active material, a conductive agent, a binder, and a solvent such as N-methyl-2-pyrrolidone (NMP) to both surfaces of the positive electrode current collector. , made by drying and pressing.
- positive electrode active materials include lithium-transition metal composite oxides containing transition metal elements such as Co, Mn, and Ni.
- conductive agents include carbon materials such as carbon black (CB), acetylene black (AB), ketjen black, and graphite.
- binders include fluorine-based resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide (PI), acrylic resins, and polyolefin-based resins.
- fluorine-based resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVdF), polyacrylonitrile (PAN), polyimide (PI), acrylic resins, and polyolefin-based resins.
- the negative electrode 12 has a strip-shaped negative electrode current collector and negative electrode mixture layers formed on both sides of the negative electrode current collector.
- the negative electrode current collector for example, a foil of a metal such as copper, a film in which the metal is arranged on the surface layer, or the like is used.
- the negative electrode mixture layer is produced, for example, by applying a negative electrode mixture slurry containing a negative electrode active material, a binder, water, etc. on both sides of the negative electrode current collector, followed by drying and compression.
- negative electrode active materials include carbon materials such as natural graphite and artificial graphite, metals such as Si and Sn that are alloyed with lithium, and alloys and oxides containing these.
- binders include styrene-butadiene rubber (SBR), CMC or its salts, polyacrylic acid or its salts, polyvinyl alcohol and the like.
- a porous sheet having ion permeability and insulation is used as the separator 13 .
- porous sheets include microporous membranes, woven fabrics, and non-woven fabrics.
- olefin resins such as polyethylene and polypropylene are preferable.
- Carbonates, lactones, ethers, ketones, esters, and the like can be used as the non-aqueous solvent (organic solvent) for the non-aqueous electrolyte contained in the outer can 15, and two or more of these solvents can be used. They can be mixed and used. When using a mixture of two or more solvents, it is preferable to use a mixed solvent containing a cyclic carbonate and a chain carbonate.
- cyclic carbonates such as ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC) can be used, and chain carbonates such as dimethyl carbonate (DMC), ethylmethyl carbonate (EMC), and diethyl carbonate ( DEC) and the like can be used.
- LiPF 6 LiPF 6 , LiBF 4 , LiCF 3 SO 3 and mixtures thereof can be used.
- the amount of the electrolyte salt dissolved in the non-aqueous solvent can be, for example, 0.5 mol/L to 2.0 mol/L.
- the inside of the secondary battery 10 is hermetically sealed by closing the opening of the outer can 15 with the sealing member 16 .
- An upper insulating plate 17 and a lower insulating plate 18 are inserted above and below the electrode body 14, respectively.
- the positive electrode lead 19 extends upward through the through hole of the upper insulating plate 17 and is welded to the lower surface of the filter 22 which is the bottom plate of the sealing member 16 .
- the cap 27, which is the top plate of the sealing member 16 electrically connected to the filter 22, serves as a positive terminal.
- the negative electrode lead 20 extends through the through hole of the lower insulating plate 18 to the bottom side of the outer can 15 and is welded to the inner surface of the bottom of the outer can 15 .
- the outer can 15 serves as a negative electrode terminal.
- the outer can 15 has a cylindrical shape with a bottom, and has a grooved portion 21 at the opening.
- the outer can 15 is made of metal, for example.
- the grooved portion 21 supports the sealing member 16 on its upper surface, as will be described later.
- the electrode body 14 and the non-aqueous electrolyte are accommodated in a portion of the outer can 15 below the grooved portion 21 .
- the grooved portion 21 is present in an annular shape along the circumferential direction of the outer can 15 .
- the grooved portion 21 can be formed, for example, by pressing the side portion of the outer can 15 from the outside.
- the sealing member 16 is crimped and fixed between the grooved part 21 and the opening end of the outer can 15 at the opening.
- the sealing body 16 has a filter 22, a lower valve body 23, an insulating member 24, an upper valve body 25, a PTC thermistor plate 26, and a cap 27, which are stacked in order from the electrode body 14 side.
- Each member constituting the sealing member 16 has, for example, a disk shape or a ring shape, and each member other than the insulating member 24 is electrically connected to each other.
- the lower valve body 23 and the upper valve body 25 are connected to each other at their central portions, and an insulating member 24 is interposed between their peripheral edge portions.
- the lower valve body 23 breaks, causing the upper valve body 25 to swell toward the cap 27 and separate from the lower valve body 23, thereby interrupting the electrical connection between the two. .
- the upper valve body 25 is broken and the gas is discharged from the opening of the cap 27 .
- the temperature of the PTC thermistor plate 26 rises, causing the resistance value of the PTC thermistor plate 26 to rise sharply, thereby interrupting the current.
- FIG. 1 the upper insulating plate 17 will be described with reference to FIGS. 1 and 2.
- FIG. 1 the upper insulating plate 17 will be described with reference to FIGS. 1 and 2.
- the upper insulating plate 17 includes a disk-shaped first insulating plate 17a smaller than the inner diameter of the grooved portion 21 and a ring-shaped second insulating plate 17b arranged below the first insulating plate 17a. and As a result, the first insulating plate 17a can be positioned toward the inside of the grooved portion 21 while the second insulating plate 17b is arranged under the grooved portion 21, so that the accommodating portion for the electrode assembly 14 can be enlarged and The battery capacity of the secondary battery 10 can be improved.
- the ring width of the second insulating plate 17b may be larger than the length of protrusion of the grooved portion 21 toward the inside of the outer can 15 . Thereby, the second insulating plate 17b can support the first insulating plate 17a from below while suppressing the contact between the outer can 15 and the upper portion of the electrode body 14 .
- FIG. 2 is a perspective view showing an exploded state of the upper insulating plate 17 in one example of the embodiment.
- the diameter of the first insulating plate 17a is larger than the inner diameter of the ring of the second insulating plate 17b and smaller than the outer diameter of the ring of the second insulating plate 17b.
- the first insulating plate 17a may have a first hole 30 and a second hole 32, as shown in FIG.
- the first hole 30 and the second hole 32 are holes penetrating the first insulating plate 17a.
- the first hole 30 has a function of releasing gas generated by the reaction between the electrode and the non-aqueous electrolyte to the upper part of the secondary battery 10 .
- the shape of the first hole 30 is not particularly limited, it is, for example, a circle. Moreover, the number of first holes 30 is not particularly limited as long as it is one or more.
- the second hole 32 is a hole for passing the positive electrode lead 19 .
- the second hole 32 is, for example, larger than the first hole 30 and has a substantially semicircular shape.
- the first insulating plate 17a has higher heat resistance than the second insulating plate 17b. As a result, even if the secondary battery 10 overheats or ignites, the first insulating plate 17a maintains its shape and secures an exhaust path for gas generated inside the battery, preventing the secondary battery 10 from bursting. It is possible to suppress the discharge of gas from other than the opening hole of the cap 27 .
- thermosetting resins such as phenol resin, epoxy resin, and unsaturated polyester resin impregnated with insulating fibers such as glass fibers.
- phenolic resin (GP) mixed with glass fiber is preferable.
- Examples of materials for the second insulating plate 17b include polypropylene (PP) and polyethylene (PE). PP is preferable as the material of the second insulating plate 17b. Since PP is easy to process, the second insulating plate 17b made of PP is easy to manufacture. In addition, since PP is easily deformed, even if the secondary battery 10 is deformed by an external impact, the second insulating plate 17b does not break and contact between the outer can 15 and the upper part of the electrode body 14 is suppressed. can be done.
- PP polypropylene
- PE polyethylene
- the thickness of the first insulating plate 17a is preferably greater than the thickness of the second insulating plate 17b. Thereby, the heat resistance of the secondary battery 10 can be improved. Also, by making the second insulating plate 17b thinner than the first insulating plate 17a, the battery capacity of the secondary battery 10 can be improved. In addition, by making the second insulating plate 17b into a thin ring shape, even if the secondary battery 10 is deformed by an external impact, the second insulating plate 17b will not break, and the outer can 15 and the upper portion of the electrode body 14 will not break. contact can be suppressed.
- the thickness of the first insulating plate 17a is, for example, 0.2 mm to 0.5 mm. Also, the thickness of the second insulating plate 17b is, for example, 0.1 mm to 0.2 mm.
- Example 1 [Preparation of positive electrode] A lithium transition metal composite oxide represented by LiNi 0.8 Co 0.15 Al 0.05 O 2 was used as a positive electrode active material. 100 parts by mass of this positive electrode active material, 2.0 parts by mass of acetylene black (AB) as a conductive agent, and 2.0 parts by mass of polyvinylidene fluoride (PVdF) as a binder are mixed, and , N-methyl-2-pyrrolidone (NMP) was added in an appropriate amount to prepare a positive electrode mixture slurry.
- AB acetylene black
- PVdF polyvinylidene fluoride
- NMP N-methyl-2-pyrrolidone
- this positive electrode mixture slurry was applied to both sides of a positive electrode current collector made of aluminum foil, dried, cut into a predetermined electrode size, and rolled using a roller to obtain a band-shaped positive electrode.
- a positive electrode exposed portion in which the mixture layer was not present and the surface of the current collector was exposed was provided approximately in the center of the positive electrode in the longitudinal direction, and an aluminum positive electrode lead was welded to the positive electrode exposed portion.
- Graphite was used as a negative electrode active material. 100 parts by mass of this negative electrode active material, 1.0 parts by mass of styrene-butadiene rubber (SBR) as a binder, and 1.0 parts by mass of carboxymethyl cellulose (CMC) as a thickener are mixed, and An appropriate amount of water was added to prepare a negative electrode mixture slurry. Next, this negative electrode mixture slurry was applied to both sides of a negative electrode current collector made of copper foil, dried, cut into a predetermined electrode size, and rolled using a roller to obtain a band-shaped negative electrode. A negative electrode exposed portion where the current collector surface was exposed without the mixture layer being present was provided at the winding outer end of the negative electrode, and a nickel-copper negative electrode lead was welded to the negative electrode exposed portion.
- SBR styrene-butadiene rubber
- CMC carboxymethyl cellulose
- a spirally wound electrode body was produced by spirally winding the produced positive electrode and negative electrode with a microporous membrane separator made of an olefin resin interposed therebetween. At that time, one end to which the positive electrode lead of the positive electrode was connected was positioned at the inner end of the winding, and one end to which the negative electrode lead of the negative electrode was connected was positioned at the outer end of the winding.
- LiPF 6 was added to a mixed solvent in which ethylene carbonate (EC) and diethyl carbonate (DEC) were mixed so that the volume ratio of EC:DMC was 40:60, and LiPF 6 was added so as to be 1 mol/L.
- An electrolyte was prepared.
- Phenol resin (GP) mixed with glass fiber was selected as the material of the first insulating plate.
- Polypropylene (PP) was selected as the material for the second insulating plate.
- the first insulating plate was formed in a disc shape having first and second holes, and the second insulating plate was formed in a ring shape.
- the outer diameter of the first insulating plate is set so as to substantially inscribe the inner diameter of the grooved portion of the outer can.
- the thickness of the first insulating plate was set to 0.3 mm.
- the outer diameter of the second insulating plate was set so as to substantially inscribe the outer can.
- the ring width of the second insulating plate was set to a size that can sufficiently cover the inward protruding length of the grooved portion in order to ensure sufficient insulation between the outer can and the electrode body.
- the thickness of the second insulating plate was 0.1 mm. It should be noted that this thickness is thinner than the insulating plate that has been used conventionally.
- a bottomed cylindrical metal can having a diameter of 18 mm and a height of 65 mm was used as an outer can.
- a lower insulating plate was placed under the electrode assembly, and the electrode assembly was housed in an outer can with the first insulating plate and the second insulating plate placed above the electrode assembly in this order.
- the negative electrode lead is welded to the bottom of the outer can, the sealing body is welded to the positive electrode lead, and a groove is formed in the opening of the outer can by pressing, and then the non-aqueous electrolyte is injected into the outer can. did.
- the opening of the outer can was sealed by crimping the sealing member with a gasket 28 interposed therebetween to produce a cylindrical non-aqueous electrolyte secondary battery.
- the rated capacity of the produced secondary battery was 5 Ah.
- Example 1 A battery was fabricated in the same manner as in Example 1, except that PP was selected as the material for the first insulating plate in fabricating the upper insulating plate.
- Example 2 A battery was fabricated in the same manner as in Example 1, except that GP was selected as the material for the second insulating plate in fabricating the upper insulating plate.
- Example 3 A battery was fabricated in the same manner as in Example 1, except that PP was selected as the material for the first insulating plate and GP was selected as the material for the second insulating plate in fabricating the upper insulating plate.
- PP was selected as the material, and a fourth insulating plate having a shape similar to that of the first insulating plate in plan view and having the same outer diameter as that of the second insulating plate was produced.
- a battery was fabricated in the same manner as in Example 1, except that this was used as the upper insulating plate.
- the thickness of the fourth insulating plate was the same as that of the first insulating plate.
- Table 1 shows the evaluation results of Examples and Comparative Examples. Table 1 shows the number of batteries in which short-circuit marks were confirmed in the flat plate crush test and the number of batteries in which rupture or pinholes were confirmed in the combustion test. In the combustion test, if any of the five batteries was found to be damaged, these batteries were not checked for pinholes. Table 1 also shows the materials and shapes of the first insulating plate and the second insulating plate.
- 10 secondary battery 11 positive electrode, 12 negative electrode, 13 separator, 14 electrode body, 15 outer can, 16 sealing body, 17 upper insulating plate, 17a first insulating plate, 17b second insulating plate, 18 lower insulating plate, 19 positive electrode Lead, 20 negative electrode lead, 21 grooved portion, 22 filter, 23 lower valve body, 24 insulating member, 25 upper valve body, 26 PTC thermistor plate, 27 cap, 28 gasket, 30 first hole, 32 second hole
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Sealing Battery Cases Or Jackets (AREA)
Abstract
Description
[正極の作製]
正極活物質として、LiNi0.8Co0.15Al0.05O2で表されるリチウム遷移金属複合酸化物を用いた。この正極活物質を100質量部と、導電剤としてのアセチレンブラック(AB)を2.0質量部と、結着剤としてのポリフッ化ビニリデン(PVdF)を2.0質量部とを混合し、さらに、N-メチル-2-ピロリドン(NMP)を適量加えて、正極合剤スラリーを調製した。次に、この正極合剤スラリーをアルミニウム箔からなる正極集電体の両面に塗布し、乾燥させた後、所定の電極サイズに切り取り、ローラを用いて圧延して帯状の正極を得た。正極の長手方向の略中央部に、合剤層が存在せず集電体表面が露出した正極露出部を設け、アルミニウム製の正極リードを正極露出部に溶接した。
負極活物質として、グラファイトを用いた。この負極活物質100質量部と、結着剤としてのスチレン―ブタジエンゴム(SBR)1.0質量部と、増粘剤としてのカルボキシメチルセルロース(CMC)1.0質量部とを混合し、さらに、水を適量加えて、負極合剤スラリーを調製した。次に、この負極合剤スラリーを、銅箔からなる負極集電体の両面に塗布し、乾燥させた後、所定の電極サイズに切り取り、ローラを用いて圧延して帯状の負極を得た。負極の巻外端部に合剤層が存在せず集電体表面が露出した負極露出部を設け、ニッケル‐銅製の負極リードを負極露出部に溶接した。
作製された正極及び負極を、オレフィン系樹脂からなる微多孔膜のセパレータを介して渦巻状に巻回することにより、巻回型の電極体を作製した。その際、正極の正極リードが接続された一端部が巻内端部に位置し、負極の負極リードが接続された一端部が巻外端部に位置するようにした。
エチレンカーボネート(EC)と、ジエチルカーボネート(DEC)とを、体積比でEC:DMC=40:60となるように混合した混合溶媒に、LiPF6を1モル/Lとなるように添加し非水電解液を調製した。
第1絶縁板の素材としてガラス繊維を混合したフェノール樹脂(GP)を選択した。また、第2絶縁板の素材として、ポリプロピレン(PP)を選択した。図2に示すように、第1絶縁板は、第1孔及び第2孔を有する円盤状に形成し、第2絶縁板は、リング状に形成した。第1絶縁板の外径は、外装缶の溝入部の内径に略内接する大きさとした。また、第1絶縁板の厚みは、0.3mmとした。第2絶縁板の外径は、外装缶に略内接する大きさとした。また、第2絶縁板のリング幅は、外装缶と電極体の絶縁性を十分に確保するために、溝入部の内側方向への突出長さを十分に覆うことができる大きさに設定した。第2絶縁板の厚みは、0.1mmとした。なお、この厚みは、従来使用されてきた絶縁板より薄いものである。
直径φ18mm、高さ65mmの有底円筒形状の金属缶を外装缶とした。電極体の下部には下部絶縁板を配置し、電極体の上部には上から第1絶縁板、第2絶縁板の順に上部絶縁板を配置した状態で、電極体を外装缶に収容した。次に、負極リードを外装缶の底部に溶接し、正極リードに封口体を溶接し、外装缶の開口部にプレスで溝入部を形成してから、外装缶の内部に非水電解質を注液した。その後、外装缶の開口部を、ガスケット28を介して封口体をかしめるように封口して、円筒形非水電解質二次電池を作製した。作製した二次電池の定格容量は、5Ahであった。
上部絶縁板の作製において、第1絶縁板の素材としてPPを選択したこと以外は、実施例1と同様にして電池を作製した。
上部絶縁板の作製において、第2絶縁板の素材としてGPを選択したこと以外は、実施例1と同様にして電池を作製した。
上部絶縁板の作製において、第1絶縁板の素材としてPPを選択し、第2絶縁板の素材としてGPを選択したこと以外は、実施例1と同様にして電池を作製した。
上部絶縁板の作製において、素材としてGPを選択し、平面視における形状が第1絶縁板に相似な形状で、外径が第2絶縁板と同じになるような、第3絶縁板を作製して、これを上部絶縁板としたこと以外は、実施例1と同様にして電池を作製した。なお、第3絶縁板の厚みは、第1絶縁板と同じであった。
上部絶縁板の作製において、素材としてPPを選択し、平面視における形状が第1絶縁板に相似な形状で、外径が第2絶縁板と同じになるような、第4絶縁板を作製して、これを上部絶縁板としたこと以外は、実施例1と同様にして電池を作製した。なお、第4絶縁板の厚みは、第1絶縁板と同じであった。
実施例及び比較例に係る各電池10個ずつについて、平板圧壊試験を行った。まず、25℃の環境下で、0.3Itの定電流で電池電圧が4.2Vになるまで充電を行い、4.2Vで電流値が1/50Itになるまで定電圧充電を行った。その後、0.2Itの定電流で電池電圧が2.5Vになるまで放電を行った。次に、25℃の環境下で、20cm×20cmの正方形のステンレス板で、放電後の二次電池を側面方向から、荷重20kN、スピード15mm/秒の条件で加圧した。外装缶の直径に対して10%変形するまで圧壊したものを5個と、外装缶の直径に対して25%変形するまで圧壊したものを5個作製した。試験後の電池を分解し、上部絶縁板が破壊されたことにより、電極体の上部において短絡が発生していないかを確認した。
満実施例及び比較例に係る各電池5個ずつについて、燃焼試験を行った。まず、25℃の環境下で、0.3Itの定電流で電池電圧が4.2Vになるまで充電を行い、4.2Vで電流値が1/50Itになるまで定電圧充電を行った。充電後の電池を、金属製の網の上に寝かした状態で載置し、金属製の網の上をアルミニウム製の網籠で覆い、網の直下38mm離れたバーナーの炎で二次電池の側面を加熱した。試験後の電池について、破裂していないかと、ピンホールが発生していないかを確認した。
Claims (2)
- 有底円筒形状で、開口部に溝入部を有する外装缶と、
前記外装缶に収容される、電極体及び非水電解質と、
前記開口部において、前記溝入部と開口端部との間にかしめ固定される封口体と、
前記電極体と前記封口体との間に挿入された上部絶縁板とを備え、
前記上部絶縁板は、前記溝入部の内径よりも小さい円盤状の第1絶縁板と、前記第1絶縁板の下に配置されるリング状の第2絶縁板とを有し、
前記第1絶縁板は、前記第2絶縁板よりも耐熱性が高い、円筒形非水電解質二次電池。 - 前記第2絶縁板のリング幅は、前記溝入部の前記外装缶の内側方向への突出長さよりも大きい、請求項1に記載の円筒形非水電解質二次電池。
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US18/281,668 US20240154280A1 (en) | 2021-03-24 | 2022-03-09 | Cylindrical non-aqueous electrolyte secondary battery |
JP2023508959A JPWO2022202311A1 (ja) | 2021-03-24 | 2022-03-09 | |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62103169U (ja) * | 1985-12-19 | 1987-07-01 | ||
JPH08264173A (ja) * | 1995-03-20 | 1996-10-11 | Hitachi Maxell Ltd | アルカリ蓄電池 |
JPH1140135A (ja) * | 1997-07-17 | 1999-02-12 | Fuji Photo Film Co Ltd | 筒状電池 |
JP2014053262A (ja) | 2012-09-10 | 2014-03-20 | Panasonic Corp | 密閉型二次電池 |
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- 2022-03-09 US US18/281,668 patent/US20240154280A1/en active Pending
- 2022-03-09 CN CN202280019555.3A patent/CN116964861A/zh active Pending
- 2022-03-09 JP JP2023508959A patent/JPWO2022202311A1/ja active Pending
- 2022-03-09 WO PCT/JP2022/010201 patent/WO2022202311A1/ja active Application Filing
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62103169U (ja) * | 1985-12-19 | 1987-07-01 | ||
JPH08264173A (ja) * | 1995-03-20 | 1996-10-11 | Hitachi Maxell Ltd | アルカリ蓄電池 |
JPH1140135A (ja) * | 1997-07-17 | 1999-02-12 | Fuji Photo Film Co Ltd | 筒状電池 |
JP2014053262A (ja) | 2012-09-10 | 2014-03-20 | Panasonic Corp | 密閉型二次電池 |
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