WO2013046644A1 - コイン形電池 - Google Patents
コイン形電池 Download PDFInfo
- Publication number
- WO2013046644A1 WO2013046644A1 PCT/JP2012/006094 JP2012006094W WO2013046644A1 WO 2013046644 A1 WO2013046644 A1 WO 2013046644A1 JP 2012006094 W JP2012006094 W JP 2012006094W WO 2013046644 A1 WO2013046644 A1 WO 2013046644A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- side wall
- sealing plate
- coin
- curved portion
- battery
- Prior art date
Links
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- 239000003792 electrolyte Substances 0.000 claims abstract description 8
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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
- H01M50/102—Primary casings; Jackets or wrappings characterised by their shape or physical structure
- H01M50/109—Primary casings; Jackets or wrappings characterised by their shape or physical structure of button or coin shape
-
- 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
- H01M50/147—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
- 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
- H01M50/184—Sealing members characterised by their shape or structure
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/191—Inorganic material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to a coin-type battery, and more particularly, to a coin-type battery with improved rust prevention effect and resistance to leakage by improving a sealing plate.
- Coin-type batteries also called flat batteries, are small and thin, and are widely used in applications that require downsizing, such as watches and keyless entries, taking advantage of their features.
- Coin-type batteries are also used in applications requiring long-term use such as memory backup for OA devices and FA devices, as well as various meters and power supplies for measurement, and the applications are constantly expanding.
- the usage environment of coin-type batteries is also expanding from a normal temperature range to a low temperature range or a high temperature range.
- the coin battery is composed of a power generation element and an exterior body that accommodates the power generation element.
- the exterior body includes a shallow cylindrical battery case, a sealing plate that closes the opening of the battery case, and a gasket that is interposed between the opening end of the battery case and the peripheral portion of the sealing plate. And after placing the positive electrode and the negative electrode in the battery case facing each other via a separator and filling the electrolyte solution, the opening end of the battery case is crimped to the peripheral edge of the sealing plate via the gasket, The interior of the exterior body is sealed.
- stainless steel is conventionally used for the sealing plate and the battery case. Since stainless steel has high mechanical strength, the battery case can be firmly crimped to the peripheral edge of the sealing plate while suppressing deformation, and the power generation element is excellent in sealing performance.
- sealing plate If the sealing plate is deformed, liquid leakage may occur or the nickel plating may crack when the coin-type battery is used in severe vibration environments or continuously in a hot and humid environment.
- the sealing plate may rust.
- an object of the present invention is to provide a highly reliable coin-type battery excellent in rust prevention effect and resistance to leakage.
- One aspect of the present invention includes a positive electrode, a negative electrode, a power generation element including an electrolyte and a separator interposed between the positive electrode and the negative electrode, and an exterior body that houses the power generation element.
- a cylindrical battery case having a bottom wall and a first side wall rising from a peripheral edge of the bottom surface; a top plate and a sealing plate having a second side wall extending from the peripheral edge of the top surface to the inside of the first side wall;
- a gasket having at least a portion interposed between the first side wall and the second side wall, and the sealing plate includes a first curved portion formed at a boundary between the top surface portion and the second side wall.
- the ratio of the curvature radius R2 of the outer surface side of the second bending portion: R1 / R2 is a 0.22 to 1.88, to a coin-shaped battery.
- the deformation of the sealing plate can be significantly suppressed. Therefore, the reliability when using the coin-type battery in a harsh environment is improved. Further, even when an inexpensive steel material is used for the sealing plate, deformation of the sealing plate can be suppressed, so that the manufacturing cost of the coin-type battery can be greatly reduced.
- the coin battery of the present invention includes a positive electrode, a negative electrode, a power generation element including a separator and an electrolyte interposed between the positive electrode and the negative electrode, and an exterior body that houses the power generation element.
- the exterior body has a bottom surface and a cylindrical battery case having a first side wall rising from the periphery of the bottom surface, and a sealing member having a second side wall extending from the periphery of the top surface and the top surface to the inside of the first side wall of the battery case.
- a plate and a gasket at least partially interposed between the first side wall and the second side wall.
- the sealing plate is formed following the first curved portion formed at the boundary between the top surface portion and the second side wall, the second curved portion formed following the first curved portion, and the second curved portion.
- the sealing plate has a ratio of R1 / R2 between the curvature radius R1 on the outer surface side of the first curved portion and the curvature radius R2 on the outer surface side of the second curved portion so as to be 0.22 to 1.88. Is formed.
- the opening edge part namely, edge part of the 1st side wall
- the applied pressure can be distributed over a wider range. Therefore, as a matter of course, when stainless steel is used, even when a steel material having relatively low strength is used as the material of the sealing plate, deformation of the sealing plate during caulking can be significantly suppressed. In addition, since the amount of deformation of the sealing plate is reduced during processing to form the sealing plate and during caulking, peeling and cracking of the plating layer is suppressed even when using a material with a plated surface. The Therefore, generation
- the sealing plate is made of ordinary steel.
- ordinary steel it is possible to significantly reduce the manufacturing cost of the coin-type battery compared to the case of using stainless steel.
- the battery case is preferably made of stainless steel. This is because the battery case is more easily corroded than the sealing plate due to a potential difference between the positive electrode and the negative electrode.
- the battery case is more easily corroded than the sealing plate due to a potential difference between the positive electrode and the negative electrode.
- an organic electrolyte it is preferable to use lithium or a lithium alloy for the negative electrode.
- the battery voltage is about 3V. Therefore, when ordinary steel is used as the battery case material, corrosion of the battery case due to oxidation tends to occur.
- the radius of curvature R1 on the outer surface side of the first curved portion of the sealing plate makes it possible to disperse the applied pressure over a wider range with respect to the pressurization during caulking, and to greatly suppress deformation of the sealing plate.
- the thickness is preferably 0.3 to 0.5 mm.
- an adhesive sealant is interposed between the gasket and at least one selected from the first side wall of the battery case and the second side wall of the sealing plate.
- FIG. 1 is a cross-sectional view showing a configuration of a coin-type battery according to an embodiment of the present invention.
- the coin-type battery 100 includes an exterior body that includes a battery case 1, a sealing plate 6, and a gasket 5.
- the battery case 1 is a cylindrical battery having a bottom surface 1a and a first side wall 1b rising from the periphery of the bottom surface 1a, and is a shallow battery can.
- the sealing plate 6 has a top surface portion 6 a and a second side wall 6 b extending from the periphery of the top surface portion 6 a to the inside of the first side wall 1 b of the battery case 1.
- a part of the gasket 5 is interposed between the first side wall 1 b of the battery case 1 and the second side wall 6 b of the sealing plate 6, thereby sealing a gap between the battery case 1 and the sealing plate 6.
- the gasket 5 has an annular groove that fits into the peripheral edge of the sealing plate 6.
- polypropylene PP
- polyphenylene sulfide PPS
- PEEK polyether ether ketone
- a sticky sealant may be interposed between the gasket 5 and the first side wall 1b. Moreover, you may interpose the sealing agent which has adhesiveness between the gasket 5 and the 2nd side wall 6b.
- the sealant pitch, asphalt, vinyl polymer, silicon polymer, rubber polymer, fluorine polymer, or the like can be used.
- the sealant may contain mineral oil.
- FIG. 2 is a cross-sectional view of the main part of the sealing plate 6 included in the coin battery 100.
- the sealing plate 6 includes a first bending portion 8 formed at the boundary between the top surface portion 6a and the second side wall 6b, a second bending portion 9 formed following the first bending portion 8, and a second bending portion 9
- the third bending portion 10 formed subsequent to the third bending portion 10 and the downward falling portion 12 formed following the third bending portion 10 are provided.
- the horizontal distance Dd (the distance in the direction parallel to the top surface portion 6a) between the points P 1 and P 3 is, for example, 0.4 to 1.0 mm.
- the sealing plate 6 has a ratio R1 / R2 of the curvature radius R1 on the outer surface side of the first curved portion 8 to the curvature radius R2 on the outer surface side of the second curved portion 9 is 0.22 to 1.88. It is formed as follows. By setting the R1 / R2 ratio in the range of 0.22 to 1.88, when the first side wall 1b of the battery case 1 is pressed against the second side wall 6b of the sealing plate 6 via the gasket 5, the second side wall 1b is pressed. It is possible to disperse the pressure applied to the side wall 6b in a wider range. Therefore, deformation of the sealing plate during caulking can be greatly suppressed.
- the R1 / R2 ratio is more preferably in the range of 0.30 to 1.50, and still more preferably in the range of 0.50 to 1.00, from the viewpoint of maintaining high capacity and excellent pressure resistance. .
- R1 / R2 ratio is greater than 1.88, the second curved portion 9 of the sealing plate 6 tends to be excessively deformed toward the inner diameter direction during caulking. Therefore, a slight gap is easily generated between the second side wall 6b of the sealing plate 6 and the gasket 5, and liquid leakage is likely to occur. Moreover, when R1 / R2 ratio is smaller than 0.22, the clearance gap between the sealing board 6 and the 1st side wall 1b of the battery case 1 tends to become excessively small at the time of caulking. Therefore, the gasket 5 protrudes from between the first side wall 1b and the second side wall 6b, or the position of the sealing agent applied to the surface of the gasket is shifted, and the sealing effect is lowered.
- the shape of the sealing plate 6 is not limited to the shape shown in FIG. FIG. 3 shows a cross-sectional view of the main part of another sealing plate.
- the sealing plate 6A of FIG. 3 has a top surface portion 6Aa and a second side wall 6Ab that falls from the peripheral edge thereof, and a first curved portion 8A and a first curved portion 8A at the boundary between the top surface portion 6Aa and the second side wall 6Ab. It is the same as the sealing plate 6 in that it includes a second bending portion 9A following the second bending portion 9A, a third bending portion 10A following the second bending portion 9A, and a downward falling portion 12A following the third bending portion 10A. is there.
- the falling part 12 ⁇ / b> A has a folded structure with its endmost part folded back to the outer surface side of the battery.
- the strength of the second side wall 6Ab of the sealing plate 6A is increased, and the reliability of the sealing portion is further improved.
- a coin-type battery is a cylindrical battery having a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a power generation element including an electrolyte, and a cylindrical battery having a bottom surface portion and a first side wall rising from the periphery of the bottom surface portion
- a step (i) of preparing a case a step (ii) of preparing a sealing plate having a top surface portion and a second side wall falling from the periphery of the top surface portion, and at least a part between the first side wall and the second side wall
- Step (iii) of preparing a gasket for interposing the battery case and after accommodating the power generation element in the battery case, the opening of the electronic case is closed with the sealing plate, and the opening end of the battery case is connected to the sealing plate through the gasket.
- the battery case 1 is formed by forming a stainless steel plate into a bottomed cylindrical shape by drawing. It is preferable that nickel plating is given to the surface of the stainless steel plate at least on the outer surface side of the battery.
- the thickness of the stainless steel plate is, for example, 0.15 to 0.35 mm.
- a sealing plate having a predetermined shape is formed by, for example, pressing a metal plate.
- the metal plate is formed following the first curved portion formed at the boundary between the top surface portion and the second side wall, the second curved portion formed following the first curved portion, and the second curved portion.
- the R1 / R2 ratio can be controlled by the mold shape, press pressure, etc. during press working.
- a stainless steel plate can be used, but from the viewpoint of manufacturing cost, it is desirable to use a steel plate such as inexpensive ordinary steel or carbon steel. It is preferable that nickel plating is given to the surface of the outer surface side of a battery of the metal plate used for a sealing board.
- the thickness of the metal plate is, for example, 0.10 to 0.40 mm.
- ordinary steel is steel such as SS material, SM material and SPCC material specified in JIS.
- Carbon steel is not special steel such as stainless steel (SUS material), which is represented by high alloy among special steels, but is a steel material such as S10C, S20C, S30C, S45C, and S55C. Belongs to alloy steel. Among these, carbon steel is preferable because it is inexpensive and excellent in workability and corrosion resistance.
- the thickness of the nickel plating layer applied to the constituent material of the battery case or the sealing plate is preferably 0.5 ⁇ m to 8 ⁇ m, more preferably 1 ⁇ m to 4 ⁇ m. If the nickel plating layer is too thin, the rust prevention effect is weakened. On the other hand, if the nickel plating layer is too thick, the rust prevention effect is not changed, but the production cost is increased.
- the nickel-plated material is then preferably heat treated. The temperature of the heat treatment is, for example, 200 to 700 ° C.
- the deformation amount of the sealing plate during caulking is sufficiently reduced. Can do. Thereby, even when nickel plating is given to the steel plate, peeling and cracking of the nickel plating layer are suppressed. Therefore, even when the nickel plating layer is relatively thin (for example, in the case of 0.5 to 1.0 ⁇ m), the rust prevention effect is unlikely to decrease.
- step (iv) that is, in the battery assembly step including caulking, first, the power generation element is accommodated in the battery case, and a gasket is disposed on the inner surface of the first side wall of the battery case. And after arrange
- the power generation element includes a positive electrode 2, a negative electrode 3, a separator 4, and an electrolytic solution (not shown).
- a current collector 14 is disposed between the positive electrode 2 and the bottom surface portion 1 a of the battery case 1.
- the positive electrode 2 is obtained by press-molding a positive electrode mixture containing a positive electrode active material, a conductive additive and a binder into a coin-like pellet.
- the type of the positive electrode active material is not particularly limited, but is an oxide (for example, manganese dioxide) or a composite containing at least one selected from the group consisting of transition metals such as manganese, cobalt, nickel, magnesium, copper, iron, and niobium.
- An oxide can be used.
- a composite oxide containing lithium and containing at least one selected from the group consisting of metals such as manganese, cobalt, nickel, magnesium, copper, iron, and niobium (for example, LiCoO 2 ) can also be used.
- fluorinated graphite can also be used.
- a positive electrode active material may be used individually by 1 type, and may be used in combination of 2 or more type.
- carbon black such as acetylene black and ketjen black
- graphite such as artificial graphite
- a conductive support material may be used individually by 1 type, and may be used in combination of 2 or more type.
- binders include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), modified PVDF, tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer.
- fluorine resins such as a polymer (PFA) and a vinylidene fluoride-hexafluoropropylene copolymer, styrene butadiene rubber (SBR), a modified acrylonitrile rubber, and an ethylene-acrylic acid copolymer.
- a binder may be used individually by 1 type, and may be used in combination of 2 or more type.
- the negative electrode 3 is formed, for example, by coining lithium metal or a lithium alloy.
- the lithium alloy include a Li—Al alloy, a Li—Sn alloy, a Li—Si alloy, and a Li—Pb alloy.
- the negative electrode 3 may be a negative electrode mixture containing a negative electrode active material and a binder, which is pressure-molded into a pellet shape.
- the type of the negative electrode active material is not particularly limited, but carbon materials such as natural graphite, artificial graphite, and non-graphitizable carbon, and metal oxides such as silicon oxide, lithium titanate, niobium pentoxide, and molybdenum dioxide may be used. it can.
- As a binder the material illustrated as a material which can be used for a positive electrode, for example can be used arbitrarily.
- a conductive additive may be included in the negative electrode mixture.
- an organic electrolyte is composed of a non-aqueous solvent and a solute (salt) that dissolves therein.
- the solute concentration in the electrolytic solution is preferably 0.3 to 2.0 mol / L.
- Nonaqueous solvents include cyclic carbonates such as propylene carbonate, ethylene carbonate, butylene carbonate and vinylene carbonate, chain carbonates such as dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate, 1,2-dimethoxyethane, diglyme (diethylene glycol methyl). Ether), triglyme (triethylene glycol dimethyl ether), tetraglyme (tetraethylene glycol dimethyl ether), 1,2-dimethoxyethane, 1,2-diethoxymethane, tetrahydrofuran, and the like can be used. These may be used alone or in combination of two or more.
- LiBF 4 LiPF 6 , LiAsF 6 , LiSbF 6 , LiClO 4 , LiCF 3 SO 3 , LiC 4 F 9 SO 3 , LiN (CF 3 SO 2 ) 2 , LiN (C 2 F 5 SO 2 ) 2 Etc. are used.
- the separator 4 may be any material that can prevent a short circuit between the positive electrode 2 and the negative electrode 3, but a material that has excellent electrolyte permeability and low resistance to ion migration is desirable. As such material, it was formed with polyolefin, polyester, polycarbonate, polyacrylate, polymethacrylate, polyamide, polytetrafluoroethylene, polyvinylidene fluoride, polysulfone, polyethersulfone, polybenzimidazole, polyetheretherketone, polyphenylene, etc. A woven fabric, a nonwoven fabric, a microporous film, etc. are mentioned.
- Example Next, the present invention will be specifically described based on examples. However, the following examples do not limit the present invention.
- a coin-type battery having a structure as shown in FIG. 1 was produced.
- (Ii) Sealing plate A plurality of sealing plates 6 were produced by variously changing the curvature radius R1 on the outer surface side of the first bending portion 8 and the curvature radius R2 on the outer surface side of the second bending portion 9.
- a steel steel carbon steel plate (thickness: 200 ⁇ m) having a nickel plating layer with a thickness of 3 ⁇ m on the surface was used.
- This steel sheet was processed into a predetermined shape with a diameter of the top surface portion 6a of 17 mm by pressing.
- the height difference Hd 1 between the height H 1 of the point P 1 with the highest curvature of the first curved portion 8 and the height H 3 of the point P 3 with the highest curvature of the third curved portion 10 is: 0.9 mm
- the horizontal distance between the point P 1 and point P 3: Dd is 0.6 mm
- the height difference between the height H 4 of the lowermost point P 4 of the height H 3 and falling part 12: Hd 2 was 1.3 mm.
- R1 was 0.30 mm, 0.40 mm, or 0.50 mm.
- R2 was varied in the range of 0.16 to 2.00 mm (Examples 1 to 24) or 0.10 to 2.00 mm (Comparative Examples 1 to 15). In Examples 1 to 24, the R1 / R2 ratio was controlled to 0.22 to 1.88. In Comparative Examples 1 to 15, the R1 / R2 ratio was controlled to 0.15 to 5.00. Table 1 shows the combinations of R1 and R2 and the R1 / R2 ratio.
- Positive electrode A positive electrode mixture is prepared by mixing 100 parts by mass of manganese dioxide, which is a positive electrode active material, 7 parts by mass of graphite, which is a conductive additive, and 1 part by mass of polytetrafluoroethylene, which is a binder. did. The positive electrode mixture was formed into a coin-shaped pellet having a diameter of 15 mm and a thickness of 2 mm to obtain a positive electrode 2.
- Negative electrode A metal lithium foil having a thickness of 0.6 mm was punched into a circle having a diameter of 16 mm to obtain a negative electrode.
- Electrolytic Solution An organic electrolytic solution in which LiClO 4 was dissolved as a solute at a concentration of 1.0 mol / L in a nonaqueous solvent in which propylene carbonate and 1,2-dimethoxyethane were mixed at a volume ratio of 2: 1 was used. .
- (Viii) Battery assembly A gasket 5 coated with a sealant made of bron asphalt and mineral oil is disposed inside the first side wall 1b of the battery case 1, and a current collector made of SUS444 is disposed on the bottom surface 1a. And the positive electrode 2 was mounted on it. Next, the separator 4 was placed on the positive electrode 2, and then the organic electrolyte was poured into the battery case 1. On the other hand, the negative electrode 3 was attached to the inside of the top surface portion 6 a of the sealing plate 6. Then, the sealing plate 6 was disposed so as to close the opening of the battery case 1 with the sealing plate 6, and the first side wall 1 b was crimped to the second side wall of the sealing plate via the gasket 5. As a result, a coin-type battery was completed.
- the coin battery has a diameter of 20 mm, a thickness of 3.2 mm, and an electric capacity of 225 mAh.
- the manufacturing cost can be greatly reduced by using an inexpensive steel material for the sealing plate of the coin-type battery, battery leakage due to deformation of the sealing plate can be prevented, and storage can be further performed.
- the reliability of the antirust effect at the time can be greatly improved. Therefore, it is useful in various applications.
- 1 battery case, 1a: bottom portion, 1b: first side wall, 2: positive electrode, 3: negative electrode, 4: separator, 5: gasket, 6: sealing plate, 6a: top surface portion, 6b: second side wall, 8: First bending portion, 9: second bending portion, 10: third bending portion, 12, 12A: falling portion
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Abstract
Description
ここで、封口板は、第一湾曲部の外面側の曲率半径R1と第二湾曲部の外面側の曲率半径R2との比:R1/R2が、0.22~1.88になるように形成されている。
コイン形電池100は、電池ケース1と、封口板6と、ガスケット5と、で構成される外装体を具備する。電池ケース1は、底面部1aおよび底面部1aの周縁から立ち上がる第一側壁1bを有する円筒型であり、底浅の電池缶である。封口板6は、天面部6aおよび天面部6aの周縁から電池ケース1の第一側壁1bの内側へと延びる第二側壁6bを有する。ガスケット5の一部は、電池ケース1の第一側壁1bと封口板6の第二側壁6bとの間に介在することにより、電池ケース1と封口板6との隙間を封止している。ガスケット5は、封口板6の周縁部に勘合する環状の溝部を有している。
封口板6は、天面部6aと第二側壁6bとの境界に形成された第一湾曲部8と、第一湾曲部8に続いて形成された第二湾曲部9と、第二湾曲部9に続いて形成された第三湾曲部10と、第三湾曲部10に続いて形成された下方への立ち下り部12とを具備する。第一湾曲部8の最も曲率の高い点P1の高さH1と、第三湾曲部10の最も曲率の高い点P3の高さH3との高さの差:Hd1は、例えば0.1~2.0mmである。
コイン形電池は、正極、負極、正極と負極との間に介在するセパレータおよび電解液を含む発電要素を準備する工程と、底面部および底面部の周縁から立ち上がる第一側壁を有する円筒型の電池ケースを準備する工程(i)と、天面部および天面部の周縁から立ち下がる第二側壁を有する封口板を準備する工程(ii)と、第一側壁と第二側壁との間に少なくとも一部を介在させるガスケットを準備する工程(iii)と、電池ケースに発電要素を収容した後、封口板で電子ケースの開口を塞ぎ、電池ケースの開口端部を、ガスケットを介して、封口板の第2側壁に加締める工程(iv)と、を具備する。
発電要素は、正極2、負極3、セパレータ4および電解液(図示せず)を含む。正極2と電池ケース1の底面部1aとの間には、集電体14が配置されている。
次に、本発明を実施例に基づいて具体的に説明する。ただし、以下の実施例は本発明を限定するものではない。なお、本実施例では図1に示すような構造のコイン形電池を作製した。
電池ケース1には、表面に厚み3μmのニッケルめっき層を形成したステンレス鋼板(SUS430、厚み200μm)を使用した。このステンレス鋼板を絞り加工して、底面部の直径が20mm、第1側壁1bの高さが2.8mmの有底の円筒型に成形した。
第一湾曲部8の外面側の曲率半径R1と第二湾曲部9の外面側の曲率半径R2とを様々に変化させて、複数の封口板6を作製した。
ここでは、表面に厚み3μmのニッケルめっき層を有する鉄鋼材の炭素鋼板(厚み200μm)を使用した。この鋼板をプレス加工により、天面部6aの直径が17mmである所定形状に加工した。ここでは、第一湾曲部8の最も曲率の高い点P1の高さH1と第三湾曲部10の最も曲率の高い点P3の高さH3との高さの差:Hd1は0.9mm、点P1と点P3との水平距離:Ddは0.6mm、高さH3と立ち下り部12の最下点P4の高さH4との高さの差:Hd2は1.3mmとした。
R2は、0.16~2.00mm(実施例1~24)または0.10~2.00mm(比較例1~15)の範囲で様々に変化させた。
実施例1~24では、R1/R2比を0.22~1.88に制御した。
比較例1~15では、R1/R2比を0.15~5.00に制御した。
R1とR2との組み合わせ、並びに、R1/R2比を表1に示す。
正極活物質である二酸化マンガン100質量部と、導電助剤である黒鉛7質量部と、結着剤であるポリテトラフルオロエチレン1質量部とを混合して、正極合剤を調製した。正極合剤を直径15mm、厚さ2mmのコイン形ペレットに成形して、正極2とした。
厚さ0.6mmの金属リチウム箔を直径16mmの円形に打ち抜いて、負極とした。
厚さ300μmのポリプロピレン製不織布をセパレータ4として用いた。
プロピレンカーボネートと1,2-ジメトキシエタンとを体積比2:1で混合した非水溶媒に、溶質としてLiClO4を濃度1.0mol/Lで溶解させた有機電解液を用いた。
ポリプロピレン製のガスケット5を用いた。第1側壁1bと第二側壁6bとの間に介在させる部分の初期厚みは0.3mmとした。
電池ケース1の第一側壁1bの内側に、ブロンアスファルトと鉱物油からなる封止剤を塗布したガスケット5を配置するとともに、底面部1aにSUS444製の集電体を配置し、その上に、正極2を載置した。次に、正極2の上にセパレータ4を載置し、その後、有機電解液を電池ケース1内に注液した。一方、負極3は、封口板6の天面部6aの内側に貼り付けた。そして、封口板6で電池ケース1の開口を塞ぐように封口板6を配置し、第一側壁1bを、ガスケット5を介して、封口板の第2側壁に加締めた。これにより、コイン形電池を完成させた。コイン形電池の直径は20mm、厚さは3.2mm、電気容量は225mAhである。
実施例1~24および比較例1~15のコイン形電池を、それぞれ200個作製した。
(漏液発生数)
それぞれ100個の電池について、振動試験と熱衝撃試験を実施した後、漏液の有無を確認した。まず、200Hzの周波数振動をX、Y、Zの3方向にそれぞれ1時間ずつ付与する振動試験を実施した。続いて、-60℃で1時間、60℃で1時間を1サイクルとする熱衝撃試験を360サイクル繰り返した。その後、漏液が発生した電池の個数を確認した。結果を表1に示す。
それぞれ100個の電池を、60℃/90%RHの高温多湿環境下に100日保存する保存試験を実施した。その後、保存後の電池の外観を観察し、錆が発生した電池の個数を確認した。結果を表1に示す。
Claims (5)
- 正極、負極、前記正極と前記負極との間に介在するセパレータおよび電解液を含む発電要素と、前記発電要素を収容する外装体と、を備え、
前記外装体は、底面部および前記底面部の周縁から立ち上がる第一側壁を有する円筒型の電池ケースと、天面部および前記天面部の周縁から前記第一側壁の内側へと延びる第二側壁を有する封口板と、前記第一側壁と前記第二側壁との間に少なくとも一部が介在するガスケットと、を具備し、
前記封口板は、
前記天面部と前記第二側壁との境界に形成された第一湾曲部と、
前記第一湾曲部に続いて形成された第二湾曲部と、
前記第二湾曲部に続いて形成された第三湾曲部と、
前記第三湾曲部に続いて形成された立ち下り部と、を具備し、
前記第一湾曲部の外面側の曲率半径R1と第二湾曲部の外面側の曲率半径R2との比:R1/R2が、0.22~1.88である、コイン形電池。 - 前記封口板が、普通鋼により形成されている、請求項1記載のコイン形電池。
- 前記電池ケースが、ステンレス鋼により形成されている、請求項1または2記載のコイン形電池。
- 前記曲率半径R1が、0.3~0.5mmである、請求項1~3のいずれか1項記載のコイン形電池。
- 前記ガスケットと、前記第1側壁および前記第2側壁より選ばれる少なくとも一方と、の間に、粘着性を有する封止剤が介在している、請求項1~4のいずれか1項記載のコイン形電池。
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US14/236,241 US9515301B2 (en) | 2011-09-30 | 2012-09-25 | Coin battery having a sealing plate which suppresses deformation |
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Also Published As
Publication number | Publication date |
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CN103718331B (zh) | 2016-03-16 |
CN103718331A (zh) | 2014-04-09 |
US20140170472A1 (en) | 2014-06-19 |
JPWO2013046644A1 (ja) | 2015-03-26 |
JP6044789B2 (ja) | 2016-12-14 |
US9515301B2 (en) | 2016-12-06 |
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