JP2013048116A - Sealed battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sealed battery with increased pouring and impregnation property of an electrolyte while the shape of a battery element and the battery outer packaging itself remain the same, and variations in characteristics and process failures of the sealed battery being suppressed while the energy density of the sealed battery is maintained.SOLUTION: A sealed battery is formed by: laminating a positive electrode plate 1 in which a positive electrode mixture layer 1b is formed on a positive electrode collector 1a and a negative electrode plate 3 in which a negative electrode mixture layer 3b is formed on a negative electrode collector 3a via a separator 2; obtaining a wound battery element by winding the laminated body; sticking a winding stop tape 4 on the outermost peripheral part of the wound battery element; and housing the battery element in an outer packaging case. The outermost peripheral part includes the exposed portion of the electrode collectors where both two surfaces of either the positive electrode collector 1a or the negative electrode collector 3a are exposed, and holes are formed on the exposed portion of the electrode collectors, the total area of hole openings being 10 to 40% of that of the exposed portion of the electrode collectors.

Description

  The present invention relates to a sealed battery suitable for use in portable devices, information devices, home appliances, and the like, in particular, small and portable devices.

  In recent years, advances in electro technology have made it possible to reduce the size and increase the functionality of electronic devices. As a result, the market for portable devices has grown rapidly, and as a power source for driving these devices, development of sealed batteries with high energy density and long life has been demanded. Under such circumstances, in order to improve the energy density, improvement of electrode materials that are battery elements and thinning of separators are being promoted. For the electrodes, energy density is being improved by adjusting the rolling method and the particle size of the material itself, and thinning of the separator is also being considered while maintaining piercing and tensile strength.

  In such a battery with improved energy density, the gap between the battery can and the battery element is extremely small, and there is a problem that the liquid injection property of the electrolytic solution is lowered. For example, in a sealed battery, there is a step of sealing a battery can by performing sealing after pouring, but a sealing failure may occur. In addition, even if a predetermined amount of electrolyte can be injected, there is a concern that variations in cycle characteristics and battery characteristics may occur due to insufficient impregnation of the battery element with the electrolyte, and it is desired to improve liquid injection. .

  Conventionally, in order to improve liquid injection properties, holes are formed in the current collector (see Patent Document 1), grooves are formed on the surface of the negative electrode active material layer (see Patent Document 2), and the positive electrode active material A technique for dispersing microcapsules on the surface of a layer (Patent Document 3) has been proposed.

Japanese Patent Laid-Open No. 10-162801 JP-A-9-298057 JP 2005-228642 A

  In the prior art, when forming holes in the current collector, the active material of the positive and negative electrodes cannot be formed in the vicinity of the holes, so that the amount of active material filling is reduced, and the active material layer of the positive and negative electrodes is grooved. Even when a capsule is provided or capsules are sprayed, the active material filling amount is reduced, or the active material layer surface becomes uneven, which is not preferable.

  Under such circumstances, the object of the present invention is to improve the pouring and impregnating properties of the electrolyte while maintaining the shape of the battery element and the battery outer package itself, while maintaining the energy density of the battery. An object of the present invention is to provide a sealed battery that suppresses variations and process defects.

  The present invention has been made as a result of finding that the liquid injection property is improved by providing a hole in the outermost periphery of the battery element for a sealed battery in which a battery element is formed by winding a strip electrode and a separator. It is.

  In the sealed battery of the present invention, a positive electrode plate in which a positive electrode mixture layer is formed on a positive electrode current collector and a negative electrode plate in which a negative electrode mixture layer is formed on a negative electrode current collector are interposed via a separator. A battery element that is stacked and wound, a tear-off tape attached to the outermost periphery of the battery element, and an outer case that houses the electrical element and the tear-off tape are provided. In this aspect, the outermost peripheral portion includes a current collector exposed portion where both surfaces of the positive electrode current collector or the negative electrode current collector are exposed. And the void | hole part is formed in the collector exposed part by the total opening area of the ratio of 10 to 40% with respect to the area of a collector exposed part, It is characterized by the above-mentioned.

  Further, it is preferable that the squeezing tape is made of a porous film, and the squeezing tape is made of a porous film having a density of 0.6 g / cm 3 to 1.5 g / cm 3.

  According to the sealed battery of the present invention, the liquid injection property of the battery element itself can be improved, and the occurrence of defects due to overflow of the electrolyte in the sealing step can be reduced. Further, when the squeezing tape is made of a porous film, the squeezing tape itself has a liquid retention property, so that the separator can be supplied with an electrolytic solution, and liquid drainage during the charge / discharge cycle can be prevented.

The front view which stuck the tear-off tape on the battery element of the sealed battery of this invention. Sectional drawing which shows the battery element of the sealed battery of this invention. The fragmentary sectional view which expanded the A section of FIG. The partial front view of the B section of FIG. The perspective view which shows the winding middle of the battery element of the sealed battery of this invention. The perspective view which shows the state which stuck the tear-off tape on the battery element of the sealed battery of this invention. The perspective view of the sealed battery of this invention.

  Next, embodiments of the present invention will be described with reference to the drawings.

  FIG. 1 is a front view of a battery element of a sealed battery according to the present invention with a squeeze tape applied thereto, FIG. 2 is a cross-sectional view showing the battery element of the sealed battery of the present invention, and FIG. FIG. 4 is a partial front view of a portion B in FIG. 3.

  As shown in FIG. 2, in the battery element of the sealed battery of the present invention, a positive electrode mixture layer mainly composed of a positive electrode active material is formed on a positive electrode current collector made of a conductive foil such as aluminum, aluminum alloy, or titanium. A positive electrode plate 1 and a negative electrode plate 3 in which a negative electrode mixture layer mainly composed of a negative electrode active material is formed on a negative electrode current collector made of a conductive foil such as copper, nickel, SUS, silver, etc. It is the structure which laminated | stacked through and wound.

The positive electrode active material is preferably LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ or the like. In addition, V ₂ O ₅ , MnO ₂ , MoS ₂ , TiS ₂ or the like having a potential difference with the negative electrode of 1 V or more can be applied. The positive electrode active material is mixed with a binder and a conductive auxiliary material such as polyvinylidene fluoride, polytetrafluoroethylene, and polyethylene, and applied to the positive electrode current collector as a positive electrode mixture layer to form the positive electrode plate 1. .

  The negative electrode active material is a carbonaceous material, and natural graphite or artificial graphite, which is graphite, is preferable. A binder such as polyvinylidene fluoride, polyethylene, styrene butadiene and the like and a conductive auxiliary material are mixed with such graphite and applied to the negative electrode current collector as a negative electrode mixture layer to form the negative electrode plate 3. .

  The separator 2 is not limited as long as it prevents the positive electrode plate 1 and the negative electrode plate 3 from being short-circuited and has ionic conductivity, but is preferably a porous polyolefin film, such as a polyethylene oxide derivative, polystyrene, polybutadiene, and The copolymer, polyvinylidene fluoride, etc. can be applied. Moreover, you may use a well-known solid electrolyte as an insulating layer.

  As shown in FIG. 3, the outer peripheral portion of the battery element is composed of a positive electrode plate in which the positive electrode mixture layer 1b is formed on one surface inside the battery element of the positive electrode current collector 1a, and the outermost peripheral portion is the positive electrode current collector 1a. Consists of only. The positive electrode current collector 1a at the outermost periphery is in contact with the positive electrode current collector 1a of the positive electrode plate having the positive electrode mixture layer 1b formed on one side inside one circumference. Further, the positive electrode mixture layer 1 b has a structure facing the negative electrode mixture layer 3 b formed on the negative electrode current collector 3 a with the separator 2 interposed therebetween. Note that whether the positive electrode plate or the negative electrode plate is arranged on the outer peripheral portion is determined by the material of the exterior material. Here, for example, when an aluminum can is used for the exterior material, since the aluminum can of the exterior material is on the positive electrode side, a positive electrode plate is attached to the outer peripheral portion so that there is no problem even if the outer peripheral portion of the exterior material and the battery element come into contact. Although it arrange | positioned, when an iron-type material is used for an exterior material, it is good to arrange | position a negative electrode plate to an outer peripheral part.

  As shown in FIG. 4, the outermost peripheral positive electrode current collector 1a has a structure in which a hole portion 1c is provided. The hole part 1c is provided in the exposed part of the positive electrode current collector in which the positive electrode mixture layer is not formed on both surfaces, and the current collector of the same polarity as the outermost peripheral part of the positive electrode current collector provided with the hole part 1c. It becomes the structure where the surface in which the positive mix layer of a body is not formed opposes. Further, the total area of the hole portions may be formed so as to be 10% to 40% of the area of the corresponding current collector, that is, the area of the outermost peripheral positive electrode current collector alone, % To 30% is more preferable. When the pore area is smaller than 10%, no improvement is observed in the liquid injection property, and when it is larger than 40%, there is a concern about breakage due to a decrease in mechanical strength of the current collector itself. .

As shown in FIG. 1, the battery element has its outermost peripheral surface fixed by a scooping tape 4. It is not always necessary for the tear-off tape to cover the entire surface of the battery element. In particular, when a porous tape is not used, it is preferable not to cover the entire pores. The wrapping tape 4 is not particularly limited as long as it is resistant to the electrolytic solution, but a material having a high affinity for the electrolytic solution is particularly effective. Polystyrene, polyvinylidene fluoride, polybutadiene, and copolymers thereof. Is mentioned. From the viewpoint of the electrolyte solution holding, it is preferably a porous, density ^{0.6g / cm 3 ~1.5g / cm 3} , preferably to 0.8g ^/ cm ³ ~1.2g ^/ cm 3 Is desirable. If it is less than 0.6 g / cm ³ , there is a problem in mechanical strength, and there is a concern about the assembling property, and if it is more than 1.5 g / cm ^3, sufficient liquid retention cannot be obtained.

In order to function as a battery, it is necessary to impregnate a non-aqueous electrolyte solution. As the electrolyte solution, an electrolyte solution in which salts are dissolved in an organic solvent can be used. Examples of the salts include LiClO ₄ , LiBF ₄ , LiPF ₆ , LiAsF _{6 and the} like, and one or a mixture of two or more of these can be applied. Examples of the organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, γ-butyl lactone, 1,2-dimethoxyethane, tetrohydrofuran, and the like, and one or a mixture of two or more thereof can be applied.

  In the sealed battery according to the present invention, existing materials can be used as various constituent materials not described above such as a battery can, a battery can lid, a safety structure, and an electrode terminal.

(Example)
Hereinafter, the present invention will be specifically described based on examples.

Example 1
LiCoO ₂ was used as a positive electrode active material, 94 parts by weight thereof, 3 parts by weight of polyvinylidene fluoride, 3 parts by weight of acetylene black as a conductive material, and 50 parts by weight of N-methyl 2pyrrolidone were mixed to form a slurry. This slurry was applied to a positive electrode current collector made of an aluminum foil having a thickness of 15 μm, dried, and rolled to form a positive electrode mixture layer to produce a positive electrode plate. On the other hand, scaly graphite was used as the negative electrode active material, and 97 parts by weight thereof, 3 parts by weight of polyvinylidene fluoride, and 60 parts by weight of N-methyl-2-pyrrolidone were mixed to form a slurry. This slurry was applied to a negative electrode current collector made of a copper foil having a thickness of 10 μm, dried, and rolled to form a negative electrode mixture layer to produce a negative electrode plate.

  FIG. 5 is a perspective view showing the winding process of the battery element of the sealed battery according to the present invention, and FIG. 6 is a perspective view showing a state in which a tear-off tape is applied to the battery element of the sealed battery of the present invention. FIG. 7 is a perspective view of the sealed battery of the present invention. After the positive electrode plate produced as described above is slit to 40 mm width and the negative electrode plate to 41 mm width, a plurality of Φ1 mm circular holes are provided in the exposed portion of the positive electrode plate current collector, and 15% of the total area of the corresponding portion is empty. After providing the holes, the positive electrode plate 1 and the negative electrode plate 3 are wound through a separator 2 made of porous polyethylene having a thickness of 20 μm and a width of 43 mm so that the positive electrode plate 1 becomes the outer periphery as shown in FIG. After the element was fabricated, the battery element was fixed with a winding tape 4 having a width of 41 mm and a thickness of 14 μm made of a polyvinylidene fluoride porous film having a density of 0.60 g / cm 3 as shown in FIG.

  After the fixed battery element is inserted into an aluminum can for a predetermined rectangular sealed battery as shown in FIG. 7, the lid is laser welded according to a predetermined process so that the amount of electrolyte from the sealing portion 5 reaches the maximum standard value. Then, 1000 sealed batteries were prepared and the sealing failure rate was determined. In addition, a charge / discharge cycle test was carried out using a sealed battery prepared with a lower limit of the amount of electrolyte. For the charge / discharge cycle test, based on the battery capacity calculated from the coating amount of the positive electrode active material, charging was performed for 2.5 hours under a constant current of 1 C and 4.2 V, and the terminal voltage was 3 at a current of 1 C. The discharge until reaching 0 V was repeated. The test atmosphere was 20 ° C., and the capacity retention rate after 500 cycles was confirmed. Table 1 shows the sealing failure rate and the capacity retention rate (average value of 3 pieces) in the cycle characteristics.

(Example 2)
Polyvinylidene fluoride porous material having a density of 0.90 g / cm ³ by providing a plurality of circular holes of Φ1 mm in the exposed part of the positive electrode current collector on the outermost periphery of the positive electrode plate to provide a hole part of 25% of the total area A sealed battery was prepared and tested in the same manner as in Example 1 except that a film-fastening tape was used.

(Example 3)
Polyvinylidene fluoride porous having a density of 1.50 g / cm ³ by providing a plurality of Φ1 mm circular holes in the exposed portion of the positive electrode current collector at the outermost periphery of the positive electrode plate A sealed battery was prepared and tested in the same manner as in Example 1 except that a film-fastening tape was used.

Example 4
Polyvinylidene fluoride porous having a density of 1.00 g / cm ³ by providing a plurality of circular holes of Φ1 mm in the exposed portion of the positive electrode current collector on the outermost periphery of the positive electrode plate, providing a hole of 30% of the total area A sealed battery was prepared and tested in the same manner as in Example 1 except that a film-fastening tape was used.

(Example 5)
Polyvinylidene fluoride porous having a density of 1.80 g / cm ³ by providing a plurality of circular holes of Φ1 mm in the exposed portion of the positive electrode current collector on the outermost periphery of the positive electrode plate to provide a hole of 30% of the total area A sealed battery was prepared and tested in the same manner as in Example 1 except that a film-fastening tape was used.

(Comparative Example 1)
The same as Example 1 except that a hole was not provided in the exposed portion of the positive electrode current collector on the outermost periphery of the positive electrode plate, and a wrapping tape made of a polyvinylidene fluoride porous film having a density of 1.00 g / cm ³ was used. A sealed battery was prepared and tested.

(Comparative Example 2)
The same as Example 1 except that a hole was not provided in the exposed portion of the positive electrode current collector on the outermost periphery of the positive electrode plate, and a tear-off tape made of a polyvinylidene fluoride porous film having a density of 0.70 g / cm ³ was used. A sealed battery was prepared and tested.

  Table 1 shows the sealing failure rate and the capacity retention rate in cycle characteristics in Examples 2 to 5 and Comparative Examples 1 and 2.

DESCRIPTION OF SYMBOLS 1 Positive electrode plate 1a Positive electrode collector 1b Positive electrode mixture layer 1c Hole part 2 Separator 3 Negative electrode plate 3a Negative electrode collector 3b Negative electrode mixture layer 4 Winding-off tape 5 Sealing part

Claims (3)

A positive electrode plate in which a positive electrode mixture layer is formed on a positive electrode current collector and a negative electrode plate in which a negative electrode mixture layer is formed on a negative electrode current collector are laminated and wound via a separator. A battery element;
A squeeze tape affixed to the outermost periphery of the battery element;
In a sealed battery comprising the battery element and an outer case in which the squeeze tape is housed,
The outermost peripheral portion includes a current collector exposed portion in which both surfaces of the positive electrode current collector or the negative electrode current collector are exposed,
A sealed battery, wherein a hole portion is formed in the current collector exposed portion with a total opening area of 10 to 40% of the area of the current collector exposed portion. The sealed battery according to claim 1, wherein the wrapping tape is made of a porous film. ^3. The sealed battery according to claim 2, wherein the density of the crease-proof tape is 0.6 g / cm ^{3 to} 1.5 g / cm ³ .

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