JP2016154092A - Power storage element - Google Patents

Power storage element Download PDF

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JP2016154092A
JP2016154092A JP2015031584A JP2015031584A JP2016154092A JP 2016154092 A JP2016154092 A JP 2016154092A JP 2015031584 A JP2015031584 A JP 2015031584A JP 2015031584 A JP2015031584 A JP 2015031584A JP 2016154092 A JP2016154092 A JP 2016154092A
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case
liquid injection
injection hole
power storage
liquid
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伸介 吉竹
Shinsuke Yoshitake
伸介 吉竹
村上　聡
Satoshi Murakami
聡 村上
康夫 辻野
Yasuo Tsujino
康夫 辻野
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GS Yuasa Corp
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    • 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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Abstract

PROBLEM TO BE SOLVED: To provide a power storage element in which the roughening of welding due to an electrolytic solution attached to a cover plate when injecting the electrolytic solution in a welding position of a case and a liquid plug.SOLUTION: A power storage element comprises: a case to which a liquid hole 325 for injecting an electrolytic solution is formed; a liquid plug 326 for closing the liquid hole 325, and the liquid plug 326 includes: a head part 327 that is arranged along with an outer surface of the case, and is welded to the case; and an insertion part 328 that extends from the head part 327, and is inserted to the liquid hole 325. At least one of an inner peripheral surface of the liquid plug 326 and the liquid hole 325 has a shape so to prevent the liquid plug 326 from having a contact with the electric solution attached to a position including an opening edge for defying an opening of the liquid hole 325 in an inner surface of the case in the inner peripheral surface.SELECTED DRAWING: Figure 3

Description

本発明は、充放電が可能な蓄電素子に関する。   The present invention relates to a power storage element that can be charged and discharged.

従来から充放電が可能な密閉式電池が知られている（特許文献１参照）。図９に示すように、密閉式電池１００は、開口部を有し且つ渦巻電極体を収容する外装缶１０１と、外装缶１０１の開口部を塞ぎ且つ注液孔１０２が形成された封口板１０３と、注液孔１０２を封止する封止栓１０４と、を備える。封止栓１０４は、封口板１０３に沿って配置されるベース部１０５と、ベース部１０５から延び且つ注液孔１０２に填り込む先端部１０６と、を有する。先端部１０６は、注液孔１０２に圧入される径を有する圧入部１０７と、圧入部１０７からテーパ状に延びる縮径部１０８とを有する。外装缶１０１及び封口板１０３は、Ａｌ−Ｍｎ係の合金によって形成され、封止栓１０４は、アルミ合金によって形成されている。   Conventionally, a sealed battery that can be charged and discharged is known (see Patent Document 1). As shown in FIG. 9, a sealed battery 100 includes an outer can 101 having an opening and accommodating a spiral electrode body, and a sealing plate 103 that closes the opening of the outer can 101 and has a liquid injection hole 102 formed therein. And a sealing plug 104 that seals the liquid injection hole 102. The sealing plug 104 has a base portion 105 disposed along the sealing plate 103 and a tip portion 106 that extends from the base portion 105 and fits into the liquid injection hole 102. The distal end portion 106 includes a press-fit portion 107 having a diameter that is press-fitted into the liquid injection hole 102, and a reduced diameter portion 108 that extends from the press-fit portion 107 in a tapered shape. The outer can 101 and the sealing plate 103 are made of an Al—Mn alloy, and the sealing plug 104 is made of an aluminum alloy.

この密閉式電池１００は、非水電解液が注液孔１０２から注入されて渦巻電極体に含浸されることで、充放電可能となる。注液孔１０２は、非水電解液の注入後に封止栓１０４の先端部１０６（詳しくは圧入部１０７）が圧入され、ベース部１０５の周縁と封口板１０３とがレーザ溶接されることで封止（密閉）される。   The sealed battery 100 can be charged and discharged by injecting a non-aqueous electrolyte from the liquid injection hole 102 and impregnating the spiral electrode body. The liquid injection hole 102 is sealed by laser-welding the peripheral edge of the base portion 105 and the sealing plate 103 by inserting the tip end portion 106 (specifically, the press-fitting portion 107) of the sealing plug 104 after injecting the non-aqueous electrolyte. Stopped (sealed).

密閉式電池１００の封止栓１０４において、先端部１０６における圧入部１０７の長さ寸法が、封口板１０３の厚さ寸法より大きい。このため、非水電解液を注入したときに封口板１０３（例えば、注液孔１０２の内周面等）に非水電解液が付着していると、先端部１０６が注液孔１０２に圧入されたときに、圧入部１０７が封口板１０３に付着している非水電解液と接触する。このように先端部１０６（圧入部１０７）と封口板１０３に付着した非水電解液とが接触すると、毛細管現象等によって非水電解液が先端部１０６と注液孔１０２の内周面との間を通ってベース部１０５と封口板１０３との間まで移動する（いわゆる液上がりが生じる）。このように、液上がりが生じた状態で、ベース部１０５と封口板１０３とがレーザ溶接されると、非水電解液が反応して、溶接部位にピッチング等の溶接荒れが発生する。   In the sealing plug 104 of the sealed battery 100, the length dimension of the press-fit portion 107 at the distal end portion 106 is larger than the thickness dimension of the sealing plate 103. For this reason, if the nonaqueous electrolyte is attached to the sealing plate 103 (for example, the inner peripheral surface of the injection hole 102) when the nonaqueous electrolyte is injected, the tip 106 is press-fitted into the injection hole 102. When this is done, the press-fit portion 107 comes into contact with the nonaqueous electrolytic solution adhering to the sealing plate 103. When the tip portion 106 (press-fit portion 107) and the non-aqueous electrolyte adhering to the sealing plate 103 come into contact with each other in this way, the non-aqueous electrolyte solution is brought into contact between the tip portion 106 and the inner peripheral surface of the injection hole 102 by capillary action or the like. It moves to the space between the base portion 105 and the sealing plate 103 (so-called liquid rising occurs). As described above, when the base portion 105 and the sealing plate 103 are laser-welded in a state where the liquid has risen, the nonaqueous electrolytic solution reacts to cause rough welding such as pitching at the welded portion.

特開２０００−２６８８１１号公報JP 2000-268811 A

そこで、本発明は、ケースと注液栓との溶接部位において電解液の注入時に蓋板に付着した電解液に起因する溶接荒れが抑えられた蓄電素子を提供することを目的とする。   Therefore, an object of the present invention is to provide a power storage device in which the welding roughness due to the electrolytic solution attached to the lid plate at the time of injection of the electrolytic solution at the welding site between the case and the injection plug is suppressed.

本発明に係る蓄電素子は、
電解液を注入する注液孔の形成されたケースと、
前記注液孔を塞ぐ注液栓と、を備え、
前記注液栓は、
前記ケースの外面に沿って配置される頭部であって前記ケースと溶接されている頭部と、
前記頭部から延び且つ前記注液孔に挿入されている挿入部と、を有し、
前記注液栓、及び前記注液孔の内周面の少なくとも一方は、該注液栓と、該内周面において前記ケースの内面における前記注液孔の開口を画定する開口縁を含む位置に付着する電解液と、の接触を避ける形状を有する。 The electricity storage device according to the present invention is:
A case in which an injection hole for injecting an electrolyte is formed;
A liquid stopper for closing the liquid injection hole,
The injection stopper is
A head disposed along the outer surface of the case and welded to the case;
An insertion portion extending from the head and inserted into the liquid injection hole,
At least one of the liquid injection stopper and the inner peripheral surface of the liquid injection hole is at a position including the liquid injection stopper and an opening edge that defines an opening of the liquid injection hole in the inner surface of the case on the inner peripheral surface. It has a shape that avoids contact with the attached electrolyte.

かかる構成によれば、電解液の注入後に注液栓の挿入部を注液孔に挿入したときに、挿入部と、蓋板に付着した電解液（例えば、電解液の液滴）と、の接触を避けることができる。このため、ケース（注液孔の内周面等）と注液栓との間の電解液の液上がりが抑えられ、これにより、ケース内への電解液の注入後にケースと注液栓とを溶接（例えば、レーザ溶接）して注液孔を密閉したときの溶接部位において、蓋板に付着した電解液に起因する溶接荒れが生じ難い。その結果、ケースと注液栓との溶接部位において溶接荒れの抑えられた蓄電素子が得られる。   According to such a configuration, when the insertion portion of the injection stopper is inserted into the injection hole after the injection of the electrolytic solution, the insertion portion and the electrolytic solution attached to the lid plate (for example, a droplet of the electrolytic solution) Contact can be avoided. This prevents the electrolyte from rising between the case (inner peripheral surface of the injection hole, etc.) and the injection stopper, and thus the case and the injection stopper are connected after the electrolyte is injected into the case. Rough welding due to the electrolytic solution adhering to the lid plate is unlikely to occur at the welded site when the injection hole is sealed by welding (for example, laser welding). As a result, an electric storage element in which welding roughness is suppressed at the welded portion between the case and the liquid filling tap can be obtained.

前記蓄電素子では、
前記挿入部の長さ寸法は、前記ケースにおける前記注液孔の形成された壁の厚さ寸法より小さくてもよい。 In the storage element,
The length of the insertion portion may be smaller than the thickness of the wall in the case where the liquid injection hole is formed.

注液孔が形成された壁の厚さ寸法より挿入部の長さ寸法を小さくするといった簡素な構成によって、電解液の注入後に注液栓の挿入部を注液孔に挿入したときの、挿入部と、蓋板に付着した電解液との接触を防ぐことができる。   Insertion when the insertion part of the injection plug is inserted into the injection hole after injection of the electrolyte by a simple configuration such as making the length of the insertion part smaller than the thickness dimension of the wall in which the injection hole is formed Can be prevented from contacting the electrolyte solution adhering to the cover plate.

前記蓄電素子では、
前記挿入部の先端部は、先端に向かうほど縮径していることが好ましい。 In the storage element,
It is preferable that the distal end portion of the insertion portion is reduced in diameter toward the distal end.

かかる構成によれば、ケース内への電解液の注入後に注液栓によって注液孔を塞ぐ際に、注液栓の挿入部を注液孔に挿入し易くなる。   According to such a configuration, when the liquid injection hole is closed by the liquid injection plug after the electrolytic solution is injected into the case, the insertion part of the liquid injection plug can be easily inserted into the liquid injection hole.

以上より、本発明によれば、ケースと注液栓との溶接部位において電解液の注入時に蓋板に付着した電解液に起因する溶接荒れが抑えられた蓄電素子を提供することができる。   As described above, according to the present invention, it is possible to provide a power storage device in which the welding roughness due to the electrolytic solution attached to the lid plate at the time of injection of the electrolytic solution is suppressed at the welded portion between the case and the injection plug.

図１は、本実施形態に係る蓄電素子の斜視図である。FIG. 1 is a perspective view of a power storage device according to this embodiment. 図２は、図１のＩＩ−ＩＩ位置における断面図である。2 is a cross-sectional view taken along the line II-II in FIG. 図３は、図２の注液栓及びその周辺の拡大図である。FIG. 3 is an enlarged view of the liquid injection stopper of FIG. 2 and its surroundings. 図４は、前記蓄電素子における注液栓の断面斜視図である。FIG. 4 is a cross-sectional perspective view of the liquid filling tap in the electricity storage device. 図５は、注液孔の内周面に付着した電解液の液滴の半径の求め方を説明するための図である。FIG. 5 is a diagram for explaining how to obtain the radius of the droplet of the electrolyte attached to the inner peripheral surface of the liquid injection hole. 図６は、他実施形態に係る蓄電素子の注液栓及びその周辺の拡大断面図である。FIG. 6 is an enlarged cross-sectional view of a liquid filling cap and its surroundings of a power storage device according to another embodiment. 図７は、他実施形態に係る蓄電素子の注液栓及びその周辺の拡大断面図である。FIG. 7 is an enlarged cross-sectional view of a liquid filling cap and its surroundings of a power storage device according to another embodiment. 図８は、前記蓄電素子を含む蓄電装置の斜視図である。FIG. 8 is a perspective view of a power storage device including the power storage element. 図９は、従来の密閉式電池の封止栓及びその周辺の拡大断面図である。FIG. 9 is an enlarged cross-sectional view of a sealing plug of a conventional sealed battery and its surroundings.

以下、本発明に係る蓄電素子の一実施形態について、図１〜図５を参照しつつ説明する。蓄電素子には、一次電池、二次電池、キャパシタ等がある。本実施形態では、蓄電素子の一例として、充放電可能な二次電池について説明する。尚、本実施形態の各構成部材（各構成要素）の名称は、本実施形態におけるものであり、背景技術における各構成部材（各構成要素）の名称と異なる場合がある。   Hereinafter, an embodiment of a power storage device according to the present invention will be described with reference to FIGS. Examples of the power storage element include a primary battery, a secondary battery, and a capacitor. In the present embodiment, a chargeable / dischargeable secondary battery will be described as an example of a power storage element. In addition, the name of each component (each component) of this embodiment is a thing in this embodiment, and may differ from the name of each component (each component) in background art.

本実施形態の蓄電素子は、非水電解質二次電池である。より詳しくは、蓄電素子は、リチウムイオンの移動に伴って生じる電子移動を利用したリチウムイオン二次電池である。この種の蓄電素子は、電気エネルギーを供給する。蓄電素子は、単一又は複数で使用される。具体的に、蓄電素子は、要求される出力及び要求される電圧が小さいときには、単一で使用される。一方、蓄電素子は、要求される出力及び要求される電圧の少なくとも一方が大きいときには、他の蓄電素子と組み合わされて蓄電装置に用いられる。前記蓄電装置では、該蓄電装置に用いられる蓄電素子が電気エネルギーを供給する。   The electricity storage device of this embodiment is a nonaqueous electrolyte secondary battery. More specifically, the power storage element is a lithium ion secondary battery that utilizes electron transfer that occurs as lithium ions move. This type of power storage element supplies electrical energy. One or a plurality of power storage elements are used. Specifically, the storage element is used singly when the required output and the required voltage are small. On the other hand, when at least one of a required output and a required voltage is large, the power storage element is used in a power storage device in combination with another power storage element. In the power storage device, a power storage element used in the power storage device supplies electric energy.

蓄電素子は、図１〜図４に示すように、電解液を注入する注液孔３２５が形成されたケース３と、注液孔３２５を塞ぐ注液栓３２６と、を備える。また、蓄電素子１は、正極及び負極を含み且つケース３に収容される電極体２、ケース３の外側に配置される外部端子４、及び、電極体２と外部端子４とを導通させる集電体５等を備える。   As shown in FIGS. 1 to 4, the power storage element includes a case 3 in which a liquid injection hole 325 for injecting an electrolytic solution is formed, and a liquid injection plug 326 that closes the liquid injection hole 325. The power storage element 1 includes a positive electrode and a negative electrode, and an electrode body 2 accommodated in the case 3, an external terminal 4 disposed outside the case 3, and a current collector that electrically connects the electrode body 2 and the external terminal 4. A body 5 is provided.

電極体２は、巻芯２１と、正極と負極とが互いに絶縁された状態で積層された積層体２２であって、巻芯２１の周囲に巻回された積層体２２と、を備える（図２参照）。電極体２においてリチウムイオンが正極と負極との間を移動することにより、蓄電素子１が充放電する。   The electrode body 2 includes a core 21, and a laminate 22 in which the positive electrode and the negative electrode are insulated from each other, and the laminate 22 is wound around the core 21 (see FIG. 2). As the lithium ions move between the positive electrode and the negative electrode in the electrode body 2, the power storage device 1 is charged and discharged.

巻芯２１は、絶縁材料によって形成される。巻芯２１は、筒形状である。本実施形態の巻芯２１は、偏平な筒形状である。   The winding core 21 is formed of an insulating material. The winding core 21 has a cylindrical shape. The core 21 of the present embodiment has a flat cylindrical shape.

本実施形態の電極体２では、正極と負極とがセパレータによって絶縁された状態で巻回される。即ち、本実施形態の電極体２では、正極、負極、及びセパレータの積層体２２が巻回される。セパレータは、絶縁性を有する部材である。また、セパレータは、ケース３内において、電解液を保持する。これにより、蓄電素子１の充放電時において、リチウムイオンが、セパレータを挟んで交互に積層される正極と負極との間を移動可能となる。   In the electrode body 2 of the present embodiment, the positive electrode and the negative electrode are wound in a state where they are insulated by the separator. That is, in the electrode body 2 of this embodiment, the laminated body 22 of a positive electrode, a negative electrode, and a separator is wound. The separator is an insulating member. The separator holds the electrolytic solution in the case 3. Thereby, at the time of charging / discharging of the electrical storage element 1, a lithium ion becomes movable between the positive electrode and negative electrode which are laminated | stacked alternately on both sides of a separator.

ケース３は、開口を有するケース本体３１と、ケース本体３１の開口を塞ぐ（閉じる）蓋板３２と、を有する。ケース３は、電極体２及び集電体５等と共に、電解液を内部空間３３に収容する。ケース３は、電解液に耐性を有する金属によって形成される。本実施形態のケース３は、例えば、アルミニウム、又は、アルミニウム合金等のアルミニウム系金属材料によって形成される。ケース３は、ステンレス鋼及びニッケル等の金属材料、又は、アルミニウムにナイロン等の樹脂を接着した複合材料等によって形成されてもよい。   The case 3 includes a case main body 31 having an opening and a cover plate 32 that closes (closes) the opening of the case main body 31. The case 3 houses the electrolytic solution in the internal space 33 together with the electrode body 2 and the current collector 5. Case 3 is formed of a metal having resistance to the electrolytic solution. The case 3 of the present embodiment is formed of an aluminum metal material such as aluminum or an aluminum alloy, for example. The case 3 may be formed of a metal material such as stainless steel and nickel, or a composite material obtained by bonding a resin such as nylon to aluminum.

電解液は、非水溶液系電解液である。電解液は、有機溶媒に電解質塩を溶解させることによって得られる。有機溶媒は、例えば、プロピレンカーボネート及びエチレンカーボネートなどの環状炭酸エステル類、ジメチルカーボネート、ジエチルカーボネート、及びエチルメチルカーボネートなどの鎖状カーボネート類である。電解質塩は、ＬｉＣｌＯ４、ＬｉＢＦ４、及びＬｉＰＦ６等である。本実施形態の電解液は、プロピレンカーボネート、ジメチルカーボネート、及びエチルメチルカーボネートを、プロピレンカーボネート：ジメチルカーボネート：エチルメチルカーボネート＝３：２：５の割合で調整した混合溶媒に、１ｍｏｌ／ＬのＬｉＰＦ６を溶解させたものである。 The electrolytic solution is a non-aqueous electrolytic solution. The electrolytic solution is obtained by dissolving an electrolyte salt in an organic solvent. Examples of the organic solvent include cyclic carbonates such as propylene carbonate and ethylene carbonate, and chain carbonates such as dimethyl carbonate, diethyl carbonate, and ethyl methyl carbonate. The electrolyte salt is LiClO 4 , LiBF 4 , LiPF 6 or the like. The electrolyte solution of this embodiment is prepared by mixing 1 mol / L LiPF 6 in a mixed solvent in which propylene carbonate, dimethyl carbonate, and ethyl methyl carbonate are adjusted at a ratio of propylene carbonate: dimethyl carbonate: ethyl methyl carbonate = 3: 2: 5. Is dissolved.

ケース本体３１は、板状の閉塞部３１１であってケース３の内側を向く内面とケース３の外側を向く外面とを有する閉塞部３１１と、閉塞部３１１の周縁に接続される胴部３１２であって、閉塞部３１１の内面側に延び且つ該内面を包囲する筒状の胴部３１２とを備える。   The case main body 31 is a plate-like closing portion 311 having a closing portion 311 having an inner surface facing the inside of the case 3 and an outer surface facing the outer side of the case 3, and a body portion 312 connected to the periphery of the closing portion 311. And a cylindrical body 312 extending toward the inner surface of the closing portion 311 and surrounding the inner surface.

閉塞部３１１は、開口が上を向くようにケース本体３１が配置されたときに、ケース本体３１の下端に位置する（即ち、前記開口が上を向いたときのケース本体３１の底壁となる）部位である。以下では、図１及び図２に示すように、閉塞部３１１の長辺方向をＸ軸方向とし、閉塞部３１１の短辺方向をＹ軸方向とし、閉塞部３１１の法線方向をＺ軸方向とする。   The closing portion 311 is located at the lower end of the case main body 31 when the case main body 31 is arranged so that the opening faces upward (that is, it becomes the bottom wall of the case main body 31 when the opening faces upward). ) Part. In the following, as shown in FIGS. 1 and 2, the long side direction of the blocking portion 311 is the X-axis direction, the short side direction of the blocking portion 311 is the Y-axis direction, and the normal direction of the blocking portion 311 is the Z-axis direction. And

本実施形態の胴部３１２は、角筒形状を有する。詳しくは、胴部３１２は、偏平な角筒形状を有する。   The body portion 312 of the present embodiment has a rectangular tube shape. Specifically, the body portion 312 has a flat rectangular tube shape.

以上のように、ケース本体３１は、開口方向（Ｚ軸方向）における一方の端部が塞がれた角筒形状（即ち、有底角筒形状）を有する。   As described above, the case body 31 has a rectangular tube shape (that is, a bottomed rectangular tube shape) in which one end portion in the opening direction (Z-axis direction) is closed.

蓋板３２は、ケース本体３１の開口を塞ぐ板状の部材である。具体的に、蓋板３２は、ケース本体３１の開口を塞ぐようにケース本体３１に当接する。より具体的には、蓋板３２が開口を塞ぐように、蓋板３２の周縁部がケース本体３１の開口周縁部に重ねられる。開口周縁部と蓋板３２とが重ねられた状態で、蓋板３２とケース本体３１との境界部が溶接され、これにより、ケース３が構成される。この蓋板３２には、注液孔３２５が形成されている。   The lid plate 32 is a plate-like member that closes the opening of the case body 31. Specifically, the cover plate 32 contacts the case body 31 so as to close the opening of the case body 31. More specifically, the periphery of the cover plate 32 is overlapped with the periphery of the opening of the case body 31 so that the cover plate 32 closes the opening. In a state where the opening peripheral edge portion and the lid plate 32 are overlapped, the boundary portion between the lid plate 32 and the case main body 31 is welded, whereby the case 3 is configured. A liquid injection hole 325 is formed in the lid plate 32.

注液孔３２５は、ケース３の内部と外部とを連通する。本実施形態の注液孔３２５は、上述のように、蓋板３２に形成される。具体的に、注液孔３２５は、蓋板３２をＺ軸方向（厚さ方向）に貫通する円形の穴である。尚、ケース３において注液孔３２５の形成される部位は、蓋板３２に限定されず、ケース本体３１であってもよい。   The liquid injection hole 325 communicates the inside and the outside of the case 3. The liquid injection hole 325 of the present embodiment is formed in the lid plate 32 as described above. Specifically, the liquid injection hole 325 is a circular hole that penetrates the cover plate 32 in the Z-axis direction (thickness direction). In addition, the part in which the liquid injection hole 325 is formed in the case 3 is not limited to the cover plate 32 but may be the case main body 31.

注液栓３２６は、注液孔３２５を密閉する（塞ぐ）。詳しくは、蓄電素子１の製造工程において、電解液が注液孔３２５からケース３内に注入された後に、注液栓３２６が注液孔３２５に挿入されて該注液孔３２５が塞がれ、注液栓３２６とケース３（本実施形態の例では蓋板３２）とがレーザ溶接されることによって、注液孔３２５が密閉される。この注液栓３２６は、具体的には、ケース３の外面に沿って配置される頭部３２７と、頭部３２７から延び且つ注液孔３２５に挿入されている挿入部３２８とを有する。本実施形態の注液栓３２６は、溶接によってケース３（本実施形態の例では蓋板３２）に固定されている。詳しくは、蓋板３２と頭部３２７の周縁とがレーザ溶接されている。   The liquid injection stopper 326 seals (closes) the liquid injection hole 325. Specifically, in the manufacturing process of the electricity storage device 1, after the electrolytic solution is injected into the case 3 from the injection hole 325, the injection plug 326 is inserted into the injection hole 325 to close the injection hole 325. The liquid injection hole 325 is sealed by laser welding the liquid injection stopper 326 and the case 3 (the cover plate 32 in the example of this embodiment). Specifically, the liquid injection stopper 326 includes a head 327 disposed along the outer surface of the case 3 and an insertion portion 328 extending from the head 327 and inserted into the liquid injection hole 325. The liquid injection stopper 326 of the present embodiment is fixed to the case 3 (the cover plate 32 in the example of the present embodiment) by welding. Specifically, the lid plate 32 and the periphery of the head 327 are laser welded.

頭部３２７は、注液孔３２５を覆う部位である。頭部３２７は、Ｚ軸方向視において注液孔３２５より大きい。具体的に、頭部３２７は、板状の部位であり、蓋板３２と重なるようにして注液孔３２５を覆う。本実施形態の頭部３２７は、Ｚ軸方向視において略円形の輪郭を有する。即ち、頭部３２７は、円板状の部位である。   The head 327 is a part that covers the liquid injection hole 325. The head 327 is larger than the liquid injection hole 325 when viewed in the Z-axis direction. Specifically, the head 327 is a plate-shaped part and covers the liquid injection hole 325 so as to overlap the lid plate 32. The head 327 of the present embodiment has a substantially circular outline when viewed in the Z-axis direction. That is, the head 327 is a disk-shaped part.

頭部３２７における蓋板３２と対向する面と反対の面の中央に、基準凹部３２９が設けられる。基準凹部３２９は、頭部３２７の周縁と蓋板３２とをレーザ溶接（自動溶接）するときの溶接位置を決めるための基準等として用いられる。   A reference recess 329 is provided at the center of the surface of the head 327 opposite to the surface facing the cover plate 32. The reference recess 329 is used as a reference for determining a welding position when laser welding (automatic welding) of the periphery of the head 327 and the lid plate 32 is performed.

挿入部３２８は、頭部３２７から注液孔３２５内に延びる柱状の部位である。本実施形態の挿入部３２８は、頭部３２７から該頭部３２７の拡がり方向（ケース３の外面が拡がる方向）と直交する方向に延びる略円柱状の部位である。挿入部３２８の長さ寸法は、ケース３における注液孔３２５の形成された壁（本実施形態の例では蓋板３２）の厚さ寸法より小さい（図３参照）。この挿入部３２８は、注液孔３２５に圧入される径を有する圧入部３２８１と、圧入部３２８１からテーパ状に延びる縮径部（先端部、又は挿入部３２８における先端を含む部位）３２８２とを有する。   The insertion portion 328 is a columnar portion extending from the head 327 into the liquid injection hole 325. The insertion portion 328 of the present embodiment is a substantially cylindrical portion that extends from the head 327 in a direction orthogonal to the direction in which the head 327 extends (the direction in which the outer surface of the case 3 expands). The length dimension of the insertion part 328 is smaller than the thickness dimension of the wall (the cover plate 32 in the example of this embodiment) in which the liquid injection hole 325 is formed in the case 3 (see FIG. 3). The insertion portion 328 includes a press-fit portion 3281 having a diameter to be press-fitted into the liquid injection hole 325, and a reduced diameter portion (a tip portion or a portion including the tip of the insert portion 328) 3282 extending in a tapered shape from the press-fit portion 3281. Have.

圧入部３２８１の外径は、蓋板３２の注液孔３２５の内径よりも僅かに大きい。このため、注液栓３２６を蓋板３２に取り付けるときには、挿入部３２８（圧入部３２８１）が注液孔３２５に圧入される。圧入部３２８１の長さ寸法（挿入部３２８が延びる方向の寸法）は、挿入部３２８が注液孔３２５に圧入された状態で頭部３２７の周縁と蓋板３２とがレーザ溶接されるときに、蓋板３２に対して注液栓３２６が動かない（例えば傾かない）ような大きさに設定されている。   The outer diameter of the press-fit portion 3281 is slightly larger than the inner diameter of the liquid injection hole 325 of the lid plate 32. For this reason, when the liquid injection stopper 326 is attached to the lid plate 32, the insertion portion 328 (press-fit portion 3281) is press-fitted into the liquid injection hole 325. The length dimension of the press-fit portion 3281 (the dimension in the direction in which the insert portion 328 extends) is determined when the peripheral edge of the head 327 and the lid plate 32 are laser-welded in a state where the insert portion 328 is press-fitted into the liquid injection hole 325. The liquid injection stopper 326 is set to a size that does not move (for example, does not tilt) with respect to the cover plate 32.

縮径部３２８２の外径は、挿入部３２８の先端に向かって漸減する、即ち、縮径部３２８２は、先端に向かうほど縮径している。   The outer diameter of the reduced diameter portion 3282 gradually decreases toward the distal end of the insertion portion 328. That is, the reduced diameter portion 3282 decreases in diameter toward the distal end.

本実施形態の注液栓３２６は、注液孔３２５の内周面３２５１においてケース３の内面における注液孔３２５の開口を画定する開口縁（エッジ）３２５２を含む位置に付着する電解液の液滴を避けた形状を有する（図３参照）。即ち、注液孔３２５の内周面３２５１における開口縁３２５２を含む位置に電解液の液滴７０が付着した状態で、注液栓３２６の挿入部３２８が注液孔３２５に挿入されたときに、挿入部３２８が液滴７０と接触しない。挿入部３２８の詳しい形状は、以下の通りである。   The liquid injection plug 326 of the present embodiment is a liquid electrolyte solution attached to a position including an opening edge (edge) 3252 defining an opening of the liquid injection hole 325 on the inner surface of the case 3 on the inner peripheral surface 3251 of the liquid injection hole 325. It has a shape that avoids drops (see FIG. 3). That is, when the insertion portion 328 of the liquid injection plug 326 is inserted into the liquid injection hole 325 in a state where the droplet 70 of the electrolytic solution adheres to the position including the opening edge 3252 on the inner peripheral surface 3251 of the liquid injection hole 325. , The insertion portion 328 does not contact the droplet 70. The detailed shape of the insertion portion 328 is as follows.

先ず、液滴７０の曲率半径を求める。このとき、液滴７０が半球（半球形状）７２であると見なし、この半球７２の半径ｒを液滴の半径ｒと見なす。これは、重力によって液滴７０が半球７２と比べて下方に垂れた形状となるため、挿入部３２８が半球７２に接しない形状を有していれば、挿入部３２８が液滴７０と接触しないからである。   First, the radius of curvature of the droplet 70 is obtained. At this time, the droplet 70 is regarded as a hemisphere (hemisphere shape) 72, and the radius r of the hemisphere 72 is regarded as the radius r of the droplet. This is because the droplet 70 is drooped downward due to gravity compared to the hemisphere 72, so that the insertion portion 328 does not contact the droplet 70 if the insertion portion 328 has a shape that does not contact the hemisphere 72. Because.

液滴７０に働く力を図５に示す。この図５において、矢印γＳＧは、固体と液体との界面の表面張力であり、矢印γＬＧは、液体と気体との界面の表面張力であり、矢印γＳＬは、固体と液体との界面の表面張力であり、ｍは、液滴７０と見なした半球７２の質量であり、ｇは、重力加速度であり、ρは、液滴７０と見なした半球７２を構成する電解液の密度であり、ｒは、液滴７０と見なした半球７２の半径である。また、液滴７０の固体との接触角（内周面３２５１と、固体と液体との界面の表面張力の方向とのなす角）をθとする。 The force acting on the droplet 70 is shown in FIG. In FIG. 5, arrow γ SG is the surface tension of the interface between the solid and liquid, arrow γ LG is the surface tension of the interface between the liquid and gas, and arrow γ SL is the interface between the solid and the liquid. M is the mass of the hemisphere 72 regarded as the droplet 70, g is the acceleration of gravity, and ρ is the density of the electrolyte that constitutes the hemisphere 72 regarded as the droplet 70. Where r is the radius of the hemisphere 72 considered to be a droplet 70. Further, the contact angle of the droplet 70 with the solid (the angle formed by the inner peripheral surface 3251 and the surface tension direction of the interface between the solid and the liquid) is defined as θ.

液滴７０に働く力の釣り合いは、以下の式（１）で表される。

Figure 2016154092
ここで、ｍｇは、以下の式（２）で求められる。
Figure 2016154092
 これら式（１）及び式（２）から、
Figure 2016154092
 The balance of forces acting on the droplet 70 is expressed by the following equation (1).
Figure 2016154092
 Here, mg is calculated | required by the following formula | equation (2).
Figure 2016154092
 From these formulas (1) and (2),
Figure 2016154092

また、ケース３の注液孔３２５が設けられた壁（本実施形態の例では蓋板３２）の厚さ寸法（Ｚ軸方向の寸法）をｌとし、注液孔３２５の内周面３２５１における液滴７０（詳しくは、液滴７０と見なした半球７２）が存在するＺ軸方向の範囲をｄとすると、内周面３２５１において液滴７０が存在しないＺ軸方向の範囲Δｘは、以下のようにして求められる。

Figure 2016154092
ここで、式（３）で求められたｒを式（４）に代入すると、
Figure 2016154092
 Further, the thickness dimension (dimension in the Z-axis direction) of the wall (the cover plate 32 in the example of the present embodiment) provided with the liquid injection hole 325 of the case 3 is l, and the inner peripheral surface 3251 of the liquid injection hole 325 is Assuming that the range in the Z-axis direction where the droplet 70 (specifically, the hemisphere 72 regarded as the droplet 70) exists is d, the range Δx in the Z-axis direction where the droplet 70 does not exist on the inner peripheral surface 3251 is It is calculated as follows.
Figure 2016154092
 Here, substituting r obtained by Equation (3) into Equation (4),
Figure 2016154092

挿入部３２８は、以上のようにして求められた半径ｒの半球７２と、接触しないような形状を有する。本実施形態の挿入部３２８では、圧入部３２８１の長さ寸法が、式（５）で求められたΔｘより小さく設定され、且つ、縮径部３２８２の形状が、半径ｒの半球７２と接触しないテーパ形状に設定されている。   The insertion portion 328 has a shape that does not contact the hemisphere 72 having the radius r determined as described above. In the insertion portion 328 of the present embodiment, the length dimension of the press-fit portion 3281 is set to be smaller than Δx obtained by Expression (5), and the shape of the reduced diameter portion 3282 does not contact the hemisphere 72 having the radius r. The taper shape is set.

外部端子４は、他の蓄電素子の外部端子又は外部機器等と電気的に接続される部位である。外部端子４は、導電性を有する部材によって形成される。   The external terminal 4 is a part that is electrically connected to an external terminal of another power storage element or an external device. The external terminal 4 is formed of a conductive member.

集電体５は、ケース３内に配置され、電極体２と通電可能に直接又は間接に接続される。集電体５は、導電性を有する部材によって形成される。本実施形態の集電体５は、外部端子４と電極体２とを通電可能に接続する。集電体５は、蓄電素子１の正極と負極とにそれぞれ配置される。   The current collector 5 is disposed in the case 3 and is directly or indirectly connected to the electrode body 2 so as to be energized. The current collector 5 is formed of a conductive member. The current collector 5 of the present embodiment connects the external terminal 4 and the electrode body 2 so as to allow energization. The current collector 5 is disposed on each of the positive electrode and the negative electrode of the power storage device 1.

蓄電素子１は、電極体２とケース３とを絶縁する絶縁部材６等も備える。本実施形態の絶縁部材６は、例えば、絶縁カバーである。絶縁カバー６は、ケース３（詳しくはケース本体３１）と電極体２との間に配置される。絶縁カバー６は、絶縁性を有する部材によって形成される。   The power storage element 1 also includes an insulating member 6 that insulates the electrode body 2 from the case 3. The insulating member 6 of this embodiment is an insulating cover, for example. The insulating cover 6 is disposed between the case 3 (specifically, the case body 31) and the electrode body 2. The insulating cover 6 is formed of an insulating member.

以上の蓄電素子１によれば、電解液の注入後に注液栓３２６の挿入部３２８を注液孔３２５に挿入したときに、挿入部３２８と、蓋板３２に付着した電解液（例えば、電解液の液滴）との接触を避けることができる。このため、ケース３（注液孔３２５の内周面３２５１等）と注液栓３２６との間の電解液の液上がりが抑えられる。これにより、ケース３内への電解液の注入後にケース３と注液栓３２６とを溶接（本実施形態の例ではレーザ溶接）して注液孔３２５を密閉したときの溶接部位において、蓋板３２に付着した電解液に起因する溶接荒れが生じ難い。その結果、ケース３と注液栓３２６との溶接部位において溶接荒れの抑えられた蓄電素子１が得られる。   According to the power storage device 1 described above, when the insertion portion 328 of the liquid injection plug 326 is inserted into the liquid injection hole 325 after the electrolytic solution has been injected, the electrolytic solution (for example, electrolysis) attached to the insertion portion 328 and the cover plate 32. Contact with liquid droplets) can be avoided. For this reason, the rising of the electrolyte solution between the case 3 (inner peripheral surface 3251 of the injection hole 325 and the like) and the injection plug 326 is suppressed. As a result, the lid 3 is welded when the case 3 and the injection plug 326 are welded (laser welding in the example of the present embodiment) and the injection hole 325 is sealed after the electrolyte is injected into the case 3. Rough welding due to the electrolytic solution adhering to 32 is unlikely to occur. As a result, it is possible to obtain the electricity storage device 1 in which the welding roughness is suppressed at the welded portion between the case 3 and the liquid filling plug 326.

本実施形態の蓄電素子１では、挿入部３２８の長さ寸法がケース３における注液孔３２５の形成された壁（本実施形態の例では蓋板３２）の厚さ寸法より小さい。このような簡素な構成によって、電解液の注入後に注液栓３２６の挿入部３２８を注液孔３２５に挿入したときの、挿入部３２８と、蓋板３２に付着した電解液との接触を防ぐことができる。   In the electricity storage device 1 of the present embodiment, the length dimension of the insertion portion 328 is smaller than the thickness dimension of the wall (the cover plate 32 in the example of the present embodiment) in which the liquid injection hole 325 is formed. Such a simple configuration prevents contact between the insertion portion 328 and the electrolyte attached to the cover plate 32 when the insertion portion 328 of the injection plug 326 is inserted into the injection hole 325 after the injection of the electrolyte. be able to.

本実施形態の蓄電素子では、挿入部３２８の縮径部（先端部）３２８２は、先端に向かうほど縮径している。このため、ケース３内への電解液の注入後に注液栓３２６によって注液孔３２５を塞ぐ（密閉する）際に、注液栓３２６の挿入部３２８を注液孔３２５に挿入し易い。   In the electricity storage device of this embodiment, the reduced diameter portion (tip portion) 3282 of the insertion portion 328 is reduced in diameter toward the tip. For this reason, when the liquid injection hole 325 is closed (sealed) by the liquid injection plug 326 after the electrolyte is injected into the case 3, the insertion portion 328 of the liquid injection plug 326 is easily inserted into the liquid injection hole 325.

尚、本発明の蓄電素子は、上記実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲内において種々変更を加え得ることは勿論である。例えば、ある実施形態の構成に他の実施形態の構成を追加することができ、また、ある実施形態の構成の一部を他の実施形態の構成に置き換えることができる。さらに、ある実施形態の構成の一部を削除することができる。   In addition, the electrical storage element of this invention is not limited to the said embodiment, Of course, a various change can be added in the range which does not deviate from the summary of this invention. For example, the configuration of another embodiment can be added to the configuration of a certain embodiment, and a part of the configuration of a certain embodiment can be replaced with the configuration of another embodiment. Furthermore, a part of the configuration of an embodiment can be deleted.

注液栓３２６における挿入部３２８の具体的な形状は、限定されない。上記実施形態では、挿入部３２８は、圧入部３２８１と縮径部３２８２とを有するが、例えば、縮径部３２８２のない構成、即ち、圧入部３２８１のみによって構成されてもよい。また、圧入部３２８１から延びる部位（上記実施形態の例では、縮径部３２８２）は、図６に示すように、圧入部３２８１より径の小さな小径部３２８３であってもよい。即ち、挿入部３２８は、段差形状等であってもよい。この場合も、小径部３２８３の径は、内周面３２５１の開口縁３２５２を含む位置に付着した電解液の液滴７０と接触しない大きさに設定される。以上のように、挿入部３２８は、内周面３２５１における開口縁３２５２を含む位置に付着する電解液の液滴７０を避けた形状を有していればよい。   The specific shape of the insertion part 328 in the liquid injection stopper 326 is not limited. In the above-described embodiment, the insertion portion 328 includes the press-fit portion 3281 and the reduced diameter portion 3282. For example, the insertion portion 328 may be configured only by the press-fit portion 3281 without the reduced diameter portion 3282. Further, the portion extending from the press-fit portion 3281 (in the example of the above embodiment, the reduced diameter portion 3282) may be a small-diameter portion 3283 having a smaller diameter than the press-fit portion 3281 as shown in FIG. That is, the insertion portion 328 may have a step shape or the like. Also in this case, the diameter of the small diameter portion 3283 is set to a size that does not contact the droplet 70 of the electrolytic solution adhering to the position including the opening edge 3252 of the inner peripheral surface 3251. As described above, the insertion portion 328 only needs to have a shape that avoids the electrolyte droplet 70 adhering to the position including the opening edge 3252 on the inner peripheral surface 3251.

上記実施形態の注液栓３２６における挿入部３２８の長さ寸法は、蓋板３２の厚さ寸法より小さいが、この構成に限定されない。挿入部３２８は、例えば、小径部３２８３の先端がケース３の内面よりも突出した形状でもよい（図６の破線参照）。即ち、挿入部３２８は、内周面３２５１における開口縁３２５２を含む位置に付着する電解液の液滴７０を避けた形状であれば、ケース３における注液孔３２５が形成された壁の厚さ寸法より大きな長さ寸法を有していてもよい。   Although the length dimension of the insertion part 328 in the liquid injection stopper 326 of the said embodiment is smaller than the thickness dimension of the cover plate 32, it is not limited to this structure. For example, the insertion portion 328 may have a shape in which the tip of the small diameter portion 3283 protrudes from the inner surface of the case 3 (see the broken line in FIG. 6). That is, if the insertion portion 328 has a shape that avoids the electrolyte droplet 70 adhering to a position including the opening edge 3252 on the inner peripheral surface 3251, the thickness of the wall in which the liquid injection hole 325 in the case 3 is formed. It may have a length dimension greater than the dimension.

また、上記実施形態の蓄電素子１では、注液栓３２６の挿入部３２８が、該挿入部３２８と、内周面３２５１における開口縁３２５２を含む位置に付着する電解液の液滴７０と、の接触を避けた形状を有しているが、この構成に限定されない。例えば、図７に示すように、注液孔３２５の内周面３２５１が、挿入部３２８と、内周面３２５１における開口縁３２５２を含む位置に付着する電解液の液滴７０と、の接触を避けた形状を有してもよい。また、挿入部３２８と注液孔３２５の内周面３２５１との両方の形状によって、挿入部３２８と、内周面３２５１における開口縁３２５２を含む位置に付着する電解液の液滴７０と、の接触を避けてもよい。   Further, in the electricity storage device 1 of the above-described embodiment, the insertion portion 328 of the liquid injection plug 326 includes the insertion portion 328 and the electrolyte droplet 70 attached to a position including the opening edge 3252 on the inner peripheral surface 3251. Although it has a shape that avoids contact, it is not limited to this configuration. For example, as shown in FIG. 7, the inner peripheral surface 3251 of the liquid injection hole 325 makes contact with the insertion portion 328 and the electrolyte droplet 70 attached to the position including the opening edge 3252 on the inner peripheral surface 3251. It may have an avoiding shape. Further, depending on the shapes of both the insertion portion 328 and the inner peripheral surface 3251 of the liquid injection hole 325, the insertion portion 328 and the droplet 70 of the electrolytic solution adhering to the position including the opening edge 3252 on the inner peripheral surface 3251 Contact may be avoided.

また、上記実施形態においては、蓄電素子が充放電可能な非水電解質二次電池（例えばリチウムイオン二次電池）として用いられる場合について説明したが、蓄電素子の種類や大きさ（容量）は任意である。また、上記実施形態において、蓄電素子の一例として、リチウムイオン二次電池について説明したが、これに限定されるものではない。例えば、本発明は、種々の二次電池、その他、一次電池や、電気二重層キャパシタ等のキャパシタの蓄電素子にも適用可能である。   Moreover, in the said embodiment, although the case where an electrical storage element was used as a nonaqueous electrolyte secondary battery (for example, lithium ion secondary battery) which can be charged / discharged was demonstrated, the kind and magnitude | size (capacity | capacitance) of an electrical storage element are arbitrary. It is. Moreover, in the said embodiment, although the lithium ion secondary battery was demonstrated as an example of an electrical storage element, it is not limited to this. For example, the present invention can be applied to various secondary batteries, other primary batteries, and power storage elements of capacitors such as electric double layer capacitors.

蓄電素子（例えば電池）は、図８に示すような蓄電装置（蓄電素子が電池の場合は電池モジュール）１１に用いられてもよい。蓄電装置１１は、少なくとも二つの蓄電素子１と、二つの（異なる）蓄電素子１同士を電気的に接続するバスバ部材１２と、を有する。この場合、本発明の技術が少なくとも一つの蓄電素子１に適用されていればよい。   The power storage element (for example, battery) may be used in a power storage device 11 (a battery module when the power storage element is a battery) 11 as shown in FIG. The power storage device 11 includes at least two power storage elements 1 and a bus bar member 12 that electrically connects two (different) power storage elements 1 to each other. In this case, the technique of the present invention only needs to be applied to at least one power storage element 1.

１…蓄電素子、２…電極体、２１…巻芯、２２…積層体、３…ケース、３１…ケース本体、３１１…閉塞部、３１２…胴部、３２…蓋板、３２５…注液孔、３２５１…内周面、３２５２…開口縁、３２６…注液栓、３２７…頭部、３２８…挿入部、３２８１…圧入部、３２８２…縮径部、３２８３…小径部、３２９…基準凹部、３３…内部空間、４…外部端子、５…集電体、６…絶縁部材（絶縁カバー）、１１…蓄電装置、１２…バスバ部材、７０…液滴、７２…半球、ｒ…液滴と見なす半球の半径   DESCRIPTION OF SYMBOLS 1 ... Power storage element, 2 ... Electrode body, 21 ... Core, 22 ... Laminated body, 3 ... Case, 31 ... Case main body, 311 ... Closure part, 312 ... Body part, 32 ... Cover plate, 325 ... Injection hole, 3251 ... Inner peripheral surface, 3252 ... Opening edge, 326 ... Injection stopper, 327 ... Head, 328 ... Insertion part, 3281 ... Press-fitting part, 3282 ... Reduced diameter part, 3283 ... Small diameter part, 329 ... Reference recess, 33 ... Internal space, 4 ... external terminal, 5 ... current collector, 6 ... insulating member (insulating cover), 11 ... power storage device, 12 ... bus bar member, 70 ... droplet, 72 ... hemisphere, r ... hemisphere regarded as droplet radius

Claims (3)

電解液を注入する注液孔の形成されたケースと、
前記注液孔を塞ぐ注液栓と、を備え、
前記注液栓は、
前記ケースの外面に沿って配置される頭部であって前記ケースと溶接されている頭部と、
前記頭部から延び且つ前記注液孔に挿入されている挿入部と、を有し、
前記注液栓、及び前記注液孔の内周面の少なくとも一方は、該注液栓と、該内周面において前記ケースの内面における前記注液孔の開口を画定する開口縁を含む位置に付着する電解液と、の接触を避ける形状を有する、蓄電素子。 A case in which an injection hole for injecting an electrolyte is formed;
A liquid stopper for closing the liquid injection hole,
The injection stopper is
A head disposed along the outer surface of the case and welded to the case;
An insertion portion extending from the head and inserted into the liquid injection hole,
At least one of the liquid injection stopper and the inner peripheral surface of the liquid injection hole is at a position including the liquid injection stopper and an opening edge that defines an opening of the liquid injection hole in the inner surface of the case on the inner peripheral surface. A power storage element having a shape that avoids contact with an attached electrolytic solution. 前記挿入部の長さ寸法は、前記ケースにおける前記注液孔の形成された壁の厚さ寸法より小さい、請求項１に記載の蓄電素子。   The power storage element according to claim 1, wherein a length dimension of the insertion portion is smaller than a thickness dimension of a wall in the case where the liquid injection hole is formed. 前記挿入部の先端部は、先端に向かうほど縮径している、請求項１又は２に記載の蓄電素子。   The electric storage element according to claim 1, wherein the distal end portion of the insertion portion is reduced in diameter toward the distal end.
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