JP2003132866A - Safety valve for battery - Google Patents
Safety valve for batteryInfo
- Publication number
- JP2003132866A JP2003132866A JP2001324968A JP2001324968A JP2003132866A JP 2003132866 A JP2003132866 A JP 2003132866A JP 2001324968 A JP2001324968 A JP 2001324968A JP 2001324968 A JP2001324968 A JP 2001324968A JP 2003132866 A JP2003132866 A JP 2003132866A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- safety valve
- metal foil
- substrate
- hole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電池用安全弁に属
する。TECHNICAL FIELD The present invention relates to a safety valve for a battery.
【０００２】[0002]
【従来の技術】携帯電話等の小型電子機器に内蔵される
電池として、リチウムイオン二次電池が多く使用され
る。リチウムイオン二次電池には、高温時などの異常時
に発生するガスによって電池が破裂するのを防止するた
めに、電池内圧の上昇に伴って開く安全弁などの安全機
構が必要である。従来より安全弁としては、プレス加工
により作製されるプレス品が知られているが、プレス品
には、機械的強度が低く、よって電池全体が歪んだとき
に亀裂が入って電解液の漏液を起こしやすいという欠点
がある。また安全弁として、クラッド加工により作製さ
れるクラッドメタルが知られている（特開平７−５０１
５９号、特開平１１−１６５５８号、特開平１１−７３
９３５号、特開平１１−１６２４３５号、特許第３１０
８３６０号公報）。クラッドメタルには、上記のような
欠点が無く、従ってより一般的に使用されている。図１
に、クラッドメタルタイプの安全弁を使用したリチウム
イオン二次電池を斜視図として示す。2. Description of the Related Art Lithium ion secondary batteries are often used as batteries incorporated in small electronic devices such as mobile phones. The lithium-ion secondary battery requires a safety mechanism such as a safety valve that opens with an increase in the internal pressure of the battery in order to prevent the battery from exploding due to a gas generated during abnormal conditions such as high temperature. Conventionally, as a safety valve, a press product manufactured by press work is known, but the press product has low mechanical strength, and therefore cracks occur when the entire battery is distorted to prevent electrolyte leakage. It has the drawback of being easy to wake up. As a safety valve, clad metal produced by clad processing is known (Japanese Patent Laid-Open No. 7-501).
59, JP-A-11-16558, JP-A-11-73.
No. 935, JP-A No. 11-162435, and Patent No. 310.
8360). Clad metals do not have the drawbacks mentioned above and are therefore more commonly used. Figure 1
Fig. 1 shows a perspective view of a lithium ion secondary battery using a clad metal type safety valve.
【０００３】この電池１は、正極板、負極板及びこれら
の間に介在して非水電解液を保持するセパレータからな
る発電要素２を備え、発電要素２は角形のケース３に収
納されている。ケース３の上面は開口しており、その面
には、図２、３にそれぞれ平面図及び断面図として示す
蓋４がレーザー溶接されている。蓋４は、金属製の基板
４ａと、アルミニウムを主成分とする金属箔４ｂとをク
ラッド加工により積層させてなる。蓋４の中央部には、
基板４ａ及び金属箔４ｂを貫通し、電池端子５を挿入可
能な孔４ｃが設けられている。また蓋４の端部には、基
板４ａを貫通する通気孔４ｄが設けられており、この通
気孔４ｄは金属箔４ｂによって閉塞されている。電池内
に異常なガスが発生して内圧が所定値まで上昇した時、
金属箔４ｂの通気孔４ｂ部分は破れ、その結果、電池内
のガスは外部へ排出される。つまり、この電池１では、
蓋４が安全弁として機能する。This battery 1 is provided with a power generating element 2 composed of a positive electrode plate, a negative electrode plate, and a separator interposed therebetween to hold a nonaqueous electrolytic solution. The power generating element 2 is housed in a rectangular case 3. . The upper surface of the case 3 is open, and a lid 4 shown in FIGS. 2 and 3 as a plan view and a cross-sectional view is laser-welded to the top surface of the case 3. The lid 4 is formed by laminating a metal substrate 4a and a metal foil 4b containing aluminum as a main component by clad processing. At the center of the lid 4,
A hole 4c that penetrates the substrate 4a and the metal foil 4b and into which the battery terminal 5 can be inserted is provided. A vent hole 4d penetrating the substrate 4a is provided at the end of the lid 4, and the vent hole 4d is closed by a metal foil 4b. When abnormal gas is generated in the battery and the internal pressure rises to a predetermined value,
The vent hole 4b portion of the metal foil 4b is broken, and as a result, the gas in the battery is discharged to the outside. That is, in this battery 1,
The lid 4 functions as a safety valve.
【０００４】[0004]
【発明が解決しようとする課題】しかし、従来のクラッ
ドメタルタイプの安全弁では、金属箔４ｂが破れるとき
に、最初にピンホール状に破れてその孔が徐々に拡大す
る。そのため、通気孔４ｄが全開するまで時間が掛か
り、電池内圧を瞬時に下げることができない。よって、
電池の安全性が十分でない。それ故、本発明の課題は、
電池の安全性をより高めることが可能な電池用安全弁を
提供することにある。However, in the conventional clad metal type safety valve, when the metal foil 4b is torn, it is first torn in a pinhole shape and the hole gradually expands. Therefore, it takes time until the vent hole 4d is fully opened, and the battery internal pressure cannot be instantaneously lowered. Therefore,
The battery is not safe enough. Therefore, the object of the present invention is to
An object of the present invention is to provide a battery safety valve that can further enhance the safety of the battery.
【０００５】[0005]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討を重ねた結果、本発明に至っ
た。即ち、本発明の電池用安全弁は、貫通孔を有する基
板と、アルミニウムを主成分とし、前記貫通孔を閉塞す
るように前記基板に積層された金属箔とを備える電池用
安全弁において、前記金属箔のアルミニウム純度が、９
９．０〜９９．８重量％であることを特徴とする。The inventors of the present invention have made extensive studies in order to solve the above problems, and as a result, arrived at the present invention. That is, the battery safety valve of the present invention is a battery safety valve comprising a substrate having a through hole and a metal foil mainly composed of aluminum and laminated on the substrate so as to close the through hole, wherein the metal foil is used. Has an aluminum purity of 9
It is characterized by being 9.0 to 99.8% by weight.
【０００６】基板の材料としては、例えば、アルミニウ
ム、銅、ステンレス、ニッケル、ニッケル−鉄合金など
の金属を使用することができる。基板に貫通孔を形成さ
せる方法については、特に限定はなく、打ち抜きプレス
やエッチングなどの公知の方法を採用すると良い。金属
箔は、例えば、冷間圧延法により作製される。また、冷
間圧延後に焼鈍処理しても良い。金属箔の厚さは１５〜
２９μｍが望ましい。基板と金属箔とを接合させるに
は、クラッド加工すると良い。そのためには、例えば真
空中で冷間圧接する。As the material of the substrate, for example, metal such as aluminum, copper, stainless steel, nickel, nickel-iron alloy can be used. The method of forming the through hole in the substrate is not particularly limited, and a known method such as punching press or etching may be adopted. The metal foil is produced, for example, by a cold rolling method. Moreover, you may anneal-process after cold rolling. The thickness of the metal foil is 15 ~
29 μm is desirable. In order to join the substrate and the metal foil, clad processing may be performed. For that purpose, cold pressure welding is performed in a vacuum, for example.
【０００７】本発明は、金属箔として純Ａｌではなく、
Ａｌ９９．８重量％以下の合金を用いている。即ち、少
量の他成分がＡｌの粒成長を抑制し、金属箔全体を緻密
化し、強度を高めていると考えられる。従って別の局面
から見れば、本発明は、貫通孔を有する基板と、アルミ
ニウムを主成分とし、前記貫通孔を閉塞するように前記
基板に積層された金属箔とを備える電池用安全弁におい
て、前記金属箔の構成粒子の平均粒径が、０．０２０〜
０．０４５ｍｍであることを特徴とする。ここで、粒径
とは、金属箔面方向における粒子の長さを言う。According to the present invention, the metal foil is not pure Al but
An alloy containing 99.8% by weight or less of Al is used. That is, it is considered that a small amount of other component suppresses grain growth of Al, densifies the entire metal foil, and enhances strength. Therefore, from another aspect, the present invention is a battery safety valve comprising a substrate having a through hole and a metal foil mainly composed of aluminum and laminated on the substrate so as to close the through hole, The average particle size of the constituent particles of the metal foil is 0.020 to
It is characterized by being 0.045 mm. Here, the particle size refers to the length of the particles in the surface direction of the metal foil.
【０００８】本発明の電池用安全弁は、リチウムイオン
二次電池に好適に適用されうる。この場合、発電要素と
しては、例えば、コバルト酸リチウム等の活物質材料が
塗布された正極板、リチウム塩を含む有機電解液が保持
するセパレータ、及び炭素等のホスト物質が塗布された
負極板を順に積層して渦状に巻いたものがある。発電要
素を収納するケースとしては、アルミニウム等の金属か
らなる角形のケースを使用することができる。本発明の
安全弁は、ケースの側壁や蓋にレーザー溶接により接合
されると良い。また、本発明の安全弁が、ケースの蓋を
兼ねていても良い。The battery safety valve of the present invention can be suitably applied to a lithium ion secondary battery. In this case, as the power generation element, for example, a positive electrode plate coated with an active material such as lithium cobalt oxide, a separator held by an organic electrolyte containing a lithium salt, and a negative electrode plate coated with a host material such as carbon. There is one that is laminated in order and wound in a spiral shape. A rectangular case made of metal such as aluminum can be used as a case for accommodating the power generation element. The safety valve of the present invention may be joined to the side wall and the lid of the case by laser welding. Further, the safety valve of the present invention may also serve as a cover for the case.
【０００９】[0009]
【実施例】図１に示すリチウムイオン二次電池を以下の
ようにして製造した。まず、上面が開口した５．１ｍｍ
×３０ｍｍ×４８ｍｍのアルミニウム製のケース３を用
意した。別途、ケース３上面を封口できる大きさのアル
ミニウム製基板４ａの整数倍以上の大きさのアルミニウ
ム板、及びそれとほぼ同じサイズでアルミニウムを主成
分とし、表１に示す種々の組成、厚さ及び平均粒径の合
金からなる金属箔を準備した。そして、アルミニウム板
の所定位置に打ち抜きプレスにより通気孔４ｄを開け、
続いてそのアルミニウム板と金属箔とをクラッドした。
クラッドされた合板を切断することにより、アルミニウ
ム板と金属箔との大きさを揃えた後、端子用の凹部４ｅ
をプレス成形し、次いで端子用の貫通孔４ｃを打ち抜
き、最後に凹部４ｅ及び通気孔４ｄを囲む一単位全体を
打ち抜くことによって、蓋４を得た。EXAMPLE A lithium ion secondary battery shown in FIG. 1 was manufactured as follows. First, the top surface is open 5.1 mm
An aluminum case 3 having a size of 30 mm and 48 mm was prepared. Separately, an aluminum plate having an integer multiple or more of an aluminum substrate 4a having a size capable of sealing the upper surface of the case 3, and aluminum having the same size as the main component and having various compositions, thicknesses and averages A metal foil made of an alloy having a grain size was prepared. Then, the ventilation hole 4d is opened at a predetermined position of the aluminum plate by a punching press,
Then, the aluminum plate and the metal foil were clad.
After cutting the clad plywood to make the sizes of the aluminum plate and the metal foil uniform, the recesses 4e for terminals are formed.
Was press-molded, then the through hole 4c for the terminal was punched out, and finally the entire unit surrounding the recess 4e and the vent hole 4d was punched out to obtain the lid 4.
【００１０】[0010]
【表１】 [Table 1]
【００１１】続いて、コバルト酸リチウム８７重量部、
ポリフッ化ビニリデン８重量部及びアセチレンブラック
５重量部を混合し、適宜Ｎ−メチルピロリドンを加えて
ペースト状に調製した後、これをアルミニウム箔の両面
に塗布、乾燥することによって、正極板を作製した。さ
らに、黒鉛９０重量部とポリフッ化ビニリデン１０重量
部とを混合し、適宜Ｎ−メチルピロリドンを加えてペー
スト状に調製した後、これを銅箔に塗布、乾燥すること
によって、負極板を作製した。そして、ポリエチレン製
の微多孔フィルムからなるセパレータを正極板と負極板
とで挟み、これを長円渦状に巻回した。これにより、発
電要素２を得た。Subsequently, 87 parts by weight of lithium cobalt oxide,
8 parts by weight of polyvinylidene fluoride and 5 parts by weight of acetylene black were mixed, and N-methylpyrrolidone was appropriately added to prepare a paste, which was then coated on both sides of an aluminum foil and dried to prepare a positive electrode plate. . Furthermore, 90 parts by weight of graphite and 10 parts by weight of polyvinylidene fluoride were mixed, and N-methylpyrrolidone was appropriately added to prepare a paste, which was then applied to a copper foil and dried to prepare a negative electrode plate. . Then, a separator made of a polyethylene microporous film was sandwiched between a positive electrode plate and a negative electrode plate, and this was wound into an elliptical spiral shape. Thereby, the power generation element 2 was obtained.
【００１２】次いで、蓋４の中央部の孔４ｃに電池端子
５を挿入した後、発電要素２の負極板を電池端子５の下
端に接続させ、さらに正極板を蓋４の金属箔４ｂに集電
ワッシャーを介して接続させた。そして、発電要素２を
ケース３に収納し、ＬｉＰＦ 6を１ｍｏｌ／ｌ含むエチ
レンカーボネート：メチルエチルカーボネート＝４：６
（体積比）の混合液を注入した。その後、蓋４をケース
３の上面に填め込み、レーザー溶接することによって密
封した。これにて、蓋４の異なる４種類のリチウムイオ
ン二次電池１を得た。各電池の公称容量は、７４０ｍＡ
ｈである。Next, a battery terminal is placed in the hole 4c at the center of the lid 4.
After inserting 5, the negative electrode plate of the power generating element 2 is placed under the battery terminal 5.
Connect to the end and collect the positive plate on the metal foil 4b of the lid 4
It was connected via a washer. And the power generation element 2
Stored in Case 3, LiPF 6Ethyl containing 1 mol / l
Ren carbonate: methyl ethyl carbonate = 4: 6
The mixed solution (volume ratio) was injected. After that, cover 4
3 by fitting it on the upper surface and laser welding
I sealed it. With this, 4 types of lithium ion with different lids 4
A secondary battery 1 was obtained. Nominal capacity of each battery is 740mA
h.
【００１３】得られた各電池１を２５℃の温度で３時間
充電し、過充電時に蓋４が安全弁として正常に作動する
かどうかを試験した。充電条件は、０．５Ｃ、１２Ｖの
定電流定電圧、１Ｃ、１２Ｖの定電流定電圧、及び１．
５Ｃ、１２Ｖの定電流定電圧の３条件とした。尚、この
試験には、各種類の電池１を３個ずつ供した。また、各
電池１を２５０℃に加熱したホットプレート上に固定す
ることによって、高温時に蓋４が安全弁として正常に作
動するかを試験した。尚、この試験には、各種類の電池
１を３個ずつ供した。Each of the batteries 1 thus obtained was charged at a temperature of 25 ° C. for 3 hours, and it was tested whether the lid 4 normally operates as a safety valve when overcharged. The charging conditions are 0.5 C, 12 V constant current constant voltage, 1 C, 12 V constant current constant voltage, and 1.
Three conditions were used: constant current and constant voltage of 5C and 12V. In this test, three batteries 1 of each type were provided. Further, by fixing each battery 1 on a hot plate heated to 250 ° C., it was tested whether the lid 4 normally operates as a safety valve at a high temperature. In this test, three batteries 1 of each type were provided.
【００１４】さらに、各電池１を１．５ｍの高さから落
下させ、金属箔４ｂの通気孔４ｄを閉塞する部分が、衝
撃により破れないかどうかを試験した。このとき、１回
の落下毎に電池１の向きを変えることによって、電池１
の６面全てが順に地面に衝突するようにし、それを３０
サイクル繰り返した。各試験の結果を表２に示す。表２
中、○は蓋４が正常に作動したことを、×は蓋４が正常
に作動せずにケース３が破壊したことを、ＯＫは蓋４の
金属箔４ｂが破れなかったことを、それぞれ意味する。Further, each battery 1 was dropped from a height of 1.5 m, and it was tested whether the portion of the metal foil 4b which closes the ventilation hole 4d could be broken by impact. At this time, by changing the direction of the battery 1 for each drop, the battery 1
Make sure that all six surfaces of the
The cycle was repeated. The results of each test are shown in Table 2. Table 2
In the table, ○ means that the lid 4 worked normally, × means that the lid 4 did not work normally, and the case 3 was destroyed, and OK means that the metal foil 4b of the lid 4 did not break. To do.
【００１５】[0015]
【表２】 [Table 2]
【００１６】表２に見られるように、実施例１〜３の蓋
４を使用した電池１では、いずれの条件で過充電試験を
行っても蓋４が正常に作動し、また加熱試験でも正常に
作動した。さらに、落下試験によって、蓋４の金属箔４
ｂが破れることがなかった。それに対して、比較例の蓋
４を使用した電池では、加熱試験及び落下試験について
は違いがないものの、１．５Ｃ、１２Ｖの過充電試験で
２個の電池１が蓋４を正常にさせなかった。この結果よ
り、電池１の安全性の向上のためには、金属箔４ｂのア
ルミニウム純度は９９．０〜９９．８重量％が望ましい
こと、及び平均粒径は０．０２０〜０．０４５ｍｍ望ま
しいことが判った。As can be seen from Table 2, in the battery 1 using the lid 4 of Examples 1 to 3, the lid 4 operates normally regardless of the overcharge test under any condition, and the battery 4 is normal in the heating test. Worked. Furthermore, by a drop test, the metal foil 4 of the lid 4
b did not break. On the other hand, in the battery using the lid 4 of the comparative example, there was no difference in the heating test and the drop test, but the two batteries 1 did not make the lid 4 normal in the overcharge test of 1.5C and 12V. It was From this result, in order to improve the safety of the battery 1, the aluminum purity of the metal foil 4b is preferably 99.0 to 99.8% by weight, and the average particle size is preferably 0.020 to 0.045 mm. I understood.
【００１７】[0017]
【発明の効果】本発明の電池用安全弁によると、電池の
安全性を従来よりも高めることができる。According to the battery safety valve of the present invention, the safety of the battery can be improved more than before.
【図１】リチウムイオン二次電池を示す斜視図である。FIG. 1 is a perspective view showing a lithium-ion secondary battery.
【図２】リチウムイオン二次電池の蓋を示す平面図であ
る。FIG. 2 is a plan view showing a lid of a lithium ion secondary battery.
【図３】リチウムイオン二次電池の蓋を示す断面図であ
る。FIG. 3 is a cross-sectional view showing a lid of a lithium ion secondary battery.
１電池 ２発電要素 ３ケース ４蓋（安全弁） ４ａ基板、４ｂ金属箔 ５電池端子 1 battery 2 power generation elements 3 cases 4 lids (safety valve) 4a substrate, 4b metal foil 5 battery terminals
フロントページの続き (72)発明者 小暮 正紀 京都府京都市南区吉祥院新田壱ノ段町５番 地 ジーエス・メルコテック株式会社内 Ｆターム(参考） 5H012 AA07 BB02 DD01 EE04 FF01 GG01 JJ01 JJ10 Continued front page (72) Inventor Masanori Kogure 5 Nitta Ichinodancho, Kichijoin, Minami-ku, Kyoto-shi, Kyoto Prefecture Within GS Melcotech Co., Ltd. F-term (reference) 5H012 AA07 BB02 DD01 EE04 FF01 GG01 JJ01 JJ10
Claims (3)
成分とし、前記貫通孔を閉塞するように前記基板に積層
された金属箔とを備える電池用安全弁において、 前記金属箔のアルミニウム純度が、９９．０〜９９．８
重量％であることを特徴とする電池用安全弁。1. A battery safety valve comprising a substrate having a through hole and a metal foil mainly composed of aluminum and laminated on the substrate so as to close the through hole, wherein the aluminum purity of the metal foil is: 99.0-99.8
A safety valve for a battery, characterized in that the content is% by weight.
る請求項１に記載の電池用安全弁。2. The safety valve for a battery according to claim 1, wherein the metal foil has a thickness of 15 to 29 μm.
成分とし、前記貫通孔を閉塞するように前記基板に積層
された金属箔とを備える電池用安全弁において、 前記金属箔の構成粒子の平均粒径が、０．０２０〜０．
０４５ｍｍであることを特徴とする電池用安全弁。3. A battery safety valve comprising a substrate having a through hole and a metal foil mainly composed of aluminum and laminated on the substrate so as to close the through hole, wherein an average of constituent particles of the metal foil. The particle size is 0.020-0.
Safety valve for batteries, which is 045 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001324968A JP2003132866A (en) | 2001-10-23 | 2001-10-23 | Safety valve for battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001324968A JP2003132866A (en) | 2001-10-23 | 2001-10-23 | Safety valve for battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003132866A true JP2003132866A (en) | 2003-05-09 |
Family
ID=19141609
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001324968A Pending JP2003132866A (en) | 2001-10-23 | 2001-10-23 | Safety valve for battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003132866A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11289767B2 (en) | 2016-12-22 | 2022-03-29 | Cps Technology Holdings Llc | Valve assembly for a battery cover |
| US11411280B2 (en) | 2017-06-09 | 2022-08-09 | Cps Technology Holdings Llc | Absorbent glass mat battery |
| US11936032B2 (en) | 2017-06-09 | 2024-03-19 | Cps Technology Holdings Llc | Absorbent glass mat battery |
-
2001
- 2001-10-23 JP JP2001324968A patent/JP2003132866A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11289767B2 (en) | 2016-12-22 | 2022-03-29 | Cps Technology Holdings Llc | Valve assembly for a battery cover |
| US11411280B2 (en) | 2017-06-09 | 2022-08-09 | Cps Technology Holdings Llc | Absorbent glass mat battery |
| US11870096B2 (en) | 2017-06-09 | 2024-01-09 | Cps Technology Holdings Llc | Absorbent glass mat battery |
| US11936032B2 (en) | 2017-06-09 | 2024-03-19 | Cps Technology Holdings Llc | Absorbent glass mat battery |
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