JPH0732006B2 - Organic electrolyte battery - Google Patents

Organic electrolyte battery

Info

Publication number
JPH0732006B2
JPH0732006B2 JP61248648A JP24864886A JPH0732006B2 JP H0732006 B2 JPH0732006 B2 JP H0732006B2 JP 61248648 A JP61248648 A JP 61248648A JP 24864886 A JP24864886 A JP 24864886A JP H0732006 B2 JPH0732006 B2 JP H0732006B2
Authority
JP
Japan
Prior art keywords
valve body
battery
sealing plate
organic electrolyte
electrolyte battery
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.)
Expired - Fee Related
Application number
JP61248648A
Other languages
Japanese (ja)
Other versions
JPS63102160A (en
Inventor
文夫 大尾
正規 児島
誠 樋口
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Priority to JP61248648A priority Critical patent/JPH0732006B2/en
Publication of JPS63102160A publication Critical patent/JPS63102160A/en
Publication of JPH0732006B2 publication Critical patent/JPH0732006B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

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
    • H01M50/30—Arrangements for facilitating escape of gases
    • H01M50/342—Non-re-sealable arrangements
    • H01M50/3425—Non-re-sealable arrangements in the form of rupturable membranes or weakened parts, e.g. pierced with the aid of a sharp member
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Gas Exhaust Devices For Batteries (AREA)

Description

【発明の詳細な説明】 産業上の利用分野 本発明は、負極活物質としてリチウム等の軽金属を用い
て構成される有機電解質電池の防爆用封口板に関するも
のである。Description: TECHNICAL FIELD The present invention relates to an explosion-proof sealing plate for an organic electrolyte battery, which is composed of a light metal such as lithium as a negative electrode active material.

従来の技術 昨今、ICやLSIをはじめとするエレクトロニクスの進展
はめざましく、これらを応用した電子精密機器の消費電
流は数μＡ程度で極めて微弱な電流しか必要としなくな
ってきている。またこれ等の電源としての一次電池に
も、小型軽量、高エネルギー密度、長期信頼性が求めら
れている。これ等の要件を満たす電池として、金属リチ
ウムまたはリチウム−アルミニウム（Li−Al）合金等の
リチウム系合金を負極活物質として、電解液として非プ
ロトン系高誘電率、低粘度の非水系の電界液を用い、正
極活物質として二酸化マンガン，酸化銅等の金属酸化
物、あるいはフッ化炭素を用いて構成される有機電解質
電池がある。これ等の電池を長期に渡って作動させる場
合、電池設定上においては、長期間に渡って安定した密
閉性，気密性が要求され、極めて気密度の高い封口がな
されている。しかしその反面、万一電池が内部短絡や外
部短絡、あるいは漏れ電流などによる充電がされると、
電池内部にガスが発生し、電池内圧が異常に上昇した場
合、電池が破壊し極めて危険性の高いものであった。従
って従来においては第２図に示すように、電池の封口板
Ｂの中に、肉薄な金属板、合成樹脂、ゴム板からなる薄
板を弁体４として設け、内圧が20〜40kg/cm2に上昇した
時、この弁体４が裂けて電池内のガスを逃がす方法がと
られていた。2. Description of the Related Art In recent years, the progress of electronics such as ICs and LSIs has been remarkable, and the current consumption of electronic precision equipment to which these are applied is about several microamperes, requiring only extremely weak currents. In addition, small size and light weight, high energy density, and long-term reliability are also required for primary batteries as the power source for these. As a battery satisfying these requirements, a lithium-based alloy such as metallic lithium or a lithium-aluminum (Li-Al) alloy is used as a negative electrode active material, and an aprotic high-dielectric constant, low-viscosity non-aqueous electrolytic solution is used as an electrolytic solution. There is an organic electrolyte battery including a metal oxide such as manganese dioxide or copper oxide, or fluorocarbon as a positive electrode active material. When these batteries are operated for a long period of time, stable battery tightness and airtightness are required for a long period of time in terms of battery settings, and a sealing with an extremely high airtightness is performed. However, on the other hand, if the battery is charged due to internal short circuit, external short circuit, or leakage current,
When gas is generated inside the battery and the internal pressure of the battery rises abnormally, the battery breaks, which is extremely dangerous. Therefore, conventionally, as shown in FIG. 2, a thin plate made of a thin metal plate, a synthetic resin, and a rubber plate is provided as the valve body 4 in the sealing plate B of the battery so that the internal pressure is 20 to 40 kg / cm 2 . When rising, the valve body 4 is torn to release the gas in the battery.

発明が解決しようとする問題点 上記の場合にあっては、合成樹脂、ゴム等の弾性体を弁
体として低圧作動性を具体化するには、その肉厚を0.1
〜0.3m/m程度にする必要があり、このような厚みの薄板
材では、大気中の水分、あるいはその他の産業廃棄ガス
等を極めて容易に電池内部へ透過しやすく、特に水分の
存在をきらう有機電解質電池、例えばリチウム電池にお
いては不適当である。また弁体としての作動性を考えた
場合、極めて弾性に富む特徴を有しているため作動圧が
一定しないという欠点があった。一方、水分透過性及び
各種の気体透過性の少ない弁体材料としては金属素材が
考えられるが、20〜40kg/cm2での低圧作動性を考慮する
と、実験的にその厚みとして数十μｍのオーダにする必
要があり、また、コストならびに材料自身の機械的性質
を考慮すると、アルミニウム，鉛，錫等、ビッカース硬
度が100以下の比較的軟かい素材が適当である。しかし
ながらアルミニウム，鉛，錫等の薄板は、他の金属素材
に比べて軟かいため、弾性に富み、弁体としての作動性
を考えた場合、作動圧の安定性にやはり問題があった。Problems to be Solved by the Invention In the above case, in order to realize low pressure operability by using an elastic body such as synthetic resin or rubber as a valve body, its wall thickness is 0.1
It is necessary to set the thickness to approximately 0.3 m / m.Thin sheet materials with such a thickness can easily penetrate moisture in the atmosphere or other industrial waste gases into the battery, and especially avoid the presence of moisture. It is unsuitable for organic electrolyte batteries such as lithium batteries. Further, when considering the operability as a valve body, there is a drawback that the operating pressure is not constant because it has a feature of being extremely elastic. On the other hand, a metal material can be considered as a valve body material having low water permeability and various gas permeability, but in consideration of the low pressure operability at 20 to 40 kg / cm 2 , its thickness is tens of μm experimentally. A relatively soft material having a Vickers hardness of 100 or less, such as aluminum, lead, and tin, is suitable in view of cost and mechanical properties of the material itself. However, since thin plates of aluminum, lead, tin, etc. are softer than other metal materials, they are rich in elasticity, and when considering operability as a valve body, there is still a problem in stability of working pressure.

問題点を解決するための手段 本発明は上記問題点を解決する封口板を提供するもので
あり、前述の金属薄板を、金属薄板の破損圧以下の圧力
でもって、硬さの硬い微粒子を金属薄板の受圧部に衝突
させて、金属薄板の受圧部を他の部分より硬くする方
法、つまりショットピーニングによって加工することを
特徴とする。Means for Solving the Problems The present invention provides a sealing plate that solves the above problems, in which the above-mentioned metal thin plate is treated with a metal having a hardness of fine particles with a pressure not higher than the breaking pressure of the metal thin plate. The method is characterized in that the pressure-receiving portion of the thin plate is made to be harder than other portions by colliding with the pressure-receiving portion of the thin plate, that is, processing is performed by shot peening.

作用 この構成法による封口板を使用することにより、低圧で
しかも安定した作動性を示し、大気中の水分などの電池
内への透過を防止し、電池特性の優れる安全弁装置を提
供できるものである。By using the sealing plate according to this construction method, it is possible to provide a safety valve device that exhibits stable operability at low pressure, prevents moisture in the atmosphere from penetrating into the battery, and has excellent battery characteristics. .

実施例 以下、本発明の実施例を第１図を参照して説明する。Embodiment An embodiment of the present invention will be described below with reference to FIG.

第１図は、本発明の封口板を用いた円筒形リチウム電池
の例を示し、図において、Ａは発電要素群であり、正極
としてはフッ素炭素，二酸化マンガン、酸化銅等を主材
として、これに導電材，結着剤を加えたものからなる。
負極としては、金属リチウムを用い、この正負極を、ポ
リプロピレン不織布や、マイクロポーラスフィルムから
なるセパレータ材を介して渦巻状に構成した極板群であ
る。この極板群に電解液として、1,2−ジメトキシエタ
ン，ジオキソラン，γ−ブチロラクトン等の混合溶媒を
単独か、あるいは混合したものを使用し、溶質としてLi
BF4，LiClO4等を溶解させたものを電解液として含浸さ
せて発電要素を形成している。１は前記極板群の負極活
物質である金属リチウムの集電体リード２をスポット溶
接により溶接した電池容器で、負極端子を兼ねている。
その材質としては0.3mm程度の厚みを有した耐電解液性
ステンレス鋼材、あるいは耐食メッキを施した鉄が用い
られる。Ｂは本発明による弁体４を配した封口板で、そ
の構成法は第３図Ａに示すように、弁孔3aを２段目の水
平部3bの内底面に有した封口板のケース３を用意し、弁
体４をこのケースの１段目の水平部3cに挿入載置する工
程と、ガス排出孔5aを凸状部5bに有し、その周縁部5cを
平坦にしたキャップ５をケース３に嵌合させ、ケース３
の開口折曲縁3dを内方に金型でもってカシメて、弁体４
をケース３の１段目の水平部3cと、キャップ５の周縁平
坦部5cによって圧接固定する工程からなるものである。
弁体の構成としては第４図に示すように厚みが50〜120
μｍ、硬度が100以下、詳しくは50〜80で、受圧部に円
弧状の膨出部4aを設けて受圧面積が常に一定になるよう
に成形加工した金属薄板を、治具ｃでもって固定し、膨
出部4aに前記金属薄板の破損圧以下の圧力、具体的には
５〜7kg/cm2の圧力で硬さが硬く粒径が20〜80μｍの微
粒子、例えば砂，アランダム，カーボランダム，ジルコ
ニア−アルミナ，炭化ケイ素等の微粒子を含んだ圧縮空
気を衝突させる方法、つまり、ショットピーニングによ
って、第４図Ｂに示す如く金属薄板の膨出部4aの硬度を
300〜500となるように加工したものである。ケース３の
材質としては厚みが0.3mm程度の耐食メッキを施した鉄
材、あるいは耐食性特殊ステンレス材よりなる。このケ
ース３の底面には、前記極板群Ａの正極活物質からの集
電リード６がスポット溶接により一体化され、従って封
口板Ｂは正極端子を兼ねる。また封口板Ｂは発電要素Ａ
を組み込んだ電池容器１の開口部1bを低透湿性、耐電解
液性のポリプロピレンからなる絶縁パッキング７を介し
て気密封口している。次に本発明による製造法によって
得られた封口板と、従来の方法で得られた封口板の作動
特性について比較した結果を示す。第５図は、弁体４の
金属薄板として厚みが50,100,及び120μｍ、ビッカース
硬度60のアルミニウム薄板を使用し、第４図Ｂに示す如
く外径10mm,中央膨出部径4.5mm,高さ1.0mm、この部分の
硬度を150,200,300,500とした弁体を製作加工し、封口
板Ｂを構成し、その時の作動圧を測定した結果を示す。
表１は、その時の作動圧の平均値，標準偏差，最大値，
最少値を示したものである。なおテスト数は各々100個
である。あおアルミニウムの厚みを50〜120μｍで検討
したのは50μｍ以下では、ショットピーニング加工する
場合、厚みが薄いため機械的強度が弱くカーボランダム
等の微粒子が衝突する時に破れを生じるからである。逆
に120μｍより暑いものにあっては、破損圧が極めて大
となり低圧作動性の安全弁として不適当であり、厚みが
厚いためショットピーニングの効果が期待できない。ま
たショットピーニングで硬化させる硬度を300〜500で検
討した機は、硬度が300以下では、軟らかすぎるため、
作動圧が一定しないからであり、逆に500以上にあって
は、長時間ショットピーニング処理するため、膨出部に
微細なクラックやピンホールが発生し、弁体の機能を有
しなくなるからである。FIG. 1 shows an example of a cylindrical lithium battery using the sealing plate of the present invention. In the figure, A is a power generation element group, and the positive electrode is mainly made of fluorocarbon, manganese dioxide, copper oxide, etc. It consists of a conductive material and a binder added to this.
Metallic lithium is used as the negative electrode, and this positive and negative electrode is a spirally wound electrode plate group that is formed via a polypropylene nonwoven fabric or a separator material made of a microporous film. As the electrolytic solution, a mixed solvent of 1,2-dimethoxyethane, dioxolane, γ-butyrolactone or the like was used alone or in a mixture in this electrode plate group.
Those dissolved BF 4, LiClO 4, etc. impregnated as an electrolyte solution to form a power generating element. Reference numeral 1 denotes a battery container in which a current collector lead 2 of metallic lithium, which is the negative electrode active material of the electrode plate group, is welded by spot welding and also serves as a negative electrode terminal.
As the material thereof, an electrolytic solution resistant stainless steel material having a thickness of about 0.3 mm or iron plated with corrosion resistance is used. B is a sealing plate on which the valve element 4 according to the present invention is arranged. As shown in FIG. 3A, B is a sealing plate case having a valve hole 3a on the inner bottom surface of the second horizontal portion 3b. And the step of inserting and mounting the valve body 4 in the first horizontal portion 3c of the case, and the cap 5 having the gas discharge hole 5a in the convex portion 5b and flattening the peripheral edge portion 5c thereof. It fits in Case 3, and Case 3
The opening bent edge 3d is swaged inward with a die, and the valve body 4
Is constituted by a step of press-contacting and fixing with the horizontal part 3c of the first stage of the case 3 and the flat peripheral part 5c of the cap 5.
As shown in Fig. 4, the valve body has a thickness of 50-120.
μm, hardness of 100 or less, more specifically 50 to 80, the arc-shaped bulging portion 4a is provided in the pressure receiving portion, and the metal thin plate that is formed so that the pressure receiving area is always constant is fixed with the jig c. , Fine particles having a hardness of 20-80 μm and a hardness of less than the breaking pressure of the thin metal plate in the bulging portion 4a, specifically, a pressure of 5 to 7 kg / cm 2 , such as sand, alundum, carborundum , Zirconia-alumina, silicon carbide and other compressed air containing fine particles, that is, shot peening, the hardness of the bulging portion 4a of the thin metal plate as shown in FIG. 4B.
It was processed to be 300-500. The case 3 is made of a corrosion-resistant plated iron material having a thickness of about 0.3 mm or a corrosion-resistant special stainless steel material. On the bottom surface of the case 3, the current collecting leads 6 from the positive electrode active material of the electrode plate group A are integrated by spot welding, so that the sealing plate B also serves as a positive electrode terminal. Further, the sealing plate B is the power generation element A.
The opening 1b of the battery container 1 in which the above is incorporated is hermetically sealed via an insulating packing 7 made of polypropylene having low moisture permeability and electrolytic solution resistance. Next, the results of comparing the operating characteristics of the sealing plate obtained by the manufacturing method according to the present invention and the sealing plate obtained by the conventional method are shown. Fig. 5 shows that the thin metal plate of the valve body 4 is an aluminum thin plate having a thickness of 50, 100, and 120 µm and a Vickers hardness of 60. As shown in Fig. 4B, the outer diameter is 10 mm, the central bulge diameter is 4.5 mm, and the height is 4.5 mm. A valve body having a hardness of 1.0 mm and a hardness of this portion of 150, 200, 300, 500 was manufactured and processed to form the sealing plate B, and the working pressure at that time was measured.
Table 1 shows the average value, standard deviation, and maximum value of the operating pressure at that time.
It shows the minimum value. The number of tests is 100 each. The reason for studying the thickness of the aluminium in the range of 50 to 120 μm is that when the thickness is 50 μm or less, the mechanical strength is weak when shot peening is performed, and the mechanical strength is weak so that the fine particles such as carborundum are broken. On the other hand, if it is hotter than 120 μm, the breakage pressure becomes extremely large and it is unsuitable as a low-pressure actuated safety valve, and since the thickness is thick, the effect of shot peening cannot be expected. Also, the hardness of 300 to 500, which is hardened by shot peening, is too soft when the hardness is 300 or less.
This is because the operating pressure is not constant, and conversely, when it is 500 or more, shot peening is performed for a long time, so minute cracks and pinholes occur in the bulging portion, and the valve body has no function. is there.

発明の効果 以上、表１より明らかなごとく、本発明による封口板
は、極めてバラツキの少ない安定した動作性を示す。こ
れは、金属薄板が電池内の内圧により負荷が加わった
時、受圧部の硬度が大であるため伸びの現象が吸収さ
れ、電池内圧が金属薄板の硬度の軟かい部分に均一に集
中して極めて安定した圧力で金属薄板の軟かい部分を破
損するためである。また、本発明に用いたショットピー
ニングは厚みの薄い金属材料の表面硬化法に最適であ
り、他の方法、つまり浸炭法，拡散被覆法，高周波焼入
れ法，放電硬化法等では、金属薄板が溶融，破損，変形
などが発生したり、部分的な硬化が不適であったり、装
置的に高価となるなどの欠点があるのに反して、極めて
信頼性の高い、安定した品質のものが安価に提供できる
ものである。 EFFECTS OF THE INVENTION As is clear from Table 1 above, the sealing plate according to the present invention exhibits stable operability with very little variation. This is because when the metal thin plate receives a load due to the internal pressure inside the battery, the hardness of the pressure receiving part is large and the phenomenon of elongation is absorbed, and the battery internal pressure is uniformly concentrated on the soft part of the metal thin plate. This is because the soft part of the thin metal plate is damaged by the extremely stable pressure. Further, the shot peening used in the present invention is most suitable for the surface hardening method of a thin metal material, and in other methods, that is, the carburizing method, the diffusion coating method, the induction hardening method, the discharge hardening method, etc., the metal thin plate is melted. Despite the drawbacks such as breakage, deformation, partial curing not suitable, and expensive equipment, extremely reliable and stable quality is cheaper. Can be provided.

【図面の簡単な説明】[Brief description of drawings]

第１図は本発明の構成による弁体を使用した電池の断面
図、第２図は従来の弁体を使用した電池の断面図、第３
図A,Bは本発明の封口板の構成法を示す断面図、第４図
A,Bは本発明の弁体の加工法，加工形状を示す断面図、
第５図は本発明の弁体、従来の弁体による作動特性を示
す図である。 １……電池容器、2,6……集電体リード、３……ケー
ス、3a……弁体、４……弁体、4a……弁体膨出部、５…
…キャップ、5a……ガス排出孔、７……封口パッキン
グ、Ａ……発電要素、Ｂ……封口板。FIG. 1 is a sectional view of a battery using a valve body according to the constitution of the present invention, FIG. 2 is a sectional view of a battery using a conventional valve body, and FIG.
4A and 4B are cross-sectional views showing a method of constructing the sealing plate of the present invention, FIG.
A and B are sectional views showing the processing method and processing shape of the valve body of the present invention,
FIG. 5 is a diagram showing operating characteristics of the valve body of the present invention and the conventional valve body. 1 ... Battery container, 2,6 ... Current collector lead, 3 ... Case, 3a ... Valve element, 4 ... Valve element, 4a ... Valve element bulging portion, 5 ...
… Cap, 5a… Gas discharge hole, 7… Seal packing, A… Power generation element, B… Seal plate.

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】有機溶媒を電解液として用い電池容器を封
口する封口板のケース内底面に弁孔を有し、かつこの弁
孔を封口板の内側から閉塞する弁体を内蔵した有機電解
質電池であって、上記弁孔を常時閉塞する弁体として、
受圧部分の硬度を他の部分より硬くした金属薄板を用
い、上記弁体はその周縁がガス抜き孔を有するキャップ
と上記封口板のケースとの間にはさまれ、ケースの開口
端部を内方へ折曲げることでカシメ固定されており、前
記受圧部分はキャップの方向に円弧状の膨出部を形成し
ている有機電解質電池。1. An organic electrolyte battery having a valve hole on the inner bottom surface of a case of a sealing plate for sealing a battery container using an organic solvent as an electrolytic solution, and a valve body for closing the valve hole from the inside of the sealing plate. And as a valve body that always closes the valve hole,
A thin metal plate whose pressure receiving portion is harder than the other portions is used.The valve body has its peripheral edge sandwiched between the cap having the gas vent hole and the case of the sealing plate, and the open end of the case is The organic electrolyte battery is fixed by crimping by bending in one direction, and the pressure receiving portion forms an arc-shaped bulging portion in the direction of the cap. 【請求項２】金属薄板は、ビッカース硬度が50〜80、厚
みが50〜120μｍで、受圧部分のビッカース硬度が、300
〜500である特許請求の範囲第１項記載の有機電解質電
池。2. The thin metal plate has a Vickers hardness of 50 to 80, a thickness of 50 to 120 μm, and a Vickers hardness of the pressure receiving portion of 300.
The organic electrolyte battery according to claim 1, which is ˜500.
JP61248648A 1986-10-20 1986-10-20 Organic electrolyte battery Expired - Fee Related JPH0732006B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP61248648A JPH0732006B2 (en) 1986-10-20 1986-10-20 Organic electrolyte battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP61248648A JPH0732006B2 (en) 1986-10-20 1986-10-20 Organic electrolyte battery

Publications (2)

Publication Number Publication Date
JPS63102160A JPS63102160A (en) 1988-05-07
JPH0732006B2 true JPH0732006B2 (en) 1995-04-10

Family

ID=17181247

Family Applications (1)

Application Number Title Priority Date Filing Date
JP61248648A Expired - Fee Related JPH0732006B2 (en) 1986-10-20 1986-10-20 Organic electrolyte battery

Country Status (1)

Country Link
JP (1) JPH0732006B2 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02110171U (en) * 1989-02-20 1990-09-04
CN105190939B (en) * 2013-03-25 2018-04-06 株式会社丰田自动织机 Electrical storage device
JP6107344B2 (en) * 2013-04-05 2017-04-05 株式会社豊田自動織機 Power storage device

Also Published As

Publication number Publication date
JPS63102160A (en) 1988-05-07

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