JP2002008729A - Flat nonaqueous electrolyte secondary battery - Google Patents
Flat nonaqueous electrolyte secondary batteryInfo
- Publication number
- JP2002008729A JP2002008729A JP2000183000A JP2000183000A JP2002008729A JP 2002008729 A JP2002008729 A JP 2002008729A JP 2000183000 A JP2000183000 A JP 2000183000A JP 2000183000 A JP2000183000 A JP 2000183000A JP 2002008729 A JP2002008729 A JP 2002008729A
- Authority
- JP
- Japan
- Prior art keywords
- battery
- negative electrode
- positive electrode
- case
- electrode
- 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.)
- Granted
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Secondary Cells (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は扁平形非水電解質二
次電池に係わり、特に、リード端子溶接時のセパレー
タ、電極の損傷を防止する扁平形非水電解質二次電池に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flat non-aqueous electrolyte secondary battery, and more particularly to a flat non-aqueous electrolyte secondary battery for preventing damage to separators and electrodes during welding of lead terminals.
【０００２】[0002]
【従来の技術】正極作用物質にＭｎＯ2 やＶ2 Ｏ5 など
の金属酸化物、フッ化黒鉛などの無機化合物、あるいは
ポリアニリンやポリアセン構造体などの有機化合物を用
い、負極に金属リチウム、リチウム合金、ポリアセン構
造体などの有機化合物、リチウムを吸蔵・放出可能な炭
素質材料、あるいはチタン酸リチウムやリチウム含有珪
素酸化物のような酸化物を用い、電解質にプロピレンカ
ーボネート、エチレンカーボネート、ブチレンカーボネ
ート、ジエチルカーボネート、ジメチルカーボネート、
メチルエチルカーボネート、ジメトキシエタン、γ−ブ
チロラクトンなどの非水溶媒にＬｉＣｌＯ4 、ＬｉＰＦ
6 、ＬｉＢＦ4 、ＬｉＣＦ3 ＳＯ3 、ＬｉＮ（ＣＦ3 Ｓ
Ｏ2 ）2 、ＬｉＮ（Ｃ2 Ｆ5 ＳＯ2 ）2 などの支持塩を
溶解した非水電解質を用いたコイン形やボタン形の扁平
形非水電解質二次電池は既に商品化されており、放電電
流が数〜数十μＡ程度の軽負荷で放電が行われるＳＲＡ
ＭやＲＴＣのバックアップ用電源や電池交換不要腕時計
の主電源といった用途に適用されている。Metal oxides such as MnO 2 and V 2 O 5 of the Related Art cathode agent, an organic compound such as an inorganic compound such as graphite fluoride, or polyaniline or polyacene structure, metallic lithium negative electrode, a lithium alloy , An organic compound such as a polyacene structure, a carbonaceous material capable of occluding and releasing lithium, or an oxide such as lithium titanate or lithium-containing silicon oxide, and propylene carbonate, ethylene carbonate, butylene carbonate, diethyl ether as an electrolyte. Carbonate, dimethyl carbonate,
LiClO 4 , LiPF in a non-aqueous solvent such as methyl ethyl carbonate, dimethoxyethane, γ-butyrolactone
6 , LiBF 4 , LiCF 3 SO 3 , LiN (CF 3 S
A coin-shaped or button-shaped flat non-aqueous electrolyte secondary battery using a non-aqueous electrolyte in which a supporting salt such as O 2 ) 2 and LiN (C 2 F 5 SO 2 ) 2 is dissolved has already been commercialized. SRA that discharges at a light load with a discharge current of several to several tens μA
It is applied to applications such as a backup power supply for M and RTC and a main power supply for a wristwatch that does not require battery replacement.
【０００３】一方、携帯電話やＰＤＡなどの小型情報端
末を中心に使用機器の小型化が加速しており、主電源で
ある二次電池についても小型化を図ることが要求されて
いる。これに対し、特願平１１−２２４０９６４号や特
願平１１−２４１２９０号に示すような負極端子を兼ね
る金属製の負極ケースと、正極端子を兼ねる金属製の正
極ケースが、絶縁ガスケットを介し嵌合され、さらに前
記正極ケースまたは負極ケースが加締め加工により加締
められた封口構造を有し、その内部に少なくとも正極、
セパレータ、負極を含む発電要素と、非水電解質を内包
した扁平形非水電解質二次電池において、扁平形電池の
扁平面に平行な垂直な方向の断面を見た場合に、少なく
とも３面以上の正極と負極がセパレータを介し対向して
いる正負極対向面を有した電極群が収納され、かつ、電
極群内の正負極対向面積の総和が絶縁ガスケットの開口
面積よりも大きくしている扁平形非水電解質二次電池が
小型化の要求を満たす電池として提案されている。On the other hand, the miniaturization of equipment used has been accelerated, especially for small information terminals such as mobile phones and PDAs, and there is a demand for miniaturization of secondary batteries as a main power supply. On the other hand, a metal negative electrode case also serving as a negative electrode terminal and a metal positive electrode case also serving as a positive electrode terminal as shown in Japanese Patent Application Nos. 11-2240964 and 11-241290 are fitted via an insulating gasket. The positive electrode case or the negative electrode case further has a sealing structure crimped by crimping, at least the positive electrode inside,
In a flat nonaqueous electrolyte secondary battery including a separator and a negative electrode, and a nonaqueous electrolyte, when viewed in a cross section in a direction perpendicular to the flat surface of the flat battery, at least three or more surfaces A flat type in which an electrode group having a positive / negative electrode facing surface in which a positive electrode and a negative electrode face each other via a separator is housed, and the sum of the positive / negative electrode facing areas in the electrode group is larger than the opening area of the insulating gasket. Non-aqueous electrolyte secondary batteries have been proposed as batteries that satisfy the demand for miniaturization.
【０００４】しかしながら、これらの扁平形非水電解質
二次電池を機器に組み込む場合、その多くは正極、負極
ケースの外側にリード端子を抵抗溶接にて溶接し、端子
部と機器とをはんだ付けして組み込むのが一般である。
前述したように正極、負極、セパレータからなる電極層
の厚さが１．０ｍｍ以下である電極群を積層もしくは捲
回し、電池内に内包する扁平形非水電解質二次電池で
は、一枚の電極の厚さが１ｍｍ以下の薄い正負極電極と
０．５ｍｍ以下のポリエチレン、ポリプロピレン製など
の薄膜セパレータを介して積層または捲回された電極群
を直接、正極及び負極ケースに接触させている。However, when these flat non-aqueous electrolyte secondary batteries are incorporated in equipment, most of them are formed by welding lead terminals to the outside of the positive and negative electrode cases by resistance welding, and soldering the terminal portion and the equipment. It is common to incorporate.
As described above, a flat non-aqueous electrolyte secondary battery in which the electrode group including the positive electrode, the negative electrode, and the electrode layer including the separator has a thickness of 1.0 mm or less is laminated or wound, and is included in the battery, has one electrode. The electrode group laminated or wound via a thin positive / negative electrode having a thickness of 1 mm or less and a thin film separator made of polyethylene or polypropylene having a thickness of 0.5 mm or less is directly contacted with the positive electrode and the negative electrode case.
【０００５】このような電池系において抵抗溶接を行う
ために、電池ケースに５００Ｖ程度の電圧を印加した場
合、溶接時に発生する熱が電池ケースを通じて電極、セ
パレータにまで到達してしまい、セパレータの穴あきや
収縮を起こし、容量劣化や電池内ショートを起こす。ま
た、溶接部分に電圧が集中するため溶接部分に通じる電
極が集電体から剥げ落ちるなどの不具合が生じ、電池と
しての機能の低下を引き起こす。また、溶接時の出力を
下げた場合、上記のような不具合は起こらなくなるが、
溶接強度が弱くなるため、リード端子が取れたり、電池
とリード端子の接触が悪くなってしまうという不具合が
ある。また、リード端子の溶接方法をレーザー溶接など
に変更しても熱の発生は抑えられず、同様の不具合を招
く恐れがある。In order to perform resistance welding in such a battery system, when a voltage of about 500 V is applied to the battery case, heat generated during welding reaches the electrodes and the separator through the battery case, and the holes in the separator are opened. It causes vacancy and shrinkage, causing capacity deterioration and short circuit in the battery. In addition, since the voltage is concentrated on the welded portion, a problem such as the electrode leading to the welded portion peeling off from the current collector occurs, and the function as a battery is reduced. In addition, when the output during welding is reduced, the above-mentioned problems do not occur,
Since the welding strength is weak, there is a problem that the lead terminal is removed or the contact between the battery and the lead terminal is deteriorated. Further, even if the welding method of the lead terminals is changed to laser welding or the like, the generation of heat cannot be suppressed, and the same problem may be caused.
【０００６】[0006]
【発明が解決しようとする課題】本発明者らは上記状況
に鑑みてなされたもので、その目的はリード端子溶接に
より発生する熱の集中を分散させ、電池ケース内の電
極、セパレータの破壊を抑制し、容量劣化や電池内ショ
ートを防止する扁平形非水電解質二次電池を提供するこ
とにある。DISCLOSURE OF THE INVENTION The present inventors have made in view of the above-mentioned circumstances, an object of the present invention is to disperse the concentration of heat generated by lead terminal welding and to prevent the electrodes and separators in a battery case from being broken. An object of the present invention is to provide a flat non-aqueous electrolyte secondary battery that suppresses capacity deterioration and short-circuit in the battery.
【０００７】[0007]
【課題を解決するための手段】本発明者らは鋭意研究を
重ねた結果、扁平形非水電解質二次電池において、正極
及び負極ケースと電極群との間に、金属ネットを設ける
ことにより、前記正極及び負極ケースに電池外部からリ
ード端子を溶接するときに発生する熱の集中を分散さ
せ、電池ケース内の電極及びセパレータの破壊を抑制で
きることを見出した。Means for Solving the Problems As a result of intensive studies, the present inventors have found that in a flat nonaqueous electrolyte secondary battery, a metal net is provided between a positive electrode and a negative electrode case and an electrode group. It has been found that the concentration of heat generated when the lead terminals are welded to the positive and negative electrode cases from the outside of the battery can be dispersed, and the destruction of the electrodes and the separator in the battery case can be suppressed.
【０００８】すなわち、負極端子を兼ねる金属製の負極
ケースと、正極端子を兼ねる金属製の正極ケースが、絶
縁ガスケットを介し嵌合され、さらに前記正極ケースま
たは負極ケースが加締め加工により加締められた封口構
造を有し、その内部に少なくとも正極、負極、シャット
ダウン機能のある薄膜セパレータを合わせた電極群と、
非水電解質とを収納した扁平形非水電解質二次電池にお
いて、該正極または負極ケースと電極群との間に、金属
ネットを設けることにより、リード端子溶接時により発
生する熱の集中を分散させ、かつ電池ケースと電極群の
距離を離すことで、電池内の電極やセパレータの破壊を
抑制できることを見出した。That is, a metal negative electrode case also serving as a negative electrode terminal and a metal positive electrode case also serving as a positive electrode terminal are fitted through an insulating gasket, and the positive electrode case or the negative electrode case is caulked by caulking. Having a closed structure, at least a positive electrode, a negative electrode, an electrode group including a thin film separator having a shutdown function therein,
In a flat non-aqueous electrolyte secondary battery containing a non-aqueous electrolyte, a metal net is provided between the positive electrode or negative electrode case and the electrode group to disperse the concentration of heat generated during lead terminal welding. In addition, it has been found that by increasing the distance between the battery case and the electrode group, destruction of the electrodes and the separator in the battery can be suppressed.
【０００９】以下、本発明者らが本発明の扁平形非水電
解質二次電池（以下単に電池と称する）を如何にして実
現したかを説明する。リード端子溶接時に発生する熱の
集中を分散させるには電池ケース外部と電極群との距離
を離すことが有効である。これには電池ケースと電極群
との間に、導電性のある材料を挿入することで実現され
る。特に熱伝導を抑制するために金属ネットを用いるこ
とが好ましい。The following describes how the present inventors have realized the flat nonaqueous electrolyte secondary battery of the present invention (hereinafter simply referred to as battery). To disperse the concentration of heat generated during lead terminal welding, it is effective to increase the distance between the outside of the battery case and the electrode group. This is realized by inserting a conductive material between the battery case and the electrode group. In particular, it is preferable to use a metal net in order to suppress heat conduction.
【００１０】金属ネットの形状は、電池ケースとの間に
空隙が得られ、空隙内に電解液を取り込めるものが良
い。金属ネットとしては金網、エキスパンドメタル、パ
ンチドメタル、発泡体などが挙げられる。空隙内の電解
液は、熱や電圧の集中を起き難くさせる作用がある。ま
た、集電体の形や開口度には特に規制はない。The shape of the metal net is preferably such that a gap is obtained between the metal net and the battery case, and the electrolyte can be taken into the gap. Examples of the metal net include a wire net, an expanded metal, a punched metal, and a foam. The electrolyte in the gap has an effect of making it difficult for heat and voltage to concentrate. There are no particular restrictions on the shape or aperture of the current collector.
【００１１】また、金属ネットの厚さは缶の厚さを足し
た厚さが問題になるが、その厚さが薄いと熱の集中を分
散させる効果が薄くなり目的が達せられない。逆に、そ
の厚さが厚いと熱の集中を分散させるのは可能である
が、電池内に組み込まれる電極が多く取り込めなくな
り、電池容量の低下につながる。これらを考慮して正極
または負極ケースと金属ネットの合計の厚さは０．３０
ｍｍ以上０．４５ｍｍ以下が適切である。[0011] The thickness of the metal net is a problem in which the thickness of the can is added, but if the thickness is small, the effect of dispersing the concentration of heat is reduced and the object cannot be achieved. Conversely, if the thickness is large, it is possible to disperse the concentration of heat, but it is impossible to take in many electrodes incorporated in the battery, leading to a reduction in battery capacity. Considering these, the total thickness of the positive or negative electrode case and the metal net is 0.30
It is appropriate that the thickness is equal to or more than 0.45 mm.
【００１２】また、金属ネットはあらかじめ、電池ケー
スの内面に溶接すると密着性が向上し、優れた導電が得
られるのでよい。金属ネットの材料に関してはいかなる
ものでも可能であるが、金属酸化物等の高電位を有する
作用物質を正極に用いた場合、正極作用物質より卑な溶
解電位を持つ金属ネットを用いると、電池保存中に高電
位のために劣化が起こり電池の性能に影響を及ぼす。こ
のため、正極側の金属ネットはアルミニウムやチタン、
またはクロム、モリブデンを多く含むようなステンレス
鋼がよい。負極側の金属ネットに関しては正極よりも電
位がかなり卑であるため、正極ほど耐食性に配慮する必
要はなく、ステンレス鋼やニッケル、銅などがあげられ
る。また電極群と金属ネットとの接触抵抗を下げるため
に金属ネットの表面に導電性塗料を塗布することが好ま
しい。Further, if the metal net is welded in advance to the inner surface of the battery case, the adhesion is improved and excellent conductivity can be obtained. Any material can be used for the material of the metal net. However, when an active substance having a high potential such as a metal oxide is used for the positive electrode, if a metal net having a dissolution potential lower than that of the positive electrode active substance is used, the battery can be stored. Degradation occurs due to the high potential during the operation, which affects battery performance. For this reason, the metal net on the positive electrode side is aluminum, titanium,
Alternatively, stainless steel containing a large amount of chromium and molybdenum is preferable. Since the potential of the metal net on the negative electrode side is considerably lower than that of the positive electrode, it is not necessary to consider corrosion resistance as much as the positive electrode, and examples thereof include stainless steel, nickel, and copper. It is preferable to apply a conductive paint to the surface of the metal net in order to reduce the contact resistance between the electrode group and the metal net.
【００１３】本発明の電池は電極を含めた電池の構造に
主点をおいたものであり、正極作用物質は特に限定され
るものではない。すなわち、ＭｎＯ2 、Ｖ2 Ｏ5 、Ｎｂ
2 Ｏ 5 、ＬｉＴｉ2 Ｏ4 、ＬｉＴｉ5 Ｏ12、ＬｉＦｅ2
Ｏ4 、コバルト酸リチウム、ニッケル酸リチウム、マン
ガン酸リチウムなどの金属酸化物、あるいはフッ化黒
鉛、ＦｅＳ2 などの無機化合物、あるいはポリアニリン
やポリアセン構造体などの有機化合物などあらゆる物が
適用可能である。ただし、この中で作動電位が高く、サ
イクル特性に優れるという点でコバルト酸リチウム、ニ
ッケル酸リチウム、マンガン酸リチウムやそれらの混合
物やそれらの元素の一部を他の金属元素で置換したリチ
ウム含有酸化物がより好ましく、長期間に亘り使用され
ることもある扁平形非水電解質二次電池においては、高
容量で電解液や水分との反応性が低く化学的に安定であ
るという点でコバルト酸リチウムがさらに好ましい。The battery of the present invention has a battery structure including electrodes.
The main point is that the positive electrode active substance is particularly limited.
Not something. That is, MnOTwo, VTwoOFive, Nb
TwoO Five, LiTiTwoOFour, LiTiFiveO12, LiFeTwo
OFour, Lithium cobaltate, lithium nickelate, man
Metal oxides such as lithium ganate, or fluorinated black
Lead, FeSTwoSuch as inorganic compounds, or polyaniline
And all kinds of organic compounds such as polyacene structures
Applicable. However, the operating potential is high and the
Lithium cobalt oxide, nickel
Lithium ckerlate, lithium manganate and mixtures thereof
Objects and some of those elements are replaced with other metal elements
Oxides are more preferred and are used for extended periods of time.
Flat non-aqueous electrolyte secondary batteries
Low capacity and low reactivity with electrolyte and moisture
Lithium cobaltate is more preferable in that respect.
【００１４】また、本発明の電池の負極については特に
限定されるものではなく、金属リチウム、あるいはＬｉ
−Ａｌ、Ｌｉ−Ｉｎ、Ｌｉ−Ｓｉ、Ｌｉ−Ｇｅ、Ｌｉ−
Ｂｉ、Ｌｉ−Ｐｂなどのリチウム合金、あるいはＮｂ2
Ｏ5 、ＬｉＴｉ2 Ｏ4 、Ｌｉ 4 Ｔｉ5 Ｏ12やＬｉ含有珪
素酸化物のような酸化物などあらゆる物が適用可能であ
るが、サイクル特性に優れ、作動電位が低く、高容量で
あるという点でＬｉを吸蔵、放出可能な炭素質材料が好
ましく、特に放電末期においても電池作動電圧の低下が
少ないという点で天然黒鉛や人造黒鉛、膨張黒鉛、メソ
フェーズピッチ焼成体、メソフェーズピッチ繊維焼成体
などのｄ002 の面間隔が０．３３８ｎｍ以下の黒鉛構造
が発達した炭素質材料が好ましい。The negative electrode of the battery of the present invention is particularly
Without limitation, metallic lithium or Li
-Al, Li-In, Li-Si, Li-Ge, Li-
Bi, Li-Pb or other lithium alloy, or NbTwo
OFive, LiTiTwoOFour, Li FourTiFiveO12And Li-containing silicon
Any material such as oxides such as oxides can be applied.
High cycle capacity, low operating potential, high capacity
Carbonaceous materials that can store and release Li
Particularly, even at the end of discharge, the operating voltage of the battery
Natural graphite, artificial graphite, expanded graphite, meso
Phase pitch fired body, meso phase pitch fiber fired body
D002Graphite structure with plane spacing of 0.338nm or less
Is preferred.
【００１５】次に、本発明の電池の電極については、正
負極とも従来の顆粒合剤の成形方式や金属ネットの金属
基盤に合剤を充填する方法を用いてもよいが、肉薄電極
の作製が行い易いという点で金属箔にスラリー状の合剤
を塗布、乾燥したものがよく、さらにそれを圧延したも
のも用いることもできる。また、前記のような金属箔に
作用物質を含む合剤層を塗工した電極を用いる場合、電
極群の内部に用いる電極は金属箔の両面に作用物質層を
形成したものを用いるのが容積効率の上から好ましく、
電極群の両端の金属ネットに接触する電極構成材露出部
については接触抵抗を低減させるために電極構成材の
内、特に金属箔を露出させるのが好ましい。これに関し
て、この部分に限り片面にのみ作用物質層を形成した電
極を用いてもよいし、一旦、両面に作用物質層を形成し
た後、片面のみ作用物質層を除去してもよい。Next, as for the electrodes of the battery of the present invention, for the positive and negative electrodes, a conventional method of molding a granular mixture or a method of filling the metallic base of a metal net with the mixture may be used. It is preferable that a slurry-like mixture is applied to a metal foil and dried, and a rolled version of the mixture can also be used in that it is easy to perform. In addition, when using an electrode in which a mixture layer containing an active substance is applied to a metal foil as described above, the electrode used inside the electrode group is formed by forming an active substance layer on both sides of the metal foil. Preferred for efficiency,
It is preferable to expose the metal foil, particularly the metal foil, of the electrode component material in order to reduce the contact resistance with respect to the electrode component material exposed portions that come into contact with the metal nets at both ends of the electrode group. In this regard, an electrode having an active substance layer formed only on one side may be used only for this portion, or the active substance layer may be formed on both sides, and then the active substance layer may be removed only on one side.
【００１６】また、電池に溶接するリード端子の材料に
ついては、導電性の得られるものであればいずれのもの
でも良いが、その汎用性等からステンレス製のものが好
ましい。また、端子の厚さ、形においても特に限定され
るものではない。The material for the lead terminal to be welded to the battery may be any material as long as it can provide conductivity, but stainless steel is preferred from the viewpoint of versatility and the like. Also, the thickness and shape of the terminal are not particularly limited.
【００１７】[0017]
【発明の実施の形態】以下、本発明の実施例及び比較例
について詳細に説明する。 （実施例１）図１は本発明の実施例１の扁平形非水電解
質二次電池の断面図である。図において、本実施例１の
扁平形非水電解質二次電池の電池ケースは、ステンレス
製の金属ネット２が内面に溶接されたステンレス製の正
極ケース１に、金属ネット６を内面に溶接し、絶縁ガス
ケット７を一体化した負極ケース５を嵌合しており、こ
の電池ケース内には正極作用物質含有層３と負極作用物
質含有層４の間にポリエチレン微多孔膜からなるセパレ
ータ８を介し渦巻状に捲回された発電要素が収納されて
いる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, examples and comparative examples of the present invention will be described in detail. Embodiment 1 FIG. 1 is a sectional view of a flat nonaqueous electrolyte secondary battery according to Embodiment 1 of the present invention. In the figure, the battery case of the flat nonaqueous electrolyte secondary battery of Example 1 has a stainless steel positive electrode case 1 in which a stainless steel metal net 2 is welded to the inner surface, and a metal net 6 welded to the inner surface. A negative electrode case 5 in which an insulating gasket 7 is integrated is fitted, and inside this battery case, a spiral is formed between the positive electrode active material containing layer 3 and the negative electrode active material containing layer 4 via a separator 8 made of a polyethylene microporous film. The power generation element wound in a shape is stored.
【００１８】次に、本実施例１の扁平形非水電解質二次
電池の製造方法を説明する。まず、ＬｉＣｏＯ2 １００
質量部に対し導電材としてアセチレンブラック５質量部
と黒鉛粉末５質量部を加え、結着剤としてポリフッ化ビ
ニリデンを５質量部加え、Ｎ−メチルピロリドンで希
釈、混合し、スラリー状の正極合剤を得た。この正極合
剤を、正極集電体である厚さ０．０２ｍｍのアルミ箔の
片面にドクターブレード法により塗工、乾燥を行い、ア
ルミ箔表面に正極作用物質含有層３を形成した。以後、
正極作用物質含有層３の塗膜厚さが両面で０．１５ｍｍ
となるまで塗工、乾燥を繰り返し、両面塗工正極を作製
した。次に、この電極体の片面の端から１０ｍｍ部分の
作用物質含有層を除去し、アルミ層を剥き出し通電部と
し、幅１５ｍｍ、長さ１２０ｍｍ、厚さ０．１５ｍｍに
切り出した正極板を作製した。Next, a method of manufacturing the flat nonaqueous electrolyte secondary battery of the first embodiment will be described. First, LiCoO 2 100
5 parts by mass of acetylene black and 5 parts by mass of graphite powder as a conductive material are added to 5 parts by mass, and 5 parts by mass of polyvinylidene fluoride are added as a binder, and the mixture is diluted and mixed with N-methylpyrrolidone. Got. This positive electrode mixture was applied to one surface of a 0.02 mm thick aluminum foil as a positive electrode current collector by a doctor blade method and dried to form a positive electrode active substance containing layer 3 on the aluminum foil surface. Since then
The coating thickness of the positive electrode active substance containing layer 3 is 0.15 mm on both sides.
Coating and drying were repeated until a positive electrode was prepared. Next, a positive electrode plate cut out to a width of 15 mm, a length of 120 mm and a thickness of 0.15 mm was prepared by removing the active substance-containing layer of 10 mm from one end of the electrode body and exposing the aluminum layer to serve as a current-carrying part. .
【００１９】次に、黒鉛化メソフェーズピッチ炭素繊維
粉末１００質量部に、結着剤としてスチレンブタジエン
ゴム（ＳＢＲ）とカルボキシメチルセルロース（ＣＭ
Ｃ）をそれぞれ２．５質量部を添加し、イオン交換水で
希釈、混合し、スラリー状の負極合剤を得た。得られた
負極合剤を負極集電体である厚さ０．０２ｍｍの銅箔に
負極作用物質含有層４の厚さが０．１５ｍｍとなるよう
に正極の場合と同様に塗工、乾燥を繰り返し実施し両面
塗工負極を作製した。この電極体の片面の端から１０ｍ
ｍ部分の作用物質含有層を除去し、銅層を剥き出し通電
部とし、幅１５ｍｍ、長さ１２０ｍｍ、厚さ０．１５ｍ
ｍに切り出した負極板を作製した。Next, styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CM) were used as binders in 100 parts by mass of the graphitized mesophase pitch carbon fiber powder.
C) was added in an amount of 2.5 parts by mass, respectively, and diluted and mixed with ion-exchanged water to obtain a slurry-like negative electrode mixture. The obtained negative electrode mixture is applied and dried on a 0.02 mm thick copper foil as a negative electrode current collector in the same manner as in the case of the positive electrode so that the thickness of the negative electrode active material containing layer 4 becomes 0.15 mm. This was repeatedly performed to produce a double-sided coated negative electrode. 10 m from one side edge of this electrode body
m part of the active substance-containing layer is removed, and the copper layer is exposed to serve as a current-carrying part. The width is 15 mm, the length is 120 mm, and the thickness is 0.15 m.
The negative electrode plate cut into m was prepared.
【００２０】次に、正負極通電部面を外周巻き終わり側
とし、これら正極と負極の間に厚さ２５μｍのポリエチ
レン微多孔膜からなるセパレータ８を介し渦巻状に捲回
し、扁平形電池の扁平面に対し水平方向に正負極対向部
を持つように一定方向に捲回電極の中心部の空間がなく
なるまで加圧した。Next, the positive / negative electrode conducting surface is set to the outer peripheral winding end side, and spirally wound between the positive electrode and the negative electrode with a separator 8 made of a 25 μm-thick polyethylene microporous film interposed therebetween to form a flat battery. Pressure was applied in a fixed direction so that the space at the center of the wound electrode was exhausted so as to have the positive and negative electrode facing portions in the horizontal direction with respect to the surface.
【００２１】作製した電極群を８５℃で１２時間乾燥し
た後、厚さ０．０３ｍｍのステンレス製の金属ネット６
を内面に溶接した、絶縁ガスケット７を一体化した負極
金属ケース５の内底面に電極群の片面塗工負極板の未塗
工側が金属ネットに接するように配置し、エチレンカー
ボネートとメチルエチルカーボネートを体積比１：１の
割合で混合した溶媒に支持塩としてＬｉＰｆ6 を１ｍｏ
ｌ／ｌの割合で溶解せしめた非水電解質を注液し、さら
に電極群の片面塗工正極板の未塗工側に接するように厚
さ０．０３ｍｍのステンレス製の金属ネット２が内面に
溶接されたステンレス製の正極ケース１を嵌合し、上下
反転後、正極ケースに加締め加工を実施し、封口し、厚
さ３ｍｍ、直径φ２４．５ｍｍの実施例１の扁平形非水
電解質二次電池を製作した。正極及び負極ケースの厚さ
と該金属ネットの厚さの合計はそれぞれ０．２８ｍｍで
ある。After drying the produced electrode group at 85 ° C. for 12 hours, a 0.03 mm-thick stainless steel metal net 6 was formed.
Is disposed on the inner bottom surface of the negative electrode metal case 5 in which the insulating gasket 7 is integrated so that the uncoated side of the single-side coated negative electrode plate of the electrode group is in contact with the metal net, and ethylene carbonate and methyl ethyl carbonate are welded. LiPf 6 was added as a supporting salt in a solvent mixed at a volume ratio of 1: 1 with 1 mol of LiPf 6 .
A non-aqueous electrolyte dissolved at a ratio of 1 / l was injected, and a metal net 2 made of stainless steel having a thickness of 0.03 mm was formed on the inner surface so as to be in contact with the uncoated side of the single-side coated positive electrode plate of the electrode group. The welded stainless steel positive electrode case 1 was fitted, turned upside down, then crimped to the positive electrode case, sealed, and closed to obtain a flat nonaqueous electrolyte 2 of Example 1 having a thickness of 3 mm and a diameter of 24.5 mm. The next battery was manufactured. The sum of the thicknesses of the positive and negative electrode cases and the metal net is 0.28 mm, respectively.
【００２２】（実施例２）厚さが０．０５ｍｍの金属ネ
ットを正極及び負極ケースの内面に溶接し、正極及び負
極ケースの厚さと該金属ネットの厚さの合計がそれぞれ
０．３０ｍｍである以外は実施例１と同様に電池を作製
した。Example 2 A metal net having a thickness of 0.05 mm was welded to the inner surfaces of a positive electrode and a negative electrode case, and the total thickness of the positive and negative electrode cases and the thickness of the metal net was 0.30 mm each. A battery was fabricated in the same manner as in Example 1 except for the above.
【００２３】（実施例３）正極及び負極の作用物質含有
層の厚さを０．１４ｍｍとし、厚さが０．１０ｍｍの金
属ネットを正極及び負極ケースの内面に溶接し、正極及
び負極ケースの厚さと該金属ネットの厚さの合計がそれ
ぞれ０．３５ｍｍである以外は実施例１と同様に電池を
作製した。Example 3 The thickness of the active substance-containing layers of the positive electrode and the negative electrode was set to 0.14 mm, and a metal net having a thickness of 0.10 mm was welded to the inner surfaces of the positive electrode and the negative electrode case. A battery was produced in the same manner as in Example 1, except that the total of the thickness and the thickness of the metal net was 0.35 mm, respectively.
【００２４】（実施例４）正極及び負極の作用物質含有
層の厚さを０．１３ｍｍとし、厚さが０．１５ｍｍの金
属ネットを正極及び負極ケースの内面に溶接し、正極及
び負極ケースの厚さと該金属ネットの厚さの合計がそれ
ぞれ０．４０ｍｍである以外は実施例１と同様に電池を
作製した。(Example 4) The thickness of the active substance-containing layers of the positive electrode and the negative electrode was set to 0.13 mm, and a metal net having a thickness of 0.15 mm was welded to the inner surfaces of the positive electrode and the negative electrode case. A battery was produced in the same manner as in Example 1, except that the total of the thickness and the thickness of the metal net was 0.40 mm.
【００２５】（実施例５）正極及び負極の作用物質含有
層の厚さを０．１２ｍｍとし、厚さが０．２０ｍｍの金
属ネットを正極及び負極ケースの内面に溶接し、正極及
び負極ケースの厚さと該金属ネットの厚さの合計がそれ
ぞれ０．４５ｍｍである以外は実施例１と同様に電池を
作製した。Example 5 The thickness of the active substance-containing layers of the positive electrode and the negative electrode was set to 0.12 mm, and a metal net having a thickness of 0.20 mm was welded to the inner surfaces of the positive electrode and the negative electrode case. A battery was produced in the same manner as in Example 1, except that the total of the thickness and the thickness of the metal net was 0.45 mm, respectively.
【００２６】（実施例６）正極及び負極の作用物質含有
層の厚さを０．１０ｍｍとし、厚さが０．３０ｍｍの金
属ネットを正極及び負極ケースの内面に溶接し、正極及
び負極ケースの厚さと該金属ネットの厚さの合計がそれ
ぞれ０．５５ｍｍである以外は実施例１と同様に電池を
作製した。Example 6 The thickness of the active substance-containing layers of the positive electrode and the negative electrode was set to 0.10 mm, and a metal net having a thickness of 0.30 mm was welded to the inner surfaces of the positive electrode and the negative electrode case. A battery was manufactured in the same manner as in Example 1, except that the total of the thickness and the thickness of the metal net was 0.55 mm, respectively.
【００２７】（比較例１）金属ネットを用いず、厚さが
０．２５ｍｍの電池ケースの内面に導電性塗料を塗布し
た正極及び負極ケースを用いた以外は実施例１と同様に
電池を作製した。以上の通り作製した本実施例および比
較例の電池３００個の正極、負極両電池ケースに厚さ
０．２ｍｍのステンレス製のリード端子を４８０±１０
Ｖの溶接出力で抵抗溶接を行った。これらの電池をラン
ダムに５０個抜き取り、電池を分解し、正負極側のセパ
レータの穴あき、収縮、及び電極の剥げ落ち具合を観察
した。また、これらの電池において、４．２Ｖ、３ｍＡ
の定電流定電圧で４８時間初充電を実施し、３日間室温
で放置後、開路電圧を測定した。その後、３日後の開路
電圧が４．０Ｖ以上であった電池を１ｍＡの定電流で
３．０Ｖまで放電を実施し放電容量を求めた。Comparative Example 1 A battery was manufactured in the same manner as in Example 1 except that a metal net was not used, and a positive electrode and a negative electrode case each having a 0.25 mm thick battery case coated with a conductive paint were used. did. A stainless-steel lead terminal having a thickness of 0.2 mm was attached to the positive and negative battery cases of 300 batteries of the present example and the comparative example manufactured as described above.
Resistance welding was performed with a welding power of V. Fifty of these batteries were randomly taken out, the batteries were disassembled, and the holes on the positive and negative electrode side separators, shrinkage, and peeling of the electrodes were observed. In these batteries, 4.2 V, 3 mA
The battery was initially charged at a constant current and constant voltage of 48 hours, left at room temperature for 3 days, and then the open circuit voltage was measured. Thereafter, the battery having an open circuit voltage of 4.0 V or more after 3 days was discharged to 3.0 V at a constant current of 1 mA to obtain a discharge capacity.
【００２８】正負極側のセパレータの穴あき、収縮、及
び電極の剥げ落ち発生率を表１に示した。また、初充電
後、電池を３日間放置後の開路電圧と、その後、３日後
の開路電圧が４．０Ｖ以上であった電池の放電容量の平
均値を表２に示した。Table 1 shows the rate of occurrence of holes, shrinkage, and peeling of the electrodes of the separators on the positive and negative electrode sides. In addition, Table 2 shows the average open circuit voltage of the battery after the battery was left for 3 days after the initial charge and the average discharge capacity of the battery whose open circuit voltage after 3 days was 4.0 V or more.
【００２９】表より明らかであるが本発明の各実施例の
電池は、比較例１の電池に比べて電池にリード端子を抵
抗溶接した後の正負極側のセパレータの穴あき、収縮、
及び電極の剥げ落ちが大幅に改善されており、電池のシ
ョートも改善されている。なお、正極ケース及び負極ケ
ースの厚さと該金属ネットの厚さの合計がそれぞれ０．
３０ｍｍ以上である実施例に関しては、電池に比べて電
池にリード端子を抵抗溶接した後の正負極側のセパレー
タ穴あき、収縮、及び電極の剥げ落ちが見られない。実
施例１の電池は、抵抗溶接後の正極、負極側のセパレー
タの収縮が若干みられたが、電池内での内部短絡が起こ
る程のものではない。実施例２、３、４、５の電池にお
いては金属ネットの厚さが最適であるため電池内に電極
を多く詰め込め、高容量の電池が得られる。このため、
正極及び負極ケースの厚さと該金属ネットの厚さの合計
が０．３０ｍｍ以上０．４５ｍｍ以下のものが更によ
い。As is clear from the table, the batteries of the examples of the present invention are different from the batteries of Comparative Example 1 in that the separators on the positive and negative electrode sides after the lead terminals are resistance-welded to the battery, shrinkage and shrinkage.
In addition, the peeling of the electrode has been greatly improved, and the short circuit of the battery has also been improved. In addition, the total of the thickness of the positive electrode case and the negative electrode case and the thickness of the metal net is each 0.1.
With respect to the examples having a length of 30 mm or more, the separator holes on the positive and negative electrodes after the lead terminals were resistance-welded to the battery, shrinkage, and peeling of the electrodes were not observed as compared with the battery. In the battery of Example 1, although the separators on the positive electrode and the negative electrode side after the resistance welding slightly shrink, the internal short circuit in the battery is not so large. In the batteries of Examples 2, 3, 4, and 5, the thickness of the metal net is optimal, so that many electrodes are packed in the battery, and a high-capacity battery can be obtained. For this reason,
It is more preferable that the sum of the thickness of the positive and negative electrode cases and the thickness of the metal net is 0.30 mm or more and 0.45 mm or less.
【００３０】[0030]
【表１】 [Table 1]
【００３１】[0031]
【表２】 [Table 2]
【００３２】なお、本発明の実施例は、非水電解質に非
水溶媒を用いた扁平形非水溶媒二次電池を用いて説明
し、また電池形状については正極ケースの加締め加工に
より封口するコイン形非水電解質をもとに説明したが、
正負極電極を入れ替え、負極ケースの加締め加工により
封口することも可能である。さらに、電池形状について
も円形のコイン形である必要はなく小判形などの特殊形
状を有する扁平形非水電解質二次電池においても適用可
能である。The embodiment of the present invention will be described using a flat non-aqueous solvent secondary battery using a non-aqueous solvent for the non-aqueous electrolyte, and the shape of the battery is sealed by caulking the positive electrode case. Although explained based on the coin-shaped non-aqueous electrolyte,
It is also possible to replace the positive and negative electrodes and seal the negative electrode case by crimping. Further, the shape of the battery does not need to be a circular coin shape, and can be applied to a flat nonaqueous electrolyte secondary battery having a special shape such as an oval shape.
【００３３】[0033]
【発明の効果】以上説明したとおり、本発明によれば、
電池の高容量を維持したまま、電池にリード端子を抵抗
溶接した後の正負極側のセパレータの穴あき、収縮、及
び電極の剥げ落ちの不具合を解消できるので、工業的価
値の非常に優れた扁平形非水電解質二次電池を提供する
ことができる。As described above, according to the present invention,
While maintaining the high capacity of the battery, it is possible to eliminate the problems of perforation, shrinkage, and electrode peeling of the separator on the positive and negative electrodes after resistance welding of the lead terminals to the battery, which is extremely excellent in industrial value. A flat nonaqueous electrolyte secondary battery can be provided.
【図１】本発明の実施例１の電池の断面図。FIG. 1 is a sectional view of a battery according to a first embodiment of the present invention.
１…正極ケース、２…金属ネット（正極側）、３…正極
作用物質含有層、４…負極作用物質含有層、５…負極ケ
ース、６…金属ネット（負極側）、７…絶縁ガスケッ
ト、８…セパレータ。DESCRIPTION OF SYMBOLS 1 ... Positive electrode case, 2 ... Metal net (positive electrode side), 3 ... Positive electrode active substance containing layer, 4 ... Negative electrode active substance containing layer, 5 ... Negative electrode case, 6 ... Metal net (negative electrode side), 7 ... Insulating gasket, 8 ... separator.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 宇田川 和男 東京都品川区南品川三丁目４番10号 東芝 電池株式会社内 Ｆターム(参考） 5H017 AA03 AS02 CC05 HH03 HH05 5H029 AJ03 AJ14 AK02 AK03 AL06 AL12 AM03 AM04 AM05 AM07 BJ03 BJ16 DJ02 DJ07 DJ12 HJ04 HJ12 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Kazuo Udagawa 3-4-10 Minamishinagawa, Shinagawa-ku, Tokyo F-term in Toshiba Battery Corporation (reference) 5H017 AA03 AS02 CC05 HH03 HH05 5H029 AJ03 AJ14 AK02 AK03 AL06 AL12 AM03 AM04 AM05 AM07 BJ03 BJ16 DJ02 DJ07 DJ12 HJ04 HJ12
Claims (2)
正極端子を兼ねる金属製の正極ケースが絶縁ガスケット
を介し嵌合され、さらに前記正極ケースまたは負極ケー
スが加締め加工により加締められた封口構造を有し、そ
の内部に少なくとも正極、負極、薄膜セパレータを合わ
せた電極群と、非水電解質を収納した扁平形非水電解質
二次電池において、前記正極または負極ケースと前記電
極層との間に金属ネットを設けたことを特徴とする扁平
形非水電解質二次電池。1. A closure in which a metal negative electrode case also serving as a negative electrode terminal and a metal positive electrode case also serving as a positive electrode terminal are fitted via an insulating gasket, and the positive electrode case or the negative electrode case is caulked by caulking. In a flat non-aqueous electrolyte secondary battery containing a non-aqueous electrolyte containing at least a positive electrode, a negative electrode, and a thin film separator having a structure therein, between the positive electrode or the negative electrode case and the electrode layer A flat nonaqueous electrolyte secondary battery characterized by having a metal net provided thereon.
厚さと前記金属ネットの厚さの合計が０．３０ｍｍ以上
０．４５ｍｍ以下であることを特徴とする請求項１記載
の扁平形非水電解質二次電池。2. The flat nonaqueous electrolyte according to claim 1, wherein the sum of the thickness of the positive electrode case or the negative electrode case and the thickness of the metal net is 0.30 mm or more and 0.45 mm or less. Next battery.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000183000A JP4656698B2 (en) | 2000-06-19 | 2000-06-19 | Flat non-aqueous electrolyte secondary battery |
| TW089116426A TW504854B (en) | 1999-08-27 | 2000-08-15 | Flat non-aqueous electrolyte secondary cell |
| US09/641,267 US6521373B1 (en) | 1999-08-27 | 2000-08-17 | Flat non-aqueous electrolyte secondary cell |
| EP00117368.1A EP1079454B1 (en) | 1999-08-27 | 2000-08-23 | Flat non-aqueous electrolyte secondary cell |
| KR1020000049510A KR100559363B1 (en) | 1999-08-27 | 2000-08-25 | Flat non-aqueous electrolyte secondary cell |
| CNB001262041A CN1180504C (en) | 1999-08-27 | 2000-08-25 | Flat nonaqueous electrolyte secondary cell |
| HK01106014A HK1035605A1 (en) | 1999-08-27 | 2001-08-27 | Flat non-aqueous electrolyte secondary cell. |
| US10/318,177 US7378186B2 (en) | 1999-08-27 | 2002-12-13 | Flat non-aqueous electrolyte secondary cell |
| US11/176,400 US7566515B2 (en) | 1999-08-27 | 2005-07-08 | Flat non-aqueous electrolyte secondary cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000183000A JP4656698B2 (en) | 2000-06-19 | 2000-06-19 | Flat non-aqueous electrolyte secondary battery |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010176152A Division JP4657377B2 (en) | 2010-08-05 | 2010-08-05 | Flat non-aqueous electrolyte secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002008729A true JP2002008729A (en) | 2002-01-11 |
| JP4656698B2 JP4656698B2 (en) | 2011-03-23 |
Family
ID=18683649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000183000A Expired - Lifetime JP4656698B2 (en) | 1999-08-27 | 2000-06-19 | Flat non-aqueous electrolyte secondary battery |
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| JP (1) | JP4656698B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57130958U (en) * | 1981-02-10 | 1982-08-14 | ||
| JPS5912470U (en) * | 1982-07-13 | 1984-01-25 | 日立マクセル株式会社 | flat lithium battery |
| JPS59144765U (en) * | 1983-03-16 | 1984-09-27 | 日立マクセル株式会社 | Flat battery with lead terminal |
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| JPS6116863U (en) * | 1984-07-05 | 1986-01-31 | 富士電気化学株式会社 | Flat non-aqueous electrolyte battery with lead terminals |
| JPH02265173A (en) * | 1989-04-04 | 1990-10-29 | Seiko Electronic Components Ltd | Manufacture of battery |
| JPH03127455A (en) * | 1989-10-06 | 1991-05-30 | Matsushita Electric Ind Co Ltd | Flat type cell |
| JPH05115710A (en) * | 1991-10-25 | 1993-05-14 | Toshiba Corp | Apparatus for controlling injection of flocculant |
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| JPH09213307A (en) * | 1995-11-30 | 1997-08-15 | Elna Co Ltd | Nonaqueous electrolyte system secondary cell |
| JPH10172538A (en) * | 1996-12-05 | 1998-06-26 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary battery and manufacture thereof |
| JPH11102672A (en) * | 1997-09-25 | 1999-04-13 | Matsushita Electric Ind Co Ltd | Manufacture of battery case and battery |
| JPH11250872A (en) * | 1998-02-27 | 1999-09-17 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary battery |
| JP2000113864A (en) * | 1998-10-06 | 2000-04-21 | Toshiba Battery Co Ltd | Flat nonaqueous electrolyte battery |
| JP2001068143A (en) * | 1999-08-27 | 2001-03-16 | Toshiba Battery Co Ltd | Flat nonaqueous electrolyte secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57130958U (en) * | 1981-02-10 | 1982-08-14 | ||
| JPS5912470U (en) * | 1982-07-13 | 1984-01-25 | 日立マクセル株式会社 | flat lithium battery |
| JPS59144765U (en) * | 1983-03-16 | 1984-09-27 | 日立マクセル株式会社 | Flat battery with lead terminal |
| JPS6017858A (en) * | 1983-07-12 | 1985-01-29 | Fuji Elelctrochem Co Ltd | Nonaqueous electrolyte battery |
| JPS616259U (en) * | 1984-06-18 | 1986-01-14 | 富士電気化学株式会社 | Battery for board mounting |
| JPS6116863U (en) * | 1984-07-05 | 1986-01-31 | 富士電気化学株式会社 | Flat non-aqueous electrolyte battery with lead terminals |
| JPH02265173A (en) * | 1989-04-04 | 1990-10-29 | Seiko Electronic Components Ltd | Manufacture of battery |
| JPH03127455A (en) * | 1989-10-06 | 1991-05-30 | Matsushita Electric Ind Co Ltd | Flat type cell |
| JPH05115710A (en) * | 1991-10-25 | 1993-05-14 | Toshiba Corp | Apparatus for controlling injection of flocculant |
| JPH05325918A (en) * | 1992-03-31 | 1993-12-10 | Sumitomo Metal Ind Ltd | Stainless steel plate for button type battery case |
| JPH09213307A (en) * | 1995-11-30 | 1997-08-15 | Elna Co Ltd | Nonaqueous electrolyte system secondary cell |
| JPH10172538A (en) * | 1996-12-05 | 1998-06-26 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary battery and manufacture thereof |
| JPH11102672A (en) * | 1997-09-25 | 1999-04-13 | Matsushita Electric Ind Co Ltd | Manufacture of battery case and battery |
| JPH11250872A (en) * | 1998-02-27 | 1999-09-17 | Toshiba Battery Co Ltd | Nonaqueous solvent secondary battery |
| JP2000113864A (en) * | 1998-10-06 | 2000-04-21 | Toshiba Battery Co Ltd | Flat nonaqueous electrolyte battery |
| JP2001068143A (en) * | 1999-08-27 | 2001-03-16 | Toshiba Battery Co Ltd | Flat nonaqueous electrolyte secondary battery |
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| Publication number | Publication date |
|---|---|
| JP4656698B2 (en) | 2011-03-23 |
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