JP2002134073A - Flattened non-aqueous electrolytic secondary battery - Google Patents
Flattened non-aqueous electrolytic secondary batteryInfo
- Publication number
- JP2002134073A JP2002134073A JP2000328332A JP2000328332A JP2002134073A JP 2002134073 A JP2002134073 A JP 2002134073A JP 2000328332 A JP2000328332 A JP 2000328332A JP 2000328332 A JP2000328332 A JP 2000328332A JP 2002134073 A JP2002134073 A JP 2002134073A
- Authority
- JP
- Japan
- Prior art keywords
- secondary battery
- battery
- positive electrode
- aqueous electrolytic
- gas
- 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
-
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は重負荷放電特性及び
その安全性に優れた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 nonaqueous electrolyte secondary battery excellent in heavy load discharge characteristics and safety thereof.
【０００２】[0002]
【従来の技術】従来のコイン形やボタン形の扁平形非水
電解質二次電池は、小型でシンプルな構造であることか
ら軽負荷の用途に大量に使用されている。しかし、電池
を主電源とする携帯電話、ＡＶ機器などの小型化、薄型
化に伴い、小型で薄型の中〜重負荷に耐えられる電池が
要求されてきた。2. Description of the Related Art Conventional coin-shaped or button-shaped flat non-aqueous electrolyte secondary batteries have been used in large quantities for light-load applications because of their small size and simple structure. However, with the miniaturization and thinning of mobile phones and AV equipment that use a battery as a main power source, a small and thin battery that can withstand a medium to heavy load has been demanded.
【０００３】そこで、本発明者らは扁平形非水電解質二
次電池で、電極面積が大きくとれる渦巻き状に正極、負
極、セパレータを巻き込んで圧縮加工した構成の電極群
を提案してコイン形及び、ボタン形電池に収めた。これ
により小型でも大電流の取り出せる二次電池が得られた
が、同時に内部短絡などの異常事態でガス発生量も多く
なる機会が増えた。このような二次電池は構成上、防爆
機構を設けることが困難で且つ、ガスの発生を完全に防
止することも極めて難しく、対策のないのが実状であっ
た。Accordingly, the present inventors have proposed a flat non-aqueous electrolyte secondary battery in which a positive electrode, a negative electrode, and a separator are formed in a spiral shape in which a large electrode area is obtained, and a compression process is performed. In a button-type battery. As a result, a secondary battery capable of taking out a large current even with a small size was obtained, but at the same time, the chance of generating a large amount of gas due to an abnormal situation such as an internal short circuit increased. In such a secondary battery, it is difficult to provide an explosion-proof mechanism because of its configuration, and it is extremely difficult to completely prevent the generation of gas.
【０００４】[0004]
【発明が解決しようとする課題】一般に、二次電池は充
放電を繰り返して使用するので、ガスの発生は避けられ
ない。そのため、円筒形の各種二次電池には防爆装置が
設けられている。この防爆装置はいわゆる復帰型タイプ
で繰り返し作動してガスのみを外部に排出する機能を有
している。又、一次電池における防爆装置は円筒形アル
カリ電池に代表されるように、破壊型の防爆装置が設置
され、その役目は１回の作動で機能を失っていた。Generally, since secondary batteries are used repeatedly by charging and discharging, generation of gas is inevitable. Therefore, various cylindrical secondary batteries are provided with an explosion-proof device. This explosion-proof device has a function of repeatedly operating as a so-called return type and discharging only gas to the outside. Further, as the explosion-proof device of the primary battery, a destruction-type explosion-proof device is installed, as represented by a cylindrical alkaline battery, and its function has been lost by one operation.
【０００５】また、扁平形非水電解質二次電池は、その
構成から電極面積が大きく大電流を発生するので、内部
短絡、過放電などの不測の事態ではガス発生量が多く、
破裂に至る可能性がある。しかし、破裂予防装置が設け
られてないので異常に多量のガスが発生すると電池が破
裂し、電池内容物、容器が飛散して使用機器の破損はい
うに及ばず、人身に危害を加える恐れもある。Further, the flat non-aqueous electrolyte secondary battery has a large electrode area due to its configuration and generates a large current. Therefore, in an unexpected situation such as an internal short circuit or overdischarge, a large amount of gas is generated.
It can lead to a rupture. However, since there is no rupture prevention device, if an abnormally large amount of gas is generated, the battery will rupture and the battery contents and container will be scattered, not only to damage the equipment used, but also to cause harm to humans. is there.
【０００６】[0006]
【課題を解決するための手段】上記課題を解決するため
に、本発明の扁平形非水電解質二次電池は、正極容器封
口部に縦溝を加工し薄板部を構成することで、電池内に
異常なガスが発生し内圧が上昇した場合は、正極容器封
口部の縦溝薄板部を負極容器が押し上げ、変形破断して
低圧力で二枚貝のように負極容器が開くことでガスを電
池外部に排出し、負極容器が電池本体から分離して、電
池内容物と共に飛散するような破裂を回避するように構
成されている。Means for Solving the Problems In order to solve the above-mentioned problems, a flat nonaqueous electrolyte secondary battery of the present invention has a thin plate portion formed by forming a vertical groove in a sealing portion of a positive electrode container. When an abnormal gas is generated and the internal pressure rises, the negative electrode container pushes up the vertical groove thin plate part of the positive electrode container sealing part, deforms and breaks, and the negative electrode container opens like a bivalve at low pressure, and the gas is discharged outside the battery. , And the anode container is separated from the battery main body, and is configured to avoid rupture such as scattering with the battery contents.
【０００７】[0007]
【発明の実施の形態】以下、本発明の実施の形態を図を
参照して説明する。図１は本発明の実施例であるコイン
形非水電解質二次電池の断面図であり、図２と図３はそ
れぞれ図１の正極容器封口Ｒ部薄板部の外観図と半断面
図である。Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a cross-sectional view of a coin-type non-aqueous electrolyte secondary battery according to an embodiment of the present invention. FIGS. 2 and 3 are an external view and a half cross-sectional view of a thin plate portion of a positive electrode container sealing R portion of FIG. .
【０００８】（実施例１）図１に示す実施例１は、外径
２４ｍｍ、高さ３．０ｍｍのコイン形非水電解質二次電
池である。以下本実施例１の電池の製造方法を説明す
る。１はステンレス鋼よりなる板厚さ０．２５ｍｍの正
極端子を兼ねた正極ケースで、５はステンレス鋼よりな
る板厚さ０．２０ｍｍの負極端子を兼ねた負極ケースで
ある。まず、ＬｉＣｏＯ2１００質量部に対し導電剤と
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稀釈、混合し、スラリー状
の正極合剤を得た。次にこの正極合剤を、正極集合体で
ある厚さ０．０２ｍｍのアルミ箔の両面にドクターブレ
ード法により塗工、乾燥を行い、正極作用物質含有層の
塗膜厚さが両面で０．１５ｍｍの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にし通電部
とし、幅１５ｍｍ、長さ１２０ｍｍに切り出し正極板２
を作製した。Example 1 Example 1 shown in FIG. 1 is a coin-shaped non-aqueous electrolyte secondary battery having an outer diameter of 24 mm and a height of 3.0 mm. Hereinafter, a method for manufacturing the battery of Example 1 will be described. Reference numeral 1 denotes a positive electrode case made of stainless steel and also serving as a positive electrode terminal having a plate thickness of 0.25 mm, and reference numeral 5 denotes a negative electrode case made of stainless steel and serving as a negative electrode terminal having a plate thickness of 0.20 mm. First, 5 parts by mass of acetylene black and 5 parts by mass of graphite powder as a conductive agent were added to 100 parts by mass of LiCoO 2 , 5 parts by mass of polyvinylidene fluoride was added as a binder, and the mixture was diluted with N-methylpyrrolidone and mixed. A positive electrode mixture was obtained. Next, this positive electrode mixture is applied to both surfaces of a 0.02 mm thick aluminum foil as a positive electrode assembly by a doctor blade method and dried, and the coating thickness of the positive electrode active substance-containing layer is 0.1 mm on both surfaces. A 15 mm double-sided coated positive electrode was prepared. Next, the active substance-containing layer of 10 mm portion was removed from the end of one side of the electrode body, and the aluminum layer was exposed and used as a current-carrying part, cut out to a width of 15 mm and a length of 120 mm, and cut into a positive electrode plate 2.
Was prepared.
【０００９】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（ＣＭＣ）
をそれぞれ２．５質量部を添加し、イオン交換水で稀
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の銅箔両面
にドクターブレード法により塗工、乾燥を行い、作用物
質含有層の厚さが０．１５ｍｍの両面塗工負極を作製し
た。次に、この電極体片面の端から１０ｍｍ部分の作用
物質含有層を除去し、銅層を剥き出しにし通電部とし、
幅１５ｍｍ、長さ１２０ｍｍに切り出した負極板４を作
製した。Next, styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) are used as binders in 100 parts by mass of the graphitized mesophase pitch carbon fiber powder.
Was added and diluted with ion-exchanged water and mixed to obtain a slurry-like negative electrode mixture. The obtained negative electrode mixture is applied to both sides of a copper foil having a thickness of 0.02 mm as a negative electrode current collector by a doctor blade method and dried, and a double-sided coated negative electrode having an active substance-containing layer having a thickness of 0.15 mm is applied. Was prepared. Next, the active substance-containing layer of 10 mm portion was removed from one end of the electrode body, and the copper layer was exposed to form a current-carrying part.
A negative electrode plate 4 cut out to a width of 15 mm and a length of 120 mm was produced.
【００１０】次に、正負極板通電部面を外周巻き終り側
とし、これら正極板２と負極板４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３を介して渦
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 current-carrying surface of the positive and negative electrode plates is set to the outermost winding end side, and spirally wound between the positive electrode plate 2 and the negative electrode plate 4 via a separator 3 made of a 25 μm-thick polyethylene microporous film. Then, 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 flat surface of the flat battery.
【００１１】作製した電極群を８５℃で１２ｈ乾燥した
後、絶縁ガスケット６を一体化した負極金属ケース５の
内底面に電極群の負極板の作用物質含有層除去部が接す
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１ｍｏｌ／ｌの割合で溶解せし
めた非水電解質を注液し、さらに電極群の正極板の作用
物質含有層除去部に接するように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１に径方向お
よび高さ方向のかしめ加工を実施し、封口した。After the produced electrode group is dried at 85 ° C. for 12 hours, the electrode group is placed such that the active substance-containing layer removed portion of the negative electrode plate of the electrode group contacts the inner bottom surface of the negative electrode metal case 5 with the insulating gasket 6 integrated therewith. A non-aqueous electrolyte obtained by dissolving LiPF 6 at a ratio of 1 mol / l as a supporting salt in a solvent in which ethylene carbonate and methyl ethyl carbonate are mixed at a volume ratio of 1: 1 is injected, and the function of the positive electrode plate of the electrode group The positive electrode case 1 made of stainless steel was fitted so as to be in contact with the material-containing layer removed portion, and after turning upside down, the positive electrode case 1 was subjected to caulking in the radial direction and the height direction and sealed.
【００１２】正極ケース１において、図２には開口端部
より溝薄板長さｈが１．５ｍｍの薄板部の外観が示され
ており、また図３には正極ケース１の輪切り状断面が示
されており、溝薄板部１ａを１本加工してある。この溝
薄板部１ａの厚さｓは０．０５ｍｍから０．０２ｍｍ刻
みに０．１７ｍｍ迄の７種類用意し、これらの電池につ
いて４．２Ｖ，３ｍＡの定電流定電圧で４８時間初充電
実施後、３００ｍＡｈ、６時間の定電流強制放電試験と
昇温速度５℃／１分で１６０℃／１０分持続加熱し、そ
れぞれ１０個試験を行い、破裂試験の結果及び、４５℃
−９３％Ｒｈで１００日間貯蔵した電解液漏液試験を各
３０個評価した。In the positive electrode case 1, FIG. 2 shows the appearance of a thin plate portion having a groove thin plate length h of 1.5 mm from the opening end, and FIG. One groove thin plate portion 1a is machined. The thickness s of the grooved thin plate portion 1a is prepared in seven types from 0.05 mm to 0.17 mm in increments of 0.02 mm, and after initial charging for 48 hours at a constant current and constant voltage of 4.2 V, 3 mA. , 300 mAh, constant current forced discharge test for 6 hours, continuous heating at 160 ° C. for 10 minutes at a heating rate of 5 ° C. for 1 minute, 10 tests for each, the results of the burst test and 45 ° C.
Each of 30 electrolyte leakage tests stored at −93% Rh for 100 days was evaluated.
【００１３】（実施例２）実施例１と同様の二次電池で
正極容器の溝薄板部を２ヶ所にした場合の評価を同様の
内容で実施した。(Example 2) An evaluation was performed with the same contents in the same secondary battery as in Example 1 except that the groove portion of the positive electrode container was provided at two places.
【００１４】表１に試験結果を示したが、実施例１と同
様の結果を示した。溝薄板部厚さが０．１７ｍｍでは、
溝数１、２本共に薄板部の破断が起こらず電池の内容物
が飛散する破裂の発生が見られた。又、薄板厚さが０．
０５ｍｍでは漏液の発生が溝数１、２本共にみられた
が、原因は薄板部の厚さが薄すぎて封口加工時に亀裂が
発生し封口性が損なわれたことによる。Table 1 shows the test results, and the same results as in Example 1 were shown. If the groove thin plate thickness is 0.17mm,
In each of the one and two grooves, the thin plate portion did not break, and rupture in which the contents of the battery were scattered was observed. In addition, the thickness of the thin plate is 0.
In the case of 05 mm, the generation of liquid leakage was observed in both the one and two grooves, but the reason was that the thickness of the thin plate portion was too thin and cracks were generated at the time of sealing processing, and the sealing property was impaired.
【００１５】[0015]
【表１】 [Table 1]
【００１６】この結果より、薄板部の厚さは０．０７ｍ
ｍから０．１５ｍｍの範囲にすることで、破裂を防止で
き、貯蔵による漏液もない扁平形非水溶媒二次電池が得
られる。From these results, the thickness of the thin plate was 0.07 m.
By setting the range of m to 0.15 mm, a flat nonaqueous solvent secondary battery in which rupture can be prevented and liquid leakage due to storage can be obtained.
【００１７】尚、本発明の実施例１及び実施例２は、非
水溶液電解質に非水溶媒を使用した扁平形非水溶媒二次
電池を用いて説明したが、非水電解質にポリマー電解質
を用いたポリマー二次電池や固体電解質を用いた固体電
解質二次電池についても、同様の効果が得られ、更に
は、アルカリ電解液を使用したボタン形アルカリ電池に
ついても同様の効果が得られる。Although Embodiments 1 and 2 of the present invention have been described using a flat non-aqueous solvent secondary battery using a non-aqueous solvent for the non-aqueous electrolyte, a polymer electrolyte is used for the non-aqueous electrolyte. The same effect can be obtained for a polymer secondary battery or a solid electrolyte secondary battery using a solid electrolyte, and the same effect can be obtained for a button-type alkaline battery using an alkaline electrolyte.
【００１８】[0018]
【発明の効果】以上説明したとおり、本発明によると、
正極ケースの封口部に溝加工して薄板部を設けること
で、不測の事態で多量にガスが発生しても低圧力で破断
させて内部ガスを排出し、電池内容物が飛散することの
ない安全性の高い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,
By forming a groove in the sealing part of the positive electrode case and providing a thin plate part, even if a large amount of gas is generated unexpectedly, it is broken at low pressure and the internal gas is discharged, and the battery contents are not scattered A highly safe flat nonaqueous electrolyte secondary battery can be provided.
【図１】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。FIG. 1 is a cross-sectional view of a flat nonaqueous electrolyte secondary battery according to Embodiment 1 of the present invention.
【図２】図１の扁平形非水電解質二次電池の外観図。FIG. 2 is an external view of the flat nonaqueous electrolyte secondary battery of FIG.
【図３】図１の正極ケースの半断面図。FIG. 3 is a half sectional view of the positive electrode case of FIG. 1;
１…正極ケース、１ａ…正極容器溝薄板部、２…正極
板、３…セパレータ、４…負極板、５…負極ケース、６
…絶縁ガスケット。DESCRIPTION OF SYMBOLS 1 ... Positive case, 1a ... Positive container groove thin plate part, 2 ... Positive plate, 3 ... Separator, 4 ... Negative plate, 5 ... Negative case, 6
... an insulating gasket.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鈴木 正美 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 (72)発明者 酒井 広隆 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） 5H011 AA13 JJ04 KK01 5H029 AJ12 AK03 AL07 AM03 AM05 AM07 BJ03 BJ14 CJ04 DJ02 HJ04 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masami Suzuki 3-4-1-10 Minamishinagawa, Shinagawa-ku, Tokyo Inside Toshiba Battery Corporation (72) Inventor Hirotaka Sakai 3-4-1 Minamishinagawa, Shinagawa-ku, Tokyo F-term in Toshiba Battery Corporation (reference) 5H011 AA13 JJ04 KK01 5H029 AJ12 AK03 AL07 AM03 AM05 AM07 BJ03 BJ14 CJ04 DJ02 HJ04
Claims (2)
し２本の溝を加工し薄板部を構成したことを特徴とする
扁平形非水電解質二次電池。1. A flat nonaqueous electrolyte secondary battery in which one or two grooves are machined in a longitudinal direction of a sealing R portion of a positive electrode container to form a thin plate portion.
池において、溝加工による薄板部の厚さは、０．０７ｍ
ｍから０．１５ｍｍの範囲としたことを特徴とする扁平
形非水電解質二次電池。2. The flat nonaqueous electrolyte secondary battery according to claim 1, wherein the thickness of the thin plate portion formed by the groove processing is 0.07 m.
A flat non-aqueous electrolyte secondary battery characterized by having a range of m to 0.15 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000328332A JP2002134073A (en) | 2000-10-27 | 2000-10-27 | Flattened non-aqueous electrolytic secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000328332A JP2002134073A (en) | 2000-10-27 | 2000-10-27 | Flattened non-aqueous electrolytic secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002134073A true JP2002134073A (en) | 2002-05-10 |
Family
ID=18805202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000328332A Pending JP2002134073A (en) | 2000-10-27 | 2000-10-27 | Flattened non-aqueous electrolytic secondary battery |
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| Country | Link |
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| JP (1) | JP2002134073A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003045379A (en) * | 2001-07-31 | 2003-02-14 | Matsushita Electric Ind Co Ltd | Coin-shaped battery |
| US20200185755A1 (en) | 2009-02-09 | 2020-06-11 | Varta Microbattery Gmbh | Button cells and method of producing same |
| US10804506B2 (en) | 2009-06-18 | 2020-10-13 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
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| JPS575262A (en) * | 1980-06-12 | 1982-01-12 | Casio Comput Co Ltd | Alkaline battery |
| JPS60140361U (en) * | 1984-02-28 | 1985-09-17 | 日本電池株式会社 | sealed battery |
| JPH10269997A (en) * | 1997-03-21 | 1998-10-09 | Shin Kobe Electric Mach Co Ltd | Closed cylindrical storage battery |
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Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003045379A (en) * | 2001-07-31 | 2003-02-14 | Matsushita Electric Ind Co Ltd | Coin-shaped battery |
| US11233264B2 (en) | 2009-02-09 | 2022-01-25 | Varta Microbattery Gmbh | Button cells and method of producing same |
| US11791493B2 (en) | 2009-02-09 | 2023-10-17 | Varta Microbattery Gmbh | Button cells and method of producing same |
| US11276875B2 (en) | 2009-02-09 | 2022-03-15 | Varta Microbattery Gmbh | Button cells and method of producing same |
| US11233265B2 (en) | 2009-02-09 | 2022-01-25 | Varta Microbattery Gmbh | Button cells and method of producing same |
| US11258092B2 (en) | 2009-02-09 | 2022-02-22 | Varta Microbattery Gmbh | Button cells and method of producing same |
| US20200185755A1 (en) | 2009-02-09 | 2020-06-11 | Varta Microbattery Gmbh | Button cells and method of producing same |
| US11024869B2 (en) | 2009-02-09 | 2021-06-01 | Varta Microbattery Gmbh | Button cells and method of producing same |
| US11024905B2 (en) | 2009-06-18 | 2021-06-01 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
| US11024906B2 (en) | 2009-06-18 | 2021-06-01 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
| US10971776B2 (en) | 2009-06-18 | 2021-04-06 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
| US11024907B1 (en) | 2009-06-18 | 2021-06-01 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
| US10804506B2 (en) | 2009-06-18 | 2020-10-13 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
| US11024904B2 (en) | 2009-06-18 | 2021-06-01 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
| US11217844B2 (en) | 2009-06-18 | 2022-01-04 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
| US11362385B2 (en) | 2009-06-18 | 2022-06-14 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
| US11362384B2 (en) | 2009-06-18 | 2022-06-14 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
| US11791512B2 (en) | 2009-06-18 | 2023-10-17 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
| US11158896B2 (en) | 2009-06-18 | 2021-10-26 | Varta Microbattery Gmbh | Button cell having winding electrode and method for the production thereof |
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