JPH03190061A - Cylindrical lithium secondary battery - Google Patents
Cylindrical lithium secondary batteryInfo
- Publication number
- JPH03190061A JPH03190061A JP1330110A JP33011089A JPH03190061A JP H03190061 A JPH03190061 A JP H03190061A JP 1330110 A JP1330110 A JP 1330110A JP 33011089 A JP33011089 A JP 33011089A JP H03190061 A JPH03190061 A JP H03190061A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- electrodes
- positive
- battery
- negative
- 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
- 229910052744 lithium Inorganic materials 0.000 title claims description 31
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 29
- 239000011255 nonaqueous electrolyte Substances 0.000 claims description 4
- 238000004804 winding Methods 0.000 abstract description 10
- 230000001788 irregular Effects 0.000 abstract description 2
- -1 nO1 Chemical class 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000037303 wrinkles Effects 0.000 description 6
- 238000007599 discharging Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、リチウムを負極材料として使用した円筒形リ
チウム二次電池に関し、更に詳述すると高放電容量を示
し、充放電特性、安全性に優れたスパイラル構造電極を
有する円筒形リチウム二次電池に関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a cylindrical lithium secondary battery using lithium as a negative electrode material. This invention relates to a cylindrical lithium secondary battery having an excellent spiral structure electrode.
近年、リチウム等のアルカリ金属を負極活物質に用いた
非水電解質電池は、高電圧、高エネルギー密度で優れた
自己放電特性を示すことから注目されており、更にこれ
らを充放電可能とした二次電池、特に電極を円筒形とし
た高容量二次電池は、ポータプル機器等各種のエレクト
ロニクス機器の主電源用途として期待されている。In recent years, nonaqueous electrolyte batteries that use alkali metals such as lithium as negative electrode active materials have attracted attention because they exhibit excellent self-discharge characteristics at high voltage and high energy density. Secondary batteries, especially high-capacity secondary batteries with cylindrical electrodes, are expected to be used as main power sources for various electronic devices such as portable devices.
従来、円筒形電池においては、大きな放電電流を取り出
せるように薄板状の正極板と負極板とをセパレーターを
介してスパイラル状に形成し、電池反応にあずかる電極
表面積を広くした構造が好ましく採用されており、特に
リチウム二次電池のように充放電に伴ってリチウムイオ
ンが可逆的に移動するような反応機構の場合、単位面積
当りの電流値、即ちイオンの移動量が少ない方がハイレ
ートな放電ができ、しかも充電時の電流密度を低減化で
きるので良好な充放電サイクル特性が得られる。このた
め、スパイラル構造を採ることば円筒形リチウム電池の
二次電池化を達成するためには欠くことのできない条件
の一つである。Conventionally, cylindrical batteries have preferably adopted a structure in which a thin positive electrode plate and a negative electrode plate are formed in a spiral shape with a separator interposed between them so that a large discharge current can be extracted, thereby increasing the electrode surface area that participates in the battery reaction. In particular, in the case of a reaction mechanism such as a lithium secondary battery in which lithium ions move reversibly during charging and discharging, the smaller the current value per unit area, that is, the amount of ion movement, the higher the rate of discharge. Moreover, since the current density during charging can be reduced, good charge-discharge cycle characteristics can be obtained. Therefore, adopting a spiral structure is one of the indispensable conditions for converting a cylindrical lithium battery into a secondary battery.
ここで、電池に要求される基本的条件の一つとして、安
全性を確保するために内部短絡を確実に防止することが
挙げられる。特にスパイラル構造をもつ円筒形リチウム
電池においては、内部短絡が発生すると、急激に大電流
が流れ、電池内部の発熱により電解液の分解等の不都合
が生じ、電池性能を低下させるばかりでなく、電池破裂
の危険をも生じさせる。Here, one of the basic conditions required of batteries is to reliably prevent internal short circuits in order to ensure safety. In particular, in cylindrical lithium batteries with a spiral structure, if an internal short circuit occurs, a large current will suddenly flow, causing problems such as decomposition of the electrolyte due to heat generation inside the battery, which not only reduces battery performance but also It also creates a risk of rupture.
内部短絡は、正極と負極との接触により発生するもので
あるが、上述のようなスパイラル構造では、正極板と負
極板とを隔てているセパレーターの欠陥部から両極板が
接触したり、両極板のズレ等により両極板の端部がセパ
レーターよりはみ出し、このはみ出した両極板の端部同
士が互いに接触することなどにより、短絡が発生し易い
。特に、スパイラル構造に巻かれた後、電池容器に収納
するとき、電池容器底部においてセパレーターが不規則
につぶされ、セパレーターの開口部より両極板が接触し
たり、あるいはリチウム負極を用いた二次電池の場合は
、充電時にリチウム負極端部にデンドライト状の析出物
が発生し易い傾向にあり、これが上記セパレーターの開
口部を通して短絡を引き起こす可能性が高い。Internal short circuits occur due to contact between the positive and negative electrodes, but in the spiral structure described above, the two electrode plates may come into contact through a defective part of the separator that separates the positive and negative electrode plates, or the two electrode plates may Due to misalignment or the like, the ends of the bipolar plates protrude from the separator, and the protruding ends of the bipolar plates come into contact with each other, thereby easily causing a short circuit. In particular, when stored in a battery container after being wound into a spiral structure, the separator may be crushed irregularly at the bottom of the battery container, causing the two electrode plates to come into contact through the opening of the separator, or secondary batteries using lithium negative electrodes. In this case, dendrite-like precipitates tend to form at the lithium negative end during charging, and this is likely to cause a short circuit through the openings of the separator.
このような現象による正・負極間の短絡を防ぐためには
、両極板より巾の広いセパレーターで一方の電極をはさ
み込み、該極板からはみ出した部分を熱融着して、一方
の電極を袋詰め状態とし、もう一方の極板と共にスパイ
ラル状に巻き上げることにより５両極の短絡を防止する
ことが考えられる。また、特開平１−１２２５７４号公
報に見るように渦巻状に巻回して、上下にはみ出したセ
パレータ一端面部を巻芯方向に折曲げ、かつ熱融着する
方法が提案されている。In order to prevent short circuits between the positive and negative electrodes due to this phenomenon, one electrode is sandwiched between separators that are wider than the two electrode plates, and the protruding portion of the electrode is heat-sealed, and one electrode is placed in a bag. It is conceivable to prevent a short circuit between the five electrodes by placing them in a packed state and rolling them up in a spiral together with the other electrode plate. Furthermore, as seen in Japanese Patent Application Laid-Open No. 1-122574, a method has been proposed in which the separator is wound in a spiral shape, one end surface of the separator that protrudes upward and downward is bent in the direction of the winding core, and heat-sealed.
ところが、上述した改善法に本発明者らが検討を加えた
ところ、種々の問題点が存在することが明らかになった
。However, when the present inventors investigated the above-mentioned improvement method, it became clear that there were various problems.
即ち、セパレーターで一方の電極板を予め袋詰めし、こ
れを他方の電極板と共にスパイラル構造に巻き上げると
、内側となるセパレーターに極板の長手方向に対し、円
弧状のしわが発生するという問題を生じる。これは、例
えば予め負極板をセパレーターで挾み、開口部を熱融着
したものを用いると、負極板は通常０．１〜０．３園の
厚みを持っているため、スパイラル状に巻き上げるとき
に負極板の内側と外側で局長に差異が生じ、このため内
側部では外側部に対して長さが過剰となり、しわを生じ
るものである。このようなしわを生じるとスパイラル状
に巻いた電極の充填率を下げ、放電容量の低下を招くと
共に、二次電池とした場合には、発生したしわが軟らか
いリチウム負極板上に転写され、該極板の厚みにバラツ
キが生じることになり、サイクル寿命を大きく減じる結
果となる。That is, if one electrode plate is packed in a bag in advance with a separator and then rolled up together with the other electrode plate in a spiral structure, the problem of arc-shaped wrinkles occurring in the inner separator in the longitudinal direction of the electrode plate can be solved. arise. For example, if a negative electrode plate is sandwiched between separators and the opening is heat-sealed, the negative electrode plate usually has a thickness of 0.1 to 0.3 mm, so when it is rolled up in a spiral shape, There is a difference in the length between the inside and outside of the negative electrode plate, and as a result, the inside part is longer than the outside part, causing wrinkles. When such wrinkles occur, the filling rate of the spirally wound electrode decreases, leading to a decrease in discharge capacity, and when used as a secondary battery, the wrinkles are transferred onto the soft lithium negative electrode plate. This results in variations in the thickness of the electrode plates, resulting in a significant reduction in cycle life.
また、はみ出したセパレーターの上下端部を折込み、か
つ熱融着すると確かに短絡を防止でき。Additionally, folding the upper and lower ends of the protruding separator and heat-sealing it will certainly prevent short circuits.
かつ袋詰め状態における問題点は解決できる。ところが
、この電池を約６０℃以上で長期間保存したり、その温
度で充放電を行った場合や、大電流放電、外部短絡耐久
テストなどで電池の温度が上昇する場合には、セパレー
ターは熱に反応し、幅方向へも収縮しようとする力が働
く。そのときにセパレーターの両端部は折曲げ融着され
ているために拘束され、セパレーターの微孔が大きくな
ったり、また極板のエッチ等でセパレーターが傷つけら
れて亀裂が生じる場合があり、ミクロ的な短絡が発生し
易くなる。その結果、例えば高温保存下での容量の保持
率が低下するという結果を招く。In addition, problems associated with bagging can be solved. However, if this battery is stored for a long period of time at temperatures above approximately 60°C, or if it is charged or discharged at that temperature, or if the temperature of the battery rises due to high current discharge or external short circuit durability tests, the separator will heat up. In response to this, a force that tries to contract in the width direction also acts. At that time, both ends of the separator are bent and fused, so they are restrained, and the micropores in the separator may become larger, or the separator may be damaged by etching of the electrode plate, causing cracks. Short circuits are more likely to occur. As a result, for example, the capacity retention rate under high temperature storage is reduced.
本発明は、上記事情に鑑みなされたもので、高放電容量
を示し、充放電特性に優れると共に、内部短絡を生じる
ことのない安全性の高いスパイラル構造を有する円筒形
リチウム二次電池を提供することを目的とする。The present invention has been made in view of the above circumstances, and provides a cylindrical lithium secondary battery that exhibits high discharge capacity, excellent charge and discharge characteristics, and has a highly safe spiral structure that does not cause internal short circuits. The purpose is to
〔課題を解決するための手段〕
本発明は上記目的を達成するため、正極とリチウムを含
む負極とがセパレーターを介して渦巻き状に巻かれたス
パイラル構造電極が電池容器内に充填され、非水電解液
が上記正負極間に介在されてなる円筒形リチウム二次電
池において、上記セパレーターが上記スパイラル構造電
極の両端からそれぞれはみ出し、かつ該セパレーターの
電池容器底面側はみ出し部が、両電極の片端面を覆うよ
うに折り曲げられていることを特徴とする円筒形リチウ
ム二次電池を提供する。[Means for Solving the Problems] In order to achieve the above object, the present invention has a spiral structure electrode in which a positive electrode and a negative electrode containing lithium are spirally wound with a separator interposed therebetween. In a cylindrical lithium secondary battery in which an electrolyte is interposed between the positive and negative electrodes, the separator protrudes from both ends of the spiral structure electrode, and the protruding portion of the separator on the bottom side of the battery container is located on one end surface of both electrodes. To provide a cylindrical lithium secondary battery characterized by being bent to cover the cylindrical lithium secondary battery.
本発明の円筒形リチウム二次電池は、上記構成としたこ
とにより、高放電容量、充放電特性の向上及び高い安全
性を達成したものである。The cylindrical lithium secondary battery of the present invention achieves high discharge capacity, improved charge/discharge characteristics, and high safety by having the above structure.
即ち、本発明電池のスパイラル構造電極は、電池容器底
部に当たる部分のセパレーターが画電極端部からはみ呂
していると共に、折曲げられており、両電極の電池容器
底面側端面が該セパレーターのはみ出し部で覆われてい
るため、セパレーターの不規則なつぶれが生じることな
く両電極を収容でき、このためこの部分での短絡が完全
に防止できる。また電極がセパレーターで袋詰め状とさ
れていないので、スパイラル構造へ巻き上げるときに生
じる極板の内側と外側との局長差にセパレーターが追随
し、セパレーターにしわを生じることなくスパイラル構
造を形成することができ、かつセパレーターが折り曲げ
られている端面ば短絡を起こし易い電池容器底面側に限
られているため、高温下に置かれてもセパレーターは十
分巾方向に収縮が可能であり、前述したような両端面の
折曲げ、融着によるセパレーターの拘束に基づく微孔の
拡大や損傷の発生を抑制できるものである。That is, in the spiral structure electrode of the battery of the present invention, the separator at the bottom of the battery container protrudes from the end of the picture electrode and is bent, and the end surfaces of both electrodes on the bottom side of the battery container are aligned with the separator. Since the separator is covered with protruding parts, both electrodes can be accommodated without irregular collapse of the separator, thereby completely preventing short circuits in this part. In addition, since the electrodes are not packed in a bag with separators, the separators follow the difference in the length between the inside and outside of the electrode plate that occurs when it is rolled up into a spiral structure, and the spiral structure can be formed without wrinkles in the separators. However, since the bent end face of the separator is limited to the bottom side of the battery container where short circuits are likely to occur, the separator can sufficiently shrink in the width direction even when placed under high temperatures, and the It is possible to suppress the expansion of micropores and the occurrence of damage due to the restraint of the separator due to bending and fusing of both end faces.
以上の如く、本発明の円筒形リチウム二次電池は正負両
極間の短絡を確実に防止することができ、従って高放電
容量、優れた充放電特性及び高い安全性を確保し得るも
のである。As described above, the cylindrical lithium secondary battery of the present invention can reliably prevent short circuits between the positive and negative electrodes, thereby ensuring high discharge capacity, excellent charge/discharge characteristics, and high safety.
以下、本発明の一実施例につき図面を参照して説明する
。Hereinafter, one embodiment of the present invention will be described with reference to the drawings.
第１図は、本発明に係る円筒形リチウム二次電池の一実
施例を示すもので、この円筒形リチウム二次電池は、正
極板１と負極板２とをこれら正負極板１，２の図中上下
方向両端部よりはみ出するように巾広のセパレーター３
を介して重ね合わせると共に、これを巻き芯４に渦巻き
状に巻いて正負極１，２内にセパレーター３が介装され
たスパイラル構造電極５の両端からはみ出したセパレー
ター３のはみ出し部６ａ、６ｂの電池容器底面側はみ出
し部６ｂを巻き芯４側（中心側）に向けて折り曲げ、こ
れらはみ出し部６ｂで正負極板の１．２片端面を被覆し
、これを円筒形電池容器７に収容してなるもので、正極
板１と負極板２との間には非水電解液が介在されている
。なお、図中８は電池蓋、９は絶縁板、１０は正極端子
、１１はリード線であり、上記電池容器７と電池蓋８は
負極端子を構成し、正極端子１０は特に図示していない
が絶縁パツキン等により電池蓋８とＭｌされた状態にな
っている。FIG. 1 shows an embodiment of a cylindrical lithium secondary battery according to the present invention. This cylindrical lithium secondary battery has a positive electrode plate 1 and a negative electrode plate 2. A wide separator 3 protrudes from both ends in the vertical direction in the figure.
The protruding portions 6a and 6b of the separator 3 protrude from both ends of the spiral structure electrode 5, in which the separator 3 is interposed in the positive and negative electrodes 1 and 2 by spirally winding this around the winding core 4. The protruding parts 6b on the bottom side of the battery container are bent toward the winding core 4 side (center side), and these protruding parts 6b cover 1.2 end faces of the positive and negative electrode plates, and this is housed in the cylindrical battery container 7. A non-aqueous electrolyte is interposed between the positive electrode plate 1 and the negative electrode plate 2. In the figure, 8 is a battery cover, 9 is an insulating plate, 10 is a positive terminal, and 11 is a lead wire, the battery container 7 and the battery cover 8 constitute a negative terminal, and the positive terminal 10 is not particularly shown. is in a state where it is connected to the battery cover 8 by an insulating gasket or the like.
ここで、上記正極（板）１としては、薄板状に形成され
たｖ２０．、ＶＧＯ，、、ＬｉＶ、Ｏ，、ＭｎＯ２゜Ｍ
ｎＯ１等の金属酸化物、ＴｉＳ２．Ｍｏ８２等の金属硫
化物、ポリアニリン等の導電性ポリマーなどを使用する
ことができる。Here, as the positive electrode (plate) 1, v20. ,VGO,,,LiV,O,,MnO2゜M
Metal oxides such as nO1, TiS2. Metal sulfides such as Mo82, conductive polymers such as polyaniline, etc. can be used.
また、負極（板）２としては、リチウムを含むものであ
るが、具体的には、リチウム金属、リチウムとアルミニ
ウム、インジウム、錫、鉛、ビスマス、カドミウム、亜
鉛等との合金などを挙げることができる。これらの中で
は特にリチウム金属。The negative electrode (plate) 2 contains lithium, and specifically includes lithium metal, alloys of lithium with aluminum, indium, tin, lead, bismuth, cadmium, zinc, and the like. Among these, especially lithium metal.
リチウム−アルミニウム合金が好適に使用される。Lithium-aluminum alloys are preferably used.
上記正・負極間に介装するセパレーターとしては、両極
の接触を確実に防止し得、かつ電解液を通したり含んだ
りすることのできる材料、例えばポリテトラフルオロエ
チレン、ポリプロピレンやポリエチレン等の合成樹脂製
の不織布、織布、多孔体や網などを挙げることができる
が、特に厚さ２０〜５〇−程度のポリプロピレン又はポ
リエチレン製の微孔質フィルムが好ましく用いられる。The separator interposed between the positive and negative electrodes is made of a material that can reliably prevent contact between the two electrodes and that can pass or contain the electrolyte, such as synthetic resin such as polytetrafluoroethylene, polypropylene, or polyethylene. Examples include nonwoven fabrics, woven fabrics, porous bodies, and nets, but particularly preferred are microporous films made of polypropylene or polyethylene with a thickness of about 20 to 50 mm.
このセパレーターのはみ出し部の長さ（はみ出し巾）は
、上記正・負極の厚みにより適宜設定されるが、はみ出
し部の長さは正負極板１，２の電池容器底面側端面を完
全に被覆し得るようにすることが好適で、通常は１〜５
ＩＩＩｌである。即ち、はみ出し部が短かすぎると、こ
れを折り曲げた際、正・負極板の端面を完全に被覆する
ことができず、デンドライト等による両極の短絡の危険
を生じる場合があり、一方長すぎると折り曲げられたセ
パレーターの重なりが厚くなり、電池内容積に対する電
池高さ方向の充填効率が低下し、電池性能を低下させる
場合がある。また、上記セパレーターのはみ出し部を折
り曲げる方法としては、特に制限されるものではないが
、熱板等によりスパイラル構造の中心へ向けて折り込ん
で行き、はみ出し部に完全な型付は処理を施す方法が好
適に採用される。この場合、熱板の温度は、ポリプロピ
レンの微孔性シートをセパレーターとして用いた場合は
１５０〜１７０℃程度とすることが好ましい。The length of the protruding part (protruding width) of this separator is set appropriately depending on the thickness of the positive and negative electrodes, but the length of the protruding part is such that the protruding part completely covers the bottom side end surface of the battery container of the positive and negative electrode plates 1 and 2. It is preferable to obtain
It is III. In other words, if the protruding part is too short, when it is bent, it may not be able to completely cover the end faces of the positive and negative electrode plates, and there is a risk of a short circuit between the two poles due to dendrites, etc. On the other hand, if the protruding part is too long, The overlap of the folded separators becomes thick, and the filling efficiency in the battery height direction relative to the battery internal volume decreases, which may reduce battery performance. There are no particular restrictions on the method of folding the protruding portion of the separator, but a method of folding the protruding portion of the separator toward the center of the spiral structure using a hot plate, etc., and then applying a process to completely form the protruding portion is a method. Suitably adopted. In this case, the temperature of the hot plate is preferably about 150 to 170°C when a microporous polypropylene sheet is used as a separator.
また、折り曲げたセパレータ一部分はうまく型付けされ
ているだけでもよく、セパレーター同士の熱融着は特に
必要はない。Furthermore, it is sufficient that a portion of the folded separator is well-shaped, and there is no particular need for heat-sealing the separators together.
上記正・負極間に介在させる非水電解液としては、リチ
ウムイオンを含むものであり、このリチウムイオン源と
しては、リチウム塩、特にＬｉＣＱＯ，、ＬｉＢＦ４．
ＬｉＰＦ、、ＬｉＣＦ、ＳＯ２及びＬ ｉＡ ｓ Ｆ
Ｇから選ばれた１種又は２種以上が好適であり、これら
の電解質は、通常溶媒により溶解された状態で使用され
る。この場合、溶媒としては特に限定されるものではな
いが、プロピレンカーボネート、テトラヒドロフラン、
エチレンカーボネート、ジメトキシエタン、ジエチルカ
ーボネート、γ−ブチロラクトン、ジオキソラン。The nonaqueous electrolyte interposed between the positive and negative electrodes contains lithium ions, and the lithium ion source includes lithium salts, particularly LiCQO, LiBF4.
LiPF, , LiCF, SO2 and LiA s F
One or more electrolytes selected from G are suitable, and these electrolytes are usually used in a state dissolved in a solvent. In this case, the solvent is not particularly limited, but propylene carbonate, tetrahydrofuran,
Ethylene carbonate, dimethoxyethane, diethyl carbonate, γ-butyrolactone, dioxolane.
ブチレンカーボネート及びジメチルホルムアミドから選
ばれた１種又は２種以上の有機溶媒が好適である。One or more organic solvents selected from butylene carbonate and dimethylformamide are suitable.
なおまた、本発明の円筒形リチウム二次電池は、上記実
施例に限定されるものではなく、本発明の要旨の範囲内
で種々変更することができる。Furthermore, the cylindrical lithium secondary battery of the present invention is not limited to the above-mentioned embodiments, and can be variously modified within the scope of the gist of the present invention.
以上説明したように、本発明の円筒形リチウム二次電池
は、高放電容量を示し、充放電特性に優れると共に、内
部短絡を生じることのない安全性の高いものである。As explained above, the cylindrical lithium secondary battery of the present invention exhibits high discharge capacity, excellent charge and discharge characteristics, and is highly safe without causing internal short circuits.
次に、実験例を示し、本発明の効果を具体的に説明する
。Next, experimental examples will be shown to specifically explain the effects of the present invention.
下記の構造を有する３種類のスパイラル構造電極をそれ
ぞれ有底円筒形電池容器に収容し、この容器内に１ｍｏ
ｌ／ＱのＬｉＰＦ６を含むプロピレンカーボネート溶液
を注ぎ込み、封口して第１〜４図に示す如き４種類の単
３型電池を作製した。なお、第２．３．４図において第
１図と同一構成部材には第１図と同一の参照付帯を付し
、その説明を省略する。Three types of spiral structure electrodes having the following structures are housed in a bottomed cylindrical battery container, and 1 mo.
A propylene carbonate solution containing 1/Q of LiPF6 was poured into the container, and the container was sealed to produce four types of AA batteries as shown in FIGS. 1 to 4. In addition, in FIG. 2.3.4, the same reference symbols as in FIG. 1 are given to the same constituent members as in FIG. 1, and the explanation thereof will be omitted.
電極Ａ（第１図）：実施例
負極２として厚み１００ ｔｍ を巾４０ｎｍのリチウ
ムシートを、正極１として化学式Ｌ ｉ Ｖ ａ Ｏｓ
で示されるバナジウム酸化物（活物質）とアセチレンブ
ラック（導電剤）とポリテトラフルオロエチレン粉末（
結着剤）とを混合して厚さ１００−ｙ巾４０ｒｍの板状
に形成したものをそれぞれ用いた。Electrode A (Figure 1): Example A lithium sheet with a thickness of 100 tm and a width of 40 nm was used as the negative electrode 2, and the chemical formula L i Va Os was used as the positive electrode 1.
vanadium oxide (active material), acetylene black (conductive agent), and polytetrafluoroethylene powder (
A plate-like material having a thickness of 100 mm and a width of 40 rms was used.
これら正負極間及び負極板２側にはそれぞれ厚さ２５
ｉｔｓ ＋巾４４■のポリプロピレン製微孔質フィルム
をセパレーター３として両極の巾方向両端縁から２ｍｍ
ずつはみ出すように配し、得られた一体化物を正極板１
が巻き芯４と接触するように巻き芯４を中心としてスパ
イラル状に形成し、画電極１．２の電池容器底面側の端
面よりはみ出したセパレーターのはみ出し部６ｂを中心
に向けて折り曲げ、他方のはみ出し部６ａはそのままと
した。There is a thickness of 25 mm between these positive and negative electrodes and on the negative electrode plate 2 side.
A microporous polypropylene film with a width of 44 cm is used as the separator 3 at a distance of 2 mm from both edges in the width direction of both poles.
Place the resulting integrated product on the positive electrode plate 1.
The separator is formed in a spiral shape around the winding core 4 so that it is in contact with the winding core 4, and the protruding part 6b of the separator that protrudes from the bottom end of the battery container of the picture electrode 1.2 is bent toward the center, and the other The protruding portion 6a was left as is.
！監ｌ（第２図）：比較例１
電極Ａと同様の正、負極板及びセパレーターを用い、予
め負極板をセパレーター３で包み込み、はみ出し部６ａ
及び６ｂを熱融着して袋詰状態とした後、正極板ととも
に巻き上げた。! Supervision (Figure 2): Comparative Example 1 Using the same positive and negative electrode plates and separators as electrode A, wrap the negative electrode plate in advance with separator 3, and remove the protruding part 6a.
and 6b were thermally fused to form a bag, and then rolled up together with the positive electrode plate.
ｌ１旦（第３図）：比較例２
電極Ａと同様の正、負極板とセパレーターを同様にして
巻き上げたが、セパレーターのはみ出し部６ａ及び６ｂ
は電池容器底面部及び上部とも折曲げて熱融着した。11 (Figure 3): Comparative Example 2 The same positive and negative electrode plates and separator as electrode A were rolled up in the same manner, but the protruding parts 6a and 6b of the separator
Both the bottom and top of the battery container were bent and heat-sealed.
１１旦（第４図）：比較例３
電極Ａと同様の正、負極板とセパレーターを同様にして
巻き上げたが、はみ出し部分６ａ及び・６ｂはそのまま
で折曲げず、上下方向に突出した状態とした。11 (Figure 4): Comparative Example 3 The same positive and negative electrode plates and separator as electrode A were rolled up in the same manner, but the protruding parts 6a and 6b were left as they were and were not bent, so that they protruded in the vertical direction. did.
上記４種類の電池につき、下記方法により初期放電容量
、充放電サイクル性能及び衝撃時、高充電電流時におけ
る短絡性及び高温保存性を評価した。結果を第１表に示
す。The above four types of batteries were evaluated for initial discharge capacity, charge/discharge cycle performance, short-circuit properties at impact, high charging current, and high temperature storage stability using the following methods. The results are shown in Table 1.
初期放電容量：
電流値１５０ｍＡにおいて２．Ｏｖを下限電圧として放
電したときの測定値を電池５本の平均値で示した。Initial discharge capacity: 2 at a current value of 150 mA. The measured values when discharging with Ov as the lower limit voltage are shown as the average value of five batteries.
充放電サイクル性能：
上限電圧３．３Ｖ、下限電圧２．ＯＶ、放電電流１５０
ｍＡ、充電電流６０ｍＡの条件で充放電を繰り返し、放
電容量が初期容量の８０％に低下するまでの充放電サイ
クル回数を調べ、電池５本の平均値を示した。Charge/discharge cycle performance: Upper limit voltage 3.3V, lower limit voltage 2. OV, discharge current 150
Charging and discharging were repeated under the conditions of mA and charging current of 60 mA, and the number of charging and discharging cycles until the discharge capacity decreased to 80% of the initial capacity was determined, and the average value of the five batteries was shown.
衝撃時短絡性：
１０個の電池について、それぞれ１．８ｍの高さからコ
ンクリート上に正極端子を上にして５回、正極端子を下
にして５回、計１０回垂直に落下させ、極板のズレ等に
よる短絡を生じた電池の個数を調べた。Short-circuit property upon impact: 10 batteries were vertically dropped onto concrete from a height of 1.8 m 5 times with the positive terminal facing up, and 5 times with the positive terminal facing down, for a total of 10 times. The number of batteries that suffered from short circuits due to misalignment, etc. was investigated.
高充電電流時短絡性：
５個の電池について、上記充放電サイクル性能試験にお
いて充電電流を１２０ｍＡに上げ、１００サイクルまで
充放電を繰り返し、その充放電曲線を測定し、該曲線に
異常が生じるか調べた。Short-circuit property at high charging current: For 5 batteries, increase the charging current to 120 mA in the above charge-discharge cycle performance test, repeat charging and discharging up to 100 cycles, measure the charge-discharge curve, and check whether any abnormality occurs in the curve. Examined.
この場合異常が発生したときは、その発生サイクル数を
測定した。In this case, when an abnormality occurred, the number of cycles in which it occurred was measured.
高温保存性：
６０℃中に４０日間保持した後の放電容量を初期放電容
量に対する保持率として調べ、電池５本の平均値で示し
た。High-temperature storage stability: The discharge capacity after being kept at 60° C. for 40 days was examined as a retention rate with respect to the initial discharge capacity, and the average value of five batteries was shown.
第 １ 表
第１表に示した如く、負極板をセパレーターで袋詰にし
た比較例１の電池は、短絡に関しては全く心配がないが
、予め負極板を袋詰にしているため充填率を高くできず
、また巻き上げ時にしわが生じるため、初期放電容量は
低く、またサイクル性能も低い。また、セパレーターの
上下面方向とも折曲げ熱融着した比較例２では、放電容
量、サイクル性能及び短絡性は良好なものの、高温保存
時の大きな低下が見られる。セパレーターを巻上げその
ままの状態である比較例３では、放電容量、サイクル性
能に関してはある程度の性能を示すが、短絡の危険性が
非常に高い。Table 1 As shown in Table 1, the battery of Comparative Example 1, in which the negative plate was packed in a bag with a separator, had no concerns about short circuits, but since the negative plate was packed in a bag in advance, the filling rate was high. In addition, wrinkles occur during winding, resulting in low initial discharge capacity and poor cycle performance. In addition, in Comparative Example 2, in which the separator was bent and heat-sealed in both the upper and lower surface directions, the discharge capacity, cycle performance, and short circuit performance were good, but a large decrease was observed during high-temperature storage. Comparative Example 3, in which the separator was wound up as it was, showed a certain degree of performance in terms of discharge capacity and cycle performance, but the risk of short circuiting was extremely high.
これらの電池に比べ、実施例の電池はすべてに優れた性
能を示しており、本発明の優れた効果が確認された。Compared to these batteries, the batteries of Examples exhibited superior performance in all respects, confirming the excellent effects of the present invention.
第１図は、本発明円筒形リチウ本二次電池の一実施例を
示す断面図、第２〜４図はそれぞれ比較例１，２及び３
の円筒形リチウム二次電池を示す断面図である。
１・・・正極（板） ２・・・負極（板）３・
・・セパレーター ４・・・巻き芯５・・・スパ
イラル構造電極 ６ａ、６ｂ・・・はみ出し部７・・・
電池容器 ８・・・電池蓋９・・・絶縁板
１０・・・正極端子１１・・・リード線FIG. 1 is a sectional view showing one embodiment of the cylindrical lithium secondary battery of the present invention, and FIGS. 2 to 4 are comparative examples 1, 2, and 3, respectively.
FIG. 2 is a cross-sectional view showing a cylindrical lithium secondary battery. 1...Positive electrode (plate) 2...Negative electrode (plate) 3.
... Separator 4 ... Winding core 5 ... Spiral structure electrode 6a, 6b ... Protrusion part 7 ...
Battery container 8...Battery cover 9...Insulating plate
10... Positive terminal 11... Lead wire
Claims (1)
て渦巻き状に巻かれたスパイラル構造電極が電池容器内
に充填され、非水電解液が上記正負極間に介在されてな
る円筒形リチウム二次電池において、上記セパレーター
が上記スパイラル構造電極の両端からそれぞれはみ出し
、かつ該セパレーターの電池容器底面側はみ出し部が、
両電極の片端面を覆うように折り曲げられていることを
特徴とする円筒形リチウム二次電池。1. A cylindrical lithium secondary battery in which a spiral structure electrode in which a positive electrode and a negative electrode containing lithium are spirally wound through a separator is filled in a battery container, and a non-aqueous electrolyte is interposed between the positive and negative electrodes. In the battery, the separator protrudes from both ends of the spiral structure electrode, and a protruding portion of the separator on the bottom side of the battery container,
A cylindrical lithium secondary battery characterized by having both electrodes bent to cover one end surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1330110A JPH03190061A (en) | 1989-12-20 | 1989-12-20 | Cylindrical lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1330110A JPH03190061A (en) | 1989-12-20 | 1989-12-20 | Cylindrical lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03190061A true JPH03190061A (en) | 1991-08-20 |
Family
ID=18228909
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1330110A Pending JPH03190061A (en) | 1989-12-20 | 1989-12-20 | Cylindrical lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03190061A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6007938A (en) * | 1997-03-24 | 1999-12-28 | Alcatel | Battery with spiral electrode assembly |
| KR20040042373A (en) * | 2002-11-14 | 2004-05-20 | 삼성에스디아이 주식회사 | Cylindrical secondary battery |
| JP2009522744A (en) * | 2006-01-04 | 2009-06-11 | エルジー・ケム・リミテッド | Battery assembly for use with a sealed upper separator and secondary battery having the assembly |
| JP2011129299A (en) * | 2009-12-16 | 2011-06-30 | Toyota Motor Corp | Lithium ion secondary battery, vehicle, and battery loading equipment |
| JP2012109102A (en) * | 2010-11-17 | 2012-06-07 | Toyota Motor Corp | Nonaqueous electrolyte secondary battery |
| US8257849B2 (en) | 2008-05-29 | 2012-09-04 | Sony Corporation | Winding electrode body, nonaqueous electrolyte secondary battery, and method for manufacturing winding electrode body |
-
1989
- 1989-12-20 JP JP1330110A patent/JPH03190061A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6007938A (en) * | 1997-03-24 | 1999-12-28 | Alcatel | Battery with spiral electrode assembly |
| KR20040042373A (en) * | 2002-11-14 | 2004-05-20 | 삼성에스디아이 주식회사 | Cylindrical secondary battery |
| JP2009522744A (en) * | 2006-01-04 | 2009-06-11 | エルジー・ケム・リミテッド | Battery assembly for use with a sealed upper separator and secondary battery having the assembly |
| US8257849B2 (en) | 2008-05-29 | 2012-09-04 | Sony Corporation | Winding electrode body, nonaqueous electrolyte secondary battery, and method for manufacturing winding electrode body |
| JP2011129299A (en) * | 2009-12-16 | 2011-06-30 | Toyota Motor Corp | Lithium ion secondary battery, vehicle, and battery loading equipment |
| JP2012109102A (en) * | 2010-11-17 | 2012-06-07 | Toyota Motor Corp | Nonaqueous electrolyte secondary battery |
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