JPH1173994A - Lithium secondary battery - Google Patents
Lithium secondary batteryInfo
- Publication number
- JPH1173994A JPH1173994A JP9234037A JP23403797A JPH1173994A JP H1173994 A JPH1173994 A JP H1173994A JP 9234037 A JP9234037 A JP 9234037A JP 23403797 A JP23403797 A JP 23403797A JP H1173994 A JPH1173994 A JP H1173994A
- Authority
- JP
- Japan
- Prior art keywords
- electrode plate
- positive electrode
- positive
- battery
- lithium secondary
- 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 claims abstract description 36
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 34
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 9
- 238000004804 winding Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 238000009826 distribution Methods 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000011149 active material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 5
- 239000010439 graphite Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 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
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 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
【０００１】[0001]
【発明の属する技術分野】本発明は、リチウム二次電池
に関し、詳しくはリチウム二次電池の電極構造に関す
る。The present invention relates to a lithium secondary battery, and more particularly, to an electrode structure of a lithium secondary battery.
【０００２】[0002]
【従来の技術】リチウム二次電池は、単位重量当たりの
エネルギー密度が大きいので、携帯電話や携帯パソコ
ン、ワープロなどの移動通信用電源として広く利用され
ており、種々の用途に対応するためにサイズの異なる各
種の形状（円筒形、角形、楕円形など）のものが市販さ
れている。そして、近年では大出力を要する電気自動車
の駆動電源や電力貯蔵用の媒体としての利用を図るた
め、電池の一層の大型化が図られつつある。2. Description of the Related Art Lithium secondary batteries have a high energy density per unit weight and are therefore widely used as mobile communication power sources for mobile phones, mobile personal computers, word processors, and the like. Of various shapes (cylindrical, square, elliptical, etc.) are commercially available. In recent years, batteries have been further increased in size in order to be used as a drive power source for electric vehicles requiring a large output or as a medium for storing power.
【０００３】[0003]
【発明が解決しようとする課題】ところが、従来のリチ
ウム二次電池は、何れも負極板と正極板の枚数比が１／
１で構成されている。然るに、負極板と正極板の枚数比
が１／１の従来の構成のままで、電極板を大きくする
と、電極板の電気抵抗に起因する電位分布差が顕著にな
り、充放電に際して電極板の一部で過充電や過放電が生
じる。この結果、当該部分における活物質の結晶構造が
破壊される等により発電能力が急速に低下する。また、
対向する正負極の容量にアンバランスが生じるため、活
物質の利用率が低下し出力低下を招く。However, in any of the conventional lithium secondary batteries, the ratio of the number of the negative electrode plate to the number of the positive electrode plate is 1 /.
1. However, if the electrode plate is enlarged with the conventional configuration in which the number ratio of the negative electrode plate to the positive electrode plate is 1/1, the potential distribution difference caused by the electric resistance of the electrode plate becomes remarkable, and the charge and discharge of the electrode plate become large. Overcharge or overdischarge occurs in some parts. As a result, the power generation capacity is rapidly reduced due to the destruction of the crystal structure of the active material in the portion. Also,
Since imbalance occurs in the capacity of the opposite positive and negative electrodes, the utilization rate of the active material is reduced, and the output is reduced.
【０００４】上記した電位分布差は、負極板よりも正極
板において一層顕著に現れる。この理由は、炭素材料等
の正極活物質を保持する負極板に比べ、金属酸化物等の
正極活物質を保持する正極板の方が導電性に劣るからで
ある。このため、電池の大型化を図るに際しては、先ず
正極板における電位分布差に起因する過充電や過放電が
問題になり、特に一枚の負極板に一枚の正極板を対応さ
せた巻回型のリチウム二次電池においては、部分的な過
充電や過放電に起因するトラブルが電池性能や電池寿命
を直接的に左右する原因になるため、問題が一層深刻と
なる。[0004] The above-mentioned potential distribution difference appears more remarkably in the positive electrode plate than in the negative electrode plate. The reason for this is that a positive electrode plate that holds a positive electrode active material such as a metal oxide has lower conductivity than a negative electrode plate that holds a positive electrode active material such as a carbon material. For this reason, when attempting to increase the size of the battery, first, overcharging and overdischarging due to the potential distribution difference in the positive electrode plate become a problem, and in particular, winding in which one negative electrode plate corresponds to one positive electrode plate In a lithium secondary battery of the type, the problem becomes more serious because troubles caused by partial overcharge or overdischarge directly affect battery performance and battery life.
【０００５】本発明は、リチウム二次電池における上記
問題点を解消することを目的とするものであり、部分的
な過充電や過放電が生じ難く、かつ電極板の一部でトラ
ブルが生じた場合であっても、直ちに電池寿命の終焉を
招かない構造のリチウム二次電池を提供することを目的
とする。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems in a lithium secondary battery, in which partial overcharging or overdischarging hardly occurs and trouble occurs in a part of an electrode plate. Even in such a case, an object of the present invention is to provide a lithium secondary battery having a structure that does not immediately end the battery life.
【０００６】[0006]
【課題を解決するための手段】上記目的を達成するため
に、本発明は次のように構成されている。請求項１記載
の発明は、集電リードを備えた正極板と、集電リードを
備えた負極板とがセパレータを介して対向してなる発電
体が電池缶に収容されたリチウム二次電池において、前
記発電体が、負極板に対する正極板の枚数比を２以上と
したものであることを特徴とする。In order to achieve the above object, the present invention is configured as follows. The invention according to claim 1 is a lithium secondary battery in which a power generator in which a positive electrode plate provided with a current collecting lead and a negative electrode plate provided with a current collecting lead are opposed via a separator is housed in a battery can. The power generator is characterized in that the number ratio of the positive electrode plate to the negative electrode plate is 2 or more.
【０００７】上記したごとく、リチウム二次電池の電極
板内における電位分布の不均一性は、負極板よりも正極
板において大きいので、正負極板の対向枚数比が１であ
ると、部分的な過充電や過放電が生じ易い。ここで、一
枚の負極板に複数枚の正極板を対向させた上記構成であ
ると、正極板における電位分布差を小さくできるので、
充放電が円滑になされる。よって、上記構成によると、
電池を大型化した場合であっても、過放電、過充電によ
る活物質の結晶構造の破壊等が抑制され、その結果とし
て長寿命の電池が得られる。As described above, the nonuniformity of the potential distribution in the electrode plate of the lithium secondary battery is larger in the positive electrode plate than in the negative electrode plate. Overcharge and overdischarge are likely to occur. Here, with the above configuration in which a plurality of positive plates are opposed to one negative plate, the potential distribution difference in the positive plate can be reduced,
Charging and discharging are performed smoothly. Therefore, according to the above configuration,
Even when the size of the battery is increased, destruction of the crystal structure of the active material due to overdischarge and overcharge is suppressed, and as a result, a long-life battery is obtained.
【０００８】また、複数枚の正極板を用いる上記構成で
は、複数枚の正極板の一枚にトラブルが起きても、他の
正極板は当該正極板と独立的に存在しているので、直ち
に電池寿命の終焉に直結しない。なお、上記構成におけ
る発電体には、負極板を１枚とし、この負極板に複数枚
の正極板を対向させた構成、または複数枚の負極板のそ
れぞれに複数枚の正極板を対向させた構成の双方を含
む。Further, in the above-described configuration using a plurality of positive plates, even if a trouble occurs in one of the plurality of positive plates, the other positive plates are present independently of the positive plates, so Does not directly lead to the end of battery life. Note that the power generator in the above configuration has a single negative electrode plate and a plurality of positive electrode plates opposed to the negative electrode plate, or a plurality of positive electrode plates opposed to each of the plurality of negative electrode plates. Includes both configurations.
【０００９】請求項２記載の発明は、請求項１に記載の
リチウム二次電池において、前記複数枚の正極板が、正
極集電リードを介して、各々の正極板に対応させて設け
た電池缶外の外部端子にそれぞれ接続されていることを
特徴とする。According to a second aspect of the present invention, in the lithium secondary battery according to the first aspect, the plurality of positive plates are provided corresponding to each of the positive plates via a positive current collecting lead. It is characterized in that it is connected to an external terminal outside the can.
【００１０】この構成であると、電池の外より外部端子
を通して各々の正極板の出力状態（トラブルの発生を含
む）を容易に検出することができる。よって、この検出
結果に基づいて、過充電や過放電が発生する恐れのある
正極板、或いは過充電や過放電に起因するトラブルが発
生した正極板を不使用にし、正常に機能している正極板
のみを使用するようにすることができる。これにより常
に良好な状態で電池を動作させることができるので、電
池の安全性が高まると共に、電池性能の極端な低下を防
止できる。なお、活物質層の厚みや活物質組成にバラツ
キがある場合においても、部分的な過充電や過放電が発
生するが、本発明によればこのような過充電や過放電を
も検知可能であるので、本発明は大型以外の電池につい
ても有効に機能する。With this configuration, the output state (including occurrence of trouble) of each positive electrode plate can be easily detected through an external terminal from outside the battery. Therefore, based on the detection result, the positive electrode plate in which overcharging or overdischarging may occur or the positive electrode plate in which trouble due to overcharging or overdischarging occurs is disused, and a positive electrode that functions normally Only plates can be used. As a result, the battery can always be operated in a good state, so that the safety of the battery is enhanced and the battery performance can be prevented from being extremely lowered. Note that, even when the thickness of the active material layer and the active material composition vary, partial overcharge or overdischarge occurs, but according to the present invention, such overcharge or overdischarge can be detected. As such, the present invention works effectively for non-large batteries.
【００１１】請求項３記載の発明は、請求項２に記載の
リチウム二次電池において、前記正極板のそれぞれの集
電リードの途中に熱スイッチが取り付けられていること
を特徴とする。According to a third aspect of the present invention, in the lithium secondary battery according to the second aspect, a heat switch is mounted in the middle of each current collecting lead of the positive electrode plate.
【００１２】ここで熱スイッチとは、外部からの熱の付
与、または通電による発熱によって通電が遮断されるも
ので、ヒューズなどに代表されるものをいう。この構成
であると、正極板（又はこの正極に対応する負極板領
域）のトラブルにより、集電リードに過電流が流れた場
合、通電が自動的に遮断される。よって、電池の安全性
が向上すると共に、発電体の一部で発生したトラブルに
より電池全体の性能が大幅に低下するのを防止できる。Here, the heat switch is a switch which is interrupted by the application of heat from the outside or the heat generated by energization, and is represented by a fuse or the like. With this configuration, when an overcurrent flows through the current collecting lead due to a trouble in the positive electrode plate (or the negative electrode plate region corresponding to the positive electrode), the current is automatically cut off. Therefore, the safety of the battery is improved, and the performance of the entire battery can be prevented from being significantly reduced due to a trouble occurring in a part of the power generator.
【００１３】請求項４記載の発明は、請求項１ないし３
に記載のリチウム二次電池において前記発電体が、正極
板と負極板とをセパレータを介し重ね合わせて巻回した
渦巻型の発電体であることを特徴とする。The invention described in claim 4 is the first to third aspects of the present invention.
Wherein the power generator is a spiral-type power generator in which a positive electrode plate and a negative electrode plate are superposed and wound with a separator interposed therebetween.
【００１４】渦巻型発電体であると、電極板を長くし巻
回回数を増やすことにより、容易に電池の高出力化を図
ることができるが、電極板を長くすると、電位分布が不
均一になるという問題がより深刻になる。また電極板の
一部におけるトラブルが電池全体の性能を大幅に低下さ
せる原因になる。よって、このような渦巻型発電体にお
いて、請求項１ないし３の構成を採用した場合、上記し
た作用効果が一層顕著に発揮される。In the case of a spiral power generator, the output of the battery can be easily increased by lengthening the electrode plate and increasing the number of windings. However, when the electrode plate is lengthened, the potential distribution becomes non-uniform. Problem becomes more serious. In addition, a trouble in a part of the electrode plate causes the performance of the whole battery to be significantly reduced. Therefore, in such a spiral type power generator, when the configurations of claims 1 to 3 are adopted, the above-described effects are more remarkably exhibited.
【００１５】[0015]
【実施の形態】本発明の代表的な実施の形態を、図１〜
図２に基づいて説明する。図１は、本発明リチウム二次
電池の主要部分の構造を模式的に示す説明図であり、図
２は、負極板と正極板との対応関係を説明するための図
である。DESCRIPTION OF THE PREFERRED EMBODIMENTS A typical embodiment of the present invention is shown in FIGS.
A description will be given based on FIG. FIG. 1 is an explanatory view schematically showing a structure of a main part of the lithium secondary battery of the present invention, and FIG. 2 is a view for explaining a correspondence between a negative electrode plate and a positive electrode plate.
【００１６】図１において、１は正負極板をセパレータ
を介して巻回した渦巻型発電体であり、２は複数の正極
板のそれぞれに設けられた正極集電リード、３は正極集
電リードの途中に設けられたヒューズ（熱スイッチ）、
４は正極集電リードに接続される正極外部端子、６は電
池缶、７は電池缶を密閉するための電池缶蓋である。こ
こで、上記正極外部端子４は、電池缶蓋７から外方に突
出して形成されており、正極外部端子４と電池缶蓋７と
は電気絶縁されている。また、上記渦巻発電体１は、図
２に示す一枚の負極板１０にセパレータ１２を介して複
数の正極板１１が一定の間隔で（５〜１５ｍｍ程度）配
列されて、負極板１０と正極板１１が対向する状態で巻
回されている。In FIG. 1, reference numeral 1 denotes a spiral power generator in which positive and negative plates are wound via a separator, 2 denotes a positive current collecting lead provided on each of a plurality of positive plates, and 3 denotes a positive current collecting lead. Fuse (thermal switch) provided in the middle of
4 is a positive electrode external terminal connected to the positive electrode current collecting lead, 6 is a battery can, and 7 is a battery can lid for sealing the battery can. Here, the positive electrode external terminal 4 is formed to protrude outward from the battery can lid 7, and the positive electrode external terminal 4 and the battery can lid 7 are electrically insulated. In the spiral power generator 1, a plurality of positive plates 11 are arranged at regular intervals (about 5 to 15 mm) on a single negative plate 10 shown in FIG. The plate 11 is wound so as to face the same.
【００１７】この電池は更に、渦巻型発電体１と共に電
池缶内に収容される非水電解液（不図示）や、負極板１
０に固定された負極集電リード５、及びこの負極集電リ
ード５に接続された負極外部端子を更に備えている。な
お、図１では作図の都合上、正極集電リードおよび正極
外部端子の数を５個としてあるが、１枚の負極板に対向
させる正極板１１の数は２枚以上であればよく、好まし
くは２０枚以下、より好ましくは１５枚以下とする。通
常の大型リチウム二次電池においては、正負極板の枚数
比を２０とすれば十分な効果が得られる一方、無用に枚
数比を大きくすると、却ってエネルギー密度の低下を招
くからである。The battery further includes a non-aqueous electrolyte (not shown) housed in a battery can together with the spiral power generator 1 and a negative electrode plate 1.
It further includes a negative electrode current collecting lead 5 fixed to 0 and a negative electrode external terminal connected to the negative electrode current collecting lead 5. In FIG. 1, for convenience of drawing, the number of the positive electrode current collecting lead and the number of the positive electrode external terminals are set to five, but the number of the positive electrode plates 11 opposed to one negative electrode plate may be two or more, and is preferable. Is 20 or less, and more preferably 15 or less. This is because, in a normal large-sized lithium secondary battery, a sufficient effect can be obtained if the number ratio of the positive and negative electrodes is set to 20, whereas if the number ratio is increased unnecessarily, the energy density is rather lowered.
【００１８】上記構造のリチウム二次電池において、渦
巻発電体１を構成する負極板としては、リチウム金属や
リチウム合金、または銅箔等からなる集電体の両面に黒
鉛、コークスなどの炭素材料、或いはＬｉx Ｆｅ2 Ｏ3
やＬｉx ＷＯ2 などの金属酸化物、更にはポリアセチレ
ン等の導電性高分子などを固着したものを例示できる。
このうち黒鉛等の炭素材料を固着した負極板を本発明電
池の負極板として用いるのが、サイクル寿命を長くでき
る点で好ましい。In the lithium secondary battery having the above structure, the negative electrode plate constituting the spiral power generator 1 includes a carbon material such as graphite and coke on both surfaces of a current collector made of lithium metal, a lithium alloy, or copper foil. Or Li x Fe 2 O 3
And a metal oxide such as Li x WO 2 or a conductive polymer such as polyacetylene.
Of these, it is preferable to use a negative electrode plate to which a carbon material such as graphite is fixed as the negative electrode plate of the battery of the present invention since the cycle life can be extended.
【００１９】なお、炭素材料としては、黒鉛やコークス
を粉砕したものをそのまま負極活物質として用いてもよ
く、酸やアルカリで処理したもの、加熱処理（５００〜
３７００℃）したもの、膨張化処理したものを用いるの
もよい。更に、黒鉛を負極活物質として用いる場合は、
好ましくは格子面（００２）面におけるｄ値（ｄ002）
が３．３５Å以上、３．３７Å以下で、Ｌｃ値が４００
Å以上のものを用いる。このような特性値の黒鉛は、容
量および電圧平坦性に優れるからである。As the carbon material, a material obtained by pulverizing graphite or coke may be used as it is as a negative electrode active material, a material treated with an acid or an alkali, a heat treatment (500 to
(3700 ° C.) or expanded. Furthermore, when graphite is used as the negative electrode active material,
Preferably, the d value (d 002 ) on the lattice plane (002) plane
Is 3.35 ° or more and 3.37 ° or less and the Lc value is 400
用 い る Use more than one. This is because graphite having such characteristic values is excellent in capacity and voltage flatness.
【００２０】他方、上記渦巻型発電体１の構成部材であ
る正極板１１としては、ニッケル箔等よりなる集電体の
両面に例えばＬｉＣｏＯ2 、ＬｉＮｉＯ2 、ＬｉＭｎ2
Ｏ4などの金属酸化物、又はこれらの複合酸化物を固着
したものが例示できる。また、非水電解液としては、エ
チレンカーボネート、ジエチルカーボネート、ジメトキ
シエタン、スルホランなどの溶媒またはこれらを混合し
た溶媒に、ＬｉＰＦ6、ＬｉＣｌＯ4 、ＬｉＣＦ3 ＳＯ
3 などの電解質塩を０．７〜１．５ｍｏｌ／Ｌの割合で
溶解したものが例示できる。On the other hand, as a positive electrode plate 11, which is a component of the spiral power generator 1, for example, LiCoO 2 , LiNiO 2 , LiMn 2
Examples thereof include a metal oxide such as O 4 or a composite oxide of these metal oxides. Examples of the non-aqueous electrolyte include a solvent such as ethylene carbonate, diethyl carbonate, dimethoxyethane, and sulfolane, or a mixture of these solvents, and LiPF 6 , LiClO 4 , and LiCF 3 SO.
Examples thereof include those in which an electrolyte salt such as 3 is dissolved at a ratio of 0.7 to 1.5 mol / L.
【００２１】また、上記熱スイッチとしては、ヒューズ
などの熱による切断式のもの、温度が上昇すると電気抵
抗が増大する特性をもった高分子材料を用いた電流切断
素子、バイメタルなどが例示できる。Examples of the above-mentioned heat switch include a cut-off type using heat such as a fuse, a current cutting element using a polymer material having a characteristic that the electric resistance increases as the temperature rises, and a bimetal.
【００２２】上記構造のリチウム二次電池は、特別な製
法によることなく製造でき、以下に記述すること以外に
ついては従来のリチウム二次電池の製造方法に準ずれば
よい。すなわち、本発明にかかるリチウム二次電池は、
正極板／負極板の枚数比が２以上であるので、例えば正
極板と負極板の枚数比が１／１の関係にある従来のリチ
ウム二次電池の正極板を複数枚に分割して用いればよ
く、分割された各々の正極板に少なくとも１つ正極集電
リードを設け、かつ各々の正極集電リードに対応する数
の外部端子を電池外に突出させて設ければよい。The lithium secondary battery having the above-described structure can be manufactured without using a special manufacturing method, and may be in accordance with a conventional manufacturing method of a lithium secondary battery except as described below. That is, the lithium secondary battery according to the present invention,
Since the number ratio of the positive electrode plate / negative electrode plate is 2 or more, for example, if the positive electrode plate of a conventional lithium secondary battery in which the number ratio of the positive electrode plate and the negative electrode plate is 1/1 is used by dividing it into a plurality of sheets, At least one positive current collecting lead may be provided on each of the divided positive electrode plates, and the number of external terminals corresponding to each positive current collecting lead may be provided so as to protrude outside the battery.
【００２３】具体的な製法例を示すと、負極板との枚数
比（分割数）に応じ、正極体（負極板と略同サイズの分
割前のもの）の所定箇所に正極集電リードを予め電気溶
接等で固定しておく。次に、図３に示すようにして負極
板と正極体とをセパレータを間に鋏みながら巻回し、分
割数に応じた距離だけ正極体が巻かれたところで正極体
を切断する。更に正極板同志が接触しない程度の隙間を
設けて、再び正極体を加えて巻回し、分割数に応じた距
離だけ正極体が巻かれたところで２回目の切断を行う。
このようにして負極板と正極板とをセパレータを介して
巻回しながら、一定の巻回長に達した段階で正極体のみ
切断し、再び巻回を続行する方法により上記した渦巻型
発電体１を作製する。A specific example of the manufacturing method is as follows. According to the number ratio of the negative electrode plate to the negative electrode plate (the number of divisions), a positive electrode current collector lead is previously placed at a predetermined position of a positive electrode body (before division having the same size as the negative electrode plate). It is fixed by electric welding or the like. Next, as shown in FIG. 3, the negative electrode plate and the positive electrode body are wound with scissors between the separators, and the positive electrode body is cut when the positive electrode body is wound by a distance corresponding to the number of divisions. Further, a gap is provided so that the positive electrodes do not come into contact with each other, the positive electrode body is added again and wound, and the second cutting is performed when the positive electrode body is wound by a distance corresponding to the number of divisions.
While the negative electrode plate and the positive electrode plate are wound through the separator in this way, only the positive electrode body is cut when a certain winding length is reached, and the spiral-type power generator 1 is wound again by a method of continuing the winding again. Is prepared.
【００２４】次に、上記で作製した渦巻型発電体１を電
池缶６内に収容し、正極集電リードのそれぞれを電池缶
蓋７から突出させた正極外部端子４にそれぞれに接続す
る。また、負極集電リードについても同様に負極外部端
子に接続する。この後、電池缶内に非水電解液を注液
し、電池缶蓋を電池缶に嵌合等させて電池缶を密閉す
る。Next, the spiral power generator 1 produced above is housed in a battery can 6, and each of the positive current collecting leads is connected to a positive external terminal 4 protruding from a battery can lid 7. Also, the negative electrode current collecting lead is similarly connected to the negative electrode external terminal. Thereafter, a non-aqueous electrolyte is poured into the battery can, and the battery can is sealed by fitting the battery can lid to the battery can.
【００２５】なお、図１の電池においては、巻回に際し
て正負極板に付設された集電リードの上下関係が逆向き
になるように巻回してあるので、負極外部端子は電池缶
蓋７と反対側に設けられている（図１、２参照）。ま
た、上記においては、電極板や電池缶等の各部材のサイ
ズを記載してないが、各部材のサイズは所望する出力や
電池缶の形状等に合わせて適当に設定すればよい。In the battery shown in FIG. 1, the current collecting leads attached to the positive and negative electrodes are wound in such a way that the vertical relationship is reversed. It is provided on the opposite side (see FIGS. 1 and 2). In the above description, the size of each member such as the electrode plate and the battery can is not described, but the size of each member may be appropriately set according to the desired output, the shape of the battery can, and the like.
【００２６】更に、正負極板に付設する集電リードの位
置としては、特に限定されるものではないが、リチウム
イオンを挿入脱離させるタイプのリチウム二次電池の場
合においては、好ましくは正負集電リードが直接的に対
向しない位置とし、より好ましくは負極集電リードを正
極活物質のない位置とするのがよい。正極活物質と対向
する位置に負極集電リードを配置した場合、負極側にリ
チウムイオンの納まるべき場所（負極活物質）がないた
め金属リチウムが析出する恐れがあるからである。この
ことからして、正極板とその隣の正極板との間に位置さ
せて負極集電リードを設けるのもよい。The position of the current collecting lead attached to the positive / negative electrode plate is not particularly limited. However, in the case of a lithium secondary battery of a type in which lithium ions are inserted and desorbed, it is preferable that the positive and negative current collecting leads are provided. It is preferable that the current collecting lead is not directly opposed to each other, and more preferably that the negative electrode current collecting lead is a position where no positive electrode active material exists. This is because, when the negative electrode current collecting lead is arranged at a position facing the positive electrode active material, there is no place (negative electrode active material) where lithium ions can be accommodated on the negative electrode side, so that metallic lithium may be deposited. For this reason, the negative electrode current collecting lead may be provided between the positive electrode plate and the adjacent positive electrode plate.
【００２７】ところで、以上では巻回型リチウム二次電
池を例にして説明したが、本発明はこれに限定されるも
のではなく、積層型のリチウム二次電池についても適用
できる。また、上記では負極板の枚数を一枚としたが、
２枚以上の負極板のそれぞれに複数の正極板を対向させ
るものであってもよい。更に、複数枚の負極板のそれぞ
れに複数枚の正極板を対向させる構成においては、正極
板のみでなく、複数の負極板のそれぞれに負極集電リー
ドと負極外部端子を設けるのもよい。この構成である
と、負極板内における電位分布差を低減でき、また負極
にトラブルが発生した場合、トラブル発生領域の負極板
と正極板を不使用にする態様での使用が可能になる。よ
って、この構成は、１０Ａｈ程度以上の超大型のリチウ
ム二次電池に特に有効である。Although the above description has been made with reference to a wound lithium secondary battery as an example, the present invention is not limited to this, and can also be applied to a stacked lithium secondary battery. In the above description, the number of the negative electrode plates is one, but
A plurality of positive plates may be opposed to each of two or more negative plates. Further, in a configuration in which a plurality of positive plates are opposed to a plurality of negative plates, a negative current collecting lead and a negative external terminal may be provided on each of the plurality of negative plates in addition to the positive plate. With this configuration, the potential distribution difference in the negative electrode plate can be reduced, and when a trouble occurs in the negative electrode, it is possible to use the negative electrode plate and the positive electrode plate in a trouble occurrence area in a mode where they are not used. Therefore, this configuration is particularly effective for an ultra-large lithium secondary battery of about 10 Ah or more.
【００２８】[0028]
【実施例】実施例に基づいて本発明の内容を更に具体的
に説明する。 〔負極板の作製〕格子面（００２）面におけるｄ値（ｄ
002 ）が３．３５６Åであり、Ｌｃ値が１０００Åを超
える黒鉛塊をジェット粉砕した後、篩にかけて平均粒子
径１０μｍの負極活物質としての黒鉛粉末を作製した。
他方、結着剤であるポリフッ化ビニリデンをＮ−メチル
−２−ピロリドン（ＮＭＰ）に溶解したＮＭＰ溶液を作
製した。そして、上記黒鉛粉末にこのＮＭＰ溶液を、黒
鉛粉末とポリフッ化ビニリデンの重量比が８５：１５に
なるように加えて混練し、負極活物質スラリーを調製し
た。この負極活物質スラリーを負極集電体としての銅箔
の両面にドクターブレード法により塗布し、１５０℃で
２時間減圧乾燥し負極板を製した。EXAMPLES The contents of the present invention will be described more specifically based on examples. [Production of Negative Electrode Plate] The d value (d
002 ) is 3.356 ° and the Lc value exceeds 1000 ° was jet-pulverized, and then sieved to prepare a graphite powder as a negative electrode active material having an average particle diameter of 10 μm.
On the other hand, an NMP solution in which polyvinylidene fluoride as a binder was dissolved in N-methyl-2-pyrrolidone (NMP) was prepared. Then, this NMP solution was added to the graphite powder so that the weight ratio of the graphite powder to polyvinylidene fluoride became 85:15 and kneaded to prepare a negative electrode active material slurry. This negative electrode active material slurry was applied to both surfaces of a copper foil as a negative electrode current collector by a doctor blade method, and dried under reduced pressure at 150 ° C. for 2 hours to produce a negative electrode plate.
【００２９】〔正極板の作製〕リチウムの水酸化物とコ
バルトの水酸化物を混合し、空気中で８００℃で２４時
間焼成して正極活物質としてのＬｉＣｏＯ2 を作製し
た。この正極活物質と導電剤としての人造黒鉛を重量比
９０：５の比で混合して、正極合剤となした。次いでこ
の正極合剤に上記と同様のＮＭＰ溶液を、上記正極合剤
とポリフッ化ビニリデンの重量比が９５：５になるよう
に加え混練して正極活物質スラリーを調製した。[Preparation of Positive Electrode Plate] A hydroxide of lithium and a hydroxide of cobalt were mixed and fired in air at 800 ° C. for 24 hours to prepare LiCoO 2 as a positive electrode active material. This positive electrode active material and artificial graphite as a conductive agent were mixed at a weight ratio of 90: 5 to form a positive electrode mixture. Next, the same NMP solution as described above was added to the positive electrode mixture so that the weight ratio of the positive electrode mixture and polyvinylidene fluoride became 95: 5, and kneaded to prepare a positive electrode active material slurry.
【００３０】なお、正極負極活物質スラリーの塗布に際
しては、後の工程で正極集電リードを固定する部位（巻
回方向の端部；図２参照）にはスラリーが塗布されない
ようにした。In applying the positive and negative electrode active material slurry, the portion where the positive electrode current collecting lead was fixed in the subsequent step (end in the winding direction; see FIG. 2) was not coated with the slurry.
【００３１】上記正極活物質スラリーを正極集電体とし
てのアルミニウム箔の両面にドクターブレード法により
塗布し、１５０℃で２時間減圧乾燥した。このようにし
て上記負極板と同様なサイズの正極体（分割前の正極
板）を作製した。The positive electrode active material slurry was applied to both surfaces of an aluminum foil as a positive electrode current collector by a doctor blade method, and dried under reduced pressure at 150 ° C. for 2 hours. Thus, a positive electrode body (positive electrode plate before division) having the same size as the above negative electrode plate was produced.
【００３２】〔正負集電リードの取付け〕活物質が塗布
されていない箇所に、集電リードを電気溶接し固定し
た。なお、この固定をリベットや、または集電リードと
集電体を重ね、針等の金属棒で貫通穴を開けた後、両部
材をプレスする方法で行ってもよい。[Attachment of Positive and Negative Current Collector Leads] A current collector lead was fixed by welding to a portion where the active material was not applied. The fixing may be performed by a method in which a rivet or a current collecting lead and a current collector are overlapped, a through hole is opened with a metal rod such as a needle, and both members are pressed.
【００３３】〔電解液の調製〕エチレンカーボネートと
ジエチルカーボネートとを体積比１：１の割合で混合し
た混合溶媒に、ＬｉＰＦ6 を１Ｍ（モル／リットル）の
割合で溶かし非水電解液とした。[Preparation of Electrolyte Solution] LiPF 6 was dissolved at a ratio of 1M (mol / liter) in a mixed solvent of ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1 to obtain a non-aqueous electrolyte solution.
【００３４】〔電池の組立〕イオン透過性のポリエチレ
ンからなるセパレータを上記正負極板の間に鋏みなが
ら、正負極板とセパレータとを巻回し正極体が所定の長
さまで巻回されたとき、正極体を切断し１枚目の正極板
とした。次いで、この正極板の終端から約１０ｍｍずら
した位置に正極体を配置し再び巻回し、この（２枚目）
の巻回始端から所定の長さまで巻回されたときに、正極
体を切断し２枚目の正極板とした。このようにして順次
巻回を行った。そして、負極板と正極板との枚数比が、
１（切断しないもの；比較例）、２、５、１０、１５、
２０の６通りの渦巻型発電体を作製した。なお、この巻
回方法は前記図３で示した方法と同じである。[Assembly of Battery] While the separator made of ion-permeable polyethylene is scissored between the positive and negative electrode plates, the positive and negative electrode plates and the separator are wound, and when the positive electrode body is wound to a predetermined length, the positive electrode body is removed. This was cut into a first positive electrode plate. Next, the positive electrode body was arranged at a position shifted by about 10 mm from the end of the positive electrode plate, and wound again, and this (second sheet)
Was wound to a predetermined length from the winding start end, and the positive electrode body was cut to obtain a second positive electrode plate. In this way, winding was performed sequentially. Then, the number ratio of the negative electrode plate and the positive electrode plate is
1 (not cut; Comparative Example) 2, 5, 10, 15,
Twenty six types of spiral power generators were produced. This winding method is the same as the method shown in FIG.
【００３５】上記で作製した渦巻型発電体を金属製の電
池缶に入れ、正負極板に付設された集電リードのそれぞ
れを、金属製の電池缶蓋に設けられた対応する外部端子
にそれぞれ電気溶接した。この後、電池缶に上記電解液
を入れ、電池缶蓋を被せて電池を密閉した。このように
して正負極板の枚数比のみが異なる６通りのリチウム二
次電池（電池容量１０Ａｈ）を作製した。これらの電池
を、実施例１（正負極板枚数比２）、実施例２（同
５）、実施例３（同１０）、実施例４（同１５）、実施
例５（同２０）、および比較例１（同１）の電池とす
る。The spiral power generator prepared above is placed in a metal battery can, and each of the current collecting leads attached to the positive and negative electrode plates is connected to a corresponding external terminal provided on the metal battery can lid. Electric welding. Thereafter, the above-mentioned electrolytic solution was put into a battery can, and the battery was sealed by covering the battery can lid. In this way, six types of lithium secondary batteries (battery capacity 10 Ah) differing only in the number ratio of the positive and negative electrode plates were manufactured. These batteries were used in Examples 1 (the ratio of the number of positive and negative electrodes 2), Example 2 (the same as in the fifth example), Example 3 (the same as the above 10), Example 4 (the same as the above 15), Example 5 (the same as the above 20), and The battery of Comparative Example 1 (Same as 1) was used.
【００３６】〔電池の評価〕上記で作製した各種電池の
初期容量と２００サイクル後の放電容量を下記条件で測
定した。また、この測定結果に基づいて２００サイクル
における劣化率を数１に従い算出した。[Evaluation of Battery] The initial capacity and the discharge capacity after 200 cycles of the various batteries prepared above were measured under the following conditions. Further, based on the measurement result, the deterioration rate in 200 cycles was calculated according to Equation 1.
【００３７】（放電容量の測定方法）室温にて、４．０
Ａｈ定電流で充電終止電圧が４．１Ｖになるまで充電し
た後、４．０Ａｈ定電流で放電終止電圧が２．７５Ｖに
なるまで放電するサイクルを２００サイクル行った。そ
して、１サイクル目の放電容量と２００サイクル目の放
電容量を測定した。(Method of measuring discharge capacity) At room temperature, 4.0
After charging until the end-of-charge voltage reached 4.1 V with a constant current of Ah, 200 cycles of discharging until the end-of-discharge voltage reached 2.75 V with a constant current of 4.0 Ah were performed. Then, the discharge capacity at the first cycle and the discharge capacity at the 200th cycle were measured.
【００３８】[0038]
【数１】 (Equation 1)
【００３９】測定結果を表１に示した。表１から、正極
分割数（正負極板枚数比）が１の比較例に比較し、正極
分割数を２以上とした実施例１〜５の電池は何れも２０
０サイクルにおける劣化率が小さいことが確認された。
また、表１において、正極分割数が多くなるにつれ劣化
率が小さくなる傾向があることが確認された。但し、こ
の電池（容量１０Ａｈ）においては、正負極板の枚数比
を１５を越えるようにしても、更なる効果の向上がなか
った。Table 1 shows the measurement results. From Table 1, the batteries of Examples 1 to 5 in which the number of divided positive electrodes was 2 or more were 20 compared to the comparative example in which the number of divided positive electrodes (ratio of the number of positive and negative electrodes) was 1.
It was confirmed that the deterioration rate in 0 cycle was small.
Further, in Table 1, it was confirmed that the deterioration rate tended to decrease as the number of divided positive electrodes increased. However, in this battery (capacity: 10 Ah), the effect was not further improved even if the ratio of the number of positive / negative plates exceeded 15.
【００４０】[0040]
【表１】 [Table 1]
【００４１】[0041]
【発明の効果】以上から明らかなように、本発明による
と、極めて簡単な方法でサイクル劣化率の小さいリチウ
ム二次電池が得られ、本発明によると、サイクル特性や
安全性に優れた高出力のリチウム二次電池を安価に提供
できる。As is clear from the above, according to the present invention, a lithium secondary battery having a small cycle deterioration rate can be obtained by an extremely simple method. According to the present invention, a high output having excellent cycle characteristics and safety can be obtained. Can be provided at a low cost.
【図１】本発明リチウム二次電池の主要部分の構造を示
す説明図である。FIG. 1 is an explanatory view showing a structure of a main part of a lithium secondary battery of the present invention.
【図２】本発明にかかるリチウム二次電池の負極板と正
極板との対応関係を示す説明図である。FIG. 2 is an explanatory diagram showing a correspondence between a negative electrode plate and a positive electrode plate of a lithium secondary battery according to the present invention.
【図３】本発明にかかる渦巻型発電体の製造方法を説明
するための図である。FIG. 3 is a view for explaining a method of manufacturing a spiral power generator according to the present invention.
１ 巻回型発電体 ２ 正極集電リード ３ 熱スイッチ（ヒューズ） ４ 正極外部端子 ５ 負極集電リード ６ 電池缶 ７ 電池缶蓋 １０ 負極板 １１ 正極板 １２ セパレータ DESCRIPTION OF SYMBOLS 1 Winding type power generator 2 Positive electrode current collecting lead 3 Thermal switch (fuse) 4 Positive electrode external terminal 5 Negative current collecting lead 6 Battery can 7 Battery can lid 10 Negative electrode plate 11 Positive electrode plate 12 Separator
フロントページの続き (72)発明者 野上 光造 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 米津 育郎 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内 (72)発明者 西尾 晃治 大阪府守口市京阪本通２丁目５番５号 三 洋電機株式会社内Continued on the front page. (72) Inventor Kozo Nogami 2-5-1-5, Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Ikuro Yonezu 2-5-2-5, Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd. (72) Inventor Koji Nishio 2-5-5 Keihanhondori, Moriguchi-shi, Osaka Sanyo Electric Co., Ltd.
Claims (4)
ドを備えた負極板とがセパレータを介して対向してなる
発電体が電池缶に収容されたリチウム二次電池におい
て、 前記発電体は、負極板に対する正極板の枚数比が２以上
であることを特徴とするリチウム二次電池。1. A lithium secondary battery in which a power generating body in which a positive electrode plate provided with a current collecting lead and a negative electrode plate provided with a current collecting lead are opposed via a separator is accommodated in a battery can. A lithium secondary battery, wherein the body has a ratio of the number of positive electrodes to the number of negative electrodes of 2 or more.
を介して、各々の正極板に対応させて設けた電池缶外の
外部端子にそれぞれ接続されていることを特徴とする請
求項１に記載のリチウム二次電池。2. The battery according to claim 1, wherein the plurality of positive plates are connected to external terminals outside the battery can provided corresponding to the respective positive plates via the current collecting leads. 2. The lithium secondary battery according to 1.
中には、熱スイッチが取り付けられていることを特徴と
する請求項２に記載のリチウム二次電池。3. The lithium secondary battery according to claim 2, wherein a heat switch is mounted in the middle of each of the current collecting leads of the positive electrode plate.
レータを介し重ね合わせて巻回した渦巻型の発電体であ
ることを特徴とする請求項１ないし３に記載のリチウム
二次電池。4. The lithium secondary battery according to claim 1, wherein the power generator is a spiral-type power generator in which a positive electrode plate and a negative electrode plate are overlapped and wound with a separator interposed therebetween. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9234037A JPH1173994A (en) | 1997-08-29 | 1997-08-29 | Lithium secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9234037A JPH1173994A (en) | 1997-08-29 | 1997-08-29 | Lithium secondary battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH1173994A true JPH1173994A (en) | 1999-03-16 |
Family
ID=16964584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9234037A Pending JPH1173994A (en) | 1997-08-29 | 1997-08-29 | Lithium secondary battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH1173994A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006156365A (en) * | 2004-11-29 | 2006-06-15 | Samsung Sdi Co Ltd | Lithium secondary battery |
| JP2009176582A (en) * | 2008-01-25 | 2009-08-06 | Hitachi Maxell Ltd | Non-aqueous electrolyte secondary battery |
| WO2017110662A1 (en) * | 2015-12-25 | 2017-06-29 | 株式会社日立製作所 | Lithium ion battery |
| JPWO2023242982A1 (en) * | 2022-06-15 | 2023-12-21 |
-
1997
- 1997-08-29 JP JP9234037A patent/JPH1173994A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006156365A (en) * | 2004-11-29 | 2006-06-15 | Samsung Sdi Co Ltd | Lithium secondary battery |
| JP2009176582A (en) * | 2008-01-25 | 2009-08-06 | Hitachi Maxell Ltd | Non-aqueous electrolyte secondary battery |
| WO2017110662A1 (en) * | 2015-12-25 | 2017-06-29 | 株式会社日立製作所 | Lithium ion battery |
| JPWO2023242982A1 (en) * | 2022-06-15 | 2023-12-21 |
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