JP3419311B2 - Bipolar lithium-ion secondary battery - Google Patents
Bipolar lithium-ion secondary batteryInfo
- Publication number
- JP3419311B2 JP3419311B2 JP20060898A JP20060898A JP3419311B2 JP 3419311 B2 JP3419311 B2 JP 3419311B2 JP 20060898 A JP20060898 A JP 20060898A JP 20060898 A JP20060898 A JP 20060898A JP 3419311 B2 JP3419311 B2 JP 3419311B2
- Authority
- JP
- Japan
- Prior art keywords
- battery
- negative electrode
- positive electrode
- current collector
- collector foil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、バイポーラ型リチ
ウムイオン２次電池の構造の改良に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to improvement of the structure of a bipolar lithium ion secondary battery.
【０００２】[0002]
【従来の技術】従来より、リチウムイオン２次電池を複
数直列に接続したものを１個の電池としたバイポーラ型
リチウムイオン２次電池が使用されている。このような
バイポーラ型リチウムイオン２次電池は、正極と負極と
の間に電解質を含みリチウムイオン導電性のあるセパレ
ータを挟んで電池構成体を形成し、これを電極方向に積
層し、各電池構成体を直列接続することにより形成して
いた。このようなバイポーラ型リチウムイオン２次電池
の例が特開昭５９−９０３５９号公報に開示されてい
る。2. Description of the Related Art Conventionally, a bipolar type lithium ion secondary battery has been used in which a plurality of lithium ion secondary batteries connected in series is used as one battery. In such a bipolar lithium ion secondary battery, a battery assembly is formed by sandwiching a separator containing an electrolyte between a positive electrode and a negative electrode and having lithium ion conductivity, and the battery assembly is stacked in the electrode direction. It was formed by connecting the bodies in series. An example of such a bipolar lithium ion secondary battery is disclosed in Japanese Patent Laid-Open No. 59-90359.
【０００３】図１５には、本従来例のバイポーラ型リチ
ウムイオン２次電池の断面図が示される。図１５におい
て、電池ケース１００の中には、正極集電箔１０上に正
極活物質１２を塗布して形成された正極と、負極集電箔
１４上に負極活物質１６を塗布して形成された負極との
間に、リチウムイオン導電性を有するセパレータ１８を
挟んで電池構成体とし、この電池構成体が複数電極方向
に積層された構造を有するバイポーラ型リチウムイオン
２次電池が収容されている。このようにして構成された
バイポーラ型リチウムイオン２次電池の両方の積層端面
は、それぞれ正極集電箔１０と負極集電箔１４になって
おり、これらに正極端子リード２０及び負極端子リード
２２が接続されている。FIG. 15 shows a sectional view of a bipolar type lithium ion secondary battery of this conventional example. 15, in the battery case 100, a positive electrode formed by applying the positive electrode active material 12 on the positive electrode current collector foil 10 and a negative electrode active material 16 applied on the negative electrode current collector foil 14 are formed. A bipolar type lithium ion secondary battery having a structure in which a separator 18 having lithium ion conductivity is sandwiched between the negative electrode and the negative electrode to form a battery structure, and the battery structure is stacked in a plurality of electrode directions is accommodated. . Both of the laminated end surfaces of the bipolar lithium-ion secondary battery configured in this way are the positive electrode current collector foil 10 and the negative electrode current collector foil 14, respectively, and the positive electrode terminal lead 20 and the negative electrode terminal lead 22 are attached to them. It is connected.
【０００４】[0004]
【発明が解決しようとする課題】しかし、上記従来のバ
イポーラ型リチウムイオン２次電池においては、各電池
構成体を、その積層方向には薄くすることができるが、
これと同時に大きな容量を得るためには、正極及び負極
の面積を大きくする必要がある。このため、正極、負極
の面積方向にコンパクト化するのが困難であるという問
題があった。However, in the above-mentioned conventional bipolar type lithium ion secondary battery, each battery component can be thinned in the stacking direction.
At the same time, in order to obtain a large capacity, it is necessary to increase the area of the positive electrode and the negative electrode. Therefore, there is a problem that it is difficult to make the positive electrode and the negative electrode compact in the area direction.
【０００５】また、各電池構成体の間隔が、数１０〜１
００μｍと薄いので、電池構成体の周囲の絶縁処理が難
しいという問題もあった。Further, the interval between the battery components is several tens to one.
Since it is as thin as 00 μm, there is also a problem that it is difficult to insulate the periphery of the battery structure.
【０００６】本発明は、上記従来の課題に鑑みなされた
ものであり、その目的は、容量が大きくかつコンパクト
化が可能であり、絶縁性の向上したバイポーラ型リチウ
ムイオン２次電池を提供することにある。The present invention has been made in view of the above conventional problems, and an object thereof is to provide a bipolar type lithium ion secondary battery having a large capacity, a compact size, and improved insulation. It is in.
【０００７】[0007]
【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、バイポーラ型リチウムイオン２次電池で
あって、正極と負極との間にセパレータを挟んだ状態で
捲回される電池構成体が、絶縁体を介して複数個同心円
状に捲回され、内側の電池構成体から外側の電池構成体
に向かって、順次電気的に直列に接続され、各接続部で
は、内側の電池構成体の正極または負極の集電箔と外側
の電池構成体の負極または正極の集電箔とが接続され、
内側の電池構成体と外側の電池構成体との接続部を構成
する集電箔が、内側の電池構成体の外周全体を包む構造
となっていることを特徴とする。 In order to achieve the above object, the present invention relates to a bipolar lithium ion secondary battery, which is wound with a separator sandwiched between a positive electrode and a negative electrode. A plurality of components are concentrically wound via an insulator, and are sequentially electrically connected in series from the inner battery component toward the outer battery component, and at each connection portion.
Is the positive or negative collector foil of the inner battery assembly and the outer
Is connected to the negative electrode or positive electrode current collector foil of the battery assembly of
Configures the connection between the inner battery structure and the outer battery structure
A structure in which the current collecting foil wraps around the entire outer periphery of the inner battery structure
It is characterized in that.
【０００８】また、バイポーラ型リチウムイオン２次電
池であって、正極と負極との間にセパレータを挟んだ状
態で捲回される電池構成体が、絶縁体を介して複数個同
心円状に捲回され、内側の電池構成体から外側の電池構
成体に向かって、順次電気的に直列に接続され、各接続
部では、内側の電池構成体の正極または負極の集電箔と
外側の電池構成体の負極または正極の集電箔とが接続さ
れ、内側の電池構成体と外側の電池構成体の電気容量は
同じで、内部抵抗を内側の電池構成体ほど高くしたこと
を特徴とする。Further, in a bipolar type lithium ion secondary battery, a plurality of battery constituents wound in a state where a separator is sandwiched between a positive electrode and a negative electrode are concentrically wound through an insulator. Are sequentially and electrically connected in series from the inner battery structure toward the outer battery structure, and at each connection part, the positive electrode or negative electrode current collector foil of the inner battery structure and the outer battery structure are connected. The negative electrode or the positive electrode current collector foil is connected , and the electric capacities of the inner battery component and the outer battery component are
The same is also characterized in that the inner resistance of the inner battery structure is made higher .
【０００９】[0009]
【００１０】[0010]
【００１１】[0011]
【００１２】[0012]
【発明の実施の形態】以下、本発明の実施の形態（以下
実施形態という）を、図面に従って説明する。BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention (hereinafter referred to as embodiments) will be described below with reference to the drawings.
【００１３】実施形態１．図１及び図２には、本実施形
態に係るバイポーラ型リチウムイオン２次電池を構成す
る電池構成体の例が示される。図１において、正極集電
箔１０の上に正極活物質１２を塗布して構成された正極
と、負極集電箔１４の上に負極活物質１６を塗布して構
成された負極との間にリチウムイオン導電性を有するセ
パレータ１８を挟んで電池構成体２６を構成する。この
電池構成体２６は、図１に示されるように捲回される。
この場合、負極集電箔１４の外側には、絶縁フィルム２
４が積層されている。これにより、上記電池構成体２６
を捲回したときに、正極集電箔１０と負極集電箔１４と
が短絡することを防止している。このようにして捲回し
た電池構成体２６の断面図が図２に示される。図２に示
されるように、電池構成体２６は、その最内部に正極集
電箔１０が、また最外部に負極集電箔１４が露出してい
る。Embodiment 1. FIG. 1 and FIG. 2 show an example of a battery structure that constitutes the bipolar lithium-ion secondary battery according to this embodiment. In FIG. 1, between the positive electrode formed by applying the positive electrode active material 12 on the positive electrode current collector foil 10 and the negative electrode formed by applying the negative electrode active material 16 on the negative electrode current collector foil 14. The battery structure 26 is configured with the lithium ion conductive separator 18 interposed therebetween. The battery structure 26 is wound as shown in FIG.
In this case, the insulating film 2 is provided outside the negative electrode current collector foil 14.
4 are stacked. Thereby, the battery structure 26
This prevents the positive electrode current collector foil 10 and the negative electrode current collector foil 14 from being short-circuited when being wound. A cross-sectional view of the battery structure 26 wound in this manner is shown in FIG. As shown in FIG. 2, the battery assembly 26 has the positive electrode current collector foil 10 exposed at the innermost part and the negative electrode current collector foil 14 exposed at the outermost part.
【００１４】なお、図１に示された例では、正極集電箔
１０及び負極集電箔１４には、その片側に正極活物質１
２及び負極活物質１６が塗布されているが、これを図３
に示されるように、それぞれの集電箔１０、１４の両側
に各々正極活物質１２及び負極活物質１６を塗布する構
成としてもよい。この場合には、積層された各層のう
ち、正極集電箔１０と負極集電箔１４との内側に位置す
る正極活物質１２と負極活物質１６との間にセパレータ
１８ａが挟み込まれている。また、負極集電箔１４の外
側の負極活物質１６の更に外側には、やはり同じセパレ
ータ１８ｂが配置されている。これを、矢印Ａの方向に
捲回していくと、上述した内側の正極活物質１２及び負
極活物質１６がセパレータ１８ａを介して対向配置され
るとともに、外側の正極活物質１２及び負極活物質１６
も、負極活物質１６の外側に配置されたセパレータ１８
ｂを介して対向配置されることになる。この場合、負極
集電箔１４の負極活物質１６が塗布されていない部分の
長さを十分に確保しておけば、図３の矢印Ａ方向に捲回
した場合、最内部に正極集電箔１０が露出し、最外部に
負極集電箔１４が露出した構造の電池構成体２６を得る
ことができる。In the example shown in FIG. 1, the positive electrode current collector foil 10 and the negative electrode current collector foil 14 have positive electrode active material 1 on one side thereof.
2 and the negative electrode active material 16 are applied.
As shown in, the positive electrode active material 12 and the negative electrode active material 16 may be applied to both sides of each of the current collector foils 10 and 14, respectively. In this case, the separator 18a is sandwiched between the positive electrode active material 12 and the negative electrode active material 16 located inside the positive electrode current collector foil 10 and the negative electrode current collector foil 14 among the laminated layers. Further, the same separator 18b is also arranged on the outer side of the negative electrode active material 16 on the outer side of the negative electrode current collector foil 14. When this is wound in the direction of arrow A, the inner positive electrode active material 12 and the negative electrode active material 16 described above are arranged to face each other with the separator 18a interposed therebetween, and the outer positive electrode active material 12 and the negative electrode active material 16 are arranged.
The separator 18 disposed outside the negative electrode active material 16
It will be arranged facing each other via b. In this case, if the length of the portion of the negative electrode current collector foil 14 on which the negative electrode active material 16 is not applied is sufficiently secured, when the negative electrode current collector foil 14 is wound in the direction of arrow A in FIG. A battery structure 26 having a structure in which 10 is exposed and the negative electrode current collector foil 14 is exposed at the outermost part can be obtained.
【００１５】図２に示された電池構成体２６は、絶縁体
で覆い、更にこの外周に、図１に示された電池構成体２
６を同心円状に捲回していく。このように、複数の電池
構成体２６が、絶縁体を介して同心円状に捲回され、内
側の電池構成体から外側の電池構成体に向かって、順次
電気的に直列に接続され、本実施形態に係るバイポーラ
型リチウムイオン２次電池が構成される。このように、
電池構成体２６を捲回することにより、捲回しないで積
層する場合に比べコンパクト化でき、容量が大きくかつ
コンパクト化されたバイポーラ型リチウムイオン２次電
池とすることができる。The battery structure 26 shown in FIG. 2 is covered with an insulator, and the battery structure 2 shown in FIG.
6 is wound concentrically. In this way, the plurality of battery components 26 are concentrically wound with the insulator interposed therebetween, and are sequentially electrically connected in series from the inner battery component toward the outer battery component. A bipolar lithium-ion secondary battery according to the aspect is configured. in this way,
By winding the battery structure 26, the bipolar type lithium ion secondary battery can be made compact as compared with the case of stacking without winding, and has a large capacity and a compact size.
【００１６】以上のようなバイポーラ型リチウムイオン
２次電池の断面図が図４に示される。図４において、最
内部の電池構成体２６ａから最外部の電池構成体２６ｄ
までは、絶縁容器２８を介して同心円状に捲回されてい
る。これらが電池ケース１００内に収められ、内側の電
池構成体２６ａから順次電池構成体２６ｂ、２６ｃ、２
６ｄの順番に直列接続用リード線３０によって直列接続
されていく。前述したように、電池構成体２６の最内部
には、正極集電箔１０が露出しているので、これに正極
端子リード２０を接続し、電池構成体２６の最外部に
は、負極集電箔１４が露出しているのでこれに負極端子
リード２２を接続する。A cross-sectional view of the bipolar type lithium ion secondary battery as described above is shown in FIG. In FIG. 4, from the innermost battery structure 26a to the outermost battery structure 26d.
Up to the above, they are wound concentrically via the insulating container 28. These are housed in the battery case 100, and the battery components 26b, 26c, and 2 are sequentially arranged from the inner battery component 26a.
The lead wires 30 for serial connection are connected in series in the order of 6d. As described above, since the positive electrode current collector foil 10 is exposed at the innermost part of the battery structure 26, the positive electrode terminal lead 20 is connected to this, and the positive electrode current collector foil 10 is provided at the outermost part of the battery structure 26. Since the foil 14 is exposed, the negative terminal lead 22 is connected to it.
【００１７】図５には、図４に示された本実施形態に係
るバイポーラ型リチウムイオン２次電池のＶ−Ｖ断面図
が示される。ただし、電池ケース１００は省略してあ
る。本実施形態においては、４つの電池構成体２６ａ、
２６ｂ、２６ｃ、２６ｄが、それぞれ内側の電池構成体
２６ａから順次その外側に同心円状に捲回され、内側の
電池構成体２６ａから外側の電池構成体２６ｄに向かっ
て直列に接続されている。このバイポーラ型リチウムイ
オン２次電池を使用する場合には、正極端子リード２０
と負極端子リード２２とを介して充放電を行わせる。FIG. 5 shows a VV sectional view of the bipolar lithium ion secondary battery according to this embodiment shown in FIG. However, the battery case 100 is omitted. In this embodiment, four battery components 26a,
26b, 26c, and 26d are sequentially wound concentrically from the inner battery structure 26a to the outer side thereof, and are connected in series from the inner battery structure 26a toward the outer battery structure 26d. When using this bipolar type lithium ion secondary battery, the positive electrode terminal lead 20
Charge and discharge is performed via the negative electrode terminal lead 22 and the negative electrode terminal lead 22.
【００１８】なお、本実施形態では、最内部に正極が、
最外部に負極が形成されているが、電池構成体２６の積
層順または捲回方向を逆にして、正極と負極との配置を
逆にすることもできる。In this embodiment, the positive electrode is the innermost
Although the negative electrode is formed on the outermost part, the stacking order or the winding direction of the battery structure 26 may be reversed to reverse the arrangement of the positive electrode and the negative electrode.
【００１９】以下に、本実施形態に係るバイポーラ型リ
チウムイオン２次電池の具体例を実施例１として説明す
る。A specific example of the bipolar type lithium ion secondary battery according to this embodiment will be described below as Example 1.
【００２０】実施例１．正極活物質１２としてＬｉＭｎ
2Ｏ4を使用し、これを正極集電箔１０としてのアルミニ
ウム箔上に塗布して正極を構成した。また、負極活物質
１６として黒鉛を使用し、これを負極集電箔１４として
の銅箔上に塗布して負極を構成した。また、セパレータ
１８として不織布を使用した。これらを図１に示される
ように積層し、これを捲回して電池構成体２６とした。
このように構成した電池構成体２６を、絶縁容器２８と
してのポリプロピレン（ＰＰ）製の袋に入れ、さらにそ
の外周に以上に述べたと同様の電池構成体２６を捲回し
て、この全体もポリプロピレン製の袋に入れた。このよ
うに、ポリプロピレン製の袋に入れた電池構成体の外周
にさらに電池構成体を捲回していき、図４に示されるよ
うに絶縁容器２８としてのポリプロピレン製の袋を介し
て４個の電池構成体２６ａ、２６ｂ、２６ｃ、２６ｄを
同心円状に捲回した。Example 1. LiMn as the positive electrode active material 12
2 O 4 was used and applied on an aluminum foil as the positive electrode current collector foil 10 to form a positive electrode. Further, graphite was used as the negative electrode active material 16, and this was applied onto a copper foil as the negative electrode current collector foil 14 to form a negative electrode. A nonwoven fabric was used as the separator 18. These were laminated as shown in FIG. 1 and wound to form a battery structure 26.
The battery structure 26 thus configured is put in a polypropylene (PP) bag as the insulating container 28, and the battery structure 26 similar to the one described above is further wound around the bag, and the whole structure is also made of polypropylene. I put it in the bag. In this way, the battery component is further wound around the outer periphery of the battery component placed in the polypropylene bag, and four batteries are inserted through the polypropylene bag as the insulating container 28 as shown in FIG. Constituent bodies 26a, 26b, 26c and 26d were wound concentrically.
【００２１】次に、ＥＣ：ＤＥＣ＝１：１の液体にＬｉ
ＰＦ6を１ｍｏｌ／ｌ溶解させた溶液とＰＶＤＦ−ＨＦ
Ｐとを、その重量比が７：１となるように混合したもの
を電解液として準備した。この電解液を、上述したポリ
プロピレン製の袋に入れられた各電池構成体２６、２６
ｂ、２６ｃ、２６ｄに含浸させ、１２０℃に加熱した後
室温に戻し、電解液を正、負極及びセパレータ１８中で
ゲル化させた。その後ポリプロピレン製の袋の開口部を
熱プレスにより閉じ、各電池構成体２６、２６ｂ、２６
ｃ、２６ｄを完全に封止し分離した。その後、内側の電
池構成体２６ａから外側の電池構成体２６ｄに向かっ
て、直列接続用リード線３０によって順次電気的に直列
に接続した。最後にこれらを電池ケース１００内に封入
し、最内部の正極集電箔１０と最外部の負極集電箔１４
とに、それぞれ正極端子リード２０及び負極端子リード
２２を接続し、本実施例に係るバイポーラ型リチウムイ
オン２次電池を得た。Next, a liquid of EC: DEC = 1: 1 was added to Li.
PVDF-HF and a solution in which PF 6 was dissolved at 1 mol / l
An electrolyte was prepared by mixing P and P in a weight ratio of 7: 1. Each of the battery components 26, 26 contained in the above-mentioned polypropylene bag is filled with the electrolytic solution.
b, 26c, and 26d were impregnated, heated to 120 ° C., and then returned to room temperature to cause the electrolytic solution to gel in the positive electrode, the negative electrode, and the separator 18. After that, the opening of the polypropylene bag was closed by hot pressing, and each battery structure 26, 26b, 26 was closed.
c and 26d were completely sealed and separated. Then, from the inner battery structure 26a toward the outer battery structure 26d, they were sequentially electrically connected in series by the series connection lead wire 30. Finally, these are enclosed in a battery case 100, and the innermost positive electrode current collector foil 10 and the outermost negative electrode current collector foil 14 are enclosed.
A positive electrode terminal lead 20 and a negative electrode terminal lead 22 were connected to and, respectively, to obtain a bipolar lithium ion secondary battery according to this example.
【００２２】このようにして得たバイポーラ型リチウム
イオン２次電池を評価したところ、平均電圧として１
５．８Ｖを得ることができた。また、充電状態で１０日
間放置した後も、その電圧は１５．６Ｖを保持してい
た。比較例として、図１に示された電池構成体２６を捲
回せずに、積層した状態で、その周囲を絶縁したバイポ
ーラ型リチウムイオン２次電池を同様に評価した。その
結果、当初１５．８Ｖの電圧が得られたが、１０日間放
置した後には、１０．８Ｖまで低下した。これは、各電
池構成体２６の厚さが数１０〜１００μｍ程度と薄いの
で、周囲の絶縁処理が困難であることから、漏れ電流が
大きいためと考えられる。The bipolar lithium-ion secondary battery thus obtained was evaluated and found to have an average voltage of 1
It was possible to obtain 5.8V. Further, the voltage was kept at 15.6 V even after being left for 10 days in a charged state. As a comparative example, a bipolar lithium-ion secondary battery, in which the battery structure 26 shown in FIG. 1 was laminated without being wound, and the periphery of which was insulated was similarly evaluated. As a result, a voltage of 15.8V was initially obtained, but after leaving it for 10 days, it dropped to 10.8V. It is considered that this is because the thickness of each battery structure 26 is as thin as several tens to 100 μm, and it is difficult to insulate the surroundings, so that the leakage current is large.
【００２３】実施形態２．図６には、本実施形態に係る
バイポーラ型リチウムイオン２次電池の構成の断面図が
示される。また、図７には、図６に示されたバイポーラ
型リチウムイオン２次電池を構成する電池構成体２６の
断面図が示される。Embodiment 2. FIG. 6 shows a cross-sectional view of the configuration of the bipolar lithium-ion secondary battery according to this embodiment. Further, FIG. 7 shows a cross-sectional view of the battery structure 26 that constitutes the bipolar lithium-ion secondary battery shown in FIG.
【００２４】図７において、正極集電箔１０の両面には
正極活物質１２が塗布され、正極を構成している。ま
た、負極集電箔１４の両面には負極活物質１６が塗布さ
れ、負極を構成している。これらの正極活物質１２と負
極活物質１６のうち、内側に配置されたもの同士がセパ
レータ１８ａを介して対向配置されている。また、正極
活物質１２のうち正極集電箔１０の負極と反対側（外
側）に形成されたものには、さらにセパレータ１８ｂが
形成されている。これにより、電池構成体２６が捲回さ
れたときに、外側に配置された正極活物質１２と負極活
物質１６同士がセパレータ１８ｂを介して対向配置され
ることになる。このような電池構成体２６は、一方の正
極集電箔１０と他方の負極集電箔１４とが接続部３２で
接続され、複数個の電池構成体２６が直列に接続されて
いる。このように、正極集電箔１０と他方の負極集電箔
１４とを直接つなぐことにより、接触抵抗を小さくする
ことができる。In FIG. 7, the positive electrode active material 12 is applied to both surfaces of the positive electrode current collector foil 10 to form a positive electrode. Further, the negative electrode active material 16 is applied to both surfaces of the negative electrode current collector foil 14 to form a negative electrode. Among the positive electrode active material 12 and the negative electrode active material 16, those arranged inside are opposed to each other via the separator 18a. Further, a separator 18b is further formed on the positive electrode active material 12 that is formed on the opposite side (outer side) of the positive electrode current collector foil 10 from the negative electrode. As a result, when the battery structure 26 is wound, the positive electrode active material 12 and the negative electrode active material 16 arranged outside are arranged to face each other with the separator 18b interposed therebetween. In such a battery structure 26, one positive electrode current collector foil 10 and the other negative electrode current collector foil 14 are connected at a connecting portion 32, and a plurality of battery structure members 26 are connected in series. In this way, by directly connecting the positive electrode current collector foil 10 and the other negative electrode current collector foil 14, the contact resistance can be reduced.
【００２５】以上のようにして構成された電池構成体
を、図７に示された矢印Ａの方向に捲回すると、図６に
示されるような構造のバイポーラ型リチウムイオン２次
電池を得ることができる。図６においては、正極と負極
との間にセパレータ１８ａ、ｂを挟んだ状態で捲回され
た電池構成体２６が複数個同心円状に捲回された構造と
なっている。また、図７に示されるように、電池構成体
２６は接続部３２により直列に接続されているので、図
６においても、内側の電池構成体２６から外側の電池構
成体２６に向かって、順次電気的に直列に接続された構
造となっている。When the battery assembly thus constructed is wound in the direction of arrow A shown in FIG. 7, a bipolar lithium ion secondary battery having a structure as shown in FIG. 6 is obtained. You can In FIG. 6, a plurality of battery components 26 are wound in a concentric manner with the separators 18a and 18b sandwiched between the positive electrode and the negative electrode. Further, as shown in FIG. 7, since the battery components 26 are connected in series by the connecting portions 32, the battery components 26 in FIG. The structure is such that they are electrically connected in series.
【００２６】この際に、一方の電池構成体２６と他方の
電池構成体２６とを接続する正極集電箔１０及び負極集
電箔１４の捲回方向の長さは、それぞれ捲回していく場
合に集電箔１０、１４のみで内側の電池構成体２６の外
周を一周以上捲回できる長さとしておく。これにより内
側の電池構成体２６の外周全体が集電箔により包まれる
構造となり、内側の電池構成体２６と外側の電池構成体
２６の正極及び負極が短絡することを防止できる。この
際に、２つの電池構成体を接続する集電箔１０、１４の
接続部３２における捲回方向と垂直方向の幅は、電極が
構成されている部分よりも大きくするのが望ましい。こ
れは、電池構成体２６を捲回した後円筒形状となったバ
イポーラ型リチウムイオン２次電池の上下端から電解質
が隣の電池構成体に移動し電解質短絡が発生することを
防止するためである。At this time, the lengths in the winding direction of the positive electrode current collector foil 10 and the negative electrode current collector foil 14 that connect the one battery constituent member 26 and the other battery constituent member 26 are different from each other. In addition, the outer periphery of the inner battery structure 26 is set to have a length that allows one or more windings with only the current collecting foils 10 and 14. As a result, the entire outer periphery of the inner battery component 26 is wrapped with the current collector foil, and it is possible to prevent the positive electrode and the negative electrode of the inner battery component 26 and the outer battery component 26 from being short-circuited. At this time, it is desirable that the width of the connection portion 32 of the current collector foils 10 and 14 connecting the two battery components in the direction perpendicular to the winding direction is larger than that of the portion where the electrodes are formed. This is to prevent the electrolyte from moving from the upper and lower ends of the bipolar lithium-ion secondary battery having a cylindrical shape after winding the battery structure 26 to the adjacent battery structure and causing an electrolyte short circuit. .
【００２７】以上のようにして構成した図６に示される
バイポーラ型リチウムイオン２次電池は、その最内部に
正極集電箔１０が、最外部に負極集電箔１４が露出して
いるので、それぞれに正極端子リード２０及び負極端子
リード２２を接続する。なお、本実施形態においても、
最内部と最外部の正極と負極とを逆に構成することも可
能である。また、図６では、電池ケース１００は省略さ
れている。The bipolar type lithium ion secondary battery shown in FIG. 6 constructed as described above has the positive electrode current collector foil 10 exposed at the innermost portion and the negative electrode current collector foil 14 exposed at the outermost portion. The positive electrode terminal lead 20 and the negative electrode terminal lead 22 are connected to each. Note that, also in this embodiment,
The innermost and outermost positive and negative electrodes can be configured in reverse. Further, in FIG. 6, the battery case 100 is omitted.
【００２８】図８（ａ），（ｂ）には、本実施形態に係
る電池構成体２６の変形例が示される。本変形例におい
て特徴的な点は、一方の電池構成体２６の正極集電箔１
０と他方の電池構成体２６の負極集電箔１４とを接続す
るために、ステンレス鋼等の接続用集電箔３４を使用し
たことにある。この接続用集電箔３４は、電池構成体２
６の捲回方向に対して９０°方向の幅が電極部分よりも
大きくなっている。これにより、電池構成体２６を捲回
した場合に、円筒型のバイポーラ型リチウムイオン２次
電池の上下の端から電解質が漏れ出て短絡することを防
止することができる。FIGS. 8A and 8B show a modified example of the battery structure 26 according to this embodiment. The characteristic point of this modified example is that the positive electrode current collector foil 1 of one of the battery components 26 is
This is because the connection current collector foil 34 made of stainless steel or the like was used to connect the negative electrode current collector foil 14 of the other battery assembly 26. This connection current collector foil 34 is used for the battery assembly 2
The width of 6 in the 90 ° direction with respect to the winding direction is larger than that of the electrode portion. Thereby, when the battery structure 26 is wound, it is possible to prevent the electrolyte from leaking out from the upper and lower ends of the cylindrical bipolar lithium-ion secondary battery and causing a short circuit.
【００２９】本実施形態に係るバイポーラ型リチウムイ
オン２次電池においても、実施形態１と同様に正極集電
箔１０としてアルミニウム箔を使用し、負極集電箔１４
として銅箔を使用した。また、正極活物質１２としては
ＬｉＭｎ2Ｏ4を使用し、負極活物質１６として黒鉛を使
用した。これらの活物質は結着剤ＰＶＤＦと混合したも
のを上述の集電箔１０、１４上に塗布して形成したもの
である。また、セパレータ１８としては不織布を使用し
た。これらの正極、負極及びセパレータ１８には、実施
形態１と同様の電解液を含浸させ、１２０℃に加熱した
後室温に戻しゲル化させている。Also in the bipolar type lithium ion secondary battery according to this embodiment, an aluminum foil is used as the positive electrode current collector foil 10 and the negative electrode current collector foil 14 is used as in the first embodiment.
Copper foil was used as. LiMn 2 O 4 was used as the positive electrode active material 12, and graphite was used as the negative electrode active material 16. These active materials are formed by coating the current collector foils 10 and 14 with a mixture with the binder PVDF. A non-woven fabric was used as the separator 18. The positive electrode, the negative electrode, and the separator 18 are impregnated with the same electrolytic solution as in Embodiment 1, heated to 120 ° C., and then returned to room temperature to be gelled.
【００３０】実施形態３．図９には、本実施形態に係る
バイポーラ型リチウムイオン２次電池の構成の断面図が
示される。また、図１０（ａ），（ｂ）には、図９に示
されたバイポーラ型リチウムイオン２次電池を構成する
電池構成体２６の断面図及び平面図が示される。Embodiment 3. FIG. 9 shows a cross-sectional view of the configuration of the bipolar lithium-ion secondary battery according to this embodiment. 10 (a) and 10 (b) are a cross-sectional view and a plan view of a battery structure 26 that constitutes the bipolar lithium-ion secondary battery shown in FIG.
【００３１】図１０（ａ）に示されるように、本実施形
態における電池構成体２６は、正極集電箔１０の片面の
みに正極活物質１２が形成されており、負極集電箔１４
の片面のみに負極活物質１６が形成されている。これら
の正極活物質１２及び負極活物質１６は、セパレータ１
８を介して対向配置されている。また、一方の電池構成
体２６の正極集電箔１０と他方の電池構成体２６の負極
集電箔１４とは、接続部３２で接続されており、電池構
成体２６が直列接続されている。As shown in FIG. 10 (a), in the battery assembly 26 of this embodiment, the positive electrode active material 12 is formed only on one surface of the positive electrode current collector foil 10, and the negative electrode current collector foil 14 is formed.
The negative electrode active material 16 is formed on only one surface of the. The positive electrode active material 12 and the negative electrode active material 16 are used in the separator 1
8 are arranged opposite to each other. Further, the positive electrode current collector foil 10 of one of the battery components 26 and the negative electrode current collector foil 14 of the other battery component 26 are connected by the connecting portion 32, and the battery components 26 are connected in series.
【００３２】本実施形態において特徴的な点は、各電池
構成体２６が、接続部３２を除いて、ポリプロピレンフ
ィルム等から成る絶縁フィルム３６で覆われていること
である。このような構成により、実施形態２のように、
内側の電池構成体２６の外周に外側の電池構成体２６を
巻き付ける際に、内側の電池構成体２６の外周の一周分
以上にわたって集電箔を捲回しなくても、内側の電池構
成体２６と外側の電池構成体２６とが短絡することがな
くなる。このため、図９に示されるように、本実施形態
に係るバイポーラ型リチウムイオン２次電池において
は、接続部３２において正極集電箔１０と負極集電箔１
４とを接続する際に、使用する集電箔の長さを短くする
ことができ、そのぶん体積当たりの電気容量を増加させ
ることができる。A feature of this embodiment is that each battery structure 26 is covered with an insulating film 36 made of polypropylene film or the like except the connecting portion 32. With such a configuration, as in the second embodiment,
When winding the outer battery component 26 around the outer periphery of the inner battery component 26, the inner battery component 26 and the inner battery component 26 need not be wound around the outer periphery of the inner battery component 26 for one or more rounds. The outer battery structure 26 is not short-circuited. Therefore, as shown in FIG. 9, in the bipolar lithium-ion secondary battery according to the present embodiment, the positive electrode current collector foil 10 and the negative electrode current collector foil 1 are provided at the connection portion 32.
When connecting with 4, the length of the current collector foil used can be shortened, and the electric capacity per volume can be increased accordingly.
【００３３】なお、図９には、３つの電池構成体が、ぞ
れぞれ内側のものの外周に外側のものが巻き付けられ、
それぞれ内側から外側に向かって直列に接続された例が
示されている。この電池構成体の数は、３つに限られる
ものではなく、４つあるいはそれ以上のものを順次捲回
していくことができる。Incidentally, in FIG. 9, three battery components are wound around the inside of the battery and the outside of the battery,
An example is shown in which each is connected in series from the inside to the outside. The number of battery components is not limited to three, and four or more can be wound in sequence.
【００３４】以下に、本実施形態に係るバイポーラ型リ
チウムイオン２次電池の具体例を実施例２として説明す
る。A specific example of the bipolar type lithium ion secondary battery according to this embodiment will be described below as Example 2.
【００３５】実施例２．正極集電箔１０としてアルミニ
ウム箔を使用し、負極集電箔１４として銅箔を使用し
た。また、正極活物質１２としてＬｉＭｎ2Ｏ4を、負極
活物質１６として黒鉛を使用した。これらの活物質を結
着剤ＰＶＤＦと混合してペーストとし、各集電箔の片面
のみに塗布した。また、セパレータ１８としては不織布
を使用し、実施形態１及び２と同様に、ＥＣ：ＤＥＣ＝
１：１の液体にＬｉＰＦ6を１ｍｏｌ／ｌ溶かした溶液
とＰＶＤＦ−ＨＦＰとの重量比が７：１となるように混
合した電解液を含浸させた。これを１２０℃に加熱した
後室温に戻し、含浸させた電解液をゲル化させた。なお
この電解液は、セパレータ１８の他、上述した正極及び
負極にも含浸されている。Example 2. An aluminum foil was used as the positive electrode current collector foil 10, and a copper foil was used as the negative electrode current collector foil 14. Further, LiMn 2 O 4 was used as the positive electrode active material 12, and graphite was used as the negative electrode active material 16. These active materials were mixed with a binder PVDF to form a paste, which was applied to only one surface of each current collector foil. A nonwoven fabric is used as the separator 18, and EC: DEC =
An electrolyte solution was prepared by impregnating a 1: 1 liquid solution of LiPF 6 dissolved in 1 mol / l and PVDF-HFP in a weight ratio of 7: 1. This was heated to 120 ° C. and then returned to room temperature to gel the impregnated electrolytic solution. In addition to the separator 18, the electrolytic solution is impregnated into the positive electrode and the negative electrode.
【００３６】このように構成した電池構成体２６を、ポ
リプロピレンフィルムで正極集電箔１０及び負極集電箔
１４の端部を除いて覆い、熱圧着することにより封止し
た。この状態で電池特性を評価し、短絡、容量のばらつ
き等をチェックした。The battery structure 26 thus constructed was covered with a polypropylene film except the ends of the positive electrode current collector foil 10 and the negative electrode current collector foil 14, and thermocompression-bonded to seal. In this state, the battery characteristics were evaluated, and short circuits, variations in capacity, etc. were checked.
【００３７】次に、このように構成した各電池構成体２
６の正極集電箔１０と負極集電箔１４とをスポット溶接
により接続し、図１０（ａ），（ｂ）に示される捲回方
向Ａに捲回し本実施例に係るバイポーラ型リチウムイオ
ン２次電池を得た。この際、最内部に露出した正極集電
箔１０には正極端子リード２０を取り付け、最外部に露
出した負極集電箔１４には、負極端子リード２２を取り
付けた。なおこの負極端子リードは、最外部の負極集電
箔１４を、電池構成体２６を収納する電池ケース１００
（図示せず）に接触させ、この電池ケース１００に負極
端子リード２２を取り付けることとしてもよい。また、
本実施例においても、最内部を負極、最外部を正極とす
ることも可能である。Next, each battery assembly 2 thus constructed
The positive electrode current collector foil 10 and the negative electrode current collector foil 14 of No. 6 are connected by spot welding and wound in the winding direction A shown in FIGS. 10 (a) and 10 (b), and the bipolar lithium ion 2 according to the present embodiment. The next battery was obtained. At this time, the positive electrode terminal lead 20 was attached to the positive electrode collector foil 10 exposed to the innermost portion, and the negative electrode terminal lead 22 was attached to the negative electrode collector foil 14 exposed to the outermost portion. The negative electrode terminal lead has a battery case 100 in which the outermost negative electrode current collector foil 14 is housed in the battery structure 26.
The negative electrode terminal lead 22 may be attached to the battery case 100 by contacting it (not shown). Also,
Also in this embodiment, the innermost part may be the negative electrode and the outermost part may be the positive electrode.
【００３８】以上の方法により、４つの電池構成体２６
からなるバイポーラ型リチウムイオン２次電池を構成
し、その電気特性を評価した。By the above method, four battery components 26
A bipolar lithium-ion secondary battery consisting of was constructed and its electrical characteristics were evaluated.
【００３９】本実施例に係る電池構成体２６は、それぞ
れ正極集電箔１０と負極集電箔１４の片面のみに正極活
物質１２及び負極活物質１６が形成されているので、こ
れを捲回する前からリチウムイオン２次電池として完成
しているので、個々の電池構成体の容量チェック及び短
絡チェックが可能である。本実施例に使用した電池構成
体２６は、容量のばらつきが最大２０％あるが、上述し
たように、個々の電池構成体２６の容量をあらかじめ測
定することができるので、容量ばらつきの小さい電池構
成体のみでバイポーラ型リチウムイオン２次電池を構成
することが可能となる。これにより、サイクル特性を向
上させることができる。In the battery structure 26 according to this embodiment, the positive electrode active material 12 and the negative electrode active material 16 are formed on only one surface of the positive electrode current collector foil 10 and the negative electrode current collector foil 14, respectively. Since it was completed as a lithium-ion secondary battery before that, it is possible to check the capacity and short circuit of each battery constituent. The battery assembly 26 used in this example has a maximum capacity variation of 20%. However, as described above, since the capacity of each battery assembly 26 can be measured in advance, the battery assembly having a small capacity variation can be obtained. It is possible to form a bipolar lithium ion secondary battery with only the body. As a result, cycle characteristics can be improved.
【００４０】容量ばらつきが５％以内の電池構成体２６
のみを４つ直列接続し、図１０（ａ），（ｂ）に示され
る捲回方向Ａに捲回し、バイポーラ型リチウムイオン２
次電池を構成し、１２Ｖ−１７Ｖの間で、１Ｃの一定電
流で充放電させたところ、１００サイクル後の容量維持
率が８７％と良好な値を得ることができた。Battery structure 26 having a capacity variation of 5% or less
Only four of them are connected in series and wound in the winding direction A shown in FIGS.
When the secondary battery was constructed and charged and discharged at a constant current of 1 C between 12V and 17V, the capacity retention ratio after 100 cycles was 87%, which was a good value.
【００４１】実施形態４．図１１には、本実施形態に係
るバイポーラ型リチウムイオン２次電池の構成の断面図
が示される。また、図１２（ａ），（ｂ）には、図１１
に示されたバイポーラ型リチウムイオン２次電池を構成
する電池構成体２６の断面図及び平面図が示される。Embodiment 4. FIG. 11 shows a cross-sectional view of the configuration of the bipolar lithium-ion secondary battery according to this embodiment. In addition, in FIGS. 12A and 12B, FIG.
A cross-sectional view and a plan view of a battery structure 26 that constitutes the bipolar lithium-ion secondary battery shown in FIG.
【００４２】図１２（ａ）において、正極集電箔１０の
片面のみに、正極活物質１２を形成して正極を構成し
た。また、負極集電箔１４の片面のみに負極活物質１６
を形成し、負極を構成した。これらの正極及び負極は、
セパレータ１８を介してそれぞれの活物質１２、１６が
対向するように配置され、電池構成体２６を構成してい
る。本実施形態に係る電池構成体２６は、正極活物質１
２と負極活物質１６とセパレータ１８の両端部に絶縁部
材３８が設けられており、これにより電池構成体２６の
正極集電箔１０と負極集電箔１４とを密着させている。
これにより正極活物質１２と負極活物質１６とをセパレ
ータ１８とからなる内容物を密閉し、電解質の漏れを防
止できる。従って、電解質の短絡による電圧低下を防止
することができる。In FIG. 12A, the positive electrode active material 12 was formed on only one surface of the positive electrode current collector foil 10 to form a positive electrode. In addition, the negative electrode active material 16 is provided only on one surface of the negative electrode current collector foil 14.
To form a negative electrode. These positive and negative electrodes are
The active materials 12 and 16 are arranged so as to face each other with the separator 18 in between, and constitute a battery structure 26. The battery structure 26 according to the present embodiment has the positive electrode active material 1
Insulating members 38 are provided at both ends of the negative electrode active material 16, the negative electrode active material 16, and the separator 18, and thereby the positive electrode current collector foil 10 and the negative electrode current collector foil 14 of the battery structure 26 are brought into close contact with each other.
Thereby, the contents including the positive electrode active material 12 and the negative electrode active material 16 and the separator 18 can be sealed to prevent leakage of the electrolyte. Therefore, it is possible to prevent a voltage drop due to a short circuit of the electrolyte.
【００４３】図１２（ｂ）には、活物質１２、１６が塗
布された集電箔１０、１４と周囲を絶縁部材３８で囲ま
れたセパレータ１８とが示される。これらにより電池構
成体２６を形成する場合には、絶縁部材３８で囲まれた
部分に活物質１２、１６が収容され、セパレータ１８と
接するようにそれぞれ正極と負極とを絶縁部材３８には
め合わせる。これにより、図１２（ａ）に示されるよう
な電池構成体２６を得ることができる。FIG. 12B shows collector foils 10 and 14 coated with active materials 12 and 16 and a separator 18 surrounded by an insulating member 38. When the battery structure 26 is formed by these, the active materials 12 and 16 are housed in the portion surrounded by the insulating member 38, and the positive electrode and the negative electrode are fitted to the insulating member 38 so as to be in contact with the separator 18. As a result, the battery structure 26 as shown in FIG. 12 (a) can be obtained.
【００４４】このような電池構成体２６は、図１２
（ａ）に示されるように、集電箔、活物質、セパレータ
が積層されて構成されており、その積層構造の上下の積
層端面は正極集電箔１０及び負極集電箔１４となってい
る。したがって、これを図１２（ａ）に示される矢印Ａ
の方向に捲回し、最内部に正極集電箔が、最外部に負極
集電箔が来るようにし、さらに、この最外周の負極集電
箔に、次の電池構成体２６の最内周の正極集電箔１０が
電気的に接触するように外側に捲回することができる。
以後同様にして所定個数の電池構成体２６を順次外側に
捲回していく。これにより、図１１に示されるように、
内側から外側に向かって電池構成体２６が直列に接続さ
れたバイポーラ型リチウムイオン２次電池を得ることが
できる。このようにして組み立てたバイポーラ型リチウ
ムイオン２次電池は、その最内部の正極集電箔に正極端
子リード２０を接続し、最外部の負極集電箔に負極端子
リード２２を接続する。本実施形態においても、最内部
を負極、最外部を正極とすることも可能である。Such a battery structure 26 is shown in FIG.
As shown in (a), a current collector foil, an active material, and a separator are laminated, and upper and lower laminated end faces of the laminated structure are a positive electrode current collector foil 10 and a negative electrode current collector foil 14. . Therefore, this is indicated by the arrow A shown in FIG.
In such a manner that the positive electrode current collector foil comes to the innermost part and the negative electrode current collector foil comes to the outermost part. The positive electrode current collector foil 10 can be wound outside so as to make electrical contact.
Thereafter, similarly, a predetermined number of battery components 26 are sequentially wound outward. As a result, as shown in FIG.
It is possible to obtain a bipolar lithium ion secondary battery in which the battery components 26 are connected in series from the inside to the outside. In the bipolar lithium-ion secondary battery thus assembled, the positive electrode terminal lead 20 is connected to the innermost positive electrode current collector foil, and the negative electrode terminal lead 22 is connected to the outermost negative electrode current collector foil. Also in this embodiment, the innermost part may be the negative electrode and the outermost part may be the positive electrode.
【００４５】なお、本実施形態に係る電池構成体２６
は、捲回せずに従来同様積層してもバイポーラ型リチウ
ムイオン２次電池を得ることができる。The battery assembly 26 according to the present embodiment.
A bipolar lithium-ion secondary battery can be obtained by stacking as in the prior art without winding.
【００４６】以下に、本実施形態に係るバイポーラ型リ
チウムイオン２次電池の具体例を実施例３として説明す
る。A specific example of the bipolar type lithium ion secondary battery according to this embodiment will be described below as Example 3.
【００４７】実施例３．正極集電箔１０としてアルミニ
ウム箔を使用し、この片面のみに、その周囲に余白を作
って活物質を印刷乾燥し正極とした。正極活物質１２と
しては、ＬｉＭｎ2Ｏ4を使用し、これに導電剤として天
然黒鉛を混合した。また、ゲル電解質としてＥＣ：ＤＥ
Ｃ＝１：１の液体にＬｉＰＦ6を１ｍｏｌ／ｌ溶解した
溶液とＰＶＤＦ−ＨＦＰとを３：１としたものを使用し
た。また、ペースト化するための有機溶媒としてテトラ
ヒドロフラン（ＴＨＦ）を使用した。これらを、その混
合比として、ＬｉＭｎ2Ｏ4：天然黒鉛：ゲル電界質：有
機溶媒＝１０：１：１０：３０で混合し、正極ペースト
とし、上記正極集電箔１０に塗布した。Example 3. An aluminum foil was used as the positive electrode current collector foil 10, and the active material was printed and dried to form a blank on the periphery of only one surface of the aluminum foil to obtain a positive electrode. LiMn 2 O 4 was used as the positive electrode active material 12, and natural graphite was mixed therein as a conductive agent. In addition, EC: DE is used as the gel electrolyte.
A solution in which 1 mol / l of LiPF 6 was dissolved in a liquid of C = 1: 1 and PVDF-HFP in 3: 1 were used. Tetrahydrofuran (THF) was used as an organic solvent for forming a paste. These were mixed at a mixing ratio of LiMn 2 O 4 : natural graphite: gel electrolyte: organic solvent = 10: 1: 10: 30 to prepare a positive electrode paste, which was applied to the positive electrode current collector foil 10.
【００４８】また、負極集電箔１４として銅箔を使用
し、この片面のみに、その周囲に余白を作って活物質を
印刷乾燥し負極とした。負極活物質としては天然黒鉛を
使用し、ゲル電解質及び有機溶媒として上記正極と同じ
ものを使用した。これらを、その混合比として天然黒
鉛：ゲル電解質：有機溶媒＝１：１：４で混合し、負極
ペーストとし、これを上記負極集電箔１４に塗布した。Further, a copper foil was used as the negative electrode current collector foil 14, and a margin was formed around the copper foil only on this one surface to print and dry the active material to obtain a negative electrode. Natural graphite was used as the negative electrode active material, and the same gel electrolyte and organic solvent as those used in the positive electrode were used. These were mixed at a mixing ratio of natural graphite: gel electrolyte: organic solvent = 1: 1: 4 to prepare a negative electrode paste, which was applied to the negative electrode current collector foil 14.
【００４９】また、セパレータ１８としては、不織布に
ゲル電解質と有機溶媒とを含浸させ乾燥させたものを使
用した。ゲル電解質としてはＥＣ：ＤＥＣ＝１：１の液
体にＬｉＰＦ6を１ｍｏｌ／ｌ溶解させた溶液とＰＶＤ
Ｆ−ＨＦＰとを５：１の割合で混合したものを使用し、
有機溶媒としてＴＨＦを使用した。ゲル電解質と有機溶
媒との混合比は１：２とした。このようにして形成した
セパレータ１８は、ゲル電解質が漏れないようにポリプ
ロピレンフィルムから成る絶縁部材３８により周囲を囲
んだ。さらに、このセパレータ１８を介して上述した正
極及び負極の活物質１２、１４が対向するように配置
し、熱プレスすることにより正極集電箔１０−絶縁部材
３８−セパレータ１８−絶縁部材３８−負極集電箔１４
が熱圧着され、内容物を密封した。この熱プレスにより
正極活物質１２、セパレータ１８、負極活物質１６の中
にあるゲル電解質も熱溶融後再ゲル化され、ゲル間での
空隙がなくなり、イオン伝導性が向上される。As the separator 18, a non-woven fabric impregnated with a gel electrolyte and an organic solvent and dried was used. As the gel electrolyte, a solution in which 1 mol / l of LiPF 6 was dissolved in a liquid of EC: DEC = 1: 1 and PVD
Using a mixture of F-HFP at a ratio of 5: 1,
THF was used as the organic solvent. The mixing ratio of the gel electrolyte and the organic solvent was 1: 2. The separator 18 thus formed was surrounded by an insulating member 38 made of polypropylene film so that the gel electrolyte would not leak. Further, the positive electrode and the negative electrode active materials 12 and 14 described above are arranged so as to face each other with the separator 18 interposed therebetween, and hot pressed to collect the positive electrode current collector foil 10-insulating member 38-separator 18-insulating member 38-negative electrode. Collector foil 14
Was thermocompressed and the contents were sealed. By this hot pressing, the gel electrolyte in the positive electrode active material 12, the separator 18, and the negative electrode active material 16 is also re-gelled after being melted by heat, voids between gels are eliminated, and ionic conductivity is improved.
【００５０】以上のようにして構成した電池構成体２６
を、その容量及び短絡の有無をチェックした後、図示し
ない電池ケース内で四重に捲回し、内側の電池構成体２
６から外側の電池構成体２６に向かって電気的に直列に
接続し、バイポーラ型リチウムイオン２次電池を得た。The battery assembly 26 constructed as described above
After checking its capacity and whether or not there is a short circuit, it is quadrupled in a battery case (not shown), and the inner battery assembly 2
Electrically connected in series from No. 6 to the outer battery structure 26 to obtain a bipolar lithium ion secondary battery.
【００５１】このようにして本実施例に係るバイポーラ
型リチウムイオン２次電池は、初期に１６．４Ｖまで充
電した状態で１０日間放置しても、電圧が１５．６Ｖま
での低下に留まった。これに対して、セパレータ１８の
周囲をあらかじめ絶縁部材３８で覆わずに電池構成体２
６を捲回し、その後に電解質が露出した部分をエポキシ
樹脂等で絶縁したものは、１０日間放置した後、１６．
４Ｖの電圧が３．８Ｖまで低下していた。これにより、
本実施例に係るバイポーラ型リチウムイオン２次電池の
絶縁性が極めて良好であることがわかる。As described above, the bipolar lithium-ion secondary battery according to this example had a voltage drop to 15.6V even after being left for 10 days while being initially charged to 16.4V. On the other hand, the periphery of the separator 18 is not covered with the insulating member 38 in advance, and
After winding 6 and insulating the exposed portion of the electrolyte with epoxy resin or the like, after leaving it for 10 days, 16.
The voltage of 4V had dropped to 3.8V. This allows
It can be seen that the bipolar lithium-ion secondary battery according to this example has extremely good insulating properties.
【００５２】実施形態５．以上に述べた各実施形態に係
るバイポーラ型リチウムイオン２次電池においては、充
放電電流が大きくなった場合、内側にある電池構成体２
６ほど温度が高くなる。このため、内側の電池構成体２
６ほどリチウムイオン伝導性が良好となり、外側の電池
構成体２６よりも内部抵抗が低下する。各電池構成体２
６は直列に接続されており、同じ大きさの電流が流れる
ので、内部抵抗が高い外側の電池構成体２６の方が電圧
が高くなる。このため、高電圧が印加されると、特に外
側の電池構成体２６の電界液の劣化や集電箔の溶出等に
より電池の劣化が起こる可能性がある。従って、個々の
電池構成体２６の内部抵抗が、使用時に等しくなるよう
に調整するのが好適である。Embodiment 5. In the bipolar lithium-ion secondary battery according to each of the embodiments described above, when the charging / discharging current becomes large, the inner battery structure 2
The temperature rises by about 6. Therefore, the inner battery assembly 2
6, the lithium ion conductivity is better, and the internal resistance is lower than that of the outer battery component 26. Each battery structure 2
Since 6 is connected in series and the same amount of current flows, the voltage is higher in the outer battery component 26 having the higher internal resistance. Therefore, when a high voltage is applied, there is a possibility that the battery may deteriorate due to deterioration of the electrolytic solution of the outer battery structure 26 or elution of the current collector foil. Therefore, it is preferable to adjust the internal resistances of the individual battery components 26 so that they are equal in use.
【００５３】図１３には、このような各電池構成体２６
の内部抵抗が使用時に等しくなるバイポーラ型リチウム
イオン２次電池の構成の断面図が示される。また、図１
４には、図１３に示されたバイポーラ型リチウムイオン
２次電池を構成するための電池構成体２６の断面図が示
される。図１４において、図１３に示されたバイポーラ
型リチウムイオン２次電池を構成する場合には、図の矢
印Ａの方向に電池構成体２６を捲回していくので、図の
左側の電池構成体２６の方が図の右側の電池構成体２６
よりも内側になる。このため、図の左側の電池構成体２
６の内部抵抗をあらかじめ高くしておけば、使用中に内
側の電池構成体２６の温度が高くなり、内部抵抗が低く
なった場合にも、外側に来る図の右側の電池構成体２６
の内部抵抗と等しくすることができる。以降同様にして
外側に配置される電池構成体２６ほどその内部抵抗があ
らかじめ低くなるように構成しておく。FIG. 13 shows each of such battery components 26.
A cross-sectional view of the structure of a bipolar lithium-ion secondary battery in which the internal resistances of the two are equal in use is shown. Also, FIG.
4 shows a sectional view of a battery structure 26 for forming the bipolar lithium ion secondary battery shown in FIG. In FIG. 14, when the bipolar lithium ion secondary battery shown in FIG. 13 is formed, the battery structure 26 is wound in the direction of arrow A in the drawing. Is the battery assembly 26 on the right side of the figure.
Will be more inside. Therefore, the battery assembly 2 on the left side of the figure
If the internal resistance of 6 is increased in advance, the temperature of the inner battery assembly 26 becomes high during use, and even if the internal resistance becomes low, the battery assembly 26 on the right side in the figure that comes to the outside
Can be equal to the internal resistance of. Thereafter, similarly, the battery components 26 arranged on the outer side are configured such that the internal resistance thereof is lowered in advance.
【００５４】内部抵抗を調整する方法としては、各電極
の活物質の総量と空隙率とを一定にしておき、活物質の
厚さを調整し、結果として有効面積すなわちセパレータ
１８と対向している活物質層の面積を制御する方法があ
る。すなわち、厚さを厚くすれば、その分有効面積が小
さくなり抵抗が高くなる。As a method of adjusting the internal resistance, the total amount of the active material and the porosity of each electrode are kept constant, the thickness of the active material is adjusted, and as a result, the effective area, that is, the separator 18 is opposed. There is a method of controlling the area of the active material layer. That is, if the thickness is increased, the effective area is reduced accordingly and the resistance is increased.
【００５５】他方、目付量すなわち単位面積当たりの活
物質の重量と有効面積とを一定にし、活物質の厚さを調
整し、その空隙率を変化させることによっても内部抵抗
を調整することができる。すなわち、プレスにより活物
質の厚さを変化させ、空隙率を小さくするほど、活物質
間に存在する電解質が減少し、イオン伝導性が低くなっ
て抵抗が増加する。On the other hand, the internal resistance can also be adjusted by keeping the weight per unit area, that is, the weight of the active material per unit area and the effective area constant, adjusting the thickness of the active material, and changing the porosity. . That is, as the thickness of the active material is changed by pressing to reduce the porosity, the electrolyte existing between the active materials decreases, the ionic conductivity decreases, and the resistance increases.
【００５６】このように、活物質の総量及び空隙率を一
定とした状態で厚さを変えて有効面積で抵抗を調整する
か、あるいは目付量及び有効面積を一定にし、活物質の
空隙率を調整し内部抵抗を調整する方法が好適と考えら
れる。As described above, the resistance is adjusted by the effective area by changing the thickness while keeping the total amount of active material and the porosity constant, or the porosity of the active material is adjusted by making the basis weight and effective area constant. A method of adjusting the internal resistance is considered to be suitable.
【００５７】以上のような内部抵抗の調整方法の具体例
を、実施例４、実施例５として説明する。Specific examples of the method of adjusting the internal resistance as described above will be described as Examples 4 and 5.
【００５８】実施例４．本実施例においては、４つの電
池構成体２６を使用し、それぞれの内部抵抗を変化させ
る。４つの電池構成体２６は、最も内側に捲回されるも
のから外側に捲回されるものの順にＩ、ＩＩ、ＩＩＩ、
ＩＶとし、それぞれの正極及び負極の有効面積の値を表
１に示す。なお、本実施例においては、各電極の総活物
質量と空隙率を一定に保ち、目付量を変化させることに
より有効面積を変化させた。Example 4. In this embodiment, four battery components 26 are used and the internal resistance of each is varied. The four battery components 26 are I, II, III, in this order from the innermost wound one to the outer one.
Table 1 shows the values of the effective areas of the positive electrode and the negative electrode, respectively. In this example, the effective area was changed by keeping the total active material amount and porosity of each electrode constant and changing the basis weight.
【００５９】[0059]
【表１】
なお、各活物質の空隙率は、正極、負極共に４５％とし
た。[Table 1] The porosity of each active material was 45% for both the positive electrode and the negative electrode.
【００６０】実施例５．４つの電池構成体２６Ｉ，Ｉ
Ｉ，ＩＩＩ，ＩＶの正極及び負極の目付量はそれぞれ２
０．４ｍｇ／ｃｍ2、１０．２ｍｇ／ｃｍ2の一定とし、
有効面積も１００ｃｍ2の一定とした。このような正極
及び負極の活物質を、プレスにより以下に示す厚さと
し、その空隙率を調整した。Example 5. Four battery assemblies 26I, I
The weight of the positive and negative electrodes of I, III, and IV is 2 each.
0.4mg / cm 2, a constant of 10.2mg / cm 2,
The effective area was also fixed at 100 cm 2 . The positive electrode and negative electrode active materials were pressed to have the thicknesses shown below, and the porosity thereof was adjusted.
【００６１】[0061]
【表２】
電池構成体ＩＶの場合には、空隙率が５０％であり、こ
れ以上空隙率を上げると活物質間の接触抵抗が増大し膜
厚増加と共に抵抗が増加するので、この厚みが限界と考
えられる。この電池構成体ＩＶの膜厚以下では、膜厚の
減少と共に空隙率が減少し、活物質間の電解質量が減少
してイオン伝導度が低くなり、抵抗が高くなる。すなわ
ち、活物質のプレス圧を高くするほど抵抗が高くなる。[Table 2] In the case of the battery structure IV, the porosity is 50%, and if the porosity is further increased, the contact resistance between the active materials increases and the resistance increases with the increase in the film thickness, so this thickness is considered to be the limit. . Below the film thickness of the battery structure IV, the porosity decreases as the film thickness decreases, the electrolytic mass between the active materials decreases, the ionic conductivity decreases, and the resistance increases. That is, the higher the pressing pressure of the active material, the higher the resistance.
【００６２】以上の２つの実施例に対して、４つの電池
構成体Ｉ，ＩＩ，ＩＩＩ，ＩＶとも全て正極目付量を２
０．４ｍｇ／ｃｍ2、負極目付量を１０．２ｍｇ／ｃ
ｍ2、空隙率４５％としたものを作成して、上記２つの
実施例と共に評価した。With respect to the above two embodiments, all the four battery components I, II, III, IV have a positive electrode basis weight of 2
0.4 mg / cm 2 , negative electrode basis weight 10.2 mg / c
Those having m 2 and porosity of 45% were prepared and evaluated together with the above two examples.
【００６３】以上のようにして得たバイポーラ型リチウ
ムイオン２次電池を、１２−１７Ｖの電圧で１Ｃの定電
流充放電をさせたところ、１００サイクル後の容量維持
率は、実施例４が９０％、実施例５が９１％、比較例が
８７％であった。このため、実施例４及び実施例５のよ
うに、内側の電池構成体ほど内部抵抗を高くすることに
より、サイクル特性を向上させることができた。When the bipolar type lithium ion secondary battery obtained as described above was charged and discharged at a constant current of 1 C at a voltage of 12-17 V, the capacity retention rate after 100 cycles was 90% in Example 4. %, Example 5 was 91%, and Comparative Example was 87%. Therefore, like Example 4 and Example 5, the cycle characteristics could be improved by increasing the internal resistance of the inner battery components.
【００６４】[0064]
【発明の効果】以上説明したように、本発明によれば、
電池構成体を捲回してバイポーラ型リチウムイオン２次
電池としているので、コンパクトで容量の大きな電池を
得ることができる。As described above, according to the present invention,
Since the battery structure is wound to form a bipolar lithium-ion secondary battery, a compact and large-capacity battery can be obtained.
【００６５】また、内側の電池構成体と外側の電池構成
体との電気的接続を集電体同士を直接つなぐことにより
行うので、接触抵抗を小さくすることができる。Further, since the inner battery structure and the outer battery structure are electrically connected by directly connecting the current collectors to each other, the contact resistance can be reduced.
【００６６】また、内側の電池構成体の外周を一周以上
集電箔を捲回するので、電解質短絡を防止でき、絶縁性
を向上できるとともに、集電箔のみで短絡を防止するの
で、セパレータあるいは絶縁フィルムを使用する必要が
なく、その分コンパクト化を図ることができる。Further, since the current collector foil is wound around the outer periphery of the inner battery structure for one or more turns, the electrolyte short circuit can be prevented and the insulating property can be improved, and the short circuit can be prevented only by the current collector foil. Since it is not necessary to use an insulating film, the size can be reduced accordingly.
【００６７】また、内側の電池構成体の最外周の集電箔
と外側の電池構成体の最内周の集電箔とを直接接触させ
て電気的に接続するので、接触面積が大きくなり、内部
抵抗を低下させることができる。Further, since the outermost current collecting foil of the inner battery component and the outermost current collecting foil of the outer battery component are directly contacted and electrically connected, the contact area becomes large, The internal resistance can be reduced.
【００６８】また、内側に位置する電池構成体ほど内部
抵抗を高くするので、使用時にはすべての電池構成体の
内部抵抗がほぼ等しくなり、各電池構成体にかかる電圧
をほぼ等しくできるので、電池の劣化を抑制することが
できる。In addition, since the internal resistance of the battery components located closer to the inside is made higher, the internal resistances of all the battery components become substantially equal during use, and the voltages applied to the respective battery components can be made approximately equal. Deterioration can be suppressed.
【図１】 本発明に係るバイポーラ型リチウムイオン２
次電池の実施形態１に使用される電池構成体の断面図で
ある。FIG. 1 is a bipolar lithium ion 2 according to the present invention.
1 is a cross-sectional view of a battery structure used in a first battery of Embodiment 1.
【図２】 図１に示された電池構成体を捲回した場合の
説明図である。FIG. 2 is an explanatory diagram when the battery structure shown in FIG. 1 is wound.
【図３】 実施形態１に使用される電池構成体の変形例
を示す断面図である。FIG. 3 is a cross-sectional view showing a modified example of the battery structure used in the first embodiment.
【図４】 実施形態１に係るバイポーラ型リチウムイオ
ン２次電池の構成の断面図である。FIG. 4 is a cross-sectional view of the configuration of the bipolar lithium-ion secondary battery according to the first embodiment.
【図５】 図４に示されたバイポーラ型リチウムイオン
２次電池のＶ−Ｖ断面図である。5 is a VV cross-sectional view of the bipolar lithium-ion secondary battery shown in FIG.
【図６】 本発明に係るバイポーラ型リチウムイオン２
次電池の実施形態２の断面図である。FIG. 6 is a bipolar lithium ion 2 according to the present invention.
It is sectional drawing of Embodiment 2 of the following battery.
【図７】 図６に示されたバイポーラ型リチウムイオン
２次電池を構成する電池構成体の断面図である。FIG. 7 is a cross-sectional view of a battery structure that constitutes the bipolar lithium-ion secondary battery shown in FIG.
【図８】 図６に示されたバイポーラ型リチウムイオン
２次電池を構成する電池構成体の変形例を示す図であ
る。FIG. 8 is a diagram showing a modified example of the battery structure that constitutes the bipolar lithium-ion secondary battery shown in FIG.
【図９】 本発明に係るバイポーラ型リチウムイオン２
次電池の実施形態３の断面図である。FIG. 9: Bipolar lithium ion 2 according to the present invention
It is sectional drawing of Embodiment 3 of the following battery.
【図１０】 図９に示されたバイポーラ型リチウムイオ
ン２次電池を構成する電池構成体の断面図及び平面図で
ある。FIG. 10 is a cross-sectional view and a plan view of a battery structure that constitutes the bipolar lithium-ion secondary battery shown in FIG.
【図１１】 本発明に係るバイポーラ型リチウムイオン
２次電池の実施形態４の断面図である。FIG. 11 is a cross-sectional view of Embodiment 4 of a bipolar lithium-ion secondary battery according to the present invention.
【図１２】 図１１に示されたバイポーラ型リチウムイ
オン２次電池を構成する電池構成体の断面図及び平面図
である。12 is a cross-sectional view and a plan view of a battery constituent body that constitutes the bipolar lithium-ion secondary battery shown in FIG.
【図１３】 本発明に係るバイポーラ型リチウムイオン
２次電池の実施形態４の断面図である。FIG. 13 is a cross-sectional view of Embodiment 4 of a bipolar lithium-ion secondary battery according to the present invention.
【図１４】 図１３に示されたバイポーラ型リチウムイ
オン２次電池を構成する電池構成体の断面図である。FIG. 14 is a cross-sectional view of a battery structure that constitutes the bipolar lithium-ion secondary battery shown in FIG.
【図１５】 従来におけるバイポーラ型リチウムイオン
２次電池の断面図である。FIG. 15 is a cross-sectional view of a conventional bipolar lithium-ion secondary battery.
１０ 正極集電箔、１２ 正極活物質、１４ 負極集電
箔、１６ 負極活物質、１８ セパレータ、２０ 正極
端子リード、２２ 負極端子リード、２４ 絶縁フィル
ム、２６ 電池構成体、２８ 絶縁容器、３０ 直列接
続用リード線、３２ 接続部、３４ 接続用集電箔、３
６ 絶縁フィルム、３８ 絶縁部材、１００ 電池ケー
ス。10 positive electrode current collector foil, 12 positive electrode active material, 14 negative electrode current collector foil, 16 negative electrode active material, 18 separator, 20 positive electrode terminal lead, 22 negative electrode terminal lead, 24 insulating film, 26 battery component, 28 insulating container, 30 series Connection lead wire, 32 connection part, 34 connection current collector foil, 3
6 insulating film, 38 insulating member, 100 battery case.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 10/40 H01M 2/20 - 2/34 H01M 10/04 ─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields investigated (Int.Cl. 7 , DB name) H01M 10/40 H01M 2/20-2/34 H01M 10/04
Claims (2)
状態で捲回される電池構成体が、絶縁体を介して複数個
同心円状に捲回され、内側の電池構成体から外側の電池
構成体に向かって、順次電気的に直列に接続され、各接
続部では、内側の電池構成体の正極または負極の集電箔
と外側の電池構成体の負極または正極の集電箔とが接続
され、前記内側の電池構成体と外側の電池構成体との接
続部を構成する集電箔が、内側の電池構成体の外周全体
を包む構造となっていることを特徴とするバイポーラ型
リチウムイオン２次電池。1. A plurality of battery constituents wound in a state where a separator is sandwiched between a positive electrode and a negative electrode are concentrically wound through an insulator, and a battery outside the inner battery constituent. To the structure, they are sequentially electrically connected in series and each connection
In the sequel, the positive or negative current collector foil of the inner battery assembly
Connected to the negative electrode or positive electrode current collector foil of the outer battery structure
Contact between the inner battery structure and the outer battery structure.
The current collector foil that forms the connecting part is the entire outer circumference of the battery structure inside.
A bipolar lithium-ion secondary battery having a structure that encloses
状態で捲回される電池構成体が、絶縁体を介して複数個
同心円状に捲回され、内側の電池構成体から外側の電池
構成体に向かって、順次電気的に直列に接続され、前記
内側の電池構成体と外側の電池構成体の電気容量は同じ
で、内部抵抗を内側の電池構成体ほど高くしたことを特
徴とするバイポーラ型リチウムイオン２次電池。2. A plurality of battery constituents wound in a state where a separator is sandwiched between a positive electrode and a negative electrode are concentrically wound with an insulator interposed therebetween, and the battery constituents from the inner constituent to the outer constituent. Towards the structure, connected in series electrically in sequence ,
The inner battery structure and the outer battery structure have the same electrical capacity
Then, a bipolar lithium-ion secondary battery characterized in that the internal resistance is made higher toward the inner battery structure .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20060898A JP3419311B2 (en) | 1998-07-15 | 1998-07-15 | Bipolar lithium-ion secondary battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20060898A JP3419311B2 (en) | 1998-07-15 | 1998-07-15 | Bipolar lithium-ion secondary battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000030746A JP2000030746A (en) | 2000-01-28 |
| JP3419311B2 true JP3419311B2 (en) | 2003-06-23 |
Family
ID=16427205
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20060898A Expired - Fee Related JP3419311B2 (en) | 1998-07-15 | 1998-07-15 | Bipolar lithium-ion secondary battery |
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| Country | Link |
|---|---|
| JP (1) | JP3419311B2 (en) |
Cited By (2)
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|---|---|---|---|---|
| WO2012146589A1 (en) | 2011-04-26 | 2012-11-01 | Commissariat à l'énergie atomique et aux énergies alternatives | Bipolar electrochemical li-ion battery having increased capacity |
| US8512888B2 (en) | 2010-03-11 | 2013-08-20 | Toyota Jidosha Kabushiki Kaisha | Current collector and method for producing the same, battery and method for producing the same |
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| JP4007026B2 (en) * | 2002-03-18 | 2007-11-14 | 新神戸電機株式会社 | Winding cylindrical battery |
| JP4594590B2 (en) | 2002-12-27 | 2010-12-08 | パナソニック株式会社 | Electrochemical element |
| JP4461686B2 (en) * | 2003-02-13 | 2010-05-12 | トヨタ自動車株式会社 | Secondary battery, manufacturing apparatus and manufacturing method thereof |
| KR101189533B1 (en) * | 2004-03-30 | 2012-10-11 | 가부시끼가이샤 구레하 | Material for negative electrode of nonaqueous electrolyte secondary battery, process for producing the same, negative electrode and battery |
| JP4857896B2 (en) * | 2006-05-11 | 2012-01-18 | トヨタ自動車株式会社 | Battery pack and vehicle |
| FR2927727B1 (en) * | 2008-02-19 | 2017-11-17 | Batscap Sa | MULTIBOBIN ELECTRIC ENERGY STORAGE ASSEMBLY. |
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| FR2943854B1 (en) * | 2009-03-26 | 2011-06-10 | Commissariat Energie Atomique | BIPOLAR BATTERY WITH IMPROVED OPERATION |
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| JP5664414B2 (en) * | 2011-03-31 | 2015-02-04 | Tdk株式会社 | Bipolar type secondary battery |
| KR101551135B1 (en) * | 2011-10-28 | 2015-09-07 | 아사히 가세이 가부시키가이샤 | Non-aqueous secondary battery |
| FR2996360B1 (en) | 2012-10-01 | 2014-10-17 | Commissariat Energie Atomique | CURRENT COLLECTOR WITH INTEGRATED SEALING MEANS, BIPOLAR BATTERY COMPRISING SUCH A MANIFOLD, METHOD OF MAKING SUCH A BATTERY. |
| CN107851853A (en) | 2015-12-16 | 2018-03-27 | 株式会社东芝 | Nonaqueous electrolyte battery and battery pack |
| WO2019125085A1 (en) * | 2017-12-21 | 2019-06-27 | 주식회사 엘지화학 | Flexible secondary battery comprising bipolar electrode |
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1998
- 1998-07-15 JP JP20060898A patent/JP3419311B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8512888B2 (en) | 2010-03-11 | 2013-08-20 | Toyota Jidosha Kabushiki Kaisha | Current collector and method for producing the same, battery and method for producing the same |
| WO2012146589A1 (en) | 2011-04-26 | 2012-11-01 | Commissariat à l'énergie atomique et aux énergies alternatives | Bipolar electrochemical li-ion battery having increased capacity |
| US9318748B2 (en) | 2011-04-26 | 2016-04-19 | Commissariat à l'énergie atomique et aux énergies alternatives | Bipolar electrochemical Li-ion battery having increased capacity |
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| JP2000030746A (en) | 2000-01-28 |
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