JP3447610B2 - Electrode separator laminate, method for producing the same, and battery using the same - Google Patents
Electrode separator laminate, method for producing the same, and battery using the sameInfo
- Publication number
- JP3447610B2 JP3447610B2 JP11707299A JP11707299A JP3447610B2 JP 3447610 B2 JP3447610 B2 JP 3447610B2 JP 11707299 A JP11707299 A JP 11707299A JP 11707299 A JP11707299 A JP 11707299A JP 3447610 B2 JP3447610 B2 JP 3447610B2
- Authority
- JP
- Japan
- Prior art keywords
- separator
- electrode
- porous
- thermoplastic polymer
- negative electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は多孔質の正極、負極
およびセパレータを積層した、電池等のデバイスに用い
られる電極セパレータ積層体に関し、さらにそれを用い
た充電可能なリチウム二次電池に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode separator laminate in which a porous positive electrode, a negative electrode and a separator are laminated and used in a device such as a battery, and further relates to a rechargeable lithium secondary battery using the same.
【０００２】[0002]
【従来の技術】電池においては、正極、負極およびセパ
レータが互いに密着し層間剥離が起きないようにするこ
とが重要である。金属缶に収納した巻回型のリチウムイ
オン二次電池が広く普及しているが、これは単に正極、
負極およびセパレータを重ねあわせて巻回しているだけ
であるので、正極、負極およびセパレータを密着させる
力となっているのは巻回していることと金属缶に収納し
ていることから生じる外的な力である。そのため、繰り
返し充放電などにより電極巻回体の内部にたわみが生じ
て層間剥離が起こるといった問題があった。2. Description of the Related Art In a battery, it is important that the positive electrode, the negative electrode and the separator are in close contact with each other and delamination does not occur. The wound-type lithium-ion secondary battery housed in a metal can is widely used.
Since only the negative electrode and the separator are wound on top of each other, the force that brings the positive electrode, the negative electrode and the separator into close contact is the external force generated by the winding and the fact that they are housed in a metal can. Power. Therefore, there is a problem that the electrode winding body is bent due to repeated charge and discharge, and the interlayer peeling occurs.
【０００３】一方、近年の電子機器薄型化の要求の高ま
りから、電池のより一層の薄型化が望まれており、複数
の平板状の正極、負極およびセパレータを積層した積層
型電池が期待されている。積層型電池においては、正
極、負極およびセパレータを密着させる力として巻回す
る手段が使えないことから、外装金属缶からの外力によ
って密着力を得る等の方法が知られているが、金属缶の
重量による重量エネルギー密度のロス等の問題があっ
た。On the other hand, with the recent increasing demand for thinner electronic devices, there is a demand for even thinner batteries, and a laminated battery in which a plurality of flat plate-like positive electrodes, negative electrodes and separators are laminated is expected. There is. In a laminated battery, a method of winding the positive electrode, the negative electrode, and the separator as a force for adhering to each other cannot be used. Therefore, a method of obtaining an adhesive force by an external force from an outer metal can is known. There was a problem such as loss of weight energy density due to weight.
【０００４】これらの問題に対し、正極、負極およびセ
パレータを、外力によって密着させるのではなく、これ
らを接着することによる内的な力によって密着性を維持
する方法が提案されている。例えば、特開平１０−１７
２６０６号公報には、電極とセパレータとの間に多孔性
の接着性樹脂層を設けることが開示されている。また、
特開平１０−１７２６１３号公報には、表面に可塑剤を
含むポリマーを塗布したセパレータと電極を積層し、熱
および圧力を加えて一体化させる方法が開示されてい
る。また、特表平９−５００４８５号公報には、可塑剤
を含むポリマーで電極とセパレータとの一体化物を作製
し、可塑剤を除去してから電解液を導入する方法が開示
されている。また、特開平１０−２８９７３２号公報に
は、有機ビニル化合物の架橋重合体で電極とセパレータ
を接着する方法が開示されている。To solve these problems, a method has been proposed in which the positive electrode, the negative electrode, and the separator are not brought into close contact with each other by an external force, but the adhesion is maintained by an internal force by adhering them. For example, JP-A-10-17
2606 discloses that a porous adhesive resin layer is provided between an electrode and a separator. Also,
Japanese Unexamined Patent Publication No. 10-172613 discloses a method in which a separator having a surface coated with a polymer containing a plasticizer and an electrode are laminated and integrated by applying heat and pressure. Further, Japanese Patent Publication (Kokoku) No. 9-500485 discloses a method of producing an integrated body of an electrode and a separator with a polymer containing a plasticizer, removing the plasticizer, and then introducing an electrolytic solution. Further, JP-A-10-289732 discloses a method of adhering an electrode and a separator with a cross-linked polymer of an organic vinyl compound.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、リチウ
ムイオン電池で用いられているような多孔質正極や多孔
質負極（以下まとめて多孔質電極と称する）と、ポリオ
レフィン製マイクロポーラスセパレータ等の多孔質セパ
レータを接着する方法として、上述したような従来提案
されてきた方法を用いた場合、以下に述べるような問題
点があった。However, a porous positive electrode or a porous negative electrode (hereinafter collectively referred to as a porous electrode) as used in a lithium ion battery, and a porous separator such as a polyolefin microporous separator. When the above-mentioned conventionally proposed method is used as a method for adhering the above, there are the following problems.
【０００６】第一の問題は、高温において接着材料が軟
化し、接着力が低下するという問題である。特開平１０
−１７２６０６号公報、特開平１０−１７２６１３号公
報、および特表平９−５００４８５号公報において例示
されている接着用樹脂の材料は、いずれも非架橋型の熱
可塑性樹脂であった。そのため、特に電解液として非水
系有機溶媒を用いた場合、高温において接着用樹脂が非
水系有機溶媒に膨潤または溶解し、接着力が低下すると
いう問題があった。The first problem is that the adhesive material is softened at high temperature and the adhesive strength is lowered. JP-A-10
The materials for the adhesive resin illustrated in Japanese Patent Application Laid-Open No. 172606, Japanese Patent Application Laid-Open No. 10-172613, and Japanese Patent Application Laid-Open No. 9-500485 were all non-crosslinking type thermoplastic resins. Therefore, particularly when a non-aqueous organic solvent is used as the electrolytic solution, there is a problem that the adhesive resin swells or dissolves in the non-aqueous organic solvent at a high temperature and the adhesive strength is reduced.
【０００７】第二の問題は、接着強度と層間イオン伝導
性との間でトレードオフの関係があり、両立が難しかっ
たという問題である。特開平１０−２８９７３２号公報
に記載の方法では、セパレータの全面に接着剤を塗布し
ていること、および、イオン伝導性を確保するために接
着剤に電解液を保持させてゲル状としていることから、
次のような問題が生じていた。すなわち、電解液を保持
させなければ接着層がイオン伝導の妨げになり、電池の
内部抵抗を増大させてしまう一方で、電解液を保持させ
ると接着層の力学強度が減少し、接着強度が減少すると
いうトレードオフが生じるという問題である。また、同
様なトレードオフの関係は接着剤塗布量と層間イオン伝
導性との間にも存在する。特開平１０−１７２６０６号
公報および特開平１０−１７２６１３号公報に記載の方
法では、セパレータへ接着剤を多く塗布するとそれだけ
強い接着強度が得られるが、セパレータの細孔をも塞い
でしまうことになり、セパレータ中でのイオン伝導性に
支障をきたすことになる一方、接着剤塗布量が少なけれ
ばセパレータの細孔を塞ぐことは少なくなるが、セパレ
ータと電極との界面近傍のごく薄い領域にのみ接着層が
形成され、強い接着力が得られにくい。特にセパレータ
の材質がポリオレフィンである場合、表面の接着力が弱
く剥がれやすい。The second problem is that there is a trade-off between the adhesive strength and the interlayer ionic conductivity, and it is difficult to achieve both at the same time. In the method described in Japanese Patent Application Laid-Open No. 10-289732, an adhesive is applied to the entire surface of the separator, and the adhesive holds an electrolytic solution in order to ensure ion conductivity and is in a gel form. From
The following problems were occurring. That is, if the electrolytic solution is not held, the adhesive layer will hinder ionic conduction and increase the internal resistance of the battery, while holding the electrolytic solution will reduce the mechanical strength of the adhesive layer and decrease the adhesive strength. The problem is that there is a trade-off of doing so. A similar trade-off relationship also exists between the adhesive coating amount and the interlayer ionic conductivity. In the methods described in JP-A-10-172606 and JP-A-10-172613, when a large amount of adhesive is applied to the separator, a stronger adhesive strength is obtained, but the pores of the separator are also blocked. , It will hinder the ionic conductivity in the separator, but if the amount of adhesive applied is small, it will not close the pores of the separator, but it will only adhere to a very thin area near the interface between the separator and the electrode. A layer is formed and it is difficult to obtain a strong adhesive force. In particular, when the material of the separator is polyolefin, the adhesive strength on the surface is weak and the separator is easily peeled off.
【０００８】第三の問題は、接着用樹脂に当初含まれて
いる有機溶媒が電池作製後にも残存するという問題であ
る。特開平１０−１７２６０６号公報や特開平１０−１
７２６１３号公報に記載の方法においては、いずれも接
着用樹脂を塗布したセパレータに電極を密着させてから
有機溶媒を乾燥除去する工程を含んでいるので、正極、
セパレータ、負極の３者を貼りあわせた状態では界面の
通気性が悪く、有機溶媒を完全に除去することが困難で
あり、電池内部に有機溶媒が残存し、それが電池特性に
影響する恐れがあるという問題があった。特表平９−５
００４８５号公報に記載の方法では、正極、負極、およ
びセパレータを接着した後、エーテルに浸漬して可塑剤
を洗浄除去しているが、複数の正極、負極、およびセパ
レータを多数層積層した多層積層体に対してはすべての
層の内部の方の接着剤まで可塑剤を完全に除去すること
はやはり難しい。The third problem is that the organic solvent initially contained in the adhesive resin remains after the battery is manufactured. JP-A-10-172606 and JP-A-10-1
In the method described in Japanese Patent No. 72613, all of them include a step of adhering an electrode to a separator coated with an adhesive resin and then removing the organic solvent by drying.
When the separator and the negative electrode are bonded together, the air permeability at the interface is poor, it is difficult to completely remove the organic solvent, and the organic solvent remains inside the battery, which may affect the battery characteristics. There was a problem. Special table flat 9-5
In the method described in Japanese Patent Publication No. 00485, the positive electrode, the negative electrode, and the separator are adhered and then immersed in ether to wash and remove the plasticizer. However, a plurality of positive electrodes, negative electrodes, and separators are laminated in multiple layers. It is still difficult for the body to completely remove the plasticizer up to the adhesive on the inside of all layers.
【０００９】第四の問題は、正極、負極、およびセパレ
ータを接着した後に電解液を含浸する際に、電解液を迅
速に電極内部まで含浸することが難しく、また、複数の
正極、負極、およびセパレータを多数層積層した多層積
層体に対してすべての層の電極内部まで電解液を含浸す
ることが困難であるという問題である。電極とセパレー
タを接着しない従来の一般のリチウムイオン電池では、
正極、負極、およびセパレータを積層した後に電極とセ
パレータの界面での毛管現象を用いて層の横から電解液
を電極およびセパレータに含浸することが可能である。
ところが正極、負極、およびセパレータを接着する系で
従来知られているものでは、接着剤をセパレータの全面
に塗布しているので、正極、負極、およびセパレータを
接着した後では、電極とセパレータの間の界面が塞がり
毛管現象が起こりにくくなり、層の横から電解液を迅速
に電極内部まで含浸することが難しかった。特表平９−
５００４８５号公報に記載の方法では、電極活物質が多
孔質ポリマーで結着されており、集電体もグリッド状の
ものを用いているので、層の面方向から電解液を含浸す
ることが可能であるが、複数の正極、負極、およびセパ
レータを多数層積層した多層積層体に対してはすべての
層の電極内部まで電解液を迅速に含浸することはやはり
難しい。A fourth problem is that when the positive electrode, the negative electrode, and the separator are adhered and then impregnated with the electrolytic solution, it is difficult to quickly impregnate the electrolytic solution into the inside of the electrode, and a plurality of positive electrodes, negative electrodes, and The problem is that it is difficult to impregnate the inside of the electrodes of all the layers with an electrolytic solution in a multilayer laminate in which a large number of separators are laminated. In the conventional general lithium-ion battery that does not bond the electrode and the separator,
After laminating the positive electrode, the negative electrode, and the separator, it is possible to impregnate the electrode and the separator with the electrolytic solution from the side of the layer by using the capillary phenomenon at the interface between the electrode and the separator.
However, in the conventionally known system for bonding the positive electrode, the negative electrode, and the separator, since the adhesive is applied to the entire surface of the separator, after bonding the positive electrode, the negative electrode, and the separator, the space between the electrode and the separator is reduced. It was difficult to cause the capillary phenomenon to occur due to the blocking of the interface, and it was difficult to rapidly impregnate the inside of the electrode with the electrolytic solution from the side of the layer. Special table flat 9-
In the method described in Japanese Patent No. 500485, since the electrode active material is bound by the porous polymer and the current collector also has a grid shape, it is possible to impregnate the electrolytic solution from the surface direction of the layer. However, it is still difficult to rapidly impregnate the inside of the electrodes of all layers with the electrolytic solution in a multilayer laminate in which a plurality of positive electrodes, negative electrodes, and separators are laminated.
【００１０】上記の四つの問題を同時に解決する電極／
セパレータ接着法は従来知られていなかった。An electrode that solves the above four problems at the same time
The separator bonding method has not been known so far.
【００１１】本発明の目的は、電極とセパレータを接着
することにより、電池使用中に電極とセパレータが剥離
したり電極巻回体にたわみが生じることによる特性劣化
や電池の膨れを抑制すること、また、金属缶等からの外
力による電極／セパレータ層間密着手段を不要とするこ
とであって、高温においても接着力が低下せず、電極と
セパレータの間のイオン伝導に支障をきたすことが無
く、ポリオレフィン等の接着しにくい材質のセパレータ
を用いた場合でも、強い接着強度を持ち、不要な有機溶
媒が電池に残存することが無く、複数の正極、負極、セ
パレータを多数層積層した積層体に対しても内部まで迅
速に電解液を含浸することが可能な接着方法を提供する
ことにある。An object of the present invention is to prevent the deterioration of characteristics and the swelling of the battery due to the separation of the electrode and the separator during use of the battery and the bending of the electrode winding body by bonding the electrode and the separator, In addition, since the electrode / separator interlayer adhesion means due to external force from the metal can or the like is not required, the adhesive force does not decrease even at high temperature, and ionic conduction between the electrode and the separator is not hindered. Even when using a separator such as polyolefin that is difficult to adhere to, it has a strong adhesive strength and does not leave unnecessary organic solvent in the battery. For a laminate in which a plurality of positive electrodes, negative electrodes, and separators are laminated However, it is still another object of the present invention to provide a bonding method capable of rapidly impregnating the inside with an electrolytic solution.
【００１２】また本発明の他の目的は、上記の接着方法
において、セパレータの損傷を抑えるために低いプロセ
ス温度で上記の接着を行うことを可能とする接着用材料
を提供することにある。Another object of the present invention is to provide a bonding material which enables the above bonding at a low process temperature in order to suppress damage to the separator in the above bonding method.
【００１３】[0013]
【課題を解決するための手段】本発明は、多孔質正極と
多孔質負極の間に多孔質セパレータが配置された電極セ
パレータ積層体において、前記多孔質正極、多孔質負極
および多孔質セパレータの３者が、ポリマー架橋物によ
って、積層された面内の不連続した位置において互いに
層間接着されていることを特徴とする電極セパレータ積
層体に関する。The present invention provides an electrode-separator laminate in which a porous separator is disposed between a porous positive electrode and a porous negative electrode, wherein the porous positive electrode, the porous negative electrode and the porous separator are 3 The present invention relates to an electrode separator laminate, wherein the polymer is cross-linked with each other at discontinuous positions in the laminated plane by a polymer cross-linked product.
【００１４】また本発明は、多孔質正極と多孔質負極の
間に多孔質セパレータが配置された電極セパレータ積層
体の製造方法において、前記多孔質セパレータ、多孔質
正極および多孔質負極の少なくとも一つに対し、熱可塑
性ポリマーを積層面内の不連続した位置に付着させたも
のを用いて、前記多孔質正極および多孔質負極の間に前
記多孔質セパレータが挟まれるように重ね合わせ、その
後加熱して熱可塑性ポリマーを溶融して、前記多孔質セ
パレータ、多孔質正極および多孔質負極の各細孔内部に
流入させる工程と、熱可塑性ポリマーを架橋させる工程
とを有する電極セパレータ積層体の製造方法に関する。The present invention also provides a method for producing an electrode separator laminate in which a porous separator is arranged between a porous positive electrode and a porous negative electrode, wherein at least one of the porous separator, the porous positive electrode and the porous negative electrode is used. On the other hand, by using the one in which the thermoplastic polymer is attached at a discontinuous position in the laminated surface, the porous positive electrode and the porous negative electrode are stacked so that the porous separator is sandwiched between them, and then heated. Relating to a method for manufacturing an electrode separator laminate having a step of causing a thermoplastic polymer to melt and flowing into the pores of the porous separator, the porous positive electrode and the porous negative electrode, and a step of crosslinking the thermoplastic polymer. .
【００１５】さらに本発明は、これらの電極セパレータ
積層体に電解液を含浸させた電池に関する。Further, the present invention relates to a battery in which these electrode separator laminates are impregnated with an electrolytic solution.
【００１６】[0016]
【発明の実施の形態】本発明の電極セパレータ積層体の
代表的構造を図１を参照しながら説明する。多孔質正極
は、正極集電体１と、その上に成膜された正極活物質粒
子２の結着体の層を有している。同様に多孔質負極は、
負極集電体５と、その上に成膜された負極活物質粒子４
の結着体の層を有している。正極活物質粒子２の結着体
の層および負極活物質粒子４の結着体の層において、活
物質粒子は、互いに結着剤により結着して層内では連続
体となっており、また残された隙間により多孔質となっ
ている。そして、正極と負極の間は多孔質セパレータ３
によって隔てられており、さらにポリマー架橋物６が、
セパレータ３と正極活物質粒子の結着体層、セパレータ
３と負極活物質粒子の結着体層の間にわたって形成され
てそれぞれを接着している。本発明では、このようにセ
パレータと多孔質正極および多孔質負極との間の接着
を、ポリマー架橋物を用いて行うので、高温においても
溶融したり電解液に溶解することがなく、接着力が低下
しない。BEST MODE FOR CARRYING OUT THE INVENTION A typical structure of an electrode separator laminate of the present invention will be described with reference to FIG. The porous positive electrode has a positive electrode current collector 1 and a layer of a binder of the positive electrode active material particles 2 formed thereon. Similarly, the porous negative electrode is
Negative electrode current collector 5 and negative electrode active material particles 4 formed thereon
Has a binder layer. In the layer of the binder of the positive electrode active material particles 2 and the layer of the binder of the negative electrode active material particles 4, the active material particles are bound to each other by the binder to form a continuous body in the layer, and It is porous due to the remaining gaps. The porous separator 3 is provided between the positive electrode and the negative electrode.
Are separated by the polymer cross-linked product 6,
The separator 3 and the positive electrode active material particle binder layer, and the separator 3 and the negative electrode active material particle binder layer are formed and bonded to each other. In the present invention, since the adhesion between the separator and the porous positive electrode and the porous negative electrode is thus performed by using the polymer cross-linked product, the adhesive strength is not melted even at high temperature or dissolved in the electrolytic solution. Does not fall.
【００１７】その際、ポリマー架橋物６は、セパレータ
の積層面内の全面に形成されているのではなく、図に示
すように、面内で不連続した位置に形成されている。そ
れにより、ポリマー架橋物の存在しない部分でイオンが
多孔質正極、多孔質セパレータ、多孔質負極の間で自由
に行き来することができるので、層間イオン伝導に支障
をきたすことがなく、良好なイオン伝導性を示すのであ
る。At this time, the cross-linked polymer 6 is not formed on the entire surface of the laminated surface of the separator, but is formed at discontinuous positions in the surface as shown in the figure. As a result, ions can freely move back and forth between the porous positive electrode, the porous separator, and the porous negative electrode in the portion where the polymer cross-linked product does not exist, so that good ionization can be achieved without interfering with interlayer ionic conduction. It exhibits conductivity.
【００１８】本発明に用いる活物質粒子の粒子径として
は、正極、負極いずれの場合も８０μｍ以下が好まし
く、さらに３０μｍ以下が好ましい。また、粒径が小さ
すぎても結着体を形成しにくくなるので、通常０．５μ
ｍ以上、好ましくは５μｍ以上である。これらの粒子が
結着した結着体の層の空隙率は１〜５０％であることが
好ましく、さらに１０〜４０％が好ましい。また、結着
体の層厚としては、通常５０〜４００μｍ程度である。The particle size of the active material particles used in the present invention is preferably 80 μm or less, and more preferably 30 μm or less in both the positive electrode and the negative electrode. If the particle size is too small, it is difficult to form a binder, so 0.5 μm is usually used.
m or more, preferably 5 μm or more. The porosity of the binder layer in which these particles are bound is preferably 1 to 50%, more preferably 10 to 40%. The layer thickness of the binder is usually about 50 to 400 μm.
【００１９】正極活物質粒子として用いられる材料とし
ては、リチウムイオンを吸蔵保存できるものが好まし
く、一般にリチウム二次電池の正極活物質として用いら
れるものが挙げられ、例えばマンガン酸リチウム、Ｌｉ
ＣｏＯ2、ＬｉＮｉＯ2、およびＬｉｘＶ2Ｏ5（０＜ｘ＜
２）等のリチウム複合酸化物、ポリアニリンおよびポリ
チオフェン等の高分子化合物を挙げることができる。こ
の中でもＬｉＭｎ2Ｏ4等のマンガン酸リチウム、ＬｉＣ
ｏＯ2、ＬｉＮｉＯ2が好ましい。As the material used as the positive electrode active material particles, those capable of storing and storing lithium ions are preferable, and those generally used as the positive electrode active material of a lithium secondary battery can be mentioned, for example, lithium manganate and Li.
CoO 2 , LiNiO 2 , and LixV 2 O 5 (0 <x <
Examples thereof include lithium composite oxides such as 2) and polymer compounds such as polyaniline and polythiophene. Among them, lithium manganate such as LiMn 2 O 4 and LiC
OO 2 and LiNiO 2 are preferable.
【００２０】また負極として用いられる材料としては、
リチウムイオンを吸蔵保存できるものが好ましく、一般
にリチウム二次電池の負極活物質として用いられるもの
が挙げられ、例えばグラファイト粒子、アモルファスカ
ーボン粒子、天然黒鉛、石炭・石油ピッチを高温で熱処
理して得られる黒鉛化炭素のような結晶質カーボン、石
油ピッチコークス、石炭ピッチコークス、アセナフチレ
ンピッチコークスを熱処理して得られる非晶質カーボン
等のカーボン系材料、ポリアセン、およびリチウム−ア
ルミニウム合金粉末等を挙げることができる。この中で
もグラファイト粒子、アモルファスカーボン粒子、天然
黒鉛、ポリアセンが好ましい。The material used for the negative electrode is
Those capable of occluding and storing lithium ions are preferable, and those generally used as a negative electrode active material of a lithium secondary battery can be mentioned, for example, graphite particles, amorphous carbon particles, natural graphite, obtained by heat-treating coal / petroleum pitch at high temperature. Crystalline carbon such as graphitized carbon, petroleum pitch coke, coal pitch coke, carbon-based material such as amorphous carbon obtained by heat treatment of acenaphthylene pitch coke, polyacene, and lithium-aluminum alloy powder be able to. Of these, graphite particles, amorphous carbon particles, natural graphite and polyacene are preferable.
【００２１】また、活物質を結着させるための結着剤と
しては、樹脂バインダーが好ましく、例えばポリフッ化
ビニリデン、ビニリデンフロライド−ヘキサフルオロプ
ロピレン共重合体、ビニリデンフロライド−テトラフル
オロエチレン共重合体、スチレン・ブタジエン共重合ゴ
ム、ポリテトラフルオロエチレン、ポリプロピレン、ポ
リエチレン、ポリイミド等を挙げることができる。この
中でも特にポリフッ化ビニリデン、スチレン・ブタジエ
ン共重合ゴム、ポリイミドが好ましい。Further, as the binder for binding the active material, a resin binder is preferable, for example, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer. , Styrene / butadiene copolymer rubber, polytetrafluoroethylene, polypropylene, polyethylene, polyimide and the like. Among these, polyvinylidene fluoride, styrene / butadiene copolymer rubber, and polyimide are particularly preferable.
【００２２】また、集電体としては金属箔や金属メッシ
ュが挙げられる。正極の場合はアルミニウム箔、負極の
場合は銅箔が好ましく、厚さは、例えば５〜５０μｍで
ある。これらの集電体に対して、活物質の結着体は、結
着剤により接着されている。The current collector may be a metal foil or a metal mesh. Aluminum foil is preferable for the positive electrode and copper foil is preferable for the negative electrode, and the thickness is, for example, 5 to 50 μm. The binder of the active material is bonded to these current collectors with a binder.
【００２３】また本発明で用いられる多孔質セパレータ
は、一般的にはマイクロポーラスセパレータを用いる
が、本発明の効果が得られれば織布、不織布を用いるこ
ともできる。マイクロポーラスセパレータとしては、例
えば孔径０．１〜５μｍ、空孔率３０〜７０％、厚さ１
〜５０μｍのものを用いることができる。また、織布、
不織布を用いる場合は、繊維径１〜１００μｍ程度で、
空隙率３０〜７０％、厚さ１〜５０μｍのものが好まし
い。セパレータの材質は、ポリエチレン、ポリプロピレ
ン等のポリオレフィン系樹脂、ポリエステルなどを用い
ることができる。本発明では、特にポリオレフィン系樹
脂を用いた多孔質セパレータであっても、セパレータと
電極の間の接着が十分に行われる。As the porous separator used in the present invention, a microporous separator is generally used, but a woven fabric or a non-woven fabric may be used as long as the effect of the present invention can be obtained. As the microporous separator, for example, the pore diameter is 0.1 to 5 μm, the porosity is 30 to 70%, and the thickness is 1
A film having a thickness of up to 50 μm can be used. Woven cloth,
When a non-woven fabric is used, the fiber diameter is about 1 to 100 μm,
Those having a porosity of 30 to 70% and a thickness of 1 to 50 μm are preferable. As a material of the separator, a polyolefin resin such as polyethylene or polypropylene, polyester, or the like can be used. In the present invention, the adhesion between the separator and the electrode is sufficiently performed even in the case of the porous separator using the polyolefin resin.
【００２４】本発明で用いられるポリマー架橋物は、高
温においても溶融せず、電解液に不溶もしくは難溶とな
るような程度に架橋されている必要がある。その程度と
しては、１００℃において１ＭＰａ以上の力学強度を持
つものが好ましく、また、エチレンカーボネート、プロ
ピレンカーボネート、γ−ブチロラクトン、炭酸ジエチ
ルといったカーボネート系溶媒またはラクトン系溶媒
に、１００℃においても溶解しないものが好ましい。The crosslinked polymer used in the present invention must be crosslinked to such an extent that it does not melt even at a high temperature and becomes insoluble or hardly soluble in the electrolytic solution. As its degree, those having a mechanical strength of 1 MPa or more at 100 ° C. are preferable, and those which are not dissolved even at 100 ° C. in a carbonate solvent or lactone solvent such as ethylene carbonate, propylene carbonate, γ-butyrolactone or diethyl carbonate. Is preferred.
【００２５】本発明のポリマー架橋物は、具体的には、
後述するようにセパレータと電極とを貼り合わせてから
架橋して得られるようなものである。The polymer cross-linked product of the present invention is specifically
As will be described later, it is obtained by bonding a separator and an electrode and then cross-linking them.
【００２６】このポリマー架橋物は、セパレータの面内
の不連続した位置に存在している。即ち、イオンが電極
およびセパレータの層間で行き来できて、また後述する
ように電解液を充填する際に妨げにならない程度に不連
続になっていれば良い。例えば平面的に見たときにポリ
マー架橋物が独立した島状に多数形成されており、その
一つ一つの形状が円形状、矩形状、十字状等であって、
それらが面内に規則的にまたはランダムに分布している
パターン；互い違いに切れ目のあるストライプ状を多数
形成したパターン；切れ目のある網状パターン等を挙げ
ることができる。特に、本発明の電極セパレータ積層体
を巻回して用いる場合は、巻回方向に長細く、互い違い
に切れ目のあるストライプ状を多数形成したパターンの
ポリマー架橋物を形成すると、たわみ発生を効果的に抑
制できる。これは、たとえば角型の巻回型電池の場合、
充放電を繰り返すことなどにより電極やセパレータがた
わむことによるしわが主として巻回方向と垂直方向にで
きる傾向があるためである。また、積層体の周囲部分に
枠状にポリマー架橋物を形成してもよい。この場合、横
から電解液が入りやすくするように、途切れ途切れに形
成することが好ましい。The crosslinked polymer is present at discontinuous positions within the surface of the separator. That is, it suffices that the ions can move back and forth between the layers of the electrode and the separator and are discontinuous to the extent that they do not hinder the filling of the electrolytic solution as described later. For example, when viewed two-dimensionally, a large number of polymer cross-linked products are formed in independent islands, and each shape is circular, rectangular, cross-shaped,
Examples thereof include a pattern in which they are regularly or randomly distributed in a plane; a pattern in which a large number of stripes having alternating cuts are formed; and a net-like pattern having cuts. In particular, when the electrode separator laminate of the present invention is wound and used, when a polymer cross-linked product having a pattern in which a large number of stripes with staggered staggers are formed in the winding direction is effective, the occurrence of bending is effectively generated. Can be suppressed. For example, in the case of a square wound battery,
This is because wrinkles due to bending of the electrodes and the separator due to repeated charging and discharging tend to be formed mainly in the direction perpendicular to the winding direction. In addition, a polymer cross-linked product may be formed in a frame shape around the periphery of the laminate. In this case, it is preferable that the electrolytic solution is formed intermittently so that the electrolytic solution can easily enter from the side.
【００２７】ポリマー架橋物が面内で占める面積の割合
は、層間接着強度、イオン伝導性、および後述するよう
に電解液を毛細管現象により含浸させるときの容易さを
考慮すると、０．０１〜３０％であることが好ましく、
特に０．１〜１０％が好ましい。The ratio of the area occupied by the crosslinked polymer in the plane is 0.01 to 30 in consideration of the interlaminar adhesive strength, the ionic conductivity, and the ease of impregnating the electrolytic solution by the capillary phenomenon as described later. % Is preferable,
Particularly, 0.1 to 10% is preferable.
【００２８】また、ポリマー架橋物の面内での分布状態
は、毛細管現象による電解液含浸の容易さと共に、必要
な接着強度がとれるように、適宜面内に均一にまたはラ
ンダムに分布させることが好ましい。Further, the distribution state of the crosslinked polymer in the plane may be appropriately or uniformly distributed in the plane so that the impregnation with the electrolytic solution by the capillary phenomenon is facilitated and the necessary adhesive strength is obtained. preferable.
【００２９】図１に示した例では、ポリマー架橋物６
が、正極、セパレータ、負極の各細孔内部の３つの領域
にわたる連続体となっている。すなわち、セパレータと
正極（負極）の２者の間だけを層間接着しているのでは
なく、一つの連続したポリマー架橋物が３者を共に層間
接着している。こうすることにより、片方の極とセパレ
ータだけが接着されるのでなく、正極と負極との間でも
接着力が働き、電極セパレータ積層体全体として剥離し
にくい一体化物とすることができる。特に、セパレータ
として一般の接着剤で接着しにくいポリオレフィン系樹
脂のマイクロポーラスセパレータを用いた場合でも、ポ
リオレフィン表面と接着剤との界面での接着力とは関係
なく、正極と負極との間で接着力が働くので好ましい。In the example shown in FIG. 1, the crosslinked polymer 6
Is a continuous body extending over three regions inside the pores of the positive electrode, the separator, and the negative electrode. That is, not only the two members, the separator and the positive electrode (negative electrode), are bonded to each other by an interlayer, but one continuous polymer cross-linked product bonds the three members together. By doing so, not only the one electrode and the separator are bonded, but also the adhesive force acts between the positive electrode and the negative electrode, so that the electrode separator laminate as a whole can be made into an integrated product that is difficult to peel off. In particular, even when using a microporous separator of a polyolefin-based resin that is difficult to bond with a general adhesive as a separator, regardless of the adhesive force at the interface between the polyolefin surface and the adhesive, bonding between the positive electrode and the negative electrode It is preferable because the force works.
【００３０】図１に示した例では、さらに、ポリマー架
橋物６が、正極および負極の細孔内においてアンカー形
状を有している。ここでアンカー形状とは、粒子が集ま
って形成される狭い空間や広い空間が複合した連続空間
を満たすように粒子の裏側にも入り込んだ形状である。
ポリマー架橋物がこのような形状を有していることによ
り、上述したような正極と負極との間で働く接着力をよ
り強固なものとすることができる。このとき、通常、正
極、負極に対して、２０〜７０μｍ程度の深さまでポリ
マー架橋物が流入してもぐり込んでいることが好まし
い。In the example shown in FIG. 1, the polymer cross-linked product 6 further has an anchor shape in the pores of the positive electrode and the negative electrode. Here, the anchor shape is a shape that also enters the back side of the particles so as to fill a continuous space in which a narrow space formed by gathering particles and a wide space are combined.
Since the crosslinked polymer has such a shape, the adhesive force acting between the positive electrode and the negative electrode as described above can be made stronger. At this time, normally, it is preferable that the crosslinked polymer penetrates into the positive electrode and the negative electrode even if the crosslinked polymer flows to a depth of about 20 to 70 μm.
【００３１】本発明の電池は、このような電極セパレー
タ積層体に、電解液を含浸して形成される電池である。
本発明の電池では、層間を接着するポリマー架橋物用い
ていても、従来の通常のリチウムイオン電池の場合と同
様に、正極、負極、およびセパレータの積層後・層間接
着後に毛管現象を用いて積層体の横からスムーズに電解
液を内部に含浸することが可能である。これは、層間接
着剤であるポリマー架橋物が、面内に部分的に形成され
ているので、ポリマー架橋物が形成されていない部分で
は従来と同様にセパレータと電極との界面で毛管現象が
起こり、そこを経由して電池全体に電解液を含浸させる
ことができるからである。The battery of the present invention is a battery formed by impregnating such an electrode separator laminate with an electrolytic solution.
In the battery of the present invention, even if a polymer cross-linked product that adheres between layers is used, the positive electrode, the negative electrode, and the separator are laminated using the capillary phenomenon after lamination and interlayer adhesion, as in the case of the conventional ordinary lithium ion battery. It is possible to smoothly impregnate the inside of the electrolyte from the side of the body. This is because the polymer crosslinked product which is the interlayer adhesive is partially formed in the plane, so that the capillary phenomenon occurs at the interface between the separator and the electrode in the portion where the polymer crosslinked product is not formed as in the conventional case. The reason for this is that the entire battery can be impregnated with the electrolytic solution therethrough.
【００３２】電解液としては、例えばＬｉＰＦ6をエチ
レンカーボネート／プロピレンカーボネート混合溶媒に
１Ｍの濃度で溶解したものが用いられる。その他、Ｌｉ
ＢＦ 4、ＬｉＣＦ3ＳＯ3、ＬｉＮ（Ｃ2Ｆ5ＳＯ2）2等を
ジメチルカーボネート、ジエチルカーボネート、γ−ブ
チロラクトン等に溶解した溶液でも良い。As the electrolytic solution, for example, LiPF 6 is used.6Echi
For ren carbonate / propylene carbonate mixed solvent
What was dissolved at a concentration of 1M is used. Others, Li
BF Four, LiCF3SO3, LiN (C2FFiveSO2)2Etc.
Dimethyl carbonate, diethyl carbonate, γ-bu
It may be a solution dissolved in tyrolactone or the like.
【００３３】また、本発明の電極セパレータ積層体で
は、複数の層を積層することもできる。即ち、図２に示
すように正極、負極とも集電体の両面に活物質粒子の結
着体を接着させたものを用い（但し、最も外側の電極は
片面）、複数のそれらとセパレータとを多数層積層して
形成することで、電池容量を上げることができる。図２
では積層の一部分を示しており、上下にも積層されてい
る。このように多数層とした場合でも、従来の通常のリ
チウムイオン電池の場合と同様に、電極とセパレータの
積層後・層間接着後に毛管現象を用いて積層体の横から
スムーズに電解液を内部に含浸することが可能である。Further, in the electrode separator laminate of the present invention, a plurality of layers can be laminated. That is, as shown in FIG. 2, a positive electrode and a negative electrode each having a binder of active material particles adhered to both sides of a current collector (however, the outermost electrode is one side) are used, and a plurality of them and a separator are used. The battery capacity can be increased by stacking a large number of layers. Figure 2
In the figure, a part of the stacked layers is shown, and they are stacked on top and bottom. Even in the case of multiple layers like this, as in the case of the conventional ordinary lithium ion battery, after the electrode and the separator are laminated and after the interlayer adhesion, the electrolytic solution is smoothly introduced from the side of the laminate by using the capillary phenomenon. Impregnation is possible.
【００３４】本発明の電極セパレータ積層体が巻き回さ
れた形態のときは、正極と負極の間にセパレータが挟ま
れた状態で巻き回されていればよく、例えば、負極、セ
パレータ、正極、セパレータの順に重ねて巻き回された
形態のように正極および負極がそれぞれ１枚である場合
の他、複数の正極および複数の負極が間にセパレータが
挟まれて巻き回された形態であってもよい（以下、巻回
し型ともいう）。When the electrode-separator laminate of the present invention is wound, the separator may be wound with the separator sandwiched between the positive electrode and the negative electrode. For example, the negative electrode, the separator, the positive electrode, the separator. In addition to the case where each of the positive electrode and the negative electrode is one as in the form of being wound in a laminated manner in the order of, the separator may be wound with a plurality of positive electrodes and a plurality of negative electrodes sandwiched therebetween. (Hereinafter, also referred to as a roll type).
【００３５】次に本発明の電極セパレータ積層体の製造
方法を説明する。Next, a method for manufacturing the electrode separator laminate of the present invention will be described.
【００３６】図３は、本発明の電極セパレータ積層体の
製造方法の実施の形態の一つの例を説明するための模式
図である。FIG. 3 is a schematic view for explaining one example of the embodiment of the method for producing an electrode separator laminate according to the present invention.
【００３７】まず、本発明では、図３に示すように、例
えば、多孔質セパレータ３に、熱可塑性ポリマー７を面
内に部分的に付着させたものを用いる。付着させる方法
としては、架橋性ポリマーの溶融液あるいは無機溶媒や
有機溶媒に溶解した溶液を塗布する方法が挙げられる。
なお、本発明で用いられる熱可塑性ポリマーは、架橋可
能なポリマーである。この時、例えば直径１ｍｍの円形
パターン等のパターン状に熱可塑性ポリマーを付着させ
ることが好ましい。この時さらに、セパレータの両面に
位置を合わせてパターン状に熱可塑性ポリマーを付着さ
せることが好ましい。こうすることにより、熱可塑性ポ
リマーをセパレータの両面に盛り上がった状態で付着さ
せることができ、セパレータの細孔内部にも充填され、
セパレータの両面にわたる連続体を形成することができ
る。熱可塑性ポリマーを付着させる際、セパレータの全
面積に対する熱可塑性ポリマーの占める面積の割合を、
０．０１〜３０％、特に０．１〜１０％となるように行
うことが好ましい。First, in the present invention, as shown in FIG. 3, for example, a porous separator 3 in which a thermoplastic polymer 7 is partially adhered in-plane is used. Examples of the method for attaching include a method of applying a melt of a crosslinkable polymer or a solution dissolved in an inorganic solvent or an organic solvent.
The thermoplastic polymer used in the present invention is a crosslinkable polymer. At this time, it is preferable to attach the thermoplastic polymer in a pattern such as a circular pattern having a diameter of 1 mm. At this time, it is further preferable that the thermoplastic polymer is attached in a pattern in alignment with both surfaces of the separator. By doing so, it is possible to adhere the thermoplastic polymer in a raised state on both sides of the separator, is also filled inside the pores of the separator,
It is possible to form a continuum over both sides of the separator. When attaching the thermoplastic polymer, the ratio of the area occupied by the thermoplastic polymer to the total area of the separator,
It is preferably carried out so as to be 0.01 to 30%, particularly 0.1 to 10%.
【００３８】工法としては凸版印刷、凹版印刷、インク
ジェット印刷法等およびスプレー法等を用いることがで
きる。スプレー法を用いる場合は、ベタ塗りにせずに、
塗布量を微量とし、熱可塑性ポリマーが不連続な島状に
形成されるようにする。As the construction method, relief printing, intaglio printing, ink jet printing method, spray method and the like can be used. When using the spray method, do not apply solid coating,
The coating amount is set to a small amount so that the thermoplastic polymer is formed into discontinuous islands.
【００３９】次に、上記のセパレータを正極および負極
で挟み込んで（図３（ａ））、適当に加圧しながら加熱
することにより、正極および負極の各細孔内部に熱可塑
性ポリマー７を溶融させ流入させる（同図（ｂ））。こ
うすることにより、正極、負極、セパレータの各細孔内
部の３つの領域にわたるアンカー形状の熱可塑性ポリマ
ーの連続体を形成することができる。ここで、熱可塑性
ポリマーとして、常温で固体であり、かつその融点また
は軟化点（好ましくは融点）が、セパレータの融点（融
点が存在しないときは軟化点）よりも低いものを用い、
前記の加熱の際に、熱可塑性ポリマーの融点または軟化
点（好ましくは融点）以上かつセパレータの融点または
軟化点以下の温度で系全体を加熱することが好ましい。
常温で固体である架橋性ポリマーを用いることにより、
特開平１０−２８９７３２号公報に記載されている低分
子モノマーを塗布する方法において見られるような成分
の揮発や液だれが無くなるので、セパレータへの接着剤
の塗布（付着）が、量的に制御性良く、能率良く行うこ
とができる。またこの後の熱架橋反応時にモノマーが揮
発するという問題も無くなる。Next, the above-mentioned separator is sandwiched between the positive electrode and the negative electrode (FIG. 3 (a)) and heated while being appropriately pressurized to melt the thermoplastic polymer 7 inside the pores of the positive electrode and the negative electrode. Inflow ((b) of the same figure). By doing so, an anchor-shaped thermoplastic polymer continuum can be formed over three regions inside each of the pores of the positive electrode, the negative electrode, and the separator. Here, as the thermoplastic polymer, one that is solid at room temperature and has a melting point or softening point (preferably melting point) lower than the melting point of the separator (softening point when no melting point exists) is used,
In the heating, it is preferable to heat the entire system at a temperature not lower than the melting point or softening point (preferably melting point) of the thermoplastic polymer and not higher than the melting point or softening point of the separator.
By using a crosslinkable polymer that is solid at room temperature,
Since the volatilization of components and the dripping as seen in the method of applying a low molecular weight monomer described in JP-A-10-289732 are eliminated, the application (adhesion) of the adhesive to the separator is quantitatively controlled. It can be done efficiently and efficiently. Further, there is no problem that the monomer is volatilized during the subsequent thermal crosslinking reaction.
【００４０】尚、巻回し型の電極セパレータ積層体を製
造するときは、巻き回したときに正極と負極の間にセパ
レータが挟まれるように必要枚数を重ねて巻き回して、
それから適当に加圧しながら加熱することにより、正極
および負極の各細孔内部に熱可塑性ポリマーを溶融させ
流入させればよい。When manufacturing a wound-type electrode separator laminate, the necessary number of layers are stacked and wound so that the separator is sandwiched between the positive electrode and the negative electrode when wound.
Then, the thermoplastic polymer may be melted and flowed into the pores of the positive electrode and the negative electrode by heating while appropriately applying pressure.
【００４１】次に、セパレータを正極および負極と挟ん
だ状態で、前記熱可塑性ポリマー７を架橋させ、ポリマ
ー架橋物とする。こうして、正極、負極、セパレータの
各細孔内部の３つの領域にわたるアンカー形状のポリマ
ー架橋体の連続体を形成することができる。そうするこ
とにより、外部からの加圧を取り除いた後も、正極と負
極とでセパレータを圧縮した状態の、強固な接着力を持
つ電極セパレータ積層体が得られる。Next, with the separator sandwiched between the positive electrode and the negative electrode, the thermoplastic polymer 7 is crosslinked to obtain a polymer crosslinked product. In this way, a continuous anchor-shaped polymer cross-linked body can be formed over the three regions inside the pores of the positive electrode, the negative electrode, and the separator. By doing so, it is possible to obtain an electrode-separator laminate having a strong adhesive force in a state where the separator is compressed by the positive electrode and the negative electrode even after removing the external pressure.
【００４２】熱可塑性ポリマーを架橋させる方法として
は、あらかじめ熱重合開始剤を熱可塑性ポリマーに含ま
せておき、上記のように熱可塑性ポリマーを溶融させて
多孔質の正極・負極に流入させた後、さらに加熱して架
橋させることが好ましい。As a method for crosslinking the thermoplastic polymer, a thermopolymerization initiator is contained in advance in the thermoplastic polymer, and the thermoplastic polymer is melted as described above and allowed to flow into the porous positive and negative electrodes. It is preferable to further heat and crosslink.
【００４３】ここで用いられる熱重合開始剤としては、
アゾビスイソブチロニトリル、ベンゾイルパーオキサイ
ド、メチルエチルケトンパーオキサイド、ジ−ｔ−ブチ
ルパーオキサイド、ｔ−ブチルパーオキシネオデカノエ
ート、ｔ−ヘキシルパーオキシピバレート、ｔ−ブチル
パーオキシ−２−エチルヘキサノエート、ビス（４−ｔ
−ブチルシクロヘキシル）パーオキシジカーボネート、
ラウロイルパーオキサイド等を挙げることができる。こ
れらの中から、分解温度とセパレータの融点または軟化
点を考慮して適宜選ぶことができる。中でも、常温で固
体であり融点がセパレータの融点または軟化点よりも低
いものを選ぶことが好ましい。そうすることにより、熱
可塑性ポリマーを形成したセパレータの常温保存中の熱
重合開始剤の劣化を抑制し、加熱して架橋反応させる際
に効果的にポリマーに作用させることができる。As the thermal polymerization initiator used here,
Azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, di-t-butyl peroxide, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl peroxy-2-ethyl Hexanoate, bis (4-t
-Butylcyclohexyl) peroxydicarbonate,
Examples thereof include lauroyl peroxide. From these, it can be appropriately selected in consideration of the decomposition temperature and the melting point or softening point of the separator. Above all, it is preferable to select one that is solid at room temperature and has a melting point lower than the melting point or softening point of the separator. By doing so, deterioration of the thermal polymerization initiator during storage of the separator formed with the thermoplastic polymer at room temperature can be suppressed, and the polymer can be effectively acted upon by heating to cause a crosslinking reaction.
【００４４】架橋の為の加熱温度はセパレータの融点ま
たは軟化点以下の温度で行うことが好ましい。架橋のた
めの加熱は、熱可塑性ポリマーを溶融して電極細孔に流
入させるときの加熱に引き続いて行っても、また別個に
異なる温度を設定してもどちらでもよい。また、熱重合
開始剤の使用割合は、熱可塑性ポリマーに対して、０．
０１〜２０重量％、好ましくは０．１〜１０重量％であ
る。The heating temperature for crosslinking is preferably a temperature below the melting point or softening point of the separator. The heating for crosslinking may be performed subsequent to the heating when the thermoplastic polymer is melted and allowed to flow into the electrode pores, or may be separately set at different temperatures. The ratio of the thermal polymerization initiator used is 0.
It is from 01 to 20% by weight, preferably from 0.1 to 10% by weight.
【００４５】なお、熱可塑性ポリマーとして、ポリオレ
フィン系のものを用いると、ポリオレフィン系セパレー
タとの密着性が良くなり好ましい。さらに側鎖にビニル
を持つものを用いると、末端にのみ架橋性機能基を有す
るものに比べて低い温度で架橋することができ、ポリオ
レフィン系マイクロポーラスセパレータなどのような熱
に弱いセパレータを用いた場合に都合がよく、水酸基、
カルボキシル基、イソシアネート基、グリシジル基など
の他の架橋性機能基を用いた場合に比べて、副反応物が
無いこと、リチウムのトラップが起きないこと等の観点
から好ましい。It is preferable to use a polyolefin-based thermoplastic polymer as the thermoplastic polymer because the adhesion with the polyolefin-based separator is improved. Furthermore, when a vinyl chain-containing one is used, it can be crosslinked at a lower temperature than that having a crosslinkable functional group only at the terminal, and a heat-sensitive separator such as a polyolefin microporous separator was used. Convenient for the case,
Compared with the case where other crosslinkable functional groups such as a carboxyl group, an isocyanate group, and a glycidyl group are used, it is preferable from the viewpoints of no side reaction products and no lithium trap.
【００４６】以上述べたいくつかの観点において好まし
い架橋性ポリマーの例としては、１，２−ポリブタジエ
ンを挙げることができる。その際、１，２−結合は１０
０％である必要はなく、好ましくは８０％以上である。
またこのような、１，２−ポリブタジエンを５０重量％
以上含むコポリマーまたはポリマー混合物であっても良
い。As an example of the crosslinkable polymer preferable in some of the above-mentioned aspects, 1,2-polybutadiene can be mentioned. At that time, 1,2-bond is 10
It does not need to be 0%, and is preferably 80% or more.
In addition, 50% by weight of such 1,2-polybutadiene is used.
It may be a copolymer or polymer mixture containing the above.
【００４７】この他に、例えばエチレン−プロピレン−
ジエン共重合体、側鎖にビニル基を持つポリシロキサ
ン、末端ビニル化ポリシロキサン等の変性ポリシロキサ
ン、１，４−ポリブタジエン、スチレン−ブタジエン共
重合体、アクリロニトリル−ブタジエン共重合体、ポリ
イソプレン、ポリイソブチレン等も、架橋させる温度を
高くすれば使用できる。その際、セパレータとしてはポ
リエステル等の高耐熱性の材質のものを用いることが好
ましい。Besides this, for example, ethylene-propylene-
Diene copolymers, polysiloxanes having vinyl groups on the side chains, modified polysiloxanes such as terminal vinylated polysiloxanes, 1,4-polybutadiene, styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, polyisoprene, poly Isobutylene and the like can also be used if the temperature for crosslinking is increased. At that time, it is preferable to use a highly heat-resistant material such as polyester as the separator.
【００４８】また、トリメチロールプロパントリアクリ
レート、ジビニルベンゼン等の架橋剤を熱可塑性ポリマ
ーに添加してもよい。また、硫黄を添加（加硫）しても
よい。Further, a crosslinking agent such as trimethylolpropane triacrylate or divinylbenzene may be added to the thermoplastic polymer. Further, sulfur may be added (vulcanized).
【００４９】このように本発明の製造方法では、電極と
セパレータを貼り合わせた状態で接着材料から有機溶媒
を除去する工程が無い。従って従来のように電池内部に
不要な有機溶媒を残存させる恐れがない。また、セパレ
ータへの接着剤塗布の直後に正極、負極を貼り合わせて
接着する必要がなくなるので、熱可塑性ポリマーを付着
させたものを長期にわたりストックしておき、必要に応
じて積層し加熱するだけで目的の接着された電極積層体
を製造することもできる。接着剤塗布工程と電極積層工
程を分離することができれば、スループットの向上、ド
ライルーム中の設備を最小限にできる等のメリットが得
られる。特に、熱可塑性ポリマーが常温で固体であり、
かつ添加する熱重合開始剤が常温で固体のものを選ぶこ
とにより、熱重合開始剤が添加された熱可塑性ポリマー
を付着させたものを長期にわたり劣化させずにストック
することができ、必要に応じて積層し加熱するだけで、
さらに効果的に架橋された目的の接着された電極積層体
を製造することができる。As described above, in the manufacturing method of the present invention, there is no step of removing the organic solvent from the adhesive material with the electrode and the separator attached to each other. Therefore, unlike the conventional case, there is no fear that an unnecessary organic solvent remains inside the battery. In addition, since it is not necessary to bond the positive electrode and negative electrode together immediately after applying the adhesive to the separator, it is necessary to stock the one with the thermoplastic polymer attached for a long period of time, and stack and heat as needed. It is also possible to produce the desired bonded electrode laminate. If the adhesive application process and the electrode laminating process can be separated, there are advantages such as improvement in throughput and minimization of equipment in a dry room. In particular, the thermoplastic polymer is solid at room temperature,
And by selecting the solid thermal polymerization initiator to be added at room temperature, it is possible to stock the one to which the thermoplastic polymer to which the thermal polymerization initiator is added is attached without deteriorating for a long period of time. Simply stack and heat
Further, it is possible to effectively produce a desired bonded electrode laminate that is crosslinked.
【００５０】以上の説明で、セパレータに架橋性ポリマ
ーをパターン状に付着させる方法を例示したが、電極の
方に付着させてもよい。In the above description, the method of attaching the crosslinkable polymer to the separator in a pattern is exemplified, but it may be attached to the electrode.
【００５１】上記の形態では、架橋性ポリマーを、正
極、負極、およびセパレータの各細孔内部の３つの領域
にわたる連続体とした場合を示したが、セパレータの細
孔内部および一方の電極の細孔内部の２つの領域にわた
る連続体となっていてもよい。In the above embodiment, the case where the crosslinkable polymer is a continuous body extending over three regions inside each of the positive electrode, the negative electrode and the inside of each of the pores of the separator has been described. It may be a continuous body extending over two regions inside the hole.
【００５２】[0052]
【実施例】以下に実施例を示して本発明をさらに詳細に
説明するが、本発明は実施例に限定されるものではな
い。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples.
【００５３】（実施例１）スピネル構造を持つマンガン
酸リチウム粉末、炭素質導電性付与剤、アセチレンブラ
ック、およびポリフッ化ビニリデンを、８８：５：２：
５の重量比でＮ―メチル−２−ピロリドン（以下ＮＭＰ
と称する）に混合、分散し、攪拌して電極スラリーとし
た。ＮＭＰの量はスラリーが適当な粘度となるように調
整した。この電極スラリーをドクターブレード法によ
り、正極集電体となる厚さ２０μｍのアルミニウム箔の
片面に均一に塗布し、１００℃で２時間真空乾燥させ
た。このときの塗膜の付着重量は２０ｍｇ／ｃｍ2であ
った。同様にもう一方の面にもスラリーを塗布し真空乾
燥させた。最後にロールプレスを行って、正極集電体の
両面に正極活物質粒子結着体が接着した正極を得た。(Example 1) 88: 5: 2: lithium manganate powder having a spinel structure, carbonaceous conductivity-imparting agent, acetylene black, and polyvinylidene fluoride were added.
N-methyl-2-pyrrolidone (hereinafter referred to as NMP) in a weight ratio of 5
(Referred to below) as the electrode slurry. The amount of NMP was adjusted so that the slurry had an appropriate viscosity. This electrode slurry was uniformly applied to one side of a 20 μm thick aluminum foil serving as a positive electrode current collector by a doctor blade method, and vacuum dried at 100 ° C. for 2 hours. The adhesion weight of the coating film at this time was 20 mg / cm 2 . Similarly, the other surface was coated with the slurry and vacuum dried. Finally, roll pressing was performed to obtain a positive electrode in which the positive electrode active material particle binder was adhered to both surfaces of the positive electrode current collector.
【００５４】この正極活物質粒子結着体の空孔率は、ス
ピネル構造を持つマンガン酸リチウム粉末、炭素質導電
性付与剤、アセチレンブラック、およびポリフッ化ビニ
リデンの真密度と上記の塗膜付着重量と膜厚から計算し
たところ、２５％であった。これを、１７ｃｍ×６ｃｍ
の長方形に切り出した。これらの正極に、活物質の一部
を削り取ってそこに正極リードとしての長細いアルミニ
ウム箔を超音波溶接により取り付けた。The porosity of this positive electrode active material particle binder is the true density of the lithium manganate powder having a spinel structure, the carbonaceous conductivity-imparting agent, acetylene black, and polyvinylidene fluoride, and the above-mentioned coating weight. And calculated from the film thickness was 25%. This is 17 cm x 6 cm
Cut out into a rectangle. A part of the active material was scraped off from these positive electrodes, and a long thin aluminum foil as a positive electrode lead was attached thereto by ultrasonic welding.
【００５５】一方、アモルファスカーボン粉末、アセチ
レンブラック、およびポリフッ化ビニリデンを８７：
１：１２の重量比でＮＭＰに混合、分散し、攪拌して負
極スラリーとした。ＮＭＰの量はスラリーが適当な粘度
となるように調整した。この負極スラリーをドクターブ
レード法により、負極集電体となる厚さ１０μｍの銅箔
の片面に均一に塗布し、１００℃で２時間真空乾燥させ
た。このときの塗膜の付着量は８ｍｇ／ｃｍ2前後と
し、負極層の単位面積当たりの理論容量と正極層の単位
面積当たりの理論容量が等しくなるように調節した。同
様にもう一方の面にもスラリーを塗布し真空乾燥させ
た。最後にロールプレスを行って、負極集電体の両面に
接着した負極活物質粒子結着体を得た。On the other hand, 87: amorphous carbon powder, acetylene black, and polyvinylidene fluoride were added.
A weight ratio of 1:12 was mixed with NMP, dispersed, and stirred to obtain a negative electrode slurry. The amount of NMP was adjusted so that the slurry had an appropriate viscosity. This negative electrode slurry was uniformly applied to one surface of a copper foil having a thickness of 10 μm to be a negative electrode current collector by a doctor blade method, and vacuum dried at 100 ° C. for 2 hours. The amount of coating film deposited at this time was around 8 mg / cm 2, and was adjusted so that the theoretical capacity per unit area of the negative electrode layer and the theoretical capacity per unit area of the positive electrode layer were equal. Similarly, the other surface was coated with the slurry and vacuum dried. Finally, roll pressing was performed to obtain a negative electrode active material particle binder adhered to both surfaces of the negative electrode current collector.
【００５６】この負極活物質粒子結着体の空孔率は、ア
モルファスカーボン粉末、アセチレンブラック、および
ポリフッ化ビニリデンの真密度と上記の塗膜付着量と膜
厚から計算したところ、３５％であった。これを、１７
ｃｍ×６ｃｍの長方形に何枚か切り出した。また同様に
して、片面のみに負極活物質層を形成した１７ｃｍ×６
ｃｍの負極も何枚か用意した。これらの負極に、活物質
の一部を削り取ってそこに負極リードとしての長細い銅
箔を超音波溶接により取り付けた。The porosity of this negative electrode active material particle binder was 35% as calculated from the true densities of the amorphous carbon powder, acetylene black, and polyvinylidene fluoride, and the above-mentioned coating amount and film thickness. It was This is 17
Several pieces were cut into a rectangle of cm × 6 cm. Similarly, the negative electrode active material layer was formed on only one side 17 cm × 6
A few cm negative electrodes were also prepared. A part of the active material was scraped off from these negative electrodes, and a long thin copper foil as a negative electrode lead was attached thereto by ultrasonic welding.
【００５７】また他方、ポリプロピレン／ポリエチレン
／ポリプロピレンの３層構造を持つマイクロポーラスセ
パレータ（ヘキストセラニーズ社製、セルガード２３０
０）を、１８ｃｍ×７ｃｍの大きさに切り出した。これ
に、１，２−ポリブタジエン（ＪＳＲ製、商品名ＲＢ８
１０、１，２結合の含有比率９０％、融点７１℃、平均
分子量１０数万）が５重量％、ラウロイルパーオキサイ
ドが０．１重量％溶解したトルエン溶液を、円形パター
ン状に印刷した。パターン直径は約１ｍｍ、パターン間
隔は縦方向、横方向共に１ｃｍ、パターン当たりの液量
は０．２μｌとした。片面に印刷した後、裏返して、同
じ円形パターン部分に重複して印刷されるよう位置合わ
せをした上で同様にパターン印刷を行った。このときの
パターン形状を図４に示す。パターン印刷は判子型の板
を用いて行った。その後、４０℃２時間の真空乾燥を行
った。これを、１７ｃｍ×６ｃｍの長方形に切り出し
た。On the other hand, a microporous separator having a three-layer structure of polypropylene / polyethylene / polypropylene (Celguard 230 manufactured by Hoechst Celanese Co., Ltd.)
0) was cut into a size of 18 cm × 7 cm. 1,2-polybutadiene (JSR, trade name RB8
A toluene solution having a content ratio of 10,1,2 bonds of 90%, a melting point of 71 ° C., an average molecular weight of 100,000) of 5% by weight and lauroyl peroxide of 0.1% by weight was printed in a circular pattern. The pattern diameter was about 1 mm, the pattern interval was 1 cm in both the vertical and horizontal directions, and the liquid amount per pattern was 0.2 μl. After printing on one side, it was turned upside down, aligned so that the same circular pattern portion was printed overlappingly, and then the same pattern printing was performed. The pattern shape at this time is shown in FIG. The pattern printing was performed using a disc-shaped plate. Then, vacuum drying was performed at 40 ° C. for 2 hours. This was cut into a 17 cm × 6 cm rectangle.
【００５８】以上のようにして１，２−ポリブタジエン
（以下ＰＢＤ）を塗布したセパレータの塗布部分の断面
をＳＥＭ観察したところ、細孔内部にもＰＢＤが形成さ
れ、セパレータの表と裏に連続したポリマー層となって
いることが確認された。SEM observation of the cross section of the coated portion of the separator coated with 1,2-polybutadiene (hereinafter referred to as PBD) as described above revealed that PBD was formed inside the pores and was continuous on the front and back of the separator. It was confirmed that it was a polymer layer.
【００５９】以上のようにして用意した、両面に活物質
を形成した正極（以下両面正極）５枚、両面負極４枚、
片面負極２枚、セパレータ１０枚を、片面負極／セパレ
ータ／両面正極／セパレータ／両面負極／セパレータ／
両面正極／・・・／セパレータ／片面負極、という順に
積層した。これを真空パックしたものを卓上熱プレス機
で熱プレスした。条件は予備加熱８０℃５分、その後本
プレスを圧力２０ｋｇ／ｃｍ2、温度８０℃、時間５分
とした。次に１ｋｇ／ｃｍ2に圧力をゆるめ、温度は８
０℃のまま、１２時間加熱し続けた。Five positive electrodes (hereinafter, double-sided positive electrodes) having active materials formed on both sides, four double-sided negative electrodes, prepared as described above,
2 single-sided negative electrodes, 10 separators, single-sided negative electrode / separator / double-sided positive electrode / separator / double-sided negative electrode / separator /
Double-sided positive electrode /.../ Separator / single-sided negative electrode were laminated in this order. This was vacuum-packed and hot-pressed with a desktop heat press. The conditions were as follows: preheating at 80 ° C. for 5 minutes, then the main press at a pressure of 20 kg / cm 2 , temperature at 80 ° C., and time for 5 minutes. Next, the pressure is released to 1 kg / cm 2 , and the temperature is set to 8
Heating was continued for 12 hours at 0 ° C.
【００６０】以上の工程により、正極、負極、およびセ
パレータが互いに強く接着した電極積層体一体化物が得
られた。断面をＳＥＭ観察したところ、ＰＢＤ接着層
が、正極、負極、およびセパレータの各細孔内部の３つ
の領域にわたる連続体となっており、正極および負極の
細孔内においてアンカー形状を有していることが確認さ
れた。またＰＢＤ接着層を試料から一部削り取り、トル
エンに浸漬したところ、溶解しなかった。Through the above steps, an integrated electrode laminate having the positive electrode, the negative electrode, and the separator strongly bonded to each other was obtained. As a result of SEM observation of the cross section, the PBD adhesive layer is a continuous body extending over three regions inside each pore of the positive electrode, the negative electrode, and the separator, and has an anchor shape in the pores of the positive electrode and the negative electrode. It was confirmed. Further, when the PBD adhesive layer was partially scraped from the sample and immersed in toluene, it did not dissolve.
【００６１】以上のようにして得られた電極積層体から
引き出された正極リード同士、負極リード同士を互いに
溶接し、それぞれに電池端子タブとしての細長いアルミ
箔および銅箔を溶接して取り付けた。これをアルミニウ
ムラミネートフィルムの袋に入れ、そこにさらにエチレ
ンカーボネート／プロピレンカーボネートの１：１混合
溶媒に１Ｍの濃度でＬｉＰＦ6を溶解した電解液を注入
し、１分間減圧することによって電解液を電極積層体に
減圧含浸した。最後に電池端子タブを引き出した状態で
アルミニウムラミネートフィルムを封口した。このよう
にして薄型ラミネートタイプの本発明の電池を得た。な
お、電解液の注入から最後の封口処理までの工程はドラ
イボックスの中で行った。The positive electrode leads and the negative electrode leads drawn out from the electrode laminate obtained as described above were welded to each other, and a long aluminum foil and a copper foil as battery terminal tabs were welded and attached to each. This was put in a bag of aluminum laminate film, and an electrolyte solution in which LiPF 6 was dissolved at a concentration of 1M in a 1: 1 mixed solvent of ethylene carbonate / propylene carbonate was poured into the bag, and the pressure was reduced for 1 minute to make the electrolyte solution an electrode. The laminate was vacuum impregnated. Finally, the aluminum laminate film was sealed with the battery terminal tab pulled out. Thus, a thin laminate type battery of the present invention was obtained. The steps from the injection of the electrolytic solution to the final sealing treatment were performed in a dry box.
【００６２】この電池の充放電特性を次のようにして評
価した。３６０ｍＡの定電流で端子間電圧が４．２Ｖと
なるまで充電し、次に４．２Ｖで電流が充分絞り込まれ
るまで定電圧充電を行った。次に３６０ｍＡで定電流放
電を行い、端子間電圧が３Ｖとなるまで行って放電容量
を測定したところ、１７８０ｍＡｈの容量であった。同
様に充電を行い、１８００ｍＡで放電を行った場合の放
電容量は、１６５０ｍＡｈであった。The charge / discharge characteristics of this battery were evaluated as follows. Charging was performed at a constant current of 360 mA until the voltage between terminals reached 4.2 V, and then constant voltage charging was performed at 4.2 V until the current was sufficiently narrowed. Next, constant current discharge was performed at 360 mA, and the discharge capacity was measured by performing the discharge until the voltage between terminals became 3 V. The discharge capacity was 1780 mAh. Similarly, when the battery was charged and discharged at 1800 mA, the discharge capacity was 1650 mAh.
【００６３】また、電解液を含浸する前の上記のものと
同じ電極積層体一体化物を別途作製し、後に述べる電解
液含浸性評価および電解液耐熱性評価に供した。Separately, the same electrode laminate integrated body as that described above before being impregnated with the electrolytic solution was separately prepared and subjected to electrolytic solution impregnation evaluation and electrolytic solution heat resistance evaluation described later.
【００６４】一方、ＰＢＤ接着層の材料そのものの評価
を行った。ＰＢＤ接着層形成に用いた上記のトルエン溶
液をガラス板にキャストしてキャスト膜を作製し、真空
下で８０℃１２時間加熱した。加熱後の膜をトルエンに
浸漬したところ、溶解しなかった。また、１００℃に保
ったエチレンカーボネート／プロピレンカーボネート混
合液（重量比１：１）にこの膜を浸漬したところ、溶解
しなかった。また、加熱後の膜の引張弾性率を測定した
ところ、４０℃において１０ＭＰａ、１００℃において
２ＭＰａであった。On the other hand, the material itself of the PBD adhesive layer was evaluated. The above toluene solution used for forming the PBD adhesive layer was cast on a glass plate to prepare a cast film, which was heated under vacuum at 80 ° C. for 12 hours. When the heated membrane was immersed in toluene, it did not dissolve. Further, when this membrane was immersed in a mixed solution of ethylene carbonate / propylene carbonate (weight ratio 1: 1) kept at 100 ° C., it was not dissolved. The tensile modulus of the film after heating was measured and found to be 10 MPa at 40 ° C. and 2 MPa at 100 ° C.
【００６５】（比較例１）実施例１で用いたものと同じ
セパレータ、正極、負極を用意した。セパレータにポリ
フッ化ビニリデンの５％ジメチルホルムアミド溶液を塗
布した。塗布は溶液を両面にスプレーすることにより行
った。スプレー量は乾燥後のポリマーが多孔性となるよ
うに調節した。溶液塗布直後に正極と負極を貼り合わせ
た。このようにして順次セパレータと電極を接着・積層
していき、最後に４０℃２時間の真空乾燥を行った。こ
のようにして実施例１と同じ大きさ・枚数の電極積層体
一体化物を得た。Comparative Example 1 The same separator, positive electrode and negative electrode as those used in Example 1 were prepared. A 5% dimethylformamide solution of polyvinylidene fluoride was applied to the separator. The application was performed by spraying the solution on both sides. The amount of spray was adjusted so that the polymer after drying became porous. Immediately after applying the solution, the positive electrode and the negative electrode were attached. In this way, the separator and the electrode were sequentially bonded and laminated, and finally vacuum dried at 40 ° C. for 2 hours. In this manner, the same size and number of electrode laminated body integrated products as in Example 1 were obtained.
【００６６】（比較例２）実施例１で用いたものと同じ
セパレータ、正極、負極を用意した。セパレータの両面
にジメタクリル酸エチレングリコール、メタクリル酸メ
チル、およびアゾビスイソブチロニトリルを４９：５
０：１の重量比で混合した混合物を塗布した。なお、混
合物塗布によりセパレータの細孔が閉塞されないよう、
塗布量を調節した。塗布直後に正極と負極を貼り合わ
せ、８０℃２時間加熱プレスした。このようにして順次
セパレータと電極を接着・積層していき、最後に４０℃
２時間の真空乾燥を行った。このようにして実施例１と
同じ大きさ・枚数の電極積層体一体化物を得た。(Comparative Example 2) The same separator, positive electrode and negative electrode as those used in Example 1 were prepared. 49: 5 ethylene glycol dimethacrylate, methyl methacrylate, and azobisisobutyronitrile on both sides of the separator
The mixture was applied in a weight ratio of 0: 1. In addition, so that the pores of the separator are not blocked by the mixture application,
The coating amount was adjusted. Immediately after coating, the positive electrode and the negative electrode were bonded together and heated and pressed at 80 ° C. for 2 hours. In this way, the separator and the electrode are sequentially bonded and laminated, and finally 40 ° C.
Vacuum drying was performed for 2 hours. In this manner, the same size and number of electrode laminated body integrated products as in Example 1 were obtained.
【００６７】（試料の評価方法および結果）実施例１及
び比較例１、２における電極積層体の電解液含浸性と高
温電解液中での接着強度変化を以下のようにして評価し
た。(Evaluation Method and Results of Samples) The electrode laminates of Example 1 and Comparative Examples 1 and 2 were evaluated for the impregnation with the electrolytic solution and the change in adhesive strength in the high temperature electrolytic solution as follows.
【００６８】エチレンカーボネート／プロピレンカーボ
ネートの１：１混合溶媒に１Ｍの濃度でＬｉＰＦ6を溶
解した電解液に電極積層体を浸漬し、１分間減圧した後
大気圧に戻し、電極積層体を取り出して、電極を剥が
し、電極積層体の中心部まで電解液が浸透しているかど
うかを調べた。The electrode laminate was immersed in an electrolytic solution prepared by dissolving LiPF 6 at a concentration of 1 M in a 1: 1 mixed solvent of ethylene carbonate / propylene carbonate, depressurized for 1 minute and then returned to atmospheric pressure, and the electrode laminate was taken out. Then, the electrode was peeled off, and it was examined whether or not the electrolytic solution had penetrated to the central portion of the electrode laminate.
【００６９】また一方、電極積層体を２ｃｍ×２ｃｍに
切り出したものを、サンプル瓶の中で上記と同じ電解液
に浸漬し、減圧含浸した後、サンプル瓶ごと１００℃で
２時間加熱した。系を４０℃まで降温し、電極積層体の
電極を電解液中で剥がし、セパレータと電極活物質層と
の接着強度を調べた。電極積層体作製直後の大気中での
接着強度との比較で評価した。On the other hand, the electrode laminate cut into a size of 2 cm × 2 cm was immersed in the same electrolytic solution as described above in a sample bottle, impregnated under reduced pressure, and then heated together with the sample bottle at 100 ° C. for 2 hours. The system was cooled to 40 ° C., the electrode of the electrode laminate was peeled off in the electrolytic solution, and the adhesive strength between the separator and the electrode active material layer was examined. The evaluation was made by comparison with the adhesive strength in the air immediately after the production of the electrode laminate.
【００７０】以上のようにして行った評価結果を表１に
示す。実施例１及び比較例１、２における電極積層体の
電解液含浸性と高温電解液中での接着強度変化の評価結
果を示す。従来の電極／セパレータ接着法を用いた比較
例１、比較例２では電解液含浸性、高温電解液中での接
着強度に問題があった。電解液含浸性は、比較例１、比
較例２とも接着層がパターン状ではなく面全体に形成さ
れているためと考えられる。また高温電解液中での接着
強度低下は、比較例１ではポリフッ化ビニリデンが高温
において電解液に溶解または膨潤したためであり、比較
例２ではセパレータの細孔閉塞を防ぐため接着剤溶液塗
布量を少量とせざるを得なかったためであると考えられ
る。それに対し本発明を適用した実施例１では、１７×
６ｃｍで１０層の電極積層体に対しても中心部まで電解
液含浸を確実に行うことができ、高温電解液中でも接着
強度が低下しなかった。Table 1 shows the evaluation results obtained as described above. The evaluation results of the electrolytic solution impregnation of the electrode laminates in Example 1 and Comparative Examples 1 and 2 and the change in adhesive strength in a high temperature electrolytic solution are shown. In Comparative Example 1 and Comparative Example 2 using the conventional electrode / separator bonding method, there were problems in electrolytic solution impregnation and adhesive strength in a high temperature electrolytic solution. It is considered that the electrolytic solution impregnating property is due to the adhesive layer being formed not on the pattern but on the entire surface in both Comparative Example 1 and Comparative Example 2. The decrease in the adhesive strength in the high temperature electrolytic solution is because polyvinylidene fluoride was dissolved or swollen in the electrolytic solution at a high temperature in Comparative Example 1, and the adhesive solution coating amount was increased in Comparative Example 2 in order to prevent pore clogging of the separator. It is thought that this is because the amount had to be small. On the other hand, in Example 1 to which the present invention is applied, 17 ×
It was possible to surely impregnate the central part with the electrolytic solution even for an electrode laminated body of 10 cm at 6 cm, and the adhesive strength did not decrease even in the high temperature electrolytic solution.
【００７１】[0071]
【表１】 [Table 1]
【００７２】（実施例２）実施例１における正極および
負極の作製方法と同様な方法で、両面にそれぞれ活物質
結着体が設けられている幅３７ｍｍ、長さ４３５ｍｍの
長尺状の正極１枚、および幅３９ｍｍ、長さ５００ｍｍ
の長尺状の負極１枚を作製した。これらの正極および負
極にそれぞれ細長いアルミニウム箔および銅箔を超音波
溶接により取り付け、電極リードとした。また、実施例
１と同様な方法で、ＰＢＤが円形パターン状に印刷され
た長尺状のセパレータを２枚を作製した。パターン形状
は図４に示されるものである。セパレータのサイズは上
記の正極および負極よりもやや大きくした。(Example 2) A long positive electrode 1 having a width of 37 mm and a length of 435 mm, provided with active material binders on both surfaces, was prepared by the same method as the method for producing the positive electrode and the negative electrode in Example 1. Sheet, width 39 mm, length 500 mm
One long negative electrode was prepared. Elongated aluminum foil and copper foil were attached to these positive electrode and negative electrode by ultrasonic welding to form electrode leads. Further, in the same manner as in Example 1, two long-sized separators having PBD printed in a circular pattern were produced. The pattern shape is as shown in FIG. The size of the separator was slightly larger than that of the positive electrode and the negative electrode.
【００７３】これらを、負極／セパレータ／正極／セパ
レータという順に重ね、断面楕円形状の巻き芯で多数回
巻き上げてから巻き芯を抜き扁平状の電極群を作製し
た。これを真空パックしたものを卓上熱プレス機で熱プ
レスした。条件は予備加熱８０℃５分、その後本プレス
を圧力２０ｋｇ／ｃｍ２、温度８０℃、時間５分とし
た。次に１ｋｇ／ｃｍ２に圧力をゆるめ、温度は８０℃
のまま、１２時間加熱し続けた。このようにして層間接
着された扁平状巻回電極群を得た。These were stacked in the order of negative electrode / separator / positive electrode / separator, and wound up a number of times with a winding core having an elliptical cross section, and then the winding core was removed to produce a flat electrode group. This was vacuum-packed and hot-pressed with a desktop heat press. The conditions were preheating at 80 ° C. for 5 minutes, then the main press at a pressure of 20 kg / cm 2, temperature of 80 ° C., and time of 5 minutes. Next, the pressure is released to 1 kg / cm2 and the temperature is 80 ° C.
Then, heating was continued for 12 hours. In this way, a flat wound electrode group with interlayer adhesion was obtained.
【００７４】これをアルミニウムラミネートフィルムの
袋に入れ、そこにさらに実施例１で用いたものと同じ電
解液を注入し、１分間減圧することによって電解液を電
極積層体に減圧含浸した。最後に電極リードを引き出し
た状態でアルミニウムラミネートフィルムを封口した。
このようにして本発明の電池を得た。なお、電解液の注
入から最後の封口処理までの工程はドライボックスの中
で行った。This was put in a bag of an aluminum laminate film, and the same electrolytic solution as that used in Example 1 was further injected into the bag, and the pressure was reduced for 1 minute to impregnate the electrode laminate with the electrolytic solution under reduced pressure. Finally, the aluminum laminate film was sealed with the electrode leads pulled out.
Thus, the battery of the present invention was obtained. The steps from the injection of the electrolytic solution to the final sealing treatment were performed in a dry box.
【００７５】この電池の充放電特性を次のようにして評
価した。５００ｍＡの定電流で端子間電圧が４．３５Ｖ
となるまで充電し、次に４．３５Ｖで電流が充分絞り込
まれるまで定電圧充電を行った。次に５００ｍＡで定電
流放電を行い、端子間電圧が３Ｖとなるまで行って放電
容量を測定したところ、５２０ｍＡｈの容量であった。The charge / discharge characteristics of this battery were evaluated as follows. Terminal voltage is 4.35V with constant current of 500mA
Then, constant voltage charging was performed until the current was sufficiently reduced at 4.35V. Next, constant current discharge was carried out at 500 mA, and the discharge capacity was measured until the voltage between the terminals reached 3 V. The discharge capacity was 520 mAh.
【００７６】この充放電操作を５００回繰り返した後、
Ｘ線ＣＴにより断面を観察したところ、巻回電極群の層
間剥がれやたわみはほとんど観測されなかった。After repeating this charging / discharging operation 500 times,
When the cross section was observed by X-ray CT, almost no interlayer peeling or bending of the wound electrode group was observed.
【００７７】（実施例３）実施例２において、ＰＢＤの
印刷パターンを、図５に示す形状にした他は、実施例２
と同様にして電池を作製した。図５の横方向が巻回方向
となるようにした。実施例２と同様にこの電池に対し充
放電操作を５００回繰り返した後、Ｘ線ＣＴにより断面
を観察したところ、巻回電極群の層間剥がれやたわみは
全く観測されなかった。実施例２の電池よりも層間剥が
れ抑制効果は大きかった。これは、セパレータへのＰＢ
Ｄ形成パターンを、巻回方向に長細く、互い違いに切れ
目のあるストライプ状を多数形成したパターンとしたた
め、巻回方向と垂直方向にできやすいしわの発生を効果
的に抑制できたものと考えられる。(Embodiment 3) Embodiment 2 is different from Embodiment 2 except that the print pattern of the PBD has the shape shown in FIG.
A battery was prepared in the same manner as in. The horizontal direction of FIG. 5 was set to be the winding direction. After repeating the charging / discharging operation for this battery 500 times in the same manner as in Example 2, the cross-section was observed by X-ray CT. As a result, delamination or bending of the wound electrode group was not observed at all. The effect of suppressing interlayer peeling was greater than that of the battery of Example 2. This is the PB to the separator
It is considered that since the D formation pattern was a pattern in which a large number of stripes each having a long and narrow shape in the winding direction and staggered cuts were formed, it was possible to effectively suppress the generation of wrinkles that are easily formed in the direction perpendicular to the winding direction. .
【００７８】（比較例３）実施例２において、セパレー
タにＰＢＤを印刷せずに用いたこと以外は実施例２と同
様にして電池を作製した。実施例２と同様にこの電池に
対し充放電操作を５００回繰り返した後、Ｘ線ＣＴによ
り断面を観察したところ、巻回電極群の層間剥がれやた
わみが観測された。(Comparative Example 3) A battery was prepared in the same manner as in Example 2 except that PBD was not printed on the separator in Example 2. After repeating the charging / discharging operation for this battery 500 times in the same manner as in Example 2, the cross-section was observed by X-ray CT. As a result, delamination and bending of the wound electrode group were observed.
【００７９】[0079]
【発明の効果】以上説明したように、本発明によれば、
電極とセパレータを接着することにおいて、高温におい
ても接着力が低下せず、電極とセパレータの間のイオン
伝導に支障をきたすことが無く、ポリオレフィン等の接
着しにくい材質のセパレータを用いた場合でも、強い接
着強度を持ち、不要な有機溶媒が電池に残存することが
無く、複数の正極、負極、セパレータを多数層積層した
積層体に対しても内部まで迅速に電解液を含浸すること
が可能な接着を行うことができる。それにより、電池使
用中に電極とセパレータが剥離したり電極巻回体にたわ
みが生じることによる特性劣化や電池の膨れを抑制する
ことができ、また、金属缶等からの外力による電極／セ
パレータ層間密着手段を不要とすることができる。As described above, according to the present invention,
In adhering the electrode and the separator, the adhesive force does not decrease even at high temperature, does not hinder the ionic conduction between the electrode and the separator, even when using a separator such as polyolefin that is difficult to adhere, It has a strong adhesive strength, no unnecessary organic solvent remains in the battery, and it is possible to quickly impregnate the inside of the electrolyte even for a laminated body in which multiple positive electrodes, negative electrodes, and separators are laminated. Bonding can be done. As a result, it is possible to suppress the characteristic deterioration and the swelling of the battery due to the peeling of the electrode and the separator or the bending of the electrode winding body during the use of the battery, and also to prevent the electrode / separator layer from being separated by the external force from the metal can. The contact means can be eliminated.
【図１】本発明の電極セパレータの実施形態の一つを模
式的に示した図である。FIG. 1 is a view schematically showing one of embodiments of an electrode separator of the present invention.
【図２】本発明の電極セパレータの他の実施形態を模式
的に示した図である。FIG. 2 is a view schematically showing another embodiment of the electrode separator of the present invention.
【図３】本発明の電極セパレータの製造方法を説明する
ための模式図である。FIG. 3 is a schematic diagram for explaining a method for manufacturing an electrode separator of the present invention.
【図４】本発明の電極セパレータ積層体における熱可塑
性ポリマーの印刷パターンの１例を示す図である。FIG. 4 is a diagram showing an example of a printed pattern of a thermoplastic polymer in the electrode separator laminate of the present invention.
【図５】本発明の電極セパレータ積層体における熱可塑
性ポリマーの印刷パターンの異なる１例を示す図であ
る。FIG. 5 is a diagram showing an example in which a printed pattern of a thermoplastic polymer in the electrode separator laminate of the present invention is different.
１ 正極集電体 ２ 正極活物質粒子 ３ 多孔質セパレータ ４ 負極活物質粒子 ５ 負極集電体 ６ ポリマー架橋物 ７ 熱可塑性ポリマー 1 Positive electrode current collector 2 Positive electrode active material particles 3 Porous separator 4 Negative electrode active material particles 5 Negative electrode current collector 6 crosslinked polymer 7 Thermoplastic polymer
───────────────────────────────────────────────────── フロントページの続き (72)発明者 坂内 裕 東京都港区芝五丁目７番１号 日本電気 株式会社内 (72)発明者 佐藤 正春 東京都港区芝五丁目７番１号 日本電気 株式会社内 (72)発明者 白方 雅人 東京都港区芝五丁目７番１号 日本電気 株式会社内 (72)発明者 大山 宣英 神奈川県横浜市港北区新横浜二丁目５番 ５号 エヌイーシーモリエナジー株式会 社内 (56)参考文献 特開 平10−172606（ＪＰ，Ａ) 特開 平10−172537（ＪＰ，Ａ) 特開 平７−201315（ＪＰ，Ａ) 特開 昭63−69154（ＪＰ，Ａ) 特開 平10−289732（ＪＰ，Ａ) 特開 平９−167608（ＪＰ，Ａ) 特開 平８−306366（ＪＰ，Ａ) 特開 平７−249408（ＪＰ，Ａ) 特開 平10−189054（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01M 2/16 H01M 10/40 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yu Sakauchi 5-7 Shiba 5-1, Minato-ku, Tokyo NEC Electric Co., Ltd. (72) Masaharu Sato 5-7-1 Shiba, Minato-ku, Tokyo NEC Co., Ltd. (72) Inventor Masato Shirokata 5-7 Shiba, Minato-ku, Tokyo NEC Corporation (72) Inventor Nobuhide Oyama 2-5-5 Shin-Yokohama, Kohoku-ku, Yokohama-shi, Kanagawa Mori Energy Co., Ltd. (56) Reference JP 10-172606 (JP, A) JP 10-172537 (JP, A) JP 7-201315 (JP, A) JP 63-69154 ( JP, A) JP 10-289732 (JP, A) JP 9-167608 (JP, A) JP 8-306366 (JP, A) JP 7-249408 (JP, A) JP Flat 10-189054 (JP, A) (58) Minutes surveyed Field (Int.Cl. 7 , DB name) H01M 2/16 H01M 10/40
Claims (24)
パレータが配置された電極セパレータ積層体において、 前記多孔質正極、多孔質負極および多孔質セパレータの
３者が、ポリマー架橋物によって、積層された面内の不
連続した位置において互いに層間接着されていることを
特徴とする電極セパレータ積層体。1. An electrode separator laminate in which a porous separator is arranged between a porous positive electrode and a porous negative electrode, wherein the porous positive electrode, the porous negative electrode and the porous separator are An electrode-separator laminate, wherein layers are adhered to each other at discontinuous positions in a plane where the layers are laminated.
ーが架橋されたものである請求項１記載の電極セパレー
タ積層体。2. The electrode separator laminate according to claim 1, wherein the crosslinked polymer is a crosslinked thermoplastic polymer.
であり、かつその融点または軟化点が、前記多孔質セパ
レータの融点または軟化点よりも低いものである請求項
２記載の電極セパレータ積層体。3. The electrode separator laminate according to claim 2, wherein the thermoplastic polymer is solid at room temperature and has a melting point or softening point lower than that of the porous separator.
および多孔質負極の細孔内においてアンカー形状を有し
ていることを特徴とする請求項１〜３のいずれかに記載
の電極セパレータ積層体。4. The electrode separator laminate according to claim 1, wherein the polymer cross-linked product has an anchor shape in the pores of the porous positive electrode and the porous negative electrode. body.
の細孔内部と、多孔質正極または多孔質負極のどちらか
一方の電極の細孔内部との２つの領域にわたる連続体と
なっている請求項１〜４のいずれかに記載の電極セパレ
ータ積層体。5. The polymer cross-linked product is a continuous body extending over two regions, that is, inside the pores of the separator and inside the pores of either one of the porous positive electrode and the porous negative electrode. The electrode separator laminate according to any one of 1 to 4.
タ、多孔質正極および多孔質負極の各細孔内部の３つの
領域にわたる連続体となっている請求項１〜４のいずれ
かに記載の電極セパレータ積層体。6. The electrode separator according to claim 1, wherein the polymer cross-linked product is a continuous body over three regions inside each pore of the separator, the porous positive electrode and the porous negative electrode. Laminate.
イクロポーラスセパレータである請求項１〜６のいずれ
かに記載の電極セパレータ積層体。7. The electrode separator laminate according to claim 1, wherein the separator is a polyolefin microporous separator.
ン系樹脂である請求項２〜７のいずれかに記載の電極セ
パレータ積層体。8. The electrode separator laminate according to claim 2, wherein the thermoplastic polymer is a polyolefin resin.
基を有するものである請求項２〜８のいずれかに記載の
電極セパレータ積層体。9. The electrode separator laminate according to claim 2, wherein the thermoplastic polymer has a vinyl group in a side chain.
リブタジエンを含有するポリマーである請求項９記載の
電極セパレータ積層体。10. The electrode separator laminate according to claim 9, wherein the thermoplastic polymer is a polymer containing 1,2-polybutadiene.
セパレータが配置された電極セパレータ積層体の製造方
法において、 前記多孔質セパレータ、多孔質正極および多孔質負極の
少なくとも一つに対し、熱可塑性ポリマーを積層面内の
不連続した位置に付着させたものを用いて、前記多孔質
正極および多孔質負極の間に前記多孔質セパレータが挟
まれるように重ね合わせ、その後加熱して熱可塑性ポリ
マーを溶融して、前記多孔質セパレータ、多孔質正極お
よび多孔質負極の各細孔内部に流入させる工程と、 熱可塑性ポリマーを架橋させる工程とを有する電極セパ
レータ積層体の製造方法。11. A method of manufacturing an electrode separator laminate in which a porous separator is arranged between a porous positive electrode and a porous negative electrode, wherein at least one of the porous separator, the porous positive electrode and the porous negative electrode is: Using a thermoplastic polymer adhered to discontinuous positions in the lamination plane, the porous positive electrode and the porous negative electrode are superposed so that the porous separator is sandwiched between them, and then heated to be thermoplastic. A method for producing an electrode separator laminate, comprising a step of melting a polymer and causing the polymer to flow into the pores of the porous separator, the porous positive electrode and the porous negative electrode, and a step of crosslinking a thermoplastic polymer.
体であるポリマーを用い、前記熱可塑性ポリマーを溶融
して流入させる工程において、加熱温度を、前記熱可塑
性ポリマーの融点または軟化点以上かつセパレータの融
点または軟化点以下の温度とする請求項１１記載の電極
セパレータ積層体の製造方法。12. A polymer that is solid at room temperature is used as the thermoplastic polymer, and in the step of melting and inflowing the thermoplastic polymer, the heating temperature is set to the melting point or softening point of the thermoplastic polymer or more and the melting point of the separator. Alternatively, the method for producing the electrode-separator laminate according to claim 11, wherein the temperature is equal to or lower than the softening point.
させる工程において、前記熱可塑性ポリマーを、前記セ
パレータの細孔内部および一方の電極の細孔内部の２つ
の領域にわたる連続体となるように流入させる請求項１
１または１２記載の電極セパレータ積層体の製造方法。13. In the step of melting and inflowing the thermoplastic polymer, the thermoplastic polymer is introduced so as to be a continuous body over two regions inside the pores of the separator and inside the pores of one of the electrodes. Claim 1
13. The method for producing an electrode separator laminate according to 1 or 12.
させる工程において、前記熱可塑性ポリマーを、前記セ
パレータ、多孔質正極および多孔質負極の各細孔内部の
３つの領域にわたる連続体となるように流入させる請求
項１１または１２記載の電極セパレータ積層体の製造方
法。14. In the step of melting and inflowing the thermoplastic polymer, the thermoplastic polymer is formed into a continuous body over three regions inside each pore of the separator, the porous positive electrode and the porous negative electrode. The method for producing an electrode separator laminate according to claim 11 or 12, wherein the electrode separator laminate is allowed to flow.
程において、前記熱可塑性ポリマーを前記セパレータに
パターン状に付着させる請求項１１〜１４のいずれかに
記載の電極セパレータ積層体の製造方法。15. The method for producing an electrode separator laminate according to claim 11, wherein in the step of attaching the thermoplastic polymer, the thermoplastic polymer is attached to the separator in a pattern.
ータの両面に表と裏で同じ位置になるように位置を合わ
せてパターン状に付着させる請求項１５記載の電極セパ
レータ積層体の製造方法。16. The method for producing an electrode separator laminate according to claim 15, wherein the thermoplastic polymer is attached on both surfaces of the separator in a pattern so that the front and back surfaces are in the same position.
マイクロポーラスセパレータである請求項１１〜１６の
いずれかに記載の電極セパレータ積層体の製造方法。17. The method for producing an electrode separator laminate according to claim 11, wherein the separator is a polyolefin microporous separator.
ィン系樹脂である請求項１１〜１７のいずれかに記載の
電極セパレータ積層体の製造方法。18. The method for producing an electrode separator laminate according to claim 11, wherein the thermoplastic polymer is a polyolefin resin.
ル基を有するものである請求項１１〜１８のいずれかに
記載の電極セパレータ積層体の製造方法。19. The method for producing an electrode separator laminate according to claim 11, wherein the thermoplastic polymer has a vinyl group in a side chain.
リブタジエンを含有するポリマーである請求項１９記載
の電極セパレータ積層体の製造方法。20. The method for producing an electrode separator laminate according to claim 19, wherein the thermoplastic polymer is a polymer containing 1,2-polybutadiene.
しされた形態であることを特徴とする請求項１〜１０の
いずれかに記載の電極セパレータ積層体。21. The electrode separator laminate according to claim 1, wherein the electrode separator laminate has a wound form.
に前記多孔質セパレータが挟まれるように重ね合わせる
際に、多孔質正極、多孔質負極および多孔質セパレータ
を重ね合わせて巻き回し、その後加熱して熱可塑性ポリ
マーを溶融して、前記多孔質セパレータ、多孔質正極お
よび多孔質負極の各細孔内部に流入させることを特徴と
する請求項１１〜２０のいずれかに記載の電極セパレー
タの製造方法。22. When stacking the porous positive electrode and the porous negative electrode so that the porous separator is sandwiched between the porous positive electrode and the porous negative electrode, the porous positive electrode, the porous negative electrode and the porous separator are stacked and wound, and then heated. 21. The electrode separator according to any one of claims 11 to 20, wherein the thermoplastic polymer is melted and allowed to flow into the pores of the porous separator, the porous positive electrode and the porous negative electrode. Method.
は請求項２１に記載の電極セパレータ積層体に、電解液
を含浸した電池。23. A battery in which the electrode separator laminate according to any one of claims 1 to 10 or claim 21 is impregnated with an electrolytic solution.
リチウムイオンを吸蔵放出する粒子の結着体を含み、前
記電解液は、リチウム塩を含む非水系有機溶媒である請
求項２３記載の電池。24. The porous positive electrode and the porous negative electrode,
24. The battery according to claim 23, comprising a binder of particles that absorb and release lithium ions, and the electrolytic solution is a non-aqueous organic solvent containing a lithium salt.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11707299A JP3447610B2 (en) | 1999-04-23 | 1999-04-23 | Electrode separator laminate, method for producing the same, and battery using the same |
| CA002306360A CA2306360A1 (en) | 1999-04-23 | 2000-04-19 | Electrode-separator laminate, method of producing the same, and battery using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11707299A JP3447610B2 (en) | 1999-04-23 | 1999-04-23 | Electrode separator laminate, method for producing the same, and battery using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000306569A JP2000306569A (en) | 2000-11-02 |
| JP3447610B2 true JP3447610B2 (en) | 2003-09-16 |
Family
ID=14702727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11707299A Expired - Lifetime JP3447610B2 (en) | 1999-04-23 | 1999-04-23 | Electrode separator laminate, method for producing the same, and battery using the same |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP3447610B2 (en) |
| CA (1) | CA2306360A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160131476A (en) * | 2015-05-07 | 2016-11-16 | 주식회사 엘지화학 | An electrode assembly for a electrochemical device |
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| JP4945855B2 (en) * | 2000-05-15 | 2012-06-06 | 株式会社デンソー | Method for producing porous membrane for non-aqueous electrolyte secondary battery or electric double layer capacitor, method for producing electrode for non-aqueous electrolyte secondary battery or electric double layer capacitor, for non-aqueous electrolyte secondary battery or electric double layer capacitor Porous membrane and non-aqueous electrolyte secondary battery or electric double layer capacitor |
| JP2004323827A (en) * | 2003-04-09 | 2004-11-18 | Nitto Denko Corp | Adhesive-carrying porous film for battery separator and use of the same |
| TWI283493B (en) * | 2003-05-30 | 2007-07-01 | Lg Chemical Ltd | Rechargeable lithium battery using separator partially coated with gel polymer |
| JP2005158816A (en) * | 2003-11-20 | 2005-06-16 | Tdk Corp | Electrochemical device and manufacturing method thereof |
| JP4601323B2 (en) * | 2004-05-17 | 2010-12-22 | 日東電工株式会社 | Electrode element for large-sized lithium ion secondary battery and manufacturing method thereof |
| JP4601338B2 (en) * | 2004-06-24 | 2010-12-22 | 日東電工株式会社 | Battery positive electrode / reactive polymer-supported porous film / negative electrode laminate |
| JP4526352B2 (en) | 2004-11-08 | 2010-08-18 | 日東電工株式会社 | Reactive polymer-supported porous film for battery separator and battery manufacturing method using the same |
| PL2927993T3 (en) * | 2008-01-30 | 2019-01-31 | Lg Chem, Ltd. | Separator for an electrochemical device |
| JP5327540B2 (en) * | 2009-09-28 | 2013-10-30 | トヨタ自動車株式会社 | Separator for lithium ion secondary battery and manufacturing method thereof |
| CN102610773B (en) * | 2012-03-06 | 2017-06-06 | 宁德新能源科技有限公司 | A kind of polymer Li-ion battery and its barrier film |
| KR101535023B1 (en) * | 2013-11-22 | 2015-07-08 | 주식회사 엘지화학 | Electrode assembly and radical unit for the same |
| KR20150057481A (en) * | 2013-11-19 | 2015-05-28 | 삼성에스디아이 주식회사 | Separator for lithium battery, lithium battery including the same, and method for preparing the lithium battery |
| JP6302400B2 (en) * | 2013-11-27 | 2018-03-28 | 旭化成株式会社 | Power storage device separator, power storage device, and lithium ion secondary battery |
| JP6688006B2 (en) * | 2015-04-02 | 2020-04-28 | 旭化成株式会社 | Wound body |
| KR101977639B1 (en) * | 2016-02-16 | 2019-05-14 | 주식회사 엘지화학 | Electrode assembly and manufacturing method of thereof |
| DE102017201233A1 (en) * | 2017-01-26 | 2018-07-26 | Robert Bosch Gmbh | Process for producing an electrode laminate for a solid-state battery |
| JP6907694B2 (en) * | 2017-05-17 | 2021-07-21 | 株式会社村田製作所 | Rechargeable battery manufacturing method and rechargeable battery |
| KR20210062004A (en) * | 2018-09-28 | 2021-05-28 | 니폰 제온 가부시키가이샤 | Secondary battery and its manufacturing method |
| CN115136370A (en) * | 2020-02-14 | 2022-09-30 | 三洋电机株式会社 | Nonaqueous electrolyte secondary battery |
| JP7209660B2 (en) * | 2020-03-13 | 2023-01-20 | パナソニックホールディングス株式会社 | BATTERY MANUFACTURING METHOD AND BATTERY |
| CN111613758B (en) * | 2020-04-21 | 2023-02-21 | 浙江锋锂新能源科技有限公司 | Separator without polyolefin substrate, preparation method thereof and lithium battery containing separator |
-
1999
- 1999-04-23 JP JP11707299A patent/JP3447610B2/en not_active Expired - Lifetime
-
2000
- 2000-04-19 CA CA002306360A patent/CA2306360A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160131476A (en) * | 2015-05-07 | 2016-11-16 | 주식회사 엘지화학 | An electrode assembly for a electrochemical device |
| KR102019474B1 (en) | 2015-05-07 | 2019-11-14 | 주식회사 엘지화학 | An electrode assembly for a electrochemical device |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2306360A1 (en) | 2000-10-23 |
| JP2000306569A (en) | 2000-11-02 |
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