JP6587157B2 - Electrode assembly and electrochemical device including the same - Google Patents
Electrode assembly and electrochemical device including the same Download PDFInfo
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- JP6587157B2 JP6587157B2 JP2017020780A JP2017020780A JP6587157B2 JP 6587157 B2 JP6587157 B2 JP 6587157B2 JP 2017020780 A JP2017020780 A JP 2017020780A JP 2017020780 A JP2017020780 A JP 2017020780A JP 6587157 B2 JP6587157 B2 JP 6587157B2
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Images
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
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- Secondary Cells (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Connection Of Batteries Or Terminals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、二次電池における電極の短絡を防止するための技術に対するものである。 The present invention relates to a technique for preventing a short circuit of an electrode in a secondary battery.
近年、充放電が可能で、且つ軽いながらもエネルギー密度及び出力密度の高いリチウム二次電池がワイヤレスモバイル機器のエネルギー源として幅広く用いられている。また、ガソリン車両、ディーゼル車両など化石燃料を用いる既存の内燃機関自動車の大気汚染及び温室ガス問題を解決するための代替方案として、ハイブリッド電気自動車(HEV)、プラグインハイブリッド電気自動車(PHEV)、バッテリー電気自動車(BEV)、電気自動車(EV)などが提示されているが、リチウム二次電池はこのような内燃機関代替自動車の動力源としても注目されている。 In recent years, lithium secondary batteries that can be charged and discharged and that are light but have high energy density and high output density have been widely used as energy sources for wireless mobile devices. In addition, hybrid electric vehicles (HEV), plug-in hybrid electric vehicles (PHEV), batteries are available as alternatives to solve the air pollution and greenhouse gas problems of existing internal combustion engine vehicles using fossil fuels such as gasoline vehicles and diesel vehicles. Although electric vehicles (BEV), electric vehicles (EV), and the like have been presented, lithium secondary batteries are also attracting attention as a power source for such internal combustion engine alternative vehicles.
リチウム二次電池は、電解液の種類に応じて液体電解質を用いるリチウムイオン電池と、高分子電解質を用いるリチウムポリマー電池とに分類され、電極組立体が収容される外装材の形状によって円筒型、角型又はパウチ型に分類される。 Lithium secondary batteries are classified into lithium ion batteries that use liquid electrolytes and lithium polymer batteries that use polymer electrolytes depending on the type of electrolyte, and are cylindrical depending on the shape of the exterior material that houses the electrode assembly. It is classified as a square type or a pouch type.
このうち、パウチ型は金属層(ホイル)と、前記金属層の上面と下面にコーティングされる合成樹脂層の多層膜とで構成されるパウチ外装材を用いて外観を構成するので、金属カンを用いる円筒型又は角型よりも電池の重さを著しく減らすことができ、電池の軽量化が可能であり、多様な形態への変化が可能であるとのメリットがある。 Among these, the pouch type has an appearance using a pouch exterior material composed of a metal layer (foil) and a multilayer film of a synthetic resin layer coated on the upper surface and the lower surface of the metal layer. The weight of the battery can be remarkably reduced as compared with the cylindrical type or the square type used, and there is an advantage that the battery can be reduced in weight and can be changed into various forms.
このようなパウチ外装材は、矩形外装材を一辺の長さ方向に基づいて中間を摺綴して形成された上部外装材と下部外装材からなるが、下部外装材にはプレス(press)加工などを介して電極組立体を収容するための空間部が形成される。下部外装材の空間部には、主に板状の正極、分離膜及び負極が積層された構造の多様な電極組立体が収容される。その後、電解液が注入され、前記下部外装材の空間部の周囲の縁部と、これに対応する上部外装材の縁を密着させ、密着された部分を熱融着すると、密封された形態のパウチ型二次電池が形成される。 Such a pouch exterior material is composed of an upper exterior material and a lower exterior material formed by sliding a rectangular exterior material on the basis of the length direction of one side, and the lower exterior material is press processed. A space for accommodating the electrode assembly is formed through the like. Various electrode assemblies having a structure in which a plate-like positive electrode, a separation membrane, and a negative electrode are mainly stacked are accommodated in the space of the lower exterior material. Thereafter, an electrolyte is injected, and the peripheral edge of the space of the lower exterior material and the edge of the corresponding upper exterior material are brought into close contact with each other. A pouch-type secondary battery is formed.
図1には、従来の代表的なパウチ型二次電池の一般的な構造が分解斜視図として模式的に示されている。 FIG. 1 schematically shows a general structure of a conventional typical pouch-type secondary battery as an exploded perspective view.
図1を参照すれば、パウチ型二次電池1は、電極組立体10、電極組立体10から延長されてい
る電極タブ31、32、電極タブ31、32に溶接されている電極リード51、52、及び電極組立体
10を収容する電池ケース20を含むものとして構成されている。
Referring to FIG. 1, a pouch-type secondary battery 1 includes an
The
電極組立体10は、分離膜が介在された状態で正極と負極が順次積層されている発電素子であって、スタック型又はスタック/折り畳み型構造からなっている。電極タブ31、32は電極組立体10の各極板から延長されており、電極リード51、52は各極板から延長された複数
個の電極タブ31、32と、例えば、溶接によってそれぞれ電気的に連結されており、電池ケース20の外部へ一部が露出している。また、電極リード51、52の上下面の一部には、電池
ケース20との密封度を高めるとともに電気的絶縁状態を確保するために絶縁フィルム53が
付着されている。
The
さらに、多数の正極、負極タブ31、32が一体に結合されて溶着部を形成することによって、電池ケース20の内部上端は電極組立体10の上端面から一定の距離ほど離隔されており、溶着部のタブ31、32は略V字状に折曲されている(電極タブなどと電極リードの結合部位をV-フォーミング(V-forming)41、42部位と称したりする)。電池ケース20はアルミニウムラ
ミネートシートからなり、電極組立体10を収容することのできる空間を提供し、全体的にパウチ状を有している。二次電池は、電池ケース20の収納部に電極組立体10を内装して電
解液(図示せず)を注入した後、電池ケース20の上部ラミネートシートと下部ラミネートシートが接する外周面を熱融着させる過程を介して製造される。
In addition, a large number of positive and
図2は、前述した電極組立体の構造の問題を説明するための概念図である。 FIG. 2 is a conceptual diagram for explaining the problem of the structure of the electrode assembly described above.
図2に示されているように、電極組立体10は正極と負極の積層構造で具現され、正極及び負極を構成する集電体と連結される電極タブ31、32を備えている。このとき、図2でアルミニウムホイル(Al foil)31で示された部分が正極タブ31であり、銅ホイル(Cu foil)32で示された部分が負極タブ32である。特に、前記電極組立体は、集電体上に正極活物質がコーティングされる正極(cathode)と、集電体上の負極活物質がコーティングされる負極(Anode)が積層され、正極と負極の物理的短絡を防止するために分離膜(separator)が挿入される。この場合、通常、電極組立体の正極と負極の物理的短絡のリスクを低めるため、正極より負極を大きく製作するようになるが、高温の雰囲気で分離膜の収縮などによって正極と負極の物理的短絡が頻繁に起こるようになる問題が生じる。
As shown in FIG. 2, the
本発明は、前述した問題を解決するために案出されたものであって、本発明の目的は電極組立体の構造で正極のタブとして用いられる正極集電体の末端部(タブ部)に絶縁層を形成することにより、正極/分離膜/負極の順次積層構造で正極と負極の物理的短絡を防止できるようにする二次電池を提供することにある。 The present invention has been devised to solve the above-described problems, and the object of the present invention is to provide a terminal (tab portion) of a positive electrode current collector used as a positive electrode tab in the structure of an electrode assembly. It is an object of the present invention to provide a secondary battery that can prevent a physical short circuit between a positive electrode and a negative electrode by forming an insulating layer in a sequentially laminated structure of positive electrode / separation membrane / negative electrode.
前述した課題を解決するための手段として、本発明は分離膜を挟んで正極集電体及び負極集電体上にそれぞれ正極活物質及び負極活物質がコーティングされる正極及び負極と、前記正極及び負極との間に配置される分離膜からなる電極組立体であって、前記正極を構成する正極集電体のタブ部に絶縁層が形成されている電極組立体を提供し、正極/分離膜/負極の順次積層構造で正極と負極の物理的短絡を防止できるようにする。 As means for solving the above-described problems, the present invention provides a positive electrode and a negative electrode in which a positive electrode current collector and a negative electrode current collector are coated on a positive electrode current collector and a negative electrode current collector, respectively, with the separation membrane interposed therebetween, Provided is an electrode assembly comprising a separation membrane disposed between a negative electrode and an electrode assembly in which an insulating layer is formed on a tab portion of a positive electrode current collector constituting the positive electrode. / Sequential lamination structure of negative electrode to prevent physical short circuit between positive and negative electrodes.
本発明によれば、電極組立体の構造で正極のタブとして用いられる正極集電体の末端部(タブ部)に絶縁層を形成することにより、正極/分離膜/負極の順次積層構造で正極と負極
の物理的短絡を防止できるようにする効果がある。
According to the present invention, the positive electrode / separation membrane / negative electrode are sequentially stacked to form the positive electrode by forming an insulating layer at the terminal portion (tab portion) of the positive electrode current collector used as the positive electrode tab in the structure of the electrode assembly. This has the effect of preventing the physical short circuit between the negative electrode and the negative electrode.
以下では、図を参照して本発明に係る構成及び作用を具体的に説明する。図を参照して説明するにおいて、図面符号に係りなく同一の構成要素は同一の参照番号を付与し、これに対する重複説明は略する。第1、第2などの用語は多様な構成要素などを説明するために用いられ得るが、前記構成要素などは前記用語などによって限定されてはならない。前記用語などは一つの構成要素を他の構成要素から区別する目的のみに用いられる。 Hereinafter, the configuration and operation according to the present invention will be specifically described with reference to the drawings. In the description with reference to the drawings, the same constituent elements are given the same reference numerals regardless of the reference numerals, and the redundant description thereof will be omitted. The terms such as “first” and “second” may be used to describe various components and the like, but the components and the like should not be limited by the terms and the like. The terms and the like are used only for the purpose of distinguishing one component from other components.
図3は、本発明に係る電極組立体の構造を示した断面図であり、図4は正極集電体タブ部上
に絶縁層を形成する方法を示した平面図である。
FIG. 3 is a cross-sectional view showing the structure of the electrode assembly according to the present invention, and FIG. 4 is a plan view showing a method of forming an insulating layer on the positive electrode current collector tab portion.
図3及び図4を参照すれば、本発明に係る電極組立体は分離膜130を挟んで正極集電体110上
に正極活物質120がコーティングされる正極122、及び負極集電体150上に負極活物質140が
コーティングされる負極142と、前記正極及び負極との間に配置される分離膜130、及び前
記正極122を構成する正極集電体110のタブ部に形成される絶縁層160とを含んで構成され
得る。
Referring to FIGS. 3 and 4, the electrode assembly according to the present invention includes a
特に、本発明に係る前記絶縁層160は、前記正極集電体110と分離膜130との間に配置され
、前記負極活物質140の塗布領域と一部がオーバーラップ(overlap)されるように配置され得る。すなわち、負極の大きさが正極より大きく形成されるところ、前記負極と正極との間には互いに重ならない部分の領域T3が存在し、一般的にこの領域によって電極の短絡が行われるところ、前記領域T3に絶縁層160を形成することを特徴とする。
In particular, the
すなわち、前記絶縁層160は、前記負極活物質140の塗布領域と一部がオーバーラップされ
るように配置され、通常、前記絶縁層は前記正極活物質120の塗布領域の末端と連結されるように形成することができる。また、前記絶縁層160は前記タブ部の一端が露出する露出部T2が形成されるように具現するのが好ましい。さらに、前記絶縁層の幅(T3領域)は1m
m〜20mmの範囲で形成されるのが好ましく、この場合、絶縁層自体の厚さは1μm〜100μ
mに形成するのが好ましい。前記露出部T2と絶縁層の形成領域(T3領域)の総長さT1は通常
20mm〜30mm程度に具現される。
That is, the
It is preferably formed in the range of m to 20 mm. In this case, the thickness of the insulating layer itself is 1 μm to 100 μm
It is preferable to form m. The total length T1 of the exposed portion T2 and the insulating layer formation region (T3 region) is usually
It is embodied in 20mm to 30mm.
図4は、図3で正極集電体110上に正極活物質120がコーティングされた状態の正極122の平
面図を示したものである。
FIG. 4 is a plan view of the
前記絶縁層160の形成方式は、図3に示されているように、正極集電体110の正極活物質120
の塗布領域の末端部に、絶縁物質を集電体の幅方向にコーティングする方式で具現され得
る。
The formation method of the
In this case, an insulating material may be coated in the width direction of the current collector at the end of the coating area.
図4でのように前記絶縁層160を具現する方式は、少なくとも1以上のセラミック物質を含
有した絶縁物質を塗布して具現することができる。例えば、前記絶縁層は、二酸化チタン、カルシウムカーボネート、硫酸バリウムのうち選択されるいずれか一つ又は二つ以上の混合した物質を適用するか、又は二酸化チタン、カルシウムカーボネート、硫酸バリウムを10〜90%重量比で含有した水溶液又は塗料を塗布して具現することができる。
As shown in FIG. 4, the insulating
さらに、前記絶縁層は、重量平均分子量が20万以下の高分子フィルム又はエマルジョンを前記タブ部上に合着及び塗布して具現することができる。この場合、前記高分子フィルムは、ポリアクリレート、ポリスチレン、ポリアクリル酸、ポリアクリロニトリル、ポリエチレン、ポリプロピレン、ポリイミド、ポリウレタン、ポリエチレンテレフタレートのうち選択される一つ以上の物質で具現することができ、SBR系重合体を利用しても具現され得る。 Furthermore, the insulating layer can be realized by attaching and applying a polymer film or emulsion having a weight average molecular weight of 200,000 or less on the tab portion. In this case, the polymer film may be implemented with one or more substances selected from polyacrylate, polystyrene, polyacrylic acid, polyacrylonitrile, polyethylene, polypropylene, polyimide, polyurethane, polyethylene terephthalate, and SBR type. It can also be realized by using a polymer.
すなわち、本発明に係る前記絶縁層160は、前述した絶縁物質を電界紡糸するか、プリンティング、スプレーコーティング、テーピングなどの多様な方式を介して具現することができる。
That is, the insulating
以下では、このような本発明に係る電極リードを備えた二次電池を介して接触不良の発生可否を確認する実験例を説明する。本発明に係る前記電極組立体は、巻取型、スタック型又はスタック/折り畳み型構造のうちいずれか一つからなる構造で二次電池を構成することができる。以下、本発明を実施例を挙げてさらに詳しく説明する。以下の実施例は、発明の詳細な説明のためのものであるだけで、これによって権利範囲を制限しようとする意図ではないことを明らかにする。 Hereinafter, an experimental example for confirming whether or not contact failure occurs through a secondary battery including the electrode lead according to the present invention will be described. The electrode assembly according to the present invention may constitute a secondary battery having a structure of any one of a winding type, a stack type, and a stack / folding type structure. Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of rights.
正極集電体のタブ部において、正極活物質の末端部から幅10mm、厚さ10μmで絶縁層を形
成したことを除いては、当業界に知られた材料及び方法で電極組立体を製造した。
The electrode assembly was manufactured using materials and methods known in the art, except that the tab portion of the positive electrode current collector was formed with an insulating layer having a width of 10 mm and a thickness of 10 μm from the end of the positive electrode active material. .
本実施例で、前記絶縁層はSBR系重合体を変成させたポリマーとしてブチルアクリレート、スチレンを主要構成とし、アクリル酸、アクリロニトリル及びエチルヘキシルアクリレートのうち選択される一つ以上の単量体を少量含む重合体を含む水溶液を利用するか、二酸化チタンをメチルアルコール又は水に分散させた溶液を利用しており、このような絶縁層を利用して100個の電極組立体を製造した。電池ケースの収納部に前記で製造したそれぞれの電極組立体を内装し、電極組立体の集電体から延長されて突出されている多数の電極タブなどとリード部を溶接してV-フォーミング部を形成した後、電解液を注入し、電池ケースの上部ラミネートシートと下部ラミネートが接する外周面を熱融着させ、電池ケースをシーリングすることにより総100個のパウチ型二次電池を製造した。 In this embodiment, the insulating layer is mainly composed of butyl acrylate and styrene as a polymer obtained by modifying the SBR polymer, and contains a small amount of one or more monomers selected from acrylic acid, acrylonitrile and ethylhexyl acrylate. An aqueous solution containing a polymer was used, or a solution in which titanium dioxide was dispersed in methyl alcohol or water was used, and 100 electrode assemblies were manufactured using such an insulating layer. Each electrode assembly manufactured as described above is housed in the battery case housing part, and a number of electrode tabs extending from the current collector of the electrode assembly and the lead part are welded to the V-forming part. Then, an electrolytic solution was injected, the outer peripheral surface of the battery case where the upper laminate sheet and the lower laminate were in contact with each other was thermally fused, and the battery case was sealed to produce a total of 100 pouch-type secondary batteries.
[比較例]
絶縁層を形成しないことを除いては、前記実施例と同一の方法でパウチ型二次電池を製作した。
[Comparative example]
A pouch-type secondary battery was manufactured by the same method as in the above example except that the insulating layer was not formed.
[実験例]
前記実施例及び比較例でそれぞれ製造された電池を対象として、100℃、150℃、200℃に露出させるテストの結果を下記表1に示した。
[Experimental example]
Table 1 below shows the results of a test in which the batteries manufactured in Examples and Comparative Examples were exposed to 100 ° C, 150 ° C, and 200 ° C.
本実験では、それぞれ100個の電池などに対し繰り返して行っており、負極部位の短絡の可否を測定した。 In this experiment, each test was repeated for 100 batteries, and the possibility of short circuit at the negative electrode portion was measured.
以下では、前述した本発明に係る絶縁層を形成させた電極組立体を構成する個別構成要素の具体的な材料及び構成上の特徴を説明する。 Hereinafter, specific materials and structural features of the individual components constituting the electrode assembly on which the insulating layer according to the present invention is formed will be described.
[正極構造]
本発明で前記基本単位体に形成される電極は正極又は負極に区別され、前記正極及び負極をその間に分離膜を介在させた状態で互いに結合させて製造される。正極は、例えば、正極集電体上に正極活物質を、導電材及びバインダの混合物を塗布した後、乾燥及びプレッシングして製造され、必要に応じて前記混合物に充填剤をさらに添加したりする。このような構造は、シート状で具現されてローディングロールに装着される形態で工程に適用され得る。
[Positive electrode structure]
In the present invention, the electrode formed on the basic unit body is classified into a positive electrode or a negative electrode, and is manufactured by bonding the positive electrode and the negative electrode to each other with a separation membrane interposed therebetween. The positive electrode is manufactured, for example, by applying a positive electrode active material on a positive electrode current collector, applying a mixture of a conductive material and a binder, and then drying and pressing, and further adding a filler to the mixture as necessary. . Such a structure can be applied to the process in the form of a sheet and mounted on a loading roll.
[正極集電体]
前記正極集電体は、一般的に3〜500μmの厚さで作製する。このような正極集電体は、当該電池に化学的変化を誘発することなく高い導電性を有するものであれば特に制限されるものではなく、例えば、ステンレススチール、アルミニウム、ニッケル、チタン、焼成炭素、又はアルミニウムやステンレススチールの表面にカーボン、ニッケル、チタン、銀などで表面処理したものなどが用いられ得る。集電体はその表面に微細な凹凸を形成し、正極活物質の接着力を高めることもでき、フィルム、シート、ホイル、ネット、多孔質体、発泡体、不織布体など多様な形態が可能である。前述した本発明に係る実施例で電極タブの場合、前記正極集電体の材質と同一の材質を有するように形成され得る。
[Positive electrode current collector]
The positive electrode current collector is generally produced with a thickness of 3 to 500 μm. Such a positive electrode current collector is not particularly limited as long as it has high conductivity without inducing a chemical change in the battery. For example, stainless steel, aluminum, nickel, titanium, calcined carbon Alternatively, a surface of aluminum or stainless steel whose surface is treated with carbon, nickel, titanium, silver, or the like can be used. The current collector can form fine irregularities on its surface and enhance the adhesion of the positive electrode active material. Various forms such as films, sheets, foils, nets, porous bodies, foams, and nonwoven fabrics are possible. is there. In the above-described embodiment according to the present invention, the electrode tab may be formed to have the same material as that of the positive electrode current collector.
[正極活物質]
前記正極活物質はリチウム二次電池の場合、例えば、リチウムコバルト酸化物(LiCoO2)、リチウムニッケル酸化物(LiNiO2)などの層状化合物や、1又はそれ以上の転移金属に置換された化合物;化学式Li1+xMn2-xO4(ここで、xは0〜0.33である)、LiMnO3、LiMn2O3、LiMnO2などのリチウムマンガン酸化物;リチウム銅酸化物(Li2CuO2);LiV3O8、LiFe3O4、V2O5、Cu2V2O7などのバナジウム酸化物;化学式LiNi1-xMxO2(ここで、M=Co、Mn、Al、Cu、Fe、Mg、B又はGaであり、x=0.01〜0.3である)で表現されるNiサイト型リチウムニッケル酸化物;化学式LiMn2-xMxO2(ここで、M=Co、Ni、Fe、Cr、Zn又はTaで、x=0.01〜0.1である)又はLi2Mn3MO8(ここで、M=Fe、Co、Ni、Cu又はZnである)で表現されるリチウムマンガン複合酸化物;化学式のLiの一部がアルカリ土金属イオンに置換されたLiMn2O4;ジスルフィド化合物;Fe2(MoO4)3などを挙げることができるが、これらだけで限定されるものではない。
[Positive electrode active material]
In the case of a lithium secondary battery, the positive electrode active material is, for example, a layered compound such as lithium cobalt oxide (LiCoO 2 ) or lithium nickel oxide (LiNiO 2 ), or a compound substituted with one or more transition metals; Chemical formula Li 1 + xMn 2 -xO 4 (where x is 0 to 0.33), lithium manganese oxide such as LiMnO 3 , LiMn 2 O 3 , LiMnO 2 ; lithium copper oxide (Li 2 CuO 2 ); Vanadium oxides such as LiV 3 O 8 , LiFe 3 O 4 , V 2 O 5 , Cu 2 V 2 O 7 ; chemical formula LiNi 1 -xMxO 2 (where M = Co, Mn, Al, Cu, Fe, Mg Ni-site type lithium nickel oxide represented by the formula LiMn 2 -xMxO 2 (where M = Co, Ni, Fe, Cr, Zn or Ta) X = 0.01 to 0.1) or Li 2 Mn 3 MO 8 (where M = Fe, Co, Ni, Cu or Zn); Is replaced with alkaline earth metal ions And LiMn 2 O 4; disulfide compounds; Fe 2 but (MoO 4) 3, and the like, but is not limited by these alone.
前記導電材は、通常、正極活物質を含む混合物の全体重量に基づいて1ないし50重量%に添加される。このような導電材は、当該電池に化学的変化を誘発することなく導電性を有するものであれば特に制限されるものではなく、例えば、天然黒煙や人造黒煙などの黒煙;カーボンブラック、アセチレンブラック、ケッチェンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラックなどのカーボンブラック;炭素繊維や金属繊維などの導電性繊維;フッ化カーボン、アルミニウム、ニッケル粉末などの金属粉末;酸化亜鉛、チタン酸カリウムなどの導電性ウィスカー;酸化チタンなどの導電性金属酸化物;ポリフェニレン誘導体などの導電性素材などが用いられ得る。 The conductive material is usually added in an amount of 1 to 50% by weight based on the total weight of the mixture including the positive electrode active material. Such a conductive material is not particularly limited as long as it has conductivity without inducing a chemical change in the battery. For example, black smoke such as natural black smoke or artificial black smoke; carbon black Carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black, etc .; conductive fiber such as carbon fiber and metal fiber; metal powder such as carbon fluoride, aluminum, nickel powder; zinc oxide Conductive whiskers such as potassium titanate; conductive metal oxides such as titanium oxide; and conductive materials such as polyphenylene derivatives can be used.
前記バインダは、活物質と導電材などの結合と集電体に対する結合に助力する成分であって、通常に負極活物質を含む混合物全体重量に基づいて1ないし50重量%に添加される。このようなバインダの例としては、ポリフッ化ビニリデン、ポリビニルアルコール、カルボキシメチルセルロース(CMC)、澱粉、ヒドロキシプロピルセルロース、再生セルロース、ポリビニルピロリドン、テトラフルオロエチレン、ポリエチレン、ポリプロピレン、エチレン-プロピレン-ジエンテルポリマー(EPDM)、スルホン化EPDM、スチレンブチレンゴム、フッ素ゴム、多様な共重合剤などを挙げることができる。 The binder is a component that assists in the bonding of the active material and the conductive material and the bonding to the current collector, and is usually added to 1 to 50% by weight based on the total weight of the mixture including the negative electrode active material. Examples of such binders include polyvinylidene fluoride, polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer ( EPDM), sulfonated EPDM, styrene butylene rubber, fluororubber, and various copolymerization agents.
前記充填剤は、正極の膨張を抑制する成分として選択的に用いられ、当該電池に化学的変化を誘発することのない繊維状材料であれば特に制限されるものではなく、例えば、ポリエチレン、ポリプロピレンなどのオレフィン系重合剤;ガラス繊維、炭素繊維などの繊維状物質が用いられる。 The filler is not particularly limited as long as it is a fibrous material that is selectively used as a component that suppresses expansion of the positive electrode and does not induce a chemical change in the battery. For example, polyethylene, polypropylene Olefin-based polymerization agents such as glass fibers and carbon fibers are used.
[負極構造]
負極は、負極集電体上に負極活物質を塗布、乾燥及びプレッシングして製造され、必要に応じて前記のような導電材、バインダ、充填剤などが選択的にさらに含まれ得る。このような構造はシート状で具現され、ローディングロールに装着される形態で工程に適用され得るようになる。
[Negative electrode structure]
The negative electrode is manufactured by applying, drying, and pressing a negative electrode active material on a negative electrode current collector, and may optionally further include the above-described conductive material, binder, filler, and the like as necessary. Such a structure is realized in the form of a sheet and can be applied to the process in a form mounted on a loading roll.
[負極集電体]
前記負極集電体は、一般的に3〜500μmの厚さで作製される。このような負極集電体は、当該電池に化学的変化を誘発することなく導電性を有するものであれば特に制限されるものではなく、例えば、銅、ステンレススチール、アルミニウム、ニッケル、チタン、焼成炭素、銅やステンレススチールの表面にカーボン、ニッケル、チタン、銀などで表面処理したもの、アルミニウム−カドミウム合金などが用いられ得る。また、正極集電体と同様に、表面に微細な凹凸を形成して負極活物質の結合力を強化させることもでき、フィルム、シート、ホイル、ネット、多孔質体、発泡体、不織布体など多様な形態で用いられ得る。前述した本発明に係る実施例で電極タブの場合、前記負極集電体の材質と同一の材質を有するように形成され得る。
[Negative electrode current collector]
The negative electrode current collector is generally produced with a thickness of 3 to 500 μm. Such a negative electrode current collector is not particularly limited as long as it has conductivity without inducing chemical changes in the battery. For example, copper, stainless steel, aluminum, nickel, titanium, fired A surface of carbon, copper or stainless steel that has been surface-treated with carbon, nickel, titanium, silver or the like, an aluminum-cadmium alloy, or the like can be used. Also, like the positive electrode current collector, it is possible to reinforce the binding force of the negative electrode active material by forming fine irregularities on the surface, such as films, sheets, foils, nets, porous bodies, foams, nonwoven fabric bodies, etc. It can be used in various forms. In the above-described embodiment according to the present invention, the electrode tab may be formed to have the same material as that of the negative electrode current collector.
[負極活物質]
前記負極活物質は、例えば、難黒煙化炭素、黒煙系炭素などの炭素;LixFe2O3(0≦x≦1), LixWO2(0≦x≦1), SnxMe1-xMe'yOz (Me: Mn, Fe, Pb, Ge; Me':Al、B、P、Si、周期律表の1族、2族、3族元素、ハロゲン;0<x≦1;1≦y≦3;1≦z≦8)などの金属複合酸化物;リチウム金属;リチウム合金;ケイ素系合金;錫系合金;SnO, SnO2, PbO, PbO2, Pb2O3, Pb3O4, Sb2O3, Sb2O4, Sb2O5, GeO, GeO2, Bi2O3, Bi2O4, and Bi2O5などの金属酸化物;ポリアセチレンなどの導電性高分子;Li-Co-Ni系材料などを用いることができる。
[Negative electrode active material]
The negative electrode active material is, for example, carbon such as non-smoky carbon or black smoke-based carbon; LixFe 2 O 3 (0 ≦ x ≦ 1), LixWO 2 (0 ≦ x ≦ 1), SnxMe 1 -xMe'yOz (Me: Mn, Fe, Pb, Ge; Me ′: Al, B, P, Si, Group 1, Group 2, Group 3 element of the periodic table, halogen; 0 <x ≦ 1, 1 ≦ y ≦ 3; Metal composite oxides such as 1 ≦ z ≦ 8); lithium metal; lithium alloy; silicon-based alloy; tin-based alloy; SnO, SnO 2 , PbO, PbO 2 , Pb 2 O 3 , Pb 3 O 4 , Sb 2 O 3 , metal oxides such as Sb 2 O 4 , Sb 2 O 5 , GeO, GeO 2 , Bi 2 O 3 , Bi 2 O 4 , and Bi 2 O 5 ; conductive polymers such as polyacetylene; Li-Co- Ni-based materials can be used.
[分離膜]
本発明に係る分離膜は、折り畳み工程やロール(roll)工程とは係りなく、単なる積層工程により基本単位体を形成して単純積層を具現することになる。特に、ラミネートでの分離膜と正極、負極の接着は、ラミネートの内部で分離膜シート自体が熱によって溶融されて接着固定されるようにするものである。これにより、圧力が引き続き維持されるようにするところ、電極と分離膜シートとの間の安定的な界面接触を可能にする。
[Separation membrane]
The separation membrane according to the present invention realizes simple lamination by forming a basic unit body by a simple lamination process regardless of a folding process or a roll process. In particular, the adhesion between the separation membrane, the positive electrode, and the negative electrode in the laminate is such that the separation membrane sheet itself is melted by heat and bonded and fixed inside the laminate. This allows stable interfacial contact between the electrode and the separation membrane sheet so that the pressure continues to be maintained.
前記分離膜シート又はセルの正極と負極との間に介在される分離膜は絶縁性を現わし、イオンの移動が可能な多孔性構造であれば、その素材が特に制限されるものではなく、前記分離膜と分離膜シートは同一の素材である場合も、そうでない場合もある。 The separation membrane interposed between the separation membrane sheet or the positive electrode and the negative electrode of the cell exhibits insulation, and the material is not particularly limited as long as it is a porous structure capable of ion migration, The separation membrane and the separation membrane sheet may or may not be the same material.
前記分離膜又は分離膜シートは、例えば、高いイオン透過度と機械的強度を有する絶縁性の薄い薄膜が用いられ得、分離膜又は分離膜シートの気孔直径は一般的に0.01〜10μmであり、厚さは一般的に5〜300μmである。このような分離膜又は分離膜シートとしては、例えば、耐化学性及び疎水性のポリプロピレンなどのオレフィン系ポリマー;ガラス繊維又はポリエチレンなどで作製されたシートや不織布などが用いられる。電解質としてポリマーなどの固体電解質が用いられる場合は、固体電解質が分離膜を兼ねることもできる。好ましくは、ポリエチレンフィルム、ポリプロピレンフィルム、又はこれらフィルムの組合せによって製造される多層フィルムやポリビニリデンフルオライド(polyvinylidene fluoride)、ポリエチレンオキシド(polyethylene oxide)、ポリアクリロニトリル(polyacrylonitrile)、又はポリビニリデンフルオライドヘキサフルオロプロピレン(polyvinylidene fluoride hexafluoropropylene)共重合体などの高分子電解質用、又はゲル型高分子電解質用高分子フィルムであり得る。 As the separation membrane or separation membrane sheet, for example, an insulating thin thin film having high ion permeability and mechanical strength can be used, and the pore diameter of the separation membrane or separation membrane sheet is generally 0.01 to 10 μm, The thickness is generally 5 to 300 μm. As such a separation membrane or separation membrane sheet, for example, a olefin polymer such as chemically resistant and hydrophobic polypropylene; a sheet made of glass fiber or polyethylene, a nonwoven fabric, or the like is used. When a solid electrolyte such as a polymer is used as the electrolyte, the solid electrolyte can also serve as a separation membrane. Preferably, a multilayer film, polyvinylidene fluoride, polyethylene oxide, polyacrylonitrile, or polyvinylidene fluoride hexafluoro produced by a polyethylene film, a polypropylene film, or a combination of these films. It may be a polymer film for a polymer electrolyte such as a propylene (polyvinylidene fluoride hexafluoropropylene) copolymer or a gel type polymer electrolyte.
前記分離膜は、基本単位セルを構成するために熱融着による接着機能を有するのが好ましく、前記分離膜シートは必ずそのような機能を有する必要はないが、接着機能を有するものを用いるのが好ましい。 The separation membrane preferably has an adhesive function by heat fusion in order to constitute a basic unit cell, and the separation membrane sheet does not necessarily have such a function, but a material having an adhesive function is used. Is preferred.
本発明に係る前記電極組立体は、正極と負極の電気化学的反応によって電気を生産する電気化学セルに適用され得るところ、電気化学セルの代表的な例としては、スーパーキャパシタ(super capacitor)、ウルトラキャパシタ(ultra capacitor)、二次電池、燃料電池、各種センサ、電気分解装置、電気化学的反応器などを挙げることができ、そのうち二次電池が特に好ましい。 The electrode assembly according to the present invention can be applied to an electrochemical cell that produces electricity by an electrochemical reaction between a positive electrode and a negative electrode. As a representative example of the electrochemical cell, a super capacitor, Examples include an ultracapacitor, a secondary battery, a fuel cell, various sensors, an electrolyzer, an electrochemical reactor, etc. Among them, a secondary battery is particularly preferable.
前記二次電池は、充放電が可能な電極組立体がイオン含有電解液で含浸された状態で、電池ケースに内装している構造となっており、一つの好ましい例として、前記二次電池はリチウム二次電池であり得る。 The secondary battery has a structure in which a chargeable / dischargeable electrode assembly is impregnated with an ion-containing electrolyte, and is embedded in a battery case. As one preferred example, the secondary battery includes: It may be a lithium secondary battery.
近年、リチウム二次電池は小型モバイル機器だけでなく、大型デバイスの電源として多くの関心を集めており、そのような分野への適用時に小さい重量を有するのが好ましい。二次電池の重量を減らす一つの方案として、アルミニウムラミネートシートのパウチ型ケースに電極組立体を内装した構造が好ましい。このようなリチウム二次電池に対しては当業界に公知されているので、本明細書には関連説明を略する。 In recent years, lithium secondary batteries have attracted much attention as power sources for large devices as well as small mobile devices, and preferably have a low weight when applied to such fields. As one method for reducing the weight of the secondary battery, a structure in which an electrode assembly is housed in a pouch-type case made of an aluminum laminate sheet is preferable. Since such a lithium secondary battery is known in the art, a related description is omitted in this specification.
また、前記で説明したように、中大型デバイスの電源として用いる際には、長期間の使用時にも作動性能の低下現象を最大限抑制し、寿命特性が優れ、且つ安い費用で大量生産することのできる構造の二次電池が好ましい。このような観点で本発明の電極組立体を含む二次電池は、これを単位電池とする中大型電池モジュールに好ましく用いられ得る。 In addition, as described above, when used as a power source for medium- and large-sized devices, mass production should be performed at a low cost with excellent lifetime characteristics and maximum reduction in operating performance during long-term use. A secondary battery having a structure that can be used is preferable. From such a point of view, the secondary battery including the electrode assembly of the present invention can be preferably used for a medium-to-large battery module using this as a unit battery.
多数の二次電池を含む電池モジュールを含む電池パックの場合、パワーツール(power tool);電気車(Electric Vehicle, EV)、ハイブリッド電気車(Hybrid Electric Vehicle, HEV)及びプラグインハイブリッド電気車(Plug-in Hybrid Electric Vehicle, PHEV)からなる群より選択された電気車;E-バイク(E-bike);E-スクーター(E-scooter);電気ゴルフカート(Electric golf cart);電気トラック;及び電気商用車からなる中大型デバイスの群より選択された一つ以上の電源で用いられ得る。 In the case of a battery pack including a battery module including a number of secondary batteries, a power tool (electric vehicle, EV), a hybrid electric vehicle (HEV), and a plug-in hybrid electric vehicle (Plug) -Electric vehicle selected from the group consisting of Hybrid Electric Vehicle (PHEV); E-bike; E-scooter; Electric golf cart; Electric truck; and Electric It can be used with one or more power sources selected from a group of medium to large devices consisting of commercial vehicles.
中大型電池モジュールは、多数の単位電池などをシリーズ方式又はシリーズ/パラレルを方式で連結して高出力・大容量を提供するように構成されており、それに対しては当業界に公知されているので本明細書には関連説明を略する。
前述したような本発明の詳細な説明では、具体的な実施例に関して説明した。しかし、本発明の範疇から外れない限度内では、多様な変形が可能である。本発明の技術的思想は、本発明の記述した実施例に限って定められてはならず、特許請求の範囲だけではなく、この特許請求の範囲と均等なものなどによって定められなければならない。
以下に、実施形態の一例を項目として記す。
[項目1]
正極集電体上に正極活物質がコーティングされる正極;
負極集電体上に負極活物質がコーティングされる負極;及び
前記正極及び負極との間に配置される分離膜を含む電極組立体であって、
前記正極を構成する正極集電体のタブ部に絶縁層が形成され、
前記絶縁層は、前記正極集電体と前記分離膜との間で、前記正極集電体、前記正極活物質の塗布領域の末端、及び前記分離膜の何れにも接合されるように配置され、
前記正極集電体の表面には凹凸が形成されていることを特徴とする電極組立体。
[項目2]
前記絶縁層は、
前記負極活物質の塗布領域と一部がオーバーラップ(overlap)されるように配置される項目1に記載の電極組立体。
[項目3]
前記絶縁層は、前記タブ部の一端が露出する露出部が形成されるように具現される項目1に記載の電極組立体。
[項目4]
前記絶縁層の幅は、1mm〜20mmである項目3に記載の電極組立体。
[項目5]
前記絶縁層の厚さは、1μm〜100μmである項目4に記載の電極組立体。
[項目6]
前記絶縁層は、少なくとも1以上のセラミック物質を含有した絶縁物質であることを特徴とする項目1に記載の電極組立体。
[項目7]
前記絶縁層は、二酸化チタン、カルシウムカーボネート及び硫酸バリウムからなる群より選択されるいずれか一つ、又は二つ以上を混合した物質である項目6に記載の電極組立体。
[項目8]
前記絶縁層は、二酸化チタン、カルシウムカーボネート及び硫酸バリウムからなる群より選択される一つ、又は二つ以上を混合した物質を10〜90%重量比で含有した水溶液又は塗料を乾燥した物質であることを特徴とする項目7に記載の電極組立体。
[項目9]
前記絶縁層は、重量平均分子量20万以下の高分子フィルム又はエマルジョンであることを特徴とする項目1に記載の電極組立体。
[項目10]
前記高分子フィルムは、ポリアクリレート、ポリスチレン、ポリアクリル酸、ポリアクリロニトリル、ポリエチレン、ポリプロピレン、ポリイミド、ポリウレタン、ポリエチレンテレフタレート、及びこれらの組合せからなる群より選択されるいずれか一つで形成される項目9に記載の電極組立体。
[項目11]
前記絶縁層は、SBR系重合体である項目1に記載の電極組立体。
[項目12]
項目1から項目11のいずれかの電極組立体を1以上含む電気化学素子。
[項目13]
前記電気化学素子は、二次電池、多数の二次電池を含む電池モジュール及び多数の電池のモジュールを含む電池パックからなる群より選択されるいずれか一つである項目12に記載の電気化学素子。
Medium and large-sized battery modules are configured to provide high output and large capacity by connecting a large number of unit batteries, etc. in series or series / parallel, and are well known in the art. Therefore, a related description is omitted in this specification.
In the foregoing detailed description of the invention, specific embodiments have been described. However, various modifications can be made without departing from the scope of the present invention. The technical idea of the present invention should not be defined only by the embodiments described in the present invention, but should be defined not only by the claims but also by the equivalents of the claims.
Below, an example of embodiment is described as an item.
[Item 1]
A positive electrode in which a positive electrode active material is coated on a positive electrode current collector;
A negative electrode coated with a negative electrode active material on the negative electrode current collector; and
An electrode assembly including a separation membrane disposed between the positive electrode and the negative electrode,
An insulating layer is formed on the tab portion of the positive electrode current collector constituting the positive electrode,
The insulating layer is disposed between the positive electrode current collector and the separation membrane so as to be bonded to any of the positive electrode current collector, a terminal of the positive electrode active material coating region, and the separation membrane. ,
The electrode assembly is characterized in that irregularities are formed on a surface of the positive electrode current collector.
[Item 2]
The insulating layer is
2. The electrode assembly according to item 1, wherein the electrode active material is disposed so that a part of the negative electrode active material application region overlaps.
[Item 3]
2. The electrode assembly according to item 1, wherein the insulating layer is embodied such that an exposed portion from which one end of the tab portion is exposed is formed.
[Item 4]
Item 4. The electrode assembly according to Item 3, wherein the width of the insulating layer is 1 mm to 20 mm.
[Item 5]
Item 5. The electrode assembly according to Item 4, wherein the insulating layer has a thickness of 1 µm to 100 µm.
[Item 6]
2. The electrode assembly according to item 1, wherein the insulating layer is an insulating material containing at least one ceramic material.
[Item 7]
Item 7. The electrode assembly according to Item 6, wherein the insulating layer is one selected from the group consisting of titanium dioxide, calcium carbonate, and barium sulfate, or a mixture of two or more.
[Item 8]
The insulating layer is a substance obtained by drying an aqueous solution or a paint containing 10 to 90% by weight of one or a mixture of two or more selected from the group consisting of titanium dioxide, calcium carbonate and barium sulfate. 8. The electrode assembly according to item 7, wherein
[Item 9]
Item 2. The electrode assembly according to Item 1, wherein the insulating layer is a polymer film or emulsion having a weight average molecular weight of 200,000 or less.
[Item 10]
The polymer film is formed of any one selected from the group consisting of polyacrylate, polystyrene, polyacrylic acid, polyacrylonitrile, polyethylene, polypropylene, polyimide, polyurethane, polyethylene terephthalate, and combinations thereof. An electrode assembly according to claim 1.
[Item 11]
Item 2. The electrode assembly according to Item 1, wherein the insulating layer is an SBR polymer.
[Item 12]
An electrochemical device comprising one or more electrode assemblies according to any one of items 1 to 11.
[Item 13]
The electrochemical element according to
Claims (4)
負極集電体上に負極活物質がコーティングされる複数の板状の負極;及び
前記正極及び負極との間に配置される分離膜を含むパウチ型二次電池に用いられる電極組立体であって、
前記複数の正極と前記複数の負極とが順次積層され、
前記正極のタブとして用いられる正極集電体のタブ部に絶縁層が形成され、
前記タブ部は前記正極集電体の極板から延長して突出し、
前記絶縁層は、前記正極集電体と前記分離膜との間で、前記正極集電体、前記正極活物質の塗布領域の末端、及び前記分離膜の何れにも接合されるように配置され、
前記絶縁層は、前記タブ部の一端が露出する露出部が形成されるように具現され、
前記絶縁層は、二酸化チタン、カルシウムカーボネート及び硫酸バリウムからなる群より選択されるいずれか一つ、若しくは二つ以上を混合した物質、またはSBR系重合体であり、
前記分離膜は、前記正極活物質と接着し、前記絶縁層と接合し、
前記絶縁層は、
前記負極活物質の塗布領域と一部がオーバーラップ(overlap)されるように配置され、
前記分離膜はシート状であり、
前記絶縁層の幅T3は1mmから20mmの範囲であり、正極集電体の露出部の幅T2と絶縁層の幅との総長さT1は20mmから30mmの範囲であり、絶縁層の厚さは1μm〜100μmであることを特徴とする電極組立体。 A plurality of plate-like positive electrodes coated with a positive electrode active material on a positive electrode current collector;
An electrode assembly for use in a pouch-type secondary battery, comprising: a plurality of plate-like negative electrodes coated with a negative electrode active material on a negative electrode current collector; and a separation membrane disposed between the positive electrode and the negative electrode. ,
The plurality of positive electrodes and the plurality of negative electrodes are sequentially laminated,
An insulating layer is formed on the tab portion of the positive electrode current collector used as the positive electrode tab,
The tab portion extends and projects from the electrode plate of the positive electrode current collector,
The insulating layer is disposed between the positive electrode current collector and the separation membrane so as to be bonded to any of the positive electrode current collector, a terminal of the positive electrode active material coating region, and the separation membrane. ,
The insulating layer is embodied such that an exposed portion from which one end of the tab portion is exposed is formed,
The insulating layer is any one selected from the group consisting of titanium dioxide, calcium carbonate, and barium sulfate, or a substance in which two or more are mixed, or an SBR polymer.
The separation membrane is bonded to the positive electrode active material, bonded to the insulating layer ,
The insulating layer is
The negative electrode active material coating region is disposed so as to partially overlap (overlap),
The separation membrane is in sheet form,
The width T3 of the insulating layer ranges from 1 mm to 20 mm, the total length T1 of the width T2 of the exposed portion of the positive electrode current collector and the width of the insulating layer ranges from 20 mm to 30 mm, and the thickness of the insulating layer is An electrode assembly having a thickness of 1 μm to 100 μm .
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