JP2006286365A - Current collector with terminal, and electrochemical element using the same - Google Patents

Current collector with terminal, and electrochemical element using the same Download PDF

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JP2006286365A
JP2006286365A JP2005103915A JP2005103915A JP2006286365A JP 2006286365 A JP2006286365 A JP 2006286365A JP 2005103915 A JP2005103915 A JP 2005103915A JP 2005103915 A JP2005103915 A JP 2005103915A JP 2006286365 A JP2006286365 A JP 2006286365A
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terminal
current collector
main body
nickel
expanded metal
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JP4868761B2 (en
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Kazuya Sato
和哉 佐藤
Toshiaki Takase
俊明 高瀬
Masanao Tanaka
政尚 田中
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Japan Vilene Co Ltd
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    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a current collector with strong jointing strength between a terminal and the current collector and having a low resistance due to the low resistance of the terminal itself and the low resistance between the current collector and the terminal. <P>SOLUTION: The current collector with the terminal is a current collector, wherein the terminal made of an expanded metal is jointed to a current collector body which is filled with an active material to be an electrode. The terminal is made of the expanded metal with a ratio (LW/SW) of center-to-center distance (LW) between holes, in the long direction to center-to-center distance (SW) between holes in a short direction is 1.9-5 and number-of-holes density of 30-130 holes/cm<SP>2</SP>. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は端子付集電材及びこれを用いた電気化学素子、例えば、アルカリ二次電池、リチウムイオン二次電池、若しくは電気二重層キャパシタに関する。   The present invention relates to a current collector with a terminal and an electrochemical element using the current collector, for example, an alkaline secondary battery, a lithium ion secondary battery, or an electric double layer capacitor.

従来、アルカリ二次電池は、高信頼性でかつ小型軽量化が可能であるため、ポータブル機器から産業用大型設備までの各種装置の電源として多用されている。このアルカリ二次電池においては、一般的に正極としてニッケル電極が使用され、このニッケル電極は、集電機能を分担する集電材に、電池反応を生起させるための正極活物質を担持させたものからなる。この集電材として、ニッケル粉末を焼結した焼結ニッケル板やパンチングニッケル板などが広く用いられてきた。電池の容量は集電材の空隙中に充填された活物質の量によって決まり、この活物質の充填量は集電材の空隙率によって決まるため、集電材の空隙率はできるだけ大きいのが好ましい。   2. Description of the Related Art Conventionally, alkaline secondary batteries are highly reliable and can be reduced in size and weight, and thus are widely used as power sources for various devices ranging from portable devices to industrial large facilities. In this alkaline secondary battery, a nickel electrode is generally used as a positive electrode, and this nickel electrode is obtained by carrying a positive electrode active material for causing a battery reaction on a current collector that shares a current collecting function. Become. As the current collector, a sintered nickel plate or a punched nickel plate obtained by sintering nickel powder has been widely used. Since the capacity of the battery is determined by the amount of the active material filled in the gap of the current collector, and the amount of the active material is determined by the porosity of the current collector, it is preferable that the porosity of the current collector is as large as possible.

ところが従来の焼結ニッケル板やパンチングニッケル板は空隙率が７５〜８０％と低い上に、活物質を高密度に充填することが困難であるため、空隙率が高く、活物質を高密度に充填することができる集電材として、本願出願人は「スルホン化処理、フッ素ガス処理又はビニルモノマーのグラフト処理により親水化された不織布と、前記不織布の表面に形成されたニッケルめっき膜とを備えたアルカリ二次電池用集電材」を提案した（特許文献１）。この集電材は帯状に形成され、電池の封入板又は電池の缶底へと導電させる外部端子を取り付ける箇所を押し潰し、活物質を含むペーストを充填、乾燥、圧延した後、更に前記押し潰した箇所に外部端子としてのニッケル片をスポット溶接して、端子付電極（端子付正極又は端子付負極）となる。そして、この端子付正極と端子付負極との間にセパレータを介在させた電極群を形成し、この電極群を電池ケースへ収容して電池を形成できる。この集電材自体は確かに集電性能の高いものであったが、通常外部端子として使用されているニッケル片をスポット溶接して端子付電極を製造すると、集電材と外部端子との接合強度が弱いため電極群を形成する際に外部端子が外れるという問題や、外部端子と集電材との間の抵抗が高いため、ハイレート放電特性に劣る、などの問題があった。   However, since the conventional sintered nickel plate and punched nickel plate have a low porosity of 75 to 80% and it is difficult to fill the active material with a high density, the porosity is high and the active material has a high density. As a current collector that can be filled, the applicant of the present application is provided with a nonwoven fabric hydrophilized by sulfonation treatment, fluorine gas treatment or vinyl monomer graft treatment, and a nickel plating film formed on the surface of the nonwoven fabric. A current collector for alkaline secondary batteries was proposed (Patent Document 1). This current collector is formed in a band shape, crushes the location where the external terminal for conducting electricity to the battery encapsulating plate or the battery can bottom is crushed, filled with paste containing the active material, dried, rolled, and then further crushed A nickel piece as an external terminal is spot-welded to a location to form an electrode with a terminal (a positive electrode with a terminal or a negative electrode with a terminal). An electrode group in which a separator is interposed between the positive electrode with terminal and the negative electrode with terminal is formed, and the electrode group is accommodated in a battery case to form a battery. Although this current collector itself was certainly high in current collection performance, when a terminal-attached electrode was manufactured by spot welding a nickel piece normally used as an external terminal, the bonding strength between the current collector and the external terminal was high. There is a problem that the external terminal is detached when forming the electrode group because it is weak, and a high resistance between the external terminal and the current collector is high, resulting in inferior high-rate discharge characteristics.

このような問題点を解決するために、「ニッケルめっきが施された不織布からなる集電材に、１又は２以上の正極又は負極端子が金属テープを介して前記集電材に溶接されたアルカリ二次電池用電極」が提案されている（特許文献２）。この金属テープとしては、ニッケル線を編んだ網又はニッケル線からなる不織布を開示している。この電極はニッケル線を編んだ網又はニッケル線からなる不織布を溶接しているため溶接強度は強いものの、ニッケル線を編んだ網又はニッケル線からなる不織布自体の抵抗が高く、ハイレート放電特性に劣る、という問題があった。   In order to solve such a problem, an alkaline secondary in which one or two or more positive or negative terminals are welded to the current collector via a metal tape on a current collector made of a non-woven fabric plated with nickel A battery electrode "has been proposed (Patent Document 2). As the metal tape, a net woven of nickel wire or a non-woven fabric made of nickel wire is disclosed. This electrode is welded with a mesh made of nickel wire or a non-woven fabric made of nickel wire, so the welding strength is strong, but the resistance of the non-woven fabric itself made of a mesh made of nickel wire or nickel wire is high and inferior in high-rate discharge characteristics. There was a problem.

以上はアルカリ二次電池に関してであるが、他の電気化学素子（例えば、リチウムイオン二次電池又は電気二重層キャパシタ）においても同様の問題があった。   Although the above is about an alkaline secondary battery, the same problem also exists in other electrochemical elements (for example, a lithium ion secondary battery or an electric double layer capacitor).

特開２００１−３１３０３８号公報（特許請求の範囲、段落番号００３２、実施例５〜６など）JP-A-2001-313038 (Claims, paragraph number 0032, Examples 5-6, etc.) 特開２００２−３１９４１０号公報（請求項１、請求項５など）JP 2002-319410 A (Claim 1, Claim 5, etc.)

本発明は上述のような問題点を解決するためになされたもので、端子と集電材との間の接合強度が強く、また端子自体及び集電材と端子との間の抵抗が低いことによって抵抗の低い端子付集電材を提供することを目的とする。また、この端子付集電材を用いた電気化学素子を提供することも目的とする。   The present invention has been made in order to solve the above-described problems, and has a high bonding strength between the terminal and the current collector, and a low resistance between the terminal itself and the current collector and the terminal. An object of the present invention is to provide a current collector with a low terminal. It is another object of the present invention to provide an electrochemical element using the current collector with terminal.

本発明の請求項１にかかる発明は、「活物質が充填されて電極となる集電材本体に、エキスパンドメタルからなる端子が接合された端子付集電材であり、前記端子は孔の長目方向中心間距離（ＬＷ）の、孔の短目方向中心間距離（ＳＷ）に対する比（ＬＷ／ＳＷ）が１．９〜５、かつ孔数密度が３０〜１３０個／ｃｍ２のエキスパンドメタルからなることを特徴とする端子付集電材。」である。 The invention according to claim 1 of the present invention is a current collector with a terminal in which a terminal made of expanded metal is joined to a current collector main body filled with an active material to be an electrode, and the terminal is in the long direction of the hole A ratio (LW / SW) of the center-to-center distance (LW) to the center-to-center distance (SW) in the short direction of the holes is 1.9 to 5, and the hole density is 30 to 130 holes / cm 2. It is a current collector with a terminal characterized by this. "

本発明の請求項２にかかる発明は、「集電材本体が、不織布にめっきを施しただけで、不織布を熱分解除去していないものからなることを特徴とする、請求項１記載の端子付集電材。」である。   The invention according to claim 2 of the present invention is as follows: “The current collector main body is formed by plating the nonwoven fabric and not thermally removing the nonwoven fabric. Current collector. "

本発明の請求項３にかかる発明は、「集電材本体が長方形状を有し、集電材本体の一辺全てに端子が接合されていることを特徴とする、請求項１又は請求項２に記載の端子付集電材。」である。   The invention according to claim 3 of the present invention is as follows: “The current collector main body has a rectangular shape, and terminals are joined to all sides of the current collector main body. Current collector with terminal. "

本発明の請求項４にかかる発明は、「更に金属片からなる外部端子が端子に接合されていることを特徴とする、請求項３記載の端子付集電材。」である。   The invention according to claim 4 of the present invention is “the current collector with terminal according to claim 3, wherein an external terminal made of a metal piece is joined to the terminal”.

本発明の請求項５にかかる発明は、「請求項１〜請求項４のいずれかに記載の端子付集電材を用いた電気化学素子。」である。   The invention according to claim 5 of the present invention is "an electrochemical element using the current collector with a terminal according to any one of claims 1 to 4."

本発明の請求項６にかかる発明は、「アルカリ二次電池、リチウムイオン二次電池、電気二重層キャパシタの中から選ばれる電気化学素子であることを特徴とする、請求項５記載の電気化学素子。」である。   The invention according to claim 6 of the present invention is an electrochemical device according to claim 5, which is an electrochemical element selected from an alkaline secondary battery, a lithium ion secondary battery, and an electric double layer capacitor. Element. "

本発明の請求項１にかかる発明は、端子が特定のエキスパンドメタルからなり、アンカー効果によって、集電材本体と端子との接合強度が強いため、電極群の形成時に端子が外れることがなく、しかも集電材本体と端子との間の抵抗が低い。また、従来のニッケル線を編んだ網やニッケル線からなる不織布は、ニッケル線同士の交差点は接触の程度が低かったり、接触していないニッケル線もあるなど、抵抗が高いものであったのに対して、本発明の端子付集電材の端子であるエキスパンドメタルは孔の周囲は完全に繋がった状態にあり、抵抗が低いため、抵抗の低い端子付集電材である。   In the invention according to claim 1 of the present invention, the terminal is made of a specific expanded metal, and the anchoring effect provides a strong bonding strength between the current collector main body and the terminal, so that the terminal does not come off when the electrode group is formed. Low resistance between current collector body and terminals. In addition, a conventional non-woven fabric made of a nickel wire woven net or nickel wire has a high resistance, such as a low degree of contact between nickel wires or a non-contact nickel wire. On the other hand, the expanded metal which is the terminal of the current collector with terminal of the present invention is a current collector with terminal having low resistance because the periphery of the hole is completely connected and the resistance is low.

本発明の請求項２にかかる発明は、集電材本体が不織布を熱分解除去していないめっきした不織布からなるため、端子を接続する際に、端子構成金属とめっき金属との接合のみではなく、めっきした不織布を構成する樹脂が溶け出すことによるアンカー効果も作用し、接合強度が強い。   In the invention according to claim 2 of the present invention, since the current collector main body is made of a plated nonwoven fabric in which the nonwoven fabric is not thermally decomposed and removed, when connecting the terminals, not only the joining of the terminal constituent metal and the plated metal, The anchor effect due to the dissolution of the resin constituting the plated nonwoven fabric also acts, and the bonding strength is strong.

本発明の請求項３にかかる発明は、電極群を形成した後、端子に集電板を接合することによって、ハイレート放電を可能とすることができる。   In the invention according to claim 3 of the present invention, high rate discharge can be achieved by joining the current collector plate to the terminal after forming the electrode group.

本発明の請求項４にかかる発明は、外部端子が端子に接合されているため、電気化学素子を製造する際に、端子に集電板を接合するという、機械的に複雑な工程を省くことができる、簡易に電気化学素子を製造できるものである。   In the invention according to claim 4 of the present invention, since the external terminal is joined to the terminal, a mechanically complicated process of joining the current collector plate to the terminal is omitted when manufacturing the electrochemical element. It is possible to easily manufacture an electrochemical element.

本発明の請求項５にかかる発明は、端子と集電材本体との接合強度が強い端子付集電材を使用しているため、電極群構成時に端子が外れることによる不良を発生させることなく製造できる電気化学素子である。また、端子自体の抵抗及び端子と集電材本体との間の抵抗が低いため、電極からの電気の出し入れがスムーズで、充放電効率の高いものである。そのため利用率が高く、高率充放電特性に優れた電気化学素子であることができる。   The invention according to claim 5 of the present invention uses the current collector with a terminal having a strong bonding strength between the terminal and the current collector main body, and therefore can be manufactured without causing a defect due to the terminal coming off during the electrode group configuration. It is an electrochemical element. In addition, since the resistance of the terminal itself and the resistance between the terminal and the current collector main body are low, the electricity can be smoothly taken in and out, and the charge / discharge efficiency is high. Therefore, it can be an electrochemical device having a high utilization rate and excellent high rate charge / discharge characteristics.

本発明の請求項６にかかる発明は、不良を発生させることなく製造でき、また、充放電効率が高く、利用率が高く、しかも高率充放電特性に優れるアルカリ二次電池、リチウムイオン二次電池、又は電気二重層キャパシタであることができる。特に、請求項３にかかる発明の端子付集電材を使用したアルカリ二次電池はハイレート放電できるアルカリ二次電池であることができる。   The invention according to claim 6 of the present invention is an alkaline secondary battery, lithium ion secondary battery that can be manufactured without causing defects, has high charge / discharge efficiency, high utilization, and excellent high-rate charge / discharge characteristics. It can be a battery or an electric double layer capacitor. In particular, the alkaline secondary battery using the current collector with terminal of the invention according to claim 3 can be an alkaline secondary battery capable of high-rate discharge.

本発明の集電材本体は充填された活物質を担持するとともに、活物質の電荷を集める作用をするもので、公知のものを使用できる。例えば、焼結ニッケル板、パンチングニッケル板、発泡体や不織布などの多孔体にめっきを施したもの（発泡体や不織布を熱分解除去しても、していなくても良い）などを使用できる。   The current collector main body of the present invention supports the filled active material and collects the charge of the active material, and a known material can be used. For example, a sintered nickel plate, a punched nickel plate, or a porous body such as a foam or a nonwoven fabric plated (a foam or a nonwoven fabric may be removed by thermal decomposition) or the like can be used.

これらの中でも、不織布にめっきを施しただけで、不織布を熱分解除去していないものを集電材本体として好適に使用できる。端子を接続する際に、端子構成金属とめっき金属との接合のみではなく、めっきした不織布を構成する樹脂が溶け出すことによるアンカー効果によって、集電材本体と端子との接合強度が強くなるためである。また、不織布は従来の発泡ニッケルや金属箔などと比較して比表面積が大きく、活物質や活性炭との接触面積が大きいため、利用率が高く、高率充放電特性に優れた電気化学素子を製造することができる。更には、不織布は柔軟性に優れるため、電極群作製時（例えば、巻回時）にひび割れが生じず、ひび割れにより生じるエッジが原因の短絡が発生しないという効果、及び電極群(正極、負極及びセパレータ)の密着性が向上し、内部インピーダンスが低くなり、利用率が高く、高率充放電特性に優れた電気化学素子を製造できるという効果を奏する。この集電材本体の中でも、親水化処理した不織布にめっきを施したものを特に好適に使用できる。めっき膜と不織布との密着性に優れ、電気化学素子の組み立て時や充放電を繰り返してもめっき膜が脱落したりすることがないためである。   Among these, the non-woven fabric that is not thermally decomposed and removed by simply plating the nonwoven fabric can be suitably used as the current collector main body. When connecting the terminals, not only the bonding of the metal constituting the terminal and the plated metal, but also the anchor effect due to the dissolution of the resin constituting the plated non-woven fabric, the bonding strength between the current collector main body and the terminal is increased. is there. Nonwoven fabrics have a large specific surface area compared to conventional foamed nickel and metal foil, and a large contact area with the active material and activated carbon. Can be manufactured. Furthermore, since the nonwoven fabric is excellent in flexibility, there is no cracking at the time of electrode group production (for example, at the time of winding), an effect that an edge caused by the crack does not occur, and an electrode group (positive electrode, negative electrode and Adhesion of the separator) is improved, the internal impedance is lowered, the utilization factor is high, and an electrochemical element excellent in high rate charge / discharge characteristics can be produced. Among the current collector main bodies, those obtained by plating hydrophilic nonwoven fabrics can be particularly preferably used. This is because the adhesion between the plating film and the non-woven fabric is excellent, and the plating film does not fall off even when the electrochemical device is assembled or repeated charging and discharging.

本発明の集電材本体は常法により製造することができる。例えば、好適である親水化処理した不織布にめっきを施した集電材本体は、次のようにして製造することができる。まず、カード法、エアレイ法、メルトブロー法、或いはスパンボンド法のような乾式法により、又は湿式法により繊維ウエブを形成する。なお、繊維ウエブを構成する繊維は端子付集電材の使用用途（電気化学素子）によって異なる。例えば、アルカリ二次電池用に用いる場合には、ポリオレフィン系繊維及び／又はポリアミド系繊維を使用することができ、リチウムイオン二次電池用に用いる場合には、ポリオレフィン系繊維、芳香族ポリアミド繊維、ポリイミド繊維、全芳香族ポリエステル繊維、ポリアミドイミド繊維、芳香族ポリエーテルアミド繊維、及び／又はポリベンゾイミダゾール繊維を使用することができ、電気二重層キャパシタ用に用いる場合には、ポリアミド系繊維、ポリオレフィン系繊維、ポリエステル系繊維、及び／又はセルロース系繊維を使用することができる。   The current collector main body of the present invention can be produced by a conventional method. For example, a current collector main body obtained by plating a suitable non-woven fabric subjected to hydrophilic treatment can be manufactured as follows. First, a fiber web is formed by a dry method such as a card method, an air lay method, a melt blow method, a spun bond method, or a wet method. In addition, the fiber which comprises a fiber web changes with the uses (electrochemical element) of the collector material with a terminal. For example, when used for alkaline secondary batteries, polyolefin fibers and / or polyamide fibers can be used, and when used for lithium ion secondary batteries, polyolefin fibers, aromatic polyamide fibers, Polyimide fiber, wholly aromatic polyester fiber, polyamideimide fiber, aromatic polyetheramide fiber, and / or polybenzimidazole fiber can be used. When used for electric double layer capacitors, polyamide fiber, polyolefin Base fibers, polyester fibers, and / or cellulosic fibers can be used.

次いで、絡合処理（水流絡合処理、ニードルパンチ処理）、融着処理或いは接着処理を単独で、又は併用して前記繊維ウエブを結合して、不織布を製造できる。特に、融着処理によって繊維を融着させると、不織布の強度に優れているため好適である。なお、融着処理によって繊維を融着させる場合には、繊維として他の繊維よりも融点の低い樹脂（低融点樹脂）を繊維表面に備えた低融点繊維（特には、低融点樹脂に加えて、低融点樹脂よりも融点の高い高融点樹脂を備える複合繊維が好ましい）を繊維ウエブ中に含ませておくのが好ましい。   Subsequently, the nonwoven fabric can be produced by combining the fiber webs by entanglement treatment (water entanglement treatment, needle punching treatment), fusing treatment or adhesion treatment alone or in combination. In particular, it is preferable to fuse fibers by a fusion treatment because the strength of the nonwoven fabric is excellent. In addition, when fusing a fiber by a fusing process, a low melting point fiber (particularly, in addition to a low melting point resin) having a fiber having a lower melting point than other fibers (low melting point resin) as a fiber. It is preferable to include a composite fiber having a high melting point resin having a higher melting point than that of the low melting point resin) in the fiber web.

次いで、常法により不織布に親水化処理を実施する。この親水化処理としては、例えば、スルホン化処理、フッ素ガス処理、ビニルモノマーのグラフト処理、或いはコロナ放電処理などを挙げることができる。   Next, the nonwoven fabric is hydrophilized by a conventional method. Examples of the hydrophilization treatment include sulfonation treatment, fluorine gas treatment, vinyl monomer graft treatment, or corona discharge treatment.

そして、常法により親水化処理した不織布をめっきして、集電材本体を製造することができる。例えば、無電解めっき法により親水化処理した不織布をめっきすることができ、無電解めっき法により親水化処理された不織布に無電解めっき膜を形成した後に、更に電解めっき法により電解めっき膜を形成するのが好ましい。なお、親水化処理した不織布へのメッキ量は集電材本体の質量の３０〜７０％であるのが好ましい。３０％未満であると、抵抗が高くなる傾向があり、７０％を超えると、めっき金属により繊維が太くなり、集電材本体の孔径が小さくなる結果、活物質の充填性が悪くなる傾向があるためである。また、めっき金属の種類は電解液や電気化学素子の反応により劣化が起こらない金属であれば良く、例えばアルカリ二次電池ではニッケル、リチウムイオン二次電池では負極用として銅、正極及び負極用としてニッケル又はチタン、電気二重層キャパシタではニッケル又はチタンを挙げることができる。   Then, the current collector main body can be manufactured by plating the nonwoven fabric hydrophilized by a conventional method. For example, a non-woven fabric that has been hydrophilized by electroless plating can be plated. After forming an electroless plating film on a non-woven fabric that has been hydrophilized by electroless plating, an electroplating film is further formed by electroplating. It is preferable to do this. In addition, it is preferable that the plating amount to the nonwoven fabric which performed the hydrophilic treatment is 30 to 70% of the mass of the current collector main body. If it is less than 30%, the resistance tends to be high, and if it exceeds 70%, the fiber is thickened by the plated metal, and the pore diameter of the current collector main body is reduced, so that the active material filling property tends to be poor. Because. Also, the type of plating metal may be any metal that does not deteriorate due to the reaction of the electrolytic solution or electrochemical element. For example, nickel is used for alkaline secondary batteries, and copper is used for negative electrodes for lithium ion secondary batteries. Nickel or titanium and nickel or titanium can be used for electric double layer capacitors.

本発明の端子付集電材は上述のような集電材本体にエキスパンドメタルからなる端子が接合されたもので、エキスパンドメタルは孔のある凹凸構造を有するため、アンカー効果によって集電材本体との接合強度が強い。そのため、電極群の形成時に端子が外れることがなく、しかも集電材本体と端子との間の抵抗が低いものである。また、エキスパンドメタルはスリットを入れた後にスリット方向と直交する方向に引き伸ばすことによって孔を形成したもので、孔の周囲は完全に繋がった状態にあり、端子自体の抵抗が低いため、抵抗の低い端子付集電材である。つまり、従来提案されているようなニッケル線を編んだ網やニッケル線からなる不織布は、ニッケル線同士の交差点において接触の程度が低かったり、接触していないニッケル線もあるなど、抵抗が高いものであったのに対して、本発明の端子付集電材の端子であるエキスパンドメタルの孔の周囲は完全に繋がった状態にあり、端子自体の抵抗が低いため、抵抗の低い端子付集電材である。   The current collector with a terminal of the present invention is obtained by joining a terminal made of expanded metal to the current collector main body as described above, and the expanded metal has a concavo-convex structure with holes, so that the joint strength with the current collector main body by the anchor effect Is strong. Therefore, the terminal does not come off when the electrode group is formed, and the resistance between the current collector main body and the terminal is low. Expanded metal is a hole that is formed by stretching in a direction perpendicular to the slit direction after slitting. The periphery of the hole is completely connected, and the resistance of the terminal itself is low, so the resistance is low. A current collector with terminals. In other words, the conventionally proposed non-woven fabric made of nickel wire or nickel wire has a high resistance, such as a low degree of contact at the intersection of nickel wires or a non-contact nickel wire. In contrast, the periphery of the expanded metal hole, which is a terminal of the current collector with terminal of the present invention, is in a completely connected state, and the resistance of the terminal itself is low. is there.

また、この端子は端子付集電材の使用用途（電気化学素子）に適した金属から構成されていれば良く、特に限定するものではないが、例えば、アルカリ二次電池ではニッケル、リチウムイオン二次電池では負極用として銅、正極及び負極用としてニッケル又はチタン、電気二重層キャパシタではニッケル又はチタンを挙げることができる。   Moreover, this terminal should just be comprised from the metal suitable for the use application (electrochemical element) of the current collector with a terminal, and although it does not specifically limit, For example, in an alkaline secondary battery, nickel, lithium ion secondary In the battery, copper can be used for the negative electrode, nickel or titanium can be used for the positive electrode and the negative electrode, and in the electric double layer capacitor, nickel or titanium can be used.

ここで、エキスパンドメタルからなる端子について、図１をもとに説明する。エキスパンドメタル１は貫通孔２と、貫通孔２を取り囲むストランド３を多数備えており、ストランド３同士の接合部（図１における３ａ、３ｂ、３ｃ、３ｄ）は完全に繋がった状態にある。   Here, a terminal made of expanded metal will be described with reference to FIG. The expanded metal 1 is provided with a through hole 2 and a large number of strands 3 surrounding the through hole 2, and the joint portions (3a, 3b, 3c, 3d in FIG. 1) of the strands 3 are completely connected.

このようなエキスパンドメタル（端子）において、孔の長目方向中心間距離（図１におけるＬＷ）の、孔の短目方向中心間距離（図１におけるＳＷ）に対する比（ＬＷ／ＳＷ）が１．９〜５、かつ孔数密度が３０〜１３０個／ｃｍ２である必要がある。比（ＬＷ／ＳＷ）が１．９未満であると、エキスパンドメタル製造時にストランド３同士の接合部にひびが入りやすく、エキスパンドメタル自体の抵抗が高くなる傾向があり、他方で、比（ＬＷ／ＳＷ）が５を超えると、貫通孔１つあたりの面積が小さくなり、集電材本体とのアンカー効果が作用しにくく、端子と集電材との密着性が低くなり、抵抗が高くなる傾向があるためで、好ましい比（ＬＷ／ＳＷ）は２〜５であり、更に好ましい比（ＬＷ／ＳＷ）は３〜５である。 In such an expanded metal (terminal), the ratio (LW / SW) of the distance between the center in the long direction of the hole (LW in FIG. 1) to the distance between the centers in the short direction of the hole (SW in FIG. 1) is 1. 9 to 5 and the hole number density needs to be 30 to 130 / cm 2 . When the ratio (LW / SW) is less than 1.9, the joint between the strands 3 tends to crack during the production of the expanded metal, and the resistance of the expanded metal itself tends to increase. On the other hand, the ratio (LW / SW) When SW) exceeds 5, the area per through-hole becomes small, the anchor effect with the current collector body hardly acts, the adhesion between the terminal and the current collector becomes low, and the resistance tends to increase. Therefore, a preferable ratio (LW / SW) is 2 to 5, and a more preferable ratio (LW / SW) is 3 to 5.

また、孔数密度が３０個／ｃｍ２未満であると、集電材本体とのアンカー効果が作用しにくく、端子と集電材との密着性が低くなり、抵抗が高くなる傾向があり、他方で、孔数密度が１３０個／ｃｍ２を超えると、貫通孔が多くなり過ぎて、端子自体の抵抗が高くなる傾向があるためで、好ましい孔数密度は４０〜１２０であり、更に好ましい孔数密度は６０〜１００である。 Moreover, when the hole number density is less than 30 / cm 2 , the anchor effect with the current collector main body hardly acts, the adhesion between the terminal and the current collector tends to be low, and the resistance tends to be high. When the hole number density exceeds 130 holes / cm 2 , the number of through-holes tends to increase so that the resistance of the terminal itself tends to increase. The density is 60-100.

なお、エキスパンドメタルの孔の長目方向中心間距離（ＬＷ）及び孔の短目方向中心間距離（ＳＷ）は、前記比（ＬＷ／ＳＷ）が１．９〜５の範囲内にあれば良く、特に限定するものではないが、例えば、集電材本体が長方形（接合辺の長さ：２００ｍｍ程度）を有し、集電材本体の一辺全てに端子を接合（接合幅：３ｍｍ程度）する場合には、長目方向中心間距離（ＬＷ）が３ｍｍ以下で、短目方向中心間距離（ＳＷ）が１．５ｍｍ以下であるのが好ましい。より好ましくは、長目方向中心間距離（ＬＷ）が２．５ｍｍ以下で、短目方向中心間距離（ＳＷ）が１．３ｍｍ以下で、更に好ましくは長目方向中心間距離（ＬＷ）が１．５ｍｍ以下で、短目方向中心間距離（ＳＷ）が０．７ｍｍ以下である。なお、アンカー効果を効果的に発揮できる限り、下限は特に限定するものではないが、長目方向中心間距離（ＬＷ）が０．５ｍｍ以上であるのが好ましく、短目方向中心間距離（ＳＷ）が０．２ｍｍ以上であるのが好ましい。   It should be noted that the distance (LW) between the long direction centers of the expanded metal holes and the distance (SW) between the short direction centers of the holes should be within the range of 1.9 to 5 (LW / SW). Although not particularly limited, for example, when the current collector main body has a rectangular shape (joint side length: about 200 mm) and the terminal is joined to all sides of the current collector main body (joint width: about 3 mm). Is preferably 3 mm or less in the center direction in the long direction (LW) and 1.5 mm or less in the short direction center (SW). More preferably, the center distance (LW) in the long direction is 2.5 mm or less, the center distance (SW) in the short direction is 1.3 mm or less, and more preferably the center distance (LW) in the long direction is 1. .5 mm or less, and the distance (SW) between the short direction directions is 0.7 mm or less. The lower limit is not particularly limited as long as the anchor effect can be effectively exerted, but the long-center distance (LW) is preferably 0.5 mm or more, and the short-center distance (SW) ) Is preferably 0.2 mm or more.

また、エキスパンドメタルの厚さ（図１におけるＴ）は端子付集電材の使用用途（電気化学素子）によって異なり、特に限定するものではない。例えば、円筒型の電池に用いる場合、電極群を形成する際に端子付集電材とセパレータとを円筒状に巻回する必要があり、巻回することのできる柔軟性が必要であるため、エキスパンドメタルの厚さは０．５ｍｍ以下であるのが好ましい。他方で、薄すぎるとエキスパンドメタルの強度が弱くなり、また、電気抵抗が高くなる傾向があるため、０．０１ｍｍ以上であるのが好ましい。これらのバランスを考慮すると、エキスパンドメタルの厚さは０．０５〜０．３ｍｍであるのがより好ましい。   Further, the thickness of the expanded metal (T in FIG. 1) varies depending on the use application (electrochemical element) of the current collector with terminal, and is not particularly limited. For example, when used in a cylindrical battery, it is necessary to wind the current collector with a terminal and the separator in a cylindrical shape when forming the electrode group, and the flexibility that can be wound is necessary. The thickness of the metal is preferably 0.5 mm or less. On the other hand, if it is too thin, the strength of the expanded metal becomes weak and the electrical resistance tends to increase. Considering these balances, the expanded metal thickness is more preferably 0.05 to 0.3 mm.

また、エキスパンドメタルの目開きの形状（つまり貫通孔２の形状）は特に限定するものではないが、例えば、菱形、亀甲形、銀杏形などを挙げることができる。   Moreover, the shape of the opening of the expanded metal (that is, the shape of the through hole 2) is not particularly limited, and examples thereof include a rhombus, a turtle shell shape, and a ginkgo shape.

このようなエキスパンドメタルからなる端子と集電材本体との接合は、抵抗が低いように、エキスパンドメタルの長目方向が電気の移動方向（例えば、アルカリ二次電池の場合には蓋方向、又は電池缶底方向）と一致するように接合するのが好ましい。   In the joining of the terminal made of expanded metal and the current collector main body, the long direction of the expanded metal is the direction of movement of electricity (for example, the lid direction in the case of an alkaline secondary battery, or the battery so that the resistance is low. It is preferable to join so as to coincide with the direction of the bottom of the can.

このような端子の形状は特に限定するものではないが、一般的に長方形である。   The shape of such a terminal is not particularly limited, but is generally rectangular.

また、端子は、例えば、スポット溶接機、シーム溶接機、超音波溶接機、或いはヒートシーラー等によって、集電材本体と接合することができる。なお、集電材本体がめっきした不織布で、不織布が熱分解除去していないものからなる場合には、端子と集電材本体との接合強度が強くなるように、不織布を構成する樹脂が溶け出る条件下で接合するのが好ましい。   The terminal can be joined to the current collector main body by, for example, a spot welder, a seam welder, an ultrasonic welder, or a heat sealer. In addition, in the case where the current collector main body is a non-woven fabric plated and the nonwoven fabric is not thermally decomposed and removed, the condition that the resin constituting the non-woven fabric melts so that the bonding strength between the terminal and the current collector main body is increased. It is preferred to join below.

なお、端子は集電材本体の一部に接合されていれば良いが、図２に端子付集電材の平面図を示すように、集電材本体１１が長方形状を有し、集電材本体１１の一辺全てに端子１２が接合されていると、この端子付集電材１０を用いて電極群を形成した後、端子１２に集電板を接合することによって、ハイレート放電が可能な電気化学素子を製造することができるという特長がある。   The terminal may be joined to a part of the current collector main body. However, as shown in the plan view of the current collector with terminal in FIG. 2, the current collector main body 11 has a rectangular shape. When the terminal 12 is bonded to all sides, an electrode group is formed using the current collector 10 with a terminal, and then a current collector plate is bonded to the terminal 12 to manufacture an electrochemical element capable of high-rate discharge. There is a feature that can be.

また、別の端子付集電材の平面図を図３に示すように、上述のような端子付集電材の端子（以下、「ベース端子」ということがある）に、更に金属片からなる外部端子２３を接合した端子付集電材２０（以下、「第２端子付集電材」といい、上述の端子付集電材を「第１端子付集電材」という）を挙げることができる。この第２端子付集電材は外部端子２３が更に接合されているため、電気化学素子を製造する際に、端子に集電板を接合するという、機械的に複雑な工程を省くことができる、簡易に電気化学素子を製造できるものである。なお、図３における第２端子付集電材においては、外部端子２３が１本しか接合されていないが、ベース端子２２からの集電性を向上させるために、複数本接合されているのがより好ましい。   In addition, as shown in FIG. 3 which is a plan view of another current collector with terminal, an external terminal made of a metal piece is further added to the terminal of the current collector with terminal as described above (hereinafter sometimes referred to as “base terminal”). The terminal-equipped current collector 20 (hereinafter referred to as “second-terminal current collector”, and the above-mentioned current collector with terminal is referred to as “first-terminal current collector”). Since the external terminal 23 is further joined to the current collector with the second terminal, a mechanically complicated process of joining the current collector plate to the terminal can be omitted when manufacturing the electrochemical element. An electrochemical device can be easily produced. In addition, in the current collector with the second terminal in FIG. 3, only one external terminal 23 is joined. However, in order to improve the current collecting performance from the base terminal 22, a plurality of the external terminals 23 are joined. preferable.

この外部端子である金属片も電解液や電気化学素子の反応により劣化が起こらない金属からなれば良く、例えば、アルカリ二次電池ではニッケル、リチウムイオン二次電池では負極用として銅、正極及び負極用としてニッケル又はチタン、電気二重層キャパシタではニッケル又はチタンを挙げることができる。   The metal piece as the external terminal may be made of a metal that does not deteriorate due to the reaction of the electrolytic solution or the electrochemical element. For example, nickel for an alkaline secondary battery, copper for a negative electrode for a lithium ion secondary battery, a positive electrode, and a negative electrode For use, nickel or titanium can be used, and for electric double layer capacitors, nickel or titanium can be used.

この外部端子のベース端子への接合はベース端子と集電材本体との接合と同様に、スポット溶接機、シーム溶接機、超音波溶接機、或いはヒートシーラー等によって実施することができる。なお、外部端子のベース端子への接合はベース端子と集電材本体との接合と一緒に実施することができるし、別に実施することもできる。また、外部端子はベース端子と集電材本体との間に介在させても、ベース端子の外側に配置させても良い。   The joining of the external terminal to the base terminal can be performed by a spot welding machine, a seam welding machine, an ultrasonic welding machine, a heat sealer, or the like, similarly to the joining of the base terminal and the current collector main body. Note that the joining of the external terminal to the base terminal can be performed together with the joining of the base terminal and the current collector main body, or can be performed separately. In addition, the external terminal may be interposed between the base terminal and the current collector main body, or may be disposed outside the base terminal.

本発明の電気化学素子は上述のような本発明の第１又は第２端子付集電材を用いたものであるため、電極群を形成する際に端子が外れることなく製造できるものであり、また、抵抗が低く、ハイレート放電特性にも優れている。本発明の電気化学素子としては、特に限定するものではないが、例えば、アルカリ二次電池、リチウムイオン二次電池、若しくは電気二重層キャパシタなどを挙げることができる。   Since the electrochemical device of the present invention uses the current collector with the first or second terminal of the present invention as described above, it can be manufactured without detaching the terminal when forming the electrode group. Low resistance and excellent high-rate discharge characteristics. Although it does not specifically limit as an electrochemical element of this invention, For example, an alkaline secondary battery, a lithium ion secondary battery, or an electric double layer capacitor can be mentioned.

本発明の電気化学素子は本発明の第１又は第２端子付集電材を用いていること以外は、従来の電気化学素子と全く同様であることができる。例えば、ニッケル水素電池は、正極活物質として水酸化ニッケルを本発明の第１又は第２端子付集電材に充填し、担持させて正極を構成し、負極活物質として水素吸蔵合金を本発明の第１又は第２端子付集電材に充填し、担持させて負極を構成する。また、正極と負極との間にセパレータが介在した電極群がアルカリ電解液と一緒に電池缶に封入された構造を有する。正極はベース端子又は外部端子を通じて電池缶の蓋に接合され、負極は電池缶内部側面に接触或いはベース端子又は外部端子によって電池缶底に接合された状態にある。なお、ハイレート用のアルカリ二次電池の場合には、集電材本体が長方形状を有し、集電材本体の一辺全てにベース端子が接合された第１端子付集電材を用いた電極群が、集電板を介して電池缶の蓋に接合された構造を有するのが好ましい。   The electrochemical device of the present invention can be exactly the same as the conventional electrochemical device except that the current collector with the first or second terminal of the present invention is used. For example, in a nickel metal hydride battery, nickel hydroxide as a positive electrode active material is filled in and supported by the current collector with the first or second terminal of the present invention to form a positive electrode, and a hydrogen storage alloy is used as the negative electrode active material of the present invention. The current collector with the first or second terminal is filled and supported to form the negative electrode. In addition, an electrode group in which a separator is interposed between the positive electrode and the negative electrode is sealed in a battery can together with an alkaline electrolyte. The positive electrode is joined to the lid of the battery can through the base terminal or the external terminal, and the negative electrode is in contact with the inner side of the battery can or joined to the bottom of the battery can by the base terminal or the external terminal. In the case of an alkaline secondary battery for high rate, the current collector body has a rectangular shape, and an electrode group using a current collector with a first terminal in which a base terminal is joined to all sides of the current collector body, It is preferable to have a structure joined to the lid of the battery can via a current collector plate.

別の電気化学素子であるリチウムイオン二次電池は、例えば、正極活物質としてリチウム含有金属酸化物、硫化物または塩化物のようなリチウム含有金属化合物のペーストを、本発明の第１又は第２端子付集電材に充填し、担持させて正極を構成し、負極活物質としてリチウム金属やリチウム合金、及びリチウムを吸蔵、放出可能なカーボンまたはグラファイトを含む炭素材料（例えばコークス、天然黒鉛や人造黒鉛などの炭素材料）、複合スズ酸化物を本発明の第１又は第２端子付集電材に充填し、担持させて負極を構成する。また、正極と負極との間にセパレータが介在した電極群が電解液（例えば、エチレンカーボネートとジエチルカーボネートの混合溶媒にＬｉＰＦ６を溶解させた非水電解液）と一緒に電池缶に封入された構造を有する。正極はベース端子又は外部端子を通じて電池缶の蓋に接合され、負極は電池缶内部側面に接触或いはベース端子又は外部端子によって電池缶底に接合された状態にある。 The lithium ion secondary battery, which is another electrochemical element, includes, for example, a paste containing a lithium-containing metal compound such as a lithium-containing metal oxide, sulfide, or chloride as the positive electrode active material. A current collector with a terminal is filled and supported to constitute a positive electrode, and a lithium metal or lithium alloy as a negative electrode active material, and a carbon material containing carbon or graphite capable of occluding and releasing lithium (for example, coke, natural graphite or artificial graphite) And the like, and the composite tin oxide is filled in the current collector with the first or second terminal of the present invention and supported thereon to constitute the negative electrode. In addition, an electrode group in which a separator is interposed between the positive electrode and the negative electrode is enclosed in a battery can together with an electrolytic solution (for example, a nonaqueous electrolytic solution in which LiPF 6 is dissolved in a mixed solvent of ethylene carbonate and diethyl carbonate). It has a structure. The positive electrode is bonded to the lid of the battery can through the base terminal or the external terminal, and the negative electrode is in contact with the inner side surface of the battery can or bonded to the bottom of the battery can by the base terminal or the external terminal.

なお、リチウムイオン二次電池に使用されている集電材としては、従来、厚さが１０〜２０μｍ程度の箔が使用されているため、本発明の第１又は第２端子付集電材も目付が低く、薄いものが適しているが、目付を低くすると金属量も少なくなり、ベース端子として金属シートを用いた場合には、ベース端子の接合が困難となる傾向があるが、めっきを施しただけで不織布を熱分解除去していない集電材本体を使用すると、めっきした不織布を構成する樹脂が溶け出すことによるアンカー効果により、金属量が少なくなっても強い接合強度が得られるため、目付が低く、薄い第１又は第２端子付集電材を備えたリチウムイオン二次電池も製造できる。   In addition, as the current collector used in the lithium ion secondary battery, since a foil having a thickness of about 10 to 20 μm has been conventionally used, the current collector with the first or second terminal according to the present invention also has a basis weight. Low and thin materials are suitable. However, if the basis weight is lowered, the amount of metal decreases, and when a metal sheet is used as the base terminal, it tends to be difficult to join the base terminal. If the current collector is not thermally decomposed and removed, the anchoring effect caused by the dissolution of the resin that forms the plated nonwoven fabric provides a strong bonding strength even if the amount of metal decreases, resulting in a low basis weight. Also, a lithium ion secondary battery including a thin current collector with the first or second terminal can be manufactured.

更に別の電気化学素子である電気二重層キャパシタは、例えば、少なくとも活性炭を含有する分極性電極材に導電性炭素粒子を添加し、アルコール類、ケトン類、エステル類、アミド類を溶媒としたペーストを、本発明の第１又は第２端子付集電材に充填し、担持させた正極及び負極から構成される。また、正極と負極との間にセパレータが介在した電極群が電解液（テトラフルオロボレート塩、パークロライド塩、ヘキサフルオロフォスフェート塩などの電解質が、カーボネート類、ラクトン類、エーテル類、ジメチルスルホキシドなどの溶媒に溶解させたもの）と一緒に外装缶に封入された構造を有する。正極はベース端子又は外部端子を通じて外装缶の蓋に接合され、負極はベース端子又は外部端子によって缶底に接合された状態にある。   Furthermore, the electric double layer capacitor which is another electrochemical element is, for example, a paste in which conductive carbon particles are added to a polarizable electrode material containing at least activated carbon, and alcohols, ketones, esters and amides are used as solvents. Is composed of a positive electrode and a negative electrode loaded and supported in the current collector with the first or second terminal of the present invention. In addition, an electrode group in which a separator is interposed between the positive electrode and the negative electrode is an electrolyte (electrolyte such as tetrafluoroborate salt, perchloride salt, hexafluorophosphate salt, carbonates, lactones, ethers, dimethyl sulfoxide, etc. And a structure enclosed in an outer can together. The positive electrode is joined to the lid of the outer can through the base terminal or the external terminal, and the negative electrode is joined to the bottom of the can by the base terminal or the external terminal.

以下に、本発明の実施例を記載するが、本発明は以下の実施例に限定されるものではない。   Examples of the present invention will be described below, but the present invention is not limited to the following examples.

（実施例１〜６、比較例１〜４）
ポリプロピレンを芯成分とし、高密度ポリエチレンを鞘成分とする芯鞘型複合繊維Ａ（繊度：６．６ｄｔｅｘ、繊維長：５ｍｍ）を７０ｍａｓｓ％と、ポリプロピレンを芯成分とし、高密度ポリエチレンを鞘成分とする芯鞘型複合繊維Ｂ（繊度：０．８ｄｔｅｘ、繊維長：５ｍｍ）を３０ｍａｓｓ％とを混合したスラリーを用い、湿式抄造法により繊維ウエブを形成した後、繊維ウエブを温度１３５℃に設定した熱風ドライヤーへ供給し、芯鞘型複合繊維Ａ及びＢの鞘成分を融着させて、目付が７０ｇ／ｍ２の不織布を製造した。その後、この不織布を発煙硫酸へ浸漬することによってスルホン化処理を実施し、スルホン化不織布を製造した。そして、このスルホン化不織布を無電解メッキ法によりニッケルめっきを施し、集電材本体（めっき量：１０５ｇ／ｍ２、熱分解除去していない、４０ｍｍ×１００ｍｍの長方形）を製造した。 (Examples 1-6, Comparative Examples 1-4)
Core-sheath type composite fiber A (fineness: 6.6 dtex, fiber length: 5 mm) having polypropylene as the core component and high-density polyethylene as the sheath component is 70 mass%, polypropylene as the core component, and high-density polyethylene as the sheath component A fiber web was formed by wet papermaking using a slurry in which core-sheath type composite fiber B (fineness: 0.8 dtex, fiber length: 5 mm) was mixed with 30 mass%, and then the fiber web was set at a temperature of 135 ° C. It supplied to the hot air dryer, the sheath component of the core sheath type composite fiber A and B was fused, and the nonwoven fabric of 70 g / m < 2 > of fabric weights was manufactured. Thereafter, the non-woven fabric was immersed in fuming sulfuric acid to carry out a sulfonation treatment, and a sulfonated non-woven fabric was produced. And this sulfonated nonwoven fabric was nickel-plated by the electroless plating method, and the current collector main body (plating amount: 105 g / m 2 , 40 mm × 100 mm rectangle not thermally removed) was manufactured.

他方、ベース端子として、表１に示す各種エキスパンドメタル（４ｍｍ×４０ｍｍの長方形）を用意した。また、外部端子として、ニッケルリボン（４ｍｍ×５０ｍｍの長方形）を用意した。   On the other hand, various expanded metals (4 mm × 40 mm rectangle) shown in Table 1 were prepared as base terminals. Further, a nickel ribbon (4 mm × 50 mm rectangle) was prepared as an external terminal.

次いで、前記集電材本体の短辺の中間点に４ｍｍだけ重なるように前記ニッケルリボンを配置し、更にその上に、集電材本体の短辺全てを覆うように、エキスパンドメタルベース端子を重ねた後、シーム溶接機によりそれぞれ溶接し、第２端子付集電材を製造した。なお、エキスパンドメタルベース端子は長目方向が集電材本体の長辺と平行となるように、集電材本体の端部から４ｍｍの幅で溶接した。また、この溶接により不織布構成樹脂が溶け出した状態にあった。   Next, after placing the nickel ribbon so as to overlap the middle point of the short side of the current collector main body by 4 mm, and further overlapping the expanded metal base terminal so as to cover all the short sides of the current collector main body Each of them was welded by a seam welder to produce a current collector with a second terminal. The expanded metal base terminal was welded with a width of 4 mm from the end of the current collector main body so that the long direction was parallel to the long side of the current collector main body. Moreover, it was in the state by which the nonwoven fabric constituent resin melt | dissolved by this welding.

（比較例５）
ベース端子としてニッケルシートを用いたこと以外は、実施例１と全く同様にして正極を作製しようとしたが、集電材本体とニッケルシートとを溶接することができず、第２端子付集電材を製造することができなかった。これはニッケルシートが平滑でアンカー効果が生じないためであった。 (Comparative Example 5)
Except for using a nickel sheet as the base terminal, an attempt was made to produce a positive electrode in exactly the same way as in Example 1, but the current collector main body and the nickel sheet could not be welded, and the current collector with the second terminal was Could not be manufactured. This was because the nickel sheet was smooth and the anchor effect did not occur.

（比較例６）
ベース端子として１００メッシュのニッケル網を用いたこと以外は、実施例１と全く同様にして、第２端子付集電材を製造した。 (Comparative Example 6)
A current collector with a second terminal was produced in the same manner as in Example 1 except that a 100 mesh nickel net was used as the base terminal.

（抵抗低下率の測定）
各第２端子付集電材の抵抗低下率を次の手順により測定した。
（１）集電材本体の対向する短辺間の抵抗（Ｒｂ）をＬＣＲメーターにより１ｋＨｚの条件下で測定した。
（２）第２端子付集電材のニッケルリボンとニッケルリボン溶接辺に対向する短辺との間の抵抗（Ｒａ）をＬＣＲメーターにより１ｋＨｚの条件下で測定した。
（３）次の式から抵抗低下率（Ｒｄ）を算出した。
Ｒｄ＝｛（Ｒｂ−Ｒａ）／Ｒｂ｝×１００ (Measurement of resistance reduction rate)
The resistance reduction rate of each current collector with a second terminal was measured by the following procedure.
(1) The resistance (Rb) between the opposing short sides of the current collector main body was measured with an LCR meter under a condition of 1 kHz.
(2) The resistance (Ra) between the nickel ribbon of the current collector with the second terminal and the short side facing the welded side of the nickel ribbon was measured with an LCR meter under the condition of 1 kHz.
(3) The resistance reduction rate (Rd) was calculated from the following equation.
Rd = {(Rb−Ra) / Rb} × 100

この結果は表２に示す通りであった。なお、この抵抗低下率の値が大きい方が、抵抗が大きく下がることを意味するため、この値が大きい方が抵抗が低く、好ましい。   The results are shown in Table 2. In addition, since the one where this resistance decreasing rate value is large means that resistance falls greatly, the one where this value is large has low resistance, and is preferable.

（溶接強度の測定）
各第２端子付集電材のニッケルリボンとニッケルリボン溶接辺に対向する短辺とを、引張強さ試験機（オリエンテック製、テンシロンＵＴＭ−III−１００）のチャック間に固定（チャック間距離：１００ｍｍ）し、速度１００ｍｍ／ｍｉｎ．で引張り、ベース端子剥離時の強さを測定した。この測定を各第２端子付集電材ともに５回づつ行い、その算術平均値を溶接強度とした。この結果は表２に示す通りであった。 (Measurement of welding strength)
Fix the nickel ribbon of the current collector with each second terminal and the short side facing the welded side of the nickel ribbon between chucks of a tensile strength tester (Orientec, Tensilon UTM-III-100) (distance between chucks: 100 mm) and a speed of 100 mm / min. The strength at the time of peeling the base terminal was measured. This measurement was performed five times for each current collector with the second terminal, and the arithmetic average value was taken as the welding strength. The results are shown in Table 2.

Figure 2006286365
Figure 2006286365

Figure 2006286365
Figure 2006286365

表２から明らかなように、本発明の第２端子付集電材は溶接強度が４１Ｎ以上と、集電材本体とベース端子とが強固に接合されたものであり、しかも本発明の第２端子付集電材は抵抗低下率が１０．１％以上の抵抗の低いものであったため、利用率が高く、高率充放電特性に優れた電気化学素子を製造できるものであった。   As is apparent from Table 2, the current collector with the second terminal of the present invention has a welding strength of 41 N or more, the current collector main body and the base terminal are firmly joined, and the second terminal of the present invention. Since the current collector had a low resistance reduction rate of 10.1% or more, an electrochemical device having a high utilization rate and an excellent high rate charge / discharge characteristic could be produced.

エキスパンドメタルの斜視図Expanded metal perspective view 第１端子付集電材の平面図Top view of current collector with first terminal 第２端子付集電材の平面図Plan view of current collector with second terminal

符号の説明Explanation of symbols

１ エキスパンドメタル
２ 貫通孔
３ ストランド
３ａ、３ｂ、３ｃ、３ｄ ストランド同士の接合部
１０ （第１）端子付集電材
１１ 集電材本体
１２ （ベース）端子
２０ （第２）端子付集電材
２１ 集電材本体
２２ ベース端子
２３ 外部端子
DESCRIPTION OF SYMBOLS 1 Expanded metal 2 Through-hole 3 Strand 3a, 3b, 3c, 3d Joining part 10 of a strand 10 (1st) Current collection material with a terminal 11 Current collection material main body 12 (Base) terminal 20 (2nd) Current collection material with a terminal 21 Current collection material Body 22 Base terminal 23 External terminal

Claims (6)

活物質が充填されて電極となる集電材本体に、エキスパンドメタルからなる端子が接合された端子付集電材であり、前記端子は孔の長目方向中心間距離（ＬＷ）の、孔の短目方向中心間距離（ＳＷ）に対する比（ＬＷ／ＳＷ）が１．９〜５、かつ孔数密度が３０〜１３０個／ｃｍ２のエキスパンドメタルからなることを特徴とする端子付集電材。 It is a current collector with a terminal in which a terminal made of expanded metal is joined to a current collector main body that is filled with an active material and becomes an electrode, and the terminal is a short hole with a center distance (LW) in the long direction of the hole. A current collector with a terminal, characterized by being made of an expanded metal having a ratio (LW / SW) to a distance between centers (SW) of 1.9 to 5 and a hole density of 30 to 130 / cm 2 . 集電材本体が、不織布にめっきを施しただけで、不織布を熱分解除去していないものからなることを特徴とする、請求項１記載の端子付集電材。 The current collector with a terminal according to claim 1, wherein the current collector main body is formed by plating the nonwoven fabric but not thermally removing the nonwoven fabric. 集電材本体が長方形状を有し、集電材本体の一辺全てに端子が接合されていることを特徴とする、請求項１又は請求項２に記載の端子付集電材。 The current collector with a terminal according to claim 1 or 2, wherein the current collector main body has a rectangular shape, and a terminal is joined to all sides of the current collector main body. 更に金属片からなる外部端子が端子に接合されていることを特徴とする、請求項３記載の端子付集電材。 4. The current collector with a terminal according to claim 3, wherein an external terminal made of a metal piece is joined to the terminal. 請求項１〜請求項４のいずれかに記載の端子付集電材を用いた電気化学素子。 The electrochemical element using the current collector with a terminal in any one of Claims 1-4. アルカリ二次電池、リチウムイオン二次電池、電気二重層キャパシタの中から選ばれる電気化学素子であることを特徴とする、請求項５記載の電気化学素子。
6. The electrochemical device according to claim 5, wherein the electrochemical device is selected from an alkaline secondary battery, a lithium ion secondary battery, and an electric double layer capacitor.
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