JP2008192476A - Manufacturing method of electrode substrate for battery, electrode for battery using it, and battery - Google Patents
Manufacturing method of electrode substrate for battery, electrode for battery using it, and battery Download PDFInfo
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Abstract
Description
本発明は電池用の電極として用いられる不織布を基材とする電池用電極基板並びにこれを用いた電極及び電池に関する。 The present invention relates to a battery electrode substrate based on a nonwoven fabric used as a battery electrode, and an electrode and a battery using the same.
従来、ニッケル水素電池やニッカド電池などのアルカリ二次電池の電極としては、ポリオレフィン系、ポリ塩化ビニル系、ポリアクリロニトリル系、ポリアミド系等の繊維からなる不織布にニッケルめっきを施したものが検討されている。 Conventionally, as an electrode of an alkaline secondary battery such as a nickel metal hydride battery or a nickel cadmium battery, a non-woven fabric made of polyolefin, polyvinyl chloride, polyacrylonitrile, polyamide or the like is subjected to nickel plating. Yes.
特許文献１には、繊維長が１〜５０ｍｍのポリオレフィン系樹脂繊維からなるウェブに水流交絡処理を施した後にニッケルめっきを施すことによって引っ張り強度が強いニッケルめっき不織布を製造する方法が開示されている。
特許文献２には、従来の、ニッケルめっきを施す以前の不織布にコロナ処理を施す不織布電極の製造方法では、繊維とめっき膜との接着性が不十分であることに鑑み、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処理されたポリオレフィン系繊維からなる不織布を親水化処理し、これにニッケルめっきを施すことにより、ニッケルめっきの密着性を向上したニッケルめっき不織布を製造する方法が開示されている。
Patent Document 1 discloses a method of manufacturing a nickel-plated nonwoven fabric having a high tensile strength by applying a hydroentanglement treatment to a web made of polyolefin resin fibers having a fiber length of 1 to 50 mm, followed by nickel plating. .
In Patent Document 2, a conventional non-woven fabric electrode manufacturing method in which corona treatment is applied to a non-woven fabric prior to nickel plating is insufficient in view of the insufficient adhesion between the fiber and the plating film. A method for producing a nickel-plated nonwoven fabric with improved nickel plating adhesion by hydrophilizing a nonwoven fabric made of polyolefin fiber that has been hydrophilized by gas treatment or vinyl monomer grafting, and applying nickel plating to the nonwoven fabric. Is disclosed.
特許文献３には、親水化処理を施したポリオレフィン系繊維からなる不織布１１の表面に不織布繊維表面のめっき断面積が２０μｍ2〜１３０μｍ2の範囲となるようにニッケルめっき膜を形成することにより、この不織布を用いた電池はめっき膜の表面抵抗が低く、ハイレート充放電が可能な電池を製造できることが可能であることが開示されている。
特許文献４には、ポリオレフィン系繊維からなる不織布にニッケルめっきを施して得た単位体積当たりの比表面積が、０．１３ｍ２／ｃｍ３〜０．３５ｍ２／ｃｍ３である集電材に、粘度が０．３Ｐａ・ｓ以下の活物質ペーストを充填し乾燥して得た電極を用いることによりアルカリ電池を高出力化することが開示されている。
Patent Document 3, by forming a nickel plating layer as plated cross-sectional area of the surface to the nonwoven fiber surface of the nonwoven fabric 11 made of polyolefin fibers subjected to hydrophilic treatment in the range of 20μm 2 ~130μm 2, It is disclosed that a battery using this non-woven fabric has a low surface resistance of the plating film and can produce a battery capable of high rate charge / discharge.
Patent Document 4, the specific surface area per unit volume obtained by applying a nickel plating to a nonwoven fabric made of polyolefin-based fibers, the is current collector at 0.13m 2 / cm 3 ~0.35m 2 / cm 3, viscosity Is disclosed to increase the output of an alkaline battery by using an electrode obtained by filling and drying an active material paste of 0.3 Pa · s or less.
上記特許文献記載のものは、いずれもポリオレフィン系繊維からなる不織布にニッケルめっきを施したものを電極用基板として用いている。
しかしながら、これらの電極基板は、基材の表面に繊維端部が飛び出しており、電池作製時に短絡の危険性が大きい。湿式で不織布を作製する場合繊維長が短く、繊維の端部の数自体が多いことに加え、電池用の基板とするために、電池の容量を大きくするために不織布の厚さを厚くしなければならず、繊維が厚さ方向に立った状態になりやすい。また、乾式で作製する場合は繊維長が比較的長いが、電池の容量を大きくするために不織布の厚さを厚くしなければならず、そのためには太い繊維を使う必要があり、やはり繊維が厚さ方向に立った状態になりやすい。この結果、不織布表面には繊維の端部が飛び出すことになり、このような基材を用いて作製した電極をセパレーター及び対極とともに捲回した場合に、繊維端部がセパレーターを突き破って対極と接触し、電池短絡が起きる。
In all of the above-mentioned patent documents, a non-woven fabric made of polyolefin fibers is subjected to nickel plating and used as an electrode substrate.
However, in these electrode substrates, fiber ends protrude from the surface of the base material, and there is a high risk of short circuit during battery production. In the case of producing a nonwoven fabric by a wet method, the fiber length is short and the number of fiber ends itself is large. In addition, the thickness of the nonwoven fabric must be increased in order to increase the capacity of the battery in order to provide a battery substrate. The fibers tend to stand in the thickness direction. In addition, the fiber length is relatively long when made dry, but in order to increase the capacity of the battery, it is necessary to increase the thickness of the non-woven fabric. It tends to stand in the thickness direction. As a result, the end of the fiber protrudes from the surface of the nonwoven fabric, and when the electrode produced using such a substrate is wound together with the separator and the counter electrode, the fiber end breaks through the separator and comes into contact with the counter electrode. Battery short circuit occurs.
本発明は、電極基板の基材表面に繊維の端部が存在する割合を低くすることにより、電極をセパレーター及び対極とともに捲回した際に繊維端部がセパレーターを突き破って短絡を起こすことのない電池用電極基板並びにこれを用いた電極及び電池を提供することを目的とする。 In the present invention, by reducing the ratio of the end of the fiber on the substrate surface of the electrode substrate, the fiber end does not break through the separator and cause a short circuit when the electrode is wound together with the separator and the counter electrode. It aims at providing the electrode substrate for batteries, the electrode using the same, and a battery.
本発明者等は、樹脂からなる不織布の繊維表面にニッケルを含有する金属を被覆した電池用電極において、樹脂からなる不織布の繊維目付量、厚さ、繊維の繊度及び長さが所定の関係を満たすときに、前記の課題が解決できることを見出して本発明を完成した。すなわち、本発明は以下に記載するとおりのものである。 In the battery electrode in which the metal surface containing nickel is coated on the fiber surface of the nonwoven fabric made of resin, the present inventors have a predetermined relationship between the fiber basis weight, thickness, fiber fineness and length of the nonwoven fabric made of resin. The present invention has been completed by finding that the above-mentioned problems can be solved when satisfied. That is, the present invention is as described below.
（１）樹脂からなる不織布の繊維表面にニッケルを含有する金属を被覆した電池用電極であって、樹脂からなる不織布の繊維目付量をｗ（ｇ／ｍ２）、厚さをｔ（ｍｍ）、繊維の繊度をｘ（ｄＴｅｘ）、長さをｌ（ｃｍ）としたとき、０．０１≦ｗ／（ｔ＊ｘ＊ｌ）≦６．０であることを特徴とする電池用電極基板。
（２）樹脂からなる不織布の繊維が、ポリプロピレンとポリエチレンから成る繊維であることを特徴とする上記（１記載の電池用電極基板。
（３）樹脂からなる不織布の厚さが０．９ｍｍ以上５．０ｍｍ以下であることを特徴とする上記（１）又は（２）の記載の電池用電極基板。
（４）被覆されたニッケルを含有する金属量が１５０〜２５０ｇ／ｍ２であることを特徴とする上記（１〜３のいずれかに記載の電池用電極基板。
（５）上記（１）〜（４）のいずれかに記載の電池用電極基板に、水酸化ニッケルを主体とする活物質合剤を担持してなることを特徴とする電池用電極
（６）上記（５）に記載の電池用電極基板を使用した電池。
(1) A battery electrode in which the surface of a non-woven fabric made of resin is coated with a metal containing nickel, and the basis weight of the non-woven fabric made of resin is w (g / m 2 ) and the thickness is t (mm). An electrode substrate for a battery, wherein 0.01 ≦ w / (t * x * l) ≦ 6.0 when the fineness of the fiber is x (dTex) and the length is 1 (cm).
(2) The battery electrode substrate as described in (1) above, wherein the nonwoven fabric fibers made of resin are fibers made of polypropylene and polyethylene.
(3) The battery electrode substrate as described in (1) or (2) above, wherein the nonwoven fabric made of resin has a thickness of 0.9 mm to 5.0 mm.
(4) The battery electrode substrate as described in any one of (1) to (3) above, wherein the amount of metal containing nickel coated is 150 to 250 g / m 2 .
(5) A battery electrode (6), wherein the battery electrode substrate according to any one of (1) to (4) above carries an active material mixture mainly composed of nickel hydroxide. A battery using the battery electrode substrate according to the above (5).
本発明の電池用電極基板は、長い繊維を使うことで端部の数自体を減らすことに加え、不織布の厚さに対して繊維が十分長いため繊維が厚さ方向に立った状態になりにくくなり、不織布表面に繊維端部の飛び出しが少なくできるので、捲回時にセパレーターに突き刺さるような繊維端部の飛び出しが少なくなり、電池を作製するときの短絡危険性が減少するという効果を奏する。 In addition to reducing the number of end portions itself by using long fibers, the battery electrode substrate of the present invention has a sufficiently long fiber with respect to the thickness of the nonwoven fabric, so that the fibers are less likely to stand in the thickness direction. Thus, since the fiber end portion can be prevented from jumping out on the surface of the nonwoven fabric, the fiber end portion that sticks into the separator at the time of winding is reduced, and the short-circuit risk when producing the battery is reduced.
本発明における不織布を構成する繊維は、耐アルカリ性の繊維であれば特に限定されないが、ポリオレフィン系繊維が好ましい例として挙げられる。この繊維は、すでに電池のセパレーターとして使用されている実績があり、２０〜３５重量％ＫＯＨ水溶液と接触しても繊維が溶解しないため物性の変化がなく、耐アルカリ性に優れるとともに安価であり汎用性が高いものである。 Although the fiber which comprises the nonwoven fabric in this invention will not be specifically limited if it is an alkali-resistant fiber, A polyolefin-type fiber is mentioned as a preferable example. This fiber has already been used as a battery separator, and even when it comes into contact with 20 to 35 wt% KOH aqueous solution, the fiber does not dissolve, so there is no change in physical properties, it is excellent in alkali resistance, and is inexpensive and versatile. Is expensive.
ポリオレフィン系繊維を構成する樹脂としては、ポリエチレン、ポリプロピレン、ポリメチルペンテン、エチレン−プロピレンコポリマー、エチレン−ブテン−プロピレンコポリマー、エチレン−ビニルアルコールコポリマー等が挙げられる。ポリオレフィン系繊維としては、これらの樹脂の一種からなるもの又は２種以上からなる複合繊維を挙げることができる。 Examples of the resin constituting the polyolefin fiber include polyethylene, polypropylene, polymethylpentene, ethylene-propylene copolymer, ethylene-butene-propylene copolymer, and ethylene-vinyl alcohol copolymer. Examples of polyolefin fibers include those composed of one of these resins or composite fibers composed of two or more.
不織布がポリオレフィン系繊維からなる場合、前記の例示の中でも、耐アルカリ性及び耐酸性に優れるポリエチレン又はポリプロピレンからなる繊維、又はポリエチレン及びポリプロピレンを組合せた複合繊維が好ましい
特に、ポリプロピレンからなる芯の周囲をポリエチレンからなる鞘で覆った芯鞘型複合繊維は、耐アルカリ性と強度特性を同時に満たすことができるので好適である。
When the nonwoven fabric is made of polyolefin fibers, among the above examples, fibers made of polyethylene or polypropylene excellent in alkali resistance and acid resistance, or composite fibers in which polyethylene and polypropylene are combined are particularly preferred. A core-sheath type composite fiber covered with a sheath made of is preferable because it can satisfy both alkali resistance and strength characteristics at the same time.
不織布は、例えば、不織布を構成する繊維のウエブを形成した後、繊維同士を結合することにより製造することができる。繊維のウエブは、カード法やエアレイ法、又は紡糸状態から連続的にシート化するメルトブロー法やスパンボンド法のような乾式法、或いは繊維を水に分散し、それを抄きとる湿式法等により製造することができる。
不織布については、繊維目付量は２０ｇ／ｍ２〜６５ｇ／ｍ２、繊度は１〜１５ｄＴｅｘ、厚さは０．５ｍｍ〜５ｍｍとすることが好ましい。
また、繊維長については、繊維の太さと長さのバランスを取る必要があり、上記繊度の範囲では数ｍｍ〜１００ｍｍ程度とすることが好ましい。
A nonwoven fabric can be manufactured, for example, by forming a web of fibers constituting the nonwoven fabric and then bonding the fibers together. The fiber web can be obtained by a card method, an air lay method, a dry method such as a melt blow method or a spun bond method in which a sheet is continuously formed from a spun state, or a wet method in which fibers are dispersed in water and drawn. Can be manufactured.
As for the nonwoven fabric, it is preferable that the fiber basis weight is 20 g / m 2 to 65 g / m 2 , the fineness is 1 to 15 dTex, and the thickness is 0.5 mm to 5 mm.
Further, the fiber length needs to balance the thickness and length of the fiber, and is preferably about several mm to 100 mm within the above fineness range.
繊維同士の結合方法としては、非常に細かい高圧の水ジェットを衝撃的に与える水流交絡処理、ニードルパンチによる交絡処理、繊維をその軟化点以上、熱分解温度未満に加熱して、繊維を互いの接触点で局部的に融着させる熱処理等の方法を例示できる。前記交絡処理及び熱処理の一方のみでもよいが、交絡処理を行った後に熱処理を行うと、得られる不織布の強度特性が向上するので好適である。又、前記交絡処理及び熱処理により、空隙率を適正な値に調整することもできる。なお、繊維としてポリプロピレンの周囲がポリエチレンで覆われている前記の芯鞘型複合繊維を用いた場合、熱処理の温度は１１０〜１４０℃であることが好ましい。 The fiber-to-fiber bonding method includes hydroentanglement treatment that impacts a very fine high-pressure water jet, entanglement treatment with a needle punch, heating the fiber to above its softening point and below the thermal decomposition temperature, Examples thereof include a heat treatment method for locally fusing at the contact point. Although only one of the entanglement treatment and the heat treatment may be performed, it is preferable to perform the heat treatment after the entanglement treatment because the strength characteristics of the resulting nonwoven fabric are improved. Further, the porosity can be adjusted to an appropriate value by the entanglement treatment and the heat treatment. In addition, when the said core-sheath-type composite fiber with which the circumference | surroundings of polypropylene are covered with polyethylene as a fiber is used, it is preferable that the temperature of heat processing is 110-140 degreeC.
不織布とニッケルを含有する金属の被覆層との密着度を向上するために、繊維表面の親水化処理を行ってもよい。親水化処理としては、フッ素処理、コロナ放電処理、スルホン化処理、ビニルモノマーのグラフト重合、親水性樹脂による処理、又は界面活性剤処理等を挙げることができる。 In order to improve the adhesion between the nonwoven fabric and the nickel coating layer, the fiber surface may be hydrophilized. Examples of the hydrophilization treatment include fluorine treatment, corona discharge treatment, sulfonation treatment, vinyl monomer graft polymerization, treatment with a hydrophilic resin, or surfactant treatment.
本発明の電池用電極基板は、前記不織布を構成する繊維表面にニッケルを含有する金属を被覆することにより、得ることができる。被覆の方法としては、無電解メッキやスパッタリング法により不織布の繊維の表面にニッケルを含有する金属の層を形成し表面を導電化した後電解メッキを行う方法等が挙げられる。 The battery electrode substrate of the present invention can be obtained by coating the surface of the fibers constituting the nonwoven fabric with a metal containing nickel. Examples of the coating method include a method in which a metal layer containing nickel is formed on the surface of the nonwoven fabric fiber by electroless plating or sputtering, and the surface is made conductive, followed by electrolytic plating.
スパッタリングや無電解メッキは、一般的なスパッタリングや無電解メッキと同様な条件により行うことができる。例えば、無電解メッキは、不織布を触媒付与槽に浸漬して触媒付与を行い、次いでメッキ槽へ浸漬してメッキする（無電解メッキ工程）方法により行うことができる。触媒付与は、例えば、塩化第一錫の塩酸水溶液で不織布を処理した後に塩化パラジウムの塩酸水溶液で触媒化する方法により行うことができる。無電解メッキ工程は、例えば、硝酸ニッケル、塩化ニッケル、硫酸ニッケル等のニッケル塩を含有する水溶液に不織布を浸し、ニッケルをヒドラジン誘導体等の還元剤にて還元する方法により行うことができる。 Sputtering and electroless plating can be performed under the same conditions as general sputtering and electroless plating. For example, the electroless plating can be performed by a method in which a non-woven fabric is immersed in a catalyst applying tank to apply a catalyst, and then immersed in a plating tank and plated (electroless plating step). The catalyst application can be performed, for example, by treating the nonwoven fabric with a stannous chloride aqueous hydrochloric acid solution and then catalyzing with a palladium chloride aqueous hydrochloric acid solution. The electroless plating step can be performed, for example, by a method in which a non-woven fabric is immersed in an aqueous solution containing a nickel salt such as nickel nitrate, nickel chloride, or nickel sulfate, and nickel is reduced with a reducing agent such as a hydrazine derivative.
電解メッキは、例えば、ワット浴、塩化浴、スルファミン酸浴等のメッキ浴を用いて行われる。前記の無電解メッキやスパッタリングにより繊維の表面が導電化された不織布をメッキ浴に浸し、不織布を陰極に、ニッケル対極板を陽極に接続して直流或いはパルス断続電流を通電させることにより、無電解メッキやスパッタリングにより形成されたニッケル層上に、さらにニッケルの被覆を形成することができる。 Electrolytic plating is performed using, for example, a plating bath such as a watt bath, a chloride bath, or a sulfamic acid bath. By immersing a non-woven fabric in which the surface of the fiber is made conductive by electroless plating or sputtering in a plating bath, and connecting the non-woven fabric to the cathode and the nickel counter electrode to the anode and applying a direct current or pulse intermittent current, A nickel coating can be further formed on the nickel layer formed by plating or sputtering.
ニッケルを含有する金属の目付量としては、電気伝導性及び電池寿命を確保する観点から、１５０ｇ／ｍ２〜２５０ｇ／ｍ２の範囲が好ましい。ここで、ニッケルを含有する金属の目付量とは、無電解メッキやスパッタリング、電解メッキ等により被覆されるニッケルを含有する金属の重量（ｇ）を電池用電極基板の面積で除したものであり、電池用電極基板の単位面積当たりのニッケルを含有する金属被覆量を意味する。 The basis weight of the metal containing nickel, in order to ensure the electrical conductivity and the battery life is preferably in the range of 150g / m 2 ~250g / m 2 . Here, the basis weight of the metal containing nickel is the weight (g) of the metal containing nickel coated by electroless plating, sputtering, electrolytic plating, etc. divided by the area of the battery electrode substrate. Means the amount of metal coating containing nickel per unit area of the battery electrode substrate.
ニッケルを含有する金属の目付量が１５０ｇ未満であると、この電池用電極基板の電気伝導度が低下してこれを用いて製造された電極の集電特性が低下する傾向がある。集電特性が低下すると利用率が低下しやすくなり、特に電池の放電時の電流率が高い場合（ハイレート放電）この問題が顕著である。又、ニッケルを含有する金属量の目付量を１５０ｇ／ｍ２以上とすることにより、繊維量に対するニッケルを含有する金属量が多くなるので、得られた電池用電極基板は溶接性に優れこの点でも好ましい。
電池用電極基板の電気伝導度はニッケルを含有する金属量の目付量が増大する程向上する傾向があるが、２５０ｇ／ｍ２を越えてニッケルを含有する金属量の目付量を増大しても電気伝導度はそれほど向上しないので、コストメリットの点からも２５０ｇ／ｍ２以下が好ましい。
When the basis weight of the metal containing nickel is less than 150 g, the electric conductivity of the battery electrode substrate is lowered, and the current collecting characteristics of an electrode manufactured using the battery substrate tend to be lowered. When the current collection characteristic is lowered, the utilization rate is liable to be lowered, and this problem is particularly remarkable when the current rate during battery discharge is high (high rate discharge). In addition, by setting the basis weight of the amount of metal containing nickel to 150 g / m 2 or more, the amount of metal containing nickel with respect to the amount of fiber increases, so the obtained battery electrode substrate has excellent weldability. However, it is preferable.
The electric conductivity of the battery electrode substrate tends to improve as the amount of metal containing nickel increases, but even if the amount of metal containing nickel exceeds 250 g / m 2 , Since electric conductivity does not improve so much, 250 g / m 2 or less is preferable from the viewpoint of cost merit.
活物質としては、水酸化ニッケルを主体とする活物質合剤を挙げることができ、活物質ペーストは、活物質以外に導電助剤としてコバルト又はニッケル粉末を含むことができる。
また、電池の容量は電極基板の空隙中に充填される活物質の量によって決定され、活物質の充填量は電極板の空隙率、厚みによって決定されるため、ニッケル板の空隙率、厚みはできるだけ大きくすることが望まれる。本発明の電極基板は空隙率が９０〜９８％であり、また、厚みが０．９ｍｍ以上であることが好ましい。空隙率が９０〜９８％であると、活物質を高密度に充填することができ、また、厚みが大きいと水酸化ニッケルの充填量が増加するので、アルカリ２次電池の更なる高容量化が期待できる。
Examples of the active material include an active material mixture mainly composed of nickel hydroxide, and the active material paste can include cobalt or nickel powder as a conductive additive in addition to the active material.
In addition, since the capacity of the battery is determined by the amount of the active material filled in the gap of the electrode substrate, and the filling amount of the active material is determined by the porosity and thickness of the electrode plate, the porosity and thickness of the nickel plate are It is desirable to make it as large as possible. The electrode substrate of the present invention preferably has a porosity of 90 to 98% and a thickness of 0.9 mm or more. When the porosity is 90 to 98%, the active material can be filled with high density, and when the thickness is large, the filling amount of nickel hydroxide increases, so that the capacity of the alkaline secondary battery is further increased. Can be expected.
本発明においては、不織布の繊維目付量をｗ（ｇ／ｍ２）、厚さをｔ（ｍｍ）、繊維の繊度をｘ（ｄＴｅｘ）、長さをｌ（ｃｍ）としたとき、これらの数値が次の式（１）に示す関係を満たすことが必要である。
０．０１≦ｗ／（ｔ＊ｘ＊ｌ）≦６．０ ・・・・・（１）
上記関係を満たさない場合は、不織布の繊維端部の飛び出しが多くなり、作製した電極の捲回時にセパレーターに突き刺さって短絡危険性が増加する。
また、より好ましい条件は０．１≦ｗ／（ｔ＊ｘ＊ｌ）≦３．０である。
In the present invention, when the basis weight of the nonwoven fabric is w (g / m 2 ), the thickness is t (mm), the fineness of the fiber is x (dTex), and the length is 1 (cm), these numerical values are used. Must satisfy the relationship shown in the following equation (1).
0.01 ≦ w / (t * x * l) ≦ 6.0 (1)
When the above relationship is not satisfied, the fiber ends of the nonwoven fabric jump out, and the separator is pierced when the produced electrode is wound, increasing the risk of short circuit.
A more preferable condition is 0.1 ≦ w / (t * x * l) ≦ 3.0.
［実施例１〜３］
ＰＰ／ＰＥ芯鞘構造の繊維からなる、繊維目付量、厚さ、繊度、繊維長さがそれぞれ表１に示したような数値を示す不織布を電極用基材として用い、これに無電解メッキ法によりニッケルを含有する金属膜を形成して導電化処理をした後、電解メッキを行って、ニッケルを含有する金属総目付量が２００ｇ／ｍ２の実施例１〜３の電池用電極基板を作製した。
得られた電池用電極基板について、端部数の評価を行った。その結果を表１に示す。
端部数は、作製した基材の表裏についてＳＥＭ（４０倍）で１ｍｍ×１ｍｍの視野を１０箇所観察し、見つかった繊維端部数の平均値である。
[Examples 1 to 3]
A non-woven fabric made of PP / PE core-sheath fibers, each having a fiber weight per unit area, thickness, fineness, and fiber length as shown in Table 1, is used as an electrode base material. After forming a metal film containing nickel and conducting a conductive treatment, electrolytic plating is performed to produce battery electrode substrates of Examples 1 to 3 having a total metal basis weight containing nickel of 200 g / m 2. did.
About the obtained battery electrode substrate, the number of edges was evaluated. The results are shown in Table 1.
The number of ends is an average value of the number of ends of fibers found by observing 10 fields of view of 1 mm × 1 mm with SEM (40 times) on the front and back of the produced base material.
［比較例１〜３］
ＰＰ／ＰＥ芯鞘構造の繊維からなる、繊維目付量、厚さ、繊度、繊維長さがそれぞれ表１に示したような数値を示す不織布を電極用基材として用い、実施例１と同様にしてニッケルを含有する金属総目付量が２００ｇ／ｍ２の比較例１〜３の電池用電極基板を作製した。
[Comparative Examples 1-3]
A non-woven fabric made of PP / PE core-sheath fibers, each having a fiber weight per unit area, thickness, fineness, and fiber length as shown in Table 1, was used as the electrode substrate, and the same as in Example 1. Thus, battery electrode substrates of Comparative Examples 1 to 3 having a total metal basis weight of 200 g / m 2 containing nickel were prepared.
比較例１では繊維長さが短いため繊維本数が増え、実施例１に比べて端部数が多いと考えられる。
比較例２では繊度が小さいため繊維本数が増え、実施例２に比べて端部数が多いと考えられる。
比較例３では厚さが小さいため、繊維本数は実施例３と変わらないが表面近傍に存在する端部の数が増えたと考えられる。
以上のように、本発明の範囲内で電池用電極基板を作製することによって、電池短絡の原因となる基材表面への繊維端部の飛び出しを抑制し、安全な電池用電極を作製することができる。
In Comparative Example 1, since the fiber length is short, the number of fibers is increased, and it is considered that the number of ends is larger than that in Example 1.
In Comparative Example 2, since the fineness is small, the number of fibers is increased, and it is considered that the number of ends is larger than that in Example 2.
Since the thickness in Comparative Example 3 is small, the number of fibers is not different from that in Example 3, but it is considered that the number of ends existing near the surface has increased.
As described above, by producing a battery electrode substrate within the scope of the present invention, it is possible to suppress the jumping of the fiber end to the surface of the base material causing a battery short circuit, and to produce a safe battery electrode. Can do.
本発明の電極基板は電極をセパレーター及び対極とともに捲回した際に繊維端部がセパレーターを突き破って短絡を起こすことがないので、アルカリ二次電池等の電池用電極として好適に使用することができる。 The electrode substrate of the present invention can be suitably used as an electrode for a battery such as an alkaline secondary battery because the fiber end does not break through the separator when the electrode is wound together with the separator and the counter electrode. .
Claims (6)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08203534A (en) * | 1995-01-27 | 1996-08-09 | Mitsubishi Paper Mills Ltd | Manufacture of nickel plated nonwoven electrode substrate |
| JPH08250125A (en) * | 1995-03-13 | 1996-09-27 | Mitsubishi Paper Mills Ltd | Nickel-plated nonwoven fabric electrode substrate |
| JPH08329956A (en) * | 1995-05-31 | 1996-12-13 | Furukawa Battery Co Ltd:The | Current collector for battery electrode and nickel electrode using it |
| JP2003109600A (en) * | 2001-09-28 | 2003-04-11 | Japan Vilene Co Ltd | Current collector material for battery, and battery using the same |
| JP2006310261A (en) * | 2005-01-14 | 2006-11-09 | Sumitomo Electric Ind Ltd | Current collector and electrode base plate for battery and their manufacturing method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08203534A (en) * | 1995-01-27 | 1996-08-09 | Mitsubishi Paper Mills Ltd | Manufacture of nickel plated nonwoven electrode substrate |
| JPH08250125A (en) * | 1995-03-13 | 1996-09-27 | Mitsubishi Paper Mills Ltd | Nickel-plated nonwoven fabric electrode substrate |
| JPH08329956A (en) * | 1995-05-31 | 1996-12-13 | Furukawa Battery Co Ltd:The | Current collector for battery electrode and nickel electrode using it |
| JP2003109600A (en) * | 2001-09-28 | 2003-04-11 | Japan Vilene Co Ltd | Current collector material for battery, and battery using the same |
| JP2006310261A (en) * | 2005-01-14 | 2006-11-09 | Sumitomo Electric Ind Ltd | Current collector and electrode base plate for battery and their manufacturing method |
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