JP2015043295A - Evaluation method of leak resistance performance of cell separator unwoven fabric - Google Patents
Evaluation method of leak resistance performance of cell separator unwoven fabric Download PDFInfo
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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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- Y02E60/10—Energy storage using batteries
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Abstract
Description
本発明は、ニッケル−カドミウム電池、ニッケル−亜鉛電池、ニッケル−水素電池等のアルカリ二次電池に好適に使用できる電池セパレータ用不織布の耐リーク性の評価方法に関するものである。 The present invention relates to a method for evaluating the leakage resistance of a nonwoven fabric for battery separator that can be suitably used for alkaline secondary batteries such as nickel-cadmium batteries, nickel-zinc batteries, and nickel-hydrogen batteries.
ニッケル−カドミウム電池やニッケル−水素電池等のアルカリ二次電池は、充放電特性、過充放電特性に優れ、長寿命で繰り返し使用できるため、コードレス電話、ノートパソコン、オーディオ機器等の小型電子機器の他、電動工具、電動自転車等の小型動力用途、ハイブリッド自動車、電気自動車等の大型動力用途等にも広く使用されている。このアルカリ二次電池に用いられている電池用セパレータの役割としては、正極と負極の分離、短絡の防止、電解液（高濃度アルカリ性水溶液）の吸液及び保持、また、電極反応により生じるガスの透過等が挙げられる。 Alkaline secondary batteries such as nickel-cadmium batteries and nickel-hydrogen batteries have excellent charge / discharge characteristics and overcharge / discharge characteristics, and can be used repeatedly with a long service life. Therefore, they can be used in small electronic devices such as cordless phones, laptop computers, and audio equipment. In addition, it is widely used for small power applications such as electric tools and electric bicycles, and large power applications such as hybrid cars and electric cars. The role of the battery separator used in the alkaline secondary battery is to separate the positive electrode and the negative electrode, prevent short circuit, absorb and retain the electrolyte (high concentration alkaline aqueous solution), and prevent the gas generated by the electrode reaction. For example, transmission.
従来、電池用セパレータとしては、一般に不織布が用いられてきた。ニッケル−カドミウム電池では、電解液に濡れやすく、その保液量が大きく、しかも電解液を含んだ状態で電気抵抗の低いポリアミド系繊維からなる不織布が使用されてきた。しかし、ニッケル−水素電池では、ポリアミド系繊維の加水分解による分解生成物が自己放電を促進してしまうために、耐アルカリ性及び耐酸化性に優れたポリオレフィン系繊維を主体とする不織布が主として使用されている。 Conventionally, a nonwoven fabric has generally been used as a battery separator. In a nickel-cadmium battery, a nonwoven fabric made of a polyamide fiber that is easily wetted by an electrolyte, has a large amount of liquid retention, and has a low electrical resistance in a state containing the electrolyte has been used. However, in nickel-hydrogen batteries, the decomposition products of polyamide fiber hydrolysis promote self-discharge, so nonwoven fabrics mainly composed of polyolefin fibers with excellent alkali resistance and oxidation resistance are mainly used. ing.
一方、ポリオレフィン系繊維を主体とする不織布は親水性が低いため、スルホン化処理、親水性単量体のグラフト処理、コロナ放電処理、界面活性剤付与処理等が施されるのが一般的である。 On the other hand, since nonwoven fabrics mainly composed of polyolefin fibers have low hydrophilicity, they are generally subjected to sulfonation treatment, hydrophilic monomer grafting treatment, corona discharge treatment, surfactant application treatment, and the like. .
このうち、スルホン化処理は、発煙硫酸や濃硫酸等によって不織布にスルホン酸基を導入する方法である（例えば、特許文献１〜３参照）。スルホン化処理を施した不織布は電解液の保液性が優れると共に、電池の自己放電反応を抑制できる長所がある。一方、強烈な酸化反応により、スルホン化処理の条件やスルホン化の進み具合によっては、繊維自体が脆化しやすく、強度物性の低下が起きやすいため、耐リーク性が悪化しやすい欠点がある。 Among these, the sulfonation treatment is a method of introducing a sulfonic acid group into the nonwoven fabric by fuming sulfuric acid, concentrated sulfuric acid, or the like (see, for example, Patent Documents 1 to 3). The non-woven fabric subjected to the sulfonation treatment has the advantages that the electrolyte retainability is excellent and the self-discharge reaction of the battery can be suppressed. On the other hand, due to the intense oxidation reaction, depending on the conditions of the sulfonation treatment and the progress of sulfonation, the fibers themselves tend to become brittle and the strength properties are liable to deteriorate, so that the leak resistance tends to deteriorate.
スルホン化処理に用いられる不織布としては、乾式不織布、又は湿式不織布が用いられる。電池の高容量化や内部短絡防止のため、地合の均一性に優れる不織布が求められており、その観点からは、一般的に乾式不織布よりも湿式不織布が優れている。 As the nonwoven fabric used for the sulfonation treatment, a dry nonwoven fabric or a wet nonwoven fabric is used. In order to increase the capacity of batteries and prevent internal short circuits, nonwoven fabrics with excellent uniformity of formation are required. From this viewpoint, wet nonwoven fabrics are generally superior to dry nonwoven fabrics.
近年の電子機器の小型軽量化に伴い、アルカリ二次電池の高容量化が要求されていることから、電池セパレータ用不織布の容積（坪量）を減少させ、厚みを薄くすることによって、正極活物質及び負極活物質の量を増やし、アルカリ電池の高容量化を図ろうとする試みがなされている。 As electronic devices have become smaller and lighter in recent years, there is a demand for higher capacity of alkaline secondary batteries. By reducing the volume (basis weight) of nonwoven fabrics for battery separators and reducing the thickness, Attempts have been made to increase the capacity of alkaline batteries by increasing the amount of materials and negative electrode active materials.
電池セパレータ用不織布の容積（坪量）を減少させ、厚みを薄くした場合、電池構成機の群巻回作業の際に、正極から微小クラークが発生した場合や、極板のエッジにバリが存在すると、その微小クラークやバリが電池セパレータ用不織布を貫通して短絡を発生させたり、極板の厚みやエッジで電池セパレータ用不織布に破れを発生させたりすることがあり、歩留まりを悪化させる問題があった。 When the volume (basis weight) of the nonwoven fabric for battery separator is reduced and the thickness is reduced, or when micro-clark is generated from the positive electrode during the group winding operation of the battery component machine, or there is a burr on the edge of the electrode plate Then, the micro clerk and burrs may penetrate the nonwoven fabric for battery separator and cause a short circuit, or the nonwoven fabric for battery separator may be torn at the thickness and edge of the electrode plate, which deteriorates the yield. there were.
耐ショート性を評価する方法としては、ハンディー圧縮試験機に取り付けられたステンレス製ジグ（厚さ：０．５ｍｍ、先端の刃先角度：６０度）で垂直に突き刺し、セパレータを切断するのに要する力を測定するエッジ式耐貫通力や、同試験機に取り付けられたニードル（先端部における曲率半径：０．５ｍｍ、直径：１ｍｍ、治具からの突出長さ：２ｍｍ）を、垂直に突き刺し、ニードルが突き抜けるのに要する力を測定するニードル式耐貫通力を測定する方法が開示されている（例えば、特許文献４参照）。しかしながら、これらの評価方法による値や、一般的な強度特性である引張強度や引裂強度だけでは、実際に電池を組んで評価したリーク不良率とは一致しないことがあった。 As a method for evaluating short-circuit resistance, the force required to cut the separator vertically with a stainless steel jig (thickness: 0.5 mm, tip edge angle: 60 degrees) attached to a handy compression tester. Edge-type penetration resistance to measure the needle and needle (curvature radius at the tip: 0.5 mm, diameter: 1 mm, protruding length from the jig: 2 mm) attached to the test machine, pierced vertically, needle Has disclosed a method of measuring the needle penetration resistance that measures the force required to penetrate through (for example, see Patent Document 4). However, the values obtained by these evaluation methods and the tensile strength and tear strength, which are general strength characteristics, may not coincide with the leakage failure rate actually evaluated by assembling the battery.
本発明の課題は、電池構成機での群巻回作業時における耐リーク性を簡易に評価できる電池セパレータ用不織布の耐リーク性の評価方法を提供することにある。 The subject of this invention is providing the leak resistance evaluation method of the nonwoven fabric for battery separators which can evaluate easily the leak resistance at the time of the group winding operation | work with a battery construction machine.
この課題を解決するために鋭意検討を行った結果、本発明の電池セパレータ用不織布の耐リーク性の評価方法に関する下記解決手段を見出した。 As a result of diligent studies to solve this problem, the following means for solving the leak resistance evaluation method for the nonwoven fabric for battery separator of the present invention have been found.
電池セパレータ用不織布の耐リーク性を評価する方法において、ＪＩＳ Ｐ ８１１３に準じて、所定のセパレータ幅に裁断した試験片を準備し、引張強度試験機を用いて、上チャック部分に試験片の一端をセットし、下チャック部分に、該セパレータ幅より７ｍｍ狭い幅で厚みが３ｍｍのＬ字鋼を被せながら、試験片のもう一端をセットし、引張強度と伸度を測定することを特徴とする電池セパレータ用不織布の耐リーク性の評価方法。 In the method for evaluating the leak resistance of the nonwoven fabric for battery separator, a test piece cut to a predetermined separator width is prepared according to JIS P 8113, and one end of the test piece is placed on the upper chuck portion using a tensile strength tester. The other end of the test piece is set while covering the lower chuck portion with an L-shaped steel having a width 7 mm narrower than the separator width and a thickness of 3 mm, and the tensile strength and the elongation are measured. Evaluation method of leak resistance of nonwoven fabric for battery separator.
本発明において、電池セパレータ用不織布の幅より７ｍｍ狭い幅で、厚みが３ｍｍのＬ字鋼のエッジが、該不織布を引っ張った際に食い込み、該不織布が伸ばされ、引き千切られるまでの引張強度と伸度を測定することによって、電池構成機の群巻回作業の際に、正極から発生した微小クラークや、極板のエッジのバリが電池セパレータ用不織布を貫通して短絡を発生させたり、極板の厚みやエッジで電池セパレータ用不織布に破れを発生させたりするのを防ぐのに必要な引張強度や伸度を把握することができる。そして、実際に電池を組んでリーク不良率との関係を調査しておくことにより、その後に、電池セパレータ用不織布を改良したい際に、実際に電池を組み、多額の費用を掛けてリーク不良率を調査しなくても、簡易な評価方法で精度高く、選別することができる。 In the present invention, the edge of the L-shaped steel having a width of 7 mm narrower than the width of the nonwoven fabric for battery separator and a thickness of 3 mm bites in when the nonwoven fabric is pulled, and the tensile strength until the nonwoven fabric is stretched and chopped off. By measuring the elongation, during the group winding operation of the battery constituting machine, the micro clerk generated from the positive electrode or the burrs on the edge of the electrode plate penetrate the nonwoven fabric for the battery separator, The tensile strength and elongation required to prevent the nonwoven fabric for battery separator from being broken by the thickness and edge of the plate can be grasped. And by actually assembling the battery and investigating the relationship with the leak failure rate, when you want to improve the non-woven fabric for the battery separator after that, you actually assembled the battery and spent a lot of money on the leak failure rate Even if it is not investigated, it is possible to sort with high accuracy by a simple evaluation method.
本発明で用いる引張強度試験機は、引張強度と伸度が測定できれば、特に限定されない。例えば、（株）オリエンテック製の卓上型材料試験機（装置名：ＳＴＡ−１１５０）を用い、ＪＩＳ Ｐ ８１１３に準じ、チャックの大きさは５０ｍｍ×５０ｍｍ、チャック間隔は１００ｍｍ、引張速度は３００ｍｍ／ｍｉｎで行うことができる。 The tensile strength tester used in the present invention is not particularly limited as long as the tensile strength and the elongation can be measured. For example, using a desktop material testing machine (equipment name: STA-1150) manufactured by Orientec Co., Ltd., the size of the chuck is 50 mm × 50 mm, the chuck interval is 100 mm, and the tensile speed is 300 mm / It can be performed in min.
本発明で用いるＬ字鋼の材質は、不織布の引張強度に負けて曲がらない強度があれば、特に限定されない。ステンレス製やアルミ製が好適に用いることができる。Ｌ字鋼の幅方向の長さは、セパレータ幅よりも７ｍｍ狭くし、セパレータ幅に対して、片側３．５ｍｍ内側にセットする。そうすることで、電極のエッジに見立てた測定が可能である。Ｌ字鋼の厚みは、不織布の引張強度試験に負けて曲がらない強度が確保できれば、特に限定されないが、群巻回作業での電極の厚みにより不織布が伸ばされる観点から１ｍｍ以上が好ましい。Ｌ字鋼の縦の長さは、特に限定されないが、外寸で２５ｍｍ〜５０ｍｍの長さが好ましい。 The material of the L-shaped steel used in the present invention is not particularly limited as long as it has a strength that does not bend due to the tensile strength of the nonwoven fabric. Stainless steel or aluminum can be suitably used. The length in the width direction of the L-shaped steel is 7 mm narrower than the separator width, and is set on the inner side of 3.5 mm with respect to the separator width. By doing so, it is possible to perform measurement that looks like the edge of an electrode. The thickness of the L-shaped steel is not particularly limited as long as it can secure a strength that does not bend due to the tensile strength test of the nonwoven fabric, but is preferably 1 mm or more from the viewpoint of the nonwoven fabric being stretched by the thickness of the electrode in the group winding operation. The vertical length of the L-shaped steel is not particularly limited, but is preferably 25 mm to 50 mm in outer dimensions.
本発明において評価される電池セパレータ用不織布は、乾式不織布でも湿式不織布でも特に限定されない。親水化処理は、スルホン化処理、グラフト重合処理、フッ素処理、コロナ処理、プラズマ放電処理、界面活性剤処理等の何れの処理も、特に限定されない。カレンダー処理によって調整される不織布の厚みは特に限定されない。 The nonwoven fabric for battery separator evaluated in the present invention is not particularly limited to a dry nonwoven fabric or a wet nonwoven fabric. The hydrophilization treatment is not particularly limited to any treatment such as sulfonation treatment, graft polymerization treatment, fluorine treatment, corona treatment, plasma discharge treatment, and surfactant treatment. The thickness of the nonwoven fabric adjusted by the calendar process is not particularly limited.
電池セパレータ用不織の坪量及び厚みは、適用する電池の特性に応じて、適宜選択できる。ここで目付は、ＪＩＳ Ｐ ８１２４に規定されている坪量を表し、厚みはＪＩＳ Ｐ ８１１８に規定される厚さを表す。 The basis weight and thickness of the non-woven fabric for the battery separator can be appropriately selected according to the characteristics of the applied battery. Here, the basis weight represents the basis weight defined in JIS P 8124, and the thickness represents the thickness defined in JIS P 8118.
本発明を実施例により、更に詳細に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.
（電池セパレータ用不織布１）
芯成分がポリプロピレンで、鞘成分が高密度ポリエチレンであるポリオレフィン系芯鞘型複合繊維（繊度０．８ｄｔｅｘ、繊維径１０．３μｍ、繊維長５．０ｍｍ、乾強度３．３ｃＮ／ｄｔｅｘ）１００質量部を、パルパーの水中で離解、分散させ、アジテーターで緩やかに撹拌して均一な抄造用スラリーを調製した。この抄造用スラリーを傾斜ワイヤー型短網抄紙機による湿式抄造法を用いてウェブを形成し、１３８℃に設定されたヤンキードライヤーと１４０℃の熱風フードで乾燥させると共に、ポリオレフィン系芯鞘型複合繊維の鞘部分を熱溶融接着させ、不織布の巻き取りを得た。
(Nonwoven fabric for battery separator 1)
100 parts by mass of polyolefin core-sheath composite fiber (fineness 0.8 dtex, fiber diameter 10.3 μm, fiber length 5.0 mm, dry strength 3.3 cN / dtex) whose core component is polypropylene and whose sheath component is high-density polyethylene Was dispersed and dispersed in water of a pulper, and gently stirred with an agitator to prepare a uniform papermaking slurry. A web is formed from the slurry for papermaking by a wet papermaking method using a slanted wire short net paper machine, and the web is dried with a Yankee dryer set at 138 ° C and a hot air hood at 140 ° C. The sheath portion was heat-melted and bonded to obtain a nonwoven fabric.
このようにして得られた不織布に対して、三酸化硫黄ガスを含む７５℃の乾燥空気中で、２５秒間スルホン化処理を行い、２．５質量％の水酸化ナトリウム水溶液で中和し、イオン交換水で十分洗浄し、次いで、界面活性剤として、アルキルジフェニルエーテルジスルホン酸ナトリウムを、スルホン化処理後の不織布に対して０．３質量％となるようにスプレー塗布し、乾燥後、カレンダー処理により厚み調整して、硫黄含有率０．５０質量％、坪量６２．２ｇ／ｍ２、マイクロメーターで測定した厚さが１８０μｍの電池セパレータ用不織布を得た。 The nonwoven fabric thus obtained was sulfonated for 25 seconds in 75 ° C. dry air containing sulfur trioxide gas, neutralized with a 2.5% by mass aqueous sodium hydroxide solution, Wash thoroughly with exchange water, then spray-apply sodium alkyldiphenyl ether disulfonate as a surfactant to 0.3% by mass with respect to the non-woven fabric after sulfonation treatment, dry, and then calender the thickness. By adjusting, a nonwoven fabric for battery separator having a sulfur content of 0.50% by mass, a basis weight of 62.2 g / m 2 , and a thickness of 180 μm measured with a micrometer was obtained.
（電池セパレータ用不織布２）
芯成分がポリプロピレンで、鞘成分が高密度ポリエチレンであるポリオレフィン系芯鞘型複合繊維（繊度１．２ｄｔｅｘ、繊維径１２．９μｍ、繊維長５．０ｍｍ、乾強度２．８ｃＮ／ｄｔｅｘ）１００質量部を使用した以外は、実施例１と同様にして、不織布を抄造し、スルホン化処理し、界面活性剤を付着させ、カレンダー処理を行い、硫黄含有率０．５５質量％、坪量６３．４ｇ／ｍ２、マイクロメーターで測定した厚さが１８０μｍの電池セパレータ用不織布を得た。
(Nonwoven fabric for battery separator 2)
100 parts by mass of polyolefin core-sheath composite fiber (fineness 1.2 dtex, fiber diameter 12.9 μm, fiber length 5.0 mm, dry strength 2.8 cN / dtex) whose core component is polypropylene and whose sheath component is high-density polyethylene In the same manner as in Example 1 except that the nonwoven fabric was used, a nonwoven fabric was made, sulfonated, attached with a surfactant and calendered, with a sulfur content of 0.55 mass% and a basis weight of 63.4 g. / m 2, thickness was measured with a micrometer was obtained nonwoven battery separator 180 [mu] m.
（電池セパレータ用不織布３）
芯成分がポリプロピレンで、鞘成分が高密度ポリエチレンであるポリオレフィン系芯鞘型複合繊維（繊度０．８ｄｔｅｘ、繊維径１０．５μｍ、繊維長１０．０ｍｍ、乾強度３．２ｃＮ／ｄｔｅｘ）１００質量部を使用した以外は、実施例１と同様にして、不織布を抄造し、スルホン化処理し、界面活性剤を付着させ、カレンダー処理を行い、硫黄含有率０．５５質量％、坪量６３．０ｇ／ｍ２、マイクロメーターで測定した厚さが１８０μｍの電池セパレータ用不織布を得た。
(Nonwoven fabric for battery separator 3)
100 parts by mass of polyolefin core-sheath composite fiber (fineness 0.8 dtex, fiber diameter 10.5 μm, fiber length 10.0 mm, dry strength 3.2 cN / dtex) whose core component is polypropylene and whose sheath component is high-density polyethylene In the same manner as in Example 1 except that the nonwoven fabric was used, a nonwoven fabric was made, sulfonated, attached with a surfactant, calendered, sulfur content 0.55% by mass, basis weight 63.0 g. / m 2, thickness was measured with a micrometer was obtained nonwoven battery separator 180 [mu] m.
（電池セパレータ用不織布４）
芯成分がポリプロピレンで、鞘成分が高密度ポリエチレンであるポリオレフィン系芯鞘型複合繊維（繊度０．８ｄｔｅｘ、繊維径１０．５μｍ、繊維長１２．０ｍｍ、乾強度３．５ｃＮ／ｄｔｅｘ）１００質量部を使用した以外は、実施例１と同様にして、不織布を抄造し、スルホン化処理し、界面活性剤を付着させ、カレンダー処理を行い、硫黄含有率０．５０質量％、坪量６３．５ｇ／ｍ２、マイクロメーターで測定した厚さが１８３μｍの電池セパレータ用不織布を得た。
(Nonwoven fabric for battery separator 4)
100 parts by mass of polyolefin core-sheath composite fiber (fineness 0.8 dtex, fiber diameter 10.5 μm, fiber length 12.0 mm, dry strength 3.5 cN / dtex) whose core component is polypropylene and whose sheath component is high-density polyethylene In the same manner as in Example 1 except that the nonwoven fabric was used, a nonwoven fabric was made, sulfonated, attached with a surfactant and calendered, with a sulfur content of 0.50 mass% and a basis weight of 63.5 g. / m 2, thickness was measured with a micrometer was obtained nonwoven battery separator 183Myuemu.
（電池セパレータ用不織布５）
芯成分がポリプロピレンで、鞘成分が高密度ポリエチレンであるポリオレフィン系芯鞘型複合繊維（繊度０．８ｄｔｅｘ、繊維径１０．５μｍ、繊維長５．０ｍｍ、乾強度２．９ｃＮ／ｄｔｅｘ）１００質量部を使用した以外は、実施例１と同様にして、不織布を抄造し、スルホン化処理し、界面活性剤を付着させ、カレンダー処理を行い、硫黄含有率０．５２質量％、坪量５４．７ｇ／ｍ２、マイクロメーターで測定した厚さが１２１μｍの電池セパレータ用不織布を得た。
(Nonwoven fabric for battery separator 5)
100 parts by mass of polyolefin core-sheath type composite fiber (fineness 0.8 dtex, fiber diameter 10.5 μm, fiber length 5.0 mm, dry strength 2.9 cN / dtex) whose core component is polypropylene and whose sheath component is high-density polyethylene In the same manner as in Example 1, a nonwoven fabric was made, sulfonated, attached with a surfactant, calendered, sulfur content 0.52% by mass, basis weight 54.7 g. / m 2, thickness was measured with a micrometer was obtained nonwoven battery separator 121Myuemu.
（電池セパレータ用不織布６）
芯成分がポリプロピレンで、鞘成分が高密度ポリエチレンであるポリオレフィン系芯鞘型複合繊維（繊度０．８ｄｔｅｘ、繊維径１０．５μｍ、繊維長１３．５ｍｍ、乾強度３．５ｃＮ／ｄｔｅｘ）１００質量部を使用した以外は、実施例１と同様にして、不織布を抄造し、スルホン化処理し、界面活性剤を付着させ、カレンダー処理を行い、硫黄含有率０．５１質量％、坪量５５．０ｇ／ｍ２、マイクロメーターで測定した厚さが１２８μｍの電池セパレータ用不織布を得た。
(Nonwoven fabric for battery separator 6)
100 parts by mass of polyolefin core-sheath composite fiber (fineness 0.8 dtex, fiber diameter 10.5 μm, fiber length 13.5 mm, dry strength 3.5 cN / dtex) whose core component is polypropylene and whose sheath component is high-density polyethylene In the same manner as in Example 1 except that the nonwoven fabric was used, a nonwoven fabric was made, sulfonated, attached with a surfactant, calendered, sulfur content 0.51% by mass, basis weight 55.0 g. / m 2, thickness was measured with a micrometer was obtained nonwoven battery separator 128 .mu.m.
（電池セパレータ用不織布７）
芯成分がポリプロピレンで、鞘成分が高密度ポリエチレンであるポリオレフィン系芯鞘型複合繊維（繊度０．８ｄｔｅｘ、繊維径１０．６μｍ、繊維長５．０ｍｍ、乾強度４．４ｃＮ／ｄｔｅｘ）１００質量部を使用した以外は、実施例１と同様にして、不織布を抄造し、スルホン化処理し、界面活性剤を付着させ、カレンダー処理を行い、硫黄含有率０．４９質量％、坪量５４．５ｇ／ｍ２、マイクロメーターで測定した厚さが１２５μｍの電池セパレータ用不織布を得た。
(Nonwoven fabric for battery separator 7)
100 parts by mass of polyolefin core / sheath composite fiber (fineness 0.8 dtex, fiber diameter 10.6 μm, fiber length 5.0 mm, dry strength 4.4 cN / dtex) whose core component is polypropylene and whose sheath component is high-density polyethylene In the same manner as in Example 1 except that the non-woven fabric was used, a nonwoven fabric was made, sulfonated, attached with a surfactant, calendered, sulfur content 0.49% by mass, basis weight 54.5 g. A non-woven fabric for a battery separator having a thickness measured by a micrometer of 125 μm / m 2 was obtained.
（電池セパレータ用不織布８）
芯成分がポリプロピレンで、鞘成分が高密度ポリエチレンであるポリオレフィン系芯鞘型複合繊維（繊度０．８ｄｔｅｘ、繊維径１０．６μｍ、繊維長５．０ｍｍ、乾強度４．４ｃＮ／ｄｔｅｘ）を７０質量部とポリプロピレン繊維（繊度０．８ｄｔｅｘ、繊維径１０．６μｍ、繊維長５．０ｍｍ、乾強度５．２ｃＮ／ｄｔｅｘ）３０部を使用した以外は、実施例１と同様にして、不織布を抄造し、スルホン化処理し、界面活性剤を付着させ、カレンダー処理を行い、硫黄含有率０．５０質量％、坪量５４．７ｇ／ｍ２、マイクロメーターで測定した厚さが１２６μｍの電池セパレータ用不織布を得た。
(Nonwoven fabric for battery separator 8)
70 mass of polyolefin core-sheath composite fiber (fineness 0.8 dtex, fiber diameter 10.6 μm, fiber length 5.0 mm, dry strength 4.4 cN / dtex) whose core component is polypropylene and whose sheath component is high-density polyethylene The nonwoven fabric was made in the same manner as in Example 1, except that 30 parts of polypropylene fiber (fineness 0.8 dtex, fiber diameter 10.6 μm, fiber length 5.0 mm, dry strength 5.2 cN / dtex) were used. Non-woven fabric for battery separator having a sulfur content of 0.50% by mass, a basis weight of 54.7 g / m 2 , and a thickness measured by a micrometer of 126 μm. Got.
［硫黄含有率］
スルホン化処理された電池セパレータ用不織布から直径３５ｍｍの試料を採取し、イオン交換水２００ｍＬ中で１０分間、２回洗浄し、６０℃で１０分間乾燥して測定用試料を作製した。この試料をホルダーにセットして、蛍光Ｘ線装置（装置名：ＺＳＸ Ｐｒｉｍｕｓ II、Ｒｈターゲット、５０ｋＶ−５０ｍＡ、（株）リガク製）で全元素測定を行った。硫黄含有率は、測定値を半定量分析法であるＳＱＸ計算することで算出し、スルホン化処理量を質量％で見積もった。
[Sulfur content]
A sample having a diameter of 35 mm was collected from the sulfonated nonwoven fabric for battery separator, washed twice in 200 mL of ion-exchanged water for 10 minutes, and dried at 60 ° C. for 10 minutes to prepare a measurement sample. This sample was set in a holder, and all elemental measurements were performed with a fluorescent X-ray apparatus (device name: ZSX Primus II, Rh target, 50 kV-50 mA, manufactured by Rigaku Corporation). The sulfur content was calculated by calculating the measured value by SQX, which is a semi-quantitative analysis method, and the sulfonation treatment amount was estimated by mass%.
＜評価＞
実施例で得られた電池セパレータ用不織布について、下記の評価を行い、結果を表１に示した。
<Evaluation>
About the nonwoven fabric for battery separators obtained in the Example, the following evaluation was performed and the results are shown in Table 1.
［坪量の評価］
水分平衡状態の不織布から、５０ｍｍ×２００ｍｍの試料片を幅方向から１０枚採取し、各サンプルの質量を測定し、質量×１００で１ｍ２当たりの坪量に換算し、その平均値を求めた。
[Evaluation of basis weight]
Ten specimens of 50 mm × 200 mm from the width direction were collected from the moisture-balanced nonwoven fabric, the mass of each sample was measured, and the average value was calculated by converting the basis weight per 1 m 2 with mass × 100. .
［厚みの評価]
坪量を測定した各試料片について、直径６．３５ｍｍのマイクロメーターを用いて、四角の厚さを４点測定し、平均値を求め、更に、試料片１０枚の平均値を求めた。
[Evaluation of thickness]
About each sample piece which measured the basic weight, using a micrometer with a diameter of 6.35 mm, square thickness was measured 4 points | pieces, the average value was calculated | required, and also the average value of 10 sample pieces was calculated | required.
［引張強度と最大点伸度の評価］
坪量を測定した試料片１０枚について、ＪＩＳ Ｐ ８１１３に準じて、卓上型材料試験機（装置名：ＳＴＡ−１１５０、（株）オリエンテック製）を用いて、引張強度と最大点伸度を測定し、１０枚の平均値を不織布の引張強度と最大点伸度とした。但し、チャック間隔は１００ｍｍ、引張速度は３００ｍｍ／ｍｉｎとする。
[Evaluation of tensile strength and maximum elongation]
Ten sample pieces whose basis weights were measured were measured for tensile strength and maximum point elongation using a desktop material testing machine (apparatus name: STA-1150, manufactured by Orientec Co., Ltd.) according to JIS P8113. The average value of 10 sheets was taken as the tensile strength and maximum point elongation of the nonwoven fabric. However, the chuck interval is 100 mm and the tensile speed is 300 mm / min.
［突刺強度の評価］
先端に曲率１．６の丸みをつけた直径１ｍｍの金属針を卓上型材料試験機（装置名：ＳＴＡ−１１５０、（株）オリエンテック製）に装着し、試料面に対して直角に１ｍｍ／秒の一定速度で貫通するまで降ろした。この時の最大荷重（Ｎ）で計測し、幅方向で等間隔に１０箇所の平均値を求めた。
[Evaluation of puncture strength]
A metal needle with a diameter of 1 mm with a curvature of 1.6 at the tip is mounted on a desktop material testing machine (device name: STA-1150, manufactured by Orientec Co., Ltd.), and 1 mm / perpendicular to the sample surface. It was lowered until it penetrated at a constant speed of seconds. The measurement was performed with the maximum load (N) at this time, and the average value of 10 locations was obtained at equal intervals in the width direction.
［横方向の引裂強度の評価］
流れ方向６３ｍｍ、幅方向７６ｍｍの試験片を幅方向から１０枚採取し、ＪＩＳ Ｐ ８１１６−２０００に準じて、エレメンドルフ引裂度試験機を用いて、１枚ずつ測定し、１６枚に換算した値を求め、試験片１０枚の平均値を求めた。
[Evaluation of tear strength in the transverse direction]
10 specimens from the width direction were sampled in the flow direction of 63 mm and the width direction of 76 mm, measured according to JIS P 8116-2000 one by one using an Elmendorf Tear Tester, and converted into 16 pieces. And the average value of 10 test pieces was obtained.
［Ｌ字鋼挿入時の引張強度と最大点伸度の評価］
図１は、本発明の電池セパレータ用不織布の耐リーク性評価方法において、引張強度試験機のチャック部分を示した正面図である。水分平衡状態の電池セパレータ用不織布から、４２ｍｍ×２００ｍｍの試料片を幅方向から１０枚採取した。ＪＩＳ Ｐ ８１１３に準じて、卓上型材料試験機（装置名：ＳＴＡ−１１５０、（株）オリエンテック製）を用いて、上チャック部分４に試験片１の一端をセットし、下チャック部分３に、Ｌ字鋼の横方向の幅３５ｍｍ、厚み３ｍｍ、Ｌ字の縦方向の外寸長さ２５ｍｍのＬ字鋼を試験片に被せながら、試験片１のもう一端をセットし、引張強度と最大点伸度を測定した。１０枚の平均値を、不織布の「Ｌ字引張強度」と「Ｌ字最大点伸度」とした。但し、チャック間隔は１００ｍｍ、引張速度は３００ｍｍ／ｍｉｎとする。
[Evaluation of tensile strength and maximum elongation at insertion of L-shaped steel]
FIG. 1 is a front view showing a chuck portion of a tensile strength tester in a method for evaluating leakage resistance of a nonwoven fabric for battery separator according to the present invention. Ten specimens of 42 mm × 200 mm were collected from the width direction from the nonwoven fabric for battery separator in a moisture equilibrium state. In accordance with JIS P 8113, using a tabletop material testing machine (device name: STA-1150, manufactured by Orientec Co., Ltd.), one end of the test piece 1 is set in the upper chuck portion 4 and the lower chuck portion 3 The other end of the test piece 1 is set while covering the L-shaped steel with a lateral width of 35 mm, a thickness of 3 mm, and an L-shaped vertical dimension of 25 mm. The point elongation was measured. The average value of 10 sheets was defined as “L-shaped tensile strength” and “L-shaped maximum point elongation” of the nonwoven fabric. However, the chuck interval is 100 mm and the tensile speed is 300 mm / min.
［電池の作製］
電極の集電体として、発泡ニッケル基材を用いたペースト式水酸化ニッケル正極（４０ｍｍ幅）と、ニッケルメッキパンチングメタル基材を用いた水素吸蔵合金負極（４０ｍｍ幅）を１枚ずつ用い、これらの電極の間に、４２ｍｍ幅の実施例で得られた電池セパレータ用不織布を介在させて、電池構成機を用いて巻き取り、渦巻状極板群を作製した。該渦巻状極板群を円筒形の金属ケースに収納した後、１Ｎ水酸化リチウムを含む７Ｎ水酸化カリウム水溶液を主体とするアルカリ電解液を一定量注入した後、安全弁付きの封印蓋を取り付けて、公称容量が１．７Ａｈの単３形密閉式ニッケル水素電池を１万個作製した。その後、正極と負極との間に２４０Ｖの電圧を印加し、電気抵抗が１ｋΩを超えるものを正常とし、超えないものをリーク不良として、その割合を求めた。
[Production of battery]
As the electrode current collector, a paste type nickel hydroxide positive electrode (40 mm width) using a foamed nickel base material and a hydrogen storage alloy negative electrode (40 mm width) using a nickel-plated punching metal base material are used one by one. A non-woven fabric for a battery separator obtained in an example having a width of 42 mm was interposed between the electrodes, and wound using a battery construction machine to produce a spiral electrode group. After the spiral electrode plate group is stored in a cylindrical metal case, a certain amount of alkaline electrolyte mainly composed of 7N potassium hydroxide aqueous solution containing 1N lithium hydroxide is injected, and then a sealing lid with a safety valve is attached. Ten thousand AA sealed nickel-metal hydride batteries having a nominal capacity of 1.7 Ah were produced. Thereafter, a voltage of 240 V was applied between the positive electrode and the negative electrode, and those having an electric resistance exceeding 1 kΩ were regarded as normal, and those not exceeding were regarded as leak defects, and the ratio was determined.
図２〜図７は、リーク不良率と、引張強度（図２）、最大点伸度（図３）、突刺強度（図４）、引裂強度（図５）、Ｌ字引張強度（図６）、Ｌ字最大点伸度（図７）との関係を表したグラフである。 2 to 7 show the leakage failure rate, tensile strength (FIG. 2), maximum point elongation (FIG. 3), puncture strength (FIG. 4), tear strength (FIG. 5), L-shaped tensile strength (FIG. 6). It is a graph showing the relationship with L-shaped maximum point elongation (FIG. 7).
図２から、引張強度が高い方がリーク不良率は良好な傾向が見られるが、電池セパレータ用不織布８のように配合を変えると、引張強度が低下することがあり、累乗近似を取ると相関係数Ｒ２が０．０７２であり、リーク不良率と引張強度の相関は見られなかった。 From FIG. 2, the higher the tensile strength, the better the defective leak rate tends to be seen. However, if the composition is changed as in the battery separator nonwoven fabric 8, the tensile strength may decrease. correlation coefficient R 2 is 0.072, the correlation of tensile leak failure rate intensity was not observed.
図３から、累乗近似を取ると相関係数Ｒ２が０．１５３であり、リーク不良率と最大点伸度の相関は見られなかった。 From Figure 3, a correlation coefficient R 2 to take power approximation is 0.153, the correlation of the leakage failure rate and the maximum point elongation was observed.
図４から、累乗近似を取ると相関係数Ｒ２が０．３４９であり、リーク不良率と突刺強度の相関は低かった。 From FIG. 4, when taking the power approximation, the correlation coefficient R 2 was 0.349, and the correlation between the leak failure rate and the puncture strength was low.
図５から、引裂強度が高い方がリーク不良率は良好な傾向が見られるが、累乗近似を取ると相関係数Ｒ２が０．４４９であり、リーク不良率と横方向の引裂強度の相関はまだ低かった。 From Figure 5, although it is leak defect rate tear strength is higher favorable trend is observed a correlation coefficient wherein R 2 is 0.449 to take power approximation, the correlation of the tear strength of the leak defect rate and lateral Was still low.
図６から、累乗近似を取ると相関係数Ｒ２が０．９１８であり、リーク不良率とＬ字引張強度の相関が高く、他の強度試験と比較して、Ｌ字引張強度は優れた評価方法である。 From FIG. 6, when taking a power approximation, the correlation coefficient R 2 is 0.918, the correlation between the leak failure rate and the L-shaped tensile strength is high, and the L-shaped tensile strength is superior compared to other strength tests. It is an evaluation method.
図７から、累乗近似を取ると相関係数Ｒ２が０．８０７であり、リーク不良率とＬ字最大点伸度の相関も高く、Ｌ字最大点伸度も優れた評価方法である。 From FIG. 7, when taking power approximation, the correlation coefficient R 2 is 0.807, the correlation between the leakage failure rate and the L-shaped maximum point elongation is high, and the evaluation method is excellent in the L-shaped maximum point elongation.
本発明は、ニッケル−カドミウム二次電池、ニッケル−水素二次電池等のアルカリ二次電池セパレータ用不織布の耐リーク性の評価に活用できる。 INDUSTRIAL APPLICATION This invention can be utilized for evaluation of the leak resistance of the nonwoven fabric for alkaline secondary battery separators, such as a nickel-cadmium secondary battery and a nickel-hydrogen secondary battery.
１ 試験片
２ Ｌ字鋼
３ 下チャック部分
４ 上チャック部分
1 Test piece 2 L-shaped steel 3 Lower chuck part 4 Upper chuck part
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018174224A1 (en) * | 2017-03-24 | 2018-09-27 | 三菱製紙株式会社 | Semipermeable membrane support body |
| US11998879B2 (en) | 2017-03-24 | 2024-06-04 | Mitsubishi Paper Mills Limited | Semipermeable membrane support |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018174224A1 (en) * | 2017-03-24 | 2018-09-27 | 三菱製紙株式会社 | Semipermeable membrane support body |
| JPWO2018174224A1 (en) * | 2017-03-24 | 2020-01-23 | 三菱製紙株式会社 | Semipermeable membrane support |
| JP2021119006A (en) * | 2017-03-24 | 2021-08-12 | 三菱製紙株式会社 | Translucent membrane support |
| JP2022107809A (en) * | 2017-03-24 | 2022-07-22 | 三菱製紙株式会社 | Translucent membrane support |
| JP7464655B2 (en) | 2017-03-24 | 2024-04-09 | 三菱製紙株式会社 | Semipermeable membrane support |
| US11998879B2 (en) | 2017-03-24 | 2024-06-04 | Mitsubishi Paper Mills Limited | Semipermeable membrane support |
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