JP2001076705A - Separator for alkaline battery and alkaline battery using it - Google Patents
Separator for alkaline battery and alkaline battery using itInfo
- Publication number
- JP2001076705A JP2001076705A JP25390999A JP25390999A JP2001076705A JP 2001076705 A JP2001076705 A JP 2001076705A JP 25390999 A JP25390999 A JP 25390999A JP 25390999 A JP25390999 A JP 25390999A JP 2001076705 A JP2001076705 A JP 2001076705A
- Authority
- JP
- Japan
- Prior art keywords
- separator
- oxalyl chloride
- alkaline battery
- polymer material
- alkaline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ニッケル・カドミ
ウム電池やニッケル水素（金属水素化物）電池などのア
ルカリ電池およびそのセパレ−タの改良に関するもので
ある。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an alkaline battery such as a nickel-cadmium battery and a nickel hydride (metal hydride) battery, and to an improvement in a separator therefor.
【０００２】[0002]
【従来の技術】近年、エレクトロニクスや通信の分野に
おいて、半導体の急速な進歩とともに電子機器の小型軽
量化が図られてきたが、その進歩に伴って駆動源である
電池の高性能化が求められている。これら用途で現在実
用化されている電池として、ニッケル・カドミウム電池
やニッケル水素電池などのアルカリ電池がある。アルカ
リ電池は負極と正極との間にセパレ−タを介在させ、電
解液としてアルカリ水溶液を用いて構成されるが、電池
のさらなる高性能化や低価格化を目指して、積極的にこ
れら構成材料の技術開発が展開されている。中でも、セ
パレ−タ技術の重要性が増してきている。2. Description of the Related Art In recent years, in the field of electronics and communications, rapid progress in semiconductors has led to reductions in the size and weight of electronic devices. ing. Alkaline batteries such as nickel-cadmium batteries and nickel-metal hydride batteries are currently in practical use for these purposes. Alkaline batteries are constructed using an aqueous alkaline solution as an electrolyte with a separator between the negative and positive electrodes. These components are actively used to further improve the performance and reduce the price of the battery. Technology development has been deployed. Above all, the importance of separator technology is increasing.
【０００３】従来からアルカリ電池用セパレ−タとし
て、電解液への親水性や保液性に優れたポリアミド不織
布であるナイロン・セパレ−タが主に用いられてきた。
しかしながら、ポリアミド系セパレ−タは耐アルカリ性
や耐酸化性に問題があり、高温下で電池が使用された場
合、ナイロン繊維が容易に酸化分解されて劣化し、電池
の短絡や内部抵抗の増大をきたしたり、分解生成物であ
る窒素化合物が原因となり、電池の自己放電を加速する
などの欠点がある。[0003] Conventionally, as a separator for an alkaline battery, a nylon separator which is a polyamide nonwoven fabric excellent in hydrophilicity and liquid retaining property for an electrolytic solution has been mainly used.
However, polyamide-based separators have problems in alkali resistance and oxidation resistance. When batteries are used at high temperatures, nylon fibers are easily oxidized and degraded and deteriorate, resulting in short-circuiting of batteries and increase in internal resistance. There are disadvantages such as accretion and acceleration of self-discharge of the battery due to nitrogen compounds which are decomposition products.
【０００４】そこで、ポリアミド系不織布に代えて、耐
アルカリ性や耐酸化性に優れたポリオレフィン系不織布
がアルカリ電池、特にニッケル水素電池のセパレ−タと
して適用されている。しかしながら、ポリプロピレンや
ポリエチレンに代表されるポリオレフィン繊維は本質的
に疎水性であるために、電解液への親水性や保液性をい
かに永続的に付与するかが大きな技術課題となってい
る。Therefore, instead of the polyamide-based nonwoven fabric, a polyolefin-based nonwoven fabric having excellent alkali resistance and oxidation resistance has been applied as a separator for an alkaline battery, particularly a nickel-metal hydride battery. However, since polyolefin fibers typified by polypropylene and polyethylene are inherently hydrophobic, how to permanently impart hydrophilicity and liquid retention to an electrolytic solution is a major technical problem.
【０００５】現在主流の親水化方法の一つとして、ポリ
オレフィン繊維の表面に、アクリル酸などのビニルモノ
マ−をグラフ重合してカルボキシル基を導入するグラフ
ト化処理がある。例えば、ビニルモノマ−と重合開始剤
を含む溶液中に不織布を浸漬し加熱処理する方法や、不
織布に電子線などを照射した後にビニルモノマ−溶液に
接触させるか、光増感剤を含むビニルモノマ−溶液に不
織布を含浸した後に紫外線照射する方法によってグラフ
ト化されている。しかしながら、いずれも液相ラジカル
反応系であるために、グラフト処理後に未反応モノマ−
や溶媒の除去、副反応生成物であるホモポリマ−の除去
などの工程が必要であり、製造法が煩雑であること、ま
た、不織布の表層部での反応が起こり易く内部まで均一
に極性基を導入できないこと、繊維表面にビニルモノマ
−が枝状に重合付加されるために、不織布基布の目付量
の増大や通気度の低下を伴い、品質制御や薄型化が困難
であること等の問題があり、従来のグラフト重合法に替
わる製造工程の簡素な品質制御が容易なカルボン酸基を
不織布に導入する親水化技術が強く望まれている。[0005] As one of the currently mainstream methods of hydrophilization, there is a grafting treatment in which a vinyl monomer such as acrylic acid is graph-polymerized on the surface of a polyolefin fiber to introduce a carboxyl group. For example, a method in which a nonwoven fabric is immersed in a solution containing a vinyl monomer and a polymerization initiator and then heat-treated, or the nonwoven fabric is irradiated with an electron beam or the like and then brought into contact with the vinyl monomer solution or the vinyl monomer solution containing a photosensitizer is used. It is grafted by a method of irradiating ultraviolet rays after impregnating the nonwoven fabric. However, since all of them are liquid-phase radical reaction systems, unreacted monomer
It is necessary to carry out steps such as removal of the solvent and the solvent, and removal of the homopolymer which is a by-product, and the production method is complicated. It cannot be introduced, and the vinyl monomer is polymerized and added to the fiber surface in the form of a branch, which increases the weight per unit area of the nonwoven fabric and decreases the air permeability. There is a strong demand for a hydrophilization technique for introducing a carboxylic acid group into a nonwoven fabric, which can easily control the quality of the production process in place of the conventional graft polymerization method.
【０００６】[0006]
【発明が解決しようとする課題】本発明は上記の技術課
題や問題点に鑑みてなされたものであり、その目的とす
るところは、ポリオレフィン系不織布にカルボキシル基
を導入し親水化する技術において、親水性および保液性
に優れ、且つ品質制御が容易で簡素な工程で製造可能な
アルカリ電池用セパレ−タを提供するものである。SUMMARY OF THE INVENTION The present invention has been made in view of the above technical problems and problems, and an object of the present invention is to provide a technique for introducing a carboxyl group into a polyolefin-based nonwoven fabric to make it hydrophilic. An object of the present invention is to provide a separator for an alkaline battery which is excellent in hydrophilicity and liquid retention, easy to control quality, and can be manufactured by a simple process.
【０００７】特に、電池の高エネルギ−密度化に対して
は、電池容量とは無関係なセパレ−タの占有体積を極限
まで削減しなければならず、セパレ−タの薄型化が不可
欠となってきている。しかしながら、従来のグラフト重
合法では、適正な親水性・保液性を得るにはグラフト率
５〜１５重量％を要し、しかも繊維表面に枝状ポリマ−
として付加するので、基布自体の目付量の増大に加えて
厚み増加を伴う。そのため、所要のセパレ−タ（目付、
厚さ）を得るには、より低目付のより薄い不織布を基布
として用いる必要があり、セパレ−タ厚さとして０．１
２ｍｍが限界となっている。In particular, in order to increase the energy density of the battery, the volume occupied by the separator irrespective of the battery capacity must be reduced to the utmost, and it is indispensable to reduce the thickness of the separator. ing. However, in the conventional graft polymerization method, a graft ratio of 5 to 15% by weight is required to obtain appropriate hydrophilicity and liquid retention, and the fiber surface has a branched polymer.
Therefore, in addition to an increase in the basis weight of the base cloth itself, an increase in thickness is accompanied. Therefore, required separators (basis weight,
In order to obtain (thickness), it is necessary to use a thinner nonwoven fabric having a lower basis weight as a base cloth.
2 mm is the limit.
【０００８】本発明は、図１に示すように、アクリル酸
のグラフト重合法とは異なり、カルボキシル基のみを高
分子繊維の主鎖に付加するものであり、基布の特性を損
なうことなく親水化可能なために、セパレ−タの薄型化
が容易であり、電池の高エネルギ−密度化対応の親水性
に優れたポリオレフィン系の薄型セパレ−タを提供でき
るものである。In the present invention, as shown in FIG. 1, unlike the graft polymerization method of acrylic acid, only a carboxyl group is added to the main chain of the polymer fiber, and the hydrophilicity is maintained without impairing the properties of the base fabric. Therefore, it is easy to make the separator thinner, and it is possible to provide a polyolefin thin separator excellent in hydrophilicity and capable of increasing the energy density of the battery.
【０００９】[0009]
【課題を解決するための手段】本発明は上記目的を達成
するために、分子構造中に炭素・水素（ＣＨ）結合を持
つ高分子材料から構成されるセパレ−タにおいて、該高
分子材料を、塩化オキサリル〔（ＣＯＣｌ）2 〕を含む
反応ガス中にて、あるいは塩化オキサリルを含有した状
態にて、活性エネルギ−線の照射下で処理し、水により
加水分解することでカルボキシル基を導入することを特
徴とするアルカリ電池用セパレータである。In order to achieve the above object, the present invention provides a separator comprising a polymer material having a carbon-hydrogen (CH) bond in a molecular structure. In a reaction gas containing oxalyl chloride [(COCl) 2 ], or in a state containing oxalyl chloride, it is treated under irradiation with active energy rays, and the carboxyl group is introduced by hydrolysis with water. It is a separator for alkaline batteries characterized by the above-mentioned.
【００１０】前記反応ガスは主成分である塩化オキサリ
ルと不活性ガスとの混合ガスであり、活性エネルギ−線
が紫外線からなる紫外光である。The reaction gas is a mixed gas of oxalyl chloride as a main component and an inert gas, and the active energy ray is ultraviolet light composed of ultraviolet rays.
【００１１】前記高分子材料は、ポリオレフィン系繊維
の不織布、織布あるいは多孔性のポリオレフィン・フィ
ルムである。The polymer material is a non-woven fabric, a woven fabric, or a porous polyolefin film of a polyolefin fiber.
【００１２】また、本発明は、正極と負極がセパレ−タ
を介して構成されるアルカリ電池において、該セパレ−
タが分子構造中に炭素・水素（ＣＨ）結合を持つ高分子
材料から構成され、該高分子材料を、塩化オキサリル
〔（ＣＯＣｌ）2 〕を含む反応ガス中にて、あるいは塩
化オキサリルを含有した状態にて、活性エネルギ−線の
照射下で処理し、水により加水分解することでカルボキ
シル基を導入したことを特徴とするアルカリ電池であ
る。Further, the present invention relates to an alkaline battery in which a positive electrode and a negative electrode are formed via a separator.
Is composed of a polymer material having a carbon-hydrogen (CH) bond in the molecular structure, and the polymer material is contained in a reaction gas containing oxalyl chloride [(COCl) 2 ] or containing oxalyl chloride. An alkaline battery characterized in that it is treated under irradiation of an active energy ray in a state and hydrolyzed with water to introduce a carboxyl group.
【００１３】前記セパレ−タの基布はポリオレフィン系
不織布であり、そのイオン交換能はカリウムのイオン交
換量にして０．０２〜０．２ミリ当量／ｇ、通気度（透
気度）が６〜３０ｃｃ／ｃｍ2 ／秒である。The base fabric of the separator is a polyolefin-based nonwoven fabric, and has an ion exchange capacity of 0.02 to 0.2 meq / g in terms of potassium ion exchange capacity and an air permeability (air permeability) of 6%. ３０30 cc / cm 2 / sec.
【００１４】[0014]
【発明の実施の形態】本発明は、炭化水素構造を持つ高
分子材料から構成されるセパレ−タ基布を、 塩化オキサリルを含む反応ガス中にて、あるいは塩化
オキサリルを含有させた状態にて、活性エネルギ−線の
照射下で処理して、クロロカルボニル化した後に、水
で加水分解してカルボキシル基に変換し、親水化するも
のである。の反応は、次式に示すように、気相での光
化学反応であるので、セパレ−タ基布の形状を維持した
状態で処理することが可能であり、基布の表面のみなら
ず内部にまで均一に極性基を導入することができる。BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a method of separating separator base cloth composed of a polymer material having a hydrocarbon structure in a reaction gas containing oxalyl chloride or in a state containing oxalyl chloride. Chlorocarbonylation by irradiation with active energy rays, and then hydrolyze with water to convert to carboxyl groups and hydrophilize. Is a photochemical reaction in the gas phase, as shown in the following formula, so that it is possible to perform the treatment while maintaining the shape of the separator base cloth, and not only on the surface of the base cloth but also inside. The polar group can be introduced uniformly up to the maximum.
【００１５】 塩化オキサリル〔（ＣＯＣｌ）2 〕は、沸点６３℃の常
温で液体の化合物であり、高い蒸気圧を持つため気相で
の常圧処理が容易であり、また、高分子材料を浸漬する
ことで容易に塩化オキサリルを含有させることができ
る。反応ガスとしては、塩化オキサリルと窒素、アルゴ
ン、ヘリウムなどの不活性ガスとの混合気体が望まし
い。また、活性エネルギ−線としては、Ｘ線や電子線な
どが使用できるが、紫外線からなる紫外光が最も好まし
い。[0015] Oxalyl chloride [(COCl) 2 ] is a compound that is liquid at room temperature with a boiling point of 63 ° C. and has a high vapor pressure, so that it can be easily treated at normal pressure in the gas phase. Oxalyl chloride can be easily contained. As the reaction gas, a mixed gas of oxalyl chloride and an inert gas such as nitrogen, argon, and helium is desirable. X-rays and electron beams can be used as the active energy rays, but ultraviolet rays composed of ultraviolet rays are most preferable.
【００１６】クロロカルボニル化の導入量は、即ち最終
的にはカルボン酸基の導入量は、反応ガス中の塩化オキ
サリルの濃度や基布との接触時間を調整することで容易
に制御できる。The amount of chlorocarbonylation introduced, that is, the amount of carboxylic acid groups finally introduced, can be easily controlled by adjusting the concentration of oxalyl chloride in the reaction gas and the contact time with the substrate.
【００１７】高分子材料としては、ポリアミド、ポリビ
ニルアルコ−ル、ポリエステル、ポリプロピレン、ポリ
エチレンなどや、これらの共重合体などから構成される
不織布、織布、多孔性フィルムが適用される。特に、ニ
ッケル水素電池用セパレ−タの基布としては、ポリオレ
フィン系繊維の不織布が適しており、目付量：３０〜１
００ｇ／ｍ2 、厚さ：０．１〜０．３ｍｍ、通気度：６
〜３０ｃｃ／ｃｍ2 ／秒の範囲のものが用いられる。Examples of the polymer material include polyamide, polyvinyl alcohol, polyester, polypropylene, polyethylene, and the like, and nonwoven fabrics, woven fabrics, and porous films composed of copolymers thereof. In particular, a non-woven fabric of a polyolefin fiber is suitable as a base fabric of a separator for a nickel-metal hydride battery.
00 g / m 2 , thickness: 0.1-0.3 mm, air permeability: 6
Those having a range of ３０30 cc / cm 2 / sec are used.
【００１８】の反応は、次式に示すような加水分解反
応であり、前記のクロロカルボニル化したセパレ−タを
水中に浸漬し、カルボン酸基とするものである。また、
アルカリ水溶液中で処理してもよく、その場合には、ア
ルカリ塩となる。The reaction is a hydrolysis reaction represented by the following formula, in which the chlorocarbonylated separator is immersed in water to form a carboxylic acid group. Also,
The treatment may be carried out in an aqueous alkali solution, in which case it becomes an alkali salt.
【００１９】 Ｒ−ＣＯＣｌ＋Ｈ2 Ｏ → Ｒ−ＣＯＯＨ＋ＨＣｌ Ｒ−ＣＯＣｌ＋２ＫＯＨ → Ｒ−ＣＯＯＫ＋ＫＣｌ＋
Ｈ2 Ｏ アルカリ電池用セパレ−タとして充分な親水性を保持す
るには、イオン交換能が、カリウムのイオン交換量にし
て０．０２〜０．２ミリ当量／ｇの範囲であればよい。
０．０２ミリ当量／ｇ未満では親水性・保液性が乏し
く、０．２ミリ当量／ｇでほぼ反応が飽和し、それ以上
の付加は基布の目付量の増大や通気度の低下を生じる。R-COCl + H 2 O → R-COOH + HCl R-COCl + 2KOH → R-COOK + KCl +
Separator for H 2 O alkaline batteries - to keep a sufficient hydrophilicity as data, the ion exchange capacity may be in the range of 0.02 to 0.2 meq / g and an ion exchange capacity of potassium.
When the amount is less than 0.02 meq / g, the hydrophilicity and liquid retention are poor, and when the amount is 0.2 meq / g, the reaction is almost saturated. Occurs.
【００２０】このような本発明のセパレ−タは、親水性
および保液性に優れるために、アルカリ電池、例えば、
ニッケル・カドミウム電池、ニッケル水素電池、ニッケ
ル亜鉛電池、空気亜鉛電池、アルカリマンガン電池など
の１次電池および２次電池に適用した場合、長期にわた
って安定した性能を持続することができるものである。Such a separator of the present invention is excellent in hydrophilicity and liquid retention, and is therefore an alkaline battery, for example,
When applied to primary batteries and secondary batteries such as nickel-cadmium batteries, nickel-metal hydride batteries, nickel zinc batteries, air zinc batteries, and alkaline manganese batteries, stable performance can be maintained for a long period of time.
【００２１】以下に、本発明のセパレ−タの実施例を記
載するが、本発明はこれら実施例に限定されるものでは
ない。Hereinafter, embodiments of the separator of the present invention will be described, but the present invention is not limited to these embodiments.
【００２２】[0022]
【実施例】ポリオレフィン系繊維の不織布（厚さ０．１
０ｍｍ，目付量４０ｇ／ｍ2 ）を基布として、図２に示
すような装置を用いて、ガラス製の反応容器内に収容し
た後に、塩化オキサリルと乾燥窒素ガスの混合気体を常
圧下で反応容器内に導入し、高圧水銀灯（３００Ｗ）の
硫酸銅水溶液透過光（３６６ｎｍ）を照射して、クロロ
カルボニル化を行った。同処理は、浸漬によって塩化オ
キサリル液を含有させた基布を用いても同様であった。
クロロカルボニル化率は反応時間（光量子数）を変える
ことで調整した。一例を図３に示す。その後、クロロカ
ルボニル化した基布を、水に浸漬し加水分解し、カルボ
キシル基に変換し、アルカリ電池用セパレ−タを作製し
た。ここでは、ポリオレフィン系繊維の不織布として、
ポリプロピレンとポリエチレンからなる複合分割型繊維
を湿式抄造し水流絡合して作製したものを用いた。EXAMPLE A nonwoven fabric of a polyolefin fiber (having a thickness of 0.1
0 mm, a basis weight of 40 g / m 2 ) was placed in a glass reaction vessel using a device as shown in FIG. 2 and reacted with a mixed gas of oxalyl chloride and dry nitrogen gas under normal pressure. The mixture was introduced into a container, and irradiated with transmitted light (366 nm) of a copper sulfate aqueous solution from a high-pressure mercury lamp (300 W) to perform chlorocarbonylation. The same treatment was performed using a base fabric containing an oxalyl chloride solution by immersion.
The chlorocarbonylation rate was adjusted by changing the reaction time (photon number). An example is shown in FIG. Thereafter, the chlorocarbonylated base fabric was immersed in water and hydrolyzed to be converted into a carboxyl group, thereby producing a separator for an alkaline battery. Here, as a nonwoven fabric of polyolefin fiber,
A composite fiber made of polypropylene and polyethylene was prepared by wet papermaking and hydroentanglement.
【００２３】こうして得られたセパレ−タは、そのイオ
ン交換能が０．０２〜０．２ミリ当量／ｇの範囲におい
て、親水性および保液性に優れるが、０．０２ミリ当量
／ｇ未満ではアルカリ電解液の吸液速度が遅く、且つ保
液率が低下した。本発明のセパレ−タの代表的特性値を
表１に示す。The separator thus obtained is excellent in hydrophilicity and liquid retention when the ion exchange capacity is in the range of 0.02 to 0.2 meq / g, but less than 0.02 meq / g. In this case, the absorption rate of the alkaline electrolyte was low, and the retention rate was low. Table 1 shows typical characteristic values of the separator of the present invention.
【００２４】[0024]
【表１】 [Table 1]
【００２５】本発明セパレ−タの親水持続性を見るため
に、７モル／ｌのＫＯＨ水溶液中で８０℃にて３ケ月間
浸漬した後のイオン交換量を調べた。イオン交換量の低
下はほとんど認められず、親水性は持続されることがわ
かった。In order to observe the hydrophilicity persistence of the separator of the present invention, the amount of ion exchange after immersion in a 7 mol / l KOH aqueous solution at 80 ° C. for 3 months was examined. Almost no decrease in the ion exchange amount was observed, indicating that the hydrophilicity was maintained.
【００２６】次に、このセパレ−タを用いて円筒型密閉
式ニッケル水素電池を作製して性能評価した。正極に
は、９５％多孔度のニッケル繊維あるいは発泡状基板に
水酸化ニッケルを主成分とした活物質を充填し、所定の
寸法・厚みとしたニッケル電極を用いた。また、負極に
は、ＭｍＮｉＣｏＡｌＭｎの５元系の希土類系水素吸蔵
合金粉末に導電剤とバインダ−を混合してペ−スト状と
し、穿孔鋼板に塗布した後に、所定の寸法・厚みとした
水素吸蔵合金電極を用いた。これら正極と負極を前記セ
パレ−タを介して渦巻状に巻いて、電槽に挿入し、７モ
ル／ｌのＫＯＨ水溶液を電解液として注液した後に、封
口・密閉してＡＡサイズ電池を作製した。比較例とし
て、従来のナイロンセパレ−タおよびアニオン系界面活
性剤にて処理したポリオレフィン系不織布をそれぞれ用
いて前記と同様の電池を作製した。本発明電池と比較電
池の温度４５℃での寿命特性を図４に示す。ナイロンセ
パレ−タおよび界面活性剤処理セパレ−タを使用した電
池は早期に容量低下を来したのに対して、本発明セパレ
−タ使用電池は良好な特性を示した。電池を解体してセ
パレ−タを調べたところ、ナイロンセパレ−タは酸化分
解し短繊維化しており、界面活性剤処理セパレ−タは親
水性および保液性の低下が見られ電気抵抗が著しく増大
していた。本発明セパレ−タは初期と同様の親水性、保
液性、イオン交換量を保持しており、劣化はほとんど認
められなかった。Next, a cylindrical sealed nickel-metal hydride battery was manufactured using this separator, and its performance was evaluated. For the positive electrode, a nickel electrode having a predetermined size and thickness by filling a 95% porous nickel fiber or a foamed substrate with an active material mainly containing nickel hydroxide was used. Also, the negative electrode is made of a pentagonal rare earth-based hydrogen storage alloy powder of MmNiCoAlMn mixed with a conductive agent and a binder to form a paste, applied to a perforated steel sheet, and then formed into a predetermined size and thickness. An alloy electrode was used. The positive electrode and the negative electrode are spirally wound through the separator, inserted into a battery case, injected with a 7 mol / l KOH aqueous solution as an electrolytic solution, and then sealed and sealed to produce an AA size battery. did. As comparative examples, batteries similar to those described above were produced using a conventional nylon separator and a polyolefin-based nonwoven fabric treated with an anionic surfactant, respectively. FIG. 4 shows the life characteristics of the battery of the present invention and the comparative battery at a temperature of 45 ° C. Batteries using the nylon separator and the surfactant-treated separator rapidly decreased in capacity, whereas the batteries using the separator of the present invention showed good characteristics. When the battery was disassembled and the separator was examined, the nylon separator was oxidized and decomposed into short fibers, and the surfactant-treated separator exhibited a decrease in hydrophilicity and liquid retention, and the electrical resistance was remarkable. Was growing. The separator of the present invention retained the same hydrophilicity, liquid retaining property and ion exchange amount as in the initial stage, and hardly any deterioration was observed.
【００２７】また、電池の容量保持特性においても、本
発明セパレ−タの優位性が認められた。４５℃にて１４
日間放置後の容量保持率は、ナイロンセパレ−タ使用電
池では３３％、本発明セパレ−タ使用電池では７２％で
あり、本発明セパレ−タはニッケル水素電池の自己放電
を抑制する効果を合わせ持つことがわかった。Also, the superiority of the separator of the present invention was recognized in the capacity retention characteristics of the battery. 14 at 45 ° C
The capacity retention after standing for a day is 33% for the battery using the nylon separator and 72% for the battery using the separator of the present invention. The separator of the present invention has the effect of suppressing the self-discharge of the nickel-metal hydride battery. I found it to have.
【００２８】[0028]
【発明の効果】以上のように、本発明によれば、ポリオ
レフィン系不織布あるいは多孔性のポリオレフィンフィ
ルムを塩化オキサリルの光化学反応にてクロロカルボニ
ル化してカルボキシル基を導入するという簡素な製造工
程にて、親水性に優れた高エネルギ−密度対応の薄型セ
パレ−タが作製可能となり、寿命や容量保持性に優れた
アルカリ電池を提供できるものである。As described above, according to the present invention, a polyolefin-based nonwoven fabric or a porous polyolefin film is chlorocarbonylated by a photochemical reaction of oxalyl chloride to introduce a carboxyl group. A thin separator with high hydrophilicity and high energy density can be manufactured, and an alkaline battery having excellent life and capacity retention can be provided.
【図１】本発明とグラフト重合法の分子構造の模式図で
ある。FIG. 1 is a schematic view of a molecular structure of the present invention and a graft polymerization method.
【図２】本発明によるクロロカルボニル化反応装置の概
略図である。FIG. 2 is a schematic view of a chlorocarbonylation reactor according to the present invention.
【図３】本発明におけるセパレータのイオン交換量と反
応時間との関係図である。FIG. 3 is a diagram showing the relationship between the ion exchange amount of the separator and the reaction time in the present invention.
【図４】本発明電池と比較電池の温度４５℃での寿命特
性図である。FIG. 4 is a life characteristic diagram of a battery of the present invention and a comparative battery at a temperature of 45 ° C.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 押谷 政彦 大阪府高槻市古曽部町２丁目３番21号 株 式会社ユアサコーポレーション内 (72)発明者 立花 一弘 兵庫県神戸市垂水区本多聞６丁目23番５号 (72)発明者 三木 定雄 京都府京都市左京区上高野山ノ橋町20−１ Ｆターム(参考） 5H021 BB09 BB15 CC02 EE02 EE04 HH00 HH07 5H024 AA02 AA03 AA11 CC02 DD09 EE09 FF09 HH00 5H028 AA05 BB10 EE06 HH00 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masahiko Oshiya 2-3-2, Furusobe-cho, Takatsuki-shi, Osaka Inside Yuasa Corporation (72) Inventor Kazuhiro Tachibana 6-23 Hondamon, Tarumizu-ku, Kobe-shi, Hyogo Prefecture No. 5 (72) Inventor Sadao Miki 20-1 Kamikoya Yamanohashicho, Sakyo-ku, Kyoto, Kyoto F-term (reference) 5H021 BB09 BB15 CC02 EE02 EE04 HH00 HH07 5H024 AA02 AA03 AA11 CC02 DD09 EE09 FF09 HH00 5H028 AA05 BB10 EE HH00
Claims (5)
持つ高分子材料から構成されるセパレ−タにおいて、該
高分子材料を、塩化オキサリル〔（ＣＯＣｌ）2 〕を含
む反応ガス中にて、あるいは塩化オキサリルを含有させ
た状態にて、活性エネルギ−線の照射下で処理し、水に
より加水分解することでカルボキシル基を導入したこと
を特徴とするアルカリ電池用セパレ−タ。1. A separator comprising a polymer material having a carbon-hydrogen (CH) bond in a molecular structure, wherein the polymer material is introduced into a reaction gas containing oxalyl chloride [(COCl) 2 ]. A separator for alkaline batteries, characterized in that the separator is treated under irradiation with active energy rays in the presence of oxalyl chloride or hydrolyzed with water to introduce carboxyl groups.
リルと不活性ガスとの混合ガスであり、活性エネルギ−
線が紫外線からなる紫外光であることを特徴とする請求
項１記載のアルカリ電池用セパレ−タ。2. The method according to claim 1, wherein the reactive gas is a mixed gas of oxalyl chloride, which is a main component, and an inert gas.
2. The separator for an alkaline battery according to claim 1, wherein the line is ultraviolet light composed of ultraviolet rays.
維の不織布、織布あるいは多孔性のポリオレフィンフィ
ルムであることを特徴とする請求項１記載のアルカリ電
池用セパレ−タ。3. The separator for an alkaline battery according to claim 1, wherein the polymer material is a nonwoven fabric, a woven fabric, or a porous polyolefin film of polyolefin fibers.
れるアルカリ電池において、該セパレ−タが分子構造中
に炭素・水素（ＣＨ）結合を持つ高分子材料から構成さ
れ、該高分子材料を、塩化オキサリル〔（ＣＯＣ
ｌ）2 〕を含む反応ガス中にて、あるいは塩化オキサリ
ルを含有させた状態にて、活性エネルギ−線の照射下で
処理し、水により加水分解することでカルボキシル基を
導入したことを特徴とするアルカリ電池。4. An alkaline battery in which a positive electrode and a negative electrode are formed via a separator, wherein the separator is formed of a polymer material having a carbon-hydrogen (CH) bond in a molecular structure. Oxalyl chloride [(COC
l) In a reaction gas containing 2 ] or in a state containing oxalyl chloride, a carboxyl group is introduced by treatment under irradiation with active energy rays and hydrolysis with water. Alkaline batteries.
の不織布であり、そのイオン交換能はカリウムのイオン
交換量にして０．０２〜０．２ミリ当量／ｇであり、通
気度が６〜３０ｃｃ／ｃｍ2 ／秒であることを特徴とす
る請求項４記載のアルカリ電池。5. The separator is a nonwoven fabric of a polyolefin fiber, and has an ion exchange capacity of 0.02 to 0.2 meq / g in terms of potassium ion exchange quantity, and a gas permeability of 6 to 30 cc. 5. The alkaline battery according to claim 4, wherein the alkaline battery has a ratio of / cm 2 / sec.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25390999A JP3742256B2 (en) | 1999-09-08 | 1999-09-08 | Method for producing separator for alkaline battery and method for producing alkaline battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25390999A JP3742256B2 (en) | 1999-09-08 | 1999-09-08 | Method for producing separator for alkaline battery and method for producing alkaline battery |
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| Publication Number | Publication Date |
|---|---|
| JP2001076705A true JP2001076705A (en) | 2001-03-23 |
| JP3742256B2 JP3742256B2 (en) | 2006-02-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006265451A (en) * | 2005-03-25 | 2006-10-05 | Kyoto Institute Of Technology | Magnetic microsphere having functional group on surface |
| JP2006265452A (en) * | 2005-03-25 | 2006-10-05 | Kyoto Institute Of Technology | Method for modifying spherical polymer material by liquid-phase chemical reaction and modified spherical polymer material |
-
1999
- 1999-09-08 JP JP25390999A patent/JP3742256B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006265451A (en) * | 2005-03-25 | 2006-10-05 | Kyoto Institute Of Technology | Magnetic microsphere having functional group on surface |
| JP2006265452A (en) * | 2005-03-25 | 2006-10-05 | Kyoto Institute Of Technology | Method for modifying spherical polymer material by liquid-phase chemical reaction and modified spherical polymer material |
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| Publication number | Publication date |
|---|---|
| JP3742256B2 (en) | 2006-02-01 |
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