JP6394203B2 - Capacitor electrode for lead acid battery - Google Patents
Capacitor electrode for lead acid battery Download PDFInfo
- Publication number
- JP6394203B2 JP6394203B2 JP2014179922A JP2014179922A JP6394203B2 JP 6394203 B2 JP6394203 B2 JP 6394203B2 JP 2014179922 A JP2014179922 A JP 2014179922A JP 2014179922 A JP2014179922 A JP 2014179922A JP 6394203 B2 JP6394203 B2 JP 6394203B2
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- JP
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- Prior art keywords
- lead
- capacitor
- capacitor electrode
- layer
- adhesive
- 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.)
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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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、鉛蓄電池に用いられる鉛蓄電池用キャパシタ電極に関するものである。 The present invention relates to a capacitor electrode for a lead storage battery used in a lead storage battery.
正極活物質として二酸化鉛、負極活物質として鉛を使用し、電解液に硫酸を使用した鉛蓄電池は、他の二次電池と比較して安価で大電流放電に適することから多くの産業にて使用されており、リチウムイオン二次電池等の高容量二次電池が隆盛を誇る今日もその重要性は失われておらず、現在でも鉛蓄電池性能向上の検討が精力的に行われている。 Lead-acid batteries that use lead dioxide as the positive electrode active material, lead as the negative electrode active material, and sulfuric acid as the electrolyte are inexpensive and suitable for high-current discharge in many industries compared to other secondary batteries. Even today, the importance of high-capacity secondary batteries such as lithium-ion secondary batteries is prominent, and their importance has not been lost.
近年、鉛蓄電池の長所である短時間の大電流放電特性の向上、ならびに短所である放電深度を大きくした場合のサイクル特性低下の改善に関して、活性炭を使用した技術が報告されている。 In recent years, a technique using activated carbon has been reported regarding the improvement of short-time high-current discharge characteristics, which is an advantage of a lead-acid battery, and the improvement of cycle characteristics deterioration when the discharge depth is increased.
例えば、鉛蓄電池の充電速度を速めたり、放電深度の改善のために正極と負極との間にキャパシタ層を設けたりすることが行われている。特許文献１においては、鉛極板上にキャパシタ層形成用のスラリーを塗工することにより、キャパシタ層を形成している。また、特許文献２においては、（ｉ）支持体として用いられるＰＥＴ（ポリエチレンテレフタレート）フィルム上にキャパシタ層を乾式法により成形し、鉛極板上にキャパシタ層を圧着してからＰＥＴフィルムを剥離する方法、（ｉｉ）支持体として用いられるＰＥＴフィルム上にキャパシタ層を乾式法により成形してからＰＥＴフィルムを剥離し、鉛極板上にキャパシタ層を圧着する方法が開示されている。 For example, increasing the charging speed of a lead storage battery or providing a capacitor layer between a positive electrode and a negative electrode in order to improve the depth of discharge. In Patent Document 1, a capacitor layer is formed by applying a slurry for forming a capacitor layer on a lead electrode plate. In Patent Document 2, (i) a capacitor layer is formed on a PET (polyethylene terephthalate) film used as a support by a dry method, the capacitor layer is pressure-bonded on a lead electrode plate, and then the PET film is peeled off. Method (ii) A method of forming a capacitor layer on a PET film used as a support by a dry method, peeling the PET film, and pressing the capacitor layer on a lead electrode plate is disclosed.
しかし、特許文献１のようにスラリーを塗工し乾燥させると、バインダーのマイグレーションが起こるため、得られる鉛キャパシタ蓄電池の抵抗が増加する。また、特許文献２の場合、（ｉ）のように鉛電極に圧着後にＰＥＴフィルムを剥離するとキャパシタ層の強度が弱くなり、さらに強度を保つためにＰＥＴフィルムをキャパシタ層に密着させたままにするとＰＥＴフィルムが抵抗成分となるため、得られる鉛キャパシタ蓄電池の抵抗が増加する。また、抵抗が増加しすぎると容量も低下する。さらに、（ｉｉ）のようにキャパシタ層を乾式法により成形して後にＰＥＴフィルムを剥離し、鉛極板上にキャパシタ層を圧着する場合には、支持体がない状態で鉛極板上にキャパシタ層を圧着することとなるため、キャパシタ層の強度が弱くなる。 However, when the slurry is applied and dried as in Patent Document 1, binder migration occurs, and thus the resistance of the obtained lead capacitor storage battery increases. Further, in the case of Patent Document 2, if the PET film is peeled off after being pressure-bonded to the lead electrode as in (i), the strength of the capacitor layer becomes weak, and if the PET film is kept in close contact with the capacitor layer in order to maintain further strength. Since the PET film becomes a resistance component, the resistance of the obtained lead capacitor storage battery increases. Further, if the resistance increases too much, the capacity also decreases. Further, when the capacitor layer is formed by a dry method as in (ii) and the PET film is peeled off and the capacitor layer is pressure-bonded on the lead electrode plate, the capacitor is formed on the lead electrode plate without a support. Since the layers are pressure-bonded, the strength of the capacitor layer is weakened.
本発明の目的は、強度に優れ、抵抗が小さく、さらに容量の大きい鉛蓄電池用キャパシタ電極を提供することである。 The objective of this invention is providing the capacitor electrode for lead acid batteries which is excellent in intensity | strength, has small resistance, and is also large capacity | capacitance.
本発明者は、上記課題を解決するために鋭意検討の結果、鉛蓄電池用キャパシタ電極に所定の支持体を用いることにより、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies in order to solve the above problems, the present inventor has found that the above object can be achieved by using a predetermined support for the capacitor electrode for a lead storage battery, and has completed the present invention.
即ち、本発明によれば、
（１） 接着剤が塗布された支持体と、キャパシタ電極活物質、導電材および結着剤を含む複合粒子を乾式成形したキャパシタ層とを含む鉛蓄電池用キャパシタ電極であり、前記支持体の接着力が０．２Ｎ／ｍ以上であり、厚さが１５μｍ以上１５０μｍ未満である鉛蓄電池用キャパシタ電極、
（２） 前記支持体と前記キャパシタ層の間に接着剤層が存在する（１）の鉛蓄電池用キャパシタ電極、
（３） 前記複合粒子の平均粒子径が５０μｍ以上３５０μｍ未満である（１）または（２）の鉛蓄電池用キャパシタ電極、
（４） 前記支持体が、繊維状であることを特徴とする（１）〜（３）の何れかに記載の鉛蓄電池用キャパシタ電極、
（５） 前記接着剤が、電解液に溶解することを特徴とする（１）〜（４）の何れかに記載の鉛蓄電池用キャパシタ電極
が提供される。
That is, according to the present invention,
(1) A lead-acid battery capacitor electrode comprising: a support coated with an adhesive; and a capacitor layer obtained by dry-molding composite particles including a capacitor electrode active material, a conductive material and a binder, and bonding the support A lead-acid battery capacitor electrode having a force of 0.2 N / m or more and a thickness of 15 μm or more and less than 150 μm;
(2) The capacitor electrode for a lead storage battery according to (1), wherein an adhesive layer is present between the support and the capacitor layer,
(3) The capacitor electrode for a lead storage battery according to (1) or (2), wherein an average particle diameter of the composite particles is 50 μm or more and less than 350 μm,
(4) The capacitor electrode for a lead storage battery according to any one of (1) to (3), wherein the support is fibrous.
(5) The lead-acid battery capacitor electrode according to any one of (1) to (4), wherein the adhesive is dissolved in an electrolytic solution.
本発明によれば、強度に優れ、抵抗が小さく、さらに容量の大きい鉛蓄電池用キャパシタ電極が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the capacitor electrode for lead acid batteries which is excellent in intensity | strength, has small resistance, and is large in capacity is provided.
以下、本発明の実施の形態に係る鉛蓄電池用キャパシタ電極について説明する。本発明の鉛蓄電池用キャパシタ電極は、接着剤が塗布された支持体と、キャパシタ電極活物質、導電材および結着剤を含む複合粒子を乾式成形したキャパシタ層とを含む鉛蓄電池用キャパシタ電極であり、前記支持体の接着力が０．２Ｎ／ｍ以上であり、厚さが１５μｍ以上１５０μｍ未満である。 Hereinafter, a capacitor electrode for a lead storage battery according to an embodiment of the present invention will be described. A capacitor electrode for a lead storage battery according to the present invention is a capacitor electrode for a lead storage battery including a support coated with an adhesive and a capacitor layer obtained by dry molding composite particles including a capacitor electrode active material, a conductive material and a binder. Yes, the adhesive strength of the support is 0.2 N / m or more, and the thickness is 15 μm or more and less than 150 μm.
（キャパシタ層）
本発明に用いるキャパシタ層は、キャパシタ電極活物質、導電材および結着剤を含む複合粒子を乾式成形することにより得られる。
(Capacitor layer)
The capacitor layer used in the present invention can be obtained by dry-molding composite particles containing a capacitor electrode active material, a conductive material and a binder.
（キャパシタ電極活物質）
本発明に用いるキャパシタ電極活物質は、電極内で電子の受け渡しをする物質である。
本発明に用いるキャパシタ電極活物質としては、電気二重層キャパシタ用電極に用いる電極活物質、具体的には、炭素の同素体が用いられる。炭素の同素体の具体例としては、活性炭、ポリアセン、カーボンウィスカ及びグラファイト等が挙げられ、これらの粉末または繊維を使用することができる。好ましい電極活物質は活性炭であり、具体的にはフェノール樹脂、レーヨン、アクリロニトリル樹脂、石油ピッチ、およびヤシ殻等を原料とする活性炭が好ましい。また、これらの炭素の同素体として、フェノール樹脂等を炭化させ、必要に応じて賦活させ、次いで粉砕したものを用いてもよい。
(Capacitor electrode active material)
The capacitor electrode active material used in the present invention is a substance that transfers electrons in the electrode.
As the capacitor electrode active material used in the present invention, an electrode active material used for an electric double layer capacitor electrode, specifically, an allotrope of carbon is used. Specific examples of the allotrope of carbon include activated carbon, polyacene, carbon whisker, and graphite, and these powders or fibers can be used. A preferable electrode active material is activated carbon, and specifically, activated carbon made from phenol resin, rayon, acrylonitrile resin, petroleum pitch, coconut shell, or the like is preferable. In addition, as an allotrope of these carbons, a carbonized phenol resin or the like, activated as necessary, and then pulverized may be used.
キャパシタ電極活物質の体積平均粒子径は、通常０．１〜１００μｍ、好ましくは１〜５０μｍ、更に好ましくは５〜２０μｍである。 The volume average particle diameter of the capacitor electrode active material is usually 0.1 to 100 μm, preferably 1 to 50 μm, and more preferably 5 to 20 μm.
キャパシタ電極活物質の比表面積は、３０ｍ2／ｇ以上、好ましくは５００〜５，０００ｍ2／ｇ、より好ましくは１，０００〜３，０００ｍ2／ｇである。キャパシタ電極活物質の比表面積が大きいほど得られるキャパシタ層の密度は小さくなる傾向があるので、キャパシタ電極活物質を適宜選択することで、所望の密度を有するキャパシタ層を得ることができる。 The specific surface area of the capacitor electrode active material, 30 m 2 / g or more, preferably 500~5,000m 2 / g, more preferably 1,000~3,000m 2 / g. Since the density of the obtained capacitor layer tends to decrease as the specific surface area of the capacitor electrode active material increases, a capacitor layer having a desired density can be obtained by appropriately selecting the capacitor electrode active material.
（導電材）
本発明に用いる導電材は、導電性を有し、電気二重層を形成し得る細孔を有さない粒子状の炭素の同素体からなり、具体的には、ファーネスブラック、アセチレンブラック、及びケッチェンブラック（アクゾノーベル ケミカルズ ベスローテン フェンノートシャップ社の登録商標）などのカーボンブラックが挙げられる。これらの中でも、アセチレンブラックおよびケッチェンブラックが好ましい。
(Conductive material)
The conductive material used in the present invention is composed of an allotrope of particulate carbon that has conductivity and does not have pores that can form an electric double layer. Specifically, furnace black, acetylene black, and ketjen And carbon black such as black (registered trademark of Akzo Nobel Chemicals Besloten Fennaut Shap). Among these, acetylene black and ketjen black are preferable.
本発明に用いる導電材の体積平均粒子径は、キャパシタ電極活物質の体積平均粒子径よりも小さいものが好ましく、より少ない使用量で高い導電性が得られる観点から、通常０．００１〜１０μｍ、好ましくは０．００５〜５μｍ、より好ましくは０．０１〜１μｍである。これらの導電材は、単独でまたは二種類以上を組み合わせて用いることができる。 The volume average particle diameter of the conductive material used in the present invention is preferably smaller than the volume average particle diameter of the capacitor electrode active material, and is usually 0.001 to 10 μm from the viewpoint of obtaining high conductivity with a smaller amount used. Preferably it is 0.005-5 micrometers, More preferably, it is 0.01-1 micrometer. These conductive materials can be used alone or in combination of two or more.
導電材の量は、得られる鉛蓄電池用キャパシタ電極の容量を高く且つ内部抵抗を低くすることができる観点から、キャパシタ電極活物質１００重量部に対して通常０．１〜５０重量部、好ましくは０．５〜１５重量部、より好ましくは１〜１０重量部である。導電材の量が多すぎると、得られる鉛蓄電池用キャパシタ電極の容量が少なくなり、導電材の量が少なすぎると、得られる鉛蓄電池用キャパシタ電極の内部抵抗が高くなる。 The amount of the conductive material is usually 0.1 to 50 parts by weight, preferably 100 to 50 parts by weight, preferably 100 parts by weight of the capacitor electrode active material, from the viewpoint of increasing the capacity of the obtained lead storage battery capacitor electrode and reducing the internal resistance. 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight. If the amount of the conductive material is too large, the capacity of the obtained lead storage battery capacitor electrode is reduced, and if the amount of the conductive material is too small, the internal resistance of the obtained lead storage battery capacitor electrode is increased.
（結着剤）
キャパシタ層に用いる結着剤は、キャパシタ電極活物質や上記導電材を相互に結着させることができる化合物であれば特に制限はない。結着剤としては、溶媒に分散する性質のある分散型結着剤と、溶媒に溶解する溶解型結着剤とが挙げられる。結着剤は単独もしくは2種類以上用いることができる。分散型結着剤として、例えば、フッ素重合体、ジエン重合体、アクリル重合体、ポリイミド、ポリアミド、ポリウレタン重合体等の高分子化合物が挙げられ、ジエン重合体、アクリル重合体が好ましい。
(Binder)
The binder used for the capacitor layer is not particularly limited as long as it is a compound that can bind the capacitor electrode active material and the conductive material to each other. Examples of the binder include a dispersion-type binder having a property of being dispersed in a solvent and a dissolution-type binder that is soluble in a solvent. Binders can be used alone or in combination of two or more. Examples of the dispersion-type binder include polymer compounds such as fluoropolymers, diene polymers, acrylic polymers, polyimides, polyamides, polyurethane polymers, and diene polymers and acrylic polymers are preferable.
ジエン重合体は、共役ジエンの単独重合体もしくは共役ジエンを含む単量体混合物を重合して得られる共重合体、またはそれらの水素添加物である。ジエン重合体の具体例としては、ポリブタジエンやポリイソプレンなどの共役ジエン単独重合体；カルボキシ変性されていてもよいスチレン・ブタジエン共重合体（ＳＢＲ）などの芳香族ビニル・共役ジエン共重合体；アクリロニトリル・ブタジエン共重合体（ＮＢＲ）などのシアン化ビニル・共役ジエン共重合体；水素化ＳＢＲ、水素化ＮＢＲ等が挙げられる。 The diene polymer is a homopolymer of a conjugated diene or a copolymer obtained by polymerizing a monomer mixture containing a conjugated diene, or a hydrogenated product thereof. Specific examples of the diene polymer include conjugated diene homopolymers such as polybutadiene and polyisoprene; aromatic vinyl / conjugated diene copolymers such as carboxy-modified styrene / butadiene copolymer (SBR); acrylonitrile -Vinyl cyanide * conjugated diene copolymers, such as a butadiene copolymer (NBR); Hydrogenated SBR, hydrogenated NBR, etc. are mentioned.
アクリル重合体は、アクリル酸エステルもしくはメタクリル酸エステルの単独重合体またはこれらと共重合可能な単量体を含む単量体混合物を重合して得られる共重合体である。前記共重合可能な単量体としては、アクリル酸、メタクリル酸、イタコン酸、フマル酸などの不飽和カルボン酸類；エチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、トリメチロールプロパントリアクリレートなどの２つ以上の炭素−炭素二重結合を有するカルボン酸エステル類；スチレン、クロロスチレン、ビニルトルエン、ｔ−ブチルスチレン、ビニル安息香酸、ビニル安息香酸メチル、ビニルナフタレン、クロロメチルスチレン、ヒドロキシメチルスチレン、α−メチルスチレン、ジビニルベンゼン等のスチレン系単量体；アクリルアミド、Ｎ−メチロールアクリルアミド、アクリルアミド−２−メチルプロパンスルホン酸などのアミド系単量体；アクリロニトリル、メタクリロニトリルなどのα，β−不飽和ニトリル化合物；エチレン、プロピレン等のオレフィン類；ブタジエン、イソプレン等のジエン系単量体；塩化ビニル、塩化ビニリデン等のハロゲン原子含有単量体；酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、安息香酸ビニル等のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、ブチルビニルエーテル等のビニルエーテル類；メチルビニルケトン、エチルビニルケトン、ブチルビニルケトン、ヘキシルビニルケトン、イソプロペニルビニルケトン等のビニルケトン類；Ｎ−ビニルピロリドン、ビニルピリジン、ビニルイミダゾール等の複素環含有ビニル化合物；β−ヒドロキシエチルアクリレート、β−ヒドロキシエチルメタクリレート等のヒドロキシアルキル基含有化合物等が挙げられる。 The acrylic polymer is a copolymer obtained by polymerizing a homopolymer of acrylic ester or methacrylic ester or a monomer mixture containing a monomer copolymerizable therewith. Examples of the copolymerizable monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, and fumaric acid; two or more carbons such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and trimethylolpropane triacrylate. -Carboxylic acid ester having a carbon double bond; styrene, chlorostyrene, vinyl toluene, t-butyl styrene, vinyl benzoic acid, vinyl benzoate methyl, vinyl naphthalene, chloromethyl styrene, hydroxymethyl styrene, α-methyl styrene, Styrene monomers such as divinylbenzene; Amide monomers such as acrylamide, N-methylolacrylamide, and acrylamide-2-methylpropane sulfonic acid; α, β-defect such as acrylonitrile and methacrylonitrile Japanese nitrile compounds; olefins such as ethylene and propylene; diene monomers such as butadiene and isoprene; monomers containing halogen atoms such as vinyl chloride and vinylidene chloride; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate Vinyl esters such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, etc .; Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, butyl vinyl ketone, hexyl vinyl ketone, isopropenyl vinyl ketone; N-vinyl pyrrolidone, vinyl Heterocycle-containing vinyl compounds such as pyridine and vinylimidazole; and hydroxyalkyl group-containing compounds such as β-hydroxyethyl acrylate and β-hydroxyethyl methacrylate.
これらのなかでも、キャパシタ電極活物質や導電材とともに複合粒子にして乾式成形を行う場合の強度の観点から、ジエン重合体を用いることが好ましく、アクリロニトリル・ブタジエン共重合体（以下、「ＮＢＲ」と記載することがある。）を用いることがより好ましい。また、前記アクリロニトリル・ブタジエン共重合体を用いる場合における結着剤中の１，３−ブタジエン単量体単位の比率は、４０〜７５重量％であることが好ましく、４５〜７５重量％であることがより好ましい。また、アクリロニトリル・ブタジエン共重合体を用いる場合における結着剤中のアクリロニトリル単量体単位の比率は、２０〜６０重量％であることが好ましく、２０〜４５重量％であることがより好ましい。 Among these, it is preferable to use a diene polymer from the viewpoint of strength when dry forming a composite particle together with a capacitor electrode active material and a conductive material, and an acrylonitrile-butadiene copolymer (hereinafter referred to as “NBR”). It is more preferable to use. The ratio of the 1,3-butadiene monomer unit in the binder in the case of using the acrylonitrile-butadiene copolymer is preferably 40 to 75% by weight, and 45 to 75% by weight. Is more preferable. Further, when the acrylonitrile-butadiene copolymer is used, the ratio of the acrylonitrile monomer unit in the binder is preferably 20 to 60% by weight, and more preferably 20 to 45% by weight.
アクリロニトリル・ブタジエン共重合体は、１，３−ブタジエンおよびアクリロニトリルの他に、さらにアクリル酸やメタクリル酸等の上述の不飽和カルボン酸類の単量体単位を含むことが好ましい。不飽和カルボン酸類としては、メタクリル酸が好ましい。この場合において、結着剤中の、不飽和カルボン酸類の単量体の比率は、下限は３重量％以上であることが好ましく、５重量％以上であることがより好ましく、上限は３９重量％以下であることが好ましく、３５重量％以下であることがより好ましい。 The acrylonitrile-butadiene copolymer preferably further contains monomer units of the aforementioned unsaturated carboxylic acids such as acrylic acid and methacrylic acid in addition to 1,3-butadiene and acrylonitrile. As unsaturated carboxylic acids, methacrylic acid is preferable. In this case, the lower limit of the ratio of the unsaturated carboxylic acid monomer in the binder is preferably 3% by weight or more, more preferably 5% by weight or more, and the upper limit is 39% by weight. Or less, more preferably 35% by weight or less.
本発明に用いる分散型結着剤のガラス転移温度（以下、「Ｔｇ」という）は、好ましくは−４０〜＋４０℃、より好ましくは−３０〜＋３０℃である。結着剤のＴｇが高すぎると得られるキャパシタ層が柔軟性に劣り、結着剤のＴｇが低すぎるとキャパシタ層の成形が困難となる。また、分散型結着剤は融点を有するものであってもよい。 The glass transition temperature (hereinafter referred to as “Tg”) of the dispersion-type binder used in the present invention is preferably −40 to + 40 ° C., more preferably −30 to + 30 ° C. When the Tg of the binder is too high, the obtained capacitor layer is inferior in flexibility, and when the Tg of the binder is too low, it is difficult to mold the capacitor layer. Further, the dispersion type binder may have a melting point.
分散型結着剤の形状は、結着性の向上、電極の容量の低下、および内部抵抗の増大を最小限に抑えるために、粒子状であることが最も好ましく、例えば、ラテックスのような結着剤樹脂の粒子が溶媒に分散した状態のものや、このような分散液を乾燥して得られる粉末状のものが挙げられる。 The shape of the dispersion-type binder is most preferably particulate in order to minimize the increase in binding properties, decrease in electrode capacity, and increase in internal resistance, for example, a latex-like binder. Examples include those in which particles of the adhesive resin are dispersed in a solvent, and powders obtained by drying such a dispersion.
分散型結着剤の粒子径は特に限定されないが、体積平均粒子径で、１００〜５００ｎｍであることが好ましい。 The particle size of the dispersion-type binder is not particularly limited, but is preferably 100 to 500 nm in terms of volume average particle size.
分散型結着剤の製造方法は特に限定されず、所定の比率で各単量体を含む組成物を用いた乳化重合法、懸濁重合法、分散重合法または溶液重合法等の公知の重合法を採用することができる。中でも、乳化重合法で製造することが、分散型結着剤の粒子径の制御が容易であるので好ましい。特に水を主溶媒とした水系での重合法が好ましい。 The method for producing the dispersion-type binder is not particularly limited, and a known weight such as an emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method or a solution polymerization method using a composition containing each monomer at a predetermined ratio. Legal can be adopted. Among these, it is preferable to produce by an emulsion polymerization method because it is easy to control the particle size of the dispersion-type binder. In particular, an aqueous polymerization method using water as a main solvent is preferred.
分散型結着剤の量は、キャパシタ電極活物質１００重量部に対して通常２〜２０重量部、好ましくは３〜１５重量部、より好ましくは４〜１２重量部である。結着剤の量が多すぎると得られる鉛蓄電池用キャパシタ電極の内部抵抗が高くなり、結着剤の量が少なすぎると、得られる鉛蓄電池用キャパシタ電極の強度が不十分となる。 The amount of the dispersion-type binder is usually 2 to 20 parts by weight, preferably 3 to 15 parts by weight, and more preferably 4 to 12 parts by weight with respect to 100 parts by weight of the capacitor electrode active material. If the amount of the binder is too large, the internal resistance of the obtained lead storage battery capacitor electrode becomes high, and if the amount of the binder is too small, the strength of the resulting lead storage battery capacitor electrode becomes insufficient.
結着剤として、上述した溶解型結着剤を用いる場合に、その具体例としては、カルボキシメチルセルロース、メチルセルロース、エチルセルロースおよびヒドロキシプロピルセルロースなどのセルロース系ポリマー、ならびにこれらのアンモニウム塩またはアルカリ金属塩；ポリ（メタ）アクリル酸ナトリウムなどのポリ（メタ）アクリル酸塩；ポリビニルアルコール、変性ポリビニルアルコール、ポリエチレンオキシド；ポリビニルピロリドン、ポリカルボン酸、酸化スターチ、リン酸スターチ、カゼイン、各種変性デンプン、キチン、キトサン誘導体などが挙げられる。これらの溶解型結着剤は、それぞれ単独でまたは２種以上を組み合わせて使用でき、さらに、前述の分散型結着剤と組み合わせて用いることもできる。中でも、セルロース系ポリマーが好ましく、カルボキシメチルセルロースまたはそのアンモニウム塩もしくはアルカリ金属塩が特に好ましい。尚、溶解型結着剤は、キャパシタ電極活物質、導電材及び分散型結着剤を分散させる分散剤としての機能も有する場合があるため、その場合は分散剤として用いることもできる。 When the above-mentioned dissolution type binder is used as the binder, specific examples thereof include cellulosic polymers such as carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxypropyl cellulose, and ammonium salts or alkali metal salts thereof; Poly (meth) acrylates such as sodium (meth) acrylate; polyvinyl alcohol, modified polyvinyl alcohol, polyethylene oxide; polyvinyl pyrrolidone, polycarboxylic acid, oxidized starch, phosphate starch, casein, various modified starches, chitin, chitosan derivatives Etc. These soluble binders can be used alone or in combination of two or more, and can also be used in combination with the above-mentioned dispersion-type binder. Among these, a cellulose polymer is preferable, and carboxymethyl cellulose or an ammonium salt or an alkali metal salt thereof is particularly preferable. In addition, since a melt | dissolution type | mold binder may also have a function as a dispersing agent which disperse | distributes a capacitor electrode active material, a electrically conductive material, and a dispersion | distribution type binder, it can also be used as a dispersing agent in that case.
複合粒子中の溶解型結着剤の量は、複合粒子中の活性炭の重量に対して、好ましくは０．１重量％以上２０重量％未満、より好ましくは０．５重量％以上１０重量％未満、さらに好ましくは０．８重量％以上５重量％未満である。 The amount of the soluble binder in the composite particles is preferably 0.1% by weight or more and less than 20% by weight, more preferably 0.5% by weight or more and less than 10% by weight, based on the weight of the activated carbon in the composite particles. More preferably, it is 0.8 wt% or more and less than 5 wt%.
キャパシタ層は、さらに必要に応じてその他の添加剤を含有していてもよい。具体的には、後述するスラリーの電気的な安定性向上のため、アニオン性、カチオン性、ノニオン性、あるいはノニオニックアニオン等の両性の界面活性剤や、アミノカルボン酸系キレート化合物、ホスホン酸系キレート化合物、グルコン酸、クエン酸、リンゴ酸、酒石酸などのキレート化合物、前記溶解型結着剤以外の分散剤などが挙げられる。 The capacitor layer may further contain other additives as necessary. Specifically, in order to improve the electrical stability of the slurry described later, amphoteric surfactants such as anionic, cationic, nonionic or nonionic anions, aminocarboxylic acid chelate compounds, phosphonic acids Examples thereof include chelate compounds such as chelates, gluconic acid, citric acid, malic acid, and tartaric acid, and dispersants other than the above-mentioned soluble binder.
（キャパシタ層の製造方法）
本発明に用いるキャパシタ層は、キャパシタ電極活物質、導電材、結着剤および必要に応じて用いられるその他の成分とを含んでなる複合粒子を含む。また、キャパシタ層は、支持体上に複合粒子を乾式成形することにより得られる。
(Capacitor layer manufacturing method)
The capacitor layer used in the present invention includes composite particles including a capacitor electrode active material, a conductive material, a binder, and other components used as necessary. The capacitor layer can be obtained by dry-molding composite particles on a support.
乾式成形法は、キャパシタ電極活物質、結着剤及び導電材と、必要に応じて用いる前記任意成分とからなる複合粒子を調製し、これを支持体上にシート成形し、必要に応じてロール成形して得る方法であり、得られる鉛蓄電池用キャパシタ電極の容量を高く、且つ内部抵抗を低減できる点で好ましい。 In the dry molding method, composite particles comprising a capacitor electrode active material, a binder and a conductive material and the optional components used as necessary are prepared, formed into a sheet on a support, and rolled as necessary. This is a method obtained by molding, which is preferable in that the capacity of the obtained lead storage battery capacitor electrode can be increased and the internal resistance can be reduced.
（乾式成形法）
（複合粒子の調製）
本発明に用いるキャパシタ層を、乾式成形法により成形する場合において、キャパシタ層を形成するキャパシタ層組成物は、前述のようにキャパシタ電極活物質、導電材および結着剤を少なくとも含んでなる、複合粒子である。キャパシタ層組成物が複合粒子であることにより、得られる鉛蓄電池用キャパシタ電極の電極強度を高くしたり、内部抵抗を低減したりすることができる。
(Dry molding method)
(Preparation of composite particles)
In the case where the capacitor layer used in the present invention is molded by a dry molding method, the capacitor layer composition for forming the capacitor layer is a composite comprising at least a capacitor electrode active material, a conductive material and a binder as described above. Particles. When the capacitor layer composition is composite particles, the electrode strength of the obtained lead storage battery capacitor electrode can be increased, or the internal resistance can be reduced.
本発明でいう複合粒子とは、キャパシタ電極活物質、導電材および結着剤の必須成分、並びに必要に応じて用いる任意成分等、複数の材料が一体化した粒子をさす。また、好適に用いることができる複合粒子は、キャパシタ電極活物質、導電材および結着剤の必須成分、並び必要に応じて任意成分を用いて造粒することにより製造される。 The composite particles referred to in the present invention refer to particles in which a plurality of materials such as capacitor electrode active materials, conductive materials and binders, and optional components used as necessary, are integrated. Moreover, the composite particle which can be used suitably is manufactured by granulating using the essential component of a capacitor electrode active material, a electrically conductive material, and a binder, and arbitrary components as needed.
複合粒子の造粒方法は特に制限されず、噴霧乾燥造粒法、転動層造粒法、圧縮型造粒法、攪拌型造粒法、押出し造粒法、破砕型造粒法、流動層造粒法、流動層多機能型造粒法、および溶融造粒法などの公知の造粒法により製造することができる。中でも、表面付近に結着剤および導電材が偏在した複合粒子を容易に得られるので、噴霧乾燥造粒法が好ましい。噴霧乾燥造粒法で得られる複合粒子を用いることにより、鉛蓄電池用キャパシタ電極を高い生産性で得ることができる。また、該電極の内部抵抗をより低減することができる。 The granulation method of the composite particles is not particularly limited, and is spray drying granulation method, rolling bed granulation method, compression granulation method, stirring granulation method, extrusion granulation method, crushing granulation method, fluidized bed It can be produced by a known granulation method such as a granulation method, a fluidized bed multifunctional granulation method, or a melt granulation method. Among them, the spray-drying granulation method is preferable because composite particles in which the binder and the conductive material are unevenly distributed near the surface can be easily obtained. By using the composite particles obtained by the spray drying granulation method, a capacitor electrode for a lead storage battery can be obtained with high productivity. In addition, the internal resistance of the electrode can be further reduced.
前記噴霧乾燥造粒法では、まず上記したキャパシタ電極活物質、導電材および結着剤の必須成分、並びに必要に応じて用いる任意成分を溶媒に分散または溶解して、キャパシタ電極活物質、導電材および結着剤の必須成分、並びに任意成分が分散または溶解されてなるスラリーを得る。 In the spray drying granulation method, first, the capacitor electrode active material, the conductive material and the essential components of the binder, and optional components used as necessary are dispersed or dissolved in a solvent to obtain the capacitor electrode active material and the conductive material. And a slurry in which the essential components of the binder and the optional components are dispersed or dissolved.
スラリーを得るために用いる溶媒は、特に限定されないが、上記の溶解型結着剤を用いる場合には、溶解型結着剤を溶解可能な溶媒が好適に用いられる。具体的には、通常水が用いられるが、有機溶媒を用いることもできるし、水と有機溶媒との混合溶媒を用いてもよい。有機溶媒としては、例えば、メチルアルコール、エチルアルコール、プロピルアルコール等のアルキルアルコール類；アセトン、メチルエチルケトン等のアルキルケトン類；テトラヒドロフラン、ジオキサン、ジグライム等のエーテル類；ジエチルホルムアミド、ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、ジメチルイミダゾリジノン等のアミド類；ジメチルスルホキサイド、スルホラン等のイオウ系溶剤；等が挙げられる。この中でも有機溶媒としては、アルコール類が好ましい。水と、水よりも沸点の低い有機溶媒とを併用すると、噴霧乾燥時に、乾燥速度を速くすることができる。また、水と併用する有機溶媒の量または種類によって、分散型結着剤の分散性または溶解型結着剤の溶解性が変わる。これにより、スラリーの粘度や流動性を調整することができ、生産効率を向上させることができる。 The solvent used for obtaining the slurry is not particularly limited, but when using the above-mentioned soluble binder, a solvent capable of dissolving the soluble binder is preferably used. Specifically, water is usually used, but an organic solvent may be used, or a mixed solvent of water and an organic solvent may be used. Examples of the organic solvent include alkyl alcohols such as methyl alcohol, ethyl alcohol and propyl alcohol; alkyl ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran, dioxane and diglyme; diethylformamide, dimethylacetamide and N-methyl- Amides such as 2-pyrrolidone and dimethylimidazolidinone; sulfur solvents such as dimethyl sulfoxide and sulfolane; and the like. Among these, alcohols are preferable as the organic solvent. When water and an organic solvent having a lower boiling point than water are used in combination, the drying rate can be increased during spray drying. Further, the dispersibility of the dispersion-type binder or the solubility of the dissolution-type binder varies depending on the amount or type of the organic solvent used in combination with water. Thereby, the viscosity and fluidity | liquidity of a slurry can be adjusted and production efficiency can be improved.
スラリーを調製するときに使用する溶媒の量は、スラリーの固形分濃度が、通常１〜５０重量％、好ましくは５〜５０重量％、より好ましくは１０〜３０重量％の範囲となる量である。固形分濃度がこの範囲にあるときに、結着剤が均一に分散するため好適である。 The amount of the solvent used when preparing the slurry is such that the solid content concentration of the slurry is usually in the range of 1 to 50% by weight, preferably 5 to 50% by weight, more preferably 10 to 30% by weight. . When the solid content concentration is in this range, the binder is preferably dispersed uniformly.
キャパシタ電極活物質、導電材および結着剤の必須成分と、任意成分とを溶媒に分散または溶解する方法または手順は特に限定されず、例えば、溶媒に、キャパシタ電極活物質、導電材、結着剤等を添加し混合する方法；溶媒に溶解型結着剤を溶解した後、溶媒に分散させた結着剤（例えば、ラテックス）を添加して混合し、最後にキャパシタ電極活物質および導電材を添加して混合する方法；溶媒に分散させた結着剤にキャパシタ電極活物質および導電材を添加して混合し、この混合物に溶媒に溶解させた溶解型結着剤を添加して混合する方法等が挙げられる。混合の手段としては、例えば、ボールミル、サンドミル、ビーズミル、顔料分散機、らい潰機、超音波分散機、ホモジナイザー、ホモミキサー、プラネタリーミキサー等の混合機器が挙げられる。混合は、通常、室温〜８０℃の範囲で、１０分〜数時間行う。 The method or procedure for dispersing or dissolving the essential component of the capacitor electrode active material, the conductive material and the binder and the optional component in the solvent is not particularly limited. For example, the capacitor electrode active material, the conductive material, the binder is dissolved in the solvent. A method of adding and mixing an agent, etc .; after dissolving a soluble binder in a solvent, a binder (for example, latex) dispersed in the solvent is added and mixed, and finally a capacitor electrode active material and a conductive material And adding a capacitor electrode active material and a conductive material to a binder dispersed in a solvent, mixing, and adding a mixed binder dissolved in a solvent to the mixture. Methods and the like. Examples of the mixing means include mixing equipment such as a ball mill, a sand mill, a bead mill, a pigment disperser, a crusher, an ultrasonic disperser, a homogenizer, a homomixer, and a planetary mixer. Mixing is usually performed in the range of room temperature to 80 ° C. for 10 minutes to several hours.
スラリーの粘度は、室温において、通常１０〜３，０００ｍＰａ・ｓ、好ましくは３０〜１，５００ｍＰａ・ｓ、より好ましくは５０〜１，０００ｍＰａ・ｓの範囲である。スラリーの粘度がこの範囲にあると、複合粒子の生産性を上げることができる。また、スラリーの粘度が高いほど、噴霧液滴が大きくなり、得られる複合粒子の体積平均粒子径が大きくなる。 The viscosity of the slurry is usually in the range of 10 to 3,000 mPa · s, preferably 30 to 1,500 mPa · s, more preferably 50 to 1,000 mPa · s at room temperature. When the viscosity of the slurry is within this range, the productivity of the composite particles can be increased. Moreover, the higher the viscosity of the slurry, the larger the spray droplets, and the larger the volume average particle diameter of the resulting composite particles.
次に、上記で得たスラリーを噴霧乾燥して造粒し、複合粒子を得る。噴霧乾燥は、熱風中にスラリーを噴霧して乾燥することにより行う。スラリーの噴霧に用いる装置としてアトマイザーが挙げられる。アトマイザーは、回転円盤方式と加圧方式との二種類の装置がある。回転円盤方式は、高速回転する円盤のほぼ中央にスラリーを導入し、円盤の遠心力によってスラリーが円盤の外に放たれ、その際にスラリーを霧状にする方式である。円盤の回転速度は円盤の大きさに依存するが、通常は５，０００〜３０，０００ｒｐｍ、好ましくは１５，０００〜３０，０００ｒｐｍである。円盤の回転速度が低いほど、噴霧液滴が大きくなり、得られる複合粒子の体積平均粒子径が大きくなる。回転円盤方式のアトマイザーとしては、ピン型とベーン型が挙げられるが、好ましくはピン型アトマイザーである。ピン型アトマイザーは、噴霧盤を用いた遠心式の噴霧装置の一種であり、該噴霧盤が上下取付円板の間にその周縁に沿ったほぼ同心円状に着脱自在に複数の噴霧用コロを取り付けたもので構成されている。スラリーは噴霧盤中央から導入され、遠心力によって噴霧用コロに付着し、コロ表面を外側へと移動し、最後にコロ表面から離れ噴霧される。一方、加圧方式は、スラリーを加圧してノズルから霧状にして乾燥する方式である。 Next, the slurry obtained above is spray-dried and granulated to obtain composite particles. Spray drying is performed by spraying the slurry in hot air and drying. An atomizer is used as an apparatus used for spraying slurry. There are two types of atomizers: a rotating disk method and a pressure method. The rotating disk system is a system in which slurry is introduced almost at the center of a disk that rotates at a high speed, and the slurry is released out of the disk by the centrifugal force of the disk, and the slurry is atomized at that time. The rotational speed of the disc depends on the size of the disc, but is usually 5,000 to 30,000 rpm, preferably 15,000 to 30,000 rpm. The lower the rotational speed of the disk, the larger the spray droplets and the larger the volume average particle diameter of the resulting composite particles. Examples of the rotating disk type atomizer include a pin type and a vane type, and a pin type atomizer is preferable. A pin-type atomizer is a type of centrifugal spraying device that uses a spraying plate, and the spraying plate has a plurality of spraying rollers attached between upper and lower mounting disks in a substantially concentric manner along its periphery. It consists of The slurry is introduced from the center of the spray platen, adheres to the spraying roller by centrifugal force, moves outside the roller surface, and finally sprays away from the roller surface. On the other hand, the pressurization method is a method in which the slurry is pressurized and sprayed from a nozzle to be dried.
噴霧されるスラリーの温度は、通常は室温であるが、加温して室温以上にしたものであってもよい。また、噴霧乾燥時の熱風温度は、通常８０〜２５０℃、好ましくは１００〜２００℃である。噴霧乾燥において、熱風の吹き込み方法は特に制限されず、例えば、熱風と噴霧方向が横方向に並流する方式、乾燥塔頂部で噴霧され熱風と共に下降する方式、噴霧した滴と熱風が向流接触する方式、噴霧した滴が最初熱風と並流し次いで重力落下して向流接触する方式等が挙げられる。 The temperature of the slurry to be sprayed is usually room temperature, but may be heated to room temperature or higher. Moreover, the hot air temperature at the time of spray-drying is 80-250 degreeC normally, Preferably it is 100-200 degreeC. In spray drying, the method of blowing hot air is not particularly limited, for example, a method in which the hot air and the spray direction flow in the horizontal direction, a method in which the hot air is sprayed at the top of the drying tower and descends with the hot air, and the sprayed droplet and the hot air are in countercurrent contact And a system in which sprayed droplets first flow in parallel with hot air and then drop by gravity to make countercurrent contact.
上記の噴霧乾燥により、複合粒子が得られる。該複合粒子の平均粒子径は、流動性がよく、薄膜化が可能である観点から、５０〜３５０μｍ、好ましくは６０〜３００μｍ、より好ましくは８０〜２５０μｍである。複合粒子の体積平均粒子径が大きすぎると、得られる電極の厚み精度が低くなり、複合粒子の体積平均粒子径が小さすぎると、該複合粒子の流動性が悪化する。ここで、複合粒子の体積平均粒子径は、レーザ回折式粒度分布測定装置を用いて複合粒子を圧搾空気により加圧噴霧して測定される体積平均粒子径である。 Composite particles are obtained by spray drying. The average particle diameter of the composite particles is 50 to 350 μm, preferably 60 to 300 μm, more preferably 80 to 250 μm, from the viewpoint of good fluidity and thinning. When the volume average particle diameter of the composite particles is too large, the thickness accuracy of the obtained electrode is lowered, and when the volume average particle diameter of the composite particles is too small, the fluidity of the composite particles is deteriorated. Here, the volume average particle diameter of the composite particles is a volume average particle diameter measured by pressurizing and spraying the composite particles with compressed air using a laser diffraction particle size distribution analyzer.
上記の製造方法で得られた複合粒子は、必要に応じて粒子製造後の後処理を実施することもできる。具体例としては、複合粒子に上記のキャパシタ電極活物質、導電材、結着剤等と混合することによって、粒子表面を改質して、球状複合粒子の流動性を向上または低下させる、連続加圧成形性を向上させる、球状複合粒子の電気伝導性を向上させることなどができる。 The composite particles obtained by the above production method can be subjected to post-treatment after the production of the particles, if necessary. As a specific example, the composite particles are mixed with the above capacitor electrode active material, conductive material, binder, etc. to modify the particle surface and improve or decrease the fluidity of the spherical composite particles. It is possible to improve the press formability and the electrical conductivity of the spherical composite particles.
（ロール成形）
本発明のキャパシタ層を乾式成形法で製造する場合は、複合粒子からなるキャパシタ層をロール成形により接着剤が塗布された支持体上にシート成形することにより鉛蓄電池用キャパシタ電極を得る方法が挙げられる。なお、この鉛蓄電池用キャパシタ電極を得る方法における支持体には、鉛電極に使用される集電体は含まれない。
(Roll molding)
When the capacitor layer of the present invention is produced by a dry molding method, a method of obtaining a capacitor electrode for a lead storage battery by forming a capacitor layer made of composite particles on a support coated with an adhesive by roll molding is mentioned. It is done. In addition, the support body in the method for obtaining the capacitor electrode for the lead storage battery does not include the current collector used for the lead electrode.
ロール成形を行う場合には、複合粒子と、接着剤が塗布された支持体とを、略水平に配置された一対のプレス用ロール又はベルトに供給し、前記一対のプレス用ロール又はベルトにより前記複合粒子をシート状成形体に成形することによりキャパシタ層を得るとともに、これを前記支持体の面に圧着する。 When roll forming is performed, the composite particles and the support coated with the adhesive are supplied to a pair of press rolls or belts arranged substantially horizontally, and the pair of press rolls or belts A capacitor layer is obtained by molding the composite particles into a sheet-like molded body, and this is pressure-bonded to the surface of the support.
（支持体）
支持体は、キャパシタ層を支持し、さらに、キャパシタ層を鉛電極に貼り合わせるために使用するものである。本発明において、支持体を構成する材料は特に限定されないが、繊維状のものが好ましく、紙等のセルロース由来のものや炭素由来のものがより好ましい。また、支持体はこれらの材料で構成される層を重ねた多層構造であってもよい。
(Support)
The support is used for supporting the capacitor layer and further bonding the capacitor layer to the lead electrode. In the present invention, the material constituting the support is not particularly limited, but is preferably a fibrous material, more preferably a cellulose-derived material such as paper or a carbon-derived material. The support may have a multilayer structure in which layers composed of these materials are stacked.
支持体の厚さは、１５〜１５０μｍ、好ましくは１５〜１００μｍ、より好ましくは１５〜５０μｍである。支持体が厚すぎると、得られる鉛蓄電池用キャパシタ電極の内部抵抗が高くなる。また、キャパシタ電極活物質の有効部分が減る。 The thickness of the support is 15 to 150 μm, preferably 15 to 100 μm, more preferably 15 to 50 μm. When a support body is too thick, the internal resistance of the capacitor electrode for lead acid batteries obtained will become high. In addition, the effective portion of the capacitor electrode active material is reduced.
支持体の幅は、特に限定されないが１００〜１０００ｍｍ、さらには１００〜５００ｍｍが好適である。支持体の引っ張り強度は特に限定されないが、キャパシタ層の製造時の破断を防ぐ観点から、３０〜５００ＭＰａが好適であり、３０〜３００ＭＰａがより好適である。支持体の製造方法は特に限定されないが、セルロース由来のものである場合には、パルプ化工程、調整工程、抄造工程、仕上げ工程を経て製造されることが好ましい。 Although the width | variety of a support body is not specifically limited, 100-1000 mm, Furthermore, 100-500 mm is suitable. Although the tensile strength of a support body is not specifically limited, From a viewpoint of preventing the fracture | rupture at the time of manufacture of a capacitor layer, 30-500 MPa is suitable and 30-300 MPa is more suitable. Although the manufacturing method of a support body is not specifically limited, When it is a thing derived from a cellulose, it is preferable to manufacture through a pulping process, an adjustment process, a papermaking process, and a finishing process.
本発明に用いられる支持体上には接着剤が塗布されている。ここで、接着剤としては、支持体とキャパシタ層を相互に接着させることができる物質であれば特に制限はなく、水溶性接着剤、またはラテックス等の接着剤が挙げられる。また、支持体とキャパシタ層の間に接着剤層が存在することが好ましい。 An adhesive is applied on the support used in the present invention. Here, the adhesive is not particularly limited as long as it can adhere the support and the capacitor layer to each other, and examples thereof include water-soluble adhesives and adhesives such as latex. Moreover, it is preferable that an adhesive layer exists between the support and the capacitor layer.
水溶性接着剤としては、例えば、ポリビニルアルコール、変性ポリビニルアルコール、澱粉類、ゼラチン、カゼイン、メチルセルロース、ヒドロキシエチルセルロース、アクリル酸アミド−アクリル酸エステル共重合体、アクリル酸アミド−アクリル樹脂−メタクリル酸３元共重合体、スチレン−アクリル樹脂、イソブチレン−無水マレイン酸樹脂、カルボキシメチルセルロース等のアニオン性水溶性接着剤や、ポリエチレンイミン；ポリＮ−ヒドロキシルエチレンイミン、カルボキシメチル化ポリエチレンイミン・ナトリウム塩等のポリエチレンイミン誘導体；ポリプロピレンイミン；ポリＮ−２− ジヒドロシキルプロピレンイミン等のポリプロピレンイミン誘導体等のカチオン性水溶性接着剤が挙げられる。 Examples of the water-soluble adhesive include polyvinyl alcohol, modified polyvinyl alcohol, starches, gelatin, casein, methyl cellulose, hydroxyethyl cellulose, acrylic acid amide-acrylic acid ester copolymer, acrylic acid amide-acrylic resin-methacrylic acid ternary. Anionic water-soluble adhesives such as copolymers, styrene-acrylic resins, isobutylene-maleic anhydride resins, carboxymethylcellulose, and polyethyleneimines; polyethyleneimines such as poly N-hydroxylethyleneimine, carboxymethylated polyethyleneimine and sodium salts Derivatives; polypropyleneimine; and cationic water-soluble adhesives such as polypropyleneimine derivatives such as poly N-2-dihydroxypropyleneimine.
ラテックス接着剤としては、アクリル系エマルジョン、酢酸ビニル系エマルジョン、塩化ビニリデンエマルジョン、ポリエステル系エマルジョン、塩化ビニリデンエマルジョン、ポリエステル系エマルジョン、スチレン−ブタジエンラテックス、アクリロニトリル−ブタジエンラテックス、アクリルニトリル−ブタジエンラテックス等が挙げられる。 Examples of the latex adhesive include acrylic emulsion, vinyl acetate emulsion, vinylidene chloride emulsion, polyester emulsion, vinylidene chloride emulsion, polyester emulsion, styrene-butadiene latex, acrylonitrile-butadiene latex, and acrylonitrile-butadiene latex. .
これらのなかでも、得られる鉛蓄電池用キャパシタ電極の抵抗が低減できるため、電界液に溶解する水溶性接着剤が好ましく、カチオン性水溶性接着剤が特に好ましい。 Among these, since the resistance of the obtained lead-acid battery capacitor electrode can be reduced, a water-soluble adhesive that dissolves in an electrolysis solution is preferable, and a cationic water-soluble adhesive is particularly preferable.
接着剤層の形成方法は、特に制限されない。例えば、ドクターブレード法、ディップ法、リバースロール法、ダイレクトロール法、グラビア法、エクストルージョン法、ハケ塗りなどによって、支持体上に接着剤層が形成される。また、剥離紙上に、接着剤層を形成した後に、これを支持体に転写してもよい。 The method for forming the adhesive layer is not particularly limited. For example, the adhesive layer is formed on the support by a doctor blade method, a dip method, a reverse roll method, a direct roll method, a gravure method, an extrusion method, brushing, or the like. Further, after an adhesive layer is formed on the release paper, it may be transferred to a support.
接着剤が塗布された支持体の接着力の評価は、接着剤が塗布された支持体と厚さ５０μｍのＰＥＴフィルムとをロールプレスにて線圧０．５ｔ／ｍの条件で貼り付けた後、１８０°剥離試験をおこなうことにより実施した。具体的には、ＰＥＴフィルム面を上にして固定し、ＰＥＴフィルムを５０ｍｍ／分の速度で１８０°方向に引きはがしたときの応力を測定した。ここで、接着剤が塗布された支持体の接着力は、０．２Ｎ／ｍ以上、好ましくは０．５Ｎ／ｍ以上、より好ましくは１．０Ｎ／ｍ以上である。接着力が小さすぎると、支持体とキャパシタ層が十分に接着しない。 The adhesive strength of the support coated with the adhesive is evaluated after the support coated with the adhesive and a PET film having a thickness of 50 μm are pasted on a roll press under a linear pressure of 0.5 t / m. The 180 ° peel test was performed. Specifically, the PET film surface was fixed upward, and the stress when the PET film was peeled off in the 180 ° direction at a speed of 50 mm / min was measured. Here, the adhesive strength of the support coated with the adhesive is 0.2 N / m or more, preferably 0.5 N / m or more, more preferably 1.0 N / m or more. When the adhesive force is too small, the support and the capacitor layer are not sufficiently bonded.
また、接着剤層の厚みは、０．０５〜１０μｍ、好ましくは０．１〜５．０μｍ、より好ましくは０．１〜１．０μｍである。接着剤層の厚みが厚すぎると、得られる鉛蓄電池用キャパシタ電極の内部抵抗が高くなる。また、接着剤層の厚みが薄すぎると、接着力が弱くなる。 Moreover, the thickness of an adhesive bond layer is 0.05-10 micrometers, Preferably it is 0.1-5.0 micrometers, More preferably, it is 0.1-1.0 micrometer. When the thickness of the adhesive layer is too thick, the internal resistance of the obtained lead-acid battery capacitor electrode is increased. On the other hand, if the thickness of the adhesive layer is too thin, the adhesive strength becomes weak.
図１は、複合粒子を接着剤が塗布された支持体上に供給し、略水平に配置された一対のプレス用ロールにより加圧成形し、シート状のキャパシタ層を得るとともに前記支持体の接着剤が塗布された面と圧着する工程の具体的な態様を表す図である。 FIG. 1 shows a method for supplying composite particles onto a support coated with an adhesive and press-molding with a pair of press rolls arranged substantially horizontally to obtain a sheet-like capacitor layer and bonding the support. It is a figure showing the specific aspect of the process of crimping | bonding with the surface where the agent was apply | coated.
図１では、接着剤が塗布された支持体１４をプレス用ロール１２方向へ送り出す。次いで、複合粒子１３をスクリューフィーダー等の供給装置により略水平に配置された一対のプレス用ロール１２に供給し、一対のプレス用ロールにより加圧成形することにより、複合粒子をシート状成形体に成形するとともに、これを支持体１４の接着剤が塗布された面に圧着する。そして、キャパシタ層を形成した支持体をワインダー１０で巻き取り、支持体およびキャパシタ層の巻収体が得られる。 In FIG. 1, the support 14 coated with the adhesive is sent out toward the press roll 12. Next, the composite particles 13 are supplied to a pair of press rolls 12 arranged substantially horizontally by a supply device such as a screw feeder, and press-molded by the pair of press rolls, whereby the composite particles are formed into a sheet-like molded body. While being molded, this is pressure-bonded to the surface of the support 14 to which the adhesive has been applied. And the support body in which the capacitor layer was formed is wound up with the winder 10, and the winding body of a support body and a capacitor layer is obtained.
なお、図１に示されている一対のプレス用ロールは、一対のプレス用ベルトに置き換えることができる。 The pair of pressing rolls shown in FIG. 1 can be replaced with a pair of pressing belts.
また、ロール成形における成形時の温度は、良好な接着力が発現する観点から、通常２５〜２００℃、好ましくは５０〜１５０℃、より好ましくは６０〜１２０℃である。また、成形速度は通常０．１〜２０ｍ／分、好ましくは４〜２０ｍ／分である。 Moreover, the temperature at the time of shaping | molding in roll shaping | molding is 25-200 degreeC normally from a viewpoint that favorable adhesive force expresses, Preferably it is 50-150 degreeC, More preferably, it is 60-120 degreeC. Moreover, a shaping | molding speed is 0.1-20 m / min normally, Preferably it is 4-20 m / min.
また、ロール間のプレス線圧は、均一なキャパシタ層を成形する観点から、通常１０〜１０００ｋＮ／ｍ、好ましくは２００〜９００ｋＮ／ｍ、より好ましくは３００〜６００ｋＮ／ｍである。また、プレス用ロールに代えてプレス用ベルトを用いる場合の成形速度は、通常１〜１５ｍ／分、好ましくは５〜１０ｍ／分である。また、プレス用ベルト間の圧力は、通常５〜５０ＭＰａ、好ましくは１０〜３０ＭＰａである。 Moreover, the press linear pressure between rolls is 10-1000 kN / m normally from a viewpoint of shape | molding a uniform capacitor layer, Preferably it is 200-900 kN / m, More preferably, it is 300-600 kN / m. The forming speed when using a press belt instead of the press roll is usually 1 to 15 m / min, preferably 5 to 10 m / min. The pressure between the pressing belts is usually 5 to 50 MPa, preferably 10 to 30 MPa.
本発明において、成形したキャパシタ層の厚さのばらつきをなくし、キャパシタ層の密度を上げて高容量化をはかるために、必要に応じてさらに後加圧を行っても良い。後加圧の方法は、ロールプレス工程が一般的である。ロールプレス工程では、２本の円柱状のロールをせまい間隔で平行に上下にならべ、それぞれを反対方向に回転させて、その間に電極をかみこませ加圧する。ロールプレス工程で用いるロールは加熱または冷却等して温度調節しても良い。 In the present invention, post-pressurization may be further performed as necessary in order to eliminate the variation in the thickness of the molded capacitor layer and increase the density of the capacitor layer to increase the capacity. The post-pressing method is generally a roll press process. In the roll press process, two cylindrical rolls are arranged in parallel at a narrow interval in the vertical direction, and each is rotated in the opposite direction. The temperature of the roll used in the roll press process may be adjusted by heating or cooling.
また、キャパシタ層の密度は、特に制限されないが、通常は０．３０〜１０ｇ／ｃｍ3、好ましくは０．３５〜５．０ｇ／ｃｍ3、より好ましくは０．４０〜３．０ｇ／ｃｍ3である。また、キャパシタ層の厚さは、特に制限されないが、通常は５〜１０００μｍ、好ましくは２０〜５００μｍ、より好ましくは３０〜４００μｍである。 The density of the capacitor layer is not particularly limited, but is usually 0.30 to 10 g / cm 3 , preferably 0.35 to 5.0 g / cm 3 , more preferably 0.40 to 3.0 g / cm 3. It is. The thickness of the capacitor layer is not particularly limited, but is usually 5 to 1000 μm, preferably 20 to 500 μm, and more preferably 30 to 400 μm.
また、前記略水平に配置された一対のプレス用ロール又はベルトに供給する際に、複合粒子は加温されていてもよい。そのときの複合粒子の温度は、プレス用ロール又はベルトの表面に複合粒子の滑りがなく、複合粒子が連続的にかつ均一にプレス用ロール又はベルトに供給されるので、膜厚が均一で、密度のばらつきが小さいキャパシタ層を得ることができる観点から、好ましくは４０〜１６０℃、より好ましくは７０〜１４０℃である。 Further, the composite particles may be heated when supplied to the pair of press rolls or belts arranged substantially horizontally. The temperature of the composite particles at that time is such that there is no slip of the composite particles on the surface of the press roll or belt, and the composite particles are continuously and uniformly supplied to the press roll or belt. From the viewpoint of obtaining a capacitor layer with small variation in density, the temperature is preferably 40 to 160 ° C, more preferably 70 to 140 ° C.
（鉛キャパシタ蓄電池）
本発明の鉛蓄電池用キャパシタ電極の使用態様としては、かかる電極を用いた鉛キャパシタ蓄電池などが挙げられる。例えば鉛キャパシタ蓄電池は、正極と負極と、正極と負極の間に配置されるセパレータと、電解液とを含み、前記正極とセパレータとの間および負極とセパレータとの間の少なくとも一方に上述の鉛蓄電池用キャパシタ電極が配置される。
(Lead capacitor battery)
The usage mode of the capacitor electrode for a lead storage battery of the present invention includes a lead capacitor storage battery using such an electrode. For example, a lead capacitor storage battery includes a positive electrode and a negative electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolytic solution, and the above-mentioned lead is provided between at least one of the positive electrode and the separator and between the negative electrode and the separator. A storage battery capacitor electrode is disposed.
鉛キャパシタ蓄電池は通常、セパレータを介して正極と負極が対向するように配置され、正極とセパレータとの間および負極とセパレータとの間の少なくとも一方に上述の鉛蓄電池用キャパシタ電極が配置された構造を複数対有しており、正極同士、または負極同士はそれぞれ電気的に短絡された構造である。このような構造とすることにより、鉛キャパシタ蓄電池の容量を大きくすることができる。
また、鉛キャパシタ蓄電池において、上述した以外の構成要素としては、上述の構成要素を収納する電槽及びふたが挙げられる。
A lead capacitor storage battery is usually arranged such that a positive electrode and a negative electrode face each other with a separator interposed therebetween, and the above-mentioned lead storage battery capacitor electrode is arranged between at least one of the positive electrode and the separator and between the negative electrode and the separator. The positive electrodes or the negative electrodes are electrically short-circuited. By setting it as such a structure, the capacity | capacitance of a lead capacitor storage battery can be enlarged.
Moreover, in the lead capacitor storage battery, examples of components other than those described above include a battery case and a lid that house the above-described components.
（正極電極および負極電極）
正極電極および負極電極は、鉛活物質層を含んでなる。鉛活物質層は、通常の鉛蓄電池の活物質として使用される鉛、一酸化鉛、二酸化鉛、三酸化二鉛、四酸化三鉛（鉛丹）、硫酸鉛などの、鉛および鉛化合物を主体とする層を指す。これらの鉛および鉛化合物は、単独でまたは混合物を適宜選択して使用することができる。鉛活物質層中の鉛原子が占める割合は、活物質層のエネルギー密度を高める観点から、通常は層全体の重量に対して５０重量％以上、好ましくは７０重量％以上である。正極電極に含まれる鉛活物質層である正極活物質層に用いられる鉛含有材料としては二酸化鉛または一酸化鉛が好ましく、負極電極に含まれる鉛活物質層である負極活物質層に用いられる鉛含有材料としては一酸化鉛または鉛が好ましい。
(Positive electrode and negative electrode)
The positive electrode and the negative electrode comprise a lead active material layer. Lead active material layer contains lead and lead compounds such as lead, lead monoxide, lead dioxide, dilead trioxide, trilead tetroxide (lead red), lead sulfate, etc. Refers to the main layer. These lead and lead compounds can be used alone or in a suitable mixture. From the viewpoint of increasing the energy density of the active material layer, the proportion of lead atoms in the lead active material layer is usually 50% by weight or more, preferably 70% by weight or more, based on the weight of the entire layer. The lead-containing material used in the positive electrode active material layer that is the lead active material layer included in the positive electrode is preferably lead dioxide or lead monoxide, and is used in the negative electrode active material layer that is the lead active material layer included in the negative electrode. As the lead-containing material, lead monoxide or lead is preferable.
鉛活物質層は、鉛含有材料の他に、ポリエステル繊維などの強化材、リグニンなどの界面活性剤、硫酸バリウムなどを含んでいてもよい。また、アンチモン、亜鉛、カドミウム、銀およびビスマスの酸化物、水酸化物もしくは硫酸塩から選ばれる添加剤なども使用することができる。さらに、鉛含有材料のペーストを作製して鉛活物質層を形成する場合は、硫酸を加えることもできる。 In addition to the lead-containing material, the lead active material layer may contain a reinforcing material such as polyester fiber, a surfactant such as lignin, barium sulfate, and the like. Further, an additive selected from oxides, hydroxides or sulfates of antimony, zinc, cadmium, silver and bismuth can be used. Further, when a lead active material layer is formed by producing a paste of a lead-containing material, sulfuric acid can be added.
（鉛活物質層の形成方法）
鉛活物質層は、鉛含有材料に溶媒、添加剤を加えてペーストを作製し、このペーストを格子状集電体上に充填させることにより形成することができる。
(Method for forming lead active material layer)
The lead active material layer can be formed by preparing a paste by adding a solvent and an additive to a lead-containing material and filling the paste on a grid-like current collector.
例えば格子状集電体を用いる場合、格子状集電体の格子平面の一部に鉛活物質層を形成する、格子状集電体の格子全面に鉛活物質層を形成する、などが挙げられる。 For example, when using a grid current collector, a lead active material layer is formed on a part of the grid plane of the grid current collector, a lead active material layer is formed on the entire grid surface of the grid current collector, and the like. It is done.
（鉛活物質層とキャパシタ層の積層方法）
鉛活物質層とキャパシタ層は、電気的に導通がとれている必要がある。そのため、これらの層は加圧接着することが好ましい。例えば、上記の鉛活物質層の形成方法によって格子状集電体に充填された鉛活物質層の上に、鉛蓄電池用キャパシタ電極を加圧成形する。このとき、鉛蓄電池用キャパシタ電極のキャパシタ層側が鉛活物質層に対向するように配置して加圧成形する。
(Lamination method of lead active material layer and capacitor layer)
The lead active material layer and the capacitor layer must be electrically connected. Therefore, these layers are preferably pressure bonded. For example, a lead storage battery capacitor electrode is pressure-molded on the lead active material layer filled in the grid-like current collector by the above-described method of forming a lead active material layer. At this time, it arrange | positions so that the capacitor layer side of the capacitor electrode for lead acid batteries may oppose a lead active material layer, and it pressure-molds.
（集電体）
集電体は、キャパシタ電極活物質および鉛含有材料と鉛蓄電池外との電気的導通をとるためのものである。集電体としては、板状、箔状、クラッド式と呼ばれる多孔性チューブの中心に鉛合金芯金を挿入したもの、および格子状集電体などが挙げられる。中でも、電極活物質層の維持と集電性に優れる点から格子状集電体が好ましい。格子状集電体としては、標準格子、ラジアル格子、エキスパンド式のいずれも使用できる。
(Current collector)
The current collector is for establishing electrical continuity between the capacitor electrode active material and the lead-containing material and the outside of the lead storage battery. Examples of the current collector include a plate-shaped, foil-shaped, clad-type porous tube in which a lead alloy core is inserted, and a grid-shaped current collector. Among these, a grid-like current collector is preferable from the viewpoint of maintaining the electrode active material layer and excellent current collecting properties. As the grid current collector, any of a standard grid, a radial grid, and an expanded type can be used.
格子状集電体の材質としては、鉛−カルシウム合金、鉛−アンチモン合金、鉛−錫合金等の鉛含有合金が用いられる。前記鉛合金の組成の一部として、砒素、錫、銅、銀、アルミなどを含んでいても良い。 As the material of the grid-like current collector, a lead-containing alloy such as a lead-calcium alloy, a lead-antimony alloy, or a lead-tin alloy is used. Arsenic, tin, copper, silver, aluminum, or the like may be included as part of the composition of the lead alloy.
（セパレータ）
鉛キャパシタ蓄電池で使用されるセパレータとしては、抄紙、微多孔性ポリエチレン、微多孔性ポリプロピレン、微多孔性ゴム、リテイナーマット、ガラスマット、などのセパレータを１つまたは複数組み合わせて使用することができる。
(Separator)
As the separator used in the lead capacitor storage battery, one or a combination of separators such as papermaking, microporous polyethylene, microporous polypropylene, microporous rubber, retainer mat, and glass mat can be used.
（電解液）
鉛キャパシタ蓄電池で使用される電解液は通常、硫酸が使用される。充放電状態によって硫酸の密度は変動するが、鉛蓄電池を化成処理後、満充電の状態で密度１．２５〜１．３０ｇ／ｃｍ3（２０℃）であることが好ましい。
(Electrolyte)
In general, sulfuric acid is used as the electrolyte used in the lead capacitor storage battery. Although the density of sulfuric acid varies depending on the charge / discharge state, the density is preferably 1.25 to 1.30 g / cm 3 (20 ° C.) in a fully charged state after chemical conversion treatment of the lead storage battery.
（電槽、ふた）
鉛キャパシタ蓄電池において、正極、負極、セパレータ、鉛蓄電池用キャパシタ電極および電解液を収納する電槽及びふたとしては、エチレン−プロピレン共重合体、ポリエチレン、ポリプロピレン、ポリアクリロニトリル−スチレン共重合体、ポリアクリロニトリル−ブタジエン−スチレン共重合体を原料とするものを使用することができる。
(Battery, lid)
In a lead capacitor battery, a positive electrode, a negative electrode, a separator, a capacitor electrode for a lead battery, and a battery case and lid for storing an electrolyte include ethylene-propylene copolymer, polyethylene, polypropylene, polyacrylonitrile-styrene copolymer, polyacrylonitrile. -A butadiene-styrene copolymer can be used as a raw material.
（組電池）
上述のようにセパレータを介して正極と負極が対向するように配置され、正極とセパレータとの間および負極とセパレータとの間の少なくとも一方に上述の鉛蓄電池用キャパシタ電極が配置された構造を複数対有し、正極同士および負極同士のそれぞれを短絡させた構造である鉛キャパシタ蓄電池を複数用意して直列に接続することができる。このようにすることで鉛キャパシタ蓄電池の全体の起電力を大きくすることができる。直列に接続するために電槽を複数用意する必要はなく、１つの電槽の中に複数の仕切りを設け、その仕切り毎に上述の正極、負極、セパレータおよび鉛蓄電池用キャパシタ電極を含む構造を収納し、それを直列接続すれば、一体化した起電力の高い鉛キャパシタ蓄電池を作製することができる。
(Battery)
As described above, a plurality of structures in which the positive electrode and the negative electrode are opposed to each other with the separator interposed therebetween, and the above-described lead storage battery capacitor electrode is disposed between at least one of the positive electrode and the separator and between the negative electrode and the separator. A plurality of lead capacitor storage batteries having a structure in which a pair of positive electrodes and negative electrodes are short-circuited can be prepared and connected in series. By doing in this way, the electromotive force of the whole lead capacitor storage battery can be enlarged. There is no need to prepare a plurality of battery cases in order to connect in series. A plurality of partitions are provided in one battery case, and the structure including the above-described positive electrode, negative electrode, separator, and lead-acid battery capacitor electrode is provided for each partition. If it is housed and connected in series, an integrated lead capacitor battery with high electromotive force can be produced.
以下に、実施例を挙げて本発明を説明するが、本発明はこれに限定されるものではない。なお、本実施例における部および％は、特記しない限り重量基準である。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto. In the examples, parts and% are based on weight unless otherwise specified.
実施例および比較例において、キャパシタ電極強度、容量および内部抵抗の評価は、以下のように行った。 In Examples and Comparative Examples, the evaluation of capacitor electrode strength, capacitance, and internal resistance was performed as follows.
（キャパシタ電極強度）
ＪＩＳ Ｋ６２５１に準じて測定した。実施例および比較例において、支持体上にキャパシタ層をシート状に成形することにより得られたキャパシタ電極を１６０℃で４０分乾燥した後、１号形のダンベル状試験片の形状に打ち抜き、雰囲気温度２５℃にて引張速度５０ｍｍ／分で引張試験を行い、破断時の最大荷重を測定した。この測定を６回繰り返し、最大荷重の平均値をシートの断面積で除した値をこのキャパシタ電極の引張り強度とし、以下の基準により評価した。結果を表１に示した。
キャパシタ電極の引張り強度が大きいほど、亀裂、破壊が生じにくく、形状保持性に優れることを示す。
Ａ：０．５ＭＰａ以上
Ｂ：０．４ＭＰａ以上０．５ＭＰa未満
Ｃ：０．３ＭＰａ以上０．４ＭＰa未満
Ｄ：０．３ＭＰａ未満
(Capacitor electrode strength)
It measured according to JIS K6251. In the examples and comparative examples, the capacitor electrode obtained by forming the capacitor layer on the support in the form of a sheet was dried at 160 ° C. for 40 minutes, then punched into the shape of No. 1 dumbbell-shaped test piece, and the atmosphere A tensile test was performed at a temperature of 25 ° C. and a tensile speed of 50 mm / min, and the maximum load at break was measured. This measurement was repeated 6 times, and the value obtained by dividing the average value of the maximum load by the cross-sectional area of the sheet was taken as the tensile strength of the capacitor electrode, and evaluated according to the following criteria. The results are shown in Table 1.
It shows that as the tensile strength of the capacitor electrode is larger, cracking and breakage are less likely to occur and the shape retention is better.
A: 0.5 MPa or more B: 0.4 MPa or more and less than 0.5 MPa C: 0.3 MPa or more and less than 0.4 MPa D: Less than 0.3 MPa
（容量）
実施例および比較例において得られたキャパシタ電極を、直径１２ｍｍの円形状に打ち抜き、このキャパシタ電極およびガラスファイバー製セパレータに十分電解液を含浸させ、次いで２枚のキャパシタ電極を、セパレータを介して対向させ、それぞれのキャパシタ電極が電気的に接触しないように配置して、電気二重層キャパシタを作製した。電解液には硫酸を用いた。
(capacity)
The capacitor electrodes obtained in the examples and comparative examples were punched into a circular shape having a diameter of 12 mm, the capacitor electrodes and the glass fiber separator were sufficiently impregnated with the electrolyte, and then the two capacitor electrodes were opposed to each other through the separator. Then, each capacitor electrode was arranged so as not to be in electrical contact, and an electric double layer capacitor was manufactured. Sulfuric acid was used as the electrolyte.
この電気二重層キャパシタの充放電試験を行うことにより容量を求めた。即ち、充電電流は、電極の単位面積あたりの電流値が６．６ｍＡ／ｃｍ2となる電流値を用いて行い、電圧が１．０Ｖに達したら、１０分間その電圧を保って定電圧充電とし、充電を完了した。次いで、充電終了直後に定電流放電を充電時に用いたのと同様な電流値で０Ｖに達するまで行う。容量は放電時の電力量からエネルギー換算法を用いて算出し、以下の基準により評価した。結果を表１に示した。
Ａ：５０Ｆ／ｇ以上
Ｂ：４５Ｆ／ｇ以上５０Ｆ／ｇ未満
Ｃ：４０Ｆ／ｇ以上４５Ｆ／ｇ未満
Ｄ：４０Ｆ／ｇ未満
The capacity was determined by conducting a charge / discharge test of the electric double layer capacitor. That is, the charging current is performed using a current value at which the current value per unit area of the electrode is 6.6 mA / cm 2, and when the voltage reaches 1.0 V, the voltage is maintained for 10 minutes for constant voltage charging. Completed charging. Then, immediately after the end of charging, constant current discharging is performed until the voltage reaches 0 V at a current value similar to that used during charging. The capacity was calculated from the amount of power at the time of discharge using an energy conversion method, and evaluated according to the following criteria. The results are shown in Table 1.
A: 50 F / g or more B: 45 F / g or more and less than 50 F / g C: 40 F / g or more and less than 45 F / g D: Less than 40 F / g
（内部抵抗）
上記で得られた容量を用いて、電気二重層キャパシタの充放電速度が一定になるように５ｍＡ／Ｆの定電流で充電を開始し、定電流充電と定電圧充電の充電時間を合わせて２０分間行った時点で充電完了とし、さらに、充電終了直後に定電流放電を充電時に用いたのと同様な電流値で０Ｖに達するまで行った。
(Internal resistance)
Using the capacity obtained above, charging is started at a constant current of 5 mA / F so that the charge / discharge rate of the electric double layer capacitor is constant, and the charging time of constant current charging and constant voltage charging is combined to be 20 The charging was completed at the time when the charging was performed for a minute, and further, constant current discharging was performed immediately after the end of charging until the voltage reached 0 V at the same current value used during charging.
内部抵抗は、放電開始から所定時間までの電圧データの最小二乗法による近似曲線の外挿からもとめた放電開始時電圧降下量を放電電流値で除した値とし、体積当たりの抵抗率、すなわち体積抵抗率として表し、以下の基準により評価した。但し、所定時間は全放電時間の５％とした。結果を表１に示した。
Ａ：０．６Ω未満
Ｂ：０．６以上０．８Ω未満
Ｃ：０．８以上１．０Ω未満
Ｄ：１．０Ω以上
The internal resistance is a value obtained by dividing the amount of voltage drop at the start of discharge from the extrapolation of the approximate curve by the least square method of voltage data from the start of discharge to the predetermined time divided by the discharge current value, and the resistivity per volume, that is, the volume Expressed as resistivity and evaluated according to the following criteria. However, the predetermined time was 5% of the total discharge time. The results are shown in Table 1.
A: Less than 0.6Ω B: 0.6 or more and less than 0.8Ω C: 0.8 or more and less than 1.0Ω D: 1.0Ω or more
（実施例１）
（バインダーの作製）
窒素置換した重合反応器に、アクリロニトリル（ＡＮ）４５部、１，３−ブタジエン（ＢＤ）５０部、メタクリル酸（ＭＭＡ）５部、ｔ−ドデシルメルカプタン（ＴＤＭ）０．２部、軟水１３２部、ドデシルベンゼンスルホン酸ナトリウム３．０部、β−ナフタリンスルホン酸ホルマリン縮合物ナトリウム塩０．５部、過硫酸カリウム０．３部及びエチレンジアミン四酢酸ナトリウム塩０．０５部を仕込み、重合温度４０℃を保持しながら重合転化率が９０％に達するまで反応させた。その後、重合停止剤としてジメチルジチオカルバミン酸ナトリウム０．１部を添加して重合反応を停止した。得られた共重合体粒子水分散液から未反応単量体を除去した後、共重合体粒子水分散液のｐＨ及び固形分濃度を調整して、固形分濃度４０％、ｐＨ８の共重合体粒子水分散液を得た。得られた共重合体粒子水分散液を１週間保存した後、防腐剤としてＢＩＴ（１，２−ベンズ−２−メチル−４−イソチアゾリン−３−オン）を共重合体粒子水分散液の固形分１００部に対して０．２部添加、撹拌し、バインダーＡ（ＮＢＲ）を得た。バインダーＡのＴｇは−２０℃、体積平均粒子径は１００ｎｍであった。
Example 1
(Preparation of binder)
In a nitrogen-substituted polymerization reactor, acrylonitrile (AN) 45 parts, 1,3-butadiene (BD) 50 parts, methacrylic acid (MMA) 5 parts, t-dodecyl mercaptan (TDM) 0.2 parts, soft water 132 parts, 3.0 parts of sodium dodecylbenzenesulfonate, 0.5 part of β-naphthalenesulfonic acid formalin condensate sodium salt, 0.3 part of potassium persulfate and 0.05 part of sodium ethylenediaminetetraacetate were added, and the polymerization temperature was 40 ° C. While maintaining, the reaction was continued until the polymerization conversion reached 90%. Thereafter, 0.1 part of sodium dimethyldithiocarbamate was added as a polymerization terminator to terminate the polymerization reaction. After removing unreacted monomers from the obtained aqueous dispersion of copolymer particles, the pH of the aqueous dispersion of copolymer particles and the solid content concentration are adjusted to obtain a copolymer having a solid content concentration of 40% and a pH of 8 An aqueous particle dispersion was obtained. After the obtained copolymer particle aqueous dispersion was stored for one week, BIT (1,2-benz-2-methyl-4-isothiazolin-3-one) as a preservative was solidified in the copolymer particle aqueous dispersion. 0.2 part was added to 100 parts per minute and stirred to obtain Binder A (NBR). The binder A had a Tg of −20 ° C. and a volume average particle size of 100 nm.
（複合粒子の作製）
キャパシタ電極活物質としてフェノール樹脂を原料とするアルカリ賦活活性炭である、体積平均粒子径が８μｍの活性炭粉末（ＭＳＰ−２０：関西熱化学社製）を１００部、導電材としてアセチレンブラック（商品名「デンカブラック粉状」：電気化学工業社製）を５部、溶解型結着剤としてカルボキシメチルセルロースの１．５％水溶液（商品名「ＷＳ−Ｃ」：ダイセル化学工業社製）を固形分相当量で１．４部、分散型結着剤としてバインダーＡを固形分相当量で１０部混合し、さらにイオン交換水を固形分濃度が２０％となるように加え、混合分散を行い、スラリーを得た。このスラリーを、スプレー乾燥機（大川原化工機社製）を使用し、回転円盤方式のアトマイザ（直径６５ｍｍ）の回転数２５，０００ｒｐｍ、熱風温度１５０℃、粒子回収出口の温度が９０℃で噴霧乾燥造粒を行い、球状複合粒子を得た。この球状複合粒子の平均体積粒子径は１００μｍであった。
(Production of composite particles)
100 parts of activated carbon powder (MSP-20: manufactured by Kansai Thermochemical Co., Ltd.), which is an alkali-activated activated carbon made from phenol resin as a capacitor electrode active material and having a volume average particle size of 8 μm, is acetylene black (trade name “ DENKA BLACK POWDER ”manufactured by Denki Kagaku Kogyo Co., Ltd.) 5 parts, 1.5% aqueous solution of carboxymethyl cellulose (trade name“ WS-C ”manufactured by Daicel Chemical Industries, Ltd.) as a solid binder 1.4 parts, 10 parts of binder A as a dispersion-type binder in an amount corresponding to the solid content is mixed, and ion-exchanged water is added so that the solid content concentration becomes 20%, and the mixture is dispersed to obtain a slurry. It was. This slurry is spray-dried using a spray dryer (Okawara Chemical Co., Ltd.) at a rotational speed of 25,000 rpm of a rotating disk type atomizer (diameter 65 mm), a hot air temperature of 150 ° C., and a particle recovery outlet temperature of 90 ° C. Granulation was performed to obtain spherical composite particles. The average volume particle diameter of the spherical composite particles was 100 μm.
（鉛蓄電池用キャパシタ電極の作製）
得られた球状複合粒子を、接着剤としてのポリエチレンイミンが０．５μｍの厚みで塗布された厚さ２０μｍの紙製の支持体面上に散布し、６５℃に加熱した加圧ロール（成形速度２０ｍ／分、プレス線圧５．０ｋＮ／ｃｍ（５００ｋＮ／ｍ））でシート成形を行い、支持体上にキャパシタ層がシート状に成形された鉛蓄電池用キャパシタ電極を得た。なお、実施例１で用いた、ポリエチレンイミンが塗布された支持体の接着力は、２．０Ｎ／ｍであった。
(Production of capacitor electrodes for lead-acid batteries)
The resulting spherical composite particles were sprayed on a 20 μm thick paper support coated with polyethyleneimine as an adhesive in a thickness of 0.5 μm and heated to 65 ° C. (molding speed 20 m). Sheet forming was performed at a pressing linear pressure of 5.0 kN / cm (500 kN / m)) to obtain a capacitor electrode for a lead storage battery in which the capacitor layer was formed into a sheet shape on the support. The adhesive strength of the support coated with polyethyleneimine used in Example 1 was 2.0 N / m.
（実施例２）
塗布されたポリエチレンイミンの厚みが１．０μｍである支持体を用いたこと以外は、実施例１と同様に鉛蓄電池用キャパシタ電極の作製を行った。なお、実施例２で用いた、ポリエチレンイミンが塗布された支持体の接着力は、４．０Ｎ／ｍであった。
(Example 2)
A lead-acid battery capacitor electrode was produced in the same manner as in Example 1 except that a support having a coated polyethyleneimine thickness of 1.0 μm was used. The adhesive strength of the support coated with polyethyleneimine used in Example 2 was 4.0 N / m.
（実施例３）
接着剤としてポリエチレンイミンに代えてアクリル系エマルジョンを用いたこと以外は、実施例１と同様に鉛蓄電池用キャパシタ電極の作製を行った。なお、実施例３で用いた、アクリル系エマルジョンが塗布された支持体の接着力は、０．８Ｎ／ｍであった。
(Example 3)
A capacitor electrode for a lead storage battery was produced in the same manner as in Example 1 except that an acrylic emulsion was used instead of polyethyleneimine as the adhesive. In addition, the adhesive force of the support body coated with the acrylic emulsion used in Example 3 was 0.8 N / m.
（実施例４）
厚さが５０μｍの支持体を用いた以外は、実施例１と同様に鉛蓄電池用キャパシタ電極の作製を行った。なお、実施例４で用いた、ポリエチレンイミンが塗布された支持体の接着力は、２．０Ｎ／ｍであった。
(Example 4)
A lead-acid battery capacitor electrode was produced in the same manner as in Example 1 except that a support having a thickness of 50 μm was used. In addition, the adhesive force of the support body coated with polyethyleneimine used in Example 4 was 2.0 N / m.
（比較例１）
接着剤としてのポリエチレンイミンに代えて、カーボンコートを塗布した支持体を用いたこと以外は、実施例１と同様に鉛蓄電池用キャパシタ電極の作製を行ったが、電極巻き取り時にキャパシタ層の一部が欠落したため、評価に必要な電極が得られなかった。なお、比較例１で用いた、カーボンコートが塗布された支持体の接着力は、０．１Ｎ／ｍであった。
(Comparative Example 1)
A lead-acid battery capacitor electrode was produced in the same manner as in Example 1 except that a carbon coated support was used instead of polyethyleneimine as an adhesive. Since the part was missing, the electrode required for evaluation was not obtained. In addition, the adhesive force of the support body coated with the carbon coat used in Comparative Example 1 was 0.1 N / m.
（比較例２）
厚さが１０μｍの支持体を用いた以外は、実施例１と同様に鉛蓄電池用キャパシタ電極の作製を行ったが、複合粒子を支持体上にプレスする際に紙製の支持体が破断したため、成形できず電極が得られなかった。
(Comparative Example 2)
A lead-acid battery capacitor electrode was produced in the same manner as in Example 1 except that a support having a thickness of 10 μm was used, but the paper support was broken when the composite particles were pressed onto the support. The electrode could not be obtained because it could not be molded.
（比較例３）
厚さが２００μｍの支持体を用いた以外は、実施例１と同様に鉛蓄電池用キャパシタ電極の作製を行った。
(Comparative Example 3)
A capacitor electrode for a lead storage battery was prepared in the same manner as in Example 1 except that a support having a thickness of 200 μm was used.
（比較例４）
複合粒子の作製に用いるためのスラリーから複合粒子を作製せず、このスラリーを、接着剤としてのポリエチレンイミンが０．５μｍの厚みで塗布された厚さ２０μｍの紙製の支持体面上に塗布し、鉛蓄電池用キャパシタ電極の作製を行ったが、塗布したスラリーの水分により紙製の支持体の強度が低下し、電極作成途中に支持体が切れたため電極が得られなかった。
(Comparative Example 4)
The composite particles are not prepared from the slurry for use in the preparation of the composite particles, and this slurry is applied on a paper support surface having a thickness of 20 μm and polyethyleneimine as an adhesive having a thickness of 0.5 μm. The capacitor electrode for a lead storage battery was manufactured, but the strength of the paper support was lowered by the moisture of the applied slurry, and the electrode was not obtained because the support was cut during the electrode preparation.
表１に示すように、接着剤が塗布された支持体と、キャパシタ電極活物質、導電材および結着剤を含む複合粒子を乾式成形したキャパシタ層とを含む鉛蓄電池用キャパシタ電極であり、前記支持体の接着力が０．２Ｎ／ｍ以上であり、厚さが１５μｍ以上１５０μｍ未満であると、キャパシタ電極強度、容量および内部抵抗のいずれもが良好であった。 As shown in Table 1, a lead-acid battery capacitor electrode including a support coated with an adhesive and a capacitor layer obtained by dry-molding composite particles including a capacitor electrode active material, a conductive material, and a binder, When the adhesive strength of the support was 0.2 N / m or more and the thickness was 15 μm or more and less than 150 μm, all of capacitor electrode strength, capacitance, and internal resistance were good.
１０…ワインダー、１２…プレス用ロール、１３…複合粒子、１４…支持体 DESCRIPTION OF SYMBOLS 10 ... Winder, 12 ... Roll for press, 13 ... Composite particle, 14 ... Support
Claims (4)
キャパシタ電極活物質、導電材および結着剤を含む複合粒子を乾式成形したキャパシタ層とを含む鉛蓄電池用キャパシタ電極であり、
前記支持体と前記キャパシタ層との間に接着剤層が存在し、
前記接着剤が塗布された前記支持体と厚さ５０μｍのＰＥＴフィルムとをロールプレスにて線圧０．５ｔ／ｍの条件で貼り付けた後、前記ＰＥＴフィルム面を上にして固定し、前記ＰＥＴフィルムを５０ｍｍ／分の速度で１８０°方向に引きはがしたときの応力として測定される前記支持体の接着力が０．２Ｎ／ｍ以上であり、厚さが１５μｍ以上１５０μｍ未満である鉛蓄電池用キャパシタ電極。 A support coated with an adhesive;
A capacitor electrode for a lead-acid battery comprising a capacitor layer obtained by dry-molding composite particles containing a capacitor electrode active material, a conductive material and a binder,
An adhesive layer is present between the support and the capacitor layer;
After pasting the support coated with the adhesive and a PET film having a thickness of 50 μm with a roll press under a condition of a linear pressure of 0.5 t / m, the PET film surface is fixed and fixed, Lead having an adhesive strength of 0.2 N / m or more and a thickness of 15 μm or more and less than 150 μm, measured as stress when the PET film is peeled off at 180 ° at a speed of 50 mm / min. Capacitor electrode for storage battery.
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |