JP4905492B2 - Electric double layer capacitor - Google Patents

Electric double layer capacitor Download PDF

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JP4905492B2
JP4905492B2 JP2009085655A JP2009085655A JP4905492B2 JP 4905492 B2 JP4905492 B2 JP 4905492B2 JP 2009085655 A JP2009085655 A JP 2009085655A JP 2009085655 A JP2009085655 A JP 2009085655A JP 4905492 B2 JP4905492 B2 JP 4905492B2
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active material
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material layer
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negative electrode
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JP2010238935A (en
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良彦 大橋
桂太 小林
秀毅 伊藤
一夫 片井
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TDK Corp
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Priority to CN201010155000A priority patent/CN101853742A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an electric double layer capacitor for attaining both high output and long life. <P>SOLUTION: Electrode bodies 4a, 4b of the electric double layer capacitor 100 are connected in series; a ratio of the area of an active material layer 24a for positive electrodes to that of an active material layer 34a for negative electrodes ranges from 78 to 128%; a ratio of the area of an active material layer 24b for positive electrodes to that of an active material layer 34b for negative electrodes ranges from 78 to 128%; a ratio of the maximum value to the minimum value of the area of the active material layers 24a, 24b for positive electrodes in the electrode bodies 4a, 4b is 105% or below; and a ratio of the maximum value to the minimum value of the area of the active material layers 34a, 34b for negative electrodes in the electrode bodies 4a, 4b is 105% or below. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

本発明は、電気二重層キャパシタに関するものである。   The present invention relates to an electric double layer capacitor.

近年、電子機器の高出力化に伴い、電源としての電気二重層キャパシタの使用電圧を向上させることが試みられている。電気二重層キャパシタの使用電圧を向上させる方法の一つとしては、複数のセルを直列接続する方法が提案されている（例えば、下記特許文献１参照）。特許文献１では、複数のコンデンサ素子を、導電性ゴムシートを間に介して面接触させて、直列に接触させて金属ケース内に収納した電気二重層キャパシタが開示されている。   In recent years, with the increase in output of electronic devices, attempts have been made to improve the working voltage of an electric double layer capacitor as a power source. As one method for improving the working voltage of the electric double layer capacitor, a method of connecting a plurality of cells in series has been proposed (for example, refer to Patent Document 1 below). Patent Document 1 discloses an electric double layer capacitor in which a plurality of capacitor elements are brought into surface contact with a conductive rubber sheet interposed therebetween and are contacted in series and housed in a metal case.

このように直列接続されたセルを用いた電気二重層キャパシタは、個々のセルの保持電圧にばらつきが生じてしまうと、過充電されたセルが充放電サイクルに伴い劣化してしまうことにより、電気二重層キャパシタ全体の寿命が劣化してしまう場合がある。そのため、このようなセルの保持電圧のばらつきを抑制することが検討されている（例えば、下記特許文献２参照）。特許文献２では、個々のセルの漏洩電流の相違に起因して生じる保持電圧のばらつきを抑制する電気二重層キャパシタが開示されている。   In such an electric double layer capacitor using cells connected in series, if the holding voltage of each cell varies, the overcharged cell deteriorates along with the charge / discharge cycle. The entire life of the double layer capacitor may be deteriorated. Therefore, it has been studied to suppress such variation in the holding voltage of the cell (for example, see Patent Document 2 below). Patent Document 2 discloses an electric double layer capacitor that suppresses variation in holding voltage caused by a difference in leakage current between individual cells.

特開２０００−２０８３７８号公報JP 2000-208378 A 特開２００２−１４２３６９号公報JP 2002-142369 A

しかし、特許文献１，２の電気二重層キャパシタでは、複数のセルを直列接続することで高出力化されるものの、電気二重層キャパシタの寿命は十分ではなかった。そのため、高出力化及び長寿命化が高水準に両立可能な電気二重層キャパシタが求められている。   However, in the electric double layer capacitors of Patent Documents 1 and 2, although the output is increased by connecting a plurality of cells in series, the life of the electric double layer capacitor is not sufficient. Therefore, there is a demand for an electric double layer capacitor that can achieve both high output and long life at a high level.

本発明は、上記課題を鑑みてなされたものであり、高出力化及び長寿命化が高水準に両立可能な電気二重層キャパシタを提供することを目的とする。   The present invention has been made in view of the above problems, and an object of the present invention is to provide an electric double layer capacitor capable of achieving both high output and long life at a high level.

本発明者らは、上述した電気二重層キャパシタの寿命が十分でない要因について検討したところ、従来の電気二重層キャパシタにおいて、容量の向上やインピーダンスの低減のために正極及び負極の電極面積を異ならせる場合があり、これにより個々のセルの保持電圧にばらつきが生じる場合があることに原因があることを見出した。このような保持電圧のばらつきに起因して、過充電されたセルが充放電サイクルに伴い劣化してしまい、電気二重層キャパシタ全体の寿命が劣化してしまうところ、本発明者らは、正極及び負極の電極面積を所定の条件を満たすようにすることで、このような問題を解決可能であることを見出した。   The inventors of the present invention have examined the above-mentioned factors that the electric double layer capacitor does not have a sufficient lifetime. In the conventional electric double layer capacitor, the electrode areas of the positive electrode and the negative electrode are made different in order to improve the capacity and reduce the impedance. In some cases, it has been found that the cause is that the holding voltage of each cell may vary. Due to such variation in holding voltage, the overcharged cell is deteriorated along with the charge / discharge cycle, and the life of the entire electric double layer capacitor is deteriorated. It has been found that such a problem can be solved by satisfying a predetermined condition for the electrode area of the negative electrode.

本発明は、集電体上に活物質層が形成された正極と負極とがセパレータを挟んで積層された複数の電極体を備え、複数の電極体が電気的に直列に接続され、複数の電極体のそれぞれにおいて、負極の活物質層の面積に対する正極の活物質層の面積の比が７８〜８１％又は１０２〜１２８％であり、複数の電極体において正極の活物質層の面積の最小値に対する正極の活物質層の面積の最大値の比が１０５％以下であり、複数の電極体において負極の活物質層の面積の最小値に対する負極の活物質層の面積の最大値の比が１０５％以下である、電気二重層キャパシタを提供する。 The present invention includes a plurality of electrode bodies in which an active material layer formed on a current collector and a negative electrode are stacked with a separator interposed therebetween, the plurality of electrode bodies being electrically connected in series, in each of the electrode body, the area of the positive electrode active material layer to the area of the active material layer of the negative electrode ratio Ri is 78 to 81%, or 102 to 128% der, of the area of the positive electrode active material layer in a plurality of electrode bodies The ratio of the maximum value of the area of the positive electrode active material layer to the minimum value is 105% or less, and the ratio of the maximum value of the area of the negative electrode active material layer to the minimum value of the area of the negative electrode active material layer in the plurality of electrode bodies An electric double layer capacitor is provided, wherein

本発明では、直列接続された複数の電極体のそれぞれにおいて負極の活物質層の面積に対する正極の活物質層の面積の比が７８〜１２８％であると共に、異なる電極体における同極の電極同士の活物質層の面積の最小値に対する活物質層の面積の最大値の比が１０５％以下であることにより、面積の相違に起因する保持電圧のばらつきの発生が抑制される。これにより、複数の電極体のそれぞれに均等に電圧が印加されることとなり、電気二重層キャパシタの充放電サイクルに伴う劣化を抑制することができる。したがって、高出力化及び長寿命化を高水準に両立可能となる。   In the present invention, the ratio of the area of the positive electrode active material layer to the area of the negative electrode active material layer in each of the plurality of electrode bodies connected in series is 78 to 128%, and the electrodes of the same polarity in different electrode bodies The ratio of the maximum value of the area of the active material layer to the minimum value of the area of the active material layer is 105% or less, so that occurrence of variations in holding voltage due to the difference in area is suppressed. Thereby, a voltage will be equally applied to each of a some electrode body, and the deterioration accompanying the charging / discharging cycle of an electric double layer capacitor can be suppressed. Therefore, it is possible to achieve both high output and long life at a high level.

本発明によれば、高出力化及び長寿命化が高水準に両立可能な電気二重層キャパシタが提供される。   ADVANTAGE OF THE INVENTION According to this invention, the electrical double layer capacitor which can make high output and long lifetime compatible to a high level is provided.

本発明の一実施形態の電気二重層キャパシタをその一部を切り欠いて示す斜視図である。1 is a perspective view showing a part of an electric double layer capacitor according to an embodiment of the present invention. 図１のＩＩ−ＩＩ線断面図である。It is the II-II sectional view taken on the line of FIG.

以下、添付図面を参照しながら、本発明の好適な実施形態について詳細に説明する。なお、図面の説明において、同一または相当要素には同一の符号を付し、重複する説明は省略する。また、各図面の寸法比率は、必ずしも実際の寸法比率とは一致していない。   Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In the description of the drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant description is omitted. In addition, the dimensional ratio in each drawing does not necessarily match the actual dimensional ratio.

まず、本実施形態の電気二重層キャパシタ１００について図１，２を参照して説明する。図１は、本実施形態の電気二重層キャパシタ１００をその一部を切り欠いて示す斜視図である。図２は、図１のＩＩ−ＩＩ線断面図である。   First, the electric double layer capacitor 100 of this embodiment will be described with reference to FIGS. FIG. 1 is a perspective view showing the electric double layer capacitor 100 of the present embodiment with a part thereof cut away. 2 is a cross-sectional view taken along line II-II in FIG.

電気二重層キャパシタ１００は、２つの電極体４ａ，４ｂが隔壁６を介して積層された積層体８と、積層体８を収容する外装体１０と、リード５０ａ，５０ｂ，５２ａ，５２ｂとを備えている。   The electric double layer capacitor 100 includes a laminated body 8 in which two electrode bodies 4a and 4b are laminated via a partition wall 6, an exterior body 10 that houses the laminated body 8, and leads 50a, 50b, 52a, and 52b. ing.

電極体４ａは、帯状の正極２０ａ／帯状のセパレータ４０／帯状の負極３０ａ／帯状のセパレータ４０の順に積層された帯状の積層体が長手方向に巻かれた巻回体である。電極体４ｂは、帯状の正極２０ｂ／帯状のセパレータ４０／帯状の負極３０ｂ／帯状のセパレータ４０の順に積層された帯状の積層体が長手方向に巻かれた巻回体である。電極体４ａ，４ｂは、帯状の積層体の幅方向に垂直な断面が略楕円状を呈している。電極体４ａ，４ｂは、帯状の積層体の幅方向の一端が外装体１０の開口部１２に面するように配置されており、電極体４ａ，４ｂのそれぞれの一側面は、隔壁６に接している。   The electrode body 4a is a wound body in which a belt-like laminate that is laminated in the order of the belt-like positive electrode 20a / the belt-like separator 40 / the belt-like negative electrode 30a / the belt-like separator 40 is wound in the longitudinal direction. The electrode body 4b is a wound body in which a belt-like laminate that is laminated in the order of the belt-like positive electrode 20b / the belt-like separator 40 / the belt-like negative electrode 30b / the belt-like separator 40 is wound in the longitudinal direction. The electrode bodies 4a and 4b have a substantially elliptical cross section perpendicular to the width direction of the belt-like laminate. The electrode bodies 4 a and 4 b are arranged so that one end in the width direction of the belt-shaped laminate is facing the opening 12 of the exterior body 10, and one side surface of each of the electrode bodies 4 a and 4 b is in contact with the partition wall 6. ing.

正極２０ａは、帯状の正極用集電体２２ａと、正極用集電体２２ａの表面及び裏面に形成された正極用活物質層２４ａとを備える。負極３０ａは、帯状の負極用集電体３２ａと、負極用集電体３２ａの表面及び裏面に形成された負極用活物質層３４ａとを備える。正極２０ｂは、帯状の正極用集電体２２ｂと、正極用集電体２２ｂの表面及び裏面に形成された正極用活物質層２４ｂとを備える。負極３０ｂは、帯状の負極用集電体３２ｂと、負極用集電体３２ｂの表面及び裏面に形成された負極用活物質層３４ｂとを備える。なお、本実施形態において、「正極」とは、電気二重層キャパシタに電圧を印加した際に、電解質溶液中のアニオンが吸着する電極であり、「負極」とは、電気二重層キャパシタに電圧を印加した際に、電解質溶液中のカチオンが吸着する電極である。なお、電気二重層キャパシタに対して一度特定の正負の向きに電圧を印加して充電した後に再充電する際には、通常最初と同じ向きに充電を行い、逆向きに電圧を印加して充電することは少ない。   The positive electrode 20a includes a strip-shaped positive electrode current collector 22a and a positive electrode active material layer 24a formed on the front and back surfaces of the positive electrode current collector 22a. The negative electrode 30a includes a strip-shaped negative electrode current collector 32a and a negative electrode active material layer 34a formed on the front and back surfaces of the negative electrode current collector 32a. The positive electrode 20b includes a strip-shaped positive electrode current collector 22b and a positive electrode active material layer 24b formed on the front and back surfaces of the positive electrode current collector 22b. The negative electrode 30b includes a strip-shaped negative electrode current collector 32b and a negative electrode active material layer 34b formed on the front and back surfaces of the negative electrode current collector 32b. In this embodiment, the “positive electrode” is an electrode that adsorbs anions in the electrolyte solution when a voltage is applied to the electric double layer capacitor, and the “negative electrode” is a voltage applied to the electric double layer capacitor. When applied, the electrode adsorbs cations in the electrolyte solution. In addition, when recharging after applying a voltage to the electric double layer capacitor once in a specific positive / negative direction, charging is usually performed in the same direction as the first and charged by applying a voltage in the opposite direction. There is little to do.

正極用集電体２２ａ，２２ｂ及び負極用集電体３２ａ，３２ｂとしては、一般的に高い導電性を有する材料であれば特に限定されないが、低電気抵抗の金属材料が好ましく用いられ、例えば、銅、アルミニウム、ニッケル等が用いられる。正極用集電体２２ａ，２２ｂ及び負極用集電体３２ａ，３２ｂの厚みは、例えば１０〜５０μｍ程度である。正極用集電体２２ａ，２２ｂ及び負極用集電体３２ａ，３２ｂには、リード接続用のタブ５４が設けられており、タブ５４は、電極体４ａ，４ｂにおいて外装体１０の開口部１２側に突出している。   The positive electrode current collectors 22a and 22b and the negative electrode current collectors 32a and 32b are not particularly limited as long as they are generally highly conductive materials, but metal materials having low electrical resistance are preferably used. Copper, aluminum, nickel or the like is used. The thicknesses of the positive electrode current collectors 22a and 22b and the negative electrode current collectors 32a and 32b are, for example, about 10 to 50 μm. The positive electrode current collectors 22a and 22b and the negative electrode current collectors 32a and 32b are provided with tabs 54 for lead connection. The tabs 54 are located on the opening 12 side of the outer package 10 in the electrode bodies 4a and 4b. Protruding.

正極用活物質層２４ａ，２４ｂ及び負極用活物質層３４ａ，３４ｂは、活物質及びバインダを含み、好ましくは導電助剤を含む。   The positive electrode active material layers 24a and 24b and the negative electrode active material layers 34a and 34b include an active material and a binder, and preferably include a conductive additive.

活物質としては、種々の電子伝導性を有する多孔体が挙げられ、例えば、天然黒鉛、人造黒鉛、メソカーボンマイクロビーズ、メソカーボンファイバー（ＭＣＦ）、コークス類、ガラス状炭素、有機化合物焼成体等の炭素材料が挙げられる。   Examples of the active material include porous bodies having various electronic conductivities, such as natural graphite, artificial graphite, mesocarbon microbeads, mesocarbon fibers (MCF), cokes, glassy carbon, and organic compound fired bodies. The carbon material is mentioned.

バインダとしては、上記の活物質、及び好ましくは導電助剤を集電体に固定することができれば特に限定されず、種々の結着剤を使用できる。バインダとしては、例えば、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリテトラフルオロエチレン（ＰＴＦＥ）等のフッ素樹脂や、スチレン−ブタジエンゴム（ＳＢＲ）と水溶性高分子（カルボキシメチルセルロース、ポリビニルアルコール、ポリアクリル酸ナトリウム、デキストリン、グルテン等）との混合物等が挙げられる。   The binder is not particularly limited as long as the above active material and preferably the conductive auxiliary agent can be fixed to the current collector, and various binders can be used. Examples of the binder include fluorine resins such as polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), styrene-butadiene rubber (SBR) and water-soluble polymers (carboxymethylcellulose, polyvinyl alcohol, sodium polyacrylate, Dextrin, gluten, etc.) and the like.

導電助剤は、正極用活物質層２４ａ，２４ｂ及び負極用活物質層３４ａ，３４ｂの電子伝導性を高めるために添加される材料である。導電助剤としては、例えば、カーボンブラック、アセチレンブラック等の炭素材料、銅、ニッケル、ステンレス、鉄等の金属微粉、炭素材料及び金属微粉の混合物、ＩＴＯ等の導電性酸化物が挙げられる。   The conductive additive is a material added to increase the electron conductivity of the positive electrode active material layers 24a and 24b and the negative electrode active material layers 34a and 34b. Examples of the conductive aid include carbon materials such as carbon black and acetylene black, fine metal powders such as copper, nickel, stainless steel, and iron, a mixture of carbon materials and fine metal powders, and conductive oxides such as ITO.

正極用活物質層２４ａ，２４ｂ及び負極用活物質層３４ａ，３４ｂの厚さは、例えば１〜２００μｍ程度である。正極用活物質層２４ａ，２４ｂ及び負極用活物質層３４ａ，３４ｂは、リードが設けられるタブ５４を避けるように集電体上に形成されている。正極用活物質層２４ａ，２４ｂ及び負極用活物質層３４ａ，３４ｂは、公知の方法で作製することができる。   The thicknesses of the positive electrode active material layers 24a and 24b and the negative electrode active material layers 34a and 34b are, for example, about 1 to 200 μm. The positive electrode active material layers 24a and 24b and the negative electrode active material layers 34a and 34b are formed on the current collector so as to avoid the tabs 54 provided with leads. The positive electrode active material layers 24a and 24b and the negative electrode active material layers 34a and 34b can be produced by a known method.

セパレータ４０は、正極２０ａ及び負極３０ａ間と、正極２０ｂ及び負極３０ｂ間とをそれぞれ電気的に絶縁するものであって、電気絶縁性の多孔体である。セパレータ４０としては、特に限定されず、種々のセパレータ材料を使用することができる。例えば、電気絶縁性の多孔体としては、ポリエチレン、ポリプロピレン又はポリオレフィンからなるフィルムの単層体、積層体や、上記樹脂の混合物の延伸膜、或いは、セルロース、ポリエステル及びポリプロピレンからなる群より選択される少なくとも１種の構成材料からなる繊維不織布が挙げられる。セパレータ４０の厚さは、例えば５〜５０μｍ程度である。   The separator 40 electrically insulates between the positive electrode 20a and the negative electrode 30a and between the positive electrode 20b and the negative electrode 30b, and is an electrically insulating porous body. The separator 40 is not particularly limited, and various separator materials can be used. For example, the electrically insulating porous body is selected from the group consisting of monolayers and laminates of films made of polyethylene, polypropylene or polyolefin, stretched films of a mixture of the above resins, or cellulose, polyester and polypropylene. Examples thereof include a fiber nonwoven fabric made of at least one constituent material. The thickness of the separator 40 is, for example, about 5 to 50 μm.

隔壁６は、２つの電極体４ａ、４ｂにそれぞれ含まれる後述の電解質溶液を透過させない材料からなり、例えばエポキシ樹脂等の合成樹脂や、アルミニウム，ステンレス等の金属シートを樹脂フィルム（ポリプロピレン等）でラミネートしたものにより形成されている。隔壁６の厚さは、例えば１０〜１００μｍ程度である。隔壁６を設けることにより、２つの電極体４ａ、４ｂにそれぞれ含まれる電解質溶液が互いに混合することが抑制され、電気二重層キャパシタ１００の電圧の低下を抑制できる。   The partition wall 6 is made of a material that does not allow the later-described electrolyte solution contained in each of the two electrode bodies 4a and 4b to pass therethrough. For example, a synthetic resin such as an epoxy resin, or a metal sheet such as aluminum or stainless steel is used as a resin film (polypropylene or the like). It is formed by laminating. The thickness of the partition wall 6 is, for example, about 10 to 100 μm. By providing the partition wall 6, the electrolyte solutions contained in the two electrode bodies 4a and 4b are suppressed from mixing with each other, and the voltage drop of the electric double layer capacitor 100 can be suppressed.

リード５０ａ，５０ｂ，５２ａ，５２ｂは、正極用集電体２２ａ，２２ｂ及び負極用集電体３２ａ，３２ｂに対して電流の入出力端子の役割を果たす導電性部材であり、矩形板形状をなしている。リード５０ａ，５０ｂ，５２ａ，５２ｂの厚さは、例えば５０〜１０００μｍ程度である。   The leads 50a, 50b, 52a, 52b are conductive members that serve as current input / output terminals for the positive current collectors 22a, 22b and the negative current collectors 32a, 32b, and have a rectangular plate shape. ing. The thickness of the leads 50a, 50b, 52a, 52b is, for example, about 50 to 1000 μm.

リード５０ａの長手方向の一端は、一方の電極体４ａにおける正極２０ａの正極用集電体２２ａに電気的に接続されており、リード５２ａの長手方向の一端は、電極体４ａにおける負極３０ａの負極用集電体３２ａに電気的に接続されており、リード５０ｂの長手方向の一端は、他方の電極体４ｂにおける正極２０ｂの正極用集電体２２ｂに電気的に接続されており、リード５２ｂの長手方向の一端は、電極体４ｂにおける負極３０ｂの負極用集電体３２ｂに電気的に接続されている。リード５０ａ，５０ｂ，５２ａ，５２ｂと各集電体に設けられたタブ５４とは、例えば、導電性の接着剤、ハンダ、溶接等により固定されている。リード５０ａ，５０ｂ，５２ａ，５２ｂは、各リードの上記一端から、開口部１２を通って外装体１０の外側へ伸びている。   One end in the longitudinal direction of the lead 50a is electrically connected to the positive electrode current collector 22a of the positive electrode 20a in one electrode body 4a, and one end in the longitudinal direction of the lead 52a is the negative electrode of the negative electrode 30a in the electrode body 4a. One end of the lead 50b in the longitudinal direction is electrically connected to the positive electrode current collector 22b of the positive electrode 20b in the other electrode body 4b, and the lead 52b One end in the longitudinal direction is electrically connected to the negative electrode current collector 32b of the negative electrode 30b in the electrode body 4b. The leads 50a, 50b, 52a, 52b and the tab 54 provided on each current collector are fixed by, for example, conductive adhesive, solder, welding, or the like. The leads 50 a, 50 b, 52 a, 52 b extend from the one end of each lead to the outside of the exterior body 10 through the opening 12.

リード５０ａ及びリード５２ｂは、開口部１２における電極体４ａ，４ｂの積層方向に離隔して対向する位置からそれぞれ突出しており、外装体１０の外部で互いに接触し、電気的に接続されている。これにより、互いに極性の異なる集電体に接続されたリード５０ａ，５２ｂ同士が電気的に接続されることによって、２つの電極体４ａ、４ｂ同士を直列接続し、電気二重層キャパシタ１００の電圧を向上させることができる。   The lead 50a and the lead 52b protrude from positions opposed to each other in the stacking direction of the electrode bodies 4a and 4b in the opening 12, and are in contact with each other outside the exterior body 10 and are electrically connected. As a result, the leads 50a and 52b connected to the current collectors having different polarities are electrically connected to each other so that the two electrode bodies 4a and 4b are connected in series, and the voltage of the electric double layer capacitor 100 is increased. Can be improved.

外装体１０は、電極体４ａ，４ｂを密封し、ケース内部へ空気や水分が進入するのを防止するものである。外装体１０としては、例えば、エポキシ樹脂等の合成樹脂や、アルミニウム，ステンレス等の金属シートを樹脂フィルム（ポリプロピレン、ポリエチレン等）でラミネートしたものを使用することができる。外装体１０の壁の厚さは、例えば１０〜５００μｍ程度である。   The exterior body 10 seals the electrode bodies 4a and 4b and prevents air and moisture from entering the inside of the case. As the exterior body 10, for example, a synthetic resin such as an epoxy resin or a metal sheet such as aluminum or stainless steel laminated with a resin film (polypropylene, polyethylene, or the like) can be used. The wall thickness of the exterior body 10 is, for example, about 10 to 500 μm.

外装体１０の開口部１２におけるリード５０ａ，５０ｂ，５２ａ，５２ｂの周囲には、封止部材６０が配置されており、この封止部材６０が外装体１０の内壁と各リードと密着することにより、開口部１２が封止されている。封止部材６０としては、開口部１２との熱融着時に、開口部１２との密着性が良好である材料を用いればよく、具体的には、エチレン−酢酸ビニル共重合体、エチレン−アクリレート共重合体、ポリプロピレン重合体、等を用いることができる。   A sealing member 60 is disposed around the leads 50a, 50b, 52a, and 52b in the opening 12 of the outer package 10, and the sealing member 60 is in close contact with the inner wall of the outer package 10 and each lead. The opening 12 is sealed. As the sealing member 60, a material having good adhesion to the opening 12 at the time of heat-sealing with the opening 12 may be used. Specifically, an ethylene-vinyl acetate copolymer, ethylene-acrylate is used. A copolymer, a polypropylene polymer, and the like can be used.

外装体１０の内部空間には、電解質溶液（図示せず）が充填され、その一部は、正極２０ａ，２０ｂ、負極３０ａ，３０ｂ及びセパレータ４０の内部に含浸されている。   The internal space of the outer package 10 is filled with an electrolyte solution (not shown), and a part thereof is impregnated inside the positive electrodes 20a and 20b, the negative electrodes 30a and 30b, and the separator 40.

電解質溶液としては、電解質を有機溶媒に溶解させたものが使用される。電解質としては、例えば、テトラエチルアンモニウムテトラフルオロボレート（ＴＥＡ＋ＢＦ４ −）、トリエチルモノメチルアンモニウムテトラフルオロボレート（ＴＥＭＡ＋ＢＦ４ −）等の４級アンモニウム塩を用いるのが好ましい。 As the electrolyte solution, a solution in which an electrolyte is dissolved in an organic solvent is used. As the electrolyte, for example, tetraethylammonium tetrafluoroborate (TEA + BF 4 -), triethyl monomethyl ammonium tetrafluoroborate (TEMA + BF 4 -) is preferably used a quaternary ammonium salt or the like.

なお、これらの電解質は１種を単独で使用してもよく、２種以上を併用してもよい。   In addition, these electrolytes may be used individually by 1 type, and may use 2 or more types together.

また、有機溶媒としては、公知の溶媒を使用することができる。有機溶媒としては、例えば、プロピレンカーボネート、エチレンカーボネート、及び、ジエチルカーボネート等が好ましく挙げられる。これらは単独で使用してもよく、２種以上を任意の割合で混合して使用してもよい。   Moreover, a well-known solvent can be used as an organic solvent. Preferred examples of the organic solvent include propylene carbonate, ethylene carbonate, and diethyl carbonate. These may be used alone or in combination of two or more at any ratio.

次に、電極体４ａの正極２０ａ及び負極３０ａと、電極体４ｂの正極２０ｂ及び負極３０ｂとにおける活物質層の面積の相関関係について説明する。なお、活物質層の面積は、巻回されて電気二重層キャパシタとして機能する状態での面積であるが、通常、この面積は巻回される前の帯状の電極の活物質層の面積と同等である。また、本実施形態において、一方の電極の活物質層の面積とは、１つの電極体の一方の電極の全ての活物質層の面積の合計である。活物質層の面積は、集電体の長さや幅、集電体上に形成する活物質層の長さや幅等を変えることにより容易に調節することができる。   Next, the correlation between the areas of the active material layers in the positive electrode 20a and the negative electrode 30a of the electrode body 4a and the positive electrode 20b and the negative electrode 30b of the electrode body 4b will be described. The area of the active material layer is an area in a state where it is wound and functions as an electric double layer capacitor, but this area is usually equal to the area of the active material layer of the strip-shaped electrode before being wound. It is. In this embodiment, the area of the active material layer of one electrode is the sum of the areas of all the active material layers of one electrode of one electrode body. The area of the active material layer can be easily adjusted by changing the length and width of the current collector, the length and width of the active material layer formed on the current collector, and the like.

そして、一方の電極体４ａにおける、負極３０ａの負極用活物質層３４ａの面積に対する正極２０ａの正極用活物質層２４ａの面積の比、及び、他方の電極体４ｂにおける、負極３０ｂの負極用活物質層３４ｂの面積に対する正極２０ｂの正極用活物質層２４ｂの面積の比は、７８〜１２８％であり、電極体４ａ，４ｂ間の電圧バランスを最適化する観点から、８０〜１２５％が好ましく、８１〜１２３％がより好ましい。   Then, the ratio of the area of the positive electrode active material layer 24a of the positive electrode 20a to the area of the negative electrode active material layer 34a of the negative electrode 30a in one electrode body 4a and the negative electrode active material of the negative electrode 30b in the other electrode body 4b. The ratio of the area of the positive electrode active material layer 24b of the positive electrode 20b to the area of the material layer 34b is 78 to 128%, and 80 to 125% is preferable from the viewpoint of optimizing the voltage balance between the electrode bodies 4a and 4b. 81 to 123% is more preferable.

また、２つの電極体４ａ，４ｂにおいて、正極２０ａの正極用活物質層２４ａの面積、及び、正極２０ｂの正極用活物質層２４ｂの面積のうちの最小値に対する最大値の比は、１０５％以下であり、直列接続された電極体４ａ，４ｂの容量比を整合させ、劣化を低減させる観点から、１００〜１０５％が好ましく、１００〜１０３％がより好ましい。例えば、正極２０ａの正極用活物質層２４ａの面積が正極２０ｂの正極用活物質層２４ｂの面積よりも大きい場合には、正極用活物質層２４ｂの面積に対する正極用活物質層２４ａの面積の比は、１０５％以下である。   In the two electrode bodies 4a and 4b, the ratio of the maximum value to the minimum value of the area of the positive electrode active material layer 24a of the positive electrode 20a and the area of the positive electrode active material layer 24b of the positive electrode 20b is 105%. From the viewpoint of matching the capacity ratio of the electrode bodies 4a and 4b connected in series and reducing the deterioration, 100 to 105% is preferable, and 100 to 103% is more preferable. For example, when the area of the positive electrode active material layer 24a of the positive electrode 20a is larger than the area of the positive electrode active material layer 24b of the positive electrode 20b, the area of the positive electrode active material layer 24a with respect to the area of the positive electrode active material layer 24b The ratio is 105% or less.

更に、２つの電極体４ａ，４ｂにおいて、負極３０ａの負極用活物質層３４ａの面積、及び、負極３０ｂの負極用活物質層３４ｂの面積のうちの最小値に対する最大値の比は、１０５％以下であり、直列接続された電極体４ａ，４ｂの容量比を整合させ、劣化を低減させる観点から、１００〜１０５％が好ましく、１００〜１０３％がより好ましい。例えば、負極３０ａの負極用活物質層３４ａの面積が負極３０ｂの負極用活物質層３４ｂの面積よりも大きい場合には、負極用活物質層３４ｂの面積に対する負極用活物質層３４ａの面積の比は、１０５％以下である。   Further, in the two electrode bodies 4a and 4b, the ratio of the maximum value to the minimum value of the area of the negative electrode active material layer 34a of the negative electrode 30a and the area of the negative electrode active material layer 34b of the negative electrode 30b is 105%. From the viewpoint of matching the capacity ratio of the electrode bodies 4a and 4b connected in series and reducing the deterioration, 100 to 105% is preferable, and 100 to 103% is more preferable. For example, when the area of the negative electrode active material layer 34a of the negative electrode 30a is larger than the area of the negative electrode active material layer 34b of the negative electrode 30b, the area of the negative electrode active material layer 34a relative to the area of the negative electrode active material layer 34b The ratio is 105% or less.

なお、これらの関係を満たす限り、正極活物質層２４ａ，２４ｂ及び負極活物質層３４ａ，３４ｂの形状や、これらの層の各集電体の表面及び裏面間における面積の分配比は、特に限定されない。なお、２４ａ，２４ｂ及び負極用活物質層３４ａ，３４ｂは、それぞれ、集電体の表面及び裏面において同じ面積であることが好ましい。   As long as these relationships are satisfied, the shapes of the positive electrode active material layers 24a and 24b and the negative electrode active material layers 34a and 34b and the distribution ratio of the area between the front and back surfaces of the current collectors of these layers are particularly limited. Not. In addition, it is preferable that 24a and 24b and the active material layers 34a and 34b for negative electrodes are the same areas in the surface and the back surface of a collector, respectively.

本実施形態では、直列接続された各電極体４ａ，４ｂにおいて、負極３０ａの負極用活物質層３４ａの面積に対する正極２０ａの正極用活物質層２４ａの面積の比、及び、負極３０ｂの負極用活物質層３４ｂの面積に対する正極２０ｂの正極用活物質層２４ｂの面積の比がそれぞれ７８〜１２８％であると共に、電極体４ａにおける正極２０ａの正極用活物質層２４ａの面積及び電極体４ｂにおける正極２０ｂの正極用活物質層２４ｂの面積のうちの最小値に対する最大値の比が１０５％以下であり、更に、電極体４ａにおける負極３０ａの負極用活物質層３４ａの面積及び電極体４ｂにおける負極３０ｂの負極用活物質層３４ｂの面積のうちの最小値に対する最大値の比が１０５％以下である。これにより、面積の相違に起因する電極体４ａ，４ｂの保持電圧のばらつきの発生が抑制される。そのため、電極体４ａ，４ｂのそれぞれに均等に電圧が印加されることとなり、電気二重層キャパシタ１００の充放電サイクルに伴う劣化を抑制することができる。したがって、高出力化及び長寿命化を高水準に両立可能となる。   In the present embodiment, in each of the electrode bodies 4a and 4b connected in series, the ratio of the area of the positive electrode active material layer 24a of the positive electrode 20a to the area of the negative electrode active material layer 34a of the negative electrode 30a and the negative electrode for the negative electrode 30b The ratio of the area of the positive electrode active material layer 24b of the positive electrode 20b to the area of the active material layer 34b is 78 to 128%, respectively, and the area of the positive electrode active material layer 24a of the positive electrode 20a in the electrode body 4a and the area of the electrode body 4b The ratio of the maximum value to the minimum value of the area of the positive electrode active material layer 24b of the positive electrode 20b is 105% or less, and further, the area of the negative electrode active material layer 34a of the negative electrode 30a in the electrode body 4a and the electrode body 4b The ratio of the maximum value to the minimum value in the area of the negative electrode active material layer 34b of the negative electrode 30b is 105% or less. Thereby, the occurrence of variations in the holding voltage of the electrode bodies 4a and 4b due to the difference in area is suppressed. Therefore, a voltage is equally applied to each of the electrode bodies 4a and 4b, and deterioration accompanying the charge / discharge cycle of the electric double layer capacitor 100 can be suppressed. Therefore, it is possible to achieve both high output and long life at a high level.

本発明は上記実施形態に限られず、様々な変形態様が可能である。例えば、上記実施形態では、２つの電極体４ａ，４ｂが直列接続されているが、３つ以上の電極体が直列接続されていてもよい。３つ以上の電極体が直列接続されている場合であっても、各電極体のいずれにおいても負極用活物質層の面積に対する正極用活物質層の面積の比が７８〜１２８％であり、全電極体における正極用活物質層の面積の最小値に対する正極用活物質層の面積の最大値の比が１０５％以下であり、かつ、全電極体における負極用活物質層の面積の最小値に対する負極用活物質層の面積の最大値の比が１０５％以下であればよい。   The present invention is not limited to the above-described embodiment, and various modifications can be made. For example, in the above embodiment, the two electrode bodies 4a and 4b are connected in series, but three or more electrode bodies may be connected in series. Even in the case where three or more electrode bodies are connected in series, the ratio of the area of the positive electrode active material layer to the area of the negative electrode active material layer in each of the electrode bodies is 78 to 128%, The ratio of the maximum area of the positive electrode active material layer to the minimum area of the positive electrode active material layer in all electrode bodies is 105% or less, and the minimum value of the area of the negative electrode active material layer in all electrode bodies The ratio of the maximum value of the area of the negative electrode active material layer to the negative electrode may be 105% or less.

また、各活物質層は、各集電体の一方の面のみに形成されていてもよい。更に、上記実施形態では、電極体４ａ，４ｂは巻回体であるが、これに限られるものではなく、積層体、九十九折り体等であってもよい。   Each active material layer may be formed only on one surface of each current collector. Furthermore, in the said embodiment, although the electrode bodies 4a and 4b are winding bodies, it is not restricted to this, A laminated body, a 99-fold body, etc. may be sufficient.

本発明の電気二重層キャパシタは、自走式のマイクロマシン、ＩＣカード等の電源や、プリント基板上又はプリント基板内に配置される分散電源の用途にも使用することが可能である。   The electric double layer capacitor of the present invention can also be used for a power source of a self-propelled micromachine, an IC card, or a distributed power source disposed on or in a printed board.

以下、実施例及び比較例を挙げて本発明について更に詳しく説明するが、本発明はこれらの実施例に何ら限定されるものではない。   EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in more detail, this invention is not limited to these Examples at all.

（実施例１）
活物質として活性炭粒子（クラレケミカル社製、商品名：ＲＰ−２０）を、バインダとしてＰＶＤＦを用い、活物質：バインダ＝７０：３０の質量割合となるようにこれらを混合し、得られた混合物にＮ−メチルピロリドンを加えて混練することにより、塗布液を調製した。次に、上記塗布液をドクターブレード法でアルミニウム箔（厚さ：２０μｍ）の両面上に塗布し乾燥させ、厚さ２０μｍの活物質層が両面上に積層されたシートを得た。そして、活物質層の長さ及び幅が表１の値となるように、リード接続用のタブを設けた帯状の電極を上記シートから４つ打ち抜き、これらの電極のタブにアルミニウム箔からなるリード（厚さ：１００μｍ）を超音波溶接法により接続した。 Example 1
Activated carbon particles (trade name: RP-20, manufactured by Kuraray Chemical Co., Ltd.) are used as the active material, PVDF is used as the binder, and these are mixed so that the mass ratio of active material: binder = 70: 30 is obtained. A coating solution was prepared by adding N-methylpyrrolidone to the mixture and kneading. Next, the coating solution was applied onto both sides of an aluminum foil (thickness: 20 μm) by the doctor blade method and dried to obtain a sheet in which an active material layer having a thickness of 20 μm was laminated on both sides. Then, four strip-like electrodes provided with lead connection tabs are punched from the sheet so that the length and width of the active material layer are the values shown in Table 1, and the lead made of aluminum foil is formed on the tab of these electrodes. (Thickness: 100 μm) were connected by ultrasonic welding.

次に、一つの電極の両面をセパレータとしての再生セルロース製不織布（厚さ：３０μｍ、大きさ：１４ｍｍ×１９５ｍｍ）で覆ってから、他の一つの電極と対向させ、１００℃、１ｋｇ／ｃｍ２、１０秒の条件で加熱加圧して、帯状の積層体を得た。この積層体を端部から円筒状に巻回し、巻き終わり部を巻き止めテープで止め、巻回型の電極体を得た。残りの２つの電極を用いて、同様に巻回型の電極体をもう１つ作製した。 Next, after covering both surfaces of one electrode with a regenerated cellulose nonwoven fabric (thickness: 30 μm, size: 14 mm × 195 mm) as a separator, the electrode is opposed to the other electrode, 100 ° C., 1 kg / cm 2. Heating and pressing were performed under conditions of 10 seconds to obtain a strip-shaped laminate. This laminate was wound in a cylindrical shape from the end, and the end of the winding was stopped with a winding tape to obtain a wound electrode body. Using the remaining two electrodes, another wound-type electrode body was similarly produced.

次に、一辺に開口部を有し、隔壁で内部が２つの空間に仕切られたアルミニウムラミネートフイルム製の外装体を用意した。そして、２つの空間に１つずつ上記電極体を収容した後、開口部から外装体内部に電解質溶液を注入した。電解質溶液は、電解質としてのテトラエチルアンモニウムテトラフルオロボレート（ＴＥＡ＋ＢＦ４ −）を、有機溶媒としてのプロピレンカーボネート（ＰＣ）に溶解したものであり、電解質溶液中の電解質濃度は１．０ｍｏｌ／Ｌとした。 Next, an exterior body made of an aluminum laminate film having an opening on one side and partitioned into two spaces by a partition was prepared. And after accommodating the said electrode body one by one in two spaces, the electrolyte solution was inject | poured in the exterior body from the opening part. The electrolyte solution is obtained by dissolving tetraethylammonium tetrafluoroborate (TEA + BF 4 − ) as an electrolyte in propylene carbonate (PC) as an organic solvent, and the electrolyte concentration in the electrolyte solution is 1.0 mol / L. did.

次に、電極体に接続されたリードを外装体の開口部から取り出し、リードを挟んでラミネートフィルムの開口部を封止部材としてのポリプロピレンを用いて熱融着し、外装体を密封した。そして、２つの電極体における極性の異なる電極に接続された一対のリードを外装体の外部で電気的に接続し、２つの電極体を直列接続した。このようにして、表１の長さ及び幅の活物質層を集電体の両面に有する２０ｍｍ×２０ｍｍ×２７ｍｍのサイズの電気二重層キャパシタを得た。   Next, the lead connected to the electrode body was taken out from the opening of the exterior body, and the opening of the laminate film was heat-sealed using polypropylene as a sealing member with the lead interposed therebetween, and the exterior body was sealed. Then, a pair of leads connected to electrodes having different polarities in the two electrode bodies were electrically connected outside the exterior body, and the two electrode bodies were connected in series. In this way, an electric double layer capacitor having a size of 20 mm × 20 mm × 27 mm having active material layers having the length and width shown in Table 1 on both surfaces of the current collector was obtained.

（実施例２〜３、５〜６、８、１０〜１９、参考例４、７、９、比較例１〜１３）
活物質層の長さ及び幅を表１の各実施例及び比較例の値に変更した以外は実施例１と同様にして、実施例２〜３、５〜６、８、１０〜１９、参考例４、７、９及び比較例１〜１３の電気二重層キャパシタを得た。 (Examples 2-3, 5-6, 8, 10-19, Reference Examples 4, 7, 9, Comparative Examples 1-13)
Examples 2-3, 5-6, 8, 10-19, Reference , except that the length and width of the active material layer were changed to the values of the examples and comparative examples shown in Table 1. The electric double layer capacitors of Examples 4, 7, and 9 and Comparative Examples 1 to 13 were obtained.

（実施例２０〜２４、比較例１４〜１６）
活物質層の長さ及び幅を表３の各実施例及び比較例の値に変更し、３つの電極体を実施例１と同様にして作製した。また、隔壁で内部が３つの空間に仕切られたアルミニウムラミネートフイルム製の外装体の３つの空間に１つずつ電極体を収容した。更に、３つの電極体に接続されたリードを外装体の外部で電気的に接続し、３つの電極体を直列接続した。これら以外を実施例１と同様にして、表３の長さ及び幅の活物質層を集電体の両面に有する実施例２０〜２４及び比較例１４〜１６の電気二重層キャパシタを得た。 (Examples 20-24, Comparative Examples 14-16)
The length and width of the active material layer were changed to the values of each Example and Comparative Example in Table 3, and three electrode bodies were produced in the same manner as Example 1. Further, one electrode body was housed in each of the three spaces of the exterior body made of an aluminum laminate film that was partitioned into three spaces by partition walls. Furthermore, the leads connected to the three electrode bodies were electrically connected outside the exterior body, and the three electrode bodies were connected in series. Except these, it carried out similarly to Example 1, and obtained the electrical double layer capacitor of Examples 20-24 and Comparative Examples 14-16 which have the active material layer of the length and width of Table 3 on both surfaces of a collector.

＜面積の比の算出＞
実施例１〜３、５〜６、８、１０〜１９、参考例４、７、９及び比較例１〜１３について、２つの電極体（表１，２中「＋直列」及び「−直列」と表記する。）における活物質層の長さ及び幅の値を用いて、正極及び負極の活物質層の一方面の面積をそれぞれ算出した。なお、「＋直列」の電極体の負極と「−直列」の電極体の正極とが電気的に接続されているものとする。そして、「＋直列」及び「−直列」の電極体それぞれにおける負極の活物質層の面積に対する正極の活物質層の面積の比、「＋直列」及び「−直列」の電極体における正極の活物質層の面積の最小値に対する最大値の比、及び、「＋直列」及び「−直列」の電極体における負極の活物質層の面積の最小値に対する最大値の比を算出した。その結果を表１に示す。 <Calculation of area ratio>
For Examples 1 to 3, 5 to 6, 8, 10 to 19, Reference Examples 4, 7, and 9 and Comparative Examples 1 to 13, two electrode bodies ("+ series" and " -series " in Tables 1 and 2) The area of one surface of each of the active material layers of the positive electrode and the negative electrode was calculated using the length and width values of the active material layer in FIG. It is assumed that the negative electrode of the “+ series” electrode body and the positive electrode of the “− series” electrode body are electrically connected. Then, the ratio of the area of the active material layer of the positive electrode to the area of the active material layer of the negative electrode in each of the “+ series” and “− series” electrode bodies, the activity of the positive electrode in the “+ series” and “− series” electrode bodies. The ratio of the maximum value to the minimum value of the area of the material layer and the ratio of the maximum value to the minimum value of the area of the active material layer of the negative electrode in the “+ series” and “− series” electrode bodies were calculated. The results are shown in Table 1.

実施例２０〜２４及び比較例１４〜１６について、３つの電極体（表３〜５中「直列１」、「直列２」及び「直列３」と表記する。）における活物質層の長さ及び幅の値を用いて、表３に示すように、正極及び負極の活物質層の一方面の面積をそれぞれ算出した。なお、「直列１」の電極体の負極と「直列２」の電極体の正極とが電気的に接続され、「直列２」の電極体の負極と「直列３」の電極体の正極とが電気的に接続されているものとする。そして、「直列１」〜「直列３」の電極体それぞれにおける負極の活物質層の面積に対する正極の活物質層の面積の比、「直列１」〜「直列３」の電極体における正極の活物質層の面積の最小値に対する最大値の比、及び、「直列１」〜「直列３」の電極体における負極の活物質層の面積の最小値に対する最大値の比を算出した。その結果を表４に示す。   For Examples 20 to 24 and Comparative Examples 14 to 16, the length of the active material layer in the three electrode bodies (indicated as “series 1”, “series 2”, and “series 3” in Tables 3 to 5) and Using the width value, as shown in Table 3, the area of one surface of each of the positive electrode and negative electrode active material layers was calculated. The negative electrode of the “series 1” electrode body and the positive electrode of the “series 2” electrode body are electrically connected, and the negative electrode of the “series 2” electrode body and the positive electrode of the “series 3” electrode body are connected to each other. It shall be electrically connected. Then, the ratio of the area of the active material layer of the positive electrode to the area of the active material layer of the negative electrode in each of the “series 1” to “series 3” electrode bodies, the activity of the positive electrode in the “series 1” to “series 3” electrode bodies The ratio of the maximum value to the minimum value of the area of the material layer and the ratio of the maximum value to the minimum value of the area of the active material layer of the negative electrode in the “series 1” to “series 3” electrode bodies were calculated. The results are shown in Table 4.

なお、上記全実施例、参考例及び比較例では、各電極は集電体の両面にそれぞれ活物質層を有しているので、面積の比の計算に用いる各電極の活物質層の面積は活物質層の両面の面積の合計値であるが、全実施例、参考例及び比較例において各電極の活物質層の両面の面積が互いに等しいことから、面積の比の計算に用いる各電極の活物質層の面積に、両面の合計値を用いても、一方面の値を用いても結果は変わらない。 In all the above examples , reference examples and comparative examples, each electrode has an active material layer on both sides of the current collector, so the area of the active material layer of each electrode used for calculating the area ratio is Although the total area of both surfaces of the active material layer is the same, the areas of both surfaces of the active material layer of each electrode in each of the examples , reference examples, and comparative examples are equal to each other. Even if the total value of both surfaces is used for the area of the active material layer or the value of one surface is used, the result does not change.

＜保持電圧測定＞
実施例１〜３、５〜６、８、１０〜１９、参考例４、７、９及び比較例１〜１３の電気二重層キャパシタを５Ｖで１時間充電し、２時間放置した。そして、直列接続した全電圧（Ｖｔ）、及び、各電極体の電圧（Ｖｐ及びＶｍ）を測定し、電圧バランス（＝Ｖｐ／（Ｖｔ／２））を算出した。その結果を表２に示す。 <Measurement of holding voltage>
The electric double layer capacitors of Examples 1 to 3, 5 to 6, 8, 10 to 19, Reference Examples 4, 7, and 9 and Comparative Examples 1 to 13 were charged at 5 V for 1 hour and left for 2 hours. Then, the total voltage connected in series (V t), and a voltage (V p and V m) of the electrode body is measured, voltage balance (= V p / (V t / 2)) was calculated. The results are shown in Table 2.

実施例２０〜２４及び比較例１４〜１６の電気二重層キャパシタを７．５Ｖで１時間充電し、２時間放置した。そして、直列接続した全電圧（Ｖｔ）、及び、各電極体の電圧を測定した。また、電圧バランスとして、（「直列１」〜「直列３」の電圧の最大値）／（Ｖｔ／３）、及び、（「直列１」〜「直列３」の電圧の最小値）／（Ｖｔ／３）を算出した。その結果を表５に示す。 The electric double layer capacitors of Examples 20 to 24 and Comparative Examples 14 to 16 were charged at 7.5 V for 1 hour and left for 2 hours. Then, the total voltage (V t ) connected in series and the voltage of each electrode body were measured. Further, as the voltage balance, (maximum value of voltage of “series 1” to “series 3”) / (V t / 3) and (minimum value of voltage of “series 1” to “series 3”) / ( V t / 3) was calculated. The results are shown in Table 5.

＜インピーダンス測定＞
実施例１〜３、５〜６、８、１０〜１９、参考例４、７、９及び比較例１〜１３の電気二重層キャパシタについて、充放電前のインピーダンス値（Ｉ０）を測定した。そして、１Ａで５．７Ｖまで５秒間、定電流定電圧充電（ＣＣ−ＣＶ充電）し、３Ａで０Ｖまで５秒間ＣＣ−ＣＶ放電する工程を１サイクルとして、５０００サイクル後にインピーダンス値（Ｉ）を測定した。インピーダンス値の測定は、２５℃においてＳｏｌａｒｔｒｏｎ（東陽テクニカ社製，商品名）を用いて周波数１ＫＨｚで測定した。インピーダンス値の変化（＝Ｉ／Ｉ０×１００）を表２に示す。 <Impedance measurement>
For the electric double layer capacitors of Examples 1 to 3, 5 to 6, 8, 10 to 19, Reference Examples 4, 7, and 9 and Comparative Examples 1 to 13, the impedance value (I 0 ) before charging and discharging was measured. Then, constant current constant voltage charging (CC-CV charging) to 5.7V for 5 seconds at 1A, and CC-CV discharging for 5 seconds to 0V at 3A is taken as 1 cycle, and impedance value (I) is set after 5000 cycles. It was measured. The impedance value was measured at 25 ° C. using a Solartron (manufactured by Toyo Technica Co., Ltd., trade name) at a frequency of 1 KHz. The change in impedance value (= I / I 0 × 100) is shown in Table 2.

実施例２０〜２４及び比較例１４〜１６の電気二重層キャパシタについて、充放電前のインピーダンス値（Ｉ０）を測定した。そして、１Ａで８．５Ｖまで８秒間、定電流定電圧充電（ＣＣ−ＣＶ充電）し、３Ａで０Ｖまで８秒間ＣＣ−ＣＶ放電する工程を１サイクルとして、５０００サイクル後にインピーダンス値（Ｉ）を測定した。インピーダンス値の測定は、２５℃においてＳｏｌａｒｔｒｏｎ（東陽テクニカ社製，商品名）を用いて周波数１ＫＨｚで測定した。インピーダンス値の変化（＝Ｉ／Ｉ０×１００）を表５に示す。 For the electric double layer capacitor of Example 20 to 24 and Comparative Examples 14 to 16 were measured impedance value before charge-discharge (I 0). Then, constant current constant voltage charge (CC-CV charge) to 8.5V at 1A for 8 seconds and CC-CV discharge to 3V at 0V for 8 seconds is taken as one cycle, and impedance value (I) is set after 5000 cycles. It was measured. The impedance value was measured at 25 ° C. using a Solartron (manufactured by Toyo Technica Co., Ltd., trade name) at a frequency of 1 KHz. The change in impedance value (= I / I 0 × 100) is shown in Table 5.

＜総合評価＞
電圧バランスが全て０．９５〜１．０５の範囲内であると共に、インピーダンス値の変化が１５０％以内の場合を良好なものとして「Ａ」と表記し、両方或いは一方を満たさない場合を「Ｂ」と表記した。評価結果を表２，５に示す。 <Comprehensive evaluation>
When the voltage balance is all within the range of 0.95 to 1.05 and the change in the impedance value is within 150%, it is described as “A” as good, and the case where both or one of them is not satisfied is represented by “B ". The evaluation results are shown in Tables 2 and 5.

Figure 0004905492
Figure 0004905492

Figure 0004905492
Figure 0004905492

Figure 0004905492
Figure 0004905492

Figure 0004905492
Figure 0004905492

Figure 0004905492
Figure 0004905492

４ａ，４ｂ…電極体、２０ａ，２０ｂ…正極、３０ａ，３０ｂ…負極、２２ａ，２２ｂ…正極用集電体、２４ａ，２４ｂ…正極用活物質層、３２ａ，３２ｂ…負極用集電体、３４ａ，３４ｂ…負極用活物質層、４０…セパレータ、１００…電気二重層キャパシタ。   4a, 4b ... electrode body, 20a, 20b ... positive electrode, 30a, 30b ... negative electrode, 22a, 22b ... current collector for positive electrode, 24a, 24b ... active material layer for positive electrode, 32a, 32b ... current collector for negative electrode, 34a 34b ... active material layer for negative electrode, 40 ... separator, 100 ... electric double layer capacitor.

Claims (2)

集電体上に活物質層が形成された正極と負極とがセパレータを挟んで積層された複数の電極体を備え、
前記複数の前記電極体が電気的に直列に接続され、
前記複数の前記電極体のそれぞれにおいて、前記負極の前記活物質層の面積に対する前記正極の前記活物質層の面積の比が７８〜８１％又は１０２〜１２８％であり、
前記複数の前記電極体において前記正極の前記活物質層の面積の最小値に対する前記正極の前記活物質層の面積の最大値の比が１０５％以下であり、
前記複数の前記電極体において前記負極の前記活物質層の面積の最小値に対する前記負極の前記活物質層の面積の最大値の比が１０５％以下である、電気二重層キャパシタ。 A plurality of electrode bodies in which a positive electrode and a negative electrode each having an active material layer formed on a current collector are stacked with a separator interposed therebetween,
The plurality of electrode bodies are electrically connected in series;
In each of the plurality of the electrode body, Ri the positive electrode wherein the ratio is 78 to 81%, or 102 to 128% der of the area of the active material layer of to the area of the active material layer of the negative electrode,
In the plurality of electrode bodies, a ratio of a maximum value of the area of the active material layer of the positive electrode to a minimum value of the area of the active material layer of the positive electrode is 105% or less,
The electric double layer capacitor, wherein a ratio of a maximum value of the area of the active material layer of the negative electrode to a minimum value of the area of the active material layer of the negative electrode in the plurality of electrode bodies is 105% or less. 前記複数の電極体を収容する外装体を更に備え、It further comprises an exterior body that houses the plurality of electrode bodies,
電解質を含む電解質溶液が前記外装体の内部に充填されており、An electrolyte solution containing an electrolyte is filled in the exterior body,
前記電解質が４級アンモニウム塩を含有する、請求項１に記載の電気二重層キャパシタ。The electric double layer capacitor according to claim 1, wherein the electrolyte contains a quaternary ammonium salt.
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