JP2008218890A - Electrode material for electrochemical capacitor and electrochemical capacitor - Google Patents

Electrode material for electrochemical capacitor and electrochemical capacitor Download PDF

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JP2008218890A
JP2008218890A JP2007057298A JP2007057298A JP2008218890A JP 2008218890 A JP2008218890 A JP 2008218890A JP 2007057298 A JP2007057298 A JP 2007057298A JP 2007057298 A JP2007057298 A JP 2007057298A JP 2008218890 A JP2008218890 A JP 2008218890A
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electrode
electrochemical capacitor
electrode material
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composite oxide
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Tadashi Inaba
忠司 稲葉
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Toyota Central R&D Labs Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a new electrode material for an electrochemical capacitor which contains composite oxide. <P>SOLUTION: An electrode material for an electrochemical capacitor contains composite oxide the general formula of which is M<SB>m</SB>WO<SB>n</SB>(m is either 1 or 2, n is either 4 or 6, and M is at least one kind of material selected from among Mn, Fe, Co, Ni, Cu, Zn, Mg, Ca, Sr, and Bi). Preferably, this composite oxide is Fe<SB>2</SB>WO<SB>6</SB>. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、電気化学キャパシタ用電極材料及び電気化学キャパシタに関する。   The present invention relates to an electrode material for an electrochemical capacitor and an electrochemical capacitor.

従来、電気化学キャパシタとしては、ルテニウム酸をナノシート状に形成し、このナノシートを積層して電極とし、活性面積を増大させた電気化学キャパシタが提案されている（例えば、特許文献１参照）。また、タングステン、コバルト及び鉄などから選ばれるアモルファス酸化物をナノ粒子として電極としエネルギー密度を高めた電気化学キャパシタが提案されている（例えば、特許文献２参照）。
特開２００４−３１５３４７号公報 特開２００５−２５２２１７号公報 Conventionally, as an electrochemical capacitor, an electrochemical capacitor has been proposed in which ruthenic acid is formed in a nanosheet shape, and this nanosheet is laminated to form an electrode, thereby increasing the active area (see, for example, Patent Document 1). In addition, an electrochemical capacitor has been proposed in which an amorphous oxide selected from tungsten, cobalt, iron, and the like is used as an electrode as an electrode to increase the energy density (see, for example, Patent Document 2).
JP 2004-315347 A JP 2005-252217 A

しかしながら、この特許文献１に記載された電気化学キャパシタでは、高い蓄電容量を示すが希少なルテニウムを利用しているためコストが高いという問題があった。一方、特許文献２に記載された電気化学キャパシタでは、コストは低いがキャパシタとしての性能は酸化ルテニウムに遙かに及ばないという問題があった。このような観点から、新規な電気化学キャパシタ用電極材料の開発が望まれている。   However, the electrochemical capacitor described in Patent Document 1 has a problem of high cost because it shows high storage capacity but uses rare ruthenium. On the other hand, the electrochemical capacitor described in Patent Document 2 has a problem that its performance as a capacitor is much lower than that of ruthenium oxide although the cost is low. From such a viewpoint, development of a new electrode material for an electrochemical capacitor is desired.

本発明は、このような課題に鑑みなされたものであり、複合酸化物を含む新規な電気化学キャパシタ用電極材料及び電気化学キャパシタを提供することを目的とする。   This invention is made | formed in view of such a subject, and it aims at providing the novel electrode material for electrochemical capacitors and electrochemical capacitor containing complex oxide.

上述した目的を達成するために、本発明者らは、タングステンと、他の遷移元素やアルカリ土類などと、を含む複合酸化物を備えた電極を用いた電気化学キャパシタを作製したところ、有用な性能を有することを見いだし、本発明を完成するに至った。   In order to achieve the above-mentioned object, the present inventors have produced an electrochemical capacitor using an electrode including a composite oxide containing tungsten and other transition elements, alkaline earths, and the like. The present invention has been found to have excellent performance, and the present invention has been completed.

即ち、本発明の電気化学キャパシタ用電極材料は、
一般式がＭmＷＯn（ｍは１及び２のいずれかであり、ｎは４及び６のいずれかであり、ＭはＭｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｍｇ，Ｃａ，Ｓｒ及びＢｉから選ばれた少なくとも一種）である複合酸化物を含むものである。 That is, the electrode material for an electrochemical capacitor of the present invention is
The general formula is M m WO n (m is either 1 or 2, n is either 4 or 6, M is Mn, Fe, Co, Ni, Cu, Zn, Mg, Ca, Sr and A composite oxide which is at least one selected from Bi).

本発明の電気化学キャパシタ用電極材料によれば、複合酸化物を含む有用な性能を有する新規な電気化学キャパシタを提供することができる。   According to the electrode material for an electrochemical capacitor of the present invention, a novel electrochemical capacitor having a useful performance including a composite oxide can be provided.

本発明の電気化学キャパシタ用電極材料は、一般式がＭmＷＯn（ｍは１及び２のいずれかであり、ｎは４及び６のいずれかである）のものであり、Ｍは、Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕなど複数の酸化数を有する遷移金属元素や、Ｍｇ，Ｃａ，Ｓｒなどのアルカリ土類金属元素、ＺｎやＢｉなどの典型金属元素から選ばれた少なくとも一種である複合酸化物を含むものである。例えば、複合酸化物は、ＣｏＷＯ4であるものとしてもよいし、Ｆｅ2ＷＯ6であるものとしてもよい。Ｆｅは、資源として豊富にあり、比較的コストを低く押さえることができるため、電極材料としてより好ましい。 The electrode material for an electrochemical capacitor of the present invention has a general formula of M m WO n (m is 1 or 2 and n is 4 or 6), and M is Mn , Fe, Co, Ni, Cu, a transition metal element having a plurality of oxidation numbers, an alkaline earth metal element such as Mg, Ca, Sr, and a composite metal that is at least one selected from typical metal elements such as Zn and Bi It contains an oxide. For example, the composite oxide may be CoWO 4 or Fe 2 WO 6 . Fe is more preferable as an electrode material because it is abundant as a resource and can keep costs relatively low.

本発明の電気化学キャパシタ用電極材料において、複合酸化物は、窒素吸着のＢＥＴ法で測定した比表面積が１２０ｃｍ2／ｇ以上であることが好ましい。こうすれば、蓄電特性を向上させることができる。なお、材料作製の容易性を考慮すると、比表面積が２０００ｍ2／ｇ以下であることが好ましい。また、複合酸化物は、走査型電子顕微鏡で観察した平均粒径が１００ｎｍ以下であることが好ましく、８０ｎｍ以下であることがより好ましい。こうすれば、充放電するサイトが増えるため、蓄電性能を向上することができる。なお、材料作製の容易性を考慮すると、平均粒径が１ｎｍ以上であることが好ましい。 In the electrode material for an electrochemical capacitor of the present invention, the composite oxide preferably has a specific surface area of 120 cm 2 / g or more measured by a nitrogen adsorption BET method. In this way, the storage characteristics can be improved. In view of ease of material production, the specific surface area is preferably 2000 m 2 / g or less. In addition, the composite oxide preferably has an average particle diameter of 100 nm or less, more preferably 80 nm or less, observed with a scanning electron microscope. By doing so, the number of sites to be charged / discharged increases, so that the power storage performance can be improved. In view of ease of material production, the average particle diameter is preferably 1 nm or more.

本発明の電気化学キャパシタ用電極材料は、目的の組成となるように、Ｍｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｍｇ，Ｃａ，Ｓｒ及びＢｉから選ばれた少なくとも一種と、Ｗとを秤量し、この秤量した原料粉末をボールミルやアトライターなどを用いて湿式混合、粉砕し、得られたスラリーを乾燥したのち所定温度で焼成することにより作製することが好ましい。原料粉体は、酸化物としてもよいし、炭酸塩や硝酸塩、シュウ酸などとしてもよい。焼成温度は、原料粉体にもよるが、７００℃〜１２００℃が好ましい。得られた焼成物を粉砕し、導電補助材や結着剤を混合し、電極基材に接着して電極を作製してもよい。電極基材は、ステンレスや銅などの板やメッシュなどを用いることができる。導電補助材は、例えば炭素や金属繊維、金属粉末類、有機導電性材料などを用いることができる。また結着剤は、例えばテフロン（登録商標）などを用いることができる。導電補助剤と結着剤は、電極材料に対してそれぞれ５重量％とするのが好ましい。   The electrode material for an electrochemical capacitor of the present invention weighs at least one selected from Mn, Fe, Co, Ni, Cu, Zn, Mg, Ca, Sr, and Bi and W so as to have a target composition. The weighed raw material powder is preferably wet-mixed and pulverized using a ball mill or attritor, and the resulting slurry is dried and then fired at a predetermined temperature. The raw material powder may be an oxide, carbonate, nitrate, oxalic acid, or the like. The firing temperature is preferably 700 ° C. to 1200 ° C., although it depends on the raw material powder. The obtained fired product may be pulverized, mixed with a conductive auxiliary material or a binder, and bonded to an electrode substrate to produce an electrode. As the electrode base material, a plate such as stainless steel or copper, a mesh, or the like can be used. As the conductive auxiliary material, for example, carbon, metal fibers, metal powders, organic conductive materials, or the like can be used. As the binder, for example, Teflon (registered trademark) can be used. The conductive auxiliary agent and the binder are each preferably 5% by weight based on the electrode material.

あるいは、上述と同様に目的の組成となるように原料粉末を秤量し、この秤量した原料粉末を硝酸などの水溶液に溶解させ、更にポリエチレングリコールを添加し、得られた溶液を電極基材（例えば導電性ガラス）に塗布して焼成してもよい。このとき、原料粉末は、水溶液に可溶な塩を用いることが好ましい。こうすれば、比表面積の高い電極を得ることができる。   Alternatively, the raw material powder is weighed so as to have the desired composition in the same manner as described above, the weighed raw material powder is dissolved in an aqueous solution such as nitric acid, polyethylene glycol is further added, and the resulting solution is used as an electrode substrate (for example, It may be applied to conductive glass and fired. At this time, it is preferable to use a salt soluble in an aqueous solution as the raw material powder. In this way, an electrode having a high specific surface area can be obtained.

こうして得られた本発明の電極材料を備えた電極を用いて電気化学キャパシタを作製する。例えば、コイン型の電気化学キャパシタでは、上述した一対の電極の間に電解液を浸したセパレータを設けコイン型のケースに封入することにより作製することができ、シリンダ型の電気化学キャパシタでは、シート状の電極を作製し、この一対の電極シートの間に電解液を浸したセパレータを設け、全体を渦巻き状に巻回してシリンダ型のケースに封入することにより作製することができる。セパレータは、例えば、ポリプロピレン製不織布やポリフェニレンスルフィド製不織布などの高分子不織布、ポリエチレンやポリプロピレンなどのオレフィン系樹脂の微多孔フィルムが挙げられる。これらは単独で用いてもよいし、複合して用いてもよい。電解液は、例えば硫酸などの酸水溶液や水酸化ナトリウムなどのアルカリ溶液を用いることができる。本発明の電気化学キャパシタは、上述した電気化学キャパシタ用電極材料を備えているため、上述した電気化学キャパシタ用電極材料と同様の効果を得ることができる。   An electrochemical capacitor is produced using the electrode provided with the electrode material of the present invention thus obtained. For example, a coin-type electrochemical capacitor can be manufactured by providing a separator in which an electrolytic solution is immersed between the pair of electrodes described above and enclosing the separator in a coin-type case. It is possible to fabricate a cylindrical electrode by providing a separator in which an electrolytic solution is immersed between the pair of electrode sheets, winding the whole in a spiral shape, and enclosing it in a cylindrical case. Examples of the separator include polymer nonwoven fabrics such as polypropylene nonwoven fabrics and polyphenylene sulfide nonwoven fabrics, and microporous films of olefinic resins such as polyethylene and polypropylene. These may be used alone or in combination. As the electrolytic solution, for example, an acid aqueous solution such as sulfuric acid or an alkaline solution such as sodium hydroxide can be used. Since the electrochemical capacitor of the present invention includes the above-described electrode material for an electrochemical capacitor, the same effects as those of the above-described electrode material for an electrochemical capacitor can be obtained.

なお、本発明は上述した実施形態に何ら限定されることはなく、本発明の技術的範囲に属する限り種々の態様で実施し得ることはいうまでもない。   It should be noted that the present invention is not limited to the above-described embodiment, and it goes without saying that the present invention can be implemented in various modes as long as it belongs to the technical scope of the present invention.

（実施例１）
Ｆｅ2ＷＯ6の組成となるようにＦｅ2Ｏ3とＷＯ3とを秤量し、秤量した原料粉末と、分散媒としてエタノールを入れ、ボールミルで２０ｈ湿式混合、粉砕を行った。得られたスラリーを乾燥したのち、１１００℃、２ｈの条件で大気中で焼成した。得られた焼成物を粉砕して実施例１の電極粉を得た。この電極粉と、導電補助材として炭素（電気化学工業製デンカブラック）と、結着剤としてテフロン（三井デュポンフロロケミカル製６Ｊ）とを、９０：５：５の重量比で混合し、ＳＵＳ網（寸法０．５ｃｍ×１０ｃｍ、厚さ０．０２ｃｍ）の先端に押し付け、形状を矩形板状に整えて実施例１の電極とした。 (Example 1)
Were weighed Fe 2 O 3 and WO 3 as a composition of Fe 2 WO 6, and the raw material powder was weighed, ethanol was placed as a dispersion medium, 20h wet mixed by a ball mill, pulverization was carried out. The obtained slurry was dried and then calcined in air at 1100 ° C. for 2 hours. The obtained fired product was pulverized to obtain the electrode powder of Example 1. This electrode powder, carbon (Denka Black manufactured by Denki Kagaku Kogyo) as a conductive auxiliary material, and Teflon (6J manufactured by Mitsui DuPont Fluorochemical) as a binder are mixed at a weight ratio of 90: 5: 5, and a SUS network is mixed. The electrode of Example 1 was prepared by pressing against the tip of (size 0.5 cm × 10 cm, thickness 0.02 cm) and adjusting the shape to a rectangular plate.

（実施例２）
ＣｏＷＯ4の組成となるようにＣｏ3Ｏ4とＷＯ3とを秤量し、秤量した原料粉末と、分散媒としてエタノールを入れ、ボールミルで２０ｈ湿式混合、粉砕を行った。得られたスラリーを乾燥したのち、１２００℃、２ｈの条件で大気中で焼成した。得られた焼成物を粉砕して実施例２の電極粉を得た。実施例１に記載したのと同様に、この電極粉と、導電補助材として炭素と、結着剤としてテフロンとを、９０：５：５の重量比で混合し、ＳＵＳ網の先端に押し付け、形状を矩形板状に整えて実施例２の電極とした。 (Example 2)
Co 3 O 4 and WO 3 were weighed so as to have the composition of CoWO 4 , weighed raw material powder and ethanol as a dispersion medium were added, and wet mixed and pulverized by a ball mill for 20 hours. The obtained slurry was dried and then calcined in the air at 1200 ° C. for 2 hours. The obtained fired product was pulverized to obtain the electrode powder of Example 2. In the same manner as described in Example 1, this electrode powder, carbon as a conductive auxiliary material, and Teflon as a binder are mixed at a weight ratio of 90: 5: 5, and pressed against the tip of the SUS net, The shape was adjusted to a rectangular plate to obtain an electrode of Example 2.

（実施例３）
Ｆｅ（ＮＯ3）3と（ＮＨ4）10Ｗ12Ｏ41とを化学量論比が１：１となるように混合し、０．０５Ｍの硝酸水溶液０．２Ｌに溶解させた。更に、ポリエチレングリコールを５０ｖｏｌ％添加し、得られた溶液を導電性ガラス（Ｆ−ＳｎＯ2：寸法１０ｃｍ×１０ｃｍ、厚さ１ｍｍ）に塗布し、７００℃、３ｈ焼成を行った。得られたものを実施例３の電極とした。更に、この電極面に形成された物質を削り落とし、得られた粉体を実施例３の電極粉とした。なお、この実施例３の電極粉の比表面積を、日本ベル製ＢＥＬＳＯＲＰにより窒素吸着の１点ＢＥＴ法で測定したところ、１２０ｍ2／ｇであった。また、実施例３の電極粉を走査型電子顕微鏡（日本電子製ＪＳＭ−８９０）を用いて観察したところ、平均粒径が８０ｎｍであった。 (Example 3)
Fe (NO 3 ) 3 and (NH 4 ) 10 W 12 O 41 were mixed so that the stoichiometric ratio was 1: 1, and dissolved in 0.2 L of 0.05 M nitric acid aqueous solution. Furthermore, 50 vol% of polyethylene glycol was added, and the obtained solution was applied to conductive glass (F-SnO 2 : dimensions 10 cm × 10 cm, thickness 1 mm), followed by baking at 700 ° C. for 3 hours. The obtained electrode was used as the electrode of Example 3. Further, the material formed on the electrode surface was scraped off, and the obtained powder was used as the electrode powder of Example 3. In addition, it was 120 m < 2 > / g when the specific surface area of the electrode powder of this Example 3 was measured by the 1-point BET method of nitrogen adsorption by BELSORP made from Nippon Bell. Moreover, when the electrode powder of Example 3 was observed using the scanning electron microscope (JEOL JSM-890), the average particle diameter was 80 nm.

（実施例４）
ＳｒＷＯ4の組成となるようにＳｒＯとＷＯ3とを秤量し、秤量した原料粉末と、分散媒としてエタノールを入れ、ボールミルで２０ｈ湿式混合、粉砕を行った。得られたスラリーを乾燥したのち、１１００℃、２ｈの条件で大気中で焼成した。得られた焼成物を粉砕して実施例４の電極粉を得た。実施例１に記載したのと同様に、この電極粉と、導電補助材として炭素と、結着剤としてテフロンとを、９０：５：５の重量比で混合し、ＳＵＳ網の先端に押し付け、形状を矩形板状に整えて実施例４の電極とした。 Example 4
SrO and WO 3 were weighed so as to have a composition of SrWO 4 , weighed raw material powder and ethanol as a dispersion medium were added, and wet-mixed and pulverized with a ball mill for 20 hours. The obtained slurry was dried and then calcined in air at 1100 ° C. for 2 hours. The obtained fired product was pulverized to obtain the electrode powder of Example 4. In the same manner as described in Example 1, this electrode powder, carbon as a conductive auxiliary material, and Teflon as a binder are mixed at a weight ratio of 90: 5: 5, and pressed against the tip of the SUS net, The shape was adjusted to a rectangular plate to obtain an electrode of Example 4.

（実施例５）
ＺｎＷＯ4の組成となるようにＺｎＯとＷＯ3とを秤量し、秤量した原料粉末と、分散媒としてエタノールを入れ、ボールミルで２０ｈ湿式混合、粉砕を行った。得られたスラリーを乾燥したのち、１１００℃、２ｈの条件で大気中で焼成した。得られた焼成物を粉砕して実施例５の電極粉を得た。実施例１に記載したのと同様に、この電極粉と、導電補助材として炭素と、結着剤としてテフロンとを、９０：５：５の重量比で混合し、ＳＵＳ網の先端に押し付け、形状を矩形板状に整えて実施例５の電極とした。 (Example 5)
ZnO and WO 3 were weighed so as to have a composition of ZnWO 4 , weighed raw material powder and ethanol as a dispersion medium were added, and wet mixed and pulverized by a ball mill for 20 hours. The obtained slurry was dried and then calcined in air at 1100 ° C. for 2 hours. The obtained fired product was pulverized to obtain the electrode powder of Example 5. In the same manner as described in Example 1, this electrode powder, carbon as a conductive auxiliary material, and Teflon as a binder are mixed at a weight ratio of 90: 5: 5, and pressed against the tip of the SUS net, The shape was adjusted to a rectangular plate to obtain an electrode of Example 5.

（Ｘ線回折測定）
実施例１〜５の電極粉のＸ線回折測定をＸ線回折装置（リガク製ＲＩＮＴ２２００）によりＣｕＫα線を用いて行った。 (X-ray diffraction measurement)
X-ray diffraction measurement of the electrode powders of Examples 1 to 5 was performed using CuKα rays by an X-ray diffractometer (RINT2200 manufactured by Rigaku).

（ＣＶ特性評価）
実施例１〜５の電極を用い、図１に示すＣＶ評価装置を用いてＣＶ特性の評価を行った。図１に示すように、実施例１〜３のいずれかの電極とＡｇ／ＡｇＣｌの参照極との距離を１ｃｍとし、この参照極とＰｔの対極との距離を２ｃｍとし、それぞれの電極を、容積０．０５Ｌの０．１ＭのＮａＯＨ水溶液に入れ、ポテンショスタットを用いて電位走査速度を１０〜２００ｍＶ／ｓとしてサイクリックボルタモグラム（ＣＶ）を測定した。なお、対極の寸法は、上述したように０．５ｃｍ×１０ｃｍ、厚さ０．０２ｃｍとした。 (CV characteristic evaluation)
Using the electrodes of Examples 1 to 5, CV characteristics were evaluated using the CV evaluation apparatus shown in FIG. As shown in FIG. 1, the distance between any of the electrodes of Examples 1 to Ag / AgCl reference electrode is 1 cm, the distance between the reference electrode and the counter electrode of Pt is 2 cm, A cyclic voltammogram (CV) was measured using a potentiostat at a potential scanning speed of 10 to 200 mV / s using a potentiostat. The dimensions of the counter electrode were 0.5 cm × 10 cm and the thickness was 0.02 cm as described above.

（評価結果）
Ｘ線回折の測定結果は、図２に示すように、実施例１がＦｅ2ＷＯ6の結晶となっていることが確認された。また、実施例３も同様であった。図３に示すように、実施例１は、そのＣＶ特性がヒステリシスを示し電荷が蓄積される現象が確認されたため、蓄電性能を持つことが明らかとなった。また、電位走査速度を１０，５０，１００，２００ｍＶ／ｓと変化させても電流飽和領域が大きく減少することはなく、高速の充放電にも対応できることがわかった。実施例１の電極のＣＶ特性から算出される容量は１２Ｆ／ｇであった。また、図４に示すＸ線回折の結果から、実施例２がＣｏＷＯ4の結晶となっていることが確認された。図５に示すように、実施例２は、そのＣＶ特性がヒステリシスを示し電荷が蓄積される現象が確認されたため、蓄電性能を持つことが明らかとなった。なお、図５は電位走査速度５０ｍＶ／ｓのデータである。実施例２の電極のＣＶ特性から算出される容量は１０Ｆ／ｇであった。また、図６に示すように、実施例３は、実施例１よりも高いＣＶ特性を示すことがわかった。なお、図６は電位走査速度５０ｍＶ／ｓのデータである。この実施例３の電極のＣＶ特性から算出される容量は２１０Ｆ／ｇであった。したがって、電極は、数十ｎｍ以下の粒子で電極を構成し、比表面積を向上させることにより蓄電性能が向上することがわかった。また、図７に示すように、実施例４のＳｒＷＯ4や、図８に示す実施例５のＺｎＷＯ4についても、電位走査速度５０ｍＶ／ｓでＣＶ特性を評価したところ、このＣＶ特性がヒステリシスを示し電荷が蓄積される現象が確認されたため、蓄電性能を持つことが明らかとなった。 (Evaluation results)
As shown in FIG. 2, the X-ray diffraction measurement results confirmed that Example 1 was Fe 2 WO 6 crystals. Moreover, Example 3 was also the same. As shown in FIG. 3, it was revealed that Example 1 has a storage performance because the phenomenon that the CV characteristic shows hysteresis and charge is accumulated is confirmed. Further, it was found that even when the potential scanning speed was changed to 10, 50, 100, and 200 mV / s, the current saturation region was not greatly reduced, and high-speed charging / discharging could be handled. The capacity calculated from the CV characteristics of the electrode of Example 1 was 12 F / g. Further, from the result of X-ray diffraction shown in FIG. 4, it was confirmed that Example 2 was a CoWO 4 crystal. As shown in FIG. 5, it was revealed that Example 2 has a power storage performance because the phenomenon that the CV characteristic shows hysteresis and charge is accumulated is confirmed. FIG. 5 shows data at a potential scanning speed of 50 mV / s. The capacity calculated from the CV characteristics of the electrode of Example 2 was 10 F / g. Moreover, as shown in FIG. 6, Example 3 showed that CV characteristic higher than Example 1 was shown. FIG. 6 shows data at a potential scanning speed of 50 mV / s. The capacity calculated from the CV characteristics of the electrode of Example 3 was 210 F / g. Therefore, it was found that the electrode is composed of particles of several tens of nanometers or less and the power storage performance is improved by improving the specific surface area. Further, as shown in FIG. 7, the SrWO 4 and Example 4, for the ZnWO 4 of Example 5 shown in FIG. 8, it was evaluated CV characteristics at a potential scan rate 50 mV / s, this CV characteristic hysteresis Since the phenomenon of the accumulated charge was confirmed, it became clear that it has power storage performance.

本発明は、蓄電材料に関する分野に利用可能である。   The present invention can be used in the field related to power storage materials.

電気化学キャパシタの説明図である。It is explanatory drawing of an electrochemical capacitor. 実施例１のＸ線回折の測定チャートである。2 is a measurement chart of X-ray diffraction of Example 1. FIG. 実施例１のＣＶ特性の評価結果を表す図である。It is a figure showing the evaluation result of the CV characteristic of Example 1. 実施例２のＸ線回折の測定チャートである。6 is a measurement chart of X-ray diffraction of Example 2. 実施例２のＣＶ特性の評価結果を表す図である。It is a figure showing the evaluation result of the CV characteristic of Example 2. 実施例３のＣＶ特性の評価結果を表す図である。It is a figure showing the evaluation result of the CV characteristic of Example 3. 実施例４のＣＶ特性の評価結果を表す図である。It is a figure showing the evaluation result of the CV characteristic of Example 4. 実施例５のＣＶ特性の評価結果を表す図である。It is a figure showing the evaluation result of the CV characteristic of Example 5.

Claims (4)

一般式がＭmＷＯn（ｍは１及び２のいずれかであり、ｎは４及び６のいずれかであり、ＭはＭｎ，Ｆｅ，Ｃｏ，Ｎｉ，Ｃｕ，Ｚｎ，Ｍｇ，Ｃａ，Ｓｒ及びＢｉから選ばれた少なくとも一種）である複合酸化物を含む、電気化学キャパシタ用電極材料。 The general formula is M m WO n (m is either 1 or 2, n is either 4 or 6, M is Mn, Fe, Co, Ni, Cu, Zn, Mg, Ca, Sr and An electrode material for an electrochemical capacitor, comprising a composite oxide that is at least one selected from Bi. 前記複合酸化物は、Ｆｅ2ＷＯ6である、請求項１に記載の電気化学キャパシタ用電極材料。 The electrode material for an electrochemical capacitor according to claim 1, wherein the composite oxide is Fe 2 WO 6 . 前記複合酸化物は、比表面積が１２０ｃｍ2／ｇ以上である、請求項１又は２に記載の電気化学キャパシタ用電極材料。 The electrode material for an electrochemical capacitor according to claim 1, wherein the complex oxide has a specific surface area of 120 cm 2 / g or more. 請求項１〜３のいずれかに記載の電気化学キャパシタ用電極材料を備えた、電気化学キャパシタ。   The electrochemical capacitor provided with the electrode material for electrochemical capacitors in any one of Claims 1-3.
JP2007057298A 2007-03-07 2007-03-07 Electrode material for electrochemical capacitor and electrochemical capacitor Pending JP2008218890A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013155106A (en) * 2012-01-31 2013-08-15 Toyota Motor Engineering & Manufacturing North America Inc Water oxidation catalyst

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013155106A (en) * 2012-01-31 2013-08-15 Toyota Motor Engineering & Manufacturing North America Inc Water oxidation catalyst

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