JP2006063403A - Metal fine grain coated with carbon and redox type capacitor using the fine grain as electrode material - Google Patents
Metal fine grain coated with carbon and redox type capacitor using the fine grain as electrode material Download PDFInfo
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Abstract
Description
本発明は、レドックス型キャパシタの電極材料として有用な炭素で被覆された金属微粒子、このものからなる電極および該電極を備えたレドックス型キャパシタに関する。 The present invention relates to a metal fine particle coated with carbon useful as an electrode material of a redox capacitor, an electrode comprising the same, and a redox capacitor provided with the electrode.
電気二重層キャパシタ(Electric Double Layer Capacitor: EDLC)は、イオン伝導性の電解液と活性炭等の分極性電極との界面に形成される電気二重層に蓄積される電荷を蓄電デバイスとして利用したものであり、二次電池と比較して大電流放電、充放電サイクル特性などの点で優れており、本質的に長寿命なこと、使用温度範囲も広いことなどから、既に、パソコン等のバックアップ電源などに実用化されている。 Electric Double Layer Capacitor (EDLC) uses electric charge accumulated in the electric double layer formed at the interface between an ion conductive electrolyte and a polarizable electrode such as activated carbon as an electricity storage device. Yes, it is superior to secondary batteries in terms of large current discharge, charge / discharge cycle characteristics, etc., and has a long service life and a wide operating temperature range. Has been put to practical use.
更に、近年、このＥＤＬＣを小型分散型エネルギーシステムでのエネルギー貯蔵デバイス、あるいは電気自動車の電源等としての使用を目的とする新しい用途展開の試みや研究開発が盛んに行われている。 Furthermore, in recent years, attempts and research and development of new applications for the purpose of using this EDLC as an energy storage device in a small distributed energy system or a power source of an electric vehicle have been actively conducted.
しかし、従来の活性炭や活性炭素繊維等に代表される多孔性炭素材料を用いた電気二重相キャパシタでは、電極の高表面化にも限界があり、エネルギー密度の高度化、高容量化、高電圧駆動化が達成することが極めて困難であり、また、高容量化のために大表面積の電極を使用する必要があった。 However, conventional electric double phase capacitors using porous carbon materials such as activated carbon and activated carbon fiber have limitations in increasing the surface of the electrode, so that the energy density is increased, the capacity is increased, and the voltage is increased. Driving is extremely difficult to achieve, and it is necessary to use an electrode with a large surface area for high capacity.
このため、電気二重層キャパシタに代わるキャパシタとして、キャパシタの作動条件下で価数変化を伴う遷移金属の酸化物を電極とし水系電解液中での該遷移金属化合物の水和酸化物の組成変化反応を利用したものや、非水系電解液中での導電性高分子電極へのイオンのドープ−脱ドープ反応、あるいは炭素電極へのイオンの挿入−脱入反応などの電荷移動を伴う反応を利用するキャパシタが提案されるに至った。 For this reason, as a capacitor instead of an electric double layer capacitor, a composition change reaction of a hydrated oxide of the transition metal compound in an aqueous electrolyte using an oxide of a transition metal accompanied by a valence change as an electrode under the operating conditions of the capacitor And reactions involving charge transfer such as doping and dedoping of ions to conductive polymer electrodes or insertion and desorption of ions to carbon electrodes in non-aqueous electrolytes Capacitors have been proposed.
このキャパシタは酸化還元（レドックス）反応を伴うことから、本来の電気二重層キャパシタ(double layer capacitor)と区別してレドックスキャパシタあるいは疑似容量キャパシタと呼ばれている。 Since this capacitor is accompanied by an oxidation-reduction (redox) reaction, it is called a redox capacitor or pseudocapacitance capacitor in distinction from an original double layer capacitor.
レドックス型キャパシタの電極材料としては、これまでに、ルテニウム、イリジウム、白金、金、ロジウム、コバルト、ニッケル、タングステン、モリブデン、マンガン、の酸化物や硫化鉄などが知られており、そのキャパシタの原理は必ずしも明確ではないが、これらの遷移金属が硫酸などの電解液中での分極の繰り返しによって、水和酸化物を形成すること、遷移金属種の価数変化が起き、水和酸化物の組成変化が起きること等による電解移動反応が広い電位範囲で生じることに依るものとされている（非特許文献１）。 As electrode materials for redox capacitors, ruthenium, iridium, platinum, gold, rhodium, cobalt, nickel, tungsten, molybdenum, manganese oxides and iron sulfides have been known so far. Is not always clear, but these transition metals form hydrated oxides by repeated polarization in electrolytes such as sulfuric acid, the valence change of transition metal species occurs, and the composition of hydrated oxides It is said that the electrolytic transfer reaction due to a change or the like occurs in a wide potential range (Non-Patent Document 1).
しかし、これらの遷移金属化合物は導電性が不十分であり、また割れなどのために塗布電極の作成が容易でなく、更には擬似容量発現のための水和反応が十分に進行しないといった難点があった。
したがって、燃料電池自動車、ハイブリッド型自動車等の補助電源、エネルギー回生等に使用することができる高容量型レドックスキャパシタの開発が強く望まれていた。
However, these transition metal compounds have insufficient conductivity, and it is not easy to produce a coated electrode due to cracks and the like, and furthermore, the hydration reaction for the pseudo capacity development does not proceed sufficiently. there were.
Accordingly, there has been a strong demand for the development of a high-capacity redox capacitor that can be used for auxiliary power sources such as fuel cell vehicles and hybrid vehicles, and energy regeneration.
一方、本発明者らは、アルミニウム、ケイ素、チタン、マグネシウム、カルシウム、鉄の酸化物を炭素被覆することで、炭素と酸化物の両方の機能性をもつ複合化物の合成を研究してきたが（非特許文献２）、タングステン及びモリブデンの酸化物や炭化物等を選択し、それを炭素被覆し、炭素被覆型酸化物の創生およびそのキャパシタ特性の評価検討は十分にはなされていなかった。 On the other hand, the present inventors have studied the synthesis of composites having both the functions of carbon and oxide by carbon-coating oxides of aluminum, silicon, titanium, magnesium, calcium, and iron ( Non-patent document 2), oxides and carbides of tungsten and molybdenum, etc., were selected and covered with carbon, and the creation of a carbon-covered oxide and evaluation of its capacitor characteristics were not sufficiently studied.
本発明は、疑似容量効果の発現のための水和反応が促進され、導電性、成型性に優れると共に金属酸化物の疑似容量効果が高く、高容量のキャパシタ特性を発現するための電極材料として有用な特定な炭素被覆金属酸化物、およびこれを電極とした、燃料電池自動車、ハイブリッド型自動車等の補助電源、エネルギー回生等としての応用が可能な高容量のレドックス型キャパシタを提供することを目的とする。 As an electrode material for the present invention, the hydration reaction for the development of the pseudocapacitance effect is promoted, the conductivity and moldability are excellent, and the pseudocapacitance effect of the metal oxide is high, and the high capacity capacitor characteristics are developed. It is an object to provide a useful specific carbon-coated metal oxide, and a high-capacity redox capacitor that can be used as an auxiliary power source, energy regeneration, etc. for fuel cell vehicles, hybrid type vehicles, etc., using this as an electrode. And
本発明者等は、種々の遷移金属化合物の炭素被覆体を鋭意検討した結果、炭素で被覆された、タングステン微粒子およびモリブデン微粒子が導電性、成型性に優れると共に疑似容量効果が高く、高容量のキャパシタ特性を発現するための電極材料として極めて有用であることを知見し本発明を完成するに至った。
すなわち、本発明によれば、以下の発明が提供される。
（１） 炭素で被覆されたタングステン微粒子又はモリブデン微粒子。
（２） タングステン又はモリブデンが、その単体、酸化物および炭化物から選ばれた少なくとも一種であることを特徴とする上記（１）に記載の炭素被覆タングステン微粒子又は炭素被覆モリブデン微粒子。
（３） 粒径が５〜５００ｎｍであることを特徴とする上記（１）又は（２）に記載の炭素被覆タングステン微粒子又は炭素被覆モリブデン微粒子。
（４） 上記（１）乃至（３）何れかに記載の炭素被覆タングステン微粒子又は炭素被覆モリブデン微粒子からなる電極。
（５） 上記（４）に記載の電極を備えたレドックス型キャパシタ。
As a result of intensive studies on carbon coatings of various transition metal compounds, the present inventors have found that tungsten fine particles and molybdenum fine particles coated with carbon have excellent conductivity and moldability, and have a high pseudo-capacitance effect, and have a high capacity. The present invention has been completed upon finding out that it is extremely useful as an electrode material for exhibiting capacitor characteristics.
That is, according to the present invention, the following inventions are provided.
(1) Tungsten fine particles or molybdenum fine particles coated with carbon.
(2) The carbon-coated tungsten fine particles or the carbon-coated molybdenum fine particles according to (1) above, wherein the tungsten or molybdenum is at least one selected from the simple substance, oxide, and carbide.
(3) The carbon-coated tungsten fine particles or carbon-coated molybdenum fine particles according to (1) or (2) above, wherein the particle size is 5 to 500 nm.
(4) An electrode comprising the carbon-coated tungsten fine particles or carbon-coated molybdenum fine particles according to any one of (1) to (3).
(5) A redox capacitor including the electrode according to (4).
本発明に係る炭素被覆タングステン微粒子および炭素被覆モリブデン微粒子は、疑似容量効果の発現のための水和反応能が高く、かつ導電性、成型性に優れると共に疑似容量効果も高く、高容量のキャパシタ特性を発現するための電極材料として有用である。
上記炭素被覆タングステン微粒子および炭素被覆モリブデン微粒子を電極材料としたレドックス型キャパシタは、疑似容量効果が高く、高容量のキャパシタ特性を示すので、燃料電池自動車、ハイブリッド型自動車等の補助電源、エネルギー回生等として応用することができる。
The carbon-coated tungsten fine particles and the carbon-coated molybdenum fine particles according to the present invention have a high hydration reaction ability for manifesting a pseudocapacitance effect, and are excellent in electrical conductivity and moldability, and also have a high pseudocapacitance effect, and have high capacity capacitor characteristics. It is useful as an electrode material for developing
Redox type capacitors using carbon-coated tungsten fine particles and carbon-coated molybdenum fine particles as electrode materials have a high pseudo-capacitance effect and show high-capacitance capacitor characteristics. Therefore, auxiliary power sources such as fuel cell vehicles and hybrid vehicles, energy regeneration, etc. It can be applied as
本発明に係る炭素被覆金属微粒子は、タングステン微粒子又はモリブデン微粒子の表面が炭素で被覆されていることを特徴とする。 The carbon-coated metal fine particles according to the present invention are characterized in that the surfaces of tungsten fine particles or molybdenum fine particles are coated with carbon.
本発明の炭素被覆金属微粒子の粒子径は、５〜５００ｎｍ好ましくは５〜１００ｎｍである。また、炭素被覆膜の膜厚は、２〜２０ｎｍ好ましくは５〜１０ｎｍである。
また、本発明の炭素被覆金属微粒子の表面積は、５０〜３００ｍ２／ｇであり、かさ密度は、２〜２０ｇ／ｃｍ３である。
The particle diameter of the carbon-coated metal fine particles of the present invention is 5 to 500 nm, preferably 5 to 100 nm. The carbon coating film has a thickness of 2 to 20 nm, preferably 5 to 10 nm.
The carbon-coated metal fine particles of the present invention have a surface area of 50 to 300 m 2 / g and a bulk density of 2 to 20 g / cm 3 .
金属源である、タングステンおよびモリブデン微粒子としては、単体、酸化物、炭化物、アンモニウム塩等が挙げられる。
具体的には、酸化数が６価から４価のタングステンを含む酸化タングステン（WO3）、タングステン酸アンモニウム((NH4)6W7O24・4H2O)、H2WO4、WCl5、酸化数が６価から４価のモリブデンを含む酸化モリブデン(MoO3)、モリブデン酸アンモニウム((NH4)6Mo7O24・4H2O)、MoCl5、H2MoO4が挙げられる。
また、タングステン酸カリウム(K2WO4)およびモリブデン酸カリウム(K2MoO4)等のカリウム塩類などの水溶性塩を水溶液としても使用することができる。
Examples of the tungsten and molybdenum fine particles that are metal sources include simple substances, oxides, carbides, and ammonium salts.
Specifically, tungsten oxide (WO 3 ), tungsten tungstate ((NH 4 ) 6 W 7 O 24 · 4H 2 O), H 2 WO 4 , WCl 5 containing tungsten having a valence of 6 to 4 And molybdenum oxide (MoO 3 ) containing molybdenum having an oxidation number of 6 to 4; ammonium molybdate ((NH 4 ) 6 Mo 7 O 24 · 4H 2 O), MoCl 5 and H 2 MoO 4 .
Also, water-soluble salts such as potassium salts such as potassium tungstate (K 2 WO 4 ) and potassium molybdate (K 2 MoO 4 ) can be used as an aqueous solution.
また、炭素源は、特に制約されず、熱処理過程で溶融するものであれば何れのものも使用でき、たとえばポリビニルアルコール、ポリ塩化ビニル、ポリエチレンテレフタレートなどの熱可塑性樹脂やヒドロキプロピルセルロースなど溶媒中でゲル化できる有機物（炭素前駆体）が用いられる。 The carbon source is not particularly limited, and any carbon source can be used as long as it melts in the heat treatment process. For example, in a solvent such as a thermoplastic resin such as polyvinyl alcohol, polyvinyl chloride, polyethylene terephthalate, or hydroxypropyl cellulose. An organic substance (carbon precursor) that can be gelled is used.
本発明の炭素被覆金属微粒子は、固相法あるいは液相法のいずれでも製造することができる。 The carbon-coated metal fine particles of the present invention can be produced by either a solid phase method or a liquid phase method.
［固相法］
固相法の場合、金属源として、例えば、上記した酸化数が６価の金属を含む酸化タングステン（WO3）、タングステン酸アンモニウム((NH4)6W7O24・4H2O)、酸化モリブデン(MoO3)、モリブデン酸アンモニウム((NH4)6Mo7O24・4H2O)を使用し、炭素源として、たとえば粉末のポリビニルアルコール（PVA）を用い、原料金属源とPVAを1：1程度の質量比で乾式混合し、セラミックスボート等の容器に充填して電気炉で焼成すればよい。
焼成条件は、たとえばアルゴンなどの不活性ガス雰囲気下(60mL/min)、昇温速度（5℃/min）、焼成時間（1時間）で所定の温度まで昇温し、適宜保持したのち放冷する方法などを採ればよい。
[Solid phase method]
In the case of the solid phase method, examples of the metal source include tungsten oxide (WO 3 ), ammonium tungstate ((NH 4 ) 6 W 7 O 24 · 4H 2 O) containing a metal having an oxidation number of 6 as described above, and oxidation. Molybdenum (MoO 3 ), ammonium molybdate ((NH 4 ) 6 Mo 7 O 24 · 4H 2 O) are used, and for example, powdered polyvinyl alcohol (PVA) is used as the carbon source. : Dry mixing at a mass ratio of about 1, filling a container such as a ceramic boat and firing in an electric furnace.
The firing conditions are, for example, in an inert gas atmosphere such as argon (60 mL / min), the temperature rising rate (5 ° C / min), the firing time (1 hour) to a predetermined temperature, and holding it appropriately and then allowing to cool What is necessary is just to take the method etc.
［液相法］
液相法の場合、金属源として、タングステン酸カリウム(K2WO4)およびモリブデン酸カリウム(K2MoO4)等の水溶性の塩を、炭素源として、たとえば、ヒドロキシプロピルセルロース(Hydroxypropyl cellulose: HPC)を用い、タングステン又はモルブデンの塩類を溶解した水溶液中にHPCを徐々に添加し、混練を続け、HPCが溶液を含んだゲル状態を得、このゲルを液体窒素温度で凍結乾燥させ、キセロゲル（Xerogel）を得た後、固相法と同様な条件で焼成すればよい。
この液相法によれば、固相法より微細な炭素被覆微粒子が得られ、また多孔質体を得ることができる。
[Liquid phase method]
In the case of the liquid phase method, water-soluble salts such as potassium tungstate (K 2 WO 4 ) and potassium molybdate (K 2 MoO 4 ) are used as a metal source, and hydroxypropyl cellulose (Hydroxypropyl cellulose: HPC), gradually add HPC into an aqueous solution in which salts of tungsten or morbuden are dissolved, continue kneading to obtain a gel state in which HPC contains the solution, freeze-dry this gel at liquid nitrogen temperature, and xerogel (Xerogel) may be obtained and then fired under the same conditions as in the solid phase method.
According to this liquid phase method, finer carbon-coated fine particles can be obtained than in the solid phase method, and a porous body can be obtained.
上記各方法によって得られた炭素被覆微粒子の同定は、これを粉砕した後、3mol/Lの塩酸および蒸留水を用いて洗浄し105℃で乾燥した後、X線回折測定（XRD）によって結晶相を、走査型電子顕微鏡（SEM）と透過型電子顕微鏡（TEM）により形態観察を、窒素吸着等温線測定から比表面積（BET法）を、微粒子の炭素含有量は熱重量測定（TG）で求めることによって行えばよい。 The carbon-coated fine particles obtained by the above methods were identified by pulverizing, washing with 3 mol / L hydrochloric acid and distilled water, drying at 105 ° C., and then measuring the crystal phase by X-ray diffraction measurement (XRD). Morphological observation with scanning electron microscope (SEM) and transmission electron microscope (TEM), specific surface area (BET method) from nitrogen adsorption isotherm measurement, and carbon content of fine particles by thermogravimetry (TG) You can do that.
上記のようにして得られる炭素被覆金属微粒子は、ナノメートルからサブマイクロメートルの微粒子であり、炭素−金属微粒子の良好な接着性、高表面積、易成型性といった特性を有することから、これを電極材料とした電気化学キャパシタは、疑似容量効果が高く、高容量のキャパシタ特性を示すので、燃料電池自動車、ハイブリッド型自動車等の補助電源、エネルギー回生等として応用することができる。 The carbon-coated fine metal particles obtained as described above are nanometer to submicrometer fine particles, and have good adhesion, high surface area, and easy moldability of the carbon-metal fine particles. The electrochemical capacitor used as a material has a high pseudo-capacitance effect and exhibits high-capacitance capacitor characteristics, and thus can be applied as an auxiliary power source, energy regeneration, etc. for fuel cell vehicles and hybrid vehicles.
本発明の炭素被覆金属微粒子を用いて電気化学キャパシタの電極を作製するには以下のようにすればよい。
前記方法によって調整した炭素被覆金属微粒子を用いて電気化学キャパシタの電極を作製するには、該炭素被覆金属微粒子を乳鉢やミルなどで粉砕した後、ポリテトラフルオロエチレンやポリフッ化ビニリデンなどの結着剤を加えて混合し、得られた電極合剤を適宜の手法で成形すればよい。例えば、上記電極合剤を金型に充填し、加圧成形してディスク状などに成形する方法が挙げられる。また、上記電極合剤を溶剤に分散させて電極合剤含有ペーストを調整し（この場合、結着剤はあらかじめ溶剤に溶解あるいは分散させておいてから複合材料と混合してもよい）、得られた電極合剤含有ペーストを金属箔や金属網などからなる集電体に塗布し、乾燥して薄膜状の電極合剤層を形成する工程を経て電極を作製してもよい。ただし、電極の作製方法は、前記例示の方法に限られることなく、他の方法によってもよい。例えば、前記炭素被覆金属微粒子の分散液に上記同様の集電体を浸漬し、集電体に分散液を付着させた後に加熱乾燥処理することによって電極を作製してもよいし、上記炭素被覆金属微粒子の分散液にポリテトラフルオロエチレンの水性分散液などを適量加え、混合してペースト状にし、そのペーストを集電体に塗布し、加熱処理することによって電極を作製してもよい。
An electrode for an electrochemical capacitor can be produced using the carbon-coated metal fine particles of the present invention as follows.
In order to produce an electrode of an electrochemical capacitor using the carbon-coated metal fine particles prepared by the above method, the carbon-coated metal fine particles are pulverized with a mortar or a mill and then bound with polytetrafluoroethylene or polyvinylidene fluoride. An agent may be added and mixed, and the obtained electrode mixture may be formed by an appropriate technique. For example, a method of filling the above-mentioned electrode mixture into a mold and press-molding it into a disk shape or the like can be mentioned. Moreover, the electrode mixture-containing paste is prepared by dispersing the electrode mixture in a solvent (in this case, the binder may be dissolved or dispersed in the solvent in advance and then mixed with the composite material). The electrode mixture-containing paste thus obtained may be applied to a current collector made of a metal foil, a metal net, or the like, and dried to form a thin-film electrode mixture layer to produce an electrode. However, the manufacturing method of the electrode is not limited to the above-described method, and other methods may be used. For example, the electrode may be produced by immersing a current collector similar to the above in a dispersion of the carbon-coated metal fine particles, and attaching the dispersion to the current collector, followed by heat-drying treatment. An electrode may be produced by adding an appropriate amount of an aqueous dispersion of polytetrafluoroethylene or the like to a dispersion of fine metal particles, mixing it into a paste, applying the paste to a current collector, and subjecting it to a heat treatment.
また、電気化学キャパシタの電解液としては、従来公知のものがそのまま使用することができ、たとえば、硫酸、塩酸、硝酸等の種々の濃度の酸性水溶液や、水酸化カリウム、水酸化ナトリウム等の種々の濃度のアルカリ性水溶液や、塩化カリウム等を種々の濃度含む中性水溶液など、電解質を含んだ水溶液が用いられる In addition, as the electrolytic solution of the electrochemical capacitor, conventionally known ones can be used as they are, for example, acidic aqueous solutions having various concentrations such as sulfuric acid, hydrochloric acid and nitric acid, and various kinds such as potassium hydroxide and sodium hydroxide. Aqueous solutions containing electrolytes, such as alkaline aqueous solutions of various concentrations and neutral aqueous solutions containing various concentrations of potassium chloride, etc. are used.
電気化学キャパシタを製造するにはそれ自体公知の方法がそのまま適用することができ、つぎのようにして作製すればよい。
シート状に作製した２枚の電極の間にセパレータを介在させて巻回し、その巻回構造の電極体を円筒形の容器内に装填し、封口することによって行われる。また、角形の電気化学キャパシタを製造する場合は、シート状の電極とセパレータとをサンドイッチ状に積層し、必要に応じてその積層体をさらに複数層積層し、その積層構造の電極体あるいは前記巻回構造の電極体を押圧して扁平状にしたものを角形の容器内に装填し、封口することによって行われる。さらに、コイン形の電気化学キャパシタを製造する場合は、上記積層構造の電極体を扁平な円形容器内に装填し、封口することによって行われる。したがって、その形状は円筒形、角形、コイン形など特に制限されることはない。
In order to produce an electrochemical capacitor, a method known per se can be applied as it is, and it may be produced as follows.
A sheet is wound between two electrodes produced in a sheet form, and the electrode body having the winding structure is loaded into a cylindrical container and sealed. In the case of manufacturing a rectangular electrochemical capacitor, a sheet-like electrode and a separator are laminated in a sandwich shape, and if necessary, a plurality of laminated bodies are laminated, and the laminated electrode body or the above-described winding body is laminated. This is done by pressing and flattening an electrode body having a round structure into a rectangular container and sealing it. Further, when manufacturing a coin-shaped electrochemical capacitor, the electrode body having the above laminated structure is loaded in a flat circular container and sealed. Therefore, the shape is not particularly limited, such as a cylindrical shape, a square shape, or a coin shape.
以下、本発明を実施例により更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１
［固相法］
酸化タングステン（WO3）５ｇと粉末のポリビニルアルコール（PVA）５ｇを1：1の質量比でめのう乳鉢によって乾式混合し、セラミックスボートに充填して電気炉で焼成した。焼成条件はアルゴン雰囲気(60mL/min)、昇温速度5℃/minで所定の温度まで昇温し、1時間保持したのち放冷した後、粉砕後、3mol/Lの塩酸および蒸留水を用いて洗浄し105℃で乾燥し、炭素被覆タングステン微粒子を得た。
得られた微粒子について、X線回折測定（XRD）によって結晶相を同定した。また、比表面積（BET法）を窒素吸着等温線測定により、炭素含有量を熱重量測定（TG）により、また、かさ密度をタッピング法により算出し、3回測定しその平均値として求めた。その結果を表１に示す。
なお、微粒子の形態観察を走査型電子顕微鏡（SEM）と透過型電子顕微鏡（TEM）により行った、その結果を図１及び図２に示す。
Example 1
[Solid phase method]
5 g of tungsten oxide (WO 3 ) and 5 g of powdered polyvinyl alcohol (PVA) were dry-mixed with an agate mortar at a mass ratio of 1: 1, filled in a ceramic boat and fired in an electric furnace. The firing conditions were an argon atmosphere (60 mL / min), the temperature was raised to a predetermined temperature at a heating rate of 5 ° C / min, held for 1 hour, allowed to cool, then pulverized, and then 3 mol / L hydrochloric acid and distilled water were used. And washed at 105 ° C. to obtain carbon-coated tungsten fine particles.
About the obtained fine particles, the crystal phase was identified by X-ray diffraction measurement (XRD). Further, the specific surface area (BET method) was calculated by nitrogen adsorption isotherm, the carbon content was calculated by thermogravimetry (TG), and the bulk density was calculated by tapping method, and measured three times to obtain the average value. The results are shown in Table 1.
In addition, the form observation of microparticles | fine-particles was performed with the scanning electron microscope (SEM) and the transmission electron microscope (TEM), and the result is shown in FIG.1 and FIG.2.
実施例２〜６
実施例１において、金属源および焼成温度を表１に記載のものに代えた以外は実施例１と同様にして炭素被覆タングステン及びモリブデン微粒子を合成した。その結果を表１に示す。
Examples 2-6
In Example 1, carbon-coated tungsten and molybdenum fine particles were synthesized in the same manner as in Example 1 except that the metal source and the firing temperature were changed to those shown in Table 1. The results are shown in Table 1.
実施例７
［液相法］
タングステン酸カリウム(K2WO4)５ｇを溶解させた水溶液中にヒドロキシプロピルセルロース (Hydroxypropyl cellulose: HPC)５ｇを徐々に添加し、混練を続け、得られたゲルを液体窒素温度で凍結乾燥させてキセロゲル（Xerogel）を得た。このゲルを実施例１と同条件で処理し炭素被覆タングステン微粒子を得た。このものの特性を実施例１と同様な方法で測定した。その結果を表２に示す。なお、微粒子の形態観察を走査型電子顕微鏡（SEM）と透過型電子顕微鏡（TEM）により行った、その結果を図３及び図４に示す。
Example 7
[Liquid phase method]
5 g of hydroxypropyl cellulose (HPC) is gradually added to an aqueous solution in which 5 g of potassium tungstate (K 2 WO 4 ) is dissolved, kneading is continued, and the resulting gel is lyophilized at liquid nitrogen temperature. Xerogel was obtained. This gel was treated under the same conditions as in Example 1 to obtain carbon-coated tungsten fine particles. The characteristics of this product were measured in the same manner as in Example 1. The results are shown in Table 2. In addition, the form observation of microparticles | fine-particles was performed with the scanning electron microscope (SEM) and the transmission electron microscope (TEM), and the result is shown in FIG.3 and FIG.4.
実施例８〜１５
実施例７において、金属源、金属源と炭素源の使用割合および焼成温度を表２に記載のものに代えた以外は実施例７と同様にして炭素被覆タングステン及びモリブデン微粒子を合成した。その結果を表２に示す。
Examples 8-15
Carbon-coated tungsten and molybdenum fine particles were synthesized in the same manner as in Example 7 except that the metal source, the use ratio of the metal source and the carbon source, and the firing temperature were changed to those shown in Table 2. The results are shown in Table 2.
実施例１６
［電気化学測定］
実施例８で得た炭素被覆タングステン微粒子を粉砕し、10mg秤量し、バインダー（ポリテトラフルオロエチレン）10重量％、カーボンブラック10重量％とともにアセトンを滴下して混練し、錠剤成型器で直径１cm、厚さ約0.5mmの円盤状ペレットを作製した。成型したペレットを100℃で1時間真空乾燥し、冷却後直ちに秤量して電極重量とした。ペレットを白金メッシュおよびガラス繊維ろ紙(孔径1μm)と共に2枚のテフロン（登録商標）板で挟みこむことによって作用極とした。対極には白金板、参照極は銀/塩化銀を使用した。電解液には1 mol/L硫酸を用い、デシケータの真空下で測定セルに充填した。常時窒素ガスをバブリングして溶存酸素を除去して試験セルを作製した。
この試験セルによって炭素被覆タングステン微粒子電極の以下の特性を調べた。すなわち、定電流充放電測定による比容量、サイクリックボルタモグラムによる電位−電流特性と比容量である。それらの測定結果を図５、図６に示し、算出された比容量を表３に示す。
図５に示した200mA/gの定電流による充放電測定において、１００回目の放電曲線より、比容量は６２F/gと求められた。図６に示したサイクリックボルタモグラムは良好なボックス型を示しており、０．５Vにおける比容量は１０４F/gと求められた。この実施例８は表１に示したとおり、13wt%の炭素含有量であるので、上記の比容量の発現は炭素分のみに由来するのではなく、タングステン微粒子の寄与があることは明らかである。図７に電気化学測定後の電極材料のＸ線回折図形を示す。炭化タングステンは完全に水和酸化物の状態へ変化しており、この変化に起因して電気化学的キャパシタ挙動が現れたと考えられる。
Example 16
[Electrochemical measurement]
The carbon-coated tungsten fine particles obtained in Example 8 were pulverized, weighed 10 mg, kneaded by adding acetone together with 10% by weight of binder (polytetrafluoroethylene) and 10% by weight of carbon black, and 1 cm in diameter with a tablet molding machine. A disk-shaped pellet having a thickness of about 0.5 mm was produced. The molded pellets were vacuum-dried at 100 ° C. for 1 hour, and weighed immediately after cooling to obtain the electrode weight. The pellet was sandwiched between two Teflon (registered trademark) plates together with platinum mesh and glass fiber filter paper (pore diameter: 1 μm) to form a working electrode. A platinum plate was used for the counter electrode, and silver / silver chloride was used for the reference electrode. 1 mol / L sulfuric acid was used as the electrolyte, and the measurement cell was filled under a desiccator vacuum. A test cell was prepared by constantly bubbling nitrogen gas to remove dissolved oxygen.
This test cell investigated the following characteristics of the carbon-coated tungsten fine particle electrode. That is, specific capacity by constant current charge / discharge measurement, potential-current characteristics and specific capacity by cyclic voltammogram. The measurement results are shown in FIGS. 5 and 6, and the calculated specific capacity is shown in Table 3.
In the charge / discharge measurement at a constant current of 200 mA / g shown in FIG. 5, the specific capacity was determined to be 62 F / g from the discharge curve at the 100th time. The cyclic voltammogram shown in FIG. 6 shows a good box shape, and the specific capacity at 0.5 V was determined to be 104 F / g. Since Example 8 has a carbon content of 13 wt% as shown in Table 1, it is clear that the expression of the specific capacity is not derived only from the carbon content but contributed by the tungsten fine particles. . FIG. 7 shows an X-ray diffraction pattern of the electrode material after electrochemical measurement. Tungsten carbide is completely changed to a hydrated oxide state, and it is considered that electrochemical capacitor behavior appears due to this change.
実施例１７，１８
実施例１６において電極を作成する炭素被覆金属微粒子を表３に記載のものに代えた以外は実施例１６と同様にして電極を作成し電気化学測定を行った。それらの結果を図８，９及び表３に示す。
Examples 17 and 18
An electrode was prepared and subjected to electrochemical measurement in the same manner as in Example 16 except that the carbon-coated metal fine particles for producing the electrode in Example 16 were replaced with those described in Table 3. The results are shown in FIGS.
比較例１
実施例１６の電極を、炭素が被覆されていない市販の炭化タングステンに代えた以外は実施例１６と同様にして試験セルを作製した
実施例１６と同様にして電気化学挙動を調べた。その結果を表４に示す。炭素被覆されていないために、電気化学的活性が発現していないと考えられる。
Comparative Example 1
A test cell was prepared in the same manner as in Example 16 except that the electrode of Example 16 was replaced with commercially available tungsten carbide not coated with carbon. The electrochemical behavior was examined in the same manner as in Example 16. The results are shown in Table 4. It is considered that the electrochemical activity is not expressed because it is not coated with carbon.
比較例２〜４
実施例１６の電極を、表４に示す材料に代えた以外は実施例１６と同様にして試験セルを作製した。それらの電気化学挙動は表４にまとめた。いずれも比較例１と同様に、電気化学的活性を示さず、有意な比容量を与えない。
これらのことから、金属を微粒子状に調整し、かつその表面を炭素被覆した炭素被覆金属微粒子を調整することによって、良好な電気化学キャパシタ用電極材料としうることが示された。
Comparative Examples 2-4
A test cell was produced in the same manner as in Example 16 except that the electrode of Example 16 was replaced with the material shown in Table 4. Their electrochemical behavior is summarized in Table 4. None, like Comparative Example 1, does not exhibit electrochemical activity and does not give significant specific capacity.
From these facts, it was shown that a good electrode material for an electrochemical capacitor can be obtained by adjusting the metal into fine particles and adjusting the carbon-coated metal fine particles whose surface is coated with carbon.
Claims (5)
A redox capacitor comprising the electrode according to claim 4.
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