JP2005314152A - Layered manganese dioxide nanobelt and method of manufacturing the same - Google Patents

Layered manganese dioxide nanobelt and method of manufacturing the same Download PDF

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JP2005314152A
JP2005314152A JP2004133154A JP2004133154A JP2005314152A JP 2005314152 A JP2005314152 A JP 2005314152A JP 2004133154 A JP2004133154 A JP 2004133154A JP 2004133154 A JP2004133154 A JP 2004133154A JP 2005314152 A JP2005314152 A JP 2005314152A
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manganese dioxide
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layered manganese
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Yoshio Bando
義雄 板東
Takayoshi Sasaki
高義 佐々木
Ma Renzhi
ルンチィ・マ
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National Institute for Materials Science
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a layered manganese dioxide nanobelt having uniform dimension, high catalytic reaction rate and capable of easily inserting and releasing cation, and a method of manufacturing the same. <P>SOLUTION: The layered manganese dioxide nanobelt is obtained by heating dimanganese trioxide powder in a sodium hydroxide aqueous solution at 150-200°C for ≥72 hr and has 5-15 nm width, 3-15 nm thickness and length ranging from several μm to several tens μm. The layered manganese dioxide nanobelt is a layered, so called, birnessite manganese dioxide, has high catalytic reaction rate, is capable of easily inserting and releasing cation and is inexpensively manufactured at a low temperature by a hydrothermal method. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、触媒、イオンシーブ、蓄電池の電極材料などとして使用できる、層状二酸化マンガンナノベルト及びその製造方法に関する。   The present invention relates to a layered manganese dioxide nanobelt that can be used as a catalyst, an ion sieve, an electrode material for a storage battery, and the like, and a method for producing the same.

二酸化マンガンは、従来から触媒、イオンシーブ、蓄電池の電極材料などの酸化還元材料として用いられている。蓄電池の電極材料として、例えばＬｉの正極活物質となる二酸化マンガンは、Ｌｉ+ （リチウム陽イオン）の電気化学的挿入（インターカレーション）と抽出（デインターカレーション）とによりリチウム二次電池の充放電特性を改善する材料である。この二酸化マンガンの触媒活性などの向上のために、二酸化マンガンのナノ構造体の研究が行われている。
二酸化マンガンの一次元単結晶ナノワイヤは、硫酸マンガンを過硫酸アンモニウムや過マンガン酸カリウムで酸化処理することにより製造されている（非特許文献１〜３参照）。また、良好な配向性を有する二酸化マンガンナノワイヤも硫酸マンガン−ビピリジル系配位結合重合体を水酸化ナトリウム水溶液中で処理することにより製造されている（非特許文献４参照）。これらのナノワイヤはいずれもトンネル状の構造を有している。 Manganese dioxide has been conventionally used as a redox material such as an electrode material for catalysts, ion sieves, and storage batteries. As an electrode material of a storage battery, for example, manganese dioxide, which is a positive electrode active material of Li, is obtained by electrochemical insertion (intercalation) and extraction (deintercalation) of Li + (lithium cation). It is a material that improves charge / discharge characteristics. In order to improve the catalytic activity of manganese dioxide, research on manganese dioxide nanostructures has been conducted.
One-dimensional single crystal nanowires of manganese dioxide are produced by oxidizing manganese sulfate with ammonium persulfate or potassium permanganate (see Non-Patent Documents 1 to 3). Further, manganese dioxide nanowires having good orientation are also produced by treating a manganese sulfate-bipyridyl-based coordination bond polymer in an aqueous sodium hydroxide solution (see Non-Patent Document 4). Each of these nanowires has a tunnel-like structure.

一方、二次元の層状構造を有するバーネサイト型の二酸化マンガンは、非特許文献５による報告の後、多数の研究が行われている。この二次元の層状構造を有するバーネサイト型の二酸化マンガンは、約７Åの層間距離を有しているので、層間に入ったカチオン（陽イオン）が容易に移動できる特徴を有している。   On the other hand, after research by Non-Patent Document 5, many studies have been conducted on the burntite-type manganese dioxide having a two-dimensional layered structure. The birnessite-type manganese dioxide having a two-dimensional layered structure has an interlayer distance of about 7 mm, and thus has a feature that cations (cations) entering the layer can easily move.

最近、単層で２次元構造を有するバーネサイト型二酸化マンガンのナノシートが製作され、その厚さは０．７７ｎｍ（ナノメートル）で二次元方向の寸法が数百ｎｍであることが報告されている（非特許文献６参照）。
また、このナノシートをＬｉと共に積層構造にすると、新規なＬｉ−バーネサイト型二酸化マンガン構造となり、リチウム二次電池の正極活物質として使用され、そして、バーネサイト型二酸化マンガンナノシートへのＬｉ+ イオンの挿入及び抽出によりリチウム二次電池の充放電特性が円滑であることが報告されている（非特許文献７参照）。 Recently, a nano-sheet of birnessite-type manganese dioxide having a two-dimensional structure with a single layer has been produced, and its thickness is reported to be 0.77 nm (nanometer) and the dimension in the two-dimensional direction is several hundred nm ( Non-patent document 6).
Further, when this nanosheet is laminated with Li to form a new Li-bernesite-type manganese dioxide structure, it is used as a positive electrode active material of a lithium secondary battery, and the insertion of Li + ions into the burntite-type manganese dioxide nanosheet and It has been reported that the charge and discharge characteristics of the lithium secondary battery are smooth by extraction (see Non-Patent Document 7).

X. Wang, 他、"Selected-Control Hydrothermal Synthesis of α- and β- MnO2 Single Crystal Nanowires", 2002, J. Am. Chem. Soc., vo1.124, pp.2880-2881X. Wang, et al., "Selected-Control Hydrothermal Synthesis of α- and β-MnO2 Single Crystal Nanowires", 2002, J. Am. Chem. Soc., Vo1.124, pp.2880-2881 X. Wang, 他、"Rational Synthesis ofα- MnO2 single-crystal nanorods", 2002, Chem. Commun., pp.764-765X. Wang, et al., "Rational Synthesis of α-MnO2 single-crystal nanorods", 2002, Chem. Commun., Pp.764-765 X. Wang, 他 "Synthesis and Formation Mechanism of Manganese Dioxide Nanowires/Nanorods", 2003, Chem. Eur. J., vo1.9, pp.300-306X. Wang, et al. "Synthesis and Formation Mechanism of Manganese Dioxide Nanowires / Nanorods", 2003, Chem. Eur. J., vo1.9, pp.300-306 Y. J. Xiong他、"Growth of Well-Aligned γ- MnO2 Monocrystalline Nanowires through a Coordination-Polymer-Precursor Route", 2003, Chem. Eur. J. vo1.9, pp.1645-1651Y. J. Xiong et al., "Growth of Well-Aligned γ-MnO2 Monocrystalline Nanowires through a Coordination-Polymer-Precursor Route", 2003, Chem. Eur. J. vo1.9, pp.1645-1651 J. Parant 他４名、"Sur-quelques nouvelles phases de formule Na x MnO2(x ≦1)", 1971, J. Solid State Chem., vo1.3 , pp.1-11J. Parant and 4 others, "Sur-quelques nouvelles phases de formule Na x MnO2 (x ≤ 1)", 1971, J. Solid State Chem., Vo1.3, pp.1-11 Y. Omomo 他３名、"Redoxable Nanosheet Crystallite of MnO2 Derived via Delamination of Layered Manganese Oxide", 2003, J. Am. Chem. Soc., vo1.125, pp.3568-3575Y. Omomo and three others, "Redoxable Nanosheet Crystallite of MnO2 Derived via Delamination of Layered Manganese Oxide", 2003, J. Am. Chem. Soc., Vo1.125, pp.3568-3575 L. Wang 他７名、"Synthesis of a Li-Mn-oxide with Disordered Layer Stacking through Flocculation of Exfoliated MnO2 Nanosheets, and Its Electrochemical properties", 2003, Chem. Mater., vo1.15, pp.4508-4514L. Wang and 7 others, "Synthesis of a Li-Mn-oxide with Disordered Layer Stacking through Flocculation of Exfoliated MnO2 Nanosheets, and Its Electrochemical properties", 2003, Chem. Mater., Vo1.15, pp.4508-4514

上記単層バーネサイト型二酸化マンガンナノシートを、再現性良く製造することは、困難であるという課題がある。
また、触媒、イオンシーブ、蓄電池の電極材料等の酸化還元材料として、Ｌｉイオンなどの電気化学的挿入及び抽出を効率良く行うためには、一次元や二次元の層状のバーネサイト型二酸化マンガンのナノ構造体の実現が要求されている。しかしながら、一次元の層状構造を有するバーネサイト型二酸化マンガンの一次元ナノベルトが得られないという課題がある。 There is a problem that it is difficult to produce the single-layered birnessite-type manganese dioxide nanosheet with good reproducibility.
In order to efficiently perform electrochemical insertion and extraction of Li ion as a redox material such as catalyst, ion sieve, and storage battery electrode material, the nanostructure of one-dimensional or two-dimensional layered birnessite-type manganese dioxide Realization of the body is required. However, there is a problem in that a one-dimensional nanobelt of banesite-type manganese dioxide having a one-dimensional layered structure cannot be obtained.

本発明は上記課題に鑑み、寸法が均一で、触媒反応速度が高く、かつ、カチオンの挿入及び抽出が容易にできる、層状二酸化マンガンナノベルト及びその製造方法を提供することを目的としている。   In view of the above problems, an object of the present invention is to provide a layered manganese dioxide nanobelt having a uniform size, a high catalytic reaction rate, and easy insertion and extraction of cations and a method for producing the same.

上記目的を達成するために、本発明の層状二酸化マンガンナノベルトは、幅５ｎｍ〜１５ｎｍ、厚さ３ｎｍ〜１５ｎｍ、長さ数μｍ〜数十μｍであることを特徴とする。   In order to achieve the above object, the layered manganese dioxide nanobelt of the present invention is characterized by having a width of 5 nm to 15 nm, a thickness of 3 nm to 15 nm, and a length of several μm to several tens of μm.

また、本発明の層状二酸化マンガンナノベルトは、水酸化ナトリウム水溶液中で、三酸化二マンガン粉末を１５０℃〜２００℃の温度範囲で、７２時間以上加熱することにより得られる層状二酸化マンガンナノベルトであり、幅５ｎｍ〜１５ｎｍ、厚さ３ｎｍ〜１５ｎｍ、長さ数μｍ〜数十μｍであることを特徴とする。   The layered manganese dioxide nanobelt of the present invention is a layered manganese dioxide nanobelt obtained by heating a manganese dioxide trioxide powder in a sodium hydroxide aqueous solution at a temperature range of 150 ° C. to 200 ° C. for 72 hours or more. And having a width of 5 nm to 15 nm, a thickness of 3 nm to 15 nm, and a length of several μm to several tens of μm.

上記構成によれば、層状二酸化マンガンナノベルトの幅と厚さがｎｍオーダーであり、その長さがμｍオーダであるので比表面積が高い。また、その厚さ方向の層間距離が約７Åであるため、カチオンの挿入及び抽出が容易にできる。したがって、触媒反応速度が高く、かつ、カチオンの挿入及び抽出が容易にできる、バーネサイト型の層状二酸化マンガンナノベルトを提供することができる。   According to the above configuration, the width and thickness of the layered manganese dioxide nanobelt are on the order of nm, and the length is on the order of μm, so the specific surface area is high. Further, since the interlayer distance in the thickness direction is about 7 mm, insertion and extraction of cations can be easily performed. Therefore, it is possible to provide a birnessite-type layered manganese dioxide nanobelt that has a high catalytic reaction rate and can easily insert and extract cations.

また、本発明の層状二酸化マンガンナノベルトの製造方法は、水酸化ナトリウム水溶液中で、三酸化二マンガン粉末を１５０℃〜２００℃の温度範囲で、７２時間以上加熱することにより層状二酸化マンガンナノベルトを得ることを特徴とする。
また、水酸化ナトリウム水溶液の濃度は、好ましくは、５ｍｏｌ／ｌｔｒ〜１０ｍｏｌ／ｌｔｒの範囲であり、三酸化二マンガン粉末の量は、好ましくは、水酸化ナトリウム水溶液４０ｃｍ3 当たり、２ｇ〜３ｇの範囲である。 Moreover, the manufacturing method of the layered manganese dioxide nanobelt of this invention is a layered manganese dioxide nanobelt by heating a dimanganese trioxide powder for 72 hours or more in the temperature range of 150 to 200 degreeC in sodium hydroxide aqueous solution. It is characterized by obtaining.
The concentration of the aqueous sodium hydroxide is preferably in the range of 5 mol / ltr to 10 mol / ltr, and the amount of the dimanganese trioxide powder is preferably in the range of 2 to 3 g per 40 cm 3 of the aqueous sodium hydroxide. It is.

この方法によれば、三酸化二マンガン粉末を原料として、水酸化ナトリウム水溶液を用いる水熱法により、１５０℃〜２００℃の温度範囲で７２時間以上加熱することにより、層状二酸化マンガンナノベルトを製造することができる。
また、この方法により製造される層状二酸化マンガンナノベルトは、幅と厚さがｎｍオーダーであり、その長さがμｍオーダであるので比表面積が高い。また、その厚さ方向の層間距離が約７Åであるため、カチオンの挿入及び抽出が容易にできる。したがって、触媒反応速度が高く、かつ、カチオンの挿入及び抽出が容易にできる、バーネサイト型の層状二酸化マンガンナノベルトを低温で、容易に、かつ、低コストで製造することが可能になる。 According to this method, a layered manganese dioxide nanobelt is produced by heating for 72 hours or more in a temperature range of 150 ° C. to 200 ° C. by a hydrothermal method using a sodium hydroxide aqueous solution, using dimanganese trioxide powder as a raw material. can do.
In addition, the layered manganese dioxide nanobelt manufactured by this method has a width and thickness on the order of nm, and the length is on the order of μm, so that the specific surface area is high. Further, since the interlayer distance in the thickness direction is about 7 mm, insertion and extraction of cations can be easily performed. Therefore, it is possible to easily produce a birnessite-type layered manganese dioxide nanobelt having a high catalytic reaction rate and easy insertion and extraction of cations at a low temperature and at a low cost.

本発明の層状二酸化マンガンナノベルトは、幅と厚さがｎｍオーダーであり、その長さ
がμｍオーダであるので比表面積が高く、また、厚さ方向の間隔がカチオンが通電できる７Å程度であるので、従来の層状二酸化マンガンよりも触媒反応速度が高い。また、カチオンの挿入及び抽出が容易にできる。
また、本発明の方法によれば、層状二酸化マンガンナノベルトを、低温で、かつ、低コストで製造することができる。 The layered manganese dioxide nanobelt of the present invention has a width and thickness on the order of nm, and its length is on the order of μm, so that the specific surface area is high, and the interval in the thickness direction is about 7 mm at which cations can be energized. Therefore, the catalytic reaction rate is higher than that of the conventional layered manganese dioxide. In addition, insertion and extraction of cations can be facilitated.
Moreover, according to the method of the present invention, the layered manganese dioxide nanobelt can be produced at a low temperature and at a low cost.

以下、本発明の層状二酸化マンガンナノベルト及びその製造方法を図面を参照して詳細に説明する。
初めに、本発明の層状二酸化マンガン（ＭｎＯ2 ）ナノベルトについて説明する。
本発明の層状二酸化マンガンナノベルトは、幅５ｎｍ( ナノメートル、１０-9ｍ）〜１５ｎｍ、厚さ３ｎｍ〜１５ｎｍ、長さは数μｍ( マイクロメートル、１０-6ｍ）〜数十μｍである。そして、厚さ方向の層間距離は、７Åの層状であり、所謂バーネサイト型二酸化マンガンである。 Hereinafter, the layered manganese dioxide nanobelt of the present invention and the manufacturing method thereof will be described in detail with reference to the drawings.
First, the layered manganese dioxide (MnO 2 ) nanobelt of the present invention will be described.
The layered manganese dioxide nanobelt of the present invention has a width of 5 nm (nanometer, 10 −9 m) to 15 nm, a thickness of 3 nm to 15 nm, and a length of several μm (micrometer, 10 −6 m) to several tens of μm. . The interlayer distance in the thickness direction is 7 mm, which is so-called burntite type manganese dioxide.

次に、本発明の層状二酸化マンガンナノベルトの製造方法について説明する。水熱法により、最初に、三酸化二マンガン（Ｍｎ2 Ｏ3 ）粉末を水酸化ナトリウム（ＮａＯＨ）水溶液に分散させ、分散液を調製する。
水酸化ナトリウム水溶液の濃度は、５ｍｏｌ／ｌｔｒ（リットル、１０００ｃｍ3 ）〜１０ｍｏｌ／ｌｔｒの範囲で行えばよい。三酸化二マンガンから二酸化マンガンへの変換には１０ｍｏｌ／ｌｔｒの濃度で十分であるので、これ以上の濃度にする必要はない。また、５ｍｏｌ／ｌｔｒ以下の濃度では原料の三酸化二マンガンが二酸化マンガンに変換されないので望ましくない。
三酸化二マンガン粉末の量は水酸化ナトリウム水溶液４０ｃｍ3 当たり、２ｇ〜３ｇの範囲で行えばよい。三酸化二マンガン粉末の量が３ｇ以上では最終生成物の層状二酸化マンガンナノベルト中に未反応の三酸化二マンガンが残存し、望ましくない。また、三酸化二マンガン粉末の量が２ｇより少ないと、反応には差し支えないが仕込み歩留まりが減少するので望ましくない。 Next, the manufacturing method of the layered manganese dioxide nanobelt of this invention is demonstrated. First, by a hydrothermal method, dimanganese trioxide (Mn 2 O 3 ) powder is dispersed in an aqueous sodium hydroxide (NaOH) solution to prepare a dispersion.
The concentration of the aqueous sodium hydroxide solution may be in the range of 5 mol / ltr (liter, 1000 cm 3 ) to 10 mol / ltr. Since the concentration of 10 mol / ltr is sufficient for the conversion from dimanganese trioxide to manganese dioxide, it is not necessary to make the concentration higher than this. Further, when the concentration is 5 mol / ltr or less, the raw material dimanganese trioxide is not converted to manganese dioxide, which is not desirable.
The amount of the dimanganese trioxide powder may be in the range of 2 g to 3 g per 40 cm 3 of the aqueous sodium hydroxide solution. If the amount of the dimanganese trioxide powder is 3 g or more, unreacted dimanganese trioxide remains in the layered manganese dioxide nanobelt as the final product, which is not desirable. On the other hand, if the amount of the dimanganese trioxide powder is less than 2 g, the reaction may be carried out, but it is not desirable because the charging yield decreases.

この分散液をポリテトラフルオロエチレンで内張りしたオートクレーブに入れる。次に、このオートクレーブを乾燥機の中に設置し、１５０℃〜２００℃で、７２時間以上加熱する。これにより、加熱処理後、黒色の粉末が沈殿する。
加熱温度は１５０℃〜２００℃の温度範囲が適当であり、２００℃以上では、蒸気発生による圧力が高くなり、安全上望ましくなく、また、１５０℃以下では反応の進行が不十分である。
また、加熱時間は７２時間以上必要であり、７２時間より少ないと、最終生成物の層状二酸化マンガンナノベルトの中に、マンガンのオキサイド−ハイドロオキサイド構造が混入するので望ましくない。 This dispersion is placed in an autoclave lined with polytetrafluoroethylene. Next, this autoclave is set in a dryer and heated at 150 ° C. to 200 ° C. for 72 hours or more. Thereby, black powder precipitates after heat processing.
The heating temperature is suitably in the range of 150 ° C. to 200 ° C. If the heating temperature is 200 ° C. or higher, the pressure due to the generation of steam is high, which is not desirable for safety, and if it is 150 ° C. or lower, the progress of the reaction is insufficient.
Further, the heating time is required to be 72 hours or longer. If the heating time is shorter than 72 hours, manganese oxide-hydroxide structure is mixed in the final layered manganese dioxide nanobelt, which is not desirable.

次に、この沈殿物をろ過し、希塩酸（ＨＣｌ）と脱イオン水で十分に洗浄する。その後、室温で３日間風乾することにより、黒色粉末の層状二酸化マンガンナノベルトが得られる。   The precipitate is then filtered and washed thoroughly with dilute hydrochloric acid (HCl) and deionized water. Then, the layered manganese dioxide nanobelt of black powder is obtained by air drying at room temperature for 3 days.

次に、実施例に基づいてさらに詳細に説明する。
水酸化ナトリウム（関東化学（株）製、純度９７．０％）を用いて、濃度１０ｍｏｌ／ｌｔｒの水溶液４０ｃｍ3 を作製した。この溶液の中に、三酸化二マンガン粉末（高純度化学研究所（株）製）２ｇを分散させ、分散液を調製した。
この分散液を、容量５０ｃｍ3 のポリテトラフルオロエチレンで内張りしたオートクレーブの中に仕込んだ。このオートクレーブを乾燥機の中に入れ、乾燥機の温度を１７０℃に保った。この加熱時間を１２時間から１週間までそれぞれ変えた。加熱後、オートクレーブの中に、黒色の粉末が沈殿した。沈殿物をろ過し、濃度０．１ｍｏｌ／ｌｔｒの希塩酸と脱イオン水で十分に洗浄した。この沈殿物を室温で３日間風乾した。収量は、約１．５ｇであった。 Next, it demonstrates still in detail based on an Example.
A 40 cm 3 aqueous solution having a concentration of 10 mol / ltr was prepared using sodium hydroxide (manufactured by Kanto Chemical Co., Inc., purity 97.0%). In this solution, 2 g of dimanganese trioxide powder (manufactured by Kojundo Chemical Laboratory Co., Ltd.) was dispersed to prepare a dispersion.
This dispersion was charged into an autoclave lined with polytetrafluoroethylene having a capacity of 50 cm 3 . This autoclave was put in a dryer, and the temperature of the dryer was kept at 170 ° C. The heating time was changed from 12 hours to 1 week. After heating, a black powder precipitated in the autoclave. The precipitate was filtered and thoroughly washed with dilute hydrochloric acid and deionized water having a concentration of 0.1 mol / ltr. The precipitate was air dried at room temperature for 3 days. Yield was about 1.5 g.

図１は、実施例で得られた黒色粉末および原料として用いた三酸化二マンガン粉末の粉末Ｘ線回折結果を示す図である。図の横軸は角度２θ（度）を示し、縦軸は回折Ｘ線強度（任意目盛り）を示している。
図において、（ａ）が１２時間、（ｂ）が４８時間、（ｃ）が７２時間以上の加熱であり、最も下に示すデータが三酸化二マンガン粉末からの回折Ｘ強度である。
図から明らかなように、原料の三酸化二マンガン粉末には、左端ピークの約７．１Åのピークは現れていないが、加熱時間を（ａ）１２時間、（ｂ）４８時間、（ｃ）７２時間と長くするにつれて、７．１Åのピークが増大していくのが分かる。
また、（ｂ）の４８時間処理では４．５５Å（２θ＝１９．５°）にマンガンオキサイド−ハイドロオキサイドのピークが存在し、まだ完全にはバーネサイト型二酸化マンガンにはなっていない。
さらに、（ｃ）の７２時間処理で、このピークが完全に消失し、バーネサイト型二酸化マンガンが得られていることが確認できた。 FIG. 1 is a diagram showing the powder X-ray diffraction results of the black powder obtained in the example and the dimanganese trioxide powder used as a raw material. In the figure, the horizontal axis indicates the angle 2θ (degrees), and the vertical axis indicates the diffracted X-ray intensity (arbitrary scale).
In the figure, (a) is heating for 12 hours, (b) is 48 hours, (c) is heating for 72 hours or more, and the data shown at the bottom is the diffraction X intensity from the dimanganese trioxide powder.
As is clear from the figure, the starting manganese dioxide powder does not show a peak at about 7.1% of the leftmost peak, but the heating time is (a) 12 hours, (b) 48 hours, (c) It can be seen that the peak at 7.1 cm increases as the time increases to 72 hours.
Further, in the treatment for 48 hours of (b), a peak of manganese oxide-hydroxide is present at 4.55 mm (2θ = 19.5 °), and it has not yet been completely converted into a benesite type manganese dioxide.
Further, it was confirmed that this peak disappeared completely by the treatment for 72 hours in (c), and that a benesite type manganese dioxide was obtained.

図２は、実施例の１７０℃で７２時間の加熱処理で得られた生成物の透過型電子顕微鏡（ＴＥＭ）像を示す図である。
図から明らかなように、多数の黒い繊維が形成されているのが分かる。この黒い繊維のそれぞれが、一次元の層状二酸化マンガンナノベルトである。さらに、高倍率の透過電子顕微鏡及び走査型電子顕微鏡（ＳＥＭ）での測定により、層状二酸化マンガンナノベルトの寸法は、幅５ｎｍ〜１５ｎｍ、厚さ３ｎｍ〜１５ｎｍ、長さは数μｍ〜数十μｍであり、そして、厚さ方向の層間距離は７Åであることが分かった。また、得られた生成物中には、直線状だけでなく、曲がったナノベルトも存在していた。さらに、全体の１０％程度、幅数百ｎｍのシート状構造も含有されていた。 FIG. 2 is a transmission electron microscope (TEM) image of the product obtained by heat treatment at 170 ° C. for 72 hours in the example.
As can be seen from the figure, many black fibers are formed. Each of these black fibers is a one-dimensional layered manganese dioxide nanobelt. Furthermore, the dimensions of the layered manganese dioxide nanobelt are 5 nm to 15 nm, the thickness is 3 nm to 15 nm, and the length is several μm to several tens of μm, as measured with a high-magnification transmission electron microscope and scanning electron microscope (SEM). It was found that the interlayer distance in the thickness direction was 7 mm. Further, in the obtained product, not only a linear shape but also a bent nanobelt was present. Furthermore, a sheet-like structure having a width of about several hundreds of nanometers was also contained.

図３は、実施例の１７０℃で７２時間の加熱処理で得られた生成物のエネルギー分散型Ｘ線分析（ＥＤＳ）結果を示す図である。図の横軸はＸ線エネルギー（ｅＶ）を示し、縦軸はＸ線強度（任意目盛り）を示している。
図から明らかなように、生成物は、マンガン及び酸素からなり、マンガンと酸素との原子比は１：２である。これから、化学量論的組成の二酸化マンガンが得られることが分かった。なお、銅のピークは試料作製のために用いた銅グリッドに由来するものである。 FIG. 3 is a diagram showing the results of energy dispersive X-ray analysis (EDS) of the product obtained by heat treatment at 170 ° C. for 72 hours in the example. In the figure, the horizontal axis represents X-ray energy (eV), and the vertical axis represents X-ray intensity (arbitrary scale).
As is apparent from the figure, the product consists of manganese and oxygen, and the atomic ratio of manganese to oxygen is 1: 2. From this, it was found that manganese dioxide having a stoichiometric composition can be obtained. The copper peak is derived from the copper grid used for sample preparation.

次に、実施例で得たバーネサイト型二酸化マンガンである層状二酸化マンガンナノベルトのリチウムに対する電気化学特性について説明する。
電気化学特性は、実施例で得た層状二酸化マンガンナノベルトをリチウム二次電池の正極活物質として用いることで調べた。
リチウム二次電池は次のようにして作製した。乾燥した層状二酸化マンガンナノベルトを０．２ｇと、カーボンブラック２０ｗｔ％（重量％）及びポリテトラフルオロエチレン１０ｗｔ％の混合物と、電解質として体積比１：１の炭酸エチレンと炭酸ジエチルの混合物に１ｍｏｌ／ｌｔｒの過塩素酸リチウムと、を用いてコイン型に成形して陰極とした。また、陽極には金属リチウムを用いた。 Next, the electrochemical characteristic with respect to lithium of the layered manganese dioxide nanobelt which is the birnessite type manganese dioxide obtained in the Example is demonstrated.
The electrochemical characteristics were examined by using the layered manganese dioxide nanobelts obtained in the examples as the positive electrode active material of the lithium secondary battery.
The lithium secondary battery was produced as follows. 0.2 mol of the dried layered manganese dioxide nanobelt, a mixture of 20 wt% (wt%) of carbon black and 10 wt% of polytetrafluoroethylene, and 1 mol / l of a mixture of ethylene carbonate and diethyl carbonate at a volume ratio of 1: 1 as an electrolyte. The cathode was molded into a coin shape using ltr lithium perchlorate. Moreover, metallic lithium was used for the anode.

図４は、実施例の層状二酸化マンガンナノベルトを用いたリチウム二次電池の放電容量のサイクル依存性を示す図である。図の横軸は充放電のサイクル数を示し、縦軸は層状二酸化マンガンナノベルト１ｇ当たりの放電容量（ｍＡｈ／ｇ）を示している。充放電特性の測定は、電圧１．０〜４．８Ｖを印加し、一定の電流密度０．２３ｍＡ／ｃｍ2 で充放
電を行った。
図から明らかなように、１サイクルの目の放電プロセスでは、３７５ｍＡｈ／ｇの高い放電容量が得られ、２サイクル目で２９０ｍＡｈ／ｇになり、３サイクル目以降の平均の容量低下は１サイクル当り１％で、３０サイクル後でも２３０ｍＡｈ／ｇの容量を有していることが分かる。このように、実施例の層状二酸化マンガンナノベルトが正極活物質として有効に作用している。これにより、実施例のバーネサイト型である層状二酸化マンガンナノベルトの中でのカチオン、すなわちリチウム陽イオンの挿入、放出の可逆性が良好であることが分かる。 FIG. 4 is a diagram showing the cycle dependency of the discharge capacity of the lithium secondary battery using the layered manganese dioxide nanobelt of the example. The horizontal axis of the figure indicates the number of charge / discharge cycles, and the vertical axis indicates the discharge capacity (mAh / g) per 1 g of the layered manganese dioxide nanobelt. The charge / discharge characteristics were measured by applying a voltage of 1.0 to 4.8 V and charging / discharging at a constant current density of 0.23 mA / cm 2 .
As is apparent from the figure, in the discharge process of the first cycle, a high discharge capacity of 375 mAh / g was obtained, and in the second cycle, it became 290 mAh / g, and the average capacity decrease after the third cycle was per cycle. It can be seen that it has a capacity of 230 mAh / g even after 30 cycles at 1%. Thus, the layered manganese dioxide nanobelt of an Example is acting effectively as a positive electrode active material. This shows that the reversibility of insertion and release of cations, that is, lithium cations, in the layered manganese dioxide nanobelt that is the birnessite type of the example is good.

上記結果から、本発明の層状二酸化マンガンナノベルトは、バーネサイト型二酸化マンガンのナノ構造体であり、カチオンに対する電気化学特性が良好であることが分かる。   From the above results, it can be seen that the layered manganese dioxide nanobelt of the present invention is a birnessite-type manganese dioxide nanostructure and has good electrochemical properties with respect to cations.

本発明は、上記実施の形態に限定されることなく、特許請求の範囲に記載した発明の範囲内で種々の変形が可能であり、それらも本発明の範囲内に含まれることはいうまでもない。   The present invention is not limited to the above-described embodiment, and various modifications are possible within the scope of the invention described in the claims, and it goes without saying that these are also included in the scope of the present invention. Absent.

実施例で得られた黒色粉末および原料として用いた三酸化二マンガン粉末の粉末Ｘ線回折結果を示す図である。It is a figure which shows the powder X-ray-diffraction result of the black powder obtained in the Example, and the dimanganese trioxide powder used as a raw material. 実施例の１７０℃で７２時間の加熱処理で得られた生成物の透過型電子顕微鏡（ＴＥＭ）像を示す図である。It is a figure which shows the transmission electron microscope (TEM) image of the product obtained by the heat processing for 72 hours at 170 degreeC of an Example. 実施例の１７０℃で７２時間の加熱処理で得られた生成物のＸ線分析（ＥＤＳ）結果を示す図である。It is a figure which shows the X-ray-analysis (EDS) result of the product obtained by heat processing for 72 hours at 170 degreeC of an Example. 実施例の層状二酸化マンガンナノベルトを用いたリチウム二次電池の放電容量のサイクル依存性を示す図である。It is a figure which shows the cycle dependence of the discharge capacity of the lithium secondary battery using the layered manganese dioxide nanobelt of an Example.

Claims (5)

幅５ｎｍ〜１５ｎｍ、厚さ３ｎｍ〜１５ｎｍ、長さ数μｍ〜数十μｍであることを特徴とする、層状二酸化マンガンナノベルト。   A layered manganese dioxide nanobelt characterized by having a width of 5 nm to 15 nm, a thickness of 3 nm to 15 nm, and a length of several μm to several tens of μm. 水酸化ナトリウム水溶液中で、三酸化二マンガン粉末を１５０℃〜２００℃の温度範囲で、７２時間以上加熱することにより得られる層状二酸化マンガンナノベルトであり、幅５ｎｍ〜１５ｎｍ、厚さ３ｎｍ〜１５ｎｍ、長さ数μｍ〜数十μｍであることを特徴とする、層状二酸化マンガンナノベルト。   A layered manganese dioxide nanobelt obtained by heating dimanganese trioxide powder in a sodium hydroxide aqueous solution at a temperature range of 150 ° C. to 200 ° C. for 72 hours or more, having a width of 5 nm to 15 nm and a thickness of 3 nm to 15 nm. A layered manganese dioxide nanobelt having a length of several μm to several tens of μm. 水酸化ナトリウム水溶液中で、三酸化二マンガン粉末を１５０℃〜２００℃の温度範囲で、７２時間以上加熱することにより層状二酸化マンガンナノベルトを得ることを特徴とする、層状二酸化マンガンナノベルトの製造方法。   Production of a layered manganese dioxide nanobelt, characterized in that a layered manganese dioxide nanobelt is obtained by heating a manganese dioxide trioxide powder in a sodium hydroxide aqueous solution at a temperature range of 150 ° C to 200 ° C for 72 hours or more. Method. 前記水酸化ナトリウム水溶液の濃度は、５ｍｏｌ／ｌｔｒ〜１０ｍｏｌ／ｌｔｒの範囲であることを特徴とする、請求項３に記載の層状二酸化マンガンナノベルトの製造方法。   The method for producing a layered manganese dioxide nanobelt according to claim 3, wherein the concentration of the sodium hydroxide aqueous solution is in the range of 5 mol / ltr to 10 mol / ltr. 前記三酸化二マンガン粉末の量は、水酸化ナトリウム水溶液４０ｃｍ3 当たり、２ｇ〜３ｇの範囲であることを特徴とする、請求項３又は４に記載の層状二酸化マンガンナノベルトの製造方法。 5. The method for producing a layered manganese dioxide nanobelt according to claim 3, wherein the amount of the dimanganese trioxide powder ranges from 2 g to 3 g per 40 cm 3 of the aqueous sodium hydroxide solution.
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