成果報告書詳細
管理番号20110000001166
タイトル*平成22年度中間年報 ナノテク・先端部材実用化研究開発/ハイブリッドナノカーボン電極による水系電気化学スーパーキャパシタの開発
公開日2011/9/9
報告書年度2010 - 2010
委託先名国立大学法人大分大学 独立行政法人産業技術総合研究所 東洋炭素株式会社 NECトーキン株式会社
プロジェクト番号P05023
部署名電子・材料・ナノテクノロジー部
和文要約和文要約等以下本編抜粋:1. 研究開発の内容及び成果等
(1)「膨張化炭素繊維による高容量電極材の調製」
平成21年度で終了した.
(2)「窒素ドーピングによる疑似容量の高度化の研究」
平成21年度で終了した.
(3)「ハイブリッドナノカーボン材料の開発」
大分大学では、膨張化炭素繊維と窒素ドーピングの組み合わせにより,100m2/gを超える膨張化炭素繊維のエッジ面への窒素原子のドーピング手法と最適量の検討を行った。具体的手法として、アンモニア雰囲気下での膨張化炭素繊維の熱処理により窒素ドープ量の向上を試みた。しかしながら、アンモニア雰囲気の焼成下では必ずしも窒素ドープ量が向上せず、容量増加に結びつかなかった。この他に、電極として使用されている活性炭への窒素ドープによるハイブリッド化を検討した。炭素骨格内への窒素ドープは、NO2ガス処理により検討を行った。800℃以下での処理では炭素の損耗が少なく、窒素分があまり増えないにもかかわらず、容量が2割程度増加することが明らかになった。また、ホウ素添加メラミン樹脂から窒素含有多孔質炭素の合成とその特性について検討を行い、表面積が500 m2/g小さいにもにもかかわらず400 F/gを超える容量を発現できることを見出した。
英文要約Hybridization by nitrogen doping to the miniaturized carbon such as exfoliated carbon fibers (ExCFs) or activated carbon using as an electrode was examined. Its nitrogen doping to carbon framewrok carried out by NO2 gas treatment. Capacity increased at about 20% in spite of nitrogen doping quantity being little. Porous carbon materials including nitrogen prepared from melamine resin including boron was prepared under inert atmosphere. Its electrical performances characterized through charge/discharge or CV. It was found that the capacity which exceeds 400 F/g in spite of the small surface area less than 500 m2/g could be manifested.
Preparation of hybrid electrode using ExCFs or activated carbon with BBL polymer developed at last year was examined. Using the active carbon (Tokin A) which was standard sample in positive electrode, 124 F/g mass conversion capacity was achieved under standard charge/discharge testing, when hybridized material of BBL/ExCFs = 80/20 (mass ratio) of the same in the mass was made to be negative electrode. This value exceeds 600 F/g obtaining in single electrode capacity estimated by three electrode cell. It seems to make capacity enhancement by making hybridized material.
It confirmed that it examined preparation condition of porous carbon materials from mixture of magnesium citrate and precursor of citric acid in detail and showed 495 F/g in standard condition and 460 F/g in the high power test by using three electrodes cell.
In selection of raw materials, it was possible production cost of raw materials became under 1/3 to be selected the general grade of PAN-based carbon fibers. Carbon source to prepare the hybrid nanocarbon was selected the magnesium citrate and ExCFs. It succeeded in the preparation of the porous carbon which contains the nitrogen. As a result, preparation per kilogram became possible. It became that ExCFs with 300 m2 /g could also constantly prepare. Though preparation ability of ExCFs was 5 g/day by last year, it was improved to about 100 g/day. In establishment of hybridization technique and exfoliation technique of carbon fibers, preparation ability of the hybrid nanocarbon became 50 kg/month.
Capacitor of the thin mold shape was designed as a prototype. Regulations of its standard capacitor are 4.2V rated voltage, 0.13F design capacity, and size is 27mm×14mm, 2.2mm thickness, and the volume is 0.8cc. The capacitor using new carbon materials developed will be showing about 0.6 F capacity in those standards regulations.
 Metal mold was designed in order to produce of capacitor having outer of resin mold in trial production. The trial production (prototype capacitor) was carried out using simple mold equipment introduced in previous year. Hybrid carbon which ExCFs prepared by TOYO TANSO and nanocarbon including nitrogen was combined at proportion of 30:70 was used for the electrode materials. Electrode material mentioned above was mixed with organic solvent, binder, conductive support material, and it was printed on the gasket rubber, and then cell electrode was produced as a sheet electrode. There was the improvement of about 2.5 times the volume capacity of the paste electrode in the simple substrate cell. However, volume capacity decreased in comparison with the active carbon because of high solvent fraction. Pore volume and particle size having new carbon developed is related it and optimization seems to be necessary.
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