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2015 Fiscal Year Annual Research Report

3次元ナノ界面の大規模創製と、蓄電デバイス電極への展開

Research Project

Project/Area Number 25249111
Research InstitutionWaseda University

Principal Investigator

野田 優  早稲田大学, 理工学術院, 教授 (50312997)

Project Period (FY) 2013-10-21 – 2017-03-31
Keywordsナノ界面 / 3次元化 / カーボンナノチューブ / シリコン / 高速製膜 / 蓄電応用
Outline of Annual Research Achievements

①急速蒸着法によるCNT-金属複合集電体創成と活物質複合化によるポーラス電極開発
Cu箔はLi二次電池負極の主要な集電体で、軽量化が課題である。CNTとCu蒸着膜が直接接合したバインダーレスの三次元集電体を開発した。CNT垂直配向膜にCuを蒸着、自己組織化でCNT壁状構造体を実現した。さらにSi-Cuを蒸着、40サイクルで1500 mAh/g-Si, 2 mAh/cm2の高い放電容量を実現した。Al箔はLi二次電池正極やキャパシタ電極の集電体として多用される。CNTスポンジ膜やCNT垂直配向膜などへのAl蒸着により多様なCNT-Al三次元集電体を実現、さらに活物質層にAlを蒸着する逆転の発想を行い、レート特性に優れたCNT-活性炭/Alキャパシタ電極を実現した。

②CNTスポンジ膜中への活物質包含によるソフト電極開発
S@CNTソフト電極では、昇華法に注力して特性向上を進めた。S包含量は60 wt%程度で最も優れた特性が得られた。高濃度電解液を併用、100サイクル時に約800 mAh/g-Sの高い放電容量を実現した。Si@CNTソフト電極では、Siナノ粒子の粒径制御、Si/CNT比制御により性能向上を進め、100サイクルで900 mAh/g-Si, 0.7 mAh/cm2の放電容量を実現した。さらに現行電池で正負極に用いられているLiCoO2、黒鉛を用いたソフト電極を作製、両者を組み合わせた全電池を開発した。1 wt%のCNTで99 wt%の活物質を保持、130 mAh/g-LiCoO2, 353 mAh/g-graphiteと実用電池と同等性能を実現した。バインダーレス、金属箔レスのため、電極総質量あたりの性能はとても良好であった。さらに50 mm角のラミネートセルを作製、金属箔の櫛形電極で動作、CNTによりバインダーと金属を実電池からほぼ無くせることを示した。

Current Status of Research Progress
Current Status of Research Progress

1: Research has progressed more than it was originally planned.

Reason

本課題では、Cu箔上の組成傾斜を有したSi系多孔質膜によるリチウム二次電池負極と、CNTスポンジに活物質を包含した電気化学キャパシタ電極から入り、最終年度にCNTスポンジをベースとしたリチウム二次電池の正負極まで取り組む計画であった。前倒しで検討が進み、H26年度にはS@CNT、Si@CNTソフト正負極に着手、H27年度に上記の良好な特性を達成した。また、蓄電デバイスに欠かせないCu箔に関して、バインダーを用いず、CNTが突き刺さったCu箔およびAl箔を急速蒸着法で開発できた。蓄電デバイス中で大きな重量割合を占める金属箔集電体を軽量化し、かつ界面を三次元化できるこの集電体は、当初計画にはなかったが、本研究開発の途中で着想し、2件の特許出願にも繋がった。さらに、CNTスポンジを用いLiCoO2と負極の正負極を開発、その全電池動作、さらにはラミネートセル動作も実現した。申請額の2/3という限られた予算で、人件費と消耗品費でそのほとんどを使い切ってしまう状況が続いているが、グローブボックス等の必須設備を連携者に借用し、また技術面でも支援して頂くことで、計画以上のペースで進んでいる。

Strategy for Future Research Activity

本研究課題は順調に立ち上がり、H25-27年度を通して当初計画以上のペースで前倒し+αで進んでいる。今後も現状の進め方を維持し、計画以上の成果をあげたい。
ただ、予算は申請額の2/3と限られ、人件費と消耗品費でそのほとんどを使い切ってしまう状況が続いており、追加の可能性があればご検討頂きたい。

  • Research Products

    (44 results)

All 2016 2015 Other

All Int'l Joint Research (1 results) Journal Article (4 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 4 results,  Open Access: 2 results,  Acknowledgement Compliant: 1 results) Presentation (36 results) (of which Int'l Joint Research: 16 results,  Invited: 6 results) Remarks (2 results) Patent(Industrial Property Rights) (1 results) (of which Overseas: 1 results)

  • [Int'l Joint Research] Georgia Institute of Technology(米国)

    • Country Name
      U.S.A.
    • Counterpart Institution
      Georgia Institute of Technology
  • [Journal Article] Biomass-derived carbonaceous positive electrodes for sustainable lithium-ion storage2016

    • Author(s)
      T. Liu, R. Kavian, Z. Chen, S.S. Cruz, S. Noda, and S.W. Lee
    • Journal Title

      Nanoscale

      Volume: 8 Pages: 3671-3677

    • DOI

      10.1039/C5NR07064C

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Electrochemical polymerization of pyrene derivatives on functionalized carbon nanotubes for pseudocapacitive electrodes2015

    • Author(s)
      J. C. Bachman, R. Kavian, D. J. Graham, D.Y. Kim, S. Noda, D. G. Nocera, Y. Shao-Horn, and S.W. Lee
    • Journal Title

      Nature Communications

      Volume: 6 Pages: 7040

    • DOI

      10.1038/ncomms8040

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Overcoming the quality-quantity tradeoff in dispersion and printing of carbon nanotubes by a repetitive dispersion-extraction process2015

    • Author(s)
      H. Shirae, D.Y. Kim, K. Hasegawa, T. Takenobu, Y. Ohno, and S. Noda
    • Journal Title

      Carbon

      Volume: 91 Pages: 20-29

    • DOI

      10.1016/j.carbon.2015.04.033

    • Peer Reviewed
  • [Journal Article] One-minute deposition of micrometre-thick porous Si-Cu anodes with compositional gradients on Cu current collectors for lithium secondary batteries2015

    • Author(s)
      J. Lee, K. Hasegawa, T. Momma, T. Osaka, and S. Noda
    • Journal Title

      Journal of Power Sources

      Volume: 286 Pages: 540-550

    • DOI

      10.1016/j.jpowsour.2015.04.024

    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Carbon nanotube papers capturing Si nanoparticles for binder-free anodes of lithium ion batteries2016

    • Author(s)
      ○Takayuki Kowase, Kei Hasegawa, and Suguru Noda
    • Organizer
      2016 MRS Spring Meeting
    • Place of Presentation
      Phoenix, Arizona, USA
    • Year and Date
      2016-03-31
    • Int'l Joint Research
  • [Presentation] CNT sponge-based sulfur cathodes with GO-enhanced separator for lithium-sulfur batteries2016

    • Author(s)
      ○Keisuke Hori, Kei Hasegawa, Yuta Nishina, and Suguru Noda
    • Organizer
      2016 MRS Spring Meeting
    • Place of Presentation
      Phoenix, Arizona, USA
    • Year and Date
      2016-03-30
    • Int'l Joint Research
  • [Presentation] Continuous dispersion of carbon nanotubes with minimal loss and damage2016

    • Author(s)
      ○Hiroyuki Shirae, Kei Hasegawa, and Suguru Noda
    • Organizer
      EMN Meeting on Nanotubes
    • Place of Presentation
      Honolulu, Hawaii
    • Year and Date
      2016-03-27 – 2016-03-31
  • [Presentation] 1 wt% carbon nanotube lithium ion batteries without binder nor metal foil2016

    • Author(s)
      ○長谷川 馨,野田 優
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-15
  • [Presentation] Carbon nanotube sponge-based sulfur cathode for lithium-sulfur batteries2016

    • Author(s)
      ○堀 圭佑,長谷川 馨,仁科 勇太,門間 聰之,逢坂 哲彌,野田 優
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-15
  • [Presentation] Creation of oxygen reduction reaction catalyst by supporting ZrO2 on carbon nanotube papers2016

    • Author(s)
      ○葛原 颯己,長谷川 馨,野田 優
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-15
  • [Presentation] Carbon nanotube papers capturing Si nanoparticles for binder-free anodes of Li secondary batteries2016

    • Author(s)
      ○小輪瀬 敬之,長谷川 馨,門間 聰之,逢坂 哲彌,野田 優
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-15
  • [Presentation] Gas-phase continuous production of carbon nanotubes of smaller diameters at higher yields2016

    • Author(s)
      ○野田 優,山口 麻衣,岡田 翔平,大場 一哲,杉野 裕亮,栗谷 匡明,長谷川 馨,大沢 利男
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-14
  • [Presentation] Fluidized-bed production of long carbon nanotubes and creation of three-dimensional electrodes for electric storage devices2016

    • Author(s)
      ○野田 優,陳 忠明,川端 孝祐,蜂谷 宗一郎,キンテーロ リカルド,許 乃傲,成林 美里,堀 圭佑,小輪瀬 敬之,長谷川 馨,大沢 利男
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-14
  • [Presentation] Rapid vapor deposition of active materials and current collectors toward high-capacity, light- weight electric storage devices2016

    • Author(s)
      ○野田 優,李 重昊,青井 慈喜,本田 陽一郎,長谷川 馨,大沢 利男
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-14
  • [Presentation] Fabrication, microstructure control, and electrochemical performance evaluation of graphene oxide-carbon nanotube hybrid electrodes2016

    • Author(s)
      ○許 乃傲,キンテーロ リカルド,陳 忠明,長谷川 馨,仁科 勇太,野田 優
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-14
  • [Presentation] Fluidized bed production of carbon nanotubes using gas-phase supported catalyst on ceramic powders2016

    • Author(s)
      ○川端 孝祐,長谷川 馨,大沢 利男,野田 優
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-14
  • [Presentation] Fluidized bed production of single-wall carbon nanotubes using carefully sputtered catalyst on beads2016

    • Author(s)
      ○蜂谷 宗一郎,陳 忠明,川端 孝祐,長谷川 馨,大沢 利男,野田 優
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-14
  • [Presentation] Creation of carbon nanotube-aluminium hybrid structures and their application to electronic energy storage devices2016

    • Author(s)
      ○本田 陽一郎,青井 慈喜,長谷川 馨,野田 優
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-14
  • [Presentation] LiFePO4 cathode based on three-dimensional current collector of carbon nanotubes for lithium secondary batteries2016

    • Author(s)
      ○山片 豪,長谷川 馨,野田 優
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-14
  • [Presentation] Creation of carbon nanotube-copper hybrid foils and their application to lithium secondary batteries2016

    • Author(s)
      ○青井 慈喜,長谷川 馨,野田 優
    • Organizer
      化学工学会第81年会
    • Place of Presentation
      大阪府
    • Year and Date
      2016-03-14
  • [Presentation] 1 wt% carbon nanotubes/active material freestanding electrodes and binder-free, minimum current collector lithium ion battery2016

    • Author(s)
      ○長谷川 馨,野田 優
    • Organizer
      第50回フラーレン・ナノチューブ・グラフェン総合シンポジウム
    • Place of Presentation
      東京都
    • Year and Date
      2016-02-20
  • [Presentation] Fluidized-bed production of sub-millimeter-long carbon nanotubes and their application to electrochemical energy storage devices2015

    • Author(s)
      ○Suguru Noda
    • Organizer
      The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem2015)
    • Place of Presentation
      Honolulu, Hawaii
    • Year and Date
      2015-12-18
    • Int'l Joint Research / Invited
  • [Presentation] Efficient production of carbon nanotubes in 3D for electrochemical energy storage2015

    • Author(s)
      ○Suguru Noda
    • Organizer
      3rd DGIST-Waseda Workshop on Electrochemistry
    • Place of Presentation
      Tokyo, Japan
    • Year and Date
      2015-12-11
    • Int'l Joint Research
  • [Presentation] Carbon nanotube papers capturing Si nanoparticles for binder-free anodes of lithium ion batteries2015

    • Author(s)
      ○Takayuki Kowase, Kei Hasegawa, and Suguru Noda
    • Organizer
      3rd DGIST-Waseda Workshop on Electrochemistry
    • Place of Presentation
      Tokyo, Japan
    • Year and Date
      2015-12-10
    • Int'l Joint Research
  • [Presentation] CNT sponge-based sulfur cathodes with GO-enhanced separator for lithium-sulfur batteries2015

    • Author(s)
      Keisuke Hori, Kei Hasegawa, Yuta Nishina, and Suguru Noda
    • Organizer
      3rd DGIST-Waseda Workshop on Electrochemistry
    • Place of Presentation
      Tokyo, Japan
    • Year and Date
      2015-12-10
    • Int'l Joint Research
  • [Presentation] Overcoming the quality-quantity tradeoff in dispersion and printing of carbon nanotubes by a repetitive dispersion-extraction process2015

    • Author(s)
      ○Hiroyuki Shirae, Dong Young Kim, Kei Hasegawa, Taishi Takenobu, Yutaka Ohno, and Suguru Noda
    • Organizer
      The World Engineering Conference and Convention 2015 (WECC2015)
    • Place of Presentation
      Kyoto, Japan
    • Year and Date
      2015-12-02
    • Int'l Joint Research
  • [Presentation] Simple fabrication of carbon nanotube-based materials for energy storage and electronic applications2015

    • Author(s)
      ○Suguru Noda
    • Organizer
      The 6th A3 Symposium on Emerging Materials - Nanomaterials for Electronics, Energy, and Environment
    • Place of Presentation
      Fukuoka, Japan
    • Year and Date
      2015-11-11
    • Int'l Joint Research / Invited
  • [Presentation] CNT sponge-based sulfur cathodes with GO-enhanced separator for lithium-sulfur batteries2015

    • Author(s)
      ○Keisuke Hori, Kei Hasegawa, Yuta Nishina, and S. Noda
    • Organizer
      The 6th A3 Symposium on Emerging Materials - Nanomaterials for Electronics, Energy, and Environment
    • Place of Presentation
      Fukuoka, Japan
    • Year and Date
      2015-11-10
    • Int'l Joint Research
  • [Presentation] Carbon nanotube papers capturing Si nanoparticles for binder-free anodes of lithium ion batteries2015

    • Author(s)
      ○Takayuki Kowase, Kei Hasegawa, and S. Noda
    • Organizer
      The 6th A3 Symposium on Emerging Materials - Nanomaterials for Electronics, Energy, and Environment
    • Place of Presentation
      Fukuoka, Japan
    • Year and Date
      2015-11-09
    • Int'l Joint Research
  • [Presentation] カーボンナノチューブのカスタム合成:基板上合成,気相合成,流動層合成と,応用2015

    • Author(s)
      ○野田 優
    • Organizer
      早稲田大学各務記念材料技術研究所オープンセミナー「炭素材料・軽元素材料が拓く次世代デバイス」
    • Place of Presentation
      東京都
    • Year and Date
      2015-10-20
    • Invited
  • [Presentation] One-minute deposition of micrometre-thick porous Si and Si-Cu anodes on Cu current collectors for lithium secondary batteries2015

    • Author(s)
      ○Jungho Lee, Kei Hasegawa, Toshiyuki Momma, Tetsuya Osaka, and Suguru Noda
    • Organizer
      APCChE2015
    • Place of Presentation
      Melbourne, Australia
    • Year and Date
      2015-09-29
    • Int'l Joint Research
  • [Presentation] Fluidized-bed production of sub-millimeter-long, >99%-pure carbon nanotubes and their application to electrochemical energy storage2015

    • Author(s)
      ○Zhongming Chen, Ricardo Quintero, Misato Narubayashi, Kei Hasegawa, and Suguru Noda
    • Organizer
      APCChE2015
    • Place of Presentation
      Melbourne, Australia
    • Year and Date
      2015-09-29
    • Int'l Joint Research
  • [Presentation] Overcoming the quality-quantity tradeoff in dispersion and printing of carbon nanotubes by a repetitive dispersion-extraction process2015

    • Author(s)
      ○白江 宏之,金 東榮,長谷川 馨,竹延 大志,大野 雄高,野田 優
    • Organizer
      化学工学会第47秋季大会
    • Place of Presentation
      北海道
    • Year and Date
      2015-09-09
  • [Presentation] Carbon nanotube papers capturing Si nanoparticles for binder-free anodes of lithium ion batteries2015

    • Author(s)
      ○小輪瀬 敬之,長谷川 馨,野田 優
    • Organizer
      第49回フラーレン・ナノチューブ・グラフェン総合シンポジウム
    • Place of Presentation
      福岡県
    • Year and Date
      2015-09-07
  • [Presentation] カーボンナノチューブの触媒成長の理解とカスタム合成2015

    • Author(s)
      ○野田 優
    • Organizer
      日本セラミックス協会 第49回基礎科学部会セミナー
    • Place of Presentation
      愛知県
    • Year and Date
      2015-07-17
    • Invited
  • [Presentation] Overcoming the quality-quantity tradeoff in dispersion and printing of carbon nanotubes by a repetitive dispersion-extraction process2015

    • Author(s)
      ○Hiroyuki Shirae, Dong Young Kim, Kei Hasegawa, Taishi Takenobu, Yutaka Ohno, and Suguru Noda
    • Organizer
      The Sixteenth International Conference on the Science and Application of Nanotubes (NT15)
    • Place of Presentation
      Nagoya, Japan
    • Year and Date
      2015-07-02
    • Int'l Joint Research
  • [Presentation] Hybrid electrodes of self-supporting carbon nanotube films with MnO2 particles for electrochemical capacitors2015

    • Author(s)
      ○Misato Narubayashi, Kei Hasegawa, Zhongming Chen, Toshiyuki Momma, Tetsuya Osaka, and Suguru Noda
    • Organizer
      The Sixteenth International Conference on the Science and Application of Nanotubes (NT15)
    • Place of Presentation
      Nagoya, Japan
    • Year and Date
      2015-07-02
    • Int'l Joint Research
  • [Presentation] カーボンナノチューブおよびグラフェンの基板上成長機構と合成技術2015

    • Author(s)
      ○野田 優
    • Organizer
      触媒学会千葉地区講演会「触媒と炭素材料」
    • Place of Presentation
      千葉県
    • Year and Date
      2015-06-05
    • Invited
  • [Presentation] Understanding and controlling chemistries for CNT synthesis in scales from catalysts to reactors2015

    • Author(s)
      ○Suguru Noda
    • Organizer
      Guadalupe Workshop VII: Workshop on Nucleation and Growth Mechanisms of Single Wall Carbon Nanotubes
    • Place of Presentation
      Bandera, TX, USA
    • Year and Date
      2015-04-13
    • Int'l Joint Research / Invited
  • [Presentation] Separate fluidized beds for catalyst deposition and CNT array growth on ceramic powders from less-reactive carbon source2015

    • Author(s)
      ○Kosuke Kawabata, Soichiro Hachiya, Zhongming Chen, Kei Hasegawa, Toshio Osawa, and Suguru Noda
    • Organizer
      Guadalupe Workshop VII: Workshop on Nucleation and Growth Mechanisms of Single Wall Carbon Nanotubes
    • Place of Presentation
      Bandera, TX, USA
    • Year and Date
      2015-04-11
    • Int'l Joint Research
  • [Remarks] 野田研究室ホームページ

    • URL

      http://www.f.waseda.jp/noda/index-j.html

  • [Remarks] Noda Lab's Home Page

    • URL

      http://www.f.waseda.jp/noda/

  • [Patent(Industrial Property Rights)] 複合膜及びその製造方法2016

    • Inventor(s)
      野田 優,青井 慈喜,森川 裕介,本田 陽一郎
    • Industrial Property Rights Holder
      学校法人早稲田大学,JX日鉱日石エネルギー株式会社
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      PCT/JP2016/055888
    • Filing Date
      2016-02-26
    • Overseas

URL: 

Published: 2017-01-06   Modified: 2022-01-28  

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