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2015 年度 実績報告書

Metal-Organic Framework-based Cathode Active Materials for Lithium Batteries

研究課題

研究課題/領域番号 15H06265
研究機関名古屋大学

研究代表者

張 中岳  名古屋大学, 物質科学国際研究センター, 助教 (00755704)

研究期間 (年度) 2015-08-28 – 2017-03-31
キーワードMetal-Organic Framework / Energy storage / Battery / Hybrid material
研究実績の概要

In this fiscal year, we have prepared the nanocrystals of Cu(2,7-AQDC) and Cu(2,6-AQDC) . Their electrochemical performances have been tested. Comparing with the pristine MOF crystals which are ground to ~1um, the nanocrystals with a size distribution of 200-500nm did exhibit a moderately improved battery performance. The capacity fade in first 20 cycles is slightly smaller than the case of original MOF. (130mAh/g vs. 105mAh/g for 20th cycle) But the improvement is not significant and we didn't achieve the 100% capacity retention with the nanoparticles.
On the other hand, we also attempted using functionalized carbon nanotubes to grow the crystal of Cu(2,7-AQDC) MOF. We are expecting the carbon nanotubes to be embedded in the crystals of MOF, but the microscopic data suggested what we obtained is a simple mixture of carbon nanotubes and micro-sized crystals. The cyclic voltammetry indicated an enhanced stability of the hybrid material, and the capacity after 50 cycles was improved by >20%.
Although the battery performance of upper mentioned materials didn't meet our initial expectation, the current result does suggest the nanoscale morphology and the hybridization with carbon material will enhance the electrochemical efficiency. Therefore, further efforts could be invested on the development of hybrid MOF materials, such as MOF/reduced graphene oxides.

現在までの達成度 (区分)
現在までの達成度 (区分)

2: おおむね順調に進展している

理由

We have attempted the proposed material: the nanoparticles of redox active MOFs and the MOF/carbon nanotube hybridization. However we have encountered two issues: first, since the redox active Cu-MOF we used had 2-D structure instead of a 3D architecture, it is difficult to achieve the desired material: a pristine crystal that is penetrated by multiple carbon nanotubes. The microscopic study indicated we obtained nanoparticles of MOF on an amorphous substrate. Second, compared with the pristine MOF, the hybridized material did exhibit an improved battery performance in terms of stability and capacity, while the improvement didn't really meet the initial expectation. We still observed the capacity fade within a small cycle number. Therefore, it is challenging to obtain outstanding properties with this pre-reported hybridization method.
Therefore, we decided to bypass this section and put some effort on the other type of hybridization and modulation method to manipulate the electrochemical properties of MOFs. Also, we employed the equipment to test the Li-S batteries, therefore, we decided to investigate the performance of crystalline porous materials, which are used as a sulfur host in the cathode of Li-S batteries.

今後の研究の推進方策

Based on the current result, two directions will be majorly tested in the next fiscal year.The first one is, since the currently obtained MOFs containing electron accepting groups, small molecules with strong electron donating effect will be introduced into the pores of MOFs, forming charge transfer complexes. By this method, we should be able to modulate the electronic conductivity of MOFs with different guests, meanwhile, the battery performance, especially the density of energy storage will be promoted comparing with the pristine material.
The other proposed research topic is to develop novel porous materials with functional groups and unique morphology and use them as hosts of sulfur storage. Li-S batteries is a promising technology in the future market of electrical energy storage devices for the cheap cost and large energy capacity. The main issue of current materials is the fast capacity fade of batteries when they are reused many times. This is caused by the dissolve and escape of sulfur the from cathodes. By introducing binding groups which may form covalent bond with polysulfides, MOFs may act as a strong sulfur binder and host, which could be used as a cathode active material of sulfur batteries. Moreover, with designed morphology such as thin films or hollowspheres, the MOF-based devices may accomodate large amount of sulfur without losing them significantly during the electrochemical process.

  • 研究成果

    (5件)

すべて 2016 2015

すべて 雑誌論文 (2件) (うち査読あり 2件、 謝辞記載あり 2件) 学会発表 (3件) (うち国際学会 2件)

  • [雑誌論文] Discovery of a Bipolar Charging Mechanism in the Solid-State Electrochemical Process of a Flexible Metal-Organic Framework2016

    • 著者名/発表者名
      Zhongyue Zhang, Hirofumi Yoshikawa, Kunio Awaga
    • 雑誌名

      Chemistry of Materials

      巻: 28 ページ: 1298-1303

    • DOI

      10.1021/acs.chemmater.5b04075

    • 査読あり / 謝辞記載あり
  • [雑誌論文] Synthesis of Vanadium-Incorporated, Polyoxometalate-Based Open Frameworks and Their Applications for Cathode-Active Materials2016

    • 著者名/発表者名
      Zhenxin Zhang, Hirofumi Yoshikawa, Zhongyue Zhang, Toru Murayama, Masahiro Sadakane, Yasunori Inoue, Wataru Ueda, Kunio Awaga, Michikazu Hara
    • 雑誌名

      European Journal of Inorganic Chemistry

      巻: 8 ページ: 1242-1250

    • DOI

      10.1002/ejic.201501396

    • 査読あり / 謝辞記載あり
  • [学会発表] Redox Active MOF Brings New Mechanism to the Lithium Batteries2016

    • 著者名/発表者名
      Zhongyue Zhang, Kunio Awaga
    • 学会等名
      International Conference of Coordination Chemistry (ICCC) 42
    • 発表場所
      Brest, France
    • 年月日
      2016-07-03 – 2016-07-08
    • 国際学会
  • [学会発表] Redox Active MOF Brings New Mechanism to the Lithium Batteries2016

    • 著者名/発表者名
      Zhongyue Zhang, Kunio Awaga
    • 学会等名
      The 96th Chemical Society of Japan Annual Meeting
    • 発表場所
      Kyotanabe Campus, Doshisha University, Kyoto, Japan
    • 年月日
      2016-03-24 – 2016-03-27
  • [学会発表] Redox active metal-organic frameworks (MOFs) as high performance cathode active materials for lithium batteries2015

    • 著者名/発表者名
      Zhongyue Zhang, Kunio Awaga
    • 学会等名
      Pacifichem 2015
    • 発表場所
      Hawaii, USA
    • 年月日
      2015-12-15 – 2015-12-20
    • 国際学会

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公開日: 2017-01-06  

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