高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (11): 1941.doi: 10.7503/cjcu20170126

• 研究论文: 无机化学 • 上一篇    下一篇

纳米纤维素基多层级孔道结构碳气凝胶的制备及在锂电池中的应用

孔雪琳1,2, 卢芸2(), 叶贵超1, 李道浩1, 孙瑾3, 杨东江3, 殷亚方2   

  1. 1. 青岛大学材料科学与工程学院, 青岛 266071
    2. 中国林业科学研究院木材工业研究所, 北京 100091
    3. 青岛大学环境科学与工程学院, 青岛 266071
  • 收稿日期:2017-03-01 出版日期:2017-11-10 发布日期:2017-10-30
  • 作者简介:联系人简介: 卢 芸, 女, 博士, 助理研究员, 主要从事生物纳米材料及气凝胶研究. E-mail: y.lu@criwi.org.cn
  • 基金资助:
    国家自然科学基金(批准号: 31500468)和中央级公益性科研院所基本科研业务费专项(批准号: CAFYBB2016QB012)资助

Nanofibrillated Cellulose Derived Hierarchical Porous Carbon Aerogels: Efficient Anode Material for Lithium Ion Battery

KONG Xuelin1,2, LU Yun2,*(), YE Guichao1, LI Daohao1, SUN Jin3, YANG Dongjiang3, YIN Yafang2   

  1. 1. School of Materials Science and Engineering, Qingdao University, Qingdao 266071, China
    2. Research Institute of Wood Industry, Chinese Academy of Forestry, Beijing 100091, China
    3. School of Environmental Science and Engineering, Qingdao University, Qingdao 266071, China
  • Received:2017-03-01 Online:2017-11-10 Published:2017-10-30
  • Contact: LU Yun E-mail:y.lu@criwi.org.cn
  • Supported by:
    † Supported by the National Natural Science Foundation of China(No.31500468) and the Fundamental Research Funds for the Central Non-profit Research Institution of CAF(No.CAFYBB2016QB012)

摘要:

采用纳米精磨法对商品桉木浆进行纳米纤丝化处理, 得到了高长径比、 尺寸均一的纳米纤丝化纤维素(NFC), 平均直径为230.10 nm, 长度达数十微米. 将其组装、 干燥后制得具有大量介孔的纳米纤丝化纤维素气凝胶(NFCA). 将NFCA在氮气氛围下高温碳化制得碳气凝胶(CNFA), 或在氢氧化钾条件下辅助碳化制得具有多层级孔道结构的碳气凝胶(CNFA-A), 在保留的碳气凝胶骨架结构上进行孔洞构建. 通过扫描电子显微镜(SEM)、 透射电子显微镜(TEM)表征及Nanomeasure®统计分析, 发现NFC的平均直径经碳化后减小到53.16 nm. 利用X射线衍射(XRD)、 BET比表面积测试和拉曼光谱揭示了碳化处理对纳米纤维素结构、 比表面积、 石墨化程度和缺陷的影响. 结果表明, KOH辅助碳化处理后的碳气凝胶不仅保留了纤维素气凝胶前驱体的网络结构, 还在其骨架上二次构建了更多的微孔和介孔, 其比表面积高达488.92 m2/g, 总孔容为0.404 cm3/g, 所得的碳骨架被部分石墨化, 具有良好的导电性. 这类源于生物质的高比表面积碳气凝胶在被用作锂离子电池(LIB)负极材料时表现出优异的电化学性能, 在电流密度1 A/g下连续充放电1000次后比容量达到409 mA·h/g, 在电流密度高达20 A/g下, 比容量还能维持在219 mA·h/g.

关键词: 纳米纤丝化纤维素, 气凝胶, 碳化, 多层级结构, 锂离子电池

Abstract:

The nanofibrillated cellulose(NFC) with large aspect ratio and uniform size(mean diameter is 230.10 nm) was fabricated from commercial eucalyptus pulps by scale-up nano-grinding. Then the NFC was assembled to NFC aerogels(NFCA) with three-dimensional(3D) frameworks. After carbonization of NFCA under N2 atmosphere, the carbon nanofiber aerogels(CNFA) were generated with the inherited 3D network structure. With futher KOH-assisted annealing of CNFA, the hierarchical porous carbon aerogels(denoted as CNFA-A) were finally obtained. CNFA-A combined the inherited original 3D network from NFCA and the secondary constructed micropore-mesopore structure. The mean diameter of CNFA-A was diminished to 53.16 nm. The structures of three kinds of cellulose-based aerogels were characterized by scanning electron microscopy(SEM) and transmission electron microscopy(TEM), and the statistic diameter of nanofibril building-blocks was obtained by Nanomeasure®. The graphitization degree of cellulose-based aerogels was investigated by X-ray diffraction(XRD) and Raman spectroscopy, and the specific surface area was measured through BET specific surface area test. The specific surface area of CNFA-A is as high as 488.92 m2/g and the total pore volume can reach up to 0.404 cm3/g. In addition, as anode material for lithium ion battery, the CNFA-A exhibits a high reversible capacity(448 mA·h/g at 1 A/g), an excellent rate capability(219 mA·h/g at 20 A/g) and an outstanding cycling performance(409 mA·h/g at 1 A/g after 1000 cycles).

Key words: Nanofibrillated cellulose, Aerogel, Carbonization, Hierarchical structure, Lithium ion battery

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