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    面向世界科技前沿,面向国家重大需求,面向国民经济主战场,率先实现科学技术跨越发展,率先建成国家创新人才高地,率先建成国家高水平科技智库,率先建设国际一流科研机构。

    ——中国科学院办院方针

    首页 > 科研进展

    青岛能源所开发出基于石墨炔的高性能储钠材料

    2019-09-30 青岛生物能源与过程研究所
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      中国科学院青岛生物能源与过程研究所碳基材料与能源应用研究组研究发现,通过对石墨炔碳材料进行分子设计控制炔键的数目,增加更多的储钠位点和传输通道,进而制备出具有更好电化学表现的储钠材料,其优异的比容量和超长的循环稳定性表明石墨炔类碳材料在储能方面具有巨大的应用潜力。

      由于钠元素在全球含量丰富且廉价易得,钠离子电池和电容器的成本相较于锂离子电池显著降低,特别是对于大型储能装置,钠离子电池和电容器更兼具可持续性的优势,因此,钠离子电池的研究迅速引起了全世界科研工作者的关注。然而商用石墨作为钠离子电池和电容器的负极材料所能够提供的比容量太低,严重制约了钠离子电池和电容器的进一步发展,为此,世界范围的研究组已经开展了对新型负极材料的探索研究工作,包括对新型碳基材料的发展和探索。

      近年来研发的碳化石墨、硬碳、石墨烯等作为钠离子电池和电容器的负极材料,具有成本低、电位低、容量大等优点,被认为是很有前途的候选材料。然而,这些碳负极普遍存在的低容量和循环稳定性是一直有待改善的问题。碳基材料与能源应用研究组长期致力于钠离子电池和电容器电极材料的研究,开发制备了基于石墨炔的钠离子电池和电容器负极材料,凭借其本身富含炔键的特点,石墨炔负极在储钠方面表现出更优异的电化学表现,包括,多孔石墨炔直接应用于钠离子电池负极(J. Mater. Chem. A 2017, 5, 2045-2051),掺氮石墨炔实现兼具高功率密度和能量密度的钠离子电容器(ChemElectroChem 2018, 5, 1435-1443),石墨炔纳米墙获得高性能钠离子电容器(ACS Appl. Mater. Interface, 2017, 9, 40604-40613。在此基础上,通过对石墨炔进行分子设计,引入氢元素并制备了具有均匀缺陷的氢取代石墨炔类碳材料,而这些引入氢取代石墨炔,在储钠方面均表现出了更高的理论比容量(>1200 mAh g-1)和实验比容量(>600 mAh g-1),同时具有优秀倍率性能的循环稳定性能(Nat. Commun., 2017, 8, 1172)。

      特别是近期,研究组设计制备了氢取代石墨炔(HsGY),其中大量的炔键大孔和中孔构造有利于电解质的快速渗透,缩短了其扩散和传输的路径,提高了电极的倍率性能和循环稳定性能(如图所示)。在100 mAh g-1电流密度下,HsGY电极能够得到高达680 mAh g-1的高可逆比容量。即使在高达5000 mA g-1的电流密度下,HsGY电极的比容量仍可以稳定在330 mAh g-1。得益于HsGY电极材料兼备二维和三维层状多孔材料的特点,钠离子能够大量存储在HsGY的面内和面外,同时钠离子能够很容易地在HsGY层内扩散迁移或层间穿越传输。稳定性测试表明,在5000 mAh g-1的大电流密度下循环5900次,其可逆容量也能稳定在320 mAh g-1,得到96%的优异容量保持率。相关成果已经发表在国际期刊《材料化学学报A》(J. Mater. Chem. A (2019, 7, 11186-11194))上。

      上述研究成果对于新型碳基材料的设计制备及其储能、催化具有重要的指导意义,同时表明石墨炔类碳材料在能源设备的开发应用方面具有巨大潜力。

      研究得到国家自然科学基金项目、中科院前沿重点项目、山东省自然科学基金的支持。

    图:HsGY及其电化学性能。(a) 倍率性能,(b) 钠离子存储示意图,(c) 钠离子迁移路径示意图,(d) 循环性能,插图是组装的SIBs可保持LED设备持续点亮。

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