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Role of anions on structure and pseudocapacitive performance of metal double hydroxides decorated with nitrogen-doped graphene

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Abstract

Electrochemical capacitors (EC) bear faster charge-discharge; however, their real applications are still on a long away due to lower capacitance and energy densities which mainly arise from simple surface charge accumulation or/and reaction. Here, a novel synthesis strategy was designed to obtain the purposeful hybrids of nickel cobalt double hydroxide (NiCoDH) with genetic morphology to improve their electrochemical performance as electrode of EC. Nanostructures of metal hydroxides were grown on the nitrogen-doped graphene (NG) sheets by utilizing defects as nucleation sites and their composition was optimized both by tuning the ratio of Ni: Co as well as the counter halogen and carbonate anions to improve the porosity, stabilize the structure and mediate the redox reaction. The growth of the hybrids was guided by the Co ions through topochemical transformation supported by hoping charge transfer process and olation growth. NG overcoating successfully protects the nanostructure of NiCoDH during electrochemical test and enhances overall conductivity of the electrode, improving the mass and ionic transportations. As a result, the hybrid exhibits excellent capacitance of 2925 F g−1 at 1 A g−1, as well as long cyclic stability of 10,000 cycles with good capacity retention of 90% at 16 A g−1. Furthermore, the hybrid shows excellent energy and power densities of 52 W h kg−1 and 3191 W kg−1, respectively at discharge rate of 16 A g−1. It is expected that this strategy can be readily extended to other metal hydroxides, oxides and sulphides to improve their electrochemical performances.

摘要

超级电容器因为具有充放电时间短的特点引起了人们的广泛关注. 然而, 由于电极表面的电荷积聚和化学反应, 电容器的比电容及能量密度大大降低, 限制了超级电容器的实际应用. 本文提出了一种新颖的合成方法用以制备基于镍钴双氢氧化物的复合材料, 该复合材料作为超级电容器的电极具有优异的电化学性能. 利用氮掺杂石墨烯的缺陷, 金属氢氧化物纳米结构在氮掺杂石墨烯表面生长, 形成复合结构. 通过调节并优化镍钴的元素比以及卤素离子、 碳酸根离子的含量, 能够改善材料的孔隙度、 提高材料结构的稳定性以及促进电化学反应. 金属氢氧化物的形成由钴离子的氧化反应引导, 并通过定向生长方式形成一维结构. 氮掺杂石墨烯有效保护镍钴双氢氧化物的纳米结构, 使其在电化学测试中不被破坏, 同时, 氮掺杂石墨烯还能够提高电极的导电性, 利于物质及离子传输. 电化学测试表明, 该复合材料在电流密度为1 A g−1时, 比电容高达2925 F g−1, 并且在高电流密度下(16 A g−1)展现出了优异的循环稳定性, 在10,000次循环后比电容仍然保持在90%. 在16 A g−1的电流密度下, 材料的能量密度和功率密度分别达到了52 Wh kg−1和3191 W kg−1. 该合成方法为制备基于金属氢氧化物、 氧化物、 硫化物等高性能超级电容器电极提供了新的途径.

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Correspondence to Chuanbao Cao or Yanglong Hou.

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These authors contributed equally to this work.

Nasir Mahmood obtained his BSc degree in 2009 in Chemistry from Punjab University and MSc degree in 2011 in Materials and Surface Engineering from National University of Science and Technology, Pakistan. He joined Peking University in 2011, where he is currently pursuing his PhD in Materials Science and Engineering under the guidance of Prof. Yanglong Hou. His research involves the synthesis of graphene/graphene-based nanomaterials and their application in energy storage and conversion devices.

Muhammad Tahir obtained his BSc and MSc degree in 2008 and 2011 from Center for High Energy Physics, University of the Punjab, Lahore, Pakistan. Later in 2011, he joined Beijing Institute of Technology, where he is currently pursuing his PhD in Materials Physics and Chemistry under the supervision of Prof. Chuanbao Cao. His research focus is towards energy harvesting applications of nanomaterials like supercapacitors and photocatalyst. He is also working on fabrication of novel nanostructures of carbon nitride.

Chuanbao Cao is currently the Chief Responsible Professor of School of Materials Science and Engineering, Director of Research Center of Materials Science of Beijing Institute of Technology. His research focuses on the electrochemical energy storage and conversion technology include electrode materials of Lithium ion battery, supercapacitors and photoelectrochemical materials. Until now, he has published more than 240 peer-review research papers, holds or has filed 37 patents and patent applications.

Yanglong Hou received his PhD in Materials Science from Harbin Institute of Technology, China in 2000. After a short post-doctoral training at Peking University, he worked at the University of Tokyo from 2002–2005 as JSPS foreign special researcher and also at Brown University from 2005–2007 as postdoctoral researcher. He joined Peking University in 2007, and now is a Professor of Materials Science. His research interests include the design and chemical synthesis of functional nanoparticles and graphene-based nanocomposites, and their biomedical and energy related applications.

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Mahmood, N., Tahir, M., Mahmood, A. et al. Role of anions on structure and pseudocapacitive performance of metal double hydroxides decorated with nitrogen-doped graphene. Sci. China Mater. 58, 114–125 (2015). https://doi.org/10.1007/s40843-015-0028-3

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