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Optimizing nanostructure and constructing heterostructure via Mo/W incorporation to improve electrochemical properties of NiCoP for hybrid supercapacitors

引入Mo/W优化形貌并构建异质结构提高NiCoP作为 混合电容器电极的电化学性能

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Abstract

Transition metal phosphides (TMPs) are promising battery-type electrodes for hybrid supercapacitors (HSCs) due to their high electrical conductivity and electrochemical activity. Constructing TMPs with fast kinetics and stable structure is requisite to realize high-performance HSCs but remains a challenge. Herein, we incorporate Mo (or W) into NiCoP to form Ni-Co-Mo-P (or Ni-Co-W-P) heterostructures with a unique three-dimensional (3D) open morphology and modified electronic structure. Electrochemical analyses and density functional theory (DFT) calculations reveal that the incorporation of Mo/W enables NiCoP with optimized nanostructure, high conductivity, abundant reaction active sites and enhanced reaction kinetics. As a result, the designed Ni-Co-Mo-P heterostructure delivers a high areal capacity of 4.08 C cm−2 (703 C g−1) at 2 mA cm−2 and 3.25 C cm−2 at 30 mA cm−2 with a good cycling stability, superior to those of NiCoP and Ni-Co-W-P counterparts. The practical feasibility of the Ni-Co-Mo-P heterostructure is further demonstrated by an energy conversion and storage system consisting of commercial solar cell and Ni-Co-Mo-P//activated carbon (AC) device, which could obtain a high energy density of 53.3 W h kg−1 at a power density of 800 W kg−1. All-solid-state Ni-Co-Mo-P//AC device further illustrates the superior flexibility and makes a strong candidate for wearable energy storage electronics.

摘要

过渡金属磷化物具有高电导率和高电化学活性, 是一类新兴的 混合电容器电极材料. 然而制备具有快速反应动力学和稳定结构的过 渡金属磷化物仍然是一大挑战. 本文将Mo或W引入到NiCoP中, 得到 具有三维开放结构的纳米阵列和优化电子结构的异质结构. 相比于Ni-CoP纳米阵列, Ni-Co-Mo-P或Ni-Co-W-P纳米阵列具有更大的比表面 积和更多的空隙, 这种独特的结构不仅有助于电解液的渗透, 还可以缓 解氧化还原过程中的体积变化. 密度泛函理论计算结果显示引入高价 Mo或W元素形成异质结构提高了材料的本征电导率, 加快了反应动力 学. Ni-Co-Mo-P纳米阵列在2 mA cm−2 的电流密度下表现出 4.08 C cm−2 (703 C g−1) 的高面积比容量; 在30 mA cm−2下, 比容量还 能保持在3.25 C cm−2. 此外, Ni-Co-Mo-P纳米阵列与活性炭组装成的 水系混合超级电容器表现出800 W kg−1的高能量密度. 本研究为高性 能过渡金属磷化物基电极材料的设计拓宽了思路, 有助于促进其在混 合电容器中的应用.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51772267), and the Science and Technology Program of Guangxi Zhuang Autonomous Region (ZD20302001).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. College of Materials and Chemistry, China Jiliang University, Hangzhou, 310018, China

    Quan Zong  (宗泉) & Jiangying Wang  (王疆瑛)

  2. School of Materials Science and Engineering, State Key Lab Silicon Mat, Zhejiang University, Hangzhou, 310027, China

    Quan Zong  (宗泉), Daiwen Tao  (陶代文), Hui Yang  (杨辉), Jianhui Zhan  (詹建辉), Xiong Liu  (刘雄) & Qilong Zhang  (张启龙)

  3. ZJU-Guangxi-ASEAN Innovation & Research Center, Nanning, 530022, China

    Hui Yang  (杨辉) & Qilong Zhang  (张启龙)

  4. Department of Materials Science and Engineering, University of Washington, Seattle, WA, 98195, USA

    Guozhong Cao  (曹国忠)

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  1. Quan Zong  (宗泉)
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Contributions

Zong Q and Tao D designed and prepared the samples; Zhan J and Liu X performed the characterizations; Yang H and Wang J finished the first-principles calculation; Zong Q and Tao D performed data analysis and wrote the paper with support from Zhang Q and Cao G. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Quan Zong  (宗泉), Qilong Zhang  (张启龙) or Guozhong Cao  (曹国忠).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Quan Zong received his PhD degree (2021) from the School of Materials Science and Engineering, Zhejiang University. He is currently working at the College of Materials and Chemistry, China Jiliang University. His current research interests include the synthesis and characterization of nanomaterials for electrochemical energy conversion and storage technologies.

Daiwen Tao received his MS degree from Northwest Normal University, China, in 2020. Afterwards, he joined Prof. Qilong Zhang’s group at Zhejiang University, China, for pursuing his PhD degree in materials science and engineering. His research interests focus on the electrochemical energy storage devices and their application in renewable energy storage and hybrid-electric vehicles.

Qi-Long Zhang received his PhD degree in materials science and engineering from Zhejiang University, China. He is currently a professor at Zhejiang University, China. His main research interests focus on novel organic-inorganic nanocomposites for energy-storage, energy harvesting and flexible sensors, electric ceramics/thin films and micro-devices for modern communication.

Guozhong Cao is a Boeing-Steiner Professor of materials science and engineering, Professor of chemical engineering and adjunct, Professor of mechanical engineering at the University of Washington. His current research focuses on chemical processing of nanomaterials for solar cells, batteries, and supercapacitors as well as actuators and sensors for aviation and biomedical applications.

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Optimizing nanostructure and constructing heterostructure via Mo/W incorporation to improve electrochemical properties of NiCoP for hybrid supercapacitors

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Zong, Q., Tao, D., Yang, H. et al. Optimizing nanostructure and constructing heterostructure via Mo/W incorporation to improve electrochemical properties of NiCoP for hybrid supercapacitors. Sci. China Mater. 65, 1195–1206 (2022). https://doi.org/10.1007/s40843-021-1904-x

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