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Superhydrophilic nickel hydroxide ultrathin nanosheets enable high-performance asymmetric supercapacitors

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Abstract

Superhydrophilic surfaces have been applied for supercapacitor; however, during energy storage reaction, how the wettability affects the process of electrochemical reaction specifically is still unclear. Herein, we demonstrate superhydrophilic surface for promotion of electrochemical reactions by liquid affinity and further explain the mechanism, where the transition of the wettability state caused by the change in surface free energy is the main reason for the obvious increase in specific capacitance. Through citric acid assistance strategy, an intrinsically hydrophobic Ni(OH)2 thick nanosheets (HNHTNs, 16 nm) can be transitioned into superhydrophilic Ni(OH)2 ultrathin nanosheets (SNHUNs, 6.8 nm), where the water contact angle was 0° and the surface free energy increased from 8.6 to 65.8 mN·m−1, implying superhydrophilicity. Compared with HNHTNs, the specific capacitance of SNHUNs is doubled: from 1230 F·g−1 (HNHTNs) to 2350 F·g−1 (2 A·g−1) and, even at 20 A·g−1, from 833 F·g−1 (HNHTNs) to 1670 F·g−1. The asymmetric capacitors assembled by SNHUNs and activated carbon show 52.44 Wh·kg−1 at 160 W·kg−1 and excellent stability with ~ 90% retention after 5000 cycles (~ 80% retention after 9500 cycles). The promotion of electrochemical performances is ascribed to the change of surface wettability caused by surface free energy, which greatly increase affinity of electrode to the surrounding liquid environment to reduce the interface resistance and optimize the electron transport path.

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摘要

超亲水表面已应用于超级电容器, 但在储能反应过程中, 电极材料的润湿性如何影响电化学反应过程尚不清楚. 我们证实了超亲水电极材料的表面自由能变化引起的润湿性状态的转变可以有效的提升电化学性能. 首先, 通过柠檬酸辅助策略, l可以将本质疏水的Ni(OH)2厚纳米片(16 nm)转变为超亲水Ni(OH)2超薄纳米片(6.8 nm), 其表面自由能由8.6 mN·m−1增加到65.8 mN·m−1. 与疏水Ni(OH)2相比, 超亲水Ni(OH)2超级电容器的比电容大约是其两倍. 在2 A·g−1下, 疏水Ni(OH)2为1230 F·g−1, 超亲水Ni(OH)2为2350 F·g−1; 即使在20 A·g−1, 疏水Ni(OH)2为833 F·g−1, 超亲水Ni(OH)2为1670 F·g−1. 由超亲水Ni(OH)2和活性炭组合而成的非对称电容器在160 W·kg−1的功率密度下展示了52.44 Wh·kg−1的能量密度. 在5000次循环后比电容的留存率为90%, 9500次循环后比电容的留存率为80%. 我们提出了润湿性对电化学性能提升的影响机制: 由于表面自由能引起表面润湿性的改变, 极大地提高了电极对周围液体环境的亲和力, 从而降低了界面电阻, 优化了电子传递路径.

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Acknowledgements

This study was financially supported by the National Natural Science Foundation of China (Nos. 22278349 and 62071413), Hebei Natural Science Foundation (Nos. B2020203013 and F2020203056), the Science and Technology Project of Hebei Education Department (No. QN2020137), Subsidy for Hebei Key Laboratory of Applied Chemistry after Operation Performance (No. 22567616H), the Cultivation Project for Basic Research Innovation of Yanshan University (No. 2021LGZD015), the Natural Science Foundation of Heilongjiang Province of China (No. LH2022B025) and the Fundamental Research Funds for the Provincial Universities of Heilongjiang Province (No. KYYWF10236190104).

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Authors and Affiliations

  1. State Key Laboratory of Metastable Materials Science and Technology (MMST), Hebei Key Laboratory of Applied Chemistry, Yanshan University, Qinhuangdao, 066004, China

    Yi-Ran Wang, Fei Zhang, Jian-Min Gu, Ran Zhao, Xing Wang, Jing Wang, Ji-Dong Wang & De-Song Wang

  2. School of Sciences, Hebei University of Science and Technology, Shijiazhuang, 050018, China

    De-Song Wang

  3. School of Chemical Science and Engineering, Tongji University, Shanghai, 200092, China

    Tian-Hui Wu

  4. Department of Food and Pharmaceutical Engineering, Suihua University, Suihua, 152000, China

    Xiao-Yu Zhao

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  1. Yi-Ran Wang
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Wang, YR., Zhang, F., Gu, JM. et al. Superhydrophilic nickel hydroxide ultrathin nanosheets enable high-performance asymmetric supercapacitors. Rare Met. 43, 138–147 (2024). https://doi.org/10.1007/s12598-023-02386-x

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