润湿特性对超级电容器储能动力学的影响机理

引用本文: 杨化超, 薄拯, 帅骁睿, 严建华, 岑可法. 润湿特性对超级电容器储能动力学的影响机理[J]. 物理化学学报, 2019, 35(2): 200-207. doi: 10.3866/PKU.WHXB201803083 shu

Citation: YANG Huachao, BO Zheng, SHUAI Xiaorui, YAN Jianhua, CEN Kefa. Influence of Wettability on the Charging Dynamics of Electric Double-Layer Capacitors[J]. Acta Physico-Chimica Sinica, 2019, 35(2): 200-207. doi: 10.3866/PKU.WHXB201803083 shu

润湿特性对超级电容器储能动力学的影响机理

浙江大学能源清洁利用国家重点实验室，能源工程学院，杭州 310027

通讯作者: 薄拯, bozh@zju.edu.cn

基金项目:

国家自然科学基金(51306159)和浙江省自然科学基金(LR17E060002)资助项目

摘要: 润湿特性对超级电容器储能性能有着至关重要的影响。借助分子动力学模拟，本文研究了润湿特性对超级电容器储能动力学行为的影响。以石墨烯和晶体铜作为疏电解液和亲电解液电极材料。结果表明，在充电过程中，亲电解液铜电极呈现出非对称的U型微分电容曲线，负极电容是正极的~5.77倍，不同于经典双电层理论Gouy-Chapman-Stern(对称U型)和疏电解液型。该现象与离子自由能阻力分布密切相关，负极自由能阻力远小于正极(~2倍)和疏电解液电极，进而有利于强化双电层结构对电极电压的响应能力，导致更高微分电容。通过微分离子电荷密度，本文再现了微分电容演变规律，并发现改善润湿性会显著降低双电层厚度。最后，我们指出润湿性直接影响储能微观机理，将电荷储存机制从离子吸附和交换共同主导(疏电解液)转变到离子吸附主导(亲电解液)。本文所得结论揭示了润湿特性对储能动力学行为影响的原子层级机理，对超级电容器材料设计、构筑与润湿特性调控具有重要指导意义。

关键词:

English

Influence of Wettability on the Charging Dynamics of Electric Double-Layer Capacitors

State Key Laboratory of Clean Energy Utilization, College of Energy Engineering, Zhejiang University, Hangzhou 310027, P. R. China

Corresponding author: BO Zheng, Email: bozh@zju.edu.cn; Tel.: +86-571-87951369

Received Date: 10 February 2018
Accepted Date: 06 March 2018
Revised Date: 05 March 2018
Available Online: 15 January 2019
Fund Project:

The project was supported by the National Natural Science Foundation of China (51306159) and Zhejiang Provincial Natural Science Foundation, China (LR17E060002)

Abstract: Electric double-layer capacitors (EDLCs) are advanced electrochemical devices that have attracted tremendous attention because of their high power density, ultra-fast charging/discharging rate, and superior lifespan. A major challenge is how to further improve their energy density. At present, a large number of research efforts are primarily focusing on engineering the morphology and microstructure of electrodes to achieve better performance, for example, enlarging the specific surface area and designing the pore size. More importantly, wettability plays a crucial role in maximizing the effective utilization and accessibility of electrode materials. However, its primary mechanisms/phenomena are still partially resolved. Here, we explore the effects of wettability on the charging dynamics of EDLCs using molecular dynamics (MD) simulations. Typically, hydrophobic graphene (GP) and hydrophilic copper (Cu) are employed as the electrode materials. Differential capacitances (C_D) as a function of electrode potentials (ϕ) are computed by means of Poisson and Gaussian equation calculations. Simulation results show that during the charging process of EDLCs, the differential capacitances of hydrophobic GP are insensitive to the electrode potentials. However, superhydrophilic Cu electrode exhibits an asymmetric U-shaped C_D–ϕ curve, in which the capacitance at the negative polarization can be ~5.77 times greater than that of the positive counterpart. Such an unusual behavior is obviously different with the conventional Gouy-Chapman-Stern theory (i.e., symmetric U-shaped), room temperature ionic liquids (i.e., camel-, or bell-shaped), and hydrophobic counterpart, which is closely correlated with the free energy barrier distributions. Compared with the positive polarization or hydrophobic case, the energy barriers near the negative hydrophilic electrodes are remarkably suppressed, which benefits ion populations at the interface and enables the convenient orientation or distribution of ions to shield the external electric fields from electrodes, thereby yielding higher differential capacitances. With differentiating the ion charge density, the as-obtained C_D–ϕ curves are well resembled, quantitatively establishing the correlations between EDL microstructures and differential capacitances. Besides, we also point out that enhancing the wettability could significantly decrease the EDL thickness from ~1.0 nm (hydrophobic) to ~0.5 nm (hydrophilic). In the end, we demonstrate that wetting property also impacts a prominent role in the charge storage behavior of EDLCs, transforming the charging mechanism dominated by counter-ion adsorption and ion exchange (hydrophobic) to pure counter-ion adsorption (hydrophilic). The as-obtained insights highlight the significance of wettability in regulating charging dynamics and mechanisms, providing useful guidelines for precisely controlling the wetting property of electrode materials for advanced charge storage of EDLCs.

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

润湿特性对超级电容器储能动力学的影响机理

通讯作者: 薄拯, bozh@zju.edu.cn

English

Influence of Wettability on the Charging Dynamics of Electric Double-Layer Capacitors

Corresponding author: BO Zheng, Email: bozh@zju.edu.cn; Tel.: +86-571-87951369

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

润湿特性对超级电容器储能动力学的影响机理

通讯作者: 薄拯, bozh@zju.edu.cn

English

Influence of Wettability on the Charging Dynamics of Electric Double-Layer Capacitors

Corresponding author: BO Zheng, Email: bozh@zju.edu.cn; Tel.: +86-571-87951369

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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