高氯酸锂与含氧碳纸的界面效应研究

IF 2.1 4区化学 Q3 CHEMISTRY, PHYSICAL

Surface Science Pub Date : 2024-09-21 DOI:10.1016/j.susc.2024.122615

Yibing Xie , Chen Yao

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引用次数: 0

摘要

与高氯酸锂相互作用的含氧碳纸（LiClO4-OCP）被设计为具有电活性的超级电容器电极基板，用于储能应用。OCP 是通过在 H2O2 反应介质中对碳纸进行水热活化处理制成的。OCP 由石墨间距组成，表层为超薄石墨烯结构，石墨化程度更高。极化静电力诱导界面吸附的 LiClO4-OCP 比范德华力诱导界面吸附的 LiClO4-CP 显示出更强烈的相互作用，有助于促进 LiClO4-OCP 的界面电荷转移。与 LiClO4-CP 相比，LiClO4-OCP 显示出更有效的界面电荷转移和更可行的电解质扩散，因而具有更高的电化学双层电容。含有含氧基团的 LiClO4-OCP 可进行可逆的氧化还原过程，从而提供额外的法拉第电容。在扫描速率为 5∼100 mV s-1 时，平均响应电流从 LiClO4-CP 的 0.10 ∼ 1.34 mA cm-2 增加到 LiClO4-OCP 的 0.19 ∼ 2.31 mA cm-2，表明 LiClO4-OCP 的电化学活性有所提高。基于循环伏安法的电容从 LiClO4-CP 的 19.91 ∼ 13.01 mF cm-2 mF g-1 增加到 LiClO4-OCP 的 37.76 ∼ 23.06 mF cm-2。电静态充放电电容从 LiClO4-CP 的 13.84 ∼ 3.97 mF cm-2 下降到 LiClO4-OCP 的 29.71 ∼ 12.92 mF cm-2。基于密度泛函理论的模拟计算证明，分子距离如此之短的 LiClO4-OCP 可以发生强烈的静电作用，这种作用是由高氯酸根离子引起的含氧基团极化造成的。与 LiClO4-CP 相比，LiClO4-OCP 具有更低的界面能、更低的带隙和更高的费米能级态密度，这表明 LiClO4-OCP 的界面相互作用和导电性能得到了改善。实验测量和理论计算的结果一致，LiClO4-OCP 电极衬底具有更高的电化学活性，从而显示出其优越的电容性能。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Interfacial effect investigation of lithium perchlorate-interacted oxygen-containing carbon paper

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Interfacial effect investigation of lithium perchlorate-interacted oxygen-containing carbon paper

The lithium perchlorate-interacted oxygen-containing carbon paper (LiClO4-OCP) is designed to act as electroactive supercapacitor electrode substrates for the energy storage application. The OCP is fabricated through hydrothermal activation treatment of carbon paper in H₂O₂ reaction medium. The OCP is composed of graphite pitches with ultra-thin graphene structure of top layer, showing the improved graphitization degree. The LiClO4-OCP with the polarized electrostatic force-induced interfacial adsorption reveals much more intensive interaction than LiClO4-CP with van der Waals force-induced interfacial adsorption, contributing to promoting interfacial charge transfer of LiClO4-OCP. LiClO4-OCP reveals more effective interface charge transfer and more feasible electrolyte diffusion than LiClO4-CP, contributing to higher electrochemical double-layer capacitance. LiClO4-OCP with oxygen-containing groups conducts reversible redox process to supply additional Faradaic capacitance. Mean response current is increased from 0.10 ∼ 1.34 mA cm^-2 for LiClO4-CP to 0.19 ∼ 2.31 mA cm^-2 for LiClO4-OCP at scan rates of 5∼100 mV s^-1, indicating the improved electrochemical activity of LiClO4-OCP. The cyclic voltammetry-based capacitance increases from 19.91 ∼ 13.01 mF cm^-2 mF g-1 for LiClO4-CP to 37.76 ∼ 23.06 mF cm^-2 for LiClO4-OCP. The galvanostatic charge/discharge-based capacitance decreases from 13.84 ∼ 3.97 mF cm^-2 for LiClO4-CP to 29.71 ∼ 12.92 mF cm^-2 for LiClO4-OCP. Density-functional theory-based simulation calculation proves LiClO4-OCP with such a short molecular distance is allowed to occur strong electrostatic interaction which is caused by the perchlorate ion-induced polarization of oxygen-containing groups. The LiClO4-OCP has lower interfacial energy, lower band gap and higher density of states at Fermi energy level than LiClO4-CP, indicating the improved interfacial interaction and electrical conductivity of LiClO4-OCP. The experimental measurement and theoretical calculation achieve the consistent results of higher electrochemical activity of LiClO4-OCP electrode substrate to present its superior capacitance performance.

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来源期刊

Surface Science 化学-物理：凝聚态物理

CiteScore

3.30

自引率

5.30%

发文量

137

审稿时长

25 days

期刊介绍： Surface Science is devoted to elucidating the fundamental aspects of chemistry and physics occurring at a wide range of surfaces and interfaces and to disseminating this knowledge fast. The journal welcomes a broad spectrum of topics, including but not limited to: • model systems (e.g. in Ultra High Vacuum) under well-controlled reactive conditions • nanoscale science and engineering, including manipulation of matter at the atomic/molecular scale and assembly phenomena • reactivity of surfaces as related to various applied areas including heterogeneous catalysis, chemistry at electrified interfaces, and semiconductors functionalization • phenomena at interfaces relevant to energy storage and conversion, and fuels production and utilization • surface reactivity for environmental protection and pollution remediation • interactions at surfaces of soft matter, including polymers and biomaterials. Both experimental and theoretical work, including modeling, is within the scope of the journal. Work published in Surface Science reaches a wide readership, from chemistry and physics to biology and materials science and engineering, providing an excellent forum for cross-fertilization of ideas and broad dissemination of scientific discoveries.