纳米Au-氮掺杂碳纳米管一体化复合正极的构筑及锂氧气电池性能研究

姜巧娟; 李靖靖; 李玉玲; 陈菲; 王焕锋

纳米Au-氮掺杂碳纳米管一体化复合正极的构筑及锂氧气电池性能研究

郑州工程技术学院　化工食品学院, 郑州 450044

基金项目: 河南省高校国家级大学生创新创业训练计划项目(No.202211068009)；河南省高等学校重点科研项目(No.22B150021)；郑州工程技术学院课程思政教育教学改革研究与实践项目(KCSZJG202102)

详细信息

通讯作者:
王焕锋，博士研究生，副教授，研究方向为能源材料　E-mail: whfzzgc@163.com

中图分类号: (O643.36)
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- 被引次数: 0
出版历程
- 收稿日期: 2022-11-14
- 修回日期: 2022-12-12
- 录用日期: 2022-12-31
- 网络出版日期: 2023-02-02

Construction of nano Au-nitrogen doped carbon nanotubes integrated composite cathode and performance study for lithium-oxygen batteries

College of Chemical and Food, Zhengzhou University of Technology, Zhengzhou 450044, China

Funds: National Innovation and Entrepreneurship Training Program for College Students in Henan Province (No.202211068009)；Key Scientific Research Project of Higher Education of Henan Province, China (No.22B150021); Course Ideology and Politics Education Teaching Reform Research and Practice Project of Zhengzhou University of Technology (KCSZJG202102)

摘要

摘要: 碳材料具有多孔性、轻质、高导电性和可调谐电子结构等优点，广泛应用于锂氧气电池正极催化剂，然而碳正极与放电中间体之间的副反应产生一系列副产物在正极上积累，导致正极钝化，催化活性降低，过电位升高；同时传统悬浮液正极制备法中粘结剂的使用使得电极机械稳定性低，导致电极脱落等问题，严重影响了电极的电化学稳定性，使得电池的倍率性能、循环性能差。本文通过化学气相沉积、光还原两步合成工艺，将具有高催化活性的Au纳米粒子原位负载在具有三维贯穿结构的氮掺杂碳纳米管/不锈钢网上，得到了具有互相渗透孔道结构的一体化正极Au/N-CNT/SS。Au-N-CNT/SS正极具有合适的孔道结构、高电导率、超强的机械性能、结构稳定性等，克服了传统电极机械稳定性差、碳电极易分解、副反应严重等问题。将Au-N-CNT/SS电极用作锂氧气电池正极，一体化电极的设计避免了粘结剂的使用，极大地提高了电池的机械强度，提升了电池的电化学/化学稳定性；正极的高导电率和互相渗透的电极结构为电荷转移提供了通道；充足的孔道结构确保了氧气活性物质和锂离子的快速扩散；Au纳米粒子高效催化剂的使用，有效地提升了正极的氧还原/氧析出反应动力学，加快了放电产物的生成与分解，有效提升了电池的倍率性能(1.0 mA·cm⁻²的高电流密度下放电电压保持在2.4 V)、放电容量(8.47 mA·h·cm⁻²)和循环性能(160圈)。1Au-N-CNT/SS、N-CNT/SS、N-CNT-SS电极的(a)充放电曲线、(b)倍率性能和(c)循环性能对比
- 碳纳米管 /
- 锂氧气电池 /
- 一体化正极 /
- 氧还原/氧析出 /
- 电催化活性
Abstract: Highly efficient, stable cathode is crucial to lithium-oxygen battery. A high performance, integrated Au-N-CNT/SS cathode with interpermeable channels was constructed by chemical vapor deposition and photoreduction, in which the high catalytic Au nanoparticles were loaded on nitrogen doped carbon nanotubes with three-dimensional permeable of stainless steel mesh. The morphology and composition of the Au-N-CNT/SS were investigated by SEM, TEM, XPS, XRD and Raman spectrum. The problems of poor mechanical stability, carbonaceous cathode decomposition and serious side reactions were avoided by the suitable channel structure, high conductivity, superior mechanical properties, structural stability of Au-N-CNT/SS. Taking Au-N-CNT/SS as the integrated cathode for lithium-oxygen battery, the utilization of binder is avoided. The mechanical strength of the lithium-oxygen battery is enhanced, and the side reactions are effectively reduced, contributing to the enhanced electrochemical/chemical stability. The high conductivity, interpenetrated structure and sufficient pores provide a fast electron transport and mass transfer channel. The highly efficient Au nanoparticles are favorable to improving the oxygen reduction/oxygen evolution reaction kinetics on cathode, accelerating the generation and decomposition of discharge products. The rate performance (keeping the discharge voltage at 2.4 V with a high current density of 1.0 mA·cm⁻²), specific capacity (8.47 mA·h·cm⁻²) and cycle performance (160 cycles) of lithium-oxygen battery are greatly improved.
- carbon nanotube /
- lithium-oxygen battery /
- integrated cathode /
- oxygen reduction/oxygen evolution /
- electrocatalytic activity

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图 1 Au纳米粒子原位负载氮掺杂碳纳米管/不锈钢网一体化电极(Au-N-CNT/SS)的合成示意图

Figure 1. Schematic illustration of the synthesis procedure for the Au nanoparticles in situ loaded with nitrogen-doped carbon nanotubes/stainless steel mesh integrated electrodes (Au-N-CNT/SS)

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图 2 (a) SS的SEM图，(b-d) 不同放大倍数下Au-N-CNT/SS的SEM图，(e) Au-N-CNT/SS, N-CNT/SS及SS的XRD谱图，(f) Au-N-CNT/SS及N-CNT/SS的Raman光谱

Figure 2. (a) SEM image of SS, (b-d) SEM images of Au-N-CNT/SS at different magnifications, (e) XRD patterns of Au-N-CNT/SS, CNT/SS and SS, (f) Raman spectra of Au-N-CNT/SS and N-CNT/SS

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图 3 (a-b)不同放大倍数下N-CNT-SS电极的SEM图，(c) Au-N-CNT/SS的TEM图，(d) Au-N-CNT/SS的高分辨TEM图，(e) Au-N-CNT/SS电极中Au 4 f的XPS谱图，(f) N-CNT/SS的紫外可见吸收光谱图

Figure 3. (a-b) SEM images of N-CNT-SS at different magnifications, (c) TEM image of the Au-N-CNT/SS, (d) High resolution TEM image of the Au-N-CNT/SS, (e) XPS spectra of Au 4 f in Au-N-CNT/SS, (f) UV-vis absorption spectra of Au-N-CNT/SS and N-CNT/SS

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图 4 基于Au-N-CNT/SS, N-CNT/SS及N-CNT-SS电极的锂氧气电池(a)首圈充放电曲线，(b) 循环伏安曲线，(c)不同电流密度下的放电电压变化，(d) 电化学交流阻抗谱图，(e)放电容量, (f)循环性能

Figure 4. (a) The first discharge-charge curves, (b) cyclic voltammetry curves, (c) discharge voltage variation at different current densities, (d) electrochemical impedance spectroscopy, (e) discharge capacity, (f) cycling performance of the lithium-oxygen battery with Au-N-CNT/SS, N-CNT/SS and N-CNT-SS

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图 5 首次放电和充电后Au-N-CNT/SS正极(a-b)、N-CNT/SS正极(c-d)和N-CNT-SS (e-f)正极的SEM图，(g) 首次放电和充电后Au-N-CNT/SS、N-CNT/SS和N-CNT-SS正极的红外光谱图，其中Li₂O₂，Li₂CO₃，HCO₂Li和CH₃CO₂Li的光谱供参考

Figure 5. SEM images of the recharged Au-N-CNT/SS cathode (a-b), N-CNT/SS cathode (c-d) and N-CNT-SS cathode (e-f) after 1 st discharged and charged process, (g) FTIR spectra of the Au-N-CNT/SS, N-CNT/SS, and N-CNT-SS cathodes after 1 st discharged and charged process, in which the spectra for Li₂O₂, Li₂CO₃, HCO₂Li, and CH₃CO₂Li are also shown for reference

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图 6 (a)不同含量商业Li₂O₂的紫外可见光谱，(b)放电后不同电极的紫外可见光谱

Figure 6. (a) UV-visible spectra of the commercial Li₂O₂ with different contents, (b) UV-vis spectra of the discharged Au-N-CNT/SS, N-CNT/SS, and N-CNT-SS

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图 7 第20次充电后Au-N-CNT/SS(a)、N-CNT/SS(b)和N-CNT-SS正极(c)的SEM图(电流密度为0.2 mA cm⁻²，充电容量为1.0 mA h cm⁻²)，(d) 第20次充电后Au-N-CNT/SS、N-CNT/SS和N-CNT-SS正极的¹H核磁共振谱图，其中TEGDME，CH₃COOD和HCOOD的谱图供参考

Figure 7. SEM images of the Au-N-CNT/SS (a), N-CNT/SS (b), and N-CNT-SS cathodes (c) at a current density of 0.2 mA cm⁻² with a charge capacity of 1.0 mA h cm⁻² after the 20 th recharge. (d) ¹H NMR spectra of the Au-N-CNT/SS, N-CNT/SS and N-CNT-SS cathodes after the 20 th recharge, in which the spectra for TEGDME, CH₃COOD and HCOOD are also shown for reference

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