Intrinsic Carbon Defects in Nitrogen and Sulfur Doped Porous Carbon Nanotubes Accelerate Oxygen Reduction and Sulfur Reduction for Electrochemical Energy Conversion and Storage
Intrinsic Carbon Defects in Nitrogen and Sulfur Doped Porous Carbon Nanotubes Accelerate Oxygen Reduction and Sulfur Reduction for Electrochemical Energy Conversion and Storage
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DOI：
10.1021/acsanm.3c02803
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发表时间：
2023-08
影响因子：
5.9
通讯作者：
Minjie Zhou;Bing Chen;Na Zhang;Xianglin Deng;Xiating Jia;Jie Yang;Haihua Yang
中科院分区：
文献类型：
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作者：
Minjie Zhou;Bing Chen;Na Zhang;Xianglin Deng;Xiating Jia;Jie Yang;Haihua Yang
缺陷和形貌工程是提高碳基材料电化学能量转换和存储性能的有效策略。本研究首先以甲基橙和氯化铁组成的胶束为软模板，通过热解预先合成的聚苯胺纳米管获得氮/硫共掺杂碳纳米管（NS-CNT）。此外，引入固有碳缺陷和介孔，通过氨蚀刻获得蚀刻NS-CNT（ENS-CNT）复合材料。内在/外在缺陷和多孔纳米管形貌特征的合理组合有利于ENS-CNTs电极的氧还原反应（ORR）和硫还原反应（SRR）性能。内在碳缺陷和外在N/S掺杂剂的共存可以为电化学过程创造大量的催化活性位点，而多孔一维纳米管状碳框架则负责催化活性位点的可及性、物种托管、导电性、传质和稳定性。因此，ORR 的 ENS-CNTs-30（其中 30 代表相应的蚀刻时间（以分钟为单位））电极显示出相对于 RHE 为 859 mV 的高半波电位、6.65 mA cm-2 的扩散限制电流密度、令人赞叹的稳定性和甲醇耐受性。以 ENS-CNTs-30 作为空气阴极活性材料组装的固体锌空气电池（ZAB）显示出显着的功率密度（137 mW cm-2）和比容量（1467.4 mAh g-1Zn）。同时，用于 SRR 的 ENS-CNTs-30 电极还表现出改善的锂多硫化物 (LiPS) 捕获能力和 Li2S 沉积动力学。以ENS-CNTs-30为硫主体材料的锂硫电池（LSB）在0.2 C和2 C下的初始容量分别为1100和883 mAh g-1，在0.2 C下循环200次后容量保持率为82.0%。这项工作为电化学能量转换和存储领域多功能碳基催化剂的缺陷和形貌工程提供了可行的策略。
Defects and morphology engineering is a serviceable strategy to boost the electrochemical energy conversion and storage performance of carbon-based materials. In this study, nitrogen/sulfur codoped carbon nanotubes (NS-CNTs) were first obtained via the pyrolysis of presynthesized polyaniline nanotubes with micelles composed of methyl orange and ferric chloride acting as the soft template. Furthermore, intrinsic carbon defects and mesopores were introduced to obtain etched NS-CNTs (ENS-CNTs) composites by ammonia etching. The rational combination of intrinsic/extrinsic defects and porous nanotube morphology features is beneficial to the oxygen reduction reaction (ORR) and sulfur reduction reaction (SRR) performances of the ENS-CNTs electrode. The coexistence of intrinsic carbon defects and extrinsic N/S dopants can create massive catalytically active sites for electrochemical processes, while the porous one-dimensional nanotube-like carbon framework is responsible for accessibility of catalytic active sites, species hosting, electrical conductivity, mass transport, and stability. Consequently, the ENS-CNTs-30 (where 30 represents the corresponding etching time in minutes) electrode for ORR displayed a high half-wave potential of 859 mV vs RHE, a diffusion limiting current density of 6.65 mA cm–2, admirable stability, and methanol tolerance. The solid Zn–air battery (ZAB) assembled with ENS-CNTs-30 as the active material for the air cathode revealed remarkable power density (137 mW cm–2) and specific capacity (1467.4 mAh g–1Zn). Meanwhile, the ENS-CNTs-30 electrode for SRR also demonstrated ameliorative lithium–polysulfide (LiPS) trapping capability and Li2S deposition kinetics. The lithium–sulfur battery (LSB) with ENS-CNTs-30 as sulfur host material unfolded initial capacities of 1100 and 883 mAh g–1at 0.2 and 2 C, respectively, and a capacity retention ratio of 82.0% after 200 cycles at 0.2 C. This work provides a feasible strategy for defects and morphology engineering of multifunctional carbon-based catalysts in electrochemical energy conversion and storage fields.