Feng Xin, Bai Ying, Zheng Lumin, Liu Mingquan, Li Ying, Zhao Ran, Li Yu, Wu Chuan
Beijing Key Laboratory of Environmental Science and Engineering, School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China.
Yangtze Delta Region Academy of Beijing Institute of Technology, Jiaxing 314019, China.
ACS Appl Mater Interfaces. 2021 Dec 1;13(47):56285-56295. doi: 10.1021/acsami.1c18464. Epub 2021 Nov 16.
Nitrogen doping carbon materials are considered to be promising candidates for Na storage anodes. However, hitherto, the effects and mechanism of specific single N configuration (among pyrrolic N, quaternary N, and pyridinic N), on the sodium storage behaviors of carbon materials, are still puzzling, owing to the difficulties in accurately synthesizing a certain type of single N configuration dominated carbon materials (NCDCMs). Here, various NCDCMs have been successfully controlled and synthesized by small molecule polymerization methods, and their synthesis process has been also verified by NMR, MOLDI-TOF, TG-MS, etc. When serving as sodium ion battery anodes, the NCDCMs dominated by a high concentration of pyrrolic N (>80.3%) exhibits a satisfactory reversible capacity (434.5 mA h g at 50 mA g and 146.7 mA h g at 2000 mA g, respectively). It is revealed that pyrrolic N has more suitable adsorption energy and larger interlayer spacing, by density functional theory calculations and electron orbital theory, respectively, which synergistically makes the material obtain excellent electrochemical performance. This research exhibits a more efficient way to reveal the differences in the sodium ions storage behavior of different nitrogen configurations doped carbon, and provides new insight for the precise design and synthesis of a certain type of heteroatom doping to achieve satisfactory electrochemical performance.
氮掺杂碳材料被认为是有潜力的钠存储负极材料。然而，迄今为止，由于难以精确合成某一种单一氮构型主导的碳材料（NCDCMs），特定单一氮构型（吡咯氮、季氮和吡啶氮）对碳材料储钠行为的影响及机制仍不明确。在此，通过小分子聚合方法成功调控并合成了多种NCDCMs，其合成过程也通过核磁共振（NMR）、基质辅助激光解吸电离飞行时间质谱（MOLDI - TOF）、热重 - 质谱联用（TG - MS）等手段得到了验证。当用作钠离子电池负极时，高浓度吡咯氮（>80.3%）主导的NCDCMs表现出令人满意的可逆容量（在50 mA g时为434.5 mA h g，在2000 mA g时为146.7 mA h g）。分别通过密度泛函理论计算和电子轨道理论表明，吡咯氮具有更合适的吸附能和更大的层间距，二者协同作用使材料获得了优异的电化学性能。本研究展示了一种更有效的方法来揭示不同氮构型掺杂碳储钠行为的差异，并为精确设计和合成某类杂原子掺杂以实现令人满意的电化学性能提供了新的见解。
