富氮多孔碳纳米片的氮掺杂构型调控及其储锌性能

doi:10.16085/j.issn.1000-6613.2023-2063

摘要/Abstract

摘要：

基于多孔碳正极和锌金属负极构建的水性锌离子电容器（ZICs）具有成本低、环境友好、安全性高和长期耐用等优点，近年来受到广泛关注。本文以具有共价有机框架结构（COF）的富氮聚合物为碳源前体，通过简单的炭化自活化策略，合成了富氮多孔碳纳米片（NPCN-x）。研究表明，基于聚合物前体丰富的COF结构特点，炭化温度对所制备碳材料的氮含量和氮掺杂构型有显著影响，且碳材料表面的吡咯氮含量与其储锌性能呈现高度线性相关。优化后的NPCN-800其吡咯氮原子分数高达2.15%，作为ZICs的正极材料，在0.5A/g的电流密度下，展现出158mAh/g的高比容量和优异的循环稳定性。结合密度泛函理论计算发现，碳材料表面的吡咯氮构型具有优异的电化学活性，能够显著增强Zn离子的化学吸脱附过程。该研究为高性能ZICs用碳基电极材料的设计构建提供了新思路。

关键词: 多孔碳纳米片, 氮掺杂调控, 锌离子存储, 电化学, 优化设计

Abstract:

Aqueous zinc ion capacitors (ZICs) composed of porous carbon cathode and Zn metal anode have attracted great research interest in recent years due to their advantages of low cost, environmental friendliness, high safety, and long-term durability. This work first synthesized a N-containing polymer as the precursor by condensation of melamine chloride and p-phenylenediamine, and then fabricated N-enriched porous carbon nanosheets (NPCN-x) with a high N content (>10%) by a carbonization and self-activation strategy. The influence of carbonization temperature on the morphology, microstructure, surface chemical properties, and electrochemical performance of NPCN-x was investigated in detail. The results showed that carbonization temperature had a significant regulation effect on the N-doped configurations. It was revealed that the pyrrolic N configuration within NPCN-x materials played a crucial role in improving their electrochemical performance. As a consequence, the optimized NPCN-800 sample with the highest pyrrolic N content of 2.15% delivered a high specific capacity up to 158mAh/g at 0.5A/g and excellent cycling performance as the cathode for ZICs. To further explore the storage mechanism of Zn ions on the N-doped carbon surface during the electrochemical process, density functional theory (DFT) calculations were performed, which showed that the pyrrolic N configuration possessed the strongest adsorption capability for Zn ions, suggesting superior electrochemical activity in comparison to other N-doped configurations. This work provided a new insight from both theoretical and experimental perspectives for constructing porous carbon materials for high-performance ZICs.

Key words: porous carbon nanosheets, N-doped configurations, zinc ion storage, electrochemistry, optimal design

中图分类号:

TQ127.1⁺1

刘思宇, 杨卷, 陈培, 陈祖田, 闫斌, 刘育红, 邱介山. 富氮多孔碳纳米片的氮掺杂构型调控及其储锌性能[J]. 化工进展, 2024, 43(5): 2673-2683.

LIU Siyu, YANG Juan, CHEN Pei, CHEN Zutian, YAN Bin, LIU Yuhong, QIU Jieshan. Tuning N-doped configurations of N-enriched porous carbon nanosheets for high-performance zinc ion storage[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2673-2683.

图/表 9

图1 富氮聚合物衍生NPCN-x的合成示意图

图2 富氮聚合物前体的SEM和红外光谱表征

图3 NPCN-x的微观形貌表征

图4 NPCN-x的XRD、氮气吸附/脱附、拉曼和XPS表征

表1 基于XPS分峰拟合的NPCN-x中不同氮构型的比例及其含量

样品	总氮原子分数/%	不同氮构型原子分数/%			不同氮构型占比/%
样品	总氮原子分数/%	吡啶氮	吡咯氮	石墨氮	吡啶氮	吡咯氮	石墨氮
NPCN-700	15.32	4.45	1.34	9.53	29.1	8.7	62.2
NPCN-800	11.38	2.47	2.15	6.76	21.7	18.9	59.4
NPCN-900	7.91	1.25	1.54	5.12	15.7	19.5	64.8

图5 所组装ZICs示意图及其电化学性能

图6 NPCN-800电极不同状态下的SEM和EDS元素分布

图7 不同基底模型及其吸附Zn离子的构型对比（模型图中灰色、白色、蓝色和绿色小球分别代表C、H、N和Zn）

图8 不同碳基底吸附Zn离子在相同等值面上的差分电荷密度

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