聚(乙烯基二甲基吩嗪)的分子量对其电化学行为的影响研究

doi:10.6023/cjoc202406004

有机化学 ›› 2025, Vol. 45 ›› Issue (1): 325-330.DOI: 10.6023/cjoc202406004 上一篇下一篇

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聚(乙烯基二甲基吩嗪)的分子量对其电化学行为的影响研究

王梓恒^a^,^b, 段安^b, 黄晓宇^a^,^b^,^*(), 李永军^b^,^*()

a 上海大学微电子学院上海 201800
b 中国科学院上海有机化学研究所上海 200032

收稿日期:2024-06-03 修回日期:2024-06-28 发布日期:2024-07-18
基金资助:
国家自然科学基金(52273086); 国家自然科学基金(U22A20131); 上海市科技计划(22520711700)

Impact of the Molecular Weight of Poly(vinyl dimethylphenazine) on Its Electrochemical Behavior

Ziheng Wang^a^,^b, An Duan^b, Xiaoyu Huang^a^,^b(), Yongjun Li^b()

a School of Microelectronics, Shanghai University, Shanghai 201800
b Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2024-06-03 Revised:2024-06-28 Published:2024-07-18
Contact: *E-mail: xyhuang@mail.sioc.ac.cn; liyongjun78@sioc.ac.cn
Supported by:
National Natural Science Foundation of China(52273086); National Natural Science Foundation of China(U22A20131); Shanghai Scientific and Technological Innovation Project(22520711700)

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摘要/Abstract

5,10-二甲基吩嗪(DMP)是一种高性能的有机电极材料, 但是小分子在电解液中易溶解, 降低了电极材料的循环性能. 含有DMP的聚(2-乙烯基-5,10-二甲基吩嗪)(PVDMP)在电解液中有较低的溶解性, 但是聚合物的分子量与其电化学性能之间的关系还未被阐明. 合成了两种分子量的PVDMP-2K(分子量为2300)和PVDMP-12K(分子量为12000), 循环伏安(CV)结果表明低浓度时PVDMP的峰电流(i_p)与聚合物浓度呈线性关系, 而高浓度时聚合物的分子量对PVDMP的电化学活性有一定影响. 聚合物的形貌分析揭示了不同分子量的PVDMP在溶剂中形成具有不同粒径的球形聚集体, 因此对其在电化学反应中的扩散系数和活性基团利用率产生影响, 从而表现出不同的电化学行为.

关键词: 聚(乙烯基二甲基吩嗪), 分子量, 电化学行为, 有机电极材料

5,10-Dimethylphenazine (DMP) is a recently reported high-performance organic electrode material, however, its high solubility in electrolyte solution is responsible for the capacity decay during cycling. Poly(2-vinyl-5,10-dimethyl- phenazine) (PVDMP), containing DMP as active groups, shows limited solubility in electrolytes, whereas the impact of its molecular weight on the electrochemical properties has not been well investigated. Here, PVDMPs with two molecular weights, PVDMP-2K (M_w=2300 g•mol^－1) and PVDMP-12K (M_w=12000 g•mol^－1) were prepared. Cyclic voltammetry (CV) characterization shows that the peak current (i_p) increased linearly with the concentration of PVDMP at low concentrations, while at high concentrations, there was a poor linear relationship between i_p and M_w. This result demonstrated that the molecular weight of PVDMP affected its electrochemical behaviors. From the morphology investigation, it can be seen that PVDMP presented spherical aggregates with different diameters in solution and the diameter is increased with the molecular weight of PVDMP. Therefore, this spherical aggregate could influence the diffusion efficiency of PVDMP during the electrochemical reaction and the utilization of the active groups, and thus demonstrated different electrochemical behavior.

Key words: poly(vinyl dimethylphenazine), molecular weight, electrochemical behavior, organic electrode materials

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王梓恒, 段安, 黄晓宇, 李永军. 聚(乙烯基二甲基吩嗪)的分子量对其电化学行为的影响研究[J]. 有机化学, 2025, 45(1): 325-330.

Ziheng Wang, An Duan, Xiaoyu Huang, Yongjun Li. Impact of the Molecular Weight of Poly(vinyl dimethylphenazine) on Its Electrochemical Behavior[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 325-330.

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图/表 5

图1. PVDMP的合成路线(a)及其核磁共振氢谱(b)与GPC (c)表征

Figure 1. Synthesis route of PVDMP (a), 1H NMR characterization (b) and GPC curves (c)

图2. 不同浓度PVDMP-2K和PVDMP-12K的循环伏安曲线(a, b)及其峰电流与浓度之间的关系(c, d)

Figure 2. CV curves of PVDMP-2K and PVDMP-12K with different concentrations (a, b), and the relationship between peak current and concentration (c, d)

图3. 浓度为0.5 mmol/L的PVDMP-2K (a)和PVDMP-12K (b)在不同扫速的循环伏安曲线及其峰电流与扫速平方根间的线性关系

Figure 3. CV curves of PVDMP-2K (a) and PVDMP-12K (b) at different sweep speeds with concentrations of 0.5 mmol/L, and the linear relationship between peak current and square root of scan rate

图4. PVDMP-2K (a, c)和PVDMP-12K (b, d)溶解在二氯甲烷中的TEM图、流体力学直径和粒径分布

Figure 4. TEM images, hydrodynamic diameter and size distribution of PVDMP-2K (a, c) and PVDMP-12K (b, d) dissolved in DCM

图5. PVDMP在不同氧化还原状态下的粒径变化示意图

Figure 5. Evolution of aggregate size of PVDMP at four redox states

参考文献 15

[1]	Cano, Z. P.; Banham, D.; Ye, S.; Hintennach, A.; Lu, J.; Fowler, M.; Chen, Z. Nat. Energy 2018, 3, 279.
[2]	Kittner, N.; Lill, F.; Kammen, D. M. Nat. Energy 2017, 2, 17125.
[3]	Zhang, C.; Huang, Z.; Yang, Y.; Wang, D.; He, D. Chin. J. Org. Chem. 2014, 34, 1347 (in Chinese).
	(张春明, 黄昭, 杨扬, 王丹, 何丹农, 有机化学, 2014, 34, 1347.)
[4]	Jin, Z.; Sui, Y.; Wei, F.; Qi, J.; Huang, T.; Li, T.; Shi, M.; Zhang, Y.; Xue, X. Acta Chim. Sinica 2022, 80, 1618 (in Chinese).
	(金钟, 隋艳伟, 委福祥, 戚继球, 黄天龙, 李天琳, 石美瑜, 张洋, 薛晓兰, 化学学报, 2022, 80, 1618.)
[5]	Zhang, K.; Han, X.; Hu, Z.; Zhang, X.; Tao, Z.; Chen, J. Chem. Soc. Rev. 2015, 44, 699.
[6]	Li, Z.; Xu, B.; Cao, X.; Xia, H.; Zhang, W. Chin. J. Org. Chem. 2024, 44, 148 (in Chinese).
	(李峥沄, 徐彬瑜, 曹昕, 夏欢, 章炜, 有机化学, 2024, 44, 148.)
[7]	Xie, J.; Zhang, Q. Small 2019, 15, e1805061.
[8]	Wu, S.; Hu, Z.; He, P.; Ren, L.; Huang, J.; Luo, J. eScience 2023, 3, 100120.
[9]	Liang, Y.; Dong, H.; Aurbach, D.; Yao, Y. Nat. Energy 2020, 5, 646.
[10]	Kwon, G.; Lee, S.; Hwang, J.; Shim, H.-S.; Lee, B.; Lee, M. H.; Ko, Y.; Jung, S.-K.; Ku, K.; Hong, J.; Kang, K. Joule 2018, 2, 1771.
[11]	Duan, A.; Wang, Z.; Huang, X.; Li, Y. Angew. Chem., Int. Ed. 2023, 62, e202302754.
[12]	Muench, S.; Wild, A.; Friebe, C.; Haupler, B.; Janoschka, T.; Schubert, U. S. Chem. Rev. 2016, 116, 9438.
[13]	Lee, M.; Hong, J.; Lee, B.; Ku, K.; Lee, S.; Park, C. B.; Kang, K. Green Chem. 2017, 19, 2980.
[14]	Nagarjuna, G.; Hui, J.; Cheng, K. J.; Lichtenstein, T.; Shen, M.; Moore, J. S.; Rodríguez-López, J. J. Am. Chem. Soc. 2014, 136, 16309.
[15]	Bard, A. J.; Faulkner, L. R. Electrochemical Methods: Fundamentals and Applications, 2nd ed., Wiley, New York, 2001, pp. 226-232.

聚(乙烯基二甲基吩嗪)的分子量对其电化学行为的影响研究

Impact of the Molecular Weight of Poly(vinyl dimethylphenazine) on Its Electrochemical Behavior

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