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模拟分子的结构和行为有助于更深刻地分析电荷输运特性变化的微观机理。本研究采用分子动力学模拟方法，深入探究氢键对马来酸（MA）接枝聚丙烯（PP）/聚偏二氟乙烯（PVDF）复合体系分子结构演变与电荷输运特性的调控机制，并对其分子间相互作用能、自由体积、电子态密度、电荷差分密度以及陷阱能级进行仿真分析。研究结果表明：随着MA接枝量的增加，氢键数量显著增多。当MA质量分数为36.22wt.%时，氢键数量达到20的峰值，分子间相互作用能增至极大值2171.63kcal·mol-1，自由体积分布达到极小值16.03%，此时分子内部结构最为紧密。当MA质量分数为52.97wt.%时，复合材料的带隙达到极小值3.13eV，陷阱能级深度亦达到极大值3.06eV，此时PP/PVDF复合材料在氢键形成的区域显示出更高的电子密度积累，电子逸出概率显著降低。至此，模拟结果证实了氢键的作用不仅改变了材料的分子结构，还通过改变局部电荷分布状态直接影响电荷输运特性，为设计功能性高分子复合电介质材料提供了理论依据。Simulating molecular structures and dynamic behaviors offers critical insights into the microscopic mechanisms governing variations in charge transport properties. In this work, molecular dynamics (MD) simulations integrated with the Compass II force field and molecular modeling (including geometry optimization, annealing, and dynamic equilibration) were systematically conducted to analyze intermolecular interaction energy, free volume distribution, electronic density of states (DOS), charge differential density, and trap energy levels. This comprehensive approach aims to unravel the regulatory role of hydrogen bonds in the structural evolution and charge transport dynamics of polypropylene (PP)/polyvinylidene fluoride (PVDF) composite systems. A quantitative framework was further established to correlate hydrogen bond density with key material performance metrics, such as free volume fraction, bandgap energy, and trap energy depth. This elucidates the hydrogen bond-mediated modulation of molecular architecture and charge transport behavior in PP/PVDF composites. Simulation results reveal a pronounced dependence of hydrogen bond formation on MA grafting content. At an MA mass fraction of 36.22wt.%, the hydrogen bond count reaches a maximum of 20, coinciding with a peak intermolecular interaction energy of 2171.63kcal·mol-1 and a minimized free volume fraction of 16.03%, indicative of a highly compact molecular packing structure and further increasing the MA content to 52.97wt.% induces a notable reduction in the composite’s bandgap to 3.13eV (minimum) and a concurrent deepening of trap energy levels to 3.06eV (maximum). Spatial charge differential density analysis demonstrates enhanced electron density localization near hydrogen-bonded regions, suppressing electron escape probability by over 40% compared to non-bonded domains. These findings collectively highlight a dual mechanism: hydrogen bonds not only reconfigure the molecular topology but also reshape localized charge distribution, directly impeding carrier mobility and altering charge transport pathways. The findings establish a robust structure-property relationship, demonstrating that hydrogen bond engineering serves as a pivotal strategy to tailor dielectric performance in polymer composites. By optimizing hydrogen bond density, the trade-off between structural compactness and electronic confinement can be strategically balanced, enabling the design of PP-based dielectrics with low carbon footprints and superior insulating properties. This mechanistic understanding provides actionable guidelines for advancing high-performance insulating materials in energy storage systems, aerospace components, and next-generation electrical devices, where precise control over charge transport is paramount.
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Keywords:
- polypropylene /
- hydrogen bond /
- molecular dynamics /
- charge transport
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[1] Li H, Gadinski M R, Huang Y Q 2020 ENERG ENVIRON SCI 13 1279
[2] Tan D Q 2020 Adv. Funct. Mater. 30 1808567
[3] Pablo A R, Baltus C B, Sebastião V C, Sílvia H P 2024 CHEM ENG SCI 298 120319
[4] Yin J X, Wang Q H 2024 Acta Phys. Sin. 73 157401 (in Chinese) [殷嘉鑫，王强华 2024 73 157401]
[5] Luo B, Li J L, Wang S J, Hu S X, Xu Y S, Xiao W, Xu G Y, He J L, Li Q 2024 Proceedings of the CSEE 44 3371 (in Chinese) [罗兵，李君洛，王少杰，胡世勋，徐永生，肖微，徐刚毅，何金良，李琦 2024 中国电机工程学报 44 3371]
[6] Fan L Z, Li Q, Yuan H, Huang S S, He J L 2022 Proceedings of the CSEE 45 4227 (in Chinese) [樊林禛，李琦，袁浩，黄上师，何金良 2022 中国电机工程学报 42 4227]
[7] Ohuk L, Kim D, Kim H, Seong H L, Taehoon K, Kwon I, Keisuke S, Masayuki H, Jin H L, Dae H L, Kim M H, Masahiro K, Yu S G 2025 COMPOS SCI TECHNOL 259 110939
[8] Hu S, Zhou Y, Yuan C, Wang W, Hu J 2020 High Voltage 5 249
[9] Fan L Z, Hao G H, Zhang W J, Dong X H, Tu Y P, Hu S X, Shao Q, Zheng Z, Wang W, Yuan H, Li Q, He J L 2023 Proceedings of the CSEE 45 5251 (in Chinese) [樊林禛，郝国辉，张雯嘉，董新华，屠幼萍，胡世勋，邵清，郑重，王伟，袁浩，李琦，何金良 2023 中国电机工程学报 45 5251]
[10] Li L, Wang X, Sun W F, Lei Q Q 2013 Acta Phys. Sin. 62 106201 (in Chinese) [李琳，王暄，孙伟峰，雷清泉 2013 62 106201]
[11] Li L L, Zhang X H, Wang Y L 2017 Acta Phys. Sin. 66 316 (in Chinese) [李丽丽，张晓虹，王玉龙 2017 66 087201]
[12] Ulian G, Moro D, Valdrè G 2018 Micro Nano Lett. 13 4
[13] Duan X H, Wah H S, Martin G, John L, He J L 2020 High Voltage 5 397
[14] Etcheverry M, Barbosa S E 2012 Materials 5 1084
[15] Kang J W, Choi K, John W H, Hu S L 1998 Polymer 39 7079
[16] Pang X, Zhu S J, Xu T L 2024 High Voltage Engineering 1 13 (in Chinese) [庞曦，朱思佳，许天蕾 2024 高电压技术 1 13]
[17] Ma C, Min D M, Li S T, Zheng X, Li X Y, Min C, Zhan H Y 2017 Acta Phys. Sin. 66 067701 (in Chinese) [马超，闵道敏，李盛涛，郑旭，李西育，闵超，湛海涯 2017 66 067701]
[18] Xiao M, Zhang Z, Du B, Wang B, Cao J 2024 IEEE Trans. Appl. Supercond. 34 8
[19] Zhang W J, Hu H X, Zhang Y R, Zhang Q, Wang M T, Li J 2023 IEEE Trans. Dielectr. Electr. Insul. 30 5
[20] Peng X Y, Yao C, Yu X, Hu S X, Fan Y Z, He J L 2023 High Voltage Engineering 49 4480 (in Chinese) [彭向阳，姚驰，余欣，胡世勋，范亚洲，何金良 2023 高电压技术 49 4480]
[21] Legnani C, Ventura A, Terzaghi C 2010 INT ORTHOP 34 465
[22] Chen C, Li W Z 2009 Acta Phys. -Chim. Sin. 25 507 (in Chinese) [陈聪，李维仲 2009 物理化学学报 25 507]
[23] Feng Y, Qu G H, Li S T 2024 High Voltage Engineering 50 2363 (in Chinese) [冯阳，渠广昊，李盛涛 2024 高电压技术 50 2363]
[24] Ran Z Y, Luo Z, Li J L, Meng L, Liu Y H, Hu J 2024 IEEE 5th International Conference on Dielectrics France, August 2—6, 2024, p1241
[25] Fan J Z, Fang Z B, Luo C J, Zhang H 2022 Acta Phys. Sin. 71 127103 (in Chinese) [樊金泽，方展伯，罗超杰，张汇 2022 71 127103]
[26] Li G C, Liu T Z, Gu Z L, Chen X L, Sun B B, Zhu Y W, Li S T, Wei Y H 2024 High Voltage 85 2397
[27] Hong D K, Liu L, Guo X 2015 Proceedings of the CSEE 35 6099 (in Chinese) [洪迪昆，刘亮，郭欣 2015 中国电机工程学报 35 6099]
[28] Li Q, Yao F Z, Liu Yang 2018 Annu. Rev. Mater. Res. 48 219
[29] Gabriel P, Jacob P T, Mikhail I, Wu Z G, John W L 2025 J. Chem. Phys. 162 054709
[30] Wang J, Wang J X, Zeng F G, Wu X L 2010 Acta Chim. Sin. 68 1653 (in Chinese) [王进，王军霞，曾凡桂，吴秀玲 2010 化学学报 68 1653]
[31] Xiao M, Chen Y Y, Zhao Y S, Du B X 2024 High Voltage Engineering 50 2319 (in Chinese) [肖萌，陈毓妍，赵亦烁，杜伯学 2024 高电压技术 50 2319]
[32] Le G C, Blaise G 2021 IEEE Trans. Appl. Supercond. 27 472
[33] Li H, Ai D, Ren L, L 2019 Adv. Mater. 31 1900875
[34] Zhou Y, Li Q, Dang B 2018 Adv. Mater. 30 1805672
[35] Li S T, Xie D R, Min D M 2019 Proceedings of the CSEE 39 6122 (in Chinese) [李盛涛，谢东日，闵道敏 2019 中国电机工程学报 39 6122]
[36] Wang J, David B A, Carlos A F, De L, Zhang D X, Alexander B, Aart W V, David S 2022 COMPOS PART A-APPL S 159 16993
[37] Guo J H 2014 Simulation of Morphology and Dielectric Properties of Polyethylene /Montmorillonite Nano-composite (Harbin: Harbin University of Science and Technology) (in Chinese) [国家辉 2014 硕士学位论文 (哈尔滨：哈尔滨理工大学)]
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