硫掺杂的碳点作为双功能电解液添加剂实现高性能水系锌离子电池

引用本文: 马千里, 宋天兵, 何天乐, 张熙荣, 熊焕明. 硫掺杂的碳点作为双功能电解液添加剂实现高性能水系锌离子电池[J]. 物理化学学报, 2025, 41(9): 100106. doi: 10.1016/j.actphy.2025.100106 shu

Citation: Qianli Ma, Tianbing Song, Tianle He, Xirong Zhang, Huanming Xiong. Sulfur-doped carbon dots: a novel bifunctional electrolyte additive for high-performance aqueous zinc-ion batteries[J]. Acta Physico-Chimica Sinica, 2025, 41(9): 100106. doi: 10.1016/j.actphy.2025.100106 shu

硫掺杂的碳点作为双功能电解液添加剂实现高性能水系锌离子电池

复旦大学化学系, 上海市资源电热转化与循环重点实验室(筹), 上海 200438

通讯作者: 熊焕明, hmxiong@fudan.edu.cn

基金项目:
国家自然科学基金 U24A20565

国家自然科学基金 21975048

摘要: 水系锌离子电池因其高安全性、环境友好性和低成本等优势，被视为一种富有前景的新型储能器件。然而，不可控的锌枝晶生长以及有害的副反应严重限制了水系锌电池的电化学性能。在众多改善策略中，电解液添加剂因其成本低廉和操作简便的优势，相较于人工界面涂层和电极结构设计更具应用潜力。本研究采用一种新型零维纳米材料——硫掺杂的碳点，作为电解液添加剂，通过多种表征手段对其结构和性质进行了系统分析，并组装成电池以评估这种碳点对电池性能的影响。实验结果表明，碳点通过其表面磺酸基团诱导锌电极表面择优形成稳定的(002)晶面，并重构水合Zn²⁺的溶剂化壳层，显著提升了电池的循环稳定性。在碳点添加剂的作用下，对称电池在10 mA∙cm⁻²的高电流密度下实现了近2000 h的稳定循环，Zn||NH₄V₄O₁₀和Zn||MnO₂全电池也表现出优异的电化学性能和显著提升的循环稳定性。本研究为开发高性能水系锌离子电池提供了新的思路和理论依据。

关键词:

English

Sulfur-doped carbon dots: a novel bifunctional electrolyte additive for high-performance aqueous zinc-ion batteries

Department of Chemistry, Shanghai Key Laboratory of Electrochemical and Thermochemical Conversion for Resources Recycling, Fudan University, Shanghai 200438, China

Corresponding author: Huanming Xiong, Email: hmxiong@fudan.edu.cn

Received Date: 16 April 2025
Accepted Date: 22 May 2025
Revised Date: 13 May 2025
Available Online: 15 September 2025
Fund Project:
the National Natural Science Foundation of China

the National Natural Science Foundation of China

Abstract: Aqueous zinc-ion batteries (AZIBs) have gained considerable attention as next-generation energy storage devices due to their inherent safety, environmental friendliness, and cost-effectiveness. However, their widespread application is severely hampered by uncontrolled zinc dendrite growth and detrimental side reactions (e.g., hydrogen evolution, corrosion, and passivation), which lead to reduced Coulombic efficiency and shortened cycle life. Current strategies to improve zinc anode stability mainly focus on artificial interface coatings, electrode structure design, and electrolyte optimization. Among these approaches, electrolyte additive engineering is considered the most promising for practical applications due to its simplicity, low cost, and excellent scalability. Nevertheless, conventional additives (including metal ions, polymers, and surfactants) typically address only single issues (either dendrite suppression or side reaction mitigation), failing to achieve synergistic effects. In this work, we developed sulfur-doped carbon dots (S-CDs) as a novel bifunctional electrolyte additive to significantly enhance AZIB performance. The carbon dot additive was synthesized via a facile calcination method, followed by systematic characterization of its structure and properties using methods such as Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and density functional theory (DFT) calculations. Comprehensive electrochemical evaluations were conducted to investigate the influence of S-CDs on zinc deposition behavior and overall battery performance. Experimental results demonstrate the successful synthesis of sulfur-doped carbon dots with abundant surface functional groups. During battery operation, the strong binding affinity between S-CDs and Zn²⁺ effectively reconstructs the Zn²⁺ solvation shell, reducing water molecule content and thereby minimizing electrode corrosion and side reactions caused by interfacial active water molecules. Moreover, the S-CDs induce the formation of stable (002) crystallographic planes that continuously renew during plating/stripping cycles, with particularly pronounced effects under high current densities, significantly enhancing the structural stability of the electrode. The synergistic effect of these dual functions leads to remarkable improvement in zinc electrode performance and ultimately endows the battery with ultra-long cycling life. Benefiting from the positive effects of the carbon dot additive, the symmetric cell achieves exceptional stability for nearly 2000 h at a high current density of 10 mA∙cm⁻², far outperforming conventional electrolyte systems. Furthermore, both Zn||NH₄V₄O₁₀ and Zn||MnO₂ full cells exhibit superior electrochemical performance and significantly enhanced cycling stability, confirming the excellent compatibility of the carbon dot additive with various cathode materials. This study provides novel insights and fundamental theoretical guidance for developing high-performance AZIBs, representing a significant advancement in sustainable energy storage technologies.

Key words:

1. [1]
  Y. H. Li, H. Yao, X. J. Liu, X. T. Yang, D. Yuan, Nano Res. 16 (2023) 9179-9194, https://doi.org/10.1007/s12274-023-5637-7. doi: 10.1007/s12274-023-5637-7
2. [2]
  J. D. Huang, Y. H. Zhu, Y. Feng, Y. H. Han, Z. Y. Gu, R.X. Liu, D.Y. Yang, K. Chen, X. Y. Zhang, W. Sun; et al., Acta Phys. -Chim. Sin. 38 (2022) 2208008, https://doi.org/10.3866/PKU.WHXB202208008. doi: 10.3866/PKU.WHXB202208008
3. [3]
  M. Song, H. Tan, D. L. Chao, H. J. Fan, Adv. Funct. Mater. 28 (2018) 1802564, https://doi.org/10.1002/adfm.201802564. doi: 10.1002/adfm.201802564
4. [4]
  Z. H. Yi, G. Y. Chen, F. Hou, L. Q. Wang, J. Liang, Adv. Energy Mater. 11 (2020) 2003065, https://doi.org/10.1002/aenm.202003065. doi: 10.1002/aenm.202003065
5. [5]
  B. Qiu, L. Z. Xie, G. Q. Zhang, K. J. Cheng, Z. W. Lin, W. Liu, C. X. He, P. X. Zhang, H. W. Mi, Chem. Eng. J. 449 (2022) 137843, https://doi.org/10.1016/j.cej.2022.137843. doi: 10.1016/j.cej.2022.137843
6. [6]
  B. Qiu, K. Y. Liang, W. Huang, G. Q. Zhang, C. X. He, P. X. Zhang, H. W. Mi, Adv. Energy Mater. 13 (2023) 2301193, https://doi.org/10.1002/aenm.202301193. doi: 10.1002/aenm.202301193
7. [7]
  Z. Zhao, R. Wang, C. Peng, W. Chen, T. Wu, B. Hu, W. Weng, Y. Yao, J. Zeng, Z. Chen, P. Liu, Y. Liu, G. Li, J. Guo, H. Lu, Z. Guo, Nat. Commun. 12 (2021) 6606, https://doi.org/10.1038/s41467-021-26947-9. doi: 10.1038/s41467-021-26947-9
8. [8]
  X. Wang, J. P. Meng, X. G. Lin, Y. D. Yang, S. Zhou, Y. P. Wang, A. Q. Pan, Adv. Funct. Mater. 31 (2021) 2106114, https://doi.org/10.1002/adfm.202106114. doi: 10.1002/adfm.202106114
9. [9]
  Z. Yi, J. Liu, S. Tan, Z. Sang, J. Mao, L. Yin, X. Liu, L. Wang, F. Hou, S. X. Dou, H. Cheng, J. Liang, Adv. Mater. 34 (2022) e2203835, https://doi.org/10.1002/adma.202203835. doi: 10.1002/adma.202203835
10. [10]
  H. Lu, Q. Jin, X. Jiang, Z. M. Dang, D. Zhang, Y. Jin, Small 18 (2022) e2200131, https://doi.org/10.1002/smll.202200131. doi: 10.1002/smll.202200131
11. [11]
  Y. E. Qi, Y. Y. Xia, Acta Phys. -Chim. Sin. 39 (2023), https://doi.org/10.3866/Pku.Whxb202205045. doi: 10.3866/Pku.Whxb202205045
12. [12]
  X.C. Liang, X.F. Chen, Z.X. Zhai, R.S. Huang, T.Q. Yu, S.B. Yin, Chem. Eng. J. 480 (2024) 148040, https://doi.org/10.1016/j.cej.2023.148040. doi: 10.1016/j.cej.2023.148040
13. [13]
  J. Cao, M. Sun, D. Zhang, Y. Zhang, C. Yang, D. Luo, X. Yang, X. Zhang, J. Qin, B. Huang, Z. Zeng, J. Lu, ACS Nano 18 (2024) 16610, https://doi.org/10.1021/acsnano.4c00288. doi: 10.1021/acsnano.4c00288
14. [14]
  R. X. Zhang, Y. X. Cui, L. L. Liu, S. M. Chen, J. Power Sources 602 (2024) 234351, https://doi.org/10.1016/j.jpowsour.2024.234351. doi: 10.1016/j.jpowsour.2024.234351
15. [15]
  C. Xia, S. Zhu, T. Feng, M. Yang, B. Yang, Adv. Sci. 6 (2019) 1901316, https://doi.org/10.1002/advs.201901316. doi: 10.1002/advs.201901316
16. [16]
  L. Ai, R. Shi, J. Yang, T. Zhang, S. Lu, Small 17 (2021) e2007523, https://doi.org/10.1002/smll.202007523. doi: 10.1002/smll.202007523
17. [17]
  J. Gao, M. M. Zhu, H. Huang, Y. Liu, Z. H. Kang, Inorg. Chem. Front. 4 (2017) 1963, https://doi.org/10.1039/c7qi00614d. doi: 10.1039/C7QI00614D
18. [18]
  M. G. Yi, M. J. Jing, Y. C. Yang, Y. J. Huang, G. Q. Zou, T. J. Wu, H. S. Hou, X. B. Ji, Adv. Funct. Mater. 34 (2024) 2400001, https://doi.org/10.1002/adfm.202400001. doi: 10.1002/adfm.202400001
19. [19]
  R. T. Guo, L. Li, B. W. Wang, Y. G. Xiang, G. Q. Zou, Y. R. Zhu, H. S. Hou, X. B. Ji, Energy Stor. Mater. 37 (2021) 8, https://doi.org/10.1016/j.ensm.2021.01.020. doi: 10.1016/j.ensm.2021.01.020
20. [20]
  H. Zhang, R. T. Guo, S. Li, C. Liu, H. Y. Li, G. Q. Zou, J. G. Hu, H. S. Hou, X. B. Ji, Nano Energy 92 (2022) 106752, https://doi.org/10.1016/j.nanoen.2021.106752. doi: 10.1016/j.nanoen.2021.106752
21. [21]
  W. Zhang, M. Dong, K. Jiang, D. Yang, X. Tan, S. Zhai, R. Feng, N. Chen, G. King, H. Zhang, H. Zeng, H. Li, M. Antonietti, Z. Li, Nat. Commun. 13 (2022) 5348, https://doi.org/10.1038/s41467-022-32955-0. doi: 10.1038/s41467-022-32955-0
22. [22]
  T. B. Song, Z. H. Huang, X. R. Zhang, J. W. Ni, H. M. Xiong, Small 19 (2023) e2205558, https://doi.org/10.1002/smll.202205558. doi: 10.1002/smll.202205558
23. [23]
  Q. Luo, H. Ding, X. Hu, J. Xu, A. Sadat, M. Xu, F. L. Primo, A. C. Tedesco, H. Zhang, H. Bi, Dalton Trans. 49 (2020) 6950, https://doi.org/10.1039/d0dt01187h. doi: 10.1039/d0dt01187h
24. [24]
  S. J. Mohammed, K. M. Omer, F. E. Hawaiz, RSC Adv. 13 (2023) 14340, https://doi.org/10.1039/d3ra01646c. doi: 10.1039/D3RA01646C
25. [25]
  P. P. Zhu, Z. Cheng, L. L. Du, Q. Chen, K. J. Tan, Langmuir 34 (2018) 9982, https://doi.org/10.1021/acs.langmuir.8b01230. doi: 10.1021/acs.langmuir.8b01230
26. [26]
  J. Duan, J. Yu, S. Feng, L. Su, Talanta 153 (2016) 332, https://doi.org/10.1016/j.talanta.2016.03.035. doi: 10.1016/j.talanta.2016.03.035
27. [27]
  L. Li, Y. Li, Y. Ye, R. Guo, A. Wang, G. Zou, H. Hou, X. Ji, ACS Nano 15 (2021) 6872, https://doi.org/10.1021/acsnano.0c10624. doi: 10.1021/acsnano.0c10624
28. [28]
  Y. Park, J. Yoo, B. Lim, W. Kwon, S. W. Rhee, J. Mater. Chem. A 4 (2016) 11582, https://doi.org/10.1039/c6ta04813g. doi: 10.1039/C6TA04813G
29. [29]
  P. Boulanger, J. Riga, J. Delhalle, J. J. Verbist, Polymer 29 (1988) 797-801, https://doi.org/10.1016/0032-3861(88)90135-8. doi: 10.1016/0032-3861(88)90135-8
30. [30]
  W. W. Liu, M. Li, G. P. Jiang, G. R. Li, J. B. Zhu, M. L. Xiao, Y. F. Zhu, R. Gao, A. P. Yu, M. Feng; et al., Adv. Energy. Mater. 10 (2020) 2001275, https://doi.org/10.1002/aenm.202001275. doi: 10.1002/aenm.202001275
31. [31]
  X. Fan, L. Chen, Y. Wang, X. Xu, X. Jiao, P. Zhou, Y. Liu, Z. Song, J. Zhou, Nanomicro Lett 16 (2024) 270, https://doi.org/10.1007/s40820-024-01475-5. doi: 10.1007/s40820-024-01475-5
32. [32]
  J. Hao, L. Yuan, C. Ye, D. Chao, K. Davey, Z. Guo, S. Z. Qiao, Angew. Chem. Int. Ed. Engl. 60 (2021) 7366-7375, https://doi.org/10.1002/anie.202016531. doi: 10.1002/anie.202016531
33. [33]
  N. N. Chang, T. Y. Li, R. Li, S. N. Wang, Y. B. Yin, H. M. Zhang, X. F. Li, Energy Environ Sci 13 (2020) 3527-3535, https://doi.org/10.1039/d0ee01538e. doi: 10.1039/D0EE01538E
34. [34]
  Z. Cao, X. Zhu, S. Gao, D. Xu, Z. Wang, Z. Ye, L. Wang, B. Chen, L. Li, M. Ye; et al., Small 18 (2022) e2103345, https://doi.org/10.1002/smll.202103345. doi: 10.1002/smll.202103345
35. [35]
  F. X. Xie, H. Li, X. S. Wang, X. Zhi, D. L. Chao, K. Davey, S. Z. Qiao, Adv. Energy. Mater. 11 (2021) 2003419, https://doi.org/10.1002/aenm.202003419. doi: 10.1002/aenm.202003419
36. [36]
  J. L. Cong, X. Shen, Z. P. Wen, X. Wang, L. Q. Peng, J. Zeng, J. B. Zhao, Energy Storage Mater 35 (2021) 586-594, https://doi.org/10.1016/j.ensm.2020.11.041. doi: 10.1016/j.ensm.2020.11.041
37. [37]
  Z. M. Zhao, J. W. Zhao, Z. L. Hu, J. D. Li, J. J. Li, Y. J. Zhang, C. Wang, G. L. Cui, Energy Environ Sci 12 (2019) 1938-1949, https://doi.org/10.1039/c9ee00596j. doi: 10.1039/C9EE00596J
38. [38]
  G. D. Wilcox, P. J. Mitchell, J. Power Sources 28 (1989) 345-359, https://doi.org/10.1016/0378-7753(89)80064-3. doi: 10.1016/0378-7753(89)80064-3
39. [39]
  M. Chen, Y. Gong, Y. Zhao, Y. Song, Y. Tang, Z. Zeng, S. Liang, P. Zhou, B. Lu, X. Zhang; et al., Natl Sci Rev 11 (2024) nwae205, https://doi.org/10.1093/nsr/nwae205. doi: 10.1093/nsr/nwae205
40. [40]
  W. Y. Chen, S. Guo, L. P. Qin, L. Y. Li, X. X. Cao, J. Zhou, Z. G. Luo, G. Z. Fang, S. Q. Liang, Adv. Funct. Mater. 32 (2022) 2112609, https://doi.org/10.1002/adfm.202112609. doi: 10.1002/adfm.202112609
41. [41]
  D. L. Han, Z. X. Wang, H. T. Lu, H. Li, C. J. Cui, Z. C. Zhang, R. Sun, C. N. Geng, Q. H. Liang, X. X. Guo; et al., Adv. Energy. Mater. 12 (2022) 2102982, https://doi.org/10.1002/aenm.202102982. doi: 10.1002/aenm.202102982
42. [42]
  K. Ouyang, S. Chen, W. Ling, M. Cui, Q. Ma, K. Zhang, P. Zhang, Y. Huang, Angew. Chem. Int. Ed. Engl. 62 (2023) e202311988, https://doi.org/10.1002/anie.202311988. doi: 10.1002/anie.202311988
43. [43]
  M. Qiu, P. Sun, Y. Wang, L. Ma, C. Zhi, W. Mai, Angew. Chem. Int. Ed. Engl. 61 (2022) e202210979, https://doi.org/10.1002/anie.202210979. doi: 10.1002/anie.202210979
44. [44]
  D. Xu, Z. Wang, C. Liu, H. Li, F. Ouyang, B. Chen, W. Li, X. Ren, L. Bai, Z. Chang; et al., Adv. Mater. 36 (2024) e2403765, https://doi.org/10.1002/adma.202403765. doi: 10.1002/adma.202403765
45. [45]
  Y. H. Tao, Y.J. Cui, H. X. Wang, Z. L. Li, Z. J. S. Qian, P. P. Zhang, H. J. Zhou, M. J. Shi, Adv. Funct. Mater. 35 (2024) 2414805, https://doi.org/10.1002/adfm.202414805. doi: 10.1002/adfm.202414805
46. [46]
  Y. H. Tao, J. Jin, Y. J. Cui, H. X. Wang, Z. J. S. Qian, M. J. Shi, ACS Sustain Chem Eng 12 (2024) 16434-16443, https://doi.org/10.1021/acssuschemeng.4c06939. doi: 10.1021/acssuschemeng.4c06939

扫一扫看文章

计量

PDF下载量: 0
文章访问数: 18
HTML全文浏览量: 1

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

硫掺杂的碳点作为双功能电解液添加剂实现高性能水系锌离子电池

通讯作者: 熊焕明, hmxiong@fudan.edu.cn

English

Sulfur-doped carbon dots: a novel bifunctional electrolyte additive for high-performance aqueous zinc-ion batteries

Corresponding author: Huanming Xiong, Email: hmxiong@fudan.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

硫掺杂的碳点作为双功能电解液添加剂实现高性能水系锌离子电池

通讯作者: 熊焕明, hmxiong@fudan.edu.cn

English

Sulfur-doped carbon dots: a novel bifunctional electrolyte additive for high-performance aqueous zinc-ion batteries

Corresponding author: Huanming Xiong, Email: hmxiong@fudan.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs