Citation: Guihuang Fang, Ying Liu, Yangyang Feng, Ying Pan, Hongwei Yang, Yongchuan Liu, Maoxiang Wu. Tuning the ion-dipole interactions between fluoro and carbonyl (EC) by electrolyte design for stable lithium metal batteries[J]. Chinese Chemical Letters, ;2025, 36(1): 110385. doi: 10.1016/j.cclet.2024.110385 shu

Tuning the ion-dipole interactions between fluoro and carbonyl (EC) by electrolyte design for stable lithium metal batteries

Guihuang Fang ^{a, b, 1} ,
Ying Liu ^{b, 1} ,
Yangyang Feng ^b ,
Ying Pan ^b ,
Hongwei Yang ^{a, *,} ,
Yongchuan Liu ^{b, *,} ,
Maoxiang Wu ^{b, *,}

a.
Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China
b.
Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China

hongweiy@kust.edu.cn

ycliu@fjirsm.ac.cn

mxwu@fjirsm.ac.cn

Received Date: 9 July 2024
Revised Date: 22 July 2024
Accepted Date: 29 August 2024
Available Online: 3 September 2024

Figures(4)

Ethylene carbonate (EC) is the conventional and promising solvent to achieve high energy lithium metal battery. However, the innate low energy level of lowest unoccupied molecular orbital (LUMO) in EC makes it incompatible with lithium metal, causing uncontrolled lithium growth and low Coulombic efficiency (CE). Herein, we introduced bis(2,2,2-trifluoroethyl) carbonate (TFEC), a carbonate with a strong electron-withdrawing effect (-CF₃), which enhances the stability of EC at electrode interface by reducing ion-dipole interactions between Li⁺ and EC. As the interaction between Li and EC weakens, TFEC and more PF₆⁻ anions coordinate with Li⁺, promoting the formation of contact ion pairs (CIPs) and aggregates (AGGs), thereby increasing the inorganic composition within the solid electrolyte interphase. Additionally, the distinct solvated sheath structure favors the decomposition of fluorinated solvents and PF₆⁻ anions, forming inorganic-rich electrode-electrolyte interfaces (SEI and CEI), thereby ensuring high stability for both the Li anode and high-voltage cathode. Hence, when applied in the full-cell LiLiMn_0.8Fe_0.2PO₄, it displays consistent cycling performance, exhibiting minimal capacity decay with a retention rate of 62.5% after 800 cycles, substantially surpassing that of cells using base electrolytes (29.8%).
- Lithium-ion batteries,
- LiMn_0.8Fe_0.2PO₄,
- High-voltage,
- Solvation structure,
- Ethylene carbonate,
- Bis(2,2,2-trifluoroethyl) carbonate
1. [1]
  J.M. Tarascon, M. Armand, Nature 414 (2001) 359–367. doi: 10.1038/35104644
2. [2]
  Y. Huang, J. Li, Adv. Energy Mater. 12 (2022) 48.
3. [3]
  X. Ren, P. Gao, L. Feng, W. Xu, Proc. Natl. Acad. Sci. U. S. A. 117 (2020) 28603–28613. doi: 10.1073/pnas.2010852117
4. [4]
  J. Zhang, Y. Su, Y. Zhang, Nanoscale 12 (2020) 15528–15559. doi: 10.1039/D0NR03833D
5. [5]
  H. Kim, G. Jeong, Y. Kim, et al., Chem. Rev. 42 (2013) 9011–9034.
6. [6]
  W. Xu, J. Wang. F. Ding, et al., Energy Environ. Sci. 7 (2014) 513–537. doi: 10.1039/C3EE40795K
7. [7]
  G.H. Fang, Y. Pan, H.W. Yang, et al., J. Phys. Chem. C 128 (2024) 6877–6886. doi: 10.1021/acs.jpcc.4c00459
8. [8]
  M. Du, J.Z. Guo, S.H. Zheng, et al., Chin. Chem. Lett. 34 (2023) 107706. doi: 10.1016/j.cclet.2022.07.049
9. [9]
  H.Y. Wang, H.X. Chen, C. Chen, et al., Chin. Chem. Lett. 34 (2023) 107465. doi: 10.1016/j.cclet.2022.04.063
10. [10]
  C. Wei, C. Liu, Y. Xiao, et al., Adv. Funct Mater. 33 (2023) 2314306.
11. [11]
  G. H Fang, W. Chen, H.S. Fang, et al., Chin. Chem. Lett. 35 (2024) 108799. doi: 10.1016/j.cclet.2023.108799
12. [12]
  Y. Liu, Y.Q. Chen, Y.S. Ling, et al., ACS Nano 17 (2023) 19625–19639. doi: 10.1021/acsnano.3c01895
13. [13]
  D. Zhang, Z. Liu, Y. Wu, et al., Adv. Sci. 9 (2022) 322.
14. [14]
  W. Xu, W. Dong, J. Zhou, et al., Adv. Sci. 6 (2024) 2400466.
15. [15]
  J. Zhang, W. Xu, J. Xiao, et al., Chem. Rev. 120 (2020) 13312. doi: 10.1021/acs.chemrev.0c00275
16. [16]
  X. Zhang, X. Chen, X. Cheng, et al., Angew. Chem. Int. Ed. 57 (2018) 5301–5305. doi: 10.1002/anie.201801513
17. [17]
  C. Yan, Y. Yao, X. Chen, et al., Angew. Chem. Int. Ed. 57 (2018) 14055–14059. doi: 10.1002/anie.201807034
18. [18]
  X. Zheng, L. Huang, W. Luo, et al., ACS Energy Lett. 6 (2021) 2054. doi: 10.1021/acsenergylett.1c00647
19. [19]
  L. Hou, N. Yao, J. Xie, et al., Angew. Chem. Int. Ed. 61 (2022) 20.
20. [20]
  T.D. Pham, K.K. Lee, Small 17 (2021) 20.
21. [21]
  J. Wu, T. Zhou, B. Zhong, et al., ACS Appl. Mater. Interfaces 14 (2022) 27873–27881. doi: 10.1021/acsami.2c05098
22. [22]
  J. Holoubek, M. Yu, S. Yu, et al., ACS Energy Lett. 5 (2020) 1438–1447. doi: 10.1021/acsenergylett.0c00643
23. [23]
  X. Yuan, T. Dong, J. Liu, et al., Angew. Chem. Int. Ed. 62 (2023) 1–12.
24. [24]
  C.V. Amanchukwu, Z. Yu, X. Kong, et al., J. Am. Chem. Soc. 142 (2020) 7393–7403. doi: 10.1021/jacs.9b11056
25. [25]
  Z. Wang, Z. Sun, J. Li, et al., Chem. Soc. Rev. 50 (2021) 3178–3210. doi: 10.1039/D0CS01017K
26. [26]
  X. Liu, X. Shen, L. Luo, et al., ACS Energy Lett. 6 (2021) 4282–4290. doi: 10.1021/acsenergylett.1c02194
27. [27]
  O. Borodin, M. Olguin, P. Ganesh, et al., Phys. Chem. Chem. Phys. 18 (2016) 164–175. doi: 10.1039/C5CP05121E
28. [28]
  S. Uchida, T. Kiyobayashi, Phys. Chem. Chem. Phys. 23 (2021) 10875–10887. doi: 10.1039/D1CP00967B
29. [29]
  O. Borodin, G.D. Smith, J. Phys. Chem. B 113 (2009) 1763–1776. doi: 10.1021/jp809614h
30. [30]
  H. Su, Z. Chen, M. Li, et al., Adv. Mater. 35 (2023) 29.
31. [31]
  J. Ding, R. Xu, N. Yao, et al., Angew. Chem. Int. Ed. 60 (2021) 11442–11447. doi: 10.1002/anie.202101627
32. [32]
  L. Zhao, Z. Wu, Z. Wang, et al., ACS Nano 16 (2022) 20891–20901. doi: 10.1021/acsnano.2c08441
33. [33]
  P. Xiao, Y. Zhao, Z. Piao, et al., Energy Environ. Sci. 15 (2022) 2435–2444. doi: 10.1039/D1EE02959B
34. [34]
  B.D. Adams, J. Zheng, X. Ren, et al., Adv. Energy Mater. 8 (2018) 1702097. doi: 10.1002/aenm.201702097
35. [35]
  W. Zhang, T. Yang, X. Liao, et al., Energy Storage Mater. 57 (2023) 2549 -259.
36. [36]
  S. Zhang, S. Li, X. Wang, et al., Nano Energy 114 (2023) 108639. doi: 10.1016/j.nanoen.2023.108639
37. [37]
  W. Martin, Y. Tian, J. Xiao, J. Electrochem. Soc. 168 (2021) 060513. doi: 10.1149/1945-7111/ac0647
38. [38]
  D.J. Yoo, S. Yang, K.J. Kim, et al., Angew. Chem. Int. Ed. 59 (2020) 14869–14876. doi: 10.1002/anie.202003663
39. [39]
  S.H. Han, S.D. Han, O. Borodin, et al., J. Phys. Chem. C 119 (2015) 8492–8500. doi: 10.1021/acs.jpcc.5b00826
40. [40]
  B. Horstmann, J. Shi, R. Amine, et al., Energy Environ. Sci. 14 (2021) 5289–5314. doi: 10.1039/D1EE00767J
41. [41]
  X. Zhang, X. Cheng, X. Chen, et al., Adv. Funct Mater. 27 (2017) 10.
42. [42]
  Z. Chang, Y. Qiao, H. Yang, et al., Angew. Chem. Int. Ed. 60 (2021) 15572–15581. doi: 10.1002/anie.202104124
43. [43]
  K. Yoshida, M. Nakamura, Kazue Y, et al., J. Am. Chem. Soc. 133 (2011) 13121–13129. doi: 10.1021/ja203983r
44. [44]
  A Guéguen, L. Castro, R. Dedryvre, et al., J. Electrochem. Soc. 160 (2013) A387–A393. doi: 10.1149/2.019303jes
1. [1]
  Guihuang Fang , Wei Chen , Hongwei Yang , Haisheng Fang , Chuang Yu , Maoxiang Wu . Improved performance of LiMn_0.8Fe_0.2PO₄ by addition of fluoroethylene carbonate electrolyte additive. Chinese Chemical Letters, 2024, 35(6): 108799-. doi: 10.1016/j.cclet.2023.108799
2. [2]
  Xi Tang , Chunlei Zhu , Yulu Yang , Shihan Qi , Mengqiu Cai , Abdullah N. Alodhayb , Jianmin Ma . Additive regulating Li⁺ solvation structure to construct dual LiF−rich electrode electrolyte interphases for sustaining 4.6 V Li||LiCoO₂ batteries. Chinese Chemical Letters, 2024, 35(12): 110014-. doi: 10.1016/j.cclet.2024.110014
3. [3]
  Haining Peng , Huijun Liu , Chengzong Li , Yingfu Li , Qizhi Chen , Tao Li . Diluent modified weakly solvating electrolyte for fast-charging high-voltage lithium metal batteries. Chinese Chemical Letters, 2025, 36(1): 109556-. doi: 10.1016/j.cclet.2024.109556
4. [4]
  Mei-Chen Liu , Qing-Song Liu , Yi-Zhou Quan , Jia-Ling Yu , Gang Wu , Xiu-Li Wang , Yu-Zhong Wang . Phosphorus-silicon-integrated electrolyte additive boosts cycling performance and safety of high-voltage lithium-ion batteries. Chinese Chemical Letters, 2024, 35(8): 109123-. doi: 10.1016/j.cclet.2023.109123
5. [5]
  Zhong-Hui Sun , Yu-Qi Zhang , Zhen-Yi Gu , Dong-Yang Qu , Hong-Yu Guan , Xing-Long Wu . CoPSe nanoparticles confined in nitrogen-doped dual carbon network towards high-performance lithium/potassium ion batteries. Chinese Chemical Letters, 2025, 36(1): 109590-. doi: 10.1016/j.cclet.2024.109590
6. [6]
  Xingang Kong , Yabei Su , Cuijuan Xing , Weijie Cheng , Jianfeng Huang , Lifeng Zhang , Haibo Ouyang , Qi Feng . Facile synthesis of porous TiO₂/SnO₂ nanocomposite as lithium ion battery anode with enhanced cycling stability via nanoconfinement effect. Chinese Chemical Letters, 2024, 35(11): 109428-. doi: 10.1016/j.cclet.2023.109428
7. [7]
  Hui Gu , Mingyue Gao , Kuan Shen , Tianli Zhang , Junhao Zhang , Xiangjun Zheng , Xingmei Guo , Yuanjun Liu , Fu Cao , Hongxing Gu , Qinghong Kong , Shenglin Xiong . F127 assisted fabrication of Ge/rGO/CNTs nanocomposites with three-dimensional network structure for efficient lithium storage. Chinese Chemical Letters, 2024, 35(9): 109273-. doi: 10.1016/j.cclet.2023.109273
8. [8]
  Wendi Dou , Guangying Wan , Tiefeng Liu , Lin Han , Wu Zhang , Chuang Sun , Rensheng Song , Jianhui Zheng , Yujing Liu , Xinyong Tao . Conductive composite binder for recyclable LiFePO₄ cathode. Chinese Chemical Letters, 2024, 35(11): 109389-. doi: 10.1016/j.cclet.2023.109389
9. [9]
  Peng Zhou , Ziang Jiang , Yang Li , Peng Xiao , Feixiang Wu . Sulphur-template method for facile manufacturing porous silicon electrodes with enhanced electrochemical performance. Chinese Chemical Letters, 2024, 35(8): 109467-. doi: 10.1016/j.cclet.2023.109467
10. [10]
  Mianying Huang , Zhiguang Xu , Xiaoming Lin . Mechanistic analysis of Co2VO4/X (X = Ni, C) heterostructures as anode materials of lithium-ion batteries. Chinese Journal of Structural Chemistry, 2024, 43(7): 100309-100309. doi: 10.1016/j.cjsc.2023.100309
11. [11]
  Xinyu Liu , Jialin Yang , Zonglin He , Jiaoyan Ai , Lina Song , Baohua Liu . Linear polyurethanes with excellent comprehensive properties from poly(ethylene carbonate) diol. Chinese Chemical Letters, 2025, 36(1): 110236-. doi: 10.1016/j.cclet.2024.110236
12. [12]
  Yue Wang , Caixia Xu , Xingtao Tian , Siyu Wang , Yan Zhao . Challenges and Modification Strategies of High-Voltage Cathode Materials for Li-ion Batteries. Chinese Journal of Structural Chemistry, 2023, 42(10): 100167-100167. doi: 10.1016/j.cjsc.2023.100167
13. [13]
  Shengyu Zhao , Xuan Yu , Yufeng Zhao . A water-stable high-voltage P3-type cathode for sodium-ion batteries. Chinese Chemical Letters, 2024, 35(9): 109933-. doi: 10.1016/j.cclet.2024.109933
14. [14]
  Lingjiang Kou , Yong Wang , Jiajia Song , Taotao Ai , Wenhu Li , Mohammad Yeganeh Ghotbi , Panya Wattanapaphawong , Koji Kajiyoshi . Mini review: Strategies for enhancing stability of high-voltage cathode materials in aqueous zinc-ion batteries. Chinese Chemical Letters, 2025, 36(1): 110368-. doi: 10.1016/j.cclet.2024.110368
15. [15]
  Yuanchao LI , Weifeng HUANG , Pengchao LIANG , Zifang ZHAO , Baoyan XING , Dongliang YAN , Li YANG , Songlin WANG . Effect of heterogeneous dual carbon sources on electrochemical properties of LiMn_0.8Fe_0.2PO₄/C composites. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 751-760. doi: 10.11862/CJIC.20230252
16. [16]
  Jinge Zhu , Ailing Tang , Leyi Tang , Peiqing Cong , Chao Li , Qing Guo , Zongtao Wang , Xiaoru Xu , Jiang Wu , Erjun Zhou . Chlorination of benzyl group on the terminal unit of A₂-A₁-D-A₁-A₂ type nonfullerene acceptor for high-voltage organic solar cells. Chinese Chemical Letters, 2025, 36(1): 110233-. doi: 10.1016/j.cclet.2024.110233
17. [17]
  Xin Li , Ling Zhang , Yunyan Fan , Shaojing Lin , Yong Lin , Yongsheng Ying , Meijiao Hu , Haiying Gao , Xianri Xu , Zhongbiao Xia , Xinchuan Lin , Junjie Lu , Xiang Han . Carbon interconnected microsized Si film toward high energy room temperature solid-state lithium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109776-. doi: 10.1016/j.cclet.2024.109776
18. [18]
  Ruofan Yin , Zhaoxin Guo , Rui Liu , Xian-Sen Tao . Ultrafast synthesis of Na₃V₂(PO₄)₃ cathode for high performance sodium-ion batteries. Chinese Chemical Letters, 2025, 36(2): 109643-. doi: 10.1016/j.cclet.2024.109643
19. [19]
  Xin-Tong Zhao , Jin-Zhi Guo , Wen-Liang Li , Jing-Ping Zhang , Xing-Long Wu . Two-dimensional conjugated coordination polymer monolayer as anode material for lithium-ion batteries: A DFT study. Chinese Chemical Letters, 2024, 35(6): 108715-. doi: 10.1016/j.cclet.2023.108715
20. [20]
  Ya Song , Mingxia Zhou , Zhu Chen , Huali Nie , Jiao-Jing Shao , Guangmin Zhou . Integrated interconnected porous and lamellar structures realized fast ion/electron conductivity in high-performance lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(6): 109200-. doi: 10.1016/j.cclet.2023.109200

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(98)
HTML views(2)

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