Citation: CHENG Zhenjie, MAO Yayun, DONG Qingyu, JIN Feng, SHEN Yanbin, CHEN Liwei. Fluoroethylene Carbonate as an Additive for Sodium-Ion Batteries: Effect on the Sodium Cathode[J]. Acta Physico-Chimica Sinica, ;2019, 35(8): 868-875. doi: 10.3866/PKU.WHXB201811033 shu

Fluoroethylene Carbonate as an Additive for Sodium-Ion Batteries: Effect on the Sodium Cathode

CHENG Zhenjie ^1,2 ,
MAO Yayun ^2,3 ,
DONG Qingyu ^1,2 ,
JIN Feng ^1,2 ,
SHEN Yanbin ^2,, ,
CHEN Liwei ²

1.
School of Nano Technology and Nano Bionics, University of Science and Technology of China, Hefei 230026, P. R. China
2.
i-Lab, CAS Center for Excellence in Nanoscience, Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123, Jiangsu Province, P. R. China
3.
School of Materials Science and Engineering, Shanghai University, Shanghai 200444, P. R. China

Corresponding author: SHEN Yanbin, ybshen2017@sinano.ac.cn
Received Date: 20 November 2018
Revised Date: 9 December 2018
Accepted Date: 10 December 2018
Available Online: 12 August 2018
Fund Project: the "Strategic Priority Research Program" of the CAS XDA09010600the National Natural Science Foundation of China 21733012the National Natural Science Foundation of China 21625304The project was supported by the Ministry of Science and Technology, China (2016YFB0100102), the "Strategic Priority Research Program" of the CAS (XDA09010600, XDA09010303), and the National Natural Science Foundation of China (21625304, 21733012)the "Strategic Priority Research Program" of the CAS XDA09010303the Ministry of Science and Technology, China 2016YFB0100102

Driven by the wide-scale implementation of intermittent renewable energy generating technologies, such as wind and solar, sodium-ion batteries have recently attracted attention as an inexpensive energy storage system due to the abundance, low cost, and relatively low redox potential of sodium. However, in comparison with lithium-ion batteries, which are known for long cycle life, sodium-ion batteries usually suffer from significant capacity fading during long-term cycling due to the large volume expansion/contraction of the electrode active materials caused by insertion/extraction of the large sodium ion. In recent years, intense effort has been focused on the search for high performance electrode materials and electrolytes to improve the cyclability of sodium-ion batteries, and some progress has been achieved. The incorporation of additives into the electrolyte is a simple and efficient method of improving the cycle stability of sodium-ion batteries. Fluoroethylene carbonate (FEC) is generally considered to be a suitable additive for the formation of the anode solid electrolyte interphase (SEI), due to a relatively low-lying lowest unoccupied molecular orbital (LUMO). However, it is suggested that FEC it will not be oxidized on the cathode since it also has a relatively low highest occupied molecular orbital (HOMO). In this study, we investigated the effect of FEC as an additive on the cycle life of a sodium-ion battery with a P2-Na_xCo_0.7Mn_0.3O₂ (x ≈ 1) layered sodium transition metal oxide as the cathode active material, a sodium metal foil anode, a glass fiber separator, and an electrolyte composed of NaClO₄ and a varying mass content of FEC dissolved in propylene carbonate (PC). We analyzed the effect of the FEC additive on the morphology and chemical composition of the separator and cathode electrode surface using scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS), and studied the evolution of the crystalline structure of the cathode active material during charge and discharge using in situ X-ray diffraction (XRD). We found that an appropriate amount of FEC additive significantly suppressed the decomposition of the PC solvent, and assisted the formation of a NaF-rich protective layer on the cathode surface, which helped to maintain the structural stability of the cathode material, thereby improving the cycle stability of the sodium-ion battery. Density functional theory (DFT) calculations showed that FEC coordinates more readily with the ClO₄^- anion on the cathode surface than does the PC solvent. This drives the formation of the NaF-rich protective layer on the cathode surface. We believe these results could provide inspiration in the design of electrolyte additives for protection of the sodium cathode during cycling, thus improving the cycling performance of sodium-ion batteries.
- Electrolyte additive,
- Fluoroethylene carbonate,
- Sodium ion battery,
- Cathode materials,
- In situ XRD
1. [1]
  Armand, M.; Tarascon, J. M. Nature 2008, 451, 652. doi: 10.1038/451652a doi: 10.1038/451652a
2. [2]
  Etacheri, V.; Marom, R.; Elazari, R.; Salitra, G.; Aurbach, D. Energy Environ. Sci. 2011, 4, 3243. doi: 10.1039/c1ee01598b doi: 10.1039/c1ee01598b
3. [3]
  Xu, K. Chem. Rev. 2014, 114, 11503. doi: 10.1021/cr500003w doi: 10.1021/cr500003w
4. [4]
  Hong, S. Y.; Kim, Y.; Park, Y.; Choi, A.; Choi, N. S.; Lee, K. T. Energy Environ. Sci. 2013, 6, 2067. doi: 10.1039/c3ee40811f doi: 10.1039/c3ee40811f
5. [5]
  Palomares, V.; Serras, P.; Villaluenga, I.; Hueso, K. B.; Carretero-Gonzalez, J.; Rojo, T. Energy Environ. Sci. 2012, 5, 5884. doi: 10.1039/c2ee02781j doi: 10.1039/c2ee02781j
6. [6]
  Yabuuchi, N.; Kajiyama, M.; Iwatate, J.; Nishikawa, H.; Hitomi, S.; Okuyama, R.; Usui, R.; Yamada, Y.; Komaba, S. Nat. Mater. 2012, 11, 512. doi: 10.1038/nmat3309 doi: 10.1038/nmat3309
7. [7]
  Yuan, D.; Liang, X.; Wu, L.; Cao, Y.; Ai, X.; Feng, J.; Yang, H. Adv. Mater. 2014, 26, 6301. doi: 10.1002/adma.201401946 doi: 10.1002/adma.201401946
8. [8]
  Fang, Y.; Xiao, L.; Ai, X.; Cao, Y.; Yang, H. Adv. Mater. 2015, 27, 5895. doi: 10.1002/adma.201502018 doi: 10.1002/adma.201502018
9. [9]
  Fang, Y.; Xiao, L.; Qian, J.; Ai, X.; Yang, H.; Cao, Y. Nano Lett. 2014, 14, 3539. doi: 10.1021/nl501152f doi: 10.1021/nl501152f
10. [10]
  Komaba, S.; Murata, W.; Ishikawa, T.; Yabuuchi, N.; Ozeki, T.; Nakayama, T.; Ogata, A.; Gotoh, K.; Fujiwara, K. Adv. Funct. Mater. 2011, 21, 3859. doi: 10.1002/adfm.201100854 doi: 10.1002/adfm.201100854
11. [11]
  Cao, Y.; Xiao, L.; Sushko, M. L.; Wang, W.; Schwenzer, B.; Xiao, J.; Nie, Z.; Saraf, L. V.; Yang, Z.; Liu, J. Nano Lett. 2012, 12, 3783. doi: 10.1021/nl3016957 doi: 10.1021/nl3016957
12. [12]
  Wu, L.; Lu, H.; Xiao, L.; Qian, J.; Ai, X.; Yang, H.; Cao, Y. J. Mater. Chem. A 2014, 2, 16424. doi: 10.1039/c4ta03365e doi: 10.1039/c4ta03365e
13. [13]
  Qu, B.; Ma, C.; Ji, G.; Xu, C.; Xu, J.; Meng, Y. S.; Wang, T.; Lee, J. Y. Adv. Mater. 2014, 26, 3854. doi: 10.1002/adma.201306314 doi: 10.1002/adma.201306314
14. [14]
  Lee, Y.; Lee, J.; Kim, H.; Kang, K.; Choi, N. S. J. Power Sources 2016, 320, 49. doi: 10.1016/j.jpowsour.2016.04.070 doi: 10.1016/j.jpowsour.2016.04.070
15. [15]
  Wrodnigg, G. H.; Besenhard, J. O.; Winter, M. J. Electrochem. Soc. 1999, 146, 470. doi: 10.1149/1.1391630 doi: 10.1149/1.1391630
16. [16]
  Weadock, N.; Varongchayakul, N.; Wan, J.; Lee, S.; Seog, J.; Hu, L. Nano Energy 2013, 2, 713. doi: 10.1016/j.nanoen.2013.08.005 doi: 10.1016/j.nanoen.2013.08.005
17. [17]
  Komaba, S.; Ishikawa, T.; Yabuuchi, N. ACS Appl. Mater. Interfaces 2011, 3, 4165. doi: 10.1021/am200973k doi: 10.1021/am200973k
18. [18]
  Ji, L.; Gu, M.; Shao, Y.; Li, X.; Engelhard, M. H.; Arey, B. W.; Wang, W.; Nie, Z.; Xiao, J.; Wang, C.; et al. Adv. Mater. 2014, 26, 2901. doi: 10.1002/adma.201304962 doi: 10.1002/adma.201304962
19. [19]
  Xu, C.; Lindgren, F.; Philippe, B.; Gustafsson, T. Chem. Mater. 2015, 27, 2591. doi: 10.1021/acs.chemmater.5b00339 doi: 10.1021/acs.chemmater.5b00339
20. [20]
  Horowitz, Y.; Han, H. L.; Soto, F. A.; Ralston, W. T.; Somorjai, G. A. Nano Lett. 2018, 18, 1145. doi: 10.1021/acs.nanolett.7b04688 doi: 10.1021/acs.nanolett.7b04688
21. [21]
  Horowitz, Y.; Steinruck, H. G.; Han, H. L.; Cao, C.; Tsao, Y. Nano Lett. 2018, 18, 2105. doi: 10.1021/acs.nanolett.8b00298 doi: 10.1021/acs.nanolett.8b00298
22. [22]
  Shen, Y.; Birgisson, S.; Iversen, B. B. J. Mater. Chem. A 2016, 4, 12281. doi: 10.1039/c6ta03630a doi: 10.1039/c6ta03630a
23. [23]
  Paulsen, J. M.; Dahn, J. R. Solid State Ionics 1999, 126, 3. doi: 10.1016/s0167-2738(99)00147-2 doi: 10.1016/s0167-2738(99)00147-2
24. [24]
  Tang, W. J.; Peng, W. J.; Yan, G. C.; Guo, H. J.; Li, X. H.; Zhou, Y. Ionics 2017, 23, 3281. doi: 10.1007/s11581-017-2143-5 doi: 10.1007/s11581-017-2143-5
25. [25]
  Gireaud, L.; Grugeon, S.; Laruelle, S.; Pilard, S.; Tarascon, J.-M. J.Electrochem. Soc. 2005, 152, A850. doi: 10.1149/1.1872673 doi: 10.1149/1.1872673
26. [26]
  Aurbach, D.; Daroux, M. L.; Faguy, P. W.; Yeager, E. J. Electrochem. Soc. 1987, 134, 1611. doi: 10.1149/1.2100722 doi: 10.1149/1.2100722
27. [27]
  Li, B.; Wang, Y.; Lin, H.; Liu, J.; Xing, L.; Xu, M.; Li, W. Electrochim. Acta 2014, 141, 263. doi: 10.1016/j.electacta.2014.07.085 doi: 10.1016/j.electacta.2014.07.085
28. [28]
  A.N. Mansour, D.G. Kwabi, R.A. Quinlan, Y.-C. Lu, Y. Shao-Horn. J. Electrochem. Soc.2016, 163, A2911. doi: 10.1149/2.0331614jes doi: 10.1149/2.0331614jes
29. [29]
  Lindgren, F.; Xu, C.; Niedzicki, L.; Marcinek, M.; Gustafsson, T.; Bjorefors, F.; Edstrom, K.; Younesi, R. ACS Appl. Mater. Interfaces 2016, 8, 15758. doi: 10.1021/acsami.6b02650 doi: 10.1021/acsami.6b02650
30. [30]
  Chen, X.; Li, X.; Mei, D.; Feng, J.; Hu, M. Y.; Hu, J.; Engelhard, M.; Zheng, J.; Xu, W.; Xiao, J.; Liu, J.; Zhang, J. G. ChemSusChem 2014, 7, 549. doi: 10.1002/cssc.201300770 doi: 10.1002/cssc.201300770
31. [31]
  Lee, Y.; Lee, J.; Lee, J.; Kim, K.; Cha, A.; Kang, S.; Wi, T.; Kang, S. J.; Lee, H. W.; Choi, N. S. ACS Appli. Mater. Interfaces 2018, 10, 15270. doi: 10.1021/acsami.8b02446 doi: 10.1021/acsami.8b02446
32. [32]
  Purushotham, U.; Takenaka, N.; Nagaoka, M. RSC Adv. 2016, 6, 65232. doi: 10.1039/c6ra09560g doi: 10.1039/c6ra09560g
33. [33]
  Li, J.; Li, W.; You, Y.; Manthiram, A. Adv. Energy Mater. 2018, 8. doi: 10.1002/aenm.201801957 doi: 10.1002/aenm.201801957
34. [34]
  Liu, D.; Qian, K.; He, Y. B.; Luo, D.; Li, H.; Wu, M.; Kang, F.; Li, B. Electrochim. Acta 2018, 269, 378. doi: 10.1016/j.electacta.2018.02.151 doi: 10.1002/aenm.201801957
1. [1]
  Yuyao Wang , Zhitao Cao , Zeyu Du , Xinxin Cao , Shuquan Liang . Research Progress of Iron-based Polyanionic Cathode Materials for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(4): 100035-0. doi: 10.3866/PKU.WHXB202406014
2. [2]
  Zifang ZHAO , Jingteng FENG , Jiaxin LI , Cong YANG , Linhan XING , Weifeng HUANG , Mingming HAN . Research progress and prospects on electrolyte additives for aqueous Zn-I₂ battery. Chinese Journal of Inorganic Chemistry, 2026, 42(7): 1345-1367. doi: 10.11862/CJIC.20260066
3. [3]
  Li Peicai , Wang Xubin , Zhang Qinghua , Wang Bowen , Rong Xiaohui , Hu Yong-Sheng , Li Zhongtao . High-rate and long-cycling P2-type cathode material for sodium-ion batteries. Acta Physico-Chimica Sinica, 2026, 42(5): 100214-. doi: 10.1016/j.actphy.2025.100214
4. [4]
  Zhuo Han , Danfeng Zhang , Haixian Wang , Guorui Zheng , Ming Liu , Yanbing He . Research Progress and Prospect on Electrolyte Additives for Interface Reconstruction of Long-Life Ni-Rich Lithium Batteries. Acta Physico-Chimica Sinica, 2024, 40(9): 2307034-0. doi: 10.3866/PKU.WHXB202307034
5. [5]
  Jianbao Mei , Bei Li , Shu Zhang , Dongdong Xiao , Pu Hu , Geng Zhang . Enhanced Performance of Ternary NASICON-Type Na_3.5−xMn_0.5V_1.5−xZr_x (PO₄)₃/C Cathodes for Sodium-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(12): 2407023-0. doi: 10.3866/PKU.WHXB202407023
6. [6]
  Jiahe LIU , Gan TANG , Kai CHEN , Mingda ZHANG . Effect of low-temperature electrolyte additives on low-temperature performance of lithium cobaltate batteries. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 719-728. doi: 10.11862/CJIC.20250023
7. [7]
  Qiang Huang , Yue Wang , Xuejie Wang , Lyubov G. Bulusheva , Tao Liu . La-Ce双掺杂调控电子结构及离子传输增强Na₄Fe₃(PO₄)₂P₂O₇正极的超快储钠性能. Acta Physico-Chimica Sinica, 2026, 42(11): 100339-. doi: 10.1016/j.actphy.2026.100339
8. [8]
  Lingbang Qiu , Jiangmin Jiang , Libo Wang , Lang Bai , Fei Zhou , Gaoyu Zhou , Quanchao Zhuang , Yanhua Cui . In Situ Electrochemical Impedance Spectroscopy Monitoring of the High-Temperature Double-Discharge Mechanism of Nb₁₂WO₃₃ Cathode Material for Long-Life Thermal Batteries. Acta Physico-Chimica Sinica, 2025, 41(5): 100040-0. doi: 10.1016/j.actphy.2024.100040
9. [9]
  Ziying YUAN , Zhen DUAN , Dan LIU , Jingrui NIU , Feiyan LAI , Xiaohui ZHANG , Guangchang YANG . Modification of O3-type Na_0.86Ni_1/3Fe_1/3Mn_1/3O₂ cathode material via Ti⁴⁺/P⁵⁺ dual-site co-doping. Chinese Journal of Inorganic Chemistry, 2026, 42(8): 1647-1657. doi: 10.11862/CJIC.20260041
10. [10]
  Zilin Hu , Yaoshen Niu , Xiaohui Rong , Yongsheng Hu . Suppression of Voltage Decay through Ni³⁺ Barrier in Anionic-Redox Active Cathode for Na-Ion Batteries. Acta Physico-Chimica Sinica, 2024, 40(6): 2306005-0. doi: 10.3866/PKU.WHXB202306005
11. [11]
  Yu Guo , Zhiwei Huang , Yuqing Hu , Junzhe Li , Jie Xu . Recent Advances in Iron-based Heterostructure Anode Materials for Sodium Ion Batteries. Acta Physico-Chimica Sinica, 2025, 41(3): 100022-0. doi: 10.3866/PKU.WHXB202311015
12. [12]
  Wang Shuang , Fu Xiaoqi , Yao Shanshan . Synergistic optimization of ion migration and electron transfer in sodium-ion battery cathode materials. Acta Physico-Chimica Sinica, 2026, 42(5): 100206-. doi: 10.1016/j.actphy.2025.100206
13. [13]
  Shan Zhao , Xu Liu , Haotian Guo , Zonglin Liu , Pengfei Wang , Jie Shu , Tingfeng Yi . Synergistic design of high-entropy P2/O3 biphasic cathodes for high-performance sodium-ion batteries. Acta Physico-Chimica Sinica, 2026, 42(1): 100129-0. doi: 10.1016/j.actphy.2025.100129
14. [14]
  Rongzhan LOU , Qiaoling KANG , Zhenchao BAI , Dongyun LI , Yang XU , Rui WANG , Qingyi LU . Research progress of sodium ion high entropy layered oxide cathode. Chinese Journal of Inorganic Chemistry, 2025, 41(12): 2411-2428. doi: 10.11862/CJIC.20250142
15. [15]
  Qingtang ZHANG , Xiaoyu WU , Zheng WANG , Xiaomei WANG . Performance of nano Li₂FeSiO₄/C cathode material co-doped by potassium and chlorine ions. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1689-1696. doi: 10.11862/CJIC.20240115
16. [16]
  Pengyang FAN , Shan FAN , Qinjin DAI , Xiaoying ZHENG , Wei DONG , Mengxue WANG , Xiaoxiao HUANG , Yong ZHANG . Preparation and performance of rich 1T-MoS₂ nanosheets for high-performance aqueous zinc ion battery cathode materials. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 675-682. doi: 10.11862/CJIC.20240339
17. [17]
  Liangliang Song , Haoyan Liang , Shunqing Li , Bao Qiu , Zhaoping Liu . Challenges and strategies on high-manganese Li-rich layered oxide cathodes for ultrahigh-energy-density batteries. Acta Physico-Chimica Sinica, 2025, 41(8): 100085-0. doi: 10.1016/j.actphy.2025.100085
18. [18]
  Mengxue WANG , Shan FAN , Wei DONG , Yichen REN , Yong ZHANG . Preparation and performance of Mo-doped MnO₂ cathode materials for zinc-ion batteries. Chinese Journal of Inorganic Chemistry, 2026, 42(9): 2033-2040. doi: 10.11862/CJIC.20260111
19. [19]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
20. [20]
  Débora Ferreira dos Santos Morais , José Luis Tirado , Carlos Pérez-Vicente , Fabiana Villela da Motta , Pedro Lavela , Mauricio Bomio , Sergio Lavela . Unlocking the performance of sodium-ion batteries by coating Na₃V₂(PO₄)₃ with Nb₂O₅. Acta Physico-Chimica Sinica, 2026, 42(2): 100180-0. doi: 10.1016/j.actphy.2025.100180

Get Citation

PDF

XML

Metrics

PDF Downloads(34)
Abstract views(3672)
HTML views(788)

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