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Nano Research 2022, 15(8): 7172-7179 https://doi.org/10.1007/s12274-022-4349-8
Research Article | Issue | Published: 04 May 2022

High-rate sodium metal batteries enabled by trifluormethylfullerene additive

Show Author's Information Pengju Li1,  Xiaobo Huang1,  Zhipeng Jiang1,2,  Han Zhang1,2,  Pengwei Yu1,  Xing Lu1( ),  Jia Xie2( )
State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
State Key Laboratory of Advanced Electromagnetic Engineering and Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
Keywords:
fullerene, high rate, sodium metal anode, electrolyte additive, trifluormethylfullerene
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Li P, Huang X, Jiang Z, et al. High-rate sodium metal batteries enabled by trifluormethylfullerene additive. Nano Research, 2022, 15(8): 7172-7179. https://doi.org/10.1007/s12274-022-4349-8
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Abstract Full text Electronic supplementary material About this article

Sodium metal is a promising anode for sodium batteries due to its high theoretical capacity and low cost. However, the serious Na dendrite growth and low Coulombic efficiency, especially at high current densities/cycling capacities, severely limit the application of sodium metal anodes. Herein, trifluoromethylfullerene, C60(CF3)6, is designed as an electrolyte additive to enable the high-rate cycling of sodium metal anodes with high Coulombic efficiency. The CF3 groups contribute to the formation of stable NaF-rich solid electrolyte interface layer, while C60 cages induce the uniform distribution of sodium ions and promote the formation of smooth and compact morphology. Thus, Na||Cu cell with C60(CF3)6 can be cycled at 2 mA·cm−2 and 10 mAh·cm−2 over 180 cycles with an average Coulombic efficiency of 99.9%, and Na||Na cell can be cycled at 10 mA·cm−2 over 600 cycles. Furthermore, Na||NaV2(PO4)3@C full cell exhibits high capacity retention of 84% over 2,000 cycles at 20 C (~ 3 mA·cm−2).


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Electronic supplementary material
About this article

High-rate sodium metal batteries enabled by trifluormethylfullerene additive

Show Author's information Pengju Li1, Xiaobo Huang1, Zhipeng Jiang1,2, Han Zhang1,2, Pengwei Yu1, Xing Lu1( ), Jia Xie2( )
State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China
State Key Laboratory of Advanced Electromagnetic Engineering and Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

Abstract

Sodium metal is a promising anode for sodium batteries due to its high theoretical capacity and low cost. However, the serious Na dendrite growth and low Coulombic efficiency, especially at high current densities/cycling capacities, severely limit the application of sodium metal anodes. Herein, trifluoromethylfullerene, C60(CF3)6, is designed as an electrolyte additive to enable the high-rate cycling of sodium metal anodes with high Coulombic efficiency. The CF3 groups contribute to the formation of stable NaF-rich solid electrolyte interface layer, while C60 cages induce the uniform distribution of sodium ions and promote the formation of smooth and compact morphology. Thus, Na||Cu cell with C60(CF3)6 can be cycled at 2 mA·cm−2 and 10 mAh·cm−2 over 180 cycles with an average Coulombic efficiency of 99.9%, and Na||Na cell can be cycled at 10 mA·cm−2 over 600 cycles. Furthermore, Na||NaV2(PO4)3@C full cell exhibits high capacity retention of 84% over 2,000 cycles at 20 C (~ 3 mA·cm−2).

Keywords: fullerene, high rate, sodium metal anode, electrolyte additive, trifluormethylfullerene

References(55)

1

Wang, Y. X.; Wang, Y. X.; Wang, Y. X.; Feng, X. M.; Chen, W. H.; Ai, X. P.; Yang, H. X.; Cao, Y. L. Developments and perspectives on emerging high-energy-density sodium-metal batteries. Chem 2019, 5, 2547–2570.
DOI Google Scholar
2

Lee, B.; Paek, E.; Mitlin, D.; Lee, S. W. Sodium metal anodes: Emerging solutions to dendrite growth. Chem. Rev. 2019, 119, 5416–5460.
DOI Google Scholar
3

Wang, H.; Matios, E.; Luo, J. M.; Li, W. Y. Combining theories and experiments to understand the sodium nucleation behavior towards safe sodium metal batteries. Chem. Soc. Rev. 2020, 49, 3783–3805.
DOI Google Scholar
4

Zhao, Y.; Adair, K. R.; Sun, X. L. Recent developments and insights into the understanding of Na metal anodes for Na-metal batteries. Energy Environ. Sci. 2018, 11, 2673–2695.
DOI Google Scholar
5

Zheng, X. Y.; Bommier, C.; Luo, W.; Jiang, L. H.; Hao, Y. N.; Huang, Y. H. Sodium metal anodes for room-temperature sodium-ion batteries: Applications, challenges and solutions. Energy Storage Mater. 2019, 16, 6–23.
DOI Google Scholar
6

Bao, C. Y.; Wang, B.; Liu, P.; Wu, H.; Zhou, Y.; Wang, D. L.; Liu, H. K.; Dou, S. X. Solid electrolyte interphases on sodium metal anodes. Adv. Funct. Mater. 2020, 30, 2004891.
DOI Google Scholar
7

Ma, C. Y.; Xu, T. T.; Wang, Y. Advanced carbon nanostructures for future high performance sodium metal anodes. Energy Storage Mater. 2020, 25, 811–826.
DOI Google Scholar
8

Lee, Y.; Lee, J.; Lee, J.; Kim, K.; Cha, A. M.; Kang, S. J.; Wi, T.; Kang, S. J.; Lee, H. W.; Choi, N. S. Fluoroethylene carbonate-based electrolyte with 1 M sodium bis(fluorosulfonyl)imide enables high-performance sodium metal electrodes. ACS Appl. Mater. Interfaces 2018, 10, 15270–15280.
DOI Google Scholar
9

Yi, Q.; Lu, Y.; Sun, X. R.; Zhang, H.; Yu, H. L.; Sun, C. W. Fluorinated ether based electrolyte enabling sodium-metal batteries with exceptional cycling stability. ACS Appl. Mater. Interfaces 2019, 11, 46965–46972.
DOI Google Scholar
10

Mogensen, R.; Brandell, D.; Younesi, R. Solubility of the solid electrolyte interphase (SEI) in sodium ion batteries. ACS Energy Lett. 2016, 1, 1173–1178.
DOI Google Scholar
11

Fan, J. J.; Dai, P.; Shi, C. G.; Wen, Y. F.; Luo, C. X.; Yang, J.; Song, C.; Huang, L.; Sun, S. G. Synergistic dual-additive electrolyte for interphase modification to boost cyclability of layered cathode for sodium ion batteries. Adv. Funct. Mater. 2021, 31, 2010500.
DOI Google Scholar
12

Shi, Q. W.; Zhong, Y. R.; Wu, M.; Wang, H. Z.; Wang, H. L. High-performance sodium metal anodes enabled by a bifunctional potassium salt. Angew. Chem., Int. Ed. 2018, 57, 9069–9072.
DOI Google Scholar
13

Wang, H.; Wang, C. L.; Matios, E.; Li, W. Y. Facile stabilization of the sodium metal anode with additives: Unexpected key role of sodium polysulfide and adverse effect of sodium nitrate. Angew. Chem., Int. Ed. 2018, 57, 7734–7737.
DOI Google Scholar
14

Wang, S. Y.; Cai, W. B.; Sun, Z. H.; Huang, F. Y.; Jie, Y. L.; Liu, Y.; Chen, Y. W.; Peng, B.; Cao, R. G.; Zhang, G. Q. et al. Stable cycling of Na metal anodes in a carbonate electrolyte. Chem. Commun. 2019, 55, 14375–14378.
DOI Google Scholar
15

Jiang, R.; Hong, L.; Liu, Y. C.; Wang, Y. D.; Patel, S.; Feng, X. Y.; Xiang, H. F. An acetamide additive stabilizing ultra-low concentration electrolyte for long-cycling and high-rate sodium metal battery. Energy Storage Mater. 2021, 42, 370–379.
DOI Google Scholar
16

Miao, X. G.; Di, H. X.; Ge, X. L.; Zhao, D. Y.; Wang, P.; Wang, R. T.; Wang, C. X.; Yin, L. W. AlF3-modified anode-electrolyte interface for effective Na dendrites restriction in nasicon-based solid-state electrolyte. Energy Storage Mater. 2020, 30, 170–178.
DOI Google Scholar
17

Zhu, M.; Li, L. L.; Zhang, Y. J.; Wu, K.; Yu, F. F.; Huang, Z. Y.; Wang, G. Y.; Li, J. Y.; Wen, L. Y.; Liu, H. K. et al. An in-situ formed stable interface layer for high-performance sodium metal anode in a non-flammable electrolyte. Energy Storage Mater. 2021, 42, 145–153.
DOI Google Scholar
18

Zheng, X. Y.; Fu, H. Y.; Hu, C. C.; Xu, H.; Huang, Y.; Wen, J. Y.; Sun, H. B.; Luo, W.; Huang, Y. H. Toward a stable sodium metal anode in carbonate electrolyte: A compact, inorganic alloy interface. J. Phys. Chem. Lett. 2019, 10, 707–714.
DOI Google Scholar
19

Fang, W.; Jiang, H.; Zheng, Y.; Zheng, H.; Liang, X.; Sun, Y.; Chen, C. H.; Xiang, H. F. A bilayer interface formed in high concentration electrolyte with SbF3 additive for long-cycle and high-rate sodium metal battery. J. Power Sources 2020, 455, 227956.
DOI Google Scholar
20

Lee, Y.; Lee, J.; Kim, H.; Kang, K.; Choi, N. S. Highly stable linear carbonate-containing electrolytes with fluoroethylene carbonate for high-performance cathodes in sodium-ion batteries. J. Power Sources 2016, 320, 49–58.
DOI Google Scholar
21

Zhu, M.; Zhang, Y. J.; Yu, F. F.; Huang, Z. Y.; Zhang, Y.; Li, L. L.; Wang, G. Y.; Wen, L. Y.; Liu, H. K.; Dou, S. X. et al. Stable sodium metal anode enabled by an interface protection layer rich in organic sulfide salt. Nano Lett. 2021, 21, 619–627.
DOI Google Scholar
22

Zhong, Y. R.; Shi, Q. W.; Zhu, C. Q.; Zhang, Y. F.; Li, M.; Francisco, J. S.; Wang, H. L. Mechanistic insights into fast charging and discharging of the sodium metal battery anode: A comparison with lithium. J. Am. Chem. Soc. 2021, 143, 13929–13936.
DOI Google Scholar
23

Goryunkov, A. A.; Kuvychko, I. V.; Ioffe, I. N.; Dick, D. L.; Sidorov, L. N.; Strauss, S. H.; Boltalina, O. V. Isolation of C60(CF3)n (n = 2, 4, 6, 8, 10) with high compositional purity. J. Fluorine Chem. 2003, 124, 61–64.
DOI Google Scholar
24

Jiang, Z. P.; Zeng, Z. Q.; Yang, C. K.; Han, Z. L.; Hu, W.; Lu, J.; Xie, J. Nitrofullerene, a C60-based bifunctional additive with smoothing and protecting effects for stable lithium metal anode. Nano Lett. 2019, 19, 8780–8786.
DOI Google Scholar
25

Ardhi, R. E. A.; Liu, G. C.; Lee, J. K. Metal-semiconductor ohmic and schottky contact interfaces for stable Li-metal electrodes. ACS Energy Lett. 2021, 6, 1432–1442.
DOI Google Scholar
26

Xu, Q. S.; Lin, J. J.; Ye, C. C.; Jin, X. J.; Ye, D. Q.; Lu, Y. Y.; Zhou, G. M.; Qiu, Y. C.; Li, W. S. Air-stable and dendrite-free lithium metal anodes enabled by a hybrid interphase of C60 and Mg. Adv. Energy Mater. 2020, 10, 1903292.
DOI Google Scholar
27

Li, P. J.; Jiang, Z. P.; Huang, X. B.; Lu, X.; Xie, J.; Cheng, S. J. Nitrofullerene as an electrolyte-compatible additive for high-performance sodium metal batteries. Nano Energy 2021, 89, 106396.
DOI Google Scholar
28

Gu, Y.; Wang, W. W.; Li, Y. J.; Wu, Q. H.; Tang, S.; Yan, J. W.; Zheng, M. S.; Wu, D. Y.; Fan, C. H.; Hu, W. Q. et al. Designable ultra-smooth ultra-thin solid-electrolyte interphases of three alkali metal anodes. Nat. Commun. 2018, 9, 1339.
DOI Google Scholar
29

Hoen, S.; Chopra, N. G.; Xiang, X. D.; Mostovoy, R.; Hou, J. G.; Vareka, W. A.; Zettl, A. Elastic properties of a van der waals solid: C60. Phys. Rev. B 1992, 46, 12737–12739.
DOI Google Scholar
30

Pikhurov, D. V.; Zuev, V. V. The effect of fullerene C60 on the dielectric behaviour of epoxy resin at low nanofiller loading. Chem. Phys. Lett. 2014, 601, 13–15.
DOI Google Scholar
31

Song, P. A.; Liu, L. N.; Huang, G. B.; Yu, Y. M.; Guo, Q. P. Largely enhanced thermal and mechanical properties of polymer nanocomposites via incorporating C60@graphene nanocarbon hybrid. Nanotechnology 2013, 24, 505706.
DOI Google Scholar
32

Jiang, Z. P.; Zhao, Y. M.; Lu, X.; Xie, J. Fullerenes for rechargeable battery applications: Recent developments and future perspectives. J. Energy Chem. 2021, 55, 70–79.
DOI Google Scholar
33

McHedlov-Petrossyan, N. O. Fullerenes in liquid media: An unsettling intrusion into the solution chemistry. Chem. Rev. 2013, 113, 5149–5193.
DOI Google Scholar
34

Han, J. G.; Hwang, C.; Kim, S. H.; Park, C.; Kim, J.; Jung, G. Y.; Baek, K.; Chae, S.; Kang, S. J.; Cho, J. et al. An antiaging electrolyte additive for high-energy-density lithium-ion batteries. Adv. Energy Mater. 2020, 10, 2000563.
DOI Google Scholar
35

Hou, Z.; Wang, W. H.; Chen, Q. W.; Yu, Y. K.; Zhao, X. X.; Tang, M.; Zheng, Y. Y.; Quan, Z. W. Hybrid protective layer for stable sodium metal anodes at high utilization. ACS Appl. Mater. Interfaces 2019, 11, 37693–37700.
DOI Google Scholar
36

Zhang, X.; Hao, F.; Cao, Y. J.; Xie, Y. H.; Yuan, S. Y.; Dong, X. L.; Xia, Y. Y. Dendrite-free and long-cycling sodium metal batteries enabled by sodium-ether cointercalated graphite anode. Adv. Funct. Mater. 2021, 31, 2009778.
DOI Google Scholar
37

Zhao, Y.; Goncharova, L. V.; Zhang, Q.; Kaghazchi, P.; Sun, Q.; Lushington, A.; Wang, B. Q.; Li, R. Y.; Sun, X. L. Inorganic–organic coating via molecular layer deposition enables long life sodium metal anode. Nano Lett. 2017, 17, 5653–5659.
DOI Google Scholar
38

Zheng, X. Y.; Gu, Z. Y.; Liu, X. Y.; Wang, Z. Q.; Wen, J. Y.; Wu, X. L.; Luo, W.; Huang, Y. H. Bridging the immiscibility of an all-fluoride fire extinguishant with highly-fluorinated electrolytes toward safe sodium metal batteries. Energy Environ. Sci. 2020, 13, 1788–1798.
DOI Google Scholar
39

Han, M.; Zhu, C. B.; Ma, T.; Pan, Z.; Tao, Z. L.; Chen, J. In situ atomic force microscopy study of nano–micro sodium deposition in ester-based electrolytes. Chem. Commun. 2018, 54, 2381–2384.
DOI Google Scholar
40

Liu, X. Y.; Zheng, X. Y.; Dai, Y. M.; Wu, W. Y.; Huang, Y. Y.; Fu, H. Y.; Huang, Y. H.; Luo, W. Fluoride-rich solid-electrolyte-interface enabling stable sodium metal batteries in high-safe electrolytes. Adv. Funct. Mater. 2021, 31, 2103522.
DOI Google Scholar
41

Wu, J. Y.; Li, X. W.; Rao, Z. X.; Xu, X. N.; Cheng, Z. X.; Liao, Y. Q.; Yuan, L. X.; Xie, X. L.; Li, Z.; Huang, Y. H. Electrolyte with boron nitride nanosheets as leveling agent towards dendrite-free lithium metal anodes. Nano Energy 2020, 72, 104725.
DOI Google Scholar
42

Chen, X.; Shen, X.; Hou, T. Z.; Zhang, R.; Peng, H. J.; Zhang, Q. Ion-solvent chemistry-inspired cation-additive strategy to stabilize electrolytes for sodium-metal batteries. Chem 2020, 6, 2242–2256.
DOI Google Scholar
43

Zheng, X. Y.; Gu, Z. Y.; Fu, J.; Wang, H. T.; Ye, X. L.; Huang, L. Q.; Liu, X. Y.; Wu, X. L.; Luo, W.; Huang, Y. H. Knocking down the kinetic barriers towards fast-charging and low-temperature sodium metal batteries. Energy Environ. Sci. 2021, 14, 4936–4947.
DOI Google Scholar
44

Choudhury, S.; Wei, S. Y.; Ozhabes, Y.; Gunceler, D.; Zachman, M. J.; Tu, Z. Y.; Shin, J. H.; Nath, P.; Agrawal, A.; Kourkoutis, L. F. et al. Designing solid-liquid interphases for sodium batteries. Nat. Commun. 2017, 8, 898.
DOI Google Scholar
45

Xie, J.; Liao, L.; Gong, Y. J.; Li, Y. B.; Shi, F. F.; Pei, A.; Sun, J.; Zhang, R. F.; Kong, B.; Subbaraman, R. et al. Stitching h-BN by atomic layer deposition of LiF as a stable interface for lithium metal anode. Sci. Adv. 2017, 3, eaao3170.
DOI Google Scholar
46

Schafzahl, L.; Hanzu, I.; Wilkening, M.; Freunberger, S. A. An electrolyte for reversible cycling of sodium metal and intercalation compounds. ChemSusChem 2017, 10, 401–408.
DOI Google Scholar
47

Le, P. M. L.; Vo, T. D.; Pan, H. L.; Jin, Y.; He, Y.; Cao, X.; Nguyen, H. V.; Engelhard, M. H.; Wang, C. M.; Xiao, J. et al. Excellent cycling stability of sodium anode enabled by a stable solid electrolyte interphase formed in ether-based electrolytes. Adv. Funct. Mater. 2020, 30, 2001151.
DOI Google Scholar
48

Seh, Z. W.; Sun, J.; Sun, Y. M.; Cui, Y. A highly reversible room-temperature sodium metal anode. ACS Cent. Sci. 2015, 1, 449–455.
DOI Google Scholar
49

Wang, S. Y.; Chen, Y. W.; Jie, Y. L.; Lang, S. Y.; Song, J. H.; Lei, Z. W.; Wang, S.; Ren, X. D.; Wang, D.; Li, X. L. et al. Stable sodium metal batteries via manipulation of electrolyte solvation structure. Small Methods 2020, 4, 1900856.
DOI Google Scholar
50

Cao, R. G.; Mishra, K.; Li, X. L.; Qian, J. F.; Engelhard, M. H.; Bowden, M. E.; Han, K. S.; Mueller, K. T.; Henderson, W. A.; Zhang, J. G. Enabling room temperature sodium metal batteries. Nano Energy 2016, 30, 825–830.
DOI Google Scholar
51

Zheng, J. M.; Chen, S. R.; Zhao, W. G.; Song, J. H.; Engelhard, M. H.; Zhang, J. G. Extremely stable sodium metal batteries enabled by localized high-concentration electrolytes. ACS Energy Lett. 2018, 3, 315–321.
DOI Google Scholar
52
Doi, K.; Yamada, Y.; Okoshi, M.; Ono, J.; Chou, C. P.; Nakai, H.; Yamada, A. Reversible sodium metal electrodes: Is fluorine an essential interphasial component? Angew. Chem., Int. Ed. 2019, 58, 8024–8028.
53

Zhou, L.; Cao, Z.; Zhang, J.; Sun, Q. J.; Wu, Y. Q.; Wahyudi, W.; Hwang, J. Y.; Wang, L. M.; Cavallo, L.; Sun, Y. K. et al. Engineering sodium-ion solvation structure to stabilize sodium anodes: Universal strategy for fast-charging and safer sodium-ion batteries. Nano Lett. 2020, 20, 3247–3254.
DOI Google Scholar
54

Han, B.; Zou, Y. C.; Zhang, Z.; Yang, X. M.; Shi, X. B.; Meng, H.; Wang, H.; Xu, K.; Deng, Y. H.; Gu, M. Probing the Na metal solid electrolyte interphase via cryo-transmission electron microscopy. Nat. Commun. 2021, 12, 3066.
DOI Google Scholar
55

Xue, W. J.; Huang, M. J.; Li, Y. T.; Zhu, Y. G.; Gao, R.; Xiao, X. H.; Zhang, W. X.; Li, S. P.; Xu, G. Y.; Yu, Y. et al. Ultra-high-voltage Ni-rich layered cathodes in practical Li metal batteries enabled by a sulfonamide-based electrolyte. Nat Energy 2021, 6, 495–505.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 10 January 2022
Revised: 01 March 2022
Accepted: 22 March 2022
Published: 04 May 2022
Issue date: August 2022

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© Tsinghua University Press 2022

Acknowledgements

Acknowledgements

This work was supported by the National Science Foundation of China (Nos. 21925104, 51672093, 51821005, U1966214, 51902116, and 21975087). We thank the Analytical and Testing Center of HUST for all related measurements.

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