Citation: Jian Liu, Yuanli Cai, Huan Pang, Bin Cao, Chengzhi Luo, Zhenghao Hu, Chaoqun Xiao, Hu Zhang, Fulu Lv, Yitao Cao, Lei Yu. Chloro-free synthesis of LiPF₆ using the fluorine-oxygen exchange technique[J]. Chinese Chemical Letters, ;2022, 33(8): 4061-4063. doi: 10.1016/j.cclet.2021.12.068 shu

Chloro-free synthesis of LiPF₆ using the fluorine-oxygen exchange technique

Jian Liu ^{a, b} ,
Yuanli Cai ^{a, b} ,
Huan Pang ^a ,
Bin Cao ^{a, b} ,
Chengzhi Luo ^b ,
Zhenghao Hu ^b ,
Chaoqun Xiao ^b ,
Hu Zhang ^b ,
Fulu Lv ^b ,
Yitao Cao ^c ,
Lei Yu ^{a, *,}

a.
School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou 225002, China
b.
Tianzhu Hongfu Lithium Industry Technology Development Company Limited, Wuwei 733200, China
c.
Royal Holloway, University of London, Egham TW20 0QR, United Kingdom

yulei@yzu.edu.cn

Received Date: 8 November 2021
Revised Date: 23 December 2021
Accepted Date: 24 December 2021
Available Online: 29 December 2021

Figures(3)

A hydrogen fluoride-free and chloro-free method for synthesizing LiPF₆ was developed. Employing CaF₂ as the direct fluorinating reagent instead of hydrogen fluoride made it much safer and more environment-friendly than conventional methods and reduced the metal residues in product owing to the relatively low-acid reaction conditions less corrosive to equipments. The use of P₂O₅ as phosphorus source instead of traditionally employed PCl₅ significantly reduced the chloro residue in product. Ca(H₂PO₄)₂, the only by-product of the process, could be easily converted into Ca₃(PO₄)₂, a best-selling chemical. The above advantages not only reduce the production costs by ca. 20%, but also significantly improve the product purity. The fluorine-oxygen exchange reaction is a completely new technique for LiPF₆ production and may bring about technological revolution in the related industry.
- Lithium,
- Fluorine,
- Electrolyte,
- High purity,
- Green chemistry,
- Process
1. [1]
  Y. Wang, L. Zhang, F. Zhang, et al., J. Energy Chem.58 (2021) 602–609. doi: 10.1016/j.jechem.2020.10.019
2. [2]
  M. Liu, J. Vatamanu, X. Chen, et al., ACS Energy Lett. 6 (2021) 2096–2102. doi: 10.1021/acsenergylett.1c00707
3. [3]
  Y. Wu, S.H. Bo, Y. Xia, J. Power Sources 467 (2020) 228292. doi: 10.1016/j.jpowsour.2020.228292
4. [4]
  L. Liu, S. Gu, S. Wang, X. Zhang, S. Chen, RSC Adv. 10 (2020) 1704–1710. doi: 10.1039/c9ra09841k
5. [5]
  Z. Chen, N. Xu, W. Li, et al., J. Mater. Chem. A 7 (2019) 16347–16355. doi: 10.1039/c9ta01810g
6. [6]
  H. Jia, B. Billmann, H. Onishi, et al., Chem. Mater. 31 (2019) 4025–4033. doi: 10.1021/acs.chemmater.9b00555
7. [7]
  J.G. Han, K. Kim, Y. Lee, N.S. Choi, Adv. Mater. 31 (2019) 1804822. doi: 10.1002/adma.201804822
8. [8]
  T. Thomberg, R. Väli, J. Eskusson, et al., J. Electrochem. Soc. 165 (2018) A3862–A3870. doi: 10.1149/2.0661816jes
9. [9]
  G.W. Zheng, T. Wei, Nat. Energy 2 (2017) 17029. doi: 10.1038/nenergy.2017.29
10. [10]
  A.A. Smagin, V.A. Matyukha, V.P. Korobtsev, J. Power Sources 68 (1997), 326–327. doi: 10.1016/S0378-7753(97)02652-9
11. [11]
  H.B. Han, S.S. Zhou, D.J. Zhang, et al. J. Power Sources 196 (2011) 3623–3632. doi: 10.1016/j.jpowsour.2010.12.040
12. [12]
  J. Liu, Y. Cai, C. Xiao, et al., Ind. Eng. Chem. Res. 58 (2019), 20491–20494. doi: 10.1021/acs.iecr.9b04958
13. [13]
  M. Magallanes-Perdomo, A.H. De Aza, I. Sobrados, J. Sanz, P. Pena, Acta Biomater. 8 (2012) 820–829. doi: 10.1016/j.actbio.2011.10.017
14. [14]
  M. Magallanes-Perdomo, A.H. De Aza, I. Sobrados, et al., J. Am. Ceram. Soc. 100 (2017) 4288–4304. doi: 10.1111/jace.14943
15. [15]
  W. Ding, Y. Zhang, B. Wang, W. Zhu, R. Zhang, J. Alloy Compd. 815 (2020) 152661. doi: 10.1016/j.jallcom.2019.152661
16. [16]
  A.R. Kadam, R.L. Kohale, G.C. Mishra, S.J. Dhoble, New J. Chem. 45 (2021) 7285–7307. doi: 10.1039/d0nj05930g
17. [17]
  D.V. Deyneko, D, A., Spassky, V.A. Morozov, et al., Inorg. Chem. 60 (2021) 3961–3971. doi: 10.1021/acs.inorgchem.0c03813
18. [18]
  F. Zhao, Z. Song, Q. Liu, Inorg. Chem. 60 (2021) 3952–3960. doi: 10.1021/acs.inorgchem.0c03773
19. [19]
  B. Ravdel, K. Abraham, R. Gitzendanner, et al., J. Power Sources119-121 (2003) 805–810. doi: 10.1016/S0378-7753(03)00257-X
20. [20]
  C. Chen, Y. Cao, X. Wu, et al., Chin. Chem. Lett. 31 (2020) 1078–1082. doi: 10.1016/j.cclet.2019.12.019
21. [21]
  B. Zhang, C. Qiu, S. Wang, et al., Sci. Bull. 66 (2021) 562–569.
22. [22]
  J.Y. Chen, C.T. Zhong, Q.W. Gui, et al., Chin. Chem. Lett. 32 (2021) 475–479. doi: 10.1016/j.cclet.2020.09.034
23. [23]
  Y. Wu, J.Y. Chen, J. Ning, et al., Green Chem. 23 (2021) 3950–3954. doi: 10.1039/d1gc00562f
24. [24]
  Z.L. Wu, J.Y. Chen, X.Z. Tian, et al., Chin. Chem. Lett. 33 (2022) 1501–1504.
25. [25]
  W. Zhao, F. Ren, Q. Yan, H. Liu, Y. Yang, Chin. Chem. Lett. 31 (2020) 3209–3212.
26. [26]
  L. Yu, P. Li, J. Liu, Y. Cai, B. Cao, Patent, CN 110615421A, 2019.
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10. [10]
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11. [11]
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12. [12]
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13. [13]
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14. [14]
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15. [15]
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16. [16]
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17. [17]
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Chloro-free synthesis of LiPF6 using the fluorine-oxygen exchange technique

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通讯作者: 陈斌, bchen63@163.com

Chloro-free synthesis of LiPF₆ using the fluorine-oxygen exchange technique