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Enabling the reversibility of anhydrous copper(II) fluoride cathodes for rechargeable lithium batteries via fluorinated high-concentration electrolytes

氟化高浓电解液实现无水氟化铜正极的可逆循环

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Abstract

Anhydrous copper(II) fluoride (CuF2) has a high specific capacity of 528 mA h g−1 with an operating voltage of 3.55 V vs. Li/Li+, achieving a high gravimetric energy density of 1874 W h kg−1, which makes it a promising cathode candidate for next-generation rechargeable lithium (Li) batteries. However, the notorious dissolution of Cu during charging triggers the rapid failure of the CuF2 cathode, impeding its development. In this work, the reversibility of the anhydrous CuF2 electrode was enabled via the use of a fluorinated high-concentration (FHC) electrolyte to effectively suppress the dissolution of Cu. With the FHC electrolyte, the CuF2-Ketjen Black nanocomposite cathode delivered a reversible capacity of 228 mA h g−1 after 30 cycles, which nearly tripled that of the baseline electrolyte. Thus, the strategy of electrolyte engineering is proposed to harness CuF2 as a high-capacity cathode material for Li batteries.

摘要

无水氟化铜(CuF2)有望成为下一代锂电池正极材料, 其高比容量 (528 mA h g−1)和高工作电压(3.55 V vs. Li/Li+)使得其能量密度高达 1874 W h kg−1. 然而, 由于充电时铜的溶解, CuF2正极容易失活, 这限 制了其发展. 本研究采用氟化高浓电解液抑制铜的溶解, 从而实现了 CuF2正极的可逆循环. 采用氟化高浓电解液后, CuF2正极的容量在30 次循环后仍保有228 mA h g−1 是使用传统碳酸酯类电解液的电池容量 的近三倍. 综上, 本研究提出了一种电解质工程策略, 可以实现CuF2正 极的可逆充放电.

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References

  1. Winter M, Barnett B, Xu K. Before Li ion batteries. Chem Rev, 2018, 118: 11433–11456

    Article  CAS  Google Scholar 

  2. Wu F, Maier J, Yu Y. Guidelines and trends for next-generation rechargeable lithium and lithium-ion batteries. Chem Soc Rev, 2020, 49: 1569–1614

    Article  CAS  Google Scholar 

  3. Sandstrom SK, Chen X, Ji X. A review of halide charge carriers for rocking-chair and dual-ion batteries. Carbon Energy, 2021, 3: 627–653

    Article  CAS  Google Scholar 

  4. Zhang K, Hu Z, Tao Z, et al. Inorganic & organic materials for rechargeable Li batteries with multi-electron reaction. Sci China Mater, 2014, 57: 42–58

    Article  Google Scholar 

  5. Liu Q, Wang Y, Yang X, et al. Rechargeable anion-shuttle batteries for low-cost energy storage. Chem, 2021, 7: 1993–2021

    Article  CAS  Google Scholar 

  6. Krishnamurthy V, Viswanathan V. Beyond transition metal oxide cathodes for electric aviation: The case of rechargeable CFx. ACS Energy Lett, 2020, 5: 3330–3335

    Article  CAS  Google Scholar 

  7. Chakraborty A, Kunnikuruvan S, Kumar S, et al. Layered cathode materials for lithium-ion batteries: Review of computational studies on LiNi1−x−yCoxMnyO2 and LiNi1−x−yCoxAlyO2. Chem Mater, 2020, 32: 915–952

    Article  CAS  Google Scholar 

  8. Wang L, Wu Z, Zou J, et al. Li-free cathode materials for high energy density lithium batteries. Joule, 2019, 3: 2086–2102

    Article  CAS  Google Scholar 

  9. Zou J, Yuan K, Zhao J, et al. Delithiation-driven topotactic reaction endows superior cycling performances for high-energy-density FeS (1 ≤ x ≤ 1.14) cathodes. Energy Storage Mater, 2021, 43: 579–584

    Article  Google Scholar 

  10. Ke B, Wang X, Cheng S, et al. Ultrahigh-power iron oxysulfide thin films for microbatteries. Sci China Mater, 2023, 66: 118–126

    Article  CAS  Google Scholar 

  11. Wu F, Srot V, Chen S, et al. 3D honeycomb architecture enables a highrate and long-life iron(III) fluoride-lithium battery. Adv Mater, 2019, 31: 1905146

    Article  CAS  Google Scholar 

  12. Lai C, Chen K, Zheng Y, et al. Tailored deep-eutectic solvent method to enable 3D porous iron fluoride bricks for conversion-type lithium batteries. J Energy Chem, 2023, 78: 178–187

    Article  CAS  Google Scholar 

  13. Chen K, Lei M, Yao Z, et al. Construction of solid-liquid fluorine transport channel to enable highly reversible conversion cathodes. Sci Adv, 2021, 7: eabj1491

    Article  CAS  Google Scholar 

  14. Wu F, Srot V, Chen S, et al. Metal-organic framework-derived nano-confinements of CoF2 and mixed-conducting wiring for high-performance metal fluoride-lithium battery. ACS Nano, 2021, 15: 1509–1518

    Article  CAS  Google Scholar 

  15. Hua X, Eggeman AS, Castillo-Martínez E, et al. Revisiting metal fluorides as lithium-ion battery cathodes. Nat Mater, 2021, 20: 841–850

    Article  CAS  Google Scholar 

  16. Chen M, Zhao L, Li X, et al. Artificial cathode solid electrolyte interphase to endow highly stable lithium storage of FeF2 nanocrystals. Sci China Mater, 2022, 65: 629–636

    Article  CAS  Google Scholar 

  17. Zhao X, Zhao-Karger Z, Fichtner M, et al. Halide-based materials and chemistry for rechargeable batteries. Angew Chem Int Ed, 2020, 59: 5902–5949

    Article  CAS  Google Scholar 

  18. Hu J, Chen K, Yao Z, et al. Unlocking solid-state conversion batteries reinforced by hierarchical microsphere stacked polymer electrolyte. Sci Bull, 2021, 66: 694–707

    Article  CAS  Google Scholar 

  19. Zhang Y, Meng J, Chen K, et al. Garnet-based solid-state lithium fluoride conversion batteries benefiting from eutectic interlayer of superior wettability. ACS Energy Lett, 2020, 5: 1167–1176

    Article  CAS  Google Scholar 

  20. Maulana AY, Futalan CM, Kim J. MOF-derived FeF2 nanoparticles@ graphitic carbon undergoing in situ phase transformation to FeF3 as a superior sodium-ion cathode material. J Alloys Compd, 2020, 840: 155719

    Article  CAS  Google Scholar 

  21. Hwang I, Jung SK, Jeong ES, et al. NaF-FeF2 nanocomposite: New type of Na-ion battery cathode material. Nano Res, 2017, 10: 4388–4397

    Article  CAS  Google Scholar 

  22. Sun Z, Fu W, Liu MZ, et al. A nanoconfined iron(III) fluoride cathode in a NaDFOB electrolyte: Towards high-performance sodium-ion batteries. J Mater Chem A, 2020, 8: 4091–4098

    Article  CAS  Google Scholar 

  23. Zheng Y, Zhang P, Wu SQ, et al. First-principles studies on the structural and electronic properties of Li-ion battery cathode material CuF2. Solid State Commun, 2012, 152: 1703–1706

    Article  CAS  Google Scholar 

  24. Ji E, Huang J, Yu Z, et al. Electrochemical characterization of CuF2/CNTs cathode materials prepared by a coprecipitation method. Funct Mater Lett, 2022, 15: 2251036

    Article  CAS  Google Scholar 

  25. Krahl T, Marroquin Winkelmann F, Martin A, et al. Novel synthesis of anhydrous and hydroxylated CuF2 nanoparticles and their potential for lithium ion batteries. Chem Eur J, 2018, 24: 7177–7187

    Article  CAS  Google Scholar 

  26. Seo JK, Cho HM, Takahara K, et al. Revisiting the conversion reaction voltage and the reversibility of the CuF2 electrode in Li-ion batteries. Nano Res, 2017, 10: 4232–4244

    Article  CAS  Google Scholar 

  27. Chun J, Jo C, Sahgong S, et al. Ammonium fluoride mediated synthesis of anhydrous metal fluoride-mesoporous carbon nanocomposites for high-performance lithium ion battery cathodes. ACS Appl Mater Interfaces, 2016, 8: 35180–35190

    Article  CAS  Google Scholar 

  28. Hua X, Robert R, Du LS, et al. Comprehensive study of the CuF2 conversion reaction mechanism in a lithium ion battery. J Phys Chem C, 2014, 118: 15169–15184

    Article  CAS  Google Scholar 

  29. Wang F, Robert R, Chernova NA, et al. Conversion reaction mechanisms in lithium ion batteries: Study of the binary metal fluoride electrodes. J Am Chem Soc, 2011, 133: 18828–18836

    Article  CAS  Google Scholar 

  30. Cui YH, Xue MZ, Zhou YN, et al. The investigation on electrochemical reaction mechanism of CuF2 thin film with lithium. Electrochim Acta, 2011, 56: 2328–2335

    Article  CAS  Google Scholar 

  31. Mansour AN, Badway F, Yoon WS, et al. In situ X-ray absorption spectroscopic investigation of the electrochemical conversion reactions of CuF2-MoO3 nanocomposite. J Solid State Chem, 2010, 183: 3029–3038

    Article  CAS  Google Scholar 

  32. Wang F, Kim SW, Seo DH, et al. Ternary metal fluorides as high-energy cathodes with low cycling hysteresis. Nat Commun, 2015, 6: 6668

    Article  CAS  Google Scholar 

  33. Huang Y, Zhang W, Li S, et al. Activate metallic copper as high-capacity cathode for lithium-ion batteries via nanocomposite technology. Nano Energy, 2018, 54: 59–65

    Article  CAS  Google Scholar 

  34. Omenya F, Zagarella NJ, Rana J, et al. Intrinsic challenges to the electrochemical reversibility of the high energy density copper(II) fluoride cathode material. ACS Appl Energy Mater, 2019, 2: 5243–5253

    Article  CAS  Google Scholar 

  35. Zhao Y, Wei K, Wu H, et al. LiF splitting catalyzed by dual metal nanodomains for an efficient fluoride conversion cathode. ACS Nano, 2019, 13: acsnano.8b09453

    Article  Google Scholar 

  36. Xia J, Wang Z, Rodrig ND, et al. Super-reversible CuF2 cathodes enabled by Cu2+-coordinated alginate. Adv Mater, 2022, 34: 2205229

    Article  CAS  Google Scholar 

  37. Zhao Q, Lu Y, Zhu Z, et al. Rechargeable lithium-iodine batteries with iodine/nanoporous carbon cathode. Nano Lett, 2015, 15: 5982–5987

    Article  CAS  Google Scholar 

  38. Hashizaki K, Dobashi S, Okada S, et al. Suppression mechanism for dissolution of conversion-type CuCl2 electrode in LiPF6/methyl di-fluoroacetate electrolyte. J Electrochem Soc, 2019, 166: A568–A573

    Article  CAS  Google Scholar 

  39. Li G, Duan X, Liu X, et al. Locking active Li metal through localized redistribution of fluoride enabling stable Li-metal batteries. Adv Mater, 2023, 35: 2207310

    Article  CAS  Google Scholar 

  40. Geng L, Meng J, Wang X, et al. Eutectic electrolyte with unique solvation structure for high-performance zinc-ion batteries. Angew Chem Int Ed, 2022, 61: e202206717

    Article  CAS  Google Scholar 

  41. Fang C, Ye Z, Wang Y, et al. Immobilizing an organic electrode material through π-π interaction for high-performance Li-organic batteries. J Mater Chem A, 2019, 7: 22398–22404

    Article  CAS  Google Scholar 

  42. Dubouis N, Marchandier T, Rousse G, et al. Extending insertion electrochemistry to soluble layered halides with superconcentrated electrolytes. Nat Mater, 2021, 20: 1545–1550

    Article  CAS  Google Scholar 

  43. Yang C, Chen J, Ji X, et al. Aqueous Li-ion battery enabled by halogen conversion-intercalation chemistry in graphite. Nature, 2019, 569: 245–250

    Article  CAS  Google Scholar 

  44. Suo L, Hu YS, Li H, et al. A new class of solvent-in-salt electrolyte for high-energy rechargeable metallic lithium batteries. Nat Commun, 2013, 4: 1481

    Article  Google Scholar 

  45. Hou LP, Li Z, Yao N, et al. Weakening the solvating power of solvents to encapsulate lithium polysulfides enables long-cycling lithium-sulfur batteries. Adv Mater, 2022, 34: 2205284

    Article  CAS  Google Scholar 

  46. Su YS, Manthiram A. Lithium-sulphur batteries with a microporous carbon paper as a bifunctional interlayer. Nat Commun, 2012, 3: 1166

    Article  Google Scholar 

  47. Huang C, Xiao J, Shao Y, et al. Manipulating surface reactions in lithium-sulphur batteries using hybrid anode structures. Nat Commun, 2014, 5: 3015

    Article  Google Scholar 

  48. Cuisinier M, Cabelguen PE, Adams BD, et al. Unique behaviour of nonsolvents for polysulphides in lithium-sulphur batteries. Energy Environ Sci, 2014, 7: 2697–2705

    Article  CAS  Google Scholar 

  49. Azimi N, Xue Z, Bloom I, et al. Understanding the effect of a fluorinated ether on the performance of lithium-sulfur batteries. ACS Appl Mater Interfaces, 2015, 7: 9169–9177

    Article  CAS  Google Scholar 

  50. Tachikawa N, Yamauchi K, Takashima E, et al. Reversibility of electrochemical reactions of sulfur supported on inverse opal carbon in glyme-Li salt molten complex electrolytes. Chem Commun, 2011, 47: 8157–8159

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This work was supported by the Fundamental Research Funds for the Central Universities and the Institute of Carbon Neutrality of Tongji University.

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Authors and Affiliations

  1. Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University, Shanghai, 201804, China

    Yiming Dai  (戴一铭), Xuyang Liu  (刘旭阳), Wangyan Wu  (伍旺炎), Ying Huang  (黄瑛), Tengrui Wang  (王腾锐), Zhenyou Song  (宋振友), Renyuan Zhang  (张任远) & Wei Luo  (罗巍)

  2. Institute of Carbon Neutrality, Tongji University, Shanghai, 200092, China

    Wei Luo  (罗巍)

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  1. Yiming Dai  (戴一铭)
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  2. Xuyang Liu  (刘旭阳)
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  4. Ying Huang  (黄瑛)
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  8. Wei Luo  (罗巍)
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Contributions

Dai Y, Zhang R and Luo W conceived the idea. Huang Y, Liu X, and Wu W provided important experimental insights. Dai Y, Wang T and Song Z performed material fabrication and tests. Dai Y and Luo W co-wrote the paper. All the authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Renyuan Zhang  (张任远) or Wei Luo  (罗巍).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Supporting data are available in the online version of the paper.

Yiming Dai received his BE degree from the East China University of Science and Technology in 2019. He is now a PhD candidate at the Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University. His research interest mainly focuses on conversion-type cathode materials for energy storage devices.

Renyuan Zhang received his PhD degree from Fudan University. He is currently a professor at the Institute of New Energy for Vehicles, School of Materials Science and Engineering, Tongji University. His research interest mainly focuses on energy storage materials, mesoporous materials, and nanomaterials.

Wei Luo is currently a professor at the School of Materials Science and Engineering, Tongji University. He received his PhD degree from Huazhong University of Science and Technology. Prior to his current position, he worked as a postdoctoral researcher at Oregon State University and the University of Maryland (UMD) until being promoted to assistant research professor at UMD. His research interests include solid-state batteries, liquid metals, and high-entropy materials.

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40843_2023_2468_MOESM1_ESM.pdf

Enabling the reversibility of anhydrous copper(II) fluoride cathodes for rechargeable lithium batteries via fluorinated high-concentration electrolytes

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Dai, Y., Liu, X., Wu, W. et al. Enabling the reversibility of anhydrous copper(II) fluoride cathodes for rechargeable lithium batteries via fluorinated high-concentration electrolytes. Sci. China Mater. 66, 3039–3045 (2023). https://doi.org/10.1007/s40843-023-2468-5

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