Synthesis of Nano-CuF₂ with Superior Electrochemical Performances via a Mixed Solvent Coprecipitation Method

Abstract

Nano-scale CuF₂ with superior electrochemical activity was successfully prepared by a mixed solvent co-precipitation method. The SEM and TEM analyses demonstrated that the methanol concentration had a pronounced effect on both the particle size and the extent of agglomeration. With the increase in methanol content, the particle size and agglomeration of CuF₂ decreased first and then increased. When the volume ratio of methanol to deionized water was 1:1, the CuF₂ particles exhibited the smallest size and the lowest degree of agglomeration. CuF₂ synthesized with 50% methanol exhibited superior electrochemical performances with a voltage plateau above 3 V and a 1st discharge capacity of 525.8 mAh·g⁻¹ at 0.01 C due to the synergistic influence of the particle size and dispersion. The analysis results using electrochemical impedance spectroscopy (EIS) and constant current intermittent titration technique (GITT) affirmed the addition of methanol was beneficial for promoting Li⁺ diffusion and accelerating electrochemical reaction kinetics of CuF₂.

Keywords

CuF₂ / lithium-ion battery / mixed solvent / co-precipitation method / electrochemical performances

References

[1] Alsamet M A M M, Burgaz E. Synthesis and Characterization of Nano-Sized LiFePO₄ by Using Consecutive Combination of Col-Gel and Hydrothermal Methods[J]. Electrochim. Acta, 2021, 367: 137 530

[2] Shi X, Zheng T, Xiong J, et al.. Stable Electrode/Electrolyte Interface for High-Voltage NCM 523 Cathode Constructed by Synergistic Positive and Passive Approaches[J]. ACS Appl. Mater. Interfaces, 2021, 13(48): 57 107-57 117

[3] Lee D, Kim H, Jeong S M. Unveiling the Future of Li-Ion Batteries: Real-Time Insights into the Synthesis of Advanced Layered Cathode Materials[J]. ACS Energy Lett., 2024, 9(94 255-4 264

[4] Zhu Z, Yu D, Shi Z, et al.. Gradient-Morph LiCoO₂ Single Crystals with Stabilized Energy Density Above 3 400 Wh·L⁻¹[J]. Energ. Environ. Sci., 2020, 13(6): 1 865-1 878

[5] Liu A, Yuan H, Wang Y, et al.. Reviewing Metal Fluorides as the Cathode Materials for High Performance Li Batteries[J]. Information & Functional Materials, 2024, 1(1): 26-67

[6] Li X, Shen Y, Wang X, et al.. Emerging Halides as a New Class of High-Performance Cathodes[J]. Energy Storage Mater., 2024, 71: 103 660

[7] Luo S, Gao M, Cai D, et al.. Thermodynamic Properties and Composites Design Principles of Metal Fluoride as Active Cathode Material for Lithium Batteries[J]. J. Energy Storage, 2023, 73: 108 483

[8] Wang F, Kim S-W, Seo D-H, et al.. Ternary Metal Fluorides as High-Energy Cathodes with Low Cycling Hysteresis[J]. Nat. Commun., 2015, 6(1): 6 668

[9] Lian J L, Wu Y, Guo Y C A, et al.. Design of Hierarchical and Mesoporous FeF₃/rGO Hybrids as Cathodes for Superior Lithium-Ion Batteries[J]. Chinese Chem. Lett., 2022, 33(83 931-3 935

[10] Gao Y, Li J, Hua Y, et al.. Recent Advances of Metal Fluoride Compounds Cathode Materials for Lithium Ion Batteries: a Review[J]. Mater. Futures, 2024, 3(3032 101

[11] Li C, Chen K, Zhou X, et al.. Electrochemically Driven Conversion Reaction in Fluoride Electrodes for Energy Storage Devices[J]. Npj Comput. Mater., 2018, 4(122

[12] Zhang J, Qiao J, Sun K, et al.. Balancing Particle Properties for Practical Lithium-Ion Batteries[J]. Particuology, 2022, 61: 18-29

[13] Badway F, Pereira N, Cosandey F, et al.. Carbon-Metal Fluoride Nano-composites: Structure and Electrochemistry[J]. J. Electrochem. Soc., 2003, 150(9A1 209

[14] Owen N, Zhang Q. Investigations of Aluminum Fluoride as a New Cathode Material for Lithium-Ion Batteries[J]. J. Appl. Electrochem., 2017, 47(4417-431

[15] Baumgärtner J F, Krumeich F, Wörle M, et al.. Thermal Synthesis of Conversion-Type Bismuth Fluoride Cathodes for High-Energy-Density Li-Ion Batteries[J]. Commun. Chem., 2022, 5(1): 6

[16] Konishi H, Minato T, Abe T, et al.. Difference of Rate Performance Between Discharge and Charge Reactions for Bismuth Fluoride Electrode in Lithium-Ion Battery[J]. J. Electroanal. Chem., 2017, 806: 82-87

[17] Piras C C, Fernández-Prieto S, De Borggraeve W M. Ball Milling: a Green Technology for the Preparation and Functionalisation of Nano-cellulose Derivatives[J]. Nanoscale Adv., 2019, 1(3937-947

[18] Krahl T, Marroquin Winkelmann F, Martin A, et al.. Novel Synthesis of Anhydrous and Hydroxylated CuF₂ Nanoparticles and Their Potential for Lithium Ion Batteries[J]. Chem.-Eur. J., 2018, 24(28): 7 177-7 187

[19] Sun H, Zhou H, Xu Z, et al.. Preparation of Anhydrous Iron Fluoride with Porous Fusiform Structure and Its Application for Li-Ion Batteries[J]. Micropor. Mesopor. Mat., 2017, 253: 10-17

[20] Huang Y, Li X, Ding R, et al.. Tetragonal MF₂ (M=Ni, Co) Micro/Nanocrystals Anodes for Lithium/Sodium-Ion Capacitors[J]. Electrochim. Acta, 2020, 329: 135 138

[21] Guntlin C P, Zünd T, Kravchyk K V, et al.. Nanocrystalline FeF₃ and MF₂ (M = Fe, Co, and Mn) from Metal Trifluoroacetates and Their Li(Na)-Ion Storage Properties[J]. J. Mater. Chem. A, 2017, 5(16): 7 383-7 393

[22] Li Y, Yao F, Cao Y, et al.. The Mediated Synthesis of FeF₃ Nanocrystals Through (NH₄)₃FeF₆ Precursors as the Cathode Material for High Power Lithium Ion Batteries[J]. Electrochim. Acta, 2017, 253: 545-553

[23] Ji E, Huang J, Yu Z, et al.. Electrochemical Characterization of CuF₂/CNTs Cathode Materials Prepared by a Coprecipitation Method[J]. Funct. Mater. Lett., 2022, 15(05225 1036

[24] Feng C, Zhang L, Wang Z, et al.. Synthesis of Copper Sulfide Nanowire Bundles in a Mixed Solvent as a Cathode Material for Lithium-Ion Batteries[J]. J. Power Sources, 2014, 269: 550-555

[25] Shen Y, Ju X, Zhang J, et al.. A Convenient Co-Precipitation Method to Prepare High Performance LiNi_0.5Mn_1.5O₄ Cathode for Lithium Ion Batteries[J]. Mater. Chem. Phys., 2020, 240: 122 137

[26] He L, Xue L, Kuai H, et al.. N, N-Dimethylacetamide-Water Mixed Solvent Synthesis of Mesoporous MnC₂O₄ Rod as High Performance Anode Material for Lithium-Ion Batteries[J]. Ionics, 2021, 27(41 413-1 422

[27] Chen H I, Chang H Y. Homogeneous Precipitation of Cerium Dioxide Nanoparticles in Alcohol/Water Mixed Solvents[J]. Colloid Surface A, 2004, 242(1–361-69

[28] Babick F. Suspensions of Colloidal Particles and Aggregates, 2016, Berlin, Springer M]

[29] Wu K J, Tse E C M, Shang C, et al.. Nucleation and Growth in Solution Synthesis of Nanostructures-from Fundamentals to Advanced Applications[J]. Prog. Mater. Sci., 2022, 123: 100 821

[30] Hu Q X, Yu Z Y, Tian L J, et al.. Porous Anhydrous CuF₂ with a Micro-Nano-Hierarchical Structure as High-Performance Cathode Material for Li-Ion Battery[J]. J. Mater. Sci., 2023, 58(2410 120-10 130

[31] Hu Q X, Yu Z Y, Tian L J, et al.. Porous CuF2 Integrated with a Three-Dimensional Conductive Network of CNTs as Cathode Materials for Lithium-Ion Batteries[J]. J. Mater. Sci.-Mater. EL, 2023, 34(131 076

[32] Weppner W, Huggins R A. Determination of the Kinetic Parameters of Mixed-Conducting Electrodes and Application to the System Li₃Sb[J]. J. Electrochem. Soc., 1977, 124(101 569

RIGHTS & PERMISSIONS

Wuhan University of Technology and Springer-Verlag GmbH Germany, Part of Springer Nature