Electrolyte Design via Hydrogen Bonding Between Solvent and Non-Solvating Cosolvent Enabling Stable Lithium Metal Batteries at −20°C

Abstract

Lithium metal batteries (LMBs) have great significance in enhancing energy density. However, low ion diffusion in bulk electrolytes, high desolvation energy of Li⁺, and sluggish ion transport kinetics in electrode interphases at low temperatures cause LMBs to have a short cycle life (usually below 300 cycles). In this study, we designed a low-temperature electrolyte to overcome these issues. The medium-chain length isopropyl formate (IPF) was employed as main solvent in the designed electrolyte. Especially, the hydrogen bonding between non-solvating cosolvent (1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether [TFE]) and IPF can be formed, leading to the weakened interaction between Li⁺ and the solvents. Thus, a fast Li⁺ desolvation can be achieved. Additionally, the designed electrolyte can maintain a high conductivity (6.37 mS cm⁻¹) at −20°C and achieve higher Li⁺ transference numbers (0.62). Finally, Li||LiFePO₄ full cells using the designed electrolyte exhibit a capacity of 113 mAh g⁻¹ after 480 cycles at 0.1C under −20°C. Meanwhile, Li||LiFePO₄ can deliver 150 mAh g⁻¹ after 120 cycles at 50°C. This study provides a novel pathway for optimizing electrolytes for next-generation LMBs during low-temperature operations.

Keywords

high conductivity / ion transport kinetics / lithium metal batteries / solvation structure

References

[1] J. Liu, Z. Bao, Y. Cui, et al., “Pathways for Practical High-Energy Long-Cycling Lithium Metal Batteries,” Nature Energy 4 (2019): 180–186.

[2] G. Song, Z. Yi, F. Su, et al., “Boosting the Low-Temperature Performance for Li-Ion Batteries in LiPF₆-Based Local High-Concentration Electrolyte,” ACS Energy Letters 8 (2023): 1336–1343.

[3] L. Luo, K. Chen, H. Chen, et al., “Enabling Ultralow-Temperature (−70°C) Lithium-Ion Batteries: Advanced Electrolytes Utilizing Weak-Solvation and Low-Viscosity Nitrile Cosolvent,” Advanced Materials 36 (2023): 2308881.

[4] P. Lai, B. Huang, X. Deng, et al., “A Localized High Concentration Carboxylic Ester-Based Electrolyte for High-Voltage and Low Temperature Lithium Batteries,” Chemical Engineering Journal 461 (2023): 141904.

[5] Y. Lin, Z. Yang, X. Zhang, et al., “Activating Ultra-Low Temperature Li-Metal Batteries by Tetrahydrofuran-Based Localized Saturated Electrolyte,” Energy Storage Materials 58 (2023): 184–194.

[6] M. T. F. Rodrigues, G. Babu, H. Gullapalli, et al., “A Materials Perspective on Li-Ion Batteries at Extreme Temperatures,” Nature Energy 2 (2017): 17108.

[7] Z. Wang, F. Qi, L. Yin, et al., “An Anion−Tuned Solid Electrolyte Interphase With Fast Ion Transfer Kinetics for Stable Lithium Anodes,” Advanced Energy Materials 10 (2020): 1903843.

[8] J. Chen, Y. Zhang, H. Lu, et al., “Electrolyte Solvation Chemistry to Construct an Anion-Tuned Interphase for Stable High-Temperature Lithium Metal Batteries,” eScience 3 (2023): 100135.

[9] J. Yu, X. Lin, J. Liu, et al., “In Situ Fabricated Quasi-Solid Polymer Electrolyte for High-Energy-Density Lithium Metal Battery Capable of Subzero Operation,” Advanced Energy Materials 12 (2022): 2102932.

[10] H. Li, F. Zhang, W. Wei, et al., “Promoting Air Stability of Li Anode via an Artificial Organic/Inorganic Hybrid Layer for Dendrite-Free Lithium Batteries,” Advanced Energy Materials 13 (2023): 2301023.

[11] Y. He, W. Shang, and P. Tan, “Insight into Rechargeable Batteries in Extreme Environment for Deep Space Exploration,” Carbon Neutralization 3 (2024): 773–780.

[12] S. Lei, Z. Zeng, H. Yan, et al., “Nonpolar Cosolvent Driving LUMO Energy Evolution of Methyl Acetate Electrolyte to Afford Lithium-Ion Batteries Operating at −60°C,” Advanced Functional Materials 33 (2023): 2301028.

[13] Y. Yang, W. Yang, H. Yang, et al., “Electrolyte Design Principles for Low-Temperature Lithium-Ion Batteries,” eScience 4 (2023): 100170.

[14] R. Fang, S. Zhao, K. Chen, D. W. Wang, and F. Li, “Binary Graphene-Based Cathode Structure for High-Performance Lithium-Sulfur Batteries,” Journal of Physics: Energy 2 (2020): 015003.

[15] E. Fan, L. Li, Z. Wang, et al., “Sustainable Recycling Technology for Li-Ion Batteries and Beyond: Challenges and Future Prospects,” Chemical Reviews 120 (2020): 7020–7063.

[16] T. Ma, Y. Ni, Q. Wang, et al., “Optimize Lithium Deposition at Low Temperature by Weakly Solvating Power Solvent,” Angewandte Chemie International Edition 61 (2022): e202207927.

[17] Y. Zhang, S. Wu, and Q. H. Yang, “Revisiting Lithium Metal Anodes From a Dynamic and Realistic Perspective,” EnergyChem 3 (2021): 100063.

[18] A. Zhamu, G. Chen, C. Liu, et al., “Reviving Rechargeable Lithium Metal Batteries: Enabling Next-Generation High-Energy and High-Power Cells,” Energy & Environmental Science 5 (2012): 5701–5707.

[19] X. B. Cheng, R. Zhang, C. Z. Zhao, and Q. Zhang, “Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review,” Chemical Reviews 117 (2017): 10403–10473.

[20] J. G. Zhang, W. Xu, J. Xiao, X. Cao, and J. Liu, “Lithium Metal Anodes With Nonaqueous Electrolytes,” Chemical Reviews 120 (2020): 13312–13348.

[21] Q. Zhang, J. Pan, P. Lu, et al., “Synergetic Effects of Inorganic Components in Solid Electrolyte Interphase on High Cycle Efficiency of Lithium Ion Batteries,” Nano Letters 16 (2016): 2011–2016.

[22] H. Zeng, K. Yu, J. Li, et al., “Beyond LiF: Tailoring Li₂O-Dominated Solid Electrolyte Interphase for Stable Lithium Metal Batteries,” ACS Nano 18 (2024): 1969–1981.

[23] Y. Yang, W. Yang, H. Yang, et al., “Electrolyte Design Principles for Low-Temperature Lithium-Ion Batteries,” eScience 4 (2023): 100170.

[24] Y. Liu, J. Li, X. Deng, et al., “Regulating Electrolyte Solvation Structures via Diluent-Solvent Interactions for Safe High-Voltage Lithium Metal Batteries,” Small 10 (2024): 2311812.

[25] G. Zhang, J. Li, S. S. Chi, et al., “Molecular Design of Competitive Solvation Electrolytes for Practical High-Energy and Long-Cycling Lithium-Metal Batteries,” Advanced Functional Materials 34 (2024): 202312413.

[26] J. Moon, D. O. Kim, L. Bekaert, et al., “Non-Fluorinated Non-Solvating Cosolvent Enabling Superior Performance of Lithium Metal Negative Electrode Battery,” Nature Communications 13 (2022): 4538.

[27] Y. Yamada, J. Wang, S. Ko, E. Watanabe, and A. Yamada, “Advances and Issues in Developing Salt−Concentrated Battery Electrolytes,” Nature Energy 4, no. 12019 (2019): 269–280.

[28] S. Chen, J. Zheng, D. Mei, et al., “High-Voltage Lithium-Metal Batteries Enabled by Localized High-Concentration Electrolytes,” Advanced Materials 30 (2018): 1706102.

[29] J. Holoubek, K. Kim, Y. Yin, et al., “Electrolyte Design Implications of Ion-Pairing in Low-Temperature Li Metal Batteries,” Energy & Environmental Science 15 (2022): 1647–1658.

[30] S. Kim, J. Lee, T. Lee, et al., “Wide-Temperature-Range Operation of Lithium-Metal Batteries Using Partially and Weakly Solvating Liquid Electrolytes,” Energy & Environmental Science 16 (2023): 5108–5122.

[31] J. Holoubek, M. Yu, S. Yu, et al., “An All-Fluorinated Ester Electrolyte For Stable High-Voltage Li Metal Batteries Capable of Ultra-Low-Temperature Operation,” ACS Energy Letters 5 (2020): 1438–1447.

[32] Y. Cho, M. Li, J. Holoubek, et al., “Enabling the Low-Temperature Cycling of NMC||Graphite Pouch Cells With an Ester-Based Electrolyte,” ACS Energy Letters 6 (2021): 2016–2023.

[33] Z. Piao, X. Wu, H. R. Ren, et al., “A Semi-Solvated Sole-Solvent Electrolyte for High-Voltage Lithium Metal Batteries,” Journal of the American Chemical Society 145 (2023): 24260–24271.

[34] E. Markevich, G. Salitra, F. Chesneau, M. Schmidt, and D. Aurbach, “Very Stable Lithium Metal Stripping-Plating at A High Rate and High Areal Capacity in Fluoroethylene Carbonate-Based Organic Electrolyte Solution,” ACS Energy Letters 2 (2017): 1321–1326.

[35] J. Holoubek, H. Liu, Z. Wu, et al., “Tailoring Electrolyte Solvation for Li Metal Batteries Cycled at Ultra-Low Temperature,” Nature Energy 6 (2021): 303–313.

[36] L. Suo, F. Zheng, Y. S. Hu, and L. Chen, “FT-Raman Spectroscopy Study of Solvent-in-Salt Electrolytes,” Chinese Physics B 25 (2016): 016101.

[37] J. Wu, Z. Gao, Y. Tian, et al., “Unique Tridentate Coordination Tailored Solvation Sheath Toward Highly Stable Lithium Metal Batteries,” Advanced Materials 35 (2023): 2303347.

[38] A. C. Thenuwara, P. P. Shetty, and M. T. McDowell, “Distinct Nanoscale Interphases and Morphology of Lithium Metal Electrodes Operating at Low Temperatures,” Nano Letters 19 (2019): 8664–8672.

[39] W. W. Han, R. E. A. Ardhi, and G. C. Liu, “Dual Impact of Superior SEI and Separator Wettability to Inhibit Lithium Dendrite Growth,” Rare Metals 41 (2022): 353–355.

[40] X. Zheng, L. Huang, W. Luo, et al., “Tailoring Electrolyte Solvation Chemistry Toward an Inorganic-Rich Solid-Electrolyte Interphase at a Li Metal Anode,” ACS Energy Letters 6 (2021): 2054–2063.

[41] W. Zhang, Q. Wu, J. Huang, et al., “Colossal Granular Lithium Deposits Enabled by the Grain-Coarsening Effect for High-Efficiency Lithium Metal Full Batteries,” Advanced Materials 32 (2020): 2001740.

[42] T. Kondo and Y. Yamada, “Kinetics of Interfacial Ion Transfer in Lithium-Ion Batteries: Mechanism Understanding and Improvement Strategies,” ACS Applied Materials & Interfaces 14 (2022): 22706–22718.

[43] A. Hu, F. Li, W. Chen, et al., “Ion Transport Kinetics in Low-Temperature Lithium Metal Batteries,” Advanced Energy Materials 12 (2022): 2202432.

[44] D. Hubble, D. Brown, Y. Zhao, et al., “Liquid Electrolyte Development for Low-Temperature Lithium-Ion Batteries,” Energy & Environmental Science 15 (2022): 550–578.

[45] Y. Feng, L. Zhou, H. Ma, et al., “Challenges and Advances in Wide-Temperature Rechargeable Lithium Batteries,” Energy & Environmental Science 15 (2022): 1711–1759.

[46] Z. Wang, Z. Sun, Y. Shi, et al., “Lithium Metal Batteries: Ion-Dipole Chemistry Drives Rapid Evolution of Li Ions Solvation Sheath in Low-Temperature Li Batteries,” Advanced Energy Materials 11 (2021): 2100935.

[47] X. Shangguan, G. Xu, Z. Cui, et al., “Additive-Assisted Novel Dual-Salt Electrolyte Addresses Wide Temperature Operation of Lithium–Metal Batteries,” Small 15 (2019): 1900269.

[48] Y. Zou, F. Cheng, Y. Lu, Y. Xu, C. Fang, and J. Han, “High Performance Low-Temperature Lithium Metal Batteries Enabled by Tailored Electrolyte Solvation Structure,” Small 19 (2023): 2203394.

[49] Y. Yang, Y. Yin, D. Davies, et al., “Liquefied Gas Electrolytes for Wide-Temperature Lithium Metal Batteries,” Energy & Environmental Science 13 (2020): 2209–2219.

[50] J. Shi, C. Xu, J. Lai, et al., “An Amphiphilic Molecule-Regulated Core-Shell-Solvation Electrolyte for Li-Metal Batteries at Ultra-Low Temperature,” Angewandte Chemie International Edition 62 (2023): e202218151.

[51] S. Tan, Z. Shadike, J. Li, et al., “Additive Engineering for Robust Interphases to Stabilize High−Ni Layered Structures at Ultra-High Voltage of 4.8 V,” Nature Energy 7 (2022): 484–494.

[52] C. Yan, H. R. Li, X. Chen, et al., “Regulating the Inner Helmholtz Plane for Stable Solid Electrolyte Interphase on Lithium Metal Anodes,” Journal of the American Chemical Society 141 (2019): 9422–9429.

[53] Z. Wen, W. Fang, F. Wang, et al., “Dual−Salt Electrolyte Additive Enables High Moisture Tolerance and Favorable Electric Double Layer for Lithium Metal Battery,” Angewandte Chemie International Edition 63 (2024): e202314876.

[54] T. Yang, H. Zeng, W. Wang, et al., “Lithium Bisoxalatodifluorophosphate (LiBODFP) as a Multifunctional Electrolyte Additive for 5 V LiNi_0.5Mn_1.5O₄-Based Lithium-Ion Batteries With Enhanced Electrochemical Performance,” Journal of Materials Chemistry A 7 (2019): 8292–8301.

[55] B. Nan, L. Chen, N. D. Rodrigo, et al., “Enhancing Li⁺ Transport in NMC811 ||Graphite Lithium-Ion Batteries at Low Temperatures by Using Low-Polarity-Solvent Electrolytes,” Angewandte Chemie 61 (2022): e2022059.

[56] Q. Jiang, M. Li, J. Li, et al., “LiF-Rich Cathode Electrolyte Interphases Homogenizing Li⁺ Fluxes Toward Stable Interface in Li-Rich Mn-Based Cathodes,” Advanced Materials 37 (2025): 2417620.

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