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Rational design of anti-freezing electrolytes for extremely low-temperature aqueous batteries

Nature Energy (2024)Cite this article

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Abstract

Designing anti-freezing electrolytes through choosing suitable H2O–solute systems is crucial for low-temperature aqueous batteries (LTABs). However, the lack of an effective guideline for choosing H2O–solute systems based on decisive temperature-limiting factors hinders the development of LTABs. Here we identified two decisive factors: thermodynamic eutectic temperature (Te) and kinetic glass-transition temperature (Tg), with Tg being applicable for LTABs only when H2O–solute systems have strong super-cooling ability. We proposed a general strategy wherein low-Te and strong-super-cooling ability electrolytes can be realized by creating multiple-solute systems via introducing assisted salts with high ionic-potential cations (for example, Al3+, Ca2+) or cosolvents with high donor numbers (for example, ethylene glycol). As a demonstration in Na-based systems, we designed electrolytes with ultralow Te (−53.5 to −72.6 °C) and Tg (−86.1 to −117.1 °C), showcasing battery performances including 80 Wh kg−1 and 5,000 cycles at 25 °C, and 12.5 Wh kg−1 at −85 °C. The work provides effective guidelines for the design of anti-freezing electrolytes for extremely low-temperature applications.

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Fig. 1: Schematic evolution of a dilute solution in the H2O–solute system during cooling process and the difference between traditional and our proposed strategies.
Fig. 2: Design of low-Te and strong-SCA aqueous electrolytes.
Fig. 3: The low-Te mechanisms in designed electrolytes.
Fig. 4: The strong-SCA mechanisms in designed electrolytes.
Fig. 5: Battery demonstrations in designed electrolytes.

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The datasets analysed and generated during the current study are included in the paper and its Supplementary Information.

References

  1. Xu, J. et al. Electrolyte design for Li-ion batteries under extreme operating conditions. Nature 614, 694–700 (2023).

    Article  Google Scholar 

  2. Rodrigues, M.-T. F. et al. A materials perspective on Li-ion batteries at extreme temperatures. Nat. Energy 2, 17108 (2017).

    Article  Google Scholar 

  3. Zhu, G. et al. Rechargeable Na/Cl2 and Li/Cl2 batteries. Nature 596, 525–530 (2021).

    Article  Google Scholar 

  4. Ai, F. et al. Heteropoly acid negolytes for high-power-density aqueous redox flow batteries at low temperatures. Nat. Energy 7, 417–426 (2022).

    Article  Google Scholar 

  5. Jiang, L. W., Hu, Y.-C., Ai, F., Liang, Z. J. & Lu, Y.-C. Rational design of anti-freezing electrolyte concentrations via freeze concentration process. Energy Environ. Sci. 17, 2815–2824 (2024).

    Article  Google Scholar 

  6. Jiang, L., Dong, D. & Lu, Y.-C. Design strategies for low temperature aqueous electrolytes. Nano Res. Energy 1, e9120003 (2022).

    Article  Google Scholar 

  7. Guo, Q., Han, S., Lu, Y., Chen, L. & Hu, Y.-S. Low-temperature aqueous Na-ion batteries: strategies and challenges of electrolyte design. Chin. Phys. Lett. 40, 028801 (2023).

    Article  Google Scholar 

  8. Yue, J. et al. Aqueous interphase formed by CO2 brings electrolytes back to salt-in-water regime. Nat. Chem. 13, 1061–1069 (2021).

    Article  Google Scholar 

  9. Jiang, L. et al. Building aqueous K-ion batteries for energy storage. Nat. Energy 4, 495–503 (2019).

    Article  Google Scholar 

  10. Zhang, Q. et al. Chaotropic anion and fast-kinetics cathode enabling low-temperature aqueous Zn batteries. ACS Energy Lett. 6, 2704–2712 (2021).

    Article  Google Scholar 

  11. Tang, L. et al. Strengthening aqueous electrolytes without strengthening water. Angew. Chem. Int. Ed. 62, e202307212 (2023).

    Article  Google Scholar 

  12. Qiu, M. et al. Tailoring water structure with high-tetrahedral-entropy for antifreezing electrolytes and energy storage at −80 °C. Nat. Commun. 14, 601 (2023).

    Article  Google Scholar 

  13. Zhu, K. et al. Inorganic electrolyte for low‐temperature aqueous sodium ion batteries. Small 18, 2107662 (2022).

    Article  Google Scholar 

  14. Zhu, K. et al. Tailoring pure inorganic electrolyte for aqueous sodium‐ion batteries operating at −60 °C. Batter. Supercaps. 5, e202200308 (2022).

    Article  Google Scholar 

  15. Nian, Q. S. et al. Aqueous batteries operated at −50 °C. Angew. Chem. Int. Ed. 58, 16994–16999 (2019).

    Article  Google Scholar 

  16. Suo, L. et al. ‘Water-in-salt’ electrolytes enable green and safe Li-ion batteries for large scale electric energy storage applications. J. Mater. Chem. A 4, 6639–6644 (2016).

    Article  Google Scholar 

  17. Nian, Q. et al. Regulating frozen electrolyte structure with colloidal dispersion for low temperature aqueous batteries. Angew. Chem. Int. Ed. 62, e202217671 (2023).

    Article  Google Scholar 

  18. Sun, Y. et al. Salty ice electrolyte with superior ionic conductivity towards low‐temperature aqueous zinc ion hybrid capacitors. Adv. Funct. Mater. 31, 2101277 (2021).

    Article  Google Scholar 

  19. Guo, Z. et al. An organic/inorganic electrode-based hydronium-ion battery. Nat. Commun. 11, 959 (2020).

    Article  Google Scholar 

  20. Sui, Y. et al. Reversible Cl2/Cl– redox for low-temperature aqueous batteries. ACS Energy Lett. 8, 988–994 (2023).

    Article  Google Scholar 

  21. Jiang, L. & Lu, Y.-C. Building a long-lifespan aqueous K-ion battery operating at −35 °C. ACS Energy Lett. 9, 985–991 (2024).

    Article  Google Scholar 

  22. Zhang, Q. et al. Modulating electrolyte structure for ultralow temperature aqueous zinc batteries. Nat. Commun. 11, 4463 (2020).

    Article  Google Scholar 

  23. Monnin, C., Dubois, M., Papaiconomou, N. & Simonin, J.-P. Thermodynamics of the LiCl+ H2O system. J. Chem. Eng. Data 47, 1331–1336 (2002).

    Article  Google Scholar 

  24. Wang, Q., Zhao, L., Li, C. & Cao, Z. The decisive role of free water in determining homogenous ice nucleation behavior of aqueous solutions. Sci. Rep. 6, 26831 (2016).

    Article  Google Scholar 

  25. Corti, H. R., Nores-Pondal, F. J. & Angell, C. A. Heat capacity and glass transition in P2O5-H2O solutions: support for Mishima’s conjecture on solvent water at low temperature. Phys. Chem. Chem. Phys. 13, 19741–19748 (2011).

    Article  Google Scholar 

  26. Pillai, S. B., Wilcox, R. J., Hillis, B. G., Losey, B. P. & Martin, J. D. Understanding the water-in-salt to salt-in-water characteristics across the zinc chloride: water phase diagram. J. Phys. Chem. B 126, 2265–2278 (2022).

    Article  Google Scholar 

  27. Jiang, H. et al. A high‐rate aqueous proton battery delivering power below −78 °C via an unfrozen phosphoric acid. Adv. Energy Mater. 10, 2000968 (2020).

    Article  Google Scholar 

  28. Gibout, S., Franquet, E., Haillot, D., Bédécarrats, J.-P. & Dumas, J.-P. Challenges of the usual graphical methods used to characterize phase change materials by differential scanning calorimetry. Appl. Sci. 8, 66 (2018).

    Article  Google Scholar 

  29. Ding, M., Xu, K. & Jow, T. Phase diagram of EC–DMC binary system and enthalpic determination of its eutectic composition. J. Therm. Anal. Calorim. 62, 177–186 (2000).

    Article  Google Scholar 

  30. Franquet, E., Gibout, S., Bédécarrats, J. P., Haillot, D. & Dumas, J. P. Inverse method for the identification of the enthalpy of phase change materials from calorimetry experiments. Thermochim. Acta 546, 61–80 (2012).

    Article  Google Scholar 

  31. Zhao, L., Pan, L., Cao, Z. & Wang, Q. Confinement-induced vitrification of aqueous sodium chloride solutions. Chem. Phys. Lett. 647, 170–174 (2016).

    Article  Google Scholar 

  32. Zhao, L. S., Cao, Z. X. & Wang, Q. Glass transition of aqueous solutions involving annealing-induced ice recrystallization resolves liquid-liquid transition puzzle of water. Sci. Rep. 5, 15714 (2015).

    Article  Google Scholar 

  33. Wang, X., Huang, W., Liu, F., Liu, N. & Huang, X. Determination and graphics expression of ice-salt eutectic points of the multicomponent electrolyte solutions. Fluid Phase Equilib. 458, 115–122 (2018).

    Article  Google Scholar 

  34. Yu, D., Xue, Z. & Mu, T. Eutectics: formation, properties, and applications. Chem. Soc. Rev. 50, 8596–8638 (2021).

    Article  Google Scholar 

  35. Walrafen, G. E. Raman spectral studies of the effects of temperature on water structure. J. Chem. Phys. 47, 114–126 (1967).

    Article  Google Scholar 

  36. Hare, D. E. & Sorensen, C. M. Raman spectroscopic study of bulk water supercooled to −33 °C. J. Chem. Phys. 93, 25–33 (1990).

    Article  Google Scholar 

  37. Wang, Y. H. et al. In situ Raman spectroscopy reveals the structure and dissociation of interfacial water. Nature 600, 81–85 (2021).

    Article  Google Scholar 

  38. Yang, B., Cao, X., Wang, C., Wang, S. & Sun, C. Investigation of hydrogen bonding in water/DMSO binary mixtures by Raman spectroscopy. Spectrochim. Acta A Mol. Biomol. Spectrosc. 228, 117704 (2020).

    Article  Google Scholar 

  39. Hu, Y.-C. & Tanaka, H. Physical origin of glass formation from multicomponent systems. Sci. Adv. 6, eabd2928 (2020).

    Article  Google Scholar 

  40. Tanaka, H. Bond orientational order in liquids: towards a unified description of water-like anomalies, liquid–liquid transition, glass transition, and crystallization. Eur. Phys. J. E 35, 113 (2012).

    Article  Google Scholar 

  41. Hu, Y.-C. & Tanaka, H. Revealing the role of liquid preordering in crystallisation of supercooled liquids. Nat. Commun. 13, 4519 (2022).

    Article  Google Scholar 

  42. Jiang, L. et al. High-voltage aqueous Na-ion battery enabled by inert-cation-assisted water-in-salt electrolyte. Adv. Mater. 32, 1904427 (2020).

    Article  Google Scholar 

  43. Reber, D., Kühnel, R.-S. & Battaglia, C. Suppressing crystallization of water-in-salt electrolytes by asymmetric anions enables low-temperature operation of high-voltage aqueous batteries. ACS Mater. Lett. 1, 44–51 (2019).

    Article  Google Scholar 

  44. Wu, X. Y. et al. Energetic aqueous rechargeable sodium‐ion battery based on Na2CuFe(CN)6–NaTi2(PO4)3 intercalation chemistry. Chem. Sus. Chem. 7, 407–411 (2014).

    Article  Google Scholar 

  45. Fernández-Ropero, A. J., Saurel, D., Acebedo, B., Rojo, T. & Casas-Cabanas, M. Electrochemical characterization of NaFePO4 as positive electrode in aqueous sodium-ion batteries. J. Power Sources 291, 40–45 (2015).

    Article  Google Scholar 

  46. Zhang, Y. et al. All-climate aqueous Na-ion batteries using ‘water-in-salt’ electrolyte. Sci. Bull. 67, 161–170 (2022).

    Article  Google Scholar 

  47. Yue, J. et al. Interface concentrated‐confinement suppressing cathode dissolution in water‐in‐salt electrolyte. Adv. Energy Mater. 10, 2000665 (2020).

    Article  Google Scholar 

  48. Ding, M. S. & Xu, K. Phase diagram, conductivity, and glass transition of LITFSI–H2O binary electrolytes. J. Phys. Chem. C. 122, 16624–16629 (2018).

    Article  Google Scholar 

  49. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).

    Article  Google Scholar 

  50. Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996).

    Article  Google Scholar 

  51. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865 (1996).

    Article  Google Scholar 

  52. Dion, M., Rydberg, H., Schroder, E., Langreth, D. C. & Lundqvist, B. I. Van der Waals density functional for general geometries. Phys. Rev. Lett. 92, 246401 (2004).

    Article  Google Scholar 

  53. Nosé, S. A unified formulation of the constant temperature molecular dynamics methods. J. Chem. Phys. 81, 511–519 (1984).

    Article  Google Scholar 

  54. Hoover, W. G. Canonical dynamics: equilibrium phase-space distributions. Phys. Rev. A 31, 1695 (1985).

    Article  Google Scholar 

  55. Martínez, L., Andrade, R., Birgin, E. G. & Martínez, J. M. PACKMOL: a package for building initial configurations for molecular dynamics simulations. J. Comput. Chem. 30, 2157–2164 (2009).

    Article  Google Scholar 

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (grant nos. 52122214 received by Y.L. and 52072370 received by J.Z.), Youth Innovation Promotion Association of the Chinese Academy of Sciences (grant no. 2020006 received by Y.L.), Jiangsu Province Carbon Peak and Neutrality Innovation Program (Industry tackling on prospect and key technology grant no. BE2022002-5 received by Y.-S.H.), Beijing Natural Science Foundation (grant no. 2222078 received by J.Z.), Guangxi Power Grid Project (grant no. GXKJXM20210260 received by Y.-S.H.) and the Research Grant Council of the Hong Kong Special Administrative Region, China (grant nos. CUHK 14308622 and C1002-21G received by Y.-C.L.). We are grateful to B. Dunn for his suggestions on understanding electrolyte performance and mechanisms.

Author information

Author notes

  1. These authors contributed equally: Liwei Jiang, Shuai Han, Yuan-Chao Hu.

Authors and Affiliations

  1. Key Laboratory for Renewable Energy, Beijing Key Laboratory for New Energy Materials and Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China

    Liwei Jiang, Shuai Han, Yang Yang, Yaxiang Lu, Liquan Chen & Yong-Sheng Hu

  2. College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing, China

    Liwei Jiang, Shuai Han, Yang Yang & Yong-Sheng Hu

  3. Electrochemical Energy and Interfaces Laboratory, Department of Mechanical and Automation Engineering, The Chinese University of Hong Kong, Hong Kong, China

    Liwei Jiang & Yi-Chun Lu

  4. Songshan Lake Materials Laboratory, Dongguan, China

    Yuan-Chao Hu

  5. Yangtze River Delta Physics Research Center Co. Ltd, Liyang, China

    Yaxiang Lu & Yong-Sheng Hu

  6. CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China

    Junmei Zhao

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Contributions

L.J., Y.-S.H., J.Z., Y.-C.L. and Y.L. conceived the project. L.J. synthesized the NaFeMnHCF cathode and carried out electrochemical tests, DSC tests, AIMD simulations and DFT calculations. S.H. synthesized the NaTi2(PO4)3 anode and carried out NMR and DSC tests. Y.-C.H. contributed to the electrolyte strong-SCA mechanisms. L.J., S.H., Y.-C.H., Y.L, Y.-C.L., J.Z. and Y.-S.H. wrote the paper. All the authors participated in the preparation of paper.

Corresponding authors

Correspondence to Yaxiang Lu, Yi-Chun Lu, Junmei Zhao or Yong-Sheng Hu.

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Y.-S.H. is employed by HiNa Battery Technology Co., Ltd. The other authors declare no competing interests.

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Nature Energy thanks Xiulei Ji and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Notes 1–4, Figs. 1–24 and Tables 1–7.

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Jiang, L., Han, S., Hu, YC. et al. Rational design of anti-freezing electrolytes for extremely low-temperature aqueous batteries. Nat Energy (2024). https://doi.org/10.1038/s41560-024-01527-5

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