Issue

Vol. 17 (2025)

Advances in Anion Chemistry in the Electrolyte Design for Better Lithium Batteries

https://doi.org/10.1007/s40820-024-01629-5
Hecong Xiao
College of Chemistry, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Xiang Li
College of Chemistry, Zhengzhou University, Zhengzhou 450001, People’s Republic of China
Yongzhu Fu
College of Chemistry, Zhengzhou University, Zhengzhou 450001, People’s Republic of China

Corresponding Author: Yongzhu Fu

yfu@zzu.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 149

Abstract

Electrolytes are crucial components in electrochemical energy storage devices, sparking considerable research interest. However, the significance of anions in the electrolytes is often underestimated. In fact, the anions have significant impacts on the performance and stability of lithium batteries. Therefore, comprehensively understanding anion chemistry in electrolytes is of crucial importance. Herein, in-depth comprehension of anion chemistry and its positive effects on the interface, solvation structure of Li-ions, as well as the electrochemical performance of the batteries have been emphasized and summarized. This review aims to present a full scope of anion chemistry and furnish systematic cognition for the rational design of advanced electrolytes for better lithium batteries with high energy density, lifespan, and safety. Furthermore, insightful analysis and perspectives based on the current research are proposed. We hope that this review sheds light on new perspectives on understanding anion chemistry in electrolytes.


Highlights:
1 The impact of anions on the interface is summarized, including forming a solid electrolyte interphase (SEI), repairing the damaged SEI, and modulate electric double layer.
2 The influence of anions on the solvation structure is presented, including enhancing desolvation process of the Li-ions and the antioxidant property of the electrolyte.
3 This review also emphasizes the important role of anions in enhancing battery safety through their flame-retardant properties, as well as their impact on energy density and power density by altering reaction pathways and accelerating reactions.

Keywords

Anion chemistry Electrolyte Interface Solvation structure
Xiao, Hecong, Xiang Li, and Yongzhu Fu. 2025. “Advances in Anion Chemistry in the Electrolyte Design for Better Lithium Batteries”. Nano-Micro Letters 17 (February):149. https://doi.org/10.1007/s40820-024-01629-5.
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References
  1. J. Xu, J. Zhang, T.P. Pollard, Q. Li, S. Tan et al., Electrolyte design for Li-ion batteries under extreme operating conditions. Nature 614, 694–700 (2023). https://doi.org/10.1038/s41586-022-05627-8
  2. A.-M. Li, O. Borodin, T.P. Pollard, W. Zhang, N. Zhang et al., Methylation enables the use of fluorine-free ether electrolytes in high-voltage lithium metal batteries. Nat. Chem. 16, 922–929 (2024). https://doi.org/10.1038/s41557-024-01497-x
  3. Q. Li, C.-G. Han, S. Wang, C.-C. Ye, X. Zhang et al., Anionic entanglement-induced giant thermopower in ionic thermoelectric material Gelatin-CF3SO3K–CH3SO3K. eScience 3, 100169 (2023). https://doi.org/10.1016/j.esci.2023.100169
  4. X. Fan, C. Wang, High-voltage liquid electrolytes for Li batteries: progress and perspectives. Chem. Soc. Rev. 50, 10486–10566 (2021). https://doi.org/10.1039/d1cs00450f
  5. Y. Qiao, H. Yang, Z. Chang, H. Deng, X. Li et al., A high-energy-density and long-life initial-anode-free lithium battery enabled by a Li2O sacrificial agent. Nat. Energy 6, 653–662 (2021). https://doi.org/10.1038/s41560-021-00839-0
  6. Y. Yamada, J. Wang, S. Ko, E. Watanabe, A. Yamada, Advances and issues in developing salt-concentrated battery electrolytes. Nat. Energy 4, 269–280 (2019). https://doi.org/10.1038/s41560-019-0336-z
  7. J. Alvarado, M.A. Schroeder, T.P. Pollard, X. Wang, J.Z. Lee et al., Bisalt ether electrolytes: a pathway towards lithium metal batteries with Ni-rich cathodes. Energy Environ. Sci. 12, 780–794 (2019). https://doi.org/10.1039/C8EE02601G
  8. X. Ren, L. Zou, S. Jiao, D. Mei, M.H. Engelhard et al., High-concentration ether electrolytes for stable high-voltage lithium metal batteries. ACS Energy Lett. 4, 896–902 (2019). https://doi.org/10.1021/acsenergylett.9b00381
  9. C. Tian, K. Qin, L. Suo, Concentrated electrolytes for rechargeable lithium metal batteries. Mater. Futur. 2, 012101 (2023). https://doi.org/10.1088/2752-5724/acac68
  10. S. Lin, H. Hua, P. Lai, J. Zhao, A multifunctional dual-salt localized high-concentration electrolyte for fast dynamic high-voltage lithium battery in wide temperature range. Adv. Energy Mater. 11, 2101775 (2021). https://doi.org/10.1002/aenm.202101775
  11. S. Chen, J. Zheng, D. Mei, K.S. Han, M.H. Engelhard et al., High-voltage lithium-metal batteries enabled by localized high-concentration electrolytes. Adv. Mater. 30, 1706102 (2018). https://doi.org/10.1002/adma.201706102
  12. T.D. Pham, A. Bin Faheem, J. Kim, H.M. Oh, K.K. Lee, Practical high-voltage lithium metal batteries enabled by tuning the solvation structure in weakly solvating electrolyte. Small 18, e2107492 (2022). https://doi.org/10.1002/smll.202107492
  13. T.D. Pham, K.K. Lee, Simultaneous stabilization of the solid/cathode electrolyte interface in lithium metal batteries by a new weakly solvating electrolyte. Small 17, e2100133 (2021). https://doi.org/10.1002/smll.202100133
  14. S. Zhu, J. Chen, Dual strategy with Li-ion solvation and solid electrolyte interphase for high Coulombic efficiency of lithium metal anode. Energy Storage Mater. 44, 48–56 (2022). https://doi.org/10.1016/j.ensm.2021.10.007
  15. T. Cai, Q. Sun, Z. Cao, Z. Ma, W. Wahyudi et al., Electrolyte additive-controlled interfacial models enabling stable antimony anodes for lithium-ion batteries. J. Phys. Chem. C 126, 20302–20313 (2022). https://doi.org/10.1021/acs.jpcc.2c07094
  16. R. Zhao, S. Shen, D. Chai, S. Tang, Y. Liao et al., Interface engineering enabling non-corrosive sulfonimide salt for 4.4 V class lithium batteries. J. Power Sour. 616, 235125 (2024). https://doi.org/10.1016/j.jpowsour.2024.235125
  17. Y.-W. Song, L. Shen, N. Yao, S. Feng, Q. Cheng et al., Anion-involved solvation structure of lithium polysulfides in lithium-sulfur batteries. Angew. Chem. Int. Ed. 63, e202400343 (2024). https://doi.org/10.1002/anie.202400343
  18. J. Chen, Y. Zhang, H. Lu, J. Ding, X. Wang et al., Electrolyte solvation chemistry to construct an anion-tuned interphase for stable high-temperature lithium metal batteries. eScience 3, 100135 (2023). https://doi.org/10.1016/j.esci.2023.100135
  19. J. Xu, V. Koverga, A. Phan, A. Min Li, N. Zhang et al., Revealing the anion-solvent interaction for ultralow temperature lithium metal batteries. Adv. Mater. 36, e2306462 (2024). https://doi.org/10.1002/adma.202306462
  20. J. Wu, Z. Gao, Y. Wang, X. Yang, Q. Liu et al., Electrostatic interaction tailored anion-rich solvation sheath stabilizing high-voltage lithium metal batteries. Nano-Micro Lett. 14, 147 (2022). https://doi.org/10.1007/s40820-022-00896-4
  21. R. Zhao, X. Li, Y. Si, S. Tang, W. Guo et al., Cu(NO3)2 as efficient electrolyte additive for 4 V class Li metal batteries with ultrahigh stability. Energy Storage Mater. 37, 1–7 (2021). https://doi.org/10.1016/j.ensm.2021.01.030
  22. J. Zhang, H. Zhang, S. Weng, R. Li, D. Lu et al., Multifunctional solvent molecule design enables high-voltage Li-ion batteries. Nat. Commun. 14, 2211 (2023). https://doi.org/10.1038/s41467-023-37999-4
  23. Q. Sun, Z. Gong, T. Zhang, J. Li, X. Zhu et al., Molecule-level multiscale design of nonflammable gel polymer electrolyte to build stable SEI/CEI for lithium metal battery. Nano-Micro Lett. 17, 18 (2024). https://doi.org/10.1007/s40820-024-01508-z
  24. N. Chen, M. Feng, C. Li, Y. Shang, Y. Ma et al., Anion-dominated conventional-concentrations electrolyte to improve low-temperature performance of lithium-ion batteries. Adv. Funct. Mater. 34, 2400337 (2024). https://doi.org/10.1002/adfm.202400337
  25. J.A. Weeks, J.N. Burrow, J. Diao, A.G. Paul-Orecchio, H.S. Srinivasan et al., In situ engineering of inorganic-rich solid electrolyte interphases via anion choice enables stable, lithium anodes. Adv. Mater. 36, e2305645 (2024). https://doi.org/10.1002/adma.202305645
  26. M. Qin, Z. Zeng, Q. Wu, F. Ma, Q. Liu et al., Microsolvating competition in Li+ solvation structure affording PC-based electrolyte with fast kinetics for lithium-ion batteries. Adv. Funct. Mater. 34, 2406357 (2024). https://doi.org/10.1002/adfm.202406357
  27. G. Yang, S. Zhang, S. Weng, X. Li, X. Wang et al., Anionic effect on enhancing the stability of a solid electrolyte interphase film for lithium deposition on graphite. Nano Lett. 21, 5316–5323 (2021). https://doi.org/10.1021/acs.nanolett.1c01436
  28. H. Cheng, Q. Sun, L. Li, Y. Zou, Y. Wang et al., Emerging era of electrolyte solvation structure and interfacial model in batteries. ACS Energy Lett. 7, 490–513 (2022). https://doi.org/10.1021/acsenergylett.1c02425
  29. X. Zhu, J. Chen, G. Liu, Y. Mo, Y. Xie et al., Non-fluorinated cyclic ether-based electrolyte with quasi-conjugate effect for high-performance lithium metal batteries. Angew. Chem. Int. Ed. 64, e202412859 (2025). https://doi.org/10.1002/anie.202412859
  30. J. Chen, Z. Cheng, Y. Liao, L. Yuan, Z. Li et al., Selection of redox mediators for reactivating dead Li in lithium metal batteries. Adv. Energy Mater. 12, 2201800 (2022). https://doi.org/10.1002/aenm.202201800
  31. C.-B. Jin, X.-Q. Zhang, O.-W. Sheng, S.-Y. Sun, L.-P. Hou et al., Reclaiming inactive lithium with a triiodide/iodide redox couple for practical lithium metal batteries. Angew. Chem. Int. Ed. 60, 22990–22995 (2021). https://doi.org/10.1002/anie.202110589
  32. S. Qin, J. Zhang, M. Xu, P. Xu, J. Zou et al., Formulating self-repairing solid electrolyte interface via dynamic electric double layer for practical zinc ion batteries. Angew. Chem. Int. Ed. 63, e202410422 (2024). https://doi.org/10.1002/anie.202410422
  33. H. Wang, J. Zhang, H. Zhang, W. Li, M. Chen et al., Regulating interfacial structure enables high-voltage dilute ether electrolytes. Cell Rep. Phys. Sci. 3, 100919 (2022). https://doi.org/10.1016/j.xcrp.2022.100919
  34. W. Zhang, Y. Lu, L. Wan, P. Zhou, Y. Xia et al., Engineering a passivating electric double layer for high performance lithium metal batteries. Nat. Commun. 13, 2029 (2022). https://doi.org/10.1038/s41467-022-29761-z
  35. D. Chai, H. Yan, X. Wang, X. Li, Y. Fu, Retuning solvating ability of ether solvent by anion chemistry toward 4.5 V class Li metal battery. Adv. Funct. Mater. 34, 2310516 (2024). https://doi.org/10.1002/adfm.202310516
  36. Z. Wang, F. Qi, L. Yin, Y. Shi, C. Sun et al., Lithium anodes: an anion-tuned solid electrolyte interphase with fast ion transfer kinetics for stable lithium anodes (adv. energy mater. 14/2020). Adv. Energy Mater. 10, 2070063 (2020). https://doi.org/10.1002/aenm.202070063
  37. S. Yuan, S. Cao, X. Chen, J. Wei, Z. Lv et al., Deshielding anions enable solvation chemistry control of LiPF6-based electrolyte toward low-temperature lithium-ion batteries. Adv. Mater. 36, e2311327 (2024). https://doi.org/10.1002/adma.202311327
  38. K. Xu, C. Wang, Batteries: widening voltage windows. Nat. Energy 1, 16161 (2016). https://doi.org/10.1038/nenergy.2016.161
  39. L. Wu, F. Pei, D. Cheng, Y. Zhang, H. Cheng et al., Flame-retardant polyurethane-based solid-state polymer electrolytes enabled by covalent bonding for lithium metal batteries. Adv. Funct. Mater. 34, 2310084 (2024). https://doi.org/10.1002/adfm.202310084
  40. J.H. Yang, Y.K. Jeong, W. Kim, M.A. Lee, J.W. Choi et al., Dual flame-retardant mechanism-assisted suppression of thermal runaway in lithium metal batteries with improved electrochemical performances. Adv. Energy Mater. 2304366 (2024). https://doi.org/10.1002/aenm.202304366
  41. Z. Huang, X. Li, Z. Chen, P. Li, X. Ji et al., Anion chemistry in energy storage devices. Nat. Rev. Chem. 7, 616–631 (2023). https://doi.org/10.1038/s41570-023-00506-w
  42. Z. Song, X. Wang, W. Feng, M. Armand, Z. Zhou et al., Designer anions for better rechargeable lithium batteries and beyond. Adv. Mater. 36, 2310245 (2024). https://doi.org/10.1002/adma.202310245
  43. B. Jagger, M. Pasta, Solid electrolyte interphases in lithium metal batteries. Joule 7, 2228–2244 (2023). https://doi.org/10.1016/j.joule.2023.08.007
  44. Y. Zhu, W. Li, L. Zhang, W. Fang, Q. Ruan et al., Electrode/electrolyte interphases in high-temperature batteries: a review. Energy Environ. Sci. 16, 2825–2855 (2023). https://doi.org/10.1039/d3ee00439b
  45. J. Popovic, The importance of electrode interfaces and interphases for rechargeable metal batteries. Nat. Commun. 12, 6240 (2021). https://doi.org/10.1038/s41467-021-26481-8
  46. W. Gu, G. Xue, Q. Dong, R. Yi, Y. Mao et al., Trimethoxyboroxine as an electrolyte additive to enhance the 4.5 ​V cycling performance of a Ni-rich layered oxide cathode. eScience 2, 486–493 (2022). https://doi.org/10.1016/j.esci.2022.05.003
  47. L. Lv, H. Zhang, D. Lu, Y. Yu, J. Qi et al., A low-concentration sulfone electrolyte enables high-voltage chemistry of lithium-ion batteries. Energy Mater. 2, 200030 (2022). https://doi.org/10.20517/energymater.2022.38
  48. F. Qiu, X. Li, H. Deng, D. Wang, X. Mu et al., A concentrated ternary-salts electrolyte for high reversible Li metal battery with slight excess Li. Adv. Energy Mater. 9, 1803372 (2019). https://doi.org/10.1002/aenm.201803372
  49. Q. Wu, M.T. McDowell, Y. Qi, Effect of the electric double layer (EDL) in multicomponent electrolyte reduction and solid electrolyte interphase (SEI) formation in lithium batteries. J. Am. Chem. Soc. 145, 2473–2484 (2023). https://doi.org/10.1021/jacs.2c11807
  50. Q. Zhao, S. Stalin, L.A. Archer, Stabilizing metal battery anodes through the design of solid electrolyte interphases. Joule 5, 1119–1142 (2021). https://doi.org/10.1016/j.joule.2021.03.024
  51. J.-F. Ding, R. Xu, C. Yan, B.-Q. Li, H. Yuan et al., A review on the failure and regulation of solid electrolyte interphase in lithium batteries. J. Energy Chem. 59, 306–319 (2021). https://doi.org/10.1016/j.jechem.2020.11.016
  52. H. Wang, J. Liu, J. He, S. Qi, M. Wu et al., Pseudo-concentrated electrolytes for lithium metal batteries. eScience 2, 557–565 (2022). https://doi.org/10.1016/j.esci.2022.06.005
  53. L. Chen, J. Lu, Y. Wang, P. He, S. Huang et al., Double-salt electrolyte for Li-ion batteries operated at elevated temperatures. Energy Storage Mater. 49, 493–501 (2022). https://doi.org/10.1016/j.ensm.2022.04.036
  54. H. Zhou, Z. Fang, J. Li, LiPF6 and lithium difluoro(oxalato)borate/ethylene carbonate + dimethyl carbonate + ethyl(methyl)carbonate electrolyte for Li4Ti5O12 anode. J. Power Sources 230, 148–154 (2013). https://doi.org/10.1016/j.jpowsour.2012.11.060
  55. R. Weber, M. Genovese, A.J. Louli, S. Hames, C. Martin et al., Long cycle life and dendrite-free lithium morphology in anode-free lithium pouch cells enabled by a dual-salt liquid electrolyte. Nat. Energy 4, 683–689 (2019). https://doi.org/10.1038/s41560-019-0428-9
  56. S. Yan, F. Liu, Y. Ou, H.-Y. Zhou, Y. Lu et al., Asymmetric trihalogenated aromatic lithium salt induced lithium halide rich interface for stable cycling of all-solid-state lithium batteries. ACS Nano 17, 19398–19409 (2023). https://doi.org/10.1021/acsnano.3c07246
  57. S. Wan, K. Song, J. Chen, S. Zhao, W. Ma et al., Reductive competition effect-derived solid electrolyte interphase with evenly scattered inorganics enabling ultrahigh rate and long-life span sodium metal batteries. J. Am. Chem. Soc. 145, 21661–21671 (2023). https://doi.org/10.1021/jacs.3c08224
  58. M. Yang, X. Chang, L. Wang, X. Wang, M. Gu et al., Interface modulation of metal sulfide anodes for long-cycle-life sodium-ion batteries. Adv. Mater. 35, e2208705 (2023). https://doi.org/10.1002/adma.202208705
  59. H. Jiang, Y. Han, C. Li, W. Sun, J. Zheng et al., Ultra-high voltage solid-state Li metal batteries enabled by in situ construction of cathode electrolyte interphase through synergistic dual-anion decomposition. Electrochim. Acta 457, 142439 (2023). https://doi.org/10.1016/j.electacta.2023.142439
  60. J. Zheng, M.H. Engelhard, D. Mei, S. Jiao, B.J. Polzin et al., Electrolyte additive enabled fast charging and stable cycling lithium metal batteries. Nat. Energy 2, 17012 (2017). https://doi.org/10.1038/nenergy.2017.12
  61. A. Fu, J. Lin, Z. Zhang, C. Xu, Y. Zou et al., Synergistical stabilization of Li metal anodes and LiCoO2 cathodes in high-voltage Li∥LiCoO2 batteries by potassium selenocyanate (KSeCN) additive. ACS Energy Lett. 7, 1364–1373 (2022). https://doi.org/10.1021/acsenergylett.2c00316
  62. J. Chen, Y. Peng, Y. Yin, M. Liu, Z. Fang et al., High energy density Na-metal batteries enabled by a tailored carbonate-based electrolyte. Energy Environ. Sci. 15, 3360–3368 (2022). https://doi.org/10.1039/D2EE01257J
  63. C. Wang, X. Zhao, D. Li, C. Yan, Q. Zhang et al., Anion-modulated ion conductor with chain conformational transformation for stabilizing interfacial phase of high-voltage lithium metal batteries. Angew. Chem. Int. Ed. 63, e202317856 (2024). https://doi.org/10.1002/anie.202317856
  64. K. Dong, Y. Xu, J. Tan, M. Osenberg, F. Sun et al., Unravelling the mechanism of lithium nucleation and growth and the interaction with the solid electrolyte interface. ACS Energy Lett. 6, 1719–1728 (2021). https://doi.org/10.1021/acsenergylett.1c00551
  65. D. Aurbach, E. Zinigrad, Y. Cohen, H. Teller, A short review of failure mechanisms of lithium metal and lithiated graphite anodes in liquid electrolyte solutions. Solid State Ion. 148, 405–416 (2002). https://doi.org/10.1016/S0167-2738(02)00080-2
  66. D. Lin, Y. Liu, Y. Cui, Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 12, 194–206 (2017). https://doi.org/10.1038/nnano.2017.16
  67. C. Fang, X. Wang, Y.S. Meng, Key issues hindering a practical lithium-metal anode. Trends Chem. 1, 152–158 (2019). https://doi.org/10.1016/j.trechm.2019.02.015
  68. C. Fang, J. Li, M. Zhang, Y. Zhang, F. Yang et al., Quantifying inactive lithium in lithium metal batteries. Nature 572, 511–515 (2019). https://doi.org/10.1038/s41586-019-1481-z
  69. C. Jin, T. Liu, O. Sheng, M. Li, T. Liu et al., Rejuvenating dead lithium supply in lithium metal anodes by iodine redox. Nat. Energy 6, 378–387 (2021). https://doi.org/10.1038/s41560-021-00789-7
  70. O. Sheng, H. Hu, T. Liu, Z. Ju, G. Lu et al., Interfacial and ionic modulation of poly (ethylene oxide) electrolyte via localized iodization to enable dendrite-free lithium metal batteries. Adv. Funct. Mater. 32, 2111026 (2022). https://doi.org/10.1002/adfm.202111026
  71. S. Ma, J. Zhao, Q. Gao, C. Song, H. Xiao et al., Breaking mass transport limitations by iodized polyacrylonitrile anodes for extremely fast-charging lithium-ion batteries. Angew. Chem. Int. Ed. 62, e202315564 (2023). https://doi.org/10.1002/anie.202315564
  72. Y. Xia, P. Zhou, X. Kong, J. Tian, W. Zhang et al., Designing an asymmetric ether-like lithium salt to enable fast-cycling high-energy lithium metal batteries. Nat. Energy 8, 934–945 (2023). https://doi.org/10.1038/s41560-023-01282-z
  73. P. Zhou, H. Zhou, Y. Xia, Q. Feng, X. Kong et al., Rational lithium salt molecule tuning for fast charging/discharging lithium metal battery. Angew. Chem. Int. Ed. 63, e202316717 (2024). https://doi.org/10.1002/anie.202316717
  74. Y. Qin, H. Wang, J. Zhou, R. Li, C. Jiang et al., Binding FSI- to construct a self-healing SEI film for Li-metal batteries by in situ crosslinking vinyl ionic liquid. Angew. Chem. Int. Ed. 63, e202402456 (2024). https://doi.org/10.1002/anie.202402456
  75. J. Liu, J. Wang, Y. Ni, J. Liu, Y. Zhang et al., Tuning interphase chemistry to stabilize high-voltage LiCoO2 cathode material via spinel coating. Angew. Chem. Int. Ed. 61, e202207000 (2022). https://doi.org/10.1002/anie.202207000
  76. S. Mao, J. Mao, Z. Shen, Q. Wu, S. Zhang et al., Specific adsorption-oxidation strategy in cathode inner Helmholtz plane enabling 4.6 V practical lithium-ion full cells. Nano Lett. 23, 7014–7022 (2023). https://doi.org/10.1021/acs.nanolett.3c01700
  77. J. Zhang, Y. Yan, X. Wang, Y. Cui, Z. Zhang et al., Bridging multiscale interfaces for developing ionically conductive high-voltage iron sulfate-containing sodium-based battery positive electrodes. Nat. Commun. 14, 3701 (2023). https://doi.org/10.1038/s41467-023-39384-7
  78. Z. Wen, W. Fang, F. Wang, H. Kang, S. Zhao et al., Dual-salt electrolyte additive enables high moisture tolerance and favorable electric double layer for lithium metal battery. Angew. Chem. Int. Ed. 63, e202314876 (2024). https://doi.org/10.1002/anie.202314876
  79. J. Ming, Z. Cao, W. Wahyudi, M. Li, P. Kumar et al., New insights on graphite anode stability in rechargeable batteries: Li ion coordination structures prevail over solid electrolyte interphases. ACS Energy Lett. 3, 335–340 (2018). https://doi.org/10.1021/acsenergylett.7b01177
  80. Z. Tian, Y. Zou, G. Liu, Y. Wang, J. Yin et al., Electrolyte solvation structure design for sodium ion batteries. Adv. Sci. 9, 2201207 (2022). https://doi.org/10.1002/advs.202201207
  81. N. Yao, S.-Y. Sun, X. Chen, X.-Q. Zhang, X. Shen et al., The anionic chemistry in regulating the reductive stability of electrolytes for lithium metal batteries. Angew. Chem. Int. Ed. 61, e202210859 (2022). https://doi.org/10.1002/anie.202210859
  82. S. Liu, C. Shu, Y. Yan, L. Ren, D. Du et al., Regulating solvation environment of Li ions via high donor number anions for high-performance Li-metal batteries. Chem. Eng. J. 450, 138369 (2022). https://doi.org/10.1016/j.cej.2022.138369
  83. H. Fu, X. Ye, Y. Zhang, Y. Zhong, X. Wang et al., Toward ultralow temperature lithium metal batteries: advancing the feasibility of 1, 3-dioxolane based localized high-concentration electrolytes via lithium nitrate. Adv. Energy Mater. 14, 2401961 (2024). https://doi.org/10.1002/aenm.202401961
  84. S. Kim, T.K. Lee, S.K. Kwak, N.-S. Choi, Solid electrolyte interphase layers by using lithiophilic and electrochemically active ionic additives for lithium metal anodes. ACS Energy Lett. 7, 67–69 (2022). https://doi.org/10.1021/acsenergylett.1c02461
  85. J. You, Q. Wang, R. Wei, L. Deng, Y. Hu et al., Boosting high-voltage practical lithium metal batteries with tailored additives. Nano-Micro Lett. 16, 257 (2024). https://doi.org/10.1007/s40820-024-01479-1
  86. D. Chai, Y. Zhu, C. Guan, T. Zhang, S. Tang et al., Achieving stable interphases toward lithium metal batteries by a dilute and anion-rich electrolyte. Energy Storage Mater. 62, 102957 (2023). https://doi.org/10.1016/j.ensm.2023.102957
  87. L. Zheng, F. Guo, T. Kang, Y. Fan, W. Gu et al., Stable lithium-carbon composite enabled by dual-salt additives. Nano-Micro Lett. 13, 111 (2021). https://doi.org/10.1007/s40820-021-00633-3
  88. Z. Jiang, T. Yang, C. Li, J. Zou, H. Yang et al., Synergistic additives enabling stable cycling of ether electrolyte in 4.4 V Ni-rich/Li metal batteries. Adv. Funct. Mater. 33, 2306868 (2023). https://doi.org/10.1002/adfm.202306868
  89. R. Zhao, X. Li, Y. Si, W. Guo, Y. Fu, Tuning solvation behavior of ester-based electrolytes toward highly stable lithium-metal batteries. ACS Appl. Mater. Interfaces 13, 40582–40589 (2021). https://doi.org/10.1021/acsami.1c10279
  90. X. Li, R. Zhao, Y. Fu, A. Manthiram, Nitrate additives for lithium batteries: mechanisms, applications, and prospects. eScience 1, 108–123 (2021). https://doi.org/10.1016/j.esci.2021.12.006
  91. Y. Zhu, X. Li, Y. Si, X. Zhang, P. Sang et al., Regulating dissolution chemistry of nitrates in carbonate electrolyte for high-stable lithium metal batteries. J. Energy Chem. 73, 422–428 (2022). https://doi.org/10.1016/j.jechem.2022.06.046
  92. M. Xia, M. Lin, G. Liu, Y. Cheng, T. Jiao et al., Stable cycling and fast charging of high-voltage lithium metal batteries enabled by functional solvation chemistry. Chem. Eng. J. 442, 136351 (2022). https://doi.org/10.1016/j.cej.2022.136351
  93. J. Jung, H. Chu, I. Kim, D.H. Lee, G. Doo et al., Confronting sulfur electrode passivation and Li metal electrode degradation in lithium-sulfur batteries using thiocyanate anion. Adv. Sci. 10, e2301006 (2023). https://doi.org/10.1002/advs.202301006
  94. Z. Jiang, C. Li, T. Yang, Y. Deng, J. Zou et al., Fluorine-free lithium metal batteries with a stable LiF-free solid electrolyte interphase. ACS Energy Lett. 9, 1389–1396 (2024). https://doi.org/10.1021/acsenergylett.3c02724
  95. J.-X. Chen, J.-H. Zhang, X.-Z. Fan, F.-F. Wang, W. Tang et al., Solvating lithium and tethering aluminium using di-coordination-strength anions for low-temperature lithium metal batteries. Energy Environ. Sci. 17, 4036–4043 (2024). https://doi.org/10.1039/D3EE03809B
  96. X. Chen, Q. Zhang, Atomic insights into the fundamental interactions in lithium battery electrolytes. Acc. Chem. Res. 53, 1992–2002 (2020). https://doi.org/10.1021/acs.accounts.0c00412
  97. K.W. Schroder, A.G. Dylla, L.D.C. Bishop, E.R. Kamilar, J. Saunders et al., Effects of solute-solvent hydrogen bonding on nonaqueous electrolyte structure. J. Phys. Chem. Lett. 6, 2888–2891 (2015). https://doi.org/10.1021/acs.jpclett.5b01216
  98. H. Li, Y. Kang, W. Wei, C. Yan, X. Ma et al., Branch-chain-rich diisopropyl ether with steric hindrance facilitates stable cycling of lithium batteries at –20 °C. Nano-Micro Lett. 16, 197 (2024). https://doi.org/10.1007/s40820-024-01419-z
  99. J. Wang, J. Zhang, J. Wu, M. Huang, L. Jia et al., Interfacial “single-atom-in-defects” catalysts accelerating Li+ desolvation kinetics for long-lifespan lithium-metal batteries. Adv. Mater. 35, e2302828 (2023). https://doi.org/10.1002/adma.202302828
  100. Y. Huang, J. Geng, Z. Jiang, M. Ren, B. Wen et al., Solvation structure with enhanced anionic coordination for stable anodes in lithium-oxygen batteries. Angew. Chem. Int. Ed. 62, e202306236 (2023). https://doi.org/10.1002/anie.202306236
  101. X. Zhou, Y. Huang, B. Wen, Z. Yang, Z. Hao et al., Regulation of anion-Na+ coordination chemistry in electrolyte solvates for low-temperature sodium-ion batteries. Proc. Natl. Acad. Sci. U.S.A. 121, e2316914121 (2024). https://doi.org/10.1073/pnas.2316914121
  102. H. Su, Z. Chen, M. Li, P. Bai, Y. Li et al., Achieving practical high-energy-density lithium-metal batteries by a dual-anion regulated electrolyte. Adv. Mater. 35, e2301171 (2023). https://doi.org/10.1002/adma.202301171
  103. P. Liang, H. Hu, Y. Dong, Z. Wang, K. Liu et al., Competitive coordination of ternary anions enabling fast Li-ion desolvation for low-temperature lithium metal batteries. Adv. Funct. Mater. 34, 2309858 (2024). https://doi.org/10.1002/adfm.202309858
  104. X. Ren, L. Zou, X. Cao, M.H. Engelhard, W. Liu et al., Enabling high-voltage lithium-metal batteries under practical conditions. Joule 3, 1662–1676 (2019). https://doi.org/10.1016/j.joule.2019.05.006
  105. C. Niu, H. Lee, S. Chen, Q. Li, J. Du et al., High-energy lithium metal pouch cells with limited anode swelling and long stable cycles. Nat. Energy 4, 551–559 (2019). https://doi.org/10.1038/s41560-019-0390-6
  106. Z. Wu, R. Li, S. Zhang, L. lv, T. Deng et al., Deciphering and modulating energetics of solvation structure enables aggressive high-voltage chemistry of Li metal batteries. Chem 9, 650–664 (2023). https://doi.org/10.1016/j.chempr.2022.10.027
  107. Y. Chen, Z. Yu, P. Rudnicki, H. Gong, Z. Huang et al., Steric effect tuned ion solvation enabling stable cycling of high-voltage lithium metal battery. J. Am. Chem. Soc. 143, 18703–18713 (2021). https://doi.org/10.1021/jacs.1c09006
  108. Y.-X. Yao, X. Chen, C. Yan, X.-Q. Zhang, W.-L. Cai et al., Regulating interfacial chemistry in lithium-ion batteries by a weakly solvating electrolyte. Angew. Chem. Int. Ed. 60, 4090–4097 (2021). https://doi.org/10.1002/anie.202011482
  109. Z. Jiang, J. Mo, C. Li, H. Li, Q. Zhang et al., Anion-regulated weakly solvating electrolytes for high-voltage lithium metal batteries. Energy Environ. Mater. 6, 12440 (2023). https://doi.org/10.1002/eem2.12440
  110. Y.-F. Tian, S.-J. Tan, Z.-Y. Lu, D.-X. Xu, H.-X. Chen et al., Insights into anion-solvent interactions to boost stable operation of ether-based electrolytes in pure-SiOx||LiNi0.8Mn0.1Co0.1O2 full cells. Angew. Chem. Int. Ed. 62, 202305988 (2023). https://doi.org/10.1002/anie.202305988
  111. X. Min, C. Han, S. Zhang, J. Ma, N. Hu et al., Highly oxidative-resistant cyano-functionalized lithium borate salt for enhanced cycling performance of practical lithium-ion batteries. Angew. Chem. Int. Ed. 62, e202302664 (2023). https://doi.org/10.1002/anie.202302664
  112. D. Wu, C. Zhu, M. Wu, H. Wang, J. Huang et al., Highly oxidation-resistant electrolyte for 4.7 V sodium metal batteries enabled by anion/cation solvation engineering. Angew. Chem. Int. Ed. 61, e202214198 (2022). https://doi.org/10.1002/anie.202214198
  113. S. Zhang, S. Li, Y. Lu, Designing safer lithium-based batteries with nonflammable electrolytes: a review. eScience 1, 163–177 (2021). https://doi.org/10.1016/j.esci.2021.12.003
  114. Z. Gao, S. Rao, T. Zhang, W. Li, X. Yang et al., Design strategies of flame-retardant additives for lithium ion electrolyte. J. Electrochem. Energy Convers. Storage 19, 030910 (2022). https://doi.org/10.1115/1.4053968
  115. R. He, K. Deng, D. Mo, X. Guan, Y. Hu et al., Active diluent-anion synergy strategy regulating nonflammable electrolytes for high-efficiency Li metal batteries. Angew. Chem. Int. Ed. 63, e202317176 (2024). https://doi.org/10.1002/anie.202317176
  116. Y. Zou, G. Liu, Y. Wang, Q. Li, Z. Ma et al., Intermolecular interactions mediated nonflammable electrolyte for high-voltage lithium metal batteries in wide temperature. Adv. Energy Mater. 13, 2300443 (2023). https://doi.org/10.1002/aenm.202300443
  117. D.-J. Yoo, Q. Liu, O. Cohen, M. Kim, K.A. Persson et al., Rational design of fluorinated electrolytes for low temperature lithium-ion batteries. Adv. Energy Mater. 13, 2204182 (2023). https://doi.org/10.1002/aenm.202204182
  118. M. Qin, Z. Zeng, F. Ma, C. Gu, X. Chen et al., Doping in solvation structure: enabling fluorinated carbonate electrolyte for high-voltage and high-safety lithium-ion batteries. ACS Energy Lett. 9, 2536–2544 (2024). https://doi.org/10.1021/acsenergylett.4c00790
  119. P. Xiao, Y. Zhao, Z. Piao, B. Li, G. Zhou et al., A nonflammable electrolyte for ultrahigh-voltage (4.8 V-class) Li||NCM811 cells with a wide temperature range of 100 °C. Energy Environ. Sci. 15, 2435–2444 (2022). https://doi.org/10.1039/D1EE02959B
  120. L. Tan, S. Chen, Y. Chen, J. Fan, D. Ruan et al., Intrinsic nonflammable ether electrolytes for ultrahigh-voltage lithium metal batteries enabled by chlorine functionality. Angew. Chem. Int. Ed. 61, e202203693 (2022). https://doi.org/10.1002/anie.202203693
  121. M. Zheng, X. Li, J. Sun, X. Wang, G. Liu et al., Research progress on chloride solid electrolytes for all-solid-state batteries. J. Power Sources 595, 234051 (2024). https://doi.org/10.1016/j.jpowsour.2024.234051
  122. D.H.S. Tan, A. Banerjee, Z. Chen, Y.S. Meng, From nanoscale interface characterization to sustainable energy storage using all-solid-state batteries. Nat. Nanotechnol. 15, 170–180 (2020). https://doi.org/10.1038/s41565-020-0657-x
  123. A. Manthiram, X. Yu, S. Wang, Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater. 2, 16103 (2017). https://doi.org/10.1038/natrevmats.2016.103
  124. C. Zuo, D. Dong, H. Wang, Y. Sun, Y.-C. Lu, Bromide-based nonflammable electrolyte for safe and long-life sodium metal batteries. Energy Environ. Sci. 17, 791–799 (2024). https://doi.org/10.1039/d3ee03332e
  125. Y. He, Y. Zhang, P. Yu, F. Ding, X. Li et al., Ion association tailoring SEI composition for Li metal anode protection. J. Energy Chem. 45, 1–6 (2020). https://doi.org/10.1016/j.jechem.2019.09.033
  126. Z. Jiang, Y. Deng, J. Mo, Q. Zhang, Z. Zeng et al., Switching reaction pathway of medium-concentration ether electrolytes to achieve 4.5 V lithium metal batteries. Nano Lett. 23, 8481–8489 (2023). https://doi.org/10.1021/acs.nanolett.3c02013
  127. Y. Yang, J. Wang, Z. Li, Z. Yang, B. Wang et al., Constructing LiF-dominated interphases with polymer interwoven outer layer enables long-term cycling of Si anodes. ACS Nano 18, 7666–7676 (2024). https://doi.org/10.1021/acsnano.4c00998
  128. S. Xue, J. Shang, X. Pu, H. Cheng, L. Zhang et al., Dual anionic doping strategy towards synergistic optimization of Co9S8 for fast and durable sodium storage. Energy Storage Mater. 55, 33–41 (2023). https://doi.org/10.1016/j.ensm.2022.11.040
  129. B. Wang, Y. Huang, Y. Wang, H. Wang, Synergistic solvation of anion: an effective strategy toward economical high-performance dual-ion battery. Adv. Funct. Mater. 33, 2212287 (2023). https://doi.org/10.1002/adfm.202212287
  130. H. Jiang, X. Han, X. Du, Z. Chen, C. Lu et al., A PF6––permselective polymer electrolyte with anion solvation regulation enabling long-cycle dual-ion battery. Adv. Mater. 34, e2108665 (2022). https://doi.org/10.1002/adma.202108665
  131. X. Tong, X. Ou, N. Wu, H. Wang, J. Li et al., High oxidation potential ≈6.0 V of concentrated electrolyte toward high-performance dual-ion battery. Adv. Energy Mater. 11, 2100151 (2021). https://doi.org/10.1002/aenm.202100151
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