Balancing Ionic Conductivity and Oxidative Stability in UCl3-Type Halide Solid Electrolytes

doi:10.15541/jim20260213

Abstract

Abstract: Halide solid electrolytes that exhibit both high ionic conductivity and good oxidative stability are critical for high-energy-density all-solid-state lithium batteries (ASSLBs), yet these two properties usually are rarely achieved simultaneously. Herein, synergistic co-doping of cation and anion is developed to tailor the structural and electrochemical properties of UCl₃-type Li_0.388Ta_0.238La_0.475Cl₃ (LTLC) electrolytes. Fluorine substitution at anion sites extends the electrochemical window, while subsequent Zr⁴⁺ incorporation increases the ionic conductivity through expanding Li⁺ transport channels and weakening Li-F interactions. The optimized co-doped Li_0.447Ta_0.179Zr_0.059La_0.475Cl_2.6F_0.4 (LTZ_0.059LCF_0.4) electrolytes achieve the ionic conductivity of 0.87 mS·cm^-1 at 30 ℃, and the upper electrochemical window above 4.52 V. ASSLBs using these electrolytes and LiCoO₂ cathodes deliver the initial specific capacity of 182.3 mAh·g^-1 at 0.1C (1C=180 mA·g^-1) and capacity retention of 81.2% after 300 cycles. Furthermore, these electrolytes demonstrate excellent compatibility with LiNi_0.9Co_0.05Mn_0.05O₂ (NCM9055) cathodes, maintaining the reversible capacity of 109.8 mAh·g^-1 at 0.1C after 240 cycles. Thin and homogeneous CEI layers are uniformly formed on the cathode surfaces, effectively protecting the cathodes from severe interfacial side reactions. This work establishes a feasible co-doping strategy for advanced halide electrolytes toward high-energy-density ASSLBs.

Key words: halide solid electrolyte, cation-anion co-doping, ionic conductivity, electrochemical window, all-solid-state lithium battery

CLC Number:

TM911

BAO Maohao, DOU Shuming, LIU Binhui, CUI Zhonghui, ZHAO Ning, GUO Xiangxin. Balancing Ionic Conductivity and Oxidative Stability in UCl₃-Type Halide Solid Electrolytes[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260213.

References

[1] LI M, LU J, CHEN Z W, et al. 30 years of lithium-ion batteries. Advanced Materials, 2018, 30(33): 24.
[2] JOSHI A, MISHRA D K, SINGH R, et al. A comprehensive review of solid-state batteries. Applied Energy, 2025, 386: 21.
[3] WANG J C, CHEN L Q, LI H, et al. Anode interfacial issues in solid-state Li batteries: mechanistic understanding and mitigating strategies. Energy & Environmental Materials, 2023, 6(4): 21.
[4] CEN G J, YU H L, XIAO R J, et al. Adaptive interphase enabled pressure-free all-solid-state lithium metal batteries. Nature Sustainability, 2025, 8(11): 14.
[5] ZHANG Z Z, SHAO Y J, LOTSCH B, et al. New horizons for inorganic solid state ion conductors. Energy & Environmental Science, 2018, 11(8): 1945-1976.
[6] CHEN R S, LI Q H, YU X Q, et al. Approaching practically accessible solid-state batteries: stability issues related to solid electrolytes and interfaces. Chemical Reviews, 2020, 120(14): 6820.
[7] FAMPRIKIS T, CANEPA P, DAWSON J A, et al. Fundamentals of inorganic solid-state electrolytes for batteries. Nature Materials, 2019, 18(12): 1278.
[8] MEI H X, PICCARDO P, CINGOLANI A, et al. Unconventional solid-state electrolytes for lithium-based batteries: recent advances and challenges. Journal of Power Sources, 2023, 553: 29.
[9] TAO B R, ZHONG D L, LI H D, et al. Halide solid-state electrolytes for all-solid-state batteries: structural design, synthesis, environmental stability, interface optimization and challenges. Chemical Science, 2023, 14(33): 8693.
[10] KATO Y, HORI S, SAITO T, et al. High-power all-solid-state batteries using sulfide superionic conductors. Nature Energy, 2016, 1: 7.
[11] TUO K, SUN C W, LIU S Q.Recent progress in and perspectives on emerging halide superionic conductors for all-solid-state batteries.Electrochemical Energy Reviews, 2023, 6(1): 46.
[12] QU J, WU H, WANG X Y, et al. Advances in non/low-crystalline solid-state electrolytes enabled by halide-based electrolytes. Joule, 2026, 10(2): 16.
[13] CHEN X, ZHAO N, LIU B H, et al. A viscoelastic oxyhalide catholyte for 4.5 V all-solid-state batteries under low stack pressures. Applied Physics Letters, 10.1063/5.0338242.
[14] WU J H, LI J H, YAO X Y.Exploring the potential of halide electrolytes for next-generation all-solid-state lithium batteries.Advanced Functional Materials, 2025, 35(10): 30.
[15] SCHLEM R, BANIK A, OHNO S, et al. Insights into the lithium sub-structure of superionic conductors Li₃YCl₆ and Li₃YBr₆. Chemistry of Materials, 2021, 33(1): 327.
[16] WANG C H, LIANG J W, KIM J T, et al. Prospects of halide-based all-solid-state batteries: from material design to practical application. Science Advances, 2022, 8(36): 13.
[17] GANESAN P, SOANS M, CAMBAZ M A, et al. Fluorine-substituted halide solid electrolytes with enhanced stability toward the lithium metal. ACS Applied Materials & Interfaces, 2023, 15(32): 38391.
[18] YIN Y C, YANG J T, LUO J D, et al. A LaCl₃-based lithium superionic conductor compatible with lithium metal. Nature, 2023, 616(7955): 19.
[19] LI X A, XU Y, ZHAO C T, et al. The universal super cation-conductivity in multiple-cation mixed chloride solid-state electrolytes. Angewandte Chemie International Edition, 2023, 62(48): 8.
[20] FU C, LI Y, XU W, et al. LaCl₃-based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries. Nature Communications, 2024, 15(1): 4315.
[21] ZHANG S M, ZHAO F P, WANG S, et al. Advanced high-voltage all-solid-state Li-ion batteries enabled by a dual-halogen solid electrolyte. Advanced Energy Materials, 2021, 11(32): 10.
[22] QIAN L, TU S B, WANG Y, et al. Near-saturated coordinated cations in oxyhalide superionic conductors boost high-rate all-solid-state batteries. Journal of the American Chemical Society, 2025, 147(26): 23170.
[23] YE Y, GENG J Z, ZUO D X, et al. High-voltage long-cycling all-solid-state lithium batteries with high-valent-element-doped halide electrolytes. ACS Nano, 2024, 18(28): 18368.
[24] HELM B, SCHLEM R, WANKMILLER B, et al. Exploring aliovalent substitutions in the lithium halide superionic conductor Li₃-_xIn₁-_xZr_xCl₆(0≤x≤0.5). Acta Crystallographica a-Foundation and Advances, 2021, 77: A66.
[25] WANG H, LI Y X, TANG Y, et al. Electrochemically stable Li₃-_xIn₁-_xHf_xCl₆ halide solid electrolytes for all-solid-state batteries. ACS Applied Materials & Interfaces, 2023, 15(4): 5504.
[26] YANG J L, CHEN S W, YUAN Q, et al. UCl₃-type crystalline oxychloride electrolytes for all-solid-state lithium-ion batteries. Journal of the American Chemical Society, 2025, 147(40): 36557.
[27] LUO J D, ZHANG Y X, CHENG X B, et al. Halide superionic conductors with non-close-packed anion frameworks. Angewandte Chemie International Edition, 2024, 63(17): 10.
[28] WANG W Z, JING K X, MA H, et al. Simultaneously enhance humidity tolerance and ionic conductivity of halide electrolytes by cation-anion co-doping. Small, 2025, 21(21): 10.
[29] TOBY B H, VON DREELE R B. GSAS-II: the genesis of a modern open-source all purpose crystallography software package.Journal of Applied Crystallography, 2013, 46: 544.
[30] O'DONNELL J H, VON DREELE R B, CHAN M K Y, et al. A scripting interface for GSAS-II. Journal of Applied Crystallography, 2018, 51: 1244.
[31] PERDEW J P, BURKE K, ERNZERHOF M.Generalized gradient approximation made simple.Physical Review Letters, 1996, 77(18): 3865.
[32] GRIMME S, EHRLICH S, GOERIGK L.Effect of the damping function in dispersion corrected density functional theory.Journal of Computational Chemistry, 2011, 32(7): 1456.
[33] WEIGEND F, AHLRICHS R.Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: design and assessment of accuracy.Physical Chemistry Chemical Physics, 2005, 7(18): 3297.
[34] ADAMS S.From bond valence maps to energy landscapes for mobile ions in ion-conducting solids.Solid State Ionics, 2006, 177(19-25): 1625.
[35] KRESSE G, JOUBERT D.From ultrasoft pseudopotentials to the projector augmented-wave method.Physical Review B, 1999, 59(3): 1758.
[36] CHEN H M, WONG L L, ADAMS S.SoftBV - a software tool for screening the materials genome of inorganic fast ion conductors.Acta Crystallographica Section B-Structural Science Crystal Engineering and Materials, 2019, 75: 18.
[37] ZHANG Y N, SONG Z Y, WANG L K, et al. A Li-rich fluorinated lithium zirconium chloride solid electrolyte for 4.8 V-class all-solid-state batteries. Small, 2025, 21(2): 9.
[38] YU Y W, LIU G X, CHEN R B, et al. Constructing robust solid electrolyte interphase by coating Li_6.4La₃Zr_1.4Ta_0.6O₁₂ on silicon anodes for high-performance lithium-ion batteries. Science China-Technological Sciences, 2025, 68(11): 9.
[39] GAO Y J, ZHANG S M, ZHAO F P, et al. Fluorinated superionic oxychloride solid electrolytes for high-voltage all-solid-state lithium batteries. ACS Energy Letters, 2024, 9(4): 1735.
[40] ZHOU L H, ZHANG S D, LI W P, et al. Amorphous-nanocrystalline fluorinated halide electrolytes with high ionic conductivity and high-voltage stability. Journal of the American Chemical Society, 2025, 147(18): 15136.
[41] WANG K, REN Q Y, GU Z Q, et al. A cost-effective and humidity-tolerant chloride solid electrolyte for lithium batteries. Nature Communications, 2021, 12(1): 11.
[42] WU X, LIANG L X, DU B X, et al. High-conductivity argyrodite electrolyte with self-passivating stability for single-electrolyte all-solid-state lithium batteries. Angewandte Chemie-International Edition, 2026, 65(4): 12.
[43] SHEN L, LI J L, KONG W J, et al. Anion-engineering toward high-voltage-stable halide superionic conductors for all-solid-state lithium batteries. Advanced Functional Materials, 2024, 34(48): 10.

Balancing Ionic Conductivity and Oxidative Stability in UCl₃-Type Halide Solid Electrolytes

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