Boosting the Power Characteristics of All-Solid-State Batteries Through Improved Electrochemical Stability: Site-Specific Nb Doping in Argyrodite

Abstract

Enhancing the energy density of all-solid-state batteries (ASSBs) with lithium metal anodes is crucial, but lithium dendrite-induced short circuits limit fast-charging capability. This study presents a high-power ASSB employing a novel, robust solid electrolyte (SE) with exceptionally high stability at the lithium metal/SE interface, achieved via site-specific Nb doping in the argyrodite structure. Pentavalent Nb incorporation into Wyckoff 48h sites enhances structural stability, as confirmed by neutron diffraction, X-ray absorption spectroscopy, magic angle spinning nuclear magnetic resonance, and density functional theory calculations. While Nb doping slightly reduces ionic conductivity, it significantly improves interfacial stability, suppressing dendrite formation and enabling a full cell capable of charging in just 6 min (10-C rate, 16 mA cm⁻²). This study highlights, for the first time, that electrochemical stability, rather than ionic conductivity, is key to achieving high-power performance, advancing the commercialization of lithium metal-based ASSBs.

Keywords

all-solid-state batteries / argyrodites / lithium ionic conductors / solid electrolytes

References

[1] Y. Cao, M. Li, J. Lu, J. Liu, and K. Amine, “Bridging the Academic and Industrial Metrics for Next-Generation Practical Batteries,” Nature Nanotechnology 14, no. 3 (2019): 200–207.

[2] J. Janek and W. G. Zeier, “A Solid Future for Battery Development,” Nature Energy 1, no. 9 (2016): 16141.

[3] Y. Kato, S. Hori, T. Saito, et al., “High-Power All-Solid-State Batteries Using Sulfide Superionic Conductors,” Nature Energy 1 (2016): 16030.

[4] F. Zhao, J. Liang, C. Yu, et al., “A Versatile Sn-Substituted Argyrodite Sulfide Electrolyte for All-Solid-State Li Metal Batteries,” Advanced Energy Materials 10, no. 9 (2020): 1903422.

[5] H. Kwak, J. S. Kim, D. Han, et al., “Boosting the Interfacial Superionic Conduction of Halide Solid Electrolytes for All-Solid-State Batteries,” Nature Communications 14, no. 1 (2023): 2459.

[6] Y. Lee, J. Jeong, H. J. Lee, et al., “Lithium Argyrodite Sulfide Electrolytes With High Ionic Conductivity and Air Stability for All-Solid-State Li-Ion Batteries,” ACS Energy Letters 7, no. 1 (2021): 171–179.

[7] D. H. Kim, Y.-H. Lee, Y. B. Song, H. Kwak, S.-Y. Lee, and Y. S. Jung, “Thin and Flexible Solid Electrolyte Membranes With Ultrahigh Thermal Stability Derived From Solution-Processable Li Argyrodites for All-Solid-State Li-Ion Batteries,” ACS Energy Letters 5, no. 3 (2020): 718–727.

[8] Y. Li, S. Song, H. Kim, et al., “A Lithium Superionic Conductor for Millimeter-Thick Battery Electrode,” Science 381, no. 6653 (2023): 50–53.

[9] Y. Kato, S. Shiotani, K. Morita, K. Suzuki, M. Hirayama, and R. Kanno, “All-Solid-State Batteries With Thick Electrode Configurations,” Journal of Physical Chemistry Letters 9, no. 3 (2018): 607–613.

[10] L. Zhou, T.-T. Zuo, C. Y. Kwok, et al., “High Areal Capacity, Long Cycle Life 4 V Ceramic All-Solid-State Li-Ion Batteries Enabled by Chloride Solid Electrolytes,” Nature Energy 7, no. 1 (2022): 83–93.

[11] G. Oh, M. Hirayama, O. Kwon, K. Suzuki, and R. Kanno, “Bulk-Type All Solid-State Batteries With 5 V Class LiNi_0.5Mn_1.5O₄ Cathode and Li₁₀GeP₂S₁₂ Solid Electrolyte,” Chemistry of Materials 28, no. 8 (2016): 2634–2640.

[12] Z. Chen, X. Ma, Y. Hou, et al., “Grafted MXenes Based Electrolytes for 5V-Class Solid-State Batteries,” Advanced Functional Materials 33, no. 23 (2023): 2214539.

[13] Y.-G. Lee, S. Fujiki, C. Jung, et al., “High-Energy Long-Cycling All-Solid-State Lithium Metal Batteries Enabled by Silver–Carbon Composite Anodes,” Nature Energy 5, no. 4 (2020): 299–308.

[14] U.-H. Kim, T.-Y. Yu, J. W. Lee, et al., “Microstructure- and Interface-Modified Ni-Rich Cathode for High-Energy-Density All-Solid-State Lithium Batteries,” ACS Energy Letters 8, no. 1 (2023): 809–817.

[15] Y. Han, S. H. Jung, H. Kwak, et al., “Single- or Poly-Crystalline Ni-Rich Layered Cathode, Sulfide or Halide Solid Electrolyte: Which Will Be the Winners for All-Solid-State Batteries?,” Advanced Energy Materials 11, no. 21 (2021): 2100126.

[16] Y. Park, J. H. Chang, G. Oh, et al., “Enhanced Electrochemical Stability and Extended Cycle Life in Sulfide-Based All-Solid-State Batteries: The Role of Li₁₀SnP₂S₁₂ Coating on Ni-Rich NCM Cathode,” Small 20 (2024): 2305758.

[17] A. Jain, S. P. Ong, G. Hautier, et al., “Commentary: The Materials Project: A Materials Genome Approach to Accelerating Materials Innovation,” APL Materials 1 (2013): 11002.

[18] M. Rana, Y. Rudel, P. Heuer, et al., “Toward Achieving High Areal Capacity in Silicon-Based Solid-State Battery Anodes: What Influences the Rate-Performance?,” ACS Energy Letters 8, no. 7 (2023): 3196–3203.

[19] Z. Zhang, Z. Sun, X. Han, et al., “An All-Electrochem-Active Silicon Anode Enabled by Spontaneous Li–Si Alloying for Ultra-High Performance Solid-State Batteries,” Energy & Environmental Science 17, no. 3 (2024): 1061–1072.

[20] X. Xing, Y. Li, S. Wang, et al., “Graphite-Based Lithium-Free 3D Hybrid Anodes for High Energy Density All-Solid-State Batteries,” ACS Energy Letters 6, no. 5 (2021): 1831–1838.

[21] Z. Zhang, J. Wang, Y. Jin, G. Liu, S. Yang, and X. Yao, “Insights on Lithium Plating Behavior in Graphite-Based All-Solid-State Lithium-Ion Batteries,” Energy Storage Materials 54 (2023): 845–853.

[22] S. Chen, J. Zhang, L. Nie, et al., “All-Solid-State Batteries With a Limited Lithium Metal Anode at Room Temperature Using a Garnet-Based Electrolyte,” Advanced Materials 33, no. 1 (2021): 2002325.

[23] Z. Shen, W. Zhang, G. Zhu, Y. Huang, Q. Feng, and Y. Lu, “Design Principles of the Anode–Electrolyte Interface for All Solid-State Lithium Metal Batteries,” Small Methods 4, no. 1 (2020): 1900592.

[24] S. Y. Han, C. Lee, J. A. Lewis, et al., “Stress Evolution During Cycling of Alloy-Anode Solid-State Batteries,” Joule 5, no. 9 (2021): 2450–2465.

[25] X. Zhang, S. Wang, C. Xue, et al., “Self-Suppression of Lithium Dendrite in All-Solid-State Lithium Metal Batteries With Poly(Vinylidene Difluoride)-Based Solid Electrolytes,” Advanced Materials 31, no. 11 (2019): 1806082.

[26] P. Albertus, V. Anandan, C. Ban, et al., “Challenges for and Pathways Toward Li-Metal-Based All-Solid-State Batteries,” ACS Energy Letters 6, no. 4 (2021): 1399–1404.

[27] C. Doerrer, I. Capone, S. Narayanan, et al., “High Energy Density Single-Crystal NMC/Li₆PS₅Cl Cathodes for All-Solid-State Lithium-Metal Batteries,” ACS Applied Materials & Interfaces 13, no. 31 (2021): 37809–37815.

[28] J.-M. Doux, H. Nguyen, D. H. S. Tan, et al., “Stack Pressure Considerations for Room-Temperature All-Solid-State Lithium Metal Batteries,” Advanced Energy Materials 10, no. 1 (2020): 1903253.

[29] C. Lee, S. Y. Han, J. A. Lewis, et al., “Stack Pressure Measurements to Probe the Evolution of the Lithium–Solid-State Electrolyte Interface,” ACS Energy Letters 6, no. 9 (2021): 3261–3269.

[30] B. Hu, S. Zhang, Z. Ning, et al., “Deflecting Lithium Dendritic Cracks in Multi-Layered Solid Electrolytes,” Joule 8 (2024): 2623–2638.

[31] S. Li, S.-J. Yang, G.-X. Liu, et al., “A Dynamically Stable Mixed Conducting Interphase for All-Solid-State Lithium Metal Batteries,” Advanced Materials 36, no. 3 (2024): 2307768.

[32] F. Zhao, Q. Sun, C. Yu, et al., “Ultrastable Anode Interface Achieved by Fluorinating Electrolytes for All-Solid-State Li Metal Batteries,” ACS Energy Letters 5, no. 4 (2020): 1035–1043.

[33] S. Lee, K. Lee, S. Kim, et al., “Design of a Lithiophilic and Electron-Blocking Interlayer for Dendrite-Free Lithium-Metal Solid-State Batteries,” Science Advances 8, no. 30 (2022): eabq0153.

[34] L. Ye and X. Li, “A Dynamic Stability Design Strategy for Lithium Metal Solid State Batteries,” Nature 593, no. 7858 (2021): 218–222.

[35] C. Wu, B. Emley, L. Zhao, et al., “Understanding the Chemomechanical Function of the Silver–Carbon Interlayer in Sheet-Type All-Solid-State Lithium–Metal Batteries,” Nano Letters 23, no. 10 (2023): 4415–4422.

[36] H. Liu, Q. Zhu, C. Wang, et al., “High Air Stability and Excellent Li Metal Compatibility of Argyrodite-Based Electrolyte Enabling Superior All-Solid-State Li Metal Batteries,” Advanced Functional Materials 32, no. 32 (2022): 2203858.

[37] L. Zhou, N. Minafra, W. G. Zeier, and L. F. Nazar, “Innovative Approaches to Li-Argyrodite Solid Electrolytes for All-Solid-State Lithium Batteries,” Accounts of Chemical Research 54, no. 12 (2021): 2717–2728.

[38] D. H. S. Tan, E. A. Wu, H. Nguyen, et al., “Elucidating Reversible Electrochemical Redox of Li₆PS₅Cl Solid Electrolyte,” ACS Energy Letters 4, no. 10 (2019): 2418–2427.

[39] E. Zhao, L. He, Z. Zhang, et al., “New Insights Into Li Distribution in the Superionic Argyrodite Li₆PS₅Cl,” Chemical Communications 57, no. 82 (2021): 10787–10790.

[40] A. Gautam, M. Ghidiu, E. Suard, M. A. Kraft, and W. G. Zeier, “On the Lithium Distribution in Halide Superionic Argyrodites by Halide Incorporation in Li_7−xPS_6−xCl_x,” ACS Applied Energy Materials 4, no. 7 (2021): 7309–7315.

[41] A. Gautam, M. Sadowski, M. Ghidiu, et al., “Engineering the Site-Disorder and Lithium Distribution in the Lithium Superionic Argyrodite Li₆PS₅Br,” Advanced Energy Materials 11, no. 5 (2021): 2003369.

[42] B. He, F. Zhang, Y. Xin, et al., “Halogen Chemistry of Solid Electrolytes in All-Solid-State Batteries,” Nature Reviews Chemistry 7, no. 12 (2023): 826–842.

[43] R. Schlenker, A.-L. Hansen, A. Senyshyn, et al., “Structure and Diffusion Pathways in Li₆PS₅Cl Argyrodite From Neutron Diffraction, Pair-Distribution Function Analysis, and NMR,” Chemistry of Materials 32, no. 19 (2020): 8420–8430.

[44] A. Banerjee, H. Tang, X. Wang, et al., “Revealing Nanoscale Solid-Solid Interfacial Phenomena for Long-Life and High-Energy All-Solid-State Batteries,” ACS Applied Materials & Interfaces 11, no. 46 (2019): 43138–43145.

[45] Y.-T. Chen, M. A. T. Marple, D. H. S. Tan, et al., “Investigating Dry Room Compatibility of Sulfide Solid-State Electrolytes for Scalable Manufacturing,” Journal of Materials Chemistry A 10, no. 13 (2022): 7155–7164.

[46] C. Dietrich, D. A. Weber, S. Culver, et al., “Synthesis, Structural Characterization, and Lithium Ion Conductivity of the Lithium Thiophosphate Li₂P₂S₆,” Inorganic Chemistry 56, no. 11 (2017): 6681–6687.

[47] W. Arnold, D. A. Buchberger, Y. Li, M. Sunkara, T. Druffel, and H. Wang, “Halide Doping Effect on Solvent-Synthesized Lithium Argyrodites Li₆PS₅X (X = Cl, Br, I) Superionic Conductors,” Journal of Power Sources 464 (2020): 228158.

[48] T. Takeuchi, H. Kageyama, K. Nakanishi, et al., “Rapid Preparation of Li₂S-P₂S₅ Solid Electrolyte and Its Application for graphite/Li₂S All-Solid-State Lithium Secondary Battery,” ECS Electrochemistry Letters 3, no. 5 (2014): A31–A35.

[49] P. Partovi-Azar, T. D. Kühne, and P. Kaghazchi, “Evidence for the Existence of Li₂S₂ Clusters in Lithium–Sulfur Batteries: Ab Initio Raman Spectroscopy Simulation,” Physical Chemistry Chemical Physics 17, no. 34 (2015): 22009–22014.

[50] J. Lim, Y. Zhou, R. H. Powell, T. Ates, S. Passerini, and L. J. Hardwick, “Localised Degradation Within Sulfide-Based All-Solid-State Electrodes Visualised by Raman Mapping,” Chemical Communications 59, no. 51 (2023): 7982–7985.

[51] C. J. Carmalt, E. S. Peters, I. P. Parkin, T. D. Manning, and A. L. Hector, “Chemical Vapor Deposition of Niobium Disulfide Thin Films,” European Journal of Inorganic Chemistry 2004, no. 22 (2004): 4470–4476.

[52] X. Feng, P.-H. Chien, Y. Wang, et al., “Enhanced Ion Conduction by Enforcing Structural Disorder in Li-Deficient Argyrodites Li_6−xPS_5−xCl_1+x,” Energy Storage Materials 30 (2020): 67–73.

[53] S. Li, J. Lin, M. Schaller, et al., “High-Entropy Lithium Argyrodite Solid Electrolytes Enabling Stable All-Solid-State Batteries,” Angewandte Chemie International Edition 62, no. 50 (2023): e202314155.

[54] A. C. Olson, J. M. Keith, E. R. Batista, et al., “Using Solution-And Solid-State S K-Edge X-Ray Absorption Spectroscopy With Density Functional Theory to Evaluate M–S Bonding for MS₄²⁻ (M = Cr, Mo, W) Dianions,” Dalton Transactions 43, no. 46 (2014): 17283–17295.

[55] T. Shi, Q. Tu, Y. Tian, et al., “High Active Material Loading in All-Solid-State Battery Electrode via Particle Size Optimization,” Advanced Energy Materials 10, no. 1 (2020): 1902881.

[56] E. Schlautmann, A. Weiß, O. Maus, et al., “Impact of the Solid Electrolyte Particle Size Distribution in Sulfide-Based Solid-State Battery Composites,” Advanced Energy Materials 13, no. 41 (2023): 2302309.

[57] T. Swamy, X. Chen, and Y.-M. Chiang, “Electrochemical Redox Behavior of Li Ion Conducting Sulfide Solid Electrolytes,” Chemistry of Materials 31, no. 3 (2019): 707–713.

[58] T. K. Schwietert, V. A. Arszelewska, C. Wang, et al., “Clarifying the Relationship Between Redox Activity and Electrochemical Stability in Solid Electrolytes,” Nature Materials 19, no. 4 (2020): 428–435.

[59] J. Kasemchainan, S. Zekoll, D. Spencer Jolly, et al., “Critical Stripping Current Leads to Dendrite Formation on Plating in Lithium Anode Solid Electrolyte Cells,” Nature Materials 18, no. 10 (2019): 1105–1111.

[60] Z. Ning, G. Li, D. L. R. Melvin, et al., “Dendrite Initiation and Propagation in Lithium Metal Solid-State Batteries,” Nature 618, no. 7964 (2023): 287–293.

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