A New Class of Oxyhalide Solid Electrolytes NaNbCl 6‐2x O x for Solid‐state Sodium Batteries

Kmiec, Steven; Ruoff, Erick; Manthiram, Arumugam

doi:10.1002/ange.202416979

Title: A New Class of Oxyhalide Solid Electrolytes NaNbCl _6‐2x O _x for Solid‐state Sodium Batteries

Journal Article · 12 November 2024 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202416979 · OSTI ID:2477058

Kmiec, Steven ^[1]; Ruoff, Erick ^[1];

^[1]

Materials Science and Engineering Program and Texas Materials Institute The University of Texas at Austin Austin Texas 78712 USA

Abstract Sodium‐based batteries are gaining momentum due to the abundance and lower cost of sodium compared to lithium. Solid‐state sodium batteries can also provide further safety advantages. However, sodium‐based solid‐state electrolytes (SSEs) that meet all the rigorous requirements, such as high ionic conductivity, oxidative stability with the cathode, and ease of processability, are lacking. We present here a new class of sodium‐based oxyhalide electrolytes NaNbCl _6‐2x O _x with a facile mechanochemical synthesis. The oxyhalide NaNbCl ₄ O exhibits close to two orders of magnitude higher ambient‐temperature sodium‐ion conductivity (1.03×10 ⁻⁴ S cm ⁻¹ ) compared to the halide counterpart NaNbCl ₆ (3×10 ⁻⁶ S cm ⁻¹ ). Structural motifs unique to the oxygen content in NaNbCl _6‐2x O _x are identified with ²³ Na and ⁹³ Nb magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy and x‐ray diffraction (XRD). Solid‐state sodium batteries assembled with NaNbCl ₄ O electrolyte and the cobalt‐ and nickel‐free layered Na _0.70 Fe _0.3 Mn _0.65 Al _0.05 O ₂ cathode exhibit a maximum discharge capacity of 155 mAh g ⁻¹ with good cycle life at ambient temperature.

View Accepted Manuscript (Publisher)

Cite

Export

Save

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0005397

OSTI ID:: 2477058

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 5 Vol. 137; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

References (45)

Halide Heterogeneous Structure Boosting Ionic Diffusion and High‐Voltage Stability of Sodium Superionic Conductors Fu, Jiamin; Wang, Shuo; Wu, Duojie Advanced Materials, Vol. 36, Issue 3 https://doi.org/10.1002/adma.202308012	journal	October 2023
Solid‐State Li–Metal Batteries: Challenges and Horizons of Oxide and Sulfide Solid Electrolytes and Their Interfaces Kim, Kun Joong; Balaish, Moran; Wadaguchi, Masaki Advanced Energy Materials, Vol. 11, Issue 1 https://doi.org/10.1002/aenm.202002689	journal	November 2020
All‐Solid‐State Batteries: New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe³⁺‐Substituted Li₂ZrCl₆ (Adv. Energy Mater. 12/2021) Kwak, Hiram; Han, Daseul; Lyoo, Jeyne Advanced Energy Materials, Vol. 11, Issue 12 https://doi.org/10.1002/aenm.202170045	journal	March 2021
Visualizing the Chemical Incompatibility of Halide and Sulfide‐Based Electrolytes in Solid‐State Batteries Rosenbach, Carolin; Walther, Felix; Ruhl, Justine Advanced Energy Materials, Vol. 13, Issue 6 https://doi.org/10.1002/aenm.202203673	journal	December 2022
Challenges and Prospects of Sodium‐Ion and Potassium‐Ion Batteries for Mass Production Sada, Krishnakanth; Darga, Joe; Manthiram, Arumugam Advanced Energy Materials, Vol. 13, Issue 39 https://doi.org/10.1002/aenm.202302321	journal	September 2023
Crack‐Free Single‐Crystalline LiNiO₂ for High Energy Density All‐Solid‐State Batteries Lee, Dongsoo; Mesnier, Alex; Manthiram, Arumugam Advanced Energy Materials, Vol. 14, Issue 19 https://doi.org/10.1002/aenm.202303490	journal	March 2024
New Oxyhalide Solid Electrolytes with High Lithium Ionic Conductivity >10 mS cm⁻¹ for All‐Solid‐State Batteries Tanaka, Yoshiaki; Ueno, Koki; Mizuno, Keita Angewandte Chemie International Edition, Vol. 62, Issue 13 https://doi.org/10.1002/anie.202217581	journal	February 2023
Industrialization of Layered Oxide Cathodes for Lithium‐Ion and Sodium‐Ion Batteries: A Comparative Perspective Darga, Joe; Lamb, Julia; Manthiram, Arumugam Energy Technology, Vol. 8, Issue 12 https://doi.org/10.1002/ente.202000723	journal	October 2020
Achieving High Stability and Performance in P2‐Type Mn‐Based Layered Oxides with Tetravalent Cations for Sodium‐Ion Batteries Vanaphuti, Panawan; Yao, Zeyi; Liu, Yangtao Small, Vol. 18, Issue 19 https://doi.org/10.1002/smll.202201086	journal	April 2022
Li+ conduction in aliovalent-substituted monoclinic Li2ZrCl6 for all-solid-state batteries: Li2+xZr1-xMxCl6 (M = In, Sc) Kwak, Hiram; Han, Daseul; Son, Jun Pyo Chemical Engineering Journal, Vol. 437 https://doi.org/10.1016/j.cej.2022.135413	journal	June 2022
On the failure mechanism of Nb electrodeposition from NbCl5 in alkylmethylpyrrolidinium TFSI ionic liquids Seidl, Lukas; Yesilbas, Göktug; Fischer, Pauline Electrochimica Acta, Vol. 362 https://doi.org/10.1016/j.electacta.2020.137176	journal	December 2020
Reviewing the current status and development of polymer electrolytes for solid-state lithium batteries Wang, Hangchao; Sheng, Li; Yasin, Ghulam Energy Storage Materials, Vol. 33 https://doi.org/10.1016/j.ensm.2020.08.014	journal	December 2020
Origin of Fast Li+-Ion Conductivity in the Compressible Oxyhalide LiNbOCl4 Adams, Stefan Energy Storage Materials, Vol. 68 https://doi.org/10.1016/j.ensm.2024.103359	journal	April 2024
High-Efficiency Lithium Metal Batteries with Fire-Retardant Electrolytes Chen, Shuru; Zheng, Jianming; Yu, Lu Joule, Vol. 2, Issue 8 https://doi.org/10.1016/j.joule.2018.05.002	journal	August 2018
Study of a dry room in a battery manufacturing plant using a process model Ahmed, Shabbir; Nelson, Paul A.; Dees, Dennis W. Journal of Power Sources, Vol. 326 https://doi.org/10.1016/j.jpowsour.2016.06.107	journal	September 2016
Superionic amorphous NaTaCl6 halide electrolyte for highly reversible all-solid-state Na-ion batteries Hu, Yang; Fu, Jiamin; Xu, Jiabin Matter, Vol. 7, Issue 3 https://doi.org/10.1016/j.matt.2023.12.017	journal	March 2024
Flammability parameters of lithium-ion battery electrolytes Swiderska-Mocek, A.; Jakobczyk, P.; Rudnicka, E. Journal of Molecular Liquids, Vol. 318 https://doi.org/10.1016/j.molliq.2020.113986	journal	November 2020
Technological pathways toward sustainable batteries Manthiram, Arumugam; Lutkenhaus, Jodie L.; Fu, Yongzhu One Earth, Vol. 5, Issue 3 https://doi.org/10.1016/j.oneear.2022.02.010	journal	March 2022
Controlling Defects to Achieve Reproducibly High Ionic Conductivity in Na₃SbS₄ Solid Electrolytes Shimoda, Masaki; Maegawa, Mayu; Yoshida, Suguru Chemistry of Materials, Vol. 34, Issue 12 https://doi.org/10.1021/acs.chemmater.2c00944	journal	June 2022
Molecular Dynamics Modeling of the Structure and Na ⁺ -Ion Transport in Na ₂ S + SiS ₂ Glassy Electrolytes Dive, A.; Benmore, C.; Wilding, M. The Journal of Physical Chemistry B, Vol. 122, Issue 30 https://doi.org/10.1021/acs.jpcb.8b04353	journal	June 2018
Characterizing the Structural Change of Na₃PS₄ Solid Electrolytes in a Humid N₂ Atmosphere Nakano, Takumi; Kimura, Takuya; Sakuda, Atsushi The Journal of Physical Chemistry C, Vol. 126, Issue 17 https://doi.org/10.1021/acs.jpcc.2c00421	journal	April 2022
Electrode–Electrolyte Interface in Li-Ion Batteries: Current Understanding and New Insights Gauthier, Magali; Carney, Thomas J.; Grimaud, Alexis The Journal of Physical Chemistry Letters, Vol. 6, Issue 22 https://doi.org/10.1021/acs.jpclett.5b01727	journal	October 2015
Stable Thiophosphate-Based All-Solid-State Lithium Batteries through Conformally Interfacial Nanocoating Cao, Daxian; Zhang, Yubin; Nolan, Adelaide M. Nano Letters, Vol. 20, Issue 3 https://doi.org/10.1021/acs.nanolett.9b02678	journal	September 2019
Na _{3– x} Er _{1– x} Zr _x Cl ₆ —A Halide-Based Fast Sodium-Ion Conductor with Vacancy-Driven Ionic Transport Schlem, Roman; Banik, Ananya; Eckardt, Mirco ACS Applied Energy Materials, Vol. 3, Issue 10 https://doi.org/10.1021/acsaem.0c01870	journal	September 2020
In Search of the Best Solid Electrolyte-Layered Oxide Pairing for Assembling Practical All-Solid-State Batteries Koç, Tuncay; Marchini, Florencia; Rousse, Gwenaëlle ACS Applied Energy Materials, Vol. 4, Issue 12 https://doi.org/10.1021/acsaem.1c02187	journal	November 2021
Surface-Modified Na(Ni _0.3 Fe _0.4 Mn _0.3 )O ₂ Cathodes with Enhanced Cycle Life and Air Stability for Sodium-Ion Batteries Lamb, Julia; Manthiram, Arumugam ACS Applied Energy Materials, Vol. 4, Issue 10 https://doi.org/10.1021/acsaem.1c02485	journal	October 2021
Formation of Passivate Interphases by Na₃BS₃-Glass Solid Electrolytes in All-Solid-State Sodium-Metal Batteries Nasu, Akira; Inaoka, Takeaki; Tsuji, Fumika ACS Applied Materials & Interfaces, Vol. 14, Issue 21 https://doi.org/10.1021/acsami.2c05090	journal	May 2022
Electrochemically Stable Li_3–xIn_1–xHf_xCl₆ Halide Solid Electrolytes for All-Solid-State Batteries Wang, Heng; Li, Yuxiang; Tang, Ya ACS Applied Materials & Interfaces, Vol. 15, Issue 4 https://doi.org/10.1021/acsami.2c21022	journal	January 2023
NaAlCl₄: New Halide Solid Electrolyte for 3 V Stable Cost-Effective All-Solid-State Na-Ion Batteries Park, Juhyoun; Son, Jun Pyo; Ko, Wonseok ACS Energy Letters, Vol. 7, Issue 10 https://doi.org/10.1021/acsenergylett.2c01514	journal	September 2022
Extending the Electrochemical Window of Na⁺ Halide Nanocomposite Solid Electrolytes for 5 V-Class All-Solid-State Na-Ion Batteries Park, Juhyoun; Han, Daseul; Son, Jun Pyo ACS Energy Letters, Vol. 9, Issue 5 https://doi.org/10.1021/acsenergylett.4c00490	journal	April 2024
Insights on Na₃PS₄ Solid-State Electrolyte Dry Films: Interfacial Stability and Dry Room Compatibility Xu, Dapeng; Tang, Wei; Li, Feng ACS Energy Letters, Vol. 9, Issue 5 https://doi.org/10.1021/acsenergylett.4c00659	journal	April 2024
4 V Na Solid State Batteries Enabled by a Scalable Sodium Metal Oxyhalide Solid Electrolyte Zhou, Laidong; Bazak, J. David; Li, Chang ACS Energy Letters, Vol. 9, Issue 8 https://doi.org/10.1021/acsenergylett.4c01855	journal	July 2024
NaMCl₆ (M = Nb and Ta): A New Class of Sodium-Conducting Halide-Based Solid Electrolytes Huang, Zheng; Yoshida, Suguru; Akamatsu, Hirofumi ACS Materials Letters, Vol. 6, Issue 5, p. 1732-1738 https://doi.org/10.1021/acsmaterialslett.4c00315	journal	April 2024
Raman Spectroscopic and ab initio Quantum Chemical Investigations of Molecules and Complex Ions in the Molten System CsCl-NbCl5-NbOCl3 Rosenkilde, Christian; Voyiatzis, George; Jensen, Vidar R. Inorganic Chemistry, Vol. 34, Issue 17 https://doi.org/10.1021/ic00121a014	journal	August 1995
Critical Role of Framework Flexibility and Disorder in Driving High Ionic Conductivity in LiNbOCl₄ Singh, Baltej; Wang, Yubo; Liu, Jue Journal of the American Chemical Society, Vol. 146, Issue 25 https://doi.org/10.1021/jacs.4c03142	journal	June 2024
A reflection on lithium-ion battery cathode chemistry Manthiram, Arumugam Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-15355-0	journal	March 2020
High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes Han, Fudong; Westover, Andrew S.; Yue, Jie Nature Energy, Vol. 4, Issue 3 https://doi.org/10.1038/s41560-018-0312-z	journal	January 2019
Sodium is the new lithium Ohno, S.; Zeier, W. G. Nature Energy, Vol. 7, Issue 8 https://doi.org/10.1038/s41560-022-01084-9	journal	July 2022
Chloride electrode composed of ubiquitous elements for high-energy-density all-solid-state sodium-ion batteries Tanibata, Naoto; Nonaka, Naoki; Makino, Keisuke Scientific Reports, Vol. 14, Issue 1 https://doi.org/10.1038/s41598-024-53154-5	journal	February 2024
Preparation and characterization of highly sodium ion conducting Na ₃ PS ₄ –Na ₄ SiS ₄ solid electrolytes Tanibata, Naoto; Noi, Kousuke; Hayashi, Akitoshi RSC Adv., Vol. 4, Issue 33 https://doi.org/10.1039/C4RA00996G	journal	January 2014
Compatibility issues between electrodes and electrolytes in solid-state batteries Tian, Yaosen; Shi, Tan; Richards, William D. Energy & Environmental Science, Vol. 10, Issue 5 https://doi.org/10.1039/C7EE00534B	journal	January 2017
Optoelectronic properties of valence-state-controlled amorphous niobium oxide Onozato, Takaki; Katase, Takayoshi; Yamamoto, Akira Journal of Physics: Condensed Matter, Vol. 28, Issue 25 https://doi.org/10.1088/0953-8984/28/25/255001	journal	May 2016
The 2021 battery technology roadmap Ma, Jianmin; Li, Yutao; Grundish, Nicholas S. Journal of Physics D: Applied Physics, Vol. 54, Issue 18 https://doi.org/10.1088/1361-6463/abd353	journal	February 2021
Electrical Energy Storage for the Grid: A Battery of Choices Dunn, B.; Kamath, H.; Tarascon, J. -M. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1212741	journal	November 2011
Finding the Right Blend: Interplay Between Structure and Sodium Ion Conductivity in the System Na5AlS4–Na4SiS4 Harm, Sascha; Hatz, Anna-Katharina; Schneider, Christian Frontiers in Chemistry, Vol. 8 https://doi.org/10.3389/fchem.2020.00090	journal	February 2020

Similar Records

A New Class of Oxyhalide Solid Electrolytes NaNbCl _6‐2x O _x for Solid‐state Sodium Batteries

Journal Article · 2024 · Angewandte Chemie (International Edition) · OSTI ID:2536794

Kmiec, Steven; Ruoff, Erick; Manthiram, Arumugam

Ambient‐Temperature All‐Solid‐State Sodium Batteries with a Laminated Composite Electrolyte

Journal Article · 2020 · Advanced Functional Materials · OSTI ID:1618505

Yu, Xingwen; Xue, Leigang; Goodenough, John B.; +1 more

Tailored Organic Electrode Material Compatible with Sulfide Electrolyte for Stable All‐Solid‐State Sodium Batteries

Journal Article · 2018 · Angewandte Chemie · OSTI ID:1419899

Chi, Xiaowei; Liang, Yanliang; Hao, Fang; +6 more

Title: A New Class of Oxyhalide Solid Electrolytes NaNbCl 6‐2x O x for Solid‐state Sodium Batteries

Citation Formats

References (45)

Similar Records

Related Subjects

Title: A New Class of Oxyhalide Solid Electrolytes NaNbCl _6‐2x O _x for Solid‐state Sodium Batteries