LaCl3-based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries

Fu, Chengyu; Li, Yifan; Xu, Wenjie; Feng, Xuyong; Gu, Weijian; Liu, Jue; Deng, Wenwen; Wang, Wei; Abeykoon, A. M. Milinda; Su, Laisuo; Zhu, Lingyun; Wu, Xiaojun; Xiang, Hongfa

doi:10.1038/s41467-024-48712-4

Title: LaCl₃-based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries

Journal Article · 20 May 2024 · Nature Communications

DOI: https://doi.org/10.1038/s41467-024-48712-4 · OSTI ID:2432547

Fu, Chengyu ^[1]; Li, Yifan ^[2]; Xu, Wenjie ^[2];

^[1]; Gu, Weijian ^[1];

^[3]; Deng, Wenwen ^[4]; Wang, Wei ^[5]; Abeykoon, A. M. Milinda ^[6];

^[7];

^[8];

^[2];

^[1]

Hefei University of Technology (China)
University of Science and Technology of China, Hefei (China)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Suzhou University of Science and Technology (China)
Chinese Academy of Sciences (CAS), Fuzhou (China). Key Laboratory of Design and Assembly of Functional Nanostructures
Brookhaven National Laboratory (BNL), Upton, NY (United States)
University of Texas at Dallas, Richardson, TX (United States)
Anhui University, Hefei (China)

To enable high performance of all solid-state batteries, a catholyte should demonstrate high ionic conductivity, good compressibility and oxidative stability. Here, a LaCl₃-based Na⁺ superionic conductor (Na_1–xZr_xLa_1–xCl₄) with high ionic conductivity of 2.9 × 10^–4 S cm^–1 (30 °C), good compressibility and high oxidative potential (3.80 V vs. Na₂Sn) is prepared via solid state reaction combining mechanochemical method. X-ray diffraction reveals a hexagonal structure (P6₃/m) of Na_1–xZr_xLa_1–xCl₄, with Na⁺ ions forming a one-dimensional diffusion channel along the c-axis. First-principle calculations combining with X-ray absorption fine structure characterization etc. reveal that the ionic conductivity of Na_1–xZr_xLa_1–xCl₄ is mainly determined by the size of Na⁺-channels and the Na⁺/La³⁺ mixing in the one-dimensional diffusion channels. When applied as a catholyte, the NaCrO₂||Na_0.7Zr_0.3La_0.7Cl₄||Na₃PS₄||Na₂Sn all-solid-state batteries demonstrate an initial capacity of 114 mA h g^–1 and 88% retention after 70 cycles at 0.3 C. In addition, a high capacity of 94 mA h g^–1 can be maintained at 1 C current density.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: Anhui Provincial Natural Science Foundation; Chinese Academy of Sciences; Fundamental Research Funds for the Central Universities; Major Science and Technology Projects in Anhui Province; National Natural Science Foundation for Distinguished Young Scholars; National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 2432547

Report Number(s):: BNL--225924-2024-JAAM

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 15; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Complex Hydrides for Electrochemical Energy Storage Unemoto, Atsushi; Matsuo, Motoaki; Orimo, Shin-ichi Advanced Functional Materials, Vol. 24, Issue 16 https://doi.org/10.1002/adfm.201303147	journal	January 2014
Studies of Functional Defects for Fast Na-Ion Conduction in Na ₃₋ _y PS ₄₋ _x Cl _x with a Combined Experimental and Computational Approach Feng, Xuyong; Chien, Po-Hsiu; Zhu, Zhuoying Advanced Functional Materials, Vol. 29, Issue 9 https://doi.org/10.1002/adfm.201807951	journal	January 2019
Solid Halide Electrolytes with High Lithium-Ion Conductivity for Application in 4 V Class Bulk-Type All-Solid-State Batteries Asano, Tetsuya; Sakai, Akihiro; Ouchi, Satoru Advanced Materials, Vol. 30, Issue 44 https://doi.org/10.1002/adma.201803075	journal	September 2018
Borohydride-Scaffolded Li/Na/Mg Fast Ionic Conductors for Promising Solid-State Electrolytes Cuan, Jing; Zhou, You; Zhou, Tengfei Advanced Materials, Vol. 31, Issue 1 https://doi.org/10.1002/adma.201803533	journal	October 2018
Vacancy-Contained Tetragonal Na ₃ SbS ₄ Superionic Conductor Zhang, Long; Zhang, Dechao; Yang, Kun Advanced Science, Vol. 3, Issue 10 https://doi.org/10.1002/advs.201600089	journal	April 2016
Superionic Conduction of Sodium and Lithium in Anion-Mixed Hydroborates Na ₃ BH ₄ B ₁₂ H ₁₂ and (Li _0.7 Na _0.3 ) ₃ BH ₄ B ₁₂ H ₁₂ Sadikin, Yolanda; Brighi, Matteo; Schouwink, Pascal Advanced Energy Materials, Vol. 5, Issue 21 https://doi.org/10.1002/aenm.201501016	journal	August 2015
New Cost‐Effective Halide Solid Electrolytes for All‐Solid‐State Batteries: Mechanochemically Prepared Fe ³⁺ ‐Substituted Li ₂ ZrCl ₆ Kwak, Hiram; Han, Daseul; Lyoo, Jeyne Advanced Energy Materials, Vol. 11, Issue 12 https://doi.org/10.1002/aenm.202003190	journal	January 2021
Enhancing the Dendrite Tolerance of NaSICON Electrolytes by Suppressing Edge Growth of Na Electrode along Ceramic Surface Ma, Qianli; Ortmann, Till; Yang, Aikai Advanced Energy Materials, Vol. 12, Issue 40 https://doi.org/10.1002/aenm.202201680	journal	August 2022
Vacancy-Controlled Na ⁺ Superion Conduction in Na ₁₁ Sn ₂ PS ₁₂ Duchardt, Marc; Ruschewitz, Uwe; Adams, Stefan Angewandte Chemie International Edition, Vol. 57, Issue 5 https://doi.org/10.1002/anie.201712769	journal	January 2018
Water‐Mediated Synthesis of a Superionic Halide Solid Electrolyte Li, Xiaona; Liang, Jianwen; Chen, Ning Angewandte Chemie International Edition, Vol. 58, Issue 46 https://doi.org/10.1002/anie.201909805	journal	November 2019
Heavily Tungsten‐Doped Sodium Thioantimonate Solid‐State Electrolytes with Exceptionally Low Activation Energy for Ionic Diffusion Feng, Xuyong; Fang, Hong; Liu, Pengcheng Angewandte Chemie International Edition, Vol. 60, Issue 50 https://doi.org/10.1002/anie.202110699	journal	November 2021
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
Die Chloride Na3xM2-xCl6 (M = La?Sm) und NaM2Cl6 (M = Nd, Sm): Derivate des UCl3-Typs. Synthese, Kristallstruktur und R�ntgenabsorptionsspektroskopie (XANES) Lissner, Falk; Kr�mer, Karl; Schleid, Thomas Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 620, Issue 3 https://doi.org/10.1002/zaac.19946200307	journal	March 1994
Recent advances in Li1+xAlxTi2−x(PO4)3 solid-state electrolyte for safe lithium batteries Xiao, Wei; Wang, Jingyu; Fan, Linlin Energy Storage Materials, Vol. 19 https://doi.org/10.1016/j.ensm.2018.10.012	journal	May 2019
Na2ZrCl6 enabling highly stable 3 V all-solid-state Na-ion batteries Kwak, Hiram; Lyoo, Jeyne; Park, Juhyoun Energy Storage Materials, Vol. 37 https://doi.org/10.1016/j.ensm.2021.01.026	journal	May 2021
Fabrication of Li1+xAlxGe2-x(PO4)3 thin films by sputtering for solid electrolytes Mousavi, T.; Chen, X.; Doerrer, C. Solid State Ionics, Vol. 354 https://doi.org/10.1016/j.ssi.2020.115397	journal	October 2020
Role of Na ⁺ Interstitials and Dopants in Enhancing the Na ⁺ Conductivity of the Cubic Na ₃ PS ₄ Superionic Conductor Zhu, Zhuoying; Chu, Iek-Heng; Deng, Zhi Chemistry of Materials, Vol. 27, Issue 24 https://doi.org/10.1021/acs.chemmater.5b03656	journal	December 2015
Diffusion Mechanism of the Sodium-Ion Solid Electrolyte Na ₃ PS ₄ and Potential Improvements of Halogen Doping de Klerk, Niek J. J.; Wagemaker, Marnix Chemistry of Materials, Vol. 28, Issue 9 https://doi.org/10.1021/acs.chemmater.6b00698	journal	April 2016
Yttrium–Sodium Halides as Promising Solid-State Electrolytes with High Ionic Conductivity and Stability for Na-Ion Batteries Qie, Yu; Wang, Shuo; Fu, Sijie The Journal of Physical Chemistry Letters, Vol. 11, Issue 9 https://doi.org/10.1021/acs.jpclett.0c00010	journal	April 2020
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
Ultrastable All-Solid-State Sodium Rechargeable Batteries Yang, Jing; Liu, Gaozhan; Avdeev, Maxim ACS Energy Letters, Vol. 5, Issue 9 https://doi.org/10.1021/acsenergylett.0c01432	journal	August 2020
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
Defect-Mediated Conductivity Enhancements in Na _{3– x} Pn _{1– x} W _x S ₄ (Pn = P, Sb) Using Aliovalent Substitutions Fuchs, Till; Culver, Sean P.; Till, Paul ACS Energy Letters, Vol. 5, Issue 1 https://doi.org/10.1021/acsenergylett.9b02537	journal	November 2019
A New Superionic Plastic Polymorph of the Na ⁺ Conductor Na ₃ PS ₄ Famprikis, Theodosios; Dawson, James A.; Fauth, François ACS Materials Letters, Vol. 1, Issue 6 https://doi.org/10.1021/acsmaterialslett.9b00322	journal	October 2019
Atomic-Scale Investigation of Defects, Dopants, and Lithium Transport in the LiFePO ₄ Olivine-Type Battery Material Islam, M. Saiful; Driscoll, Daniel J.; Fisher, Craig A. J. Chemistry of Materials, Vol. 17, Issue 20 https://doi.org/10.1021/cm050999v	journal	October 2005
Site-Occupation-Tuned Superionic Li _x ScCl _{3+ x} Halide Solid Electrolytes for All-Solid-State Batteries Liang, Jianwen; Li, Xiaona; Wang, Shuo Journal of the American Chemical Society, Vol. 142, Issue 15 https://doi.org/10.1021/jacs.0c00134	journal	March 2020
Superionic Conducting Halide Frameworks Enabled by Interface-Bonded Halides Fu, Jiamin; Wang, Shuo; Liang, Jianwen Journal of the American Chemical Society, Vol. 145, Issue 4 https://doi.org/10.1021/jacs.2c09446	journal	December 2022
Design and synthesis of the superionic conductor Na10SnP2S12 Richards, William D.; Tsujimura, Tomoyuki; Miara, Lincoln J. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11009	journal	March 2016
Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries Hayashi, Akitoshi; Noi, Kousuke; Sakuda, Atsushi Nature Communications, Vol. 3, Issue 1 https://doi.org/10.1038/ncomms1843	journal	January 2012
A lithium superionic conductor Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro Nature Materials, Vol. 10, Issue 9, p. 682-686 https://doi.org/10.1038/nmat3066	journal	July 2011
A sodium-ion sulfide solid electrolyte with unprecedented conductivity at room temperature Hayashi, A.; Masuzawa, N.; Yubuchi, S. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-13178-2	journal	November 2019
A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries Wu, Erik A.; Banerjee, Swastika; Tang, Hanmei Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-21488-7	journal	February 2021
A cost-effective and humidity-tolerant chloride solid electrolyte for lithium batteries Wang, Kai; Ren, Qingyong; Gu, Zhenqi Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-24697-2	journal	July 2021
An electrochemically stable homogeneous glassy electrolyte formed at room temperature for all-solid-state sodium batteries Chi, Xiaowei; Zhang, Ye; Hao, Fang Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-30517-y	journal	May 2022
Fundamental investigations on the sodium-ion transport properties of mixed polyanion solid-state battery electrolytes Deng, Zeyu; Mishra, Tara P.; Mahayoni, Eunike Nature Communications, Vol. 13, Issue 1 https://doi.org/10.1038/s41467-022-32190-7	journal	August 2022
Boosting the interfacial superionic conduction of halide solid electrolytes for all-solid-state batteries Kwak, Hiram; Kim, Jae-Seung; Han, Daseul Nature Communications, Vol. 14, Issue 1 https://doi.org/10.1038/s41467-023-38037-z	journal	April 2023
Statistical variances of diffusional properties from ab initio molecular dynamics simulations He, Xingfeng; Zhu, Yizhou; Epstein, Alexander npj Computational Materials, Vol. 4, Issue 1 https://doi.org/10.1038/s41524-018-0074-y	journal	April 2018
Ultra-stable all-solid-state sodium metal batteries enabled by perfluoropolyether-based electrolytes Wang, Xiaoen; Zhang, Cheng; Sawczyk, Michal Nature Materials, Vol. 21, Issue 9 https://doi.org/10.1038/s41563-022-01296-0	journal	July 2022
A LaCl3-based lithium superionic conductor compatible with lithium metal Yin, Yi-Chen; Yang, Jing-Tian; Luo, Jin-Da Nature, Vol. 616, Issue 7955 https://doi.org/10.1038/s41586-023-05899-8	journal	April 2023
Electrolyte design strategies and research progress for room-temperature sodium-ion batteries Che, Haiying; Chen, Suli; Xie, Yingying Energy & Environmental Science, Vol. 10, Issue 5 https://doi.org/10.1039/C7EE00524E	journal	January 2017
Room temperature demonstration of a sodium superionic conductor with grain conductivity in excess of 0.01 S cm ⁻¹ and its primary applications in symmetric battery cells Ma, Qianli; Tsai, Chih-Long; Wei, Xian-Kui Journal of Materials Chemistry A, Vol. 7, Issue 13 https://doi.org/10.1039/C9TA00048H	journal	January 2019
A new halospinel superionic conductor for high-voltage all solid state lithium batteries Zhou, Laidong; Kwok, Chun Yuen; Shyamsunder, Abhinandan Energy & Environmental Science, Vol. 13, Issue 7 https://doi.org/10.1039/D0EE01017K	journal	January 2020
Materials design of sodium chloride solid electrolytes Na₃MCl₆ for all-solid-state sodium-ion batteries Park, Dongsu; Kim, Kwangnam; Chun, Gin Hyung Journal of Materials Chemistry A, Vol. 9, Issue 40 https://doi.org/10.1039/D1TA07050A	journal	January 2021
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996

Similar Records

A stable cathode-solid electrolyte composite for high-voltage, long-cycle-life solid-state sodium-ion batteries

Journal Article · 2021 · Nature Communications · OSTI ID:1783756

Wu, Erik A.; Banerjee, Swastika; Tang, Hanmei; +17 more

Room-Temperature All-solid-state Rechargeable Sodium-ion Batteries with a Cl-doped Na₃PS₄ Superionic Conductor

Journal Article · 2016 · Scientific Reports · OSTI ID:1559138

Chu, Iek-Heng; Kompella, Christopher S.; Nguyen, Han; +5 more

Synthesis and post-heating treatment of inorganic NaF·Na₃SbS₄ solid electrolytes

Journal Article · 2025 · Nano Energy · OSTI ID:2561402

Halacoglu, Selim; Guo, Xiaolin; Chen, Yan; +4 more

Related Subjects

36 MATERIALS SCIENCE
Batteries

Title: LaCl3-based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries

Citation Formats

References (48)

Similar Records

Related Subjects

Title: LaCl₃-based sodium halide solid electrolytes with high ionic conductivity for all-solid-state batteries