Studies of Functional Defects for Fast Na-Ion Conduction in Na 3-yPS4-xClx with a Combined Experimental and Computational Approach

Feng, Xuyong; Chien, Po-Hsiu; Zhu, Zhuoying; Chu, Iek-Heng; Wang, Pengbo; Immediato-Scuotto, Marcello; Arabzadeh, Hesam; Ong, Shyue Ping; Hu, Yan-Yan

doi:10.1002/adfm.201807951

Title: Studies of Functional Defects for Fast Na-Ion Conduction in Na _3-_yPS_4-_xCl_x with a Combined Experimental and Computational Approach

Journal Article · Fri Jan 18 00:00:00 EST 2019 · Advanced Functional Materials

DOI:https://doi.org/10.1002/adfm.201807951· OSTI ID:1542272

Feng, Xuyong ^[1]; Chien, Po-Hsiu ^[1]; Zhu, Zhuoying ^[2]; Chu, Iek-Heng ^[2]; Wang, Pengbo ^[1]; Immediato-Scuotto, Marcello ^[1]; Arabzadeh, Hesam ^[1]; Ong, Shyue Ping ^[2];

^[3]

Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry
Univ. of California, San Diego, CA (United States). Dept. of NanoEngineering
Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry and Biochemistry; National High Magnetic Field Lab., Tallahassee, FL (United States). Center for Interdisciplinary Magnetic Resonance

Abstract All‐solid‐state rechargeable sodium (Na)‐ion batteries are promising for inexpensive and high‐energy‐density large‐scale energy storage. In this contribution, new Na solid electrolytes, Na ₃₋ _y PS ₄₋ _x Cl _x , are synthesized with a strategic approach, which allows maximum substitution of Cl for S ( x = 0.2) without significant compromise of structural integrity or Na deficiency. A maximum conductivity of 1.96 mS cm ⁻¹ at 25 °C is achieved for Na _3.0 PS _3.8 Cl _0.2 , which is two orders of magnitude higher compared with that of tetragonal Na ₃ PS ₄ (t‐Na ₃ PS ₄ ). The activation energy ( E _a ) is determined to be 0.19 eV. Ab initio molecular dynamics simulations shed light on the merit of maximizing Cl‐doping while maintaining low Na deficiency in enhanced Na‐ion conduction. Solid‐state nuclear magnetic resonance (NMR) characterizations confirm the successful substitution of Cl for S and the resulting change of P oxidation state from 5+ to 4+, which is also verified by spin moment analysis. Ion transport pathways are determined with a tracer‐exchange NMR method. The functional detects that promote Na ‐ion transport are maximized for further improvement in ionic conductivity. Full‐cell performance is demonstrated using Na/Na _3.0 PS _3.8 Cl _0.2 /Na ₃ V ₂ (PO ₄ ) ₃ with a reversible capacity of ≈100 mAh g ^‐1 at room temperature.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012118

OSTI ID:: 1542272

Alternate ID(s):: OSTI ID: 1491266

Journal Information:: Advanced Functional Materials, Vol. 29, Issue 9; ISSN 1616-301X

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 34 works

Citation information provided by
Web of Science

References (30)

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
Crystal structures and crystal chemistry in the system Na1+xZr2SixP3−xO12 Hong, H. Y-P. Materials Research Bulletin, Vol. 11, Issue 2 https://doi.org/10.1016/0025-5408(76)90073-8	journal	February 1976
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
Fast Na+-ion transport in skeleton structures Goodenough, J. B.; Hong, H. Y-P.; Kafalas, J. A. Materials Research Bulletin, Vol. 11, Issue 2 https://doi.org/10.1016/0025-5408(76)90077-5	journal	February 1976
Refinement of the crystal structure of Li ₄ P ₂ S ₆ using NMR crystallography Neuberger, Sven; Culver, Sean P.; Eckert, Hellmut Dalton Transactions, Vol. 47, Issue 33 https://doi.org/10.1039/C8DT02619J	journal	January 2018
Synthesis, structure determination, and ionic conductivity of sodium tetrathiophosphate Jansen, M.; Henseler, U. Journal of Solid State Chemistry, Vol. 99, Issue 1 https://doi.org/10.1016/0022-4596(92)90295-7	journal	July 1992
Lithium Ion Pathway within Li ₇ La ₃ Zr ₂ O ₁₂ -Polyethylene Oxide Composite Electrolytes Zheng, Jin; Tang, Mingxue; Hu, Yan-Yan Angewandte Chemie International Edition, Vol. 55, Issue 40 https://doi.org/10.1002/anie.201607539	journal	September 2016
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
Exceptionally High Ionic Conductivity in Na ₃ P _0.62 As _0.38 S ₄ with Improved Moisture Stability for Solid-State Sodium-Ion Batteries Yu, Zhaoxin; Shang, Shun-Li; Seo, Joo-Hwan Advanced Materials, Vol. 29, Issue 16 https://doi.org/10.1002/adma.201605561	journal	February 2017
Elastic Properties of Alkali Superionic Conductor Electrolytes from First Principles Calculations Deng, Zhi; Wang, Zhenbin; Chu, Iek-Heng Journal of The Electrochemical Society, Vol. 163, Issue 2 https://doi.org/10.1149/2.0061602jes	journal	November 2015
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
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
High temperature sodium batteries: status, challenges and future trends Hueso, Karina B.; Armand, Michel; Rojo, Teófilo Energy & Environmental Science, Vol. 6, Issue 3 https://doi.org/10.1039/c3ee24086j	journal	January 2013
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
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
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy APL Materials, Vol. 1, Issue 1 https://doi.org/10.1063/1.4812323	journal	July 2013
Conductivity measurements on nasicon and nasicon-modified materials Bohnke, O. Solid State Ionics, Vol. 122, Issue 1-4 https://doi.org/10.1016/S0167-2738(99)00062-4	journal	July 1999
Canonical dynamics: Equilibrium phase-space distributions Hoover, William G. Physical Review A, Vol. 31, Issue 3 https://doi.org/10.1103/PhysRevA.31.1695	journal	March 1985
Structural and Na-ion conduction characteristics of Na ₃ PS _x Se _4−x Bo, Shou-Hang; Wang, Yan; Ceder, Gerbrand Journal of Materials Chemistry A, Vol. 4, Issue 23 https://doi.org/10.1039/C6TA03027K	journal	January 2016
High-power all-solid-state batteries using sulfide superionic conductors Kato, Yuki; Hori, Satoshi; Saito, Toshiya Nature Energy, Vol. 1, Issue 4 https://doi.org/10.1038/nenergy.2016.30	journal	March 2016
Data-Driven First-Principles Methods for the Study and Design of Alkali Superionic Conductors Deng, Zhi; Zhu, Zhuoying; Chu, Iek-Heng Chemistry of Materials, Vol. 29, Issue 1 https://doi.org/10.1021/acs.chemmater.6b02648	journal	September 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
Algorithms and tools for high-throughput geometry-based analysis of crystalline porous materials Willems, Thomas F.; Rycroft, Chris H.; Kazi, Michaeel Microporous and Mesoporous Materials, Vol. 149, Issue 1 https://doi.org/10.1016/j.micromeso.2011.08.020	journal	February 2012
A unified formulation of the constant temperature molecular dynamics methods Nosé, Shuichi The Journal of Chemical Physics, Vol. 81, Issue 1 https://doi.org/10.1063/1.447334	journal	July 1984
Li ₃ Y(PS ₄ ) ₂ and Li ₅ PS ₄ Cl ₂ : New Lithium Superionic Conductors Predicted from Silver Thiophosphates using Efficiently Tiered Ab Initio Molecular Dynamics Simulations Zhu, Zhuoying; Chu, Iek-Heng; Ong, Shyue Ping Chemistry of Materials, Vol. 29, Issue 6 https://doi.org/10.1021/acs.chemmater.6b04049	journal	November 2016
Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav Computational Materials Science, Vol. 68 https://doi.org/10.1016/j.commatsci.2012.10.028	journal	February 2013
Probing Solid–Solid Interfacial Reactions in All-Solid-State Sodium-Ion Batteries with First-Principles Calculations Tang, Hanmei; Deng, Zhi; Lin, Zhuonan Chemistry of Materials, Vol. 30, Issue 1 https://doi.org/10.1021/acs.chemmater.7b04096	journal	December 2017
Lithium Ion Pathway within Li 7 La 3 Zr 2 O 12 -Polyethylene Oxide Composite Electrolytes Zheng, Jin; Tang, Mingxue; Hu, Yan-Yan Angewandte Chemie, Vol. 128, Issue 40 https://doi.org/10.1002/ange.201607539	journal	September 2016
Amorphization-induced surface electronic states modulation of cobaltous oxide nanosheets for lithium-sulfur batteries Li, Ruilong; Rao, Dewei; Zhou, Jianbin Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23349-9	journal	May 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-58835-5	journal	February 2020

Cited By (1)

Enhanced sodium ion conductivity in Na ₃ VS ₄ by P-doping He, Yu; Lu, Fengqi; Kuang, Xiaojun RSC Advances, Vol. 9, Issue 67 https://doi.org/10.1039/c9ra08900d	journal	January 2019

Similar Records

Vanadyl Phosphates A_xVOPO₄ (A = Li, Na, K) as Multielectron Cathodes for Alkali-Ion Batteries

Journal Article · Fri Oct 30 00:00:00 EDT 2020 · Advanced Energy Materials · OSTI ID:1542272

Chernova, Natasha A.; Hidalgo, Marc V.; Kaplan, Carol; +14 more

Structure of amorphous materials in the NASICON system Na 1+x Ti ₂ Si _x P 3−x O ₁₂

Journal Article · Thu Apr 13 00:00:00 EDT 2023 · Journal of Physics. Condensed Matter · OSTI ID:1542272

Mendes Da Silva, Rita; Zeidler, Anita; Bradtmüller, Henrik; +4 more

New Cost-Effective Halide Solid Electrolytes for All-Solid-State Batteries: Mechanochemically Prepared Fe³⁺-Substituted Li₂ZrCl₆

Journal Article · Mon Jan 18 00:00:00 EST 2021 · Advanced Energy Materials · OSTI ID:1542272

Kwak, Hiram; Han, Daseul; Lyoo, Jeyne; +8 more

Related Subjects

36 MATERIALS SCIENCE
all-solid-state sodium ion batteries
functional defects
NMR
sodium solid electrolyte
thiophosphate

Title: Studies of Functional Defects for Fast Na-Ion Conduction in Na 3-yPS4-xClx with a Combined Experimental and Computational Approach

Citation Formats

References (30)

Cited By (1)

Similar Records

Related Subjects

Title: Studies of Functional Defects for Fast Na-Ion Conduction in Na _3-_yPS_4-_xCl_x with a Combined Experimental and Computational Approach