Origin of Outstanding Phase and Moisture Stability in a Na3P1–x AsxS4 Superionic Conductor

Shang, Shun-Li; Yu, Zhaoxin; Wang, Yi; Wang, Donghai; Liu, Zi-Kui

doi:10.1021/acsami.7b03606

Title: Origin of Outstanding Phase and Moisture Stability in a Na₃P_1–x As_xS₄ Superionic Conductor

Journal Article · Thu May 04 00:00:00 EDT 2017 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.7b03606· OSTI ID:1484768

^[1]; Yu, Zhaoxin ^[2];

^[1];

^[3]; Liu, Zi-Kui ^[1]

Pennsylvania State Univ., University Park, PA (United States). Dept. of Materials Science and Engineering
Pennsylvania State Univ., University Park, PA (United States). Dept. of Mechanical and Nuclear Engineering
Pennsylvania State Univ., University Park, PA (United States). Dept. of Mechanical and Nuclear Engineering

Sodium ion (Na) solid-state electrolytes (SSEs) are critical to address notorious safety issues associated with liquid electrolytes used in the current Na ion batteries. Fulfilling multiple innovations is a grand challenge but is imperative for advanced Na ion SSEs, such as a combination of high ionic conductivity and excellent chemical stability. Here, our first-principles and phonon calculations reveal that Na₃P_1–xAs_xS₄ (0 ≤ x ≤ 1) is a solid-state superionic conductor stabilized at 0 K by zero-point vibrational energy and at finite temperatures by vibrational and configurational entropies. Especially, our integrated first-principles and experimental approach indicates that Na₃P_1–xAs_xS₄ is dry-air stable. Additionally, the alloying element arsenic greatly enhances the moisture (i.e., H₂O) stability of Na₃P_1–xAs_xS₄ by shifting the reaction products from the easy-forming oxysulfides (such as Na₃POS₃ and Na₃PO₂S₂ with H₂S release) to the difficult-forming hydrates (such as Na₃P_1–xAs_xS₄·$$n$$H₂O with n = 8 and/or 9) due mainly to a weaker As–O affinity compared to that of P–O. The present work demonstrates that alloying is able to achieve multiple innovations for solid-state electrolytes, such as a desirable superionic conductor with not only a high ionic conductivity (for example, 1.46 mS/cm at room temperature achieved in Na₃P_0.62As_0.38S₄) but also an excellent chemical stability with respect to temperature, composition, and moisture.

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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)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1484768

Journal Information:: ACS Applied Materials and Interfaces, Vol. 9, Issue 19; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 40 works

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References (57)

The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage Kundu, Dipan; Talaie, Elahe; Duffort, Victor Angewandte Chemie International Edition, Vol. 54, Issue 11 https://doi.org/10.1002/anie.201410376	journal	February 2015
Ambient Temperature Sodium-Sulfur Batteries Manthiram, Arumugam; Yu, Xingwen Small, Vol. 11, Issue 18 https://doi.org/10.1002/smll.201403257	journal	January 2015
Research Development on Sodium-Ion Batteries Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500192f	journal	October 2014
Non-aqueous electrolytes for sodium-ion batteries Ponrouch, A.; Monti, D.; Boschin, A. Journal of Materials Chemistry A, Vol. 3, Issue 1 https://doi.org/10.1039/C4TA04428B	journal	January 2015
Development of Sodium-Sulfur Batteries Oshima, Taku; Kajita, Masaharu; Okuno, Akiyasu International Journal of Applied Ceramic Technology, Vol. 1, Issue 3 https://doi.org/10.1111/j.1744-7402.2004.tb00179.x	journal	July 2004
Air-stable, high-conduction solid electrolytes of arsenic-substituted Li ₄ SnS ₄ Sahu, Gayatri; Lin, Zhan; Li, Juchuan Energy Environ. Sci., Vol. 7, Issue 3 https://doi.org/10.1039/C3EE43357A	journal	January 2014
Na ₃ SbS ₄ : A Solution Processable Sodium Superionic Conductor for All-Solid-State Sodium-Ion Batteries Banerjee, Abhik; Park, Kern Ho; Heo, Jongwook W. Angewandte Chemie, Vol. 128, Issue 33 https://doi.org/10.1002/ange.201604158	journal	July 2016
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
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
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
High sodium ion conductivity of glass–ceramic electrolytes with cubic Na3PS4 Hayashi, Akitoshi; Noi, Kousuke; Tanibata, Naoto Journal of Power Sources, Vol. 258 https://doi.org/10.1016/j.jpowsour.2014.02.054	journal	July 2014
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
Na ₃ PSe ₄ : A Novel Chalcogenide Solid Electrolyte with High Ionic Conductivity Zhang, Long; Yang, Kun; Mi, Jianli Advanced Energy Materials, Vol. 5, Issue 24 https://doi.org/10.1002/aenm.201501294	journal	October 2015
Room-Temperature All-solid-state Rechargeable Sodium-ion Batteries with a Cl-doped Na3PS4 Superionic Conductor Chu, Iek-Heng; Kompella, Christopher S.; Nguyen, Han Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep33733	journal	September 2016
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
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
In search of an optimized electrolyte for Na-ion batteries Ponrouch, Alexandre; Marchante, Elena; Courty, Matthieu Energy & Environmental Science, Vol. 5, Issue 9 https://doi.org/10.1039/c2ee22258b	journal	January 2012
Sustainability and in situ monitoring in battery development Grey, C. P.; Tarascon, J. M. Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4777	journal	December 2016
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
X-ray Crystal Structure Analysis of Sodium-Ion Conductivity in 94 Na ₃ PS ₄ ⋅6 Na ₄ SiS ₄ Glass-Ceramic Electrolytes Tanibata, Naoto; Noi, Kousuke; Hayashi, Akitoshi ChemElectroChem, Vol. 1, Issue 7 https://doi.org/10.1002/celc.201402016	journal	June 2014
Multicomponent multisublattice alloys, nonconfigurational entropy and other additions to the Alloy Theoretic Automated Toolkit van de Walle, Axel Calphad, Vol. 33, Issue 2 https://doi.org/10.1016/j.calphad.2008.12.005	journal	June 2009
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
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
Data Mined Ionic Substitutions for the Discovery of New Compounds Hautier, Geoffroy; Fischer, Chris; Ehrlacher, Virginie Inorganic Chemistry, Vol. 50, Issue 2 https://doi.org/10.1021/ic102031h	journal	January 2011
The inorganic crystal structure data base Bergerhoff, G.; Hundt, R.; Sievers, R. Journal of Chemical Information and Modeling, Vol. 23, Issue 2 https://doi.org/10.1021/ci00038a003	journal	May 1983
Structure of trisodium monothioarsenate dodecahydrate Kempa, P. B.; Wiebcke, M.; Felsche, J. Acta Crystallographica Section C Crystal Structure Communications, Vol. 46, Issue 5 https://doi.org/10.1107/S0108270189009650	journal	May 1990
Disorder in the structure of trisodium phosphorothioate dodecahydrate Goldstein, B. M. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 4 https://doi.org/10.1107/S056774088200510X	journal	April 1982
The solid phases of deuterium sulphide by powder neutron diffraction Cockcroft, Jeremy K.; Fitch, Andrew N. Zeitschrift für Kristallographie, Vol. 193, Issue 1-2, p. 1-19 https://doi.org/10.1524/zkri.1990.193.1-2.1	journal	January 1990
High-throughput computational design of cathode coatings for Li-ion batteries Aykol, Muratahan; Kim, Soo; Hegde, Vinay I. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms13779	journal	December 2016
Aqueous Stability of Alkali Superionic Conductors from First-Principles Calculations Radhakrishnan, Balachandran; Ong, Shyue Ping Frontiers in Energy Research, Vol. 4 https://doi.org/10.3389/fenrg.2016.00016	journal	April 2016
Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states Persson, Kristin A.; Waldwick, Bryn; Lazic, Predrag Physical Review B, Vol. 85, Issue 23 https://doi.org/10.1103/PhysRevB.85.235438	journal	June 2012
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
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 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
Insight into structural, elastic, phonon, and thermodynamic properties of α-sulfur and energy-related sulfides: a comprehensive first-principles study Shang, ShunLi; Wang, Yi; Guan, Pinwen Journal of Materials Chemistry A, Vol. 3, Issue 15 https://doi.org/10.1039/C4TA07062C	journal	January 2015
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
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I. Physical Review Letters, Vol. 100, Issue 13 https://doi.org/10.1103/PhysRevLett.100.136406	journal	April 2008
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
A mixed-space approach to first-principles calculations of phonon frequencies for polar materials Wang, Y.; Wang, J. J.; Wang, W. Y. Journal of Physics: Condensed Matter, Vol. 22, Issue 20 https://doi.org/10.1088/0953-8984/22/20/202201	journal	April 2010
YPHON: A package for calculating phonons of polar materials Wang, Yi; Chen, Long-Qing; Liu, Zi-Kui Computer Physics Communications, Vol. 185, Issue 11 https://doi.org/10.1016/j.cpc.2014.06.023	journal	November 2014
First-principles calculations of lattice dynamics and thermal properties of polar solids Wang, Yi; Shang, Shun-Li; Fang, Huazhi npj Computational Materials, Vol. 2, Issue 1 https://doi.org/10.1038/npjcompumats.2016.6	journal	May 2016
Thermodynamic properties of Al, Ni, NiAl, and Ni3Al from first-principles calculations Wang, Y.; Liu, Z. -K.; Chen, L. -Q. Acta Materialia, Vol. 52, Issue 9 https://doi.org/10.1016/j.actamat.2004.02.014	journal	May 2004
First-principles thermodynamics from phonon and Debye model: Application to Ni and Ni3Al Shang, Shun-Li; Wang, Yi; Kim, DongEung Computational Materials Science, Vol. 47, Issue 4 https://doi.org/10.1016/j.commatsci.2009.12.006	journal	February 2010
First-principles calculations of pure elements: Equations of state and elastic stiffness constants Shang, S. L.; Saengdeejing, A.; Mei, Z. G. Computational Materials Science, Vol. 48, Issue 4 https://doi.org/10.1016/j.commatsci.2010.03.041	journal	June 2010
A comprehensive first-principles study of pure elements: Vacancy formation and migration energies and self-diffusion coefficients Shang, Shun-Li; Zhou, Bi-Cheng; Wang, William Y. Acta Materialia, Vol. 109 https://doi.org/10.1016/j.actamat.2016.02.031	journal	May 2016
Elastic constants of ice samples by Brillouin spectroscopy Gammon, P. H.; Kiefte, H.; Clouter, M. J. The Journal of Physical Chemistry, Vol. 87, Issue 21 https://doi.org/10.1021/j100244a004	journal	October 1983
High-Pressure Brillouin Study on Orientationally Disordered Solid Phase I of H ₂ S and D ₂ S Sasaki, Shigeo; Shimizu, Hiroyasu Journal of the Physical Society of Japan, Vol. 64, Issue 9 https://doi.org/10.1143/JPSJ.64.3309	journal	September 1995
High-Pressure Brillouin Studies and Elastic Properties of Single-Crystal H2S Grown in a Diamond Cell Shimizu, H.; Sasaki, S. Science, Vol. 257, Issue 5069 https://doi.org/10.1126/science.257.5069.514	journal	July 1992
Structural investigations of yNa2S+(1−y)PS5/2 glasses using Raman and infrared spectroscopies Bischoff, Christian; Schuller, Katherine; Haynes, Michael Journal of Non-Crystalline Solids, Vol. 358, Issue 23 https://doi.org/10.1016/j.jnoncrysol.2012.09.023	journal	December 2012
Das thermische Verhalten der Mischungen Na2S?P4S10 und Na4Ge4S10?P4S10 des Systems Na2S?GeS2?P4S10 Blachnik, R.; Rabe, U. Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 462, Issue 1 https://doi.org/10.1002/zaac.19804620122	journal	March 1980
Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 124, Issue 21 https://doi.org/10.1063/1.2204597	journal	June 2006
Hydrogen bonds in α-Na3PS4·8H2O: X-ray diffraction and vibrational spectroscopic study Mereiter, K.; Preisinger, A.; Zellner, A. Inorganica Chimica Acta, Vol. 72 https://doi.org/10.1016/S0020-1693(00)81697-7	journal	January 1983
Crystal Structures of Na3PO2S2 · 11H2O and Na3POS3 · 11H2O Pompetzki, Markus; Jansen, Martin Monatshefte für Chemie / Chemical Monthly, Vol. 133, Issue 7 https://doi.org/10.1007/s007060200067	journal	July 2002
Sodium dithiophosphate(V): Crystal structure, sodium ionic conductivity and dismutation Pompetzki, Markus; Dinnebier, Robert E.; Jansen, Martin Solid State Sciences, Vol. 5, Issue 11-12 https://doi.org/10.1016/j.solidstatesciences.2003.07.002	journal	November 2003
Natriumtrithiophosphat(V): Kristallstruktur und Natriumionenleitfähigkeit Pompetzki, M.; Jansen, M. Zeitschrift für anorganische und allgemeine Chemie, Vol. 629, Issue 11 https://doi.org/10.1002/zaac.200300170	journal	October 2003
Natriummonothiophosphat(V): Kristallstruktur und Natriumionenleitfähigkeit Pompetzki, M.; Jansen, M. Zeitschrift für anorganische und allgemeine Chemie, Vol. 628, Issue 3 https://doi.org/10.1002/1521-3749(200203)628:3<641::AID-ZAAC641>3.0.CO;2-8	journal	March 2002
Comprehensive Handbook of Chemical Bond Energies Luo, Yu-Ran https://doi.org/10.1201/9781420007282	book	March 2007

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