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

Abstract

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.

Authors:

^[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

Publication Date:: Thu May 04 00:00:00 EDT 2017

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

Sponsoring Org.:: USDOE Office of Science (SC)

OSTI Identifier:: 1484768

Grant/Contract Number:: AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Materials and Interfaces

Additional Journal Information:: Journal Volume: 9; Journal Issue: 19; Journal ID: ISSN 1944-8244

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Shang, Shun-Li, Yu, Zhaoxin, Wang, Yi, Wang, Donghai, and Liu, Zi-Kui. Origin of Outstanding Phase and Moisture Stability in a Na3P1–x AsxS4 Superionic Conductor.  United States: N. p., 2017. 
Web.  doi:10.1021/acsami.7b03606.

Copy to clipboard


                    Shang, Shun-Li, Yu, Zhaoxin, Wang, Yi, Wang, Donghai, & Liu, Zi-Kui. Origin of Outstanding Phase and Moisture Stability in a Na3P1–x AsxS4 Superionic Conductor.  United States.  https://doi.org/10.1021/acsami.7b03606

Copy to clipboard


                    Shang, Shun-Li, Yu, Zhaoxin, Wang, Yi, Wang, Donghai, and Liu, Zi-Kui. Thu .  
"Origin of Outstanding Phase and Moisture Stability in a Na3P1–x AsxS4 Superionic Conductor".  United States.  https://doi.org/10.1021/acsami.7b03606.  https://www.osti.gov/servlets/purl/1484768.

Copy to clipboard


                    
@article{osti_1484768,

  title        = {Origin of Outstanding Phase and Moisture Stability in a Na3P1–x AsxS4 Superionic Conductor},

  author       = {Shang, Shun-Li and Yu, Zhaoxin and Wang, Yi and Wang, Donghai and Liu, Zi-Kui},

  abstractNote = {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 Na3P1–xAsxS4 (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 Na3P1–xAsxS4 is dry-air stable. Additionally, the alloying element arsenic greatly enhances the moisture (i.e., H2O) stability of Na3P1–xAsxS4 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 Na3P1–xAsxS4·$n$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 Na3P0.62As0.38S4) but also an excellent chemical stability with respect to temperature, composition, and moisture.},

  doi          = {10.1021/acsami.7b03606},

  journal      = {ACS Applied Materials and Interfaces},

  number       = 19,

  volume       = 9,

  place        = {United States},

  year         = {Thu May 04 00:00:00 EDT 2017},

  month        = {Thu May 04 00:00:00 EDT 2017}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1021/acsami.7b03606

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 40 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage
journal, February 2015

Kundu, Dipan; Talaie, Elahe; Duffort, Victor
Angewandte Chemie International Edition, Vol. 54, Issue 11
DOI: 10.1002/anie.201410376

Ambient Temperature Sodium-Sulfur Batteries
journal, January 2015

Manthiram, Arumugam; Yu, Xingwen
Small, Vol. 11, Issue 18
DOI: 10.1002/smll.201403257

Research Development on Sodium-Ion Batteries
journal, October 2014

Yabuuchi, Naoaki; Kubota, Kei; Dahbi, Mouad
Chemical Reviews, Vol. 114, Issue 23
DOI: 10.1021/cr500192f

Non-aqueous electrolytes for sodium-ion batteries
journal, January 2015

Ponrouch, A.; Monti, D.; Boschin, A.
Journal of Materials Chemistry A, Vol. 3, Issue 1
DOI: 10.1039/C4TA04428B

Development of Sodium-Sulfur Batteries
journal, July 2004

Oshima, Taku; Kajita, Masaharu; Okuno, Akiyasu
International Journal of Applied Ceramic Technology, Vol. 1, Issue 3
DOI: 10.1111/j.1744-7402.2004.tb00179.x

Air-stable, high-conduction solid electrolytes of arsenic-substituted Li ₄ SnS ₄
journal, January 2014

Sahu, Gayatri; Lin, Zhan; Li, Juchuan
Energy Environ. Sci., Vol. 7, Issue 3
DOI: 10.1039/C3EE43357A

Na ₃ SbS ₄ : A Solution Processable Sodium Superionic Conductor for All-Solid-State Sodium-Ion Batteries
journal, July 2016

Banerjee, Abhik; Park, Kern Ho; Heo, Jongwook W.
Angewandte Chemie, Vol. 128, Issue 33
DOI: 10.1002/ange.201604158

A lithium superionic conductor
journal, July 2011

Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro
Nature Materials, Vol. 10, Issue 9, p. 682-686
DOI: 10.1038/nmat3066

High-power all-solid-state batteries using sulfide superionic conductors
journal, March 2016

Kato, Yuki; Hori, Satoshi; Saito, Toshiya
Nature Energy, Vol. 1, Issue 4
DOI: 10.1038/nenergy.2016.30

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries
journal, January 2012

Hayashi, Akitoshi; Noi, Kousuke; Sakuda, Atsushi
Nature Communications, Vol. 3, Issue 1
DOI: 10.1038/ncomms1843

High sodium ion conductivity of glass–ceramic electrolytes with cubic Na3PS4
journal, July 2014

Hayashi, Akitoshi; Noi, Kousuke; Tanibata, Naoto
Journal of Power Sources, Vol. 258
DOI: 10.1016/j.jpowsour.2014.02.054

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
journal, February 2017

Yu, Zhaoxin; Shang, Shun-Li; Seo, Joo-Hwan
Advanced Materials, Vol. 29, Issue 16
DOI: 10.1002/adma.201605561

Na ₃ PSe ₄ : A Novel Chalcogenide Solid Electrolyte with High Ionic Conductivity
journal, October 2015

Zhang, Long; Yang, Kun; Mi, Jianli
Advanced Energy Materials, Vol. 5, Issue 24
DOI: 10.1002/aenm.201501294

Room-Temperature All-solid-state Rechargeable Sodium-ion Batteries with a Cl-doped Na3PS4 Superionic Conductor
journal, September 2016

Chu, Iek-Heng; Kompella, Christopher S.; Nguyen, Han
Scientific Reports, Vol. 6, Issue 1
DOI: 10.1038/srep33733

Design and synthesis of the superionic conductor Na10SnP2S12
journal, March 2016

Richards, William D.; Tsujimura, Tomoyuki; Miara, Lincoln J.
Nature Communications, Vol. 7, Issue 1
DOI: 10.1038/ncomms11009

Role of Na ⁺ Interstitials and Dopants in Enhancing the Na ⁺ Conductivity of the Cubic Na ₃ PS ₄ Superionic Conductor
journal, December 2015

Zhu, Zhuoying; Chu, Iek-Heng; Deng, Zhi
Chemistry of Materials, Vol. 27, Issue 24
DOI: 10.1021/acs.chemmater.5b03656

In search of an optimized electrolyte for Na-ion batteries
journal, January 2012

Ponrouch, Alexandre; Marchante, Elena; Courty, Matthieu
Energy & Environmental Science, Vol. 5, Issue 9
DOI: 10.1039/c2ee22258b

Sustainability and in situ monitoring in battery development
journal, December 2016

Grey, C. P.; Tarascon, J. M.
Nature Materials, Vol. 16, Issue 1
DOI: 10.1038/nmat4777

Synthesis, structure determination, and ionic conductivity of sodium tetrathiophosphate
journal, July 1992

Jansen, M.; Henseler, U.
Journal of Solid State Chemistry, Vol. 99, Issue 1
DOI: 10.1016/0022-4596(92)90295-7

X-ray Crystal Structure Analysis of Sodium-Ion Conductivity in 94 Na ₃ PS ₄ ⋅6 Na ₄ SiS ₄ Glass-Ceramic Electrolytes
journal, June 2014

Tanibata, Naoto; Noi, Kousuke; Hayashi, Akitoshi
ChemElectroChem, Vol. 1, Issue 7
DOI: 10.1002/celc.201402016

Multicomponent multisublattice alloys, nonconfigurational entropy and other additions to the Alloy Theoretic Automated Toolkit
journal, June 2009

van de Walle, Axel
Calphad, Vol. 33, Issue 2
DOI: 10.1016/j.calphad.2008.12.005

Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
APL Materials, Vol. 1, Issue 1
DOI: 10.1063/1.4812323

Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis
journal, February 2013

Ong, Shyue Ping; Richards, William Davidson; Jain, Anubhav
Computational Materials Science, Vol. 68
DOI: 10.1016/j.commatsci.2012.10.028

Data Mined Ionic Substitutions for the Discovery of New Compounds
journal, January 2011

Hautier, Geoffroy; Fischer, Chris; Ehrlacher, Virginie
Inorganic Chemistry, Vol. 50, Issue 2
DOI: 10.1021/ic102031h

The inorganic crystal structure data base
journal, May 1983

Bergerhoff, G.; Hundt, R.; Sievers, R.
Journal of Chemical Information and Modeling, Vol. 23, Issue 2
DOI: 10.1021/ci00038a003

Structure of trisodium monothioarsenate dodecahydrate
journal, May 1990

Kempa, P. B.; Wiebcke, M.; Felsche, J.
Acta Crystallographica Section C Crystal Structure Communications, Vol. 46, Issue 5
DOI: 10.1107/S0108270189009650

Disorder in the structure of trisodium phosphorothioate dodecahydrate
journal, April 1982

Goldstein, B. M.
Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 4
DOI: 10.1107/S056774088200510X

The solid phases of deuterium sulphide by powder neutron diffraction
journal, January 1990

Cockcroft, Jeremy K.; Fitch, Andrew N.
Zeitschrift für Kristallographie, Vol. 193, Issue 1-2, p. 1-19
DOI: 10.1524/zkri.1990.193.1-2.1

High-throughput computational design of cathode coatings for Li-ion batteries
journal, December 2016

Aykol, Muratahan; Kim, Soo; Hegde, Vinay I.
Nature Communications, Vol. 7, Issue 1
DOI: 10.1038/ncomms13779

Aqueous Stability of Alkali Superionic Conductors from First-Principles Calculations
journal, April 2016

Radhakrishnan, Balachandran; Ong, Shyue Ping
Frontiers in Energy Research, Vol. 4
DOI: 10.3389/fenrg.2016.00016

Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states
journal, June 2012

Persson, Kristin A.; Waldwick, Bryn; Lazic, Predrag
Physical Review B, Vol. 85, Issue 23
DOI: 10.1103/PhysRevB.85.235438

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Kresse, G.; Furthmüller, J.
Physical Review B, Vol. 54, Issue 16, p. 11169-11186
DOI: 10.1103/PhysRevB.54.11169

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

Kresse, G.; Furthmüller, J.
Computational Materials Science, Vol. 6, Issue 1, p. 15-50
DOI: 10.1016/0927-0256(96)00008-0

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Kresse, G.; Joubert, D.
Physical Review B, Vol. 59, Issue 3, p. 1758-1775
DOI: 10.1103/PhysRevB.59.1758

Insight into structural, elastic, phonon, and thermodynamic properties of α-sulfur and energy-related sulfides: a comprehensive first-principles study
journal, January 2015

Shang, ShunLi; Wang, Yi; Guan, Pinwen
Journal of Materials Chemistry A, Vol. 3, Issue 15
DOI: 10.1039/C4TA07062C

Generalized Gradient Approximation Made Simple
journal, October 1996

Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
DOI: 10.1103/PhysRevLett.77.3865

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008

Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
Physical Review Letters, Vol. 100, Issue 13
DOI: 10.1103/PhysRevLett.100.136406

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
The Journal of Chemical Physics, Vol. 132, Issue 15
DOI: 10.1063/1.3382344

A mixed-space approach to first-principles calculations of phonon frequencies for polar materials
journal, April 2010

Wang, Y.; Wang, J. J.; Wang, W. Y.
Journal of Physics: Condensed Matter, Vol. 22, Issue 20
DOI: 10.1088/0953-8984/22/20/202201

YPHON: A package for calculating phonons of polar materials
journal, November 2014

Wang, Yi; Chen, Long-Qing; Liu, Zi-Kui
Computer Physics Communications, Vol. 185, Issue 11
DOI: 10.1016/j.cpc.2014.06.023

First-principles calculations of lattice dynamics and thermal properties of polar solids
journal, May 2016

Wang, Yi; Shang, Shun-Li; Fang, Huazhi
npj Computational Materials, Vol. 2, Issue 1
DOI: 10.1038/npjcompumats.2016.6

Thermodynamic properties of Al, Ni, NiAl, and Ni3Al from first-principles calculations
journal, May 2004

Wang, Y.; Liu, Z. -K.; Chen, L. -Q.
Acta Materialia, Vol. 52, Issue 9
DOI: 10.1016/j.actamat.2004.02.014

First-principles thermodynamics from phonon and Debye model: Application to Ni and Ni3Al
journal, February 2010

Shang, Shun-Li; Wang, Yi; Kim, DongEung
Computational Materials Science, Vol. 47, Issue 4
DOI: 10.1016/j.commatsci.2009.12.006

First-principles calculations of pure elements: Equations of state and elastic stiffness constants
journal, June 2010

Shang, S. L.; Saengdeejing, A.; Mei, Z. G.
Computational Materials Science, Vol. 48, Issue 4
DOI: 10.1016/j.commatsci.2010.03.041

A comprehensive first-principles study of pure elements: Vacancy formation and migration energies and self-diffusion coefficients
journal, May 2016

Shang, Shun-Li; Zhou, Bi-Cheng; Wang, William Y.
Acta Materialia, Vol. 109
DOI: 10.1016/j.actamat.2016.02.031

Elastic constants of ice samples by Brillouin spectroscopy
journal, October 1983

Gammon, P. H.; Kiefte, H.; Clouter, M. J.
The Journal of Physical Chemistry, Vol. 87, Issue 21
DOI: 10.1021/j100244a004

High-Pressure Brillouin Study on Orientationally Disordered Solid Phase I of H ₂ S and D ₂ S
journal, September 1995

Sasaki, Shigeo; Shimizu, Hiroyasu
Journal of the Physical Society of Japan, Vol. 64, Issue 9
DOI: 10.1143/JPSJ.64.3309

High-Pressure Brillouin Studies and Elastic Properties of Single-Crystal H2S Grown in a Diamond Cell
journal, July 1992

Shimizu, H.; Sasaki, S.
Science, Vol. 257, Issue 5069
DOI: 10.1126/science.257.5069.514

Structural investigations of yNa2S+(1−y)PS5/2 glasses using Raman and infrared spectroscopies
journal, December 2012

Bischoff, Christian; Schuller, Katherine; Haynes, Michael
Journal of Non-Crystalline Solids, Vol. 358, Issue 23
DOI: 10.1016/j.jnoncrysol.2012.09.023

Das thermische Verhalten der Mischungen Na2S?P4S10 und Na4Ge4S10?P4S10 des Systems Na2S?GeS2?P4S10
journal, March 1980

Blachnik, R.; Rabe, U.
Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 462, Issue 1
DOI: 10.1002/zaac.19804620122

Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
The Journal of Chemical Physics, Vol. 124, Issue 21
DOI: 10.1063/1.2204597

Hydrogen bonds in α-Na3PS4·8H2O: X-ray diffraction and vibrational spectroscopic study
journal, January 1983

Mereiter, K.; Preisinger, A.; Zellner, A.
Inorganica Chimica Acta, Vol. 72
DOI: 10.1016/S0020-1693(00)81697-7

Crystal Structures of Na3PO2S2 · 11H2O and Na3POS3 · 11H2O
journal, July 2002

Pompetzki, Markus; Jansen, Martin
Monatshefte für Chemie / Chemical Monthly, Vol. 133, Issue 7
DOI: 10.1007/s007060200067

Sodium dithiophosphate(V): Crystal structure, sodium ionic conductivity and dismutation
journal, November 2003

Pompetzki, Markus; Dinnebier, Robert E.; Jansen, Martin
Solid State Sciences, Vol. 5, Issue 11-12
DOI: 10.1016/j.solidstatesciences.2003.07.002

Natriumtrithiophosphat(V): Kristallstruktur und Natriumionenleitfähigkeit
journal, October 2003

Pompetzki, M.; Jansen, M.
Zeitschrift für anorganische und allgemeine Chemie, Vol. 629, Issue 11
DOI: 10.1002/zaac.200300170

Natriummonothiophosphat(V): Kristallstruktur und Natriumionenleitfähigkeit
journal, March 2002

Pompetzki, M.; Jansen, M.
Zeitschrift für anorganische und allgemeine Chemie, Vol. 628, Issue 3
DOI: 10.1002/1521-3749(200203)628:3<641::AID-ZAAC641>3.0.CO;2-8

Comprehensive Handbook of Chemical Bond Energies
book, March 2007

Luo, Yu-Ran
DOI: 10.1201/9781420007282

Works referencing / citing this record:

Sulfide Solid Electrolytes for Lithium Battery Applications
journal, August 2018

Lau, Jonathan; DeBlock, Ryan H.; Butts, Danielle M.
Advanced Energy Materials, Vol. 8, Issue 27
DOI: 10.1002/aenm.201800933

Electrolytes and Interphases in Sodium‐Based Rechargeable Batteries: Recent Advances and Perspectives
journal, April 2020

Eshetu, Gebrekidan Gebresilassie; Elia, Giuseppe Antonio; Armand, Michel
Advanced Energy Materials, Vol. 10, Issue 20
DOI: 10.1002/aenm.202000093

Electrolytes and Interphases in Sodium-Based Rechargeable Batteries : Recent Advances and Perspectives
text, January 2020

Eshetu, Gebrekidan Gebresilassie; Elia, Giuseppe Antonio; Armand, Michel
RWTH Aachen University
DOI: 10.18154/rwth-2020-04398

Electrolytes and Interphases in Sodium-Based Rechargeable Batteries: Recent Advances and Perspectives
text, January 2020

Eshetu, Gebrekidan Gebresilassie; Elia, Giuseppe Antonio; Armand, Michel
Karlsruhe
DOI: 10.5445/ir/1000118522

Similar Records in DOE PAGES and OSTI.GOV collections:

Moisture Stability of Sulfide Solid-State Electrolytes

Journal Article Yersak, Thomas A. ; Zhang, Yubin ; Hao, Fang ; ... - Frontiers in Energy Research

In this report we detail a comprehensive study on the moisture stability of sulfide solid-state electrolytes in dry room environments. Although sulfide SSEs have many favorable attributes, this class of materials suffers from poor stability with water. Sulfide SSEs react with water to form gaseous H₂S and a variety of solid byproducts like Li₃PO₄ and LiOH, which go on to increase the interfacial impedance of solid-state batteries. Lab-scale research typically utilizes gloveboxes with <1 ppm water, however, the large-scale manufacturing of Li-ion batteries occurs in –40°C dewpoint dry rooms with around 126 ppm water. Consequently, the moisture stability of sulfidemore »« less
https://doi.org/10.3389/fenrg.2022.882508

Full Text Available
Solid electrolyte for solid-state batteries: Have lithium-ion batteries reached their technical limit?

Journal Article Kartini, Evvy ; Manawan, Maykel - AIP Conference Proceedings

With increasing demand for electrical power on a distribution grid lacking storage capabilities, utilities and project developers must stabilize what is currently still intermittent energy production. In fact, over half of utility executives say “the most important emerging energy technology” is energy storage. Advanced, low-cost battery designs are providing promising stationary storage solutions that can ensure reliable, high-quality power for customers, but research challenges and questions lefts. Have lithium-ion batteries (LIBs) reached their technical limit? The industry demands are including high costs, inadequate energy densities, long recharge times, short cycle-life times and safety must be continually addressed. Safety is stillmore »« less
https://doi.org/10.1063/1.4941462
Evidence for a Solid-Electrolyte Inductive Effect in the Superionic Conductor Li₁₀Ge_1–xSn_xP₂S₁₂

Journal Article Culver, Sean P. ; Squires, Alexander G. ; Minafra, Nicolò ; ... - Journal of the American Chemical Society

Strategies to enhance ionic conductivities in solid electrolytes typically focus on the effects of modifying their crystal structures or of tuning mobile-ion stoichiometries. A less-explored approach is to modulate the chemical bonding interactions within a material to promote fast lithium-ion diffusion. Recently, the idea of a solid-electrolyte inductive effect has been proposed, whereby changes in bonding within the solid-electrolyte host framework modify the potential energy landscape for the mobile ions, resulting in an enhanced ionic conductivity. Direct evidence for a solid-electrolyte inductive effect, however, is lacking—in part because of the challenge of quantifying changes in local bonding interactions within amore »« less
https://doi.org/10.1021/jacs.0c10735

Full Text Available
Revealing the Structural Stability and Na-Ion Mobility of 3D Superionic Conductor Na₃SbS₄ at Extremely Low Temperatures

Journal Article Wang, Hui ; Chen, Yan ; Hood, Zachary D. ; ... - ACS Applied Energy Materials

All-solid-state batteries that employ superionic solid conductor potentially enable the broadening of battery operation in harsh environments, such as under subzero temperatures and even lower. The solid electrolyte as the key component requires structural stability, high-efficiency of ion transportation channels, and low activation energy to maintain the fast-ionic conduction against temperature drop. Herein, we use 3D superionic conductor Na₃SbS₄ as a model to investigate the structure and conductive mechanism at extremely low temperature. Cryogenic in situ neutron and X-ray diffractions reveal that Na₃SbS₄ maintains a stable tetragonal crystal structure and the anisotropic lattice contraction upon cooling. The dimensions of themore »« less
Cited by 11
https://doi.org/10.1021/acsaem.8b01449

Full Text Available
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 Feng, Xuyong ; Chien, Po-Hsiu ; Zhu, Zhuoying ; ... - Advanced Functional Materials

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 ).more »« less
Cited by 34
https://doi.org/10.1002/adfm.201807951

Full Text Available

Similar Records

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

Abstract

Citation Formats

The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage journal, February 2015

Ambient Temperature Sodium-Sulfur Batteries journal, January 2015

Research Development on Sodium-Ion Batteries journal, October 2014

Non-aqueous electrolytes for sodium-ion batteries journal, January 2015

Development of Sodium-Sulfur Batteries journal, July 2004

Air-stable, high-conduction solid electrolytes of arsenic-substituted Li 4 SnS 4 journal, January 2014

Na 3 SbS 4 : A Solution Processable Sodium Superionic Conductor for All-Solid-State Sodium-Ion Batteries journal, July 2016

A lithium superionic conductor journal, July 2011

High-power all-solid-state batteries using sulfide superionic conductors journal, March 2016

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries journal, January 2012

High sodium ion conductivity of glass–ceramic electrolytes with cubic Na3PS4 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 journal, February 2017

Na 3 PSe 4 : A Novel Chalcogenide Solid Electrolyte with High Ionic Conductivity journal, October 2015

Room-Temperature All-solid-state Rechargeable Sodium-ion Batteries with a Cl-doped Na3PS4 Superionic Conductor journal, September 2016

Design and synthesis of the superionic conductor Na10SnP2S12 journal, March 2016

Role of Na + Interstitials and Dopants in Enhancing the Na + Conductivity of the Cubic Na 3 PS 4 Superionic Conductor journal, December 2015

In search of an optimized electrolyte for Na-ion batteries journal, January 2012

Sustainability and in situ monitoring in battery development journal, December 2016

Synthesis, structure determination, and ionic conductivity of sodium tetrathiophosphate 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 journal, June 2014

Multicomponent multisublattice alloys, nonconfigurational entropy and other additions to the Alloy Theoretic Automated Toolkit journal, June 2009

Commentary: The Materials Project: A materials genome approach to accelerating materials innovation journal, July 2013

Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis journal, February 2013

Data Mined Ionic Substitutions for the Discovery of New Compounds journal, January 2011

The inorganic crystal structure data base journal, May 1983

Structure of trisodium monothioarsenate dodecahydrate journal, May 1990

Disorder in the structure of trisodium phosphorothioate dodecahydrate journal, April 1982

The solid phases of deuterium sulphide by powder neutron diffraction journal, January 1990

High-throughput computational design of cathode coatings for Li-ion batteries journal, December 2016

Aqueous Stability of Alkali Superionic Conductors from First-Principles Calculations journal, April 2016

Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states journal, June 2012

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal, October 1996

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set journal, July 1996

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Insight into structural, elastic, phonon, and thermodynamic properties of α-sulfur and energy-related sulfides: a comprehensive first-principles study journal, January 2015

Generalized Gradient Approximation Made Simple journal, October 1996

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal, April 2008

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu journal, April 2010

A mixed-space approach to first-principles calculations of phonon frequencies for polar materials journal, April 2010

YPHON: A package for calculating phonons of polar materials journal, November 2014

First-principles calculations of lattice dynamics and thermal properties of polar solids journal, May 2016

Thermodynamic properties of Al, Ni, NiAl, and Ni3Al from first-principles calculations journal, May 2004

First-principles thermodynamics from phonon and Debye model: Application to Ni and Ni3Al journal, February 2010

First-principles calculations of pure elements: Equations of state and elastic stiffness constants journal, June 2010

A comprehensive first-principles study of pure elements: Vacancy formation and migration energies and self-diffusion coefficients journal, May 2016

Elastic constants of ice samples by Brillouin spectroscopy journal, October 1983

High-Pressure Brillouin Study on Orientationally Disordered Solid Phase I of H 2 S and D 2 S journal, September 1995

High-Pressure Brillouin Studies and Elastic Properties of Single-Crystal H2S Grown in a Diamond Cell journal, July 1992

Structural investigations of yNa2S+(1−y)PS5/2 glasses using Raman and infrared spectroscopies journal, December 2012

Das thermische Verhalten der Mischungen Na2S?P4S10 und Na4Ge4S10?P4S10 des Systems Na2S?GeS2?P4S10 journal, March 1980

Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)] journal, June 2006

Hydrogen bonds in α-Na3PS4·8H2O: X-ray diffraction and vibrational spectroscopic study journal, January 1983

Crystal Structures of Na3PO2S2 · 11H2O and Na3POS3 · 11H2O journal, July 2002

Sodium dithiophosphate(V): Crystal structure, sodium ionic conductivity and dismutation journal, November 2003

Natriumtrithiophosphat(V): Kristallstruktur und Natriumionenleitfähigkeit journal, October 2003

Natriummonothiophosphat(V): Kristallstruktur und Natriumionenleitfähigkeit journal, March 2002

Comprehensive Handbook of Chemical Bond Energies book, March 2007

Sulfide Solid Electrolytes for Lithium Battery Applications journal, August 2018

Electrolytes and Interphases in Sodium‐Based Rechargeable Batteries: Recent Advances and Perspectives journal, April 2020

Electrolytes and Interphases in Sodium-Based Rechargeable Batteries : Recent Advances and Perspectives text, January 2020

Electrolytes and Interphases in Sodium-Based Rechargeable Batteries: Recent Advances and Perspectives text, January 2020

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

The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage
journal, February 2015

Ambient Temperature Sodium-Sulfur Batteries
journal, January 2015

Research Development on Sodium-Ion Batteries
journal, October 2014

Non-aqueous electrolytes for sodium-ion batteries
journal, January 2015

Development of Sodium-Sulfur Batteries
journal, July 2004

Air-stable, high-conduction solid electrolytes of arsenic-substituted Li ₄ SnS ₄
journal, January 2014

Na ₃ SbS ₄ : A Solution Processable Sodium Superionic Conductor for All-Solid-State Sodium-Ion Batteries
journal, July 2016

A lithium superionic conductor
journal, July 2011

High-power all-solid-state batteries using sulfide superionic conductors
journal, March 2016

Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries
journal, January 2012

High sodium ion conductivity of glass–ceramic electrolytes with cubic Na3PS4
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
journal, February 2017

Na ₃ PSe ₄ : A Novel Chalcogenide Solid Electrolyte with High Ionic Conductivity
journal, October 2015

Room-Temperature All-solid-state Rechargeable Sodium-ion Batteries with a Cl-doped Na3PS4 Superionic Conductor
journal, September 2016

Design and synthesis of the superionic conductor Na10SnP2S12
journal, March 2016

Role of Na ⁺ Interstitials and Dopants in Enhancing the Na ⁺ Conductivity of the Cubic Na ₃ PS ₄ Superionic Conductor
journal, December 2015

In search of an optimized electrolyte for Na-ion batteries
journal, January 2012

Sustainability and in situ monitoring in battery development
journal, December 2016

Synthesis, structure determination, and ionic conductivity of sodium tetrathiophosphate
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
journal, June 2014

Multicomponent multisublattice alloys, nonconfigurational entropy and other additions to the Alloy Theoretic Automated Toolkit
journal, June 2009

Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis
journal, February 2013

Data Mined Ionic Substitutions for the Discovery of New Compounds
journal, January 2011

The inorganic crystal structure data base
journal, May 1983

Structure of trisodium monothioarsenate dodecahydrate
journal, May 1990

Disorder in the structure of trisodium phosphorothioate dodecahydrate
journal, April 1982

The solid phases of deuterium sulphide by powder neutron diffraction
journal, January 1990

High-throughput computational design of cathode coatings for Li-ion batteries
journal, December 2016

Aqueous Stability of Alkali Superionic Conductors from First-Principles Calculations
journal, April 2016

Prediction of solid-aqueous equilibria: Scheme to combine first-principles calculations of solids with experimental aqueous states
journal, June 2012

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Insight into structural, elastic, phonon, and thermodynamic properties of α-sulfur and energy-related sulfides: a comprehensive first-principles study
journal, January 2015

Generalized Gradient Approximation Made Simple
journal, October 1996

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

A mixed-space approach to first-principles calculations of phonon frequencies for polar materials
journal, April 2010

YPHON: A package for calculating phonons of polar materials
journal, November 2014

First-principles calculations of lattice dynamics and thermal properties of polar solids
journal, May 2016

Thermodynamic properties of Al, Ni, NiAl, and Ni3Al from first-principles calculations
journal, May 2004

First-principles thermodynamics from phonon and Debye model: Application to Ni and Ni3Al
journal, February 2010

First-principles calculations of pure elements: Equations of state and elastic stiffness constants
journal, June 2010

A comprehensive first-principles study of pure elements: Vacancy formation and migration energies and self-diffusion coefficients
journal, May 2016

Elastic constants of ice samples by Brillouin spectroscopy
journal, October 1983

High-Pressure Brillouin Study on Orientationally Disordered Solid Phase I of H ₂ S and D ₂ S
journal, September 1995

High-Pressure Brillouin Studies and Elastic Properties of Single-Crystal H2S Grown in a Diamond Cell
journal, July 1992

Structural investigations of yNa2S+(1−y)PS5/2 glasses using Raman and infrared spectroscopies
journal, December 2012

Das thermische Verhalten der Mischungen Na2S?P4S10 und Na4Ge4S10?P4S10 des Systems Na2S?GeS2?P4S10
journal, March 1980

Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

Hydrogen bonds in α-Na3PS4·8H2O: X-ray diffraction and vibrational spectroscopic study
journal, January 1983

Crystal Structures of Na3PO2S2 · 11H2O and Na3POS3 · 11H2O
journal, July 2002

Sodium dithiophosphate(V): Crystal structure, sodium ionic conductivity and dismutation
journal, November 2003

Natriumtrithiophosphat(V): Kristallstruktur und Natriumionenleitfähigkeit
journal, October 2003

Natriummonothiophosphat(V): Kristallstruktur und Natriumionenleitfähigkeit
journal, March 2002

Comprehensive Handbook of Chemical Bond Energies
book, March 2007

Sulfide Solid Electrolytes for Lithium Battery Applications
journal, August 2018

Electrolytes and Interphases in Sodium‐Based Rechargeable Batteries: Recent Advances and Perspectives
journal, April 2020

Electrolytes and Interphases in Sodium-Based Rechargeable Batteries : Recent Advances and Perspectives
text, January 2020

Electrolytes and Interphases in Sodium-Based Rechargeable Batteries: Recent Advances and Perspectives
text, January 2020