Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions
Abstract
Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na2B12H12, which contains large, icosahedral, divalent B12H122– anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li2B12H12, possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB11H12 and NaCB11H12 salts, which contain icosahedral, monovalent CB11H12– anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, and truly stellar ionic conductivities (>0.1 S cm–1) unmatched by any other known polycrystalline materials at these temperatures. Furthermore with proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.
- Authors:
-
- National Institute of Standards and Technology, Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
- Tohoku Univ., Sendai (Japan)
- National Institute of Standards and Technology, Gaithersburg, MD (United States)
- Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office (HFTO)
- OSTI Identifier:
- 1327910
- Report Number(s):
- SAND-2016-9600J
Journal ID: ISSN 1754-5692; EESNBY; 647755
- Grant/Contract Number:
- AC04-94AL85000
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Energy & Environmental Science
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 12; Journal ID: ISSN 1754-5692
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
Citation Formats
Tang, Wan Si, Unemoto, Atsushi, Zhou, Wei, Stavila, Vitalie, Matsuo, Motoaki, Wu, Hui, Orimo, Shin-ichi, and Udovic, Terrence J. Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions. United States: N. p., 2015.
Web. doi:10.1039/c5ee02941d.
Tang, Wan Si, Unemoto, Atsushi, Zhou, Wei, Stavila, Vitalie, Matsuo, Motoaki, Wu, Hui, Orimo, Shin-ichi, & Udovic, Terrence J. Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions. United States. https://doi.org/10.1039/c5ee02941d
Tang, Wan Si, Unemoto, Atsushi, Zhou, Wei, Stavila, Vitalie, Matsuo, Motoaki, Wu, Hui, Orimo, Shin-ichi, and Udovic, Terrence J. Thu .
"Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions". United States. https://doi.org/10.1039/c5ee02941d. https://www.osti.gov/servlets/purl/1327910.
@article{osti_1327910,
title = {Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions},
author = {Tang, Wan Si and Unemoto, Atsushi and Zhou, Wei and Stavila, Vitalie and Matsuo, Motoaki and Wu, Hui and Orimo, Shin-ichi and Udovic, Terrence J.},
abstractNote = {Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na2B12H12, which contains large, icosahedral, divalent B12H122– anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li2B12H12, possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB11H12 and NaCB11H12 salts, which contain icosahedral, monovalent CB11H12– anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, and truly stellar ionic conductivities (>0.1 S cm–1) unmatched by any other known polycrystalline materials at these temperatures. Furthermore with proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.},
doi = {10.1039/c5ee02941d},
journal = {Energy & Environmental Science},
number = 12,
volume = 8,
place = {United States},
year = {Thu Oct 08 00:00:00 EDT 2015},
month = {Thu Oct 08 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Metal Cation−Methyl Interactions in CB 11 Me 12 - Salts of Me 3 Ge + , Me 3 Sn + , and Me 3 Pb +
journal, September 2004
- Zharov, Ilya; Weng, Tsu-Chien; Orendt, Anita M.
- Journal of the American Chemical Society, Vol. 126, Issue 38
The Disk Chopper Spectrometer at NIST: a new instrument for quasielastic neutron scattering studies
journal, August 2003
- Copley, J. R. D.; Cook, J. C.
- Chemical Physics, Vol. 292, Issue 2-3
Nuclear Magnetic Resonance Study of Atomic Motion in A 2 B 12 H 12 (A = Na, K, Rb, Cs): Anion Reorientations and Na + Mobility
journal, November 2013
- Skripov, Alexander V.; Babanova, Olga A.; Soloninin, Alexei V.
- The Journal of Physical Chemistry C, Vol. 117, Issue 49
Lithium Fast-Ionic Conduction in Complex Hydrides: Review and Prospects
journal, January 2011
- Matsuo, Motoaki; Orimo, Shin-ichi
- Advanced Energy Materials, Vol. 1, Issue 2
Update 1 of: Chemistry of the Carba- closo -dodecaborate(−) Anion, CB 11 H 12 –
journal, August 2013
- Douvris, Christos; Michl, Josef
- Chemical Reviews, Vol. 113, Issue 10
Evidence of a transition to reorientational disorder in the cubic alkali-metal dodecahydro-closo-dodecaborates
journal, November 2011
- Verdal, Nina; Wu, Hui; Udovic, Terrence J.
- Journal of Solid State Chemistry, Vol. 184, Issue 11
The structure of monoclinic Na 2 B 10 H 10 : a combined diffraction, spectroscopy, and theoretical approach
journal, January 2015
- Wu, Hui; Tang, Wan Si; Zhou, Wei
- CrystEngComm, Vol. 17, Issue 18
Exceptional Superionic Conductivity in Disordered Sodium Decahydro- closo -decaborate
journal, October 2014
- Udovic, Terrence J.; Matsuo, Motoaki; Tang, Wan Si
- Advanced Materials, Vol. 26, Issue 45
High temperature sodium batteries: status, challenges and future trends
journal, January 2013
- Hueso, Karina B.; Armand, Michel; Rojo, Teófilo
- Energy & Environmental Science, Vol. 6, Issue 3
Lithium superionic conduction in lithium borohydride accompanied by structural transition
journal, November 2007
- Matsuo, Motoaki; Nakamori, Yuko; Orimo, Shin-ichi
- Applied Physics Letters, Vol. 91, Issue 22
Complex Hydrides for Electrochemical Energy Storage
journal, January 2014
- Unemoto, Atsushi; Matsuo, Motoaki; Orimo, Shin-ichi
- Advanced Functional Materials, Vol. 24, Issue 16
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
Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993
- Rodríguez-Carvajal, Juan
- Physica B: Condensed Matter, Vol. 192, Issue 1-2
A lithium superionic conductor
journal, July 2011
- Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro
- Nature Materials, Vol. 10, Issue 9, p. 682-686
Lead palladium titanate: A room temperature nanoscale multiferroic thin film
journal, February 2020
- Mishra, K. K.; Instan, Alvaro A.; Kumari, Shalini
- Scientific Reports, Vol. 10, Issue 1
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011
- Momma, Koichi; Izumi, Fujio
- Journal of Applied Crystallography, Vol. 44, Issue 6
Nuclear Magnetic Resonance Study of Atomic Motion in the Mixed Borohydride–Amide Na 2 (BH 4 )(NH 2 )
journal, June 2014
- Soloninin, Alexei V.; Babanova, Olga A.; Medvedev, Evgeny Y.
- The Journal of Physical Chemistry C, Vol. 118, Issue 27
Conductivity measurements on nasicon and nasicon-modified materials
journal, July 1999
- Bohnke, O.
- Solid State Ionics, Vol. 122, Issue 1-4
Anion Reorientations in the Superionic Conducting Phase of Na 2 B 12 H 12
journal, July 2014
- Verdal, Nina; Udovic, Terrence J.; Stavila, Vitalie
- The Journal of Physical Chemistry C, Vol. 118, Issue 31
Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12.
journal, December 2007
- Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner
- ChemInform, Vol. 38, Issue 50
Ionic Conductivity of the Lithium Titanium Phosphate (Li[sub 1+X]M[sub X]Ti[sub 2−X](PO[sub 4])[sub 3], M = Al, Sc, Y, and La) Systems
journal, January 1989
- Aono, Hiromichi
- Journal of The Electrochemical Society, Vol. 136, Issue 2
A study of the electrical properties of single-crystal and polycrystalline β-alumina using complex plane analysis
journal, August 1977
- Hooper, A.
- Journal of Physics D: Applied Physics, Vol. 10, Issue 11
Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries
journal, October 2014
- Giri, Santanab; Behera, Swayamprabha; Jena, Puru
- Angewandte Chemie, Vol. 126, Issue 50
Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries
journal, October 2014
- Giri, Santanab; Behera, Swayamprabha; Jena, Puru
- Angewandte Chemie International Edition, Vol. 53, Issue 50
Sodium ionic conduction in complex hydrides with [BH 4 ] − and [NH 2 ] − anions
journal, May 2012
- Matsuo, Motoaki; Kuromoto, Shingo; Sato, Toyoto
- Applied Physics Letters, Vol. 100, Issue 20
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
Altering the structural properties of A2B12H12 compounds via cation and anion modifications
journal, October 2015
- Tang, Wan Si; Udovic, Terrence J.; Stavila, Vitalie
- Journal of Alloys and Compounds, Vol. 645
Lithium Ionic Conductor Thio-LISICON: The Li2S-GeS2-P2S5 System
journal, January 2001
- Kanno, Ryoji; Murayama, Masahiro
- Journal of The Electrochemical Society, Vol. 148, Issue 7, p. A742-A746
Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12
journal, October 2007
- Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner
- Angewandte Chemie International Edition, Vol. 46, Issue 41, p. 7778-7781
AgI-type solid electrolytes
journal, January 1976
- Funke, K.
- Progress in Solid State Chemistry, Vol. 11
DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009
- Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
- Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
First-order phase transition in the Li2B12H12 system
journal, January 2013
- Paskevicius, Mark; Pitt, Mark P.; Brown, David H.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 38
The design of a bismuth-based auxiliary filter for the removal of spurious background scattering associated with filter-analyzer neutron spectrometers
journal, April 2008
- Udovic, T. J.; Brown, C. M.; Leão, J. B.
- Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 588, Issue 3
Anionic Oligomerization of Li 2 [B 12 H 12 ] and Li[CB 11 H 12 ]: An Experimental and Computational Study
journal, January 2013
- Dávalos, Juan Z.; González, Javier; Guerrero, Andrés
- The Journal of Physical Chemistry C, Vol. 117, Issue 3
Complex high-temperature phase transitions in Li2B12H12 and Na2B12H12
journal, April 2014
- Verdal, Nina; Her, Jae-Hyuk; Stavila, Vitalie
- Journal of Solid State Chemistry, Vol. 212
Structure and dynamics from combined neutron scattering and first-principles studies
journal, November 2000
- Yildirim, Taner
- Chemical Physics, Vol. 261, Issue 1-2
An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries
journal, May 2015
- Tutusaus, Oscar; Mohtadi, Rana; Arthur, Timothy S.
- Angewandte Chemie International Edition, Vol. 54, Issue 27
Development of bulk-type all-solid-state lithium-sulfur battery using LiBH 4 electrolyte
journal, August 2014
- Unemoto, Atsushi; Yasaku, Syun; Nogami, Genki
- Applied Physics Letters, Vol. 105, Issue 8
Thermal, structural and possible ionic-conductor behaviour of CsB10CH13 and CsB11CH12
journal, April 1993
- Romerosa, A. M.
- Thermochimica Acta, Vol. 217
The least coordinating anion
journal, May 1986
- Shelly, Kenneth.; Reed, Christopher A.; Lee, Young Ja.
- Journal of the American Chemical Society, Vol. 108, Issue 11
Alkali and alkaline-earth metal dodecahydro-closo-dodecaborates: Probing structural variations via neutron vibrational spectroscopy
journal, September 2011
- Verdal, Nina; Zhou, Wei; Stavila, Vitalie
- Journal of Alloys and Compounds, Vol. 509
High ionic conductivity in lithium lanthanum titanate
journal, June 1993
- Inaguma, Yoshiyuki; Liquan, Chen; Itoh, Mitsuru
- Solid State Communications, Vol. 86, Issue 10, p. 689-693
Structural Behavior of Li 2 B 10 H 10
journal, March 2015
- Wu, Hui; Tang, Wan Si; Stavila, Vitalie
- The Journal of Physical Chemistry C, Vol. 119, Issue 12
A profile refinement method for nuclear and magnetic structures
journal, June 1969
- Rietveld, H. M.
- Journal of Applied Crystallography, Vol. 2, Issue 2, p. 65-71
Crystal Structure of Li 2 B 12 H 12 : a Possible Intermediate Species in the Decomposition of LiBH 4
journal, November 2008
- Her, Jae-Hyuk; Yousufuddin, Muhammed; Zhou, Wei
- Inorganic Chemistry, Vol. 47, Issue 21
Ab initio Force Constant Approach to Phonon Dispersion Relations of Diamond and Graphite
journal, December 1995
- Kresse, G.; Furthmüller, J.; Hafner, J.
- Europhysics Letters (EPL), Vol. 32, Issue 9
New, Highly Ion-Conductive Crystals Precipitated from Li2S-P2S5 Glasses
journal, April 2005
- Mizuno, F.; Hayashi, A.; Tadanaga, K.
- Advanced Materials, Vol. 17, Issue 7, p. 918-921
An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries
journal, May 2015
- Tutusaus, Oscar; Mohtadi, Rana; Arthur, Timothy S.
- Angewandte Chemie, Vol. 127, Issue 27
Role of Cation Size on the Structural Behavior of the Alkali-Metal Dodecahydro- closo -Dodecaborates
journal, June 2009
- Her, Jae-Hyuk; Zhou, Wei; Stavila, Vitalie
- The Journal of Physical Chemistry C, Vol. 113, Issue 26
Molekularzustand und elektrisches Leitvermögen kristallisierter Salze
journal, January 1914
- Tubandt, C.; Lorenz, Erich
- Zeitschrift für Physikalische Chemie, Vol. 87U, Issue 1
Works referencing / citing this record:
Dynamics of porous and amorphous magnesium borohydride to understand solid state Mg-ion-conductors
journal, June 2020
- Heere, Michael; Hansen, Anna-Lena; Payandeh, SeyedHosein
- Scientific Reports, Vol. 10, Issue 1
Liquid‐Like Ionic Conduction in Solid Lithium and Sodium Monocarba‐ closo ‐Decaborates Near or at Room Temperature
journal, February 2016
- Tang, Wan Si; Matsuo, Motoaki; Wu, Hui
- Advanced Energy Materials, Vol. 6, Issue 8
Solid-State Sodium Batteries
journal, February 2018
- Zhao, Chenglong; Liu, Lilu; Qi, Xingguo
- Advanced Energy Materials, Vol. 8, Issue 17
A complex hydride lithium superionic conductor for high-energy-density all-solid-state lithium metal batteries
journal, March 2019
- Kim, Sangryun; Oguchi, Hiroyuki; Toyama, Naoki
- Nature Communications, Vol. 10, Issue 1
Chemistry Design Towards a Stable Sulfide‐Based Superionic Conductor Li 4 Cu 8 Ge 3 S 12
journal, April 2019
- Wang, Yingqi; Lü, Xujie; Zheng, Chong
- Angewandte Chemie, Vol. 131, Issue 23
Combining proton and silaborane-based superhalogen anions – an effective route to new superacids as verified via systematic DFT calculations
journal, January 2019
- Luo, Lan; Zhou, Fu-Qiang; Zhao, Ru-Fang
- Dalton Transactions, Vol. 48, Issue 43
Fundamentals of inorganic solid-state electrolytes for batteries
journal, August 2019
- Famprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A.
- Nature Materials, Vol. 18, Issue 12
Lightweight complex metal hydrides for Li-, Na-, and Mg-based batteries
journal, March 2019
- Guzik, Matylda N.; Mohtadi, Rana; Sartori, Sabrina
- Journal of Materials Research, Vol. 34, Issue 6
Low-temperature paddlewheel effect in glassy solid electrolytes
journal, March 2020
- Smith, Jeffrey G.; Siegel, Donald J.
- Nature Communications, Vol. 11, Issue 1
Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB 11 H 12 and NaCB 11 H 12
journal, February 2018
- Dimitrievska, Mirjana; Shea, Patrick; Kweon, Kyoung E.
- Advanced Energy Materials, Vol. 8, Issue 15
Complex Metal Hydrides for Hydrogen, Thermal and Electrochemical Energy Storage
journal, October 2017
- Møller, Kasper; Sheppard, Drew; Ravnsbæk, Dorthe
- Energies, Vol. 10, Issue 10
Borohydride-Scaffolded Li/Na/Mg Fast Ionic Conductors for Promising Solid-State Electrolytes
journal, October 2018
- Cuan, Jing; Zhou, You; Zhou, Tengfei
- Advanced Materials, Vol. 31, Issue 1
A 3D Analogue of Phenyllithium: Solution‐Phase, Solid‐State, and Computational Study of the Lithiacarborane [Li−CB 11 H 11 ] −
journal, November 2019
- Dontha, Rakesh; Zhu, Tian‐Cheng; Shen, Yunjun
- Angewandte Chemie, Vol. 131, Issue 52
Ultra stable superatomic structure of doubly magic Ga 13 and Ga 13 Li electrolyte
journal, January 2020
- Steenbergen, Krista G.; Gaston, Nicola
- Nanoscale, Vol. 12, Issue 1
Machine Learning Enabled Computational Screening of Inorganic Solid Electrolytes for Suppression of Dendrite Formation in Lithium Metal Anodes
journal, August 2018
- Ahmad, Zeeshan; Xie, Tian; Maheshwari, Chinmay
- ACS Central Science, Vol. 4, Issue 8
The renaissance of hydrides as energy materials
journal, December 2016
- Mohtadi, Rana; Orimo, Shin-ichi
- Nature Reviews Materials, Vol. 2, Issue 3
Reorientational motion and -ion transport in system: Molecular dynamics study
journal, July 2019
- Sau, Kartik; Ikeshoji, Tamio; Kim, Sangryun
- Physical Review Materials, Vol. 3, Issue 7
Multifunctionality of silver closo-boranes
journal, April 2017
- Paskevicius, Mark; Hansen, Bjarne R. S.; Jørgensen, Mathias
- Nature Communications, Vol. 8, Issue 1
Sur-/interfacial regulation in all-solid-state rechargeable Li-ion batteries based on inorganic solid-state electrolytes: advances and perspectives
journal, January 2019
- Liang, Longwei; Sun, Xuan; Zhang, Jinyang
- Materials Horizons, Vol. 6, Issue 5
Chemistry Design Towards a Stable Sulfide-Based Superionic Conductor Li 4 Cu 8 Ge 3 S 12
journal, April 2019
- Wang, Yingqi; Lü, Xujie; Zheng, Chong
- Angewandte Chemie International Edition, Vol. 58, Issue 23
Sodium-Ion Battery Electrolytes: Modeling and Simulations
journal, February 2018
- Åvall, Gustav; Mindemark, Jonas; Brandell, Daniel
- Advanced Energy Materials, Vol. 8, Issue 17
Magnesium‐Based Clusters as Building Blocks of Electrolytes in Lithium‐Ion Batteries
journal, July 2019
- Sikorska, Celina
- ChemPhysChem, Vol. 20, Issue 17
Building Better Batteries in the Solid State: A Review
journal, November 2019
- Mauger, Alain; Julien, Christian M.; Paolella, Andrea
- Materials, Vol. 12, Issue 23, p. 3892
A 3D Analogue of Phenyllithium: Solution-Phase, Solid-State, and Computational Study of the Lithiacarborane [Li−CB 11 H 11 ] −
journal, November 2019
- Dontha, Rakesh; Zhu, Tian-Cheng; Shen, Yunjun
- Angewandte Chemie International Edition, Vol. 58, Issue 52
Building Better Batteries in the Solid State: A Review
journal, November 2019
- Mauger, Alain; Julien, Christian M.; Paolella, Andrea
- Materials, Vol. 12, Issue 23, p. 3892
Complex Hydrides for Energy Storage, Conversion, and Utilization
journal, July 2019
- He, Teng; Cao, Hujun; Chen, Ping
- Advanced Materials, Vol. 31, Issue 50
Dynamics of porous and amorphous magnesium borohydride to understand solid state Mg-ion-conductors
text, January 2020
- Heere, M.; Hansen, A. -L.; Payandeh, S. H.
- Nature Research
A complex hydride lithium superionic conductor for high-energy-density all-solid-state lithium metal batteries
journal, March 2019
- Kim, Sangryun; Oguchi, Hiroyuki; Toyama, Naoki
- Nature Communications, Vol. 10, Issue 1
Vacancies in functional materials for clean energy storage and harvesting: the perfect imperfection
journal, January 2017
- Li, Guowei; Blake, Graeme R.; Palstra, Thomas T. M.
- Chemical Society Reviews, Vol. 46, Issue 6
Interatomic potential construction with self-learning and adaptive database
journal, October 2017
- Miwa, Kazutoshi; Ohno, Hiroshi
- Physical Review Materials, Vol. 1, Issue 5