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Title: Design of superionic polymer electrolytes

Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Current Opinion in Chemical Engineering
Additional Journal Information:
Journal Volume: 7; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-03-27 00:53:13; Journal ID: ISSN 2211-3398
Country of Publication:
United Kingdom

Citation Formats

Wang, Yangyang, and Sokolov, Alexei P. Design of superionic polymer electrolytes. United Kingdom: N. p., 2015. Web. doi:10.1016/j.coche.2014.09.002.
Wang, Yangyang, & Sokolov, Alexei P. Design of superionic polymer electrolytes. United Kingdom. doi:10.1016/j.coche.2014.09.002.
Wang, Yangyang, and Sokolov, Alexei P. 2015. "Design of superionic polymer electrolytes". United Kingdom. doi:10.1016/j.coche.2014.09.002.
title = {Design of superionic polymer electrolytes},
author = {Wang, Yangyang and Sokolov, Alexei P.},
abstractNote = {},
doi = {10.1016/j.coche.2014.09.002},
journal = {Current Opinion in Chemical Engineering},
number = C,
volume = 7,
place = {United Kingdom},
year = 2015,
month = 2

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.coche.2014.09.002

Citation Metrics:
Cited by: 13works
Citation information provided by
Web of Science

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  • 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, Na 2B 12H 12, which contains large, icosahedral, divalent B 12H 12 2– anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li 2B 12H 12, possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB 11H 12 and NaCB 11H 12 salts, which contain icosahedral, monovalent CB 11H 12more » 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.« less
  • The attractive safety and long-term stability of all solid-state batteries has added a new impetus to the discovery and development of solid electrolytes for lithium batteries. Recently several superionic lithium conducting solid electrolytes have been discovered. All the superionic lithium containing compounds (β-Li 3PS 4 and Li 10GeP 2S 12 and oxides, predominantly in the garnet phase) have partially occupied sites. This naturally begs the question of understanding the role of partial site occupancies (or site disorder) in optimizing ionic conductivity in these family of solids. In this paper, we find that for a given topology of the host lattice,more » maximizing the number of sites with similar Li-ion adsorption energies, which gives partial site occupancy, is a natural way to increase the configurational entropy of the system and optimize the conductivity. For a given topology and density of Li-ion adsorption sites, the ionic conductivity is maximal when the number of mobile Li-ions are equal to the number of mobile vacancies, also the very condition for achieving maximal configurational entropy. We demonstrate applicability of this principle by elucidating the role of Li-ion site disorder and the local chemical environment in the high ionic conductivity of β-Li 3PS 4. In addition, for β-Li 3PS 4 we find that a significant density of vacancies in the Li-ion sub-lattice (~25%) leads to sub-lattice melting at (~600 K) leading to a molten form for the Li-ions in an otherwise solid anionic host. This gives a lithium site occupancy that is similar to what is measured experimentally. We further show that quenching this disorder can improve conductivity at lower temperatures. As a consequence, we discover that (a) one can optimize ionic conductivity in a given topology by choosing a chemistry/composition that maximizes the number of mobile-carriers i.e. maximizing both mobile Li-ions and vacancies, and (b) when the concentration of vacancies becomes significant in the Li-ion sub-lattice, it becomes energetically as well as entropically favorable for it to remain molten well below the bulk decomposition temperature of the solid. Finally, this principle may already apply to several known superionic conducting solids.« less
  • Li 2B 12H 12, Na 2B 12H 12, and their closo-borate relatives exhibit unusually high ionic conductivity, making them attractive as a new class of candidate electrolytes in solid-state Li- and Na-ion batteries. However, further optimization of these materials requires a deeper understanding of the fundamental mechanisms underlying ultrafast ion conduction. To this end, we use ab initio molecular dynamics simulations and density-functional calculations to explore the motivations for cation diffusion. We find that superionic behavior in Li 2B 12H 12 and Na 2B 12H 12 results from a combination of key structural, chemical, and dynamical factors that introduce intrinsicmore » frustration and disorder. A statistical metric is used to show that the structures exhibit a high density of accessible interstitial sites and site types, which correlates with the flatness of the energy landscape and the observed cation mobility. Furthermore, cations are found to dock to specific anion sites, leading to a competition between the geometric symmetry of the anion and the symmetry of the lattice itself, which can facilitate cation hopping. Finally, facile anion reorientations and other low-frequency thermal vibrations lead to fluctuations in the local potential that enhance cation mobility by creating a local driving force for hopping. In conclusion, we discuss the relevance of each factor for developing new ionic conductivity descriptors that can be used for discovery and optimization of closo-borate solid electrolytes, as well as superionic conductors more generally.« less
  • Mechanical properties and conductivity were computed for several composite polymer electrolyte structures. A multi-phase effective medium approach was used to estimate effective conductivity. The Mori-Tanaka approach was applied for calculating the effective stiffness tensor of the composites. An analysis of effective mechanical properties was performed in order to identify the composite structures, which would be capable of blocking the dendrites forming in Li-ion battery when Li metal is used as anode. The data on conductivity, elastic modulus, and Poisson s ratio can be used to formulate design criteria for solid electrolytes that would exhibit appropriate stiffness and compressibility to suppressmore » lithium dendrite growth while maintaining high effective conductivities.« less