Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 135, Issue 26, Pages 9898-9906Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja404189t
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Funding
- National Science Foundation (Solid State Chemistry) [DMR-1005827]
- NSF [DMR-0521267]
- MRSEC program of the National Science Foundation [DMR-0520513]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-06CH11357]
- Batteries for Advanced Transportation Technologies (BATT) Program, U.S. Department of Energy [DE-AC02-06CH11357]
- NSF-NSEC
- NSF-MRSEC
- Keck Foundation
- state of Illinois
- NU
- W. M. Keck Foundation, NU
- NIH
- Rice Foundation
- Robert H. Lurie Comprehensive Cancer center
- Division Of Materials Research
- Direct For Mathematical & Physical Scien [1005827] Funding Source: National Science Foundation
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We present structural and electrochemical analyses of a new double-wolframite compound: AgNa-(VO2F2)(2) or SSVOF. SSVOF is fully ordered and displays electrochemical characteristics that give insight into electrode design for energy storage beyond lithium-ion chemistries. The compound contains trioxovanadium fluoride octahedra that combine to form one-dimensional chain like basic building units, characteristic of wolframite (NaWO4). The ID chains are stacked to create 2D layers; the cations Ag+ and Na+ lie between these layers. The vanadium oxide-fluoride octahedra are ordered by the use of cations (Ag+, Na+) that differ in polarizability. In the case of sodium-ion batteries, thermodynamically, the use of a sodium anode introduces a 300 mV loss in overall cell voltage as compared to a lithium anode; however, this can be counter balanced by introduction of fluoride into the framework to raise the reduction potentials via an inductive effect This allows sodium-ion batteries to have comparable voltages to lithium systems. With SSVOF as a baseline compound, we have identified new materials design rules for emerging sodium-ion systems that do not apply to lithium-ion systems. These strategies can be applied broadly to provide materials of interest for fundamental structural chemistry and appreciable voltages for sodium-ion electrochemistry.
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