Closo-Hydroborate Sodium Salts as an Emerging Class of Room-Temperature Solid Electrolytes
Source abstract
Abstract
Na-based hydroborates, such as NaCB9H10, Na2B10H10, NaCB11H12, and Na2B12H12, are known for their high ionic conductivity above a phase transition, usually far from room temperature. Here, a systematic investigation to suppress this phase transition and thus to stabilize novel crystal structures is conducted by means of anion mixing. The obtained compounds crystallize either with hexagonal and cubic close packed (hcp and ccp) or body-centered cubic (bcc) arrangement of anions without polymorphic evolution in the temperature range 100 < T < 700 K. The high symmetry and the configurational ionic disorder, which characterize all crystals, give room-temperature Na+ conductivity close or above 1 mS cm−1. Finally, high oxidative electrochemical stability between 3 and 4 V versus Na+/Na results from the aromatic nature of the boron cage, making Na-based hydroborates potentially suitable as efficient solid electrolytes for next-generation, high-voltage, Na-ion batteries.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Hydrogen Storage and Materials · Advanced Battery Materials and Technologies · Chemical Synthesis and Characterization
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (55)
Show source-provided references
1. 2019
2. The breakdown of β-alumina ceramic electrolyte10.1016/0013-4686(74)85065-6 ↗
3. Demonstration of high current densities and extended cycling in the garnet Li7La3Zr2O12 solid electrolyte10.1016/j.jpowsour.2018.06.055 ↗
4. Vapor pressures and thermophysical properties of ethylene carbonate, propylene carbonate, γ-valerolactone, and γ-butyrolactone10.1021/acs.jced.7b00578 ↗
5. Complex hydride for composite negative electrode—applicable to bulk-type all-solid-state Li-ion battery with wide temperature operation10.1016/j.ssi.2015.07.013 ↗
6. Complex hydrides for electrochemical energy storage10.1002/adfm.201303147 ↗
7. A stable 3 V all-solid-state sodium-ion battery based on a closo-borate electrolyte10.1039/C7EE02420G ↗
8. A complex hydride lithium superionic conductor for high-energy-density all-solid-state lithium metal batteries10.1038/s41467-019-09061-9 ↗
9. Room-temperature-operating Na solid-state battery with complex hydride as electrolyte10.1016/j.elecom.2019.106534 ↗
10. Modified anion packing of Na2B12H12 in close to room temperature superionic conductors10.1021/acs.inorgchem.7b00013 ↗
11. Phase stability and fast ion conductivity in the hexagonal LiBH4–LiBr–LiCl solid solution10.1021/acs.chemmater.9b01035 ↗
12. A highly stable sodium solid-state electrolyte based on a dodeca/deca-borate equimolar mixture10.1039/C7CC00794A ↗
13. A mixed anion hydroborate/carba-hydroborate as a room temperature Na-ion solid electrolyte10.1016/j.jpowsour.2018.09.085 ↗
14. Electrochemistry and boron-11 nuclear magnetic resonance spectra of monocarbon carboranes10.1021/ic50122a016 ↗
15. Chemistry of boranes. VIII. Salts and acids of B10H10-2 and B12H12-210.1021/ic50013a030 ↗
16. Thermal decomposition of anhydrous alkali metal dodecaborates M2B12H12 (M = Li, Na, K)10.3390/en81112326 ↗
17. Complex high-temperature phase transitions in Li2B12H12 and Na2B12H1210.1016/j.jssc.2014.01.006 ↗
18. Nuclear magnetic resonance study of atomic motion in A2B12H12 (A = Na, K, Rb, Cs): anion reorientations and Na+ mobility10.1021/jp4106585 ↗
19. Structural, chemical, and dynamical frustration: origins of superionic conductivity in closo-borate solid electrolytes10.1021/acs.chemmater.7b02902 ↗
20. Maximal symmetry transition paths for reconstructive phase transitions
21. Disordering phenomena in superionic conductors10.1088/0953-8984/14/32/201 ↗
22. Stabilizing superionic-conducting structures via mixed-anion solid solutions of monocarba- closo -borate salts10.1021/acsenergylett.6b00310 ↗
23. Anion reorientations and cation diffusion in LiCB11H12 and NaCB11H12: 1H, 7Li, and 23Na NMR studies10.1021/acs.jpcc.5b10055 ↗
24. Exceptional superionic conductivity in disordered sodium decahydro-closo-decaborate10.1002/adma.201403157 ↗
25. Liquid-like ionic conduction in solid lithium and sodium monocarba- closo -decaborates near or at room temperature10.1002/aenm.201502237 ↗
26. Local structure of the superionic conducting α-AgI type AgI1-xBrx solid-solution10.1016/0167-2738(88)90220-2 ↗
27. Silbersulfidbromid Ag3SBr und silbersulfidjodid Ag3SJ. II. Die kristallstrukturen von Ag3SBr, β- und α-Ag3SJ10.1002/zaac.19653400308 ↗
28. Nido-borate/Closo-borate mixed-anion electrolytes for all-solid-state batteries10.1021/acs.chemmater.9b03933 ↗
29. Limiting behavior of ac conductivity in ionically conducting crystals and glasses: A new universality10.1103/PhysRevLett.67.1559 ↗
30. Ionic conduction mechanism in the Na2(B12H12)0.5(B10H10)0.5closo-borate solid-state electrolyte: interplay of disorder and ion-ion interactions10.1021/acs.chemmater.9b00610 ↗
31. Electroceramics: characterization by impedance spectroscopy10.1002/adma.19900020304 ↗
32. On the origin of the universal dielectric response in condensed matter10.1038/277185a0 ↗
33. Heat capacity at the glass transition10.1103/PhysRevB.83.014201 ↗
34. Understanding ionic conductivity trends in polyborane solid electrolytes from ab initio molecular dynamics10.1021/acsenergylett.6b00620 ↗
35. Meyer–Neldel rule and anti Meyer–Neldel rule of ionic conductivity: conclusions from the coupling model10.1016/S0167-2738(97)00469-4 ↗
36. Origin and consequences of the compensation (Meyer-Neldel) law10.1103/PhysRevB.46.12244 ↗
37. Influence of lattice polarizability on the ionic conductivity in the lithium superionic argyrodites Li6PS5X (X = Cl, Br, I)10.1021/jacs.7b06327 ↗
38. Designing ionic conductors: the interplay between structural phenomena and interfaces in thiophosphate-based solid-state batteries10.1021/acs.chemmater.8b01293 ↗
39. Increased compressibility of pseudobrookite-type MgTi2O5 caused by cation disorder10.1126/science.277.5334.1965 ↗
40. A lithium superionic conductor10.1038/nmat3066 ↗
41. Mechanochemical synthesis of Li-argyrodite Li6PS5X (X = Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application10.1016/j.ssi.2012.06.008 ↗
42. Electrochemical oxidative stability of hydroborate-based solid-state electrolytes10.1021/acsaem.9b01487 ↗
43. Kinetics of electrochemical oxidative coupling of decahydroclovodecaborate(2–) in acetonitrile10.1021/ja00970a006 ↗
44. An efficient halogen-free electrolyte for use in rechargeable magnesium batteries10.1002/anie.201412202 ↗
45. Carboranes: a new class of weakly coordinating anions for strong electrophiles, oxidants, and superacids10.1021/ar970230r ↗
46. Stability and three-dimensional aromaticity of closo-monocarbaborane anions, CB(n)(-)(1)H(n)(-), and closo-dicarboranes, C(2)B(n)(-)(2)H(n)10.1021/ic980110v ↗
47. Three-dimensional aromaticity of polyhedral boranes10.1021/ja00479a015 ↗
48. Grimes · 2016
49. Pressure-induced phase transitions in Na2B12H12, structural investigation on a candidate for solid-state electrolyte10.1107/S2052520619004670 ↗
50. AMPLIMODES: symmetry-mode analysis on the Bilbao Crystallographic Server10.1107/S0021889809028064 ↗
51. Mode crystallography of distorted structures10.1107/S0108767310016247 ↗
52. FOX, ‘free objects for crystallography’: a modular approach to ab initio structure determination from powder diffraction10.1107/S0021889802015236 ↗
53. Whole-profile structure solution from powder diffraction data using simulated annealing10.1107/S002188980000248X ↗
54. VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data10.1107/S0021889811038970 ↗
55. The detrimental effects of carbon additives in Li10GeP2S12-based solid-state batteries10.1021/acsami.7b11530 ↗