Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)

Soloninin, A. V.; Skoryunov, R. V.; Babanova, O. A.; Skripov, A. V.; Dimitrievska, M.; Udovic, T. J.

doi:10.1016/j.jallcom.2019.06.019

Title: Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: ¹H and ²³Na NMR studies of solid-solution Na₂(CB₉H₁₀)(CB₁₁H₁₂)

Full Record
Other Related Research

Abstract

The hexagonal mixed-anion solid solution Na₂(CB₉H₁₀)(CB₁₁H₁₂) shows the highest room-temperature ionic conductivity among all known Na-ion conductors. To study the dynamical properties of this compound, we have measured the ¹H and ²³Na nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates in Na₂(CB₉H₁₀)(CB₁₁H₁₂) over the temperature range of 80-435 K. It is found that the diffusive motion of Na+ ions can be described in terms of two jump processes: the fast localized motion within the pairs of tetrahedral interstitial sites of the hexagonal close-packed lattice formed by large anions and the slower jump process via octahedral sites leading to long-range diffusion. Below 350 K, the slower Na⁺ jump process is characterized by the activation energy of 353(11) meV. Although Na⁺ mobility in Na₂(CB₉H₁₀)(CB₁₁H₁₂) found from our NMR experiments is higher than in other ionic conductors, it appears to be an order-of-magnitude lower than that expected on the basis of the conductivity measurements. This result suggests that the complex diffusion mechanism and/or correlations between Na⁺ jumps should be taken into account. The measured 1H spin-lattice relaxation rates for Na₂(CB₉H₁₀)(CB₁₁H₁₂) are consistent with a coexistence of at least two anion reorientational jump processes occurring at different frequency scales. Near room temperature, bothmore »« less

Authors:

^[1]; Skoryunov, R. V. ^[1];

^[1]; Skripov, A. V. ^[1]; Dimitrievska, M. ^[2]; Udovic, T. J. ^[3]

Russian Academy of Sciences (RAS), Ekaterinburg (Russian Federation)
National Renewable Energy Lab. (NREL), Golden, CO (United States); National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

Publication Date:: Wed Jun 05 00:00:00 EDT 2019

Research Org.:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office

OSTI Identifier:: 1542764

Alternate Identifier(s):: OSTI ID: 1529435

Report Number(s):: NREL/JA-5900-74309
Journal ID: ISSN 0925-8388

Grant/Contract Number:: AC36-08GO28308

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Alloys and Compounds

Additional Journal Information:: Journal Volume: 800; Journal Issue: C; Journal ID: ISSN 0925-8388

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 25 ENERGY STORAGE; energy storage materials; diffusion; nuclear resonances

Citation Formats


                    Soloninin, A. V., Skoryunov, R. V., Babanova, O. A., Skripov, A. V., Dimitrievska, M., and Udovic, T. J. Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12).  United States: N. p., 2019. 
Web.  doi:10.1016/j.jallcom.2019.06.019.

Copy to clipboard


                    Soloninin, A. V., Skoryunov, R. V., Babanova, O. A., Skripov, A. V., Dimitrievska, M., & Udovic, T. J. Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12).  United States.  https://doi.org/10.1016/j.jallcom.2019.06.019

Copy to clipboard


                    Soloninin, A. V., Skoryunov, R. V., Babanova, O. A., Skripov, A. V., Dimitrievska, M., and Udovic, T. J. Wed .  
"Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)".  United States.  https://doi.org/10.1016/j.jallcom.2019.06.019.  https://www.osti.gov/servlets/purl/1542764.

Copy to clipboard


                    
@article{osti_1542764,

  title        = {Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)},

  author       = {Soloninin, A. V. and Skoryunov, R. V. and Babanova, O. A. and Skripov, A. V. and Dimitrievska, M. and Udovic, T. J.},

  abstractNote = {The hexagonal mixed-anion solid solution Na2(CB9H10)(CB11H12) shows the highest room-temperature ionic conductivity among all known Na-ion conductors. To study the dynamical properties of this compound, we have measured the 1H and 23Na nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates in Na2(CB9H10)(CB11H12) over the temperature range of 80-435 K. It is found that the diffusive motion of Na+ ions can be described in terms of two jump processes: the fast localized motion within the pairs of tetrahedral interstitial sites of the hexagonal close-packed lattice formed by large anions and the slower jump process via octahedral sites leading to long-range diffusion. Below 350 K, the slower Na+ jump process is characterized by the activation energy of 353(11) meV. Although Na+ mobility in Na2(CB9H10)(CB11H12) found from our NMR experiments is higher than in other ionic conductors, it appears to be an order-of-magnitude lower than that expected on the basis of the conductivity measurements. This result suggests that the complex diffusion mechanism and/or correlations between Na+ jumps should be taken into account. The measured 1H spin-lattice relaxation rates for Na2(CB9H10)(CB11H12) are consistent with a coexistence of at least two anion reorientational jump processes occurring at different frequency scales. Near room temperature, both reorientational processes are found to be faster than the Na+ jump process responsible for the long-range diffusion.},

  doi          = {10.1016/j.jallcom.2019.06.019},

  journal      = {Journal of Alloys and Compounds},

  number       = C,

  volume       = 800,

  place        = {United States},

  year         = {Wed Jun 05 00:00:00 EDT 2019},

  month        = {Wed Jun 05 00:00:00 EDT 2019}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Accepted Manuscript (DOE)

Publisher's Version of Record

https://doi.org/10.1016/j.jallcom.2019.06.019

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 10 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

Complex high-temperature phase transitions in Li{sub 2}B{sub 12}H{sub 12} and Na{sub 2}B{sub 12}H{sub 12}

Journal Article Verdal, Nina ; Department of Materials Science and Engineering, University of Maryland, College Park, MD 20742-2115 ; Her, Jae-Hyuk ; ... - Journal of Solid State Chemistry

Differential scanning calorimetry measurements of Li{sub 2}B{sub 12}H{sub 12} and Na{sub 2}B{sub 12}H{sub 12} indicate hysteretic transformations to high-temperature phases at ≈615 K and 529 K, respectively, upon heating (1 K/min) from room temperature. X-ray and neutron powder diffraction measurements corroborate the phase-change behavior. For Li{sub 2}B{sub 12}H{sub 12}, the diffraction data are consistent with a previous study suggesting that the overall face-centered-cubic arrangement of icosahedral B{sub 12}H{sub 12}{sup 2−} anions is maintained upon transformation to the high-temperature polymorph, although the anions are now orientationally disordered and the Li{sup +} cations crystallographically disordered within an enlarged lattice. For Na{sub 2}B{submore »« less
https://doi.org/10.1016/J.JSSC.2014.01.006
Structural and Dynamical Properties of Potassium Dodecahydro-monocarba-closo-dodecaborate: KCB₁₁H₁₂

Journal Article Dimitrievska, Mirjana ; Wu, Hui ; Stavila, Vitalie ; ... - Journal of Physical Chemistry. C

MCB₁₁H₁₂ (M: Li, Na) dodecahydro-monocarba-closo-dodecaborate salt compounds are known to have stellar superionic Li⁺ and Na⁺ conductivities in their high-temperature disordered phases, making them potentially appealing electrolytes in all-solid-state batteries. Nonetheless, it is of keen interest to search for other related materials with similar conductivities while at the same time exhibiting even lower (more device-relevant) disordering temperatures, a key challenge for this class of materials. With this in mind, the unknown structural and dynamical properties of the heavier KCB₁₁H₁₂ congener were investigated in detail by X-ray powder diffraction, differential scanning calorimetry, neutron vibrational spectroscopy, nuclear magnetic resonance, quasielastic neutron scattering, and AC impedance measurements. This salt indeed undergoes an entropy-driven, reversible, order–disorder transformation and with a lower onset temperature (348 K upon heating and 340 K upon cooling) in comparison to the lighter LiCB₁₁H₁₂ and NaCB₁₁H₁₂ analogues. The K⁺ cations in both the low-T ordered monoclinic (P2_1/c) and high-T disordered cubic (more »« less
https://doi.org/10.1021/acs.jpcc.0c05038

Full Text Available
Nature of Decahydro-closo-decaborate Anion Reorientations in an Ordered Alkali-Metal Salt: Rb₂B₁₀H₁₀

Journal Article Dimitrievska, Mirjana ; Stavila, Vitalie ; Soloninin, Alexei V. ; ... - Journal of Physical Chemistry. C

The ordered monoclinic phase of the alkali-metal decahydro-closo-decaborate salt Rb₂B₁₀H₁₀ was found to be stable from about 250 K all the way up to an order-disorder phase transition temperature of ~762 K. The broad temperature range for this phase allowed for a detailed quasielastic neutron scattering (QENS) and nuclear magnetic resonance (NMR) study of the protypical B₁₀H₁₀^2- anion reorientational dynamics. The QENS and NMR combined results are consistent with an anion reorientational mechanism comprised of two types of rotational jumps expected from the anion geometry and lattice structure, namely, more rapid 90 degree jumps around the anion C₄ symmetry axismore »« less
Cited by 6
https://doi.org/10.1021/acs.jpcc.8b04385

Full Text Available
Na+ Diffusivity in Carbon-Substituted Nido- and Closo-Hydroborate Salts: Pulsed-Field-Gradient NMR Studies of Na-7-CB10H13 and Na2(CB9H10)(CB11H12)

Journal Article Skripov, A. V. ; Majer, G. ; Babanova, O. A. ; ... - Journal of Alloys and Compounds

The mixed-anion solid-solution closo-carbahydroborate Na2(CB9H10)(CB11H12) shows the highest room-temperature ionic conductivity among all known solid Na-ion and Li-ion conductors, and the related nido-type carbahydroborate Na-7-CB10H13 exhibits superionic conductivity above the order-disorder phase transition temperature, ~320 K. To study the Na-ion diffusivity that is closely related to the ionic conductivity in these compounds, we have measured the diffusion coefficients of Na+ cations in Na2(CB9H10)(CB11H12) and Na-7-CB10H13 using the pulsed-field-gradient (PFG) spin-echo technique over the temperature ranges of 298–403 K and 320–403 K, respectively. These measurements have revealed the exceptionally high Na+ diffusivities (exceeding 2 × 10-6 cm2/s) for both compounds. Inmore »« less
https://doi.org/10.1016/j.jallcom.2020.156781
The relationship between reorientational molecular motions and phase transitions in [Mg(H{sub 2}O){sub 6}](BF{sub 4}){sub 2}, studied with the use of {sup 1}H and {sup 19}F NMR and FT-MIR

Journal Article Mikuli, Edward ; Hetmańczyk, Joanna ; Grad, Bartłomiej ; ... - Journal of Chemical Physics

A {sup 1}H and {sup 19}F nuclear magnetic resonance study of [Mg(H{sub 2}O){sub 6}](BF{sub 4}){sub 2} has confirmed the existence of two phase transitions at T{sub c1} ≈ 257 K and T{sub c2} ≈ 142 K, detected earlier by the DSC method. These transitions were reflected by changes in the temperature dependences of both proton and fluorine of second moments M{sub 2}{sup H} and M{sub 2}{sup F} and of spin-lattice relaxation times T{sub 1}{sup H} and T{sub 1}{sup F}. The study revealed anisotropic reorientations of whole [Mg(H{sub 2}O){sub 6}]{sup 2+} cations, reorientations by 180° jumps of H{sub 2}O ligands, andmore »« less
https://doi.org/10.1063/1.4907372

Similar Records

Title: Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: 1H and 23Na NMR studies of solid-solution Na2(CB9H10)(CB11H12)

Abstract

Citation Formats

Title: Comparison of anion and cation dynamics in a carbon-substituted closo-hydroborate salt: ¹H and ²³Na NMR studies of solid-solution Na₂(CB₉H₁₀)(CB₁₁H₁₂)