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Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba-closo-borate Salts
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† NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States
‡ Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742-2115, United States
§ Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
∥ Institute of Metal Physics, Ural Branch of the Russian Academy of Sciences, Ekaterinburg 620990, Russia
⊥ National Renewable Energy Laboratory, Golden, Colorado 80401, United States
# Energy Nanomaterials, Sandia National Laboratories, Livermore, California 94551, United States
∇ WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
*E-mail: [email protected]
*E-mail: [email protected]
*E-mail: [email protected]
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ACS Energy Letters

Cite this: ACS Energy Lett. 2016, 1, 4, 659–664
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https://doi.org/10.1021/acsenergylett.6b00310
Published September 1, 2016

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Abstract

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Solid lithium and sodium closo-polyborate-based salts are capable of superionic conductivities surpassing even liquid electrolytes, but often only at above-ambient temperatures where their entropically driven disordered phases become stabilized. Here we show by X-ray diffraction, quasielastic neutron scattering, differential scanning calorimetry, NMR, and AC impedance measurements that by introducing “geometric frustration” via the mixing of two different closo-polyborate anions, namely, 1-CB9H10– and CB11H12–, to form solid-solution anion-alloy salts of lithium or sodium, we can successfully suppress the formation of possible ordered phases in favor of disordered, fast-ion-conducting alloy phases over a broad temperature range from subambient to high temperatures. This result exemplifies an important advancement for further improving on the remarkable conductive properties generally displayed by this class of materials and represents a practical strategy for creating tailored, ambient-temperature, solid, superionic conductors for a variety of upcoming all-solid-state energy devices of the future.

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We have previously shown that the broad class of closo-polyborate salt compounds containing lithium and sodium cations routinely exhibit entropy-driven order–disorder transitions to become impressive superionic conductors. (1-4) The most spectacular ones to date are based on the more weakly coordinating monovalent CB11H12– and 1-CB9H10– anions. For example, NaCB9H10 displays a room-temperature Na+ conductivity of about 0.03 S cm–1, (4) which well surpasses that of any known polycrystalline Na or Li competitors, (5-7) including many liquid Na+ or Li+ electrolytes. (8-10) The ionic saltlike nature of all these compounds guarantees negligible electronic conductivity. Moreover, the overly large cagelike anions, although orientationally extremely mobile, remain translationally rigid within high-symmetry [face-centered-cubic (fcc), body-centered-cubic (bcc), or hexagonal], disordered, cation-vacancy-rich lattices, and their pseudoaromatic nature (11) leads to high chemical and electrochemical stability. All these observed disordered symmetries exhibit superionic conductivities, and although it is believed from purely geometric arguments that the bcc lattice is relatively superior for cation diffusion, (12) the more subtle effects of lattice structure on conductivity for these types of compounds seem to be overwhelmed by other factors such as the cooperative effects of anion reorientational motions on cation translations.
To make these materials more relevant for near-ambient-temperature device technologies, we need strategies for lowering (well below room temperature) or completely eliminating the transition temperature to the structurally disordered phases responsible for superionic conduction. This can be potentially accomplished in various ways. One obvious approach is to chemically modify the anions. A good example is the replacement of one apical boron atom of B10H102– with carbon to form 1-CB9H10– anions. The resulting NaCB9H10 salt possesses a lower transition temperature and a higher conductivity than Na2B10H10. (2, 4) More recently, we successfully demonstrated a second approach: that the disordered structures, and thus superionic conductivity, for a variety of closo-polyborate salts could indeed typically be stabilized at room temperature and below by crystallite nanosizing/disordering via mechanical milling. (13)
Here we demonstrate a third approach to stabilize disordered superionic structures well below room temperature without the need for mechanical milling, i.e., by synthesizing mixed-closo-polyborate-anion compounds from solutions. In particular, we formed Li2(CB9H10)(CB11H12) and Na2(CB9H10)(CB11H12) compound mixtures by drying aqueous solutions with equimolar amounts of either LiCB9H10 + LiCB11H12 or NaCB9H10 + NaCB11H12. Figure 1 displays the room-temperature X-ray powder diffraction (XRPD) patterns of the resulting precipitated mixtures after final vacuum drying steps overnight at 473 K. Rietveld refinement results for Li2(CB9H10)(CB11H12) confirm the formation of two equally prevalent disordered phases, one hexagonal (but with a slightly larger unit cell) like that found for pristine superionic LiCB9H10 above ≈350 K (4) and another fcc (but with a slightly smaller unit cell) like that found for pristine superionic LiCB11H12 above ≈395 K. (3) The different phases are due to either similar-energy disordered polymorphs, which is possible for closo-polyborates (1, 3) or incomplete homogenization yielding two mixture fractions, one that is slightly CB9H10-rich (hexagonal) and one that is slightly CB11H12-rich (fcc). The larger hexagonal lattice is consistent with the substitution of larger CB11H12– anions for smaller CB9H10– anions in the LiCB9H10-like disordered hexagonal structure, and the smaller fcc lattice is consistent with the substitution of smaller CB9H10– anions for larger CB11H12– anions in the LiCB11H12-like disordered fcc structure. In addition, a very minor fraction of a third disordered phase seems to be present, similar to the additional hexagonal (h2) polymorph previously observed at 428 K for NaCB11H12. (3) We stress that these different hexagonal and fcc disordered structures have been shown to be superionic for the single-anion analogs. (3, 4)

Figure 1

Figure 1. Room-temperature XRPD data [experimental (blue circles), fitted (orange line), and difference (black line) patterns] for solution-dried (a) Li2(CB9H10)(CB11H12) and (b) Na2(CB9H10)(CB11H12). Vertical green and red bars indicate the positions of Bragg peaks for the high-T hexagonal and fcc phases, respectively. The refined unit cell parameters for the Li-mixed sample are a = 6.8589(5) Å, c = 11.0116(11) Å, and V = 448.64(6) Å3 for the hexagonal structure; a = 9.7541(7) Å and V = 928.03(11) Å3 for the fcc structure (χ2 = 2.40; Rp = 0.110; Rwp = 0.0965). Refinement indicated an additional disordered phase (purple bars) indexed by profile matching to a probable hexagonal unit cell with parameters a = 6.86 Å and c = 16.85 Å. The refined unit cell parameters for the Na-mixed sample are a = 6.9905(11) Å, c = 11.3390(17) Å, and V = 479.88(13) Å3 for the hexagonal structure; a = 9.855(3) Å and V = 957.1(5) Å3 for the fcc structure (χ2 = 3.19; Rp = 0.156; Rwp = 0.132). (c) The disordered hexagonal structure with orange Li+/Na+ cation positions and large green (B/C atoms) and gray (H atoms) spheres denoting the diffraction-average spherical shells of scattering from the orientationally disordered CB9H10– and CB11H12– anions (superimposed).

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For Na2(CB9H10)(CB11H12), Rietveld refinement results confirm the formation of a predominant disordered hexagonal phase (but with a slightly larger unit cell) like that found for pristine superionic NaCB9H10 above ≈310 K (4) (with a minute fraction of fcc phase also present). The larger lattice again is consistent with the substitution of larger CB11H12– anions for CB9H10– anions in the NaCB9H10-like disordered hexagonal structure. We point out that the relatively low scattering from the liquidlike sublattice of cations associated with both the Na- and Li-based disordered mixtures precluded us from determining the distribution and occupations of cation interstitial sites using XRPD data. This will require additional neutron powder diffraction studies with 11B-enriched, deuterated samples, which are currently unavailable.
Differential scanning calorimetry (DSC) measurements for both mixtures cycled between 200 and 473 K (Figure S1 of the Supporting Information) displayed no obvious endothermic or exothermic phase transitions, indicating that the disordered solid-solution phases are stable at least within this temperature range.
Figure 2 shows NMR measurements of the 1H spin–lattice relaxation rates R1H for Li2(CB9H10)(CB11H12) and Na2(CB9H10)(CB11H12). For comparison, this figure also includes the fitted R1H(T) results (14) for the pristine LiCB11H12 and NaCB11H12 compounds undergoing their order–disorder phase transitions near 384 and 376 K, respectively. Figure 2 indicates that both Li- and Na-based mixtures retain high anion reorientational mobilities down to low temperatures because of the suppression of transitions to ordered phases. Indeed, the R1H(T) maximum (corresponding to the H jump rate of ≈108 s–1) is observed near 230 K for Li2(CB9H10)(CB11H12) and near 220 K for Na2(CB9H10)(CB11H12). For both mixtures, room temperature corresponds to the high-T slope of the R1H(T) peak (fast-motion limit), and a rough estimate of the H jump rate at 300 K gives 1010 s–1. It is interesting to note that for both mixtures, the high-T slope of the relaxation rate peak looks like a continuation of the slope for the disordered phase of the corresponding MCB11H12 compound. The activation energies for reorientational motion estimated from the high-T slopes are 220 meV for Li2(CB9H10)(CB11H12) and 180 meV for Na2(CB9H10)(CB11H12), values close to the activation energies found for the disordered phases of both LiCB11H12 and NaCB11H12 (177 meV). (14) Moreover, the experimental R1H(T) data for both mixtures indicate the presence of certain distributions of H jump rates. The characteristic signs of such distributions (15) include (i) the considerably smaller R1H(T)-peak amplitudes for the solid solutions compared to those for the pure component salts (14) and (ii) the steeper high-T slopes of the R1H(T) peaks compared to the low-T slopes (see Figure 2). Distributions of reorientational jump rates are expected, because there are two types of anions, and their disordered local environments will vary from one anion to the next. While for Na2(CB9H10)(CB11H12) the proton spin–lattice relaxation is found to be single-exponential over the studied temperature range, deviations from the single-exponential relaxation are observed for Li2(CB9H10)(CB11H12) below 270 K. (In this range, Figure 2 shows the results of a single-exponential approximation.) This feature is likely related to the coexistence of two disordered phases (hexagonal and fcc), as indicated in Figure 1a. To probe the cation mobility, we have also measured the 23Na NMR spectra in Na2(CB9H10)(CB11H12) and found an extremely narrow 23Na NMR line (0.4 kHz fwhm) at room temperature, indicating a fast, long-range diffusive motion of Na+ cations with a jump rate exceeding at least ≈104 s–1 (the lower limit from the 23Na NMR spectral measurements).

Figure 2

Figure 2. Proton spin–lattice relaxation rates measured at 28 MHz versus inverse temperature for Li2(CB9H10)(CB11H12) and Na2(CB9H10)(CB11H12). The black lines show the fits to the proton spin–lattice relaxation rates at the same frequency for LiCB11H12 and NaCB11H12 from ref 14 undergoing their order–disorder phase transitions near 384 and 376 K, respectively.

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In agreement with the NMR results, neutron-elastic-scattering fixed-window scans (FWSs) between 100 and 400 K for the Li and Na sample mixtures in Figure 3 also indicate highly mobile anion reorientational motions already approaching 108 jumps s–1 by around 240 and 210 K, respectively, as signaled by the onset of the drop in neutron elastic intensity near these temperatures. The jump rates attain the order of 1010 reorientational jumps s–1 by around 330 and 300 K, respectively, as the FWS intensities level off again. For comparison, the much sharper intensity changes for the FWSs for the pure component salts at higher temperatures mark the more abrupt hysteretic phase-change behaviors from relatively immobile anions in the lower-T ordered phases (<108 jumps s–1) to significantly more mobile anions in the high-T disordered phases (>1010 jumps s–1). The high anion mobility seen for the anion mixtures by both NMR and FWSs is representative behavior of superionic-conducting disordered closo-polyborate phases. (3, 4, 14)

Figure 3

Figure 3. Neutron elastic-scattering FWSs for Li2(CB9H10)(CB11H12) and Na2(CB9H10)(CB11H12) compared with those for the various single-anion component compounds, summed over detectors covering a Q range of 0.87–1.68 Å–1. Arrows differentiate heating and cooling scans. For a reasonable qualitative comparison, the individual data sets were scaled so as to have similar minimum and maximum intensities.

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Figure 4 shows the T-dependent ionic conductivity for Li2(CB9H10)(CB11H12) and Na2(CB9H10)(CB11H12) compared with that for the component compounds. (3, 4) As for the component compounds, (3, 4) the complex impedance plots of the solid solutions in Figure S2 represent purely ionic conductors. The Li2(CB9H10)(CB11H12) conductivity seems to match that for disordered LiCB9H10 (ref 4) and Li10GeP2S12 (ref 5) at 350 K (≈0.04 S cm–1) and above, remaining somewhat lower than that for disordered LiCB11H12 (ref 3) above 380 K. Below 350 K, the Li2(CB9H10)(CB11H12) conductivity decreases below that of Li10GeP2S12 to ≈4 μS cm–1 by 243 K. The Na2(CB9H10)(CB11H12) conductivity is much more impressive, seemingly even better than disordered NaCB9H10 and NaCB11H12 at all temperatures, (3, 4) and decreasing much less rapidly with temperature, from ≈0.07 S cm–1 at 300 K to ≈5 mS cm–1 at 243 K. This disordered solid-solution Na+ conductor displays conductivity substantially higher than that of any known solid Na+ or Li+ conductor. Indeed, a 300 K comparison in Figure 4 shows that it is roughly 50× more conductive than its closest Na+ competitor, Na3PSe4, (6) and around 7× better than Li10GeP2S12. (5) The relatively larger cell constants, higher anion mobility, and potentially weaker cation–anion interactions for Na2(CB9H10)(CB11H12) [compared to Li2(CB9H10)(CB11H12)] likely all contribute to its unmatched conductivity.

Figure 4

Figure 4. (a) Temperature dependences of the ionic conductivities (σ) for solution-dried, cold-pressed Li2(CB9H10)(CB11H12) and Na2(CB9H10)(CB11H12) using Li and Au electrodes, respectively, compared with those for the single-anion compounds (3, 4) and the closest-performing competitors, Li10GeP2S12 and Na3PSe4, (5, 6) and (b) ln(σT) vs T–1 and resulting fitted activation energies for the two mixed compounds. Closed and open symbols denote heating and cooling cycles, respectively.

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The conductivity barriers estimated in Figure 4 [311(2) meV and 226(2) meV for Li+ and Na+, respectively] above room temperature, are in general agreement with those for the single-anion compounds. (3, 4) The apparent changes in the overall barriers at subambient temperatures [to 743(2) and 348(2) meV, respectively] signal changes in the rate-limiting steps. If the highly reorientationally mobile anions are enabling a reduced conductivity barrier at higher temperatures via a cooperative dynamical effect with the diffusing cations, a higher barrier emerging with decreasing temperatures may be indicating their reducing influence due to decreasing mobility. Further insights still await molecular dynamics computations.
The combined experimental results above suggest that mixing anions of slightly different geometric “flavors” such as CB9H10– (ellipsoidal) and CB11H12– (icosahedral) entail an enthalpic penalty upon formation of any possible ordered phase. In particular, trying to incorporate either CB11H12– into an ordered LiCB9H10 or NaCB9H10 lattice (4, 16) or 1-CB9H10– into an ordered LiCB11H12 or NaCB11H12 lattice (3) likely leads to some degree of geometric frustration with the surrounding cations. Hence, it appears that the disordered phase is favored outright, in which the exact geometric flavor of orientationally disordered anions is much less important within the more accommodating disordered cation sublattice.
Although solution-drying is likely the preferred route for accomplishing molecular-level mixing of these anions, and past experience indicates that it can also work for synthesizing mixed Li+ and Na+ cation phases with closo-borate anions, (17) we know that not all such anions can be effectively mixed in this way. For example, our earlier attempts to form a 1:1 solid solution of Na2B12H12 and Na2B10H10 in this way proved to be unsuccessful. One main reason is that each of these fast-ion-conducting compounds can possess varying solubilities and tend to form different stable solid hydrates during precipitation. Upon precipitation, the hydrates of the different compounds often form independently into large crystallites with little mixing. Further vacuum drying leads to coarse mixtures of the original single-anion compounds. Because the anion translational mobilities are extremely low, annealing these coarse mixtures at reasonable temperatures is insufficient to cause molecular-level intermixing of the anions on an acceptable time scale. In these cases, mechanically milling anhydrous compound mixtures is one way to ensure such intimate intermixing, as was demonstrated for a ball-milled 1:1 Na2B12H12:Na2B10H10 mixture, (13) which exhibited a room-temperature bcc-like disordered phase reminiscent of superionic Na2B12H12, (18) but with a smaller unit-cell volume intermediate between those for pure Na2B12H12 and Na2B10H10.
It is worth mentioning that inadvertent yet advantageous anion-mixing effects leading to enhanced cationic conductivity may also be occurring during the alternative solvent-free-synthesis method for producing B12H122–-based compounds via reaction of MH or MBH4 with B10H14. (19, 20) It is known that other anions, most notably B10H102– anions, are routinely present in nontrivial amounts, (19, 20) so that the final M2B12H12 may actually be a mixed-anion phase, which based on what we now know, can lead to a solid solution with structural disorder and unexpected conductivity behavior. Indeed, this may explain the much higher room-temperature ionic conductivities observed for Li2B12H12 and the anomalous order–disorder transition temperature observed for LiNaB12H12 (with ∼14% B10H102– anions), both compounds which were synthesized by the solvent-free method, (21, 22) compared to the corresponding properties for Li2B12H12 and LiNaB12H12 samples known to be largely free of such anion impurities. (13, 17) From the viewpoint of producing a better ionic conductor, such impurities are desirable and can lead to stabilization of the desired superionic disordered phases at room temperature and below.
We further tested the ball-milling strategy with the present carborate compounds by separately ball-milling 1:1 anhydrous LiCB9H10:LiCB11H12 and NaCB9H10:NaCB11H12 mixtures. Room-temperature XRPD patterns (Figure S3) confirmed that both ball-milled mixtures formed predominantly hexagonal disordered structures like the pure disordered MCB9H10 compounds (but with slightly expanded unit cells and broadened Bragg peaks), consistent with nanosized crystallites and more complete homogenization. However, annealing these samples for only 1 h at 473 K led to a sharpening of the Bragg peaks presumably due to sintering. The Na-based mixture remained hexagonal, with an XRPD pattern closely resembling that of its solution-dried analog in Figure 1. The Li-based mixture shifted from predominantly hexagonal to a combination of hexagonal and fcc, again with an XRPD pattern closely resembling its solution-dried analog. DSC measurements again showed no phase transitions between 200 and 473 K, and FWSs (Figure S4) indicated anion reorientational mobility behaviors similar to those for the solution-dried samples. Finally, conductivities (Figure S5) followed trends with temperature similar to those of the solution-dried samples, although the values observed for the ball-milled samples (compared to the solution-dried samples) were around 2× larger for Na+ and 2–7× smaller for Li+. The reasons for these variations are not yet clear and will require more extensive studies, but they may have something to do with the preparation-dependent differences in particle morphologies, anion mixing, and anion degradations.
Despite these conductivity differences, both methods confirm that anion mixing indeed leads to intimately anion-mixed solid solutions with disordered superionic structures down to subambient temperatures. Further work is in progress to tune the procedures that will yield optimal conductivity properties. Such spectacular mixture-induced behavior is an additional promising development that further enhances the prospects of this broad class of large polyhedral-anion-based compounds for successful incorporation into next-generation, all-solid-state energy-storage devices.

Experimental Methods

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Anhydrous lithium and sodium 1-carba-closo-decaborates and carba-closo-dodecaborates (LiCB9H10, NaCB9H10, LiCB11H12, and NaCB11H12) were used as starting materials. (N.B., as there are two possible CB9H10– isomers, 1-carba- refers to carbon occupying an apical position of the bicapped-square-antiprismatic CB9H10– anion. Here, it is assumed that CB9H10– refers to the 1-CB9H10– isomer.) Mixed-anion solid-solution phases Li2(CB9H10)(CB11H12) and Na2(CB9H10)(CB11H12) were synthesized by first dissolving equimolar amounts of the respective pure anhydrous components in water followed by solid-hydrate precipitation by room-temperature evacuation of the excess water, and finally by complete removal of any remaining solid-hydrate waters by overnight evacuation at 473 K. For comparison, 100 h ball-milled, 1:1 anhydrous mixtures of LiCB9H10:LiCB11H12 and NaCB9H10:NaCB11H12 were prepared according to procedures in ref 13. More complete information about starting materials and experimental details concerning XRPD, NMR, DSC, FWSs, and conductivity measurements can be found in the Supporting Information.
Structural depictions were made using the VESTA (Visualization for Electronic and Structural Analysis) software. (23) For all figures, standard uncertainties are commensurate with the observed scatter in the data, if not explicitly designated by vertical error bars.

Supporting Information

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsenergylett.6b00310.

  • Experimental details; DSC scans; complex impedance plots for solution-dried sample mixtures; and XRPD, FWS, and ionic conductivity data for analogous ball-milled sample mixtures (PDF)

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Author Information

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  • Corresponding Authors
    • Wan Si Tang - NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States;  Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742-2115, United States;  Email: [email protected]
    • Shin-ichi Orimo - Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan;  WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan;  Email: [email protected]
    • Terrence J. Udovic - NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States;  Email: [email protected]
  • Authors
    • Koji Yoshida - Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
    • Alexei V. Soloninin - Institute of Metal Physics, Ural Branch of the Russian Academy of Sciences, Ekaterinburg 620990, Russia
    • Roman V. Skoryunov - Institute of Metal Physics, Ural Branch of the Russian Academy of Sciences, Ekaterinburg 620990, Russia
    • Olga A. Babanova - Institute of Metal Physics, Ural Branch of the Russian Academy of Sciences, Ekaterinburg 620990, Russia
    • Alexander V. Skripov - Institute of Metal Physics, Ural Branch of the Russian Academy of Sciences, Ekaterinburg 620990, Russia
    • Mirjana Dimitrievska - NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States;  National Renewable Energy Laboratory, Golden, Colorado 80401, United States
    • Vitalie Stavila - Energy Nanomaterials, Sandia National Laboratories, Livermore, California 94551, United States
  • Notes
    The authors declare no competing financial interest.

Acknowledgment

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This work was performed, in part, in collaboration between members of IEA HIA Task 32–Hydrogen-based Energy Storage. The authors gratefully acknowledge support from the Collaborative Research Center on Energy Materials, Tohoku University; JSPS KAKENHI under Grant Nos. 25220911 and 26820311; the Russian Federal Agency of Scientific Organizations under Program “Spin” No. 01201463330; and the Russian Foundation for Basic Research under Grant No. 15-03-01114. M.D. gratefully acknowledges research support from the U.S. DOE Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office, under Contract No. DE-AC36-08GO28308. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. DOE’s National Nuclear Security Administration under Contract No. DE-AC04-94AL85000. This work utilized facilities supported in part by the National Science Foundation under Agreement DMR-0944772.

References

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This article references 23 other publications.

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    Energy & Environmental Science (2015), 8 (12), 3637-3645CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
    Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of org. liq. 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 cond., albeit only above its 529 K phase transition. Its lithium congener, Li2B12H12, possesses an even more technol. prohibitive transition temp. above 600 K. Here we show that the chem. related LiCB11H12 and NaCB11H12 salts, which contain icosahedral, monovalent CB11H12- anions, both exhibit much lower transition temps. near 400 K and 380 K, resp., and truly stellar ionic conductivities (>0.1 S cm-1) unmatched by any other known polycryst. materials at these temps. With proper modifications, we are confident that room-temp.-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.
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  4. 4
    Tang, W. S.; Matsuo, M.; Wu, H.; Stavila, V.; Zhou, W.; Talin, A. A.; Soloninin, A. V.; Skoryunov, R. V.; Babanova, O. A.; Skripov, A. V. Liquid-like Ionic Conduction in Solid Lithium and Sodium Monocarba-Closo-Decaborates near or at Room Temperature Adv. Energy Mater. 2016, 6, 1502237 DOI: 10.1002/aenm.201502237
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    Kamaya, N.; Homma, K.; Yamakawa, Y.; Hirayama, M.; Kanno, R.; Yonemura, M.; Kamiyama, T.; Kato, Y.; Hama, S.; Kawamoto, K. A Lithium Superionic Conductor Nat. Mater. 2011, 10, 682– 686 DOI: 10.1038/nmat3066
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    A lithium superionic conductor
    Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, Akio
    Nature Materials (2011), 10 (9), 682-686CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
    Batteries are a key technol. in modern society. They are used to power elec. and hybrid elec. vehicles and to store wind and solar energy in smart grids. Electrochem. devices with high energy and power densities can currently be powered only by batteries with org. liq. electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10-2 S/cm) only at 50-80°, which is one order of magnitude lower than those of org. liq. electrolytes. Here, the authors report a Li superionic conductor, Li10GeP2S12 that has a new 3-dimensional framework structure. It exhibits an extremely high Li ionic cond. of 12 mS/cm at room temp. This represents the highest cond. achieved in a solid electrolyte, exceeding even those of liq. org. electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochem. properties (high cond. and wide potential window).
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  6. 6
    Sadikin, Y.; Brighi, M.; Schouwink, P.; Černý, R. Superionic Conduction of Sodium and Lithium in Anion-Mixed Hydroborates Na3BH4B12H12 and (Li0.7Na0.3)3BH4B12H12 Adv. Energy Mater. 2015, 5, 1501016 DOI: 10.1002/aenm.201501016
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    Zhang, L.; Yang, K.; Mi, J.; Lu, L.; Zhao, L.; Wang, L.; Li, Y.; Zeng, H. Na3PSe4: A Novel Chalcogenide Solid Electrolyte with High Ionic Conductivity Adv. Energy Mater. 2015, 5, 1501294 DOI: 10.1002/aenm.201501294
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    Monti, D.; Jónsson, E.; Palacín, M. R.; Johansson, P. Ionic Liquid Based Electrolytes for Sodium-Ion Batteries: Na+ Solvation and Ionic Conductivity J. Power Sources 2014, 245, 630– 636 DOI: 10.1016/j.jpowsour.2013.06.153
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    8
    Ionic liquid based electrolytes for sodium-ion batteries: Na+ solvation and ionic conductivity
    Monti, Damien; Jonsson, Erlendur; Palacin, M. Rosa; Johansson, Patrik
    Journal of Power Sources (2014), 245 (), 630-636CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
    Ionic liq. (IL) based sodium-ion (Na+) battery electrolytes obtained by mixing imidazolium-TFSI ILs (EMIm-TFSI and BMIm-TFSI) with the corresponding sodium salt (NaTFSI) were studied using a wide range of characterization techniques: dielec. spectroscopy, DSC, densitometry, viscometry, and Raman spectroscopy. The sodium ion conducting electrolytes exhibit excellent ionic conductivities, up to 5.5 mS cm-1 at room temp., and a useful thermal window of -86° to 150°. In more detail, Raman data anal. supported by DFT calcns. on Na+-TFSI complexes, allow one to det. the sodium ion solvation and charge carrier nature as a function of salt concn. The results are compared to data for the corresponding Li systems and while such electrolytes essentially form [Li(TFSI)2]- as the main Li+ carrier, the sodium systems seem to dominantly form [Na(TFSI)3]2- complexes. The effects on cond. and viscosity and the consequences for sodium-ion battery implementation are discussed.
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  9. 9
    Ding, M. S.; Xu, K.; Zhang, S. S.; Amine, K.; Henriksen, G. L.; Jow, T. R. Change of Conductivity with Salt Content, Solvent Composition, and Temperature for Electrolytes of LiPF6 in Ethylene Carbonate-Ethyl Methyl Carbonate J. Electrochem. Soc. 2001, 148, A1196– A1204 DOI: 10.1149/1.1403730
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    9
    Change of conductivity with salt content, solvent composition, and temperature for electrolytes of LiPF6 in ethylene carbonate-ethyl methyl carbonate
    Ding, M. S.; Xu, K.; Zhang, S. S.; Amine, K.; Henriksen, G. L.; Jow, T. R.
    Journal of the Electrochemical Society (2001), 148 (10), A1196-A1204CODEN: JESOAN; ISSN:0013-4651. (Electrochemical Society)
    We measured the electrolytic conductivities of the electrolytes of LiPF6 in ethylene carbonate-Et Me carbonate at different salt contents, solvent compns., and temps. in the ranges of their practical values. To these data, we fitted a fourth degree trivariate polynomial and obtained a close fit. We then plotted this function as surface and contour plots in the coordinates of salt content and solvent compn. for a series of temps. These plots showed the change of cond. with the simultaneous changes of salt content and solvent compn. and the influence of temp. on this change, thus mapping the locations for the optimal combinations of salt content and solvent compn. for max. cond. of the electrolytes at desired temps. Here we also discuss and interpret qual. the trends found in the change of cond. with salt content, solvent compn., and temp., based on the dependency on the same variables of these three factors: the no. of dissocd. ions in the electrolyte, the dielec. const. of the solvent, and the viscosity of the electrolyte.
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  10. 10
    Kalhoff, J.; Eshetu, G. G.; Bresser, D.; Passerini, S. Safer Electrolytes for Lithium-Ion Batteries: State of the Art and Perspectives ChemSusChem 2015, 8, 2154– 2175 DOI: 10.1002/cssc.201500284
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    10
    Safer Electrolytes for Lithium-Ion Batteries: State of the Art and Perspectives
    Kalhoff, Julian; Eshetu, Gebrekidan Gebresilassie; Bresser, Dominic; Passerini, Stefano
    ChemSusChem (2015), 8 (13), 2154-2175CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
    A review. Li-ion batteries are becoming increasingly important for electrifying the modern transportation system and, thus, hold the promise to enable sustainable mobility in the future. However, their large-scale application is hindered by severe safety concerns when the cells are exposed to mech., thermal, or elec. abuse conditions. These safety issues are intrinsically related to their superior energy d., combined with the (present) use of highly volatile and flammable org.-solvent-based electrolytes. Herein, state-of-the-art electrolyte systems and potential alternatives are briefly surveyed, with a particular focus on their (inherent) safety characteristics. The challenges, which so far prevent the widespread replacement of org. carbonate-based electrolytes with LiPF6 as the conducting salt, are also reviewed herein. Starting from rather facile electrolyte modifications by (partially) replacing the org. solvent or Li salt and/or the addn. of functional electrolyte additives, conceptually new electrolyte systems, including ionic liqs., solvent-free, and/or gelled polymer-based electrolytes, as well as solid-state electrolytes, are also considered. Indeed, the opportunities for designing new electrolytes appear to be almost infinite, which certainly complicates strict classification of such systems and a fundamental understanding of their properties. Nevertheless, these innumerable opportunities also provide a great chance of developing highly functionalized, new electrolyte systems, which may overcome the afore-mentioned safety concerns, while also offering enhanced mech., thermal, physicochem., and electrochem. performance.
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  11. 11
    Lipscomb, W. H. Boron Hydrides; W. A. Benjamin, Inc.: New York, 1963.
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    Wang, Y.; Richards, W. D.; Ong, S. P.; Miara, L. J.; Kim, J. C.; Mo, Y.; Ceder, G. Design Principles for Solid-State Lithium Superionic Conductors Nat. Mater. 2015, 14, 1026– 1031 DOI: 10.1038/nmat4369
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    Design principles for solid-state lithium superionic conductors
    Wang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J.; Kim, Jae Chul; Mo, Yifei; Ceder, Gerbrand
    Nature Materials (2015), 14 (10), 1026-1031CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
    Lithium solid electrolytes can potentially address two key limitations of the org. electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochem. stability. However, achieving a Li+ cond. in the solid state comparable to existing liq. electrolytes (>1 mS cm-1) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centered cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic cond., and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.
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  13. 13
    Tang, W. S.; Matsuo, M.; Wu, H.; Stavila, V.; Unemoto, A.; Orimo, S.; Udovic, T. J. Stabilizing Lithium and Sodium Fast-Ion Conduction in Solid Polyhedral-Borate Salts at Device-Relevant Temperatures Energy Storage Mater. 2016, 4, 79– 83 DOI: 10.1016/j.ensm.2016.03.004
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    Skripov, A. V.; Skoryunov, R. V.; Soloninin, A. V.; Babanova, O. A.; Tang, W. S.; Stavila, V.; Udovic, T. J. Anion Reorientations and Cation Diffusion in LiCB11H12 and NaCB11H12: 1H, 7Li, and 23Na NMR Studies J. Phys. Chem. C 2015, 119, 26912– 26918 DOI: 10.1021/acs.jpcc.5b10055
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    14
    Anion Reorientations and Cation Diffusion in LiCB11H12 and NaCB11H12: 1H, 7Li, and 23Na NMR Studies
    Skripov, Alexander V.; Skoryunov, Roman V.; Soloninin, Alexei V.; Babanova, Olga A.; Tang, Wan Si; Stavila, Vitalie; Udovic, Terrence J.
    Journal of Physical Chemistry C (2015), 119 (48), 26912-26918CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    To study the dynamical properties of the monocarba-closo-dodecaborates LiCB11H12 and NaCB11H12 showing the exceptionally high ionic conductivities in the high-temp. disordered phases, the authors have measured the temp. dependences of the 1H, 7Li, and 23Na NMR spectra and spin-lattice relaxation rates in these compds. below and above the phase transition points. For both compds. the transition from the low-T ordered to the high-T disordered phase (near 384 and 376 K for LiCB11H12 and NaCB11H12, resp.) is accompanied by a nearly 3 orders of magnitude increase in the reorientational jump rate of [CB11H12]- anions. The results of the authors' 7Li and 23Na NMR measurements indicate that the phase transitions from the low-T to the high-T phases of both LiCB11H12 and NaCB11H12 are also accompanied by a strong acceleration of translational diffusion of (Li+ or Na+). In the high-T phases of LiCB11H12 and NaCB11H12, the cation diffusion was characterized by low activation energies: 92(7) and 152(8) meV, resp. These results are consistent with the high superionic cond. in the disordered phases of LiCB11H12 and NaCB11H12; also, probably the enhanced reorientational mobility of large nearly spherical anions may facilitate the translational mobility of the cations.
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  15. 15
    Markert, J. T.; Cotts, E. J.; Cotts, R. M. Hydrogen Diffusion in the Metallic Glass a-Zr3RhH3.5 Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, 6446– 6452 DOI: 10.1103/PhysRevB.37.6446
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    Wu, H.; Tang, W. S.; Zhou, W.; Tarver, J. D.; Stavila, V.; Brown, C. M.; Udovic, T. J. The Low-Temperature Structural Behavior of Sodium 1-Carba-Closo-Decaborate: NaCB9H10 J. Solid State Chem. 2016, 243, 162– 167 DOI: 10.1016/j.jssc.2016.08.024
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    16
    The low-temperature structural behavior of sodium 1-carba-closo-decaborate: NaCB9H10
    Wu, Hui; Tang, Wan Si; Zhou, Wei; Tarver, Jacob D.; Stavila, Vitalie; Brown, Craig M.; Udovic, Terrence J.
    Journal of Solid State Chemistry (2016), 243 (), 162-167CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
    Two ordered phases of the novel solid superionic conductor Na 1-carba-closo-decaborate (NaCB9H10) were identified via synchrotron x-ray powder diffraction in combination with 1st-principles calcns. and neutron vibrational spectroscopy. A monoclinic packing of the large ellipsoidal CB9H-10 anions prevails at the lowest temps., but a 1st-order transformation to a slightly modified orthorhombic packing is largely complete by 240 K. The CB9H-10 anion orientational alignments and Na+ cation interstitial sitings in both phases are arranged so as to minimize the cation proximities to the uniquely more pos. C-bonded H atoms of the anions. These results provide valuable structural information pertinent to understanding the relatively low-temp., entropy-driven, order-disorder phase transition for this compd.
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  17. 17
    Tang, W. S.; Udovic, T. J.; Stavila, V. Altering the Structural Properties of A2B12H12 Compounds via Cation and Anion Modifications J. Alloys Compd. 2015, 645, S200– S204 DOI: 10.1016/j.jallcom.2015.01.061
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    17
    Altering the structural properties of A2B12H12 compounds via cation and anion modifications
    Tang, Wan Si; Udovic, Terrence J.; Stavila, Vitalie
    Journal of Alloys and Compounds (2015), 645 (Suppl._1), S200-S204CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
    The recent discovery of unusually high cationic cond. in Na2B12H12 above its entropy-driven, order-disorder phase transition near 529 K and the expected similar cond. behavior in Li2B12H12 above its transition near 615 K led the authors to study modifications of these two materials in an effort to reduce their transition temps. and thus extend their high conductivities to more technol. favorable values. DSC measurements of perhalogenated Na2B12X12 (X = Cl and I), which are larger anion relatives of Na2B12H12, suggest unfavorably higher transition temps. near 730 K and 816 K, resp. New mixed-cation LiyNa2-yB12H12 phases show intermediate transition temps. between those of Li2B12H12 and Na2B12H12. X-ray diffraction measurements and neutron vibrational spectra corroborate low-temp. ordered structures (for y = 0.67, 1, and 1.33) similar to Li2B12H12, with Li+ and Na+ disordered among the near-trigonal cation sites. Crystallog. data and at. coordinates are given.
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  18. 18
    Verdal, N.; Her, J.-H.; Stavila, V.; Soloninin, A. V.; Babanova, O. A.; Skripov, A. V.; Udovic, T. J.; Rush, J. J. High-Temperature Phase Transitions in Li2B12H12 and Na2B12H12 J. Solid State Chem. 2014, 212, 81– 91 DOI: 10.1016/j.jssc.2014.01.006
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    18
    Complex high-temperature phase transitions in Li2B12H12 and Na2B12H12
    Verdal, Nina; Her, Jae-Hyuk; Stavila, Vitalie; Soloninin, Alexei V.; Babanova, Olga A.; Skripov, Alexander V.; Udovic, Terrence J.; Rush, John J.
    Journal of Solid State Chemistry (2014), 212 (), 81-91CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
    Differential scanning calorimetry measurements of Li2B12H12 and Na2B12H12 indicate hysteretic transformations to high-temp. phases at ≈615 K and 529 K, resp., upon heating (1 K/min) from room temp. X-ray and neutron powder diffraction measurements corroborate the phase-change behavior. For Li2B12H12, the diffraction data are consistent with a previous study suggesting that the overall fcc. arrangement of icosahedral B12H122- anions is maintained upon transformation to the high-temp. polymorph, although the anions are now orientationally disordered and the Li+ cations crystallog. disordered within an enlarged lattice. For Na2B12H12, the diffraction data indicate the existence of three different high-temp. phases in addn. to the known low-temp. monoclinic phase. The highest-temp. structure possesses Im‾3m symmetry and exhibits a bcc. arrangement of orientationally disordered anions. The interstitial, disordered Na+ cations appear to favor off-center positions within the distorted tetrahedral sites formed by the anions in this structure. An intermediate Pm‾3n-sym. phase at lower temp. is the result of a partial ordering of this higher-temp. structure. A third, minor, fcc. phase coexists with these high-temp. polymorphs. 1H NMR measurements of Li2B12H12 and Na2B12H12 reveal an approx. two-orders-of-magnitude increase in the reorientational jump rate of the anions in both cases upon transformation to their high-temp. structures. The enhanced anion mobilities were corroborated by neutron scattering fixed-window scans across the resp. phase boundaries. The inherent cation disorder assocd. with these high-temp. polymorphs suggests their potential use as superionic conductors.
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    Sivaev, I. B.; Bregadze, V. I.; Sjöberg, S. Chemistry of Closo-Dodecaborate Anion [B12H12]2–: A Review Collect. Czech. Chem. Commun. 2002, 67, 679– 727 DOI: 10.1135/cccc20020679
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    19
    Chemistry of closo-dodecaborate anion [B12H12]2-: a review
    Sivaev, Igor B.; Bregadze, Vladimir I.; Sjoberg, Stefan
    Collection of Czechoslovak Chemical Communications (2002), 67 (6), 679-727CODEN: CCCCAK; ISSN:0010-0765. (Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic)
    A review. Synthesis and chem. properties of the closo-dodecaborate anion [B12H12]2- and its derivs. are reviewed. Attention is also paid to potential applications of the closo-dodecaborate derivs. with emphasis on medical applications. A review with 325 refs.
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  20. 20
    He, L.; Li, H.-W.; Hwang, S.-J.; Akiba, E. Facile Solvent-Free Synthesis of Anhydrous Alkali Metal Dodecaborate M2B12H12 (M = Li, Na, K) J. Phys. Chem. C 2014, 118, 6084– 6089 DOI: 10.1021/jp500253k
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    20
    Facile Solvent-Free Synthesis of Anhydrous Alkali Metal Dodecaborate M2B12H12 (M = Li, Na, K)
    He, Liqing; Li, Hai-Wen; Hwang, Son-Jong; Akiba, Etsuo
    Journal of Physical Chemistry C (2014), 118 (12), 6084-6089CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
    Metal dodecaborate, widely regarded as an obstacle of the rehydrogenation of high-d. H storage materials metal borohydrides M(BH4), is generally synthesized using liq.-phase process followed by a careful dehydration process. The authors propose a new and facile solvent-free synthesis process of dodecaborates using B10H14 with a low m.p. of 99.6° as a B source. As a case study, the authors' 1st challenge focused on the syntheses of anhyd. M2B12H12 (M = Li, Na, and K) by heat treatment of starting materials (a) 2MH + 1.2B10H14 or (b) 2MBH4 + B10H14 at 200-450° conditions, which are successful for the 1st time by XRD, Raman, and NMR anal. Starting materials (b) 2MBH4 + B10H14 show better reactivity than that of (a) 2MH + 1.2B10H14, which demonstrates that synthesis of anhyd. M2B12H12 by heat treatment of 2MBH4 + B10H14 is a feasible solvent-free process.
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  21. 21
    Teprovich, J. A., Jr.; Colón-Mercado, H.; Washington, A. L., II; Ward, P. A.; Greenway, S.; Missimer, D. M.; Hartman, H.; Velten, J.; Christian, J. H.; Zidan, R. Bi-functional Li2B12H12 for Energy Storage and Conversion Applications: Solid-State Electrolyte and Luminescent Down-Conversion Dye J. Mater. Chem. A 2015, 3, 22853– 22859 DOI: 10.1039/C5TA06549F
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    21
    Bi-functional Li2B12H12 for energy storage and conversion applications: solid-state electrolyte and luminescent down-conversion dye
    Teprovich, Joseph A.; Colon-Mercado, Hector; Washington, Aaron L., II; Ward, Patrick A.; Greenway, Scott; Missimer, David M.; Hartman, Hope; Velten, Josef; Christian, Jonathan H.; Zidan, Ragaiy
    Journal of Materials Chemistry A: Materials for Energy and Sustainability (2015), 3 (45), 22853-22859CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
    Our investigation of the chem. and phys. properties of the alkali-metal dodecahydro-closo-dodecaborate, Li2B12H12, detd. that it is a bi-functional material that can be used as a solid state electrolyte in lithium ion batteries and as a luminescent down conversion dye in scalable transparent displays. A series of electrochem. measurements of morphol. altered samples, via mech. milling, was conducted. The measurements indicated that mech. alternations of the Li2B12H12 morphol. makes it an excellent lithium ion conductor in the solid state with exceptional ionic cond. at room temp. (0.31 mS cm-1) and is compatible with a metallic lithium electrode up to 6.0 V. In addn., all solid state half and full electrochem. cells were assembled and successfully cycled using Li2B12H12 as a solid state electrolyte at temps. as low as 30 °C with good capacity retention. The photophys. properties of Li2B12H12 were also investigated. Li2B12H12 has an emission max. of ∼460 nm in a variety of solvents with Stokes' shifts up to 175 nm obsd. Li2B12H12 was incorporated in a polyvinyl alc. (PVA) thin film to demonstrate its application as a luminescent down-conversion dye in a transparent head-up display when excited by a UV projection source.
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    He, L.; Li, H.-W.; Nakajima, H.; Tumanov, N.; Filinchuk, Y.; Hwang, S.-J.; Sharma, M.; Hagemann, H.; Akiba, E. Synthesis of a Bimetallic Dodecaborate LiNaB12H12 with Outstanding Superionic Conductivity Chem. Mater. 2015, 27, 5483– 5486 DOI: 10.1021/acs.chemmater.5b01568
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    22
    Synthesis of a Bimetallic Dodecaborate LiNaB12H12 with Outstanding Superionic Conductivity
    He, Liqing; Li, Hai-Wen; Nakajima, Hironori; Tumanov, Nikolay; Filinchuk, Yaroslav; Hwang, Son-Jong; Sharma, Manish; Hagemann, Hans; Akiba, Etsuo
    Chemistry of Materials (2015), 27 (16), 5483-5486CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
    A bimetallic dodecaborate LiNaB12H12 was successfully synthesized for the 1st time, through a sintering process of LiBH4, NaBH4 and B10H14. LiNaB12H12 has a cubic Pa-3 space group symmetry at room temp., and transforms into a high temp. phase with Fm-3m symmetry at 488 K, which is lower than that of Li2B12H12 and Na2B12H12. The ionic cond. at 550 K reaches 0.79 S/cm, which is ∼8 times higher than that of Na2B12H12 and 11 times higher than that of Li2B12H12. The Li/Na compositional and thus an induced positional disorder in LiNaB12H12 probably are responsible for the reduced phase transition temp. and the improved super ionic cond. compared to its monometallic counterparts.
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    Momma, K.; Izumi, F. VESTA 3 for Three-Dimensional Visualization of Crystal, Volumetric and Morphology Data J. Appl. Crystallogr. 2011, 44, 1272– 1276 DOI: 10.1107/S0021889811038970
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    VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
    Momma, Koichi; Izumi, Fujio
    Journal of Applied Crystallography (2011), 44 (6), 1272-1276CODEN: JACGAR; ISSN:0021-8898. (International Union of Crystallography)
    VESTA is a 3D visualization system for crystallog. studies and electronic state calcns. It was upgraded to the latest version, VESTA 3, implementing new features including drawing the external morphpol. of crysals; superimposing multiple structural models, volumetric data and crystal faces; calcn. of electron and nuclear densities from structure parameters; calcn. of Patterson functions from the structure parameters or volumetric data; integration of electron and nuclear densities by Voronoi tessellation; visualization of isosurfaces with multiple levels, detn. of the best plane for selected atoms; an extended bond-search algorithm to enable more sophisticated searches in complex mols. and cage-like structures; undo and redo is graphical user interface operations; and significant performance improvements in rendering isosurfaces and calcg. slices.
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Cite this: ACS Energy Lett. 2016, 1, 4, 659–664
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  • Abstract

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    Figure 1

    Figure 1. Room-temperature XRPD data [experimental (blue circles), fitted (orange line), and difference (black line) patterns] for solution-dried (a) Li2(CB9H10)(CB11H12) and (b) Na2(CB9H10)(CB11H12). Vertical green and red bars indicate the positions of Bragg peaks for the high-T hexagonal and fcc phases, respectively. The refined unit cell parameters for the Li-mixed sample are a = 6.8589(5) Å, c = 11.0116(11) Å, and V = 448.64(6) Å3 for the hexagonal structure; a = 9.7541(7) Å and V = 928.03(11) Å3 for the fcc structure (χ2 = 2.40; Rp = 0.110; Rwp = 0.0965). Refinement indicated an additional disordered phase (purple bars) indexed by profile matching to a probable hexagonal unit cell with parameters a = 6.86 Å and c = 16.85 Å. The refined unit cell parameters for the Na-mixed sample are a = 6.9905(11) Å, c = 11.3390(17) Å, and V = 479.88(13) Å3 for the hexagonal structure; a = 9.855(3) Å and V = 957.1(5) Å3 for the fcc structure (χ2 = 3.19; Rp = 0.156; Rwp = 0.132). (c) The disordered hexagonal structure with orange Li+/Na+ cation positions and large green (B/C atoms) and gray (H atoms) spheres denoting the diffraction-average spherical shells of scattering from the orientationally disordered CB9H10– and CB11H12– anions (superimposed).

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    Figure 2

    Figure 2. Proton spin–lattice relaxation rates measured at 28 MHz versus inverse temperature for Li2(CB9H10)(CB11H12) and Na2(CB9H10)(CB11H12). The black lines show the fits to the proton spin–lattice relaxation rates at the same frequency for LiCB11H12 and NaCB11H12 from ref 14 undergoing their order–disorder phase transitions near 384 and 376 K, respectively.

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    Figure 3

    Figure 3. Neutron elastic-scattering FWSs for Li2(CB9H10)(CB11H12) and Na2(CB9H10)(CB11H12) compared with those for the various single-anion component compounds, summed over detectors covering a Q range of 0.87–1.68 Å–1. Arrows differentiate heating and cooling scans. For a reasonable qualitative comparison, the individual data sets were scaled so as to have similar minimum and maximum intensities.

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    Figure 4

    Figure 4. (a) Temperature dependences of the ionic conductivities (σ) for solution-dried, cold-pressed Li2(CB9H10)(CB11H12) and Na2(CB9H10)(CB11H12) using Li and Au electrodes, respectively, compared with those for the single-anion compounds (3, 4) and the closest-performing competitors, Li10GeP2S12 and Na3PSe4, (5, 6) and (b) ln(σT) vs T–1 and resulting fitted activation energies for the two mixed compounds. Closed and open symbols denote heating and cooling cycles, respectively.

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  • References

    This article references 23 other publications.

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      Impedance measurements indicate that Na2B12H12 exhibits dramatic Na+ cond. (∼0.1 S cm-1) above its order-disorder phase-transition at ≈529 K, rivaling that of current, solid-state, ceramic-based, Na-battery electrolytes. Superionicity may be aided by the large size, quasispherical shape, and high rotational mobility of the B12H122- anions.
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      Sodium decahydro-closo-decaborate forms a disordered, fcc. phase above about 360 K, possessing a vacancy-rich Na+ cation sublattice. This cation sublattice is highly mobile within the spacious corridors formed by the large B10H102- anions and exhibits remarkable superionic cond. (e.g., σ = 0.01 Scm-1 at 383 K) to substantially lower temps. than for Na2B12H12. This cond. is more than an order of magnitude higher than that of all other solid-state Na-based complex-hydride materials investigated to date in this temp. region. This discovery represents a major advancement in the field of solid-state Na+ fast-ion conduction at technol. relevant device temps.
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      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXitVCitbzP&md5=7d8a4bfda5f3f3d7266de084306d9b2d
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      Tang, W. S.; Unemoto, A.; Zhou, W.; Stavila, V.; Matsuo, M.; Wu, H.; Orimo, S.; Udovic, T. J. Unparalleled Lithium and Sodium Superionic Conduction in Solid Electrolytes with Large Monovalent Cage-like Anions Energy Environ. Sci. 2015, 8, 3637– 3645 DOI: 10.1039/C5EE02941D
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      Energy & Environmental Science (2015), 8 (12), 3637-3645CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)
      Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of org. liq. 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 cond., albeit only above its 529 K phase transition. Its lithium congener, Li2B12H12, possesses an even more technol. prohibitive transition temp. above 600 K. Here we show that the chem. related LiCB11H12 and NaCB11H12 salts, which contain icosahedral, monovalent CB11H12- anions, both exhibit much lower transition temps. near 400 K and 380 K, resp., and truly stellar ionic conductivities (>0.1 S cm-1) unmatched by any other known polycryst. materials at these temps. With proper modifications, we are confident that room-temp.-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.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhs1amsr%252FL&md5=6ce33938ab3579da7ee531eb41f73964
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      Tang, W. S.; Matsuo, M.; Wu, H.; Stavila, V.; Zhou, W.; Talin, A. A.; Soloninin, A. V.; Skoryunov, R. V.; Babanova, O. A.; Skripov, A. V. Liquid-like Ionic Conduction in Solid Lithium and Sodium Monocarba-Closo-Decaborates near or at Room Temperature Adv. Energy Mater. 2016, 6, 1502237 DOI: 10.1002/aenm.201502237
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      Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, Akio
      Nature Materials (2011), 10 (9), 682-686CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      Batteries are a key technol. in modern society. They are used to power elec. and hybrid elec. vehicles and to store wind and solar energy in smart grids. Electrochem. devices with high energy and power densities can currently be powered only by batteries with org. liq. electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10-2 S/cm) only at 50-80°, which is one order of magnitude lower than those of org. liq. electrolytes. Here, the authors report a Li superionic conductor, Li10GeP2S12 that has a new 3-dimensional framework structure. It exhibits an extremely high Li ionic cond. of 12 mS/cm at room temp. This represents the highest cond. achieved in a solid electrolyte, exceeding even those of liq. org. electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochem. properties (high cond. and wide potential window).
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXpsFaisLc%253D&md5=30637e2968f742a3e1da5f7fa4250644
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      Sadikin, Y.; Brighi, M.; Schouwink, P.; Černý, R. Superionic Conduction of Sodium and Lithium in Anion-Mixed Hydroborates Na3BH4B12H12 and (Li0.7Na0.3)3BH4B12H12 Adv. Energy Mater. 2015, 5, 1501016 DOI: 10.1002/aenm.201501016
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      Zhang, L.; Yang, K.; Mi, J.; Lu, L.; Zhao, L.; Wang, L.; Li, Y.; Zeng, H. Na3PSe4: A Novel Chalcogenide Solid Electrolyte with High Ionic Conductivity Adv. Energy Mater. 2015, 5, 1501294 DOI: 10.1002/aenm.201501294
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      Monti, D.; Jónsson, E.; Palacín, M. R.; Johansson, P. Ionic Liquid Based Electrolytes for Sodium-Ion Batteries: Na+ Solvation and Ionic Conductivity J. Power Sources 2014, 245, 630– 636 DOI: 10.1016/j.jpowsour.2013.06.153
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      Monti, Damien; Jonsson, Erlendur; Palacin, M. Rosa; Johansson, Patrik
      Journal of Power Sources (2014), 245 (), 630-636CODEN: JPSODZ; ISSN:0378-7753. (Elsevier B.V.)
      Ionic liq. (IL) based sodium-ion (Na+) battery electrolytes obtained by mixing imidazolium-TFSI ILs (EMIm-TFSI and BMIm-TFSI) with the corresponding sodium salt (NaTFSI) were studied using a wide range of characterization techniques: dielec. spectroscopy, DSC, densitometry, viscometry, and Raman spectroscopy. The sodium ion conducting electrolytes exhibit excellent ionic conductivities, up to 5.5 mS cm-1 at room temp., and a useful thermal window of -86° to 150°. In more detail, Raman data anal. supported by DFT calcns. on Na+-TFSI complexes, allow one to det. the sodium ion solvation and charge carrier nature as a function of salt concn. The results are compared to data for the corresponding Li systems and while such electrolytes essentially form [Li(TFSI)2]- as the main Li+ carrier, the sodium systems seem to dominantly form [Na(TFSI)3]2- complexes. The effects on cond. and viscosity and the consequences for sodium-ion battery implementation are discussed.
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      Ding, M. S.; Xu, K.; Zhang, S. S.; Amine, K.; Henriksen, G. L.; Jow, T. R. Change of Conductivity with Salt Content, Solvent Composition, and Temperature for Electrolytes of LiPF6 in Ethylene Carbonate-Ethyl Methyl Carbonate J. Electrochem. Soc. 2001, 148, A1196– A1204 DOI: 10.1149/1.1403730
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      Change of conductivity with salt content, solvent composition, and temperature for electrolytes of LiPF6 in ethylene carbonate-ethyl methyl carbonate
      Ding, M. S.; Xu, K.; Zhang, S. S.; Amine, K.; Henriksen, G. L.; Jow, T. R.
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      We measured the electrolytic conductivities of the electrolytes of LiPF6 in ethylene carbonate-Et Me carbonate at different salt contents, solvent compns., and temps. in the ranges of their practical values. To these data, we fitted a fourth degree trivariate polynomial and obtained a close fit. We then plotted this function as surface and contour plots in the coordinates of salt content and solvent compn. for a series of temps. These plots showed the change of cond. with the simultaneous changes of salt content and solvent compn. and the influence of temp. on this change, thus mapping the locations for the optimal combinations of salt content and solvent compn. for max. cond. of the electrolytes at desired temps. Here we also discuss and interpret qual. the trends found in the change of cond. with salt content, solvent compn., and temp., based on the dependency on the same variables of these three factors: the no. of dissocd. ions in the electrolyte, the dielec. const. of the solvent, and the viscosity of the electrolyte.
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      10
      Safer Electrolytes for Lithium-Ion Batteries: State of the Art and Perspectives
      Kalhoff, Julian; Eshetu, Gebrekidan Gebresilassie; Bresser, Dominic; Passerini, Stefano
      ChemSusChem (2015), 8 (13), 2154-2175CODEN: CHEMIZ; ISSN:1864-5631. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Li-ion batteries are becoming increasingly important for electrifying the modern transportation system and, thus, hold the promise to enable sustainable mobility in the future. However, their large-scale application is hindered by severe safety concerns when the cells are exposed to mech., thermal, or elec. abuse conditions. These safety issues are intrinsically related to their superior energy d., combined with the (present) use of highly volatile and flammable org.-solvent-based electrolytes. Herein, state-of-the-art electrolyte systems and potential alternatives are briefly surveyed, with a particular focus on their (inherent) safety characteristics. The challenges, which so far prevent the widespread replacement of org. carbonate-based electrolytes with LiPF6 as the conducting salt, are also reviewed herein. Starting from rather facile electrolyte modifications by (partially) replacing the org. solvent or Li salt and/or the addn. of functional electrolyte additives, conceptually new electrolyte systems, including ionic liqs., solvent-free, and/or gelled polymer-based electrolytes, as well as solid-state electrolytes, are also considered. Indeed, the opportunities for designing new electrolytes appear to be almost infinite, which certainly complicates strict classification of such systems and a fundamental understanding of their properties. Nevertheless, these innumerable opportunities also provide a great chance of developing highly functionalized, new electrolyte systems, which may overcome the afore-mentioned safety concerns, while also offering enhanced mech., thermal, physicochem., and electrochem. performance.
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    11. 11
      Lipscomb, W. H. Boron Hydrides; W. A. Benjamin, Inc.: New York, 1963.
      There is no corresponding record for this reference.
    12. 12
      Wang, Y.; Richards, W. D.; Ong, S. P.; Miara, L. J.; Kim, J. C.; Mo, Y.; Ceder, G. Design Principles for Solid-State Lithium Superionic Conductors Nat. Mater. 2015, 14, 1026– 1031 DOI: 10.1038/nmat4369
      12
      Design principles for solid-state lithium superionic conductors
      Wang, Yan; Richards, William Davidson; Ong, Shyue Ping; Miara, Lincoln J.; Kim, Jae Chul; Mo, Yifei; Ceder, Gerbrand
      Nature Materials (2015), 14 (10), 1026-1031CODEN: NMAACR; ISSN:1476-1122. (Nature Publishing Group)
      Lithium solid electrolytes can potentially address two key limitations of the org. electrolytes used in today's lithium-ion batteries, namely, their flammability and limited electrochem. stability. However, achieving a Li+ cond. in the solid state comparable to existing liq. electrolytes (>1 mS cm-1) is particularly challenging. In this work, we reveal a fundamental relationship between anion packing and ionic transport in fast Li-conducting materials and expose the desirable structural attributes of good Li-ion conductors. We find that an underlying body-centered cubic-like anion framework, which allows direct Li hops between adjacent tetrahedral sites, is most desirable for achieving high ionic cond., and that indeed this anion arrangement is present in several known fast Li-conducting materials and other fast ion conductors. These findings provide important insight towards the understanding of ionic transport in Li-ion conductors and serve as design principles for future discovery and design of improved electrolytes for Li-ion batteries.
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    13. 13
      Tang, W. S.; Matsuo, M.; Wu, H.; Stavila, V.; Unemoto, A.; Orimo, S.; Udovic, T. J. Stabilizing Lithium and Sodium Fast-Ion Conduction in Solid Polyhedral-Borate Salts at Device-Relevant Temperatures Energy Storage Mater. 2016, 4, 79– 83 DOI: 10.1016/j.ensm.2016.03.004
      There is no corresponding record for this reference.
    14. 14
      Skripov, A. V.; Skoryunov, R. V.; Soloninin, A. V.; Babanova, O. A.; Tang, W. S.; Stavila, V.; Udovic, T. J. Anion Reorientations and Cation Diffusion in LiCB11H12 and NaCB11H12: 1H, 7Li, and 23Na NMR Studies J. Phys. Chem. C 2015, 119, 26912– 26918 DOI: 10.1021/acs.jpcc.5b10055
      14
      Anion Reorientations and Cation Diffusion in LiCB11H12 and NaCB11H12: 1H, 7Li, and 23Na NMR Studies
      Skripov, Alexander V.; Skoryunov, Roman V.; Soloninin, Alexei V.; Babanova, Olga A.; Tang, Wan Si; Stavila, Vitalie; Udovic, Terrence J.
      Journal of Physical Chemistry C (2015), 119 (48), 26912-26918CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      To study the dynamical properties of the monocarba-closo-dodecaborates LiCB11H12 and NaCB11H12 showing the exceptionally high ionic conductivities in the high-temp. disordered phases, the authors have measured the temp. dependences of the 1H, 7Li, and 23Na NMR spectra and spin-lattice relaxation rates in these compds. below and above the phase transition points. For both compds. the transition from the low-T ordered to the high-T disordered phase (near 384 and 376 K for LiCB11H12 and NaCB11H12, resp.) is accompanied by a nearly 3 orders of magnitude increase in the reorientational jump rate of [CB11H12]- anions. The results of the authors' 7Li and 23Na NMR measurements indicate that the phase transitions from the low-T to the high-T phases of both LiCB11H12 and NaCB11H12 are also accompanied by a strong acceleration of translational diffusion of (Li+ or Na+). In the high-T phases of LiCB11H12 and NaCB11H12, the cation diffusion was characterized by low activation energies: 92(7) and 152(8) meV, resp. These results are consistent with the high superionic cond. in the disordered phases of LiCB11H12 and NaCB11H12; also, probably the enhanced reorientational mobility of large nearly spherical anions may facilitate the translational mobility of the cations.
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    15. 15
      Markert, J. T.; Cotts, E. J.; Cotts, R. M. Hydrogen Diffusion in the Metallic Glass a-Zr3RhH3.5 Phys. Rev. B: Condens. Matter Mater. Phys. 1988, 37, 6446– 6452 DOI: 10.1103/PhysRevB.37.6446
      There is no corresponding record for this reference.
    16. 16
      Wu, H.; Tang, W. S.; Zhou, W.; Tarver, J. D.; Stavila, V.; Brown, C. M.; Udovic, T. J. The Low-Temperature Structural Behavior of Sodium 1-Carba-Closo-Decaborate: NaCB9H10 J. Solid State Chem. 2016, 243, 162– 167 DOI: 10.1016/j.jssc.2016.08.024
      16
      The low-temperature structural behavior of sodium 1-carba-closo-decaborate: NaCB9H10
      Wu, Hui; Tang, Wan Si; Zhou, Wei; Tarver, Jacob D.; Stavila, Vitalie; Brown, Craig M.; Udovic, Terrence J.
      Journal of Solid State Chemistry (2016), 243 (), 162-167CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
      Two ordered phases of the novel solid superionic conductor Na 1-carba-closo-decaborate (NaCB9H10) were identified via synchrotron x-ray powder diffraction in combination with 1st-principles calcns. and neutron vibrational spectroscopy. A monoclinic packing of the large ellipsoidal CB9H-10 anions prevails at the lowest temps., but a 1st-order transformation to a slightly modified orthorhombic packing is largely complete by 240 K. The CB9H-10 anion orientational alignments and Na+ cation interstitial sitings in both phases are arranged so as to minimize the cation proximities to the uniquely more pos. C-bonded H atoms of the anions. These results provide valuable structural information pertinent to understanding the relatively low-temp., entropy-driven, order-disorder phase transition for this compd.
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    17. 17
      Tang, W. S.; Udovic, T. J.; Stavila, V. Altering the Structural Properties of A2B12H12 Compounds via Cation and Anion Modifications J. Alloys Compd. 2015, 645, S200– S204 DOI: 10.1016/j.jallcom.2015.01.061
      17
      Altering the structural properties of A2B12H12 compounds via cation and anion modifications
      Tang, Wan Si; Udovic, Terrence J.; Stavila, Vitalie
      Journal of Alloys and Compounds (2015), 645 (Suppl._1), S200-S204CODEN: JALCEU; ISSN:0925-8388. (Elsevier B.V.)
      The recent discovery of unusually high cationic cond. in Na2B12H12 above its entropy-driven, order-disorder phase transition near 529 K and the expected similar cond. behavior in Li2B12H12 above its transition near 615 K led the authors to study modifications of these two materials in an effort to reduce their transition temps. and thus extend their high conductivities to more technol. favorable values. DSC measurements of perhalogenated Na2B12X12 (X = Cl and I), which are larger anion relatives of Na2B12H12, suggest unfavorably higher transition temps. near 730 K and 816 K, resp. New mixed-cation LiyNa2-yB12H12 phases show intermediate transition temps. between those of Li2B12H12 and Na2B12H12. X-ray diffraction measurements and neutron vibrational spectra corroborate low-temp. ordered structures (for y = 0.67, 1, and 1.33) similar to Li2B12H12, with Li+ and Na+ disordered among the near-trigonal cation sites. Crystallog. data and at. coordinates are given.
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    18. 18
      Verdal, N.; Her, J.-H.; Stavila, V.; Soloninin, A. V.; Babanova, O. A.; Skripov, A. V.; Udovic, T. J.; Rush, J. J. High-Temperature Phase Transitions in Li2B12H12 and Na2B12H12 J. Solid State Chem. 2014, 212, 81– 91 DOI: 10.1016/j.jssc.2014.01.006
      18
      Complex high-temperature phase transitions in Li2B12H12 and Na2B12H12
      Verdal, Nina; Her, Jae-Hyuk; Stavila, Vitalie; Soloninin, Alexei V.; Babanova, Olga A.; Skripov, Alexander V.; Udovic, Terrence J.; Rush, John J.
      Journal of Solid State Chemistry (2014), 212 (), 81-91CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
      Differential scanning calorimetry measurements of Li2B12H12 and Na2B12H12 indicate hysteretic transformations to high-temp. phases at ≈615 K and 529 K, resp., upon heating (1 K/min) from room temp. X-ray and neutron powder diffraction measurements corroborate the phase-change behavior. For Li2B12H12, the diffraction data are consistent with a previous study suggesting that the overall fcc. arrangement of icosahedral B12H122- anions is maintained upon transformation to the high-temp. polymorph, although the anions are now orientationally disordered and the Li+ cations crystallog. disordered within an enlarged lattice. For Na2B12H12, the diffraction data indicate the existence of three different high-temp. phases in addn. to the known low-temp. monoclinic phase. The highest-temp. structure possesses Im‾3m symmetry and exhibits a bcc. arrangement of orientationally disordered anions. The interstitial, disordered Na+ cations appear to favor off-center positions within the distorted tetrahedral sites formed by the anions in this structure. An intermediate Pm‾3n-sym. phase at lower temp. is the result of a partial ordering of this higher-temp. structure. A third, minor, fcc. phase coexists with these high-temp. polymorphs. 1H NMR measurements of Li2B12H12 and Na2B12H12 reveal an approx. two-orders-of-magnitude increase in the reorientational jump rate of the anions in both cases upon transformation to their high-temp. structures. The enhanced anion mobilities were corroborated by neutron scattering fixed-window scans across the resp. phase boundaries. The inherent cation disorder assocd. with these high-temp. polymorphs suggests their potential use as superionic conductors.
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    19. 19
      Sivaev, I. B.; Bregadze, V. I.; Sjöberg, S. Chemistry of Closo-Dodecaborate Anion [B12H12]2–: A Review Collect. Czech. Chem. Commun. 2002, 67, 679– 727 DOI: 10.1135/cccc20020679
      19
      Chemistry of closo-dodecaborate anion [B12H12]2-: a review
      Sivaev, Igor B.; Bregadze, Vladimir I.; Sjoberg, Stefan
      Collection of Czechoslovak Chemical Communications (2002), 67 (6), 679-727CODEN: CCCCAK; ISSN:0010-0765. (Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic)
      A review. Synthesis and chem. properties of the closo-dodecaborate anion [B12H12]2- and its derivs. are reviewed. Attention is also paid to potential applications of the closo-dodecaborate derivs. with emphasis on medical applications. A review with 325 refs.
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    20. 20
      He, L.; Li, H.-W.; Hwang, S.-J.; Akiba, E. Facile Solvent-Free Synthesis of Anhydrous Alkali Metal Dodecaborate M2B12H12 (M = Li, Na, K) J. Phys. Chem. C 2014, 118, 6084– 6089 DOI: 10.1021/jp500253k
      20
      Facile Solvent-Free Synthesis of Anhydrous Alkali Metal Dodecaborate M2B12H12 (M = Li, Na, K)
      He, Liqing; Li, Hai-Wen; Hwang, Son-Jong; Akiba, Etsuo
      Journal of Physical Chemistry C (2014), 118 (12), 6084-6089CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)
      Metal dodecaborate, widely regarded as an obstacle of the rehydrogenation of high-d. H storage materials metal borohydrides M(BH4), is generally synthesized using liq.-phase process followed by a careful dehydration process. The authors propose a new and facile solvent-free synthesis process of dodecaborates using B10H14 with a low m.p. of 99.6° as a B source. As a case study, the authors' 1st challenge focused on the syntheses of anhyd. M2B12H12 (M = Li, Na, and K) by heat treatment of starting materials (a) 2MH + 1.2B10H14 or (b) 2MBH4 + B10H14 at 200-450° conditions, which are successful for the 1st time by XRD, Raman, and NMR anal. Starting materials (b) 2MBH4 + B10H14 show better reactivity than that of (a) 2MH + 1.2B10H14, which demonstrates that synthesis of anhyd. M2B12H12 by heat treatment of 2MBH4 + B10H14 is a feasible solvent-free process.
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    21. 21
      Teprovich, J. A., Jr.; Colón-Mercado, H.; Washington, A. L., II; Ward, P. A.; Greenway, S.; Missimer, D. M.; Hartman, H.; Velten, J.; Christian, J. H.; Zidan, R. Bi-functional Li2B12H12 for Energy Storage and Conversion Applications: Solid-State Electrolyte and Luminescent Down-Conversion Dye J. Mater. Chem. A 2015, 3, 22853– 22859 DOI: 10.1039/C5TA06549F
      21
      Bi-functional Li2B12H12 for energy storage and conversion applications: solid-state electrolyte and luminescent down-conversion dye
      Teprovich, Joseph A.; Colon-Mercado, Hector; Washington, Aaron L., II; Ward, Patrick A.; Greenway, Scott; Missimer, David M.; Hartman, Hope; Velten, Josef; Christian, Jonathan H.; Zidan, Ragaiy
      Journal of Materials Chemistry A: Materials for Energy and Sustainability (2015), 3 (45), 22853-22859CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)
      Our investigation of the chem. and phys. properties of the alkali-metal dodecahydro-closo-dodecaborate, Li2B12H12, detd. that it is a bi-functional material that can be used as a solid state electrolyte in lithium ion batteries and as a luminescent down conversion dye in scalable transparent displays. A series of electrochem. measurements of morphol. altered samples, via mech. milling, was conducted. The measurements indicated that mech. alternations of the Li2B12H12 morphol. makes it an excellent lithium ion conductor in the solid state with exceptional ionic cond. at room temp. (0.31 mS cm-1) and is compatible with a metallic lithium electrode up to 6.0 V. In addn., all solid state half and full electrochem. cells were assembled and successfully cycled using Li2B12H12 as a solid state electrolyte at temps. as low as 30 °C with good capacity retention. The photophys. properties of Li2B12H12 were also investigated. Li2B12H12 has an emission max. of ∼460 nm in a variety of solvents with Stokes' shifts up to 175 nm obsd. Li2B12H12 was incorporated in a polyvinyl alc. (PVA) thin film to demonstrate its application as a luminescent down-conversion dye in a transparent head-up display when excited by a UV projection source.
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    22. 22
      He, L.; Li, H.-W.; Nakajima, H.; Tumanov, N.; Filinchuk, Y.; Hwang, S.-J.; Sharma, M.; Hagemann, H.; Akiba, E. Synthesis of a Bimetallic Dodecaborate LiNaB12H12 with Outstanding Superionic Conductivity Chem. Mater. 2015, 27, 5483– 5486 DOI: 10.1021/acs.chemmater.5b01568
      22
      Synthesis of a Bimetallic Dodecaborate LiNaB12H12 with Outstanding Superionic Conductivity
      He, Liqing; Li, Hai-Wen; Nakajima, Hironori; Tumanov, Nikolay; Filinchuk, Yaroslav; Hwang, Son-Jong; Sharma, Manish; Hagemann, Hans; Akiba, Etsuo
      Chemistry of Materials (2015), 27 (16), 5483-5486CODEN: CMATEX; ISSN:0897-4756. (American Chemical Society)
      A bimetallic dodecaborate LiNaB12H12 was successfully synthesized for the 1st time, through a sintering process of LiBH4, NaBH4 and B10H14. LiNaB12H12 has a cubic Pa-3 space group symmetry at room temp., and transforms into a high temp. phase with Fm-3m symmetry at 488 K, which is lower than that of Li2B12H12 and Na2B12H12. The ionic cond. at 550 K reaches 0.79 S/cm, which is ∼8 times higher than that of Na2B12H12 and 11 times higher than that of Li2B12H12. The Li/Na compositional and thus an induced positional disorder in LiNaB12H12 probably are responsible for the reduced phase transition temp. and the improved super ionic cond. compared to its monometallic counterparts.
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    23. 23
      Momma, K.; Izumi, F. VESTA 3 for Three-Dimensional Visualization of Crystal, Volumetric and Morphology Data J. Appl. Crystallogr. 2011, 44, 1272– 1276 DOI: 10.1107/S0021889811038970
      23
      VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
      Momma, Koichi; Izumi, Fujio
      Journal of Applied Crystallography (2011), 44 (6), 1272-1276CODEN: JACGAR; ISSN:0021-8898. (International Union of Crystallography)
      VESTA is a 3D visualization system for crystallog. studies and electronic state calcns. It was upgraded to the latest version, VESTA 3, implementing new features including drawing the external morphpol. of crysals; superimposing multiple structural models, volumetric data and crystal faces; calcn. of electron and nuclear densities from structure parameters; calcn. of Patterson functions from the structure parameters or volumetric data; integration of electron and nuclear densities by Voronoi tessellation; visualization of isosurfaces with multiple levels, detn. of the best plane for selected atoms; an extended bond-search algorithm to enable more sophisticated searches in complex mols. and cage-like structures; undo and redo is graphical user interface operations; and significant performance improvements in rendering isosurfaces and calcg. slices.
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  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsenergylett.6b00310.

    • Experimental details; DSC scans; complex impedance plots for solution-dried sample mixtures; and XRPD, FWS, and ionic conductivity data for analogous ball-milled sample mixtures (PDF)


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