Liquid‐Like Ionic Conduction in Solid Lithium and Sodium Monocarba‐<i>closo</i>‐Decaborates Near or at Room Temperature

Tang, Wan Si; Matsuo, Motoaki; Wu, Hui; Stavila, Vitalie; Zhou, Wei; Talin, A. Alec; Soloninin, Alexei V.; Skoryunov, Roman V.; Babanova, Olga A.; Skripov, A. V.; Unemoto, Atsushi; Orimo, Shin Ichi; Udovic, Terrence J.

doi:10.1002/aenm.201502237

Cited by 202 publications

(310 citation statements)

References 22 publications

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“…[1] Thiophosphates, such as Li 10 GeP 2 S 12 with 12 × 10 −3 S cm −1 and Li 2 S-P 2 S 5 with 17 × 10 −3 S cm −1 , have recently emerged as a promising alternative with conductivities at room temperature comparable to organic liquid electrolytes. [6,9] For the reference sample x = 3/4, our measurements reproduce a conductivity of 2 × 10 −4 S cm −1 at 40 °C with an activation energy of 0.34 eV in agreement with previous reports. [3] Li + conduction was also discovered in complex hydrides, which have been studied extensively as potential hydrogen function of temperature extracted from the intercept of impedance with the horizontal axis of the Nyquist plots are shown in Figure 1a for both heating and cooling cycles.…”

Section: Introductionsupporting

confidence: 91%

A Lithium Amide‐Borohydride Solid‐State Electrolyte with Lithium‐Ion Conductivities Comparable to Liquid Electrolytes

Yan

Kühnel

Remhof

et al. 2017

Advanced Energy Materials

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storage materials. [4] As SSEs for lithiumion batteries, they offer multiple advantages including the natural abundance of their constituent elements, their light weight, negligible electronic conduction, and low grain boundary resistance. [5] The prototypical example is LiBH 4 , whose Li + conductivity increases abruptly to >1 × 10 −3 S cm −1 above 100 °C due to a structural phase transition. [6] This superionic high-temperature phase can be stabilized at room temperature by incorporation of lithium halides (LiBH 4 -LiX, X = Cl, Br, I). Among these materials, the solid solution with lithium iodide displays the highest conductivity at room temperature of >10 −5 S cm −1 . [7] Conductivities reaching 10 −4 S cm −1 near room temperature have also been reported for two compounds of the lithium amide-borohydride Li(BH 4 ) 1−x (NH 2 ) x system, namely, for the cubic α phase (x = 3/4) and for the trigonal β phase (x = 1/2). [4,8] Here, we report the discovery of a transition to even higher Li + conductivities of up to 6.4 × 10 −3 S cm −1 near room temperature (40 °C) in BH 4 -rich lithium amide-borohydride (x = 2/3). We discuss the conduction mechanism in light of latent heat absorbed/released during the transition upon heating/cooling, respectively. We further demonstrate an allsolid-state Li 4 Ti 5 O 12 -based half-cell (employing the BH 4 -rich electrolyte) with excellent rate capability and cycling stability, comparable to a reference cell with standard liquid electrolyte representing an important step toward an all-solid-state amideborohydride-based battery. Results and DiscussionLi(BH 4 ) 1−x (NH 2 ) x powders, employing LiBH 4 and LiNH 2 precursors in amounts equivalent to x = 2/3, were prepared via reactive ball milling for 45 min and subsequent heat treatment at 120 °C for 12 h (see the Experimental Section for details). A reference sample with x = 3/4 (cubic α phase) and intermediate compositions were also synthesized.Ionic conductivities were determined for pellets pressed from the powders via temperature-dependent impedance spectroscopy. For low to intermediate conductivities, Nyquist plots take the typical form composed of a single semicircle and the electrode polarization tail (see Figure S1 in the Supporting Information for exemplary Nyquist plots). Conductivities as a High ionic conductivity of up to 6.4 × 10 −3 S cm −1 near room temperature (40 °C) in lithium amide-borohydrides is reported, comparable to values of liquid organic electrolytes commonly employed in lithium-ion batteries. Density functional theory is applied coupled with X-ray diffraction, calorimetry, and nuclear magnetic resonance experiments to shed light on the conduction mechanism. A Li 4 Ti 5 O 12 half-cell battery incorporating the lithium amide-borohydride electrolyte exhibits good rate performance up to 3.5 mA cm −2 (5 C) and stable cycling over 400 cycles at 1 C at 40 °C, indicating high bulk and interfacial stability. The results demonstrate the potential of lithium amide-borohydrides as solid-state electrolytes for high-power...

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Section: Introductionsupporting

confidence: 91%

A Lithium Amide‐Borohydride Solid‐State Electrolyte with Lithium‐Ion Conductivities Comparable to Liquid Electrolytes

Yan

Kühnel

Remhof

et al. 2017

Advanced Energy Materials

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“…In other reports, high lithium [30][31][32][33] and sodium 30,[32][33][34][35] , have been discovered. Repeated battery operation of all-solid-state batteries by using some of the above materials has been successfully demonstrated.…”

Section: Resultsmentioning

confidence: 89%

Development of 4V-Class Bulk-Type All-Solid-State Lithium Rechargeable Batteries by a Combined Use of Complex Hydride and Sulfide Electrolytes for Room Temperature Operation

et al. 2017

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We have operated a 4V-class bulk-type, all-solid-state LiCoO 2 /Li battery at room temperature. The battery consisted of a Li 4 (BH 4 ) 3 I complex hydride electrolyte as the electrolyte layer, and a 80Li 2 S 20P 2 S 5 sul de glass as an electrolyte in the positive electrode layer. The assembled battery exhibited a 92 mAh g −1 initial discharge capacity at 298 K and 0.1 C. The discharge capacity for the 20 th cycle remained as high as 83 mAh g −1 , corresponding to a capacity retention ratio of nearly 90%.

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“…[8][9][10][11] LiBH 4 shows fast Li-ion conductivity above a polymorphic phase transition, which can be stabilized to room temperature by anion substitution of BH4 -by I -12,13 or by nanoconfinement. 14 [15][16][17][18][19] The high conductivity in these compounds is linked to the highly disordered high temperature polymorphs, where partially occupied cation sites and fast reorientational dynamics of the anion promote excellent cation mobility. Perchlorinated lithium-closo-boranes, Li 2 B 12 Cl 12 and Li 2 B 10 Cl 10 , were proposed as liquid electrolytes in Li/SOCl 2 battery cells in the early 1980s, where the extraordinary stability of [B n Cl n ] 2--anions (n = 10, 12) towards temperature and the Li anode were a significant advantage.…”

Section: Introductionmentioning

confidence: 99%

Halogenated Sodium-closo-Dodecaboranes as Solid-State Ion Conductors

et al. 2017

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Sodium compounds containing large weakly coordinating anions are explored as ion conductors. The halogenated sodium-closo-dodecaboranes (Na 2 B 12 Cl 12 , Na 2 B 12 Br 12 , and Na 2 B 12 I 12 ) are all isostructural (Pa-3) at room temperature. These compounds undergo an order-disorder polymorphic transition to Fm-3m where Na + partially occupies two crystallographic sites and [B 12 X 12 ] 2-anions undergo reorientational motion. These dynamic structural properties promote extreme Na + ion conductivity up to 0.162 S/cm at elevated temperature (500 °C). The polymorphic transition temperatures increase down the halogen group (Cl < Br < I). These temperatures are much higher (475, 525 and 570 °C) than for Na 2 B 12 H 12 (266 °C), which could be related to increasing anion size, mass and the anisotropic electron density in the covalently bound halogens (B-X). The halogens may form Na−X interactions with increasing strength and directionality, which restrict dynamic motion until high temperature. The halogenated sodium-closo-dodecaboranes demonstrate excellent thermal stabilities (up to 500 °C) and may facilitate the development of new high temperature ion conductors.

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Liquid‐Like Ionic Conduction in Solid Lithium and Sodium Monocarba‐closo‐Decaborates Near or at Room Temperature

Cited by 202 publications

References 22 publications

A Lithium Amide‐Borohydride Solid‐State Electrolyte with Lithium‐Ion Conductivities Comparable to Liquid Electrolytes

A Lithium Amide‐Borohydride Solid‐State Electrolyte with Lithium‐Ion Conductivities Comparable to Liquid Electrolytes

Development of 4V-Class Bulk-Type All-Solid-State Lithium Rechargeable Batteries by a Combined Use of Complex Hydride and Sulfide Electrolytes for Room Temperature Operation

Halogenated Sodium-closo-Dodecaboranes as Solid-State Ion Conductors

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