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Fast sodium ionic conduction in Na2B10H10-Na2B12H12 pseudo-binary complex hydride and application to a bulk-type all-solid-state battery
被引:86
作者:
Yoshida, Koji
[1
]
Sato, Toyoto
[1
]
Unemoto, Atsushi
[2
]
Matsuo, Motoaki
[3
]
Ikeshoji, Tamio
[1
]
Udovic, Terrence J.
[4
]
Orimo, Shin-ichi
[1
,5
]
机构:
[1] Tohoku Univ, Inst Mat Res, Aoba Ku, Katahira 2-1-1, Sendai, Miyagi 9808577, Japan
[2] Hitachi Ltd, Ctr Technol Innovat, Res & Dev Grp, 7-1-1 Omika, Hitachi, Ibaraki 3191292, Japan
[3] Kwansei Gakuin Univ, Sch Sci & Technol, 2-1 Gakuen, Sanda, Hyogo 6691337, Japan
[4] NIST, Ctr Neutron Res, Gaithersburg, MD 20899 USA
[5] Tohoku Univ, WPI AIMR, Aoba Ku, Katahira 2-1-1, Sendai, Miyagi 9808577, Japan
关键词:
SUPERIONIC CONDUCTION;
LITHIUM;
ELECTROLYTES;
DESIGN;
D O I:
10.1063/1.4977885
中图分类号:
O59 [应用物理学];
学科分类号:
摘要:
In the present work, we developed highly sodium-ion conductive Na2B10H10-Na2B12H12 pseudobinary complex hydride via mechanically ball-milling admixtures of the pure Na2B10H10 and Na2B12H12 components. Both of these components show a monoclinic phase at room temperature, but ball-milled mixtures partially stabilized highly ion-conductive, disordered cubic phases, whose fraction and favored structural symmetry (body-centered cubic or face-centered cubic) depended on the conditions of mechanical ball-milling and molar ratio of the component compounds. First-principles molecular-dynamics simulations demonstrated that the total energy of the closo-borane mixtures and pure materials is quite close, helping to explain the observed stabilization of the mixed compounds. The ionic conductivity of the closo-borane mixtures appeared to be correlated with the fraction of the body-centered-cubic phase, exhibiting a maximum at a molar ratio of Na2B10H10:Na2B12H12 = 1:3. A conductivity as high as log(sigma/S cm(-1)) = -3.5 was observed for the above ratio at 303 K, being approximately 2-3 orders of magnitude higher than that of either pure material. A bulk-type all-solid-state sodium-ion battery with a closo-borane-mixture electrolyte, sodium-metal negative-electrode, and TiS2 positive-electrode demonstrated a high specific capacity, close to the theoretical value of NaTiS2 formation and a stable discharge/charge cycling for at least eleven cycles, with a high discharge capacity retention ratio above 91% from the second cycle.
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页数:5
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