Enhanced lithium ionic conductivity of lithium perchlorate in the metal-organic framework matrix
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ORIGINAL PAPER
Enhanced lithium ionic conductivity of lithium perchlorate in the metal-organic framework matrix Artem Ulihin 1 & Valentina Ponomareva 1,2 & Nikolai Uvarov 1,2,3 & Konstantin Kovalenko 4 & Vladimir Fedin 4 Received: 10 April 2020 / Revised: 11 August 2020 / Accepted: 6 September 2020 # Springer-Verlag GmbH Germany, part of Springer Nature 2020
Abstract Nanocomposite solid electrolytes were prepared by impregnation of LiClO4 into pores of the metal-organic framework Cr3[C6H4(COO)2]3F (MIL-101(Cr)), and their conductivity was investigated. At temperatures 25–150 °C and relative humidity of 50%, the composites easily absorb water with formation liquid phase in the pores and have conductivity values typical for water solutions. Conductivity decreases with diminishing the humidity; however, complete dehydration may be achieved only after prolonged heating in vacuum at 180 °C. The concentration dependence of conductivity of dehydrated samples goes through the maximum at nearly 6 mol% of MIL-101(Cr) and reaches 3 × 10−3 S/cm at 160 °C; the activation energy decreases in the nanocomposites. Using the volt-amperometric technique on the sample with two nickel electrodes, the electrochemical decomposition voltage value was found to be nearly 3.5 V at 160 °C. It suggests that the ionic conductivity is caused by lithium cations rather than protons or electrons. Keywords Nanocomposite solid electrolytes . Metal-organic frameworks . MIL-101(Cr) . Effect of humidity on conductivity . Decomposition voltage . High lithium ion conductivity
Introduction All-solid-state lithium-ion batteries containing solid electrolytes have attracted much attention because of their high energy density, design flexibility, and safety. Wide electrochemical window and excellent thermal and mechanical stability are important merits in terms of energy storage applications. However, relatively low conductivity of solid electrolytes compared with that of liquid electrolytes could not afford widespread applications. To date, many lithium ion– conducting solid electrolytes are known [1–3]. Mostly, these electrolytes are ceramic and should be prepared using solidstate synthesis at elevated temperatures. Such electrolytes are * Artem Ulihin [email protected] 1
Institute of Solid State Chemistry and Mechanochemistry, SB RAS, Novosibirsk, Russia 630090
2
Novosibirsk State University, Novosibirsk, Russia 630090
3
Novosibirsk State Technical University, Novosibirsk, Russia 630071
4
Nikolayev Institute of Inorganic Chemistry, SB RAS, Novosibirsk, Russia 630090
brittle and mechanically incompatible with electrode materials used in the batteries. In this regard, composite solid electrolytes are of special interest as their physical properties may be easily adapted to a particular application by variation of the type and concentration of the components. Examples of such solid electrolytes with lithium ion conductivity are composites LinX-Al2O3 (X = I− [4–6], Cl− [7], SO42− [8, 9]). Earlier, we have investigated a series of composite solid ele
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