Sergey N. Marshenya, Alexey G. Scherbakov, Artem D. Dembitskiy, Alexander A. Golubnichiy, Ivan A. Trussov, Aleksandra A. Savina, Sergey M. Kazakov, Dmitry A. Aksyonov, Evgeny V. Antipov, Stanislav S. Fedotov
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引用次数: 0
Abstract
The synthesis of langbeinite-type phosphates with small cations such as Li+ or Na+via a high-temperature solid-state reaction is a challenging task due to the predominant formation of a related NaSICON-type phase. This work reports on the synthesis route, crystal structure, thermal behavior, and Na-conductive properties of the langbeinite-type NaZr2(PO4)3 prepared by a mechanochemically activated ion-exchange reaction between hydrothermally prepared NH4Zr2(PO4)3 and NaNO3. The crystal structure of NaZr2(PO4)3 is refined based on X-ray diffraction data and validated by Fourier-transformed infrared spectroscopy. NaZr2(PO4)3 is found to be stable up to 730 °C, undergoing a transformation into the NaSICON phase with further heating. Notably, in the 25–500 °C range, the material shows negative thermal expansion. The Na+ conductivity within the range of 50–225 °C amounts to 1.7 × 10−8 S cm−1 at 50 °C and 1 × 10−6 S cm−1 at 225 °C with an activation energy of 0.44 eV, accompanied by a sufficiently low (∼10−12 S cm−1) electronic conductivity. The bandgap of 4.44 eV and the electrochemical stability window covering the 1.39–4.18 V vs. Na/Na+ range are calculated using density functional theory. The obtained results open up opportunities for designing langbeinite-structured phosphates as potential solid electrolytes for Na-ion batteries.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.