Electrochemical properties of superionic conductors CsAg4Br3-хI2+х

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CsAg4Br3–хI2+х solid solutions with x=0.38; 0.50; 0.63 were prepared by solid-phase synthesis; the single-phase of the products was confirmed by X-ray diffraction and differential scanning calorimetry. Studies of the electrical transport characteristics of CsAg4Br3–хI2+х included measurements of the ionic conductivity by the four-probe method in the range of –50…+120°C and an evaluation of the electronic component of the conductivity by the Hebb-Wagner method. It was shown that the ionic conductivity of CsAg4Br3–хI2+х solid solutions in the studied range of compositions is practically independent of x and is very close to that of the well-known superionic conductor RbAg4I5. The activation energy of conduction for all studied compounds is about 10 kJ mol–1. The oxidation potential determined by the stepwise polarization technique for CsAg4Br3–хI2+х solid solutions is noticeably higher than that of RbAg4I5, and is in the range of 0.75–0.78 V (vs. Ag0/Ag+). The high electrochemical characteristics of CsAg4Br3–хI2+х (0.38≤x≤0.63) and the absence of polymorphic transitions in the studied range from –160°C to the melting point (175 – 178°С) make these materials promising for use in electrochemical devices based on solid electrolytes, especially for low temperature applications.

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A. Glukhov

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences

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Email: 0511alex@mail.ru
俄罗斯联邦, Chernogolovka

O. Reznitskikh

Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences

Email: 0511alex@mail.ru
俄罗斯联邦, Yekaterinburg

T. Yaroslavtseva

Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences

Email: tanya_yaroslavtseva@mail.ru
俄罗斯联邦, Yekaterinburg

N. Urusova

Institute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences

Email: 0511alex@mail.ru
俄罗斯联邦, Yekaterinburg

A. Ukshe

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences

Email: 0511alex@mail.ru
俄罗斯联邦, Chernogolovka

Yu. Dobrovolsky

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences

Email: 0511alex@mail.ru
俄罗斯联邦, Chernogolovka

O. Bushkova

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry of the Russian Academy of Sciences

Email: 0511alex@mail.ru
俄罗斯联邦, Chernogolovka

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2. Fig. 1. Experimental (dots) and calculated (line) X-ray diffraction patterns of solid electrolytes CsAg4Br3-хI2+х, where x = 0.38 (a), 0.50 (b) and 0.63 (c). Dashes are the angular positions of Bragg reflections. Below is the difference between calculation and experiment.

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3. Fig. 2. DSC curves for synthesized samples of solid electrolytes CsAg4Br3-хI2+х (x = 0.38; 0.50; 0.63) and RbAg4I5.

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4. Fig. 3. Temperature dependences of the conductivity of solid electrolytes RbAg4I5 and CsAg4Br3-хI2+х (where x = 0.38; 0.50; 0.63).

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5. Fig. 4. Volt-ampere characteristics of solid electrolytes CsAg4Br3-xI2+x (a) and assessment of the oxidation potential Eox using the example of CsAg4Br2.37I2.63 (b). (For ease of comparison of curves in Fig. 4a, the current density values ​​are multiplied by the thickness of the electrolyte; the cross-sectional areas of all electrolyte samples are the same and equal to 0.20 cm2.)

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