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Lithium ion conducting glass-ceramics with NASICON-type structure based on the Li1+x Crx (Gey Ti1-y)2-x (PO4)3 system

Abstract : The primary goal of this work is to develop a new NASICON-structured glass-ceramic with high Li-ion conductivity. Therefore, this work introduces a new series of NASICON-type compositions based on the Li1+xCrx(GeyTi1-y)2-x(PO4)3 system. At first, a specific composition of this system is synthesized by the melt-quenching method, followed by crystallization. The crystallization behavior of the precursor glass is examined by differential scanning calorimetry and infrared spectroscopy. The main results indicate that the precursor glass presents homogeneous nucleation, has considerable glass stability and crystallizes a NASICON-like phase, which allows solid electrolytes to be obtained by the glass-ceramic route. As a second step, we examine the effect of substituting Ti by Cr and Ge on the glass stability of the precursor glass, on the structural parameters of NASICON-like phase and the electrical properties of the glass-ceramics. Hence, a set of sixteen compositions of this system is synthesized. The main results indicate that the glass stability increases when Ti is replaced by Ge and Cr. After crystallization, all the glass-ceramics present NASICON-like phase, and their lattice parameters decrease with Ge and increase with Cr content, making it possible to adjust the unit cell volume of the NASICON-type structure. Furthermore, the ionic conductivity and activation energy for lithium conduction in the glass-ceramics are notably dependent on the unit cell volume of the NASICON-type structure. Finally, the electrochemical stability window of the NASICON-structured glass-ceramics of highest ionic conductivity is investigated. Cyclic voltammetry measurements are followed by in situ electrochemical impedance spectroscopy, enabling the effect of oxidation and reduction reactions on the electrical properties of the glass-ceramics in question to be determined. X-ray photoelectron spectroscopy, in turn, is applied to determine which chemical species undergo reduction/oxidation. Our findings reveal that the electrochemical stability of this material is limited by the reduction of Ti+4 cations in low potentials and by the oxidation of O-2 anions in high potentials. At high potentials, similar behavior is also encountered for other well-known NASICON-like Li-ion conducting suggesting that the electrochemical behavior in oxidative potentials could be generalized for NASICON-structured phosphates.
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Rafael Nuernberg. Lithium ion conducting glass-ceramics with NASICON-type structure based on the Li1+x Crx (Gey Ti1-y)2-x (PO4)3 system. Other. Université Montpellier; Universidade federal de São Carlos, 2018. English. ⟨NNT : 2018MONTS141⟩. ⟨tel-02286223⟩

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