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Thermokinetic and thermodynamics of Pechini derived Li7−3xAlxLa3Zr2O12 (X = 0.0–0.2) xerogel decomposition under oxidative conditions

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Abstract

Solid electrolytes for all-solid-state Li-ion batteries have attracted significant interest with their outstanding safety. But their poor ionic conductivity limits their widespread use. Li7La3Zr2O12 solid electrolytes have the potential of showing comparable ionic conductivities with commercially available electrolytes. However, its high ion conductive cubic phase is not stable at room temperature. Studies demonstrated that the cubic Li7La3Zr2O12 phase can be stabilized easier than solid-state method by modified Pechini method and very little work has been done in order to understand what makes the phase transformation easier. For this purpose, thermal decomposition behavior, model-free kinetics and thermodynamics of Li7La3Zr2O12 xerogels synthesized by modified Pechini method were investigated and the effect of stabilizer (Al) addition was discussed in this study. The results showed the presence of four peak zones and the main reaction zone includes multiple reactions. Different statistical functions were tested for deconvolution of main reaction zone and the best fits were obtained by Bigaussian and Asym2sig statistical functions. The multiple reactions in the main thermal degradation zone were separated into three reaction zones and thermokinetic and thermodynamic calculations were employed using model-free approach. The results also showed that Al incorporation expanded the main thermal decomposition zone of LLZO and resulted in changes in kinetic and thermodynamic parameters.

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Abbreviations

A :

Pre-exponential factor (s−1)

E a :

Activation energy (kJ mol−1)

h :

Planck constant (6.626 × 10–34 J s).

K B :

Boltzmann constant (1.381 × 10–23 J K−1)

R :

Universal gas constant (8.3144 × 10−3 kJ mol−1 K−1)

t :

Time (s)

T :

Temperature (K)

T m :

Temperature at the maximum conversion rate (K)

w t :

Mass at time t (mg)

w o :

Mass at the initial stage of the reaction (mg)

w f :

Mass at the final stage of the reaction (mg)

α :

Conversion degree

β :

Heating rate (K min−1)

x̅ :

Mean value

k(T):

Temperature function

f(α):

Reaction model function

g(α):

Integrated form of reaction model

p(u):

Temperature integral

ΔG :

Gibbs free energy change (kJ mol−1)

ΔH :

Enthalpy change (kJ mol−1)

ΔS :

Entropy change (J mol−1 K−1)

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Acknowledgements

The study was funded by Eskisehir Technical University Scientific Research Projects Unit with a grant number of 1802F030. Authors would also like to thank Prof. Dr. Ender Suvacı and Dr. Tümerkan Kesim for their valuable support on TGA analysis. Data collection and analysis were performed by Dr. Kamil Burak Dermenci and Dr. Gamzenur Özsin. Writing review and editing were performed by Prof. Dr. Servet Turan. All authors read and approved the final manuscript.

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Authors and Affiliations

  1. Department of Chemical Engineering, Faculty of Engineering, Bilecik Şeyh Edebali University, 11230, Bilecik, Turkey

    Gamzenur Özsin

  2. Department of Materials Science and Engineering, Faculty of Engineering, Eskişehir Technical University, 26555, Eskisehir, Turkey

    Kamil Burak Dermenci & Servet Turan

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  1. Gamzenur Özsin
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Correspondence to Kamil Burak Dermenci.

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Özsin, G., Dermenci, K.B. & Turan, S. Thermokinetic and thermodynamics of Pechini derived Li7−3xAlxLa3Zr2O12 (X = 0.0–0.2) xerogel decomposition under oxidative conditions. J Therm Anal Calorim 146, 1405–1420 (2021). https://doi.org/10.1007/s10973-020-10462-y

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