Non-isothermal reaction mechanism and kinetic analysis for the synthesis of monoclinic lithium zirconate (m-Li2ZrO3) during solid-state reaction

Juan P Yasnó,Gustavo Suárez,Susana Conconi,Arnaldo Visintin

doi:10.1186/s40543-021-00267-5

Abstract

Non-isothermal reaction mechanism and kinetic analysis for the synthesis of monoclinic lithium zirconate (m-Li2ZrO3) were investigated by processing of TG-DTA, along with XRD, DLS, and HRTEM. For this purpose, the solid-state reaction of Li2CO3 with ZrO2 was carried out by TG-DTA at different heating rates (10, 20, and 30 °C/min) from room temperature to 1100 °C. The thermal data was used to calculate the kinetic parameters by two types of isoconversional methods: Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS). The reaction mechanism was determined by the model-fitting method, applying the Coats-Redfern (CR) approximation to the different solid-state reaction models. The results confirmed the formation of pure m-Li2ZrO3, consists of semispherical particles of about 490 nm, using a very short reaction time. The average activation energy obtained by FWO and KAS methods were 274.73 and 272.50 kJ/mol, respectively. It was found that the formation of m-Li2ZrO3 from Li2CO3 with ZrO2 is governed by the three-dimensional diffusion mechanism. Based on these results, a microscopic reaction model of the formation of m-Li2ZrO3 was proposed.

Highlights

Monoclinic lithium zirconate (m-Li2ZrO3) is a ceramic material that has potential applications in different fields including solid-state lithium-ion batteries (Dong et al 2015; Sherstobitova et al 2016; Zhan et al 2018), solid sorbent for CO2 capture (Ida and Lin 2003; Kordatos et al 2017; Chattaraj 2017), and nuclear reactors (Taddia et al 2005; Oyaidzu et al 2006; Chitnis et al 2018)
Non-isothermal reaction mechanism and kinetic parameters have been determined for the first time for the synthesis of monoclinic lithium zirconate (m-Li2ZrO3) via solid-state reaction of Li2CO3 with ZrO2
Kinetic analysis was investigated by processing of TG-differential-thermal analysis (DTA), along with Xray diffraction (XRD), dynamic light scattering (DLS), and HRTEM

Summary

Introduction

Monoclinic lithium zirconate (m-Li2ZrO3) is a ceramic material that has potential applications in different fields including solid-state lithium-ion batteries (Dong et al 2015; Sherstobitova et al 2016; Zhan et al 2018), solid sorbent for CO2 capture (Ida and Lin 2003; Kordatos et al 2017; Chattaraj 2017), and nuclear reactors (Taddia et al 2005; Oyaidzu et al 2006; Chitnis et al 2018). The most common analytical method used in kinetic analysis is TGA due its simplicity and good repeatability (Khawam and Flanagan 2006; Ghuge and Mandal 2017; Ebrahimi-Kahrizsangi and Abbasi 2008; Jiang and Wei 2018; Liu et al 2020; Marinović-Cincović et al 2013). It has been involved in the study, only by model-fitting method, of the reaction kinetics for the synthesis of other Li-based ceramics such as Li2TiO3 (Mandal 2014), LiDyO2 (Ghuge and Mandal 2017), and LiNiO2 (Lu and Wei-Cheng 2000)

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