Quantification of hydroxide in co-precipitated nickel, manganese, cobalt carbonate precursor via TG-MS analyses

IF 3.1 2区化学 Q2 CHEMISTRY, ANALYTICAL

Thermochimica Acta Pub Date : 2025-05-18 DOI:10.1016/j.tca.2025.180035

Valérie Charbonneau , François Larouche , Kamyab Amouzegar , Gervais Soucy , Jocelyn Veilleux

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Abstract

A significant obstacle associated with the synthesis of carbonate precursors for lithium nickel manganese cobalt oxides (NMC) is the concurrent precipitation of nickel hydroxide. Depending on the synthesis conditions and on the desired transition metals stoichiometric ratio, nickel may precipitate solely in its hydroxide form, even with excess carbonate present in the synthesis medium. The present work investigates the use of thermogravimetry-mass spectrometry (TG-MS) technique to quantify the dehydration, dehydroxylation and decarbonation of such mixed precursors. A calibration curve built for the dehydroxylation of nickel hydroxide with a copper sulfate internal standard allowed for the differentiation of sample weight loss associated to either hydrates or hydroxides. Thereafter, the numerical deconvolution of derivative TG and MS peaks obtained for NMC precursors enabled the calculation of atomic percentages of metal hydroxides and carbonates. Various commonly cited mathematical models for deconvolution are examined to investigate the quality of fitted data. According to this research, asymmetric double sigmoidal functions best represented the TG-MS data obtained for NMC carbonate precursors.

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用TG-MS法定量共沉淀镍、锰、碳酸钴前驱体中的氢氧化物

锂镍锰钴氧化物（NMC）碳酸盐前驱体合成的一个重要障碍是氢氧化镍的同时沉淀。根据合成条件和所需过渡金属的化学计量比，镍可以仅以氢氧化物形式析出，即使在合成介质中存在过量的碳酸盐。本研究研究了热重质谱（TG-MS）技术对这种混合前体的脱水、去羟基化和脱碳的定量。用硫酸铜内标建立的氢氧化镍去羟基化的校准曲线允许区分与水合物或氢氧化物相关的样品重量损失。此后，对NMC前驱体的导数TG和MS峰进行数值反褶积，可以计算金属氢氧化物和碳酸盐的原子百分比。检查了各种常用的反褶积数学模型，以调查拟合数据的质量。研究表明，非对称双s型函数最能代表NMC碳酸盐前驱体的TG-MS数据。

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来源期刊

Thermochimica Acta 化学-分析化学

CiteScore

6.50

自引率

8.60%

发文量

210

审稿时长

40 days

期刊介绍： Thermochimica Acta publishes original research contributions covering all aspects of thermoanalytical and calorimetric methods and their application to experimental chemistry, physics, biology and engineering. The journal aims to span the whole range from fundamental research to practical application. The journal focuses on the research that advances physical and analytical science of thermal phenomena. Therefore, the manuscripts are expected to provide important insights into the thermal phenomena studied or to propose significant improvements of analytical or computational techniques employed in thermal studies. Manuscripts that report the results of routine thermal measurements are not suitable for publication in Thermochimica Acta. The journal particularly welcomes papers from newly emerging areas as well as from the traditional strength areas: - New and improved instrumentation and methods - Thermal properties and behavior of materials - Kinetics of thermally stimulated processes