Thermodynamically self-consistent method to predict thermophysical properties of ionic oxides

Seifitokaldani, Ali; Gheribi, Aïmen E.

doi:10.1016/j.commatsci.2015.06.003

Cited by 20 publications

(18 citation statements)

References 48 publications

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“…Considering thermodynamic properties of the system, the values of enthalpy of the formation of pure LiFePO 4 and FePO 4 compounds have been measured from the oxides or from the elements . The heat capacity functions of both LiFePO 4 and FePO 4 were predicted in our previous work by combining DFT to a self‐constant method based on quasi‐harmonic approximation (QHA) and a minimization procedure to ensure that the Maxwell relations are respected . Our predictions were found to be in very good agreement with the experimental data reported in the range from 2–773 K and from 2–300 K for LiFePO 4 and FePO 4 , respectively.…”

Section: Literature Reviewsupporting

confidence: 67%

Modelling of phase equilibria of LiFePO₄‐FePO₄ olivine join for cathode material

2019

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A thermodynamic model for the FePO 4 -LiFePO 4 olivine join has been developed in order to provide support for the understanding of the charge transport behaviour within the cathode material during the battery operation. The Gibbs energy model for the olivine solution is based on the compound energy formalism with long-range-order and has been calibrated using the CALPHAD method, permitting the computation of phase equilibria by Gibbs energy minimization techniques. The model can simultaneously reproduce the reported eutectoid reaction, the 3 low-temperature miscibility gaps, the enthalpy of mixing, and the change of the voltage plateau with temperature during the delithiation process, in agreement with the available experimental data. The spinodal decomposition, which is possibly associated with fast charge transport within the cathode material, involves up to two sub-spinodal decompositions. Hence, the unique low-temperature miscibility gap of this system is considered as a blend of the two sub-miscibility gaps.

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Section: Literature Reviewsupporting

confidence: 67%

Modelling of phase equilibria of LiFePO₄‐FePO₄ olivine join for cathode material

2019

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“…The TSC method is, in summary, an extension of the QHA satisfying the Maxwell relations to compel the results to conform to the fundamental thermodynamic laws, ensuring thermodynamic consistency. This method has been already examined for ionic oxides and metallic systems, and showed precise and consistent results more accurate than those from the classical QHA method 28 29 30 31 . The TSC iterative method, is based on the solution of a system of interrelated thermodynamic equations for the intrinsic properties of materials, in which the Debye temperature is one of the inputs provided from first-principle calculations.…”

Section: Methodsmentioning

confidence: 96%

“…In the QHA method, whatever success it may have, there lacks a systematic way of preserving the consistency of the properties and so conforming to thermodynamic laws. This deficiency has been recently eliminated through the TSC method 28 , which simultaneously conserves the thermodynamic laws. The TSC method is, in summary, an extension of the QHA satisfying the Maxwell relations to compel the results to conform to the fundamental thermodynamic laws, ensuring thermodynamic consistency.…”

Section: Methodsmentioning

confidence: 99%

Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism

Seifitokaldani

Gheribi

Phan

et al. 2016

Sci Rep

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A new thermodynamically self-consistent (TSC) method, based on the quasi-harmonic approximation (QHA), is used to obtain the Debye temperatures of LiFePO4 (LFP) and FePO4 (FP) from available experimental specific heat capacities for a wide temperature range. The calculated Debye temperatures show an interesting critical and peculiar behavior so that a steep increase in the Debye temperatures is observed by increasing the temperature. This critical behavior is fitted by the critical function and the adjusted critical temperatures are very close to the magnetic phase transition temperatures in LFP and FP. Hence, the critical behavior of the Debye temperatures is correlated with the magnetic phase transitions in these compounds. Our first-principle calculations support our conjecture that the change in electronic structures, i.e. electron density of state and electron localization function, and consequently the change in thermophysical properties due to the magnetic transition may be the reason for the observation of this peculiar behavior of the Debye temperatures.

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“…The quasi-harmonic approximation is typically coupled with DFT simulations to evaluate the c P evolution of a given solid phase as a function of temperature [10]. Examples of our DFT simulations based on a thermodynamically self-consistent method [11,12] used to determine the c P function of compounds are illustrated in Figure 2 for the AlNi 2 Ti phase (a Heusler compound with an L2 1 structure-Fm3m) and for the Al 3 Zr intermetallic (D0 23 structure-I4/mmm), respectively. In this figure, the heat capacities of these two compounds have been predicted from DFT simulations and compared with available experimental data.…”

Section: T Re Fmentioning

confidence: 99%

On the Application of the FactSage Thermochemical Software and Databases in Materials Science and Pyrometallurgy

et al. 2020

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The discovery of new metallic materials is of prime importance for the development of new technologies in many fields such as electronics, aerial and ground transportation as well as construction. These materials require metals which are obtained from various pyrometallurgical processes. Moreover, these materials need to be synthesized under extreme conditions of temperature where liquid solutions are produced and need to be contained. The design and optimization of all these pyrometallurgical processes is a key factor in this development. We present several examples in which computational thermochemistry is used to simulate complex pyrometallurgical processes including the Hall–Heroult process (Al production), the PTVI process (Ni production), and the steel deoxidation from an overall mass balance and energy balance perspective. We also show how computational thermochemistry can assist in the material selection in these extreme operation conditions to select refractory materials in contact with metallic melts. The FactSage thermochemical software and its specialized databases are used to perform these simulations which are proven here to match available data found in the literature.

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Thermodynamically self-consistent method to predict thermophysical properties of ionic oxides

Cited by 20 publications

References 48 publications

Modelling of phase equilibria of LiFePO₄‐FePO₄ olivine join for cathode material

Modelling of phase equilibria of LiFePO₄‐FePO₄ olivine join for cathode material

Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism

On the Application of the FactSage Thermochemical Software and Databases in Materials Science and Pyrometallurgy

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Thermodynamically self-consistent method to predict thermophysical properties of ionic oxides

Cited by 20 publications

References 48 publications

Modelling of phase equilibria of LiFePO4‐FePO4 olivine join for cathode material

Modelling of phase equilibria of LiFePO4‐FePO4 olivine join for cathode material

Important Variation in Vibrational Properties of LiFePO4 and FePO4 Induced by Magnetism

On the Application of the FactSage Thermochemical Software and Databases in Materials Science and Pyrometallurgy

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Modelling of phase equilibria of LiFePO₄‐FePO₄ olivine join for cathode material

Modelling of phase equilibria of LiFePO₄‐FePO₄ olivine join for cathode material