Study of the phase transition and thermodynamic functions of LiMn2O4

Knyazev, A. V.; Mączka, Mirosław; Смирнова, Н. Н.; Knyazeva, S.S.; Черноруков, Н. Г.; Ptak, Maciej; Shushunov, A. N.

doi:10.1016/j.tca.2014.08.020

Cited by 16 publications

(4 citation statements)

References 20 publications

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“…where the obtained A to E coefficients are listed in Table 3(b). The resulted specific heat at 298 K on our slightly overstoichiometric Li 1+x Mn 2Àx O 4 sample with x = 0.03, c p (LiMn 2 O 4 ) = 0.81 J g À1 K À1 is in good agreement with the recent reported values by Knyazev et al 22 using adiabatic calorimetry measurements up to 347 K on a stoichiometric LiMn 2 O 4 sample, showing the existence of the reversible orthorhombic-cubic known phase transition below room temperature (Fig. 2(a), inset graph).…”

Section: Specific Heat Capacitysupporting

confidence: 92%

Thermophysical properties of LiCoO₂–LiMn₂O₄blended electrode materials for Li-ion batteries

Gotcu-Freis

Seifert

2016

Phys. Chem. Chem. Phys.

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Thermophysical properties of two cathode types for lithium-ion batteries were measured by dependence on temperature. The cathode materials are commercial composite thick films containing LiCoO2 and LiMn2O4 blended active materials, mixed with additives (binder and carbon black) deposited on aluminium current collector foils. The thermal diffusivities of the cathode samples were measured by laser flash analysis up to 673 K. The specific heat data was determined based on measured composite specific heat, aluminium specific heat data and their corresponding measured mass fractions. The composite specific heat data was measured using two differential scanning calorimeters over the temperature range from 298 to 573 K. For a comprehensive understanding of the blended composite thermal behaviour, measurements of the heat capacity of an additional LiMn2O4 sample were performed, and are the first experimental data up to 700 K. Thermal conductivity of each cathode type and their corresponding blended composite layers were estimated from the measured thermal diffusivity, the specific heat capacity and the estimated density based on metallographic methods and structural investigations. Such data are highly relevant for simulation studies of thermal management and thermal runaway in lithium-ion batteries, in which the bulk properties are assumed, as a common approach, to be temperature independent.

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Section: Specific Heat Capacitysupporting

confidence: 92%

Thermophysical properties of LiCoO₂–LiMn₂O₄blended electrode materials for Li-ion batteries

Gotcu-Freis

Seifert

2016

Phys. Chem. Chem. Phys.

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“…The parameters in the model are optimized based on the data of heat capacity, − enthalpy of formation, ,− phase diagram, , and open cell voltages . The optimized thermodynamic parameters are summarized in Table S1.…”

Section: Methodsmentioning

confidence: 99%

High-Throughput Description of Infinite Composition–Structure–Property–Performance Relationships of Lithium–Manganese Oxide Spinel Cathodes

et al. 2018

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Lithium−manganese oxide based spinel is attractive as cathode materials in lithium ion batteries. A wide range of spinel solid solution can be directly sintered and result in different properties of identical compositions during the battery operation, making it extremely difficult to understand the intrinsic properties and evaluate the battery performance. In this work, a high-throughput computational framework combining ab initio calculations and a CALPHAD (Calculation of Phase Diagrams) approach is developed to systematically describe infinite composition− structure−property−performance relationships under sintered and battery states of spinel cathodes. Depending on composition and crystallography, various properties (physical, thermochemical, and electrochemical) relating key factors (cyclability, safety, and energy density) are quantitatively mapped. The overall performance is consequently evaluated and validated by key experiments. Finally, 4 V spinel cathodes with codoping of reasonable Li and vacancies on the octahedral sites have been proposed. The presented strategy provides a general guide to evaluate the performance of cathodes with wide composition ranges.

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“…Thermodynamic data related to LiMn 2 O 4 were not available in the HSC 9 database. Therefore, a separate database was created using the entropy and heat capacity data published by Knyazev 41 and enthalpy data published by Lai. 42 These extensions of the database permitted the extrapolation of ΔG 0 until 126.85 °C.…”

Section: Co (G) 2li O(s)mentioning

confidence: 99%

Chemical Transformations in Li-Ion Battery Electrode Materials by Carbothermic Reduction

Lombardo

Ebin

Foreman

et al. 2019

ACS Sustainable Chem. Eng.

122

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The effects of pyrolysis on the composition of the battery cell materials as a function of treatment time and temperature were investigated. Waste of Li-ion batteries was pyrolyzed in a nitrogen atmosphere at 400, 500, 600, and 700 °C for 30, 60, and 90 min. Thermodynamic calculations for the carbothermic reduction of active materials LiCoO2, LiMn2O4, and LiNiO2 by graphite and gas products were performed and compared to the experimental data. Ni, Mn, and Co (NMC) cathode materials recovered from spent Li-ion batteries were also studied. The results indicate that the organic compounds and the graphite are oxidized by oxygen from the active material and provide the reductive atmosphere. Such removal of the organic components increases the purity of the metal bearing material. Reactions with C and CO(g) led to a reduction of metal oxides with Co, CoO, Ni, NiO, Mn, Mn3O4, Li2O, and Li2CO3 as the main products. The reduction reactions transformed the metal compounds in the untreated LiB black mass to more soluble chemical forms. It was concluded that the pyrolysis can be used as an effective tool for the battery waste pretreatment to increase the efficiency of the leaching in hydrometallurgical processing of the black mass. The results obtained can help to optimize the parameters in the industrial processing already used for Li-ion battery recycling, especially if followed by hydrometallurgical treatment. Such optimization will decrease the energy demand and increase the metal recovery rate and utilization of the byproducts.

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Study of the phase transition and thermodynamic functions of LiMn2O4

Cited by 16 publications

References 20 publications

Thermophysical properties of LiCoO₂–LiMn₂O₄blended electrode materials for Li-ion batteries

Thermophysical properties of LiCoO₂–LiMn₂O₄blended electrode materials for Li-ion batteries

High-Throughput Description of Infinite Composition–Structure–Property–Performance Relationships of Lithium–Manganese Oxide Spinel Cathodes

Chemical Transformations in Li-Ion Battery Electrode Materials by Carbothermic Reduction

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Study of the phase transition and thermodynamic functions of LiMn2O4

Cited by 16 publications

References 20 publications

Thermophysical properties of LiCoO2–LiMn2O4blended electrode materials for Li-ion batteries

Thermophysical properties of LiCoO2–LiMn2O4blended electrode materials for Li-ion batteries

High-Throughput Description of Infinite Composition–Structure–Property–Performance Relationships of Lithium–Manganese Oxide Spinel Cathodes

Chemical Transformations in Li-Ion Battery Electrode Materials by Carbothermic Reduction

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Thermophysical properties of LiCoO₂–LiMn₂O₄blended electrode materials for Li-ion batteries

Thermophysical properties of LiCoO₂–LiMn₂O₄blended electrode materials for Li-ion batteries