Review and prospects of Mn-based spinel compounds as cathode materials for lithium-ion batteries

Dou, Shumei

doi:10.1007/s11581-015-1545-5

Cited by 50 publications

(31 citation statements)

References 161 publications

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“…To solve these problems, several strategies were used by researchers: Partial replacement of Mn or O to stabilize host structure; surface modification to improve the interface; particle size, pore structure, and morphology to improve kinetic performance by reducing length of lithium ions’ and electrons’ transport paths [ 20 ]. Of all these approaches, (1) partial substitution of Mn 3+ ions and (2) particle size control have proven to be effective in improving rate capability, cycle life, and discharge capacity at elevated temperatures of LMO [ 21 ].…”

Section: Introductionmentioning

confidence: 99%

Kinetic and Thermodynamic Studies on Synthesis of Mg-Doped LiMn2O4 Nanoparticles

2020

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In this work, a first study on kinetics and thermodynamics of thermal decomposition for synthesis of doped LiMn2O4 nanoparticles is presented. The effect of Mg doping concentration on thermal decomposition of synthesis precursors, prepared by ultrasound-assisted Pechini-type sol–gel process, and its significance on nucleation and growth of Mg-doped LiMn2O4 nanoparticles was studied through a method based on separation of multistage processes in single-stage reactions by deconvolution and transition state theory. Four zones of thermal decomposition were identified: Dehydration, polymeric matrix decomposition, carbonate decomposition and spinel formation, and spinel decomposition. Kinetic and thermodynamic analysis focused on the second zone. First-order Avrami-Erofeev equation was selected as reaction model representing the polymer matrix thermal decomposition. Kinetic and thermodynamic parameters revealed that Mg doping causes an increase in thermal inertia on conversion rate, and CO2 desorption was the limiting step for formation of thermodynamically stable spinel phases. Based on thermogravimetry experiments and the effect of Mg on thermal decomposition, an optimal two-stage heat treatment was determined for preparation of LiMgxMn2-xO4 (x = 0.00, 0.02, 0.05, 0.10) nanocrystalline powders as promising cathode materials for lithium-ion batteries. Crystalline structure, morphology, and stoichiometry of synthesized powders were characterized by XRD, FE-SEM, and AAS, respectively.

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Section: Introductionmentioning

confidence: 99%

Kinetic and Thermodynamic Studies on Synthesis of Mg-Doped LiMn2O4 Nanoparticles

2020

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“…pinel compounds-typically represented as AB 2 O 4 , with A and B as metal ions-form an important class of materials [1][2][3][4][5] . Spinels are found as naturally occurring minerals all over the globe 6 and have traditionally been utilized as precious stones, such as red or blue spinels containing either Cr +3 or Fe +2 / Zn +2 ions, respectively 7,8 .…”

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confidence: 99%

Prediction of structure and cation ordering in an ordered normal-inverse double spinel

et al. 2020

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Spinels represent an important class of technologically relevant materials, used in diverse applications ranging from dielectrics, sensors and energy materials. While solid solutions combining two “single spinels” have been explored in a number of past studies, no ordered “double” spinels have been reported. Based on our first principles computations, here we predict the existence of such a double spinel compound MgAlGaO4, formed by an equimolar mixing of MgAl2O4 normal and MgGa2O4 inverse spinels. After studying the details of its atomic and electronic structure, we use a cluster expansion based effective Hamiltonian approach with Monte Carlo simulations to study the thermodynamic behavior and cation distribution as a function of temperature. Our simulations provide strong evidence for short-ranged cation order in the double spinel structure, even at significantly elevated temperatures. Finally, an attempt was made to synthesize the predicted double spinel compound. Energy Dispersive X-ray Spectrometry and X-ray diffraction Rietveld refinements were performed to characterize the single-phase chemical composition and local configurational environments, which showed a favorable agreement with the theoretical predictions. These findings suggest that a much larger number of compounds can potentially be realized within this chemical space, opening new avenues for the design of spinel-structured materials with tailored functionality.

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“…Morphology and particle size control, surface modification, and doping have been the main methodologies studied. [ 82–84 ] LiMn 2 O 4 (LMO) is commonly employed in blended cathodes for rechargeable automotive batteries because of its low cost and excellent rate capability. [ 85,86 ] Li ion can be inserted in the λ‐MnO 2 cubic phase by a topotactic insertion reaction with isotropical expansion of the cell to form LiMn 2 O 4 .…”

Section: Intercalation Electrodesmentioning

confidence: 99%

Electrochemical Methods for Lithium Recovery: A Comprehensive and Critical Review

et al. 2020

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Due to the ubiquitous presence of lithium‐ion batteries in portable applications, and their implementation in the transportation and large‐scale energy sectors, the future cost and availability of lithium is currently under debate. Lithium demand is expected to grow in the near future, up to 900 ktons per year in 2025. Lithium utilization would depend on a strong increase in production. However, the currently most extended lithium extraction method, the lime‐soda evaporation process, requires a period of time in the range of 1–2 years and depends on weather conditions. The actual global production of lithium by this technology will soon be far exceeded by market demand. Alternative production methods have recently attracted great attention. Among them, electrochemical lithium recovery, based on electrochemical ion‐pumping technology, offers higher capacity production, it does not require the use of chemicals for the regeneration of the materials, reduces the consumption of water and the production of chemical wastes, and allows the production rate to be controlled, attending to the market demand. Here, this technology is analyzed with a special focus on the methodology, materials employed, and reactor designs. The state‐of‐the‐art is reevaluated from a critical perspective and the viability of the different proposed methodologies analyzed.

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Review and prospects of Mn-based spinel compounds as cathode materials for lithium-ion batteries

Cited by 50 publications

References 161 publications

Kinetic and Thermodynamic Studies on Synthesis of Mg-Doped LiMn2O4 Nanoparticles

Kinetic and Thermodynamic Studies on Synthesis of Mg-Doped LiMn2O4 Nanoparticles

Prediction of structure and cation ordering in an ordered normal-inverse double spinel

Electrochemical Methods for Lithium Recovery: A Comprehensive and Critical Review

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