Enhancement of battery performance of LiMn<sub>2</sub>O<sub>4</sub>: correlations between electrochemical and magnetic properties

Demirel, Serkan; Öz, Erdinç; Altın, S.; Bayri, Ali; Altın, E.; Avcı, Sevda

doi:10.1039/c6ra05032h

Cited by 18 publications

(8 citation statements)

References 85 publications

(82 reference statements)

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“…Further, it has been noticed that such Jahn–Teller-like distortion has a pronounced effect on the electrochemical properties. For instance, Demirel et al reported the enhanced capacity of LiMn 2 O 4 due to the suppression of Jahn–Teller distortion while substituting Mn 3+ with another element. Further, the existence of Jahn–Teller distortion in LiNiO 2 has led to the instability of the cathode material .…”

Section: Discussionmentioning

confidence: 99%

Unique Structure-Induced Magnetic and Electrochemical Activity in Nanostructured Transition Metal Tellurates Co_1 – xNi_xTeO₄ (x = 0, 0.5, and 1)

Patel

Panda

Rani

et al. 2020

ACS Appl. Energy Mater.

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The emergence of cutting-edge nanomaterials with rational design, primarily with a structure-driven functionality, is a prerequisite for achieving advancement in current energy scenarios. This report presents facile sol−gel-grown, first-of-its-kind, nanostructured transition metal tellurates Co 1 − x Ni x TeO 4 (x = 0, 0.5, and 1). These are a class of promising magnetic and energy storage materials. Along with electronic structure signatures of individual nanocrystals through electron energy loss spectroscopy, microstructural and high-resolution synchrotron X-ray diffraction analysis results in a new structural model, which further sheds light on the structure-driven performances of these tellurates. Antiferromagnetic interactions observed at ∼48, 58, and 76 K for x = 0, 0.5, and 1, respectively, surpass numerous antiferromagnets. The robust electrochemical activity of NiTeO 4 against Li metal shows a high reversible specific capacity of ∼1271 mA h g −1 in the first discharge cycle, with 80% capacity retention over long-term cycles. Thorough ex situ X-ray absorption fine-structure spectroscopy and transmission electron microscopy investigations performed on several charging/discharging cycled electrodes establish a conversion-based battery reaction mechanism. The resulting anode, thus, displays unprecedentedly high stability in comparison to existing transition metal-based anode materials for Li-ion batteries. The observed outcomes are further understood to stem from different degrees of the Jahn−Teller-like z-out and z-in distortion in the respective d orbitals of Co 2+ and Ni 2+ .

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Section: Discussionmentioning

confidence: 99%

Unique Structure-Induced Magnetic and Electrochemical Activity in Nanostructured Transition Metal Tellurates Co_1 – xNi_xTeO₄ (x = 0, 0.5, and 1)

Patel

Panda

Rani

et al. 2020

ACS Appl. Energy Mater.

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“…This points to different proportions of high and low spin configurations within the produced Mn 3+ states in uncoated and VO x -coated samples. Generally, Mn 4+ and Mn 3+ in octahedral coordination are both in high spin (HS) configuration, with the latter showing a higher spin state. − The HS Mn 3+ Jahn–Teller active phase has been correlated to the capacity loss in spinel LiMn 2 O 4 , with the Jahn–Teller distortions destabilizing the structure during electrochemical cycling. − The strong μ Mn drop upon charge in the uncoated material suggests the formation of a Mn environment corresponding to that of layered rhombohedral r -LiMnO 2 , where theoretical calculations predict the Mn 3+ in the not Jahn–Teller active low spin (LS) configuration . Interestingly, the theoretical simulation of this phase predicts several potential advantages for a good electrochemical activity and agrees with the results reported here, in fact it explains the shift of the main Mn K-edge absorption feature toward higher energy during the charge, generally associated with oxidation, while Mn is actually partially reducing.…”

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confidence: 99%

Role of Manganese in Lithium- and Manganese-Rich Layered Oxides Cathodes

Simonelli

Sorrentino

Marini

et al. 2019

J. Phys. Chem. Lett.

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Lithium-rich transition-metal-oxide cathodes are among the most promising materials for the next lithium-ion-batteries generation because they operate at high voltages and deliver high capacities. However, their cycle-life remains limited and individual roles of the transition-metals are still not fully understood. By bulk-sensitive X-ray absorption and emission spectroscopy on Li[Li 0.2 Ni 0.16 Mn 0.56 Co 0.08 ]O 2 we inspect the behavior of Mn, generally considered inert upon the electrochemical process. During the first charge Mn appears to be redox-active showing a partial transformation from high-spin Mn 4+ to Mn 3+ in both high and low spin configurations, where the latter is expected to favor reversible cycling. The Mn redox-state along cycling continues changing in opposition to the expected charge compensation and is correlated with Ni oxidation/reduction, also spatially. The findings suggest the strain induced on the Mn-O sublattice by the Ni oxidation to trigger the Mn reduction. These results unravel the Mn role in controlling the electrochemistry of Li-rich cathodes. The wide use of rechargeable lithium-ion batteries and the continuously growing demands of increased energy and power densities stimulate the investigation of novel high-voltage cathode materials. 1, 2 Lithiated transition-metal-oxides are under intensive investigation as cathode materials for Li-ion batteries. The best performing cathodes show an ordered layered structure, which locates the Li ions in between the metal-oxygen layers. 3, 4 Generally these materials offer the best cycle life when the layered structure is maintained during the delithiation/lithiation process. Among Mn, Co, and Ni, only Co 3+ and Ni 3+ enable 2D layered Li-based oxides. LiNiO 2 , however, has various drawbacks related to its crystal structure: difficulty to be synthesized, poor cycling performance, and poor thermal stability. 5 As a matter of fact, LiCoO 2 is the 2D layered oxide showing the best electrochemical performance and the most commonly used material in Li-ion batteries 6. The

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“…Susceptibility of the samples increases with increasing Ru content and the transition temperature gradually shifts from ~150 K to ~170 K. μ eff values of the samples were calculated by the linear part of χ −1 ‐T graph as seen in Figure B. Details of μ eff calculation procedure can be found in ref . The calculated μ eff and theta values are listed in Table .…”

Section: Resultsmentioning

confidence: 99%

Structural, magnetic, electrical, and electrochemical properties of Sr–Co–Ru–O: A hybrid‐capacitor application

et al. 2018

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In this study, we report the synthesis of SrCo1−xRuxO3−δ nominal compositions, where x = 0.0‐1.0, using solid‐state reaction technique. XRD analysis confirms the structure of x = 0 sample as hexagonal Sr6Co5O15. As the Co ions are substituted by Ru, a two‐phase structure (hexagonal R32 and orthorhombic Pbnm) emerges up to x ≤ 0.5. As the Ru content is increased further, the hexagonal R32 phase disappears completely and an orthorhombic Pbnm phase becomes the main phase. SEM images show that grain size of the samples decreases with increasing Ru content. Temperature‐dependent electrical conductivity studies indicate upon Ru substitution in the nominal SrCo1−xRuxO3−δ compounds, resistivity decreases due to appearance of metallic SrRuO3 phase. The cyclic voltammogram (CV) of the samples show capacitive properties upon Ru substitution. The cycle measurements of the capacitors yield promising results for potential supercapacitor applications.

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Enhancement of battery performance of LiMn₂O₄: correlations between electrochemical and magnetic properties

Abstract: We report the results of a systematic investigation of structural, electrical transport, magnetic, and electrochemical properties of LiBxMn2−xO4 (where x = 0.0–1), synthesized via a one-step solid state reaction technique.

Cited by 18 publications

References 85 publications

Unique Structure-Induced Magnetic and Electrochemical Activity in Nanostructured Transition Metal Tellurates Co_1 – xNi_xTeO₄ (x = 0, 0.5, and 1)

Unique Structure-Induced Magnetic and Electrochemical Activity in Nanostructured Transition Metal Tellurates Co_1 – xNi_xTeO₄ (x = 0, 0.5, and 1)

Role of Manganese in Lithium- and Manganese-Rich Layered Oxides Cathodes

Structural, magnetic, electrical, and electrochemical properties of Sr–Co–Ru–O: A hybrid‐capacitor application

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Enhancement of battery performance of LiMn2O4: correlations between electrochemical and magnetic properties

Abstract: We report the results of a systematic investigation of structural, electrical transport, magnetic, and electrochemical properties of LiBxMn2−xO4 (where x = 0.0–1), synthesized via a one-step solid state reaction technique.

Cited by 18 publications

References 85 publications

Unique Structure-Induced Magnetic and Electrochemical Activity in Nanostructured Transition Metal Tellurates Co1 – xNixTeO4 (x = 0, 0.5, and 1)

Unique Structure-Induced Magnetic and Electrochemical Activity in Nanostructured Transition Metal Tellurates Co1 – xNixTeO4 (x = 0, 0.5, and 1)

Role of Manganese in Lithium- and Manganese-Rich Layered Oxides Cathodes

Structural, magnetic, electrical, and electrochemical properties of Sr–Co–Ru–O: A hybrid‐capacitor application

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Enhancement of battery performance of LiMn₂O₄: correlations between electrochemical and magnetic properties

Unique Structure-Induced Magnetic and Electrochemical Activity in Nanostructured Transition Metal Tellurates Co_1 – xNi_xTeO₄ (x = 0, 0.5, and 1)

Unique Structure-Induced Magnetic and Electrochemical Activity in Nanostructured Transition Metal Tellurates Co_1 – xNi_xTeO₄ (x = 0, 0.5, and 1)