Dataset Information

Mechanochemical synthesis of Li?MnO? shell/LiMO? (M = Ni, Co, Mn) core-structured nanocomposites for lithium-ion batteries.

ABSTRACT: Core/shell-like nanostructured xLi2MnO3·(1-x)LiMO2 (M = Ni, Co, Mn) composite cathode materials are successfully synthesized through a simple solid-state reaction using a mechanochemical ball-milling process. The LiMO2 core is designed to have a high-content of Ni, which increases the specific capacity. The detrimental surface effects arising from the high Ni-content are countered by the Li2MnO3 shell, which stabilizes the nanoparticles. The electrochemical performances and thermal stabilities of the synthesized nanocomposites are compared with those of bare LiMO2. In particular, the results of time-resolved X-ray diffraction (TR-XRD) analyses of xLi2MnO3·(1-x)LiMO2 nanocomposites as well as their differential scanning calorimetry (DSC) profiles demonstrate that the Li2MnO3 shell is effective in stabilizing the LiMO2 core at high temperatures, making the nanocomposites highly suitable from a safety viewpoint.

SUBMITTER: Noh JK

PROVIDER: S-EPMC4007074 | biostudies-literature | 2014 May

REPOSITORIES: biostudies-literature

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Publications

Mechanochemical synthesis of Li₂MnO₃ shell/LiMO₂ (M = Ni, Co, Mn) core-structured nanocomposites for lithium-ion batteries.

Noh Jae-Kyo JK Kim Soo S Kim Haesik H Choi Wonchang W Chang Wonyoung W Byun Dongjin D Cho Byung-Won BW Chung Kyung Yoon KY

Scientific reports 20140502

Core/shell-like nanostructured xLi2MnO3·(1-x)LiMO2 (M = Ni, Co, Mn) composite cathode materials are successfully synthesized through a simple solid-state reaction using a mechanochemical ball-milling process. The LiMO2 core is designed to have a high-content of Ni, which increases the specific capacity. The detrimental surface effects arising from the high Ni-content are countered by the Li2MnO3 shell, which stabilizes the nanoparticles. The electrochemical performances and thermal stabilities o ...[more]

PMID: 24784478

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Project description:Transition metal oxides are characterized by an acute structure and composition dependent electrocatalytic activity toward the oxygen evolution (OER) and oxygen reduction (ORR) reactions. For instance, Mn containing oxides are among the most active ORR catalysts, while Ni based compounds tend to show high activity toward the OER in alkaline solutions. In this study, we show that incorporation of Ni into α-MnO2, by adding Ni precursor into the Mn-containing hydrothermal solution, can generate distinctive sites with different electronic configurations and contrasting electrocatalytic activity. The structure and composition of the Ni modified hollandite α-MnO2 phase were investigated by X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), transmission electron microscopy coupled to energy-dispersive X-ray spectroscopy (TEM-EDX), inductively coupled plasma-optical emission spectroscopy (ICP-OES), and X-ray photoelectron spectroscopy (XPS). Our analysis suggests that Mn replacement by Ni into the α-MnO2 lattice (site A) occurs up to approximately 5% of the total Mn content, while further increasing Ni content promotes the nucleation of separate Ni phases (site B). XAS and XRD show that the introduction of sites A and B have a negligible effect on the overall Mn oxidation state and bonding characteristics, while very subtle changes in the XPS spectra appear to suggest changes in the electronic configuration upon Ni incorporation into the α-MnO2 lattice. On the other hand, changes in the electronic structure promoted by site A have a significant impact in the pseudocapacitive responses obtained by cyclic voltammetry in KOH solution at pH 13, revealing the appearance of Mn 3d orbitals at the energy (potential) range relevant to the ORR. The evolution of Mn 3d upon Ni replacement significantly increases the catalytic activity of α-MnO2 toward the ORR. Interestingly, the formation of segregated Ni phases (site B) leads to a decrease in the ORR activity while increasing the OER rate.

Dataset Information

Mechanochemical synthesis of Li?MnO? shell/LiMO? (M = Ni, Co, Mn) core-structured nanocomposites for lithium-ion batteries.

Publications

Mechanochemical synthesis of Li₂MnO₃ shell/LiMO₂ (M = Ni, Co, Mn) core-structured nanocomposites for lithium-ion batteries.

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