Lithium ionic diffusion in lithium cobalt oxides prepared by mechanical milling

Nakamura, Kōichi; Hirano, Hiroshi; Nishioka, Daisuke; Michihiro, Yoshitaka; Moriga, Toshihiro

doi:10.1016/j.ssi.2008.04.012

Cited by 10 publications

(7 citation statements)

References 8 publications

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“…So, one can expect modifications of the surface properties between samples LiCoU, LiCoU45, and LiCoU45‐700 since their specific surface areas are 0.5, 22, and 2 m 2 g −1 , respectively. Several works examined the interaction between the LiCoO 2 electrodes and water through different analytical and theoretical methods: density functional theory calculations (DFT), microcalorimetry in conjunction with a vapor dosing system, X‐ray photoelectron spectroscopy (XPS), synchrotron XPS, and X‐ray absorption near edge structure. It has been documented that, under normal conditions, “defect‐free” LiCoO 2 surfaces have very weak interaction with water, whereas surface defects in layer damaged LiCoO 2 structures can strongly increase this interaction .…”

Section: Resultsmentioning

confidence: 99%

Water‐Based Paintable LiCoO₂Microelectrodes: A High‐Rate Li‐Ion Battery Free of Conductive and Binder Additives

Martínez

Exantus

Dallel

et al. 2019

Adv Materials Technologies

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A simple, low‐cost, and environmentally friendly water‐based colloidal spray‐painting process is developed to obtain mechanically stable microelectrodes of pure LiCoO2 on stainless steel disks, which display reversible high‐rate discharge capacity and good cyclability. By using a simple nanostructuring process with commercially available LiCoO2, the use of dispersant, conductive, and binder additives during the electrode preparation is completely avoided. The nanostructuring approach is based on: i) planetary ball milling and annealing of LiCoO2 microparticles and ii) LiCoO2 surface modification through dissociative H2O adsorption during contact with air‐ and water‐based colloid preparation. The coating technique involves: i) water‐based colloid preparation, ii) spray‐coating, and iii) post‐treatment (drying and calcination) processes. The effects of particle size distribution, shape, crystallinity, specific surface area, and LiCoO2 surface modification on the electrode architecture (roughness, thickness, packing density, and porosity) are studied, together with their impact on the final electrochemical performances of batteries assembled with such a LiCoO2 electrode.

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Section: Resultsmentioning

confidence: 99%

Water‐Based Paintable LiCoO₂Microelectrodes: A High‐Rate Li‐Ion Battery Free of Conductive and Binder Additives

Martínez

Exantus

Dallel

et al. 2019

Adv Materials Technologies

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“…The difference found is attributed to two different hexagonal phases. Further investigations by Nakamura et al on lithium-ion migration in ball-milled LCO powder by complex resistivity measurements and NMR yielded activation energies between 0.29 and 0.36 eV, depending on the milling time.…”

Section: Introductionmentioning

confidence: 99%

Lithium-Ion Diffusion in Near-Stoichiometric Polycrystalline and Monocrystalline LiCoO₂

et al. 2023

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Lithium-metal-oxide-based cathode materials like LiCoO2 are an essential part of lithium-ion batteries, which are intensively researched and continuously improved. For a basic understanding of kinetic processes that control lithium incorporation and removal into/from electrodes, the lithium-ion transport in the cathode material is of high relevance. This concerns lithium diffusivities, as well as defect structures, transport mechanisms, and confined diffusion paths, such as grain boundaries. In the present study, lithium tracer self-diffusion is investigated by means of isotope exchange and secondary ion mass spectrometry in polycrystalline sintered bulk samples of stoichiometric LiCoO2 with an average grain size of about 70 nm and in single crystalline LiCoO2 in the ab-plane and c-axis in the temperature range between 200 and 700 °C. For the polycrystals, we found an activation enthalpy of ΔH = 0.75 eV. In the single crystal, the lithium-ion diffusivities along the ab-plane are identical to the diffusivities in polycrystalline LiCoO2. This indicates that diffusion along grain boundaries is similar to bulk diffusion and does not play a dominating role for the overall lithium-ion migration. Along the c-axis, diffusivities are some orders of magnitude lower, but only a slightly higher activation energy of 0.94 eV is found. This provides the experimental evidence of the often-claimed sluggish lithium diffusion along the c-axis. We suggest that lithium diffusion along the c-axis is most likely determined by fast diffusion in the ab-plane and a slow transfer of lithium ions across the CoO2 layers.

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“…In contrast, the analogous investigations on layered alkali metal oxides ( e.g ., titanates, niobates) are more limited despite their diverse compositions/structures, which provide another dimension for defect engineering and property tuning. It is known that the mechanical treatment leads to the change of unit-cell parameters, ,, generation of active surfaces and defects, , elemental redistributions, , phase transformation, or amorphization. ,− Accordingly, structural and compositional characterizations across multiple length scales ( i.e ., local, long-range, and nano/micro) are vital for a better understanding of the processes taking place during such treatments. An exploration of the chemical/physical properties of the resulting materials is also worthwhile.…”

Section: Introductionmentioning

confidence: 99%

Structural and Compositional Characteristics of Ball-Milled Lepidocrocite Alkali Titanate and the Correlation to Its Surface Acidic–Basic Properties

et al. 2021

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The studies on mechanical treatments of layered alkali metal oxides are limited despite their diverse compositions/ structures and potential for property tuning. In this work, we vibratory mill Cs 0.7 Zn 0.35 Ti 1.65 O 4 , K 0.8 Zn 0.4 Ti 1.6 O 4 , and Cs 2 Ti 6 O 13 for up to 4 h, during which the lepidocrocite-type structure and the plate-like morphology are well preserved. X-ray diffraction (XRD) indicates a tiny (≤0.6 Å) interlayer expansion accompanied by the enhancement of the preferred orientation along the stacking direction. Chemical analyses across multiple length scales suggest Cs deintercalation, elemental redistributions, and bulk-to-surface (or crystal edge) Cs migration. This ball-milling-induced Cs-rich moiety partially blocks the surface acid sites, although the solids still show a dominating acidic character. The ball-milled samples Cs 0.7−p Zn 0.35−q Ti 1.65 O 4−δ contain vacancies between the sheets (p) and at the sheets (q and δ). It is deduced from Sanderson's electronegativity equalization principle and experimentally verified by Xray photoelectron spectroscopy (XPS) that ball milling increases (decreases) the partial charge at the surface acidic Ti 4+ /Zn 2+ (basic O 2− ) sites. These nonporous solids (≤20 m 2 •g −1 ) contain water sorbed on the external surface as high as 1.1 mol•mol −1 , which is comparable to that in a water-intercalated sample. Our work expands the current understanding of the reactivity vs robustness in layered alkali titanates under physically demanding conditions, complementing knowledge gathered via the soft chemistry approach.

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Lithium ionic diffusion in lithium cobalt oxides prepared by mechanical milling

Cited by 10 publications

References 8 publications

Water‐Based Paintable LiCoO₂Microelectrodes: A High‐Rate Li‐Ion Battery Free of Conductive and Binder Additives

Water‐Based Paintable LiCoO₂Microelectrodes: A High‐Rate Li‐Ion Battery Free of Conductive and Binder Additives

Lithium-Ion Diffusion in Near-Stoichiometric Polycrystalline and Monocrystalline LiCoO₂

Structural and Compositional Characteristics of Ball-Milled Lepidocrocite Alkali Titanate and the Correlation to Its Surface Acidic–Basic Properties

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Lithium ionic diffusion in lithium cobalt oxides prepared by mechanical milling

Cited by 10 publications

References 8 publications

Water‐Based Paintable LiCoO2Microelectrodes: A High‐Rate Li‐Ion Battery Free of Conductive and Binder Additives

Water‐Based Paintable LiCoO2Microelectrodes: A High‐Rate Li‐Ion Battery Free of Conductive and Binder Additives

Lithium-Ion Diffusion in Near-Stoichiometric Polycrystalline and Monocrystalline LiCoO2

Structural and Compositional Characteristics of Ball-Milled Lepidocrocite Alkali Titanate and the Correlation to Its Surface Acidic–Basic Properties

Contact Info

Product

Resources

About

Water‐Based Paintable LiCoO₂Microelectrodes: A High‐Rate Li‐Ion Battery Free of Conductive and Binder Additives

Water‐Based Paintable LiCoO₂Microelectrodes: A High‐Rate Li‐Ion Battery Free of Conductive and Binder Additives

Lithium-Ion Diffusion in Near-Stoichiometric Polycrystalline and Monocrystalline LiCoO₂