Flux growth of patterned LiCoO<sub>2</sub> crystal arrays directly on a Pt substrate in molten LiNO<sub>3</sub>

Yoda, T.; Zettsu, Nobuyuki; Onodera, Hitoshi; Mizuno, Yusuke; Kondo, Hitoshi; Teshima, Katsuya

doi:10.1039/c5ra17459g

Cited by 8 publications

(6 citation statements)

References 36 publications

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“…S1). Very similar results were observed in our previous reports that describe the formation of hollow-structured LiCoO 2 , LiMn 2 O 4 , and LiNi 0.5 Co 0.2 Mn 0.3 O 2 from the conversion of electrodeposited Co, Mn, and stacked Ni/Co/Mn dots in molten salts at high temperatures, respectively 23,24 . Based on these results, the oxide formation on the Nb substrate could limit the reaction kinetics, since the amount of dissolved oxygen is normally small in the molten salts.…”

Section: Resultssupporting

confidence: 91%

Thin and Dense Solid-solid Heterojunction Formation Promoted by Crystal Growth in Flux on a Substrate

Zettsu

Shiiba

Onodera

et al. 2018

Sci Rep

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In this work, we demonstrate the direct growth of cubic Li5La3Nb2O12 crystal layer on the LiCoO2 substrate through the conversion of ultra-thin Nb substrate in molten LiOH flux. The initial thickness of the Nb layer determines that of the crystal layer. SEM and TEM observations reveal that the surface is densely covered with well-defined polyhedral crystals. Each crystal is connected to neighboring ones through the formation of tilted grain boundaries with Σ3 (2–1–1) = (1–21) symmetry which show small degradation in lithium ion conductivity comparing to that of bulk. Furthermore, the sub-phase formation at the interface is naturally mitigated during the growth since the formation of Nb2O5 thin film limits the whole reaction kinetics. Using the newly developed stacking approach for stacking solid electrolyte layer on the electrode layer, the grown crystal layer could be an ideal ceramic separator with a dense thin-interface for all-solid-state batteries.

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Section: Resultssupporting

confidence: 91%

Thin and Dense Solid-solid Heterojunction Formation Promoted by Crystal Growth in Flux on a Substrate

Zettsu

Shiiba

Onodera

et al. 2018

Sci Rep

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“…The LiNi 0.5 Mn 1.5 O 4− δ crystals used were prepared by the flux growth method171819202122. As shown in Fig.…”

Section: Resultsmentioning

confidence: 99%

Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries

Zettsu

Kida

Uchida

et al. 2016

Sci Rep

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We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4−δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4−δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn3+ from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF.

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“…Very recently, we proposed the extension of the flux growth concept to create a structure in which high-quality LiCoO 2 crystals were obtained from Co metal in molten LiCl (flux). 29 Specifically, a micro-sized hemispherical Co dot, which was directly deposited onto a Pt substrate using electroplating, reacted with LiNO 3 flux causing the formation of high-quality LiCoO 2 crystals. Time-dependent scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses suggested that the conversion process kinetics involved different reactions, including low LiCoO 2 phase formation leading to hollow structures based on the Kirkendall effect [30][31][32][33] and, also, rapid growth of LiCoO 2 crystals that promoted anisotropic growth.…”

Section: Introductionmentioning

confidence: 99%

Growth of hollow-structured LiMn₂O₄crystals starting from Mn metal in molten KCl through the microscale Kirkendall effect

et al. 2016

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Hollow-structured LiMn 2 O 4 crystals are grown in molten KCl (flux) for the first time via an oxidation reaction of metallic Mn followed by a lithiation reaction. Characterization of the formation process, which is achieved using thermogravimetric differential thermal analysis, X-ray diffraction, and scanning electron microscopy observation, reveals that the hollow structures are formed via a mechanism analogous to the microscale Kirkendall effect, which results from the difference between the solid-state diffusion rates of the core materials and the rate of O 2 diffusion through the shell at elevated temperatures occurring during oxidation. Interestingly, the development of well-defined crystal facets is observed on the surfaces of the LiMn 2 O 4 crystals, implying that the crystal growth is driven by supersaturation in the same manner as the flux growth. We also examine two possible approaches to reduce the volume of the inner space in the crystal: crystal growth under O 2 flow for enhancement of the O 2 diffusion and insertion of a Co and Ni layer between Mn and the substrate to induce the formation of the LiNi 1/3 Co 1/3 Mn 1/3 O 2 phase.

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Flux growth of patterned LiCoO₂ crystal arrays directly on a Pt substrate in molten LiNO₃

Abstract: We demonstrate a new way to prepare hollow-structured LiCoO2 crystals directly on a Pt substrate for the first time through a combination of semi-additive electrodeposition of a Co core and subsequent flux growth in molten LiNO3.

Cited by 8 publications

References 36 publications

Thin and Dense Solid-solid Heterojunction Formation Promoted by Crystal Growth in Flux on a Substrate

Thin and Dense Solid-solid Heterojunction Formation Promoted by Crystal Growth in Flux on a Substrate

Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries

Growth of hollow-structured LiMn₂O₄crystals starting from Mn metal in molten KCl through the microscale Kirkendall effect

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Flux growth of patterned LiCoO2 crystal arrays directly on a Pt substrate in molten LiNO3

Abstract: We demonstrate a new way to prepare hollow-structured LiCoO2 crystals directly on a Pt substrate for the first time through a combination of semi-additive electrodeposition of a Co core and subsequent flux growth in molten LiNO3.

Cited by 8 publications

References 36 publications

Thin and Dense Solid-solid Heterojunction Formation Promoted by Crystal Growth in Flux on a Substrate

Thin and Dense Solid-solid Heterojunction Formation Promoted by Crystal Growth in Flux on a Substrate

Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries

Growth of hollow-structured LiMn2O4crystals starting from Mn metal in molten KCl through the microscale Kirkendall effect

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Flux growth of patterned LiCoO₂ crystal arrays directly on a Pt substrate in molten LiNO₃

Growth of hollow-structured LiMn₂O₄crystals starting from Mn metal in molten KCl through the microscale Kirkendall effect