Low-temperature growth of idiomorphic cubic-phase Li7La3Zr2O12crystals using LiOH flux

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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“…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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“…On the basis of the above, we have explored the flux growth of battery materials; the liquid-phase crystal growth technique can produce high-quality idiomorphic crystals with no thermal strains. ,− Our group has reported the flux growth of idiomorphic crystals of LiCoO 2 , Li 4 Ti 5 O 12 , LiMn 2 O 4 , LiFePO 4 , NCM, Li 5 La 3 Nb 2 O 12 , Li 7 La 3 Zr 2 O 12 , and Li 5 La 3 Ta 2 O 12 , all of which have potential as Li + -conducting materials. − The growth mechanisms of these crystals in fluxes of molten salts can be classified into three categories. First, supersaturation by the evaporation of flux is a strong driving force for crystal growth.…”

Section: Introductionmentioning

confidence: 99%

Growth Manner of Octahedral-Shaped Li(Ni_1/3Co_1/3Mn_1/3)O₂ Single Crystals in Molten Na₂SO₄

Kimijima

Zettsu

Teshima

2016

Crystal Growth & Design

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The synthesis of shape-controlled crystals has been a highly attractive research topic in modern materials chemistry. In this work, the growth of Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 (NCM) crystals in molten sulfate or carbonate salts (flux) at 1000 °C was systematically studied under various conditions. In situ X-ray diffraction during the growth and thermogravimetry-differential thermal analysis revealed that the growth of NCM crystals in the flux was controlled by liquid-phase sintering according to the Ostwald ripening principle. We studied the effect of Na + in the flux on the crystal shapes and found that Na + was critical in forming octahedral crystals with well-developed facets. Single crystals with well-developed facets were obtained homogeneously from Na 2 SO 4 , while truncated polyhedral crystals of smaller size were obtained from Li 2 SO 4 . The shape-controlled NCM crystals showed discharge capacities approaching 160 mAh g −1 in the operating voltage range of 2.8−4.4 V vs Li/Li + under a low current density of 0.1 C, independent of flux composition. This suggests that the Li + and transition-metal ions in the individual NCM crystals were highly ordered into hexagonal arrangements belonging to the R3̅ m space group, without cation mixing.

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“…The flux method, a liquid-phase single crystal growth technique used to prepare inorganic materials, is a promising approach for controlling the final shape of single crystals and to lower reaction temperatures. , Awaka et al and Tietz et al reported preparing Li 7 La 3 Zr 2 O 12 single crystals at around 1000 °C in two steps using Li 2 CO 3 flux. Kimijima et al . successfully grew Li 7 La 3 Zr 2 O 12 single crystals at 700 °C using LiOH flux in one step.…”

Section: Introductionmentioning

confidence: 99%

“…12,13 Awaka et al 14 and Tietz et al 15 reported preparing Li 7 La 3 Zr 2 O 12 single crystals at around 1000 °C in two steps using Li 2 CO 3 flux. Kimijima et al 16 successfully grew Li 7 La 3 Zr 2 O 12 single crystals at 700 °C using LiOH flux in one step. These results indicated that alkali metal hydroxide fluxes were effective for the crystal growth of mixed oxides at low temperatures, due to their low melting point and high solubility behavior.…”

Section: ■ Introductionmentioning

confidence: 99%

Unique Growth Manner of Li₅La₃Ta₂O₁₂ Crystals from Lithium Hydroxide Flux at Low Temperature

Xiao¹,

Wagata²,

Hayashi³

et al. 2015

Crystal Growth & Design

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Garnet-type Li 5+x Ln 3 M IV 2-y M V y O 12+z (x, y = 0-2, z = 0-1; Ln = La, Pr, Nd; M = Ta, Zr, Nb) compounds are promising Li-ion conducting solid electrolytes, but their growth mode is still unclear. Herein, the analysis of the low-temperature growth of idiomorphic Li 5 La 3 Ta 2 O 12 single crystals as a function of holding temperature and time, cooling rate, flux type, and solute concentration revealed a unique growth mode. Li 5 La 3 Ta 2 O 12 crystals were grown at 500 °C from LiOH flux, and transformed into Li 7 La 3 Ta 2 O 13 at 700 °C. Pseudo-perovskite-type LiLa 2 TaO 6 phase, initially formed during the holding at 500 °C, was efficiently transformed into Li 5 La 3 Ta 2 O 12 phase with increasing holding time. The growth of Li 5 La 3 Ta 2 O 12 single crystals was independent of the cooling rate, but was affected by flux type and solute concentration. A low solute concentration (1 or 5 mol%) was the key to obtain well-dispersed and idiomorphic single crystals. The optimum growth conditions involved a holding temperature of 500 °C, a solute concentration of 1 or 5 mol%, and a holding time of 10 h. These findings indicate that formation and growth of Li 5 La 3 Ta 2 O 12 single crystals are not only controlled by a general flux growth process, but also involve chemical reactions between solutes and LiOH flux. Finally, high-resolution TEM and selected area diffraction images highlighted products with high crystallinity and well-developed {110} and {211} facets. ABSTRACT Garnet-type Li 5+x Ln 3 M IV 2-y M V y O 12+z (x, y = 0-2, z = 0-1; Ln = La, Pr, Nd; M = Ta, Zr, Nb) compounds are promising Li-ion conducting solid electrolytes, but their growth mode is still unclear. Herein, the analysis of the low-temperature growth of idiomorphic Li 5 La 3 Ta 2 O 12 single crystals as a function of holding temperature and time, cooling rate, flux type, and solute concentration revealed a unique growth mode. Li 5 La 3 Ta 2 O 12 crystals were grown at 500 °C from LiOH flux, and transformed into Li 7 La 3 Ta 2 O 13 at 700 °C. Pseudo-perovskite-type LiLa 2 TaO 6 phase, initially formed during the holding at 500 °C, was efficiently transformed into Li 5 La 3 Ta 2 O 12 phase with increasing holding time. The growth of Li 5 La 3 Ta 2 O 12 single crystals was independent of the cooling rate, but was affected by kind of flux and solute concentration. A low solute concentration (1 or 5 mol%) was the key to obtain well-dispersed and idiomorphic single crystals. The optimum growth conditions involved a holding temperature of 500 °C, a solute concentration of 1 or 5 mol%, and a holding time of 10 h. These findings indicate that formation and growth of Li 5 La 3 Ta 2 O 12 single crystals are not only controlled by a general flux growth process, but also involve chemical reactions between solutes and LiOH flux. Finally, high-resolution TEM and selected area diffraction images highlighted products with high crystallinity and well-developed {110} and {211} facets.

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Low-temperature growth of idiomorphic cubic-phase Li₇La₃Zr₂O₁₂crystals using LiOH flux

Cited by 6 publications

References 36 publications

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

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

Growth Manner of Octahedral-Shaped Li(Ni_1/3Co_1/3Mn_1/3)O₂ Single Crystals in Molten Na₂SO₄

Unique Growth Manner of Li₅La₃Ta₂O₁₂ Crystals from Lithium Hydroxide Flux at Low Temperature

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Low-temperature growth of idiomorphic cubic-phase Li7La3Zr2O12crystals using LiOH flux

Cited by 6 publications

References 36 publications

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

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

Growth Manner of Octahedral-Shaped Li(Ni1/3Co1/3Mn1/3)O2 Single Crystals in Molten Na2SO4

Unique Growth Manner of Li5La3Ta2O12 Crystals from Lithium Hydroxide Flux at Low Temperature

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Low-temperature growth of idiomorphic cubic-phase Li₇La₃Zr₂O₁₂crystals using LiOH flux

Growth Manner of Octahedral-Shaped Li(Ni_1/3Co_1/3Mn_1/3)O₂ Single Crystals in Molten Na₂SO₄

Unique Growth Manner of Li₅La₃Ta₂O₁₂ Crystals from Lithium Hydroxide Flux at Low Temperature