Combined wet milling and heat treatment in water vapor for producing amorphous to crystalline ultrafine Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte particles

Kozawa, Takahiro

doi:10.1039/d1ra02039k

Cited by 13 publications

(8 citation statements)

References 53 publications

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“…The bands observed between 600 and 700 cm –1 in the FTIR spectra (Figure i) were the (TiO 6 ) stretching vibrations in LATP and the bands at 900–1300 cm –1 were the chemical bonds between P and O (Figure i). The FT-IR spectra also confirmed there was not any organic species adsorbed on the LATP particle surface. , …”

Section: Resultsmentioning

confidence: 65%

A Multiscale Hollow Spherical LATP Active Filler Improves Conductivity and Mechanical Strength in Composite Solid Electrolytes for Li Batteries

2022

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Polymer-based electrolytes would be ideal for all-solid-state Li metal batteries due to the superior processability of polymers and their ability to make good interfaces with electrode materials. However, polymer electrolytes have lower room temperature Li+ conductivities than desired. Composite solid electrolytes (CSEs) containing both polymer and ceramic filler have far greater conductivity than the polymer alone, and it is believed this is due to conduction paths along the polymer–ceramic interface. A strategy often pursued for increasing conductivity has been to engineer the filler with a high aspect ratio shape, such as nanorods or interconnected nanofibers. In this work we employ a multiscale hollow spherical filler, which is not directional but achieves similar conductivity to those with fibrous morphologies. The hollow spherical shape avoids agglomeration and provides continuous Li+ transfer channels. We fabricated multiscale hollow spherical ceramic Li1.3Al0.3Ti1.7(PO4)3 (LATP) nanoparticles for use in a poly(ethylene oxide) (PEO) matrix. This network also provided structural support and enhanced the mechanical properties of the polymer matrix, which is important for a battery electrolyte. The resulting CSE membrane had room temperature ionic conductivity of 1.64 × 10–4 S/cm. Li/Li symmetric cells using this CSE showed no short circuits for 500 h cycling at a current density 0.1 mA cm–2. Control cells using standard LATP powder showed higher overpotential and dendrite failure, as did the polymer membrane with no LATP.

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Section: Resultsmentioning

confidence: 65%

A Multiscale Hollow Spherical LATP Active Filler Improves Conductivity and Mechanical Strength in Composite Solid Electrolytes for Li Batteries

2022

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“…Accordingly, the spectra for LATP particles obtained from LF-FSP and in situ precipitation overlap within experimental error, confirming that the two synthesis routes yield the same amorphous material. Both spectra show two broad bands, i.e., 600–800 and 900–1300 cm –1 , associated with Ti–O and P–O stretching modes, respectively . For PEO, peaks located at 2876, 1465, and 1341 cm –1 are attributed to C–H stretching, scissoring, and wagging modes, respectively.…”

Section: Resultsmentioning

confidence: 99%

Contiguous High-Mobility Interphase Surrounding Nano-Precipitates in Polymer Matrix Solid Electrolyte

Wang

Kieffer

2022

ACS Appl. Mater. Interfaces

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We establish that an interfacial region develops around amorphous Li1.3Al0.3Ti1.7(PO4)3 (LATP) nanoparticles in a poly(ethylene oxide) (PEO), which exhibits a 30 times higher Li+ mobility than the polymer matrix. To take advantage of this gain throughout the material, nanoparticles must be uniformly dispersed across the matrix, so that the interphase formation is minimally blocked by LATP particle agglomeration. This is achieved using a water-based in situ precipitation method, carefully controlling the temperature schedule during processing. A maximum conductivity of 3.80 × 10–4 S cm–1 at 20 °C for an ethylene oxide to Li ratio of 10 is observed at 25 wt % (12.5 vol %) particle loading, as predicted by our tri-phase model. Comparative infrared spectroscopy reveals softening and broadening of the C–O–C stretching modes, reflecting increased disorder in the polymer backbone that is consistent with opening passageways for cation migration. A transition state theory-based approach for analyzing the temperature dependence of the ionic conductivity reveals that thermally activated processes within the interphase benefit more from higher activation entropy than from the decrease in activation enthalpy. The lithium infusion from LATP particles is small, and the charge carriers tend to concentrate in a space-charge configuration near the particle/polymer interface.

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“…These laminar interconnect structure greatly reduced the porosity of the ceramic pellet and brought the particles into close contact with each other in multiple dimensions; thus, the relative density was over 90% after sintering at 750 °C. The appearance of this laminar interpenetrated structure in LATP-C was mainly due to that (a) the disorder amorphous phase in the LATP-C crystals with high free energy effectively promoted mass transfer and could be regarded as “binder” connect adjacent grain during the sintering process, which led to further grain fusion, blurred the grain boundaries, and decreased the threshold for intercrystalline fusion, , therefore accelerated densification even with sintering at low temperatures; and (b) the presence of small amounts of a LiTiPO 5 second phase, which prevented the growth of anomalous grains, promoted homogenization of the structure and facilitated densification of the gains. , As the temperature was increased to 850 °C [Figure (b3)], the particles began to grow, and the interconnected grains gradually evolved independently into polyhedra. At this time, the particles were more closely stacked and still had good contact with each other, and the porosity was lower than that seen after sintering at 750 °C, so the relative density was also improved to 92%.…”

Section: Resultsmentioning

confidence: 99%

Facile Route to Synthesize a Highly Sinterable Li_1.3Al_0.3Ti_1.7(PO₄)₃ Solid Electrolyte

Luo,

Zhao,

Zhang

et al. 2024

ACS Appl. Mater. Interfaces

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NASICON-type Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 (LATP) is a widely used solid electrolyte in solid-state lithium batteries, owing to its excellent chemical stability against moisture and high total ionic conductivity. However, traditionally, densification of LATP has been achieved through a high-temperature sintering process (approximately 1000 °C) owing to its poor sinterability. Herein, we report a facile synthesis route to obtain highly sinterable LATP solid electrolyte using tetrabutyl titanate (C 16 H 36 O 4 Ti) as the titanium source and incorporating the traditional solid-state reaction method. The synthetic LATP powder mixed with a low ratio of LiTiPO 5 exhibited a hybrid crystalline−amorphous phase structure, which facilitated grain fusion, promoted structural homogeneity, and facilitated structural densification under low-temperature sintering. The sintered LATP pellet, which exhibited an interconnected structure and indistinct grain boundaries, achieved a relative density of >90% and an ionic conductivity of 0.667 mS/cm at a sintering temperature of only 750 °C. Additionally, we systematically studied and demonstrated the synthesis reaction mechanism, sintering behavior, and ionic diffusion kinetics of LATP electrolytes. Our study paves the way for synthesizing highly sinterable LATP solid electrolytes using a simple, additive-free, and cost-effective method.

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Combined wet milling and heat treatment in water vapor for producing amorphous to crystalline ultrafine Li_1.3Al_0.3Ti_1.7(PO₄)₃ solid electrolyte particles

Abstract: The preparation of ultrafine particles through combined wet planetary ball milling and heat treatment in water vapor contributes to the fabrication of extensive composite electrodes with solid electrolytes for bulk-type all-solid-state batteries.

Cited by 13 publications

References 53 publications

A Multiscale Hollow Spherical LATP Active Filler Improves Conductivity and Mechanical Strength in Composite Solid Electrolytes for Li Batteries

A Multiscale Hollow Spherical LATP Active Filler Improves Conductivity and Mechanical Strength in Composite Solid Electrolytes for Li Batteries

Contiguous High-Mobility Interphase Surrounding Nano-Precipitates in Polymer Matrix Solid Electrolyte

Facile Route to Synthesize a Highly Sinterable Li_1.3Al_0.3Ti_1.7(PO₄)₃ Solid Electrolyte

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Combined wet milling and heat treatment in water vapor for producing amorphous to crystalline ultrafine Li1.3Al0.3Ti1.7(PO4)3 solid electrolyte particles

Abstract: The preparation of ultrafine particles through combined wet planetary ball milling and heat treatment in water vapor contributes to the fabrication of extensive composite electrodes with solid electrolytes for bulk-type all-solid-state batteries.

Cited by 13 publications

References 53 publications

A Multiscale Hollow Spherical LATP Active Filler Improves Conductivity and Mechanical Strength in Composite Solid Electrolytes for Li Batteries

A Multiscale Hollow Spherical LATP Active Filler Improves Conductivity and Mechanical Strength in Composite Solid Electrolytes for Li Batteries

Contiguous High-Mobility Interphase Surrounding Nano-Precipitates in Polymer Matrix Solid Electrolyte

Facile Route to Synthesize a Highly Sinterable Li1.3Al0.3Ti1.7(PO4)3 Solid Electrolyte

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Product

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About

Combined wet milling and heat treatment in water vapor for producing amorphous to crystalline ultrafine Li_1.3Al_0.3Ti_1.7(PO₄)₃ solid electrolyte particles

Facile Route to Synthesize a Highly Sinterable Li_1.3Al_0.3Ti_1.7(PO₄)₃ Solid Electrolyte