An official website of the United States government
Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) is a promising inorganic solid electrolyte due to its high Li + conductivity and electrochemical stability for all-solid-state batteries. Mechanical characterization of LLZTO is limited by the synthesis of the condensed phase. Here we systematically measure the elastic modules, hardness, and fracture toughness of LLZTO polycrystalline pellets of different densities using the customized environmental nanoindentation. The LLZTO samples are sintered using the hot-pressing method with different amounts of Li 2 CO 3 additives, resulting in the relative density of the pellets varying from 83% to 98% and the largest grain size of 13.21 ± 5.22 μm. The mechanical properties show a monotonic increase as the sintered sample densifies, elastic modulus and hardness reach 158.47 ± 10.10 GPa and 11.27 ± 1.38 GPa, respectively, for LLZTO of 98% density. Similarly, fracture toughness increases from 0.44 to 1.51 MPa⋅m 1/2 , showing a transition from the intergranular to transgranular fracture behavior as the pellet density increases. The ionic conductivity reaches 4.54 × 10 −4 S/cm in the condensed LLZTO which enables a stable Li plating/stripping in a symmetric solid-state cell for over 100 cycles. This study puts forward a quantitative study of the mechanical behavior of LLZTO of different microstructures that is relevant to the mechanical stability and electrochemical performance of all-solid-state batteries.
more »
« less
Thermal properties and lattice anharmonicity of Li-ion conducting garnet solid electrolyte Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12
This work reports the thermal properties of garnet electrolyte LLZTO. The aged LLZTO exhibits an enhanced thermal conductivity, attributed to the formation of Li2CO3.
more »
« less
- PAR ID:
- 10541585
- Publisher / Repository:
- Royal Society of Chemistry
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 12
- Issue:
- 29
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 18248 to 18257
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Tantalum‐doped lithium lanthanum zirconate garnet (Li7−xLa3Zr2−xTaxO12[LLZTO]) has received interest as a solid electrolyte for solid‐state lithium batteries due to its good electrochemical properties and ionic conductivity. However, the source of discrepancies for reported values of ionic conductivity in nominally or nearly equivalent compositions of LLZTO is not completely clear. Herein, synthesis‐related factors that may contribute to the differences in performance of garnet electrolytes are systematically characterized. The conductivity of samples with composition Li6.4La3Zr1.4Ta0.6O12prepared by various methods including solid‐state reaction (SSR), combustion, and molten salt synthesis is compared. Varying levels of elemental inhomogeneity, comprising a variation in Ta and Zr content on the level of individual LLZTO particles, are identified. The elemental inhomogeneity is found to be largely preserved even after high‐temperature sintering and correlated with reduced ionic conductivity. It is shown that the various synthesis and processing‐related variables in each of the preparation methods play a role in these compositional variations, and that even LLZTO synthesized via conventional, high‐temperature SSR can exhibit substantial variability in local composition. However, by improving reagent mixing and using LLZTO powder with low agglomeration and small particle size distribution, the compositional uniformity, and hence, ionic conductivity, of sintered garnet electrolytes can be improved.more » « less
-
Abstract The preparation of 0.58 Li2S + 0.315 SiS2+ 0.105 LiPO3glass, and the impacts of polysulfide and P1Pdefect structure impurities on the glass transition temperature (Tg), crystallization temperature (Tc), working range (ΔT≡ Tc‐ Tg), fragility index, and the Raman spectra were evaluated using statistical analysis. In this study, 33 samples of this glass composition were synthesized through melt‐quenching. Thermal analysis was conducted to determine the glass transition temperature, crystallization temperature, working range, and fragility index through differential scanning calorimetry. The quantity of the impurities described above was determined through Raman spectroscopy peak analysis. Elemental sulfur was doped into a glass to quantify the wt% sulfur content in the glasses. Linear regression analysis was conducted to determine the impact of polysulfide impurities and P1Pdefect impurities on the thermal properties. Polysulfide impurities were found to decrease theTgat rate of nearly 12°C per 1 wt% increase in sulfur concentration. The sulfur concentration does not have a statistically significant impact on the other properties (α = 0.05). The P1Pdefect structure appears to decrease the resistance to crystallization of the glass by measurably decreasing the working range of the glasses, but further study is necessary to fully quantify and determine this.more » « less
-
Abstract Solid state lithium metal batteries using garnet solid electrolytes such as LLZTO (Li6.4La3Zr1.5Ta0.5O12) promise substantial improvements in energy density and safety. However, practical implementation is hindered by lithium dendrite penetration at high current densities. Recent work shows that internal electrochemically induced mechanical stresses are large enough to propagate lithium dendrites and subsequently fracture solid electrolytes. This study builds on this understanding and demonstrates that stress‐driven dendrite propagation can be controlled via deflection at weakly bonded internal interfaces. This approach, based on a fracture‐mechanics analysis of multilayered composites, is investigated with a variety of interlayer materials that are embedded into LLZTO. The viability and effectiveness of dendrite deflection are most clearly evident with reduced graphene oxide where the critical current density increased from 0.6 to 3.8 mA cm−2. In this material, both the weak interface with LLZTO and the mixed ionic–electronic conducting nature of the interlayer appear to contribute to the improved performance. Additional insight into the mechanics of multilayered electrolytes is also obtained with finite element modeling. The overall results present a promising proof‐of‐concept demonstration along with important generalized design guidelines for creating multilayered solid electrolyte architectures that can enable high‐performance solid‐state batteries.more » « less
-
Abstract Thermal transport in amorphous lithium‐sulfur (a‐LixS) is systematically investigated using molecular dynamics and the contributions from different types of heat carriers are quantitatively evaluated. In general, the thermal conductivity (TC) ofa‐LixS changes largely by varying the concentration (x) of Li ions ina‐LixS. Interestingly, the TC ofa‐LixS shows three distinct regimes of dependence on Li concentration. For low Li concentration (x = 0.4–1.2), the TC grows slowly, followed by a rapid increase in TC for medium Li concentration (x = 1.2–1.6), where the growth rate is three times that of the first regime, and finally, the TC is independent of Li concentration (x = 1.6–2.0). The TC enhancement in the first and second regimes is mainly attributed to propagating and non‐propagating vibrational modes ina‐LixS, respectively. In contrast, the stable thermal transport regime is governed by the competition between propagating and non‐propagating phonons. These investigations provide quantitative TC data of various polysulfides for shuttling analysis, and a fundamental understanding of the thermal transport mechanism of complexa‐LixS structures, which is beneficial for the rational design of thermal management of Li‐S batteries.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d4ta02264e
