Spatially resolved stoichiometry determination of Li7La3Zr2O12 solid-state electrolytes using LA-ICP-OES

Smetaczek, Stefan; Bonta, Maximilian; Wachter-Welzl, Andreas; Taibl, Stefanie; Wagner, Reinhard; Rettenwander, Daniel; Fleig, Jürgen; Limbeck, Andreas

doi:10.1039/d0ja00051e

Cited by 7 publications

(5 citation statements)

References 52 publications

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“…Thus, for sample x Ga=1.140 apfu, the content of Zr is slightly lower and that of Li slightly higher than expected, which is attributed to the 7 % La 2 Zr 2 O 7 pyrochlore secondary phase affecting overall structure and composition. The measured Zr deficit is a curious result, although decreased Zr content relative to target Ga‐LLZO composition has been reported elsewhere [33–36] . All reagent oxides (Li 2 CO 3 , La 2 O 3 , ZrO 2 , and Ga 2 O 3 ) were verified as phase‐pure prior to synthesis.…”

Section: Resultsmentioning

confidence: 54%

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li_7‐3xGa_xLa₃Zr₂O₁₂ Garnet‐Type Electrolytes

Birkner

Estes

et al. 2021

ChemSusChem

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One of the most promising electrolytes for all‐solid‐state lithium batteries is Li7La3Zr2O12. Previously, their thermodynamic stability, Li‐ion conductivity, and structural features induced by Ga‐doping have not been empirically determined or correlated. Here, their interplay was examined for Li7−3xGaxLa3Zr2O12 with target xGa=0, 0.25, 0.50, 0.75, and 1.00 atoms per formula unit (apfu). Formation enthalpies, obtained with calorimetry and found to be exothermic at all compositions, linearly decreased in stability with increased xGa. At dilute xGa substitution, the formation enthalpy curve shifted stepwise endothermically, and the conductivity increased to a maximum, coinciding with 0.529 Ga apfu. This correlated with percolation threshold analysis (0.558 Ga apfu). Further substitution (0.787 Ga apfu) produced a large decrease in the stability and conductivity due to a large increase in point defects and blocked Li‐migration pathways. At xGa=1.140 apfu, a small exothermic shift was related to defect cluster organization extending the Li hopping distance and decreased Li‐ion conductivity.

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Section: Resultsmentioning

confidence: 54%

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li_7‐3xGa_xLa₃Zr₂O₁₂ Garnet‐Type Electrolytes

Birkner

Estes

et al. 2021

ChemSusChem

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“…Furthermore, the elemental distribution of dopants in a single crystal is homogeneous compared to polycrystalline samples. [ 38 ] In the context of this study, the advantage lies foremost in the fact that a large single crystal could be produced. The starting materials Li 2 CO 3 (Alfa Aesar, 99.999%), La 2 O 3 (Fox Chemicals, 99.999%), Ga 2 O 3 (Fox Chemicals, 99.999%), and ZrO 2 (Merck, Optipur) were dried and then mixed with an excess of 10 wt% of Li 2 CO 3 .…”

Section: Methodsmentioning

confidence: 99%

The Electronic Conductivity of Single Crystalline Ga‐Stabilized Cubic Li₇La₃Zr₂O₁₂: A Technologically Relevant Parameter for All‐Solid‐State Batteries

Philipp

Gadermaier

Posch

et al. 2020

Adv Materials Inter

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The next‐generation of all‐solid‐state lithium batteries need ceramic electrolytes with very high ionic conductivities. At the same time a negligible electronic conductivity σeon is required to eliminate self‐discharge in such systems. A non‐negligible electronic conductivity may also promote the unintentional formation of Li dendrites, being currently one of the key issues hindering the development of long‐lasting all‐solid‐state batteries. This interplay is suggested recently for garnet‐type Li7La3Zr2O12 (LLZO). It is, however, well known that the overall macroscopic electronic conductivity may be governed by a range of extrinsic factors such as impurities, chemical inhomogeneities, grain boundaries, morphology, and size effects. Here, advantage of Czochralski‐grown single crystals, which offer the unique opportunity to evaluate intrinsic properties of a chemically homogeneous matrix, is taken to measure the electronic conductivity σeon. Via long‐time, high‐precision potentiostatic polarization experiments an upper limit of σeon in the order of 5 × 10−10 S cm−1 (293 K) is estimated. This value is by six orders of magnitude lower than the corresponding total conductivity σtotal = 10−3 S cm−1 of Ga‐LLZO. Thus, it is concluded that the high values of σeon recently reported for similar systems do not necessarily mirror intragrain bulk properties of chemically homogenous systems but may originate from chemically inhomogeneous interfacial areas.

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“…Details on the instrumental parameters used for the ICP-OES can be found in the supplementary information (Table S1). More information regarding the chemical analysis of LLZO via ICP-OES can be found elsewhere 26 .…”

Section: Llzo Synthesismentioning

confidence: 99%

Investigating the electrochemical stability of Li₇La₃Zr₂O₁₂ solid electrolytes using field stress experiments

et al. 2021

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Spatially resolved stoichiometry determination of Li₇La₃Zr₂O₁₂ solid-state electrolytes using LA-ICP-OES

Abstract: LA-ICP-OES in combination with matrix-matched calibration standards and proper signal normalization enables reliable laterally resolved stoichiometry determination of Al stabilized LLZO (Li7−3xAlxLa3Zr2O12) solid electrolytes.

Cited by 7 publications

References 52 publications

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li_7‐3xGa_xLa₃Zr₂O₁₂ Garnet‐Type Electrolytes

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li_7‐3xGa_xLa₃Zr₂O₁₂ Garnet‐Type Electrolytes

The Electronic Conductivity of Single Crystalline Ga‐Stabilized Cubic Li₇La₃Zr₂O₁₂: A Technologically Relevant Parameter for All‐Solid‐State Batteries

Investigating the electrochemical stability of Li₇La₃Zr₂O₁₂ solid electrolytes using field stress experiments

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Spatially resolved stoichiometry determination of Li7La3Zr2O12 solid-state electrolytes using LA-ICP-OES

Abstract: LA-ICP-OES in combination with matrix-matched calibration standards and proper signal normalization enables reliable laterally resolved stoichiometry determination of Al stabilized LLZO (Li7−3xAlxLa3Zr2O12) solid electrolytes.

Cited by 7 publications

References 52 publications

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li7‐3xGaxLa3Zr2O12 Garnet‐Type Electrolytes

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li7‐3xGaxLa3Zr2O12 Garnet‐Type Electrolytes

The Electronic Conductivity of Single Crystalline Ga‐Stabilized Cubic Li7La3Zr2O12: A Technologically Relevant Parameter for All‐Solid‐State Batteries

Investigating the electrochemical stability of Li7La3Zr2O12 solid electrolytes using field stress experiments

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Spatially resolved stoichiometry determination of Li₇La₃Zr₂O₁₂ solid-state electrolytes using LA-ICP-OES

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li_7‐3xGa_xLa₃Zr₂O₁₂ Garnet‐Type Electrolytes

Gallium‐Doping Effects on Structure, Lithium‐Conduction, and Thermochemical Stability of Li_7‐3xGa_xLa₃Zr₂O₁₂ Garnet‐Type Electrolytes

The Electronic Conductivity of Single Crystalline Ga‐Stabilized Cubic Li₇La₃Zr₂O₁₂: A Technologically Relevant Parameter for All‐Solid‐State Batteries

Investigating the electrochemical stability of Li₇La₃Zr₂O₁₂ solid electrolytes using field stress experiments