Investigation of Mg2+, Sc3+ and Zn2+ doping effects on densification and ionic conductivity of low-temperature sintered Li7La3Zr2O12 garnets

Jiang, Yue; Zhu, Xiaohong; Qin, Shiying; Ling, Ming’en; Zhu, Jiliang

doi:10.1016/j.ssi.2016.12.005

Cited by 61 publications

(28 citation statements)

References 25 publications

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“…In general, dense LLZO pellets are assembled in a two-step process, where the first step is the fabrication of the compact pellet through cold pressing and the second step is high-temperature sintering that helps to densify the ceramic. To improve the densification of LLZO during the sintering process, either external pressure is applied using a hot isostatic press, , or sintering aids are added to form a liquid phase at high temperature that improves the relative density (liquid phase sintering). ,,, Further, studies suggest that the choice of dopant has an influence on the relative density of LLZO, − as does the source of lithium, with differences reported between Li 2 CO 3 and LiOH·H 2 O . Some studies show that smaller LLZO particles can achieve 95% relative density at around 1100 °C temperature .…”

Section: Introductionmentioning

confidence: 99%

Investigating the Calcination and Sintering of Li₇La₃Zr₂O₁₂ (LLZO) Solid Electrolytes Using Operando Synchrotron X-ray Characterization and Mesoscale Modeling

et al. 2021

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The crystallographic structure and microstructure of solid electrolytes, such as Li7La3Zr2O12 (LLZO), have a profound impact on their reactivity, conductivity, and stability toward dendrites in solid-state batteries. Controlling the material’s structure and morphology requires fine control during the synthesis process, where multiple conditions (precursor particle size/distribution, calcination/sintering temperature, ramp rate, etc.) influence performance. This paper describes, for the first time, the operando characterization of the calcination process using synchrotron X-ray diffraction combined with a mesoscale model of grain growth during the calcination and densification of LLZO. The model is then used to guide synthesis conditions to enhance the densification process. The X-ray data reveal significant coarsening of the initial nanophase lanthanum zirconate precursors during conversion to LLZO. The mesoscale model shows that the activation energy for diffusion during calcination is lower than that during sintering, indicating the inherent coupling between the chemical reaction and grain growth processes. Simulations suggest that particles with small and bimodal size distribution experience better densification, as does precise grading (smaller particles near the surface and larger particles at the center) of different-sized particles. The approach described here can be adapted to understand and guide the synthesis of other materials that undergo calcination and sintering (e.g., transition metal oxide cathodes).

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Section: Introductionmentioning

confidence: 99%

Investigating the Calcination and Sintering of Li₇La₃Zr₂O₁₂ (LLZO) Solid Electrolytes Using Operando Synchrotron X-ray Characterization and Mesoscale Modeling

et al. 2021

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“…The structure of LLZO is formed by the common edge of ZrO 6 octahedron and LaO 8 dodecahedron, where Li ions filled the voids in the framework, allowing the size of the lithium migration channel to be modified by www.springer.com/journal/40145 doping at the La or Zr sites (Table 3) [57,60,61,75,93,95,[99][100][101][102][103][104][105][106][107][108][109][110][111][112][113][114]. There are few reports about lanthanum doping.…”

Section: Change Of Bottleneck Size On Mobilitymentioning

confidence: 99%

“…Furthermore, the introduction of Al 3+ in the crystal structure increased the conductivity [73][74][75]82]. Thus, it is essential to www.springer.com/journal/40145 regulate the concentration rate during element doping, since these may alter the Li concentration [94,103].…”

Section: Coordinated Regulation Of Lithium-ion Concentration and Mobilitymentioning

confidence: 99%

Garnet-type solid electrolyte: Advances of ionic transport performance and its application in all-solid-state batteries

et al. 2021

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All-solid-state lithium batteries (ASSLBs), which use solid electrolytes instead of liquid ones, have become a hot research topic due to their high energy and power density, ability to solve battery safety issues, and capabilities to fulfill the increasing demand for energy storage in electric vehicles and smart grid applications. Garnet-type solid electrolytes have attracted considerable interest as they meet all the properties of an ideal solid electrolyte for ASSLBs. The garnet-type Li7La3Zr2O12 (LLZO) has excellent environmental stability; experiments and computational analyses showed that this solid electrolyte has a high lithium (Li) ionic conductivity (10−4–10−3 S·cm−1), an electrochemical window as wide as 6 V, stability against Li metal anode, and compatibility with most of the cathode materials. In this review, we present the fundamentals of garnet-type solid electrolytes, preparation methods, air stability, some strategies for improving the conductivity based on experimental and computational results, interfacial issues, and finally applications and challenges for future developments of LLZO solid electrolytes for ASSLBs.

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“…(b) Experimental single substitutions of the different LLZO crystal sites (Li, La, Zr) with their corresponding total ionic conductivity (color map), and relative density (RD%). 59,63,81,99,[105][106][107][108][109][110][111][112][113][114][115][116][117][118]…”

Section: Impact Of Substitutions On Solid Electrolyte Metricsmentioning

confidence: 99%

The role of metal substitutions in the development of Li batteries, part II: solid electrolytes

Jonderian

McCalla

2021

Mater. Adv.

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Investigation of Mg2+, Sc3+ and Zn2+ doping effects on densification and ionic conductivity of low-temperature sintered Li7La3Zr2O12 garnets

Cited by 61 publications

References 25 publications

Investigating the Calcination and Sintering of Li₇La₃Zr₂O₁₂ (LLZO) Solid Electrolytes Using Operando Synchrotron X-ray Characterization and Mesoscale Modeling

Investigating the Calcination and Sintering of Li₇La₃Zr₂O₁₂ (LLZO) Solid Electrolytes Using Operando Synchrotron X-ray Characterization and Mesoscale Modeling

Garnet-type solid electrolyte: Advances of ionic transport performance and its application in all-solid-state batteries

The role of metal substitutions in the development of Li batteries, part II: solid electrolytes

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Investigation of Mg2+, Sc3+ and Zn2+ doping effects on densification and ionic conductivity of low-temperature sintered Li7La3Zr2O12 garnets

Cited by 61 publications

References 25 publications

Investigating the Calcination and Sintering of Li7La3Zr2O12 (LLZO) Solid Electrolytes Using Operando Synchrotron X-ray Characterization and Mesoscale Modeling

Investigating the Calcination and Sintering of Li7La3Zr2O12 (LLZO) Solid Electrolytes Using Operando Synchrotron X-ray Characterization and Mesoscale Modeling

Garnet-type solid electrolyte: Advances of ionic transport performance and its application in all-solid-state batteries

The role of metal substitutions in the development of Li batteries, part II: solid electrolytes

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Product

Resources

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Investigating the Calcination and Sintering of Li₇La₃Zr₂O₁₂ (LLZO) Solid Electrolytes Using Operando Synchrotron X-ray Characterization and Mesoscale Modeling

Investigating the Calcination and Sintering of Li₇La₃Zr₂O₁₂ (LLZO) Solid Electrolytes Using Operando Synchrotron X-ray Characterization and Mesoscale Modeling