Exploring the relationship between solvent-assisted ball milling, particle size, and sintering temperature in garnet-type solid electrolytes
Abstract
Garnet-type solid electrolytes, such as Li6.4La3Zr1.4Ta0.6O12 (LLZTO), are promising materials for solid-state batteries, but processing remains a challenge, in part due to the high sintering temperature required for densification. Additionally, this temperature can be lowered by decreasing the initial particle size via solvent-assisted ball milling, but the relationship between solvent choice, particle properties, sintering behavior, and ionic conductivity is not well understood. In this work, we systematically explore these parameters, showing that milling in commonly used protic solvents, such as alcohols, effectively decreases the particle size but results in lithium loss (through Li+/H+ exchange) that leads to poor sintering. By contrast, milling in aprotic solvents with surfactant reduces the particle size to ~220 nm without lithium loss, enabling the fabrication of dense samples (5.1 g/cm3) with good ionic conductivity (0.43 mS/cm at 25 °C) at a lower sintering temperature (1000 °C). We compare ionic conductivities and activation energies for samples prepared with different particle sizes and sintering temperatures and use multiphase-field simulations to identify the mass transport and microstructural mechanisms responsible for the observed sintering dependence on particle size. These results further clarify the relationship between processing parameters and performance and represent important progress toward overcoming fabrication challenges for thesemore »
- Authors:
-
[1];
[1];
[3];
[1];
[1];
[1]
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Cornell Univ., Ithaca, NY (United States)
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of Texas, El Paso, TX (United States)
- Publication Date:
- Research Org.:
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; USDOE Laboratory Directed Research and Development (LDRD) Program
- OSTI Identifier:
- 1769095
- Alternate Identifier(s):
- OSTI ID: 1809615
- Report Number(s):
- LLNL-JRNL-811534
Journal ID: ISSN 0378-7753; 1017493
- Grant/Contract Number:
- AC52-07NA27344
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Power Sources
- Additional Journal Information:
- Journal Volume: 484; Journal Issue: na; Journal ID: ISSN 0378-7753
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 25 ENERGY STORAGE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Solid-state electrolytes; garnet; LLZO; sintering temperature; ball milling; phase-field modeling
Citation Formats
Wood, Marissa, Gao, Xiaosi, Shi, Rongpei, Heo, Tae Wook, Espitia, Jose Ali, Duoss, Eric B., Wood, Brandon C., and Ye, Jianchao. Exploring the relationship between solvent-assisted ball milling, particle size, and sintering temperature in garnet-type solid electrolytes. United States: N. p., 2020.
Web. doi:10.1016/j.jpowsour.2020.229252.
Wood, Marissa, Gao, Xiaosi, Shi, Rongpei, Heo, Tae Wook, Espitia, Jose Ali, Duoss, Eric B., Wood, Brandon C., & Ye, Jianchao. Exploring the relationship between solvent-assisted ball milling, particle size, and sintering temperature in garnet-type solid electrolytes. United States. https://doi.org/10.1016/j.jpowsour.2020.229252
Wood, Marissa, Gao, Xiaosi, Shi, Rongpei, Heo, Tae Wook, Espitia, Jose Ali, Duoss, Eric B., Wood, Brandon C., and Ye, Jianchao. Tue .
"Exploring the relationship between solvent-assisted ball milling, particle size, and sintering temperature in garnet-type solid electrolytes". United States. https://doi.org/10.1016/j.jpowsour.2020.229252. https://www.osti.gov/servlets/purl/1769095.
@article{osti_1769095,
title = {Exploring the relationship between solvent-assisted ball milling, particle size, and sintering temperature in garnet-type solid electrolytes},
author = {Wood, Marissa and Gao, Xiaosi and Shi, Rongpei and Heo, Tae Wook and Espitia, Jose Ali and Duoss, Eric B. and Wood, Brandon C. and Ye, Jianchao},
abstractNote = {Garnet-type solid electrolytes, such as Li6.4La3Zr1.4Ta0.6O12 (LLZTO), are promising materials for solid-state batteries, but processing remains a challenge, in part due to the high sintering temperature required for densification. Additionally, this temperature can be lowered by decreasing the initial particle size via solvent-assisted ball milling, but the relationship between solvent choice, particle properties, sintering behavior, and ionic conductivity is not well understood. In this work, we systematically explore these parameters, showing that milling in commonly used protic solvents, such as alcohols, effectively decreases the particle size but results in lithium loss (through Li+/H+ exchange) that leads to poor sintering. By contrast, milling in aprotic solvents with surfactant reduces the particle size to ~220 nm without lithium loss, enabling the fabrication of dense samples (5.1 g/cm3) with good ionic conductivity (0.43 mS/cm at 25 °C) at a lower sintering temperature (1000 °C). We compare ionic conductivities and activation energies for samples prepared with different particle sizes and sintering temperatures and use multiphase-field simulations to identify the mass transport and microstructural mechanisms responsible for the observed sintering dependence on particle size. These results further clarify the relationship between processing parameters and performance and represent important progress toward overcoming fabrication challenges for these materials.},
doi = {10.1016/j.jpowsour.2020.229252},
journal = {Journal of Power Sources},
number = na,
volume = 484,
place = {United States},
year = {Tue Dec 08 00:00:00 EST 2020},
month = {Tue Dec 08 00:00:00 EST 2020}
}
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