Fluid-enhanced surface diffusion controls intraparticle phase transformations
Abstract
Phase transformations driven by compositional change require mass flux across a phase boundary. In some anisotropic solids, however, the phase boundary moves along a non-conductive crystallographic direction. One such material is LiXFePO4, an elec- trode for lithium-ion batteries. With poor bulk ionic transport along the direction of phase separation, it is unclear how lithium migrates during phase transformations. Here, we show that lithium migrates along the solid/liquid interface without leaving the particle, whereby charge carriers do not cross the double layer. X-ray diffraction and microscopy experiments as well as ab initio molecular dynamics simulations show that organic solvent and water molecules promote this surface ion diffusion, effectively rendering LiXFePO4 a three-dimensional lithium-ion conductor. Phase-field simulations capture the effects of sur- face diffusion on phase transformation. Lowering surface diffusivity is crucial towards supressing phase separation. This work establishes fluid-enhanced surface diffusion as a key dial for tuning phase transformation in anisotropic solids.
- Authors:
-
- Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States); Sandia National Lab. (SNL-CA), Livermore, CA (United States)
- Univ. of Bath, Bath (United Kingdom)
- Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Stanford Univ., Stanford, CA (United States)
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- National Institute of Chemistry, Ljubljana (Slovenia)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Univ. of Ljubljana, Ljubljana (Slovenia)
- Stanford Univ., Stanford, CA (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1490653
- Alternate Identifier(s):
- OSTI ID: 1512363
- Grant/Contract Number:
- AC02-76SF00515; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Materials
- Additional Journal Information:
- Journal Volume: 17; Journal Issue: 10; Journal ID: ISSN 1476-1122
- Publisher:
- Springer Nature - Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Li, Yiyang, Chen, Hungru, Lim, Kipil, Deng, Haitao D., Lim, Jongwoo, Fraggedakis, Dimitrios, Attia, Peter M., Lee, Sang Chul, Jin, Norman, Moškon, Jože, Guan, Zixuan, Gent, William E., Hong, Jihyun, Yu, Young -Sang, Gaberšček, Miran, Islam, M. Saiful, Bazant, Martin Z., and Chueh, William C. Fluid-enhanced surface diffusion controls intraparticle phase transformations. United States: N. p., 2018.
Web. doi:10.1038/s41563-018-0168-4.
Li, Yiyang, Chen, Hungru, Lim, Kipil, Deng, Haitao D., Lim, Jongwoo, Fraggedakis, Dimitrios, Attia, Peter M., Lee, Sang Chul, Jin, Norman, Moškon, Jože, Guan, Zixuan, Gent, William E., Hong, Jihyun, Yu, Young -Sang, Gaberšček, Miran, Islam, M. Saiful, Bazant, Martin Z., & Chueh, William C. Fluid-enhanced surface diffusion controls intraparticle phase transformations. United States. https://doi.org/10.1038/s41563-018-0168-4
Li, Yiyang, Chen, Hungru, Lim, Kipil, Deng, Haitao D., Lim, Jongwoo, Fraggedakis, Dimitrios, Attia, Peter M., Lee, Sang Chul, Jin, Norman, Moškon, Jože, Guan, Zixuan, Gent, William E., Hong, Jihyun, Yu, Young -Sang, Gaberšček, Miran, Islam, M. Saiful, Bazant, Martin Z., and Chueh, William C. Mon .
"Fluid-enhanced surface diffusion controls intraparticle phase transformations". United States. https://doi.org/10.1038/s41563-018-0168-4. https://www.osti.gov/servlets/purl/1490653.
@article{osti_1490653,
title = {Fluid-enhanced surface diffusion controls intraparticle phase transformations},
author = {Li, Yiyang and Chen, Hungru and Lim, Kipil and Deng, Haitao D. and Lim, Jongwoo and Fraggedakis, Dimitrios and Attia, Peter M. and Lee, Sang Chul and Jin, Norman and Moškon, Jože and Guan, Zixuan and Gent, William E. and Hong, Jihyun and Yu, Young -Sang and Gaberšček, Miran and Islam, M. Saiful and Bazant, Martin Z. and Chueh, William C.},
abstractNote = {Phase transformations driven by compositional change require mass flux across a phase boundary. In some anisotropic solids, however, the phase boundary moves along a non-conductive crystallographic direction. One such material is LiXFePO4, an elec- trode for lithium-ion batteries. With poor bulk ionic transport along the direction of phase separation, it is unclear how lithium migrates during phase transformations. Here, we show that lithium migrates along the solid/liquid interface without leaving the particle, whereby charge carriers do not cross the double layer. X-ray diffraction and microscopy experiments as well as ab initio molecular dynamics simulations show that organic solvent and water molecules promote this surface ion diffusion, effectively rendering LiXFePO4 a three-dimensional lithium-ion conductor. Phase-field simulations capture the effects of sur- face diffusion on phase transformation. Lowering surface diffusivity is crucial towards supressing phase separation. This work establishes fluid-enhanced surface diffusion as a key dial for tuning phase transformation in anisotropic solids.},
doi = {10.1038/s41563-018-0168-4},
journal = {Nature Materials},
number = 10,
volume = 17,
place = {United States},
year = {Mon Sep 17 00:00:00 EDT 2018},
month = {Mon Sep 17 00:00:00 EDT 2018}
}
Web of Science
Figures / Tables:
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