Fluid-enhanced surface diffusion controls intraparticle phase transformations

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.

doi:10.1038/s41563-018-0168-4

Fluid-enhanced surface diffusion controls intraparticle phase transformations

Journal Article · Mon Sep 17 00:00:00 EDT 2018 · Nature Materials

DOI:https://doi.org/10.1038/s41563-018-0168-4· OSTI ID:1490653

^[1]; Chen, Hungru ^[2]; Lim, Kipil ^[3]; Deng, Haitao D. ^[4]; Lim, Jongwoo ^[3]; ^[5]; ^[4]; Lee, Sang Chul ^[4]; Jin, Norman ^[4]; Moškon, Jože ^[6]; Guan, Zixuan ^[4]; ^[4]; ^[3]; Yu, Young -Sang ^[7]; Gaberšček, Miran ^[8]; Islam, M. Saiful ^[2]; Bazant, Martin Z. ^[9]; Chueh, William C. ^[3]

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)

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 Li_XFePO₄, an electrode 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 Li_XFePO₄ a three-dimensional lithium-ion conductor. Phase-field simulations capture the effects of surface diffusion on phase transformation. Lowering surface diffusivity is crucial towards supressing phase separation. In conclusion, this work establishes fluid-enhanced surface diffusion as a key dial for tuning phase transformation in anisotropic solids.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1490653

Alternate ID(s):: OSTI ID: 1512363

Journal Information:: Nature Materials, Journal Name: Nature Materials Journal Issue: 10 Vol. 17; ISSN 1476-1122

Publisher:: Springer Nature - Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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