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Title: Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO 4 [Accommodation of High Transformation Strain in Battery Electrodes via Formation of Nanoscale Intermediate Phases: Operando Structure Investigation of Olivine Sodium Iron Phosphate]

Virtually all intercalation compounds used as battery electrodes exhibit significant changes in unit cell volume during use. Na xFePO 4 (0 < x < 1, NFP) olivine, of interest as a cathode for sodium-ion batteries, is a model for topotactic, high strain systems as it exhibits one of the largest discontinuous volume changes (~17% by volume) during its first-order transition between two otherwise isostructural phases. Using synchrotron radiation powder X-ray diffraction (PXD) and pair distribution function (PDF) analysis, we discover a new strain-accommodation mechanism wherein a third, <10 nm scale nanocrystalline phase forms to buffer the large lattice mismatch between primary phases. The new phase has a and b lattice parameters matching one crystalline endmember phase and c lattice parameter matching the other, and is not detectable by powder diffraction alone. Finally, we suggest that this strain-accommodation mechanism may apply to systems with large transformation strains but in which true “amorphization” does not occur.
ORCiD logo [1] ;  [1] ;  [2] ;  [3] ;  [3] ;  [1] ;  [4] ;  [4] ;  [4] ;  [4] ; ORCiD logo [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Southern Denmark (Denmark)
  3. Rice Univ., Houston, TX (United States)
  4. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Grant/Contract Number:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 17; Journal Issue: 3; Journal ID: ISSN 1530-6984
American Chemical Society
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
25 ENERGY STORAGE; batteries; olivines; operando; phase transformations; sodium iron phosphate; pair-distribution function
OSTI Identifier: