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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.
Authors:
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:
AC02-06CH11357
Type:
Accepted Manuscript
Journal Name:
Nano Letters
Additional Journal Information:
Journal Volume: 17; Journal Issue: 3; Journal ID: ISSN 1530-6984
Publisher:
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
Language:
English
Subject:
25 ENERGY STORAGE; batteries; olivines; operando; phase transformations; sodium iron phosphate; pair-distribution function
OSTI Identifier:
1373931

Xiang, Kai, Xing, Wenting, Ravnsbaek, Dorthe B., Hong, Liang, Tang, Ming, Li, Zheng, Wiaderek, Kamila M., Borkiewicz, Olaf J., Chapman, Karena W., Chupas, Peter J., and Chiang, Yet -Ming. Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO4 [Accommodation of High Transformation Strain in Battery Electrodes via Formation of Nanoscale Intermediate Phases: Operando Structure Investigation of Olivine Sodium Iron Phosphate]. United States: N. p., Web. doi:10.1021/acs.nanolett.6b04971.
Xiang, Kai, Xing, Wenting, Ravnsbaek, Dorthe B., Hong, Liang, Tang, Ming, Li, Zheng, Wiaderek, Kamila M., Borkiewicz, Olaf J., Chapman, Karena W., Chupas, Peter J., & Chiang, Yet -Ming. Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO4 [Accommodation of High Transformation Strain in Battery Electrodes via Formation of Nanoscale Intermediate Phases: Operando Structure Investigation of Olivine Sodium Iron Phosphate]. United States. doi:10.1021/acs.nanolett.6b04971.
Xiang, Kai, Xing, Wenting, Ravnsbaek, Dorthe B., Hong, Liang, Tang, Ming, Li, Zheng, Wiaderek, Kamila M., Borkiewicz, Olaf J., Chapman, Karena W., Chupas, Peter J., and Chiang, Yet -Ming. 2017. "Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO4 [Accommodation of High Transformation Strain in Battery Electrodes via Formation of Nanoscale Intermediate Phases: Operando Structure Investigation of Olivine Sodium Iron Phosphate]". United States. doi:10.1021/acs.nanolett.6b04971. https://www.osti.gov/servlets/purl/1373931.
@article{osti_1373931,
title = {Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO4 [Accommodation of High Transformation Strain in Battery Electrodes via Formation of Nanoscale Intermediate Phases: Operando Structure Investigation of Olivine Sodium Iron Phosphate]},
author = {Xiang, Kai and Xing, Wenting and Ravnsbaek, Dorthe B. and Hong, Liang and Tang, Ming and Li, Zheng and Wiaderek, Kamila M. and Borkiewicz, Olaf J. and Chapman, Karena W. and Chupas, Peter J. and Chiang, Yet -Ming},
abstractNote = {Virtually all intercalation compounds used as battery electrodes exhibit significant changes in unit cell volume during use. NaxFePO4 (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.},
doi = {10.1021/acs.nanolett.6b04971},
journal = {Nano Letters},
number = 3,
volume = 17,
place = {United States},
year = {2017},
month = {2}
}