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]

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

doi:10.1021/acs.nanolett.6b04971

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]

Journal Article · Tue Feb 21 00:00:00 EST 2017 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.6b04971· OSTI ID:1373931

^[1]; Xing, Wenting ^[1]; Ravnsbaek, Dorthe B. ^[2]; Hong, Liang ^[3]; Tang, Ming ^[3]; Li, Zheng ^[1]; Wiaderek, Kamila M. ^[4]; Borkiewicz, Olaf J. ^[4]; Chapman, Karena W. ^[4]; Chupas, Peter J. ^[4]; ^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Univ. of Southern Denmark (Denmark)
Rice Univ., Houston, TX (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Virtually all intercalation compounds used as battery electrodes exhibit significant changes in unit cell volume during use. Na_xFePO₄ (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.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1373931

Journal Information:: Nano Letters, Journal Name: Nano Letters Journal Issue: 3 Vol. 17; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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