Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO4

Kai Xiang; Wenting Xing; Dorthe B. Ravnsbæk; Liang Hong; Ming Tang; Zheng Li; Kamila M. Wiaderek; Olaf J. Borkiewicz; Karena W. Chapman; Peter J. Chupas; Yet-Ming Chiang

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

Kai Xiang
, Wenting Xing
, Dorthe B. Ravnsbæk
, Liang Hong
, Ming Tang
, Zheng Li
, Kamila M. Wiaderek
, Olaf J. Borkiewicz
, Karena W. Chapman
, Peter J. Chupas
, Yet-Ming Chiang

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

60 Citations (Scopus)

Abstract

Virtually all intercalation compounds exhibit significant changes in unit cell volume as the working ion concentration varies. 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, amorphous phase forms to buffer the large lattice mismatch between primary phases. The amorphous phase has short-range order over ∼1nm domains that is characterized by a and b parameters matching one crystalline end-member phase and a c parameter matching the other, but is not detectable by powder diffraction alone. We suggest that this strain-accommodation mechanism may generally apply to systems with large transformation strains.

Original language	English
Journal	Nano Letters
Volume	17
Issue	3
Pages (from-to)	1696-1702
ISSN	1530-6984
DOIs	https://doi.org/10.1021/acs.nanolett.6b04971
Publication status	Published - 2017
Externally published	Yes

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Xiang, K., Xing, W., Ravnsbæk, D. B., Hong, L., Tang, M., Li, Z., Wiaderek, K. M., Borkiewicz, O. J., Chapman, K. W., Chupas, P. J., & Chiang, Y.-M. (2017). Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO₄. Nano Letters, 17(3), 1696-1702. https://doi.org/10.1021/acs.nanolett.6b04971

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title = "Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO4",

abstract = "Virtually all intercalation compounds exhibit significant changes in unit cell volume as the working ion concentration varies. 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, amorphous phase forms to buffer the large lattice mismatch between primary phases. The amorphous phase has short-range order over ∼1nm domains that is characterized by a and b parameters matching one crystalline end-member phase and a c parameter matching the other, but is not detectable by powder diffraction alone. We suggest that this strain-accommodation mechanism may generally apply to systems with large transformation strains.",

author = "Kai Xiang and Wenting Xing and Ravnsb{\ae}k, \{Dorthe B.\} and Liang Hong and Ming Tang and Zheng Li and Wiaderek, \{Kamila M.\} and Borkiewicz, \{Olaf J.\} and Chapman, \{Karena W.\} and Chupas, \{Peter J.\} and Yet-Ming Chiang",

year = "2017",

doi = "10.1021/acs.nanolett.6b04971",

language = "English",

volume = "17",

pages = "1696--1702",

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Xiang, K, Xing, W, Ravnsbæk, DB, Hong, L, Tang, M, Li, Z, Wiaderek, KM, Borkiewicz, OJ, Chapman, KW, Chupas, PJ & Chiang, Y-M 2017, 'Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO₄', Nano Letters, vol. 17, no. 3, pp. 1696-1702. https://doi.org/10.1021/acs.nanolett.6b04971

Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases: Operando Investigation of Olivine NaFePO₄. / Xiang, Kai; Xing, Wenting; Ravnsbæk, Dorthe B. et al.
In: Nano Letters, Vol. 17, No. 3, 2017, p. 1696-1702.

Research output: Contribution to journal/Conference contribution in journal/Contribution to newspaper › Journal article › Research › peer-review

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T1 - Accommodating High Transformation Strains in Battery Electrodes via the Formation of Nanoscale Intermediate Phases

T2 - Operando Investigation of Olivine NaFePO4

AU - Xiang, Kai

AU - Xing, Wenting

AU - Ravnsbæk, Dorthe B.

AU - Hong, Liang

AU - Tang, Ming

AU - Li, Zheng

AU - Wiaderek, Kamila M.

AU - Borkiewicz, Olaf J.

AU - Chapman, Karena W.

AU - Chupas, Peter J.

AU - Chiang, Yet-Ming

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N2 - Virtually all intercalation compounds exhibit significant changes in unit cell volume as the working ion concentration varies. 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, amorphous phase forms to buffer the large lattice mismatch between primary phases. The amorphous phase has short-range order over ∼1nm domains that is characterized by a and b parameters matching one crystalline end-member phase and a c parameter matching the other, but is not detectable by powder diffraction alone. We suggest that this strain-accommodation mechanism may generally apply to systems with large transformation strains.

AB - Virtually all intercalation compounds exhibit significant changes in unit cell volume as the working ion concentration varies. 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, amorphous phase forms to buffer the large lattice mismatch between primary phases. The amorphous phase has short-range order over ∼1nm domains that is characterized by a and b parameters matching one crystalline end-member phase and a c parameter matching the other, but is not detectable by powder diffraction alone. We suggest that this strain-accommodation mechanism may generally apply to systems with large transformation strains.

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