Infrared-active optical phonons in LiFePO4 single crystals

Stanislavchuk, T. N.; Middlemiss, D. S.; Syzdek, J. S.; Janssen, Y.; Basistyy, R.; Sirenko, A. A.; Khalifah, P. G.; Grey, C. P.; Kostecki, R.

doi:10.1063/1.4995282

Title: Infrared-active optical phonons in LiFePO₄ single crystals

Journal Article · Fri Jul 28 00:00:00 EDT 2017 · Journal of Applied Physics

DOI:https://doi.org/10.1063/1.4995282· OSTI ID:1425022

Stanislavchuk, T. N. ^[1]; Middlemiss, D. S. ^[2]; Syzdek, J. S. ^[3]; Janssen, Y. ^[4]; Basistyy, R. ^[1]; Sirenko, A. A. ^[1]; Khalifah, P. G. ^[5]; Grey, C. P. ^[6]; Kostecki, R. ^[3]

New Jersey Inst. of Technology, Newark, NJ (United States)
Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Stony Brook Univ., NY (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
Univ. of Cambridge (United Kingdom)

Infrared-active optical phonons were studied in olivine LiFePO oriented single crystals by means of both rotating analyzer and rotating compensator spectroscopic ellipsometry in the spectral range between 50 and 1400 cm . The eigenfrequencies, oscillator strengths, and broadenings of the phonon modes were determined from fits of the anisotropic harmonic oscillator model to the data. Optical phonons in a heterosite FePO crystal were measured from the delithiated ab-surface of the LiFePO crystal and compared with the phonon modes of the latter. Good agreement was found between experimental data and the results of solid-state hybrid density functional theory calculations for the phonon modes in both LiFePO and FePO . 4 4 4 4 4 -1

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

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

Grant/Contract Number:: SC0012704; AC02-05CH11231; AC02-98CH10886; FG02-07ER46382; SC0001294

OSTI ID:: 1425022

Alternate ID(s):: OSTI ID: 1372950; OSTI ID: 1772905

Report Number(s):: BNL-200004-2018-JAAM; TRN: US1802004

Journal Information:: Journal of Applied Physics, Vol. 122, Issue 4; ISSN 0021-8979

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 4 works

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References (33)

Optimized LiFePO[sub 4] for Lithium Battery Cathodes Yamada, A.; Chung, S. C.; Hinokuma, K. Journal of The Electrochemical Society, Vol. 148, Issue 3 https://doi.org/10.1149/1.1348257	journal	January 2001
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Phonon calculation on olivine-like LiMPO4 (M = Ni, Co, Fe) and Raman scattering of the iron-containing compound Paraguassu, W.; Freire, P. T. C.; Lemos, V. Journal of Raman Spectroscopy, Vol. 36, Issue 3 https://doi.org/10.1002/jrs.1278	journal	January 2005
Raman and FTIR Spectroscopic Study of Li[sub x]FePO[sub 4] (0≤x≤1) Burba, Christopher M.; Frech, Roger Journal of The Electrochemical Society, Vol. 151, Issue 7 https://doi.org/10.1149/1.1756885	journal	January 2004
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Vibrational studies of olivine-type compounds—II Orthophosphates, -arsenates and -vanadates AIBIIXVO4 Paques-Ledent, M. Th.; Tarte, P. Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 30, Issue 3 https://doi.org/10.1016/0584-8539(74)80190-X	journal	March 1974
Reciprocal Salt Flux Growth of LiFePO ₄ Single Crystals with Controlled Defect Concentrations Janssen, Yuri; Santhanagopalan, Dhamodaran; Qian, Danna Chemistry of Materials, Vol. 25, Issue 22 https://doi.org/10.1021/cm4027682	journal	November 2013
Calculation of the vibration frequencies of ?-quartz: The effect of Hamiltonian and basis set Zicovich-Wilson, C. M.; Pascale, F.; Roetti, C. Journal of Computational Chemistry, Vol. 25, Issue 15 https://doi.org/10.1002/jcc.20120	journal	January 2004
Nondilute diffusion from first principles: Li diffusion in ${Li}_{x} {TiS}_{2}$ Van der Ven, Anton; Thomas, John C.; Xu, Qingchuan Physical Review B, Vol. 78, Issue 10 https://doi.org/10.1103/PhysRevB.78.104306	journal	September 2008
Lattice dynamics, thermodynamics, and bonding strength of lithium-ion battery materials LiMPO ₄ (M = Mn, Fe, Co, and Ni): a comparative first-principles study Shang, S. L.; Wang, Y.; Mei, Z. G. J. Mater. Chem., Vol. 22, Issue 3 https://doi.org/10.1039/C1JM13547C	journal	January 2012
Synchrotron radiation-based far-infrared spectroscopic ellipsometer with full Mueller-matrix capability Stanislavchuk, T. N.; Kang, T. D.; Rogers, P. D. Review of Scientific Instruments, Vol. 84, Issue 2 https://doi.org/10.1063/1.4789495	journal	February 2013
Magnetic Structures of the Triphylite LiFePO ₄ and of Its Delithiated Form FePO ₄ Rousse, G.; Rodriguez-Carvajal, J.; Patoux, S. Chemistry of Materials, Vol. 15, Issue 21 https://doi.org/10.1021/cm0300462	journal	October 2003
IR Near-Field Spectroscopy and Imaging of Single Li _x FePO ₄ Microcrystals Lucas, I. T.; McLeod, A. S.; Syzdek, J. S. Nano Letters, Vol. 15, Issue 1 https://doi.org/10.1021/nl5010898	journal	December 2014
In situ Raman spectroscopy of LiFePO ₄ : size and morphology dependence during charge and self-discharge Wu, Jing; Dathar, Gopi Krishna Phani; Sun, Chunwen Nanotechnology, Vol. 24, Issue 42 https://doi.org/10.1088/0957-4484/24/42/424009	journal	September 2013
Electron Microscopy Study of the LiFePO[sub 4] to FePO[sub 4] Phase Transition Chen, Guoying; Song, Xiangyun; Richardson, Thomas J. Electrochemical and Solid-State Letters, Vol. 9, Issue 6 https://doi.org/10.1149/1.2192695	journal	January 2006
Kinetics of non-equilibrium lithium incorporation in LiFePO4 Malik, Rahul; Zhou, Fei; Ceder, G. Nature Materials, Vol. 10, Issue 8 https://doi.org/10.1038/nmat3065	journal	July 2011
Lithium deintercalation in LiFePO4 nanoparticles via a domino-cascade model Delmas, C.; Maccario, M.; Croguennec, L. Nature Materials, Vol. 7, Issue 8 https://doi.org/10.1038/nmat2230	journal	July 2008
Rotatable broadband retarders for far-infrared spectroscopic ellipsometry Kang, T. D.; Standard, E.; Carr, G. L. Thin Solid Films, Vol. 519, Issue 9 https://doi.org/10.1016/j.tsf.2010.12.057	journal	February 2011
Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr Miehlich, Burkhard; Savin, Andreas; Stoll, Hermann Chemical Physics Letters, Vol. 157, Issue 3 https://doi.org/10.1016/0009-2614(89)87234-3	journal	May 1989
Approaching Theoretical Capacity of LiFePO[sub 4] at Room Temperature at High Rates Huang, H.; Yin, S. -C.; Nazar, L. F. Electrochemical and Solid-State Letters, Vol. 4, Issue 10 https://doi.org/10.1149/1.1396695	journal	January 2001
The calculation of the vibrational frequencies of crystalline compounds and its implementation in the CRYSTAL code: Crystalline Compounds and the CRYSTAL Code Pascale, F.; Zicovich-Wilson, C. M.; López Gejo, F. Journal of Computational Chemistry, Vol. 25, Issue 6 https://doi.org/10.1002/jcc.20019	journal	March 2004
Positive Electrode Materials for Li-Ion and Li-Batteries ^† Ellis, Brian L.; Lee, Kyu Tae; Nazar, Linda F. Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm902696j	journal	February 2010
First-principles study of lattice dynamics of LiFePO4 Shi, Siqi; Zhang, Hua; Ke, Xuezhi Physics Letters A, Vol. 373, Issue 44 https://doi.org/10.1016/j.physleta.2009.09.014	journal	October 2009
Study of the LiFePO ₄ /FePO ₄ Two-Phase System by High-Resolution Electron Energy Loss Spectroscopy Laffont, L.; Delacourt, C.; Gibot, P. Chemistry of Materials, Vol. 18, Issue 23 https://doi.org/10.1021/cm0617182	journal	November 2006
CRYSTAL: a computational tool for the ab initio study of the electronic properties of crystals Dovesi, Roberto; Orlando, Roberto; Civalleri, Bartolomeo Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 5/6 https://doi.org/10.1524/zkri.220.5.571.65065	journal	January 2005
Spectroscopic Ellipsometry Fujiwara, Hiroyuki https://doi.org/10.1002/9780470060193	book	January 2007
Phonons, lithium diffusion and thermodynamics of LiMPO ₄ (M = Mn, Fe) Goel, Prabhatasree; Gupta, M. K.; Mittal, R. J. Mater. Chem. A, Vol. 2, Issue 35 https://doi.org/10.1039/C4TA01291G	journal	January 2014
Mueller matrices for anisotropic metamaterials generated using 4×4 matrix formalism Rogers, P. D.; Kang, T. D.; Zhou, T. Thin Solid Films, Vol. 519, Issue 9 https://doi.org/10.1016/j.tsf.2010.12.066	journal	February 2011
Phospho-olivines as Positive-Electrode Materials for Rechargeable Lithium Batteries Padhi, A. K. Journal of The Electrochemical Society, Vol. 144, Issue 4, p. 1188-1194 https://doi.org/10.1149/1.1837571	journal	April 1997
Ultimate Limits to Intercalation Reactions for Lithium Batteries Whittingham, M. Stanley Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr5003003	journal	October 2014
Antiferromagnetism in LiFePO4 Santoro, R. P.; Newnham, R. E. Acta Crystallographica, Vol. 22, Issue 3 https://doi.org/10.1107/S0365110X67000672	journal	March 1967
A general method to obtain well localized Wannier functions for composite energy bands in linear combination of atomic orbital periodic calculations Zicovich-Wilson, Claudio M.; Dovesi, Roberto; Saunders, Victor R. The Journal of Chemical Physics, Vol. 115, Issue 21 https://doi.org/10.1063/1.1415745	journal	December 2001
Thermal Stability of LiFePO[sub 4]-Based Cathodes Andersson, Anna S. Electrochemical and Solid-State Letters, Vol. 3, Issue 2 https://doi.org/10.1149/1.1390960	journal	January 1999

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