Anomalous magnetic structure and spin dynamics in magnetoelectric LiFePO4

Toft-Petersen, Rasmus; Reehuis, Manfred; Jensen, Thomas B.  S.; Andersen, Niels H.; Li, Jiying; Le, Manh Duc; Laver, Mark; Niedermayer, Christof; Klemke, Bastian; Lefmann, Kim; Vaknin, David

doi:10.1103/PhysRevB.92.024404

Title: Anomalous magnetic structure and spin dynamics in magnetoelectric LiFePO₄

Journal Article · Mon Jul 06 00:00:00 EDT 2015 · Physical Review. B, Condensed Matter and Materials Physics

DOI:https://doi.org/10.1103/PhysRevB.92.024404· OSTI ID:1227391

Toft-Petersen, Rasmus ^[1]; Reehuis, Manfred ^[1]; Jensen, Thomas B. S. ^[2]; Andersen, Niels H. ^[2]; Li, Jiying ^[3]; Le, Manh Duc ^[4]; Laver, Mark ^[5]; Niedermayer, Christof ^[6]; Klemke, Bastian ^[1]; Lefmann, Kim ^[7]; Vaknin, David ^[3]

Helmholtz Zentrum Berlin Fur Materialien und Energie, Berlin (Germany)
Technical Univ. of Denmark, Lyngby (Denmark)
Iowa State Univ., Ames, IA (United States)
Helmholtz Zentrum Berlin Fur Materialien und Energie, Berlin (Germany); Institute for Basic Science (IBS), Seoul (Korea)
Technical Univ. of Denmark, Lyngby (Denmark); Paul Scherrer Institut, Villigen (Switzerland); Univ. of Birmingham, Birmingham (United Kingdom)
Paul Scherrer Inst. (PSI), Villigen (Switzerland)
Univ. of Copenhagen (Denmark)

We report significant details of the magnetic structure and spin dynamics of LiFePO₄ obtained by single-crystal neutron scattering. Our results confirm a previously reported collinear rotation of the spins away from the principal b axis, and they determine that the rotation is toward the a axis. In addition, we find a significant spin-canting component along c. Furthermore, the possible causes of these components are discussed, and their significance for the magnetoelectric effect is analyzed. Inelastic neutron scattering along the three principal directions reveals a highly anisotropic hard plane consistent with earlier susceptibility measurements. While using a spin Hamiltonian, we show that the spin dimensionality is intermediate between XY- and Ising-like, with an easy b axis and a hard c axis. As a result, it is shown that both next-nearest neighbor exchange couplings in the bc plane are in competition with the strongest nearest neighbor coupling.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

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

Grant/Contract Number:: DANSCATT; PP002-102831; AC02-07CH11358

OSTI ID:: 1227391

Alternate ID(s):: OSTI ID: 1198669

Report Number(s):: IS-J-8744; PRBMDO

Journal Information:: Physical Review. B, Condensed Matter and Materials Physics, Vol. 92, Issue 2; ISSN 1098-0121

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 37 works

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References (45)

Multiferroic and magnetoelectric materials Eerenstein, W.; Mathur, N. D.; Scott, J. F. Nature, Vol. 442, Issue 7104 https://doi.org/10.1038/nature05023	journal	August 2006
Multiferroics: a magnetic twist for ferroelectricity Cheong, Sang-Wook; Mostovoy, Maxim Nature Materials, Vol. 6, Issue 1 https://doi.org/10.1038/nmat1804	journal	January 2007
Magnetic Inversion Symmetry Breaking and Ferroelectricity in ${TbMnO}_{3}$ Kenzelmann, M.; Harris, A. B.; Jonas, S. Physical Review Letters, Vol. 95, Issue 8 https://doi.org/10.1103/PhysRevLett.95.087206	journal	August 2005
Towards a magnetoelectric memory Bibes, Manuel; Barthélémy, Agnès Nature Materials, Vol. 7, Issue 6 https://doi.org/10.1038/nmat2189	journal	June 2008
LiMnPO4 – A next generation cathode material for lithium-ion batteries Aravindan, Vanchiappan; Gnanaraj, Joe; Lee, Yun-Sung Journal of Materials Chemistry A, Vol. 1, Issue 11 https://doi.org/10.1039/c2ta01393b	journal	January 2013
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
Identify capacity fading mechanism in a commercial LiFePO4 cell Dubarry, Matthieu; Liaw, Bor Yann Journal of Power Sources, Vol. 194, Issue 1 https://doi.org/10.1016/j.jpowsour.2009.05.036	journal	October 2009
Graphene-modified LiFePO4 cathode for lithium ion battery beyond theoretical capacity Lung-Hao Hu, By; Wu, Feng-Yu; Lin, Cheng-Te Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms2705	journal	April 2013
Field-induced magnetic phases and electric polarization in ${LiNiPO}_{4}$ Jensen, Thomas Bagger Stibius; Christensen, Niels Bech; Kenzelmann, Michel Physical Review B, Vol. 79, Issue 9 https://doi.org/10.1103/PhysRevB.79.092412	journal	March 2009
Linear Magnetoelectric Effect by Orbital Magnetism Scaramucci, A.; Bousquet, E.; Fechner, M. Physical Review Letters, Vol. 109, Issue 19 https://doi.org/10.1103/PhysRevLett.109.197203	journal	November 2012
Magnetic phase diagram of magnetoelectric LiMnPO $_{4}$ Toft-Petersen, Rasmus; Andersen, Niels H.; Li, Haifeng Physical Review B, Vol. 85, Issue 22 https://doi.org/10.1103/PhysRevB.85.224415	journal	June 2012
Spin dynamics in the magnetoelectric effect compound ${LiCoPO}_{4}$ Tian, Wei; Li, Jiying; Lynn, Jeffrey W. Physical Review B, Vol. 78, Issue 18 https://doi.org/10.1103/PhysRevB.78.184429	journal	November 2008
The linear magnetoelectric effect in LiCoPO ₄ Revisited Rivera, J. -P. Ferroelectrics, Vol. 161, Issue 1 https://doi.org/10.1080/00150199408213364	journal	November 1994
Magnetoelectric properties of ${LiCoPO}_{4}$ and ${LiNiPO}_{4}$ Kornev, I.; Bichurin, M.; Rivera, J. -P. Physical Review B, Vol. 62, Issue 18 https://doi.org/10.1103/PhysRevB.62.12247	journal	November 2000
Antiferromagnetism in LiFePO4 Santoro, R. P.; Newnham, R. E. Acta Crystallographica, Vol. 22, Issue 3 https://doi.org/10.1107/S0365110X67000672	journal	March 1967
Magnetic properties of LiCoPO4 and LiNiPO4 Santoro, R. P.; Segal, D. J.; Newnham, R. E. Journal of Physics and Chemistry of Solids, Vol. 27, Issue 6-7 https://doi.org/10.1016/0022-3697(66)90097-7	journal	June 1966
Spin-waves in antiferromagnetic single-crystal $Li Fe P O_{4}$ Li, Jiying; Garlea, Vasile O.; Zarestky, Jerel L. Physical Review B, Vol. 73, Issue 2 https://doi.org/10.1103/PhysRevB.73.024410	journal	January 2006
Weakly coupled antiferromagnetic planes in single-crystal ${LiCoPO}_{4}$ Vaknin, D.; Zarestky, J. L.; Miller, L. L. Physical Review B, Vol. 65, Issue 22 https://doi.org/10.1103/PhysRevB.65.224414	journal	May 2002
Towards a microscopic theory of toroidal moments in bulk periodic crystals Ederer, Claude; Spaldin, Nicola A. Physical Review B, Vol. 76, Issue 21 https://doi.org/10.1103/PhysRevB.76.214404	journal	December 2007
Observation of ferrotoroidic domains Van Aken, Bas B.; Rivera, Jean-Pierre; Schmid, Hans Nature, Vol. 449, Issue 7163 https://doi.org/10.1038/nature06139	journal	October 2007
Anisotropy of antiferromagnetic 180° domains in magnetoelectric LiMPO4 (M = Fe, Co, Ni) Zimmermann, A. S.; Van Aken, B. B.; Schmid, H. The European Physical Journal B, Vol. 71, Issue 3 https://doi.org/10.1140/epjb/e2009-00223-3	journal	June 2009
Antiferromagnetism in the magnetoelectric effect single crystal ${LiMnPO}_{4}$ Li, Jiying; Tian, Wei; Chen, Ying Physical Review B, Vol. 79, Issue 14 https://doi.org/10.1103/PhysRevB.79.144410	journal	April 2009
Anomalous spin waves and the commensurate-incommensurate magnetic phase transition in ${LiNiPO}_{4}$ Jensen, T. B. S.; Christensen, N. B.; Kenzelmann, M. Physical Review B, Vol. 79, Issue 9 https://doi.org/10.1103/PhysRevB.79.092413	journal	March 2009
High-field magnetic phase transitions and spin excitations in magnetoelectric LiNiPO $_{4}$ Toft-Petersen, Rasmus; Jensen, Jens; Jensen, Thomas Bagger Stibius Physical Review B, Vol. 84, Issue 5 https://doi.org/10.1103/PhysRevB.84.054408	journal	August 2011
Commensurate-Incommensurate Magnetic Phase Transition in Magnetoelectric Single Crystal ${LiNiPO}_{4}$ Vaknin, D.; Zarestky, J. L.; Rivera, J. -P. Physical Review Letters, Vol. 92, Issue 20 https://doi.org/10.1103/PhysRevLett.92.207201	journal	May 2004
Anisotropy in magnetic properties and electronic structure of single-crystal $Li Fe P O_{4}$ Liang, Gan; Park, Keeseong; Li, Jiying Physical Review B, Vol. 77, Issue 6 https://doi.org/10.1103/PhysRevB.77.064414	journal	February 2008
Analysis of the Spin Exchange Interactions and the Ordered Magnetic Structures of Lithium Transition Metal Phosphates LiMPO ₄ (M = Mn, Fe, Co, Ni) with the Olivine Structure Dai, D.; Whangbo, M. -H.; Koo, H. -J. Inorganic Chemistry, Vol. 44, Issue 7 https://doi.org/10.1021/ic048431w	journal	April 2005
Raman scattering in a LiNiPO4 single crystal Fomin, V. I.; Gnezdilov, V. P.; Kurnosov, V. S. Low Temperature Physics, Vol. 28, Issue 3 https://doi.org/10.1063/1.1468525	journal	March 2002
Recent advances in magnetic structure determination by neutron powder diffraction Rodríguez-Carvajal, Juan Physica B: Condensed Matter, Vol. 192, Issue 1-2 https://doi.org/10.1016/0921-4526(93)90108-I	journal	October 1993
Gains from the upgrade of the cold neutron triple-axis spectrometer FLEXX at the BER-II reactor Le, M. D.; Quintero-Castro, D. L.; Toft-Petersen, R. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 729 https://doi.org/10.1016/j.nima.2013.07.007	journal	November 2013
Nano-network electronic conduction in iron and nickel olivine phosphates Herle, P. Subramanya; Ellis, B.; Coombs, N. Nature Materials, Vol. 3, Issue 3 https://doi.org/10.1038/nmat1063	journal	February 2004
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
Representation analysis of magnetic structures Bertaut, E. F. Acta Crystallographica Section A: Crystal Physics, Diffraction, Theoretical and General Crystallography, Vol. 24, Issue 1 https://doi.org/10.1107/S0567739468000306	journal	January 1968
Magnetic Structure Analysis and Group Theory Bertaut, E. F. Le Journal de Physique Colloques, Vol. 32, Issue C1 https://doi.org/10.1051/jphyscol:19711156	journal	February 1971
On group theoretical techniques in magnetic structure analysis Bertaut, E. F. Journal of Magnetism and Magnetic Materials, Vol. 24, Issue 3 https://doi.org/10.1016/0304-8853(81)90081-0	journal	October 1981
Lithium extraction/insertion in LiFePO4: an X-ray diffraction and Mössbauer spectroscopy study Andersson, A. Solid State Ionics, Vol. 130, Issue 1-2 https://doi.org/10.1016/S0167-2738(00)00311-8	journal	May 2000
Solid state synthesis of LiFePO4 studied by in situ high energy X-ray diffraction Chen, Zonghai; Ren, Yang; Qin, Yan Journal of Materials Chemistry, Vol. 21, Issue 15 https://doi.org/10.1039/c0jm04049e	journal	January 2011
Neutron diffraction study of ${YVO}_{3}$ , ${NdVO}_{3}$ , and ${TbVO}_{3}$ Reehuis, M.; Ulrich, C.; Pattison, P. Physical Review B, Vol. 73, Issue 9 https://doi.org/10.1103/PhysRevB.73.094440	journal	March 2006
Anisotropic Superexchange Interaction and Weak Ferromagnetism Moriya, Tôru Physical Review, Vol. 120, Issue 1 https://doi.org/10.1103/PhysRev.120.91	journal	October 1960
The magnetic susceptibility of LiFePO4 and LiCoPO4 Creer, J. G.; Troup, G. J. Physics Letters A, Vol. 32, Issue 6 https://doi.org/10.1016/0375-9601(70)90044-7	journal	August 1970
Mechanism of the Magnetoelectric Effect in an Antiferromagnet Rado, George T. Physical Review Letters, Vol. 6, Issue 11 https://doi.org/10.1103/PhysRevLett.6.609	journal	June 1961
Magnetic anisotropy in doped and undoped LiFePO4 single crystals Chen, D. P.; Wang, Xiaolin; Hu, Y. S. Journal of Applied Physics, Vol. 101, Issue 9 https://doi.org/10.1063/1.2712326	journal	May 2007
Investigation of magnon dispersion relations and neutron scattering cross sections with special attention to anisotropy effects Lindgård, P. A.; Kowalska, A.; Laut, P. Journal of Physics and Chemistry of Solids, Vol. 28, Issue 8 https://doi.org/10.1016/0022-3697(67)90264-8	journal	August 1967
Multi-step-like Magnetization of LiNiPO4 in a Pulse Magnetic Field Khrustalyov, V. M.; Savitsky, V. N.; Kharchenko, N. F. Czechoslovak Journal of Physics, Vol. 54, Issue S4 https://doi.org/10.1007/s10582-004-0023-5	journal	December 2004
Magnetic field induced spin reorientation in the strongly anisotropic antiferromagnetic crystal LiCoPO4 Kharchenko, N. F.; Khrustalev, V. M.; Savitskiĭ, V. N. Low Temperature Physics, Vol. 36, Issue 6 https://doi.org/10.1063/1.3457377	journal	June 2010

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