Mechanism of the Delithiation/Lithiation Process in LiFe0.4Mn0.6PO4: in Situ and ex Situ Investigations on Long-Range and Local Structures

Bezza, Ilham; Kaus, Maximilian; Heinzmann, Ralf; Yavuz, Murat; Knapp, Michael; Mangold, Stefan; Doyle, Stephen; Grey, Clare P.; Ehrenberg, Helmut; Indris, Sylvio; Saadoune, Ismael

doi:10.1021/jp513032r

Mechanism of the Delithiation/Lithiation Process in LiFe_0.4Mn_0.6PO₄: in Situ and ex Situ Investigations on Long-Range and Local Structures

Journal Article · Tue Mar 31 00:00:00 EDT 2015 · Journal of Physical Chemistry. C

DOI:https://doi.org/10.1021/jp513032r· OSTI ID:1385987

Bezza, Ilham ^[1]; Kaus, Maximilian ^[2]; Heinzmann, Ralf ^[3]; Yavuz, Murat ^[4]; Knapp, Michael ^[5]; Mangold, Stefan ^[2]; Doyle, Stephen ^[2]; Grey, Clare P. ^[6]; Ehrenberg, Helmut ^[5]; Indris, Sylvio ^[5]; Saadoune, Ismael ^[7]

Cadi Ayyad Univ., Marrakesh (Morocco); Karlsruhe Inst. of Technology (KIT) (Germany)
Karlsruhe Inst. of Technology (KIT) (Germany)
Bruker Biospin GmbH (Germany)
Karlsruhe Inst. of Technology (KIT) (Germany); Helmholtz Institute Ulm for Electrochemical Energy Storage (HIU) (Germany); Technical Univ. of Darmstadt (Germany)
Karlsruhe Inst. of Technology (KIT) (Germany); Helmholtz Institute Ulm for Electrochemical Energy Storage (HIU) (Germany)
Univ. of Cambridge (United Kingdom)
Cadi Ayyad Univ., Marrakesh (Morocco)

LiFe_0.4Mn_0.6PO₄ olivine was prepared by a sol–gel route, using citric acid as a chelating agent and NH₄H₂PO₄ as a phosphorus source. Sucrose was used as the source for the carbon-coating of the particles. The correlation between the physicochemical and the electrochemical properties of this positive electrode material was explored. The electrochemical tests showed an initial discharge capacity of 121 mAh/g at a C/20 rate with a good reversibility of the lithiation/delithiation reactions. In situ XRD on LiFe_0.4Mn_0.6PO₄ reveals the occurrence of new phases upon cycling, which disappeared again at the end of discharge. The single phase observed after one complete cycle is identical to the pristine one. In situ XAS spectroscopy in combination with ⁵⁷Fe Mössbauer and ⁷Li NMR spectroscopy were used to investigate the changes in the local structure and the oxidation states of the transition metals and thus to complete the overall characterization of the lithiation/delithiation mechanism. All findings reveal a high reversibility of the reactions in this electrode material.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Northeastern Center for Chemical Energy Storage (NECCES)

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

Grant/Contract Number:: SC0001294; SC0012583

OSTI ID:: 1385987

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 17 Vol. 119; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (36)

Systematic trends of the 57Fe Mössbauer isomer shifts in (FeOn) and (FeFn) polyhedra. Evidence of a new correlation between the isomer shift and the inductive effect of the competing bond T-X (→ Fe) (where X is O or F and T any element with a formal positive charge) Menil, Francis Journal of Physics and Chemistry of Solids, Vol. 46, Issue 7 https://doi.org/10.1016/0022-3697(85)90001-0	journal	January 1985
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
Surface graphitization of Furan-resin-derived carbon Tanabe, Yasuhiro; Yamanaka, Junji; Hoshi, Kazuhito Carbon, Vol. 39, Issue 15 https://doi.org/10.1016/S0008-6223(01)00069-0	journal	December 2001
Raman microspectroscopy of soot and related carbonaceous materials: Spectral analysis and structural information Sadezky, A.; Muckenhuber, H.; Grothe, H. Carbon, Vol. 43, Issue 8 https://doi.org/10.1016/j.carbon.2005.02.018	journal	July 2005
LiFe1−xMIIxPO4/C (MII=Co, Ni, Mg) as cathode materials for lithium-ion batteries Novikova, Svetlana; Yaroslavtsev, Sergey; Rusakov, Vyacheslav Electrochimica Acta, Vol. 122 https://doi.org/10.1016/j.electacta.2013.08.118	journal	March 2014
One-pot, glycine-assisted combustion synthesis and characterization of nanoporous LiFePO4/C composite cathodes for lithium-ion batteries Kalaiselvi, N.; Manthiram, A. Journal of Power Sources, Vol. 195, Issue 9 https://doi.org/10.1016/j.jpowsour.2009.11.054	journal	May 2010
Conductive additive content balance in Li-ion battery cathodes: Commercial carbon blacks vs. in situ carbon from LiFePO4/C composites Palomares, Verónica; Goñi, Aintzane; Muro, Izaskun Gil de Journal of Power Sources, Vol. 195, Issue 22 https://doi.org/10.1016/j.jpowsour.2010.05.048	journal	November 2010
Review and analysis of nanostructured olivine-based lithium recheargeable batteries: Status and trends Zaghib, K.; Guerfi, A.; Hovington, P. Journal of Power Sources, Vol. 232 https://doi.org/10.1016/j.jpowsour.2012.12.095	journal	June 2013
Study of C-coated LiFe0.33Mn0.67PO4 as positive electrode material for Li-ion batteries Perea, A.; Castro, L.; Aldon, L. Journal of Solid State Chemistry, Vol. 192 https://doi.org/10.1016/j.jssc.2012.04.016	journal	August 2012
A new promising sol?gel synthesis of phospho-olivines as environmentally friendly cathode materials for Li-ion cells Piana, M. Solid State Ionics, Vol. 175, Issue 1-4 https://doi.org/10.1016/j.ssi.2004.06.021	journal	November 2004
The hydrothermal synthesis and characterization of olivines and related compounds for electrochemical applications Chen, Jiajun; Vacchio, Michael J.; Wang, Shijun Solid State Ionics, Vol. 178, Issue 31-32 https://doi.org/10.1016/j.ssi.2007.10.015	journal	January 2008
Identifying the Structure of the Intermediate, Li _2/3 CoPO ₄ , Formed during Electrochemical Cycling of LiCoPO ₄ Strobridge, Fiona C.; Clément, Raphaële J.; Leskes, Michal Chemistry of Materials, Vol. 26, Issue 21 https://doi.org/10.1021/cm502680w	journal	October 2014
MAS NMR Study of the Metastable Solid Solutions Found in the LiFePO ₄ /FePO ₄ System ^† Cabana, Jordi; Shirakawa, Junichi; Chen, Guoying Chemistry of Materials, Vol. 22, Issue 3 https://doi.org/10.1021/cm902714v	journal	February 2010
Hyperfine Fields at the Li Site in LiFePO ₄ -Type Olivine Materials for Lithium Rechargeable Batteries: A ⁷ Li MAS NMR and SQUID Study Tucker, Michael C.; Doeff, Marca M.; Richardson, Thomas J. Journal of the American Chemical Society, Vol. 124, Issue 15 https://doi.org/10.1021/ja017838m	journal	April 2002
Spin-Transfer Pathways in Paramagnetic Lithium Transition-Metal Phosphates from Combined Broadband Isotropic Solid-State MAS NMR Spectroscopy and DFT Calculations Clément, Raphaële J.; Pell, Andrew J.; Middlemiss, Derek S. Journal of the American Chemical Society, Vol. 134, Issue 41 https://doi.org/10.1021/ja306876u	journal	October 2012
Structural Evolution of Li ₂ Fe _{1- y} Mn _y SiO ₄ ( y = 0, 0.2, 0.5, 1) Cathode Materials for Li-Ion Batteries upon Electrochemical Cycling Chen, Ruiyong; Heinzmann, Ralf; Mangold, Stefan The Journal of Physical Chemistry C, Vol. 117, Issue 2 https://doi.org/10.1021/jp310935j	journal	January 2013
Electrochemical Delithiation/Relithiation of LiCoPO ₄ : A Two-Step Reaction Mechanism Investigated by in Situ X-ray Diffraction, in Situ X-ray Absorption Spectroscopy, and ex Situ ⁷ Li/ ³¹ P NMR Spectroscopy Kaus, Maximilian; Issac, Ibrahim; Heinzmann, Ralf The Journal of Physical Chemistry C, Vol. 118, Issue 31 https://doi.org/10.1021/jp503306v	journal	July 2014
LiMnPO ₄ Nanoplate Grown via Solid-State Reaction in Molten Hydrocarbon for Li-Ion Battery Cathode Choi, Daiwon; Wang, Donghai; Bae, In-Tae Nano Letters, Vol. 10, Issue 8 https://doi.org/10.1021/nl1007085	journal	August 2010
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
Development and challenges of LiFePO ₄ cathode material for lithium-ion batteries Yuan, Li-Xia; Wang, Zhao-Hui; Zhang, Wu-Xing Energy Environ. Sci., Vol. 4, Issue 2 https://doi.org/10.1039/C0EE00029A	journal	January 2011
Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides Shannon, R. D. Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767 https://doi.org/10.1107/S0567739476001551	journal	September 1976
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
Reaction Mechanism of the Olivine-Type Li[sub x](Mn[sub 0.6]Fe[sub 0.4])PO[sub 4] (0≤x≤1) Yamada, Atsuo; Kudo, Yoshihiro; Liu, Kuang-Yu Journal of The Electrochemical Society, Vol. 148, Issue 7 https://doi.org/10.1149/1.1375167	journal	January 2001
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
Phase Diagram of Li[sub x](Mn[sub y]Fe[sub 1−y])PO[sub 4] (0≤x, y≤1) Yamada, Atsuo; Kudo, Yoshihiro; Liu, Kuang-Yu Journal of The Electrochemical Society, Vol. 148, Issue 10 https://doi.org/10.1149/1.1401083	journal	January 2001
Reducing Carbon in LiFePO[sub 4]/C Composite Electrodes to Maximize Specific Energy, Volumetric Energy, and Tap Density Chen, Zhaohui; Dahn, J. R. Journal of The Electrochemical Society, Vol. 149, Issue 9 https://doi.org/10.1149/1.1498255	journal	January 2002
Effect of Surface Carbon Structure on the Electrochemical Performance of LiFePO₄ Doeff, Marca M.; Hu, Yaoqin; McLarnon, Frank Electrochemical and Solid-State Letters, Vol. 6, Issue 10, p. A207-A209 https://doi.org/10.1149/1.1601372	journal	July 2003
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
Effect of Structure on the Fe[sup 3+]∕Fe[sup 2+] Redox Couple in Iron Phosphates Padhi, A. K. Journal of The Electrochemical Society, Vol. 144, Issue 5 https://doi.org/10.1149/1.1837649	journal	January 1997
Synchrotron Diffraction Study of Lithium Extraction from LiMn[sub 0.6]Fe[sub 0.4]PO[sub 4] Bramnik, Natalia N.; Bramnik, Kirill G.; Nikolowski, Kristian Electrochemical and Solid-State Letters, Vol. 8, Issue 8 https://doi.org/10.1149/1.1940487	journal	January 2005
Electrochemical Studies of the LiFePO[sub 4] Thin Films Prepared with Pulsed Laser Deposition Song, Seung-Wan; Reade, Ronald P.; Kostecki, Robert Journal of The Electrochemical Society, Vol. 153, Issue 1 https://doi.org/10.1149/1.2128763	journal	January 2006
Enhanced Electrochemical Performance of Mesoparticulate LiMnPO[sub 4] for Lithium Ion Batteries Kwon, Nam-Hee; Drezen, Thierry; Exnar, Ivan Electrochemical and Solid-State Letters, Vol. 9, Issue 6 https://doi.org/10.1149/1.2191432	journal	January 2006
Nanoscale LiFePO[sub 4] and Li[sub 4]Ti[sub 5]O[sub 12] for High Rate Li-Ion Batteries Jaiswal, A.; Horne, C. R.; Chang, O. Journal of The Electrochemical Society, Vol. 156, Issue 12 https://doi.org/10.1149/1.3223987	journal	January 2009
The Electrode/Electrolyte Reactivity of LiFe _0.33 Mn _0.67 PO ₄ Compared to LiFePO ₄ Guéguen, A.; Castro, L.; Dedryvère, R. Journal of The Electrochemical Society, Vol. 160, Issue 2 https://doi.org/10.1149/2.019303jes	journal	December 2012
Nonstochiometry in LiFe _0.5 Mn _0.5 PO ₄ : Structural and Electrochemical Properties Amisse, Robin; Hamelet, Stéphane; Hanzel, Darko Journal of The Electrochemical Society, Vol. 160, Issue 9 https://doi.org/10.1149/2.068309jes	journal	January 2013
High Performance LiMn _{1− x} Fe _x PO ₄ (0 ≤ x ≤ 1) Synthesized via a Facile Polymer-Assisted Mechanical Activation Xiao, P. F.; Ding, B.; Lai, M. O. Journal of The Electrochemical Society, Vol. 160, Issue 6 https://doi.org/10.1149/2.116306jes	journal	January 2013

Cited By (4)

Electrochemical tuning of olivine-type lithium transition-metal phosphates as efficient water oxidation catalysts Liu, Yayuan; Wang, Haotian; Lin, Dingchang Energy & Environmental Science, Vol. 8, Issue 6 https://doi.org/10.1039/c5ee01290b	journal	January 2015
In situ analytical techniques for battery interface analysis Tripathi, Alok M.; Su, Wei-Nien; Hwang, Bing Joe Chemical Society Reviews, Vol. 47, Issue 3 https://doi.org/10.1039/c7cs00180k	journal	January 2018
Electrochemical Lithium Extraction and Insertion Process of Sol-Gel Synthesized LiMnPO ₄ via Two-Phase Mechanism Esmezjan, Lars; Mikhailova, Daria; Etter, Martin Journal of The Electrochemical Society, Vol. 166, Issue 6 https://doi.org/10.1149/2.1311906jes	journal	January 2019
Electrochemical Lithium Extraction and Insertion Process of Sol-Gel Synthesized $LiMnPO_{4}$ via Two-Phase Mechanism Esmezjan, Lars; Mikhailova, Daria; Etter, Martin Deutsches Elektronen-Synchrotron, DESY, Hamburg https://doi.org/10.3204/pubdb-2019-02078	text	January 2019

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