Direct synthesis and characterization of mixed-valent Li0.5$$-$$δCoPO4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO4
Abstract
While the majority of research activities on LiCoPO4 is focussed on the thermodynamically stable olivine-type Pnma polymorph, the metastable Pna21 and Cmcm modifications have recently attracted considerable attention due to their interesting material properties. In this study, we present the first Li-deficient structural derivative of the Cmcm modification with the nominal composition Li0.5–δCoPO4. As opposed to the substoichiometric olivine (Pnma) phases LixCoPO4 (x = 0; 2/3), which are exclusively accessible by electrochemical or chemical Li extraction techniques, this is also the first time that a direct soft-chemical synthesis route towards a LixCoPO4-type material is accomplished. X-ray and neutron diffraction studies indicate that Cmcm-type Li0.5–δCoPO4 shows vacancies on both the Li and Co sites, whereas X-ray absorption spectra demonstrate that the structure features heterovalent Co ions (+2/+3) to compensate for the Li deficit. Magnetic measurements reveal a long-range antiferromagnetic order below 10.5 K. A thorough investigation of the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and temperature-dependent in situ X-ray powder diffraction demonstrates that Li0.5–δCoPO4 is metastable and exhibits a complex, multi-step thermal decomposition mechanism. In the first step at 394 °C, it decomposes to α-Co2P2O7 (P21/c) and LiCoPO4 (Cmcm) upon O2 release. The LiCoPO4 (Cmcm) intermediate is then irreversiblymore »
- Authors:
-
[1]
- Technical Univ. of Munich, Garching (Germany)
- Bavarian Academy of Sciences and Humanities, Garching (Germany)
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Instituto de Ciencia de Materiales de Aragon, Zaragoza (Spain); Institut Laue-Langevin, Grenoble Cedex (France)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1369476
- Grant/Contract Number:
- AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- RSC Advances
- Additional Journal Information:
- Journal Volume: 7; Journal Issue: 45; Journal ID: ISSN 2046-2069
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
Citation Formats
Ludwig, Jennifer, Alarcon-Suesca, Carlos, Geprags, Stephan, Nordlund, Dennis, Doeff, Marca M., Orench, Ines Puente, and Nilges, Tom. Direct synthesis and characterization of mixed-valent Li0.5$-$δCoPO4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO4. United States: N. p., 2017.
Web. doi:10.1039/c7ra04043a.
Ludwig, Jennifer, Alarcon-Suesca, Carlos, Geprags, Stephan, Nordlund, Dennis, Doeff, Marca M., Orench, Ines Puente, & Nilges, Tom. Direct synthesis and characterization of mixed-valent Li0.5$-$δCoPO4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO4. United States. https://doi.org/10.1039/c7ra04043a
Ludwig, Jennifer, Alarcon-Suesca, Carlos, Geprags, Stephan, Nordlund, Dennis, Doeff, Marca M., Orench, Ines Puente, and Nilges, Tom. Fri .
"Direct synthesis and characterization of mixed-valent Li0.5$-$δCoPO4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO4". United States. https://doi.org/10.1039/c7ra04043a. https://www.osti.gov/servlets/purl/1369476.
@article{osti_1369476,
title = {Direct synthesis and characterization of mixed-valent Li0.5$-$δCoPO4, a Li-deficient derivative of the Cmcm polymorph of LiCoPO4},
author = {Ludwig, Jennifer and Alarcon-Suesca, Carlos and Geprags, Stephan and Nordlund, Dennis and Doeff, Marca M. and Orench, Ines Puente and Nilges, Tom},
abstractNote = {While the majority of research activities on LiCoPO4 is focussed on the thermodynamically stable olivine-type Pnma polymorph, the metastable Pna21 and Cmcm modifications have recently attracted considerable attention due to their interesting material properties. In this study, we present the first Li-deficient structural derivative of the Cmcm modification with the nominal composition Li0.5–δCoPO4. As opposed to the substoichiometric olivine (Pnma) phases LixCoPO4 (x = 0; 2/3), which are exclusively accessible by electrochemical or chemical Li extraction techniques, this is also the first time that a direct soft-chemical synthesis route towards a LixCoPO4-type material is accomplished. X-ray and neutron diffraction studies indicate that Cmcm-type Li0.5–δCoPO4 shows vacancies on both the Li and Co sites, whereas X-ray absorption spectra demonstrate that the structure features heterovalent Co ions (+2/+3) to compensate for the Li deficit. Magnetic measurements reveal a long-range antiferromagnetic order below 10.5 K. A thorough investigation of the thermal stability using thermogravimetric analysis, differential scanning calorimetry, and temperature-dependent in situ X-ray powder diffraction demonstrates that Li0.5–δCoPO4 is metastable and exhibits a complex, multi-step thermal decomposition mechanism. In the first step at 394 °C, it decomposes to α-Co2P2O7 (P21/c) and LiCoPO4 (Cmcm) upon O2 release. The LiCoPO4 (Cmcm) intermediate is then irreversibly transformed to olivine-type LiCoPO4 (Pnma) at 686 °C. Furthermore, the material properties of Li0.5–δCoPO4 are further compared to the fully lithiated, isostructural LiCoPO4 (Cmcm) phase, for which an improved structure solution as well as Co L2,3-edge X-ray absorption spectra are reported for the first time.},
doi = {10.1039/c7ra04043a},
journal = {RSC Advances},
number = 45,
volume = 7,
place = {United States},
year = {Fri May 26 00:00:00 EDT 2017},
month = {Fri May 26 00:00:00 EDT 2017}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 4 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Correlation between Raman wavenumbers and P?O bond lengths in crystalline inorganic phosphates
journal, January 2005
- Popovi?, L.; de Waal, D.; Boeyens, J. C. A.
- Journal of Raman Spectroscopy, Vol. 36, Issue 1
Identifying the Structure of the Intermediate, Li 2/3 CoPO 4 , Formed during Electrochemical Cycling of LiCoPO 4
journal, October 2014
- Strobridge, Fiona C.; Clément, Raphaële J.; Leskes, Michal
- Chemistry of Materials, Vol. 26, Issue 21
Raman and FTIR Spectroscopic Study of Li[sub x]FePO[sub 4] (0≤x≤1)
journal, January 2004
- Burba, Christopher M.; Frech, Roger
- Journal of The Electrochemical Society, Vol. 151, Issue 7
Issues and challenges facing rechargeable lithium batteries
journal, November 2001
- Tarascon, J.-M.; Armand, M.
- Nature, Vol. 414, Issue 6861, p. 359-367
Microwave-Assisted Solvothermal Synthesis of Three Polymorphs of LiCoPO 4 and Their Electrochemical Properties
journal, August 2015
- Kreder, Karl J.; Assat, Gaurav; Manthiram, Arumugam
- Chemistry of Materials, Vol. 27, Issue 16
High pressure polymorphs of LiCoPO4 and LiCoAsO4
journal, February 2009
- Amador, U.; Gallardo-Amores, J. M.; Heymann, G.
- Solid State Sciences, Vol. 11, Issue 2
Vibrational studies of olivine-type compounds—II Orthophosphates, -arsenates and -vanadates AIBIIXVO4
journal, March 1974
- Paques-Ledent, M. Th.; Tarte, P.
- Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 30, Issue 3
In Situ Studies and Magnetic Properties of the Cmcm Polymorph of LiCoPO4 with a Hierarchical Dumbbell-Like Morphology Synthesized by Easy Single-Step Polyol Synthesis
journal, November 2016
- Alarcón-Suesca, Carlos; Ludwig, Jennifer; Hlukhyy, Viktor
- Inorganics, Vol. 4, Issue 4
Hydrothermal and Solvothermal Process Towards Development of LiMPO4 (M = Fe, Mn) Nanomaterials for Lithium-Ion Batteries
journal, March 2012
- Devaraju, Murukanahally Kempaiah; Honma, Itaru
- Advanced Energy Materials, Vol. 2, Issue 3
Crystal and magnetic structures of electrochemically delithiated Li1−xCoPO4 phases
journal, January 2009
- Ehrenberg, Helmut; Bramnik, Natalia N.; Senyshyn, Anatoliy
- Solid State Sciences, Vol. 11, Issue 1
Anomalous dispersion calculations near to and on the long-wavelength side of an absorption edge
journal, March 1981
- Cromer, D. T.; Liberman, D. A.
- Acta Crystallographica Section A, Vol. 37, Issue 2
An unusual high-spin ground state of Co 3+ in octahedral coordination in brownmillerite-type cobalt oxide
journal, January 2015
- Istomin, S. Ya.; Tyablikov, O. A.; Kazakov, S. M.
- Dalton Transactions, Vol. 44, Issue 23
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
journal, July 2014
- Kaus, Maximilian; Issac, Ibrahim; Heinzmann, Ralf
- The Journal of Physical Chemistry C, Vol. 118, Issue 31
Vibrational spectroscopic investigation of structurally-related LiFePO4, NaFePO4, and FePO4 compounds
journal, September 2006
- Burba, Christopher M.; Frech, Roger
- Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 65, Issue 1
Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993
- Rodríguez-Carvajal, Juan
- Physica B: Condensed Matter, Vol. 192, Issue 1-2
Hydrothermal synthesis of lithium iron phosphate
journal, May 2006
- Chen, J.; Whittingham, M.
- Electrochemistry Communications, Vol. 8, Issue 5
Different Look at the Spin State of Ions in a Pyramidal Coordination
journal, May 2004
- Hu, Z.; Wu, Hua; Haverkort, M. W.
- Physical Review Letters, Vol. 92, Issue 20
Olivine LiCoPO[sub 4] as 4.8 V Electrode Material for Lithium Batteries
journal, January 1999
- Amine, K.
- Electrochemical and Solid-State Letters, Vol. 3, Issue 4
Mean-field theory of the three-dimensional anisotropic Ising model as a four-dimensional mapping
journal, June 1983
- Jensen, M. Høgh; Bak, Per
- Physical Review B, Vol. 27, Issue 11
Co Polyoxometalates and a Co 3 O 4 Thin Film Investigated by L-Edge X-ray Absorption Spectroscopy
journal, February 2015
- Hibberd, Amber M.; Doan, Hoang Q.; Glass, Elliot N.
- The Journal of Physical Chemistry C, Vol. 119, Issue 8
Magnetic field induced spin reorientation in the strongly anisotropic antiferromagnetic crystal LiCoPO4
journal, June 2010
- Kharchenko, N. F.; Khrustalev, V. M.; Savitskiĭ, V. N.
- Low Temperature Physics, Vol. 36, Issue 6
Olivine-type cathodes
journal, June 2003
- Yamada, Atsuo; Hosoya, Mamoru; Chung, Sai-Cheong
- Journal of Power Sources, Vol. 119-121
Battery materials for ultrafast charging and discharging
journal, March 2009
- Kang, Byoungwoo; Ceder, Gerbrand
- Nature, Vol. 458, Issue 7235, p. 190-193
Synthesis of LiFePO[sub 4] Nanoparticles in Polyol Medium and Their Electrochemical Properties
journal, January 2006
- Kim, Dong-Han; Kim, Jaekook
- Electrochemical and Solid-State Letters, Vol. 9, Issue 9
Experimental investigations on the electrochemical and thermal behaviour of LiCoPO4-based cathode
journal, January 2013
- Theil, Simon; Fleischhammer, Meike; Axmann, Peter
- Journal of Power Sources, Vol. 222
2 p x-ray absorption of 3 d transition-metal compounds: An atomic multiplet description including the crystal field
journal, September 1990
- de Groot, F. M. F.; Fuggle, J. C.; Thole, B. T.
- Physical Review B, Vol. 42, Issue 9
β-Dicobalt pyrophosphate
journal, April 1994
- El Belghitti, A.; Boukhari, A.; Holt, E. M.
- Acta Crystallographica Section C Crystal Structure Communications, Vol. 50, Issue 4
Positive Electrode Materials for Li-Ion and Li-Batteries †
journal, February 2010
- Ellis, Brian L.; Lee, Kyu Tae; Nazar, Linda F.
- Chemistry of Materials, Vol. 22, Issue 3
Weak ferromagnetism in the antiferromagnetic magnetoelectric crystal LiCoPO4
journal, September 2001
- Kharchenko, N. F.; Kharchenko, Yu. N.; Szymczak, R.
- Low Temperature Physics, Vol. 27, Issue 9
Synthesis and characterization of metastable, 20 nm-sized Pna 2 1 -LiCoPO 4 nanospheres
journal, April 2017
- Ludwig, Jennifer; Nordlund, Dennis; Doeff, Marca M.
- Journal of Solid State Chemistry, Vol. 248
Facile, ethylene glycol-promoted microwave-assisted solvothermal synthesis of high-performance LiCoPO 4 as a high-voltage cathode material for lithium-ion batteries
journal, January 2016
- Ludwig, Jennifer; Marino, Cyril; Haering, Dominik
- RSC Advances, Vol. 6, Issue 86
Thermal Stability of LiCoPO[sub 4] Cathodes
journal, January 2008
- Bramnik, Natalia N.; Nikolowski, Kristian; Trots, Dmytro M.
- Electrochemical and Solid-State Letters, Vol. 11, Issue 6
Hydrothermal synthesis of LiCoPO4 cathode materials for rechargeable lithium ion batteries
journal, February 2005
- Huang, Xiang; Ma, Junfeng; Wu, Pingwei
- Materials Letters, Vol. 59, Issue 5
Rerefinement of cobalt diphosphate against new intensity data
journal, April 2002
- El Bali, Brahim; Bolte, Michael
- Acta Crystallographica Section E Structure Reports Online, Vol. 58, Issue 5
Local structure and redox energies of lithium phosphates with olivine- and Nasicon-like structures
journal, February 2005
- Salah, A.; Jozwiak, P.; Garbarczyk, J.
- Journal of Power Sources, Vol. 140, Issue 2
Review and analysis of nanostructured olivine-based lithium recheargeable batteries: Status and trends
journal, June 2013
- Zaghib, K.; Guerfi, A.; Hovington, P.
- Journal of Power Sources, Vol. 232
Morphology-controlled microwave-assisted solvothermal synthesis of high-performance LiCoPO4 as a high-voltage cathode material for Li-ion batteries
journal, February 2017
- Ludwig, Jennifer; Marino, Cyril; Haering, Dominik
- Journal of Power Sources, Vol. 342
Phase Transitions Occurring upon Lithium Insertion−Extraction of LiCoPO 4
journal, February 2007
- Bramnik, Natalia N.; Nikolowski, Kristian; Baehtz, Carsten
- Chemistry of Materials, Vol. 19, Issue 4
Electronic structure and spin-state transition of
journal, June 1993
- Abbate, M.; Fuggle, J. C.; Fujimori, A.
- Physical Review B, Vol. 47, Issue 24
Crystallographic Computing System JANA2006: General features
journal, January 2014
- Petříček, Václav; Dušek, Michal; Palatinus, Lukáš
- Zeitschrift für Kristallographie - Crystalline Materials, Vol. 229, Issue 5
A new LiCoPO4 polymorph via low temperature synthesis
journal, January 2013
- Jähne, Carsten; Neef, Christoph; Koo, Changhyun
- Journal of Materials Chemistry A, Vol. 1, Issue 8
The linear magnetoelectric effect in LiCoPO 4 Revisited
journal, November 1994
- Rivera, J. -P.
- Ferroelectrics, Vol. 161, Issue 1
Influence of the Structure on the Electrochemical Performance of Lithium Transition Metal Phosphates as Cathodic Materials in Rechargeable Lithium Batteries: A New High-Pressure Form of LiMPO 4 (M = Fe and Ni)
journal, May 2001
- García-Moreno, O.; Alvarez-Vega, M.; García-Jaca, J.
- Chemistry of Materials, Vol. 13, Issue 5
Unusual spin fluctuations and magnetic frustration in olivine and non-olivine LiCoPO detected by and nuclear magnetic resonance
journal, April 2014
- Baek, S. -H.; Klingeler, R.; Neef, C.
- Physical Review B, Vol. 89, Issue 13
Cathode properties of phospho-olivine LiMPO4 for lithium secondary batteries
journal, July 2001
- Okada, Shigeto; Sawa, Shoichiro; Egashira, Minato
- Journal of Power Sources, Vol. 97-98
Works referencing / citing this record:
In Situ Probing Multiple-Scale Structures of Energy Materials for Li-Ion Batteries
journal, May 2019
- Zhu, He; Huang, Yalan; Zhu, Hekang
- Small Methods