In situ XAS study of the local structure of the nano-Li2FeSiO4/C cathode

Kucuk, Kamil; Aryal, Shankar; Moazzen, Elahe; Timofeeva, Elena V.; Segre, Carlo U.

doi:10.1088/2515-7655/abf543

In situ XAS study of the local structure of the nano-Li₂FeSiO₄/C cathode

Journal Article · Mon Jun 28 00:00:00 EDT 2021 · JPhys Energy

DOI:https://doi.org/10.1088/2515-7655/abf543· OSTI ID:1812062

^[1]; ^[1]; ^[2]; ^[3]; ^[3]

Illinois Institute of Technology, Chicago, IL (United States). Dept. of Physics. CSRRI
Illinois Institute of Technology, Chicago, IL (United States). Dept. of Chemistry; Northwestern Univ., Evanston, IL (United States). Dept. of Materials Science and Engineering
Illinois Institute of Technology, Chicago, IL (United States). Dept. of Chemistry

Despite the challenges in achieving its full theoretical capacity of reversible extraction of two Li ions, the Li₂FeSiO₄ (LFS) cathode shows a remarkable cycling stability once its low electronic conductivity is addressed. By studying the local structure around the iron during electrochemical cycling using in situ x-ray absorption spectroscopy (XAS), it is possible to gain insight into the factors which determine the electrochemical properties of this material. In order to practically perform in situ XAS studies, the charge/discharge of LFS was maximized using two approaches: (a) reducing the particle size of LFS samples from micro-scale to nano-scale in order to reduce the diffusion path for intercalating ions; and (b) applying a conductive coating to each nanoparticle to facilitate electron transfer. A family of LFS materials was synthesized and characterized using x-ray diffraction, and scanning electron microscopy with energy dispersive analysis for structural and morphological analysis, as well as cyclic voltammetry and cycling tests for electrochemical performance diagnosis. This material was then characterized by in situ XAS. The results provide insight into the stable electrochemical performance of LFS and suggest new synthetic routes to reaching the theoretical capacity.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Illinois Institute of Technology, Chicago, IL (United States)

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357; AR0000387

OSTI ID:: 1812062

Alternate ID(s):: OSTI ID: 1812926

Journal Information:: JPhys Energy, Journal Name: JPhys Energy Journal Issue: 3 Vol. 3; ISSN 2515-7655

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

References (36)

Hollow Micro-/Nanostructures: Synthesis and Applications Lou, Xiong Wen (David); Archer, Lynden A.; Yang, Zichao Advanced Materials, Vol. 20, Issue 21 https://doi.org/10.1002/adma.200800854	journal	November 2008
Wet Chemical Synthesis of Graphene Eigler, Siegfried; Enzelberger-Heim, Michael; Grimm, Stefan Advanced Materials, Vol. 25, Issue 26 https://doi.org/10.1002/adma.201300155	journal	May 2013
Li-ion batteries: basics, progress, and challenges Deng, Da Energy Science & Engineering, Vol. 3, Issue 5 https://doi.org/10.1002/ese3.95	journal	September 2015
Scanning electron microscopy 1928-1965 McMullan, D. Scanning, Vol. 17, Issue 3 https://doi.org/10.1002/sca.4950170309	journal	May 1995
Spin State Behavior in Some Cobaltites (III) and (IV) with Perovskite or Related Structure Pouchard, Michel; Villesuzanne, Antoine; Doumerc, Jean-Pierre Journal of Solid State Chemistry, Vol. 162, Issue 2 https://doi.org/10.1006/jssc.2001.9294	journal	December 2001
Materials and processing for lithium-ion batteries Daniel, Claus JOM, Vol. 60, Issue 9 https://doi.org/10.1007/s11837-008-0116-x	journal	September 2008
Electrochemical performance of Li2FeSiO4 as a new Li-battery cathode material Nytén, Anton; Abouimrane, Ali; Armand, Michel Electrochemistry Communications, Vol. 7, Issue 2 https://doi.org/10.1016/j.elecom.2004.11.008	journal	February 2005
On-demand design of polyoxianionic cathode materials based on electronegativity correlations: An exploration of the Li2MSiO4 system (M=Fe, Mn, Co, Ni) Arroyo-de Dompablo, M. E.; Armand, M.; Tarascon, J. M. Electrochemistry Communications, Vol. 8, Issue 8 https://doi.org/10.1016/j.elecom.2006.06.003	journal	August 2006
Structural investigations of LiFePO4 electrodes and in situ studies by Fe X-ray absorption spectroscopy Deb, Aniruddha; Bergmann, Uwe; Cramer, S. P. Electrochimica Acta, Vol. 50, Issue 25-26 https://doi.org/10.1016/j.electacta.2005.02.086	journal	September 2005
Facile synthesis of Li2FeSiO4/C composites with triblock copolymer P123 and their application as cathode materials for lithium ion batteries Wu, Xiaozhen; Jiang, Xin; Huo, Qisheng Electrochimica Acta, Vol. 80 https://doi.org/10.1016/j.electacta.2012.06.122	journal	October 2012
Multi-spectroscopic study of Fe(II) in silicate glasses: Implications for the coordination environment of Fe(II) in silicate melts Jackson, William E.; Farges, Francois; Yeager, Mark Geochimica et Cosmochimica Acta, Vol. 69, Issue 17 https://doi.org/10.1016/j.gca.2005.01.008	journal	September 2005
Synthesis and electrochemical performance of Li2FeSiO4/C/carbon nanosphere composite cathode materials for lithium ion batteries Yang, Jinlong; Kang, Xiaochun; Hu, Lin Journal of Alloys and Compounds, Vol. 572 https://doi.org/10.1016/j.jallcom.2013.03.256	journal	September 2013
In-situ XAS study on Li2MnSiO4 and Li2FeSiO4 cathode materials Dominko, R.; Arčon, I.; Kodre, A. Journal of Power Sources, Vol. 189, Issue 1 https://doi.org/10.1016/j.jpowsour.2008.11.077	journal	April 2009
Synthesis and characterization of Li2Fe0.97M0.03SiO4 (M=Zn2+, Cu2+, Ni2+) cathode materials for lithium ion batteries Deng, C.; Zhang, S.; Yang, S. Y. Journal of Power Sources, Vol. 196, Issue 1 https://doi.org/10.1016/j.jpowsour.2010.06.064	journal	January 2011
The Fe K-edge X-ray absorption characteristics of La1−xSrxFeO3−δ prepared by solid state reaction Haas, O.; Vogt, U. F.; Soltmann, C. Materials Research Bulletin, Vol. 44, Issue 6 https://doi.org/10.1016/j.materresbull.2008.11.026	journal	June 2009
Li-ion battery materials: present and future Nitta, Naoki; Wu, Feixiang; Lee, Jung Tae Materials Today, Vol. 18, Issue 5 https://doi.org/10.1016/j.mattod.2014.10.040	journal	June 2015
Recent progress in cathode materials research for advanced lithium ion batteries Xu, Bo; Qian, Danna; Wang, Ziying Materials Science and Engineering: R: Reports, Vol. 73, Issue 5-6 https://doi.org/10.1016/j.mser.2012.05.003	journal	May 2012
Direct preparation of conductive carbon layer (CCL) on alumina as a model system for direct preparation of carbon coated particles of the composite Li-ion electrodes Molenda, M. Solid State Ionics, Vol. 179, Issue 1-6 https://doi.org/10.1016/j.ssi.2007.12.034	journal	March 2008
Impact of Cl Doping on Electrochemical Performance in Orthosilicate (Li ₂ FeSiO ₄ ): A Density Functional Theory Supported Experimental Approach Singh, Shivani; Raj, Anish K.; Sen, Raja ACS Applied Materials & Interfaces, Vol. 9, Issue 32 https://doi.org/10.1021/acsami.7b07502	journal	August 2017
Lithium Iron Orthosilicate Cathode: Progress and Perspectives Ni, Jiangfeng; Jiang, Yu; Bi, Xuanxuan ACS Energy Letters, Vol. 2, Issue 8 https://doi.org/10.1021/acsenergylett.7b00452	journal	July 2017
The lithium extraction/insertion mechanism in Li ₂ FeSiO ₄ Nytén, Anton; Kamali, Saeed; Häggström, Lennart J. Mater. Chem., Vol. 16, Issue 23 https://doi.org/10.1039/B601184E	journal	January 2006
Electrochemistry of orthosilicate-based lithium battery cathodes: a perspective Ferrari, Stefania; Capsoni, Doretta; Casino, Simone Phys. Chem. Chem. Phys., Vol. 16, Issue 22 https://doi.org/10.1039/C4CP00511B	journal	January 2014
Template-free hydrothermal synthesis of Li ₂ FeSiO ₄ hollow spheres as cathode materials for lithium-ion batteries Xu, Yimeng; Shen, Wei; Zhang, Aili Journal of Materials Chemistry A, Vol. 2, Issue 32 https://doi.org/10.1039/C4TA02384F	journal	January 2014
Effect of Fe ²⁺ substitution on the structure and electrochemistry of LiCoPO ₄ prepared by mechanochemically assisted carbothermal reduction Kosova, N. V.; Podgornova, O. A.; Devyatkina, E. T. J. Mater. Chem. A, Vol. 2, Issue 48 https://doi.org/10.1039/C4TA04221B	journal	January 2014
Advances in high-capacity Li ₂ MSiO ₄ (M = Mn, Fe, Co, Ni, …) cathode materials for lithium-ion batteries Girish, H. -N.; Shao, G. -Q. RSC Advances, Vol. 5, Issue 119 https://doi.org/10.1039/C5RA18594G	journal	January 2015
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
Hierarchical porous Li2FeSiO4/C composite with 2 Li storage capacity and long cycle stability for advanced Li-ion batteries Chen, Zhongxue; Qiu, Shen; Cao, Yuliang Journal of Materials Chemistry A, Vol. 1, Issue 16 https://doi.org/10.1039/c3ta00611e	journal	January 2013
The Scherrer Formula for X-Ray Particle Size Determination Patterson, A. L. Physical Review, Vol. 56, Issue 10 https://doi.org/10.1103/PhysRev.56.978	journal	November 1939
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
A profile refinement method for nuclear and magnetic structures Rietveld, H. M. Journal of Applied Crystallography, Vol. 2, Issue 2, p. 65-71 https://doi.org/10.1107/S0021889869006558	journal	June 1969
The structure of magnetite: defect structure II Fleet, M. E. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 38, Issue 6 https://doi.org/10.1107/S056774088200702X	journal	June 1982
IFEFFIT : interactive XAFS analysis and FEFF fitting Newville, Matthew Journal of Synchrotron Radiation, Vol. 8, Issue 2 https://doi.org/10.1107/S0909049500016964	journal	March 2001
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Redetermination of the low-temperature polymorph of Li ₂ MnSiO ₄ from single-crystal X-ray data Sato, Mineo; Ishigaki, Tadashi; Uematsu, Kazuyoshi Acta Crystallographica Section E Structure Reports Online, Vol. 68, Issue 9 https://doi.org/10.1107/S1600536812035040	journal	August 2012
A Review on the Structural Studies of Batteries and Host Materials by X-Ray Absorption Spectroscopy Giorgetti, Marco ISRN Materials Science, Vol. 2013 https://doi.org/10.1155/2013/938625	journal	January 2013
Nano/Micro Lithium Transitionmetal (Fe, Mn, Co and Ni) Silicate Cathode Materials for Lithium Ion Batteries Zhang, Qingtang; Zhao, Yongle; Su, Ce Recent Patents on Nanotechnology, Vol. 5, Issue 3 https://doi.org/10.2174/1872210511105030225	journal	November 2011

Similar Records

Ex Situ and Operando XRD and XAS Analysis of MoS₂: A Lithiation Study of Bulk and Nanosheet Materials

Journal Article · Wed Sep 25 20:00:00 EDT 2019 · ACS Applied Energy Materials · OSTI ID:1604319

Elucidating the mechanism underlying the augmented capacity of MoO₂ as an anode material in Li-ion batteries

Journal Article · Wed Oct 11 20:00:00 EDT 2023 · Journal of Materials Chemistry. A · OSTI ID:2558844

Mechanism of Exact Transition between Cationic and Anionic Redox Activities in Cathode Material Li₂FeSiO₄

Journal Article · Mon Oct 15 20:00:00 EDT 2018 · Journal of Physical Chemistry Letters · OSTI ID:1594900

Related Subjects

25 ENERGY STORAGE

In situ XAS study of the local structure of the nano-Li2FeSiO4/C cathode

Citation Formats

References (36)

Similar Records

Related Subjects

In situ XAS study of the local structure of the nano-Li₂FeSiO₄/C cathode