Use of In Situ XAS to Elucidate Surface Structural Changes and Capacity Loss during Electrochemical Cycling of nanoscale LiCoO2

ABSTRACTLixMn2O4 materials are of considerable interest in battery research and development. The crystal structure of this material can significantly affect the electrochemical performance. The ability to monitor the changes of the crystal structure during use, that is during electrochemical cycling, would prove useful to verify these types of structural changes. We report in-situ XRD measurements of LiMn2O4 cathodes with the use of an electrochemical cell designed for in-situ X-ray analysis. Cells prepared using this cell design allow investigation of the changes in the LiMn2O4 structure during charge and discharge. We describe the variation in lattice parameters along the voltage plateaus and consider the structural changes in terms of the electrochemical results on each cell. Kinetic effects of LiMn2O4 phase changes are also addressed. Applications of the in-situ cell to other compounds such as LiCoO2 cathodes and carbon anodes are presented as well.

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Structural changes in a commercial lithium-ion battery during electrochemical cycling: An in situ neutron diffraction study

Journal of Power Sources ◽

10.1016/j.jpowsour.2010.06.114 ◽

2010 ◽

Vol 195 (24) ◽

pp. 8258-8266 ◽

Cited By ~ 136

Author(s):

Neeraj Sharma ◽

Vanessa K. Peterson ◽

Margaret M. Elcombe ◽

Maxim Avdeev ◽

Andrew J. Studer ◽

...

Keyword(s):

Neutron Diffraction ◽

Diffraction Study ◽

Lithium Ion Battery ◽

Structural Changes ◽

Lithium Ion ◽

Neutron Diffraction Study ◽

Electrochemical Cycling ◽

In Situ Neutron Diffraction

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Fast operando X-ray pair distribution function using the DRIX electrochemical cell

Journal of Synchrotron Radiation ◽

10.1107/s160057752000747x ◽

2020 ◽

Vol 27 (5) ◽

pp. 1190-1199

Author(s):

Maria Diaz-Lopez ◽

Geoffrey L. Cutts ◽

Phoebe K. Allan ◽

Dean S. Keeble ◽

Allan Ross ◽

...

Keyword(s):

Distribution Function ◽

Pair Distribution Function ◽

Structural Changes ◽

Structural Information ◽

Scattering Data ◽

Cell Design ◽

Total Scattering ◽

X Ray ◽

Electrochemical Cycling

In situ electrochemical cycling combined with total scattering measurements can provide valuable structural information on crystalline, semi-crystalline and amorphous phases present during (dis)charging of batteries. In situ measurements are particularly challenging for total scattering experiments due to the requirement for low, constant and reproducible backgrounds. Poor cell design can introduce artefacts into the total scattering data or cause inhomogeneous electrochemical cycling, leading to poor data quality or misleading results. This work presents a new cell design optimized to provide good electrochemical performance while performing bulk multi-scale characterizations based on total scattering and pair distribution function methods, and with potential for techniques such as X-ray Raman spectroscopy. As an example, the structural changes of a nanostructured high-capacity cathode with a disordered rock-salt structure and composition Li4Mn2O5 are demonstrated. The results show that there is no contribution to the recorded signal from other cell components, and a very low and consistent contribution from the cell background.

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Structure-Stability Correlations in Li-ion Battery Cathode Materials

MRS Proceedings ◽

10.1557/opl.2014.412 ◽

2014 ◽

Vol 1655 ◽

Author(s):

Christopher Patridge ◽

Corey Love ◽

Wojtek Dmowski ◽

David Ramaker ◽

Michelle Johannes ◽

...

Keyword(s):

Structural Changes ◽

High Energy ◽

Ex Situ ◽

Structure Stability ◽

X Ray Diffraction ◽

X Ray ◽

Capacity Loss ◽

Pair Density ◽

Pdf Analysis

ABSTRACTDetailed structural studies of two lithiated metal oxides, Li2CuO2 and nanoscale LiCoO2, have been carried out using ex situ high-energy X-ray diffraction (XRD) and in situ X-ray absorption spectroscopy (XAS) with the objective of understanding structural changes that might cause capacity loss during cycling. XRD on the cuprate was studied at various states of charge and phase composition, and the bulk state was determined by Rietveld refinement and pair density function (PDF) analysis. Results showed a largely irreversible structural change of the material upon oxidation of Cu2+ as well as CuO formation. The in-situ XAS of the LiCoO2 was analyzed through a difference method to extract the changes in the local structure that occur upon cycling in both the near edge (XANES) and extended region (EXAFS). Results suggest that cycling causes site exchange of the Co and Li ions near the surface of the nanoscale LiCoO2.

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An In-Situ XAS Study of the Structural Changes in a CuO-CeO2/Al2O3 Catalyst during Total Oxidation of Propane

10.1063/1.2644635 ◽

2007 ◽

Cited By ~ 1

Author(s):

Geert Silversmith ◽

Maria Olea ◽

Hilde Poelman ◽

Veerle Balcaen ◽

Philippe Heynderickx ◽

...

Keyword(s):

Structural Changes ◽

Total Oxidation ◽

In Situ Xas ◽

Al2o3 Catalyst

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A furnace forin situX-ray diffraction studies of insertion processes in electrode materials at elevated temperatures

Journal of Applied Crystallography ◽

10.1107/s0021889801011864 ◽

2001 ◽

Vol 34 (5) ◽

pp. 654-657 ◽

Cited By ~ 1

Author(s):

T. Eriksson ◽

A. M. Andersson ◽

Ö. Bergström ◽

K. Edström ◽

T. Gustafsson ◽

...

Keyword(s):

Structural Changes ◽

Electrode Materials ◽

Elevated Temperatures ◽

Lithium Ion ◽

X Ray Diffraction ◽

X Ray ◽

Electrochemical Cycling ◽

Flat Cell ◽

And Storage

A furnace is described forin situX-ray diffraction studies, in transmission mode, of structural changes in electrode materials for Li-ion (polymer) batteries in the ambient to 300°C temperature range. The method exploits the thin flat-cell geometry of the lithium-polymer battery concept. The flat sample is able to oscillate about a horizontal axis in its own plane in the X-ray beam, to provide better averaging during the diffraction experiment. The use of the device is demonstrated in a study of lithium intercalation in graphite (a commonly used anode material in lithium-ion batteries) during electrochemical cycling and storage at 70°C.

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In situ XAFS study on cathode materials for lithium-ion batteries

MRS Proceedings ◽

10.1557/proc-658-gg9.6 ◽

2000 ◽

Vol 658 ◽

Cited By ~ 1

Author(s):

Takamasa Nonaka ◽

Chikaaki Okuda ◽

Yoshio Ukyo ◽

Tokuhiko Okamoto

Keyword(s):

Structural Changes ◽

Chemical Shifts ◽

Lithium Ion ◽

Capacity Fading ◽

Teller Distortion ◽

Jahn Teller ◽

Electrochemical Cycling ◽

X Ray Absorption ◽

Jahn Teller Distortion

ABSTRACTNi and Co K-edge X-ray absorption spectra of LiNi0.8Co0.2O2 have been collected using in situ coin cells. To investigate the electronic and structural changes accompanied by the capacity fading during electrochemical cycling and keeping batteries at high temperatures, the cells with different cycling states and keeping conditions (temperature, time) were prepared. Upon charging the cell, the Ni and Co K absorption edge shifted towards higher energy, and the good correlation between the range of chemical shifts upon charging and the capacity of the cell was observed. From quantitative analysis of EXAFS data, it was revealed that the capacity fading is closely related to the Jahn-Teller distortion of the NiO6 octahedron.

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In situ XRD and operando spectra-electrochemical investigation of tetragonal WO3-x nanowire networks for electrochromic supercapacitors

NPG Asia Materials ◽

10.1038/s41427-021-00319-7 ◽

2021 ◽

Vol 13 (1) ◽

Author(s):

Shen Wang ◽

Hongbo Xu ◽

Tingting Hao ◽

Peiyuan Wang ◽

Xiang Zhang ◽

...

Keyword(s):

Reaction Mechanism ◽

Electronic Device ◽

High Capacity ◽

Optical Modulation ◽

Function Evaluation ◽

Dual Function ◽

Electrochemical Performances ◽

Electrochemical Cycling ◽

Nanowire Networks

AbstractElectrochromic supercapacitors (ESCs) are appealing for smart electronic device applications due to their advantages of dual-function integration. Unfortunately, the synchronous dual-function evaluation and the essential reaction mechanism are ambiguous. Herein, we constructed a 3D WO3-x nanowire networks/fluorine-doped tin oxide (WO3-x NWNs/FTO) bifunctional electrode for ESCs by a solvothermal self-crystal seeding method. The synchronous correspondence relationship between the optical and electrochemical performances of the WO3-x NWNs/FTO electrode was explored using an operando spectra-electrochemical characterization method. It reveals an excellent areal capacity of 57.57 mF cm−2 with a high corresponding optical modulation (ΔT) of 85.05% and high optical-electrochemical cycling stability. Furthermore, the synergistic reaction mechanism between the Al3+ ion intercalation behavior and the surface pseudocapacitance reaction during electrochemical cycling is revealed utilizing in situ X-ray diffraction. Based on these results, an ESC device was constructed by pairing WO3-x/FTO as the cathode with V2O5 nanoflowers/FTO (V2O5 NFs/FTO) as the anode, which simultaneously deliver high capacity and large optical modulation. Moreover, the energy storage level of the ESC device could be visually monitored by rapid and reversible color transitions in real time. This work provides a promising pathway to developing multi-functional integrated smart supercapacitors.

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