Applying chemometrics to study battery materials: Towards the comprehensive analysis of complex operando datasets

Fehse, Marcus; Iadecola, Antonella; Sougrati, Moulay Tahar; Conti, Paolo; Giorgetti, Marco; Stievano, Lorenzo

doi:10.1016/j.ensm.2019.02.002

Cited by 55 publications

(49 citation statements)

References 77 publications

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“…Considering the difficulty of accurately analyzing each spectrum separately, a chemometric approach implying principal component analysis (PCA) and multivariate curve resolution–alternating least squares (MCR–ALS) analyses was conducted to extract the maximum useful information from this large dataset. A detailed description of this analytical approach is given by Fehse et al The PCA variance plot shown in Figure SI‐4, Supporting Information, suggests that at least three components are needed to describe the whole dataset. These three pure components were reconstructed thanks to the MCR–ALS algorithm (Figure c).…”

Section: Resultsmentioning

confidence: 99%

“…The energy calibration and normalization of the operando XAS spectra were performed using the Athena software . The normalized operando spectra were analyzed globally using a chemometric approach implying PCA and MCR–ALS, via a procedure described in detail by Fehse et al This analysis allows one to extract the pure spectral components that are necessary to describe, via adapted linear combinations, the entire dataset. Such components, as well as the ex situ spectra, were finally analyzed using the Arthemis software .…”

Section: Methodsmentioning

confidence: 99%

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Reversible High Capacity and Reaction Mechanism of Cr₂(NCN)₃ Negative Electrodes for Li‐Ion Batteries

et al. 2020

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A detailed study of the electrochemical reaction mechanism between lithium and the trivalent transition‐metal carbodiimide Cr2(NCN)3, which shows excellent performance as a negative electrode material in Li‐ion batteries, is conducted combining complementary operando analyses and state‐of‐the‐art density functional theory (DFT) calculations. As predicted by DFT, and evidenced by operando X‐ray diffraction and Cr K‐edge absorption spectroscopy, a two‐step reaction pathway involving two redox couples (Cr3+/Cr2+ and Cr2+/Cr0) and a concomitant formation of Cr metal nanoparticles is apparent, thus indicating that the conversion reaction of this carbodiimide upon lithiation occurs only after a preliminary intercalation step involving two Li per unit formula. This mechanism, evidenced for the first time in transition‐metal carbodiimides, is likely behind its outstanding electrochemical performance as Cr2(NCN)3 can maintain more than 600 mAh g−1 for 900 cycles at a high rate of 2 C.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Reversible High Capacity and Reaction Mechanism of Cr₂(NCN)₃ Negative Electrodes for Li‐Ion Batteries

et al. 2020

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“…At last, the lithiation of FeNCN was followed experimentally by operando Fe K-edge XAS in order to corroborate or falsify the theoretical findings. [28] In particular, the extended fine structure of the XAS spectrum (EXAFS) [29] is very sensitive to the modification of the nearest-neighbor shell of the Fe atoms and is hence used to validate the DFT-predicted ternary intermediates. The complete operando data set depicting the evolution of Fe K-edge XAS spectra acquired during the first electrochemical discharge of FeNCN vs. Li is presented as a contour plot in Figure 5 a.…”

Section: Resultsmentioning

confidence: 99%

Quantum‐Chemical Study of the FeNCN Conversion‐Reaction Mechanism in Lithium‐ and Sodium‐Ion Batteries

et al. 2020

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We report a computational study on 3d transition‐metal (Cr, Mn, Fe, and Co) carbodiimides in Li‐ and Na‐ion batteries. The obtained cell voltages semi‐quantitatively fit the experiments, highlighting the practicality of PBE+U as an approach for modeling the conversion‐reaction mechanism of the FeNCN archetype with lithium and sodium. Also, the calculated voltage profiles agree satisfactorily with experiment both for full (Li‐ion battery) and partial (Na‐ion battery) discharge, even though experimental atomistic knowledge is missing up to now. Moreover, we rationalize the structural preference of intermediate ternaries and their characteristic lowering in the voltage profile using chemical‐bonding and Mulliken‐charge analysis. The formation of such ternary intermediates for the lithiation of FeNCN and the contribution of at least one ternary intermediate is also confirmed experimentally. This theoretical approach, aided by experimental findings, supports the atomistic exploration of electrode materials governed by conversion reactions.

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“…The Mn 2+ /Mn 3+ redox couple reactions took place at a high state of charge in the hydrated system; the oxidation of both Mn and Fe gradually increased during the whole charging process. Similar works were reported by other researchers recently …”

Section: Xas Techniques For Prussian Blue Analogues For Sibsmentioning

confidence: 99%

Understanding Challenges of Cathode Materials for Sodium‐Ion Batteries using Synchrotron‐Based X‐Ray Absorption Spectroscopy

Chen

Chou

Dou

2019

Batteries & Supercaps

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An in-depth understanding of the electrochemical behavior of cathode materials in a complex chemical environment is critical for the development of state-of-the-art sodium-ion batteries. Advanced synchrotron-based characterization is a powerful tool for collecting valuable information on complicated reaction mechanisms. X-ray absorption spectroscopy can be used to precisely monitor the valence state and corresponding changes during cycling of various elements. Information on the local structure, such as coordination number and bond information can also be extracted from the fitting data in Fourier transform extended X-ray absorption fine structure. In this review, we summarize findings on state-of-the-art cathode materials using ex-situ/in-situ X-ray absorption spectroscopy to probe fundamental discoveries on sodium-ion battery systems and what important and valuable results have been obtained. Further possible improvements and practical operating advice are also discussed in detail. . (a) Crystal structure of Na 3 V 2 (PO 4 ) 2 F 3 with space group Amam. (b) V K-edge XANES spectra at C/10. Reprinted with permission from (a) to (b). [51] Copyright 2017American Chemical Society. (c) Crystal structure of ɛ-VOPO 4 and corresponding charge/discharge curve. V K-edge in-situ XAS spectra of Mo 0.05 V 0.95 OPO 4 for (d) high-voltage discharge and (e) low-voltage discharge.

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Applying chemometrics to study battery materials: Towards the comprehensive analysis of complex operando datasets

Cited by 55 publications

References 77 publications

Reversible High Capacity and Reaction Mechanism of Cr₂(NCN)₃ Negative Electrodes for Li‐Ion Batteries

Reversible High Capacity and Reaction Mechanism of Cr₂(NCN)₃ Negative Electrodes for Li‐Ion Batteries

Quantum‐Chemical Study of the FeNCN Conversion‐Reaction Mechanism in Lithium‐ and Sodium‐Ion Batteries

Understanding Challenges of Cathode Materials for Sodium‐Ion Batteries using Synchrotron‐Based X‐Ray Absorption Spectroscopy

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Applying chemometrics to study battery materials: Towards the comprehensive analysis of complex operando datasets

Cited by 55 publications

References 77 publications

Reversible High Capacity and Reaction Mechanism of Cr2(NCN)3 Negative Electrodes for Li‐Ion Batteries

Reversible High Capacity and Reaction Mechanism of Cr2(NCN)3 Negative Electrodes for Li‐Ion Batteries

Quantum‐Chemical Study of the FeNCN Conversion‐Reaction Mechanism in Lithium‐ and Sodium‐Ion Batteries

Understanding Challenges of Cathode Materials for Sodium‐Ion Batteries using Synchrotron‐Based X‐Ray Absorption Spectroscopy

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Reversible High Capacity and Reaction Mechanism of Cr₂(NCN)₃ Negative Electrodes for Li‐Ion Batteries

Reversible High Capacity and Reaction Mechanism of Cr₂(NCN)₃ Negative Electrodes for Li‐Ion Batteries