In-Situ Infrared Spectroscopic Studies of Electrochemical Energy Conversion and Storage

Li, Jun‐Tao; Zhou, Zhi‐You; Broadwell, Ian; Sun, Shi‐Gang

doi:10.1021/ar200215t

Cited by 112 publications

(95 citation statements)

References 49 publications

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“…This has motivated the use of many surface-science techniques for the characterization of the surface of battery electrodes, especially in the last two decades for the study of lithium-ion batteries. [ 10,35 ] By investigating the SEI formation and evolution on amorphous silicon Li-ion electrodes by in situ FTIR, the present study intends to reveal a detailed image of the surface phenomena at the silicon/electrolyte interface under its original chemical environment and obtain quantitative information about its evolution. Even though thin fi lms cannot be used in practical battery designs (except for microbatteries), they represent a well-controlled geometry allowing for quantitative measurements of electrode evolutions.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

Corte

Caillon

Jordy

et al. 2015

Advanced Energy Materials

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special environment for its characterization appear as steps which in most cases might strongly modify the active material. [ 1 ] Benefi ting from characterization techniques able to analyze the electrodes in situ and in operando therefore appears of uttermost importance for obtaining information of direct relevance regarding the electrode processes. We show in the present work that such pieces of information can be obtained by using in situ Fourier-transform infrared (FTIR) spectroscopy in a suitable geometry, which avoids the traditional limitations associated with this technique and allows for quantitative information to be extracted. [ 2 ] This approach therefore brings significant complementary information to other useful techniques operating in the electrochemical environment, which focus either on electrode materials, such as nuclear magnetic resonance (NMR) [ 3,4 ] or X-ray absorption, diffraction or imaging, [ 5,6 ] or on electrode surfaces, such as scanning probe microscopies. [ 7,8 ] Using infrared spectroscopy at the electrochemical interface has already been attempted in the context of the study of battery electrodes. [9][10][11] The geometry adopted for these studies was however severely limiting the sensitivity, and imposing stringent limitations for the electrochemical conditions (especially in terms of mass-transport limitations), which have direct impact on the obtained results. [ 12 ] Here, we use an alternative approach based on the multiple-internal-refl ection geometry, which allows for benefi ting from an enhanced sensitivity and working in electrochemical conditions similar to those of standard batteries for studying thin-fi lm electrodes. As shown hereafter, such a capability provides useful information of direct relevance for both interfacial and bulk electrode processes.The present study has been devoted to silicon electrodes, studied in a half-cell confi guration against a lithium-metal electrode. Silicon represents an impressive gain in energy density for negative electrodes in Li-ion batteries. One strategy to overcome the poor capacity retention associated with the massive volume expansion of silicon during lithiation is the use of nanosized geometries, for instance, particles, [13][14][15][16] wires, [17][18][19] and tubes. [ 20,21 ] The use of a thin-fi lm geometry also prevents Multiple-internal-refl ection infrared spectroscopy allows for the study of thin-fi lm amorphous silicon electrodes in situ and in operando, in conditions typical of those used in Li-ion batteries. It brings an enhanced sensitivity, and the attenuated-total-refl ection geometry allows for the extraction of quantitative information. When electrodes are cycled in representative electrolytes, the simultaneously recorded infrared spectra give an insight into the solid/electrolyte interphase (SEI) composition. They also unravel the dynamic behavior of this SEI layer by quantitatively assessing its thickness, which increases during silicon lithiation and partially decreases during delithiation. Li-ion solvation ...

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Section: Introductionmentioning

confidence: 99%

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

Corte

Caillon

Jordy

et al. 2015

Advanced Energy Materials

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“…Vibrational spectroscopy plays an important role in species identification at catalytic surfaces and provides essential information about reaction intermediates and pathways [1]. This is necessary for rational design of effective catalysts.…”

Section: Introductionmentioning

confidence: 99%

Towards Accurate Spectroscopic Identification of Species at Catalytic Surfaces: Anharmonic Vibrations of Formate on AuPt

et al. 2012

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We present a calculation of vibrational frequencies of formate on the AuPt(111) surface alloy including full anharmonicity and coupling of all six intramolecular degrees of freedom. This species is a key intermediate in methanol oxidation on this material. We use a modified version of the method of Manzhos and Carrington to compute the spectrum directly from a small number (<10,000) of DFT single-point energies, bypassing the construction of a potential energy surface. This is the first such calculation for a 4-atomic species at a surface. The spectrum is obtained using rectangular collocation and a small basis set of parameterized Hermite functions. The achievable accuracy of the order of several cm -1 corresponds to the typical experimental resolution. Using normal coordinates makes the equations simple and general and easily applicable to other systems. This calculation is doable on a PC. We predict that anharmonicity and coupling lower the fundamental frequencies by dozens of cm -1 , which could affect species assignment.

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“…There have been few review articles on FTIR's applications in batteries . More articles with technical details of ex situ and in situ FTIR have been published on catalysts …”

Section: Applications Of Ftir Spectroscopy In Secondary Battery Studiesmentioning

confidence: 99%

Applications of Conventional Vibrational Spectroscopic Methods for Batteries Beyond Li‐Ion

Deng

Dong

et al. 2018

Small Methods

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Advanced energy‐storage devices are in tremendous demand to meet the ever‐growing electrification of the economy. To design batteries, it is critical to understand the evolving structures of the electrode materials, the compositions of the solid electrolyte interphase, and the reaction intermediates during the electrochemical processes. To this end, a plethora of characterization techniques are employed in battery research to bridge the fundamental understanding to practical optimization of battery systems. Vibrational spectroscopy methods, including Raman spectroscopy, and Fourier transform infrared (FTIR) spectroscopy are powerful analytic tools for the purposes of battery studies. Here, the usage of Raman and FTIR spectroscopy techniques for secondary batteries, such as lithium‐ion batteries, lithium–sulfur batteries, lithium–oxygen batteries, sodium‐ion batteries, and potassium‐ion batteries, is described.

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In-Situ Infrared Spectroscopic Studies of Electrochemical Energy Conversion and Storage

Cited by 112 publications

References 49 publications

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

Spectroscopic Insight into Li‐Ion Batteries during Operation: An Alternative Infrared Approach

Towards Accurate Spectroscopic Identification of Species at Catalytic Surfaces: Anharmonic Vibrations of Formate on AuPt

Applications of Conventional Vibrational Spectroscopic Methods for Batteries Beyond Li‐Ion

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