MicroRaman spectroscopy on LiMn2O4: warnings on laser-induced thermal decomposition

Paolone, A.; Sacchetti, A.; Corridoni, T.; Postorino, P.; Cantelli, R.; Rousse, Gwenaëlle; Masquelier, Christian

doi:10.1016/j.ssi.2004.02.002

Cited by 47 publications

(41 citation statements)

References 20 publications

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“…The difference between our experimental results and those of Ref. [12] may be due to the following three reasons. Firstly, samples prepared by different methods may have different microstructures and properties, which unavoidably affect the Raman spectra of samples.…”

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confidence: 80%

“…Finally, the laser power in this study, which is different from that in Ref. [12], reduces the Mn 4+ concentration in the material instead of the chemical decomposition because of the increase in the local temperature of the measured area. The decomposition of LiMn 2 O 4 would not occur until the laser power reached a critical value.…”

mentioning

confidence: 66%

“…• C. Paolone et al [12] studied the dependence of the Raman spectrum of spinel LiMn 2 O 4 on the excitation laser power. They concluded that the spinel LiMn 2 O 4 in the irradiated area by higher laser power transformed into Mn 3 O 4 because of laser-induced thermal decomposition.…”

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confidence: 99%

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Raman spectroscopy study of in situ change in laser irradiated LiMn2O4

Liu

Han

2012

中国光学快报

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A spinel LiMn2O4 is investigated via Raman spectroscopy at 514.5-nm excitation and X-ray diffraction. The dependence of Raman spectra on the different irradiated laser powers is determined and found to be different from that at 632.8-nm excitation. Based on our extensive analysis, our experimental results can be attributed to the laser heating effect, which reduces the Mn 4+ cation concentration in the local area. Consequently, the decrease in average Mn valence in the local area unavoidably induces the Jahn-Teller effect and local lattice distortion, which accounts for the evolution of the measured Raman spectra of spinel LiMn2O4.

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confidence: 80%

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confidence: 66%

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Raman spectroscopy study of in situ change in laser irradiated LiMn2O4

Liu

Han

2012

中国光学快报

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“…∼1.5 mW laser power), which might be too strong for the hydrated copper sulfate. The continuous laser irradiation has been shown to induce some localized heating at the surface of the sample, [38,39] which can subsequently accelerate the dehydration process.…”

Section: Thermo-raman Spectroscopymentioning

confidence: 99%

Use of thermo‐Raman spectroscopy and chemometric analysis to identify dehydration steps of hydrated inorganic samples—application to copper sulfate pentahydrate

Widjaja

Chong

Tjahjono

2009

J Raman Spectroscopy

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In situ thermo-Raman spectroscopy (TRS) measurements were performed in order to investigate solid-phase transformation of the copper sulfate pentahydrate from room temperature up to 300 • C. Band-target entropy minimization (BTEM), a blind-source separation algorithm, was employed in order to identify and reconstruct the pure component spectra of the species involved in the dehydration process. In spite of low signal-to-noise ratio and elevated baseline spectral data, BTEM was successfully utilized to identify and reconstruct four pure component spectra of copper sulfate pentahydrate, trihydrate, monohydrate, and anhydrate, which were formed during this thermally induced process. Subsequent mapping of these four pure component spectral estimates back onto the preprocessed spectra yielded the relative concentrations of each individual species. Finally, the transition temperatures of each dehydration step could be unambiguously deduced from the obtained concentration profile. The current study shows that combined thermo-Raman spectroscopy and chemometric analysis provides an effective tool to determine the dehydration temperatures as well as to identify the structures of each individual species involved in a solid-phase dehydration process.

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“…For example, Song et al [13] reported significant phase changes in LiCoO 2 /Co samples upon exposure to a laser beam, and laserinduced decomposition of spinel LiMn 2 O 4 has been reported by Paolone and coworkers. [14] In this communication, we explore some of the limitations associated with Raman spectroscopic measurements of FePO 4 -based cathode materials, paying special attention to thermal sensitivity.…”

Section: Introductionmentioning

confidence: 99%

Laser‐induced phase changes in olivine FePO₄: a warning on characterizing LiFePO₄‐based cathodes with Raman spectroscopy

Burba

Palmer

Holinsworth

2008

J Raman Spectroscopy

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Raman spectroscopy is an excellent technique for probing lithium intercalation reactions of many diverse lithium ion battery electrode materials. The technique is especially useful for probing LiFePO 4 -based cathodes because the intramolecular vibrational modes of the PO 4 3− anions yield intense bands in the Raman spectrum, which are sensitive to the presence of Li + ions. However, the high power lasers typically used in Raman spectroscopy can induce phase transitions in solid-state materials. These phase transitions may appear as changes in the spectroscopic data and could lead to erroneous conclusions concerning the delithiation mechanism of LiFePO 4 . Therefore, we examine the effect of exposing olivine FePO 4 to a range of power settings of a 532-nm laser. Laser power settings higher than 1.3 W/mm 2 are sufficient to destroy the FePO 4 crystal structure and result in the formation of disordered FePO 4 . After the laser is turned off, the amorphous FePO 4 compound crystallizes in the electrochemically inactive α-FePO 4 phase. The present experimental results strongly suggest that the power setting of the excitation laser should be carefully controlled when using Raman spectroscopy to characterize fundamental lithium ion intercalation processes of olivine materials. In addition, Raman spectra of the amorphous intermediate might provide insight into the α-FePO 4 to olivine FePO 4 phase transition that is known to occur at temperatures higher than 450 • C.

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MicroRaman spectroscopy on LiMn2O4: warnings on laser-induced thermal decomposition

Cited by 47 publications

References 20 publications

Raman spectroscopy study of in situ change in laser irradiated LiMn2O4

Raman spectroscopy study of in situ change in laser irradiated LiMn2O4

Use of thermo‐Raman spectroscopy and chemometric analysis to identify dehydration steps of hydrated inorganic samples—application to copper sulfate pentahydrate

Laser‐induced phase changes in olivine FePO₄: a warning on characterizing LiFePO₄‐based cathodes with Raman spectroscopy

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MicroRaman spectroscopy on LiMn2O4: warnings on laser-induced thermal decomposition

Cited by 47 publications

References 20 publications

Raman spectroscopy study of in situ change in laser irradiated LiMn2O4

Raman spectroscopy study of in situ change in laser irradiated LiMn2O4

Use of thermo‐Raman spectroscopy and chemometric analysis to identify dehydration steps of hydrated inorganic samples—application to copper sulfate pentahydrate

Laser‐induced phase changes in olivine FePO4: a warning on characterizing LiFePO4‐based cathodes with Raman spectroscopy

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Laser‐induced phase changes in olivine FePO₄: a warning on characterizing LiFePO₄‐based cathodes with Raman spectroscopy