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Operando XPS

Operando X-ray photoelectron spectroscopy, to monitor the chemical and electronic interface evolution in all-solid-state batteries

Degradation of the solid-electrolyte interface occurring during cycling is currently one of the most challenging issues for the development of all-solid-state batteries. Here we designed a unique electrochemical custom made cell for operando X-ray photoelectron spectroscopy (XPS) capable of maintaining high mechanical pressure with reliable electrochemistry and able to monitor in real-time the surface (electro-)chemical reactivity at the interfaces between the different composite.

 

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XPEEM post mortem/operando

Post mortem/operando XPEEM: for studying the surface of single particle in Li-ion battery electrodes

X-ray photoemission electron microscopy (XPEEM) with its excellent spatial resolution is a well-suited technique to elucidate the complex electrode-electrolyte interface reactions in Li-ion batteries. It provides element-specific contrast images and enables the acquisition of local X-ray absorption spectra on single particles. Here we demonstrate the strength of post mortem measurements and we show the first electrochemical cell dedicated for operando experiments in all-solid-state batteries.

 

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half-cell with the LiI-LPS solid electrolyte layer and the working electrode

Excellent cycling stability of graphite in all-solid-state battery using sulfide solid electrolyte

All-solid-state lithium ion batteries represent a promising battery technology for boosting the volumetric energy density and promising a superior safety. In this study excellent cycling stability of graphite anode material have been demonstrated in combination with sulfide-based solid electrolyte. Furthermore we evaluated the stability of the graphite-electrolyte interface by analyzing the normalized cumulative irreversible charge during cycling experiments.

 

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Li-rich nanoparticles

High performance doped Li-rich Li1+xMn2-xO4 cathodes nanoparticles synthesized by facile, fast and efficient microwave-assisted hydrothermal route

Li-rich nanoparticles of Li1+xMn2-xO4 doped with Al, Co or Ni are successfully synthesized using a facile, fast and efficient microwave-assisted hydrothermal route. In this study, we demonstrate that nanocrystallinity and cationic doping play an important role in improving the electrochemical performance with respect to LiMn2O4 microparticles. They significantly reduce the charge-transfer resistance, lower the 1st cycle irreversible capacity to 6%, and achieve a capacity retention between 85 and 90% after 380 cycles, with excellent columbic efficiency close to 99%.

 

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Schematic representation of the degradation mechanism at the LCO-LPS interface

Reactivity and potential profile across the electrified LiCoO2-Li3PS4 interface probed by operando X-ray photoelectron spectroscopy

All-solid-state lithium batteries are a promising alternative for next generation of safe energy storage devices, provided that parasitic side reactions and the resulting hindrances in ionic transport at the electrolyte-electrode interface can be overcome. Motivated by the need for a fundamental understanding of such interface, we present here real-time measurements of the (electro-)chemical reactivity and local surface potential at the electrified interface Li3PS4 and LiCoO2 using operando X-ray photoelectron spectroscopy.

 

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Structural formula of (a) EMIM+ cation, (b) TFSI- and (c) FSI- anions.

Li-ion solvation in TFSI and FSI - based ionic liquid electrolytes probed by X-ray photoelectron spectroscopy

We demonstrate the capability of conventional laboratory XPS to determine the anions solvation shell of Li+ cation within 1M of LiTFSI and 1M of LiFSI salts dissolved in (EMIM+-FSI-) and (EMIM+-TFSI-) ionic liquids. The binding energy difference between the N1s components originating from the EMIM+ cation and from TFSI- or FSI- anions, solvating the Li+, confirms that both TFSI- and FSI- contribute simultaneously to the Li+ solvation. Additionally, the degradation of the TFSI and FSI -based electrolytes under X-ray exposure is proved.   

 

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High quality 90 nm and 50 nm Li4Ti5O12 films integrated on silicon substrates

Integration of Li4Ti5O12 crystalline films on silicon towards high-rate performance lithionic devices

The growth of crystalline Li-based oxide thin films on silicon substrates is essential for the integration of next-generation solid-state lithionic and electronic devices. In this work, we employ a 2 nm γ-Al2O3 buffer layer on Si substrates in order to grow high quality crystalline thin films Li4Ti5O12 (LTO). Long-term galvanostatic cycling of 50 nm LTO demonstrates exceptional electrochemical performance, specific capacity of 175 mAh g-1 and 56 mAh g-1 at 100C and 5000C respectively, with a capacity retention of 91% after 5000 cycles.

 

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