Didier Gourier

Electron paramagnetic resonance imaging for real-time monitoring of Li-ion batteries

Batteries for electrical storage are central to any future alternative energy paradigm. The ability to probe the redox mechanisms occurring at electrodes during their operation is essential to improve battery performances. Here we present the first report on Electron Paramagnetic Resonance operando spectroscopy and in situ imaging of a Li-ion battery using Li2Ru0.75Sn0.25O3, a high-capacity (>270 mAh g−1) Li-rich layered oxide, as positive electrode. By monitoring operando the electron paramagnetic resonance signals of Ru5+ and paramagnetic oxygen species, we unambiguously prove the formation of reversible (O2)n− species that contribute to their high capacity. In addition, we visualize by imaging with micrometric resolution the plating/stripping of Li at the negative electrode and highlight the zones of nucleation and growth of Ru5+/oxygen species at the positive electrode. This efficient way to locate ‘electron’-related phenomena opens a new area in the field of battery characterization that should enable future breakthroughs in battery research.

Photostimulation induced persistent luminescence in Y 3 Al 2 Ga 3 O 12 :Cr 3+

Cr3+-activated Y3Al2Ga3O12 garnet (YAGG:Cr3+) persistent phosphor has been recently reported as a potential candidate material for in vivo imaging application. Temperature dependence of photoluminescence (PL) spectra and thermostimulated luminescence (TSL) glow curves with several conditions, especially photostimulation wavelength dependence, were carefully investigated with the perspective of deep trap utilization for long-term in vivo imaging. The PL spectrum showed typical Cr3+ emission due to 2E→4A2 and 4T2→4A2 transitions. The integrated PL intensity of Cr3+ luminescence (2E→4A2 plus 4T2→4A2 transitions) does not suffer from temperature quenching up to 600 K. From the TSL glow curve measurements, it was found that the persistent luminescence cannot be activated by visible light excitation. However, photostimulation induced persistent luminescence by red to near-infrared light can be possible in this material.

EPR of Primitive Organic Matter: A Tool for Astrobiology

Insoluble organic matter (IOM) conserved in ancient sedimentary rocks and in carbonaceous meteorites can reveal valuable information about the origin of Life on Earth and on the birth of the Solar System, respectively. These IOMs are also reference materials for the search for possible organic traces of extinct life on Mars. The combination of continuous-wave and pulsed EPR of the radicals in IOM provided several markers distinguishing these materials and related to their histories. For terrestrial IOM, the EPR linewidth of the radicals is mostly determined by unresolved 1H hyperfine interactions for IOM younger than 2500 million years (H-rich), and by dipolar interactions for older (H-depleted) IOM. The age of very primitive IOM could be estimated through the lineshape, which continuously evolves from Lorentzian to stretched Lorentzian upon ageing due to a change in the dimensionality of the radical spatial distribution. Nuclear spins within or near the radicals and the hyperfine interactions probed by pulsed EPR (through ESEEM and HYSCORE sequences) clearly distinguish meteoritic from terrestrial IOM. Radicals in meteorites are massively enriched in deuterium compared to terrestrial radicals, as a result of specific deuterium enrichment processes in the outer early Solar System. Meteoritic and terrestrial IOMs are also distinguished by the isotropic vs dipolar relative contributions in the 1H hyperfine interactions and by the 13C/1H HYSCORE signal ratio. Strong 31P and 14N HYSCORE signals were detected in terrestrial IOM, which point to possible P and N rich biological precursors. The spin states of the radicals could also be determined either indirectly from the temperature dependence of the EPR intensity or directly by transient nutation spectroscopy. Meteoritic IOM, in addition to S = 1/2 radicals, specifically contains species with either triplet ground state or thermally excited triplet states, which are lacking in terrestrial IOM.

Persistent Luminescence Cr3+ Doped Spinels and Use as Biomarker for In Vivo Imaging

ZnGa2O4 (ZGO) is a normal spinel. When doped with Cr3+ ions, ZGO:Cr becomes a high brightness persistent luminescence material with an emission spectrum perfectly matching the transparency window of living tissues. It allows in vivo mouse imaging with a better signal to background ratio than classical quantum dots. The most interesting characteristic of ZGO:Cr lies in the fact that its LLP can be excited with red light, well below its band gap energy and in the transparency window of living tissues. A mechanism based on the trapping of carriers localized around a special type of Cr3+ ions namely CrN2 can explain this singularity. The antisite defects of the structure are the main responsible traps in the persistent luminescence mechanism. When located around Cr3+ ions, they allow, via Cr3+ absorption, the storage of not only UV light but also all visible light from the excitation source.