ORALS

SESSION: SolidStateChemistryMonPM2-R6	Alario-Franco international Symposium (2nd Intl Symp on Solid State Chemistry for Applications & Sustainable Development)
Mon. 28 Nov. 2022 / Room: Andaman 1
Session Chairs: TBA Session Monitor: TBA

17:10: [SolidStateChemistryMonPM212] OS
“Fluoroperovskites and other Fluoride Materials for Applications in Energy, Electronics, Photonics and Sustainable Issues”
Alain Tressaud¹ ; ¹ICMCB-CNRS, University Bordeaux, Pessac, France;
Paper Id: 506 [Abstract]

Solid-state inorganic fluorides are present today as components in many advanced technologies, including energy storage and conversion, microphotonics, fluorescent chemical sensors, solid-state lasers, nonlinear optics, nuclear cycle, superhydrophobic coatings, etc. Most of these outstanding properties can be correlated to the exceptional electronic properties of element fluorine “F2”, yielding almost unique types of bonding with the other elements [1]. The strategic importance of Solid-state inorganic fluoride materials will be illustrated by some examples taken from various fields.: - Use of fluoride materials as electrodes in Li-ion batteries and in catalysis; - Nanocrystalline metal fluorides derived from fluorite- (CaF2) or tysonite- (LaF3) types with high F--anionic conductivity and used as solid electrolytes in F- ion-based all-solid-state batteries. - Fluorides in photonics: luminescence, up- and down-conversion, frequency-doubling fluorides and solid-state lasers ; - Multiferroics based on d-transition metal fluorides derived from the perovskite, i.e. layered BaMF4 or TTB-K3Fe5F15, in which magnetism and ferroelectricity coexist. - F-doped SnO2 for photo-voltaic applications exhibiting a rather good transparency in the visible range and high infrared absorption associated to its conductivity due to n-type charge carriers -Perovskite-related solid-state fluorides based on d-transition metals exhibit a huge variety of structural and magnetic behaviors. Layered BaMF4 and iron fluorides (TTB- K3Fe5F15), are important families of multiferroics, -Intercalated fluoride ion in several networks of oxides allowing to tune the transition metal oxidation state. F-based superconductors created by F-doping in cuprate systems La2CuO4 and Sr2CuO3 or in F-doped oxypnictide LnFePnO1-xFx (Tc ~58 K) - Finally, nanoparticles of solid-state inorganic fluorides are used in many advanced domains such as dye-sensitized solar cell (DSSC), transparent conducting films (TCF), solid state lasers, nonlinear optics (NLO), up- and down-conversion luminescence, UV absorbers, frequency doubling. Their role is decisive in medicine and biotechnologies, where nano-crystals of doped rare-earth fluorides can be used as theranostic nano-agents that integrate imaging probes and therapeutic and are therefore able to perform both therapy and diagnostic within a single nano-object.

References:
[1] “Progress in Fluorine Science”, A. Tressaud Series Editor, Elsevier, Vol. 1 –
“Photonic & Electronic Properties of Fluoride Materials”, A.Tressaud & K. Poeppelmeier
Eds. (2016). // Vol. 2 – “New Forms of Fluorinated Carbons”, O. Boltalina & T. Nakajima, Eds. (2016). // Vol. 3 – “Modern Synthesis Processes and Reactivity of Fluorinated Compounds”, H. Groult, F. Leroux & A. Tressaud, Eds. (2017). // Vol. 4 – “Fluorine & Health: Pharmaceuticals, Medicinal Diagnostics, and Agrochemicals”, G. Haufe, & F. Leroux Eds. ( 2018). // Vol. 5 – “Fluorine, a Paradoxical Element”, A. Tressaud, (2019).

SESSION: BatteryTuePM1-R9	Yazami International Symposium (7th Intl. Symp. on Sustainable Secondary Battery Manufacturing & Recycling)
Tue. 29 Nov. 2022 / Room: Similan 2
Session Chairs: Alain Tressaud; Xuejie Huang; Session Monitor: TBA

14:00: [BatteryTuePM105] OS
NANO-FLUORIDE MATERIALS AS ACTIVE COMPONENTS IN PRIMARY AND SECONDARY LI-BATTERIES
Alain Tressaud¹ ; Henri Groult² ; Etienne Durand³ ; Wei Li⁴ ; Damien Dambournet⁵ ; ¹ICMCB-CNRS, University Bordeaux, Pessac, France; ²Sorbonne University, Paris, France; ³ICMCB-CNRS, PESSAC, France; ⁴Nankai University, Tianjin, China; ⁵Sorbonne Uuniversity, Paris, France;
Paper Id: 507 [Abstract]

Energy storage is one of the most important challenges for the 21st century. The improvement of the electrochemical performances implies the development of new class of electrode materials, allowing higher energy density, longer cycle life, moderate cost, etc. In this context, nano-fluoride materials may occupy a noticeable place in both primary and secondary batteries. 1) Nano-CFx in primary Li batteries - The electrochemical performances of primary Li-battery, can be improved by developing new materials with higher potential and energy density values [1-4]. New kinds of carbon-fluorine nanoparticles are suitable since they allow combining the physical properties of CFx with the effect of nanosized particles. These materials allow having higher OCV and suppressing the potential delay, generally observed during the first time of the discharge reaction in commercial graphite fluorides. 2) CoF3-based materials in secondary Li batteries In reversible Li batteries, several types of transition metal trifluorides and derived (MX3, with M=Ti, Mn, Fe, Co) have been tested for increasing the electrochemical performances because these compounds may incorporate three electrons per 3d-metal during the process, thus delivering higher energy density, and exhibiting longer cycle life Nano-CoF3 have been synthesized by direct fluorination (with F2-gas) of cobalt nanoparticles at various temperatures (up to 300°C). When handled in very dry atmospheres, CoF3-based samples are stable vs. traces of humidity and can be used to prepare electrodes in fairly good conditions for batteries. The best electrochemical performances were obtained with nano-CoF3 powders prepared at TF2 = 100 °C, for which a reversible capacity of about 390 mAh/g was obtained after subsequent cycles [5]. More recently, high-energy X-ray data, showed that in fact CoF3 decomposes during the discharge process into an intermediate compound with a new structure/composition [6]. Using the pair distribution function, the structure was elucidated to correspond to a defect corundum phase exhibiting Co vacancies, i.e., Co1.26IICo0.16III0.58F3.

References:
1) A.Tressaud, in Fluorine-carbon and fluoride-carbon materials, Chap. 2, M. Dekker, NY, 1995, 32.
2) C. Delabarre, M. Dubois , J. Giraudet, K. Guerin, R. Yazami, A. Hamwi, Electrochemical society transactions, 36, (2007),153-163.
3) K. Le Van, H. Groult, F. Lantelme, M. Dubois, D. Avignant, A. Tressaud, S. Komaba, N. Kumagai, S. Sigrist, Electrochim. Acta, 54, (2009), 4566-4573.
4) A. Tressaud, H. Groult, J. Fluor. Chem. 219, (2019 ), p.1-9,
5) H. Groult, S. Neveu , S. Leclerc , A.-G. Porras-Gutierrez , C.M. Julien, A. Tressaud, E. Durand, N. Penin, C. Labrugere, J. Fluor. Chem. vol. 196, (2017), p. 117-127.
6) W. Li, H. Groult, O. J. Borkiewicz, D. Dambournet, J. Fluor. Chem. 205 (2018) pp.43-48.