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Axis 2 : Materials for energy

Materials for energy

Axis 2: Materials for energy

 

Action 2.1: Fluorinated materials for energy

The unique properties of fluorine are at the origin of remarkable fluorinated materials that will be assets in the framework of the energy transition and the respect of sustainable development. Our research is based on the discovery of new chemical compositions via reasoned methodologies such as the decomposition of fluorinated precursors or topotactic oxidation. In order to exacerbate the properties of our materials for applications in the fields of batteries, catalysis, electrocatalysis and photovoltaics, our expertise has been extended to their nanostructuring in the form of nanoparticles and organized porous inorganic fluorides (FIPO) but also by their deposition in thin films.

The activity in the field of batteries is based on an incremental research of new cathode materials for Li or Na ion batteries. The thermal decomposition of original precursors has given access to a wide range of new fluorinated materials: crystallized hydroxyfluorides FeF3-x(OH)x of pyrochore and HTB structure and amorphous oxyfluorides with mixed cations M2+Fe3+2F8-2xOx and M2+Fe3+F5-2xOx (M = Co, Ni, Cu, Mn) (Fig. 6, left). Some of these compounds reveal properties of interest as active compounds of positive electrodes for Li+ ion batteries [1–3]. The ANR FLUOBAT 2012-17 project was part of a technological breakthrough on electrochemical storage with the development of an all-solid fluoride ion battery and the identification of an optimal electrolyte (tysonite type) with respect to ionic conduction (Fig. 6, right) [4–7]. The next step of this work concerns the PVD processing of very dense thin films of this electrolyte with a clear improvement of the intrinsic conductivity properties, close to those of a single crystal.

 

 

Fig. 1.  Electrochemical properties of lithium insertion in pyrochlore and HTB iron hydroxyfluorides (left) and representation of the tysonite-like structure (right).

 

The first mesoporous OPIFs, prepared, in collaboration with of the POL thematic, by a patented method [8], have demonstrated significant potential in heterogeneous catalysis given their superior ability to withstand the extreme conditions of the catalytic fluorination reaction under gaseous HF compared to nanoparticles [9]. This work is being continued in the context of the ANR PRCE OPIFCat project (2021-24) coordinated by a member of the thematic.

It was recently established that mixed oxyfluorides based on (Co,Ni)/Fe present equivalent performances to reference materials (Ir, Ru) of anode for the water oxidation reaction [10]. The innovative character of this work has been rewarded by an Emergence project (INC-CNRS, 2020), a Samuel de Champlain Program (Conseil franco-québécois de coopération universitaire) and an International Emerging Action (CNRS 2022).  The intellectual protection of these new electrocatalysts is in progress and their valorisation will performed for 18 months from 2022 in the framework of a CNRS pre-maturation project.

Fig. 2. Efficiency of a solar cell covered by the xMn2+-0.75Tm3+ doped ZZBAY glass

Finally, the UV-blue IR frequency conversion on fluorinated glasses/vitroceramics with different dopants (Pr3+, Tm3+, Cr3+)/Yb3+, Tm3+, Mn2+/Tm3+ has been measured [11–16], with results to be consolidated (Fig. 2)

 

Action 2.2: Oxides for energy

 

Cationic diffusion between solid oxide fuel cell core materials is an issue that occurs both during device fabrication and operation due to the high temperatures used in both cases. A reactivity between the oxide ion conductor La2Mo2O9 (LM) and the cathode material La0.8Sr0.2MnO3-d (LSM) exists and its origin had to be determined. The cationic diffusion at the LM/LSM interface was studied by X-ray diffraction and FIB-SIMS (Imperial College collaboration, London, UK). Various reaction products were identified as well as the reaction mechanisms leading to them [17]. The highest diffusion coefficient by far is that of Mo in LSM, making the use of La2Mo2O9 as a battery electrolyte inappropriate without an effective buffer layer [18].

Fig. 3. Adjustment of synthesis parameters using a polyol route for fabricating La2Mo2O9

 

The adjustment of the parameters of the synthesis of La2Mo2O9 by a polyol route allowed to obtain without grinding or pollution nano-structured powders (Fig. 3) of specific surface 24 m2/g and dense pellets (compactness 95%) with little modified ionic conductivity [19]. The reduction kinetics of the powders obtained by solid-state synthesis and polyol (Diethylene Glycol, Ethylene Glycol) were studied up to the mixed conductive amorphous phase La2Mo2O6.7 (Fig. 3, [20]), whose local order [21]) was determined by EXAFS (joint work with Centro Atomico Bariloche, Argentina). The performance of this phase as an anode material in innovative fuel cells [22] has been measured (Joint work with Institut Jean Rouxel, Nantes).

The already very low thermal conductivity of La2Mo2O9 could be decreased by about 15(4)% by replacing half of the lanthanum by praseodymium (0.9 W.m-1K-1 at 700°C – joint work with GREMAN, Tours), making LaPrMo2O9 an interesting candidate as a thermal barrier [23].

Fig. 4. Structure of Li1.3Al0.3Ti1.7(PO4)3  

 

A modified Pechini method has been developed in order to obtain one of the best Li+ based conductors at room temperature, the compound Li1.3Al0.3Ti1.7(PO4)3 (LATPO) with NASICON structure [24]. NMR study of LATPO by 31P, 27Al, and 7Li nuclei revealed that the octahedra of the NASICON backbone were statistically occupied by Al3+ and Ti4+ ions (Fig. 4, [24]) and that all Li+ ions had the same environment [25]. Migration of Li+ ions into the structure requires passage through triangular oxygen windows bounded by [(Ti,Al)O6] octahedra and [PO4] tetrahedra of the framework. NMR showed that the local and coordinated distortions of the (Al,Ti)2(PO4)3 framework [26] facilitated their crossing by Li+ ions in LATPO, thus explaining its excellent conductivity. This work is the last one of our colleague J. Emery (Pr. emeritus until 2015) who performed numerous NMR studies of Li+ ion conductors in the subject.

 

Action 2.3: Solid state NMR characterization

Solid state NMR has been used to characterize the structure and eventually the disorder and dynamics, mainly of energy materials, through three projects or collaborations:

Fig. 5. 19F EXSY spectrum of La0.97Ba0.03F2.97.

1) The ANR FLUOBAT project (see action 2.1) for which 19F NMR was a valuable tool since it allowed to characterize the environment and mobility of fluoride ions in solid electrolytes La1-xBaxF3-x [4,6,27] (Fig. 5), Sm1-xCaxF3-x [5] and Ce1-xSrxF3-x [7].

2) It was also important to quantify fluorine and to identify and quantify the various environments of fluoride ions in a hydroxyfluorinated anatase whose cationic sub-lattice is deficient, before but also after insertion of lithium, magnesium and aluminium [28–35].

3) The collaboration initiated more than 10 years ago with N. Mercier (MOLTECH Anjou - UMR 6200 CNRS, University of Angers) by the study of a hybrid perovskite, continued with the study by NMR of the paramagnetic solid of zwitterions hydrated or not [36] and associated to an inorganic part [37]. It is intensified with the study of hybrid perovskites as material of the active layer of photovoltaic cells, within the framework of the ANR MORELESS project (More stable and less lead for perovskite solar cells) [38,39].

 

 

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