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With the aim to meet the greatest challenge facing organic batteries, namely the low conductivity of the electrodes, the electrochemical properties of a series of substituted perylene diimides able to form semi-conductive columnar material are investigated. Depending on the substituent group, a strong influence of this group on the reversibility, redox potential but especially on the gravimetric capacity of the electrodes is observed. In the case of substitution by a simple propyl group, the corresponding diimide shows a complete electrochemical activity with only 10% by mass of conductive additive and even shows a half-capacity activity without any additive and without particular electrode engineering. Extensive research has highlighted the intrinsic reactivity of the columnar material but also its perpetual rearrangement during charge/discharge cycles. This study shows that the amount of conductive additive can be significantly reduced by adapting the design of the molecular material and favoring the assembly of redox units in the form of a conductive column., (© 2023 Wiley-VCH GmbH.)

This paper describes the simple, highly reproducible, and robust synthesis of a new solid organic/inorganic electrolyte based on the ionic liquid (IL) 1-butyl-3-(carboxyundecyl)imidazolium bis(trifluoromethylsulfonyl)imide tethered to zirconia nanoparticles (15-25 nm) by coordination and named ZrO 2 @IL. The IL monolayer formation, ensured by two-dimensional solid-state NMR, at the nanoparticles' surface considerably reduces both the IL's consumption and the IL amount at the ZrO 2 surface compared to the IL-based hybrid electrolytes reported in the literature. After LiTFSI, used as a lithium source, content optimization (26 wt %), the hybrid exhibits unprecedented stable conductivity passing from 0.6 × 10 -4 S.cm -1 to 0.15 × 10 -4 S.cm -1 , respectively, from 85 °C to room temperature (25 °C). Unlike silica which is commonly adopted for this type of hybrid material, zirconia makes it possible to produce more impact-resistant pellets that are easier to compact, thus being favorable for accurate conductivity studies and battery development by electrode/composite/solid electrolyte layer stacking. The ZrO 2 @IL/LiTFSI solid hybrid electrolyte's thermal stability (up to 300 °C) and performance make this electrolyte suitable for lithium conduction in all-solid-state batteries.

The increasing demand for rechargeable batteries induces the development of greener and better devices. Significant advances have been made in the last decade together with a renewed interest in organic electrode materials. Thus, stable electron-donating organic materials are candidates for "greener" molecular batteries (metal-free). Herein, we report the design of a monomeric p-type N-substituted phenothiazine salt as an efficient anionic host structure working reversibly in a dual-ion cell configuration using lithium as the negative electrode. Investigation of different electrolyte salts, LiClO 4 , LiPF 6 , and LiTFSI in PC (propylene carbonate), reveals that lithium 4-(10H-phenothiazin-10-yl) benzoate (LiPHB) exhibits a high operating potential (≈3.7 vs. Li + /Li) corresponding to a one-electron process with a reversible specific capacity of 86 mAh g -1 in a LiClO 4 -based electrolyte, exhibiting an extraordinary cycling stability over 500 cycles at 0.2 C. Such impressive results are rendering LiPHB a promising scaffold for developing next-generation molecular organic batteries., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new series of supported organocatalysts, prepared by a simple method, were used for selective sugar oxidation. This approach is based on the immobilization of a nitroxide derivative through a carboxylic function on nanometric metal oxides (TiO 2 , Al 2 O 3 and CeO 2 ), allowing the recovery of the catalyst. These hybrid materials were carefully characterized by Diffuse Reflectance FT-IR spectroscopy (DRIFT), ThermoGravimetric Analysis (TGA), X-Ray Diffraction (XRD), Brunauer-Emmet-Teller surface area measurements (B.E.T.), elemental and electrochemical analyses, showing different characteristics and behaviors depending on the nature of the metal oxide used. The activity of the supported nitroxide catalyst was evaluated on methyl α-d-glucoside oxidation, used as model reaction. In all cases, high catalytic activity was highlighted, with up to 25 times less nitroxyl radical required for complete conversion than under homogeneous conditions. The influence of several experimental conditions such as the use of phosphate buffer and recyclability of the catalyst were also investigated., (Copyright © 2018 Elsevier Inc. All rights reserved.)

Anatase TiO2, a wide bandgap semiconductor, likely the most worldwide studied inorganic material for many practical applications, offers unequal characteristics for applications in photocatalysis and sun energy conversion. However, the lack of controllable, cost-effective methods for scalable fabrication of homogeneous thin films of anatase TiO2 at low temperatures (ie. < 100 °C) renders up-to-date deposition processes unsuited to flexible plastic supports or to smart textile fibres, thus limiting these wearable and easy-to-integrate emerging technologies. Here, we present a very versatile template-free method for producing robust mesoporous films of nanocrystalline anatase TiO2 at temperatures of/or below 80 °C. The individual assembly of the mesoscopic particles forming ever-demonstrated high optical quality beads of TiO2 affords, with this simple methodology, efficient light capture and confinement into the photo-anode, which in flexible dye-sensitized solar cell technology translates into a remarkable power conversion efficiency of 7.2% under A.M.1.5G conditions.

This work sheds light on the exceptional robustness of anatase TiO2 when it is downsized to an extreme value of 4 nm. Since at this size the surface contribution to the volume becomes predominant, it turns out that the material becomes significantly resistant against particles coarsening with temperature, entailing a significant delay in the anatase to rutile phase transition, prolonging up to 1000 °C in air. A noticeable alteration of the phase stability diagram with lithium insertion is also experienced. Lithium insertion in such nanocrystalline anatase TiO2 converts into a complete solid solution until almost Li1TiO2, a composition at which the tetragonal to orthorhombic transition takes place without the formation of the emblematic and unwished rock salt Li1TiO2 phase. Consequently, excellent reversibility in the electrochemical process is experienced in the whole portion of lithium content.

Iron-doped nanocrystalline particles of anatase TiO2 (denoted x% Fe-TiO2, with x the nominal [Fe] atom % in solution) have been successfully synthesized at room temperature by a controlled two-step process. Hydrolysis of titanium isopropoxide is first achieved to precipitate Ti(OH)4 species. A fine control of the pH allows one to maintain (i) soluble iron species and (ii) a sluggish solubility of Ti(OH)4 to promote a dissolution and condensation of titanium clusters incorporating iron, leading to the precipitation of iron-doped anatase TiO2. The pH does then influence both the nature and crystallinity of the final phase. After 2 months of aging at pH = 2, well-dispersed nanocrystalline iron-doped TiO2 particles have been achieved, leading to 5-6 nm particle size and offering a high surface area of ca. 280 m(2)/g. This dissolution/recrystallization process allows the incorporation of a dopant concentration of up to 7.7 atom %; the successful incorporation of iron in the structure is demonstrated by X-ray diffraction, high-resolution transmission electron microscopy, and Mössbauer spectroscopy. This entails optical-band-gap narrowing from 3.05 to 2.30 eV. The pros and cons effects of doping on the electrochemical properties of TiO2 versus lithium are herein discussed. We reveal that doping improves the power rate capability of the electrode but, in turn, deserves the electrolyte stability, leading to early formation of SEI. Finally, we highlight a beneficial effect of low iron introduction into the anatase lattice for photocatalytic applications under standard AM1.5G visible-light illumination.

We report an in-depth study focusing on the stability of a benchmark electrolyte composition based on a low-volatile 3-methoxypropionitrile (MPN) solvent employed in dye-sensitized solar cells. In the presence of TiO2, the semi-conductor surface plays a catalytic role in the thermal degradation of the electrolyte, which induces, among other effects, the nucleation and growth of a uniform solid electrolyte interphase (SEI) layer that wraps TiO2. On the basis of our actual understanding, we argue that SEI formation is responsible for triiodide depletion in the electrolyte during ageing and also has a simultaneous impact on TiO2 optoelectronic properties through the onset of a visible-light absorption tail, energy modification of intraband trap states, and the induction of an increase in both electron lifetime and transport time in TiO2. In-depth characterization of this layer by using XPS and ToF-SIMS indicates that the chemical composition of this SEI results from solvent and additive degradation, that is, iodide, sulfur, cyano, nitrogen, carbon, and imidazolium rings. The SEI thickness, its content, and the concentration profile strongly vary depending on the ageing conditions. The outcome of this new finding is discussed in comparison with literature observations and stresses the difficulties in reaching long-term stability at 85 °C by using MPN-based electrolytes unless new interfacial engineering is accomplished to impede pinholes between dye molecules on TiO2., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We investigated CdSe-sensitized TiO(2) solar cells by means of electrodeposition under galvanostatic control. The electrodeposition of CdSe within the mesoporous film of TiO(2) gives rise to a uniform, thickness controlled, conformal layer of nanostructured CdSe particles intimately wrapping the anatase TiO(2) nanoparticles. This technique has the advantage of providing not only a fast method for sensitization ( < 5 min) but also being easily scalable to the sensitization of large-area panels. XRD together with SAED analysis highlight that the deposit of CdSe is exclusively constituted of the hexagonal polymorph. In addition, hierarchical growth has also been shown, starting from the formation of a TiO(2)-CdSe core-shell structure followed by the growth of an assembly of CdSe nanoparticles resembling cauliflowers. This assembly exhibits at its core a mosaic texture with crystallites of about 3 nm in size, in contrast to a shell composed of well-crystallized single crystals between 5 and 10 nm in size. Preliminary results on the photovoltaic performance of such a nanostructured composite of TiO(2) and CdSe show 0.8% power conversion efficiency under A.M.1.5 G conditions-100 mW cm(-2) in association with a new regenerative redox couple based on cobalt(+III/+II) polypyridil complex (V(oc ) = 485 mV, J(sc ) = 4.26 mA cm (-2), ff=0.37).

Li-S rechargeable batteries are attractive for electric transportation because of their low cost, environmentally friendliness, and superior energy density. However, the Li-S system has yet to conquer the marketplace, owing to its drawbacks, namely, soluble polysulfide formation. To tackle this issue, we present here a strategy based on the use of a mesoporous chromium trimesate metal-organic framework (MOF) named MIL-100(Cr) as host material for sulfur impregnation. Electrodes containing sulfur impregnated within the pores of the MOF were found to show a marked increase in the capacity retention of Li-S cathodes. Complementary transmission electron microscopy and X-ray photoelectron spectroscopy measurements demonstrated the reversible capture and release of the polysulfides by the pores of MOF during cycling and evidenced a weak binding between the polysulphides and the oxygenated framework. Such an approach was generalized to other mesoporous oxide structures, such as mesoporous silica, for instance SBA-15, having the same positive effect as the MOF on the capacity retention of Li-S cells. Besides pore sizes, the surface activity of the mesoporous additives, as observed for the MOF, appears to also have a pronounced effect on enhancing the cycle performance. Increased knowledge about the interface between polysulfide species and oxide surfaces could lead to novel approaches in the design and fabrication of long cycle life S electrodes.