The Role of Al3+ -Based Aqueous Electrolytes in the Charge Storage Mechanism of MnOx Cathodes.

Rechargeable aqueous aluminium batteries are the subject of growing interest, however, the charge storage mechanisms at manganese oxide-based cathodes remain poorly understood. In essense, every study proposes a different mechanism. Here, an in situ spectroelectrochemical methodology is used to unambiguously demonstrate that reversible proton-coupled MnO2 -to-Mn2+ conversion is the main charge storage mechanism occurring at MnO2 cathodes for a range of slightly acidic Al3+ -based aqueous electrolytes, with the Al3+ hexaaquo complex playing the key role of proton donor. In Zn/MnO2 assemblies, this mechanism is associated with high gravimetric capacities and discharge potentials, up to 560 mAh g-1 and 1.65 V respectively, attractive efficiencies (CE > 99.5% and EE > 82%) and excellent cyclability (almost 100% capacity retention over 1 400 cycles at 2 A g-1 ). Finally, a critical analysis of the data previously published on MnOx cathodes in Al3+ -based aqueous electrolytes is conducted to conclude on a universal charge storage mechanism, i.e., the reversible electrodissolution/electrodeposition of MnO2 .

Low Conductive Electrodeposited Poly(2,5-dimethoxyaniline) as a Key Material in a Double Lateral Heterojunction, for Sub-ppm Ammonia Sensing in Humid Atmosphere.

We present a new device called a double lateral heterojunction (DLH) as an ammonia sensor in humid atmosphere. It combines polyaniline derivatives in their poor conducting state with a highly conductive molecular material, lutetium bisphthalocyanine, LuPc2. Polyaniline and poly(2,5-dimethoxyaniline) are electrodeposited on ITO interdigitated electrodes, leading to an original device that can be obtained only by electrochemistry and not by other solution processing techniques. Both polymers lead to highly conducting materials that require a neutralization step before their coverage by LuPc2. While the device based on polyaniline shows ohmic behavior, the nonlinear I- V characteristics of the poly(2,5-dimethoxyaniline)-based DLH prove the existence of energy barriers at the interfaces, as demonstrated by impedance spectroscopy. It exhibits a particularly interesting sensitivity to ammonia, at room temperature and in a broad relative humidity range. Thanks to its higher energy barriers, the poly(2,5-dimethoxyaniline)/LuPc2 DLH is the most sensitive device with a limit of detection of 320 ppb. This work paves the way for the use of substituted polyanilines in conductometric sensors not only in the field of air quality monitoring but also in the field of health diagnosis by measurement in human breath.

Comprehensive Study of Poly(2,3,5,6-tetrafluoroaniline): From Electrosynthesis to Heterojunctions and Ammonia Sensing.

In this work, we report for the first time on a comprehensive study of poly(2,3,5,6-tetrafluoroaniline) (PTFANI). Contrary to the nonfluorinated polyaniline (PANI) or its analogues bearing one fluorine atom, PTFANI is a poorly conductive material. We present a comprehensive study of the electrosynthesized PTFANI from its monomer in an acidic aqueous medium. PTFANI was fully characterized by a potential-pH diagram, spectroelectrochemistry, and electrochemical quartz crystal microbalance (EQCM) measurements, as well as by a morphological study. Combined with the X-ray photoelectron spectroscopy (XPS) analysis, it allowed us to understand the redox properties of this polymer compared to those of the unsubstituted PANI. At pH < 1.85, no proton transfer occurred during the electrochemical process, but the insertion of anions at the site of the protonated imines was demonstrated through the EQCM and XPS experiments. PTFANI showed a lower ratio of 1 ClO4- per 3 2,3,5,6-tetrafluoroaniline units compared to that of PANI. The behavior at pH > 1.85 was different; no anion upload was observed during the electron transfer, but 1 H+ per electron was involved during the transition between the leucoemeraldine and emeraldine base forms. It should also be noted that the oxidation of the emeraldine into the pernigraniline form was not accessible in PTFANI because of the electron-withdrawing effects of the fluorine atoms. However, we took advantage of the unique behavior of PTFANI to build heterojunctions, by combining with a highly conductive molecular material, namely lutetium bisphthalocyanine, LuPc2. The obtained double-lateral heterojunction exhibited a particularly interesting sensitivity to ammonia, even under humid atmospheres, with a limit of detection of 450 ppb. This work paves the way for the use of PTFANI in other electronic devices and as a sensor not only in the field of air quality monitoring but also in the field of health diagnosis in measuring the human breath.