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Salt bridge formation between ferrocenecarboxylic acid and an excess of a N,N′-diethylsubstituted benzamidine leads to a -0.27 V shift in the half-wave potential of the ferrocene moiety, corresponding to a 26 kJ mol-1 stabilisation of the ferrocenium state. [Copyright &y& Elsevier]

Abstract: Keggin-type dodecatungstosilicates polyoxometallates (POMs) ([SiW12O40]4−) were immobilized in a straightforward manner by electrostatic interactions on ammonium layers covalently grafted on silicon. This method does not require any POM modification synthetical steps. The presence of [SiW12O40]4− on the surface is demonstrated by X-ray Photoelectron Spectroscopy from a specific modification of the tungsten 4f7/2 signal. Moreover the surface coverage of [SiW12O40]4− has been improved by 35% upon changing the nature of the anchoring ammonium groups from protonated to methylated amino groups. The organic–inorganic composite films have also been characterized by cyclic voltammetry showing that POMs have a specific behavior on silicon surfaces. In addition the use of a polyallylamine capping layer proved to stabilize efficiently the POM electrochemical response. [Copyright &y& Elsevier]

We describe the electrochemically controlled hydrogen bonding interactions between the isobutyl flavin/2,6-diferrocenylamidopyridine (2·5) and 9,10-phenanthrenequinone/1-ferrocenyl-3-hexylurea (4·6) dyads. Cyclic and square wave voltammetry studies have shown that the binding efficiencies between these moieties can be electrochemically actuated in non-polar (CH2Cl2 for 2·5) or polar (DMF for 4·6) organic solvents between three distinct states. [Copyright &y& Elsevier]

We have investigated the electrochemically controlled hydrogen bonding interactions between tetrathiafulvalene host 3 and guests 4 or 5. Stabilisation of the 3+⋅ state is dependent upon the nature of the guest species, whereas both guests prevent precipitation of the electrochemically generated 32+ species at the working electrode via hydrogen bonded molecular recognition processes. [Copyright &y& Elsevier]

Abstract Herein we report the successful use of a polyisoindigo derivative (P(iso)) as a new conductive binder inside electrode formulations containing silicon nanoparticles covered with a carbon shell (Si@C) for Li-ion batteries. The expected role of the carbon shell is to stabilize the Solid Electrolyte Interphase layer (SEI) to prevent it from cracking under nanoparticle volume variations during lithiation processes. The P(iso) conducting polymer is used to act both as mechanical binder and n-type conductive component in replacement of usual carbonaceous additive materials. Ultimately, the cumulative contributions of both materials inside a two-electrode component formulation (Si@C P(iso)) aim to address the stability drawbacks commonly faced by silicon electrodes. Physico-chemical characterizations revealed that the Si@C nanoparticles are uniformly embedded inside the polymeric matrix. Electrochemical measurements in half-cells clearly show the formation of Li Si alloys during cycling. Moreover specific capacities up to 1400 mAh/g with a remarkable stability until 500 cycles have been achieved, proving this conductive polymer to be a valid alternative to classical polymeric binders mixed with carbonaceous additives. These very promising results highlight the use of this polyisoindigo family as new conductive binders inside Si@C electrode formulations for Li-ion battery applications. Highlights • Synthesis of a polyisoindigo derivative (P(iso)) by Yamamoto cross-coupling. • Characterization of the (P(iso)) as a new conductive binder with Si@C nanoparticles. • High stability of the Si@C P(iso) electrode (1400 mAh/g) over 500 cycles. • Higher capacity retention for Si@C P(iso) electrode than Si@C/CMC/CB electrode. [ABSTRACT FROM AUTHOR]

Abstract Chemically tuned pillared graphene structures show ability to limit restacking of graphene sheets for electrochemical energy storage in SCs. A comprehensive electrochemical characterization using various ion sizes allowed identification of ion-sieving in the cross-linked galleries of reduced pillared graphene materials (RPs). The access to the cross-linked galleries, which provide additional ion sorption sites, offered slightly increased capacitances in RPs compared to completely restacked sheets in reduced graphene oxide (RGO). We performed electrochemical impedance analyses on RPs and RGO to understand the ion transport inside the cross-linked graphene galleries. RGO adsorbs ions in the inter-particle micro/meso pores and the ion access to such sites from the bulk electrolyte occurs with relative ease. RPs sieve ions into their inter-layer gallery pores based on effective ion sizes and the ion transport process is resistive compared to RGO. A control study using 3D pillared graphene hydrogel with improved macro porosity assigns this resistive behavior and the moderate capacitances to limited ion access to the active sites due to excess number of pillars. The obtained results on the ion transport dynamics between graphene layers provide perspectives towards further optimization of these graphene materials for SCs. Graphical abstract Ion transport inside the inter-layer galleries of pillared graphene materials is impeded by the pillars. Image 1 [ABSTRACT FROM AUTHOR]

Graphene hydrogels with high electrical conductivity were prepared by a one-step process using hydrazine hydrate as gel assembly agent (GH-HD). Conventional two-step process of gel formation and further reduction to prepare highly conducting gels was replaced by a single step involving equivalent amount of hydrazine. Optimized graphene oxide concentration was established to facilitate such monolith formation. Extensive characterization and control studies enabled understanding of the material properties and gel formation mechanism. The synthesized gel shows a high electrical conductivity of 1141 S/m. The supercapacitor based on GH-HD delivers a high specific capacitance of 190 F/g at a current density of 0.5 A/g and 123 F/g at very high current density of 100 A/g. Furthermore, excellent power capability and cyclic stability were also observed. 3D macroporous morphology of GH-HD makes it ideal for high rate supercapacitor applications. [ABSTRACT FROM AUTHOR]