Tale Of A Non-Interacting Additive In A Lithium-Ion Electrolyte: Effect On Ionic Speciation And Electrochemical Properties

New lithium electrolytes compatible with high energy density cells are critical for lithium metal battery applications, but dendrite formation associated with the use of dilute organic electrolytes complicates their realization. High-concentration electrolytes mitigate some of the issues of the electrolytes but introduce additional problems, such as low conductivity and high cost. Hence, pseudo-concentrated electrolytes, wherein a co-solvent is added to a dilute electrolyte, have been presented as a possible alternative to both dilute and concentrated electrolytes. However, the effect that the co-solvent has on the electrolyte properties at both macroscopic and microscopic levels is unknown. Here, a study of the structure and electrochemical properties of two electrolytes as a function of co-solvent concentration is presented using an array of spectroscopies (FTIR, ATR-FTIR, and nuclear magnetic resonance) and computational methods (density functional theory calculations). The chosen electrolytes comprised two different lithium salts (LiPF6 and LiTFSI) in a mixture of dimethyl carbonate (DMC) with 1,1,1,3,3-pentafluorobutane (PFB) as the co-solvent. Our results show that in the case of the LiPF6/DMC electrolyte, the addition of a co-solvent (PFB) with a larger dielectric constant results in the strengthening of the lithium-anion interaction and the formation of aggregate species since PFB does not interact with the anion. Conversely, in the LiTFSI/DMC electrolyte, the co-solvent appears to interact with the anion via hydrogen bonds, which leads to the dissociation of contact ion pairs. The change in ionic speciation of the electrolytes upon addition of PFB provides a reasonable framework to explain the different trends in both the bulk and interfacial macroscopic properties, such as conductivity, viscosity, and electrochemical stability. Overall, our findings demonstrate that the interactions between the anion and the co-solvent must be taken into consideration when adding a co-solvent because they play a major role in determining the final electrolyte properties

Cobalt-based molecular electrocatalysis of nitrile reduction: evolving sustainability beyond hydrogen

Two new cobalt bis-iminopyridines, [Co(DDP)(H2O)2](NO3)2 (1, DDP = cis-[1,3-bis(2-pyridinylenamine)] cyclohexane) and [Co(cis-DDOP)(NO3)](NO3) (2, cis-DDOP = cis-3,5-bis[(2- Pyridinyleneamin]-trans-hydroxycyclohexane) electrocatalyse the 4-proton, 4-electron reduction of acetonitrile to ethylamine. For 1, this reduction occurs in preference to reduction of protons to H2. A coordinating hydroxyl proton relay in 2 reduces the yield of ethylamine and biases the catalytic system back towards H2

Photocatalytic Carbon Dioxide Reduction with Rhodium-based Catalysts in Solution and Heterogenized within Metal-Organic Frameworks

SSCI-VIDE+ING:+JOB:JEC:DFAInternational audienceThe first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Formate has wide industrial applications and is seen as valuable within fuel cell technologies as well as an interesting H-2-storage compound. Heterogenization of molecular rhodium catalysts is accomplished via the synthesis, post-synthetic linker exchange, and characterization of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and selective. Furthermore it can be recycled without loss of activity. For formate production, an optimal catalyst loading of approximate to 10% molar Rh incorporation is determined. Increased incorporation of rhodium catalyst favors thermal decomposition of formate into H-2. There is no precedent for a MOF catalyzing the latter reaction so far