A sulfur/carbon composite has been prepared to serve as a cathode for lithium/sulfur batteries. The effects of seven different liquid electrolytes on the electrochemical performance were investigated using galvanostatic discharge–charge tests on coin cells. The electrolytes included ether, sulfone, and carbonate solvents with common lithium salts. It was found that the solvent plays a key role on the electrochemical performance of the lithium/sulfur battery cathode while the lithium salt has no significant effects. Additional characterization, using in situ sulfur K-edge X-ray absorption spectroscopy (XAS), provided insights into the soluble sulfur species in the discharged and charged batteries. We find that the use of low-viscosity ethereal solvents results in a more complete reduction of soluble polysulfides, while soluble polysulfides remained more oxidized in viscous ethereal solvents. Moreover, XAS revealed that reduced sulfur species chemically react with carbonate-based solvents, making this class of solvents inappropriate for elemental sulfur cathodes of lithium batteries.
A three-electrode differential electrochemical mass spectrometry (DEMS) cell has been developed to study the oxidative decomposition of electrolytes at high voltage cathode materials of Li-ion batteries. In this DEMS cell, the working electrode used was the same as the cathode electrode in real Li-ion batteries, i.e., a lithium metal oxide deposited on a porous aluminum foil current collector. A charged LiCoO2 or LiMn2O4 was used as the reference electrode, because of their insensitivity to air, when compared to lithium. A lithium sheet was used as the counter electrode. This DEMS cell closely approaches real Li-ion battery conditions, and thus the results obtained can be readily correlated with reactions occurring in real Li-ion batteries. Using DEMS, the oxidative stability of three electrolytes (1 M LiPF6 in EC/DEC, EC/DMC, and PC) at three cathode materials including LiCoO2, LiMn2O4, and LiNi(0.5)Mn(1.5)O4 were studied. We found that 1 M LiPF6 + EC/DMC electrolyte is quite stable up to 5.0 V, when LiNi(0.5)Mn(1.5)O4 is used as the cathode material. The EC/DMC solvent mixture was found to be the most stable for the three cathode materials, while EC/DEC was the least stable. The oxidative decomposition of the EC/DEC mixture solvent could be readily observed under operating conditions in our cell even at potentials as low as 4.4 V in 1 M LiPF6 + EC/DEC electrolyte on a LiCoO2 cathode, as indicated by CO2 and O2 evolution. The features of this DEMS cell to unveil solvent and electrolyte decomposition pathways are also described.
The redox reactions of DMcT at PEDOT-modified glassy carbon electrodes (GCEs) in acetonitrile (AN) have been investigated via cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM) in order to elucidate the redox reaction mechanism. A redox couple at -0.29 V versus Ag/Ag+ was assigned to the dimerization process of singly protonated DMcT (DMcT-1H), and a second couple observed at +0.42 V was assigned to the polymerization process of the protonated DMcT dimer. Our investigations revealed further that the anodic current response at +0.55 V (polymerization process) has a shoulder at +0.38 V ascribed to the dimerization process of doubly protonated DMcT (DMcT-2H), indicating that the redox couple at +0.42 V is the overlapping response of the polymerization of the protonated DMcT dimer and the dimerization of the DMcT-2H monomer. It was also confirmed that the dimerization process of DMcT-1H at -0.29 V proceeded not only at the surface of a PEDOT film but also inside the film as previously suggested. Moreover, the thermodynamics of these redox reactions at PEDOT-modified GCEs are dependent on the basicity (or acidity) of the solution, as anticipated and previously shown at unmodified GCEs. The oxidation of DMcT occurs at less positive potentials and the reduction occurs at more negative potentials in the presence of base. On the basis of the results obtained, the full redox reaction scheme for DMcT at a PEDOT-modified GCE is proposed.
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