A Stable High-Capacity Lithium-Ion Battery Using a Biomass-Derived Sulfur-Carbon Cathode and Lithiated Silicon Anode.

A full lithium-ion-sulfur cell with a remarkable cycle life was achieved by combining an environmentally sustainable biomass-derived sulfur-carbon cathode and a pre-lithiated silicon oxide anode. X-ray diffraction, Raman spectroscopy, energy dispersive spectroscopy, and thermogravimetry of the cathode evidenced the disordered nature of the carbon matrix in which sulfur was uniformly distributed with a weight content as high as 75 %, while scanning and transmission electron microscopy revealed the micrometric morphology of the composite. The sulfur-carbon electrode in the lithium half-cell exhibited a maximum capacity higher than 1200 mAh gS -1 , reversible electrochemical process, limited electrode/electrolyte interphase resistance, and a rate capability up to C/2. The material showed a capacity decay of about 40 % with respect to the steady-state value over 100 cycles, likely due to the reaction with the lithium metal of dissolved polysulfides or impurities including P detected in the carbon precursor. Therefore, the replacement of the lithium metal with a less challenging anode was suggested, and the sulfur-carbon composite was subsequently investigated in the full lithium-ion-sulfur battery employing a Li-alloying silicon oxide anode. The full-cell revealed an initial capacity as high as 1200 mAh gS -1 , a retention increased to more than 79 % for 100 galvanostatic cycles, and 56 % over 500 cycles. The data reported herein well indicated the reliability of energy storage devices with extended cycle life employing high-energy, green, and safe electrode materials.

Organic Polyradicals as Redox Mediators: Effect of Intramolecular Radical Interactions on Their Efficiency.

The spin-spin interactions between unpaired electrons in organic (poly)radicals, especially nitroxides, are largely investigated and are of crucial importance for their applications in areas such as organic magnetism, molecular charge transfer, or multiple spin labeling in structural biology. Recently, 2,2,6,6-tetramethylpiperidinyloxyl and polymers functionalized with nitroxides have been described as successful redox mediators in several electrochemical applications; however, the study of spin-spin interaction effect in such an area is absent. This communication reports the preparation of a novel family of discrete polynitroxide molecules, with the same number of radical units but different arrangements to study the effect of intramolecular spin-spin interactions on their electrochemical potential and their use as oxidation redox mediators in a Li-oxygen battery. We find that the intensity of interactions, as measured by the d1/d electron paramagnetic resonance parameter, progressively lowers the reduction potential. This allows us to tune the charging potential of the battery, optimizing its energy efficiency.

Alternative lithium-ion battery using biomass-derived carbons as environmentally sustainable anode.

Disordered carbons derived from biomass are herein efficiently used as an alternative anode in lithium-ion battery. Carbon precursor obtained from cherry pit is activated by using either KOH or H3PO4, to increase the specific surface area and enable porosity. Structure, morphology and chemical characteristics of the activated carbons are investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetry (TG), Raman spectroscopy, nitrogen and mercury porosimetry. The electrodes are studied in lithium half-cell by galvanostatic cycling, cyclic voltammetry, and electrochemical impedance spectroscopy (EIS). The study evidences substantial effect of chemical activation on the carbon morphology, electrode resistance, and electrochemical performance. The materials reveal the typical profile of disordered carbon with initial irreversibility vanishing during cycles. Carbons activated by H3PO4 show higher capacity at the lower C-rates, while those activated by KOH reveal improved reversible capacity at the high currents, with efficiency approaching 100% upon initial cycles, and reversible capacity exceeding 175 mAh g-1. Therefore, the carbons and LiFePO4 cathode are combined in lithium-ion cells delivering 160 mAh g-1 at 2.8 V, with a retention exceeding 95% upon 200 cycles at C/3 rate. Hence, the carbons are suggested as environmentally sustainable anode for Li-ion battery.

Combined Influence of Meso- and Macroporosity of Soft-Hard Templated Carbon Electrodes on the Performance of Li-O2 Cells with Different Configurations.

Li-O2 batteries can offer large discharge capacities, but this depends on the morphology of the discharged Li2O2, which in turn is strongly affected by the nanostructured carbon used as support in the air cathode. However, the relation with the textural parameters is complex. To investigate the combined effect of channels of different sizes, meso-macroporous carbons with similar mesopore volume but different pore size distribution were prepared from the polymerization of resorcinol-formaldehyde (RF) in the presence of surfactants and micro-CaCO3 particles. The carbon materials were used as active materials of air cathodes flooded by ionic liquid-based electrolytes in Li-O2 cells with two different configurations, one with a static electrolyte and the other with a stirred electrolyte, which favor a film-like and large particle deposition, respectively. The presence of large pores enhances the discharge capacity with both mechanisms. Conversely, with respect to the reversible capacity, the trend depends on the cell configuration, with macroporosity favoring better performance with static, but poorer with stirred electrolytes. However, all mesoporous carbons demonstrated larger reversible capacity than a purely macroporous electrode made of carbon black. These results indicate that in addition to pore volume, a proper arrangement of large and small pores is important for discharge capacity, while an extended interface can enhance reversibility in Li-O2 battery cathodes.

Spatial Distributions of Discharged Products of Lithium-Oxygen Batteries Revealed by Synchrotron X-ray Transmission Microscopy.

The discharge products of ether-based Li-O2 cells were grown directly on common carbon-coated TEM grids and observed by oxidation-state-sensitive full field transmission soft X-ray microscopy (TXM). The acquired data have permitted to quantify and localize with spatial resolution the distribution of the oxygen discharge products in these samples (i.e., lithium superoxide, peroxide, and carbonates) and appreciate several compositional, structural, and morphological aspects. Most of the peroxide particles had a toroidal shape, often with a central hole usually open on only one side, and which included significant amounts of superoxide-like phases (LiO2/Li2O2 ratio between 0.2 and 0.5). Smaller particles had smaller or no superoxide content, from which we infer that abundance of soluble LiO2 may have a role in toroid formation. Significant amount of carbonates were found irregularly distributed on the electrode surface, occasionally appearing as small particles and aggregates, and mostly coating lithium peroxide particles. This suggests the formation of a barrier that, similar to the solid electrolyte interface (SEI) critical in Li-ion batteries, requires an appropriate management for a reversible operation.

Mass-transport Control on the Discharge Mechanism in Li-O2 Batteries Using Carbon Cathodes with Varied Porosity.

By comparing carbon electrodes with varying porosity in Li-O2 cells, we show that the effect of electrolyte stirring at a given current density can result in a change from 2D to 3D growth of discharged deposits. The change of morphology is evident using electron microscopy and by analyzing electrode pore size distribution with respect to discharge capacity. As a consequence, carbon electrodes with different textural properties exhibit different capacity enhancements in stirred-electrolyte cells. We demonstrate that mass transport can directly control the discharge mechanism, similar to the electrolyte composition and current density, which have already been recognized as determining factors.

Influence of the operation conditions on CO2 capture by CaO-derived sorbents prepared from synthetic CaCO3.

In this work, a statistical experimental design is performed in order to prepare CaCO3 materials for use as CaO-based CO2 sorbent precursors. The influence of different operational parameters such as synthesis temperature (ST), stirring rate (SR) and surfactant percent (SP) on CO2 capture is studied by applying Response Surface Methodology (RSM). The samples were characterized using different analytical techniques including X-ray diffraction, N2 adsorption isotherm analysis and Scanning Electron Microscopy-X-ray Energy Dispersive Spectroscopy (SEM-EDX). CO2 capture capacity was determined by means of a thermogravimetric analyzer which recorded the mass uptake of the samples when these were exposed to a gas stream containing diluted (15%) CO2. The statistical approach used in this work provides a rapid way of predicting and optimizing the main preparation variables of CaO-derived sorbents for CO2 sorption. The results obtained clearly indicate that four parameters statistically influence CO2 uptake: SR, the square of SR, its interaction with SP and the square of SP.

Modification of carbon screen-printed electrodes by adsorption of chemically synthesized Bi nanoparticles for the voltammetric stripping detection of Zn(II), Cd(II) and Pb(II).

A simple procedure for the chemical synthesis of bismuth nanoparticles and subsequent adsorption on commercial screen-printed carbon electrodes offer reliable quantitation of trace zinc, cadmium and lead by anodic stripping square-wave voltammetry in nondeareated water samples. The influence of two hydrodynamic configurations (convective cell and flow cell) and the effect of various experimental variables upon the stripping signals at the bismuth-coated sensor are explored. The square-wave peak current signal is linear over the low ng mL(-1) range (120 s deposition), with detections limits ranging from 0.9 to 4.9 ng mL(-1) and good precision. Applicability to waste water certified reference material and drinking water samples is demonstrated. The attractive behaviour of the new disposable Bi nanoparticles modified carbon strip electrodes, coupled with the negligible toxicity of bismuth, hold great promise for decentralized heavy metal testing in environmental and industrial effluents waters.