Nitrogen-Doped Carbon Aerogels Derived from Starch Biomass with Improved Electrochemical Properties for Li-Ion Batteries.

Among all advanced anode materials, graphite is regarded as leading and still-unrivaled. However, in the modern world, graphite-based anodes cannot fully satisfy the customers because of its insufficient value of specific capacity. Other limitations are being nonrenewable, restricted natural graphite resources, or harsh conditions required for artificial graphite production. All things considered, many efforts have been made in the investigation of novel carbonaceous materials with desired properties produced from natural, renewable resources via facile, low-cost, and environmentally friendly methods. In this work, we obtained N-doped, starch-based carbon aerogels using melamine and N2 pyrolysis as the source of nitrogen. The materials were characterized by X-ray powder diffraction, elemental analysis, X-ray photoelectron spectroscopy, galvanostatic charge-discharge tests, cyclic voltammetry, and electrochemical impedance spectroscopy. Depending on the doping method and the nitrogen amount, synthesized samples achieved different electrochemical behavior. N-doped, bioderived carbons exhibit far better electrochemical properties in comparison with pristine ones. Materials with the optimal amount of nitrogen (such as MCAGPS-N8.0%-carbon aerogel made from potato starch modified with melamine and CAGPS-N1.2%-carbon aerogel made from potato starch modified by N2 pyrolysis) are also competitive to graphite, especially for high-performance battery applications. N-doping can enhance the efficiency of Li-ion cells mostly by inducing more defects in the carbon matrix, improving the binding ability of Li+ and charge-transfer process.

A Strategy to Optimize the Performance of Bio-Derived Carbon Aerogels by a Structuring Additive.

In this work, we investigated the influence of gum arabic (GA) as a structuring additive, on the electrochemical behavior of bio-derived carbon aerogels (CAGs). Modified carbonaceous materials were prepared by the gelatinization process of potato starch (PS) with the addition of GA in various quantities, followed by the thermal treatment of the obtained gels in an inert gas atmosphere. The obtained anode materials were examined by X-ray diffraction (XRD), elemental analysis (EA), galvanostatic charge/discharge tests (GCDT), extensive cycling (LT-GCDT) and cyclic voltammetry (CV) methods. The highest electrochemical performance was achieved for carbon aerogel material, in which 1% w/w GA was added. The results showed that the proper composition of carbon precursor with a structuring promoter improves the rheological properties of starch gel and stabilizes the final aerogel structure affecting CAG functional properties.

The Temperature Effect on the Electrochemical Performance of Sulfur-Doped LiMn2O4 in Li-Ion Cells.

The application of modified spinel materials in commercial systems relates to the verification of their parameters under different conditions. Hence, in this study, the influence of temperature on the electrochemical behavior of sulfur-doped spinel (LiMn2O3.97S0.03), with reference to stoichiometric spinel (LiMn2O4), was investigated. The electrochemical characteristics of Li-ion cells based on the fabricated spinels were investigated using galvanostatic charge-discharge tests (GCDT), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The results show that introducing sulfur into the spinel structure improves the electrochemical properties at each of the studied temperatures (3, 22 and 61 °C). LiMn2O3.97S0.03 exhibits higher specific capacities, enhanced diffusivity and charge-discharge rates (particularly at low temperatures), and much better cycling stability, regardless of the testing conditions. Our research proves that an S-doping system is a better alternative to LiMn2O4 in the context of working parameters, while maintaining environmental friendliness and low manufacturing costs.

Electrochemical Properties and Structure Evolution of Starch-Based Carbon Nanomaterials as Li-Ion Anodes with Regard to Thermal Treatment.

The influence of the pyrolysis temperature on the structural, textural, and electrochemical properties of carbon aerogels obtained from potato, maize, and rice starches was analyzed. The carbonization of organic precursors, followed by gelatinization, exchange of solvent, and drying process, was carried out in an argon atmosphere at temperatures ranging from 600 °C to 1600 °C. The nanostructured carbons were characterized by X-ray powder diffraction (XRD) as well as N2-adsorption/desorption (N2-BET) methods. The electrochemical behavior of Li-ion cells based on the fabricated carbon anodes was investigated using the galvanostatic charge/discharge tests (GCDT) and electrochemical impedance spectroscopy (EIS). The results show that the thermal treatment stage has a crucial impact on the proper formation of the aerogel material's porous structures and also on their working parameters as anode materials. The highest relative development of the external surface was obtained for the samples pyrolysed at 700 °C, which exhibited the best electrochemical characteristics (the highest specific capacities as well as the lowest charge transfer resistances).

Multifunctional Carbon Aerogels Derived by Sol-Gel Process of Natural Polysaccharides of Different Botanical Origin.

In this manuscript, we describe the results of our recent studies on carbon aerogels derived from natural starches. A facile method for the fabrication of carbon aerogels is presented. Moreover, the complete analysis of the carbonization process of different starch aerogels (potato, maize, and rice) was performed using thermogravimetric studies combined with a detailed analysis of evolved decomposition products. The prepared carbon aerogels were studied in terms of their morphology and electrical properties to relate the origin of starch precursor with final properties of carbon materials. The obtained results confirmed the differences in carbon aerogels' morphology, especially in materials' specific surface areas, depending on the botanical origin of precursors. The electrical conductivity measurements suggest that carbon aerogels with the best electrical properties can be obtained from potato starch.

Enhancement of Electrochemical Performance of LiMn2O4 Spinel Cathode Material by Synergetic Substitution with Ni and S.

Nickel and sulfur doped lithium manganese spinels with a nominal composition of LiMn2-xNixO4-ySy (0.1 ≤ x ≤ 0.5 and y = 0.01) were synthesized by a xerogel-type sol-gel method followed by subsequent calcinations at 300 and 650 °C in air. The samples were investigated in terms of physicochemical properties using X-ray powder diffraction (XRD), transmission electron microscopy (EDS-TEM), N2 adsorption-desorption measurements (N2-BET), differential scanning calorimetry (DSC), and electrical conductivity studies (EC). Electrochemical characteristics of Li/Li⁺/LiMn2-xNixO4-ySy cells were examined by galvanostatic charge/discharge tests (CELL TEST), electrochemical impedance spectroscopy (EIS), and cyclic voltammetry (CV). The XRD showed that for samples calcined at 650 °C containing 0.1 and 0.2 mole of Ni single phase materials of Fd-3m group symmetry and nanoparticles size of around 50 nm were obtained. The energy dispersive X-ray spectroscopy (EDS) mapping confirmed homogenous distribution of nickel and sulfur in the obtained spinel materials. Moreover, it was revealed that the adverse phase transition at around room temperature typical for the stoichiometric spinel was successfully suppressed by Ni and S substitution. Electrochemical results indicated that slight substitution of nickel (x = 0.1) and sulfur (y = 0.01) in the LiMn2O4 enhances the electrochemical performance along with the rate capability and capacity retention.

Nature of the Electrochemical Properties of Sulphur Substituted LiMn2O4 Spinel Cathode Material Studied by Electrochemical Impedance Spectroscopy.

In this work, nanostructured LiMn2O4 (LMO) and LiMn2O3.99S0.01 (LMOS1) spinel cathode materials were comprehensively investigated in terms of electrochemical properties. For this purpose, electrochemical impedance spectroscopy (EIS) measurements as a function of state of charge (SOC) were conducted on a representative charge and discharge cycle. The changes in the electrochemical performance of the stoichiometric and sulphur-substituted lithium manganese oxide spinels were examined, and suggested explanations for the observed dependencies were given. A strong influence of sulphur introduction into the spinel structure on the chemical stability and electrochemical characteristic was observed. It was demonstrated that the significant improvement in coulombic efficiency and capacity retention of lithium cell with LMOS1 active material arises from a more stable solid electrolyte interphase (SEI) layer. Based on EIS studies, the Li ion diffusion coefficients in the cathodes were estimated, and the influence of sulphur on Li⁺ diffusivity in the spinel structure was established. The obtained results support the assumption that sulphur substitution is an effective way to promote chemical stability and the electrochemical performance of LiMn2O4 cathode material.