RESUMEN
Repeated charge/discharge in aqueous zinc-ion batteries (ZIBs) commonly results in surface corrosion/passivation and dendrite formation on zinc anodes, which is a major challenge for the commercialization of zinc-based batteries. In this work, metallic Zn modified by self-assembled monolayers is described as a viable anode for ZIBs. ω-mercaptoundecanoic acid that is spontaneously adsorbed on Zn (MUDA/Zn) contributes to the simultaneous suppression of side reactions and dendrite formation in ZIBs. Though one-molecular-thick, densely packed alkyl chains prohibit H2 O and H+ from making direct contact with the underlying Zn, and surface carboxylate moieties (-COO- ) effectively repel anionic species (OH- ) in a solution, which renders a Zn anode inert against zincate formation within a wide range of pH. In contrast, the electrostatic attraction between surface-carboxylates and cations increases the concentration of Zn2+ on the surface of MUDA/Zn to facilitate Zn plating/stripping with less overpotentials. The high concentration of Zn2+ also results in an increased number of nucleation sites, which enhances the lateral growth of Zn with no formation of dendrites. As a result, MUDA/Zn shows excellent stability during prolonged Zn plating/stripping within a wide range of pH. The advantageous properties of MUDA/Zn are also retained in full-cells coupled with δ-MnO2 cathodes.
RESUMEN
Multi-walled carbon nanotubes (MWNT) was utilized as a conductive additive to enhance the capacity and rate capability of carbon coated LiFePO4 (C-LFP). Composites of C-LFP with MWNT (C-LFP-MWNT) were prepared by blending MWNT at different stages of C-LFP synthesis. The pre-blending (PrB) of MWNT (5, 10, 15 wt%) with LFP precursor (PrB-C-LFP-MWNT) before calcination in a reducing environment (5 vol% H2 in N2) at 750 degrees C, produced phase pure crystalline LFP with a reduction in particle size as increase in MWNT content. This was contrasted with post-blending (PoB) of MWNT with as-synthesized C-LFP (PoB-C-LFP-MWNT), which gave inferior electrochemical performances. The PrB-C-LFP-MWNT (10 wt%) composite showed better cycle stability, higher rate capability, and faster Li diffusion characteristics than PoB-C-LFP-MWNT.
RESUMEN
The structural and electrochemical properties of W-doped LiMn2O4 and LiAl0.025Mn1.975O4 have been investigated to determine the role of W. The cathodic materials were synthesized by sol-gel method, using citric acid as the chelating agent. The results revealed that the substitution of W affects the lattice dimension, the morphology, and the electrochemical performance. Substitution of Al induces an obvious decrease in the electrochemical capacity (but higher capacity retention) and in the case of W the decrease was drastic. As observed from XRD, only a fraction of W is included in the spinel structure. However, for the LiAl0.025W0.025Mn1.95O4, a compromised value is reached between the Al-doped and W-doped LiMn2O4 in terms of capacity and cyclic performance. The pristine spinel LiMn2O4 synthesized by this method shows a relatively superior electrochemical performance at high C-rate with excellent capacity retention.
RESUMEN
A tandem (two-step) particle swarm optimization (PSO) algorithm is implemented in the argyrodite-based multidimensional composition space for the discovery of an optimal argyrodite composition, i.e., with the highest ionic conductivity (7.78 mS cm-1 ). To enhance the industrial adaptability, an elaborate pellet preparation procedure is not used. The optimal composition (Li5.5 PS4.5 Cl0.89 Br0.61 ) is fine-tuned to enhance its practical viability by incorporating oxygen in a stepwise manner. The final composition (Li5.5 PS4.23 O0.27 Cl0.89 Br0.61 ), which exhibits an ionic conductivity (σion ) of 6.70 mS cm-1 and an activation barrier of 0.27 eV, is further characterized by analyzing both its moisture and electrochemical stability. Relative to the other compositions, the exposure of Li5.5 PS4.23 O0.27 Cl0.89 Br0.61 to a humid atmosphere results in the least amount of H2 S released and a negligible change in structure. The improvement in the interfacial stability between the Li(Ni0.9 Co0.05 Mn0.05 )O2 cathode and Li5.5 PS4.23 O0.27 Cl0.89 Br0.61 also results in greater specific capacity during fast charge/discharge. The structural and chemical features of Li5.5 PS4.5 Cl0.89 Br0.61 and Li5.5 PS4.23 O0.27 Cl0.89 Br0.61 argyrodites are characterized using synchrotron X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. This work presents a novel argyrodite composition with favorably balanced properties while providing broad insights into material discovery methodologies with applications for battery development.
RESUMEN
Herein, we propose Ca2+-based dual-carbon batteries (DCBs) that undergo a simultaneous occurrence of reversible accommodations of Ca2+ in a graphite anode (mesocarbon microbeads) and of bis(trifluoromethanesulfonyl)imide (TFSI-) in a graphite cathode (KS6L). For this purpose, we precisely tune electrolytes composed of Ca2+ complexed with a single tetraglyme molecule ([Ca:G4]) in N-butyl-N-methylpyrrolidinium TFSI (Pyr14TFSI) ionic liquid (IL). This ternary electrolyte is required for the enhancement of anodic stability that is needed to accomplish maximal TFSI- intercalation into KS6L at a high potential. A solution of 0.5 M [Ca:G4] in IL ([Ca:G4]/IL) is found to be optimal for DCBs. First, the electrochemical properties and the structural evolution of each graphite in a half-cell configuration are described to demonstrate excellent electrochemical performance. Second, the negligible intercalation of Pyr14+ into an MCMB anode is ascertained in 0.5 M [Ca:G4]/IL. Finally, DCBs are constructed by coupling two electrodes to show high capacity (54.0 mA h g-1 at 200 mA g-1) and reasonable cyclability (capacity fading of 0.022 mA h g-1 cycle-1 at 200 mA g-1 during 300 charge/discharge cycles). This work is the first to examine DCBs based on Ca2+ intercalation and helps pave the way for the development of a new type of next-generation batteries.
RESUMEN
Despite remarkable developments in electrolyte systems over the past 2 decades, magnesium-ion batteries still suffer from corrosion susceptibility and low anodic limits. Herein we describe how graphene oxide (GO), coated onto non-noble metals (Al, Cu, and stainless steel) via electrophoretic deposition, can solve this problem. In all phenyl complex electrolytes, GO coating results in a significant suppression of corrosion and extends the anodic limits (up to 4.0 V vs Mg/Mg2+) with no impact on reversible Mg plating/stripping reactions. The same effect of GO coating is also established in magnesium aluminum chloride complex electrolytes. This remarkable improvement is associated with the electrostatic interaction between the ionic charges of electrolytes and the surface-functional groups of GO. In addition, GO coating does not aggravate the cathode performance of Mo6S8, which allows the use of non-noble metals as current collectors. We also discuss the role of GO in increasing anodic limits when it is hybridized with α-MnO2.
RESUMEN
An alternating stack (SG/GN) consisting of SnO2-functionalized graphene oxide (SG) and amine-functionalized GO (GN) is prepared in solution. The thermally reduced SG/GN (r(SG/GN)) with decreased micro-mesopores and completely eliminated macropores, results in a high reversible capacity and excellent capacity retention (872 mA h g⻹ after 200 cycles at 100 mA g⻹) when compared to a composite without GN.
Asunto(s)
Aminas/química , Suministros de Energía Eléctrica , Grafito/química , Litio/química , Óxidos/química , Compuestos de Estaño/química , Nanocompuestos/química , Nanocompuestos/ultraestructura , Nitrógeno/químicaRESUMEN
The preparation of Hg(II)-modified multi walled carbon nanotube (MWCNT) by reaction of oxidized MWCNT with aqueous HgCl(2) was carried out. The Hg(II)-modified multi walled carbon nanotube (Hg(II)/MWCNT) dispersed in Nafion solution was used to coat the polished graphite electrode surface. The Hg(II)/MWCNT modified graphite electrode was held at a cathodic potential (-1.0 V) to reduce the coordinated Hg(II) to Hg forming nanodroplets of Hg. The modified electrode was characterized by FESEM/EDAX which provided useful insights on the morphology of the electrode. The SEM images showed droplets of Hg in the size of around 260 nm uniformly distributed on the MWCNT. Differential pulse anodic stripping voltammetry (DPASV) and electrochemical impedance spectroscopy were used to study the Hg(II) binding with MWCNT. Differential pulse anodic stripping voltammetry of ppb levels of cadmium and lead using the modified electrode yielded well-defined peaks with low background current under a short deposition time. Detection limit of 0.94 and 1.8 ng L(-1) were obtained following a 3 min deposition for Pb(II) and Cd(II), respectively. Various experimental parameters were characterized and optimized. High reproducibility was observed from the RSD values for 20 repetitive measurements of Pb(II) and Cd(II) (1.7 and 1.9%, respectively). The determination of Pb(II) and Cd(II) in tap water and Pb(II) in human hair samples was carried out. The above method of fabrication of Hg(II)/MWCNT modified graphite electrode clearly suggests a safe route for preparing Hg immobilized electrode for stripping analysis.
Asunto(s)
Cadmio/análisis , Técnicas Electroquímicas/métodos , Plomo/análisis , Mercurio/química , Nanotubos de Carbono/química , Espectroscopía Dieléctrica , Técnicas Electroquímicas/instrumentación , Electrodos , Agua Dulce/análisis , Grafito , Cabello/química , Humanos , Límite de Detección , Reproducibilidad de los ResultadosRESUMEN
A stable electro active thin film of cobalt hexacyanoferrate (CoHCF) was deposited on the surface of an amine adsorbed graphite wax composite electrode using a simple method. Cyclic voltammetric experiments showed two pairs of well defined peaks for this CoHCF modified electrode which exhibited excellent electrocatalytic property for the oxidation of paracetomol at a reduced overpotential of 100 mV and over a concentration range of 3.33x10(-6) to 1.0x10(-3)M with a slope of 0.208 microA/microM with good sensitivity. The influence of the supporting electrolyte on peak current and peak potential were also obtained in addition with effects of common interference (e.g., ascorbic acid) on the response of the modified electrode. Various parameters that influence the electrochemical behavior of the modified electrode were optimized by varying scan rates and pH. Electrochemical impedance spectroscopy studies suggested that the electrode reaction of the CoHCF film is mainly controlled by transport of counter ion. The immobilized CoHCF maintained its redox activity showing a surface controlled electrode reaction with the electron transfer rate constant (K(s)) of 0.94 s(-1) and charge transfer coefficient of 0.42. Hydrodynamic and chronoamperometric studies were done to explore the utility of the modified electrode in dynamic systems. The results of the differential pulse voltammetry (DPV) using the modified electrode was applied for the determination of paracetomol in commercially available tablets. The results obtained reveal that the electrode under study could be used as an effective sensor for online monitoring of paracetomol.
RESUMEN
A cobalt hexacyanoferrate (CoHCF)-modified graphite paraffin wax composite electrode was prepared by a new approach. An amine-functionalised graphite powder was used for the fabrication of the electrode. A functionalised graphite paraffin wax composite electrode was prepared and the surface of the electrode was modified with a thin film of CoHCF. Various parameters that influence the electrochemical behaviour of the modified electrode were studied by varying the background electrolytes, scan rates and pH. The modified electrode showed good electrocatalytic activity towards the oxidation of butylated hydroxyanisole (BHA) under optimal conditions and showed a linear response over the range from 7.9 x 10(-7) to 1.9 x 10(-4) M of BHA with a correlation coefficient of 0.9988. The limit of detection was 1.9 x 10(-7) M. Electrocatalytic oxidation of BHA was effective at the modified electrode at a significantly reduced potential and at a broader pH range. The utility of the modified electrode as an amperometric sensor for the determination of BHA in flow systems was evaluated by carrying out hydrodynamic and chronoamperometric experiments. The modified electrode showed very good stability and a longer shelf life. The modified electrode was applied for the determination of BHA in spiked samples of chewing gum and edible sunflower oil. The advantage of this method is the ease of electrode fabrication, good stability, longer shelf life, low cost and its diverse application for BHA determination.