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Photo-switchable coatings for lithium ion batteries (LIB) can offer the possibility to control the diffusion processes from the electrode materials to the electrolyte and thus, for example, reducing the energy loss in the fully charged state. Fulgide derivatives, as known photo-switches, are investigated concerning their use as coating for vanadium pentoxide, a potential cathode material for LIB. With the help of Density Functional Theory calculations, two fulgide derivatives are characterized with respect to their photophysics, their aggregation behaviour on the cathode material and the ability to form self-assembled monolayers (SAM). Furthermore, the two states of the photo-switchable coating are tested with respect to lithium diffusion from the cathode material, passing the SAM and entering the electrolyte. We found a difference for the energy barriers depending on the state of the photo-switch, preferring its closed form. This behaviour can be used to prevent the loss of charge in batteries of portable devices.
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Molybdenum trioxide is an abundant natural, low-cost, and environmentally friendly material that has gained considerable attention from many researchers in a variety of high-impact applications. It is an attractive inorganic oxide that has been widely studied because of its layered structure, which results in intercalation ability through tetrahedral/octahedral holes and extension channels and leads to superior charge transfer. Shape-related properties such as high specific capacities, the presence of exposed active sites on the oxygen-rich structure, and its natural tendency to oxygen vacancy that leads to a high ionic conductivity are also attractive to technological applications. Due to its chemistry with multiple valence states, high thermal and chemical stability, high reduction potential, and electrochemical activity, many studies have focused on the development of molybdenum oxide-based systems in the last few years. Thus, this article aims to briefly review the latest advances in technological applications of MoO3 and MoO3-based materials in gas sensors, lithium-ion batteries, and water pollution treatment using adsorption and photocatalysis techniques, presenting the most relevant and new information on heterostructures, metal doping, and non-stoichiometric MoO3-x.
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Lithium iron phosphate (LiFePO4, LFP) is the most promising cathode material for use in safe electric vehicles (EVs), due to its long cycle stability, low cost, and low toxicity, but it suffers from low conductivity and ion diffusion. In this work, we present a simple method to obtain LFP/carbon (LFP/C) composites with different types of NC: cellulose nanocrystal (CNC) and cellulose nanofiber (CNF). Microwave-assisted hydrothermal synthesis was used to obtain LFP with nanocellulose inside the vessel, and the final LFP/C composite was achieved by heating the mixture under a N2 atmosphere. The resulting LFP/C indicated that the NC in the reaction medium not only acts as the reducing agent that aqueous iron solutions need (avoiding the use of other chemicals), but also as a stabiliser of the nanoparticles produced in the hydrothermal synthesis, obtaining fewer agglomerated particles compared to synthesis without NC. The sample with the best coating-and, therefore, the best electrochemical response-was the sample with 12.6% carbon derived from CNF in the composite instead of CNC, due to its homogeneous coating. The utilisation of CNF in the reaction medium could be a promising method to obtain LFP/C in a simple, rapid, and low-cost way, avoiding the waste of unnecessary chemicals.
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A regulator based on a converter with step-down/up characteristics is discussed in this paper, which is suitable for processing energy from a lithium-ion battery pack, where the voltage fluctuates from above or below the nominal value. However, this regulator can also be used for applications such as unregulated line rectifiers and renewable energy sources, among others. The converter consists of a non-cascaded interconnection of boost and buck-boost converters such that part of the input energy is transferred directly to the output without reprocessing. Furthermore, it has a non-pulsating input current and a non-inverting output voltage, making it easier to feed the power to other devices. For control purposes, non-linear and linear converter models are derived. The transfer functions of the linear model are used to implement the regulator using a current-mode control scheme. Finally, experimental results for a nominal output voltage of 48 V at 500 W are obtained for the converter in open-loop and closed-loop tests.
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Spinel LiMn2O4is a promising cathode material for lithium-ion batteries. However, bulk LiMn2O4commonly suffers from capacity fading due to the dissolution of Mn into the electrolyte during cycling. Moreover, bulk LiMn2O4exhibits a low Li+diffusion coefficient that limits the volume available to Li+storage. Herein, we report the synthesis of small hollow porous LiMn2O4nanostructures with a mean size of 51 nm exhibiting exposed (111) planes, assembled by nanoparticles of about 6 nm in size. The morphological features of these nanostructures ensure a large contact area between the material and the electrolyte, shorten the pathways for Li+diffusion and provide effective accommodation of the volume change during cycling. Therefore, these hollow nanostructures exhibit improved discharge capacity retention (nearly 82% after 200 cycles) and a greater Li+diffusion coefficient (3.46 × 10-7cm s-1) compared with that of bulk LiMn2O4.
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In this work, a first study on kinetics and thermodynamics of thermal decomposition for synthesis of doped LiMn2O4 nanoparticles is presented. The effect of Mg doping concentration on thermal decomposition of synthesis precursors, prepared by ultrasound-assisted Pechini-type sol-gel process, and its significance on nucleation and growth of Mg-doped LiMn2O4 nanoparticles was studied through a method based on separation of multistage processes in single-stage reactions by deconvolution and transition state theory. Four zones of thermal decomposition were identified: Dehydration, polymeric matrix decomposition, carbonate decomposition and spinel formation, and spinel decomposition. Kinetic and thermodynamic analysis focused on the second zone. First-order Avrami-Erofeev equation was selected as reaction model representing the polymer matrix thermal decomposition. Kinetic and thermodynamic parameters revealed that Mg doping causes an increase in thermal inertia on conversion rate, and CO2 desorption was the limiting step for formation of thermodynamically stable spinel phases. Based on thermogravimetry experiments and the effect of Mg on thermal decomposition, an optimal two-stage heat treatment was determined for preparation of LiMgxMn2-xO4 (x = 0.00, 0.02, 0.05, 0.10) nanocrystalline powders as promising cathode materials for lithium-ion batteries. Crystalline structure, morphology, and stoichiometry of synthesized powders were characterized by XRD, FE-SEM, and AAS, respectively.
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This work focuses on the synthesis of LiFePO4-PANI hybrid materials and studies their electrochemical properties (capacity, cyclability and rate capability) for use in lithium ion batteries. PANI synthesis and optimization was carried out by chemical oxidation (self-assembly process), using ammonium persulfate (APS) and H3PO4, obtaining a material with a high degree of crystallinity. For the synthesis of the LiFePO4-PANI hybrid, a thermal treatment of LiFePO4 particles was carried out in a furnace with polyaniline (PANI) and lithium acetate (AcOLi)-coated particles, using Ar/H2 atmosphere. The pristine and synthetized powders were characterized by XRD, SEM, IR and TGA. The electrochemical characterizations were carried out by using CV, EIS and galvanostatic methods, obtaining a capacity of 95 mAhg-1 for PANI, 120 mAhg-1 for LiFePO4 and 145 mAhg-1 for LiFePO4-PANI, at a charge/discharge rate of 0.1 C. At a charge/discharge rate of 2 C, the capacities were 70 mAhg-1 for LiFePO4 and 100 mAhg-1 for LiFePO4-PANI, showing that the PANI also had a favorable effect on the rate capability.
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A novel series of single lithium-ion conducting polymer electrolytes (SLICPE) based on sp3 boron and poly(ethylene glycol) (PEG) bridges is presented, in the context of the development of a new generation of batteries, with the aim to overcome the problems related to concentration overpotential and low ion transport numbers in conventional solid polymer electrolytes (SPE). The phase separation generated by the physical mixture of SPE with plasticizers such as poly(ethylene oxide) is still a serious problem. In this work, the use of PEG with different chain lengths, for the polycondensation reaction with LiB(OCH3)4, to synthesize SLICPE allows preventing phase separation while tuning the predominant conduction mechanism, and thus the electrical properties, especially the lithium-ion transference number. The ionic transport is promoted by chain mobility as the chain length is increased. SLICPE with the best ionic conductivity values (4.95 ± 0.05) × 10-6 S cm-1 was the one synthesized from poly(ethylene glycol) with an average MN of 400 (BEG8), having an O/Li+ ratio of 20. The lithium transference number ( tLi+) and electrochemical stability window of SLICPE membranes at 25 °C decreased as the PEG bridge length between sp3 boron atoms increased from 0.97 to 0.88 and 5.4 to 4.2 V vs Li0/Li+, respectively, for SLICPE synthesized from PEG with an average MN of 50-400 (BEG1 to BEG8).
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In this study, cobalt (Co) was recycled from spent lithium ion batteries (LIBs) and used to synthesize cobalt ferrite (CoFe2O4-LIBs), which was applied as a catalyst for heterogeneous photo Fenton reactions that discolored methylene blue (MB) dye. The co-precipitation method was used to synthesize CoFe2O4-LIBs and CoFe2O4-R nanoparticles with spinel structures using as raw materials of the LIB cathodes and commercial reagents. X-ray diffraction (XRD) identified the formation of spinel-type CoFe2O4, which formed clusters that could be seen under scanning electron microscopy (SEM) analysis and nanometric particles seen under transmission electron microscopy (TEM). Inductively Coupled Plasma Optical Emission Spectrometer (ICP OES) analysis was used to determine the concentrations of metals present in the ferrite, which reached 6.5% (w/w) of Co. The optimal conditions for discoloring the dye were evaluated using a factorial design. Using CoFe2O4 as a catalyst, the best conditions for catalytic reaction were pH 3, 30.0 mg of catalyst, and 8.0 mL of H2O2 73% (v/v). Discoloration efficiencies of 87.3% and 87.7% were obtained from CoFe2O4-R and CoFe2O4-LIBs, respectively. Therefore, CoFe2O4-LIBs proved to be an efficient catalyst for discoloring MB dye using heterogeneous photo-Fenton reactions. This work is of scientific, social, economic, and environmental interest. It investigates the process of synthesizing,characterizing CoFe2O4LIBs and the efficiency of degrading MB dye, subjects that have economic and environmental, and therefore, social interest. The work has scientific interest particularly because of the correlation between the structure of the recycled material and its catalytic properties.