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Operando synchrotron radiation-based techniques are a precious tool in battery research, as they enable the detection of metastable intermediates and ensure characterization under realistic cycling conditions. However, they do not come exempt of risks. The interaction between synchrotron radiation and samples, particularly within an active electrochemical cell, can induce relevant effects at the irradiated spot, potentially jeopardizing the experiment's reliability and biasing data interpretation. With the aim of contributing to this ongoing debate, a systematic investigation into these phenomena was carried out by conducting a root cause analysis of beam-induced effects during the operando characterization of two of the most commonly employed positive electrode materials in commercial Li-ion batteries: LiNi0.33Mn0.33Co0.33O2 and LiFePO4. The study spans across diverse experimental conditions involving different cell types and absorption and scattering techniques and seeks to correlate beam effects with factors such as radiation energy, photon flux, exposure time, and other parameters associated with radiation dosage. Finally, it provides a comprehensive set of guidelines and recommendations for assessing and mitigating beam-induced effects that may affect the outcome of battery operando experiments.
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An operando dual-edge X-ray absorption spectroscopy on both transition-metal ordered and disordered LiNi0.5Mn1.5O4 during electrochemical delithiation and lithiation was carried out. The large data set was analyzed via a chemometric approach to gain reliable insights into the redox activity and the local structural changes of Ni and Mn throughout the electrochemical charge and discharge reaction. Our findings confirm that redox activity relies predominantly on the Ni2+/4+ redox couple involving a transient Ni3+ phase. Interestingly, a reversible minority contribution of Mn3+/4+ is also evinced in both LNMO materials. While the reaction steps and involved reactants of both ordered and disordered LNMO materials generally coincide, we highlight differences in terms of reaction dynamics as well as in local structural evolution induced by the TM ordering.
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Synchrotron-based techniques have been key tools in the discovery, understanding, and development of battery materials. In this review, some of the most suitable X-ray spectroscopy related techniques employed for addressing diverse scientific cases connected to battery science are highlighted. Furthermore, current shortcomings, intrinsic limitations, and ongoing challenges of individual techniques are pointed out, providing an outlook of future trends that are relevant to the battery research community. In particular, the ongoing development of next generation synchrotrons, machine learning algorithms for data analysis and combined theoretical/experimental approaches will enhance the already powerful assets of these advanced spectroscopic methods.
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Developing multifunctional polymeric binders is key to the design of energy storage technologies with value-added features. We report that a multigram-scale synthesis of perylene diimide polymer (PPDI), from a single batch via polymer analogous reaction route, yields high molecular weight polymers with suitable thermal stability and minimized solubility in electrolytes, potentially leading to improved binding affinity toward electrode particles. Further, it develops strategies for designing copolymers with virtually any desired composition via a subsequent grafting, leading to purpose-built binders. PPDI dye as both binder and electroactive additive in lithium half-cells using lithium iron phosphate exhibits good electrochemical performance.
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We report a computational study on 3d transition-metal (Cr, Mn, Fe, and Co) carbodiimides in Li- and Na-ion batteries. The obtained cell voltages semi-quantitatively fit the experiments, highlighting the practicality of PBE+U as an approach for modeling the conversion-reaction mechanism of the FeNCN archetype with lithium and sodium. Also, the calculated voltage profiles agree satisfactorily with experiment both for full (Li-ion battery) and partial (Na-ion battery) discharge, even though experimental atomistic knowledge is missing up to now. Moreover, we rationalize the structural preference of intermediate ternaries and their characteristic lowering in the voltage profile using chemical-bonding and Mulliken-charge analysis. The formation of such ternary intermediates for the lithiation of FeNCN and the contribution of at least one ternary intermediate is also confirmed experimentally. This theoretical approach, aided by experimental findings, supports the atomistic exploration of electrode materials governed by conversion reactions.
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Pyrolysis is an effective way to convert biomass into biofuel while obtaining highly porous active carbon materials. In this study, a facile approach, involving hydrothermal and pyrolysis steps, is described for preparing hybrid metal oxide nanoparticle-embedded porous hard carbon matrices (MnO/C) from the biowaste rice husk and organometallic precursors. It was found that the pyrolysis/calcination temperature had a strong influence over the microstructure, especially over the porosity, but also over the carbon content and crystallinity of the nanocomposites; hence, the electrical properties can be controlled. Galvanostatic measurements showed that the nanocomposite obtained at 600 °C exhibited the highest charge/discharge capacity and best stability, delivering an initial discharge capacity of 1104 mA·h·g-1 at a current density of 200 mA·g-1, and retaining a value of 830 mA·h·g-1 after 200 cycles, suggesting excellent cycle stability. A discharge capacity of 581 mA·h·g-1 was obtained even at a current density as high as 2400 mA·g-1, demonstrating superb rate capability. This outstanding electrochemical performance, ascribed to high electrochemical activity of the embedded MnO nanoparticles enhanced by electrical conductivity provided through the high surface area of the active porous carbon support, is discussed in relation to the microstructure of the nanocomposite.
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Miniaturized rechargeable batteries with high specific power are required for substitution of the large sized primary batteries currently prevalent in integrated systems since important implications in dimensions and power are expected in future miniaturized applications. Commercially available secondary microbatteries are based on lithium metal which suffers from several well-known safety and manufacturing issues and low specific power when compared to (super) capacitors. A high specific power and novel dual-metal-ion microbattery based on LiMn2O4, zinc, and an aqueous electrolyte is presented in this work. Specific power densities similar to the ones exhibited by typical electrochemical supercapacitors (3400 W kg-1) while maintaining specific energies in the range of typical Li-ion batteries are measured (â¼100 Wh kg-1). Excellent stability with very limited degradation (99.94% capacity retention per cycle) after 300 cycles is also presented. All of these features, together with the intrinsically safe nature of the technology, allow anticipation of this alternative micro power source to have high impact, particularly in the high demand field of newly miniaturized applications.
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LiMn2O4 (LMO) thin films are deposited on Si-based substrates with Pt current collector via multi-layer pulsed-laser-deposition technique. The LMO thin films feature unique kinetics that yield outstanding electrochemical cycling performance in an aqueous environment. At extremely high current densities of up to 1880 µA cm-2 (≈ 348 C), a reversible capacity of 2.6 µAh cm-2 is reached. Furthermore, the electrochemical cycling remains very stable for over 3500 cycles with a remarkable capacity retention of 99.996% per cycle. We provide evidence of significant nondiffusion-controlled, pseudocapacitive-like storage contribution of the LMO electrode.
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Titania materials are gaining interest as negative electrode materials in Li-ion batteries due to their high power capability and enhanced safety. Today, Li4 Ti5 O12 is the material of choice for commercial batteries, but other titania materials, namely polymorphs of TiO2 , are being explored because of their similar electrochemical behavior and higher theoretical specific charge capacity. In practice, the specific charge capacity of TiO2 remains far below the theoretical value of 336â mA h g-1 due to poor electrical conductivity and slow Li-ion mobility. This Minireview describes the main strategies developed to overcome the limitations of TiO2 polymorphs. Special attention is given to TiO2 (B) since its outstanding Li-ion mobility, the highest mobility among all TiO2 polymorphs, has led to superior electrochemical performance. Finally, the potential of titania materials in sodium-ion batteries is also discussed.
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The upper part of the frontispiece shows the operating potential vs. the practical specific charge capacity of different positive and negative Li-ion battery materials. The stability window of todays liquid electrolyte solutions is confined by the formation of the cathode electrolyte interphase (CEI) and the solid electrolyte interphase (SEI). In the lower part of the frontispiece, the overall performance of conventional carbonaceous and titania based materials are compared. In this mini review, Fehse and Ventosa illustrate the promising role of TiO2 (B) as battery material with enhanced safety, cycle stability and rate performance.