Photoelectron spectroscopy (PES) is an important technique for tracing and understanding the side reactions responsible for decreasing performance of Li-ion batteries. Interpretation of different ...spectral components is dependent on correct binding energy referencing, and for battery electrodes, this is highly complex. In this work, we investigate the effect on binding energy reference points in PES in correlation to solid electrolyte interphase (SEI) formation, changing electrode potentials, and state of charge variations in Li-ion battery electrodes. The results show that components in the SEI have a significantly different binding energy reference point relative to the bulk electrode material (i.e., up to 2 eV). It is also shown that electrode components with electronically insulating/semiconducting nature are shifted as a function of electrode potential relative to highly conducting materials. Further, spectral changes due to lithiation are highly depending on the nature of the active material and its lithiation mechanism. Finally, a strategy for planning and evaluating PES experiments on battery electrodes is proposed where some materials require careful choice of one or more internal reference points while others may be treated essentially without internal calibration.
In cycled Li-ion batteries, the carbon negative electrode is buried under a thin passivating layer referred to as the solid electrolyte interphase (SEI). In the present study, the increased depth ...sensitivity of hard X-ray photoelectron spectroscopy (HAXPES) as compared to conventional X-ray photoelectron spectroscopy (XPS) is used to study electrochemical changes at such a buried carbon/SEI. Samples from graphite/LiFePO4 cells cycled to specific potentials during the first four charge/discharge cycles were studied. The results show dynamic changes in the SEI during cycling. Reversible, state of charge (SOC) dependent changes in the SEI thickness as well as amounts of lithium oxide, lithium fluoride, lithium and carbon active material were discussed. Moreover, the results indicate lithium enrichment close to the carbon active material surface, which could not be explained by intercalation of lithium into carbon with LiC6 structure or by SEI formation at the surface. Potential dependent shifts in the binding energy of the carbon active material C1s feature showed the importance of internal energy calibration with an SEI feature rather than carbon active material.
Intelligent surfaces: Electrochemical reactions can be induced on a conducting surface placed in an electric field. In this way, a bipolar electrode is formed, and this effect can be used to create ...molecular gradients (see picture). The major advantage of the technique is that the electrode can be of virtually any thickness, shape, and material—as long as it is conductive.
Freestanding, lightweight and flexible Si paper anodes are prepared via a straightforward paper-making process using Cladophora nanocellulose, silicon nanoparticles and carbon nanotubes as the ...building blocks. The uniform Si particle distribution and strong adhesion of the Si nanoparticles to the porous, conductive and flexible nanocellulose/carbon nanotube 3D matrix yield specific capacities of up to 800 mA h g super(-1) (based on the weight of whole electrode) and very good cycling performances.
Galvanostatically electrodeposited coatings of pure Sb or co-deposited Sb and Sb2O3 nanoparticles, prepared from antimony tartrate solutions, were studied as anode materials in Li-ion batteries. It ...is demonstrated that the co-deposition of 20−25% (w/w) Sb2O3 results from a local pH increase at the cathode (due to protonation of liberated tartrate) in poorly buffered solutions. This causes precipitation of Sb2O3 nanoparticles and inclusion of some of the particles in the deposit where they become coated with a protecting layer of Sb. Chronopotentiometric cycling of the deposits, which also were characterized using, e.g., SEM, TEM, and XRD, clearly showed that the Sb2O3-containing deposits were superior as anode materials. While the Sb/Sb2O3 coatings exhibited a specific capacity close to the Sb theoretical value of 660 mA·h·g-1 during more than 50 cycles, the capacity for the Sb coatings gradually decreased to about 250 mA·h·g-1. This indicates that the influence of the significant volume changes present upon the formation and oxidation of Li3Sb was much smaller for the Sb/Sb2O3 nanoparticle coatings. The improved performance can be explained by significant formation of Sb2O3 during the reoxidation, the presence of smaller Sb particles in the Sb/Sb2O3 coatings, and the formation of buffering nanoparticles of Li2O in a matrix of Sb during the first reduction cycle for the Sb/Sb2O3 deposits.
A bilayered cellulose‐based separator design is presented that can enhance the electrochemical performance of lithium‐ion batteries (LIBs) via the inclusion of a porous redox‐active layer. The ...proposed flexible redox‐active separator consists of a mesoporous, insulating nanocellulose fiber layer that provides the necessary insulation between the electrodes and a porous, conductive, and redox‐active polypyrrole‐nanocellulose layer. The latter layer provides mechanical support to the nanocellulose layer and adds extra capacity to the LIBs. The redox‐active separator is mechanically flexible, and no internal short circuits are observed during the operation of the LIBs, even when the redox‐active layer is in direct contact with both electrodes in a symmetric lithium–lithium cell. By replacing a conventional polyethylene separator with a redox‐active separator, the capacity of the proof‐of‐concept LIB battery containing a LiFePO4 cathode and a Li metal anode can be increased from 0.16 to 0.276 mA h due to the capacity contribution from the redox‐active separator. As the presented redox‐active separator concept can be used to increase the capacities of electrochemical energy storage systems, this approach may pave the way for new types of functional separators.
The performance of lithium‐ion batteries can be enhanced by replacing the separator with a flexible redox‐active separator comprising a cellulose layer and an electrically conducting and redox‐active layer.
Highly porous polypyrrole (PPy)-nanocellulose paper sheets have been evaluated as inexpensive and disposable electrochemically controlled three-dimensional solid phase extraction materials. The ...composites, which had a total anion exchange capacity of about 1.1 mol kg(-1), were used for extraction and subsequent release of negatively charged fluorophore tagged DNA oligomers via galvanostatic oxidation and reduction of a 30-50 nm conformal PPy layer on the cellulose substrate. The ion exchange capacity, which was, at least, two orders of magnitude higher than those previously reached in electrochemically controlled extraction, originated from the high surface area (i.e. 80 m(2) g(-1)) of the porous composites and the thin PPy layer which ensured excellent access to the ion exchange material. This enabled the extractions to be carried out faster and with better control of the PPy charge than with previously employed approaches. Experiments in equimolar mixtures of (dT)(6), (dT)(20), and (dT)(40) DNA oligomers showed that all oligomers could be extracted, and that the smallest oligomer was preferentially released with an efficiency of up to 40% during the reduction of the PPy layer. These results indicate that the present material is very promising for the development of inexpensive and efficient electrochemically controlled ion-exchange membranes for batch-wise extraction of biomolecules.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
This paper deals with the use of reaction gradients on bipolar electrodes for the patterning of electrode surfaces. More specifically, the potential and current density distributions in two setups ...containing bipolar electrodes were investigated to optimize and design specific gradient geometries. Comparisons with simulations based on simple conductivity models showed a good qualitative agreement, demonstrating that these models could be used to predict bipolar behavior in more complex setups. In conjunction with imaging surface plasmon resonance (iSPR) experiments, the reaction gradients on bipolar electrodes could further be visualized. It was, for example, found that the gradient in potential difference was approximately linearly distributed in the center of the bipolar electrode and that these potential differences could be determined using an ordinary Ag/AgCl reference electrode. The present results thus provide a better understanding of the processes relevant for bipolar patterning. This approach was finally used to generate a circular gradient region in a self-assembled monolayer, thereby showing the possibilities to create interesting substrates for biosensors and microarray applications.
We present a novel conducting polypyrrole-based composite material, obtained by polymerization of pyrrole in the presence of iron(III) chloride on a cellulose substrate derived from the ...environmentally polluting Cladophora sp. algae. The material, which was doped with chloride ions, was molded into paper sheets and characterized using scanning and transmission electron microscopy, N2 gas adsorption analysis, cyclic voltammetry, chronoamperometry and conductivity measurements at varying relative humidities. The specific surface area of the composite was found to be 57 m2/g and the fibrous structure of the Cladophora cellulose remained intact even after a 50 nm thick layer of polypyrrole had been coated on the cellulose fibers. The composite could be repeatedly used for electrochemically controlled extraction and desorption of chloride and an ion exchanging capacity of 370 C per g of composite was obtained as a result of the high surface area of the cellulose substrate. The influence of the oxidation and reduction potentials on the chloride ion exchange capacity and the nucleation of delocalized positive charges, forming conductive paths in the polypyrrole film, was also investigated. The creation of conductive paths during oxidation followed an effective medium rather than a percolative behavior, indicating that some conduction paths survive the polymer reduction steps. The present high surface area material should be well-suited for use in, e.g., electrochemically controlled ion exchange or separation devices, as well as sensors based on the fact that the material is compact, light, mechanically stable, and moldable into paper sheets.
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