Dry Electrode Manufacturing in a Calender: The Role of Powder Premixing for Electrode Quality and Electrochemical Performance

The dry manufacturing of battery electrodes has the potential to significantly reduce costs and the environmental impact of battery production but deteriorates the electrode quality due to drawbacks in the processability of the materials. By varying the mixing intensity of the powder mixtures, this work investigates the impact of blend homogeneity on the flow properties and the processability of the dry mixtures. Furthermore, the electrochemical performance of dry laminated electrodes made of LiNi0.6Mn0.2Co0.2O2 is investigated with respect to their initial mixture homogeneities and compared to slurry-based electrodes. An improvement of the powder flowability is observed for mixtures with a homogeneously distributed PVDF binder, which acts as a temporary lubricant in dry electrode manufacturing due to its ability to shear, resulting also in filament formation. Capacity and rate performance of electrodes made of homogeneous mixtures are the highest with 169 mAh/g at C/20 and 70 mAh/g at 3C compared to 169 and 49 mAh/g for the slurry-based electrodes, respectively. Cyclic voltammetry indicates lower overpotentials for incompletely homogenized electrodes due to the existence of carbon black aggregates that establish better long-range conductivity. Overall, electrodes from highly homogenized powders show the best electrochemical performance in terms of C-rate capability due to their favorable electrode thickness and porosity resulting from better processability in combination with a sufficiently distributed carbon binder domain

Structure–activity correlation of thermally activated graphite electrodes for vanadium flow batteries

Thermal activation of graphite felts has proven to be a valuable technique for electrodes in vanadium flow batteries to improve their sluggish reaction kinetics. In the underlying work, a novel approach is presented to describe the morphological, microstructural, and chemical changes that occur as a result of the activation process. All surface properties were monitored at different stages of thermal activation and correlated with the electrocatalytic activity. The subsequently developed model consists of a combined ablation and damaging process observed by Raman spectroscopy, X-ray photoelectron spectroscopy and scanning electron microscopy. Initially, the outermost layer of adventitious carbon is removed and sp(2) layers of graphite are damaged in the oxidative atmosphere, which enhances the electrocatalytic activity by introducing small pores with sharp edges. In later stages, the concentration of reaction sites does not increase further, but the defect geometry changes significantly, leading to lower activity. This new perspective on thermal activation allows several correlations between structural and functional properties of graphite for the vanadium redox couple, describing the importance of structural defects over surface chemistry

Origin of the catalytic activity at graphite electrodes in vanadium flow batteries

For many electrochemical devices that use carbon-based materials such as electrolyzers, supercapacitors, and batteries, oxygen functional groups (OFGs) are considered essential to facilitate electron transfer. Researchers implement surface-active OFGs to improve the electrocatalytic properties of graphite felt electrodes in vanadium flow batteries. Herein, we show that graphitic defects and not OFGs are responsible for lowering the activation energy barrier and thus enhance the charge transfer properties. This is proven by a thermal deoxygenation procedure, in which specific OFGs are removed before electrochemical cycling. The electronic and microstructural changes associated with deoxygenation are studied by quasi in situ X-ray photoelectron and Raman spectroscopy. The removal of oxygen groups at basal and edge planes improves the activity by introducing new active edge sites and carbon vacancies. OFGs hinder the charge transfer at the graphite–electrolyte interface. This is further proven by modifying the sp2 plane of graphite felt electrodes with oxygen-containing pyrene derivatives. The electrochemical evolution of OFGs and graphitic defects are studied during polarization and long-term cycling conditions. The hypothesis of increased activity caused by OFGs was refuted and hydrogenated graphitic edge sites were identified as the true reason for this increase

Direct Observation of Reductive Coupling Mechanism between Oxygen and Iron/Nickel in Cobalt-Free Li-Rich Cathode Material: An in Operando X-Ray Absorption Spectroscopy Study

Li-rich cathodes possess high capacity and are promising candidates in next-generation high-energy density Li-ion batteries. This high capacity is partly attributed to its poorly understood oxygen-redox activity. The present Li-rich cathodes contain expensive and environmentally-incompatible cobalt as a main transition metal. In this work, cobalt-free, iron-containing Li-rich cathode material (nominal composition Li$_{1.2}$Mn$_{0.56}$Ni$_{0.16}$Fe$_{0.08}$O$_{2}$) is synthesized, which exhibits excellent discharge capacity (≈250 mAh g$^{-1}$ and cycling stability. In operando, X-ray absorption spectroscopy at Mn, Fe, and Ni K edges reveals its electrochemical mechanism. X-ray absorption near edge structure (XANES) features of Fe and Ni K edges show unusual behavior: when an electrode is charged to 4.5 V, Fe and Ni K edges’ XANES features shift to higher energies, evidence for Fe$^{3+}$→Fe$^{4+}$ and Ni$^{2+}$→Ni$^{4+}$ oxidation. However, when charged above 4.5 V, XANES features of Fe and Ni K edges shift back to lower energies, indicating Fe$^{4+}$→Fe$^{3+}$ and Ni$^{4+}$→Ni$^{3+}$ reduction. This behavior can be linked to a reductive coupling mechanism between oxygen and Fe/Ni. Though this mechanism is observed in Fe-containing Li-rich materials, the only electrochemically active metal in such cases is Fe. Li$_{1.2}$Mn$_{0.56}$Ni$_{0.16}$Fe$_{0.08}$O$_{2}$ has multiple electrochemically active metal ions; Fe and Ni, which are investigated simultaneously and the obtained results will assist tailoring of cost-effective Li-rich materials

La5Zn2Sn

A single crystal of penta­lanthanum dizinc stannide, La5Zn2Sn, was obtained from the elements in a resistance furnace. It belongs to the Mo5SiB2 structure type, which is a ternary ordered variant of the Cr5B3 structure type. The space is filled by bicapped tetra­gonal anti­prisms from lanthanum atoms around tin atoms sharing their vertices. Zinc atoms fill voids between these bicapped tetra­gonal anti­prisms. All four atoms in the asymmetric unit reside on special positions with the following site symmetries: La1 (..m); La2 (4/m..); Zn (m.2m); Sn (422)

Systematic characterization of degraded anion exchange membranes retrieved from vanadium redox flow battery field tests

Commercially available anion exchange membranes were retrieved from VRFB field tests and their degradation due to the various operation conditions is analyzed by in-situ and ex-situ measurements. Ion exchange capacity, permeability and swelling power are used as direct criteria for irreversible changes. Small-angle X-ray scattering (SAXS) and Differential scanning calorimetry (DSC) analyses are used as fingerprint methods and provide information about the morphology and change of the structural properties. A decrease in crystallinity can be detected due to membrane degradation, and, in addition, an indication of reduced polymer chain length is found. While the proton diffusion either increase or decline significantly, the ion exchange capacity and swelling power both are reduced. The observed extent of changes was in good agreement with in-situ measurements in a test cell, where the coulombic and voltage efficiencies are reduced compared to a pristine reference material due to the degradation process

Influence of Process Parameters on the Electrochemical Properties of Hierarchically Structured Na₃V₂(PO₄)₃/C Composites

Sodium vanadium phosphate Na3V2(PO4)3 (NVP) is a promising next-generation cathode material for sodium-ion batteries (SIB) but the practical application as a cathode active material for SIBs is hindered by its poor electronic conductivity. To overcome this limitation and to improve the electrochemical performance in terms of rate capability and cycling stability, carbon coatings are a viable approach. In this work, we utilized a spray-drying synthesis process and systematically varied the processing parameters to optimize the electrochemical performance of NVP/carbon composite materials. The spray-drying process yields spherical, porous granules of NVP particles embedded in a carbon matrix, which is formed by the thermal decomposition of polyacrylic acid or β-lactose