Important Impact of the Slurry Mixing Speed on Water-Processed Li4Ti5O12 Lithium-Ion Anodes in the Presence of H3PO4 as the Processing Additive.

The aqueous processing of lithium transition metal oxides into battery electrodes is attracting a lot of attention as it would allow for avoiding the use of harmful N-methyl-2-pyrrolidone (NMP) from the cell fabrication process and, thus, render it more sustainable. The addition of slurry additives, for instance phosphoric acid (PA), has been proven to be highly effective for overcoming the corresponding challenges such as aluminum current collector corrosion and stabilization of the active material particle. Herein, a comprehensive investigation of the effect of the ball-milling speed on the effectiveness of PA as a slurry additive is reported using Li4Ti5O12 (LTO) as an exemplary lithium transition metal oxide. Interestingly, at elevated ball-milling speeds, rod-shaped lithium phosphate particles are formed, which remain absent at lower ball-milling speeds. A detailed surface characterization by means of SEM, EDX, HRTEM, STEM-EDX, XPS, and EIS revealed that in the latter case, a thin protective phosphate layer is formed on the LTO particles, leading to an improved electrochemical performance. As a result, the corresponding lithium-ion cells comprising LTO anodes and LiNi0.5Mn0.3Co0.2O2 (NMC532) cathodes reveal greater long-term cycling stability and higher capacity retention after more than 800 cycles. This superior performance originates from the less resistive electrode-electrolyte interphase evolving upon cycling, owing to the interface-stabilizing effect of the lithium phosphate coating formed during electrode preparation. The results highlight the importance of commonly neglected─frequently not even reported─electrode preparation parameters.

Enhanced Electrochemical Capacity of Spherical Co-Free Li1.2 Mn0.6 Ni0.2 O2 Particles after a Water and Acid Treatment and its Influence on the Initial Gas Evolution Behavior.

Li-rich layered oxides (LRLO) with specific energies beyond 900 Wh kg-1 are one promising class of high-energy cathode materials. Their high Mn-content allows reducing both costs and the environmental footprint. In this work, Co-free Li1.2 Mn0.6 Ni0.2 O2 was investigated. A simple water and acid treatment step followed by a thermal treatment was applied to the LRLO to reduce surface impurities and to establish an artificial cathode electrolyte interface. Samples treated at 300 °C show an improved cycling behavior with specific first cycle capacities of up to 272 mAh g-1 , whereas powders treated at 900 °C were electrochemically deactivated due to major structural changes of the active compounds. Surface sensitive analytical methods were used to characterize the structural and chemical changes compared to the bulk material. Online DEMS measurements were conducted to get a deeper understanding of the effect of the treatment strategy on O2 and CO2 evolution during electrochemical cycling.

Impact of the Transition Metal Dopant in Zinc Oxide Lithium-Ion Anodes on the Solid Electrolyte Interphase Formation.

Conversion/alloying materials (CAMs) provide substantially higher specific capacities than graphite, the state-of-the-art lithium-ion battery anode material. The ability to host much more lithium per unit weight and volume is, however, accompanied by significant volume changes, which challenges the realization of a stable solid electrolyte interphase (SEI). Herein, the comprehensive characterization of the composition and evolution of the SEI on transition metal (TM) doped zinc oxide as CAM model compound, is reported, with a particular focus on the impact of the TM dopant (Fe or Co). The results unveil that the presence of iron specifically triggers the electrolyte decomposition. However, this detrimental effect can be avoided by stabilizing the interface with the electrolyte by a carbonaceous coating. These findings provide a great leap forward toward the enhanced understanding of such doped materials and (transition) metal oxide active materials in general.

Scalable Synthesis of Microsized, Nanocrystalline Zn0.9 Fe0.1 O-C Secondary Particles and Their Use in Zn0.9 Fe0.1 O-C/LiNi0.5 Mn1.5 O4 Lithium-Ion Full Cells.

Conversion/alloying materials (CAMs) are a potential alternative to graphite as Li-ion anodes, especially for high-power performance. The so far most investigated CAM is carbon-coated Zn0.9 Fe0.1 O, which provides very high specific capacity of more than 900 mAh g-1 and good rate capability. Especially for the latter the optimal particle size is in the nanometer regime. However, this leads to limited electrode packing densities and safety issues in large-scale handling and processing. Herein, a new synthesis route including three spray-drying steps that results in the formation of microsized, spherical secondary particles is reported. The resulting particles with sizes of 10-15 µm are composed of carbon-coated Zn0.9 Fe0.1 O nanocrystals with an average diameter of approximately 30-40 nm. The carbon coating ensures fast electron transport in the secondary particles and, thus, high rate capability of the resulting electrodes. Coupling partially prelithiated, carbon-coated Zn0.9 Fe0.1 O anodes with LiNi0.5 Mn1.5 O4 cathodes results in cobalt-free Li-ion cells delivering a specific energy of up to 284 Wh kg-1 (at 1 C rate) and power of 1105 W kg-1 (at 3 C) with remarkable energy efficiency (>93 % at 1 C and 91.8 % at 3 C).

Epitaxial Bottom-up Growth of Silicon Nanowires on Oxidized Silicon by Alloy-Catalyzed Gas-Phase Synthesis.

High-yield epitaxial bottom-up growth of silicon nanowires is still challenging but desirable for various applications such as antireflective coatings, solar cells, and high-aspect-ratio scanning probes. Hence, pristine single-crystalline silicon surfaces are, in principle, required as a growth substrate, but reoxidation occurring prior to nanowire growth obstructs epitaxial growth significantly. Here, we present an approach that relies on Al/Au alloy catalysts for gas-phase silicon nanowire synthesis, allowing intrinsically an in situ removal of a native silicon-oxide layer during the initial growth stages. This approach yields reliable and superior epitaxial growth of silicon nanowires on single-crystalline silicon substrates.

Calcium vanadate sub-microfibers as highly reversible host cathode material for aqueous zinc-ion batteries.

For the first time, CaV6O16·3H2O (CVO), synthesized via a highly efficient and fast microwave reaction, is used as a cathode material for aqueous zinc-ion batteries. Ex situ X-ray diffraction confirms the structure of this material to be stable upon reversible Zn2+ intercalation, due to its large interlayer distance (8.08 Å). The pillaring effect of calcium makes the as-prepared CVO an excellent Zn2+ cation host.

Cobalt Disulfide Nanoparticles Embedded in Porous Carbonaceous Micro-Polyhedrons Interlinked by Carbon Nanotubes for Superior Lithium and Sodium Storage.

Transition metal sulfides are appealing electrode materials for lithium and sodium batteries owing to their high theoretical capacity. However, they are commonly characterized by rather poor cycling stability and low rate capability. Herein, we investigate CoS2, serving as a model compound. We synthesized a porous CoS2/C micro-polyhedron composite entangled in a carbon-nanotube-based network (CoS2-C/CNT), starting from zeolitic imidazolate frameworks-67 as a single precursor. Following an efficient two-step synthesis strategy, the obtained CoS2 nanoparticles are uniformly embedded in porous carbonaceous micro-polyhedrons, interwoven with CNTs to ensure high electronic conductivity. The CoS2-C/CNT nanocomposite provides excellent bifunctional energy storage performance, delivering 1030 mAh g-1 after 120 cycles and 403 mAh g-1 after 200 cycles (at 100 mA g-1) as electrode for lithium-ion (LIBs) and sodium-ion batteries (SIBs), respectively. In addition to these high capacities, the electrodes show outstanding rate capability and excellent long-term cycling stability with a capacity retention of 80% after 500 cycles for LIBs and 90% after 200 cycles for SIBs. In situ X-ray diffraction reveals a significant contribution of the partially graphitized carbon to the lithium and at least in part also for the sodium storage and the report of a two-step conversion reaction mechanism of CoS2, eventually forming metallic Co and Li2S/Na2S. Particularly the lithium storage capability at elevated (dis-)charge rates, however, appears to be substantially pseudocapacitive, thus benefiting from the highly porous nature of the nanocomposite.

Ultrafast Ionic Liquid-Assisted Microwave Synthesis of SnO Microflowers and Their Superior Sodium-Ion Storage Performance.

Tin oxide (SnO) is considered one of the most promising metal oxides for utilization as anode material in sodium ion batteries (SIBs), because of its ease of synthesis, high specific gravimetric capacity, and satisfactory cycling performance. However, to aim at practical applications, the Coulombic efficiency during cycling needs to be further improved, which requires a deeper knowledge of its working mechanism. Here, a microflower-shaped SnO material is synthesized by means of an ultrafast ionic liquid-assisted microwave method. The as-prepared SnO anode active material exhibits excellent cycling performance, good Coulombic efficiency as well as a large capacity delivered at low potential, which is fundamental to maximize the energy output of SIBs. These overall merits were never reported before for pure SnO anodes (i.e., not in a composite with, for example, graphene). Additionally, by combining ex situ XRD and XPS, it is clearly demonstrated for the first time that the Sn-Na alloy, which is formed during the initial sodium sodiation, desodiates in two successive but fully separated steps. Totally different from the previous report, the pristine SnO phase is not regenerated upon desodiation up to 3 V vs Na/Na+. The newly disclosed reaction route provides an alternative view of the complex reaction mechanism of these families of metal oxides for sodium ion batteries.

Numerical correction of anti-symmetric aberrations in single HRTEM images of weakly scattering 2D-objects.

Here, we present a numerical post-processing method for removing the effect of anti-symmetric residual aberrations in high-resolution transmission electron microscopy (HRTEM) images of weakly scattering 2D-objects. The method is based on applying the same aberrations with the opposite phase to the Fourier transform of the recorded image intensity and subsequently inverting the Fourier transform. We present the theoretical justification of the method, and its verification based on simulated images in the case of low-order anti-symmetric aberrations. Ultimately the method is applied to experimental hardware aberration-corrected HRTEM images of single-layer graphene and MoSe2 resulting in images with strongly reduced residual low-order aberrations, and consequently improved interpretability. Alternatively, this method can be used to estimate by trial and error the residual anti-symmetric aberrations in HRTEM images of weakly scattering objects.

Practical aspects of the use of the X(2) holder for HRTEM-quality TEM sample preparation by FIB.

The X(2) holder enables the effective production of thin, electron transparent samples for high-resolution transmission electron microscopy (HRTEM). Improvements to the X(2) holder for high-quality transmission electron microscopy (TEM) sample preparation are presented in this paper. We discuss the influence of backscattered electrons (BSE) from the sample holder in determining the lamella thickness in situ and demonstrate that a significant improvement in thickness determination can be achieved by comparatively simple means using the relative BSE intensity. We show (using Monte Carlo simulations) that by taking into account the finite collection angle of the electron backscatter detector, an approximately 20% underestimation of the lamella thickness in a silicon sample can be avoided. However, a correct thickness determination for light-element lamellas still remains a problem with the backscatter method; we introduce a more accurate method using the energy dispersive X-ray spectroscopy (EDX) signal for in situ thickness determination. Finally, we demonstrate how to produce a thin lamella with a nearly damage-free surface using the X(2) holder in combination with sub-kV polishing in the Fischione Instruments׳ NanoMill(®) TEM specimen preparation system.

Aberration correction and electron holography.

Electron holography has been shown to allow a posteriori aberration correction. Therefore, an aberration corrector in the transmission electron microscope does not seem to be needed with electron holography to achieve atomic lateral resolution. However, to reach a signal resolution sufficient for detecting single light atoms and very small interatomic fields, the aberration corrector has turned out to be very helpful. The basic reason is the optimized use of the limited number of "coherent" electrons that are provided by the electron source, as described by the brightness. Finally, quantitative interpretation of atomic structures benefits from the holographic facilities of fine-tuning of the aberration coefficients a posteriori and from evaluating both amplitude and phase.

Off-axis electron holography in an aberration-corrected transmission electron microscope.

Electron holography allows the reconstruction of the complete electron wave, and hence offers the possibility of correcting aberrations. In fact, this was shown by means of the uncorrected CM30 Special Tübingen transmission electron microscope (TEM), revealing, after numerical aberration correction, a resolution of approximately 0.1 nm, both in amplitude and phase. However, it turned out that the results suffer from a comparably poor signal-to-noise ratio. The reason is that the limited coherent electron current, given by gun brightness, has to illuminate a width of at least four times the point-spread function given by the aberrations. As, using the hardware corrector, the point-spread function shrinks considerably, the current density increases and the signal-to-noise ratio improves correspondingly. Furthermore, the phase shift at the atomic dimensions found in the image plane also increases because the collection efficiency of the optics increases with resolution. In total, the signals of atomically fine structures are better defined for quantitative evaluation. In fact, the results achieved by electron holography in a Tecnai F20 Cs-corr TEM confirm this.

Electron holography with a Cs-corrected transmission electron microscope.

Cs correctors have revolutionized transmission electron microscopy (TEM) in that they substantially improve point resolution and information limit. The object information is found sharply localized within 0.1 nm, and the intensity image can therefore be interpreted reliably on an atomic scale. However, for a conventional intensity image, the object exit wave can still not be detected completely in that the phase, and hence indispensable object information is missing. Therefore, for example, atomic electric-field distributions or magnetic domain structures cannot be accessed. Off-axis electron holography offers unique possibilities to recover completely the aberration-corrected object wave with uncorrected microscopes and hence we would not need a Cs-corrected microscope for improved lateral resolution. However, the performance of holography is affected by aberrations of the recording TEM in that the signal/noise properties ("phase detection limit") of the reconstructed wave are degraded. Therefore, we have realized off-axis electron holography with a Cs-corrected TEM. The phase detection limit improves by a factor of four. A further advantage is the possibility of fine-tuning the residual aberrations by a posteriori correction. Therefore, a combination of both methods, that is, Cs correction and off-axis electron holography, opens new perspectives for complete TEM analysis on an atomic scale.

Ordered mesoporous silicon carbide (OM-SiC) via polymer precursor nanocasting.

Ordered mesoporous SiC with high specific surface area (650-800 m(2) g(-1)) and well ordered pore structure was obtained via nanocasting of polycarbosilanes into SBA-15 and subsequent conversion of the polymer at 1300 degrees C.