Entropy-Mediated Stable Structural Evolution of Prussian White Cathodes for Long-Life Na-Ion Batteries.

The high-entropy approach is applied to monoclinic Prussian White (PW) Na-ion cathodes to address the issue of unfavorable multilevel phase transitions upon electrochemical cycling, leading to poor stability and capacity decay. A series of Mn-based samples with up to six metal species sharing the N-coordinated positions was synthesized. The material of composition Na1.65 Mn0.4 Fe0.12 Ni0.12 Cu0.12 Co0.12 Cd0.12 [Fe(CN)6 ]0.92 □0.08 ⋅ 1.09H2 O was found to exhibit superior cyclability over medium/low-entropy and conventional single-metal PWs. We also report, to our knowledge for the first time, that a high-symmetry crystal structure may be advantageous for high-entropy PWs during battery operation. Computational comparisons of the formation enthalpy demonstrate that the compositionally less complex materials are prone to phase transitions, which negatively affect cycling performance. Based on data from complementary characterization techniques, an intrinsic mechanism for the stability improvement of the disordered PW structure upon Na+ insertion/extraction is proposed, namely the dual effect of suppression of phase transitions and mitigation of gas evolution.

Synergy of cations in high entropy oxide lithium ion battery anode.

High entropy oxides (HEOs) with chemically disordered multi-cation structure attract intensive interest as negative electrode materials for battery applications. The outstanding electrochemical performance has been attributed to the high-entropy stabilization and the so-called 'cocktail effect'. However, the configurational entropy of the HEO, which is thermodynamically only metastable at room-temperature, is insufficient to drive the structural reversibility during conversion-type battery reaction, and the 'cocktail effect' has not been explained thus far. This work unveils the multi-cations synergy of the HEO Mg0.2Co0.2Ni0.2Cu0.2Zn0.2O at atomic and nanoscale during electrochemical reaction and explains the 'cocktail effect'. The more electronegative elements form an electrochemically inert 3-dimensional metallic nano-network enabling electron transport. The electrochemical inactive cation stabilizes an oxide nanophase, which is semi-coherent with the metallic phase and accommodates Li+ ions. This self-assembled nanostructure enables stable cycling of micron-sized particles, which bypasses the need for nanoscale pre-modification required for conventional metal oxides in battery applications. This demonstrates elemental diversity is the key for optimizing multi-cation electrode materials.

Operando acoustic emission monitoring of degradation processes in lithium-ion batteries with a high-entropy oxide anode.

In recent years, high-entropy oxides are receiving increasing attention for electrochemical energy-storage applications. Among them, the rocksalt (Co0.2Cu0.2Mg0.2Ni0.2Zn0.2)O (HEO) has been shown to be a promising high-capacity anode material. Because high-entropy oxides constitute a new class of electrode materials, systematic understanding of their behavior during ion insertion and extraction is yet to be established. Here, we probe the conversion-type HEO material in lithium half-cells by acoustic emission (AE) monitoring. Especially the clustering of AE signals allows for correlations of acoustic events with various processes. The initial cycle was found to be the most acoustically active because of solid-electrolyte interphase formation and chemo-mechanical degradation. In the subsequent cycles, AE was mainly detected during delithiation, a finding we attribute to the progressive crack formation and propagation. Overall, the data confirm that the AE technology as a non-destructive operando technique holds promise for gaining insight into the degradation processes occurring in battery cells during cycling.

High-Entropy Metal-Organic Frameworks for Highly Reversible Sodium Storage.

Prussian blue analogues (PBAs) are reported to be efficient sodium storage materials because of the unique advantages of their metal-organic framework structure. However, the issues of low specific capacity and poor reversibility, caused by phase transitions during charge/discharge cycling, have thus far limited the applicability of these materials. Herein, a new approach is presented to substantially improve the electrochemical properties of PBAs by introducing high entropy into the crystal structure. To achieve this, five different metal species are introduced, sharing the same nitrogen-coordinated site, thereby increasing the configurational entropy of the system beyond 1.5R. By careful selection of the elements, high-entropy PBA (HE-PBA) presents a quasi-zero-strain reaction mechanism, resulting in increased cycling stability and rate capability. The key to such improvement lies in the high entropy and associated effects as well as the presence of several active redox centers. The gassing behavior of PBAs is also reported. Evolution of dimeric cyanogen due to oxidation of the cyanide ligands is detected, which can be attributed to the structural degradation of HE-PBA during battery operation. By optimizing the electrochemical window, a Coulombic efficiency of nearly 100% is retained after cycling for more than 3000 cycles.

High Entropy and Low Symmetry: Triclinic High-Entropy Molybdates.

Metal molybdates constitute a promising class of materials with a wide application range. Here, we report, to our knowledge for the first time, on the preparation and characterization of medium-entropy and high-entropy metal molybdates, synthesized by an oxalate-based coprecipitation approach. The high-entropy molybdate crystallizes in a triclinic structure, thus rendering it as high-entropy material with the lowest symmetry reported so far. This is noteworthy because high-entropy materials usually tend to crystallize into highly symmetrical structures. It is expected that application of the high-entropy concept to metal molybdates alters the material's characteristics and adds the features of high-entropy systems, that is, tailorable composition and properties. The phase purity and solid solution nature of the molybdates were confirmed by XRD, Raman spectroscopy, TEM, XPS, and ICP-OES.

Lithium containing layered high entropy oxide structures.

Layered Delafossite-type Lix(M1M2M3M4M5…Mn)O2 materials, a new class of high-entropy oxides, were synthesized by nebulized spray pyrolysis and subsequent high-temperature annealing. Various metal species (M = Ni, Co, Mn, Al, Fe, Zn, Cr, Ti, Zr, Cu) could be incorporated into this structure type, and in most cases, single-phase oxides were obtained. Delafossite structures are well known and the related materials are used in different fields of application, especially in electrochemical energy storage (e.g., LiNixCoyMnzO2 [NCM]). The transfer of the high-entropy concept to this type of materials and the successful structural replication enabled the preparation of novel compounds with unprecedented properties. Here, we report on the characterization of a series of Delafossite-type high-entropy oxides by means of TEM, SEM, XPS, ICP-OES, Mössbauer spectroscopy, XRD including Rietveld refinement analysis, SAED and STEM mapping and discuss about the role of entropy stabilization. Our experimental data indicate the formation of uniform solid-solution structures with some Li/M mixing.

Tailoring Threshold Voltages of Printed Electrolyte-Gated Field-Effect Transistors by Chromium Doping of Indium Oxide Channels.

Printed systems spark immense interest in industry, and for several parts such as solar cells or radio frequency identification antennas, printed products are already available on the market. This has led to intense research; however, printed field-effect transistors (FETs) and logics derived thereof still have not been sufficiently developed to be adapted by industry. Among others, one of the reasons for this is the lack of control of the threshold voltage during production. In this work, we show an approach to adjust the threshold voltage (V th) in printed electrolyte-gated FETs (EGFETs) with high accuracy by doping indium-oxide semiconducting channels with chromium. Despite high doping concentrations achieved by a wet chemical process during precursor ink preparation, good on/off-ratios of more than five orders of magnitude could be demonstrated. The synthesis process is simple, inexpensive, and easily scalable and leads to depletion-mode EGFETs, which are fully functional at operation potentials below 2 V and allows us to increase V th by approximately 0.5 V.

High-Entropy Oxides: Fundamental Aspects and Electrochemical Properties.

High-entropy materials, especially high-entropy alloys and oxides, have gained significant interest over the years due to their unique structural characteristics and correlated possibilities for tailoring of functional properties. The developments in the area of high-entropy oxides are highlighted here, with emphasis placed on their fundamental understanding, including entropy-dominated phase-stabilization effects and prospective applications, e.g., in the field of electrochemical energy storage. Critical comments on the different classes of high-entropy oxides are made and the underlying principles for the observed properties are summarized. The diversity of materials design, provided by the entropy-mediated phase-stabilization concept, allows engineering of new oxide candidates for practical applications, warranting further studies in this emerging field of materials science.

High entropy oxides for reversible energy storage.

In recent years, the concept of entropy stabilization of crystal structures in oxide systems has led to an increased research activity in the field of "high entropy oxides". These compounds comprise the incorporation of multiple metal cations into single-phase crystal structures and interactions among the various metal cations leading to interesting novel and unexpected properties. Here, we report on the reversible lithium storage properties of the high entropy oxides, the underlying mechanisms governing these properties, and the influence of entropy stabilization on the electrochemical behavior. It is found that the stabilization effect of entropy brings significant benefits for the storage capacity retention of high entropy oxides and greatly improves the cycling stability. Additionally, it is observed that the electrochemical behavior of the high entropy oxides depends on each of the metal cations present, thus providing the opportunity to tailor the electrochemical properties by simply changing the elemental composition.

Printed Electronics Based on Inorganic Semiconductors: From Processes and Materials to Devices.

Following the ever-expanding technological demands, printed electronics has shown palpable potential to create new and commercially viable technologies that will benefit from its unique characteristics, such as, large-area and wide range of substrate compatibility, conformability and low-cost. Through the last few decades, printed/solution-processed field-effect transistors (FETs) and circuits have witnessed immense research efforts, technological growth and increased commercial interests. Although printing of functional inks comprising organic semiconductors has already been initiated in early 1990s, gradually the attention, at least partially, has been shifted to various forms of inorganic semiconductors, starting from metal chalcogenides, oxides, carbon nanotubes and very recently to graphene and other 2D semiconductors. In this review, the entire domain of printable inorganic semiconductors is considered. In fact, thanks to the continuous development of materials/functional inks and novel design/printing strategies, the inorganic printed semiconductor-based circuits today have reached an operation frequency up to several hundreds of kilohertz with only a few nanosecond time delays at the individual FET/inverter levels; in this regard, often circuits based on hybrid material systems have been found to be advantageous. At the end, a comparison of relative successes of various printable inorganic semiconductor materials, the remaining challenges and the available future opportunities are summarized.

Formation of nanocrystalline graphene on germanium.

Graphitization of a polymer layer provides a convenient route to synthesize nanocrystalline graphene on dielectric surfaces. The transparent and conducting wafer scale material is of interest as a membrane and a coating, and for the generation and detection of light, or strain sensing. In this work, we study the formation of nanocrystalline graphene on germanium, a surface which promotes the CVD synthesis of monocrystalline graphene. The surprising result that we obtained through graphitization is the formation of cavities in germanium, over which nanocrystalline graphene is suspended. Depending on the crystallographic orientation of the germanium surface, either trenches in (110)-Ge or pits in (111)-Ge are formed, and their dimensions depend on the graphitization temperature. Using Raman spatial imaging, we can show that nanocrystalline graphene is formed across the entire wafer in spite of the cavity formation. Interestingly, the Raman intensity is suppressed when the material is supported by germanium and is enhanced when the material is suspended. Through simulations, we can show that these effects are induced by the high refractive index of germanium and by interferences of the light field depending on the spacing between graphene and germanium. Using atomic force and scanning electron microscopy, we determined that ripples in the suspended material are induced by the mismatch of thermal expansion coefficients. Our results provide a new route to lithography-free fabrication of suspended membranes.

Silicon Nanoparticles with a Polymer-Derived Carbon Shell for Improved Lithium-Ion Batteries: Investigation into Volume Expansion, Gas Evolution, and Particle Fracture.

Silicon (Si) and composites thereof, preferably with carbon (C), show favorable lithium (Li) storage properties at low potential, and thus hold promise for application as anode active materials in the energy storage area. However, the high theoretical specific capacity of Si afforded by the alloying reaction with Li involves many challenges. In this article, we report the preparation of small-size Si particles with a turbostratic carbon shell from a polymer precoated powder material. Galvanostatic charge/discharge experiments conducted on electrodes with practical loadings resulted in much improved capacity retention and kinetics for the Si/C composite particles compared to physical mixtures of pristine Si particles and carbon black, emphasizing the positive effect that the core-shell-type morphology has on the cycling performance. Using in situ differential electrochemical mass spectrometry, pressure, and acoustic emission measurements, we gain insights into the gassing behavior, the bulk volume expansion, and the mechanical degradation of the Si/C composite-containing electrodes. Taken together, our research data demonstrate that some of the problems of high-content Si anodes can be mitigated by carbon coating. Nonetheless, continuous electrolyte decomposition, particle fracture, and electrode restructuring due to the large volume changes during battery operation (here, ∼170% in the voltage range of 600-30 mV vs Li+/Li) remain as serious hurdles toward practical implementation.

Facile synthesis of C-FeF2 nanocomposites from CFx: influence of carbon precursor on reversible lithium storage.

Transition metal fluorides are an important class of cathode materials for lithium batteries owing to their high specific energy and safety. However, metal fluorides are electrical insulators, exhibiting slow reaction kinetics with Li. Consequently, metal fluorides can show poor electrochemical performance. Instead, carbon-metal fluoride nanocomposites (CMNFCs) were suggested to enhance electrochemical activity. Chemical synthesis of CMNFCs poses particular challenges due to the poor chemical stability of metal fluorides. Recently, we reported a facile one-step method to synthesize carbon-FeF2 nanocomposites by reacting fluorinated carbon (CFx) with iron pentacarbonyl (Fe(CO)5) at 250 °C. The method resulted in C-FeF2 nanocomposites with improved electrochemical properties. Here, we have synthesized four different C-FeF2 nanocomposites by reacting four different CFx precursors made of petro-coke, carbon black, graphite, and carbon-fibers with Fe(CO)5. Electrochemical performance of all four C-FeF2 nanocomposites was evaluated at 25 °C and 40 °C. It is shown that the nature of CFx has a critical impact on the electrochemical performance of the corresponding C-FeF2 nanocomposites. The C-FeF2 nanocomposites were characterized by using various experimental techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, resistivity measurement, and 57Fe Mössbauer spectroscopy to shed light on the differences in electrochemical behaviour of different C-FeF2 nanocomposites.

Embroidered Copper Microwire Current Collector for Improved Cycling Performance of Silicon Anodes in Lithium-Ion Batteries.

Si holds great promise as an alloying anode material for Li-ion batteries with improved energy density because of its high theoretical specific capacity and favorable operation voltage range. However, the large volume expansion of Si during electrochemical reaction with Li and the associated adverse effects strongly limit its prospect for application. Here, we report on the use of three-dimensional instead of flat current collectors for high-capacity Si anodes in an attempt to mitigate the loss of electrical contact of active electrode regions as a result of structural disintegration with cycling. The current collectors were produced by technical embroidery and consist of interconnected Cu wires of diameter <150 µm. In comparison to Si/Li cells using a conventional Cu foil current collector, the embroidered microwire network-based cells show much enhanced capacity and reversibility due to a higher degree of tolerance to cycling.

[Ag115S34(SCH2C6H4t Bu)47(dpph)6]: synthesis, crystal structure and NMR investigations of a soluble silver chalcogenide nanocluster.

With the aim to synthesize soluble cluster molecules, the silver salt of (4-(tert-butyl)phenyl)methanethiol [AgSCH2C6H4t Bu] was applied as a suitable precursor for the formation of a nanoscale silver sulfide cluster. In the presence of 1,6-(diphenylphosphino)hexane (dpph), the 115 nuclear silver cluster [Ag115S34(SCH2C6H4t Bu)47(dpph)6] was obtained. The molecular structure of this compound was elucidated by single crystal X-ray analysis and fully characterized by spectroscopic techniques. In contrast to most of the previously published cluster compounds with more than a hundred heavy atoms, this nanoscale inorganic molecule is soluble in organic solvents, which allowed a comprehensive investigation in solution by UV-Vis spectroscopy and one- and two-dimensional NMR spectroscopy including 31P/109Ag-HSQC and DOSY experiments. These are the first heteronuclear NMR investigations on coinage metal chalcogenides. They give some first insight into the behavior of nanoscale silver sulfide clusters in solution. Additionally, molecular weight determinations were performed by 2D analytical ultracentrifugation and HR-TEM investigations confirm the presence of size-homogeneous nanoparticles present in solution.

Microwave synthesis of high-quality and uniform 4 nm ZnFe2O4 nanocrystals for application in energy storage and nanomagnetics.

Magnetic nanocrystals with a narrow size distribution hold promise for many applications in different areas ranging from biomedicine to electronics and energy storage. Herein, the microwave-assisted sol-gel synthesis and thorough characterization of size-monodisperse zinc ferrite nanoparticles of spherical shape is reported. X-ray diffraction, 57Fe Mössbauer spectroscopy and X-ray photoelectron spectroscopy all show that the material is both chemically and phase-pure and adopts a partially inverted spinel structure with Fe3+ ions residing on tetrahedral and octahedral sites according to (Zn0.32Fe0.68)tet[Zn0.68Fe1.32]octO4±Î´. Electron microscopy and direct-current magnetometry confirm the size uniformity of the nanocrystals, while frequency-dependent alternating-current magnetic susceptibility measurements indicate the presence of a superspin glass state with a freezing temperature of about 22 K. Furthermore, as demonstrated by galvanostatic charge-discharge tests and ex situ X-ray absorption near edge structure spectroscopy, the as-prepared zinc ferrite nanocrystals can be used as a high-capacity anode material for Li-ion batteries, showing little capacity fade - after activation - over hundreds of cycles. Overall, in addition to the good material characteristics, it is remarkable that the microwave-based synthetic route is simple, easily reproducible and scalable.

In situ and operando atomic force microscopy of high-capacity nano-silicon based electrodes for lithium-ion batteries.

Silicon is a promising next-generation anode material for high-energy-density lithium-ion batteries. While the alloying of nano- and micron size silicon with lithium is relatively well understood, the knowledge of mechanical degradation and structural rearrangements in practical silicon-based electrodes during operation is limited. Here, we demonstrate, for the first time, in situ and operando atomic force microscopy (AFM) of nano-silicon anodes containing polymer binder and carbon black additive. With the help of this technique, the surface topography is analyzed while electrochemical reactions are occurring. In particular, changes in particle size as well as electrode structure and height are visualized with high resolution. Furthermore, the formation and evolution of the solid-electrolyte interphase (SEI) can be followed and its thickness determined by phase imaging and nano-indentation, respectively. Major changes occur in the first lithiation cycle at potentials below 0.6 V with respect to Li/Li(+) due to increased SEI formation - which is a dynamic process - and alloying reactions. Overall, these results provide insight into the function of silicon-based composite electrodes and further show that AFM is a powerful technique that can be applied to important battery materials, without restriction to thin film geometries.

Hierarchical Carbon with High Nitrogen Doping Level: A Versatile Anode and Cathode Host Material for Long-Life Lithium-Ion and Lithium-Sulfur Batteries.

Nitrogen-rich carbon with both a turbostratic microstructure and meso/macroporosity was prepared by hard templating through pyrolysis of a tricyanomethanide-based ionic liquid in the voids of a silica monolith template. This multifunctional carbon not only is a promising anode candidate for long-life lithium-ion batteries but also shows favorable properties as anode and cathode host material owing to a high nitrogen content (>8% after carbonization at 900 °C). To demonstrate the latter, the hierarchical carbon was melt-infiltrated with sulfur as well as coated by atomic layer deposition (ALD) of anatase TiO2, both of which led to high-quality nanocomposites. TiO2 ALD increased the specific capacity of the carbon while maintaining high Coulombic efficiency and cycle life: the composite exhibited stable performance in lithium half-cells, with excellent recovery of low rate capacities after thousands of cycles at 5C. Lithium-sulfur batteries using the sulfur/carbon composite also showed good cyclability, with reversible capacities of ∼700 mA·h·g(-1) at C/5 and without obvious decay over several hundred cycles. The present results demonstrate that nitrogen-rich carbon with an interconnected multimodal pore structure is very versatile and can be used as both active and inactive electrode material in high-performance lithium-based batteries.

Influence of particle size and fluorination ratio of CF x precursor compounds on the electrochemical performance of C-FeF2 nanocomposites for reversible lithium storage.

Systematical studies of the electrochemical performance of CF x -derived carbon-FeF2 nanocomposites for reversible lithium storage are presented. The conversion cathode materials were synthesized by a simple one-pot synthesis, which enables a reactive intercalation of nanoscale Fe particles in a CF x matrix, and the reaction of these components to an electrically conductive C-FeF2 compound. The pretreatment and the structure of the utilized CF x precursors play a crucial role in the synthesis and influence the electrochemical behavior of the conversion cathode material. The particle size of the CF x precursor particles was varied by ball milling as well as by choosing different C/F ratios. The investigations led to optimized C-FeF2 conversion cathode materials that showed specific capacities of 436 mAh/g at 40 °C after 25 cycles. The composites were characterized by Raman spectroscopy, X-Ray diffraction measurements, electron energy loss spectroscopy and TEM measurements. The electrochemical performances of the materials were tested by galvanostatic measurements.

Improving the energy density and power density of CFx by mechanical milling: a primary lithium battery electrode.

The effect of high energy ball milling on the electrochemical performance of graphite fluoride (CFx) was investigated. A significant improvement was observed in both energy density and power density. The volumetric energy density was increased up to a factor of 3 with ball milled materials compared with pristine materials. The gravimetric energy density was increased up to a factor of 2, depending on the discharge rates. At 6C the ball milled material still delivered 40% of its nominal capacity, whereas the pristine material did not exhibit any capacity any more. We achieved the power density of 9860 W/kg with a gravimetric energy density of 800 Wh/kg for the optimized material.