Using Hierarchically Structured, Nanoporous Particles as Building Blocks for NCM111 Cathodes.

Nanoparticles have many advantages as active materials, such as a short diffusion length, low charge transfer resistance, or a reduced probability of cracking. However, their low packing density makes them unsuitable for commercial battery applications. Hierarchically structured microparticles are synthesized from nanoscale primary particles by targeted aggregation. Due to their open accessible porosity, they retain the advantages of nanomaterials but can be packed much more densely. However, the intrinsic porosity of the secondary particles leads to limitations in processing properties and increases the overall porosity of the electrode, which must be balanced against the improved rate stability and increased lifetime. This is demonstrated for an established cathode material for lithium-ion batteries (LiNi0.33Co0.33Mn0.33O2, NCM111). For active materials with low electrical or ionic conductivity, especially post-lithium systems, hierarchically structured particles are often the only way to produce competitive electrodes.

Cycling Stability of Lithium-Ion Batteries Based on Fe-Ti-Doped LiNi0.5 Mn1.5 O4 Cathodes, Graphite Anodes, and the Cathode-Additive Li3 PO4.

This study addresses the improved cycling stability of Li-ion batteries based on Fe-Ti-doped LiNi0.5 Mn1.5 O4 (LNMO) high-voltage cathode active material and graphite anodes. By using 1 wt% Li3 PO4 as cathode additive, over 90% capacity retention for 1000 charge-discharge cycles and remaining capacities of 109 mAh g-1 are reached in a cell with an areal capacity of 2.3 mAh cm- 2 (potential range: 3.5-4.9 V). Cells without the additive, in contrast, suffer from accelerated capacity loss and increase polarization, resulting in capacity retention of only 78% over 1000 cycles. An electrolyte consisting of ethylene carbonate, dimethyl carbonate, and LiPF6 is used without additional additives. The significantly improved cycling stability of the full cells is mainly due to two factors, namely, the low MnIII content of the Fe-Ti-doped LNMO active material and the use of the cathode-additive Li3 PO4 . Crystalline Li3 PO4 yields a drastic reduction of transition metal deposition on the graphite anode and prevents Li loss and the propagation of cell polarization. Li3 PO4 is added to the cathode slurry that makes it a very simple and scalable process, first reported herein. The positive effects of crystalline Li3 PO4 as electrode additive, however, should apply to other cell chemistries as well.

Dielectric Behavior of Thin Polymerized Composite Layers Fabricated by Inkjet-Printing.

A detailed study of the dielectric behavior of printed capacitors is given, in which the dielectric consists of a thin (<1 µm) ceramic/polymer composite layer with high permittivities of εr 20-69. The used ink contains surface-modified Ba0.6Sr0.4TiO3 (BST), a polymeric crosslinking agent and a thermal initiator, which allows the immediate polymerization of the ink during printing, leading to homogenous layers. To validate the results of the calculated permittivities, different layer thicknesses of the dielectric are printed and the capacitances, as well as the loss factors, are measured. Afterwards, the exact layer thicknesses are determined with cross sectional SEM images of ion-etched samples. Then, the permittivities are calculated with the known effective area of the capacitors. Furthermore, the ink composition is varied to obtain different ceramic/polymer ratios and thus different permittivities. The packing density of all composites is analyzed via SEM to show possible pores and validate the target ratio, respectively. The correlation between the chosen ratio and the measured permittivity is discussed using models from the literature. In addition, the leakage current of some capacitors is measured and discussed. For that, the dielectric was printed on different bottom electrodes as the nature of the electrode was found to be crucial for the performance.

Network-Structured BST/MBO Composites Made from Core-Shell-Structured Granulates.

A finite element method (FEM)-based simulation approach to predict the tunability in composite materials was developed and tested with analytical data. These tests showed good prediction capabilities of the simulation for the test data. The simulation model was then used to predict the tunability of a network-structured composite, where the dielectric phase formed clusters in a paraelectric network. This was achieved by simulating a reciprocal core-shell unit cell of said network. The simulation showed a high tunability for this network model, exceeding the tunability of the analytically evaluated layered, columnar, and particulate model. The simulation results were experimentally verified with a Ba0.6Sr0.4TiO3/Mg3B2O6 (BST/MBO) composite, where core-shell granulates were made with a two-step granulation process. These structured samples showed higher tunability and dielectric loss than the unstructured samples made for comparison. Overall, the structured samples showed higher tunability to loss ratios, indicating their potential for use in tunable radio frequency applications, since they may combine high performance with little energy loss.

Impact of Particle and Crystallite Size of Ba0.6Sr0.4TiO3 on the Dielectric Properties of BST/P(VDF-TrFE) Composites in Fully Printed Varactors.

In the field of printed electronics, electronic components such as varactors are of special interest. As ferroelectric materials, Ba0.6Sr0.4TiO3 (BST) and poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) are promising compounds to be used in functional inks for the fabrication of fully inkjet-printed dielectric layers. In BST/P(VDF-TrFE) composite inks, the influence of the particle and crystallite size is investigated by using different grinding media sizes and thermal treatments at varying temperatures. It was found that with an increasing particle and crystallite size, both the relative permittivity and tunability increase as well. However, the thermal treatment which impacts both the particle and crystallite size has a greater effect on the dielectric properties. An additional approach is the reduction in the dielectric layer thickness, which has a significant effect on the maximal tunability. Here, with a thickness of 0.9 µm, a tunability of 29.6% could be achieved in an external electric field of 34 V µm-1.

A multipurpose laboratory diffractometer for operando powder X-ray diffraction investigations of energy materials.

Laboratory X-ray diffractometers are among the most widespread instruments in research laboratories around the world and are commercially available in different configurations and setups from various manufacturers. Advances in detector technology and X-ray sources push the data quality of in-house diffractometers and enable the collection of time-resolved scattering data during operando experiments. Here, the design and installation of a custom-built multipurpose laboratory diffractometer for the crystallographic characterization of battery materials are reported. The instrument is based on a Huber six-circle diffractometer equipped with a molybdenum microfocus rotating anode with 2D collimated parallel-beam X-ray optics and an optional two-bounce crystal monochromator. Scattered X-rays are detected with a hybrid single-photon-counting area detector (PILATUS 300K-W). An overview of the different diffraction setups together with the main features of the beam characteristics is given. Example case studies illustrate the flexibility of the research instrument for time-resolved operando powder X-ray diffraction experiments as well as the possibility to collect higher-resolution data suitable for diffraction line-profile analysis.

Strong-Acid-Catalyzed Formation of Crystalline LiNbO3 at Low Ambient Temperatures.

A crystalline LiNbO3 material was synthesized at 80 °C by an optimized sol-gel method using a double alkoxide alcoholic solution in the presence of hydrogen peroxide (H2O2) and strong acids. The same reaction in the presence of water or acetic acid resulted in amorphous powders with fewer impurities but which crystallized only at 450 °C and higher temperatures. The purity of the crystalline material obtained at 80 °C is strongly dependent on the Li/Nb molar ratio used for the reaction. It appears that the combination of strong acids with H2O2 in air generates perfect conditions for the synthesis of low-temperature crystalline lithium niobate oxide derivatives and can be extended to various other metal oxides. The developed synthetic method opens the potential for the coating of low-melting-point conductive polymer materials with LiNbO3 crystalline films.

Enhancing the Stability of LiNi0.5Mn1.5O4 by Coating with LiNbO3 Solid-State Electrolyte: Novel Chemically Activated Coating Process versus Sol-Gel Method.

LiNbO3-coated LiNi0.5Mn1.5O4 spinel was fabricated by two methods: using hydrogen-peroxide as activating agent and sol-gel method. The structure of the obtained cathode materials was investigated using a scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and the electrochemical properties of the prepared cathodes were probed by charge-discharge studies. The morphology of the coating material on the surface and the degree of coverage of the coated particles were investigated by SEM, which showed that the surface of LiNi0.5Mn1.5O4 particles is uniformly encapsulated by lithium innovate coating. The influence of the LiNbO3 coating layer on the spinel's properties was explored, including its effect on the crystal structure and electrochemical performance. XRD studies of the obtained coated active materials revealed very small expansion or contraction of the unit cell. From the capacity retention tests a significant improvement of the electrochemical properties resulted when a novel chemically activated coating process was used. Poorer results, however, were obtained using the sol-gel method. The results also revealed that the coated materials by the new method exhibit enhanced reversibility and stability compared to the pristine and reference ones. It was shown that the morphology of the coating material and possible improvement of communication between the substrates play an important role.

Fabrication of Flexible Multilayer Composite Capacitors Using Inkjet Printing.

This paper shows a straightforward method for printing multilayer composite capacitors with three dielectric layers on flexible substrates. As known from multilayer ceramic chip capacitors (MLCCs), it is possible to create a parallel connection of the layers without enlarging the needed area. Hence, the overall capacitance is increased, as the capacitances of the single dielectric layers add up. To realize printed capacitors, a special ceramic/polymer composite ink is used. The ink consists of surface-modified Ba0.6Sr0.4TiO3 (BST), a polymeric crosslinking agent and a thermal initiator, which allows an immediate polymerization of the ink, leading to very homogenous layers. The dielectric behavior of the capacitors is examined for each completed dielectric layer (via impedance spectroscopy) so that the changes with every following layer can be analyzed. It is demonstrated that the concept works, and capacitors with up to 3420 pF were realized (permittivity of ~40). However, it was also shown that the biggest challenge is the printing of the needed silver electrodes. They show a strong coffee stain effect, leading to thicker edge areas, which are difficult to overprint. Only with the help of printed supporting structures was it possible to lower the failure rate when printing thin dielectric layers.

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).

Polymerizable Ceramic Ink System for Thin Inkjet-Printed Dielectric Layers.

An innovative ceramic ink system for thin inkjet-printed dielectric layers is presented, with which it is possible to avoid undesired drying effects. This system contains surface-modified Ba0.6Sr0.4TiO3 (BST) particles, a cross-linking agent, and a thermal radical initiator. The polymerization starts immediately after the ink drop contacts the heated substrate and therefore leads to very homogeneous topographies. Since an organic/inorganic composite ink is used, no sintering is needed after printing and thus printing on flexible substrates is possible. A comparison of the printing and drying behavior between modified and nonmodified BST with the described ink system is performed. The successful surface modification is confirmed via X-ray photoelectron spectroscopy (XPS). Topographies of different printed structures are compared by white light interferometry, the occurring polymerization is confirmed by measurements with an oscillatory rheometer, layer thicknesses are determined by scanning electron microscopy (SEM) images, and the capacitance of a printed capacitor is measured via impedance spectroscopy. It is successfully shown that the developed ink system enables the production of thin ceramic layers (<1 µm) with very homogeneous topographies since undesired drying effects can be avoided. The printed dielectric layers on flexible substrates have a high ceramic content and a high permittivity of 40.

Structural insights into the formation and voltage degradation of lithium- and manganese-rich layered oxides.

One major challenge in the field of lithium-ion batteries is to understand the degradation mechanism of high-energy lithium- and manganese-rich layered cathode materials. Although they can deliver 30 % excess capacity compared with today's commercially- used cathodes, the so-called voltage decay has been restricting their practical application. In order to unravel the nature of this phenomenon, we have investigated systematically the structural and compositional dependence of manganese-rich lithium insertion compounds on the lithium content provided during synthesis. Structural, electronic and electrochemical characterizations of LixNi0.2Mn0.6Oy with a wide range of lithium contents (0.00 ≤ x ≤ 1.52, 1.07 ≤ y < 2.4) and an analysis of the complexity in the synthesis pathways of monoclinic-layered Li[Li0.2Ni0.2Mn0.6]O2 oxide provide insight into the underlying processes that cause voltage fading in these cathode materials, i.e. transformation of the lithium-rich layered phase to a lithium-poor spinel phase via an intermediate lithium-containing rock-salt phase with release of lithium/oxygen.

Fabrication and Characterization of Fully Inkjet Printed Capacitors Based on Ceramic/Polymer Composite Dielectrics on Flexible Substrates.

The preparation of fully inkjet printed capacitors containing ceramic/polymer composites as the dielectric material is presented. Therefore, ceramic/polymer composite inks were developed, which allow a fast one-step fabrication of the composite thick films. Ba0.6Sr0.4TiO3 (BST) is used as the ceramic component and poly(methyl methacrylate) (PMMA) as the polymer. The use of such composites allows printing on flexible substrates. Furthermore, it results in improved values for the permittivity compared to pure polymers. Three composite inks with varying ratio of BST to PMMA were used for the fabrication of composite thick films consisting of 33, 50 and 66 vol% BST, respectively. All inks lead to homogeneous structures with precise transitions between the different layers in the capacitors. Besides the microstructures of the printed thick films, the dielectric properties were characterized by impedance spectroscopy over a frequency range of 100 Hz to 200 kHz. In addition, the influence of a larger ceramic particle size was investigated, to raise permittivity. The printed capacitors exhibited dielectric constants of 20 up to 55 at 1 kHz. Finally, the experimental results were compared to different theoretical models and their suitability for the prediction of εcomposite was assessed.

Improving mechanical fatigue resistance by optimizing the nanoporous structure of inkjet-printed Ag electrodes for flexible devices.

The development of highly conductive metallic electrodes with long-term reliability is in great demand for real industrialization of flexible electronics, which undergo repeated mechanical deformation during service. In the case of vacuum-deposited metallic electrodes, adequate conductivity is provided, but it degrades gradually during cyclic mechanical deformation. Here, we demonstrate a long-term reliable Ag electrode by inkjet printing. The electrical conductivity and the mechanical reliability during cyclic bending are investigated with respect to the nanoporous microstructure caused by post heat treatment, and are compared to those of evaporated Ag films of the same thickness. It is shown that there is an optimized nanoporous microstructure for inkjet-printed Ag films, which provides a high conductivity and improved reliability. It is argued that the nanoporous microstructure ensures connectivity within the particle network and at the same time reduces plastic deformation and the formation of fatigue damage. This concept provides a new guideline to develop an efficient method for highly conductive and reliable metallic electrodes for flexible electronics.