Thermal behaviour of LixMeO2 (Me = Co or Ni + Mn + Co) cathode materials.

Thermal behaviour and thermophysical properties of two typical cathodes for lithium-ion batteries were studied in dependence of temperature. The cathode materials are composite thick films containing a mixture of 90 wt% LiMeO2 active material (with Me = Co or Me = Ni + Mn + Co, respectively) and additives (binder and carbon black), deposited on aluminium current collector foils. The thermal conductivity of each cathode type and their corresponding composite layers were determined up to 573 K from the measured thermal diffusivity, the specific heat capacity and the estimated density based on metallographic methods and structural investigations. In addition, the impact of lithiation degree x in LixMeO2 on the transport properties of cathode samples was also investigated. The quantitative determination and the homogeneity of Li content on the surface and within the bulk of the samples were validated by laser induced breakdown spectrometry. The results presented here explain at cell component level, i.e. cathode material, the thermal runaway behaviour of lithium-ion batteries in a combined approach of application oriented and fundamental research. Therefore, these data are significant for improving the simulation studies of their thermal management, in which the bulk properties are assumed, as a common approach, temperature and lithiation degree independent.

Electrochemical Properties of Laser-Printed Multilayer Anodes for Lithium-Ion Batteries.

New electrode architectures promise huge potential for improving batteries' electrochemical properties, such as power density, energy density, and lifetime. In this work, the use of laser-induced forward transfer (LIFT) was employed and evaluated as a tool for the development of advanced electrode architectures. For this purpose, it was first confirmed that the printing process has no effect on the transferred battery material by comparing the electrochemical performance of the printed anodes with state-of-the-art coated ones. For this, polyvinylidene fluoride (PVDF) was used as a binder and n-methyl-2-pyrrolidone (NMP) as a solvent, which is reported to be printable. Subsequently, multilayer electrodes with flake-like and spherical graphite particles were printed to test if a combination of their electrochemical related properties can be realized with measured specific capacities ranging from 321 mAh·g-1 to 351 mAh·g-1. Further, a multilayer anode design with a silicon-rich intermediate layer was printed and electrochemically characterized. The initial specific capacity was found to be 745 mAh·g-1. The presented results show that the LIFT technology offers the possibility to generate alternative electrode designs, promoting research in the optimization of 3D battery systems.

Modelling and Optimisation of Laser-Structured Battery Electrodes.

An electrochemical multi-scale model framework for the simulation of arbitrarily three-dimensional structured electrodes for lithium-ion batteries is presented. For the parameterisation, the electrodes are structured via laser ablation, and the model is fit to four different, experimentally electrochemically tested cells. The parameterised model is used to optimise the parameters of three different pattern designs, namely linear, gridwise, and pinhole geometries. The simulations are performed via a finite element implementation in two and three dimensions. The presented model is well suited to depict the experimental cells, and the virtual optimisation delivers optimal geometrical parameters for different C-rates based on the respective discharge capacities. These virtually optimised cells will help in the reduction of prototyping cost and speed up production process parameterisation.

Multiobjective Optimization of Laser Polishing of Additively Manufactured Ti-6Al-4V Parts for Minimum Surface Roughness and Heat-Affected Zone.

Metal parts produced by additive manufacturing often require postprocessing to meet the specifications of the final product, which can make the process chain long and complex. Laser post-processes can be a valuable addition to conventional finishing methods. Laser polishing, specifically, is proving to be a great asset in improving the surface quality of parts in a relatively short time. For process development, experimental analysis can be extensive and expensive regarding the time requirement and laboratory facilities, while computational simulations demand the development of numerical models that, once validated, provide valuable tools for parameter optimization. In this work, experiments and simulations are performed based on the design of experiments to assess the effects of the parametric inputs on the resulting surface roughness and heat-affected zone depths. The data obtained are used to create both linear regression and artificial neural network models for each variable. The models with the best performance are then used in a multiobjective genetic algorithm optimization to establish combinations of parameters. The proposed approach successfully identifies an acceptable range of values for the given input parameters (laser power, focal offset, axial feed rate, number of repetitions, and scanning speed) to produce satisfactory values of Ra and HAZ simultaneously.

Ultrafast-Laser Micro-Structuring of LiNi0.8Mn0.1Co0.1O2 Cathode for High-Rate Capability of Three-Dimensional Li-ion Batteries.

Femtosecond ultrafast-laser micro-patterning was employed to prepare a three-dimensional (3D) structure for the tape-casting Ni-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathode. The influences of laser structuring on the electrochemical performance of NMC811 were investigated. The 3D-NMC811 cathode retained capacities of 77.8% at 2 C of initial capacity at 0.1 C, which was thrice that of 2D-NMC811 with an initial capacity of 27.8%. Cyclic voltammetry (CV) and impedance spectroscopy demonstrated that the 3D electrode improved the Li+ ion transportation at the electrode-electrolyte interface, resulting in a higher rate capability. The diffusivity coefficient DLi+, calculated by both CV and electrochemical impedance spectroscopy, revealed that 3D-NMC811 delivered faster Li+ ion transportation with higher DLi+ than that of 2D-NMC811. The laser ablation of the active material also led to a lower charge-transfer resistance, which represented lower polarization and improved Li+ ion diffusivity.

Laser-Treated Surfaces for VADs: From Inert Titanium to Potential Biofunctional Materials.

Objective. Laser-treated surfaces for ventricular assist devices. Impact Statement. This work has scientific impact since it proposes a biofunctional surface created with laser processing in bioinert titanium. Introduction. Cardiovascular diseases are the world's leading cause of death. An especially debilitating heart disease is congestive heart failure. Among the possible therapies, heart transplantation and mechanical circulatory assistance are the main treatments for its severe form at a more advanced stage. The development of biomaterials for ventricular assist devices is still being carried out. Although polished titanium is currently employed in several devices, its performance could be improved by enhancing the bioactivity of its surface. Methods. Aiming to improve the titanium without using coatings that can be detached, this work presents the formation of laser-induced periodic surface structures with a topology suitable for cell adhesion and neointimal tissue formation. The surface was modified by femtosecond laser ablation and cell adhesion was evaluated in vitro by using fibroblast cells. Results. The results indicate the formation of the desired topology, since the cells showed the appropriate adhesion compared to the control group. Scanning electron microscopy showed several positive characteristics in the cells shape and their surface distribution. The in vitro results obtained with different topologies point that the proposed LIPSS would provide enhanced cell adhesion and proliferation. Conclusion. The laser processes studied can create new interactions in biomaterials already known and improve the performance of biomaterials for use in ventricular assist devices.

Electrochemical Performance of Thick-Film Li(Ni0.6Mn0.2Co0.2)O2 Cathode with Hierarchic Structures and Laser Ablation.

The electrochemical performance of lithium-ion batteries is directly influenced by type of active material as well as its morphology. In order to evaluate the impact of particle morphology in thick-film electrodes, Li(Ni0.6Mn0.2Co0.2)O2 (NMC 622) cathodes with bilayer structure consisting of two different particle sizes were manufactured and electrochemically characterized in coin cells design. The hierarchical thick-film electrodes were generated by multiple casting using NMC 622 (TA) with small particle size of 6.7 µm and NMC 622 (BA) with large particle size of 12.8 µm. Besides, reference electrodes with one type of active material as well as with two type of materials established during mixing process (BT) were manufactured. The total film thickness of all hierarchical composite electrodes were kept constant at 150 µm, while the thicknesses of TA and BA were set at 1:2, 1:1, and 2:1. Meanwhile, three kinds of thin-film cathodes with 70 µm were applied to represent the state-of-the-art approach. Subsequently, ultrafast laser ablation was applied to generate groove structures inside the electrodes. The results demonstrate that cells with thin-film or thick-film cathode only containing TA, cells with bilayer electrode containing TBA 1:2, and cells with laser-structured electrodes show higher capacity at C/2 to 5C, respectively.

The Effect of Silicon Grade and Electrode Architecture on the Performance of Advanced Anodes for Next Generation Lithium-Ion Cells.

To increase the specific capacity of anodes for lithium-ion cells, advanced active materials, such as silicon, can be utilized. Silicon has an order of magnitude higher specific capacity compared to the state-of-the-art anode material graphite; therefore, it is a promising candidate to achieve this target. In this study, different types of silicon nanopowders were introduced as active material for the manufacturing of composite silicon/graphite electrodes. The materials were selected from different suppliers providing different grades of purity and different grain sizes. The slurry preparation, including binder, additives, and active material, was established using a ball milling device and coating was performed via tape casting on a thin copper current collector foil. Composite electrodes with an areal capacity of approximately 1.70 mAh/cm² were deposited. Reference electrodes without silicon were prepared in the same manner, and they showed slightly lower areal capacities. High repetition rate, ultrafast laser ablation was applied to these high-power electrodes in order to introduce line structures with a periodicity of 200 µm. The electrochemical performance of the anodes was evaluated as rate capability and operational lifetime measurements including pouch cells with NMC 622 as counter electrodes. For the silicon/graphite composite electrodes with the best performance, up to 200 full cycles at a C-rate of 1C were achieved until end of life was reached at 80% relative capacity. Additionally, electrochemical impedance spectroscopies were conducted as a function of state of health to correlate the used silicon grade with solid electrolyte interface (SEI) formation and charge transfer resistance values.

Characterization and Laser Structuring of Aqueous Processed Li(Ni0.6Mn0.2Co0.2)O2 Thick-Film Cathodes for Lithium-Ion Batteries.

Lithium-ion batteries have led the revolution in portable electronic devices and electrical vehicles due to their high gravimetric energy density. In particular, layered cathode material Li(Ni0.6Mn0.2Co0.2)O2 (NMC 622) can deliver high specific capacities of about 180 mAh/g. However, traditional cathode manufacturing involves high processing costs and environmental issues due to the use of organic binder polyvinylidenfluoride (PVDF) and highly toxic solvent N-methyl-pyrrolidone (NMP). In order to overcome these drawbacks, aqueous processing of thick-film NMC 622 cathodes was studied using carboxymethyl cellulose and fluorine acrylic hybrid latex as binders. Acetic acid was added during the mixing process to obtain slurries with pH values varying from 7.4 to 12.1. The electrode films could be produced with high homogeneity using slurries with pH values smaller than 10. Cyclic voltammetry measurements showed that the addition of acetic acid did not affect the redox reaction of active material during charging and discharging. Rate capability tests revealed that the specific capacities with higher slurry pH values were increased at C-rates above C/5. Cells with laser structured thick-film electrodes showed an increase in capacity by 40 mAh/g in comparison to cells with unstructured electrodes.

A review: Learning from the flight of beetles.

Some Coleoptera (popularly referred to as beetles) can fly at a low Reynolds number with their deployable hind wings, which directly enables a low body weight-a good bioinspiration strategy for miniaturization of micro-air vehicles (MAVs). The hind wing is a significant part of the body and has a folding/unfolding mechanism whose unique function benefits from different structures and materials. This review summarizes the actions, factors, and mechanisms of beetle flight and bioinspired MAVs with deployable wings. The elytron controlled by muscles is the protected part for the folded hind wing and influences flight performance. The resilin, the storage material for elasticity, is located in the folding parts. The hind wings' folding/unfolding mechanism and flight performance can be influenced by vein structures of hollow, solid and wrinkled veins, the hemolymph that flows in hollow veins and its hydraulic mechanism, and various mechanical properties of veins. The action of beetle flight includes flapping flight, hovering, gliding, and landing. The hind wing is passively deformed through force and hemolymph, and the attack angle of the hind wing and the nanomechanics of the veins, muscles and mass body determine the flight performance. Based these factors, bioinspired MAVs with a new deployable wing structure and new materials will be designed to be much more effective and miniaturized. The new fuels and energy supply are significant aspects of MAVs.

Investigation of Fast-Charging and Degradation Processes in 3D Silicon-Graphite Anodes.

The 3D battery concept applied on silicon-graphite electrodes (Si/C) has revealed a significant improvement of battery performances, including high-rate capability, cycle stability, and cell lifetime. 3D architectures provide free spaces for volume expansion as well as additional lithium diffusion pathways into the electrodes. Therefore, the cell degradation induced by the volume change of silicon as active material can be significantly reduced, and the high-rate capability can be achieved. In order to better understand the impact of 3D electrode architectures on rate capability and degradation process of the thick film silicon-graphite electrodes, we applied laser-induced breakdown spectroscopy (LIBS). A calibration curve was established that enables the quantitative determination of the elemental concentrations in the electrodes. The structured silicon-graphite electrode, which was lithiated by 1C, revealed a homogeneous lithium distribution within the entire electrode. In contrast, a lithium concentration gradient was observed on the unstructured electrode. The lithium concentration was reduced gradually from the top to the button of the electrode, which indicated an inhibited diffusion kinetic at high C-rates. In addition, the LIBS applied on a model electrode with micropillars revealed that the lithium-ions principally diffused along the contour of laser-generated structures into the electrodes at elevated C-rates. The rate capability and electrochemical degradation observed in lithium-ion cells can be correlated to lithium concentration profiles in the electrodes measured by LIBS.

Two-Step Laser Post-Processing for the Surface Functionalization of Additively Manufactured Ti-6Al-4V Parts.

Laser powder bed fusion (LPBF) is one of the additive manufacturing methods used to build metallic parts. To achieve the design requirements, the LPBF process chain can become long and complex. This work aimed to use different laser techniques as alternatives to traditional post-processes, in order to add value and new perspectives on applications, while also simplifying the process chain. Laser polishing (LP) with a continuous wave laser was used for improving the surface quality of the parts, and an ultrashort pulse laser was applied to functionalize it. Each technique, individually and combined, was performed following distinct stages of the process chain. In addition to removing asperities, the samples after LP had contact angles within the hydrophilic range. In contrast, all functionalized surfaces presented hydrophobicity. Oxides were predominant on these samples, while prior to the second laser processing step, the presence of TiN and TiC was also observed. The cell growth viability study indicated that any post-process applied did not negatively affect the biocompatibility of the parts. The presented approach was considered a suitable post-process option for achieving different functionalities in localized areas of the parts, for replacing certain steps of the process chain, or a combination of both.

Microfluidic chips for the crystallization of biomacromolecules by counter-diffusion and on-chip crystal X-ray analysis.

Microfluidic devices were designed to perform on micromoles of biological macromolecules and viruses the search and the optimization of crystallization conditions by counter-diffusion, as well as the on-chip analysis of crystals by X-ray diffraction. Chips composed of microchannels were fabricated in poly-dimethylsiloxane (PDMS), poly-methyl-methacrylate (PMMA) and cyclo-olefin-copolymer (COC) by three distinct methods, namely replica casting, laser ablation and hot embossing. The geometry of the channels was chosen to ensure that crystallization occurs in a convection-free environment. The transparency of the materials is compatible with crystal growth monitoring by optical microscopy. The quality of the protein 3D structures derived from on-chip crystal analysis by X-ray diffraction using a synchrotron radiation was used to identify the most appropriate polymers. Altogether the results demonstrate that for a novel biomolecule, all steps from the initial search of crystallization conditions to X-ray diffraction data collection for 3D structure determination can be performed in a single chip.

Research on the Methods for the Mass Production of Multi-Scale Organs-On-Chips.

The success of labs- and organs-on-chips as transformative technologies in the biomedical arena relies on our capacity of solving some current challenges related to their design, modeling, manufacturability, and usability. Among present needs for the industrial scalability and impact promotion of these bio-devices, their sustainable mass production constitutes a breakthrough for reaching the desired level of repeatability in systematic testing procedures based on labs- and organs-on-chips. The use of adequate biomaterials for cell-culture processes and the achievement of the multi-scale features required, for in vitro modeling the physiological interactions among cells, tissues, and organoids, which prove to be demanding requirements in terms of production. This study presents an innovative synergistic combination of technologies, including: laser stereolithography, laser material processing on micro-scale, electroforming, and micro-injection molding, which enables the rapid creation of multi-scale mold cavities for the industrial production of labs- and organs-on-chips using thermoplastics apt for in vitro testing. The procedure is validated by the design, rapid prototyping, mass production, and preliminary testing with human mesenchymal stem cells of a conceptual multi-organ-on-chip platform, which is conceived for future studies linked to modeling cell-to-cell communication, understanding cell-material interactions, and studying metastatic processes.

A chip-based platform for the in vitro generation of tissues in three-dimensional organization.

We describe a multi-purpose platform for the three-dimensional cultivation of tissues. The device is composed of polymer chips featuring a microstructured area of 1-2 cm(2). The chip is constructed either as a grid of micro-containers measuring 120-300 x 300 x 300 microm (h x l x w), or as an array of round recesses (300 microm diameter, 300 microm deep). The micro-containers may be separately equipped with addressable 3D-micro-electrodes, which allow for electrical stimulation of excitable cells and on-site measurements of electrochemically accessible parameters. The system is applicable for the cultivation of high cell densities of up to 8 x 10(6) cells and, because of the rectangular grid layout, allows the automated microscopical analysis of cultivated cells. More than 1000 micro-containers enable the parallel analysis of different parameters under superfusion/perfusion conditions. Using different polymer chips in combination with various types of bioreactors we demonstrated the principal suitability of the chip-based bioreactor for tissue culture applications. Primary and established cell lines have been successfully cultivated and analysed for functional properties. When cells were cultured in non-perfused chips, over time a considerable degree of apoptosis could be observed indicating the need for an active perfusion. The system presented here has also been applied for the differentiation analysis of pluripotent embryonic stem cells and may be suitable for the analysis of the stem cell niche.

Bi2O3 nanoparticles encapsulated in surface mounted metal-organic framework thin films.

We describe a novel procedure to fabricate a recyclable hybrid-photocatalyst based on Bi2O3@HKUST-1 MOF porous thin films. Bi2O3 nanoparticles (NPs) were synthesized within HKUST-1 (or Cu3(BTC)2) surface-mounted metal-organic frame-works (SURMOFs) and characterized using X-ray diffraction (XRD), a quartz crystal microbalance (QCM) and transmission electron microscopy (TEM). The Bi2O3 semiconductor NPs (diameter 1-3 nm)/SURMOF heterostructures exhibit superior photo-efficiencies compared to NPs synthesized using conventional routes, as demonstrated via the photodegradation of the nuclear fast red (NFR) dye.

Tailored surface-enhanced Raman nanopillar arrays fabricated by laser-assisted replication for biomolecular detection using organic semiconductor lasers.

Organic semiconductor distributed feedback (DFB) lasers are of interest as external or chip-integrated excitation sources in the visible spectral range for miniaturized Raman-on-chip biomolecular detection systems. However, the inherently limited excitation power of such lasers as well as oftentimes low analyte concentrations requires efficient Raman detection schemes. We present an approach using surface-enhanced Raman scattering (SERS) substrates, which has the potential to significantly improve the sensitivity of on-chip Raman detection systems. Instead of lithographically fabricated Au/Ag-coated periodic nanostructures on Si/SiO2 wafers, which can provide large SERS enhancements but are expensive and time-consuming to fabricate, we use low-cost and large-area SERS substrates made via laser-assisted nanoreplication. These substrates comprise gold-coated cyclic olefin copolymer (COC) nanopillar arrays, which show an estimated SERS enhancement factor of up to ∼ 10(7). The effect of the nanopillar diameter (60-260 nm) and interpillar spacing (10-190 nm) on the local electromagnetic field enhancement is studied by finite-difference-time-domain (FDTD) modeling. The favorable SERS detection capability of this setup is verified by using rhodamine 6G and adenosine as analytes and an organic semiconductor DFB laser with an emission wavelength of 631.4 nm as the external fiber-coupled excitation source.

Organic semiconductor distributed feedback laser pixels for lab-on-a-chip applications fabricated by laser-assisted replication.

The integration of organic semiconductor distributed feedback (DFB) laser sources into all-polymer chips is promising for biomedical or chemical analysis. However, the fabrication of DFB corrugations is often expensive and time-consuming. Here, we apply the method of laser-assisted replication using a near-infrared diode laser beam to efficiently fabricate inexpensive poly(methyl methacrylate) (PMMA) chips with spatially localized organic DFB laser pixels. This time-saving fabrication process enables a pre-defined positioning of nanoscale corrugations on the chip and a simultaneous generation of nanoscale gratings for organic edge-emitting laser pixels next to microscale waveguide structures. A single chip of size 30 mm × 30 mm can be processed within 5 min. Laser-assisted replication allows for the subsequent addition of further nanostructures without a negative impact on the existing photonic components. The minimum replication area can be defined as being as small as the diode laser beam focus spot size. To complete the fabrication process, we encapsulate the chip in PMMA using laser transmission welding.