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Anode-free lithium batteries (AFLBs) present an opportunity to eliminate the need for conventional graphite electrodes or excess lithium–metal anodes, thus increasing the cell energy density and streamlining the manufacturing process. However, their attributed poor coulombic efficiency leads to rapid capacity decay, underscoring the importance of achieving stable plating and stripping of Li on the negative electrode for the success of this cell configuration. A promising approach is the utilization of lithiophilic coatings such as silver to mitigate the Li nucleation overpotential on the Cu current collector, thereby improving the process of Li plating/stripping. On the other hand, inkjet printing (IJP) emerges as a promising technique for electrode modification in the manufacturing process of lithium batteries, offering a fast and scalable technology capable of depositing both thin films and patterned structures. In this work, a Fujifilm Dimatix inkjet printer was used to deposit Ag sites on a Cu current collector, aiming to modulate the interfacial electrochemistry of the system. Samples were fabricated with varying areas of coverage and the electrochemical performance of the system was systematically evaluated from bare Cu (non-lithiophilic) to a designed pattern (partially lithiophilic) and the fully coated thin film case (lithiophilic). Increasing lithiophilicity resulted in lower charge transfer resistance, higher exchange current density and reduced Li nucleation overpotential (from 55.75 mV for bare Cu to 13.5 mV for the fully coated case). Enhanced half-cell cyclability and higher coulombic efficiency were also achieved (91.22% CE over 76 cycles for bare Cu, 97.01% CE over 250 cycles for the fully coated case), alongside more uniform lithium deposition and fewer macroscopic irregularities. Moreover, our observations demonstrated that surface patterning through inkjet printing could represent an innovative, easy and scalable strategy to provide preferential Li nucleation sites to guide the subsequent Li deposition.

Supersaturated alloys can exhibit superior properties and electrodeposition is a cost-effective and versatile technique to produce them. In this review, the chemical, mechanical and structural properties of supersaturated alloys are discussed, and connections with metallic glasses and high entropy alloys are also exposed. After discussing mechanisms causing supersaturation in electrodeposited alloys, an overview of the most important electrodeposited metastable alloys is provided, showing that they are mainly used as protective coatings able to improve corrosion resistance and tribological performance of a large variety of industrial components. Composition of the electrolytic baths and deposition parameters are also considered and discussed.

The integration of multifunctional elements directly embedded in three-dimensional (3D) printed parts is the cutting-edge of additive manufacturing (AM) and it is crucial for enlarging as well as for strengthening AM role in industrial applications. Here, a straightforward and low-cost method that synergically combines stereolithography (SLA) and selective electroless metallization (EM) is presented for the fabrication of 3D parts characterized by complex shapes and end-use multifunctionalities (conductive, magnetic, mechanical properties). To this end, a novel photocurable composite based on acrylate resin loaded with nickel (Ni) particles is developed for high-resolution SLA-printing of features with self-catalytic properties for EM. Ni particles are loaded in the resin to trigger metal deposition avoiding time consuming and expensive laser-based surface activation. The effect of Ni content on SLA behavior as well as on the efficiency of EM process is studied. Metallized SLA cured samples show good electrical and magnetic properties as well as improved robustness with respect to their non-loaded counterparts. Then, selective metallization of 3D printed parts is successfully achieved by implementing a multi-material SLA-printing where loaded and non-loaded resins are properly interchanged with strong adhesion at the interface, thus offering a cost-effective approach for rapid prototyping of functional free-form features on 3D structures.

Zinc-ion batteries (ZIBs) are currently being studied as an alternative to lithium-ion batteries (LIBs). The nucleation and growth of the zinc deposition mechanism is a critical field of research in ZIBs, as it directly affects the battery efficiency and lifespan. It is of paramount importance in mitigating the formation of porous, dendritic Zn structures that may cause cell inefficiency and, eventually, short-circuiting failures. Interfacial engineering plays a key role in providing reversible plating and stripping of metallic Zn in ZIBs through the proper regulation of the electrode–electrolyte interface. In this work, we investigated the behavior and characteristics of Zn plating on inkjet-printed Ti3C2Tx MXene-coated substrates according to the different electrolyte compositions. Specifically, ZnCl2 and ZnSO4 solutions were employed, evaluating the effect of a relatively low-molecular-weight polyethylene glycol (PEG400) addition to the electrolyte as additive. Electrochemical analyses demonstrated higher deposition kinetics in chloride-based electrolytes rather than sulfate ones, resulting in lower nucleation overpotentials. However, the morphology and microstructure of the plated Zn, investigated via scanning electron microscopy (SEM) and X-ray diffraction (XRD), revealed that the electrolytic solution played a predominant role in the Zn crystallite formation rather than the Ti3C2Tx MXene coating. Specifically, the preferential Zn [002] orientation could be favored when using additive-free ZnSO4 solution, and a PEG addition was found to be an efficient texturing agent only in ZnCl2 solution.

In the last few years, the manufacturing of microelectromechanical systems (MEMS) by means of innovative tridimensional and bidimensional printing technologies has significantly catalyzed the attention of researchers. Inkjet material deposition, in particular, can become a key enabling technology for the production of polymer-based inertial sensors characterized by low cost, high manufacturing scalability and superior sensitivity. In this paper, a fully inkjet-printed polymeric accelerometer is proposed, and its manufacturing steps are described. The manufacturing challenges connected with the inkjet deposition of SU-8 as a structural material are identified and addressed, resulting in the production of a functional spring-mass sensor. A step-crosslinking process allows optimization of the final shape of the device and limits defects typical of inkjet printing. The resulting device is characterized from a morphological point of view, and its functionality is assessed in performing optical readout. The acceleration range of the optimized device is 0–0.7 g, its resolution is 2 × 10−3 g and its sensitivity is 6745 nm/g. In general, the work demonstrates the feasibility of polymeric accelerometer production via inkjet printing, and these characteristic parameters demonstrate their potential applicability in a broad range of uses requiring highly accurate acceleration measurements over small displacements.

CO2 accumulation is inducing an effect of global warming. Adsorption using solid sorbents is proving as an effective strategy for CO2 capture and reuse. The aim of this study was to develop amino-functionalized magnetic nanoparticles by depositing various amines through co-precipitation or impregnation-sonication. Structural characteristics were studied through SEM, BET and XRD analyses, evidencing coarse particles with low crystallinity and surface areas of 100–150 m2 g−1, while FT-IR confirmed CO2 interacting with substrate. The load of functional group, particles stability, and CO2 sorption capacity were assessed through elemental and thermogravimetric analysis. It was found that loads of functional groups ranging from 1.6 to 6.1 wt.%. were deposited, and most samples showed sound stability up to 100°C. Sorption capacities were in the range 0.2–1.5 g gNH2−1, the highest being 1.46 g gNH2−1 for ɛ-aminocaproic acid. Such sample also exhibited good recyclability, with a performance drop of 11% after many cycles. CO2 uptake decreased with increasing temperature in the range 25–45°C, suggesting a chemical bond between CO2 and amines. Amino functionalized particles could thus be an interesting solution for CO2 capture and utilization thanks to fast kinetics, recyclability, and ease of separation.

Hypothesis: In recent years, gel polymer electrolytes (quasi-solid state electrolytes) have attracted great attention as a suitable substitute for liquid electrolytes. On the other hand, ionic liquids could dramatically enhance the ionic conductivity of electrolytes. In this work, gel polymer electrolytes based on poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)/poly(ethylene oxide) (PEO) blends (for application in dye-sensitized solar cells (DSSCs)) and imidazolium-based ionic liquids were prepared. It is supposed that blending these two polymers could reduce the degree of crystallization and increase the porosity of the electrolyte blend to yield a higher electrolyte uptake and ionic conductivity. Methods: Polymer blend electrolytes were prepared in different blend ratios and in the presence of either one of the ionic liquids including BMII or BMIMBF4 through phase inversion method and their properties were investigated by differential scanning calorimetry (DSC), mercury porosimetry, electrolyte uptake, and morphology to optimize the blend ratio. Findings: It was found that the blend ratio of 60/40 (w/w) PVDF-HFP/PEO has the highest porosity and electrolyte uptake. Crystallization investigations by DSC showed that there is a direct relationship between the decrease of crystallinity of two polymers and the increment of electrolyte ionic conductivity. Electrolyte uptake gradually increased with increasing PEO component concentration up to 40 wt%, and reached a maximum of 98.49% and 89.48% for BMIMBF4 and BMII, respectively. Beyond this concentration, a decrease in electrolyte uptake was seen, which is an undesirable feature for the produced samples. In this blend ratio ionic conductivity was measured as 2.07 mS/cm and 1.78 mS/cm for PVDF-HFP/PEO/BMIMBF4 and PVDF-HFP/PEO/BMII electrolytes, respectively.

Ultrasonic-Assisted Liquid Phase Exfoliation (UALPE) is considered one of the most promising approaches for the scale-up of graphene production. The process is based on the isolation and stabilization of layers of 2D materials, such as graphene: the selection of a proper stabilizing/exfoliating agent is crucial to achieve a stable Few-Layers-Graphene (FLG) dispersion. In the present work we propose the use of alkali lignin (AL) as a polymeric stabilizing agent for the rapid (≤ 3 hours) synthesis of FLG. Sonication time and graphite-to-lignin (Gr/AL) ratios were investigated as the primary operational parameters to identify the optimal working conditions. Spectroscopical characterization of the samples were employed to assess the quality of the synthesized material: the analysis of the Raman and XPS spectra provided insight on the number of layers and the nature of the limited defects introduced with the exfoliation procedure.Low-defectivity FLG was obtained at Gr/AL = 8 and a sonication time of 3 hours. Furthermore, Scanning Electron Microscopy and Dynamic Light Scattering were performed to investigate the size of the exfoliated flakes (∼ 400 nm). The procedure proposed represents a rapid route for the synthesis of FLG, which will be further explored for composites in chemiresistive devices.

The demand for robust engineering materials demonstrating good tribological performance under arduous service conditions has forged the development of novel coating materials and techniques. In the field of surface engineering, multilayer structures have attracted great interest. Electrodeposition offers a versatile and controlled route to engineering coatings in tribology. Electrodeposited coatings can provide tailored electronic, magnetic, mechanical, wear-resistant and corrosion-resistant characteristics as well as an improved load-bearing capability. The performance of multilayered electrodeposits can significantly exceed that of single layers. This paper critically reviews the fabrication, microstructure, engineering properties and potential applications of electrodeposited multilayer coatings. Such coatings can provide powerful, complementary additions to the toolkit for engineering electrodeposition, enabling future advances. Critical aspects requiring further R & D endeavors are identified.

Targeted drug delivery from untethered microrobots is a topic of major interest in current biomedical research. The possibility to load smart materials able to administer active principles on remotely in vivo guidable microdevices constitutes one of the most attractive opportunities to overcome the drawbacks of classical untargeted delivery methodologies. Hydrogels, in particular, are ideal candidates as drug-carrying materials due to their biocompatibility, low cost, and ease of manufacturing. On the other hand, these polymers suffer from poor control over release rate and overall released amount. Starting from these premises, the present article demonstrates the possibility to tune the release of hydrogels applied on magnetically steerable microrobots by fabricating microsystems via layer-by-layer self-assembly. By doing this, the diffusion of chemicals from the hydrogel layers to the external environment can be optimized and the phenomenon of burst release can be strongly limited. The microrobotic platforms employed to transport the hydrogel active material are fabricated by employing 3D printing in combination with wet metallization and present a gold layer on their surface to enhance biocompatibility. The maneuverability of microdevices coated with both thin and thick multilayers is investigated, individuating optimized parameters for efficient actuation.

Aerogels are commonly regarded as soft and versatile materials for multiple applications thanks to their features such as elastic behavior, swelling ability and responsive characteristics. In the last decades these qualities have ensured them multiple uses in biomedical field as controlled drug delivery systems and scaffolds for tissue engineering applications. Recently their employment as sensors has attracted great interest especially thanks to their tunability and the possibility to be used as soft material instead of conventional and many times unreliable sensors in multiple sensing applications. In this work we synthetized graphene oxide/polyaniline aerogels by in situ chemical polymerization of aniline monomer in aqueous dispersion of graphene oxide sheets. We characterized the system through chemical and mechanical analysis, and we its responsivity as gas sensing device was verified. Moreover, we investigated the influence of the encapsulation of graphene nanoplatelets on the responsive ability of the device. The addition of the graphene moieties improves the conductivity of the system, its compressive mechanical resistance and the applicability of these devices as gas sensors.

Ethylene glycol-based solutions containing metal precursor chloride salts were investigated for the electrodeposition of cobalt thin films and nanowires. The electrochemical behavior of 0.5 M Co(II) chloride solution at 70 °C was studied by means of cyclic voltammetry (CV) on a Pt substrate. The reduction process was shown to be irreversible, with high faradaic efficiencies (85–90 %). A diffusion coefficient (D0) of 2.29 × 10−6 cm2 s−1 for the Co species was estimated from the electrochemical behavior at different scan rates (from 25 to 125 mV s−1). The electrodeposition process was also studied on a copper substrate at different cathodic potentials (from −0.75 V vs Pt to −0.95 V vs Pt). Field-emission scanning electron microscopy (FE-SEM) and electron dispersive spectroscopy (EDS) revealed high-purity, compact films. Template-assisted electrodeposition resulted in ~16–18 μm long cobalt nanowires with an aspect ratio L/D > 100. X-ray diffraction (XRD) analysis of Co thin films showed a preferential orientation along the HCP [100] direction, which was even more marked for the nanowires. Vibrating sample magnetometry (VSM) highlighted that the fact that Co thin films were magnetized in-plane, while in nanowires a competition between shape and magnetocrystalline anisotropy led to similar magnetic behavior for the in-plane and out-of-plane directions. Keywords: Organic solvent, Magnetization, Non-aqueous, Electroplating, Alumina template

Targeted drug delivery is currently emerging as a promising approach to overcome the limits of currently employed administration techniques. The most convenient methodology to control drug delivery is the application of stimuli-responsive materials, which can release drugs only when required, to remotely controlled microdevices able to navigate human body. Thanks to this synergy, release can be controlled both spatially and temporally. Spatial control is guaranteed by the maneuverability of the devices, which can be precisely guided to release in targeted locations. Temporal control, conversely, is guaranteed by the functionalization introduced in the stimuli-responsive material. In this context, the present work describes the coating of magnetically controlled microdevices with functionalized alginate-based hydrogels able to release drugs at pH values lower than 4.5. Hydrogels are functionalized binding the drug with either an azidoethyl ester bond or an amidic bond, following an innovative synthesis route. After fabrication, release from hydrogel coated microdevices as a function of the environmental pH is characterized. Finally, devices are magnetically actuated and the possibility to achieve spatially and temporally controlled release is demonstrated. The functional microtransporters described in the present work are particularly promising for in-vivo applications in environments where pH differences are present, like the digestive apparatus.

Flexible and economic sensor devices are the focus of increasing interest for their potential and wide applications in medicine, food analysis, pollution, water quality, etc. In these areas, the possibility of using stable, reproducible, and pocket devices can simplify the acquisition of data. Among recent prototypes, sensors based on laser-induced graphene (LIGE) on Kapton represent a feasible choice. In particular, LIGE devices are also exploited as electrodes for sensing in liquids. Despite a characterization with electrochemical (EC) methods in the literature, a closer comparison with traditional graphite electrodes is still missing. In this study, we combine atomic force microscopy with an EC cell (EC-AFM) to study, in situ, electrode oxidation reactions when LIGE or other graphite samples are used as anodes inside an acid electrolyte. This investigation shows the quality and performance of the LIGE electrode with respect to other samples. Finally, an ex situ Raman spectroscopy analysis allows a detailed chemical analysis of the employed electrodes.

A chloride-free solution based on ethylene glycol was shown to be suitable for the electrodeposition of copper onto zinc, allowing the fabrication of a Mo/Zn/Cu/Sn metallic precursor stack. The addition of diethanolamine (DEA) played an essential role in minimizing displacement reactions by shifting copper reduction towards a more negative potential. The electrochemical behavior of copper species with and without DEA was studied by cyclic voltammetry, and subsequently confirmed by displacement reaction assessment (OCV and ICP-OES measurements). The metallic stack was characterized by SEM and AFM, showing the effectiveness of the copper plating solution. Reactive annealing was carried out in a tubular furnace to obtain the CZTS kesterite semiconductor, as confirmed by XRD and Raman spectroscopy. Keywords: Organic solution, Ethylene glycol, Diethanolamine, Chloride-free, CZTS

In this work the design, fabrication and testing of the first 3D-printed and wet metallized capacitive z-axis accelerometer with a volume of 3.4 cm × 8 mm × 2.5 mm is presented. Preliminary results well match the modelling, both in terms of electromechanical parameters and of measured sensitivity, thus validating the proposed concept and fabrication process. With a spring thickness of 300 µm and a gap size of 200 µm for capacitive read-out, the presented device and the shown results can be considered as the first step toward 3D-printed MEMS (Micro-Electro-Mechanical Systems) inertial sensors.

A single-use disposable in vitro electrochemical immunosensor for the detection of HbA1c in undiluted human serum using differential pulse voltammetry (DPV) was developed. A three-electrode configuration electrochemical biosensor consisted of 10-nm-thin gold film working and counter electrodes and a thick-film printed Ag/AgCl reference electrode was fabricated on a polyethylene terephthalate (PET) substrate. Micro-fabrication techniques including sputtering vapor deposition and thick-film printing were used to fabricate the biosensor. This was a roll-to-roll cost-effective manufacturing process making the single-use disposable in vitro HbA1c biosensor a reality. Self-assembled monolayers of 3-Mercaptopropionic acid (MPA) were employed to covalently immobilize anti-HbA1c on the surface of gold electrodes. Electrochemical impedance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS) confirmed the excellent coverage of MPA-SAM and the upward orientation of carboxylic groups. The hindering effect of HbA1c on the ferricyanide/ferrocyanide electron transfer reaction was exploited as the HbA1c detection mechanism. The biosensor showed a linear range of 7.5–20 µg/mL of HbA1c in 0.1 M PBS. Using undiluted human serum as the test medium, the biosensor presented an excellent linear behavior (R2 = 0.999) in the range of 0.1–0.25 mg/mL of HbA1c. The potential application of this biosensor for in vitro measurement of HbA1c for diabetic management was demonstrated.