Andrea Macrelli

Owing to the huge theoretical specific capacity, nanostructured silicon is a promising anode material for all‐solid‐state lithium‐ion batteries. However, the massive volume expansion associated with the formation of Li‐rich alloys results in severe degradation and rapid failure. This study explores pulsed laser deposition (PLD) as a versatile technique for synthesizing nanostructured porous silicon thin films with tailored morphology and nanocrystallinity, intended for electrochemical testing in cells with Li ₆ PS ₅ Cl solid electrolyte. By systematically varying the deposition parameters, such as laser fluence, gas composition and pressure, substrate, and time, the transition from compact‐amorphous to nanoporous‐nanocrystalline silicon is achieved. Electrochemical testing reveals a strong correlation between nanoporosity and performance: the nanoporous film grown at 100 Pa of Ar + H ₂ delivers a first‐lithiation capacity of 3388 mAh g ⁻¹ (94.7% of theoretical capacity), with stable cycling over 30 cycles, outperforming denser films. Post‐mortem microscopy, Raman, and X‐ray photoelectron spectroscopy analyses clarify lithiation‐induced phase transitions and degradation pathways. Despite some still open challenges (such as low mass loading and poor initial Coulombic efficiency), this work demonstrates, for the first time, the rational application of PLD for silicon electrodes in solid‐state lithium‐ion cells, paving the way for further optimization and full‐cell integration.

In pulsed laser deposition, along the traditionally exploited deposition on the front‐side of the plasma‐plume, a coating forms on the surface of the target as well. For reproducibility, this residue is usually cleaned and discarded. Here we instead investigate the target‐side coated materials and employ them as a binder‐free supercapacitor electrode. The ballistic‐aggregated, target‐side nanofoam is compact and features a larger fraction of sp²‐carbon, higher nitrogen content with higher graphitic‐N and lower oxygen content with fewer COOH groups than that of diffusive‐aggregated conventional nanofoams. They are highly hydrogenated graphite‐like amorphous carbon and superhydrophilic. The resulting symmetric micro‐supercapacitor delivers higher volumetric capacitance of 522 mF/cm³ at 100 mV/s and 104 % retention after 10000 charge‐discharge cycles over conventional nanofoam (215 mF/cm³ and 85 % retention) with an areal capacitance of 134 μF/cm² at 120 Hz and ultrafast frequency response. Utilizing the normally discarded target‐side material can therefore enable high performing devices while reducing waste, cost and energy input per usable product, leading towards a greater sustainability of nanomaterials synthesis and deposition techniques.

Among post-lithium ion battery technologies, rechargeable chemistries with Zn anodes bear notable technological promise owing to their high theoretical energy density, lower manufacturing cost, availability of raw materials and inherent safety. However, Zn anodes, when employed in aqueous electrolytes, suffer from hydrogen evolution, passivation, and shape changes. Alternative electrolytes can help tackle these issues, preserving the green and safe characteristics of aqueous-based ones. Deep eutectic solvents (DESs) are promising green and low-cost non-aqueous solvents for battery electrolytes. Specifically, the cycling of Zn anodes in DESs is expected to be reversible, chiefly owing to their dendrite-suppression capability. Nevertheless, apart from a few studies on Zn plating, insight into the cathodic–anodic electrochemistry of Zn in DESs is still very limited. In view of developing DES-based battery electrolytes, it is crucial to consider that a potential drawback might be their low ionic conductivity. Water molecules can be added to the eutectic mixtures by up to 40% to increase the diffusion coefficient of the electroactive species and lower the electrolyte viscosity without destroying the eutectic nature. In this study, we address the electrochemistry of Zn in two different hydrated DESs (ChU and ChEG with ~30% H₂O). Fundamental electrokinetic and electrocrystallization studies based on cyclic voltammetry and chronoamperometry at different cathodic substrates are completed with a galvanostatic cycling test of Zn|Zn symmetric CR2032 coin cells, SEM imaging of electrodes and in situ SERS spectroscopy. This investigation concludes with the proposal of a specific DES/H₂O/ZnSO₄-based electrolyte that exhibits optimal functional performance, rationalized on the basis of fundamental electrochemical data, morphology evaluation and modeling of the cycling response.

As renewable energy is becoming a crucial energy source to meet the global demand, electrochemical energy storage devices become indispensable for efficient energy storage and reliable supply. The electrode material is the key factor determining the energy storage capacity and the power delivery of the devices. Carbon-based materials, specifically graphite, activated carbons etc, are extensively used as electrodes, yet their low energy densities impede the development of advanced energy storage materials. Decoration by nanoparticles of metals, metal oxides, nitrides, carbides, phosphides, chalcogenides and bimetallic components is one of the most promising and easy-to-implement strategies to significantly enhance the structural and electronic properties, pore refinement, charge storage and charge-transfer kinetics of both pristine and doped carbon structures, thereby making their performance promising for next-generation energy storage devices. Structuring the materials at nanoscale is another probable route for better rate performance and charge-transfer kinetics. This review covers the state-of-art nanoparticle decorated nanocarbons (NCs) as materials for battery anode, metal-ion capacitor anode and supercapacitor electrode. A critical analysis of the elemental composition, structure, associated physico-chemical properties and performance relationships of nanoparticle-decorated NC electrodes is provided as well to inform the future development of the next-generation advanced energy storage materials and devices.

The applications of SERS in therapeutic drug monitoring, or other fields of analytical chemistry, require the availability of sensitive sensors and experimental approaches that can be implemented in affordable ways. In this contribution, we show the production of cost-effective SERS sensors obtained by depositing Lee-Meisel Ag colloids on filter paper either by natural sedimentation or centrifugation. We have characterized the morphological and plasmonic features of the sensors by optical microscopy, SEM, and UV-Vis spectroscopy. Such sensors can be used to quantify by SERS the anti-epileptic drug Perampanel (in the concentration range 1 × 10⁻⁴–5 × 10⁻⁶ M) by spinning them during the micro-Raman measurements on the top of a custom device obtained from spare part hard disk drives. This approach minimizes laser-induced heating effects and allows averaging over the spatial non-uniformity of the sensor.