Dynamic Manipulation of Droplets on Liquid-Infused Surfaces Using Photoresponsive Surfactant.

Fast and programmable transport of droplets on a substrate is desirable in microfluidic, thermal, biomedical, and energy devices. Photoresponsive surfactants are promising candidates to manipulate droplet motion due to their ability to modify interfacial tension and generate "photo-Marangoni" flow under light stimuli. Previous works have demonstrated photo-Marangoni droplet migration in liquid media; however, migration on other substrates, including solid and liquid-infused surfaces (LIS), remains an outstanding challenge. Moreover, models of photo-Marangoni migration are still needed to identify optimal photoswitches and assess the feasibility of new applications. In this work, we demonstrate 2D droplet motion on liquid surfaces and on LIS, as well as rectilinear motion in solid capillary tubes. We synthesize photoswitches based on spiropyran and merocyanine, capable of tension changes of up to 5.5 mN/m across time scales as short as 1.7 s. A millimeter-sized droplet migrates at up to 5.5 mm/s on a liquid, and 0.25 mm/s on LIS. We observe an optimal droplet size for fast migration, which we explain by developing a scaling model. The model also predicts that faster migration is enabled by surfactants that maximize the ratio between the tension change and the photoswitching time. To better understand migration on LIS, we visualize the droplet flow using tracer particles, and we develop corresponding numerical simulations, finding reasonable agreement. The methods and insights demonstrated in this study enable advances for manipulation of droplets for microfluidic, thermal and water harvesting devices.

Depinning of Multiphase Fluid Using Light and Photo-Responsive Surfactants.

The development of noninvasive and robust strategies for manipulation of droplets and bubbles is crucial in applications such as boiling and condensation, electrocatalysis, and microfluidics. In this work, we realize the swift departure of droplets and bubbles from solid substrates by introducing photoresponsive surfactants and applying asymmetric illumination, thereby inducing a "photo-Marangoni" lift force. Experiments show that a pinned toluene droplet can depart the substrate in only 0.38 s upon illumination, and the volume of an air bubble at departure is reduced by 20%, indicating significantly faster departure. These benefits can be achieved with moderate light intensities and dilute surfactant concentrations, without specially fabricated substrates, which greatly facilitates practical applications. Simulations suggest that the net departure force includes contributions from viscous stresses directly caused by the Marangoni flow, as well as from pressure buildup due to flow stagnation at the contact line. The manipulation scheme proposed here shows potential for applications requiring droplet and bubble removal from working surfaces.

Dynamic spatial progression of isolated lithium during battery operations.

The increasing demand for next-generation energy storage systems necessitates the development of high-performance lithium batteries1-3. Unfortunately, current Li anodes exhibit rapid capacity decay and a short cycle life4-6, owing to the continuous generation of solid electrolyte interface7,8 and isolated Li (i-Li)9-11. The formation of i-Li during the nonuniform dissolution of Li dendrites12 leads to a substantial capacity loss in lithium batteries under most testing conditions13. Because i-Li loses electrical connection with the current collector, it has been considered electrochemically inactive or 'dead' in batteries14,15. Contradicting this commonly accepted presumption, here we show that i-Li is highly responsive to battery operations, owing to its dynamic polarization to the electric field in the electrolyte. Simultaneous Li deposition and dissolution occurs on two ends of the i-Li, leading to its spatial progression toward the cathode (anode) during charge (discharge). Revealed by our simulation results, the progression rate of i-Li is mainly affected by its length, orientation and the applied current density. Moreover, we successfully demonstrate the recovery of i-Li in Cu-Li cells with >100% Coulombic efficiency and realize LiNi0.5Mn0.3Co0.2O2 (NMC)-Li full cells with extended cycle life.

Integrated cooling (i-Cool) textile of heat conduction and sweat transportation for personal perspiration management.

Perspiration evaporation plays an indispensable role in human body heat dissipation. However, conventional textiles tend to focus on sweat removal and pay little attention to the basic thermoregulation function of sweat, showing limited evaporation ability and cooling efficiency in moderate/profuse perspiration scenarios. Here, we propose an integrated cooling (i-Cool) textile with unique functional structure design for personal perspiration management. By integrating heat conductive pathways and water transport channels decently, i-Cool exhibits enhanced evaporation ability and high sweat evaporative cooling efficiency, not merely liquid sweat wicking function. In the steady-state evaporation test, compared to cotton, up to over 100% reduction in water mass gain ratio, and 3 times higher skin power density increment for every unit of sweat evaporation are demonstrated. Besides, i-Cool shows about 3 °C cooling effect with greatly reduced sweat consumption than cotton in the artificial sweating skin test. The practical application feasibility of i-Cool design principles is well validated based on commercial fabrics. Owing to its exceptional personal perspiration management performance, we expect the i-Cool concept can provide promising design guidelines for next-generation perspiration management textiles.

Correlating Li-Ion Solvation Structures and Electrode Potential Temperature Coefficients.

Temperature coefficients (TCs) for either electrochemical cell voltages or potentials of individual electrodes have been widely utilized to study the thermal safety and cathode/anode phase changes of lithium (Li)-ion batteries. However, the fundamental significance of single electrode potential TCs is little known. In this work, we discover that the Li-ion desolvation process during Li deposition/intercalation is accompanied by considerable entropy change, which significantly contributes to the measured Li/Li+ electrode potential TCs. To explore this phenomenon, we compare the Li/Li+ electrode potential TCs in a series of electrolyte formulations, where the interaction between Li-ion and solvent molecules occurs at varying strength as a function of both solvent and anion species as well as salt concentrations. As a result, we establish correlations between electrode potential TCs and Li-ion solvation structures and further verify them by ab initio molecular dynamics simulations. We show that measurements of Li/Li+ electrode potential TCs provide valuable knowledge regarding the Li-ion solvation environments and could serve as a screening tool when designing future electrolytes for Li-ion/Li metal batteries.

Designing a Nanoscale Three-phase Electrochemical Pathway to Promote Pt-catalyzed Formaldehyde Oxidation.

Gas-phase heterogeneous catalysis is a process spatially constrained on the two-dimensional surface of a solid catalyst. Here, we introduce a new toolkit to open up the third dimension. We discovered that the activity of a solid catalyst can be dramatically promoted by covering its surface with a nanoscale-thin layer of liquid electrolyte while maintaining efficient delivery of gas reactants, a strategy we call three-phase catalysis. Introducing the liquid electrolyte converts the original surface catalytic reaction into an electrochemical pathway with mass transfer facilitated by free ions in a three-dimensional space. We chose the oxidation of formaldehyde as a model reaction and observed a 25000-times enhancement in the turnover frequency of Pt in three-phase catalysis as compared to conventional heterogeneous catalysis. We envision three-phase catalysis as a new dimension for catalyst design and anticipate its applications in more chemical reactions from pollution control to the petrochemical industry.

Underpotential lithium plating on graphite anodes caused by temperature heterogeneity.

Rechargeability and operational safety of commercial lithium (Li)-ion batteries demand further improvement. Plating of metallic Li on graphite anodes is a critical reason for Li-ion battery capacity decay and short circuit. It is generally believed that Li plating is caused by the slow kinetics of graphite intercalation, but in this paper, we demonstrate that thermodynamics also serves a crucial role. We show that a nonuniform temperature distribution within the battery can make local plating of Li above 0 V vs. Li0/Li+ (room temperature) thermodynamically favorable. This phenomenon is caused by temperature-dependent shifts of the equilibrium potential of Li0/Li+ Supported by simulation results, we confirm the likelihood of this failure mechanism during commercial Li-ion battery operation, including both slow and fast charging conditions. This work furthers the understanding of nonuniform Li plating and will inspire future studies to prolong the cycling lifetime of Li-ion batteries.

COVID-19: Effects of Environmental Conditions on the Propagation of Respiratory Droplets.

As coronavirus disease 2019 (COVID-19) continues to spread, a detailed understanding on the transmission mechanisms is of paramount importance. The disease transmits mainly through respiratory droplets and aerosol. Although models for the evaporation and trajectory of respiratory droplets have been developed, how the environment impacts the transmission of COVID-19 is still unclear. In this study, we investigate the propagation of respiratory droplets and aerosol particles generated by speech under a wide range of temperatures (0-40 °C) and relative humidity (0-92%) conditions. We show that droplets can travel three times farther in low-temperature and high-humidity environment, whereas the number of aerosol particles increases in high-temperature and low-humidity environments. The results also underscore the importance of proper ventilation, as droplets and aerosol spread significantly farther in airstreams. This study contributes to the understanding of the environmental impact on COVID-19 transmission.

Electrotunable liquid sulfur microdroplets.

Manipulating liquids with tunable shape and optical functionalities in real time is important for electroactive flow devices and optoelectronic devices, but remains a great challenge. Here, we demonstrate electrotunable liquid sulfur microdroplets in an electrochemical cell. We observe electrowetting and merging of sulfur droplets under different potentiostatic conditions, and successfully control these processes via selective design of sulfiphilic/sulfiphobic substrates. Moreover, we employ the electrowetting phenomena to create a microlens based on the liquid sulfur microdroplets and tune its characteristics in real time through changing the shape of the liquid microdroplets in a fast, repeatable, and controlled manner. These studies demonstrate a powerful in situ optical battery platform for unraveling the complex reaction mechanism of sulfur chemistries and for exploring the rich material properties of the liquid sulfur, which shed light on the applications of liquid sulfur droplets in devices such as microlenses, and potentially other electrotunable and optoelectronic devices.

Fast lithium growth and short circuit induced by localized-temperature hotspots in lithium batteries.

Fast-charging and high-energy-density batteries pose significant safety concerns due to high rates of heat generation. Understanding how localized high temperatures affect the battery is critical but remains challenging, mainly due to the difficulty of probing battery internal temperature with high spatial resolution. Here we introduce a method to induce and sense localized high temperature inside a lithium battery using micro-Raman spectroscopy. We discover that temperature hotspots can induce significant lithium metal growth as compared to the surrounding lower temperature area due to the locally enhanced surface exchange current density. More importantly, localized high temperature can be one of the factors to cause battery internal shorting, which further elevates the temperature and increases the risk of thermal runaway. This work provides important insights on the effects of heterogeneous temperatures within batteries and aids the development of safer batteries, thermal management schemes, and diagnostic tools.

Wrinkled Graphene Cages as Hosts for High-Capacity Li Metal Anodes Shown by Cryogenic Electron Microscopy.

Lithium (Li) metal has long been considered the "holy grail" of battery anode chemistry but is plagued by low efficiency and poor safety due to its high chemical reactivity and large volume fluctuation, respectively. Here we introduce a new host of wrinkled graphene cage (WGC) for Li metal. Different from recently reported amorphous carbon spheres, WGC show highly improved mechanical stability, better Li ion conductivity, and excellent solid electrolyte interphase (SEI) for continuous robust Li metal protection. At low areal capacities, Li metal is preferentially deposited inside the graphene cage. Cryogenic electron microscopy characterization shows that a uniform and stable SEI forms on the WGC surface that can shield the Li metal from direct exposure to electrolyte. With increased areal capacities, Li metal is plated densely and homogeneously into the outer pore spaces between graphene cages with no dendrite growth or volume change. As a result, a high Coulombic efficiency (CE) of ∼98.0% was achieved under 0.5 mA/cm2 and 1-10 mAh/cm2 in commercial carbonate electrolytes, and a CE of 99.1% was realized with high-concentration electrolytes under 0.5 mA/cm2 and 3 mAh/cm2. Full cells using WGC electrodes with prestored Li paired with Li iron phosphate showed greatly improved cycle lifetime. With 10 mAh/cm2 Li metal deposition, the WGC/Li composite anode was able to provide a high specific capacity of ∼2785 mAh/g. With its roll-to-roll compatible fabrication procedure, WGC serves as a highly promising material for the practical realization of Li metal anodes in next-generation high energy density secondary batteries.

In Situ Investigation on the Nanoscale Capture and Evolution of Aerosols on Nanofibers.

Aerosol-induced haze problem has become a serious environmental concern. Filtration is widely applied to remove aerosols from gas streams. Despite classical filtration theories, the nanoscale capture and evolution of aerosols is not yet clearly understood. Here we report an in situ investigation on the nanoscale capture and evolution of aerosols on polyimide nanofibers. We discovered different capture and evolution behaviors among three types of aerosols: wetting liquid droplets, nonwetting liquid droplets, and solid particles. The wetting droplets had small contact angles and could move, coalesce, and form axisymmetric conformations on polyimide nanofibers. In contrast, the nonwetting droplets had a large contact angle on polyimide nanofibers and formed nonaxisymmetric conformations. Different from the liquid droplets, the solid particles could not move along the nanofibers and formed dendritic structures. This study provides an important insight for obtaining a deep understanding of the nanoscale capture and evolution of aerosols and benefits future design and development of advanced filters.

Coexistence of Pinning and Moving on a Contact Line.

Textured surfaces are instrumental in water repellency or fluid wicking applications, where the pinning and depinning of the liquid-gas interface plays an important role. Previous work showed that a contact line can exhibit nonuniform behavior due to heterogeneities in surface chemistry or roughness. We demonstrate that such nonuniformities can be achieved even without varying the local energy barrier. Around a cylindrical pillar, an interface can reside in an intermediate state where segments of the contact line are pinned to the pillar top while the rest of the contact line moves along the sidewall. This partially pinned mode is due to the global nonaxisymmetric pattern of the surface features and exists for all textured surfaces, especially when superhydrophobic surfaces are about to be flooded or when capillary wicks are close to dryout.

Prediction and Characterization of Dry-out Heat Flux in Micropillar Wick Structures.

Thin-film evaporation in wick structures for cooling high-performance electronic devices is attractive because it harnesses the latent heat of vaporization and does not require external pumping. However, optimizing the wick structures to increase the dry-out heat flux is challenging due to the complexities in modeling the liquid-vapor interface and the flow through the wick structures. In this work, we developed a model for thin-film evaporation from micropillar array wick structures and validated the model with experiments. The model numerically simulates liquid velocity, pressure, and meniscus curvature along the wicking direction by conservation of mass, momentum, and energy based on a finite volume approach. Specifically, the three-dimensional meniscus shape, which varies along the wicking direction with the local liquid pressure, is accurately captured by a force balance using the Young-Laplace equation. The dry-out condition is determined when the minimum contact angle on the pillar surface reaches the receding contact angle as the applied heat flux increases. With this model, we predict the dry-out heat flux on various micropillar structure geometries (diameter, pitch, and height) in the length scale range of 1-100 µm and discuss the optimal geometries to maximize the dry-out heat flux. We also performed detailed experiments to validate the model predictions, which show good agreement. This work provides insights into the role of surface structures in thin-film evaporation and offers important design guidelines for enhanced thermal management of high-performance electronic devices.

Dynamic Evolution of the Evaporating Liquid-Vapor Interface in Micropillar Arrays.

Capillary assisted passively pumped thermal management devices have gained importance due to their simple design and reduction in energy consumption. The performance of these devices is strongly dependent on the shape of the curved interface between the liquid and vapor phases. We developed a transient laser interferometry technique to investigate the evolution of the shape of the liquid-vapor interface in micropillar arrays during evaporation heat transfer. Controlled cylindrical micropillar arrays were fabricated on the front side of a silicon wafer, while thin-film heaters were deposited on the reverse side to emulate a heat source. The shape of the meniscus was determined using the fringe patterns resulting from interference of a monochromatic beam incident on the thin liquid layer. We studied the evolution of the shape of the meniscus on these surfaces under various operating conditions including varying the micropillar geometry and the applied heating power. By monitoring the transient behavior of the evaporating liquid-vapor interface, we accurately measured the absolute location and shape of the meniscus and calculated the contact angle and the maximum capillary pressure. We demonstrated that the receding contact angle which determines the capillary pumping limit is independent of the microstructure geometry and the rate of evaporation (i.e., the applied heating power). The results of this study provide fundamental insights into the dynamic behavior of the liquid-vapor interface in wick structures during phase-change heat transfer.

Real-time manipulation with magnetically tunable structures.

Magnetically tunable micropillar arrays with uniform, continuous and extreme tilt angles for real-time manipulation are reported. We experimentally show uniform tilt angles ranging from 0° to 57°, and develop a model to accurately capture the behavior. Furthermore, we demonstrate that the flexible uniform responsive microstructures (µFUR) can dynamically manipulate liquid spreading directionality, control fluid drag, and tune optical transmittance over a large range.

Unified model for contact angle hysteresis on heterogeneous and superhydrophobic surfaces.

Understanding the complexities associated with contact line dynamics on chemically heterogeneous and superhydrophobic surfaces is important for a wide variety of engineering problems. Despite significant efforts to capture the behavior of a droplet on these surfaces over the past few decades, modeling of the complex dynamics at the three-phase contact line is needed. In this work, we demonstrate that contact line distortion on heterogeneous and superhydrophobic surfaces is the key aspect that needs to be accounted for in the dynamic droplet models. Contact line distortions were visualized and modeled using a thermodynamic approach to develop a unified model for contact angle hysteresis on chemically heterogeneous and superhydrophobic surfaces. On a surface comprised of discrete wetting defects on an interconnected less wetting area, the advancing contact angle was determined to be independent of the defects, while the relative fraction of the distorted contact line with respect to the baseline surface was shown to govern the receding contact angle. This behavior reversed when the relative wettability of the discrete defects and interconnected area was inverted. The developed model showed good agreement with the experimental advancing and receding contact angles, both at low and high solid fractions. The thermodynamic model was further extended to demonstrate its capability to capture droplet shape evolution during liquid addition and removal in our experiments and those in literature. This study offers new insight extending the fundamental understanding of solid-liquid interactions required for design of advanced functional coatings for microfluidics, biological, manufacturing, and heat transfer applications.