Designing Mesoporous Photonic Structures for High-Performance Passive Daytime Radiative Cooling.

Passive daytime radiative cooling (PDRC) has drawn significant attention recently for electricity-free cooling. Porous polymers are attractive for PDRC since they have excellent performance and scalability. A fundamental question remaining is how PDRC performance depends on pore properties (e.g., radius, porosity), which is critical to guiding future structure designs. In this work, optical simulations are carried out to answer this question, and effects of pore size, porosity, and thickness are studied. We find that mixed nanopores (e.g., radii of 100 and 200 nm) have a much higher solar reflectance R̅solar (0.951) than the single-sized pores (0.811) at a thickness of 300 µm. With an Al substrate underneath, R̅solar, thermal emittance ε̅LWIR, and net cooling power Pcool reach 0.980, 0.984, and 72 W/m2, respectively, under a semihumid atmospheric condition. These simulation results provide a guide for designing high-performance porous coating for PDRC applications.

A Flexible Solid Composite Electrolyte with Vertically Aligned and Connected Ion-Conducting Nanoparticles for Lithium Batteries.

Replacing flammable organic liquid electrolytes with solid Li-ion conductors is a promising approach to realize safe rechargeable batteries with high energy density. Composite solid electrolytes, which are comprised of a polymer matrix with ceramic Li-ion conductors dispersed inside, are attractive, since they combine the flexibility of polymer electrolytes and high ionic conductivities of ceramic electrolytes. However, the high conductivity of ceramic fillers is largely compromised by the low conductivity of the matrix, especially when nanoparticles (NPs) are used. Therefore, optimizations of the geometry of ceramic fillers are critical to further enhance the conductivity of composite electrolytes. Here we report the vertically aligned and connected Li1+xAlxTi2-x(PO4)3 (LATP) NPs in the poly(ethylene oxide) (PEO) matrix to maximize the ionic conduction, while maintaining the flexibility of the composite. This vertically aligned structure can be fabricated by an ice-templating-based method, and its conductivity reaches 0.52 × 10-4 S/cm, which is 3.6 times that of the composite electrolyte with randomly dispersed LATP NPs. The composite electrolyte also shows enhanced thermal and electrochemical stability compared to the pure PEO electrolyte. This method opens a new approach to optimize ion conduction in composite solid electrolytes for next-generation rechargeable batteries.

Ambient-Air Stable Lithiated Anode for Rechargeable Li-Ion Batteries with High Energy Density.

An important requirement of battery anodes is the processing step involving the formation of the solid electrolyte interphase (SEI) in the initial cycle, which consumes a significant portion of active lithium ions. This step is more critical in nanostructured anodes with high specific capacity, such as Si and Sn, due to their high surface area and large volume change. Prelithiation presents a viable approach to address such loss. However, the stability of prelithiation reagents is a big issue due to their low potential and high chemical reactivity toward O2 and moisture. Very limited amount of prelithiation agents survive in ambient air. In this research, we describe the development of a trilayer structure of active material/polymer/lithium anode, which is stable in ambient air (10-30% relative humidity) for a period that is sufficient to manufacture anode materials. The polymer layer protects lithium against O2 and moisture, and it is stable in coating active materials. The polymer layer is gradually dissolved in the battery electrolyte, and active materials contact with lithium to form lithiated anode. This trilayer-structure not only renders electrodes stable in ambient air but also leads to uniform lithiation. Moreover, the degree of prelithiation could vary from compensating SEI to fully lithiated anode. With this strategy, we have achieved high initial Coulombic efficiency of 99.7% in graphite anodes, and over 100% in silicon nanoparticles anodes. The cycling performance of lithiated anodes is comparable or better than those not lithiated. We also demonstrate a Li4Ti5O12/lithiated graphite cell with stable cycling performance. The trilayer structure represents a new prelithiation method to enhance performance of Li-ion batteries.

Broadband directional control of thermal emission.

Controlling the directionality of emitted far-field thermal radiation is a fundamental challenge. Photonic strategies enable angular selectivity of thermal emission over narrow bandwidths, but thermal radiation is a broadband phenomenon. The ability to constrain emitted thermal radiation to fixed narrow angular ranges over broad bandwidths is an important, but lacking, capability. We introduce gradient epsilon-near-zero (ENZ) materials that enable broad-spectrum directional control of thermal emission. We demonstrate two emitters consisting of multiple oxides that exhibit high (>0.7, >0.6) directional emissivity (60° to 75°, 70° to 85°) in the p-polarization for a range of wavelengths (10.0 to 14.3 micrometers, 7.7 to 11.5 micrometers). This broadband directional emission enables meaningful radiative heat transfer primarily in the high emissivity directions. Decoupling the conventional limitations on angular and spectral response improves performance for applications such as thermal camouflaging, solar heating, radiative cooling, and waste heat recovery.

Colored and paintable bilayer coatings with high solar-infrared reflectance for efficient cooling.

Solar reflective and thermally emissive surfaces offer a sustainable way to cool objects under sunlight. However, white or silvery reflectance of these surfaces does not satisfy the need for color. Here, we present a paintable bilayer coating that simultaneously achieves color and radiative cooling. The bilayer comprises a thin, visible-absorptive layer atop a nonabsorptive, solar-scattering underlayer. The top layer absorbs appropriate visible wavelengths to show specific colors, while the underlayer maximizes the reflection of near-to-short wavelength infrared (NSWIR) light to reduce solar heating. Consequently, the bilayer attains higher NSWIR reflectance (by 0.1 to 0.51) compared with commercial paint monolayers of the same color and stays cooler by as much as 3.0° to 15.6°C under strong sunlight. High NSWIR reflectance of 0.89 is realized in the blue bilayer. The performances show that the bilayer paint design can achieve both color and efficient radiative cooling in a simple, inexpensive, and scalable manner.

Hierarchically porous polymer coatings for highly efficient passive daytime radiative cooling.

Passive daytime radiative cooling (PDRC) involves spontaneously cooling a surface by reflecting sunlight and radiating heat to the cold outer space. Current PDRC designs are promising alternatives to electrical cooling but are either inefficient or have limited applicability. We present a simple, inexpensive, and scalable phase inversion-based method for fabricating hierarchically porous poly(vinylidene fluoride-co-hexafluoropropene) [P(VdF-HFP)HP] coatings with excellent PDRC capability. High, substrate-independent hemispherical solar reflectances (0.96 ± 0.03) and long-wave infrared emittances (0.97 ± 0.02) allow for subambient temperature drops of ~6°C and cooling powers of ~96 watts per square meter (W m-2) under solar intensities of 890 and 750 W m-2, respectively. The performance equals or surpasses those of state-of-the-art PDRC designs, and the technique offers a paint-like simplicity.

Nanostructured fibers as a versatile photonic platform: radiative cooling and waveguiding through transverse Anderson localization.

Broadband high reflectance in nature is often the result of randomly, three-dimensionally structured materials. This study explores unique optical properties associated with one-dimensional nanostructures discovered in silk cocoon fibers of the comet moth, Argema mittrei. The fibers are populated with a high density of air voids randomly distributed across the fiber cross-section but are invariant along the fiber. These filamentary air voids strongly scatter light in the solar spectrum. A single silk fiber measuring ~50 µm thick can reflect 66% of incoming solar radiation, and this, together with the fibers' high emissivity of 0.88 in the mid-infrared range, allows the cocoon to act as an efficient radiative-cooling device. Drawing inspiration from these natural radiative-cooling fibers, biomimetic nanostructured fibers based on both regenerated silk fibroin and polyvinylidene difluoride are fabricated through wet spinning. Optical characterization shows that these fibers exhibit exceptional optical properties for radiative-cooling applications: nanostructured regenerated silk fibers provide a solar reflectivity of 0.73 and a thermal emissivity of 0.90, and nanostructured polyvinylidene difluoride fibers provide a solar reflectivity of 0.93 and a thermal emissivity of 0.91. The filamentary air voids lead to highly directional scattering, giving the fibers a highly reflective sheen, but more interestingly, they enable guided optical modes to propagate along the fibers through transverse Anderson localization. This discovery opens up the possibility of using wild silkmoth fibers as a biocompatible and bioresorbable material for optical signal and image transport.

Scalable, "Dip-and-Dry" Fabrication of a Wide-Angle Plasmonic Selective Absorber for High-Efficiency Solar-Thermal Energy Conversion.

A galvanic-displacement-reaction-based, room-temperature "dip-and-dry" technique is demonstrated for fabricating selectively solar-absorbing plasmonic-nanoparticle-coated foils (PNFs). The technique, which allows for facile tuning of the PNFs' spectral reflectance to suit different radiative and thermal environments, yields PNFs which exhibit excellent, wide-angle solar absorptance (0.96 at 15°, to 0.97 at 35°, to 0.79 at 80°), and low hemispherical thermal emittance (0.10) without the aid of antireflection coatings. The thermal emittance is on par with those of notable selective solar absorbers (SSAs) in the literature, while the wide-angle solar absorptance surpasses those of previously reported SSAs with comparable optical selectivities. In addition, the PNFs show promising mechanical and thermal stabilities at temperatures of up to 200 °C. Along with the performance of the PNFs, the simplicity, inexpensiveness, and environmental friendliness of the "dip-and-dry" technique makes it an appealing alternative to current methods for fabricating selective solar absorbers.

Using Voronoi tessellations to assess nanoparticle-nanoparticle interactions and ordering in monolayer films formed through electrophoretic deposition.

Monolayers of iron oxide nanoparticles of two different sizes, 9.6 nm and 16.5 nm, were fabricated through electrophoretic deposition. The arrangements of nanoparticles within the films were analyzed using the technique of Voronoi tessellations. These analyses indicated that the films possessed equivalent degrees of ordering, and that the films were uniform over centimeter length scales. Precise measurements of the interparticle spacing were obtained, and the magnitudes of magnetic dipole interactions were calculated. The dipole-dipole interaction among the larger nanoparticles was 14 times larger than that of the smaller nanoparticles, indicating that magnetic coupling interactions could not have been the lone source of ordering in the system.