Self-oscillating polymeric refrigerator with high energy efficiency.

Electrocaloric1,2 and electrostrictive3,4 effects concurrently exist in dielectric materials. Combining these two effects could achieve the lightweight, compact localized thermal management that is promised by electrocaloric refrigeration5. Despite a handful of numerical models and schematic presentations6,7, current electrocaloric refrigerators still rely on external accessories to drive the working bodies8-10 and hence result in a low device-level cooling power density and coefficient of performance (COP). Here we report an electrocaloric thin-film device that uses the electro-thermomechanical synergy provided by polymeric ferroelectrics. Under one-time a.c. electric stimulation, the device is thermally and mechanically cycled by the working body itself, resulting in an external-driver-free, self-cycling, soft refrigerator. The prototype offers a directly measured cooling power density of 6.5 W g-1 and a peak COP exceeding 58 under a zero temperature span. Being merely a 30-µm-thick polymer film, the device achieved a COP close to 24 under a 4 K temperature span in an open ambient environment (32% thermodynamic efficiency). Compared with passive cooling, the thin-film refrigerator could immediately induce an additional 17.5 K temperature drop against an electronic chip. The soft, polymeric refrigerator can sense, actuate and pump heat to provide automatic localized thermal management.

Toward Ultrahigh Rate and Cycling Performance of Cathode Materials of Sodium Ion Battery by Introducing a Bicontinuous Porous Structure.

The emerging sodium-ion batteries (SIBs) are one of the most promising candidates expected to complement lithium-ion batteries and diversify the battery market. However, the exploitation of cathode materials with high-rate performance and long-cycle stability for SIBs has remained one of the major challenges. To this end, an efficient approach to enhance rate and cycling performance by introducing an ordered bicontinuous porous structure into cathode materials of SIBs is demonstrated. Prussian blue analogues (PBAs) are selected because they are recognized as a type of most promising SIB cathode materials. Thanks to the presence of 3D continuous channels enabling fast Na+ ions diffusion as well as the intrinsic mechanical stability of bicontinuous architecture, the resultant PBAs exhibit excellent rate capability (80 mAh g-1 at 2.5 A g-1) and ultralong cycling life (>3000 circulations at 0.5 A g-1), reaching the top performance of the reported PBA-based cathode materials. This study opens a new avenue for boosting sluggish ion diffusion kinetics in electrodes of rechargeable batteries and also provides a new paradigm for solving the dilemma that electrodes' failure due to high-stress concentration upon ion storage.

Low-k nano-dielectrics facilitate electric-field induced phase transition in high-k ferroelectric polymers for sustainable electrocaloric refrigeration.

Ferroelectric polymer-based electrocaloric effect may lead to sustainable heat pumps and refrigeration owing to the large electrocaloric-induced entropy changes, flexible, lightweight and zero-global warming potential. Herein, low-k nanodiamonds are served as extrinsic dielectric fillers to fabricate polymeric nanocomposites for electrocaloric refrigeration. As low-k nanofillers are naturally polar-inactive, hence they have been widely applied for consolidate electrical stability in dielectrics. Interestingly, we observe that the nanodiamonds markedly enhances the electrocaloric effect in relaxor ferroelectrics. Compared with their high-k counterparts that have been extensively studied in the field of electrocaloric nanocomposites, the nanodiamonds introduces the highest volumetric electrocaloric enhancement (~23%/vol%). The resulting polymeric nanocomposite exhibits concurrently improved electrocaloric effect (160%), thermal conductivity (175%) and electrical stability (125%), which allow a fluid-solid coupling-based electrocaloric refrigerator to exhibit an improved coefficient of performance from 0.8 to 5.3 (660%) while maintaining high cooling power (over 240 W) at a temperature span of 10 K.

Self-regulated underwater phototaxis of a photoresponsive hydrogel-based phototactic vehicle.

Incorporating a negative feedback loop in a synthetic material to enable complex self-regulative behaviours akin to living organisms remains a design challenge. Here we show that a hydrogel-based vehicle can follow the directions of photonic illumination with directional regulation inside a constraint-free, fluidic space. By manipulating the customized photothermal nanoparticles and the microscale pores in the polymeric matrix, we achieved strong chemomechanical deformation of the soft material. The vehicle swiftly assumes an optimal pose and creates directional flow around itself, which it follows to achieve robust full-space phototaxis. In addition, this phototaxis enables a series of complex underwater locomotions. We demonstrate that this versatility is generated by the synergy of photothermofluidic interactions resulting in closed-loop self-control and fast reconfigurability. The untethered, electronics-free, ambient-powered hydrogel vehicle manoeuvres through obstacles agilely, following illumination cues of moderate intensities, similar to that of natural sunlight.

Colossal electrocaloric effect in an interface-augmented ferroelectric polymer.

The electrocaloric effect demands the maximized degree of freedom (DOF) of polar domains and the lowest energy barrier to facilitate the transition of polarization. However, optimization of the DOF and energy barrier-including domain size, crystallinity, multiconformation coexistence, polar correlation, and other factors in bulk ferroelectrics-has reached a limit. We used organic crystal dimethylhexynediol (DMHD) as a three-dimensional sacrificial master to assemble polar conformations at the heterogeneous interface in poly(vinylidene fluoride)-based terpolymer. DMHD was evaporated, and the epitaxy-like process induced an ultrafinely distributed, multiconformation-coexisting polar interface exhibiting a giant conformational entropy. Under a low electric field, the interface-augmented terpolymer had a high entropy change of 100 J/(kg·K). This interface polarization strategy is generally applicable to dielectric capacitors, supercapacitors, and other related applications.

Statistical Mechanical Model of the Giant Electrocaloric Effect in Ferroelectric Polymers.

The development of highly efficient cooling technologies has been identified as a key strategy to address the mitigation of global warming. Especially, electrocaloric materials have emerged as promising candidates for cooling applications, owing to their potential to provide high cooling capacity with low energy consumption. To advance the development of electrocaloric materials with a significant electrocaloric effect (ECE), a thorough understanding of the underlying mechanisms is required. Previous studies have estimated the maximum ECE temperature change by calculating the entropy change between two assumed states of a dipole model, assuming polarization saturation with a sufficiently large electric field. However, it is more relevant to assess the ECE under continuously changing electric fields as this is more reflective of real-world conditions. To this end, we establish a continuous transition between the complete disorder state and the polarization saturation state using the partition function to derive the entropy change. Our results demonstrate excellent agreement with experimental data, and our analysis of energy items within the partition function attributes the increase in the ECE entropy change with decreasing crystal size to interfacial effects. This statistical mechanical model reveals the in-depth ferroelectric polymers producing the ECE and offers significant potential for predicting the ECE in ferroelectric polymers and thus guides the design of high-performance ECE materials.

Fluoropolymer ferroelectrics: Multifunctional platform for polar-structured energy conversion.

Ferroelectric materials are currently some of the most widely applied material systems and are constantly generating improved functions with higher efficiencies. Advancements in poly(vinylidene fluoride) (PVDF)-based polymer ferroelectrics provide flexural, coupling-efficient, and multifunctional material platforms for applications that demand portable, lightweight, wearable, and durable features. We highlight the recent advances in fluoropolymer ferroelectrics, their energetic cross-coupling effects, and emerging technologies, including wearable, highly efficient electromechanical actuators and sensors, electrocaloric refrigeration, and dielectric devices. These developments reveal that the molecular and nanostructure manipulations of the polarization-field interactions, through facile defect biasing, could introduce enhancements in the physical effects that would enable the realization of multisensory and multifunctional wearables for the emerging immersive virtual world and smart systems for a sustainable future.

Ladderphane copolymers for high-temperature capacitive energy storage.

For capacitive energy storage at elevated temperatures1-4, dielectric polymers are required to integrate low electrical conduction with high thermal conductivity. The coexistence of these seemingly contradictory properties remains a persistent challenge for existing polymers. We describe here a class of ladderphane copolymers exhibiting more than one order of magnitude lower electrical conductivity than the existing polymers at high electric fields and elevated temperatures. Consequently, the ladderphane copolymer possesses a discharged energy density of 5.34 J cm-3 with a charge-discharge efficiency of 90% at 200 °C, outperforming the existing dielectric polymers and composites. The ladderphane copolymers self-assemble into highly ordered arrays by π-π stacking interactions5,6, thus giving rise to an intrinsic through-plane thermal conductivity of 1.96 ± 0.06 W m-1 K-1. The high thermal conductivity of the copolymer film permits efficient Joule heat dissipation and, accordingly, excellent cyclic stability at elevated temperatures and high electric fields. The demonstration of the breakdown self-healing ability of the copolymer further suggests the promise of the ladderphane structures for high-energy-density polymer capacitors operating under extreme conditions.

Chemical adsorption on 2D dielectric nanosheets for matrix free nanocomposites with ultrahigh electrical energy storage.

Relaxor ferroelectric polymers display great potential in capacitor dielectric applications because of their excellent flexibility, light weight, and high dielectric constant. However, their electrical energy storage capacity is limited by their high conduction losses and low dielectric strength, which primarily originates from the impact-ionization-induced electronmultiplication, low mechanical modulus, and low thermal conductivity of the dielectric polymers. Here a matrix free strategy is developed to effectively suppress electron multiplication effects and to enhance mechanical modulus and thermal conductivity of a dielectric polymer, which involves the chemical adsorption of an electron barrier layer on boron nitride nanosheet surfaces by chemically adsorbing an amino-containing polymer. A dramatic decrease of leakage current (from 2.4 × 10-6 to 1.1 × 10-7 A cm-2 at 100 MV m-1) and a substantial increase of breakdown strength (from 340 to 742 MV m-1) were achieved in the nanocompostes, which result in a remarkable increase of discharge energy density (from 5.2 to 31.8 J cm-3). Moreover, the dielectric strength of the nanocomposites suffering an electrical breakdown could be restored to 88% of the original value. This study demonstrates a rational design for fabricating dielectric polymer nanocomposites with greatly enhanced electric energy storage capacity.

Relaxor ferroelectric polymer exhibits ultrahigh electromechanical coupling at low electric field.

Electromechanical (EM) coupling-the conversion of energy between electric and mechanical forms-in ferroelectrics has been used for a broad range of applications. Ferroelectric polymers have weak EM coupling that severely limits their usefulness for applications. We introduced a small amount of fluorinated alkyne (FA) monomers (<2 mol %) in relaxor ferroelectric poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (PVDF-TrFE-CFE) terpolymer that markedly enhances the polarization change with strong EM coupling while suppressing other polarization changes that do not contribute to it. Under a low-dc bias field of 40 megavolts per meter, the relaxor tetrapolymer has an EM coupling factor (k33) of 88% and a piezoelectric coefficient (d33) >1000 picometers per volt. These values make this solution-processed polymer competitive with ceramic oxide piezoelectrics, with the potential for use in distinct applications.

High-entropy polymer produces a giant electrocaloric effect at low fields.

More than a decade of research on the electrocaloric (EC) effect has resulted in EC materials and EC multilayer chips that satisfy a minimum EC temperature change of 5 K required for caloric heat pumps1-3. However, these EC temperature changes are generated through the application of high electric fields4-8 (close to their dielectric breakdown strengths), which result in rapid degradation and fatigue of EC performance. Here we report a class of EC polymer that exhibits an EC entropy change of 37.5 J kg-1 K-1 and a temperature change of 7.5 K under 50 MV m-1, a 275% enhancement over the state-of-the-art EC polymers under the same field strength. We show that converting a small number of the chlorofluoroethylene groups in poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) terpolymer into covalent double bonds markedly increases the number of the polar entities and enhances the polar-nonpolar interfacial areas of the polymer. The polar phases in the polymer adopt a loosely correlated, high-entropy state with a low energy barrier for electric-field-induced switching. The polymer maintains performance for more than one million cycles at the low fields necessary for practical EC cooling applications, suggesting that this strategy may yield materials suitable for use in caloric heat pumps.

Interface-Strengthened Polymer Nanocomposites with Reduced Dielectric Relaxation Exhibit High Energy Density at Elevated Temperatures Utilizing a Facile Dual Crosslinked Network.

High-temperature ceramic/polymer nanocomposites with large energy density as the reinforcement exhibit great potential for energy storage applications in modern electronic and electrical power systems. Yet, a general drawback is that the increased dielectric constant is usually achieved at the cost of decreased breakdown strength, thus leading to moderate improvement of energy density and even displaying a marked deterioration under high temperatures and high electric fields. Herein, a new strategy is reported to simultaneously improve breakdown strength and discharged energy density by a step-by-step, controllable dual crosslinking process, which constructs a strengthened interface as well as reduces molecular chains relaxation under elevated temperatures. Great breakdown strength and discharged energy density is achieved in the dual crosslinked network BT-BCB@DPAES nanocomposites at elevated temperatures when compared to noninterfacial-strengthened, BT/DPAES composites, i.e., an enhanced breakdown strength and a discharged energy density of 442 MV m-1 and 3.1 J cm-3 , increasing by 66% and 162%, and a stable cyclic performance over 10 000 cycles is demonstrated at 150 °C. Moreover, the enhancement through the synergy of two crosslinked networks is rationalized via a comprehensive phase-field model for the composites. This work offers a strategy to enhance the electric storage performances of composites at high temperatures.

Artificial phototropism for omnidirectional tracking and harvesting of light.

Many living organisms track light sources and halt their movement when alignment is achieved. This phenomenon, known as phototropism, occurs, for example, when plants self-orient to face the sun throughout the day. Although many artificial smart materials exhibit non-directional, nastic behaviour in response to an external stimulus, no synthetic material can intrinsically detect and accurately track the direction of the stimulus, that is, exhibit tropistic behaviour. Here we report an artificial phototropic system based on nanostructured stimuli-responsive polymers that can aim and align to the incident light direction in the three-dimensions over a broad temperature range. Such adaptive reconfiguration is realized through a built-in feedback loop rooted in the photothermal and mechanical properties of the material. This system is termed a sunflower-like biomimetic omnidirectional tracker (SunBOT). We show that an array of SunBOTs can, in principle, be used in solar vapour generation devices, as it achieves up to a 400% solar energy-harvesting enhancement over non-tropistic materials at oblique illumination angles. The principle behind our SunBOTs is universal and can be extended to many responsive materials and a broad range of stimuli.

Bioinspired Polymer Nanocomposites Exhibit Giant Energy Density and High Efficiency at High Temperature.

Polymer dielectrics are ubiquitous in advanced electric energy storage systems. However, the relatively low operating temperature significantly menaces their widespread application at high temperatures, such as for hybrid vehicles and aerospace power electronics. Spider silk, a natural nanocomposite comprised of biopolymer chains and crystal protein nanosheets combined by multiple interfacial interactions, exhibits excellent mechanical properties even at elevated temperatures. Inspired by the hierarchical nanostructure of spider silk, poly(aryl ether sulfone) is anchored to the surface of wide bandgap artificial nanosheets to prepare the nanocomposites with nanoconfinement effect. The bioinspired strategy successfully improves the mechanical and electrical performances of the nanocomposite. Owing to the structural-enabled enhancements, the nanocomposites exhibit excellent breakdown strength and electrical energy storage performance at high temperatures. In detail, giant discharged energy density (2.7 J cm-3 ) and high charge-discharge efficiency (>90%) are simultaneously achieved at 150 °C and 400 MV m-1 . Notably, under 500 MV m-1 , the discharged energy density reaches 4.2 J cm-3 , which is the record high discharged energy density among polymer-based dielectrics at 150 °C. This work demonstrates a viable strategy to design high-temperature polymer dielectrics by constructing nanoconfinement in the nanocomposites.

Soft phototactic swimmer based on self-sustained hydrogel oscillator.

Oscillations are widely found in living organisms to generate propulsion-based locomotion often driven by constant ambient conditions, such as phototactic movements. Such environment-powered and environment-directed locomotions may advance fully autonomous remotely steered robots. However, most man-made oscillations require nonconstant energy input and cannot perform environment-dictated movement. Here, we report a self-sustained soft oscillator that exhibits perpetual and untethered locomotion as a phototactic soft swimming robot, remotely fueled and steered by constant visible light. This particular out-of-equilibrium actuation arises from a self-shadowing-enabled negative feedback loop inherent in the dynamic light-material interactions, promoted by the fast and substantial volume change of the photoresponsive hydrogel. Our analytical model and governing equation unveil the oscillation mechanism and design principle with key parameters identified to tune the dynamics. On this autonomous oscillator platform, we establish a broadly applicable principle for converting a continuous input into a discontinuous output. The modular design can be customized to accommodate various forms of input energy and to generate diverse oscillatory behaviors. The hydrogel oscillator showcases agile life-like omnidirectional motion in the entire three-dimensional space with near-infinite degrees of freedom. The large force generated by the powerful and long-lasting oscillation can sufficiently overcome water damping and effectively self-propel away from a light source. Such a hydrogel oscillator-based all-soft swimming robot, named OsciBot, demonstrated high-speed and controllable phototactic locomotion. This autonomous robot is battery free, deployable, scalable, and integratable. Artificial phototaxis opens broad opportunities in maneuverable marine automated systems, miniaturized transportation, and solar sails.

Sodium Ion Capacitor Using Pseudocapacitive Layered Ferric Vanadate Nanosheets Cathode.

Sodium ion capacitors (SICs) are designed to deliver both high energy and power densities at low cost. Electric double-layer capacitive cathodes are typically used in these devices, but they lead to very limited capacity. Herein, we apply a pseudocapacitive layered ferric vanadate (Fe-V-O) as cathode to construct non-aqueous SICs with both high energy and power densities. The Fe-V-O nanosheets cathode displays remarkable rate capability and cycling stability. The pseudocapacitive sodium storage mechanism of Fe-V-O, with over 83% of total capacity from capacitive contribution, is confirmed by kinetics analysis and ex situ characterizations. The capacitive-adsorption mechanism of hard carbon (HC) anode is demonstrated, and it delivers excellent rate capability. Based on as-synthesized materials, the assembled HC//Fe-V-O SIC delivers a maximum energy density of 194 Wh kg-1 and power density of 3,942 W kg-1. Our work highlights the advantages of pseudocapacitive cathodes for achieving both high energy and power densities in sodium storage devices.

Bioinspired Hydrogel Interferometer for Adaptive Coloration and Chemical Sensing.

Living organisms ubiquitously display colors that adapt to environmental changes, relying on the soft layer of cells or proteins. Adoption of soft materials into an artificial adaptive color system has promoted the development of material systems for environmental and health monitoring, anti-counterfeiting, and stealth technologies. Here, a hydrogel interferometer based on a single hydrogel thin film covalently bonded to a reflective substrate is reported as a simple and universal adaptive color platform. Similar to the cell or protein soft layer of color-changing animals, the soft hydrogel layer rapidly changes its thickness in response to external stimuli, resulting in instant color change. Such interference colors provide a visual and quantifiable means of revealing rich environmental metrics. Computational model is established and captures the key features of hydrogel stimuli-responsive swelling, which elucidates the mechanism and design principle for the broad-based platform. The single material-based platform has advantages of remarkable color uniformity, fast response, high robustness, and facile fabrication. Its versatility is demonstrated by diverse applications: a volatile-vapor sensor with highly accurate quantitative detection, a colorimetric sensor array for multianalyte recognition, breath-controlled information encryption, and a colorimetric humidity indicator. Portable and easy-to-use sensing systems are demonstrated with smartphone-based colorimetric analysis.

A Room Temperature Ultrasensitive Magnetoelectric Susceptometer for Quantitative Tissue Iron Detection.

Iron is a trace mineral that plays a vital role in the human body. However, absorbing and accumulating excessive iron in body organs (iron overload) can damage or even destroy an organ. Even after many decades of research, progress on the development of noninvasive and low-cost tissue iron detection methods is very limited. Here we report a recent advance in a room-temperature ultrasensitive biomagnetic susceptometer for quantitative tissue iron detection. The biomagnetic susceptometer exploits recent advances in the magnetoelectric (ME) composite sensors that exhibit an ultrahigh AC magnetic sensitivity under the presence of a strong DC magnetic field. The first order gradiometer based on piezoelectric and magnetostrictive laminate (ME composite) structure shows an equivalent magnetic noise of 0.99 nT/rt Hz at 1 Hz in the presence of a DC magnetic field of 0.1 Tesla and a great common mode noise rejection ability. A prototype magnetoelectric liver susceptometry has been demonstrated with liver phantoms. The results indicate its output signals to be linearly responsive to iron concentrations from normal iron dose (0.05 mg Fe/g liver phantom) to 5 mg Fe/g liver phantom iron overload (100X overdose). The results here open up many innovative possibilities for compact-size, portable, cost-affordable, and room-temperature operated medical systems for quantitative determinations of tissue iron.

Electrocaloric response near room temperature in Zr- and Sn-doped BaTiO3 systems.

The electrocaloric effect (ECE) in (1-x)BaZr0.18 Ti0.82O3-(x)BaSn0.11Ti0.89O3 (BZT18-BST11, 0.1≤x≤0.5) ceramics is investigated near room temperature using a calorimetry method. The ceramics exhibit relaxor-like ferroelectric characteristics and by merging phases, a large electrocaloric (EC) response is observed in the system. The largest entropy change is 4.8 Jkg(-1) K(-1) (along with a temperature change of 3.5 K), which is induced under an electric field of 10 MV m(-1) for the 0.8 BaZr0.18Ti0.82O3-0.2 BaSn0.11Ti0.89O3 ceramics. This result reveals that the coexistence of multiple phases improves the ECE of the ceramics, which provides an effective route to achieve a large EC response using a small electric field.This article is part of the themed issue 'Taking the temperature of phase transitions in cool materials'.

An Ultrasensitive Magnetoelectric Sensor System For the Quantitative Detection of Liver Iron.

Ultrasensitive magnetoelectric (ME) sensors have been developed using magnetostrictive/piezoelectric laminate heterostructures. This paper discusses a highly interdisciplinary design of a room temperature biomagnetic liver susceptometry system (BLS) based on the ME sensors. The ME-sensor based BLS maintains the ultrahigh sensitivity to detect the weak AC biomagnetic signals and introduces a low equivalent magnetic noise. The results reveal a "turning point" and successfully indicate the output signals to be linearly responsive to iron concentrations from normal iron level (0.05 mgFe/gliver phantom) to 5 mgFe/gliver phantom iron overload level (100X overdose). Further, the introduction of the water-bag technique shows the promise on the automatic deduction of the background (tissue) signal, enabling an even higher sensitivity and better signal-to-noise (SNR). With these improvements, it becomes feasible to get improved characterization flexibility and the field distribution mapping potential via signal processing from the correlations of multiple sensors in the system. Considering the wide presence of biomagnetic signals in human organs, the potential impact of such biomagnetic devices on medicine and health care could be enormous and far-reaching.