Energy harvesting from acid mine drainage using a highly proton/ion-selective thin polyamide film.

A huge chemical potential difference exists between the acid mine drainage (AMD) and the alkaline neutralization solution, which is wasted in the traditional AMD neutralization process. This study reports, for the first time, the harvest of this chemical potential energy through a controlled neutralization of AMD using H+-conductive films. Polyamide films with controllable thickness achieved much higher H+ conductance than a commercially available cation exchange membrane (CEM). Meanwhile, the optimal polyamide film had an excellent H+/Ca2+ selectivity of 63.7, over two orders of magnitude higher than that of the CEM (0.3). The combined advantages of fast proton transport and high proton/ion selectivity greatly enhanced the power generation of the AMD battery. The power density was 3.1 W m-2, which is over one order of magnitude higher than that of the commercial CEM (0.2 W m-2). Our study provides a new sustainable solution to address the environmental issues of AMD while simultaneously enabling clean energy production.

A Self-Assembled 3D/0D Quasi-Core-Shell Structure as Internal Encapsulation Layer for Stable and Efficient FAPbI3 Perovskite Solar Cells and Modules.

FAPbI3 perovskites have garnered considerable interest owing to their outstanding thermal stability, along with near-theoretical bandgap and efficiency. However, their inherent phase instability presents a substantial challenge to the long-term stability of devices. Herein, this issue through a dual-strategy of self-assembly 3D/0D quasi-core-shell structure is tackled as an internal encapsulation layer, and in situ introduction of excess PbI2 for surface and grain boundary defects passivating, therefore preventing moisture intrusion into FAPbI3 perovskite films. By utilizing this method alone, not only enhances the stability of the FAPbI3 film but also effectively passivates defects and minimizes non-radiative recombination, ultimately yielding a champion device efficiency of 23.23%. Furthermore, the devices own better moisture resistance, exhibiting a T80 lifetime exceeding 3500 h at 40% relative humidity (RH). Meanwhile, a 19.51% PCE of mini-module (5 × 5 cm2) is demonstrated. This research offers valuable insights and directions for the advancement of stable and highly efficient FAPbI3 perovskite solar cells.

Modulation of Radical Intermediates in Rechargeable Organic Batteries.

Organic materials have been considered as promising electrodes for next-generation rechargeable batteries in view of their sustainability, structural flexibility, and potential recyclability. The radical intermediates generated during the redox process of organic electrodes have profound effect on the reversible capacity, operation voltage, rate performance, and cycling stability. However, the radicals are highly reactive and have very short lifetime during the redox of organic materials. Great efforts have been devoted to capturing and investigating the radical intermediates in organic electrodes. Herein, this review summarizes the importance, history, structures, and working principles of organic radicals in rechargeable batteries. More importantly, challenges and strategies to track and regulate the radicals in organic batteries are highlighted. Finally, further perspectives of organic radicals are proposed for the development of next-generation high-performance rechargeable organic batteries.

Ultrasensitive Flexible Thermal Sensor Arrays based on High-Thermopower Ionic Thermoelectric Hydrogel.

Ionic circuits using ions as charge carriers have demonstrated great potential for flexible and bioinspired electronics. The emerging ionic thermoelectric (iTE) materials can generate a potential difference by virtue of selective thermal diffusion of ions, which provide a new route for thermal sensing with the merits of high flexibility, low cost, and high thermopower. Here, ultrasensitive flexible thermal sensor arrays based on an iTE hydrogel consisting of polyquaternium-10 (PQ-10), a cellulose derivative, as the polymer matrix and sodium hydroxide (NaOH) as the ion source are reported. The developed PQ-10/NaOH iTE hydrogel achieves a thermopower of 24.17 mV K-1 , which is among the highest values reported for biopolymer-based iTE materials. The high p-type thermopower can be attributed to thermodiffusion of Na+ ions under a temperature gradient, while the movement of OH- ions is impeded by the strong electrostatic interaction with the positively charged quaternary amine groups of PQ-10. Flexible thermal sensor arrays are developed through patterning the PQ-10/NaOH iTE hydrogel on flexible printed circuit boards, which can perceive spatial thermal signals with high sensitivity. A smart glove integrated with multiple thermal sensor arrays is further demonstrated, which endows a prosthetic hand with thermal sensation for human-machine interaction.

A Gradient Lithiophilic Structure for Stable Lithium Metal Anodes with Ultrahigh Rate and Ultradeep Capacity.

Using three-dimensional current collectors (3DCC) as frameworks for lithium metal anodes (LMAs) is a promising approach to inhibit dendrite growth. However, the intrinsically accumulated current density on the top surface and limited Li-ion transfer in the interior of 3DCC still lead to the formation of lithium dendrites, which can pose safety risks. In this study, it reports that gradient lithiophilic structures can induce uniform lithium deposition within the interior of the 3DCC, greatly suppressing dendrite formation, as confirmed by COMSOL simulations and experimental results. With this concept, a gradient-structured zinc oxide-loaded copper foam (GSZO-CF) is synthesized via an easy solution-combustion method at low cost. The resulting Li@GSZO-CF symmetric cells demonstrate stable cycling performance for over 800 cycles, with an ultra-deep capacity of 10 mAh cm-2 even under an ultra-high current density of 50 mA cm-2 , the top results reported in the literature. Moreover, when combined with a LiFePO4 (LFP) cathode under a low negative/positive (N/P) capacity ratio of 2.9, the Li@GSZO-CF||LFP full cells exhibit stable performance for 200 cycles, with a discharge capacity of 130 mAh g-1 and retention of 85.5% at a charging/discharging rate of 1C. These findings suggest a promising strategy for the development of new-generation LMAs.

Co-Solvent Engineering Contributing to Achieve High-Performance Perovskite Solar Cells and Modules Based on Anti-Solvent Free Technology.

The pinhole-free and defect-less perovskite film is crucial for achieving high efficiency and stable perovskite solar cells (PSCs), which can be prepared by widely used anti-solvent crystallization strategies. However, the involvement of anti-solvent requires precise control and inevitably brings toxicity in fabrication procedures, which limits its large-scale industrial application. In this work, a facile and effective co-solvent engineering strategy is introduced to obtain high- quality perovskite film while avoiding the usage of anti-solvent. The uniform and compact perovskite polycrystalline films have been fabricated through the addition of co-solvent that owns strong coordination capacity with perovskite components , meanwhile possessing the weaker interaction with main solvent . With those strategies, a champion power conversion efficiency (PCE) of 22% has been achieved with the optimal co-solvent, N-methylpyrrolidone (NMP) and without usage of anti-solvent. Subsequently, PSCs based on NMP show high repeatability and good shelf stability (80% PCE remains after storing in ambient condition for 30 days). Finally, the perovskite solar module (5 × 5 cm) with 7 subcells connects in series yielding champion PCE of 16.54%. This strategy provides a general guidance of co-solvent selection for PSCs based on anti-solvent free technology and promotes commercial application of PSCs.

Cinnamate-Functionalized Cellulose Nanocrystals as Interfacial Layers for Efficient and Stable Perovskite Solar Cells.

The poor interfacial contact and imperfections between the charge transport layer and perovskite film often result in carrier recombination, inefficient charge collection, and inferior stability of perovskite solar cells (PSCs). Therefore, interface engineering is quite crucial to achieve high-performance and stable PSCs. Here, we introduced a cinnamate-functionalized cellulose nanocrystals (Cin-CNCs) interfacial layer between SnO2 and perovskite active layer for enhancing carrier transport ability and crystal growth of perovskite, meanwhile endowing additional functional of long-term device stability against ultraviolet light. The enhancement of interfacial contact between SnO2 and perovskite layer and cascade energy alignment are realized, which is beneficial for obtaining the desirable perovskite film morphology, passivating the interfacial defects, and restraining charge recombination in the SnO2/perovskite interface. An efficiency as high as 23.18%, with an open-circuit voltage of 1.15 V and a significantly enhanced fill factor of 81.07%, is achieved. In addition, the unencapsulated PSCs maintain 75% of the initial PCE after aging for over 1500 h under 25 °C and 30% relative humidity, with better light-soaking stability. These results exhibit the vital role for Cin-CNCs in interfacial modification and constructing high-performance perovskite solar cells.

Rational Design of Porous Nanowall Arrays of Ultrafine Co4N Nanoparticles Confined in a La2O2CN2 Matrix on Carbon Cloth for a High-Performing Supercapacitor Electrode.

Transition metal nitrides (TMNs) have received special concern as important energy storage materials, owing to their high conductibility, good mechanical strength, and superior corrosion resistance. However, their insufficient capacitance and poor cycling stability limit their practical applications for supercapacitors. Here, a novel three-dimensional (3D) self-supported integrated electrode consisted of porous nanowall arrays of ultrafine cobalt nitride (Co4N) nanoparticles encapsulated in a lanthanum oxycyanamide (LOC) matrix on carbon cloth (Co4N@LOC/CC) for outstanding electrochemical energy storage is rationally designed and fabricated. The 3D monolithic configuration of porous nanowall arrays facilitates the mass/charge transfer, the exposure of electroactive sites, and the enhancement of electrical conductivity. Meanwhile, the unique core-shell structure of Co4N@LOC can prevent ultrafine Co4N nanoparticles from sintering, agglomeration, and oxidation and promotes electron transfer dynamics during the redox reaction, meanwhile enhancing the stability of the electrode. Additionally, the synergy of Co4N and LOC can result in an efficient electron/ion transport in the process of the charge-discharge. Because of these features, the Co4N@LOC/CC electrode displays superior specific capacitance (895.6 mF cm-2 or 613.4 F g-1 at 1 mA cm-2) and admirable cycling durability (87.9% capacitance reservation after 10 000 cycles), surpassing the majority of nitride-based electrodes reported thus far. Furthermore, after being assembled into an asymmetric supercapacitor using active carbon (AC) as an anode, the obtained Co4N@LOC/CC//AC/CC device displays a high energy density of 41.7 Wh kg-1 at the power density of 875.8 W kg-1 with a high capacitance reservation of 87.6% after 5000 cycles at 2 mA cm-2. This work offers an efficient approach of combining TMNs with rare earth compounds to enhance the capacitance and stability of TMNs for supercapacitor electrodes.

Unveiling the Growth of Polyamide Nanofilms at Water/Organic Free Interfaces: Toward Enhanced Water/Salt Selectivity.

The permeance and selectivity of a reverse osmosis (RO) membrane are governed by its ultrathin polyamide film, yet the growth of this critical film during interfacial polymerization (IP) has not been fully understood. This study investigates the evolution of a polyamide nanofilm at the aqueous/organic interface over time. Despite its thickness remaining largely constant (∼15 nm) for the IP reaction time ranging from 0.5 to 60 min, the density of the polyamide nanofilm increased from 1.25 to 1.36 g cm-3 due to the continued reaction between diffused m-phenylenediamine and dangling acyl chloride groups within the formed polyamide film. This continued growth of the polyamide nanofilm led to a simultaneous increase in its crosslinking degree (from 50.1 to 94.3%) and the healing of nanosized defects, resulting in a greatly enhanced rejection of 99.2% for NaCl without sacrificing water permeance. Using humic acid as a molecular probe for sealing membrane defects, the relative contributions of the increased crosslinking and reduced defects toward better membrane selectivity were resolved, which supports our conceptual model involving both enhanced size exclusion and healed defects. The fundamental insights into the growth mechanisms and the structure-property relationship of the polyamide nanofilm provide crucial guidance for the further development and optimization of high-performance RO membranes.

Additive Engineering in Antisolvent for Widening the Processing Window and Promoting Perovskite Seed Formation in Perovskite Solar Cells.

The chlorobenzene (CB) antisolvent is widely used to fabricate high-efficiency perovskite solar cells (PSCs). However, the narrow processing window and the strict volume ratio of a binary mixed solvent limit the fabrication of large-area and high-quality perovskite films. In this work, by systematic investigation of additives with the CB antisolvent, a universal guideline is achieved wherein a small amount of additive with a donor number between 9.0 and 27.0 kcal/mol can significantly widen the antisolvent treating time slot from 2 to 40 s while simultaneously enlarging the processor binary mixed solvent (dimethylformamide/dimethyl sulfoxide) from 7:3 to 0:10. Moreover, this process facilitates the formation of perovskite seeds as templates for perovskite crystal growth, effectively reducing the bulk defects in perovskite films. Finally, the obtained PSCs show remarkable power conversion efficiencies (PCEs) of 22.22 and 19.74% for rigid and flexible devices, respectively.

Hydrogels as Soft Ionic Conductors in Flexible and Wearable Triboelectric Nanogenerators.

Flexible triboelectric nanogenerators (TENGs) have attracted increasing interest since their advent in 2012. In comparison with other flexible electrodes, hydrogels possess transparency, stretchability, biocompatibility, and tunable ionic conductivity, which together provide great potential as current collectors in TENGs for wearable applications. The development of hydrogel-based TENGs (H-TENGs) is currently a burgeoning field but research efforts have lagged behind those of other common flexible TENGs. In order to spur research and development of this important area, a comprehensive review that summarizes recent advances and challenges of H-TENGs will be very useful to researchers and engineers in this emerging field. Herein, the advantages and types of hydrogels as soft ionic conductors in TENGs are presented, followed by detailed descriptions of the advanced functions, enhanced output performance, as well as flexible and wearable applications of H-TENGs. Finally, the challenges and prospects of H-TENGs are discussed.

On-Demand, Direct Printing of Nanodiamonds at the Quantum Level.

The quantum defects in nanodiamonds, such as nitrogen-vacancy (NV) centers, are emerging as a promising candidate for nanoscale sensing and imaging, and the controlled placement with respect to target locations is vital to their practical applications. Unfortunately, this prerequisite continues to suffer from coarse positioning accuracy, low throughput, and process complexity. Here, it is reported on direct, on-demand electrohydrodynamic printing of nanodiamonds containing NV centers with high precision control over quantity and position. After thorough characterizations of the printing conditions, it is shown that the number of printed nanodiamonds can be controlled at will, attaining the single-particle level precision. This printing approach, therefore, enables positioning NV center arrays with a controlled number directly on the universal substrate without any lithographic process. The approach is expected to pave the way toward new horizons not only for experimental quantum physics but also for the practical implementation of such quantum systems.

Biomechanical Energy Harvesters Based on Ionic Conductive Organohydrogels via the Hofmeister Effect and Electrostatic Interaction.

The recent use of cryoprotectant replacement method for solving the easy drying problem of hydrogels has attracted increasing research interest. However, the conductivity decrease of organohydrogels due to the induced insulating solvent limited their electronic applications. Herein, we introduce the Hofmeister effect and electrostatic interaction to generate hydrogen and sodium bonds in the hydrogel. Combined with its double network, an effective charge channel that will not be affected by the solvent replacement, is therefore built. The developed organohydrogel-based single-electrode triboelectric nanogenerator (OHS-TENG) shows low conductivity decrease (one order) and high output (1.02-1.81 W/m2), which is much better than reported OHS-TENGs (2-3 orders, 41.2-710 mW/m2). Moreover, replacing water with glycerol in the hydrogel enables the device to exhibit excellent long-term stability (four months) and temperature tolerance (-50-100 °C). The presented strategy and mechanism can be extended to common organohydrogel systems aiming at high performance in electronic applications.

Three-Dimensional Perovskite Nanopixels for Ultrahigh-Resolution Color Displays and Multilevel Anticounterfeiting.

Hybrid perovskites are emerging as a promising, high-performance luminescent material; however, the technological challenges associated with generating high-resolution, free-form perovskite structures remain unresolved, limiting innovation in optoelectronic devices. Here, we report nanoscale three-dimensional (3D) printing of colored perovskite pixels with programmed dimensions, placements, and emission characteristics. Notably, a meniscus comprising femtoliters of ink is used to guide a highly confined, out-of-plane crystallization process, which generates 3D red, green, and blue (RGB) perovskite nanopixels with ultrahigh integration density. We show that the 3D form of these nanopixels enhances their emission brightness without sacrificing their lateral resolution, thereby enabling the fabrication of high-resolution displays with improved brightness. Furthermore, 3D pixels can store and encode additional information into their vertical heights, providing multilevel security against counterfeiting. The proof-of-concept experiments demonstrate the potential of 3D printing to become a platform for the manufacture of smart, high-performance photonic devices without design restrictions.

Self-Densified Optically Transparent VO2 Thermochromic Wood Film for Smart Windows.

Optically transparent wood has emerged as a promising glazing material. Thanks to the high optical transmittance, strong mechanical properties, and excellent thermal insulation capability of transparent wood, it offers a potential alternative to glass for window applications. Recently, thermo-, electro-, and photochromic transparent woods that dynamically modulate light transmittance have been investigated to improve building energy efficiency. However, it remains challenging to widely replace windows with transparent wood because of its poor weather resistance. In this study, an environment-friendly thermochromic transparent wood film (TTWF) with thermal switching of transmittance is proposed and demonstrated. To achieve thermochromism, the bleached wood is impregnated with the vanadium dioxide (VO2)/polyvinyl alcohol composite. Due to the self-densification of cellulose microfibrils during the evaporation of solvents, the transparent wood is in the form of thin films, which can be attached on the inner face of a window to protect it from severe weather conditions, making the installation convenient and low-cost. Furthermore, the surface of VO2-TTWF is modified by octadecyltrichlorosilane to enhance the waterproof ability and achieve self-cleaning and antidust functions. The proposed VO2-TTWF shows great potential for application in energy-efficient buildings using sustainable materials with advanced optical properties (i.e., Tlum = 50.5%, ΔTsol = 3.4%, and haze = 70%) that are mechanically robust (i.e., σ = 130.6 MPa along the wood growth direction), have low-thermal conductivity (i.e., K = 0.29 W m-1 K-1 along the perpendicular direction to the wood fibers), and demonstrate hydrophobic self-cleaning and antidust functions (i.e., contact angle: 121.9°). An experiment, using a model house, showed that the VO2-TTWF attached on the inner face of the window could significantly reduce the indoor air temperature by 33.9 °C compared with a bare glass panel, proving that VO2-TTWF has potential to be applied as a new-generation energy-efficient material for smart windows.

Three-Dimensional Printing of Self-Assembled Dipeptides.

Peptide-based materials are emerging as smart building blocks for nanobiodevices due to the programmability of their properties via the molecular constituents or arrangements. Many clever molecular self-assembly approaches have been devised to produce peptide crystalline structures. However, their freeform shaping remains a challenge due to the intrinsic self-assembly nature. Here, we report the fabrication of freeform, crystalline diphenylalanine (FF) peptide structures by combining meniscus-guided 3D printing with molecular self-assembly. Self-assembly in 3D-printed FF arises from mild thermal activation under precise temperature control of the build platform. After thorough characterizations, we demonstrate layer-by-layer, crystalline 3D printing with a high spatial resolution of 2 µm laterally and 200 nm vertically. The 3D-printed FF exhibits piezoelectricity originating from its crystalline character, showing the potential to become a key constituent for bioelectronic devices. We expect this technique to open up the possibility to create functional devices based on self-assembled organic materials without design restrictions.

Electrodeposition of (111)-oriented and nanotwin-doped nanocrystalline Cu with ultrahigh strength for 3D IC application.

The mechanical performance of electroplated Cu plays a crucial role in next-generation Cu-to-Cu direct bonding for the three-dimension integrated circuit (3D IC). This work reports direct-current electroplated (111)-preferred and nanotwin-doped nanocrystalline Cu, of which strength is at the forefront performance compared with all reported electroplated Cu materials. Tension and compression tests are performed to present the ultrahigh ultimate strength of 977 MPa and 1158 MPa, respectively. The microstructure of nanoscale Cu grains with an average grain size around 61 nm greatly contributes to the ultrahigh strength as described by the grain refinement effect. A gap between the obtained yield strength and the Hall-Petch relationship indicates the presence of extra strengthening mechanisms. X-ray diffraction and transmission electron microscopy analysis identify the highly (111) oriented texture and sporadic twins with optimum thicknesses, which can effectively impede intragranular dislocation movements, thus further advance the strength. Via filling capability and high throughput are also demonstrated in the patterned wafer plating. The combination of ultrahigh tensile/compressive strength, (111) preferred texture, superfilling capability and high throughput satisfies the critical requirement of Cu interconnects plating technology towards the industrial manufacturing in advanced 3D IC packaging application.

Interfacial stabilization for inverted perovskite solar cells with long-term stability.

Perovskite solar cells (PSCs) commonly exhibit significant performance degradation due to ion migration through the top charge transport layer and ultimately metal electrode corrosion. Here, we demonstrate an interfacial management strategy using a boron chloride subphthalocyanine (Cl6SubPc)/fullerene electron-transport layer, which not only passivates the interfacial defects in the perovskite, but also suppresses halide diffusion as evidenced by multiple techniques, including visual element mapping by electron energy loss spectroscopy. As a result, we obtain inverted PSCs with an efficiency of 22.0% (21.3% certified), shelf life of 7000 h, T80 of 816 h under damp heat stress (compared to less than 20 h without Cl6SubPc), and initial performance retention of 98% after 2000 h at 80 °C in inert environment, 90% after 2034 h of illumination and maximum power point tracking in ambient for encapsulated devices and 95% after 1272 h outdoor testing ISOS-O-1. Our strategy and results pave a new way to move PSCs forward to their potential commercialization solidly.

Giant thermopower of ionic gelatin near room temperature.

Harvesting heat from the environment into electricity has the potential to power Internet-of-things (IoT) sensors, freeing them from cables or batteries and thus making them especially useful for wearable devices. We demonstrate a giant positive thermopower of 17.0 millivolts per degree Kelvin in a flexible, quasi-solid-state, ionic thermoelectric material using synergistic thermodiffusion and thermogalvanic effects. The ionic thermoelectric material is a gelatin matrix modulated with ion providers (KCl, NaCl, and KNO3) for thermodiffusion effect and a redox couple [Fe(CN)6 4-/Fe(CN)6 3-] for thermogalvanic effect. A proof-of-concept wearable device consisting of 25 unipolar elements generated more than 2 volts and a peak power of 5 microwatts using body heat. This ionic gelatin shows promise for environmental heat-to-electric energy conversion using ions as energy carriers.

Rational Design of Reversible Redox Shuttle for Highly Efficient Light-Driven Microswimmer.

The light-driven micro/nanomotor (LMNM) is machinery that harvests photon energy and generates self-propulsion in varieties of liquid media. Though visions are made that these tiny swimming machines can serve future medicine for accurate drug delivery and noninvasive microsurgery, their biomedical application is still impeded by the insufficient propulsion efficiency. Here we provide a holistic model of LMNM by considering (i) photovoltaic, (ii) electrochemical, and (iii) electrokinetic processes therein. Such a quantitative model revealed the pivotal role of reaction kinetics and diffusion properties of shuttle ions in the propulsion efficiency of LMNM. With the guidance of this model, a group of ferrocene-based reversible redox shuttles, which generate slow-diffusion ions, was identified, showcasing a high locomotion velocity of ∼500 µm/s (∼100 body length per second) at an ultralow concentration (70 µM). Owing to the in-depth understanding of the fundamental energy conversion processes in LMNM, we anticipate that the development of other high-performance supporting chemicals and LMNM systems will be greatly motivated, foreseeing the advent of LMNM systems with superior efficiency.