Water- and heat-activated dynamic passivation for perovskite photovoltaics.

Further improvements in perovskite solar cells (PSCs) require better control of ionic defects in the perovskite photoactive layer during the manufacturing stage and their usage1-5. Here, we report a living passivation strategy using a hindered urea/thiocarbamate bond6-8 Lewis acid-base material (HUBLA), where dynamic covalent bonds with water and heat-activated characteristics can dynamically heal the perovskite to ensure device performance and stability. Upon exposure to moisture or heat, HUBLA generates new agents and further passivates defects in the perovskite. This passivation strategy achieved high-performance devices with a power conversion efficiency (PCE) of 25.1%. HUBLA devices retained 94% of their initial PCE for approximately 1500 hours of aging at 85 °C in N2 and maintained 88% of their initial PCE after 1000 hours of aging at 85 °C and 30% relative humidity (RH) in air.

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.

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.

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.

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.

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.

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.

An Air Knife-Assisted Recrystallization Method for Ambient-Process Planar Perovskite Solar Cells and Its Dim-Light Harvesting.

The photovoltaic performance of perovskite solar cells is highly dependent on the control of morphology and crystallization of perovskite film, which usually requires a controlled atmosphere. Therefore, fully ambient fabrication is a desired technology for the development of perovskite solar cells toward real production. Here, an air-knife assisted recrystallization method is reported, based on a simple bath-immersion to prepare high-quality perovskite absorbers. The resulted film shows a strong crystallinity with pure domains and low trap-state density, which contribute to the device performance and stability. The proposed method can operate in a wide process window, such as variable relative humidity and bath-immersion conditions, demonstrating a power conversion efficiency over 19% and 27% under 1 sun and 500-2000 lux dim-light illumination respectively, which is among the highest performance of ambient-process perovskite solar cells.

Study of the growth mechanisms of nanoporous Ag flowers for non-enzymatic glucose detection.

Highly sensitive and selective non-enzymatic glucose detection was developed using nanoporous Ag flowers on a Ni substrate. The cyclic scanning electrodeposition (CSE) method was used to fabricate Ag flowers on a Ni substrate in an alkaline electrolyte. The nanoporous Ag flowers were then formed by repeated CSE in NaOH. The growth mechanisms of the nanoporous Ag flowers were systematically studied, and these mechanisms can be extended to the formation of other metal, bimetal or metal oxide. The synthesized three-dimensional nanoporous Ag flowers on the Ni substrate were used in the electro-oxidation of glucose, demonstrating a wide linear range (0.1 µM to 1 mM), fast response time (<2 s), low detection limit of 0.1 µM (S/N = 3) and a high sensitivity to detect glucose in the presence of uric acid (UA) and ascorbic acid (AA) at the level of their physiological concentrations. Apart from the nanoporous Ag flowers, the formation of a NiO thin layer on the Ni substrate during CSE also contributed to the high selectivity. This work indicates the potential for developing a fast, sensitive, selective and stable electrochemical sensor for diabetes diagnosis.

Tannic Acid/Fe3+ Nanoscaffold for Interfacial Polymerization: Toward Enhanced Nanofiltration Performance.

Conventional thin-film composite (TFC) membranes suffer from the trade-off relationship between permeability and selectivity, known as the "upper bound". In this work, we report a high performance thin-film composite membrane prepared on a tannic acid (TA)-Fe nanoscaffold (TFCn) to overcome such upper bound. Specifically, a TA-Fe nanoscaffold was first coated onto a polysulfone substrate, followed by performing an interfacial polymerization reaction between trimesoyl chloride (TMC) and piperazine (PIP). The TA-Fe nanoscaffold enhanced the uptake of amine monomers and provided a platform for their controlled release. The smaller surface pore size of the TA-Fe coated substrate further eliminated the intrusion of polyamide into the substrate pores. The resulting membrane TFCn showed a water permeability of 19.6 ± 0.5 L m2- h-1 bar-1, which was an order of magnitude higher than that of control TFC membrane (2.2 ± 0.3 L m-2 h-1 bar-1). The formation of a more order polyamide rejection layer also significantly enhanced salt rejection (e.g., NaCl, MgCl2, Na2SO4, and MgSO4) and divalent to monovalent ion selectivity (e.g., NaCl/MgSO4). Compared to conventional TFC nanofiltration membranes, the novel TFCn membrane successfully overcame the longstanding permeability and selectivity trade-off. The current work paves a new avenue for fabricating high performance TFC membranes.

Electric-Field-Tunable Conductivity in Graphene/Water and Graphene/Ice Systems.

This study demonstrates that the application of an external electrical potential to a phenyl-sulfonic functionalized graphene (SG)/water suspension distinctly enhances its electrical conductivity via the structural transition from isolated clusters to a 3D SG network. Microstructural and alternating current impedance spectroscopy studies indicate that the surface charge plays an important role in the state of dispersion and connectivity of the SG in the suspension due to the potential-dependent interactions with functional groups on the SG surface in the presence of an external electrical potential. In addition, the conductive SG/ice can be produced via liquid-solid phase transition of the SG/water suspension in the presence of an external electrical potential, which shows a one-order magnitude improvement in electrical conductivity compared with pure ice. The electric-field-tunable property advances the understanding of nanofluid systems and has many potential applications.

Temperature-dependent effect of percolation and Brownian motion on the thermal conductivity of TiO2-ethanol nanofluids.

Ethanol-based nanofluids have attracted much attention due to the enhancement in heat transfer and their potential applications in nanofluid-type fuels and thermal storage. Most research has been conducted on ethanol-based nanofluids containing various nanoparticles in low mass fraction; however, to-date such studies based on high weight fraction of nanoparticles are limited due to the poor stability problem. In addition, very little existing work has considered the inevitable water content in ethanol for the change of thermal conductivity. In this paper, the highly stable and well-dispersed TiO2-ethanol nanofluids of high weight fraction of up to 3 wt% can be fabricated by stirred bead milling, which enables the studies of thermal conductivity of TiO2-ethanol nanofluids over a wide range of operating temperatures. Our results provide evidence that the enhanced thermal conductivity is mainly contributed by the percolation network of nanoparticles at low temperatures, while it is in combination with both Brownian motion and local percolation of nanoparticle clustering at high temperatures.

"Thermal Charging" Phenomenon in Electrical Double Layer Capacitors.

Electrical double layer capacitors (EDLCs) are usually charged by applying a potential difference across the positive and negative electrodes. In this paper, we demonstrated that EDLCs can be charged by heating. An open circuit voltage of 80-300 mV has been observed by heating the supercapacitor to 65 °C. The charge generated at high temperature can be stored in the device after its returning to the room temperature, thus allowing the lighting up of LEDs by connecting the "thermally charged" supercapacitors in a series. The underlying mechanism is related to a thermo-electrochemical process that enhances the kinetics of Faradaic process at the electrode surface (e.g., surface redox reaction of functional group, or chemical adsorption/desorption of electrolyte ions) at higher temperature. Effects of "thermal charging" times, activation voltage, rate, and times on "thermally charged" voltage are studied and possible mechanisms are discussed.

High electrocatalytic and wettable nitrogen-doped microwave-exfoliated graphene nanosheets as counter electrode for dye-sensitized solar cells.

In this paper, high electrocatalytic and wettable nitrogen-doped microwave-exfoliated graphene (N-MEG) nanosheets are used as Pt-free counter electrode (CE) for dye-sensitized solar cells (DSSCs). A low cost solution-based process is developed by using cyanamide (NH2 CN) at room temperature and normal pressure. The pyrrolic and pyridinic N atoms are doped into the carbon conjugated lattice to enhance electrocatalytic activity. N-MEG film having N-doping active sites and large porosity provides a wettable surface to facilitate electrolyte diffusion so that improves fill factor. Moreover, the control of the air exposure time after completing N-MEG film is found to be crucial to obtain a reliable N-MEG CE. A high DSSC efficiency up to 7.18% can be achieved based on N-MEG CE, which is nearly comparable to conventional Pt CE.

Direct electroplated metallization on indium tin oxide plastic substrate.

Looking foward to the future where the device becomes flexible and rollable, indium tin oxide (ITO) fabricated on the plastic substrate becomes indispensable. Metallization on the ITO plastic substrate is an essential and required process. Electroplating is a cost-effective and high-throughput metallization process; however, the poor surface coverage and interfacial adhesion between electroplated metal and ITO plastic substrate limits its applications. This paper develops a new method to directly electroplate metals having strong adhesion and uniform deposition on an ITO plastic substrate by using a combination of 3-mercaptopropyl-trimethoxysilane (MPS) self-assembled monolayers (SAMs) and a sweeping potential technique. An impedance capacitive analysis supports the proposed bridging link model for MPS SAMs at the interface between the ITO and the electrolyte.

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.

Reliable contact fabrication on nanostructured Bi2Te3-based thermoelectric materials.

A cost-effective and reliable Ni-Au contact on nanostructured Bi2Te3-based alloys for a solar thermoelectric generator (STEG) is reported. The use of MPS SAMs creates a strong covalent binding and more nucleation sites with even distribution for electroplating contact electrodes on nanostructured thermoelectric materials. A reliable high-performance flat-panel STEG can be obtained by using this new method.

Thermal percolation in stable graphite suspensions.

Different from the electrical conductivity of conductive composites, the thermal conductivity usually does not have distinctive percolation characteristics. Here we report that graphite suspensions show distinct behavior in the thermal conductivity at the electrical percolation threshold, including a sharp kink at the percolation threshold, below which thermal conductivity increases rapidly while above which the rate of increase is smaller, contrary to the electrical percolation behavior. Based on microstructural and alternating current impedance spectroscopy studies, we interpret this behavior as a result of the change of interaction forces between graphite flakes when isolated clusters of graphite flakes form percolated structures. Our results shed light on the thermal conductivity enhancement mechanisms in nanofluids and have potential applications in energy systems.

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.

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.