Critical Effects of Insoluble Additives in Liquid Electrolytes for Metal Batteries.

Rechargeable metal batteries have received widespread attention due to their high energy density by using pure metal as the anode. However, there are still many fundamental problems that need to be solved before approaching practical applications. The critical ones are low charge/discharge current due to slow ion transport, short cycle lifetime due to poor anode/cathode stability, and unsatisfied battery safety. To tackle these problems, various strategies have been suggested. Among them, electrolyte additive is one of the most widely used strategies. Most of the additives currently studied are soluble, but their reliability is questionable, and they can easily affect the electrochemical process, causing unwanted battery performance decline. On the contrary, insoluble additives with excellent chemical stability, high mechanical strength, and dimensional tunability have attracted considerable research exploration recently. However, there is no timely review on insoluble additives in metal batteries yet. This review summarizes various functions of insoluble additives: ion transport modulation, metal anode protection, cathode amelioration, as well as battery safety enhancement. Future research directions and challenges for insoluble solid additives are also proposed. It is expected this review will stimulate inspiration and arouse extensive studies on further improvement in the overall performance of metal batteries.

Recent advances in conductive hydrogels: classifications, properties, and applications.

Hydrogel-based conductive materials for smart wearable devices have attracted increasing attention due to their excellent flexibility, versatility, and outstanding biocompatibility. This review presents the recent advances in multifunctional conductive hydrogels for electronic devices. First, conductive hydrogels with different components are discussed, including pure single network hydrogels based on conductive polymers, single network hydrogels with additional conductive additives (i.e., nanoparticles, nanowires, and nanosheets), double network hydrogels based on conductive polymers, and double network hydrogels with additional conductive additives. Second, conductive hydrogels with a variety of functionalities, including self-healing, super toughness, self-growing, adhesive, anti-swelling, antibacterial, structural color, hydrophobic, anti-freezing, shape memory and external stimulus responsiveness are introduced in detail. Third, the applications of hydrogels in flexible devices are illustrated (i.e., strain sensors, supercapacitors, touch panels, triboelectric nanogenerator, bioelectronic devices, and robot). Next, the current challenges facing hydrogels are summarized. Finally, an imaginative but reasonable outlook is given, which aims to drive further development in the future.

In Operando Neutron Scattering Multiple-Scale Studies of Lithium-Ion Batteries.

Real-time observation of the electrochemical mechanistic behavior at various scales offers new insightful information to improve the performance of lithium-ion batteries (LIBs). As complementary to the X-ray-based techniques and electron microscopy-based methodologies, neutron scattering provides additional and unique advantages in materials research, owing to the different interactions with atomic nuclei. The non-Z-dependent elemental contrast, in addition to the high penetration ability and weak interaction with matters, makes neutron scattering an advanced probing tool for the in operando mechanistic studies of LIBs. The neutron-based techniques, such as neutron powder diffraction, small-angle neutron scattering, neutron reflectometry, and neutron imaging, have their distinct functionalities and characteristics regimes. These result in their scopes of application distributed in different battery components and covering the full spectrum of all aspects of LIBs. The review surveys the state-of-the-art developments of real-time investigation of the dynamic evolutions of electrochemically active compounds at various scales using neutron techniques. The atomic-scale, the mesoscopic-scale, and at the macroscopic-scale within LIBs during electrochemical functioning provide insightful information to battery researchers. The authors envision that this review will popularize the applications of neutron-based techniques in LIB studies and furnish important inspirations to battery researchers for the rational design of the new generation of LIBs.

Bimetallic-MOF-Derived ZnxCo3-xO4/Carbon Nanofiber Composited Sorbents for High-Temperature Coal Gas Desulfurization.

Desulfurization sorbent with a high active component utilization is of importance for the removal of H2S from coal gas at high temperatures. Thus, the hypothesis for producing ZnxCo3-xO4/carbon nanofiber sorbents via the combinations of electrospinning, in situ hydrothermal growth, and carbonization technique has been rationally constructed in this study. ZnxCo3-xO4 nanoparticles derived from metal-organic frameworks are uniformly loaded on the electrospun carbon nanofibers (CNFs) with high dispersion. ZnxCo3-xO4/CNFs sorbents possess the highest breakthrough sulfur adsorption capacity (12.4 g S/100 g sorbent) and an excellent utilization rate of the active component (83.2%). The excellent performance of ZnxCo3-xO4/CNFs can be attributed to the synergetic effect of the hierarchical structure and widely distributed ZnxCo3-xO4 on the CNFs supporter. The decomposition of Zn/Co-ZIFs not only generates the nucleus of oxides but also realizes their physical isolation through the formation of carbon grids on the surface of CNFs, avoiding the aggregation of oxides. Furthermore, ZnxCo3-xO4/CNFs sorbents show an overwhelming superiority over the ZnO/CNFs sorbent, which is attributed to the introduction of Co and then the promotion of the stability of Zn at high temperatures. The presence of Co also accelerates the adsorption of H2S on the active site of the oxide surface. The presented method is beneficial for promoting desulfurization performances and producing sorbents with high utilization of active components.

2D Hybrid Halide Perovskites: Structure, Properties, and Applications in Solar Cells.

2D metal-halide perovskites have attracted intense research interest due to superior long-term stability under ambient environments. Compared to their 3D analog, the alternate arrangement of organic and inorganic layers leads to forming a multilayer quantum well (MQW), which endows 2D perovskites with anisotropic optoelectronic properties. In addition, the spacer layer functions as a hydrophobic barrier to effectively prevent 2D perovskite films from ion migration and moisture penetrating, thus realizing outstanding stability. Recently, 2D perovskites have been widely developed with abundant species. The stunning photovoltaic performance with the coexistence of long-term stability and high-power conversion efficiency (PCE) has been realized in 2D perovskite solar cells (PSCs), which paves an avenue for commercialization of PSCs. This review begins with an introduction of crystal structure and crystallization kinetics to illustrate the unique layer characters in 2D perovskites. Then, electron structure, excitons, dielectric confinement, and intrinsic stability properties are discussed in detail. Next, the photovoltaic performance based on recent Ruddlesden-Popper (RP), Dion-Jacobson (DJ), and alternating cations in the interlayer (ACI) phase 2D-PSCs is comprehensively summarized. Finally, the confronting challenges and strategies toward structural design and optoelectronic studies of 2D perovskites are proposed to offer insight into the advanced underlying properties of this family of materials.

Thermal-Responsive and Fire-Resistant Materials for High-Safety Lithium-Ion Batteries.

As one of the most efficient electrochemical energy storage devices, the energy density of lithium-ion batteries (LIBs) has been extensively improved in the past several decades. However, with increased energy density, the safety risk of LIBs becomes higher too. The frequently occurred battery accidents worldwide remind us that safeness is a crucial requirement for LIBs, especially in environments with high safety concerns like airplanes and military platforms. It is generally recognized that the catastrophic thermal runaway (TR) event is the major cause of LIBs related accidents. Tremendous efforts have been devoted to coping with the TR concerns in LIBs, and thus enhance battery safety. This review first gives an introduction to the fundamentals of LIBs and the origins of safety issues. Then, the authors summarize the recent advances to improve the safety of LIBs with a unique focus on thermal-responsive and fire-resistant materials. Finally, a perspective is proposed to guide future research directions in this field. It is anticipated this review will stimulate inspiration and arouse extensive studies on further improvement in battery safety.

Commercialization-Driven Electrodes Design for Lithium Batteries: Basic Guidance, Opportunities, and Perspectives.

Current lithium-ion battery technology is approaching the theoretical energy density limitation, which is challenged by the increasing requirements of ever-growing energy storage market of electric vehicles, hybrid electric vehicles, and portable electronic devices. Although great progresses are made on tailoring the electrode materials from methodology to mechanism to meet the practical demands, sluggish mass transport, and charge transfer dynamics are the main bottlenecks when increasing the areal/volumetric loading multiple times to commercial level. Thus, this review presents the state-of-the-art developments on rational design of the commercialization-driven electrodes for lithium batteries. First, the basic guidance and challenges (such as electrode mechanical instability, sluggish charge diffusion, deteriorated performance, and safety concerns) on constructing the industry-required high mass loading electrodes toward commercialization are discussed. Second, the corresponding design strategies on cathode/anode electrode materials with high mass loading are proposed to overcome these challenges without compromising energy density and cycling durability, including electrode architecture, integrated configuration, interface engineering, mechanical compression, and Li metal protection. Finally, the future trends and perspectives on commercialization-driven electrodes are offered. These design principles and potential strategies are also promising to be applied in other energy storage and conversion systems, such as supercapacitors, and other metal-ion batteries.

Mechanically Reinforced Localized Structure Design to Stabilize Solid-Electrolyte Interface of the Composited Electrode of Si Nanoparticles and TiO2 Nanotubes.

Silicon anode with extremely high theoretical specific capacity (≈4200 mAh g-1 ), experiences huge volume changes during Li-ion insertion and extraction, causing mechanical fracture of Si particles and the growth of a solid-electrolyte interface (SEI), which results in a rapid capacity fading of Si electrodes. Herein, a mechanically reinforced localized structure is designed for carbon-coated Si nanoparticles (C@Si) via elongated TiO2 nanotubes networks toward stabilizing Si electrode via alleviating mechanical strain and stabilizing the SEI layer. Benefited from the rational localized structure design, the carbon-coated Si nanoparticles/TiO2 nanotubes composited electrode (C@Si/TiNT) exhibits an ideal electrode thickness swelling, which is lower than 1% after the first cycle and increases to about 6.6% even after 1600 cycles. While for traditional C@Si/carbon nanotube composited electrode, the initial swelling ratio is about 16.7% and reaches ≈190% after 1600 cycles. As a result, the C@Si/TiNT electrode exhibits an outstanding capacity of 1510 mAh g-1 at 0.1 A g-1 with high rate capability and long-time cycling performance with 95% capacity retention after 1600 cycles. The rational design on mechanically reinforced localized structure for silicon electrode will provide a versatile platform to solve the current bottlenecks for other alloyed-type electrode materials with large volume expansion toward practical applications.

Fluoroethylene Carbonate Enabling a Robust LiF-rich Solid Electrolyte Interphase to Enhance the Stability of the MoS2 Anode for Lithium-Ion Storage.

As a high-capacity anode for lithium-ion batteries (LIBs), MoS2 suffers from short lifespan that is due in part to its unstable solid electrolyte interphase (SEI). The cycle life of MoS2 can be greatly extended by manipulating the SEI with a fluoroethylene carbonate (FEC) additive. The capacity of MoS2 in the electrolyte with 10 wt % FEC stabilizes at about 770 mAh g-1 for 200 cycles at 1 A g-1 , which far surpasses the FEC-free counterpart (ca. 40 mAh g-1 after 150 cycles). The presence of FEC enables a robust LiF-rich SEI that can effectively inhibit the continual electrolyte decomposition. A full cell with a LiNi0.5 Co0.3 Mn0.2 O2 cathode also gains improved performance in the FEC-containing electrolyte. These findings reveal the importance of controlling SEI formation on MoS2 toward promoted lithium storage, opening a new avenue for developing metal sulfides as high-capacity electrodes for LIBs.

Understanding the Role of Dynamic Wettability for Condensate Microdrop Self-Propelling Based on Designed Superhydrophobic TiO2 Nanostructures.

The ability to release the adhered drops on superhydrophobic surfaces is very important for self-cleaning, antifrosting/icing, microfluidic device, and heat transfer applications. In this paper, three types of in situ electrochemical anodizing TiO2 nanostructure films are rationally designed and fabricated on titanium substrates with special superwettability, viz., TiO2 nanotube arrays, irregular TiO2 nanotube arrays, and hierarchical TiO2 particle arrays (HTPA), and their corresponding behavior in condensate microdrop self-propelling (CMDSP) is investigated. Compared to the flat titanium counterpart, all three types of rough TiO2 samples demonstrate a uniform distribution of smaller microscale droplets. Among the treated surfaces, the HTPA possesses the highest condensate density, and more than 80% of the droplets possess a diameter below 10 µm. Theoretical analysis indicates that the feature is mainly due to the morphology and structure induced extremely low droplet adhesion on super-antiwetting TiO2 hierarchical surfaces, where the excess surface energy released from the migration leads to the self-propelling of merged microdrop. This work offers a way to rationally construct CMDSP surfaces with excellent self-cleaning, antifrosting/icing ability, and enhanced condensation heat transfer efficiency.

Immobilization of Pt Nanoparticles via Rapid and Reusable Electropolymerization of Dopamine on TiO2 Nanotube Arrays for Reversible SERS Substrates and Nonenzymatic Glucose Sensors.

Inspired by mussel-adhesion phenomena in nature, polydopamine (PDA) coatings are a promising route to multifunctional platforms for decorating various materials. The typical self-polymerization process of dopamine is time-consuming and the coatings of PDA are not reusable. Herein, a reusable and time-saving strategy for the electrochemical polymerization of dopamine (EPD) is reported. The PDA layer is deposited on vertically aligned TiO2 nanotube arrays (NTAs). Owing to the abundant catechol and amine groups in the PDA layer, uniform Pt nanoparticles (NPs) are deposited onto the TiO2 NTAs and can effectively prevent the recombination of electron-hole pairs generated from photo-electrocatalysis and transfer the captured electrons to participate in the photo-electrocatalytic reaction process. Compared with pristine TiO2 NTAs, the as-prepared Pt@TiO2 NTA composites exhibit surface-enhanced Raman scattering sensitivity for detecting rhodamine 6G and display excellent UV-assisted self-cleaning ability, and also show promise as a nonenzymatic glucose biosensor. Furthermore, the mussel-inspired electropolymerization strategy and the fast EPD-reduced nanoparticle decorating process presented herein can be readily extended to various functional substrates, such as conductive glass, metallic oxides, and semiconductors. It is the adaptation of the established PDA system for a selective, robust, and generalizable sensing system that is the emphasis of this work.

Recent Advances in TiO2 -Based Nanostructured Surfaces with Controllable Wettability and Adhesion.

Bioinspired surfaces with special wettability and adhesion have attracted great interest in both fundamental research and industry applications. Various kinds of special wetting surfaces have been constructed by adjusting the topographical structure and chemical composition. Here, recent progress of the artificial superhydrophobic surfaces with high contrast in solid/liquid adhesion has been reviewed, with a focus on the bioinspired construction and applications of one-dimensional (1D) TiO2-based surfaces. In addition, the significant applications related to artificial super-wetting/antiwetting TiO2-based structure surfaces with controllable adhesion are summarized, e.g., self-cleaning, friction reduction, anti-fogging/icing, microfluidic manipulation, fog/water collection, oil/water separation, anti-bioadhesion, and micro-templates for patterning. Finally, the current challenges and future prospects of this renascent and rapidly developing field, especially with regard to 1D TiO2-based surfaces with special wettability and adhesion, are proposed and discussed.

Fast Energy Storage of SnS2 Anode Nanoconfined in Hollow Porous Carbon Nanofibers for Lithium-Ion Batteries.

The development of conversion-typed anodes with ultrafast charging and large energy storage is quite challenging due to the sluggish ions/electrons transfer kinetics in bulk materials and fracture of the active materials. Herein, the design of porous carbon nanofibers/SnS2 composite (SnS2 @N-HPCNFs) for high-rate energy storage, where the ultrathin SnS2 nanosheets are nanoconfined in N-doped carbon nanofibers with tunable void spaces, is reported. The highly interconnected carbon nanofibers in three-dimensional (3D) architecture provide a fast electron transfer pathway and alleviate the volume expansion of SnS2 , while their hierarchical porous structure facilitates rapid ion diffusion. Specifically, the anode delivers a remarkable specific capacity of 1935.50 mAh g-1 at 0.1 C and excellent rate capability up to 30 C with a specific capacity of 289.60 mAh g-1 . Meanwhile, at a high rate of 20 C, the electrode displays a high capacity retention of 84% after 3000 cycles and a long cycle life of 10 000 cycles. This work provides a deep insight into the construction of electrodes with high ionic/electronic conductivity for fast-charging energy storage devices.

Dual-strategy engineered nickel phosphide for achieving efficient hydrazine-assisted hydrogen production in seawater.

Electrocatalytic hydrogen production in seawater to alleviate freshwater shortage pressures is promising, but is hindered by the sluggish oxygen evolution reaction and detrimental chloride electrochemistry. Herein, a dual strategy approach of Fe-doping and CeO2-decoration in nickel phosphide (Fe-Ni2P/CeO2) is rationally designed to achieve superior bifunctional catalytic performance for the hydrogen evolution reaction (HER) and hydrazine oxidation reaction (HzOR) in seawater. Notably, the two-electrode Fe-Ni2P/CeO2-based hybrid seawater electrolyzer realizes energy-efficient and chlorine-free hydrogen production with ultralow cell voltages of 0.051 and 0.597 V at 10 and 400 mA cm-2, which are significantly lower than those needed in the hydrazine-free seawater electrolyzer. Density functional theory calculations manifest that the combination of Fe doping and heterointerface construction between Fe-Ni2P and CeO2 can adjust the electronic structure of the Ni2P and optimize the water dissociation barrier and hydrogen adsorption free energy, leading to improvement of the intrinsic catalytic performance. This route affords a feasible solution for future large-scale hydrogen generation using abundant ocean water.

Rational Construction of MOF-Derived Porous ZnTiO3/TiO2 Heterostructured Photocatalysts with Remarkable Photocatalytic Performance.

TiO2 has been widely used in photodegradation of pollutants, but it suffers from inferior photocatalytic performance under solar light illumination. Thus, novel porous ZnTiO3/TiO2 heterostructured photocatalysts are constructed by hydrothermal and carbonization techniques using ZIF-8 as a sacrificial template. After coating with TiO2, ZIF-8 nanocubes are selectively etched and subsequently coprecipitated with Ti ions during the hydrothermal process. Thereafter, the pores generated from carbonized ZIF-8 provide a large specific surface area and abundant active reaction sites for photocatalysis after annealing, producing stable ZnTiO3/TiO2 nanocomposites. Thus, porous ZnTiO3/TiO2 heterostructured photocatalysts exhibit excellent photocatalytic performance under solar light irradiation due to the boosted electron-hole separation/transfer. The kinetic constant of ZnTiO3/TiO2 nanocomposites (4.66 × 10-1 min-1) is almost 100 and 3.7 times higher than that of self-degradation (4.69 × 10-3 min-1) and TiO2 (1.27 × 10-1 min-1), respectively. This facile strategy provides a deep insight into synthesizing heterostructured photocatalysts with high efficiency in the field of environmental remediation.

Hierarchical Mn-Ni2P/NiFe LDH nanosheet arrays as an efficient bifunctional electrocatalyst for energy-saving hydrogen production via urea electrolysis.

Hierarchical Mn-Ni2P/NiFe LDH arrays were developed as a self-supported electrode. Because of the synergistic effect and self-supported structure, it presents brilliant bifunctional catalytic activities for the HER and UOR. Surprisingly, the voltage of a urea electrolytic cell coupling the HER with the UOR was as low as 1.494 V at 10 mA cm-2.

Durable modulation of Zn(002) plane deposition via reproducible zincophilic carbon quantum dots towards low N/P ratio zinc-ion batteries.

Aqueous zinc-ion batteries (ZIBs) are promising candidates for next-generation energy storage systems due to their intrinsic safety, environmental friendliness, and low cost. However, the uncontrollable Zn dendrite growth during cycling is still a critical challenge for the long-term operation of ZIBs, especially under harsh lean-Zn conditions. Herein, we report nitrogen and sulfur-codoped carbon quantum dots (N,S-CDs) as zincophilic electrolyte additives to regulate the Zn deposition behaviors. The N,S-CDs with abundant electronegative groups can attract Zn2+ ions and co-deposit with Zn2+ ions on the anode surface, inducing a parallel orientation of the (002) crystal plane. The deposition of Zn preferentially along the (002) crystal direction fundamentally avoids the formation of Zn dendrites. Moreover, the co-depositing/stripping feature of N,S-CDs under an electric field force ensures the reproducible and long-lasting modulation of the Zn anode stability. Benefiting from these two unique modulation mechanisms, stable cyclability of the thin Zn anodes (10 and 20 µm) at a high depth of discharge (DOD) of 67% and high Zn||Na2V6O16·3H2O (NVO, 11.52 mg cm-2) full-cell energy density (144.98 W h Kg-1) at a record-low negative/positive (N/P) capacity ratio of 1.05 are achieved using the N,S-CDs as an additive in ZnSO4 electrolyte. Our findings not only offer a feasible solution for developing actual high-energy density ZIBs but also provide in-depth insights into the working mechanism of CDs in regulating Zn deposition behaviors.

Smart surfaces with reversibly switchable wettability: Concepts, synthesis and applications.

As a growing hot research topic, manufacturing smart switchable surfaces has attracted much attention in the past a few years. The state-of-the-art study on reversibly switchable wettability of smart surfaces has been presented in this systematic review. External stimuli are brought about to render the alteration in chemical conformation and surface morphology to drive the wettability switch. Here, starting from the fundamental theories related to the surfaces wetting principles, highlights on different triggers for switchable wettability, such as pH, light, ions, temperature, electric field, gas, mechanical force, and multi-stimuli are discussed. Different applications that have various wettability requirement are targeted, including oil-water separation, droplets manipulation, patterning, liquid transport, and so on. This review aims to provide a deep insight into responsive interfacial science and offer guidance for smart surface engineering. It ends with a summary of current challenges, future opportunities, and potential solutions on smart switch of wettability on superwetting surfaces.

Surface Passivation Using 2D Perovskites toward Efficient and Stable Perovskite Solar Cells.

3D perovskite solar cells (PSCs) have shown great promise for use in next-generation photovoltaic devices. However, some challenges need to be addressed before their commercial production, such as enormous defects formed on the surface, which result in severe SRH recombination, and inadequate material interplay between the composition, leading to thermal-, moisture-, and light-induced degradation. 2D perovskites, in which the organic layer functions as a protective barrier to block the erosion of moisture or ions, have recently emerged and attracted increasing attention because they exhibit significant robustness. Inspired by this, surface passivation by employing 2D perovskites deposited on the top of 3D counterparts has triggered a new wave of research to simultaneously achieve higher efficiency and stability. Herein, we exploited a vast amount of literature to comprehensively summarize the recent progress on 2D/3D heterostructure PSCs using surface passivation. The review begins with an introduction of the crystal structure, followed by the advantages of the combination of 2D and 3D perovskites. Then, the surface passivation strategies, optoelectronic properties, enhanced stability, and photovoltaic performance of 2D/3D PSCs are systematically discussed. Finally, the perspectives of passivation techniques using 2D perovskites to offer insight into further improved photovoltaic performance in the future are proposed.

A Breathable Knitted Fabric-Based Smart System with Enhanced Superhydrophobicity for Drowning Alarming.

Wearable strain sensors have aroused increasing interest in human motion monitoring, even for the detection of small physiological signals such as joint movement and pulse. Stable monitoring of underwater human motion for a long time is still a notable challenge, as electronic devices can lose their effectiveness in a wet environment. In this study, a superhydrophobic and conductive knitted polyester fabric-based strain sensor was fabricated via dip coating of graphene oxide and polydimethylsiloxane micro/nanoparticles. The water contact angle of the obtained sample was 156°, which was retained above 150° under deformation (stretched to twice the original length or bent to 80°). Additionally, the sample exhibited satisfactory mechanical stability in terms of superhydrophobicity and conductivity after 300 abrasion cycles and 20 accelerated washing cycles. In terms of sensing performance, the strain sensor showed a rapid and obvious response to different deformations such as water vibration, underwater finger bending, and droplet shock. With the good combination of superhydrophobicity and conductivity, as well as the wearability and stretchability of the knitted polyester fabric, this wireless strain sensor connected with Bluetooth can allow for the remote monitoring of water sports, e.g., swimming, and can raise an alert under drowning conditions.