Anomalous Channel‐Length Dependence in Nanofluidic Osmotic Energy Conversion

Recent advances in materials science and nanotechnology have lead to considerable interest in constructing ion‐channel‐mimetic nanofluidic systems for energy conversion and storage. The conventional viewpoint suggests that to gain high electrical energy, the longitudinal dimension of the nanochannels (L) should be reduced so as to bring down the resistance for ion transport and provide high ionic flux. Here, counterintuitive channel‐length dependence is described in nanofluidic osmotic power generation. For short nanochannels (with length L < 400 nm), the converted electric power persistently decreases with the decreasing channel length, showing an anomalous, non‐Ohmic response. The combined thermodynamic analysis and numerical simulation prove that the excessively short channel length impairs the charge selectivity of the nanofluidic channels and induces strong ion concentration polarization. These two factors eventually undermine the osmotic power generation and its energy conversion efficiency. Therefore, the optimal channel length should be between 400 and 1000 nm in order to maximize the electric power, while balancing the efficiency. These findings reveal the importance of a long‐overlooked element, the channel length, in nanofluidic energy conversion and provide guidance to the design of high‐performance nanofluidic energy devices.     

Heterogeneous MXene/PS-b-P2VP Nanofluidic Membranes with Controllable Ion Transport for Osmotic Energy Conversion

Membrane-based osmotic power harvesting is a strategy for sustainable power generation. 2D nanofluids with high ion conductivity and selectivity are emerging candidates for osmotic energy conversion. However, the ion diffusion under nanoconfinement is hindered by homogeneous 2D membranes with monotonic charge regulation and severe concentration polarization, which results in an undesirable power conversion performance. Here, an asymmetric nanochannel membrane with a two-layered structure is reported, in which the angstrom-scale channels of 2D transition metal carbides/nitrides (MXenes) act as a screening layer for controlling ion transport, and the nanoscale pores of the block copolymer (BCP) are the pH-responsive arrays with an ordered nanovoid structure. The heterogeneous nanofluidic device exhibits an asymmetric charge distribution and enlarged 1D BCP porosity under acidic and alkaline conditions, respectively; this improves the gradient-driven ion diffusion, allowing a high-performance osmotic energy conversion with a power density of up to 6.74 W m⁻² by mixing artificial river water and seawater. Experiments and theoretical simulations indicate that the tunable asymmetric heterostructure contributes to impairing the concentration polarization and enhancing the ion flux. This efficient osmotic energy generator can advance the fundamental understanding of the MXene-based heterogeneous nanofluidic devices as a paradigm for membrane-based energy conversion technologies.     

Bamboo-Membrane Inspired Multilevel Ultrafast Interlayer Ion Transport for Superior Volumetric Energy Storage

Interlayer transport of charges and carriers of 2D nanomaterials is a critical parameter that governs the material and device performance in energy storage applications. Inspired by multilevel natural bamboo-membrane with ultrafast water and electrolyte transport properties to support its super-rapid growth rate, 2D–2D multilevel heterostructured graphene-based membranes with tailored gradient interlayer channels are rationally designed for achieving ultrafast interlayer ion transport. The bioinspired heterostructured membranes possess multilevel interlayer spacing distributions, where the closely packed layers with sub-nanosized interlayer space provide ultrafast confined interlayer ion transport, while the loosely stacked outer layers consisting of open channels with large distances up to few micrometres are favorable for rapid wetting and penetration of liquid electrolytes. The combination of advantages of large-size open channels and nanosized confined channels offers ultrafast electrolyte wetting and permeation and interlayer ion transport and provide the devices with superior volumetric capacity as free-standing electrodes for rechargeable batteries.     

High-Strength,Thin PBO Nanofiber Membrane with Long-Term Stability for Osmotic Energy Conversion

Ion-selective membrane embedded in a reverse electrodialysis system can achieve the conversion of osmotic energy into electricity. However, the ingenious design and development of pure polymer membranes that simultaneously satisfy excellent mechanical strength, long-term stability, high power density, and increased testing area is a crucial challenge. Here, high-strength, thin PBO nanofiber membranes (PBONM) with 3D nanofluidic channels and a thickness of 0.81 µm are prepared via a simple vacuum-assisted filtration technology. The thin PBONM exhibits excellent mechanical properties: stress of 235.8 MPa and modulus of 16.96 GPa, outperforming the state-of-the-art nanofluidic membranes. The obtained PBONM reveals surface-charge-governed ion transport behavior and high ion selectivity of 0.88 at a 50-fold concentration gradient. The PBO membrane-based generator delivers a power density of 7.7 and 40.2 W m⁻² at 50-fold and 500-fold concentration gradient. Importantly, this PBONM presents excellent stability in response to different external environments including various saline solutions, pH, and temperature. In addition, the maximum power density of PBONM reaches up to 5.9 W m⁻² under an increased testing area of 0.79 mm², exceeding other membrane-based generators with comparable testing areas. This work paves the way for constructing high-strength fiber nanofluidic membranes for highly efficient osmotic energy conversion.     

In Situ Growth of Imine-Bridged Anion-Selective COF/AAO Membrane for Ion Current Rectification and Nanofluidic Osmotic Energy Conversion

Facing the energy crisis, using the salinity gradient between seawater and freshwater for osmotic energy conversion is a direct way to obtain energy. So far, most nanofluidic membranes utilized for osmotic energy generation are cation-selective. Given that both anion- and cation-selective membranes have the identical importance for energy conversion devices, it is of great significance to develop anion-selective membranes. Herein, an anion-selective membrane is synthesized by in situ growth of imine-bridged covalent organic framework (COF) on ordered anodic aluminum oxide (AAO) at room temperature. The imine groups and residual amino groups of COF can combine with protons in neutral solution, enabling the COF positively charged and efficiently transport of anions. Particularly, due to the asymmetry in the charge and structure of COF/AAO, the as-prepared membrane exhibits excellent ionic current rectification property, which can inhibit ion concentration polarization effectively and possess high ion selectivity and permeability. Using the present COF/AAO membrane, salinity gradient energy can be successfully harvested from solutions with high salt content, and the output power density reached 17.95W m⁻² under a 500-fold salinity gradient. The study provides a new avenue for construction and application of anion-selective membranes in the smart ion transport and efficient energy conversion.     

Bio‐Inspired Photonic Materials: Prototypes and Structural Effect Designs for Applications in Solar Energy Manipulation

Natural creatures have evolved elaborate photonic nanostructures on multiple scales and dimensions in a hierarchical, organized way to realize controllable absorption, reflection, or transmitting the desired wavelength of the solar spectrum. A bio‐inspired strategy is a powerful and promising way for solar energy manipulation. This feature article presents the state‐of‐the‐art progress on bio‐inspired photonic materials on this particular application. The article first briefly recalls the physical origins of natural photonic effects and catalogues the typical natural photonic prototypes including light harvesting, broadband reflection, selective reflection, and UV/IR response. Next, typical applications are categorized into two primary areas: solar energy utilization and reflection. Recent advances including solar‐to‐electricity, solar‐to‐fuels, solar‐thermal (e.g., photothermal converters, infrared detectors, thermoelectric materials, smart windows, and solar steam generation) are highlighted in the first part. Meanwhile, solar energy reflection involving infrared stealth, radiative cooling, and micromirrors are also addressed. In particular, this article focuses on bioinspired design principles, structural effects on functions, and future trends. Finally, the main challenges and prospects for the next generation of bioinspired photonic materials are discussed, including new design concepts, emerging ideas, and possible strategies.     

Engineering the Thermal Conductivity of Functional Phase‐Change Materials for Heat Energy Conversion,Storage, and Utilization

Thermal energy storage technologies based on phase‐change materials (PCMs) have received tremendous attention in recent years. These materials are capable of reversibly storing large amounts of thermal energy during the isothermal phase transition and offer enormous potential in the development of state‐of‐the‐art renewable energy infrastructure. Thermal conductivity plays a vital role in regulating the thermal charging and discharging rate of PCMs and improving the heat‐utilization efficiency. The strategies for tuning the thermal conductivity of PCMs and their potential energy applications, such as thermal energy harvesting and storage, thermal management of batteries, thermal diodes, and other forms of energy utilization, are summarized systematically. Furthermore, a research perspective is given to highlight emerging research directions of engineering advanced functional PCMs for energy applications.     

Insights of Heteroatoms Doping-Enhanced Bifunctionalities on Carbon Based Energy Storage and Conversion

Ever-developing energy storage technologies demand the pursuit of advanced materials with multiple functionalities. Recent studies revealed that multiple heteroatom-doped carbon has been wildly used for bi-functional or even tri-functional energy storage and conversion. However, few efforts have been made to uncover the origin of multi-functionalities. Herein, a nitrogen, phosphorus, and sulfur tri-doped carbon is designed in this work with large porosity, rich heteroatoms doping and high mass density, exhibiting excellent bifunctionalities on supercapacitors and oxygen reduction reaction. Importantly, the density functional theory calculations demonstrate the relevant co-doping and tri-doping generate more active sites on neighboring carbon atoms than single doping, and the same type of active sites may enhance bifunctionalities simultaneously. The present investigations provide a promising guidance on the design of multi-functional materials for future energy storage and conversion applications.     

Irradiation of Transition Metal Dichalcogenides Using a Focused Ion Beam: Controlled Single‐Atom Defect Creation

Manipulation and structural modifications of 2D materials for nanoelectronic and nanofluidic applications remain obstacles to their industrial‐scale implementation. Here, it is demonstrated that a 30 kV focused ion beam can be utilized to engineer defects and tailor the atomic, optoelectronic, and structural properties of monolayer transition metal dichalcogenides (TMDs). Aberration‐corrected scanning transmission electron microscopy is used to reveal the presence of defects with sizes from the single atom to 50 nm in molybdenum (MoS₂) and tungsten disulfide (WS₂) caused by irradiation doses from 10¹³ to 10¹⁶ ions cm^?2. Irradiated regions across millimeter‐length scales of multiple devices are sampled and analyzed at the atomic scale in order to obtain a quantitative picture of defect sizes and densities. Precise dose value calculations are also presented, which accurately capture the spatial distribution of defects in irradiated 2D materials. Changes in phononic and optoelectronic material properties are probed via Raman and photoluminescence spectroscopy. The dependence of defect properties on sample parameters such as underlying substrate and TMD material is also investigated. The results shown here lend the way to the fabrication and processing of TMD nanodevices.     

Electromagnetic Response and Energy Conversion for Functions and Devices in Low‐Dimensional Materials

Low‐dimensional materials have been long sought after for their particular electromagnetic (EM) functions, with promising applications in EM wave absorbing and shielding, communicating and imaging, sensing and detecting, driving and actuating, etc. Herein, across the whole EM spectrum, low‐dimensional EM functional materials and devices are highly focused on. The crystal engineering and function‐guiding features addressed relate to crystal and electronic structures, EM responses and properties, energy conversion, as well as EM wave absorbing and shielding. Moreover, insight is given into this rapidly broadening field, the main challenges are proposed and future directions are predicted.     

Photoinduced Directional Proton Transport through Printed Asymmetric Graphene Oxide Superstructures: A New Driving Mechanism under Full‐Area Light Illumination

2D‐material‐based membranes with densely packed sub‐nanometer‐height fluidic channels show exceptional transport properties, and have attracted broad research interest for energy‐, environment‐, and healthcare‐related applications. Recently, light‐controlled active transport of ionic species in abiotic materials have received renewed attention. However, its dependence on inhomogeneous or site‐specific illumination is a challenge for scalable application. Here, directional proton transport through printed asymmetric graphene oxide superstructures (GOSs) is demonstrated under full‐area illumination. The GOSs are composed of partially stacked graphene oxide multilayers formed by a two‐step direct ink writing process. The direction of the photoinduced proton current is determined by the position of top graphene oxide multilayers, which functions as a photogate to modulate the horizontal ion transport through the beneath lamellar nanochannels. This transport phenomenon unveils a new driving mechanism that, in asymmetric nanofluidic structures, the decay of local light intensity in depth direction breaks the balance of electric potential distribution in horizontal direction, and thus generates a photoelectric driving force for ion transport. Following this mechanism, the GOSs are developed into photonic ion transistors with three different gating modes. The asymmetrically printed photonic‐ionic devices provide fundamental elements for light‐harvesting nanofluidic circuits, and may find applications for artificial photosynthesis and artificial electric organs.     

Polyanion Sodium Vanadium Phosphate for Next Generation of Sodium‐Ion Batteries—A Review

Polyanion‐type sodium (Na) vanadium phosphate in the form of Na₃V₂(PO₄)₃ has demonstrated reasonably high capacity, good rate capability, and excellent cyclability. Two of three Na ions per formula can be deintercalated at a potential 3.4 V versus Na⁺/Na with oxidation of V^3+/4+. In the reversible process, two Na ions intercalate back resulting in a discharge capacity of 117.6 mAh g^?1. Further intercalation is possible but at a low potential of 1.4 V versus Na⁺/Na accompanied by vanadium reduction V^3+/2+, leading to a capacity of 60 mAh g^?1. Due to its marvelous electrochemical performance, it has attracted a lot of attention since its discovery in the 1990s. To develop truly useable polyanion‐type vanadium phosphate, better understanding of its crystal configuration, sodium ions' transportation, and electronic structure is essential. Therefore, this review only focuses on the inside of crystal configuration and electronic structure of polyanion‐type vanadium phosphate, Na₃V₂(PO₄)₃, since there are a few good reviews on various processing technologies.     

Layer‐by‐Layer Synthesis of Thick Mesoporous TiO2 Films with Vertically Oriented Accessible Nanopores and Their Application for Lithium‐Ion Battery Negative Electrodes

TiO₂ films of varying thicknesses (up to ≈1.0 µm) with vertically oriented, accessible 7–9 nm nanopores are synthesized using an evaporation‐induced self‐assembly layer‐by‐layer technique. The hypothesis behind the approach is that epitaxial alignment of hydrophobic blocks of surfactant templates induces a consistent, accessible mesophase orientation across a multilayer film, ultimately leading to continuous, vertically aligned pore channels. Characterization using grazing incidence X‐ray scattering, scanning electron microscopy, and impedance spectroscopy indicates that the pores are oriented vertically even in relatively thick films (up to 1 µm). These films contain a combination of amorphous and nanocrystalline anatase titania of value for electrochemical energy storage. When applied as negative electrodes in lithium‐ion batteries, a capacity of 254 mAh g^?1 is obtained after 200 cycles for a single‐layer TiO₂ film prepared on modified substrate, higher than on unmodified substrate or nonporous TiO₂ film, due to the high accessibility of the vertically oriented channels in the films. Thicker films on modified substrate have increased absolute capacity because of higher mass loading but a reduced specific capacity because of transport limitations. These results suggest that the multilayer epitaxial approach is a viable way to prepare high capacity TiO₂ films with vertically oriented continuous nanopores.     

Fabrication of Bio‐Inspired 2D MOFs/PAA Hybrid Membrane for Asymmetric Ion Transport

Biological ion channels are known as membrane proteins which can turn on and off under environmental stimulus to regulate ion transport and energy conversion. Rapid progress made in biological ion channels provides inspiration for developing artificial nanochannels to mimic the structures and functions of ion transport systems and energy conversion in biological ion channels. Due to the advantages of abundant pore channels, metal–organic frameworks (MOFs) have become competitive materials to control the nanofluidic transport. Herein, a facile in situ synthesis method is developed to prepare hybrid nanochannels constructed by 2D MOFs and porous anodic aluminum (PAA). The introduction of asymmetries in the chemical composition and surface charge properties gives the hybrid outstanding ion current rectification properties and excellent ion selectivity. A power density of 1.6 W m^?2 is achieved by integrating it into a salinity‐gradient‐driven device. With advantages of facile fabrication method and high ion selectivity, the prepared 2D MOFs/PAA hybrid membrane offers a promising candidate for power conversion and water desalination.     

Shape Selectivity in Adsorption of n‐ and Iso‐alkanes on a Zeotile‐2 Microporous/Mesoporous Hybrid and Mesoporous MCM‐48

The adsorption of linear and branched C5–C9 alkanes in the temperature range 50–250 °C on mesoporous MCM‐48 material and its microporous/mesoporous variant Zeotile‐2 at low surface coverage is investigated using the pulse chromatographic technique. On MCM‐48, the differences in adsorption between linear and branched alkanes are merely a result of differences in volatility, indicating that the MCM‐48 material does not present shape‐selective adsorption sites. On Zeotile‐2, there is a preferential adsorption of linear over branched alkanes. The difference arises from a difference in adsorption entropy rather than enthalpy. Upon their adsorption on Zeotile‐2 branched alkanes lose relatively more entropy than their linear isomers do. Zeolitic molecular pockets embedded in the walls of the mesoporous Zeotile‐2 impose steric constraints on the bulky isoalkanes. Zeotile‐2 combines adsorption properties from microporous and mesoporous materials. Compared to the nitrogen molecule, linear and branched C5–C9 alkanes are superior probes for investigating micropores and micropockets in hierarchical materials.     

A Stable Conversion and Alloying Anode for Potassium‐Ion Batteries: A Combined Strategy of Encapsulation and Confinement

Potassium‐ion batteries based on conversion/alloying reactions have high potential applications in new‐generation large‐scale energy storage. However, their applications are hindered by inherent large‐volume variations and sluggish kinetics of the conversion/alloying‐type electrode materials during the repeated insertion and extraction of bulky K⁺ ions. Although some efforts have been focused on this issue, the reported potassium‐ion batteries still suffer from poor cycling lifespans. Here, a superior stable antimony selenide (Sb₂Se₃) anode is reported for high‐performance potassium‐ion batteries through a combined strategy of conductive encapsulation and 2D confinement. The Sb₂Se₃ nanorods are uniformly coated with a conductive N‐doped carbon layer and then confined between graphene nanosheets. The synergistic effects between conductive coating and confinement effectively buffer the large volumetric variation of the conversion/alloying anodes, which can maintain structural stability for superior cyclability. The as‐prepared anodes exhibit a high reversible specific capacity of ≈590 mA h g^?1 and outstanding cycling stability over 350 cycles. In situ and ex situ characterizations reveal a high structural integration of the large‐volume‐change Sb₂Se₃ anodes during a reversible K storage mechanism of two‐step conversion and multistep alloying processes. This work can open up a new possibility for the design of stable conversion/alloying‐based anodes for high‐performance potassium‐ion batteries.     

Simultaneously Dual Modification of Ni‐Rich Layered Oxide Cathode for High‐Energy Lithium‐Ion Batteries

A critical challenge in the commercialization of layer‐structured Ni‐rich materials is the fast capacity drop and voltage fading due to the interfacial instability and bulk structural degradation of the cathodes during battery operation. Herein, with the guidance of theoretical calculations of migration energy difference between La and Ti from the surface to the inside of LiNi_0.8Co_0.1Mn_0.1O₂, for the first time, Ti‐doped and La₄NiLiO₈‐coated LiNi_0.8Co_0.1Mn_0.1O₂ cathodes are rationally designed and prepared, via a simple and convenient dual‐modification strategy of synchronous synthesis and in situ modification. Impressively, the dual modified materials show remarkably improved electrochemical performance and largely suppressed voltage fading, even under exertive operational conditions at elevated temperature and under extended cutoff voltage. Further studies reveal that the nanoscale structural degradation on material surfaces and the appearance of intergranular cracks associated with the inconsistent evolution of structural degradation at the particle level can be effectively suppressed by the synergetic effect of the conductive La₄NiLiO₈ coating layer and the strong Ti? O bond. The present work demonstrates that our strategy can simultaneously address the two issues with respect to interfacial instability and bulk structural degradation, and it represents a significant progress in the development of advanced cathode materials for high‐performance lithium‐ion batteries.     

Layered Materials in the Magnesium Ion Batteries: Development History,Materials Structure,and Energy Storage Mechanism

Layered crystal materials have blazed a promising trail in the design and optimization of electrodes for magnesium ion batteries (MIBs). The layered crystal materials effectively improve the migration kinetics of the Mg²⁺ storage process to deliver a high energy and power density. To meet the future demand for high-performance MIBs, significant work has been applied to layered crystal materials, including crystal modification, mechanism investigation, and micro/nanostructure design. Herein, this review presents a comprehensive overview of layered crystal materials applied to MIBs, from development history to current applications. It focuses on the relationship between the layered crystal structure and the energy storage mechanism. Meanwhile, recent achievements in the design principles of layered crystal materials and their application to electrodes are summarized. Finally, future perspectives on the application of layered materials in MIBs are presented. The overview of the development process and structural characteristics contributes to a thorough understanding of these materials, while a discussion of design strategies and practical applications can inspire further research. Therefore, this review provides guidance and assistance for constructing high-performance MIBs.     

Understanding the Origin of Li2MnO3 Activation in Li‐Rich Cathode Materials for Lithium‐Ion Batteries

Li‐rich layered cathode materials have been considered as a family of promising high‐energy density cathode materials for next generation lithium‐ion batteries (LIBs). However, although activation of the Li₂MnO₃ phase is known to play an essential role in providing superior capacity, the mechanism of activation of the Li₂MnO₃ phase in Li‐rich cathode materials is still not fully understood. In this work, an interesting Li‐rich cathode material Li_1.87Mn_0.94Ni_0.19O₃ is reported where the Li₂MnO₃ phase activation process can be effectively controlled due to the relatively low level of Ni doping. Such a unique feature offers the possibility of investigating the detailed activation mechanism by examining the intermediate states and phases of the Li₂MnO₃ during the controlled activation process. Combining powerful synchrotron in situ X‐ray diffraction analysis and observations using advanced scanning transmission electron microscopy equipped with a high angle annular dark field detector, it has been revealed that the subreaction of O₂ generation may feature a much faster kinetics than the transition metal diffusion during the Li₂MnO₃ activation process, indicating that the latter plays a crucial role in determining the Li₂MnO₃ activation rate and leading to the unusual stepwise capacity increase over charging cycles.