金属氰胺化合物的结构、合成及电化学储能应用

金属氰胺化合物M_x(NCN)_y作为类氧硫族化合物, 是一类新兴的无机功能材料。准线性[NCN]^2-阴离子赋予其空旷和具有孔道的晶体结构、独特的电子结构和新奇的物化性质, 金属氰胺化合物在固态发光、光/电催化及电化学储能等诸多领域展现出应用前景, 近年来逐渐成为研究热点。本文简要回顾了金属氰胺化合物的研究历史, 概述了金属氰胺化合物的晶体结构及物化性质, 总结了常见合成方法及策略, 探讨了金属氰胺化合物在电化学储能领域的应用, 重点论述了其作为锂钠离子电池新型负极材料的电化学性能及存储机制。     

Rational design of MXene-based films for energy storage: Progress,prospects

Two-dimensional (2D) transition metal carbides, nitrides, and carbonitrides (MXenes) have been synthesized and developed into a wide range of applications including energy storage, optoelectronics, electromagnetic interference shielding, biomedicine, and sensors, etc. Compared to other 2D materials, MXenes possess a unique set of properties such as superior mechanical strength, outstanding hydrophily, and excellent dispersion quality, making them particularly suitable for fabricating films/membranes featuring designed microstructures and tunable nanochannels. 2D MXene-based films (MBFs) have demonstrated excellent ion storage, electron transport and ionic selectivity properties for electrochemical energy storage and have received enormous interest in recent years. Compared with conventional electrode materials and structures, MBFs show great advantages in the aspects of flexibility, tailorability and functionality, which are suitable for flexible, portable, and highly integrated energy storage systems. This review summarizes recent advances and well-developed strategies of the MBFs design and fabrication toward applications of metal-ion batteries (MIBs, including Li, Na, K-ions), lithium-sulfur (Li-S) batteries and supercapacitors (SCs). Special attentions are given to the design principles of MBFs based microstructures, inter-layer nanochannels and in-plane nanochannels for energy storage. Finally, the current challenges and promising perspectives of the MBFs for energy storage devices are presented.     

Nanoionics: ion transport and electrochemical storage in confined systems

The past two decades have shown that the exploration of properties on the nanoscale can lead to substantially new insights regarding fundamental issues, but also to novel technological perspectives. Simultaneously it became so fashionable to decorate activities with the prefix 'nano' that it has become devalued through overuse. Regardless of fashion and prejudice, this article shows that the crystallizing field of 'nanoionics' bears the conceptual and technological potential that justifies comparison with the well-acknowledged area of nanoelectronics. Demonstrating this potential implies both emphasizing the indispensability of electrochemical devices that rely on ion transport and complement the world of electronics, and working out the drastic impact of interfaces and size effects on mass transfer, transport and storage. The benefits for technology are expected to lie essentially in the field of room-temperature devices, and in particular in artificial self-sustaining structures to which both nanoelectronics and nanoionics might contribute synergistically.     

Nanoarchitectonics for Controlling the Number of Dopant Atoms in Solid Electrolyte Nanodots

Controlling movements of electrons and holes is the key task in developing today's highly sophisticated information society. As transistors reach their physical limits, the semiconductor industry is seeking the next alternative to sustain its economy and to unfold a new era of human civilization. In this context, a completely new information token, i.e., ions instead of electrons, is promising. The current trend in solid‐state nanoionics for applications in energy storage, sensing, and brain‐type information processing, requires the ability to control the properties of matter at the ultimate atomic scale. Here, a conceptually novel nanoarchitectonic strategy is proposed for controlling the number of dopant atoms in a solid electrolyte to obtain discrete electrical properties. Using α‐Ag_2+δS nanodots with a finite number of nonstoichiometry excess dopants as a model system, a theory matched with experiments is presented that reveals the role of physical parameters, namely, the separation between electrochemical energy levels and the cohesive energy, underlying atomic‐scale manipulation of dopants in nanodots. This strategy can be applied to different nanoscale materials as their properties strongly depend on the number of doping atoms/ions, and has the potential to create a new paradigm based on controlled single atom/ion transfer.     

Rechargeable Seawater Batteries—From Concept to Applications

Harvesting energy from natural resources is of significant interest because of their abundance and sustainability. Seawater is the most abundant natural resource on earth, covering two‐thirds of the surface. The rechargeable seawater battery is a new energy storage platform that enables interconversion of electrical energy and chemical energy by tapping into seawater as an infinite medium. Here, an overview of the research and development activities of seawater batteries toward practical applications is presented. Seawater batteries consist of anode and cathode compartments that are separated by a Na‐ion conducting membrane, which allows only Na⁺ ion transport between the two electrodes. The roles and drawbacks of the three key components, as well as the development concept and operation principles of the batteries on the basis of previous reports are covered. Moreover, the prototype manufacturing lines for mass production and automation, and potential applications, particularly in marine environments are introduced. Highlighting the importance of engineering the cell components, as well as optimizing the system level for a particular application and thereby successful market entry, the key issues to be resolved are discussed, so that the seawater battery can emerge as a promising alternative to existing rechargeable batteries.     

Multishelled Transition Metal‐Based Microspheres: Synthesis and Applications for Batteries and Supercapacitors

With the rapid growth of material innovations, multishelled hollow nanostructures are of tremendous interest due to their unique structural features and attractive physicochemical properties. Continued effort has been made in the geometric manipulation, composition complexity, and construction diversity of this material, expanding its applications. Energy storage technology has benefited from the large surface area, short transport path, and excellent buffering ability of the nanostructures. In this work, the general synthesis of multishelled hollow structures, especially with architecture versatility, is summarized. A wealth of attractive properties is also discussed for a wide area of potential applications based on energy storage systems, including Li‐ion/Na‐ion batteries, supercapacitors, and Li–S batteries. Finally, the emerging challenges and outlook for multishelled hollow structures are mentioned.     

Highly Efficient Ionic Photocurrent Generation through WS2‐Based 2D Nanofluidic Channels

The unique feature of nacre‐like 2D layered materials provides a facile, yet highly efficient way to modulate the transmembrane ion transport from two orthogonal transport directions, either vertical or horizontal. Recently, light‐driven active transport of ionic species in synthetic nanofluidic systems attracts broad research interest. Herein, taking advantage of the photoelectric semiconducting properties of 2D transition metal dichalcogenides, the generation of a directional and greatly enhanced cationic flow through WS₂‐based 2D nanofluidic membranes upon asymmetric visible light illumination is reported. Compared with graphene‐based materials, the magnitude of the ionic photocurrent can be enhanced by tens of times, and its photo‐responsiveness can be 2–3.5 times faster. This enhancement is explained by the coexistence of semiconducting and metallic WS₂ nanosheets in the hybrid membrane that facilitates the asymmetric diffusion of photoexcited charge carriers on the channel wall, and the high ionic conductance due to the neat membrane structure. To further demonstrate its application, photonic ion switches, photonic ion diodes, and photonic ion transistors as the fundamental elements for light‐controlled nanofluidic circuits are further developed. Exploring new possibilities in the family of liquid processable colloidal 2D materials provides a way toward high‐performance light‐harvesting nanofluidic systems for artificial photosynthesis and sunlight‐driven desalination.     

1D Nanomaterials: Design,Synthesis, and Applications in Sodium–Ion Batteries

Sodium–ion batteries (SIBs) have received extensive attention as ideal candidates for large‐scale energy storage systems (ESSs) owing to the rich resources and low cost of sodium (Na). However, the larger size of Na⁺ and the less negative redox potential of Na⁺/Na result in low energy densities, short cycling life, and the sluggish kinetics of SIBs. Therefore, it is necessary to develop appropriate Na storage electrode materials with the capability to host larger Na⁺ and fast ion diffusion kinetics. 1D materials such as nanofibers, nanotubes, nanorods, and nanowires, are generally considered to be high‐capacity and stable electrode materials, due to their uniform structure, orientated electronic and ionic transport, and strong tolerance to stress change. Here, the synthesis of 1D nanomaterials and their applications in SIBs are reviewed. In addition, the prospects of 1D nanomaterials on energy conversion and storage as well as the development and application orientation of SIBs are presented.     

3D Porous Hydrogel/Conducting Polymer Heterogeneous Membranes with Electro‐/pH‐Modulated Ionic Rectification

Heterogeneous membranes composed of asymmetric structures or compositions have enormous potential in sensors, molecular sieves, and energy devices due to their unique ion transport properties such as ionic current rectification and ion selectivity. So far, heterogeneous membranes with 1D nanopores have been extensively studied. However, asymmetric structures with 3D micro‐/nanoscale pore networks have never been investigated. Here, a simple and versatile approach to low‐costly fabricate hydrogel/conducting polymer asymmetric heterogeneous membranes with electro‐/pH‐responsive 3D micro‐/nanoscale ion channels is introduced. Due to the asymmetric heterojunctions between positively charged nanoporous polypyrrole (PPy) and negatively charged microscale porous hydrogel poly (acrylamide‐co‐acrylic acid) (P(AAm‐co‐AA)), the membrane can rectify ion transmembrane transport in response to both electro‐ and pH‐stimuli. Numerical simulations based on coupled Poisson and Nernst–Plank equations are carried out to explain the ionic rectification mechanisms for the membranes. The membranes are not dependent on elaborately fabricated 1D ion channel substrates and hence can be facilely prepared in a low‐cost and large‐area way. The hybridization of hydrogel and conducting polymer offers a novel strategy for constructing low‐cost, large‐area and multifunctional membranes, expanding the tunable ionic rectification properties into macroscopic membranes with micro‐/nanoscale pores, which would stimulate practical applications of the membranes.     

Niobium‐Based Oxides Toward Advanced Electrochemical Energy Storage: Recent Advances and Challenges

Niobium‐based oxides including Nb₂O₅, TiNb_xO_2+2.5x compounds, M–Nb–O (M = Cr, Ga, Fe, Zr, Mg, etc.) family, etc., as the unique structural merit (e.g., quasi‐2D network for Li‐ion incorporation, open and stable Wadsley– Roth shear crystal structure), are of great interest for applications in energy storage systems such as Li/Na‐ion batteries and hybrid supercapacitors. Most of these Nb‐based oxides show high operating voltage (>1.0 V vs Li⁺/Li) that can suppress the formation of solid electrolyte interface film and lithium dendrites, ensuring the safety of working batteries. Outstanding rate capability is impressive, which can be derived from their fast intercalation pseudocapacitive kinetics. However, the intrinsic poor electrical conductivity hinders their energy storage applications. Various strategies including structure optimization, surface engineering, and carbon modification are effectively used to overcome the issues. This review provides a comprehensive summary on the latest progress of Nb‐based oxides for advanced electrochemical energy storage applications. Major impactful work is outlined, promising research directions, and various performance‐optimizing strategies, as well as the energy storage mechanisms investigated by combining theoretical calculations and various electrochemical characterization techniques. In addition, challenges and perspectives for future research and commercial applications are also presented.     

Light‐Powered Directional Nanofluidic Ion Transport in Kirigami‐Made Asymmetric Photonic‐Ionic Devices

Nacre‐mimetic 2D nanofluidic materials with densely packed sub‐nanometer‐height lamellar channels find widespread applications in water‐, energy‐, and environment‐related aspects by virtue of their scalable fabrication methods and exceptional transport properties. Recently, light‐powered nanofluidic ion transport in synthetic materials gained considerable attention for its remote, noninvasive, and active control of the membrane transport property using the energy of light. Toward practical application, a critical challenge is to overcome the dependence on inhomogeneous or site‐specific light illumination. Here, asymmetric photonic‐ionic devices based on kirigami‐tailored graphene oxide paper are fabricated, and directional nanofluidic ion transport properties therein powered by full‐area light illumination are demonstrated. The in‐plane asymmetry of the graphene oxide paper is essential to the generation of photoelectric driving force under homogeneous illumination. This light‐powered ion transport phenomenon is explained based on a modified carrier diffusion model. In asymmetric nanofluidic structures, enhanced recombination of photoexcited charge carriers at the membrane boundary breaks the electric potential balance in the horizontal direction, and thus drives the ion transport in that direction under symmetric illumination. The kirigami‐based strategy provides a facile and scalable way to fabricate paper‐like photonic‐ionic devices with arbitrary shapes, working as fundamental elements for large‐scale light‐harvesting nanofluidic circuits.     

Ionic liquids for electrochemical energy storage devices applications

Ionic liquids, defined here as room-temperature molten salts, composed mainly of organic cations and (in)organic anions ions that may undergo almost unlimited structural variations with melting points below 100?°C. They offer a unique series of physical and chemical properties that make them extreme important candidates for several energy applications, especially for clean and sustainable energy storage and conversion materials and devices. Ionic liquids exhibit high thermal and electrochemical stability coupled with low volatility, create the possibility of designing appropriate electrolytes for different type batteries and supercapacitors. Herein, varieties of ionic liquids applications are reviewed on their utilization as electrolytes for Li-ion batteries, Na-ion batteries, Li-O₂(air) batteries, Li-Sulfur (Li-S) batteries, supercapacitors and as precursors to prepare and modify the electrode materials, meanwhile, some important research results in recent years are specially introduced, and the perspective on novel application of ionic liquids is also discussed.     

Hybrid Nanostructures for Energy Storage Applications

Materials engineering plays a key role in the field of energy storage. In particular, engineering materials at the nanoscale offers unique properties resulting in high performance electrodes and electrolytes in various energy storage devices. Consequently, considerable efforts have been made in recent years to fulfill the future requirements of electrochemical energy storage using these advanced materials. Various multi‐functional hybrid nanostructured materials are currently being studied to improve energy and power densities of next generation storage devices. This review describes some of the recent progress in the synthesis of different types of hybrid nanostructures using template assisted and non‐template based methods. The potential applications and recent research efforts to utilize these hybrid nanostructures to enhance the electrochemical energy storage properties of Li‐ion battery and supercapacitor are discussed. This review also briefly outlines some of the recent progress and new approaches being explored in the techniques of fabrication of 3D battery structures using hybrid nanoarchitectures.     

Porous Polymers as Multifunctional Material Platforms toward Task‐Specific Applications

Exploring advanced porous materials is of critical importance in the development of science and technology. Porous polymers, being famous for their all‐organic components, tailored pore structures, and adjustable chemical components, have attracted an increasing level of research interest in a large number of applications, including gas adsorption/storage, separation, catalysis, environmental remediation, energy, optoelectronics, and health. Recent years have witnessed tremendous research breakthroughs in these fields thanks to the unique pore structures and versatile skeletons of porous polymers. Here, recent milestones in the diverse applications of porous polymers are presented, with an emphasis on the structural requirements or parameters that dominate their properties and functionalities. The Review covers the following applications: i) gas adsorption, ii) water treatment, iii) separation, iv) heterogeneous catalysis, v) electrochemical energy storage, vi) precursors for porous carbons, and vii) other applications (e.g., intelligent temperature control textiles, sensing, proton conduction, biomedicine, optoelectronics, and actuators). The key requirements for each application are discussed and an in‐depth understanding of the structure–property relationships of these advanced materials is provided. Finally, a perspective on the future research directions and challenges in this field is presented for further studies.     

Ti‐Based Oxide Anode Materials for Advanced Electrochemical Energy Storage: Lithium/Sodium Ion Batteries and Hybrid Pseudocapacitors

Titanium‐based oxides including TiO₂ and M‐Ti‐O compounds (M = Li, Nb, Na, etc.) family, exhibit advantageous structural dynamics (2D ion diffusion path, open and stable structure for ion accommodations) for practical applications in energy storage systems, such as lithium‐ion batteries, sodium‐ion batteries, and hybrid pseudocapacitors. Further, Ti‐based oxides show high operating voltage relative to the deposition of alkali metal, ensuring full safety by avoiding the formation of lithium and sodium dendrites. On the other hand, high working potential prevents the decomposition of electrolyte, delivering excellent rate capability through the unique pseudocapacitive kinetics. Nevertheless, the intrinsic poor electrical conductivity and reaction dynamics limit further applications in energy storage devices. Recently, various work and in‐depth understanding on the morphologies control, surface engineering, bulk‐phase doping of Ti‐based oxides, have been promoted to overcome these issues. Inspired by that, in this review, the authors summarize the fundamental issues, challenges and advances of Ti‐based oxides in the applications of advanced electrochemical energy storage. Particularly, the authors focus on the progresses on the working mechanism and device applications from lithium‐ion batteries to sodium‐ion batteries, and then the hybrid pseudocapacitors. In addition, future perspectives for fundamental research and practical applications are discussed.     

Research progress on electrode materials and electrolytes for supercapacitors北大核心CSCD

Supercapacitors have great potential applications for electronic devices, and energy recyling and storage areas owing to their high power density, long cycle life, high safety and excellent performance at low temperatures. The electrode materials and electrolytes are two key factors that influence their performance. The electrode materials used in supercapacitors include carbon materials such as activated carbons, carbon nanotubes, graphene, carbon nanofibers and carbon nano-onions, metal oxides, conductive polymers and their composites. The electrolytes are aqueous electrolytes, organic electrolytes or ionic liquids. Here research progress on the electrode materials and liquid electrolytes for supercapacitors is summarized, their advantages and disadvantages are analyzed, and new electrode materials and electrolytes are suggested.     

Localized Electrons Enhanced Ion Transport for Ultrafast Electrochemical Energy Storage

The rate-determining process for electrochemical energy storage is largely determined by ion transport occurring in the electrode materials. Apart from decreasing the distance of ion diffusion, the enhancement of ionic mobility is crucial for ion transport. Here, a localized electron enhanced ion transport mechanism to promote ion mobility for ultrafast energy storage is proposed. Theoretical calculations and analysis reveal that highly localized electrons can be induced by intrinsic defects, and the migration barrier of ions can be obviously reduced. Consistently, experiment results reveal that this mechanism leads to an enhancement of Li/Na ion diffusivity by two orders of magnitude. At high mass loading of 10 mg cm⁻² and high rate of 10C, a reversible energy storage capacity up to 190 mAh g⁻¹ is achieved, which is ten times greater than achievable by commercial crystals with comparable dimensions.     

Molecularly Hybridized Conduction in DPP-Based Donor–Acceptor Copolymers toward High-Performance Iono-Electronics

Iono-electronics, that is, transducing devices able to translate ionic injection into electrical output, continue to demand a variety of mixed ionic–electronic conductors (MIECs). Though polar sidechains are widely used in designing novel polymer MIECs, it remains unclear to chemists how much balance is needed between the two antagonistic modes of transport (ion permeability and electronic charge transport) to yield high-performance materials. Here, the impact of molecularly hybridizing ion permeability and charge mobility in semiconducting polymers on their performance in electrochemical and synaptic transistors is investigated. A series of diketopyrrolopyrrole (DPP)-based copolymers are employed to demonstrate the multifunctionality attained by controlling the density of polar sidechains along the backbone. Notably, efficient electrochemical signal transduction and reliable synaptic plasticity are demonstrated via controlled ion insertion and retention. The newly designed DPP-based copolymers further demonstrate unprecedented thermal tolerance among organic mixed ionic–electronic conductors, a key property in the manufacturing of organic electronics.     

Advanced Covalent Organic Framework-Based Membranes for Recovery of Ionic Resources

Membrane technology has shown a viable potential in conversion of liquid-waste or high-salt streams to fresh waters and resources. However, the non-adjustability pore size of traditional membranes limits the application of ion capture due to their low selectivity for target ions. Recently, covalent organic frameworks (COFs) have become a promising candidate for construction of advanced ion separation membranes for ion resource recovery due to their low density, large surface area, tunable channel structure, and tailored functionality. This tutorial review aims to analyze and summarize the progress in understanding ion capture mechanisms, preparation processes, and applications of COF-based membranes. First, the design principles for target ion selectivity are illustrated in terms of theoretical simulation of ions transport in COFs, and key properties for ion selectivity of COFs and COF-based membranes. Next, the fabrication methods of diverse COF-based membranes are classified into pure COF membranes, COF continuous membranes, and COF mixed matrix membranes. Finally, current applications of COF-based membranes are highlighted: desalination, extraction, removal of toxic metal ions, radionuclides and lithium, and acid recovery. This review presents promising approaches for design, preparation, and application of COF-based membranes in ion selectivity for recovery of ionic resources.     

Charged Layered Boron Nitride‐Nanoflake Membranes for Efficient Ion Separation and Water Purification

2D layered nanomaterials have attracted considerable attention for their potential for highly efficient separations, among other applications. Here, a 2D lamellar membrane synthesized using hexagonal boron nitride nanoflakes (h‐BNF) for highly efficient ion separation is reported. The ion‐rejection performance and the water permeance of the membrane as a function of the ionic radius, ion valance, and solution pH are investigated. The nonfunctionalized h‐BNF membranes show excellent ion rejection for small sized salt ions as well as for anionic dyes (>97%) while maintaining a high water permeability, ≈1.0 × 10^?3 L m m^?2 h^?1 bar^?1). Experiments show that the ion‐rejection performance of the membrane can be tuned by changing the solution pH. The results also suggest that the rejection is influenced by the ionic size and the electrostatic repulsion between fixed negative charges on the BN surface and the mobile ions, and is consistent with the Donnan equilibrium model. These simple‐to‐fabricate h‐BNF membranes show a unique combination of excellent ion selectivity and high permeability compared to other 2D membranes.