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.     

超级电容器电解质研究进展

电解质作为超级电容器的重要组成部分,对器件性能起着关键性作用。本文对近些年来超级电容器各种电解质,包括水系、有机液体、离子液体、固态/准固态聚合物电解质和氧化还原体系电解质的特点和最新研究成果进行了描述;重点介绍了固态/准固态聚合物电解质的分类及其性能研究概况。提出了发展电位窗口宽、离子电导率高、电化学性能稳定的离子液体和机械强度等综合性能优良的凝胶聚合物电解质是将来超级电容器电解质发展领域的趋势,最后对超级电容器电解质的发展前景进行了展望。     

Electrolytes and Electrolyte/Electrode Interfaces in Sodium‐Ion Batteries: From Scientific Research to Practical Application

Sodium‐ion batteries (SIBs) have drawn considerable interest as power‐storage devices owing to the wide abundance of their constituents and low cost. To realize a high performance–price ratio, the cathode and anode materials must be optimized. As essential components of SIBs, electrolytes should have wide electrochemical windows, high thermal stability, and exceptional ionic conductivity. Therefore, improved electrolytes, based on various materials and compositions, are developed to meet the practical demands of SIBs, including organic electrolytes, ionic liquids, aqueous, solid electrolytes, and hybrid electrolytes. Although mature organic electrolytes are currently used in production, aqueous and solid electrolytes show advantages for future applications, as discussed here in detail. Current efforts in modifying electrolytes to optimize their interfacial compatibility with electrodes, leading to longer battery lifetimes and greater safety, are described. The advanced characterization techniques used to investigate the properties of electrolytes and interfaces are introduced, and the reaction processes and degradation mechanisms of SIBs are revealed. Furthermore, the practical prospects of SIBs promoted by high‐quality electrolytes appropriately matched with electrodes are predicted and directions for developing next‐generation SIBs are suggested.     

Capillary electrophoretic application of 1-alkyl-3-methylimidazolium-based ionic liquids

Ionic substances with melting points at or close to room temperature are referred to as ionic liquids. Interest in ionic liquids for their potential in different chemical processes is increasing, because they are environmentally benign and are good solvents for a wide range of both organic and inorganic materials. In this study, a capillary electrophoretic method for resolving phenolic compounds found in grape seed extracts is reported. The method, in which 1-alkyl-3-methylimidazolium-based ionic liquids are used as the running electrolytes, is simple and reproducible. The separation mechanism seems to involve association between the imidazolium cations and the polyphenols. The role of the alkyl substituents on the imidazolium cations was investigated and will be discussed.     

Carbons and Electrolytes for Advanced Supercapacitors

Electrical energy storage (EES) is one of the most critical areas of technological research around the world. Storing and efficiently using electricity generated by intermittent sources and the transition of our transportation fleet to electric drive depend fundamentally on the development of EES systems with high energy and power densities. Supercapacitors are promising devices for highly efficient energy storage and power management, yet they still suffer from moderate energy densities compared to batteries. To establish a detailed understanding of the science and technology of carbon/carbon supercapacitors, this review discusses the basic principles of the electrical double‐layer (EDL), especially regarding the correlation between ion size/ion solvation and the pore size of porous carbon electrodes. We summarize the key aspects of various carbon materials synthesized for use in supercapacitors. With the objective of improving the energy density, the last two sections are dedicated to strategies to increase the capacitance by either introducing pseudocapacitive materials or by using novel electrolytes that allow to increasing the cell voltage. In particular, advances in ionic liquids, but also in the field of organic electrolytes, are discussed and electrode mass balancing is expanded because of its importance to create higher performance asymmetric electrochemical capacitors.     

Borohydride‐Scaffolded Li/Na/Mg Fast Ionic Conductors for Promising Solid‐State Electrolytes

Borohydride solid‐state electrolytes with room‐temperature ionic conductivity up to ≈70 mS cm^?1 have achieved impressive progress and quickly taken their place among the superionic conductive solid‐state electrolytes. Here, the focus is on state‐of‐the‐art developments in borohydride solid‐state electrolytes, including their competitive ionic‐conductive performance, current limitations for practical applications in solid‐state batteries, and the strategies to address their problems. To open, fast Li/Na/Mg ionic conductivity in electrolytes with BH₄ ^? groups, approaches to engineering borohydrides with enhanced ionic conductivity, and later on the superionic conductivity of polyhedral borohydrides, their correlated conductive kinetics/thermodynamics, and the theoretically predicted high conductive derivatives are discussed. Furthermore, the validity of borohydride pairing with coated oxides, sulfur, organic electrodes, MgH₂, TiS₂, Li₄Ti₅O₁₂, electrode materials, etc., is surveyed in solid‐state batteries. From the viewpoint of compatible cathodes, the stable electrochemical windows of borohydride solid‐state electrolytes, the electrode/electrolyte interface behavior and battery device design, and the performance optimization of borohydride‐based solid‐state batteries are also discussed in detail. A comprehensive coverage of emerging trends in borohydride solid‐state electrolytes is provided and future maps to promote better performance of borohydride SSEs are sketched out, which will pave the way for their further development in the field of energy storage.     

High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes

We demonstrate the high performance of supercapacitors fabricated with vertically aligned carbon nanotubes and nonaqueous electrolytes such as ionic liquids and conventional organic electrolytes. Specific capacitance, maximum power and energy density of the supercapacitor measured in ionic liquid were ~75 F g(-1), ~987 kW kg(-1) and ~27 W h kg(-1), respectively. The high power performance was consistently indicated by a fast relaxation time constant of 0.2 s. In addition, electrochemical oxidation of the carbon nanotubes improved the specific capacitance (~158 F g(-1)) and energy density (~53 W h kg(-1)). Both high power and energy density could be attributed to the fast ion transport realized by the alignment of carbon nanotubes and the wide operational voltage defined by the ionic liquid. The demonstrated carbon-nanotube- and nonaqueous-electrolyte-based supercapacitors show great potential for the development of high-performance energy storage devices.     

Ionic liquids confined in porous matrices: Physicochemical properties and applications

Ionic liquids are emerging as important materials for applications in electrochemical devices, green chemistry etc. For device applications, ionic liquids are generally, either incorporated in polymer matrices or confined in porous matrices (giving rise to an interesting class of materials ‘Ionogels’). This review deals with the science and technological applications of ionic liquids confined in nano-pores. A comprehensive overview is given about the experimental studies dealing with the changes in the physico-chemical properties of ionic liquids like thermal phase transition, stability, dynamical behavior, optical properties etc. Recent theoretical studies highlighting the layering and structural heterogeneity of ionic liquids confined in nano-pores are also discussed. To make the review self-reading, basic ideas about ionic liquids and the phenomena of confinement are also briefly included.     

Lithium-Ion Battery Separators for Ionic-Liquid Electrolytes: A Review

Ionic liquids (ILs) are widely studied as a safer alternative electrolyte for lithium-ion batteries. The properties of IL electrolytes compared to conventional electrolytes make them more thermally stable, but they also have poor wetting with commercial separators. In a lithium-ion battery, the electrolyte should completely wet out the separator and electrodes to reduce the cell internal resistance. Investigations of cell materials with IL electrolytes have shown that the wetting issues in IL–electrolyte cells are most likely due to poor separator compatibility, not electrode compatibility. A compatible separator must be developed before IL electrolytes can be used in commercial lithium-ion batteries. Herein, separators for IL electrolytes, including commercial and novel separators, are reviewed. Separators with different processing methods, polymers, additives, and different IL electrolytes are considered. Collated, the separator studies show a strong correlation between ionic conductivity and membrane porosity, even more than the electrolyte type. The challenge of a suitable separator for IL electrolytes is not solved yet. Herein, it is revealed that a separator for IL electrolytes will most likely require a combination of high thermal and mechanical stability polymer, ceramic additives, and an optimized manufacturing process.     

MOF‐Derived Metal Oxide Composites for Advanced Electrochemical Energy Storage

Over the past two decades, metal–organic frameworks (MOFs), a type of porous material, have aroused great interest as precursors or templates for the derivation of metal oxides and composites for the next generation of electrochemical energy storage applications owing to their high specific surface areas, controllable structures, and adjustable pore sizes. The electrode materials, which affect the performance in practical applications, are pivotal components of batteries and supercapacitors. Metal oxide composites derived from metal–organic frameworks possessing high reversible capacity and superior rate and cycle performance are excellent electrode materials. In this Review, potential applications for MOF‐derived metal oxide composites for lithium‐ion batteries, sodium‐ion batteries, lithium–oxygen batteries, and supercapacitors are studied and summarized. Finally, the challenges and opportunities for future research on MOF‐derived metal oxide composites are proposed on the basis of academic knowledge from the reported literature as well as from experimental experience.     

Toward High-Energy-Density Lithium Metal Batteries: Opportunities and Challenges for Solid Organic Electrolytes

With increasing demands for safe, high capacity energy storage to support personal electronics, newer devices such as unmanned aerial vehicles, as well as the commercialization of electric vehicles, current energy storage technologies are facing increased challenges. Although alternative batteries have been intensively investigated, lithium (Li) batteries are still recognized as the preferred energy storage solution for the consumer electronics markets and next generation automobiles. However, the commercialized Li batteries still have disadvantages, such as low capacities, potential safety issues, and unfavorable cycling life. Therefore, the design and development of electromaterials toward high-energy-density, long-life-span Li batteries with improved safety is a focus for researchers in the field of energy materials. Herein, recent advances in the development of novel organic electrolytes are summarized toward solid-state Li batteries with higher energy density and improved safety. On the basis of new insights into ionic conduction and design principles of organic-based solid-state electrolytes, specific strategies toward developing these electrolytes for Li metal anodes, high-energy-density cathode materials (e.g., high voltage materials), as well as the optimization of cathode formulations are outlined. Finally, prospects for next generation solid-state electrolytes are also proposed.     

Preparation of Inorganic Materials Using Ionic Liquids

Conventional synthesis of inorganic materials relies heavily on water and organic solvents. Alternatively, the synthesis of inorganic materials using, or in the presence of, ionic liquids represents a burgeoning direction in materials chemistry. Use of ionic liquids in solvent extraction and organic catalysis has been extensively studied, but their use in inorganic synthesis has just begun. Ionic liquids are a family of non‐conventional molten salts that can act as templates and precursors to inorganic materials, as well as solvents. They offer many advantages, such as negligible vapor pressures, wide liquidus ranges, good thermal stability, tunable solubility for both organic and inorganic molecules, and much synthetic flexibility. In this Review, the use of ionic liquids in the preparation of several categories of inorganic and hybrid materials (i.e., metal structures, non‐metal elements, silicas, organosilicas, metal oxides, metal chalcogenides, metal salts, open‐framework structures, ionic liquid‐functionalized materials, and supported ionic liquids) is summarized. The status quo of the research field is assessed, and some future perspectives are furnished.     

Molten salts for rechargeable batteries

The growing demand of advanced electrochemical energy storage devices for various applications, including portable electronic products, electric vehicles, and large-scale energy storage grids, has triggered extensive research interests and efforts on various rechargeable batteries such as lithium/sodium-ion batteries (LIBs/NIBs), aluminium-ion batteries (AIBs), liquid metal batteries (LMBs), and molten-air batteries (MABs) in the past decades. A key issue to push forward the development of these batteries is the exploration of high-performance electrodes and electrolytes, which calls for efficient and versatile synthetic methods. Molten salts (MSs), liquid-phase ionic compounds or mixtures, provide an effective platform to widen the reaction temperatures and enrich the chemical environments for the synthesis of novel electrode materials and electrolytes. In this review, the general principles of molten salts and recent research progresses on molten salt-based battery materials are surveyed. Molten-salt synthesis of electrode materials, including sintering and electrolysis, are emerging as competitive substitutes for conventional synthesis techniques. These methods have shown their effectiveness and uniqueness in adjusting the crystal structure, morphology, and performance of electrode materials for LIBs/NIBs, as suggested by recent progresses and applications of diverse cathodes (layered oxides, spinel oxides, polyanions, etc.) and anodes (metal oxides, alloys, carbons, etc.). Furthermore, the applications of molten salts as effective electrolytes are demonstrated in representative new-type secondary batteries including AIBs, LMBs and MABs. Finally, the emerging opportunities, challenges, and interesting research trends are envisioned to promote the further development of molten-salt methodology for rechargeable batteries.     

25th Anniversary Article: “Cooking Carbon with Salt”: Carbon Materials and Carbonaceous Frameworks from Ionic Liquids and Poly(ionic liquid)s

This review surveys recent work on the use of ionic liquids (ILs) and polymerized ionic liquids (PILs) as precursors to synthesize functional carbon materials. As solvents or educts with negligible vapour pressure, these systems enable simple processing, composition, and structural control of the resulting carbons under rather simple and green synthesis conditions. Recent applications of the resulting nanocarbons across a multitude of fields, such as fuel cells, energy storage in batteries and supercapacitors, catalysis, separation, and sorption materials are highlighted.     

Emerging 2D Copper-Based Materials for Energy Storage and Conversion: A Review and Perspective

2D materials have shown great potential as electrode materials that determine the performance of a range of electrochemical energy technologies. Among these, 2D copper-based materials, such as Cu–O, Cu–S, Cu–Se, Cu–N, and Cu–P, have attracted tremendous research interest, because of the combination of remarkable properties, such as low cost, excellent chemical stability, facile fabrication, and significant electrochemical properties. Herein, the recent advances in the emerging 2D copper-based materials are summarized. A brief summary of the crystal structures and synthetic methods is started, and innovative strategies for improving electrochemical performances of 2D copper-based materials are described in detail through defect engineering, heterostructure construction, and surface functionalization. Furthermore, their state-of-the-art applications in electrochemical energy storage including supercapacitors (SCs), alkali (Li, Na, and K)-ion batteries, multivalent metal (Mg and Al)-ion batteries, and hybrid Mg/Li-ion batteries are described. In addition, the electrocatalysis applications of 2D copper-based materials in metal–air batteries, water-splitting, and CO₂ reduction reaction (CO₂RR) are also discussed. This review also discusses the charge storage mechanisms of 2D copper-based materials by various advanced characterization techniques. The review with a perspective of the current challenges and research outlook of such 2D copper-based materials for high-performance energy storage and conversion applications is concluded.     

Recent advances in electrospun carbon nanofibers and their application in electrochemical energy storage

Carbon nanofibers (CNFs) have been widely used in electrochemical energy storage devices because of their excellent conductivities, extremely large surface areas and structural stability. In energy storage devices like rechargeable batteries and supercapacitors, CNFs play multi-functional roles as active electrode materials, conductive additives and substrates for supporting active metal (oxides). Electrospinning offers a low cost and scalable technique to fabricate CNFs and their hybrids with tunable nanostructures. This paper summarizes various design strategies for producing random, aligned and core/shell structured fibers, and elucidates the influences of polymer precursors, processing parameters, conductive additives and catalysts on functional, morphological and structural characteristics of CNFs. The current start-of-the-art developments for applications in Li-ion batteries, supercapacitors, Na-ion batteries, Li–O₂ batteries and Li–S batteries are reviewed. Key issues that affect the electrochemical performance of the electrodes, such as the chemical and atomic structures, electrical conductivities, surface areas and pore size distribution of CNFs, and the particle size, shape and dispersion of metal (oxides) encapsulated in CNFs, are discussed and their solutions suggested. Future prospects on further optimization of the structure and performance, and challenges encountered in large-scale applications of electrospun CNFs are proposed.     

Liquid Quinones for Solvent‐Free Redox Flow Batteries

Liquid benzoquinone and naphthoquinone having diethylene glycol monomethyl ether groups are designed and synthesized as redox active materials that dissolve supporting electrolytes. The Li‐ion batteries based on the liquid quinones using LiBF₄/PC show good performance in terms of voltage, capacity, energy efficiency, and cyclability in both static and flow modes. A battery is constructed without using intentionally added organic solvent, and its high energy density (264 W h L^?1) demonstrates the potential of solvent‐free organic redox flow batteries using liquid active materials.     

Research Advances of Amorphous Metal Oxides in Electrochemical Energy Storage and Conversion

Amorphous metal oxides (AMOs) have aroused great enthusiasm across multiple energy areas over recent years due to their unique properties, such as the intrinsic isotropy, versatility in compositions, absence of grain boundaries, defect distribution, flexible nature, etc. Here, the materials engineering of AMOs is systematically reviewed in different electrochemical applications and recent advances in understanding and developing AMO‐based high‐performance electrodes are highlighted. Attention is focused on the important roles that AMOs play in various energy storage and conversion technologies, such as active materials in metal‐ion batteries and supercapacitors as well as active catalysts in water splitting, metal–air batteries, and fuel cells. The improvements of electrochemical performance in metal‐ion batteries and supercapacitors are reviewed regarding the enhancement in active sites, mechanical strength, and defect distribution of amorphous structures. Furthermore, the high electrochemical activities boosted by AMOs in various fundamental reactions are elaborated on and they are related to the electrocatalytic behaviors in water splitting, metal–air batteries, and fuel cells. The applications in electrochromism and high‐conducting sensors are also briefly discussed. Finally, perspectives on the existing challenges of AMOs for electrochemical applications are proposed, together with several promising future research directions.     

室温离子液体在材料合成中的应用

室温离子液体的物理和化学性质相对稳定,具有结构可调的特性.作为一种新功能材料广泛用于材料合成领域.根据离子液体在材料合成中的不同作用,本文从离子液体作为反应溶剂、模板剂、电解液、以及同时作为溶剂和模板剂这4个方面介绍了其在材料合成中的应用研究进展.