Understanding the Solid-Electrolyte-Interface (SEI) Formation in Glyme Electrolyte Using Time-Of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS).

Lithium-ion batteries are commonly used for energy storage due to their long lifespan and high energy density, but the use of unsafe electrolytes poses significant health and safety concerns. An alternative source is necessary to maintain electrochemical efficacy. This research demonstrates new safe glyme-based electrolytes for silica/carbon (SiOx/C) nanocomposite derived from Australian rice husk (RH). The quality of SiOx/C was preserved by using deep eutectic solvent-based pre-treatment and single-step carbonization, which was confirmed through the X-ray analysis of the crystalline phase of silica. The electrochemical assessment of SiOx/C anode using various glyme-based electrolytes for LIBs was carried out. Among them, the resultant half cells based on diglyme electrolyte is superior to others with the first discharge capacity at 1274 mAh/g and a reversible discharge capacity of 759.7 mAh/g. Ex-situ SEM and Time-of-Flight Secondary Ion Mass Spectrometry (ToF- SIMS) analysis of the electrode indicated that diglyme not only improves the capacity but also sustains the electrode architecture for longer cycle life with more LiF-based components and also showed the absence of HF components. Importantly, the addition of fluoroethylene carbonate (FEC) additive enhanced the cycling stability. These results provide a new perspective on developing advanced SiOx/C anode using glyme electrolytes for Li-ion batteries.

Doping Regulation Stabilizing δ-MnO2 Cathode for High-Performance Aqueous Aluminium-ion Batteries.

δ-MnO2 is a promising cathode material for aqueous aluminium-ion batteries (AAIBs) for its layered crystalline structure with large interlayer spacing. However, the excellent Al ion storage performance of δ-MnO2 cathode remains elusive due to the frustrating structural collapse during the intercalation of high ionic potential Al ion species. Here, it is discovered that introducing heterogeneous metal dopants with high bond dissociation energy when bonded to oxygen can significantly reinforce the structural stability of δ-MnO2 frameworks. This reinforcement translates to stable cycling properties and high specific capacity in AAIBs. Vanadium-doped δ-MnO2 (V-δ-MnO2 ) can deliver a high specific capacity of 518 mAh g-1 at 200 mA g-1 with remarkable cycling stability for 400 cycles and improved rate capabilities (468, 339, and 285 mAh g-1 at 0.5, 1, and 2 A g-1 , respectively), outperforming other doped δ-MnO2 materials and the reported AAIB cathodes. Theoretical and experimental studies indicate that V doping can substantially improve the cohesive energy of δ-MnO2 lattices, enhance their interaction with Al ion species, and increase electrical conductivity, collectively contributing to high ion storage performance. These findings provide inspiration for the development of high-performance cathodes for battery applications.

Design and Advanced Manufacturing of NU-1000 Metal-Organic Frameworks with Future Perspectives for Environmental and Renewable Energy Applications.

Metal-organic frameworks (MOFs) represent a relatively new family of materials that attract lots of attention thanks to their unique features such as hierarchical porosity, active metal centers, versatility of linkers/metal nodes, and large surface area. Among the extended list of MOFs, Zr-based-MOFs demonstrate comparably superior chemical and thermal stabilities, making them ideal candidates for energy and environmental applications. As a Zr-MOF, NU-1000 is first synthesized at Northwestern University. A comprehensive review of various approaches to the synthesis of NU-1000 MOFs for obtaining unique surface properties (e.g., diverse surface morphologies, large surface area, and particular pore size distribution) and their applications in the catalysis (electro-, and photo-catalysis), CO2 reduction, batteries, hydrogen storage, gas storage/separation, and other environmental fields are presented. The review further outlines the current challenges in the development of NU-1000 MOFs and their derivatives in practical applications, revealing areas for future investigation.

Graphene-Based Metal-Organic Framework Hybrids for Applications in Catalysis, Environmental, and Energy Technologies.

Current energy and environmental challenges demand the development and design of multifunctional porous materials with tunable properties for catalysis, water purification, and energy conversion and storage. Because of their amenability to de novo reticular chemistry, metal-organic frameworks (MOFs) have become key materials in this area. However, their usefulness is often limited by low chemical stability, conductivity and inappropriate pore sizes. Conductive two-dimensional (2D) materials with robust structural skeletons and/or functionalized surfaces can form stabilizing interactions with MOF components, enabling the fabrication of MOF nanocomposites with tunable pore characteristics. Graphene and its functional derivatives are the largest class of 2D materials and possess remarkable compositional versatility, structural diversity, and controllable surface chemistry. Here, we critically review current knowledge concerning the growth, structure, and properties of graphene derivatives, MOFs, and their graphene@MOF composites as well as the associated structure-property-performance relationships. Synthetic strategies for preparing graphene@MOF composites and tuning their properties are also comprehensively reviewed together with their applications in gas storage/separation, water purification, catalysis (organo-, electro-, and photocatalysis), and electrochemical energy storage and conversion. Current challenges in the development of graphene@MOF hybrids and their practical applications are addressed, revealing areas for future investigation. We hope that this review will inspire further exploration of new graphene@MOF hybrids for energy, electronic, biomedical, and photocatalysis applications as well as studies on previously unreported properties of known hybrids to reveal potential "diamonds in the rough".

Nitrogen and Sulfur Co-Doped Hierarchically Porous Carbon Nanotubes for Fast Potassium Ion Storage.

Exploration of advanced carbon anode material is the key to circumventing the sluggish kinetics and poor rate capability for potassium ion storage. Herein, a synergistic synthetic strategy of engineering both surface and structure is adopted to design N, S co-doped carbon nanotubes (NS-CNTs). The as-designed NS-CNTs exhibit unique features of defective carbon surface, hollow tubular channel, and enlarged interlayer space. These features significantly contribute to a large potassium storage capacity of 307 mA h g-1 at 1 A g-1 and a remarkable rate performance with a capacity of 151 mA h g-1 even at 5 A g-1 . Furthermore, an excellent cyclability with 98% capacity retention after 500 cycles at 2 A g-1 is also achieved. Systematic analysis by in situ Raman spectroscopy and ex situ TEM demonstrates the structural stability and reversibility in the charge-discharge process. Although the kinetics studies reveal the capacitive-dominated process for potassium storage, density functional theory calculations provide evidence that N, S co-doping contributes to expanding the interlayer space to promote the K-ion insertion, improving the electronic conductivity, and providing ample defective sites to favor the K-ion adsorption.

MOF-derived nanoporous carbons with diverse tunable nanoarchitectures.

Metal-organic frameworks (MOFs), or porous coordination polymers, are crystalline porous materials formed by coordination bonding between inorganic and organic species on the basis of the self-assembly of the reacting units. The typical characteristics of MOFs, including their large specific surface areas, ultrahigh porosities and excellent thermal and chemical stabilities, as well as their great potential for chemical and structural modifications, make them excellent candidates for versatile applications. Their poor electrical conductivity, however, has meant that they have not been useful for electrochemical applications. Fortuitously, the direct carbonization of MOFs results in a rearrangement of the carbon atoms of the organic units into a network of carbon atoms, which means that the products have useful levels of conductivity. The direct carbonization of zeolitic imidazolate framework (ZIF)-type MOFs, particularly ZIF-8, has successfully widened the scope of possible applications of MOFs to include electrochemical reactions that could be used in, for example, energy storage, energy conversion, electrochemical biosensors and capacitive deionization of saline water. Here, we present the first detailed protocols for synthesizing high-quality ZIF-8 and its modified forms of hollow ZIF-8, core-shell ZIF-8@ZIF-67 and ZIF-8@mesostuctured polydopamine. Typically, ZIF-8 synthesis takes 27 h to complete, and subsequent nanoarchitecturing procedures leading to hollow ZIF-8, ZIF-8@ZIF-67 and ZIF-8@mPDA take 6, 14 and 30 h, respectively. The direct-carbonization procedure takes 12 h. The resulting nanoporous carbons are suitable for electrochemical applications, in particular as materials for supercapacitors.

Expeditious Electrochemical Synthesis of Mesoporous Chalcogenide Flakes: Mesoporous Cu2 Se as a Potential High-Rate Anode for Sodium-Ion Battery.

Nanostructured copper selenide (Cu2 Se) attracts much interest as it shows outstanding performance as thermoelectric, photo-thermal, and optical material. The mesoporous structure is also a promising morphology to obtain better performance for electrochemical and catalytic applications, thanks to its high surface area. A simple one-step electrochemical method is proposed for mesoporous chalcogenides synthesis. The synthesized Cu2 Se material has two types of mesopores (9 and 18 nm in diameter), which are uniformly distributed inside the flakes. These materials are also implemented for sodium (Na) ion battery (NIB) anode as a proof of concept. The electrode employing the mesoporous Cu2 Se exhibits superior and more stable specific capacity as a NIB anode compared to the non-porous samples. The electrode also exhibits excellent rate tolerance at each current density, from 100 to 1000 mA g-1 . It is suggested that the mesoporous structure is advantageous for the insertion of Na ions inside the flakes. Electrochemical analysis indicates that the mesoporous electrode possesses more prominent diffusion-controlled kinetics during the sodiation-desodiation process, which contributes to the improvement of Na-ion storage performance.

Progress in Solid Polymer Electrolytes for Lithium-Ion Batteries and Beyond.

Solid-state polymer electrolytes (SPEs) for high electrochemical performance lithium-ion batteries have received considerable attention due to their unique characteristics; they are not prone to leakage, and they exhibit low flammability, excellent processability, good flexibility, high safety levels, and superior thermal stability. However, current SPEs are far from commercialization, mainly due to the low ionic conductivity, low Li+ transference number (tLi+ ), poor electrode/electrolyte interface contact, narrow electrochemical oxidation window, and poor long-term stability of Li metal. Recent work on improving electrochemical performance and these aspects of SPEs are summarized systematically here with a particular focus on the underlying mechanisms, and the improvement strategies are also proposed. This review could lead to a deeper consideration of the issues and solutions affecting the application of SPEs and pave a new pathway to safe, high-performance lithium-ion batteries.

Efficient lithium-ion storage using a heterostructured porous carbon framework and its in situ transmission electron microscopy study.

A heterostructured porous carbon framework (PCF) composed of reduced graphene oxide (rGO) nanosheets and metal organic framework (MOF)-derived microporous carbon is prepared to investigate its potential use in a lithium-ion battery. As an anode material, the PCF exhibits efficient lithium-ion storage performance with a high reversible specific capacity (771 mA h g-1 at 50 mA g-1), an excellent rate capability (448 mA h g-1 at 1000 mA g-1), and a long lifespan (75% retention after 400 cycles). The in situ transmission electron microscopy (TEM) study demonstrates that its unique three-dimensional (3D) heterostructure can largely tolerate the volume expansion. We envisage that this work may offer a deeper understanding of the importance of tailored design of anode materials for future lithium-ion batteries.

Rational Design of Graphene Derivatives for Electrochemical Reduction of Nitrogen to Ammonia.

The conversion of nitrogen to ammonia offers a sustainable and environmentally friendly approach for producing precursors for fertilizers and efficient energy carriers. Owing to the large energy density and significant gravimetric hydrogen content, NH3 is considered an apt next-generation energy carrier and liquid fuel. However, the low conversion efficiency and slow production of ammonia through the nitrogen reduction reaction (NRR) are currently bottlenecks, making it an unviable alternative to the traditional Haber-Bosch process for ammonia production. The rational design and engineering of catalysts (both photo- and electro-) represent a crucial challenge for improving the efficiency and exploiting the full capability of the NRR. In the present review, we highlight recent progress in the development of graphene-based systems and graphene derivatives as catalysts for the NRR. Initially, the history, fundamental mechanism, and importance of the NRR to produce ammonia are briefly discussed. We also outline how surface functionalization, defects, and hybrid structures (single-atom/multiatom as well as composites) affect the N2 conversion efficiency. The potential of graphene and graphene derivatives as NRR catalysts is highlighted using pertinent examples from theoretical simulations as well as machine learning based performance predictive methods. The review is concluded by identifying the crucial advantages, drawbacks, and challenges associated with principal scientific and technological breakthroughs in ambient catalytic NRR.

Tunable Graphene Oxide Nanofiltration Membrane for Effective Dye/Salt Separation and Desalination.

Effective dye separation and desalination are critical for the treatment of highly saline textile wastewater with dye mixtures. In this study, a graphene oxide (GO) membrane with a tunable interlayer distance (d) was fabricated to generate clean water via two-stage filtration, namely, the dye/salt separation and desalination stages. In the first stage, under low pressure (e.g., 0.3 MPa), the membrane with a d value of ca. 7.60 Å was suitable for removing the dye from the saline wastewater. The dye and salt (i.e., Na2SO4) rejection rates of >99% and <6.5% were achieved, respectively, indicating the significant potential to recycle the dyes from the highly saline dye wastewater. In the second stage, under a higher pressure (e.g., 0.8 MPa), the d value was reduced to ca. 7.15 Å, bestowing the membrane with a desalination function. The desalination rate of a single filtration process could reach up to 51.8% from 1.0 g/L saline (i.e., Na2SO4) water. The as-prepared membrane also exhibited excellent practical advantages, including ultrahigh permeability, significant antifouling (against dye) performance, and excellent stability. Furthermore, with the stacking of multistage filtration systems, the proposed membrane technology will be capable of regenerating dye and producing clean water.

KOH-Activated Hollow ZIF-8 Derived Porous Carbon: Nanoarchitectured Control for Upgraded Capacitive Deionization and Supercapacitor.

Herein, the synergistic effects of hollow nanoarchitecture and high specific surface area of hollow activated carbons (HACs) are reported with the superior supercapacitor (SC) and capacitive deionization (CDI) performance. The center of zeolite imidazolate framework-8 (ZIF-8) is selectively etched to create a hollow cavity as a macropore, and the resulting hollow ZIF-8 (HZIF-8) is carbonized to obtain hollow carbon (HC). The distribution of nanopores is, subsequently, optimized by KOH activation to create more nanopores and significantly increase specific surface area. Indeed, as-prepared hollow activated carbons (HACs) show significant improvement not only in the maximum specific capacitance and desalination capacity but also capacitance retention and mean desalination rates in SC and CDI, respectively. As a result, it is confirmed that well-designed nanoarchitecture and porosity are required to allow efficient diffusion and maximum electrosorption of electrolyte ions.

Nitrogen-Doped Mesoporous Carbon Microspheres by Spray Drying-Vapor Deposition for High-Performance Supercapacitor.

Nitrogen-doped mesoporous carbon microspheres have been successfully synthesized via a spray drying-vapor deposition method for the first time, using commercial Ludox silica nanoparticles as hard templates. Compared to freeze-drying and air-drying methods, mesoporous carbon with a higher packing density can be achieved through the spray drying method. Vapor deposition of polypyrrole followed by carbonization and etching is beneficial for the generation of ultra-thin carbon network. The mesoporous carbon microspheres possess a mesopore-dominate (95%) high surface area of 1528 m2 g-1, a wall thickness of 1.8 nm, and a nitrogen content of 8 at% in the framework. Benefiting from the increased apparent density, high mesopore surface area, and considerable nitrogen doping, the resultant mesoporous carbon microspheres show superior gravimetric/volumetric capacitance of 533.6 F g-1 and 208.1 F cm-3, good rate performance and excellent cycling stability in electric double-layer capacitors.

True Meaning of Pseudocapacitors and Their Performance Metrics: Asymmetric versus Hybrid Supercapacitors.

The development of pseudocapacitive materials for energy-oriented applications has stimulated considerable interest in recent years due to their high energy-storing capacity with high power outputs. Nevertheless, the utilization of nanosized active materials in batteries leads to fast redox kinetics due to the improved surface area and short diffusion pathways, which shifts their electrochemical signatures from battery-like to the pseudocapacitive-like behavior. As a result, it becomes challenging to distinguish "pseudocapacitive" and "battery" materials. Such misconceptions have further impacted on the final device configurations. This Review is an earnest effort to clarify the confusion between the battery and pseudocapacitive materials by providing their true meanings and correct performance metrics. A method to distinguish battery-type and pseudocapacitive materials using the electrochemical signatures and quantitative kinetics analysis is outlined. Taking solid-state supercapacitors (SSCs, only polymer gel electrolytes) as an example, the distinction between asymmetric and hybrid supercapacitors is discussed. The state-of-the-art progress in the engineering of active materials is summarized, which will guide for the development of real-pseudocapacitive energy storage systems.

Sandwich-Structured Ordered Mesoporous Polydopamine/MXene Hybrids as High-Performance Anodes for Lithium-Ion Batteries.

Organic polymers have attracted significant interest as electrodes for energy storage devices because of their advantages, including molecular flexibility, cost-effectiveness, and environmentally friendly nature. Nevertheless, the real implementation of polymer-based electrodes is restricted by their poor stability, low capacity, and slow electron-transfer/ion diffusion kinetics. In this work, a sandwich-structured composite of ordered mesoporous polydopamine (OMPDA)/Ti3C2Tx has been fabricated by in situ polymerization of dopamine on the surface of Ti3C2Tx via employing the PS-b-PEO block polymer as a soft template. The OMPDA layers with vertically oriented, accessible nanopores (∼20 nm) provide a continuous pore channel for ion diffusion, while the Ti3C2Tx layers guarantee a fast electron-transfer path. The OMPDA/Ti3C2Tx composite anode exhibits high reversible capacity, good rate performance, and excellent cyclability for lithium-ion batteries. The in situ transmission electron microscopy analysis reveals that the OMPDA in the composite only shows a small volume expansion and almost preserves the initial morphology during lithiation. Moreover, these in situ experiments also demonstrate the generation of a stable and ultrathin solid electrolyte interphase layer surrounding the active material, which acts as an electrode protective film during cycling. This study demonstrates the method to develop polymer-based electrodes for high-performance rechargeable batteries.

Modulating Ion Diffusivity and Electrode Conductivity of Carbon Nanotube@Mesoporous Carbon Fibers for High Performance Aluminum-Selenium Batteries.

Selenium (Se)-based rechargeable aluminum batteries (RABs), known as aluminum-selenium (Al-Se) batteries, are an appealing new battery design that holds great promise for addressing the low-capacity problem of current RAB technology. However, their applications are hindered by mediocre high-rate capacity (≈100 mAh g-1 at 0.5 A g-1 ) and insufficient cycling life (50 cycles). Herein, the synthesis of mesoporous carbon fibers (MCFs) by coating mesoporous carbon with short-length mesopores and tunable mesopore sizes (2.7 to 8.9 nm) coaxially on carbon nanotubes (CNT) is reported. When compositing MCFs with Se for Al-Se batteries, a positive correlation between mesopore size and electrolyte ion diffusivity is observed, however when pore size is increased to 8.9 nm, large voids are created at the interface of CNT core and mesoporous carbon shell, leading to decreased electrode conductivity. The trade-off between ion diffusivity and interfacial connectivity/conductivity determines MCF with pore size of 7.1 nm as the best host material for Al-Se batteries. The composite cathode delivers high specific capacities (366 and 230 mAh g-1 at 0.5 and 1 A g-1 ), good rate performance, and excellent cycling stability (152 mAh g-1 after 500 cycles at 2 A g-1 ), superior over previously reported Se cathodes and other cathodes for RABs.

Molecular Design Strategies for Electrochemical Behavior of Aromatic Carbonyl Compounds in Organic and Aqueous Electrolytes.

To sustainably satisfy the growing demand for energy, organic carbonyl compounds (OCCs) are being widely studied as electrode active materials for batteries owing to their high capacity, flexible structure, low cost, environmental friendliness, renewability, and universal applicability. However, their high solubility in electrolytes, limited active sites, and low conductivity are obstacles in increasing their usage. Here, the nucleophilic addition reaction of aromatic carbonyl compounds (ACCs) is first used to explain the electrochemical behavior of carbonyl compounds during charge-discharge, and the relationship of the molecular structure and electrochemical properties of ACCs are discussed. Strategies for molecular structure modifications to improve the performance of ACCs, i.e., the capacity density, cycle life, rate performance, and voltage of the discharge platform, are also elaborated. ACCs, as electrode active materials in aqueous solutions, will become a future research hotspot. ACCs will inevitably become sustainable green materials for batteries with high capacity density and high power density.

Pore-tuning to boost the electrocatalytic activity of polymeric micelle-templated mesoporous Pd nanoparticles.

Understanding how mesoporous noble metal architectures affect electrocatalytic performance is very important for the rational design and preparation of high-performance electrocatalysts. Herein, by using polymeric micelle-assembled structures as templates, mesoporous Pd nanoparticles with tunable porous constructions are synthesized by simply tuning the solvent compositions. The effect of porous Pd nanoparticles on the electrocatalytic performance is thoroughly studied. Their superior electrocatalytic activity can be attributed to the mass transport efficiency and open porous structures.

Double-Layered Modified Separators as Shuttle Suppressing Interlayers for Lithium-Sulfur Batteries.

The shuttling phenomena in lithium-sulfur batteries lead to drastic attenuation of the capacity. This can be suppressed effectively by modifying the separator. Herein, a double-layered separator composed of a macroporous polypropylene (PP) matrix layer and an arrayed poly(methyl methacrylate) (PMMA) microsphere retarding layer is designed as the separator for lithium-sulfur batteries. A sulfur positive electrode with the PP/PMMA separator exhibits a high initial capacity of 1100.10 mAh g-1 at a current density of 0.1 mA cm-2 along with a high Coulombic efficiency, which is higher than the corresponding first discharge capacity results obtained using the standard PP separator (948.60 mAh g-1). In the double-layered separator, the arrayed PMMA microspheres can inhibit the diffusion of polysulfides through physical and chemical adsorption, thereby improving the electrochemical performance of lithium-sulfur batteries. In addition, the PMMA microspheres enhance the affinity of the separator to the electrolyte, which will increase the adsorption of the electrolyte to the separator and accelerate the diffusion rate of lithium ions.