Sulfonated Graphene as Cation‐Selective Coating: A New Strategy for High‐Performance Membrane Capacitive Deionization

Membrane capacitive deionization (MCDI) featuring both high electrosorption capacity and high energy efficiency holds promise for desalination. However, the large‐scale applications of MCDI are limited greatly by the high cost of commercial ion‐exchange membranes and the interfacial resistance. Here, a new strategy for high‐performance MCDI is established using sulfonated graphene (SG) as cation‐selective coating. A continuous ultrathin SG coating via self‐assembly is formed and attached tightly onto the surface of electrospun carbon nanofibers (CNFs) by a simple yet effective dip‐coating technique, yielding SG‐CNF composites with a hydrophilic surface, high electrochemical specific capacitance, and greatly reduced interfacial charge transfer rate. These result in significantly enhanced capacitive deionization performance in terms of both electrosorption capacity and charge efficiency. The SG coating shows excellent cation selectivity for an asymmetric cell with SG–CNFs as a cathode. The new approach may pave a way to novel micro‐MCDI, i.e. novel applications of functional graphene‐based materials for high‐performance, energy‐efficient, and cost‐effective desalination.     

超薄MnOx修饰多孔碳纳米纤维及其电容脱盐

MnO₂具有较高的理论比电容而作为良好的电容器材料,但因其导电性和循环稳定性较差,从而限制其电化学应用。本研究以静电纺丝技术制备的多孔碳纳米纤维（PCNF）为载体,经KMnO₄浸泡后,高温退火获得超薄MnO_x层修饰的复合碳纳米纤维（APCNF-MnO_x）。通过接触角、SEM、TEM、电化学表征及电容脱盐测试对比分析了碳纤维多孔结构对MnO_x形貌及电化学性能的影响。电化学测试结果表明：APCNF-MnO_x电极的比电容是退火的MnO_x修饰无孔碳纳米纤维（ACNF-MnO_x）电极的4倍（20 mV/s）。以APCNF-MnO_x为电容器负极材料,成功制得电容器去离子器件,其电容脱盐量达到9.23 mg/g,比ACNF-MnO_x提高了29%。     

Controlled Air‐Etching Synthesis of Porous‐Carbon Nanotube Aerogels with Ultrafast Charging at 1000 A g−1

Supercapacitors are energy storage systems capable of fast charging and discharging, thus generating superior power density. Porous carbon with high surface area and tunable pore size represents a promising candidate to construct ultrafast supercapacitors; so far, most porous carbon–based electrodes can only be charged to a moderate current density (100–200 A g^?1), also with significant capacitance loss at increasing rate. Here, it is shown that a 3D aerogel consisting of interconnected 1D porous‐carbon nanotubes (PCNs) can serve as a freestanding supercapacitor electrode with excellent rate performance. As a result, the PCN aerogel electrodes achieve 1) ultrafast charging at current densities up to 1000 A g^?1 (corresponding to a charge period of 16 ms), which is the highest value among other porous carbon–based supercapacitors, 2) superior cycling stability at high charging rates (88% capacitance retention after 10⁵ cycles at 1000 A g^?1). Mechanism study reveals favorable kinetics including a centralized pore size distribution at 0.8 nm which is a dominant factor to allow high‐rate charging, a low and linear IR drop, and a metallic feature of 1D PCNs by theoretical calculation. The results indicate that 1D PCNs with controlled porous structures have potential applications in ultrafast energy conversion and storage.     

Nitrogen‐Doped Graphene‐Buffered Mn2O3 Nanocomposite Anodes for Fast Charging and High Discharge Capacity Lithium‐Ion Batteries

Mn₂O₃ is a promising anode material for lithium‐ion batteries (LIBs) because of its high theoretical capacity and low discharge potential. However, low electronic conductivity and capacity fading limits its practical application. In this work, Mn₂O₃ with 1D nanowire geometry is synthesized in neutral aqueous solutions by a facile and effective hydrothermal strategy for the first time, and then Mn₂O₃ nanoparticle and nitrogen‐doped reduced graphene oxide (N‐rGO) are composited with Mn₂O₃ nanowires (Mn₂O₃‐GNCs) to enhance its volume utilization and conductivity. When used as an anode material for LIBs, the Mn₂O₃‐GNCs exhibit high reversible capacity (1350 mAh g^?1), stable cycling stability, and good rate capability. Surprisingly, the Mn₂O₃‐GNC electrodes can also show fast charging capability; even after 200 cycles (charge: 10 A g^?1; discharge: 0.5 A g^?1), its discharge capacity can also keep at ≈500 mAh g^?1. In addition, the Mn₂O₃‐GNCs also have considerable full cell and supercapacitor performance. The excellent electrochemical performances can be ascribed to the N‐rGO network structure and 1D nanowire structure, which can ensure fast ion and electron transportation.     

Ultra‐light Hierarchical Graphene Electrode for Binder‐Free Supercapacitors and Lithium‐Ion Battery Anodes

A mild and environmental‐friendly method is developed for fabricating a 3D interconnected graphene electrode with large‐scale continuity. Such material has interlayer pores between reduced graphene oxide nanosheets and in‐plane pores. Hence, a specific surface area up to 835 m² g⁻¹ and a high powder conductivity up to 400 S m⁻¹ are achieved. For electrochemical applications, the interlayer pores can serve as “ion‐buffering reservoirs” while in‐plane ones act as “channels” for shortening the mass cross‐plane diffusion length, reducing the ion response time, and prevent the interlayer restacking. As binder‐free supercapacitor electrode, it delivers a specific capacitance up to 169 F g⁻¹ with surface‐normalized capacitance close to 21 μF cm⁻² (intrinsic capacitance) and power density up to 7.5 kW kg⁻¹, in 6 m KOH aqueous electrolyte. In the case of lithium‐ion battery anode, it shows remarkable advantages in terms of the initiate reversible Coulombic efficiency (61.3%), high specific capacity (932 mAh g⁻¹ at 100 mA g⁻¹), and robust long‐term retention (93.5% after 600 cycles at 2000 mAh g⁻¹).     

Hierarchical 3D All‐Carbon Composite Structure Modified with N‐Doped Graphene Quantum Dots for High‐Performance Flexible Supercapacitors

Flexible supercapacitors have shown enormous potential for portable electronic devices. Herein, hierarchical 3D all‐carbon electrode materials are prepared by assembling N‐doped graphene quantum dots (N‐GQDs) on carbonized MOF materials (cZIF‐8) interweaved with carbon nanotubes (CNTs) for flexible all‐solid‐state supercapacitors. In this ternary electrode, cZIF‐8 provides a large accessible surface area, CNTs act as the electrical conductive network, and N‐GQDs serve as highly pseudocapactive materials. Due to the synergistic effect and hierarchical assembly of these components, N‐GQD@cZIF‐8/CNT electrodes exhibit a high specific capacitance of 540 F g^?1 at 0.5 A g^?1 in a 1 m H₂SO₄ electrolyte and excellent cycle stability with 90.9% capacity retention over 8000 cycles. The assembled supercapacitor possesses an energy density of 18.75 Wh kg^?1 with a power density of 108.7 W kg^?1. Meanwhile, three supercapacitors connected in series can power light‐emitting diodes for 20 min. All‐solid‐state N‐GQD@cZIF‐8/CNT flexible supercapacitor exhibits an energy density of 14 Wh kg^?1 with a power density of 89.3 W kg^?1, while the capacitance retention after 5000 cycles reaches 82%. This work provides an effective way to construct novel electrode materials with high energy storage density as well as good cycling performance and power density for high‐performance energy storage devices via the rational design.     

In Situ Formation of Hierarchical Bismuth Nanodots/Graphene Nanoarchitectures for Ultrahigh‐Rate and Durable Potassium‐Ion Storage

Metallic bismuth (Bi) has been widely explored as remarkable anode material in alkali‐ion batteries due to its high gravimetric/volumetric capacity. However, the huge volume expansion up to ≈406% from Bi to full potassiation phase K₃Bi, inducing the slow kinetics and poor cycling stability, hinders its implementation in potassium‐ion batteries (PIBs). Here, facile strategy is developed to synthesize hierarchical bismuth nanodots/graphene (BiND/G) composites with ultrahigh‐rate and durable potassium ion storage derived from an in situ spontaneous reduction of sodium bismuthate/graphene composites. The in situ formed ultrafine BiND (≈3 nm) confined in graphene layers can not only effectively accommodate the volume change during the alloying/dealloying process but can also provide high‐speed channels for ionic transport to the highly active BiND. The BiND/G electrode provides a superior rate capability of 200 mA h g^?1 at 10 A g^?1 and an impressive reversible capacity of 213 mA h g^?1 at 5 A g^?1 after 500 cycles with almost no capacity decay. An operando synchrotron radiation‐based X‐ray diffraction reveals distinctively sharp multiphase transitions, suggesting its underlying operation mechanisms and superiority in potassium ion storage application.     

Hierarchical NiO@N‐Doped Carbon Microspheres with Ultrathin Nanosheet Subunits as Excellent Photocatalysts for Hydrogen Evolution

Achieving highly efficient hierarchical photocatalysts for hydrogen evolution is always challenging. Herein, hierarchical mesoporous NiO@N‐doped carbon microspheres (HNINC) are successfully fabricated with ultrathin nanosheet subunits as high‐performance photocatalysts for hydrogen evolution. The unique architecture of N‐doped carbon layers and hierarchical mesoporous structures from HNINC could effectively facilitate the separation and transfer of photo‐induced electron–hole pairs and afford rich active sites for photocatalytic reactions, leading to a significantly higher H₂ production rate than NiO deposited with platinum. Density functional theory calculations reveal that the migration path of the photo‐generated electron transfer is from Ni 3d and O 2p hybrid states of NiO to the C 2p state of graphite, while the photo‐generated holes locate at Ni 4s and Ni 4p hybrid states of NiO, which is beneficial to improve the separation of photo‐generated electron–hole pairs. Gibbs free energy of the intermediate state for hydrogen evolution reaction is calculated to provide a fundamental understanding of the high H₂ production rate of HNINC. This research sheds light on developing novel photocatalysts for efficient hydrogen evolution.     

Insights into the Effect of Structural Heterogeneity in Carbonized Electrospun Fibrous Mats for Flow Battery Electrodes by X‐Ray Tomography

Electrospun custom made flow battery electrodes are imaged in 3D using X‐ray computed tomography. A variety of computational methods and simulations are applied to the images to determine properties including the porosity, fiber size, and pore size distributions as well as the material permeability and flow distributions. The simulations are performed on materials before and after carbonization to determine the effect it has in the internal microstructure and material properties. It is found that the deposited fiber size is constantly changing throughout the electrospinning process. The results also show that the surfaces of the fibrous material are the most severely altered during carbonization and that the rest of the material remained intact. Pressure driven flow is modeled using the lattice Boltzmann method and excellent agreement with experimental results is found. The simulations coupled with the material analysis also demonstrate the highly heterogeneous nature of the flow. Most of the flow is concentrated to regions with high porosity while regions with low porosity shield other pores and starve them of flow. The importance of imaging these materials in 3D is highlighted throughout.     

Flexible Graphene‐Wrapped Carbon Nanotube/Graphene@MnO2 3D Multilevel Porous Film for High‐Performance Lithium‐Ion Batteries

The ingenious design of a freestanding flexible electrode brings the possibility for power sources in emerging wearable electronic devices. Here, reduced graphene oxide (rGO) wraps carbon nanotubes (CNTs) and rGO tightly surrounded by MnO₂ nanosheets, forming a 3D multilevel porous conductive structure via vacuum freeze‐drying. The sandwich‐like architecture possesses multiple functions as a flexible anode for lithium‐ion batteries. Micrometer‐sized pores among the continuously waved rGO layers could extraordinarily improve ion diffusion. Nano‐sized pores among the MnO₂ nanosheets and CNT/rGO@MnO₂ particles could provide vast accessible active sites and alleviate volume change. The tight connection between MnO₂ and carbon skeleton could facilitate electron transportation and enhance structural stability. Due to the special structure, the rGO‐wrapped CNT/rGO@MnO₂ porous film as an anode shows a high capacity, excellent rate performance, and superior cycling stability (1344.2 mAh g⁻¹ over 630 cycles at 2 A g⁻¹, 608.5 mAh g⁻¹ over 1000 cycles at 7.5 A g⁻¹). Furthermore, the evolutions of microstructure and chemical valence occurring inside the electrode after cycling are investigated to illuminate the structural superiority for energy storage. The excellent electrochemical performance of this freestanding flexible electrode makes it an attractive candidate for practical application in flexible energy storage.     

Promoting Reversible Redox Kinetics by Separator Architectures Based on CoS2/HPGC Interlayer as Efficient Polysulfide‐Trapping Shield for Li–S Batteries

Main obstacles from the shuttle effect and slow conversion rate of soluble polysulfide compromise the sulfur utilization and cycling life for lithium sulfur (Li–S) batteries. In pursuit of a practically viable high performance Li–S battery, a separator configuration (CoS₂/HPGC/interlayer) as efficient polysulfide trapping barrier is reported. This configuration endows great advantages, particularly enhanced conductivity, promoted polysulfide trapping capability, accelerated sulfur electrochemistry, when using the functional interlayer for Li–S cells. Attributed to the above merits, such cell shows excellent cyclability, with a capacity of 846 mAh g^?1 after 250 cycles corresponding to a high capacity retention of 80.2% at 0.2 C, and 519 mAh g^?1 after 500 cycles at 1C (1C = 1675 mA g^?1). In addition, the optimized separator exhibits a high initial areal capacity of 4.293 mAh cm^?2 at 0.1C. Moreover, with CoS₂/HPGC/interlayer, the sulfur cell enables a low self‐discharge rate with a very high capacity retention of 97.1%. This work presents a structural engineering of the separator toward suppressing the dissolution of soluble Li₂Sn moieties and simultaneously promoting the sulfur conversion kinetics, thus achieving durable and high capacity Li–S batteries.     

Combining X‐Ray Whole Powder Pattern Modeling,Rietveld and Pair Distribution Function Analyses as a Novel Bulk Approach to Study Interfaces in Heteronanostructures: Oxidation Front in FeO/Fe3O4 Core/Shell Nanoparticles as a Case Study

Understanding the microstructure in heterostructured nanoparticles is crucial to harnessing their properties. Although microscopy is ideal for this purpose, it allows for the analysis of only a few nanoparticles. Thus, there is a need for structural methods that take the whole sample into account. Here, a novel bulk‐approach based on the combined analysis of synchrotron X‐ray powder diffraction with whole powder pattern modeling, Rietveld and pair distribution function is presented. The microstructural temporal evolution of FeO/Fe₃O₄ core/shell nanocubes is studied at different time intervals. The results indicate that a two‐phase approach (FeO and Fe₃O₄) is not sufficient to successfully fit the data and two additional interface phases (FeO and Fe₃O₄) are needed to obtain satisfactory fits, i.e., an onion‐type structure. The analysis shows that the Fe₃O₄ phases grow to some extent (≈1 nm) at the expense of the FeO core. Moreover, the FeO core progressively changes its stoichiometry to accommodate more oxygen. The temporal evolution of the parameters indicates that the structure of the FeO/Fe₃O₄ nanocubes is rather stable, although the exact interface structure slightly evolves with time. This approach paves the way for average studies of interfaces in different kinds of heterostructured nanoparticles, particularly in cases where spectroscopic methods have some limitations.