CO2 Nanoenrichment and Nanoconfinement in Cage of Imine Covalent Organic Frameworks for High‐Performance CO2 Cathodes in Li‐CO2 Batteries

The Li‐CO₂ battery is an emerging green energy technology coupling CO₂ capture and conversion. The main drawback of present Li‐CO₂ batteries is serious polarization and poor cycling caused by random deposition of lithium ions and big insulated Li₂CO₃ formation on the cathode during discharge. Herein, covalent organic frameworks (COF) are identified as the porous catalyst in the cathode of Li‐CO₂ batteries for the first time. Graphene@COF is fabricated, graphene with thin and uniform imine COF loading, to enrich and confine CO₂ in the nanospaces of micropores. The discharge voltage is raised by higher local CO₂ concentration, which is predicted by the Nernst equation and realized by CO₂ nanoenrichment. Moreover, uniform lithium ion deposition directed by the graphene@COF nanoconfined CO₂ can produce smaller Li₂CO₃ particles, leading to easier Li₂CO₃ decomposition and thus lower charge voltage. The graphene@COF cathode with 47.5% carbon content achieves a discharge capacity of 27833 mAh g^?1 at 75 mA g^?1, while retaining a low charge potential of 3.5 V at 0.5 A g^?1 for 56 cycles.     

Functional Separator Enabled by Covalent Organic Frameworks for High-Performance Li Metal Batteries

Uncontrolled ion transport and susceptible SEI films are the key factors that induce lithium dendrite growth, which hinders the development of lithium metal batteries (LMBs). Herein, a TpPa-2SO₃H covalent organic framework (COF) nanosheet adhered cellulose nanofibers (CNF) on the polypropylene separator (COF@PP) is successfully designed as a battery separator to respond to the aforementioned issues. The COF@PP displays dual-functional characteristics with the aligned nanochannels and abundant functional groups of COFs, which can simultaneously modulate ion transport and SEI film components to build robust lithium metal anodes. The Li//COF@PP//Li symmetric cell exhibits stable cycling over 800 h with low ion diffusion activation energy and fast lithium ion transport kinetics, which effectively suppresses the dendrite growth and improves the stability of Li+ plating/stripping. Moreover, The LiFePO4//Li cells with COF@PP separator deliver a high discharge capacity of 109.6 mAh g⁻¹ even at a high current density of 3 C. And it exhibits excellent cycle stability and high capacity retention due to the robust LiF-rich SEI film induced by COFs. This COFs-based dual-functional separator promotes the practical application of lithium metal batteries.     

Pyrolytic Carbon Nanosheets for Ultrafast and Ultrastable Sodium‐Ion Storage

Na‐ion cointercalation in the graphite host structure in a glyme‐based electrolyte represents a new possibility for using carbon‐based materials (CMs) as anodes for Na‐ion storage. However, local microstructures and nanoscale morphological features in CMs affect their electrochemical performances; they require intensive studies to achieve high levels of Na‐ion storage performances. Here, pyrolytic carbon nanosheets (PCNs) composed of multitudinous graphitic nanocrystals are prepared from renewable bioresources by heating. In particular, PCN‐2800 prepared by heating at 2800 °C has a distinctive sp² carbon bonding nature, crystalline domain size of ≈44.2 Å, and high electrical conductivity of ≈320 S cm^?1, presenting significantly high rate capability at 600 C (60 A g^?1) and stable cycling behaviors over 40 000 cycles as an anode for Na‐ion storage. The results of this study show the unusual graphitization behaviors of a char‐type carbon precursor and exceptionally high rate and cycling performances of the resulting graphitic material, PCN‐2800, even surpassing those of supercapacitors.     

One-Dimensional Covalent Organic Framework as High-Performance Cathode Materials for Lithium-Ion Batteries

Covalent organic frameworks (COFs) have emerged as a new class of cathode materials for energy storage in recent years. However, they are limited to two-dimensional (2D) or three-dimensional (3D) framework structures. Herein, this work reports designed synthesis of a redox-active one-dimensional (1D) COF and its composites with 1D carbon nanotubes (CNTs) via in situ growth. Used as cathode materials for Li-ion batteries, the 1D COF@CNT composites with unique dendritic core–shell structure can provide abundant and easily accessible redox-active sites, which contribute to improve diffusion rate of lithium ions and the corresponding specific capacity. This synergistic structural design enables excellent electrochemical performance of the cathodes, giving rise to 95% utilization of redox-active sites, high rate capability (81% capacity retention at 10 C), and long cycling stability (86% retention after 600 cycles at 5 C). As the first example to explore the application of 1D COFs in the field of energy storage, this study demonstrates the great potential of this novel type of linear crystalline porous polymers in battery technologies.     

Recent Progress in the Design of Advanced Cathode Materials and Battery Models for High‐Performance Lithium‐X (X = O2, S,Se, Te,I2, Br2) Batteries

Recent advances and achievements in emerging Li‐X (X = O₂, S, Se, Te, I₂, Br₂) batteries with promising cathode materials open up new opportunities for the development of high‐performance lithium‐ion battery alternatives. In this review, we focus on an overview of recent important progress in the design of advanced cathode materials and battery models for developing high‐performance Li‐X (X = O₂, S, Se, Te, I₂, Br₂) batteries. We start with a brief introduction to explain why Li‐X batteries are important for future renewable energy devices. Then, we summarize the existing drawbacks, major progress and emerging challenges in the development of cathode materials for Li‐O₂ (S) batteries. In terms of the emerging Li‐X (Se, Te, I₂, Br₂) batteries, we systematically summarize their advantages/disadvantages and recent progress. Specifically, we review the electrochemical performance of Li‐Se (Te) batteries using carbonate‐/ether‐based electrolytes, made with different electrode fabrication techniques, and of Li‐I₂ (Br₂) batteries with various cell designs (e.g., dual electrolyte, all‐organic electrolyte, with/without cathode‐flow mode, and fuel cell/solar cell integration). Finally, the perspective on and challenges for the development of cathode materials for the promising Li‐X (X = O₂, S, Se, Te, I₂, Br₂) batteries is presented.     

Ultralong Lifespan and Ultrafast Li Storage: Single‐Crystal LiFePO4 Nanomeshes

A novel LiFePO₄ material, in the shape of a nanomesh, has been rationally designed and synthesized based on the low crystal‐mismatch strategy. The LiFePO₄ nanomesh possesses several advantages in morphology and crystal structure, including a mesoporous structure, its crystal orientation that is along the [010] direction, and a shortened Li‐ion diffusion path. These properties are favorable for their application as cathode in Li‐ion batteries, as these will accelerate the Li‐ion diffusion rate, improve the Li‐ion exchange between the LiFePO₄ nanomesh and the electrolyte, and reduce the Li‐ion capacitive behavior during Li intercalation. So the LiFePO₄ nanomesh exhibits a high specific capacity, enhanced rate capability, and strengthened cyclability. The method developed here can also be extended to other similar systems, for instance, LiMnPO₄, LiCoPO₄, and LiNiPO₄, and may find more applications in the designed synthesis of functional materials.     

Electrostatically Assembling 2D Nanosheets of MXene and MOF‐Derivatives into 3D Hollow Frameworks for Enhanced Lithium Storage

As an essential member of 2D materials, MXene (e.g., Ti₃C₂T_x) is highly preferred for energy storage owing to a high surface‐to‐volume ratio, shortened ion diffusion pathway, superior electronic conductivity, and neglectable volume change, which are beneficial for electrochemical kinetics. However, the low theoretical capacitance and restacking issues of MXene severely limit its practical application in lithium‐ion batteries (LIBs). Herein, a facile and controllable method is developed to engineer 2D nanosheets of negatively charged MXene and positively charged layered double hydroxides derived from ZIF‐67 polyhedrons into 3D hollow frameworks via electrostatic self‐assembling. After thermal annealing, transition metal oxides (TMOs)@MXene (CoO/Co₂Mo₃O₈@MXene) hollow frameworks are obtained and used as anode materials for LIBs. CoO/Co₂Mo₃O₈ nanosheets prevent MXene from aggregation and contribute remarkable lithium storage capacity, while MXene nanosheets provide a 3D conductive network and mechanical robustness to facilitate rapid charge transfer at the interface, and accommodate the volume expansion of the internal CoO/Co₂Mo₃O₈. Such hollow frameworks present a high reversible capacity of 947.4 mAh g^?1 at 0.1 A g^?1, an impressive rate behavior with 435.8 mAh g^?1 retained at 5 A g^?1, and good stability over 1200 cycles (545 mAh g^?1 at 2 A g^?1).     

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.     

Ultrathin 2D Mesoporous TiO2/rGO Heterostructure for High‐Performance Lithium Storage

Lithium‐ion batteries (LIBs) have been widely applied and studied as an effective energy supplement for a variety of electronic devices. Titanium dioxide (TiO₂), with a high theoretical capacity (335 mAh g^?1) and low volume expansion ratio upon lithiation, has been considered as one of the most promising anode materials for LIBs. However, the application of TiO₂ is hindered by its low electrical conductivity and slow ionic diffusion rate. Herein, a 2D ultrathin mesoporous TiO₂/reduced graphene (rGO) heterostructure is fabricated via a layer‐by‐layer assembly process. The synergistic effect of ultrathin mesoporous TiO₂ and the rGO nanosheets significantly enhances the ionic diffusion and electron conductivity of the composite. The introduced 2D mesoporous heterostructure delivers a significantly improved capacity of 350 mAh g^?1 at a current density of 200 mA g^?1 and excellent cycling stability, with a capacity of 245 mAh g^?1 maintained over 1000 cycles at a high current density of 1 A g^?1. The in situ transmission electron microscopy analysis indicates that the volume of the as‐prepared 2D heterostructures changes slightly upon the insertion and extraction of Li⁺, thus contributing to the enhanced long‐cycle performance.     

锂离子电池正极材料LiNi-x-yCoxMnyO2的研究现状

正极材料对锂离子电池的性能和价格具有决定性的作用，对正极材料的研究一直是锂离子电池研究中的热点。主要对一类新型正极材料LiNi-x-yCoxMnyO2的国内外研究现状进行了综述，并比较了不同合成方法对其电化学性能的影响，最后对这类正极材料的研究给予了展望。     

Structural Approaches to Control Interlayer Interactions in 2D Covalent Organic Frameworks

The ability to design and synthesize monomers can affect fundamental aspects in 2D covalent organic frameworks, such as dimensionality, topology, and pore size. Besides this, the structure of the monomers can also affect interlayer interactions, which provide an additional means to influence crystallinity, layer arrangement, interlayer distances, and exfoliability. Herein, some of the effects that the structure of monomers can have on the interlayer interactions in 2D covalent organic frameworks and related materials are illustrated.     

New Layered Triazine Framework/Exfoliated 2D Polymer with Superior Sodium‐Storage Properties

The efficient synthesis of 2D polymers (2DPs) with tailorable structures and properties is highly desired but remains a considerable challenge. Here, the first solution synthesis of millimeter‐size crystalline covalent triazine frameworks (CTFs) with a clear lamellar structure, which can be exfoliated into micrometer‐size few‐layer 2DP sheets via both micromechanical cleavage and liquid sonication, is reported. The obtained CTFs or 2DPs show a unique staggered AB stacking with a dominant pore size of ≈0.6 nm, which is different from the common eclipsed AA stacking in various covalent organic frameworks. The preference for AB stacking is due to the specific interaction of triflic acid with CTFs as revealed computationally. When explored as new polymeric anodes for sodium‐ion batteries, both crystalline bulk CTF and exfoliated 2DP exhibit very high capacities (225 and 262 mA h g^?1 at 0.1 A g^?1, respectively), impressive rate capabilities (67 and 119 mA h g^?1 at 5.0 A g^?1, respectively), and excellent cycling stability (95% capacity retention after 1200 cycles) due to their robust conjugated porous structure, outperforming most organic/polymeric sodium‐ion battery anodes ever reported.     

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.     

Ultrahigh Responsivity Photodetectors of 2D Covalent Organic Frameworks Integrated on Graphene

2D materials exhibit superior properties in electronic and optoelectronic fields. The wide demand for high-performance optoelectronic devices promotes the exploration of diversified 2D materials. Recently, 2D covalent organic frameworks (COFs) have emerged as next-generation layered materials with predesigned π-electronic skeletons and highly ordered topological structures, which are promising for tailoring their optoelectronic properties. However, COFs are usually produced as solid powders due to anisotropic growth, making them unreliable to integrate into devices. Here, by selecting tetraphenylethylene monomers with photoelectric activity, elaborately designed photosensitive 2D-COFs with highly ordered donor-acceptor topologies are in situ synthesized on graphene, ultimately forming COF-graphene heterostructures. Ultrasensitive photodetectors are successfully fabricated with the COF_ETBC–TAPT-graphene heterostructure and exhibited an excellent overall performance with a photoresponsivity of ≈3.2 × 10⁷ A W⁻¹ at 473 nm and a time response of ≈1.14 ms. Moreover, due to the high surface area and the polarity selectivity of COFs, the photosensing properties of the photodetectors can be reversibly regulated by specific target molecules. The research provides new strategies for building advanced functional devices with programmable material structures and diversified regulation methods, paving the way for a generation of high-performance applications in optoelectronics and many other fields.     

锂离子电池阴极材料Li_(1+x)Mn_2O_4的合成与特性

对Ｌｉ１＋ｘＭｎ２Ｏ４的合成性能进行了初步的探索。原材料采用分析纯Ｌｉ２ＣＯ３和电解二氧化锰，对原材料ＭｎＯ２进行热处理，使之成为ε相并排除结晶水。制备了四个系列的样品，其各自的ｘ含量、首次加热温度、再次加热温度、退火方式有所不同。对样品进行ＸＲＤ分析及电性能测试，说明了ＭｎＯ２中必须除去结晶水的原因，找到了最佳合成温度范围，确定了最佳性能时的ｘ值。     

Tin Nanodots Derived From Sn2+/Graphene Quantum Dot Complex as Pillars into Graphene Blocks for Ultrafast and Ultrastable Sodium‐Ion Storage

Tin (Sn) is considered to be an ideal candidate for the anode of sodium ion batteries. However, the design of Sn‐based electrodes with maintained long‐term stability still remains challenging due to their huge volume expansion (≈420%) and easy pulverization during cycling. Herein, a facile and versatile strategy for the synthesis of nitrogen‐doped graphene quantum dot (GQD) edge‐anchored Sn nanodots as the pillars into reduced graphene oxide blocks (NGQD/Sn‐NG) for ultrafast and ultrastable sodium‐ion storage is reported. Sn nanodots (2–5 nm) anchored at the edges of “octopus‐like” GQDs via covalent Sn? O? C/Sn? N? C bonds function as the pillars that ensure fast Na‐ion/electron transport across the graphene blocks. Moreover, the chemical and spatial (layered structure) confinements not only suppress Sn aggregation, but also function as physical barriers for buffering volume change upon sodiation/desodiation. Consequently, the NGQD/Sn‐NG with high structural stability exhibits excellent rate performance (555 mAh g^?1 at 0.1 A g^?1 and 198 mAh g^?1 at 10 A g^?1) and ultra‐long cycling stability (184 mAh g^?1 remaining even after 2000 cycles at 5 A g^?1). The confinement‐induced synthesis together with remarkable electrochemical performances should shed light on the practical application of highly attractive tin‐based anodes for next generation rechargeable sodium batteries.     

Carbon‐Coated Na3.32Fe2.34(P2O7)2 Cathode Material for High‐Rate and Long‐Life Sodium‐Ion Batteries

Rechargeable sodium‐ion batteries are proposed as the most appropriate alternative to lithium batteries due to the fast consumption of the limited lithium resources. Due to their improved safety, polyanion framework compounds have recently gained attention as potential candidates. With the earth‐abundant element Fe being the redox center, the uniform carbon‐coated Na_3.32Fe_2.34(P₂O₇)₂/C composite represents a promising alternative for sodium‐ion batteries. The electrochemical results show that the as‐prepared Na_3.32Fe_2.34(P₂O₇)₂/C composite can deliver capacity of ≈100 mA h g^?1 at 0.1 C (1 C = 120 mA g^?1), with capacity retention of 92.3% at 0.5 C after 300 cycles. After adding fluoroethylene carbonate additive to the electrolyte, 89.6% of the initial capacity is maintained, even after 1100 cycles at 5 C. The electrochemical mechanism is systematically investigated via both in situ synchrotron X‐ray diffraction and density functional theory calculations. The results show that the sodiation and desodiation are single‐phase‐transition processes with two 1D sodium paths, which facilitates fast ionic diffusion. A small volume change, nearly 100% first‐cycle Coulombic efficiency, and a pseudocapacitance contribution are also demonstrated. This research indicates that this new compound could be a potential competitor for other iron‐based cathode electrodes for application in large‐scale Na rechargeable batteries.