Fluorine Substitution Promotes Air-Stability of P'2-Type Layered Cathodes for Sodium-Ion Batteries

As one of the most promising cathode materials in sodium-ion batteries, manganese-based layered oxides have aroused wide attention due to their high specific capacity and plentiful reserves. However, they are plagued by poor air stability rooting in water/Na⁺ exchange and adverse structural reconstruction, hindering their practical applications. Herein, it is demonstrated that utilizing fluorine to substitute oxygen atoms can narrow the interlayer spacing of novel P'2-Na_0.67MnO_1.97F_0.03 (NMOF) cathode material, which resists the attack of water molecules, significantly prolonging exposure time in air. Density functional theory (DFT) calculation results indicate that fluorine substitution alleviates the insertion of water molecules and spontaneous extraction of Na⁺ effectively. Benefiting from the structural modulation, NMOF can deliver a high specific capacity of 227.1 mAh g^-1 at 20 mA g^-1 and a promising capacity retention of 84.0% after 100 cycles at 200 mA g^-1. This facile and available strategy provides a feasible way to strengthen the air-stability and expands the scope of practical applications of layered oxide cathodes.     

V2O5 Textile Cathodes with High Capacity and Stability for Flexible Lithium-Ion Batteries

Textile-based energy-storage devices are highly appealing for flexible and wearable electronics. Here, a 3D textile cathode with high loading, which couples hollow multishelled structures (HoMSs) with conductive metallic fabric, is reported for high-performance flexible lithium-ion batteries. V₂O₅ HoMSs prepared by sequential templating approach are used as active materials and conductive metallic fabrics are applied as current collectors and flexible substrates. Taking advantage of the desirable structure of V₂O₅ HoMSs that effectively buffers the volume expansion and alleviates the stress/strain during repeated Li-insertion/extraction processes, as well as the robust flexible metallic-fabric current collector, the as-prepared fabric devices show excellent electrochemical performance and ultrahigh stability. The capacity retains a high value of 222.4 mA h g⁻¹ at a high mass loading of 2.5 mg cm⁻² even after 500 charge/discharge cycles, and no obvious performance degradation is observed after hundreds of cycles of bending and folding. These results indicate that V₂O₅ HoMSs/metallic-fabric cathode electrode is promising for highly flexible lithium-ion batteries.     

Polyimide@Ketjenblack Composite: A Porous Organic Cathode for Fast Rechargeable Potassium‐Ion Batteries

Potassium‐ion batteries (PIBs) configurated by organic electrodes have been identified as a promising alternative to lithium‐ion batteries. Here, a porous organic Polyimide@Ketjenblack is demonstrated in PIBs as a cathode, which exhibits excellent performance with a large reversible capacity (143 mAh g^?1 at 100 mA g^?1), high rate capability (125 and 105 mAh g^?1 at 1000 and 5000 mA g^?1), and long cycling stability (76% capacity retention at 2000 mA g^?1 over 1000 cycles). The domination of fast capacitive‐like reaction kinetics is verified, which benefits from the porous structure synthesized using in situ polymerization. Moreover, a renewable and low‐cost full cell is demonstrated with superior rate behavior (106 mAh g^?1 at 3200 mA g^?1). This work proposes a strategy to design polymer electrodes for high‐performance organic PIBs.     

Highly Stable Sb/C Anode for K+ and Na+ Energy Storage Enabled by Pulsed Laser Ablation and Polydopamine Coating

Potassium- and sodium-ion batteries (PIBs and SIBs) have great potential as the next-generation energy application owing to the natural abundance of K and Na. Antimony (Sb) is a suitable alloying-type anode for PIBs and SIBs due to its high theoretical capacity and proper operation voltage; yet, the severe volume variation remains a challenge. Herein, a preparation of N-doped carbon-wrapped Sb nanoparticles (L-Sb/NC) using pulsed laser ablation and polydopamine coating techniques, is reported. As the anode for PIB and SIB, the L-Sb/NC delivers superior rate capabilities and excellent cycle stabilities (442.2 and 390.5 mA h g⁻¹ after 250 cycles with the capacity decay of 0.037% and 0.038% per cycle) at the current densities of 0.5 and 1.0 A g⁻¹, respectively. Operando X-ray diffraction reveals the facilitated and stable potassiation and sodiation mechanisms of L-Sb/NC enabled by its optimal core–shell structure. Furthermore, the SIB full cell fabricated with L-Sb/NC and Na₃V₂(PO₄)₂F₃ shows outstanding electrochemical performances, demonstrating its practical energy storage application.     

Cathodes Coating Layer with Li-Ion Diffusion Selectivity Employing Interactive Network of Metal-Organic Polyhedras for Li-Ion Batteries (Small 5/2023)

Surface modification of cathodes using Ni-rich coating layers prevents bulk and surface degradation for the stable operation of Li–ion batteries at high voltages. However, insulating and dense inorganic coating layers often impede charge transfer and ion diffusion kinetics. In this study, the fabrication of dual functional coating materials using metal–organic polyhedra (MOP) with 3D networks within microporous units of Li–ion batteries for surface stabilization and facile ion diffusion is proposed. Zr-based MOP is modified by introducing acyl groups as a chemical linkage (MOPAC), and MOPAC layers are homogenously coated by simple spray coating on the cathode. The coating allow the smooth transport of electrons and ions. MOPAC effectively suppress side reactions between the cathode and electrolyte and protect active materials against aggressive fluoride ions by forming a Li–ion selective passivation film. The MOPAC-coated Ni-rich layered cathode exhibited better cycle retention and enhanced kinetic properties than pristine and MOP-coated cathodes. Reduction of undesirable gas evolution on the cathode by MOPAC is also verified. Microporous MOPAC coating can simultaneously stabilize both the bulk and surface of the Ni-rich layered cathode and maintain good electrochemical reaction kinetics for high-performance Li–ion batteries.     

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.     

Graphdiyne: A Brilliant Hole Accumulator for Stable and Efficient Planar Perovskite Solar Cells

Traditional carbon materials have demonstrated immense potential in perovskite solar cells (PSCs) owing to their superior electrical properties and environmental stability. Graphdiyne (GDY), as an emerging carbon allotrope, features uniformly distributed pores, endless design flexibility, and unique electronic character compared with traditional carbon materials. Herein, graphdiyne is introduced into the upper part of the perovskite (CH₃NH₃PbI₃) layer by utilizing a GDY‐containing antisolvent during the one‐step synthesis of perovskite. Intriguingly, GDY plays an essential role in hole accumulation and transportation because of its higher Fermi level than perovskite. As a result, the automatic separation of photogenerated carriers inside the perovskite film is achieved. Furthermore, the Schottky barrier formed on the interface between perovskite and GDY guarantees the unidirectional hole transport from perovskite to GDY, thereby benefiting further extraction to the hole transport layer. Consequently, GDY‐modified perovskite‐based planar PSCs exhibit a boosted J_sc of 24.21 mA cm^?2 and up to 19.6% power conversion efficiency owing to the increased efficient light utilization and charge extraction. The device with GDY modification exhibits less than 10% shrinkage after a month in ambience. Overall, this work demonstrates an easy method for the utilization of GDY to boost the charge extraction and environmental stability in PSCs.     

A Novel NASICON-Type Na4MnCr(PO4)3 Demonstrating the Energy Density Record of Phosphate Cathodes for Sodium-Ion Batteries

Sodium-ion batteries (SIBs) have attracted incremental attention as a promising candidate for grid-scale energy-storage applications. To meet practical requirements, searching for new cathode materials with high energy density is of great importance. Herein, a novel Na superionic conductor (NASICON)-type Na₄MnCr(PO₄)₃ is developed as a high-energy cathode for SIBs. The Na₄MnCr(PO₄)₃ nanoparticles homogeneously embedded in a carbon matrix can present an extraordinary reversible capacity of 160.5 mA h g⁻¹ with three-electron reaction at ≈3.53 V during the Na⁺ extraction/insertion process, realizing an unprecedentedly high energy density of 566.5 Wh kg⁻¹ in the phosphate cathodes for SIBs. It is intriguing to reveal the underlying mechanism of the unique Mn²⁺/Mn³⁺, Mn³⁺/Mn⁴⁺, and Cr³⁺/Cr⁴⁺ redox couples via X-ray absorption near-edge structure spectroscopy. The whole electrochemical reaction undergoes highly reversible single-phase and biphasic transitions with a moderate volume change of 7.7% through in situ X-ray diffraction and ex situ high-energy synchrotron X-ray diffraction. Combining density functional theory (DFT) calculations with the galvanostatic intermittent titration technique, the superior performance is ascribed to the low ionic-migration energy barrier and desirable Na-ion diffusion kinetics. The present work can offer a new insight into the design of multielectron-reaction cathode materials for SIBs.     

锂离子电池用有机电解液和聚合物电解质的研究进展

从导电锂盐、有机溶剂和添加剂三个方面详细综述了锂离子电池用有机电解液的研究进展。同时针对聚合物电解质的组成、结构和性能的差异，将其分为四类，阐述了它们的优缺点及其在锂离子电池中的应用与研究进展。最后展望了电解质的发展前景。     

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.     

Cross-Linked Sodium Alginate as A Multifunctional Binder to Achieve High-Rate and Long-Cycle Stability for Sodium-Ion Batteries

Sodium-ion batteries (SIBs) hold great promise owing to the naturally abundant sodium resource and high safety. The research focus of SIBs is usually directed toward electrode materials, while the binder as an important component is rarely investigated. Herein, a cross-linked sodium alginate (SA)/graphene oxide (GO) binder is judiciously designed to serve as a robust artificial interphase on the surface of both anode and cathode of SIBs. Benefiting from the cross-linking continuous network structure as well as the highly hydrophilic nature, the SA-GO binder possesses a large tensile strength of 197.7 Mpa and a high ionic conductivity of 0.136 mS cm⁻¹, superior to pure SA (93.8 Mpa, 0.025 mS cm⁻¹). Moreover, the structural design of SA-GO binder exhibits a strong binding ability to guarantee structural integrity during cycling. To demonstrate its effectiveness, polyanion-type phosphates (e.g., Na₃(VO)₂(PO₄)₂F) and chalcogenides (e.g., MoS₂, VS₂) are adopted as cathode and anode materials of SIBs, respectively. As compared to traditional binders (e.g., PVDF, SA), electrodes with the SA-GO binder exhibits significantly increased rate capability and cycling stability, such as Na₃(VO)₂(PO₄)₂F (40 C fast-charge, 84% capacity retention after 1000 cycles). This work highlights the role of novel aqueous-based binders in developing next-generation sodium-storage devices.     

Reversible Iron Oxyfluoride (FeOF)-Graphene Composites as Sustainable Cathodes for High Energy Density Lithium Batteries

Two large barriers are impeding the wide implementation of electric vehicles, namely driving-range and cost, primarily due to the low specific energy and high cost of mono-valence cathodes used in lithium-ion batteries. Iron is the ideal element for cathode materials considering its abundance, low cost and toxicity. However, the poor reversibility of (de)lithiation and low electronic conductivity prevent iron-based high specific energy multi-valence conversion cathodes from practical applications. In this work, a sustainable FeOF nanocomposite is developed with extraordinary performance. The specific capacity and energy reach 621 mAh g⁻¹ and 1124 Wh kg⁻¹ with more than 100 cycles, which triples the specific capacity, and doubles the specific energy of current mono-valence intercalation LiCoO₂. This is the result of an effective approach, combing the nanostructured FeOF with graphene, realized by making the (de)lithiation reversible by immobilizing FeOF nanoparticles and the discharge products over the graphene surface and providing the interparticle electric conduction. Importantly, it demonstrates that introducing small amount of graphene can create new materials with desired properties, opening a new avenue for altering the (de)lithiation process. Such extraordinary performance represents a significant breakthrough in developing sustainable conversion materials, eventually overcoming the driving range and cost barriers.     

Graphdiyne Derivative as Multifunctional Solid Additive in Binary Organic Solar Cells with 17.3% Efficiency and High Reproductivity

Morphology tuning of the blend film in organic solar cells (OSCs) is a key approach to improve device efficiencies. Among various strategies, solid additive is proposed as a simple and new way to enable morphology tuning. However, there exist few solid additives reported to meet such expectations. Herein, chlorine-functionalized graphdiyne (GCl) is successfully applied as a multifunctional solid additive to fine-tune the morphology and improve device efficiency as well as reproductivity for the first time. Compared with 15.6% efficiency for control devices, a record high efficiency of 17.3% with the certified one of 17.1% is obtained along with the simultaneous increase of short-circuit current (J_sc) and fill factor (FF), displaying the state-of-the-art binary organic solar cells at present. The redshift of the film absorption, enhanced crystallinity, prominent phase separation, improved mobility, and decreased charge recombination synergistically account for the increase of J_sc and FF after introducing GCl into the blend film. Moreover, the addition of GCl dramatically reduces batch-to-batch variations benefiting mass production owing to the nonvolatile property of GCl. All these results confirm the efficacy of GCl to enhance device performance, demonstrating a promising application of GCl as a multifunctional solid additive in the field of OSCs.     

High-Efficiency Cathode Sodium Compensation for Sodium-Ion Batteries

Sodium-ion batteries have gained much attention for their potential application in large-scale stationary energy storage due to the low cost and abundant sodium sources in the earth. However, the electrochemical performance of sodium-ion full cells (SIFCs) suffers severely from the irreversible consumption of sodium ions of cathode during the solid electrolyte interphase (SEI) formation of hard carbon anode. Here, a high-efficiency cathode sodiation compensation reagent, sodium oxalate (Na₂C₂O₄), which possesses both a high theoretical capacity of 400 mA h g⁻¹ and a capacity utilization as high as 99%, is proposed. The implementation of Na₂C₂O₄ as sacrificial sodium species is successfully realized by decreasing its oxidation potential from 4.41 to 3.97 V through tuning conductive additives with different physicochemical features, and the corresponding mechanism of oxidation potential manipulation is analyzed. Electrochemical results show that in the full cell based on a hard carbon anode and a P2-Na_2/3Ni_1/3Mn_1/3Ti_1/3O₂ cathode with Na₂C₂O₄ as a sodium reservoir to compensate for sodium loss during SEI formation, the capacity retention is increased from 63% to 85% after 200 cycles and the energy density is improved from 129.2 to 172.6 W h kg⁻¹. This work can provide a new avenue for accelerating the development of SIFCs.     

Spontaneously Splitting Copper Nanowires into Quantum Dots on Graphdiyne for Suppressing Lithium Dendrites

As an emerging carbon allotrope, the controllable growth of graphdiyne has been an important means to explore its unique scientific properties and applications. In this work, the effect of the crystal structure of copper (Cu) on the growth of graphdiyne is systematically studied. It is found that the crystal boundaries are the origin of the reaction activity. The polycrystalline Cu nanowire with many crystal boundaries is spontaneously split into Cu quantum dots (about 3 nm) by the grown graphdiyne. These Cu quantum dots are uniformly dispersed on the graphdiyne, and they block the long-range ordered growth of the graphdiyne. These Cu quantum dots in situ supported on graphdiyne demonstrate high efficiency in inhibiting the growth of lithium dendrites in lithium metal batteries. Based on this interesting finding, the Cu quantum dots anchored on the all-carbon graphdiyne can be prepared on a large scale, and unique applications of Cu quantum dots in electrochemical fields can be implemented.     

Controllable Solid Electrolyte Interphase in Nickel‐Rich Cathodes by an Electrochemical Rearrangement for Stable Lithium‐Ion Batteries

The layered nickel‐rich materials have attracted extensive attention as a promising cathode candidate for high‐energy density lithium‐ion batteries (LIBs). However, they have been suffering from inherent structural and electrochemical degradation including severe capacity loss at high electrode loading density (>3.0 g cm^?3) and high temperature cycling (>60 °C). In this study, an effective and viable way of creating an artificial solid–electrolyte interphase (SEI) layer on the cathode surface by a simple, one‐step approach is reported. It is found that the initial artificial SEI compounds on the cathode surface can electrochemically grow along grain boundaries by reacting with the by‐products during battery cycling. The developed nickel‐rich cathode demonstrates exceptional capacity retention and structural integrity under industrial electrode fabricating conditions with the electrode loading level of ≈12 mg cm^?2 and density of ≈3.3 g cm^?3. This finding could be a breakthrough for the LIB technology, providing a rational approach for the development of advanced cathode materials.     

A Superlattice-Stabilized Layered Oxide Cathode for Sodium-Ion Batteries

Sodium-ion batteries are in high demand for large-scale energy storage applications. Although it is the most prevalent cathode, layered oxide is associated with significant undesirable characteristics, such as multiple plateaus in the charge−discharge profiles, and cation migration during repeated cycling of Na-ions insertion and extraction, which results in sluggish kinetics, capacity loss, and structural deterioration. Here, a new strategy, i.e., the manipulation of transition-metal ordering in layered oxides, is proposed to show a prolonged charge−discharge plateau and cation-migration-free structural evolution. The results demonstrate that the transition-metal ordering with a honeycomb-type superlattice can adjust the crystal lattice and suppress cation migration by modifying the crystal strain to realize a large reversible capacity and excellent cycling performance, which are not characteristics of the widely used common layered oxides. These findings can provide new insight that can be used to improve the design of high-performance electrode materials for secondary-ion batteries.