Multidimensional Synergistic Nanoarchitecture Exhibiting Highly Stable and Ultrafast Sodium‐Ion Storage

Conversion‐type anodes with multielectron reactions are beneficial for achieving a high capacity in sodium‐ion batteries. Enhancing the electron/ion conductivity and structural stability are two key challenges in the development of high‐performance sodium storage. Herein, a novel multidimensionally assembled nanoarchitecture is presented, which consists of V₂O₃ nanoparticles embedded in amorphous carbon nanotubes that are then coassembled within a reduced graphene oxide (rGO) network, this materials is denoted V₂O₃?C‐NTs?rGO. The selective insertion and multiphase conversion mechanism of V₂O₃ in sodium‐ion storage is systematically demonstrated for the first time. Importantly, the naturally integrated advantages of each subunit synergistically provide a robust structure and rapid electron/ion transport, as confirmed by in situ and ex situ transmission electron microscopy experiments and kinetic analysis. Benefiting from the synergistic effects, the V₂O₃?C‐NTs?rGO anode delivers an ultralong cycle life (72.3% at 5 A g^?1 after 15 000 cycles) and an ultrahigh rate capability (165 mAh g^?1 at 20 A g^?1, ≈30 s per charge/discharge). The synergistic design of the multidimensionally assembled nanoarchitecture produces superior advantages in energy storage.     

Metallic Graphene‐Like VSe2 Ultrathin Nanosheets: Superior Potassium‐Ion Storage and Their Working Mechanism

Potassium‐ion batteries (KIBs) are receiving increasing interest in grid‐scale energy storage owing to the earth abundant and low cost of potassium resources. However, their development still stays at the infancy stage due to the lack of suitable electrode materials with reversible depotassiation/potassiation behavior, resulting in poor rate performance, low capacity, and cycling stability. Herein, the first example of synthesizing single‐crystalline metallic graphene‐like VSe₂ nanosheets for greatly boosting the performance of KIBs in term of capacity, rate capability, and cycling stability is reported. Benefiting from the unique 2D nanostructure, high electron/K⁺‐ion conductivity, and outstanding pseudocapacitance effects, ultrathin VSe₂ nanosheets show a very high reversible capacity of 366 mAh g^?1 at 100 mA g^?1, a high rate capability of 169 mAh g^?1 at 2000 mA g^?1, and a very low decay of 0.025% per cycle over 500 cycles, which are the best in all the reported anode materials in KIBs. The first‐principles calculations reveal that VSe₂ nanosheets have large adsorption energy and low diffusion barriers for the intercalation of K⁺‐ion. Ex situ X‐ray diffraction analysis indicates that VSe₂ nanosheets undertake a reversible phase evolution by initially proceeding with the K⁺‐ion insertion within VSe₂ layers, followed by the conversion reaction mechanism.     

CuO Nanoplates for High‐Performance Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) are promising alternatives to lithium‐ion batteries because of the abundance and low cost of K. However, an important challenge faced by KIBs is the search for high‐capacity materials that can hold large‐diameter K ions. Herein, copper oxide (CuO) nanoplates are synthesized as high‐performance anode materials for KIBs. CuO nanoplates with a thickness of ≈20 nm afford a large electrode–electrolyte contact interface and short K⁺ ion diffusion distance. As a consequence, a reversible capacity of 342.5 mAh g^?1 is delivered by the as‐prepared CuO nanoplate electrode at 0.2 A g^?1. Even after 100 cycles at a high current density of 1.0 A g^?1, the capacity of the electrode remains over 206 mAh g^?1, which is among the best values for KIB anodes reported in the literature. Moreover, a conversion reaction occurs at the CuO anode. Cu nanoparticles form during the first potassiation process and reoxidize to Cu₂O during the depotassiation process. Thereafter, the conversion reaction proceeds between the as‐formed Cu₂O and Cu, yielding a reversible theoretical capacity of 374 mAh g^?1. Considering their low cost, easy preparation, and environmental benignity, CuO nanoplates are promising KIB anode materials.     

The Promise and Challenge of Phosphorus‐Based Composites as Anode Materials for Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) are a core energy storage device that can meet the need for scalable and affordable stationary applications because they use low‐cost and earth‐abundant potassium. In addition, KIB shares a similar storage mechanism with current Li‐ion batteries. As the key to optimizing a battery's performance, the development of high‐performance electrode materials helps to increase the feasibility of KIB technology. In this sense, phosphorus‐based materials (i.e., phosphorus and metal phosphide) with high theoretical capacity and low redox potential tick all the right boxes as a material of choice. A rapid glimpse at recent studies on phosphorus‐based anode materials for advanced KIBs is provided, covering the synthetic methods, reaction mechanisms, electrochemical properties, and performances. In addition, several promising strategies are highlighted to address the imminent challenges faced by phosphorus‐based anode materials, hoping to cast an insightful outlook for possible future direction in this field.     

A Novel Potassium‐Ion‐Based Dual‐Ion Battery

In this work, combining both advantages of potassium‐ion batteries and dual‐ion batteries, a novel potassium‐ion‐based dual‐ion battery (named as K‐DIB) system is developed based on a potassium‐ion electrolyte, using metal foil (Sn, Pb, K, or Na) as anode and expanded graphite as cathode. When using Sn foil as the anode, the K‐DIB presents a high reversible capacity of 66 mAh g^?1 at a current density of 50 mA g^?1 over the voltage window of 3.0–5.0 V, and exhibits excellent long‐term cycling performance with 93% capacity retention for 300 cycles. Moreover, as the Sn foil simultaneously acts as the anode material and the current collector, dead load and dead volume of the battery can be greatly reduced, thus the energy density of the K‐DIB is further improved. It delivers a high energy density of 155 Wh kg^?1 at a power density of 116 W kg^?1, which is comparable with commercial lithium‐ion batteries. Thus, with the advantages of environmentally friendly, cost effective, and high energy density, this K‐DIB shows attractive potential for future energy storage application.     

Surface‐Engineered Black Niobium Oxide@Graphene Nanosheets for High‐Performance Sodium‐/Potassium‐Ion Full Batteries

Nanoscale surface‐engineering plays an important role in improving the performance of battery electrodes. Nb₂O₅ is one typical model anode material with promising high‐rate lithium storage. However, its modest reaction kinetics and low electrical conductivity obstruct the efficient storage of larger ions of sodium or potassium. In this work, partially surface‐amorphized and defect‐rich black niobium oxide@graphene (black Nb₂O_5?x@rGO) nanosheets are designed to overcome the above Na/K storage problems. The black Nb₂O_5?x@rGO nanosheets electrodes deliver a high‐rate Na and K storage capacity (123 and 73 mAh g^?1, respectively at 3 A g^?1) with long‐term cycling stability. Besides, both Na‐ion and K‐ion full batteries based on black Nb₂O_5?x@rGO nanosheets anodes and vanadate‐based cathodes (Na_0.33V₂O₅ and K_0.5V₂O₅ for Na‐ion and K‐ion full batteries, respectively) demonstrate promising rate and cycling performance. Notably, the K‐ion full battery delivers higher energy and power densities (172 Wh Kg^?1 and 430 W Kg^?1), comparable to those reported in state‐of‐the‐art K‐ion full batteries, accompanying with a capacity retention of ≈81.3% over 270 cycles. This result on Na‐/K‐ion batteries may pave the way to next‐generation post‐lithium batteries.     

Ultrafast Sodium/Potassium‐Ion Intercalation into Hierarchically Porous Thin Carbon Shells

The large‐scale application of sodium/potassium‐ion batteries is severely limited by the low and slow charge storage dynamics of electrode materials. The crystalline carbons exhibit poor insertion capability of large Na⁺/K⁺ ions, which limits the storage capability of Na/K batteries. Herein, porous S and N co‐doped thin carbon (S/N@C) with shell‐like (shell size ≈20–30 nm, shell wall ≈8–10 nm) morphology for enhanced Na⁺/K⁺ storage is presented. Thanks to the hollow structure and thin shell‐wall, S/N@C exhibits an excellent Na⁺/K⁺ storage capability with fast mass transport at higher current densities, leading to limited compromise over charge storage at high charge/discharge rates. The S/N@C delivers a high reversible capacity of 448 mAh g^‐1 for Na battery, at the current density of 100 mA g^‐1 and maintains a discharge capacity up to 337 mAh g^‐1 at 1000 mA g^‐1. Owing to shortened diffusion pathways, S/N@C delivers an unprecedented discharge capacity of 204 and 169 mAh g^‐1 at extremely high current densities of 16 000 and 32 000 mA g^‐1, respectively, with excellent reversible capacity for 4500 cycles. Moreover, S/N@C exhibits high K⁺ storage capability (320 mAh g^‐1 at current density of 50 mA g^‐1) and excellent cyclic life.     

Pistachio‐Shuck‐Like MoSe2/C Core/Shell Nanostructures for High‐Performance Potassium‐Ion Storage

Potassium‐ion batteries (KIBs) have recently attracted intensive attention because of the abundant potassium resources and their low cost and high safety. However, the major challenge faced by KIBs lies in the lack of stable and high‐capacity materials for the intercalation/deintercalation of large‐size potassium ions. A unique pistachio‐shuck‐like MoSe₂/C core/shell nanostructure (PMC) is synthesized herein as an advanced anode for boosting the performance of KIBs. This PMC is featured with a few layers of molybdenum selenide as the core with an expanded interlayer spacing of ≈0.85 nm, facilitating the intercalation/deintercalation of K ions, and a thin amorphous carbon as the shell, which can confine the active molybdenum selenide nanosheets during cycling for maintaining the high structural stability. Most importantly, as a whole, the PMC has the advantages of reducing the surplus hollow interior space for improving its packing density and buffering the volume expansion during the K‐ion intercalation for further enhancing the stability. As a consequence, the PMC shows a very high capacity of 322 mAh g^?1 at 0.2 A g^?1 over 100 cycles, and can still remain 226 mAh g^?1 at 1.0 A g^?1 for a long period of 1000 cycles, which is among the best‐reported KIBs anodes.     

ZIF‐8@ZIF‐67‐Derived Nitrogen‐Doped Porous Carbon Confined CoP Polyhedron Targeting Superior Potassium‐Ion Storage

Potassium ion batteries (KIB) have become a compelling energy‐storage system owing to their cost effectiveness and the high abundance of potassium in comparison with lithium. However, its practical applications have been thwarted by a series of challenges, including marked volume expansion and sluggish reaction kinetics caused by the large radius of potassium ions. In line with this, the exploration of reliable anode materials affording high electrical conductivity, sufficient active sites, and structural robustness is the key. The synthesis of ZIF‐8@ZIF‐67 derived nitrogen‐doped porous carbon confined CoP polyhedron architectures (NC@CoP/NC) to function as innovative KIB anode materials is reported. Such composites enable an outstanding rate performance to harvest a capacity of ≈200 mAh g^?1 at 2000 mA g^?1. Additionally, a high cycling stability can be gained by maintaining a high capacity retention of 93% after 100 cycles at 100 mA g^?1. Furthermore, the potassium ion storage mechanism of the NC@CoP/NC anode is systematically probed through theoretical simulations and experimental characterization. This contribution may offer an innovative and feasible route of emerging anode design toward high performance KIBs.     

2D Film of Carbon Nanofibers Elastically Astricted MnO Microparticles: A Flexible Binder‐Free Anode for Highly Reversible Lithium Ion Storage

MnO as anode materials has received particular interest owing to its high specific capacity, abundant resources, and low cost. However, serious problems related to the large volume change (>170%) during the lithiation/delithiation processes still results in poor rate capability and fast capacity decay. With homogenous crystals of MnO grown in the network of carbon nanofibers (CNF), binding effect of CNF can effectively weaken the volume change of MnO during cycles. In this work, a CNF/MnO flexible electrode for lithium‐ion batteries is designed and synthesized. The CNF play the roles of conductive channel and elastically astricting MnO particles during lithiation/delithiation. CNF/MnO as binder‐free anode delivers specific capacity of 983.8 mAh g^?1 after 100th cycle at a current density of 0.2 A g^?1, and 600 mAh g^?1 at 1 A g^?1 which are much better than those of pure MnO and pure CNF. The ex‐situ morphologies clearly show the relative volume change of MnO/CNF as anode under various discharging and charging times. CNF can elastically buffer the volume change of MnO during charging/discharging cycles. A facile and scalable approach for synthesizing a novel flexible binder‐free anode of CNF/MnO for potential application in highly reversible lithium storage devices is presented.     

Layered Oxide Cathode for Potassium‐Ion Battery: Recent Progress and Prospective

Rechargeable potassium‐ion batteries (KIBs) have demonstrated great potential as alternative technologies to the currently used lithium‐ion batteries on account of the competitive price and low redox potential of potassium which is advantageous to applications in the smart grid. As the critical component determining the energy density, appropriate cathode materials are of vital need for the realization of KIBs. Layered oxide cathodes are promising candidates for KIBs due to high reversible capacity, appropriate operating potential, and most importantly, facile and easily scalable synthesis. In light of this trend, the recent advancements and progress in layered oxides research for KIBs cathodes, covering material design, structural evolution, and electrochemical performance are comprehensively reviewed. The structure–performance correlation and some effective optimization strategies are also discussed. Furthermore, challenges and prospects of these layered cathodes are included, with the purpose of providing fresh impetus for future development of these materials for advanced energy storage systems.     

Flexible Membrane Consisting of MoP Ultrafine Nanoparticles Highly Distributed Inside N and P Codoped Carbon Nanofibers as High‐Performance Anode for Potassium‐Ion Batteries

Rechargeable potassium‐ion batteries (PIBs) have attracted tremendous attention as potential electrical energy storage systems due to the special merit of abundant resources and low cost of potassium. However, one critical barrier to achieve practical application of PIBs has been the lack of suitable electrode materials. Here, a novel flexible membrane consisting of N, P codoped carbon nanofibers decorated with MoP ultrafine nanoparticles (MoP@NPCNFs) is fabricated via a simple electrospinning method combined with the later carbonization and phosphorization process. The 3D porous CNF structure in the as‐synthesized composite can shorten the transport pathways of K‐ions and improve the conductivity of electrons. The ultrafine MoP nanoparticles can guarantee high specific capacity and the N, P co‐doping could improve wettability of electrodes to electrolytes. As expected, the free‐standing MoP@NPCNF electrode demonstrates a high capacity of 320 mAh g^?1 at 100 mA g^?1, a superior rate capability maintaining 220 mAh g^?1 at 2 A g^?1, as well as a capacity retention of more than 90% even after 200 cycles. The excellent rate performance, high reversible capacity, long‐term cycling stability, and facile synthesis routine make this hybrid membrane promising anode for potassium‐ion batteries.     

Sulfur‐Grafted Hollow Carbon Spheres for Potassium‐Ion Battery Anodes

Sulfur‐rich carbons are minimally explored for potassium‐ion batteries (KIBs). Here, a large amount of S (38 wt%) is chemically incorporated into a carbon host, creating sulfur‐grafted hollow carbon spheres (SHCS) for KIB anodes. The SHCS architecture provides a combination of nanoscale (≈40 nm) diffusion distances and C? S chemical bonding to minimize cycling capacity decay and Coulombic efficiency (CE) loss. The SHCS exhibit a reversible capacity of 581 mAh g^?1 (at 0.025 A g^?1), which is the highest reversible capacity reported for any carbon‐based KIB anode. Electrochemical analysis of S‐free carbon spheres baseline demonstrates that both the carbon matrix and the sulfur species are highly electrochemically active. SHCS also show excellent rate capability, achieving 202, 160, and 110 mAh g^?1 at 1.5, 3, and 5 A g^?1, respectively. The electrode maintains 93% of the capacity from the 5th to 1000th cycle at 3 A g^?1, with steady‐state CE being near 100%. Raman analysis indicates reversible breakage of C? S and S? S bonds upon potassiation to 0.01 V versus K/K⁺. The galvanostatic intermittent titration technique (GITT) analysis provides voltage‐dependent K⁺ diffusion coefficients that range from 10^?10 to 10^?12 cm² s^?1 upon potassiation and depotassiation, with approximately five times higher coefficient for the former.     

Nanoscale Engineering of Heterostructured Anode Materials for Boosting Lithium‐Ion Storage

Rechargeable lithium‐ion batteries (LIBs), as one of the most important electrochemical energy‐storage devices, currently provide the dominant power source for a range of devices, including portable electronic devices and electric vehicles, due to their high energy and power densities. The interest in exploring new electrode materials for LIBs has been drastically increasing due to the surging demands for clean energy. However, the challenging issues essential to the development of electrode materials are their low lithium capacity, poor rate ability, and low cycling stability, which strongly limit their practical applications. Recent remarkable advances in material science and nanotechnology enable rational design of heterostructured nanomaterials with optimized composition and fine nanostructure, providing new opportunities for enhancing electrochemical performance. Here, the progress as to how to design new types of heterostructured anode materials for enhancing LIBs is reviewed, in the terms of capacity, rate ability, and cycling stability: i) carbon‐nanomaterials‐supported heterostructured anode materials; ii) conducting‐polymer‐coated electrode materials; iii) inorganic transition‐metal compounds with core@shell structures; and iv) combined strategies to novel heterostructures. By applying different strategies, nanoscale heterostructured anode materials with reduced size, large surfaces area, enhanced electronic conductivity, structural stability, and fast electron and ion transport, are explored for boosting LIBs in terms of high capacity, long cycling lifespan, and high rate durability. Finally, the challenges and perspectives of future materials design for high‐performance LIB anodes are considered. The strategies discussed here not only provide promising electrode materials for energy storage, but also offer opportunities in being extended for making a variety of novel heterostructured nanomaterials for practical renewable energy applications.     

Localized Electrons Enhanced Ion Transport for Ultrafast Electrochemical Energy Storage

The rate-determining process for electrochemical energy storage is largely determined by ion transport occurring in the electrode materials. Apart from decreasing the distance of ion diffusion, the enhancement of ionic mobility is crucial for ion transport. Here, a localized electron enhanced ion transport mechanism to promote ion mobility for ultrafast energy storage is proposed. Theoretical calculations and analysis reveal that highly localized electrons can be induced by intrinsic defects, and the migration barrier of ions can be obviously reduced. Consistently, experiment results reveal that this mechanism leads to an enhancement of Li/Na ion diffusivity by two orders of magnitude. At high mass loading of 10 mg cm⁻² and high rate of 10C, a reversible energy storage capacity up to 190 mAh g⁻¹ is achieved, which is ten times greater than achievable by commercial crystals with comparable dimensions.     

Enhanced Capacity and Rate Capability of Nitrogen/Oxygen Dual‐Doped Hard Carbon in Capacitive Potassium‐Ion Storage

The intercalation of potassium ions into graphite is demonstrated to be feasible, while the electrochemical performance of potassium‐ion batteries (KIBs) remains unsatisfying. More effort is needed to improve the specific capacity while maintaining a superior rate capability. As an attempt, nitrogen/oxygen dual‐doped hierarchical porous hard carbon (NOHPHC) is introduced as the anode in KIBs by carbonizing and acidizing the NH₂‐MIL‐101(Al) precursor. Specifically, the NOHPHC electrode delivers high reversible capacities of 365 and 118 mA h g^?1 at 25 and 3000 mA g^?1, respectively. The capacity retention reaches 69.5% at 1050 mA g^?1 for 1100 cycles. The reasons for the enhanced electrochemical performance, such as the high capacity, good cycling stability, and superior rate capability, are analyzed qualitatively and quantitatively. Quantitative analysis reveals that mixed mechanisms, including capacitance and diffusion, account for the K‐ion storage, in which the capacitance plays a more important role. Specifically, the enhanced interlayer spacing (0.39 nm) enables the intercalation of large K ions, while the high specific surface area of ≈1030 m² g^?1 and the dual‐heteroatom doping (N and O) are conducive to the reversible adsorption of K ions.     

Construction of Bimetallic Selenides Encapsulated in Nitrogen/Sulfur Co‐Doped Hollow Carbon Nanospheres for High‐Performance Sodium/Potassium‐Ion Half/Full Batteries

Metallic selenides have been widely investigated as promising electrode materials for metal‐ion batteries based on their relatively high theoretical capacity. However, rapid capacity decay and structural collapse resulting from the larger‐sized Na⁺/K⁺ greatly hamper their application. Herein, a bimetallic selenide (MoSe₂/CoSe₂) encapsulated in nitrogen, sulfur‐codoped hollow carbon nanospheres interconnected reduced graphene oxide nanosheets (rGO@MCSe) are successfully designed as advanced anode materials for Na/K‐ion batteries. As expected, the significant pseudocapacitive charge storage behavior substantially contributes to superior rate capability. Specifically, it achieves a high reversible specific capacity of 311 mAh g^?1 at 10 A g^?1 in NIBs and 310 mAh g^?1 at 5 A g^?1 in KIBs. A combination of ex situ X‐ray diffraction, Raman spectroscopy, and transmission electron microscopy tests reveals the phase transition of rGO@MCSe in NIBs/KIBs. Unexpectedly, they show quite different Na⁺/K⁺ insertion/extraction reaction mechanisms for both cells, maybe due to more sluggish K⁺ diffusion kinetics than that of Na⁺. More significantly, it shows excellent energy storage properties in Na/K‐ion full cells when coupled with Na₃V₂(PO₄)₂O₂F and PTCDA@450 °C cathodes. This work offers an advanced electrode construction guidance for the development of high‐performance energy storage devices.