Nanosheets‐Assembled CuSe Crystal Pillar as a Stable and High‐Power Anode for Sodium‐Ion and Potassium‐Ion Batteries

Thanks to low costs and the abundance of the resources, sodium‐ion (SIBs) and potassium‐ion batteries (PIBs) have emerged as leading candidates for next‐generation energy storage devices. So far, only few materials can serve as the host for both Na⁺ and K⁺ ions. Herein, a cubic phase CuSe with crystal‐pillar‐like morphology (CPL‐CuSe) assembled by the nanosheets are synthesized and its dual functionality in SIBs and PIBs is comprehensively studied. The electrochemical measurements demonstrate that CPL‐CuSe enables fast Na⁺ and K⁺ storage as well as the sufficiently long duration. Specifically, the anode delivers a specific capacity of 295 mA h g^?1 at current density of 10 A g^?1 in SIBs, while 280 mA h g^?1 at 5 A g^?1 in PIBs, as well as the high capacity retention of nearly 100% over 1200 cycles and 340 cycles, respectively. Remarkably, CPL‐CuSe exhibits a high initial coulombic efficiency of 91.0% (SIBs) and 92.4% (PIBs), superior to most existing selenide anodes. A combination of in situ X‐ray diffraction and ex situ transmission electron microscopy tests fundamentally reveal the structural transition and phase evolution of CuSe, which shows a reversible conversion reaction for both cells, while the intermediate products are different due to the sluggish K⁺ insertion reaction.     

Graphitic Carbon Nanocage as a Stable and High Power Anode for Potassium‐Ion Batteries

As an emerging electrochemical energy storage device, potassium‐ion batteries (PIBs) have drawn growing interest due to the resource‐abundance and low cost of potassium. Graphite‐based materials, as the most common anodes for commercial Li‐ion batteries, have a very low capacity when used an anode for Na‐ion batteries, but they show reasonable capacities as anodes for PIBs. The practical application of graphitic materials in PIBs suffers from poor cyclability, however, due to the large interlayer expansion/shrinkage caused by the intercalation/deintercalation of potassium ions. Here, a highly graphitic carbon nanocage (CNC) is reported as a PIBs anode, which exhibits excellent cyclability and superior depotassiation capacity of 175 mAh g^?1 at 35 C. The potassium storage mechanism in CNC is revealed by cyclic voltammetry as due to redox reactions (intercalation/deintercalation) and double‐layer capacitance (surface adsorption/desorption). The present results give new insights into structural design for graphitic anode materials in PIBs and understanding the double‐layer capacitance effect in alkali metal ion batteries.     

Hard Carbon Microtubes Made from Renewable Cotton as High‐Performance Anode Material for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have attracted more and more attention for scalable electrical energy storage due to the abundance and wide distribution of Na resources. However, the anode still remains a great challenge for the application of SIBs. Here the production of uniform hard carbon microtubes (HCTs) made from natural cotton through one simple carbonization process and their application as an anode are reported. The study shows that the electrochemical performance of the HCTs is seriously affected by the carbonization temperature due to the difference in their microstructure and heteroatomic content. The HCTs carbonized at 1300 °C deliver the highest reversible capacity of 315 mAh g^?1 and good rate capability due to their unique tubular structure. This contribution not only provides a new approach for the preparation of hard carbon materials with unique tubular microstructure using natural inspiration, but it also deepens the fundamental understanding of the sodium storage mechanism.     

Sulfur/Oxygen Codoped Porous Hard Carbon Microspheres for High‐Performance Potassium‐Ion Batteries

Potassium‐ion batteries (KIBs) are very promising alternatives to lithium‐ion batteries (LIBs) for large‐scale energy storage. However, traditional carbon anode materials usually show poor performance in KIBs due to the large size of K ions. Herein, a carbonization‐etching strategy is reported for making a class of sulfur (S) and oxygen (O) codoped porous hard carbon microspheres (PCMs) material as a novel anode for KIBs through pyrolysis of the polymer microspheres (PMs) composed of a liquid crystal/epoxy monomer/thiol hardener system. The as‐made PCMs possess a porous architecture with a large Brunauer–Emmett–Teller surface area (983.2 m² g^?1), an enlarged interlayer distance (0.393 nm), structural defects induced by the S/O codoping and also amorphous carbon nature. These new features are important for boosting potassium ion storage, allowing the PCMs to deliver a high potassiation capacity of 226.6 mA h g^?1 at 50 mA g^?1 over 100 cycles and be displaying high stability by showing a potassiation capacity of 108.4 mA h g^?1 over 2000 cycles at 1000 mA g^?1. The density functional theory calculations demonstrate that S/O codoping not only favors the adsorption of K to the PCMs electrode but also reduces its structural deformation during the potassiation/depotassiation. The present work highlights the important role of hierarchical porosity and S/O codoping in potassium storage.     

Fabrication of Hierarchical Potassium Titanium Phosphate Spheroids: A Host Material for Sodium‐Ion and Potassium‐Ion Storage

Identifying suitable electrode materials for sodium‐ion and potassium‐ion storage holds the key to the development of earth‐abundant energy‐storage technologies. This study reports an anode material based on self‐assembled hierarchical spheroid‐like KTi₂(PO₄)₃@C nanocomposites synthesized via an electrospray method. Such an architecture synergistically combines the advantages of the conductive carbon network and allows sufficient space for the infiltration of the electrolyte from the porous structure, leading to an impressive electrochemical performance, as reflected by the high reversible capacity (283.7 mA h g^?1 for Na‐ion batteries; 292.7 mA h g^?1 for K‐ion batteries) and superior rate capability (136.1 mA h g^?1 at 10 A g^?1 for Na‐ion batteries; 133.1 mA h g^?1 at 1 A g^?1 for K‐ion batteries) of the resulting material. Moreover, the different ion diffusion behaviors in the two systems are revealed to account for the difference in rate performance. These findings suggest that KTi₂(PO₄)₃@C is a promising candidate as an anode material for sodium‐ion and potassium‐ion batteries. In particular, the present synthetic approach could be extended to other functional electrode materials for energy‐storage materials.     

Lithium‐Pretreated Hard Carbon as High‐Performance Sodium‐Ion Battery Anodes

Hard carbon (HC) is the state‐of‐the‐art anode material for sodium‐ion batteries (SIBs). However, its performance has been plagued by the limited initial Coulombic efficiency (ICE) and mediocre rate performance. Here, experimental and theoretical studies are combined to demonstrate the application of lithium‐pretreated HC (LPHC) as high‐performance anode materials for SIBs by manipulating the solid electrolyte interphase in tetraglyme (TEGDME)‐based electrolyte. The LPHC in TEGDME can 1) deliver > 92% ICE and ≈220 mAh g^?1 specific capacity, twice of the capacity (≈100 mAh g^?1) in carbonate electrolyte; 2) achieve > 85% capacity retention over 1000 cycles at 1000 mA g^?1 current density (4 C rate, 1 C = 250 mA g^?1) with a specific capacity of ≈150 mAh g^?1, ≈15 times of the capacity (10 mAh g^?1) in carbonate. The full cell of Na₃V₂(PO₄)₃‐LPHC in TEGDME demonstrated close to theoretical specific capacity of ≈98 mAh g^?1 based on Na₃V₂(PO₄)₃ cathode, ≈2.5 times of the value (≈40 mAh g^?1) with nontreated HC. This work provides new perception on the anode development for SIBs.     

3D Amorphous Carbon with Controlled Porous and Disordered Structures as a High‐Rate Anode Material for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have a promising application prospect for energy storage systems due to the abundant resource. Amorphous carbon with high electronic conductivity and high surface area is likely to be the most promising anode material for SIBs. However, the rate capability of amorphous carbon in SIBs is still a big challenge because of the sluggish kinetics of Na⁺ ions. Herein, a three‐dimensional amorphous carbon (3DAC) with controlled porous and disordered structures is synthesized via a facile NaCl template‐assisted method. Combination of open porous structures of 3DAC, the increased disordered structures can not only facilitate the diffusion of Na⁺ ions but also enhance the reversible capacity of Na storage. When applied as anode materials for SIBs, 3DAC exhibits excellent rate capability (66 mA h g^?1 at 9.6 A g^?1) and high reversible capacity (280 mA h g^?1 at a low current density of 0.03 A g^?1). Moreover, the controlled porous structures by the NaCl template method provide an appropriate specific surface area, which contributes to a relatively high initial Coulombic efficiency of 75%. Additionally, the high‐rate 3DAC material is prepared via a green approach originating from low‐cost pitch and NaCl template, demonstrating an appealing development of carbon anode materials for SIBs.     

An Ultrafast Rechargeable Hybrid Sodium‐Based Dual‐Ion Capacitor Based on Hard Carbon Cathodes

Hybrid sodium‐based dual‐ion capacitors (NDICs), which integrate the advantages of supercapacitors and sodium‐ion batteries, have attracted tremendous attention recently. In this work, hybrid sodium‐based dual‐ion capacitors are successfully developed with nitrogen‐doped microporous hard carbon as the cathode and soft carbon as the anode. N‐doping is beneficial to the functional groups, porous structure, and electric conductivity of hard carbon. Hybrid NDICs possess a wide voltage range (0.01–4.7 V), high‐energy density of 245.7 W h kg^?1 at a power density of 1626 W kg^?1, long cycle life (1000 cycles), and outstanding rate performance.     

A Dual‐Carbon Battery Based on Potassium‐Ion Electrolyte

Although potassium‐ion batteries (KIBs) have been considered to be promising alternatives to conventional lithium‐ion batteries due to large abundance and low cost of potassium resources, their development still stays at the infancy stage due to the lack of appropriate cathode and anode materials with reversible potassium insertion/extraction as well as good rate and cycling performance. Herein, a novel dual‐carbon battery based on a potassium‐ion electrolyte (named as K‐DCB), utilizing expanded graphite as cathode material and mesocarbon microbead as anode material is developed. The working mechanism of the K‐DCB is investigated, which is further demonstrated to deliver a high reversible capacity of 61 mA h g^‐1 at a current density of 1C over a voltage window of 3.0–5.2 V, as well as good cycling performance with negligible capacity decay after 100 cycles. Moreover, the high working voltage with medium discharge voltage of 4.5 V also enables the K‐DCB to meet the requirement of some high‐voltage devices. With the merits of environmental friendliness, low cost and high energy density, the K‐DCB shows attractive potential for future energy storage application.     

Sodium‐Ion Batteries: From Academic Research to Practical Commercialization

Sodium‐ion batteries (SIBs) have been considered as the most promising candidate for large‐scale energy storage system owing to the economic efficiency resulting from abundant sodium resources, superior safety, and similar chemical properties to the commercial lithium‐ion battery. Despite the long period of academic research, how to realize sodium‐ion battery commercialization for market applications is still a great challenge. Thus, from the perspective of future practical application, this review will identify the factors that are restricting commercialization, and evaluate the existing active materials and sodium‐ion‐based full‐cell system. The design and development trends that are needed for SIBs to meet the requirements of practical applications in large‐scale energy storage will also be discussed in detail.     

CuS Microspheres with Tunable Interlayer Space and Micropore as a High‐Rate and Long‐Life Anode for Sodium‐Ion Batteries

Layered transition metal sulfides (LTMSs) have tremendous commercial potential in anode materials for sodium‐ion batteries (SIBs) in large‐scale energy storage application. However, it is a great challenge for most LTMS electrodes to have long cycling life and high‐rate capability due to their larger volume expansion and the formation of soluble polysulfide intermediates caused by the conversion reaction. Herein, layered CuS microspheres with tunable interlayer space and pore volumes are reported through a cost‐effective interaction method using a cationic surfactant of cetyltrimethyl ammonium bromide (CTAB). The CuS–CTAB microsphere as an anode for SIBs reveals a high reversible capacity of 684.6 mAh g^?1 at 0.1 A g^?1, and 312.5 mAh g^?1 at 10 A g^?1 after 1000 cycles with high capacity retention of 90.6%. The excellent electrochemical performance is attributed to the unique structure of this material, and a high pseudocapacitive contribution ensures its high‐rate performance. Moreover, in situ X‐ray diffraction is applied to investigate their sodium storage mechanism. It is found that the long chain CTAB in the CuS provides buffer space, traps polysulfides, and restrains the further growth of Cu particles during the conversion reaction process that ensure the long cycling stability and high reversibility of the electrode material.     

Advanced Carbon‐Based Anodes for Potassium‐Ion Batteries

The ever‐increasing demand for large‐scale energy storage systems requires novel battery technologies with low‐cost and sustainable properties. Due to earth‐abundance and cost effectiveness, the development of rechargeable potassium ion batteries (PIBs) has recently attracted much attention. Since carbon‐based materials are abundant, inexpensive, nontoxic, and safe, extensive feasibility investigations have suggested that they can become promising anode materials for PIBs. This review not only attempts to provide better understanding of the potassium storage mechanism, but also summarizes the availability of new carbon‐based materials and their electrochemical performance covering graphite, graphene, and hard carbon materials plus carbon‐based composites. Finally, the critical issues, challenges, and perspectives are discussed to demonstrate the developmental direction of PIBs.     

Soft Carbon as Anode for High‐Performance Sodium‐Based Dual Ion Full Battery

Sodium‐based dual ion full batteries (NDIBs) are reported with soft carbon as anode and graphite as cathode for the first time. The NDIBs operate at high discharge voltage plateau of 3.58 V, with superior discharge capacity of 103 mA h g^?1, excellent rate performance, and long‐term cycling stability over 800 cycles with capacity retention of 81.8%. The mechanism of Na⁺ and PF₆^? insertion/desertion during the charging/discharging processes is proposed and discussed in detail, with the support of various spectroscopies.     

Electrochemical Performance of Porous Carbon/Tin Composite Anodes for Sodium‐Ion and Lithium‐Ion Batteries

The electrochemical performance of mesoporous carbon (C)/tin (Sn) anodes in Na‐ion and Li‐ion batteries is systematically investigated. The mesoporous C/Sn anodes in a Na‐ion battery shows similar cycling stability but lower capacity and poorer rate capability than that in a Li‐ion battery. The desodiation potentials of Sn anodes are approximately 0.21 V lower than delithiation potentials. The low capacity and poor rate capability of C/Sn anode in Na‐ion batteries is mainly due to the large Na‐ion size, resulting in slow Na‐ion diffusion and large volume change of porous C/Sn composite anode during alloy/dealloy reactions. Understanding of the reaction mechanism between Sn and Na ions will provide insight towards exploring and designing new alloy‐based anode materials for Na‐ion batteries.     

Anodes and Sodium‐Free Cathodes in Sodium Ion Batteries

The increase in electricity generation poses growing demands on energy storage systems, thus offering a chance for the success of the reliable and cost‐effective energy storage technologies. Sodium ion batteries are emerging as such a technology, which is however not yet mature enough to enter the market. At the crux of building practical sodium ion batteries is the development of electrode materials that promise sufficient cost‐ and performance‐competitiveness. As such, herein, all typical sodium storage materials are discussed, considering their fabrication methods and sodiation mechanisms in detail. A comprehensive cross‐literature and cross‐material comparison, which also includes the related thermodynamic analysis of their sodiation products, is also provided. The review focusses particularly on anodes and sodium‐free cathodes, as they both play the role of the acceptor rather than the donor of sodium ions in their operation in batteries; their difference lies in the (de‐)sodiation voltage. In the discussion, special attention is paid to contradictory observations and interpretations in contemporary sodium ion battery research, since debates on these controversies are likely to fuel future sodium battery research.