Nanoarchitectured Array Electrodes for Rechargeable Lithium‐ and Sodium‐Ion Batteries

Rechargeable ion batteries have contributed immensely to shaping the modern world and been seriously considered for the efficient storage and utilization of intermittent renewable energies. To fulfill their potential in the future market, superior battery performance of high capacity, great rate capability, and long lifespan is undoubtedly required. In the past decade, along with discovering new electrode materials, the focus has been shifting more and more toward rational electrode designs because the performance is intimately connected to the electrode architectures, particularly their designs at the nanoscale that can alleviate the reliance on the materials' intrinsic nature. The utilization of nanoarchitectured arrays in the design of electrodes has been proven to significantly improve the battery performance. A comprehensive summary of the structural features and fabrications of the nanoarchitectured array electrodes is provided, and some of the latest achievements in the area of both lithium‐ and sodium‐ion batteries are highlighted. Finally, future challenges and opportunities that would allow further development of such advanced electrode configuration are discussed.     

Electrospun NaVPO4F/C Nanofibers as Self‐Standing Cathode Material for Ultralong Cycle Life Na‐Ion Batteries

NaVPO₄F has received a great deal of attention as cathode material for Na‐ion batteries due to its high theoretical capacity (143 mA h g^?1), high voltage platform, and structural stability. Novel NaVPO₄F/C nanofibers are successfully prepared via a feasible electrospinning method and subsequent heat treatment as self‐standing cathode for Na‐ion batteries. Based on the morphological and microstructural characterization, it can be seen that the NaVPO₄F/C nanofibers are smooth and continuous with NaVPO₄F nanoparticles (≈6 nm) embedded in porous carbon matrix. For Na‐storage, this electrode exhibits extraordinary electrochemical performance: a high capacity (126.3 mA h g^?1 at 1 C), a superior rate capability (61.2 mA h g^?1 at 50 C), and ultralong cyclability (96.5% capacity retention after 1000 cycles at 2 C). 1D NaVPO₄F/C nanofibers that interlink into 3D conductive network improve the conductivity of NaVPO₄F, and effectively restrain the aggregation of NaVPO₄F particles during charge/discharge process, leading to the high performance.     

Nanoconfined Carbon‐Coated Na3V2(PO4)3 Particles in Mesoporous Carbon Enabling Ultralong Cycle Life for Sodium‐Ion Batteries

Na₃V₂(PO₄)₃ (denoted as NVP) has been considered as a promising cathode material for room temperature sodium ion batteries. Nevertheless, NVP suffers from poor rate capability resulting from the low electronic conductivity. Here, the feasibility to approach high rate capability by designing carbon‐coated NVP nanoparticles confined into highly ordered mesoporous carbon CMK‐3 matrix (NVP@C@CMK‐3) is reported. The NVP@C@CMK‐3 is prepared by a simple nanocasting technique. The electrode exhibits superior rate capability and ultralong cyclability (78 mA h g^?1 at 5 C after 2000 cycles) compared to carbon‐coated NVP and pure NVP cathode. The improved electrochemical performance is attributed to double carbon coating design that combines a variety of advantages: very short diffusion length of Na⁺/e^? in NVP, easy access of electrolyte, and short transport path of Na⁺ through carbon toward the NVP nanoparticle, high conductivity transport of electrons through the 3D interconnected channels of carbon host. The optimum design of the core–shell nanostructures with double carbon coating permits fast kinetics for both transported Na⁺ ions and electrons, enabling high‐power performance.     

Heteroatom‐Doped Mesoporous Hollow Carbon Spheres for Fast Sodium Storage with an Ultralong Cycle Life

Carbon materials have attracted significant attention as anode materials for sodium ion batteries (SIBs). Developing a carbon anode with long‐term cycling stability under ultrahigh rate is essential for practical application of SIBs in energy storage systems. Herein, sulfur and nitrogen codoped mesoporous hollow carbon spheres are developed, exhibiting high rate performance of 144 mA h g^?1 at 20 A g^?1, and excellent cycling durability under ultrahigh current density. Interestingly, during 7000 cycles at a current density of 20 A g^?1, the capacity of the electrode gradually increases to 180 mA h g^?1. The mechanisms for the superior electrochemical performance and capacity improvement of the cells are studied by electrochemical tests, ex situ transmission electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, and Raman analysis of fresh and cycled electrodes. The unique and robust structure of the material can enhance transport kinetics of electrons and sodium ions, and maintain fast sodium storage from the capacitive process under high rate. The self‐rearrangement of the carbon structure, induced by continuous discharge and charge, lead to the capacity improvement with cycles. These results demonstrate a new avenue to design advanced anode materials for SIBs.     

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.     

Bifunctional Conducting Polymer Coated CoP Core–Shell Nanowires on Carbon Paper as a Free‐Standing Anode for Sodium Ion Batteries

This study proposes a conformal surface coating of conducting polymer for protecting 1D nanostructured electrode material, thereby enabling a free‐standing electrode without binder for sodium ion batteries. Here, polypyrrole (PPy), which is one of the representative conducting polymers, encapsulated cobalt phosphide (CoP) nanowires (NWs) grown on carbon paper (CP), finally realizes 1D core–shell CoP@PPy NWs/CP. The CoP core is connected to the PPy shell via strong chemical bonding, which can maintain a Co–PPy framework during charge/discharge. It also possesses bifunctional features that enhances the charge transfer and buffers the volume expansion. Consequently, 1D core–shell CoP@PPy NWs/CP demonstrates superb electrochemical performance, delivering a high areal capacity of 0.521 mA h cm^?2 at 0.15 mA cm^?2 after 100 cycles, and 0.443 mA h cm^?2 at 1.5 mA cm^?2 even after 1000 cycles. Even at a high current density of 3 mA cm^?2, a significant areal discharge capacity reaching 0.285 mA h cm^?2 is still maintained. The outstanding performance of the CoP@PPy NWs/CP free‐standing anode provides not only a novel insight into the modulated volume expansion of anode materials but also one of the most effective strategies for binder‐free and free‐standing electrodes with decent mechanical endurance for future secondary batteries.     

Boosting Fast Sodium Storage of a Large‐Scalable Carbon Anode with an Ultralong Cycle Life

Sodium‐ion batteries (SIBs) are considered to be a promising alternative for large‐scale electricity storage. However, it is urgent to develop new anode materials with superior ultralong cycle life performance at high current rates. Herein, a low‐cost and large‐scalable sulfur‐doped carbon anode material that exhibits the best high‐rate cycle performance and the longest cycle life ever reported for carbon anodes is developed. The material delivers a reversible capacity of 142 mA h g^?1 at a current rate up to 10 A g^?1. After 10 000 cycles the capacity is remained at 126.5 mA h g^?1; 89.1% of the initial value. Density functional theory computations demonstrate that the sulfur‐doped carbon has a strong binding affinity for sodium which promotes sodium storage. Meanwhile, the kinetics analysis identifies the capacitive charge storage as a large contributor to sodium storage, which favors ultrafast storage of sodium ions. These results demonstrate a new way to design carbon‐based SIBs anodes for next‐generation large‐scale electricity storage.