In P2-type layered oxide cathodes, Na site-regulation strategies are proposed to modulate the Na+ distribution and structural stability. However, their impact on the oxygen redox reactions remains poorly understood. Herein, the incorporation of K+ in the Na layer of Na0.67Ni0.11Cu0.22Mn0.67O2 is successfully applied. The effects of partial substitution of Na+ with K+ on electrochemical properties, structural stability, and oxygen redox reactions have been extensively studied. Improved Na+ diffusion kinetics of the cathode is observed from galvanostatic intermittent titration technique (GITT) and rate performance. The valence states and local structural environment of the transition metals (TMs) are elucidated via operando synchrotron X-ray absorption spectroscopy (XAS). It is revealed that the TMO2 slabs tend to be strengthened by K-doping, which efficiently facilitates reversible local structural change. Operando X-ray diffraction (XRD) further confirms more reversible phase changes during the charge/discharge for the cathode after K-doping. Density functional theory (DFT) calculations suggest that oxygen redox reaction in Na0.62K0.03Ni0.11Cu0.22Mn0.67O2 cathode has been remarkably suppressed as the nonbonding O 2p states shift down in the energy. This is further corroborated experimentally by resonant inelastic X-ray scattering (RIXS) spectroscopy, ultimately proving the role of K+ incorporated in the Na layer.

Prussian blue analogs (PBAs) have been widely recognized as superior cathode materials for sodium-ion batteries (SIBs) owing to numerous merits. However, originating from the rapid crystal growth, PBAs still suffer from considerable vacancy defects and interstitial water, making the preparation of long-cycle-life PBAs the greatest challenge for its practical application. Herein, a novel equilibrium chelation strategy is first proposed to synthesize a high crystallinity (94.7%) PBAs, which is realized by modulating the chelating potency of strong chelating agents via \"acid effect\" to achieve a moderate chelating effect, forcefully breaking through the bottleneck of poor cyclic stability for PBAs cathodes. Impressively, the as-prepared highly crystalline PBAs represent an unprecedented level of electrochemical performance including ultra-long lifespan (10000 cycles with 86.32% capacity maintenance at 6 A g-1), excellent rate capability (82.0 mAh g-1 at 6 A g-1). Meanwhile, by pairing with commercial hard carbon, the as-prepared PBAs-based SIBs exhibit high energy density (350 Wh kg-1) and excellent capacity retention (82.4% after 1500 cycles), highlighting its promising potential for large-scale energy storage applications.

Residual alkali is one of the biggest challenges for the commercialization of sodium-based layered transition metal oxide cathode materials since it can even inevitably appear during the production process. Herein, taking O3-type Na0.9Ni0.25Mn0.4Fe0.2Mg0.1Ti0.05O2 as an example, an active strategy is proposed to reduce residual alkali by slowing the cooling rate, which can be achieved in one-step preparation method. It is suggested that slow cooling can significantly enhance the internal uniformity of the material, facilitating the reintegration of Na+ into the bulk material during the calcination cooling phase, therefore substantially reducing residual alkali. The strategy can remarkably suppress the slurry gelation and gas evolution and enhance the structural stability. Compared to naturally cooled cathode materials, the capacity retention of the slowly cooled electrode material increases from 76.2% to 85.7% after 300 cycles at 1 C. This work offers a versatile approach to the development of advanced cathode materials toward practical applications.

Cost-effectiveness plays a decisive role in sustainable operating of rechargeable batteries. As such, the low cost-consumption of sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) provides a promising direction for \"how do SIBs/PIBs replace Li-ion batteries (LIBs) counterparts\" based on their resource abundance and advanced electrochemical performance. To rationalize the SIBs/PIBs technologies as alternatives to LIBs from the unit energy cost perspective, this review gives the specific criteria for their energy density at possible electrode-price grades and various battery-longevity levels. The cost ($ kWh-1 cycle-1) advantage of SIBs/PIBs is ascertained by the cheap raw-material compensation for the cycle performance deficiency and the energy density gap with LIBs. Furthermore, the cost comparison between SIBs and PIBs, especially on cost per kWh and per cycle, is also involved. This review explicitly manifests the practicability and cost-effectiveness toward SIBs are superior to PIBs whose commercialization has so far been hindered by low energy density. Even so, the huge potential on sustainability of PIBs, to outperform SIBs, as the mainstream energy storage technology is revealed as long as PIBs achieve long cycle life or enhanced energy density, the related outlook of which is proceeded as the next development directions for commercial applications.

Sodium-ion batteries (SIBs), recognized for balanced energy density and cost-effectiveness, are positioned as a promising complement to lithium-ion batteries (LIBs) and a substitute for lead-acid batteries, particularly in low-speed electric vehicles and large-scale energy storage. Despite their extensive potential, concerns about range anxiety due to lower energy density underscore the importance of fast-charging technologies, which drives the exploration of high-rate electrode materials. Polyanionic cathode materials are emerging as promising candidates in this regard. However, their intrinsic limitation in electronic conductivity poses challenges for synchronized electron and ion transport, hindering their suitability for fast-charging applications. This review provides a comprehensive analysis of sodium ion migration during charging/discharging, highlighting it as a critical rate-limiting step for fast charging. By delving into intrinsic dynamics, we identify and summarize key factors that constrain fast-charging characteristics. Innovative modification routes are then introduced, with a focus on shortening migration paths and increasing diffusion coefficients, providing detailed insights into feasible strategies. Moreover, the discussion extends beyond half cells to full cells, addressing challenges and opportunities in transitioning polyanionic materials from the laboratory to practical applications. This review aims to offer valuable insights into the development of high-rate polyanionic cathodes, acknowledging their pivotal role in advancing fast-charging SIBs. This article is protected by copyright. All rights reserved.

Hard carbon anode demonstrates exceptional potential in sodium-ion batteries due to their cost-effectivenss and superior plateau capacity. However, the proximity of the plateau capacity to the cut-off voltage of battery operation and the premature cut-off voltage response caused by polarization at high rates greatly limit the exploitation of plateau capacities, raising big concerns about inferior rate performance of high-plateau-capacity hard carbon. In this work, a facile pre-oxidation strategy is proposed for fabricating lignin-derived hard carbon. Both high-plateau capacity and sodiation kinetics are significantly enhanced due to the introduction of expanded pseudo-graphitic domains and high-speed closed pores. Impressively, the optimized hard carbon exhibits an increased reversible capacity from 252.1 to 302.0 mAh g-1, alongside superior rate performance (174.7 mAh g-1 at 5 C) and stable cyclability over 500 cycles. This study paves a low-cost and effective pathway to modulate the microstructure of biomass-derived hard carbon materials for facilitating plateau sodium storage kinetics.

Sodium-ion battery (SIB) is a candidate for the stationary energy storage systems because of the low cost and high abundance of sodium. However, the energy density and lifespan of SIBs suffer severely from the irreversible consumption of the Na-ions for the formation of the solid electrolyte interphase (SEI) layer and other side reactions on the electrodes. Here, Na3.5C6O6 is proposed as an air-stable high-efficiency sacrificial additive in the cathode to compensate for the lost sodium. It is characteristic of low desodiation (oxidation) potential (3.4-3.6 V vs. Na+/Na) and high irreversible desodiation capacity (theoretically 378 mAh g-1). The feasibility of using Na3.5C6O6 as a sodium compensation additive is verified with the improved electrochemical performances of a Na2/3Ni1/3Mn1/3Ti1/3O2ǀǀhard carbon cells and cells using other cathode materials. In addition, the structure of Na3.5C6O6 and its desodiation path are also clarified on the basis of comprehensive physical characterizations and the density functional theory (DFT) calculations. This additive decomposes completely to supply abundant Na ions during the initial charge without leaving any electrochemically inert species in the cathode. Its decomposition product C6O6 enters the carbonate electrolyte without bringing any detectable negative effects. These findings open a new avenue for elevating the energy density and/or prolonging the lifetime of the high-energy-density secondary batteries.

Sodium-ion batteries (SIBs) have emerged as a compelling alternative to lithium-ion batteries (LIBs), exhibiting comparable electrochemical performance while capitalizing on the abundant availability of sodium resources. In SIBs, P2/O3 biphasic cathodes, despite their high energy, require furthur improvements in stability to meet current energy demands. This study introduces a systematic methodology that leverages the meta-heuristically assisted NSGA-II algorithm to optimize multi-element doping in electrode materials, aiming to transcend conventional trial-and-error methods and enhance cathode capacity by the synergistic integration of P2 and O3 phases. A comprehensive phase analysis of the meta-heuristically designed cathode material Na0.76Ni0.20Mn0.42Fe0.30Mg0.04Ti0.015Zr0.025O2 (D-NFMO) is presented, showcasing its remarkable initial reversible capacity of 175.5 mAh g-1 and exceptional long-term cyclic stability in sodium cells. The investigation of structural composition and the stabilizing mechanisms is performed through the integration of multiple characterization techniques. Remarkably, the irreversible phase transition of P2→OP4 in D-NFMO is observed to be dramatically suppressed, leading to a substantial enhancement in cycling stability. The comparison with the pristine cathode (P-NFMO) offers profound insights into the long-term electrochemical stability of D-NFMO, highlighting its potential as a high-voltage cathode material utilizing abundant earth elements in SIBs. This study opens up new possibilities for future advancements in sodium-ion battery technology.

Manganese (Mn)-based Prussian blue analogs (PBAs) are of great interest as a prospective cathode material for sodium-ion batteries (SIBs) due to their high redox potential, easy synthesis, and low cost. However, the Jahn-Teller effect and low electrical conductivity of Mn-based PBA cause poor structure stability and unsatisfactory performance during the cycling. Herein, a novel nickel- and copper-codoped K2Mn[Fe(CN)6] cathode is developed via a simple coprecipitation strategy. The doping elements improve the electrical conductivity of Mn-based PBA by reducing the bandgap, as well as suppress the Jahn-Teller effect by stabilizing the framework, as verified by the density functional theory calculations. Simultaneously, the substitution of sodium with potassium in the lattice is beneficial for filling vacancies in the PBA framework, leading to higher average operating voltages and superior structural stability. As a result, the as-prepared Mn-based cathode exhibits excellent reversible capacity (116.0 mAh g-1 at 0.01 A g-1) and superior cycling stability (81.8% capacity retention over 500 cycles at 0.1 A g-1). This work provides a profitable doping strategy to inhibit the Jahn-Teller structural deformation for designing stable cathode material of SIBs.

2D layered molybdenum disulfide (MoS2) has garnered considerable attention as an attractive electrode material in sodium-ion batteries (SIBs), but sluggish mass transfer kinetic and capacity fading make it suffer from inferior cycle capability. Herein, hierarchical MoS2 nanosheets decorated porous TiO2 nanofibers (MoS2 NSs@TiO2 NFs) with rich oxygen vacancies are engineered by microemulsion electrospinning method and subsequent hydrothermal/heat treatment. The MoS2 NSs@TiO2 NFs improves ion/electron transport kinetic and long-term cycling performance through distinctive porous structure and heterogeneous component. Consequently, the electrode exhibits excellent long-term Na storage capacity (298.4 mAh g-1 at 5 A g-1 over 1100 cycles and 235.6 mAh g-1 at 10 A g-1 over 7200 cycles). Employing Na3V2(PO4)3 as cathode, the full cell maintains a desirable capacity of 269.6 mAh g-1 over 700 cycles at 1.0 A g-1. The stepwise intercalation-conversion and insertion/extraction endows outstanding Na+ storage performance, which yields valuable insight into the advancement of fast-charging and long-cycle life SIBs anode materials.