Layered oxides of sodium-ion batteries suffer from severe side reactions on the electrode/electrolyte interface, leading to fast capacity degradation. Although surface reconstruction strategies are widely used to solve the above issues, the utilization of the low-cost wet chemical method is extremely challenging for moisture-sensitive Na-based oxide materials. Here, the solvation tuning strategy is proposed to overcome the deterioration of NaNi1/3Mn1/3Fe1/3O2 in water-based solution and conduct the surface reconstruction. When capturing the water molecules by the solvation structure of cations, here is Li+, the structural collapse and degradation of layered oxides in water-based solvents are greatly mitigated. Furthermore, Li(H2O)3EA+ promotes the profitable Li+/Na+ exchange to build a robust surface, which hampers the decomposition of electrolytes and the structural evolution upon cycling. Accordingly, the lifespan of Li-reinforced materials is prolonged to three times that of the pristine one. This work represents a step forward in understanding the surface reconstruction operated in a water-based solution for high-performance sodium layered oxide cathodes.

From basic research to industry process, battery energy storage systems have played a great role in the informatization, mobility, and intellectualization of modern human society. Some potential systems such as Li, Na, K, Mg, Zn, and Al secondary batteries have attracted much attention to maintain social progress and sustainable development. As one of the components in batteries, electrolytes play an important role in the upgrade and breakthrough of battery technology. Since room-temperature ionic liquids (ILs) feature high conductivity, nonflammability, nonvolatility, high thermal stability, and wide electrochemical window, they have been widely applied in various battery systems and show great potential in improving battery stability, kinetics performance, energy density, service life, and safety. Thus, it is a right time to summarize these progresses. In this review, the composition and classification of various ILs and their recent applications as electrolytes in diverse metal-ion batteries (Li, Na, K, Mg, Zn, Al) are outlined to enhance the battery performances.

Electrochemical irreversibility and sluggish mobility of Na+ in the cathode materials result in poor cycle stability and rate capability for sodium-ion batteries. Herein, a new strategy of introducing Mg ions into the hinging sites of Mn-based tunnel-structured cathode material is designed. Highly reversible electrochemical reaction and phase transition in this cathode are realized. The resulted Na0.44Mn0.95Mg0.05O2 with Mg2+ in the hinging Mn-O5 square pyramidal exhibits promising cycle stability and rate capability. At a current density of 2 C, 67% of the initial discharge capacity is retained after 800 cycles (70% at 20 C), much improved than the undoped Na0.44MnO2. The improvement is attribute to the enhanced Na+ diffusion kinetics and the lowered desodiation energy after Mg doping. Highly reversible charge compensation and structure evolution are proved by synchrotron-based X-ray techniques. Differential charge density and atom population analysis of the average electron number of Mn indicate that Na0.44Mn0.95Mg0.05O2 is more electron-abundant in Mn 3d orbits near the Fermi level than that in Na0.44MnO2, leading to higher redox participation of Mn ions.

The electrochemical intercalation/deintercalation of solvated sodium ions into graphite is a highly reversible process, but leads to large, undesired electrode expansion/shrinkage (\"breathing\"). Herein, two strategies to mitigate the electrode expansion are studied. Starting with the standard configuration (-) sodium | diglyme (2G) electrolyte | graphite (poly(vinylidene difluoride) (PVDF) binder) (+), the PVDF binder is first replaced with a binder made of the sodium salt of carboxymethyl cellulose (CMC). Second, ethylenediamine (EN) is added to the electrolyte solution as a co-solvent. The electrode breathing is followed in situ (operando) through electrochemical dilatometry (ECD). It is found that replacing PVDF with CMC is only effective in reducing the electrode expansion during initial sodiation. During cycling, the electrode breathing for both binders is comparable. Much more effective is the addition of EN. The addition of 10 v/v EN to the diglyme electrolyte strongly reduces the electrode expansion during the initial sodiation (+100% with EN versus +175% without EN) as well as the breathing during cycling. A more detailed analysis of the ECD signals reveals that solvent co-intercalation temporarily leads to pillaring of the graphite lattice and that the addition of EN to 2G leads to a change in the sodium storage mechanism.

Germanium (Ge)-based materials have been considered as potential anode materials for sodium-ion batteries owing to their high theoretical specific capacity. However, the poor conductivity and Na+ diffusivity of Ge-based materials result in retardant ion/electron transportation and insufficient sodium storage efficiency, leading to sluggish reaction kinetics. To intrinsically maximize the sodium storage capability of Ge, the nitrogen doped carbon-coated Cu3Ge/Ge heterostructure material (Cu3Ge/Ge@N-C) is developed for enhanced sodium storage. The pod-like structure of Cu3Ge/Ge@N-C exposes numerous active surface to shorten ion transportation pathway while the uniform encapsulation of carbon shell improves the electron transportation, leading to enhanced reaction kinetics. Theoretical calculation reveals that Cu3Ge/Ge heterostructure can offer decent electron conduction and lower the Na+ diffusion barrier, which further promotes Ge alloying reaction and improves its sodium storage capability close to its theoretical value. In addition, the uniform encapsulation of nitrogen-doped carbon on Cu3Ge/Ge heterostructure material efficiently alleviates its volume expansion and prevents its decomposition, further ensuring its structural integrity upon cycling. Attributed to these unique superiorities, the as-prepared Cu3Ge/Ge@N-C electrode demonstrates admirable discharge capacity, outstanding rate capability and prolonged cycle lifespan (178 mAh g-1 at 4.0 A g-1 after 4000 cycles).

Iron/manganese-based layered transition metal oxides have risen to prominence as prospective cathodes for sodium-ion batteries (SIBs) owing to their abundant resources and high theoretical specific capacities, yet they still suffer from rapid capacity fading. Herein, a dual-strategy is developed to boost the Na-storage performance of the Fe/Mn-based layered oxide cathode by copper (Cu) doping and nanoengineering. The P2-Na0.76Cu0.22Fe0.30Mn0.48O2 cathode material synthesized by electrospinning exhibits the pearl necklace-like hierarchical nanostructures assembled by nanograins with sizes of 50-150 nm. The synergistic effects of Cu doping and nanotechnology enable high Na+ coefficients and low ionic migration energy barrier, as well as highly reversible structure evolution and Cu/Fe/Mn valence variation upon repeated sodium insertion/extraction; thus, the P2-Na0.76Cu0.22Fe0.30Mn0.48O2 nano-necklaces yield fabulous rate capability (125.4 mA h g-1 at 0.1 C with 56.5 mA h g-1 at 20 C) and excellent cyclic stability (≈79% capacity retention after 300 cycles). Additionally, a promising energy density of 177.4 Wh kg-1 is demonstrated in a prototype soft-package Na-ion full battery constructed by the tailored nano-necklaces cathode and hard carbon anode. This work symbolizes a step forward in the development of Fe/Mn-based layered oxides as high-performance cathodes for SIBs.

Metal sulfides have been intensively investigated for efficient sodium-ion storage due to their high capacity. However, the mechanisms behind the reaction pathways and phase transformation are still unclear. Moreover, the effects of designed nanostructure on the electrochemical behaviors are rarely reported. Herein, a hydrangea-like CuS microsphere is prepared via a facile synthetic method and displays significantly enhanced rate and cycle performance. Unlike the traditional intercalation and conversion reactions, an irreversible amorphization process is evidenced and elucidated with the help of in situ high-resolution synchrotron radiation diffraction analyses, and transmission electron microscopy. The oriented (006) crystal plane growth of the primary CuS nanosheets provide more channels and adsorption sites for Na ions intercalation and the resultant low overpotential is beneficial for the amorphous Cu-S cluster, which is consistent with the density functional theory calculation. This study can offer new insights into the correlation between the atomic-scale phase transformation and macro-scale nanostructure design and open a new principle for the electrode materials\' design.

3D electrode design is normally opted for multiple advantages, however, instability/detachment of active material causes the pulverization and degradation of the structure, and ultimately poor cyclic stability. Here, a dually protected, highly compressible, and freestanding anode is presented for sodium-ion batteries, where 3D carbon nanotube (CNT) sponge is decorated with homogeneously dispersed CoSe2 nanoparticles (NPs) which are protected under carbon overcoat (CNT/CoSe2/C). The 3D CNT sponge delivers enough space for high mass loading while providing high mechanical strength and faster conduction pathway among the NPs. The outer amorphous carbon overcoat controls the formation of solid electrolyte interphase film by avoiding direct contact of CoSe2 with electrolyte, accommodates large volume changes, and ultimately enhances the overall conductivity of cell and assists in transmitting electron to an external circuit. Moreover, the hybrid can be densified up to 11-fold without affecting its microstructure that results in ultrahigh areal mass loading of 17.4 mg cm-2 and an areal capacity of 7.03 mAh cm-2 along with a high gravimetric capacity of 531 mAh g-1 at 100 mA g-1. Thus, compact and smart devices can be realized by this new electrode design for heavy-duty commercial applications.

In this paper, the synthesis of ultrasmall Na2FePO4F nanoparticles (≈3.8 nm) delicately embedded in porous N-doped carbon nanofibers (denoted as Na2FePO4F@C) by electrospinning is reported. The as-prepared Na2FePO4F@C fiber film tightly adherent on aluminum foil features great flexibility and is directly used as binder-free cathode for sodium-ion batteries, exhibiting admirable electrochemical performance with high reversible capacity (117.8 mAh g-1 at 0.1 C), outstanding rate capability (46.4 mAh g-1 at 20 C), and unprecedentedly high cyclic stability (85% capacity retention after 2000 cycles). The reaction kinetics and mechanism are explored by a combination study of cyclic voltammetry, ex situ structure/valence analyses, and first-principles computations, revealing the highly reversible phase transformation of Na2FeIIPO4F ↔ NaFeIIIPO4F, the facilitated Na+ diffusion dynamics with low energy barriers, and the desirable pseudocapacitive behavior for fast charge storage. Pouch-type Na-ion full batteries are also assembled employing the Na2FePO4F@C nanofibers cathode and the carbon nanofibers anode, demonstrating a promising energy density of 135.8 Wh kg-1 and a high capacity retention of 84.5% over 200 cycles. The distinctive network architecture of ultrafine active materials encapsulated into interlinked carbon nanofibers offers an ideal platform for enhancing the electrochemical reactivity, electronic/ionic transmittability, and structural stability of Na-storage electrodes.

There is an ever-increasing demand for rechargeable batteries with fast charging, long cycling, high safety, and low cost in new energy storage systems. Herein, a heterogeneous architecture composed of MoS2-coupled carbon nanosheets encapsulated on sodium titanate nanowires is developed and demonstrated as an advanced anode for sodium-ion batteries (SIBs). Owing to the synergistic effects of ultrastable substrate of 1D sodium titanate (NTO) nanowires, high-capacity promoter of 2D MoS2 nanosheets as well as the 2D conductive carbon matrix, the resulting 1D/2D-2D hybrid demonstrates excellent high-rate capacity and super-durable cyclability, delivering a stable capacity of up to 425.5 mAh g-1 at 200 mA g-1. Even at an ultrafast charging/discharging process within 80 s, the capacity can be maintained at 201 mAh g-1 after 16 000 cycles with only 0.0012% capacity loss per cycle, one of the best high-rate capacities and cyclabilities for NTO-based hybrid composites. The present work highlights the designing protocol of hierarchical nanoarchitectures with stable substrate and high-capacity electrodes for next-generation energy storage applications.