The ever‐increasing demand of lithium‐ion batteries (LIBs) caused by the rapid development of various electronics and electric vehicles will be hindered by the limited lithium resource. Thus sodium‐ion batteries (SIBs) have been considered as a promising potential alternative for LIBs owing to the abundant sodium resource and similar electrochemical performances. In recent years, significant achievements regarding anode materials which restricted the development of SIBs in the past decades have been attained. Significantly, the sodium storage feasibility of carbon materials with abundant resource, low cost, nontoxicity and high safety has been confirmed, and extensive investigation have demonstrated that the carbonaceous materials can become promising electrode candidates for SIBs. In this review, the recent progress of the sodium storage performances of carbonaceous materials, including graphite, amorphous carbon, heteroatom‐doped carbon, and biomass derived carbon, are presented and the related sodium storage mechanism is also summarized. Additionally, the critical issues, challenges and perspectives are provided to further understand the carbonaceous anode materials.

A new methodology for the synthesis of carbon quantum dots (CQDs) for large production is proposed. The as-obtained CQDs can be transformed into 3D porous carbon frameworks exhibiting superb sodium storage properties with ultralong cycle life and ultrahigh rate capability, comparable to state-of-the-art carbon anode materials for sodium-ion batteries.

Large‐area phosphorus‐doped carbon nanosheets (P‐CNSs) are first obtained from carbon dots (CDs) through self‐assembly driving from thermal treatment with Na catalysis. This is the first time to realize the conversion from 0D CDs to 2D nanosheets doped with phosphorus. The sodium storage behavior of phosphorus‐doped carbon material is also investigated for the first time. As anode material for sodium‐ion batteries (SIBs), P‐CNSs exhibit superb performances for electrochemical storage of sodium. When cycled at 0.1 A g−1, the P‐CNSs electrode delivers a high reversible capacity of 328 mAh g−1, even at a high current density of 20 A g−1, a considerable capacity of 108 mAh g−1 can still be maintained. Besides, this material also shows excellent cycling stability, at a current density of 5 A g−1, the reversible capacity can still reach 149 mAh g−1 after 5000 cycles. This work will provide significant value for the development of both carbon materials and SIBs anode materials.

Designing potential anodes for sodium-ion battery with both remarkable durability and high-rate capability has captured enormous attention so far. The engineering of size and morphology is deemed as an effective manner to boost the electrochemical properties. Owing to the anisotropic self-assembly of iron selenide, rod-like FeSe 2 coates with nitrogen-doped carbon is prepared through the thermal reaction of Prussian blue with selenium. Notably, the cyano groups are effectively transformed into N-doped carbon with FeNC bonds, which uniformly coats FeSe 2 , prompting Na + transportations. Interestingly, the particle size is tailored by heating rates, along with increased carbon content, leading to broadened energy levels for redox reaction. Bestowed by these advantages, the FeSe 2 /N-C as Na-storage anode delivers impressive electrochemical properties. Even at a rather high rate of 10.0 A g −1 , a considerable capacity of 308 mAh g −1 is yielded over 10 000 loops. Supported by the detailed analysis of kinetic features, reduced size of particles could bring about the enhanced contributions of pseudocapacitive and quickening rate of ions transferring. The phase evolutions are further investigated by in situ EIS and ex-situ technologies. The work is expected to provide a new strategy to prepare metal-selenide with controllable size and induce the faster kinetic of high-rate materials.

Carbon dots inducing petal-like rutile TiO wrapped by ultrathin graphene-rich layers are proposed to fabricate superior anodes for sodium-ion batteries, featuring high-rate capabilities and long-term cyclelife, benefiting from promoted electron transport and a shortened Na diffusion length. High capacities of 144.4 mA h g (at 837.5 mA g ) after 1100 cycles and 74.6 mA h g (at 3350 mA g ) after 4000 cycles are delivered outstandingly.

Nanostructured black anatase titania with oxygen vacancies (OVs) is efficiently obtained and employed as an anode in sodium-ion batteries (SIBs) for the first time. The incorporation of OVs into TiO2 is demonstrated to render considerably enhanced-rate performances, higher initial capacities, and an accelerated electrochemical activation process during cycling, derived from the boosted intrinsic electric conductivity and improved kinetics of Na uptake. Bestowed with the integrated merits of OVs and shortened Na ion diffusion length in the nanostructure, black titania delivers a reversible specific capacity of 207.6 mAh g(-1) at 0.2 C, retains 99.1% over 500 cycles at 1 C stably, and still maintains 91.2 mAh g(-1) even at the high rate of 20 C. Density functional theory (DFT) calculations suggest that the lower sodiation energy barrier of anatase with OVs enables a more favorable Na intercalation into black anatase. Thus, it is of great significance to introduce OVs into TiO2 to stimulate ultrafast and durable sodium-storage properties, which also offers a potential strategy to project more superior electrodes, utilizing internal defects.

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/smll.201905842. Rechargeable Zn/MnO 2 batteries using mild aqueous electrolytes are attracting extensive attention due to their low cost, high safety, and environmental friendliness. However, the charge-storage mechanism involved remains a topic of controversy so far. Also, the practical energy density and cycling stability are still major issues for their applications. Herein, a free-standing α-MnO 2 cathode for aqueous zinc-ion batteries (ZIBs) is directly constructed with ultralong nanowires, leading to a rather high energy density of 384 mWh g −1 for the entire electrode. Greatly, the H + /Zn 2+ coinsertion mechanism of α-MnO 2 cathode for aqueous ZIBs is confirmed by a combined analysis of in situ X-ray diffractometry, ex situ transmission electron microscopy, and electrochemical methods. More interestingly, the Zn 2+ -insertion is found to be less reversible than H + -insertion in view of the dramatic capacity fading occurring in the Zn 2+ -insertion step, which is further evidenced by the discovery of an irreversible ZnMn 2 O 4 layer at the surface of α-MnO 2 . Hence, the H + -insertion process actually plays a crucial role in maintaining the cycling performance of the aqueous Zn/α-MnO 2 battery. This work is believed to provide an insight into the charge-storage mechanism of α-MnO 2 in aqueous systems and paves the way for designing aqueous ZIBs with high energy density and long-term cycling ability. www.advancedsciencenews.com

Liquid phase exfoliation of few-layer phosphorene (FL-P) is extensively explored in recent years. Nevertheless, their deficiencies such as ultralong sonication time, limited flake size distribution, and uncontrollable thicknesses are major hurdles for the development of phosphorene-based materials. Herein, electrochemical cationic intercalation has been introduced to prepare phosphorene, through which large-area FL-P without surface functional groups can be efficiently attained (less than 1 h). More importantly, its layer number (from 2 to 11 layers) can be manipulated by changing the applied potential. The as-obtained phosphorene delivers superior sodium-storage performances when directly utilized as an anode material in sodium-ion batteries. This electrochemical cation insertion method to prepare phosphorene should greatly facilitate the development of phosphorene-based technologies. Moreover, this work provides the possibility for the scalable preparation of monolayer 2D materials by exploring intercalation ions. Additionally, the successful electrochemical exfoliation of phosphorene can promote the application of electrochemical exfoliation in other 2D materials.