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, key factors that constrain fast-charging characteristics are identified and summarized. 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.

Designing artificial interface is a promising strategy to protect Zn metal anode but achieving long Zn plating/stripping lifespans and efficient nucleation/deposition kinetics, particularly at high current densities, remains a challenge. In this study, a permselective zincophilic heterogeneous interface consisting of metallic Ag layer and poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is designed via a simple chemical displacement and drop casting process. The artificial interface plays a multifunctional role in inhibiting dendrite growth/side reactions by reducing the nucleation barrier through a large number of Zn nucleation sites offered by the bottom Ag layer, homogenizing electrical field/Zn2+ flux and shielding SO4 2- migration via the compact, conducting, and Zn2+ -permselective PEDOT:PSS supporting layer. Moreover, the heterogeneous interface demonstrates enhanced structural integrity owing to the binder effect of PEDOT:PSS. As a result, the modified Zn anode demonstrates a cyclic lifespan of 200 h and a reduced voltage hysteresis of ≈150 mV at 20 mA cm-2 /5 mAh cm-2 , far surpassing its counterparts. Moreover, the protected Zn anode allows the LiMn2 O4 -based full cells with remarkable rate and cycling performance. These findings provide new insight into the design of an efficient artificial interface for highly reversible and high-rate Zn electrodeposition.

The practical application of aqueous Zn-ion batteries is still greatly hindered by the unstable Zn anode with severe Zn dendrites growth and side reactions. As it is accessible and economical, the exploitation of electrolyte additives is one of the most promising strategies to stabilize the Zn electrode/electrolyte interface. Herein, the penta-potassium triphosphate (KTPP) as a novel trifunctional electrolyte additive is introduced to tune the electrode/electrolyte interface. First, the KTPP additive can induce an ion-conducting and mechanically robust solid electrolyte interphase film to stabilize the Zn anode. Second, the KTPP can complex with Zn2+ ions to reconstitute the dissolution sheath structure of the Zn2+ ion. Finally, the K+ cations in KTPP adsorb on the tips of the Zn anode surface as a shielding film to regulate Zn2+ ion flux. As a result, Zn//Zn symmetric cells can achieve significantly prolonged cycling stability (e.g., from 1077 to 3800 h at 1 mA cm-2 /1 mAh cm-2 , from 256 to 2500 h at 2 mA cm-2 /2 mAh cm-2 ), and ultrahigh cumulative capacity of 6400/7200 mAh cm-2 at high current density (40/20 mA cm-2 ). A four-layer Zn-MnO2 pouch full cell with a high capacity of 9 mAh can be constructed, showing impressive practical application potential.

High-capacity metal oxides based on non-toxic earth-abundant elements offer unique opportunities as advanced anodes for lithium-ion batteries (LIBs). But they often suffer from large volumetric expansion, particle pulverization, extensive side reactions, and fast degradations during cycling. Here, an easy synthesis method is reported to construct amorphous borate coating network, which stabilizes conversion-type iron oxide anode for the high-energy-density semi-solid-state bipolar LIBs. The nano-borate coated iron oxide anode has high tap density (1.6 g cm-3 ), high capacity (710 mAh g-1 between 0.5 - 3.0 V, vs Li/Li+ ), good rate performance (200 mAh g-1 at 50 C), and excellent cycling stability (≈100% capacity resention over 1,000 cycles at 5 A g-1 ). When paired with high-voltage cathode LiCoO2 , it enables Cu current collector-free pouch-type classic and bipolar full cells with high voltage (7.6 V with two stack layers), achieving high energy density (≈350 Wh kg-1 ), outstanding power density (≈6,700 W kg-1 ), and extended cycle life (75% capacity retention after 2,000 cycles at 2 C), superior to the state-of-the-art high-power LIBs using Li4 Ti5 O12 anode. The design and methodology of the nanoscale polyanion-like coating can be applied to other metal oxides electrode materials, as well as other electrochemical materials and devices.

Flexible aqueous zinc batteries are promising candidates as safe power sources for fast-growing portable and wearable electronics. However, the low working voltage, poor rate capability, and cycling stability have greatly restricted their development and applications. Here, a new family of flexible bimetallic phosphide/carbon nanotube hybrid fiber electrodes with unique macroscopic microcrack structure and microscopic porous nanoflower structure is reported. The hierarchical microcrack structure not only facilitates the penetration of electrolyte for effective exposure of active sites, but also can serve as buffers to relieve the stress concentrations of the fiber electrode under deformations, enabling impressive electrochemical performance and mechanical flexibility. Particularly, the fabricated flexible aqueous zinc batteries demonstrate high working voltage plateau and specific capacity (≈1.7 V, 258.9 mAh g-1 at 2 A g-1 ), ultrahigh rate capability (135.8 mAh g-1 at 50 A g-1 , fully charged in only 9.8 s) and impressive power density of 79 000 W kg-1 . Moreover, the flexible batteries show ultralong cycling life with 74.6% capacity retention after 20 000 cycles. The fiber batteries are also highly flexible and can be easily knitted into soft electronic textiles to power a smartphone, which are particularly promising for the next-generation of flexible and wearable electronics.

Ammonia is a large-scale commodity essential to fertilizer production, but the Haber-Bosch process leads to massive emissions of carbon dioxide. Electrochemical ammonia synthesis is an attractive alternative pathway, but the process is still limited by low ammonia production rate and faradaic efficiency. Herein, guided by our theoretical model, we present a highly efficient lithium-mediated process enabled by using different lithium salts, leading to the formation of a uniform solid-electrolyte interphase (SEI) layer on a porous copper electrode. The uniform lithium-fluoride-enriched SEI layer provides an ammonia production rate of 2.5 ± 0.1 μmol s-1 cmgeo -2 at a current density of -1 A cmgeo -2 with 71% ± 3% faradaic efficiency under 20 bar nitrogen. Experimental X-ray analysis reveals that the lithium tetrafluoroborate electrolyte induces the formation of a compact and uniform SEI layer, which facilitates homogeneous lithium plating, suppresses the undesired hydrogen evolution as well as electrolyte decomposition, and enhances the nitrogen reduction.

Most reported cathode materials for rechargeable aqueous Al metal batteries are based on an intercalative-type chemistry mechanism. Herein, iodine embedded in MOF-derived N-doped microporous carbon polyhedrons (I2 @ZIF-8-C) is proposed to be a conversion-type cathode material for aqueous aluminum-ion batteries based on \"water-in-salt\" electrolytes. Compared with the conventional Al-I2 battery using ionic liquid electrolyte, the proposed aqueous Al-I2 battery delivers much enhanced electrochemical performance in terms of specific capacity and voltage plateaus. Benefitting from the confined liquid-solid conversion of iodine in hierarchical N-doped microporous carbon polyhedrons and enhanced reaction kinetics of aqueous electrolytes, the I2 @ZIF-8-C electrode delivers high reversibility, superior specific capacity (≈219.8 mAh g-1 at 2 A g-1 ), and high rate performance (≈102.6 mAh g-1 at 8 A g-1 ). The reversible reaction between I2 and I- , with I3 - and I5 - as intermediates, is confirmed via ex situ Raman spectra and X-ray photoelectron spectroscopy. Furthermore, solid-state hydrogel electrolyte is employed to fabricate a flexible Al-I2 battery, which shows performance comparable to batteries using liquid electrolyte and can be integrated to power wearable devices as a reliable energy supply.

Although lithium metal is the best anode for lithium-based batteries, the uncontrollable lithium dendrites especially under deep stripping and plating states hamper its practical applications. Here, a dendrite-free lithium anode is developed based on vertically oriented lithium-copper-lithium arrays, which can be facilely produced via traditional rolling or repeated stacking approaches. Such vertically oriented arrays not only enable both the lithium-ion flux and the electric field to be regulated, but also can act as a \"dam\" to guide the regular plating of lithium, thus efficiently buffering the volume change of the lithium anode upon cycling. As a consequence, the vertically oriented anode exhibits an excellent deep stripping and plating capability upto 50 mAh cm-2 , high rate capabilities (20 mA cm-2 ), and long cycle life (2000 h). Based on this anode, a full lithium battery with a LiCoO2 cathode delivers a good cycle life, holding great potential for practical lithium-metal batteries with high energy densities.

The widespread implementation of lithium-metal batteries (LMBs) with Li metal anodes of high energy density has long been prevented due to the safety concern of dendrite-related failure. Here a solid-liquid hybrid electrolyte consisting of composite polymer electrolyte (CPE) soaked with liquid electrolyte is reported. The CPE membrane composes of self-healing polymer and Li+-conducting nanoparticles. The electrodeposited lithium metal in a uniform, smooth, and dense behavior is achieved using a hybrid electrolyte, rather than dendritic and pulverized structure for a conventional separator. The Li foil symmetric cells can deliver remarkable cycling performance at ultrahigh current density up to 20 mA cm-2 with an extremely low voltage hysteresis over 1500 cycles. A large areal capacity of 10 mAh cm-2 at 10 mA cm-2 could also be obtained. Furthermore, the Li|Li4Ti5O12 cells based on the hybrid electrolyte achieve a higher specific capacity and longer cycling life than those using conventional separators. The superior performances are mainly attributed to strong adhesion, volume conformity, and self-healing functionality of CPE, providing a novel approach and a significant step toward cost-effective and large-scalable LMBs.

Lithium-sulfur batteries (LSBs) are receiving extensive attention because of their high theoretical energy density. However, practical applications of LSBs are still hindered by their rapid capacity decay and short cycle life, especially at high rates. Herein, a highly N-doped (≈13.42 at %) hierarchical carbon sponge (HNCS) with strong chemical adsorption for lithium polysulfide is fabricated through a simple sol-gel route followed by carbonization. Upon using the HNCS as the sulfur host material in the cathode and an HNCS-coated separator, the battery delivers an excellent cycling stability with high specific capacities of 424 and 326 mA h g-1 and low capacity fading rates of 0.033 % and 0.030 % per cycle after 1000 cycles under high rates of 5 and 10 C, respectively, which are superior to those of other reported carbonaceous materials. These impressive cycling performances indicate that such a battery could promote the practical application prospects of LSBs.