Promising Cathode Materials for Sodium-Ion Batteries from Lab to Application.

Sodium-ion batteries (SIBs) are seen as an emerging force for future large-scale energy storage due to their cost-effective nature and high safety. Compared with lithium-ion batteries (LIBs), the energy density of SIBs is insufficient at present. Thus, the development of high-energy SIBs for realizing large-scale energy storage is extremely vital. The key factor determining the energy density in SIBs is the selection of cathodic materials, and the mainstream cathodic materials nowadays include transition metal oxides, polyanionic compounds, and Prussian blue analogs (PBAs). The cathodic materials would greatly improve after targeted modulations that eliminate their shortcomings and step from the laboratory to practical applications. Before that, some remaining challenges in the application of cathode materials for large-scale energy storage SIBs need to be addressed, which are summarized at the end of this Outlook.

Controllable fabrication of vanadium selenium nanosheets for a high-performance Na-ion battery anode.

Vanadium selenium has gained attention as a potential anode for sodium-ion batteries (SIBs) due to the tunable crystal structure, effective channels for Na+ diffusion, and high theoretical specific capacity. However, the pursuit of vanadium selenium remains an enormous challenge. Herein, we demonstrated that V2Se9 nanosheets could be fabricated facilely and efficiently via a one-pot synthesis method with the careful selection of the solvent/surfactant. The V2Se9 anode have demonstrated excellent electrochemical performance for SIBs. An intercalation and conversion mechanism of Na-storage in V2Se9 were clarified by ex situ X-ray diffraction. This work develops an effective strategy to fabricate transition metal chalcogenides for high-performance sodium storage.

Enhancing Interfacial Strength and Wettability for Wide-Temperature Sodium Metal Batteries.

Development of high-performance sodium metal batteries (SMBs) with a wide operating temperature range (from -40 to 55 °C) is highly challenging. Herein, an artificial hybrid interlayer composed of sodium phosphide (Na3 P) and metal vanadium (V) is constructed for wide-temperature-range SMBs via vanadium phosphide pretreatment. As evidenced by simulation, the VP-Na interlayer can regulate redistribution of Na+ flux, which is beneficial for homogeneous Na deposition. Moreover, the experimental results confirm that the artificial hybrid interlayer possesses a high Young's modulus and a compact structure, which can effectively suppress Na dendrite growth and alleviate the parasitic reaction even at 55 °C. In addition, the VP-Na interlayer exhibits the capability to knock down the kinetic barriers for fast Na+ transportation, realizing a 30-fold decrease in impedance at -40 °C. Symmetrical VP-Na cells present a prolonged lifespan reaching 1200, 500, and 500 h at room temperature, 55 °C and -40 °C, respectively. In Na3 V2 (PO4 )3 ||VP-Na full cells, a high reversible capacity of 88, 89.8, and 50.3 mAh g-1 can be sustained after 1600, 1000, and 600 cycles at room temperature, 55 °C and -40 °C, respectively. The pretreatment formed artificial hybrid interlayer proves to be an effective strategy to achieve wide-temperature-range SMBs.

Construction of Inorganic/Organic Hybrid Layer for Stable Na Metal Anode Operated under Wide Temperatures.

Sodium metal battery is supposed to be a propitious technology for high-energy storage application owing to the advantages of natural abundance and low cost. Unfortunately, the uncontrollable dendrite growth critically hampers its practical implementation. Herein, an inorganic/organic hybrid layer of NaF/CF/CC on the surface of Na foil (IOHL-Na) is designed and synthesized through the in situ reaction of polyvinylidene fluoride (PVDF) and metallic sodium. This protective layer possesses satisfactory Young's modulus, good kinetic property, and sodiophilicity, which can distinctly stabilize Na metal anode. As a result, the symmetric IOHL-Na cell achieves a lifespan of 770 h at 1 mAh cm-2 /1 mA cm-2 in carbonate electrolyte. The assembled full battery of IOHL-Na||Na3 V2 (PO4 )3 delivers a high discharge capacity of 85 mAh g-1 at 10 C after 600 cycles under ambient temperature. Furthermore, the IOHL-Na||Na3 V2 (PO4 )3 cell still can steadily operate at 10 C for 600 cycles at 55 °C. And when testing at an ultralow temperature of -40 °C, the full cell achieves 40 mAh g-1 at 0.5 C with a prolonged lifespan of 450 cycles. This work offers a new approach to protect the metal sodium anode without dendrite growth under wide temperatures.

Interfacial Engineering of Na3V2(PO4)2O2F Cathode for Low-Temperature (-40 °C) Sodium-Ion Batteries.

Na3V2(PO4)2O2F (NVPOF) is considered a promising cathode material for sodium-ion batteries (SIBs) on account of its attractive electrochemical properties such as high theoretical capacity, stable structure, and high working platform. Nevertheless, the inevitable interface problems like sluggish interfacial electrochemical reaction kinetics and poor interfacial ion storage capacity seriously hinder its application. Construction of chemical bonding is a highly effective way to solve interface problems. Herein, NVPOF with interfacial V-F-C bonding (CB-NVPOF) is developed. The CB-NVPOF cathode exhibits high rate capability (65 mA h g-1 at 40C) and long-term cycling stability (a capacity retention of 77% after 2000 cycles at 20C). Furthermore, it shows impressive electrochemical performance at temperatures as low as -40 °C, delivering a capacity of 56 mA h g-1 at 10C and a capacity retention of ∼80% after 500 cycles at 2C. The interfacial V-F-C bond engineering significantly advances the electronic conductivity, Na+ diffusion, as well as interface compatibility at -40 °C. This study provides a novel idea for improving the electrochemical performance of NVPOF-based cathodes for SIBs aiming for low-temperature applications.

Vanadium fluorophosphates: advanced cathode materials for next-generation secondary batteries.

Next-generation secondary batteries including sodium-ion batteries (SIBs) and potassium-ion batteries (PIBs) are considered the most promising candidates for application to large-scale energy storage systems due to their abundant, evenly distributed and cost-effective sodium/potassium raw materials. The electrochemical performance of SIBs (PIBs) significantly depends on the inherent characteristics of the cathode material. Among the wide variety of cathode materials, sodium/potassium vanadium fluorophosphate (denoted as MVPF, M = Na and K) composites are widely investigated due to their fast ion transportation and robust structure. However, their poor electron conductivity leads to low specific capacity and poor rate capacity, limiting the further application of MVPF cathodes in large-scale energy storage. Accordingly, several modification strategies have been proposed to improve the performance of MVPF such as conductive coating, morphological regulation, and heteroatomic doping, which boost the electronic conductivity of these cathodes and enhance Na (K) ion transportation. Furthermore, the development and application of MVPF cathodes in SIBs at low temperatures are also outlined. Finally, we present a brief summary of the remaining challenges and corresponding strategies for the future development of MVPF cathodes.

A Multifunctional Interphase Layer Enabling Superior Sodium-Metal Batteries under Ambient Temperature and -40 °C.

The sodium (Na)-metal anode with high theoretical capacity and low cost is promising for construction of high-energy-density metal batteries. However, the unsatisfactory interface between Na and the liquid electrolyte induces tardy ion transfer kinetics and dendritic Na growth, especially at ultralow temperature (-40 °C). Herein, an artificial heterogeneous interphase consisting of disodium selenide (Na2 Se) and metal vanadium (V) is produced on the surface of Na (Na@Na2 Se/V) via an in situ spontaneous chemical reaction. Such interphase layer possesses high sodiophilicity, excellent ionic conductivity, and high Young's modulus, which can promote Na-ion adsorption and transport, realizing homogenous Na deposition without dendrites. The symmetric Na@Na2 Se/V cell exhibits outstanding cycling life span of over 1790 h (0.5 mA cm-2 /1 mAh cm-2 ) in carbonate-based electrolyte. More remarkably, ab initio molecular dynamics simulations reveal that the artificial Na2 Se/V hybrid interphase can accelerate the desolvation of solvated Na+ at -40 °C. The Na@Na2 Se/V electrode thus exhibits exceptional electrochemical performance in symmetric cell (over 1500 h at 0.5 mA cm-2 /0.5 mAh cm-2 ) and full cell (over 700 cycles at 0.5 C) at -40 °C. This work provides an avenue to design artificial heterogeneous interphase layers for superior high-energy-density metal batteries at ambient and ultralow temperatures.

Multi-component surface engineering of Na3V2(PO4)2O2F for low-temperature (-40 °C) sodium-ion batteries.

A functional Na3V2(PO4)2O2F (NVPOF) cathode with a multi-component (Na3V(PO4)2, V2O3, and reduced graphene oxide) surface coating is developed via a facile hydrothermal reaction followed by calcination, and exhibits high reversible capability, and long-term cycling stability even at a low temperature of -40 °C. It is demonstrated that the multi-component-coating layer can significantly accelerate the e-/Na+ transport and reduce the interfacial resistance at low temperature. This work provides a novel strategy to boost the kinetics and stability of electrode materials for low-temperature sodium ion batteries.