Inhibiting the Jahn-Teller Effect of Manganese Hexacyanoferrate via Ni and Cu Codoping for Advanced Sodium-Ion Batteries.

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.

High-Voltage Potassium Hexacyanoferrate Cathode via High-Entropy and Potassium Incorporation for Stable Sodium-Ion Batteries.

Prussian blue analogues (PBAs) used as sodium ion battery (SIB) cathodes are usually the focus of attention due to their three-dimensional open frame and high theoretical capacity. Nonetheless, the disadvantages of a low working voltage and inferior structural stability of PBAs prevent their further applications. Herein, we propose constructing the Kx(MnFeCoNiCu)[Fe(CN)6] (HE-K-PBA) cathode by high-entropy and potassium incorporation strategy to simultaneously realize high working voltage and cycling stability. The reaction mechanism of metal cations in HE-K-PBA are revealed by synchrotron radiation X-ray absorption spectroscopy (XAS), ex situ X-ray photoelectron spectroscopy (XPS), and in situ Raman spectra. We also investigate the entropy stabilization mechanism via finite element simulation, demonstrating that HE-K-PBA with small von Mises stress and weak structure strain can significantly mitigate the structural distortion. Benefit from the stable structure and everlasting K+ (de)intercalation, the HE-K-PBA delivers high output voltage (3.46 V), good reversible capacity (120.5 mAh g-1 at 0.01 A g-1), and capacity retention of 90.4% after 1700 cycles at 1.0 A g-1. Moreover, the assembled full cell and all-solid-state batteries with a stable median voltage of 3.29 V over 3000 cycles further demonstrate the application prospects of the HE-K-PBA cathode.

Multi-Scale Structure Engineering of ZnSnO3 for Ultra-Long-Life Aqueous Zinc-Metal Batteries.

Suppressing the severe water-induced side reactions and uncontrolled dendrite growth of zinc (Zn) metal anodes is crucial for aqueous Zn-metal batteries to achieve ultra-long cyclic lifespans and promote their practical applications. Herein, a concept of multi-scale (electronic-crystal-geometric) structure design is proposed to precisely construct the hollow amorphous ZnSnO3 cubes (HZTO) for optimizing Zn metal anodes. In situ gas chromatography demonstrates that Zn anodes modified by HZTO (HZTO@Zn) can effectively inhibit the undesired hydrogen evolution. The pH stabilization and corrosion suppression mechanisms are revealed via operando pH detection and in situ Raman analysis. Moreover, comprehensive experimental and theoretical results prove that the amorphous structure and hollow architecture endow the protective HZTO layer with strong Zn affinity and rapid Zn2+ diffusion, which are beneficial for achieving the ideal dendrite-free Zn anode. Accordingly, excellent electrochemical performances for the HZTO@Zn symmetric battery (6900 h at 2 mA cm-2 , 100 times longer than that of bare Zn), HZTO@Zn||V2 O5 full battery (99.3% capacity retention after 1100 cycles), and HZTO@Zn||V2 O5 pouch cell (120.6 Wh kg-1 at 1 A g-1 ) are achieved. This work with multi-scale structure design provides significant guidance to rationally develop advanced protective layers for other ultra-long-life metal batteries.

Toward Complete Transformation of Sodium Polysulfides by Regulating the Second-Shell Coordinating Environment of Atomically Dispersed Fe.

Room temperature sodium-sulfur (RT Na-S) batteries are highly competitive as potential energy storage devices. Nevertheless, their actually achieved reversible capacities are far below the theoretical value due to incomplete transformation of polysulfides. Herein, atomically dispersed Fe-N/S active center by regulating the second-shell coordinating environment of Fe single atom is proposed. The Fe-N4 S2 coordination structure with enhanced local electronic concentration around the Fermi level is revealed via synchrotron radiation X-ray absorption spectroscopy (XAS) and theoretical calculations, which can not only significantly promote the transformation kinetics of polysulfides, but induce uniform Na deposition for dendrite-free Na anode. As a result, the obtained S cathode delivers a high initial reversible capacity of 1590 mAh g-1 , nearly the theoretical value. This work opens up a new avenue to facilitate the complete transformation of polysulfides for RT Na-S batteries.

Room-Temperature Sodium-Sulfur Batteries: Rules for Catalyst Selection and Electrode Design.

Seeking an optimal catalyst to accelerate conversion reaction kinetics of room-temperature sodium-sulfur (RT Na-S) batteries is crucial for improving their electrochemical performance and promoting the practical applications. Herein, theoretical calculations of interfacial interactions of catalysts and polysulfides in terms of the surface adsorption state, interfacial ions migration, and electronic concentration around the Fermi level are systematically proposed as guiding principles of catalyst selection for RT Na-S batteries. As a case, MoN catalyst is accurately selected from transition metal nitrides with different d orbital electrons, and for experiment, it is introduced into the carbon nanofibers as a dual-functioning host (MoN@CNFs). The MoN@CNFs can effectively anchor polysulfides and accelerate their conversion reaction. In addition, for the sodium anode, the MoN@CNFs can also induce uniform deposition of Na and inhibit dendrite growth, which are supported by in situ characterizations and finite element simulation technique. As a result, the as-prepared RT Na-S battery displays high reversible capacity of 990 mAh g-1 at 0.2 A g-1 after 100 cycles and long lifespan over 1500 cycles at 2 A g-1 . Even with high S loading of 5 mg cm-2 , the RT Na-S battery still exhibits a high areal capacity of 2.5 mAh cm-2 .

An Open-Ended Ni3 S2 -Co9 S8 Heterostructures Nanocage Anode with Enhanced Reaction Kinetics for Superior Potassium-Ion Batteries.

Sulfides are perceived as promising anode materials for potassium-ion batteries (PIBs) due to their high theoretical specific capacity and structural diversity. Nonetheless, the poor structural stability and sluggish kinetics of sulfides lead to unsatisfactory electrochemical performance. Herein, Ni3 S2 -Co9 S8 heterostructures with an open-ended nanocage structure wrapped by reduced graphene oxide (Ni-Co-S@rGO cages) are well designed as the anode for PIBs via a selective etching and one-step sulfuration approach. The hollow Ni-Co-S@rGO nanocages, with large surface area, abundant heterointerfaces, and unique open-ended nanocage structure, can reduce the K+ diffusion length and promote reaction kinetics. When used as the anode for PIBs, the Ni-Co-S@rGO exhibits high reversible capacity and low capacity degradation (0.0089% per cycle over 2000 cycles at 10 A g-1 ). A potassium-ion full battery with a Ni-Co-S@rGO anode and Prussian blue cathode can display a superior reversible capacity of 400 mAh g-1 after 300 cycles at 2 A g-1 . The unique structural advantages and electrochemical reaction mechanisms of the Ni-Co-S@rGO are revealed by finite-element-simulation in situ characterizations. The universal synthesis technology of bimetallic sulfide anodes for advanced PIBs may provide vital guidance to design high-performance energy-storage materials.

Artificial Heterogeneous Interphase Layer with Boosted Ion Affinity and Diffusion for Na/K-Metal Batteries.

Metallic Na (K) are considered a promising anode materials for Na-metal and K-metal batteries because of their high theoretical capacity, low electrode potential, and abundant resources. However, the uncontrolled growth of Na (K) dendrites severely damages the stability of the electrode/electrolyte interface, resulting in battery failure. Herein, a heterogeneous interface layer consisting of metal vanadium nanoparticles and sodium sulfide (potassium sulfide) is introduced on the surface of a Na (K) foil (i.e., Na2 S/V/Na or K2 S/V/K). Experimental studies and theoretical calculations indicate that a heterogeneous Na2 S/V (K2 S/V) protective layer can effectively improve Na (K)-ion adsorption and diffusion kinetics, inhibiting the growth of Na (K) dendrites during Na (K) plating/stripping. Based on the novel design of the heterogeneous layer, the symmetric Na2 S/V/Na cell displays a long lifespan of over 1000 h in a carbonate-based electrolyte, and the K2 S/V/K electrode can operate for over 1300 h at 0.5 mA cm-2 with a capacity of 0.5 mAh cm-2 . Moreover, the Na full cell (Na3 V2 (PO4 )3 ||Na2 S/V/Na) exhibits a high energy density of 375 Wh kg-1 and a high power density of 23.5 kW kg-1 . The achievements support the development of heterogeneous protective layers for other high-energy-density metal batteries.

An Efficient Strategy toward Multichambered Carbon Nanoboxes with Multiple Spatial Confinement for Advanced Sodium-Sulfur Batteries.

Intricate hollow carbon structures possess vital function for anchoring polysulfides and enhancing the utilization of sulfur in room-temperature sodium-sulfur batteries. However, their synthesis is extremely challenging due to the complex structure. Here, a facile and efficient strategy is developed for the controllable synthesis of N/O-doped multichambered carbon nanoboxes (MCCBs) by selective etching and stepwise carbonization of ZIF-8 nanocubes. The MCCBs consist of porous carbon shells on the outside and connected carbon grids with a hollow structure on the inside, bringing about a MCCBs structure. As a sulfur host, the multichambered structure has better spatial encapsulation and integrated conductivity via the inner interconnected carbon grids, which combines the characteristics of short charge transfer path and superb physicochemical adsorption along with mechanical strength. As expected, the S@MCCBs cathode realizes decent cycle stability (0.045% capacity decay per cycle over 800 cycles at 5 A g-1) and enhanced rate performance (328 mA h g-1 at 10 A g-1). Furthermore, in situ transmission electron microscopy (TEM) observation confirms the good structural stability of the S@MCCBs during the (de)sodiation process. Our work demonstrates an effective strategy for the rational design and accurate construction of intricate hollow materials for high-performance energy storage systems.