In Situ Fe-Substituted Hexacyanoferrate for High-Performance Aqueous Potassium Ion Batteries.

The eco-friendliness, safety, and affordability of aqueous potassium batteries (AKIBs) have made them popular for large-scale energy storage devices. However, the cycling and rate performance of research materials, particularly cobalt hexacyanoferrate, have yet to meet satisfactory standards. Herein, a room-temperature drafted K1.66 Fe0.25 Co0.75 [Fe(CN)6 ]·0.83H2 O (KFCHCF) sample is reported using an in situ substitution strategy. A higher concentration of ferrocyanide ions decreases the water content and increases the potassium content, while citric acid works as a chelating agent and is responsible for Fe-substitution in the KFCHCF sample. The resultant KFCHCF sample exhibits good rate performance, and about 97% and 90.6% of discharge capacity are conserved after 400 and 1000 cycles at 100 and 200 mA g-1 , respectively. The full cell using the KFCHCF cathode and 1,4,5,8-naphthalenetetracarboxylic dianhydride-derived polyimide (PNTCDA) anode maintains ≈74.93% and 74.35% of discharge capacity at 200 mA g-1 and 1000 mA g-1 for 1000 and >10,000 cycles, respectively. Furthermore, ex situ characterizations demonstrate the high reversibility of K-ions and structural stability during the charge-discharge process. Such high performance is attributed to the fast K-ion migration and crystal structure stabilization caused by in situ Fe-substitution in the KFCHCF sample. Other hexacyanoferrates can be synthesized using this method and used in grid-scale storage systems.

Ion Pre-Embedding Engineering of δ-MnO2 for Chemically Self-Charging Aqueous Zinc Ions Batteries.

Aqueous zinc ion batteries (ZIBs), especially those with self-charging properties, have been promisingly developed in recent years. Yet, most inorganic materials feature high redox potential, which limit their development in the self-charging field. To achieve this target, by pre-embedding potassium ions into δ-MnO2 to reduce the energy barrier in oxygen adsorption, the first application of MnO2 in self-charging ZIBs is realized. The design features a facile two-electrode configuration with no excessively complex component to allow for energy storage and conversion. Due to the voltage difference between the oxygen in the air and the discharge products, a redox reaction can be carried out spontaneously to realize the self-charging process. After the chemical self-charging process, the Zn-K0.37 MnO2 ·0.54H2 O/C cell achieves an open circuit voltage of around 1.42 V and a discharge capacity of 201 mAh g-1 , reflecting the promising self-charging capability. Besides, the chemically self-charging ZIBs operate well in multiple modes of constant current charge/discharge/chemical charging. And decent cycling capability can also be achieved at extreme temperatures and high mass loading. This work promotes the development of ZIBs and further broadens the application of inorganic metal oxides in the self-charging systems.

Maximized Schottky Effect: The Ultrafine V2 O3 /Ni Heterojunctions Repeatedly Arranging on Monolayer Nanosheets for Efficient and Stable Water-to-Hydrogen Conversion.

The Mott-Schottky heterojunction formed at the interface of ultrafine metallic Ni and semiconducting V2 O3 nanoparticles is constructed, and the heterojunctions are "knitted" into the tulle-like monolayer nanosheets on nickel foam (NF). The greatly reduced particle sizes of both Ni and V2 O3 on the Mott-Schottky heterojunction highly enhance the number of Schottky heterojunctions per unit area of the materials. Moreover, arranging the heterojunctions into the monolayer nanosheets makes the heterojunctions repeat and expose to the electrolyte sufficiently. The Schottky heterojunctions are like countless self-powered charge transfer workstations embedded in the tulle-like monolayer nanosheets, promoting maximum of the materials to participate into the electron transfer and become catalytic active sites. In addition, the tulle-like monolayer nanosheet structure can assist in pumping liquid phase electrolyte to the surface of catalysts, owing to the capillary force. The V2 O3 /Ni/NF Mott-Schottky catalyst exhibits excellent hydrogen evolution reaction (HER) performance with a low η10 of 54 mV and needs -107 mV to get the current density of -100 mA cm-2 . Furthermore, V2 O3 /Ni/NF Schottky electrocatalyst exhibits excellent urea oxidation reaction activity: 1.40, 1.51, and 1.61 V versus reversible hydrogen electrode (RHE) voltage are required to reach a current density of 100, 500, and 1000 mA cm-2 , respectively.

Solid-solution reaction suppresses the Jahn-Teller effect of potassium manganese hexacyanoferrate in potassium-ion batteries.

Potassium manganese hexacyanoferrate (KMnHCF) suffers from poor cycling stability in potassium-ion batteries due to the Jahn-Teller effect, and experiences destabilizing asymmetric expansions and contractions during cycling. Herein, hollow nanospheres consisting of ultrasmall KMnHCF nanocube subunits (KMnHCF-S) are developed by a facile strategy. In situ XRD analysis demonstrates that the traditional phase transition for KMnHCF is replaced by a single-phase solid-solution reaction for KMnHCF-S, which effectively suppresses the Jahn-Teller effect. From DFT calculations, it was found that the calculated reaction energy for K+ extraction in the solid-solution reaction is much lower than that in the phase transition, indicating easier K+ extraction during the solid-solution reaction. KMnHCF-S delivers high capacity, outstanding rate capability, and superior cycling performance. Impressively, the K-ion full cell composed of the KMnHCF-S cathode and graphite anode also displays excellent cycling stability. The solid-solution reaction not only suppresses the Jahn-Teller effect of KMnHCF-S but also provides a strategy to enhance the electrochemical performance of other electrodes which undergo phase transitions.

Expediting the Conversion of Li2S2 to Li2S Enables High-Performance Li-S Batteries.

The solid-solid conversion of Li2S2 to Li2S is a crucial and rate-controlling step that provides one-half of the theoretical capacity of lithium-sulfur (Li-S) batteries. The catalysts in the Li-S batteries are often useless in the solid-solid conversion due to the poor contact interfaces between solid catalysts and insoluble solid Li2S2. Considering that ultrafine nanostructured materials have the properties of quantum size effects and unconventional reactivities, we design and synthesize for the pomegranate-like sulfur nanoclusters@nitrogen-doped carbon@nitrogen-doped carbon nanospheres (S@N-C@N-C NSs) with a seed-pulp-peel nanostructure. The ultrafine S@N-C subunits (diameter ≈5 nm) and effects of a spatial structure perfectly realize the rapid conversion of ultrafine Li2S2 to Li2S. The S@N-C@N-C seed-pulp-peel NS cathodes exhibit excellent sulfur utilization, superb rate performance (760 mAh g-1 at 10.0 C), and an ultralow capacity decay rate of about 0.016% per cycle over 1000 cycles at 4.0 C. The proposed strategy based on ultrafine nanostructured materials can also inform material engineering in related energy storage and conversion fields.

Construction of hierarchical yolk-shell nanospheres organized by ultrafine Janus subunits for efficient overall water splitting.

Although the bimetal sulfide is intensively pursued in catalytic systems, synthesis of ultrafine sized bimetal sulfide Janus subunits is still a great challenge. In this work, ultrafine NiS2/MoS2 Janus subunits organized on yolk-shell nanospheres (NSs) are synthesized by a novel and facile approach. The greatly reduced particle size of both two-dimensional MoS2 and one-dimensional NiS2 on the ultrafine NiS2/MoS2 Janus subunits endows the yolk-shell NSs with numerous intimate interfaces of bimetal sulfide hybrids greatly promoting the intimate electronic interaction and dissociation of water molecules. Benefiting from the ultrafine NiS2/MoS2 Janus subunits, abundant edge sites and the high density of interfaces, the as-prepared NiS2/MoS2 yolk-shell NSs exhibit high electrocatalytic activity with a low η10 value of 135 and 293 mV for the HER and OER, respectively. In addition, a low cell voltage (1.58 V) is achieved by using NiS2/MoS2 yolk-shell NSs as both anode and cathode. This study has significant indications in exploring the ultrafine nanoparticles for the water splitting reaction, fuel cells and organic synthesis.

in situ engineered ultrafine NiS2-ZnS heterostructures in micro-mesoporous carbon spheres accelerating polysulfide redox kinetics for high-performance lithium-sulfur batteries.

Host materials that can physically confine and chemically adsorb/catalyze lithium polysulfides (LiPSs) are currently receiving intensive research interest for developing lithium-sulfur (Li-S) batteries. Herein, a novel host material made of micro-mesoporous carbon nanospheres (MMC NSs) with well-dispersed ultrafine NiS2-ZnS (uNiS2-ZnS) heterostructures is synthesized for the first time via a simple in situ sulfuration process. The uNiS2-ZnS/MMC materials achieve the synergistic effect of physical confinement and the efficient chemical adsorption/catalysis of LiPSs through a micro-mesoporous structure and well-dispersed uNiS2-ZnS heterostructures. In addition, compared with bulk heterostructured materials, the uNiS2-ZnS heterostructures greatly enhance the adsorption and catalytic ability toward LiPSs because the catalysis interface effect and naturally formed in-plane interfaces can be magnified by the ultrafine dispersed nanoparticles. As a result, the prepared uNiS2-ZnS/MMC-S cathodes exhibit outstanding rate capacity (675.5 mA h g-1 at 5.0C) and cyclic stability (710.5 mA h g-1 at 1.0C after 1000 cycles with a low capacity decay of 0.033% per cycle). This work provides a certain reference for the application of heterostructured materials in Li-S batteries.

Nitrogen and Sulfur-Codoped Porous Carbon Nanospheres with Hierarchical Micromesoporous Structures and an Ultralarge Pore Volume for High-Performance Supercapacitors.

The carbon nanostructure with heteroatom doping having well-designed porosity and a large pore volume plays a vital role in high-performance supercapacitors. Herein, we synthesize hierarchical nitrogen and sulfur-codoped micromesoporous carbon nanospheres (N,S-HPCNSs) with an ultralarge pore volume of 3.684 cm3 g-1. The ultralarge pore volume in the N,S-HPCNSs can achieve fast charge storage and high electrochemical utilization due to the rapid mass transport. As a result, N,S-HPCNSs exhibit specific capacitances of 309.4 F g-1 at 0.5 A g-1 and 232.0 F g-1 at 50 A g-1 in a 1 M H2SO4 electrolyte, suggesting a superior rate property. Moreover, the N,S-HPCNSs exhibit a splendid cycling performance after 10,000 cycles with 98.5% capacitance retention. Furthermore, a symmetric supercapacitor reaches an excellent energy density of 27.8 W h kg-1 under 180.0 W kg-1 in a 1 M Na2SO4 electrolyte. The remarkable electrochemical properties of N,S-HPCNSs are caused by the ultralarge pore volume and hierarchical micromesoporous structures of the carbon NSs, which provide a significant way for designing energy storage systems.

Encapsulating Red Phosphorus in Ultralarge Pore Volume Hierarchical Porous Carbon Nanospheres for Lithium/Sodium-Ion Half/Full Batteries.

Red phosphorus (P) has been recognized as a promising material for lithium/sodium-ion batteries (LIBs/SIBs) because of their high theoretical capacity. However, tremendous volume variation and low conductivity limit its widespread applications. Hence, we design and synthesize uniformly distributed honeycomb-like hierarchical micro-mesoporous carbon nanospheres (HHPCNSs) with ultralarge pore volume (3.258 cm3 g-1) on a large scale through a facile way. The large pore volume provides enough space for loading of P and the expansion of P, and the uniform distribution of the micro-mesopores enables the red P to load uniformly. The resulting HHPCNSs/P composite exhibits extremely high capacity (2463.8 and 2367.6 mA h g-1 at 0.1 A g-1 for LIBs and SIBs, respectively), splendid rate performance (842.2 and 831.1 mA h g-1 at 10 A g-1 for LIBs and SIBs, respectively) and superior cycling stability (1201.6 and 938.4 mA h g-1 at 2 and 5 A g-1 after 1000 cycles for LIBs and 1269.4 and 861.8 mA h g-1 at 2 and 5 A g-1 after 1000 cycles for SIBs, respectively). More importantly, when coupled with LiFePO4 and Na3V2(PO4)3 cathode, lithium/sodium-ion full batteries display high capacity and superior rate and cycling performances, revealing the practicability of the HHPCNSs/P composite. The exceptional electrochemical performance is caused by the honeycomb-like carbon network with ultralarge pore volume, uniformly distributed hierarchical micro-mesoporous nanostructure, outstanding electronic conductivity, and excellent nanostructural stability, which is much better than currently reported P/C materials for both LIBs and SIBs.