ZnO Additive Boosts Charging Speed and Cycling Stability of Electrolytic Zn-Mn Batteries.

Electrolytic aqueous zinc-manganese (Zn-Mn) batteries have the advantage of high discharge voltage and high capacity due to two-electron reactions. However, the pitfall of electrolytic Zn-Mn batteries is the sluggish deposition reaction kinetics of manganese oxide during the charge process and short cycle life. We show that, incorporating ZnO electrolyte additive can form a neutral and highly viscous gel-like electrolyte and render a new form of electrolytic Zn-Mn batteries with significantly improved charging capabilities. Specifically, the ZnO gel-like electrolyte activates the zinc sulfate hydroxide hydrate assisted Mn2+ deposition reaction and induces phase and structure change of the deposited manganese oxide (Zn2Mn3O8·H2O nanorods array), resulting in a significant enhancement of the charge capability and discharge efficiency. The charge capacity increases to 2.5 mAh cm-2 after 1 h constant-voltage charging at 2.0 V vs. Zn/Zn2+, and the capacity can retain for up to 2000 cycles with negligible attenuation. This research lays the foundation for the advancement of electrolytic Zn-Mn batteries with enhanced charging capability.

One-Step Pyrolysis Construction of Bimetallic Atom-Cluster Sites for Boosting Bifunctional Catalytic Activity in Zn-Air Batteries.

Due to their unique advantages, single atoms and clusters of transition metals are expected to achieve a breakthrough in catalytic activity, but large-scale production of active materials remains a challenge. In this work, a simple solvent-free one-step annealing method is developed and applied to construct diatomic and cluster active sites in activated carbon by utilizing the strong anchoring ability of phenanthroline to metal ions, which can be scaled for mass productions. Benefiting from the synergy between the different metals, the obtained sub-nano-bimetallic atom-cluster catalysts (FeNiAC -NC) exhibit high oxygen reduction reactions (ORR) activity (E1/2 = 0.936 V vs. RHE) and a small ORR/oxygen evolution reaction (OER) potential gap of only 0.594 V. An in-house pouch Zn-air battery is assembled using an FeNiAC -NC catalyst, which demonstrates a stability of 1000 h, outperforming previous reports. The existence of clusters and their effects on catalytic activity is analyzed by density functional theory calculations to reveal the chemistry of nano-bimetallic atom-cluster catalysts.

Amorphous Vanadium Oxides with Dual ion Storage Mechanism for High-Performance Aqueous Zinc ion Batteries.

Owing to the extremely limited structural deformation caused by the introduction of guest ions that their rigid structure can sustain, crystalline materials typically fail owing to structural collapse when utilized as electrode materials. Amorphous materials, conversely, are more resistant to volume expansion during dynamic ion transport and can introduce a lot of defects as active sites. Here, The amorphous polyaniline-coated/intercalated V2O5·nH2O (PVOH) nanowires are prepared by in situ chemical oxidation combined with self-assembly strategy, which exhibited impressive electrochemical properties because of its short-range ordered crystal structure, oxygen vacancy/defect-rich, improved electronic channels, and ionic channels. Through in situ techniques, the energy storage mechanism of its Zn2+/H+ co-storage is investigated and elucidated. Additionally, this work provides new insights and perspectives for the investigation and application of amorphous cathodes for aqueous zinc ion batteries.

In Situ Fast Construction of Ni3S4/FeS Catalysts on 3D Foam Structure Achieving Stable Large-Current-Density Water Oxidation.

By increasing the content of Ni3+, the catalytic activity of nickel-based catalysts for the oxygen evolution reaction (OER), which is still problematic with current synthesis routes, can be increased. Herein, a Ni3+-rich of Ni3S4/FeS on FeNi Foam (Ni3S4/FeS@FNF) via anodic electrodeposition to direct obtain high valence metal ions for OER catalyst is presented. XPS showed that the introduction of Fe not only further increased the Ni3+ concentration in Ni3S4/FeS to 95.02%, but also inhibited the dissolution of NiOOH by up to seven times. Furthermore, the OER kinetics is enhanced by the combination of the inner Ni3S4/FeS heterostructures and the electrochemically induced surface layers of oxides/hydroxides. Ni3S4/FeS@FNF shows the most excellent OER activity with a low Tafel slope of 11.2 mV dec-1 and overpotentials of 196 and 445 mV at current densities of 10 and 1400 mA cm-2, respectively. Furthermore, the Ni3S4/FeS@FNF catalyst can be operated stably at 1500 mA cm-2 for 200 h without significant performance degradation. In conclusion, this work has significantly increased the high activity Ni3+ content in nickel-based OER electrocatalysts through an anodic electrodeposition strategy. The preparation process is time-saving and mature, which is expected to be applied in large-scale industrialization.

Continuous Amorphous Metal-Organic Frameworks Layer Boosts the Performance of Metal Anodes.

Employing metal anodes can greatly increase the volumetric/gravimetric energy density versus a conventional ion-insertion anode. However, metal anodes are plagued by dendrites, corrosion, and interfacial side reaction issues. Herein, a continuous and flexible amorphous MOF layer was successfully synthesized and used as a protective layer on metal anodes. Compared with the crystalline MOF layer, the continuous amorphous MOF layer can inhibit dendrite growth at the grain boundary and eliminate ion migration near the grain boundary, showing high interfacial adhesion and a large ion migration number (tZn2+ = 0.75). In addition, the continuous amorphous MOF layer can effectively solve several key challenges, e.g., corrosion of the zinc anode, hydrogen evolution reaction, and dendrite growth on the zinc surface. The prepared Zn anode with the continuous amorphous MOF (A-MOF) layer exhibited an ultralong cycling life (around one year, more than 7900 h) and a low overpotential (<40 mV), which is 12 times higher than that of the crystalline MOF protective layer. Even at 10 mA cm-2, it still showed high stability for more than 5500 cycles (1200 h). The enhanced performance is realized for full cells paired with a MnO2 cathode. In addition, a flexible symmetrical battery with the Zn@A-ZIF-8 anode exhibited good cyclability under different bending angles (0°, 90°, and 180°). More importantly, various metal substrates were successfully coated with compact A-ZIF-8. The A-ZIF-8 layer can obviously improve the stability of other metal anodes, including those of Mg and Al. These results not only demonstrate the high potential of amorphous MOF-decorated Zn anodes for AZIBs but also propose a type of protective layer for metal anodes.

A Facile Preparation of Sandwich-Structured Pd/Polypyrrole-Graphene/Pd Catalysts for Formic Acid Electro-Oxidation.

Direct formic acid fuel cells (DFAFCs) are one of the most promising power sources due to its high conversion efficiency; relatively low carbon emissions, toxicity, and flammability; convenience; and low-cost storage and transportation. However, the key challenge to large-scale commercial applications is its poor power performance and the catalyst's high preparation cost. In this study, a new sandwich-structured Pd/polypyrrole-graphene/Pd (Pd/PPy-Gns/Pd)-modified glassy carbon electrode (GCE) was prepared using a simple constant potential (CP) electrodeposition technique. On the basis of the unique synthetic procedure and structural advantages, the Pd/PPy-Gns/Pd shows a fast charge/mass transport rate, high electrocatalytic activity, and great stability for formic acid electro-oxidation (FAO). The mass activity of Pd/PPy-Gns/Pd electrode reaches 917 mA·mg-1Pd. The excellent catalytic activity is mainly due to the uniform embedding of Pd nanoparticles on the polypyrrole-graphene (PPy-Gns) support, which exposes more active sites, and prevents the shedding and inactivation of Pd nanoparticles. At the same time, the introduction of graphene (Gns) in the PPy further improved the conductivity of the catalyst and accelerated the transfer of electrons.

A salt-baking 'recipe' of commercial nickel-molybdenum alloy foam for oxygen evolution catalysis in water splitting.

Ni-based metal foam holds promise as an electrochemical water-splitting catalyst, due to its low cost, acceptable catalytic activity and superior stability. However, its catalytic activity must be improved before it can be used as an energy-saving catalyst. Here, a traditional Chinese recipe, salt-baking, was employed to surface engineering of nickel-molybdenum alloy (NiMo) foam. During salt-baking, a thin layer of FeOOH nano-flowers was assembled on the NiMo foam surface then the resultant NiMo-Fe catalytic material was evaluated for its ability to support oxygen evolution reaction (OER) activity. The NiMo-Fe foam catalyst generated an electric current density of 100 mA cm-2 that required an overpotential of only 280 mV, thus demonstrating that its performance far exceeded that of the benchmark catalyst RuO2 (375 mV). When employed as both the anode and cathode for use in alkaline water electrolysis, the NiMo-Fe foam generated a current density (j) output that was 3.5 times greater than that of NiMo. Thus, our proposed salt-baking method is a promising simple and environmentally friendly approach for surface engineering of metal foam for designing catalysts.

N doped FeP nanospheres decorated carbon matrix as an efficient electrocatalyst for durable lithium-sulfur batteries.

Rational design and synthesis of multifunctional electrocatalysts with high electrochemical activity and low cost are significantly important for new-generation lithium-sulfur (Li-S) batteries. Herein, N-doped FeP nanospheres decorated N doped carbon matrix is successfully synthesized by facile one-pot pyrolysis and in-situ phosphorization technique to mitigate the conversion kinetics and suppress the shuttle effect. The large specific surface area with mesopores can incorporate up to 81.5% sulfur, with the conductive carbon and nitrogen co-matrix providing Li+/e- passage and fastening the redox kinetics. The remarkable adsorption properties and the electrocatalytic activity through physical confinement and chemical immobilization is thoroughly verified. Consequently, the FeP/CN@S deliver a high reversible capacity of 1183 mAh g-1 at 0.1C compared to Co/P/CN@S (961 mAh g-1); whereas, at 1C, a negligible decay rate of 0.04% is observed for 1000 cycles, possessing outstanding cycling stability and rate capability. Hence, the cost-effective in-situ phosphorization strategy to synthesize FeP/CN@S as an efficient nanoreactor is constructive to be applied in Li-S batteries.

Electrostatically directed assembly of two-dimensional ultrathin Co2Ni-MOF/Ti3C2Tx nanosheets for electrocatalytic oxygen evolution.

Hydrogen production from water electrolysis is severely restricted by the poor reaction kinetics of oxygen evolution reaction (OER). In this work, a series of two-dimensional (2D) composites MOF/Ti3C2Tx (the MXene phase) were fabricated by electrostatically directed assembly and used as catalysts for OER. The obtained composite materials exhibit enhanced electrocatalytic properties, thanks to the ultrathin 2D/2D heterostructure with abundant active sites in Co2Ni-MOF and the high electronic conductivity of Ti3C2Tx. Among all the catalysts, Co2Ni-MOF@MX-1 achieved the best oxygen evolution performance with the lowest Tafel slope (51.7 mV dec-1) and the lowest overpotential (265 mV on carbon paper) at the current density of 10 mA cm-2. These results demonstrated that the synthesis of 2D composite materials by electrostatically directed assembly could be a feasible and promising method for the preparation of 2D heterostructure catalysts.

Identification of Catalytic Active Sites for Durable Proton Exchange Membrane Fuel Cell: Catalytic Degradation and Poisoning Perspectives.

Recent progress in synthetic strategies, analysis techniques, and computational modeling assist researchers to develop more active catalysts including metallic clusters to single-atom active sites (SACs). Metal coordinated N-doped carbons (M-N-C) are the most auspicious, with a large number of atomic sites, markedly performing for a series of electrochemical reactions. This perspective sums up the latest innovative and computational comprehension, while giving credit to earlier/pioneering work in carbonaceous assembly materials towards robust electrocatalytic activity for proton exchange membrane fuel cells via inclusive performance assessment of the oxygen reduction reaction (ORR). M-Nx -Cy are exclusively defined active sites for ORR, so there is a unique possibility to intellectually design the relatively new catalysts with much improved activity, selectivity, and durability. Moreover, some SACs structures provide better performance in fuel cells testing with long-term durability. The efforts to understand the connection in SACs based M-Nx -Cy moieties and how these relate to catalytic ORR performance are also conveyed. Owing to comprehensive practical application in the field, this study has covered very encouraging aspects to the current durability status of M-N-C based catalysts for fuel cells followed by degradation mechanisms such as macro-, microdegradation, catalytic poisoning, and future challenges.

Why does the capacity of vanadium selenide based aqueous zinc ion batteries continue to increase during long cycles?

At present, rechargeable aqueous zinc ion batteries (RZIBs) have become a rising star and highly sought after in the field of new energy. While vanadium-based RZIBs often exhibit an anomaly of increased long-cycle capacity, which has not been explored in depth. Nevertheless, it is critical to understand this phenomenon to develop high-performance RZIBs. Therefore, this study investigated the growth mechanism of VSe2-based RZIBs using VSe2/MXene as the cathode material via in-situ and ex-situ characterization techniques and electrochemical measurements. Experimental results indicated that with the interaction/extraction of Zn2+/H+ in the host material during cycling, an obvious oxidation reaction occurs at high voltage, and the formed vanadium oxide further reacts with Zn2+ from the electrolyte. As a result, Zn0.25V2O5·H2O is continuously produced and accumulated, contributing to the increasing capacity of the prepared RZIBs.

Reunderstanding the Reaction Mechanism of Aqueous Zn-Mn Batteries with Sulfate Electrolytes: Role of the Zinc Sulfate Hydroxide.

Rechargeable aqueous Zn-Mn batteries have garnered extensive attention for next-generation high-safety energy storage. However, the charge-storage chemistry of Zn-Mn batteries remains controversial. Prevailing mechanisms include conversion reaction and cation (de)intercalation in mild acid or neutral electrolytes, and a MnO2 /Mn2+ dissolution-deposition reaction in strong acidic electrolytes. Herein, a Zn4 SO4 ·(OH)6 ·xH2 O (ZSH)-assisted deposition-dissolution model is proposed to elucidate the reaction mechanism and capacity origin in Zn-Mn batteries based on mild acidic sulfate electrolytes. In this new model, the reversible capacity originates from a reversible conversion reaction between ZSH and Znx MnO(OH)2 nanosheets in which the MnO2 initiates the formation of ZSH but contributes negligibly to the apparent capacity. The role of ZSH in this new model is confirmed by a series of operando characterizations and by constructing Zn batteries using other cathode materials (including ZSH, ZnO, MgO, and CaO). This research may refresh the understanding of the most promising Zn-Mn batteries and guide the design of high-capacity aqueous Zn batteries.

A Fe3N/carbon composite electrocatalyst for effective polysulfides regulation in room-temperature Na-S batteries.

The practical application of room-temperature Na-S batteries is hindered by the low sulfur utilization, inadequate rate capability and poor cycling performance. To circumvent these issues, here, we propose an electrocatalyst composite material comprising of N-doped nanocarbon and Fe3N. The multilayered porous network of the carbon accommodates large amounts of sulfur, decreases the detrimental effect of volume expansion, and stabilizes the electrodes structure during cycling. Experimental and theoretical results testify the Fe3N affinity to sodium polysulfides via Na-N and Fe-S bonds, leading to strong adsorption and fast dissociation of sodium polysulfides. With a sulfur content of 85 wt.%, the positive electrode tested at room-temperature in non-aqueous Na metal coin cell configuration delivers a reversible capacity of about 1165 mA h g-1 at 167.5 mA g-1, satisfactory rate capability and stable capacity of about 696 mA h g-1 for 2800 cycles at 8375 mA g-1.

A facilely-synthesized polyanionic cathode with impressive long-term cycling stability for sodium-ion batteries.

In this work, nanoflower-like Na0.5VOPO4·2H2O with a large interlayer distance of 6.5295 Å is synthesized via a simple chemical precipitation method at room temperature. It is the first time that the potential of the Na0.5VOPO4·2H2O electrode as a cathode material for SIBs has been investigated, and it exhibits a high specific capacity (127 mA h g-1 at 0.2C), outstanding long-term cycling stability and superior reaction kinetics.

Design of an amperometric glucose oxidase biosensor with added protective and adhesion layers.

Enzymes have demonstrated great potential in the development of advanced electroanalysis devices due to their unique recognition and catalytic properties. However, unsatisfactory stability and limited electron communication of traditional enzyme sensors seriously hinder their large-scale application. In this work, a simple and effective method is proposed to improve the stability of enzyme sensors by using sodium hyaluronate (SH) as a protective film, MXene-Ti3C2/Glucose oxidase (GOD) as the reaction layer, and chitosan (CS) /reduced graphene oxide (rGO) as the adhesion layer. Results demonstrate that the repeatability of the designed sensor increased by 73.3% after improving the adhesion between the reaction layer and the current collector and that its response ability was greatly enhanced. Moreover, the long-term stability of the electrode surface with SH protective film proved to be superior than that without protective film, which suggests that this design can effectively improve the overall performance of the enzyme biosensor. This work proposed a multi-tier synergistic approach for improving the reliability of enzyme sensors. Graphical abstract Our proposed protective and adhesion layer can greatly improve the stability of enzyme sensor and realize the rapid detection of glucose in serum sample.

Efficient Catalytic Conversion of Polysulfides by Biomimetic Design of "Branch-Leaf" Electrode for High-Energy Sodium-Sulfur Batteries.

Rechargeable room temperature sodium-sulfur (RT Na-S) batteries are seriously limited by low sulfur utilization and sluggish electrochemical reaction activity of polysulfide intermediates. Herein, a 3D "branch-leaf" biomimetic design proposed for high performance Na-S batteries, where the leaves constructed from Co nanoparticles on carbon nanofibers (CNF) are fully to expose the active sites of Co. The CNF network acts as conductive "branches" to ensure adequate electron and electrolyte supply for the Co leaves. As an effective electrocatalytic battery system, the 3D "branch-leaf" conductive network with abundant active sites and voids can effectively trap polysulfides and provide plentiful electron/ions pathways for electrochemical reaction. DFT calculation reveals that the Co nanoparticles can induce the formation of a unique Co-S-Na molecular layer on the Co surface, which can enable a fast reduction reaction of the polysulfides. Therefore, the prepared "branch-leaf" CNF-L@Co/S electrode exhibits a high initial specific capacity of 1201 mAh g-1 at 0.1 C and superior rate performance.

A self-healing neutral aqueous rechargeable Zn/MnO2 battery based on modified carbon nanotubes substrate cathode.

Rechargeable aqueous Zn/MnO2 batteries show great potential for grid-scale storage due to their low cost, high safety, and energy density, yet suffer from continuous capacity decay during operation. Therefore, this work proposes a capacity self-healing aqueous Zn/MnO2 (Zn/cCNTs-MnO2) battery using carboxyl-modified carbon nanotubes (cCNTs) as the cathode substrate, ZnSO4 + MnSO4 mixed aqueous solution as the electrolyte, and Zn foil as the anode. Based on the controllable electrodeposition reaction of MnO2, the specific capacity of Zn/cCNTs-MnO2 batteries can be achieved or recovered by operating several cycles under a low current density (0.1 mA cm-2). Then, the batteries can stably perform under a high current density (1 mA cm-2). By repeating the above steps, a capacity self-healing usage scheme was established, which can significantly improve the cycling performance of Zn/cCNTs-MnO2 batteries. Moreover, the results of the proposed Zn/cCNTs-MnO2 batteries verify the MnO2 electrodeposition mechanism and introduce a novel method for the development of durable aqueous rechargeable Zn/MnO2 batteries.

Gelation of organic liquid electrolyte to achieve superior sodium-ion full-cells.

The irreversible consumption of active sodium in sodium-ion full-cells (SIFCs) becomes particularly serious due to the existence of unavoidable interface or side reaction, which has become the key to restrict the development of high-performance sodium-ion batteries (SIBs). Interface design and electrolyte optimization have been proved to be effective strategies to improve or solve this problem. In this work, on the basis of traditional organic liquid electrolytes, a novel gel polymer electrolyte with high ionic conductivity (1.13 × 10-3 S cm-1) and wide electrochemical stability window (~4.7 V) was designed and synthesized using bacterial cellulose film as precursor. Compared with the liquid electrolyte, the obtained electrolyte can endow better sodium storage performance in both half- and full-cells. When coupled with sodium hexacyanoferrate cathode and hard carbon anode, a capacity of 94.2 mA h g-1 can be obtained with a capacity retention of 75% after 100 cycles at a current density of 100 mA g-1, while those of with conventional liquid electrolyte can deliver a capacity of 99.0 mA h g-1 but only accompany 58% capacity retention under the same conditions. Significantly, when the current density increases to 800 mA g-1, their capacity difference reaches 23.4 mA h g-1.

Suppressed shuttling effect of polysulfides using three-dimensional nickel hydroxide polyhedrons for advanced lithium-sulfur batteries.

In this work, controlled-size hollow polyhedron assembled by crumpled nickel hydroxide (Ni(OH)2) nanosheets from silicon dioxide (SiO2)-covered zeolitic imidazole framework-67 (ZIF-67@SiO2) is prepared via a template-sacrificed method. It is found that SiO2 plays an essential role in keeping intact polyhedrons and suppressing particle growth. Benefiting from structural and compositional advantages, the Ni(OH)2@S electrode exhibits high specific capacity, excellent rate performance, and stable cycle life at 1C with a small capacity decay of 0.067% per cycle. The Ni(OH)2 hollow polyhedrons can accommodate the volume expansion to maintain the integrity of the electrode and suppress the shuttling effect of polysulfides via abundant hydroxyl groups. Hence, this strategy is beneficial to anticipate the material for large-scale applications.

Multi-step Controllable Catalysis Method for the Defense of Sodium Polysulfide Dissolution in Room-Temperature Na-S Batteries.

Room-temperature (RT) sodium-sulfur batteries hold great promise for the development of efficient, low-cost, and environmentally friendly energy storage systems. Nevertheless, the dissolution of long-chain polysulfides is a huge obstacle. In this work, a composite cathode which integrates Ni/Co bimetal nanoparticles as the catalyst and carbon spheres with abundant channels as the host is prepared for RT Na-S batteries. Moreover, a valuable strategy to reduce the dissolution of polysulfides by accurately regulating the two-step reaction kinetics of polysulfide transformation (from Na2S to long-chain polysulfides and then from polysulfides to sulfur) is presented. Through adjusting the ratio of Ni and Co, the optimal cathode with a Ni/Co ratio of 1:2 can retard the first conversion of Na2S to polysulfides and simultaneously accelerate the subsequent transformation of polysulfides to sulfur. In this case, the soluble polysulfides can immediately transform to solid sulfur as soon as it appears, thus avoiding the shuttle of polysulfides. The galvanostatic intermittent titration method and in situ Raman are employed to supervise the transformation of polysulfides during the discharge/charge process. As a result, the composite shows excellent performance as the cathode of RT liquid/quasi-solid-state Na-S batteries in terms of specific capacities, rate capability, and cycle stability.