Direct solar energy conversion on zinc-air battery.

A concept of solar energy convertible zinc-air battery (SZAB) is demonstrated through rational design of an electrode coupled with multifunction. The multifunctional electrode is fabricated using nitrogen-substituted graphdiyne (N-GDY) with large π-conjugated carbonous network, which can work as photoresponsive bifunctional electrocatalyst, enabling a sunlight-promoted process through efficient injection of photoelectrons into the conduction band of N-GDY. SZAB enables direct conversion and storage of solar energy during the charging process. Such a battery exhibits a lowered charge voltage under illumination, corresponding to a high energy efficiency of 90.4% and electric energy saving of 30.3%. The battery can display a power conversion efficiency as high as 1.02%. Density functional theory calculations reveal that the photopromoted oxygen evolution reaction kinetics originates from the transition from the alkyne bonds to double bonds caused by the transfer of excited electrons, which changes the position of highest occupied molecular orbital and lowest unoccupied molecular orbital, thus greatly promoting the formation of intermediates to the conversion process. Our findings provide conceptual and experimental confirmation that batteries are charged directly from solar energy without the external solar cells, providing a way to manufacture future energy devices.

Recycling spent LiNi1-x-yMnxCoyO2 cathodes to bifunctional NiMnCo catalysts for zinc-air batteries.

SignificanceIn recent years, lithium-ion batteries (LIBs) have been widely applied in electric vehicles as energy storage devices. However, it is a great challenge to deal with the large number of spent LIBs. In this work, we employ a rapid thermal radiation method to convert the spent LIBs into highly efficient bifunctional NiMnCo-activated carbon (NiMnCo-AC) catalysts for zinc-air batteries (ZABs). The obtained NiMnCo-AC catalyst shows excellent electrochemical performance in ZABs due to the unique core-shell structure, with face-centered cubic Ni in the core and spinel NiMnCoO4 in the shell. This work provides an economical and environment-friendly approach to recycling the spent LIBs and converting them into novel energy storage devices.

In Situ Construction of Zinc-Mediated Fe, N-Codoped Hollow Carbon Nanocages with Boosted Oxygen Reduction for Zn-Air Batteries.

The rational design of bifunctional oxygen electrocatalysts with unique morphology and luxuriant porous structure is significant but challenging for accelerating the reaction kinetics of rechargeable Zn-air batteries (ZABs). Herein, zinc-mediated Fe, N-codoped carbon nanocages (Zn-FeNCNs) are synthesized by pyrolyzing the polymerized iron-doped polydopamine on the surface of the ZIF-8 crystal polyhedron. The formation of the chelate between polydopamine and Fe serves as the covering layer to prevent the porous carbon nanocages from collapsing and boosts enough exposure and utilization of metal-based active species during carbonization. Furthermore, both the theoretical calculation and experimental results show that the strong interaction between polyhedron and polydopamine facilitates the evolution of high-activity zinc-modulated FeNx sites and electron transportation and then stimulates the excellent bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). As expected, the Zn-air battery with Zn-FeNCNs as an air cathode displays a superior power density (256 mW cm-2) and a high specific capacity (813.3 mA h gZn-1), as well as long-term stability over 1000 h. Besides, when this catalyst is applied to the solid-state battery, the device exhibited outstanding mechanical stability and a high round-trip efficiency under different bending angles.

Strategic Design and Insights into Lanthanum and Strontium Perovskite Oxides for Oxygen Reduction and Oxygen Evolution Reactions.

Perovskite oxides exhibit bifunctional activity for both oxygen reduction (ORR) and oxygen evolution reactions (OER), making them prime candidates for energy conversion in applications like fuel cells and metal-air batteries. Their intrinsic catalytic prowess, combined with low-cost, abundance, and diversity, positions them as compelling alternatives to noble metal and metal oxides catalysts. This review encapsulates the nuances of perovskite oxide structures and synthesis techniques, providing insight into pivotal active sites that underscore their bifunctional behavior. The focus centers on the breakthroughs surrounding lanthanum (La) and strontium (Sr)-based perovskite oxides, specifically their roles in zinc-air batteries (ZABs). An introduction to the mechanisms of ORR and OER is provided. Moreover, the light is shed on strategies and determinants central to optimizing the bifunctional performance of La and Sr-based perovskite oxides.

Recent Advances in Catalyst Design and Performance Optimization of Nanostructured Cathode Materials in Zinc-Air Batteries.

This review focuses on the advanced design and optimization of nanostructured zinc-air batteries (ZABs), with the aim of boosting their energy storage and conversion capabilities. The findings show that ZABs favor porous nanostructures owing to their large surface area, and this enhances the battery capacity, catalytic activity, and life cycle. In addition, the nanomaterials improve the electrical conductivity, ion transport, and overall battery stability, which crucially reduces dendrite growth on the zinc anodes and improves cycle life and energy efficiency. To obtain a superior performance, the importance of controlling the operational conditions and using custom nanostructural designs, optimal electrode materials, and carefully adjusted electrolytes is highlighted. In conclusion, porous nanostructures and nanoscale materials significantly boost the energy density, longevity, and efficiency of Zn-air batteries. It is suggested that future research should focus on the fundamental design principles of these materials to further enhance the battery performance and drive sustainable energy solutions.

Toward a Metal Anode-Free Zinc-Air Battery for Next-Generation Energy Storage.

Rechargeable aqueous zinc-air batteries (ZABs) promise high energy density and safety. However, the use of conventional zinc anodes affects the energy output from the battery, so that the theoretical energy density is not achievable under operation conditions. A large portion of the zinc is shielded by anode passivation during the discharge process and remains electrochemically unused, making the operation of rechargeable ZABs inefficient up to date. In a metal anode-free ZAB, there is no unnecessary excess zinc if the zinc reservoir can be precisely adjusted by electrodeposition of zinc from the electrolyte. In this respect, an anode-free battery uses the electrolyte offering a dual-mode functionality not only providing ionic conductivity but also being the source of zinc. In addition, it is shown that a defined porous anode architecture is crucial for high rechargeability in this new type of ZAB. 3D-spatially arranged carbon nanotubes as geometrically defined host structures allow a homogeneous zinc deposition from the electrolyte. Together with carbon nanohorns as an active 2e- catalyst on the cathode side, the rechargeability of this new concept reaches up to 92%.

Mesoporous Carbon for High-Performance Near-Neutral Zinc-Air Batteries.

Near-neutral zinc-air batteries (ZABs) have garnered significant research interest due to their high energy density, exceptional electrochemical reversibility, and adaptability to ambient air. However, these batteries suffer from substantial electrochemical polarization, low energy efficiency, and poor rate performance. In this study, a mesoporous carbon (meso-C) with a high specific surface area (1081 m2 g-1 ) and abundant porous structure for the cathode of near-neutral ZABs using a scalable synthesis method is prepared. The meso-C-based cathode is endowed with stable hydrophobicity and abundant electrochemical active sites, which considerably improve the energy efficiency, rate performance, and cycle life of the battery compare to commercial carbon black-based cathode when applied to near-neutral ZABs with 1 mol kg-1 (1 m) zinc acetate and 1 m zinc trifluoromethanesulfonate electrolytes. Additionally, the mesopores of meso-C facilitate the construction of better three-phase reaction interfaces and contribute to better electrochemical reversibility. The work presents a general and scalable approach for carbon materials in the cathode of near-neutral ZABs.

In situ Construction of Multistage Core-Shell Nanostructure as Bifunctional Catalyst for Ultrastable Zinc-Air Batteries.

Many efforts have been devoted to obtaining excellent cathode catalysts for Zinc air batteries (ZABs), but the inevitable use of binder will damage the catalytic activity and weaken long-term stability, inefficient mass transfer of oxygen is also chargable for the limited activity. Herein, in situ grown hydrogen substituted graphdiyne (HGDY) on carbon paper has been prepared and used as cathode catalyst layer in ZABs. Multiple catalytic sites are firmly combined and end with the boosted bifunctional catalytic activity of oxygen reduction and oxygen evolution. Moreover, the specific surface area, sufficient active sites, multilevel pore nanostructure and robust conductivity are fully exposed to establish efficient catalytic interface and skeleton. Cu/Co nanoparticles are uniformly distributed and warped by HGDY network, which can stably exist during the catalytic process. As a result, a current density of 18.75 mA cm-2 and a Tafel slope of 61.06 mV dec-1 for oxygen reduction and a ultralong operation for more than 2300 h in aqueous ZAB have been achieved, which is beyond many reported bifunctional catalysts in ZAB system.

Large-Scale Atomic Strain Defects on Palladium Surfaces for Enhanced Oxygen Reduction and Zinc-Air Batteries.

Designing nano-electrocatalysts rich in surface defects is critical to improve their catalytic performance. However, prevailing synthesis techniques rely heavily on complex procedures that compromise defect extensiveness and uniformity, casting a high demand for methods capable of synthesizing large-scale crystalline defects. An innovative design strategy is herein proposed that induces ample strain/dislocation defects during the growth of palladium (Pd), which is well-known as a good oxygen reduction reaction (ORR) catalyst. The controlled defect engineering on Pd core is achieved by the tensile stress exerted from an intentionally applied Fe3O4 skin layer during synthesis, which changes the surface free energy of Pd to stabilize the defect presence. With such large-scale crystalline defects, this Pd catalyst exhibits significantly higher ORR activity than commercial Pt/C, enabling its promising future in zinc-air battery catalysis. Additionally, the protective Fe3O4 skin covering the catalyst also enhances its catalytic stability. Theoretical calculations show that the superior catalytic property of such defect-engineered Pd is associated with the correspondingly modified adsorption energy of *O intermediates onto its surface, which further improves the reaction rate and thus boosts ORR kinetics. Findings here are expected to provide a paradigm for designing efficient and stable metal catalysts with plentiful large-scale strain defects.

Ultrafast Conversion of Water and Oxygen Molecules With Dissociation of Hydrogen Bonding Effect to Achieve Extra-High Energy Efficiency of Secondary Metal-Air Batteries.

Metal-air secondary batteries with ultrahigh specific energies have received vast attention and are considered new promising energy storage. The slow redox reactions between oxygen-water molecules lead to low energy efficiency (55-71%) and limited applications. Herein, it is proposed that the MIL-68(In)-derived porous carbon nanotube supports the CoNiFeP heteroconjugated alloy catalyst with an overboiling point electrolyte to achieve the ultrahigh oxidation rate of water molecules. Structural characterization and density functional theory calculations reveal that the new catalyst greatly reduces the free energy of the process, and the overboiling point further accelerates the dissociation of O─H and hydrogen bonds, and the release of O2 molecules, achieving an extra-low overpotential of 110 mV@10 mA cm-2 far lower than commercial Ir/C catalysts of 192 mV at 125 °C and state-of-the-art. Furthermore, the energy efficiency of assembled rechargeable zinc-air batteries begins to break through at 85 °C, jumps at 100 °C, and reaches ultrahigh energy efficiency of 88.1% at 125 °C with an ultralow decay rate of 0.0068% after 150 cycles far superior to those of reported metal-air batteries. This work provides a new catalyst and electrolyte joint-design strategy and reexamines the battery operating temperature to construct higher energy efficiency for secondary fuel cells.

Electrodeposition of Ni/Cu Bimetallic Conductive Metal-Organic Frameworks Electrocatalysts with Boosted Oxygen Reduction Activity for Zinc-Air Batteries.

Zinc-air batteries employing non-Pt cathodes hold significant promise for advancing cathodic oxygen reduction reaction (ORR). However, poor intrinsic electrical conductivity and aggregation tendency hinder the application of metal-organic frameworks (MOFs) as active ORR cathodes. Conductive MOFs possess various atomically dispersed metal centers and well-aligned inherent topologies, eliminating the additional carbonization processes for achieving high conductivity. Here, a novel room-temperature electrochemical cathodic electrodeposition method is introduced for fabricating uniform and continuous layered 2D bimetallic conductive MOF films cathodes without polymeric binders, employing the organic ligand 2,3,6,7,10,11-hexaiminotriphenylene (HITP) and varying the Ni/Cu ratio. The influence of metal centers on modulating the ORR performance is investigated by density functional theory (DFT), demonstrating the performance of bimetallic conductive MOFs can be effectively tuned by the unpaired 3d electrons and the Jahn-Teller effect in the doped Cu. The resulting bimetallic Ni2.1Cu0.9(HITP)2 exhibits superior ORR performance, boasting a high onset potential of 0.93 V. Moreover, the assembled aqueous zinc-air battery demonstrates high specific capacity of 706.2 mA h g-1, and exceptional long-term charge/discharge stability exceeding 1250 cycles.

Recycling the Spent LiNi1- x - yMnxCoyO2 Cathodes for High-Performance Electrocatalysts toward Both the Oxygen Catalytic and Methanol Oxidation Reactions.

The traditional recycling methods of the spent lithium ion batteries (LIBs) involve the intricate and cumbersome steps. This work proposes a facile method of acid leaching followed by the sulfurization treatment to achieve the high Li leaching efficiency, and obtain high-performance multi-function electrocatalysts for oxygen reduction (ORR), oxygen evolution (OER), and methanol oxidation reactions (MOR) from the spent LIB ternary cathodes. By this method, the Li leaching efficiency from the spent LIB ternary cathode can reach 98.3%, and the transition metal sulfide heterostructures (LNMCO-H-450S) consisting MnS, NiS2, and NiCo2S4 phases can be obtained. LNMCO-H-450S shows the superior bifunctional oxygen catalytic activities with ORR half-wave potential of 0.763 V and OER potential at 10 mA cm-2 of 1.561 V, surpassing most of the state-of-the-art electrocatalysts. LNMCO-H-450S also demonstrates the superior MOR catalytic activity with the potential at 100 mA cm-2 being 1.37 V. Using LNMCO-H-450S as the oxygen catalyst, this work can construct the aqueous and solid-state zinc-air batteries with high power density of 309 and 257 mW cm-2, respectively. This work provides a promising strategy for the efficient recovery of Li, and reutilization of Ni, Co, and Mn from the spent LIB ternary cathodes.

Highly Active CoNi-CoN3 Composite Sites Synergistically Accelerate Oxygen Electrode Reactions in Rechargeable Zinc-Air Batteries.

Reaching rapid reaction kinetics of oxygen reduction (ORR) and oxygen evolution reactions (OER) is critical for realizing efficient rechargeable zinc-air batteries (ZABs). Herein, a novel CoNi-CoN3 composite site containing CoNi alloyed nanoparticles and CoN3 moieties is first constructed in N-doped carbon nanosheet matrix (CoNi-CoN3/C). Benefiting from the high electroactivity of CoNi-CoN3 composite sites and large surface area, CoNi-CoN3/C shows a superior half-wave potential (0.88 V versus RHE) for ORR and a small overpotential (360 mV) for OER at 10 mA cm-2. Theoretical calculations have demonstrated that the introduction of CoNi alloys has modulated the electronic distributions near the CoN3 moiety, inducing the d-band center of CoNi-CoN3 composite site to shift down, thus stabilizing the valence state of Co active sites and balancing the adsorption of OER/ORR intermediates. Accordingly, the reaction energy trends exhibit optimized overpotentials for OER/ORR, leading to superior battery performances. For aqueous and flexible quasi-solid-state rechargeable ZABs with CoNi-CoN3/C as catalyst, a large power density (250 mW cm-2) and high specific capacity (804 mAh g-1) are achieved. The in-depth understanding of the electroactivity enhancement mechanism of interactive metal nanoparticles and metal coordinated with nitrogen (MNx) moieties is crucial for designing novel high-performance metal/nitrogen-doped carbon (M─N─C) catalysts.

Strong Carbon Layer-Encapsulated Cobalt Tin Sulfide-Based Nanoporous Material as a Bifunctional Electrocatalyst for Zinc-Air Batteries.

Global demands for cost-effective, durable, highly active, and bifunctional catalysts for metal-air batteries are tremendously increasing in scientific research fields. In this work, a strategy for the rational fabrication of carbon layer-encapsulated cobalt tin sulfide nanopores (CoSnOH/S@C NPs) material as a bifunctional electrocatalyst for rechargeable zinc (Zn)-air batteries by a cost-effective and facile two-step hydrothermal method is reported. Moreover, the effect of metal elements on the morphology of CoSnOH nanodisks material via the hydrothermal method is investigated. Owing to its excellent nanostructure, exclusive porous network, and high specific surface area, the optimized CoSnOH/S@C NPs material reveals superior catalytic properties. The as-prepared CoSnOH/S@C NPs electrocatalyst reveals better properties of oxygen reduction reaction (half-wave potential of -0.88 V vs reversible hydrogen electrode) and oxygen evolution reaction (overpotential of 137 mV at 10 mA cm-2) when compared with commercial Pt/C and IrO2 catalyst materials. Most significantly, the CoSnO/S@C NPs-based Zn-air battery exhibits more excellent cycling stability than the Pt/C+IrO2 catalyst-based one. Consequently, the proposed material provides a new route for fabricating more active and stable multifunctional catalyst materials for energy conversion and storage systems.

Recent Advancements of Graphene-Based Materials for Zinc-Based Batteries: Beyond Lithium-Ion Batteries.

Graphene-based materials (GBMs) possess a unique set of properties including tunable interlayer channels, high specific surface area, and good electrical conductivity characteristics, making it a promising material of choice for making electrode in rechargeable batteries. Lithium-ion batteries (LIBs) currently dominate the commercial rechargeable battery market, but their further development has been hampered by limited lithium resources, high lithium costs, and organic electrolyte safety concerns. From the performance, safety, and cost aspects, zinc-based rechargeable batteries have become a promising alternative of rechargeable batteries. This review highlights recent advancements and development of a variety of graphene derivative-based materials and its composites, with a focus on their potential applications in rechargeable batteries such as LIBs, zinc-air batteries (ZABs), zinc-ion batteries (ZIBs), and zinc-iodine batteries (Zn-I2 Bs). Finally, there is an outlook on the challenges and future directions of this great potential research field.

Flash Nitrogen-Doped Carbon Nanotubes for Energy Storage and Conversion.

In recent years, nitrogen-doped carbons show great application potentials in the fields of electrochemical energy storage and conversion. Here, the ultrafast and green preparation of nitrogen-doped carbon nanotubes (N-CNTs) via an efficient flash Joule heating method is reported. The precursor of 1D core-shell structure of CNT@polyaniline is first synthesized using an in situ polymerization method and then rapidly conversed into N-CNTs at ≈1300 K within 1 s. Electrochemical tests reveal the desirable capacitive property and oxygen catalytic activity of the optimized N-CNT material. It delivers an improved area capacitance of 101.7 mF cm-2 at 5 mV s-1 in 1 m KOH electrolyte, and the assembled symmetrical supercapacitor shows an energy density of 1.03 µWh cm-2 and excellent cycle stability over 10 000 cycles. In addition, the flash N-CNTs exhibit impressive catalytic performance toward oxygen reduction reaction with a half-wave potential of 0.8 V in alkaline medium, comparable to the sample prepared by the conventional long-time pyrolysis method. The Zn-air battery presents superior charge-discharge ability and long-term durability relative to commercial Pt/C catalyst. These remarkable electrochemical performances validate the superiorities of the Joule heating method in preparing the heteroatom-doped carbon materials for wide applications.

Rechargeable Zinc-Air Batteries: Advances, Challenges, and Prospects.

Rechargeable zinc-air batteries (Re-ZABs) are one of the most promising next-generation batteries that can hold more energy while being cost-effective and safer than existing devices. Nevertheless, zinc dendrites, non-portability, and limited charge-discharge cycles have long been obstacles to the commercialization of Re-ZABs. Over the past 30 years, milestone breakthroughs have been made in technical indicators (safety, high energy density, and long battery life), battery components (air cathode, zinc anode, and gas diffusion layer), and battery configurations (flexibility and portability), however, a comprehensive review on advanced design strategies for Re-ZABs system from multiple angles is still lacking. This review underscores the progress and strategies proposed so far to pursuit the high-efficiency Re-ZABs system, including the aspects of rechargeability (from primary to rechargeable), air cathode (from unifunctional to bifunctional), zinc anode (from dendritic to stable), electrolytes (from aqueous to non-aqueous), battery configurations (from non-portable to portable), and industrialization progress (from laboratorial to practical). Critical appraisals of the advanced modification approaches (such as surface/interface modulation, nanoconfinement catalysis, defect electrochemistry, synergistic electrocatalysis, etc.) are highlighted for cost-effective flexible Re-ZABs with good sustainability and high energy density. Finally, insights are further rendered properly for the future research directions of advanced zinc-air batteries.

Intermittent investigations on attenuation mechanism of rechargeable zinc-air batteries during charge/discharge cycles.

Rechargeable zinc-air batteries (RZABs) are an ideal substitute for energy storage, but the short cycle longevity during long-term charge/discharge operation is one of the bottleneck factors that seriously restrict commercial application. Herein, the FeCo alloy/N, S co-doped carbon aerogel (NSCA/FeCo) were prepared as catalysts of cathode for RZABs. We investigated the polarization and impedance on long-term cycles during the battery operation to explore the attenuation mechanism. The results indicated that the roundtrip efficiency of batteries during charge/discharge cycles reduced fast initially and then slow. Besides, the comparative experiment was tested through the replacement of a new electrolyte and a zinc sheet. It is manifested that the failure of the battery is mainly due to the attenuation of the air cathode performance. Therefore, to further disclose the influencing factors and internal mechanisms of air cathode performance degradation, we conducted a series of characterization and testing, including the hydrophilicity, surface morphology, elemental composition, and electrochemical performance of three-electrode systems at different cycle times. This work not only provides a theoretical basis for deeply comprehending the attenuation mechanism of the cathode but also serves a reference for the material design and operating condition optimization of RZABs.

Cobalt Oxide-Based Electrocatalysts with Bifunctionality for High-Performing Rechargeable Zinc-Air Batteries.

In recent years, the rapid growth in renewable energy applications has created a significant demand for efficient energy storage solutions on a large scale. Among the various options, rechargeable zinc-air batteries (ZABs) have emerged as an appealing choice in green energy storage technology due to their higher energy density, sustainability, and cost-effectiveness. Regarding this fact, a spotlight is shaded on air electrode for constructing high-performance ZABs. Cobalt oxide-based electrocatalysts on the air electrode have gained significant attention due to their extraordinary features. Particularly, exploration and integration of bifunctional behavior for energy storage has remarkably promoted both ORR and OER to facilitate the overall performance of the battery. The plot of this review is forwarded towards in-depth analysis of the latest advancements in electrocatalysts that are based on cobalt oxide and possess bifunctional properties along with an introduction of the fundamental aspects of ZABs, Additionally, the topic entails an examination of the morphological variations and mechanistic details mentioning about the synthesis processes. Finally, a direction is provided for future research endeavors through addressing the challenges and prospects in the advancement of next-generation bifunctional electrocatalysts to empower high-performing ZABs with bifunctional cobalt oxide.

Robust wrinkled MoS2/N-C bifunctional electrocatalysts interfaced with single Fe atoms for wearable zinc-air batteries.

The ability to create highly efficient and stable bifunctional electrocatalysts, capable of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in the same electrolyte, represents an important endeavor toward high-performance zinc-air batteries (ZABs). Herein, we report a facile strategy for crafting wrinkled MoS2/N-doped carbon core/shell nanospheres interfaced with single Fe atoms (denoted MoS2@Fe-N-C) as superior ORR/OER bifunctional electrocatalysts for robust wearable ZABs with a high capacity and outstanding cycling stability. Specifically, the highly crumpled MoS2 nanosphere core is wrapped with a layer of single-Fe-atom-impregnated, N-doped carbon shell (i.e., Fe-N-C shell with well-dispersed FeN4 sites). Intriguingly, MoS2@Fe-N-C nanospheres manifest an ORR half-wave potential of 0.84 V and an OER overpotential of 360 mV at 10 mA⋅cm-2 More importantly, density functional theory calculations reveal the lowered energy barriers for both ORR and OER, accounting for marked enhanced catalytic performance of MoS2@Fe-N-C nanospheres. Remarkably, wearable ZABs assembled by capitalizing on MoS2@Fe-N-C nanospheres as an air electrode with an ultralow area loading (i.e., 0.25 mg⋅cm-2) display excellent stability against deformation, high special capacity (i.e., 442 mAh⋅g-1Zn), excellent power density (i.e., 78 mW⋅cm-2) and attractive cycling stability (e.g., 50 cycles at current density of 5 mA⋅cm-2). This study provides a platform to rationally design single-atom-interfaced core/shell bifunctional electrocatalysts for efficient metal-air batteries.