Elucidation of Active Sites on S,N Codoped Carbon Cubes Embedding Co–Fe Carbides toward Reversible Oxygen Conversion in High‐Performance Zinc–Air Batteries

The development of high‐performance but low‐cost catalysts for the electrochemical oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is of central importance for realizing the prevailing application of metal–air batteries. Herein a facile route is devised to synthesize S, N codoped carbon cubes embedding Co–Fe carbides by pyrolyzing the Co–Fe Prussian blue analogues (PBA) coated with methionine. Via the strong metal–sulfur interaction, the methionine coating provides a robust sheath to restrain the cubic morphology of PBA upon pyrolysis, which is proved highly beneficial for promoting the specific surface area and active sites exposure, leading to remarkable bifunctionality of ORR and OER comparable to the benchmarks of Pt/C and RuO₂. Further elaborative investigations on the activity origin and postelectrolytic composition unravel that for ORR the high activity is mainly contributed by the S, N codoped carbon shell with the inactive carbide phase converting into carbonate hydroxides. For OER, the embedded Co–Fe carbides transform in situ into layered (hydr)oxides, serving as the actual active sites for promoting water oxidation. Zn–air batteries employing the developed hollow structure as the air cathode catalyst demonstrate superb rechargeability, energy efficiency, as well as portability.     

Defect Engineering of Chalcogen‐Tailored Oxygen Electrocatalysts for Rechargeable Quasi‐Solid‐State Zinc–Air Batteries

A critical bottleneck limiting the performance of rechargeable zinc–air batteries lies in the inefficient bifunctional electrocatalysts for the oxygen reduction and evolution reactions at the air electrodes. Hybridizing transition‐metal oxides with functional graphene materials has shown great advantages due to their catalytic synergism. However, both the mediocre catalytic activity of metal oxides and the restricted 2D mass/charge transfer of graphene render these hybrid catalysts inefficient. Here, an effective strategy combining anion substitution, defect engineering, and the dopant effect to address the above two critical issues is shown. This strategy is demonstrated on a hybrid catalyst consisting of sulfur‐deficient cobalt oxysulfide single crystals and nitrogen‐doped graphene nanomeshes (CoO_0.87S_0.13/GN). The defect chemistries of both oxygen‐vacancy‐rich, nonstoichiometric cobalt oxysulfides and edge‐nitrogen‐rich graphene nanomeshes lead to a remarkable improvement in electrocatalytic performance, where CoO_0.87S_0.13/GN exhibits strongly comparable catalytic activity to and much better stability than the best‐known benchmark noble‐metal catalysts. In application to quasi‐solid‐state zinc–air batteries, CoO_0.87S_0.13/GN as a freestanding catalyst assembly benefits from both structural integrity and enhanced charge transfer to achieve efficient and very stable cycling operation over 300 cycles with a low discharge–charge voltage gap of 0.77 V at 20 mA cm^?2 under ambient conditions.     

Novel MOF‐Derived Co@N‐C Bifunctional Catalysts for Highly Efficient Zn–Air Batteries and Water Splitting

Metal–organic frameworks (MOFs) and MOF‐derived materials have recently attracted considerable interest as alternatives to noble‐metal electrocatalysts. Herein, the rational design and synthesis of a new class of Co@N‐C materials (C‐MOF‐C2‐T) from a pair of enantiotopic chiral 3D MOFs by pyrolysis at temperature T is reported. The newly developed C‐MOF‐C2‐900 with a unique 3D hierarchical rodlike structure, consisting of homogeneously distributed cobalt nanoparticles encapsulated by partially graphitized N‐doped carbon rings along the rod length, exhibits higher electrocatalytic activities for oxygen reduction and oxygen evolution reactions (ORR and OER) than that of commercial Pt/C and RuO₂, respectively. Primary Zn–air batteries based on C‐MOF‐900 for the oxygen reduction reaction (ORR) operated at a discharge potential of 1.30 V with a specific capacity of 741 mA h g_Zn^–1 under 10 mA cm^–2. Rechargeable Zn–air batteries based on C‐MOF‐C2‐900 as an ORR and OER bifunctional catalyst exhibit initial charge and discharge potentials at 1.81 and 1.28 V (2 mA cm^–2), along with an excellent cycling stability with no increase in polarization even after 120 h – outperform their counterparts based on noble‐metal‐based air electrodes. The resultant rechargeable Zn–air batteries are used to efficiently power electrochemical water‐splitting systems, demonstrating promising potential as integrated green energy systems for practical applications.     

Atomic Modulation and Structure Design of Carbons for Bifunctional Electrocatalysis in Metal–Air Batteries

With the extensive research and development of renewable energy technologies, there is an increasing interest in developing metal‐free carbons as a new class of bifunctional electrocatalysts for boosting the performance of metal–air batteries. Along with significant understanding of the electrocatalytic nature and the rapid development of techniques, the activities of carbon electrocatalysts are well‐tailored by introducing particular dopants/defects and structure regulation. Herein, the recent advances regarding the rational design of carbon‐based electrocatalysts for the oxygen reduction reaction and oxygen evolution reaction are summarized, with a special focus on the bifunctional applications in Zn–air and Li–air batteries. Specifically, the atomic modulation strategies to regulate the electrocatalytic activities of carbons and structure modification are summarized to gain deep insights into bifunctional mechanisms and boost advanced Zn–air and Li–air batteries. The current challenges and future perspectives are also addressed to accelerate the exploration of promising bifunctional carbon catalysts for renewable energy technologies, particularly metal–air batteries.     

Bifunctional Transition Metal Hydroxysulfides: Room‐Temperature Sulfurization and Their Applications in Zn–Air Batteries

Bifunctional electrocatalysis for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) constitutes the bottleneck of various sustainable energy devices and systems like rechargeable metal–air batteries. Emerging catalyst materials are strongly requested toward superior electrocatalytic activities and practical applications. In this study, transition metal hydroxysulfides are presented as bifunctional OER/ORR electrocatalysts for Zn–air batteries. By simply immersing Co‐based hydroxide precursor into solution with high‐concentration S^2?, transition metal hydroxides convert to hydroxysulfides with excellent morphology preservation at room temperature. The as‐obtained Co‐based metal hydroxysulfides are with high intrinsic reactivity and electrical conductivity. The electron structure of the active sites is adjusted by anion modulation. The potential for 10 mA cm^?2 OER current density is 1.588 V versus reversible hydrogen electrode (RHE), and the ORR half‐wave potential is 0.721 V versus RHE, with a potential gap of 0.867 V for bifunctional oxygen electrocatalysis. The Co₃FeS_1.5(OH)₆ hydroxysulfides are employed in the air electrode for a rechargeable Zn–air battery with a small overpotential of 0.86 V at 20.0 mA cm^?2, a high specific capacity of 898 mAh g^?1, and a long cycling life, which is much better than Pt and Ir‐based electrocatalyst in Zn–air batteries.     

Co Nanoparticles Confined in 3D Nitrogen‐Doped Porous Carbon Foams as Bifunctional Electrocatalysts for Long‐Life Rechargeable Zn–Air Batteries

Proper design and simple preparation of nonnoble bifunctional electrocatalysts with high cost performance and strong durability for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) is highly demanded but still full of enormous challenges. In this work, a spontaneous gas‐foaming strategy is presented to synthesize cobalt nanoparticles confined in 3D nitrogen‐doped porous carbon foams (CoNCF) by simply carbonizing the mixture of citric acid, NH₄Cl, and Co(NO₃)₂·6H₂O. Thanks to its particular 3D porous foam architecture, ultrahigh specific surface area (1641 m² g^?1), and homogeneous distribution of active sites (C–N, Co–N_x, and Co–O moieties), the optimized CoNCF‐1000‐80 (carbonized at 1000 °C, containing 80 mg Co(NO₃)₂·6H₂O in precursors) catalyst exhibits a remarkable bifunctional activity and long‐term durability toward both ORR and OER. Its bifunctional activity parameter (ΔE) is as low as 0.84 V, which is much smaller than that of noble metal catalyst and comparable to state‐of‐the‐art bifunctional catalysts. When worked as an air electrode catalyst in rechargeable Zn–air batteries, a high energy density (797 Wh kg^?1), a low charge/discharge voltage gap (0.75 V), and a long‐term cycle stability (over 166 h) are achieved at 10 mA cm^?2.     

An Oxygen‐Vacancy‐Rich Semiconductor‐Supported Bifunctional Catalyst for Efficient and Stable Zinc–Air Batteries

The highly oxidative operating conditions of rechargeable zinc–air batteries causes significant carbon‐support corrosion of bifunctional oxygen electrocatalysts. Here, a new strategy for the catalyst support design focusing on oxygen vacancy (OV)‐rich, low‐bandgap semiconductor is proposed. The OVs promote the electrical conductivity of the oxide support, and at the same time offer a strong metal–support interaction (SMSI), which enables the catalysts to have small metal size, high catalytic activity, and high stability. The strategy is demonstrated by successfully synthesizing ultrafine Co‐metal‐decorated 3D ordered macroporous titanium oxynitride (3DOM‐Co@TiO_xN_y). The 3DOM‐Co@TiO_xN_y catalyst exhibits comparable activities for oxygen reduction and evolution reactions, but much higher cycling stability than noble metals in alkaline conditions. The zinc–air battery using this catalyst delivers an excellent stability with less than 1% energy efficiency loss over 900 charge–discharge cycles at 20 mA cm^?2. The high stability is attributed to the strong SMSI between Co and 3DOM‐TiO_xN_y which is verified by density functional theory calculations. This work sheds light on using OV‐rich semiconductors as a promising support to design efficient and durable nonprecious electrocatalysts.     

One‐Step Route Synthesized Co2P/Ru/N‐Doped Carbon Nanotube Hybrids as Bifunctional Electrocatalysts for High‐Performance Li–O2 Batteries

The large‐scale commercial application of lithium–oxygen batteries (LOBs) is overwhelmed by the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) associated with insoluble and insulated Li₂O₂. Herein, an elaborate design on a highly catalytic LOBs cathode constructed by N‐doped carbon nanotubes (CNT) with in situ encapsulated Co₂P and Ru nanoparticles is reported. The homogeneously dispersed Co₂P and Ru catalysts can effectively modulate the formation and decomposition behavior of Li₂O₂ during discharge/charge processes, ameliorating the electronically insulating property of Li₂O₂ and constructing a homogenous low‐impedance Li₂O₂/catalyst interface. Compared with Co/CNT and Ru/CNT electrodes, the Co₂P/Ru/CNT electrode delivers much higher oxygen reduction triggering onset potential and higher ORR and OER peak current and integral areas, showing greatly improved ORR/OER kinetics due to the synergistic effects of Co₂P and Ru. Li–O₂ cells based on the Ru/Co₂P/CNT electrode demonstrate improved ORR/OER overpotential of 0.75 V, excellent rate capability of 12 800 mAh g^?1 at 1 A g^?1, and superior cycle stability for more than 185 cycles under a restricted capacity of 1000 mAh g^?1 at 100 mA g^?1. This work paves an exciting avenue for the design and construction of bifunctional catalytic cathodes by coupling metal phosphides with other active components in LOBs.     

Strategies toward High‐Performance Cathode Materials for Lithium–Oxygen Batteries

Rechargeable aprotic lithium (Li)–O₂ batteries with high theoretical energy densities are regarded as promising next‐generation energy storage devices and have attracted considerable interest recently. However, these batteries still suffer from many critical issues, such as low capacity, poor cycle life, and low round‐trip efficiency, rendering the practical application of these batteries rather sluggish. Cathode catalysts with high oxygen reduction reaction (ORR) and evolution reaction activities are of particular importance for addressing these issues and consequently promoting the application of Li–O₂ batteries. Thus, the rational design and preparation of the catalysts with high ORR activity, good electronic conductivity, and decent chemical/electrochemical stability are still challenging. In this Review, the strategies are outlined including the rational selection of catalytic species, the introduction of a 3D porous structure, the formation of functional composites, and the heteroatom doping which succeeded in the design of high‐performance cathode catalysts for stable Li–O₂ batteries. Perspectives on enhancing the overall electrochemical performance of Li–O₂ batteries based on the optimization of the properties and reliability of each part of the battery are also made. This Review sheds some new light on the design of highly active cathode catalysts and the development of high‐performance lithium–O₂ batteries.     

Dendrite‐Free Sodium‐Metal Anodes for High‐Energy Sodium‐Metal Batteries

Sodium (Na) metal is one of the most promising electrode materials for next‐generation low‐cost rechargeable batteries. However, the challenges caused by dendrite growth on Na metal anodes restrict practical applications of rechargeable Na metal batteries. Herein, a nitrogen and sulfur co‐doped carbon nanotube (NSCNT) paper is used as the interlayer to control Na nucleation behavior and suppress the Na dendrite growth. The N‐ and S‐containing functional groups on the carbon nanotubes induce the NSCNTs to be highly “sodiophilic,” which can guide the initial Na nucleation and direct Na to distribute uniformly on the NSCNT paper. As a result, the Na‐metal‐based anode (Na/NSCNT anode) exhibits a dendrite‐free morphology during repeated Na plating and striping and excellent cycling stability. As a proof of concept, it is also demonstrated that the electrochemical performance of sodium–oxygen (Na–O₂) batteries using the Na/NSCNT anodes show significantly improved cycling performances compared with Na–O₂ batteries with bare Na metal anodes. This work opens a new avenue for the development of next‐generation high‐energy‐density sodium‐metal batteries.     

Framework‐Porphyrin‐Derived Single‐Atom Bifunctional Oxygen Electrocatalysts and their Applications in Zn–Air Batteries

High‐performance bifunctional oxygen electrocatalysis constitutes the key technique for the widespread application of clean and sustainable energy through electrochemical devices such as rechargeable Zn–air batteries. Single‐atom electrocatalysts with maximum atom efficiency are highly considered as an alternative of the present noble‐metal‐based electrocatalysts. However, the fabrication of transition metal single‐atoms is very challenging, requiring extensive attempts of precursors with novel design principles. Herein, an all‐covalently constructed cobalt‐coordinated framework porphyrin with graphene hybridization is innovatively designed and prepared as the pyrolysis precursor to fabricate single‐atom Co–N_x–C electrocatalysts. Excellent electrochemical performances are realized for both bifunctional oxygen electrocatalysis and rechargeable Zn–air batteries with regard to reduced overpotentials, improved kinetics, and prolonged cycling stability comparable with noble‐metal‐based electrocatalysts. Design principles from multiple scales are proposed and rationalized with detailed mechanism investigation. This work not only provides a novel precursor for the fabrication of high‐performance single‐atom electrocatalysts, but also inspires further attempts to develop advanced materials and emerging applications.     

Self‐Catalyzed Growth of Co–N–C Nanobrushes for Efficient Rechargeable Zn–Air Batteries

Highly efficient and stable bifunctional electrocatalysts for oxygen reduction and evolution are essential for aqueous rechargeable Zn–air batteries, which require highly active sites as well as delicate structural design for increasing effective active sites and facilitating mass/electron transfer. Herein, a scalable and facile self‐catalyzed growth strategy is developed to integrate highly active Co–N–C sites with 3D brush‐like nanostructure, achieving Co–N–C nanobrushes with Co,N‐codoped carbon nanotube branches grown on Co,N‐codoped nanoparticle assembled nanowire backbones. Systematic investigations suggest that nanobrushes deliver significantly improved electrocatalytic activity compared with nanowire or nanotube counterparts and the longer nanotube branches give the better performance. Benefiting from the increase of accessible highly active sites and enhanced mass transfer and electron transportation, the present Co–N–C nanobrush exhibits superior electrocatalytic activity and durability when used as a bifunctional oxygen catalyst. It enables a rechargeable Zn–air battery with a high peak power density of 246 mW cm^?2 and excellent cycling stability. These results suggest that the reported synthetic strategy may open up possibilities for exploring efficient electrocatalysts for diverse applications.     

Facilitated Oxygen Chemisorption in Heteroatom‐Doped Carbon for Improved Oxygen Reaction Activity in All‐Solid‐State Zinc–Air Batteries

Driven by the intensified demand for energy storage systems with high‐power density and safety, all‐solid‐state zinc–air batteries have drawn extensive attention. However, the electrocatalyst active sites and the underlying mechanisms occurring in zinc–air batteries remain confusing due to the lack of in situ analytical techniques. In this work, the in situ observations, including X‐ray diffraction and Raman spectroscopy, of a heteroatom‐doped carbon air cathode are reported, in which the chemisorption of oxygen molecules and oxygen‐containing intermediates on the carbon material can be facilitated by the electron deficiency caused by heteroatom doping, thus improving the oxygen reaction activity for zinc–air batteries. As expected, solid‐state zinc–air batteries equipped with such air cathodes exhibit superior reversibility and durability. This work thus provides a profound understanding of the reaction principles of heteroatom‐doped carbon materials in zinc–air batteries.