In Situ Two‐Step Activation Strategy Boosting Hierarchical Porous Carbon Cathode for an Aqueous Zn‐Based Hybrid Energy Storage Device with High Capacity and Ultra‐Long Cycling Life

Aqueous Zn‐based hybrid energy storage devices (HESDs) exhibit great potential for large‐scale energy storage applications for the merits of environmental friendliness, low redox potential, and high theoretical capacity of Zn anode. However, they are still subjected to low specific capacities since adsorption‐type cathodes (i.e., activated carbon, hard carbon) have limited capability to accommodate active ions. Herein, a hierarchical porous activated carbon cathode (HPAC) is prepared via an in situ two‐step activation strategy, different from the typical one‐step/postmortem activation of fully carbonized precursors. The strategy endows the HPAC with a high specific surface area and a large mesoporous volume, and thus provides abundant active sites and fast kinetics for accommodating active ions. Consequently, pairing the HPAC with Zn anode yields an aqueous Zn‐based HESD, which delivers a high specific capacity of 231 mAh g^?1 at 0.5 A g^?1 and excellent rate performance with a retained capacity of 119 mAh g^?1 at 20 A g^?1, the best result among previously reported lithium‐free HESDs based on carbon cathodes. Further, the aqueous Zn‐based HESD shows ultra‐long cycling stability with a capacity retention of ≈70% after 18 000 cycles at 10 A g^?1, indicating great potential for environmentally friendly, low‐cost, and high‐safety energy storage applications.     

Molecular‐Level Design of Hierarchically Porous Carbons Codoped with Nitrogen and Phosphorus Capable of In Situ Self‐Activation for Sustainable Energy Systems

Hierarchically porous carbons are attracting tremendous attention in sustainable energy systems, such as lithium ion battery (LIB) and fuel cell, due to their excellent transport properties that arise from the high surface area and rich porosity. The state‐of‐the‐art approaches for synthesizing hierarchically porous carbons normally require chemical‐ and/or template‐assisted activation techniques, which is complicate, time consuming, and not feasible for large scale production. Here, a molecular‐level design principle toward large‐scale synthesis of nitrogen and phosphorus codoped hierarchically porous carbon (NPHPC) through an in situ self‐activation process is proposed. The material is fabricated based on the direct pyrolysis of a well‐designed polymer, melamine polyphosphate, which is capable of in situ self‐activation to generate large specific surface area (1479 m² g^?1) and hierarchical pores in the final NPHPC. As an anode material for LIB, NPHPC delivers a high reversible capacity of 1073 mAh g^?1 and an excellent cyclic stability for 300 cycles with negligible capacity decay. The peculiar structural properties and synergistic effect of N and P codopants also enable NPHPC a promising electrocatalyst for oxygen reduction reaction, a key cathodic reaction process of many energy conversion devices (for example, fuel cells and metal air batteries). Electrochemical measurements show NPHPC a comparable electrocatalytic performance to commercial Pt/C catalyst (onset potential of 0.88 V vs reversible hydrogen electrode in alkaline medium) with excellent stability (89.8% retention after 20 000 s continuous operation) and superior methanol tolerance.     

Defective N/S‐Codoped 3D Cheese‐Like Porous Carbon Nanomaterial toward Efficient Oxygen Reduction and Zn–Air Batteries

Developing a facile and cost‐efficient method to synthesize carbon‐based nanomaterials possessing excellent structural and functional properties has become one of the most attractive topics in energy conversion and storage fields. In this study, density functional theory calculation results reveal the origin of high oxygen reduction reaction (ORR) activity predominantly derived from the synergistic effect of intrinsic defects and heteroatom dopants (e.g., N, S) that modulate the bandgap and charge density distribution of carbon matrix. Under the guidance of the first‐principle prediction, by using ultralight biomass waste as precursor of C, N, and S elements, a defect‐rich and N/S dual‐doped cheese‐like porous carbon nanomaterial is successfully designed and constructed. Herein, the intrinsic defects are artfully generated in terms of alkaline and ammonia activation. The electrochemical measurements display that such a material owns a comparable ORR activity (E_1/2 = 0.835 V) to the commercial Pt/C catalyst, along with splendid durability and methanol tolerance in alkali media. Furthermore, as cathode catalyst, it displays a high Zn–air battery performance. The excellent ORR activity of the catalyst can be attributed to its unique 3D porous architecture, abundant intrinsic defects, and high‐content active heteroatom dopants in the carbon matrix.     

Green Synthesis of Hierarchically Porous Carbon Nanotubes as Advanced Materials for High‐Efficient Energy Storage

Hierarchically porous carbon nanomaterials with well‐defined architecture can afford a promising platform for effectively addressing energy and environmental concerns. Herein, a totally green and straightforward synthesis strategy for the fabrication of hierarchically porous carbon nanotubes (HPCNTs) by a simple carbonization treatment without any assistance of soft/hard templates and activation procedures is demonstrated. A high specific surface area of 1419 m² g^?1 and hierarchical micro‐/meso‐/macroporosity can be achieved for the HPCNTs. The unique porous architecture enables the HPCNTs serving as excellent electrode/host materials for high‐performance supercapacitors and Li–sulfur batteries. The design strategy may pave a new avenue for the rational synthesis of hierarchically porous carbon nanostructures for high‐efficient energy storage applications.     

In Situ Construction of Stable Tissue‐Directed/Reinforced Bifunctional Separator/Protection Film on Lithium Anode for Lithium–Oxygen Batteries

To achieve a high reversibility and long cycle life for Li–O₂ battery system, the stable tissue‐directed/reinforced bifunctional separator/protection film (TBF) is in situ fabricated on the surface of metallic lithium anode. It is shown that a Li–O₂ cell composed of the TBF‐modified lithium anodes exhibits an excellent anodic reversibility (300 cycles) and effectively improved cathodic long lifetime (106 cycles). The improvement is attributed to the ability of the TBF, which has chemical, electrochemical, and mechanical stability, to effectively prevent direct contact between the surface of the lithium anode and the highly reactive reduced oxygen species (Li₂O₂ or its intermediate LiO₂) in cell. It is believed that the protection strategy describes here can be easily extended to other next‐generation high energy density batteries using metal as anode including Li–S and Na–O₂ batteries.     

3D Mesoporous Graphene: CVD Self‐Assembly on Porous Oxide Templates and Applications in High‐Stable Li‐S Batteries

A nanostructured carbon with high specific surface area (SSA), tunable pore structure, superior electrical conductivity, mechanically robust framework, and high chemical stability is an important requirement for electrochemical energy storage. Porous graphene fabricated by chemical activation and liquid etching has a high surface area but very limited volume of electrochemically accessible mesopores. Herein, an effective strategy of in situ formation of hierarchically mesoporous oxide templates with small pores induced by Kirkendall diffusion and large pores attributed to evaporation of deliberately introduced volatile metal is proposed for chemical vapor deposition assembly of porous graphene frameworks (PGFs). The PGFs inherit the hierarchical mesoporous structure of the templates. A high SSA of 1448 m² g⁻¹, 91.6% of which is contributed by mesopores, and a mesopore volume of 2.40 cm³ g⁻¹ are attained for PGFs serving as reservoirs of ions or active materials in electrochemical energy storage applications. When the PGFs are applied in lithium‐sulfur batteries, a very high sulfur utilization of 71% and a very low fading rate of ≈0.04% per cycle after the second cycle are achieved at a current rate of 1.0 C. This work provides a general strategy for the rational construction of mesoporous structures induced by a volatile metal, with a view toward the design of hierarchical nanomaterials for advanced energy storage.     

Ni2P@Carbon Core–Shell Nanoparticle‐Arched 3D Interconnected Graphene Aerogel Architectures as Anodes for High‐Performance Sodium‐Ion Batteries

To alleviate large volume change and improve poor electrochemical reaction kinetics of metal phosphide anode for sodium‐ion batteries, for the first time, an unique Ni₂P@carbon/graphene aerogel (GA) 3D interconnected porous architecture is synthesized through a solvothermal reaction and in situ phosphorization process, where core–shell Ni₂P@C nanoparticles are homogenously embedded in GA nanosheets. The synergistic effect between components endows Ni₂P@C/GA electrode with high structural stability and electrochemical activity, leading to excellent electrochemical performance, retaining a specific capacity of 124.5 mA h g^?1 at a current density of 1 A g^?1 over 2000 cycles. The robust 3D GA matrix with abundant open pores and large surface area can provide unblocked channels for electrolyte storage and Na⁺ transfer and make fully close contact between the electrode and electrolyte. The carbon layers and 3D GA together build a 3D conductive matrix, which not only tolerates the volume expansion as well as prevents the aggregation and pulverization of Ni₂P nanoparticles during Na⁺ insertion/extraction processes, but also provides a 3D conductive highway for rapid charge transfer processes. The present strategy for phosphides via in situ phosphization route and coupling phosphides with 3D GA can be extended to other novel electrodes for high‐performance energy storage devices.     

A 3D and Stable Lithium Anode for High‐Performance Lithium–Iodine Batteries

Lithium metal is considered as the most promising anode material due to its high theoretical specific capacity and the low electrochemical reduction potential. However, severe dendrite problems have to be addressed for fabricating stable and rechargeable batteries (e.g., lithium–iodine batteries). To fabricate a high‐performance lithium–iodine (Li–I₂) battery, a 3D stable lithium metal anode is prepared by loading of molten lithium on carbon cloth doped with nitrogen and phosphorous. Experimental observations and theoretical calculation reveal that the N,P codoping greatly improves the lithiophilicity of the carbon cloth, which not only enables the uniform loading of molten lithium but also facilitates reversible lithium stripping and plating. Dendrites formation can thus be significantly suppressed at a 3D lithium electrode, leading to stable voltage profiles over 600 h at a current density of 3 mA cm^?2. A fuel cell with such an electrode and a lithium–iodine cathode shows impressive long‐term stability with a capacity retention of around 100% over 4000 cycles and enhanced high‐rate capability. These results demonstrate the promising applications of 3D stable lithium metal anodes in next‐generation rechargeable batteries.     

Highly Porous Mn3O4 Micro/Nanocuboids with In Situ Coated Carbon as Advanced Anode Material for Lithium‐Ion Batteries

The electrochemical performance of most transition metal oxides based on the conversion mechanism is greatly restricted by inferior cycling stability, rate capability, high overpotential induced by the serious irreversible reactions, low electrical conductivity, and poor ion diffusivity. To mitigate these problems, highly porous Mn₃O₄ micro/nanocuboids with in situ formed carbon matrix (denoted as Mn₃O₄@C micro/nanocuboids) are designed and synthesized via a one‐pot hydrothermal method, in which glucose plays the roles of a reductive agent and a carbon source simultaneously. The carbon content, particle size, and pore structure in the composite can be facilely controlled, resulting in continuous carbon matrix with abundant pores in the cuboids. The as‐fabricated Mn₃O₄@C micro/nanocuboids exhibit large reversible specific capacity (879 mAh g^?1 at the current density of 100 mA g^?1) as well as outstanding cycling stability (86% capacity retention after 500 cycles) and rate capability, making it a potential candidate as anode material for lithium‐ion batteries. Moreover, this facile and effective synthetic strategy can be further explored as a universal approach for the synthesis of other hierarchical transition metal oxides and carbon hybrids with subtle structure engineering.     

Flexible Graphene‐Wrapped Carbon Nanotube/Graphene@MnO2 3D Multilevel Porous Film for High‐Performance Lithium‐Ion Batteries

The ingenious design of a freestanding flexible electrode brings the possibility for power sources in emerging wearable electronic devices. Here, reduced graphene oxide (rGO) wraps carbon nanotubes (CNTs) and rGO tightly surrounded by MnO₂ nanosheets, forming a 3D multilevel porous conductive structure via vacuum freeze‐drying. The sandwich‐like architecture possesses multiple functions as a flexible anode for lithium‐ion batteries. Micrometer‐sized pores among the continuously waved rGO layers could extraordinarily improve ion diffusion. Nano‐sized pores among the MnO₂ nanosheets and CNT/rGO@MnO₂ particles could provide vast accessible active sites and alleviate volume change. The tight connection between MnO₂ and carbon skeleton could facilitate electron transportation and enhance structural stability. Due to the special structure, the rGO‐wrapped CNT/rGO@MnO₂ porous film as an anode shows a high capacity, excellent rate performance, and superior cycling stability (1344.2 mAh g⁻¹ over 630 cycles at 2 A g⁻¹, 608.5 mAh g⁻¹ over 1000 cycles at 7.5 A g⁻¹). Furthermore, the evolutions of microstructure and chemical valence occurring inside the electrode after cycling are investigated to illuminate the structural superiority for energy storage. The excellent electrochemical performance of this freestanding flexible electrode makes it an attractive candidate for practical application in flexible energy storage.     

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.     

Rapid,High‐Temperature,In Situ Microwave Synthesis of Bulk Nanocatalysts

Carbon‐black‐supported nanoparticles (CNPs) have attracted considerable attention for their intriguing catalytic properties and promising applications. The traditional liquid synthesis of CNPs commonly involves demanding operation conditions and complex pre‐ or post‐treatments, which are time consuming and energy inefficient. Herein, a rapid, scalable, and universal strategy is reported to synthesize highly dispersed metal nanoparticles embedded in a carbon matrix via microwave irradiation of carbon black with preloaded precursors. By optimizing the amount of carbon black, the microwave absorption is dramatically improved while the thermal dissipation is effectively controlled, leading to a rapid temperature increase in carbon black, ramping to 1270 K in just 6 s. The whole synthesis process requires no capping agents or surfactants, nor tedious pre‐ or post‐treatments of carbon black, showing tremendous potential for mass production. As a proof of concept, the synthesis of ultrafine Ru nanoparticles (≈2.57 nm) uniformly embedded in carbon black using this microwave heating technique is demonstrated, which displays remarkable electrocatalytic performance when used as the cathode in a Li–O₂ battery. This microwave heating method can be extended to the synthesis of other nanoparticles, thereby providing a general methodology for the mass production of carbon‐supported catalytic nanoparticles.     

Toward Tailorable Zn‐Ion Textile Batteries with High Energy Density and Ultrafast Capability: Building High‐Performance Textile Electrode in 3D Hierarchical Branched Design

Rechargeable Zn‐ion batteries are promising candidates for wearable energy storage devices. However, their performance is severely restricted by the low conductivity and inferior mass loading. Herein, a new type of the textile based electrodes with 3D hierarchical branched design is reported. Both Ni nanoparticles and carbon nanotubes are used to build conductive coatings on the textiles. The 3D hierarchical nanostructures, consisting of the vertical‐aligned nanosheets and the fluffy‐like small flakes, grow on the conductive textiles to form the self‐supported electrodes. It ensures fast electron/ion transport and high mass loading, and maintains the structure stability during cycling. Two textile electrodes with the NiCo hydroxide and MnO₂ self‐branched nanostructures are constructed. Their faster kinetics, higher capacity and better rate capability than the solitary nanosheets based counterpart demonstrate the superiority of the hierarchical architecture. Moreover, the solid‐state Zn‐MnO₂ and Zn‐NiCo batteries are fabricated based on the textile electrodes and the polymer electrolytes. The high energy density, superior power density and good long‐term cycling stability confirm their excellent energy storage ability and fast charge/discharge capability. Particularly, the high safety under various conditions enable them promising candidates for wearable electronics.     

Enhanced Electrocatalytic Performance through Body Enrichment of Co‐Based Bimetallic Nanoparticles In Situ Embedded Porous N‐Doped Carbon Spheres

Extending available body space loading active species and controllably tailoring the d‐band center to Fermi level of catalysts are of paramount importance but extremely challenging for the enhancement of electrocatalytic performance. Herein, a melamine‐bridged self‐construction strategy is proposed to in situ embed Co‐based bimetallic nanoparticles in the body of N‐doped porous carbon spheres (CoM‐e‐PNC), and achieve the controllable tailoring of the d‐band center position by alloying of Co and another transition metal M (M = Ni, Fe, Mn, and Cu). The enrichment and exposure of the active sites in the body interior of porous carbon spheres, and the best balance between the adsorption of OH species and the desorption of O₂ induced by optimizing the d‐band center position, collectively enhance the oxygen evolution reaction (OER) performance. Meanwhile, the relationship of d‐band center position and OER activity is found to exhibit the volcano curve rule, where the CoNi‐e‐PNC catalyst shows optimal OER performance with an overpotential of 0.24 V at 10 mA cm^?2 in alkaline media, outperforming those of the ever‐reported CoNi‐based catalysts. Besides, CoNi‐e‐PNC catalyst also demonstrates high OER stability with slight current decrease after 100 h.     

A Flexible Film toward High‐Performance Lithium Storage: Designing Nanosheet‐Assembled Hollow Single‐Hole Ni–Co–Mn–O Spheres with Oxygen Vacancy Embedded in 3D Carbon Nanotube/Graphene Network

Ternary transition metal oxides (TMOs) are highly potential electrode materials for lithium ion batteries (LIBs) due to abundant defects and synergistic effects with various metal elements in a single structure. However, low electronic/ionic conductivity and severe volume change hamper their practical application for lithium storage. Herein, nanosheet‐assembled hollow single‐hole Ni–Co–Mn oxide (NHSNCM) spheres with oxygen vacancies can be obtained through a facile hydrothermal reaction, which makes both ends of each nanosheet exposed to sufficient free space for volume variation, electrolyte for extra active surface area, and dual ion diffusion paths compared with airtight hollow structures. Furthermore, oxygen vacancies could improve ion/electronic transport and ion insertion/extraction process of NHSNCM spheres. Thus, oxygen‐vacancy‐rich NHSNCM spheres embedded into a 3D porous carbon nanotube/graphene network as the anode film ensure efficient electrolyte infiltration into both the exterior and interior of porous and open spheres for a high utilization of the active material, showing an excellent electrochemical performance for LIBs (1595 mAh g^?1 over 300 cycles at 2 A g^?1, 441.6 mAh g^?1 over 4000 cycles at 10 A g^?1). Besides, this straightforward synthetic method opens an efficacious avenue for the construction of various nanosheet‐assembled hollow single‐hole TMO spheres for potential applications.