Kinetics Enhanced Nitrogen‐Doped Hierarchical Porous Hollow Carbon Spheres Boosting Advanced Potassium‐Ion Hybrid Capacitors

Potassium‐ion hybrid capacitors (PIHCs) shrewdly combine a battery‐type anode and a capacitor‐type cathode, exhibiting an energy density close to that of potassium ion batteries and a comparable power density of supercapacitors. However, the rosy scenario is compromised by the sluggish kinetics in the PIHCs device. Herein, the kinetics enhanced nitrogen‐doped hierarchical porous hollow carbon spheres (NHCS) are synthesized and successfully applied to PIHCs. As for the K half‐cell, NHCS anchored with sodium alginate delivers excellent electrochemical performance. Further evaluation shows that the binder can significantly affect the potassium storage performance of NHCS by adjusting the coatability and ionic conductivity of the NHCS anode. Moreover, kinetic analysis and density functional theory calculations reveal the origin of the superior electrochemical properties of NHCS. As expected, an advanced PIHC device is assembled with a NHCS anode and an activated NHCS cathode, demonstrating an exceptionally high energy/power density (114.2 Wh kg^?1 and 8203 W kg^?1), along with a long‐life capability. The successful construction of high‐performance PIHCs in this work opens a new avenue for the development and application of PIHCs in the future.     

Ultrathin Mesoporous NiCo2O4 Nanosheets Supported on Ni Foam as Advanced Electrodes for Supercapacitors

A facile two‐step method is developed for large‐scale growth of ultrathin mesoporous nickel cobaltite (NiCo₂O₄) nanosheets on conductive nickel foam with robust adhesion as a high‐performance electrode for electrochemical capacitors. The synthesis involves the co‐electrodeposition of a bimetallic (Ni, Co) hydroxide precursor on a Ni foam support and subsequent thermal transformation to spinel mesoporous NiCo₂O₄. The as‐prepared ultrathin NiCo₂O₄ nanosheets with the thickness of a few nanometers possess many interparticle mesopores with a size range from 2 to 5 nm. The nickel foam supported ultrathin mesoporous NiCo₂O₄ nanosheets promise fast electron and ion transport, large electroactive surface area, and excellent structural stability. As a result, superior pseudocapacitive performance is achieved with an ultrahigh specific capacitance of 1450 F g^?1, even at a very high current density of 20 A g^?1, and excellent cycling performance at high rates, suggesting its promising application as an efficient electrode for electrochemical capacitors.     

Flexible Films Derived from Electrospun Carbon Nanofibers Incorporated with Co3O4 Hollow Nanoparticles as Self‐Supported Electrodes for Electrochemical Capacitors

Flexible porous films are prepared from electrospun carbon nanofibers (CNFs) embedded with Co₃O₄ hollow nanoparticles (NPs) and are directly applied as self‐supported electrodes for high‐performance electrochemical capacitors. Uniform Co₃O₄ hollow NPs are well dispersed and/or embedded into each CNF with desirable electrical conductivity. These Co₃O₄‐CNFs intercross each other and form 3D hierarchical porous hybrid films. Benefiting from intriguing structural features, the unique binder‐free Co₃O₄ hollow NPs/CNF hybrid film electrodes exhibit high specific capacitance (SC), excellent rate capability and cycling stability. As an example, the flexible hybrid film with loading of 35.9 wt% Co₃O₄ delivers a SC of 556 F g^?1 at a current density of 1 A g^?1, and 403 F g^?1 even at a very high current density of 12 A g^?1. Remarkably, almost no decay in SC is found after continuous charge/discharge cycling for 2000 cycles at 4 A g^?1. This exceptional electrochemical performance makes such novel self‐supported Co₃O₄‐CNFs hybrid films attractive for high‐performance electrochemical capacitors.     

MoSe2‐Covered N,P‐Doped Carbon Nanosheets as a Long‐Life and High‐Rate Anode Material for Sodium‐Ion Batteries

MoSe₂ grown on N,P‐co‐doped carbon nanosheets is synthesized by a solvothermal reaction followed with a high‐temperature calcination. This composite has an interlayer spacing of MoSe₂ expanded to facilitate sodium‐ion diffusion, MoSe₂ immobilized on carbon nanosheets to improve charge‐transfer kinetics, and N and P incorporated into carbon to enhance its interaction with active species upon cycling. These features greatly improve the electrochemical performance of this composite, as compared to all the controls. It presents a specific capacity of 378 mAh g^?1 after 1000 cycles at 0.5 A g^?1, corresponding to 87% of the capacity at the second cycle. Ex situ Raman spectra and high‐resolution transmission electron microscopy images confirm that it is element Se, rather than MoSe₂, formed after the charging process. The interaction of the active species with modified carbon is simulated using density functional theory to explain this excellent stability. The superior rate capability, where the capacity at 15 A g^?1 equals ≈55% of that at 0.5 A g^?1, could be associated with the significant contribution of pseudocapacitance. By pairing with homemade Na₃V₂(PO₄)₃/C, this composite also exhibits excellent performances in full cells.     

Besides the Capacitive and Diffusion Control: Inner-Surface Controlled Bismuth Based Electrode Facilitating Potassium-Ion Energy Storage

One of the major challenges of potassium-ion hybrid capacitors (PIHCs) is to explore favorable anode materials with fast reaction kinetics to match the cathodes. Here, an “inner-surface” controlled electrochemistry mechanism based on bismuth electrode is proposed and in-depth studied, which is different from the capacitive or diffusion controlled electrode. Such inner-surface controlled electrochemistry performance gives a high K ion diffusion ability under not only room temperature (RT) but also low temperature (LT). In this study, a kind of conjunct-like bismuth nanoparticle (CBN) is fabricated to model such an advantage. The CBN anode for PIBs displays ultra-long cycling stability and excellent rate capability, especially with a reversible capacity of 212.9 mAh g⁻¹ at 30 A g⁻¹ after 5000 cycles under RT. At −20 °C, the CBN anode achieves a capacity of 191.9 mAh g⁻¹ at 10 A g⁻¹ after 10 000 cycles. Coupling with activate carbon cathode, the as-assembled PIHCs deliver high energy/power densities (111.8 Wh kg⁻¹/412.8 W kg⁻¹ and 29 Wh kg⁻¹/14 312.6 W kg⁻¹), which outperforms those of previously reported PIHCs and other hybrid capacitors. The study provides a new understanding of the energy storage mechanism for bismuth-based electrodes and accelerates the development of advancing potassium ion storage devices, especially at LT.     

Designing 3D Biomorphic Nitrogen‐Doped MoSe2/Graphene Composites toward High‐Performance Potassium‐Ion Capacitors

Potassium‐ion hybrid capacitors (KICs) reconciling the advantages of batteries and supercapacitors have stimulated growing attention for practical energy storage because of the high abundance and low cost of potassium sources. Nevertheless, daunting challenge remains for developing high‐performance potassium accommodation materials due to the large radius of potassium ions. Molybdenum diselenide (MoSe₂) has recently been recognized as a promising anode material for potassium‐ion batteries, achieving high capacity and favorable cycling stability. However, KICs based on MoSe₂ are scarcely demonstrated by far. Herein, a diatomite‐templated synthetic strategy is devised to fabricate nitrogen‐doped MoSe₂/graphene (N‐MoSe₂/G) composites with favorable pseudocapacitive potassium storage targeting a superior anode material for KICs. Benefiting from the unique biomorphic structure, high electron/K‐ion conductivity, enriched active sites, and the conspicuous pseudocapacitive effect of N‐MoSe₂/G, thus‐derived KIC full‐cell manifests high energy/power densities (maximum 119 Wh kg^?1/7212 W kg^?1), outperforming those of recently reported KIC counterparts. Furthermore, the potassium storage mechanism of N‐MoSe₂/G composite is systematically explored with the aid of first‐principles calculations in combination of in situ X‐ray diffraction and ex situ Raman spectroscopy/transmission electron microscopy/X‐ray photoelectron spectroscopy.     

Electrochemical Mechanism Investigation of Cu2MoS4 Hollow Nanospheres for Fast and Stable Sodium Ion Storage

Sodium ion batteries (SIBs) are promising alternatives to lithium ion batteries with advantages of cost effectiveness. Metal sulfides as emerging SIB anodes have relatively high electronic conductivity and high theoretical capacity, however, large volume change during electrochemical testing often leads to unsatisfactory electrochemical performance. Herein bimetallic sulfide Cu₂MoS₄ (CMS) with layered crystal structures are prepared with glucose addition (CMS1), resulting in the formation of hollow nanospheres that endow large interlayer spacing, benefitting the rate performance and cycling stability. The electrochemical mechanisms of CMS1 are investigated using ex situ X‐ray photoelectron spectroscopy and in situ X‐ray absorption spectroscopy, revealing the conversion‐based mechanism in carbonate electrolyte and intercalation‐based mechanism in ether‐electrolyte, thus allowing fast and reversible Na⁺ storage. With further introduction of reduced graphene oxide (rGO), CMS1–rGO composites are obtained, maintaining the hollow structure of CMS1. CMS1–rGO delivers excellent rate performance (258 mAh g^?1 at 50 mA g^?1 and 131.9 mAh g^?1 at 5000 mA g^?1) and notably enhanced cycling stability (95.6% after 2000 cycles). A full cell SIB is assembled by coupling CMS1–rGO with Na₃V₂(PO₄)₃‐based cathode, delivering excellent cycling stability (75.5% after 500 cycles). The excellent rate performance and cycling stability emphasize the advantage of CMS1–rGO toward advanced SIB full cells assembly.     

Temperature‐Mediated Engineering of Graphdiyne Framework Enabling High‐Performance Potassium Storage

Graphdiyne (GDY), an emerging type of carbon allotropes, possesses fascinating electrical, chemical, and mechanical properties to readily spark energy applications in the realm of Li‐ion and Na‐ion batteries. Nevertheless, rational design of GDY architectures targeting advanced K‐ion storage has rarely been reported to date. Herein, the first example of synthesizing GDY frameworks in a scalable fashion to realize superb potassium storage for high‐performance K‐ion battery (KIB) anodes is showcased. To begin with, first principles calculations provide theoretical guidances for analyzing the intrinsic potassium storage capability of GDY. Meanwhile, the specific capacity is predicted to be as high as 620 mAh g^?1, which is considerably augmented as compared with graphite (278 mAh g^?1). Experimental tests then reveal that prepared GDY framework indeed harvests excellent electrochemical performance as a KIB anode, achieving high specific capacity (≈505 mAh g^?1 at 50 mA g^?1), outstanding rate performance (150 mAh g^?1 at 5000 mA g^?1) and favorable cycling stability (a high capacity retention of over 90% after 2000 cycles at 1000 mA g^?1). Furthermore, kinetic analysis reveals that capacitive effect mainly accounts for the K‐ion storage, with operando Raman spectroscopy/ex situ X‐ray photoelectron spectroscopy identifying good electrochemical reversibility of GDY.     

Metal–Organic Framework (MOF) Derived Electrodes with Robust and Fast Lithium Storage for Li‐Ion Hybrid Capacitors

Hybrid metal–organic frameworks (MOFs) demonstrate great promise as ideal electrode materials for energy‐related applications. Herein, a well‐organized interleaved composite of graphene‐like nanosheets embedded with MnO₂ nanoparticles (MnO₂@C‐NS) using a manganese‐based MOF and employed as a promising anode material for Li‐ion hybrid capacitor (LIHC) is engineered. This unique hybrid architecture shows intriguing electrochemical properties including high reversible specific capacity 1054 mAh g^?1 (close to the theoretical capacity of MnO₂, 1232 mAh g^?1) at 0.1 A g^?1 with remarkable rate capability and cyclic stability (90% over 1000 cycles). Such a remarkable performance may be assigned to the hierarchical porous ultrathin carbon nanosheets and tightly attached MnO₂ nanoparticles, which provide structural stability and low contact resistance during repetitive lithiation/delithiation processes. Moreover, a novel LIHC is assembled using a MnO₂@C‐NS anode and MOF derived ultrathin nanoporous carbon nanosheets (derived from other potassium‐based MOFs) cathode materials. The LIHC full‐cell delivers an ultrahigh specific energy of 166 Wh kg^?1 at 550 W kg^?1 and maintained to 49.2 Wh kg^?1 even at high specific power of 3.5 kW kg^?1 as well as long cycling stability (91% over 5000 cycles). This work opens new opportunities for designing advanced MOF derived electrodes for next‐generation energy storage devices.     

LiFePO4 Particles Embedded in Fast Bifunctional Conductor rGO&C@Li3V2(PO4)3 Nanosheets as Cathodes for High‐Performance Li‐Ion Hybrid Capacitors

The sluggish kinetics of Faradaic reactions in bulk electrodes is a significant obstacle to achieve high energy and power density in energy storage devices. Herein, a composite of LiFePO₄ particles trapped in fast bifunctional conductor rGO&C@Li₃V₂(PO₄)₃ nanosheets is prepared through an in situ competitive redox reaction. The composite exhibits extraordinary rate capability (71 mAh g^?1 at 15 A g^?1) and remarkable cycling stability (0.03% decay per cycle over 1000 cycles at 10 A g^?1). Improved extrinsic pseudocapacitive contribution is the origin of fast kinetics, which endows this composite with high energy and power density, since the unique 2D nanosheets and embedded ultrafine LiFePO₄ nanoparticles can shorten the ion and electron diffusion length. Even applied to Li‐ion hybrid capacitors, the obtained devices still achieve high power density of 3.36 kW kg^?1 along with high energy density up to 77.8 Wh kg^?1. Density functional theory computations also validate that the remarkable rate performance is facilitated by the desirable ionic and electronic conductivity of the composite.     

All‐Solid‐State Asymmetric Supercapacitors with Metal Selenides Electrodes and Ionic Conductive Composites Electrolytes

All‐solid‐state flexible asymmetric supercapacitors (ASCs) are developed by utilization of graphene nanoribbon (GNR)/Co_0.85Se composites as the positive electrode, GNR/Bi₂Se₃ composites as the negative electrode, and polymer‐grafted‐graphene oxide membranes as solid‐state electrolytes. Both GNR/Co_0.85Se and GNR/Bi₂Se₃ composite electrodes are developed by a facile one‐step hydrothermal growth method from graphene oxide nanoribbons as the nucleation framework. The GNR/Co_0.85Se composite electrode exhibits a specific capacity of 76.4 mAh g^?1 at a current density of 1 A g^?1 and the GNR/Bi₂Se₃ composite electrode exhibits a specific capacity of 100.2 mAh g^?1 at a current density of 0.5 A g^?1. Moreover, the stretchable membrane solid‐state electrolytes exhibit superior ionic conductivity of 108.7 mS cm^?1. As a result, the flexible ASCs demonstrate an operating voltage of 1.6 V, an energy density of 30.9 Wh kg^?1 at the power density of 559 W kg^?1, and excellent cycling stability with 89% capacitance retention after 5000 cycles. All these results demonstrate that this study provides a simple, scalable, and efficient approach to fabricate high performance flexible all‐solid‐state ASCs for energy storage.     

Design and Synthesis of Hierarchical Nanowire Composites for Electrochemical Energy Storage

Nanocomposites of interpenetrating carbon nanotubes and vanadium pentoxide (V₂O₅) nanowires networks are synthesized via a simple in situ hydrothermal process. These fibrous nanocomposites are hierarchically porous with high surface area and good electric conductivity, which makes them excellent material candidates for supercapacitors with high energy density and power density. Nanocomposites with a capacitance up to 440 and 200 F g^?1 are achieved at current densities of 0.25 and 10 A g^?1, respectively. Asymmetric devices based on these nanocomposites and aqueous electrolyte exhibit an excellent charge/discharge capability, and high energy densities of 16 W h kg^?1 at a power density of 75 W kg^?1 and 5.5 W h kg^?1 at a high power density of 3 750 W kg^?1. This performance is a significant improvement over current electrochemical capacitors and is highly competetive with Ni–MH batteries. This work provides a new platform for high‐density electrical‐energy storage for electric vehicles and other applications.     

Molecular Design of Mesoporous NiCo2O4 and NiCo2S4 with Sub‐Micrometer‐Polyhedron Architectures for Efficient Pseudocapacitive Energy Storage

Spinel‐type NiCo₂O₄ (NCO) and NiCo₂S₄ (NCS) polyhedron architectures with sizes of 500–600 nm and rich mesopores with diameters of 1–2 nm are prepared facilely by the molecular design of Ni and Co into polyhedron‐shaped zeolitic imidazolate frameworks as solid precursors. Both as‐prepared NCO and NCS nanostructures exhibit excellent pseudocapacitance and stability as electrodes in supercapacitors. In particular, the exchange of O^2? in the lattice of NCO with S^2? obviously improves the electrochemical performance. NCS shows a highly attractive capacitance of 1296 F g^?1 at a current density of 1 A g^?1, ultrahigh rate capability with 93.2% capacitance retention at 10 A g^?1, and excellent cycling stability with a capacitance retention of 94.5% after cycling at 1 A g^?1 for 6000 times. The asymmetric supercapacitor with an NCS negative electrode and an active carbon positive electrode delivers a very attractive energy density of 44.8 Wh kg^?1 at power density 794.5 W kg^?1, and a favorable energy density of 37.7 Wh kg^?1 is still achieved at a high power density of 7981.1 W kg^?1. The specific mesoporous polyhedron architecture contributes significantly to the outstanding electrochemical performances of both NCO and NCS for capacitive energy storage.     

Layered P2‐Type K0.65Fe0.5Mn0.5O2 Microspheres as Superior Cathode for High‐Energy Potassium‐Ion Batteries

Potassium‐ion batteries have been regarded as the potential alternatives to lithium‐ion batteries (LIBs) due to the low cost, earth abundance, and low potential of K (?2.936 vs standard hydrogen electrode (SHE)). However, the lack of low‐cost cathodes with high energy density and long cycle life always limits its application. In this work, high‐energy layered P2‐type hierarchical K_0.65Fe_0.5Mn_0.5O₂ (P2‐KFMO) microspheres, assembled by the primary nanoparticles, are fabricated via a modified solvent‐thermal method. Benefiting from the unique microspheres with primary nanoparticles, the K⁺ intercalation/deintercalation kinetics of P2‐KFMO is greatly enhanced with a stabilized cathodic electrolyte interphase on the cathode. The P2‐KFMO microsphere presents a highly reversible potassium storage capacity of 151 mAh g^?1 at 20 mA g^?1, fast rate capability of 103 mAh g^?1 at 100 mA g^?1, and long cycling stability with 78% capacity retention after 350 cycles. A full cell with P2‐KFMO microspheres as cathode and hard carbon as anode is constructed, which exhibits long‐term cycling stability (>80% of retention after 100 cycles). The present high‐performance P2‐KFMO microsphere cathode synthesized using earth‐abundant elements provides a new cost‐effective alternative to LIBs for large‐scale energy storage.     

Electrochemically Derived Graphene‐Like Carbon Film as a Superb Substrate for High‐Performance Aqueous Zn‐Ion Batteries

3D graphene, as a light substrate for active loadings, is essential to achieve high energy density for aqueous Zn‐ion batteries, yet traditional synthesis routes are inefficient with high energy consumption. Reported here is a simplified procedure to transform the raw graphite paper directly into the graphene‐like carbon film (GCF). The electrochemically derived GCF contains a 2D–3D hybrid network with interconnected graphene sheets, and offers a highly porous structure. To realize high energy density, the Na:MnO₂/GCF cathode and Zn/GCF anode are fabricated by electrochemical deposition. The GCF‐based Zn‐ion batteries deliver a high initial discharge capacity of 381.8 mA h g^?1 at 100 mA g^?1 and a reversible capacity of 188.0 mA h g^?1 after 1000 cycles at 1000 mA g^?1. Moreover, a recorded energy density of 511.9 Wh kg^?1 is obtained at a power density of 137 W kg^?1. The electrochemical kinetics measurement reveals the high capacitive contribution of the GCF and a co‐insertion/desertion mechanism of H⁺ and Zn²⁺ ions. First‐principles calculations are also carried out to investigate the effect of Na⁺ doping on the electrochemical performance of layered δ‐MnO₂ cathodes. The results demonstrate the attractive potential of the GCF substrate in the application of the rechargeable batteries.     

Bamboo‐Like Hollow Tubes with MoS2/N‐Doped‐C Interfaces Boost Potassium‐Ion Storage

Potassium‐ion batteries (KIBs) are new‐concept of low‐cost secondary batteries, but the sluggish kinetics and huge volume expansion during cycling, both rooted in the size of large K ions, lead to poor electrochemical behavior. Here, a bamboo‐like MoS₂/N‐doped‐C hollow tubes are presented with an expanded interlayer distance of 10 Å as a high‐capacity and stable anode material for KIBs. The bamboo‐like structure provides gaps along axial direction in addition to inner cylinder hollow space to mitigate the strains in both radial and vertical directions that ultimately leads to a high structural integrity for stable long‐term cycling. Apart from being a constituent of the interstratified structure the N‐doped‐C layers weave a cage to hold the potassiation products (polysulfide and the Mo nanoparticles) together, thereby effectively hindering the continuing growth of solid electrolyte interphase in the interior of particles. The density functional theory calculations prove that the MoS₂/N‐doped‐C atomic interface can provide an additional attraction toward potassium ion. As a result, it delivers a high capacity at a low current density (330 mAh g^?1 at 50 mA g^?1 after 50 cycles) and a high‐capacity retention at a high current density (151 mAh g^?1 at 500 mA g^?1 after 1000 cycles).     

A New Strategy to Effectively Suppress the Initial Capacity Fading of Iron Oxides by Reacting with LiBH4

In this work, a new facile and scalable strategy to effectively suppress the initial capacity fading of iron oxides is demonstrated by reacting with lithium borohydride (LiBH₄) to form a B‐containing nanocomposite. Multielement, multiphase B‐containing iron oxide nanocomposites are successfully prepared by ball‐milling Fe₂O₃ with LiBH₄, followed by a thermochemical reaction at 25–350 °C. The resulting products exhibit a remarkably superior electrochemical performance as anode materials for Li‐ion batteries (LIBs), including a high reversible capacity, good rate capability, and long cycling durability. When cycling is conducted at 100 mA g^?1, the sample prepared from Fe₂O₃–0.2LiBH₄ delivers an initial discharge capacity of 1387 mAh g^?1. After 200 cycles, the reversible capacity remains at 1148 mAh g^?1, which is significantly higher than that of pristine Fe₂O₃ (525 mAh g^?1) and Fe₃O₄ (552 mAh g^?1). At 2000 mA g^?1, a reversible capacity as high as 660 mAh g^?1 is obtained for the B‐containing nanocomposite. The remarkably improved electrochemical lithium storage performance can mainly be attributed to the enhanced surface reactivity, increased Li⁺ ion diffusivity, stabilized solid‐electrolyte interphase (SEI) film, and depressed particle pulverization and fracture, as measured by a series of compositional, structural, and electrochemical techniques.     

Li‐CO2 Batteries Efficiently Working at Ultra‐Low Temperatures

Lithium‐carbon dioxide (Li‐CO₂) batteries are considered promising energy‐storage systems in extreme environments with ultra‐high CO₂ concentrations, such as Mars with 96% CO₂ in the atmosphere, due to their potentially high specific energy densities. However, besides having ultra‐high CO₂ concentration, another vital but seemingly overlooked fact lies in that Mars is an extremely cold planet with an average temperature of approximately ?60 °C. The existing Li‐CO₂ batteries could work at room temperature or higher, but they will face severe performance degradation or even a complete failure once the ambient temperature falls below 0 °C. Herein, ultra‐low‐temperature Li‐CO₂ batteries are demonstrated by designing 1,3‐dioxolane‐based electrolyte and iridium‐based cathode, which show both a high deep discharge capacity of 8976 mAh g^?1 and a long lifespan of 150 cycles (1500 h) with a fixed 500 mAh g^?1 capacity per cycle at ?60 °C. The easy‐to‐decompose discharge products in small size on the cathode and the suppressed parasitic reactions both in the electrolyte and on the Li anode at low temperatures together contribute to the above high electrochemical performances.     

Self‐Established Rapid Magnesiation/De‐Magnesiation Pathways in Binary Selenium–Copper Mixtures with Significantly Enhanced Mg‐Ion Storage Reversibility

Rechargeable magnesium/sulfur (Mg/S) and magnesium/selenium (Mg/Se) batteries are characterized by high energy density, inherent safety, and economical effectiveness, and therefore, are of great scientific and technological interest. However, elusive challenges, including the limited charge storage capacity, low Coulombic efficiency, and short cycle life, have been encountered due to the sluggish electrochemical kinetics and severe shuttles of ploysulfides (polyselenide). Taking selenium as model paradigm, a new and reliable Mg‐Se chemistry is proposed through designing binary selenium‐copper (Se‐Cu) cathodes. An intriguing effect of Cu powders on the electrochemical reaction pathways of the active Se microparticles is revealed in a way of forming Cu₃Se₂ intermediates, which induces an unconventional yet reversible two‐stage magnesiation mechanism: Mg‐ions first insert into Cu₃Se₂ phases; in a second step Cu‐ions in the Mg_2xCu₃Se₂ lattice exchange with Mg‐ions. As expected, binary Se‐Cu electrodes show significantly improved reversibility and elongated cycle life. More bracingly, Se/C nanostructures fabricated by facile blade coating Se nanorodes onto copper foils exhibit high output power and capacity (696.0 mAh g^?1 at 67.9 mA g^?1), which outperforms all previously reported Mg/Se batteries. This work envisions a facile and reliable strategy to achieve better reversibility and long‐term durability of selenium (sulfur) electrodes.     

Atomic Sulfur Covalently Engineered Interlayers of Ti3C2 MXene for Ultra‐Fast Sodium‐Ion Storage by Enhanced Pseudocapacitance

2D MXenes have been widely applied in the field of electrochemical energy storage owning to their high electrical conductivity and large redox‐active surface area. However, electrodes made from multilayered MXene with small interlayer spacing exhibit sluggish kinetics with low capacity for sodium‐ion storage. Herein, Ti₃C₂ MXene with expanded and engineered interlayer spacing for excellent storage capability is demonstrated. After cetyltrimethylammonium bromide pretreatment, S atoms are successfully intercalated into the interlayer of Ti₃C₂ to form a desirable interlayer‐expanded structure via Ti? S bonding, while pristine Ti₃C₂ is hardly to be intercalated. When the annealing temperature is 450 °C, the S atoms intercalated Ti₃C₂ (CT‐S@Ti₃C₂‐450) electrode delivers the improved Na‐ion capacity of 550 mAh g^?1 at 0.1 A g^?1 (≈120 mAh g^?1 at 15 A g^?1, the best MXene‐based Na⁺‐storage rate performance reported so far), and excellent cycling stability over 5000 cycles at 10 A g^?1 by enhanced pseudocapacitance. The enhanced sodium‐ion storage capability has also been verified by theoretical calculations and kinetic analysis. Coupling the CT‐S@Ti₃C₂‐450 anode with commercial AC cathode, the assembled Na⁺ capacitor delivers high energy density (263.2 Wh kg^?1) under high power density (8240 W kg^?1), and outstanding cycling performance.