A Free‐Standing and Ultralong‐Life Lithium‐Selenium Battery Cathode Enabled by 3D Mesoporous Carbon/Graphene Hierarchical Architecture

High capacity cathode materials for long‐life rechargeable lithium batteries are urgently needed. Selenium cathode has recently attracted great research attention due to its comparable volumetric capacity to but much better electrical conductivity than widely studied sulfur cathode. However, selenium cathode faces similar issues as sulfur (i.e., shuttling of polyselenides, volumetric expansion) and high performance lithium‐selenium batteries (Li–Se) have not yet been demonstrated at selenium loading >60% in the electrode. In this work, a 3D mesoporous carbon nanoparticles and graphene hierarchical architecture to storage selenium as binder‐free cathode material (Se/MCN‐RGO) for high energy and long life Li–Se batteries is presented. Such architecture not only provides the electrode with excellent electrical and ionic conductivity, but also efficiently suppresses polyselenides shuttling and accommodates volume change during charge/discharge. At selenium content of 62% in the entire cathode, the free‐standing Se/MCN‐RGO exhibits high discharge capacity of 655 mAh g^?1 at 0.1 C (97% of theoretical capacity) and long cycling stability with a very small capacity decay of 0.008% per cycle over 1300 cycles at 1 C. The present report demonstrates significant progress in the development of high capacity cathode materials for long‐life Li batteries and flexible energy storage device.     

Nitrogen‐Doped Graphene Ribbon Assembled Core–Sheath MnO@Graphene Scrolls as Hierarchically Ordered 3D Porous Electrodes for Fast and Durable Lithium Storage

Graphene scroll is an emerging 1D tubular form of graphitic carbon that has potential applications in electrochemical energy storage. However, it still remains a challenge to composite graphene scrolls with other nanomaterials for building advanced electrode configuration with fast and durable lithium storage properties. Here, a transition‐metal‐oxide‐based hierarchically ordered 3D porous electrode is designed based on assembling 1D core–sheath MnO@N‐doped graphene scrolls with 2D N‐doped graphene ribbons. In the resulting architecture, porous MnO nanowires confined in tubular graphene scrolls are mechanically isolated but electronically well‐connected, while the interwoven graphene ribbons offer continuous conductive paths for electron transfer in all directions. Moreover, the elastic graphene scrolls together with enough internal voids are able to accommodate the volume expansion of the enclosed MnO. Because of these merits, the as‐built electrode manifests ultrahigh rate capability (349 mAh g^?1 at 8.0 A g^?1; 205 mAh g^?1 at 15.0 A g^?1) and robust cycling stability (812 mAh g^?1 remaining after 1000 cycles at 2.0 A g^?1) and is the most efficient MnO‐based anode ever reported for lithium‐ion batteries. This unique multidimensional and hierarchically ordered structure design is believed to hold great potential in generalizable synthesis of graphene scrolls composited with oxide nanowires for mutifuctional energy storage.     

A Bottom‐Up Approach to Build 3D Architectures from Nanosheets for Superior Lithium Storage

Two‐dimensional (2D) atomic layers such as graphene, and metal chalcogenides have recently attracted tremendous attention due to their unique properties and potential applications. Unfortunately, in most cases, the free‐standing nanosheets easily re‐stack due to their van der Waals forces, and lose the advantages of their separated atomic layer state. Here, a bottom‐up approach is developed to build three‐dimensional (3D) architectures by 2D nanosheets such as MoS₂ and graphene oxide nanosheets as building blocks, the thin nature of which can be well retained. After simply chemical reduction, the resulting 3D MoS₂‐graphene architectures possess high surface area, porous structure, thin walls and high electrical conductivity. Such unique features are favorable for the rapid diffusions of both lithium ions and electrons during lithium storage. As a consequence, MoS₂‐graphene electrodes exhibit high reversible capacity of ≈1200 mAh g^?1, with very good cycling performance. Moreover, such a simple and low‐cost assembly protocol can provide a new pathway for the large‐scale production of various functional 3D architectures for energy storage and conversions.     

Iron Oxide Nanoparticle and Graphene Nanoribbon Composite as an Anode Material for High‐Performance Li‐Ion Batteries

A composite material made of graphene nanoribbons and iron oxide nanoparticles provides a remarkable route to lithium‐ion battery anode with high specific capacity and cycle stability. At a rate of 100 mA/g, the material exhibits a high discharge capacity of ~910 mAh/g after 134 cycles, which is >90% of the theoretical li‐ion storage capacity of iron oxide. Carbon black, carbon nanotubes, and graphene flakes have been employed by researchers to achieve conductivity and stability in lithium‐ion electrode materials. Herein, the use of graphene nanoribbons as a conductive platform on which iron oxide nanoparticles are formed combines the advantages of long carbon nanotubes and flat graphene surfaces. The high capacity over prolonged cycling achieved is due to the synergy between an electrically percolating networks of conductive graphene nanoribbons and the high lithium‐ion storage capability of iron oxide nanoparticles.     

Stable Cycling of Phosphorus Anode for Sodium‐Ion Batteries through Chemical Bonding with Sulfurized Polyacrylonitrile

Sodium‐ion batteries are attracting increasing interests as a promising alternative to lithium‐ion batteries due to the abundant resource and low cost of sodium. Despite phosphorus (P) has extremely high theoretical capacity of 2595 mAh g^?1, its wide application for sodium‐ion battery is highly hampered by its fast capacity fading and low Coulombic efficiency as a result of large volume change upon cycling. Herein, a robust phosphorus anode with long cycle life for sodium‐ion battery via hybridization with functional conductive polymer is presented. To this end, the polyacrylonitrile is first dehydrogenated by sulfur via a facile thermal treatment, forming a conductive main chain embedded with C–S–S moieties. This functional conductive polymer enables the formation of P? S bonds between phosphorus and functional conductive matrix, leading to a robust electrode that can accommodate the large volume change upon substantial volume change in cycling. Consequently, this hybrid anode delivers a high capacity of ≈1300 mAh g^?1 at a current density of 520 mA g^?1 with high Coulombic efficiency (>99%) and good cycling performance (91% capacity retention after 100 cycles).     

Ever‐Increasing Pseudocapacitance in RGO–MnO–RGO Sandwich Nanostructures for Ultrahigh‐Rate Lithium Storage

Lithium ion batteries have attained great success in commercialization owing to their high energy density. However, the relatively delaying discharge/charge severely hinders their high power applications due to intrinsically diffusion‐controlled lithium storage of the electrode. This study demonstrates an ever‐increasing surface redox capacitive lithium storage originating from an unique microstructure evolution during cycling in a novel RGO–MnO–RGO sandwich nanostructure. Such surface pseudocapacitance is dynamically in equilibrium with diffusion‐controlled lithium storage, thereby achieving an unprecedented rate capability (331.9 mAh g^?1 at 40 A g^?1, 379 mAh g^?1 after 4000 cycles at 15 A g^?1) with outstanding cycle stability. The dynamic combination of surface and diffusion lithium storage of electrodes might open up possibilities for designing high‐power lithium ion batteries.     

Reconstruction of Conformal Nanoscale MnO on Graphene as a High‐Capacity and Long‐Life Anode Material for Lithium Ion Batteries

To tackle the issue of inferior cycle stability and rate capability for MnO anode materials in lithium ion batteries, a facile strategy is explored to prepare a hybrid material consisting of MnO nanocrystals grown on conductive graphene nanosheets. The prepared MnO/graphene hybrid anode exhibits a reversible capacity as high as 2014.1 mAh g^?1 after 150 discharge/charge cycles at 200 mA g^?1, excellent rate capability (625.8 mAh g^?1 at 3000 mA g^?1), and superior cyclability (843.3 mAh g^?1 even after 400 discharge/charge cycles at 2000 mA g^?1 with only 0.01% capacity loss per cycle). The results suggest that the reconstruction of the MnO/graphene electrodes is intrinsic due to conversion reactions. A long‐term stable nanoarchitecture of graphene‐supported ultrafine manganese oxide nanoparticles is formed upon cycling, which yields a long‐life anode material for lithium ion batteries. The lithiation and delithiation behavior suggests that the further oxidation of Mn(II ) to Mn(IV ) and the interfacial lithium storage upon cycling contribute to the enhanced specific capacity. The excellent rate capability benefits from the presence of conductive graphene and a short transportation length for both lithium ions and electrons. Moreover, the as‐formed hybrid nanostructure of MnO on graphene may help achieve faster kinetics of conversion reactions.     

Ultrathin Layered Hydroxide Cobalt Acetate Nanoplates Face‐to‐Face Anchored to Graphene Nanosheets for High‐Efficiency Lithium Storage

The dramatically increasing demand of high‐energy lithium‐ion batteries (LIBs) urgently requires advanced substitution for graphite‐based anodes. Herein, inspired from the extra capacity of lithium storage in solid‐electrolyte interface (SEI) films, layered hydroxide cobalt acetates (LHCA, Co(Ac)_0.48(OH)_1.52·0.55H₂O) are introduced as novel and high‐efficiency anode materials. Furthermore, ultrathin LHCA nanoplates are face‐to‐face anchored on the surface of graphene nanosheets (GNS) through a facile solvothermal method to improve the electronic transport and avoid agglomeration during repeated cycles. Profiting from the parallel structure, LHCA//GNS nanosheets exhibit extraordinary long‐term and high‐rate performance. At the current densities of 1000 and 4000 mA g^?1, the reversible capacities maintain ≈1050 mAh g^?1 after 200 cycles and ≈780 mAh g^?1 after 300 cycles, respectively, much higher than the theoretical value of LHCA according to the conversion mechanism. Fourier transform infrared spectroscopy confirms the conversion from acetate to acetaldehyde after lithiation. A reasonable mechanism is proposed to elucidate the lithium storage behaviors referring to the electrocatalytic conversion of OH groups with Co nanocatalysts. This work can help further understand the contribution of SEI components (especially LiOH and LiAc) to lithium storage. It is envisaged that layered transition metal hydroxides can be used as advanced materials for energy storage devices.     

Nickel‐Catalyzed Synthesis of 3D Edge‐Curled Graphene for High‐Performance Lithium‐Ion Batteries

Effectively preventing graphene stacking and maintaining ultrathin layers remains a significant research effort for graphene preparation and applications. In this paper, a novel synthetic strategy based on catalyst migration on the surface of a salt template to control the growth of graphene is used to prepare 3D edge‐curled graphene (3D ECG). Under the synergistic effect of the steric hindrance and the migration of the Ni catalyst, 3D ECG forms a special structure in which the intermediate portion is flat and the edge is curled. The resultant unique structure not only effectively prevents the close stacking and aggregation of graphene, but also significantly improves its lithium storage performance. As an anode for lithium ion batteries, the reversible specific capacity can reach 907.5 and 347.8 mAh g^?1 at the current density of 0.05 and 5.0 A g^?1. Even after 1000 cycles, the specific capacity of 3D ECG can still be maintained at 605.2 mAh g^?1 at a current density of 0.5 A g^?1, demonstrating excellent rate performance and cycle performance. This new synthesis strategy and unique edge‐curled structure can be used to guide more design of 3D graphene materials for further functional applications.     

Freestanding Metallic 1T MoS2 with Dual Ion Diffusion Paths as High Rate Anode for Sodium‐Ion Batteries

This work studies for the first time the metallic 1T MoS₂ sandwich grown on graphene tube as a freestanding intercalation anode for promising sodium‐ion batteries (SIBs). Sodium is earth‐abundant and readily accessible. Compared to lithium, the main challenge of sodium‐ion batteries is its sluggish ion diffusion kinetic. The freestanding, porous, hollow structure of the electrode allows maximum electrolyte accessibility to benefit the transportation of Na⁺ ions. Meanwhile, the metallic MoS₂ provides excellent electron conductivity. The obtained 1T MoS₂ electrode exhibits excellent electrochemical performance: a high reversible capacity of 313 mAh g^?1 at a current density of 0.05 A g^?1 after 200 cycles and a high rate capability of 175 mAh g^?1 at 2 A g^?1. The underlying mechanism of high rate performance of 1T MoS₂ for SIBs is the high electrical conductivity and excellent ion accessibility. This study sheds light on using the 1T MoS₂ as a novel anode for SIBs.     

Lithium Ion Breathable Electrodes with 3D Hierarchical Architecture for Ultrastable and High‐Capacity Lithium Storage

Transition‐metal oxides show genuine potential in replacing state‐of‐the‐art carbonaceous anode materials in lithium‐ or sodium‐ion batteries because of their much higher theoretical capacity. However, they usually undergo massive volume change, which leads to numerous problems in both material and electrode levels, such as material pulverization, instable solid‐electrolyte interphase, and electrode failure. Here, it is demonstrated that lithium‐ion breathable hybrid electrodes with 3D architecture tackle all these problems, using a typical conversion‐type transition‐metal oxide, Fe₃O₄, of which nanoparticles are anchored onto 3D current collectors of Ni nanotube arrays (NTAs) and encapsulated by δ‐MnO₂ layers (Ni/Fe₃O₄@MnO₂). The δ‐MnO₂ layers reversibly switch lithium insertion/extraction of internal Fe₃O₄ nanoparticles and protect them against pulverizing and detaching from NTA current collectors, securing exceptional integrity retention and efficient ion/electron transport. The Ni/Fe₃O₄@MnO₂ electrodes exhibit superior cyclability and high‐capacity lithium storage (retaining ≈1450 mAh g^?1, ≈96% of initial value at 1 C rate after 1000 cycles).     

Facile Solid‐State Growth of 3D Well‐Interconnected Nitrogen‐Rich Carbon Nanotube–Graphene Hybrid Architectures for Lithium–Sulfur Batteries

Constructing 3D carbon structures built from carbon nanotubes (CNTs) and graphene has been considered as an effective approach to achieve superior properties in energy conversion and storage because of the synergistic combination of the advantages of each building block. Herein, a facile solid‐state growth strategy is reported for the first time to fabricate highly nitrogen doped CNT–graphene 3D nanostructures without the necessity to use chemical vapor deposition. As cathode hosts for lithium–sulfur batteries, the hybrid architectures exhibit reversible capacities of 1314 and 922 mAh g^?1 at 0.2 and 1 C, respectively, and a capacity retention of 97% after 200 cycles at a high rate of 2 C, revealing their great potential for energy storage application.     

Regulation of Breathing CuO Nanoarray Electrodes for Enhanced Electrochemical Sodium Storage

Cupric oxide (CuO) represents an attractive anode material for sodium‐ion batteries owing to its large capacity (674 mAh g^?1) associated with multiple electron transfer. However, the substantial volume swelling and shrinking (≈170%) upon Na uptake and release, which mimics an electrode breathing process, disturbs the structural integrity, leading to poor electrochemical durability and low Coulombic efficiency. Here, a structural strategy to regulate the breathing of CuO nanoarray electrodes during Na cycling using an atomic layer deposition of cohesive TiO₂ thin films is presented. CuO nanoarrays are electrochemically grown on 3D Cu foam and directly used as anodes for sodium storage. The regulated CuO electrode arrays enable a large reversible capacity (592 mAh g^?1), a high cycle efficiency (≈100%), and an excellent cycling stability (82% over 1000 cycles), which are some of the best sodium storage performance values reported for CuO systems. Electrochemical impedance and microscopic examination reveal that the enhanced performance is a direct outcome of the efficient regulation of the breathing of CuO nanowires by TiO₂ layer.     

Densified Metallic MoS2/Graphene Enabling Fast Potassium‐Ion Storage with Superior Gravimetric and Volumetric Capacities

The potassium‐ion battery (PIB) is an attractive energy storage device that possesses the potential advantages of high energy density and low cost. Herein, a pure 1T‐MoS₂ is synthesized on graphene oxide and assembled into a hydrogel. The hydrogel is further tightened to a compact 1T‐MoS₂/graphene (CTMG) bulk by a densifying strategy of capillary tension. When employed as an anode for PIBs, the CTMG electrode can store K⁺ through reversible intercalation and conversion electrochemistry, accompanied with fast kinetics since the 1T‐MoS₂ induces a pseudocapacitive storage mechanism and the extraordinary K⁺ transportation ability. Consequently, the CTMG electrode delivers the high and reversible rate capacities of 511 and 327 mAh g^‐1 at 0.1 and 1 A g^‐1, respectively. Moreover, the compact architecture reduces the electrode thickness by ≈33% enabling a high volumetric capacity (512 mAh cm^‐3 at 0.1 A g^‐1 after 100 cycles), as well as holding a promising application in thick electrode.     

Catalytic Conversion of Polysulfides on Single Atom Zinc Implanted MXene toward High‐Rate Lithium–Sulfur Batteries

Although lithium–sulfur (Li–S) batteries are one of the most promising energy storage devices owing to their high energy densities, the sluggish reaction kinetics and severe shuttle effect of the sulfur cathodes hinder their practical applications. Here, single atom zinc implanted MXene is introduced into a sulfur cathode, which can not only catalyze the conversion reactions of polysulfides by decreasing the energy barriers from Li₂S₄ to Li₂S₂/Li₂S but also achieve strong interaction with polysulfides due to the high electronegativity of atomic zinc on MXene. Moreover, it is found that the homogenously dispersed zinc atoms can also accelerate the nucleation of Li₂S₂/Li₂S on MXene layers during the redox reactions. As a result, the sulfur cathode with single atom zinc implanted MXene exhibits a high reversible capacity of 1136 mAh g^?1. After electrode optimization, a high areal capacity of 5.3 mAh cm^?2, high rate capability of 640 mAh g^?1 at 6 C, and good cycle stability (80% capacity retention after 200 cycles at 4 C) can be achieved.     

Amorphous GaN@Cu Freestanding Electrode for High‐Performance Li‐Ion Batteries

GaN is demonstrated to be an ideal anode for Li‐ion batteries (LIBs) for the first time. Amorphous GaN@Cu nanorods (a‐GaN@Cu) freestanding electrode is designed via a low‐temperature pulsed laser deposition method, which exhibits prominent rate capability and untralong lifespan as an anode for LIBs. With porous interconnected metal nanorods substrate to improve the structure integrity and electronic conductivity, the a‐GaN@Cu electrode delivers a capacity recovery of 980 mAh g^?1 after 150 cycles from 0.25 to 6.25 A g^?1 and a high discharge capacity of 509 mAh g^?1 after 3000 cycles at 10.0 A g^?1. The lithium storage in the a‐GaN is also systematically studied, which suggests a redox reaction mechanism.     

Making Ultrafast High‐Capacity Anodes for Lithium‐Ion Batteries via Antimony Doping of Nanosized Tin Oxide/Graphene Composites

Tin oxide‐based materials attract increasing attention as anodes in lithium‐ion batteries due to their high theoretical capacity, low cost, and high abundance. Composites of such materials with a carbonaceous matrix such as graphene are particularly promising, as they can overcome the limitations of the individual materials. The fabrication of antimony‐doped tin oxide (ATO)/graphene hybrid nanocomposites is described with high reversible capacity and superior rate performance using a microwave assisted in situ synthesis in tert‐butyl alcohol. This reaction enables the growth of ultrasmall ATO nanoparticles with sizes below 3 nm on the surface of graphene, providing a composite anode material with a high electric conductivity and high structural stability. Antimony doping results in greatly increased lithium insertion rates of this conversion‐type anode and an improved cycling stability, presumably due to the increased electrical conductivity. The uniform composites feature gravimetric capacity of 1226 mAh g^?1 at the charging rate 1C and still a high capacity of 577 mAh g^?1 at very high charging rates of up to 60C, as compared to 93 mAh g^?1 at 60C for the undoped composite synthesized in a similar way. At the same time, the antimony‐doped anodes demonstrate excellent stability with a capacity retention of 77% after 1000 cycles.     

A New Strategy to Build a High‐Performance P′2‐Type Cathode Material through Titanium Doping for Sodium‐Ion Batteries

Herein, Ti⁴⁺ in P′2‐Na_0.67[(Mn_0.78Fe_0.22)_0.9Ti_0.1]O₂ is proposed as a new strategy for optimization of Mn‐based cathode materials for sodium‐ion batteries, which enables a single phase reaction during de‐/sodiation. The approach is to utilize the stronger Ti–O bond in the transition metal layers that can suppress the movements of Mn–O and Fe–O by sharing the oxygen with Ti by the sequence of Mn–O–Ti–O–Fe. It delivers a discharge capacity of ≈180 mAh g^?1 over 200 cycles (86% retention), with S‐shaped smooth charge–discharge curves associated with a small volume change during cycling. The single phase reaction with a small volume change is further confirmed by operando synchrotron X‐ray diffraction. The low activation barrier energy of ≈541 meV for Na⁺ diffusion is predicted using first‐principles calculations. As a result, Na_0.67[(Mn_0.78Fe_0.22)_0.9Ti_0.1]O₂ can deliver a high reversible capacity of ≈153 mAh g^?1 even at 5C (1.3 A g^?1), which corresponds to ≈85% of the capacity at 0.1C (26 mA g^?1). The nature of the sodium storage mechanism governing the ultrahigh electrode performance in a full cell with a hard carbon anode is elucidated, revealing the excellent cyclability and good retention (≈80%) for 500 cycles (111 mAh g^?1) at 5C (1.3 A g^?1).     

A Chemically Engineered Porous Copper Matrix with Cylindrical Core–Shell Skeleton as a Stable Host for Metallic Sodium Anodes

Sodium (Na) metal is the most promising alternative for lithium metal as anode for the next‐generation energy storage systems. However, its practical implementation is hindered by the huge volume change and severe Na metal dendrite growth during electrochemical stripping/plating. Herein, the use of a chemically engineered porous copper (Cu) matrix as a stable host for metallic Na anode is presented. By treating the commercial Cu foam through a facile and cost‐effective method, a composite matrix consists of cylindrical core–shell skeleton is achieved, facilitating uniform impregnation and confinement of Na within the matrix pores promoted by the chemical interaction between Na and the matrix. The unique matrix's surface characteristic can divert the Na deposition from the skeleton towards the Na reservoirs within the pores, suppressing the volume change and mossy/dendritic Na growth. A stable Na cycling behavior is demonstrated in carbonate electrolyte without any additives at a high capacity up to 3 mAh cm^?2 with a current density up to 2 mA cm^?2. Moreover, electrochemical measurements of a full cell made of the Na composite matrix anode clearly reveal the superior performance at high rate (5C) over that using bare Na metal.     

Self‐Assembly of Flexible Free‐Standing 3D Porous MoS2‐Reduced Graphene Oxide Structure for High‐Performance Lithium‐Ion Batteries

Flexible freestanding electrodes are highly desired to realize wearable/flexible batteries as required for the design and production of flexible electronic devices. Here, the excellent electrochemical performance and inherent flexibility of atomically thin 2D MoS₂ along with the self‐assembly properties of liquid crystalline graphene oxide (LCGO) dispersion are exploited to fabricate a porous anode for high‐performance lithium ion batteries. Flexible, free‐standing MoS₂–reduced graphene oxide (MG) film with a 3D porous structure is fabricated via a facile spontaneous self‐assembly process and subsequent freeze‐drying. This is the first report of a one‐pot self‐assembly, gelation, and subsequent reduction of MoS₂/LCGO composite to form a flexible, high performance electrode for charge storage. The gelation process occurs directly in the mixed dispersion of MoS₂ and LCGO nanosheets at a low temperature (70 °C) and normal atmosphere (1 atm). The MG film with 75 wt% of MoS₂ exhibits a high reversible capacity of 800 mAh g^?1 at a current density of 100 mA g^?1. It also demonstrates excellent rate capability, and excellent cycling stability with no capacity drop over 500 charge/discharge cycles at a current density of 400 mA g^?1.