Anomalous Enhancement of Li‐O2 Battery Performance with Li2O2 Films Assisted by NiFeOx Nanofiber Catalysts: Insights into Morphology Control

It is generally understood that particle‐shaped Li₂O₂ is preferred in Li‐O₂ batteries (LOBs) because the dominance of Li₂O₂ films may lead to poor electrochemical performance. The influence of Li₂O₂ morphology and its nucleation mechanism are probed by experiments along with the first‐principle calculations. It is revealed that the LOBs with Li₂O₂ films deliver unexpectedly improved capacities, longer cycles, and significantly reduced overpotentials assisted by NiFeO_x nanofiber catalysts. The energetically favored Li 2a vacancies under LiO₂‐rich conditions, small crystallites, and large contact areas with the electrode/electrolyte explain the anomalous performance enhancement. Li₂O₂ films are formed by a heterogeneous nucleation mechanism and the voltage applied, electrolyte, electrode surface, and use of catalysts are identified as the parameters controlling the mechanisms. The mapped correlations among these parameters shed light on the control of Li₂O₂ morphology for developing high‐performance LOBs.     

A Self‐Standing and Flexible Electrode of Li4Ti5O12 Nanosheets with a N‐Doped Carbon Coating for High Rate Lithium Ion Batteries

Flexible energy‐storage devices have attracted growing attention with the fast development of bendable electronic systems. Thus, the search for reliable electrodes with both high mechanical flexibility and excellent electron and lithium‐ion conductivity has become an urgent task. Carbon‐coated nanostructures of Li₄Ti₅O₁₂ (LTO) have important applications in high‐performance lithium ion batteries (LIBs). However, these materials still need to be mixed with a binder and carbon black and pressed onto metal substrates or, alternatively, by be deposited onto a conductive substrate before they are assembled into batteries, which makes the batteries less flexible and have a low energy density. Herein, a simple and scalable process to fabricate LTO nanosheets with a N‐doped carbon coating is reported. This can be assembled into a film which can be used as a binder‐free and flexible electrode for LIBs that does not require any current collectors. Such a flexible electrode has a long life. More significantly, it exhibits an excellent rate capability due to the thin carbon coating and porous nanosheet structures, which produces a highly conductive pathway for electrons and fast transport channels for lithium ions.     

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.     

High‐Performance Sodium‐Ion Hybrid Supercapacitor Based on Nb2O5@Carbon Core–Shell Nanoparticles and Reduced Graphene Oxide Nanocomposites

Sodium‐ion hybrid supercapacitors (Na‐HSCs) have potential for mid‐ to large‐scale energy storage applications because of their high energy/power densities, long cycle life, and the low cost of sodium. However, one of the obstacles to developing Na‐HSCs is the imbalance of kinetics from different charge storage mechanisms between the sluggish faradaic anode and the rapid non‐faradaic capacitive cathode. Thus, to develop high‐power Na‐HSC anode materials, this paper presents the facile synthesis of nanocomposites comprising Nb₂O₅@Carbon core–shell nanoparticles (Nb₂O₅@C NPs) and reduced graphene oxide (rGO), and an analysis of their electrochemical performance with respect to various weight ratios of Nb₂O₅@C NPs to rGO (e.g., Nb₂O₅@C, Nb₂O₅@C/rGO‐70, ‐50, and ‐30). In a Na half‐cell configuration, the Nb₂O₅@C/rGO‐50 shows highly reversible capacity of ≈285 mA h g^?1 at 0.025 A g^?1 in the potential range of 0.01–3.0 V (vs Na/Na⁺). In addition, the Na‐HSC using the Nb₂O₅@C/rGO‐50 anode and activated carbon (MSP‐20) cathode delivers high energy/power densities (≈76 W h kg^?1 and ≈20 800 W kg^?1) with a stable cycle life in the potential range of 1.0–4.3 V. The energy and power densities of the Na‐HSC developed in this study are higher than those of similar Li‐ and Na‐HSCs previously reported.     

Graphene Oxide Gel‐Derived,Free‐Standing,Hierarchically Porous Carbon for High‐Capacity and High‐Rate Rechargeable Li‐O2 Batteries

Lithium‐oxygen (Li‐O₂) batteries are one of the most promising candidates for high‐energy‐density storage systems. However, the low utilization of porous carbon and the inefficient transport of reactants in the cathode limit terribly the practical capacity and, in particular, the rate capability of state‐of‐the‐art Li‐O₂ batteries. Here, free‐standing, hierarchically porous carbon (FHPC) derived from graphene oxide (GO) gel in nickel foam without any additional binder is synthesized by a facile and effective in situ sol‐gel method, wherein the GO not only acts as a special carbon source, but also provides the framework of a 3D gel; more importantly, the proper acidity via its intrinsic COOH groups guarantees the formation of the whole structure. Interestingly, when employed as a cathode for Li‐O₂ batteries, the capacity reaches 11 060 mA h g^?1 at a current density of 0.2 mA cm^?2 (280 mA g^?1); and, unexpectedly, a high capacity of 2020 mA h g^?1 can be obtained even the current density increases ten times, up to 2 mA cm^?2 (2.8 A g^?1), which is the best rate performance for Li‐O₂ batteries reported to date. This excellent performance is attributed to the synergistic effect of the loose packing of the carbon, the hierarchical porous structure, and the high electronic conductivity of the Ni foam.     

Advantageous Functional Integration of Adsorption‐Intercalation‐Conversion Hybrid Mechanisms in 3D Flexible Nb2O5@Hard Carbon@MoS2@Soft Carbon Fiber Paper Anodes for Ultrafast and Super‐Stable Sodium Storage

Using synergetic effects of various sodium storage modes and materials to construct high power, high energy, and long cycling flexible sodium anode materials is significant and still challenging. Here, by advantageous functional integration of adsorption‐intercalation‐conversion sodium storage mechanisms, a 3D flexible fiber paper anode with the composition of Nb₂O₅@hard carbon@MoS₂@soft carbon is designed and prepared. Based on the synergetic effects, it exhibits higher specific capacity than pure Nb₂O₅, with more excellent rate performance (245, 201, 155, 133, and 97 mAh g^?1 at the current density of 0.2, 1, 5, 10, and 20 A g^?1, respectively) than pure MoS₂ as well as admirable long‐term cycling characteristics (≈82% capacity retention after 20 000 cycles at 5 A g^?1). Relevant kinetics mechanisms are expounded in detail. This work can be helpful for preparing other types of hybrid and flexible electrodes for energy storage systems.     

MoS2‐Quantum‐Dot‐Interspersed Li4Ti5O12 Nanosheets with Enhanced Performance for Li‐ and Na‐Ion Batteries

Rational nanoscale surface engineering of electroactive nanoarchitecture is highly desirable, since it can both secure high surface‐controlled energy storage and sustain the structural integrity for long‐time and high‐rate cycling. Herein, ultrasmall MoS₂ quantum dots (QDs) are exploited as surface sensitizers to boost the electrochemical properties of Li₄Ti₅O₁₂ (LTO). The LTO/MoS₂ composite is prepared by anchoring 2D LTO nanosheets with ultrasmall MoS₂ QDs using a simple and effective assembly technique. Impressively, such 0D/2D heterostructure composites possess enhanced surface‐controlled Li/Na storage behavior. This unprecedented Li/Na storage process provides a LTO/MoS₂ composite with outstanding Li/Na storage properties, such as high capacity and high‐rate capability as well as long‐term cycling stability. As anodes in Li‐ion batteries, the materials have a stable specific capacity of 170 mAhg^?1 after 20 cycles and are able to retain 94.1% of this capacity after 1000 cycles, i.e., 160 mAhg^?1, at a high rate of 10 C. Due to these impressice performance, the presented 0D/2D heterostructure has great potential in high‐performance LIBs and sodium‐ion batteries.     

Ti3+ Self‐Doped Dark Rutile TiO2 Ultrafine Nanorods with Durable High‐Rate Capability for Lithium‐Ion Batteries

Dark‐colored rutile TiO₂ nanorods doped by electroconducting Ti³⁺ have been obtained uniformly with an average diameter of ≈7 nm, and have been first utilized as anodes in lithium‐ion batteries. They deliver a high reversible specific capacity of 185.7 mAh g^?1 at 0.2 C (33.6 mA g^?1) and maintain 92.1 mAh g^?1 after 1000 cycles at an extremely high rate 50 C with an outstanding retention of 98.4%. Notably, the coulombic efficiency of Ti³⁺–TiO₂ has been improved by approximately 10% compared with that of pristine rutile TiO₂, which can be mainly attributed to its prompt electron transfer because of the introduction of Ti³⁺. Again the synergetic merits are noticed when the promoted electronic conductivity is combined with a shortened Li⁺ diffusion length resulting from the ultrafine nanorod structure, giving rise to the remarkable rate capabilities and extraordinary cycling stabilities for applications in fast and durable charge/discharge batteries. It is of great significance to incorporate Ti³⁺ into rutile TiO₂ to exhibit particular electrochemical characteristics triggering an effective way to improve the energy storage properties.     

Self‐Standing Porous LiCoO2 Nanosheet Arrays as 3D Cathodes for Flexible Li‐Ion Batteries

Self‐standing electrodes are the key to realize flexible Li‐ion batteries. However, fabrication of self‐standing cathodes is still a major challenge. In this work, porous LiCoO₂ nanosheet arrays are grown on Au‐coated stainless steel (Au/SS) substrates via a facile “hydrothermal lithiation” method using Co₃O₄ nanosheet arrays as the template followed by quick annealing in air. The binder‐free and self‐standing LiCoO₂ nanosheet arrays represent the 3D cathode and exhibit superior rate capability and cycling stability. In specific, the LiCoO₂ nanosheet array electrode can deliver a high reversible capacity of 104.6 mA h g^?1 at 10 C rate and achieve a capacity retention of 81.8% at 0.1 C rate after 1000 cycles. By coupling with Li₄Ti₅O₁₂ nanosheet arrays as anode, an all‐nanosheet array based LiCoO₂//Li₄Ti₅O₁₂ flexible Li‐ion battery is constructed. Benefiting from the 3D nanoarchitectures for both cathode and anode, the flexible LiCoO₂//Li₄Ti₅O₁₂ battery can deliver large specific reversible capacities of 130.7 mA h g^?1 at 0.1 C rate and 85.3 mA h g^?1 at 10 C rate (based on the weight of cathode material). The full cell device also exhibits good cycling stability with 80.5% capacity retention after 1000 cycles at 0.1 C rate, making it promising for the application in flexible Li‐ion batteries.     

Au‐Decorated Cracked Carbon Tube Arrays as Binder‐Free Catalytic Cathode Enabling Guided Li2O2 Inner Growth for High‐Performance Li‐O2 Batteries

Owing to their extremely high energy density, Li‐O₂ batteries have attained increasing attention in recent studies. However, deposition of the discharge product, insulating Li₂O₂, is known to seriously limit the electrochemical performance of Li‐O₂ batteries. While extensive studies have focused on relieving electrode deactivation by controlling Li₂O₂ growth, no permanent or effective mechanism is delivered. Here, a unique design comprising a catalytic cathode constructed by cracked carbon submicron tube (CST) arrays decorated with Au nanoparticles on inner walls is proposed. The introduction of Au nanoparticles not only improves electrode conductivity but also provides catalytic sites, guiding conformal growth of thin‐layered Li₂O₂ inside the cracked CST. Density functional theory calculations support that Au decoration on CST favors the conformal growth of Li₂O₂ on inner tubular walls. This growth behavior of Li₂O₂ renders easy decomposition of Li₂O₂, prevents carbon tube electrode from full, rapid deactivation, and preserves the free space for reactants transport. Li‐O₂ cells with Au@CST exhibit good rate capability (1208 mAh g^–1 at a high current density of 1000 mA g^–1) and long cycle life (112 cycles at a current density of 400 mA g^–1 with a limited capacity of 500 mAh g^–1).     

Layered Orthorhombic Nb2O5@Nb4C3Tx and TiO2@Ti3C2Tx Hierarchical Composites for High Performance Li‐ion Batteries

Engineering electrode nanostructures is critical in developing high‐capacity, fast rate‐response, and safe Li‐ion batteries. This study demonstrates the synthesis of orthorhombic Nb₂O₅@Nb₄C₃T_x (or @Nb₂CT_x) hierarchical composites via a one‐step oxidation —in flowing CO₂ at 850 °C —of 2D Nb₄C₃T_x (or Nb₂CT_x) MXene. The composites possess a layered architecture with orthorhombic Nb₂O₅ nanoparticles decorated uniformly on the surface of the MXene flakes and interconnected by disordered carbon. The composites have a capacity of 208 mAh g^?1 at a rate of 50 mA g^?1 (0.25 C) in 1–3 V versus Li⁺/Li, and retain 94% of the specific capacity with 100% Coulombic efficiency after 400 cycles. The good electrochemical performances could be attributed to three synergistic effects: (1) the high conductivity of the interior, unoxidized Nb₄C₃T_x layers, (2) the fast rate response and high capacity of the external Nb₂O₅ nanoparticles, and (3) the electron “bridge” effects of the disordered carbon. This oxidation method was successfully extended to Ti₃C₂T_x and Nb₂CT_x MXenes to prepare corresponding composites with similar hierarchical structures. Since this is an early report on producing this structure, there is much room to push the boundaries further and achieve better electrochemical performance.     

GeOx/Reduced Graphene Oxide Composite as an Anode for Li‐Ion Batteries: Enhanced Capacity via Reversible Utilization of Li2O along with Improved Rate Performance

A self‐assembled GeO_x/reduced graphene oxide (GeO_x/RGO) composite, where GeO_x nanoparticles are grown directly on reduced graphene oxide sheets, is synthesized via a facile one‐step reduction approach and studied by X‐ray diffraction, transmission electron microscopy, energy dispersive X‐ray spectroscopy, electron energy loss spectroscopy elemental mapping, and other techniques. Electrochemical evaluation indicates that incorporation of reduced graphene oxide enhances both the rate capability and reversible capacity of GeO_x, with the latter being due to the RGO enabling reversible utilization of Li₂O. The composite delivers a high reversible capacity of 1600 mAh g^?1 at a current density of 100 mA g^?1, and still maintains a capacity of 410 mAh g^?1 at a high current density of 20 A g^?1. Owing to the flexible reduced graphene oxide sheets enwrapping the GeO_x particles, the cycling stability of the composite is also improved significantly. To further demonstrate its feasibility in practical applications, the synthesized GeO_x/RGO composite anode is successfully paired with a high voltage LiNi_0.5Mn_1.5O₄ cathode to form a full cell, which shows good cycling and rate performance.     

Binding Sulfur‐Doped Nb2O5 Hollow Nanospheres on Sulfur‐Doped Graphene Networks for Highly Reversible Sodium Storage

Orthorhombic Nb₂O₅ (T‐Nb₂O₅) has recently attracted great attention for its application as an anode for sodium ion batteries (NIBs) owing to its patulous framework and larger interplanar lattice spacing. Sulfur‐doped T‐Nb₂O₅ hollow nanospheres (diameter:180 nm) uniformly encapsulate into sulfur‐doped graphene networks (denoted: S‐Nb₂O₅ HNS@S‐rGO) using hard template method. The 3D ordered porous structure not only provides good electronic transportation path but also offers outstanding ionic conductive channels, leading to an improved sodium storage performance. In addition, the introduction of sulfur to graphene and Nb₂O₅ leads to oxygen vacancy and enhanced electronic conductivity. The sodium storage performance of S‐Nb₂O₅ HNS@S‐rGO is unprecedented. It delivers a reversible capacity 215 mAh g^?1 at 0.5 C over 100 cycles. In addition, it also possesses a great high‐rate capability, retaining a stable capacity of 100 mAh g^?1 at 20 C after 3000 cycles. This design demonstrates the potential applications of Nb₂O₅ as anode for high performance NIBs.     

Toward Optimal Performance and In‐Depth Understanding of Spinel Li4Ti5O12 Electrodes through Phase Field Modeling

Computational modeling is vital for the fundamental understanding of processes in Li‐ion batteries. However, capturing nanoscopic to mesoscopic phase thermodynamics and kinetics in the solid electrode particles embedded in realistic electrode morphologies is challenging. In particular for electrode materials displaying a first order phase transition, such as LiFePO₄, graphite, and spinel Li₄Ti₅O₁₂, predicting the macroscopic electrochemical behavior requires an accurate physical model. Herein, a thermodynamic phase field model is presented for Li‐ion insertion in spinel Li₄Ti₅O₁₂ which captures the performance limitations presented in literature as a function of all relevant electrode parameters. The phase stability in the model is based on ab initio density functional theory calculations and the Li‐ion diffusion parameters on nanoscopic nuclear magnetic resonance (NMR) measurements of Li‐ion mobility, resulting in a parameter free model. The direct comparison with prepared electrodes shows good agreement over three orders of magnitude in the discharge current. Overpotentials associated with the various charge transport processes, as well as the active particle fraction relevant for local hotspots in batteries, are analyzed. It is demonstrated which process limits the electrode performance under a variety of realistic conditions, providing comprehensive understanding of the nanoscopic to microscopic properties. These results provide concrete directions toward the design of optimally performing Li₄Ti₅O₁₂ electrodes.     

Zn(Cu)Si2+xP3 Solid Solution Anodes for High‐Performance Li‐Ion Batteries with Tunable Working Potentials

Si‐based anodes with a stiff diamond structure usually suffer from sluggish lithiation/delithiation reaction due to low Li‐ion and electronic conductivity. Here, a novel ternary compound ZnSi₂P₃ with a cation‐disordered sphalerite structure, prepared by a facile mechanochemical method, is reported, demonstrating faster Li‐ion and electron transport and greater tolerance to volume change during cycling than the existing Si‐based anodes. A composite electrode consisting of ZnSi₂P₃ and carbon achieves a high initial Coulombic efficiency (92%) and excellent rate capability (950 mAh g^?1 at 10 A g^?1) while maintaining superior cycling stability (1955 mAh g^?1 after 500 cycles at 300 mA g^?1), surpassing the performance of most Si‐ and P‐based anodes ever reported. The remarkable electrochemical performance is attributed to the sphalerite structure that allows fast ion and electron transport and the reversible Li‐storage mechanism involving intercalation and conversion reactions. Moreover, the cation‐disordered sphalerite structure is flexible to ionic substitutions, allowing extension to a family of Zn(Cu)Si_2+xP₃ solid solution anodes (x = 0, 2, 5, 10) with large capacity, high initial Coulombic efficiency, and tunable working potentials, representing attractive anode candidates for next‐generation, high‐performance, and low‐cost Li‐ion batteries.     

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.     

A Composite of Carbon‐Wrapped Mo2C Nanoparticle and Carbon Nanotube Formed Directly on Ni Foam as a High‐Performance Binder‐Free Cathode for Li‐O2 Batteries

Cathode design is indispensable for building Li‐O₂ batteries with long cycle life. A composite of carbon‐wrapped Mo₂C nanoparticles and carbon nanotubes is prepared on Ni foam by direct hydrolysis and carbonization of a gel composed of ammonium heptamolybdate tetrahydrate and hydroquinone resin. The Mo₂C nanoparticles with well‐controlled particle size act as a highly active oxygen reduction reactions/oxygen evolution reactions (ORR/OER) catalyst. The carbon coating can prevent the aggregation of the Mo₂C nanoparticles. The even distribution of Mo₂C nanoparticles results in the homogenous formation of discharge products. The skeleton of porous carbon with carbon nanotubes protrudes from the composite, resulting in extra voids when applied as a cathode for Li‐O₂ batteries. The batteries deliver a high discharge capacity of ≈10 400 mAh g^?1 and a low average charge voltage of ≈4.0 V at 200 mA g^?1. With a cutoff capacity of 1000 mAh g^?1, the Li‐O₂ batteries exhibit excellent charge–discharge cycling stability for over 300 cycles. The average potential polarization of discharge/charge gaps is only ≈0.9 V, demonstrating the high ORR and OER activities of these Mo₂C nanoparticles. The excellent cycling stability and low potential polarization provide new insights into the design of highly reversible and efficient cathode materials for Li‐O₂ batteries.     

Mesoporous NiCo2O4 Nanowire Arrays Grown on Carbon Textiles as Binder‐Free Flexible Electrodes for Energy Storage

Binary metal oxides has been regarded as a promising class of electrode materials for high‐performance energy storage devices since it offers higher electrochemical activity and higher capacity than mono‐metal oxide. Besides, rational design of electrode architectures is an effective solution to further enhance electrochemical performance of energy storage devices. Here, the advanced electrode architectures consisting of carbon textiles uniformally covered by mesoporous NiCo₂O₄ nanowire arrays (NWAs) are successfully fabricated by a simple surfactant‐assisted hydrothermal method combined with a short post annealing treatment, which can be directly applied as self‐supported electrodes for energy storage devices, such as Li‐ion batteries, supercapacitors. The as‐prepared mesoporous NiCo₂O₄ nanowires consist of numerous highly crystalline nanoparticles, leaving a large number of mesopores to alleviate the volume change during the charge/discharge process. Electrode architectures presented here promise fast electron transport by direct connection to the growth substrate and facile ion diffusion path provided by both the abundant mesoporous structure in nanowires and large open spaces between neighboring nanowires, which ensures every nanowire participates in the ultrafast electrochemical reaction. Benefiting from the intrinsic materials and architectures features, the unique binder‐free NiCo₂O₄/carbon textiles exhibit high specific capacity/capacitance, excellent rate capability, and cycling stability.