High‐Voltage Oxygen‐Redox‐Based Cathode for Rechargeable Sodium‐Ion Batteries

Recently, anionic‐redox‐based materials have shown promising electrochemical performance as cathode materials for sodium‐ion batteries. However, one of the limiting factors in the development of oxygen‐redox‐based electrodes is their low operating voltage. In this study, the operating voltage of oxygen‐redox‐based electrodes is raised by incorporating nickel into P2‐type Na_2/3[Zn_0.3Mn_0.7]O₂ in such a way that the zinc is partially substituted by nickel. As designed, the resulting P2‐type Na_2/3[(Ni_0.5Zn_0.5)_0.3Mn_0.7]O₂ electrode exhibits an average operating voltage of 3.5 V and retains 95% of its initial capacity after 200 cycles in the voltage range of 2.3–4.6 V at 0.1C (26 mA g^?1). Operando X‐ray diffraction analysis reveals the reversible phase transition: P2 to OP4 phase on charge and recovery to the P2 phase on discharge. Moreover, ex situ X‐ray absorption near edge structure and X‐ray photoelectron spectroscopy studies reveal that the capacity is generated by the combination of Ni²⁺/Ni⁴⁺ and O^2?/O^1? redox pairs, which is supported by first‐principles calculations. It is thought that this kind of high voltage redox species combined with oxygen redox could be an interesting approach to further increase energy density of cathode materials for not only sodium‐based rechargeable batteries, but other alkali‐ion battery systems.     

A 4 V Na+ Intercalation Material in a New Na‐Ion Cathode Family

Large‐scale electrochemical energy storage is a critical factor in the development of renewable energy sources to enable their intermittent power to become dispatchable. In this context, Na‐ion batteries are seen as promising alternatives to Li‐ion batteries, but their advancement requires the discovery of new materials, their electrochemical properties, and a better understanding of structure–property relationships that underpin the electrochemistry. This study presents a new class of Na⁺ insertion materials for Na‐ion batteries. By virtue of its moderately inductive polyanionic framework, the air and moisture stable selenite Na₂Co₂(SeO₃)₃ displays a highly suitable redox potential of ≈ 4 V versus Na/Na⁺ based on the Co²⁺/Co³⁺ couple, rendering it compatible with conventional liquid organic electrolytes. A microwave hydrothermal synthesis route is developed for the rapid synthesis of nanostructured Na₂Co₂(SeO₃)₃ and its conductive graphene oxide composite. The electrochemistry and structural evolution of Na₂Co₂(SeO₃)₃ determined on cycling the cathode in a Na battery was investigated by operando X‐ray diffraction, X‐ray photoelectron spectroscopy, and temperature dependent magnetic susceptibility measurements. These studies reveal good structural and electrochemical reversibility.     

Black Phosphorus Quantum Dot/Ti3C2 MXene Nanosheet Composites for Efficient Electrochemical Lithium/Sodium‐Ion Storage

The exploration of new and efficient energy storage mechanisms through nanostructured electrode design is crucial for the development of high‐performance rechargeable batteries. Herein, black phosphorus quantum dots (BPQDs) and Ti₃C₂ nanosheets (TNSs) are employed as battery and pseudocapacitive components, respectively, to construct BPQD/TNS composite anodes with a novel battery‐capacitive dual‐model energy storage (DMES) mechanism for lithium‐ion and sodium‐ion batteries. Specifically, as a battery‐type component, BPQDs anchored on the TNSs are endowed with improved conductivity and relieved stress upon cycling, enabling a high‐capacity and stable energy storage. Meanwhile, the pseudocapacitive TNS component with further atomic charge polarization induced by P? O? Ti interfacial bonds between the two components allows enhanced charge adsorption and efficient interfacial electron transfer, contributing a higher pseudocapacitive value and fast energy storage. The DMES mechanism is evidenced by substantial characterizations of X‐ray photoelectron spectroscopy and X‐ray absorption fine structure spectroscopy, density functional theory calculations, and kinetics analyses. Consequently, the composite electrode exhibits superior battery performance, especially for lithium storage, such as high capacity (910 mAh g^?1 at 100 mA g^?1), long cycling stability (2400 cycles with a capacity retention over 100%), and high rate capability, representing the best comprehensive battery performance in BP‐based anodes to date.     

High‐Performance Platinum‐Perovskite Composite Bifunctional Oxygen Electrocatalyst for Rechargeable Zn–Air Battery

Constructing highly active electrocatalysts with superior stability at low cost is a must, and vital for the large‐scale application of rechargeable Zn–air batteries. Herein, a series of bifunctional composites with excellent electrochemical activity and durability based on platinum with the perovskite Sr(Co_0.8Fe_0.2)_0.95P_0.05O_3?δ (SCFP) are synthesized via a facile but effective strategy. The optimal sample Pt‐SCFP/C‐12 exhibits outstanding bifunctional activity for the oxygen reduction reaction and oxygen evolution reaction with a potential difference of 0.73 V. Remarkably, the Zn–air battery based on this catalyst shows an initial discharge and charge potential of 1.25 and 2.02 V at 5 mA cm^?2, accompanied by an excellent cycling stability. X‐ray photoelectron spectroscopy, X‐ray absorption near‐edge structure, and extended X‐ray absorption fine structure experiments demonstrate that the superior performance is due to the strong electronic interaction between Pt and SCFP that arises as a result of the rapid electron transfer via the Pt? O? Co bonds as well as the higher concentration of surface oxygen vacancies. Meanwhile, the spillover effect between Pt and SCFP also can increase more active sites via lowering energy barrier and change the rate‐determining step on the catalysts surface. Undoubtedly, this work provides an efficient approach for developing low‐cost and highly active catalysts for wider application of electrochemical energy devices.     

Efficient Photocatalytic Nitrogen Fixation over Cuδ+‐Modified Defective ZnAl‐Layered Double Hydroxide Nanosheets

The photocatalytic reduction of nitrogen (N₂) with water (H₂O) as the reducing agent holds great promise as a sustainable future technology for the synthesis of ammonia (NH₃). Herein, the effect of oxygen vacancies and electron‐rich Cu^δ+ on the performance of zinc‐aluminium layered double hydroxide (ZnAl‐LDH) nanosheet photocatalysts for N₂ reduction to NH₃ under UV–vis excitation is systematically explored. Results show that a 0.5%‐ZnAl‐LDH nanosheet photocatalyst (containing 0.5 mol% Cu by metal basis) affords a remarkable NH₃ production rate of 110 µmol g^?1 h^?1 and excellent stability in pure water. The X‐ray absorption spectroscopy, electron paramagnetic resonance, and density functional theory calculations reveal that Cu addition imparts oxygen vacancies and coordinatively unsaturated Cu^δ+ (δ < 2) with electron‐rich property in the ZnAl‐LDH nanosheets, both of which readily contribute to efficient separation and transfer of photogenerated electrons and holes and promote N₂ adsorption, thereby both activating N₂ and facilitating its multielectrons reduction to NH₃.     

Sodium Ion Stabilized Vanadium Oxide Nanowire Cathode for High‐Performance Zinc‐Ion Batteries

Aqueous Zn‐ion batteries (ZIBs) have received incremental attention because of their cost‐effectiveness and the materials abundance. They are a promising choice for large‐scale energy storage applications. However, developing suitable cathode materials for ZIBs remains a great challenge. In this work, pioneering work on the designing and construction of aqueous Zn//Na_0.33V₂O₅ batteries is reported. The Na_0.33V₂O₅ (NVO) electrode delivers a high capacity of 367.1 mA h g^?1 at 0.1 A g^?1, and exhibits long‐term cyclic stability with a capacity retention over 93% for 1000 cycles. The improvement of electrical conductivity, resulting from the intercalation of sodium ions between the [V₄O₁₂]_n layers, is demonstrated by single nanowire device. Furthermore, the reversible intercalation reaction mechanism is confirmed by X‐ray diffraction, Raman, X‐ray photoelectron spectroscopy, scanning electron microscopy, and transmission electron microscopy analysis. The outstanding performance can be attributed to the stable layered structure and high conductivity of NVO. This work also indicates that layered structural materials show great potential as the cathode of ZIBs, and the indigenous ions can act as pillars to stabilize the layered structure, thereby ensuring an enhanced cycling stability.     

Nature of FeSe2/N‐C Anode for High Performance Potassium Ion Hybrid Capacitor

Potassium ion hybrid capacitors have great potential for large‐scale energy devices, because of the high power density and low cost. However, their practical applications are hindered by their low energy density, as well as electrolyte decomposition and collector corrosion at high potential in potassium bis(fluoro‐sulfonyl)imide‐based electrolyte. Therefore, anode materials with high capacity, a suitable voltage platform, and stability become a key factor. Here, N‐doping carbon‐coated FeSe₂ clusters are demonstrated as the anode material for a hybrid capacitor, delivering a reversible capacity of 295 mAh g^?1 at 100 mA g^?1 over 100 cycles and a high rate capability of 158 mAh g^?1 at 2000 mA g^?1 over 2000 cycles. Meanwhile, through density functional theory calculations, in situ X‐ray diffraction, and ex situ transmission electron microscopy, the evolution of FeSe₂ to Fe₃Se₄ for the electrochemical reaction mechanism is successfully revealed. The battery‐supercapacitor hybrid using commercial activated carbon as the cathode and FeSe₂/N‐C as the anode is obtained. It delivers a high energy density of 230 Wh kg^?1 and a power density of 920 W kg^?1 (the energy density and power density are calculated based on the total mass of active materials in the anode and cathode).     

High Voltage LiNi0.5Mn0.3Co0.2O2/Graphite Cell Cycled at 4.6 V with a FEC/HFDEC‐Based Electrolyte

A high voltage LiNi_0.5Mn_0.3Co_0.2O₂/graphite cell with a fluorinated electrolyte formulation 1.0 m LiPF₆ fluoroethylene carbonate/bis(2,2,2‐trifluoroethyl) carbonate is reported and its electrochemical performance is evaluated at cell voltage of 4.6 V. Comparing with its nonfluorinated electrolyte counterpart, the reported fluorinated one shows much improved Coulombic efficiency and capacity retention when a higher cut‐off voltage (4.6 V) is applied. Scanning electron microscopy/energy dispersive X‐ray spectroscopy and X‐ray photoelectron spectroscopy data clearly demonstrate the superior oxidative stability of the new electrolyte. The structural stability of the bulk cathode materials cycled with different electrolytes is extensively studied by X‐ray absorption near edge structure and X‐ray diffraction.     

Structural and optical properties of europium‐ and titanium‐doped Y2O3 nanoparticles

Luminescent nanoparticles of Y₂O₃ doped with europium (Eu) and/or titanium (Ti) were synthesized using modified sol–gel routes. The crystalline cubic phase was confirmed using X‐ray powder diffraction (XRD). Particle morphology and size were evaluated using scanning and transmission electron microscopy. High‐resolution transmission electron microscopy showed that the synthesis method affected the average particle size and the Fourier transform of the images showed the lattice plane distances, indicating that the samples presented high crystallinity degree in accordance with the XRD pattern. The Ti valence was investigated using X‐ray absorption near edge spectroscopy and the tetravalent form was the dominant oxidizing state in the samples, mainly in Eu and Ti co‐doped Y₂O₃. Optical behaviour was investigated through X‐ray excited optical luminescence and photoluminescence under ultraviolet–visible (UV–vis) and vacuum ultraviolet (VUV) excitation. Results indicated that Eu³⁺ is the emitting centre in samples doped with only Eu and with both Eu and Ti with the ⁵D₀→⁷F₂ transition as the most intense, indicating Eu³⁺ in a noncentrosymmetric site. Finally, in the Eu,Ti‐doped Y₂O₃ system, Ti³⁺ (or Ti^IV) excitation was observed but no Ti emission was present, indicating a very efficient energy transfer process from Ti to Eu³⁺. These results can aid the development of efficient nanomaterials, activated using UV, VUV, or X‐rays.     

g‐C3N4‐Based Heterostructured Photocatalysts

Photocatalysis is considered as one of the promising routes to solve the energy and environmental crises by utilizing solar energy. Graphitic carbon nitride (g‐C₃N₄) has attracted worldwide attention due to its visible‐light activity, facile synthesis from low‐cost materials, chemical stability, and unique layered structure. However, the pure g‐C₃N₄ photocatalyst still suffers from its low separation efficiency of photogenerated charge carriers, which results in unsatisfactory photocatalytic activity. Recently, g‐C₃N₄‐based heterostructures have become research hotspots for their greatly enhanced charge carrier separation efficiency and photocatalytic performance. According to the different transfer mechanisms of photogenerated charge carriers between g‐C₃N₄ and the coupled components, the g‐C₃N₄‐based heterostructured photocatalysts can be divided into the following categories: g‐C₃N₄‐based conventional type II heterojunction, g‐C₃N₄‐based Z‐scheme heterojunction, g‐C₃N₄‐based p–n heterojunction, g‐C₃N₄/metal heterostructure, and g‐C₃N₄/carbon heterostructure. This review summarizes the recent significant progress on the design of g‐C₃N₄‐based heterostructured photocatalysts and their special separation/transfer mechanisms of photogenerated charge carriers. Moreover, their applications in environmental and energy fields, e.g., water splitting, carbon dioxide reduction, and degradation of pollutants, are also reviewed. Finally, some concluding remarks and perspectives on the challenges and opportunities for exploring advanced g‐C₃N₄‐based heterostructured photocatalysts are presented.     

Understanding the Rate Capability of High‐Energy‐Density Li‐Rich Layered Li1.2Ni0.15Co0.1Mn0.55O2 Cathode Materials

The high‐energy‐density, Li‐rich layered materials, i.e., xLiMO₂(1‐x)Li₂MnO₃, are promising candidate cathode materials for electric energy storage in plug‐in hybrid electric vehicles (PHEVs) and electric vehicles (EVs). The relatively low rate capability is one of the major problems that need to be resolved for these materials. To gain insight into the key factors that limit the rate capability, in situ X‐ray absorption spectroscopy (XAS) and X‐ray diffraction (XRD) studies of the cathode material, Li_1.2Ni_0.15Co_0.1Mn_0.55O₂ [0.5Li(Ni_0.375Co_0.25 Mn_0.375)O₂·0.5Li₂MnO₃], are carried out. The partial capacity contributed by different structural components and transition metal elements is elucidated and correlated with local structure changes. The characteristic reaction kinetics for each element are identified using a novel time‐resolved XAS technique. Direct experimental evidence is obtained showing that Mn sites have much poorer reaction kinetics both before and after the initial activation of Li₂MnO₃, compared to Ni and Co. These results indicate that Li₂MnO₃ may be the key component that limits the rate capability of Li‐rich layered materials and provide guidance for designing Li‐rich layered materials with the desired balance of energy density and rate capability for different applications.     

Native Vacancy Enhanced Oxygen Redox Reversibility and Structural Robustness

Cathode materials with high energy density, long cycle life, and low cost are of top priority for energy storage systems. The Li‐rich transition metal (TM) oxides achieve high specific capacities by redox reactions of both the TM and oxygen ions. However, the poor reversible redox reaction of the anions results in severe fading of the cycling performance. Herein, the vacancy‐containing Na_4/7[Mn_6/7(?_Mn)_1/7]O₂ (?_Mn for vacancies in the Mn? O slab) is presented as a novel cathode material for Na‐ion batteries. The presence of native vacancies endows this material with attractive properties including high structural flexibility and stability upon Na‐ion extraction and insertion and high reversibility of oxygen redox reaction. Synchrotron X‐ray absorption near edge structure and X‐ray photoelectron spectroscopy studies demonstrate that the charge compensation is dominated by the oxygen redox reaction and Mn³⁺/Mn⁴⁺ redox reaction separately. In situ synchrotron X‐ray diffraction exhibits its zero‐strain feature during the cycling. Density functional theory calculations further deepen the understanding of the charge compensation by oxygen and manganese redox reactions and the immobility of the Mn ions in the material. These findings provide new ideas on searching for and designing materials with high capacity and high structural stability for novel energy storage systems.     

Superior Performance of Microporous Aluminophosphate with LTA Topology in Solar‐Energy Storage and Heat Reallocation

Hydrophilic porous materials are recognized as very promising materials for water‐sorption‐based energy storage and transformation. In this study, a porous, zeolite‐like aluminophosphate with LTA (Linde Type A) topology is inspected as an energy‐storage material. The study is motivated by the material's high predicted pore volume. According to sorption and calorimetric tests, the aluminophosphate outperforms all other zeolite‐like and metal‐organic porous materials tested so far. It adsorbs water in an extremely narrow relative‐pressure interval (0.10 < p /p ₀ < 0.15) and exhibits superior water uptake (0.42 g g^?1) and energy‐storage capacity (527 kW h m^?3). It also shows remarkable cycling stability; after 40 cycles of adsorption/desorption its capacity drops by less than 2%. Desorption temperature for this material, which is one of crucial parameters in applications, is lower from desorption temperatures of other tested materials by 10–15 °C. Furthermore, its heat‐pump performance is very high, allowing efficient cooling in demanding conditions (with cooling power up to 350 kW h m^?3 even at 30 °C temperature difference between evaporator and environment). On the microscopic scale, sorption mechanism in AlPO₄‐LTA is elucidated by X‐ray diffraction, nuclear magnetic resonance measurements, and first‐principles calculations. In this aluminophosphate, energy is stored predominately in hydrogen‐bonded network of water molecules within the pores.     

Computational Design and Preparation of Cation‐Disordered Oxides for High‐Energy‐Density Li‐Ion Batteries

Cation‐disordered lithium‐excess metal oxides have recently emerged as a promising new class of high‐energy‐density cathode materials for Li‐ion batteries, but the exploration of disordered materials has been hampered by their vast and unexplored composition space. This study proposes a practical methodology for the identification of stable cation‐disordered rocksalts. Here, it is established that the efficient method, which makes use of special quasirandom structures, correctly predicts cation‐ordering strengths in agreement with accurate Monte‐Carlo simulations and experimental observations. By applying the approach to the composition space of ternary oxides with formula unit LiA_0.5B_0.5O₂ (A, B: transition metals), this study discovers a previously unknown cation‐disordered structure, LiCo_0.5Zr_0.5O₂, that may function as the basis for a new class of cation‐disordered cathode materials. This computational prediction is confirmed experimentally by solid‐state synthesis and subsequent characterization by powder X‐ray diffraction demonstrating the potential of the computational screening of large composition spaces for accelerating materials discovery.     

Construction of Hierarchical K1.39Mn3O6 Spheres via AlF3 Coating for High‐Performance Potassium‐Ion Batteries

Potassium‐ion batteries are attracting great interest for emerging large‐scale energy storage owing to their advantages such as low cost and high operational voltage. However, they are still suffering from poor cycling stability and sluggish thermodynamic kinetics, which inhibits their practical applications. Herein, the synthesis of hierarchical K_1.39Mn₃O₆ microspheres as cathode materials for potassium‐ion batteries is reported. Additionally, an effective AlF₃ surface coating strategy is applied to further improve the electrochemical performance of K_1.39Mn₃O₆ microspheres. The as‐synthesized AlF₃ coated K_1.39Mn₃O₆ microspheres show a high reversible capacity (about 110 mA h g^?1 at 10 mA g^?1), excellent rate capability, and cycling stability. Galvanostatic intermittent titration technique results demonstrate that the increased diffusion kinetics of potassium‐ion insertion and extraction during discharge and charge processes benefit from both the hierarchical sphere structure and surface modification. Furthermore, ex situ X‐ray diffraction measurements reveal that the irreversible structure evolution can be significantly mitigated via surface modification. This work sheds light on rational design of high‐performance cathode materials for potassium‐ion batteries.     

Silica Restricting the Sulfur Volatilization of Nickel Sulfide for High‐Performance Lithium‐Ion Batteries

Nickel sulfides are regarded as promising anode materials for advanced rechargeable lithium‐ion batteries due to their high theoretical capacity. However, capacity fade arising from significant volume changes during operation greatly limits their practical applications. Herein, confined NiS_x@C yolk–shell microboxes are constructed to address volume changes and confine the active material in the internal void space. Having benefited from the yolk–shell structure design, the prepared NiS_x@C yolk–shell microboxes display excellent electrochemical performance in lithium‐ion batteries. Particularly, it delivers impressive cycle stability (460 mAh g^?1 after 2000 cycles at 1 A g^?1) and superior rate performance (225 mAh g^?1 at 20 A g^?1). Furthermore, the lithium storage mechanism is ascertained with in situ synchrotron high‐energy X‐ray diffractions and in situ electrochemical impedance spectra. This unique confined yolk–shell structure may open up new strategies to create other advanced electrode materials for high performance electrochemical storage systems.     

Recent Development of Metallic (1T) Phase of Molybdenum Disulfide for Energy Conversion and Storage

The development of a feasible and inexpensive strategy to obtain and utilize sustainable energy is an important issue for the sustainable development of human society. Over the past decade, significant progress has been made in the development of novel functional materials for energy conversion and storage. Owing to their unique physico‐chemical properties, 2D layered materials, such as graphene and transition metal dichalcogenides, have attracted great interest in energy‐related research. 1T‐MoS₂ is a metallic phase of molybdenum disulfide (MoS₂) with extraordinary electronic conductivity, enlarged interlayer spacing, and more electrochemically active sites along the basal plane, which offers intriguing benefits for energy‐related applications compared to its semiconducting counterpart (2H‐MoS₂). This review summarizes the preparation and structure–property relationships of 1T‐MoS₂, as well as the underlying relations between the metallic (1T) and semiconducting (2H) phases of MoS₂. Recent progress in the preparation and stabilization of 1T‐MoS₂ materials and their applications for energy conversion and storage are discussed, including water splitting to form hydrogen via photo/electrocatalysis and electricity storage in lithium‐ion batteries, sodium‐ion batteries, magnesium‐ion batteries, and supercapacitors. Optimization strategies of 1T‐MoS₂ to obtain enhanced practical properties based on theoretical calculations are also presented.     

Dial the Mechanism Switch of VN from Conversion to Intercalation toward Long Cycling Sodium‐Ion Battery

Transition metal nitrides are promising energy storage materials in regard to good metallic conductivity and high theoretical specific capacity, but their cycling stability is impeded by the huge volume change caused by the conversion reaction mechanism. Here, a simple strategy to produce an intercalation pseudocapacitive‐type vanadium nitride (VN) by one‐step ammonification of V₂C MXene for sodium‐ion batteries is reported. Profiting from a distinctive layered structure pillared by Al atoms in the layer spacing, it delivers a high capacity of 372 mA h g^?1 at 50 mA g^?1 and a desirable rate performance. More importantly, it shows remarkably long cycling stability over 7500 cycles without capacity attenuation at 500 mA g^?1. As expected, it is found that the intercalation pseudocapacitance plays an important role in the excellent performance, by using in situ X‐ray diffraction and ex situ X‐ray absorption structure characterization. Even more remarkable, are the high energy and power density of the sodium‐ion capacitor after coupling with a carbon‐based cathode. The hybrid device possesses an energy density of 78.43 Wh kg^?1 at power density of 260 W kg^?1. The results clearly show that such a unique‐layered VN with outstanding Na storage capability is an excellent new material for energy storage systems.     

Evaluation of trapping parameters of γ‐rays irradiated Dy3+‐doped LaPO4 phosphors

Thermoluminescence (TL) materials are widely used in radiation measurements. The best‐known applications of TL materials are in the dosimetry of ionizing radiation, and in CTV screen phosphors, scintillators, X‐ray laser materials, etc. The TL glow curve and its kinetic parameters for annealed LaPO₄ at different constant temperatures and for Dy³⁺‐doped LaPO₄ phosphors irradiated by gamma‐rays are reported here. The samples were irradiated using a ⁶⁰Co gamma‐ray source at a dose of 10 Gy and the heating rate used for TL measurements was 5ºC/s. The samples were characterized using X‐ray diffraction (XRD), Fourier transform infrared, transmission electron microscopy and TL techniques. The XRD pattern shows that the prepared phosphor has a good crystalline structure with an average crystallite size of ~ 18 nm. The samples show good TL peaks for 0.05, 0.1 and 0.2 mole % doping concentrations of Dy³⁺ ions and anneal above 400ºC. The TL glow curve characteristics of annealed LaPO₄ and Dy³⁺‐doped LaPO₄ were analyzed and trapping parameters calculated using various methods. All TL glow curves obey the second‐order kinetics with a single glow peak, which reveals that only one set of trapping parameter is set for a particular temperature. The TL sensitivity was found to depend upon the annealing temperature and Dy³⁺ doping concentration. The prepared sample may be a new nano phosphor and be useful in TL dosimetry. Copyright © 2014 John Wiley & Sons, Ltd.     

Identification of Phase Control of Carbon‐Confined Nb2O5 Nanoparticles toward High‐Performance Lithium Storage

Niobium pentoxides (Nb₂O₅) have attracted extensive interest for ultrafast lithium‐ion batteries due to their impressive rate/capacity performance and high safety as intercalation anodes. However, the intrinsic insulating properties and unrevealed mechanisms of complex phases limit their further applications. Here, a facile and efficient method is developed to construct three typical carbon‐confined Nb₂O₅ (TT‐Nb₂O₅@C, T‐Nb₂O₅@C, and H‐Nb₂O₅@C) nanoparticles via a mismatched coordination reaction during the solvothermal process and subsequent controlled heat treatment, and different phase effects are investigated on their lithium storage properties on the basis of both experimental and computational approaches. The thin carbon coating and nanoscale size can endow Nb₂O₅ with a high surface area, high conductivity, and short diffusion length. As a proof‐of‐concept application, when employed as LIB anode materials, the resulting T‐Nb₂O₅@C nanoparticles display higher rate capability and better cycling stability as compared with TT‐Nb₂O₅@C and H‐Nb₂O₅@C nanoparticles. Furthermore, a synergistic effect is investigated and demonstrated between fast diffusion pathways and stable hosts in T‐Nb₂O₅ for ultrafast and stable lithium storage, based on crystal structure analysis, in situ X‐ray diffraction analysis, and density functional theoretical calculations. Therefore, the proposed synthetic strategy and obtained deep insights will stimulate the development of Nb₂O₅ for ultrafast and long‐life LIBs.