Direct Visualization of the Reversible O2−/O− Redox Process in Li‐Rich Cathode Materials

Conventional cathodes of Li‐ion batteries mainly operate through an insertion–extraction process involving transition metal redox. These cathodes will not be able to meet the increasing requirements until lithium‐rich layered oxides emerge with beyond‐capacity performance. Nevertheless, in‐depth understanding of the evolution of crystal and excess capacity delivered by Li‐rich layered oxides is insufficient. Herein, various in situ technologies such as X‐ray diffraction and Raman spectroscopy are employed for a typical material Li_1.2Ni_0.2Mn_0.6O₂, directly visualizing O^?? O^? (peroxo oxygen dimers) bonding mostly along the c‐axis and demonstrating the reversible O^2?/O^? redox process. Additionally, the formation of the peroxo O? O bond is calculated via density functional theory, and the corresponding O? O bond length of ≈1.3 Å matches well with the in situ Raman results. These findings enrich the oxygen chemistry in layered oxides and open opportunities to design high‐performance positive electrodes for lithium‐ion batteries.     

A New Type of Li‐Rich Rock‐Salt Oxide Li2Ni1/3Ru2/3O3 with Reversible Anionic Redox Chemistry

Li‐rich oxide cathodes are of prime importance for the development of high‐energy lithium‐ion batteries (LIBs). Li‐rich layered oxides, however, always undergo irreversible structural evolution, leading to inevitable capacity and voltage decay during cycling. Meanwhile, Li‐rich cation‐disordered rock‐salt oxides usually exhibit sluggish kinetics and inferior cycling stability, despite their firm structure and stable voltage output. Herein, a new Li‐rich rock‐salt oxide Li₂Ni_1/3Ru_2/3O₃ with Fd‐3m space group, where partial cation‐ordering arrangement exists in cationic sites, is reported. Results demonstrate that a cathode fabricated from Li₂Ni_1/3Ru_2/3O₃ delivers a large capacity, outstanding rate capability as well as good cycling performance with negligible voltage decay, in contrast to the common cations disordered oxides with space group Fm‐3m. First principle calculations also indicate that rock‐salt oxide with space group Fd‐3m possesses oxygen activity potential at the state of delithiation, and good kinetics with more 0‐TM (TM = transition metals) percolation networks. In situ Raman results confirm the reversible anionic redox chemistry, confirming O^2?/O^? evolution during cycles in Li‐rich rock‐salt cathode for the first time. These findings open up the opportunity to design high‐performance oxide cathodes and promote the development of high‐energy LIBs.     

Regulating Surface and Grain‐Boundary Structures of Ni‐Rich Layered Cathodes for Ultrahigh Cycle Stability

The wide applications of Ni‐rich LiNi_1‐x‐yCo_xMn_yO₂ cathodes are severely limited by capacity fading and voltage fading during the cycling process resulting from the pulverization of particles, interfacial side reactions, and phase transformation. The canonical surface modification approach can improve the stability to a certain extent; however, it fails to resolve the key bottlenecks. The preparation of Li(Ni_0.4Co_0.2Mn_0.4)_1‐xTi_xO₂ on the surface of LiNi_0.8Co_0.1Mn_0.1O₂ particles with a coprecipitation method is reported. After sintering, Ti diffuses into the interior and mainly distributes along surface and grain boundaries. A strong surface and grain boundary strengthening are simultaneously achieved. The pristine particles are fully pulverized into first particles due to mechanical instability and high strains, which results in serious capacity fading. In contrast, the strong surface and the grain boundary strengthening can maintain the structural integrity, and therefore significantly improve the cycle stability. A general and simple strategy for the design of high‐performance Ni‐rich LiNi_1‐x‐yCo_xMn_yO₂ cathode is provided and is applicable to surface modification and grain‐boundary regulation of other advanced cathodes for batteries.     

Countering the Segregation of Transition‐Metal Ions in LiMn1/3Co1/3Ni1/3O2 Cathode for Ultralong Life and High‐Energy Li‐Ion Batteries

High‐voltage layered lithium transition‐metal oxides are very promising cathodes for high‐energy Li‐ion batteries. However, these materials often suffer from a fast degradation of cycling stability due to structural evolutions. It seriously impedes the large‐scale application of layered lithium transition‐metal oxides. In this work, an ultralong life LiMn_1/3Co_1/3Ni_1/3O₂ microspherical cathode is prepared by constructing an Mn‐rich surface. Its capacity retention ratio at 700 mA g^?1 is as large as 92.9% after 600 cycles. The energy dispersive X‐ray maps of electrodes after numerous cycles demonstrate that the ultralong life of the as‐prepared cathode is attributed to the mitigation of TM‐ions segregation. Additionally, it is discovered that layered lithium transition‐metal oxide cathodes with an Mn‐rich surface can mitigate the segregation of TM ions and the corrosion of active materials. This study provides a new strategy to counter the segregation of TM ions in layered lithium transition‐metal oxides and will help to the design and development of high‐energy cathodes with ultralong life.     

Probing the Ni(OH)2 Precursor for LiNiO2 at the Atomic Scale: Insights into the Origin of Structural Defect in a Layered Cathode Active Material

In lithium ion batteries (LIBs), the layered cathode materials of composition LiNi_1−x−yCo_xMn_yO₂ are critical for achieving high energy densities. A high nickel content (>80%) provides an attractive balance between high energy density, long lifetime, and low cost. Consequently, Ni-rich layered oxides cathode active materials (CAMs) are in high demand, and the importance of LiNiO₂ (LNO) as limiting case, is hence paramount. However, achieving perfect stoichiometry is a challenge resulting in various structural issues, which successively impact physicochemical properties and result in the capacity fade of LIBs. To better understand defect formation in LNO, the role of the Ni(OH)₂ precursor morphology in the synthesis of LNO requires in-depth investigation. By employing aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, and precession electron diffraction, a direct observation of defects in the Ni(OH)₂ precursor preparedis reported and the ex situ structural evolution from the precursor to the end product is monitored. During synthesis, the layered Ni(OH)₂ structure transforms to partially lithiated (non-layered) NiO and finally to layered LNO. The results suggest that the defects observed in commercially relevant CAMs originate to a large extent from the precursors, hence care must be taken in tuning the co-precipitation parameters to synthesize defect-free Ni-rich layered oxides CAMs.     

Recent Progress of Layered Transition Metal Oxide Cathodes for Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) are attracting increasing attention and considered to be a low‐cost complement or an alternative to lithium‐ion batteries (LIBs), especially for large‐scale energy storage. Their application, however, is limited because of the lack of suitable host materials to reversibly intercalate Na⁺ ions. Layered transition metal oxides (Na_xMO₂, M = Fe, Mn, Ni, Co, Cr, Ti, V, and their combinations) appear to be promising cathode candidates for SIBs due to their simple structure, ease of synthesis, high operating potential, and feasibility for commercial production. In the present work, the structural evolution, electrochemical performance, and recent progress of Na_xMO₂ as cathode materials for SIBs are reviewed and summarized. Moreover, the existing drawbacks are discussed and several strategies are proposed to help alleviate these issues. In addition, the exploration of full cells based on Na_xMO₂ cathodes and future perspectives are discussed to provide guidance for the future commercialization of such systems.     

High-Nickel NMA: A Cobalt-Free Alternative to NMC and NCA Cathodes for Lithium-Ion Batteries

High-nickel LiNi_1−x−yMn_xCo_yO₂ (NMC) and LiNi_1−x−yCo_xAl_yO₂ (NCA) are the cathode materials of choice for next-generation high-energy lithium-ion batteries. Both NMC and NCA contain cobalt, an expensive and scarce metal generally believed to be essential for their electrochemical performance. Herein, a high-Ni LiNi_1−x−yMn_xAl_yO₂ (NMA) cathode of desirable electrochemical properties is demonstrated benchmarked against NMC, NCA, and Al–Mg-codoped NMC (NMCAM) of identical Ni content (89 mol%) synthesized in-house. Despite a slightly lower specific capacity, high-Ni NMA operates at a higher voltage by ≈40 mV and shows no compromise in rate capability relative to NMC and NCA. In pouch cells paired with graphite, high-Ni NMA outperforms both NMC and NCA and only slightly trails NMCAM and a commercial cathode after 1000 deep cycles. Further, the superior thermal stability of NMA to NMC, NCA, and NMCAM is shown using differential scanning calorimetry. Considering the flexibility in compositional tuning and immediate synthesis scalability of high-Ni NMA very similar to NCA and NMC, this study opens a new space for cathode material development for next-generation high-energy, cobalt-free Li-ion batteries.     

Additive‐Assisted Novel Dual‐Salt Electrolyte Addresses Wide Temperature Operation of Lithium–Metal Batteries

In this study, self‐synthesized lithium trifluoro(perfluoro‐tert‐butyloxyl)borate (LiTFPFB) is combined with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) to formulate a novel 1 m dual‐salt electrolyte, which contains lithium difluorophosphate (LiPO₂F₂) additive and dominant carbonate solvents with low melting point and high boiling point. The addition of LiPO₂F₂ into this novel dual‐salt electrolyte dramatically improves cycleability and rate capability of a LiNi_0.5Mn_0.3Co_0.2O₂/Li (NMC/Li) battery, ranging from ?40 to 90 °C. The NMC/Li batteries adopt a Li–metal anode with low thickness of 100 µm (even 50 µm) and a moderately high cathode mass loading level of 10 mg cm^?2. For the first time, this paper provides valuable perspectives for developing practical lithium–metal batteries over a wide temperature range.     

In Situ Encapsulating α‐MnS into N,S‐Codoped Nanotube‐Like Carbon as Advanced Anode Material: α → β Phase Transition Promoted Cycling Stability and Superior Li/Na‐Storage Performance in Half/Full Cells

Incorporation of N,S‐codoped nanotube‐like carbon (N,S‐NTC) can endow electrode materials with superior electrochemical properties owing to the unique nanoarchitecture and improved kinetics. Herein, α‐MnS nanoparticles (NPs) are in situ encapsulated into N,S‐NTC, preparing an advanced anode material (α‐MnS@N,S‐NTC) for lithium‐ion/sodium‐ion batteries (LIBs/SIBs). It is for the first time revealed that electrochemical α → β phase transition of MnS NPs during the 1st cycle effectively promotes Li‐storage properties, which is deduced by the studies of ex situ X‐ray diffraction/high‐resolution transmission electron microscopy and electrode kinetics. As a result, the optimized α‐MnS@N,S‐NTC electrode delivers a high Li‐storage capacity (1415 mA h g^?1 at 50 mA g^?1), excellent rate capability (430 mA h g^?1 at 10 A g^?1), and long‐term cycling stability (no obvious capacity decay over 5000 cycles at 1 A g^?1) with retained morphology. In addition, the N,S‐NTC‐based encapsulation plays the key roles on enhancing the electrochemical properties due to its high conductivity and unique 1D nanoarchitecture with excellent protective effects to active MnS NPs. Furthermore, α‐MnS@N,S‐NTC also delivers high Na‐storage capacity (536 mA h g^?1 at 50 mA g^?1) without the occurrence of such α → β phase transition and excellent full‐cell performances as coupling with commercial LiFePO₄ and LiNi_0.6Co_0.2Mn_0.2O₂ cathodes in LIBs as well as Na₃V₂(PO₄)₂O₂F cathode in SIBs.     

Preparation and electrochemical characteristics of microemulsion-derived Li(Ni,Co)O<Subscript>2</Subscript> nanopowders

Nanosized LiNi_0.9Co_0.1O₂ powders used in lithium-ion batteries are successfully prepared via a water-in-oil microemulsion process. The average particle sizes of the microemulsion-derived LiNi_0.9Co_0.1O₂ powders are in nanometer scale. The obtained powders are much smaller in size than the specimens prepared via the conventional solid state and sol–gel processes. Oxygen has significant enhancement effects on the cationic ordering of the calcined powders. Highly cation-ordered LiNi_0.9Co_0.1O₂ powders with a layered structure are obtained after heat-treatment at 800 °C in O₂. In addition, the high intensity ratio of I ₀₀₃/I ₁₀₄ reveals that lithium ions and transition metal ions are regularly situated at the 3a and 3b sites, respectively, rendering the high cationic ordering. The discharge capacity of the first cycle for the specimen calcined at 800 °C in O₂ is 170.9 mAh/g. After 20 cycles, the capacity retention of LiNi_0.9Co_0.1O₂ powders is 93.2%, indicating that LiNi_0.9Co_0.1O₂ powders with good cycling characteristics are obtained via the microemulsion process.     

A High‐Rate V2O5 Hollow Microclew Cathode for an All‐Vanadium‐Based Lithium‐Ion Full Cell

V₂O₅ hollow microclews (V₂O₅‐HMs) have been fabricated through a facile solvothermal method with subsequent calcination. The synthesized V₂O₅‐HMs exhibit a 3D hierarchical structure constructed by intertangled nanowires, which could realize superior ion transport, good structural stability, and significantly improved tap density. When used as the cathodes for lithium‐ion batteries (LIBs), the V₂O₅‐HMs deliver a high capacity (145.3 mAh g^‐1) and a superior rate capability (94.8 mAh g^‐1 at 65 C). When coupled with a lithiated Li₃VO₄ anode, the all‐vanadium‐based lithium‐ion full cell exhibits remarkable cycling stability with a capacity retention of 71.7% over 1500 cycles at 6.7 C. The excellent electrochemical performance demonstrates that the V₂O₅‐HM is a promising candidate for LIBs. The insight obtained from this work also provides a novel strategy for assembling 1D materials into hierarchical microarchitectures with anti‐pulverization ability, excellent electrochemical kinetics, and enhanced tap density.     

Ti‐Substituted NaNi0.5Mn0.5‐xTixO2 Cathodes with Reversible O3−P3 Phase Transition for High‐Performance Sodium‐Ion Batteries

Sodium‐ion batteries (SIBs) have been considered as potential candidates for stationary energy storage because of the low cost and wide availability of Na sources. O3‐type layered oxides have been considered as one of the most promising cathodes for SIBs. However, they commonly show inevitable complicated phase transitions and sluggish kinetics, incurring rapid capacity decline and poor rate capability. Here, a series of sodium‐sufficient O3‐type NaNi_0.5Mn_{0.5‐ x} Ti _x O₂ (0 ≤ x ≤ 0.5) cathodes for SIBs is reported and the mechanisms behind their excellent electrochemical performance are studied in comparison to those of their respective end‐members. The combined analysis of in situ X‐ray diffraction, ex situ X‐ray absorption spectroscopy, and scanning transmission electron microscopy for NaNi_0.5Mn_0.2Ti_0.3O₂ reveals that the O3‐type phase transforms reversibly into a P3‐type phase upon Na+ deintercalation/intercalation. The substitution of Ti for Mn enlarges interslab distance and could restrain the unfavorable and irreversible multiphase transformation in the high voltage regions that is usually observed in O3‐type NaNi_0.5Mn_0.5O₂, resulting in improved Na cell performance. This integration of macroscale and atomicscale engineering strategy might open up the modulation of the chemical and physical properties in layered oxides and grasp new insight into the optimal design of high‐performance cathode materials for SIBs.     

Recent breakthroughs and perspectives of high-energy layered oxide cathode materials for lithium ion batteries

Ni-rich layered oxides (NRLOs) and Li-rich layered oxides (LRLOs) have been considered as promising next-generation cathode materials for lithium ion batteries (LIBs) due to their high energy density, low cost, and environmental friendliness. However, these two layered oxides suffer from similar problems like capacity fading and different obstacles such as thermal runaway for NRLOs and voltage decay for LRLOs. Understanding the similarities and differences of their challenges and strategies at multiple scales plays a paramount role in the cathode development of advanced LIBs. Herein, we provide a comprehensive review of state-of-the-art progress made in NRLOs and LRLOs based on multi-scale insights into electrons/ions, crystals, particles, electrodes and cells. For NRLOs, issues like structure disorder, cracks, interfacial degradation and thermal runaway are elaborately discussed. Superexchange interaction and magnetic frustration are blamed for structure disorder while strains induced by universal structural collapse result in issues like cracks. For LRLOs, we present an overview of the origin of high capacity followed by local crystal structure, and the root of voltage hysteresis/decay, which are ascribed to reduced valence of transition metal ions, phase transformation, strains, and microstructure degradation. We then discuss failure mechanism in full cells with NRLO cathode and commercial challenges of LRLOs. Moreover, strategies to improve the performance of NRLOs and LRLOs from different scales such as ion-doping, microstructure designs, particle modifications, and electrode/electrolyte interface engineering are summarized. Dopants like Na, Mg and Zr, delicate gradient concentration design, coatings like spinel LiNi_0.5Mn_1.5O₄ or Li₃PO₄ and novel electrolyte formulas are highly desired. Developing single crystals for NRLOs and new crystallographic structure or heterostructure for LRLOs are also emphasized. Finally, remaining challenges and perspectives are outlined for the development of NRLOs and LRLOs. This review offers fundamental understanding and future perspectives towards high-performance cathodes for next-generation LIBs.     

Facile preparation of core@shell and concentration-gradient spinel particles for Li-ion battery cathode materials

Core@shell and concentration-gradient particles have attracted much attention as improved cathodes for Li-ion batteries (LIBs). However, most of their preparation routes have employed a precisely-controlled co-precipitation method. Here, we report a facile preparation route of core@shell and concentration-gradient spinel particles by dry powder processing. The core@shell particles composed of the MnO₂ core and the Li(Ni,Mn)₂O₄ spinel shell are prepared by mechanical treatment using an attrition-type mill, whereas the concentration-gradient spinel particles with an average composition of LiNi_0.32Mn_1.68O₄ are produced by calcination of their core@shell particles as a precursor. The concentration-gradient LiNi_0.32Mn_1.68O₄ spinel cathode exhibits the high discharge capacity of 135.3 mA h g⁻¹, the wide-range plateau at a high voltage of 4.7 V and the cyclability with a capacity retention of 99.4% after 20 cycles. Thus, the facile preparation route of the core@shell and concentration-gradient particles may provide a new opportunity for the discovery and investigation of functional materials as well as for the cathode materials for LIBs.     

Facile preparation of core@shell and concentration-gradient spinel particles for Li-ion battery cathode materials

Abstract

Core@shell and concentration-gradient particles have attracted much attention as improved cathodes for Li-ion batteries (LIBs). However, most of their preparation routes have employed a precisely-controlled co-precipitation method. Here, we report a facile preparation route of core@shell and concentration-gradient spinel particles by dry powder processing. The core@shell particles composed of the MnO₂ core and the Li(Ni,Mn)₂O₄ spinel shell are prepared by mechanical treatment using an attrition-type mill, whereas the concentration-gradient spinel particles with an average composition of LiNi_0.32Mn_1.68O₄ are produced by calcination of their core@shell particles as a precursor. The concentration-gradient LiNi_0.32Mn_1.68O₄ spinel cathode exhibits the high discharge capacity of 135.3 mA h g^?1, the wide-range plateau at a high voltage of 4.7 V and the cyclability with a capacity retention of 99.4% after 20 cycles. Thus, the facile preparation route of the core@shell and concentration-gradient particles may provide a new opportunity for the discovery and investigation of functional materials as well as for the cathode materials for LIBs.     

Few Atomic Layered Lithium Cathode Materials to Achieve Ultrahigh Rate Capability in Lithium‐Ion Batteries

The most promising cathode materials, including LiCoO₂ (layered), LiMn₂O₄ (spinel), and LiFePO₄ (olivine), have been the focus of intense research to develop rechargeable lithium‐ion batteries (LIBs) for portable electronic devices. Sluggish lithium diffusion, however, and unsatisfactory long‐term cycling performance still limit the development of present LIBs for several applications, such as plug‐in/hybrid electric vehicles. Motivated by the success of graphene and novel 2D materials with unique physical and chemical properties, herein, a simple shear‐assisted mechanical exfoliation method to synthesize few‐layered nanosheets of LiCoO₂, LiMn₂O₄, and LiFePO₄ is used. Importantly, these as‐prepared nanosheets with preferred orientations and optimized stable structures exhibit excellent C‐rate capability and long‐term cycling performance with much reduced volume expansion during cycling. In particular, the zero‐strain insertion phenomenon could be achieved in 2–3 such layers of LiCoO₂ electrode materials, which could open up a new way to the further development of next‐generation long‐life and high‐rate batteries.     

A 3D Lithiophilic Mo2N‐Modified Carbon Nanofiber Architecture for Dendrite‐Free Lithium‐Metal Anodes in a Full Cell

The pursuit for high‐energy‐density batteries has inspired the resurgence of metallic lithium (Li) as a promising anode, yet its practical viability is restricted by the uncontrollable Li dendrite growth and huge volume changes during repeated cycling. Herein, a new 3D framework configured with Mo₂N‐mofidied carbon nanofiber (CNF) architecture is established as a Li host via a facile fabrication method. The lithiophilic Mo₂N acts as a homogeneously pre‐planted seed with ultralow Li nucleation overpotential, thus spatially guiding a uniform Li nucleation and deposition in the matrix. The conductive CNF skeleton effectively homogenizes the current distribution and Li‐ion flux, further suppressing Li‐dendrite formation. As a result, the 3D hybrid Mo₂N@CNF structure facilitates a dendrite‐free morphology with greatly alleviated volume expansion, delivering a significantly improved Coulombic efficiency of ≈99.2% over 150 cycles at 4 mA cm^?2. Symmetric cells with Mo₂N@CNF substrates stably operate over 1500 h at 6 mA cm^?2 for 6 mA h cm^?2. Furthermore, full cells paired with LiNi_0.8Co_0.1Mn_0.1O₂ (NMC811) cathodes in conventional carbonate electrolytes achieve a remarkable capacity retention of 90% over 150 cycles. This work sheds new light on the facile design of 3D lithiophilic hosts for dendrite‐free lithium‐metal anodes.     

O3‐Type Layered Ni‐Rich Oxide: A High‐Capacity and Superior‐Rate Cathode for Sodium‐Ion Batteries

Inspired by its high‐active and open layered framework for fast Li⁺ extraction/insertion reactions, layered Ni‐rich oxide is proposed as an outstanding Na‐intercalated cathode for high‐performance sodium‐ion batteries. An O3‐type Na_0.75Ni_0.82Co_0.12Mn_0.06O₂ is achieved through a facile electrochemical ion‐exchange strategy in which Li⁺ ions are first extracted from the LiNi_0.82Co_0.12Mn_0.06O₂ cathode and Na⁺ ions are then inserted into a layered oxide framework. Furthermore, the reaction mechanism of layered Ni‐rich oxide during Na⁺ extraction/insertion is investigated in detail by combining ex situ X‐ray diffraction, X‐ray photoelectron spectroscopy, and electron energy loss spectroscopy. As an excellent cathode for Na‐ion batteries, O3‐type Na_0.75Ni_0.82Co_0.12Mn_0.06O₂ delivers a high reversible capacity of 171 mAh g^?1 and a remarkably stable discharge voltage of 2.8 V during long‐term cycling. In addition, the fast Na⁺ transport in the cathode enables high rate capability with 89 mAh g^?1 at 9 C. The as‐prepared Ni‐rich oxide cathode is expected to significantly break through the limited performance of current sodium‐ion batteries.     

Electrostatically Assembling 2D Nanosheets of MXene and MOF‐Derivatives into 3D Hollow Frameworks for Enhanced Lithium Storage

As an essential member of 2D materials, MXene (e.g., Ti₃C₂T_x) is highly preferred for energy storage owing to a high surface‐to‐volume ratio, shortened ion diffusion pathway, superior electronic conductivity, and neglectable volume change, which are beneficial for electrochemical kinetics. However, the low theoretical capacitance and restacking issues of MXene severely limit its practical application in lithium‐ion batteries (LIBs). Herein, a facile and controllable method is developed to engineer 2D nanosheets of negatively charged MXene and positively charged layered double hydroxides derived from ZIF‐67 polyhedrons into 3D hollow frameworks via electrostatic self‐assembling. After thermal annealing, transition metal oxides (TMOs)@MXene (CoO/Co₂Mo₃O₈@MXene) hollow frameworks are obtained and used as anode materials for LIBs. CoO/Co₂Mo₃O₈ nanosheets prevent MXene from aggregation and contribute remarkable lithium storage capacity, while MXene nanosheets provide a 3D conductive network and mechanical robustness to facilitate rapid charge transfer at the interface, and accommodate the volume expansion of the internal CoO/Co₂Mo₃O₈. Such hollow frameworks present a high reversible capacity of 947.4 mAh g^?1 at 0.1 A g^?1, an impressive rate behavior with 435.8 mAh g^?1 retained at 5 A g^?1, and good stability over 1200 cycles (545 mAh g^?1 at 2 A g^?1).     

Surface‐Engineered Black Niobium Oxide@Graphene Nanosheets for High‐Performance Sodium‐/Potassium‐Ion Full Batteries

Nanoscale surface‐engineering plays an important role in improving the performance of battery electrodes. Nb₂O₅ is one typical model anode material with promising high‐rate lithium storage. However, its modest reaction kinetics and low electrical conductivity obstruct the efficient storage of larger ions of sodium or potassium. In this work, partially surface‐amorphized and defect‐rich black niobium oxide@graphene (black Nb₂O_5?x@rGO) nanosheets are designed to overcome the above Na/K storage problems. The black Nb₂O_5?x@rGO nanosheets electrodes deliver a high‐rate Na and K storage capacity (123 and 73 mAh g^?1, respectively at 3 A g^?1) with long‐term cycling stability. Besides, both Na‐ion and K‐ion full batteries based on black Nb₂O_5?x@rGO nanosheets anodes and vanadate‐based cathodes (Na_0.33V₂O₅ and K_0.5V₂O₅ for Na‐ion and K‐ion full batteries, respectively) demonstrate promising rate and cycling performance. Notably, the K‐ion full battery delivers higher energy and power densities (172 Wh Kg^?1 and 430 W Kg^?1), comparable to those reported in state‐of‐the‐art K‐ion full batteries, accompanying with a capacity retention of ≈81.3% over 270 cycles. This result on Na‐/K‐ion batteries may pave the way to next‐generation post‐lithium batteries.