Mg/Fe site-specific dual-doping to boost the performance of cobalt-free nickle-rich layered oxide cathode for high-energy lithium-ion batteries

Layer-type LiNi0.9Mn0.1O2is promising to be the primary cathode material for lithium-ion batteries(LIBs)due to its excellent electrochemical performance.Unfortunately,the cathode with high nickel content suffers from severely detrimental structural transformation that causes rapid capacity attenuation.Herein,site-specific dual-doping with Fe and Mg ions is proposed to enhance the structural stability of LiNi0.9Mn0.1O2.The Fe3+dopants are inserted into transition metal sites(3b)and can favorably provide additional redox potential to compensate for charge and enhance the reversibility of anionic redox.The Mg ions are doped into the Li sites(3a)and serve as O_(2)^(-)-Mg^(2+)-O_(2)^(-)pillar to reinforce the electrostatic cohesion between the two adjacent transition-metal layers,which further suppress the cracking and the generation of harmful phase transitions,ultimately improving the cyclability.The theoretical calculations,including Bader charge and crystal orbital Hamilton populations(COHP)analyses,confirm that the doped Fe and Mg can form stable bonds with oxygen and the electrostatic repulsion of O_(2)^(-)-O_(2)^(-)can be effectively suppressed,which effectively mitigates oxygen anion loss at the high delithiation state.This dual-site doping strategy offers new avenues for understanding and regulating the crystalline oxygen redox and demonstrates significant potential for designing high-performance cobalt-free nickel-rich cathodes.

High‑Entropy Layered Oxide Cathode Enabling High‑Rate for Solid‑State Sodium‑Ion Batteries

Na-ion O3-type layered oxides are prospective cathodes for Na-ion batteries due to high energy density and low-cost.Nevertheless,such cathodes usually suffer from phase transitions,sluggish kinetics and air instability,making it difficult to achieve high performance solid-state sodium-ion batteries.Herein,the high-entropy design and Li doping strategy alleviate lattice stress and enhance ionic conductivity,achieving high-rate performance,air stability and electrochemically thermal stability for Na_(0.95)Li_(0.06)Ni_(0.25)Cu_(0.05)Fe_(0.15)Mn_(0.49)O_(2).This cathode delivers a high reversible capacity(141 mAh g^(−1)at 0.2C),excellent rate capability(111 mAh g^(−1)at 8C,85 mAh g^(−1)even at 20C),and long-term stability(over 85%capacity retention after 1000 cycles),which is attributed to a rapid and reversible O3–P3 phase transition in regions of low voltage and suppresses phase transition.Moreover,the compound remains unchanged over seven days and keeps thermal stability until 279℃.Remarkably,the polymer solid-state sodium battery assembled by this cathode provides a capacity of 92 mAh g^(−1)at 5C and keeps retention of 96%after 400 cycles.This strategy inspires more rational designs and could be applied to a series of O3 cathodes to improve the performance of solid-state Na-ion batteries.

Difficulties, strategies, and recent research and development of layered sodium transition metal oxide cathode materials for high-energy sodium-ion batteries

Energy-storage systems and their production have attracted significant interest for practical applications.Batteries are the foundation of sustainable energy sources for electric vehicles(EVs),portable electronic devices(PEDs),etc.In recent decades,Lithium-ion batteries(LIBs) have been extensively utilized in largescale energy storage devices owing to their long cycle life and high energy density.However,the high cost and limited availability of Li are the two main obstacles for LIBs.In this regard,sodium-ion batteries(SIBs) are attractive alternatives to LIBs for large-scale energy storage systems because of the abundance and low cost of sodium materials.Cathode is one of the most important components in the battery,which limits cost and performance of a battery.Among the classified cathode structures,layered structure materials have attracted attention because of their high ionic conductivity,fast diffusion rate,and high specific capacity.Here,we present a comprehensive review of the classification of layered structures and the preparation of layered materials.Furthermore,the review article discusses extensively about the issues of the layered materials,namely(1) electrochemical degradation,(2) irreversible structural changes,and(3) structural instability,and also it provides strategies to overcome the issues such as elemental phase composition,a small amount of elemental doping,structural design,and surface alteration for emerging SIBs.In addition,the article discusses about the recent research development on layered unary,binary,ternary,quaternary,quinary,and senary-based O3-and P2-type cathode materials for high-energy SIBs.This review article provides useful information for the development of high-energy layered sodium transition metal oxide P2 and O3-cathode materials for practical SIBs.

Impact of Transition Metal Layer Vacancy on the Structure and Performance of P2 Type Layered Sodium Cathode Material

This study explores the impact of introducing vacancy in the transition metal layer of rationally designed Na_(0.6)[Ni_(0.3)Ru_(0.3)Mn_(0.4)]O_(2)(NRM)cathode material.The incorporation of Ru,Ni,and vacancy enhances the structural stability during extensive cycling,increases the operation voltage,and induces a capacity increase while also activating oxygen redox,respectively,in Na_(0.7)[Ni_(0.2)V_(Ni0.1)Ru_(0.3)Mn_(0.4)]O_(2)(V-NRM)compound.Various analytical techniques including transmission electron microscopy,X-ray absorption near edge spectroscopy,operando X-ray diffraction,and operando differential electrochemical mass spectrometry are employed to assess changes in the average oxidation states and structural distortions.The results demonstrate that V-NRM exhibits higher capacity than NRM and maintains a moderate capacity retention of 81%after 100 cycles.Furthermore,the formation of additional lone-pair electrons in the O 2p orbital enables V-NRM to utilize more capacity from the oxygen redox validated by density functional calculation,leading to a widened dominance of the OP4 phase without releasing O_(2) gas.These findings offer valuable insights for the design of advanced high-capacity cathode materials with improved performance and sustainability in sodium-ion batteries.

Phase engineering of Ni-Mn binary layered oxide cathodes for sodiumion batteries

Nickel-manganese binary layered oxides with high working potential and low cost are potential candidates for sodium-ion batteries,but their electrochemical properties are highly related to compositional diversity.Diverse composite materials with various phase structures of P3,P2/P3,P2,P2/O3,and P2/P3/O3 were synthesized by manipulating the sodium content and calcination conditions,leading to the construction of a synthetic phase diagram for Na_(x)Ni_(0.25)Mn_(0.75)O_(2)(0.45≤x≤1.1).Then,we compared the electrochemical characteristics and structural evolution during the desodiation/sodiation process of P2,P2/P3,P2/03,and P2/P3/O3-Na_(x)Ni_(0.25)Mn_(0.75)O_(2).Among them,P2/P3-Na0.75Ni0.25Mn0.75O2exhibits the best rate capability of 90.9 mA h g^(-1)at 5 C,with an initial discharge capacity of 142.62 mA h g^(-1)at 0.1 C and a capacity retention rate of 78.25%after 100 cycles at 1 C in the voltage range of 2-4.3 V.The observed superior sodium storage performance of P2/P3 hybrids compared to other composite phases can be attributed to the enhanced Na^(+)transfer dynamic,reduction of the Jahn-teller effect,and improved reaction reversibility induced by the synergistic effect of P2 and P3 phases.The systematic research and exploration of phases in Na_(x)Ni_(0.25)Mn_(0.75)O_(2)provide new sights into high-performance nickel-manganese binary layered oxide for sodium-ion batteries.

Cationic ordering transition in oxygen-redox layered oxide cathodes

Understanding the structural origin of the competition between oxygen 2p and transition-metal 3d orbitals in oxygen-redox(OR)layered oxides is eminently desirable for exploring reversible and high-energy-density Li/Na-ion cathodes.Here,we reveal the correlation between cationic ordering transition and OR degradation in ribbon-ordered P3-Na_(0.6)Li_(0.2)Mn_(0.8)O_(2) via in situ structural analysis.Comparing two different voltage windows,the OR capacity can be improved approximately twofold when suppressing the in-plane cationic ordering transition.We find that the intralayer cationic migration is promoted by electrochemical reduction from Mn^(4+)to Jahn–Teller Mn^(3+)and the concomitant NaO_(6) stacking transformation from triangular prisms to octahedra,resulting in the loss of ribbon ordering and electrochemical decay.First-principles calculations reveal that Mn^(4+)/Mn^(3+)charge ordering and alignment of the degenerate eg orbital induce lattice-level collective Jahn–Teller distortion,which favors intralayer Mn-ion migration and thereby accelerates OR degradation.These findings unravel the relationship between in-plane cationic ordering and OR reversibility and highlight the importance of superstructure protection for the rational design of reversible OR-active layered oxide cathodes.

Degradation analysis and doping modification optimization for high-voltage P-type layered cathode in sodium-ion batteries

Advancing high-voltage stability of layered sodium-ion oxides represents a pivotal avenue for their progress in energy storage applications.Despite this,a comprehensive understanding of the mechanisms underpinning their structural deterioration at elevated voltages remains insufficiently explored.In this study,we unveil a layer delamination phenomenon of Na_(0.67)Ni_(0.3)Mn_(0.7)O_(2)(NNM)within the 2.0-4.3 V voltage,attributed to considerable volumetric fluctuations along the c-axis and lattice oxygen reactions induced by the simultaneous Ni^(3+)/Ni^(4+)and anion redox reactions.By introducing Mg doping to diminished Ni-O antibonding,the anion oxidation-reduction reactions are effectively mitigated,and the structural integrity of the P2 phase remains firmly intact,safeguarding active sites and precluding the formation of novel interfaces.The Na_(0.67)Mg_(0.05)Ni_(0.25)Mn_(0.7)O_(2)(NMNM-5)exhibits a specific capacity of100.7 mA h g^(-1),signifying an 83%improvement compared to the NNM material within the voltage of2.0-4.3 V.This investigation underscores the intricate interplay between high-voltage stability and structural degradation mechanisms in layered sodium-ion oxides.

Early-stage latent thermal failure of single-crystal Ni-rich layered cathode

High nickel content worsens the thermal stability of layered cathodes for lithium-ion batteries,raising safety concerns for their applications.Thoroughly understanding the thermal failure process can offer valuable guidance for material optimization on thermal stability and new opportunities in monitoring battery thermal runaway(TR).Herein,this work comprehensively investigates the thermal failure process of a single-crystal nickel-rich layered cathode and finds that the latent thermal failure starts at∼120℃far below the TR temperature(225℃).During this stage of heat accumulation,sequential structure transition is revealed by atomic resolution electron microscopy,which follows the layered→cation mixing layered→LiMn_(2)O_(4)-type spinel→disordered spinel→rock salt.This progression occurs as a result of the continuous migration and densification of transition metal cations.Phase transition generates gaseous oxygen,initially confined within the isolated closed pores,thereby not showing any thermal failure phenomena at the macro-level.Increasing temperature leads to pore growth and coalescence,and eventually to the formation of open pores,causing oxygen gas release and weight loss,which are the typical TR features.We highlight that latent thermal instability occurs before the macro-level TR,suggesting that suppressing phase transitions caused by early thermal instability is a crucial direction for material optimization.Our findings can also be used for early warning of battery thermal runaway.

Recent progress in Ni-rich layered oxides and related cathode materials for Li-ion cells

Undoubtedly,the enormous progress observed in recent years in the Ni-rich layered cathode materials has been crucial in terms of pushing boundaries of the Li-ion battery(LIB)technology.The achieved improvements in the energy density,cyclability,charging speed,reduced costs,as well as safety and stability,already contribute to the wider adoption of LIBs,which extends nowadays beyond mobile electronics,power tools,and electric vehicles,to the new range of applications,including grid storage solutions.With numerous published papers and broad reviews already available on the subject of Ni-rich oxides,this review focuses more on the most recent progress and new ideas presented in the literature references.The covered topics include doping and composition optimization,advanced coating,concentration gradient and single crystal materials,as well as innovations concerning new electrolytes and their modification,with the application of Ni-rich cathodes in solid-state batteries also discussed.Related cathode materials are briefly mentioned,with the high-entropy approach and zero-strain concept presented as well.A critical overview of the still unresolved issues is given,with perspectives on the further directions of studies and the expected gains provided.

Recent Progress and Regulation Strategies of Layered Materials as Cathode of Aqueous Zinc-Ion Batteries

Aqueous zinc-ion batteries(ZIBs)have shown great potential in the fields of wearable devices,consumer electronics,and electric vehicles due to their high level of safety,low cost,and multiple electron transfer.The layered cathode materials of ZIBs hold a stable structure during charge and discharge reactions owing to the ultrafast and straightforward(de)intercalation-type storage mechanism of Zn^(2+)ions in their tunable interlayer spacing and their abilities to accommodate other guest ions or molecules.Nevertheless,the challenges of inadequate energy density,dissolution of active materials,uncontrollable byproducts,increased internal pressure,and a large de-solvation penalty have been deemed an obstacle to the development of ZIBs.In this review,recent strategies on the structure regulation of layered materials for aqueous zinc-ion energy storage devices are systematically summarized.Finally,critical science challenges and future outlooks are proposed to guide and promote the development of advanced cathode materials for ZIBs.

Lowering Sodium-Storage Lattice Strains of Layered Oxide Cathodes by Pushing Charge Transfer on Anions

Due to a high energy density,layered transition-metal oxides have gained much attention as the promising sodium-ion batteries cathodes.However,they readily suffer from multiple phase transitions during the Na extraction process,resulting in large lattice strains which are the origin of cycledstructure degradations.Here,we demonstrate that the Na-storage lattice strains of layered oxides can be reduced by pushing charge transfer on anions(O^(2-)).Specifically,the designed O3-type Ru-based model compound,which shows an increased charge transfer on anions,displays retarded O3-P3-O1 multiple phase transitions and obviously reduced lattice strains upon cycling as directly revealed by a combination of ex situ X-ray absorption spectroscopy,in situ X-ray diffraction and geometric phase analysis.Meanwhile,the stable Na-storage lattice structure leads to a superior cycling stability with an excellent capacity retention of 84%and ultralow voltage decay of 0.2 mV/cycle after 300 cycles.More broadly,our work highlights an intrinsically structure-regulation strategy to enable a stable cycling structure of layered oxides meanwhile increasing the materials’redox activity and Nadiffusion kinetics.

Boosting rate performance of layered lithium-rich cathode materials by oxygen vacancy induced surface multicomponent integration

The rapid development of electric vehicles and portable energy storage systems demands improvements in the energy density and cost-effectiveness of lithium-ion batteries,a domain in which Lithium-rich layered cathode(LLO)materials inherently excel.However,these materials face practical challenges,such as low initial Coulombic efficiency,inferior cycle/rate performance,and voltage decline during cycling,which limit practical application.Our study introduces a surface multi-component integration strategy that incorporates oxygen vacancies into the pristine LLO material Li1.2Mn_(0.6)Ni_(0.2)O_(2).This process involves a brief citric acid treatment followed by calcination,aiming to explore rate-dependent degradation behavior.The induced surface oxygen vacancies can reduce surface oxygen partial pressure and diminish the generation of O_(2)and other highly reactive oxygen species on the surface,thereby facilitating the activation of Li ions trapped in tetrahedral sites while overcoming transport barriers.Additionally,the formation of a spinel-like phase with 3D Li+diffusion channels significantly improves Li^(+)diffusion kinetics and stabilizes the surface structure.The optimally modified sample boasts a discharge capacity of 299.5 mA h g^(-1)at a 0.1 C and 251.6 mA h g^(-1)at a 1 C during the initial activation cycle,with an impressive capacity of 222.1 mA h g^(-1)at a 5 C.Most notably,it retained nearly 70%of its capacity after 300 cycles at this elevated rate.This straightforward,effective,and highly viable modification strategy provides a crucial resolution for overcoming challenges associated with LLO materials,making them more suitable for practical application.

Reversible Mn^(2+)/Mn^(4+)double-electron redox in P3-type layer-structured sodium-ion cathode

The balance between cationic redox and oxygen redox in layer-structured cathode materials is an important issue for sodium batteries to obtain high energy density and considerable cycle stability.Oxygen redox can contribute extra capacity to increase energy density,but results in lattice instability and capacity fading caused by lattice oxygen gliding and oxygen release.In this work,reversible Mn^(2+)/Mn^(4+)redox is realized in a P3-Na_(0.65)Li_(0.2)Co_(0.05)Mn_(0.75)O_(2)cathode material with high specific capacity and structure stability via Co substitution.The contribution of oxygen redox is suppressed significantly by reversible Mn^(2+)/Mn^(4+)redox without sacrificing capacity,thus reducing lattice oxygen release and improving the structure stability.Synchrotron X-ray techniques reveal that P3 phase is well maintained in a wide voltage window of 1.5-4.5 V vs.Na^(+)/Na even at 10 C and after long-term cycling.It is disclosed that charge compensation from Co/Mn-ions contributes to the voltage region below 4.2 V and O-ions contribute to the whole voltage range.The synergistic contributions of Mn^(2+)/Mn^(4+),Co^(2+)/Co^(3+),and O^(2-)/(O_n)^(2-)redox in P3-Na_(0.65)Li_(0.2)Co_(0.05)Mn_(0.75)O_(2)lead to a high reversible capacity of 215.0 m A h g^(-1)at 0.1 C with considerable cycle stability.The strategy opens up new opportunities for the design of high capacity cathode materials for rechargeable batteries.

Residual alkali-evoked cross-linked polymer layer for anti-air-sensitivity LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)cathode

High-energy density lithium-ion batteries(LIBs)with layered high-nickel oxide cathodes(LiNi_(x)Co_(y)Mn_(1-x-y)O_(2),x≥0.8)show great promise in consumer electronics and vehicular applications.However,LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)faces challenges related to capacity decay caused by residual alkalis owing to high sensitivity to air.To address this issue,we propose a hazardous substances upcycling method that fundamentally mitigates alkali content and concurrently induces the emergence of an anti-air-sensitive layer on the cathode surface.Through the neutralization of polyacrylic acid(PAA)with residual alkalis and then coupling it with 3-aminopropyl triethoxysilane(KH550),a stable and ion-conductive cross-linked polymer layer is in situ integrated into the LiNi_(0.89)Co_(0.06)Mn_(0.05)O_(2)(NCM)cathode.Our characterization and measurements demonstrate its effectiveness.The NCM material exhibits impressive cycling performance,retaining 88.4%of its capacity after 200 cycles at 5 C and achieving an extraordinary specific capacity of 170.0 mA h g^(-1) at 10 C.Importantly,this layer on the NCM efficiently suppresses unfavorable phase transitions,severe electrolyte degradation,and CO_(2)gas evolution,while maintaining commendable resistance to air exposure.This surface modification strategy shows widespread potential for creating air-stable LiNi_(x)Co_(y)Mn_(1-x-y)O_(2)cathodes,thereby advancing high-performance LIBs.

Recent progress of hybrid cathode interface layer for organic solar cells

Organic solar cells(OSCs)have gained conspicuous progress during the past few decades due to the development of materials and upgrading of the device structure.The power conversion efficiency(PCE)of the single-junction device had surpassed 19%.The cathode interface layer(CIL),by optimizing the connection between the active layer and the cathode electrode,has become a momentous part to strengthen the performances of the OSCs.Simultaneously,CIL is also indispensable to illustrating the working mechanism of OSCs and enhancing the stability of the OSCs.In this essay,hybrid CILs in OSCs have been summarized.Firstly,the advancement and operating mechanism of OSCs,and the effects and relevant design rules of CIL are briefly concluded;secondly,the significant influence of CIL on enhancing the stability and PCE of OSCs is presented;thirdly,the characteristics of organic hybrid CIL and organic-inorganic hybrid CIL are introduced.Finally,the conclusion and outlook of CIL are summarized.

Surface-engineering of layered LiNi_(0.815)Co_(0.15)Al_(0.035)O_2 cathode material for high-energy and stable Li-ion batteries

Surface engineering is an effective strategy to restrain the generation of rocksalt NiO phase on surface of layered LiNi0.815Co0.15Al0.035O2（NCA） primary nanoparticles, a representative Ni-rich layered oxides cathode materials. Herein, we demonstrate the kilogram-scale synthesis of few-layer reduced graphene oxide（rGO） conformably coated NCA primary nanoparticles cathode materials by a mechanical wet ball-milling strategy. The lightening rGO coating layer effectively avoids the direct contact of electrolyte and NCA with rapid electrons transfer. As a result, the as-obtained NCA@rGO hybrids with only 1.0 wt% rGO content can deliver a high specific capacity（196 mAh g-1 at 0.2 C） and fast charge/discharge capability（127 mAh g-1 at 5 C）, which is much higher than the corresponding NCA nanoparticles（95 mAh g-1 at 5 C）. Even after100 cycles at 1 C, 91.7% of initial reversible capacity is still maintained. Furthermore, a prismatic pouch cell（240 mAh） is also successfully assembled with the commercial graphite anode.

Thermodynamically Revealing the Essence of Order and Disorder Structures in Layered Cathode Materials

Layered transition metal(TM) oxides are one of the most widely used cathode materials in lithium-ion batteries. The atomic configuration in TM layer of these materials is often known to be random when multiple TM elements co-exist in the layer(e.g. Ni, Co and Mn). By contrast, the configuration tends to be ordered if the elements are Li and Mn. Here, by using special quasi-random structures(SQS) algorithm, the essential reasons of the ordering in a promising Li-rich Mn-based cathode material Li2MnO3 are investigated. The difference of internal energy and entropy between ordered and disordered materials is calculated. As a result, based on the Gibbs free energy, it is found that Li2MnO3 should have an ordered structure in TM layer. In comparison, structures with Ni-Mn ratio of 2:1 are predicted to have a disordered TM layer, because the entropy terms have larger impact on the structural ordering than internal energy terms.

Spray pyrolysis synthesis of nickel-rich layered cathodes LiNi_(1-2x)Co_xMn_xO_2(x = 0.075, 0.05, 0.025) for lithium-ion batteries

In this study we report a series of nickel-rich layered cathodes LiNi1-2xCoxMnxO2（x = 0.075, 0.05,0.025） prepared from chlorides solution via ultrasonic spray pyrolysis. SEM images illustrate that the samples are submicron-sized particles and the particle sizes increase with the increase of Ni content.LiNi0.85Co0.075Mn0.075O2 delivers a discharge capacity of 174.9 mAh g-1 with holding 93% reversible capacity at 1 C after 80 cycles, and can maintain a discharge capacity of 175.3 mAh g-1 at 5 C rate. With increasing Ni content, the initial specific capacity increases while the cycling and rate performance degrades in some extent. These satisfying results demonstrate that spray pyrolysis is a powerful and efficient synthesis technology for producing Ni-rich layered cathode（Ni content 〉 80%）.

Review of the electrochemical performance and interfacial issues of high-nickel layered cathodes in inorganic all-solid-state batteries

All-solid-state batteries potentially exhibit high specific energy and high safety,which is one of the development directions for nextgeneration lithium-ion batteries.The compatibility of all-solid composite electrodes with high-nickel layered cathodes and inorganic solid electrolytes is one of the important problems to be solved.In addition,the interface and mechanical problems of high-nickel layered cathodes and inorganic solid electrolyte composite electrodes have not been thoroughly addressed.In this paper,the possible interface and mechanical problems in the preparation of high-nickel layered cathodes and inorganic solid electrolytes and their interface reaction during charge–discharge and cycling are reviewed.The mechanical contact problems from phenomena to internal causes are also analyzed.Uniform contact between the high-nickel cathode and solid electrolyte in space and the ionic conductivity of the solid electrolyte are the prerequisites for the good performance of a high-nickel layered cathode.The interface reaction and contact loss between the high-nickel layered cathode and solid electrolyte in the composite electrode directly affect the passage of ions and electrons into the active material.The buffer layer constructed on the high-nickel cathode surface can prevent direct contact between the active material and electrolyte and slow down their interface reaction.An appropriate protective layer can also slow down the interface contact loss by reducing the volume change of the high-nickel layered cathode during charge and discharge.Finally,the following recommendations are put forward to realize the development vision of high-nickel layered cathodes:(1)develop electrochemical systems for high-nickel layered cathodes and inorganic solid electrolytes;(2)elucidate the basic science of interface and electrode processes between high-nickel layered cathodes and inorganic solid electrolytes,clarify the mechanisms of the interfacial chemical and electrochemical reactions between the two materials,and address the intrinsic safety issues;(3)strengthen the development of research and engineering technologies and their preparation methods for composite electrodes with high-nickel layered cathodes and solid electrolytes and promote the industrialization of all-solid-state batteries.

Unlocking high-rate O3 layered oxide cathode for Na-ion batteries via ion migration path modulation

O3-NaNi1/3Fe1/3Mn1/3O2is a promising layered cathode material with high specific capacity,low cost,and simple synthesis.However,sluggish kinetic hindrance is attributed to the size discrepancy between the large Na-ion and narrow tetrahedral interstitial positions,leading to inferior rate capacity and low reversible capacity.Herein,F with light-weight and strong electronegativity is introduced to substitute O atoms in the bulk structure,which intensifies the bond strength of transition metal and oxygen and enlarges the Na+diffusion channel.In addition,density-functional theory(DFT) calculations demonstrate that the electrostatic interaction is weakened between Na+in the tetrahedral site and the transitionmetal cation directly below it,dramatically reducing the migration barriers of Na+diffusion.Consequently,the as-obtained NaNi1/3Fe1/3Mn1/3O1.95F0.05sample displays outstanding rate performance of 86.7 mA h g^(-1)at 10 C and excellent capacity retention of 84.1% after 100 cycles at 2 C.Moreover,a full cell configuration using a hard carbon anode reaches the energy density of 307.7 Wh kg^(-1).This strategy paves the way for novel means of modulating the Na-ion migration path for high-rate O3-type layered cathode materials.