New Strategy for Boosting Cathodic Performance of Protonic Ceramic Fuel Cells Through Incorporating a Superior Hydronation Second Phase

For protonic ceramic fuel cells,it is key to develop material with high intrinsic activity for oxygen activation and bulk proton conductivity enabling water formation at entire electrode surface.However,a higher water content which benefitting for the increasing proton conductivity will not only dilute the oxygen in the gas,but also suppress the O_(2)adsorption on the electrode surface.Herein,a new electrode design concept is proposed,that may overcome this dilemma.By introducing a second phase with high-hydrating capability into a conventional cobalt-free perovskite to form a unique nanocomposite electrode,high proton conductivity/concentration can be reached at low water content in atmosphere.In addition,the hydronation creates additional fast proton transport channel along the two-phase interface.As a result,high protonic conductivity is reached,leading to a new breakthrough in performance for proton ceramic fuel cells and electrolysis cells devices among available air electrodes.

Cathodic micro-arc electro-deposition of ZrO_2 coatings in an aqueous solution containing colloidal particles

By a novel technique-cathodic micro-arc electro-deposition (CMED), ZrO_2coatings were deposited on an FeCrAl alloy. Experimental results show that the necessary conditionsfor obtaining ZrO_2 coatings are to apply a pulse peak voltage over a critical value and addmoderate amounts of ZrO_2 colloidal particles and Zr(NO_3)_4 in the aqueous solution. Theas-deposited coatings are porous because hydrogen, water, and other vapors are generated andreleased from the coatings to the solution during the spark reaction. The coatings containmonoclinic and tetragonal crystalline ZrO_2 with certain degree of amorphous structure. Theprocessing parameters and mechanism of CMED were discussed.

CATHODIC PROCESS AND WEAR RESISTANCE OF ELECTRO-DEPOSITED RE-Ni-W-P-SiC COMPOSITE COATING

Cathodic deposition current density of the composite coatings increases when SiC par-ticles and rare earth (RE) were added in the bath, which is profitable for Ni- W-P alloy to deposit in the cathod, forming Ni-W-P-SiC and RE-Ni-W-P-SiC composite coatings. On the contrary, the addition of PTFE in the bath decreases cathodic deposition current density of the coatings. The current density increases a little when the amount of RE is 7-9g/l; however, the current density increases greatly when the amount of RE is increased to 11-13g/l. Bui ij the amount of RE is raised further, the current density decreases. Hardness and wear resistance of RE-Ni-W-P-SiC composite coating have been studied, and the results show that the hardness and wear resistance of RE-Ni-W-P-SiC composite coating increase with increasing heat treatment tempera-ture, which reach peak values at 400℃; while the hardness and wear resistance of the coating decrease with the rise of heat treated temperature continuously.

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.

A defective iron-based perovskite cathode for high-performance IT-SOFCs:Tailoring the oxygen vacancies using Nb/Ta co-doping

The sluggish kinetics of the electrochemical oxygen reduction reaction(ORR)in intermediatetemperature solid oxide fuel cells(IT-SOFCs)greatly limits the overall cell performance.In this study,an efficient and durable cathode material for IT-SOFCs is designed based on density functional theory(DFT)calculations by co-doping with Nb and Ta the B-site of the SrFeO_(3-δ)perovskite oxide.The DFT calculations suggest that Nb/Ta co-doping can regulate the energy band of the parent SrFeO_(3-δ)and help electron transfer.In symmetrical cells,such cathode with a SrFe_(0.8)Nb_(0.1)Ta_(0.1)O_(3-δ)(SFNT)detailed formula achieves a low cathode polarization resistance of 0.147Ωcm^(2) at 650℃.Electron spin resonance(ESR)and X-ray photoelectron spectroscopy(XPS)analysis confirm that the co-doping of Nb/Ta in SrFeO_(3-δ)B-site increases the balanced concentration of oxygen vacancies,enhancing the electrochemical performance when compared to 20 mol%Nb single-doped perovskite oxide.The cathode button cell with NiSDC|SDC|SFNT configuration achieves an outstanding peak power density of 1.3 W cm^(-2)at 650℃.Moreover,the button cell shows durability for 110 h under 0.65 V at 600℃ using wet H_(2) as fuel.

New insights into the pre-lithiation kinetics of single-crystalline Ni-rich cathodes for long-life Li-ion batteries

Developing single-crystalline Ni-rich cathodes is an effective strategy to improve the safety and cycle life of Li-ion batteries(LIBs).However,the easy-to-loss of Li and O in high-temperature lithiation results in unsatisfactory ordered layered structure and stoichiometry.Herein,we demonstrate the synthesis of highly-ordered and fully-stoichiometric single-crystalline LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)cathodes by the regulation of pre-lithiation kinetics.The well-balanced pre-lithiation kinetics have been proved to greatly improve the proportion of layered phase in the intermediate by inhibiting the formation of metastable spinel phase,which promoted the rapid transformation of the intermediate into highly-ordered layered SC-NCM83 in the subsequent lithiation process.After coating a layer of Li_(2)O–B_(2)O_(3),the resultant cathodes deliver superior cycling stability with 90.9%capacity retention at 1C after 300 cycles in pouch-type full batteries.The enhancement mechanism has also been clarified.These findings exhibit fundamental insights into the pre-lithiation kinetics process for guiding the synthesis of high-quality singlecrystalline Ni-rich cathodes.

Manipulating Na occupation and constructing protective film of P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2) as long-term cycle stability cathode for sodium-ion batteries

P2-Na_(0.67)Ni_(0.33)Mn_(0.67)O_(2)(NNMO)is promising cathode material for sodium-ion batteries(SIBs)due to its high specific capacity and fast Na+diffusion rate.Nonetheless,the irreversible P2-O_(2)phase transformation,Na+/vacancy ordering,and transition metal(TM)dissolution seriously damage its cycling stability and restrict its commercialization process.Herein,Na occupation manipulation and interface stabilization are proposed to strengthen the phase structure of NNMO by synergistic Zn/Ti co-doping and introducing lithium difluorophosp(LiPO_(2)F_(2))film-forming electrolyte additive.The Zn/Ti co-doping regulates the occupancy ratio of Nae/Nafat Na sites and disorganizes the Na+/vacancy ordering,resulting in a faster Na+diffusion kinetics and reversible P2-Z phase transition for P2-Na_(0.67)Ni_(0.28)Zn_(0.05)Mn_(0.62)Ti_(0.05)O_(2)(NNZMTO).Meanwhile,the LiPO_(2)F_(2)additive can form homogeneous and ultrathin cathode-electrolyte interphase(CEI)on NNZMTO surface,which can stabilize the NNZMTO-electrolyte interface to prevent TM dissolution,surface structure transformation,and micro-crack generation.Combination studies of in situ and ex situ characterizations and theoretical calculations were used to elucidate the storage mechanism of NNZMTO with Li PO_(2)F_(2)additive.As a result,the NNZMTO displays outstanding capacity retention of 94.44%after 500 cycles at 1C with 0.3 wt%Li PO_(2)F_(2),excellent rate performance of 92.5 mA h g^(-1)at 8C with 0.1 wt%Li PO_(2)F_(2),and remarkable full cell capability.This work highlights the important role of manipulating Na occupation and constructing protective film in the design of layered materials,which provides a promising direction for developing high-performance cathodes for SIBs.

Phase-engineering modulation of Mn-based oxide cathode for constructing super-stable sodium storage

The Mn-based oxide cathode with enriched crystal phase structure and component diversity can provide the excellent chemistry structure for Na-ion batteries.Nevertheless,the broad application prospect is obstructed by the sluggish Na^(+)kinetics and the phase transitions upon cycling.Herein,we establish the thermodynamically stable phase diagram of various Mn-based oxide composites precisely controlled by sodium content tailoring strategy coupling with co-doping and solid-state reaction.The chemical environment of the P2/P'3 and P2/P3 biphasic composites indicate that the charge compensation mechanism stems from the cooperative contribution of anions and cations.Benefiting from the no phase transition to scavenge the structure strain,P2/P'3 electrode can deliver long cycling stability(capacity retention of 73.8%after 1000 cycles at 10 C)and outstanding rate properties(the discharge capacity of 84.08 mA h g^(-1)at 20 C)than P2/P3 electrode.Furthermore,the DFT calculation demonstrates that the introducing novel P'3 phase can significantly regulate the Na^(+)reaction dynamics and modify the local electron configuration of Mn.The effective phase engineering can provide a reference for designing other high-performance electrode materials for 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.

Electrocarboxylation of CO_(2) with Organic Substrates:Toward Cathodic Reaction

Electrocarboxylation of carbon dioxide(CO_(2))using organic substrates has emerged as a promising method for the sustainable synthesis of value-added carboxylic acids due to its renewable energy source and mild reaction conditions.The reactivity and product selectivity of electrocarboxylation are highly dependent on the cathodic behavior,involving a sequence of electron transfers and chemical reactions.Hence,it is necessary to understand the cathodic reaction mechanisms for optimizing reaction performance and product distribution.In this work,a review of recent advancements in the electrocarboxylation of CO_(2)with organic substrates based on different cathodic reaction pathways is presented to provide a reference for the development of novel methodologies of CO_(2)electrocarboxylation.Herein,cathodic reactions are particularly classified into two categories based on the initial electron carriers(i.e.,CO_(2)radical anion and substrate radical anion).Furthermore,three cathodic pathways(ENE(N),ENED,and EDEN)of substrate radical anion-induced electrocarboxylation are discussed,which differ in their electron transfer sequence,substrate dissociation,and nucleophilic reaction,to highlight their implications on reactivity and product selectivity.

Suppressed Internal Intrinsic Stress Engineering in High-Performance Ni-Rich Cathode Via Multi layered In Situ Coating Structure

LiNi_(x)Co_(y)Al_(z)O_(2)(NCA)cathode materials are drawing widespread attention,but the huge gap between the ideal and present cyclic stability still hinders their further commercial application,especially for the Ni-rich LiNi_(x)Co_(y)Al_(z)O_(2)(x>0.8,x+y+z=1)cathode material,which is owing to the structural degradation and particles'intrinsic fracture.To tackle the problems,Li_(0.5)La_(2)Al_(0.5)O_(4)in situ coated and Mn compensating doped multilayer LiNi_(0.82)Co_(0.14)Al_(0.04)O_(2)was prepared.XRD refinement indicates that La-Mn co-modifying could realize appropriate Li/Ni disorder degree.Calculated results and in situ XRD patterns reveal that the LLAO coating layer could effectively restrain crack in secondary particles benefited from the suppressed internal strain.AFM further improves as NCA-LM2 has superior mechanical property.The SEM,TEM,XPS tests indicate that the cycled cathode with LLAO-Mn modification displays a more complete morphology and less side reaction with electrolyte.DEMS was used to further investigate cathode-electrolyte interface which was reflected by gas evolution.NCA-LM2 releases less CO_(2)than NCA-P indexing on a more stable surface.The modified material presents outstanding capacity retention of 96.2%after 100 cycles in the voltage range of 3.0-4.4 V at 1C,13%higher than that of the pristine and 80.8%at 1 C after 300 cycles.This excellent electrochemical performance could be attributed to the fact that the high chemically stable coating layer of Li_(0.5)La_(2)Al_(0.5)O_(4)(LLAO)could enhance the interface and the Mn doping layer could suppress the influence of the lattice mismatch and distortion.We believe that it can be a useful strategy for the modification of Ni-rich cathode material and other advanced functional material.

Boosting oxygen reduction activity and CO_(2) resistance on bismuth ferrite-based perovskite cathode for low-temperature solid oxide fuel cells below 600℃

Developing efficient and stable cathodes for low-temperature solid oxide fuel cells(LT-SOFCs) is of great importance for the practical commercialization.Herein,we propose a series of Sm-modified Bi_(0.7-x)Sm_xSr_(0.3)FeO_(3-δ) perovskites as highly-active catalysts for LT-SOFCs.Sm doping can significantly enhance the electrocata lytic activity and chemical stability of cathode.At 600℃,Bi_(0.675)Sm_(0.025)Sr_(0.3)FeO_(3-δ)(BSSF25) cathode has been found to be the optimum composition with a polarization resistance of 0.098 Ω cm^2,which is only around 22.8% of Bi_(0.7)Sr_(0.3)FeO_(3-δ)(BSF).A full cell utilizing BSSF25 displays an exceptional output density of 790 mW cm^(-2),which can operate continuously over100 h without obvious degradation.The remarkable electrochemical performance observed can be attributed to the improved O_(2) transport kinetics,superior surface oxygen adsorption capacity,as well as O_(2)p band centers in close proximity to the Fermi level.Moreover,larger average bonding energy(ABE) and the presence of highly acidic Bi,Sm,and Fe ions restrict the adsorption of CO_(2) on the cathode surface,resulting in excellent CO_(2) resistivity.This work provides valuable guidance for systematic design of efficient and durable catalysts for LT-SOFCs.

Plasma diagnosis of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Filtered cathodic vacuum arc(FCVA)deposition is regarded as an important technique for the synthesis of tetrahedral amorphous carbon(ta-C)films due to its high ionization rate,high deposition rate and effective filtration of macroparticles.Probing the plasma characteristics of arc discharge contributes to understanding the deposition mechanism of ta-C films on a microscopic level.This work focuses on the plasma diagnosis of an FCVA discharge using a Langmuir dualprobe system with a discrete Fourier transform smoothing method.During the ta-C film deposition,the arc current of graphite cathodes and deposition pressure vary from 30 to 90 A and from 0.3 to 0.9 Pa,respectively.The plasma density increases with arc current but decreases with pressure.The carbon plasma density generated by the arc discharge is around the order of10^(10)cm^(-3).The electron temperature varies in the range of 2-3.5 eV.As the number of cathodic arc sources and the current of the focused magnetic coil increase,the plasma density increases.The ratio of the intensity of the D-Raman peak and G-Raman peak(I_(D)/I_(G))of the ta-C films increases with increasing plasma density,resulting in a decrease in film hardness.It is indicated that the mechanical properties of ta-C films depend not only on the ion energy but also on the carbon plasma density.

Preferentially selective extraction of lithium from spent LiCoO_(2)cathodes by medium-temperature carbon reduction roasting

Lithium recovery from spent lithium-ion batteries(LIBs)have attracted extensive attention due to the skyrocketing price of lithium.The medium-temperature carbon reduction roasting was proposed to preferential selective extraction of lithium from spent Li-CoO_(2)(LCO)cathodes to overcome the incomplete recovery and loss of lithium during the recycling process.The LCO layered structure was destroyed and lithium was completely converted into water-soluble Li2CO_(3)under a suitable temperature to control the reduced state of the cobalt oxide.The Co metal agglomerates generated during medium-temperature carbon reduction roasting were broken by wet grinding and ultrasonic crushing to release the entrained lithium.The results showed that 99.10%of the whole lithium could be recovered as Li2CO_(3)with a purity of 99.55%.This work provided a new perspective on the preferentially selective extraction of lithium from spent lithium batteries.

Tuning Li/Ni mixing by reactive coating to boost the stability of cobalt-free Ni-rich cathode

Cobalt-free cathode materials are attractive for their high capacity and low cost,yet they still encounter issues with structural and surface instability.AlPO_(4),in particular,has garnered attention as an effective stabilizer for bulk and surface.However,the impact of interfacial reactions and elemental interdiffusion between AlPO_(4) and LiNi_(0.95)Mn_(0.05)O_(2) upon sintering on the bulk and surface remains elusive.In this study,we demonstrate that during the heat treatment process,AlPO_(4) decomposes,resulting in Al doping into the bulk of the cathode through elemental interdiffusion.Simultaneously,PO_(4)^(3-)reacts with the surface Li of material to form a Li_3PO_(4) coating,inducing lithium deficiency,thereby increasing Li/Ni mixing.The suitable Li/Ni mixing,previously overlooked in AlPO_(4) modification,plays a pivotal role in stabilizing the bulk and surface,exceeding the synergy of Al doping and Li_3PO_(4) coating.The presence of Ni^(2+)ions in the lithium layers contributes to the stabilization of the delithiated structure via a structural pillar effect.Moreover,suitable Li/Ni mixing can stabilize the lattice oxygen and electrode-electrolyte interface by increasing oxygen removal energy and reducing the overlap between the Ni^(3+/4+)e_g and O^(2-)2p orbitals.These findings offer new perspectives for the design of stable cobalt-free cathode materials.

Enhancing thermodynamic stability of single-crystal Ni-rich cathode material via a synergistic dual-substitution strategy

Nickel(Ni)-rich cathode materials have become promising candidates for the next-generation electrical vehicles due to their high specific capacity.However,the poor thermodynamic stability(including cyclic performance and safety performance or thermal stability)will restrain their wide commercial application.Herein,a single-crystal Ni-rich Li Ni_(0.83)Co_(0.12)Mn_(0.05)O_(2) cathode material is synthesized and modified by a dual-substitution strategy in which the high-valence doping element improves the structural stability by forming strong metal–oxygen binding forces,while the low-valence doping element eliminates high Li^(+)/Ni^(2+)mixing.As a result,this synergistic dual substitution can effectively suppress H2-H3 phase transition and generation of microcracks,thereby ultimately improving the thermodynamic stability of Ni-rich cathode material.Notably,the dual-doped Ni-rich cathode delivers an extremely high capacity retention of 81%after 250 cycles(vs.Li/Li+)in coin-type half cells and 87%after 1000 cycles(vs.graphite/Li^(+))in pouch-type full cells at a high temperature of 55℃.More impressively,the dual-doped sample exhibits excellent thermal stability,which demonstrates a higher thermal runaway temperature and a lower calorific value.The synergetic effects of this dual-substitution strategy pave a new pathway for addressing the critical challenges of Ni-rich cathode at high temperatures,which will significantly advance the high-energy-density and high-safety cathodes to the subsequent commercialization.

Corrigendum to“Anthraquinone derivatives supported by Ti_(3)C_(2)(MXene)as cathode materials for aluminum-organic batteries”[J.Energy Chem.74(2022)174–183]

The authors regret that the printed version of the above article contained an error reference.We hope to correct it here.[14]B.J.M.Christophe Legein,Franck Fayon,Angew.Chem.Int.Ed.,132(2020)19409–19415.

Optical and electrical properties of BaSnO_(3) and In_2O_(3) mixed transparent conductive films deposited by filtered cathodic vacuum arc technique at room temperature

For the crystalline temperature of BaSnO_(3)(BTO)was above 650℃,the transparent conductive BTO-based films were always deposited above this temperature on epitaxy substrates by pulsed laser deposition or molecular beam epitaxy till now which limited there application in low temperature device process.In the article,the microstructure,optical and electrical of BTO and In_(2)O_(3) mixed transparent conductive BaInSnO_(x)(BITO)film deposited by filtered cathodic vacuum arc technique(FCVA)on glass substrate at room temperature were firstly reported.The BITO film with thickness of 300 nm had mainly In_(2)O_(3) polycrystalline phase,and minor polycrystalline BTO phase with(001),(011),(111),(002),(222)crystal faces which were first deposited at room temperature on amorphous glass.The transmittance was 70%–80%in the visible light region with linear refractive index of 1.94 and extinction coefficient of 0.004 at 550-nm wavelength.The basic optical properties included the real and imaginary parts,high frequency dielectric constants,the absorption coefficient,the Urbach energy,the indirect and direct band gaps,the oscillator and dispersion energies,the static refractive index and dielectric constant,the average oscillator wavelength,oscillator length strength,the linear and the third-order nonlinear optical susceptibilities,and the nonlinear refractive index were all calculated.The film was the n-type conductor with sheet resistance of 704.7Ω/□,resistivity of 0.02Ω⋅cm,mobility of 18.9 cm2/V⋅s,and carrier electron concentration of 1.6×10^(19) cm^(−3) at room temperature.The results suggested that the BITO film deposited by FCVA had potential application in transparent conductive films-based low temperature device process.

Influence of the position relationship between the cathode and magnetic separatrix on the discharge process of a Hall thruster

Previous studies have shown that there is an obvious coupling relationship between the installation location of the external cathode and the magnetic separatrix in the plume region of a Hall thruster.In this paper,the particle-in-cell simulation method is used to compare the thruster discharge process under the conditions of different position relationships between the cathode and the magnetic separatrix.By comparing the distribution of electron conduction,potential,plasma density and other microscopic parameters,we try to explain the formation mechanism of the discharge difference.The simulation results show that the cathode inside and outside the magnetic separatrix has a significant effect on the distribution of potential and plasma density.When the cathode is located on the outer side of the magnetic separatrix,the potential above the plume region is relatively low,and there is a strong potential gradient above the plume region.This potential gradient is more conducive to the radial diffusion of ions above the plume,which is the main reason for the strong divergence of the plume.The distribution of ion density is also consistent with the distribution of potential.When the cathode is located on the outer side of the magnetic separatrix,the radial diffusion of ions in the plume region is enhanced.Meanwhile,by comparing the results of electron conduction,it is found that the traiectories of electrons emitted from the cathode are significantly different between the inner and outer sides of the magnetic separatrix.This is mainly because the electrons are affected by the magnetic mirror effect of the magnetic tip,which makes it difficult for the electrons to move across the magnetic separatrix.This is the main reason for the difference in potential distribution.In this paper,the simulation results of macroscopic parameters under several conditions are also compared,and they are consistent with the experimental results.The cathode is located on the inner side of the magnetic separatrix,which can effectively reduce the plume divergence angle and improve the thrust.In this paper,the cathode moves from R=50 mm to R=35 mm along the radial direction,the thrust increases by 3.6 mN and the plume divergence angle decreases by 23.77%.Combined with the comparison of the ionization region and the peak ion density,it is found that the main reason for the change in thrust is the change in the radial diffusion of ions in the plume region.

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.