Vacancy Formation Energy Research Articles

Point Defects Stability, Hydrogen Diffusion, Electronic Structure, and Mechanical Properties of Defected Equiatomic γ(U,Zr) from First-Principles.

At present, many experimental fast reactors have adopted alloy nuclear fuels, for example, U-Zr alloy fuels. During the neutron irradiation process, vacancies and hydrogen (H) impurity atoms can both exist in U-Zr alloy fuels. Here, first-principles density functional theory (DFT) is employed to study the behaviors of vacancies and H atoms in disordered-γ(U,Zr) as well as their impacts on the electronic structure and mechanical properties. The formation energy of vacancies and hydrogen solution energy are calculated. The effect of vacancies on the migration barrier of hydrogen atoms is revealed. The effect of vacancies and hydrogen atom on densities of states and elastic constants are also presented. The results illustrate that U vacancy is easier to be formed than Zr vacancy. The H interstitial prefers the tetrahedral site. Besides, U vacancy shows H-trap ability and can raise the H migration barrier. Almost all the defects lead to decreases in electrical conductivity and bulk modulus. It is also found that the main effect of defects is on the U-5f orbitals. This work provides a theoretical understanding of the effect of defects on the electronic and mechanical properties of U-Zr alloys, which is an essential step toward tailoring their performance.

First-principles study of vacancy defects in TiVTa and TiVTaNb concentrated solid-solution alloys

The formation and migration energies of vacancy defects are studied systematically by first-principal calculations method in three concentrated solid-solution alloys (CSAs), namely equimolar TiVTa alloy, TiVTa50 alloy with Ta content increased to 50%, and equimolar TiVTaNb alloy. It is found that the vacancy formation and migration in TiVTaNb alloy are more difficult than that in TiVTa and TiVTa50 alloys. The TiVTa alloy has the larger local lattice distortion than TiVTa50 and TiVTaNb alloys, which would lead to an irregular energy landscape and make it easier to form vacancies. Vacancies are easily formed in Ti-rich environments and the trend reverses for in V-rich environments in these three alloys, originating from the large local lattice distortion in Ti-rich environments and strong binding interactions between Ti atoms and vacancies. Ti atoms with the largest size tend to migrate to neighboring vacancies in these three alloys. The addition of Nb enhances the electron interactions between atoms in TiVTaNb alloy. Compared to TiVTa and TiVTa50 alloys, the migration barrier of atoms diffusing into vacancies in TiVTaNb alloy is improved due to the combination of strong electron interactions between atoms and lattice distortion. It is implied that the influence of alloy element combination on vacancy formation and migration energies may be greater than that of alloy element content in Ti-V-Ta and Ti-V-Ta-Nb alloys. These results provide fundamental insights into the defects evolution of CSAs with body-centered cubic (bcc) structure and supply the scientific basis for the composition design of bcc CSAs.

Oxygen vacancy formation and electronic reconstruction in strained LaNiO3 and LaNiO3/LaAlO3 superlattices

By using density functional theory calculations including a Coulomb repulsion term, we explore the formation of oxygen vacancies and their impact on the electronic and magnetic properties of strained bulk ${\mathrm{LaNiO}}_{3}$ and (${\mathrm{LaNiO}}_{3}{)}_{1}$/(${\mathrm{LaAlO}}_{3}{)}_{1}$(001) superlattices. For bulk ${\mathrm{LaNiO}}_{3}$, we find that epitaxial strain induces a substantial anisotropy in the oxygen vacancy formation energy. In particular, tensile strain promotes the selective reduction of apical oxygen, which may explain why the recently observed superconductivity in infinite-layer nickelates is limited to strained films. For (${\mathrm{LaNiO}}_{3}{)}_{1}$/(${\mathrm{LaAlO}}_{3}{)}_{1}$(001) superlattices, the simulations reveal that the ${\mathrm{NiO}}_{2}$ layer is most prone to vacancy formation, whereas the ${\mathrm{AlO}}_{2}$ layer exhibits generally the highest formation energies. The reduction is consistently endothermic, and a largely repulsive vacancy-vacancy interaction is identified as a function of the vacancy concentration. The released electrons are accommodated exclusively in the ${\mathrm{NiO}}_{2}$ layer, reducing the vacancy formation energy in the ${\mathrm{AlO}}_{2}$ layer by $\ensuremath{\sim}70%$ with respect to bulk ${\mathrm{LaAlO}}_{3}$. By varying the vacancy concentration from 0 to $8.3%$ in the ${\mathrm{NiO}}_{2}$ layer at tensile strain, we observe an unexpected transition from a localized site-disproportionated ($0.5%$) to a delocalized ($2.1%$) charge accommodation, a reentrant site disproportionation leading to a metal-to-insulator transition despite a half-filled majority-spin Ni ${e}_{g}$ manifold ($4.2%$), and finally a magnetic phase transition ($8.3%$). While a band gap of up to 0.5 eV opens at $4.2%$ for compressive strain, it is smaller for tensile strain or the system is metallic, which is in sharp contrast to the defect-free superlattice. The strong interplay of electronic reconstructions and structural modifications induced by oxygen vacancies in this system highlights the key role of an explicit supercell treatment beyond rigid-band methods and exemplifies the complex response to defects in artificial transition metal oxides.

Electronegative metal dopants improve switching variability in Al2O3 resistive switching devices

Resistive switching random access memories (RRAMs) promise to overcome the limitation of time- and energy-consumption set by increased training demand in the deep neural network. These devices enable the colocation of memory and processing by storing and utilizing information in the form of conductive networks, such as those made of oxygen vacancies. However, the inherent stochastic nature of atomic motion results in poor reliability and high switching variability in these devices, hindering their widespread use. In this paper, the authors propose a method to substantially reduce the switching variability of RRAM devices by doping the RRAM oxide electrolyte with electronegative metals. They find that electronegative metals reduce the oxygen vacancy formation energy, thereby pinning the conductive filament formation along fixed, predictable paths. This improved reliability enables multibit switching and can facilitate integration into large-scale hardware neural networks.

The synergic removal mechanism for photothermocatalytic toluene over single-atom Pt/TiO2 catalysts via flame spray pyrolysis

Photothermocatalytic oxidation is an environmentally-friendly, low-temperature, and high-efficient method to remove the air pollutant. Yet, the lack of active, inexpensive, and superior stability catalysts has greatly limited its extensive utilization. In this work, the effect of single-atom Pt loading on TiO2 support has been theoretically and experimentally studied to improve photothermocatalytic performance for the toluene combustion through flame spray pyrolysis (FSP). Pt loading can play two crucial roles into TiO2 optimization: (1) The low-valence Pt cation incorporated into TiO2 lattice is dramatically responsible for the anatase-rutile transformation (ART) and formation of sufficient oxygen vacancies; (2) Introducing the defect energy level and Pt-3d orbitals remarkably promote the charge separation efficiency of single-atom catalysts. Moreover, the existence of single-atom Pt nanoparticles can signally boost the activity of surface adsorbed and lattice oxygen, as well as substantially reduce the oxygen vacancy formation energy. Thus, the toluene removal under light irradiation reaches 90% conversion below 160 °C and is maximally 18 °C lower than that under only thermocatalytic oxidation. It is attributed to larger specific surface area (SSA), outstanding low-temperature reducibility, extremely dispersed hybrid PtOx, more surface active oxygen, and higher mobility of bulk oxygen. Interestingly, when the oxygen-fuel equivalent ratio φ distinctly increases by shifting precursor solvent from xylene to ethanol, the photothermocatalytic property of toluene can be remarkably enhanced on single-atom Pt catalysts. It is due to the higher Pt dispersion resulting from more intense burning and drastic turbulent mixing, as well as the superior ratio of the metallic Pt active sites originating from higher flame temperature. Eventually, the rate-determining step of C7H8 combustion on Pt/TiO2 and Cu/TiO2 slab are all the CC bond fracture of maleic anhydride to form acetic anhydride species, with the energy barriers of 112.03 and 188.74 kJ/mol, respectively.

Electronic descriptors for vacancy formation and hydrogen solution in Be-rich intermetallics

The use of an electronic descriptor is a high-throughput approach for predicting the chemical reactivities of various materials that has the potential to significantly facilitate the material design of Be intermetallic neutron multipliers for nuclear fusion applications. However, electronic descriptors for Be intermetallics with the desired properties, including radiation tolerance and reduced hydrogen retention, have been poorly understood. Herein, we perform first-principles calculations on 42 existing binary Be intermetallics to find an effective electronic descriptor. We demonstrate that the occupied Be p band center relative to the Fermi level is a bulk descriptor, correlating with the Be vacancy formation energy; a positive and linear correlation with a coefficient of determination R2 = 0.85 was observed for Be12X (X: transition metal). The upward shift in energy of the occupied Be p states with early or middle transition metals can reduce hydrogen solution energy, which could be attributed to the less filled anti-bonding state of interstitial hydrogen atom. It is confirmed that the bulk descriptor is an experimentally measurable scale, having the strong linearity (R2 = 0.97) with the calculated; therefore, it can accelerate the material development of beryllium intermetallic neutron multipliers.

Chemistry in Advancing Thermoelectric GeTe Materials.

ConspectusThe ever-growing energy crisis and the deteriorated environment caused by carbon energy consumption motivate the exploitation of alternative green and sustainable energy supplies. Because of the unique advantages of zero-emission, no moving parts, accurate temperature control, a long steady-state operation period, and the ability to operate in extreme situations, thermoelectrics, enabling the direct conversion between heat and electricity, is a promising and sustainable option for power generation and refrigeration. However, with increasing application potentials, thermoelectrics is now facing a major challenge: developing high-performance, Pb-free, and low-toxic thermoelectric materials and devices.As one group of promising candidates, GeTe derivatives have the potential to replace the widely used thermoelectric materials containing highly toxic elements. In this Account, we summarize our recent progress in developing high-performance GeTe-based thermoelectric materials via exploring innovative strategies to enhance electron transports and dampen phonon propagations. First, we fundamentally illustrate the underlying chemistry and physical reason for an intrinsically high carrier concentration in GeTe, which enormously restrains the thermoelectric performance of GeTe. From our theoretical calculations, the formation energy of Ge vacancy is the lowest among the defects in GeTe, energetically favoring Ge vacancies in the lattice and leading to intrinsically high carrier concentrations. Accordingly, aliovalent doping/alloying is proposed to increase the formation energy of Ge vacancies and decrease the carrier concentration to the optimal level. We then outline the newly developed method to refine the band structures of GeTe with tuned electronic transport. On the basis of the molecular orbital theory, the energy offset between two valence band edges at the L and Σ points in GeTe should be ascribed to the slightly different Ge_4s orbital characters at these two points, which guides the screening of dopants for band convergence. Besides, the Rashba spin splitting is explored to increase the band degeneracy of GeTe. Afterward, we analyze the dampened phonon propagation in GeTe to minimize its lattice thermal conductivity. Alloying with the heavy Sb atoms can shift the optical phonon modes toward low frequency and reinforce the interaction of optical and acoustic phonon modes so that the inherent phonon scattering is enhanced. In addition, planar vacancies and superlattice precipitates can significantly strengthen phonon scattering to result in ultralow lattice thermal conductivity. After that, we overview the finite elemental analysis simulations to optimize the device geometry for maximizing the device performance and introduce the as-developed prototype GeTe-based thermoelectric device. In the end, we point out future directions in the development of GeTe for device applications. The strategies summarized in this Account can serve as references for developing wide materials with enhanced thermoelectric performance.

Zn-doping and oxygen vacancy effects on the reactivity and properties of monoclinic and tetragonal ZrO2: a DFT study

Zirconia oxide (ZrO2) is a material that has aroused great interest in the scientific community for its general use in various technological applications, such as fuel cells, solar cells, electronic devices, catalysis, dental biomaterial and ceramics. When it is applied as a catalyst, the doping and vacancy effects of their crystalline phases are important properties to guide new developments. This work investigates tetragonal and monoclinic crystalline phases of the Zn-doped ZrO2 by periodic density functional calculations. Changes in the electronic and acid-basic properties were performed by Bader charge analysis, the density of states calculations (DOS) and the projected density of states (PDOS). The formation of oxygen vacancies was also evaluated. The calculated oxygen vacancy formation energies indicate that it is much easier to generate oxygen vacancy in the Zn-doped ZrO2 than in the pure material; in addition, oxygen vacancy formation is favored in the monoclinic phase. Bader charge analyses and projected density of states indicated that the doping of ZrO2 with Zn creates more basic and acid sites. The most stable material is the Zn-doped 3-fold coordinated Zr atom of the m-ZrO2, which can be used for future developments and applications.

An extended theory of vacancy formation and its application to ionic conduction in the intrinsic and extrinsic regions

ABSTRACT The theory of the vacancy formation in crystals has been extended by generalising the vacancy formation energy that depends on the number of vacancies resulting from thermal activation. This extension enables to describe the freezing of defect concentrations at lower temperature, while the derived vacancy concentration reduces to the Boltzmann–Arrhenius law at higher temperature. The implications of the low-temperature patterns and its relevance to non-equilibrium process in the defect concentrations have been also touched upon. In addition, based on the approach explored, we further construct a model for the ionic conductivity in the intrinsic and extrinsic regions, which is formulated by focusing on the relation between the number concentration and the mobility of ionic charge carriers. A theoretical background to the continuity (knee) across which the both ionic conductivity patterns are smoothly connected is corroborated by the present work.

Internal friction in thin-film ferrite bismuth with an amorphous structure

The internal friction spectra of an amorphous thin-film bismuth ferrite deposited on a silicon substrate were studied. The temperature dependence of mechanical losses near the glass transition temperature revealed a wide maximum of internal friction associated with α-relaxation of the amorphous structure. In this temperature region, two linear sections in the ln Q −1 vs (1/ T ) dependence are observed with an intersection point at the glass transition temperature. According to the results of low- and high-temperature internal friction investigation of the amorphous bismuth ferrite in the α-relaxation region, the values of the migration energy and the formation energy of vacancies-like defects were estimated, which are equal to E m = 0.80 ± 0.08 eV and E v = 0.88 ± 0.08 eV, respectively. • Internal friction Q −1 in amorphous bismuth ferrite BiFeO 3 at high temperatures was studied. • The Q −1 maximum is due to α-relaxation of the amorphous structure in thin-film BiFeO 3 . • Crystallization of the amorphous structure of BiFeO 3 is confirmed by the results of DTA and X-ray diffraction analysis. • Estimates of the migration energy and the formation energy of oxygen vacancies in the amorphous BiFeO 3 were made.

Pronounced inhibitory mechanism of Cr on vacancy-like defects in Fe9Cr alloy irradiation with helium ions

• First-principles calculations combined with positron annihilation spectroscopy. • The He atoms aggregate among (1 1 0) planes in the perfect Fe and Fe9Cr models. • Fe atoms around the He clusters are inclined to emit spontaneously. • The doping of Cr repels the He atoms and weakens the growth of He clusters. First-principles calculations and positron annihilation spectroscopy were used to investigate the effect of Cr atoms on He-induced vacancy-like defects in pure Fe and Fe9Cr alloys. The He atom is not energetically favorable at both the surface and the subsurface, but it becomes stable under the third atomic layer from the surface. The diffusion of He atoms to the vacuum and aggregation of He atoms into clusters coexist. We observed that the interstitial He n clusters prefer to stay along the (1 1 0) plane. Moreover, the small He n clusters induce strong lattice distortions, and the emission of a self-interstitial Fe atom located at the adjacent He n cluster is energetically favorable for n > 2 and vacancy formation energies of Fe9Cr are higher than that of Fe. This suggests that Cr atoms could effectively enhance the stability of Fe atoms around He n clusters but that the Fe atoms would still like to shift from the vicinity of He n to the surfaces of the models. In the experiment, Fe and Fe9Cr alloys were irradiated with He ions to a dose of 1 × 10 16 cm 2 and the positron annihilation results showed that the Fe9Cr alloy has a smaller relative S (ΔS) parameter value than pure Fe. The experimental results matched well with the theoretical analysis. These results would help provide additional insights into the behavior of He in irradiated Fe and Fe9Cr surfaces, necessary for the interpretation of the growth of the He bubble.

Effects of Vacancies on the Structural, Elastic, Electronic and Thermodynamic Properties of C11b-VSi2 by First-Principles Calculations

The effects of V and Si vacancies on structural stability, elastic properties, brittleness-toughness transition, Debye temperature and electronic properties of tetragonal C11b-VSi2 are investigated using the first-principles calculations. The vacancy formation energy and phonon dispersions confirm that perfect C11b-VSi2 and C11b-VSi2 with different atomic vacancies are thermodynamically and dynamically stable. The C11b-VSi2 with V-atom vacancies is more stable than that with Si-atom vacancies. The introduction of different atomic vacancies enhances the elastic modulus and its anisotropy of C11b-VSi2. The electron density difference and densities of state of perfect VSi2 and VSi2 with different vacancies are calculated, and the chemical bonding properties of perfect VSi2 and VSi2 with vacancies are discussed and analyzed. Additionally, the results show that the chemical bond strength of VSi2 is enhanced by the introduction of vacancies. Finally, Debye temperatures of perfect VSi2 and VSi2 with vacancies are also calculated.

Modulating lattice oxygen activity of Ca2Fe2O5 brownmillerite for the co-production of syngas and high purity hydrogen via chemical looping steam reforming of toluene

The chemical looping steam reforming (CLSR) of biomass tar enables the process intensification for the co-preparation of syngas and high purity hydrogen. The practical application of brownmillerite-structured Ca2Fe2O5 is hindered by activity-related issues such as low fuel conversion and oxygen transfer capacity. Here, the doping of heteroatoms, e.g. Ni induces structural changes to the brownmillerite lattice, transforming it from a Pnma phase to a Pcmn one, with increased distortion of the FeO6 octahedra. The structural changes lead to the upwards shifts of the O 2p band of oxygen carrier, and subsequently improved lattice oxygen activity as well as oxygen transfer capacity. The formation of oxygen vacancy is a rate determining step during CLSR, while the Ni-doped Ca2Fe2O5 reduces the energy of oxygen vacancy formation and energy barrier for lattice oxygen migration through the bulk. During CLSR, Ca2Ni0.25Fe1.75O5 lead to significant improvement in syngas productivity, hydrogen purity and fuel conversion.

Density functional theory-informed dislocation density hardening within crystal plasticity: Application to modeling deformation of Ni polycrystals

In the present work, the flow response of polycrystalline Ni as a function of grain size is captured using a crystal plasticity fast Fourier transform (CPFFT) model with a dislocation density (DD) hardening law. In order to increase the robustness of the DD model, two of its parameters that are typically fit to experimental data, the normalized activation energy for overcoming the dislocation glide barrier and the generation rate of dislocation debris at high levels of strain, are obtained from first-principles calculations based on density functional theory (DFT). These parameters are related to stacking fault energy and vacancy formation energy, both of which can be accurately predicted by DFT-based calculations. The present work demonstrates a successful integration of DFT results into the DD hardening law within CPFFT, facilitating parameterization and reducing the uncertainties of calibration to macroscopic flow response.

Annealing-dependent changes in the structural and electrical properties of NiO epitaxial films

NiO and Ni-cluster-embedded NiO epitaxial films grown on c-sapphire substrates using pulsed laser deposition technique are annealed at different temperatures in an oxygen environment. The structural, morphological, and electrical properties of these samples are investigated as functions of the annealing temperature. It is observed that, in all cases, the sample surface becomes smoother with the increase in annealing temperature. The resistivity of the Ni-cluster-free NiO epilayers is found to decrease with the increase in annealing temperature beyond ∼300 °C. Annealing at 450 °C results in about a two orders of magnitude decrease of resistivity from the highly insulating state of the as-grown. The resistivity shows a gradual increase when annealed at temperatures higher than 450 °C. A reduction of resistivity with annealing can be attributed to the enhancement of the density of Ni vacancies, which are known to act as shallow acceptors in NiO. The formation energy of the Ni vacancies, which has been estimated from the versus plot, comes out to be 623 meV. The density of 60° dislocations in these films increases sharply when annealed above 500 °C. A reduction of conductivity of films annealed above 500 °C can thus be explained in terms of the enhancement of the rate of scattering of carriers by these defects. The resistivity of the Ni-cluster-embedded highly conducting NiO epilayers is found to increase rapidly by more than several orders of magnitude beyond an annealing temperature of ∼200 °C. This has been ascribed to percolation-driven metal-to-insulator transition arising as a result of the reduction of the cluster density with annealing.

Structure/Interface Coupling Effect for High-Voltage LiCoO2 Cathodes.

LiCoO2 (LCO) is widely applied in today's rechargeable battery markets for consumer electronic devices. However, LCO operations at high voltage are hindered by accelerated structure degradation and electrode/electrolyte interface decomposition. To overcome these challenges, co-modified LCO (defined as CB-Mg-LCO)that couples pillar structures with interface shielding are successfully synthesized for achieving high-energy-density and structurally stable cathode material. Benefitting from the "Mg-pillar" effect, irreversible phase transitions are significantly suppressed and highly reversible Li+ shuttling is enabled. Interestingly, bonding effects between the interfacial lattice oxygen of CB-Mg-LCO and amorphous Cox By coating layer are found to elevate the formation energy of oxygen vacancies, thereby considerably mitigating lattice oxygen loss and inhibiting irreversible phase transformation. Meanwhile, interface shielding effects are also beneficial for mitigating parasitic electrode/electrolyte reactions, subsequent Co dissolution, and ultimately enable a robust electrode/electrolyte interface. As a result, the as-designed CB-Mg-LCO cathode achieves a high capacity and excellent cycle stability with 94.6% capacity retention at an extremely high cut-off voltage of 4.6V. These findings provide new insights for cathode material modification methods, which serves to guide future cathode material design.

An embedded-atom method potential for studying the properties of Fe-Pb solid-liquid interface

A new interatomic potential for Fe-Pb binary system is developed in the framework of an embedded atom model using the force-matching method. Compared with the ab initio calculations and experiment values, the developed Fe-Pb EAM potential can accurately describe the ground state, defects and liquid properties of crystal and Fe-Pb solid-liquid interface, such as equation of state, vacancy and interstitial formation energies, adsorption and escape energies, melting point, radial distribution function and density at high temperature. High accuracy and feasibility of the developed Fe-Pb EAM potential can provide the further reliable studies on the corrosion behavior of liquid Pb on steels used in complicate environment of the irradiation, high temperature, pressure in nuclear reactors.

Rational Design of Precious-Metal Single-Atom Catalysts for Methane Combustion.

Supported precious-metal single-atom catalysts (PM SACs) have emerged as a new frontier of high-performance catalytic material with 100% atom utilization efficiency. However, the rational design of such material with guidance from fundamental understandings of the structure-activity relationship remains challenging. Here, we report the synthesis, characterizations, and mechanistic investigation of various PM SACs supported on nanoceria for CH4 combustion. Using density functional theory, two descriptors as the d-band center of PMs and oxygen vacancy formation energy are established, which jointly govern the reactivity for CH4 combustion. These descriptors are thus applied to predict a dual SAC consisting of proximate Pd and Rh sites, demonstrating a remarkable improvement versus Pd or Rh catalyst, respectively. Our results reveal the general strategy of integrating experimental and computational efforts for investigation of various PM SACs in methane combustion, thus paving the way for the next generation of advanced catalytic materials.

Sr Doping and Oxygen Vacancy Formation in La1−xSrxScO3−δ Solid Solutions: Computational Modelling

Sr-doped lanthanum scandate La1−xSrxScO3−δ (LSS) is a promising perovskite-type material for electrochemical applications such as proton conductors. Oxygen vacancy is a common defect in ABO3-type perovskites. It controls ion transport as well as proton uptake. The energetic, structural, and electronic properties of oxygen vacancy in LSS are studied deploying the DFT method with meta-GGA functional. The vacancy formation energies in LSS were calculated for various Sr concentrations. Unlike other perovskites, in this material, the electrons are trapped at the oxygen vacancy site (the F-type centres, common in ionic oxides like MgO and Al2O3) rather than localised on the nearest to the vacancy B-cations. The process of oxygen vacancy formation is considered relative to Sr concentration x and oxygen nonstoichiometry factor δ. Three primary regimes are discussed: (I) localized at the vacancy electrons, x/δ < 2, (II) electron charge balanced system, x/δ = 2, and (III) delocalized electron holes, x/δ > 2. For x/δ ≥ 2 oxygen vacancy formation energy reaches the saturation level of ~3.5 eV, which is potentially beneficial for the proton uptake.

Impurity-vibrational entropy enables quasi-zero-strain layered oxide cathodes for high-voltage sodium-ion batteries

Layered transition metal oxides based on cationic/anionic redox have gained much attention for high-energy-density sodium ion batteries (SIBs). However, irreversible oxygen activity and unstable crystal structure lead to fast capacity fading and undesired rate performance, limiting its large-scale commercial application. Based on the solid-state physics theory, here we demonstrate that the electrochemical capability in P2-type Na2/3Ni1/3Mn2/3O2 cathode can be significantly improved when impurity-vibrational entropy is increased by simultaneously constructing surface ZrO2 coating and Zr4+ doping (P2-NaNM@Zr). In-situ and ex-situ X-ray diffraction (XRD) verifies that quasi-zero-strain P2-NaNM@Zr cathode maintains P2 phase structure during the charging/discharging process, achieving an ultra-low volume change (1.18%) upon Na+ entire extraction at a high cut-off voltage of 4.5 V. Besides, according to First-principles calculations, we first investigate that the oxygen vacancy formation energy of P2-NaNM@Zr (−2.11 eV) is higher than that of sample P2-NaNM (−2.61 eV), strongly indicating stable and reversible anionic redox reaction. As a result, P2-NaNM@Zr material reveals highly Na storage performance, retaining 86% capacity retention after 1000 cycles at the rate of 5 C within the voltage range of 2.5 − 4.0 V, delivering reversible capacity of 132 mA h g−1 after 50 cycles within 2.0 − 4.5 V.