Amount Of Doping Research Articles

Synthesis and Electrochemical Performance Enhancement of Li2MnSiO4 Cathode Material for Lithium‐Ion Batteries via Mn‐Site Ni Doping

AbstractIn exploring the potential of Li2MnSiO4 as a cathode material for lithium‐ion batteries (LIBs), the key challenges often involve enhancing electronic conductivity and lithium‐ion diffusion rates. To address these issues, this paper proposes the combination of solid‐state doping and a two‐step calcination process to successfully prepare the Li2Mn1−xNixSiO4 series of cathode materials, where Ni substitutes Mn at different doping amounts (x = 0, 0.02, 0.04, 0.06, 0.08). The use of chemically equivalent Ni2+ ions to replace Mn2+ ions is an effective method. Since the ionic radius of Ni2+ is smaller than that of Mn2+, this substitution can create more voids in the lattice structure. These increased voids provide smoother channels for the transport of electrons and lithium ions, thereby improving the material's electrical conductivity. At a Ni doping amount of 0.06, the material exhibits optimal electrochemical performance, achieving a discharge capacity of 155 mAh g−1 at 0.1 C, significantly superior to undoped lithium manganese silicate. The doping of Mn sites with Ni significantly improves the conductivity and lithium‐ion diffusion capabilities of Li2MnSiO4, revealing the tremendous potential of doping strategies in optimizing the performance of LIBs cathode materials.

Biocompatibility and antimicrobial efficacy of silver-doped borosilicate bioactive glass for tissue engineering application

Borate bioactive glasses are an auspicious material for tissue engineering applications due to their enhanced dissolution rate, bioactivity, and capacity to integrate therapeutic ions. In this study, borate-based S49B4 bioactive glass doped with silver at mass fraction of 0.5, 1, and 3 wt% were studied for bioactivity, degradation, antibacterial, and cytocompatibility. Thermogravimetric analysis revealed that the bioactive glasses were thermally stable between 600 and 700 °C. Fourier transform infrared spectroscopy and X-ray diffraction confirmed the successful synthesis of an amorphous phase of the doped borosilicate bioactive glasses and the incorporation of silver ion crystals within the structure, as well as associated contributions from borate and silicate network formers in the borosilicate bioactive glass. Morphological evaluation revealed that the borosilicate bioactive glasses exhibit a uniform and spherical shape across all formulations, with the mean particle size varying from 65 to 76 nm. An in-vitro acellular bioactivity in simulated body fluid medium showed that increasing the silver content increased the degradation rate and pH. Besides, scanning electron microscopy and Energy dispersive X-ray spectroscopy analysis revealed an upsurge in apatite production on the BBGs' surfaces as well as incremental Calcium-Phosphate ratio values of 1.50, 1.65 and 1.70 as the silver content increases. The antibacterial effect was tested against Escherichia coli and Staphylococcus aureus, while cytocompatibility was tested against human gingival epithelial cells. Silver integration at 1 wt percent yielded the most promising outcomes, which were particularly bactericidal at 79.8 % for Escherichia coli and 93.41 % for Staphylococcus aureus. Similarly, its Lactate Dehydrogenase percentage is significantly similar to the negative control employed in the study, indicating its biocompatibility. In contrast, 3 wt% silver exhibited the maximum bactericidal activity while also exhibiting mild cytotoxicity. In summary, our research indicates that elevated silver concentration enhances the bioactivity and antimicrobial characteristics of borosilicate bioactive glasses; nevertheless, a higher silver weight percent in this study also increases the possibility of cytotoxicity. It is therefore essential to carefully regulate the amount of silver doping at lower concentrations in order to maximize antibacterial action and minimize toxicity to human cells. The results presented here contribute to our understanding of the prospective use of silver doped borosilicate bioactive glasses as a possible material for tissue engineering applications.

Post-growth annealing effect of Li-doped NiO thin films grown by mist chemical vapor deposition

Nickel oxide (NiO) thin films were grown by mist chemical vapor deposition (mist CVD) with various amounts of Li dopant in the precursor (0–15%). As the Li dopant readily decomposed under the high temperature above 700 °C, the post-growth annealing was conducted at 600–800 °C. The crystal quality of the undoped and Li-doped NiO films was improved by thermal annealing due to the crystal reconstruction. The optical transmittance of NiO films was decreased with increasing the amounts of Li dopants, whereas it was increased with thermal annealing. The bandgap of the NiO films was slightly red-shifted with increased amounts of Li dopants, whereas it was blue-shifted with increasing annealing temperature. The resistivity of as-grown NiO films ranged from 25–75 Ω·cm with Li doping. Electrical properties abruptly decreased under a high annealing temperature of 700 °C. Hence, an appropriate combination of Li doping and post-growth annealing might improve the structural properties of the NiO thin films while retaining the p-type conductivity.

Flexural toughness and stress-strain relationship of different types of steel fiber reinforced shotcrete in high geothermal environment

The shape of steel fiber plays a pivotal role in determining the mechanical properties of concrete. In this paper, the impacts of end-hooked, wavy and ultra-fine steel fibers (all with a doping amount of 1.0 %) on the compressive strength, flexural strength, flexural toughness, and strain-strain relationship of shotcrete under curing conditions of 20 ℃, 40 ℃, and 60 ℃ are studied. Furthermore, the flexural toughness of steel fiber shotcrete is evaluated using the energy absorption method, and a constitutive model for steel fiber shotcrete was established based on meso-damage mechanics theory. The results indicate that curing temperatures below 40 ℃ are conducive to enhancing the compressive strength, flexural strength, and flexural toughness of steel fiber shotcrete, while curing temperatures above 60 ℃ are unfavorable for the development of strength and toughness in steel fiber shotcrete. Regardless of the type of steel fiber, its incorporation can alleviate the negative impact of high-temperature curing on the strength and toughness of shotcrete. Under high-temperature curing conditions, the influence of end-hooked steel fibers on the strength of shotcrete is superior to that of corrugated and ultrafine steel fibers, while ultrafine steel fibers are beneficial for improving the flexural toughness of shotcrete. The slope, peak stress, and peak strain of the stress-strain curves of shotcrete cured at 40 ℃ and 60 ℃ with the addition of the three types of steel fibers are greater than those of concrete without steel fibers. Furthermore, the descending segment of the curve is wider and smoother, with a larger surrounding area, demonstrating good toughness, deformability, and ductility. The end-hooked steel fibers and ultrafine steel fibers exhibit superior performance in enhancing the toughness and ductility of shotcrete under high-temperature curing conditions compared to wavy steel fibers. Based on meso-damage theory, the impacts of curing temperature and steel fiber types on the constitutive model of shotcrete under axial compression were established, and the model parameters were discussed. The research results can provide theoretical support for the durability design of tunnel linings in high ground temperature environments.

Optimized TCR and MR properties of La0.7-xSmxCa0.3MnO3 ceramics by Sm3+ doping

La0.7Ca0.3MnO3 (LCMO), with its high temperature coefficient of resistance (TCR) and large magnetoresistance (MR) effect, has emerged as a leading material in the field of new multi-functional ceramics. Enhancing the magnetoresistive effect of LCMO in low magnetic field and expanding its application range is one of the main research goals of this kind of materials. In this work, La0.7-xSmxCa0.3MnO3 (LSCMO) (0 ≤ x ≤ 0.09) ceramic targets with different doping amounts were successfully prepared by sol-gel method, and the influence mechanism of Sm3+ doping on the magnetoresistive effect and electrical transport performance of LSCMO was systematically analyzed. X-ray diffraction (XRD) results showed that the lattice parameters (a,b,c,V) of LSCMO decreased slightly, indicating that the doping amount of Sm3+ at the A-site increased. Scanning electron microscopy (SEM) showed that the grains were closely connected without obvious pores, the grain size decreased slightly. The ρ-T curve shows an obvious metal-insulator (M − I) transition, with the increase of Sm3+, the increase of resistivity, metal-insulator transition temperature (TMI) and ferromagnetic-paramagnetic (FM-PM) transition temperature (TC) move towards low temperature. When x = 0.015, the peak value of TCR reaches 41.94 %·K−1, and when x = 0.06, the peak value of MR reaches 80.25 %, both TCR and MR are improved. The results show that: Sm3+ doping can effectively enhance the electromagnetic transport performance of LSCMO. This material has a very wide application prospect in the fields of magnetic storage, and infrared detection.

Research on electrical conductive properties of thulium-doped calcium zirconate solid electrolyte

To further investigate the electrochemical performance of Tm doped CaZrO3 electrolyte, the CaZr1−xTmxO3−α (x = 0, 0.025, 0.05, 0.075 and 0.1) solid electrolyte specimens were prepared by high temperature solid state method. The phase structure and microstructure of the electrolyte samples were analyzed by Raman spectrum, XRD and SEM. The electrical conductivity of the specimen was measured at the temperature of 673∼1373K in hydrogen-rich and oxygen-rich atmosphere by the two-terminal AC impedance spectroscopy method. The H/D isotope effect of the specimen at different temperature was tested to confirm the dominant conducting carrier in predetermined temperature and atmosphere. It is found that proton is the dominant charge carrier both in oxygen-rich and hydrogen-rich atmosphere at the lower temperature below 1073 K. However, at higher temperature above 1073K, the predominant charge carrier seems to be oxygen ion vacancy in hydrogen-rich, whereas to be electron hole in oxygen-rich atmosphere, based on the analysis of the atmospheric dependence of the electrical conductivity. Moreover, partial conductivities of conducting species, the active doping amount of Tm and the standard Gibbs free energy changes for interstitial proton production by dissolution of water and hydrogen in Tm doped electrolyte were estimated based on crystal defect chemistry theory.

Multi boron-doping effects in hard carbon toward enhanced sodium ion storage

Hard carbon (HC) has been considered as promising anode material for sodium-ion batteries (SIBs). The optimization of hard carbon’s microstructure and solid electrolyte interface (SEI) property are demonstrated effective in enhancing the Na+ storage capability, however, a one-step regulation strategy to achieve simultaneous multi-scale structures optimization is highly desirable. Herein, we have systematically investigated the effects of boron doping on hard carbon’s microstructure and interface chemistry. A variety of structure characterizations show that appropriate amount of boron doping can increase the size of closed pores via rearrangement of carbon layers with improved graphitization degree, which provides more Na+ storage sites. In-situ Fourier transform infrared spectroscopy/electrochemical impedance spectroscopy (FTIR/EIS) and X-ray photoelectron spectroscopy (XPS) analysis demonstrate the presence of more BC3 and less B–C–O structures that result in enhanced ion diffusion kinetics and the formation of inorganic rich and robust SEI, which leads to facilitated charge transfer and excellent rate performance. As a result, the hard carbon anode with optimized boron doping content exhibits enhanced rate and cycling performance. In general, this work unravels the critical role of boron doping in optimizing the pore structure, interface chemistry and diffusion kinetics of hard carbon, which enables rational design of sodium-ion battery anode with enhanced Na+ storage performance.

Two birds with one stone: A ferrocene-based zirconium(IV)-organic framework nanosheet denoting intrinsic high proton conductivity and acting as a fine dopant to chitosan-based composite membranes

Recently, it was demonstrated that employing metal-organic frameworks (MOFs) with prominent proton conductivity (σ) as fillers with organic substrates such as chitosan (CS) or Nafion is an effective approach for preparing composite membranes (CMs) with outstanding functionalities. Inspired by this, one extremely stable Zr(IV)-MOF (namely Zr-FDC) with a nanosheet structure produced by 1,1′-ferrocene dicarboxylic acid (H2FDA) was successfully manufactured in this research and subsequently used as a filler to synthesize a series of CS-based CMs via casting method. The alternating current (AC) impedance determinations manifested that both Zr-FDC and the related CS-based CMs (CS/MOF-x; x = 2, 4, 6, 8 being the mass percentage of Zr-MOF in the CM) showed ultrahigh σ values, indicating the structural advantages of the Zr-MOF. Further research verified that when the MOF doping quantity is 4 %, the CM's (CS/MOF-4) σ is the greatest, being 2.22 × 10−2 S/cm, which is boosted by nearly tenfold at 100 °C and 98 % relative humidity (RH) compared to the original MOF (3.2 × 10−3 S/cm). Furthermore, the CM exhibits superior thermal stability and tensile resistance. Finally, considering the structural features of the MOF and CS, activation energy data, and other determinations, we thoroughly theorized the proton conduction process within the MOF framework and CMs, referencing the subsequent proton exchange membrane design.

Structural Transformation of Metastable Two-Electron Superatom Au-Doped Cu-Rich Alloy Nanocluster.

The ability to fabricate bimetallic clusters with atomic precision offers promising prospects for elucidating the correlations between their structures and properties. Nevertheless, achieving precise control at the atomic level in the production of clusters, including the quantity of dopant, characteristic of ligands, charge state of precursors, and structural transformation, have remained a challenge. Herein, we report the synthesis, purification, and characterization of a new bimetallic hydride cluster, [AuCu11(H){S2P(OiPr)2}6(C≡CPh)3] (AuCu11H). The hydride position in AuCu11H was determined using DFT calculations. AuCu11H comprises a ligand-stabilized defective fcc Au@Cu11 cuboctahedron. AuCu11H is metastable and undergoes a spontaneous transformation through ligand exchange into the isostructural [AuCu11(Cl){S2P(OiPr)2}6(C≡CPh)3] (AuCu11Cl) and into the complete cuboctahedral [AuCu12{S2P(OiPr)2}6(C≡CPh)4]+ (AuCu12) through an increase in nuclearity. These structural transformations were tracked by NMR and mass spectrometry.

Introduction of a Hydroxyl Self-Sacrificing Surface on Ultrathin Poly(heptazine imide) Nanosheets by KCl Grafting: A New Strategy to Improve the Photocatalytic Production of H2O2.

The generation of H2O2 through photocatalysis is increasingly recognized as a viable approach for addressing the energy and environmental challenges encountered in industrial production processes. In this research, we synthesized ultrathin (1 nm) poly(heptazine imide) (PHI) nanosheets as a photocatalyst by a one-step KCl molten salt process. The utilization of Fourier transform infrared and X-ray photoelectron spectroscopy substantiated that the interlayer-bonded potassium atoms induce polarization in water molecules, facilitating the attachment of hydroxyl groups on the surfaces of nanosheets. These groups serve as self-sacrificing entities, promoting the reaction that leads to the generation of H2O2. The preparation temperature and KCl doping amount factors for the H2O2 generation rate were investigated, and the mechanism of the KCl-bonded structure on photogeneration charge separation transport was analyzed. Owing to the elevated crystallization and the presence of surface self-sacrificing hydroxyl groups, the rate of H2O2 production reaches 6117.5 and 308.35 μmol·g-1·h-1 under visible-light irradiation (λ ≥ 420 nm) in isopropanol solution and pure water, respectively. These rates are 30 and 18.7 times higher than those observed for bulk g-C3N4, respectively. The photocatalytic kinetic processes for H2O2 formation and decomposition were also calculated to investigate the catalyst activities.

Enhancing the electrochemical performance of Ni-doped CuCo2O4 electrode material through 2D layered sheets

Abstract In the present study, the structural and electrochemical properties on Ni–CuCo2O4 (0 ≤ x ≤ 10 %) was studied for the use of active electrode materials in asymmetric supercapacitors prepared by a simple hydrothermal process. The synthesized material’s morphology shows that the nanosheets are assembled with an average diameter of about 50 nm, and the X-ray diffraction results show the spinel cubic structure with the space group of Fd-3mz (No. 227). CuCo2O4 electrodes exhibit a high specific capacitance for the electrodes because of the abundant redox reactions of Co2+/Co3+ and Co3+/Co4+, and Ni at the Co site has displayed exceptional charge-discharge and cyclic stability properties. The electrochemical studies show that the Ni doped CuCo2O4 electrode has the highest pseudocapacitive nature, with ultra-specific capacitances of 803 F g−1, 889 F g−1, 924 F g−1, and 1,086 F g−1 at 1 A g−1 respectively for pure, 2, 6, and 10 % Ni doped CuCo2O4 electrodes. Further, the excellent rate capability with 82 % capacitance retention and 92.3 % Coulombic efficiency were realized after 1,000 cycles. Moreover, the M-H study at room temperature showed paramagnetic behaviour. Additionally, the electrochemical and magnetic characteristics of the CuCo2O4 system is expected to improve as the doping quantity of Ni increased. This study may pave the way for enhanced properties of Ni doped CuCo2O4 for futuristic hybrid devices applications.

In-situ formation of spinel protective layer through extremely low K-doping for enhanced performance of Ni-rich layered cathodes

Herein, we demonstrate a novel and feasible strategy to stabilize the LiNi0.83Co0.12Mn0.05O2 (NCM) structure via the in-situ formation of a superficial spinel layer with potassium (K) doping. While K+ doped NCM is not new, the formation of the protective spinel layer gives surprising results with even a trace amount of doping, which is unique and novel, and nowhere reported. The structural transformation from layered to spinel on the surface region of NCM is achieved with a K-doping level of 0.05 mol% (NCM-0.05K) and the formed spinel layer acted as a protective pillar for stabilizing the host structure, leading to substantially improved electrochemical performance. The X-ray photoelectron spectra demonstrate a large increase in nickel (Ni2+) distribution after cycling for pristine but almost no change for the NCM-0.05K, suggesting a stable preformed spinel layer. The above results reveal that the K+ doping can strongly reduce the Ni4+ to stable Ni2+ under the spinel phase formation and improves cell performances in terms of specific capacity, capacity retention, rate capability, and Li+ diffusivity. The internal micro-cracking of host NCM is also effectively suppressed by the low amount of K doping. Excessive K-doping, in contrast, leads to a reduction in (de)lithiation rate and greater polarization.

Enhanced the Catalytic Performance of CeO2 by Tuning V5+ Doping Amount in Carbonylation of n-Butyl Amine with CO2

Enhanced the Catalytic Performance of CeO2 by Tuning V5+ Doping Amount in Carbonylation of n-Butyl Amine with CO2

Mineral Interface Doping: Hydroxyapatite Deposited on Silicon to Trigger the Electronic Properties

AbstractDoping silicon wafers without using highly toxic or corrosive chemical substances has become a critical issue for semiconductor device manufacturing. In this work, ultra‐thin films of hydroxyapatite (Ca5(PO4)3OH) are prepared by tethering by aggregation and growth (T‐BAG), and further processed by spike annealing. Via in situ infrared (IR), the decomposition of hydroxyapatite and intermixing with the native silicon oxide is observed already at temperatures as low as 200 °C. Phosphate transport through the native silicon oxide is driven by a phase transformation into a more stable thermal oxide. At 700 °C, diffusion of phosphorus into the sub‐surface region of oxide‐free silicon is observed. In situ IR combined with electrical impedance spectroscopy (EIS), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS), and X‐ray photoelectron spectroscopy (XPS) measurements allows to conclude that the phosphorus is: i) transported through the silicon oxide barrier, ii)) diffused inside the oxide‐free silicon, and iii) finally modified the electrical activity of the silicon wafer. To further explain the experimental findings, density‐functional theory (DFT) is used to demonstrate the extent of the effect of phosphorus doping on the electronic nature of silicon surfaces, showing that even small amounts of doping can have a measurable effect on the electrical performance of semiconductor wafers.

Exploring the mechanism of infrared emissivity control in YSZ-based ceramics doped with Yb2O3

Due to its exceptional thermal stability and high conductivity, Yttrium stabilized zirconia (YSZ) has become an essential material in the field of infrared camouflage. Although YSZ exhibits relatively low emissivity within the 3–5 μm wavelength range, the increasing operating temperatures of aircraft necessitate further reduction in infrared emissivity within this specific band, in accordance with the Wien displacement law. This study focuses on the preparation of ceramic samples of YSZ doped with varying concentrations of Yb2O3 through a high-temperature solid-state reaction. It aims to investigate the influence of different doping concentrations on the microstructure, crystal structure, and infrared radiation characteristics of YSZ ceramic blocks. The experimental results demonstrated that the addition of Yb2O3 induces changes in the grain size and phase content of YSZ. Notably, as the amount of Yb2O3 doping increases, the infrared emissivity of YSZ samples in the 3–5 μm wavelength range exhibits a pattern of initial decrease followed by an increase. Remarkably, at a doping amount of 3 % mol, YSZ ceramics demonstrated the lowest emissivity, with the average emissivity of the 3–5 μm wavelength range decreasing from 0.41 to 0.38.

Effects of Alkali Elements on Copper Indium Gallium Aluminum Selenide Flexible Solar Cells Fabricated on Polyimide Substrates.

Polycrystalline Cu(InGaAl)Se2 (CIGAS) thin films were prepared on polyimide (PI) foils by depositing aluminum (Al) and CIGS precursor layers. Three ceramic CIGS quaternary targets with different sodium (Na) contents were used for investigating the influences of alkali doping at an annealing temperature of 500 °C. The Al concentration was enriched at the front interfaces of absorber films with different Na doping amounts after annealing. Na in the precursor layer diffused to both interfaces during the annealing process, most Na diffused into the Mo layer, and Na existed in the annealed film as compounds Na2Sex and Na2SeO3. An appropriate amount Na element could be beneficial for grain growth in the region beneath the surface. Low Na doping had no significant effect on the crystallization property. High Na doping effected the diffusion of the Cu2-xSe liquid phase and reduced the grain size. On the basis of good crystallization, the passivation effect of Na can effectively improve the performance of cells. A certified power conversion efficiency of 16.19% of a CIGAS flexible solar cell with a 0.54 cm2 active area has been achieved.

Enhancing CO2 methanation via doping CeO2 to Ni/Al2O3 and stacking catalyst beds

This work synthesized a series of Ni/CeO2/Al2O3 catalysts with varying CeO2 doping amounts to enhance low-temperature CO2 methanation. The introduction of CeO2 weakens the interaction between Ni and Al2O3, leading to the formation of Ni-CeO2 active sites. This results in a high dispersion of Ni and CeO2, improved catalyst reducibility, increased number of active sites, and enhanced the CO2 methanation. This work further investigated the impact of WHSV and catalyst stacking configuration to enhance the reaction. When the catalyst is stacked into three segments with a temperature gradient of 330 °C, 300 °C, and 250 °C under WHSV = 9000 ml·h–1·(g cat)−1, the CO2 conversion significantly increases to 95%, which is remarkably close to the thermodynamic equilibrium (96%).

Observation of magnetic dimers in the diluted triangular-lattice spin liquid candidate NaYbO2

The triangular-lattice spin liquid (QSL) candidate NaYbO2 is magnetically diluted by Lu doping, forming homogeneous solid solutions NaYb1-xLuxO2 (0≤ x<1.0). A combination of structural, magnetic, and pulsed high-field electron spin resonance analysis shows that the lattice parameters and the Curie-Weiss temperature θCW vary almost linearly with x, and the crystal electric field environment of the Yb/Lu ions persists during the Lu doping. The statistical distribution analysis of clusters and the deduced linear θCW ∼ x relation indicate that the nearest neighbor exchange J does not change with magnetic dilution. Interestingly, with the magnetization measurement at 0.39 K, we have observed Seff = 1/2 antiferromagnetic Yb-Yb dimers in NaYb0.02Lu0.98O2, which is manifested as a magnetization step at μ0Hc = 2.68 T due to the transition between singlet and triplet states. Thus, the intradimer interaction is directly determined as J/kB = −5.15 K. Surprisingly, this value is close to the interaction of undoped NaYbO2, supporting the theoretical analysis of clusters. Our study provides a method of estimating the magnetic interaction of QSL materials through magnetic dilution. The statistical distribution analysis of magnetic clusters suggests that through a small amount of Lu doping (x < 0.5), the QSL state in NaYbO2 can continue to be maintained.

Ultrafast and Highly Efficient Sodium Ion Storage in Manganese‐Based Tunnel‐Structured Cathode

AbstractNa0.44MnO2 with tunnel structure is considered a promising low‐cost cathode material for sodium‐ion batteries. However, the sluggish Na+ transport kinetics and low initial Coulombic efficiency restrict its practical applications in rechargeable sodium‐ion batteries. Herein, a manganese‐based tunnel‐structured cathode with high rate capability and high initial Coulombic efficiency is prepared by niobium doping and sodium compensation. Via materials characterizations and theoretical calculations, it is demonstrated that a proper amount of niobium doping in tunnel structure can effectively improve its structural stability and charge transport kinetics, resulting in outstanding rate capability (76.6% capacity retained from 0.5 to 30 C) and superior cycling performance (82.3% capacity retention after 800 cycles at 5 C) for the optimized Nb‐doped Na0.44MnO2 cathode (Na0.44Mn0.98Nb0.02O2). Furthermore, NaCrO2 is added into the Na0.44Mn0.98Nb0.02O2 cathode as a self‐sacrificing sodium compensation additive, and a high initial Coulombic efficiency close to 100% is achieved for the composite cathode. This work establishes a facile strategy to design advanced manganese‐based cathode materials for large‐scale energy storage applications.

Probing the thermophysical property mechanism of Mg2+-doped high-entropy oxide ceramics

To create thermal barrier coatings (TBCs) with superior thermal characteristics and high-temperature stability, understanding the microscopic process of heat transfer in high-entropy solid solutions is crucial. In this study, novel (Zr0.2(1-x)Ce0.2(1-x)Pr0.2(1-x)Y0.2(1-x)Ho0.2(1-x)Mgx)O2-δ single-phase high-entropy fluorite-structured oxides with varying Mg elemental contents were successfully synthesized at 1600 °C. Given the unique ionic radius and valence nature of Mg2+, the effects of varying the Mg doping amount on the thermophysical properties and microstructures were explored. Furthermore, the mechanism influencing high-temperature thermal conductivity was studied at the microscopic scale using first-principles calculations to clarify the nature of the thermal conductivity behavior. On one hand, an increase in oxygen vacancies leads to an enhancement of the lattice distortion degree and phonon scattering level. On the other hand, divalent Mg2+ activates the lattice via unequal substitutions, thereby reducing the thermal conductivity. The experimental and simulation results revealed that as Mg doping increases, the content of oxygen vacancies significantly increases, the degree of lattice distortion increases, phonon scattering is enhanced (19.54–21.37 THz), high-temperature thermal conductivity progressively decreases (1.91-1.20 w·m−1·K−1), and the coefficient of thermal expansion progressively increases (11.70 × 10−6-12.31 × 10−6 K−1). These results offer a novel approach for designing doped high-entropy strategies that can satisfy the performance requirements of TBCs.