Amount Of Doping Research Articles

Synthesis of bismuth-doped yttria-stabilized zirconia electrolyte and study of ionic conductivity

ABSTRACT BiYSZ, a Bi3+-doped yttria-stabilized zirconia with 4% molYO1.5, was synthesized using a lamellar liquid crystal template technique. The influence of different doping amounts of Bi3+ on crystal form, morphology and the ionic conductivity has been investigated in detail. In addition, the densification time of BiYSZ has been determined. Analytical techniques such as X-ray diffraction (XRD), Raman spectroscopy and scanning electron microscopy (SEM) have been utilized to characterize the synthesized powders. The results reveal that BiYSZ, with its stable tetragonal phase and spherical nanostructure, benefits from Bi3+ doping in 4% mol YO1.5-stabilized zirconia, leading to enhanced ionic conductivity. Notably, the optimal formulation with 3 mol% Bi3+ and 4 mol% Y3+ in yttria-stabilized zirconia reaches a maximum ionic conductivity of 7.41 × 10−5 S/cm at 500°C. This formulation also reduces the sintering temperature by 100°C compared to 4YSZ and significantly improves conductivity by an order of magnitude.

Mesoporous TiO2@g-C3N4 Nanostructure-Enhanced Photocatalytic Degradation of Tetracycline Under Full-Spectrum Sunlight.

TiO2 has broad prospects in reducing the safety risks posed by emerging pollutants in water environments. However, the high recombination rate of photogenerated carriers limits the activity and photon utilization efficiency of TiO2. In this study, mesoporous TiO2 (m-TiO2) and ultra-thin g-C3N4 nanosheets were composited using a hydrothermal method, with the m-TiO2 tightly and uniformly wrapped by g-C3N4. The chemical structure, elemental composition, and optical properties of the heterojunction were analyzed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), and ultraviolet-visible diffuse reflectance spectroscopy (UV-vis-DRS). The activity of the m-TiO2@g-C3N4 was evaluated by the degradation of tetracycline hydrochloride (TCH). Results showed that the heterojunction exhibited significantly enhanced reactivity compared to pure m-TiO2 and g-C3N4, with kinetic rates of TCH being 1.48 and 6.84 times that of pure m-TiO2 and g-C3N4, respectively. The TCH degradation kinetic rate varied from 0.194 min-1 to 0.026 min-1 and then decreased to 0.015 min-1 on the scale of the bandgap and the number of absorbed photons in m-TiO2@g-C3N4. Concurrently, a 10wt% doping amount of g-C3N4 significantly increased the reaction rate of photogenerated carriers in the system compared to the recombination rate, corresponding to excellent photon efficiency. Reproducibility was evaluated, and a possible degradation mechanism is proposed. This study opens new perspectives for the optimization of catalyst preparation processes aimed at enhancing photon efficiency.

The effect of addition sodium iodide on the thermal properties of (PEO) thin film

In this study, the thermal properties of polyethylene (PEO) thin films dispersed with a fixed amount of dopants of sodium iodide 0.1% by weight (0.1% wt.) were investigated. The thermal conductivity and thermal resistivity of pure PEO thin films and the prepared ones doped with sodium iodide composites have been studied at different temperatures. It was found that the thermal conductivity of these films increases with the increase in temperature and with the ones that doped with 0.1% sodium iodide.

Synergistic Acid-Base Action Leads to Ultrafast Decontamination of Nerve and Blister Agents by OH- Intercalated Zr4+-Doped MgAl-LDH under Ambient Conditions.

Developing materials capable of rapidly decontaminating nerve and blister agents directly under ambient conditions are crucial for practical applications. In this work, Mg3Al1- xZrx-LDH with different Zr4+ doping contents and corresponding OH- intercalated materials Mg3Al1- xZrx-LDH-OH are synthesized. First, they are used for the decontamination of nerve agents under ambient conditions, showing that increasing the Zr4+ doping amount accelerates the decontamination rate of diethyl cyanophosphonate (DECP) and soman (GD), with the half-life of DECP and GD being 3-5 times shorter with Mg3Al0.6Zr0.4-LDH (the highest Zr4+ doping content) compared to Mg3Al1-LDH. Notably, the intercalation of OH- in Mg3Al0.6Zr0.4-LDH further greatly enhances the catalytic activity for DECP and GD, the reaction half-life of DECP and GD with Mg3Al0.6Zr0.4-LDH-OH being 18s and <15s, respectively, which is the shortest recorded so far. Additionally, under ambient conditions, Mg3Al0.6Zr0.4-LDH-OH exhibits superior detoxification performance for mustard gas (HD) compared to Mg3Al0.6Zr0.4-LDH, with 92.8% of HD being removed within 6h. Mechanistic studies reveal that Mg3Al0.6Zr0.4-LDH-OH efficiently decontaminates nerve and blister agents utilizing the synergistic effect of Lewis acid-base sites (Zr4+ and laminate OH groups) and interlayer OH-. To extend the practical applications of the materials, PVA@(PAN/LDH-OH) self-detoxifying fiber loaded with Mg3Al0.6Zr0.4-LDH-OH is prepared.

Enhanced electrical reliability of Zr‐doped BaTiO3 nanoceramics: First‐principle calculations and experimental studies

AbstractWith the miniaturization of multilayer ceramic capacitors (MLCCs) and the increase of electric field on single‐layer dielectrics, it is essential for the development of nanograin high‐reliability dielectric materials. In this work, Zr‐doped BaTiO3‐based ceramics with an average grain size of 130–150 nm were prepared by a chemical coating method. The effects and intrinsic mechanisms of Zr concentration on microstructure, dielectric properties, and reliability were systematically investigated by theoretical calculations and experiments. Zr additives lower the migration barrier of the dopants, which consequently contributes to the formation of thick shell layers in the core‐shell structure and grain growth, affecting the temperature stability and DC bias characteristics of the dielectric constant. Owing to the large change rate of the Zr–O bond length, the introduction of Zr increases the migration barrier of oxygen vacancies. However, the decrease in the effective doping concentration of the shell part and the reduction in the number of grain boundaries of ceramics with high Zr content have a weakening effect on the inhibition of oxygen vacancy migration. An appropriate amount of Zr doping can adjust the dielectric properties and improve the reliability of BaTiO3‐based ceramics. This study provides a theoretical reference for the design of high‐quality MLCCs.

Investigation of the Impact of SmFeN Doping on the Anisotropic NdFeB/SmFeN Composite Magnets

By incorporating various types of permanent magnetic powders, composite magnets with cost-effectiveness and a wide range of magnetic properties can be achieved. In this study, the anisotropic composite magnets were fabricated using the hot press forming method, which involved blending neodymium iron boron (NdFeB) powder and samarium iron nitrogen (SmFeN) powder. The experiment demonstrated that the magnet density reaches its maximum point when the doping level of SmFeN reaches 20 wt.%, aligning remarkably well with the corresponding theoretical value of 19.22 wt.% achieved through a cubic stacking arrangement. In the absence of an applied magnetic field or under a sufficiently high oriented magnetic field (3 T), the remanence variation pattern in composite magnets doped with different amounts of SmFeN aligns consistently with the density pattern, yielding a maximum value of 20%. However, in the actual solidification process, the orientation field is insufficient (e.g., 1.5 T), necessitating a doping amount that exceeds the value corresponding to peak density by 28% to achieve optimal remanence. This observation suggests that the incorporation of a higher proportion of small-sized and relatively low coercivity SmFeN magnetic powder can effectively facilitate the rotational alignment of neighboring large-sized NdFeB magnetic powder under weak magnetic fields, thereby inducing a synergistic effect.

Optimizing electrical properties and efficiency of copper-doped CdS and CdTe solar cells through advanced ETL and HTL integration: a comprehensive experimental and numerical study

Abstract Copper is a commonly preferred dopant for cadmium telluride based solar cells. Even though it is widely used as it enhances the electrical properties, it has the tendency to diffuse into the CdTe layer as well as the CdS/CdTe junction interface which adversely affects the performance of CdTe solar cells. In this experimental study copper doping of buffer cadmium sulfide layer has been performed to analyse its effect on structural, electrical, and optical properties of CdS and CdTe layers. While from the X-ray diffraction analysis it was observed that there was reduction in peak intensities and crystallite sizes of both the CdS and CdTe layers with the increase in amount of copper dopant, from the electrical properties it was found that there were improvements in carrier concentration, mobility, and conductivity of both the layers. To mitigate the losses due to Cu doping, enhance the efficiency and stability of CdTe solar cells an extensive numerical modelling approach was undertaken to employ electron transport layers (ETL) and hole transport layers (HTL) to the copper-doped CdS/CdTe solar cells. We obtained optimum results with titanium dioxide and copper barium thiostannate as ETL and HTL respectively. Finally, CdTe-based solar cells were modelled integrating copper-doped CdS as the buffer layers, TiO2 as ETL and CBTS as HTL respectively. The obtained experimental values of Cu-doped CdS and CdTe layers were implemented into this model. This superstrate configuration yielded impressive output parameters: open circuit voltage of 1.07 V, short-circuit current density of 29.32 mA cm−2, fill factor of 85.08 %, and efficiency of 26.67 %.

Effect of increasing alkali layer spacing on the performance of O3-NaNi1/3Fe1/3Mn1/3O2 cathode materials

O3-Na1-xCax/2Ni1/3Fe1/3Mn1/3O2 (NaCNFMx, x=0, 0.05, 0.1, 0.15) was prepared by doping calcium ions and replacing the sodium sites in the NaNi1/3Fe1/3Mn1/3O2 (NaNFM) material using ball milling spray. XRD, SEM and XPS results demonstrated that the calcium element was successfully embedded in the lattice. The electrochemical performance of NaCNFM0.1 is the best when the doping amount of calcium ion is 0.1. The sodium diffusion coefficient of NaCNFM0.1 cathode material after 3 cycles is 1.67×10-14 cm2/s. The first specific discharge capacity at 1C is 121.1mAh/g. Even at the high current density of 5C, the 200cycles capacity of 103.6mAh/g is much higher than NaNFM's 95.2mAh/g, and the capacity retention rate is as high as 91.5%. Ex-situ XRD and SEM analyses manifested that the moderate amount of calcium doping improved the stability of the layered structure. These results show that the cathode material has great application potential.

Simultaneous structure and surface engineering of metal-organic framework derived LiNi0.5-xFe2xMn1.5-xO4 cathode material for improving high voltage performance of lithium-ion batteries

This study presents a novel material synthesis approach utilizing a terephthalic acid-based metal-organic framework as a precursor and employing an ethanol-assisted hydrothermal treatment to produce high-performance Fe-doped LiNi0.5Mn1.5O4 (LNMO) cathode material. This strategy yields a well-crystallized spinel structure with uniformly distributed transition metal ions. Additionally, the appropriate quantity of Fe dopant can achieve the desired Mn3+/Mn4+ ratio, level of structural disordering, and crystal phase purity for Fe-doped LNMO. The synthesis process also aids in forming an amorphous Li2CO3 surface layer, approximately 1 nm thick, which protects the active material from excessive reaction with electrolyte. The typical Fe-doped LNMO cathode (S-05) exhibits superior performance compared to a commercialized LNMO counterpart. It delivers an initial discharge capacity of 135 mAh g-1 at 1 C with exceptional cycling stability over 500 cycles (capacity retention of 90%) under high voltage (5.0 V vs. Li+/Li). Furthermore, its rate capability significantly improves, with a capacity retention of 85% (5 C/0.2 C). This enhanced performance aligns with evidence of activated Ni2+/Ni3+/Ni4+ redox reactions and suppressed cathode electrolyte interphase resistance, leading to promoted Li+ diffusion. Moreover, it is found the cathode helps alleviate electrolyte degradation at high voltages by inhibiting the formation of singlet oxygen in the electrolyte.

Enhanced Linear and Nonlinear Optical Characteristics of Cerium (Ce) Doped ZnO Film

ZnO and Ce-doped ZnO films with different doping concentrations (2, 4, and 6 wt%) were produced via SILAR technique, and the influence of the Ce amount on the structural, morphological, linear and nonlinear optical properties were examined in detail. Structural analyses conducted using X-ray diffraction (XRD) and Raman spectroscopy revealed the formation of hexagonal wurtzite pristine ZnO and Ce-doped ZnO nanostructures. The CeO2 phase was observed for only Ce6:ZnO samples by the XRD and Raman analyses. The morphological analyses were performed with a Scanning Electron Microscope (SEM), and it was found that the grain size decreased with Ce doping. The band gap energies decreased from 3.18eV to 2.67eV with increasing dopant (Ce) amount and increasing Urbach energy (EU). The dislocation density values (XRD) were calculated as 1.68x , 2.22x , 4.52x , and 8.65x nm-2 for ZnO, Ce2:ZnO, Ce4:ZnO, and Ce6:ZnO, respectively, which is consistent with the increasing Urbach energy. The optical characteristics such as excitation and absorption coefficient, refractive index, dielectric constant, optical conductivity, the volume (VELF) and surface (SELF) energy loss functions were estimated. The third- order nonlinear susceptibility, and the nonlinear refractive index were calculated using Miller's generalized rule with linear refractive index and Wemple-DiDomenico (W-D) model. The χ(3) and n2 values increased with Ce influence compared to undoped ZnO film. Various methods have been used to obtain Ce:ZnO films, but the low-cost SILAR method has not been reported before, and the films produced via this method showed suitable behaviours for optoelectronic devices and nonlinear applications.

AC Conductivity, Dielectric and Structural Properties of Co0.6Zn0.4-xMgxFe2O4 Co-Zn Spinel Nano Ferrites Prepared using Sol-gel Autocombustion Method

This study examined the structural, morphological, dielectric and AC conductivity properties of CoZnMg ferrite samples (Co0.6Zn0.4-xMgxFe2O4) with x = 0.00, 0.08, 0.16, 0.24, 0.32, 0.40. The sol-gel autocombustion method was used to synthesize the CoZnMg ferrite samples. The produced samples crystallize in the cubic spinel structure, according to an XRD analysis of the structural characteristics. The highly crystalline single-phase cubic spinel structure with a distinct peak in the (311) plane has been confirmed by XRD studies. The diameters of the crystallites have fluctuated between 24.92 and 9.80 nm. SEM, EDX and FTIR used to examine the morphological and elemental characteristics of the samples. According to FE-SEM, adding magnesium to the current ferrite system resulted in the loss of the porous gel structure. According to the relative stoichiometry of the Mg-substituted CoZn ferrite, the EDAX analysis verified the presence of Co, Zn, Mg and O. The investigated samples may be appropriate for a variety of uses, as indicated by the consistent conductivity at low frequencies. Within the frequency range of 100 to 5 MHz, the room temperature, electrical and dielectric properties were examined. The quantity of magnesium dopants and the microstructural features were related to the obtained results. The dielectric characteristics (ε′ and ε″) of the ferrites gradually decreased with frequency, even at higher frequencies. The samples exhibited interfacial polarization, which led to normal dielectric characteristics in line with the Maxwell-Wagner model.

The Doping of a Carbon Coating with Phosphorus as a Potential Way of Improving the Biological Properties of Diamond-like Carbon.

The potential of diamond-like carbon coatings in medicine can be increased by doping them with various elements. Such modifications especially affect the biological properties of the synthetized films. In the following research, phosphorus was introduced into the carbon matrix by means of the chemical vapor deposition technique and using an organic precursor. With the addition of about 1.6 and 4.3 at% of dopant, not only was the surface roughness increased, but significant changes in both the mechanical and biological properties were also observed. The presence of phosphorus reduced the hardness of DLC coatings but still improved this parameter in comparison to the substrate material-AISI316LVM. A biological examination revealed the bacteriostatic potential of doped coatings regardless of their chemical composition. Increasing the amount of phosphorus improved the proliferation of osteoblasts (Saos-2 cell), but the opposite effect was achieved for the endothelial cell line (EA.hy926). Another important aspect is the reduction in platelet activation, especially for low amounts of dopant.

Aspects of Fe-Incorporation into CaTiO3-SrTiO3 Perovskites and Their Catalytic Application for Ammonia SCO/SCR.

Perovskite materials in the CaTiO3-SrTiO3 system doped with different amounts of iron (1, 2 and 5 mol.%) and various Ca/Sr ratios were prepared by the modified citrate method. Additionally, the materials with 0.05 deficiency in strontium/calcium sublattice and 5 mol.% of Fe were also synthesised. The materials were subjected to structural (XRD, XANES) and microstructural (SEM) characterisation, as well as the analysis of susceptibility to reduction/oxidation processes. The structural analysis indicates a lack of iron-containing phases; thus, an incorporation of Fe into the perovskite structure was postulated. Additionally, the oxidation state of iron in the perovskite structure changes with the dopant amount. The temperature-programmed reduction measurements showed partial reversibility of the reduction processes. For the materials with the highest iron amount, the catalytic tests in NH3-SCO and NH3-SCR reactions were carried out. The materials showed high catalytic activity and high selectivity to N2 in the NH3-SCR process; however, they were inactive in NH3-SCO.

Enhanced energy storage performance of Mn-doped NBT-based flexible films by defect engineering

The rapid development of advanced flexible electronics leads to higher demands on the energy storage performance and spatial adaptability of capacitors. Here, Mn2+ is doped into 0.6(Na0.5Bi0.5)TiO3-0.4Bi(Mg0.5Zr0.5)O3 (0.6NBT-0.4BMZ), which effectively reduces the carrier content by forming defective complexes through the bonding of Mn2+ with oxygen vacancies, while maintaining a relatively high polarizability and enhancing the breakdown strength. The optimal storage performance is demonstrated by the 0.6NBT-0.4BMZ film with a Mn doping amount of 1 mol%. The observed breakdown strength, storage density, and storage efficiency are 2900 kV/cm, 60.2 J/cm3, and 60.3 %, respectively. Furthermore, the films exhibit excellent stability in various temperature ranges (25–205 ℃), frequencies (1–5 kHz), fatigue tests (at 107 charge/discharge cycles), and bending resistance tests (20,000 cycles/radius R ≈ 2 mm). These results indicate that NBT-based film materials hold great promise for future flexible energy storage applications.

Precise control of metal-insulator transition temperature in La-substituted La0.7Ca0.3MnO3 via ionic radius tuning

The peculiar physical properties of LaxCa1-xMnO3, such as the paramagnetic-ferromagnetic phase transition and colossal magnetoresistance, become prominent near the metal-insulator transition temperature (TMI). Precise control of the TMI is essential for promoting applications in fields like magnetic sensing and magnetic storage, and for advancing fundamental research and material development in emerging areas such as multifunctional heterostructures and complex strongly correlated electronic structures. In this study, La0.7Ca0.3MnO3, a composition known for its sharp metal-insulator transition, was selected as the research subject. Using the sol-gel method, we partially substituted the A-site La element with six rare earth elements (Nd, Sm, Eu, Gd, Dy, Er) to investigate the relationship between the TMI, structural parameters, and the type of doping elements. Our results indicate that for a given doping element, the TMI decreases with increasing doping amounts and shows a linear relationship with the average ionic radius of the A-site. Notably, the slope of the linear equation decreases linearly with the reduction in the ionic radius of the doping element. Based on these observations, we proposed a relational formula between the TMI and the ionic radius of the doped element, as well as the average ionic radius of the A-site. Additionally, our formula can estimate the TMI for Sr2+ doping, which shifts the transition to higher temperatures. These findings reveal the relationship between TMI and crystal structure variations, offering a promising pathway for the design and regulation of TMI in lanthanum-based manganites.

Preparation and characterization of CuBO2-based photocatalysts and doped variants

An eco-friendly CuBO2-based photocatalyst has been doped by a lanthanide for the first time. Gd3+ and Gd3+/Bi3+-doped CuBO2 are synthesized by the hydrothermal method to study their magnetic properties. Then they are analyzed by XRD, UV-Vis, SEM, and VSM. The maximum amount of doping is x= 0 − 1.5% in Cu1–3xGd3xBO2 and Cu1–3xBi3x/2Gd3x/2BO2 formulas as they are analyzed in XRD. For concentrations higher than x = 2%, the additional peak indicates that doping is incomplete. The XRD pattern of CuBO2 confirms that its crystal structure is a hexagonal one with the R3 ̅m space group. According to UV-Vis analysis, the bandgap energies are 2.711, 2.753, and 2.765 for CuBO2 and doped systems. Additionally, the morphology of particle sizes is confirmed according to SEM images. Meanwhile, the magnetic properties of synthesized material are studied by VSM, and the doped compound exhibited higher magnetic properties than CuBO2, which is associated with the exchange interaction of electron and d spins in Gd3+ and Bi3+. The study aims to provide insights into the magnetic properties of lanthanide-doped CuBO2-based photocatalysts, potentially paving the way for developing improved magnetic materials for various applications.

Chain effect of Mn4+/ Mn3+ and OLattice on La1-xSrxMnO3 catalysts for lower thermally driven CO oxidation

In this work, a series of La1-xSrxMnO3 catalysts for CO oxidation were successfully fabricated via a facile sol-gel method with multistage calcination. By modifying the Sr doping quantity at A-site, the surface Mn4+/ Mn3+ ratio was manipulated, and thus lattice oxygen and oxygen vacancy concentrations of were further regulated by the system electron migration. This domino effect produced a radically different catalytic response, of which the optimal La0.4Sr0.6MnO3 samples performed the most excellent CO oxidation at lower temperature window. In-situ DRFITS spectra revealed catalytic intermediates and demonstrated the concurrence of dominant Mv-K mechanism and secondary E-R reaction pathway in CO oxidation over La0.4Sr0.6MnO3 under three types of thermodynamic states. The study is poised to enhance the propagation and practical employment of Sr-doped LaMnO3 perovskite catalysts, while supplying theoretical perspectives for the investigation towards underlying CO reaction mechanisms.

An in-situ high-throughput study of the Invar effect in the Fe–Ni–Co system

The Fe–Ni based classical Invar alloy and the Fe–Ni–Co based super Invar alloy are the basis for designing multicomponent alloys with low thermal expansion. In this work, we applied in-situ high-throughput experimental methods to map chemical composition, crystal structure, coefficient of thermal expansion (CTE) and magnetism in the Fe–Ni–Co system. The distribution of CTE (80–200℃) measured by the in-situ micro-beam X-ray diffraction on the combinatorial materials chips (CMC) showed low CTE regions in agreement with previous reports. Combined with the MOKE measurements, the μ̅−e̅ relation of the Fe–Ni–Co ternary FCC phase is found to follow the reported FCC Fe–Ni alloys in the Slater-Pauling curve. A low CTE region is centred at e̅ = 26.7 and μ̅= 1.26 μB in the Slater-Pauling curve. The observed low CTE zone not only matches with the classical Invar and super Invar alloys but also agrees with the reported Fe–Ni–Co based multicomponent alloys with a small amount of doping (< 5 at%) by Cu, Cr, Mn etc. The effect of Cr addition (> 5 at%) to Fe–Ni–Co alloys on the Invar effect is further discussed in terms of the interplay between magnetism and austinite stability.

Theoretical Investigation on the Stability of Second Phase Formation in Ba(Zr, M)O3-Δ By Electrode Derived Ni and Co Elements

Ba(Zr,M)O3-δ is a perovskite-type oxide in which B-site is partially substituted by the dopant element M. It is expected to be applied as a solid electrolyte in proton-conducting ceramic fuel cells (PCFC). In recent years, there has been concern that the diffusion of Ni from the anode and Co from the cathode e into the solid electrolyte causes second phase formation, resulting in cell degradation. For example, depending on the type and amount of dopant, highly resistive phase, BaM 2NiO5, is reported to be precipitated [1]. Thus, understanding the precipitation conditions and precipitation mechanism of the second phase is essential to control cell degradation. Our previous studies have shown that the energetic stability of the precipitates is dominant in the formation of the precipitates by the anode-derived Ni. On the other hand, concerning the formation of cathode-derived Co precipitates, a complex oxide considered to be spinel precipitates at the grain boundary.However, not enough research has been done, and there is a possibility of other compounds precipitating as well, depending on conditions.In the present study, we referred to our previous experimental evaluation and performed first-principles calculations to theoretically examine the precipitation of the second phase associated with the solid solution of Ni and Co in Ba(Zr,M)O3. Anode-derived Ni reacts with dopant element M to form precipitates, and the formation tendency was found to be organized by the ionic radius of the dopant element M. Co from the cathode is thought to segregate with Ni at the grain boundary of the solid electrolyte, and this mechanism was investigated in terms of segregation energy and solid solution energy of Ni in spinel at the grain boundary. Furthermore, the formation energies of complex oxides involving Co for various M elements were evaluated by first-principles calculations to investigate the relative stability of the oxides under various equilibrium conditions organized by chemical potentials. The results suggest that BaCoO3 is stable in an oxidation atmosphere, and this trend was most pronounced for M=Yb. It is thought that BaCoO3 precipitation does not deplete dopants from the solid electrolyte matrix phase and is not likely to lead to degradation. At the conference, the detailed precipitation mechanism and the changes in the lattice constants of BaZrO3 due to the solid solution of different elements with respect to chemical expansion will be discussed.AcknowledgmentThis research result was obtained as a result of the commissioned work (Development of Ultra-High Efficiency Protonic Ceramic Fuel Cell Devices WP2, WP3, JPNP20003) of the New Energy and Industrial Technology Development Organization (NEDO). We would like to express our gratitude to all parties involved.Reference[1] T. Kuroha, Y. Niina, M. Shudo, G. Sakai, N.Matsunaga, T. Goto, K. Yamauchi, Y. Mikami, and Y. Okuyama, Optimum dopant of barium zirconate electrolyte for manufacturing of protonic ceramic fuel cells, Journal of power sources, 506 (15), 230134 (2021).

High Throughput Li-Ceramic Battery Electrolyte Property Optimization Based on Efficient Sample Space Exploration

Solid-state batteries (SSBs) are safer, cheaper, and higher energy density alternatives to conventional Li-ion batteries, of which the global production capacity has reached 150 GWh/year. However, development of new materials and their optimization to predicted ideal structure-property characteristics can typically take >10 years of capital-intensive research to find the best solidification and dopant strategies. Typical solid-state manufacture considers high temperature synthesis based on powder sintering for Co-free cathode material integration, which is time and labor intensive, produces a large CO2 footprint, and incurs high costs. In contrast, wet-chemical fabrication methods like sequential deposition synthesis (SDS) can realize faster achievements in direct liquid precursor to solidified electrolyte translation. Li7La3Zr2O12 (LLZO) is a promising solid electrolyte that has seen much interest in the battery field and has been demonstrated to be manufacturable with thickness between 1-15 µm via SDS. In this work, we demonstrate for the first time a high throughput experimental platform, computer-controlled SDS deposition system to rapidly fabricate LLZO and alter its structure-property characteristics with precursor and deposition modulations. Dopant amounts are adjusted in real time to easily control film composition and test a wide parameter field. In-situ annealing is achieved via an advanced heating element implemented directly into the chamber. Raman spectroscopy exhibits sufficient sensitivity to the phases under study, is a contactless and nondestructive technique, and has a low data acquisition time allowing for high-volume analysis coupled to high throughput synthesis. A quantification of Raman spectra is presented to supply a Bayesian optimization framework for greater experimental efficiency by selecting interesting regions by phase and other 2nd order characteristics of the experimental space to selectively sample for desired phases and, importantly, their high-dimensional phase boundaries. The capabilities of the new experimental framework are discussed for further work in accelerated solid-state ceramic materials discovery and we employ here careful considerations on the synthesis methods and computational approaches chosen towards the plethora of ceramic process options. This framework is capable of rapidly synthesizing solid-state electrolytes with a variety of composition and deposition conditions to optimize their properties so they can be rapidly deployed in next-generation batteries in significantly shorter times than traditional methods allow.