Engineering topics
Zhang, Dawei
Publications and source records attributed to Zhang, Dawei.
Manganese-based A-site high-entropy perovskite oxide for solar thermochemical hydrogen production
Non-stoichiometric perovskite oxides have been studied as a new family of redox oxides for solar thermochemical hydrogen (STCH) production owing to their favourable thermodynamic properties. However, conventional perovskite oxides suffer from limited phase stability and kinetic properties, and poor cyclability. Here, we report a strategy of introducing A-site multi-principal-component mixing to develop a high-entropy perovskite oxide, (La 1/6 Pr 1/6 Nd 1/6 Gd 1/6 Sr 1/6 Ba 1/6 )MnO 3 (LPNGSB_Mn), which shows desirable thermodynamic and kinetics properties as well as excellent phase stability and cycling durability. LPNGSB_Mn exhibits enhanced hydrogen production (~77.5 mmol mol oxide -1 ) compared to (La 2/3 Sr 1/3 )MnO 3 (~53.5 mmol mol oxide -1 ) in a short 1 hour redox duration and high STCH and phase stability for 50 cycles. LPNGSB_Mn possesses a moderate enthalpy of reduction (252.51–296.32 kJ (mol O) -1 ), a high entropy of reduction (126.95–168.85 J (mol O) -1 K -1 ), and fast surface oxygen exchange kinetics. All A-site cations do not show observable valence changes during the reduction and oxidation processes. In conclusion, this research preliminarily explores the use of one A-site high-entropy perovskite oxide for STCH.
New High-Entropy Perovskite Oxides with Increased Reducibility and Stability for Thermochemical Hydrogen Generation
This project aims to design, synthesize, and test a transformative class of High-Entropy Perovskite Oxides (HEPOs) as redox oxides to enable thermochemical hydrogen generation with improved stability, kinetics, and efficiency. These developed HEPOs are expected to demonstrate improved kinetics with oxygen surface exchange coefficient ( k > 7.5×10 -4 cm/s) in Budget Period (BP) 1, retain its structural stability in a broad range of oxygen non-stoichiometry (Δδ > 0.15) at a low operating reduction temperature of T red < 1400°C in BP 2, and deliver a H 2 yield of over 400 µmol per gram of oxide and high stability with less than 20% degradation after at least 50 cycles in BP 3. This project is feasible due to the unique thermodynamic properties (simultaneously increased reducibility and phase stability) and kinetic characters (stability against particle coarsening and potentially enhanced oxygen transport and surface reaction kinetics) of such HEPOs, and it is enabled by a unique active learning computational design approach. Computational studies have been conducted to investigate the oxygen vacancy formation in complex perovskite systems. * Accurate prediction of V O .. concentration with disordered A-site cations in Fe-based high-entropy perovskite oxides * Combined MC/DFT computation elucidates the mechanism of Co preference on the redox due to the strain introduced by local distortion. In this project, we explored a large number (~150) of perovskite compositions, which are listed in Tables 2 – 4). * All perovskite specimens have been synthesized through a high-throughput high-energy ball milling process, followed by the conventional sintering process. * XRD, SEM/EDS and TGA were performed to confirm the crystal structure, phase homogeneity and oxygen non-stoichiometry for compositionally complex perovskite oxides (CCPOs). * 110 compositions show single-phase from XRD * Unusual aliovalent doping effects in medium-entropy perovskite compositions. * V-shape relation between Δδ vs. x (La 1-x Sr x )(Mn 1/3 Fe 1/3 Ti 1/3 )O 3 * The highest reported hydrogen production for the CCPOs made in this project ( T re = 1350 ºC 30 min, T Ox = 1100 ºC 30 min) * B-site mixing (La 0.8 Sr 0.2 )(Mn 0.2 Fe 0.2 Co 0.4 Al 0.2 )O 3 : 89.97 ± 2.73 mmol H2 /mol oxide (395 ± 10 μmol/g oxide ) (i) No phase transformation during reactions when Co molar ratio is less than 61% (ii) Balance between intrinsic kinetics (oxygen surface exchange) and thermodynamics (oxygen non-stoichiometry) (iii) Preference of Co identified by in-situ XPS * A-site mixing (La 1/6 Pr 1/6 Nd 1/6 Gd 1/6 Ba 1/6 Sr1/6)MnO 3 : 98.48 mmol H2 /mol oxid e (~415 μmol/g oxide )
Compositionally complex perovskite oxides: Discovering a new class of solid electrolytes with interface-enabled conductivity improvements
Compositionally complex ceramics (CCCs), including high-entropy ceramics, offer a vast, unexplored compositional space for materials discovery. Herein, we propose and demonstrate strategies for tailoring CCCs via a combination of non-equimolar compositional designs and control of grain boundaries (GBs) and microstructures. Using oxide solid electrolytes for all-solid-state batteries as an example, we have discovered a class of compositionally complex perovskite oxides (CCPOs) with improved lithium ionic conductivities beyond the limit of conventional doping. For example, we demonstrate that the ionic conductivity can be improved by >60% in (Li 0.375 Sr 0.4375 )(Ta 0.375 Nb 0.375 Zr 0.125 Hf 0.125 )O 3-δ compared with the (Li 0.375 Sr 0.4375 )(Ta 0.75 Zr 0.25 )O 3-δ (LSTZ) baseline. Furthermore, the ionic conductivity can be improved by another >70% via quenching, achieving >270% of the LSTZ. Notably, we demonstrate GB-enabled conductivity improvements via both promoting grain growth and altering GB structures through compositional designs and processing. In a broader perspective, this work suggests new routes for discovering and tailoring CCCs for energy storage and many other applications.
Oxygen non-stoichiometry and point defect equilibria in (La1/6Pr1/6Nd1/6Gd1/6Ba1/6Sr1/6)MnO3-δ
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Oxygen non-stoichiometry and point defect equilibria in (La1/6Pr1/6Nd1/6Gd1/6Ba1/6Sr1/6)MnO3-δ at 1200 – 1450 oC
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Long- and short-range orders in 10-component compositionally complex ceramics
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Accurate prediction of oxygen vacancy concentration with disordered A-site cations in high-entropy perovskite oxides
Abstract Entropic stabilized ABO 3 perovskite oxides promise many applications, including the two-step solar thermochemical hydrogen (STCH) production. Using binary and quaternary A-site mixed {A}FeO 3 as a model system, we reveal that as more cation types, especially above four, are mixed on the A-site, the cell lattice becomes more cubic-like but the local Fe–O octahedrons are more distorted. By comparing four different Density Functional Theory-informed statistical models with experiments, we show that the oxygen vacancy formation energies ( $${E}_{V}^{f}$$ E V f ) distribution and the vacancy interactions must be considered to predict the oxygen non-stoichiometry ( δ ) accurately. For STCH applications, the $${E}_{V}^{f}$$ E V f distribution, including both the average and the spread, can be optimized jointly to improve Δ δ (difference of δ between the two-step conditions) in some hydrogen production levels. This model can be used to predict the range of water splitting that can be thermodynamically improved by mixing cations in {A}FeO 3 perovskites.
Compositionally Complex Perovskite Oxides for Solar Thermochemical Water Splitting
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