More Like this

1. Enhanced Piezoelectric, Ferroelectric, and Electrostrictive Properties of Lead‐Free (1‐ x )BCZT‐( x )BCST Electroceramics with Energy Harvesting Capability

   https://doi.org/10.1002/smll.202300549  

   Baraskar, Bharat G. ; Kolekar, Yesappa D. ; Thombare, Balu. R. ; James, Ajit. R. ; Kambale, Rahul C. ; Ramana, C. V. ( May 2023 , Small)

   Next‐generation electronics and energy technologies can now be developed as a result of the design, discovery, and development of novel, environmental friendly lead (Pb)‐free ferroelectric materials with improved characteristics and performance. However, there have only been a few reports of such complex materials’ design with multi‐phase interfacial chemistry, which can facilitate enhanced properties and performance. In this context, herein, novel lead‐free piezoelectric materials (1‐x)Ba_0.95Ca_0.05Ti_0.95Zr_0.05O₃‐(x)Ba_0.95Ca_0.05Ti_0.95Sn_0.05O₃, are reported, which are represented as (1‐x)BCZT‐(x)BCST, with demonstrated excellent properties and energy harvesting performance. The (1‐x)BCZT‐(x)BCST materials are synthesized by high‐temperature solid‐state ceramic reaction method by varyingxin the full range (x= 0.00–1.00). In‐depth exploration research is performed on the structural, dielectric, ferroelectric, and electro‐mechanical properties of (1‐x)BCZT‐(x)BCST ceramics. The formation of perovskite structure for all ceramics without the presence of any impurity phases is confirmed by X‐ray diffraction (XRD) analyses, which also reveals that the Ca²⁺, Zr⁴⁺, and Sn⁴⁺are well dispersed within the BaTiO₃lattice. For all (1‐x)BCZT‐(x)BCST ceramics, thorough investigation of phase formation and phase‐stability using XRD, Rietveld refinement, Raman spectroscopy, high‐resolution transmission electron microscopy (HRTEM), and temperature‐dependent dielectric measurements provide conclusive evidence for the coexistence of orthorhombic + tetragonal (Amm2+P4mm) phases at room temperature. The steady transition ofAmm2crystal symmetry toP4mmcrystal symmetry with increasingxcontent is also demonstrated by Rietveld refinement data and related analyses. The phase transition temperatures, rhombohedral‐orthorhombic (T_R‐O), orthorhombic‐ tetragonal (T_O‐T), and tetragonal‐cubic (T_C), gradually shift toward lower temperature with increasingxcontent. For (1‐x)BCZT‐(x)BCST ceramics, significantly improved dielectric and ferroelectric properties are observed, including relatively high dielectric constantε_r≈ 1900–3300 (near room temperature),ε_r≈ 8800–12 900 (near Curie temperature), dielectric loss, tanδ≈ 0.01–0.02, remanent polarizationP_r≈ 9.4–14 µC cm⁻², coercive electric fieldE_c≈ 2.5–3.6 kV cm⁻¹. Further, high electric field‐induced strainS≈ 0.12–0.175%, piezoelectric charge coefficientd₃₃≈ 296–360 pC N⁻¹, converse piezoelectric coefficient ≈ 240–340 pm V⁻¹, planar electromechanical coupling coefficientk_p≈ 0.34–0.45, and electrostrictive coefficient (Q₃₃)_avg≈ 0.026–0.038 m⁴C⁻²are attained. Output performance with respect to mechanical energy demonstrates that the (0.6)BCZT‐(0.4)BCST composition (x= 0.4) displays better efficiency for generating electrical energy and, thus, the synthesized lead‐free piezoelectric (1‐x)BCZT‐(x)BCST samples are suitable for energy harvesting applications. The results and analyses point to the outcome that the (1‐x)BCZT‐(x)BCST ceramics as a potentially strong contender within the family of Pb‐free piezoelectric materials for future electronics and energy harvesting device technologies.

    

   more » « less
2. High stability SrTi 1−x Fe x O 3−δ electrodes for oxygen reduction and oxygen evolution reactions

   https://doi.org/10.1039/c9ta07548h  

   Zhang, Shan-Lin ; Cox, Dalton ; Yang, Hao ; Park, Beom-Kyeong ; Li, Cheng-Xin ; Li, Chang-Jiu ; Barnett, Scott A. ( September 2019 , Journal of Materials Chemistry A)

   Sr(Ti 1−x Fe x )O 3−δ (STF) has recently been explored as an oxygen electrode for solid oxide electrochemical cells (SOCs). Model thin film electrode studies show oxygen surface exchange rates that generally improve with increasing Fe content when x < 0.5, and are comparable to the best Co-containing perovskite electrode materials. Recent results on porous electrodes with the specific composition Sr(Ti 0.3 Fe 0.7 )O 3−δ show excellent electrode performance and stability, but other compositions have not been tested. Here we report results for porous electrodes with a range of compositions from x = 0.5 to 0.9. The polarization resistance decreases with increasing Fe content up to x = 0.7, but increases for further increases in x . This results from the interaction of two effects – the oxygen solid state diffusion coefficient increases with increasing x , but the electrode surface area and surface oxygen exchange rate decrease due to increased sinterability and Sr surface segregation for the Fe-rich compositions. Symmetric cells showed no degradation during 1000 h life tests at 700 °C even at a current density of 1.5 A cm −2 , showing that all the STF electrode compositions worked stably in both fuel cell mode and electrolysis modes. The excellent stability may be explained by X-ray Photoelectron Spectroscopy (XPS) results showing that the amount of surface segregated Sr did not change during the long-term testing, and by relatively low polarization resistances that help avoid electrode delamination. 

   more » « less
3. Accelerated Perovskite Oxide Development for Thermochemical Energy Storage by a High‐Throughput Combinatorial Approach

   https://doi.org/10.1002/aenm.202203833  

   Cai, Runxia ; Bektas, Hilal ; Wang, Xijun ; McClintock, Kyle ; Teague, Lauren ; Yang, Kunran ; Li, Fanxing ( March 2023 , Advanced Energy Materials)

   The structural and compositional flexibility of perovskite oxides and their complex yet tunable redox properties offer unique optimization opportunities for thermochemical energy storage (TCES). To improve the relatively inefficient and empirical‐based approaches, a high‐throughput combinatorial approach for accelerated development and optimization of perovskite oxides for TCES is reported here. Specifically, thermodynamic‐based screening criteria are applied to the high‐throughput density functional theory (DFT) simulation results of over 2000 A/B‐site doped SrFeO_3−δ. 61 promising TCES candidates are selected based on the DFT prediction. Of these, 45 materials with pure perovskite phases are thoroughly evaluated. The experimental results support the effectiveness of the high‐throughput approach in determining both the oxygen capacity and the oxidation enthalpy of the perovskite oxides. Many of the screened materials exhibit promising performance under practical operating conditions: Sr_0.875Ba_0.125FeO_3−δexhibits a chemical energy storage density of 85 kJ kg_ABO3⁻¹under an isobaric condition (with air) between 400 and 800 °C whereas Sr_0.125Ca_0.875Fe_0.25Mn_0.75O_3−δdemonstrates an energy density of 157 kJ kg_ABO3⁻¹between 400 °C/0.2 atm O₂and 1100 °C/0.01 atm O₂. An improved set of optimization criteria is also developed, based on a combination of DFT and experimental results, to improve the effectiveness for accelerated development of redox‐active perovskite oxides.

    

   more » « less
4. Polaron size and shape effects on oxygen vacancy interactions in lanthanum strontium ferrite

   https://doi.org/10.1039/C7TA06948K  

   Das, Tridip ; Nicholas, Jason D. ; Qi, Yue ( January 2017 , Journal of Materials Chemistry A)

   Both aliovalent doping and the charge state of multivalent lattice ions determine the oxygen non-stoichiometry ( δ ) of mixed ionic and electronic conductors (MIECs). Unfortunately, it has been challenging for both modeling and experiments to determine the multivalent ion charge states in MIECs. Here, the Fe charge state distribution was determined for various compositions and phases of the MIEC La 1−x Sr x FeO 3−δ (LSF) using the spin-polarized density functional theory (DFT)-predicted magnetic moments on Fe. It was found that electron occupancy and crystal-field-splitting-induced differences between the Fe 3d-orbitals of the square pyramidally coordinated, oxygen-vacancy-adjacent Fe atoms and the octahedrally-coordinated, oxygen-vacancy-distant-Fe atoms determined whether the excess electrons produced during oxygen vacancy formation remained localized at the first nearest neighbor Fe atoms (resulting in small oxygen vacancy polarons, as in LaFeO 3 ) or were distributed to the second-nearest-neighbor Fe atoms (resulting in large oxygen vacancy polarons, as in SrFeO 3 ). The progressively larger polaron size and anisotropic shape changes with increasing Sr resulted in increasing oxygen vacancy interactions, as indicated by an increase in the oxygen vacancy formation energy above a critical δ threshold. This was consistent with experimental results showing that Sr-rich LSF and highly oxygen deficient compositions are prone to oxygen-vacancy-ordering-induced phase transformations, while Sr-poor and oxygen-rich LSF compositions are not. Since oxygen vacancy induced phase transformations cause a decrease in the mobile oxygen vacancy site fraction ( X ), both δ and X were predicted as a function of temperature and oxygen partial pressure, for multiple LSF compositions and phases using a combined thermodynamics and DFT approach. 

   more » « less
5. Advanced oxygen-electrode-supported solid oxide electrochemical cells with Sr(Ti,Fe)O 3−δ -based fuel electrodes for electricity generation and hydrogen production

   https://doi.org/10.1039/d0ta06678h  

   Zhang, Shan-Lin ; Wang, Hongqian ; Yang, Tianrang ; Lu, Matthew Y. ; Li, Cheng-Xin ; Li, Chang-Jiu ; Barnett, Scott A. ( December 2020 , Journal of Materials Chemistry A)

   null (Ed.)

   Sr(Ti 0.3 Fe 0.7 )O 3−δ (STF) and the associated exsolution electrodes Sr 0.95 (Ti 0.3 Fe 0.63 Ru 0.07 )O 3−δ (STFR), or Sr 0.95 (Ti 0.3 Fe 0.63 Ni 0.07 )O 3−δ (STFN) are alternatives to Ni-based cermet fuel electrodes for solid oxide electrochemical cells (SOCs). They can provide improved tolerance to redox cycling and fuel impurities, and may allow direct operation with hydrocarbon fuels. However, such perovskite-oxide-based electrodes present processing challenges for co-sintering with thin electrolytes to make fuel electrode supported SOCs. Thus, they have been mostly limited to electrolyte-supported SOCs. Here, we report the first example of the application of perovskite oxide fuel electrodes in novel oxygen electrode supported SOCs (OESCs) with thin YSZ electrolytes, and demonstrate their excellent performance. The OESCs have La 0.8 Sr 0.2 MnO 3−δ –Zr 0.92 Y 0.16 O 2−δ (LSM–YSZ) oxygen electrode-supports that are enhanced via infiltration of SrTi 0.3 Fe 0.6 Co 0.1 O 3−δ , while the fuel electrodes are either Ni-YSZ, STF, STFN, or STFR. Fuel cell power density as high as 1.12 W cm −2 is obtained at 0.7 V and 800 °C in humidified hydrogen and air with the STFR electrode, 60% higher than the same cell made with a Ni-YSZ electrode. Electrolysis current density as high as −1.72 A cm −2 is obtained at 1.3 V and 800 °C in 50% H 2 O to 50% H 2 mode; the STFR cell yields a value 72% higher than the same cell made with a Ni-YSZ electrode, and competitive with the widely used conventional Ni-YSZ-supported cells. The high performance is due in part to the low resistance of the thin YSZ electrolyte, and also to the low fuel electrode polarization resistance, which decreases with fuel electrode in the order: Ni-YSZ > STF > STFN > STFR. The high performance of the latter two electrodes is due to exsolution of catalytic metal nanoparticles; the results are discussed in terms of the microstructure and properties of each electrode material, and surface oxygen exchange resistance values are obtained over a range of conditions for STF, STFN, and STFN. The STF fuel electrodes also provide good stability during redox cycling. 

   more » « less