The structural origin of enhanced piezoelectric performance and stability in KNN-based ceramics can be attributed to the hierarchical nanodomain architecture with phase coexistence.
Owing
to growing environmental concerns, the development of lead-free
piezoelectrics with comparable performance to the benchmark Pb(Zr,Ti)O3 (PZT) becomes of great urgency. However, a further enhancement
of lead-free piezoelectrics based on existing strategies has reached
a bottleneck. Here we achieve a slush polar state with multiphase
coexistence in lead-free potassium–sodium niobate (KNN) piezoceramics,
which shows a novel relaxor behavior, i.e., frequency dispersion at
the transition between different ferroelectric phases. It is very
different from the conventional relaxor behavior which occurs at the
paraelectric–ferroelectric phase transition. We obtain an ultrahigh
piezoelectric coefficient (d
33) of 650
± 20 pC/N, the largest value of nontextured KNN-based ceramics,
outperforming that of the commercialized PZT-5H. Atomic-resolution
polarization mapping by Z-contrast imaging from different orientations
reveals the entire material to comprise polar nanoregions with multiphase
coexistence, which is again very different from conventional ferroelectric
relaxors which have polar domains within a nonpolar matrix. Theoretical
simulations validate the significantly decreased energy barrier and
polarization anisotropy, which is facilitated by the high-density
domain boundaries with easy polarization rotation bridging the multiphase-coexisting
nanodomains. This work demonstrates a new strategy for designing lead-free
piezoelectrics with further enhanced performance, which should also
be applicable to other functional materials requiring a slush (flexible)
state with respect to external stimulus.
Because of growing environmental concerns, the development of lead-free piezoelectric materials with enhanced properties has become of great interest. Here, we report a giant piezoelectric coefficient (d) of 550 pC/N and a high Curie temperature (T) of 237 °C in (1-x-y)KNaNbSbOxBiFeOyBiNaZrO (KNNS-xBF-yBNZ) ceramics by optimizing x, y, z, and w. Atomic-resolution polarization mapping by Z-contrast imaging reveals the intimate coexistence of rhombohedral (R) and tetragonal (T) phases inside nanodomains, that is, a structural origin for the R-T phase boundary in the present KNN system. Hence, the physical origin of high piezoelectric performance can be attributed to a nearly vanishing polarization anisotropy and thus low domain wall energy, facilitating easy polarization rotation between different states under an external field.
Due to growing environmental
concerns on the toxicity of lead-based
piezoelectric materials, lead-free alternatives are urgently required
but so far have not been able to reach competitive performance. Here
we employ a novel phase-boundary engineering strategy utilizing the
multiphase convergence, which induces a broad structural flexibility
in a wide phase-boundary zone with contiguous polymorphic phase transitions.
We achieve an ultrahigh piezoelectric constant (d
33) of 700 ± 30 pC/N in BaTiO3-based ceramics,
maintaining >600 pC/N over a wide composition range. Atomic resolution
polarization mapping by Z-contrast imaging reveals the coexistence
of three ferroelectric phases (T + O + R) at the nanoscale with nanoscale
polarization rotation between them. Theoretical simulations confirm
greatly reduced energy barriers facilitating polarization rotation.
Our lead-free material exceeds the performance of the majority of
lead-based systems (including the benchmark PZT-5H) in the temperature
range of 10–40 °C, making it suitable as a lead-free replacement
in practical applications. This work offers a new paradigm for designing
lead-free functional materials with superior electromechanical properties.
In this letter, we use transmission electron microscopy to study the microstructure feature of recently reported Pb-free piezoceramic Ba(Zr0.2Ti0.8)O3-x(Ba0.7Ca0.3)TiO3 across its piezoelectricity-optimal morphotropic phase boundary (MPB) by varying composition and temperature, respectively. The domain structure evolutions during such processes show that in MPB regime, the domains become miniaturized down to nanometer size with a domain hierarchy, which coincides with the d33-maximum region. Further convergent beam electron diffraction measurement shows that rhombohedral and tetragonal crystal symmetries coexist among the miniaturized domains. Strong piezoelectricity reported in such a system is due to easy polarization rotation between the coexisting nano-scale tetragonal and rhombohedral domains.
Synthesis of anisotropic nanostructures from materials with isotropic crystal structures often requires the use of seeds containing twin planes to break the crystalline symmetry and promote the preferential anisotropic growth. Controlling twinning in seeds is therefore critically important for high-yield synthesis of many anisotropic nanostructures. Here, we demonstrate a unique strategy to induce twinning in metal nanostructures for anisotropic growth by taking advantage of the large lattice mismatch between two metals. By using Au-Cu as an example, we show, both theoretically and experimentally, that deposition of Cu to the surface of single-crystalline Au seeds can build up strain energy, which effectively induces the formation of twin planes. Subsequent seeded growth allows the production of Cu nanorods with high shape anisotropy that is unachievable without the use of Au seeds. This work provides an effective strategy for the preparation of anisotropic metal nanostructures.
Achieving a functional and durable non-platinum group metal-based methanol oxidation catalyst is critical for a cost-effective direct methanol fuel cell. While Ni(OH)2 has been widely studied as methanol oxidation catalyst, the initial process of oxidizing Ni(OH)2 to NiOOH requires a high potential of 1.35 V vs. RHE. Such potential would be impractical since the theoretical potential of the cathodic oxygen reduction reaction is at 1.23 V. Here we show that a four-coordinated nickel atom is able to form charge-transfer orbitals through delocalization of electrons near the Fermi energy level. As such, our previously reported periodically arranged four-six-coordinated nickel hydroxide nanoribbon structure (NR-Ni(OH)2) is able to show remarkable methanol oxidation activity with an onset potential of 0.55 V vs. RHE and suggests the operability in direct methanol fuel cell configuration. Thus, this strategy offers a gateway towards the development of high performance and durable non-platinum direct methanol fuel cell.
High-performance piezoelectric materials are critical components for electromechanical sensors and actuators. For more than 60 years, the main strategy for obtaining large piezoelectric response has been to construct multiphase boundaries, where nanoscale domains with local structural and polar heterogeneity are formed, by tuning complex chemical compositions. We used a different strategy to emulate such local heterogeneity by forming nanopillar regions in perovskite oxide thin films. We obtained a giant effective piezoelectric coefficient d33,f* of ~1098 picometers per volt with a high Curie temperature of ~450°C. Our lead-free composition of sodium-deficient sodium niobate contains only three elements (Na, Nb, and O). The formation of local heterogeneity with nanopillars in the perovskite structure could be the basis for a general approach to designing and optimizing various functional materials.
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