Toward Ecofriendly Piezoelectric Ceramics-Reduction of Energy and Environmental Footprint from Conceptualization to Deployment.

Piezoelectric materials are widely used in electromechanical coupling components including actuators, kinetic sensors, and transducers, as well as in kinetic energy harvesters that convert mechanical energy into electricity and thus can power wireless sensing networks and the Internet of Things (IoT). Because the number of deployed energy harvesting powered systems is projected to explode, the supply of piezoelectric energy harvesters is also expected to be boosted. However, despite being able to produce green electricity from the ambient environment, high-performance piezoelectrics (i.e., piezoelectric ceramics) are energy intensive in research and manufacturing. For instance, the design of new piezoceramics relies on experimental trials, which need high process temperatures and thus cause high consumption and waste of energy. Also, the dominant element in high-performance piezoceramics is hazardous Pb, but substituting Pb with other nonhazardous elements may lead to a compromise of performance, extending the energy payback time and imposing a question of trade-offs between energy and environmental benefits. Meanwhile, piezoceramics are not well recycled, raising even more issues in terms of energy saving and environmental protection. This paper discusses these issues and then proposes solutions and provides perspectives to the future development of different aspects of piezoceramic research and industry.

A Predictive Theory for Domain Walls in Oxide Ferroelectrics Based on Interatomic Interactions and its Implications for Collective Material Properties.

Domain walls separating regions of ferroelectric material with polarization oriented in different directions are crucial for applications of ferroelectrics. Rational design of ferroelectric materials requires the development of a theory describing how compositional and environmental changes affect domain walls. To model domain wall systems, a discrete microscopic Landau-Ginzburg-Devonshire (dmLGD) approach with A- and B-site cation displacements serving as order parameters is developed. Application of dmLGD to the classic BaTiO3 , KNbO3, and PbTiO3 ferroelectrics shows that A-B cation repulsion is the key interaction that couples the polarization in neighboring unit cells of the material. dmLGD decomposition of the total energy of the system into the contributions of the individual cations and their interactions enables the prediction of different properties for a wide range of ferroelectric perovskites based on the results obtained for BaTiO3 , KNbO3, and PbTiO3 only. It is found that the information necessary to estimate the structure and energy of domain-wall "defects" can be extracted from single-domain 5-atom first-principles calculations, and that "defect-like" domain walls offer a simple model system that sheds light on the relative stabilities of the ferroelectric, antiferroelectric, and paraelectric bulk phases. The dmLGD approach provides a general theoretical framework for understanding and designing ferroelectric perovskite oxides.

A Multilevel Analytical Theory for Prediction of Ferroelectric Perovskite Oxide Properties from Composition.

Prediction of properties from composition is a fundamental goal of materials science that is particularly relevant for ferroelectric perovskite oxide solid solutions where compositional variation is a primary tool for material design. Design of ferroelectric oxide solid solutions has been guided by heuristics and first-principles and Landau-Ginzburg-Devonshire theoretical methods that become increasingly difficult to apply in ternary, quaternary, and quintary solid solutions. To address this problem, a multilevel model is developed for the prediction of the ferroelectric-to-paraelectric transition temperature (Tc ), coercive field (Ec ), and polarization (P) of PbTiO3 -derived ferroelectric solid solutions from composition. The characteristics of the materials at different length scales, starting at the level of the electronic structure and chemical bonding of the constituent ions and ending at the level of collective behavior, are analytically related by using ferroelectric domain walls and cationic off-center displacements as the key links between the different levels of the model. The obtained composition-structure-property relationships provide a unified quantitatively predictive theory for understanding PbTiO3 -derived solid solutions. Such a multilevel analytical modeling approach is likely to be generally applicable to different classes of ferroelectric perovskite oxides and to other functional properties, and to materials and properties beyond the field of ferroelectrics.