Ceramics and Nanostructures for Energy Harvesting and Storage.

In recent years, the worldwide research in the field of energy harvesting and storage has focused on the development of clean and sustainable methods that can respond to the rising energy demands of humankind [...].

Current Achievements in Flexible Piezoelectric Nanogenerators Based on Barium Titanate.

Harvesting ambient mechanical energy at the nanometric scale holds great promise for powering small electronics and achieving self-powered electronic devices. The current review is focused on kinetic energy harvesters, particularly on flexible piezoelectric nanogenerators (p-NGs) based on barium titanate (BaTiO3) nanomaterials. p-NGs based on nanotubes, nanowires, nanofibres, nanoplatelets, nanocubes or nanoparticles of BaTiO3 fabricated in vertical or lateral orientation, as well as mixed composite structures, are overviewed here. The achievable power output level is shown to depend on the fabrication method, processing parameters and potential application conditions. Therefore, the most widely studied aspects, such as influence of geometry/orientation, BaTiO3 content, poling process and other factors in the output performance of p-NGs, are discussed. The current standing of BaTiO3-based p-NGs as possible candidates for various applications is summarized, and the issues that need to be addressed for realization of practical piezoelectric energy harvesting devices are discussed.

Flash Sintered Potassium Sodium Niobate: High-Performance Piezoelectric Ceramics at Low Thermal Budget Processing.

Alternative sintering technologies promise to overcome issues associated with conventional ceramic sintering such as high thermal budgets and CO2 footprint. The sintering process becomes even more relevant for alkali-based piezoelectric ceramics such as K0.5Na0.5NbO3 (KNN) typically fired above 1100 °C for several hours that induces secondary phase formation and, thereby, degrades their electrical characteristics. Here, an ability of KNN ceramics to be of high performance is successfully demonstrated, using an electric field- and current-assisted Flash sintering technique at 900 °C only. Reported for the first time, Flash sintered KNN ceramics have room-temperature remnant polarization Pr = 21 µC/cm2 and longitudinal piezoelectric coefficient d33 = 117 pC/N, slightly superior to that of conventional ones due to the reduced content of secondary phases. High-performance KNN ceramics Flash sintered at a low-thermal budget have implications for the development of innovative low carbon technologies, electroceramics stakeholders, and piezoelectric energy harvesters.

Synergetic Effect of Polyaniline and Graphene in Their Composite Supercapacitor Electrodes: Impact of Components and Parameters of Chemical Oxidative Polymerization.

The current development of clean and high efficiency energy sources such as solar or wind energy sources has to be supported by the design and fabrication of energy storage systems. Electrochemical capacitors (or supercapacitors (SCs)) are promising devices for energy storage thanks to their highly efficient power management and possible small size. However, in comparison to commercial batteries, SCs do not have very high energy densities that significantly limit their applications. The value of energy density directly depends on the capacitance of full SCs and their cell voltage. Thus, an increase of SCs electrode specific capacitance together with the use of the wide potential window electrolyte can result in high performance SCs. Conductive polymer polyaniline (PANI) as well as carbonaceous materials graphene (G) or reduced graphene oxide (RGO) have been widely studied for usage in electrodes of SCs. Although pristine PANI electrodes have shown low cycling stability and graphene sheets can have low specific capacitance due to agglomeration during their preparation without a spacer, their synergetic effect can lead to high electrochemical properties of G/PANI composites. This review points out the best results for G/PANI composite in comparison to that of pristine PANI or graphene (or RGO). Various factors, such as the ratio between graphene and PANI, oxidants, time, and the temperature of chemical oxidative polymerization, which have been determined to influence the morphology, capacitance, cycling stability, etc. of the composite electrode materials measured in three-electrode system are discussed. Consequently, we provide an in-depth summary on diverse promising approaches of significant breakthroughs in recent years and provide strategies to choose suitable electrodes based on PANI and graphene.

Low-Temperature Dielectric Response of Strontium Titanate Thin Films Manipulated by Zn Doping.

The voltage dependence of the dielectric permittivity ε' and the low dielectric loss tanδ of incipient ferroelectrics have drawn vast attention to the use of these materials for the development of tuning elements in electronics and telecommunications. Here, we study the DC electric field dependence of low-temperature ε' in ~320 nm thick sol-gel-derived SrTi1-xZnxO3-δ thin films with x = 0.01 and 0.05, deposited on Pt/TiO2/SiO2/Si substrates. Incorporation of Zn onto Ti sites is found to decrease ε' compared to undoped SrTiO3 films, while increasing the relative tunability nr up to ~32.9% under a DC electric field of 125 kV/cm at low temperatures. The hysteresis-free variation in ε' with electric field and tanδ values below 0.6% observed for SrTi1-xZnxO3-δ film with x = 0.01 make this compound more attractive for tunable device applications.

High Q Dielectric Titanium Tellurite Thick Films on Alumina Substrates for High Frequency Telecommunications.

The vital role of high-quality-factor (Q) high-frequency (f) dielectric resonators in the growing microwave telecommunication, satellite broadcasting and intelligent transport systems has long motivated the search for new, small size, and lightweight integrated components and packages, prepared by low cost and sustainable processes. One approach is replacing the currently used bulk ceramic dielectrics by thick films of low-sintering-temperature dielectrics fabricated by affordable processes. Here we demonstrate the fabrication of high-Q TiTe3O8 thick films directly on low loss Al2O3 substrates by electrophoretic deposition using sacrificial carbon layer. Nineteen-micrometre-thick TiTe3O8 films on Al2O3 sintered at 700 °C are found to have a relative permittivity εr of 32 and Q × f > 21,000 GHz. Being thus able to measure and provide for the first time the microwave dielectric properties of these films, our results suggest that TiTe3O8 films on Al2O3 substrates are suitable for microlayer microstrip array applications.

Polar Phonon Behaviour in Polycrystalline Bi-Doped Strontium Titanate Thin Films.

Strontium titanate-based materials with ferroelectric or relaxor-like properties have drawn vast attention as polar dielectrics for electronics and telecommunications. Here, we study the lattice dynamics in sol-gel-derived Sr1-1.5xBixTiO3 thin films with x = 0.0053 and 0.167, deposited on Al2O3 substrates, using a variable-temperature far-infrared spectroscopy in a transmittance mode. Bi doping, known to induce a low-frequency dielectric relaxation in SrTiO3 (ST) ceramics and films, due to off-centre dopant ion displacements generating electric dipoles, is shown to affect the polar phonon behaviour of thin films. We show that in weakly Bi-doped films, the low-frequency polar TO1 mode softens on cooling but less than in undoped ST. In heavily Bi-doped ST films, this mode displays no significant frequency variation with temperature from 300 to 10 K. The polar phonon behaviour of polycrystalline Bi-doped ST thin films is comparable with that of Bi-doped ST ceramics, which exhibit dielectric relaxations and harden soft-mode behaviour instead of the ferroelectric phase transition.

Dielectric Relaxation, Local Structure and Lattice Dynamics in Mn-Doped Potassium Tantalate Ceramics.

Alkaline niobate and tantalate perovskites have attracted attention as polar dielectrics for electronics and telecommunications. Here, we studied the polar behaviour, lattice dynamics, and local structure in conventionally processed K0.985Mn0.015TaO3±Î´ ceramics using a combination of variable-temperature dielectric and Raman spectroscopies, and X-ray absorption fine structure (XAFS) measurements, respectively. Mn doping induces a low-frequency dielectric relaxation in KTaO3 (KT), which follows the Arrhenius law with an activation energy U ≈ 105 meV and the characteristic relaxation time τ0 ≈ 4.6 × 10-14 s. Our XAFS results support preferential Mn occupancy of the cuboctahedral sites as Mn2+, with these cations strongly off-centred in the oversized oxygen cages. Such disordered Mn displacements generate electric dipoles, which are proposed as the source of the observed dielectric relaxation. We show that in Mn-doped ceramics, the low-frequency polar TO1 mode softens on cooling and, at low temperatures, exhibits a higher frequency than in undoped KT. This mode displays no detectable splitting, which contrasts with Li-doped KT that also contains off-centred Li+ species on the cuboctahedral sites. Therefore, we conclude that the coupling between the Mn displacements and the lattice is weaker than in the Li case, and Mn-doped KT therefore exhibits a dielectric relaxation but no ferroelectric transition.

Graphene/Reduced Graphene Oxide-Carbon Nanotubes Composite Electrodes: From Capacitive to Battery-Type Behaviour.

Thanks to the advanced technologies for energy generation such as solar cells and thermo- or piezo-generators the amount of electricity transformed from light, heat or mechanical pressure sources can be significantly enhanced. However, there is still a demand for effective storage devices to conserve electrical energy which addresses the wide range of large stationary applications from electric vehicles to small portable devices. Among the large variety of energy-storage systems available today, electrochemical energy sources and, in particular, supercapacitors (SC), are rather promising in terms of cost, scaling, power management, life cycle and safety. Therefore, this review surveys recent achievements in the development of SC based on composites of such carbon-derived materials as graphene (G) and reduced graphene oxide (rGO) with carbon nanotubes (CNT). Various factors influencing the specific capacitance are discussed, while specific energy and power as well as cycling stability of SC with G/rGO-CNT composite electrode materials are overviewed.

Effect of Solution Conditions on the Properties of Sol-Gel Derived Potassium Sodium Niobate Thin Films on Platinized Sapphire Substrates.

If piezoelectric micro-devices based on K0.5Na0.5NbO3 (KNN) thin films are to achieve commercialization, it is critical to optimize the films' performance using low-cost scalable processing conditions. Here, sol-gel derived KNN thin films are deposited using 0.2 and 0.4 M precursor solutions with 5% solely potassium excess and 20% alkali (both potassium and sodium) excess on platinized sapphire substrates with reduced thermal expansion mismatch in relation to KNN. Being then rapid thermal annealed at 750 °C for 5 min, the films revealed an identical thickness of ~340 nm but different properties. An average grain size of ~100 nm and nearly stoichiometric KNN films are obtained when using 5% potassium excess solution, while 20% alkali excess solutions give the grain size of 500-600 nm and (Na + K)/Nb ratio of 1.07-1.08 in the prepared films. Moreover, the 5% potassium excess solution films have a perovskite structure without clear preferential orientation, whereas a (100) texture appears for 20% alkali excess solutions, being particularly strong for the 0.4 M solution concentration. As a result of the grain size and (100) texturing competition, the highest room-temperature dielectric permittivity and lowest dissipation factor measured in the parallel-plate-capacitor geometry were obtained for KNN films using 0.2 M precursor solutions with 20% alkali excess. These films were also shown to possess more quadratic-like and less coercive local piezoelectric loops, compared to those from 5% potassium excess solution. Furthermore, KNN films with large (100)-textured grains prepared from 0.4 M precursor solution with 20% alkali excess were found to possess superior local piezoresponse attributed to multiscale domain microstructures.

Defects and charge transport in Mn-doped K0.5Na0.5NbO3 ceramics.

The relationship between charge transport, defects and ferroelectric response is established for K0.5Na0.5NbO3 (KNN) and Mn-doped KNN ceramics. At room temperature the conduction in KNN is associated with hole transport and can be suppressed by Mn doping. Because of that a less leaky ferroelectric hysteresis loop is obtained for Mn-doped KNN. At high temperatures the conduction is dominated by the motion of ionized oxygen vacancies, the concentration of which increases with Mn doping. This work adds relevant information on KNN and leverages its potential application.