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Triboelectric energy harvesting from ambient mechanical sources relies on motion-generated surface charge transfer between materials with different electron affinities. In order to achieve highly efficient energy harvesting performance, choosing materials with a high surface charge density is crucial, and odd-numbered polyamides (Nylons), such as Nylon-11, are particularly promising due to their strong electron-donating characteristics and the possibility to achieve dipolar alignment leading to high surface potential. The use of Nylon-11 as a material for triboelectric energy harvesting has been rather limited due to the extreme processing conditions required for film fabrication, and the high voltage poling process required for dipole alignment. However, several methods to achieve “self-poled” Nylon-11 nanowires via facile nanoconfinement techniques have been demonstrated recently, leading to highly efficient Nylon-11 nanowire-based triboelectric nanogenerators. Here we review the most recent advances in the fabrication of Nylon-11 nanowires, with a focus on how nanoconfinement-based fabrication methods can be used to control phase and crystallinity. These growth methods lead to self-poled nanowires without the requirement for subsequent electrical poling, facilitating their integration into triboelectric energy harvesting devices. Strategies to fabricate Nylon-11 nanowires for applications in triboelectric devices can be extended to other polymeric families as well.

Triboelectric generators rely on contact-generated surface charge transfer between materials with different electron affinities to convert mechanical energy into useful electricity. The ability to modify the surface chemistry of polymeric materials can therefore lead to significant enhancement of the triboelectric performance. Poly(methyl methacrylate) (PMMA) is a biocompatible polymer commonly used in medical applications, but its central position on the triboelectric series, which empirically ranks materials according to their electron-donating or electron accepting tendencies, renders it unsuitable for application in triboelectric generators. Here, we show that the surface potential of PMMA fibers produced by electrospinning can be tailored through the polarity of the voltage used during the fabrication process, thereby improving its triboelectric performance, as compared to typically spin-coated PMMA films. The change in surface chemistry of the electrospun PMMA fibers is verified using X-ray photoelectron spectroscopy, and this is directly correlated to the changes in surface potential observed by Kelvin probe force microscopy. We demonstrate the enhancement of triboelectric energy harvesting capability of the electrospun PMMA fibers, suggesting that this surface potential modification approach can be more widely applied to other materials as well, for improved triboelectric performance.

A flexible and robust piezoelectric nanogenerator (NG) based on a polymer-ceramic nanocomposite structure has been successfully fabricated via a cost-effective and scalable template-assisted hydrothermal synthesis method. Vertically aligned arrays of dense and uniform zinc oxide (ZnO) nanowires (NWs) with high aspect ratio (diameter ∼250 nm, length ∼12 μm) were grown within nanoporous polycarbonate (PC) templates. The energy conversion efficiency was found to be ∼4.2%, which is comparable to previously reported values for ZnO NWs. The resulting NG is found to have excellent fatigue performance, being relatively immune to detrimental environmental factors and mechanical failure, as the constituent ZnO NWs remain embedded and protected inside the polymer matrix., The authors thank Yeonsik Choi for discussions and experimental support. S.K.-N., C.O., and A.D. are grateful for financial support from the European Research Council through an ERC Starting Grant (Grant no. ERC-2014-STG-639526, NANOGEN). F.L.B. and R.A.W. thank the EPSRC Cambridge NanoDTC, EP/G037221/1, for studentship funding. P.S.J. acknowledges the support of TEP-1900 and Talentia Postdoc Program, cofunded by the European Union’s Seventh Framework Program, Marie Skłodowska-Curie actions (COFUND Grant Agreement 267226) and the Ministry of Economy, Innovation, Science and Employment of the Junta de Andalucía. S-L.S acknowledges support through the EPSRC grant EP/M010589/1, This is the final version of the article. It first appeared from American Chemical Society via http://dx.doi.org/10.1021/acsami.6b04041.

Electrical polarization phenomena in GaN are important as they have significant impact on the operation of modern day energy efficient lighting and are fundamental to many GaN-based high power and high frequency electronics. Controlling polarization is beneficial for the optimization of these applications. GaN is also piezoelectric, and therefore mechanical stress and strain are possible handles to control its polarization. Nonetheless, polar semiconductors in general, and GaN in particular, are weak piezoelectric materials when compared to ceramics, and are therefore not considered for characteristic electromechanical applications such as sensing, actuation and mechanical energy harvesting. Here, we examine the effect of nanoscale porosity on the piezoelectricity of initially conductive GaN. We find that for 40% porosity, the previously conductive GaN layer becomes depleted, and exhibits enhanced piezoelectricity as measured using piezoresponse force microscopy, as well as by using a mechanical energy harvesting setup. The effective piezoelectric charge coefficient of the porous GaN, d33,eff, is found to be about 8 pm/V which is 2 3 times larger than bulk GaN. A macroscale device comprising a porous GaN layer delivered 100 nW/cm2 across a resistive load under a 150 kPa mechanical excitation. We performed finite element simulations to analyze the evolution of the piezoelectric properties with porosity. The simulations suggest that increased mechanical compliance due to porosity gives rise to the observed enhanced piezoelectricity in GaN. Furthermore, the simulations show that for stress-based excitations, the porous GaN electromechanical figure of merit is increased by an order of magnitude and becomes comparable to that of barium titanate piezoceramics. In addition, considering the central role played by GaN in modern electronics and optoelectronics, our study validates a very promising research direction when considering stress-based electromechanical applications which combine GaN’s semiconducting and piezoelectric properties.

Piezoelectric polymers, capable of converting mechanical vibrations into electrical energy, are attractive for use in vibrational energy harvesting due to their flexibility, robustness, ease, and low cost of fabrication. In particular, piezoelectric polymers nanostructures have been found to exhibit higher crystallinity, higher piezoelectric coefficients, and "self-poling," as compared to films or bulk. The research in this area has been mainly dominated by polyvinylidene fluoride and its copolymers, which while promising have a limited temperature range of operation due to their low Curie and/or melting temperatures. Here, the authors report the fabrication and properties of vertically aligned and "self-poled" piezoelectric Nylon-11 nanowires with a melting temperature of ≈200 °C, grown by a facile and scalable capillary wetting technique. It is shown that a simple nanogenerator comprising as-grown Nylon-11 nanowires, embedded in an anodized aluminium oxide (AAO) template, can produce an open-circuit voltage of 1 V and short-circuit current of 100 nA, when subjected to small-amplitude, low-frequency vibrations. Importantly, the resulting nanogenerator is shown to exhibit excellent fatigue performance and high temperature stability. The work thus offers the possibility of exploiting a previously unexplored low-cost piezoelectric polymer for nanowire-based energy harvesting, particularly at temperatures well above room temperature.

Piezoelectric materials can directly transduce electrical and mechanical energy, making them attractive for applications such as sensors, actuators and energy harvesting devices. The piezoelectric effect is often associated with ceramic materials, yet piezoelectric behaviour is also observed in many polymers. The flexibility, ease of processing and biocompatibility of piezoelectric polymers mean that they are often preferable for certain applications, despite their reduced piezoelectric coefficients. This review will focus on the underlying mechanisms governing piezoelectricity in polymers from both a theoretical and practical perspective, including ways by which the effect can be enhanced through processing and structural modifications, and an outlook on specific areas in biology where piezoelectric polymers can be applied. Given that many biological materials are themselves piezoelectric, there is much interest in studying how artificial piezoelectric materials influence and stimulate cellular function. Understanding and developing piezoelectric polymers is therefore relevant for applications in energy, sensing and biology, as well as for high level, fundamental research in the physical and life sciences.

Funder: Emmanuel College (University of Cambridge); doi: http://dx.doi.org/10.13039/501100000609, Triboelectric devices capable of harvesting ambient mechanical energy have attracted attention in recent years for powering biomedical devices. Typically, triboelectric energy harvesters rely on contact-generated charges between pairs of materials situated at opposite ends of the triboelectric series. However, very few biocompatible polymeric materials exist at the ‘tribopositive’ end of the triboelectric series. In order to further explore the use of triboelectric energy harvesting devices within the body, it is necessary to develop more biocompatible tribopositive materials and look into ways to improve their triboelectric performance in order to enhance the harvested power output of these devices. Poly-L-lactic acid (PLLA) is a tribopositive biocompatible polymer, frequently used in biomedical applications. Here, we present a way to improve the triboelectric output of nanostructured PLLA through fine control of its crystallinity via a customised template-assisted nanotube (NT) fabrication process. We find that PLLA NTs with higher values of crystallinity (∼41%) give rise to a threefold enhancement of the maximum triboelectric power output as compared to NTs of the same material and geometry but with lower crystallinity (∼13%). Our results thus pave the way for the production of a viable polymeric and biocompatible tribopositive material with improved power generation, for possible use in implantable triboelectric nanogenerators.

Harvesting energy from ambient mechanical sources in our environment has attracted considerable interest due to its potential to power applications such as ubiquitous wireless sensors and Internet of Things devices. In this context, piezoelectric and/or triboelectric materials offer a relatively simple means of directly converting mechanical energy from ubiquitous ambient vibrating sources into electrical power for microscale/nanoscale device applications. In particular, nanoscale energy harvesters, or nanogenerators, are capable of converting low-level ambient vibrations into electrical energy, thus are vital to the realization of the next generation of self-powered devices. Polymer-based nanogenerators are attractive as they are inherently flexible and robust, making them less prone to mechanical failure which is a key requirement for vibrational energy harvesters. They are also lightweight, easy and cheap to fabricate, lead-free and biocompatible, but in many cases their energy harvesting performance is found lacking in comparison to more commonly studied inorganic materials. Recent advances have been made in developing scalable nanofabrication techniques for flexible and low-cost polymer-based nanogenerators with improved energy conversion efficiency, including the incorporation of high-quality polymer nanowires with enhanced crystallinity, piezoelectric and/or surface charge properties. In this review, we discuss aspects of nanomaterials growth and energy harvester device design, including those involving nanowires of polymers of polyvinylidene fluoride and its co-polymers, Nylon-11, and poly-lactic acid for scalable piezoelectric and triboelectric nanogenerator applications, as well as the design and performance of polymer-ceramic nanocomposite nanogenerators. In particular, we highlight the effects of growth parameters, nanoconfinement, self-poling, surface polarization, crystalline phases, and device assembly on the energy harvesting performance of a range of recently reported nanostructured polymer-based materials and devices.