Graphene-based materials and structures for energy harvesting with fluids – A review

Graphene and graphene-based systems have recently been recognized as promising platforms for energy harvesting, microelectronic components and energy storage owing to their excellent electrical and thermal conductivity, outstanding mechanical properties, good chemical stability, area adaptability, among other significant properties. Integration of energy harvesting systems relying on the graphene/graphene-based materials in contact with fluids has been emphasized in recent years, as well as their potential impact on electric energy generation for a wide range of applications (e.g. innovative medical devices, advanced electronic systems and highly-efficient transduction systems for renewable energy). This review summarizes, for the first time, major breakthroughs carried out in the scope of energy harvesting exploiting graphene-based material systems (comprising graphene films, graphene grids, graphene membranes, 3D graphene composites and tribological structures) in contact with ionic and non-ionic fluids. Several transduction mechanisms for energy harvesting have been thoroughly analyzed. Energy outputs, materials and structures, substrates, types of fluid, manufacture methodologies, and experimental test methodologies are systematically highlighted in this review. Finally, future research directions and innovative applications of these harvesters are proposed.     

Multi-ferroic and magnetoelectric materials and interfaces

The existence of multiple ferroic orders in the same material and the coupling between them have been known for decades. However, these phenomena have mostly remained the theoretical domain owing to the fact that in single-phase materials such couplings are rare and weak. This situation has changed dramatically recently for at least two reasons: first, advances in materials fabrication have made it possible to manufacture these materials in structures of lower dimensionality, such as thin films or wires, or in compound structures such as laminates and epitaxial-layered heterostructures. In these designed materials, new degrees of freedom are accessible in which the coupling between ferroic orders can be greatly enhanced. Second, the miniaturization trend in conventional electronics is approaching the limits beyond which the reduction of the electronic element is becoming more and more difficult. One way to continue the current trends in computer power and storage increase, without further size reduction, is to use multi-functional materials that would enable new device capabilities. Here, we review the field of multi-ferroic (MF) and magnetoelectric (ME) materials, putting the emphasis on electronic effects at ME interfaces and MF tunnel junctions.     

弛豫多铁性材料研究进展

多铁性材料同时具有多种铁性(铁电性、铁磁性或铁弹性)的有序, 可实现电磁信号的相互控制, 成为近年来研究热点。在具有成分无序的复杂体系中, 长程铁性有序有可能被打破, 材料将表现出弛豫特性。我们将至少存在一种铁性弛豫特性的多铁性材料称之为弛豫多铁性材料。这类多铁性材料的极化强度(或磁化强度)在外加电场(或外加磁场)作用下响应更加灵敏, 其磁电耦合机制与长程有序的多铁性材料不同。本文结合国内外最新研究成果, 首先介绍了和弛豫铁性有序相关的物理概念, 重点阐述了多铁性材料在铁电和铁磁双弛豫态下的磁电耦合机制; 然后, 详细介绍了钙钛矿结构(包括PbB₁B₂O₃基和BiFeO₃基材料)和非钙钛矿结构(包括层状Bi结构和非正常铁电体)弛豫多铁性材料的研究进展; 最后, 对该领域亟待解决的问题进行了展望。     

Interface-induced room-temperature multiferroicity in BaTiO₃

Multiferroic materials possess two or more ferroic orders but have not been exploited in devices owing to the scarcity of room-temperature examples. Those that are ferromagnetic and ferroelectric have potential applications in multi-state data storage if the ferroic orders switch independently, or in electric-field controlled spintronics if the magnetoelectric coupling is strong. Future applications could also exploit toroidal moments and optical effects that arise from the simultaneous breaking of time-reversal and space-inversion symmetries. Here, we use soft X-ray resonant magnetic scattering and piezoresponse force microscopy to reveal that, at the interface with Fe or Co, ultrathin films of the archetypal ferroelectric BaTiO? simultaneously possess a magnetization and a polarization that are both spontaneous and hysteretic at room temperature. Ab initio calculations of realistic interface structures provide insight into the origin of the induced moments and bring support to this new approach for creating room-temperature multiferroics.     

Nonlinear dielectric thin films for high-power electric storage with energy density comparable with electrochemical supercapacitors

Although batteries possess high energy storage density, their output power is limited by the slow movement of charge carriers, and thus capacitors are often required to deliver high power output. Dielectric capacitors have high power density with fast discharge rate, but their energy density is typically much lower than electrochemical supercapacitors. Increasing the energy density of dielectric materials is highly desired to extend their applications in many emerging power system applications. In this paper, we review the mechanisms and major characteristics of electric energy storage with electrochemical supercapacitors and dielectric capacitors. Three types of in-house-produced ferroic nonlinear dielectric thin film materials with high energy density are described, including (Pb(0.97)La(0.02))(Zr(0.90)Sn(0.05)Ti(0.05))O(3) (PLZST) antiferroelectric ceramic thin films, Pb(Zn(1/3)Nb(2/3))O(3-)Pb(Mg(1/3)Nb(2/3))O(3-)PbTiO(3) (PZN-PMN-PT) relaxor ferroelectric ceramic thin films, and poly(vinylidene fluoride) (PVDF)-based polymer blend thin films. The results showed that these thin film materials are promising for electric storage with outstandingly high power density and fairly high energy density, comparable with electrochemical supercapacitors.     

Machine Detection of Enhanced Electromechanical Energy Conversion in PbZr0.2Ti0.8O3 Thin Films

Many energy conversion, sensing, and microelectronic applications based on ferroic materials are determined by the domain structure evolution under applied stimuli. New hyperspectral, multidimensional spectroscopic techniques now probe dynamic responses at relevant length and time scales to provide an understanding of how these nanoscale domain structures impact macroscopic properties. Such approaches, however, remain limited in use because of the difficulties that exist in extracting and visualizing scientific insights from these complex datasets. Using multidimensional band‐excitation scanning probe spectroscopy and adapting tools from both computer vision and machine learning, an automated workflow is developed to featurize, detect, and classify signatures of ferroelectric/ferroelastic switching processes in complex ferroelectric domain structures. This approach enables the identification and nanoscale visualization of varied modes of response and a pathway to statistically meaningful quantification of the differences between those modes. Among other things, the importance of domain geometry is spatially visualized for enhancing nanoscale electromechanical energy conversion.     

Transition temperature — Spontaneous strain — Atomic displacement relationships in ferroelastics

The Abrahams — Kurtz — Jamieson relationship, derived for ferroelectrics, has been extended to ferroelastic materials. It is shown that such relationships often shed light on the structural mechanisms that cause ferroic distortions. The ferroelastic properties of the isostructural compounds NdNbO₄ and NdTaO₄ are considered, and it is shown that the ferroelastic transition temperatures and saturated spontaneous strain components are, respectively, proportional to the square of and linearly proportional to the saturated spontaneous displacements of the Nb⁵⁺ and Ta⁵⁺ ions.     

Multi-electron reaction materials for sodium-based batteries

Sodium-based rechargeable batteries are very promising energy storage and conversion systems owing to their wide availability and the low cost of Na resources, which is beneficial to large-scale electric energy storage applications in future. In the context of attempting to achieve high-energy densities and low cost, multi-electron reaction materials for both cathodes and anodes are attracting significant attention due to high specific capacities involved. Here, we present a brief review on recently reported multi-electron reaction materials for sodium-based batteries. We mostly concentrate on true multi-electron reactions that involve individually valence changes greater than one per redox center, but in addition include materials in the discussion, which undergo multi-electron processes per formula unit. The theoretical gravimetric and volumetric (expanded state) capacities are studied for a broad range of examples. Then, the practically achievable volumetric energy density and specific energy of Na cells with hard carbon, sodium (Na), and phosphorus (P) anodes are compared. For this purpose, various data are recalculated and referred to the same basis cell. The results show the potential superiority of the cells using multi-electron reaction materials and provide an intuitive understanding of the practically achievable energy densities in future Na-based rechargeable batteries. However, these multi-electron reaction materials are facing several key challenges, which are preventing their high-performance in current cells. In order to overcome them, general strategies from particle design to electrolyte modification are reviewed and several examples in both cathode and anode materials using such strategies are studied. Finally, future trends and perspectives for achieving promising Na-based batteries with better performance are discussed.     

Hybrid multiferroic nanostructure with magnetic-dielectric coupling

The development of methods to economically synthesize single wire structured multiferroic systems with room temperature spin-charge coupling is expected to be important for building next-generation multifunctional devices with ultralow power consumption. We demonstrate the fabrication of a single nanowire multiferroic system, a new geometry, exhibiting room temperature magnetodielectric coupling. A coaxial nanotube/nanowire heterostructure of barium titanate (BaTiO(3), BTO) and cobalt (Co) has been synthesized using a template-assisted method. Room temperature ferromagnetism and ferroelectricity were exhibited by this coaxial system, indicating the coexistence of more than one ferroic interaction in this composite system.     

Direct and simultaneous observation of ferroelectric and magnetic domains

The ferroelectric/magnetic domain structure in a magnetoelectric binding BaTiO₃/Fe₈₁Ga₁₉ and the ferroelectric/crystallographic domain structure in a magnetoelectric binding PMN-34PT/Mn₅₀Ni₂₈Ga₂₂ were observed successfully by scanning electron acoustic microscopy (SEAM). Both the stripe ferroelectric domains in single crystals and the stripe magnetic domains in polycrystalline grains are obtained simultaneously, which exhibits that the scanning electron acoustic microscopy is a unique imaging technique. In addition, the experimental results show that the SEAM technique may be used in multiferroics to character two or more ferroic domains simultaneously. The imaging mechanisms of ferroelectric domains, magnetic domains, and crystallographic domains are attributed to piezoelectric coupling mechanism, magneto–elastic coupling mechanism, and thermo–wave coupling mechanism, respectively.     

Identification of novel compositions of ferromagnetic shape-memory alloys using composition spreads

Exploration of new ferroic (ferroelectric, ferromagnetic or ferroelastic) materials continues to be a central theme in condensed matter physics and to drive advances in key areas of technology. Here, using thin-film composition spreads, we have mapped the functional phase diagram of the Ni-Mn-Ga system whose Heusler composition Ni(2)MnGa is a well known ferromagnetic shape-memory alloy. A characterization technique that allows detection of martensitic transitions by visual inspection was combined with quantitative magnetization mapping using scanning SQUID (superconducting quantum interference device) microscopy. We find that a large, previously unexplored region outside the Heusler composition contains reversible martensites that are also ferromagnetic. A clear relationship between magnetization and the martensitic transition temperature is observed, revealing a strong thermodynamical coupling between magnetism and martensitic instability across a large fraction of the phase diagram.     

A comparison of the properties of hot compacted gel-spun polyethylene fibre composites with conventional gel-spun polyethylene fibre composites

In this paper we present an investigation of the ballistic and low strain rate mechanical properties of gel-spun polyethylene (GSPE) fibre composites. Composites were made using two different processing routes, a conventional prepreg route and the hot compaction process developed at the University of Leeds. Within these two groups different matrices and fibre arrangements were also investigated. Composites manufactured by the hot compaction process were found to have ballistic performance equivalent to that of the composites manufactured by the conventional prepreg route. The mechanisms of energy absorption in the two types of composite were, however, different. The hot compacted materials absorbed energy by fibre failure and back-face delamination while the composites made by the conventional prepreg route absorbed energy by fibre failure only. Interfacial strength played a very important role in the energy absorption of composites that underwent back-face delamination upon ballistic impact.     

基于共同物理基础的铁性智能材料研究概况

铁性智能材料是具有感知温度、力、电、磁等外界环境并产生驱动(位移等)效应的一类重要功能材料,主要包括形状记忆、压电和磁致伸缩三大类材料。长期以来,三类铁性智能材料的研究分布在几个不同的领域,没有形成共同的物理基础,从而导致只能运用有限的学术思路指导智能材料的研发。近年来实验探索研究成果表明:三类看似不同的铁性智能材料从序参量、畴结构到宏观性能层次具有高度的物理平行性,表明它们具有共同的物理基础,据此可望提供高性能铁性智能材料的物理新机制。     

Electromechanical coupling and output efficiency of piezoelectric bending actuators

Electromechanical coupling mechanisms in piezoelectric bending actuators are discussed in this paper based on the constitutive equations of cantilever bimorph and unimorph actuators. Three actuator characteristic parameters, (e.g., electromechanical coupling coefficient, maximum energy transmission coefficient, and maximum mechanical output energy) are discussed for cantilever bimorph and unimorph actuators. In the case of the bimorph actuator, if the effect of the bonding layer is negligible, these parameters are directly related to the transverse coupling factor lest. In the case of the unimorph actuator, these parameters also depend on the Young's modulus and the thickness of the elastic layer. Maximum values for these parameters can be obtained by choosing proper thickness ratio and Young's modulus ratio of elastic and piezoelectric layers. Calculation results on four unimorph actuators indicate that the use of stiffer elastic material is preferred to increase electromechanical coupling and output mechanical energy in unimorph actuators.     

Defect‐Mediated Polarization Switching in Ferroelectrics and Related Materials: From Mesoscopic Mechanisms to Atomistic Control

The plethora of lattice and electronic behaviors in ferroelectric and multiferroic materials and heterostructures opens vistas into novel physical phenomena including magnetoelectric coupling and ferroelectric tunneling. The development of new classes of electronic, energy‐storage, and information‐technology devices depends critically on understanding and controlling field‐induced polarization switching. Polarization reversal is controlled by defects that determine activation energy, critical switching bias, and the selection between thermodynamically equivalent polarization states in multiaxial ferroelectrics. Understanding and controlling defect functionality in ferroelectric materials is as critical to the future of oxide electronics and solid‐state electrochemistry as defects in semiconductors are for semiconductor electronics. Here, recent advances in understanding the defect‐mediated switching mechanisms, enabled by recent advances in electron and scanning probe microscopy, are discussed. The synergy between local probes and structural methods offers a pathway to decipher deterministic polarization switching mechanisms on the level of a single atomically defined defect.     

Polymer-based nanopiezoelectric generators for energy harvesting applications

Abstract

Energy harvesting from ambient vibrations originating from sources such as moving parts of machines, fluid flow and even body movement, has enormous potential for small power applications, such as wireless sensors, flexible, portable and wearable electronics, and bio-medical implants, to name a few. Nanoscale piezoelectric energy harvesters, also known as nanogenerators (NGs), can directly convert small scale ambient vibrations into electrical energy. Scavenging power from ubiquitous vibrations in this way offers an attractive route to provide power to small devices, which would otherwise require direct or indirect connection to electrical power infrastructure. Ceramics such as lead zirconium titanate and semiconductors such as zinc oxide are the most widely used piezoelectric energy harvesting materials. This review focuses on a different class of piezoelectric materials, namely, ferroelectric polymers, such as polyvinlyidene fluoride (PVDF) and its copolymers. These are potentially superior energy harvesting materials as they are flexible, robust, lightweight, easy and cheap to fabricate, as well as being lead free and biocompatible. We review some of the theoretical and experimental aspects of piezoelectric energy recovery using Polymer-based NGs with a novel emphasis on coupling to mechanical resonance, which is relevant for efficient energy harvesting from typically low frequency (<1 kHz) ambient vibrations. The realisation of highly efficient and low cost piezoelectric polymer NGs with reliable energy harvesting performance could lead to wide ranging energy solutions for the next generation of autonomous electronic and wireless devices.     

Towards local electromechanical probing of cellular and biomolecular systems in a liquid environment

Electromechanical coupling is ubiquitous in biological systems, with examples ranging from simple piezoelectricity in calcified and connective tissues to voltage-gated ion channels, energy storage in mitochondria, and electromechanical activity in cardiac myocytes and outer hair cell stereocilia. Piezoresponse force microscopy (PFM) originally emerged as a technique to study electromechanical phenomena in ferroelectric materials, and in recent years has been employed to study a broad range of non-ferroelectric polar materials, including piezoelectric biomaterials. At the same time, the technique has been extended from ambient to liquid imaging on model ferroelectric systems. Here, we present results on local electromechanical probing of several model cellular and biomolecular systems, including insulin and lysozyme amyloid fibrils, breast adenocarcinoma cells, and bacteriorhodopsin in a liquid environment. The specific features of PFM operation in liquid are delineated and bottlenecks on the route towards nanometre-resolution electromechanical imaging of biological systems are identified.