Water-Assisted Contact Electrification Properties of Selected Polymers and Surface Functionalization Molecules: A Computational Study.

Motivated by the requirements of performance stability in environments of variable humidity, the focus of this study is on the effects and role of humidity-induced water molecules and ions in the contact electrification (CE) mechanisms of triboelectric materials. In particular, the compatibility of direct charge transfer-based CE and other generally known or proposed water molecules or OH/H3O ion-facilitated CE mechanisms was assessed for a set of high-performance polymeric materials and functionalization molecules. The first set of test mechanisms included OH/H3O ion adsorption at the low-humidity limit. The adsorption resulted in physisorption or H transfer involving reactions that were not fully compatible with charge affinity-driven CE reactions on the considered contact surfaces for both ions in terms of the potential increase of the resultant density of surface charge. An alternative mechanism, which yielded compatibility at a large humidity limit, consisted of free energy-driven segregation and separation of the ions. Further test mechanisms included water adsorption-induced charge transfer and two mechanisms pertinent to charged material transfer: adsorption modulation due to formation of water monolayers and water solvation-induced separation of polymer fragments. According to the obtained results, both mechanisms could be verified as viable contributors to enhanced charge transfer. Consequently, the results allowed for conclusions regarding the general applicability of different, water-assisted CE mechanisms and the selection of particular pairs of contact materials of similar type for optimum performance in humid environments.

Comparison of Contact Electrification Mechanisms of Selected Polymers and Surface-Functionalized Molecules.

Among the possible alternatives for the improvement of contact electrification for triboelectric energy harvesting purposes, the functionalization of contact surfaces has attracted wide attention due to its versatility and cost-efficiency. Similarly, low-stiffness polymeric materials such as poly(dimethylsiloxane) (PDMS) are regarded as a promising choice of contact material for the same purpose. However, for defining the most efficient combinations of materials of the aforementioned types, a number of theoretical questions still frequently pose difficulties for practical implementation-related tasks. In this regard, the presented study theoretically assesses the possibilities of consistently selecting optimum performance combinations of contact materials. Here, the optimum is defined as the minimum energy of the charge transfer reaction and, consequently, the maximum density of the predicted triboelectric surface charge. With this aim, the most promising combinations in terms of electron-transfer energies were identified among the candidates of functionalized molecules and polymers. Based on the ordering of materials according to the basic characteristics of charge-transfer reactions─electron and hole affinities─certain differences were observed. These findings indicate that for the materials under consideration, it is not possible to establish a single triboelectric series solely based on a single characteristic. Furthermore, to evaluate the potential compatibility of charge-transfer reaction mechanisms based on electron and material transfer, molecular dynamics simulations were conducted using structures that depict pairs of polymers and self-assembled monolayers of functionalized molecules in contact and separated types of operations. The obtained results indicate that the formation of equally charged free fragments of polymer chains is likely taking place in the contact electrification for N-(2-aminoethyl)-3-aminopropyl trimethoxysilane/PDMS interfaces. At variance, a contact electrification mechanism by charge-dependent material transfer may occur for 1H, 1H, 2H, 2H-perfluorooctyl trimethoxysilane/PDMS interfaces.

Tribovoltaic Performance of TiO2 Thin Films: Crystallinity, Contact Metal, and Thermoelectric Effects.

Tribovoltaic devices are attracting increasing attention as motion-based energy harvesters due to the high local current densities that can be generated. However, while these tribovoltaic devices are being developed, debate remains surrounding their fundamental mechanism. Here, we fabricate thin films from one of the world's most common oxides, TiO2, and compare the tribovoltaic performance under contact with metals of varying work functions, contact areas, and applied pressure. The resultant current density shows little correlation with the work function of the contact metal and a strong correlation with the contact area. Considering other effects at the metal-semiconductor interface, the thermoelectric coefficients of different metals were calculated, which showed a clear correlation with the tribovoltaic current density. On the microscale, molybdenum showed the highest current density of 192 mA cm-2. This work shows the need to consider a variety of mechanisms to understand the tribovoltaic effect and design future exemplar tribovoltaic devices.

Triboelectric behaviour of selected MOFs in contact with metals.

MOFs have been effectively used to magnify the triboelectric charge of polymers. However, so far the individual triboelectric properties and charge transfer mechanisms of MOFs haven't been reported. Triboelectric property investigation for selected MOFs show that the main mechanism for MOF triboelectrification in contact with metals is electron transfer.

Probing Contact Electrification: A Cohesively Sticky Problem.

Contact electrification and the triboelectric effect are complex processes for mechanical-to-electrical energy conversion, particularly for highly deformable polymers. While generating relatively low power density, contact electrification can occur at the contact-separation interface between nearly any two polymer surfaces. This ubiquitousness of surfaces enables contact electrification to be an important phenomenon to understand energy conversion and harvesting applications. The mechanism of charge generation between polymeric materials remains ambiguous, with electron transfer, material (also known as mass) transfer, and adsorbed chemical species transfer (including induced ionization of water and other molecules) all being proposed as the primary source of the measured charge. Often, all sources of charge, except electron transfer, are dismissed in the case of triboelectric energy harvesters, leading to the generation of the "triboelectric series", governed by the ability of a polymer to lose, or accept, an electron. Here, this sole focus on electron transfer is challenged through rigorous experiments, measuring charge density in polymer-polymer (196 polymer combinations), polymer-glass (14 polymers), and polymer-liquid metal (14 polymers) systems. Through the investigation of these interfaces, clear evidence of material transfer via heterolytic bond cleavage is provided. Based on these results, a generalized model considering the cohesive energy density of polymers as the critical parameter for polymer contact electrification is discussed. This discussion clearly shows that material transfer must be accounted for when discussing the source of charge generated by polymeric mechanical energy harvesters. Thus, a correlated physical property to understand the triboelectric series is provided.

Salt concentration dependence of the mechanical properties of LiPF6/poly(propylene glycol) acrylate electrolyte at a graphitic carbon interface: A reactive molecular dynamics study.

This reactive molecular dynamics study explores the salt concentration dependence of the viscoelastic and mechanical failure properties of a poly(propylene glycol)/LiPF6-based solid polymer electrolyte (SPE) at a graphitic carbon electrode interface. To account for the finite-size effect of interface-confined SPE films, the properties of two distinct film thicknesses are compared with the respective bulk properties. Additionally, the effect of uniaxial compression in the interface-normal direction on free energy profiles of Li-ion SPE-desolvation is studied. © 2018 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 718-730.

Lithium ion solvation and diffusion in bulk organic electrolytes from first-principles and classical reactive molecular dynamics.

Lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF6(-) anion. Li(+) prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li(+) solvation. Corresponding analysis for the PF6(-) anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. These results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.