Temperature-dependent thermal conductivity in nanoporous materials studied by the Boltzmann Transport Equation

Nanostructured materials exhibit low thermal conductivity because of the additional scattering due to phonon-boundary interactions. As these interactions are highly sensitive to the mean free path (MFP) of a given phonon mode, MFP distributions in nanostructures can be dramatically distorted relative to bulk. Here we calculate the MFP distribution in periodic nanoporous Si for different temperatures, using the recently developed MFP-dependent Boltzmann Transport Equation. After analyzing the relative contribution of each phonon branch to thermal transport in nanoporous Si, we find that at room temperature optical phonons contribute 18 % to heat transport, compared to 5% in bulk Si. Interestingly, we observe a steady thermal conductivity in the nanoporous materials over a temperature range 200 K < T < 300 K, which we attribute to the ballistic transport of acoustic phonons with long intrinsic MFP. These results, which are also consistent with a recent experimental study, shed light on the origin of the reduction of thermal conductivity in nanostructured materials, and could contribute to multiscale heat transport engineering, in which the bulk material and geometry are optimized concurrently

Physically founded phonon dispersions of few-layer materials, and the case of borophene

An increasing number of theoretical calculations on few-layer materials have been reporting a non-zero sound velocity for all three acoustic phonon modes. In contrast with these reports, here we show that the lowest phonon dispersion branch of atomistically described few-layer materials should be quadratic, and this can have dramatic consequencies on calculated properties, such as the thermal conductivity. By reformulating the interatomic force constants (IFC) in terms of internal coordinates, we find that a delicate balance between the IFCs is responsible for this quadraticity. This balance is hard to obtain in ab-initio calculations even if all the symmetries are numerically enforced a posteriori, but it arises naturally in our approach. We demonstrate the phenomenon in the case of borophene, where a very subtle correction to the ab-initio IFCs yields the physically correct quadratic dispersion, while leaving the rest of the spectrum virtually unmodified. Such quadraticity nevertheless has a major effect on the computed lattice thermal conductivity, which in the case of borophene changes by more than a factor 2, and reverses its anisotropy, when the subtle IFC correction is put in place

Phonon transmission through defects in carbon nanotubes from first principles

The original published version of this article may be found on the Physical Review B website: http://dx.doi.org/10.1103/PhysRevB.77.033418 Copyright (2008) American Physical SocietyWe compute the effect of different isolated defects on the phonon transmission through carbon nanotubes, using an ab initio density functional approach. The problem of translational and rotational invariance fulfillment in the nonperiodic system is solved via a Lagrange-multiplier symmetrization technique. The need for an ab initio approach is illustrated for the case of phonon transmission through a nitrogen substitutional impurity, for which no reliable empirical interatomic potentials exist. This opens an avenue for the accurate parameterfree study of phonon transport through general systems with arbitrary composition and structure, without any need for semiempirical potential descriptions

Supercapacitance from cellulose and carbon nanotube nanocomposite fibers

Copyright © 2013 American Chemical SocietyACS AuthorChoice open access articleMultiwalled carbon nanotube (MWNT)/cellulose composite nanofibers have been prepared by electrospinning a MWNT/cellulose acetate blend solution followed by deacetylation. These composite nanofibers were then used as precursors for carbon nanofibers (CNFs). The effect of nanotubes on the stabilization of the precursor and microstructure of the resultant CNFs were investigated using thermogravimetric analysis, transmission electron microscopy and Raman spectroscopy. It is demonstrated that the incorporated MWNTs reduce the activation energy of the oxidative stabilization of cellulose nanofibers from 230 to 180 kJ mol–1. They also increase the crystallite size, structural order, and electrical conductivity of the activated CNFs (ACNFs). The surface area of the ACNFs increased upon addition of nanotubes which protrude from the fiber leading to a rougher surface. The ACNFs were used as the electrodes of a supercapacitor. The electrochemical capacitance of the ACNF derived from pure cellulose nanofibers is demonstrated to be 105 F g–1 at a current density of 10 A g–1, which increases to 145 F g–1 upon the addition of 6% of MWNTs.The authors would like to thank the [Engineering and Physical Sciences Research Council] EPSRC (EP/F036914/1 and EP/I023879/1), Guangdong and Shenzhen Innovative Research Team Program (No. 2011D052,KYPT20121228160843692), National Natural Science Foundation of China (Grant No. 21201175), R&D Funds for basic Research Program of Shenzhen (Grant No. JCYJ20120615140007998), and the Universities of Exeter and Manchester for funding this research

Phonon thermal transport in Bi2Te3 from first principles

We present first-principles calculations of the thermal and thermal transport properties of Bi2Te3 that combine an ab initio molecular dynamics (AIMD) approach to calculate interatomic force constants (IFCs) along with a full iterative solution of the Peierls-Boltzmann transport equation for phonons. The newly developed AIMD approach allows determination of harmonic and anharmonic interatomic forces at each temperature, which is particularly appropriate for highly anharmonic materials such as Bi2Te3. The calculated phonon dispersions, heat capacity, and thermal expansion coefficient are found to be in good agreement with measured data. The lattice thermal conductivity, kappa(l), calculated using the AIMD approach nicely matches measured values, showing better agreement than the kappa(l) obtained using temperature-independent IFCs. A significant contribution to kappa(l) from optic phonon modes is found. Already at room temperature, the phonon line shapes show a notable broadening and onset of satellite peaks reflecting the underlying strong anharmonicity.Funding Agencies|Knut and Alice Wallenberg Foundation (KAW) project "Isotopic Control for Ultimate Material Properties"; Swedish Foundation for Strategic Research (SSF) [SRL10-002]; S3TEC; U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001299/DE-FG02-09ER46577]</p

TDEP: Temperature Dependent Effective Potentials

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