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This study investigates the structural effects on the cross-plane thermal conductivity of Li4Ti5O12-based anode active material. Three structures are investigated: a basic structure consisting of LiBr/LiCl/Li4Ti5O12, polyvinylidene difluoride, and Super P (sample #1); a structure without Li4Ti5O12 (sample #2); and a structure without LiBr/LiCl (sample #3). Despite its high porosity level (77%), sample #1 exhibits higher thermal conductivity than sample #3 (64% porosity) in both air and vacuum conditions, potentially due to the extra structural bonding provided by LiBr/LiCl. The observed difference in cross-plane thermal conductivity between air and vacuum conditions provides insights into the configuration of the anode's active material in the heat transfer direction. The lower limit corresponds to the parallel thermal circuit configuration of active material and air, which is the product of the sample's porosity and thermal conductivity of air. Our analysis suggests that in sample #2, the anode's active material and air inside the pores demonstrate a more serial configuration, while in sample #3, they exhibit a more parallel configuration in the heat transfer direction. However, the thermal conductivity difference observed for sample #1 falls below the theoretical lower bound indicating significant thermal radiation within the pores. Furthermore, the in-plane thermal conductivity is predominantly controlled by the copper foil. Sample #2 exhibits the lowest in-plane thermal conductivity. This is attributed to the severe oxidization of the copper foil by LiBr/LiCl, which is confirmed by structure characterization. 

The temperature coefficient of resistivity (θT) of carbon-based materials is a critical property that directly determines their electrical response upon thermal impulses. It could have metal- (positive) or semiconductor-like (negative) behavior, depending on the combined temperature dependence of electron density and electron scattering. Its distribution in space is very difficult to measure and is rarely studied. Here, for the first time, we report that carbon-based micro/nanoscale structures have a strong non-uniform spatial distribution of θT. This distribution is probed by measuring the transient electro-thermal response of the material under extremely localized step laser heating and scanning, which magnifies the local θT effect in the measured transient voltage evolution. For carbon microfibers (CMFs), after electrical current annealing, θT varies from negative to positive from the sample end to the center with a magnitude change of >130% over <1 mm. This θT sign change is confirmed by directly testing smaller segments from different regions of an annealed CMF. For micro-thick carbon nanotube bundles, θT is found to have a relative change of >125% within a length of ∼2 mm, uncovering strong metallic to semiconductive behavior change in space. Our θT scanning technique can be readily extended to nm-thick samples with μm scanning resolution to explore the distribution of θT and provide a deep insight into the local electron conduction. 

The thermophysical properties of 1D micro/nanoscale materials could differ significantly from those of their bulk counterparts due to intensive energy carrier scattering by structures. This work provides an in-depth review of cutting-edge techniques employed for transient characterization of thermophysical properties at the micro/nanoscale scale. In terms of transient excitation, step Joule heating, step laser heating, pulsed laser heating, and frequency domain amplitude-modulated laser heating are covered. For thermal probing, electrical and Raman scattering-based physical principles are used. These techniques enable the measurement of thermal conductivity, thermal diffusivity, and specific heat from the sub-mm level down to the atomic level (single-atom thickness). This review emphasizes the advantages of these techniques over steady state techniques and their physics, challenges, and potential applications, highlighting their significance in unraveling the intricate thermal transport phenomena to the atomic level of 1D materials. 

In the last two decades, tremendous research has been conducted on the discovery, design and synthesis, characterization, and applications of two-dimensional (2D) materials. Thermal conductivity and interface thermal conductance/resistance of 2D materials are two critical properties in their applications. Raman spectroscopy, which measures the inelastic scattering of photons by optical phonons, can distinct a 2D material's temperature from its surrounding materials', featuring unprecedented spatial resolution (down to the atomic level). Raman-based thermometry has been used tremendously for characterizing the thermal conductivity of 2D materials (suspended or supported) and interface thermal conductance/resistance. Very large data deviations have been observed in literature, partly due to physical phenomena and factors not considered in measurements. Here, we provide a critical review, analysis, and perspectives about a broad spectrum of physical problems faced in Raman-based thermal characterization of 2D materials, namely interface separation, localized stress due to thermal expansion mismatch, optical interference, conjugated phonon, and hot carrier transport, optical–acoustic phonon thermal nonequilibrium, and radiative electron–hole recombination in monolayer 2D materials. Neglect of these problems will lead to a physically unreasonable understanding of phonon transport and interface energy coupling. In-depth discussions are also provided on the energy transport state-resolved Raman (ET-Raman) technique to overcome these problems and on future research challenges and needs. 

Abstract Raman spectroscopy-based temperature sensing usually tracks the change of Raman wavenumber, linewidth and intensity, and has found very broad applications in characterizing the energy and charge transport in nanomaterials over the last decade. The temperature coefficients of these Raman properties are highly material-dependent, and are subjected to local optical scattering influence. As a result, Raman-based temperature sensing usually suffers quite large uncertainties and has low sensitivity. Here, a novel method based on dual resonance Raman phenomenon is developed to precisely measure the absolute temperature rise of nanomaterial (nm WS 2 film in this work) from 170 to 470 K. A 532 nm laser (2.33 eV photon energy) is used to conduct the Raman experiment. Its photon energy is very close to the excitonic transition energy of WS 2 at temperatures close to room temperature. A parameter, termed resonance Raman ratio (R3) Ω = I A 1g / I E 2g is introduced to combine the temperature effects on resonance Raman scattering for the A 1g and E 2g modes. Ω has a change of more than two orders of magnitude from 177 to 477 K, and such change is independent of film thickness and local optical scattering. It is shown that when Ω is varied by 1%, the temperature probing sensitivity is 0.42 K and 1.16 K at low and high temperatures, respectively. Based on Ω, the in-plane thermal conductivity ( k ) of a ∼25 nm-thick suspended WS 2 film is measured using our energy transport state-resolved Raman (ET-Raman). k is found decreasing from 50.0 to 20.0 Wm −1 K −1 when temperature increases from 170 to 470 K. This agrees with previous experimental and theoretical results and the measurement data using our FET-Raman. The R3 technique provides a very robust and high-sensitivity method for temperature probing of nanomaterials and will have broad applications in nanoscale thermal transport characterization, non-destructive evaluation, and manufacturing monitoring.