Electrochemical ion insertion involves coupled ion–electron transfer reactions, transport of guest species and redox of the host. The hosts are typically anisotropic solids with 2D conduction planes ...but can also be materials with 1D or isotropic transport pathways. These insertion compounds have traditionally been studied in the context of energy storage but also find extensive applications in electrocatalysis, optoelectronics and computing. Recent developments in operando, ultrafast and high-resolution characterization methods, as well as accurate theoretical simulation methods, have led to a renaissance in the understanding of ion-insertion compounds. In this Review, we present a unified framework for understanding insertion compounds across timescales and length scales ranging from atomic to device levels. Using graphite, transition metal dichalcogenides, layered oxides, oxyhydroxides and olivines as examples, we explore commonalities in these materials in terms of point defects, interfacial reactions and phase transformations. We illustrate similarities in the operating principles of various ion-insertion devices, ranging from batteries and electrocatalysts to electrochromics and thermal transistors, with the goal of unifying research across disciplinary boundaries.Electrochemical ion insertion is rapidly emerging as a powerful materials design strategy. This Review discusses how ion insertion enables reversible transformation and switching of physico-chemical properties, the role of defects and interfacial reactions, and opportunities for ultrafast ionic control.
An electrochemical thermal transistor Sood, Aditya; Xiong, Feng; Chen, Shunda ...
Nature communications,
10/2018, Letnik:
9, Številka:
1
Journal Article
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The ability to actively regulate heat flow at the nanoscale could be a game changer for applications in thermal management and energy harvesting. Such a breakthrough could also enable the control of ...heat flow using thermal circuits, in a manner analogous to electronic circuits. Here we demonstrate switchable thermal transistors with an order of magnitude thermal on/off ratio, based on reversible electrochemical lithium intercalation in MoS
thin films. We use spatially-resolved time-domain thermoreflectance to map the lithium ion distribution during device operation, and atomic force microscopy to show that the lithiated state correlates with increased thickness and surface roughness. First principles calculations reveal that the thermal conductance modulation is due to phonon scattering by lithium rattler modes, c-axis strain, and stacking disorder. This study lays the foundation for electrochemically-driven nanoscale thermal regulators, and establishes thermal metrology as a useful probe of spatio-temporal intercalant dynamics in nanomaterials.
Understanding the impact of lattice imperfections on nanoscale thermal transport is crucial for diverse applications ranging from thermal management to energy conversion. Grain boundaries (GBs) are ...ubiquitous defects in polycrystalline materials, which scatter phonons and reduce thermal conductivity (κ). Historically, their impact on heat conduction has been studied indirectly through spatially averaged measurements, that provide little information about phonon transport near a single GB. Here, using spatially resolved time-domain thermoreflectance (TDTR) measurements in combination with electron backscatter diffraction (EBSD), we make localized measurements of κ within few μm of individual GBs in boron-doped polycrystalline diamond. We observe strongly suppressed thermal transport near GBs, a reduction in κ from ∼1000 W m–1 K–1 at the center of large grains to ∼400 W m–1 K–1 in the immediate vicinity of GBs. Furthermore, we show that this reduction in κ is measured up to ∼10 μm away from a GB. A theoretical model is proposed that captures the local reduction in phonon mean-free-paths due to strongly diffuse phonon scattering at the disordered grain boundaries. Our results provide a new framework for understanding phonon–defect interactions in nanomaterials, with implications for the use of high-κ polycrystalline materials as heat sinks in electronics thermal management.
Layered two-dimensional (2D) materials have highly anisotropic thermal properties between the in-plane and cross-plane directions. Conventionally, it is thought that cross-plane thermal ...conductivities (κ z ) are low, and therefore c-axis phonon mean free paths (MFPs) are small. Here, we measure κ z across MoS2 films of varying thickness (20–240 nm) and uncover evidence of very long c-axis phonon MFPs at room temperature in these layered semiconductors. Experimental data obtained using time-domain thermoreflectance (TDTR) are in good agreement with first-principles density functional theory (DFT). These calculations suggest that ∼50% of the heat is carried by phonons with MFP > 200 nm, exceeding kinetic theory estimates by nearly 2 orders of magnitude. Because of quasi-ballistic effects, the κ z of nanometer-thin films of MoS2 scales with their thickness and the volumetric thermal resistance asymptotes to a nonzero value, ∼10 m2 K GW–1. This contributes as much as 30% to the total thermal resistance of a 20 nm thick film, the rest being limited by thermal interface resistance with the SiO2 substrate and top-side aluminum transducer. These findings are essential for understanding heat flow across nanometer-thin films of MoS2 for optoelectronic and thermoelectric applications.
Genetic diversity is the prerequisite for the success of crop improvement programmes. Keeping in view, the current investigation was undertaken to assess the agro-morphological and molecular ...diversity involving 36 diverse mid-late and late cauliflower genotypes following alpha-RBD design during winter season 2021-22. Six morphological descriptors predicted as polymorphic using Shannon diversity index with maximum for leaf margin (0.94). The genotypes grouped into nine clusters based on D.sup.2 analysis with four as monogenotypic and gross plant weight (32.38%) revealed maximum contribution towards the genetic diversity. Molecular diversity analysis revealed 2-7 alleles among 36 polymorphic simple sequence repeats (SSR) with average of 4.22. Primer BoESSR492 (0.77) showed maximum polymorphic information content (PIC) with mean of 0.58. SSR analysis revealed two clusters each with two subclusters with a composite pattern of genotype distribution. STRUCTURE analysis showed homogenous mixture with least amount of gene pool introgression within the genotypes. Thus, based on morphological and molecular studies, the diverse genotypes namely, DPCaCMS-1, DPCaf-W4, DPCaf-US, DPCaf-W131W, DPCaf-S121, DPCaf-18, DPCaf-13, DPCaf-29 and DPCaf-CMS5 can be utilized in hybridization to isolate potential transgressive segregants to broaden the genetic base of cauliflower or involve them to exploit heterosis.
Porous metals are used in interfacial transport applications that leverage the combination of electrical and/or thermal conductivity and the large available surface area. As nanomaterials push toward ...smaller pore sizes to increase the total surface area and reduce diffusion length scales, electron conduction within the metal scaffold becomes suppressed due to increased surface scattering. Here we observe the transition from diffusive to quasi-ballistic thermal conduction using metal inverse opals (IOs), which are metal films that contain a periodic arrangement of interconnected spherical pores. As the material dimensions are reduced from ∼230 nm to ∼23 nm, the thermal conductivity of copper IOs is reduced by more than 57% due to the increase in surface scattering. In contrast, nickel IOs exhibit diffusive-like conduction and have a constant thermal conductivity over this size regime. The quasi-ballistic nature of electron transport at these length scales is modeled considering the inverse opal geometry, surface scattering, and grain boundaries. Understanding the characteristics of electron conduction at the nanoscale is essential to minimizing the total resistance of porous metals for interfacial transport applications, such as the total electrical resistance of battery electrodes and the total thermal resistance of microscale heat exchangers.
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