Synergistic Combination of Sb2Si2Te6 Additives for Enhanced Average ZT and Single-Leg Device Efficiency of Bi0.4Sb1.6Te3-based Composites.

Thermoelectric materials are highly promising for waste heat harvesting. Although thermoelectric materials research has expanded over the years, bismuth telluride-based alloys are still the best for near-room-temperature applications. In this work, a ≈38% enhancement of the average ZT (300-473 K) to 1.21 is achieved by mixing Bi0.4Sb1.6Te3 with an emerging thermoelectric material Sb2Si2Te6, which is significantly higher than that of most BiySb2-yTe3-based composites. This enhancement is facilitated by the unique interface region between the Bi0.4Sb1.6Te3 matrix and Sb2Si2Te6-based precipitates with an orderly atomic arrangement, which promotes the transport of charge carriers with minimal scattering, overcoming a common factor that is limiting ZT enhancement in such composites. At the same time, high-density dislocations in the same region can effectively scatter the phonons, decoupling the electron-phonon transport. This results in a ≈56% enhancement of the thermoelectric quality factor at 373 K, from 0.41 for the pristine sample to 0.64 for the composite sample. A single-leg device is fabricated with a high efficiency of 5.4% at ΔT = 164 K further demonstrating the efficacy of the Sb2Si2Te6 compositing strategy and the importance of the precipitate-matrix interface microstructure in improving the performance of materials for relatively low-temperature applications.

π-Extended Poly(benzimidazoanthradiisoquinolinedione) Ladder-type Conjugated Polymer.

Since the 1960s, poly(benzobisimidazobenzophenathrolinedione) (BBL) has been the only n-type ladder-type conjugated polymer (LCP) that is utilized in thin film electronic devices. Its high electrochemical and thermal stabilities make it a promising candidate for organic electrochemical transistors (OECTs) and thermoelectrics (OTEs) applications. Here we report the synthesis and characterization of a new π-extended poly(benzimidazoanthradiisoquinolinedione) (BAL). The tetrachlorinated BAL (Cl4-BAL) is fully soluble in methanesulfonic acid (MSA) and can be spin-coated into good quality thin films, enabling the fabrication and characterization of OTEs. Doping of Cl4-BAL films using our in-house benzyl viologen radical cation (BV●+) n-dopant shows better electrical air-stability as compared to BBL due to its very low LUMO value (-4.83 eV), making it a promising material toward air-stable n-doped conducting polymers.

Facile Synthesis of Solubilizing a Group-Free, Solution-Processable p-Type Ladder Conjugated Polymer and Its Thermoelectric Properties.

Here we report the synthesis of a new solubilizing group-free, solution-processable p-type ladder conjugated polymer, 6H-pyrrolo[3,2-b:4,5-b']bis[1,4]benzothiazine ladder (PBBTL) polymer by using a polyphosphoric acid (PPA) and phenylphosphonic acid (PhPO3H2) 1:1 binary acid solvent system together with careful control of reaction kinetics. With a good intrinsic viscosity of 3.69 dL/g in methanesulfonic acid (MSA), good quality PBBTL films can be obtained via spin-coating. Intrinsic thin film properties and thermoelectric performance of PBBTL were evaluated, making it the second solubilizing group-free, solution-processable ladder-type conjugated polymer after BBL to be used for thin-film polymer electronics. While our preliminary thermoelectric performance of the FeCl3-doped PBBTL films is modest, we believe that many opportunities lie ahead for PBBTL and hope that its successful synthesis using the new PPA:PhPO3H2 binary acid solvent system will inspire synthetic organic chemists to relook into solubilizing group-free, solution-processable ladder-type conjugated polymer systems.

Upcycling Silicon Photovoltaic Waste into Thermoelectrics.

Two decades after the rapid expansion of photovoltaics, the number of solar panels reaching end-of-life is increasing. While precious metals such as silver and copper are usually recycled, silicon, which makes up the bulk of a solar cells, goes to landfills. This is due to the defect- and impurity-sensitive nature in most silicon-based technologies, rendering it uneconomical to purify waste silicon. Thermoelectrics represents a rare class of material in which defects and impurities can be engineered to enhance the performance. This is because of the majority-carrier nature, making it defect- and impurity-tolerant. Here, the upcycling of silicon from photovoltaic (PV) waste into thermoelectrics is enabled. This is done by doping 1% Ge and 4% P, which results in a figure of merit (zT) of 0.45 at 873 K, the highest among silicon-based thermoelectrics. The work represents an important piece of the puzzle in realizing a circular economy for photovoltaics and electronic waste.

Polaron Delocalization Dependence of the Conductivity and the Seebeck Coefficient in Doped Conjugated Polymers.

Conjugated polymers are promising materials for thermoelectrics as they offer good performances at near ambient temperatures. The current focus on polymer thermoelectric research mainly targets a higher power factor (PF; a product of the conductivity and square of the Seebeck coefficient) through improving the charge mobility. This is usually accomplished via structural modification in conjugated polymers using different processing techniques and doping. As a result, the structure-charge transport relationship in conjugated polymers is generally well-established. In contrast, the relationship between the structure and the Seebeck coefficient is poorly understood due to its complex nature. A theoretical framework by David Emin (Phys. Rev. B, 1999, 59, 6205-6210) suggests that the Seebeck coefficient can be enhanced via carrier-induced vibrational softening, whose magnitude is governed by the size of the polaron. In this work, we seek to unravel this relationship in conjugated polymers using a series of highly identical pro-quinoid polymers. These polymers are ideal to test Emin's framework experimentally as the quinoid character and polaron delocalization in these polymers can be well controlled even by small atomic differences (<10 at. % per repeating unit). By increasing the polaron delocalization, that is, the polaron size, we demonstrate that both the conductivity and the Seebeck coefficient (and hence PF) can be increased simultaneously, and the latter is due to the increase in the polaron's vibrational entropy. By using literature data, we also show that this phenomenon can be observed in two closely related diketopyrrolopyrrole-conjugated polymers as well as in p-doped P3HT and PANI systems with an increasing molecular order.

Improved zT in Nb5Ge3-GeTe thermoelectric nanocomposite.

Robust electronic transport properties is a crucial in designing high performance thermoelectrics. A key similarity between superconductor and thermoelectric lies in their generally high electrical conductivity, even at above its superconducting temperature. In this work, we design a nanocomposite between Nb5Ge3 and GeTe-based thermoelectric to improve its thermoelectric figure of merit zT. Phase and microstructural characterization shows distinct Nb5Ge3 precipitates embed in Ge0.9Sb0.1Te matrix. In addition, experimental electronic and thermal transport analysis, together with density functional theory calculation were employed to show the synergistic effect of doping Sb and Nb5Ge3 nanocomposite approach. 10% Sb doping was found to optimize the electronic properties of the GeTe-based matrix. Further addition of 2 wt% Nb5Ge3 nanocomposite to the matrix enhances the phonon scattering, which consequently lowers the lattice thermal conductivity, which results in zT of up to 2.0 at 723 K. Such superconductor nanocomposite approach shown in this work can be employed to enhance the properties of other thermoelectric materials.

In situ monitoring the viscosity change of an electrolyte in a Li-S battery.

We clarify the reactions in a lithium-sulfur cell by in situ monitoring the change in viscosity of its electrolyte. The results have revealed that Li2S2 is a soluble substance in the electrolyte. This contradicts what was suggested in the literature that it is a solid precipitate on the electrode.

Building better lithium-sulfur batteries: from LiNO3 to solid oxide catalyst.

Lithium nitrate (LiNO3) is known as an important electrolyte additive in lithium-sulfur (Li-S) batteries. The prevailing understanding is that LiNO3 reacts with metallic lithium anode to form a passivation layer which suppresses redox shuttles of lithium polysulfides, enabling good rechargeability of Li-S batteries. However, this view is seeing more challenges in the recent studies, and above all, the inability of inhibiting polysulfide reduction on Li anode. A closely related issue is the progressive reduction of LiNO3 on Li anode which elevates internal resistance of the cell and compromises its cycling stability. Herein, we systematically investigated the function of LiNO3 in redox-shuttle suppression, and propose the suppression as a result of catalyzed oxidation of polysulfides to sulfur by nitrate anions on or in the proximity of the electrode surface upon cell charging. This hypothesis is supported by both density functional theory calculations and the nitrate anions-suppressed self-discharge rate in Li-S cells. The catalytic mechanism is further validated by the use of ruthenium oxide (RuO2, a good oxygen evolution catalyst) on cathode, which equips the LiNO3-free cell with higher capacity and improved capacity retention over 400 cycles.

Investigation on the Cyclability of Lithium-Oxygen Cells in a Confined Potential Window using Cathodes with Pre-filled Discharge Products.

With new chemistry and advantageous configuration, the lithium-oxygen (Li-O2) battery promises a much higher specific energy than traditional lithium-ion batteries. The limited understanding on the complicated battery reactions therein, however, has become a major bottleneck of its development for applications requiring a high energy efficiency and long cycle-life. Herein, in a confined potential window with negligible electrolyte degradation, we studied the rechargeability of Li-O2 cathodes with pre-filled well-defined discharge products of Li2O2, Li2CO3, LiOH, or their combinations. Our results suggest Li2CO3 as the most difficult species to be electrochemically decomposed among the three lithium compounds, whereas the presence of LiOH notably increases the initial charge potential. The clearly visible difference in the charge behavior and cycling stability of these artificially "discharged" electrodes provides a guideline for the development of future high-performance Li-O2 batteries.

1,1'-Bis(diphenylphosphino)ferrocene in functional molecular materials.

The bidentate ligand 1,1'-bis(diphenylphosphino)ferrocene (dppf) is a widely used component in catalytic systems and its role in this capacity has been expertly reviewed elsewhere. The focus of this Perspective is the increasing use of dppf in the synthesis and matrix of 21st century materials. The ferrocene core imparts fine control to catalytic C-C and C-X coupling reactions used to manufacture a range of functional macromolecules from tailored dyes and OLED components to precisely engineered conducting polymers and thermoplastics. This ligand's limited flexibility resembles a ball and socket joint with simultaneous rotation and constrained perpendicular freedom. This uniquely restricted range of movement stabilizes a diverse array of ground and transition states for these important transition metal catalysed coupling reactions. It may also contribute desirable mechanical or electronic functionality as a bridging or chelating component in a coordination array, metallocycle or larger supramolecular assembly. The ferrocene offers steric bulk and crystallinity to these materials aiding chemical stability and ease of handing. It's oxidizability assists characterization and may be tailored to provide or complement photo- or electroactivity. Dppf containing materials have been designed with diverse functions from cooperative luminescence to host-guest complexation. It is likely that this ubiquitous lab companion will increasingly find its way into the fabric or processing of future functional molecular materials.

[upper bond 1 start]PdCl[PPh(2)CH(2)CH(2)C[upper bond 1 end]HCH(2)CH(2)PPh(2)] as a precursor to homo- and hetero-metallic species directed by ESMS (electrospray ionisation mass spectrometry).

The cyclometallated Pd compound [upper bond 1 start]PdCl[PPh(2)CH(2)CH(2)C[upper bond 1 end]HCH(2)CH(2)PPh(2)], obtained from PdCl(2)(Ph(2)P(CH(2))(5)PPh(2)) in refluxing DMF (N,N-dimethylformamide), was characterized by NMR and X-ray single-crystal diffraction analysis. The cyclometallation of MCl(2)(Ph(2)P(CH(2))(5)PPh(2))(M = Pd, Pt) to give and its Pt(ii) analogue was probed using electrospray ionisation mass spectrometry (ESMS). The reactivity of towards neutral ligands such as phosphines and pyridines as well as basic metal complexes such as pyridine-thiolate compounds of Au(i), Hg(ii) and Pt(ii) in solution was also investigated. The results showed that the chloride trans to the Pd-C bond is susceptible to ligand replacement. A number of entry metalloligands was examined in an attempt to establish a route to cyclometallated aggregates and clusters.