In-situ resonant band engineering of solution-processed semiconductors generates high performance n-type thermoelectric nano-inks.

Thermoelectric devices possess enormous potential to reshape the global energy landscape by converting waste heat into electricity, yet their commercial implementation has been limited by their high cost to output power ratio. No single "champion" thermoelectric material exists due to a broad range of material-dependent thermal and electrical property optimization challenges. While the advent of nanostructuring provided a general design paradigm for reducing material thermal conductivities, there exists no analogous strategy for homogeneous, precise doping of materials. Here, we demonstrate a nanoscale interface-engineering approach that harnesses the large chemically accessible surface areas of nanomaterials to yield massive, finely-controlled, and stable changes in the Seebeck coefficient, switching a poor nonconventional p-type thermoelectric material, tellurium, into a robust n-type material exhibiting stable properties over months of testing. These remodeled, n-type nanowires display extremely high power factors (~500 µW m-1K-2) that are orders of magnitude higher than their bulk p-type counterparts

Robust production of purified H-2 in a stable, self-regulating, and continuously operating solar fuel generator

The development of practical solar-driven electrochemical fuel generators requires the integration of light absorbing and electrochemical components into an architecture that must also provide easy separation of the product fuels. Unfortunately, many of these components are not stable under the extreme pH conditions necessary to facilitate ionic transport between redox reaction sites. By using a controlled recirculating stream across reaction sites, this work demonstrates a stable, self-regulating and continuous purified solar-hydrogen generation from near neutral pH electrolytes that yield continuous nearly pure H-2 streams with solar-fuel efficiencies above 6.2%

Tethered tertiary amines as solid-state n-type dopants for solution-processable organic semiconductors

A scarcity of stable n-type doping strategies compatible with facile processing has been a major impediment to the advancement of organic electronic devices. Localizing dopants near the cores of conductive molecules can lead to improved efficacy of doping. We and others recently showed the effectiveness of tethering dopants covalently to an electron-deficient aromatic molecule using trimethylammonium functionalization with hydroxide counterions linked to a perylene diimide core by alkyl spacers. In this work, we demonstrate that, contrary to previous hypotheses, the main driver responsible for the highly effective doping observed in thin films is the formation of tethered tertiary amine moieties during thin film processing. Furthermore, we demonstrate that tethered tertiary amine groups are powerful and general n-doping motifs for the successful generation of free electron carriers in the solid-state, not only when coupled to the perylene diimide molecular core, but also when linked with other small molecule systems including naphthalene diimide, diketopyrrolopyrrole, and fullerene derivatives. Our findings help expand a promising molecular design strategy for future enhancements of n-type organic electronic materials

Dihexyl-Substituted Poly(3,4-Propylenedioxythiophene) as a Dual Ionic and Electronic Conductive Cathode Binder for Lithium-Ion Batteries

The polymer binders used in most lithium-ion batteries (LIBs) serve only a structural role, but there are exciting opportunities to increase performance by using polymers with combined electronic and ionic conductivity. To this end, here we examine dihexyl-substituted poly(3,4-propylenedioxythiophene) (PProDOT-Hx₂) as an electrochemically stable π-conjugated polymer that becomes electrically conductive (up to 0.1 S cm⁻¹) upon electrochemical doping in the potential range of 3.2 to 4.5 V (vs Li/Li⁺). Because this family of polymers is easy to functionalize, can be effectively fabricated into electrodes, and shows mixed electronic and ionic conductivity, PProDOT-Hx₂ shows promise for replacing the insulating polyvinylidene fluoride (PVDF) commonly used in commercial LIBs. A combined experimental and theoretical study is presented here to establish the fundamental mixed ionic and electronic conductivity of PProDOT-Hx₂. Electrochemical kinetics and electron spin resonance are first used to verify that the polymer can be readily electrochemically doped and is chemically stable in a potential range of interest for most cathode materials. A novel impedance method is then used to directly follow the evolution of both the electronic and ionic conductivity as a function of potential. Both values increase with electrochemical doping and stay high across the potential range of interest. A combination of optical ellipsometry and grazing incidence wide angle X-ray scattering is used to characterize both solvent swelling and structural changes that occur during electrochemical doping. These experimental results are used to calibrate molecular dynamics simulations, which show improved ionic conductivity upon solvent swelling. Simulations further attribute the improved ionic conductivity of PProDOT-Hx₂ to its open morphology and the increased solvation is possible because of the oxygen-containing propylenedioxythiophene backbone. Finally, the performance of PProDOT-Hx₂ as a conductive binder for the well-known cathode LiNi_(0.8)Co_(0.15)Al_(0.05)O₂ relative to PVDF is presented. PProDOT-Hx₂-based cells display a fivefold increase in capacity at high rates of discharge compared to PVDF-based electrodes at high rates and also show improved long-term cycling stability. The increased rate capability and cycling stability demonstrate the benefits of using binders such as PProDOT-Hx₂, which show good electronic and ionic conductivity, combined with electrochemical stability over the potential range for standard cathode operation

Power Factor Enhancement in Solution‐Processed Organic n‐Type Thermoelectrics Through Molecular Design

A new class of high‐performance n‐type organic thermoelectric materials, self‐doping perylene diimide derivatives with modified side chains, is reported. These materials achieve the highest n‐type thermoelectric performance of solution‐processed organic materials reported to date, with power factors as high as 1.4 μW/mK^2. These results demonstrate that molecular design is a promising strategy for enhancing organic thermoelectric performance