Polymeric, Cost-Effective, Dopant-Free Hole Transport Materials for Efficient and Stable Perovskite Solar Cells.

Perovskite solar cells (PSCs) has skyrocketed in the past decade to an unprecedented level due to their outstanding photoelectric properties and facile processability. However, the utilization of expensive hole transport materials (HTMs) and the inevitable instability instigated by the deliquescent dopants represent major concerns hindering further commercialization. Here, a series of low-cost, conjugated polymers are designed and applied as dopant-free HTMs in PSCs, featuring tuned energy levels, good temperature and humidity resistivity, and excellent photoelectric properties. Further studies highlight the critical and multifaceted roles of the polymers with respect to facilitating charge separation, passivating the surface trap sites of perovskite materials, and guaranteeing long-term stability of the devices. A stabilized power conversion efficiency (PCE) of 20.3% and remarkably enhanced device longevity are achieved using the dopant-free polymer P3 with a low concentration of 5 mg/mL, qualifying the device as one of the best PSC systems constructed on the basis of dopant-free HTMs so far. In addition, the flexible PSCs based on P3 also exhibit a PCE of 16.2%. This work demonstrates a promising route toward commercially viable, stable, and efficient PSCs.

Understanding the Dispersive Action of Nanocellulose for Carbon Nanomaterials.

This work aims at understanding the excellent ability of nanocelluloses to disperse carbon nanomaterials (CNs) in aqueous media to form long-term stable colloidal dispersions without the need for chemical functionalization of the CNs or the use of surfactant. These dispersions are useful for composites with high CN content when seeking water-based, efficient, and green pathways for their preparation. To establish a comprehensive understanding of such dispersion mechanism, colloidal characterization of the dispersions has been combined with surface adhesion measurements using colloidal probe atomic force microscopy (AFM) in aqueous media. AFM results based on model surfaces of graphene and nanocellulose further suggest that there is an association between the nanocellulose and the CN. This association is caused by fluctuations of the counterions on the surface of the nanocellulose inducing dipoles in the sp2 carbon lattice surface of the CNs. Furthermore, the charges on the nanocellulose will induce an electrostatic stabilization of the nanocellulose-CN complexes that prevents aggregation. On the basis of this understanding, nanocelluloses with high surface charge density were used to disperse and stabilize carbon nanotubes (CNTs) and reduced graphene oxide particles in water, so that further increases in the dispersion limit of CNTs could be obtained. The dispersion limit reached the value of 75 wt % CNTs and resulted in high electrical conductivity (515 S/cm) and high modulus (14 GPa) of the CNT composite nanopapers.

Electrochemically Controlled Hydrogels with Electrotunable Permeability and Uniaxial Actuation.

The unique properties of hydrogels enable the design of life-like soft intelligent systems. However, stimuli-responsive hydrogels still suffer from limited actuation control. Direct electronic control of electronically conductive hydrogels can solve this challenge and allow direct integration with modern electronic systems. An electrochemically controlled nanowire composite hydrogel with high in-plane conductivity that stimulates a uniaxial electrochemical osmotic expansion is demonstrated. This materials system allows precisely controlled shape-morphing at only -1 V, where capacitive charging of the hydrogel bulk leads to a large uniaxial expansion of up to 300%, caused by the ingress of ≈700 water molecules per electron-ion pair. The material retains its state when turned off, which is ideal for electrotunable membranes as the inherent coupling between the expansion and mesoporosity enables electronic control of permeability for adaptive separation, fractionation, and distribution. Used as electrochemical osmotic hydrogel actuators, they achieve an electroactive pressure of up to 0.7 MPa (1.4 MPa vs dry) and a work density of ≈150 kJ m-3 (2 MJ m-3  vs dry). This new materials system paves the way to integrate actuation, sensing, and controlled permeation into advanced soft intelligent systems.

Enhancing strength and toughness of cellulose nanofibril network structures with an adhesive peptide.

The mechanical properties of cellulose nanofibrils network structure are essential for their applications in functional materials. In this work, an adhesive peptide consisting of just 11 amino acid residues with a hydrophobic core sequence of FLIVI (F - phenylalanine, L - leucine, I - isoleucine, V - valine) flanked by three lysine (K) residues was adsorbed to 2,2,6,6-Tetramethyl-1-piperidinyloxy radical (TEMPO) oxidized cellulose nanofibrils (TO-CNF). Composite films were prepared by solution casting from water suspensions of TO-CNF adsorbed with the adhesive peptide. The nanofibrils network structure of the composite was characterized by atomic force microscopy (AFM). The structure of the peptide in the composites and the interactions between TO-CNF and the peptide were studied by Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The mechanical properties of the composites were characterized by tensile tests and dynamic mechanical analysis (DMA). With 6.3wt.% adhesive peptide adsorbed onto TO-CNF, the composite showed a modulus of 12.5±1.4GPa, a tensile strength of 344.5±(15.3)MPa, and a strain to failure of 7.8±0.4%, which are 34.4%, 48.8%, and 23.8% higher than those for neat TO-CNF, respectively. This resulted in significantly improved toughness (work to fracture) for the composite, 77% higher than that for the neat TO-CNF.

Nanostructured Wood Hybrids for Fire-Retardancy Prepared by Clay Impregnation into the Cell Wall.

Eco-friendly materials need "green" fire-retardancy treatments, which offer opportunity for new wood nanotechnologies. Balsa wood (Ochroma pyramidale) was delignified to form a hierarchically structured and nanoporous scaffold mainly composed of cellulose nanofibrils. This nanocellulosic wood scaffold was impregnated with colloidal montmorillonite clay to form a nanostructured wood hybrid with high flame-retardancy. The nanoporous scaffold was characterized by scanning electron microscopy and gas adsorption. Flame-retardancy was evaluated by cone calorimetry, whereas thermal and thermo-oxidative stabilities were assessed by thermogravimetry. The location of well-distributed clay nanoplatelets inside the cell walls was confirmed by energy-dispersive X-ray analysis. This unique nanostructure dramatically increased the thermal stability because of thermal insulation, oxygen depletion, and catalytic charring effects. A coherent organic/inorganic charred residue was formed during combustion, leading to a strongly reduced heat release rate peak and reduced smoke generation.

Highly conducting, strong nanocomposites based on nanocellulose-assisted aqueous dispersions of single-wall carbon nanotubes.

It is challenging to obtain high-quality dispersions of single-wall nanotubes (SWNTs) in composite matrix materials, in order to reach the full potential of mechanical and electronic properties. The most widely used matrix materials are polymers, and the route to achieving high quality dispersions of SWNT is mainly chemical functionalization of the SWNT. This leads to increased cost, a loss of strength and lower conductivity. In addition full potential of colloidal self-assembly cannot be fully exploited in a polymer matrix. This may limit the possibilities for assembly of highly ordered structural nanocomposites. Here we show that nanofibrillated cellulose (NFC) can act as an excellent aqueous dispersion agent for as-prepared SWNTs, making possible low-cost exfoliation and purification of SWNTs with dispersion limits exceeding 40 wt %. The NFC:SWNT dispersion may also offer a cheap and sustainable alternative for molecular self-assembly of advanced composites. We demonstrate semitransparent conductive films, aerogels and anisotropic microscale fibers with nanoscale composite structure. The NFC:SWNT nanopaper shows increased strength at 3 wt % SWNT, reaching a modulus of 13.3 GPa, and a strength of 307 MPa. The anisotropic microfiber composites have maximum conductivities above 200 S cm(-1) and current densities reaching 1400 A cm(-2).