Form Factor-Free Boron Nitride Nanotube-Agarose Composites for Neutron Shielding.

Boron nitride nanotubes (BNNTs) have remarkable mechanical and thermal properties and are suitable for neutron shielding due to boron. Because BNNTs exist in bundled and stiff shapes, limiting their practical applications, however, it is essential to improve their formability and processability. In this study, we demonstrate form-factor-free BNNTs and agarose composites for use in neutron shielding for the first time; they are fabricated by mixing hydrophilic agarose with noncovalently functionalized water-soluble BNNTs (p-BNNTs). The mechanical properties of the agarose/p-BNNT composite films surpass those of conventional commodity plastics. When the p-BNNT concentration increased, the neutron linear attenuation coefficient of the composite film increases from 0.574 ± 0.010 to 0.765 ± 0.062 mm-1, which is comparable to that of conventional rigid shielding materials. In particular, the addition of 10 wt % p-BNNTs to agarose results in excellent form-factor flexibility, neutron shielding, and mechanical properties, thus rendering it a promising candidate for the nuclear industry.

Enhancing biodegradation of PBAT through bio-stimulation using Pseudozyma jejuensis for effective plastic waste reduction.

Polybutylene adipate-co-terephthalate (PBAT) is a flexible and biodegradable material that finds applications in mulching film and the food packaging industry. In this study, we aimed to address the global plastic waste problem by developing an improved biodegradation system for PBAT. Our focus was on utilizing the biodegradation capabilities of Pseudozyma jejuensis, a microorganism known for its ability to decompose Polycaprolactam (PCL). Through bio-stimulation, we aimed to enhance the growth mechanism of P. jejuensis and optimize PBAT biodegradation. Our results demonstrated significant structural changes in the PBAT film, as revealed by FT-IR analysis. Moreover, FE-SEM imaging exhibited evident surface erosion and pitting, indicating physical alterations due to biodegradation. These findings provide strong evidence for the efficiency of our developed biodegradation system. To fully harness the potential of this system and enable its practical implementation, further research is warranted to optimize and scale up the process. Our work contributes to the ongoing efforts to combat the global plastic waste crisis, offering a valuable solution for the efficient biodegradation of PBAT.

Correction: Optical humidity sensors based on lead-free Cu-based perovskite nanomaterials.

[This corrects the article DOI: 10.1039/D2NA00168C.].

Optical humidity sensors based on lead-free Cu-based perovskite nanomaterials.

Organometallic halide perovskite materials possess unique and tunable optical properties with a wide range of optoelectronic applications. However, these materials suffer from humidity-driven degradation in ambient atmospheres. In this paper we investigate stable copper-based perovskite nanocrystals for potential use in humidity sensors, specifically examining their unique humidity-dependent optical properties and reversibility. We controlled stoichiometric ratios of Cu-based perovskites and demonstrated that (methylammonium)2CuBr4 nanocrystals showed excellent reversible physisorption of water molecules. These perovskite nanocrystals exhibited reversible hydro-optical properties, including transparency changes in response to variations in relative humidity under ambient conditions. The perovskite nanomaterial humidity sensor was highly reliable and stable, with a linear correlation in a relative humidity range of 7% to 98%. Accordingly, the lead-free Cu-based perovskite materials developed herein have the potential to be employed as real-time, self-consistent humidity sensors.

Comparison of polylactic acid biodegradation ability of Brevibacillus brevis and Bacillus amyloliquefaciens and promotion of PLA biodegradation by soytone.

Polylactic acid (PLA), a biodegradable plastic, is used to substitute commercial plastics in various fields such as disposable packaging materials and mulching films. Although the biodegradation of PLA under submerged or composting conditions is accelerated, increasing the biodegradability of PLA under soil burial conditions is still a challenge. This study reviews and compares the PLA biodegradation ability of Bacillus amyloliquefaciens and Brevibacillus brevis, both PLA-degrading bacteria. The biodegradation ability of a single bacteria in non-composting conditions was evaluated. In addition, in terms of biostimulation, PLA biodegradation according to nitrogen sources was compared. As a result, a higher PLA biodegradation ability was found in B. brevis than in B. amyloliquefaciens. Moreover, it was confirmed that the biodegradation of the PLA film was increased by using soytone as a nitrogen source in both bacteria. Controlling the nitrogen source could be a new way to increase the biodegradation of PLA.

Simple, green organic acid-based hydrometallurgy for waste-to-energy storage devices: Recovery of NiMnCoC2O4 as an electrode material for pseudocapacitor from spent LiNiMnCoO2 batteries.

A simple, green approach to recover NiMnCoC2O4 as an electrode material for high-performance pseudocapacitors from spent LiNiMnCoO2 (NMC) batteries is proposed. Four strategic metals (Li, Ni, Co, and Mn) were leached from spent NMC batteries using several organic acids as model green leachants. Among the various candidates of green leaching agents, 2 M citric acid and 5 wt% glucose were selected as the leachant and reductant, respectively. Microwave irradiation was conducted during the leaching step to maximize the performance of the leaching rate and efficiency. The leaching efficiencies within 0.5 h for Ni(II), Li(I), Mn(II), and Co(II) were 90.7 ± 1.6%, 98.3 ± 2.4%, 94.9 ± 4.3%, and 95.6 ± 1.4%, respectively, and were thus as efficient as using aqua regia leaching. After the leaching process, divalent metal ions, that is, Ni(II), Co(II), and Mn(II), were immediately separated at room temperature using oxalic acid. The recovered samples were not further treated and used directly for energy storage applications. The recovered NiMnCoC2O4⋅nH2O has been demonstrated as a promising electrode for pseudocapacitors, providing a specific capacitance of 1641 F/g, good rate-retention capability (80% of low-current capacitance), and good cycle stability over 4000 charge-discharge cycles.

Three-Dimensional Hierarchical Porous Carbons Derived from Betelnut Shells for Supercapacitor Electrodes.

Electrochemical energy storage (EES) systems are attracting research attention as an alternative to fossil fuels. Advances in the design and composition of energy storage materials are particularly significant. Biomass waste-derived porous carbons are particularly suitable for use in EES systems as they are capable of tuning pore networks from hierarchical porous structures with high specific surface areas. These materials are also more sustainable and environmentally friendly and less toxic and corrosive than other energy storage materials. In this study, we report the creation of a three-dimensional hierarchical porous carbon material derived from betelnut shells. The synthesized three-dimensional (3D) hierarchical porous carbon electrode showed a specific capacitance of 290 F g-1 using 1 M KOH as an electrolyte at a current density of 1 A g-1 in three-electrode systems. Moreover, it offered a high charge/discharge stability of 94% over 5000 charge-discharge cycles at a current density of 5 A g-1. Two-electrode symmetric systems show a specific capacitance of 148 F g-1, good cyclic stability of 90. 8% for 5000 charge-discharge cycles, and high energy density of 41 Wh Kg-1 at the power density of 483 W Kg-1 in aqueous electrolyte.

Joule Heating-Induced Carbon Fibers for Flexible Fiber Supercapacitor Electrodes.

Microscale fiber-based supercapacitors have become increasingly important for the needs of flexible, wearable, and lightweight portable electronics. Fiber electrodes without pre-existing cores enable a wider selection of materials and geometries than is possible through core-containing electrodes. The carbonization of fibrous precursors using an electrically driven route, different from a conventional high-temperature process, is particularly promising for achieving this structure. Here, we present a facile and low-cost process for producing high-performance microfiber supercapacitor electrodes based on carbonaceous materials without cores. Fibrous carbon nanotubes-agarose composite hydrogels, formed by an extrusion process, are converted to a composite fiber consisting of carbon nanotubes (CNTs) surrounded by an amorphous carbon (aC) matrix via Joule heating. When assembled into symmetrical two-electrode cells, the composite fiber (aC-CNTs) supercapacitor electrodes deliver a volumetric capacitance of 5.1 F cm-3 even at a high current density of 118 mA cm-3. Based on electrochemical impedance spectroscopy analysis, it is revealed that high electrochemical properties are attributed to fast response kinetics with a characteristic time constant of 2.5 s. The aC-CNTs fiber electrodes exhibit a 94% capacitance retention at 14 mA cm-3 for at least 10,000 charge-discharge cycles even when deformed (90° bend), which is essentially the same as that (96%) when not deformed. The aC-CNTs fiber electrodes also demonstrate excellent storage performance under mechanical deformation-for example, 1000 bending-straightening cycles.

Preparation of Porous Carbon Nanofibers with Tailored Porosity for Electrochemical Capacitor Electrodes.

Porous carbon electrodes that accumulate charges at the electrode/electrolyte interface have been extensively investigated for use as electrochemical capacitor (EC) electrodes because of their great attributes for driving high-performance energy storage. Here, we report porous carbon nanofibers (p-CNFs) for EC electrodes made by the formation of a composite of monodisperse silica nanoparticles and polyacrylonitrile (PAN), oxidation/carbonization of the composite, and then silica etching. The pore features are controlled by changing the weight ratio of PAN to silica nanoparticles. The electrochemical performances of p-CNF as an electrode are estimated by measuring cyclic voltammetry and galvanostatic charge/discharge. Particularly, the p-CNF electrode shows exceptional areal capacitance (13 mF cm-2 at a current of 0.5 mA cm-2), good rate-retention capability (~98% retention of low-current capacitance), and long-term cycle stability for at least 5000 charge/discharge cycles. Based on the results, we believe that this electrode has potential for use as high-performance EC electrodes.

Enhanced Electrical and Mechanical Properties of Chemically Cross-Linked Carbon-Nanotube-Based Fibers and Their Application in High-Performance Supercapacitors.

The electrical conductivity and mechanical strength of fibers constructed from single-walled carbon nanotubes (CNTs) are usually limited by the weak interactions between individual CNTs. In this work, we report a significant enhancement of both of these properties through chemical cross-linking of individual CNTs. The CNT fibers are made by wet-spinning a CNT solution that contains 1,3,5-tris(2'-bromophenyl)benzene (2TBB) molecules as the cross-linking agent, and the cross-linking is subsequently driven by Joule heating. Cross-linking with 2TBB increases the conductivity of the CNT fibers by a factor of ∼100 and increases the tensile strength on average by 47%; in contrast, the tensile strength of CNT fibers fabricated without 2TBB decreases after the same Joule heating process. Symmetrical supercapacitors made from the 2TBB-treated CNT fibers exhibit a remarkably high volumetric energy density of ∼4.5 mWh cm-3 and a power density of ∼1.3 W cm-3.

Zwitterion Nondetergent Sulfobetaine-Modified SnO2 as an Efficient Electron Transport Layer for Inverted Organic Solar Cells.

Tin oxide (SnO2) has been widely accepted as an effective electron transport layer (ETL) for optoelectronic devices because of its outstanding electro-optical properties such as its suitable band energy levels, high electron mobility, and high transparency. Here, we report a simple but effective interfacial engineering strategy to achieve highly efficient and stable inverted organic solar cells (iOSCs) via a low-temperature solution process and an SnO2 ETL modified by zwitterion nondetergent sulfobetaine 3-(4-tert-butyl-1-pyridinio)-1-propanesulfonate (NDSB-256-4T). We found that NDSB-256-4T helps reduce the work function of SnO2, resulting in more efficient electron extraction and transport to the cathode of iOSCs. NDSB-256-4T also passivates the defects in SnO2, which serves as recombination centers that greatly reduce the device performance of iOSCs. In addition, NDSB-256-4T provides the better interfacial contact between SnO2 and the active layer. Thus, a higher power conversion efficiency (PCE) and longer device stability of iOSCs are expected for a combination of SnO2 and NDSB-256-4T than for devices based on SnO2 only. With these enhanced interfacial properties, P3HT:PC60BM-based iOSCs using SnO2/NDSB-256-4T (0.2 mg/mL) as an ETL showed both a higher average PCE of 3.72%, which is 33% higher than devices using SnO2 only (2.79%) and excellent device stability (over 90% of the initial PCE remained after storing 5 weeks in ambient air without encapsulation). In an extended application of the PTB7-Th:PC70BM systems, we achieved an impressive average PCE of 8.22% with SnO2/NDSB-256-4T (0.2 mg/mL) as the ETL, while devices based on SnO2 exhibited an average PCE of only 4.45%. Thus, the use of zwitterion to modify SnO2 ETL is a promising way to obtain both highly efficient and stable iOSCs.

High energy flexible supercapacitors formed via bottom-up infilling of gel electrolytes into thick porous electrodes.

Formation of thick, high energy density, flexible solid supercapacitors is challenging because of difficulties infilling gel electrolytes into porous electrodes. Incomplete infilling results in a low capacitance and poor mechanical properties. Here we report a bottom-up infilling method to overcome these challenges. Electrodes up to 500 µm thick, formed from multi-walled carbon nanotubes and a composite of poly(3,4-ethylenedioxythiophene), polystyrene sulfonate and multi-walled carbon nanotubes are successfully infilled with a polyvinyl alcohol/phosphoric acid gel electrolyte. The exceptional mechanical properties of the multi-walled carbon nanotube-based electrode enable it to be rolled into a radius of curvature as small as 0.5 mm without cracking and retain 95% of its initial capacitance after 5000 bending cycles. The areal capacitance of our 500 µm thick poly(3,4-ethylenedioxythiophene), polystyrene sulfonate, multi-walled carbon nanotube-based flexible solid supercapacitor is 2662 mF cm-2 at 2 mV s-1, at least five times greater than current flexible supercapacitors.

Reduced Graphene Oxide/LiI Composite Lithium Ion Battery Cathodes.

Li-iodine chemistry is of interest for electrochemical energy storage because it has been shown to provide both high power and high energy density. However, Li-iodine batteries are typically formed using Li metal and elemental iodine, which presents safety and fabrication challenges (e.g., the high vapor pressure of iodine). These disadvantages could be circumvented by using LiI as a starting cathode. Here, we present fabrication of a reduced graphene oxide (rGO)/LiI composite cathode, enabling for the first time the use of LiI as the Li-ion battery cathode. LiI was coated on rGO by infiltration of an ethanolic solution of LiI into a compressed rGO aerogel followed by drying. The free-standing rGO/LiI electrodes show stable long-term cycling and good rate performance with high specific capacity (200 mAh g-1 at 0.5 C after 100 cycles) and small hysteresis (0.056 V at 1 C). Shuttling was suppressed significantly. We speculate the improved electrochemical performance is due to strong interactions between the active materials and rGO, and the reduced ion and electron transport distances provided by the three-dimensional structured cathode.

Flexible and Wearable Fiber Microsupercapacitors Based on Carbon Nanotube-Agarose Gel Composite Electrodes.

Fiber electrodes provide interesting opportunities for energy storage by providing both mechanical flexibility and the opportunity to impart multifunctionality to fabrics. We show here carbon nanotube (CNT)-embedded agarose gel composite fiber electrodes, with a diameter of ∼120 µm, consisting of 60 wt % CNTs that can serve as the basis for flexible and wearable fiber microsupercapacitors (mSCs). Via an extrusion process, CNT bundles are induced to align in an agarose filament matrix. Due to the shear alignment of the CNT bundles, the dehydrated filaments have an electrical conductivity as high as 8.3 S cm-1. The composite fiber electrodes are mechanically stable, enabling formation of twisted two-ply fiber mSCs integrated with a solid electrolyte. The fiber mSC shows a high capacitance (∼1.2 F cm-3), good rate retention (∼90%) at discharge current densities ranging from 5.1 to 38 mA cm-3, long cycle life under repeated charging/discharging (10% fade after 10 000 cycles) and good performance after at least 1000 cycles of deformation, with a radius of curvature of 12.3 mm (90° bend). After being coated with a thin layer of poly(dimethylsiloxane), the fiber mSCs could be cycled over 10 000 times under water. Impedance studies indicate that the superior performance is due to the high electrical conductivity along the aligned CNTs and the large electrode surface area that is accessible through the ion-conducting agarose.

Extremely Durable, Flexible Supercapacitors with Greatly Improved Performance at High Temperatures.

The reliability and durability of energy storage devices are as important as their essential characteristics (e.g., energy and power density) for stable power output and long lifespan and thus much more crucial under harsh conditions. However, energy storage under extreme conditions is still a big challenge because of unavoidable performance decays and the inevitable damage of components. Here, we report high-temperature operating, flexible supercapacitors (f-SCs) that can provide reliable power output and extreme durability under severe electrochemical, mechanical, and thermal conditions. The outstanding capacitive features (e.g., ∼40% enhancement of the rate capability and a maximum capacitances of 170 F g(-1) and 18.7 mF cm(-2) at 160 °C) are attributed to facilitated ion transport at elevated temperatures. Under high-temperature operation and/or a flexibility test in both static and dynamic modes at elevated temperatures >100 °C, the f-SCs showed extreme long-term stability of 100000 cycles (>93% of initial capacitance value) and mechanical durability after hundreds of bending cycles (at bend angles of 60-180°). Even at 120 °C, the versatile design of tandem serial and parallel f-SCs was demonstrated to provide both desirable energy and power requirements at high temperatures.

Manipulating the glass transition behavior of sulfonated polystyrene by functionalized nanoparticle inclusion.

Nanoscale interfaces can modify the phase transition behaviors of polymeric materials. Here, we report the double glass transition temperature (Tg) behavior of sulfonated polystyrene (sPS) by the inclusion of 14 nm amine-functionalized silica (NH2-SiO2) nanoparticles, which is different from the single Tg behaviors of neat sPS and silica (SiO2)-filled sPS. The inclusion of 20 wt% NH2-SiO2 nanoparticles results in an increase of Tg by 9.3 °C as well as revealing a second Tg reduced by 44.7 °C compared to the Tg of neat sPS. By contrast, when SiO2 nanoparticles with an identical concentration and size to NH2-SiO2 are dispersed, sPS composites possess a single Tg of 7.3 °C higher than that of the neat sPS. While a nanoscale dispersion is observed for SiO2 nanoparticles, as confirmed by microscopic and X-ray scattering analyses, NH2-SiO2 nanoparticles show the coexistence of micron-scale clustering along with a nanoscale dispersion of the individual nanoparticles. The micro-phase separation contributes to the free volume induced Tg reduction by the plasticization effect, whereas the Tg increase originates from the polymer segment mobility constrained by nanoconfinement and the rigid amorphous fractions deriving from strong polymer-particle interactions.

Self-assembly of monodisperse starburst carbon spheres into hierarchically organized nanostructured supercapacitor electrodes.

We report a three-dimensional (3D) porous carbon electrode containing both nanoscale and microscale porosity, which has been hierarchically organized to provide efficient ion and electron transport. The electrode organization is provided via the colloidal self-assembly of monodisperse starburst carbon spheres (MSCSs). The periodic close-packing of the MSCSs provides continuous pores inside the 3D structure that facilitate ion and electron transport (electrode electrical conductivity ∼0.35 S m(-1)), and the internal meso- and micropores of the MSCS provide a good specific capacitance. The capacitance of the 3D-ordered porous MSCS electrode is ∼58 F g(-1) at 0.58 A g(-1), 48% larger than that of disordered MSCS electrode at the same rate. At 1 A g(-1) the capacitance of the ordered electrode is 57 F g(-1) (95% of the 0.24 A g(-1) value), which is 64% greater than the capacitance of the disordered electrode at the same rate. The ordered electrode preserves 95% of its initial capacitance after 4000 charging/discharging cycles.

Selective wetting-induced micro-electrode patterning for flexible micro-supercapacitors.

Selective wetting-induced micro-electrode patterning is used to fabricate flexible micro-supercapacitors (mSCs). The resulting mSCs exhibit high performance, mechanical stability, stable cycle life, and hold great promise for facile integration into flexible devices requiring on-chip energy storage.

Anomalous nanoinclusion effects of 2D MoS2 and WS2 nanosheets on the mechanical stiffness of polymer nanocomposites.

Polymer inorganic nanosheet composites hold great promise in enhancing their physical and mechanical properties by increasing the interfacial area. Herein, we demonstrate the nanoinclusion effects of two-dimensional (2D) molybdenum disulfide (MoS2) and tungsten disulfide (WS2) nanosheets on the mechanical properties of the poly(vinyl alcohol) (PVA) polymer. At very small amounts of nanosheets (0.9 wt% for MoS2 and 2.0 wt% for WS2), nanocomposite films exhibit up to 65% improved mechanical properties than the neat PVA film because of strong non-covalent polymer-filler interactions by means of large contact area induced by the 2D geometry of nanosheets. As demonstrated by the decrease in the crystallinity of PVA and the increase in the glass transition temperature, 2D MoS2 is a more attractive filler than 2D WS2 in terms of reinforcing mechanical properties of PVA. These findings fit well with a modified Halpin-Tsai (H-T) model including a nanoscale interfacial layer that can support the observed reinforcements with extremely small 2D filler loadings. This study highlights the strong interplay between the polymer and inorganic nanosheets which plays an important role in greatly improving the mechanical stability of nanocomposites.

Superior pseudocapacitive behavior of confined lignin nanocrystals for renewable energy-storage materials.

Strong demand for high-performance energy-storage devices has currently motivated the development of emerging capacitive materials that can resolve their critical challenge (i.e., low energy density) and that are renewable and inexpensive energy-storage materials from both environmental and economic viewpoints. Herein, the pseudocapacitive behavior of lignin nanocrystals confined on reduced graphene oxides (RGOs) used for renewable energy-storage materials is demonstrated. The excellent capacitive characteristics of the renewable hybrid electrodes were achieved by synergizing the fast and reversible redox charge transfer of surface-confined quinone and the interplay with electron-conducting RGOs. Accordingly, pseudocapacitors with remarkable rate and cyclic performances (~96 % retention after 3000 cycles) showed a maximum capacitance of 432 F g(-1), which was close to the theoretical capacitance of 482 F g(-1) and sixfold higher than that of RGO (93 F g(-1)). The chemical strategy delineated herein paves the way to develop advanced renewable electrodes for energy-storage applications and understand the redox chemistry of electroactive biomaterials.