Engineering of Solvation Entropy by Poly(4-styrenesulfonic acid) Additive in an Aqueous Electrochemical System for Enhanced Low-Grade Heat Harvesting.

The thermally regenerative electrochemical cycle (TREC) is a reliable and efficient approach to converting low-grade heat into electricity. A high temperature coefficient (α) is the key to maximize the energy conversion efficiency of the TREC system. In this study, we present significant improvement of α of a Prussian blue analogue (PBA)-based electrochemical cell by adding poly(4-styrenesulfonic acid) (PSS) to the electrolyte. Raman spectra showed that water-soluble charged polymers strongly affect the ion hydration structure and increase the entropy change (ΔS) during ion intercalation in PBA. A large α of -2.01 mV K-1 and high absolute heat-to-electricity conversion efficiency up to 1.83% was achieved with a TREC cell in the temperature range 10-40 °C. This study provides a fundamental understanding of the origin of α and a facile method to boosting the temperature coefficient for building a highly efficient low-grade heat harvesting system.

Temperature-Dependent Fracture Resistance of Silicon Nanopillars during Electrochemical Lithiation.

During the lithation of silicon anodes, the solid-state diffusion of lithium into LixSi follows the Arrhenius law, the resulting morphology and fracture behavior are determined by the silicon anode operation temperature. Here, we reveal the temperature dependence of the lithiation mechanics of crystalline silicon nanopillars (SiNPs) via microscopic observations of the anisotropic growth and fracture behavior. We fabricated 1D SiNP structures with various orientations (⟨100⟩, ⟨110⟩, and ⟨111⟩) as working electrodes and operated them at temperatures ranging from -20 to 40 °C. The lithiation of crystalline silicon at low temperatures exhibited preferential volume expansion along ⟨110⟩ and decreased fracture resistance. Furthermore, low temperatures caused the catastrophic fracture of amorphous silicon after the second lithiation. Our findings demonstrate the importance of silicon anode temperature control to prevent mechanical fracture during the cycle of lithium-ion batteries in harsh environments (e.g., electric vehicles in winter).

Prussian Blue Nanolayer-Embedded Separator for Selective Segregation of Nickel Dissolution in High Nickel Cathodes.

Transition metal layered oxides (LiNixCoyMn1-x-yO2, NCM) have been considered as one of the most promising cathodes for lithium-ion batteries used in long-mileage electric vehicles and energy storage systems. Despite its potential interest, dissolved transition metal (TM) ions toward anode sides can catalyze parasitic reactions such as electrolytic decomposition and dendritic Li growth, ultimately leading to catastrophic safety hazards. In this study, we demonstrate that Prussian Blue (PB) nanoparticles anchored to a commercial PE separator significantly reduce cell resistance and effectively suppress TM crossover during cycling, even under harsh conditions that accelerate Ni dissolution. Therefore, using a PB-coated separator in a harsh condition to intentionally dissolve Ni2+ ions at a high cutoff potential of 4.6 V, NCM||graphite full cells maintain 50.8% of their initial capacity at the 150th cycle. Scalable production of PB-coated separator through the facile synthetic methods can help establish a new research direction for the design of high-energy-density batteries.

Association between oral health and frailty: results from the Korea National Health and Nutrition Examination Survey.

BACKGROUND: Previous research has suggested that poor oral health is positively associated with frailty. The objective of this study was to explore associations of key oral diseases (periodontal disease, tooth loss), and oral hygiene and management behaviors with the level of frailty in community-dwelling older Korean adults using national representative survey data. METHODS: This study used cross-sectional, 6th and 7th Korea National Health and Nutrition Examination Survey (KNHANES VI, VII) data. Adults aged 50+ years were included. Frailty was measured using frailty phenotype (FP) and frailty index (FI). FP was determined using five frailty criteria, i.e., weight loss, weakness, exhaustion, slowness, or low physical activity, and the level of frailty was classified with the number of criteria present (robust, none; pre-frail, 1-2; frail, 3+). FI was determined using a 44-item FI constructed according to a standard protocol, and the level of frailty was classified as robust (FI: ≤ 0.08), pre-frail (FI: 0.08-0.25), and frail (FI: ≥ 0.25). Multiple ordinal regression analyses were conducted with each type of frailty as the outcome variable. Independent variables of interest were the periodontal status, number of teeth, and practices on oral hygiene and management. Analyses were additionally adjusted for participants' socioeconomic, diet, and behavioral characteristics. RESULTS: The prevalence of frailty was 4.38% according to the FP classification (n = 4156), 10.74% according to the FI classification (n = 15,073). In the final adjusted model, having more teeth and brushing after all three meals were significantly associated with lower odds of being more frail (in both frailty models); no significant association was observed between periodontal disease and frailty. CONCLUSIONS: Findings from this study show having more teeth and practicing adequate brushing are significantly associated with frailty. Due to limitations of the study design, well-designed longitudinal studies are needed to confirm these findings.

Tear-Based Aqueous Batteries for Smart Contact Lenses Enabled by Prussian Blue Analogue Nanocomposites.

Batteries for contact lenses fabricated by conventional methods could cause severe damage to the eyes if broken. Herein, we present flexible aqueous batteries that operate in tears and provide a safe power supply to smart contact lenses. Nanocomposite flexible electrodes of carbon nanotubes and Prussian blue analogue nanoparticles for cathode and anode were embedded in UV-polymerized hydrogel as not only a soft contact lens but also an ion-permeable separator. The battery exhibited a discharging capacity of 155 µAh in an aqueous electrolyte of 0.15 M Na-ions and 0.02 M K-ions, equivalent to the ionic concentration of tears. The power supply was enough to operate a low-power static random-access memory. In addition, we verified the mechanical stability, biocompatibility and compatibility with a contact lens cleaning solution. It could ultimately enable a safe power supply for smart contact lenses without risk of injury due to the leakage or breakage of the battery.

Pseudoelasticity of SrNi2P2 Micropillar via Double Lattice Collapse and Expansion.

The maximum recoverable strain of most crystalline solids is less than 1% because plastic deformation or fracture usually occurs at a small strain. In this work, we show that a SrNi2P2 micropillar exhibits pseudoelasticity with a large maximum recoverable strain of ∼14% under uniaxial compression via unique reversible structural transformation, double lattice collapse-expansion that is repeatable under cyclic loading. Its high yield strength (∼3.8 ± 0.5 GPa) and large maximum recoverable strain bring out the ultrahigh modulus of resilience (∼146 ± 19 MJ/m3), a few orders of magnitude higher than that of most engineering materials. The double lattice collapse-expansion mechanism shows stress-strain behaviors similar to that of conventional shape-memory alloys, such as hysteresis and thermo-mechanical actuation, even though the structural changes involved are completely different. Our work suggests that the discovery of a new class of high-performance ThCr2Si2-structured materials will open new research opportunities in the field of pseudoelasticity.

Selective Ion Sweeping on Prussian Blue Analogue Nanoparticles and Activated Carbon for Electrochemical Kinetic Energy Harvesting.

Kinetic energy is an ideal energy source for powering wearable devices or internet of things (IoTs) because of its abundant availability. Currently, most kinetic energy harvesting systems are based on friction or deformation, which require high-frequency motion or high material durability for sustainable energy harvesting. Here, we introduce selective ion sweeping in a hybrid cell consisting of an ion-adsorbing activated carbon and an ion-hosting Prussian blue analogue nanoparticle for electrochemical kinetic energy harvesting. The flow of electrolyte induced by kinetic motion of the cell causes ion sweeping only on the surface of the supercapacitor and induces current flow between the supercapacitor and the battery electrode. This method exhibits 24.9 µW cm-2 as maximum power of system with 34 Ω load in half-cell test, which is several thousand times smaller than the load used in conventional methods. In a long-term test with full cell, this method supplies a continuous current flow ∼6 µA cm-2 at the flow of 40 mL min-1 for 500 cycles without performance decay. The prototype of the hybrid cell demonstrated kinetic energy harvesting from bare hand press with the various flow speeds from 0.41 to 1.39 cm s-1 as well as walking, running, and door closing, which are representative examples of low-frequency kinetic motions in daily life. We believe that the simple structure of the hybrid cell will enable power supply to various applications from miniaturized systems (e.g., IoTs and wearables) to large-scale systems (e.g., ocean wave energy harvesting).

Access to Dental Care and Depressive Illness: Results from the Korea National Health Nutrition Examination Survey.

Background and Objectives: Recent evidence suggests that oral health is associated with various systemic diseases including psychiatric illnesses. This study examined the association between depression and access to dental care in Korean adults. Materials and Methods: A cross-sectional evaluation was performed using data from the Sixth Korea National Health and Nutrition Examination Survey 2014. The general characteristics of the participants, the current depression status, and issues with access to dental care were collected to evaluate the factors for not being able to make dental visits according to care needs. Results: The study population comprised a total of 5976 participants who were 19 years of age and older and represented 40.7 million Koreans. A multivariable logistic regression analysis with weighted observations revealed that participants with current depressive illness were about two times more likely to express that they could not make dental visits in spite of their perceived care needs (adjusted odds ratio (OR) = 2.097; 95% confidence interval (CI) 1.046-4.203). The reasons for not making dental visits included financial problems, perceived importance of the dental problem, and fear of visiting dental professionals. Conclusions: Korean adults with current depressive illness were less likely to make dental visits when they had dental care needs. To improve dental health accessibility for patients with depressive illness, coordinated efforts can be considered involving multidisciplinary health care professionals.

Prevalence of Periodontitis and its Association with Reduced Pulmonary Function: Results from the Korean National Health and Nutrition Examination Survey.

Background and Objectives: The current study was performed to evaluate the prevalence of periodontitis and to examine the association between reduced pulmonary function and periodontitis using Sixth Korea National Health and Nutrition Examination Survey (KNHANES) in 2014. Materials and Methods: A cross-sectional evaluation was conducted to estimate the prevalence of periodontitis and to examine the association between periodontitis and reduced pulmonary function while adjusting for sociodemographic characteristics and current smoking status in survey participants between 40 and 79 years old. The presence of periodontitis was evaluated by community periodontal index defined by the World Health Organization, and the assessments of reduced pulmonary function data were made as "normal," "restrictive impairment," or "obstructive impairment." Results: A total of 4004 survey participants representing 25.4 million Koreans were included in the study. Overall, 41.1% of the study population were determined to have periodontitis, and 22.1% had reduced pulmonary function; 7.9% and 14.2% had restrictive- and obstructive- pulmonary impairments, respectively. Age, male gender, and current smoking status were positive predictors for periodontitis. Insurance coverage by workplace and higher education were protective factors against periodontitis. The association between periodontitis and restrictive impairment (adjusted odds ratio (OR) = 1.059, 95% CI 0.729-1.540) or obstructive impairment (adjusted OR = 1.140, 95% CI 0.849-1.530) was not significant. Conclusions: For Koreans, 40-79 years old, age, smoking status, gender, education, and insurance coverage were significant predictors of periodontitis. The prevalence of periodontitis was not significantly associated with reduced pulmonary function. To better understand the relationship between periodontitis and reduced pulmonary function, well-designed and larger scale epidemiologic studies are needed.

Ultrahigh Elastic Strain Energy Storage in Metal-Oxide-Infiltrated Patterned Hybrid Polymer Nanocomposites.

Modulus of resilience, the measure of a material's ability to store and release elastic strain energy, is critical for realizing advanced mechanical actuation technologies in micro/nanoelectromechanical systems. In general, engineering the modulus of resilience is difficult because it requires asymmetrically increasing yield strength and Young's modulus against their mutual scaling behavior. This task becomes further challenging if it needs to be carried out at the nanometer scale. Here, we demonstrate organic-inorganic hybrid composite nanopillars with one of the highest modulus of resilience per density by utilizing vapor-phase aluminum oxide infiltration in lithographically patterned negative photoresist SU-8. In situ nanomechanical measurements reveal a metal-like high yield strength (∼500 MPa) with an unusually low, foam-like Young's modulus (∼7 GPa), a unique pairing that yields ultrahigh modulus of resilience, reaching up to ∼24 MJ/m3 as well as exceptional modulus of resilience per density of ∼13.4 kJ/kg, surpassing those of most engineering materials. The hybrid polymer nanocomposite features lightweight, ultrahigh tunable modulus of resilience and versatile nanoscale lithographic patternability with potential for application as nanomechanical components which require ultrahigh mechanical resilience and strength.

Inhibitory Effects of 2N1HIA (2-(3-(2-Fluoro-4-Methoxyphenyl)-6-Oxo-1(6H)-Pyridazinyl)-N-1H-Indol-5-Ylacetamide) on Osteoclast Differentiation via Suppressing Cathepsin K Expression.

Osteoclasts are large multinucleated cells which are induced by the regulation of the receptor activator of nuclear factor kappa-Β ligand (RANKL), which is important in bone resorption. Excessive osteoclast differentiation can cause pathologic bone loss and destruction. Numerous studies have targeted molecules inhibiting RANKL signaling or bone resorption activity. In this study, 11 compounds from commercial libraries were examined for their effect on RANKL-induced osteoclast differentiation. Of these compounds, only 2-(3-(2-fluoro-4-methoxyphenyl)-6-oxo-1(6H)-pyridazinyl)-N-1H-indol-5-ylacetamide (2N1HIA) caused a significant decrease in multinucleated tartrate-resistant acid phosphatase (TRAP)-positive cell formation in a dose-dependent manner, without inducing cytotoxicity. The 2N1HIA compound neither affected the expression of osteoclast-specific gene markers such as TRAF6, NFATc1, RANK, OC-STAMP, and DC-STAMP, nor the RANKL signaling pathways, including p38, ERK, JNK, and NF-κB. However, 2N1HIA exhibited a significant impact on the expression levels of CD47 and cathepsin K, the early fusion marker and critical protease for bone resorption, respectively. The activity of matrix metalloprotease-9 (MMP-9) decreased due to 2N1HIA treatment. Accordingly, bone resorption activity and actin ring formation decreased in the presence of 2N1HIA. Taken together, 2N1HIA acts as an inhibitor of osteoclast differentiation by attenuating bone resorption activity and may serve as a potential candidate in preventing and/or treating osteoporosis, or other bone diseases associated with excessive bone resorption.

Charging-free electrochemical system for harvesting low-grade thermal energy.

Efficient and low-cost systems are needed to harvest the tremendous amount of energy stored in low-grade heat sources (<100 °C). Thermally regenerative electrochemical cycle (TREC) is an attractive approach which uses the temperature dependence of electrochemical cell voltage to construct a thermodynamic cycle for direct heat-to-electricity conversion. By varying temperature, an electrochemical cell is charged at a lower voltage than discharge, converting thermal energy to electricity. Most TREC systems still require external electricity for charging, which complicates system designs and limits their applications. Here, we demonstrate a charging-free TREC consisting of an inexpensive soluble Fe(CN)6(3-/4-) redox pair and solid Prussian blue particles as active materials for the two electrodes. In this system, the spontaneous directions of the full-cell reaction are opposite at low and high temperatures. Therefore, the two electrochemical processes at both low and high temperatures in a cycle are discharge. Heat-to-electricity conversion efficiency of 2.0% can be reached for the TREC operating between 20 and 60 °C. This charging-free TREC system may have potential application for harvesting low-grade heat from the environment, especially in remote areas.

Size Effect Suppresses Brittle Failure in Hollow Cu60Zr40 Metallic Glass Nanolattices Deformed at Cryogenic Temperatures.

To harness "smaller is more ductile" behavior emergent at nanoscale and to proliferate it onto materials with macroscale dimensions, we produced hollow-tube Cu60Zr40 metallic glass nanolattices with the layer thicknesses of 120, 60, and 20 nm. They exhibit unique transitions in deformation mode with tube-wall thickness and temperature. Molecular dynamics simulations and analytical models were used to interpret these unique transitions in terms of size effects on the plasticity of metallic glasses and elastic instability.

Fracture of crystalline silicon nanopillars during electrochemical lithium insertion.

From surface hardening of steels to doping of semiconductors, atom insertion in solids plays an important role in modifying chemical, physical, and electronic properties of materials for a variety of applications. High densities of atomic insertion in a solid can result in dramatic structural transformations and associated changes in mechanical behavior: This is particularly evident during electrochemical cycling of novel battery electrodes, such as alloying anodes, conversion oxides, and sulfur and oxygen cathodes. Silicon, which undergoes 400% volume expansion when alloying with lithium, is an extreme case and represents an excellent model system for study. Here, we show that fracture locations are highly anisotropic for lithiation of crystalline Si nanopillars and that fracture is strongly correlated with previously discovered anisotropic expansion. Contrary to earlier theoretical models based on diffusion-induced stresses where fracture is predicted to occur in the core of the pillars during lithiation, the observed cracks are present only in the amorphous lithiated shell. We also show that the critical fracture size is between about 240 and 360 nm and that it depends on the electrochemical reaction rate.

Membrane-free battery for harvesting low-grade thermal energy.

Efficient and low-cost systems are desired to harvest the tremendous amount of energy stored in low-grade heat sources (<100 °C). An attractive approach is the thermally regenerative electrochemical cycle (TREC), which uses the dependence of electrode potential on temperature to construct a thermodynamic cycle for direct heat-to-electricity conversion. By varying the temperature, an electrochemical cell is charged at a lower voltage than discharged; thus, thermal energy is converted to electricity. Recently, a Prussian blue analog-based system with high efficiency has been demonstrated. However, the use of an ion-selective membrane in this system raises concerns about the overall cost, which is crucial for waste heat harvesting. Here, we report on a new membrane-free battery with a nickel hexacyanoferrate (NiHCF) cathode and a silver/silver chloride anode. The system has a temperature coefficient of -0.74 mV K(-1). When the battery is discharged at 15 °C and recharged at 55 °C, thermal-to-electricity conversion efficiencies of 2.6% and 3.5% are achieved with assumed heat recuperation of 50% and 70%, respctively. This work opens new opportunities for using membrane-free electrochemical systems to harvest waste heat.

Transparent lithium-ion batteries.

Transparent devices have recently attracted substantial attention. Various applications have been demonstrated, including displays, touch screens, and solar cells; however, transparent batteries, a key component in fully integrated transparent devices, have not yet been reported. As battery electrode materials are not transparent and have to be thick enough to store energy, the traditional approach of using thin films for transparent devices is not suitable. Here we demonstrate a grid-structured electrode to solve this dilemma, which is fabricated by a microfluidics-assisted method. The feature dimension in the electrode is below the resolution limit of human eyes, and, thus, the electrode appears transparent. Moreover, by aligning multiple electrodes together, the amount of energy stored increases readily without sacrificing the transparency. This results in a battery with energy density of 10 Wh/L at a transparency of 60%. The device is also flexible, further broadening their potential applications. The transparent device configuration also allows in situ Raman study of fundamental electrochemical reactions in batteries.

In situ TEM of two-phase lithiation of amorphous silicon nanospheres.

To utilize high-capacity Si anodes in next-generation Li-ion batteries, the physical and chemical transformations during the Li-Si reaction must be better understood. Here, in situ transmission electron microscopy is used to observe the lithiation/delithiation of amorphous Si nanospheres; amorphous Si is an important anode material that has been less studied than crystalline Si. Unexpectedly, the experiments reveal that the first lithiation occurs via a two-phase mechanism, which is contrary to previous understanding and has important consequences for mechanical stress evolution during lithiation. On the basis of kinetics measurements, this behavior is suggested to be due to the rate-limiting effect of Si-Si bond breaking. In addition, the results show that amorphous Si has more favorable kinetics and fracture behavior when reacting with Li than does crystalline Si, making it advantageous to use in battery electrodes. Amorphous spheres up to 870 nm in diameter do not fracture upon lithiation; this is much larger than the 150 nm critical fracture diameter previously identified for crystalline Si spheres.

Vertically aligned carbon nanopillars with size and spacing control for a transparent field emission display.

A top-down fabrication method is presented for vertically aligned carbon nanopillars (CNPs) using photolithography and pyrolysis. The modified backside exposure method of photolithography fabricates vertically aligned polymer (SU-8) nanopillars. The pyrolysis process, which transforms the polymer to amorphous carbon, reliably produces vertically aligned CNPs with widths ranging from 100 to 400 nm. The CNPs can be used as a transparent field emission cathode for a transparent display and light emission is observed.

Enhancing Efficiency of Low-Grade Heat Harvesting by Structural Vibration Entropy in Thermally Regenerative Electrochemical Cycles.

The majority of waste-heat energy exists in the form of low-grade heat (<100 °C), which is immensely difficult to convert into usable energy using conventional energy-harvesting systems. Thermally regenerative electrochemical cycles (TREC), which integrate battery and thermal-energy-harvesting functionalities, are considered an attractive system for low-grade heat harvesting. Herein, the role of structural vibration modes in enhancing the efficacy of TREC systems is investigated. How changes in bonding covalency, influenced by the number of structural water molecules, impact the vibration modes is analyzed. It is discovered that even small amounts of water molecules can induce the A1g stretching mode of cyanide ligands with strong structural vibration energy, which significantly contributes to a larger temperature coefficient (ɑ) in a TREC system. Leveraging these insights, a highly efficient TREC system using a sodium-ion-based aqueous electrolyte is designed and implemented. This study provides valuable insights into the potential of TREC systems, offering a deeper understanding of the intrinsic properties of Prussian Blue analogs regulated by structural vibration modes. These insights open up new possibilities for enhancing the energy-harvesting capabilities of TREC systems.

Manipulation and Direct Characterization of Polymer/Small-Molecule Interface Morphology in Bulk-Heterojunction Solar Cell.

To investigate the effect of miscibility between conjugated polymers (CPs) and Y6 on bulk-heterojunction (BHJ) type morphology, we propose three different CPs with similar chemical structures but different miscibility with Y6. After selectively removing Y6 from the CP/Y6 blend films, their interface morphology and interlocked dimensions are quantitatively compared using a square-wave model. As CP-Y6 miscibility increases, a higher intermixed interface is formed, providing an enlarged CP-Y6 interface area. Conversely, as the miscibility between CP and Y6 decreases, the height and width of the interlocked dimensions formed by phase separation gradually decrease and increase, respectively. Additionally, when the CP-Y6 interface morphology and electrical properties of the corresponding organic photovoltaic (OPV) device are correlated, as the highly intermixed CP-Y6 interface develops, the exciton dissociation efficiency increases owing to the reduced exciton diffusion length to be dissociated, but the bimolecular recombination tends to deteriorate simultaneously. Furthermore, if the miscibility between CP and Y6 is excessive, the formation of a charge transport pathway through phase separation is interrupted, deteriorating the charge transport capability in BHJ-type OPVs. However, it was confirmed that introducing F atoms into the conjugated backbone of CP can reduce the bimolecular recombination, providing ameliorated light-harvesting efficiency.