Cathode Electrolyte Interphase Engineering for Prussian Blue Analogues in Lithium-Ion Batteries.

The increasing use of low-cost lithium iron phosphate cathodes in low-end electric vehicles has sparked interest in Prussian blue analogues (PBAs) for lithium-ion batteries. A major challenge with iron hexacyanoferrate (FeHCFe), particularly in lithium-ion systems, is its slow kinetics in organic electrolytes and valence state inactivation in aqueous ones. We have addressed these issues by developing a polymeric cathode electrolyte interphase (CEI) layer through a ring-opening reaction of ethylene carbonate triggered by OH- radicals from structural water. This facile approach considerably mitigates the sluggish electrochemical kinetics typically observed in organic electrolytes. As a result, FeHCFe has achieved a specific capacity of 125 mAh g-1 with a stable lifetime over 500 cycles, thanks to the effective activation of Fe low-spin states and the structural integrity of the CEI layers. These advancements shed light on the potential of PBAs to be viable, durable, and efficient cathode materials for commercial use.

Nickel-induced transcriptional memory in lung epithelial cells promotes interferon signaling upon nicotine exposure.

Exposure to nickel, an environmental respiratory toxicant, is associated with lung diseases including asthma, pulmonary fibrosis, bronchitis and cancers. Our previous studies have shown that a majority of the nickel-induced transcriptional changes are persistent and do not reverse even after the termination of exposure. This suggested transcriptional memory, wherein the cell 'remembers' past nickel exposure. Transcriptional memory, due to which the cells respond more robustly to a previously encountered stimulus has been identified in a number of organisms. Therefore, transcriptional memory has been described as an adaptive mechanism. However, transcriptional memory caused by environmental toxicant exposures has not been well investigated. Moreover, how the transcriptional memory caused by an environmental toxicant might influence the outcome of exposure to a second toxicant has not been explored. In this study, we investigated whether nickel-induced transcriptional memory influences the outcome of the cell's response to a second respiratory toxicant, nicotine. Nicotine, an addictive compound in tobacco, is associated with the development of chronic lung diseases including chronic obstructive pulmonary disease (COPD) and pulmonary fibrosis. Our results show that nicotine exposure upregulated a subset of genes only in the cells previously exposed to nickel. Furthermore, our analyses indicate robust activation of interferon (IFN) signaling in these cells. IFN signaling is a driver of inflammation, which is associated with many chronic lung diseases. Therefore, our results suggest that nicotine exposure of lung cells that retain the transcriptional memory of previous nickel exposure could result in increased susceptibility to developing chronic inflammatory lung diseases.

Guaiacol as an Organic Superoxide Dismutase Mimics for Anti-ageing a Ru-based Li-rich Layered Oxide Cathode.

High-capacity Li-rich layered oxides using oxygen redox as well as transition metal redox suffer from its structural instability due to lattice oxygen escaped from its structure during oxygen redox and the following electrolyte decomposition by the reactive oxygen species. Herein, we rescued a Li-rich layered oxide based on 4d transition metal by employing an organic superoxide dismutase mimics as a homogeneous electrolyte additive. Guaiacol scavenged superoxide radicals via dismutation or disproportionation to convert two superoxide molecules to peroxide and dioxygen after absorbing lithium superoxide on its partially negative oxygen of methoxy and hydroxyl groups. Additionally, guaiacol was decomposed to form a thin and stable cathode-electrolyte interphase (CEI) layer, endowing the cathode with the interfacial stability.

Near zero-strain silicon oxycarbide interphases for stable Li-ion batteries.

We investigate silicon oxycarbide nanotubes that incorporate Si, SiC, and silicon oxycarbide phases, which exhibit near zero-strain volume expansion, leading to reduced electrolyte decomposition. The composite effectively accommodates the formation of c-Li15Si4, as validated by in situ TEM analyses and electrochemical tests, thereby proposing a promising solution for Li-ion battery anodes.

Prussian Blue-Type Sodium-ion Conducting Solid Electrolytes for All Solid-State Batteries.

Conventional solid electrolyte frameworks typically consist of anions such as sulphur, oxygen, chlorine, and others, leading to inherent limitations in their properties. Despite the emergence of sulphide, oxide, and halide-based solid electrolytes for all-solid-state batteries, their utilization is hampered by issues, including the evolution of H2 S gas, the need for expensive elements, and poor contact. Here, we first introduce Prussian Blue analogue (PBA) open-framework structures as a solid electrolyte that demonstrates appreciable Na+ conductivity (>10-2 mS cm-1 ). We delve into the relationship between Na+ conductivity and the lattice parameter of N-coordinated transition metal, which is attributed to the reduced interaction between Na+ and the framework, corroborated by the distribution of relaxation times and density functional theory calculations. Among the five PBAs studied, Mn-PBA have exhibited the highest Na+ conductivity of 9.1×10-2 mS cm-1 . Feasibility tests have revealed that Mn-PBA have maintained a cycle retention of 95.1 % after 80cycles at 30 °C and a C-rate of 0.2C. Our investigation into the underlying mechanisms that play a significant role in governing the conductivity and kinetics of these materials contributes valuable insights for the development of alternative strategies to realize all-solid-state batteries.

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.

Design Principles for Fluorinated Interphase Evolution via Conversion-Type Alloying Processes for Anticorrosive Lithium Metal Anodes.

Over the past decade, lithium metal has been considered the most attractive anode material for high-energy-density batteries. However, its practical application has been hindered by its high reactivity with organic electrolytes and uncontrolled dendritic growth, resulting in poor Coulombic efficiency and cycle life. In this paper, we propose a design strategy for interface engineering using a conversion-type reaction of metal fluorides to evolve a LiF passivation layer and Li-M alloy. Particularly, we propose a LiF-modified Li-Mg-C electrode, which demonstrates stable long-term cycling for over 2000 h in common organic electrolytes with fluoroethylene carbonate (FEC) additives and over 700 h even without additives, suppressing unwanted side reactions and Li dendritic growth. With the help of phase diagrams, we found that solid-solution-based alloying not only facilitates the spontaneous evolution of a LiF layer and bulk alloy but also enables reversible Li plating/stripping inward to the bulk, compared with intermetallic compounds with finite Li solubility.

Boosting the interfacial superionic conduction of halide solid electrolytes for all-solid-state batteries.

Designing highly conductive and (electro)chemical stable inorganic solid electrolytes using cost-effective materials is crucial for developing all-solid-state batteries. Here, we report halide nanocomposite solid electrolytes (HNSEs) ZrO2(-ACl)-A2ZrCl6 (A = Li or Na) that demonstrate improved ionic conductivities at 30 °C, from 0.40 to 1.3 mS cm-1 and from 0.011 to 0.11 mS cm-1 for Li+ and Na+, respectively, compared to A2ZrCl6, and improved compatibility with sulfide solid electrolytes. The mechanochemical method employing Li2O for the HNSEs synthesis enables the formation of nanostructured networks that promote interfacial superionic conduction. Via density functional theory calculations combined with synchrotron X-ray and 6Li nuclear magnetic resonance measurements and analyses, we demonstrate that interfacial oxygen-substituted compounds are responsible for the boosted interfacial conduction mechanism. Compared to state-of-the-art Li2ZrCl6, the fluorinated ZrO2-2Li2ZrCl5F HNSE shows improved high-voltage stability and interfacial compatibility with Li6PS5Cl and layered lithium transition metal oxide-based positive electrodes without detrimentally affecting Li+ conductivity. We also report the assembly and testing of a Li-In||LiNi0.88Co0.11Mn0.01O2 all-solid-state lab-scale cell operating at 30 °C and 70 MPa and capable of delivering a specific discharge of 115 mAh g-1 after almost 2000 cycles at 400 mA g-1.

Light control using vertically aligned dichroic dye films for windshield antireflection in automotive displays.

A vertically aligned dichroic dye (VA-Dye) film, whose absorption axis is perpendicular to that of its substrates, was laminated on a display panel in which the absorption axis of the top polarizer was set to 0°. In the vertical viewing angle of the display panel, the absorption axes of the top polarizer and dichroic dye are at right angles to each other, and, so, the light emitted from the display panel can be blocked. In the horizontal viewing angle of the display panel, the absorption axes of the top polarizer and dichroic dye are parallel to each other so that the light emitted from the display panel can be transmitted. Based on these polarization optics, we achieved complete elimination of light emitted in the upward or downward direction of the display panel, while the light emitted to the left and right is transmitted. We also added a designed optical compensation film using a positive biaxial (+B) retarder to the VA-Dye film so that the light emitted in the upward and downward directions of the display panel could be blocked in a wide viewing angle range (not only in the vertical direction, but also in the diagonal direction). The display panel using the VA-Dye film with the +B retarder showed excellent optical performance, such as significantly lower transmittance over a wide viewing angle range in the upward direction and relatively higher transmittance compared to that of a reference panel without the VA-Dye film. In addition, the VA-Dye film can be manufactured with a lower thickness, easier fabrication, and lower cost when compared with other technologies.

Nanocomposite Engineering of a High-Capacity Partially Ordered Cathode for Li-Ion Batteries.

Understanding the local cation order in the crystal structure and its correlation with electrochemical performances has advanced the development of high-energy Mn-rich cathode materials for Li-ion batteries, notably Li- and Mn-rich layered cathodes (LMR, e.g., Li1.2 Ni0.13 Mn0.54 Co0.13 O2 ) that are considered as nanocomposite layered materials with C2/m Li2 MnO3 -type medium-range order (MRO). Moreover, the Li-transport rate in high-capacity Mn-based disordered rock-salt (DRX) cathodes (e.g., Li1.2 Mn0.4 Ti0.4 O2 ) is found to be influenced by the short-range order of cations, underlining the importance of engineering the local cation order in designing high-energy materials. Herein, the nanocomposite is revealed, with a heterogeneous nature (like MRO found in LMR) of ultrahigh-capacity partially ordered cathodes (e.g., Li1.68 Mn1.6 O3.7 F0.3 ) made of distinct domains of spinel-, DRX- and layered-like phases, contrary to conventional single-phase DRX cathodes. This multi-scale understanding of ordering informs engineering the nanocomposite material via Ti doping, altering the intra-particle characteristics to increase the content of the rock-salt phase and heterogeneity within a particle. This strategy markedly improves the reversibility of both Mn- and O-redox processes to enhance the cycling stability of the partially ordered DRX cathodes (nearly ≈30% improvement of capacity retention). This work sheds light on the importance of nanocomposite engineering to develop ultrahigh-performance, low-cost Li-ion cathode materials.

Selectively Enhanced Electrocatalytic Oxygen Evolution within Nanoscopic Channels Fitting a Specific Reaction Intermediate for Seawater Splitting.

Abundant availability of seawater grants economic and resource-rich benefits to water electrolysis technology requiring high-purity water if undesired reactions such as chlorine evolution reaction (CER) competitive to oxygen evolution reaction (OER) are suppressed. Inspired by a conceptual computational work suggesting that OER is kinetically improved via a double activation within 7 Å-gap nanochannels, RuO2 catalysts are realized to have nanoscopic channels at 7, 11, and 14 Å gap in average (dgap ), and preferential activity improvement of OER over CER in seawater by using nanochanneled RuO2 is demonstrated. When the channels are developed to have 7 Å gap, the OER current is maximized with the overpotential required for triggering OER minimized. The gap value guaranteeing the highest OER activity is identical to the value expected from the computational work. The improved OER activity significantly increases the selectivity of OER over CER in seawater since the double activation by the 7 Å-nanoconfined environments to allow an OER intermediate (*OOH) to be doubly anchored to Ru and O active sites does not work on the CER intermediate (*Cl). Successful operation of direct seawater electrolysis with improved hydrogen production is demonstrated by employing the 7 Å-nanochanneled RuO2 as the OER electrocatalyst.

The proximal tubule through an NBCe1-dependent mechanism regulates collecting duct phenotypic and remodeling responses to acidosis.

The renal response to acid-base disturbances involves phenotypic and remodeling changes in the collecting duct. This study examines whether the proximal tubule controls these responses. We examined mice with genetic deletion of proteins present only in the proximal tubule, either the A variant or both A and B variants of isoform 1 of the electrogenic Na+-bicarbonate cotransporter (NBCe1). Both knockout (KO) mice have spontaneous metabolic acidosis. We then determined the collecting duct phenotypic responses to this acidosis and the remodeling responses to exogenous acid loading. Despite the spontaneous acidosis in NBCe1-A KO mice, type A intercalated cells in the inner stripe of the outer medullary collecting duct (OMCDis) exhibited decreased height and reduced expression of H+-ATPase, anion exchanger 1, Rhesus B glycoprotein, and Rhesus C glycoprotein. Combined kidney-specific NBCe1-A/B deletion induced similar changes. Ultrastructural imaging showed decreased apical plasma membrane and increased vesicular H+-ATPase in OMCDis type A intercalated cell in NBCe1-A KO mice. Next, we examined the collecting duct remodeling response to acidosis. In wild-type mice, acid loading increased the proportion of type A intercalated cells in the connecting tubule (CNT) and OMCDis, and it decreased the proportion of non-A, non-B intercalated cells in the connecting tubule, and type B intercalated cells in the cortical collecting duct (CCD). These changes were absent in NBCe1-A KO mice. We conclude that the collecting duct phenotypic and remodeling responses depend on proximal tubule-dependent signaling mechanisms blocked by constitutive deletion of proximal tubule NBCe1 proteins.NEW & NOTEWORTHY This study shows that the proximal tubule regulates collecting duct phenotypic and remodeling responses to acidosis.

Unveiling the Role of PEO-Capped TiO2 Nanofiller in Stabilizing the Anode Interface in Lithium Metal Batteries.

Lithium metal batteries (LMBs) will be a breakthrough in automotive applications, but they require the development of next-generation solid-state electrolytes (SSEs) to stabilize the anode interface. Polymer-in-ceramic PEO/TiO2 nanocomposite SSEs show outstanding properties, allowing unprecedented LMBs durability and self-healing capabilities. However, the mechanism underlying the inhibition/delay of dendrite growth is not well understood. In fact, the inorganic phase could act as both a chemical and a mechanical barrier to dendrite propagation. Combining advanced in situ and ex situ experimental techniques, we demonstrate that oligo(ethylene oxide)-capped TiO2, although chemically inert toward lithium metal, imparts SSE with mechanical and dynamical properties particularly favorable for application. The self-healing characteristics are due to the interplay between mechanical robustness and high local polymer mobility which promotes the disruption of the electric continuity of the lithium dendrites (razor effect).

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).

Using Single-Crystal Graphene to Form Arrays of Nanocapsules Enabling the Observation of Light Elements in Liquid Cell Transmission Electron Microscopy.

We have designed and fabricated a TEM (transmission electron microscopy) liquid cell with hundreds of graphene nanocapsules arranged in a stack of two Si3N4-x membranes. These graphene nanocapsules are formed on arrays of nanoholes patterned on the Si3N4-x membrane by focused ion beam milling, allowing for better resolution than for the conventional graphene liquid cells, which enables the observation of light elements, such as atomic structures of silicon. We suggest that multiple nanocapsules provide opportunities for consecutive imaging under the same conditions in a single liquid cell. The use of single-crystal graphene windows offers an excellent signal-to-noise ratio and high spatial resolution. The motion of silicon nanoparticles (a low atomic number (Z) material) interacting with nanobubbles was observed, and analyzed, in detail. Our approach will help advance liquid-phase TEM observations by providing a straightforward method to encapsulate liquid between monolayers of various 2-dimensional materials.

Corrigendum: Hyperammonemia After Lung Transplantation: Systematic Review and a Mini Case Series.

[This corrects the article DOI: 10.3389/ti.2022.10433.].

DNA damage, DNA repair and carcinogenicity: Tobacco smoke versus electronic cigarette aerosol.

The allure of tobacco smoking is linked to the instant gratification provided by inhaled nicotine. Unfortunately, tobacco curing and burning generates many mutagens including more than 70 carcinogens. There are two types of mutagens and carcinogens in tobacco smoke (TS): direct DNA damaging carcinogens and procarcinogens, which require metabolic activation to become DNA damaging. Recent studies provide three new insights on TS-induced DNA damage. First, two major types of TS DNA damage are induced by direct carcinogen aldehydes, cyclic-1,N2-hydroxy-deoxyguanosine (γ-OH-PdG) and α-methyl-1, N2-γ-OH-PdG, rather than by the procarcinogens, polycyclic aromatic hydrocarbons and aromatic amines. Second, TS reduces DNA repair proteins and activity levels. TS aldehydes also prevent procarcinogen activation. Based on these findings, we propose that aldehydes are major sources of TS induce DNA damage and a driving force for carcinogenesis. E-cigarettes (E-cigs) are designed to deliver nicotine in an aerosol state, without burning tobacco. E-cigarette aerosols (ECAs) contain nicotine, propylene glycol and vegetable glycerin. ECAs induce O6-methyl-deoxyguanosines (O6-medG) and cyclic γ-hydroxy-1,N2--propano-dG (γ-OH-PdG) in mouse lung, heart and bladder tissues and causes a reduction of DNA repair proteins and activity in lungs. Nicotine and nicotine-derived nitrosamine ketone (NNK) induce the same types of DNA adducts and cause DNA repair inhibition in human cells. After long-term exposure, ECAs induce lung adenocarcinoma and bladder urothelial hyperplasia in mice. We propose that E-cig nicotine can be nitrosated in mouse and human cells becoming nitrosamines, thereby causing two carcinogenic effects, induction of DNA damage and inhibition of DNA repair, and that ECA is carcinogenic in mice. Thus, this article reviews the newest literature on DNA adducts and DNA repair inhibition induced by nicotine and ECAs in mice and cultured human cells, and provides insights into ECA carcinogenicity in mice.

Hyperammonemia After Lung Transplantation: Systematic Review and a Mini Case Series.

Background: Hyperammonemia after lung transplantation (HALT) is a rare but serious complication with high mortality. This systematic review delineates possible etiologies of HALT and highlights successful strategies used to manage this fatal complication. Methods: Seven biomedical databases and grey literature sources were searched using keywords relevant to hyperammonemia and lung transplantation for publications between 1995 and 2020. Additionally, we retrospectively analyzed HALT cases managed at our institution between January 2016 and August 2018. Results: The systematic review resulted in 18 studies with 40 individual cases. The mean peak ammonia level was 769 µmol/L at a mean of 14.1 days post-transplant. The mortality due to HALT was 57.5%. In our cohort of 120 lung transplants performed, four cases of HALT were identified. The mean peak ammonia level was 180.5 µmol/L at a mean of 11 days after transplantation. HALT in all four patients was successfully treated using a multimodal approach with an overall mortality of 25%. Conclusion: The incidence of HALT (3.3%) in our institution is comparable to prior reports. Nonetheless, ammonia levels in our cohort were not as high as previously reported and peaked earlier. We attributed these significant differences to early recognition and prompt institution of multimodal treatment approach.

Universal Solution Synthesis of Sulfide Solid Electrolytes Using Alkahest for All-Solid-State Batteries.

The wet-chemical processability of sulfide solid electrolytes (SEs) provides intriguing opportunities for all-solid-state batteries. Thus far, sulfide SEs are wet-prepared either from solid precursors suspended in solvents (suspension synthesis) or from homogeneous solutions using SEs (solution process) with restricted composition spaces. Here, a universal solution synthesis method for preparing sulfide SEs from precursors, not only Li2 S, P2 S5 , LiCl, and Na2 S, but also metal sulfides (e.g., GeS2 and SnS2 ), fully dissolved in an alkahest: a mixture solvent of 1,2-ethylenediamine (EDA) and 1,2-ethanedithiol (EDT) (or ethanethiol). Raman spectroscopy and theoretical calculations reveal that the exceptional dissolving power of EDA-EDT toward GeS2 is due to the nucleophilicity of the thiolate anions that is strong enough to dissociate the GeS bonds. Solution-synthesized Li10 GeP2 S12 , Li6 PS5 Cl, and Na11 Sn2 PS12 exhibit high ionic conductivities (0.74, 1.3, and 0.10 mS cm-1 at 30 °C, respectively), and their application for all-solid-state batteries is successfully demonstrated.