Safety concerns are impeding the applications of lithium metal batteries. Flame‐retardant electrolytes, such as organic phosphates electrolytes (OPEs), could intrinsically eliminate fire hazards and ...improve battery safety. However, OPEs show poor compatibility with Li metal though the exact reason has yet to be identified. Here, the lithium plating process in OPEs and Li/OPEs interface chemistry were investigated through ex situ and in situ techniques, and the cause for this incompatibility was revealed to be the highly resistive and inhomogeneous interfaces. Further, a nitriding interface strategy was proposed to ameliorate this issue and a Li metal anode with an improved Li cycling stability (300 h) and dendrite‐free morphology is achieved. Meanwhile, the full batteries coupled with nickel‐rich cathodes, such as LiNi0.8Co0.1Mn0.1O2, show excellent cycling stability and outstanding safety (passed the nail penetration test). This successful nitriding‐interface strategy paves a new way to handle the incompatibility between electrode and electrolyte.
A nitriding interface has been developed for the successful application of flame‐retardant electrolytes in high‐energy‐density cells using a Li metal anode and a high‐voltage, high‐capacity cathode. The homogeneity of the solid electrolyte interface (SEI) layer is crucially important for the uniform Li deposition required for high‐voltage batteries.
Full text
Available for:
BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
The interfacial processes, mainly the lithium (Li) plating/stripping and the evolution of the solid electrolyte interphase (SEI), are directly related to the performance of all‐solid‐state Li‐metal ...batteries (ASSLBs). However, the complex processes at solid‐solid interfaces are embedded under the solid‐state electrolyte, making it challenging to analyze the dynamic processes in real time. Here, using in situ electrochemical atomic force microscopy and optical microscopy, we directly visualized the Li plating/stripping/replating behavior, and measured the morphological and mechanical properties of the on‐site formed SEI at nanoscale. Li spheres plating/stripping/replating at the argyrodite solid electrolyte (Li6PS5Cl)/Li electrode interface is coupled with the formation/wrinkling/inflating of the SEI on its surface. Combined with in situ X‐ray photoelectron spectroscopy, details of the stepwise formation and physicochemical properties of SEI on the Li spheres are obtained. It is shown that higher operation rates can decrease the uniformity of the Li+‐conducting networks in the SEI and worsen Li plating/stripping reversibility. By regulating the applied current rates, uniform nucleation and reversible plating/stripping processes can be achieved, leading to the extension of the cycling life. The in situ analysis of the on‐site formed SEI at solid‐solid interfaces provides the correlation between the interfacial evolution and the electrochemical performance in ASSLBs.
Using in situ methods of atomic force microscopy, X‐ray photoelectron spectroscopy and optical microscopy, we visualized the processes of Li plating, stripping and replating tuned by the on‐site formed SEI at the argyrodite solid‐electrolyte/Li anode interface in all‐solid‐state Li‐metal batteries. Our work provides insights into correlations between the interfacial evolution and cell performance, contributing to the improvement of solid‐state energy devices.
Full text
Available for:
BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Lithium‐sulfur batteries are promising candidates of energy storage devices. Both adjusting salt/solvent ratio and applying quasi‐solid‐state electrolytes are regarded as effective strategies to ...improve the lithium (Li) anode performance. However, reaction mechanisms and interfacial properties in quasi‐solid‐state lithium‐sulfur (QSSLS) batteries with high salt concentration are not clear. Here we utilize in‐situ characterizations and molecular dynamics simulations to unravel aforesaid mysteries, and construct relationships of electrolyte structure, interfacial behaviour and performance. The generation mechanism, formation process, and mechanical/chemical/electrochemical properties of the anion‐derived solid electrolyte interphase (SEI) are deeply explored. Li deposition uniformity and dissolution reversibility are further tuned by the sustainable SEI. These straightforward evidences and deepgoing studies would guide the electrolyte design and interfacial engineering of QSSLS batteries.
The electrochemical processes at the Li anode/electrolyte interface are disclosed in quasi‐solid‐state lithium‐sulfur batteries with high salt concentration via in‐situ atomic force microscopy and optical microscopy. The 3D morphology, local mechanics, and ion conductivity of the on‐site formed solid electrolyte interphase are in‐situ measured and analyzed to reveal the regulation effect of high salt concentration on interfacial electrochemistry.
Full text
Available for:
BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Phytohormones are key regulators of plant growth, development, and signalling networks involved in responses to diverse biotic and abiotic stresses. Transcriptional reference maps of hormone ...responses have been reported for several model plant species such as Arabidopsis thaliana, Oryza sativa, and Brachypodium distachyon. However, because of species differences and the complexity of the wheat genome, these transcriptome data are not appropriate reference material for wheat studies.
We comprehensively analysed the transcriptomic responses in wheat spikes to seven phytohormones, including indole acetic acid (IAA), gibberellic acid (GA), abscisic acid (ABA), ethylene (ET), cytokinin (CK), salicylic acid (SA), and methyl jasmonic acid (MeJA). A total of 3386 genes were differentially expressed at 24 h after the hormone treatments. Furthermore, 22.7% of these genes exhibited overlapping transcriptional responses for at least two hormones, implying there is crosstalk among phytohormones. We subsequently identified genes with expression levels that were significantly and differentially induced by a specific phytohormone (i.e., hormone-specific responses). The data for these hormone-responsive genes were then compared with the transcriptome data for wheat spikes exposed to biotic (Fusarium head blight) and abiotic (water deficit) stresses.
Our data were used to develop a transcriptional reference map of hormone responses in wheat spikes.
Full text
Available for:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Adding small molecular plasticizers is the most common route to tailor the stretchability of poly(vinyl alcohol) (PVA). However, how the plasticization along with the nature of the plasticizer ...governs the structural homogeneity during stretching remains an open question to answer. Herein, two representative plasticizers, glycerol (GLY) and water, are chosen to endow the PVA films with ductility. It is found that large strain cavitations cause obvious stress whitening in the PVA/H2O films; on the contrary, most of the PVA/GLY films maintain transparent undergoing tensile deformation. Through a combination of experimental inspections and molecular dynamic simulation, it is revealed that partial water molecules that behave as free water will aggregate into microdomains, which serve as mechanical defects responsible for yielding voids. Whereas, the GLY plasticizer homogeneously disperses at a molecular level and interacts with PVA chains through strong hydrogen bonds. More interestingly, it is illustrated that the dispersion and bound states of plasticizers are closely related to the mechanical character of the plasticized PVA films. These findings offer new insight into the working mechanism of plasticization on the structural stability during stretching, and guide the design of PVA/plasticizer system to obtain excellent comprehensive mechanics.
The structural stability of plasticized PVA films during stretching strongly relies on the dispersion and bound states of plasticizers. A molecule‐level dispersion of glycerol and its tight interaction with PVA chains endow the PVA film with a facile reformation of H‐bonds after breakage. Whereas, freezable bound water and free water aggregate into microdomains responsible for forming cavitations.
Full text
Available for:
BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Portal vein tumor thrombus (PVTT) is a significant poor prognostic factor for hepatocellular carcinoma (HCC). Patients with PVTT limited to a first‐order branch of the main portal vein (MPV) or above ...could benefit from negative margin (R0) liver resection (LR). An Eastern Hepatobiliary Surgery Hospital (EHBH)/PVTT scoring system was established to predict the prognosis of HCC patients with PVTT after R0 LR and guide selection of subgroups of patients that could benefit from LR. HCC patients with PVTT limited to a first‐order branch of the MPV or above who underwent R0 LR as an initial therapy were included. The EHBH‐PVTT score was developed from a retrospective cohort in the training cohort using a Cox regression model and validated in a prospective internal validation cohort and three external validation cohorts. There were 432 patients in the training cohort, 285 in the prospective internal validation cohort, and 286, 189, and 135 in three external validation cohorts, respectively. The score was calculated using total bilirubin, α‐fetoprotein (AFP), tumor diameter, and satellite lesions. The EHBH‐PVTT score differentiated two groups of patients (≤/>3 points) with distinct long‐term prognoses (median overall survival OS, 17.0 vs. 7.9 months; P < 0.001). Predictive accuracy, as determined by the area under the time‐dependent receiver operating characteristic curves (AUCs; 0.680‐0.721), was greater than that of the other commonly used staging systems for HCC and PVTT. Conclusion: The EHBH‐PVTT scoring system was more accurate in predicting the prognosis of HCC patients with PVTT than other staging systems after LR. It selected appropriate HCC patients with PVTT limited to a first‐order branch of the MPV or above for LR. It can be used to supplement the other HCC staging systems.
Full text
Available for:
BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
Background & Aims The pathogenesis of intrahepatic cholangiocarcinoma (ICC), the second most common hepatic cancer, is poorly understood, and the incidence of ICC is increasing worldwide. We searched ...for mutations in human ICC tumor samples and investigated how they affect ICC cell function. Methods We performed whole exome sequencing of 7 pairs of ICC tumors and their surrounding nontumor tissues to detect somatic alterations. We then screened 124 pairs of ICC and nontumor samples for these mutations, including 7 exomes. We compared mutations in PTPN3 with tumor recurrence in 124 patients and PTPN3 expression levels with recurrence in 322 patients (the combination of both in 86 patients). The functional effects of PTPN3 variations were determined by RNA interference and transgenic expression in cholangiocarcinoma cell lines (RBE, HCCC-9810, and Huh28). Results Based on exome sequencing, pathways that regulate protein phosphorylation were among the most frequently altered in ICC samples and genes encoding protein tyrosine phosphatases (PTPs) were among the most frequently mutated. We identified mutations in 9 genes encoding PTPs in 4 of 7 ICC exomes. In the prevalence screen of 124 paired samples, 51.6% of ICCs contained somatic mutations in at least 1 of 9 PTP genes; 41.1% had mutations in PTPN3 . Transgenic expression of PTPN3 in cell lines increased cell proliferation, colony formation, and migration. PTPN3 L232R and PTPN3 L384H , which were frequently detected in ICC samples, were found to be gain-of-function mutations; their expression in cell lines further increased cell proliferation, colony formation, and migration. ICC-associated variants of PTPN3 altered phosphatase activity. Patients whose tumors contained activating mutations or higher levels of PTPN3 protein than nontumor tissues had higher rates of disease recurrence than patients whose tumors did not have these characteristics. Conclusions Using whole exome sequencing of ICC samples from patients, we found that more than 40% contain somatic mutations in PTPN3 . Activating mutations in and high expression levels of PTPN3 were associated with tumor recurrence.
Over the past decades, molecular knots and links have captivated the chemical community due to their promising mimicry properties in molecular machines and biomolecules and are being realized with ...increasing frequency with small molecules. Herein, we describe how to utilize stacking interactions and hydrogen-bonding patterns to form trefoil knots, figure-eight knots and 2catenanes. A transformation can occur between the unique trefoil knot and its isomeric boat-shaped tetranuclear macrocycle by the complementary concentration effect. Remarkably, the realization and authentication of the molecular figure-eight knot with four crossings fills the blank about 4
knot in knot tables. The 2catenane topology is obtained because the selective naphthalenediimide (NDI)-based ligand, which can engender favorable aromatic donor-acceptor π interactions due to its planar, electron-deficient aromatic surface. The stacking interactions and hydrogen-bond interactions play important roles in these self-assembly processes. The advantages provide an avenue for the generation of structurally and topologically complex supramolecular architectures.
Trigonal planar units with large polarizability anisotropy and high physicochemical stability are ideal structural units for exploring nonlinear optical (NLO) materials. Integrating the merits of two ...types of triangular‐like moieties, a family of second‐order NLO‐active hybrid halides, MATX (X = Cl (1), Br (2), and I (3)), are achieved. MATX crystallizes in a nonpolar space group of P6¯$P\overline 6 $2c but exhibits the optimal spatial arrangement and superior NLO performance. The low coordination planar trigonal AgX3 units enable segregation in layers of the three‐winged propeller‐like Me3TPA units. All of the layers are packed in a perfect parallel fashion, making the functional materials exhibit superior NLO performances, including the phase matchable behavior with strong SHG responses (6.2/1, 6.5/2, and 7.6/3 times that of potassium dihydrogen phosphate), large birefringence (0.232/1, 0.252/2 and 0.260/3 at 1064 nm), high laser damage threshold, wide transparent window, and easiness of crystal growth. The first‐principles calculations reveal that the coexistence of strong linear and nonlinear optical properties are ascribed to the synergistic effect of the trigonal moieties. This study points out a useful path for the rational design of excellent NLO materials.
Me3TPAAgX3X (X = Cl, Br or I) exhibits optimal planar alignment of two types of triangular‐like units and superior NLO performances, including the phase matchable behavior with strong second‐harmonic generation response, large birefringence, high LDT, wide band gap, and easiness of crystal growth.
Full text
Available for:
BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SBCE, SBMB, UL, UM, UPUK
PDF
