Unveiling the Mysteries: Acetonitrile's Dance with Weakly-Solvating Electrolytes in Shaping Gas Evolution and Electrochemical Performance of Zinc-ion Batteries.

Aqueous Zn-metal battery (AZMB) is a promising candidate for future large-scale energy storage with commendable capacity, exceptional safety characteristics, and low cost. Acetonitrile (AN) has been widely used as an effective electrolyte constituent to improve AZMBs' performance. However, its functioning mechanisms remain unclear. In this study, we unveiled the critical roles of AN in AZMBs via comparative in situ electrochemical, gaseous, and morphological analyses. Despite its limited ability to solvate Zn ions, AN-modulated Zn-ion solvation sheath with increased anions and decreased water achieves a weakly-solvating electrolyte. As a result, the Zn||Zn cell with AN addition exhibited 63 times longer cycle life than cell without AN and achieved a 4 Ah cm-2 accumulated capacity with no H2 generation. In V2O5||Zn cells, for the first time, AN suppressing CO2 generation, elevating CO2-initiation voltage from 2→2.44 V (H2: 2.43→2.55 V) was discovered. AN-impeded transit and Zn-side deposition of dissolved vanadium ions, known as "crosstalk," ameliorated inhomogeneous Zn deposition and dendritic Zn growth. At last, we demonstrated an AN-enabled high-areal-capacity AZMB (3.3 mAh cm-2) using high-mass-loading V2O5 cathode (26 mg cm-2). This study shed light on the strategy of constructing fast-desolvation electrolytes and offered insights for future electrolyte accommodation for high-voltage AZMB cathodes.

Regulating Zinc Nucleation Sites and Electric Field Distribution to Achieve High-Performance Zinc Metal Anode via Surface Texturing.

Understanding zinc (Zn) deposition behavior and improving Zn stripping and plating reversibility are significant in developing practical aqueous Zn ion batteries (AZIBs). Zn metal is abundant, cost-effective, and intrinsically safe compared with Li. However, their similar inhomogeneous growth regime harms their practicality. This work reports a facile, easily scalable, but effective method to develop a textured Zn with unidirectional scratches on the surface that electrochemically achieves a high accumulated areal capacity of 5530 mAh cm-2 with homogenized Zn deposition. In symmetric cells, textured Zn presents a stable cycling performance of 1100 hours (vs 250 h of bare Zn) at 0.5 mA cm-2 for 0.5 mAh cm-2 and lower nucleation and plating overpotentials of 120.5 and 41.8 mV. In situ optical microscopy and COMSOL simulation disclose that the textured surface topography can 1) homogenize the electron field distribution on the Zn surface and regulate Zn nucleation and growth, and 2) provides physical space to accommodate Zn deposits, prevent the detachment of "dead" Zn, and improve the structural sufficiency of Zn anode. Moreover, differential electrochemical mass spectrometry analysis find that the textured Zn with regulated interfacial electron activity also presents a higher resistance toward hydrogen evolution and other parasitic reactions.

Coulombic Efficiency for Practical Zinc Metal Batteries: Critical Analysis and Perspectives.

Climate change and energy depletion are common worries of this century. During the global clean energy transition, aqueous zinc metal batteries (AZMBs) are expected to meet societal needs due to their large-scale energy storage capability with earth-abundant, non-flammable, and economical chemistries. However, the poor reversibility of Zn poses a severe challenge to AZMB implementation. Coulombic efficiency (CE) is a quantitative index of electrode reversibility in rechargeable batteries but is not well understood in AZMBs. Thus, in this work,  the state-of-art CE to present the status quo of AZMB development is summarized.  A fictional 120 Wh kg-1 AZMB pouch cell is also proposed and evaluated revealing the improvement room and technical goal of AZMB chemistry. Despite some shared mechanisms between AZMBs and lithium metal batteries, misconceptions prevalent in AZMBs are clarified. Essentially, AZMB has its own niche in the market with unique merits and demerits. By incorporating academic and industrial insights, the development pathways of AZMB are suggested.

Cuproptosis-related genes score and its hub gene GCSH: A novel predictor for cholangiocarcinomas prognosis based on RNA seq and experimental analyses.

Background: Recent researches have demonstrated that cuproptosis, a copper-dependent cell death mechanism, is related to tumorigenesis, progression, clinical prognosis, tumor microenvironment, and drug sensitivity. Nevertheless, the function and impact of cuproptosis in cholangiocarcinoma (CCA), remain elusive. Methods: Utilizing data obtained from the Gene Expression Omnibus (GEO) and The Cancer Genome Atlas (TCGA-CHOL) datasets, we conducted subgroup typing of CCA according to cuproptosis-related genes (CRGs) and explored functional differences and prognostic value between groups. A CRG score was established considering clinical prognosis and gene expression. Furthermore, differences in the immune microenvironment, response to immunotherapy, metabolic patterns, and cancer progression characteristics between high- and low-risk groups were examined on the basis of these scores. In vitro experiments validated the function of the key gene glycine cleavage system protein H (GCSH) in cellular and tissues, respectively. Results: Prognostic models established on the basis of subgroup genetic differences achieved satisfactory results in validation. Metabolic-related gene expression levels and tumor microenvironment distribution were significantly different between the high and low CRG groups. GCSH was revealed as the singular prognostic CRG in CCA (HR =6.04; 95% CI: 1.15-31.80). Moreover, inhibition of the cupcoptosis key gene GCSH attenuated the malignant ability of CCA cell lines in vitro, including cell proliferation, migration and invasion, and this function of GCSH may be achieved via JAK-STAT signaling in CCA. Conclusion: The CRG scoring system accurately predicts prognosis and opens up new possibilities for cuproptosis-related therapy for CCA. The cuproptosis key gene GCSH has been preliminarily confirmed as a reliable therapeutic target or prognostic marker for CCA patients.

Low MARCO Expression is Associated with Poor Survival in Patients with Hepatocellular Carcinoma Following Liver Transplantation.

Background: Macrophage receptor with collagenous structure (MARCO) reportedly plays a crucial role in the occurrence and development of several cancers. However, the association between MARCO and the prognosis of hepatocellular carcinoma (HCC) post-liver transplantation remains poorly elucidated. Methods: We examined MARCO expression at mRNA and protein level in 145 HCC samples and adjacent nontumor tissues using quantitative reverse transcription PCR, Western blot and immunohistochemistry. Furthermore, we analyzed the correlation of MARCO expression with clinicopathologic features and prognosis. Results: We assessed the association between MARCO expression and clinicopathologic features and used the Cox proportional hazards regression model to explore the association between MARCO expression and clinical prognosis of patients with HCC post-liver transplantation. We observed that the expression of MARCO at mRNA and protein level in adjacent nontumor tissues was higher than that in the HCC tissues. Low MARCO expression in HCC tissues was correlated with higher alpha-fetoprotein levels, higher incidence of microvascular invasion, and a higher number of patients beyond Milan criteria. Kaplan-Meier survival curves showed that patients with HCC with low MARCO expression exhibited poor overall survival (OS) and disease-free survival (DFS). Univariate and multivariate analysis revealed that MARCO expression was an independent prognostic factor for OS (hazard ratio [HR] 2.696, 95% confidence interval [CI] 1.335-5.444, P=0.006) and DFS (HR 2.867, 95% CI 1.665-4.936, P<0.001) in patients with HCC post-liver transplantation. Based on immunofluorescence analysis, MARCO expression was primarily localized to macrophages and might be associated with M2-like macrophage polarization during HCC. Conclusion: MARCO expression was downregulated in HCC and associated with poor prognosis of patients with HCC post-liver transplantation. Moreover, it could be a potential prognostic marker and therapeutic target in post-liver transplantation HCC.

Designing Zinc Deposition Substrate with Fully Preferred Orientation to Elude the Interfacial Inhomogeneous Dendrite Growth.

The development of zinc-ion batteries with high energy density remains a great challenge due to the uncontrollable dendrite growth on their zinc metal anodes. Film anodes plated on the substrate have attracted increasing attention to alleviate these dendrite issues. Herein, we first point out that both the random crystal orientation and the low metal affinity of the substrate are important factors of zinc dendrite formation. Accordingly, the (1 0 1) fully preferred tin interface layer with high zinc affinity was fabricated by chemical tin plating on (1 0 0) oriented copper. This tin decorated copper substrate can realize high reversible zinc plating/stripping behavior, and full cell using this zinc plated substrate can be operated for more than 1000 cycles with high capacity retention (85.3%) and low electrochemical impedance. The proposed strategy can be also applied to lithium metal batteries, which demonstrates that the substrate orientation regulation and metal affinity design are the promising approaches to achieve dendrite-free metal anode and overcome the challenges of highly reactive metal anodes.