Molecular anchoring of free solvents for high-voltage and high-safety lithium metal batteries.

Constraining the electrochemical reactivity of free solvent molecules is pivotal for developing high-voltage lithium metal batteries, especially for ether solvents with high Li metal compatibility but low oxidation stability ( <4.0 V vs Li+/Li). The typical high concentration electrolyte approach relies on nearly saturated Li+ coordination to ether molecules, which is confronted with severe side reactions under high voltages ( >4.4 V) and extensive exothermic reactions between Li metal and reactive anions. Herein, we propose a molecular anchoring approach to restrict the interfacial reactivity of free ether solvents in diluted electrolytes. The hydrogen-bonding interactions from the anchoring solvent effectively suppress excessive ether side reactions and enhances the stability of nickel rich cathodes at 4.7 V, despite the extremely low Li+/ether molar ratio (1:9) and the absence of typical anion-derived interphase. Furthermore, the exothermic processes under thermal abuse conditions are mitigated due to the reduced reactivity of anions, which effectively postpones the battery thermal runaway.

Effects and safety of endovascular recanalization for non-acute symptomatic intracranial vertebral artery occlusion with different risks.

There is no consensus on the optimal treatment for non-acute symptomatic intracranial vertebral artery occlusion, and endovascular recanalization is a challenging procedure. We report our clinical experience of endovascular recanalization in patients with non-acute symptomatic intracranial vertebral artery occlusion to assess the feasibility and safety of endovascular recanalization and determine the candidate patients for this procedure. Ninety-two patients with non-acute symptomatic intracranial vertebral artery occlusion who underwent endovascular recanalization from January 2019 to December 2021 were retrospectively analyzed. we grouped all patients according to imaging examination findings, occlusion length, duration, nature, calcification, and angulation to evaluate the risk of endovascular recanalization. The overall success rate of endovascular recanalization was 83.7% (77/92), and the perioperative complication rate was 10.9% (10/92). Among the 3 classification groups, the recanalization success rate gradually decreased from the low-risk group to the high-risk group (low-risk: 100%, medium-risk: 93.3%, high-risk group: 27.8%, P = .047), while the overall perioperative complication rate showed the opposite trend (0%, 10.0%, 38.9%, respectively, P = .001); the proportion of patients with 90-day modified Rankin Scale scores of 0-2 decreased successively (100%, 83.3%, and 22.2%, respectively, P < .026); 77 patients with successful recanalization were followed; the rate of restenosis/reocclusion increased sequentially (0%, 17.9%, and 80%, respectively, P = .000). Patients in the low- and medium-risk groups showed a good clinical course after endovascular recanalization. Among 88 patients (four patients lost to follow-up), with a median clinical follow-up of 13 months (interquartile range », 7-16), the rate of stroke or death after 30 days was 17.4% (16/92). Endovascular recanalization is safe and feasible for low- and medium-risk patients with non-acute symptomatic intracranial vertebral artery occlusion; it is also an alternative to conservative therapy for the patients.

Unveiling the Critical Role of Ion Coordination Configuration of Ether Electrolytes for High Voltage Lithium Metal Batteries.

Albeit ethers are favorable electrolyte solvents for lithium (Li) metal anode, their inferior oxidation stability (<4.0 V vs. Li/Li+ ) is problematic for high-voltage cathodes. Studies of ether electrolytes have been focusing on the archetype glyme structure with ethylene oxide moieties. Herein, we unveil the crucial effect of ion coordination configuration on oxidation stability by varying the ether backbone structure. The designed 1,3-dimethoxypropane (DMP, C3) forms a unique six-membered chelating complex with Li+ , whose stronger solvating ability suppresses oxidation side reactions. In addition, the favored hydrogen transfer reaction between C3 and anion induces a dramatic enrichment of LiF (a total atomic ratio of 76.7 %) on the cathode surface. As a result, the C3-based electrolyte enables greatly improved cycling of nickel-rich cathodes under 4.7 V. This study offers fundamental insights into rational electrolyte design for developing high-energy-density batteries.

Solvent versus Anion Chemistry: Unveiling the Structure-Dependent Reactivity in Tailoring Electrochemical Interphases for Lithium-Metal Batteries.

Electrolytes are critical for the reversibility of various electrochemical energy storage systems. The recent development of electrolytes for high-voltage Li-metal batteries has been counting on the salt anion chemistry for building stable interphases. Herein, we investigate the effect of the solvent structure on the interfacial reactivity and discover profound solvent chemistry of designed monofluoro-ether in anion-enriched solvation structures, which enables enhanced stabilization of both high-voltage cathodes and Li-metal anodes. Systematic comparison of different molecular derivatives provides an atomic-scale understanding of the unique solvent structure-dependent reactivity. The interaction between Li+ and the monofluoro (-CH2F) group significantly influences the electrolyte solvation structure and promotes the monofluoro-ether-based interfacial reactions over the anion chemistry. With in-depth analyses of the compositions, charge transfer, and ion transport at interfaces, we demonstrated the essential role of the monofluoro-ether solvent chemistry in tailoring highly protective and conductive interphases (with enriched LiF at full depths) on both electrodes, as opposed to the anion-derived ones in typical concentrated electrolytes. As a result, the solvent-dominant electrolyte chemistry enables a high Li Coulombic efficiency (∼99.4%) and stable Li anode cycling at a high rate (10 mA cm-2), together with greatly improved cycling stability of 4.7 V-class nickel-rich cathodes. This work illustrates the underlying mechanism of the competitive solvent and anion interfacial reaction schemes in Li-metal batteries and offers fundamental insights into the rational design of electrolytes for future high-energy batteries.

Localized Alkaline Environment via In Situ Electrostatic Confinement for Enhanced CO2-to-Ethylene Conversion in Neutral Medium.

Electrocatalytic CO2 reduction reaction (CO2RR) is one of the most promising routes to facilitate carbon neutrality. An alkaline electrolyte is typically needed to promote the production of valuable multi-carbon molecules (such as ethylene). However, the reaction between CO2 and OH- consumes a significant quantity of CO2/alkali and causes the rapid decay of CO2RR selectivity and stability. Here, we design a catalyst-electrolyte interface with an effective electrostatic confinement of in situ generated OH- to improve ethylene electrosynthesis from CO2 in neutral medium. In situ Raman measurements indicate the direct correlation between ethylene selectivity and the intensities of surface Cu-CO and Cu-OH species, suggesting the promoted C-C coupling with the surface enrichment of OH-. Thus, we report a CO2-to-ethylene Faradaic efficiency (FE) of 70% and a partial current density of 350 mA cm-2 at -0.89 V vs the reversible hydrogen electrode. Furthermore, the system demonstrated a 50 h stable operation at 300 mA cm-2 with an average ethylene FE of ∼68%. This study offers a universal strategy to tune the reaction micro-environment, and a significantly improved ethylene FE of 64.5% was obtained even in acidic electrolytes (pH = 2).

Strongly Solvating Ether Electrolytes for High-Voltage Lithium Metal Batteries.

Ethers are promising electrolytes for lithium (Li) metal batteries (LMBs) because of their unique stability with Li metal. Although intensive research on designing anion-enriched electrolyte solvation structures has greatly improved their electrochemical stabilities, ether electrolytes are approaching an anodic bottleneck. Herein, we reveal the strong correlation between electrolyte solvation structure and oxidation stability. In contrast to previous designs of weakly solvating solvents for enhanced anion reactivities, the triglyme (G3)-based electrolyte with the largest Li+ solvation energy among different linear ethers demonstrates greatly improved stability on Ni-rich cathodes under an ultrahigh voltage of 4.7 V (93% capacity retention after 100 cycles). Ether electrolytes with a stronger Li+ solvating ability could greatly suppress deleterious oxidation side reactions by decreasing the lifetime of free labile ether molecules. This study provides critical insights into the dynamics of the solvation structure and its significant influence on the interfacial stability for future development of high-efficiency electrolytes for high-energy-density LMBs.

Safety and effect of pipeline flex embolization device for complex unruptured intracranial aneurysms.

To investigate the safety and short-term effect of Pipeline Flex devices in the treatment of complex unruptured intracranial aneurysms, a retrospective study was performed for patients with complex unruptured intracranial aneurysms who were treated with the Pipeline Flex embolization device (PED Flex device) combined with or without coiling. The clinical, endovascular, and follow-up data were analyzed. One hundred and thirty-one patients with 159 complex unruptured cerebral aneurysms were treated with the PED Flex device, with 144 Flex devices deployed. Periprocedural complications occurred in four patients, resulting in the complication rate of 3.1%, including ischemic complications in three patients (2.3%) and hemorrhagic complication in one (0.8%). At discharge, the mRS was 0 in 101 (77.1%) patients, 1 in 25 (19.1%), 2 in four (3.1%), and 4 in one (0.8%), with the good prognosis rate (mRS 0-2) of 99.2%. Clinical follow-up was carried out in 87 (66.4%) patients 3-42 months after the procedure, with the mRS of 0 in 78 (89.7%), 1 in five (5.7%), 2 in three (3.4%), and 4 in one (1.1%). No significant (P = 0.16) difference existed in the mRS at discharge compared with that at clinical follow-up. Angiographic follow-up was performed in 61 (46.7%) patients with 80 (50.3%) aneurysms at 3-40 months, with the OKM grade of D in 57 (71.3%) aneurysms, C in eight (10%), and B in 15 (18.8%). Asymptomatic instent stenosis occurred in four patients (6.6%). In conclusion: The treatment of complex intracranial aneurysms with the Pipeline Flex embolization device may be safe and effective, with a high complete occlusion rate, a decreased complication rate, and a good prognosis rate at medium follow-up.

High-safety and high-efficiency electrolyte design for 4.6 V-class lithium-ion batteries with a non-solvating flame-retardant.

Nonflammable electrolytes are critical for the safe operation of high-voltage lithium-ion batteries (LIBs). Although organic phosphates are effective flame retardants, their poor electrochemical stability with a graphite (Gr) anode and Ni-rich cathodes would lead to the deterioration of electrode materials and fast capacity decay. Herein, we develop a safe and high-performance electrolyte formulation for high-voltage (4.6 V-class) LIBs using flame-retarding ethoxy(pentafluoro) cyclotriphosphazene (PFPN) as a non-solvating diluent for the high-concentration carbonate-ether hybrid electrolyte. In contrast to conventional nonflammable additives with restricted dosage, the high level of PFPN (69% mass ratio in our electrolyte design) could significantly increase the electrolyte flash point and protect the favored anion-rich inner solvation sheath because of its non-solvating feature, thus preventing solvent co-intercalation and structural damage to the Gr anode. The nonflammable electrolyte could also form a stable LiF-rich cathode electrolyte interphase (CEI), which enables superior electrochemical performances of Gr‖LiNi0.8Mn0.1Co0.1O2 (NMC811) full cells at high voltages (∼82.0% capacity retention after 1000 cycles at 4.5 V; 89.8% after 300 cycles at 4.6 V) and high temperatures (50 °C). This work sheds light on the electrolyte design and interphase engineering for developing practical safe high-energy-density LIBs.

Hybrid-Solvent Electrolytes for Enhanced Potassium-Oxygen Battery Performance.

Rechargeable potassium-oxygen batteries (KOB) are promising next-generation energy storage devices because of the highly reversible O2/O2- redox reactions during battery charge and discharge. However, the complicated cathode reaction processes seriously jeopardize the battery reaction kinetics and discharge capacity. Herein, we propose a hybrid-solvent strategy to effectively tune the K+ solvation structure, which demonstrates a critical influence on the charge-transfer kinetics and cathode reaction mechanism. The cosolvation of K+ by 1,2-dimethoxyethane (DME) and dimethyl sulfoxide (DMSO) could greatly decrease overpotentials for the cathode processes and increase the cathode discharge capacity. Furthermore, the Coulombic efficiency for the cathode could be significantly improved with the enhanced solution-mediated KO2 growth and stripping during cycling. This work provides a promising electrolyte design approach to improve the electrochemical performance of the KOB.

Intrinsic Nonflammable Ether Electrolytes for Ultrahigh-Voltage Lithium Metal Batteries Enabled by Chlorine Functionality.

The issues of inherent low anodic stability and high flammability hinder the deployment of the ether-based electrolytes in practical high-voltage lithium metal batteries. Here, we report a rationally designed ether-based electrolyte with chlorine functionality on ether molecular structure to address these critical challenges. The chloroether-based electrolyte demonstrates a high Li Coulombic efficiency of 99.2 % and a high capacity retention >88 % over 200 cycles for Ni-rich cathodes at an ultrahigh cut-off voltage of 4.6 V (stable even up to 4.7 V). The chloroether-based electrolyte not only greatly improves electrochemical stabilities of Ni-rich cathodes under ultrahigh voltages with interphases riched in LiF and LiCl, but possesses the intrinsic nonflammable safety feature owing to the flame-retarding ability of chlorine functional groups. This study offers a new approach to enable ether-based electrolytes for high energy density, long-life and safe Li metal batteries.

Plastic Monolithic Mixed-Conducting Interlayer for Dendrite-Free Solid-State Batteries.

Solid-state electrolytes (SSEs) hold a critical role in enabling high-energy-density and safe rechargeable batteries with Li metal anode. Unfortunately, nonuniform lithium deposition and dendrite penetration due to poor interfacial solid-solid contact are hindering their practical applications. Here, solid-state lithium naphthalenide (Li-Naph(s)) is introduced as a plastic monolithic mixed-conducting interlayer (PMMCI) between the garnet electrolyte and the Li anode via a facile cold process. The thin PMMCI shows a well-ordered layered crystalline structure with excellent mixed-conducting capability for both Li+ (4.38 × 10-3  S cm-1 ) and delocalized electrons (1.01 × 10-3  S cm-1 ). In contrast to previous composite interlayers, this monolithic material enables an intrinsically homogenous electric field and Li+ transport at the Li/garnet interface, thus significantly reducing the interfacial resistance and achieving uniform and dendrite-free Li anode plating/stripping. As a result, Li symmetric cells with the PMMCI-modified garnet electrolyte show highly stable cycling for 1200 h at 0.2 mA cm-2 and 500 h at a high current density of 1 mA cm-2 . The findings provide a new interface design strategy for solid-state batteries using monolithic mixed-conducting interlayers.

An Overcrowded Water-Ion Solvation Structure for a Robust Anode Interphase in Aqueous Lithium-Ion Batteries.

The water-in-salt electrolyte (WISE) features intimate interactions between a cation and anion, which induces the formation of an anion-derived solid electrolyte interphase (SEI) and expands the aqueous electrolyte voltage window to >3.0 V. Although further increasing the salt concentration (even to >60 molality (m)) can gradually improve water stability, issues about cost and practical feasibility are concerned. An alternative approach is to intensify ion-solvent interactions in the inner solvation structure by shielding off outward electrostatic attractions from nearby ions. Here, we design an "overcrowded" electrolyte using the non-polar, hydrogen-bonding 1,4-dioxane (DX) as an overcrowding agent, thereby achieving a robust LiF-enriched SEI and wide electrolyte operation window (3.7 V) with a low salt concentration (<2 m). As a result, the electrochemical performance of aqueous Li4Ti5O12/LiMn2O4 full cells can be substantially improved (88.5% capacity retention after 200 cycles, at 0.57 C). This study points out a promising strategy to develop low-cost and stable high-voltage aqueous batteries.

Melt-spun modified poly (styrene-co-butyl acrylate) fiber as a carrier to support manganese oxide and its application in dye wastewater decolorization.

Polymer fiber, a kind of versatile material, has been widely used in many fields. However, emerging applications still urge us to develop some new kinds of fibers. Advanced oxidation processes (AOPs) have created a promising prospect for organic wastewater decontamination; thus, it is of important significance to design a kind of special fiber that can be applied in AOPs. In this work, a viable route is proposed to fabricate manganese oxide-supporting melt-spun modified poly (styrene-co-butyl acrylate) fiber, and the prepared fiber has an excellent activity to catalyze H2O2 and O3 to decolorize dye-containing water. The results show that the decolorization of a cationic blue solution can be completely accomplished within 10 min with the prepared fiber as a catalyst, and its decolorization efficiency can reach up to 96.2% within 40 min. The concentration of total organic carbon can decrease from 20.3 to 12.3 mg/L. The prepared fiber can be reused five times without any loss in decolorization efficiency. Compared with other manganese oxide-based catalysts reported in the literature, the prepared fiber also shows many advantages in decolorizing methylene blue such as easy separation, mild reaction condition, and high decolorization efficiency. Therefore, we are confident that the fiber introduced in this study will exhibit a great application potential in the field of dye wastewater treatment.

Synthesis of CdS-loaded (CuC10H26N6)3(PW12O40)2 for enhanced photocatalytic degradation of tetracycline under simulated solar light irradiation.

Largely discharged and excreted medical pollutants pose huge threats to ecosystems. However, typical photocatalysts, such as the Keggin-typed H3PW12O40, can hardly degrade these hazards under visible-light due to their broad bandgap and catalytic disability. In this work, the visible light harvesting was enabled by combining macrocyclic coordination compound CuC10H26N6Cl2O8 with H3PW12O40, and the resulting CuPW was loaded with CdS to reach robust catalytic ability to totally detoxify medicines. We prepared the CuPW-CdS composites through a facile precipitation method, and it showed excellent photocatalytic degradation for degrading tetracycline under visible-light irradiation. The (CuC10H26N6)3(PW12O40)2 with 10 wt% load of CdS shows the highest performance and is ∼6 times more efficient than the pure CuPW counterpart. The heterojunctional CuPW-CdS composites promote the separation of electrons and holes, and consequentially enhance photocatalytic activity. Thanks to migration of electrons from CdS to CuPW, the photocorrosion of CdS is prohibited, resulting in a high chemical stability during photocatalysis. In this work we design a new route to the multi-structural composite photocatalysts for practical applications in medical pollutant decontamination.

Loading AgCl@Ag on phosphotungstic acid modified macrocyclic coordination compound: Z-scheme photocatalyst for persistent pollutant degradation and hydrogen evolution.

In this work, Z-scheme photocatalysts of (CuC10H26N6)3(PW12O40)2/AgCl@Ag were designed and realized for effective removal of solvable and insolvable persistent organic pollutants and hydrogen evolution under simulated sunlight. The catalysts were synthesized via a simple hydrothermal-chemical co-precipitation method. Excellent photocatalytic abilities are demonstrated in degradations of persistent pollutant 2,4-Dinitrophenol (DNP) and tetracycline (TC) under simulated sunlight, as well as a high H2 production rate of 19.28 µâ€¯mol g-1 h-1. Through structural, morphological, radical, and electrochemical determinations, the photocatalytic mechanism was studied, and attributed to effective separations of charge carriers between the heterojunctional counterparts of (CuC10H26N6)3(PW12O40)2 and AgCl@Ag.