Trace Selenium Doping for Improving the Reaction Kinetics of ZnS Cathode for Aqueous Zn-S Batteries.

Aqueous Zinc-sulfur (Zn-S) batteries are promising for the field of energy storage due to their low cost, high theoretical capacity, and safety. However, the large volume expansion and the inherently poor conductivity of sulfur would result in electrode cracking and sluggish reaction kinetics, limiting the practical application of Zn-S batteries. Herein, commercial zinc sulfide (ZnS) is employed instead of S as cathode and proposed a doping modification strategy to solve the above problems. The designed ZnS0.93Se0.07 cathode shows good cycle stability and much-improved reaction kinetics, which is due to the smaller bandgap of ZnS0.93Se0.07 (1.40 eV) compared to ZnS (1.86 eV). As a result, the obtained ZnS0.93Se0.07 cathode exhibits a high specific capacity of 552 mAh g-1 (1672.6 mAh g-1 based on S) at 0.1 A g-1 and 330 mAh g-1 (1000 mAh g-1 based on S) at 2 A g-1. Moreover, the ZnS0.93Se0.07 cathode can provide a high areal capacity of 3.8 mAh cm-2 at a high mass loading of 10 mg cm-2 and limited electrolyte (4 µL mg-1). This work provides a simple and effective cathode modification strategy, which is conducive to promoting the practical application of Zn-S batteries.

Metal bond strength regulation enables large-scale synthesis of intermetallic nanocrystals for practical fuel cells.

Structurally ordered L10-PtM (M = Fe, Co, Ni and so on) intermetallic nanocrystals, benefiting from the chemically ordered structure and higher stability, are one of the best electrocatalysts used for fuel cells. However, their practical development is greatly plagued by the challenge that the high-temperature (>600 °C) annealing treatment necessary for realizing the ordered structure usually leads to severe particle sintering, morphology change and low ordering degree, which makes it very difficult for the gram-scale preparation of desirable PtM intermetallic nanocrystals with high Pt content for practical fuel cell applications. Here we report a new concept involving the low-melting-point-metal (M' = Sn, Ga, In)-induced bond strength weakening strategy to reduce Ea and promote the ordering process of PtM (M = Ni, Co, Fe, Cu and Zn) alloy catalysts for a higher ordering degree. We demonstrate that the introduction of M' can reduce the ordering temperature to extremely low temperatures (≤450 °C) and thus enable the preparation of high-Pt-content (≥40 wt%) L10-Pt-M-M' intermetallic nanocrystals as well as ten-gram-scale production. X-ray spectroscopy studies, in situ electron microscopy and theoretical calculations reveal the fundamental mechanism of the Sn-facilitated ordering process at low temperatures, which involves weakened bond strength and consequently reduced Ea via Sn doping, the formation and fast diffusion of low-coordinated surface free atoms, and subsequent L10 nucleation. The developed L10-Ga-PtNi/C catalysts display outstanding performance in H2-air fuel cells under both light- and heavy-duty vehicle conditions. Under the latter condition, the 40% L10-Pt50Ni35Ga15/C catalyst delivers a high current density of 1.67 A cm-2 at 0.7 V and retains 80% of the current density after extended 90,000 cycles, which exceeds the United States Department of Energy performance metrics and represents among the best cathodic electrocatalysts for practical proton-exchange membrane fuel cells.

Hybrid supercapacitors using metal-organic framework derived nickel-sulfur compounds.

HYPOTHESIS: Metal-organic frameworks (MOFs) are highly suitable precursors for supercapacitor electrode materials owing to their high porosity and stable backbone structures that offer several advantages for redox reactions and rapid ion transport. EXPERIMENTS: In this study, a carbon-coated Ni9S8 composite (Ni9S8@C-5) was prepared via sulfuration at 500 ℃ using a spherical Ni-MOF as the sacrificial template. FINDING: The stable carbon skeleton derived from Ni-MOF and positive structure-activity relationship due to the multinuclear Ni9S8 components resulted in a specific capacity of 278.06 mAh·g-1 at 1 A·g-1. Additionally, the hybrid supercapacitor (HSC) constructed using Ni9S8@C-5 as the positive electrode and the laboratory-prepared coal pitch-based activated carbon (CTP-AC) as the negative electrode achieved an energy density of 69.32 Wh·kg-1 at a power density of 800.06 W·kg-1, and capacity retention of 83.06 % after 5000 cycles of charging and discharging at 5 A·g-1. The Ni-MOF sacrificial template method proposed in this study effectively addresses the challenges associated with structural collapse and agglomeration of Ni9S8 during electrochemical reactions, thus improving its electrochemical performance. Hence, a simple preparation method is demonstrated, with broad application prospects in supercapacitor electrodes.

Tailoring Zirconia Supported Intermetallic Platinum Alloy via Reactive Metal-Support Interactions for High-Performing Fuel Cells.

Developing efficient and anti-corrosive oxygen reduction reaction (ORR) catalysts is of great importance for the applications of proton exchange membrane fuel cells (PEMFCs). Herein, we report a novel approach to prepare metal oxides supported intermetallic Pt alloy nanoparticles (NPs) via the reactive metal-support interaction (RMSI) as ORR catalysts, using Ni-doped cubic ZrO2 (Ni/ZrO2) supported L10-PtNi NPs as a proof of concept. Benefiting from the Ni migration during RMSI, the oxygen vacancy concentrations in the support are increased, leading to an electron enrichment of Pt. The optimal L10-PtNi-Ni/ZrO2-RMSI catalyst achieves remarkably low mass activity (MA) loss (17.8 %) after 400,000 accelerated durability test cycles in a half-cell and exceptional PEMFC performance (MA=0.76 A mgPt -1 at 0.9 V, peak power density=1.52/0.92 W cm-2 in H2-O2/-air, and 18.4 % MA decay after 30,000 cycles), representing the best reported Pt-based ORR catalysts without carbon supports. Density functional theory (DFT) calculations reveal that L10-PtNi-Ni/ZrO2-RMSI requires a lower energetic barrier for ORR than L10-PtNi-Ni/ZrO2 (direct loading), which is ascribed to a decreased Bader charge transfer between Pt and *OH, and the improved stability of L10-PtNi-Ni/ZrO2-RMSI compared to L10-PtNi-C can be contributed to the increased adhesion energy and Ni vacancy formation energy within the PtNi alloy.

Multifunctional Additive Enables a "5H" PEO Solid Electrolyte for High-Performance Lithium Metal Batteries.

The solid-state battery with a lithium metal anode is a promising candidate for next-generation batteries with improved energy density and safety. However, the current polymer electrolytes still cannot fulfill the demands of solid-state batteries. In this work, we propose a "5H" poly(ethylene oxide) (PEO) electrolyte via introducing a multifunctional additive of tris(pentafluorophenyl)borane (TPFPB) for high-performance lithium metal batteries. The addition of TPFPB improves the ionic conductivity from 6.08 × 10-5 to 1.54 × 10-4 S cm-1 via reducing the crystallinity of the PEO electrolyte and enhances the lithium-ion transference number from 0.19 to 0.53 via anion trapping due to its Lewis acid nature. Furthermore, the fluorine and boron segments from TPFPB can optimize the composition of the solid-electrolyte interphase and cathode-electrolyte interphase, providing a high electrochemical stability window over 4.6 V of the PEO electrolyte along with significantly improved interface stability. At last, TPFPB can ensure improved safety through a self-extinguishing effect. As a result, the "5H" electrolyte enables the Li/Li symmetric cells to achieve a stable cycle over 2200 h at the current density of 0.2 mA cm-2 with a capacity of 0.2 mA h cm-2; the LiFePO4/Li full cells with a high LFP loading of 8 mg cm-2 exhibits decay-free capacity of 140 mA h g-1 (99% capacity retention) after 100 cycles; and the NCM811/Li cells exhibit a high capacity of 160 mA h g-1 after 50 cycles at 0.5 C. This work presents an innovative approach to utilizing a "5H" electrolyte for high-performance solid-state lithium batteries.

Interface engineering and nanoconfinement strategies to synergistically enhance hydrogen evolution in acidic and basic media.

As a potential catalyst for hydrogen evolution reaction (HER), tungsten nitride (W2N) has attracted extensive attention, due to its Pt-like characteristic. Nevertheless, insufficient active sites, slow electron transfer, and lack of scale-up nano-synthesis methods significantly limit its practical application. Constructing multi-component active centers and interface-rich heterojunctions to increase exposed active sites and modulate interface electrons is a very effective modification strategy. Therefore, a nano-heterostructure formed from tungsten nitride, tungsten phosphide and tungsten encapsulated in N, P co-doped carbon nanofiber (W2N/WP/W@NPC) was synthesized by a flexible and scalable electrospinning technology. Experimental results reveal that abundant heterojunctions are formed, electron transfer occurs between tungsten nitride and tungsten phosphide, and carbon nanofibers play a confinement role. The optimized W2N/WP/W@NPC-3 electrocatalyst demonstrates excellent HER catalytic activity and robust stability in both acidic and base media. Furthermore, the overall water splitting performance is tested using W2N/WP/W@NPC as the cathode through a two-electrode electrolyzer, which also exhibits impressive electrochemical performance.

Regenerated Graphite Electrodes with Reconstructed Solid Electrolyte Interface and Enclosed Active Lithium Toward >100% Initial Coulombic Efficiency.

Solid electrolyte interface (SEI) is arguably the most important concern in graphite anodes, which determines their achievable Coulombic efficiency (CE) and cycling stability. In spent graphite anodes, there are already-formed (yet loose and/or broken) SEIs and some residual active lithium, which, if can be inherited in the regenerated electrodes, are highly desired to compensate for the lithium loss due to SEI formation. However, current graphite regenerated approaches easily destroy the thin SEIs and residue active lithium, making their reuse impossible. Herein, this work reports a fast-heating strategy (e.g., 1900 K for ≈150 ms) to upcycle degraded graphite via instantly converting the loose original SEI layer (≈100 nm thick) to a compact and mostly inorganic one (≈10-30 nm thick with a 26X higher Young's Modulus) and still retaining the activity of residual lithium. Thanks to the robust SEI and enclosed active lithium, the regenerated graphite exhibited 104.7% initial CE for half-cell and gifted the full cells with LiFePO4 significantly improved initial CE (98.8% versus 83.2%) and energy density (309.4 versus 281.4 Wh kg-1), as compared with commercial graphite. The as-proposed upcycling strategy turns the "waste" graphite into high-value prelithiated ones, along with significant economic and environmental benefits.

Uniform Al Doping in LiCoO2 for 4.55 V Lithium-Ion Pouch Cells.

As the classic cathode material, lithium cobalt oxide (LiCoO2, LCO) suffers from severe structural and interfacial degradation at voltage >4.5 V, which induces fast capacity decay of the cells. Herein, we adopt a simple and effective method, doping aluminum (Al) cations in precursors, to improve the structural stability of LCO and systematically investigate the effect of Al doping on the electrochemical performances. Doping in precursors rather than bulk particles is beneficial to realize uniform Al ions distribution. Even at 4.5 V charging voltage, the LCO/graphite pouch cells with high Al doping levels (8500 ppm) deliver initial and reversible discharge capacities of 386 and 369 mAh after 500 cycles, respectively. The capacity retention is as high as 95.5%. When the cutoff voltage reaches 4.55 V, the pouch cell maintains 79.0% of the first-cycle discharge capacity after 500 cycles. With optimized electrolyte, the pouch cell realizes 87.3% of the initial discharge capacity after 500 cycles at 45 °C. Moreover, the thermal safety performance of the pouch cells with Al doping is promising. Our work displays an excellent inspiration for developing high-voltage, long-cycle, and safe LCO cathode for commercial lithium-ion batteries.

In Operando Monitoring the Stress Evolution of Silicon Anode Electrodes during Battery Operation via Optical Fiber Sensors.

Silicon (Si) anode has attracted broad attention because of its high theoretical specific capacity and low working potential. However, the severe volumetric changes of Si particles during the lithiation process cause expansion and contraction of the electrodes, which induces a repeatedly repair of solid electrolyte interphase, resulting in an excessive consuming of electrolyte and rapid capacity decay. Clearly known the deformation and stress changing at µÎµ resolution in the Si-based electrode during battery operation provides invaluable information for the battery research and development. Here, an in operando approach is developed to monitor the stress evolution of Si anode electrodes via optical fiber Bragg grating (FBG) sensors. By implanting FBG sensor at specific locations in the pouch cells with different Si anodes, the stress evolution of Si electrodes has been systematically investigated, and Δσ/areal capacity is proposed for stress assessment. The results indicate that the differences in stress evolution are nested in the morphological changes of Si particles and the evolution characteristics of electrode structures. The proposed technique provides a brand-new view for understanding the electrochemical mechanics of Si electrodes during battery operation.

Promoting high-voltage stability through local lattice distortion of halide solid electrolytes.

Stable solid electrolytes are essential to high-safety and high-energy-density lithium batteries, especially for applications with high-voltage cathodes. In such conditions, solid electrolytes may experience severe oxidation, decomposition, and deactivation during charging at high voltages, leading to inadequate cycling performance and even cell failure. Here, we address the high-voltage limitation of halide solid electrolytes by introducing local lattice distortion to confine the distribution of Cl-, which effectively curbs kinetics of their oxidation. The confinement is realized by substituting In with multiple elements in Li3InCl6 to give a high-entropy Li2.75Y0.16Er0.16Yb0.16In0.25Zr0.25Cl6. Meanwhile, the lattice distortion promotes longer Li-Cl bonds, facilitating favorable activation of Li+. Our results show that this high-entropy halide electrolyte boosts the cycle stability of all-solid-state battery by 250% improvement over 500 cycles. In particular, the cell provides a higher discharge capacity of 185 mAh g-1 by increasing the charge cut-off voltage to 4.6 V at a small current rate of 0.2 C, which is more challenging to electrolytes|cathode stability. These findings deepen our understanding of high-entropy materials, advancing their use in energy-related applications.

Sulfur Vacancies and 1T Phase-Rich MoS2 Nanosheets as an Artificial Solid Electrolyte Interphase for 400 Wh kg-1 Lithium Metal Batteries.

Constructing large-area artificial solid electrolyte interphase (SEI) to suppress Li dendrites growth and electrolyte consumption is essential for high-energy-density Li metal batteries (LMBs). Herein, chemically exfoliated ultrathin MoS2 nanosheets (EMoS2) as an artificial SEI are scalable transfer-printed on Li-anode (EMoS2@Li). The EMoS2 with a large amount of sulfur vacancies and 1T phase-rich acts as a lithiophilic interfacial ion-transport skin to reduce the Li nucleation overpotential and regulate Li+ flux. With favorable Young's modulus and homogeneous continuous layered structure, the proposed EMoS2@Li effectively suppresses the growth of Li dendrites and repeat breaking/reforming of the SEI. As a result, the assembled EMoS2@Li||LiFePO4 and EMoS2@Li||LiNi0.8Co0.1Mn0.1O2 batteries demonstrate high-capacity retention of 93.5% and 92% after 1000 cycles and 300 cycles, respectively, at ultrahigh cathode loading of 20 mg cm-2. Ultrasonic transmission technology confirms the admirable ability of EMoS2@Li to inhibit Li dendrites in practical pouch batteries. Remarkably, the Ah-class EMoS2@Li||LiNi0.8Co0.1Mn0.1O2 pouch battery exhibits an energy density of 403 Wh kg-1 over 100 cycles with the low negative/positive capacity ratio of 1.8 and electrolyte/capacity ratio of 2.1 g Ah-1. The strategy of constructing an artificial SEI by sulfur vacancies-rich and 1T phase-rich ultrathin MoS2 nanosheets provides new guidance to realize high-energy-density LMBs with long cycling stability.

Electrolyte Regulation in Stabilizing the Interface of a Cobalt-Free Layered Cathode for 4.8 V High-Voltage Lithium-Ion Batteries.

The cobalt-free layered oxide cathode of LiNi0.65Mn0.35O2 is promising for high-energy-density lithium-ion batteries (LIBs). However, under high-voltage conditions, severe side reactions between the Co-free cathode and electrolyte, as well as grain boundary cracks and pulverization of particles, hinder its practical applications. Herein, an electrolyte regulation strategy is proposed by adding fluoroethylene carbonate (FEC) and LiPO2F2 as electrolyte additives in carbonate-based electrolytes to address the above issues. As a result, a homogeneous and dense organic-inorganic hybrid cathode electrolyte interface (CEI) film is formed on the cathode surface. The CEI film consists of C-F, LiF, Li2CO3, and LixPOyFz species, which is proven to be highly conductive and effective in suppressing structure damage and alleviating the interfacial reactions between the cathode and electrolyte. With such a CEI film, the interfacial stability of the Co-free cathode and the high-voltage cycling performance of Li||LiNi0.65Mn0.35O2 are greatly improved. A reversible capacity of 155.1 mAh g-1 and a capacity retention of 81.3% over 150 cycles are attained at a 4.8 V charge cutoff voltage with the tamed electrolyte, whereas the cell without the additives only retains 76.1% capacity retention. Therefore, our work demonstrates the synergistic effect of FEC and LiPO2F2 in stabilizing the interface of Co-free cathode materials and provides an alternative strategy for the electrolyte design of high-voltage LIBs.

Pentafluoro(phenoxy)cyclotriphosphazene Stabilizes Electrode/Electrolyte Interfaces for Sodium-Ion Pouch Cells of 145 Wh Kg-1.

Sodium-ion batteries are competitive candidates for large-scale energy storage batteries due to the abundant sodium resource. However, the electrode interface in the conventional electrolyte is unstable, deteriorating the cycle life of the cells. Introducing functional electrolyte additives can generate stable electrode interfaces. Here, pentafluoro(phenoxy)cyclotriphosphazene (FPPN) serves as a functional electrolyte additive to stabilize the interfaces of the layered oxide cathode and the hard carbon anode. The fluorine substituting groups and the π-π conjugated ─PN─ structure decrease the lowest unoccupied molecular orbital and increase the highest occupied molecular orbital of FPPN, respectively, realizing the preferential reduction and oxidization of FPPN on the anode and cathode simultaneously, which results in the formation of a uniform, ultrathin, and inorganic-rich solid electrolyte interlayer and cathode electrolyte interphase. The sodium-ion pouch cells of 5 Ah capacity rather than coin cells are assembled to evaluate the effect of FPPN. It can retain a high capacity of 4.46 Ah after 1000 cycles, corresponding to a low decay ratio of 0.01% per cycle. The pouch cell also achieves a high energy density of 145 Wh kg-1 and a wide operating temperature of -20-60 °C. This work can attract more attention to the rational electrolyte design for practical applications.

Air-Stable Li2S Cathodes Enabled by an In Situ-Formed Li+ Conductor for Graphite-Li2S Pouch Cells.

Using Li2S cathodes instead of S cathodes presents an opportunity to pair them with Li-free anodes (e.g., graphite), thereby circumventing anode-related issues, such as poor reversibility and safety, encountered in Li-S batteries. However, the moisture-sensitive nature of Li2S causes the release of hazardous H2S and the formation of insulative by-products, increasing the manufacturing difficulty and adversely affecting cathode performance. Here, Li4SnS4, a Li+ conductor that is air-stable according to the hard-soft acid-base principle, is formed in situ and uniformly on Li2S particles because Li2S itself participates in Li4SnS4 formation. When exposed to air (20% relative humidity), the protective Li4SnS4 layer maintains its components and structure, thus contributing to the enhanced stability of the Li2S@Li4SnS4 composite. In addition, the Li4SnS4 layer can accelerate the sluggish conversion of Li2S because of its favorable interfacial charge transfer, and continuously confine lithium polysulfides owing to its integrity during electrochemical processes. A graphite-Li2S pouch cell containing a Li2S@Li4SnS4 cathode is constructed, which shows stable cyclability with 97% capacity retention after 100 cycles. Hence, combining a desirable air-stable Li2S cathode and a highly reversible Li-free configuration offers potential practical applications of graphite-Li2S full cells.

Interfacial self-healing polymer electrolytes for long-cycle solid-state lithium-sulfur batteries.

Coupling high-capacity cathode and Li-anode with solid-state electrolyte has been demonstrated as an effective strategy for increasing the energy densities and safety of rechargeable batteries. However, the limited ion conductivity, the large interfacial resistance, and unconstrained Li-dendrite growth hinder the application of solid-state Li-metal batteries. Here, a poly(ether-urethane)-based solid-state polymer electrolyte with self-healing capability is designed to reduce the interfacial resistance and provides a high-performance solid-state Li-metal battery. With its dynamic covalent disulfide bonds and hydrogen bonds, the proposed solid-state polymer electrolyte exhibits excellent interfacial self-healing ability and maintains good interfacial contact. Full cells are assembled with the two integrated electrodes/electrolytes. As a result, the Li||Li symmetric cells exhibit stable long-term cycling for more than 6000 h, and the solid-state Li-S battery shows a prolonged cycling life of 700 cycles at 0.3 C. The use of ultrasound imaging technology shows that the interfacial contact of the integrated structure is much better than those of traditional laminated structure. This work provides an interesting interfacial dual-integrated strategy for designing high-performance solid-state Li-metal batteries.

Introducing Electron Buffers into Intermetallic Pt Alloys against Surface Polarization for High-Performing Fuel Cells.

Surface polarization under harsh electrochemical environments usually puts catalysts in a thermodynamically unstable state, which strictly hampers the thermodynamic stability of Pt-based catalysts in high-performance fuel cells. Here, we report a strategy by introducing electron buffers (variable-valence metals, M = Ti, V, Cr, and Nb) into intermetallic Pt alloy nanoparticle catalysts to suppress the surface polarization of Pt shells using the structurally ordered L10-M-PtFe as a proof of concept. Operando X-ray absorption spectra analysis suggests that with the potential increase, electron buffers, especially Cr, could facilitate an electron flow to form a electron-enriched Pt shell and thus weaken the surface polarization and tensile Pt strain. The best-performing L10-Cr-PtFe/C catalyst delivers superb oxygen reduction reaction (ORR) activity (mass activity = 1.41/1.02 A mgPt-1 at 0.9 V, rated power density = 14.0/9.2 W mgPt-1 in H2-air under a total Pt loading of 0.075/0.125 mgPt cm-2, respectively) and stability (20 mV voltage loss at 0.8 A cm-2 after 60,000 cycles of accelerated durability test) in a fuel cell cathode, representing one of the best reported ORR catalysts. Density functional theory calculations reveal that the optimized surface strain by introducing Cr on L10-PtFe/C accounts for the enhanced ORR activity, and the durability enhancement stems from the charge transfer contribution of Cr to the Pt shells and the increased kinetic energy barrier for Pt dissolution/Fe diffusion.

Magnetic Field Enhanced Oxygen Reduction Reaction via Oxygen Diffusion Speedup.

The mass-transfer of oxygen in liquid phases (including in the bulk electrolyte and near the electrode surface) is a critical step to deliver oxygen to catalyst sites (especially immersed catalyst sites) and use the full capacity of oxygen reduction reaction (ORR). Despite the extensive efforts of optimizing the complex three-phase reaction interfaces to enhance the gaseous oxygen transfer, strong limitations remain due to oxygen's poor solubility and slow diffusion in electrolytes. Herein, a magnetic method for boosting the directional hydrodynamic pumping of oxygen toward immersed catalyst sites is demonstrated which allows the ORR to reach otherwise inaccessible catalytic regions where high currents normally would have depleted oxygen. For Pt foil electrodes without forced oxygen saturation in KOH electrolytes, the mass-transfer-limited current densities can be improved by 60% under an external magnetic field of 435 mT due to the synergistic effect between bulk- and surface-magnetohydrodynamic (MHD) flows induced by Lorentz forces. The residual magnetic fields are further used at the surface of magnetic materials (such as CoPt alloys and Pt/FeCo heterostructures) to enhance the surface-MHD effect, which helps to retain part of the ORR enhancement permanently without applying external magnetic fields.

A Tailored Interface Design for Anode-Free Solid-State Batteries.

Anode-free solid-state batteries (AFSSBs) are considered to be one of the most promising high-safety and high-energy storage systems. However, low Coulombic efficiency stemming from severe deterioration on solid electrolyte/current collector (Cu foil) interface and undesirable Li dendrite growth impede their practical application, especially when rigid garnet electrolyte is used. Here, an interfacial engineering strategy between garnet electrolyte and Cu foil is introduced for stable and highly efficient AFSSBs. By utilizing the high Li ion conductivity of LiC6 layer, interfacial self-adaption ability arising from ductile lithiated polyacrylic acid polymer layer and regulated Li deposition via Li-Ag alloying reaction, the garnet-based AFSSB delivers a stable long-term operation. Additionally, when combined with a commercial LiCoO2 cathode (3.1 mAh cm-2 ), the cell also exhibits an outstanding capacity retention due to the tailored interface design. The strategies for novel AFSSBs architecture thus offer an alternative route to design next-generation batteries with high safety and high density.

High Chaos Induced Multiple-Anion-Rich Solvation Structure Enabling Ultrahigh Voltage and Wide Temperature Lithium-Metal Batteries.

The optimal electrolyte for ultrahigh energy density (>400 Wh/kg) lithium-metal batteries with a LiNi0.8Co0.1Mn0.1O2 cathode is required to withstand high voltage (≥4.7 V) and be adaptable over a wide temperature range. However, the battery performance is degraded by aggressive electrode-electrolyte reactions at high temperature and high voltage, while excessive growth of lithium dendrites usually occurs due to poor kinetics at low temperature. Accordingly, the development of electrolytes has encountered challenges in that there is almost no electrolyte simultaneously meeting the above requirements. Herein, a high chaos electrolyte design strategy is proposed, which promotes the formation of weak solvation structures involving multiple anions. By tailoring a Li+-EMC-DMC-DFOB--PO2F2--PF6- multiple-anion-rich solvation sheath, a robust inorganic-rich interphase is obtained for the electrode-electrolyte interphase (EEI), which is resistant to the intense interfacial reactions at high voltage (4.7 V) and high temperature (45 °C). In addition, the Li+ solvation is weakened by the multiple-anion solvation structure, which is a benefit to Li+ desolventization at low temperature (-30 °C), greatly improving the charge transfer kinetics and inhibiting the lithium dendrite growth. This work provides an innovative strategy to manipulate the high chaos electrolyte to further optimize solvation chemistry for high voltage and wide temperature applications.

Prescription pattern and effectiveness of antihypertensive drugs in patients with aortic dissection who underwent surgery.

Background: Surgical patients with aortic dissection often require multiple antihypertensive drugs to control blood pressure. However, the prescription pattern and effectiveness of antihypertensive drugs for these patients are unclear. We aimed to investigate the prescription pattern and effectiveness of different classes of antihypertensive drugs in surgical patients with aortic dissection. Methods: Newly diagnosed aortic dissection patients who underwent surgery, aged >20 years, from 1 January 2012 to 31 December 2017 were identified. Patients with missing data, in-hospital mortality, aortic aneurysms, or congenital connective tissue disorders, such as Marfan syndrome, were excluded. Prescription patterns of antihypertensive drugs were identified from medical records of outpatient visits within 90 days after discharge. Antihypertensive drugs were classified into four classes: 1) ß-blockers, 2) calcium channel blockers (CCBs), 3) renin-angiotensin system, and 4) other antihypertensive drugs. Patients were classified according to the number of classes of antihypertensive drugs as follows: 1) class 0, no exposure to antihypertensive drugs; 2) class 1, antihypertensive drugs of the same class; 3) class 2, antihypertensive drugs of two classes; 4) class 3, antihypertensive drugs of three classes; or 5) class 4, antihypertensive drugs of four classes. The primary composite outcomes included rehospitalization associated with aortic dissection, death due to aortic dissection, and all-cause mortality. Results: Most patients were prescribed two (28.87%) or three classes (28.01%) of antihypertensive drugs. In class 1, ß-blockers were most commonly used (8.79%), followed by CCBs (5.95%). In class 2, ß-blockers+CCB (10.66%) and CCB+RAS (5.18%) were the most common drug combinations. In class 3, ß-blockers + CCB+RAS (14.84%) was the most prescribed combination. Class 0 had a significantly higher hazard of the composite outcome (HR, 2.1; CI, 1.46-3.02; p < 0.001) and all-cause mortality (HR, 2.34; CI, 1.56-3.51; p < 0.001) than class 1. There were no significant differences in hazards for rehospitalization associated with aortic dissection among classes. Conclusion: Among operated patients with type A aortic dissection, no specific type of antihypertensive drug was associated with a better outcome, whereas among those with type B aortic dissection, the use of ß-blockers and CCBs was related to a significantly lower risk of the composite outcome.