A Layered Organic Cathode for High-Energy, Fast-Charging, and Long-Lasting Li-Ion Batteries.

Eliminating the use of critical metals in cathode materials can accelerate global adoption of rechargeable lithium-ion batteries. Organic cathode materials, derived entirely from earth-abundant elements, are in principle ideal alternatives but have not yet challenged inorganic cathodes due to poor conductivity, low practical storage capacity, or poor cyclability. Here, we describe a layered organic electrode material whose high electrical conductivity, high storage capacity, and complete insolubility enable reversible intercalation of Li+ ions, allowing it to compete at the electrode level, in all relevant metrics, with inorganic-based lithium-ion battery cathodes. Our optimized cathode stores 306 mAh g-1cathode, delivers an energy density of 765 Wh kg-1cathode, higher than most cobalt-based cathodes, and can charge-discharge in as little as 6 min. These results demonstrate the operational competitiveness of sustainable organic electrode materials in practical batteries.

Electrochemical Capacitance Traces with Interlayer Spacing in Two-dimensional Conductive Metal-Organic Frameworks.

Electrically conductive metal-organic frameworks (MOFs) are promising candidates for electrochemical capacitors (EC) for fast energy storage due to their high specific surface areas and potential for redox activity. To maximize energy density, traditional inorganic pseudocapacitors have utilized faradaic processes in addition to double-layer capacitance. Although conductive MOFs are usually comprised of redox active ligands which allow faradaic reactions upon electrochemical polarization, systematic studies providing deeper understanding of the charge storage processes and structure-function relationships have been scarce. Here, we investigate the charge storage mechanisms of a series of triazatruxene-based 2D layered conductive MOFs with variable alkyl functional groups, Ni3(HIR3-TAT)2 (TAT=triazatruxene; R=H, Et, n-Bu, n-Pent). Functionalization of the triazatruxene core allows for systematic variation of structural parameters while maintaining in-plane conjugation between ligands and metals. Specifically, R groups modulate interlayer spacing, which in turn shifts the charge storage mechanism from double-layer capacitance towards pseudocapacitance, leading to an increase in molar specific capacitance from Ni3(HIH3-TAT)2 to Ni3(HIBu3-TAT)2. Partial exfoliation of Ni3(HIBu3-TAT)2 renders redox active ligand moieties more accessible, and thus increases the dominance of faradaic processes. Our strategy of controlling charge storage mechanism through tuning the accessibility of redox-active sites may motivate further design and engineering of electrode materials for EC.

A dicarbonate solvent electrolyte for high performance 5 V-Class Lithium-based batteries.

Rechargeable lithium batteries using 5 V positive electrode materials can deliver considerably higher energy density as compared to state-of-the-art lithium-ion batteries. However, their development remains plagued by the lack of electrolytes with concurrent anodic stability and Li metal compatibility. Here we report a new electrolyte based on dimethyl 2,5-dioxahexanedioate solvent for 5 V-class batteries. Benefiting from the particular chemical structure, weak interaction with lithium cation and resultant peculiar solvation structure, the resulting electrolyte not only enables stable, dendrite-free lithium plating-stripping, but also displays anodic stability up to 5.2 V (vs. Li/Li+), in additive or co-solvent-free formulation, and at low salt concentration of 1 M. Consequently, the Li | |LiNi0.5Mn1.5O4 cells using the 1 M LiPF6 in 2,5-dioxahexanedioate based electrolyte retain >97% of the initial capacity after 250 cycles, outperforming the conventional carbonate-based electrolyte formulations, making this, and potentially other dicarbonate solvents promising for future Lithium-based battery practical explorations.

Towards the 4 V-class n-type organic lithium-ion positive electrode materials: the case of conjugated triflimides and cyanamides.

Organic electrode materials have garnered a great deal of interest owing to their sustainability, cost-efficiency, and design flexibility metrics. Despite numerous endeavors to fine-tune their redox potential, the pool of organic positive electrode materials with a redox potential above 3 V versus Li+/Li0, and maintaining air stability in the Li-reservoir configuration remains limited. This study expands the chemical landscape of organic Li-ion positive electrode chemistries towards the 4 V-class through molecular design based on electron density depletion within the redox center via the mesomeric effect of electron-withdrawing groups (EWGs). This results in the development of novel families of conjugated triflimides and cyanamides as high-voltage electrode materials for organic lithium-ion batteries. These are found to exhibit ambient air stability and demonstrate reversible electrochemistry with redox potentials spanning the range of 3.1 V to 3.8 V (versus Li+/Li0), marking the highest reported values so far within the realm of n-type organic chemistries. Through comprehensive structural analysis and extensive electrochemical studies, we elucidate the relationship between the molecular structure and the ability to fine-tune the redox potential. These findings offer promising opportunities to customize the redox properties of organic electrodes, bridging the gap with their inorganic counterparts for application in sustainable and eco-friendly electrochemical energy storage devices.

Bimetallic Anionic Organic Frameworks with Solid-State Cation Conduction for Charge Storage Applications.

A new phosphonate-based anionic bimetallic organic framework, with the general formula of A4 -Zn-DOBDP (wherein A is Li+ or Na+ , and DOBDP6- is the 2,5-dioxido-1,4-benzenediphosphate ligand) is prepared and characterized for energy storage applications. With four alkali cations per formula unit, the A4 -Zn-DOBDP MOF is found to be the first example of non-solvated cation conducting MOF with measured conductivities of 5.4×10-8  S cm-1 and 3.4×10-8  S cm-1 for Li4 - and Na4 - phases, indicating phase and composition effects of Li+ and Na+ shuttling through the channels. Three orders of magnitude increase in ionic conductivity is further attained upon solvation with propylene carbonate, placing this system among the best MOF ionic conductors at room temperature. As positive electrode material, Li4 -Zn-DOBDP delivers a specific capacity of 140 mAh g-1 at a high average discharge potential of 3.2 V (vs. Li+ /Li) with 90 % of capacity retention over 100 cycles. The significance of this research extends from the development of a new family of electroactive phosphonate-based MOFs with inherent ionic conductivity and reversible cation storage, to providing elementary insights into the development of highly sought yet still evasive MOFs with mixed-ion and electron conduction for energy storage applications.

Comparison between multimodality imaging approaches for measurement of the tricuspid annulus in severe tricuspid regurgitation.

BACKGROUND: Tricuspid valve (TV) sizing is crucial for surgical or interventional procedures planning. Imaging TV is frequently challenging and often requires multimodal imaging techniques. Computed tomography (CT) is the gold standard for sizing. The authors compared measurements of the tricuspid annulus (TA) acquired using echocardiography and CT. METHODS: Thirty-six patients with severe symptomatic tricuspid regurgitation were included in this retrospective analysis. During mid-diastole, the maximal two-dimensional (2D) TA diameter was directly measured in multiple views using transthoracic echocardiography (TTE) and transesophageal echocardiography (TEE). Three-dimensional (3D) TA size was assessed using cross-sectional long-axis and short-axis diameters, areas, and perimeters measured in the projected plane. The TA diameter was quantified by the perimeter measured on the CT images (CT imaging_indirect) and compared with echocardiography measurements. Tenting height and tenting area were also measured using TTE at mid systole. RESULTS: The long-axis dimensions measured using 3DTEE (3DTEE_direct) best correlated with the TA diameter (CT imaging_indirect) (R = 0.851, P = 0.0001) and the least discrepancies (difference 1.2 ± 2.4 mm, P = 0.012). The TA diameters quantified by the perimeters measured using 3DTEE (3DTEE_indirect) were smaller than the CT values (difference 2.5 ± 2.5 mm, P = 0.0001). The maximal dimensions directly measured by 2DTEE (2DTEE_direct) were modestly correlated with the CT values. Overall, the maximal dimensions by TTE_direct were less reliable than those by CT. TA eccentricity index correlated with the maximal tenting height and area. CONCLUSION: The patients with severe tricuspid regurgitation had a dilated and circular annulus. The long-axis TA dimensions (3DTEE_direct) were similar to the diameters (CT imaging_indirect).

Revealing the reversible solid-state electrochemistry of lithium-containing conjugated oximates for organic batteries.

In the rising advent of organic Li-ion positive electrode materials with increased energy content, chemistries with high redox potential and intrinsic oxidation stability remain a challenge. Here, we report the solid-phase reversible electrochemistry of the oximate organic redox functionality. The disclosed oximate chemistries, including cyclic, acyclic, aliphatic, and tetra-functional stereotypes, uncover the complex interplay between the molecular structure and the electroactivity. Among the exotic features, the most appealing one is the reversible electrochemical polymerization accompanying the charge storage process in solid phase, through intermolecular azodioxy bond coupling. The best-performing oximate delivers a high reversible capacity of 350 mAh g-1 at an average potential of 3.0 versus Li+/Li0, attaining 1 kWh kg-1 specific energy content at the material level metric. This work ascertains a strong link between electrochemistry, organic chemistry, and battery science by emphasizing on how different phases, mechanisms, and performances can be accessed using a single chemical functionality.

High performance Li-, Na-, and K-ion storage in electrically conducting coordination polymers.

Coordination polymers (CPs) made of redox-active organic moieties and metal ions emerge as an important class of electroactive materials for battery applications. However, the design and synthesis of high voltage alkali-cation reservoir anionic CPs remains challenging, hindering their practical applications. Herein, we report a family of electrically conducting alkali-cation reservoir CPs with the general formula of A2-TM-PTtSA (wherein A = Li+, Na+, or K+; TM = Fe2+, Co2+, or Mn2+; and PTtSA = benzene-1,2,4,5-tetra-methylsulfonamide). The incorporation of transition metal centers not only enables intrinsic high electrical conductivity, but also shows an impressive redox potential increase of as high as 1 V as compared to A4-PTtSA analogues, resulting in a class of organometallic cathode materials with a high average redox potential of 2.95-3.25 V for Li-, Na- and K-ion batteries. A detailed structure - composition - physicochemical properties - performance correlation study is provided relying on experimental and computational analysis. The best performing candidate shows excellent rate capability (86% of the nominal capacity retained at 10C rate), remarkable cycling stability (96.5% after 1000 cycles), outstanding tolerance to low carbon content (5 wt%), high mass loading (50 mg cm-2), and extreme utilisation conditions of low earth orbit space environment tests. The significance of the disclosed alkali-ion reservoir cathodes is further emphasized by utilizing conventional Li-host graphite anode for full cell assembly, attaining a record voltage of 3 V in an organic cathode Li-ion proof-of-concept cell.

New Cathode Materials in the Fe-PO4 -F Chemical Space for High-Performance Sodium-Ion Storage.

Sodium and iron make up the perfect combination for the growing demand for sustainable energy storage systems, given the natural abundance and sustainability of the two building block elements. However, most sodium-iron electrode chemistries are plagued by intrinsic low energy densities with continuous ongoing efforts to solve this. Herein, the chemical space of a series of (meta)stable, off-stoichiometric Fe-PO4 -F phases is analyzed. Some are found to display markedly improved electrochemical activity for sodium storage, as compared to the amorphous or thermodynamically stable phases of equivalent composition. The metastable crystalline Na1.2 Fe1.2 PO4 F0.6 delivers a reversible capacity of more than 140 mAh g-1 with an average discharge potential of 2.9 V (vs Na+ /Na0 ) resulting in a practical specific energy density of 400 Wh kg-1 (estimated at the material level), outperforming many developed Fe-PO4 analogs thus far, with further multiple possibilities to be explored toward improved energy storage metrics. Overall, this study unlocks the possibilities of off-stoichiometric Fe-PO4 -F cathode materials and reveals the importance to explore the oft-overlooked metastable or transient state materials for energy storage.

The feasibility and safety of "one-stop" left atrial appendage closure and percutaneous coronary intervention in atrial fibrillation patients with significant coronary artery disease (PCI-LAAC study).

BACKGROUND: The anti-thrombotic strategy for patients with atrial fibrillation (AF) who have undergone percutaneous coronary intervention (PCI) for coronary artery disease (CAD) is a common and difficult challenge. This pilot study aimed to assess the feasibility and safety of "one-stop" left atrial appendage closure (LAAC) combined with PCI as an alternative stroke prophylaxis strategy. METHODS: From March 2017 to October 2019, AF patients with elevated bleeding risk and significant stable CAD requiring PCI were recruited to undergo LAAC as alternative stroke prophylaxis in Fuwai Hospital, Beijing, China. LAAC was performed either in the same setting with PCI (i.e. "one-stop" LAAC/PCI), or as staged procedure after PCI. Dual antiplatelet therapy was given for all patients after LAAC. Peri-procedural and intermediate-term clinical outcomes were assessed through hospital clinical records review and standardized telephone interviews. RESULTS: A total of 24 patients were recruited including 13 (54.2%) underwent stage procedure and 11 (45.8%) underwent "one-stop" procedure respectively. The mean CHA2DS2-VASc and HAS-BLED scores were 4.5±1.4 and 3 (IQR 3,4) respectively. Six patients (46.1%) in the staged procedure cohort were treated with triple anti-thrombotic following PCI, with 2 developed minor bleeding before LAAC. One patient ("one-stop" cohort) had gastrointestinal bleeding 1 day after procedure. Otherwise, there was no device related complication or peri-procedural stroke/myocardial infarction. After a mean 19±5.4 months follow-up, there was no death, myocardial infarction, stroke and systemic embolization detected. CONCLUSIONS: In this pilot study, "one-stop" LAAC with PCI was shown to be efficacious with no stroke, MI, VARC-2 major bleeding or CV death reported over a mean follow-up of 19 months, and safe with no major peri-procedural bleeding or device related complications.

High Salt-Content Plasticized Flame-Retardant Polymer Electrolytes.

New solid polymer electrolytes are of particular interest for next-generation high-energy batteries since they can overcome the limited voltage window of conventional polyether-based electrolytes. Herein, a flame-retardant phosphorus-containing polymer, poly(dimethyl(methacryloyloxy)methyl phosphonate) (PMAPC1) is introduced as a promising polymer matrix. Free-standing membranes are easily obtained by mixing PMAPC1 with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and a small amount of acetonitrile (AN). LiTFSI/AN mixed aggregates are formed that act as plasticizers and enable ionic conductivities up to 1.6 × 10-3 S cm-1 at 100 °C. The high content of LiTFSI used in our electrolytes leads to the formation of a stable LiF solid-electrolyte interphase, which can effectively suppress Li dendrites and the chemical degradation of AN in contact with Li. Accordingly the electrolyte membranes exhibit a wide electrochemical stability window above 4.7 V versus Li+/Li and fire-retardant properties due to the presence of the phosphorus-containing polymer. Atomistic molecular modeling simulations have been performed to determine the structure of the electrolytes on the microscopic scale and to rationalize the trends in ionic conductivity and the transport regime as a function of the electrolyte composition. Finally, our electrolyte membranes enable stable cycling performance for LiFePO4|PMAPC1 + LiTFSI + AN|Li batteries.

An Electrically Conducting Li-Ion Metal-Organic Framework.

Metal-organic frameworks (MOFs) have emerged as an important, yet highly challenging class of electrochemical energy storage materials. The chemical principles for electroactive MOFs remain, however, poorly explored because precise chemical and structural control is mandatory. For instance, no anionic MOF with a lithium cation reservoir and reversible redox (like a conventional Li-ion cathode) has been synthesized to date. Herein, we report on electrically conducting Li-ion MOF cathodes with the generic formula Li2-M-DOBDC (wherein M = Mg2+ or Mn2+; DOBDC4- = 2,5-dioxido-1,4-benzenedicarboxylate), by rational control of the ligand to transition metal stoichiometry and secondary building unit (SBU) topology in the archetypal CPO-27. The accurate chemical and structural changes not only enable reversible redox but also induce a million-fold electrical conductivity increase by virtue of efficient electronic self-exchange facilitated by mix-in redox: 10-7 S/cm for Li2-Mn-DOBDC vs 10-13 S/cm for the isoreticular H2-Mn-DOBDC and Li2-Mg-DOBDC, or the Mn-CPO-27 compositional analogues. This particular SBU topology also considerably augments the redox potential of the DOBDC4- linker (from 2.4 V up to 3.2 V, vs Li+/Li0), a highly practical feature for Li-ion battery assembly and energy evaluation. As a particular cathode material, Li2-Mn-DOBDC displays an average discharge potential of 3.2 V vs Li+/Li0, demonstrates excellent capacity retention over 100 cycles, while also handling fast cycling rates, inherent to the intrinsic electronic conductivity. The Li2-M-DOBDC material validates the concept of reversible redox activity and electronic conductivity in MOFs by accommodating the ligand's noncoordinating redox center through composition and SBU design.

Conjugated sulfonamides as a class of organic lithium-ion positive electrodes.

The applicability of organic battery materials in conventional rocking-chair lithium (Li)-ion cells remains deeply challenged by the lack of Li-containing and air-stable organic positive electrode chemistries. Decades of experimental and theoretical research in the field has resulted in only a few recent examples of Li-reservoir materials, all of which rely on the archetypal conjugated carbonyl redox chemistry. Here we extend the chemical space of organic Li-ion positive electrode materials with a class of conjugated sulfonamides (CSAs) and show that the electron delocalization on the sulfonyl groups endows the resulting CSAs with intrinsic oxidation and hydrolysis resistance when handled in ambient air, and yet display reversible electrochemistry for charge storage. The formal redox potential of the uncovered CSA chemistries spans a wide range between 2.85 V and 3.45 V (versus Li+/Li0), finely tunable through electrostatic or inductive molecular design. This class of organic Li-ion positive electrode materials challenges the realm of the inorganic battery cathode, as this first generation of CSA chemistries already displays gravimetric energy storage metrics comparable to those of the stereotypical LiFePO4.

Mixed Anionic and Cationic Redox Chemistry in a Tetrathiomolybdate Amorphous Coordination Framework.

We report the electrochemistry of a hitherto unexplored Na2 MoS4 phase as a conversion electrode material for Na- and Li-ion batteries. The material adopts an amorphous coordination polymer structure with mixed Mo and S valences. XPS and XRD analysis reveal a complex interplay between Mo and S redox chemistry, while excluding the formation of free sulfur, lithium sulfide, or other crystalline phases. Na2 MoS4 behaves as a mixed ionic-electronic conductor, with electronic conductivity of 6.1×10-4  S cm-1 , that permits carbon-free application in an electrochemical cell. A reversible capacity of up to 500 mAh g-1 was attained, corresponding to a five-electron redox exchange, with species ranging from (highest oxidized state) to 5 MoS4 > (lowest oxidized state). This study emphasizes the excellent charge-storage performances of Na2 MoS4 for Li- or Na-ion batteries, and enriches the emerging library and knowledge of sulfide phases with mixed anionic and cationic redox properties.

Validation of methods for effective orifice area measurement of prosthetic valves by two-dimensional and Doppler echocardiography following transcatheter self-expanding aortic valve implantation.

BACKGROUND: The effective orifice area (EOA) is utilized to characterize the hemodynamic performance of the transcatheter heart valve (THV). However, there is no consensus on EOA measurement of self-expanding THV. We aimed to compare two echocardiographic methods for EOA measurement following transcatheter self-expanding aortic valve implantation. METHODS: EOA was calculated according to the continuity equation. Two methods were constructed. In Method 1 and Method 2, the left ventricular outflow tract diameter (LVOTd) was measured at the entry of the prosthesis (from trailing-to-leading edge) and proximal to the prosthetic valve leaflets (from trailing-to- leading edge), respectively. The velocity-time integral (VTI) of the LVOT (VTILVOT) was recorded by pulsed-wave Doppler (PW) from apical windows. The region of the PW sampling should match that of the LVOTd measurement with precise localization. The mean transvalvular pressure gradient (MG) and VTI of THV was measured by Continuous wave Doppler. RESULTS: A total of 113 consecutive patients were recruited. The mean age was 77.2 ± 5.5 years, and 72 patients (63.7%) were male. EOA1 with the use of Method 1 was larger than EOA2 (1.56 ± 0.39 cm2 vs. 1.48 ± 0.41 cm2, P = 0.001). MG correlated better with the indexed EOA1 (EOAI1) (r = -0.701, P < 0.001) than EOAI2 (r = -0.645, P < 0.001). According to EOAI (EOAI ≤ 0.65 cm2/m2, respectively), the proportion of sever prosthesis-patient mismatch with the use of EOA1 was lower than EOA2 (12.4% vs. 21.2%, P < 0.05). Compared with EOA2, EOA1 had lower interobserver and intra-observer variability (intra: 0.5% ± 17% vs. 3.8% ± 22%, P < 0.001; inter: 1.0% ± 9% vs. 3.5% ± 11%, P < 0.001). CONCLUSIONS: For transcatheter self-expanding valve EOA measurement, LVOTd should be measured in the entry of the prosthesis stent (from trailing-to-leading edge), and VTILVOT should match that of the LVOTd measurement with precise localization.

Transoesophageal echocardiography prior to catheter ablation could be avoided in atrial fibrillation patients with a low risk of stroke and without filling defects in the late-phase MDCT scan: A retrospective analysis of 783 patients.

OBJECTIVES: To test whether multidetector computed tomography (MDCT) could completely replace transoesophageal echocardiography (TEE) to detect left atrial appendage (LAA) thrombi in atrial fibrillation (AF) patients using a large sample size. METHODS: 783 patients with AF who underwent MDCT and TEE before catheter ablation were retrospectively included. Demographic data were obtained. Two radiologists blinded to clinical data made the imaging diagnosis. RESULTS: Most of the patients (96.2 %) had a CHA2DS2-VASc score (congestive heart failure, hypertension, age ≥ 75 years old (doubled), diabetes, stroke/transient ischaemic attack/thromboembolism (doubled), vascular disease, age 65-74 years, female sex) ≤ 3. Eight thrombi were identified by TEE, all of which were detected by MDCT; no thrombus was observed with TEE without the observation of filling defects by late-phase MDCT scanning in any of the patients. Using TEE as reference standard, the sensitivity, specificity, positive predictive value and negative predictive value of MDCT for thrombus detection were 100 %, 95.74 % (95 % CI 94.33 %-97.15 %), 19.51 % (95 % CI 16.73 %-22.29 %) and 100 %, respectively. CONCLUSIONS: For AF patients with low risk of stroke, when MDCT images showed no filling defect in the late phase, TEE prior to catheter ablation can be avoided. KEY POINTS: • MDCT can help detect the presence of LAA thrombus. • TEE can be avoided when late-phase MDCT shows no filling defect. • TEE is required in patients whose MDCT images indicate thrombus.

The Effect of Thermal Exfoliation Temperature on the Structure and Supercapacitive Performance of Graphene Nanosheets.

Graphene nanosheets (GSs) were prepared from graphite oxide by thermal exfoliation method. The effect of thermal exfoliation temperature on the structure and supercapacitive performance of GSs has been investigated. The results show that the GSs with pore sizes center around 4.0 nm. With an increase of thermal reduction temperature, the number of stacking layers and the structure disorder degree increase, while the oxygen-containing groups content, BET surface area, and electrical resistivity of GSs decrease. The results indicate that 673 K is the preferable thermal exfoliation temperature to acquire good supercapacitive performance. In this case, the GSs have the best supercapacitive performance (233.1 F g-1) in a 6 mol L-1 KOH electrolyte. The prepared GSs at the preferable thermal exfoliation temperature have good rate performance and cycle stability.

Detection of Hepatitis B virus in serum and liver of chickens.

Hepatitis B virus (HBV) is one of the most important human pathogens. Its existence in food animals could present a significant threat to public health. The objective of this study was to determine if HBV is present in serum and liver of chickens. A total of 129 serum samples from broiler chickens were collected for the detection of HBV antigens and antibodies, and 193 liver samples were tested for HBV DNA sequence by PCR and for the existence of HBV antigens by immunohistochemistry. The overall prevalence of HBsAg, anti-HBs, anti-HBc was 28.68%, 53.49%, 17.05%, respectively, whereas HBeAg, anti-HBe were barely detectable. Three serum samples were found to be positive for both HBsAg and HBeAg. Further analysis of these samples with transmission electron microscopy (TEM) revealed two morphologic particles with 20 nm and 40 nm in diameter, which were similar to small spherical and Danes particles of HBV. The viral DNA sequence identified in two of the chicken livers shared 92.2% of one known HBV strain and 97.9% nucleotide sequence of another HBV strain. Our results showed the existence of HBV in chickens. This would present a significant risk to people who work with live chickens or chicken products if HBV found in chicken could be confirmed to be the same as human HBV.