Strain induced electrochemical behaviors of ionic liquid electrolytes in an electrochemical double layer capacitor: Insights from molecular dynamics simulations.

Electrochemical Double Layer Capacitors (EDLCs) with ionic liquid electrolytes outperform conventional ones using aqueous and organic electrolytes in energy density and safety. However, understanding the electrochemical behaviors of ionic liquid electrolytes under compressive/tensile strain is essential for the design of flexible EDLCs as well as normal EDLCs, which are subject to external forces during assembly. Despite many experimental studies, the compression/stretching effects on the performance of ionic liquid EDLCs remain inconclusive and controversial. In addition, there is hardly any evidence of prior theoretical work done in this area, which makes the literature on this topic scarce. Herein, for the first time, we developed an atomistic model to study the processes underlying the electrochemical behaviors of ionic liquids in an EDLC under strain. Constant potential non-equilibrium molecular dynamics simulations are conducted for EMIM BF4 placed between two graphene walls as electrodes. Compared to zero strain, low compression of the EDLC resulted in compromised performance as the electrode charge density dropped by 29%, and the performance reduction deteriorated significantly with a further increase in compression. In contrast, stretching is found to enhance the performance by increasing the charge storage in the electrodes by 7%. The performance changes with compression and stretching are due to changes in the double-layer structure. In addition, an increase in the value of the applied potential during the application of strain leads to capacity retention with compression revealed by the newly performed simulations.

Exploring the Dynamic Role of Bacterial Etiology in Complicated Urinary Tract Infections.

Background and Objectives. Numerous studies have been conducted to explore the epidemiological characteristics of urinary tract infections (UTI) and sepsis. However, there is still a lack of relevant bacteriological features and prognostic information regarding urosepsis based on bacteriological etiology. The current study aims to evaluate the bacterial etiology of complicated UTI (cUTI) and bacterial resistance to antibiotics and whether they present an intrinsic risk of developing urosepsis. Materials and Methods. A retrospective study was performed that included 102 patients who were diagnosed with cUTI and admitted to the urology department of the "Sfântul Apostol Andrei" County Emergency Clinical Hospital (GCH) from September 2019 to May 2022. Results. A considerable number of patients, n = 41 (40.2%), were diagnosed with multi drug-resistant (MDR) infection. Escherichia coli (E. coli) was identified as the prevailing pathogen, accounting for 51 patients. Klebsiella manifested itself as the subsequent causative agent in 27 instances. The presence of Enterococcus spp. infection was documented in 13 patients, whereas Pseudomonas emerged as the etiological perpetrator in the clinical context of 8 patients. The current study found a substantial prevalence of resistance to first-line antibiotics. The overall resistance rate was 74.5% for penicillin, 58.82% for trimethoprim-sulfamethoxazole and 49% for fluoroquinolones; cephalosporin resistance displayed an inverse correlation with antibiotic generation with fourth-generation cephalosporins exhibiting a resistance rate of 24.5%, and first-generation cephalosporins demonstrating a resistance rate of 35.29%. Conclusions. Age, comorbidities and indwelling urinary catheters are risk factors for developing MDR infections. While the intrinsic characteristics of the causative bacterial agent in cUTI may not be a risk factor for developing urosepsis, they can contribute to increased mortality risk. For empiric antibiotic treatment in patients with cUTI who are at a high risk of developing urosepsis and experiencing a potentially unfavorable clinical course, broad-spectrum antibiotic therapy is recommended. This may include antibiotics, such as amikacin, tigecycline, carbapenems and piperacillin-tazobactam.

The Role of Biomarkers and Scores in Describing Urosepsis.

Background and Objectives: Patients with urinary tract obstruction (UTO) and systemic inflammatory response syndrome (SIRS) are at risk of developing urosepsis, whose evolution involves increased morbidity, mortality and cost. The aim of this study is to evaluate the ability of already existing scores and biomarkers to diagnose, describe the clinical status, and predict the evolution of patients with complicated urinary tract infection (UTI) and their risk of progressing to urosepsis. Materials and Methods: We conducted a retrospective study including patients diagnosed with UTI hospitalized in the urology department of" Sfântul Apostol Andrei" County Emergency Clinical Hospital (GCH) in Galati, Romania, from September 2019 to May 2022. The inclusion criteria were: UTI proven by urine culture or diagnosed clinically complicated with UTO, fever or shaking chills, and purulent collections, such as psoas abscess, Fournier Syndrome, renal abscess, and paraurethral abscess, showing SIRS. The exclusion criteria were: patients age < 18 years, pregnancy, history of kidney transplantation, hemodialysis or peritoneal dialysis, and patients with missing data. We used the Sequential (Sepsis-Related) Organ Failure Assessment (SOFA) and qSOFA (quick SOFA) scores, and procalcitonin (PCT) to describe the clinical status of the patients. The Charlson Comorbidity Index (CCI) was used to assesses pre-existing morbidities. The hospitalization days and costs and the days of intensive care were considered. Depending on the diagnosis at admission, we divided the patients into three groups: SIRS, sepsis and septic shock. The fourth group was represented by patients who died during hospitalization. Results: A total of 174 patients with complicated UTIs were enrolled in this study. From this total, 46 were enrolled in the SIRS group, 88 in the urosepsis group, and 40 in the septic shock group. A total of 23 patients died during hospitalization and were enrolled in the deceased group. An upward trend of age along with worsening symptoms was highlighted with an average of 56.86 years in the case of SIRS, 60.37 years in the sepsis group, 69.03 years in the septic shock, and 71.04 years in the case of deceased patients (p < 0.04). A statistically significant association between PCT and complex scores (SOFA, CCI and qSOFA) with the evolution of urosepsis was highlighted. Increased hospitalization costs can be observed in the case of deceased patients and those with septic shock and statistically significantly lower in the case of those with SIRS. The predictability of discriminating urosepsis stages was assessed by using the area under the ROC curve (AUC) and very good specificity and sensitivity was identified in predicting the risk of death for PCT (69.57%, 77.33%), the SOFA (91.33%, 76.82%), qSOFA (91.30%, 74.17%) scores, and CCI (65.22%, 88.74%). The AUC value was best for qSOFA (90.3%). For the SIRS group, the PCT (specificity 91.30%, sensitivity 85.71%) and SOFA (specificity 84.78%, sensitivity 78.74%), qSOFA scores (specificity 84.78%, sensitivity 76, 34%) proved to be relevant in establishing the diagnosis. In the case of the septic shock group, the qSOFA (specificity 92.5%, sensitivity 82.71%) and SOFA (specificity 97.5%, sensitivity 77.44%) as well as PCT (specificity 80%, sensitivity 85.61%) are statistically significant disease-defining variables. An important deficit in the tools needed to classify patients into the sepsis group is obvious. All the variables have an increased specificity but a low sensitivity. This translates into a risk of a false negative diagnosis. Conclusions: Although SOFA and qSOFA scores adequately describe patients with septic shock and they are independent prognostic predictors of mortality, they fail to be accurate in diagnosing sepsis. These scores should not replace the conventional triage protocol. In our study, PCT proved to be a disease-defining marker and an independent prognostic predictor of mortality. Patients with important comorbidities, CCI greater than 10, should be treated more aggressively because of increased mortality.

Lithium-ion battery degradation: how to model it.

Predicting lithium-ion battery degradation is worth billions to the global automotive, aviation and energy storage industries, to improve performance and safety and reduce warranty liabilities. However, very few published models of battery degradation explicitly consider the interactions between more than two degradation mechanisms, and none do so within a single electrode. In this paper, the first published attempt to directly couple more than two degradation mechanisms in the negative electrode is reported. The results are used to map different pathways through the complicated path dependent and non-linear degradation space. Four degradation mechanisms are coupled in PyBaMM, an open source modelling environment uniquely developed to allow new physics to be implemented and explored quickly and easily. Crucially it is possible to see 'inside the model and observe the consequences of the different patterns of degradation, such as loss of lithium inventory and loss of active material. For the same cell, five different pathways that can result in end-of-life have already been found, depending on how the cell is used. Such information would enable a product designer to either extend life or predict life based upon the usage pattern. However, parameterization of the degradation models remains as a major challenge, and requires the attention of the international battery community.

Mechanical behaviour of inorganic solid-state batteries: can we model the ionic mobility in the electrolyte with Nernst-Einstein's relation?

Inorganic solid-state lithium-metal batteries could be the next-generation batteries owing to their non-flammability and higher specific energy density. Many research efforts have been devoted to improving the ionic conductivity of inorganic solid electrolytes. For a wide range of electrolytes including liquid and solid polymer electrolytes, an independent measurement or calculation of both electrolyte conductivity and diffusion coefficient is often time-consuming and challenging. As a result, Nernst-Einstein's relation has been used to relate the ionic conductivity to ionic diffusivity after the determination of either parameter. Although Nernst-Einstein's relation has been used for different electrolytes, we demonstrate in this perspective that this relation is not directly transferable to describe the ionic mobility for many inorganic solid electrolytes. The fundamental physics of Nernst-Einstein's relation shows that the relationship between the diffusion coefficient and electrolyte conductivity is derived for ionic mobility in a viscous or a gaseous medium. This postulation contradicts state-of-the-art experimental studies measuring the mechanical behaviour of inorganic solid electrolytes, which show that inorganic solid electrolytes are usually brittle rather than viscoelastic at ambient room temperature. The measurement of loss tangent is required to justify the use of Nernst-Einstein's relation. The outcome of such measurement has two implications. First, if the loss tangent of inorganic solid electrolytes is less than unity in the range of batteries operating temperatures, the impacts of using Nernst-Einstein's relation in modelling the ionic mobility should be quantified. Secondly, if the measured loss tangent is comparable to that of solid polymers and lithium metal, inorganic solid electrolytes may behave in a viscoelastic manner as opposed to the brittle behaviour usually suggested.

The Urosepsis-A Literature Review.

Urosepsis is a very serious condition with a high mortality rate. The immune response is in the center of pathophysiology. The therapeutic management of these patients includes surgical treatment of the source of infection, antibiotic therapy and life support. The management of this pathology is multidisciplinary and requires good collaboration between the urology, intensive care, imaging and laboratory medicine departments. An imbalance of pro and anti-inflammatory cytokines produced during sepsis plays an important role in pathogenesis. The study of cytokines in sepsis has important implications for understanding pathophysiology and for development of other therapeutic solutions. If not treated adequately, urosepsis may lead to serious septic complications and organ sequelae, even to a lethal outcome.

Experimental and numerical analysis to identify the performance limiting mechanisms in solid-state lithium cells under pulse operating conditions.

Solid-state lithium batteries could reduce the safety concern due to thermal runaway while improving the gravimetric and volumetric energy density beyond the existing practical limits of lithium-ion batteries. The successful commercialisation of solid-state lithium batteries depends on understanding and addressing the bottlenecks limiting the cell performance under realistic operational conditions such as dynamic current profiles of different pulse amplitudes. This study focuses on experimental analysis and continuum modelling of cell behaviour under pulse operating conditions, with most model parameters estimated from experimental measurements. By using a combined impedance and distribution of relaxation times analysis, we show that charge transfer at both interfaces occurs between the microseconds and milliseconds timescale. We also demonstrate that a simplified set of governing equations, rather than the conventional Poisson-Nernst-Planck equations, are sufficient to reproduce the experimentally observed behaviour during pulse discharge, pulse charging and dynamic pulse. Our simulation results suggest that solid diffusion in bulk LiCoO2 is the performance limiting mechanism under pulse operating conditions, with increasing voltage loss for lower states of charge. If bulk electrode forms the positive electrode, improvement in the ionic conductivity of the solid electrolyte beyond 10-4 S cm-1 yields marginal overall performance gains due to this solid diffusion limitation. Instead of further increasing the electrode thickness or improving the ionic conductivity on their own, we propose a holistic model-based approach to cell design, in order to achieve optimum performance for known operating conditions.

A zero dimensional model of lithium-sulfur batteries during charge and discharge.

Lithium-sulfur cells present an attractive alternative to Li-ion batteries due to their large energy density, safety, and possible low cost. Their successful commercialisation is dependent on improving their performance, but also on acquiring sufficient understanding of the underlying mechanisms to allow for the development of predictive models for operational cells. To address the latter, we present a zero dimensional model that predicts many of the features observed in the behaviour of a lithium-sulfur cell during charge and discharge. The model accounts for two electrochemical reactions via the Nernst formulation, power limitations through Butler-Volmer kinetics, and precipitation/dissolution of one species, including nucleation. It is shown that the flat shape of the low voltage plateau typical of the lithium-sulfur cell discharge is caused by precipitation. During charge, it is predicted that the dissolution can act as a bottleneck, because for large enough currents the amount that dissolves becomes limited. This results in reduced charge capacity and an earlier onset of the high plateau reaction, such that the two voltage plateaus merge. By including these effects, the model improves on the existing zero dimensional models, while requiring considerably fewer input parameters and computational resources than one dimensional models. The model also predicts that, due to precipitation, the customary way of experimentally obtaining the open circuit voltage from a low rate discharge might not be suitable for lithium-sulfur. This model can provide the basis for mechanistic studies, identification of dominant effects in a real cell, predictions of operational behaviour under realistic loads, and control algorithms for applications.

Modeling the voltage loss mechanisms in lithium-sulfur cells: the importance of electrolyte resistance and precipitation kinetics.

Understanding of the complex electrochemical, transport, and phase-change phenomena in Li-S cells requires experimental characterization in tandem with mechanistic modeling. However, existing Li-S models currently contradict some key features of experimental findings, particularly the evolution of cell resistance during discharge. We demonstrate that, by introducing a concentration-dependent electrolyte conductivity, the correct trends in voltage drop due to electrolyte resistance and activation overpotentials are retrieved. In addition, we reveal the existence of an often overlooked potential drop mechanism in the low voltage-plateau which originates from the limited rate of Li2S precipitation.

Reflection of light by metal nanoparticles at electrodes.

We present model calculations for the reflection spectrum of an ordered two dimensional array of metallic nanoparticles located near an electrochemical interface. We consider three cases, nanoparticles at: (i) a metal electrode, (ii) a transparent semiconductor electrode, and (iii) an electrified liquid/liquid interface. In the case of a metal electrode, the presence of nanoparticles introduces dips in reflection, whose position and depth are affected by the distance and size of the nanoparticles. For both a transparent semiconductor electrode and a liquid/liquid interface, the presence of nanoparticles enhances reflectivity. The spectra are sensitive to the particle spacing and size. The response from all three systems exhibits a strong dependence on the polarisation of light. The dependence on the angle of incidence reveals shallow dips typical of surface plasmon resonance spectra. These findings suggest diagnostic tools for the detection and characterisation of nanoparticle monolayers on functionalised electrodes, and enable electrovariable optical devices based on the controlled assembly of nanoparticles at interfaces.

Lithium-Ion Battery Degradation: Measuring Rapid Loss of Active Silicon in Silicon-Graphite Composite Electrodes.

To increase the specific energy of commercial lithium-ion batteries, silicon is often blended into the graphite negative electrode. However, due to large volumetric expansion of silicon upon lithiation, these silicon-graphite (Si-Gr) composites are prone to faster rates of degradation than conventional graphite electrodes. Understanding the effect of this difference is key to controlling degradation and improving cell lifetimes. Here, the effects of state-of-charge and temperature on the aging of a commercial cylindrical cell with a Si-Gr electrode (LG M50T) are investigated. The use of degradation mode analysis enables quantification of separate rates of degradation for silicon and graphite and requires only simple in situ electrochemical data, removing the need for destructive cell teardown analyses. Loss of active silicon is shown to be worse than graphite under all operating conditions, especially at low state-of-charge and high temperature. Cycling the cell over 0-30% state-of-charge at 40 °C resulted in an 80% loss in silicon capacity after 4 kA h of charge throughput (∼400 equiv full cycles) compared to just a 10% loss in graphite capacity. The results indicate that the additional capacity conferred by silicon comes at the expense of reduced lifetime. Conversely, reducing the utilization of silicon by limiting the depth-of-discharge of cells containing Si-Gr will extend their lifetime. The degradation mode analysis methods described here provide valuable insight into the causes of cell aging by separately quantifying capacity loss for the two active materials in the composite electrode. These methods provide a suitable framework for any experimental investigations involving composite electrodes.

Electrical control of Faraday rotation at a liquid-liquid interface.

A theory is developed for the Faraday rotation of light from a monolayer of charged magnetic nanoparticles at an electrified liquid-liquid interface. The polarization fields of neighboring nanoparticles enhance the Faraday rotation. At such interfaces, and for realistic sizes and charges of nanoparticles, their adsorption-desorption can be controlled with a voltage variation<1 V, providing electrovariable Faraday rotation. A calculation based on the Maxwell-Garnett theory predicts that the corresponding redistribution of 40 nm nanoparticles of yttrium iron garnet can switch a cavity with a quality factor larger than 10(4) for light of wavelength 500 nm at normal incidence.

[Torsion and infarction of an accessory liver lobe]. / Lob hepatic accesoriu torsionat si infarctat.

Anatomical abnormalities of the liver are extremely rare. We report a case of a 32 year old female who has admitted with acute epigastric pain and vomiting. Physical exam revealed a mobile mass in right middle abdominal quadrant. Ultrasound and contrast--enhanced CT demonstrated a heterogeneous vascular left mass. Small bowel enema shows left jejunal loops displacement. Surgical findings: twisted, congested swelling, attached by a long pedicle to the liver's third segment. Histological examination showed recent hepatic infarction.