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In recent years, lithium bis(oxalato)borate, LiB(C2O4)2 (LiBOB) has been proposed as an alternative salt to the commonly used electrolyte, LiPF6. There is evidence of the enhanced stability of Li-ion battery electrodes in solutions of this salt, due to a unique surface chemistry developed in LiBOB solutions. The present study is aimed at further exploring the electrochemical and thermal properties of LiBOB solutions in mixtures of alkyl carbonates with non-active metal, graphite and lithium electrodes. FTIR spectroscopy, XPS, EQCM, in situ AFM imaging, and DSC were used in conjunction with standard electrochemical techniques. The study also included a comparison between LiBOB and LiPF6 solutions. The development of a favorable surface chemistry in LiBOB solutions that provides better passivation to Li and Li-graphite electrodes was clearly evident.
This paper introduces a state of charge (SOC) estimation algorithm that was implemented for an automotive lithium-ion battery system used in fuel-cell hybrid vehicles (FCHVs). The proposed online control strategy for the lithium-ion battery, based on the Ah current integration method and time-triggered controller area network (TTCAN), incorporates a signal filter and adaptive modifying concepts to estimate the Li2MnO4 battery SOC in a timely manner. To verify the effectiveness of the proposed control algorithm, road test experimentation was conducted with an FCHV using the proposed SOC estimation algorithm. It was confirmed that the control technique can be used to effectively manage the lithium-ion battery and conveniently estimate the SOC.
Both macro- and microscopic magnetic nature of Li x NiO2 ( 0.1 ≤ x ≤ 1 ) were studied by susceptibility ( χ ) and muon-spin rotation and relaxation ( μ + SR) measurements in order to understand the change in magnetism of Li x NiO2 with x. The χ measurements showed the presence of spin-glass-like freezing at T f ∼ 11 K for the samples in the whole x range measured. This implies that the macroscopic magnetism is not sensitive to x, although the crystal structure and average oxidation state of the Ni ions of Li x NiO2 alter as a function of x. On the other hand, the microscopic magnetism of Li x NiO2 is found to be quite different from the macroscopic one. That is, a static antiferromagnetic ordered phase appears at low T for the samples with 0.6 ≤ x ≤ 1 , while a spin-glass-like disordered phase presents for the 0.25 ≤ x ≤ 0.5 samples below 10K.
The electrochemical behaviors of LiPF6 and lithium oxalyldifluoroborate (LiODFB) blend salts in ethylene carbonate+propylene carbonate+dimethyl carbonate (EC+PC+DMC, 1:1:3, v/v/v) for LiFePO4/artificial graphite (AG) lithium-ion cells have been investigated in this work. It is demonstrated by conductivity test that LiPF6 and LiODFB blend salts electrolytes have superior conductivity to pure LiODFB-based electrolyte. The results show that the performances of LiFePO4/Li half cells with LiPF6 and LiODFB blend salts electrolytes are inferior to pure LiPF6-based electrolyte, the capacity and cycling efficiency of Li/AG half cells are distinctly improved by blend salts electrolytes, and the optimum LiODFB/LiPF6 molar ratio is around 4:1. A reduction peak is observed around 1.5V in LiODFB containing electrolyte systems by means of CV tests for Li/AG cells. Excellent capacity and cycling performance are obtained on LiFePO4/AG 063048-type cells tests with blend salts electrolytes. A plateau near 1.7–2.0V is shown in electrolytes containing LiODFB salt, and extends with increasing LiODFB concentration in charge curve of LiFePO4/AG cells. At 1C discharge current rate, the initial discharge capacity of 063048-type cell with the optimum electrolyte is 376.0mAh, and the capacity retention is 90.8% after 100 cycles at 25°C. When at 65°C, the capacity and capacity retention after 100 cycles are 351.3mAh and 88.7%, respectively. The performances of LiFePO4/AG cells are remarkably improved by blending LiODFB and LiPF6 salts compared to those of pure LiPF6-based electrolyte system, especially at elevated temperature to 65°C.
Computationally efficient numerical models of battery cooling systems are developed and the effects of the battery cell arrangement and the heat transfer fluid (HTF) type on the cooling performance and the parasitic power consumption of the system are investigated. A one-dimensional heat conduction model of a cylindrical battery cell is developed using a finite difference method for the cell temperature prediction and a battery module model is developed to predict the cell to cell temperature variation and the power consumption of the systems depending on the design of battery module and operating conditions. The analysis of the battery thermal management system (BTMS) design by using the numerical model is conducted for air and liquid type BTMSs. From the numerical analysis, it is found that a wide battery module with a small cell to cell gap is desirable for the air type BTMS while a narrow battery module with a small gap is desirable for a liquid type BTMS. The results also show that the air type BTMS consumes much more power compared with the liquid type BTMS especially for high heat load condition. However, under low heat load conditions, the power consumption of the air type BTMS is acceptable considering its advantages over the liquid type BTMS.
Thin silicon layers containing about 20% carbon and 20% oxygen were deposited on copper substrates by potentiostatic electroreduction from a 1M SiCl4 1-butyl-1-methyl-pyrrolidinium bis (trifluoromethyl) sulfonylimide [BMP][TFSI] electrolyte. The electrodeposition process was investigated by means of voltammetric techniques, coupled with in-situ microgravimetry (quartz crystal microbalance, QCM). The electrochemical and QCM data suggest a possible contribution of a partial Si4+ to Si2+ reduction and/or a restructuring of the metallic substrate. Considerable impact of side reactions parallel to the deposition process was indicated by QCM measurements performed under potentiostatic and potentiodynamic conditions. The deposition of silicon-based films was confirmed by energy dispersive X-ray analysis (EDX). Analysis of the chemical composition of the deposit and its elemental distribution were achieved by depth profiling X-ray photoelectron spectroscopy (XPS). The electrodeposited silicon containing layers showed stable lithiation and delithiation with capacity values of about 1200mAhg−1 and 80% capacity retention after 300 cycles in standard EC/DMC electrolytes. In ionic liquid (IL) the material displayed lower capacity of ca. 500mAhg−1, which can be attributed to the higher viscosity of this electrolyte and deposition of IL decomposition products during lithiation.
A FeSi2.7 thin film is deposited on a copper substrate by RF magnetron sputtering of a Fe–Si alloy target. The electrochemical behavior of the FeSi2.7 electrode in ionic liquid electrolyte based on 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide is investigated and compared with that of a FeSi2.7 electrode in conventional liquid electrolyte. The FeSi2.7 electrode in the ionic liquid electrolyte delivers an initial discharge capacity of 756mAhg−1 at room temperature, and its discharge capacity is maintained to be 92% of the initial discharge capacity after the 100th cycle. AC impedance and FTIR analysis reveal that the formation of a stable solid electrolyte interphase (SEI) layer on the FeSi2.7 electrode in the ionic liquid electrolyte leads to a good capacity retention. This study demonstrates that the FeSi2.7 electrode exhibits stable cycling behavior and good interfacial characteristics in the ionic liquid electrolyte without any solvents and additives.
Germanium and silicon can be used to reversibly store large amounts of lithium, but as a result, suffer from significant volumetric and structural changes during cycling. The mechanical stresses associated with these changes were investigated using in situ stress measurements on thin film electrodes. Results for germanium, with its superior transport properties, are compared to silicon, which is structurally similar. The nominal stresses developed in amorphous lithium–germanium (a-Li x Ge) were found to be roughly 30% lower than in a-Li x Si. When the cycling rate was increased, the germanium electrode showed a smaller loss in capacity than silicon. Crystalline Li15Ge4 was observed to form below 100 mV and resulted in a distinct tensile bump in nominal stress. During extended cycling, the maximum mechanical stress signal of the film electrodes irreversibly decreased without an apparent loss in capacity. In contrast to silicon films, which typically fracture and lose capacity during cycling, germanium films were capable of reorganizing into three-dimensional structures, thereby improving their mechanical response while minimizing electrochemical energy loss. The reduced nominal flow stresses observed in a-Li x Ge and their weak dependence on charge–discharge rates correlated with the reduced rate sensitivity found in germanium electrodes as compared to silicon.
Though MXenes, a new family of 2D transition metal carbides, are generating considerable interests as electrode materials for batteries and supercapacitors, further application is hindered by their low capacities and poor rate capabilities. Here we propose a simple route for the synthesis of Cu2O particle hybridized titanium carbide Ti2CTx (T=O, OH) composites via a solvothermal method. Electrodes containing Cu2O/MXene were fabricated without carbon black, and tested as anodes for lithium ion batteries. A discharge capacity of 143mAhg−1 was obtained at a discharge current density of 1000mAg−1 and the capacity retention was near 100% after 200 cycles. The hybrid electrodes with open conductive frameworks exhibited significantly improved electrochemical performance, suggesting a new method for preparing MXene-based composites for energy storage application.
Resolving the mismatch between the practical potential window (PPW) and the available capacitive potential window of supercapacitor electrodes provides a feasible way to expand the operating voltage of supercapacitors, which further boosts energy density. Here, our research unveils a unique approach to manually control the PPW of the corresponding carbon-based supercapacitors (CSCs) by rational functionalization with amino groups. The extra pair of electrons from amino N atoms naturally adsorbs cations in the electrolyte, which rationalizes the surface charge of the carbon electrode and adjusts the PPW. A remarkable voltage expansion is achieved for CSCs, from 1.4 V to its maximum limit, 1.8 V, correspondently resulting in an approximately 1-fold increase in the energy density. Importantly, such a simple strategy endows our CSCs with an outstanding maximum energy density of 7.7 mWh cm−3, which is not only among the best values reported for thin-film CSCs but also comparable to those reported for Li thin-film batteries. These encouraging results are believed to bring fundamental insights into the nature of potential control in energy storage devices.
Synthesized yttrium aluminum garnet (YAG) sol was coated on the surface of the LiCoO2 cathode particles by an in situ sol–gel process, followed by calcination at 923K for 10h in air. Based on XRD, TEM, and ESCA data, a compact YAG kernel with an average thickness of ∼20nm was formed on the surface of the core LiCoO2 particles, which ranged from ∼90 to 120nm in size. The charge–discharge cycling studies for the coated materials suggest that 0.3wt.% YAG-coated LiCoO2 heated at 923K for 10h in air, delivered a discharge capacity of 167mAhg−1 and a cycle stability of about 164 cycles with a fading rate of 0.2mAhcycle−1 at a 0.2C-rate between 2.75 and 4.40V vs. Li/Li+. The differential capacity plots revealed that impedance growth was slower for YAG surface treated LiCoO2, when cells were charged at 4.40V. DSC results exemplified that the exothermic peak at ∼468K corresponded to the release of much less oxygen and greater thermal-stability.
The influence of the immune system deregulation on the risk of schizophrenia is increasingly recognized. The aim of this study was to assess the influence of serum interleukin-6 (IL-6) level together with the polymorphism in its gene (IL6 -174G/C) and high sensitivity C-reactive protein (hsCRP) levels on clinical manifestation and cognition in schizophrenia patients. We recruited 151 patients with schizophrenia and 194 healthy control subjects. Psychopathology was evaluated using Operational Criteria for Psychotic Illness checklist, Positive and Negative Syndrome Scale (PANSS) and Scales for Assessment of Positive and Negative Symptoms. Cognitive performance in schizophrenia patients was assessed using following tests: Rey Auditory Verbal Learning Test, Trail Making Test, Verbal Fluency Tests, Stroop and subscales from Wechsler Adults Intelligence Scale-R-Pl (Similarities, Digit Symbol Coding, Digit Span Forward and Backward). Serum IL-6 and hsCRP levels were significantly higher in schizophrenia patients in comparison with healthy controls. Both hsCRP and IL-6 levels were associated with insidious psychosis onset, duration of illness and chronic schizophrenia course with deterioration. After adjustment for age, education level, number of years of completed education, illness duration, total PANSS score, depression severity and chlorpromazine equivalent, there was still a positive association between IL-6 and hsCRP levels and worse cognitive performance. The IL6 -174G/C polymorphism did not influence IL-6 level, but it was associated with the severity of positive symptoms. Our results suggest that elevated IL-6 levels may play the role in cognitive impairment and serve as potential inflammatory biomarker of deterioration in schizophrenia.
Cycle performance of a LiAl0.10Ni0.76Co0.14O2 (NCA) cathode/graphite cell closely depended on the range of depth of discharge in charge–discharge processes (ΔDOD). When ΔDOD was 10–70%, cycle performance at 25 °C was maintained even at 60 °C. Deterioration phenomena were analyzed by electrochemical method, X-ray photoelectron spectroscopy (XPS), X-ray diffractometry (XRD), and micro-cracks in NCA particles were analyzed with cross-sectional views by scanning electron microscopy (SEM). Many micro-cracks were observed only after a 0–100% DOD region cycle test. Cycle tests in several restricted ΔDOD conditions showed that the deterioration was closely related to not the upper and lower limits of DOD or operation voltage but the width of ΔDOD.
A LiFePO4/C sample was prepared via solid state reaction and characterized with X-ray powder diffraction, scanning electron microscopy and charge–discharge test. Conductive carbon and highly crystallized LiFePO4 were embedded in each other to form the as-prepared LiFePO4/C, which exhibited an excellent rate capability and capacity retention. The LiFePO4/C electrode reaction was investigated by the method of medium scan rate cyclic voltammetry (CV) under temperature variation. The limit values for the CV redox peak potentials of the LiFePO4/C electrode scanned at different rates were obtained by curve fitting. The reversibility of the LiFePO4/C electrode was studied and found to be both scan rate and temperature dependent. A higher temperature led to a higher critical CV scan rate for a reversible LiFePO4/C electrode. In the electrode process, a higher temperature resulted in a smoother Fe3+/Fe2+ redox reaction, better reversibility, lower Rcv, smaller charge transfer resistance and higher Li+ ion diffusion coefficient at the cathode of the LiFePO4/C.
Chronic obstructive pulmonary disease (COPD) imposes a substantial burden on individuals with the disease, which can include a range of symptoms (breathlessness, cough, sputum production, wheeze, chest tightness) of varying severities. We present an overview of the biomedical literature describing reported relationships between COPD symptoms and disease burden in terms of quality of life, health status, daily activities, physical activity, sleep, comorbid anxiety, and depression, as well as risk of exacerbations and disease prognosis. In addition, the substantial variability of COPD symptoms encountered (morning, daytime, and nighttime) is addressed and their implications for disease burden considered. The findings from this narrative review, which mainly focuses on real-world and observational studies, demonstrate the impact of COPD symptoms on the burden of disease and that improved recognition and understanding of their impact is central to alleviating this burden.
Li2MoO4 modified Li4Ti5O12/C anode material has been synthesized by a ball-milling assisted rheological phase reaction method. The structures, morphologies and electrochemical properties of the as-prepared materials have been analyzed by different physical and electrochemical methods. The results show that the amorphous carbon is successfully coated on the surface of Li4Ti5O12 nanoparticles with partial doping of Mo6+ into the Li4Ti5O12 structure. Electrochemical results indicate that Li2MoO4 modified Li4Ti5O12/C samples deliver improved rate capability and decreased charge transfer resistance. Among the investigated samples, the one with 5 wt% Li2MoO4 sample exhibits the optimal electrochemical properties and it shows a large capacity of 167.5mAhg−1 at 1C rate, which is close to its theoretical capacity. Even at 10C, its charge capacity is up to 137.5mAhg−1 with a high capacity retention of 92.5% after 200 cycles. The excellent electrochemical properties should be attributed to the improvement of electrochemical kinetics by the synergistic employment of reducing particle size, partial Mo6+ doping and Li2MoO4/C modification.
A new single-source precursor has been developed from the hydrothermal reaction of graphite oxide (GO), melamine resin (MR) monomers, and CoCl2 to prepare a sandwich-like hybrid of ultrathin nitrogen-doped graphene (NG) sheets and porous Co3O4 nanospheres (Co3O4/NG). This unique structure endows the Co3O4/NG hybrid with large surface area and enhanced electrochemical performances as both anode material for Li-ion batteries and electrocatalyst for oxygen reduction reaction (ORR). As an anode material, it exhibits high reversible capacity, excellent cycling stability and rate performance (1236 and 489 mAh g−1 over 200 cycles at 0.1C and 2C, respectively; 371 mAh g−1 at 5C). As an ORR electrocatalyst, it shows superior catalytic activity and high selectivity for the four-electron reduction pathway compared to the bare Co3O4 and NG alone. Moreover, the Co3O4/NG hybrid is insensitive to methanol, and is much more stable than Pt/C catalyst over long term operation.
In the present study we assessed the neuroprotective effects of the pan-caspase inhibitor z-VAD.fmk [N-benzyloxycarbony-valine-alanine-aspartate-(OMe)-fluoromethylketone], and the caspase-3 inhibitor Ac-DEVD.CHO (acetyl-aspartate-chloromethylketone) in the double-lesion rat model of striatonigral degeneration (SND), the core pathology underlying levodopa-unresponsive parkinsonism associated with multiple system atrophy (MSA). Male Wistar rats were divided into three groups, receiving either Ac-DEVD.CHO, z-VAD.fmk or normal saline before lesion surgery, comprising a sequential unilateral quinolinic acid (QA) lesion of the striatum followed by a 6-hydroxydopamine (6-OHDA) lesion of the ipsilateral medial forebrain bundle. At 2 weeks post lesion, all rats underwent testing of spontaneous nocturnal locomotor behavior in an automated Photobeam Activity System (FlexField). Immunohistochemistry was performed with tyrosine hydroxylase, dopamine and cyclic adenosine 3’,5’-monophosphate-regulated phosphoprotein and glial fibrillary acidic protein antibodies. Morphometry was performed using computerized image analysis. Behavioral and morphological analysis failed to show striatal or nigral protection in caspase inhibitor-treated animals. Our findings suggest that anti-apoptotic strategies are unrewarding in the SND rat model and, therefore, alternative neuroprotective interventions such as anti-glutamatergic agents or inhibitors of microglial activation should be explored instead.
New solid polymer electrolytes (SPEs) comprised of lithium bis(fluorosulfonyl) imide (Li[N(SO2F)2], LiFSI) and polymeric ionic liquid (i.e., poly[N,N-dimethyl-N-[2-(methacryloyloxy) ethyl]-N-[2-(2-methoxyethoxy) ethyl]ammonium] bis(fluorosulfonyl) imide, P[C5O2NMA,11]FSI) have been prepared and characterized. For comparison, the corresponding SPEs, lithium bis(trifluoromethylsulfonyl) imide (Li[N(SO2CF3)2], LiTFSI)/poly[N,N-dimethyl-N-[2-(methacryloyloxy) ethyl]-N-[2-(2-methoxyethoxy) ethyl]ammonium] bis(trifluoromethylsulfonyl) imide (P[C5O2NMA,11]TFSI), are also prepared and characterized. Their physicochemical properties have been investigated in terms of phase transition behavior, ionic conductivity, lithium-ion transference number (t Li +), electrochemical stability, and with particular attention to the interfacial behavior between lithium electrode and SPEs. It has been demonstrated that the ionic conductivities of LiFSI/P[C5O2NMA,11]FSI electrolyte are higher than those of the corresponding TFSI-based one. The interface resistances of Li symmetric cell (Li metal | polymer electrolytes | Li metal) using LiFSI/P[C5O2NMA,11]FSI electrolyte are much lower than those using LiTFSI/P[C5O2NMA,11]TFSI electrolyte. These outstanding properties of the FSI-based electrolyte make it attractive as SPEs for Li battery.
Lithium metal batteries are the most potential candidate for rechargeable batteries today to meet the urgent demands for high energy density. However, uncontrolled dendrite formation and infinite volume expansion hinder the practical application of lithium metal anode. Herein, we develop a new strategy to make physical accommodation and chemical ionic intervention well-combined to modulate the Li deposition behavior. A K+-doped nanofiber protective layer, having abundant lithophilic groups and porous framework is electrospun on current collector. It can provide high affinity with electrolyte and uniform pathway for lithium ions transportation, and a host for the volumetric change during lithium plating/stripping. Moreover, it can gradually release K+ as an inhibitor to contribute to more stable SEI layer and prevent aggregation of Li ions by forming an electrostatic shielding on the surface of electrode. As a result, the functional K+-doped nanofiber protective layer can guide uniform lithium deposition, leading to high Coulombic efficiency (98.5%) and low overpotential (∼15 mV) in symmetric cells with long lifespan. This work sheds the dawn of the research on the multi-functional protective layer material for dendrite-free lithium metal batteries.