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We report the synthesis of low and high temperature polymorphs of Li2MnSiO4 and dependence of lithium storage performance on such polymorphs. Two polymorphs namely, Pmn21 (low temperature/orthorhombic polymorph) and P21/n (high temperature/monoclinic polymorph) are isolated by controlling the calcination temperature. Among them the electrochemical performance of Pmn21 is found to be better than P21/n. Orthorhombic polymorph (Pmn21) of carbon coated Li2MnSiO4 exhibits an impressive discharge capacity of 262 mAh g−1 at 0.1C and rate performance up to 5C; in contrast P21/n delivers only a discharge capacity of 164 mAh g−1 at 0.1C at room temperature. Notably, the capacity of Pmn21 phase is almost 1.5–2 times higher than P21/n phase at all current rates. Capacity retention of 90% is reported for orthorhombic polymorph until 30 cycles at 0.1C. Further the voltage profiles and polarization of orthorhombic phase are much better than the monoclinic phase. Such perceivable differences in the rate performances and voltage profiles is argued to be due to variations in the activation energy barrier and hopping distance of lithium-ion in the crystal structures. Besides the role of polymorphism, we also show here that the structural stability during cycling is critical in retaining high storage performance.
Two phase-pure nanocrystalline anatase materials differing in the exposed crystal facets (001) or (101) are studied by electrochemical impedance spectroscopy and by transient photovoltage and photocurrent decay in dye sensitized solar cells. A larger chemical capacitance, indicating larger density of states, is observed for anatase (001). The presence of deep electron traps in (001) nanosheets is further confirmed by optical (UV-Vis) and photoemission (XPS, UPS) spectra. The difference in chemical capacitance indicates a slower diffusion of electrons in the (001) anatase material, but also a higher electron lifetime compared to (101) anatase material.
Poor rate capability and capacity degradation of LiNixCoyMnzO2 restricts its practical commercial applications at high operating voltage (>4.3 V). LiNi1/3Co1/3Mn1/3O2 is successfully modified by tungsten compound through a cost-effective ball-milling and annealing process. The rate capability of W-modified cathode is increased by 57.6% at 10C in 3.0–4.5 V. Moreover, after 100 cycles the capacity retention is improved from 80% to 96% under 0.5C. At 1C, W-modified cathode still maintains 145 mAh g−1 discharge capacity after 100 cycles, which has 16% increase than pristine LiNi1/3Co1/3Mn1/3O2. The improvements on rate and cycle performance are introduced by enhanced Li-ion diffusion and surface stability by tungsten modification.
Via Sr-site substitution, a series of Sr0.95M0.05Li2Ti6O14 (Mz+ = Na+, Cu2+, In3+) are prepared as anode materials for lithium-ion batteries. It is found that the introduction of Na+, Cu2+ or In3+ into the crystal lattice can reduce the charge-transfer resistance and improve the lithium-ion diffusion coefficient of SrLi2Ti6O14. Especially for In3+-doping, it exhibits more obvious effect on these improvements. Furthermore, the substitution of Sr2+ by In3+ can also enhance the electronic conductivity via inducing a reduction of an equivalent number of Ti cations from Ti4+ to Ti3+. As a result, Sr0.95In0.05Li2Ti6O14 shows the best cycle and rate properties among all as-prepared samples. In addition, in-situ observation also proves that Sr0.95In0.05Li2Ti6O14 is a zero-strain lithium storage compound during charge/discharge process. As a result, it delivers a lithium storage capacity of 136.4 mAh g−1 at 200 mA g−1, 126.3 mAh g−1 at 400 mA g−1 and 121.0 mAh g−1 at 600 mA g−1. In contrast, SrLi2Ti6O14 only presents a charge capacity of 138.3 mAh g−1 at 200 mA g−1, 120.3 mAh g−1 at 400 mA g−1 and 111.3 mAh g−1 at 600 mA g−1. Therefore, In3+-doping is an effective method to enhance the electrochemical properties of SrLi2Ti6O14.
This work entails a method to improve the performance of dye-sensitized nanocrystalline TiO2 solar cells by adding surface passivating elements to the electrolyte. The presence of either CO2, Li2CO3 or K2CO3 in electrolyte increases both the photocurrent and the photovoltage, resulting in higher overall conversion efficiency of these solar cells. The additives are used to form a passivation layer of lithium carbonate on the dye free surface of the TiO2 nanoparticles and the conductive substrate. This layer suppresses the rate of the main recombination reaction between the photoinjected electrons and the oxidized ions in the electrolyte solution. While blocking part of the recombination, the lithium carbonate layer allows motion of the Li+ ions towards the TiO2 surface for charge screening. Consequently using this simple treatment, the conversion efficiency of dye-sensitized solar cell most improved by 17.2% (from 6.4% to 7.5%).
Arbuscular mycorrhizal fungi (AMF) are mutualistic symbionts considered a key group in soil systems involved in the provision of several ecosystem services. Recently they have been listed by EFSA as organisms to be included in the test battery for the risk assessment of plant protection product (PPPs). This study aimed to contribute to improve the ISO Protocol (ISO 10832: 2009) by assessing the feasibility of using other AMF species under different test conditions. Overall, results showed that AMF species Gigaspora albida and Rhizophagus clarus (selected out of five AMF species) are suitable to be used in spore germination tests using the ISO protocol (14 days incubation with sand or artificial soil as substrate) to test PPPs. However, several modifications to the protocol were made in order to accommodate the use of the tested isolates, namely the incubation temperature (28 °C instead of 24 °C) and the change of reference substance (boric acid instead of cadmium nitrate). The need for these changes, plus the results obtained with the three fungicides tested (chlorothalonil, mancozeb and metalaxyl-M) and comparisons made with literature on the relevance of the origin of AMF isolates in dictating the adequate test conditions, emphasize the importance of adjusting test conditions (AMF species/isolates and test temperature) when assessing effects for prospective risk assessment targeting different climatic zones. So, further studies should be conducted with different AMF species and isolates from different climatic regions, in order to better define which species/isolate and test conditions should be used to assess effects of a particular PPP targeting a given climatic zone.
Electric double-layer capacitors (EDLCs) using carbon electrodes have been anticipated as an energy storage device for electric vehicle, distributed energy system applications, and so on. High surface-area carbons were employed for the electrode materials of EDLC to store energy in the electric double layer, and the control of the pore size distribution of its carbons was recognized to be very important. On the other hand, when the electrode material shows Faradic reactions at the electrode surface in a wide range of potential window, the energy stored by the charge transfer can be accounted as pseudocapacitance. The investigation of novel carbon materials is directly connected to the improvement of EDLC performance, since carbon is essential for capacitor electrode materials. This paper presents recent developments in carbon materials for EDLC electrodes in which the enhancement of various characteristics was achieved by various techniques such as chemical and structural control and hybridization with heteroatoms. Recently, capacitors using these novel carbon materials, having Faradic reactions and novel mechanisms to enhance the total performance, have become to be known as supercapacitors.
Rehabilitation after lower-extremity fractures is based on the physicians’ recommendation for non-, partial-, or full weight-bearing. Clinical studies rely on this assumption, but continuous compliance or objective loading rates are unknown. The purpose of this study was to determine the compliance to weight-bearing recommendations by introducing a novel, pedobarography system continuously registering postoperative ground forces into ankle, tibial shaft and proximal femur fracture aftercare and test its feasibility for this purpose.
Nitrogen-doped activated carbons (NACs) were prepared through a one-step process. The obtained NACs show high surface areas of up to 2900 m2 g−1 with a moderate N content of up to 4 wt%. Electrochemical evaluation of the NACs shows a high specific capacity of 129 mA h g−1 (185 F g−1) in an organic electrolyte at a current density of 0.4 A g−1, as well as excellent rate capability and cycling stability. The hybrid-type supercapacitor assembled using the NACs and a Si/C electrode exhibits a high material level energy density of 230 W h kg−1 at 1747 W kg−1. The hybrid device achieved 76.3% capacity retention after 8000 cycles tested at 1.6 A g−1.
The cycling behavior of Li4Ti5O12/LiCoO2 cells in the ionic liquid electrolytes based on 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (BMP-TFSI) with different additives, such as vinylene carbonate (VC), 1,3-propane sultone (PS) and their mixture is investigated. The cell assembled with BMP-TFSI containing 10wt% VC/PS (1:1 by weight) exhibits reversible cycling behavior with good capacity retention. FTIR studies reveal that the electrochemically stable solid electrolyte interphase forms on Li4Ti5O12 electrode in the presence of a mixture of VC and PS during cycling. The additives hardly affect the composition, thickness and stability of the surface film formed on the LiCoO2 cathode.
Petroleum coke graphite (PCG) and needle coke graphite (NCG) scraps with different aggregate and morphology were selected. The structural developments in the temperature range from 2400°C to 3000°C showed that the graphite crystallites in samples increased faster in the base plane direction (100) compared to that in the vertical direction (002). The crystallite volume of sample NCG is much bigger than the sample PCG under each condition because the former is easier to be graphitized to the latter. The discharge capacity of graphite scrap anode was mainly determined by its crystallite parameters. Although the discharge capacities of samples PCG or NCG were well fitted with their crystallite parameters separately, the correlation coefficients between the capacities and L c, L a and V of all the samples decreased. This is because big differences exist in the parameters of different samples. The discharge capacity of graphite anode still depends strongly on graphitization degree even if additional four needle coke artificial graphite scraps are introduced into the group of samples PCG and NCG. The equation obtained is D =166.9+1.8584× G, in which its correlation coefficient is as high as 0.9744.
This study explored the effectiveness of dance movement therapy (DMT) in obese women with emotional eating who were trying to lose weight. 158 women were recruited from a commercial weight loss programme: 92 with BMI≥28 were identified as emotional eaters and divided into: an exercise control (n =32) and non-exercisers (n =60). The non-exercises were partially randomised to non exercise control (n =30) and treatment group (n =30). Using a pre- and post-intervention design, 24 of the DMT treatment group, 28 of the exercise control and 27 of the non-exercise control completed all measures on a battery of tests for psychological distress, body image distress, self-esteem and emotional eating. Findings were analysed for statistical significance. The DMT group showed statistically decreased psychological distress, decreased body image distress, and increased self-esteem compared to controls. Emotional eating reduced in DMT and exercise groups. The authors cautiously conclude that DMT could form part of a treatment for obese women whose presentation includes emotional eating. Further research is needed with larger, fully, and blindly randomised samples, a group exercise control, longitudinal follow-up, a depression measure, ITT, and cost analyses.
The potential impact on a variety of bioassay organisms when pulp-mill biosolids from a thermomechanical pulp mill (western Canada) were applied to a reference soil has been investigated in a laboratory setup. The current research assessed acute, chronic, and reproductive impacts using a battery of terrestrial and aquatic organisms. Terrestrial organisms were exposed to soil amended with different concentrations of biosolids, while aquatic organisms were used to assess the impact of biosolids’ runoff into receiving waters. The former bioassays showed that an application rate of 20 tonneshectare−1 (tha−1) “bone-dry” biosolids applied to reference soil produced no observable adverse impact on the terrestrial organisms. In the latter assays, undiluted (100%) and 50% diluted biosolids’ runoff into receiving water had a detrimental impact on the aquatic organisms. However, concentrations not exceeding 25% (environmentally relevant concentrations) had neither an acute nor chronic impact compared to reference populations. The organisms’ abilities to reproduce were also unaltered. While this study only examined the biosolids from one mill, there is the potential that land-application of characteristically well-defined pulp mill biosolids may constitute an acceptable way of disposing of pulp and paper mill biosolid residues. However, the biosolids coming from different mills, with differing processes, must be dealt with on a case-by-case situation. Each series of biosolids must be rigorously tested for toxicological impact in the laboratory under tightly controlled conditions. Subsequently, field experimentation must be conducted before definitive conclusions can be made.
We present a theoretical framework to calculate how storage affects the energy return on energy investment (EROI) ratios of wind and solar resources. Our methods identify conditions under which it is more energetically favorable to store energy than it is to simply curtail electricity production. Electrochemically based storage technologies result in much smaller EROI ratios than large-scale geologically based storage technologies like compressed air energy storage (CAES) and pumped hydroelectric storage (PHS). All storage technologies paired with solar photovoltaic (PV) generation yield EROI ratios that are greater than curtailment. Due to their low energy stored on electrical energy invested (ESOIe) ratios, conventional battery technologies reduce the EROI ratios of wind generation below curtailment EROI ratios. To yield a greater net energy return than curtailment, battery storage technologies paired with wind generation need an ESOIe > 80. We identify improvements in cycle life as the most feasible way to increase battery ESOIe. Depending upon the battery's embodied energy requirement, an increase of cycle life to 10000–18000 (2–20 times present values) is required for pairing with wind (assuming liberal round-trip efficiency [90%] and liberal depth-of-discharge [80%] values). Reducing embodied energy costs, increasing efficiency and increasing depth of discharge will also further improve the energetic performance of batteries. While this paper focuses on only one benefit of energy storage, the value of not curtailing electricity generation during periods of excess production, similar analyses could be used to draw conclusions about other benefits as well.
A novel methacrylic gel-polymer membrane was synthesized by free radical photo polymerisation (UV-curing technique). The polymerisation was very easy, fast and reliable and the membrane shows good behaviour in terms of both conductivity and cyclability in Li cells. The anode materials were prepared by high energy ball milling obtaining nanocrystalline Ni–Sn alloys, while the hydrothermal processing in presence of a template was used to prepare nanostructured LiFePO4/C as cathode material. Every component has been characterised separately from the structural and electrochemical point of view. The first experimental data on the performance of a complete Li-ion polymer cell assembled with the components studied are also presented. The results obtained demonstrate the overall satisfying, and some superior performances of the various single components and their feasibility as a complete system.
Recent research on the electrochemical lithiation of amorphous silicon nanoparticles shows that amorphous silicon is more fracture resistant than crystalline silicon during lithiation. Nanoparticles of amorphous silicon can be lithiated and delithiated without any fracture at all. To fully exploit the potential of using amorphous silicon as electrodes for lithium ion batteries it is important to determine if larger, micron-sized, amorphous silicon structures can be lithiated and delithiated without fracture. Here we study the morphologies of initially amorphous silicon micropillars (∼2.3 μm tall) both before and after electrochemical lithiation and delithiation. No internal or external cohesive cracking is detected in lithiated pillars for any of the pillar sizes studied. Delithiated pillars exhibit some delamination at the interface between the pillar and the underlying nickel substrate. For larger diameter pillars, the initiated interfacial crack is driven upward into the delithiated pillar as the crack propagates radially inward. However, no cohesive fracture unrelated to interfacial cracking is seen in even the largest delithiated pillars. Finite element modeling provides support for the observation that the cohesive fracture resistance of amorphous silicon micropillars is representative of the fracture resistance of amorphous silicon microparticles of comparable dimensions.
MATRICS Consensus Cognitive Battery (MCCB), packaging 10 tests selected from more than 90 nominated tests, is a method developed by the Measurement and Treatment Research to Improve Cognition in Schizophrenia (MATRICS) group to evaluate the efficacy of treatments targeting cognitive impairments in schizophrenia. MCCB had been translated into a number of languages, but only the US and Spain had normative data reported. Inconsistency in translation and cultural differences make direct application of MCCB in China problematic. In this study, we administered the battery to a representative community sample based on Chinese population census in 2005 and obtained normative data. The effects of age, gender, education level, and scale of residence area on test performance were examined. The sample included 656 healthy volunteers from six sites in China. At each site, sample was stratified according to age, gender, and educational level, and scale of the area one was born in, grew up in and currently living in was recorded. We found age, gender, and education had significant effects on the normative data for MCCB in China, which are comparable to those found for the original standardized English version in the U.S. and the Spanish version in Spain. Remarkably, the residence scale effects on neuropsychological performance were significant, which should be taking into account when calculating the standardized T score for each subject. The practice effects were minor and test-retest reliability of MCCB was good, which suggests MCCB as an appropriate measure for clinical and research usage in China.
Patients with vestibular vertigo syndromes often suffer from anxiety and depression, whereas patients with psychiatric disorders often experience subjective unsteadiness, dizziness, or vertigo. Thus, it has been hypothesized that the vestibular system may be interlinked with the emotion processing systems. The aim of the current study was to evaluate this hypothesis by correlating vestibular and psychiatric symptoms with the course of the disease over 1 year. This interdisciplinary, prospective, longitudinal study included a total of 68 patients with acute vestibular vertigo syndromes. Four subgroups of patients with benign paroxysmal positioning vertigo (BPPV, n=19), acute vestibular neuritis (VN, n=14), vestibular migraine (VM, n=27), or Menière's disease (MD, n=8) were compared. All patients underwent neurological and neuro-otological examinations and filled out standardized self-report inventories including the Vertigo Symptom Scale (VSS), the Vertigo Handicap Questionnaire (VHQ) and the Symptom Checklist 90R (GSI, SCL-90R) at five different times (T0–T4) in the course of 1 year. VM patients experienced significantly more “vertigo and related symptoms” (VSS-VER), “somatic anxiety and autonomic arousal” (VSS-AA), and “vertigo induced handicap” (VHQ) than all other patients (P<0.001−P=0.006). Patients with a positive history of psychiatric disorders had significantly more emotional distress (GSI, SCL-90R), regardless of the specific phenomenology of the four diagnostic subgroups. Finally, fluctuations of vestibular excitability correlated positively with the extent of subjectively perceived vertigo. VM patients are significantly more handicapped by vertigo and related symptoms. They show significantly elevated fluctuations of vestibular excitability, which correlate with the (subjective) severity of vertigo symptoms.
A simple approach is demonstrated to prepare functionalized spongy graphene/cobalt sulfide (FG-CoS) nanocomposites as interconnected, porous 3-dimensional (3D) network crinkly sheets. Such crinkly sheets contain the reduced spongy graphene oxide (SGO) sheets and the intercalated CoS nanoparticles within the spongy graphene. The fabricated FG-CoS composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and Raman spectroscopy. The synthesized materials were tested as supercapacitor materials in 3 M KOH using cyclic voltammetry (CV) at different potential scan rates, and galvanostatic charge/discharge tests at different current densities. The FG-CoS electrodes showed a maximum specific capacitance of 1072 F/g at a scan rate of 1 mV/s and exhibited excellent cycling retention of 117% after 1000 cycles at 100 mV/s. The obtained energy density is 35.2 Wh/kg with a power density of 250 W/kg at 1.0 A/g. This high performance can be related to the synergistic effect of graphene and CoS, where CoS is sandwiched between graphene nanosheets. This makes the FG/CoS composite promising electrode material for a high-performance supercapacitor.
Surface oxidation treatment in the temperature range of 500–1400°C was applied to a graphitized boron-doped mesophase-pitch-based carbon fiber (B-MCF), anode material for Li-ion battery. The correlation between physical properties and lithium intercalation of B-MCF was investigated from measurement of heat of immersion. The surface analysis of heat of immersion and X-ray photoelectron spectroscopy (XPS) indicated that the strength of surface electrostatic field of B-MCF increased with the composition of oxygen on the surface as a result of treatment of the oxidation. Analysis of electrochemical impedance spectroscopy (EIS) indicated that the charge transfer resistance of lithium intercalated B-MCF anode decreased with increase of surface electrostatic field strength. Oxygen atoms on surface as a result of treatment of oxidation caused high surface electrostatic field strength that enhanced an affinity of B-MCF for electrolytes. It was supposed that the low impedance of oxidized B-MCF anode was due to the enhancement of surface polarity and the affinity.