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O3–KCrO2 is the only known stoichiometric layered transition metal oxide with a layered structure, which enables efficient coupling with a graphite anode for K+-shuttling batteries. O3–KCrO2, however, shows low Coulombic efficiency during 1st charge/discharge cycle and continuous capacity fading during subsequent cycles. Here, we present a slightly K+-deficient compound P′3-K0.8CrO2, synthesized from a commercially available K2CrO4, as a stable cathode in potassium ion batteries. During the 1st charge, K0·8CrO2 mostly retains its P′3-phase with a short P3 region and finally returns to a P′3-phase (K0·48CrO2). Subsequent discharge shows reversible phase transitions, but ultimately yielded a new O′3-K0.9CrO2 phase. Absence of an O3-phase and persistence of a P′3-phase during charge/discharge, result in negligible volume changes (1.08%) and facile K+-diffusion through the spacious-prismatic sites (D = 10−11 - 10−10 cm2 s−1). This eventually contributes to a significant improvement in cyclic stability (99% retention after 300 cycles at 1 C) and rate capability (52 mAh·g−1 at 2 C), respectively. We believe that the use of slightly K+-deficient chromium oxides synthesized via a simple protocol should enhance the commercial viability of KxCrO2 in potassium ion batteries.
In this study, we report electrochemical synthesis of Sn oxides with dual-pore structure by employing anodic oxidation without the use of a porous template. As-prepared Sn oxide layers contain hemispherical micropores of less than 2μm diameters and nanopores of less than 50nm diameters. The formation and size of the micropores strongly depended on the thickness of the Sn layer and the type of the underlying substrate. A two-step anodic oxidation process produced a completely open pore structure, resulting in robust interconnections between the micropores and nanopores. The tensile stresses originating from the anodized Sn oxide and the associated local distortion of the Sn metal underneath it are the likely driving forces for the formation of micropores.
PVDF–HFP/ePTFE composite separator with high thermal stability and low thermal shrinkage characteristic has been developed. The PVDF–HFP acts to absorb the electrolyte and shutdown at elevated temperature. The thermally stable ePTFE matrix is adopted to improve the mechanical strength and sustain the insulation after the shutdown. This novel separator presents good ion conductivity (up to 1.29 mS cm−1) and has a low thermal shrinkage of 8.8% at 162 °C. The composite separator shutdown at 162 °C and keep its integrity before 329 °C. Cells based on the composite separator show excellent capacities at high rate discharge and stable cycling performance.
Purpose To compare the efficacy of a battery of routine and special histologic stains for the detection of acanthamoeba keratitis. Design Observational study. Methods Nine patients with culture-proven infectious keratitis whose clinical differential diagnosis included acanthamoeba and who had undergone penetrating keratoplasty were identified. Three cases each of culture-proven acanthamoeba, fungal, and herpes simplex keratitis were reviewed. Serial sections of the keratoplasty specimens were stained with hematoxylin and eosin, periodic acid–Schiff (PAS), Gomori methanamine silver (GMS), giemsa, Gram, calcofluor white, and acridine orange. Sections were reviewed in a random order and a masked fashion and classified as positive or negative for acanthamoeba, fungus, or herpes. Results The correct diagnosis was made by examination of the hematoxylin and eosin stained slides in all cases. Correct diagnoses in decreasing order of frequency were made for slides stained with PAS, GMS, acridine orange, calcofluor white, giemsa, and Gram. There were false-positive diagnoses made only with calcofluor white and acridine orange stained slides because of staining of extracellular debris and other material. Conclusions When sections are examined by an experienced observer, hematoxylin and eosin is useful compared with calcofluor white, acridine orange, GMS, PAS, giemsa, and Gram stains for the detection of acanthamoeba keratitis.
Currently acoustic tag-detecting autonomous receivers must be visited periodically to download the files of tag detections. Hence, the information about the whereabouts of tagged fishes is not available to make prompt regulatory decisions to reduce entrainment. In contrast, real-time receivers can detect the signal from a transmitter on a passing fish and immediately transmit its identity and time of detection to a website, where they can be viewed on either a computer or cellular telephone. Real-time nodes can aid regulatory biologists in making important decisions. This is a powerful new tool for resource managers and conservation biologists.
The Fe-Ge alloy nanoparticle and amorphous iron oxide shell (FeGe@Fe2O3) composite is synthesized by a facile arc-discharge method. The thickness of shell can be tuned regularly by the substitution of precursor. And then, the nanostructured core-shell FeGe@Fe2O3 is investigated as an anode material for lithium ion battery firstly. The FeGe@Fe2O3 harvests significantly enhanced reversible capacity of 1079.3 mA h g−1 at 0.1 A g−1 and 800 mA h g−1 retention after 50 cycles, and the capacity performance is superior to Fe-Ge alloy nanoparticles (NPs). It also shows satisfactory rate capability of 467 mA h g−1 at 2 A g−1 and 232 mA h g−1 at 5 A g−1, respectively, which is much better than bare Fe-Ge NPs. These good lithium storage performances are attributed to the amorphous oxide shell and the Fe-Ge alloy. To this end, this facile and tunable method provides a reasonable idea of controlling core-shell structure material precisely and this type of material can be large-scale synthesized.
Potentiodynamic lead electrodeposition on 1010 steel was studied, so as to examine the influence of glycerol on the cathodic process of lead plating and, if possible to obtain films consistently with characteristics suitable for use in lead battery technology and corrosion protection. Under potentiodynamic conditions the lead deposits obtained on 1010 steel were not satisfactory for corrosion protection but could be transformed into high purity lead powder. Given the undercutting of the lead film during the anodic dissolution scan, it is suggested that an anodic pulse could be applied to peel off the lead film on 1010 steel. The 1010 steel substrate showed itself to be potentially useful as a cathode in the treatment of Pb/H2SO4 battery industry waste and in the production of lead powder, due to its low cost and non-adherence of lead films. With the help of scanning electron microscopy (SEM) photographs, an explanation has been offered for the influence of glycerol on the lead electrodeposition process. It was concluded that glycerol reduces the dendritic growth but does not favor the adherence of the electrodeposits.
The conduction mechanism of gel electrolyte system consisting of poly(ethylene oxide) branched poly(methyl methacrylate) (PEO-PMA) matrix and ionic liquid containing lithium salt has been investigated. The kinetics of ion conduction and the mobility of lithium ion are different by the kind of ionic liquid; 1-ethyl-3-methyl imidazolium bis(trifluoromethane sulfone)imide (EMITFSI) or hexyltrimethylammonium bis(trifluoromethane sulfone)imide (HTMATFSI). Lithium ion exhibits a significant contribution for ion conduction in the gel electrolyte containing HTMATFSI. In contrast, the mobility of lithium ion is not obvious in the gel electrolyte containing EMITFSI. Such difference is considered to originate from the difference in ‘miscibility’ of polymer component in ionic liquid.
Ultrafast rechargeable lithium-ion batteries made from low-cost and abundant electrode materials would satisfy the increasing demands for energy storage worldwide. Herein, we demonstrate a large-scale hierarchical bottom-up assembly route for the formation of lithium-ion battery anode with excellent electrochemical properties by creating composites based on embedding ZnO nanoparticles into nanocarbon matrix which uniformly dispersed on the outer and inner surfaces of a porous creased carbon bubble host, which serves to hold them tightly by the pores and creases during battery operation and sandwich them between rapid ion and electron transport pathways. We successfully increase the charging and discharging rates by nearly 300-fold over the highest rate yet reported while attaining high power density and energy density which represents the best performance for long-cycle ZnO anode so far.
Silicon/graphite/disordered carbon (Si/G/DC) is coated by Li2ZrO3 using Zr(NO3)4·5H2O and CH3COOLi·2H2O as coating reagents. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are used to characterize Li2ZrO3-coated Si/G/DC composite. The Li2ZrO3-coated Si/G/DC composite exhibits a high reversible capacity with no capacity fading from 2nd to 70th cycle, indicating its excellent cycleability when used as anode materials for lithium ion batteries. A compact and stable solid-electrolyte interphase (SEI) layer is formed on the surface of Li2ZrO3-coated Si/G/DC electrode. Analysis of electrochemical impedance spectra (EIS) shows that the resistance of the coated material exhibits less variation during cycling, which indicates the integrity of electrode structure is kept during cycling. XPS shows that F and P elements do not appear in the SEI layers of Li2ZrO3-coated Si/G/DC electrode, while they have a relatively high content in SEI layers of Si/G/DC electrode. The improvement of Li2ZrO3-coated Si/G/DC is attributed to the decrease of lithium insertion depth and the formation of stable SEI film.
Layer-structured LiNi1/3Co1/3Mn1/3O2 was successfully synthesized via a reverse microemulsion (RμE) route. Well-crystallized nanosized (around 45nm) powders were obtained with calcination at 800°C. The Rietveld refinement data revealed low degree of cationic displacement in the obtained powders. Within the voltage range of 2.5–4.5V, the microemulsion-derived LiNi1/3Co1/3Mn1/3O2 delivered 187.2 and 195.5mAhg−1 at room temperature and 55°C, respectively. The prepared powders were found to exhibit low irreversible capacity and good capacity retention. Microemulsion-derived LiNi1/3Co1/3Mn1/3O2 demonstrated better rate capability than the solid-state derived samples, owing to the reduced particle size and increased surface area. Once the upper cut-off voltage reached 4.6V, the capacity faded more rapidly than in other operation potential ranges. In this study, the microemulsion process effectively improved the electrochemical characteristics of LiNi1/3Co1/3Mn1/3O2. This soft chemical route possesses a great potential for synthesizing other types of cathode materials with multiple cations.
The influence of sulfuric acid concentration on negative plate performance has been studied on 12V/32Ah lead-acid batteries with three negative and four positive plates per cell, i.e. the negative active material limits battery capacity. Initial capacity tests, including C20 capacity, cold cranking ability and Peukert tests, have been carried out in a wide range of sulfuric acid concentrations (from 1.18 to 1.33sp.gr.). High initial capacity and good CCA performance were registered for batteries with acid concentration between 1.24 and 1.30sp.gr. The charge acceptance depends on acid concentration as well as on battery state of charge. Batteries with high SoC exhibit high charge acceptance at low acid concentrations. The cycle life tests at two discharge rates (10 and 3h discharge) evidence that sulfuric acid concentration exerts a strong effect on negative plate performance. The cycle life of batteries decreases with increase of acid concentration. The obtained results demonstrate the high impact of lead sulfate solubility on the cycle life and charge efficiency of lead-acid batteries.
In this paper, accelerated rate calorimetry (ARC) and oven exposure, are used to investigate thermal runaway (TR) in lithium-ion cells. Previous work shows that lithium iron phosphate (LFP) cells have a lower risk of TR over other Li-ion chemistries. ARC is carried out on cells at various SOC to identify which decomposition reactions are contributing to the TR behaviour of a cell at different SOC. Results show, at SOC of 100% and 110%, the negative and positive electrode reactions are the main contributors to TR, while at lower SOC it is the negative electrode reaction that dominates. Cells at 100% SOC exposed to high temperatures during oven tests show, along with the ARC analysis, that the presence of the cathode and electrolyte reactions leads to an increase in the severity of a TR event for oven temperatures above 200 ∘ C . By comparing the heat generated in ARC and oven testing, it is shown that ARC does not fully capture the self-heating and TR safety hazard of a cell, unlike oven testing. This work gives new insight into the nature of the decomposition reactions and also provides an essential data set useful for model validation which is of importance to those studying LFP cells computationally.
The polymer blend based electrolyte films consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) with lithium triflate (LiCF3SO3) as a dopant ionic salt and poly(ethylene glycol) (PEG) as plasticizer have been prepared by solution cast melt–pressed and ultrasonic assisted followed by microwave irradiated solution cast melt–pressed methods. The X–ray diffraction study infers that the amorphous phase of (PEO–PMMA)–LiCF3SO3–x wt% PEG electrolytes decreases with the increase of PEG concentration. The complex dielectric function, ac electrical conductivity, electric modulus and the impedance spectra of these electrolytes have been investigated over the frequency range from 20Hz to 1MHz. It is found that all the dielectric/electrical functions of these electrolytes vary anomalously with the increase of PEG concentration, and also with the change of samples preparation methods. The activation energies have been determined from the temperature dependent values of dc ionic conductivity, polymer segmental relaxation time and dielectric strength. Results reveal that besides the amorphicity, the ionic conductivity of these electrolytes is also governed by the relaxation time and the dielectric strength, and the transport of ions is due to hopping mechanism which is coupled with segmental motion of polymers chain. Room temperature ionic conductivity values of the PEO–PMMA blend based electrolytes are found about one to two orders of magnitude higher than that of the PEO and PMMA based electrolytes.
In this work, nickel from the positive electrode of Ni–Cd batteries was recycled by chemical precipitation and electrodeposition. The structure of the material recovered by chemical precipitation is affected by temperature. Alfa nickel hydroxide is stable at low temperature but becomes beta nickel hydroxide with increasing of the synthesis temperature. Electrodeposition was accomplished by using the galvanostatic technique. The chronopotentiometric plots presented a plateau potential in the initial stage of the deposit growth due to the reduction of ionic nickel. Charge density of the plateau potential and charge efficiency decreased with increase in current density. Charge efficiency around 81.0% was the largest for current densities between 5.0mAcm−2 and 10.0mAcm−2 for q =9.0Ccm−2. As charge density increased to 90.0Cm−2, the electrodeposition efficiency decreased. In this case, there is a second plateau potential at which the evolution of hydrogen on the nickel electrode, the principal reaction, is quickly reached. Charge density affects not only the reaction kinetics, but also the deposit morphology. A decrease in microporosity is observed with the increase in charge density. The microporosity increases as the current density increases for the same charge density.
The interactions occurring in di-urea (NHC(O)NH) cross-linked poly(oxyethylene) (POE)/siloxane hybrids (di-ureasils) doped with zinc triflate (Zn(CF3SO3)2) were investigated by Fourier Transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies. Bonding of the Zn2+ ions to the urea carbonyl oxygen atoms occurs in the entire range of compositions studied (∞> n ≥1, where n, salt content, is the molar ratio of oxyethylene moieties per Zn2+ ion). At n >20 the incorporation of the guest cations progressively reduces the number of free CO groups. At n =20 the saturation of the urea cross-links is attained and the Zn2+ ions start to coordinate to the POE chains giving rise to the formation of a crystalline POE/Zn(CF3SO3)2 complex. The latter process occurs at the expense of the destruction of the hydrogen-bonded POE/urea structures of the host di-ureasil structure. New hydrogen-bonded associations, more ordered than the urea–urea aggregates present in the non-doped matrix and including Zn2+⋯OC coordination, emerge in parallel. “Free” and weakly coordinated CF3SO3 − ions, present in all the xerogels studied, appear to be the main charge carriers of the conductivity maximum of this family of ormolytes located at n =60 at 30°C. In materials with n ≤20 contact ion pairs, “cross-link separated” ions pairs and higher ionic aggregates appear. The data reported demonstrate that the behaviour of the di-ureasils doped with triflate salts depends on the type of cation.
The concept of “micro-grids” as self-sustained power systems is driven largely by business models, which have to be developed by considering the perspectives of all the stakeholders. This study tests the feasibility of the Anchor-Business-Community model of off-grid electrification in a cluster of two Hamlets in Uttar Pradesh, from the perspective of a Renewable Energy Service Company. Telecom towers, Flour Mills and rural communities have been considered as the Anchor, Business and community customers respectively. Primary surveys have been carried out to assess socio-economic characteristics, renewable energy resource availability and energy demand. Cost savings has been assumed to be the primary incentive for the customers to switch to clean energy. Cash flow analysis has been done to estimate the level of profitability of the project with and without the current level of subsidy. Solar Photovoltaic systems, Biomass gasification systems and Solar-Biomass hybrid systems have been modelled using HOMER. The model for Solar PV system with subsidy was found to be the most robust out of all three models in the scenario analysis. Solar-Biomass hybrid systems and Biomass Standalone systems are found to have the potential to offer a healthy level of returns under the best case and most likely scenarios.
Well-formed Li1.131Mn0.504Ni0.243Co0.122O2 cathode materials are synthesized via freeze drying followed by a solid state reaction at temperatures of 750–900 °C. Among these oxides, the one synthesized at 800 °C delivers the highest initial discharge capacity of 246.5 mAh g−1 at 0.1 C (1 C = 200 mA g−1) between 2.5 V and 4.8 V. Enhancing the discharge rate to 1 C, initial capacity of 197.8 mAh g−1 is obtained, and 78.8% capacity is retained after 50 cycles. Furthermore, the diffusion coefficients of Li+ in the lithium-rich layered oxide are about 10−14 cm2 s−1 and 10−15 cm2 s−1 for the initial charge platform at 3.90 V and 4.55 V, respectively, determined by galvanostatic intermittent titration technique (GITT). The Li1.131Mn0.504Ni0.243Co0.122O2 prepared by freeze drying is a promising cathode material for lithium ion batteries.
In this study, uniformly dispersed MnO@C nanocomposite with an average MnO particle size of 10nm is synthesized via a simple wet-chemical/carbonization method. In the MnO@C nanocomposite, ultrasmall MnO nanoparticles are homogeneously coated with carbon layers. As an anode material for lithium ion batteries (LIBs), this nanocomposite shows significantly enhanced electrochemical performances compared with the non-carbon coated material due to the conductive carbon layer, which provides an ideal conductive matrix for electron/ion transfer and a buffer layer to accommodate the MnO expansion during lithiation process. As a result, the MnO@C nanocomposite exhibits a high reversible capacity of ∼750mAh/g over 600 cycles at a current density of 0.7A/g and a high-rate capability of ∼340mAh/g even at 2.1A/g, which are among the best reported electrochemical performances for MnO-based materials thus far, demonstrating its potential application in LIBs with long cycling life and high power density.
Polymer gel electrolytes with both high ionic conductivity and mechanical ductility are produced using a slide-ring (SR) gel swollen with an electrolyte solution (ES) composed of propylene carbonate (PC) and lithium salt. The SR gel was derived from polyrotaxane (PR), in which cyclic molecules known as cyclodextrins (CDs) are threaded on the axial polymer chain of polyethylene glycol (PEG) capped by bulky ends, through intermolecular crosslinking between the CDs. The molar conductivity of the SR gel electrolyte with a high swelling ratio and small crosslinking density was more than 95% for pristine ES, and the activation energy and potential window of the SR gel electrolyte was close to that of pristine ES. The compressive properties of the SR gel electrolyte were also investigated; the Young's modulus of the SR gel electrolyte decreased with the crosslinking density and the SR gel electrolyte with a low crosslinking density was not fractured under compression to almost half of the original thickness.
High-loading electrodes play a crucial role in the practical applications of high-energy-density batteries, which are especially challenging for lithium–sulfur (Li–S) batteries. Herein, a mechanically robust network binder was constructed by weaving dual biopolymers (i.e., guar gum and xanthan gum) via the intermolecular binding effect of extensive functional groups in both polymers. This network binder was capable of effectively preventing polysulfides within the electrode from shuttling and, consequently, improved electrochemical performance. A remarkably high sulfur loading of 19.8 mg cm−2 and an ultrahigh areal capacity of 26.4 mA h cm−2 were achieved as a result of the robust mechanical properties of the network binder. This study paves a new way for obtaining high-energy-density batteries by the simple application of robust network biopolymer binders that are inherently low-cost and environmentally friendly.
An activated-carbon electric-double-layer capacitor is characterized and an adaptive algorithm is derived and implemented that is commensurate with potential traction applications of these energy storage devices. The electrochemical characterization relies on a simplified equivalent circuit interpretation extracted from a more-complete mathematical representation of the capacitor system. In addition to the high power capability and potentially low costs of this class of capacitors, we clarify the substantial invariance of the device performance with respect to temperature, a distinct advantage over battery systems. The robustness of the equivalent circuit in terms of capturing the salient features of the experimental data over the temperature and voltage range of interest enables the formulation of a model-reference adaptive algorithm. The algorithm developed and implemented in this work is fully recursive in that the only variables required for on-line regression are those of the previous time step and the current time step. Successful comparisons of the algorithm's adapted state of charge and power predictions provide an initial validation of the algorithm.