Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca(2).

Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances.

Understanding the phase formation kinetics of nano-crystalline kesterite deposited on mesoscopic scaffolds via in situ multi-wavelength Raman-monitored annealing.

Kesterite, a highly promising photo-absorbing crystalline form of Cu2ZnSnS4 (CZTS), has been prepared via various routes. However, the lack of in-depth understanding of the dynamic phase formation process of kesterite leads to difficulties in optimizing its annealing conditions, hence its light harvesting performance. In this paper, in situ Raman monitored-annealing is applied to study the phase formation kinetics of nano-crystalline kesterite from a precursor deposited on a TiO2 mesoscopic scaffold. By performing in situ Raman annealing under different experimental conditions and wavelengths, several facts have been discovered: kesterite crystallization starts at as low as 170 °C, but after short time annealing at 300 °C followed by cooling, the initially formed kesterite is found to decompose. Annealing at 400 °C or higher is proven to be sufficient for stabilizing the kesterite phase. Annealing at the higher temperature of 500 °C is necessary though to promote a complete reaction and thus eliminate the parasitic copper tin sulfide (CTS) impurity intermediates identified at lower annealing temperatures. More importantly, the real-time temperature dependence of Raman peak intensity enhancement, shift and broadening for CZTS is established experimentally at 500 °C for 1 h, providing a valuable reference in future CZTS research. This work demonstrates the significance of using in situ Raman spectroscopy in elucidating the kesterite phase formation kinetics, a critical step towards full crystal phase control - a prerequisite for developing fully functional CZTS-based optoelectronic devices.

New insight into the atomic-scale bulk and surface structure evolution of Li4Ti5O12 anode.

Identifying the structure of electrodes at atomic-scale remains a key challenge but is a fertile realm for groundbreaking fundamental research in the advanced Li-ion battery material field. In this context, the subtle structure evolution taking place during lithiation/delithiation in the bulk/surface of Li(4)Ti(5)O(12) spinel (LTO) was probed using scanning transmission electron microscopy and found to undergo significant structure torque, namely Ti-O bond stretching/shrinking at different state-of-charge (SOC), which is not identified previously. This kind of nanostructure change plays an important role in facilitating the formation of capturing centers for the electron/hole pairs in a 3.80 eV insulating material as is LTO. Furthermore, with the aid of electron energy loss spectroscopy, the spontaneous charge transfer process, Ti(3+) ↔ e(-) + Ti(4+), was confirmed in the fully lithiated Li(7)Ti(5)O(12) surface as an essential step of the gas-releasing phenomenon. This new insight paves the way toward deeper comprehension and ultimately control of the electrochemical process for this and other important Li-ion battery materials.

Direct imaging of layered O3- and P2-NaxFe1/2Mn1/2O2 structures at the atomic scale.

Using aberration-corrected scanning transmission electron microscopy (STEM) with high-angle annular-dark-field (HAADF) and annular-bright-field (ABF) techniques, the atomic-scale structures of the O3 and P2 phases of NaxFe1/2Mn1/2O2 are investigated systematically. The Na, transition metal M (Fe and Mn) and O columns are well revealed and precisely assigned to the O3 and P2 phase layered structures. The O3 phase sample demonstrates larger atomic site fluctuations along [001] direction but with less structural imperfections (e.g. interlayer structure and stacking defaults) than the P2 phase sample. Furthermore, a clear surface with a regular structure is observed for the O3-NaFe1/2Mn1/2O2 sample, while a surface with a large amount of Na-M antisites is observed for the P2-Na2/3Fe1/2Mn1/2O2 sample.

Correlation between hysteresis dynamics and inductance in hybrid perovskite solar cells: studying the dependency on ETL/perovskite interfaces.

In this study, to elucidate the origin of inductance and its relationship with the phenomenon of hysteresis in hybrid perovskite solar cells (PSCs), two electron transport layer (ETL) structures have been utilized: (a) rutile titania nanorods grown over anatase titania (AR) and (b) anatase titania covering the rutile titania nanorods (RA). The rutile and anatase phases are prepared via hydrothermal synthesis and spray pyrolysis, respectively. PSCs based on an ETL with an RA structure attain higher short-circuit current density (JSC) and open-circuit voltage (VOC) while showing a slightly lower fill factor (FF) compared with their AR counterparts. Using electrochemical impedance spectroscopy (EIS) measurements, we show that the ETL plays a major role in setting the tone for ionic migration speed and consequent accumulation. Moreover, we consider the conductivity of transport layers as a determining factor in not only giving rise to inductive features but also dictating the bias region under which recombination takes place, ultimately influencing hysteresis locus.

Nanoengineering of NiO/MnO2/GO Ternary Composite for Use in High-Energy Storage Asymmetric Supercapacitor and Oxygen Evolution Reaction (OER).

Designing multifunctional nanomaterials for high performing electrochemical energy conversion and storage devices has been very challenging. A number of strategies have been reported to introduce multifunctionality in electrode/catalyst materials including alloying, doping, nanostructuring, compositing, etc. Here, we report the fabrication of a reduced graphene oxide (rGO)-based ternary composite NiO/MnO2/rGO (NMGO) having a range of active sites for enhanced electrochemical activity. The resultant sandwich structure consisted of a mesoporous backbone with NiO and MnO2 nanoparticles encapsulated between successive rGO layers, having different active sites in the form of Ni-, Mn-, and C-based species. The modified structure exhibited high conductivity owing to the presence of rGO, excellent charge storage capacity of 402 F·g-1 at a current density of 1 A·g-1, and stability with a capacitance retention of ~93% after 14,000 cycles. Moreover, the NMGO//MWCNT asymmetric device, assembled with NMGO and multi-wall carbon nanotubes (MWCNTs) as positive and negative electrodes, respectively, exhibited good energy density (28 Wh·kg-1), excellent power density (750 W·kg-1), and capacitance retention (88%) after 6000 cycles. To evaluate the multifunctionality of the modified nanostructure, the NMGO was also tested for its oxygen evolution reaction (OER) activity. The NMGO delivered a current density of 10 mA·cm-2 at the potential of 1.59 V versus RHE. These results clearly demonstrate high activity of the modified electrode with strong future potential.

Further understanding of the adsorption mechanism of N719 sensitizer on anatase TiO2 films for DSSC applications using vibrational spectroscopy and confocal Raman imaging.

Vibrational spectroscopic studies of N719 dye-adsorbed TiO(2) films have been carried out by using SERRS, ATR-FTIR, and confocal Raman imaging. The high wavenumber region (3000-4000 cm(-1)) of dye adsorbed TiO(2) is analyzed via Raman and IR spectroscopy to investigate the role of surface hydroxyl groups in the anchoring mode. As a complementary technique, confocal Raman imaging is employed to study the distribution features of key dye groups (COO-, bipyridine, and C=O) on the anatase surface. Sensitized TiO(2) films made from two different nanocrystalline anatase powders are investigated: a commercial one (Dyesol) and our synthetic variety produced through aqueous synthesis. It is proposed the binding of the N719 dye to TiO(2) to occur through two neighboring carboxylic acid/carboxylate groups via a combination of bidentate-bridging and H-bonding involving a donating group from the N719 (and/or Ti-OH) units and acceptor from the Ti-OH (and/or N719) groups. The Raman imaging distribution of COO(-)(sym) on TiO(2) was used to show the covalent bonding, while the distribution of C=O mode was applied to observe the electrostatically bonded groups.

The synthesis of aqueous-dispersible anatase TiO2 nanoplatelets.

Aqueous well-dispersed and phase-pure anatase TiO(2) truncated octahedron nanoplatelets (NPLs) were prepared via controlled hydrolysis of titanium tetrachloride (TiCl(4)) in ethylene glycol at 240 degrees C. Two shapes, square and hexagon, were observed by microscopy, exactly corresponding to the truncated octahedron NPLs. Ethylene glycol was found to produce water in situ that reacts with TiCl(4) to produce TiO(2) and HCl-the latter promoting TiO(2) colloid peptization. TiO(2) truncated octahedron NPLs are formed under the stabilizing action of ethylene glycol thermolysis derivatives, such as aldehydes. Crystal growth of the TiO(2) NPLs was affected by the reaction temperature that determines the water production rate and HCl-assisted peptization. TGA and FT-IR results showed approximately 1.2% ethylene glycol thermolysis derivatives are attached to the surface of the TiO(2) NPLs, which prevents their agglomeration, hence making them easily dispersible in aqueous media. HR-TEM and SAED results showed that the TiO(2) NPLs are well crystallized and that the SAED patterns of the single TiO(2) NPL changes with its size and shape. XRD patterns showed that the TiO(2) NPLs are phase-pure anatase and the percentage of the [101] plane in the TiO(2) NPLs to be only 18%-a structural feature that renders the TiO(2) NPLs with enhanced UV absorption and reactivity properties.

Core hole screened electron energy loss calculations of beam damaged lithium fluoride.

A method of calculating the magnitude of the core hole screening of lithium materials is implemented for the simulation of Energy Loss Near Edge Structure (ELNES). ELNES is calculated for a range of lithium materials resulting in improved agreement between calculation and experiment. The technique uses linear response theory to relate the electron density to the core hole shielding contribution from the valence electrons in a crystal. This contribution is then implemented via a non-integer core hole in final state rule calculations.

Nanoscale assembling of graphene oxide with electrophoretic deposition leads to superior percolation network in Li-ion electrodes: TiNb2O7/rGO composite anodes.

In this paper, electrophoretic deposition (EPD) is shown to promote nanoscale assembling of graphene oxide (GO) enabling the fabrication of highly homogeneous, robust, and capacity fade resistant composite titanium niobate (TiNb2O7, TNO)/rGO anodes upon reductive annealing. Control tests revealed that EPD is superior to conventional PVDF-based casting in maximizing the performance benefits from using reduced GO in Li-ion electrode fabrication as is the case of TNO that is plagued with conductivity and capacity fading problems. In this particular study, we show that there is a synergy developed between GO and EPD with the former (1) stabilizing the EPD suspension, (2) acting as a flexible binder net that affords mechanical integrity during the volume expansion of TNO, (3) serving as a conductive filler, and (4) contributing to Li-ion storage via pseudocapacitance. As a consequence, a superior percolation network is developed. Thus while both EPD- and PVDF- built TNO/rGO composite anodes exhibited high initial capacities (∼350 and 318 mA h g-1) at 0.5 C cycling, respectively, their cycling behaviour was quite different with the latter experiencing high internal polarization and extended degradation. Post-mortem PEEM-XANES analysis clearly demonstrated a highly homogeneous mesostructure in the case of the EPD-built TNO/rGO anode vs. a highly segregated and dis-jointed rGO and TNO component clustering in the PVDF-built electrode.

Progress and Status of Hydrometallurgical and Direct Recycling of Li-Ion Batteries and Beyond.

An exponential market growth of Li-ion batteries (LIBs) has been observed in the past 20 years; approximately 670,000 tons of LIBs have been sold in 2017 alone. This trend will continue owing to the growing interest of consumers for electric vehicles, recent engagement of car manufacturers to produce them, recent developments in energy storage facilities, and commitment of governments for the electrification of transportation. Although some limited recycling processes were developed earlier after the commercialization of LIBs, these are inadequate in the context of sustainable development. Therefore, significant efforts have been made to replace the commonly employed pyrometallurgical recycling method with a less detrimental approach, such as hydrometallurgical, in particular sulfate-based leaching, or direct recycling. Sulfate-based leaching is the only large-scale hydrometallurgical method currently used for recycling LIBs and serves as baseline for several pilot or demonstration projects currently under development. Conversely, most project and processes focus only on the recovery of Ni, Co, Mn, and less Li, and are wasting the iron phosphate originating from lithium iron phosphate (LFP) batteries. Although this battery type does not dominate the LIB market, its presence in the waste stream of LIBs causes some technical concerns that affect the profitability of current recycling processes. This review explores the current processes and alternative solutions to pyrometallurgy, including novel selective leaching processes or direct recycling approaches.

Aqueous-based Binary Sulfide Nanoparticle Inks for Cu2ZnSnS4 Thin Films Stabilized with Tin(IV) Chalcogenide Complexes.

Cu2ZnSnS4(CZTS) is a promising semiconductor material for photovoltaic applications,with excellent optical and electronic properties while boasting a nontoxic, inexpensive, andabundant elemental composition. Previous high-quality CZTS thin films often required eithervacuum-based deposition processes or the use of organic ligands/solvents for ink formulation,which are associated with various issues regarding performance or economic feasibility. To addressthese issues, an alternative method for depositing CZTS thin films using an aqueous-basednanoparticle suspension is demonstrated in this work. Nanoparticles of constituent binary sulfides(CuxS and ZnS) are stabilized in an ink using tin(IV)-based, metal chalcogenide complexes such as[Sn2S6]4-. This research paper provides a systematic study of the nanoparticle synthesis and inkformulation via the enabling role of the tin chalcogenide complexing power, the deposition of highqualityCZTS thin films via spin coating and annealing under sulfur vapor atmosphere, theirstructural characterization in terms of nanocrystal phase, morphology, microstructure, anddensification, and their resultant optoelectronic properties.

Lithium Photo-intercalation of CdS-Sensitized WO3 Anode for Energy Storage and Photoelectrochromic Applications.

Integration of solar-energy harvesting and storage functions has attracted significant research attention, as it holds promise for ultimate development of light-chargeable devices. In this context, a functional nanocomposite anode that not only permits electrochemical energy storage through Li-ion photo-intercalation, but also exhibits potential for photoelectrochromic applications, was investigated. The nanocomposite is made of the Li-ion intercalation compound WO3 , thinly coated with TiO2 and sensitized by the photoactive semiconductor CdS. During light exposure, the photoelectrons from CdS are transported to the WO3 /electrolyte interface, where Li-ion intercalation takes place. Photoelectron transport is facilitated by the interfacial TiO2 layer. The WO3 was shown to be functional in multiple photocharge-discharge cycles, but the CdS suffers from degradation and photocorrosion. Hence, the selection of compatible semiconductors and protective coating strategies should be pursued to overcome these issues.

Coprecipitation of arsenate with iron(III) in aqueous sulfate media: effect of time, lime as base and co-ions on arsenic retention.

The removal and immobilization of arsenic from industrial mineral-processing effluents typically involves lime neutralization and coprecipitation of arsenate with ferric iron. Despite the wide practice and environmental importance of this technique, no laboratory study has focused on the roles of lime as base and third ions like Ca2+, Ni2+ and SO(2)4(-) on the kinetics of arsenic retention by the coprecipitates. In this work, coprecipitation was performed at 22 degrees C by fast (10 min) neutralization of industrially relevant concentrated arsenate-iron(III) (Fe/As=2, 4) acidic sulfate solutions to different pHs (4, 6, 8) in batch reactors, and the concentration of arsenic was monitored up to 1 year. The tests showed that maximum removal of arsenic was achieved upon neutralization to the target pH. Arsenic was found to be released back into solution from the precipitates upon continuing mild agitation at constant pH. Near-equilibrium was attained at different times depending on the applied pH: 10 days at pH 4, 6 months at pH 6 and 9 months at pH 8. An aging treatment at pH 4 significantly enhanced arsenic retention (arsenic release was reduced by at least 50%) after the system was finally stabilized at pH 8. The retention of arsenic at pH 8 was multifold improved (by a factor x 25) when lime was used instead of NaOH. Similarly, the retention of arsenic was enhanced by the presence of calcium and nickel ions in the starting solution. Finally, evidence of Ca(II)-Fe(III)-As(V) association was found, but not sulfate incorporation at pH 8.

Nanostructural and photo-electrochemical properties of solution spin-coated Cu2ZnSnS4-TiO2 nanorod forest films with an improved photovoltaic performance.

Cu2ZnSnS4 (CZTS), other than in standard p-n junction device architecture, can be employed as a broad light absorber upon coating onto a wide bandgap electron conducting TiO2 film. Earlier CZTS sensitized TiO2 films have yielded low photoconversion efficiency and Voc. In this work, a water-ethanol solution spin coating approach has been applied to directly deposit CZTS nanocrystallites on rutile TiO2 nanorods grown on an FTO substrate (TNR) for evaluation in a sensitized solar cell configuration. The FTO@TNR@CZTS photoanode following controlled annealing is shown to exhibit improved photovoltaic properties. Focused-ion beam cross-sections of CZTS nanocoating onto TiO2 nanorod forest films have revealed nanoscale morphological details and electrochemical impedance spectroscopy helped identify TiO2 nanorod film growth characteristics for a reduced charge recombination. The band alignment of CZTS and TiO2 has been determined by XPS helping to explain the origin of Voc deficit. An all-solid state device featuring spiro OMeTAD as HTM and CdS as a buffer layer has been designed with 2% efficiency.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries.

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Stability of arsenate-bearing Fe(III)/Al(III) co-precipitates in the presence of sulfide as reducing agent under anoxic conditions.

Currently, the co-precipitation of arsenate with ferric iron at molar ratios Fe(III)/As(V) ≥ 3 by lime neutralization produces tailings solids that are stable under oxic conditions. However not much is known about the stability of these hazardous co-precipitates under anoxic conditions. These can develop in tailings storage sites by the action of co-discharged reactive sulfides, organic reagent residuals or bacterial activity. The ferric matrix can then undergo reductive dissolution reactions, which could release arsenic into the pore water. Co-ions like aluminum could provide a redox-immune sink to scavenge any mobilized arsenic as a result of reduction of ferric. As such, in this work Fe(III)/As(V) = 4 and aluminum substituted Fe(III)/Al(III)/As(V) = 2/2/1 co-precipitates were produced in a mini continuous co-precipitation process circuit and subjected to excess sulfide addition under inert gas to evaluate their stability. It was found that the ferric-arsenate co-precipitate could retain up to 99% (30 mg/L in solution) of its arsenic content despite the high pH (10.5) and extremely reducing (Eh < -200 mV) environment. There was no significant reduction of arsenate and only 45% of ferric iron was reduced. Partial aluminum substitution was found to cut the amount of mobilized arsenic by 50% (down to 15 mg/L) hence mixed Fe(III)/Al(III)-arsenate co-precipitates may offer better resistance to reductive destabilization over the long term than all iron co-precipitates.

Spontaneous reaction between an uncharged lithium iron silicate cathode and a LiPF6-based electrolyte.

The reaction between an uncharged Li2FeSiO4 (LFS) cathode and a LiPF6-EC/DMC electrolyte is revealed by in situ XANES in coin cells. This study shows clear evidence of delithiation and iron oxidation in LFS prior to cycling. Subsequent cycling appears to partially restore the original lithiation level, an observation that needs to be taken into consideration in future LFS development work.

Growth of Cu2ZnSnS4 Nanocrystallites on TiO2 Nanorod Arrays as Novel Extremely Thin Absorber Solar Cell Structure via the Successive-Ion-Layer-Adsorption-Reaction Method.

Cu2ZnSnS4 (CZTS) is an environmentally benign semiconductor with excellent optoelectronic properties that attracts a lot of interest in thin film photovoltaics. In departure from that conventional configuration, we fabricate and test a novel absorber-conductor structure featuring in situ successive-ion-layer-adsorption-reaction (SILAR)-deposited CZTS nanocrystallites as a light absorber on one-dimensional TiO2 (rutile) nanorods as an electron conductor. The effectiveness of the nanoscale heterostructure in visible light harvesting and photoelectron generation is demonstrated with an initial short circuit current density of 3.22 mA/cm(2) and an internal quantum efficiency of ∼60% at the blue light region, revealing great potential in developing CZTS extremely thin absorber (ETA) solar cells.

Incorporation of arsenic into gypsum: Relevant to arsenic removal and immobilization process in hydrometallurgical industry.

Gypsum precipitates as a major secondary mineral during the iron-arsenate coprecipitation process for the removal of arsenic from hydrometallurgical effluents. However, its role in the fixation of arsenic is still unknown. This work investigated the incorporation of arsenic into gypsum quantitatively during the crystallization process at various pHs and the initial arsenic concentrations. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), X-ray absorption near edge spectroscopy (XANES) and scanning electron microscopy (SEM) were employed to characterize the coprecipitated solids. The results showed that arsenate was measurably removed from solution during gypsum crystallization and the removal increased with increasing pH. At lower pH where the system was undersaturated with respect to calcium arsenate, arsenate ions were incorporated into gypsum structure, whereas at higher pH, calcium arsenate was formed and constituted the major arsenate bearing species in the precipitated solids. The findings may have important implications for arsenic speciation and stability of the hydrometallurgical solid wastes.