Search

The sodium-ion battery (Na-ion battery, NIB) is considered the most promising post-lithium energy storage technology, taking advantage of using the same manufacturing technology as Li-ion batteries (LIBs), while enabling the use of more abundant and economic, thus more sustainable, raw materials. Due to the inability of Na+ ions to be intercalated within the graphene-layered structure of graphite-based electrodes (the state of art anode material in LIBs), highly disordered and microporous carbons, known as hard carbons, are considered the anode material of choice for NIB technology. Biomass-derived biochar (BC) is one of the most relevant classes of hard carbons, exhibiting a good combination of sustainable fabrication, structural-morphological features and electrochemical performances. In this review, the main achievements on BC are rigorously reported from the production to the application into NIBs, with particular emphasis on the strategies to improve the electrochemical behaviour of BC by activating it and tailoring its chemical and structural properties. These strategies include selecting specific feedstocks, modulation of the pyrolysis temperature, pre- and post-production treatments, and materials engineering. The possible role of BC in sustainable NIBs development is also briefly discussed, together with some insights of its use in other post-Li energy storage systems and some concluding remarks and future direction of the research.

Pyrophosphates of the general formula A2BP2O7 (A = alkali metal and B = transition metal) find applications in several technological fields, including rechargeable Na-ion batteries. They present a rich polymorphism vs composition, which may strongly influence their functional properties. Therefore, to selectively obtain a specific structure is crucial for applications. Here, we combine structural investigation techniques (solid-state NMR, X-ray and neutron diffraction, and DFT calculations) to investigate the crystal chemistry of the series Na2(M/M’)P2O7 with couples M/M’ = Co/Zn and Co/Fe. For both the series, a phase transition vs composition is observed. A tetragonal to orthorhombic phase transition is found for the Zn/Co series, and an orthorhombic to triclinic phase transition is found for the Co/Fe series. Such changes are interpreted in view of the different electronic structures of the transition metal ion. In addition, with the support of modeling, short- and long-range structural analysis, we show that the coexistence of two polymorphs for a given composition is possible, suggesting that the final structures may be strongly dependent upon the synthesis procedure.

We report the synthesis and characterization of the first Sn-based mixed system, namely FA(1-x)MA(x)SnBr(3) (0 <= x <= 1), providing also the first study of the FASnBr(3) hybrid perovskite. The results indicate the formation of a continuous solid solution between the two end members with a huge modulation of the band gap induced by cation replacement. These results suggest the key role of protonated amines in the electronic structure in tin-based systems and a new and effective way of tuning the band gap.

The FA(1-x)MA(x)PbI(3) solid solution has been carefully investigated in terms of the MA/FA stoichiometry, crystal structure, and optical properties. This work allowed for the determination of reliable correlations between the amount of protonated amine and the physicochemical properties. The deleterious effect of aging on the mixed MA/FA. composition was observed by diffraction and optical measurements, showing progressive phase separation within the samples.

The implementation of aqueous electrode processing of cathode materials is a key for the development of greener Na-ion batteries. Herein, the development and optimization of the aqueous electrode processing for the ecofriendly Na0.44MnO2 (NMO) cathode material, employing carboxymethyl cellulose (CMC) as binder, are reported for the first time. The characterization of such an electrode reveals that the performances are strongly affected by the employed electrolyte solution, especially, the sodium salt and the use of electrolyte's additives. In particular, the best results are obtained using the 1 M solution of NaPF6 in EC/DEC (ethylene carbonate/diethyl carbonate) 3:7 (v/v) + 2 wt % FEC (fluoroethylene carbonate). With this electrolyte, the outstanding capacity of 99.7 mA h g-1 is delivered by the CMC-NMO cathode after 800 cycles at a 1C charge/discharge rate. On the basis of this excellent long-Term performance, a full sodium cell, composed of a CMC-based NMO cathode and hard carbon from biowaste (corn cob), has been assembled and tested. The cell delivers excellent performances in terms of specific capacity, capacity retention, and long-Term cycling stability. After 75 cycles at a C/5 rate, the capacity of the NMO in the full-cell approaches 109 mA h g-1 with a Coulombic efficiency of 99.9%.

Black phosphorus (BP) is a two-dimensional material potentially of great interest for applications in the fields of energy, sensing, and microelectronics. One of the most interesting methods to obtain BP is the conversion from red phosphorus (RP) by means of high-energy mechanochemical synthesis. To date, however, this synthesis process was not well characterized. In this work, starting from the mathematical model of energy transfer during the ball milling process, we investigate the effects on RP → BP conversion of three experimental parameters, the rotation speed, the milling time, and the weight ratio between the spheres and the milled material (BtPw ratio). The efficiency of the conversion process was verified by solid-state NMR, Raman spectroscopy, and X-ray diffraction. Whereas the first two parameters have a minor importance, the BtPw ratio plays a primary role in the RP → BP conversion. Yields approaching 100% can be obtained also with short milling times (15 min) and adequate rotation speed (e.g., 500 r.p.m.), provided that the BtPw ratio >40:1 is used. These results confirm the energy sustainability of the mechanochemical synthesis approach.

Lattice strain is considered a promising approach to modulate the structural and functional properties of oxide materials. In this study we investigate the effect of lattice strain on doping, hydration and proton transport for the family of scheelite-type proton conductors using both atomistic and DFT computational methods. The results suggest that tensile strain improves the dopant solubility and proton uptake of the material. The anisotropic proton pathways change from being within the a-b plane to being in the a-c plane. However, the predicted reduction in the migration barrier suggests that improvements in ionic conductivity due to lattice strain effects will be limited, in contrast with the work on oxide ion conduction. Such results are rationalized in terms of structural changes and differences in migration steps between oxide ions and protonic species.

One of the primary targets of current research in the field of energy storage and conversion is the identification of easy, low-cost approaches for synthesizing cell active materials. Herein, we present a novel method for preparing nanometric slabs of Na 0.44 MnO 2 , making use of the eco-friendly urea within a solution synthesis approach. This kind of preparation greatly reduces the time of reaction, decreases the thermal treatment temperature, and allows the obtaining of particles with smaller dimensions compared with those obtained through conventional solid-state synthesis. Such a decrease in particle size guarantees improved electrochemical performance, particularly at high current densities, where kinetic limitations become relevant. Indeed, the materials produced via solution synthesis outperform those prepared via solid-state synthesis both at 2 C, (95 mA h g −1 vs. 85 mA h g −1 , respectively) and 5 C, (78 mA h g −1 vs. 68.5 mA h g −1 , respectively). Additionally, the former material is rather stable over 200 cycles, with a high capacity retention of 75.7%.

W-doped LnNbO4+d compounds (Ln = La, Nd) have been recently proposed as novel interstitial-based oxide ion conductors. In this study, a powerful combination of neutron diffraction, ab initio calculations and classical molecular dynamic simulations is used in a complementary way to investigate the high temperature behavior of this system, identify possible oxygen interstitial positions and investigate the mechanism of oxygen diffusion at a high temperature. The results indicate that both systems (LaNb0.84W0.16O4.08; NdNb0.84W0.16O4.08) undergo a phase transition from a monoclinic to a tetragonal phase as a function of temperature. In the scheelite phase more than one interstitial site is potentially accessible based on the calculated energy differences. The accessibility of such interstitial positions poses the basis for an efficient oxygen diffusion migration that is predicted to be roughly isotropic and based on a knock-on mechanism.

Cordierite and mullite-cordierite based geopolymer binders were prepared as refractory bonds to embed coarse kyanite aggregates. Alkali activation was used to consolidate the refractory at room temperature and generate a reactive interface between the matrix and the aggregates. The flexural strength at room temperature of consolidated materials was 11 MPa without kyanite addition, whilst it reached 28 MPa when kyanite was added. The latter showed thermal expansion near to zero up to 500 °C, followed by an expansion of ∼0.5% up to 1000 °C, then a decrease between 1000 and 1050 °C, concluding with a constant value of expansion <0.5% up to 1250 °C. The increase in expansion was found to be linked to the transformation of the geopolymer into ceramic bond with the formation of crystalline phases, while the decrease was apparently related to the liquid phase sintering. The stability of mullite, cordierite and leucite formed up to 1250 °C was responsible for the constant expansion observed up to this temperature. The mechanical properties, the phase evolution and the thermal behavior of the K2O-MgO-Al2O3-SiO2 bonds, together with the refractory behavior of kyanite aggregates, were found suitable for the design of sustainable cold-setting refractory composites.

In this paper we report the preparation and characterization of Sr1-xNaxSiO3-0.5x samples, recently proposed as oxide ion conductors. We show that Na-doping unlikely takes place in the silicate phase, and that a secondary glassy phase is at the origin of the transport properties, thereby suggesting that the conductivity is due only to a limited extent to oxide ion migration in the crystalline system

Informal employment is a pervasive and persistent feature of most developing and developed economies. Labour taxation and labour market regulations are deemed two major causes for operating in the informal sector. Using data from France, Italy, and Spain, we analyse gross job flows and gross worker flows in the formal and informal sectors in the presence of lenient employment protection legislation, and investigate the way traditional policy interventions may favour transitions from one sector to the other. We show that optimal outcomes in terms of reduction and formalisation of informal jobs across the three countries examined are achieved with the combination of lower payroll taxes for permanent contracts and higher inspection rate for firms operating in the informal sector. Coupling lower firing costs with more frequent labour inspections also reduces informality, but this comes at the cost of an increased ratio of temporary to total employment.

We describe the functionalization of the layered perovskite HLaNb2O7 with n-propanol, n-decanol, 3-mercaptopropyl-trimethoxysilane, imidazole, n-decylamine, and histamine. The use of sonication is found to significantly improve the reaction yield and to reduce the reaction time, compared to conventional thermal treatment under reflux. The obtained intercalates are thoroughly characterized through the use of several complementary experimental techniques (scanning electron microscopy, IR spectroscopy, X-ray diffraction, thermogravimetric analysis, magic-angle spinning NMR), clarifying their structure and chemical bonding. The implications for the design of inorganic-organic composite materials are discussed.

LaWxNb1−xO4+x/2ceramics (x = 0.16) were prepared via a solid state route and studied with respect to phase stability and mixed ionic and electronic conductivity under conditions of technological relevance for fuel cell applications. The chemical compatibility against standard cathode materials revealed that Sr-doped LaMnO3could be used without detectable chemical interaction up to at least 1000 °C. Impedance spectroscopy measurements performed in the range 400–850 °C, using different atmospheres (air and N2+H2, both dry and water vapour saturated), suggest oxygen transport numbers equal to 1 under oxidising conditions, and decreasing when exposed to extreme reducing conditions. The total conductivity at 800 °C increases from 1.4·10−3 S cm−1in air to 2.5·10−3 S cm−1in wet hydrogen and 6.1·10−3 S cm−1in dry hydrogen, but the observed onset of n-type conductivity has little practical impact under typical fuel cell operating conditions.

Zinc oxide nanoarchitectures may be employed as binder-free, high specific capacity anodes for lithium batteries. By means of simple and low-impact wet chemistry approaches, we synthesized 1D (nanorods), 2D (single- and multi-layered nanosheets), and 3D (nanobrushes) ZnO arrays. These nanoarchitectures were compared as far as concerns their electrochemical properties and the structural modifications upon lithiation/delithiation. The best results were offered by 2D nanosheets, which showed reversible capacity of the order of 400 mAhg−1 after 100 cycles at 1 Ag−1. This was due to: i) small nanoparticles, with average diameter of about 10 nm, which maximize the array specific surface area and favor the formation of the LiZn alloy; ii) the presence of a mesoporous texture, which allows larger space for accommodating the volume changes upon lithiation/delithiation. However, also these 2D structures showed large irreversible capacity losses. Our work highlights the need for more efficient buffering solutions in ZnO binder-free nanostructured anodes.

Sodium-ion batteries (SIBs) are considered a good choice for post-lithium devices. Transition metal sodium pyrophosphates are among the most interesting cathode materials for SIBs. Here we study the electrochemical properties of the system Na 2 Fe 1´x Mn x P 2 O 7 (x = 0, 0.25, 0.5, 0.75, 1). By means of cyclic voltammetry (CV) and galvanostatic experiments, we confirm that pure Fe and Fe-rich compounds are promising for application in sodium batteries, whereas Mn-rich samples are less satisfactory, at least in case of solid-state reaction recipes and standard slurry preparations. Proper carbon coating is likely needed to improve the electrochemical behavior of Mn-rich samples.

Mixed ionic-electronic conductors (MIEC) are of growing interest for fuel cells, batteries and sensors. Here, by exploiting the unique properties of Li4C60 2D fulleride and poly(ethylene oxide) (PEO), we demonstrate the feasibility of a MIEC where the nature of transport can be tuned from ionic, to mixed, to almost entirely electronic, simply by changing the weight ratio of the two basic components. By coupling 7Li MAS-NMR, electrochemical impedance spectroscopy and open circuit voltage (OCV) measurements of a Li/composite/LiFePO4 cell we demonstrate that: i) a fraction of Li+ ions is extracted by Li4C60 and confined into PEO amorphous strands similarly to what happens in PEO-salt systems; ii) a transition between prevalently ionic and electronic conductivity takes place at 33 wt% Li4C60. This new class of MIEC is very promising for the design of both chemically and electrochemically stable semi-cells and interfaces which can be employed in batteries and supercapacitors.

Pyrophosphate-based materials, in particular Na2FeP2O7, constitute an interesting class of cathode compounds for rechargeable Na-ion batteries. In this work we investigate the effect of different synthetic procedures, namely: (i) glucose-assisted solid-state synthesis, and (ii) Pechini-based wet chemistry approach, on the electrochemical performances of Na2FeP2O7. Both the methods allow good specific gravimetric capacity during charge/discharge, with values close to the theoretical one at low current rates, good capacity retention and coulombic efficiency to be obtained. These results, which are better than those obtained from solid-state synthesis without added glucose, are quite independent on the different microstructures originating from the synthesis approaches, and can be attributed to the residuals of the organic fractions added during the synthesis. In addition we show that the glucose-assisted solid-state synthesis assures electrochemical stability even at relatively high currents rates (100 cycles at 1C rate).

Microbial Fuel Cells (MFCs) can be conveniently used for wastewater treatment and bioelectricity production. Their efficiency is strongly influenced by the physico-chemical properties of the ion-conducting membrane. In this work we prepare NafionTM-based composite membranes by using mesoscale SBA-15 silica, and organic-inorganic fillers obtained by functionalizing SBA-15 with SO3H groups. The proposed membranes are tested as alternative separators in MFCs for applications in wastewater treatment and their performances compared to those of standard NafionTM 117. Prolonged (3 months) MFC operation shows that the composite membrane with 5 wt% of SBA-15 functionalized with 10 mol% of SO3H gives maximum power density of 380 mW m−3, namely three times better than that of NafionTM after 90 days of operation. The same membrane offers a very effective COD removal after 14 days (more than 95%), an impressive coulombic efficiency of 34%, and very high resistance to biofouling. We conclude that the use of silica-based SO3H functionalized fillers is a powerful strategy to improve the performances of NafionTM membranes in MFCs.

ZnO is one of the materials of choice as anode for lithium batteries, due to its high theoretical capacity, natural abundance, low toxicity, and low cost. At present, however, its industrial exploitation is impeded by massive capacity fading, and by cycling instability due to the drastic volume expansions during the electrochemical lithiation/delithiation process. Herein, we present a novel graphite coated-ZnO anode for LiBs based on films of nanosheets, coated with graphite. The electrode is obtained by a simple and inexpensive solution hydrothermal synthesis, whereas the graphite is deposited by thermal evaporation, which is easier to perform than a wet chemistry technique. Our approach leads to a substantial increase of the permanent specific capacity, obtaining values of 600 mAhg-1 after 100 cycles at a high specific current of 1 Ag-1. This represents the best performance for long-cycled, ZnO-based anodes obtained so far. Such result derives from the peculiar porous structure of the nanosheets film (pore diameter < 1 nm), as well as by the graphite coating that works as a dimensional buffer and preserves its morphology during cycling. This appears a very promising strategy for designing more stable ZnO-based anodes for Li batteries and microbatteries.

Dion-Jacobson phases, like MLaNb2O7, are an interesting class of ion-exchangeable layered perovskites possessing electronic and photocatalytic properties. Their protonated and organo-modified homologues, in particular, have already been indicated as promising catalysts. However, the structural analysis of these highly tailorable materials is still incomplete, and both the intercalation process and thermal stability of the included organic moieties are far from being completely understood. In this study, we present a thorough solid-state NMR characterization of HLaNb2O7·xH2O intercalated with different amounts of octylamine, or with decylamine. Samples were analyzed as prepared, and after thermal treatment at different temperatures up to 220 °C. The substitution of pristine proton ions was followed via1H MAS NMR spectroscopy, whereas the alkyl chains were monitored through 13C(1H) CP MAS experiments. The interactions in the interlayer space were explored using 13C(1H) 2D heteronuclear correlation experiments. We demonstrate that some of the protons are involved in the functionalization reaction, and some of them are in close proximity to the alkyl ammonium chains. Heating of the hybrid materials leads first to a rearrangement of the alkyl chains and then to their degradation. The spatial arrangement of the chains, their interactions and the thermal behavior of the materials depend on the extent of the functionalization, and on the nature of the intercalated alkyl ammonium ions.

Evolution of pure hydrogen and oxygen by photocatalytic water splitting was attained from the opposite sides of a composite Pt/Ti/TiO2 photoelectrode. The TiO2 films were prepared by radio frequency (RF)-Magnetron Sputtering at different deposition time ranging from 1 up to 8 h and then characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and ultraviolet-visible-near infrared (UV-vis-NIR) diffuse reflectance spectroscopy. The photocatalytic activity was evaluated by incident photon to current efficiency (IPCE) measurements and by photocatalytic water splitting measurements in a two-compartment cell. The highest H2 production rate was attained with the photoelectrode prepared by 6 h-long TiO2 deposition thanks to its high content in the rutile polymorph, which is active under visible light. By contrast, the photoactivity dropped for longer deposition time, because of the increased probability of electron-hole recombination due to the longer electron transfer path.

In this paper we report on the deposition of La0.99Ca0.01NbO4 thin films with scheelite-type crystal structure. Thanks to the film's nanostructure, we were able to stabilize the tetragonal scheelite-type structure phase at room temperature, which involves a full removal of the fergusonite-scheelite phase transition.

Lattice strain is a promising possibility to improve materials performance in view of their application in thin-film devices. In particular, defect and transport properties in ionic conductors may be tailored through strain effects, since defect formation energy and migration barriers are correlated to structural parameters which, in turn, are influenced by strain-induced deformations. In this computational study we predicted that oxide-ion diffusion in perovskite-type lanthanum gallate can be improved through application of tensile strain. The structural deformations required to accommodate tensile lattice strain in the perovskite system are shown to result in a preferential localization of the oxygen vacancies in the equatorial plane of the GaO6 octahedra, while oxide-ion diffusion becomes anisotropic

Oxides characterized by a layered melilite structure, with general formula ABT1 (1)T2 (2)O7, find applications in many different technological fields due to their relevant magnetic, optical, and electrical properties. These functional properties are, in turn, related to local features such as structural defects and cation substitutions. Therefore, a complete structural characterization of these complex anisotropic compounds is mandatory, and the combined use of long-range (X-ray and neutron diffraction) and short-range (solid state NMR) techniques is a key approach to this aim. In this work, we present the full structural characterization of the series LaSrGa3-xAlxO7 (x = 0, 1, 1.5, 2, and 3), which was obtained for the first time by means of a new sol-gel approach. Analysis of neutron diffraction data revealed that the distribution of La/Sr and Ga/Al on the respective sites is random. 27Al and 71Ga solid state NMR enabled us to rationalize the local structure of the T sites in terms of nearest and next-nearest neighbors. This study provides a deep structural insight that can be helpful for the understanding of the functional properties and is a powerful strategy for the analysis of complex oxide systems