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The CO2 sorption properties of sodium hafnium oxide (Na2HfO3) were investigated in this study. Na2HfO3 was synthesized by solid-state synthesis using Na2CO3 and HfO2 as starting materials. The solid-state synthesized Na2HfO3 appeared structurally similar to other mixed metal oxides such as Na2ZrO3, but stacking disorder appeared to be common in Na2HfO3. The synthesis conditions, including the Na : Hf ratio (between 0.5 and 1.5 : 1), synthesis temperature, time and heating rate, were investigated to optimize CO2 sorption properties of Na2HfO3. The Na2HfO3 sorbent showed comparable CO2 uptake capacity, reaction rate and excellent cycling stability compared to other metal oxide sorbents. Na2HfO3 with Na : Hf = 1 : 1 and 1.25 : 1 showed the highest CO2 uptake among all Na2HfO3 samples obtained, with a CO2 uptake capacity of around 15 wt% (at 650–800 °C). The CO2 uptake rate of NHO-1 and NHO-1.25 was fast with over 80% of the equilibrium uptake reached within 250 s. Na2HfO3 remained stable even after 100 cycles with less than 3% difference in the CO2 uptake capacity between the 1st and 100th cycles. We performed kinetic analysis on the CO2 sorption data and found that the Avrami–Erofeev model fitted the kinetic data best among the kinetic models used. Apart from sorbent optimization, we showed that 3D-printing of Na2HfO3 : HfO2 mixtures can be used to produce structured Na2HfO3 sorbents with a slightly improved CO2 uptake rate and the same CO2 uptake capacity as the powder-based solid-state synthesized Na2HfO3 sorbent.

Simultaneously tuning the electronic structure of active sites and the microenvironment of the carbon matrix in metal phosphide/carbon nanohybrids is the most effective way to design and develop bi-functional electrocatalysts for electrochemically related energy storage devices. Inspired by this, a robust and advanced N/P co-doped carbon-based dodecahedron catalyst with confined Fe-doped Co2P particles was successfully prepared through a multi-doping engineering strategy. Phytic acid molecules, which were used in the synthesis of the catalyst, not only contribute to the formation of the porous structure, but also act as a phosphorus source to form the corresponding metal phosphide and the P dopant in the carbon matrix. Thanks to the unique composition and structure-dependent merits, the microenvironment of the electrocatalyst was significantly modulated, thus promoting the advantageous local charge rearrangement and smooth mass/charge transfer processes during the oxygen-related electrocatalytic reactions. As a result, the resultant catalyst exhibited significantly enhanced reversible oxygen activity, as evidenced by an ultra-small potential gap of 0.655 V (half-wave potential of 0.895 V for the oxygen reduction reaction; η10 of 320 mV for the oxygen evolution reaction), a remarkable specific capacity of 762 mA h gZn−1, and high voltaic efficiency, exceeding most previous reports. This study provides a new synthetic approach for fabricating highly efficient bi-functional oxygen catalysts and can be handily extended to the synthesis of other heterogeneous electrocatalysts for sustainable energy storage.

While lithium metal is considered an ideal anode for the next generation of high-energy-density batteries, some major issues such as huge volume change and continuous dendrite formation during lithium plating have hindered its practical applications. Zinc oxide (ZnO) modification of surfaces has shown great potential for inducing a homogeneous Li plating to attain dendrite-free lithium metal anodes. Although considerable improvements in electrochemical performance have been achieved, the detailed mechanism of the evolution of Li nucleation and growth morphology remains elusive. Here, we combine experimental and theoretical calculations to study the Li deposition behaviour during and after the initial nucleation on a thin and uniform layer of ZnO-coated 3D nickel foam. Upon lithiation of the ZnO layer, Li2O and LiZn are formed through a conversion reaction; this composite layer provides specific properties ensuring a homogeneous Li plating. The results showed that dendrite growth not only leads to the formation of cracks on the surface but also provokes the breakoff of some parts of the converted layers from the bulk surface. In addition, no new nucleation occurs upon continued Li deposition, with Li plating mainly taking place on the initial nuclei underneath the protective layer. As a result, large granular Li particles grow at the site of the initial Li nucleation centre, leading to the improvement of electrochemical performances. A deeper understanding of the mechanism of Li nucleation and growth and the morphology of the formed dendrites can help with the development of lithium metal batteries.

C-18 is a cyclo[18]carbon that consists of 18 carbon atoms. Beyond the detection of an intermediate gas phase species, the synthesis of a solid-state C-18 and elucidation of its bonding structure have remained significant scientific challenges over the past half century. Until recently, this unorthodox carbon allotrope was conceptually feasible, while experimentally elusive in the solid state. Finally, this carbon allotrope has made its long-awaited debut when a collaborative research effort successfully synthesized and revealed the structure of cyclocarbon. The long 50 years of waiting is now over with the unveiling of this new form of chemistry's most celebrated element. This article highlights the discovery of this new allotrope from the carbon family, and discusses its chemical structure, potential applications, and challenges for future research.

The conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) forms a promising alternative to conventional inorganic conductors, where deposition of thin films via vapour phase polymerization (VPP) has gained particular interest owing to high electrical conductivity within the plane of the film. The conductivity perpendicular to the film is typically much lower, which may be related not only to preferential alignment of PEDOT crystallites but also to vertical stratification across the film. In this study, we reveal non-linear vertical microstructural variations across VPP PEDOT:Tos thin films, as well as significant differences in doping level between the top and bottom surfaces. The results are consistent with a VPP mechanism based on diffusion-limited transport of polymerization precursors. Conducting polymer films with vertical inhomogeneity may find applications in gradient-index optics, functionally graded thermoelectrics, and optoelectronic devices requiring gradient doping. The fulltext is published under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence.https://creativecommons.org/licenses/by-nc/3.0/

Gallium alloying and grading in Cu(In,Ga)Se-2 (CIGS) are well-established strategies for improving performance of thin-film solar cells by tailoring band profiles within the absorber. Similarly, Ag incorporation is considered to be an effective complementary route towards further advancement of the field. Herein, we explore thermodynamics of the formation of (Ag,Cu)(In,Ga)Se-2 (ACIGS) alloy. Using first-principles methods, we reveal the existence of a miscibility gap in the Ga-rich alloys at temperatures close to those employed for the co-evaporation growth. We demonstrate that this property can result in phase separation and the formation of Ag gradients throughout the film thickness. We prove experimentally that the phase separation can indeed occur during low-temperature growth and/or post-deposition treatments. Furthermore, we uncover the anticorrelation between Ag and Ga contents, and demonstrate thermodynamically-driven formation of [Ag]/([Ag] + [Cu]) gradients in films with a steep [Ga]/([Ga] + [In]) profile. Finally, we discuss how these phenomena can influence solar cell devices. The presented results are expected to provide fundamental insight into the physics of growth and processing of ACIGS absorbers, which could be utilized to further boost the efficiency of thin-film solar cells.

Complex compound semiconductors, such as the emerging solar cell material Cu2ZnSn(S,Se)4 (CZTS), present major experimental challenges in terms of understanding and controlling growth processes and defect formation. This study aims to shed light upon the complicated interplay of the synthesis conditions and CZTS thin film properties. Composition-spread thin films are fabricated in different atmospheric conditions during the annealing step. The span of the single-phase region is identified by a phase analysis combining XRD and Raman mapping. The phase characterisation is strengthened by STEM-EDX analysis. Our results show that the stability of the CZTS phase is strongly affected by the process conditions which is observed as a shift in the secondary phase boundaries and different levels of maximum cation ordering achieved in the different samples. With regard to the photoluminescence intensity, all investigated samples show the same trends: regions with Cu3SnS4 secondary phase show the lowest intensity, while the presence of SnSx secondary phases greatly enhances the photoluminescence intensity. The single-phase region features an overall low photoluminescence intensity without a remarkable composition dependence and we propose the presence of deep defects in absence of secondary phases that limit the radiative recombination. We discuss implications for future efforts in defect engineering toward improving the efficiency of CZTS thin film devices.

Electrochromic windows and glass facades are able to impart energy efficiency jointly with indoor comfort and convenience. Long-term durability is essential for practical implementation of this technology and has recently attracted broad interest. Here we show that a simple potentiostatic pretreatment of sputterdeposited thin films of amorphous WO3-the most widely studied electrochromic material-can yield unprecedented durability for charge exchange and optical modulation under harsh electrochemical cycling in a Li-ion-conducting electrolyte and effectively evades harmful trapping of Li. The pretreatment consisted of applying a voltage of 6.0 V vs. Li/Li+ for several hours to a film backed by a transparent conducting In2O3: Sn layer. Associated compositional and structural modifications were probed by several techniques, and improved durability was associated with elemental intermixing at the WO3/ITO and ITO/glass boundaries as well as with carbonaceous solid-electrolyte interfacial layers on the WO3 films. Our work provides important new insights into long-term durability of ion-exchange-based devices.

Lithium-rich materials, such as Li1.2Ni0.2Mn0.6O2, exhibit capacities not limited by transition metal redox, through the reversible oxidation of oxide anions. Here we offer detailed insight into the degree of oxygen redox as a function of depth within the material as it is charged and cycled. Energy-tuned photoelectron spectroscopy is used as a powerful, yet highly sensitive technique to probe electronic states of oxygen and transition metals from the top few nanometers at the near-surface through to the bulk of the particles. Two discrete oxygen species are identified, On− and O2−, where n < 2, confirming our previous model that oxidation generates localised hole states on O upon charging. This is in contrast to the oxygen redox inactive high voltage spinel LiNi0.5Mn1.5O4, for which no On− species is detected. The depth profile results demonstrate a concentration gradient exists for On− from the surface through to the bulk, indicating a preferential surface oxidation of the layered oxide particles. This is highly consistent with the already well-established core–shell model for such materials. Ab initio calculations reaffirm the electronic structure differences observed experimentally between the surface and bulk, while modelling of delithiated structures shows good agreement between experimental and calculated binding energies for On−.

The instability of carbon cathode materials is one of the key problems that hinder the development of lithium–air/lithium–oxygen (Li–O2) batteries. In this contribution, a type of TiC-based cathode is developed as a suitable alternative to carbon based cathodes, and its stability with respect to its surface properties is investigated. Here, a free-standing TiC nanowire array cathode was in situ grown on a carbon textile, covering its exposed surface. The TiC nanowire array, via deposition with Ru nanoparticles, showed enhanced oxygen reduction/evolution activity and cyclability, compared to the one without Ru modification. The battery performance of the Li–O2cells with Ru–TiC was investigated by using in operando synchrotron radiation powder X-ray diffraction (SR-PXD) during a full cycle. With the aid of surface analysis, the role of the cathode substrate and surface modification is demonstrated. The presented results are a further step toward a wise design of stable cathodes for Li–O2 batteries.

To provide energy densities higher than those of conventional Li-ion batteries, a Li–O2 battery requires a cathode with high surface area to host large amounts of discharge product Li2O2. Therefore, reversible formation of discharge products needs to be investigated in Li–O2 cells containing high surface area cathodes. In this study, a binder-free oxygen electrode consisting of a 3-D graphene structure on aluminum foam, with a high defect level (ID/IG = 1.38), was directly used as the oxygen electrode in Li– O2 batteries, delivering a high capacity of about 9 *104 mA h g-1 (based on the weight of graphene) at the first full discharge using a current density of 100 mA ggraphene-1 . This performance is attributed to the 3-D porous structure of graphene foam providing both an abundance of available space for the deposition of discharge products and a high density of reactive sites for Li–O2 reactions. Furthermore, the formation of discharge products with different morphologies and their decomposition upon charge were observed by SEM. Some nanoscaled LiOH particles embedded in the toroidal Li2O2 were detected by XRD and visualized by TEM. The amount of Li2O2 formed at the end of discharge was revealed by a titration method combined with UV-Vis spectroscopy analysis. Swedish Research Council Swedish Energy Agency Ångpanneföreningen’s Foundation for Research and Development J. Gust. Richert Foundation State Key Laboratory of Fine Chemicals (KF1413) China Scholarship Council

Solid polymer electrolytes (SPEs) are promising candidates for Li metal battery applications, but the interface between these two categories of materials has so far been studied only to a limited degree. A better understanding of interfacial phenomena, primarily polymer degradation, is essential for improving battery performance. The aim of this study is to get insights into atomistic surface interaction and the early stages of solid electrolyte interphase formation between ionically conductive SPE host polymers and the Li metal electrode. A range of SPE candidates are studied, representative of major host material classes: polyethers, polyalcohols, polyesters, polycarbonates, polyamines and polynitriles. Density functional theory (DFT) calculations are carried out to study the stability and the electronic structure of such polymer/Li interfaces. The adsorption energies indicated a stronger adhesion to Li metal of polymers with ester/carbonate and nitrile functional groups. Together with a higher charge redistribution, a higher reactivity of these polymers is predicted as compared to the other electrolyte hosts. Products such as alkoxides and CO are obtained from the degradation of ester- and carbonate-based polymers by AIMD simulations, in agreement with experimental studies. Analogous to low-molecular-weight organic carbonates, decomposition pathways through C-carbonyl-O-ethereal and C-ethereal-O-ethereal bond cleavage can be assumed, with carbonate-containing fragments being thermodynamically favorable.