High-Throughput Strategies for the Design, Discovery, and Analysis of Bismuth-Based Photocatalysts.

Bismuth-based nanostructures (BBNs) have attracted extensive research attention due to their tremendous development in the fields of photocatalysis and electro-catalysis. BBNs are considered potential photocatalysts because of their easily tuned electronic properties by changing their chemical composition, surface morphology, crystal structure, and band energies. However, their photocatalytic performance is not satisfactory yet, which limits their use in practical applications. To date, the charge carrier behavior of surface-engineered bismuth-based nanostructured photocatalysts has been under study to harness abundant solar energy for pollutant degradation and water splitting. Therefore, in this review, photocatalytic concepts and surface engineering for improving charge transport and the separation of available photocatalysts are first introduced. Afterward, the different strategies mainly implemented for the improvement of the photocatalytic activity are considered, including different synthetic approaches, the engineering of nanostructures, the influence of phase structure, and the active species produced from heterojunctions. Photocatalytic enhancement via the surface plasmon resonance effect is also examined and the photocatalytic performance of the bismuth-based photocatalytic mechanism is elucidated and discussed in detail, considering the different semiconductor junctions. Based on recent reports, current challenges and future directions for designing and developing bismuth-based nanostructured photocatalysts for enhanced photoactivity and stability are summarized.

Effect of Cationic (Na+) and Anionic (F-) Co-Doping on the Structural and Electrochemical Properties of LiNi1/3Mn1/3Co1/3O2 Cathode Material for Lithium-Ion Batteries.

Elemental doping for substituting lithium or oxygen sites has become a simple and effective technique to improve the electrochemical performance of layered cathode materials. Compared with single-element doping, this work presents an unprecedented contribution to the study of the effect of Na+/F- co-doping on the structure and electrochemical performance of LiNi1/3Mn1/3Co1/3O2. The co-doped Li1-zNazNi1/3Mn1/3Co1/3O2-zFz (z = 0.025) and pristine LiNi1/3Co1/3Mn1/3O2 materials were synthesized via the sol-gel method using EDTA as a chelating agent. Structural analyses, carried out by X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy, revealed that the Na+ and F- dopants were successfully incorporated into the Li and O sites, respectively. The co-doping resulted in larger Li-slab spacing, a lower degree of cation mixing, and the stabilization of the surface structure, which substantially enhanced the cycling stability and rate capability of the cathode material. The Na/F co-doped LiNi1/3Mn1/3Co1/3O2 electrode delivered an initial specific capacity of 142 mAh g-1 at a 1C rate (178 mAh g-1 at 0.1C), and it maintained 50% of its initial capacity after 1000 charge-discharge cycles at a 1C rate.

From Solid-Solution Electrodes and the Rocking-Chair Concept to Today's Batteries.

Lithium-ion batteries (LIBs) have become ubiquitous power sources for small electronic devices, electric vehicles, and stationary energy storage systems. Despite the success of LIBs which is acknowledged by their increasing commodity market, the historical evolution of the chemistry behind the LIB technologies is laden with obstacles and yet to be unambiguously documented. This Viewpoint outlines chronologically the most essential findings related to today's LIBs, including commercial electrode and electrolyte materials, but furthermore also depicts how the today popular and widely emerging solid-state batteries were instrumental at very early stages in the development of LIBs.

O2 Adsorption Associated with Sulfur Vacancies on MoS2 Microspheres.

MoS2 is well-known for its catalytic properties, mainly to adsorb hydrogenous or carbonaceous materials. However, the effect of MoS2 on the oxygen adsorption has been investigated only a few times thus far. In this work, we first studied the adsorbability of O2 by MoS2 through the analysis of Li2O2 growth on the surface of flower-like MoS2 microspheres with different concentrations of sulfur vacancies, which can be applied as the highly active electrocatalysts for Li-O2 batteries. The enhancement of battery performance for the Def-MoS2@CTs (CTs = carbon textile substrates) with a larger concentration of sulfur vacancies (S/Mo = 1.61) can be achieved. The experimental and theoretical results confirm that the sulfur vacancies play a crucial role in the adsorption process and thus affect the morphology and nucleation of Li2O2. In addition, a fundamental catalytic mechanism for this adsorption process is also proposed. These results provide a new insight into the development of a highly active electrocatalyst by introducing a large concentration of defects for Li-O2 batteries.

Fabrication of Li4Ti5O12 (LTO) as Anode Material for Li-Ion Batteries.

The most popular anode material in commercial Li-ion batteries is still graphite. However, its low intercalation potential is close to that of lithium, which results in the dendritic growth of lithium at its surface, and the formation of a passivation film that limits the rate capability and may result in safety hazards. High-performance anodes are thus needed. In this context, lithium titanite oxide (LTO) has attracted attention as this anode material has important advantages. Due to its higher lithium intercalation potential (1.55 V vs. Li+/Li), the dendritic deposition of lithium is avoided, and the safety is increased. In addition, LTO is a zero-strain material, as the volume change upon lithiation-delithiation is negligible, which increases the cycle life of the battery. Finally, the diffusion coefficient of Li+ in LTO (2 × 10-8 cm2 s-1) is larger than in graphite, which, added to the fact that the dendritic effect is avoided, increases importantly the rate capability. The LTO anode has two drawbacks. The energy density of the cells equipped with LTO anode is lower compared with the same cells with graphite anode, because the capacity of LTO is limited to 175 mAh g-1, and because of the higher redox potential. The main drawback, however, is the low electrical conductivity (10-13 S cm-1) and ionic conductivity (10-13-10-9 cm2 s-1). Different strategies have been used to address this drawback: nano-structuration of LTO to reduce the path of Li+ ions and electrons inside LTO, ion doping, and incorporation of conductive nanomaterials. The synthesis of LTO with the appropriate structure and the optimized doping and the synthesis of composites incorporating conductive materials is thus the key to achieving high-rate capability. That is why a variety of synthesis recipes have been published on the LTO-based anodes. The progress in the synthesis of LTO-based anodes in recent years is such that LTO is now considered a substitute for graphite in lithium-ion batteries for many applications, including electric cars and energy storage to solve intermittence problems of wind mills and photovoltaic plants. In this review, we examine the different techniques performed to fabricate LTO nanostructures. Details of the synthesis recipes and their relation to electrochemical performance are reported, allowing the extraction of the most powerful synthesis processes in relation to the recent experimental results.

Recent Advances and Strategies in MXene-Based Electrodes for Supercapacitors: Applications, Challenges and Future Prospects.

With the growing demand for technologies to sustain high energy consumption, supercapacitors are gaining prominence as efficient energy storage solutions beyond conventional batteries. MXene-based electrodes have gained recognition as a promising material for supercapacitor applications because of their superior electrical conductivity, extensive surface area, and chemical stability. This review provides a comprehensive analysis of the recent progress and strategies in the development of MXene-based electrodes for supercapacitors. It covers various synthesis methods, characterization techniques, and performance parameters of these electrodes. The review also highlights the current challenges and limitations, including scalability and stability issues, and suggests potential solutions. The future outlooks and directions for further research in this field are also discussed, including the creation of new synthesis methods and the exploration of novel applications. The aim of the review is to offer a current and up-to-date understanding of the state-of-the-art in MXene-based electrodes for supercapacitors and to stimulate further research in the field.

Silver Nanocoating of LiNi0.8Co0.1Mn0.1O2 Cathode Material for Lithium-Ion Batteries.

Surface coating has become an effective approach to improve the electrochemical performance of Ni-rich cathode materials. In this study, we investigated the nature of an Ag coating layer and its effect on electrochemical properties of the LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode material, which was synthesized using 3 mol.% of silver nanoparticles by a facile, cost-effective, scalable and convenient method. We conducted structural analyses using X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy, which revealed that the Ag nanoparticle coating did not affect the layered structure of NCM811. The Ag-coated sample had less cation mixing compared to the pristine NMC811, which could be attributed to the surface protection of Ag coating from air contamination. The Ag-coated NCM811 exhibited better kinetics than the pristine one, which is attributed to the higher electronic conductivity and better layered structure provided by the Ag nanoparticle coating. The Ag-coated NCM811 delivered a discharge capacity of 185 mAh·g-1 at the first cycle and 120 mAh·g-1 at the 100th cycle, respectively, which is better than the pristine NMC811.

State-of-the-Art Electrode Materials for Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) were investigated as recently as in the seventies. However, they have been overshadowed for decades, due to the success of lithium-ion batteries that demonstrated higher energy densities and longer cycle lives. Since then, the witness a re-emergence of the SIBs and renewed interest evidenced by an exponential increase of the publications devoted to them (about 9000 publications in 2019, more than 6000 in the first six months this year). This huge effort in research has led and is leading to an important and constant progress in the performance of the SIBs, which have conquered an industrial market and are now commercialized. This progress concerns all the elements of the batteries. We have already recently reviewed the salts and electrolytes, including solid electrolytes to build all-solid-state SIBs. The present review is then devoted to the electrode materials. For anodes, they include carbons, metal chalcogenide-based materials, intercalation-based and conversion reaction compounds (transition metal oxides and sulfides), intermetallic compounds serving as functional alloying elements. For cathodes, layered oxide materials, polyionic compounds, sulfates, pyrophosphates and Prussian blue analogs are reviewed. The electrode structuring is also discussed, as it impacts, importantly, the electrochemical performance. Attention is focused on the progress made in the last five years to report the state-of-the-art in the performance of the SIBs and justify the efforts of research.

Sulfide and Oxide Inorganic Solid Electrolytes for All-Solid-State Li Batteries: A Review.

Energy storage materials are finding increasing applications in our daily lives, for devices such as mobile phones and electric vehicles. Current commercial batteries use flammable liquid electrolytes, which are unsafe, toxic, and environmentally unfriendly with low chemical stability. Recently, solid electrolytes have been extensively studied as alternative electrolytes to address these shortcomings. Herein, we report the early history, synthesis and characterization, mechanical properties, and Li+ ion transport mechanisms of inorganic sulfide and oxide electrolytes. Furthermore, we highlight the importance of the fabrication technology and experimental conditions, such as the effects of pressure and operating parameters, on the electrochemical performance of all-solid-state Li batteries. In particular, we emphasize promising electrolyte systems based on sulfides and argyrodites, such as LiPS5Cl and ß-Li3PS4, oxide electrolytes, bare and doped Li7La3Zr2O12 garnet, NASICON-type structures, and perovskite electrolyte materials. Moreover, we discuss the present and future challenges that all-solid-state batteries face for large-scale industrial applications.

Brief History of Early Lithium-Battery Development.

Lithium batteries are electrochemical devices that are widely used as power sources. This history of their development focuses on the original development of lithium-ion batteries. In particular, we highlight the contributions of Professor Michel Armand related to the electrodes and electrolytes for lithium-ion batteries.

Sputtered LiCoO2 Cathode Materials for All-solid-state Thin-film Lithium Microbatteries.

This review article presents the literature survey on radio frequency (RF)-magnetron sputtered LiCoO2 thin films used as cathode materials in all-solid-state rechargeable lithium microbatteries. As the process parameters lead to a variety of texture and preferential orientation, the influence of the sputtering conditions on the deposition of LiCoO2 thin films are considered. The electrochemical performance is examined as a function of composition of the sputter Ar/O2 gas mixture, gas flow rate, pressure, nature of substrate, substrate temperature, deposition rate, and annealing temperature. The state-of-the-art of lithium microbatteries fabricated by the rf-sputtering method is also reported.

Recent Progress on Organic Electrodes Materials for Rechargeable Batteries and Supercapacitors.

Rechargeable batteries are essential elements for many applications, ranging from portable use up to electric vehicles. Among them, lithium-ion batteries have taken an increasing importance in the day life. However, they suffer of several limitations: safety concerns and risks of thermal runaway, cost, and high carbon footprint, starting with the extraction of the transition metals in ores with low metal content. These limitations were the motivation for an intensive research to replace the inorganic electrodes by organic electrodes. Subsequently, the disadvantages that are mentioned above are overcome, but are replaced by new ones, including the solubility of the organic molecules in the electrolytes and lower operational voltage. However, recent progress has been made. The lower voltage, even though it is partly compensated by a larger capacity density, may preclude the use of organic electrodes for electric vehicles, but the very long cycling lives and the fast kinetics reached recently suggest their use in grid storage and regulation, and possibly in hybrid electric vehicles (HEVs). The purpose of this work is to review the different results and strategies that are currently being used to obtain organic electrodes that make them competitive with lithium-ion batteries for such applications.

Building Better Batteries in the Solid State: A Review.

Most of the current commercialized lithium batteries employ liquid electrolytes, despite their vulnerability to battery fire hazards, because they avoid the formation of dendrites on the anode side, which is commonly encountered in solid-state batteries. In a review two years ago, we focused on the challenges and issues facing lithium metal for solid-state rechargeable batteries, pointed to the progress made in addressing this drawback, and concluded that a situation could be envisioned where solid-state batteries would again win over liquid batteries for different applications in the near future. However, an additional drawback of solid-state batteries is the lower ionic conductivity of the electrolyte. Therefore, extensive research efforts have been invested in the last few years to overcome this problem, the reward of which has been significant progress. It is the purpose of this review to report these recent works and the state of the art on solid electrolytes. In addition to solid electrolytes stricto sensu, there are other electrolytes that are mainly solids, but with some added liquid. In some cases, the amount of liquid added is only on the microliter scale; the addition of liquid is aimed at only improving the contact between a solid-state electrolyte and an electrode, for instance. In some other cases, the amount of liquid is larger, as in the case of gel polymers. It is also an acceptable solution if the amount of liquid is small enough to maintain the safety of the cell; such cases are also considered in this review. Different chemistries are examined, including not only Li-air, Li-O2, and Li-S, but also sodium-ion batteries, which are also subject to intensive research. The challenges toward commercialization are also considered.

Doped Nanoscale NMC333 as Cathode Materials for Li-Ion Batteries.

A series of Li(Ni1/3Mn1/3Co1/3)1-xMxO2 (M = Al, Mg, Zn, and Fe, x = 0.06) was prepared via sol-gel method assisted by ethylene diamine tetra acetic acid as a chelating agent. A typical hexagonal α-NaFeO2 structure (R-3m space group) was observed for parent and doped samples as revealed by X-ray diffraction patterns. For all samples, hexagonally shaped nanoparticles were observed by scanning electron microscopy and transmission electron microscopy. The local structure was characterized by infrared, Raman, and Mössbauer spectroscopy and 7Li nuclear magnetic resonance (Li-NMR). Cyclic voltammetry and galvanostatic charge-discharge tests showed that Mg and Al doping improved the electrochemical performance of LiNi1/3Mn1/3Co1/3O2 in terms of specific capacities and cyclability. In addition, while Al doping increases the initial capacity, Mg doping is the best choice as it improves cyclability for reasons discussed in this work.

Amorphous Mo5O14-Type/Carbon Nanocomposite with Enhanced Electrochemical Capability for Lithium-Ion Batteries.

An amorphous MomO3m-1/carbon nanocomposite (m ≈ 5) is fabricated from a citrate-gel precursor heated at moderate temperature (500 °C) in inert (argon) atmosphere. The as-prepared Mo5O14-type/C material is compared to α-MoO3 synthesized from the same precursor in air. The morphology and microstructure of the as-prepared samples are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Raman scattering (RS) spectroscopy. Thermal gravimetry and elemental analysis indicate the presence of 25.8 ± 0.2% of carbon in the composite. The SEM images show that Mo5O14 is immersed inside a honeycomb-like carbon matrix providing high surface area. The RS spectrum of Mo5O14/C demonstrates an oxygen deficiency in the molybdenum oxide and the presence of a partially graphitized carbon. Outstanding improvement in electrochemical performance is obtained for the Mo5O14 encapsulated by carbon in comparison with the carbon-free MoO3.

Origin of the Fermi arcs in cuprates: a dual role of quasiparticle and pair excitations.

Angle resolved photoemission spectroscopy (ARPES) mesurements in cuprates have given key information on the temperature and angle dependence of the gap (d-wave order parameter, Fermi arcs and pseudogap). We show that these features can be understood in terms of a Bose condensation of interacting pairons (preformed hole pairs which form in their local antiferromagnetic environment). Starting from the basic properties of the pairon wavefunction, we derive the corresponding k-space spectral function. The latter explains the variation of the ARPES spectra as a function of temperature and angle up to T *, the onset temperature of pairon formation. While Bose excitations dominate at the antinode, the fermion excitations dominate around the nodal direction, giving rise to the Fermi arcs at finite temperature. This dual role is the key feature distinguishing cuprate from conventional superconductivity.

Self-assembled layer-by-layer partially reduced graphene oxide-sulfur composites as lithium-sulfur battery cathodes.

Constructing a reliable conductive carbon matrix is essential for the sulfur-containing cathode materials of lithium-sulfur batteries. A ready-made conductive matrix infiltrated with sulfur as the cathode is the usual solution. Here, a partially reduced graphene oxide-sulfur composite (prGO/S) with an ordered self-assembled layer-by-layer structure is introduced as a Li-S battery cathode. The prGO/S composites are synthesized through a facile one-step self-assembly liquid route. An appropriate amount of sulfur is in situ deposited on the surface of the prGO nanosheets by adjusting the reduction degree of the GO nanosheets. The combined effect of the electrostatic repulsions and surface energy makes the sulfur wrapped prGO nanosheets self-assemble to form an ordered layer-by-layer structure, which not only ensures the uniform distribution of sulfur but also accommodates the volume change of the sulfur species during cycling. Moreover, the conductivity of the prGO/S composites improves when the reduction time increases. XPS spectra confirm that sulfur is still chemically bonded to the prGO. After applying the prGO coating of the prGO/S composite particle and as an interlayer in a lithium-sulfur battery configuration, a high initial discharge capacity of 1275.8 mA h g-1 is achieved and the discharge capacity of the 100th cycle is 1013.8 mA h g-1 at 0.1C rate.

Universal spectral signatures in pnictides and cuprates: the role of quasiparticle-pair coupling.

Understanding the physical properties of a large variety of high-T c superconductors (SC), the cuprate family as well as the more recent iron-based superconductors, is still a major challenge. In particular, these materials exhibit the 'peak-dip-hump' structure in the quasiparticle density of states (DOS). The origin of this structure is explained within our pair-pair interaction (PPI) model: The non-superconducting state consists of incoherent pairs, a 'Cooper-pair glass' which, due to the PPI, undergoes a Bose-like condensation below T c to the coherent SC state. We derive the equations of motion for the quasiparticle operators showing that the DOS 'peak-dip-hump' is caused by the coupling between quasiparticles and excited pair states, or 'super-quasiparticles'. The renormalized SC gap function becomes energy-dependent and non retarded, reproducing accurately the experimental spectra of both pnictides and cuprates, despite the large difference in gap value.

Nanostructured MnO2 as Electrode Materials for Energy Storage.

Manganese dioxides, inorganic materials which have been used in industry for more than a century, now find great renewal of interest for storage and conversion of energy applications. In this review article, we report the properties of MnO2 nanomaterials with different morphologies. Techniques used for the synthesis, structural, physical properties, and electrochemical performances of periodic and aperiodic frameworks are discussed. The effect of the morphology of nanosized MnO2 particles on their fundamental features is evidenced. Applications as electrodes in lithium batteries and supercapacitors are examined.

Optimization of Layered Cathode Materials for Lithium-Ion Batteries.

This review presents a survey of the literature on recent progress in lithium-ion batteries, with the active sub-micron-sized particles of the positive electrode chosen in the family of lamellar compounds LiMO2, where M stands for a mixture of Ni, Mn, Co elements, and in the family of yLi2MnO3•(1 - y)LiNi½Mn½O2 layered-layered integrated materials. The structural, physical, and chemical properties of these cathode elements are reported and discussed as a function of all the synthesis parameters, which include the choice of the precursors and of the chelating agent, and as a function of the relative concentrations of the M cations and composition y. Their electrochemical properties are also reported and discussed to determine the optimum compositions in order to obtain the best electrochemical performance while maintaining the structural integrity of the electrode lattice during cycling.