Sustainable and Environmentally Friendly Na and Mg Aqueous Hybrid Batteries Using Na and K Birnessites.

Sodium and magnesium batteries with intercalation electrodes are currently alternatives of great interest to lithium in stationary applications, such as distribution networks or renewable energies. Hydrated laminar oxides such as birnessites are an attractive cathode material for these batteries. Sodium and potassium birnessite samples have been synthesized by thermal and hydrothermal oxidation methods. Hybrid electrochemical cells have been built using potassium birnessite in aqueous sodium electrolyte, when starting in discharge and with a capacity slightly higher than 70 mA h g-1. Hydrothermal synthesis generally shows slightly poorer electrochemical behavior than their thermal counterparts in both sodium and potassium batteries. The study on hybrid electrolytes has resulted in the successful galvanostatic cycling of both sodium birnessite and potassium birnessite in aqueous magnesium electrolyte, with maximum capacities of 85 and 50 mA h g-1, respectively.

Induced Rate Performance Enhancement in Off-Stoichiometric Na3+3x V2-x (PO4 )3 with Potential Applicability as the Cathode for Sodium-Ion Batteries.

Off-stoichiometric Na3+3x V2-x (PO4 )3 samples have been prepared by a sol-gel route. X-ray diffraction and XPS revealed the flexibility of the NASICON framework to accommodate these deviations of the stoichiometry; at least for low x values. X-ray photoelectron spectra evidenced the presence of Na4 P2 O7 impurities. The synergic combination of the structural deviations and the presence of Na4 P2 O7 impurities induce a significant improvement of the electrochemical performance and cycling stability at high rates, as compared to the stoichiometric Na3 V2 (PO4 )3 sample. The fast kinetic response provided by the induced off-stoichiometry involves a decrease of the cell resistance.

Insight into the Electrochemical Sodium Insertion of Vanadium Superstoichiometric NASICON Phosphate.

A slight deviation of the stoichiometry has been introduced in Na3-3xV2+x(PO4)3 (0 ≤ x ≤ 0.1) samples to determine the effect on the structural and electrochemical behavior as a positive electrode in sodium-ion batteries. X-ray diffraction and XPS results provide evidence for the flexibility of the NASICON framework to allow a limited vanadium superstoichiometry. In particular, the Na2.94V2.02(PO4)3 formula reveals the best electrochemical performance at the highest rate (40C) and capacity retention upon long cycling. It is attributed to the excellent kinetic response and interphase chemical stability upon cycling. The electrochemical performance of this vanadium superstoichiometric sample in a full sodium-ion cell is also described.

High Performance Full Sodium-Ion Cell Based on a Nanostructured Transition Metal Oxide as Negative Electrode.

A novel design of a sodium-ion cell is proposed based on the use of nanocrystalline thin films composed of transition metal oxides. X-ray diffraction, Raman spectroscopy and electron microscopy were helpful techniques to unveil the microstructural properties of the pristine nanostructured electrodes. Thus, Raman spectroscopy revealed the presence of amorphous NiO, α-Fe2 O3 (hematite) and γ-Fe2 O3 (maghemite). Also, this technique allowed the calculation of an average particle size of 23.4 Å in the amorphous carbon phase in situ generated on the positive electrode. The full sodium-ion cell performed with a reversible capacity of 100 mA h g(-1) at C/2 with an output voltage of about 1.8 V, corresponding to a specific energy density of about 180 W h kg(-1) . These promising electrochemical performances allow these transition metal thin films obtained by electrochemical deposition to be envisaged as serious competitors for future negative electrodes in sodium-ion batteries.

High-performance Ni-free sustainable cathode Na0.67Mg0.05Fe0.1Mn0.85O2 for sodium-ion batteries.

Having in mind the remarkable economic and environmental issues involved in the presence of nickel and cobalt metals in electrode compositions, new Na0.67Mg0.05Fe0.1NixMn0.85-xO2 (x=0.0, 0.05, 0.1, 0.15) with a P2 type layered structure, are synthesized to be essayed as positive electrodes in sodium-ion batteries. The sol-gel route here proposed favors the obtention of highly pure and crystalline samples with a homogeneous distribution of the constituting elements. Both galvanostatic and voltammetric tests reveal a superior electrochemical behavior for the Ni-free sample, which delivers 94 mA h g-1 at 5C. This excellent performance is associated with a good kinetic response in terms of low charge and discharge hysteresis, high Na+ diffusivity, and low cell resistance. Ex-situ measurements evidenced the combined contribution of both the reversible electrolyte insertion and the formation of peroxo species. These advantageous properties allow this electrode to reach a remarkable behavior when is cycled either to low temperatures or high rates.

A Facile Method to Transform Pickled Olive Wastes Into Sulfur-Doped Carbon for Sodium-Ion Battery Electrode.

This work provides a novel, low-cost, and effective method to prepare disordered carbon materials for advanced sodium-ion batteries using biomass. A large amount of olive stone waste is yearly produced in the world, and it could be re-used for fine applications other than fuel for heat production. After treatment with sulfuric acid solution and carbonization process, wastes of olive stone are efficiently transformed into optimized carbon electrode material. XRD, XRF and XPS, electron microscopy, and physical gas adsorption are used for the compositional, microstructural, and textural characterization of the carbons. During the synthesis, impurities are removed, C-S links are formed and micropores pores are created. Sulfuric acid acts like S-dopant. The latent pores, or pores closed to nitrogen, can be found using CO2 adsorption, and are very suitable for accommodation for sodium. The results reveal that the reversible capacity is raised from ca. 200 mAh g-1 to ca. 250 mAh g-1 for the carbon obtained through treatment with sulfuric acid. The improved electrochemistry is the result of the s-doping and the porosity.

Improving the Performance of the Layered Nickel Manganese Oxide Cathode of Sodium-Ion Batteries by Direct Coating with Sodium Niobium Oxide.

This research highlights the efficacy of NaNbO3 as a coating for P2-Na2/3Ni1/3Mn2/3O2 cathodes in sodium-ion batteries. The coating enhances the kinetic behavior and cyclability of the electrochemical cells, as shown by electrochemical measurements. XRD analysis indicates that Nb does not incorporate into the cathode structure, implying a physical interaction between the coating and the cathode material. XRF analysis and EDX mapping confirm the actual composition and uniform dispersion of elements throughout the sample, while the electron micrographs evidence the occurrence of NaNbO3 particles modifying the surface of the layered oxide. The Ni4+/Ni3+ and Ni3+/Ni2+ redox pairs, along with the partially reversible oxidation of oxide to peroxide anions, contribute significantly to cell capacity, as revealed by XPS spectra. This last effect and the appearance of a co-intercalated phase at high voltage are positive factors to provide fast kinetics. Cyclic voltammograms show that samples coated with 2-3% NaNbO3 have superior rate capability, with high capacitive response and apparent diffusion coefficients. These samples also have low impedance at the electrode-electrolyte interface, which helps deliver a high capacity at 5C. Further cycling at 1C shows improved cyclability in the bare and 3% coated samples, due to their higher diffusion coefficients on charging. Notably, the 3% NaNbO3-coated sample exhibits excellent cyclability below 0 °C, making it a promising cathode material for sodium-ion batteries.

Sustainable, low Ni-containing Mg-doped layered oxides as cathodes for sodium-ion batteries.

The supply of battery-grade nickel to produce positive electrodes of sodium-ion batteries may soon become insufficient. For this reason, it is crucial to find new electrode materials that minimize its use or even fully remove this element from synthesis. We have prepared a Na0.67Mg0.05FexNiyMnzO2 (0 ≤ x ≤ 0.2; y = 0.05, 0.15; 0.6 ≤ z ≤ 0.9) series with low Ni and Fe contents by a single and easily scalable sol-gel method. This procedure yields high-purity and crystalline samples as evidenced by structural, morphological, and spectroscopic studies, including X-ray diffraction, electron microscopy, and X-ray photoelectron spectroscopy. The electrochemical tests showed an exceptional performance for the F0N05 sample with the lowest (Ni + Fe) contents, at 5 C (ca. 100 mA h g-1), and good capacity retention after 100 cycles. This excellent behaviour was also evidenced when cycling at -15 °C. These results were confirmed by electrochemical techniques, such as cyclic voltammetry and impedance spectroscopy, that evidenced a fast exchange of sodium ions due to a significant capacitive contribution and high apparent diffusion coefficients. Post-mortem analysis of the F0N05 electrodes by XRD showed the reversible insertion and the absence of detrimental P2-O2 and P2-P2' transitions, while XPS spectra demonstrated the reversible redox activity of both transition metals and oxygen.

Review and New Perspectives on Non-Layered Manganese Compounds as Electrode Material for Sodium-Ion Batteries.

After more than 30 years of delay compared to lithium-ion batteries, sodium analogs are now emerging in the market. This is a result of the concerns regarding sustainability and production costs of the former, as well as issues related to safety and toxicity. Electrode materials for the new sodium-ion batteries may contain available and sustainable elements such as sodium itself, as well as iron or manganese, while eliminating the common cobalt cathode compounds and copper anode current collectors for lithium-ion batteries. The multiple oxidation states, abundance, and availability of manganese favor its use, as it was shown early on for primary batteries. Regarding structural considerations, an extraordinarily successful group of cathode materials are layered oxides of sodium, and transition metals, with manganese being the major component. However, other technologies point towards Prussian blue analogs, NASICON-related phosphates, and fluorophosphates. The role of manganese in these structural families and other oxide or halide compounds has until now not been fully explored. In this direction, the present review paper deals with the different Mn-containing solids with a non-layered structure already evaluated. The study aims to systematize the current knowledge on this topic and highlight new possibilities for further study, such as the concept of entatic state applied to electrodes.

Metal-Ion Intercalation Mechanisms in Vanadium Pentoxide and Its New Perspectives.

The investigation into intercalation mechanisms in vanadium pentoxide has garnered significant attention within the realm of research, primarily propelled by its remarkable theoretical capacity for energy storage. This comprehensive review delves into the latest advancements that have enriched our understanding of these intricate mechanisms. Notwithstanding its exceptional storage capacity, the compound grapples with challenges arising from inherent structural instability. Researchers are actively exploring avenues for improving electrodes, with a focus on innovative structures and the meticulous fine-tuning of particle properties. Within the scope of this review, we engage in a detailed discussion on the mechanistic intricacies involved in ion intercalation within the framework of vanadium pentoxide. Additionally, we explore recent breakthroughs in understanding its intercalation properties, aiming to refine the material's structure and morphology. These refinements are anticipated to pave the way for significantly enhanced performance in various energy storage applications.

Increasing Energy Density with Capacity Preservation by Aluminum Substitution in Sodium Vanadium Phosphate.

Highly Al-substituted C-coated Na3V2-xAlx(PO4)3 compounds with a sodium superionic conductor structure are synthesized by a single and easily scalable sol-gel route. The effect of the experimental conditions is examined. Their structural, chemical, and morphological features are described. The first-principles method is used to determine the theoretical voltage vs Na content profile during Na extraction. The electrochemical Na extraction is characterized by the presence of two plateaus. The first one at ca. 3.4 V is assigned to the V4+/V3+ redox pair and shows good cyclability. The second plateau at ca. 3.9-4.0 V can be assigned to the V5+/V4+ pair, as evidenced by X-ray photoelectron spectroscopy. This second plateau is less reversible during further discharge.

On the Beneficial Effect of MgCl2 as Electrolyte Additive to Improve the Electrochemical Performance of Li4Ti5O12 as Cathode in Mg Batteries.

Magnesium batteries are a promising technology for a new generation of energy storage for portable devices. Attention should be paid to electrolyte and electrode material development in order to develop rechargeable Mg batteries. In this study, we report the use of the spinel lithium titanate or Li4Ti5O12 (LTO) as an active electrode for Mg2+-ion batteries. The theoretical capacity of LTO is 175 mA h g-1, which is equivalent to an insertion reaction with 1.5 Mg2+ ions. The ability to enhance the specific capacity of LTO is of practical importance. We have observed that it is possible to increase the capacity up to 290 mA h g-1 in first discharge, which corresponds to the reaction with 2.5 Mg2+ ions. The addition of MgCl2·6H2O to the electrolyte solutions significantly improves their electrochemical performance and enables reversible Mg deposition. Ex-situ X-ray diffraction (XRD) patterns reveal little structural changes, while X-ray photoelectron spectrometer (XPS) (XPS) measurements suggest Mg reacts with LTO. The Ti3+/Ti4+ ratio increases with the amount of inserted magnesium. The impedance spectra show the presence of a semicircle at medium-low frequencies, ascribable to Mg2+ ion diffusion between the surface film and LTO. Further experimental improvements with exhaustive control of electrodes and electrolytes are necessary to develop the Mg battery with practical application.

Morphological adaptability of graphitic carbon nanofibers to enhance sodium insertion in a diglyme-based electrolyte.

The recent introduction of glyme-based solvents has opened new opportunities to characterize graphitic materials as anodes for sodium-ion batteries. We evaluated the electrochemical behaviour of a graphitized carbon nanofiber for the first time. X-ray diffraction, electron paramagnetic resonance and nuclear magnetic resonance allowed the sodium insertion mechanism to be untangled, in which the occurrence of an activation process during the first discharge enhances sodium accessibility to active redox centres at the interlayer space. Morphological changes observed by electron microscopy could be responsible for this behaviour. A fully graphitized carbon nanofibers/NaPF6(diglyme)/Na3V2(PO4)3 sodium-ion battery was tested to probe the reliability of this graphitic nanostructure as a negative electrode.

On the Mechanism of Magnesium Storage in Micro- and Nano-Particulate Tin Battery Electrodes.

This study reports on the electrochemical alloying-dealloying properties of Mg2Sn intermetallic compounds. 119Sn Mössbauer spectra of β-Sn powder, thermally alloyed cubic-Mg2Sn, and an intermediate MgSn nominal composition are used as references. The discharge of a Mg/micro-Sn half-cell led to significant changes in the spectra line shape, which is explained by a multiphase mechanism involving the coexistence of c-Mg2Sn, distorted Mg2−δSn, and Mg-doped β-Sn. Capacities and capacity retention were improved by using nanoparticulate tin electrodes. This material reduces significantly the diffusion lengths for magnesium and contains surface SnO and SnO2, which are partially electroactive. The half-cell potentials were suitable to be combined versus the MgMn2O4 cathodes. Energy density and cycling properties of the resulting full Mg-ion cells are also scrutinized.

Improved Surface Stability of C+MxOy@Na3V2(PO4)3 Prepared by Ultrasonic Method as Cathode for Sodium-Ion Batteries.

Coated C+MxOy@Na3V2(PO4)3 samples containing 1.5% or 3.5% wt. of MxOy (Al2O3, MgO or ZnO) have been synthesized by a two-step method including first a citric based sol-gel method for preparing the active material and second an ultrasonic stirring technique to deposit MxOy. The presence of the metal oxides properly coating the surface of the active material is evidenced by XPS and electron microscopy. Galvanostatic cycling of sodium half-cells reveals a significant capacity enhancement for samples coated with 1.5% of metal oxides and an exceptional cycling stability as evidenced by Coulombic efficiencies as high as 95.9% for ZnO@ Na3V2(PO4)3. It is correlated to their low surface layer and charge transfer resistance values. The formation of metal fluorides that remove traces of corrosive HF from the electrolyte is checked by XPS spectroscopy. The feasibility of sodium-ion batteries assembled with C+MxOy@Na3V2(PO4)3 is further verified by evaluating the electrochemical performance of full cells. Particularly, a Graphite//Al2O3@ Na3V2(PO4)3 battery delivers an energy density as high as 260 W h kg-1 and exhibits a Coulombic efficiency of 89.3% after 115 cycles.

Na3V2(PO4)3/C Nanorods with Improved Electrode-Electrolyte Interface As Cathode Material for Sodium-Ion Batteries.

Na3V2(PO4)3/C nanocomposites are synthesized by an oleic acid-based surfactant-assisted method. XRD patterns reveal high-purity samples, whereas Raman spectroscopy evidence the highly disordered character of the carbon phase. Electron micrographs show submicron agglomerates with a sea-urchin like morphology consisting of primary nanorods coated by a carbon phase. The electrode material was tested in half and full sodium cells. The electrochemical performance is clearly improved by this optimized morphology, particularly at high C rates. Thus, 76.6 mA h g(-1) was reached at 40C for Na3V2(PO4)3/C nanorods. In addition, 105.3 and 96.7 mA h g(-1) are kept after 100 cycles at rates as high as 5 and 10C. This exceptional Coulombic efficiency can be ascribed to the good mechanical stability and the low internal impedance at the electrode-electrolyte interphase.

Synthesis of Porous and Mechanically Compliant Carbon Aerogels Using Conductive and Structural Additives.

We report the synthesis of conductive and mechanically compliant monolithic carbon aerogels prepared by sol-gel polycondensation of melamine-resorcinol-formaldehyde (MRF) mixtures by incorporating diatomite and carbon black additives. The resulting aerogels composites displayed a well-developed porous structure, confirming that the polymerization of the precursors is not impeded in the presence of either additive. The aerogels retained the porous structure after etching off the siliceous additive, indicating adequate cross-linking of the MRF reactants. However, the presence of diatomite caused a significant fall in the pore volumes, accompanied by coarsening of the average pore size (predominance of large mesopores and macropores). The diatomite also prevented structural shrinkage and deformation of the as-prepared monoliths upon densification by carbonization, even after removal of the siliceous framework. The rigid pristine aerogels became more flexible upon incorporation of the diatomite, favoring implementation of binderless monolithic aerogel electrodes.

(57)Fe Mössbauer spectroscopy and electron microscopy study of metal extraction from CuFe(2)O(4) electrodes in lithium cells.

Active CuFe(2)O(4) electrode materials for lithium cells are produced by thermal decomposition of a citrate precursor. The precipitation of the metal citrate is carried out by a freeze-drying procedure. A tetragonally distorted spinel structure is prepared by the decomposition of a citrate precursor. Samples free of impurities are obtained depending on the annealing temperature. The sample heated at 800 degrees C performed at 470 mAh g(-1) after 50 cycles. Electron microscopy is used as the ultimate technique to monitor the morphological changes upon the reversible conversion reaction. Detachment of metallic particles from the starting material, the formation of a polymeric organic film, and the subsequent removal on charging are discussed as determining factors in the electrochemical behaviour of this oxide as an electrode versus lithium. The growth of metallic iron aggregates is inferred from the (57)Fe Mössbauer spectra.

X-ray absorption spectroscopic study of LiCoO2 as the negative electrode of lithium-ion batteries.

Lithium cobalt oxide (LiCoO(2)) particles are modified using rotor blade grinding and re-annealing and used as the active electrode material versus lithium in the 3-0 V potential interval, in which a maximum capacity of 903 mA h g(-1) is achieved. X-ray absorption near edge structure spectra reveal the complete reduction of Co(3+) to Co metal at 0 V. Cell recharge leads to an incomplete reoxidation of cobalt. A maximum reversible capacity of 812 mA h g(-1) is obtained, although a poor capacity retention upon prolonged cycling may limit its application.