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Lithium-ion batteries (LIBs) have gained considerable attention from the scientific community due to their outstanding properties, such as high energy density, low self-discharge, and environmental sustainability. Among the prominent candidates for anode materials in next-generation LIBs are the spinel ferrites, represented by the MFe2O4 series, which offer exceptional theoretical capacities, excellent reversibility, cost-effectiveness, and eco-friendliness. In the scope of this study, Ni0.5Mg0.5Fe1.7Mn0.3O4 nanoparticles were synthesized using a sol-gel synthesis method and subsequently coated with a carbon layer to further enhance their electrochemical performance. TEM images confirmed the presence of the carbon coating layer on the Ni0.5Mg0.5Fe1.7Mn0.3O4/C composite. The analysis of the measured X-ray diffraction (XRD) and Raman spectroscopy results confirmed the formation of nanocrystalline Ni0.5Mg0.5Fe1.7Mn0.3O4 before coating and amorphous carbon in the Ni0.5Mg0.5Fe1.7Mn0.3O4/C after the coating. The Ni0.5Mg0.5Fe1.7Mn0.3O4 anode material exhibited a much higher specific capacity than the traditional graphite material, with initial discharge/charge capacities of 1275 and 874 mA h g-1, respectively, at a 100 mA g-1 current density and a first coulombic efficiency of 68.54%. The long-term cycling test showed a slight capacity fading, retaining approximately 85% of its initial capacity after 75 cycles. Notably, the carbon-coating layer greatly enhanced the stability and slightly increased the capacity of the as-prepared Ni0.5Mg0.5Fe1.7Mn0.3O4. The first discharge/charge capacities of Ni0.5Mg0.5Fe1.7Mn0.3O4/C at 100 mA g-1 current density reached 1032 and 723 mA h g-1, respectively, and a first coulombic efficiency of 70.06%, with an increase of discharge/charge capacities to 826.6 and 806.2 mA h g-1, respectively, after 75 cycles (with a capacity retention of 89.7%), and a high-rate capability of 372 mA h g-1 at 2C. Additionally, a full cell was designed using a Ni0.5Mg0.5Fe1.7Mn0.3O4/C anode and an NMC811 cathode. The output voltage was about 2.8 V, with a high initial specific capacity of 755 mA h g-1 at 0.125C, a high rate-capability of 448 mA h g-1 at 2C, and a high-capacity retention of 91% after 30 cycles at 2C. The carbon coating layer on Ni0.5Mg0.5Fe1.7Mn0.3O4 nanoparticles played a crucial role in the excellent electrochemical performance, providing conducting, buffering, and protective effects.
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Nonuniform Li deposition causes dendrites and low Coulombic efficiency (CE), seriously hindering the practical applications of Li metal. Herein, we developed an artificial solid-state interphase (SEI) with planar polycyclic aromatic hydrocarbons (PAHs) on the surface of Li metal anodes by a facile in situ formation technology. The resultant dihydroxyviolanthron (DHV) layers serve as the protective layer to stabilize the SEI. In addition, the oxygen-containing functional groups in the soft and conformal SEI film can regulate the diffusion and transport of Li ions to homogenize the deposition of Li metal. The artificial SEI significantly improves the CEs and shows superior cyclability of over 1000 h at 4 mAh cm-2. The LiFePO4/Li cell (2.8 mAh cm-2) enables a long cyclability for 300 cycles and high CEs of 99.8%. This work offers a new strategy to inhibit Li dendrite growth and enlightens the design on stable SEI for metal anodes.
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Due to the low capacity, low working potential, and lithium coating at fast charging rates of graphite material as an anode for Li-ion batteries (LIBs), it is necessary to develop novel anode materials for LIBs with higher capacity, excellent electrochemical stability, and good safety. Among different transition-metal oxides, AB2O4 spinel oxides are promising anode materials for LIBs due to their high theoretical capacities, environmental friendliness, high abundance, and low cost. In this work, a novel, porous Zn0.5Mg0.5FeMnO4 spinel oxide was successfully prepared via the sol-gel method and then studied as an anode material for Li-ion batteries (LIBs). Its crystal structure, morphology, and electrochemical properties were, respectively, analyzed through X-ray diffraction, high-resolution scanning electron microscopy, and cyclic voltammetry/galvanostatic discharge/charge measurements. From the X-ray diffraction, Zn0.5Mg0.5FeMnO4 spinel oxide was found to crystallize in the cubic structure with Fd3¯m symmetry. However, the Zn0.5Mg0.5FeMnO4 spinel oxide exhibited a porous morphology formed by interconnected 3D nanoparticles. The porous Zn0.5Mg0.5FeMnO4 anode showed good cycling stability in its capacity during the initial 40 cycles with a retention capacity of 484.1 mAh g-1 after 40 cycles at a current density of 150 mA g-1, followed by a gradual decrease in the range of 40-80 cycles, which led to reaching a specific capacity close to 300.0 mAh g-1 after 80 cycles. The electrochemical reactions of the lithiation/delithiation processes and the lithium-ion storage mechanism are discussed and extracted from the cyclic voltammetry curves.
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Tunnel-structured MnO2 represents open-framed electrode materials for reversible energy storage. Its wide application is limited by its poor cycling stability, whose structural origin is unclear. We tracked the structure evolution of ß-MnO2 upon Li+ ion insertion/extraction by combining advanced inâ situ diagnostic tools at both electrode level (synchrotron X-ray scattering) and single-particle level (transmission electron microscopy). The instability is found to originate from a partially reversible phase transition between ß-MnO2 and orthorhombic LiMnO2 upon lithiation, causing cycling capacity decay. Moreover, the MnO2 /LiMnO2 interface exhibits multiple arrow-headed disordered regions, which severely chop into the host and undermine its structural integrity. Our findings could account for the cycling instability of tunnel-structured materials, based on which future strategies should focus on tuning the charge transport kinetics toward performance enhancement.
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Metallic Zn is a preferred anode material for rechargeable aqueous batteries towards a smart grid and renewable energy storage. Understanding how the metal nucleates and grows at the aqueous Zn anode is a critical and challenging step to achieve full reversibility of Zn battery chemistry, especially under fast-charging conditions. Here, by combining in situ optical imaging and theoretical modeling, we uncover the critical parameters governing the electrodeposition stability of the metallic Zn electrode, that is, the competition among crystallographic thermodynamics, kinetics, and Zn2+ -ion diffusion. Moreover, steady-state Zn metal plating/stripping with Coulombic efficiency above 99 % is achieved at 10-100â mA cm-2 in a reasonably high concentration (3â M) ZnSO4 electrolyte. Significantly, a long-term cycling-stable Zn metal electrode is realized with a depth of discharge of 66.7 % under 50â mA cm-2 in both Zn||Zn symmetrical cells and MnO2 ||Zn full cells.
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A few seconds flash photopyrolysis is used as efficient screening tool for the investigation of selected biomass in producing syngas, hydrogen and biochar. This innovative approach allowed rapid pyrolysis of the biomass, which was followed by a precise gas analysis and quantification, using Mass Spectrometry (MS). The analysis of the gas composition from three distinct biomass wastes in this study provides new insights into their thermochemical characteristics, expanding thus our knowledge of the potential of the selected biomass resources for the production of carbon, syngas, and/or hydrogen-rich gas production. This enhanced characterization revealed the potential of biomass transformation in contributing to innovative green energy sustainable solutions.
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This paper explores the latest developments in physical vapor deposition (PVD) techniques for fabricating silicon-carbon (Si/C) based thin films as anodes of Lithium-Ion batteries (LiBs). Properties of Si/C based materials, such as high thermal stability, electrical conductivity and mechanical strength, have addressed the critical challenges associated with the use silicon as anode material for LiBs, including as volume expansion during lithiation, structural stability and electrode degradation. The review article aims to provide recent advances in the use of Si/C-based thin film materials deposited via PVD processes as anodes for LiBs. PVD deposition processes provide numerous benefits including the precise control over the structure, thickness, morphology, as well as the design of deposited thin-film materials, and this article provides an in-depth analysis on the design and synthesis of Si/C thin films, as well as its electrochemical performance and stability when used as anode for LiBs. The primary aim of this paper is to underscore the advantages provided by PVD processes in overcoming challenges associated with using pure silicon as anode material for LiBs, or in improving the electrochemical performance of Si/C-based anode materials through the design of several Si/C films, covering both multilayer and nanocomposite Si/C film configurations outlined in sections 2 and 3, respectively. Insights into the mechanisms governing lithium-ion insertion/extraction processes within the Si/C matrix are provided, offering an understanding of the material's behavior during battery cycling.
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Amorphous Si thin films with different thicknesses were deposited on synthetic graphite electrodes by using a simple and scalable one-step physical vapor deposition (PVD) method. The specific capacities and rate capabilities of the produced electrodes were investigated. X-ray diffraction, scanning electron microscopy, Raman spectroscopy, profilometry, cyclic voltammetry, galvanostatic techniques, and in situ Raman spectroscopy were used to investigate their physicochemical and electrochemical properties. Our results demonstrated that the produced Si films covered the bare graphite electrodes completely and uniformly. Si-coated graphite, Si@G, with an optimal thickness of 1 µm exhibited good stability, with an initial discharge capacity of 628.7 mAhg-1, a capacity retention of 96.2%, and a columbic efficiency (CE) higher than 99% at C/3. A discharge capacity of 250 mAh g-1 was attained at a high current rate of 3C, which was over 2.5 times that of a bare graphite electrode, thanks to the high activated surface area (1.5 times that of pristine graphite) and reduced resistance during cycling.
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In advancing sodium-ion battery technology, we introduce a novel application of Na3NiZr(PO4)3 with a NASICON structure as an anode material. This research unveils, for the first time, its exceptional ability to maintain high specific capacity and unprecedented cycle stability under extreme current densities up to 1000 mA·g-1, within a low voltage window of 0.01-2.5 V. The core of our findings lies in the material's remarkable capacity retention and stability, which is a leap forward in addressing long-standing challenges in energy storage. Through cutting-edge in situ/operando X-ray diffraction analysis, we provide a perspective on the structural evolution of Na3NiZr(PO4)3 during operation, offering deep insights into the mechanisms that underpin its superior performance.
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Doping is a widely employed technique to enhance the functionality of lithium-ion battery materials, tailoring their performance for specific applications. In our study, we employed in situ Raman and in situ X-ray diffraction (XRD) spectroscopic techniques to examine the structural alterations and electrochemical behavior of phosphorus-doped titanium dioxide (TiO2) nanoparticles. This investigation revealed several notable changes: an increase in structural defects, enhanced ionic and electronic conductivity, and a reduction in crystallite size. These alterations facilitated higher lithiation rates and led to the first observed appearance of LiTiO2 in the Raman spectra due to anatase lithiation, resulting in a reversible double-phase transition during the charging and discharging processes. Furthermore, doping with 2, 5, and 10 wt % phosphorus resulted in an initial increase in specific capacity compared to undoped TiO2. However, higher doping levels were associated with diminished capacity retention, pinpointing an optimal doping level for phosphorus. These results underscore the critical role of in situ characterization techniques in understanding doping effects, thereby advancing the performance of anode materials, particularly TiO2, in lithium-ion batteries.
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A new Li1.2Ni0.13Mn0.54Fe0.1Co0.03O2 material with a higher content of Fe and lower content of Co was designed via a simple sol-gel method. Moreover, the effect of upper cut-off voltage on the structural stability, capacity and voltage retention was studied. The Li1.2Ni0.13Mn0.54Fe0.1Co0.03O2 electrode delivers a discharge capacity of 250 mA h g-1 with good capacity retention and coulombic efficiency at 4.6 V cut-off voltage. Importantly, improved voltage retention of 94% was achieved. Ex situ XRD and Raman proved that the electrodes cycled at 4.8 V cut-off voltage showed huge structural conversion from layered-to-spinel explaining the poor capacity and voltage retention at this cut-off voltage. In addition, ex situ FT-IR demonstrates that the upper cut-off voltage of 4.8 V exhibits a higher intensity of SEI-related peaks than 4.6 V, suggesting that reducing the upper cut-off voltage can inhibit the growth of the SEI layer. In addition, when the Li1.2Ni0.13Mn0.54Fe0.1Co0.03O2 cathode was paired with a synthesized phosphorus-doped TiO2 anode (P-doped TiO2) in a complete battery cell, it exhibits good capacity and cycling stability at 1C rate. The material developed in this study represents a promising approach for designing high-performance Li-rich, low cobalt cathodes for next-generation lithium-ion batteries.
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Nuclear-grade Spent Organic Resin (SOR) contains high concentrations of radioactive nuclides and metal contaminants, while phosphate sludge contains high amount of fine clayey particles and CO32-, both posing a major threat to the biosphere. In this study, a novel geopolymer package (GP) was proposed to directly solidify SOR loaded with 134Cs by incorporating uncalcined phosphate sludge (UPS) as feedstocks, activated by NaOH/KOH. The results showed that alkali-mixed reagents-activated GP is more advantageous in terms of chemical stability and mechanical properties than NaOH-activated GP, recording compressive strength values greater than the waste acceptance criteria and OPC. The 28-day compressive strength of solidified packages can exceed 31 MPa at the highest amount of 42 wt% UPS. The addition of NaF powder into the solidified packages generates more hybrid type gels, which are more conducive to partial dissolution and bonding UPS particles, thereby producing stable and stronger GP. Leaching results of solidified GP in presence of up to 13 wt% SORs showed that only 0.15 % of total 134Cs was leached, even under aggressive solutions. Solidification mechanism revealed that activation of UPS-MK blend forms N,K-A-S-H, (N,K,C)-A-S-H/C-S-H gels coexisting with unreacted particles, thereby solidify/stabilize metal contaminants and Cs+ by a synergetic immobilization action of hydration products via substitution and encapsulation. This study provides a promising paradigm for effective solidification of nuclear-grade resins and synergetic harmless treatment of industrial/phosphate mine solid wastes.
Assuntos
Fosfatos , Esgotos , Hidróxido de Sódio , Radioisótopos de Césio , MetaisRESUMO
Lithium-oxygen (Li-O2 ) batteries possess a high theoretical energy density, which means they could become a potential alternative to lithium-ion batteries. Nevertheless, the charging process of Li-O2 batteries requires much higher energy, due to the insulating nature of the discharge product. It has been revealed that the anion additive, lithium iodide (LiI), can tune the cell chemistry to form lithium hydroxide (LiOH) as the product and facilitate the kinetics during the charging process. Although numerous studies have been reported, the role of this additive is still under investigation. Herein, the recent advances focusing on the use of LiI in Li-O2 batteries are reviewed, its catalytic behavior on discharge and charge is discussed, and its synergistic effect with water is understood. The ambiguity existing among the studies are also revealed, and solutions to the current issues are introduced.
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Integrating solid-state electrolyte (SSE) into Li-metal anodes has demonstrated great promise to unleash the high energy density of rechargeable Li-metal batteries. However, fabricating a highly cyclable SSE/Li-metal anode remains a major challenge because the densification of the SSE is usually incompatible with the reactive Li metal. Here, a liquid-metal-derived hybrid solid electrolyte (HSE) is proposed, and a facile transfer technology to construct an artificial HSE on the Li metal is reported. By tuning the wettability of the transfer substrates, electron- and ion-conductive liquid metal is sandwiched between electron-insulating and ion-conductive LiF and oxides to form the HSE. The transfer technology renders the HSE continuous, dense, and uniform. The HSE, having high ion transport, electron shut-off, and mechanical strength, makes the composite anode deliver excellent cyclability for over 4000 h at 0.5 mA cm-2 and 1 mAh cm-2 in a symmetrical cell. When pairing with LiFePO4 and sulfur cathodes, the HSE-coated Li metal dramatically enhances the performance of full cells. Therefore, this work demonstrates that tuning the interfacial wetting properties provides an alternate approach to build a robust solid electrolyte, which enables highly efficient Li-metal anodes.
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High-capacity Ni-rich layered oxides are promising cathode materials for secondary lithium-based battery systems. However, their structural instability detrimentally affects the battery performance during cell cycling. Here, we report an Al/Zr co-doped single-crystalline LiNi0.88Co0.09Mn0.03O2 (SNCM) cathode material to circumvent the instability issue. We found that soluble Al ions are adequately incorporated in the SNCM lattice while the less soluble Zr ions are prone to aggregate in the outer SNCM surface layer. The synergistic effect of Al/Zr co-doping in SNCM lattice improve the Li-ion mobility, relief the internal strain, and suppress the Li/Ni cation mixing upon cycling at high cut-off voltage. These features improve the cathode rate capability and structural stabilization during prolonged cell cycling. In particular, the Zr-rich surface enables the formation of stable cathode-electrolyte interphase, which prevent SNCM from unwanted reactions with the non-aqueous fluorinated liquid electrolyte solution and avoid Ni dissolution. To prove the practical application of the Al/Zr co-doped SNCM, we assembled a 10.8 Ah pouch cell (using a 100 µm thick Li metal anode) capable of delivering initial specific energy of 504.5 Wh kg-1 at 0.1 C and 25 °C.
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The worldwide energy demand in electric vehicles and the increasing global temperature have called for development of high-energy and long-life lithium-ion batteries (LIBs) with improved high-temperature operational resiliency. However, current attention has been mostly focused on cycling aging at elevated temperature, leaving considerable gaps of knowledge in the failure mechanism, and practical control of abusive calendar aging and thermal runaway that are highly related to the eventual operational lifetime and safety performance of LIBs. Herein, using a combination of various in situ synchrotron X-ray and electron microscopy techniques, a multiscale understanding of surface structure effects involved in regulating the high-temperature operational tolerance of polycrystalline Ni-rich layered cathodes is reported. The results collectively show that an ultraconformal poly(3,4-ethylenedioxythiophene) coating can effectively prevent a LiNi0.8 Co0.1 Mn0.1 O2 cathode from undergoing undesired phase transformation and transition metal dissolution on the surface, atomic displacement, and dislocations within primary particles, intergranular cracking along the grain boundaries within secondary particles, and intensive bulk oxygen release during high state-of-charge and high-temperature aging. The present work highlights the essential role of surface structure controls in overcoming the multiscale degradation pathways of high-energy battery materials at extreme temperature.
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LiCoO2 (LCO) is widely applied in today's rechargeable battery markets for consumer electronic devices. However, LCO operations at high voltage are hindered by accelerated structure degradation and electrode/electrolyte interface decomposition. To overcome these challenges, co-modified LCO (defined as CB-Mg-LCO) that couples pillar structures with interface shielding are successfully synthesized for achieving high-energy-density and structurally stable cathode material. Benefitting from the "Mg-pillar" effect, irreversible phase transitions are significantly suppressed and highly reversible Li+ shuttling is enabled. Interestingly, bonding effects between the interfacial lattice oxygen of CB-Mg-LCO and amorphous Cox By coating layer are found to elevate the formation energy of oxygen vacancies, thereby considerably mitigating lattice oxygen loss and inhibiting irreversible phase transformation. Meanwhile, interface shielding effects are also beneficial for mitigating parasitic electrode/electrolyte reactions, subsequent Co dissolution, and ultimately enable a robust electrode/electrolyte interface. As a result, the as-designed CB-Mg-LCO cathode achieves a high capacity and excellent cycle stability with 94.6% capacity retention at an extremely high cut-off voltage of 4.6 V. These findings provide new insights for cathode material modification methods, which serves to guide future cathode material design.
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Effective fertilizers management is essential for sustainable agricultural practices. One way to improve agronomic practices is by using slow-release fertilizers (SRF) that have shown interesting role in optimizing nutrients availability for plants growth. Considering the current ecological concerns, coated SRF using ecofriendly materials continue to attract great attention. In this context, novel waterborne and biodegradable coating nanocomposite formulations were elaborated from cellulose nanocrystals (CNC)-filled poly (vinyl alcohol) (PVA) for slow release NPK fertilizer with water retention property. CNC were extracted from hemp stalks using sulfuric acid hydrolysis process and their physico-chemical characteristics were investigated. CNC with various weight loadings (6, 10, 14.5 wt%) were incorporated into PVA polymer via solvent mixing method to produce viscous coating nanocomposite formulations with moderated shear viscosity. Uniform PVA@CNC coating microlayer was applied on the surface of NPK fertilizer granules in Wurster chamber of a fluidized bed dryer at controlled spraying and drying parameters. The nitrogen, phosphorus and potassium release profiles from coated NPK fertilizer were determined in water and soil. It was found that the coating materials extended the N-P-K nutrients release time from 3 days for uncoated fertilizer to 10 and 30 days for neat PVA- and CNC/PVA-coated fertilizer in soil medium, indicating the positive role of the presence of CNC in the PVA-based coatings. The morphology, coating rate and crushing strength of the as-prepared coated products were investigated in addition to their effect on water holding capacity and water retention of the soil. Enhanced crushing strength and water retention with a positive effect on the soil moisture were observed after coating NPK fertilizer, mainly with high CNC content (14.5 wt%). Therefore, these proposed nanocomposite coating materials showed a great potential for producing a new class of SRF with high nutrients use efficiency and water retention capacity, which could be beneficial to sustainable crop production.
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Celulose/química , Fertilizantes , Nanocompostos/química , Nanopartículas/química , Álcool de Polivinil/química , Água/química , Interações Hidrofóbicas e Hidrofílicas , Nanocompostos/ultraestrutura , Nanopartículas/ultraestrutura , Nitrogênio/análise , Fósforo/análise , Potássio/análise , Solo/química , Temperatura , ViscosidadeRESUMO
P2-type NaMO2 sodiated layered oxides with mixed transition metals are receiving considerable attention for use as cathodes in sodium-ion batteries. A study on solid solution (1 - y)P2-NaxCoO2-(y)P2-NaxMn2/3Ni1/3O2 (y = 0, 1/3, 1/2, 2/3, 1) reveals that changing the composition of the transition metals affects the resulting structure and the stability of pure P2 phases at various temperatures of calcination. For 0 ≤ y ≤ 1.0, the P2-NaxCo(1-y)Mn2y/3Niy/3O2 solid-solution compounds deliver good electrochemical performance when cycled between 2.0 and 4.2 V versus Na+/Na with improved capacity stability in long-term cycling, especially for electrode materials with lower Co content (y = 1/2 and 2/3), despite lower discharge capacities being observed. The (1/2)P2-NaxCoO2-(1/2)P2-NaxMn2/3Ni1/3O2 composition delivers a discharge capacity of 101.04 mAh g-1 with a capacity loss of only 3% after 100 cycles and a Coulombic efficiency exceeding 99.2%. Cycling this material to a higher cutoff voltage of 4.5 V versus Na+/Na increases the specific discharge capacity to ≈140 mAh g-1 due to the appearance of a well-defined high-voltage plateau, but after only 20 cycles, capacity retention declines to 88% and Coulombic efficiency drops to around 97%. In situ X-ray absorption near-edge structure measurements conducted on composition NaxCo1/2Mn1/3Ni1/6O2 (y = 1/2) in the two potential windows studied help elucidate the operating potential of each transition metal redox couple. It also reveals that at the high-voltage plateau, all of the transition metals are stable, raising the suspicion of possible contribution of oxygen ions in the high-voltage plateau.
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Worries about lithium supplies have led to the development of research on sodium batteries. Sodium-ion batteries are regarded as the next generation of energy-storage devices thanks to the generous resources of sodium. In spite of that, structural changes in the electrode materials remain the main challenge of this storage technology. NaCoO2 has been widely investigated as a competitive candidate for LiCoO2. It has been found that the electrochemical cycling curves of this material present numerous potential steps as a result of electronic transitions and/or structural ordering. From this standpoint, this paper reports a novel cathode material, Na2/3Co0.95Ti0.05O2, where 5% of cobalt was replaced by titanium, prepared via a facile solid-state route. The sodiation/desodiation mechanism of this layered material was investigated. Na//Na2/3Co0.95Ti0.05O2 exhibits a first initial capacity of 119 mAh/g in the potential window 2-4.2 V with less potential jumps in the potential versus capacity curve compared to NaCoO2. Genuinely, the electrochemistry of this material demonstrated a reversibility upon the insertion/desinertion process with low polarization. In situ synchrotron investigations on Na2/3Co0.95Ti0.05O2 reveal the occurrence of reversible ordered phases. Ex situ magic-angle-spinning NMR disclosed different environments around sodium starting from the pristine state to the end of charge.