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International audience; NaMoO2 was synthesized as a layered oxide from the reaction between the layered oxide Na2/3MoO2 and metal sodium. Its structure was determined from high-resolution powder X-ray diffraction, and it can be described as an α-NaFeO2 distorted structure in which sodium ions and molybdenum atoms occupy octahedral interstitial sites. Chains of “diamond-like” clusters of molybdenum were evidenced in the [MoO2] layers resulting from the Peierls distortion expected in a two-dimensional triangular lattice formed by transition metal atoms with a d3 electronic configuration. Molybdenum–molybdenum distances as short as 2.58 Å were found in these clusters. The magnetic moment recorded at low temperatures and at room temperature showed that NaMoO2 presents a very low magnetic susceptibility compatible with the localization of the 4d electrons in the Mo–Mo bonds. This localization was confirmed by DFT calculation that showed the NaMoO2 was diamagnetic at 0 K. A sodium battery was built using NaMoO2 as the positive electrode material, and we found that sodium ions can be reversibly deintercalated and intercalated in NaMoO2, indicating that this compound is one of the many phases existing in the NaxMoO2 system.

International audience; This paper gives an overview of the research carried out on lithium and sodium layered materials as positive electrodes of lithium (sodium)‐ion batteries. It focuses on the solid‐state chemistry contribution to discover new materials and to optimize the properties versus the requirements imposed by the applications. Among, all material structures, which are considered, the layered ones (lithium based), are the best candidates for high energy density batteries for mobile applications. Recently, the homologous Na materials, which have lower energy, are considered for stationary applications due to their low price. Starting for LiMO2 materials or NaxMO2 (0.5 < x < 1), many substituted phases, obtained by high‐temperature solid‐state chemistry, have allowed stabilizing the layered structure in large composition domains to increase the specific capacity, which is directly related to the number of exchanged electrons during the cycling process.

International audience; Sodium transition metal layered oxides are a class of materials which exhibits fascinating properties, such as high thermoelectric power. Whereas most of the work conducted so far focused on 3d transition metals, mainly cobalt, compounds with 4d metals could be excellent materials to obtain new strongly correlated electron systems. This work is focused on NaxRhO2 compounds, with O3- and P2-type structures. The P2-type structure was obtained by ion exchange from the potassium phase P2-K0.62RhO2. This type of synthesis was conducted here for the first time on layered oxides with 4d transition metals. The phase diagram of both structures was explored by sodium electrochemical deintercalation/intercalation in a battery. The existence of single phases was shown with presumably different physical properties. As an example, the O′3-Na1/2RhO2 compound electrochemically obtained for the first time exhibits a metallic behavior, whereas the O3-NaRhO2 phase is a semiconductor. The synthesis of each single phase existing in both the O3- and P2-type systems should lead to new insights into the structure-properties relationships of this class of materials.

International audience; The comparative structural, Mössbauer, and electrochemical studies of the NaxMn2/3Fe1/3O2 and NaxMn1/2Fe1/2O2 systems show that the change in the Mn/Fe ratio has a significant influence on the overlap between the Mn3+/4+ and Fe3+/4+ redox couples. The P2-type structure is maintained in the 0.3 < x < 0.8 domain. For the highest intercalation amount, structural distortions occur due to the Jahn–Teller effect of the Mn3+ ions. The macroscopic distortion results from a competition between the opposite effects of Mn3+ and Fe3+: the isotropic character of Fe3+ tends to prevent the macroscopic distortion. For the lower sodium amounts, the instability of the interstitial trigonal prismatic space leads to the formation, by slab gliding, of a very disordered structure. Even if this structural transition is reversible, a strong capacity fading is observed if the cell is charged above 4 V verus Na/Na+.

International audience; Layered sodium transition metal oxides represent a complex class of materials that exhibit a variety of properties, for example, superconductivity, and can feature in a range of applications, for example, batteries. Understanding the structure–function relationship is key to developing better materials. In this context, the phase diagram of the NaxMoO2 system has been studied using electrochemistry combined with in situ synchrotron X-ray diffraction experiments. The many steps observed in the electrochemical curve of Na2/3MoO2 during cycling in a sodium battery suggest numerous reversible structural transitions during sodium (de)intercalation between Na0.5MoO2 and Na∼1MoO2. In situ X-ray diffraction confirmed the complexity of the phase diagram within this domain, 13 single phase domains with minute changes in sodium contents. Almost all display superstructure or modulation peaks in their X-ray diffraction patterns suggesting the existence of many NaxMoO2 specific phases that are believed to be characterized by sodium/vacancy ordering as well as Mo–Mo bonds and subsequent Mo–O distances patterning in the structures. Moreover, a room temperature triclinic distortion was evidenced in the composition range 0.58 ≤ x < 0.75, for the first time in a sodium layered oxide system. Monoclinic and triclinic subcell parameters were refined for every NaxMoO2 phase identified. Reversible [MoO2] slab glidings occur during the sodium (de)intercalation. This level of structural detail provides unprecedented insight on the phases present and their evolution, which may allow each phase to be isolated and examined in more detail.

International audience; We have investigated the microscopic magnetic nature of a novel Na battery material, P2-Na0.5VO2, in which V ions form a two-dimensional triangular lattice, by means of muon-spin rotation and relaxation (μ+SR) measurements down to 50 mK. Although magnetization measurements indicated the presence of an antiferromagnetic transition at 13 K, the internal magnetic field due to the formation of magnetic order appears not at 13 K but at 2 K. Furthermore, the magnetic order is found to have a wide field distribution even at 50 mK. Such wide field distribution is reasonably explained by a combination of multiple muon sites and the formation of a long-range magnetic order, while the reliable spin structure is still unknown.

International audience; The electrochemical properties of the O3-type NaxMn1/3Fe2/3O2 (x = 0.77) phase used as positive electrode material in Na batteries were investigated in the 1.5–3.8 V, 1.5–4.0 V and 1.5–4.3 V ranges. We show that cycling the Na cells in a wider voltage range do not induce a significant gain on long term cycling as the discharge capacities reached for the three experiments are identical after the 14th cycle. The structural changes the material undergoes from 1.5 V (fully intercalated state) to 4.3 V were investigated by operando in situ X-ray powder diffraction (XRPD) and were further characterized by ex situ synchrotron XRPD. We show that the low amount of Mn3+ ions (≈33% of total Mn+ ions) is enough to induce a cooperative Jahn–Teller effect for all MO6 octahedra in the fully intercalated state. Upon deintercalation the material exhibits several structural transitions: O′3 → O3 → P3. Furthermore, several residual phases are observed during the experiment. In particular, a small part of the O3 type is not transformed to P3 but is always involved in the electrochemical process. To explain this behaviour the hypothesis of an inhomogeneity, which is not detected by XRD, is suggested. All phases converge into a poorly crystallized phase for x ≈ 0.15. The short interslab distance of the resulting phase strongly suggests an octahedral environment for the Na+ ions. X-ray absorption spectroscopy and 57Fe Mössbauer spectroscopy were used to confirm the activity of the Mn4+/Mn3+ and Fe4+/Fe3+ redox couples in the low and high voltage regions, respectively. 57Fe Mössbauer spectroscopy also showed an increase of the disorder into the material upon deintercalation.

International audience; Sodium layered oxide, Na0.70Mn0.60Ni0.30Co0.10O2, with a P2-type structure was synthesized by a co-precipitation method and characterized as positive electrode of sodium batteries. The P2-NaxMn0.60Ni0.30Co0.10O2 electrode delivered a high specific capacity of 185 mAh/g in the 1.5–4.3 V range at 1st cycle at C/20 rate; however, rapid capacity decay is observed. In the 1.7–4.0 V range the capacity is equal to 125 mAh/g with a fading considerably reduced. The rate capability is reasonably good. According to the electrochemical profile, a potential plateau around 4.2 V vs. Na+/Na, meaning a bi-phasic domain, and several voltage drops that could be related to single phase domains in a narrow sodium content range are observed. Even if the capacity decreases when the battery is cycled above 4.0 V, there is no irreversible structural change.

International audience; The electrochemical properties of the P2-type NaxMn1/2Fe1/2O2 (x = 0.62) phase used as a positive electrode in Na batteries were tested in various voltage ranges at C/20. We show that, even if the highest capacity is obtained for the first cycles between 1.5 and 4.3 V, the best capacity after 50 cycles is obtained while cycling between 1.5 and 4.0 V (120 mAh g(-1)). The structural changes occurring in the material during the (de)intercalation were studied by operando in situ X-ray powder diffraction (XRPD) and ex situ synchrotron XRPD. We show that a phase with an orthorhombic P'2-type structure is formed for x ≈ 1, due to the cooperative Jahn-Teller effect of the Mn(3+) ions. P2 structure type stacking is observed for 0.35 < x < 0.82, while above 4.0 V, a new phase appears. A full indexation of the XRPD pattern of this latter phase was not possible because of the broadening of the diffraction peaks. However, a much shorter interslab distance was found that may imply a gliding of the MO2 slab occurring at high voltage. Raman spectroscopy was used as a local probe and showed that in this new phase the MO2 layers are maintained, but the phase exhibits a strong degree of disorder.

International audience; The new layered phase P2-Na1/2VO2 has been synthesized by sodium electrochemical deintercalation. Its structure has been studied by high resolution powder diffraction, pair distribution function analysis, and nuclear magnetic resonance spectroscopy between 300 and 350 K. An increase of 2 orders of magnitude in its electronic conductivity has been observed at approximately 322 K, and a structural transition has been found to occur simultaneously. The arrangement of sodium ordering in P2-Na1/2VO2, which maximizes sodium-sodium distances to lower electrostatic repulsions between alkali ions, is found to be unchanged across this transition. At room temperature, high resolution powder diffraction and pair distribution function analysis reveal the triangular lattice formed by vanadium ions to be distorted by the formation of pseudotrimers clusters with vanadium-vanadium distances as short as 2.581 Å. Above the transition, the pseudotrimers disappear and the triangular vanadium lattice becomes more regular with a mean vanadium-vanadium distance of 2.88 Å. At 350 K, the increase in P2-Na1/2VO2 electronic conductivity is due to enhanced charge transport resulting from the declustering of vanadium ions. These results highlight how sodium ordering between the MO2 layers and the electronic transport within the MO2 layers are intimately correlated in NaxMO2-type sodium-layered oxides.

International audience; Layered oxides are the subject of intense studies either for their properties as electrode materials for high-energy batteries or for their original physical properties due to the strong electronic correlations resulting from their unique structure. Here we present the detailed phase diagram of the layered P2-NaxVO2 system determined from electrochemical intercalation/deintercalation in sodium batteries and in situ X-ray diffraction experiments. It shows that four main single-phase domains exist within the 0.5≤x≤0.9 range. During the sodium deintercalation (intercalation), they differ from one another in the sodium/vacancy ordering between the VO2 slabs, which leads to commensurable or incommensurable superstructures. The electrochemical curve reveals that three peculiar compositions exhibit special structures for x = 1/2, 5/8 and 2/3. The detailed structural characterization of the P2-Na1/2VO2 phase shows that the Na+ ions are perfectly ordered to minimize Na+/Na+ electrostatic repulsions. Within the VO2 layers, the vanadium ions form pseudo-trimers with very short V-V distances (two at 2.581 Å and one at 2.687 Å). This original distribution leads to a peculiar magnetic behaviour with a low magnetic susceptibility and an unexpected low Curie constant. This phase also presents a first-order structural transition above room temperature accompanied by magnetic and electronic transitions. This work opens up a new research domain in the field of strongly electron-correlated materials. From the electrochemical point of view this system may be at the origin of an entire material family optimized by cationic substitutions.

International audience; The electrochemical cycling in a sodium battery of the lamellar oxide NaVO(2) is reversible in the Na(x)VO(2) composition range 1/2 ≤ x ≤ 1. The complex electrochemical curve reveals the presence of several transitions taking place during deintercalation. With the help of in situ X-ray diffraction, we observed the structural transitions taking place between Na(2/3)VO(2) and Na(1/2)VO(2). The diffractograms show the presence of several monophasic domains separated by biphasic domains. All phases present a monoclinic distortion of the α-NaFeO(2) structure in the composition range 1/2 ≤ x ≤ 2/3. Moreover the presence of a superstructure is evidenced for Na(1/2)VO(2). It is the first time that an ordered structure is reported at the Na(1/2)MO(2) composition with an O'3 oxygen stacking. A thorough investigation of electrochemically obtained O'3-Na(1/2)VO(2) was performed. The structure refinement reveals the existence of a sodium/vacancy ordering, with a peculiar arrangement of the V-V distances hinting at a pairing of vanadium atoms. Our first measurements of the physical properties of O'3-Na(1/2)VO(2) show a semiconductor behavior and a complex thermal dependence of the magnetic susceptibility related to the pairing of the vanadium atoms.

International audience; In this contribution, new data on the reversible Li+ intercalation in iron substituted sodium manganates are provided. Novel Na2/3Mn1−yFeyO2 (y = 0, 1/3 and 2/3) compounds with a P′3-type structure are prepared from freeze-dried citrate precursors at 500 °C. A new structural element is the development of three-layer oxygen stacking contrary to the well-known P2-type Na2/3MnO2 with a two-layer sequence. The effect of Fe additives on the structure of Na2/3MnO2 was examined by XRD powder diffraction and TEM analysis. The oxidation state and the distribution of transition metal ions in Na2/3Mn1−yFeyO2 were analysed using electron paramagnetic resonance spectroscopy. The lithium intercalation in Na2/3Mn1−yFeyO2 was investigated in two-electrode lithium cells of the type Li|LiPF6 (EC:DMC)|Na2/3Mn1−yFeyO2. The stability of the layered phases during lithium intercalation was studied by ex situ Raman spectroscopy. It was found that the intermediate Na2/3Mn2/3Fe1/3O2 composition is able to intercalate Li+ reversibly in high amounts. Details of the structure and its stability during the Li+ intercalation are discussed.

International audience; Manganese substituted sodium cobaltate, Na(2/3)Co(2/3)Mn(1/3)O(2), with a layered hexagonal structure (P2-type) was obtained by a co-precipitation method followed by a heat treatment at 950 °C. Powder X-ray diffraction analysis revealed that the phase is pure in the absence of long-range ordering of Co and Mn ions in the slab or Na(+) and vacancy in the interslab space. The oxidation states of the transition metal ions were studied by magnetic susceptibility measurements, electron paramagnetic resonance (ESR) and (23)Na magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The charge compensation is achieved by the stabilization of low-spin Co(3+) and Mn(4+) ions. The capability of Na(2/3)Co(2/3)Mn(1/3)O(2) to intercalate and deintercalate Na(+) reversibly was tested in electrochemical sodium cells. It appears that the P2 structure is maintained during cycling, the cell parameter evolution versus the sodium amount is given. From the features of the cycling curve the formation of an ordered phase for the Na(0.5)Co(2/3)Mn(1/3)O(2) composition is expected.

International audience; We report a X-ray absorption study at Ti K- and L2,3-edges to determine the role of TiO2 content as a nucleating agent in glass ceramics. It is found that the local Ti environment is not modified with TiO2 addition, indicating that medium range organization is responsible for its ability to promote internal versus bulk nucleation. We have identified a Ti coordination change between the nucleation front and the crystallized part of the glass ceramic. These changes correspond to conversion from 5-fold coordinated to 4-fold coordinated Ti in the remaining glassy part, resulting from compositional changes. This reveals that active sites for nucleation could be experimentally detected and that reorganization of the glass matrix during nucleation has a major influence on the ongoing nucleation processes.

International audience; This paper describes the preparation of NaxVO2 phases by means of electrochemical deintercalation. The curves V = f(x) show that the process is reversible up to x = 0.5 and they indicate the presence of multiple single phase domains in the range 1 < x < 0.5. Two single phases have been successfully isolated for Na1/2VO2 and Na2/3VO2 compositions; we report here the first X-ray powder diffraction measurements of these phases. They present a O'3-type monoclinic distortion of the O3 rhombohedral phase observed for Na1VO2. The evolution of cell parameters with sodium deintercalation is comparable with other AxMO2 layered oxides.

This work presents recent studies, concerning non linear optical properties of chalcogenide glasses. Second and third order properties are presented, on bulk glasses and in fibers. Chalcogenide glasses are based on sulfur, selenium, tellurium and the addition of other elements such as arsenic germanium, antimony gallium, etc. The interest of chalcogenide glasses is to associate high non linear properties with their infrared transmission from 0.5 - 1 /spl mu/m to 12 - 18 /spl mu/m depending on the composition.

International audience; Ordering of disordered materials occurs during the activated process of nucleation that requires the formation of critical clusters that have to surmount a thermodynamic barrier. The characterization of these clusters is experimentally challenging but mandatory to improve nucleation theory. In this paper, the nucleation of a magnesium alumino-silicate glass containing the nucleating oxide TiO 2 is investigated using neutron scattering with Ti isotopic substitution and 27 Al NMR. We identified the structural changes induced by the formation of crystals around Ti atoms and show important structural reorganization of the glassy matrix.

article i nfo Nucleation is the initiating event for the formation of any crystal from undercooled melt. Although the classical nucleation theory describes qualitatively many aspects of the crystallization process, the mechanisms favoring the first steps of nucleation are still unknown and required the full identification of the catalytic sites. In this work, we report a structural investigation of the system 2MgO-2Al2O3-5SiO2+ TiO2, a major glass-ceramic for scientific and industrial interest, in order to understand the structural influence of Ti as a nucleating agent. X-ray scattering and 27 Al Nuclear Magnetic Resonance studies were carried out on 2MgO-2Al2O3-5SiO2+xTiO2 glasses, with 0 mol% ≤x ≤15.5 mol%. No evidence of phase separation can be detected in the initial glasses by Transmission Electron Microscopy at nanoscale and Ti atoms appear to be homogeneously distributed within the glassy structure. We explain that the presence of TiO2 favors nucleation by the formation in the initial glass of high-coordinated Al species and the presence of structural fluctuations that mimic the initial crystalline phase precipitating in the glass. The understanding of the parent glass structure appears as a critical constraint to understand the pathways promoting nucleation.

International audience; The structure of the glass 2MgO–2Al2 O3 –5SiO2 –TiO2 was investigated using neutron diffraction with isotopic substitution. Reverse Monte Carlo (RMC) modeling was used to reproduce experimental structure factors derived from diffraction experiments. The local environment of titanium atoms was determined and it corresponds to an average of 5.4 ± 0.2 oxygen atoms at a mean distance of 1.86 ± 0.02 ̊A. This coordination number agrees with the predominance of fivefold coordination, with the coexistence of four- and sixfold coordination in similar amounts. 27 Al nuclear magnetic resonance (NMR) results revealed that the proportion of highly coordinated aluminum atoms in this titanium-bearing glass was higher than in the titanium-free sample. RMC modeling was used to interpret the structural role of these [5] Al species and we show a trend for preferential bonding between [5] Al and Ti atoms. This favored linkage is important to understand the role of titanium dioxide as a nucleating agent in inorganic glass-ceramics fabrication.

International audience; New class of chalcohalide glasses has been prepared in the GeS2-In2S3-CsI system with regard to their potential non-linear properties. The study of glass-forming region was undertaken to select glassy compositions, which present high non-linear (NL) optical properties with a low two-photon absorption. Thermal analyses, structural examination by Raman spectroscopy, non-linear optical measurements were investigated as a function of CsI contents. Introduction of CsI has shifted the band-gap edge towards the blue region of the absorption optical spectrum and therefore has limited the two-photon absorption. Their NL refractive index n2 are 60 times higher than silica glasses without any NL absorption. Moreover, second harmonic signal was observed in thermally poled samples similar to silica glass. However, this second order non-linearity is not temporally stable.

International audience; The structure of six glass compositions in theMgO–Al2O3–SiO2 systemwas investigated using neutron and X-ray diffraction. Reverse Monte Carlo modeling was used to reproduce experimental structure factors derived from diffraction experiments. The environment of Mg was determined and corresponds to an average of 5.1±0.1 oxygens at a mean distance of 2.00±0.02 Å with little change as the compositions vary. Tetrahedral, pentahedral and octahedral polyhedra are found with a majority of MgO5. The Al environment reveals the presence of highcoordinated Al in agreement with 27Al Nuclear Magnetic Resonance results. The Reverse Monte Carlo models were used to interpret the structural role of Mg and Al. The [5]Al species showa trend to be localized in the same regions, which have important implications to quantify the Si/Al ordering in aluminosilicate glasses and melts

International audience; High second-order susceptibilities are created by thermal poling in bulk germanium disulfide based chalcogenide glasses. Experimental conditions of the poling treatment (temperature, voltage, time) were optimized for each glass composition. The second-order nonlinear signals were recorded by using the Maker fringes experiment and a second-order coefficient χ(2) up to 8 pm V-1 was measured in the Ge25Sb10S65 glass. This value is obtained using a simulation based on accurate knowledge of the thickness of the nonlinear layer. Two mechanisms are proposed to explain the creation of a nonlinear layer under the anode: the formation and the migration of charged defects towards the anode may mainly occur in Ge20Ga5Sb10S65 and Ge25Ga5S70 glasses, whereas the migration of Na+ ions towards the cathode may be responsible for the accumulation of negative charges under the anode in Ge33S67 and Ge25Sb10S65 glasses. Different electronic conductivity behaviors seem to be at the origin of the phenomenon. In parallel, the potential effect of the poling treatment on the structural and electronic properties is studied using Raman spectroscopy and secondary ion mass spectroscopy measurements.

International audience; The non-linear optical response of sulphide glass-containing β-GeS2 microcrystallites, has been studied at a fundamental wavelength of λ=5.5 μm under additional irradiation by IR-pulses of λ=3.7 μm. A substantial increase of the non-linear susceptibility with IR-power and size of the microcrystallites has been found. Molecular dynamics calculations linked to quantum chemical calculations show that this effect could be explained by substantial contributions of the microcrystallite interfaces and due to the phonon sub-system. The role of anharmonic electron-phonon effects is experimentally confirmed by the observation of an optimal delay of 8 ps between the pump laser pulses at 3.7 μm and the probing laser pulses at 5.5 μm, which generate the observed second harmonic signal.

International audience; Permanent second-harmonic generation (SHG) has been demonstrated in chalcogenide based glass-ceramics containing non-linear micro-crystals with a size of a few micrometers. A glass composition from the Ge-Sb-S system was chosen as the reference glass for its stability against crystallization and atmospheric corrosion. Metallic cadmium was introduced in this matrix to promote crystallite formation resulting in infrared transparent glass-ceramics. A volume crystallization of β-GeS2 phase was obtained within the glass media by heating the glass samples at 370 °C for different durations. The glass-ceramics were then investigated by Raman spectroscopy, X-ray diffraction and NanoSIMS. The second-order non-linear signals were recorded by using Maker fringes experiment and were studied as a function of the crystallized volume fraction. The results indicated a non-linearity in chalcogenide glass-ceramics about one hundred times lower than α-quartz for a 1 mm thick sample heat treated 144 h.

International audience; The aim of this work is to investigate and qualify vitreous regions in new chalcogenide systems containing highly polarizable elements like S, Se, As, Sb, Bi, Pb and I. The sulfur based system, As2S3-Sb2S3-Bi2S3-PbI2, as well as the selenium containing glasses As2Se3-Sb2Se3-PbI2 have been studied. Large vitreous regions have been defined in the both systems: sulfur and selenium. Indeed, several glass compositions can accept in the vitreous network a molar concentration near 50% of PbI2. Physical properties such as glass transition temperature, crystallization temperature, optical transmission, band-gap wavelength have been measured versus glassy compositions.

This work concerns the electrochemical and structural studies carried out on two systems used aspositive electrode materials for Na-ion batteries: P2/O3-NaxMn1-yFeyO2 and O’3-NaxNiO2. Concerning theP2/O3-NaxMn1-yFeyO2 systems, in situ X-ray diffraction carried out during the charge of the batteriesshowed that both materials undergo several structural transitions. Both the P2 and O3 phases show adistorted phase for the higher intercalation rates (x) and a poorly ordered phase for the lower ones.Between these two states, P2-based materials exhibit less structural transitions than the O3-based ones.This is correlated to the better electrochemical properties the P2-based materials exhibit (better dischargecapacity, better capacity retention…). X-ray absorption and 57Fe Mössbauer spectroscopies showed thatthe Mn4+/Mn3+ and Fe4+/Fe3+ redox couples are active upon cycling, respectively at low and high voltage.Concerning O’3-NaNiO2, in situ X-ray diffraction carried out during the charge of O’3-NaNiO2//Nabatteries showed several structural transition between O’3 and P’3 structures, resulting from slab glidings.These transitions are accompanied by Na+ - vacancies ordering within the “NaO6” slabs. Upon discharge,the material does not come back to its initial state and, instead, the Na≈0.8NiO2 phase represents themaximum intercalated state. The occurrence of this limiting phase prevents O’3-NaNiO2 to be consideredas an interesting material for real Na-ion applications., Ce travail présente les études électrochimiques et structurales menées sur deux systèmes : P2/O3-NaxMn1-yFeyO2 et O’3-NaxNiO2 utilisés en tant que matériaux d’électrode positive pour batteries Na-ion.Concernant le système P2/O3-NaxMn1-yFeyO2, l’étude par diffraction des rayons X menée in situ pendantla charge de batteries a montré de nombreuses transitions structurales. Que leur structure soit de type P2ou O3, les matériaux présentent une phase distordue pour les taux d’intercalation (x) les plus élevés etune phase très peu ordonnée pour les taux d’intercalation les moins élevés. Entre ces deux étatsd’intercalation, les phases de type P2 présentent moins de transitions que les phases de type O3. Celaentraine de meilleures propriétés électrochimiques pour les phases de type P2 (meilleure capacité endécharge, meilleure rétention de capacité…). Les spectroscopies d’absorption des rayons X et Mössbauerdu 57Fe ont montré que les couples redox Mn4+/Mn3+ et Fe4+/Fe3+ sont impliqués lors du cyclage, à bas ethaut potentiel, respectivement.Concernant O’3-NaNiO2, la diffraction des rayons-X menée in situ pendant la charge de batteriesO’3-NaNiO2//Na a montré de nombreuses transitions structurales O’3 ↔ P’3 résultant du glissement desfeuillets MO2. Ces transitions s’accompagnent de mises en ordre Na+ - lacunes dans le matériau. La tailledes grains a montré avoir un intérêt majeur puisqu’elle influe sur le nombre de phases présentessimultanément dans le matériau. Lorsque la batterie est déchargée, la phase limitante Na≈0.8NiO2 estobservée et empêche le retour à O’3-NaNiO2