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High-Pressure Melting Curve of Zintl Sodium Silicide Na4si4 by in Situ

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High-Pressure Melting Curve of Zintl Sodium Silicide Na4si4 by in Situ High-Pressure Melting Curve of Zintl Sodium Silicide Na4Si4 by In Situ Electrical Measurements Alexandre Courac, Yann Le Godec, Carlos Renero-Lecuna, Hicham Moutaabbid, Ram Kumar, Cristina Coelho-Diogo, Christel Gervais, David Portehault To cite this version: Alexandre Courac, Yann Le Godec, Carlos Renero-Lecuna, Hicham Moutaabbid, Ram Kumar, et al.. High-Pressure Melting Curve of Zintl Sodium Silicide Na4Si4 by In Situ Electrical Mea- surements. Inorganic Chemistry, American Chemical Society, 2019, 58 (16), pp.10822-10828. 10.1021/acs.inorgchem.9b01108. hal-02342905 HAL Id: hal-02342905 https://hal.sorbonne-universite.fr/hal-02342905 Submitted on 10 Nov 2020 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. High Pressure Melting Curve of Zintl Sodium Silicide Na4Si4 by In Situ Electrical Measurements *,a a a a Alexandre Courac, Yann Le Godec, Carlos Renero-Lecuna, Hicham Moutaabbid, Ram Kumar,b Cristina Coelho-Diogo,c Christel Gervais,b and David Portehaultb a Sorbonne Université, CNRS, Muséum National d’Histoire Naturelle, IRD, Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC), 75005 Paris, France b Sorbonne Université, CNRS, Collège de France, Laboratoire de Chimie de la Matière Condensée de Paris (CMCP), 4 place Jussieu, F-75005, Paris, France c Sorbonne Université, CNRS, Institut des Matériaux de Paris Centre, 4 place Jussieu, F- 75005, Paris, France AUTHOR INFORMATION Corresponding Author * Corresponding author: [email protected] 1 ABSTRACT. The inorganic chemistry of the Na-Si system at high pressure is fascinating, with a large number of interesting compounds accessible in the industrial pressure scale, below 10 GPa. Especially, Na4Si4 is stable in this whole pressure range, and thus plays an important role for understanding the thermodynamics and kinetics underlying materials synthesis at high pressures and high temperatures. In the present work, the melting curve of + 4- the Zintl compound Na4Si4 made of Na and Si4 tetrahedral cluster ions is studied at high pressures up to 5 GPa, by using in situ electrical measurements. During melting, the insulating Na4Si4 solid transforms into an ionic conductive liquid that can be probed through the conductance of the whole high-pressure cell, i.e. the system constituted of the sample, the heater and the high-pressure assembly. Na4Si4 melts congruently in the studied pressure range and its melting point increases with pressure with a positive slope dTm/dp of 20(4) K/GPa. KEYWORDS Sodium silicide, High pressure, Phase diagram, Melting curve 2 INTRODUCTION The Zintl solid sodium silicide Na4Si4 bears Si species with negative oxidation state and built 4- + 1-2 on [Si4] tetrahedral clusters, which are surrounded by Na cations on each face. The presence of both covalent and ionic bonds in the structure imparts interesting chemical and 3 physical attributes. Na4Si4 itself may be considered as a strategic energy material in hydrogen technologies to generate hydrogen as a fuel (portable hydrogen fuel cell cartridges) and for 4 high energy density storage of hydrogen under low pressure. Besides, Na4Si4 is a promising precursor for the synthesis of extended Si frameworks and allotropes of technological 5-13 relevance. NaxSi46 (x ≤ 8) and NaxSi136 (x ≤ 24) (type-I and type-II clathrates, respectively) consisting of Si cages encapsulating Na have been reported from Na4Si4 14-17 decomposition. Empty Si46 and Si136 frameworks also provide tunable band gap for 15, 18 thermoelectrics and photovoltaics with Si136 exhibiting a quasi-direct bandgap of ~2 eV. Recently Na4Si4 has been used as precursor to design a new high-pressure synthetic route to 13, 19 the narrow-bandgap silicon allotrope Si-III. As a starting material, Na4Si4 is a compound of choice, as compared to ductile metallic sodium, for high pressure synthesis, since it can be finely powdered, which is crucial for homogeneity of the product. In addition, it participates in the phase equilibria11 and impacts crystallization kinetics20 in the binary Na-Si system that holds great promise to discover new technologically relevant semiconducting Si allotropes and compounds in the high pressure range. This is exemplified by the high pressure clathrate 20-21 NaSi6 that leads by Na substraction to the new orthorhombic allotrope Si24 with quasi- direct bandgap of ~1.35 eV,6 making this solid highly relevant for energy conversion.22 Overall, Na4Si4 appears as an important starting or intermediate compound that participates in the Na-Si phase equilibria during high-pressure syntheses. However, our understanding of the high pressure-temperature phase diagram and more broadly of thermodynamic data of Na4Si4 is incomplete and relies sometimes on controversial reports.23-25 3 Na4Si4 at ambient pressure has two low- and high- temperature polymorphs, α- and β- respectively.23,26 The temperature of the α-to-β transformation is ~885 K at ambient pressure.24 An isosymmetric transformation of the monoclinic α form has been also reported 27 above 10 GPa and 300 K, yielding γ-Na4Si4. The equation-of-state for α-Na4Si4 below 27,28 10 GPa suggests a bulk modulus B0 = 24(1) GPa (B’0 = 4). According to the density of the different polymorphs, β- and γ-Na4Si4 should exhibit lower and higher bulk modulus, respectively, but still close to that of the α form.29-32 In order to effectively use Na4Si4 as precursor for high-pressure syntheses, a detailed understanding of its high pressure-temperature phase diagram and physical behavior in the liquid state is an important requisite. With this objective, we have especially focused on the melting curve of Na4Si4. Because of their refractory behavior and high reactivity, assessing melting of compounds like Na4Si4 under HPHT conditions is a significant methodological challenge. Indeed, in situ X-ray diffraction (XRD) peaks are widened under HP and Na-Si solids and liquids react with most available thermocouples, thus hindering a precise evaluation of the melting temperature by regular XRD techniques. To overcome this limitation, we propose a new methodology to probe phase transitions, based on electrical conductivity measurements. EXPERIMENTAL METHODS Synthesis The silicon (~325 mesh, 99%) and NaH (95%) powder swere obtained from Sigma-Aldrich. All the synthesis and manipulations were performed inside a glove-box and on a Schlenk line under Ar atmosphere. Na4Si4 was synthesized using a procedure adapted from the one 4 reported by Ma et al.33 In a typical synthesis Si and NaH powders were mixed in 1:2.1 mole ratio and ball milled for 2 min at 20 Hz (Retsch MM400 ball mill airtight vials of 50 mL, one steel ball of 62.3 g and a diameter of 23 mm). The obtained homogeneous mixture was transferred to an h-BN crucible, covered with a lid and subsequently transferred inside a quartz tube. The reaction was performed at 420 °C for 90 hours under Ar. The product was obtained as a brown-black pellet with white residue on top. The white residue corresponded to NaOH and was carefully removed from the top of the pellet. The latter was crushed to obtain Na4Si4 powder. Characterization X-ray diffraction (XRD) was performed on a Bruker D8 Advance diffractometer operating at the Cu Kα wavelength, with a sample holder equipped with a plastic dome to maintain the sample under inert argon atmosphere. The crystallographic reference was obtained from the reference ICSD card 193513. The resulting grey powder (according to XRD, a = 12.17(2) Å, b = 6.55(1) Å, c = 11.15(2) Å, β = 119.0(3)°, space group No 15, C12/c1, which corresponds 26 29 23 to the α-Na4Si4 polymorph) was transferred and stored under argon. Si and Na magic angle spinning nuclear magnetic resonance (MAS NMR) experiments were performed on a 700 MHz AVANCE III Bruker spectrometer operating at 139.05 MHz using a 3.2 mm Bruker probe spinning at 20 kHz and at 185.20 MHz using a 4 mm Bruker probe spinning at 14 kHz respectively. A single-pulse excitation was used with a recycle delay of 500 s and 512 scans for 29Si and of 1s and 24 scans for 23Na. 29Si and 23Na chemical shifts were referenced to TMS and 0.1M NaCl (aq) respectively. The spectra were simulated with the DMFIT program.34 5 Electrical measurements at HPHT High pressure experiments have been performed using an hydraulic “Paris-Edinburgh” (PE) press applying force on tungsten carbide opposite anvils that compress a high-pressure cell (Fig. 1a). High temperatures were achieved by resistive heating (graphite ceramic or plastified graphite material, Grafoil). The pressure was calibrated with the diamond Si equation-of-state by in situ XRD at the PSICHE beamline of synchrotron SOLEIL.11 The temperature was calibrated with a Si melting standard at high pressure.35 Graphite (as ceramic or in grafoil) is a material of choice to serve simultaneously as heater and capsule material, while being chemically inert versus the Na4Si4 melt at the temperatures of interest. A typical HP cell is shown in Fig. 1a, along with the corresponding equivalent circuit (Fig. 1c) used for electrical measurements, including the heater and the sample (in parallel connection to the middle part of the heater). An alternating current was used for heating the cell by the Joule effect, simultaneously, the total resistance of the heating chain (together with voltage, current and power) has been probed.
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