____________________Dataset for Preparation of novel lithiated high-entropy spinel type oxyhalides and their electrochemical performance in Li-ion batteries____________________ Last updated: 2024-12-17 ______Contact______ * Markéta Zukalová * ORCID: 0000-0002-1773-6642 * J. Heyrovský Institute of Physical Chemistry, Czech Acad. Sci. * Dolejškova 21155/3, Praha 8, Česká republika ______Principal Investigator______ * Karel Bouzek * ORCID: 0000-0002-0394-0634 * Dept. of Inorganic Technology, Faculty of Chemical Technology, University of chemistry and Technology, Prague * Technicka 5, 166 28, Prague 6, Czech Republic ______Data manager or custodian______ * Šárka Paušová * ORCID: 0000-0003-2494-1510 * Dept. of Inorganic Technology, Faculty of Chemical Technology, University of chemistry and Technology, Prague * Technicka 5, 166 28, Prague 6, Czech Republic ______Licence______ *Dataset for Preparation of novel lithiated high-entropy spinel type oxyhalides and their electrochemical performance in Li-ion batteries © 2024 by Markéta Zukalová is licensed under CC BY *licence information: https://creativecommons.org/licenses/by/4.0/ ------------------------------------------------------------------------------------------------ ______About the dataset______ * Electrochemical characterization of novel lithiated high-entropy spinel type oxyhalides Electrochemical measurements carried out using the 2032-coin cells with the Li-metal anode have shown voltammetric charge capacities of 450, 694, and 593 mAh g-1 for HEOFe, LiHEOFeCl, and LiHEOFeF, respectively. Galvanostatic chronopotentiometry at 1 C rate confirmed high initial charge capacities for all the samples but galvanostatic curves exhibited a capacity decay over 100 charging/discharging cycles. Raman spectroelectrochemistry measured on the LiHEOFeF sample proved the reversibility of the electrochemical process for initial charging/discharging cycles. Electrochemical impedance spectroscopy revealed the lowest initial charge transfer resistance for LiHEOFeCl and its gradual decrease both for LiHEOFeCl and LiHEOFeF during galvanostatic cycling, whereas the charge transfer resistance of HEOFe slightly increases over 100 galvanostatic cycles due to different mechanism of the electrochemical reduction. * The foreign authors do not agree to provide their data ______Methods of data collection______ * Electrochemical characterization The respective electrode material (HEOFe, LiHEOFeCl, or LiHEOFeF) was mixed with a conductive carbon black C65 (Timcal), and a 2 % aqueous solution of carboxymethylcellulose (CMC from Sigma). The mass ratio of the HEO-containing active material to C65 and CMC was 7:2:1. The mixture was then diluted with deionized water to a consistency of viscous paste and coated by doctor-blading on Al foil. After drying in air at ambient temperature and subsequently at 100 °C in a vacuum overnight, the coated Al foil was cut into disc electrodes of 15 mm in diameter. The electrodes were stored in a glove box with an argon atmosphere. Coin cells were assembled with a cathode described above, a Li-foil anode (14 mm in diameter), a glass microfiber separator (Whatman), and 20 μL of electrolyte solution. The electrolyte solution consisted of 1 M LiPF6 in ethylene carbonate/dimethyl carbonate (1:1 by volume). The electrolyte solution for Raman spectroelectrochemical measurement consisted of 1M LiClO4 in ethylene carbonate/dimethyl carbonate (1:1 by volume). The scheme S1 (Supporting Info) depicts the coin cell for Raman spectroelectrochemistry. The cell was equipped with a glass window to the cathode for in situ spectral measurement. * Cyclic voltammetry Cyclic voltammetry measurements were carried out with Autolab 302N potentiostat (Metrohm) controlled by Nova SW in a potential window of 0.65 V/3.0 V vs. Li+/Li with a scan rate of 50, 20, 10, 5, 2, 1, 0.5, 0.2, and 0.1 mV s-1. All potentials in this study are referred to the Li+/Li electrode. * Galvanostatic chronopotentiometry Galvanostatic chronopotentiometry at 1C was measured in the 2032 coin-type test cells by the Neware Battery Testing System controlled by BTS 7.6 SW. * Electrochemical impedance spectra (EIS) Electrochemical impedance spectra (EIS) of the particular coin cell were measured after cyclic voltammetry measurements, then after the 50th and 100th galvanostatic cycle by the FRA2 module of Autolab 302N. EIS was investigated over a frequency range from 100 kHz to 0.1 Hz (modulation amplitude 10 mV) at 2.4 V vs. Li+/Li (which is near the open-circuit potential). Before each EIS measurement, the potential was equilibrated at 2.4 V for 1 min. * Raman spectroelectrochemistry The Raman spectra were measured on a MicroRaman system (LabRAM HR spectrometer, Horiba Jobin–Yvon) interfaced to an Olympus BX microscope. The spectra were excited by a He–Ne laser, 633 nm. The Raman spectrometer was calibrated using the F1g line of Si at 520.2 cm-1. The in-situ Raman spectra were measured during chronoamperometry in a quasi-equilibrium state, which was attained after 2 min of arresting the electrode potential at the selected value. Chronoamperometry was carried out with Autolab PGSTAT30 apparatus controlled by Nova SW in the potential window of 3.0 V -0.7 V vs. Li+/Li. ______Methods of data processing______ * Electrochemical impedance spectroscopy Spectra were evaluated using the Zview 4.0 (Scribner) software by fitting to a Randles-type circuit, in which Rs is the serial resistance, and RCT (the charge-transfer resistance) is parallel to the constant phase element (CPE) to account for non-ideal capacitive behavior of the cell. The circuit is completed by the Warburg impedance ZW element for modeling the mass transport effects at lower frequencies.The spectra were normalized to the mass of active electrode material. Alternative normalization (to the physical (BET) areas) will give a similar result– the actual surface areas are all near 4 m2 g-1 * Charge capacities vs scan rate dependence The scan-rate dependence of the charge capacities was calculated from the discharge branch of the cyclic voltammogram ------------------------------------------------------------------------------------------------ ______File name structure_____ * VZx_000_111_XXXXX_Y_0000_v1 VZx – research proposal (3 characters) 000 – order of the publication in the research proposal (3 char.) 111 – last 3 numerals of the superior indicator (3 char.) XXXXX – institution abbreviation (max. 5 char.) VSCHT - University of chemistry and technology, Prague CVUT - Czech Technical University UFCH - Institute of Physical Chemistry, Czech Academy of Sciences UK - Charles University VUT - Brno University of Technology Y – file type (1 char.): M – manuscript D – data S – supplementary information P – published version of the arctile 0000 – order of the files in the dataset (4 char.) v1 – versioning (v + version number) * example: VZ1_001_023_VSCHT_D_0001_v1.csv ______File formats______ * cyclic voltammogram - TIF File * Charge capacities vs scan rate dependence - TIF File * Galvanostatic chronopotentiometry-TIF File * Raman spectroelectrochemistry-TIF File * Electrochemical impedance spectroscopy-TIF File * SI-Raman spectroelectrochemistry instrument-PDF File * SI-Current fluctuations during measurement-TIF File ______Date formats______ * ______Units and abbreviations______ * Specific current-A/g * Potential-V * Specific capacity-mAh/g * Raman shift-1/cm * Charge transfer resistance-RCT-mΩ∙g * Electrochemical impedance-Z-Ω∙g * HEOFe-(Zn0.25Mg0.25Co0.25Cu0.25)Fe2O4 * LiHEOFeCl-Li0.5(Zn0.25Mg0.25Co0.25Cu0.25)0.5Fe2O3.5Cl0.5 * LiHEOFeF-Li0.5(Zn0.25Mg0.25Co0.25Cu0.25)0.5Fe2O3.5F0.5 ------------------------------------------------------------------------------------------------ ______List of files______ * Electrochemical characterization of novel lithiated high-entropy spinel type oxyhalides VZ1_012_021_UFCH_D_0001_v2.tif VZ1_012_021_UFCH_D_0003_v1.tif VZ1_012_021_UFCH_D_0004_v1.tif VZ1_012_021_UFCH_D_0005_v1.tif * Supporting info VZ1_012_021_UFCH_S_0006_v1.pdf VZ1_012_021_UFCH_S_0007_v1.tif VZ1_012_021_UFCH_S_0008_v1.tif