Empyrean powder diffractometer

A Bruker AV-400 NMR spectrometer was applied to record the liquid 1H NMR spectra. Solid-state 13 C NMR spectra were recorded on an AVIII 500 MHz solid-state NMR spectrometer. The FTIR spectra (KBr) were obtained using a SHIMADZU IRAffinity-1 Fourier transform infrared spectrophotometer. Thermogravimetric analysis (TGA) was recorded on a SHIMADZU DTG-60 thermal analyzer under N₂. PXRD data were collected on a PANalytical B.V. Empyrean powder diffractometer using a Cu Kα source (λ = 1.5418 Å). For scanning electron microscopy (SEM) images, JEOL JSM-6700 scanning electron microscope was applied. The transmission electron microscopy (TEM) images were obtained on JEM-2100 transmission electron microscopy.

To synthesize garnet-type solid electrolyte Li_6.25Al_0.25La₃Zr₂O₁₂ (LLZO) Li₂CO₃ (>99.0%, Sigma-Aldrich), La(OH)₃ (99.9%, Sigma-Aldrich), Al₂O₃ (99.8%, abcr), and ZrO₂ nano-powder (<100 nm, Sigma-Aldrich) were mixed in a stoichiometric ratio. This mixture was then ball-milled for 12 h at 350 rpm under pure oxygen atmosphere. After milling, the homogenized powder was pressed into large pellets in MgO-crucibles and then calcined at 1000 °C for 4 h under a 150-sccm oxygen flow. After ball-milling again for 20 h at 350 rpm, small pellets with diameters of ~8.3 mm and thicknesses of 2 mm were isostatically pressed with 380 MPa and sintered at 1230 °C in MgO-crucibles with mother powder (calcined LLZO powder) under oxygen flow. The LLZO pellets have a porosity of ~(94 ± 2)%, their ionic conductivity is (4.6 ± 0.4)10⁻⁴ S cm⁻¹. The ionic conductivity is calculated by considering the thickness, the contact area with the electrode, and the total bulk and grain boundaries resistance of the LLZO pellet in a Li|LLZO|Li symmetric cell extracted by fitting of electrochemical impedance result which is acquired in at 25 °C (supplementary Fig. 2). The sintered LLZO was characterized with x-ray diffraction by using a PANalytical Empyrean powder diffractometer in Bragg-Brentano θ-θ geometry with copper K_α radiation.

The crystallographic phase and the orientation of the films were studied by XRD. A Panalytical Empyrean powder diffractometer equipped with PIXcel linear detector and monochromator on diffracted beam was used. Data were collected in the 2θ/θ geometry using Cu Kα radiation (λ = 1.5405 Å) at 40 kV and 30 mA. Diffraction patterns were taken during 8 minutes in a 2θ range of 20–65° with a step size of ~0.039°.

Routine X-ray powder diffraction (XRPD) patterns were collected using a conventional PANalytical Empyrean powder diffractometer (PANalytical Lelyweg, Almelo, The Netherlands, θ–2θ) using λCu Kα1, and Kα2 radiation (λ = 1.54051 and 1.54433 A°). The XRPD patterns were carried out with a 2θ scan between 3–35° with a step size of 0.013° and a scanning speed of 0.1°·s⁻¹. Fourier transform infrared (FTIR) spectroscopic analyses were performed in a Nicolet 6700 (Thermo Scientific, Waltham, MA, USA) infrared spectrometer with the help of an attenuated total reflectance (ATR) diamond accessory. High-resolution transmission electron microscopy (HRTEM) images were obtained, and energy dispersive X-ray spectroscopy (EDX) elemental mapping was performed using a high-resolution transmission electron microscope (Centre of Scientific Instrumentation of the University of Granada, Granada, Spain). 25 μL of each sample was incubated on carbon-coated grids for 5 min before being washed off with ultra-pure water. Uranyl acetate was employed for negative stained samples. Grids were observed in a High-Resolution TEM (HRTEM) TITAN from FEI Company (Hillsboro, OR, USA) operated at 300 kV. Doxorubicin and Furazan fluorescence measurements were performed with a Cary Eclipse Fluorescence Spectrometer from Agilent (Santa Clara, CA, USA) and a PerkinElmer Spectrum FL 1.4.0 (Waltham, MA, USA).