Electronics Supplementary Information for. Manab Kundu, Cheuk Chi Albert Ng, Dmitri Y. Petrovykh and Lifeng Liu*

Transcription

1 Electronics Supplementary Information for Nickel foam supported mesoporous MnO 2 nanosheet arrays with superior lithium storage performance Manab Kundu, Cheuk Chi Albert Ng, Dmitri Y. Petrovykh and Lifeng Liu* International Iberian Nanotechnology Laboratory (INL), Braga, Portugal *Corresponding author. lifeng.liu@inl.int (L.L.) S1

2 Experimental details Sample preparation: Before electrodeposition, the Ni foam (110 PPI, 480 g m -2, 0.3 mm thick) was carefully cleaned with 6 M hydrochloric acid solution in an ultrasonic bath for 10 min, and then washed in sequence with copious de-ionized water ( 18 M cm) and absolute ethanol. Afterwards, the Ni foam was dried at ambient temperature. The electrodeposition was performed in a twoelectrode electrochemical cell using a piece of freshly cleaned Ni foam as working electrode and a platinum wire as counter electrode. The electrolyte was 0.02 M manganese acetate ( 99%, Sigma-Aldrich) aqueous solution. A Keithley 2400 sourcemeter was used as a power supply. The deposition was conducted at room temperature at a current density of 10.5 ma cm -2 for 3 min. After deposition, the Ni foam was thoroughly rinsed with de-ionized water and absolute ethanol for several times, and then dried in air. Subsequently, the sample was annealed in highpurity nitrogen (99.999%) at 170 C for 5 h. The weight of the sample was measured before electrodeposition and after thermal annealing using a high precision electronic balance (Sartorius CPA225D) in order to calculate the mass of the deposited active materials. Characterization: The morphology of the as-prepared MnO2 nanosheets was examined by scanning electron microscopy (FEI Quanta FEG650), and their crystal phase and microstructure were investigated by X-ray diffractometry (PanAnalytical X pert Pro) and transmission electron microscopy (FEI TITAN ChemSTEM kv, probe corrected), respectively. The surface chemistry of manganese oxide nanosheets was probed by X-ray photoelectron spectroscopy (XPS) using an ESCALAB 250 Xi system (Thermo Scientific) equipped with a monochromated Al Kα X-ray source, a hemispherical electron energy analyzer, a magnetic lens, and a video camera for viewing the analysis position. Uniform charge neutralization was provided by beams of low-energy ( 10 ev) Ar + ions and low-energy electrons guided by the S2

3 magnetic lens. The standard analysis spot of ca μm 2 was defined by the microfocused X-ray source. The measurements were performed at room temperature in an ultra-high vacuum chamber with the base pressure < mbar; the charge neutralization device produced ca mbar partial pressure of Ar during measurements. The energy of the monochromated Al Kα X-ray source was measured to be within <0.2 ev from ev. The binding energy (BE) scale of the analyzer was calibrated to produce <50 mev deviations of the three standard peaks from their standard values: ev for Au 4f7/2, ev for Ag 3d5/2, and ev for Cu 2p3/2. The aliphatic C 1s peak was observed at ev. High-resolution elemental XPS data in C 1s, O 1s, Mn 2p, and Mn 3s regions were acquired with the analyzer pass energy set to 20 ev (corresponding to energy resolution of ca ev) and the step size set to 0.1 ev. All the spectra were acquired in normal emission with an effective analyzer collection angle of ca. 30. Avantage software package (Thermo Fisher Scientific) was used to fit the elemental spectra and to quantify the standard atomic % elemental compositions based on calibrated analyzer transmission functions, Scofield sensitivity factors, and effective attenuation lengths for photoelectrons from the standard TPP-2M formalism. Electrochemical measurements: The electrochemical performance was evaluated by cyclic voltammetry (CV), galvonastatic charge/discharge technique and electrochemical impedance spectroscopy (EIS) using a Biologic VMP3 battery tester. The tests were made using 2032 type coin cells with the Ni foam supported MnO2 nanosheet arrays as working electrode and Li metal as counter as well as reference electrodes. The electrolyte consists of LiPF6 dissolved in EC: DMC (1:2 vol%). Celgard 2300 membranes were used as separator. The cells were assembled in an argon filled glove box (JACOMEX, Germany) where the moisture and oxygen levels were kept below 0.5 ppm. S3

4 Supplementary Figures Figure S1. (a) Overview and (b) Zoomed view SEM micrographs of the nickel foam (110 PPI, 480 g m -2, 0.3 mm thick) used in the experiments. S4

5 Figure S2. Charge/discharge profiles of the cells measured at current densities of (a) 700 ma g -1 and (b) 1000 ma g -1. S5

6 Figure S3. (a) The electrochemical impedance spectra (EIS) of the MnO2 NS electrode measured at different cycling intervals. Insets: zoomed view (upper right) and the fitted impedance values (lower right). Equivalent circuit models of (b) the as-assembled fresh cells and (c) the cycled cells, where Rel refers to the electrolyte resistance, Qsei the constant phase element of the SEI layer, Rsei the resistance of the SEI layer, Qdl the constant phase element of the double layer, Rct the charge-transfer resistance, and Wo the Warburg impedance. Frequency range: 1 mhz 1 MHz. It is seen that all the Nyquist plots consist of a large depressed semicircle followed by a straight slope. The depressive nature originates from the existence of a Li + ion migration process through the surface film of the electrode (e.g. SEI layer) in the high frequency region and a charge transfer process between the electrode and electrolyte in the medium frequency region. A sharp Warburg in the low frequency region indicates fast diffusion of Li + ions to the electrode. S6

7 Figure S4. SEM micrographs showing the morphology of the Ni foam supported MnO2 NSs subjected to charge/discharge for 70 cycles at various current densities. After disassembling, the electrode was ultrasonicated in isopropanol for 10 min in order to remove the remaining electrolyte. (a) Overview and (b) Zoomed view. S7