Asymmetric Supercapacitors Using 3D Nanoporous Carbon and Cobalt Oxide Electrodes Synthesized from a Single Metal-Organic Framework

Transcription

1 Supplementary Information Asymmetric Supercapacitors Using 3D Nanoporous Carbon and Cobalt Oxide Electrodes Synthesized from a Single Metal-Organic Framework Rahul R. Salunkhe, 1 Jing Tang, 1,2 Yuichiro Kamachi, 1,3 Teruyuki Nakato, 3 Jung Ho Kim*,4 and Yusuke Yamauchi*,2 [1] World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki , Japan. [2] Faculty of Science and Engineering, Waseda University, Okubo, Shinjuku, Tokyo , Japan. [3] Department of Applied Chemistry, Graduate School of Engineering, Kyushu Institute of Technology, 1-1 Sensui-Cho, Tobata, Kitakyushu, Fukuoka , Japan. [4] Institute for Superconducting and Electronic Materials, University of Wollongong, North Wollongong, New South Wales 2500, Australia. Keywords: nanoporous materials; coordination polymers; metal-organic frameworks; cobalt oxide; carbon; supercapacitors *Corresponding authors: jhk@uow.edu.au (J.H. Kim); Yamauchi.yusuke@nims.go.jp (Y. Yamauchi) S1

2 Table S1 Comparison of surface area of our Co 3 O 4 polyhedra with previously reported Co 3 O 4 nanostructures produced by different synthetic routes. Method Morphology Surface area (m 2 g - ) Ref. Hydrothermal method Ultralayered Co 3 O 4 97 S1 Chemical precipitation Co 3 O 4 Nanosheets 127 S2 Hydrothermal method Co 3 O 4 nanorod/ni foam S3 Controlled precipitation Co 3 O 4 nanosheets 75.9 S4 MOF templated method Co 3 O 4 microsheets 0.21 S5 Solution method Co 3 O 4 nanosheets S6 Topotactic transfer approach Co 3 O 4 nanotubes 7.6 S7 Co 3 O 4 Nanosheet 17.8 Hydrothermal method Co 3 O 4 Nanobelt 20.1 S8 Co 3 O 4 Nanocubes 22.6 MOF templated method Co 3 O 4 porous agglomerates S9 MOF templated method Co 3 O 4 polyhedrons 148 Our work S2

3 Table S2 Comparison of electrochemical performance of our Co 3 O 4 sample with previous reports using standard three-electrode system. Method Electrolyte Morphology Hydrothermal method Hydrothermal method Controlled precipitation method Hydrothermal method Hydrothermal method Hydrothermal method MOF templated method MOF templated Capacitance (F g -1 ) Scan rate (mv s -1 ) Current density (A g -1 ) Ref. KOH (6M) Nanorod S10 KOH (1M) Ultra layer S1 KOH (2M) Layered S4 NaOH (1M) Net-like S11 KOH (2M) Nanowire S12 KOH (6M) Flakes S13 KOH (6M) Sheets S5 KOH (6M) Porous polyhedron Our work S3

4 method Table S3 Various performance parameters for our ASC supercapacitor. Current density (A g -1 ) Discharge time Specific capacitance (F g -1 ) Specific energy (W h kg -1 ) Specific power (W kg -1 ) (s) S4

5 Table S4 Comparison of our ASC performance of different metal oxides/hydroxides. Materials Counter Electrolyte Operating Energy Power Ref. voltage (V) density (W h kg -1 ) density (W kg -1 ) Ni(OH) a-mego KOH (6M) S14 foam Co (OH) 2 GO KOH (1M) S15 nanorods MoO 3 AC LiSO S16 MnO 2 AC K 2 SO S17 (0.5 M) MnO 2 AC Na 2 SO S18 (0.5 M) Ni(OH) 2 AC KOH (1 M) S19 Co 3 O 4 Nanoporous carbon KOH (6 M) Our work GO: graphene oxide a-mego: activated microwave exfoliated graphite oxide AC: activated carbon (Note: The comparison has been made with bare metal oxides/hydroxides that used as positive electrode only and ASC calculation based on weight of active electrode materials.) S5

6 Figure S1 Figure S1. Wide angle XRD pattern of ZIF-67 crystals. Note for Figure S1: The topological information of the prepared crystals is revealed by the powder X-ray diffraction (XRD) patterns. As shown in the Figure S1, the diffraction peaks of the prepared crystals are identical to simulated crystal structure of the ZIF-67 crystals, S20 indicating the successful formation of ZIF-67 crystals. 6

7 Figure S2 Figure S2. EDS elemental mapping images of nanoporous carbon (top) and nanoporous Co 3 O 4 (bottom). Both samples contain carbon, cobalt, oxygen, and nitrogen as the main elements. (All scale bars shown are 1 μm in length.) 7

8 Figure S3 Figure S3. (a, c) Nitrogen adsorption-desorption isotherms for (a) nanoporous carbon and (c) nanoporous Co 3 O 4. (b, d) Pore size distributions of (b) nanoporous carbon and (d) nanoporous Co 3 O 4. Inset of b shows magnified view of mesopores distribution. 8

9 Figure S4 Figure S4 (a) CV curves of Co 3 O 4 //carbon ASC. The device was cycled by varying the upper cell voltage from 1 V to 1.6 V. (b) Stability study of ASC up to 2000 repeated charge-discharge cycles. Inset of (b) shows the 10 charge-discharge cycles. 9

10 Figure S5 Figure S5 SSC tests based on nanoporous carbon electrodes. (a) CV curves of carbon//carbon SSC, with the device cycled by varying the upper cell voltage from 1 V to 1.6 V; (b) galvanostatic discharge curves of the carbon//carbon SSC cell at various current densities from 1-5 A g -1 ; and (c) dependence of the specific capacitance on the applied current density. 10

11 Figure S6 Figure S6 SSC tests based on nanoporous cobalt oxide electrodes. (a) CV curves of Co 3 O 4 //Co 3 O 4 SSC, with the device cycled by varying the upper cell voltage from 0.5 V to 0.9 V; (b) galvanostatic discharge curves of Co 3 O 4 //Co 3 O 4 SSC cell at various current densities from 1-5 A g -1 ; and (c) dependence of the specific capacitance on the applied current density. 11

12 Note for Figure S5 and Figure S6: Symmetric supercapacitor (SSC) studies were carried out for the nanoporous carbon and the Co 3 O 4. Each type of electrode, with size of 1 1 cm 2, was used as both the positive and negative working electrodes. In case of the SSCs, the total mass of both electrodes was adjusted to 2 mg cm -2. Figure S5a shows the CV curves of the carbon//carbon SSC at various potential windows ranging from 1.0 V to 1.6 V. It exhibits a rectangular shape, however, and after 1.6 V, a steep peak is observed, which might be due to some irreversible chemical reactions, so the maximum working potential of this material is up to 1.6 V. The capacitance of the SSC was evaluated by galvanostatic charge-discharge measurements (Figure S5b). For this purpose, the applied current density was varied from 1 to 5 A g -1. The absence of any initial voltage loss (i.e. IR drop) indicates a fast current response with low internal resistance. The variation of specific capacitance with applied current density is shown in Figure S5c. The maximum capacitance value obtained for the symmetric carbon//carbon supercapacitor was 20 F g -1 at a current density of 1 A g -1. Similar to the tests for the carbon-based SSC, Co 3 O 4 SSC tests were carried out (Figure S6a-c). The CV studies show that the maximum working potential for the Co 3 O 4 -based supercapacitor is 0.9 V. The SSC cell shows a very rectangular shape. The maximum capacitance value of the SSC was found to be 66 F g -1 at a current density of 1 A g

13 Figure S7 Figure S7 Heating of Co 3 O 4 samples without preliminary nitrogen heat treatment at (a) 400 ºC and (b) 350 ºC, respectively. 13

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