Structural Directed Growth of Ultrathin Parallel Birnessite on

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1 Structural Directed Growth of Ultrathin Parallel Birnessite on β-mno 2 for High-Performance Asymmetric Supercapacitors Shi Jin Zhu 1, Li Li 2, Jia Bin Liu 3, Hong Tao Wang 3, Tian Wang 1, Yu Xin Zhang*,1, Lili Zhang*,, Rodney S Ruoff 5, 6,7, Fan Dong 8 1 College of Materials Science and Engineering, Chongqing University, Chongqing, China 2 College of Chemistry and Chemical Engineering, Chongqing University, Chongqing, China 3 School of Materials Science and Engineering, Zhejiang University, Hangzhou 327, China Institute of Chemical and Engineering Sciences, A*STAR, 1 Pesek Road, Jurong Island , Singapore 5 Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), Ulsan 919, Republic of Korea 6 Department of Chemistry, Ulsan National Institute of Science and Technology Ulsan 919, Republic of Korea 7 School of Materials Science and Engineering, Ulsan National Institute of Science and Technology 8 College of Environment and Resources, Chongqing Technology and BusinessUniversity, Chongqing, 67, China *Correspondence to: zhangyuxin@cqu.edu.cn; zhang_lili@ices.a-star.edu.sg; Preparation of AGO The activated graphene was prepared via a modified microwave exfoliated method that has been previously reported by the Ruoff group 1. Briefly, graphite oxide (GO) cake was synthesized from purified natural graphite (SP-1, BayCarbon, MI) by the Hummers method. Microwave exfoliated graphite oxide (MEGO) was prepared by irradiating the GO in a microwave oven (GE) in ambient conditions. Upon microwave irradiation, the very large volumetric expansion of the GO cake yields a black and fluffy MEGO powder. The as-prepared MEGO powder was then dispersed and soaked in aqueous KOH solution, followed by filtration and drying, to form the MEGO/KOH mixture for chemical activation. That mixture was then put in a tube furnace, and heated under flowing argon at a pressure of about Torr to 8 C and held at that temperature for one hour to increase the specific surface area.

2 Determining the mass ratio between birnessite and β-mno 2 We measure the weight of the substrate (MnOOH) before reaction and also the weight of the final composite (β-mno 2 /parallel birnessite) after the reaction. MnOOH is fully converted to beta-mno 2. Therefore, the mass ratio between the birnessite and beta MnO 2 is calculated according to the following equation: C birnessite/beta =(m 2-87m 1 /88)/( 87m 1 /88) Where m 1 is weight of MnOOH, m 2 is weight of β-mno 2 /parallel birnessite composite.

3 Intensity (a.u.) theta (degree) Supplementary Figure S1 (a) SEM image of MnOOH nanowires; XRD pattern of MnOOH nanowires (purple); theoretical structure values are in red

4 Intensity (a.u.) theta (degree) Supplementary Figure S2 (a) Digital image of MnOOH nanowires after they were treated with KMnO solution (5 µl concentrated sulfuric acid) at room temperature for 3 min; XRD pattern of the same nanowires.

5 Intensity (a.u.) (a) Sample 1 Sample 2 Sample 3 Sample Sample 5 Intensity (a.u.) Sample 6 Sample 7 Sample 8 Sample theta (degree) theta (degree) Intensity (a.u.) (c) Sample 1 Sample 2 Sample 3 Sample Sample 5 Intensity (a.u.) (d) Sample 6 Sample 7 Sample 8 Sample theta (degree) 2 theta (degree) Supplementary Figure S3 XRD patterns of β-mno 2 /parallel birnessite core/shell nanorod samples.

6 Supplementary Figure S SEM image of β-mno 2 /parallel birnessite core/shell nanorods (Sample 7).

7 Quantity Absorbed (cm 3 g -1 STP) 25 (a) Adsorption Desorption Relative Pressure(P/P ) DV/dD (cm3g-1nm-1) Pore Diameter (nm) Supplementary Figure S5 (a) Nitrogen adsorption and desorption isotherms; their corresponding pore-size distribution curves (adsorption part) of β-mno 2 /parallel birnessite core/shell nanorods (Sample 7).

8 Transmittance (%) Wavenumber (cm -1 ) Supplementary Figure S6 FTIR spectra of β-mno 2 /parallel birnessite core/shell nanorods (Sample 7).

9 Supplementary Figure S7 TEM image of β-mno 2 /parallel birnessite core/shell nanorod (cross section) (Sample 7)

10 Parallel birnessite (a) Parallel birnessite after 5 cycles Mn 2p O 1s Na 1s K 2p C 1s Intensity (a.u.) Na 1s F 1s as prepared Intensity (a.u.) Common birnessite after 5 cycles after 5 cycles Binding Energy (ev) Binding Energy (ev) Parallel birnessite- K 2p (c) Common birnessite- K 2p (d) as prepared Intensity (a.u.) as prepared Intensity (a.u.) after 5 cycles Binding Energy (ev) after 5 cycles Binding Energy (ev) Raw data Mn 3+ Fitting data Mn + Mn 2+ (e) Ra w da ta Mn 3+ Fit tin g da ta Mn + Mn 2 + (f) Intensity (a.u.) Common birnessite as prepared aft d isch arge Intensity (a.u.) Parallel birnessite as prepared aft discharge aft charge aft charge Binding Energy (ev) Binding Energy (ev) Supplementary Figure S8. (a) XPS wide scan of parallel birnessite. Na 1s core-level XPS spectra for common and parallel birnessite after 5 charge-discharge cycles. (c) K 2p core-level XPS spectra for parallel birnessite before and after charge-discharge cycles. (d) K 2p core-level XPS spectra for common birnessite before and after charge-discharge cycles. (e) Mn 2p spectra for commonl birnessite and (f) parallel birnessite electrodes at different states during the charge-discharge processes

11 Intensity (a.u.) O(KLL) Mn(LMM) Mn2p O1s C1s K2p K2s (a) Mn3p Mn3s Binding energy (ev) Weight (%) % 5.2 % beta-mno 2 /parallel birnessite Temperature ( o C) Supplementary Figure S9 (a) Survey XPS spectrum and TGA of beta-mno 2 /parallel birnessite.

12 Supplementary Figure S1 (a) common birnessite and parallel birnessite that was grown from β-mno 2.

13 Supplementary Figure S11 (a) SEM images of β-mno 2 /common birnessite core/shell nanorod; TEM images of a β-mno 2 /common birnessite core/shell nanorods.

14 Capacitance (F g -1 ) mv s -1 1 mv s -1 2 mv s -1 5mV s -1 mv s (a) (c) Parallel birnessite Common birnessite Z''(ohm) A g -1.5 A g A g A g -1. A g Z''(ohm) Time (s) (d) Parallel birnessite Common birnessite Z'(ohm) Z'(ohm) Supplementary Figure S12 Electrochemical properties of β-mno 2/common birnessite core/shell nanorods measured in 1 M Na2SO aqueous electrolyte in a three-electrode system (a,b); Variation of the capacitance with current density ( c ) and Nyquist plots (d) of β-mno 2/parallel birnessite core/shell nanorods and β-mno 2/common birnessite core/shell nanorods.

15 Frequency number Thickness (nm) Frequency number Thickness (nm) Frequency number Thickness (nm) Frequency number Thickness (nm) Frequency number Thickness (nm) Frequency number Thickness (nm) Frequency number Thickness (nm) Frequency number Thickness (nm) Frequency number Thickness (nm) Supplementary Figure S13 TEM images of individual nanorods in each of (a) Sample 1; Sample 2; (c) Sample 3; (d) Sample ; (e) Sample 5; (f) Sample 6; (g) Sample 7; (h) Sample 8; (i) Sample 9.

16 mv s -1 5 mv s mv s - 1 mv s -1 2 mv s (a) A g -1.5 A g A g A g -1. A g Time (s) Capacitance (F g -1 ) (c) Coulombic efficiency(%) Supplementary Figure S1 Electrochemical properties of β-mno 2/parallel birnessite core/shell nanorod (Sample1) measured in 1 M Na2SO aqueous electrolyte in a three-electrode system: (a) Cyclic voltammograms at different scan rates; Galvanostatic charge-discharge curves at different current densities; (c)variations of the capacitance and coulombic efficiency with current density.

17 mv s -1 5 mv s -1 1 mv s -1 mv s -1 2 mv s (a) Time (s) Supplementary Figure S15 Electrochemical properties of β-mno 2 /parallel birnessite core/shell nanorod (Sample 2) measured in 1 M Na2SO aqueous electrolyte in a three-electrode system: (a) Cyclic voltammograms at different scan rates; Galvanostatic charge-discharge curves at different current densities; (c) Variations of the capacitance and coulombic efficiency with current density..25 A g -1.5 A g A g A g -1. A g -1 Capacitance (F g -1 ) (c) Coulombic efficiency(%)

18 12 5 mv s -1 5 mv s -1 (a) mv s -1 mv s -1 2 mv s A g -1.5 A g A g A g -1. A g Time (s) Capacitance (F g -1 ) (c) Coulombic efficiency(%) Supplementary Figure S16 Electrochemical properties of β-mno 2 /parallel birnessite core/shell nanorod (Sample 3) measured in 1 M Na2SO aqueous electrolyte in a three-electrode system: (a) Cyclic voltammograms at different scan rates; Galvanostatic charge-discharge curves at different current densities; (c) Variations of the capacitance and coulombic efficiency with the current density.

19 Current density (A g ) 12 5 mv s -1 5 mv s -1 (a) mv s -1 mv s -1 2 mv s A g -1.5 A g A g A g -1. A g Time (s) Capacitance (F g -1 ) (c) Coulombic efficiency(%) Supplementary Figure S17 Electrochemical properties of β-mno 2 /parallel birnessite core/shell nanorod (Sample ) measured in 1 M Na2SO aqueous electrolyte in a three-electrode system: (a) Cyclic voltammograms at different scan rates; Galvanostatic charge-discharge curves at different current densities; (c) Variations of the capacitance and coulombic efficiency with the current density.

20 16 5 mv s -1 5 mv s -1 (a) mv s -1 mv s -1 2 mv s Time (s).25 A g -1.5 A g A g A g -1. A g Supplementary Figure S18 Electrochemical properties of β-mno 2 /parallel birnessite core/shell nanorod (Sample 5) measured in 1 M Na2SO aqueous electrolyte in a three-electrode system: (a) Cyclic voltammograms at different scan rates; Galvanostatic charge-discharge curves at different current densities; (c) Variations of the capacitance and coulombic efficiency with the current density. Capacitance (F g -1 ) (c) Coulombic efficiency(%)

21 mv s -1 5 mv s -1 1 mv s -1 mv s -1 2 mv s (a) A g -1.5 A g A g A g -1. A g Time (s) Capacitance (F g -1 ) (c) Coulombic efficiency(%) Supplementary Figure S19 Electrochemical properties of β-mno 2 /parallel birnessite core/shell nanorod (Sample 6) measured in 1 M Na2SO aqueous electrolyte in a three-electrode system: (a) Cyclic voltammograms at different scan rates; Galvanostatic charge-discharge curves at different current densities; (c) Variations of the capacitance and coulombic efficiency with the current density.

22 mv s -1 5 mv s -1 1 mv s -1 mv s -1 2 mv s (a) A g -1.5 A g A g A g -1. A g Time (s) Capacitance (F g -1 ) (c) Coulombic efficiency(%) Supplementary Figure S2 Electrochemical properties of β-mno 2 /parallel birnessite core/shell nanorod (Sample 7) measured in 1 M Na2SO aqueous electrolyte in a three-electrode system: (a) Cyclic voltammograms at different scan rates; Galvanostatic charge-discharge curves at different current densities; (c) Variations of the capacitance and coulombic efficiency with the current density.

23 mv s -1 5 mv s -1 1 mv s -1 mv s -1 2 mv s -1 (a) A g -1.5 A g A g A g -1. A g -1 Capacitance (F g -1 ) (c) Coulombic efficiency(%) Time (s) Supplementary Figure S21 Electrochemical properties of β-mno 2 /parallel birnessite core/shell nanorod (Sample 8) measured in 1 M Na2SO aqueous electrolyte in a three-electrode system: (a) Cyclic voltammograms at different scan rates; Galvanostatic charge-discharge curves at different current densities; (c) Variations of the capacitance and coulombic efficiency with the current density.

24 15 5 mv s -1 5 mv s -1 (a) mv s -1 mv s -1 2 mv s A g -1.5 A g A g A g -1. A g Time (s) Capacitance (F g -1 ) (c) Coulombic efficiency(%) Supplementary Figure S22 Electrochemical properties of β-mno 2 /parallel birnessite core/shell nanorod (Sample 9) measured in 1 M Na2SO aqueous electrolyte in a three-electrode system: (a) Cyclic voltammograms at different scan rates; Galvanostatic charge-discharge curves at different current densities; (c) Variations of the capacitance and coulombic efficiency with the current density.

25 V V (a) V V V V A g -1.5 A g A g A g -1.. A g Time (s) Capacitance (F g -1 ) 5 (c) Coulombic efficiency(%) Supplementary Figure S23 Electrochemical properties of β-mno 2 /parallel birnessite core/shell nanorod (Sample 7) measured in 1 M Na2SO aqueous electrolyte in three-electrode system: (a) Cyclic voltammograms with different potional windows ( V); Galvanostatic charge-discharge curves at different current densities; (c) Variations of the capacitance and coulombic efficiency with current density.

26 Supplementary Table S1 A comparison between the electrochemical performance of the β-mno2/birnessite core/shell nanorod electrode and other MnO 2 -based electrodes. Samples C(Fg -1 ) Electrolyte Testing condition references Amorphous MnO M NaCl 5 mv s -1 2 Birnessite MnO M K 2 SO 2 mv s -1 3 α-mno 2 hollow urchins M Na 2 SO 2 mv s -1 Ambigel MnO M NaCl 5 mv s -1 5 α-mno 2 nanorod M Na 2 SO 5 mv s -1 6 MnO 2 nanorod M Na 2 SO 5 mv s -1 7 MnO 2 nanowire M Na 2 SO 5 mv s -1 8 MnO 2 nanosheet M Na 2 SO.1 A g GHCS/MnO M Na 2 SO.1 A g MnO 2 microsphere 19 1 M Na 2 SO.5 A g MnO 2 /CNTs/RGO M Na 2 SO.2 A g α-mno 2 sphere 2.25 M Na 2 SO 1 A g -1 1 Graphene/Honeycomb MnO M Na 2 SO.5 A g α-mno 2 nanorod 25 1 M KOH 1 A g α- MnO 2 spherical-like particle M Na 2 SO.1 A g Graphene Hydrogel/ MnO M Na 2 SO 1 A g Mesoporous α-mno 2 network M Na 2 SO 2 mv s MnO 2 nanowire 3 1 M Na 2 SO 5 mv s MnO 2 tubular nanostructure M Na 2 SO.2 A g α-mno 2 ultralong nanowire 35.5 M Na 2 SO 1 A g MnO 2 nanoflower 37 1 M Na 2 SO 5 mv s MnO 2 hollow structure M Na 2 SO 5 mv s -1 2 Co 3 O /MnO M LiOH 2.67 A g β-mno 2 /parallel birnessite core/shell nanorod 36 1 M Na 2 SO.25 A g -1 This work 2

27 Actived Graphene Oxide Beta-MnO 2 /Birnessite core/shell nanorod Supplementary Figure S2 Cyclic voltammograms of β-mno 2 /parallel birnessite core/shell nanorod (Sample 7) (positive electrode) and amego (negative electrode).

28 8 (a) Potental (V) Time (s) Supplementary Figure S25 Electrochemical properties of amego measured in 1 M Na2SO aqueous electrolyte in three-electrode system: (a) Cyclic voltammograms with a scan rate of 5 mv s -1 ; galvanostatic charge-discharge curves at a current density of 1. A g -1.

29 V -1.6 V -1.2 V -1.8 V -1. V -2. V (a) Time (s) (c).25 A g -1.5 A g A g A g -1. A g -1 Current density (A g-1) Capacitance (F g -1 ) mv s -1 5 mv s -1 1 mv s -1 mv s -1 2 mv s -1 2 mv s (d) Coulombic efficiency(%) Supplementary Figure S26 Capacitance performances of an asymmetric supercapacitor with β-mno 2 /parallel birnessite core/shell nanorod (Sample 7) as positive electrode and amego as negative electrode: (a) CV curves at different cell voltages a scan rate of 5 mv s-1; CV curves recorded at different scan rates with a maximum cell voltage of 2. V; (c) Galvanostatic charge-discharge curves at different current densities between and 2. V; (d) Variations of the capacitance and coulombic efficiency with current densitiy.

30 Specific capacitance (F g -1 ) % retained Cycle number Supplementary Figure S27 Variations of the capacitance with cycle number of the as-assembled supercapacitor.

31 Sample 7 before dry at 12 o C Sample 7 after dry at 12 o C Intensity (a.u.) theta (degree) Supplementary Figure S28 XRD pattern of β-mno 2 /parallel birnessite core/shell nanorod (sample 7) before and after dried at 12 o C for 12 h.

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