Supporting Information. Facile and Large-Area Preparation of Polypyrrole. Film for Low-Haze Transparent Supercapacitors

Transcription

1 Supporting Information Facile and Large-Area Preparation of Polypyrrole Film for Low-Haze Transparent Supercapacitors Xin Jiao, Chenguang Zhang*, Zhihao Yuan School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, , PR China Tianjin Key Laboratory for Photoelectric Materials & Devices, Tianjin University of Technology, Tianjin, , PR China Key Laboratory of Display Materials and Photoelectric Devices, Tianjin University of Technology, Ministry of Education, Tianjin, , PR China Corresponding Authors: Prof. Chenguang Zhang (* S-1

2 Calculations: The specific areal capacitance (CA, mf cm -2 ) based on the CV curve is calculated according to Equation S1: CC AA = 2 SS vv (VV ff VV ii ) 1 VV ff II(VV)dddd VV ii (Equation S1) where S represents the area of the PPy/PET film (4 cm 2 ) for testing, v represents the scan rate (V s -1 ), Vf and Vi are the upper and lower limit of the potential window during CV testing, respectively, and I(V) represents the voltammetric current (A). The specific areal capacitance (CA, mf cm -2 ) and volumetric capacitance (CV, F cm -3 ) are calculated based on the GCD curves according to Equation S2 and S3, respectively: CC AA = II SS tt vv (Equation S2) CC VV = CC AA dd (Equation S3) where I/S is the current density (ma cm -2 ), t is the discharge time (sec), v is the working potential (0.8 V for our device) and d is the thickness of the PPy film (~300 nm for PPy-50 in our work). The areal energy density (EA, Wh cm -2 ) and power density (PA, W cm -2 ) are calculated according to Equations S4 and S5, respectively. The volumetric energy density (EV, Wh cm -3 ) and power density (PV, W cm -3 ) are calculated according to Equations S6 and S7, respectively: EE AA = 1 2 CC AA ( VV) (Equation S4) PP AA = EE AA tt 3600 (Equation S5) S-2

3 EE VV = 1 2 CC VV ( VV) (Equation S6) PP VV = EE VV 3600 (Equation S7) tt where ΔV is the discharge voltage range (0.8 V) and Δt is the discharge time (sec). S-3

4 Figures: Figure S1. UV-vis transmittance spectra of a piece of commercial PET film (Inset: a star pattern under the PET film to show the transparency). S-4

5 Figure S2. The photographs of the PET films in the different positions in the solution with different ratios of methanol to water: (a) 0:10 (floating); (b) 1:9 (floating); (c) 2:8 (sink). S-5

6 Figure S3. Photographs of the PPy/PET films prepared in the aqueous solutions containing different types of co-solvents. The left upper picture shows the PET film floated on the surface of the solution before reaction starts. The left lower picture shows the PET film. The right upper panel shows the films during the synthesis and the right lower panel shows the resultant tranpsarent PPy/PET films. The star pattern is located under the films to show the transparency. S-6

7 Table S1. The comparisons of the sheet resistances and transmittance of the PPy/PET films synthesized in aqueous solution containing different types of co-solvents. Co-solvent types Water Hydrochloric acid Methanol Ethanol Acetonitrile Acetone Mixing ratio (H2O/Cosolvent) Sheet resistance (kω/ ) -- 9:1 9:1 9:1 9:1 9: Transmittance 37.1 % 79.1 % 78.1 % 72.6 % 71.3 % 90.2 % S-7

8 Figure S4. (a-e) SEM images of PPy film synthesized with different mole ratio of Py to FeCl3 under a polymerization-time of 50 min. By fixing the amount of Py at 0.8 ml and the polymerization-time at 50 min, the morphology evolution of the PPy/PET film with an increase of the mole ratio of Py to FeCl3 is characterized by SEM (Figure S4). The synthesis with 5 different mole ratios of Py to FeCl3 were carried out (2:1, 3:2, 1:1, 2:3 and 1:2). It is found that varying the concentration of FeCl3 can affect the size of the granular PPy islands and the continuity of the PPy film. When the mole ratio of Py to FeCl3 is larger than 1, the PPy island has a larger size due to a smaller nucleation rate, and the PPy film is not continuous with appearance of gaps among the PPy islands. Further increasing the mole ratio results in reducing the size of PPy islands and improving the continuity of the PPy/PET film. However, using FeCl3 with a high concentration is not beneficial for controlling the polymerization rate and the thickness of the PPy film. S-8

9 Figure S5. (a) Raman spectrum and (b) XRD profile of the PPy film stripped from PET substrate. The inset in (a) shows the enlarged Raman spectrum in a Raman shift range from 500 to 1100 cm - 1. S-9

10 Figure S6. SEM images of PPy/PET films prepared under different polymerization-time: (a) 20 min; (b) 30 min and (c) 50 min. S-10

11 Figure S7. (a) UV-vis transmittance spectra of the PET film and PPy-t films; (b) Thickness of the PPy film versus the polymerization-time. (c-h) SEM images of the cross-sections of the PPy-t films with thickness measurements labeled. The scale bars in the SEM images are 1 μm. The thickness of the PPy film in PPy-20 can not be measured due to the formation of discontinuous film and the presence of many isolated PPy islands. S-11

12 Figure S8. FoMe values of the PPy/PET films versus polymerization-time. S-12

13 S-13

14 Figure S9. AFM characterizations of different PPy-t films. (a1), (a2), (a3), (a4), (a5) and (a6) are AFM images of the PET substrate, PPy-20, 30, 40, 50 and 60, respectively. (b1), (b2), (b3), (b4), (b5) and (b6) are 3D surface topography images of the PET substrate, PPy-20, 30, 40, 50 and 60, respectively. The graphics of the surface topography images were created using Gwyddion 2.51 S1. (c1), (c2), (c3), (c4), (c5) and (c6) are height profiles of the PET substrate, PPy-20, 30, 40, 50 and 60, respectively. S-14

15 Figure S10. (a) UV-vis transmittance spectra of the PPy-50 and EVA film. (b) Photograph of a potted plant without any blocked film in front. (c-d) Photographs of the potted plant with left half part blocked by the (c) PPy-50 film and (d) EVA film. (e) Photograph of a tower building S-15

16 visualized through a piece of low-haze PPy/PET film. The inset is magnified in the right picture, in which the specific features on the building can be distinctly observed. S-16

17 Figure S11. CV curves of (a) PPy-20, (b) PPy-30, (c) PPy-40, (d) PPy-50 (e) PPy-60 and (f) PPy- 70 at different scan rates in 1 M H3PO4 aqueous solution. S-17

18 Figure S12. GCD curves of PPy-50 at different current densities from 0.02 to 0.2 ma cm -2. S-18

19 Figure S13. UV-vis transmittance spectra of PPy-50 and a LHSC device assembled by PPy-50. S-19

20 Figure S14. Photograph of a red LED powered by a pair of sunglass model, in which the lens are fabricated by the LHSCs in series. S-20

21 Table S2. The comparisons of the transparencies and the haze levels of the transparent conductive films in the literatures, PPy/PET film, LHSC and LHMSC in our work. Electrode materials Device Method Substrate Transmittance (%) Haze (%) Ref. AgNWs -- Meyer bar-coating Polycarbonate [S2] AgNWs -- Meyer bar-coating Glass 96 2 [S3] SWCNT-AgNWs -- Meyer bar-coating PET [S4] AgNWs -- Meyer bar-coating PET 90 2 [S5] AgNWs -- Meyer bar-coating PET 94 1 [S6] AgNWs -- Meyer bar-coating PET [S7] CuNWs -- Meyer bar-coating PET [S7] Cu-AgNWs -- Coating-dipping PET [S7] GO/Cu-AgNWs -- Coating-dipping PET [S7] rgo/cu-agnws -- Coating-dipping PET [S7] AgNWs -- Spin-coating Glass [S8] AgNWs -- Spin-coating Glass -- 2 [S9] AgNWs- PEDOT:PSS -- Spin-coating PET [S10] AgNWs -- Wet-coating Polyester [S11] AgNWs -- Drop-coating Glass [S12] AgNWs -- Scraping-coating PET [S13] AgNWs -- Slot-die coating PET [S14] AgNWs-Cellulose nanopaper -- Vacuum filtration Cellulose nanopaper [S15] CuNWs@rGO -- Vacuum filtration Polytetrafluoroethyl ene porous membrane 90 2 [S16] CuNWs -- Vacuum filtration Glass [S17] AgNWs -- Electrostatic spray Glass [S18] Au-Coated AgNWs -- Electrostatic spray Polycarbonate [S19] S-21

22 AgNWs -- Electrostatic spray Polycarbonate [S20] Ag and Au metal network -- Thermal evaporation Glass 80 5 [S21] Al-ZnO -- Solution-deposited Glass [S22] PPy Solution-process PET PPy PPy-SC PET PPy PPy-MSC PET This work This work This work S-22

23 Table S3. The comparison of the electrochemical performances and the transparencies of the transparent supercapacitors in the literatures and our work. Specific capacitance Electrode material Film thickness Areal Volumetric Mass Electrode configuration T% Ref. (mf cm -2 ) (F cm -3 ) (F g -1 ) Co3O4 nanocrystal sandwich 51 % [S23] SWCNT films 50 nm % E [S24] Au@MnO sandwich 36 % [S25] Graphene membrance CVD graphene Highly aligned CNT CNF-[RGO]n hybrid paper sandwich 46.5 % [S26] sandwich 72.9 % [S27] sandwich 75 % [S28] sandwich 30 % [S29] PEDOT:PSS % E [S30] rgo thin-film sandwich 24 % [S31] Ribbon-like graphene 750 nm sandwich 50.6 % [S32] rgo/pani sandwich 57.5 % [S33] Wrinkled graphene film 600 nm sandwich 51.6 % [S34] Graphene 2 nm sandwich 75 % [S35] PPy 300 nm sandwich 46.3 % PPy 300 nm coplanar 70.2 % This work This work Measured values of T% with E in superscript represents the transmittance of the single electrode while that without represents the transmittance of the supercapacitor device. S-23

24 Figure S15. GCD curves of the LHMSC at different current densities from 5 μa cm -2 to 50 μa cm -2. S-24

25 Figure S16. The capacitance retention after 1000 charge-discharge cycles of the LHMSC fabricated by the PPy/PET film without Na2ADS doping. S-25

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