Upload
others
View
1
Download
0
Embed Size (px)
Citation preview
S1
Supplementary Information
In-situ Filling Hydrogel Electrolyte into Robust Carbon Sponge: A Type
Omni-Healable Electrode for Flexible Supercapacitors
Liaoyuan Xia, * a 1 Le Huang, a 1 Yan Qing, a Xueqin Zhang,a Yiqiang Wu,a Wenping Jiang, a
and Xihong Lu,* b ,c
a. Hunan Province Key Laboratory of Materials Surface & Interface Science and Technology,
Central South University of Forestry and Technology, Changsha 410004, P. R. China.
E-mail: [email protected]
b. School of Applied Physics and Materials, Wuyi University, Jiangmen 529020, P. R. China.
E-mail: [email protected]
c. MOE of the Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry,
Sun Yat-Sen University, Guangzhou 510275, P. R. China.
Section 1. Calculations
1. Calculation of the areal specific capacitance of the single electrode
(1) The areal specific capacitance of the electrodes was calculated from the CV curves
using Equation (1).
(1)SU
QCs
where Ca (mF/cm2) is the areal specific capacitance, Q is the average charge during electrode
charging and discharging, ΔU (V) is the working voltage window (0.8V) of the electrode, and
S (cm2) is the test area of the electrodes.
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2020
S2
(2) The mass specific capacitance of the electrodes was calculated from the CV curves
using Equation (2).
(2)mU
QCS
where Cs (F/g) is the mass specific capacitance, Q is the average charge during electrode
charging and discharging, ΔU is the voltage range (0.8V), and m is the mass of the electrode.
(3) The areal specific capacitance of the electrodes was calculated by GCD using Equation
(3).
(3)SUtICa
where I is the current during electrode discharging (A), and Δt (s) is the discharge time of the
electrode, ΔU is the voltage range (0.8V), and S (cm2) is the test area of the electrodes.
(4) The mass specific capacitance with respect to three-electrode configuration is derived
from GCD based on Equation (4).
(4)mUtICs
where I is the current during electrode discharging (A), and Δt (s) is the discharge time of the
electrode, ΔU is the voltage range (0.8V), and m is the mass of the electrode.
(5) The healing efficiency (η, %) was calculated by Equation (5).
(5)1000
CCh
where C0 and Ch are the specific capacitance of the original and the healed electrodes,
respectively.
2. Calculation of area specific capacitance, power density, and energy density of the fully
self-healable CS@PA-SC device
(1) The area specific capacitance was calculated from Equations (6).
S3
(6)acell CC 21
where Ccell is the area specific capacitance of the device, Ca is areal specific capacitance of the
electrode.
(2) The energy density (E, Wh/cm2) and power density (P, W/cm2) were calculated by the
equations (7) and (8).
(7)2)(81 UCE a
(8)t
EP
3600
where Ca is areal specific capacitance of the electrode, ΔU is the voltage range (0.8V).
Section 2. Curves and Figures
0.0 0.2 0.4 0.6 0.8-6
-3
0
3
6
90% 100%Cu
rrent
den
sity (
mA/
cm2 )
Potential (V vs. Ag/AgCl)
60% 70% 80%
0 4 8 12 16 20 24 28 32
2
4
6
8
Rct-60%
Rct-70%
Rct-80%
Rct-90%
Rct-100%
60% 70% 80% 90% 100%
Z'' (o
hm)
Z' (ohm)
0 20 40 60 80 100 120 140 1600.0
0.2
0.4
0.6
0.8
IR100%=0.0954IR90%=0.0685IR80%=0.0662IR70%=0.0389IR60%=0.0324
CS 60% 70% 80% 90% 100%
Pote
ntia
l (V vs. A
g/Ag
Cl)
Time (s)
IRCS=0.0289
(a) (b)
(c) (d)
S4
(e)
Fig. S1 (a) CV curves of CS@PANa-Fe3+-LiCl electrodes with different filling weight ratio
at scanning rate of 50 mV/s; (b) GCD curves of CS@PANa-Fe3+-LiCl electrodes with
different filling weight ratio at current densities of 2 mA/cm2; (c, d) Nyquist plots and
partly enlarge of CS@PANa-Fe3+-LiCl electrodes with different filled weight ratio; (e) Fitted
equivalent circuit of the CS@PANa-Fe3+-LiCl electrode with different filling content of PANa-
Fe3+ hydrogel.
Note to Fig. S1. For the CS@PANa-Fe3+-LiCl electrode, its self-healing performance depends
on the in-situ generated PANa-Fe3+ hydrogel. Therefore, in theory, if the filling amount of
PANa-Fe3+ is larger, the self-healing performance of CS@PANa-Fe3+-LiCl electrode is better.
From the perspective of electrochemical performance, on the other hand, the CS@PANa-Fe3+-
LiCl electrode has better capacitance characteristics and smaller resistance value when the
filling amount of PANa-Fe3+ is 60%. However, considering the two factors of self-healing and
electrochemical performance of the CS@PANa-Fe3+-LiCl electrode, the optimal filling amount
was determined to be 70%. In addition, the Rct value of the CS@PANa-Fe3+-LiCl electrode also
further confirmed that the conductivity of the electrode gradually deteriorated with the increase
of the filling amount.
S5
(b)(a)
Fig. S2 (a) Optical image of measuring the thickness of CS@PANa-Fe3+-LiCl electrode with
Vernier caliper; (b) Schematic diagram of a fully self-healable supercapacitor fabricated by the
CS@PANa-Fe3+-LiCl integrated electrode.
404 402 400 398 396
Pyridine
PyrrolicQuaternaryOxidized
Inte
nsity
Binding energy (eV)
N 1s(a)
287 286 285 284 283
C 1s
Inte
nsity
Binding energy (eV)
(b)
Fig. S3. High-resolution XPS spectra of CS template for (a) N 1s and (b) C 1s.
Note to Fig. S3. As shown in Fig. S3a, The N 1s spectrum can be fitted into four peaks using
the Gaussian method, which indicated four components attributed to pyridinic nitrogen (N-6),
pyrrolic (N-5), quaternary (N-Q), and oxidized pyridinic nitrogen (N-X).[1, 2] In the C1s
spectrum (Fig. S3b), the dominant peak located at 284.6 is characteristic of the graphitic carbon
(C–C), and the peak at 286.1 corresponds to C–O/C–N.[2, 3] The results indicate that the CS
template is a nitrogen and carbon-rich product.
S6
10 20 30 40 50 60 70 80
(100)
Inte
nsity
(a.u
)
2 Theta (degree)
CS(002)
500 1000 1500 2000 2500 3000 3500
2D-band
D-band
Inte
nsity
(a.u
.)
Raman shift (cm-1)
CS
G-band
(a) (b)
Fig. S4. XRD spectra of CS template for (a) N 1s and (b) C 1s.
Note to Fig. S4. As shown in Fig. S4a, the CS sample exhibits a typical diffraction pattern
characteristic of MWCNTs. A strong peak at ~26o and a weak peak located at ~42o can be
observed, which correspond to the (002) and (100) planes of the graphitic phase of MWCNTs,
respectively. [4] In addition, Raman are widely used to evaluate the quality of carbon materials.
As shown in Fig. S4b, the G band around 1580 cm-1 is a characteristic feature of graphitic
layers, while the D band around 1350 cm-1 corresponds to disordered carbon or defective
graphitic structures. [2, 4] These results indicate that CS is composed of graphitized MWCNT
and MF-derived amorphous carbon materials.
S7
Fig. S5. SEM images with different magnification of (a, b) MF; (c, d) M-CM; and (e, f) CS
template.
(a)
(b)
(c)
(d)after carbonized after carbonized
Fig. S6. Photograph of (a) MF sponge; (b) MF directly derived carbon sponge material; (c) M-
CM hybrid aerogel; and (d) CS template.
Fig. S7 (a-c) Optical images showing the CS compression and recovery process under the
condition of lighted a LED; (d) Compressible stress-strain curves of the CS with different
compression ratio.
S8
(a) (b)
(c) (d)
0 60 120 180 240 3000
40
80
120
160
Adso
rbed
wei
ght r
atio
(%)
Time (min)
PANa-Fe3+
CS@PANa-Fe3+
1 2 3 4 5 6 7 80
1
2
3
4
5
6
7
30 min 60 min 90 min 120 min 150 min 180 min 210 min 240 min 270 min
-Z'' (
ohm
)
Z' (ohm)
0 30 60 90 120 150 180 210 240 270 3000
30
60
90
120
150
Ioni
c co
nduc
tivity
(mS/
cm)
Time (min)
PANa-Fe3+-LiCl CS@PANa-Fe3+-LiCl
0 25 50 75 100 1250
20
40
60
80
100
30 min 60 min 90 min 120 min 150 min 180 min 210 min 240 min 270 min
-Z'' (
ohm
)
Z' (ohm)
Fig. S8. (a) Comparison of adsorbed weight ratio of CS@ PANa-Fe3+ and PANa-Fe3+ after
immersion in 5M LiCl solution for different time; (b) AC impedance spectrum of CS@PANa-
Fe3+ dry gel after soaking in 5M LiCl solution for different time; (c) AC impedance spectrum
of PANa-Fe3+ dry gel after soaking in 5M LiCl solution for different time; (d) Comparison of
ionic conductivity of CS@ PANa-Fe3+ and PANa-Fe3+ after immersion in 5M LiCl solution for
different times.
Note to Fig. S8. As shown in Fig. S8a, it can be clearly seen that CS@PANa-Fe3+ dry gel has
a stronger absorption capacity of LiCl solution than PANa-Fe3+ dry gel, which is mainly due to
CS@PANa-Fe3+ has a more continuous 3-D porous structures. More importantly, the
conductivity of the PANa-Fe3+-LiCl film is 26.0 mS/cm after soaking into LiCl solution for 240
min, while the conductivity of the CS@PANa-Fe3+-LiCl electrode is high up to 137.9 mS/cm
after soaking into LiCl solution for 240 min. This further shows that the integrated CS@PANa-
Fe3+-LiCl electrode also can fundamentally serve as a solid-state electrolyte for the storage of
ions.
S9
(a) (b)
N
(c)
OFig. S9. SEM-EDS elemental mapping images of CS@PANa-Fe3+-LiCl electrode.
(a)
0.0 0.2 0.4 0.6 0.8
-15
-10
-5
0
5
10
15
50 mV/s 75 mV/s 100 mV/s
Curre
nt d
ensit
y(m
A/cm
2 )
Potential (V vs. Ag/AgCl)
5 mV/s 10 mV/s 25 mV/s
0 100 200 300 4000.0
0.2
0.4
0.6
0.8
Pote
ntia
l (V
vs. A
g/Ag
Cl)
Time (s)
1 mA/cm2
2 mA/cm2
4 mA/cm2
6 mA/cm2
8 mA/cm2
10 mA/cm2
20 mA/cm2
0.0 0.2 0.4 0.6 0.8-12
-6
0
6
12
50 mV/s 75 mV/s 100 mV/sCu
rrent
den
sity
(mA/
cm2 )
Potential (V vs. Ag/AgCl)
5 mV/s 10 mV/s 25 mV/s
0 200 400 6000.0
0.2
0.4
0.6
0.8
Pote
ntia
l (V
vs. A
g/Ag
Cl)
Time (s)
0.5 mA/cm2
1 mA/cm2
2 mA/cm2
4 mA/cm2
6 mA/cm2
8 mA/cm2
10 mA/cm2
(b)
(c)
(d)
3 6 9 12 15 18 21 240
3
6
9
12
15
Rct
Z'' (
ohm
)
Z' (ohm)
CS CS@PANa-Fe3+-LiCl
Rct
(e)
Fig. S10. (a) CV curves of CS electrode for scanning rates of 5–100 mV/s; (b) GCD
curves of CS electrode at different current densities of 1–20 mA/cm2; (c) CV curves of
CS@PANa-Fe3+-LiCl electrode for scanning rates of 5–100 mV/s; (d) GCD curves of
CS@PANa-Fe3+-LiCl electrode at different current densities of 0.5–10 mA/cm2; (e)
Nyquist plots of CS and CS@PANa-Fe3+-LiCl electrode.
S10
Fig. S11. Optical images of the CS@PANa-Fe3+-LiCl electrode as a wire lighted a LED under
different conditions of (a) cut, (b) heal, (c) bend, (d) twist, (e) stretch, and (f) dislocate.
Fig. S12. Fitted equivalent circuit of the self-healing CS@PANa-Fe3+-LiCl electrode and
corresponding Rct value after multiple cycles of cutting and healing.
S11
0 10 20 30 40 500.0
0.2
0.4
0.6
0.8
Pote
ntia
l (V)
Time (s)
0.6 V 0.7 V 0.8 V
(a) (b)
0.0 0.2 0.4 0.6 0.8
-6
-3
0
3
6
50 mV/s 75m V/s 100 mV/s
Curre
nt d
ensit
y (m
A/cm
2 )
Potential (V)
5 mV/s 10 mV/s 25 mV/s
Fig. S13. (a) CV curves of CS@PA-SCs device for scanning rates of 5–100 mV/s; (b) GCD
curves of CS@PA-SCs device at 2 mA cm-1 under different voltage windows.
0.0 0.2 0.4 0.6 0.8
-2
-1
0
1
2
After 2nd healing After 3rd healingCu
rrent
den
sity
(mA/
cm2 )
Potential (V)
Original After 1st healing
0 10 20 30 40 500.0
0.2
0.4
0.6
0.8 After 1st healing
Pote
ntia
l (V)
Time (s)
Original
After 2nd healing After 3rd healing
(a) (b) (c)
1 2 30
20
40
60
80
100
120Based on CP (2 mA/cm2)
heal
ing
effic
ienc
y (%
)
Healing times
Based on CV (25 mV/s)
0
20
40
60
80
100
heal
ing
effic
ienc
y (%
)
Fig. S14. CV curves of CS@PA-SCs device before and after self-healing; (b) GCD curves of
CS@PA-SCs device before and after self-healing; (c) Nyquist plots of CS@PA-SCs device
before and after self-healing.
Note to Fig. S14. For the purpose of proving that the fabricated CS@PA-SCs device can
achieve the self-recovery of electrochemical functional characteristics, we compared the
electrochemical performance of the device after three times of healing. As shown in Fig. S14a,
all CV curves maintain a rectangular-alike shape of the same size, indicating that the device has
good capacitance behavior after three times of healing. The comparison of GCD curves (Fig.
S14b) proves that the device has good self-healing performance. In addition, the capacitance
retention rates of the CS@PA-SCs device after three healing cycles are still as high as 91.3%
(based on CV) and 95.7% (based on CP), respectively. These results indicate that the device
has good self-healing performance (Fig. S14c).
S12
Section 3. Table
Table S1 Wavenumber range corresponding to the characteristic functional groups.Functional groups Wavenumber range (cm-1)
-OH 3600-3200-CH3, -CH2 2848, 2918
C=C 1743-1690C-O 1650-1600C=O 1743-1690
COO- (strong) 1580-1530COO- (weak) 1420-1375
Note to Table S1. From the FTIR spectrum and Table S1, it can be seen that characteristic peak
of –OH in the carboxyl group appears at 3440 to 3320 cm-1, and two characteristic peaks of the
–COO functional group are observed at 1440 and 1560 cm-1, indicating formation of PANa-
Fe3+ hydrogel. For CS template, the characteristic peaks presenting at 3417 and 1618 cm-1 are
attributed to the stretching vibrations of O-H and C=C functional groups of the MWCNT,
respectively.
Section S4. Video
Video S1 An LED indicator (3 V) lit by four units of flexible CS@PA-SCs device (size: 1
cm×1.5 cm, one CS@PA-SCs device has undergone the processing of cut and self-heal) in
series.
Reference
[1] S. Chu, Y. Zhong, R. Cai, Z. Zhang, S. Wei, Z. Shao, Small, 2016, 12, 6724.
[2] L. Zhu, M. Gao, C. K. N. Peh, X. Wang, and G. Ho, Adv. Energy Mater., 2018, 8, 1702149.
[3] R. Zhang, X. Jin, Y. Chu, L. Wang, W. Kang, D. Wei, H. Li and S. Xiong, J. Mater. Chem.
A, 2018, 6, 17730.
[4] W. Yuan, B. Wang, H. Wu, M. Xiang, Q. Wang, H. Liu, Y. Zhang, H. Liu, S. Dou, J. Power
Sources, 2018, 379, 10.