a b c d e f - royal society of chemistrya b c c f 3 a figure s4. edx of tca electrode after...
TRANSCRIPT
1
Supporting Information for
Electron Regulation Enabled Selective Lithium Deposition for Stable Anode of Lithium-
Metal Batteries
Junling Guo,a Shupeng Zhao, a He Yang, a Fengxiang Zhang*a and Jinping Liu*b
Figure S1. The SEM (a-c) and EDX (d-f) images of the ZnO array on carbon cloth.
a State Key Laboratory of Fine Chemicals and School of Petroleum and Chemical Engineering, Dalian
University of Technology, 2 Dagong Road, Liaodongwan New District, Panjin 124221, P. R. China.
*E-mail: [email protected] b School of Chemistry, Chemical Engineering and Life Science and State Key Laboratory of Advanced
Technology for Materials Synthesis and Processing, Wuhan University of Technology, Wuhan 430070, P. R.
China.
*E-mail: [email protected]
a
c
e
b
d
f
C element
Zn element
O element
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.This journal is © The Royal Society of Chemistry 2018
2
Figure S2. Discharge-charge curves of the TCA electrode for SEI formation.
Figure S3. EDX mapping of TCA electrode after 3 cycles at 0.3 ~ 1 V for SEI formation: (a)
Scanning Acquire image; (b) C element and (C) F element.
0 5000 10000 150000.3
0.6
0.9
1.2
1.5
Volt
age
(V)
Time (s)
0.2 mA/cm2
a b
c C
F
3
Figure S4. EDX of TCA electrode after infiltration in the electrolyte for 5h at different points:
(a) Scanning Acquire image; (b) point 1, corresponding to position on the outer surface; (c-e)
points 2-4 corresponding to different positions on the inner surface.
0 10000 20000 30000 400000
10
20
30
40
50
Co
un
ts
Energy (eV)
0 10000 20000 30000 400000
10
20
30
40
50
Co
un
ts
Energy (eV)
0 10000 20000 30000 400000
10
20
30
40
50
Co
un
ts
Energy (eV)
0 10000 20000 30000 400000
10
20
30
40
50
60
Energy (eV)
Co
un
ts
1
2
3
4
200 400 600 800
0
20
40O
C
200 400 600 800
0
20
40 OC
200 400 600 800
0
20
40
O
C
200 400 600 800
0
20
40
60
FO
C
a b c
d e
4
Figure S5. EDX of TCA electrode after 3 cycles at 0.3 ~1 V at different points: (a) scanning
Acquire image; (b-c) point 1, corresponding to a position on the outer surface; (d-e) point 2,
corresponding to a position on the inner surface.
a
1
2
200 400 600 800
0
10
20
30
40
50
O
Energy (eV)
Co
un
ts
C
0 10000 20000 30000 400000
10
20
30
40
50
Energy (eV)
Co
un
ts
200 400 600 8000
10
20
30
40
50
Co
un
ts
Energy (eV)
F
C
O
0 10000 20000 30000 400000
10
20
30
40
50
Co
un
ts
Energy (eV)
b c
d e
5
Figure S6. Enlarged charge-discharge curves of (a) the SEI wrapped TCA electrode at
different cycles at 1 mA cm2; (b-d) Li plating/stripping curves of different electrodes at 1 mA
cm-2 for 2 mAh cm-2.
7 8 9 10 11-50
-25
0
25
50
Po
ten
tial
(mV
vs
Li/
Li+
) TCA electrode SEI wrapped
TCA electrode
Time (h)
SEI wrapped
TCP electrode
95 96 97 98 99-50
-25
0
25
50
Po
ten
tia
l (m
V v
s L
i/L
i+) TCA electrode
SEI wrapped
TCA electrode
Time (h)
95 96 97 98 99-600
-400
-200
0
200
400
Po
ten
tia
l (m
V v
s L
i/L
i+)
TCA electrode
SEI wrapped
TCA electrode
Time (h)
43 44 45 46 47-50
-25
0
25
50
Po
ten
tia
l (m
V v
s L
i/L
i+)
TCA electrode
SEI wrapped
TCA electrode
Time (h)
SEI wrapped
TCP electrode
43 44 45 46 47-200
0
200
400
600
800
Po
ten
tia
l (m
V v
s L
i/L
i+)
TCA electrode
SEI wrapped
TCA electrode
Time (h)
SEI wrapped
TCP electrode
1.10 1.15 1.20 1.25 1.30-0.04
-0.02
0.00
0.02
0.04
Po
ten
tia
l (V
vs
Li/
Li+
)
Areal capacity (mAh cm-2)
50 th 1 st
100 th 200 th
a
b
c
d
6
Figure S7. The nyquist plots of different cells without sulfur.
Figure S8. Li plating/stripping behavior of different electrodes at 5 mA cm-2 for 2 mAh cm-2.
0 5 10 15 20 25 300
5
10
15
20
Li/TCA cell
Li/SEI wrapped TCA cell
Li/Li cell
Zim
(oh
m)
Zre (ohm)
7
Figure S9. The SEM images of different electrodes after cycling: (a-c) SEI wrapped TCP
electrode; (d-f) TCA electrode and (g-i) SEI wrapped TCA electrode.
500 nm
500 nm
500 nm
30 μm
30 μm
30 μm
3 μm
3 μm
3 μm
a b c
e d
g
f
h i
8
Figure S10. XRD of pristine TCA electrode, TCA electrode after 5 cycles and SEI wrapped
TCA electrode after 5 cycles of charge-discharge operation.
Figure S11. TEM images of porous carbon sphere/sulfur composite.
10 20 30 40 50 60 70 800
200
400
600
800
LiOH
Inte
nsi
ty(a
.u.)
2 (deg.)
TCA electrode after 5 cycles
SEI wrapped TCA electrode after 5 cycles
Pristine TCA electrode
a b
9
Table S1. The performance comparison of our works with literature results
Strategies Coulombic
efficiency
Stable cycling performance
Current
density
Voltage hysteresis
(after 150 h)
Hollow carbon shells
loaded with Au
nanoparticles inside[23]
98% 300
cycles
Carbon
nanofibers loaded with
Ag nanoparticles[33]
98% 50
cycles
0.5
mA cm-2 ~22 mV
Covalently connected
graphite microtubes[42]
~97% 100
cycles
1
mA cm-2 24 mV
Artificial solid
electrolyte interphase
layer[18]
~98% 200
cycles
Nanodiamonds work as
an electrolyte
additive[11]
~96% 100
cycles
1
mA cm-2 100 mV
Our work 98% 200
cycles.
1
mA cm-2 ~12 mV
10
Figure S12. The nyquist plots of different sulfur cells.
Figure S13. (a) Side-view and (b) top-view SEM images of the pristine Li metal anode; (c)
side-view and (d) top-view SEM images of the Li metal anode after 100 cycles.
b a
c d
0 20 40 60 800
20
40
60
Zim
(o
hm
)
Zre (ohm)
Li-TCA/S cell
Li-SEI wrapped TCA/S cell
Li/S cell
11
Figure S14. The electrochemical performance of different Li-LiCoO2 batteries: (a) the first
charge-discharge curves; (b) the cycle performance at 0.2 C.
0 20 40 60 80 100
2.8
3.2
3.6
4.0
Battery using Li-SEI wrapped TCA anode
Capacity (mAh/g)
Po
ten
tia
l (V
)
Battery using Li- TCA anode
Battery using commercial Li anode
3.89
3.90
3.90
3.95
0 20 40 60 80 100
20
40
60
80
100
52.3 %
76.8 %
Cap
aci
ty (
mA
h/g
)
Cycle Number
Blcak: Battery using Li- TCA anode
Blue: Battery using commercial Li anode
Red: Battery using Li-SEI wrapped TCA anode
Charge
Discharge