Supplementary Information for
All-solid-state lithium-oxygen battery with high safety in wide ambient
temperature range
Hirokazu Kitaura, Haoshen Zhou*
Corresponding author:
Haoshen Zhou
Energy Technology Research Institute, Advanced Industrial Science and Technology,
Tsukuba Central 2, 1-1-1, Umezono, Tsukuba, Ibaraki 305-8568, JAPAN.
Tel.: +81-29-8615795, Fax.: +81-29-8613489
E-mail address: [email protected].
Supplementary Figures
6
20 mA
Cell voltage (V)
5
g-1
Room temperature
Thickness = 1mm
b
20 mA g-1
2
20
50
100 200
500 1000
4
3
2
1
1
0
10 mA g-1
5
4
3
6
Cell voltage (V)
a
0
100
200
300
400
Capacity (mAh g CNT-1)
0
500
0
50
100
150
Capacity (mAh g CNT-1)
200
Supplementary Figure S1 Rate performance of all-solid-state Li-O2 cell under the current
densities changed in a step by step manner. (a) Discharge-charge curves for cell using LAGP
pellet with the thickness of about 1 mm under current densities changed from 10 to 1000 mA g-1 at
room temperature and (b) enlarged view of initial data.
6
Cell voltage (V)
5
20 mA g-1
Room temperature
Thickness = 0.5mm
b
4
3
2
20 mA g-1
10 mA g-1 20
50 100 200 500
1000 2000 5000
5
4
3
2
1
1
0
6
Cell voltage (V)
a
0
200
400
600
800
Capacity (mAh gCNT-1)
1000
0
0
50
100
150
200
Capacity (mAh g CNT-1)
250
Supplementary Figure S2 Rate performance of all-solid-state Li-O2 cell under the current
densities changed in a step by step manner. (a) Discharge-charge curves for cell using LAGP
pellet with the thickness of about 0.5 mm under current densities changed from 10 to 5000 mA g-1 at
room temperature and (b) enlarged view of initial data.
6
Cell voltage (V)
5
100 mA g-1
80 oC
Thickness = 1mm
4
3
2
100 mA g-1
1
0
b
6
10 mA g-1 20 50 100 200 500
1000 2000 5000 10000
5
Cell voltage (V)
a
4
3
2
1
0
500 1000 1500 2000 2500 3000 3500
Capacity (mAh g CNT-1)
0
0
50
100
150
200
Capacity (mAh g CNT-1)
250
Supplementary Figure S3 Rate performance of all-solid-state Li-O2 cell under the current
densities changed in a step by step manner. (a) Discharge-charge curves for cell using LAGP
pellet with the thickness of about 1 mm under current densities changed from 10 to 10000 mA g-1 at
80 oC and (b) enlarged view of initial data.
Li 1s
60
58
O 1s
50 536
56
54
52
Binding energy (eV)
P 2p
138
C 1s
534
532
530
528
Binding energy (eV)
526 294 292 290 288 286 284 282 280
Binding energy (eV)
Ge 3d
136
134
132
130
Binding energy (eV)
128 38
36
Al 2p
34
32
30
Binding energy (eV)
28 80
78
76
74
72
Binding energy (eV)
70
Supplementary Figure S4 XPS spectra of LAGP-CNT cathodes before (black) and after
discharge (red) in Li 1s, O 1s, C 1s, P 2p, Ge 3d and Al 2p regions calibrated by using Ge 3d
main peak (32.3 eV) of Ge4+.
π-π*
290.5eV
294
292
290
COOH C=O
288.5eV 287.5eV
C-OH
286.0eV
288
286
Binding energy (eV)
C-C, CHx Inhomogeneous
284.5eV charged C-C
284
282
280
Supplementary Figure S5 XPS spectra of LAGP-CNT cathodes before (black) and after
discharge (red) in C 1s region calibrated by using 284.5 eV of C-C or CHx binding energy.
Supplementary Figure S6
XPS spectra of LAGP-CNT cathodes before (black), after
discharge (red) and after charge (blue) in Li 1s region calibrated by using Ge 3d main peak
(32.3 eV) of Ge4+ and Li2CO3 reagent in Li 1s region calibrated by using C 1s peak related with
carbonate (290.0 eV).
XPS analysis The XPS measurements were carried out at a Ulvac-Phi XPS-1800 spectrometer.
Monochromatic Al-Kα excitation (350 W) and a low-energy electron charge neutralizer were used.
The air electrode powder was scratched from the LAGP cell and fixed on Cu tape in the glove box.
The samples were transferred into the XPS chamber by using glove bag flowing nitrogen gas. The
spectra in Fig. S4 and S6 were calibrated by using Ge 3d main peak (32.3 eV) of Ge4+. The peak
positions of Li 1s, P 2p, and Al 2p before discharge are consistent with those of LAGP [21]. Also,
the peak positions of P 2p and Al 2p after discharge are consistent with those before discharge and it
indicates that the spectral calibration by Ge 3d is valid. On the other hand, the peak positions of C 1s
both before and after discharge are inappropriate because of the inhomogeneous charge effect owing
to the different conductivity between LAGP and carbon species [Shabtai et al., J. Am. Chem. Soc.,
2000, 122, 4959]. We compared to these spectra with the spectra of Li2CO3 reagent and mixture of
CNT and Li2CO3 reagent to determine the peak for the correct calibration. In conclusion, the second
lowest peak of C 1s spectra were calibrated to 284.5 eV as C-C or CHx binding energy (Fig. S5). The
shift of peak top in the Li 1s region after discharge in Fig. S4 is due to the formation of the lithium
compound and the predictable lithium compounds are insulative as well as LAGP. Therefore, it is
presumed that Li 1s spectrum after discharge, which contains both peaks of the insultative LAGP
and the insulative produced lithium compound, can be calibrated by using the Ge4+ peak of LAGP.
Supplementary Figure S7 Photograph of LAGP-CNT cathode on LAGP pellet after heat
treatment. Black circle area is cathode and white area is LAGP only.