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radical attack
is effective and makes the cycle life far superior to those of the cases where either liquid electro-
lytes or ILs are solely used. Throughout a series of analyses, it was found that the use of the
blended electrolyte alleviates the decomposition of PC and thus diminishes the formation of irre-
versible reaction products, such as Li
2
CO
3
, while engaging the sufficient ionic conductivity of
PC and thus enabling substantially enhanced cycling performance.
- 5 -
Figure 1. Proposed reaction schematic figure on discharge to explain formation of the com-
pound: Li propyl dicarbonate, Li formate, Li acetate, Li
2
CO
3
, CO
2
, and H
2
O.
[17]
- 6 -
Chapter 2. Experimental Procedure
2-1 Preparation of electrolyte
Propylene carbonate (PC, PANAX ETEC Co. Ltd, Korea) and N-propyl-N-methyl pyr-
rolidinium bis(trifluoromethanesulfonyl)imide (PYR
13
TFSI, C-TRI, Korea) were used as received.
The blended electrolytes were prepared by mixing PC and the IL at weight ratios of 5:5 and 3:7, re-
spectively. The concentrations of lithium salt (lithium bis(trifluoromethane-sulfonyl)imide or LiTFSI,
Aldrich, USA) for all of the electrolytes were 0.3 M. Conductivity measurements of the electrolytes
were carried out using a conductivity meter (LF340, WTW, Germany). Viscosities of the electrolytes
were measured using a vibrational viscometer (SV-10, AND, Japan).
2-2 Li-O
2
battery assemblies and electrochemical tests
In order to investigate the stability of oxygen radical anions, cyclic voltammetry (CV)
tests were performed using a three electrode beaker cell. A glassy carbon (GC, Pine Instruments Inc,
USA) disk with a 5 mm diameter, Ag/AgCl, and a Pt wire were used as working, reference, and coun-
ter electrodes, respectively. 0.05 M tetrabutylammonium bis(trimethane-sulfonyl)imide (TBATFSI)
- 7 -
salt was dissolved in each case of PC and the IL. The scan rate was 40 mV s
-1
in the voltage range of
1.3 - 0.1 V vs. Ag/Ag
+
at room temperature. The porous air electrodes were prepared by casting a
slurry of Super-P (TIMCAL, Switzerland), -manganese oxide (-MnO
2
) nanowires, and
poly(vinylidene fluoride) (PVDF, Aldrich, USA) binder onto carbon paper (TGPH-090, NARA cell-
tech, Korea). The weight ratio of the components was super-P : -MnO
2
: PVDF = 24 : 42 : 34. For
XPS analyses of the air electrodes, the air electrodes were prepared by the same procedure but with-
out the -MnO
2
catalyst. For this case, the weight ratio was Super-P : PVDF = 66 : 34. After the cast-
ing, the air cathodes were dried at 70 C for 12 h. For electrochemical characterization, Swagelok
type cells were assembled in a glove box. A Swagelok type cell was composed of a Li metal anode
(thickness = 600 m, Honjo, Japan), a glass fiber membrane (GF/D, Whatman, USA) impregnated
with the electrolyte, and the air electrode (Figure 2). Galvanostatic charge and discharge tests were
conducted using a WBCS 3000 battery cycler (WonAtech, Korea) at a current density of 200 mA g
car-
bon
-1
in the voltage range of 2.25 - 4.35 V vs. Li/Li
+
at room temperature. Electrochemical impedance
spectroscopy (EIS) tests were conducted using a VMP3 (Biologic, France) tester after charge of dif-
ferent cycles with an AC amplitude of 10 mV and a frequency range of 1 MHz to 0.1 Hz. All of the
electrochemical tests were carried out at 1 atm of pure O
2
(99.999 %) in a pressure balanced oxygen
chamber (Figure 3).
- 8 -
2-3 Surface analysis of air electrode
For the analyses of the discharged air electrodes, the discharged batteries were disas-
sembled in a glove box and the air electrodes were rinsed with dimethoxyethane (DME) and dried in
an Ar filled glove box. The chemical compositions of the air electrodes were analyzed by high resolu-
tion dispersive raman microscope (Horiba Jobin Yvon, France) and XPS (XPS, Thermo VG scientific,
England) with a Mg K
ineffective,
[32]
giving superoxide the chance of attacking PC
(Figure 4a). The attack of O
2
.
[25]
As schematically illustrated in Figure 4b, the underlying mechanism for the O
2
sta-
bilization is that the bulky cation PYR
13
+
of the IL has soft acidity and thus efficiently neutralizes soft
base O
2
- 12 -
even after the solvation with PC particularly compared to the PYR
13
cations of the IL because the ra-
dius of the IL cation is larger and its charge density is lower.
[25,32]
The weak interaction of PC with Li
+
ions can also be understood by the low donor number of PC (=15.1).
[33]
In general, the donor number
indicates the degree of nucleophilic character (electron donating, Lewis basicity). The donor number
of PC is indeed smaller than those of other solvents considered for Li-O
2
cells such as dimethylfor-
mamide (=26.8),
[33,34]
again suggesting the weaker interaction of PC with Li
+
ions. Overall, the allevi-
ation of the superoxide attack to PC is the very key motivation of using the IL to improve the cycle
lives of Li-O
2
batteries.
While the use of ILs is advantageous in many aspects of Li-O
2
battery operations, the
exclusive use of ILs would suffer from low ionic conductivities originating from their high viscosities.
As a solution, in the current investigation, a blend of electrolytes by mixing PYR
13
TFSI with PC in
different ratios is introduced. For the blended electrolytes, the ionic conductivity and viscosity were
examined prior to battery performance tests. In these characterizations, instead of testing the bare
mixtures of PC and the IL, 0.3 M lithium bis(trifluoromethane-sulfonyl)imide (LiTFSI) salt was dis-
solved in each solution because it is known that the presence of excessive lithium salt increases the
viscosity and consequently decreases the ionic conductivity due to increased ionic interaction within
the solution.
[35]
- 13 -
As shown in Figure 5, the ionic conductivity is the highest when the mass ratio of IL:PC
is 1:1, indicating that the ionic conductivity increases in the range of small IL content, but decreases
once the IL content passes a certain point. This trend of showing the maximum value in the ionic
conductivity can be interpreted in a way that in the range of small IL content, the increased content of
the IL increases the number of ions involving in the ionic transport. However, after the maximum
point, the further increase in the IL content rather increases the viscosity, which leads to decrease in
the ionic conductivity. This ionic conductivity and viscosity trend is consistent with the previous re-
ports by the Zaghib
[35]
and Balducci
[36]
groups. It should also be stated that methyl pyrrolidinium cati-
on series have planar arrangements and thus facilitate fast ionic transport.
[37]
Beside these features,
pyrrolidinium cation series are known to interact with Li metal in a quite reversible manner, which
must be beneficial to robust battery cycling.
[38]
3-2 Electrochemical characteristics and cell performance
The stability of the O
2
).
However, the scan in the opposite direction shows an almost negligible peak, implying
that the oxidation of O
2
back to O
2
is considerably impaired. The irreversible nature of the redox
couple throughout the cycle must be associated with the superoxide attack to PC and the subsequent
decomposition of PC.
[39]
In other words, the generated superoxide is consumed for the reaction with
PC and therefore loses the capability of converting back to O
2
. By contrast, the blended solvents
(PC:IL = 5:5 or 3:7) show improved reversibility between the cathodic (1.00 V at PC:IL = 5:5,
1.04 V at PC:IL = 3:7) and anodic (0.87 V at IL:PC = 5:5, 0.90 V at PC:IL = 3:7) peaks, suggest-
ing that the addition of the IL improves the reversibility of O
2
/O
2
in a cell closed
configuration, whereas the data in Figure 7a-c are associated mainly with 2Li
+
+ O
2
Li
2
O
2
in an
open cell configuration where the cathode is exposed to oxygen. Still, the effect of the IL on the en-
hanced reversibility is valid for both cases.
In order to further understand the distinctive cycling performance among the cells based
on the different electrolytes, the galvanostatic charge/discharge profiles are comparatively presented
(Figure 7). In particular, overpotentials (or halves of charge/discharge gaps) indicate the resistances at
the air electrode/electrolyte interfaces and thus give a clue on the degree of electrolyte decomposition.
Along this line, Figure 7a-c shows a consistent picture with the cycling data and validates our original
- 17 -
electrolyte design of engaging the IL. In the case of pure PC, the gap between charge and discharge
profiles becomes larger more significantly over cycling compared with that of the mixture containing
the 50 % IL. In the case of the mixture containing the 70 % IL, the overpotential becomes larger than
the 50 % case because of the increased IL content.
[28,29]
In addition, the averaged charge-discharge
potential values are indicative of dominant reaction products especially in the first cycle (Figure 7a)
for the cases of the different electrolyte combinations. The pure IL cell shows an average value of
~2.9 V, whereas the pure PC cell shows an average value of ~3.4 V. Although the average value of the
pure PC cell is a bit different from the equilibrium potential of Li
2
CO
3
(~3.86 V)
[43]
perhaps due to
formation of other lithium alkylcarbonates, the average value of the pure IL cell matches well with
the equilibrium potential of Li
2
O
2
(~2.96 V),
[44]
confirming the IL effect toward Li
2
O
2
formation dur-
ing the discharge. Electrochemical impedance spectroscopy (EIS) data also show a consistent trend
between the samples (Figure 7a-c, inset). Unlike the galvanostatic data, the EIS data show the de-
crease in the impedance during the first ten cycles for all of the four samples, which is seemingly as-
cribed to some electro-activation processes such as electrolyte wetting
[45]
and resultant uniform oxy-
gen supply. However, the trend of impedance increase after the 10
th
cycle is consistent with the
aforementioned electrochemical data: In the cycle range of 10-50 cycles, the impedances of the cells
based on PC and the IL increase much more significantly than those of the cell based on the 50 % IL.
- 18 -
Once again, the severely increased impedances of the cells based on PC and the IL are associated with
the formation of the irreversible discharge products
[17]
and the inferior ionic diffusivity/oxygen solu-
bility,
[28,29]
respectively.
3-3 Air electrodes surface analysis
In order to identify the reaction products on the air electrodes during discharge, XPS
analyses were conducted. For these analyses, the -MnO
2
catalyst was not impregnated in the air elec-
trodes because the O 1s signals from the catalyst could bury the signals from reaction products in the
same regions. From the XPS results, the following points are noteworthy:
1) The C 1s spectra (Figure 8a) clearly show the effect of the IL addition. The peak intensity of
Li
2
CO
3
at 289.7 eV
[46]
continuously decreases as the IL content increases. In the case of the pure
IL, the Li
2
CO
3
peak disappears, verifying that the formation of Li
2
CO
3
is exclusively from PC. In
addition, the peak at 293 eV corresponding to CF
3
is intensified with the IL content, as CF
3
origi-
nates from TFSI
-
in both the IL and the lithium salt.
[47]
2) The O 1s spectra (Figure 8b) indicate that the peak at 531.4 eV corresponding to Li
2
CO
3
[40]
be-
comes intensified with the PC/IL ratio. On the contrary, the peak position is shifted toward 532.7
- 19 -
eV corresponding to TFSI
-
,
[47]
as the IL/PC ratio increases, reflecting more dominant character of
the IL. Although Li
2
O
2
formation is expected to be detected at 531 eV
[48]
for the cells containing
the IL, such peaks were not observed perhaps because the amounts of the generated Li
2
O
2
are
much smaller compared to those of TFSI
-
originating from the IL with much larger amounts, re-
sulting in the burial of the Li
2
O
2
peaks by the TFSI
-
peaks. Instead, the presence of Li
2
O
2
at the
end of discharge for the cases of the IL-based electrolytes was confirmed by raman spectroscopy
characterization as discussed below.
3) The F 1s spectra (Figure 8c) indicate that, consistent with the C 1s data, the peaks at 688.9 eV cor-
responding to CF
3
of TFSI
-[47]
is enhanced with the IL/PC ratio. In contrast, the peaks at 684.9 eV
corresponding to lithium fluoride (LiF) show the opposite trend that the peak intensity decreases
with the IL/PC ratio, which is commensurate with a previous report that the LiTFSI salt is decom-
posed more significantly in carbonate-based electrolytes and forms LiF.
[49]
From this trend of the
salt stability, it can be anticipated that the addition of the IL is also beneficial for the stability of
LiTFSI. In addition, the Li 1s spectra (Figure 8d) also support the aforementioned XPS data: the
enhanced Li
2
CO
3
and LiF peaks
[50]
with a decreased IL/PC ratio.
Raman spectroscopy data (Figure 9) also verify the aforementioned trend of the dis-
charge products and the positive effect of the IL on the formation of more reversible products. While
- 20 -
the peak at 1080 cm
-1[17]
corresponding to Li
2
CO
3
is clearly visible for the cell based on PC, and the
peak completely disappears in the case of the cell based on the IL. The cell based on the 50 % IL also
shows the peak at this position, which is reflective of the presence of PC. By contrast, the peaks at
790 cm
-1[48,51]
corresponding to Li
2
O
2
are conspicuously noticeable for the cells based on the pure IL
and 50 % IL, whereas the same peak is negligible for the cell based on PC.
- 21 -
Figure 4. Schematic diagrams showing the electrolyte of LiTFSI dissolved in PC in a) the
absence and b) presence of the IL(PYR
13
TFSI). The TFSI- ion is from both LiTFSI and the
IL.
- 22 -
Figure 5. Room temperature conductivities and viscosities of the blended electrolytes with
various IL/PC ratios. 0.3 M LITFSI was dissolved in all of the electrolytes.
- 23 -
Figure 6. a) CV characterization to test the reversibility of oxygen reduction for various
electrolytes when measured at 40 mV s
-1
in the voltage range of 1.3 - 0.1 V vs. Ag/Ag
+
.
For these tests, 0.05 M TBATFSI was used as a salt in the blended electrolytes. b) Capacity
retentions of various electrolytes when measured in the voltage range of 2.25 - 4.35 V vs.
Li/Li
+
at a current density of 200 mA g
-1
carbon
.
- 24 -
Figure 7. Voltage profiles and impedance spectra (insets) of the various electrolytes at a) the
1
st
cycle, b) the 10
th
cycle, and c) the 50
th
cycle. The color codes used to denote the different
electrolytes in b) and c) are the same as in a).
- 25 -
Figure 8. XPS results of the discharged air electrodes employing the electrolytes with differ-
ent IL/PC ratios. a) C 1s, b) O 1s, c) F 1s, and d) Li 1s. The color codes used to denote the
different electrolytes in b-d) are the same as in a).
- 26 -
Figure 9. Raman spectra of the discharged air electrodes based on various electrolytes.
- 27 -
Chapter 4. Conclusion
4.1 Conclusion
This paper presents the substantially improved cycle life of Li-O
2
batteries by engaging
blended electrolytes. The key feature of using the blended electrolyte in which the IL and PC are
mixed at an optimal ratio is that these two components compensate the drawbacks of the other com-
ponent and thus bring synergistic effects to the cell performance. While the IL minimizes the decom-
position of PC and thus generates more reversible reaction products, PC makes up for the low ionic
conductivity of the IL. Based on these synergistic effects, the optimized blended electrolyte allows
the cell to demonstrate far superior cycling performance compared to the cases where either the car-
bonate-based solvent or the IL is solely used. Detailed electrochemical and surface analyses give a
consistent picture of the diminished irreversible reaction products upon the introduction of the IL.
This study suggests that the generation of reversible reaction products is very critical for the cycle life
of Li-O
2
batteries, and the blended electrolytes might be one of the most feasible solutions.
- 28 -
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