high-energy-density solid-electrolyte-based liquid li-s ... · 1 figure s1. li-s (a) and li-se (b)...
TRANSCRIPT
JOUL, Volume 4
Supplemental Information
High-Energy-Density
Solid-Electrolyte-Based
Liquid Li-S and Li-Se Batteries
Yang Jin, Kai Liu, Jialiang Lang, Xin Jiang, Zhikun Zheng, Qinghe Su, ZeyaHuang, Yuanzheng Long, Chang-an Wang, Hui Wu, and Yi Cui
1
Figure S1. Li-S (A) and Li-Se (B) phase diagram.
0 10 20 30 40 50 60 70 80 90 1000
200
400
600
800
1000
1200
1400
Li 2
Se
350.1 oC
180.6 oC 221 oC
1302 oC
Li Se
L L
99.569.5
Te
mp
era
ture
(oC
)
/%
Te
mp
era
ture
(oC
)
Li 2
S
1372 oC
L
L
365 oC
180.6 oC115 oC
95.5 oC
S/%Li
a
b
A
B
2
Figure S2. XRD measurement of LLZTO electrolyte tube after
immersion in molten lithium for 2 months at 300 oC. Peaks of theoretical
locations from structure of the LLZTO was indexed. It can be seen that the
XRD patterns (before and after soaked in molten lithium for 2 months)
both matched well with the standard pattern known as cubic garnet phase
Li5La3Nb2O12 (PDF45-0109).
20 30 40 50 60
Inte
nsi
ty (
a.u
.)
2 Theta/o
PDF45-0109
Li5AlO4 (PDF14-0540)
LiAlO2 (PDF18-0714)
Pristine
After
LiAl5O8 (PDF17-0573)
3
Figure S3. Surface SEM image of LLZTO electrolyte tube before
melting Li and after long cycling.
Figure S4. Cross section SEM image of LLZTO electrolyte tube before
melting Li and after long cycling.
10 μm
A
2 μm
C
Before cycling
Before cycling
B
D
After cycling
After cycling
10 μm
2 μm
20 μm
10 μm
Before cyclingA B
C DBefore cycling After cycling
After cycling
20 μm
10 μm
4
Figure S5. Optical image of LLZTO pillar and pellet for EIS spectra
measurement.
Figure S6. Ionic conductivity of LLZTO pellet from 25 to 300 oC
A B
5
Figure S7. EIS spectra measurement result of LLZTO pellet from 25-
300 oC (horizontal axis scale from 0 to 250000 ohm).
Figure S8. EIS spectra measurement result of LLZTO pellet from 25-
300 oC (horizontal axis scale from 0 to 2000 ohm).
6
Figure S9. EIS spectra measurement result of LLZTO pellet from 25-
300 oC (horizontal axis scale from 0 to 400 ohm).
Figure S10. EIS spectra measurement result of LLZTO pellet from 25-
300 oC (horizontal axis scale from 0 to 10 ohm).
7
Figure S11. Cross section SEM image of LLZTO electrolyte tube.
100 μm 50 μm
20 μm 5 μm
A B
C D
8
Figure S12. Schematic (A) and result (B) of the impermeability test of
LLZTO electrolyte tube. Schematic (A) and result (B) of the
impermeability test of LLZTO electrolyte tube. Gas pressure difference
(P1-P0) on inside and outside of the ceramic electrolyte tube was increased
slowly, till the maximum value the device can create (550 kPa). Gas flow
rate on the ambient air side was recorded. Thickness of the LLZTO
electrolyte tube: 1 mm.
0 100 200 300 400 500 600 700-0.2
0.0
0.2
0.4
0.6
0.8
1.0
Flo
w r
ate
/ L
/min
(P1-P
0) / KPa
A
B
P1 P0
9
Figure S13. SEM image of Li2S/C and LLZTO electrolyte interface.
Figure S14. SEM image of Li2Se/C and LLZTO electrolyte interface.
20 μm
LLZTO
Li2S/C
Interface
20 μm
LLZTO
Li2Se/C
Interface
10
Figure S15. Vapor pressure comparison of Se and S at different
temperature. Vapor pressure was calculated based on Antoine Equation.
Figure S16. Volatilization experiment results of Se and S. 1 g Se and 1
g S were put in individual open glass containers and heated in an oven full
of argon atmosphere at 300 oC. Their weights were measured every hour.
200 300 400 500 600 700-5
-4
-3
-2
-1
0
1
2
3Boiling Point
S
Se
0.014 kPa
6.3 kPa
0.0011 kPa
Boiling Point
lg(P
/kP
a)
T/oC
1.5 kPa
0 2 4 6 8 10 12 14 16 18 200.0
0.5
1.0
1.5
Se
S
Time (d)
Mas
s (g
)
11
Figure S17. Electrochemical performance of SELL-Se battery at 240
oC. Coulombic efficiency, energy efficiency and specific capacity as a
function of cycle number.
Figure S18. Electrochemical performance of SELL-Se battery at 300
oC. Coulombic efficiency, energy efficiency and specific capacity as a
function of cycle number.
0 100 200 300 400 5000
300
600
900
1200
1500
0
20
40
60
80
100
120
Sp
ec
ific
Ca
pa
cit
y (
mA
hg
-1)
Eff
icie
nc
y (
%)
Coulombic
Energy
Cycle number
3C
0 100 200 300 4000
300
600
900
1200
1500
0
20
40
60
80
100
120
Cycle number
Sp
ec
ific
Ca
pa
cit
y (
mA
hg
-1)
Eff
icie
nc
y (
%)
Energy
Coulombic
4C
12
Figure S19. C-rate performance of SELL-Se battery at 300 oC.
Figure S20. The freeze/thaw test of a SELL-Se cell 240 oC to 20 oC
during discharge/charge. A SELL-Se cell heating off (drop to 20 oC with
natural cooling) and stay at 20 oC for 25 mins during charging and
discharging process then back to 240 oC again.
0 40 80 120 160 200 2400
200
400
600
800
1000
Sp
ec
ific
Ca
pa
cit
y (
mA
hg
-1)
0.5C1C2C3C4C5C
6C4C
7C 8C9C
10C
0 1 2 3 41.0
1.5
2.0
2.5
Vo
lta
ge
(V
)
Time (h)
20 oC 20 oC
13
Figure S21. Self-discharge experiment of SELL-Se battery at
operation temperature of 300 oC with current density of about 10 mA
cm-2. The cell was fully charged to 2.3 V, then halted for 10 days (240h) at
300 oC before discharge again.
00:00 02:00 04:00 06:00 08:00 10:00 12:00 14:00 16:00 18:00 20:00
1.2
1.4
1.6
1.8
2.0
2.2
2.4
243 244 245 246 2470 1 2 3
Standing for 240 h
Time (h)
Vo
ltag
e (V
)
A
B
0 200 400 600 8001.2
1.6
2.0
2.4
Vo
ltag
e (V
)
Specific Capacity (mAh g-1)
Charge
Discharge
14
Figure S22. Sectional view of a SELL-S or SELL-Se cell.
D1
LLZTO tube
S or Se
Lithium
Battery case
D2
15
Figure S23. The calculated mass and volumetric energy density of the
SELL-S (A) and SELL-Se (B) at electrode level with the increase of
LLZTO tube diameter. Here, the energy calculation is based on the
volume and mass of the lithium anode, S or Se cathode, conductive additive,
and LLZTO tube. The wall thickness of the LLZTO tube was 1.5 mm, and
the densities of the LLZTO tube were set as 5 g cm-3.
0 2 4 6 8 10 12 14 16 18 200
200
400
600
800
1000
1200
Mass energy density (Li-Se)
Volumetric energy density (Li-Se)0
300
600
900
1200
1500
1800
Mass e
nerg
y (
Wh
kg
-1)
Vo
lum
etr
ic e
ne
rgy (
Wh
L-1
)
LLZTO tube inner diameter D1 (cm)
B
0 2 4 6 8 10 12 14 16 18 20500
1000
1500
2000
2500
Mass energy density (Li-S)
Volumetric energy density (Li-S)
500
1000
1500
2000
2500
Vo
lum
etr
ic e
nerg
y (
Wh
L-1
)
Mass e
nerg
y (
Wh
kg
-1)
LLZTO tube inner diameter D1 (cm)
A
16
Figure S24. The charge and discharge voltage profile of a SELL-Se
with 260 mAh (400 mg Se as active material), current density of 10 mA
cm-2, and the inner diameter of the LLZTO tube is 5 mm.
0 50 100 150 200 250 3001.6
1.7
1.8
1.9
2.0
2.1
2.2
Vo
lta
ge
(V
)
Cell capacity (mAh)
17
Table S1. Calculation of energy cost based on cost of cathode and anode
materials.
Cathode Cathode
cost* ($) Anode
Anode
cost* ($)
Discharge
product
Capacity
(Ah)
Average
voltage
(V)
Energy
cost
($ kWh-1)
18 mol
Se 50
36 mol
Li 30 Li2Se 965 2.0 41
18 mol
S 0.12
36 mol
Li 30 Li2S 965 2.1 15
72 mol
LiCoO2 370
36 mol
C6 24 Li0.5CoO2 965 3.7 110
45 mol
LiFePO4 76
36 mol
C6 24 Li0.2FePO4 965 3.2 32
*Price obtained from www.alibaba.com.
18
Table S2. Raw cost calculation of a LLZTO electrolyte tube with an inner
diameter of 10 mm, a length of 50 mm and a wall thickness of 1.5 mm.
Raw materials Mass (g) Unit Price* ($ g-1) Total price ($)
La2O3 6.56 0.029 0.190
Li2CO3 4.37 0.014 0.061
ZrO2 2.29 0.007 0.016
Ta2O5 1.78 0.100 0.178
Al2O3 0.17 0.007 0.001
LLZTO tube 13.5 0.03 0.446
*The prices of raw materials are obtained from www.alibaba.com.
19
Table S3. Energy cost calculation of the LLZTO electrolyte tubes with
different inner diameters (set inner diameter: length = 1:5, wall thickness
= 1.5 mm).
Inner diameter
(mm)
Length
(mm)
Mass
(g)
Energy capacity
(Wh)
Total price
($)
Energy Cost
($ kWh-1 )
10 50 13.5 13.3 0.4 30.1
20 100 50.7 107 1.5 14.0
30 150 111.5 361.5 3.3 9.1
40 200 195.3 856.7 5.9 6.9
50 250 303.3 1673.3 9.1 5.4
60 300 434 2892 13.0 4.5
70 350 589.2 4592 17.7 3.9
80 400 768 6856 23.0 3.4
90 450 969 9760.5 29.0 3.0
100 500 1195 13390 35.9 2.7
20
Here we consider a realistic cell configuration to calculate its energy
density. For LLZTO solid electrolyte, we use a tube structure with height
of L cm, wall thickness of 1.5 mm and inner diameter (D1) from 1 to 20
cm. For the outside container (cathode current collector), we use stainless
steel case with wall thickness of 2 mm and inner diameter (D2) that variable
with D1 to guarantee anode and cathode capacity matching). The cathode
consists of 90wt% S (or Se) fused into conductive carbon felt. The
conductive carbon needed for molten S and Se only occupies 10% of the
total electrode weight. Li metal occupies 90% of the internal volume of
LLZTO tubes. S or Se occupies 45% of the total space between LLZTO
tube and stainless container.
1) Suppose that D1=1cm, the total internal volume of LLZTO tube is
calculated to be V1=0.785L cm3.
2) The total volume and mass of lithium metal in LLZTO tube is
calculated to be VLi=0.71L cm3, MLi=0.534*VLi=0.38L g.
3) The total volume and mass of active S between LLZTO tube and
battery case is calculated to be VS=0.37L cm3, MS=2.36*VS=0.87L g.
4) The total volume and mass of LLZTO tube is calculated to be
Vtube=0.54L cm3, Mtube=5*Vtube=2.71L g.
5) The total volume between LLZTO tube and battery case is
calculated to be V2= VS /0.45=0.82L cm3.
The theoretical volumetric and mass energy density is
21
WV1=2800*(VS+ VLi)/( V1+ Vtube+ V2)=1403 Wh L-1
Wm1=2600*(MS+ MLi)/( MS/0.9+ Mtube+ MLi)=800 Wh kg-1
Table S4. Mass and Volumetric energy of SELL-S battery
D1(cm) Mass energy (Wh kg-1) Volumetric energy(Wh L-1)
1 800 1402
2 1242 1620
3 1495 1701
4 1658 1743
5 1772 1769
6 1856 1787
7 1921 1799
8 1972 1809
9 2014 1816
10 2048 1822
11 2077 1827
12 2102 1831
13 2123 1834
14 2141 1837
15 2158 1840
16 2172 1842
17 2185 1844
18 2197 1846
19 2207 1847
20 2217 1849
In the same way, we calculated the Mass and Volumetric energy of
22
SELL-Se battery as following:
Table S5. Mass and Volumetric energy of SELL-Se battery
D1(cm) Mass energy (Wh kg-1) Volumetric energy(Wh L-1)
1 533 1258
2 725 1437
3 815 1503
4 866 1537
5 900 1558
6 924 1572
7 941 1582
8 955 1589
9 966 1595
10 974 1600
11 982 1604
12 988 1607
13 993 1610
14 998 1612
15 1002 1614
16 1005 1616
17 1008 1618
18 1011 1619
19 1013 1620
20 1016 1622