advances.sciencemag.org/cgi/content/full/6/21/eaay5098/DC1

Supplementary Materials for

Supercooled liquid sulfur maintained in three-dimensional current collector for

high-performance Li-S batteries

Guangmin Zhou, Ankun Yang, Guoping Gao, Xiaoyun Yu, Jinwei Xu, Chenwei Liu, Yusheng Ye, Allen Pei, Yecun Wu, Yucan Peng, Yanxi Li, Zheng Liang, Kai Liu, Lin-Wang Wang, Yi Cui*

*Corresponding author. Email: yicui@stanford.edu

Published 22 May 2020, Sci. Adv. 6, eaay5098 (2020)

DOI: 10.1126/sciadv.aay5098

The PDF file includes:

Figs. S1 to S12 Legends for movies S1 to S9

Other Supplementary Material for this manuscript includes the following: (available at advances.sciencemag.org/cgi/content/full/6/21/eaay5098/DC1)

Movies S1 to S9

Supplementary Figures

Figure S1. Charge/discharge voltage profiles of the (A) Ni, (B) C, and (C) Al

electrodes at a current density of 0.05 mA cm−2

. CV curves of the (D) Ni, (E) C, and

(F) Al electrodes at a scan rate of 0.1 mV s−1

for 3 cycles.

Figure S2. (A) Charge/discharge voltage profiles of the Ni, C, and Al electrodes at a

current density of 0.05 mA cm−2

. (B) Cycling stability of the Ni, C, and Al electrodes

Potential (Volts) vs. Li+/Li Potential (Volts) vs. Li+/Li Potential (Volts) vs. Li+/Li

A B C

D E F

0 5 10 15 20 25 30 35 40 45 50

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

Cycle number

Ca

pa

cit

y (

mA

h c

m-2

)

0.05 mA cm-2

0 200 400 600 800 10000

100

200

300

400

500

600

Z'' (

)

Z' ()

0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4

1.0

1.5

2.0

2.5

3.0

Capacity(mAh/cm2)

Vo

lta

ge

(V v

s.L

i+/L

i)

NiCAl

2nd cycle

Al foil

C

Ni0

0.2

0.4

0.6

0.8

1

1.2

1.4

0.05 0.1 0.15 0.25

Ni-Al

C-Al

Al foil

Current density (mA/cm2)

Cap

acit

y (

mA

h/c

m2)

0 10000 20000 30000 40000 500000

5000

10000

15000

20000

25000

30000

Z'' (

)

Z' ()

A

C D

B

Al

C

Ni

at a current density of 0.05 mA cm−2

for 50 cycles. (C) Comparison of the rate

capacity of the Ni, C, and Al electrodes. (D) Nyquist plots of the Ni and C electrodes

at open circuit before cycling at room temperature. Inset is the Nyquist plot of the Al

electrode at open circuit before cycling at room temperature.

Figure S3. Optical images of the Al electrode in lithium polysulfide electrolyte (A) at

initial state, (B) after charging to 3.0 V, and (C) after discharging to 1.0 V. Optical

images of the C electrode in lithium polysulfide electrolyte (D) at initial state, (E)

after charging to 3.0 V, and (F) after discharging to 1.0 V. Optical images of the Ni

electrode in lithium polysulfide electrolyte (G) at initial state, (H) after charging to

3.0 V, and (I) after discharging to 1.0 V.

Figure S4. SEM images of the discharging products formed on the (A) Al, (B) C, and

(C) Ni substrates. Inset in (C) is the magnified image. SEM images of the charging

products formed on the (D) Al, (E) C, and (F) Ni substrates. Inset in (E) is the

magnified area indicated by the red circle. (G) Li 1s XPS spectra of the Ni and C

substrates. (H) S 2p XPS spectra of the Ni and C substrates.

62 60 58 56 54 52 50

C-Al

Ni-Al

Binding Energy (eV)

Inte

ns

ity

(a

.u.)

Li 1s

Charge Charge

10 μm 20 μm

Charge

2 μm

Discharge Discharge

10 μm 5 μm

NiAl C

Discharge

1 μm

A B C

D E F

G H

100 nm

Figure S5. EDS of the discharging products formed on the (A) Al, (B) C, and (C) Ni

substrates. EDS of the charging products formed on the (D) Al, (E) C, and (F) Ni

substrates.

Figure S6. Adsorption energy and configuration of S8 adsorbed on the basal plane of

graphene.

Discharge

Ni coated AlAl foil Carbon coated Al

Al

0.0 0.6 1.2 (keV)

Inte

ns

ity (

a.u

.)

1.8 2.4 3.0 3.6 4.2

O S

0.0 0.6 1.2 (keV)

Inte

ns

ity (

a.u

.)

1.8 2.4 3.0 3.6 4.2

S

O

Al

0.0 0.5 1.0 (keV)

Inte

ns

ity (

a.u

.)

1.5 2.0 2.5 3.0

C S

Al

0.0 0.5 1.0 (keV)

Inte

ns

ity (

a.u

.)

1.5 2.0 2.5 3.0

S OC

Charge

Discharge

Charge

Al Ni

0.0 1.0 2.0 (keV)

Inte

ns

ity (

a.u

.)

3.0 4.0 6.0 7.05.0 8.0 9.0

O S

Ni

Discharge

Al Ni

0.0 1.0 2.0 (keV)

Inte

ns

ity (

a.u

.)

3.0 4.0 6.0 7.05.0 8.0 9.0

O S

Ni

Charge

A B C

D E F

3.5

O

3.5

Al

Ead = -0.81 eV

Graphene basal plane

Figure S7. Configurations of the (A) Ni-O layer and (B) Al-O layer on the surface of

nickel and aluminum, respectively.

Figure S8. Cycling performance and Coulombic efficiency of the sulfur cathode

coated on Ni, C and Al current collectors at 0.2 C for 100 cycles.

Ni-O Al-O

1.10 Å 0.72 Å

A B

Ni current collector

Al current collectorC current collector

0 10 20 30 40 50 60 70 80 90 1000

200

400

600

800

1000

1200

1400

Ca

pa

cit

y (

mA

h g

-1)

0.2 C

Cycle number

0

10

20

30

40

50

60

70

80

90

100

Co

ulo

mb

ic E

ffic

ien

cy

(%)

Ni-Al current collectorC-Al current collectorAl foil current collector

Figure S9. Raman spectra of Ni foam and G/Ni foam.

Figure S10. Charge/discharge voltage profiles of the (A) Ni foam and (B) G/Ni foam

electrodes at different current densities. CV curves of the (C) Ni foam and (D) G/Ni

foam electrodes at a scan rate of 0.1 mV s−1

for 3 cycles.

0 100 200 300 400 500 600 700

1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

3.0

Capacity (mAh g-1)

Vo

lta

ge

(V

vs

. L

i/L

i+)

Ni foam

0.2 C0.5123

0 100 200 300 400 500 600 700

1.4

1.6

1.8

2.0

2.2

2.4

2.6

2.8

3.0

Capacity (mAh g-1)

Vo

ltag

e (

V v

s. L

i/L

i+)

0.2 C0.5123

G/Ni foam

4.8 mg cm-2

1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0-3

-2

-1

0

1

2

3

4

5

1st

2nd

3rd

Cu

rre

nt

(mA

)

Potential (Volts) vs Li+/Li

1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0-3

-2

-1

0

1

2

3

4

5

1st

2nd

3rd

Cu

rre

nt

(mA

)

Potential (Volts) vs Li+/Li

G/Ni foamNi foam

A

C D

B

Figure S11. Adsorption energy and configurations of Li2S adsorbed on the surface of

Ni, graphene edge, and graphene basal plane.

Figure S12. (A) Galvanostatic charge/discharge profiles of the nickel coated

melamine foam electrode at various rates within a potential window of 1.5–2.8 V

versus Li+/Li

0. (B) Rate performance of the nickel coated melamine foam electrode

at different current densities. (C) Cycling performance and Coulombic efficiency of

the nickel coated melamine foam electrode at 0.5C rate for 100 cycles.

0 200 400 600 800 1000

1.5

2.0

2.5

3.0

a

d c b

Capacity (mAh g-1)

Vo

ltag

e (

V v

s.L

i+/L

i) a

d c b

0 5 10 15 20 25 300

200

400

600

800

1000

1200

Cycle number

Ca

pa

cit

y (

mA

h g

-1)

0 10 20 30 40 50 60 70 80 90 100

0

200

400

600

800

1000

1200

Cap

acit

y (

mA

h g

-1)

Cycle number

0

20

40

60

80

100

Co

ulo

mb

ic

Eff

icie

nc

y (

%)

Discharge capacity Coulombic efficiency

0.5C

8.0 mg cm-2

0.2C

0.5C

1C

2C

0.5C

C rate 0.2 0.51.02.0

A B

C

Supplementary Movie Captions

Supplementary Movie 1

Real time imaging for the solid sulfur crystal nucleation, growth, and dissolution

processes on carbon electrode in lithium polysulfide electrolyte. The electrochemical

cell was galvanostatically charged and discharged at 0.05 mA between 3.0 and 1.0 V.

Play speed is 200x of the actual speed.

Supplementary Movie 2

Real time imaging for the liquid sulfur droplet nucleation, growth, and dissolution

processes on Ni electrode in lithium polysulfide electrolyte. The electrochemical cell

was galvanostatically charged and discharged at 0.05 mA between 3.0 and 1.0 V. Play

speed is 25x of the actual speed.

Supplementary Movie 3

Real time imaging for the liquid sulfur droplet nucleation, growth, and dissolution

processes on Ni foam electrode in lithium polysulfide electrolyte at a low

magnification. The electrochemical cell was galvanostatically charged and discharged

at 0.1 mA between 3.0 and 1.5 V. Play speed is 25x of the actual speed.

Supplementary Movie 4

Real time imaging for the liquid sulfur droplet nucleation, growth, and dissolution

processes on Ni foam electrode in lithium polysulfide electrolyte at a high

magnification. The electrochemical cell was galvanostatically charged and discharged

at 0.1 mA between 3.0 and 1.5 V. Play speed is 25x of the actual speed.

Supplementary Movie 5

Real time imaging for the solid sulfur crystal nucleation, growth, and dissolution

processes on G/Ni foam electrode in lithium polysulfide electrolyte at a low

magnification. The electrochemical cell was galvanostatically charged and discharged

at 0.1 mA between 3.0 and 1.5 V. Play speed is 25x of the actual speed.

Supplementary Movie 6

Real time imaging for the solid sulfur crystal nucleation, growth, and dissolution

processes on G/Ni foam electrode in lithium polysulfide electrolyte at a high

magnification. The electrochemical cell was galvanostatically charged and discharged

at 0.1 mA between 3.0 and 1.5 V. Play speed is 25x of the actual speed.

Supplementary Movie 7

Real time imaging for the liquid sulfur droplet nucleation and growth processes on Ni

foam electrode in lithium polysulfide electrolyte. The electrochemical cell was

constantly charged at 3.5 V. Play speed is 3x of the actual speed.

Supplementary Movie 8

Real time imaging for the solid sulfur crystal nucleation and growth processes on

G/Ni foam electrode in lithium polysulfide electrolyte. The electrochemical cell was

constantly charged at 3.5 V. Play speed is 3x of the actual speed.

Supplementary Movie 9

Real time imaging for the liquid sulfur droplet nucleation, growth, and dissolution

processes on Ni coated melamine foam electrode in lithium polysulfide electrolyte.

The electrochemical cell was galvanostatically charged and discharged at 0.08 mA

between 3.0 and 1.5 V. Play speed is 25x of the actual speed.