Electronic Supplementary Material (ESI) for ChemComm.

This journal is © The Royal Society of Chemistry 2020

Electronic Supplementary Information (ESI)

Stabilization of binder-free vanadium oxide-based oxygen

electrode using Pd clusters for Li-O2 battery

Jiade Li,a Senchuan Huang,a Guangyao Zhang,b Zhi Li,b Shengfu Tong,*a Jue Wang,*b
Mingmei Wu*a

a. MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of

Chemistry/School of Marine Sciences, Sun Yat-Sen University, Guangzhou
510275/Zhuhai 519082, China. E-mail: tongshf@mail.sysu.edu.cn;
ceswmm@mail.sysu.edu.cn.
b. Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu
Province, Yancheng Institute of Technology, Yancheng 224051, China. E-mail:
wangjue@ycit.edu.cn.

1
Experimental
Preparation of CC@VO electrode: In a typical synthesis, 5 mmol NH4VO3 and 10 mmol H2C2O2

were dissolved in 50 mL of deionized water at 80°C and stirred for 3 hours. Carbon cloths (CC)

were dipped directly into a Teflon-lined stainless-steel autoclave filled with the prepared mixture

solution, heated at 200°C for 20 h, then cooling down to room temperature naturally. The modified

CC were taken out, and followed by washing with water and alcohol for several times. After that,

the samples were annealed in air at 350°C for 2 hours to achieve CC@VO.

Preparation of CC@VO-Pd electrode: The Pd clusters were prepared by a magnetron plasma gas

aggregation cluster source, and the details of the method can be found in previous papers.[1, 2]

Briefly, a stable pressure of ～75 Pa was maintained in the aggregation tube by introducing 120

sccm argon. The Pd was deposited on the substrates with the deposition rate of 1.5 Å∙s-1 for a certain

time (typically 5, 10, and 15 min), and the Pd atomic clusters firmly adhered to the surface directly.

Material Characterization: X-ray diffraction (XRD) patterns were recorded with a Rigaku

D/MAX 2200 VPC diffractometer using Cu Kα radiation (λ=0.15045 Å). The microstructural

properties were characterized by a scanning electron microscopy (SEM, FEI Quanta 400F) and

transmission electron microscopy (TEM, FEI Tecnai G2 F30). The states of the surface elements

were estimated by X-ray photoelectron spectroscopy (XPS) (ESCALab250). The specific surface

area and pore size distribution were calculated by the Brunauer-Emmett-Teller (BET) and Barret-

Joyner-Halenda (BJH) method respectively, based on the N2 adsorption-desorption isotherms

obtained on a Micromeritics ASAP 2020m instrument at 77.4 K under vacuum. Raman

measurement was carried out on a Laser Micro-Raman spectrometer (RenishawinVia, France) with

a laser excitation at 633 nm.

Electrochemical measurements: The CR2032 coin-type LOB, assembled in an ultra-pure argon-

filled glove-box (the concentrations of O2 and moisture were both controlled below 0.1 ppm), was

utilized for all the electrochemical measurements. The system was similar as that reported in our

pervious works [3, 4] with a lithium foil or LiFePO4 as anode, a glass fiber (glass microfiber filters,

d=16 mm, Whatman) as separator, and an as-prepared binder-free CC@VO or CC@VO-Pd as

oxygen cathode (cut into square, 1 cm × 1 cm). The loaded VO (VO-Pd) was 0.4-0.6 mg cm-2, and

the specific energy density was normalized based on the mass of VO (VO-Pd). The electrolyte was

composed of LiCF3SO3 and TEGDME with a molar ratio of 1:4. The galvanostatic discharge-
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recharge was performed within the potential range of 2.0-4.5 V using a NEWARE battery tester

(Shenzhen, China).

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 (a) 60 Adsorption Desorption
0.014

dV/dD pore volume (cm3 g-1 nm-1)

Volume adsorption (cm3g-1)
0.012

50 0.010

0.008

40 0.006

0.004

30 0.002

0.000

20 1 10 100
Pore diameter (nm)

10

0.0 0.2 0.4 0.6 0.8 1.0

(b) Relative pressure (P/P0)

Adsorption Desorption
60
Volume adsorption (cm3g-1)

0.014
dV/dD pore volume (cm3 g-1 nm-1)

0.012
50
0.010

0.008
40
0.006

0.004
30
0.002

0.000
20
1 10 100
Pore diameter (nm)
10

0.0 0.2 0.4 0.6 0.8 1.0

Relative pressure (P/P0)
Figure S1 Nitrogen adsorption and desorption isotherms of (a) CC@VO and (b) CC. Insets are the
pore size distributions.

Table S1 Surface areas of CC@VO and CC

Sample Surface area (m2 g-1)

CC@VO 7.719

CC 6.686

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Figure S2 The low magnification SEM image of CC@VO

S5
(a)

(b)

Figure S3 TEM and HR-TEM images of VO.

S6
Figure S4 XRD spectra of CC, CC@VO and CC@VO-Pd, respectively.

S7
Figure S5 The SEM image (top) and EDS (bottom) spectra of CC@VO-Pd.

S8
(a)

(b)

Figure S6 The (a) HAADF-STEM and (b) TEM images of VO-Pd.

S9
Figure S7 The element mapping of VO-Pd.

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 CC@VO-Pd O 1s
CC@VO Pd 3d
Pd 3p
V 2p C 1s
Intensity (a.u.)

O 1s

V 2p
C 1s

1000 800 600 400 200 0

Binding energy (eV)
Figure S8 XPS spectra survey of CC@VO and CC@VO-Pd

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 517.4 eV V 2p

V5+
Intensity (a.u.)

524.8 eV
V5+ 523.4 eV 516.0 eV
4+
V
V4+

528 524 520 516 512

Binding energy (eV)
Figure S9 XPS spectra of V 2p for VO

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Figure S10 The XPS spectra of O 1s for VO-Pd.

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 Figure S11 The UPS spectra of CC@VO and CC@VO-Pd.

Table S2 The work function of CC@VO and CC@VO-Pd

Sample Work function

CC@VO 4.54 eV

CC@VO-Pd 5.29 eV

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Figure S12 (a) The potential cut off (2.0 V~4.5 V) galvanostatic discharge/charge voltage curves
of CC and CC-Pd; (b) the terminal discharge/charge voltages of CC and CC-Pd at the current density
of 200 mA g-1.

S15
 (a) 5
1 st Cycle
4 2 nd Cycle

Voltage (V )
3 rd Cycle

1
0 500 1000 1500 2000 2500 3000 3500
Capacity (mAh g-1 )
(b) 5
4 1 st Cycle
Voltage (V )

2 nd Cycle
3 rd Cycle

1
0 500 1000 1500 2000 2500 3000 3500
Capacity (mAh g-1 )
(c) CC@VO discharge
CC@VO charge
3000
Capacity (mAh g-1)

CC@VO-Pd discharge
CC@VO-Pd charge

2000

1000

0 5 10 15 20

Cycle number
Figure S13 The potential cut off (2.0 V~4.5 V) galvanostatic discharge-charge voltage curves of
(a) CC@VO and (b) CC@VO-Pd. (c) A cycle number dependent capacity obtained on CC@VO
and CC@VO-Pd (as indexed in the figure) at a current density of 200 mA g-1.

S16
 (a)
5

4
Voltage (V)

1st 2nd 3rd 4th

1 5th 10th 15th 20th
25th 30th 35th

0 100 200 300 400 500

Capacity (mAh g-1)

(b)
Terminal voltage (V vs. Li/Li+)

Coulumbic efficiency (%)

100
5
80
4

60
3

40
2

1 20
CC@VO-Pd discharge
CC@VO-Pd charge
0 0
0 10 20 30 40 50 60 70

Cycle number
Figure S14 (a) The cycle performance and (b) the terminal discharge-charge voltages of CC@VO-
Pd at the current density of 400 mA g-1.

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 (a) 5.0

4.5 1 st Cycle
2 nd Cycle
3 rd Cycle

Voltage (V )
4.0

3.5

3.0

2.5

2.0

0 1000 2000 3000 4000

Capacity (mAh g-1 )
(b) 5.0

4.5
1 st Cycle
2 nd Cycle
Voltage (V)

4.0
3 rd Cycle

3.5

3.0

2.5

2.0

0 1000 2000 3000 4000

-1
Capacity (mAh g )
(c) 5.0

4.5

1 st Cycle
Voltage (V )

4.0
2 nd Cycle
3 rd Cycle
3.5

3.0

2.5

2.0

0 1000 2000 3000 4000

-1
Capacity (mAh g )
Figure S15 The potential cut off (2.0 V~4.5 V) galvanostatic discharge-charge voltage curves of
CC@VO-Pd with Pd gas-phase-cluster beam deposition for (a) 5 min, (b) 10 min, and (c) 15 min.

S18
(a)

(b)

Figure S16 The SEM images of CC@VO-Pd after 120 cycles.

S19
Figure S17 The XPS spectra of CC@VO-Pd after 120 cycles.

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References
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Wang and M. Han, Electrochim. Acta, 2017, 251, 631-637.
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Wang, Adv. Mater., 2007, 19, 2979-2983.
3 S. Tong, M. Zheng, Y. Lu, Z. Lin, X. Zhang, P. He and H. Zhou, Chem.
Commun., 2015, 51, 7302-7304.
4 C. Luo, J. Li, S. Tong, S. He, J. Li, X. Yang, X. Li, Y. Meng and M. Wu,
Chem. Commun., 2018, 54, 2858-2861.

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