Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2011.

Supporting Information
for Adv. Mater., DOI: 10.1002/adma. 201103042
2D Sandwich-like Sheets of Iron Oxide Grown on Graphene as High Energy
Anode Material for Supercapacitors
Qunting Qu ,

Shubin Yang ,

and Xinliang Feng *

Submitted to
Supporting information for
2D Sandwich-like Sheets of Iron Oxide Grown on Graphene as High Energy Anode Material
for Supercapacitors
By Qunting Qu, Shubin Yang, Xinliang Feng*
[*] Dr. X. Feng, Dr. Q. Qu
College of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800
Dongchuan Road, Shanghai, 200240
Peoples Republic of China
Dr. X. Feng, Dr. Q. Qu, Dr. S. Yang
Max Planck Institute for Polymer Research
Ackermannweg 10, 55128 Mainz, Germany
E-mail: feng@mpip-mainz.mpg.de
Experimental section
Synthesis: Pure FeOOH nanorods were prepared by hydrolyzing 0.1 mol/L of FeCl3 solution
at 80OC for 5h. The product was then filtered, washed with distilled water, and dried at 60OC
overnight. For the preparation of e-Fe3O4 through the electrochemical transformation of
FeOOH, the FeOOH electrode was first prepared by pressing the mushy mixture of FeOOH,
acetylene black, and poly(tetrafluoroethylene) (PTFE) in a weight ratio of 8:1:1 onto Ni-mesh.
The FeOOH electrode was then dried and electrochemically cycled in a three-electrode cell by
using 1 mol/L of LiOH solution as electrolyte. The counter and reference electrodes were
Ni-mesh and saturated calomel electrode (SCE), respectively. The FeOOH active material
transformed into e-Fe3O4 after electrochemical cycles in the potential range of -1.350.1V
(vs. SCE). For comparison, co-Fe3O4 was prepared through a traditional coprecipitation
method. 100 mL of aqueous solution containing 0.1 mol/L of FeCl2 and 0.2 mol/L of FeCl3
was first prepared. Upon stirring this solution at room temperature, 100 ml of 0.5 mol/L
NaOH solution was added dropwise under the nitrogen atmosphere. The obtained precipitate
1

Submitted to
was filtered, washed, and then dried at 60oC. The co-Fe3O4 powder was then physically mixed
with chemically reduced graphite oxide (RGO) in the weight ratio of 9/1 in aqueous solution.
After evaporation of water, the obtained mixture is denoted as co-Fe3O4/RGO. The
co-Fe3O4/RGO electrode was prepared in the same way as that of FeOOH electrode for
electrochemical testing.
Graphite oxide (GO) was synthesized from natural graphite flake by a modified Hummers
method, as described elsewhere.[1,

2]

Chemically reduced graphite oxide was obtained by

reducing GO in 0.5 mol/L NaOH solution at 80OC for 1 h. For the preparation of iron
oxide@GO or iron oxide@RGO nanocomposites, 40 mL of 1 mg/mL GO or RGO
suspensions was ultrasonicated for 1h, into which 10 mL of 0.1 mol/L FeCl3 solution was
slowly added. The mixture solution was heated to 80oC and kept at this temperature for 5
hours. The FeOOH@GO or FeOOH@RGO product was then filtered, washed with distilled
water, and dried at 60OC overnight. The FeOOH@GO or FeOOH@RGO electrode was
prepared by the same way as that of FeOOH electrode and subject to electrochemical cycles
to realize the electrochemical transformation reaction from FeOOH to Fe3O4.
Material characterization: The morphology, microstructure, and composition of the
materials were investigated by FE-SEM (Hitachi SU8000), TEM (Philips EM 420), XRD
(Bruker D4), XPS (VG ESCA 2000), FTIR (Nicolet 730), and TGA (Mettler TGA/SDTA
851). The BET surface area was obtained through the nitrogen absorption isotherms measured
at 77 K using a Micromeritcs Tristar 3000 analyzer (USA).
Electrochemical characterization: Electrochemical measurements were performed on an
electrochemical

workstation

(CHI

760D).
2

The

obtained

co-Fe3O4/RGO,

e-Fe3O4,

Submitted to
e-Fe3O4@GO, and e-Fe3O4@RGO electrodes were tested in the three-electrode cell by using
LiOH solution as electrolyte. The galvanostatic discharge and charge was performed in the
potential range of -1.15V0.1V (vs. SCE). From the charge and discharge curves, the
specific capacitance (F/g) of the electrode material was calculated using formula C =

I t
,
m U

where I is the current (A) used for charge/discharge cycling, t is the charge time (seconds), m
is the mass (g) of the active materials (including GO or RGO) in the electrode, U is the
operating potential window (V) during the charge. The energy density (Wh/kg) was
calculated according to the formula E =

I t Ua
, where I is the current (mA), t is the charge
m

time (hours), Ua is the average working potential (V) during charge, m is the mass (g) of the
active materials in the electrode.

Supplementary figures:

Weight / %

100

90

FeOOH
80

FeOOH@RGO
70

60
0

200

400

600

800

Temperature / C

Figure S1 TG curves of FeOOH and FeOOH@RGO in the air.

Intensity / a.u.

Submitted to

FeOOH
FeOOH@RGO
20

40

60

80

2-Theta / degree

Figure S2 XRD pattern of the FeOOH@RGO nanocomposites.

0.02

1st

Current / A

0.00
-0.02
-0.04

2nd
-0.06
-0.08
-1.2

-0.8

-0.4

0.0

Potential / V vs. SCE

Figure S3 The cyclic voltammogramms of FeOOH@RGO electrode in 0.5 mol/L LiOH
solution at the scan rate of 5 mV/s.

Submitted to

100 nm

Figure S4 TEM image of the physically mixed composites of RGO and co-Fe3O4 powder.

0.01

KOH
LiOH

Current / A

0.00

-0.01

-0.02

-0.03
-1.2

-0.8

-0.4

0.0

Potential / V vs. SCE

Figure S5 The cyclic voltammogramms of the e-Fe3O4 electrode in 0.5 mol/L LiOH and KOH
solution.
The cyclic voltammogramms of the Fe3O4 electrode exhibit similar redox peaks in LiOH and
KOH solution except a little difference in the potential of anodic peak, further suggesting that
the electrochemical reaction of Fe3O4 should be based on the faradic pseudocapacitance
produced by the fast absorption or intercalation of cations.

Submitted to

200 nm

a)

b)

Figure S6 TEM images of the FeOOH@RGO nanocomposites containing about 5% (a) and
30% (b) of RGO.
As can be seen from Figure S6, the 5%RGO sample has too many FeOOH nanorods on the
graphene surface, and most FeOOH nanorods aggregate together, which is unfavorable for the
fully utilization of Fe oxide active material. In the case of 30%RGO sample, very few FeOOH
nanorods were formed, leading to non-uniformity of the obtained composites. As a result, the
graphene sheets restacked or wrinkled easily, and it is difficult to find the edges of
monolayered graphene.

[1] W. S. Hummers, R. E. Offeman, J. Am. Chem. Soc. 1958, 80, 1339.

[2] Y. Y. Liang, D. Q. Wu, X. L. Feng, K. Mllen, Adv. Mater. 2009, 21, 1679.