SUPPLEMENTARY INFORMATION

Filling the Voids of Graphene Foam with Graphene Eggshell for Improved
Lithium-ion Storage

Bee-Min Goh,#, Yu Wang,#, M.V. Reddy, Yuan Li Ding, Li Lu, Christopher Bunker and Kian Ping
Loh,*

Department of Chemistry, Graphene Research Centre, National University of Singapore, 3 Science

Drive 3, 117543, Singapore

Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1,

117576, Singapore

Air Force Research Laboratory, Propulsion Directorate, Wright-Patterson Air Force Base, Dayton,

OH 45433, USA

Catalyst Preparation
The catalysts were prepared by a conventional chemical impregnation method. In a typical experiment,
nickel powder (Alfa Aesar, spherical, APS 2.2-3.0 micron, 99.9%) was first added poly (methyl
methacrylate) PMMA (MicroChem Corp. 950 PMMA A5, 5% in anisole) and then dispersed by ultrasonication for ~20min. The PMMA-coated Ni-powder dispersion was slowly drop-casted into nickel
foams (Alantum Advanced Technology Materials (Dalian), ~380g/m2 in area density and ~1.2mm in
thickness). The as-prepared PMMA-coated Ni-powder@Ni foam was baked at 80 oC of low temperature
for 5h and then annealed at 200 oC of high temperature for 10h.

Chemical Vapor Deposition

In the CVD growth of GE@GF hybridized structure, PMMA plays two roles: (1) fixing the Ni powder
in Ni foam and (2) solid carbon source for the growth of graphene. Before the growth of GE@GF, the
CVD furnace was heated to 950 oC in Ar (100 sccm) and H2 (50 sccm). After the temperature became
stable, Ni-powder@Ni foam sample was introduced into the furnace with CH4 gas (30 sccm). After 20
min of growth, the system was cooled to room temperature under H2. Although PMMA can be used as
carbon source for the growth of 3D graphene structure, CH4 was also introduced as carbon source in
order to ensure the sufficient carbon supply. For the growth of N-doped samples, ethylenediamine (EDA)
solution was used as carbon and nitrogen source. An amount of ethylenediamine (EDA) solution was
injected into the CVD system, and then volatile EDA was carried by a mixture gas of Ar (50 sccm) and
H2 (30sccm). The reaction temperature was maintained at 1000 oC for about 25 minutes.

Characterization
The as-produced samples were characterized using SEM (Hitachi S-4300, operated at 15kV) attached to
an energy dispersive X-ray spectrometer (EDS) and high-resolution transmission electron microscopy
(HR-TEM, FEI Titan, 200 kV). After TEM images were obtained, selected area electron diffraction was
also performed. X-ray photoelectron spectroscopy (XPS) data were obtained with an ESCALab220i-XL
electron spectrometer from VG Scientific using 300W AlK radiation. For analysis, appropriate
smoothing for the raw data and background removal using the Shirley method was applied. C 1s and N
1s core-level spectra were both curve-fitted by the subpeaks with Gaussian and Lorentzian mixed
function for the asymmetric core level peak shape. Raman spectra were measured with a WITEC
CRM200 Raman system at room temperature. The excitation source was 514nm with a laser power

below 0.1mW to avoid laser-induced heating of the samples. The spot size of 514nm laser light was
estimated to be 500nm. Ex-situ NMR spectrum was collected by discharging GE@GF electrode to 0.005V
vs. Li/Li+ at 37mA/g. The coin cells were dismantled and electrodes were washed in DEC solvent and
evaporated to remove residual moisture in a glove box. The electrodes were removed and transferred into
NMR sample tubes (5 mm diameter). 7Li NMR spectra were obtained at resonance frequency of 155.5 MHz
at with a Bruker Avance DRX 400 spectrometer. Pulse delay of 2s was used for measuring the spectra of Li
intercalated into carbon (LiCx).

Figure S1. SEM images of the graphene eggshells were packed tightly into an interwoven network
within the graphene foam, which gave an interconnected electrically conducting network. (b) and (d) are
magnified SEM images of the red square in (a) and (c), respectively.

Figure S2. (a) A single Lorentzian peak in monolayer graphene; (b) The fitted four components of the
2D band in bilayer graphene; (c) the peak profile of 2D band in FLG can be fit into 2 Lorentzain peaks,
which is similar with that of graphite.

Intensity (a.u.)

600

500

400

300

200

100

Binding Energy (eV)

Intensity (a.u.)

C1s

294

292

290

288

286

284

282

280

Binding Energy (eV)

Intensity (a.u.)

N1s

410

405

400

395

390

385

Binding Envergy (eV)

Figure S3. XPS measurements of the N-doped GE@GF, and the atomic percentage of N in the samples
is about 3.6 at%.*

* Most commonly a semi-quantitative approach is applied in order to express the degree of nitrogen
atom doping. It relates the measured elemental peak intensity (area) values to so-called relative surface
concentrations through the use of a set of elemental sensitivity factors. The relative surface
concentration in at.% cx are determined from the peak intensities Ix, and the corresponding sensitivity
factors Sx:

cx =

I x / Sx
100
i I i / Si

(1)

The surface atomic concentrations are calculated from the peak areas in the N(E) spectra after
subtraction of a Shirley background,[1] using the sensitivity factors given in Ref.[2]

References:
1.

Vgh, J. On Calculating Intensity from XPS Spectra. J. Electron Spectrosc. Relat. Phenom.2006,
151, 2430.

2.

Wagner, C.D.; Riggs, W.M.; Davis, L.E., Moulder, J. F. Handbook of X-ray Spectroscopy, PerkinElmer, Eden Prairie, Minnesota, USA, 1992.

Figure S4. Electrochemical performances of N-doped GE@GF. (a) Galvanostatic profile (b) cycling of
37mA/g, 3.0-0.005V (c) cyclic voltammetry at scan rate of 58 s/V (d) rate performance at current
density range from 37-370mA/g

Figure S5. In-situ Raman spectra for commercial graphite electrodes discharge from 3.0V-0.005V vs.
Li/Li+