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 Page 1 of 29
Energy & Energy & Environmental Science
Environmental Science
Cite this: DOI: 10.1039/c0xx00000x
www.rsc.org/xxxxxx
Three-dimensional porous LiFePO4 cathode material modified with
Published on 06 January 2015. Downloaded by University of Massachusetts - Boston on 06/01/2015 11:08:18.
nitrogen-doped graphene aerogel for high-power lithium ion batteries
Bo Wang,ab Wael Al Abdulla,c Dianlong Wang*a and X. S. Zhao*bd
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5 DOI: 10.1039/b000000x
A composite cathode material consisting of (010) facet-
orientated LiFePO4 nanoplatelets wrapped in nitrogen-doped
graphene aerogel is reported. Such a composite possesses a
3D porous structure with a BET surface area as high as 199.3
10 m2·g-1. In this composite, the nitrogen-doped graphene
aerogel combined with its interconnected pore networks
provide pathways for rapid electron transfer and ion
transport, while the thin LFP nanoplatelets with large (010)
surface area enhance the active sites and shorten the Li +
15 diffusion distances. As a result, a high rate capability (78
mAh·g−1 at 100 C) as well as a long life cycling stability (89%
capacity retention over 1000 cycles at 10 C) are achieved.
Energy storage devices with both high energy and power
densities are essential to power electric vehicles (EVs) and hybrid
20 electric vehicles (HEVs).1 Lithium-ion batteries (LIBs) that have
been widely used to power portable electronic devices (e.g.,
laptops, cellular phones, and personal digital assistants) represent
an important family of the energy storage devices1-3. However, as
a power source of EVs and HEVs, the current LIB technology
25 still needed to be further advanced for improving the power
density to compete with other electrochemical energy storage
devices, such as supercapacitors.1, 3, 4 In general, the power
capability of a LIB is largely related to the ionic and electronic
transport kinetics of the electrode material used in the LIB.4, 5
30 Being a candidate of LIB cathode material, olivine structured
LiFePO4 (LFP) has various advantages, such as large theoretical
capacity (170 mAh∙g-1), high electrochemical potential, good
thermal stability, low cost, environmental friendliness, and
nontoxicity.6-8 The major problems associated with LFP however
35 still lie in the fact of its poor electric conductivity and low Li+
diffusivity along the [010] direction only.7-9 Strategies have been
developed for addressing these problems with different levels of
success, including optimizing particle size and morphology,3, 9
doping with alien ions,9-11 and surface modification with
40 electronic or ionic conductive layers.12-14 These abovementioned
strategies mainly focused on the improvement of the intrinsic
properties of LFP itself. When it comes to the LFP electrode, its
battery performance is determined by not only the LFP properties,
but also the electrode properties, such as the porous structure.15, 16
45 As has been recognized that the ion transport in the electrolyte
through the pores of the electrode to approach the LFP surface
may also be rate-limiting, especially at high rates.17, 18 Fabricating
This journal is © The Royal Society of Chemistry [year]
DynamicDOI:
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10.1039/C4EE03825H
COMMUNICATION
Energy & Environmental Science Accepted Manuscript
three-dimensional (3D) pore network in the electrode material is
considered as an efficient way to facilitate ion transport through
50 the electrode.19, 20 One of the general approaches for this purpose
is supporting the active material with a porous network,19-21 and
in many cases, 3D porous carbons are used. So far, various
carbon matrixes have been employed to prepare porous LFP-
carbon composite electrodes.21-23 These carbons are however
55 amorphous in general with a relatively poor electric conductivity
and usually take up a high mass percentage in the composite.
Graphene aerogel (GA) possesses unique advantages over
amorphous carbon in preparing 3D porous electrode materials,
such as high porosity, large surface area and good electronic
60 conductivity.24-26 As a result, it is an ideal porous network for
preparing LFP-carbon composite electrode with 3D ion diffusion
channels and good electric conductivity. Moreover, nitrogen (N)
doping is an effective way to improve the electronic conductivity
and wettability of the graphitic materials.27, 28 Therefore, it can be
65 expected that doping N in GA could further improve the electric
conductivity and Li+ transport when used in LIB.
Recently, controlling LFP crystal orientation along the (010)
facet has been demonstrated as an effective way to increase the
number of active sites for electrochemical reactions with a short
Li+ diffusion length.6, 29, 30 In a previous study,31 we observed that
70
the (010) facet-orientated LFP nanoplatelets (LFP NPs) and
reduced graphene oxide (rGO) composite electrode displayed
improved electrochemical performances. However, when come to
high current rates (> 60C), the capacity dropped dramatically due
to the sluggish mass transfer in such electrode. In this work, we
75
attempted to wrap (010) facet orientated LFP NPs with N-doped
GA (N-GA) to prepare a porous N-GA modified LFP composite.
It was anticipated that such a composite, hereinafter designated as
LFP@N-GA, would have the following advantages (Scheme 1a-
80 c): (i) a 3D porous network that enables rapid Li+ transport, (ii) a
short Li+ diffusion length in the LFP NPs, thus enhancing the
solid-state ion diffusion rate, (iii) a large electrode/electrolyte
interfacial area, increasing the number of active sites for
electrochemical reactions, and (iv) a high electronic conductivity,
85 increasing electron transfer rate in the electrode. Besides, N-GA
is also an electrochemical capacitor material, which could store
energy in electric double layer.25, 32 As reported previously,33 in a
composite electrode, the capacitor component may promote a fast
capacity response and buffer the impact on LIB component under
90 high-rate charge or discharge, and thereby, beneficial for its rate
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DOI: 10.1039/C4EE03825H

performance and cycling stability. Electrochemical test results S2†).34 The constructed LFP@GO was then dispersed in a urea-
demonstrated that the LFP@N-GA composite electrode indeed dissolved aqueous GO suspension and placed in an autoclave for
exhibited a high rate capability (78 mAh·g−1 at 100 C) and a 15 hydrothermal treatment. In the hydrothermal process, the exposed
stable cyclability (90% capacity retention over 1000 cycles at 10 GO surface in LFP@GO cross-linked with the additional GO by

Energy & Environmental Science Accepted Manuscript

5 C). taking advantage of the oxygen-containing groups as cross-
The preparation procedure of LFP@N-GA is illustrated in linking sites. Simultaneously, GO was further reduced and N-
Scheme 1d. LFP NPs were first synthesized using a solvothermal doped by urea. Thereby, a 3D hierarchical N-doped graphene
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method with ethylene glycol (EG) as the solvent (Fig. S1†).30
Graphene oxide (GO)-anchored LFP NPs (LFP@GO) were then
10 prepared through an electrostatic attraction process by co-
assembling of positively-charged aminopropyltrimethoxysilane
(APS)-modified LFP NPs and negatively-charged GO (Fig.
20 hydrogel wrapped LFP NPs was prepared. After freeze-drying
dehydration and heat treatment, the final LFP@N-GA was
obtained. The details of sample preparation refer to the
experimental section of ESI. The photograph illustration of the
synthetic procedure is shown in Fig. S3†.

25
Scheme 1 (a) Schematic of a battery based on LFP@N-GA cathode. The LFP NPs active phase is green, the porous N-GA network is grey, and the
electrolyte filled in the pores is pale blue in color. (b) Illustration of the four primary resistances in LFP@N-GA cathode, including 1) Li+ transports in the
electrolyte, 2) Li+ diffuses in LFP NPs, 3) Electrochemical reactions at LFP/electrolyte and/or LFP/FePO4 (FP) interfaces, and 4) Electrons transfer in the
electrode. (c) Schematic of the Li+ diffusion process in LFP crystal. (d) Preparation process of LFP@N-GA: 1) Interactions between positively charged
30 LFP NPs and negatively charged GO sheets via electrostatic attraction; 2) Self-assembly and N-doping; 3) Freeze-drying to obtain LFP@N-GA.

The morphology and microstructure characterizations of
LFP@N-GA are provided in Fig. 1. The scanning electron
microscopy (SEM) images at different magnification (Fig. 1a, b
and S4†) show LFP NPs of 150-200 nm in length, 70-100 nm in
35 width, and 30-40 nm in thickness were wrapped in the porous GA
network. The porous structure of LFP@N-GA was further
characterized by nitrogen isothermal adsorption/desorption
measurement. Based on the Barrett-Joyner-Halenda (BJH) model,
the pores of LFP@N-GA ranged mostly between 2 and 100 nm
40 (inset of Fig. S5a†). Meanwhile, a well-defined 4.5 nm mesopore
was obtained. The high porosity of GA offers a large surface area
for more LFP NPs to contact with the electrolyte that enhances
the active sites for electrochemical reactions. As expected, a large
Brunauer-Emmett-Teller (BET) specific surface area of LFP@N-
45 GA (Fig. S5a†) was realized (199.30 m2·g-1), which was much
higher than the linear combination of the BET surface area of
LFP NPs and N-GA by weight fraction (Figs. S5† and S6†), and
thus, suggested an alleviative agglomeration between LFP NPs.
The high surface area of LFP@N-GA combined with its unique
50 macro- and meso- porous feature, are favorable for electrolyte
accessibility and rapid Li+ transport. From the transmission
electron microscope (TEM) image of LFP@N-GA (Fig. 1c), it
can be seen the LFP NPs were tightly inlayed in a graphene-
based substrate with the dents surrounding them. Such a close
55 contact guarantees a good electronic contact between LFP NPs
and N-GA. The high-resolution TEM (HRTEM) image shown in
Fig. 1d further reveals the LFP NP was tightly anchored on a
graphene sheet (≤6 layers) with a “shell-core” structure.35 The
lattice fringe of LFP NP with space of 4.29 Å agrees well with
60 the d-space of the (101) plane of LFP crystal. The Fast Fourier
transform (FFT) pattern (inset of Fig. 1d) demonstrated LFP NPs
have a preferred crystal orientation along the (010) facet, which
will be beneficial for shortening the Li+ diffusion path in LFP
crystal. The pores surrounded by LFP NPs inside of LFP@N-GA
65 can also be observed in the HRTEM images (Fig. 1e, f). In
addition, it should be noted that the graphene layers outside the
LFP NPs cross-linked with the other graphene components to
construct an interconnected graphene network (Fig. 1d-f). Such

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Page 3 of 29 Energy & Environmental Science
an interconnected conductive network enables an efficient
electron pathway and thus improves the electronic conductivity of
the overall electrode. Fig. 1g (TEM) and h (HRTEM) show a
typical LFP NP was well wrapped by N-GA. The distinct lattice
5 fringe along [100], [011] and [010] directions further confirmed
the (010) facet orientation of LFP NP, also suggested a good
crystallization as well as expedite Li+ diffusion paths. The
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elemental mapping result (Fig. 1i) obtained from the high-angle
annular dark-field scanning TEM (HAADF-STEM) reveals the
10 Fe, P and O distributions were quite uniform with the same quasi-
rectangle shape, indicative of a LFP NP; while N and C were also
well distributed over all scope, suggesting N heteroatoms are
homogenously doped in GA.27
15 Fig. 1 (a, b) SEM images of LFP@N-GA at different magnification. Inset:
a high-resolution SEM image revealing an individual LFP NP embedded
in a porous GA matrix. (c) TEM image of LFP@N-GA. (d) HRTEM
image of LFP@N-GA corresponding to the yellow-boxed area in (c).
Inset: FFT pattern of the HRTEM image, where B denotes the beam
20 direction, indicating the (010) facet orientation. (e, f) HRTEM images
revealing the pores inside LFP@N-GA. (g, h) TEM and HRTEM images
suggesting a well-crystallized LFP NP well wrapped by N-GA. (i)
HAADF-STEM image and elemental mapping results of LFP@N-GA.
The X-ray photoelectron spectroscopy (XPS) was carried out
25 to further examine the composition and the chemical state of the
atoms in LFP@N-GA. The wide XPS spectrum of LFP@N-GA
(Fig. 2a) exhibited that the binding energy of 56.4, 132.7, 398.4
and 531.2 eV corresponded to Li 1s, P 2p, N 1s and O 1s,
respectively, with the reference binding energy at 284.8 eV for C
30 1s peak. Fig. 2b presented the high resolution XPS spectrum of
Fe 2p of LFP@N-GA. The binding energy positioned at 710.8
and 724.3 eV were ascribed to Fe 2p3/2 and Fe 2p1/2 respectively
with an energy separation (∆EFe) of 13.5 eV, which matched well
with previously reported spectra of Fe2+ in LFP.36 Fig. 2c and 2d
35 compared the C 1s high resolution XPS spectra of GO and
LFP@N-GA, the dramatic loss of oxygen-containing functional
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DOI: 10.1039/C4EE03825H
groups indicated the reduction of GO.28 The high resolution XPS
spectrum of N 1s of LFP@N-GA was shown in Fig. 2e, which
can be resolved into three components centered at 398.3, 399.5
and 401.7 eV, representing the pyridinic, pyrrolic and graphitic
Energy & Environmental Science Accepted Manuscript
40
types of N atoms, respectively.37 In addition, the XPS analysis
revealed the N-doping level was ~ 4 at.% in N-GA. Therefore,
the XPS result confirmed the high purity of LFP NPs, the
reduction of GO and the successful N-doping in GA.
45 The weight fraction of N-GA in LFP@N-GA was
demonstrated to be 15.36 wt.% through the thermogravimetric
analysis (TGA, Fig. S6†), which was much lower than the carbon
content of previously reported 3D porous LFP/Carbon
composites.18, 21, 23, 38 Interestingly, the electronic conductivity of
50 LFP@N-GA measured by a four-probe meter was higher than
them, with the value up to 7.19 S·cm−1. In addition, the measured
electronic conductivity of N-GA (261.25 S∙cm-1) was higher than
pristine GA (89.73 S∙cm-1), which further demonstrated the
positive role of N-doping in improving the electronic
55 conductivity of GA, and thus further enhancing the electronic
conductivity of the N-GA modified composites. As reported by
Huiming Cheng et al.,27 doping N in graphene not only enhances
its electronic conductivity, but also improves the wettability
between graphene and the organic electrolyte. Therefore, using
60 N-GA as the scaffold for LIB is expected to build more efficient
pathways for both Li+ and electron compared with pristine GA.
Fig. 2 (a) XPS survey of LFP@N-GA. (b) High resolution XPS spectrum
of Fe 2p for LFP@N-GA. (c) and (d) High resolution XPS spectrum of C
65 1s for LFP@N-GA and GO. (e) High resolution XPS spectrum of N 1s
for LFP@N-GA. (f) XRD patterns of LFP@N-GA and the standard LFP
(JCPDS card No. 81-1173). (g) Raman (green line) and FTIR (blue line)
spectra of LFP@N-GA.
Fig. 2f shows the X-ray diffraction (XRD) pattern of LFP@N-
70 GA. The diffraction peaks of the composite were well indexed to
the olivine structured LFP with the space group of Pnma (JCPDS
81-1173).39 All the diffraction peaks were distinct, indicating a
high crystallinity of the LFP NPs.40 A hump appearing in the
range of 22-26º was attributed to the stacking of N-doped
75 graphene sheets in N-GA.35 Raman spectroscopy was further
utilized to analyze the structure of LFP@N-GA (green line of Fig.
2g). The bands observed between 200-1100 cm-1 were owing to
the vibrational motions of LFP NPs, among them: the bands
between 900-1100 cm-1 were attributed to intermolecular
80 stretching motions and antisymmetric stretching modes of PO43-,
Journal Name, [year], [vol], 00–00 | 3

Energy & Environmental Science
the bands between 560-700 cm-1 and 400-500 cm-1 were assigned 45
to the combined antisymmetric stretching modes of PO43-, and the
bands below 400 cm-1 were caused by lattice vibrations.6 These
vibrational bands were in good agreement with the assignments
5 reported in the literature, suggesting the high purity of LFP
NPs.30 Besides, the bands observed at 1328 and 1589 cm-1 were 50
attributed to the D and G band of N-GA component.41 The G
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band is due to graphite carbon, whereas the D band is attributed
to defects in the graphite structure.27 Generally, the intensity ratio
10 of D band to G band (ID/IG) is used to estimate the disorder of
graphitic materials. As shown in Fig. S7†, N-GA and LFP@N- 55
GA shows apparently higher ID/IG (~ 1.30) than pristine GA (0.99)
suggesting a more disordered structure after N-doping, which is
consistent with the previously reported N-doped graphitic
15 materials.27, 28 In contrast with N-GA, a shift can be found for
both D and G band of LFP@N-GA (Fig. S7†), indicative of a 60
charge transfer between N-GA and LFP NPs and suggesting a
good electronic contact between these two components.28 For Li+
diffusing in LFP lattice, it is not only determined by the diffusion
20 length but also by the Fe•Li antisite defect. Thereby, the Fe•Li
antisite defect of LFP@N-GA was further examined by Fourier 65
transform infrared spectroscopy (FTIR, blue line of Fig. 2g). The
infrared absorption bands at 948 cm-1 corresponded to the
symmetric stretching vibration of P−O bond, which was close to
25 that of defect-free LFP and implied a low Fe•Li antisite defect
concentration.6 Such a good crystallinity was benefited from 70
using EG as the solvent to synthesize LFP NPs due to its much
higher viscosity (η = 21 mPa∙s) compared with H2O (η = 1.0087
× 10-3 mPa∙s). This guaranteed that the different ions species (Li+,
30 Fe2+) can match each other well in the solvothermal process.42
After the thermal annealing of the LFP@N-GA precursor, the 75
crystal structure of the LFP NPs can be further perfected.6
80
85
90
Fig. 3 Electrochemical properties: (a) Charge/discharge profiles at 0.2 C,
35 inset: The magnified selected-region comparing the potential plateaus; (b)
Rate capabilities from 0.2 C to 100 C; (c) Charge/discharge profiles at
current rate ranging from 1C to 100 C; (d) Cycling performance 95
combined with Coulombic efficiency at 10 C of commercial LFP/C and
LFP@N-GA.
40 To demonstrate the good electrochemical performance of
LFP@N-GA, an electrochemical study compared with a
100
commercial LFP/C product (Likai Co. Ltd., Taiwan, Fig. S8†)
was performed. Before fabricating the electrode, LFP@N-GA
was ground to increase its volumetric energy density without
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DOI: 10.1039/C4EE03825H
impairing its microstructure.35 Fig. 3a exhibited their typical
charge/discharge profiles at a small rate of 0.2 C, where C
corresponded to the current rate. The revisable capacity of
LFP@N-GA and commercial LFP/C at this rate was comparable
Energy & Environmental Science Accepted Manuscript
with each other (~155 mAh·g-1). However, the charge/discharge
potential-plateau of LFP@N-GA was more stable than that of
commercial LFP/C (inset of Fig. 3a), indicative of the more
expedite Li+ diffusion paths in LFP NPs.9 With the increase of
current rate, the difference in rate capability (Fig. 3b) between
these two electrodes became distinctly obvious. LFP@N-GA
presented a high discharge capacity of 132, 124 and 112 mAh∙g-1
at 5, 10 and 20 C, respectively, while commercial LFP/C only
presented 87, 59, and 16 mAh∙g-1 at the corresponding current
rates. LFP@N-GA even exhibited capacities of 96 mAh∙g-1 at 60
C and 78 mAh∙g-1 at 100 C, but the commercial LFP/C was
almost un-rechargeable at these current rates. Remarkably, the
more stable and higher discharge potential-plateau of LFP@N-
GA at each current rate (Fig. 3c and Fig. S9†) indicated both the
higher energy density (energy = capacity × voltage) and power
density (power = voltage × current).43 The good rate capability of
LFP@N-GA was ascribed to the well-crystallized nature and the
desired crystal orientation of LFP NPs as well as the bicontinuous
pathways for both Li+ and electron constructed by N-GA. The
reversible capacity of LFP@N-GA sustained 110 mAh·g-1 after
1000 cycles at 10 C with a capacity retention of 89% (Fig. 3d).
The corresponding average Coulombic efficiency approached
99.6%, suggesting the highly reversible Li+ insertion/extraction
kinetics.44 The cycling stability of LFP@N-GA was also superior
to commercial LFP/C, which sustained a reversible capacity of
29.6 mAh·g-1 with capacity retention of 50% at the same testing
conditions. The good cyclability of LFP@N-GA was attributed to
the fast capacity response of N-GA, which buffered the impact to
LFP under the high-rate cycling (Fig. S10†).33 Meanwhile, the
structural robustness of N-GA could accommodate the volume
change of the electrode during Li+ insertion/extraction.35 As
validated by TEM investigation (Fig. S11†), the original
morphology of LFP@N-GA was preserved well after the cycling
test. It should be noted, although the cycling performance of
LFP@N-GA composite is good, it still had ~10 % capacity fading,
which may be causes by the irreversible reaction between
electrolyte and LFP active materials.3, 45 Selectively coating the
exposed LFP surface with a thin layer of carbon or metal oxide
may further improve its cycling stability.14
To evaluate the electrochemical properties of pristine LFP@N-
GA in nature, a bare LFP@N-GA electrode was prepared and
tested without the addition of carbon black for contrast. As shown
in Fig. S12†, although the electrochemical performance of
LFP@N-GA was reduced without the addition of carbon black, it
was still superior to commercial LFP/C (with the addition of
carbon black). It can be expected that the conductive agent can be
reduced or even avoided for N-GA modified LFP electrode. The
loading mass of the electrode is an important factor for practical
application, and thus, the electrochemical performances of
LFP@N-GA and commercial LFP/C electrode with different
mass loadings (1.2~5.6 mg·cm-2) were studied. It can be seen
from Fig. S13† that the capacity and cycling stability of
commercial LFP/C decayed rapidly with the increase in the
loading mass due to the increased polarization, especially along
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Page 5 of 29 Energy & Environmental Science
the direction perpendicular to the current collector.1, 21 While for 45
LFP@N-GA, the capacity retention and cycling stability were
still much better than commercial LFP/C, suggesting the inside
3D bicontinuous conductive network effectively facilitate both
5 Li+ and electron transport,4 and thus, reducing the polarization.
The ionic and electronic conductivities of LFP@N-GA and 50
commercial LFP/C were studied by the cyclic voltammetry (CV)
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technique. CV profiles at a fixed scan rate of 0.1 mV·s-1 (Fig. 4a)
revealed that the potential interval between the anodic and
10 cathodic peaks of LFP@N-GA was 168 mV, much lower than
252 mV for commercial LFP/C. Moreover, the redox peak profile 55
of LFP@N-GA was more symmetric and sharper than that of
commercial LFP/C, suggesting that the redox kinetics were
enhanced due to the improved conductivity and the reduced
15 diffusion length along the [010] direction. In addition, both the
cathodic and anodic peak current (Ip) of LFP@N-GA were larger 60
than LFP/C. According to the Randles-Sevcik equation (S14 in
SEI),33 the Li+ diffusion coefficient (DLi) is proportional to Ip-1/2.
Therefore, it could be deduced qualitatively that LFP@N-GA
20 displayed larger DLi during the charge and discharge processes.
65
70
75
Fig. 4 (a) CV curves at a scan rate of 0.1 mV·s-1. (b) Ragone plot of 80
LFP@N-GA in comparison with some advanced energy storage and
conversion devices. (c) Charge current and capacity of LFP@N-GA as a
25 function of charge time. Inset: charge current and efficiency of LFP@N-
GA as a function of charge time. (d) Comparison of the volumetric energy
density of LFP@N-GA and commercial LFP/C.
85
To further evaluate the potential use of LFP@N-GA, its power
and energy densities were estimated based on the weight of
30 LFP@N-GA and a correction factor (the weight ratio of LFP in a
full commercial LFP battery is ~33 wt.%),1, 29 and compared with
some advanced energy storage and conversion devices in the 90
Ragone plot (Fig. 4b). At a low specific power of < 1 kW∙kg-1,
LFP@N-GA exhibited gravimetric energy as high as 110-180
35 Wh∙kg-1, indicating a high energy-storage performance. With
specific power increased to 2-5 kW∙kg-1, the gravimetric energies
sustained 80-100 Wh∙kg-1, suggesting a high-power capability. It 95
is worth noted an ultrahigh power density of 8.6 kW∙kg-1 can still
be realized with an energy density of 49 Wh∙kg-1. Such a
40 LFP@N-GA battery could provide much higher power densities
than current nickel metal hydride battery (100~1000 W∙kg-1) and
LIBs (800~2000 W∙kg-1), while the energy densities are several 100
times greater than that of supercapacitor technology (1~20
Wh∙kg-1).29 These data suggest LFP@N-GA with both high-
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DOI: 10.1039/C4EE03825H
power and high-energy densities has a great potential to build
advanced energy storage and conversion devices for EVs and
HEVs. Considering that charge time is an important limiting
factor for the application of EVs and HEVs,33, 39 the fast-charge
Energy & Environmental Science Accepted Manuscript
performance of LFP@N-GA was tested by charging the cell at
100 C and discharging at 1 C, and the results are shown in Fig. 4c.
It took 28 s to complete the galvanostatic charge process with a
charged capacity of 106 mAh·g-1, which is 71% (inset of Fig. 4c)
of the total charge capacity. In the followed 30 min’s constant-
voltage charge process, the charged capacity was only accounted
for 29%. After charging for 60 s, including 28 s of the
galvanostatic charge and 32 s of the constant-voltage charge, the
total charged capacity arrived 145 mAh·g-1 with an charge
efficiency of 97%, which is better than some industial standard
(30 min for 80% charged capacity). Thus, LFP@N-GA satisfied
another mandatory electrochemical feature for EVs and HEVs.
The above test results demonstrate the good electrochemical
performance of LFP@N-GA and its potential application as the
cathode material for EVs and HEVs, which can be attributed to
three main factors. First, (010) facet orientation of LFP NPs not
only effectively shortens the Li+ diffusion length in LFP crystal
but also enhances the channel density for Li+ diffusion. Moreover,
compared with the current LFP product synthesized by solid-state
methods, the well-crystallized nature of LFP NPs with low Fe•Li
antisite defect concentration provides more expedite Li+ diffusion
paths in LFP crystal. Second, the close contact between LFP NPs
and N-GA guarantees a good electronic contact between them,
which was beneficial for the electron transfer between these two
components. Third, the multi-functions of N-GA play key roles,
which include: (i) the interpenetrating meso- and macro-porous
structure of N-GA provide efficient and rapid pathways for both
Li+ and electron transport in the electrode. Compared with
pristine GA, doping N enhances the electronic conductivity and
wettability of N-GA and thus further improves the electron and
Li+ transport in LFP@N-GA.46 (ii) The loosely-stacking graphene
unit in N-GA offers a large surface area for more LFP NPs to
contact with the electrolyte, which simultaneously prevents their
aggregation. By constructing the 3D porous structure, the re-
agglomeration of graphene, which is ubiquitous for synthesis of
2D graphene modified composites, is effectively prevented; while
the merits of graphene can still be preserved or even enhanced,
such as high surface area and mechanical flexibility. (iii) N-GA
component in the composite electrode could store energy by
electric double layer with a fast capacity response, which buffer
the impact on the LFP component under high current, and
therefore, beneficial for the rate performance and cycling
stability.33 (iv) N-GA takes a relatively small weight ratio of the
composite due to its ultralight weight density and robust
mechanical strength, and serves as a buffer to accommodate the
volume change during Li+ insertion/extraction. Therefore, it can
be deduced that the synergy of the above mentioned factors to
simultaneously address the four primary resistances during
charge and discharge as schematically illustrated in Scheme 1b,
resulting in the good electrochemical performance of LFP@N-
GA. The above analysis also can be used to explain the better rate
performance of LFP@N-GA compared with the previously
reported 2D graphene-modified LFP composites (Fig. S14a†)9, 34,
39, 41, 42, 47-54
as well as other 3D porous LFP/carbon composites
Journal Name, [year], [vol], 00–00 | 5

Energy & Environmental Science
(Fig. S14b†).1, 18, 21-23, 38, 55
It worth mentioned that the tap density of LFP@N-GA was
0.93 g·cm-3, which was lower than that of commercial LFP/C
(1.32 g·cm-3), due to its porous structure. The volumetric energy
5 density of LFP@N-GA and commercial LFP/C were calculated
to be 379/540, 297/264 and 233/113 at 1, 10 and 20 C based on
their tap densities (Fig. 4d),56 respectively. Only at current rates
Published on 06 January 2015. Downloaded by University of Massachusetts - Boston on 06/01/2015 11:08:18.
higher than 10 C, the LFP@N-GA electrode showed advantage
over the commercial LFP/C electrode in the aspect of volumetric
10 energy density. Therefore, although the tap density of the active
material is not the only predictor for volumetric energy density,44
the low tap density of LFP@N-GA is still a critical issue need to
be addressed in future for commercial use.
In summary, we have demonstrated an N-GA modified LFP
15 composite with (010) facet-orientated LFP nanoplatelets wrapped
in 3D porous N-GA. The short and expedite Li+ diffusion paths
through the LFP NPs in combination with the fast Li+ and
electron transport pathways are the key for lowering the primary
resistances during charge and discharge of the electrode, thus
20 leading to both high power density and energy density as well as
good cycling stability. Such a LFP/GA cathode material may
advance the development of high-power LIB for EVs and HEVs,
and the preparation method is independent from the morphology
and the synthesis process of the electrochemically active material
25 (Fig. S15†), and therefore, compatible with many other energy-
storage materials for different applications.
Acknowledgements
BW wishes to thank the China Scholarship Council for providing
a scholarship (No. 20092302110052). Australian Research
30 Council (ARC) is acknowledged for funding FT100100897 and
DP130101870. The Centre for Microscopy and Microanalysis
(CMM) at The University of Queensland is acknowledged.
Notes and references
a
Harbin Institute of Technology, School of Chemical Engineering and
35 Technology, Xidazhi Street, 150001 Harbin, China. Fax:86 45186413721;
Tel: 86 451 86413751; E-mail: wangdianlongwbhit@163.com
b
The University of Queensland, School of Chemical Engineering, St.
Lucia, Brisbane, QLD 4072, Australia. Fax: 61 7 33654199; Tex: 61 7
33469997; E-mail: george.zhao@uq.edu.au
c
40 The University of Queensland, Australian Institute for Bioengineering
and Nanotechnology, St. Lucia, Brisbane, QLD 4072, Australia. E-mail:
w.ghafor@uq.edu.au
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
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 Energy & Environmental Science Page 8 of 29

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Graphic abstract DOI: 10.1039/C4EE03825H

Energy & Environmental Science Accepted Manuscript

LFP@N-GA with (010) facet orientated LFP NPs embedded in N-GA provides both rapid Li+
and electron pathways in the electrode as well as short Li+ diffusion length in LFP crystal.
Published on 06 January 2015. Downloaded by University of Massachusetts - Boston on 06/01/2015 11:08:18.
 Page 9 of 29 Energy & Environmental Science

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DOI: 10.1039/C4EE03825H
Broader context

Energy & Environmental Science Accepted Manuscript

Lithium ion batteries (LIBs) represent an important family of the energy storage and
conversion devices due to their high voltage, large energy density, and good cycling
stability. However, as a power source for electric and hybrid electric vehicles, the
current LIBs technology still needed to be further advanced for improving their power
density. Nanostructured LiFePO4 materials have attracted numerous research interests
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as one of the most promising cathode materials for applications in high-power LIBs.
In this work, we report a facile approach towards high-power LiFePO4 composites by
wrapping (010) facet-orientated LiFePO4 nanoplatelets within three dimensional (3D)
porous nitrogen-doped graphene aerogel. The unique structure endows both rapid
lithium ion and electron pathways in the electrode matrix as well as short lithium ion
diffusion length in LiFePO4 crystal, and thus, resulting in a remarkable
electrochemical performance when used the designed composite as cathode in LIBs.
 Energy & Environmental Science Page 10 of 29

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Energy & Environmental Science Accepted Manuscript

Supplementary Information
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Three-dimensional porous LiFePO4 cathode material

modified with nitrogen-doped graphene aerogel for high-
power lithium ion batteries

Bo Wang,ab Wael Al Abdulla,c Dianlong Wang*a and X. S. Zhao*bd

a
Harbin Institute of Technology, School of Chemical Engineering and
Technology, Xidazhi Street, 150001 Harbin, China. Fax: 86 451 86413721; Tel:
86 451 86413751; E-mail: wangdianlongwbhit@163.com
b
The University of Queensland, School of Chemical Engineering, St Lucia,
Brisbane, QLD 4072, Australia. Fax: 61 7 33654199; Tex: 61 7 33469997; E-
mail: george.zhao@uq.edu.au
c
The University of Queensland, Australian Institute for Bioengineering and
Nanotechnology, St. Lucia, Brisbane, QLD 4072, Australia.
d
Colloge of Chemical Science and Engineering, Qingdao University, Qingdao
207661, China.
 Page 11 of 29 Energy & Environmental Science

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Experimental DOI: 10.1039/C4EE03825H

Energy & Environmental Science Accepted Manuscript

Synthesis

The graphene oxide (GO) used in this work was synthesized from natural graphite using a
modified Hummers method.1 (010) facet orientated LFP NPs were prepared via a
solvothermal way.2 APS-modified LFP NPs were obtained by a surface modification
process.3 LFP@GO was fabricated according to a modified procedure as previously
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reported.4 Briefly, 20 ml GO aqueous suspension (0.75 mg ml-1) was slowly added into 200
ml APS-modified LFP NPs aqueous dispersion (0.4 mg ml-1) under magnetic stirring. The
LFP@GO was then obtained after centrifugation and washing with distilled water.

LFP@N-GA was prepared by hydrothermal assembly of LFP@GO and additional GO sheets

in a urea aqueous solution, subsequently combining with freeze-drying and thermal treatment.
In a typical process, LFP@GO was homogeneously dispersed in 13 ml urea (70 mg ml-1)
aqueous solution followed by the addition of 2 ml aqueous GO suspension (7.5 mg ml-1), and
then sealed in a 20 ml polytetrafluorethylene (Teflon)-lined autoclave. After hydrothermal
treatment at 120 °C for 3 h, the autoclave was naturally cooled to room temperature; the
obtained N-doped graphene hydrogel embedded with LFP NPs was taken out and freezing
dried, followed by annealing at 600 °C for 2h in reductive (5 vol.% of hydrogen in argon)
atmosphere to generate 3D LFP@N-GA. N-GA and GA were prepared by assembly of GO in
a similar hydrothermal process in the presence and absence of urea, respectively.

Characterization

X-ray diffraction (XRD) patterns were collected on a Rigaku diffractometer using Cu Kα

radiation. Raman spectra were recorded on a Thermo-Fischer Almega dispersive Raman
instrument. The instrument was fitted with 633 nm lasers. Powder samples were measured at
room temperature using the microscope accessory with a 50x apertures with at least 132
scans. Fourier transform infrared spectroscopy (FTIR) spectra were collected from a Nicolet
5700 FTIR spectrometer with 64 scans at a resolution of 4 cm-1. Nitrogen sorption isotherms
were measured on Tristar II 3020 at the liquid nitrogen temperature. Before measurement, the
sample was degassed at 150 °C for 24 h. The specific surface area was calculated using the
multipoint Brunauer-Emmett-Teller (BET) method. The pore size distribution was computed
using the Barrett-Joyner-Halenda (BJH) method. Thermal gravimetric analysis (TGA) was
conducted in air from room temperature up to 800 °C at a heating rate of 10 °C min-1 using a
Mettler Toledo TGA/DSC1 STARe System (Mettler Toledo, USA & Switzerland). The
electronic conductivity was measured at room temperature using a four-probe conductivity
test metre. The morphology and microstructure were characterized using JEOL 7001, 6300
field-emission scanning electron microscope (FESEM), JEOL 1010 transmission electron
microscope (TEM), and FEI Tecnai 20 high-resolution (HRTEM). Chemical compositions
were analysed using the X-ray photoelectron spectroscopy (XPS, Kratos Axis ULTRA)
technique incorporating a 165 mm hemispherical electron energy analyser.
 Energy & Environmental Science Page 12 of 29

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Electrochemical measurements DOI: 10.1039/C4EE03825H

Energy & Environmental Science Accepted Manuscript

Before electrode fabrication, the obtained LFP@N-GA monolith was ground into powder.
Then, the powder was mixed with carbon black and polyvinylidene fluoride (PVDF) in a
mass ratio of 8:1:1. The mixture was pasted onto the aluminum foils and dried at 80 ℃ for 10
h in vacuum oven before cut into disks with diameter of 1.5 cm. The disks were further
compressed at a given pressure. The N-GA electrode was prepared using the same procedure
to investigate the electrochemical performance of N-GA. The bare LFP@N-GA electrode
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without carbon black but with the same 10 wt.% of PVDF was also prepared for comparison
purpose. To investigate the influence of the loading mass on the electrochemical performance,
the loading mass of each disk was controlled by using different layers of the adhesive tape to
control the thickness of the coating materials. The average loading masses corresponding to 1
layer, 2 layers, 3 layers and 5 layers adhesive tape thicknesses were about 1.2, 2.1, 3.3, 5.6
mg·cm-2, respectively. Without special explanation, the electrochemical data were
corresponded to 5 layer adhesive tape thicknesses (~ 100 um). The CR2032 coin-type cells
were assembled in an argon-filled glove box using the prepared disks as cathode, metal
lithium disks as anode, Celgard 2500 (polypropylene) as separator, and 1 M of LiPF6 in
ethylene carbonate (EC)/ dimethyl carbonate (DMC)/ diethyl carbonate (DEC) solvent (1:1:1
in volume) as electrolyte. The cells were charged and discharged over a potential range of
2.5-4.2 V (vs. Li/Li+) at different current rates. Note that “n C” means that the
charge/discharge current is set up to achieve the nominal capacity (170 mAh∙g-1) in “1/n”
hours. Among the components of the prepared LFP@N-GA electrodes, we regarded
LFP@N-GA as the active material, so that the specific capacities were calculated based on
the total mass of LFP NPs and N-GA.

Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) data were
collected on an electrochemical workstation (CHI 660D or PARSTAT 2273). The CV
measurement was carried out at a scanning rate of 0.1 mV∙s-1 between 2.5 and 4.2 V. The EIS
measurement was performed over a frequency range of 100 kHz to 10 mHz with an applied
amplitude of 5 mV. The parameters of the equivalent circuit were calculated and analyzed by
computer simulations using the ZSimpWin software.
 Page 13 of 29 Energy & Environmental Science

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S1. Morphology information of the as-prepared LFP NPs DOI: 10.1039/C4EE03825H

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Fig. S1† (a) Low- and (b) high-magnification SEM images of the as-prepared LFP NPs, showing the length,
width and thickness of the LFP NPs are ranged of 150-200 nm, 70-100 nm and 30-40 nm, respectively, as well
as the severe agglomeration between LFP NPs.
 Energy & Environmental Science Page 14 of 29

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Energy & Environmental Science Accepted Manuscript

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Fig. S2† SEM images of LFP@GO, revealing LFP NPs were anchored on GO. With respect to LFP NPs, the
presence of crumpled and rough textures on the surfaces of LFP@GO was associated with the flexible and
corrugated nature of GO. It should be noted that some exposed GO surface can still be reserved after the
electrostatic attraction process between APS-modified LFP NPs and GO. These GO surface will cross-link with
the additional GO in the hydrothermal process for the construction of GA.
 Page 15 of 29 Energy & Environmental Science

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Fig. S3† The photograph illustration of the synthetic procedure of LFP@N-GA. It can be seen, through the
electrostatic attraction between APS-modified LFP NPs and GO, the obtained LFP@GO suspension was quite
uniform and stable. After the hydrothermal process, LFP@GO crossed linked with the additional GO and
convert to a hydrogel successfully.
 Energy & Environmental Science Page 16 of 29

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Fig. S4† SEM images of LFP@N-GA, showing LFP NPs were embedded within a porous GA.
 Page 17 of 29 Energy & Environmental Science

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S5. Nitrogen isothermal adsorption/desorption measurement of LFP@N-GA,DOI:
LFP NPs
10.1039/C4EE03825H
and N-GA

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Fig. S5† (a) Nitrogen adsorption and desorption isotherm of LFP@N-GA. Inset: The pore-size distribution plot
calculated by the BJH formula from the desorption branch isotherm. (b) Nitrogen adsorption and desorption
isotherm of LFP NPs and N-GA.

The Brunauer-Emmett-Teller (BET) specific surface area of LFP@N-GA, LFP NPs and N-
GA were 199.30, 29.07 and 436.76 m2·g-1, respectively. The linear combination of the
surface area of LFP NPs and N-GA by weight fraction (see Fig. S5†) can be calculated
according to Eq. (1):

Sc = SLFP NPs × wLFP NPs + SN-GA × wN-GA (1)

where Sc is the calculated linear-combined surface area (m2·g-1), SLFP NPs is the surface area of
LFP NPs (29.07 m2·g-1), wLFP NPs is the weight fraction of LFP NPs (84.64 wt.%), SN-GA is the
surface area of N-GA (436.76 m2·g-1), and wN-GA is the weight fraction of N-GA (15.36 wt.%).
The Sc was calculated to be (91.69 m2·g-1), which was much lower than the BET surface area
of LFP@N-GA, indicative of an alleviative agglomeration between LFP NPs in LFP@N-GA.
 Energy & Environmental Science Page 18 of 29

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Fig. S6† TGA curves of LFP@N-GA of LFP NPs, demonstrated the weight fractions of LFP NPs and N-GA in
LFP@N-GA were 84.64 wt.% and 15.36 wt.%, respectively.
 Page 19 of 29 Energy & Environmental Science

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Fig. S7† Raman spectra of GO, N-GA and LFP@N-GA. The ID/IG of GO, N-GA and LFP@N-GA were 0.99,
1.30 and 1.33 respectively, suggesting a more disordered structure after N-doping. The shift for both D and G
bond between N-GA and LFP@N-GA indicated of a charge transfer between N-GA and LFP NPs component in
LFP@N-GA.
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Energy & Environmental Science Accepted Manuscript

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Fig. S8† (a) Low- and (b) high-magnification SEM images of commercial LFP/C, revealing that the particles
are in irregular in shape with particle size ranging from tens of nm to micrometer. Severe particle agglomeration
can also be seen. On contrast to LFP@N-GA, the BET surface area of the commercial LFP/C was measured to
be only about 9.3 m2·g-1 without pores existence.5
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S9. Comparison of the middle discharge voltage of commercial LFP/C and LFP@N-GA
DOI: 10.1039/C4EE03825H

Energy & Environmental Science Accepted Manuscript

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Fig. S9† The dependency of the middle discharge voltage on current rate in the range of 0.2 C to 100 C for
commercial LFP/C and LFP@N-GA.
 Energy & Environmental Science Page 22 of 29

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S10. Electrochemical performance of N-GA DOI: 10.1039/C4EE03825H

Energy & Environmental Science Accepted Manuscript

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Fig. S10† Electrochemical performance of N-GA: (a) Charge/discharge profiles at current rate of 1 C (the
current rate is set up based on the nominal capacity of LFP 170 mAh∙g-1); (b) Cycling performance at 1C and (c)
CV profiles at a fixed scan rate of 1 mV·s-1. It can be seen N-GA displayed a typical capacitive capacity of 53
mAh·g−1 (112 F·g−1). There was no capacity fading after 600 cycles at this current rate, suggesting a good
cycling stability. From the CV curves, it can be seen there were no cathodic/anodic current peaks, indicative of a
good electrochemical stability in the chosen electrochemical potential range (2.5 - 4.2 V).
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S11. Morphology information of LFP@N-GA after cycling test DOI: 10.1039/C4EE03825H

Energy & Environmental Science Accepted Manuscript

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Fig. S11† TEM images of LFP@N-GA electrodes after 1000 electrochemical cycles at 10 C, revealing LFP NPs
remain well-confined within N-GA after cycling test. The nanoparticles irregularly dispersed around the
samples are carbon black, which widely be used as the conductive agent.
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S12. Electrochemical performance of the bare LFP@N-GA electrode DOI: 10.1039/C4EE03825H

Energy & Environmental Science Accepted Manuscript

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Fig. S12† Electrochemical performance of electrode LFP@N-GA (corresponding to 1 layer adhesive tape
thicknesses) in the absence of carbon black: (a) Rate capabilities from 0.2 C to 20 C; (b) Charge/discharge
profiles at current rate ranging from 0.2C to 20 C; (c) The dependency of the middle discharge voltage on
current rate in the range of 0.2 C to 20 C and (d) Cycling performance combined with Coulombic efficiency at
10 C. Such an electrode exhibited discharge capacities of 110 and 66 mAh∙g-1 at 10 and 20 C, respectively. The
reversible capacity of bare LFP@N-GA electrode sustained 86 mAh·g-1 after 1000 cycles at 10 C with a
capacity retention of 80%. Although the electrochemical performance of the carbon black-free LFP@N-GA
electrode was poorer than that of the electrode with carbon black, it was still superior to commercial LFP/C
(with the addition of carbon black).
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S13. Electrochemical performance of LFP@N-GA and commercial LFP/C electrode
DOI: 10.1039/C4EE03825H
with different mass loading

Energy & Environmental Science Accepted Manuscript

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Fig. S13† Electrochemical performance of LFP@N-GA and commercial LFP/C electrode with different mass
loading: (a, b) rate performance and (c) cycling stability at 10C. It can be seen the capacity and cycling stability
of commercial LFP/C decayed rapidly with the increase in loading mass due to increased polarization,
especially along the direction perpendicular to the current collector. While for LFP@N-GA, the capacity
retention and cycling stability were still much better than commercial LFP/C, suggesting the inside 3D
bicontinuous conductive network effectively facilitate both Li+ and electron transport kinetics, and thus,
reducing the polarization.
 Energy & Environmental Science Page 26 of 29

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S14. Li+ diffusion coefficient during charge/discharge View Article Online

DOI: 10.1039/C4EE03825H

Energy & Environmental Science Accepted Manuscript

Randles-Sevcik equation,5 which is always used to calculate the Li+ diffusion coefficient
during charge/discharge, is represented in Eq. (2):

𝐼𝑝 = 2.69 × 105 𝑛3/2 𝐴𝐶0 𝐷𝐿𝑖 1/2 𝑣 1/2 (2)

where Ip is the peak current (A), n is the number of electrons transferred per molecule during
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the electrochemical reaction (for LFP, n = 1), A is the active surface area of the electrode
(cm2), C0 is the molar concentration of Li+ in LFP (2.28 × 10-2 mol∙cm-3), DLi is the Li+
diffusion coefficient in LFP (cm2∙s-1), and v is the scanning rate (V∙s-1). According to this
formula, DLi is proportional to Ip-1/2.
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S15. Comparison of the rate capability of LFP@N-GA with previously reported 2D View Article Online
DOI: 10.1039/C4EE03825H
graphene-modified LFP composites and 3D porous LFP/carbon composites

Energy & Environmental Science Accepted Manuscript

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Fig. S14† Comparison of the rate capability of LFP@N-GA with previously reported 2D graphene-modified
LFP composites (a) and 3D porous LFP/carbon composites (b).
 Energy & Environmental Science Page 28 of 29

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S16. The extension of the preparation method DOI: 10.1039/C4EE03825H

Energy & Environmental Science Accepted Manuscript

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Fig. S15† The extension of the preparation method to other LFP materials with different morphlogies: (a) SEM
and TEM (inset) image showing the nanoparticle mopholgy of LFP compnent; (b) SEM and TEM (inset) image
revealing the nanorod mopholgy of LFP compnent; (c) SEM images showing the hierarchical microshpere
mopholgy of LFP compnent, and (d) SEM images revealing the microrhomb mopholgy of LFP compnent.
Moreover, the method can be easliy transfered to other electrochmical active materials, such as LiMn2O4, SnO2
and SiO etc., which is being carried out.
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1. Z. Xiong, L. L. Zhang, J. Ma and X. S. Zhao, Chem. Commun., 2010, 46, 6099-6101.DOI: 10.1039/C4EE03825H
2. L. Wang, X. He, W. Sun, J. Wang, Y. Li and S. Fan, Nano Lett., 2012, 12, 5632-5636.

Energy & Environmental Science Accepted Manuscript

3. W.-B. Luo, S.-L. Chou, Y.-C. Zhai and H.-K. Liu, J. Mater. Chem. A, 2014, 2, 4927-4931.
4. W. Wei, S. Yang, H. Zhou, I. Lieberwirth, X. Feng and K. Müllen, Adv. Mater., 2013, 25, 2909-
2914.
5. B. Wang, Q. Wang, B. Xu, T. Liu, D. Wang and G. Zhao, RSC Adv., 2013, 3, 20024-20033.
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