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A Hierarchical Porous C@LiFePO4/Carbon Nanotubes
Microsphere Composite for High-Rate Lithium-Ion
Batteries: Combined Experimental and Theoretical Study
Bo Wang,* Tiefeng Liu, Anmin Liu, Guijing Liu, Lei Wang, Tiantian Gao,
Dianlong Wang,* and Xiu Song Zhao*
Lithium-ion batteries (LIBs) have been widely investigated
in the past two decades for energy storage in electric vehicles
(EVs) and hybrid electric vehicles (HEVs) for the purpose of
displacing fossil fuel and remitting environmental issues.[1,2]
Being a promising candidate of LIBs cathode materials, oli-
vine-structured LiFePO4 (LFP) possesses numerous advan-
tages including low cost, environmental compatibility, superior
thermal stability, and safety.[3] The major problems associated
with LFP however still lie in the fact of its poor electronic con-
ductivity and low Li+ diffusivity, and thus limiting its high-
rate (>50 C) performance and practical application in EVs and
HEVs.[4–6] Correspondingly, various strategies have been devel-
oped for addressing these problems with different levels of suc-
cess, including doping with alien ions,[7,8] optimizing particle
size and morphology,[9–12] and surface modification with elec-
tronic and/or ionic conductive layers.[13–15]
Among them, carbonaceous materials have been recognized
as one of the preferred materials for wiring the surface of LFP
particles for improving their electrochemical performance.[16,17]
In general, the electronic conductivity of graphitized carbon is
considered to be superior to amorphous carbon (C), and various
kinds of graphitized carbon were introduced to decorate LFP
materials, e.g., carbon nanofiber,[18,19] carbon nanotubes[20–22]
(CNTs) and graphene.[23–25] Especially, CNTs have shown great
potential for practical applications with superior electrical,
mechanical, and surface properties as well as easy for mass
production and low cost.[26,27] For the research of CNTs modi-
fied LFP composites, the main efforts have been focused on
Dr. B. Wang, Dr. T. Liu, Dr. A. Liu, Dr. G. Liu,
Dr. L. Wang, Dr. T. Gao, Prof. D. L. Wang
MIIT Key Laboratory of Critical Materials Technology
for New Energy Conversion and Storage
School of Chemistry and Chemical Engineering
Harbin Institute of Technology
150001 Harbin, China
E-mail: wangbo19880804@163.com;
wangdianlongwbhit@163.com
Prof. X. S. Zhao
School of Chemical Engineering
The University of Queensland
Brisbane 4072, Australia
E-mail: george.zhao@uq.edu.au
Prof. X. S. Zhao
Institute of Materials for Energy and Environment
School of Materials Science and Engineering
Qingdao University
Qingdao 207661, China
DOI: 10.1002/aenm.201600426
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improving electrical conductivity, while relatively less work
were aimed to optimize regularly desired microstructure for
accelerating mass (Li+) transfer and enhancing tap density
simultaneously (Table S1, Supporting Information).[20–22,28,29]
Actually, as has been recognized that the Li+ transport in elec-
trolyte to approach the active site may also be rate-limiting
factor at high rates,[13,30] and the tap density directly influence
the volumetric energy density of the final LIBs, which is also
very important for EVs and HEVs.[10,16] On the other side, com-
pared with performance study, the theoretical research of this
area was relatively rare.[1,16] Therefore, it is still highly desirable
to design an ideal-structured LFP/CNTs composite with sub-
stantially improved electronic and ionic transport kinetics as
well as high tap density for EVs and HEVs applications, and the
inherent reason for electrochemical performance improvment
of such kind of composite was also needed to deeply undstood
from the theoretical aspect.
Herein, we presented a unique hierarchically porous C@LFP/
CNTs microsphere composite via a facile hydrothermal approach
combined with high-temperature calcinations using the relative
low-cost Fe3+ source as the raw material. In such a composite,
CNTs as an electronic conductive component were in situ and
uniformly embedded into the LFP open porous microspheres
to form a conductive CNTs network, meanwhile the interlaced
pore networks facilitated rapid Li+ supplies, which made each
C@LFP/CNTs microsphere to be an effective microreactor
for fast electrochemical reactions. Meanwhile, the amorphous
carbon bridged the CNTs network, and thus further improved
the electronic conductivity of the whole composite. Besides, the
microsphere morphology guaranteed a large tap density of the
composite for high volumetric energy density supplies. It should
be noted that CNTs is also an electrochemical capacitor material
by storing energy in electric double layer. As reported previously,
in a composite electrode, the capacitor component could promote
a fast capacity response, which buffered the influence on LIB
component under high-rate charge or discharge, and thereby,
beneficial for its rate performance and cycling stability.[13] For
comparison purpose, a composite decorated by single amor-
phous carbon (C@LFP) was also prepared and investigated.
The electrochemical test results demonstrated that the C@LFP/
CNTs composite indeed exhibited impressive rate capability
(73 mAh g−1 at 60 C) and cycling stability (98% capacity reten-
tion over 1000 cycles at 10 C) combined with a high volumetric
energy density (443 Wh L−1 at 10 C). To deeper understand the
improved electrochemical performance of C@LFP/CNTs, the
compound interfacial property of LFP and CNTs were further
studied by a density functional theoretical (DFT) calculation.
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Scheme 1.  Schematic illustrating the preparation process of C@LFP/CNTs.
Scheme 1 illustrates the preparation process of C@LFP/
CNTs. In brief, the cations including Li+ and Fe3+, were firstly
adsorbed to the outside surface of the negatively charged CNTs
(Figure S1, Supporting Information) by electrostatic interac-
tion (Figure S2, Supporting Information).[29,31] After that, with
the addition of PO43−, Li3PO4, and FePO4 as the intermedi-
ates anchored on CNTs through a fast precipitation reaction
between Li+ and PO43− as well as Fe3+ and PO43−.[12,17] During
the subsequent hydrothermal process, Li3PO4 and FePO4 nano-
particles grew and assembled into porous microspheres fol-
lowing a “nucleation-growth-assembly-fracture” mechanism
(Figure S3, Supporting Information) with CNTs simultaneously
embedded in,[32] due to the co-shaping effect of both EG and EN
(Figure S4, Supporting Information) for reducing the surface
free energy of the dispersed particles.[9,10] After the ultrasonic-
assisted rheological phase process and carbothermal treatment,
the LFP precursor turned into LFP crystal and the sucrose
was thermally decomposed into amorphous carbon without
destroyed its porous structure, and the C@LFP/CNTs com-
posite was finally obtained.
The morphology and microstructure characterizations of
both the precursor and product of C@LFP/CNTs are provided
in Figure 1. The scanning electron microscopy (SEM) image of
the precursor at low magnification (Figure 1a) shows LFP/CNTs
were perfect microspheres with diameter of 3–5 μm, which
were assembled by the interweaved nanoplates with thickness
ranged from several to dozens nm forming an open porous
structure (Figure 1b). Meanwhile, from the high magnification
SEM images (Figure 1c and Figure S5, Supporting Informa-
tion) of the breakage in a single LFP/CNTs microsphere, it can
be seen that CNTs were uniformly embedded in, suggesting the
CNTs had been successfully incorporated into the microsphere.
Further, the transmission electron microscope (TEM) images
at different magnifications (Figure 1d,e) also confirmed such a
similar phenomenon. For the C@LFP/CNTs product, as shown
in Figure 1f, the morphology and particle size were in general
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similar to those of the LFP/CNTs precursor, although the thick-
ness of the nanoplates was increased to some extent (up to
several tens nm) due to the coated amorphous carbon layer,
which indicated the original morphology of the precursor was
well maintained after the carbothermal treatment.[9,10] Analo-
gously, the inner CNTs can also be observed in the breakage
of C@LFP/CNTs microspheres, as shown in Figure 1g. From
the TEM image of a fragment in C@LFP/CNTs (Figure 1h), it
can be seen the LFP nanoparticles (LFP NPs), which assembled
to the nanoplates (Figure 1f,g), were anchored in a CNTs and
amorphous carbon co-constructed framework. The high-resolu-
tion TEM (HRTEM) image shown in Figure 1i reveals the LFP
nanoparticles (≈40 nm in diameter) coated with a carbon layer
(≈3 nm thickness) was tightly anchored on CNTs and further
surrounded by an amorphous carbon framework. Such a close
contact guarantees a good electronic contact between LFP NPs
and CNTs.[24,33]
As to the precursor and product of C@LFP (Figure S6, Sup-
porting Information), the morphology and microstructure were
similar with those of C@LFP/CNTs except for without of the
embedded CNTs in the open porous structure.
Inspired by this finding, a graphene (G) modified porous
C@LFP composite-C@LFP/G was further synthesized for
comparison, in which a 2D graphene material with size ranged
from several to several tens um was used as the graphitized
carbon component.[34] From the SEM images of LFP/G pre-
cursor (Figure S7, Supporting Information), it can be seen
due to the large 2D structure of G, which was only wrapped
on the surface of LFP porous sphere. Besides, it should be
noted some open pores of LFP spheres were sealed by gra-
phene wrapped layer, which is adverse to electrolyte penetration
and mass transfer.[35] Moreover, compared with the inner-
embedded structure for CNTs, such an outside-wrapped mode
for G has no contribution to the interior electronic conductivity
of LFP, and thus, leading to a limited improvement on elec-
tronic conductivity of the whole composite.[20] According to the
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Figure 1.  a–c) SEM images of LFP/CNTs precursor at different magnifications, suggesting LFP/CNTs were perfect microspheres with CNTs uniformly
embedded in. d,e) TEM images of LFP/CNTs precursor. f,g) SEM images of C@LFP/CNTs, revealing the original morphology of the precursor was well
maintained after the carbothermal treatment. h,i) TEM and HRTEM images of C@LFP/CNTs, indicating the LFP NPs coated with a carbon layer was
tightly anchored on CNTs and further surrounded by an amorphous carbon framework.

conductivity test results, the electronic conductivity of C@LFP/
CNTs (7.71 × 10−2 S cm−1) was almost three times higher than
C@LFP/G (2.73 × 10−2 S cm−1). Therefore, it is not difficult to
draw the conclusion that the dimension and structure of the
graphitized carbon component has an important influence on
the compound mode and property of the final composite.[16]
The elemental mapping results of C@LFP/CNTs detected by
an energy-dispersive X-ray spectrometer were shown in Figure S8
in the Supporting Information. It is clearly seen that the Fe, P,
and O distributions were quite uniform with the same sphere
shape, indicative of a LFP sphere; while C was also well dis-
tributed over all scope, suggesting uniformly distributed CNTs
and amorphous carbon co-constructed conductive network.[7]
The elemental analysis technique (Vario EL Cube, Elementar,
Germany) was further employed to measure the carbon con-
tent in the samples.[23] The results confirmed that the carbon
content in LFP/CNTs precursor was 2.78 wt%, which was
similar with the ratio of the raw CNTs addition. As to C@LFP
and C@LFP/CNTs products, the tested carbon contents were
6.39 and 6.17 wt%, respectively, revealed the total carbon con-
tent of C@LFP and C@LFP/CNTs product was comparable
with each other. However, the electronic conductivity of C@
LFP/CNTs tested by a four-probe conductivity metre was
7.71 × 10−2 S cm−1, which was ≈10 times higher than C@LFP
(5.91 × 10−3 S cm−1); indicating that the CNTs and amorphous
carbon co-constructed conductive network is more effective
than the single amorphous carbon in improving the electronic
conductivity, owing to the more efficient electron-transporting
property of the graphitized CNTs component.[22,36]
The porous structures of C@LFP/CNTs and C@LFP were
further characterized by nitrogen isothermal adsorption/de-
sorption measurement. Based on the Barrett–Joyner–Halenda
model, the pores of both the products all ranged mostly between
2 and 100 nm (Figure S9a, Supporting Information). However,
the pore volume of C@LFP/CNTs was obviously higher than
that of C@LFP. As expected, a large Brunauer–Emmett–Teller
(BET) specific surface area of C@LFP/CNTs (Figure S9b, Sup-
porting Information) was realized (74.71 m2 g−1), which was
much higher than the linear combination of the BET surface
area of C@LFP (49.02 m2 g−1) and CNTs (202.59 m2 g−1) by
weight fraction, and thus, suggested an alleviative agglomera-
tion between LFP NPs in C@LFP/CNTs.[13,33] The high surface

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Figure 2.  a) XRD patterns of C@LFP, C@LFP/CNTs, CNTs, and the standard LFP (JCPDS No. 81-1173). b) Representational crystal structure of LFP.
c) XPS survey of C@LFP/CNTs. d,e) High resolution XPS spectrum of Fe 2p and C 1s for C@LFP/CNTs. f) Raman (green line) and FTIR (blue line)
spectra of C@LFP/CNTs.
area of C@LFP/CNTs combined with its large macro- and
meso-porous feature, are favorable for electrolyte accessibility
and rapid Li+ transport.[33]
Figure 2a shows the XRD patterns of C@LFP and C@LFP/
CNTs as well as CNTs. For both C@LFP and C@LFP/CNTs, all
diffraction peaks were perfectly indexed to olivine LFP with the
space group of Pnma (JCPDS No. 81-1173, Figure 2b). There
was no clear observation of the (002) diffraction peak of CNTs
because of its low content.[15,37] The calculated crystal lattice
parameters are a = 6.0073 Å, b = 10.3403 Å, c = 4.6979 Å for
C@LFP, and a = 6.0025 Å, b = 10.3386 Å, c = 4.6946 Å for C@
LFP/CNTs. Both sets of parameters are very close to the values
of standard LFP (a = 6.019 Å, b = 10.347 Å, c = 4.704 Å), sug-
gesting a high crystallinity of both the samples.[24]
The X-ray photoelectron spectroscopy (XPS) was carried
out to further examine the composition and chemical state of
C@LFP/CNTs. The wide XPS spectrum shown in Figure 2c
exhibited that the binding energy of Li 1s, P 2p, and O 1s were
determined to be 56.2, 133.4, and 531.3 eV, respectively, with
the reference binding energy at 284.8 eV for the C 1s peak.
Figure 2d presented the high resolution XPS spectrum of Fe 2p
of C@LFP/CNTs. The binding energy positioned at 710.7 and
724.2 eV were ascribed to Fe 2p3/2 and Fe 2p1/2, respectively,
with an energy separation (ΔEFe) of 13.5 eV, which matched
well with previously reported spectra of Fe2+ in LFP.[38,39]
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Figure 2e exhibited the high resolution XPS spectrum of C 1s
of C@LFP/CNTs. After deconvolution, the C 1s spectrum dis-
played the lower binding energy featured at 284.8 eV corre-
sponding to C C carbon and the higher binding energy featured
at 287.0 and 285.9 eV followed by a shoulder at 288.7 eV, which
were typically assigned to C–O/C–O–C, C O and O–C O
arising from the residual epoxide, hydroxyl and carboxyl func-
tional groups in CNTs.[26,40,41]
Further structural information about C@LFP/CNTs was
obtained from the Raman spectrum (green line in Figure 2f).
The bands at 200–520 and 520–1100 cm−1 correspond to the
Raman vibrations of Fe–O and PO43−;[42,43] while the bands
observed at around 1312 and 1596 cm−1 were attributed to
the characteristic D and G bands of the carbon materials
(C and CNTs).[44,45] The G band is due to graphitized carbon,[46]
whereas the D band is attributed to the defects in graphitized
structure,[47] which mainly arising from CNTs and amorphous
carbon components in C@LFP/CNTs, respectively.[17] As to the
Li+ diffusing process in LFP lattice, it is highly influenced by
two important factors: diffusion length and Fe•Li antisite defect
(Figure 2b).[42,48,49] Considering the particle size of LFP NPs in
C@LFP/CNTs is already reduced to nanoscale (Figure 1), the
other influence factor—Fe•Li antisite defect was further exam-
ined by Fourier transform infrared spectroscopy (FTIR, blue
line in Figure 2f). As can been seen, the infrared absorption
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Figure 3.  Electrochemical properties: a) charge/discharge profiles at 0.2 C, inset: the magnified selected-region comparing the potential plateaus,
b) rate capabilities from 0.2 to 60 C, c) cycling stabilities combined with Coulombic efficiency at 10 C of C@LFP and C@LFP/CNTs, and (d) charge
current and capacity as well as charge efficiency of C@LFP/CNTs as a function of charge time.
bands at 951 cm−1, which corresponded to the symmetric
stretching vibration of P–O, was close to that of defect-free LFP,
indicative of a low Fe•Li antisite defect concentration in the LFP
crystals.[42,50]
An electrochemical study was then performed to compare
the electrochemical performance of C@LFP and C@LFP/
CNTs. Figure 3a exhibited the typical charge/discharge profiles
at a small current rate of 0.2 C. The discharge capacity of C@
LFP/CNTs was 155 mAh g−1, much higher than that of C@
LFP (141 mAh g−1). Furthermore, as revealed in the inset of
Figure 3a, the polarization between the charge and discharge
plateaus of C@LFP/CNTs was smaller than C@LFP and the
charge/discharge potential-plateau of C@LFP/CNTs was more
stable than C@LFP, indicating that the kinetics and utilizations
of LFP were further improved after the addition of CNTs, which
co-constructed a more effective conductive network with the
amorphous carbon component.[13,51]
The rate capabilities of C@LFP and C@LFP/CNTs were eval-
uated from 0.2 to 60 C, as shown in Figure 3b. It can be seen,
with the rising of current rate, the difference in rate capabilities
between these two electrodes became more and more obvious.
C@LFP/CNTs presented higher discharge capacities of 126,
115, and 102 mAh g−1 at 5, 10, and 20 C, respectively, while
C@LFP only presented 92, 71, and 50 mAh g−1 at these corre-
sponding current rates. C@LFP/CNTs even exhibited a capacity
of 73 mAh g−1 at 60 C, but C@LFP was almost invalid at such a
high current rate. On the other hand, for power batteries used
in EVs and HEVs, constant-power discharge is the conventional
discharge mode.[22] And thus, the discharge voltage as the other
significant factor for LIBs was further investigated. Figure S10
in the Supporting Information displayed the variations of the
middle discharge voltage (at half of the maximum discharge
capacity) in dependence of current rates for both the LFP
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electrodes. The curves clearly revealed C@LFP/CNTs exhibited
higher middle discharge voltages at the whole tested current
rates (0.2–60 C). For instance, it exhibited a value of 3.03 V at
20 C, which was much higher than 2.79 V for C@LFP. There-
fore, the larger discharge capacity combined with the higher
middle discharge voltage implied the designed C@LFP/CNTs
will deliver both higher power density (power = voltage × cur-
rent) and energy density (energy = capacity × voltage) when
used as the cathode material for LIBs.
After cycling at 10 C for 1000 times, the reversible capacity of
C@LFP/CNTs sustained at 113 mAh g−1 with a capacity reten-
tion of 98% (Figure 3c). The corresponding average Coulombic
efficiency approached 99.3%, suggested the highly reversible
Li+ insertion/extraction kinetics.[52] The cycling stability of
C@LFP/CNTs was also superior to C@LFP, which sustained
a reversible capacity of 61 mAh g−1 with capacity retention of
86% after the same test. The better cyclability of C@LFP/CNTs
may attribute to the fast capacity response of CNTs component,
which buffered the impact to LFP under high-rate cycling con-
dition (Figure S11, Supporting Information).[53] Meanwhile,
the embedded CNTs network played a role of skeleton in the
monodispersed C@LFP/CNTs microsphere, which enhanced
its holistic structure robustness, and thus, further improved
the cycling stability of the electrode (Figure S12, Supporting
Information).[54]
For the practical application of EVs and HEVs, charge time
is an important limiting factor.[13,55] Here, the fast-charge per-
formance of C@LFP/CNTs was evaluated by charging the cell
at 20 C and discharging at 1 C as shown in Figure 3d. The gal-
vanostatic charge process took 142 s with a charged capacity of
117 mAh g−1, which is 76% of the total charge capacity. In the
following 30 min constant-voltage charge process, the charged
capacity was only accounted for 24% (37 mAh g−1). After
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Figure 4.  a) CV profiles with scanning rate of 1 mV s−1. b) EIS plots in the frequency region of 106–0.01 Hz, insets 1): EIS plots at the high frequency
region, and inset 2): the simplified equivalent circuit of C@LFP and C@LFP/CNTs. c) Comparison of the volumetric energy density of C@LFP/CNTs
and commercial LFP/C. d) Schematic illustration of the bicontinuous pathways for both Li+ and electrons constructed by the pores and CNTs-based
network in C@LFP/CNTs.

charging for 200 s, including 142 s galvanostatic charge and
58 s constant-voltage charge, the total charged capacity achieved
135 mAh g−1 with a charge efficiency of ≈90%, which is much
better than some industrial standards (30 min accomplished
80% charged efficiency). Thereby, C@LFP/CNTs satisfied
another essential requirement for EVs and HEVs.
The electronic/ionic kinetics feature of C@LFP and C@
LFP/CNTs were further contrastively studied by cyclic voltam-
metry (CV) and electrochemical impedance spectrum (EIS)
techniques. The CV curves with scanning rate of 0.1 mV s−1
(Figure 4a) revealed that the potential interval between the
cathodic and anodic peaks of C@LFP/CNTs was 155 mV, much
lower than 215 mV for C@LFP. Besides, the redox peak profile
of C@LFP/CNTs was more sharp and symmetric, indicating
the redox kinetics was improved due to the enhanced conduc-
tivity. Moreover, both the anodic and cathodic peak currents (Ip)
of C@LFP/CNTs were higher than C@LFP. Therefore, it could
be deduced qualitatively that C@LFP/CNTs displayed larger Li+
diffusion coefficient (DLi) during the charge and discharge pro-
cesses according to Randles–Sevcik formula (S14 in Supporting
Information),[42] in which DLi is proportional to Ip−1/2. The
Nyquist plots (Figure 4b and inset 1)) revealed higher electronic
conductivity and lower charge-transfer resistance of C@LFP/
CNTs electrode. With the simplified equivalent circuit (inset 2)
of Figure 4b), the electronic conductivity and total resistance
of C@LFP/CNTs electrode were fitted to be 0.26 S cm−2 and
77.5 Ω cm−2, superior to 0.16 S cm−2 and 244.7 Ω cm−2 of C@
LFP electrode (Table S2, Supporting Information).[42] The DLi
at open circuit was calculated to be 1.73 × 10−13 cm2 s−1 for
C@LFP/CNTs, higher than 4.51 × 10−14 cm2 s−1 for C@LFP,
according to the slopes of the real part of the complex imped-
ance versus the square root of frequency, ω−1/2 (Figure S13,
Supporting Information).[55]
To further evaluate the potential use of C@LFP/CNTs, its
volumetric energy densities were calculated based on the tap
density (≈1.37 g cm−3), working voltages, and the capacities
at various rates,[17] and compared with a commercial LFP/C
product (Likai Co. Ltd., Taiwan, tap density ≈1.32 m2 g−1,
Figure S14, Supporting Information), as shown in Figure 4c. It
can be seen, at 0.2 C, the volumetric energy density of C@LFP/
CNTs and commercial LFP/C was comparable with each other
(≈630 Wh L−1) due to the small polarization at low current rate
condition. With the current rate rose to 10 C, the volumetric
energy density of C@LFP/CNTs sustained 443 Wh L−1, which
is ≈1/3 larger than that of commercial LFP/C (323 Wh L−1). It is
worth noted a volumetric energy density of 219 Wh L−1 can still
be realized at the current rate as high as 60 C. These data sug-
gest C@LFP/CNTs with high volumetric energy density has a
great potential to build advanced energy storage and conversion
devices for EVs and HEVs.
In order to investigate the influence of CNTs content on the
electrochemical performance of C@LFP/CNTs, the galvano-
static charge/discharge profiles of C@LFP/CNTs with various
CNTs contents, denoted as x% C@LFP/CNTs, are compared in
Figure S15 in the Supporting Information. As can be seen, the
three samples all exhibited a flat voltage plateau, indicative of
good reversibility for Li+ intercalation and deintercalation. With
the CNTs content increased from 1 to 3 wt%, the discharge

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capacity of C@LFP/CNTs enhanced from 147 to 155 mAh g−1,
suggesting a higher CNTs content with better electronic con-
ductivity would improve the kinetics and utilizations of LFP
more significantly. However, with the CNTs content rising
up to 5 wt%, the discharge capacity dropped to 151 mAh g−1,
which could be attributed to the fact that excessive CNTs substi-
tuted too much LFP and resulted in the decrease of theoretical
capacity. Thus, for C@LFP/CNTs composite, the content of
CNTs component should be controlled in an appropriate level
to guarantee both the high electronic conductivity and theoret-
ical capacity.[56]
To deeper understand the better electrochemical perfor-
mance of C@LFP/CNTs compared with C@LFP, the com-
pound interfacial property of LFP and CNTs were further
studied by a DFT calculation. For LFP, the (010) termination is
chosen as the contact facet with CNTs, because it is the domi-
nant facet based on the Wulff constructions, as the previous
work reported.[57,58] As to CNTs, for simplicity, a single-walled
CNTs is constructed as a reasonable model to adsorbed on the
surface of LFP crystal.[59] In our theoretical calculations, spin-
polarized first-principles calculations were performed using
DFT as implemented in the DMol3 module with the Perdew–
Burke–Ernzerhof functional method.[60] The cut-off energy for
the basis function is 300 eV. Structural relaxations were per-
formed until all the residual forces on atoms were less than
0.02 eV Å−1. After the structural optimization, the average
interval between LFP and CNTs was calculated to be 1.63 Å by
constructing the C–O and C–Fe chemical bonds with an adsorp-
tion energy (ΔEads) of −2.08 eV, which is consistent well with
the literatures.[59,61] Figure S16 in the Supporting Information
Figure 5. Valence electron cloud distribution at the compound interface of LFP and CNTs: CNTs compound interface has an optimal
a) front view; b) side view; c) top view, indicated after compounding with CNTs, the distribution valence electron cloud distribution and elec-
of valence electrons transferred toward to the interfacial regions.
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and Figure 5 compare the distribution of valence electrons near
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the surface of pure LFP and LFP/CNTs compound interface. It
clearly can be seen, after compounding with CNTs, the distri-
bution of valence electrons transferred toward to the interfacial
regions (≈14.69 Å) due to the difference between the electron-
egativity of LFP and CNTs.[59] Such a phenomenon will increase
the probability of occurrence for electrons arising in the inter-
face and enhance its electron-donating ability for electrochem-
ical reactions through the formed chemical bonds as the fast
electron transfer bridges.[59,61] Figure 6 displays the band struc-
tures and density of states (DOS) of free LFP surface and LFP/
CNTs interface. From Figure 6a,b, it is found that the band gap
of LFP/CNTs (0.017 eV) was much narrower than that of pure
LFP (2.267 eV).[60] Furthermore, from Figure 6c,d, it can be
seen that LFP/CNTs had more (yet still not so much) electron
states around the Fermi level, which is another favorable con-
dition to achieve higher electronic conductivity.[62] As a result,
the special electronic structure around the Fermi level ensures
LFP/CNTs compound interface exhibit higher electronic con-
ductivity as well as better electrochemical activity.[60–62]
The above test and theoretical calculation results demon-
strate the good electrochemical performance of C@LFP/CNTs
and its potential application as the cathode material for EVs and
HEVs, which can be attributed to three main factors. Firstly,
the multi-functions of CNTs component play key roles, which
include: (i) the embedded CNTs combined with the amorphous
carbon constructed an efficient conductive network for fast elec-
tron transport in the sphere composite.[17] (ii) The embedded
CNTs network offers a large surface substrate for the nucleation
of LFP crystals (Figure S2, Supporting Information), which
simultaneously prevents the aggregation
as well as the particle size of the LFP NPs.
(iii) CNTs component in the composite could
store energy through the electric double layer
with a fast capacity response, buffering the
impact on the LFP component under high
current rate, and thus, beneficial for the
rate performance.[53] (iv) CNTs with robust
mechanical strength serve as a skeleton to
enhance the holistic structure robustness of
the composite for improving the cycling sta-
bility of electrode.[56] Secondly, the porous
structure not only effectively improves the
penetration of the organic electrolyte for
shortening the Li+ diffusion length in LFP
sphere, but also accommodate the volume
change during Li+ insertion/extraction. Fur-
thermore, the microsized sphere morphology
is good at enhancing the tap density of the
composite, and thereby, be beneficial for
improving the volumetric energy density of
the electrode.[10] Thirdly, the close contact
between LFP NPs and CNTs guarantees a
good electronic contact between them, which
is in favor of fast electron transfer between
these two components. Moreover, the LFP/
tronic structure around the Fermi level,
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Figure 6.  a,b) The band structure of LFP and LFP/CNTs, showing the band gap of LFP/CNTs was much narrower than that of pure LFP. c,d) The DOS
of free LFP and LFP/CNTs, revealing LFP/CNTs had more (yet still not so much) electron states around the Fermi level.
which ensures the better electrochemical activity of this area
and offers more active sites for electrochemical reactions.[60–62]
Therefore, it can be deduced that the synergy of the above men-
tioned factors to simultaneously address the resistances from
both electron and Li+ transport as well as electrochemical reac-
tions during charge and discharge as schematically illustrated
in Figure 4d, resulting in the impressive electrochemical per-
formance of C@LFP/CNTs. The above analysis also can be
used to explain the better rate performance of C@LFP/CNTs
compared with the previously reported microsized C and/or
CNTs modified LFP composites (Figure S17, Supporting Infor-
mation).[9,10,17,20,21,63–66] Besides, It should be noted, for further
optimizing the electrochemical performance of this type com-
posites, a finer controlled porous and CNTs embedded micro-
structure should be focused, to compete with the impressive
rate capability that has been achieved by the present state of art
LFP-based nanomaterials.[13,22,51]
On the other side, by preliminarily comparing the electro-
chemical performance of both the double carbon modified
composites—C@LFP/CNTs and C@LFP/G (Figure S18, Sup-
porting Information), it is found that the former one was also
much better than the latter. Meanwhile, with the increase of
the current rate, such a superiority was more obviously, which
may due to the more effective pathways for electron and Li+
inside the C@LFP/CNTs spheres, and thus, CNTs shows more
advantages in constructing this type of microsized LFP-based
composites. Therefore, although many of the previous work
reported different level of success in improving the electro-
chemical performance of LFP materials by introducing different
graphitized conductive carbon components (CNTs, G, carbon
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nanofiber, etc.),[18–25] the advantages and mechanisms of each
graphitized carbon component are still the critical issues which
needs to be clearly understood in the future for designing more
ideal-structured LFP composite.
In summary, we have developed a new design by deco-
rating porous LFP microspheres with two types of carbona-
ceous materials-amorphous carbon and graphitized conductive
carbon (CNTs) via an in situ CNTs-embedding hydrothermal
process followed by a high-temperature annealing treatment to
improve the electrochemical properties of LFP-based cathode
materials. Such a unique double carbon modified porous
structure provides favorable kinetics for both electron and Li+.
Therefore, by combining large tap density and improved mixed
(electronic and ionic) conductivity, high volumetric energy den-
sity and superior rate capacity as well as stable cycling perfor-
mance are simultaneously achieved for C@LFP/CNTs, indica-
tive of its potential application as a promising cathode candi-
date material directed to EVs and HEVs markets. In addition,
a combined experimental and DFT calculation study is also
introduced to deeper understand its electrochemical behavior.
Furthermore, in view of the ease of fabrication in terms of
constructing these or similar structures, the synthesis process
and research concept could also be extended to many other
functional materials for different applications (Figure S19,
Supporting Information).
Supporting Information
Supporting Information is available from the Wiley Online Library or
from the author.
Adv. Energy Mater. 2016, 1600426

www.MaterialsViews.com
Acknowledgements
B.W. acknowledges the support of China Scholarship Council (No.
20092302110052) and the Fundamental Research Funds for the
Central Universities (Grant No. HIT.NSRIF.2017024). Australian
Research Council (ARC) is acknowledged for funding FT100100897 and
DP130101870. The Centre for Microscopy and Microanalysis (CMM) at
The University of Queensland is acknowledged.
Received: February 26, 2016
Revised: April 28, 2016
Published online:
[1] J. Wang, X. Sun, Energy Environ. Sci. 2015, 8, 1110.
[2] M. Armand, J. M. Tarascon, Nature 2008, 451, 652.
[3] A. K. Padhi, K. S. Nanjundaswamy, J. B. Goodenough, J. Electrochem.
Soc. 1997, 144, 1188.
[4] J. M. Tarascon, M. Armand, Nature 2001, 414, 359.
[5] B. Kang, G. Ceder, Nature 2009, 458, 190.
[6] H. Liu, F. C. Strobridge, O. J. Borkiewicz, K. M. Wiaderek,
K. W. Chapman, P. J. Chupas, C. P. Grey, Science 2014, 344,
1480.
[7] B. Wang, B. Xu, T. Liu, P. Liu, C. Guo, S. Wang, Q. Wang, Z. Xiong,
D. Wang, X. S. Zhao, Nanoscale 2014, 6, 986.
[8] F. Omenya, B. Wen, J. Fang, R. Zhang, Q. Wang, N. A. Chernova,
J. Schneider-Haefner, F. Cosandey, M. S. Whittingham, Adv. Energy
Mater. 2015, 5, 1401204.
[9] Y. Wu, Z. Wen, J. Li, Adv. Mater. 2011, 23, 1126.
[10] C. Sun, S. Rajasekhara, J. B. Goodenough, F. Zhou, J. Am. Chem.
Soc. 2011, 133, 2132.
[11] Y. Wang, Y. Wang, E. Hosono, K. Wang, H. Zhou, Angew. Chem. Int.
Ed. 2008, 47, 7461.
[12] Z. Li, Z. Peng, H. Zhang, T. Hu, M. Hu, K. Zhu, X. Wang, Nano Lett.
2015, 16, 795.
[13] B. Wang, W. Al Abdulla, D. Wang, X. S. Zhao, Energy Environ. Sci.
2015, 8, 869.
[14] S. Yoon, C. Liao, X.-G. Sun, C. A. Bridges, R. R. Unocic,
J. Nanda, S. Dai, M. P. Paranthaman, J. Mater. Chem. 2012, 22,
4611.
[15] X. Zhou, F. Wang, Y. Zhu, Z. Liu, J. Mater. Chem. 2011, 21,
3353.
[16] J. Wang, X. Sun, Energy Environ. Sci. 2012, 5, 5163.
[17] M. Chen, C. Du, B. Song, K. Xiong, G. Yin, P. Zuo, X. Cheng,
J. Power Sources 2013, 223, 100.
[18] C. Y. Wu, G. S. Cao, H. M. Yu, J. Xie, X. B. Zhao, J. Phys. Chem. C
2011, 115, 23090.
[19] H.-M. Yu, X.-B. Teng, J. Xie, G.-S. Cao, X.-B. Zhao, Electrochem. Solid
State Lett. 2011, 14, A19.
[20] Y. Zhou, J. Wang, Y. Hu, R. O’Hayre, Z. Shao, Chem. Commun.
2010, 46, 7151.
[21] J. Yang, J. Wang, X. Li, D. Wang, J. Liu, G. Liang, M. Gauthier, Y. Li,
D. Geng, R. Li, X. Sun, J. Mater. Chem. 2012, 22, 7537.
[22] X.-L. Wu, Y.-G. Guo, J. Su, J.-W. Xiong, Y.-L. Zhang, L.-J. Wan,
Adv. Energy Mater. 2013, 3, 1155.
[23] B. Wang, D. Wang, Q. Wang, T. Liu, C. Guo, X. Zhao, J. Mater.
Chem. A 2013, 1, 135.
[24] J. Yang, J. Wang, Y. Tang, D. Wang, X. Li, Y. Hu, R. Li, G. Liang,
T.-K. Sham, X. Sun, Energy Environ. Sci. 2013, 6, 1521.
[25] Y. Shi, S.-L. Chou, J.-Z. Wang, D. Wexler, H.-J. Li, H.-K. Liu, Y. Wu,
J. Mater. Chem. 2012, 22, 16465.
[26] P.-X. Hou, C. Liu, H.-M. Cheng, Carbon 2008, 46, 2003.
Adv. Energy Mater. 2016, 1600426 © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advenergymat.de
[27] J. Robertson, Mater. Today 2004, 7, 46.
COMMUNICATION
[28] J. Liu, M. N. Banis, Q. Sun, A. Lushington, R. Li, T.-K. Sham, X. Sun,
Adv. Mater. 2014, 26, 6472.
[29] M. Chen, C. Du, B. Song, K. Xiong, G. Yin, P. Zuo, X. Cheng,
J. Power Sources 2013, 223, 100.
[30] D. P. Singh, F. M. Mulder, A. M. Abdelkader, M. Wagemaker,
Adv. Energy Mater. 2013, 3, 572.
[31] S.-W. Kim, J. Ryu, C. B. Park, K. Kang, Chem. Commun. 2010, 46,
7409.
[32] R. Jin, G. Chen, Q. Wang, J. Sun, Y. Wang, J. Mater. Chem. 2011, 21,
6628.
[33] W. Wei, S. Yang, H. Zhou, I. Lieberwirth, X. Feng, K. Müllen,
Adv. Mater. 2013, 25, 2909.
[34] B. Wang, S. Wang, P. Liu, J. Deng, B. Xu, T. Liu, D. Wang, X. S. Zhao,
Mater. Lett. 2014, 118, 137.
[35] W. Wei, W. Lv, M.-B. Wu, F.-Y. Su, Y.-B. He, B. Li, F. Kang,
Q.-H. Yang, Carbon 2013, 57, 530.
[36] T. Liu, L. Zhao, J. Zhu, B. Wang, C. Guo, D. Wang, J. Mater. Chem.
A 2014, 2, 2822.
[37] Y. Ding, Y. Jiang, F. Xu, J. Yin, H. Ren, Q. Zhuo, Z. Long, P. Zhang,
Electrochem. Commun. 2010, 12, 10.
[38] F. Yu, J.-J. Zhang, Y.-F. Yang, G.-Z. Song, J. Mater. Chem. 2009, 19,
9121.
[39] H. Yang, X.-L. Wu, M.-H. Cao, Y.-G. Guo, J. Phys. Chem. C 2009, 113,
3345.
[40] Y. Song, X. Wang, C. Zhao, K. Qu, J. Ren, X. Qu, Chem. Eur. J. 2010,
16, 3617.
[41] A. E. Goode, N. D. M. Hine, S. Chen, S. D. Bergin, M. S. P. Shaffer,
M. P. Ryan, P. D. Haynes, A. E. Porter, D. W. McComb, Chem.
Commun. 2014, 50, 6744.
[42] Y. Zhao, L. Peng, B. Liu, G. Yu, Nano Lett. 2014, 14, 2849.
[43] L. Wang, X. He, W. Sun, J. Wang, Y. Li, S. Fan, Nano Lett. 2012, 12,
5632.
[44] J. Qin, C. He, N. Zhao, Z. Wang, C. Shi, E.-Z. Liu, J. Li, ACS Nano
2014, 8, 1728.
[45] J. Duan, S. Chen, S. Dai, S. Z. Qiao, Adv. Funct. Mater. 2014, 24,
2072.
[46] Z.-S. Wu, W. Ren, L. Xu, F. Li, H.-M. Cheng, ACS Nano 2011, 5,
5463.
[47] E. G. da Silveira Firmiano, A. C. Rabelo, C. J. Dalmaschio,
A. N. Pinheiro, E. C. Pereira, W. H. Schreiner, E. R. Leite, Adv. Energy
Mater. 2014, 4, 1301380.
[48] X. Zhang, M. van Hulzen, D. P. Singh, A. Brownrigg, J. P. Wright,
N. H. van Dijk, M. Wagemaker, Nat. Commun. 2015, 6, 8333.
[49] C. Zhu, L. Gu, L. Suo, J. Popovic, H. Li, Y. Ikuhara, J. Maier,
Adv. Funct. Mater. 2014, 24, 312.
[50] F. Zhou, P. Zhu, X. Fu, R. Chen, R. Sun, C.-p. Wong, CrystEngComm
2014, 16, 766.
[51] K. Zhang, J.-T. Lee, P. Li, B. Kang, J. H. Kim, G.-R. Yi, J. H. Park,
Nano Lett. 2015, 15, 6756.
[52] J. Liu, T. E. Conry, X. Song, M. M. Doeff, T. J. Richardson, Energy
Environ. Sci. 2011, 4, 885.
[53] B. Wang, Q. Wang, B. Xu, T. Liu, D. Wang, G. Zhao, RSC Adv. 2013,
3, 20024.
[54] G. Qin, Q. Ma, C. Wang, Solid State Ionics 2014, 257, 60.
[55] B. Wang, A. Liu, W. A. Abdulla, D. Wang, X. S. Zhao, Nanoscale
2015, 7, 8819.
[56] G. Qin, Q. Ma, C. Wang, Electrochim. Acta 2014, 115, 407.
[57] L. Wang, F. Zhou, Y. S. Meng, G. Ceder, Phys. Rev. B 2007, 76,
165435.
[58] G. Zeng, R. Caputo, D. Carriazo, L. Luo, M. Niederberger, Chem.
Mater. 2013, 25, 3399.
[59] W. T. Geng, D. H. Ping, J. Nara, T. Ohno, J. Phys. Chem. C 2012, 116,
17650.
wileyonlinelibrary.com (9 of 10)  1600426
 www.advenergymat.de
www.MaterialsViews.com
COMMUNICATION

[60] C. Ban, W.-J. Yin, H. Tang, S.-H. Wei, Y. Yan, A. C. Dillon, Adv. Energy
Mater. 2012, 2, 1028.
[61] Z. Ding, L. Zhao, L. Suo, Y. Jiao, S. Meng, Y.-S. Hu, Z. Wang,
L. Chen, PCCP 2011, 13, 15127.
[62] H. Zhang, Y. Tang, J. Shen, X. Xin, L. Cui, L. Chen, C. Ouyang,
S. Shi, L. Chen, Appl. Phys. A 2011, 104, 529.
[63] S. W. Oh, S.-T. Myung, S.-M. Oh, K. H. Oh, K. Amine, B. Scrosati,
Y.-K. Sun, Adv. Mater. 2010, 22, 4842.
[64] Y. Gu, W. Liu, L. Wang, G. Li, Y. Yang, CrystEngComm 2013, 15, 4865.
[65] M. Wang, Y. Yang, Y. Zhang, Nanoscale 2011, 3, 4434.
[66] J. Qian, M. Zhou, Y. Cao, X. Ai, H. Yang, J. Phys. Chem. C 2010, 114,
3477.

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