Journal of Power Sources 318 (2016) 93e112

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Journal of Power Sources

journal homepage: www.elsevier.com/locate/jpowsour

Review article

Advanced carbon materials/olivine LiFePO4 composites cathode for

lithium ion batteries
Chunli Gong a, Zhigang Xue b, *, Sheng Wen a, Yunsheng Ye b, Xiaolin Xie b, **
a
Hubei Co-Innovation Center for Utilization of Biomass Waste, Faculty of Chemistry and Material Science, Hubei Engineering University, Xiaogan 432100,
Hubei, China
b
Key Laboratory for Material Chemistry of Energy Conversion and Storage, Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong
University of Science and Technology, Wuhan 430074, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Reviews applications of advanced

carbon materials/LiFePO4 cathode.

Discusses preparation strategies of
LiFePO4 composites cathode.

Analyzes influence factors of elec-
trochemical performances.

a r t i c l e i n f o a b s t r a c t

Article history: In the past two decades, LiFePO4 has undoubtly become a competitive candidate for the cathode material
Received 5 January 2016 of the next-generation LIBs due to its abundant resources, low toxicity and excellent thermal stability,
Received in revised form etc. However, the poor electronic conductivity as well as low lithium ion diffusion rate are the two major
1 April 2016
drawbacks for the commercial applications of LiFePO4 especially in the power energy field. The intro-
Accepted 2 April 2016
duction of highly graphitized advanced carbon materials, which also possess high electronic conduc-
tivity, superior specific surface area and excellent structural stability, into LiFePO4 offers a better way to
resolve the issue of limited rate performance caused by the two obstacles when compared with tradi-
Keywords:
Lithium ion batteries
tional carbon materials. In this review, we focus on advanced carbon materials such as one-dimensional
LiFePO4 (1D) carbon (carbon nanotubes and carbon fibers), two-dimensional (2D) carbon (graphene, graphene
Carbon materials oxide and reduced graphene oxide) and three-dimensional (3D) carbon (carbon nanotubes array and 3D
Composites cathode graphene skeleton), modified LiFePO4 for high power lithium ion batteries. The preparation strategies,
Preparation methods structure, and electrochemical performance of advanced carbon/LiFePO4 composite are summarized and
discussed in detail. The problems encountered in its application and the future development of this
composite are also discussed.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction

* Corresponding author. The increasingly serious energy crisis is one of the great chal-
** Corresponding author. lenges facing mankind in the 21st century. Development of envi-
E-mail addresses: zgxue@mail.hust.edu.cn (Z. Xue), xlxie@mail.hust.edu.cn
ronmentally friendly, sustainable, and renewable energy supplies is
(X. Xie).

http://dx.doi.org/10.1016/j.jpowsour.2016.04.008
0378-7753/© 2016 Elsevier B.V. All rights reserved.
94 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112
vital to meet the increasing energy demand of modern society and
the emerging ecological concerns [1,2]. As excellent reversible en-
ergy storage devices, lithium ion batteries (LIBs) have recently
attracted more and more attention, since they have higher energy
density than conventional lead-acid, nickel-cadmium, and even
nickel-metal hydride batteries [3]. LIBs are therefore considered to
be one of the most promising candidates, which are needed ur-
gently to power increasingly emerging large-scale application fields
such as electric vehicles (EVs), hybrid electric vehicles (HEVs) and
advanced power load leveling from smart grids, to meet the de-
mands of modern mobile technology, and to revolutionize con-
sumer electronics [4].
As one of the key building blocks of LIBs, the cathode material
plays an important role in the determination of battery energy
density, safety, life cycle and cost [5]. Up to now, only three kinds of
useful cathode materials have been investigated intensively: (1) the
layered lithiated transition metal oxides LiMO2 (M ¼ Co, Ni, Mn,
etc.) and LiCoxMnyNi1-x-yO2 (0  x,y  1) [6], (2) Mn-based spinels
LiMn2O4 [7,8], and (3) the polyanion-type compounds LixMy(XO4)z
(M ¼ Fe, Mn, Co, V, etc., X ¼ P, Si, S, etc.) [9,10]. Among them,
although layered lithiated transition metal oxide, such as LiCoO2,
has been successfully commercialized in small-scale batteries for
portable electronic equipment, it can only deliver a relatively low
practical capacity of about 140 mAh g1 which is a half of its
theoretical specific capacity (275 mAh g1). Such limitation can be
ascribed to the intrinsic structural instability of LiCoO2 when the
reversible extraction of Li from Li1-xCoO2 exceeds x z 0.5. In
addition, high cost and toxicity of Co also limit its application as a
cathode material in power supplies [11]. Another spinel-type
LiMn2O4 is regarded as a promising ‘green’ 4 V cathode material
in rechargeable LIBs due to its low cost, environmental benign and
good thermal stability as compared with LiCoO2 [8]. Lithium ions
can reversibly inserted into and extracted out of the spinel phase of
LixMn2O4 in two ranges, 0  x  1 and 1  x  2, which discharge at
two voltage plateaus of 4 V and 3 V, respectively [12,13]. Moreover,
the 4 V electrode is significantly more stable to cycling than the 3 V
electrode because a Jahn-Teller distortion existing in the spinel host
structure reduces the crystal symmetry when Liþ insertion/
extraction react at 3 V [12]. Unfortunately, one serious challenge in
the using LiMn2O4 as a cathode material is that Mn2þ easily dis-
solves in the electrolyte especially in the 4 V domain which results
in a dramatical capacity fading with cycling [14]. On the other hand,
its theoretical and practical specific capacity (only 148 and
120e130 mA h g1, respectively) are too low to be directly used in
LIBs.
As one of the most representative polyanion-type cathode ma-
terials, the olivine-type LiFePO4 attracts extensive studies for a new
generation of LIBs since the pioneering work by Goodenough's
group in 1997 [15,16]. Compared with conventional layered LiCoO2
and spinel-type LiMn2O4, the specific characteristics of LiFePO4
such as excellent cyclic stability and safety, environmental friend-
liness, potential low cost and flat operating voltage (~3.5 V vs. Liþ/
Li) are its biggest competitive advantages. Therefore, LiFePO4 is
considered to be a leading competitor for the cathode materials for
the large-capacity and -power LIBs. There are numerous works to
be done about the synthesis, structure, surface and lattice defects,
physical properties and electrochemical performances of LiFePO4.
Some review articles [11,17,18] comprehensively summarized the
structure and performances of LiFePO4. And others concerned one
of these aspects, such as synthesis procedures [19], doping [20],
surface modification [21,22], graphene modified LiFePO4 [23], etc.
The purpose of the present review focus on the advanced carbon
materials, which are classified to one-dimensional (1D) carbon
(CNTs and carbon fibers), two-dimensional (2D) carbon (graphene,
graphene oxide and reduced graphene oxide) and three-
dimensional (3D) carbon (CNTs array and 3D graphene skeleton),
modified LiFePO4. And the preparation strategies and the effects of
the structure, content, synthesis method on the electrochemical
performances of LiFePO4/advanced carbon materials, and their
applications are also summarized and discussed in detail.
2. Structure and electrochemical performance of LiFePO4
The olivine-type LiFePO4 has a slightly distorted hexagonal
close-packed (hcp) oxygen array leading to an orthorhombic unit
cell (D162h-space group Pmnb) [15], which accommodates four units
of LiFePO4. The iron and lithium atoms locate in the 4a and 4c sites
in the oxygen octahedrons respectively, thus forming FeO6 and LiO6
octahedrons. Through the common corners in the bc plane, one
FeO6 octahedron is linked with four FeO6 octahedrons to fabricate
zigzag planes [11]. The LiO6 octahedrons form edge-sharing chains
along the b axis (i.e., [010] direction), creating lithium ions trans-
portation tunnels in this direction [2]. The phosphorus atoms
occupy the center position of the oxygen tetrahedrons, thereby
forming the PO4 tetrahedron structure. These alternately arranged
FeO6 octahedrons, LiO6 octahedrons and PO4 tetrahedrons form a
layer of the scaffold structure as shown in Fig. 1a [24]. The strong
covalent bonding between the oxygen and phosphorus ions form-
ing (PO4)3- polyanionic clusters allows for the greater stabilization
of the structure even at fully charged state compared with layered
metal oxides LiMO2, in which the oxide layers are weakly bounded
[15]. Consequently, it is very difficult to extract oxygen atoms from
this stable framework, thus guaranteeing the superior thermal
stability of LiFePO4. According to the TGA result of Goodenough and
coworkers [15], no appreciable changes in both LiFePO4 and FePO4
structures can be observed in nitrogen or oxygen atmosphere up to
350  C. With this kind of three-dimensional host structure, LiFePO4
can be operated under severe conditions with no temperature
limitations and no oxygen release, thereby making this material
high safety and excellent cyclic stability. Moreover, the fully
charged state of LiFePO4, FePO4 phase, has the same olivine struc-
ture as LiFePO4 also with an orthorhombic lattice structure in the
space group Pnma [15,25]. When chemical extraction of lithium
from LiFePO4, there is only 6.81% decrease in the volume and the
2.59% increase in the density. Therefore, the striking structural
similarity between LiFePO4 and FePO4 can avoid capacity fading
resulting from serious volumetric changes during the char-
geedischarge process, and meanwhile it can also compensates the
volume changes of the carbon anode during the same process
[11,26]. And thus, the superior cycling stability of this system can be
further strengthened.
It is widely accepted that lithium ions can be electrochemically
extracted from LiFePO4 and reversely inserted into FePO4 through a
two-phase reaction (LiFePO4#FePO4 þ Liþ þ e), resulting in a flat
potential of about 3.5 V vs. Liþ/Li. Fortunately, this charge/discharge
voltage is well within the electrochemical stability window of
conventional carbonate-solvent-based electrolytes [27]. Based on
this electrochemical reaction, LiFePO4 has a theoretical specific
capacity of 170 mAh g1. Nevertheless, bare LiFePO4 is difficult to
deliver its full theoretical specific capacity because of its funda-
mentally low electronic conductivity (109 S cm1 at 298 K) [28]
and low Li ion diffusion coefficient (1014 to 1016 cm2 s1)
[29,30], which results in the poor practical electrochemical per-
formance and especially poor rate capability. Numerous efforts, as
listed in Table 1, have been made to overcome the above short-
comings. In general, the electronic conductivity can be improved by
coating or depositing LiFePO4 particles with conductive materials
[21,31e58] (e.g. carbon, metal, metallic Fe2P, conductive polymers,
etc.), and doping in the Li site [59e62], Fe site [63e68], O site
[69e71] and P site [72]. On the other hand, the other key limitation
 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112 95

Fig. 1. (a) The crystal structure of olivine LiFePO4 in projection along [001] [24]. (b) schematic illustration for the transport of electrons, lithium ions and heat flow in the LiFePO4/MP
cathode, (c) TEM image of MP, (d) rate capability and (e) discharge curves at 0.1 C under different temperature of LiFePO4-based cathodes using different conductive additives [119].

Table 1
Modification methods to improve the electrochemical performances of LiFePO4.

Modification Detailed modification materials Improvement results Disadvantages

methods

Surface coating
Carbon High electronic conductivity, small particle size, and Low tap density and volumetric power
[21,31] avoiding the oxidation of Fe2þ density
Metal Ag [32], Cu [33], Sn [34], etc. High electronic conductivity and no changing the Nonuniform and unstable nano-metal
crystal structure of LiFePO4 coating, high cost
Metal oxide TiO2 [35], ZrO2 [36], CeO2 [37], CuO2 [38], RuO2 [39], ZnO Preventing direct contact between LiFePO4 and the Nonuniform coating and high cost
[40,41], La0.7Sr0.3MnO3 [42,43], V2O3 [44], etc. electrolyte, improving structural stability
Nonmetal SiO2 [45] High structural stability and low interfacial Nonuniform coating and low electronic
oxide resistance conductivity
Phosphide Fe2P [46], NiP alloy [47], etc. High electronic conductivity and high tap density Uncontrollable process, unclear
formation and modification mechanism
Phosphate Amorphous Li3PO4 [48] Low surface anisotropy and high Li-ion delivery to Controversial modification mechanism
the (010) facet of LiFePO4
Conductive PANI [49e52], Ppy [53,54], PEDOT [55,56], PPy/PEG [57], High conductivity, high electrolyte permeability and Poor mechanical properties
polymer PANI-PEG [58], etc. high power density
Heterogeneous doping
Li site doping (Mg2þ, Al3þ, Zr4þ, Ti4þ, Nb5þ) [59], Zn2þ [60], Cr3þ [61], High intrinsic electronic conductivity Low Li-ion conductivity, controversial
La3þ [62], etc. doping site and mechanism
Fe site Co2þ [63], Ni3þ/Mn2þ [64], Mg2þ [65], V3þ/V4þ [66], Cu2þ High ion conductivity High miscibility and low doping
doping [67], Zn2þ [68], etc. temperature
O site doping Cl [69,70], F [71],etc. High ion conductivity, high structural stability Controversial doping site and
mechanism
P site doping Si [72] High ion conductivity Low electronic conductivity and unclear
doping mechanism
Morphology Size reduction [73,74], Porous structure [75e77], Other High ion conductivity and rapid electrochemical Low tap density and volumetric power
control nanostructures [78,79]. kinetics density

factor, Li-ion diffusion, can be enhanced to some extent by mini-
mizing the particle size of LiFePO4 [73,74] and fabricating porous
structure [75e77] or other nanostructure [78,79] due to the
reduced length for lithium-ion transport within the particles [2].
Consequently, a large number of studies have been employed this
strategy to mitigate ionic diffusion limitations so as to improve the
high-rate capacity and cyclic stability of LiFePO4 materials. How-
ever, size reduction to nanoscale dimension often results in lower
tap density and thus lower volumetric energy density when
compared to micrometer-sized particles [80]. An alternative effec-
tive method to address this problem is fabrication of hierarchical
architectures composed of a nano-sized primary structure to gain a
high rate capability and a micro-sized secondary structures to
ensure a high tap density [81e91]. Xie et al. [81] prepared carbon
(polyacene pyrolysis) coated spherical LiFePO4 with a particle size
of 2e12 mm which exhibited a high tap density of 1.6 g cm3 and a
rapidly improved electronic conductivity in a magnitude of
101 S cm1. Meanwhile, this spherically micrometer-sized LiFePO4
displayed a high discharge capacity of 88 mAh g1 even at 20  C
and 1 C as well as a superior cyclic stability. Sun and co-workers
[84] fabricated double carbon coated hierarchical LiFePO4 which
had an 8 mm spherical particle size and a tap density of 1.5 g cm3.
This unique morphology and highly uniform carbon coating
assured high chargeedischarge reversibility both at high temper-
ature (60  C) and low temperature (20  C). Dominko et al. [82]
reported that large LiFePO4 particles (up to 20 mm) with hierar-
chically organized pores in the meso and macro range can operate
at current rates up to 50 C while showing a tap density as high as
1.9 g cm3. A large scale LiFePO4 microspheres (1e5 mm) consisting
of nanoplates or nanoparticles with an open porous microstructure
was prepared by Goodenough et al. [88]. This morphology provides
interconnected open pores that can allow carbon coating and
96 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112
electrolyte penetration, thereby enhancing the electronic conduc-
tivity while reducing the diffusion path of lithium ions. After coated
by carbon and polypyrrole, these micro/nano-structured LiFePO4
microspheres exhibited excellent rate capability (~40 mAh g1 at
30 C) and cyclic stability (no capacity loss after 1000 cycles at 5 C
and 10 C). Therefore, optimizing particle size and tailoring
morphology is very important for high-performance LiFePO4 in
their practical applications.
No matter which modification method is adopted, carbon
coating is a necessary way to resolve the limited rate capacity
resulted from the extremely low electronic conductivity of LiFePO4,
and the electrochemical performances are therefore improved in
the presence of dispersed carbon particles which provide pathways
for electron transfer. However, in addition to the low volumetric
power density, during the formation of the pure olivine phase
(600e800  C sintering temperature), it is still very difficult to
produce highly graphitized carbon coatings which is critical to in-
crease the electronic conductivity of cathode materials. Therefore,
seeking advanced carbon materials with high graphitized carbon
content to modify LiFePO4 is a major trend in the research field of
LiFePO4.
3. LiFePO4/1D carbon composites
Due to their high surface area, superior electric properties, and
excellent electrochemical activity, one-dimensional (1D) carbon
materials, including carbon fibers (CFs) and carbon nanotubes
(CNTs), have been widely applied in all kinds of energy conversion
and storage devices such as solar cells [92,93], supercapacitors,
sensors [94,95], LIBs [96], and fuel cells [97,98], etc. Compared with
other conventional carbon conductive additives (e.g. carbon black
and acetylene black), CNTs and CFs are considered to be one kind of
the most promising materials to improve the electrochemical per-
formances of LiFePO4 because these 1D materials can easily connect
the active particles to fabricate a continuous conductive network.
Moreover, the exceptional mechanical properties of the 1D carbon
materials [99] can effectively eliminate the residual stresses caused
by volume changes in the electrode materials [96,100]. Addition-
ally, it should be pointed out that the high thermal conductivity of
individual multi-walled carbon nanotubes (MWCNTs)
(3000 W m1 K1) [101], which is far beyond that of the graphite
(about 300 W m1 K1) and carbon black (<1 W m1 K1) [102].
This is beneficial to the thermal runaway caused by over-charge or
high current chargeedischarge, and thus the high safety of the LIBs
system is guaranteed. Based on these unique advantages, numerous
researches on LiFePO4/CNTs, LiFePO4/CFs and LiFePO4/CNTs/CFs
composites have been reported.
3.1. Preparation of LiFePO4/1D carbon composites
3.1.1. Physical mixing
In many literatures, pristine CNTs or CFs were often directly
added into active materials to fabricate cathodes [103e114].
Wheeler et al. [104] investigated the effect of different carbon
conductive additives on the electrochemical performances of
LiFePO4-based cathodes. They compared three different conductive
additives (vapor-grown CFs, carbon black and graphite, respec-
tively) and found that the CFs-containing cathodes performed the
best power performance because the high-aspect-ratio fibers are
better able to maintain conductivity with less sensitivity to inter-
particle contact. Li et al. [105] adopted multiwalled CNTs as a
conductive additive to prepare a novel network LiFePO4 composite
cathode. The composite cathode exhibited excellent electro-
chemical performances with an initial discharge capacity of
155 mAh g1 at 0.1 C. In order to promote the possible short and
long-range electron pathways in different scales within the LiFePO4
cathode, Liu et al. [112] used CNTs/carbon black blend conductive
additives to build a hierarchical 3D conductive scaffolds. The
LiFePO4/C cathode with such hierarchical conductive network
exhibited excellent cyclic performance. Although these cathodes
prepared by direct physical mixing showed improved specific ca-
pacities and rate performances when compared with other cath-
odes using conventional carbon conductive additives, due to the
high van der Waals forces among tubes or fibers, the poor disper-
sion of CNTs or CFs in solution limits the formation of effective
conductive networks within the cathodes [96]. Therefore, to
maximize the advantages of 1D carbon materials, some function-
alized CNTs or CFs and other composite materials preparation
techniques have been applied to fabricate homogenously dispersed
LiFePO4/CNTs or CFs composites.
In general, functionalization of carbon materials is the most
common way to improve the dispersion of them in the matrixes
[115,116]. And the simplest approach to change the surface chem-
istry of CNTs is to treat them with strong acids (concentrated HNO3,
H2SO4, or their mixture). This process introduces many eCOOH and
eOH groups, which exhibit better affinity towards the matrix in
comparison with pristine CNTs [117]. Kavan et al. [118] prepared
carboxylic acid functionalized CNTs (CNTs-ox) and studied the ef-
fect of CNTs-ox on the electrochemical properties of three different
active materials, viz. TiO2, LiMnPO4 and LiFePO4. They observed the
nanotube wiring structure existed in the three matrixes, which
keeps the amount of conductive additives in the electrode materials
at its natural minimum. In addition to the carboxyl functionaliza-
tion of CNTs, our group prepared poly (ethylene glycol) (PEG)
grafted multi-walled CNTs (MP) and used them as a novel
conductive additive in LiFePO4-based cathodes after doping with
lithium salts [119]. It was found that the grafted PEG can effectively
improve the dispersion of CNTs in the active materials, which can
not only easily connect LiFePO4 particles to fabricate a continuous
electron and heat conductive network, but also enhance lithium
ions diffusion in the electrodes. The lithium ion diffusion coefficient
in this LiFePO4/MP cathode is about 2 orders of magnitude higher
than that of LiFePO4/acetylene black (AB) cathode. Moreover, the
electrochemical performances of the LiFePO4/MP cathode both at
room temperature and low temperature were significantly
improved, as shown in Fig. 1bee.
Unlike the surface chemistry modification of CNTs, single-
walled CNTs were also noncovalently bonded by a surfactant,
carboxyl-containing amphiphilic Ru-bipyridine complexe, which is
a redox-active material with the redox potential of about 3.45 V
versus Li/Liþ [120]. Then, the as-prepared assembly of CNTs/Ru-
bipyridine complexe was adsorbed on the surface of LiFePO4,
thereby providing a material with approximately monolayer
coverage by the Ru-bipyridine complexe and about 0.04 wt% of
CNTs [121,122]. Moreover, the submicrometer-sized LiFePO4 parti-
cles were cross-linked by CNTs, which are anchored onto the
olivine surface by the media effect of Ru-bipyridine complexe.
Hence, a homogeneous composite was obtained, in which the
LiFePO4 particles were interconnected with the CNTs/Ru-bipyridine
complexe “wires”. Besides the good dispersion in the active mate-
rial, this assembly also offers a unique electrochemical activation of
LiFePO4 called “nanotube wiring”, which is very similar with “redox
targeting” [123] and “molecular wiring” [124] both based on elec-
tron/hole transport from a redox active molecule interacting with
the LiMPO4 (M ¼ Mn, Fe) surface.
3.1.2. Self-assembly of LiFePO4 on already synthesized 1D carbon
Despite the improved dispersion of 1D carbon materials after
their functionalization, inevitable structural damage during the
functionalization process, especially the sp2 carbon structure,
 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112
significantly decrease their advantages [125,126]. Consequently,
some composite materials preparation techniques were therefore
developed to avoid the aggregation of 1D carbon materials in the
LiFePO4 matrix, and thus lead to effective electrons transfer. In
summary, there are three main strategies to prepare homogeneous
LiFePO4/1D carbon composites: (1) in situ formation of LiFePO4 on
CNTs or CFs, (2) in situ formation of CNTs or CFs on LiFePO4, and (3)
simultaneous in situ formation of CNTs or CFs and LiFePO4.
Among the first preparation strategy [127e143], several tradi-
tional LiFePO4 preparation procedures have been proposed to in situ
anchor LiFePO4 particles onto the surface of 1D carbon materials.
Wang el al. [127] prepared LiFePO4/CNTs composite cathode ma-
terials by a room-temperature solid-state reaction of the mixture of
the LiFePO4 precursor (CH3COOLi, NH4H2PO4, FeC2O4$2H2O), CNTs
and citric acid under a microwave heating condition in a few mi-
nutes. Using a non-aqueous sol-gel technique, the LiFePO4/CFs
composite with 10 wt% CFs fraction [128] and hierarchically porous
LiFePO4/nitrogen-doped CNTs (N-CNTs) composite [135] were ob-
tained. For the latter, the interconnected LiFePO4 pores, which were
formed from vigorous gas evaporation during the degradation of
the FeC6H5O7 precursor, can allow the incorporation of N-CNTs as
well as serve as the channel for the penetration of the electrolyte.
Moreover, compared with pristine CNTs, highly dispersed N-CNTs
can not only adjust and control the more homogeneous porous
structure of LiFePO4, but also further enhance the electronic con-
ductivity of the composite due to its additional electron carriers
contributed by the nitrogen atom. And the better electrochemical
performance was therefore delivered. Combining of an in situ hy-
drothermal method and electro-polymerization of aniline, Qin et al.
[139] fabricated a uniform polyaniline coated LiFePO4 nanoparticles
with a mean size of 100e200 nm, which were interconnected by a
highly conductive CNTs network. After the subsequent carboniza-
tion treatment at 700  C, the polymer shell was transformed into a
thin carbon shell with a thickness of 1e3 nm that can not only
restrict the crystallite growth of LiFePO4, but also further improve
the conductivity of the LiFePO4/MWCNTs composite.
Recently, electrospinning has been considered as a simple,
inexpensive and effective technology for preparation of 1D nano-
materials [144,145]. Moreover, a polymer solution as the electro-
spinning media, which also includes Li, Fe and P sources, can be
easily converted into carbon coating during the further heat
treatment of amorphous LiFePO4 under a reduction or an inert at-
mosphere [137]. By utilization of an electrospinning method,
Hosono et al. [130] fabricated triaxial LiFePO4 nanowires by heating
treatment of the LiFePO4 precursor/vapor-grown carbon fibers
(VGCFs)/polyacrylic acid composite electrospun fibers. The triaxial
LiFePO4 nanowires consist of a VGCF core column, a LiFePO4/
amorphous carbon composite shell, and the outer amorphous
carbon surface. The VGCF core oriented in the direction of the wire
plays an important role to form an electron transportation path,
whereas the outer amorphous carbon shell can effectively inhibit
the oxidation of Fe2þ. Significantly improved capacity and rate
capability were achieved in such triaxial LiFePO4 nanowires. In
another research, LiFePO4/CNTs/C composite nanofibers were also
fabricated by using a combination of electrospinning and sol-gel
methods [133], as shown in Fig.2. It is worth pointing out that the
LiFePO4/CNT/C composite nanofibers, which were obtained by the
heat treatment of the LiFePO4 precursor/CNT/polyacrylonitrile
nanofibers, can form free-standing and flexible mats with increased
electronic conductivity while without using any polymer binders.
Apart from the electrospinning method, other novel routes are
also used to prepare 1D carbon modified LiFePO4 composites. A
facile approach consisting of synthesizing FePO4 microspheres with
carbon nanotube embedded firstly and then by chemical lithiation
to prepare LiFePO4/CNT microspheres was reported by Chen et al.
97
[138] During the synthesis process, Fe3þ ions were first anchored
onto the surface of negatively charged CNTs through an electro-
static interaction. By adjusting pH value of the solution, FePO4
nanoparticles were subsequently formed on the CNTs surface. After
that, the FePO4 nanoparticles further grew and self-assembled into
porous microspheres while with CNTs embedded during the hy-
drothermal process. The authors pointed out that decreasing the
surface tension of the dispersed particles is very necessary to
control the particle size in the micrometer range, which is benefi-
cial to form closely packed arrays and thus improve the tap density
and volumetric energy density of LiFePO4. Finally, the FePO4/CNTs
precursor was easily transformed to LiFePO4/CNT microspheres by
a chemical lithiation process. Wu et al. [137] designed a double
nano-carbon (amorphous carbon coating and graphitized con-
ducting carbon) decorated LiFePO4@C/CNT composites (as shown in
Fig. 3aed) by using a modified polyol route [146,147] followed by a
carbon coating procedure. Compared with pristine LiFePO4 and
LiFePO4@C and LiFePO4/CNT, the obtained LiFePO4@C/CNT exhibi-
ted ultrahigh rate capability (about 59% capacity retention at a rate
as high as 120 C), superior cyclic performance (98.5% capacity
retention over 500 cycles), and excellent low-temperature perfor-
mance (about 71.4% capacity retention even when discharge
at 25  C). Sun and co-workers [142] developed an atomic layer
deposition approach to grow LiFePO4 (as shown in Fig. 3eej) in a
layer-by-layer manner on the CNTs substrate to form LiFePO4/CNT
nanocomposite. During this process, atomic layer deposition can
precisely control the thickness and film composition of LiFePO4 at
the atomic level, which also promises a versatile design of nano-
structured LiFePO4 on various types of substrates and expands the
application of LiFePO4 to a broader range. Expectedly, the results
showed that the exterior surface of CNTs was uniformly covered
with the thickness of about 30 nm and 20 nm LiFePO4 layer before
and after annealing, respectively. Excitingly, the LiFePO4/CNT
nanocomposite delivered a discharge capacity of 71 mAh g1 at
60 C, while can also maintain a discharge capacity of about
120 mAh g1 after 2000 cycles at 1 C, demonstrating its excellent
rate capability and cyclic performance.
3.1.3. Self-assembly of 1D carbon on already synthesized LiFePO4
Another common strategy of producing a well dispersed and
connected network of CNTs or CFs is in situ self-assembly of CNTs or
CFs on LiFePO4 using some carbon sources for the CNTs or CFs
growth [148,149]. Sun et al. [148] investigated the influence of CNTs
as an additive on the electrochemical performance of the LiFePO4/
CNTs composite, which was prepared by in situ chemical vapor
deposition (CVD) method and the traditional mechanical mixture
method respectively. Because of the excellent interface bonding
between LiFePO4 and CNTs in the in situ CVD case, this composite
can demonstrate fully reverse discharge capacity after 100 cycles at
1 C and still maintains 94.5% retention after 20 cycles at 10 C. By
utilization of nanosized Ni-P alloy as the catalyst, Lin et al. [149]
prepared a novel network composite by in situ controlled growth
of coiled CNTs with high conductivity on the surface of LiFePO4.
During the preparation process, Ni-P alloys were pre-deposited on
LiFePO4 particles with electroless plating using Ni(NO3)2 as the
catalyst precursor and NaHP2O2 as the reducer. And then, a
controlled thermal pyrolysis of C2H2 was carried out with the
flowing C2H2/Ar at 850  C to in situ grow CNTs. Finally, highly
conductive coiled CNTs formed a 3D electron conducting network
surrounding with LiFePO4 particles. As a result, the satisfactory
discharge capacity (161.3 mAh g1 at 0.2 C and 108.0 mAh g1 at
10 C), low redox polarization and small charge-transfer resistance
can be obtained after the introduction of CNTs.
98 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112

Fig. 2. (a) Preparation diagram, (b) SEM, (c,d) TEM images of LiFePO4/CNT/C composite nanofibers and (e) rate performance [133].

Fig. 3. (a) HRTEM image, (b) schematic illustration of the prepared LFP@C/CNT nanocomposite, (c) rate and (d) cyclic performances [137]. (e) schematic illustration showing the
atomic layer deposition process of the synthesis of LiFePO4, (f) SEM and (g) HRTEM images of as-deposited LiFePO4/CNTs, (h) SEM and (i) HRTEM images of annealed LiFePO4/CNTs
(the insets in (g) and (i) are their corresponding selected area electron diffraction patterns), (j) chargeedischarge curves at different rates [142].
 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112 99

3.1.4. Simultaneous in situ formation of LiFePO4 and 1D carbon
materials
More recently, the strategy, in situ formation (or growing) of
LiFePO4 and 1D carbon at the same time, has been attracted more
attention due to the flexibility of design various structures and the
better dispersion of 1D carbon in the LiFePO4 matrix [150e154]. Wu
et al. [152] utilized a novel in situ route combined solid-phase re-
action and chemical vapor deposition (CVD) using LiOH$H2O and
FePO4$2H2O as the LiFePO4 precursor and acetylene as the carbon
source for CFs growth. The results showed that LiFePO4 and CFs
formed almost simutaneously, thereby resulting in a perfect crys-
talization of LiFePO4 and an appropriate carbon content. Moreover,
the LiFePO4/CFs composite with 450  C CVD temperature exhibited
the highest rate capability of 122 mAh g1 at 10 C and the best cyclic
stability (only 5.5% fading after 1170 cycles at 1 C) among the three
CVD products (400, 450 and 500  C CVD temperature). They
ascribed the excellent electrochemical performance of the LiFePO4/
CF composite to the efficient 3D conductive network consisted with
the interentangled CFs and carbon layer. Similarly, Deng et al. [153]
also prepared a vapor-grown CFs/pyrolytic carbon-coated LiFePO4
composite in one step through a solid-state reaction accompanied
by a gas-phase decomposition process. Lots of needle-like CFs
formed onto the surface of LiFePO4 particles (as shown in Fig. 4aec).
Moreover, the as-prepared CFs were very uniform and had an
average diameter of about 25 nm, which implied their excellent
electrical conductivity and mechanical strength.
In order to more orderly disperse CNTs into micro-sized LiFePO4,
Sun and co-workers [154] designed and fabricated core-shell
LiFePO4@CNT nanowires via a facile sol-gel route followed by
post-heating treatment, where 1D LiFePO4 nanowires with a
diameter of 20e30 nm were encapsulated into CNTs as shown in
Fig. 4def. From the preparation schematic diagram, 1D LiFePO4
presucor nanowire structure was formed by in situ polymerization
of methylmethacrylate (PMMA) on the outer surface of the LiFePO4
presucor particles, followed by formation of a shell to restrict the
growth of LiFePO4. Subsequently, core-shell LiFePO4@CNTs nano-
wires and CNTs network were obtained during the heat treatment
because of the graphitization of PMMA by the catalytic action of
Fe2þ in the composite. It should be pointed out that the core-shell
nanowire structure can not be obtained without the template role
of PMMA. Moreover, during the intercalation and deintercalation
process, lithium ions can easily diffuse into the LiFePO4 core
through the thin carbon shell with only 5e8 layer carbon walls,
which is a typical CNTs structure. Meanwhile, electrons can also be
effectively supplied into the LiFePO4 framework through the CNTs
shell and the 3D CNTs network in the composite. Due to the ho-
mogeneous CNTs shells and 3D conductive network, the LiFe-
PO4@CNTs nanowires demonstrated excellent cycling stability and
superior rate capability.

Fig. 4. (a) (b) SEM images and (c) HRTEM image of micrometer-sized LiFePO4/CFs composite [153]. (d) schematic illustrations of the synthetic route of the LiFePO4@CNT nanowires,
(e) galvanostatic cycle chargeedischarge profiles at 0.2 C, and (f) rate capability of the LiFePO4@CNT composite [154].
100 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112
3.2. Effect of 1D carbon materials on the properties of LiFePO4/1D
carbon composites
A dense electrode with a minimum amount of carbon is required
for a higher volumetric and gravimetric energy density of LIBs
[155]. Generally, in order to ensure the effective electron trans-
portation in the cathode, about 10e20 wt% of conventional carbon
conductors (e.g. acetylene black, graphite, etc.) are necessary to be
added during the electrode preparation. As for 1D carbon materials,
because of their high conductivity, tubular shape and small specific
surface area, the content of them within the cathode is far below
that of conventional carbon conductors, which is very beneficial to
increase the volumetric energy density of the LiFePO4-based
cathode. Li et al. [105] first reported that the LiFePO4/CNTs with
only 5 wt% CNTs addition exhibited higher discharge capacity and
lower electric resistance than that of the 20 wt% carbon black case.
However, it is hard to define the optimum 1D carbon content
without discussion the additional carbon conductive content in the
electrode, 1D carbon structure and the dispersion situation as well
as the structure and performance of the adopted LiFePO4. Moreover,
only a few references discussed the effect of 1D carbon content on
the performance of the LiFePO4/1D carbon composites. For
example, Jin et al. [108] added MWCNTs to LiFePO4 and indicated
that this composite with 5 wt% MWCNTs showed the better per-
formance when compared with that of the higher MWCNTs loading
(10 wt%) both under the same addition of 25 wt% carbon black
during the cathode preparation. The same optimum CNTs content,
5 wt%, was also suggested among the LiFePO4/MWCNTs composites
with three different CNTs loading (3, 5 and 8 wt%) [107] even if only
15 wt% carbon black was added in these cathodes. Another study
reported the 2 wt% may be the effective charge-percolation
threshold in the LiFePO4/oxidative MWCNTs composite in the
absence of other carbon additives [118]. In our LiFePO4/PEG grafted
MWCNTs (MP) system with 3, 5, 8, 10, 15 and 20 wt% MP fraction,
the electrode with 10 wt% MP content exhibited the best overall
electrochemical properties at room temperature and low temper-
ature (8 and 20  C) as well as the improved electronic and thermal
conductivities [119]. Although the optimum 1D carbon content
varies in different LiFePO4/1D carbon composites, this value, as
listed in Table 2, is usually not more than 10 wt% in most of the 1D
carbon modified LiFePO4 systems.
It is well known that the degree of graphitization is a key issue to
determine the electronic conductivity of carbon materials. In gen-
eral, the ratio of the graphite carbon and disordered carbon is
usually characterized as the ratio of the Raman scattering intensity
(IG/ID) at the Raman shift of ~1600 and ~1300 cm1, respectively.
Therefore, under the same dispersion situation, the higher IG/ID
ratios, the higher electronic conductivities and thus the better
electrochemical performances for the LiFePO4/1D carbon
composites.
4. LiFePO4/2D carbon composites
As discussed above, 1D nanostructured carbon materials have
been widely incorporated into LiFePO4 to improve its electro-
chemical performance due to their high electronic conductivity. In
recent years, graphene (GN), the two-dimensional (2D) carbon
material with single-atom-thick planar sheet comprising an sp2-
bonded carbon structure, has become the most intensively studied
materials in many fields [156e162] since its discovery in 2004
[163]. Especially, its extremely high surface/mass ratio (theoreti-
cally, ~2630 m2 g1 for single-layer graphene) [164], extraordinary
electronic properties and mobility of charge carriers
(200,000 cm2 V1 s1) [165], excellent thermal conductivity
(~5000 W m1 K1 for single-layer graphene) [166] and high
Young's modulus (~1100 GPa) [167] all suggest graphene could be
the most suitable candidate as an electron conducting additive in
lithium ion battery cathodes [23,157]. Accordingly, there are
numerous works with graphene as a conductive additive within
LiFePO4-based cathode, which offered a superior rate capability to
those obtained by other conductive additives. It has been generally
accepted that graphene can fabricate more effective 3D conductive
network in the cathodes than conventional carbon additives such
as carbon black because only the outer surface of carbon black is in
contact with active materials and thus only the outer layers
contribute to the electronic conductivity of active materials [157].
The unique conductive network fabricated by GN is similar and
even better than that made by 1D carbon nanomaterials such as
CNTs and CFs.
4.1. Preparation of LiFePO4/2D carbon composites
4.1.1. Mixing of already synthesized LiFePO4 and 2D carbon
To obtain LiFePO4/GN composites, the simplest and most
straightforward way is to physically mix the two components
together [168e174]. Yang and co-workers [168] firstly used this
method to constitute a GN-based conducting network in the
LiFePO4 cathode with much lower mass fraction of GN, which
demonstrated a much better performance than the system with the
commonly employed carbon additives. This was ascribed to the
excellent electronic conducting properties and flexible conducting
network through a “plane-to-point” mode, in which GN sheets
connect LiFePO4 particles more effectively than the “point-to-
point” mode constructed by conventional carbon additives. How-
ever, no significant enhancement in rate performances compared
with conventional carbon coated LiFePO4 was reported in these
LiFePO4/GN composites prepared by simple physical mixing even
with very low GN content. The possible reason is that ineffective
contact between GN nanosheets and LiFePO4 particles resulted in a
limited improvement in electron conductivity in these cases.
Considering this drawback, Yang and co-workers [170] utilized a
self-assembly process driven by the electrostatic interaction to
prepare two different LiFePO4/GN composites: One was prepared
firstly by mixing and self-assembly of positively charged LiFePO4
nanoparticles and negatively charged graphene oxide (GO) nano-
sheets, and then by reduction of GO to obtain a full wrapping of
LiFePO4 by GN (denoted as LFP@GN), as shown in Fig.5a. The other
one, partially wrapped LiFePO4/GN composite (denoted as LFP/GN),
was prepared in the similar process only except for LiFePO4 nano-
particles with no positive charge surfaces. In addition, for purpose
of reference, sucrose-derived amorphous carbon coated LiFePO4
was also prepared. Their results indicated that a partial GN wrap-
ped LiFePO4 instead of a full and tight GN wrapped LiFePO4 deliv-
ered the best electrochemical performance in the three composites.
The authors think that a partial GN wrapping can keep a balance
between the electron transport and ion diffusion within the com-
posite, while a full GN wrapping isolates LiFePO4 particles from
electrolyte and thus inhibits ion diffusion to some extent, resulting
in the larger charge transfer resistance.
In order to further optimize the contact between LiFePO4 and 2D
carbon and thereby maximum fulfil of the functionality of 2D car-
bon, Zhou et al. [171] developed a facile method combination of
spray-drying and post annealing processes to prepare GN-modified
LiFePO4 composite, in which flexible GN sheets wrapped on and
inside the LiFePO4 microspheres to integrate into a continuous 3D
conductive network. In this case, the aqueous suspension of
LiFePO4 and graphene oxide (GO) was firstly spray dried at 200  C
to form a solid LiFePO4/GO composite, and then was annealed at
600  C for 5 h under Ar to form the GN-modified LiFePO4 com-
posite. High rate capability and superior cycling stability of the GN-
 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112 101

Table 2
Comparison of electrochemical performances of representative LiFePO4/1D carbon composites.

Composites Preparation method 1D carbon Binder/cond-uctive Rate performances, mAh Cyclic stability Ref.
content (wt%) agent (wt%/wt%) g1 (rate, C)

LFP/CNTs Physical mixing 5% 5/0 155 (0.1 C), 122 (5 C) ~150 mAh g1 and ~115 mAh g1 at 0.1 C and 5 C after [105]
50 cycles
LFP/CNT/ Physical mixing 5% (CNTs: 5/0 150.8 (0.2 C), 119.1 (1.2 C) ~4% capacity increase at 0.2 C after 50 cycles [112]
CBa CB ¼ 2:1)
LFP/CNTs Physical mixing 10% 8/0 145 (0.1 C), ~130 (0.5 C) 1% fading at 0.1 C (60  C) after 30 cycles, ~6% fading at [114]
0.5 C (60  C) after 30 cycles
LFP/o-CNTsb Physical mixing 8% 12.5/12.5 161 (0.1 C), ~150 (5 C), ~130 No report [117]
(10 C)
LFP/CNTs Physical mixing 10% 5/0 ~140 (0.1 C), ~120 (5 C), No obvious fading at 0.1 C, 5 C and 10 C after 20 cycles [118]
~110 (10 C)
cLFP/CNTs-g- Physical mixing 10% 5/0 160 (0.1 C), 123 (5 C), 84 No fading at 0.1 C after 70 cycles, 11% fading at 5 C [119]
PEGc (10 C) after 50 cycles
LFP/CNTs solid-station reaction 5% 10/15 160.3 (0.3 C), 149.9 (1.2 C) 0.6% fading at 0.3 C after 50 cycles [107]
cLFP/CNTs Microwave-assisted 1% 5/15 155 (0.5 C) No obvious fading at 0.5 C after 50 cycles [127]
solid-state reaction
LFP/o-CNTs microwave-assisted sol- No report 5/15 153.3 (0.1 C), 130.1 (1 C) No report [132]
gel reaction
LFP/N-CNTsd Sol-gel reaction 10.63% 10/15 119 (0.1 C), ~80 (5 C), ~50 ~6% increase at 0.1 C after 50 cycles, ~15% fading at 5C [135]
(10 C) after 200 cycles
cLFP/CNTs Hydrothermal reaction ~4% (C NTs þ C) 5/15 160.5 (0.1 C),~122 (5 C), 0.1% fading at 1 C after 60 cycles [143]
~108 (10 C)
cLFP/VGCF Electrospinning þ sol- 33.26% 5/0 160 (0.01 A g1), 130 (1 A No obvious fading at 0.01 A g1 and 1 A g1 after 20 [130]
nanowires gel reaction (VGCF þ C) g1), 80 (1 A g1) cycles
cLFP/CNTs Electrospinning þ sol- 25.4% 0/0 169 (0.05 C), 134 (1 C), 121 No fading at 0.1 C after 50 cycles [133]
nanofibers gel reaction (CNTs þ C) (2 C)
LFP/CNTs Lithiation of FePO4/CNTs No report 10/10 142 (1 C), 121 (5 C), ~100 ~6% capacity increase at 10 C after 1000 cycles [138]
(10 C)
LFP/o-CNTs Atomic layer deposition No report 10/0 150 (0.1 C),~110 (10 C), 71 ~12% capacity increase at 0.1 C after 100 cycles, ~20% [142]
(60 C) increase at 1C after 2000 cycles
LFP/CNTs In situ CVD 13% 10/0 160.1 (0.1 C), ~125 (5 C), No fading at 0.1 C after 100 cycles, 5.5% fading at 10 C [148]
101 (10 C) after 20 cycles
LFP/CFs In situ CVD 13.3% 10/0 162 (0.1 C), 144 (1 C), 132 1.1% fading at 0.1 C after 15 cycles [149]]
(2 C)
LFP/CFs CVD þ solid-state 6.3 wt% CFs 10/15 160 (0.1 C), ~150 (1 C), 120 4% fading at 1 C after 100 cycles [150]
reaction (5 C)
cLFP/CFs CVD þ solid-state 3.7% (CFs þ C) 10/15 ~170 (0.1 C), ~140 (5 C), 122 5.5% fading at 1 C after 1170 cycles [152]
reaction (10 C)
LFP/CNTs Sol-gel and in situ 3.9% 10/15 155 (0.2 C), 102 (5 C), ~90 No fading at 0.2 C after 100 cycles [154]
nanowires carbonization (10 C), 65 (50 C)
a
CB (carbon black).
b
o-CNTs (oxidized CNTs).
c
CNTs-g-PEG (poly(ethylene glycol) grafted CNTs).
d
N-CNTs (N doped CNTs).

Fig. 5. (a) Comparison of fabrication route and TEM images of three different LiFePO4/GN composites [170]. (b) Schematic illustration of fabrication route of graphene embedded
LiFePO4 [172].

modified LiFePO4 were reported in this work. The authors ascribed and electrolyte, (2) highly graphitized GN can greatly increase the
the excellent electrochemical performance of their GN-modified electronic conductivity, and (3) continuous 3D flexible network of
LiFePO4 materials to three main factors: (1) nanosized LiFePO4 GN wrapping on the LiFePO4 particles can make electrons easily
particles can shorten the Liþ diffusion path between the cathode transferred between the surface of LiFePO4 particles and GN. In
102 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112
consideration of the simpleness and validity of this preparation
strategy, the authors also suggested that it can be easily transfer-
able to other cathode or anode materials with low conductivity.
By means of physical blend and surface coupling reaction, Kim
et al. [172] prepared micro-sized and porous graphene embedded
LiFePO4 using stable amide bonds between the two components. As
shown in Fig. 5b, the amide bonds between LiFePO4 and GN were
formed through 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide
(EDC)/N-hydroxysuccinimide (NHS) catalyzed coupling reaction of
aminopropyl-trimethoxysilane (APS) functionalized LiFePO4 and
GO with carboxy groups. It was found that the LiFePO4/GN structure
was assembled from LiFePO4 nanoparticles with GN sheets, while
with many pores in this composite. And the superior rate capability
(~98 mAh g1 at 20 C) and cyclic stability (95% capacity retention at
1 C after 100 cycles), according to their explanation, is attributed to
the co-existence of GN sheets and many pores, which can provide
the conducting path of electrons and facilitated the Li-ion diffusion
into the structure. Similarly, Luo et al. [173] also prepared a GN
encapsulated LiFePO4 composite using this strategy, in which
nanosized LiFePO4 particles were surface modified with amino-
groups, followed self-assembled with GO to form peptide bonds,
and finally the GO-encapsulated LiFePO4 composite was reduced
into the LiFePO4/GN composite in a high-temperature Ar/H2 at-
mosphere. The obtained composite demonstrated a capacity
retention of 70% at 50 C rate and less than 8.6% capacity loss after
950 cycles at 10 C.
4.1.2. Self-assembly of LiFePO4 on already synthesized 2D carbon
LiFePO4 can be in situ formed or growed on previously prepared
GN nanosheets with high graphitization degree. One of the ad-
vantages of this strategy is that it can effectively decrease the ag-
gregation and increase the dispersion of GN within LiFePO4/GN
composites, and thus fully exert the functionality of GN. The other
advantage is that there are many various LiFePO4 synthetic
methods, such as solid-state or wet chemistry processes, to be
chosen for preparation of LiFePO4/GN composites.
By utiliation of high-temperature solid-state reaction
[175e179], many LiFePO4/GN composites has been conveniently
prepared. Wang et al. [175] synthesized LiFePO4/GN composites
using Li2CO3, FeC2O4$2H2O and NH4H2PO4 as the LiFePO4 precursor
and GN nanosheets as additives. It was found that low content of
GN (5 wt%) has no effect on the phase structure of LiFePO4. This
composite exhibited high discharge capacity of 161 mAh g1 at
0.1 C and 70 mAh g1 even at 50 C. However, there were some
obviously aggregated LiFePO4/graphene particles and disordered
stacking of graphene layers in the composite. With the aim of the
better contact between LiFePO4 and GN, Wu et al. [176] reported a
facile and reliable method for the synthesis of LiFePO4 nano-
particles loaded on GN with sucrose as a linker, which possesses
lots of hydroxyl groups and thereby can effectively bind LiFePO4
nanoparticles and GN together. In this study, GO and amorphous
LiFePO4 nanoparticles were prepared by a modified Hummers'
method and co-precipitation method, respectively. And then, the
mixture of GO, amorphous LiFePO4 and sucrose were ground and
finally heated at 700  C under vacuum to form well crystalline
LiFePO4/GN composite. The composite with 5 wt% GN delivered
excellent discharge capability during 250 cycles with the rate
changes randomly from 0.5 C to 10 C. In addition to the above solid-
state reaction processes, Xu et al. [174] used GO-encapsulated
FeOOH as a raw material and successfully transformed them into
GN-encapsulated LiFePO4 nanospheres by a solid-state process.
Due to the nano-sized LiFePO4 (~20 nm average diameter) and good
GN wrapping structure, the satisfactory rate capability (166.6, 108.6
and 90.6 mAh g1 at 0.1 C, 5 C and 10 C respectively) and cyclic
stability (capacity decay of <9% when cycled 5 C and 10 C charge/
discharge for 300 times) therefore can be obtained. Recently, an
ultrasonic-assisted rheological phase method coupled with carbo-
thermal treatment was reported to synthesize rGO modified
carbon-coated LiFePO4. During the process, the homogeneous
rheological body was obtained by ultrasonic mixing of the LiFePO4
precursor (Fe(NO3)3$9H2O, NH4H2PO4, and LiNO3), sucrose (as the
carbon resource) and rGO in an ethanol medium. As expected, the
rheological phase method can decrease the calcination tempera-
ture and time to some extent for the next carbothermal reduction
process because of the uniform dispersion of the solid powders and
liquid substances in this rheological system. Moreover, the pyro-
lytic carbon can not only be used as the reducing agent, but also
form an additional carbon coating layers on the LiFePO4 powders,
thus further improving the conductive web within the composite
[179].
Although solid-state synthesis is a conventional and convenient
method for preparing LiFePO4/GN composites, obtaining a ho-
mogenous mixture of the precursors is an inherent difficulty in the
conventional solid-state process for synthesis of LiFePO4 [21]. To
overcome this limitation, solution-based wet chemistry method
provides us a promising process to produce highly homogenous
LiFePO4/GN composites under low reaction temperature. The
solution-based process generally starts from the LiFePO4 precursors
in a liquid solution, which can ensure intimate mixing of the raw
materials at the atomic level, thereby allowing highly crystalline
LiFePO4 microsized or nanosized particles to be produced by rapid
homogenous nucleation [11]. Among these solution-based routes,
the hydrothermal or solvothermal way has been widely used to in
situ grow LiFePO4 particles on GN sheets [180e190]. Wang et al.
[180] studied LiFePO4/GN composites with an effective 3D con-
ducting network by a hydrothermal method, in which 8 wt% GO
was firstly added to the aqueous solution of FeSO4$7H2O, H3PO4 and
LiOH (the molar ratio of Li:Fe:P ¼ 1:1:1), then heated at 200  C for
5 h in a Teflon-lined stainless steel autoclave, and finally annealed
the solid mixture at 600  C for 2 h in a slightly reducing atmo-
sphere. In stead of water as the solvent, Oh et al. [181] prepared
rGO-wrapped LiFePO4 nanorods by a facile, low-temperature polyol
process using tetraethylene glycol as the solvent, Fe-(CH3COO)2,
H3PO4 and Li-CH3COO as the LiFePO4 precursors, and GO as the
additives. Among these four samples, the LiFePO4/rGO composite,
which was synthesized at 220  C without need of the subsequent
high-temperature heat treatment, presented the best excellent
electrochemical properties with remarkable capacity retention ra-
tios of 99, 97.9 and 98.6%, after 100 cycles at current rates of 0.1 C,
1 C and 10 C, respectively. By introduction of the microwave-
assisted technique, the hydrothermal or solvothermal method can
synthesize LiFePO4 in a few minutes, not in a long reaction time
(5e12 h), while with a good control of particle size and
morphology. Shi et al. [182] synthesized a highly ordered LiFePO4/
GN composite via a rapid microwave-assisted hydrothermal
method in 15 min at 250  C, followed by annealing at 600  C under
a reducing gas atmosphere. Similarly, Praneetha et al. [185] also
produced LiFePO4/GN nanohybrid by a single microwave-
solvothermal process using tetraethylene glycol as the solvent.
Moreover, it is worth noting that this microwave-assisted method
proceeds quickly, which can enable highly crystalline LiFePO4
nanorods in situ growing on GN sheets within 15 min at a low
temperature (<300  C) without need any inert gas protection or
post high temperature heat treatment. This LiFePO4/GN nanohybrid
exhibits high energy storage property with excellent cyclability and
power capability. Owing to the easy preparation process, the au-
thors think this method offers the possibilities of easy scale up and
decrease in the cost of manufacturing.
In addition to the hydrothermal or solvothermal route, other
solution-based methods, such as co-precipitation [191e193] and
 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112
sol-gel [194,195], are also the common wet chemical methods for in
situ preparation of LiFePO4/GN composites. Ding et al. [191] used a
co-precipitation method in LiFePO4 precursor and GN aqueous
suspension at room temperature, and subsequently post sintered
the deposit at 700  C to prepare LiFePO4/GN composites. Atomic
force microscopy images confirmed that the LiFePO4 nanoparticles
growed on GN nanosheets scaffolds without large-diameter
LiFePO4 aggregations. The as-prepared LiFePO4/GN composite as
cathode delivered an initial discharge capacity of 160 mAh g1 at
0.2 C and the capacity retained at 110 mAh g1 at the rate as high as
10 C. Yang et al. [194] prepared a novel 3D hierarchical LiFePO4/GN
hybrid with a porous structure by a template-free sol-gel approach
using GO, LiH2PO4 and ferric citrate as raw materials. According to
their analysis, CO and CO2, which were evolved during the degra-
dation of the xerogel containing precursors and GO in the final
calcination process, play a key role in the formation of the 3D
porous structure. These uniformly dispersed GN nanosheets in the
3D porous LiFePO4 structure led to the efficient use of the active
materials. By combination of electrospinning and sol-gel tech-
niques, Toprakci et al. [195] prepared LiFePO4/GN/C composite
nanofibers, in which LiFePO4 nanoparticles were encapsulated in
graphene-containing carbon nanofiber matrix, using LiFePO4 pre-
cursor and graphene flakes as the raw materials, polyacrylonitrile
as the electrospinning media and the carbon source. The as-
prepared LiFePO4/GN/C nanofibers also demonstrated good elec-
trochemical performance.
Recently, the route, which consists of preparation of FePO4/GO
followed by a lithiation process, has been proposed for the prepa-
ration of LiFePO4/GN composites [196e200] because of its many
advantages including no worry about the oxidation of Fe2þ and
intimate contact between LiFePO4 and GN. Kim et al. [196] adopted
this strategy to successfully fabricate LiFePO4 anchored nano-
graphite platelet (NGP). During this process, NGP was first coated
with amorphous FePO4 using Fe3þ and PO3 4 precursors because the
surface defects of NGP allow heterogeneous nucleation of FePO4
preferentially occurring on the NGP. And subsequently, LiFePO4 can
easily grow on the NGP by a solid-state lithiation reaction. The NGP
framework in the LiFePO4/GN composite afforded quick electron
transport and a high structural stability, which guaranteed the
electrode with excellent cycle life and rate capability. Considering
Fig. 6. (a) Schematic illustration of the fabrication process, (b) SEM image, (c) TEM image, and (d) chargeedischarge profiles of CeLiFePO4/rGO composite [198].
103
the importance of uniform carbon coating and small particle size on
the electrochemical performances of LiFePO4-based cathodes, Ha
et al. [198] employed GO as starting scaffolds to prepare true
nanoscale hybrid C-LiFePO4/rGO composites by a size-constrained
in situ polymeriaztion method, as shown in Fig. 6. Fe3þ ions dis-
solved in the solution were first attracted to the negatively charged
GO nanosheets by the electrostatic interactions. And then, poly-
pyrrole coated FePO4 on the GO sheets was obtained because the
precipitation of FePO4 and oxidative polymerization of pyrrole
occurred simutaneously due to the oxidation catalysis effect of
Fe3þ. Subsequent annealing process under Ar atmosphere induced
a solid-state lithiation reaction between FePO4 and CH3COOLi,
thereby obtained highly crystalline LiFePO4 and also reduced GO.
The in situ polymerization of pyrrole not only restrict the further
growth of FePO4 particles resulting nano-sized polypyrrole coated
FePO4, but also form the homogeneous carbon coating layer after
the post heat treatment. The as-synthesized composite, in which
core-shell structured LiFePO4 nanoparticle of about 30 nm size
deposited on the well-dispersed GN nanosheets, exhibited superior
electrochemical performance. In order to obtain highly conductive
graphitic carbon coatings, Fei et al. [201] designed and prepared
highly crystalline LiFePO4 encapsulated in continuous and homo-
geneous GN shells (LiFePO4@GNS) nanoparticles (about 20 nm in
diameter) through a solid-station reaction between GN-coated
metallic Fe0 (Fe@GNS) nanoparticles and LiH2PO4. To transform
Fe@GNS, which possessed highly conductive graphitic carbon
coating layers and was obtained by using CH4 as carbon source and
GO sheets as space restrictors, into LiFePO4@GNS, Fe@GNS was first
oxidized to Fe3þ under a 300  C air atmosphere for 8 h after mixing
with LiH2PO4. After further annealing at 500  C for 8 h under an Ar/
H2 atmosphere, the LiFePO4@GNS was formed by the reaction be-
tween the GN-coated interior Fe source with the exterior Li and P
sources. The as-prepared LiFePO4@GNS exhibited a core-shell
structure, in which the LiFePO4 core was highly crystalline and
was coated by uniform and continuous shells consisting of about
eight-layer graphene.
4.1.3. Self-assembly of 2D carbon on already synthesized LiFePO4
Considering the difficulties in obtaining individual GN sheets or
single-layer GN during the above two kinds of preparation
104 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112
strategies, another route, similar to the preparation route of in situ
growing of 1D carbon on LiFePO4, is also adopted to prepare
LiFePO4/GN composites. Li et al. [202] fabricated GN-decorated
LiFePO4 composite by means of in situ pyrolysis of glucose and
catalytic graphitization using a trace amount of FeSO4 as the cata-
lyst precursor. Under a reduced atmosphere at 750  C, FeSO4 was
firstly reduced to Fe nano-particles and glucose was also pyrolyzed
to amorphous carbon fragments at the same time, and then the GN
nanosheets in situ growed on the surface of LiFePO4 particles
through the realignment of carbon fragments due to the catalytic
effect of Fe nano-particles. HRTEM imagems confirmed that
LiFePO4 particles were fully covered with a uniform GN shell with
8e9 layers graphene. Meanwhile, some GN sheets were stretched
out from the GN shell to form the GN “branches”, thus constructing
a crosslinked conducting network around LiFePO4 particles. The
obtained LiFePO4/GN composite exhibited a high discharge capac-
ity (167.7 mAh g1 at 0.1 C) and superior rate capability (94.3 mAh
g1 at a rate as high as 100 C). The authors also regarded this low-
cost and effective GN surface decorating technique as a general
strategy which can be broadly applied to improve other electro-
active materials used in energy storage devices. In order to fully
coat the surface of LiFePO4 by high-graphitized carbon, Ma et al.
[203] adopted ferrocene as the catalyst during the thermal treat-
ment of polyester fully wrapped LiFePO4 nanoplates to in situ
synthesize high-graphitized carbon-coated LiFePO4 nanoplates.
Moreover, by investigating the crystal orientation of LiFePO4
nanoplates, they found that the most of the exposing facets are the
(010) crystal face, which is beneficial to the fast lithium ions
diffusion along this direction. The superior electrochemical per-
formances of this as-prepared composite at high rate (100 C) and
low temperature (20  C) were achieved due to the fast electron
transport through the highly graphitic carbon layer and quick
lithium ions diffusion through the thin nanoplates. However, the
authors did not discuss the reason of the formation of this highly
orientated (010) facets.
4.1.4. Simultaneous in situ formation of LiFePO4 and 2D carbon
Simultaneous in situ formation of LiFePO4 and GN using their
respective precursors is another route to prepare LiFePO4/GN
composites. By using this strategy, Guo et al. [204] designed and
fabricated sandwich-like LiFePO4/GN hybrid nanosheets through in
situ graphitizing organic dodecylamine interlayer between the two
lamellar FePO4 layers, which were introduced Li source by
impregnating with LiCl solution in advance. During the final heat
treatment, the dodecylamine interlayer not only behaved as the
reductive agent to form the LiFePO4 from the lamellar FePO4 and
Liþ, but also provided GN interlayer as a carbon source through the
catalytic effect of Fe series at high temperature. The thin nano-
sheets in this designed sandwich-like structure can shorten the
length for fast Liþ supply, while provide more Liþ paths between
the electrode material and the electrolyte due to the more efficient
contact. In addition, the intercalated GN layer can facilitates the fast
electron transfer and thus enhance the overall electronic conduc-
tivity. Compared with the low electronic conductivity of pure
LiFePO4 (109 S cm1), the obtained sandwich-like LiFePO4/GN
composite exhibits a strikingly high electronic conductivity of
18.9 S cm1. Therefore, the high rate capability (115 mAh g1 at
10 C) and excellent cyclic stability (less than 3% decay at different
rates after 90 cycles) were achieved.
4.2. Effect of 2D carbon on the properties of LiFePO4/2D carbon
composites
4.2.1. 2D carbon content
GN sheets or reduced GO, which are introduced into the LiFePO4
active material through different routes, can improve the electro-
chemical performance of the active material due to the enhance-
ment of the overall electronic conductivity and the structural
stability of the electrode. Moreover, the electrochemical perfor-
mance of LiFePO4/GN composites can be further improved by car-
bon coating in the most of LiFePO4/GN systems
[171,182e184,188,193,205]. The reason may be that using only GN
cannot fabricate an effective conductive network within the
LiFePO4 particles because of only dotted contact between GN and
LiFePO4 [157]. In the three different LiFePO4-based composites
(5 wt% carbon coating with no GN, 5 wt% GN with no carbon
coating, 2.5 wt% GN þ2.5 wt% carbon coating) prepared by Zhou
et al. [171] through a spray-drying and annealing process. The
LiFePO4/(2.5 wt% GN þ 2.5 wt% carbon coating) sample unexpect-
edly displayed the best rate performance (70 mAh g1 at a rate as
high as 60 C) and cycling stability (ca. 5% capacity fading when
cycled under 10 C charging and 20 C discharging for 1000 times).
According to their analysis, except for the common prerequisite of
nanosized LiFePO4 particles (shorter Liþ diffusion path), glucose-
derived amorphous carbon species may interrupt the stacking of
highly graphitized GN, which enhanced the Liþ diffusion within GN
layers although slightly decreased electronic migration at the same
time. Nevertheless, Ding et al. [206] attributed the high-rate per-
formance of their carbon coated LiFePO4/GN composite to the
complementarity of two interconnected electron transport net-
works, in which overlapping GN sheets serve as an extended cur-
rent conductor to form a primary conductive network, and
continuous nanoscale carbon coating surface facilitates the rapid
charge injection and extraction and thus to form a secondary
conductive network.
Besides the carbon coating, GN and carbon coating content also
plays an important role in the determination of the electrochemical
performance of LiFePO4/GN composites. A large amount of GN will
not only bring an adverse effect on the tap density, and thus
decrease the volumetric energy density of LiFePO4/GN composites,
but also result in the poor dispersion of GN in the active material.
Therefore, it is important to determine the optimum content of GN
in LiFePO4/GN composites, so that to use GN as little as possible. Su
et al. [168] verified the effectiveness of GN as a conductive agent
and further studied the relationship between electrochemical
performances of LiFePO4/GN and GN fraction. They demonstrated
that GN with a higher fraction (e.g. 10 wt% and 20 wt%) tented to
agglomerate and was difficult to be dispersed well in the active
material, which caused higher charge transfer resistance (~255 U
and 250 U, respectively) as compare to that of 2 wt% GN (only
~126 U) revealed by electrochemical impedance spectroscopy re-
sults. The agglomeration of GN in the active material will block the
diffusion of lithium ions, which result in a heavy polariztion and a
higher irreversible capacity even if the electronic conductivity of
the active material is improved to some extent. However, with a
lower GN fraction (e.g. 0.5 wt% and 1 wt%), the discharge plateau is
not stable and the discharge capacity is apparently lower than that
of the cathode with 2 wt% GN as the additive. This reason, according
to their study, may originate from that it can not build up an
effective conducting network when the GN fraction is very low.
Therefore, 2 wt% GN may be the optimum content in their LiFePO4/
GN composite in consideration of the comprehensive performance.
However, the optimum GN or rGO content is different in various
studies. Zhu et al. [199] investigated the electrochemical perfor-
mances of LiFePO4/rGO containing different rGO contents and
found that the initial coulombic efficiency increased from 102% to
117% with the increasing content of rGO from 7 wt% to 25 wt%. They
ascribed the initial coulombic efficiency increase with rGO content
to the enhancement of lithium ions storage capacity of rGO espe-
cially below the discharge voltage of 3 V. Moreover, it did not
 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112
exhibit a maximum capacity until 25 wt% of rGO content in the
LiFePO4/rGO hybrid. But the authors admitted that very high rGO
content will result in a low density of the hybrid and they will focus
on the optimum content of rGO in their further research. Another
study reported the optimum content of rGO was 5.6 wt% among
their three LiFePO4/rGO composites with 2.8, 5.6 and 8.4 wt% rGO
content [181]. A similar optimum GN content (5 wt%) was also
reported using a solid-state reaction method [178]. As listed in
Table 3, the GN or rGO content with a wide range from 0.1 to 25 wt%
was reported in different LiFePO4/GN or rGO systems. The reason in
this difference can be mainly attributed to the different preparation
processes (including preparation conditions, methods, precursors,
etc.), which bring strong effects on the morphologies (single-, few-
and multi-layer GN or rGO) and physical characteristics (the degree
of graphitization, electronic conductivity, mechanical performance,
etc.) of the obtained GN or rGO, and thus leading to the different
electrochemical performances of LiFePO4/GN or rGO composites.
Therefore, it seems to be no great reference value to compare these
optimum GN or rGO content directly. Despite all that, in the most
literature, low fraction and good dispersion of GN or rGO are quite
important for its applications as a conductive additive in a battery
system.
4.2.2. 2D carbon structure
Undoubtedly, the structure of the 2D carbon wrapped on the
surface of LiFePO4 particles strongly influences the electrochemical
performances of LiFePO4/2D carbon composites. Similar to the 1D
carbon materials, the degree of graphitization of the 2D carbon is
also the most important structure factor in the determination of the
properties of LiFePO4/2D carbon composites. Because the main
difference from an ideal GN sheet, which composes of only trigo-
nally bonded sp2 carbon atoms, is the structure defect in the
practical GN or rGO, resulting in the coexistence of sp2-hybridized
carbon atoms (largely) and sp3-hybridized carbon atoms (partly)
[207]. It is generally reported that LiFePO4/2D carbon composites
with high IG/ID ratios (the ratio of the graphite and disordered
carbon), which can be easily determined by Raman spectroscopy
[208], exhibited more satisfactory electrochemical performances
than those of the other LiFePO4/2D carbon composites with a
higher amount of disordered carbon [209]. The obvious reason for
that is the high degree of graphitization is very crucial to contribute
to the electronic conductivity of the cathode materials. Therefore,
how to obtain the 2D carbon materials with high graphite carbon
amount is critical for the improvement of the LiFePO4-based
cathodes, which will be discussed in 4.2.3 section.
Besides the graphite carbon structure, the thickness of GN or
rGO sheets can also significantly affect the electrochemical per-
formances of LiFePO4/GN or rGO composites. Many studies have
implied that only the surface portion of the multi-layer GN nano-
sheets can be effectively utilized to enhance the electronic con-
ductivity because of the unavailability of the interior layers [210]. To
clearly prove this point, Sun and co-workers [211] compared the
impact of stacked (prepared by thermal reduction of GO) and
unfolded GN (prepared by hydrazine reduction of GO in solution)
on the properties of the LiFePO4/GN composite. In their work,
micro-scale LiFePO4 particles were obtained when stacked GN was
used, and only a few LiFePO4 particles were attached to the stacked
GN. By comparison, almost all nano-scale LiFePO4 particles
dispersed uniformly in the unfolded GN network because the
unfolded GN possesses fewer layers and a higher surface area than
the stacked GN, thereby providing more nucleation sites to anchor
LiFePO4 precursor and further restricting the size and agglomera-
tion of the LiFePO4 particles. In this case, the sufficient contact area
between the LiFePO4 and unfolded GN can allow the electrons
reach the LiFePO4 particles from all directions, resulting in full
105
utilization of LiFePO4 and decreasing polarization of the electrode.
Although increasing the electronic conductivity of LiFePO4 can
be achieved by GN or rGO decoration, lithium ions can not pass
trough the carbon atomic arrays in 2D sheets of GN or rGO.
Therefore, lithium ions have to tortuously transport between the
active material and electrolyte, resulting in a long diffusion distance
and slow chargeedischarge rate in LIBs [157]. Modified GN sheet
with high porosity is considered to be a good solution to overcome
this drawback [212,213]. Ha et al. [213] utilized chemically-
activated GN (CA-GN) with plentiful pores (as shown in Fig.7),
which prepared via the KOH activation process, to modify LiFePO4.
During the activation reaction, KOH is reduced into metallic K and
while carbon atoms of graphene are oxidized to carbon oxide and
carbonate, leading to generate many pores on the surface of GN.
Moreover, the as-formed metallic K can intercalate into the GN
layers and further facilitates the sufficient activation of almost all
the GN surface. The extremely high surface area of CA-GN (BET
surface area, 2572.6 m2 g1) is very closed to the theoretical value of
GN (2630 m2 g1) and far exceeds that of rGO (only 366.0 m2 g1). It
is worthy noted that the LiFePO4/CA-GN composite still maintain
high surface area (488.8 m2 g1) because these in-plane pores on
the surface of CA-GN are not blocked by LiFePO4 particles. The
obtained LiFePO4/CA-GN composite demonstrated the superior rate
capacity (~63 mAh g1 at a current density of 5000 mA g1) and
satisfactory cyclic stability. The excellent chargeedischarge per-
formance, according to their explaination, may be related to the
following reasons: (1) CA-GN fabricates a continuous electron
conductive network that links the embedded LiFePO4 particles
thoroughly. (2) Abundant pore channels in the CA-GN can shorten
the distance of lithium ion diffusion, and thereby quicken the
lithium ion transportation during the chargeedischarge process.
(3) The carbon skeleton can reduce the residual stresses caused by
volume changes during the intercalation and deintercalation of
lithium ions. In addition, the large surface area of the composite can
also facilitate the immersion and accessibility between the LiFePO4
particles and the surrounding electrolytes.
4.2.3. 2D carbon synthesis method
Unlike the mature preparation technology and process of CNTs
or CFs, GN faces a very big challenge of developing a simple and
mild synthesis approach to obtain GN with high quality and con-
ductivity. To date, the most popular method to synthesize GN is
reduction of the chemically exfoliated GO, which is commonly
synthesized by a modified Hummer's method due to its potential
scalability [214]. Unfortunately, the GN nanosheets obtained by this
method have a large amount of intrinsic defects, some organic
groups and grain boundaries [215,216], while accompanying with
low synthesis efficiency and severe preparation conditions [217],
resulting in the limited improvement of high-rate performance.
Therefore, synthesis of high-quality GN is very important for the
full relization of GN's high potentials, including high electronic
conductivity and high surface area.
In order to investigate the effect of the GN preparation methods
on the electrochemical performance of the LiFePO4/GN composite,
Huang and co-workers [209] adopted three kinds of GN prepara-
tion strategies, chemical vapor deposition (CVD), Wurtztype
reductive coupling (WRC) reaction and chemical exfoliation,
respectively, to prepare large-scale high-quality GN for modifying
LiFePO4. It was exhibited that the LiFePO4/GN (CVD) composite had
a negligible disorder-induced D band, while the strong intensity of
D band for the other two method, revealing the highest quality of
CVD graphene among these three GN preparation methods. And
the excellent electronic conductivity of 1097 S cm1 for CVD gra-
phene, which is much higher than those of WRC graphene
(3.0 S cm1) and chemically rGO (1.2 S cm1), also proved this
106 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112

Table 3
Comparison of electrochemical performances of representative LiFePO4/2D (and 3D) carbon composites.

Composites Preparation method 2D carbon Binder/cond- Rate performances, mAh Cyclic stability Ref.
content (wt uctive agent (wt g1 (rate, C)
%) %/wt%)

LFP/GN Physical mixing 2% No description/0 ~150 (0.1 C) No capacity fading at 0.1 C after 30 cycles [168]
LFP/GN Physical mixing of surface charged LFP 4.5% 10/10 ~150 (0.05 C), ~130 (1 C), No report [170]
and GO, and then reduction of GO ~90 (5 C)
LFP/GN Physical mixing and surface coupling ~3% 8/17 ~153 (0.1 C), ~98 (20 C) 5% capacity fading at 1 C after 100 cycles [172]
reaction
LFP/GN Physical mixing and surface amidation 4.5% 10/10 ~120 (1 C), 105 (10 C), 90 <8.6% capacity fading at 10 C after 950 [173]
reaction (30 C), 85.1 (50 C) cycles
LFP/GN Physical mixing of LFP and GO, and ~0.5% 10/10 ~160 (0.2 C), ~70 (25 C) ~24% capacity fading at 2 C after 1000 [174]
then reduction cycles
cLFP/GN Physical mixing and spray-drying 2.5% 5/15 148 (0.1 C), ~125 (10 C), 70 ~5% capacity increase at 10 C charging [171]]
GN þ 2.5% C (60 C) and 20 C discharging after 1000 cycles
LFP/GN Solid-state reaction 5% 10/10 161 (0.1 C), 116 (10 C), 96 No report [175]
(20 C), 70 (50 C)
LFP/GN Solid-state reaction 5% 10/12 165 (0.5 C), 133 (5 C), 115 No fading at rates change from 0.5 C to [176]
(10 C) 10 C after 250 cycles
cLFP/GN Solid-state reaction of GO- 12.6% 10/10 166.6 (0.1 C), 108.6 (5 C), 2.77% and 8.30% capacity fading after 300 [177]
encapsulated FeOOH, and Li and P (GN þ C 90.6 (10 C) cycles at 5 C and 10 C, respectively
resources coating)
LFP/GN Co-precipitation method 1.5% 10/10 160 (0.2 C), 120 (5 C), 109 No report [191]
(10 C)
LFP/rGO Co-precipitation method No report 10/0 161 (0.1 C), ~90 (10 C), ~50 No obvious capacity fading at 1 C after 50 [192]
(30 C), ~40 (50 C) cycles
cLFP/rGO ultrasonic-assisted rheological phase 5% 10/10 160 (0.2 C), 136 (5 C), 127 10% capacity fading at 10 C after 1000 [179]
and carbothermal route (10 C), 116 (20 C) cycles
LFP/GN Hydrothermal reaction 8% 10/20 160.3 (0.1 C), 81.5 (10 C) No obvious capacity fading at rates [180]
change from 0.1 C to 10 C after 60 cycles
LFP/GN Hydrothermal reaction ~0.8% 7/8 ~160 (0.1 C), ~110 (10 C), No report [188]
GN þ ~0.6% C 79.7 (50 C), ~60 (100 C)
LFP/GN Hydrothermal reaction 7.3% 5/15 169.4 (0.1 C), 143.6 (5 C), 7.5% capacity fading at 10 C after 600 [190]
135.5 (10 C) cycles
LFP/GN/C Solvothermal reaction 13.1% 8/12 ~160 (0.1 C), 90 (10 C), 72.7 No report [184]
GN þ 11.8% C (20 C), 42 (40 C)
cLFP/GN Solvothermal reaction 2% GN þ 6% C 10/20 162 (0.1 C), 114 (5 C) <3% capacity fading at 0.1 C after 30 [183]
coating cycles
LFP/GN Solvothermal reaction 5% 5/15 152 (0.01 A g1), 100 4% capacity fading at 0.01 A g1 after 100 [186]
(5 A g1) cycles
cLFP/ECGOa Solvothermal reaction 2% 7/8 166 (0.1 C), 133 (5 C), 115 0.65% and 2.34% capacity fading at 1 C [218]
(10 C) and 10 C after 100 cycles, respectively
cLFP/GN Solvothermal reaction No report 10/10 160 (0.1 C), 111 (10 C), 101 No capacity fading at 0.1 C after 100 [188]
(30C), 83 (60C) cycles
LFP/G-C Solvothermal reaction ~2% 10/10 160 (0.5 C), 124 (30 C), 104 ~20% capacity fading at 1 C after 450 [206]
GN þ ~2.45% (50 C) cycles
C
LFP/GN Microwave-assisted solvothermal 8% 12.5/12.5 164 (0.1 C), ~120 (5 C) No capacity fading at 0.1 C after 70 cycles [185]
reaction
LFP/GN Hydrothermal and lithiation route 2.65% 5/15 151.3 (1 C), 139.2 (5 C), 10.8% capacity fading at 5 C after 500 [197]
129.1 (10 C), 118.2 (20 C) cycles
cLFP/GN template-free sol-gel route 7% (GN þ C) 5/15 146 (17 mA g1), ~50 ~39% capacity increase at 17 mA g1 after [194]
(1700 mA g1) 100 cycles
LFP/GN/C Electrospinning and sol-gel route 0.1% 0/0 165 (0.05 C), 132 (1 C), 107 3% capacity fading at 0.05 C after 50 [195]
(2 C) cycles
LFP/nano- Lithiation of FePO4/GN ~20% 20/0 160 (0.08 C), 100 (12 C) No capacity fading at rates change from [196]
graphite 0.8 C to 24 C after 100 cycles
platelet
LFP/C-rGO Lithiation of FePO4/GO, followed by 5.35% 10/10 168 (0.05 C), 72 (60 C) No capacity fading at 1 C after 100 cycles [198]
reduction
LFP/GN Oxidation of Fe@GN and introducing of ~5.1% No 145 (0.1 C), 98 (5 C), 84 4.7% capacity fading at 1 C after 1000 [201]
Li and P (10 C), 54 (20 C) cycles
cLFP/rGO Co-precipitation and lithiation route 15% 5/10 172 (0.06 C), ~139 (11.8 C) 2.5% capacity fading at 0.06 C after 50 [199]
cycles
LFP/GN In situ growing GN on LFP particles 2.15% 8/8 167.7 (0.1 C),152.2 (10 C), 9.3% capacity fading at 1 C after 550 [202]
118.1 (50 C), 94.3 (100 C) cycles
graphitized In situ catalytic synthesis 5.8% 10/10 169.7 (0.2 C), 141 (10 C), 2% and 12% capacity fading at 50 C and [203]
carbon- 114 (20 C), 64.5 (100 C) 100 C after 100 cycles, respectively
coated LFP
Sandwich-like Simultaneously in situ formation of LFP No report 10/10 168 (0.5 C), 135 (5 C), 117 <3% capacity fading at different rates [204]
LFP/GN and GN (10 C) after 90 cycles
LFP/unfolded Sol-gel reaction 1.5% 10/15 166.2 (0.1 C), ~100 (5 C), 60 <1.3% capacity fading at 0.1 C after 100 [211]
GN (15 C) cycles
LFP/CA-GNb Activation of GO, followed by 16.8% 15/15 147.1 (20 mA g1), ~63 No obvious capacity fading at [213]
annealing of CA-GN and LFP (5000 mA g1) 5000 mA g1 after 50 cycles
 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112 107

Table 3 (continued )

Composites Preparation method 2D carbon Binder/cond- Rate performances, mAh Cyclic stability Ref.
content (wt uctive agent (wt g1 (rate, C)
%) %/wt%)

cLFP/EG Mixing of cLFP and electrochemically 2% 10/10 208 (0.1 C) No report [219]
EG
cLFP/GN Mixing of cLFP and multi-layer GN 1% 10/9 138.8 (1 C), 121.9 (10 C), No report [220]
107.8 (20 C)
LFP/3D rGO LBL and solvothermal reaction ~10% 0/0 155 (0.1 C), 121 (10 C), 103 1% capacity fading at 1 C after 100 cycles [233]
(40 C), 56 (160 C)
LFP/N-doped Physical mixing and freeze-drying 15.36% 10/10 ~155 (0.2 C), 124 (10 C), 96 11% capacity fading at 10 C after 1000 [234]
3D GN (60 C), 78 (100 C) cycles
a
ECGO (electrochemically cleaved graphite oxides).
b
CA-GN (chemically activated graphene).

Fig. 7. (a) Schematic diagrams of preparation of chemically-activated GN and LiFePO4/CA-GN, conceptual illustrations of lithium ion diffusion pathways in (b) LiFePO4/GN and (c)
LiFePO4/CA-GN composites, (d) rate performance [213].

conclusion. The LiFePO4/GN (CVD) composite consequently deliv-
ered the optimal rate capability (80 mAh g1 at 20 C) and cyclic
stability (only 3.1% and 6.9% capacity decay after 100 cycles at 1 C
and 20 C, respectively).
Although the CVD method can produce high-quality GN, the
laborious and costly preparation procedure (including low yields,
and high time, gas and energy consumptions) is still the major
limitation for the practical application of such kind of the com-
posite. In view of this, one-step electrochemical oxidation cleavage
method was reported by Zhang et al. to produce flaky GO with
hydrophilicity and good conductivity from a graphite plate [218]. In
this work, the electrochemical cleavage of graphite was carried out
using two high-purity graphite plates as the working electrode and
counter electrode in an aqueous electrolyte solution of Li3PO4 and
H3PO4. The selection of Li3PO4 and H3PO4 as the electrolytic me-
dium can avoid the introduction of impurity ions into the following
solvothermal synthesis of carbon coated LiFePO4/electrochemically
cleaved graphite oxide (cLFP/ECGO) composite. The ECGO can be
dispersed homogeneously in the electrolyte without any precipi-
tation even after 2 months, displaying its excellent hydrophilicity,
which is useful to closely combine with LiFePO4 precursors. This
cLFP/ECGO composite with a high tap density (1.52 g cm3)
demonstrated a reversible capacity as high as 166 and 115 mAh g1
at 0.1 C and 10 C, respectively. Similarly, Hu et al. [219] achieved
large quantity of exfoliated graphene (EG) also by a scalable method
electrochemical exfoliation using a graphite rod as the GN source as
well as the working electrode, a Pt wire as the grounded electrode
and an aqueous solution containing SO2 4 as the electrolyte. And
then, few-layer GN coated LiFePO4 was obtained by dropwise
adding the DMF solution of EG to LiFePO4 powders with gentle
stirring at 180  C. With the aid of DMF solvent, the EG flakes can be
wrapped on the surface of LiFePO4 particles through van der Waals
interaction. Surprisingly, a capacity of 208 mAh g1, which is
beyond the theoretical capacity of LiFePO4 (170 mAh g1), at 0.1 C
108 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112
for this GN coated LiFePO4 composite was delivered. The excess
capacity, according to their explaination, is attributed to the ultra-
high capacity of the EG flakes (>2000 mAh g1), which was
revealed by the layer-to-layer distance change during the charge
and discharge process. In addition to the exfoliation of graphite by
the electrochemical method, multi-layer GN was also prepared by
high power ultrasonic exfoliation of the worm-like expanded
graphite, which can be easily obtained via a rapid heat-treatment of
expandable graphite in isopropyl alcohol, and then by pure treat-
ment with HNO3. Due to the good dispersion of multi-layer GN in a
NMP solvent, which is also the common medium to ensure ho-
mogeneous mixing of the active materials, conductive additives
and binder, the large-size multi-layer GN sheets were embedded
into the bulk electrode as a “highway” for electronic transport
[220]. In consideration of the simple and efficient modification of a
bulk electrode by multi-layer GN, this facile and economical
approach can decrease the cost of cathode composite materials for
the commercialization of LIBs.
5. LiFePO4/3D carbon composites
As mentioned above, 2D carbon-structure graphene has both
the advantages of high surface specific area and high conductivity.
However, how to avoid the restacking of GN or rGO sheets during
the electrode preparation is still a challenge for their practical
application. Currently, 3D nanostructural carbon material, such as
CNTs arrays [221,222], 3D GN network [223e225] and other 3D
porous carbon [226,227], is a hot topic for high-performance en-
ergy devices [228,229]. Because of the structural inter-
connectivities, many advantages including hierarchical porous
channels as well as high electronic conductivity and excellent
structural mechanical stability can be possessed in the 3D carbon-
based nanostructure.
Schneider et al. [230] prepared ordered 3D CNTs arrays
comprising MWCNTs with average diameters of either 60 nm or
200 nm using a catalyst free CVD method with porous Al2O3 as a
template and then by selective etching of Al2O3 template. Subse-
quently, they used the 3D CNTs arrays as a supporting cathode
structure for electroactive LiMPO4 (M ¼ Fe, Co, Ni). Significantly
enhanced electrochemical performances of these ordered LiMPO4/
3D CNTs composites was obtained when compared with the iso-
lated LiMPO4 phosphoolivine phase. According to their analysis
[230,231], the following positive effects may be attributed to the
electrochemical performances of such a coaxially aligned com-
posite: (1) improved overall electronic conductivity; (2) enhanced
Liþ conductivity and transport within the composite due to well
directed 1D conductive pathways; (3) reduced diffusion length
because of the nanometric length scale of the CNTs arrays; (4)
better overall structure stability.
By using chemical vapor deposition (CVD) on a 3D porous Ni
template, Huang and co-workers [232] prepared highly conductive
3D graphene network to enhance the rate performance of LiFePO4
cathode. During the process, the clean Ni template was first heated
to 1000  C under a H2 flow of 2000 sccm. After annealing for
40 min, a gas mixture flow of CH4, H2 and Ar (the specific flow rate
was 2, 50 and 300 sccm, respectively) was introduced to grow GN
for 30 min, and then the sample was rapidly cooled down. The 3D
graphene was finally obtained after dissolving the Ni template in a
HCl solution and removing poly(methyl methacrylate) (PMMA),
which was coated on the GN surface to avoid its damage during the
process of dissolving Ni. Apart from the high structure quality and
electronic conductivity (~600 S cm1), the as-prepared 3D gra-
phene had lots of pores and exhibited a high specific surface area
(500e600 m2 g1), which facilitated the incorporation of LiFePO4
nanoparticles and thus formed an effective interconnected electron
transportation network within the cathode. Similarly using a Ni
foam template, Mo et al. [233] obtained a free-standing 3D com-
posite with porous structure made from reduced GO (rGO) loaded
with LiFePO4 nanoparticles by means of layer-by-layer assembly
(LBL) and solvothermal method. The route for 3D rGO-LiFePO4
composite starts with the multilayer LBL films produced by
sequential adsorption of GO-NHþ -
3 and GO-COO onto a Ni foam,
proceeds with depositing PMMA on the surface of the LBL films to
prevent the LBL composite from collapsing during removal of the Ni
template, and ends with the self-assembly and crystallization of
LiFePO4 into the rGO matrix. As a result of such composites prop-
erties, unusually high reversible rate capability (56 mAh g1 at the
rate as high as 160 C) enable them exceed those of known LiFePO4-
based cathodes, as shown in Fig. 8.
Combination of the advantages of 3D porous structure and N-
doped GN aerogel (N-GA), Wang et al. [234] prepared a 3D porous
LiFePO4 material modified with a N-GA, in which the N-GA with
interconnected porous network facilitates rapid electron the and
ion transport, while the thin LiFePO4 nanoplatelets with large (010)
surface shorten the Liþ diffusion paths. According to their prepa-
ration route, the positively charged LiFePO4 (modified by APS) and
negatively charged GO first assembly together to obtain GO-
anchored LiFePO4. After that, the LiFePO4@N-GA was obtained by
the hydrothermal treatment of LiFePO4@GO in a urea-dissolved
aqueous GO suspension and finally by a freeze-drying process.
The LiFePO4@N-GA composite cathode delivered a very high rate
capability (78 mAh g1 at 100 C) also with a satisfactory cyclic
stability (only 11% capacity loss over 1000 cycles at 10 C).
6. Applications of LiFePO4/advanced carbon composites
Apart from traditional small-scale portable energy devices,
LiFePO4 is also considered to resolve the trouble in the power and
energy storage field. Thanks to its high capacity of 170 mAh g1 and
a discharge voltage of ~3.5 V, LiFePO4 can deliver an theoretical
energy density as high as about 580 Wh kg1 [235]. If taking the
weight of binder, conductive agent and current collector into ac-
count in the general case, practical energy density of 100e120 Wh
kg1 can be achieved for a LiFePO4-based battery pack [236], which
is enough for current electric vehicles market. Particularly, the
unparalleled safety and stability of LiFePO4, which can sustain high
peak power without appreciable effect on the lifetime, has attrac-
ted the attention of the major car industries. Actually, batteries
based on carbon-coated LiFePO4 cathodes were successfully
commercialized in the HEV and PHEVs such as BMW Active Hybrid
3 and 5 series in 2011 [237]. The Fisker Karma and the Chevrolet
Spark also offered PHEVs powered by LiFePO4-based battery pack
[238]. As discussed above, compared with traditional carbon
coating, utilization of advanced carbon materials to fabricate a
high-speed network for electrons can result in a dramatic increase
of the achievable capacity both at low and high chargeedischarge
current densities. In addition, the resilient and strong base pro-
vided by this network can stabilize the electrode structure and
buffer the volume change of supported high-capacity electrode
materials [239]. Moreover, high graphitized carbon can signifi-
cantly decrease the amount of carbon additives and thus increase
the practical energy density of LiFePO4. Based on these advantages,
advanced carbon materials modified LiFePO4 has a larger applica-
tion prospective in the power battery field. Varize et al. [240]
assemblied a novel full cell using carbon-coated ZnFe2O4 (ZFO)
nanoparticles and CNT-LiFePO4 composite as the anode and cath-
ode, respectively. Such a battery showed remarkable rate capability
of about 60 mAh g1 at currents corresponding to about 20 C.
Furthermore, the pre-lithiation of the ZnFe2O4-based anode can
tune the potential of the full cell. Therefore, superior gravimetric
 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112
Fig. 8. (a) Preparation route, (b,c) photograph, (d) SEM image and (e) rate performance of layer-by-layer-assembled 3D rGO-LiFePO4 composite [233].
energy and power density values of 202 Wh kg1 and 3.72 W kg1
(these values refer to the total active material amount of both
electrodes), respectively, were achieved. Due to the excellent
reversibility of this system, such a full cell showed a very high
cycling stability of a capacity retention of 85% after 10,000 cycles
even at a high current (~10 C). In addition to the superior perfor-
mance, the authors regarded the environmental friendly nature as
the great advantage of this high power battery because of the
benign and highly abundant Fe and Zn elements. By dispersion
nano-sized LiFePO4 particles into a 3D nanoporous carbon matrix,
Wu et al. [241] fabricated superior electrode materials, in which the
mixed conducting 3D nano-network enabled both Liþ and e to
migrate and reach each active particle, thereby realizing the full
potential of LiFePO4. As a result, this nanocomposite delivered both
a high power density and energy density. Its capacity can retain
about 60% when the power density increased from 38 W kg1 to
1875 W kg1 (~50 times). Even at a power density as high as
20 kW kg1 (corresponding to a rate of 230 C), the discharge energy
density was still 87 Wh kg1. Because supercapacitors, the best
candidate to resolve the extremes of power-density needs (about
1e20 kW kg1) among current energy devices, can only deliver
about 1e20 W h kg1, such excellent power performances make
this LiFePO4/3D carbon nanocomposite may be used in superior
electrochemical energy-storage devices with both high-power and
high-energy densities.
Recently, flexible LIBs have received considerable attention
[239,242] as a key component in the emerging flexible and wear-
able electronic devices such as roll-up displays, touch screens, and
wearable sensors, etc. Except for solid-state electrolytes, the safety,
mechanical strength and electrochemical properties of electrodes
also play very important roles in determination of the overall
109
performance of flexible LIBs. Similar to the power battery field,
LiFePO4 also attracted great research interest in the flexible LIBs
field. Leijonmarck et al. [243] fabricated a flexible and stretchable
graphite/LiFePO4 paper battery by sequential filtration of the bat-
tery components instead of preparing separate components in
advance. The resulting paper battery are mechanically strong and
flexible also with a high reversible discharge capacity of 146 mAh
g1 at 0.1 C (based on LiFePO4) and good cycling performance.
Compared with paper LIBs, textile-based flexible LIBs have more
potential applications in future wearable electonics. Flexible and
stretchable film batteries composed of LiFePO4 cathode, Li4Ti5O12
anode and polyethylene oxide solid electrolyte can be cut into thin
stripes and then integrated into textiles using conventional
weaving techniques [244]. Although the batteries exhibited poorer
electrochemical performance compared to that of batteries based
on the powder electrode and liquid electrolyte, their more stable
cycling performance and flexible properties make them well suit-
able for smart textile applications.
7. Conclusions and outlook
In summary, this work provides a detailed overview of the most
recent research development in the fabrication, structure, electro-
chemical performance and applications of advanced carbon mate-
rials, including 1D, 2D and 3D nano-sized carbon, modified LiFePO4
composites as cathode materials in LIBs. Due to the superior elec-
tronic conductivity and extremely high specific surface area of
these advanced carbon materials, LiFePO4/advanced carbon com-
posites have been proved to present excellent electrochemical
performances especially high rate capability and super cyclic life.
Four fabrication strategies, which are physical mixing, self-
110 C. Gong et al. / Journal of Power Sources 318 (2016) 93e112

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