Accepted Manuscript

The best addition of graphene to LiMn0.7Fe0.3PO4/C cathode material synthesized

by wet ball milling combined with spray drying method

Liwei An, Hao Liu, Yuanyuan Liu, Zhenfei Li, Xin Ren, Liang Guangchuan

PII: S0925-8388(18)32543-X
DOI: 10.1016/[Link].2018.07.043
Reference: JALCOM 46758

To appear in: Journal of Alloys and Compounds

Received Date: 27 April 2018

Revised Date: 2 July 2018
Accepted Date: 4 July 2018

Please cite this article as: L. An, H. Liu, Y. Liu, Z. Li, X. Ren, L. Guangchuan, The best addition of
graphene to LiMn0.7Fe0.3PO4/C cathode material synthesized by wet ball milling combined with spray
drying method, Journal of Alloys and Compounds (2018), doi: 10.1016/[Link].2018.07.043.

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 ACCEPTED MANUSCRIPT

The best addition of graphene to LiMn0.7Fe0.3PO4/C cathode material

synthesized by wet ball milling combined with spray drying method

Liwei An,a Hao Liu,a Yuanyuan Liu,a Zhenfei Li,a Xin Rena, Guangchuan Lianga,b,c,*

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a
Institute of Power Source and Ecomaterials Science, Hebei University of Technology, Tianjin 300130, China
b
Key Laboratory of Special Functional Materials for Ecological Environment and Information (Hebei University

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of Technology), Ministry of Education, Tianjin 300130, China
c
Key Laboratory for New Type of Functional Materials in Hebei Province, Hebei University of Technology, Tianjin
300130, China

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Abstract

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LiMnxFe1-xPO4 with high electronic conductivity is synthesized by a
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combination of wet ball milling, spray drying, carbon thermal reduction technology
and using graphene oxide (denoted as GO) as the carbon additive. The effect of
graphene content on morphology and structure of LiMn0.7Fe0.3PO4/C cathode material is
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systematically investigated. The graphene-LiMn0.7Fe0.3PO4 composite has ordered

olivine structure and micro-spherical morphology assembles with nanosized primary
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particles. SEM and TEM images indicate that the particle size of LiMn0.7Fe0.3PO4-G2 is
about 800 nm in diameter. The initial discharge capacity of LiMn0.7Fe0.3PO4-G2
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nanoparticles is 153mAh·g−1. It shows that graphene oxide can restrict the growth of
LiMn0.7Fe0.3PO4 and improve the electrical conductivity. Through adding different
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amount of graphene, we get the best addition of graphene. The LiMn0.7Fe0.3PO4-G2

sample has a core-shell structure, not only does the surface of nanoparticles have a
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homogeneous and complete carbon coating but also exhibits a microspherical

morphology. What ’s more the surface of microspheres is fully covered with GO sheets,
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which enhances electronic conductivity. All above mention factors lead to its excellent
electrochemical performance at room temperature and low temperature.

Keywords: Lithium ion battery; Spray drying; Graphene based composite; excellent
electrochemical performance

*Corresponding author.
E-mail address: liangguangchuan@[Link] (G. Liang).
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[Link]

LiFePO4 has been considered to be the promising cathode material for electronic
equipment battery due to its good features, such as environmental friendliness,
safety, perfect cycling performance, abundance in raw materials and a bunch of
advantages [1-5]. However, its low working voltage (3.4 V) leads to low energy density,

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which can not meet the application of new energy technology in electric equipment.
LiMnPO4 has a higher working potential of 4.1 V (vs. Li+/Li) and receives more
attention all over the world. The crystal structure and theoretical capacity (171

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mAh·g−1) of LiMnPO4 are similar to those of LiFePO4 [6-11], and LiMnPO4 shows
about 20% higher energy density (~701 Wh·kg-1) than LiFePO4 (~578 Wh·kg-1).

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Therefore, LiMnxFe1-xPO4 (LMFP) is a very promising material. Many researchers
reported that the high rate cycling performance of LiNi1/3Co1/3Mn1/3O2 materials could

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be improved after mixing with LiMn1-xFexPO4. It is known that the
LiNi1/3Co1/3Mn1/3O2 cathode material is very expensive due to the rare cobalt. The
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cost of cathode material can be remarkably reduced with the addition of LMFP. So it
is very necessary to optimize the properties of LMFP material [12]. Nevertheless,
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LiMnPO4 is greatly limited by its intrinsically low electronic conductivity and poor Li+
diffusivity caused by John-Teller distortion of Mn3+ [13-15]. The intrinsically
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extremely low electronic and lithium ion conductivity of pure LiMnxFe1-xPO4 cathode
lead to its low specific discharge capacity and poor rate performance. There are three
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common ways to improve the electrochemical performance of LMFP, that is, reducing
the particle size, carbon coating and doping with cations/anions. The addition of
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graphene oxide is a very effective way to improve the performance of LiMnxFe1-xPO4

materials [16-21]. There are many ways to synthesize LiMnxFe1-xPO4 cathode
materials, such as co-precipitation method, sol-gel method, solid-state method,
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hydrothermal method, and spray drying method. Spray drying method is an excellent
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method for preparing spherical particles, which can increase the compaction density and
volumetric specific energy. Many researchers have obtained a new form of lithium
iron phosphate with a spherical secondary particles by combining spray drying
methods [22-27]. The samples exhibit high tap density and excellent electrochemical
performance. Inspired by the previous work, graphene oxide (denoted as GO) was for
the first time used as the carbon additive and a mature spray drying method [28] was
carried out by using FeC2O4·2H2O and MnC2O4·2H2O as raw materials to obtain
LMFP/GO/C composite.
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[Link]

2.1 Synthesis of LiMn0.7Fe0.3PO4/C/GO

FeC2O4·2H2O, MnC2O4·2H2O, LiH2PO4 (A.R, STL, Tianjin), and glucose were

mixed with deionized water, and then x wt‰ of GO (x =0, 1, 2 and 3) was added into
the above mixture. After ball-milling for 2 h, the precursor slurry with a solid content

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of 35wt.% was spray-dried in a pressure spray dryer (LG-5, Jianyi, Wuxi) at a rate of
100 mL/min with inlet and outlet temperatures at 280-300 °C and 100-110 °C,
respectively. The nozzle had a diameter of 1mm and an inlet pressure of 0.4 MPa.

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Finally, the spray-dried precursor (SP) was calcinated in a tube furnace at 750 °C for
5.5 h under nitrogen atmosphere. The corresponding samples prepared with 1wt.‰,

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2wt.‰, 3wt.‰ GO were marked as G1, G2 and G3, respectively. In addition,
LiMn0.7Fe0.3PO4 straw-bundle without the addition of GO synthesized under the same

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condition was named as G0. The synthetic strategy for LiMn0.7Fe0.3PO4/C/GO
composite is illustrated in Fig. 1.
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Fig. 1. Schematic illustration of the synthesis of LiMn0.7Fe0.3PO4/C/GO composites

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2.2 Electrochemical measurements

The electrochemical tests of samples were carried out using 2430-type coin cell
assembled in an argon-filled glove box. The LiMn0.7Fe0.3PO4/C/GO powder was
mixed with acetylene black and polytetrafluoroethylene (PTFE) in a weigh tratio of
[Link], then rolled into a 0.16 mm thick sheet and cut into pellets. The lithium metal
was used as anode and 1 mol/L LiPF6 in ethylene carbonate (EC)/ diethyl carbonate

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(DEC) (1:1 in volume) was used as electrolyte.

2.3 Material characterization

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The charge/discharge test was performed between 2.3 and 4.5 V on LAND
battery test system. The phase identification of samples was analyzed with an X-ray

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diffractometer (D/max-2500, Rigaku, Japan) using Cu Kα radiation (λ=0.15406 nm)
in the range of 10°-80°. The FTIR spectra using KBr pellet techniques was collected
by a Nicolet 330 FTIR spectrometer. The field emission-scanning electron

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microscopy (FE-SEM) with a FEI SIRION microscope and high-resolution
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transmission electron microscope (HR-TEM) with Philips Tecnai F20 were used to
analyze the morphology and microstructure.
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[Link] and discussion

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3.1 Sample characterization.

Fig. 2(a) shows the XRD patterns of G0, G1, G2 and G3, which match well with
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the diffraction pattern of olivine LiMnPO4 with Pmnb (62) space group (JCPDS
#74-0375), illustrating the high purity of the products. The diffraction peaks of the
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graphene oxide in the samples are not found due to its small amount. The diffraction
peaks of G0, G1, G2, and G3 samples slightly shift towards higher angle direction
with respect to the standard pattern, which can be explained by the smaller ionic
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radius of Fe2+ (0.92 Å) than that of Mn2+ (0.97 Å).

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The FTIR spectra of LiMn0.7Fe0.3PO4/C in the range of 1300-400 cm-1

corresponding to the stretching mode of PO43- anion is shown in Fig. 2(b). The first
three bands, two sharp bands at 1137 and 1106 cm-1 and a broad one at 1074 cm-1, are
attributed to asymmetric stretching mode (v3). The band at 982 cm-1 is ascribed to
symmetric stretching mode (v1), and the band near 634 cm-1 is attributed to
asymmetric bending mode (v4). The four bands at 582, 550, 499, 456 cm-1 correspond
to the bending modes (v2 and v4). It is worth mentioning that the band of v1 mode,
implying the deformation of P-O, has been shifted positively in comparison with that
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of LiFePO4 (~979 cm-1 [29]) and LiMnPO4 (~989 cm-1). This shift reflects the
difference in the lattice structure between LiMn0.7Fe0.3PO4 solid solution and LiFePO4
or LiMnPO4. The IR bands below 400 cm-1 that are assigned to external modes or
lattice vibrations of this compound are not presented here.

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Fig. 2. (a)XRD patterns of G0-G3. (b)FTIR spectra of LiMn0.7Fe0.3PO4/C
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Fig. 3 shows the SEM images of G0, G1, G2 and G3 samples. The
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LiMn0.7Fe0.3PO4/C without graphene particles (G0) are aggregates with irregular spherical
morphology, whose particle size is approximately 5 µm.
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The sphericity of G1 and G2 is better than G0. As shown in Fig.3(c-d) and (e-f),
there are some surface regions unwrapped by graphene oxide in G1. Because only a
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small amount of graphene oxide is used to synthesize G1, graphene oxide cannot
completely cover the surface of material. Because of the insufficient amount of
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graphene oxide added, the electrochemical properties of G1 are not excellent. The
surface of G2 is fully covered with graphene oxide. The sphericity of G2 is the best
among the four samples. The size of G2 nanoparticles is also reduced. As shown in
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Fig. 3(g) and (h), G3 is microspherical LiMn0.7Fe0.3PO4/GO composite with irregular

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sphericity. The graphene oxide on the surface is thick layered structure. Due to van
der Waals forces, the electrochemical properties can be affected. To investigate the
effect of graphene oxide content on the electronic conductivity of LiMn0.7Fe0.3PO4/C
cathode material, the powder electronic conductivities of the samples were measured
by two-point probe method with Jack, multimeter and vernier caliper. Table 1 lists the
electronic conductivities of G0, G1, G2 and G3 sample. The electronic conductivity
of G2 and G3 is 1.2×10-2 and 6.5×10-3 S·cm-1, respectively. The electronic
conductivity of G3 is much lower than that of G2, suggesting that the restacking of
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GO reduces the electronic conductivity. That is why the electrochemical properties of
G3 is unsatisfactory.

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Fig. 3. SEM of LMFP-G0: (a), (b); LMFP-G1: (c), (d); LMFP-G2: (e), (f); LMFP-G3: (g), (h)

The TEM images of G2 are shown in Fig. 4(a) and (b). It can be seen that the
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LiMn0.7Fe0.3PO4 primary particles are spherical, whose surface is perfectly covered by
graphene oxide, thus allowing the deeply penetration of electrolyte. Fig. 4(c-h) show
energy-dispersive X-ray spectroscopy (EDS) elemental mapping of G2. It can be seen
that the Fe, P, O, Mn and C elements are evenly distributed throughout the
composites.

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Fig. 4. (a) and (b) TEM image of LMFP-G2. (c) -(h): EDS elemental mapping of
LMFP-G2.
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Table 1. Electronic conduction of samples

Electronic conduction
Sample
(S·cm-1 )

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LiMn0.7Fe0.3PO4/C/G0 3.5×10-3
LiMn0.7Fe0.3PO4/C/G1 9.8×10-3
1.2×10-2

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LiMn0.7Fe0.3PO4/C/G2
LiMn0.7Fe0.3PO4/C/G3 6.5×10-3

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3.2 Electrochemical performance of LiMn0.7Fe0.3PO4 .
The electrochemical performances of G0-G3 samples are illustrated in Fig. 5. As
shown in Fig. 5(a), there are two characteristic potential plateaus (3.5 V and 4.0 V),

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which are associated with the redox process of Mn3+/Mn2+ and Fe3+/Fe2+, respectively.
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The plateau of Mn3+/Mn2+ at around 4.0 V is lower than that of LiMnPO4, while the
plateau of Fe3+/Fe2+ at 3.5 V is higher than that of LiFePO4. It is probably ascribed to
the super-exchange interaction between Fe-O-Mn ions. The discharge curves also
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show that the specific capacities of samples differ from each other. As shown in Fig.
5(a), there are four curves to illustrate the initial galvanostatic discharge performance
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of G0, G1, G2, G3 at 0.2 C rate and room temperature. The discharge capacities of G0,
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G1, G2, G3 are 140, 147, 153 and 143 mAh·g-1, respectively. The different specific
capacities are mainly from the potential plateau of Mn3+/Mn2+. The reason may be
that uniform nanoparticles and in situ reduction of graphene oxide is beneficial to Li
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ion diffusion and electroconductivity of LiMn0.7Fe0.3PO4 material. The electronic

conductivity of G1 and G2 is better than that of G0, therefore the discharge capacities
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of G1 and G2 are higher than that of G0, and G2 shows the highest discharge capacity.
The addition of graphene oxide increases the specific surface area of the composites.
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Obviously, a high surface area increases the number of electrochemical reaction sites.
That is why G2 exhibits excellent rate performance and specific capacity. The
discharge capacity of G3 is much lower than that of G2 because of the transport of
lithium ions is hindered by the disorderly accumulation of graphene oxide.
Fig. 5(b) shows the discharge curves of G2 and G0 at 0.2 C rate and -20 °C. As
we can see in Fig. 5(b), the discharge capacities of G2 and G0 are 117.1 and 90.2
mAh·g−1, respectively. The capacity retention rates are 80 and 64% comparing to
those at room temperature. As the temperature decreases, the charge transfer
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resistance increases, resulting in slower lithium ions diffusion. Appropriate amount of
graphene can increase lithium ion diffusion rate and reduce charge transfer resistance,
thus leading to the better low-temperature performance of G2 than G0.
The cycle performance at 1 C rate are shown in Fig. 5(c). The discharge
capacities of G0, G1, G2, G3 are 125, 150, 151, 130 mAh·g−1, respectively. The
capacity retentions are 90.0(G3), 99.0 (G2), 95.9 (G1), and 89.6% (G0), respectively,

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after 100 cycles. Among them, G2 shows superior cycling stability and higher specific
capacity. It can be concluded that the addition of graphene has a reinforcing effect on
the material, but the proper addition amount is very important.

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4.4
(a) G0
(b) G0

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4.5 G1 4.2 G2
G2
4.0
G3
4.0 3.8

3.6
Voltage/V

Voltage/V
3.4
3.5

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3.2

3.0
3.0
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2.8

2.6
2.5
2.4

0 20 40 60 80 100 120 140 160 0 20 40 60 80 100 120

-1 -1
Specific capacity/(mAh·g ) Specific capacity/(mAh·g )
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(c)
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160
Specific capacity/(mAh·g-1)

140

120
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100

80

60
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40 G0
G1
20 G2
G3
0
0 20 40 60 80 100
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Cycle number

Fig. 5. Initial discharge curves at 0.2 C rate (a); Low-temperature performance at -20 oC at 0.2 C and
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rates (b). Cycling performance curves of G0, G1, G2, G3 composites at 0.2 C rate (c);

Fig.6 shows the CV curve of G2 in the potential range of 2.3-4.5 V at a scan

rate of 25 µV·s−1. It is obvious that there are two anodic peaks and two cathodic
peaks, which are related to the insertion of lithium ions into the bulk.
Correspondingly, the peaks at 3.4 V and 3.6 V are attributed to redox process of
Fe2+/Fe3+. And the peaks at 4.26 V and 3.97 V correspond to the redox process of
Mn2+/Mn3+ [30]. It can be seen that the voltage separations of Mn2+/Mn3+ and
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Fe2+/Fe3+ are 0.27 V and 0.2 V, indicating the excellent reversibility of G2 sample.

0.003

0.002

0.001

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Current/A

0.000

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-0.001
LMFP-G2
-0.002

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-0.003
2.5 3.0 3.5 +
4.0 4.5
Potential/V(vs. Li/Li )

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Fig. 6. Cyclic voltammetry (CV) of G2 at a scan rate of 25 µV·s−1 between 2.3 V and 4.5 V
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EIS analyses were conducted to thoroughly analyze the electrochemical behavior
of materials. The EIS was performed under fully discharged state after two cycles of
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charging-discharging at 0.2C rate, and the corresponding Nyquist plots are displayed
in Fig.7a. The Nyquist plots of all samples are including a small interrupt and a
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semicircle in high frequency region and a sweep line in low frequency region.
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Generally, the high frequency intercept in Z'-axis represents the ohmic resistance (R
s ), and the semicircle in high frequency reflect the charge transfer resistance (Rct ).
The oblique line in low frequency reflects the lithium ion diffusion between the
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particles, namely, Warburg impedance (Wo ). The resistance of charge transfer is

relative to the diameter of the semicircle and the values obtained by Zview soft on the
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basis of the equivalent circuit (inset Fig. 9a) was listed in Table 2. The G2 electrode
shows the lowest charge-transfer resistance, which can be explained by the highest
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surface area and electronic conductivity. The restacking of GO sheets in the composite
results in the higher charge-transfer resistance of G3.
To further understand the solid state lithium diffusion into the electrodes, linear
fittings between Zre and the reciprocal of the square root of the angular frequency in
the low frequency region are performed, as shown in Fig. 7(b). The apparent chemical
diffusion coefficient of lithium ions can be calculated from the sloping line at the
low-frequency region using the following equation [31-35]:
DLi = R2T2/2A2n4F4C2σ2 [1]
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where, T is the absolute temperature(298K), n is the number of electrons involved in
theredox process (n=1 for the Fe3+/Fe2+ and Mn3+/Mn2+ redox couples), F is the
Faraday constant(96485 C·mol-1), C is the initial concentration of lithium ions in
LMFP crystal (0.0228 mol cm−3), A is the surface area of the active material (1.1 cm2 )
which can be calculated from the slope of the lines between Z' and ω-1/2 according to
the following equation:
Z' = Re + Rct + σω−1/2

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[2]
Herein ω is the angular frequency region, and the plot of Z' against ω-1/2 in
low-frequency region is a straight line. It is well known that there is an inverse

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relationship between the slope of the linear fittings and lithium diffusion rate. Based
on Eqs. (1) and (2), the lithium ion diffusion coefficients for G0-G3 samples are

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2.34×10-14, 2.02×10-13, 4.53×10-13, 4.73×10-14 cm2·s-1, respectively. The G2 electrode
exhibits the lowest slope among the samples. Therefore G2 had the highest lithium

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diffusion rate. Therefore, the superior rate capability and excellent cycling stability of
G2 can be explained by the lowest charge-transfer resistance and the highest lithium
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diffusion coefficient into the electrode.
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120 120

(b) LMFP-G0
(a) LMFP-G0 110
LMFP-G1
100 LMFP-G1
LMFP-G2
100 LMFP-G2
LMFP-G3 90 LMFP-G3
80
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80
-Z''/Ω

Z'/Ω

60
70
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60
40
50

20 40

30
0
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0 20 40 60 80 100 120 140 160 180 1.0 1.5 2.0 2.5 3.0 3.5
-1/2 -1/2
Z'/Ω ϖ /s

Fig 7. Nyquist plots and fitting curves of G0-G3 samples.

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Table 2 Charge transfer impedance ,Warburg factor σ and Li+ diffusion coefficient DLi of

LMFP-G0~G3

Sample Rct (Ω) σ (Ω·s-1/2) DLi (cm2·s-1)

LMFP-G0 59.89 51.42 2.34×10-14

LMFP-G1 42.89 17.49 2.02×10-13

LMFP-G2 34.78 11.62 4.53×10-13

LMFP-G3 49.11 36.16 4.73×10-14

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4. Conclusions
The graphene-LiMn0.7Fe0.3PO4/C (graphene-LMFP/C) has been synthesized by a
two-step processes, namely, a solid-state ball-mill carbon coating and spray drying
method, which has been considered as a very promising cathode material with high
redox potential. The addition of graphene enhances the electrochemical performances

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of LMFP, such as superior high rate capability and cyclic performance. In the range of
2.0-4.5 V, LMFP/C delivers a capacity of 155, 147, 143 and 140 mAh·g−1 for G2, G1,

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G0 and G3 at 25 °C, whereas graphene-LMFP/C shows an increased capacity. Among
the samples, the G2 sample exhibits the highest capacity retention of 99.0% after 100

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cycles at 1 C rate. The best addition (2wt‰) of graphene-LMFP/C material presents a
more flat and longer voltage plateau compared with LMFP/C. Because the amount of
GO is still less, the thus caused cost increase is acceptable. In the actual production

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process, the effect of using graphene-LMFP/C with other cathode materials is also
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satisfactory. The cost of cathode materials is remarkably decreased with the addition
of LMFP.
This paper may encourage further efforts to maximize the performance available
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from this material in terms of high rate capacity.

Acknowledgements
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The authors are grateful to the Natural Science Foundation of Hebei Province
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(Grant number E2015202356) for the financial support to this work.

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