Journal of Alloys and Compounds 779 (2019) 339e346

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Nanocomposites LiMnxFe1-xPO4/C synthesized via freeze drying

assisted sol-gel routine and their magnetic and electrochemical
properties
Liying Liu a, Zujie Cao a, Yanyan Cui a, Xi Ke a, Guoxun Zeng a, Jun Liu a, Dan Liu b,
Qinghai Li b, Jian Lai b, Zhicong Shi a, *, Shulei Chou c, **
a
School of Materials and Energy, Guangdong Provincial Key Laboratory of Functional Soft Condensed Matter, Smart Energy Research Centre, Guangdong
University of Technology, Guangzhou, China
b
Dynavolt Renewable Energy Technology Co., Ltd., Shenzhen, China
c
Institute for Superconducting & Electronic Materials, Australian Institute for Innovative Materials, University of Wollongong, Wollongong, Australia

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

Article history: Nanocomposites LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 2/3, 1/2) are synthesized by a sol-gel route combined with
Received 1 August 2018 freeze drying. Fe2þ substituted samples coated by high-ordered carbon have the same olivine structure of
Received in revised form LiMnPO4/C but reduced cell volumes. Fe2þ substituting greatly influences magnetic characteristics of
17 October 2018
LiMnPO4/C and slight amounts of Fe2P impurity in Fe2þ doped samples are verified by magnetic tests.
Accepted 14 November 2018
Fe2þ substituted samples exhibit much better electrochemical properties. Among them, LiMn1/2Fe1/2PO4/
Available online 22 November 2018
C displays the best rate capacity and cyclic stability. Its initial discharge capacity reaches 140.1 mAh g1
and remains at 132.5 mAh g1 after 100 cycles at 2C, remarkably higher than those of LiMnPO4/C. The
Keywords:
Lithium ion battery
superior electrochemical performances are mainly attributed to small charge-transfer impedance, fast
Cathode material Liþ diffusion, residual carbon and existence of Fe2P with excellent electronic conductivity.
Lithium manganese phosphate © 2018 Elsevier B.V. All rights reserved.
Iron substituting
Magnetic property

1. Introduction Carbon coating, metal-ions doping and nanoparticles control-

ling are effective methods to mitigate the above obstacles [13e15].
With growing demand for clean energy such as electric vehicles And these methods are often combined together to achieve ideal
(EVs), hybrid electric vehicles (HEVs) and large-scale energy stor- effects. Therefore, carbon coated LiMnxFe1-xPO4/C solid solutions
age devices etc., higher requirements on power density, energy are developed to further enhance electrochemical properties of
density as well as cycling life for lithium ion battery (LIB) have been LMP [16e18]. However, most of researches on LiMnxFe1-xPO4/C
put forward [1e4]. At present, cathode material is still the main have been devoted to their electrochemical properties. Only a few
factor hindering performance improvement and cost reduction. papers relating to magnetic properties have been published in our
Although LiFePO4 (LFP) has been popularly used in small power best knowledge [19e23]. Moreover, the relation between magnetic
tools, it can't satisfy the higher requests due to poor intrinsic and electrochemical properties hasn't been analyzed thoroughly.
electronic/ionic conductivities and low energy density [5e7]. Magnetic characteristics, determined by macroscopic electronic
Comparing with LFP, LiMnPO4 (LMP) can provide a higher operating states, are extremely sensitive to crystal structural defects and
voltage of 4.1 V with similar theoretical specific capacity [8,9] and impurities. Therefore they are indirectly vital to electrochemical
thus has drawn great attention recently. Nevertheless, LMP also performances and deserve to be researched in depth.
suffers from extremely low electronic/ionic conductivities because In this study, LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 2/3, 1/2) nano-
of the same crystal structure to LFP [10e12]. composites were synthesized by a freeze drying assisted sol-gel
method. Sol-gel method possesses advantages of good homoge-
neity of raw materials, low calcination temperature and short re-
* Corresponding author.
action time [24] and freeze drying was introduced to solve
** Corresponding author. agglomeration produced by traditional drying process. Our focus
E-mail addresses: [email protected] (Z. Shi), [email protected] (S. Chou). has been put on systematically investigating both magnetic and

https://doi.org/10.1016/j.jallcom.2018.11.174
0925-8388/© 2018 Elsevier B.V. All rights reserved.
340 L. Liu et al. / Journal of Alloys and Compounds 779 (2019) 339e346

electrochemical performances of LiMnxFe1-xPO4/C nanocomposites 633 nm He-Ne laser excitation (Raman spectra) and a HF-2000B
and the relationship between them. Magnetic tests (M(H, T) and high frequency induction combustion furnace (Wuxi, China).
c1(T)) and calculation of magnetic parameters were adopted to Magnetization and susceptibility tests were performed with an
get valuable information concerning changed microstructures and automated magnetometer (MPMS-5S from Quantum Design)
possible impurities in this paper. equipped with an SQUID in temperature range of 4e300 K.

2. Experimental 2.3. Electrochemical measurement

2.1. Materials synthesis Electrochemical properties were researched with CR2032 coin
cells assembled in an argon-filled glove box. The cathode is con-
A freeze drying assisted sol-gel route was used to synthesize sisted of as-prepared materials, acetylene black and polyvinylidene
LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 2/3, 1/2). Raw materials CH3COO- fluoride binder in weight ratio of 80:10:10. A metallic lithium foil
Li$2H2O, C4H6MnO4$4H2O, FeCl2$4H2O, NH4H2PO4 and was applied as the counter and reference electrode. A mixed so-
C6H8O7$H2O with molar ratio of 1:0.5:0.5:1:1 were separately lution of ethylene carbonate (EC)-diethyl carbonate (DEC) (1:3 in
dissolved in 100 ml deionized water. After mixing manganese ac- volume) containing 1 M LiPF6 was used as electrolyte. Galvanostatic
etate solution with citric acid solution well, FeCl2 and NH4H2PO4 charge-discharge tests were carried out on a CT2001A battery
solutions were dropped into it in turn with strongly stirring. Then testing system (NEWARE, China) between 2.5 and 4.5 V (vs Liþ/Li).
LiOH$H2O solution was added slowly under continuously magnetic Both cyclic voltammograms (CV) and electrochemical impedance
stirring at 80  C until a wet gel was formed. The above wet gel was spectroscopy (EIS) tests were performed on a CHI660E electro-
frozen and freeze dried more than 2 days, milled and sintered at chemical workstation (ChenHua, China). CV curves were recorded
350  C for 5 h in Ar atmosphere. Cooled down to room temperature within 2.45e4.55 V (vs Liþ/Li) at scan rates of 0.2e0.5 mV s1. EIS
slowly, the precursor was milled and calcined again at 700  C for were conducted in frequency range of 1e105 Hz.
10 h in flowing argon to yield final products.
3. Results and discussion
2.2. Materials characterization
Fig. 1 presents XRD refinement results of LiMnxFe1-xPO4/C. The
Crystal structures were characterized by X-ray diffraction (XRD, detected diffraction peaks are fully indexed to the orthorhombic
Rigaku D/max-RB, Japan). The surface morphology was investi- structure of LMP (ICSD#740375) without any impurity peaks and
gated with field emission scanning electron microscopy (FE-SEM, the diffraction peaks developed very well, as shown in Fig. 1aed.
Hitachi, S-4800, Japan) and high-resolution transmission electron The corresponding lattice parameters, cell volumes and corre-
microscopy (HRTEM, JEM-2010(HR), JEOL, Japan). Carbon state and sponding crystallite sizes are given in Table 1. Compared with LMP/
content were separately confirmed by a HORIBA LabRAM HR with C, Fe2þ substituted samples have smaller lattice parameters and cell

Fig. 1. XRD Rietveld refinement results of LiMnxFe1-xPO4/C (a) x ¼ 1, (b) x ¼ 5/6, (c) x ¼ 2/3 and (d) x ¼ 1/2.
 L. Liu et al. / Journal of Alloys and Compounds 779 (2019) 339e346 341

Table 1
Refined unit-cell parameters and crystallite sizes for LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 2/3, 1/2) (a, b, c: three lengths of unit cell; V: volume of unit cell).

Samples a (Å) b (Å) c (Å) V (Å3) R (%) Crystallite size (Å)

x¼1 10.4845 (1) 6.1259 (6) 4.7619 (7) 305.9 5.72 887 (1)
x ¼ 5/6 10.4405 (1) 6.1001 (6) 4.7422 (9) 302.0 8.84 821 (0)
x ¼ 2/3 10.3998 (7) 6.0683 (4) 4.7344 (0) 298.8 6.65 317 (7)
x ¼ 1/2 10.2995 (6) 5.9987 (3) 4.6803 (7) 289.2 8.69 635 (2)

Fig. 2. SEM images of LiMnxFe1-xPO4/C (a) x ¼ 1, (b) x ¼ 5/6 and (c) x ¼ 1/2, the insets are corresponding partial-zoom images; TEM (d) for x ¼ 1/2 and HRTEM (e, f) for the circle area
in Fig. (d); Raman spectra of LiMnxFe1-xPO4/C (g) x ¼ 1 and (h) x ¼ 1/2.
342 L. Liu et al. / Journal of Alloys and Compounds 779 (2019) 339e346

volumes which regularly decrease with the decrease of x. It is spacing of 0.280 nm ((031) lattice plane) can be clearly observed in
ascribed to the successful substitution of Mn2þ (0.083 nm) by Fe2þ Fig. 3f, which corresponds to the diffraction peak masked with “*”
(0.078 nm) to form a homogeneous solid solution [25]. The calcu- in Fig. 1d.
lated crystallite sizes according to Ref. [26] for these samples are in Furthermore, Raman spectra for LiMnxFe1-xPO4/C (x ¼ 1, 1/2) are
range of 32e89 nm. The residual carbon contents for LiMnxFe1- given in Fig. 2g and h to reveal the carbon nature in depth. In
xPO4/C are in the range of 7.40e8.02 wt%, whereas no visible car- Fig. 2g,h, D-band (disorder band) and G-band (graphite band)
bon diffraction peaks have been detected. [27,28] can be evidently seen in the ranges of 1271e1458/1504-
Fig. 2aec shows morphologies of LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 1/ 1634 cm1 and 1283e1464/1502-1633 cm1 with peak intensity
2). As shown in Fig. 2aec, all samples possess similar nanorod ratios (IG/ID) of 1.17 and 1.19, respectively. Only small other peaks
shapes with about 100 nm in width and 200e300 nm in length. can be found in Raman spectra. These further prove that both
Some nanoparticles with diameter in range of 50e100 nm samples possess high-ordering residual carbon which is beneficial
dispersed in them uniformly with no observed aggregation. It in- for electrochemical properties.
dicates that Fe2þ substituting have no obvious influence on Fig. 3 compares isothermal plots of magnetic moment versus
morphology and particle distribution of LMP/C. HRTEM images for applied magnetic field and corresponding temperature de-
LiMn1/2Fe1/2PO4/C (as representative) are presented in Fig. 2def. pendences of reciprocal of magnetic susceptibilities (c1 ¼ H/M)
Fig. 2d illustrates that this composite mainly consisted of nanorods for LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 2/3, 1/2), respectively. The relevant
in accord with SEM results (Fig. 2c). There are some residual carbon magnetic parameters are given in Table 2. For LMP/C, there is a peak
particles among them, for example, in the area circled by white line. in c1(T) curve with the transition temperature (TN) of 35 K. Its
Zooming this area, HRTEM results are shown in Fig. 2e and f. From antiferromagnetic behavior disappears beyond TN and then fol-
Fig. 2e,f, a uniform amorphous carbon layer with thickness of lowed by Curie-Weiss-like behavior. Moreover, magnetization
around 2 nm and a carbon “bridge” connecting two particles can be curves present linear variations at all testing temperatures. These
clearly observed, which can greatly enhance the electronic con- results coincide with the magnetic characteristics of pure LMP
ductivity. Only one kind of lattice fringes belonging to LMP with d- [29e31] indicating no detected impurities in LMP/C. However,

Fig. 3. Magnetization curves for LiMnxFe1-xPO4/C (a) x ¼ 1, (b) x ¼ 5/6, (c) x ¼ 2/3 and (d) x ¼ 1/2; the insets are corresponding temperature dependences of reverse magnetic
susceptibilities.

Table 2
Magnetic parameters for LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 2/3, 1/2).

Samples TN/K T2/K Cp/emu K mol1 m/mB Type of impurities Impurities/wt%

x¼1 35 e 3.72 5.48 None 0.00

x ¼ 2/3 40 250 2.37 4.37 Fe2P 0.31
x ¼ 5/6 44 244 1.87 3.88 Fe2P 0.42
x ¼ 1/2 47 242 0.76 2.48 Fe2P 0.94
 L. Liu et al. / Journal of Alloys and Compounds 779 (2019) 339e346 343

Fig. 4. Initial charge-discharge curves of LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 2/3, 1/2) at 0.5C (a) and 2C (b); Cycle performances of LiMnxFe1-xPO4/C at 0.5C (c) and 2C (d); SEM images of
x ¼ 1/2 after 100 cycles at 2C (e).

obvious differences can be found for Fe2þ substituted samples. First, Second, other higher transition temperatures (T2) for Fe2þ
although there also are peaks in c1 (T) curves, the TN values vary as substituted samples exist in c1 (T) curves, and paramagnetisms
a monotone increasing function of Fe2þ concentration (see Table 2). are presented only above T2. Third, non-linear behaviors in M (H, T)

Fig. 5. EIS plots of LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 2/3, 1/2) tested at (a) open circuit potential before cycling, and (b) after 100 cycles to the cut-off voltage of 2.5 V at 2C; The insets are
separately corresponding equivalent circuit.
344 L. Liu et al. / Journal of Alloys and Compounds 779 (2019) 339e346

curves for Fe2þ substituted samples are presented with different to improve electronic conductivity by 5 orders of magnitude
curvatures at low-magnetic fields and linear behaviors occur at [37e39]. The magnetic results don't agree with former XRD results
room temperature. probably owing to poor detection limit of XRD.
According to previous references [32e34], it can be deduced Magnetic parameters Cp and effective magnetic moment (m)
that some ferromagnetic impurities are included in Fe2þ calculated by Curie-Weiss law [36,40] are listed in Table 2. They all
substituted samples. The possible impurity is most likely Fe2P with decreased regularly with decreased x. The decreased magnetic
the Curie constant (Cp) below room temperature [35,36]. Further- parameters caused by Fe2þ substituting in LMP/C reflect micro-
more, the calculated fractions of Fe2P impurity (Fe content) are structure changes [41], which are probably vital to the electro-
separately 0.31 wt%, 0.42 wt% and 0.94 wt% through the formula chemical performances of LiMnxFe1-xPO4/C applied as cathode
M0 ¼ Nnm(H,T). Fe2P included in cathode materials has been proved materials for LIB.

Table 3
Simulation results of EIS spectra for LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 2/3, 1/2).

Samples RU/U before cycling RU/U after 100 cycles Rct/U before cycling Rct/U after 100 cycles

x¼1 2.601 2.070 333.0 259.7

x ¼ 5/6 1.991 2.631 156.4 208.5
x ¼ 2/3 2.304 2.010 120.2 100.7
x ¼ 1/2 2.048 1.711 86.4 36.4

Fig. 6. CV curves of LiMnxFe1-xPO4/C at varied scan rates (a) x ¼ 5/6, (b) x ¼ 2/3 and (c) x ¼ 1/2; Corresponding linear fitting of Ip vs. v1/2 at redox peaks (d) x ¼ 5/6, (e) 2/3 and (f) 1/2.
 L. Liu et al. / Journal of Alloys and Compounds 779 (2019) 339e346 345

Electrochemical performances of LiMnxFe1-xPO4/C (x ¼ 1, 5/6, 2/ homogeneously coated high-ordered carbon. Cell volumes and
3, 1/2) are displayed in Fig. 4aed. In Fig. 4a and b, LMP/C has only magnetic parameters (Cp and m) of Fe2þ substituted samples
one pair of voltage platform in the first charge/discharge curves, evidently decrease with decreased x, indicating the microstructure
whereas Fe2þ substituted samples present two pairs of plateaus at differences caused by Fe2þ substitution. Very small amounts of Fe2P
around 4.0 V and 3.5 V separately relating to Mn2þ/Mn3þ and Fe2þ/ impurity in Fe2þ doped samples are confirmed by magnetic tests.
Fe3þ redox couples. Moreover, the plateaus corresponding to Fe2þ/ Fe2þ substituting is beneficial to enhance electrochemical proper-
Fe3þ redox couple become longer with increased Fe2þ substituted ties of LiMnPO4/C. Among them, LiMn1/2Fe1/2PO4/C demonstrates
amount, which powerfully verifies the successful substitution of the best rate and cyclic ability. The initial capacities of 145.2 mAh
Mn2þ by Fe2þ. From Fig. 4c and d, it can be obviously observed that g1 and 140.1 mAh g1 are achieved at 0.5C and 2C, respectively.
Fe2þ substituted samples exhibit much better rate and cycle per- Moreover, no capacity loss occurs after 100 cycles at 0.5C. The
formances. When x ¼ 1/2, the best performances with initial improved electrochemical performances are ascribed to decreased
discharge capacities of 145.2 and 140.1 mAh g1 and capacity re- charge-transfer impedance and increased Liþ diffusion due to Fe2þ
tentions of nearly 100% and 94.6% after 100 cycles are achieved at substituting, in combination with increased electronic conductivity
0.5C and 2C, respectively. Whereas, the first discharge capacities of resulted from residual carbon and Fe2P phase.
LMP/C are only separately 99.4 mAh g1 and 81.7 mAh g1 with
capacity retentions of 86.9% and 71.2% after 100 cycles at corre- Acknowledgments
sponding current rates. The results of x ¼ 1/2 in this work are also
better than those reported in former literatures [18,21,34,35]. The work was supported by the National Natural Science
Fig. 4e shows the morphology of x ¼ 1/2 after 100 cycles at 2C. Foundation of China (NNSFC, 21673051), Guangdong Province Sci-
Comparing with Fig. 2c, no obvious differences can be found indi- ence & Technology Bureau (2017B010119003, 2016A010104015).
cating the good stability during cycling.
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