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Synthesis and electrochemical properties of

monoclinic fluorine-doped lithium manganese
Cite this: RSC Adv., 2015, 5, 90150
oxide (LixMnO2
yFy) for lithium secondary batteries
Yu Zhang, Zhi Su,* Xiang Yao and YingBo Wang

A series of monoclinic fluorine-doped lithium manganese oxide (LixMnO2
yFy) were prepared by the ion
exchange of sodium for lithium in NaxMnO2
yFy precursors that were obtained using a high-temperature
solid-state reaction. The microstructure and composition of the samples were characterized by X-ray
diffraction (XRD), scanning electron microscopy (SEM), inductively coupled plasma atomic emission
spectroscopy (ICP-AES), ion chromatography (IC), Fourier transform infrared spectroscopy (FTIR), and
X-ray photoelectron spectroscopy (XPS). The different valence states of manganese in material
LixMnO2
yFy were determined by redox titration method. The electrochemical performance of these
samples as cathode materials were studied by the galvanostatic and cyclic voltammetry method. These
materials had a high crystallite size, which was composed of 5–8 mm grains. The Li0.86MnO1.98F0.02
materials delivered an initial discharge capacity of 129.2 mA h g
1 and gradually increased to a maximum
Received 24th September 2015
Accepted 14th October 2015
discharge capacity of 210 mA h g
1 at a current density of 50 mA g
1 after 50 cycles. Moreover, the
material showed an excellent cycling behavior, even though its original structure transformed into the
DOI: 10.1039/c5ra19751a
spinel phase during cycling. The results show that the partial substitution of monoclinic LiMnO2 with
www.rsc.org/advances fluorine can improve the cycle stability and high-rate discharge capability of cathode materials.

around Mn3+ is distorted from a regular octahedron, and the

1. Introduction overall crystal structure is monoclinic due to the cooperative
Lithium manganese oxide (LiMnO2) compounds have received Jahn–Teller distortion. Therefore, it is difficult to inhibit the
attention as intercalation cathodes for rechargeable lithium ion irreversible structural transformation from layered LiMnO2 to
batteries due to their high theoretical capacity, low cost, and a spinel LiMnO2 during electrochemical cycling. According to
nontoxicity, and there has been signicant interest in mono- the rst-principles calculations, the Jahn–Teller effect should be
clinic LiMnO2 (space group C2/m, hereaer denoted as m- absent in the low-spin state, and the layered structure could be
LiMnO2) as a potential cathode material for replacing LiCoO2, stabilized in m-LiMnO2.9
which is the currently used cathode material in commercial Li- Cation doping protects the layered monoclinic structure
ion rechargeable batteries.1–3 However, m-LiMnO2 is generally against Jahn–Teller distortion10 and has superior Li insertion/
considered to be unstable compared to orthorhombic LiMnO2 extraction cycling properties for m-LiMnO2. Many studies
(space group Pmnm, hereaer denoted as o-LiMnO2).4 One have focused on stabilization of the layered material structure,
signicant drawback is the difficult synthesis of layered particularly for m-LiMnO2, by partial substitution of Mn by Cr,
m-LiMnO2 using the conventional high-temperature solid-state Al, Co, Ni and Mg.11–18 However, for m-LiMnO2 to be suitable for
reaction method because these methods always produce practical applications such as high-energy and power density
o-LiMnO2.5,6 Consequently, m-LiMnO2 was rst obtained by applications, further stabilization of the monoclinic structure is
metastable synthesis routes such as ion exchange and hydro- needed. Small amounts of additional dopants such as uorine19
thermal reactions.7,8 into the Li(Ni1/3Co1/3Mn1/3)O2 lattice have been reported to
In this compound, the O2
ions are arranged in a cubic close- improve the structural stability and enhance the cycling
packed structure, and the octahedral interstices are occupied by performance. Zheng et al. prepared the Li[Li0.2Mn0.54Ni0.13-
Li+ and Mn3+ with layered cation ordering. The neighboring Co0.13]O2
xFx (x ¼ 0, 0.05 and 0.10) composite materials with
MnO6 octahedra share a common edge. Due to the presence of different content of uorine by sol–gel method using NH4F as
high-spin Mn3+ on the octahedral sites, the local site symmetry uorine source. XRD and XPS analysis shows that the uorine
ions successfully substitute for oxygen sites. The F-doped Li
[Li0.2Mn0.54Ni0.13Co0.13]O2
xFx materials show superior cycling
College of Chemistry and Chemical Engineering, Xinjiang Normal University, Urumqi,
830054, Xinjiang, China. E-mail: suzhixj@sina.com; Fax: +86-991-4332683; Tel: +86-
performance.20 In fact, Jouanneau et al. discussed the inuence
991-4332683 of LiF additions on Li(NixCo1
2xMnx)O2 and found that

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materials could be obtained using LiF as a sintering agent with steam distillation at 160–180  C, the uoride in testing solution
almost no disturbance of the cell performance.21–23 would be released and absorbed by NaOH solution realizing the
In this work, we attempt to prepare a partial substitution of separation from matrix and other elements. Then, the content
O2
by F
layered monoclinic LiMnO2 using a high-temperature of uoride was determined by ion chromatography (IC).
solid-state reaction method with a subsequent ion-exchange
reaction. The morphology, microstructure, composition, and
2.3 Analysis of the valence states of manganese
electrochemical properties were investigated in detail to assess
the suitability of these samples as cathode materials. The total amount of manganese was determined by chemical
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conversion to permanganic radical using acidied ammonium

persulfate, the determination of Mn4+ by the acetylacetone-
2. Experimental iodometric method being carried out in the presence of Mn3+
2.1 Preparation and characterization without its interference, and the amount of the tetravalent and
trivalent manganese being determined by dissolving the
First, Mn(CH3COO)2$4H2O was heated with the ramping rate of
lithium manganese oxides in a known excess of ammonium
2  C min
1 and decomposed at 500  C for 15 h in air to produce
iron sulfate in 1 mol L
1 sulfuric acid and back-titrating the
Mn2O3. Samples of monoclinic a-NaMnO2 were prepared using
unreacted Fe2+ with standardized potassium dichromate. Based
a solid-state reaction of the stoichiometric mixture of Mn2O3
on the results obtained, the amount of bivalent manganese and
(0.01 mol, 1.58 g) and Na2CO3 (Na/Mn ¼ 1.1, 0.011 mol, 1.16 g)
average manganic valence could be calculated.24
in a closed crucible at 750  C for 24 h in air. The mixture was
quenched to room temperature and ground, and the process
was repeated. The resulting samples were stored in a desiccator. 2.4 Electrochemical performance
In the subsequent ion-exchange reaction, 1 g of a-NaMnO2 was The working electrode was prepared by compressing a mixture
mixed with 10 g LiCl in 40 ml n-hexanol and autoclaved at of the active materials with acetylene black and a binder (poly-
150  C for 12 h in a 50 ml Teon-lined stainless steel vessel. The tetrauoroethylene, PTFE) in a weight ratio of 75 : 20 : 5.
obtained m-LiMnO2 products were washed with de-ionized Lithium metal was used for the counter and reference elec-
water and then dried in an oven at 105  C for 12 h. Fluorine- trodes. The electrolyte was LiPF6 (1 M) in a mixture of ethylene
substituted materials were prepared with the molar ratio of carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl
F/Mn of 0.01/1, 0.03/1, and 0.05/1 with the homogeneous carbonate (EMC) in a weight ratio of 1 : 1 : 1. All procedures for
mixture of NH4F of 0.001 mol (0.037 g); 0.003 mol (0.0111 g); handing and fabricating the electrochemical cells were per-
and 0.005 mol (0.0185 g), respectively. The nal uorine- formed in an argon-lled glove box. The galvanostatic method
substituted materials were obtained by the above-mentioned was used to measure the electrochemical capacity and cycle life
method. of the electrodes under the charge–discharge current density of
The microstructure of the as-prepared samples was charac- 50 mA g
1 at room temperature using a LAND CT2001A
terized by X-ray diffraction (XRD, Rigaku D/max-2500) with instrument. The cut-off potentials for the charge and discharge
CuKa radiation and scanning electron microscopy (SEM, were set between 2.0–4.3 V (vs. Li+/Li). Cyclic voltammetry (CV)
HITACHI S-3500N). Elemental analysis for Na, Li, and Mn were was performed with a LK2500 electrochemical workstation,
performed using inductively coupled plasma atomic emission scanning from 2 to 4.3 V with a scan rate of 0.1 mV s
1. The
spectroscopy (ICP-AES, IRIS Advantage) and the content of electrochemical impedance spectra (EIS) were measured using
uorine by ion chromatography (ICS-2100) to determine the a Zahner IM6ex electrochemical workstation over the frequency
chemical composition of these materials. The Fourier trans- ranges from 10 kHz to 10 MHz with a 5 mV AC input signal
form infrared spectra (FTIR) of these samples were recorded applied between the working and reference electrodes.
from 400 to 4000 cm
1 at room temperature using the KBr wafer
technique in a Bio-Rad FTS 6000 FTIR instrument with a reso-
lution of 2 cm
1 in transmittance mode. The surface chemical 3. Results and discussion
state was recorded using X-ray photoelectron spectroscopy (XPS, 3.1 Composition and structure
PHI-5300 ESCA).
The composition of the as-prepared samples, which were
calculated from the results of ICP-AES, and IC determination
2.2 Determination of material composition and valence state of Mn analysis, are summarized in Table 1.
The sample was treated by HCl, HNO3 and HF at room For all samples, most of the Na+ cation can be exchanged and
temperature, H3BO3 was added to complex with excessive lithium concentration can be controlled at about 0.90 in unit.
uoride ions. Working conditions of the instrument was opti- All of the XRD patterns were rened by the Rietveld analysis, an
mized, appropriate analysis line of various elements was example of the Rietveld renement is shown in Fig. 1 for the
selected and the internal standard method was used to elimi- composition of LixMnO2
yFy. All diffraction peaks, except for
nate disturbance with yttrium selected as internal standard the market peaks, could be attributed to the small amount of
element, the content of lithium and manganese were deter- monoclinic Na0.7MnO2.05 because NaMnO2 was not stable and
mined by inductively coupled plasma emission spectroscopy was very hygroscopic in air; NaMnO2 was easily transformed to
(ICP-AES). The sample was decomposed by H2SO4. Aer water the more stable phase of Na0.7MnO2.05.25

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Table 1 Chemical composition of the m-LiMnO2 and F-substituted m-LiMnO2

Sample Design formula Precursor powders Valence of manganese Chemical composition

a NaMnO2 Na0.96MnO2 3.04 Na0.96MnO2

b LiMnO2 Na0.91MnO2 3.09 Na0.06Li0.85MnO2
c LiMnO1.99F0.01 Na0.90MnO1.98F0.02 3.08 Na0.05Li0.86MnO1.98F0.02
d LiMnO1.97F0.03 Na0.91MnO1.96F0.04 3.05 Na0.06Li0.88MnO1.96F0.04
e LiMnO1.95F0.05 Na0.92MnO1.93F0.07 3.01 Na0.06Li0.87MnO1.93F0.07
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samples could be assigned to the monoclinic structure with

space group of C2/m, which differs from o-LiMnO2.7–9 At the
same time the characteristic peak of a-NaMnO2 are not appear
noticeably in XRD, this shows that ion exchange basic
completely. Moreover, we also nd that the observed dhkl values
is greater than the standard and the 2q values is opposite. This
may be due to the material contains no exchange of sodium
(sodium ions with greater radius than lithium ion).
Lattice parameters of all samples obtained from the Rietveld
renement are listed in Table 3. With increasing uorine
content, cell volume increased from 0.0824 nm3 to 0.0839 nm3,
the increase of cell volume is attributed to the replacement of
O2
(r ¼ 0.132 nm) with greater F
(r ¼ 0.136 nm), which are in
agreement with literature values.26 From the table can be found
that the increase of the content of uorine can decrease the
valence state of Mn in material. The results attributable to the
low valence state of anion (F
) supersedes the high valence state
Fig. 1 The XRD patterns of the as-prepared samples: (a) Na0.96MnO2,
O2
, and it also demonstrated that the uorine ions successfully
(b) Na0.06Li0.85MnO2, (c) Na0.05Li0.86MnO1.98F0.02, (d) Na0.06Li0.88-
MnO1.96F0.04, and (e) Na0.06Li0.87MnO1.93F0.07. doped into the lattice structure.
The FTIR spectra of these as-prepared samples are indicated
in Fig. 2. The bands in the region of 3000–3500 cm
1 can be
assigned to OH stretching vibrations. Moreover, the bending
The Table 2 list the comparison between the observed values
mode vibration of water is observed at 1600–1800 cm
1. The
and the JCPDS-87155 standard card data. The characteristics of
weak absorptions at 2832 and 2886 cm
1 are due to C–H
the synthetic product crystal plane diffraction spacing and
stretching models, and the bands at around 1475 and 2465 cm
1
diffraction angle all can correspond well, the as-prepared
result from the absorption of the C]O group.27 Two obvious
absorption bands are observed in the infrared (IR) spectra of
these materials at around 875 and 993 cm
1 (except for
Table 2 Comparison between the observed and JCPDS-871255 Na0.96MnO2 samples), which could be attributed to the metal
values hydroxide vibration band.28 Furthermore, the IR bands in the
region of 450–750 cm
1 could be assigned to Mn–O stretching
dhkl (LiMnO2)/nm 2q/( ) vibrations in lithium-manganese-oxide compounds.29
hkl Observed JCPDS Observed JCPDS For the Na0.96MnO2 and Na0.06Li0.85MnO2 samples, one
featured band at 530 cm
1 is observed. However, for the
001 0.4849 0.4842 18.28 18.31 F-doped sample of Na0.05Li0.86MnO1.98F0.02, an obvious blue

2 0 1 0.2712 0.2711 33.02 33.01 shi is observed in the Mn–O stretching band from 532 to
110 0.2440 0.2435 36.80 36.89

1 1 1 0.2397 0.2395 37.48 37.50

2 0 2 0.2298 0.2295 39.12 39.21
111 0.2012 0.2006 45.02 45.15 Table 3 Lattice parameters of the samples after Rietveld refinement

1 1 2 0.1942 0.1942 46.46 46.74
201 0.1878 0.1875 48.45 48.49 Sample a (nm) b (nm) c (nm) Cell volume (nm3)
003 0.1626 0.1614 56.52 57.01
112 0.1560 0.1555 59.16 59.37 Na0.96MnO2 0.582 0.287 0.576 0.0962

1 1 3 0.1511 0.1505 61.26 61.56 Na0.06Li0.85MnO2 0.544 0.281 0.539 0.0824

3 1 2 0.1493 0.1487 62.12 62.36 Na0.05Li0.86MnO1.98F0.02 0.543 0.282 0.541 0.0828
020 0.1407 0.1404 66.34 66.53 Na0.06Li0.88MnO1.96F0.04 0.543 0.282 0.543 0.0831
021 0.1350 0.1348 69.54 69.66 Na0.06Li0.87MnO1.93F0.07 0.544 0.283 0.549 0.0839

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Fig. 3 shows the SEM images of the as-prepared samples. The

layered Na0.97MnO2 and monoclinic LixMnO2
yFy samples have
a similar bar-shaped morphology with a grain diameter of 5–8
mm and with small particles of about 2–3 mm in size. However,
a topotactic reaction can be observed in a morphology changes
from the SEM. Small particles can be found in Fig. 3. The things
is especially obvious with the increase of uorine content. The
results should be attributed to the primary particles become
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well-developed when the amount of uorine increases. Changes

of morphology reveal that incorporation of uorine alters the
surface energy and catalyzes the growth of the primary particles,
consistent with that reported for other cathode materials with
uorine doping.32,33

3.2 Electrochemical properties

Fig. 4 exhibits the initial charge/discharge curves of Lix-
Fig. 2 The IR spectra of (a) Na0.97MnO2, (b) Na0.07Li0.85MnO2, and (c)
MnO2
yFy (y ¼ 0, 0.02, 0.04, 0.07) at a current density of 50
Na0.06Li0.86MnO1.98F0.02.
mA g
1 (0.2 C) between 2.0 and 4.3 V. An initial discharge
capacity of 133.2 mA h g
1 is obtained for the Na0.06Li0.85MnO2
550 cm
1. The electronegativity of F (4.0), which is higher than sample, which is obviously higher than that of o-LiMnO2 ob-
that of O (3.5), can strengthen the Mn–O stretching bands, tained using the conventional high-temperature solid reaction.
whereas the thermochemical radius of F
(0.136 nm) is greater With the increase of uorine content, the discharge capacities
than the O2
ionic radius (0.132 nm), leading to the blue shi.30 of the initial discharge capacity is decreased to 129.2 mA h g
1
Certainly, with the uoride concentration increase, the blue at 0.2C for Na0.05Li0.86MnO1.98F0.02, the initial discharge
shi will become more obviously which causes the oxygen capacities of Na0.06Li0.88MnO1.96F0.04 and Na0.06Li0.87MnO1.93-
defects concentration increase in the material. Due to the F0.07 are 120.6 and 112.3 mA h g
1, respectively. This is due to
deciency of oxygen ion in the electrode material caused by the existence of the inactive substances uorine and the atomic
oxygen defects, there are positive charged oxygen vacancies in weight of uorine (19 g mol
1) slightly larger than oxygen
the structure; and then during the immersion of electrolytic atomic weight (16 g mol
1). Moreover, uorine substituted
solution to electrode surface, more oxygen defects produce materials exhibit higher charging voltage over the potential
thicker organic electrolytic liquid lm, which arise the organic range and the discharge plateau is lower than the pristine one,
electrolytic liquid lm resistance. This result implies that which is an indication of the higher polarization effect. This
oxygen defects will reduce the electrochemical capacity and similar phenomena, which is ascribed to the stronger bonding
cycling performance of the electrode material; and this is in strength of Li–F (577 kJ mol
1) bond than the Li–O bond (341 kJ
agreement with the electrochemical performance test results mol
1), are also observed and explained by previous
shown below.31 researchers.34,35

Fig. 3 The SEM images of the as-prepared samples: (a) Na0.96MnO2, (b) Na0.06Li0.85MnO2, (c) Na0.05Li0.86MnO1.98F0.02, (d) Na0.06Li0.88-
MnO1.96F0.04, and (e) Na0.06Li0.87MnO1.93F0.07.

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improved by uorine substitution, the good rate capability of

uorine substituted materials could be attributed to the exis-
tence of the strong bonding by uorine which stabilizes the host
structure and increases the stability of cathode materials.37 The
results also show that the electrochemical performances of the
materials were severely damaged with the uorine content
increased, this is related to the amount of oxygen defects in
materials. Therefore, the uorine content should be controlled
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in order to prevent more oxygen defects in synthetic materials.

In other words, the partial uorine substitution in the layered
monoclinic structure can signicantly depress this structural
transformation and slow the rate of capacity decay.
We also notice that the Na+ cation can be reserved at about
0.06 unit in all samples. The Na+ ionic radius (0.097 nm) is
larger than the Li+ ionic radius (0.060 nm). Thus, in monoclinic
Na-substituted LixMnO2, the small change of the interlayer
Fig. 4 The initial charge–discharge voltage profile (a), differential
capacity plots (b) of LixMnO2
yFy (y ¼ 0, 0.02, 0.04, 0.07) when cycled
spacing to accommodate Na allows high rechargeability and
between 2.0 and 4.3 V at a current density of 50 mA g
1. good cycle life. This result could be explained by the extraction
of a limited amount of sodium ions from the interlayer spacing
while maintaining the layered structure upon cycling.38
The rate capabilities of the materials are operated at the Initial investigation of LixMnO2
yFy were carried out using
same current densities between 2.0 and 4.3 V. Fig. 5 compares cyclic voltammetry, Fig. 6. A rate of 0.01 mV s
1 between
the discharge capacities of the electrodes at various C rates. The potential limits of 2 and 4.3 V was employed. Cycling
results of the electrochemical cycles indicated that the commenced with oxidation from the open circuit potential of
discharge capacity of monoclinic LiMnO2 was small at the 2 V. Fig. 6(a) and (b) shows typical cyclic voltammograms of the
initial cycles, gradually increased with increasing cycle number, Na0.06Li0.85MnO2 and Na0.05Li0.86MnO1.98F0.02 samples sub-
and the capacity nally stabilized. This result was consistent jected to 1, 2, 5, 10, 20 and 30 cycles and 0.1 mV s
1 over the
with the previously reported results of orthorhombic LiMnO2 potential range between 2.0 and 4.3 V (vs. Li+/Li). The striking
electrochemical cycle behavior. This phenomenon reveals that feature is the difference between the rst and subsequent
monoclinic LiMnO2 cathode materials undergo an activation cycles. In fact the difference is to be found in the original CV for
process during the electrochemical cycle, during which there is Na0.06Li0.85MnO2 shows two anodic peaks at 3.25 V and 4.18 V as
a phase transition from m-LiMnO2 to cubic spinel LixMn2O4.36 well as the corresponding cathodic peaks at 2.83 V and 3.85 V.
In comparison, the cycle stability of the Na0.06Li0.85MnO2 On repeated cycling, the peaks at 4.18 V and 3.85 V split into two
sample is not so good with a low capacity retention of 80.8 mA h peaks, which becomes more obvious aer 30 cycles. This peak
g
1 aer 50 cycles. However, the uorine substituted materials splitting suggests a gradual transformation of layered LiMnO2
show better rate capability at high charge and discharge rates. into the spinel phase.34 From Fig. 6(a), we can observe the
The capacity retention of these materials is signicantly anodic phase shows four oxidation peaks centered at 3.1 V,
4.0 V, 4.18 V, and 3.8 V aer 2 cycles, but the cathodic phase
shows only three reduction peaks with a major peak centered at
2.8 V and two minor peaks at 3.9 V and 4.1 V. The peak at 3.8 V
does not have reduced peak, which corresponds to an irrevers-
ible phase change. Similar irreversible phase changes were
observed by Paulsen et al. in O2-type Li2/3[Li1/6Mn5/6]O2 and
Li2/3[Co1/18Mn17/18]O2.39 The reason for this irreversible peak/
plateau is not presently known; however, because it is only
observed in stacking faulted compounds, the irreversible peak
could be correlated to crystallographic modication, oxygen
removal from the lattice and/or removal of the stacking faults.
For the Na0.05Li0.86MnO1.98F0.02 sample, the similar main
cathodic and anodic peaks with Na0.06Li0.85MnO2 sample in the
rst cycle are found in Fig. 6(b). From the CV curves of Fig. 6(b),
Li+ can mostly deintercalate from the structure of sample
Na0.05Li0.86MnO1.98F0.02 in the rst anode process, due to the
broader oxidizing peak about 3.8 V. But the reducing peak about
2.9 V is weaker in the rst cathode process. This result indicates
Fig. 5 Cycle performance of the as-prepared samples at different there is obvious capacity loss between the initial charge and
discharge current densities (charging at 50 mA g
1). discharge capacities, and the efficiency of reversible intercalate/

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Fig. 6 Cyclic voltammograms of the (a) Na0.067Li0.85MnO2 and (b) Na0.05Li0.86MnO1.98F0.02 subjected to 1, 2, 5, 10, 20 and 30 cycle.

deintercalate of Li+ is relatively lower, which is in accordance

with Fig. 4. As the cycle goes by, the intensity of oxidizing peak
about 3 V gradually becomes stronger, and the intensities of
reducing peak about 2.8 V and 4 V gradually become stronger.
However, the anodic or cathodic current densities change
slightly in the following cycles, evidencing the higher electro-
chemical stability of the Na0.05Li0.86MnO1.98F0.02 sample as
compared to the Na0.06Li0.85MnO2 sample.
The Fig. 5 also shows that the variation characteristics of
capacity with cycle number for the Na0.06Li0.85MnO2 and
Na0.05Li0.86MnO1.98F0.02 materials. The rst discharge of the
Na0.06Li0.85MnO2 sample is associated with a specic capacity of
133.2 mA h g
1 but this falls signicantly to 117.7 mA h g
1 at
the third cycle, then slowly increase the 190 mA h g
1 aer 20 Fig. 7 XRD patterns of (a) Na0.06Li0.85MnO2 and (b) Na0.05Li0.86-
cycles and the subsequent decay slowly. For the Na0.05Li0.86- MnO1.98F0.02 after 30 cycles.
MnO1.98F0.02 sample, the varying pattern is similar with the
Na0.06Li0.85MnO2 sample. The rst specic capacity on
discharge is 129.2 mA h g
1 but this falls signicantly to 95 mA The Nyquist plots of the electrochemical impedance spectra
h g
1 at the 5th cycle, and subsequent slowly increase to 219 mA (EIS) analyses are shown in Fig. 8. All plots consist of both
h g
1 aer 40 cycles. However, the greatest difference can be a semicircle in the high-frequency region and a slope in the low-
found in the thereaer cycle process, the capacity on discharge frequency region. The electrode reaction process is primarily
is very similar at around 218 mA h g
1. This is in accord with the controlled by a mixed process of lithium ion diffusion (Warburg
CV in Fig. 6 and reinforces the view that the electrochemical impedance, which is inversely proportional to the diffusion coef-
evidence points to a change occurring during the rst charge. cient DLi+) and the surface electrochemical reaction at a tempo-
In order to further verify the results of electrochemical test rary steady state of EIS. Compared to the Na0.07Li0.85MnO2 sample
and the inuence of uorine doping for the materials. The XRD from Table 4, the Warburg impedance of uorine-substituted
was used to conrmed by crystal structure measurements of the materials is lower, which contributes to their improved high
cycled cathode powder. Fig. 7 shows the XRD pattern of the rate capability. On the contrary, the charge-transfer resistance
Na0.067Li0.85MnO2 and Na0.05Li0.86MnO1.98F0.02 subjected to 30 increases aer uorine substitution due to the poor electro-
cycles. The diffraction peaks in the XRD pattern broadened aer chemical activity of the anions, while the Warburg impedance
electrochemical cycling, which is attributed to the creation of obviously decreases as compared to that of the Na0.07Li0.85MnO2
local lattice strain and tiny crystallites during cycling.40 The sample. Clearly, the Warburg impedance of the uorine-
results also show that the samples have been converted to the substituted material Na0.06Li0.86MnO1.98F0.02 is much smaller
cubic spinel phase LiMn2O4 upon cycling, the results are than that of the Na0.07Li0.85MnO2 sample, which is consistent with
consistent with the electrochemical experiments. However, the the improved high-rate capability demonstrated above.
layered structure LiMnO2 phase can obvious exist for the
Na0.05Li0.86MnO1.98F0.02 materials in the electrochemical
3.3 XPS spectra analysis of materials
process. This fully shows that uorine doping can effectively
inhibit the structure of the shi. The XPS spectra can provide chemical information such as the
oxidation state as well as the semi-quantitative composition of

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respectively. The peaks at the binding energy of about 641.60 eV

are similar to those observed in Mn2O3 and MnOOH.41 The
binding energy peak situated at 653.86 is close to the binding
energy of Mn 2P1/2 (653.90 eV) observed in the Mn2O3 sample.
The binding energy of Na 1s was determined to be 1071.26,
which is similar to that observed in NaF.42 Moreover, the
binding energy of F 1s is situated at 686.1 eV, which is similar to
that observed at 686.1 eV in MnF2.43 To further determine the
Published on 14 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 22/10/2015 05:12:51.

existence of uorine within the crystal structure, XPS

measurement was carried out on the four samples. Fig. 9(b)
shows the XPS spectra of F 1s for the pristine and F-doped
materials. All curve ttings were based on C 1s (C–C bonding
energy) calibration to 284.5 eV. As shown in the gure, with the
increase of the amount of F-doping, the area of the F 1s peak
proportionately increases, reecting an increase in the
concentration of the uorine ions in the doped material as the
Fig. 8 Electrochemical impedance spectra (EIS) of the as-prepared composition design. This observation is constant with the
samples at the discharged state (about 3.0 V (vs. Li+/Li)) after the 30th
consecutive changes of lattice constants shown in Section 3.1,
cycle.
which further proves that the uorine ions have been success-
fully doped into the lattice structure.
Table 4 Calculated electrochemical parameters from the AC
impedance spectra of the ion-substituted LixMnO2 samples using
ZView 2.8 softwarea
4. Conclusion
Sample (ICP-AES) Rct (U) CPE (10
5) Ws (U)
The uorine doped monoclinic LiMnO2 could be successfully
synthesized via a high-temperature solid-state reaction and
Na0.06Li0.85MnO2 122.31 1.04 270.71 subsequent ion exchange by hydrothermal method. The partial
Na0.05Li0.86MnO1.98F0.02 132.81 1.08 36.25 uorine substitution with high electronegativity anions
Na0.06Li0.88MnO1.96F0.04 152.91 1.05 112.32
strengthens the Mn–O bands in the layered monoclinic struc-
Na0.06Li0.87MnO1.93F0.07 221.62 2.91 117.31
ture, which stabilizes the structure. Though the F-doped
a
Rct represents the charge-transfer resistance, CPE represents the samples had lower initial capacities, they showed better cycle
constant phase element, and Ws represents the Warburg impedance.
performance compared with F-free samples. The Na0.05Li0.86-
MnO1.98F0.02 electrode delivers an initial discharge capacity of
129.2 mA h g
1 between 2 and 4.3 V at a current density of 50
the surface, thus enabling observation of the surface properties. mA g
1 at room temperature, which gradually increased to
a maximum discharge capacity of 219 mA h g
1 aer 40 cycles.
Fig. 9(a) shows the Mn 2p XPS spectra of the Na0.05Li0.86-
The research indicated that the different performances can be
MnO1.98F0.02 sample. The binding energies of Mn 2P1/2 and Mn
attributed to the different morphologies of the respective
2p3/2 were determined to be 653.86 eV and 641.80 eV,
materials as well as the effect of sodium ion concentration

Fig. 9 The XPS spectra of the Na0.06Li0.86MnO1.98F0.02 sample and F 1s for LixMnO2
yFy.

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Paper RSC Advances

within the structure. Therefore, controlling the morphology of 19 G. H. Kim, S. T. Myung, H. S. Kim, C. S. Yoon and Y. K. Sun, J.
the material and the amount of sodium ions in its structure may Electrochem. Soc., 2005, 152, A1707–A1713.
be advantageous for developing high quality cathode materials 20 J. M. Zheng, X. B. Wu and Y. Yang, Electrochim. Acta, 2013,
which can be diversied for specic applications in Li-ion 105, 200–208.
batteries. 21 S. Jouanneau and J. R. Dahn, J. Electrochem. Soc., 2004, 151,
A1749–A1754.
22 Q. G. Zhang, T. Y. Peng, D. Zhan and X. H. Hu, J. Power
Acknowledgements Sources, 2014, 250, 40–49.
Published on 14 October 2015. Downloaded by UNIVERSITY OF NEBRASKA on 22/10/2015 05:12:51.

23 J. L. Xie, X. Huang, Z. B. Zhu and J. H. Dai, Ceram. Int., 2011,

This work was supported by The National Natural Science
37, 419–421.
Foundation of China (21061015) and The Nature Science
24 W. S. Fyfe, Anal. Chem., 1951, 23(1), 174–175.
Foundation from Xinjiang autonomous region (2015211A037).
25 R. Chitrakar, H. Kanoh, Y. S. Kim, Y. Miyai and K. Ooi, J.
Solid State Chem., 2001, 160, 69–76.
References 26 S. H. Kang, I. Belharouak, Y. K. Sun and K. Amine, J. Power
Sources, 2005, 146, 650–653.
1 J. Reed and G. Ceder, Chem. Rev., 2004, 104, 4513–4534. 27 P. Barboux, J. M. Tarascon and F. K. Shokoohi, J. Solid State
2 P. Suresh, A. K. Shukla and N. Munichandraiah, Electrochem. Chem., 1991, 94, 185–196.
Solid-State Lett., 2005, 8, A263–A266. 28 E. Wolska, P. Piszora, W. Nowicki and J. Darul, Int. J. Inorg.
3 B. Ammundsen, J. Desilvestro, T. Groutso, D. Hassell, Mater., 2001, 6, 503–507.
J. B. Metson, E. Regan, R. Steiner and P. J. Pickering, J. 29 L. K. Kang, M. M. Zhang, Z. H. Liu and K. Ooi, Spectrochim.
Electrochem. Soc., 2000, 147, 4078–4082. Acta, Part A, 2007, 67, 864–869.
4 J. E. Greedan, N. P. Raju and I. J. Davidson, J. Solid State 30 H. D. B. Jenkins, H. K. Roobottom, J. Passmore and
Chem., 1997, 128, 209–214. L. Glasser, Inorg. Chem., 1999, 38, 3609–3620.
5 Y. J. Wei, H. Ehrenberg, N. N. Bramnik, K. Nikolowski, 31 X. Q. Wang, H. Nakamura and M. Yoshio, J. Power Sources,
C. Baehtz and H. Fuess, Solid State Ionics, 2007, 178, 253–257. 2002, 110, 19–26.
6 T. J. Kim, D. Son, J. Cho and B. Park, J. Power Sources, 2006, 32 Y.-S. He, L. Pei, X.-Z. Liao and Z.-F. Ma, J. Fluorine Chem.,
154, 268–272. 2007, 128, 139–143.
7 A. R. Armstrong and P. G. Bruce, Nature, 1996, 381, 499–500. 33 W. Oh, S. H. Park, J. H. Kim, Y. C. Bae and Y. K. Sun, J. Power
8 F. Capitaine, P. Gravereau and C. Delmas, Solid State Ionics, Sources, 2006, 157, 464–470.
1996, 89, 197–202. 34 G. H. Kim, M. H. Kim, S. T. Myung and Y. K. Sun, J. Power
9 Z. F. Huang, X. Meng, C. Z. Wang, Y. Sun and G. Chen, J. Sources, 2005, 146, 602–605.
Power Sources, 2006, 158, 1394–1400. 35 Y. S. He, L. Pei, X. Z. Liao and Z. F. Ma, J. Fluorine Chem.,
10 R. Prasad, R. Benedek and M. M. Thackeray, Phys. Rev. B: 2007, 128, 139–143.
Condens. Matter Mater. Phys., 2005, 71, 134111. 36 Y.-II Jang, B. Y. Huang, H. F. Wang, R. S. Donald and
11 G. Ceder and S. K. Mishra, Electrochem. Solid-State Lett., Y. M. Chiang, J. Electrochem. Soc., 1999, 146(9), 3217–3223.
1999, 2, 550–552. 37 P. Yue, Z. X. Wang, X. H. Li, X. H. Xiong, J. X. Wang, X. W. Wu
12 C. W. Park, I. R. Mangani, H. W. Ryu, C. J. Park, J. S. Lee, and H. J. Guo, Electrochim. Acta, 2013, 95, 112–118.
S. J. Song, J. H. Moon and J. Kim, J. Phys. Chem. Solids, 38 S. Bach, J. P. Pereira-Ramos and P. Willmann, Electrochim.
2007, 68, 1126–1130. Acta, 2006, 52, 504–510.
13 A. D. Robertson, A. R. Armstrong and P. G. Bruce, Chem. 39 J. M. Paulsen, C. L. Thomas and J. R. Dahn, J. Electrochem.
Mater., 2001, 13, 2380. Soc., 1999, 146, 3560–3565.
14 L. H. Yu, H. X. Yang, X. P. Ai and Y. L. Cao, J. Phys. Chem. B, 40 S. W. Mai, M. Q. Xu, X. L. Liao, L. D. Xing and W. S. Li, J.
2005, 109, 1148–1154. Power Sources, 2015, 273, 816–822.
15 B. Patoux, M. Dolle and M. M. Doeff, Chem. Mater., 2005, 17, 41 B. J. Tan, K. J. Klabunde and P. M. A. Sherwood, J. Am. Chem.
1044–1054. Soc., 1991, 113, 855–861.
16 J. H. Kim, C. W. Park and Y. K. Sun, Solid State Ionics, 2003, 42 V. I. Nefedov, Y. V. Salyn, G. Leonhsardt and R. Scheibe, J.
164, 43–49. Electron Spectrosc. Relat. Phenom., 1997, 10, 121–124.
17 B. J. Hwang, Y. W. Tsai, C. H. Chen and R. Santhanam, J. 43 R. G. Hayes, N. Edelstein and D. A. Shirley, Electron
Mater. Chem., 2003, 13, 1962–1968. Spectroscopy, North-Holland Publishing Company,
18 W. K. Pang, J. Y. Lee, Y. S. Wei and S. H. Wu, Mater. Chem. Amsterdam, 771-781, 1972.
Phys., 2013, 139, 241–246.

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