controllable synthesis of spherical li3v2(po4)3/c cathode material
TRANSCRIPT
Electrochimica Acta 90 (2013) 433– 439
Contents lists available at SciVerse ScienceDirect
Electrochimica Acta
jou rn al hom epa ge: www.elsev ier .com/ locate /e lec tac ta
Controllable synthesis of spherical Li3V2(PO4)3/C cathode material and its
electrochemical performance
Lu-Lu Zhanga,b, Gang Penga, Gan Liangc,∗, Peng-Chang Zhanga,d, Zhao-Hui Wangb,Yan Jiangb, Yun-Hui Huangb,∗, Hao Linb
a College of Mechanical and Material Engineering, Three Gorges University, 8 Daxue Road, Yichang 443002, Chinab State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, 1037 Luoyu
Road, Wuhan, Hubei 430074, Chinac Department of Physics, Sam Houston State University, Huntsville, TX 77341, USAd Shanghai Shanshan Tech Co., Ltd., Shanghai 201209, China
a r t i c l e i n f o
Article history:
Received 3 August 2012
Received in revised form
17 November 2012
Accepted 17 November 2012
Available online xxx
Keywords:
Lithium ion battery
Cathode material
Lithium vanadium phosphate
Spray-drying
Electrochemical performance
a b s t r a c t
Spherical Li3V2(PO4)3/C (LVP/C) composites are successfully synthesized via two different spray-drying
processes. XRD results reveal that some impurities, such as Na3V2(PO4)3, Li2NaV2(PO4)3 and Li4(P2O7),
appear when sodium salt of carboxy methyl cellulose (CMC) acts as carbon source. SEM images show
two different morphologies: solid spherical particles for LVP/C(A) prepared by adding CMC after pre-
sintering, and hollow for LVP/C(B) prepared by adding CMC before pre-sintering. Compared to LVP/C(B),
LVP(A) presents higher tap density and better electrochemical performance at any C-rate. Remarkably,
another charge/discharge plateaus or anodic/cathodic peaks around 3.85 V are detected for both LVP/C(A)
and LVP/C(B) electrodes, which is attributed to the formation of Li3−xNaxV2(PO4)3 or some other elec-
trochemically active composites containing Na+. CMC addition sequence has a significant influence on
morphology of Li3V2(PO4)3. Furthermore, acting as carbon source and Na dopant, CMC shows a notable
effect on electrochemical behavior of Li3V2(PO4)3 cathode material.
© 2012 Elsevier Ltd. All rights reserved.
1. Introduction
Monoclinic Li3V2(PO4)3 (LVP) has attracted extensive interest
as one of the most promising cathode materials for lithium-ion
batteries due to its high theoretical capacity (197 mAh g−1) and
high operating voltage (up to 4.0 V) [1–6]. Li3V2(PO4)3 consists of
a three-dimensional framework of slightly distorted VO6 octahe-
dra and PO4 tetrahedra that share oxygen vertexes hosting lithium
ions in relatively large interstitial sites [2,3]. However, poor intrin-
sic electronic conductivity of LVP, resulting from the separation
of VO6 octahedra by PO4 tetrahedra in the monoclinic structure,
limits its practical application in lithium-ion batteries. Much effort
has been made to improve the electronic conductivity and hence
the electrochemical performance in LVP by conductive metal and
carbon coating [7–28], metallic ions doping (Ti, Al, Cr, Fe, La, Mg,
Co, Na, Ca, Sc, Ti, Mn, Nb, K, etc.) [4,29–42], and surface mod-
ification (NbOPO4, MgO, etc.) [5,43]. For example, the positive
effect of Na-doping on the electrochemical performance of LVP
was recently studied by Kuang et al. [36,44]. Wang et al. [45–47]
∗ Corresponding authors. Tel.: +86 27 87558237; fax: +86 27 87558241.
E-mail addresses: phy [email protected] (G. Liang), [email protected]
(Y.-H. Huang).
also found that a suitable amount of Na-doping can improve
the electrochemical performance in some cathode materials. For
example, Wang and Yin et al. [45,46] found that Na-doping at Li-
site or Fe-site can improve the electrochemical performance of
LiFePO4 because of the enhanced electronic conductivity, decreased
potential polarization and reduced charge transfer resistance.
Park et al. [47] also reported that a small amount of Na-doped
Li1.1[Ni0.2Co0.3Mn0.4]O2 showed better cycle properties and rate
capability than that of the undoped sample due to the reduced
impedance during intercalation/deintercalation. Moreover, var-
ious synthesis methods have been developed to prepare LVP,
such as solid-state reaction [1,2,4–8,10,29,33,34,40,42], sol–gel
[12–15,17,21–23,30–32,35–37,40,41], microwave solid-state syn-
thesis [18], hydrothermal [9,26,38], rheological phase reaction
[19,28], wet coordination [24], chemical reduction and lithiation
[20], electrostatic spray deposition [27], ultrasonic spray pyrolysis
[25], and spray-drying process [11,16,48,49].
Spray-drying is a well-known method for synthesizing
fine homogeneous and multi-component powder samples
[11,16,48–51]. Compared with simple solid-state reaction and
other methods [52,26], spray-drying method is very effective to
mix raw materials by solution process at a molecular size level
and to easily obtain spherical particles. Moreover, this method
has many advantages such as cost effectiveness and easiness for
0013-4686/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.http://dx.doi.org/10.1016/j.electacta.2012.11.126
434 L.-L. Zhang et al. / Electrochimica Acta 90 (2013) 433– 439
industrial scale-up [16,53]. Recently, Huang et al. [11] synthesized a
sphere-like carbon-coated LVP composite by spray drying method
using PEG as dispersant and carbon source. Yu et al. [16,48,49]
also used spray drying and carbothermal method with citric acid
as carbon source and reductive agent to obtain LVP/C cathode
material. Compared with PEG [11] and citric acid [16,47,48] used
in spray drying method, CMC is easier to get spherical particles
[54] and hence to effectively improve the tap density of LVP [48].
In this work, carbon-coated LVP composites were prepared by
spray-drying process followed by solid-state reaction. Sodium salt
of carboxy methyl cellulose (CMC) was used not only as carbon
source, reductive agent and spray granulating agent, but also as
Na-containing dopant. The morphology was well controlled by
the sequence of CMC addition. The as-obtained LVP/C composites
were characterized with X-ray diffraction (XRD), scanning electron
microscopy (SEM) and electrochemical measurements.
2. Experimental
Li2CO3, NH4H2PO4, NH4VO3 and CMC were used as starting
materials for preparing Li3V2(PO4)3/C composites. The molar ratio
of Li:V:P was 3.06:2.00:3.00. Excess amount of Li2CO3 was used
to compensate the volatilization of lithium source during sinter-
ing process. The amount of CMC was based on the residual carbon
content of Li3V2(PO4)3/C. The LVP/C composites were prepared
via two different spray-drying processes. The first spray-drying
process is described as follows: Li2CO3, NH4H2PO4 and NH4VO3
were milled in alcohol for 6 h; then the obtained mixture was
dried overnight in an oven to evaporate alcohol, followed by pre-
sintering at 350 ◦C for 6 h under N2 flow in a tube furnace and then
cooling down to room temperature. After this, CMC was added into
the powder and ground for 10 h by ball-milling in distilled water
to obtain a homogeneous emulsion with solid content of about
22 wt%. Subsequently, the emulsion was spray-dried in a spray dry-
ing tower at a rate of 20 mL min−1 with inlet temperature 240 ◦C to
obtain spherical particles. Finally, the as-obtained CMC-contained
spherical precursor was calcined at 700 ◦C for 10 h in nitrogen
atmosphere. The second spray-drying process is different from the
first one just in CMC addition sequence. CMC was mixed with
all raw materials and ground for 10 h by ball-milling in distilled
water to ensure homogeneous mixing. The emulsion with solid
content of about 22 wt% was spray-dried under same condition
as the first process. The obtained spherical precursor (containing
CMC) was pre-sintered at 350 ◦C for 6 h followed by heat treatment
at 700 ◦C for 10 h in nitrogen atmosphere, and then cooled down to
room temperature. The products prepared by adding CMC after and
before pre-sintering are denoted as LVP/C(A) and LVP/C(B), respec-
tively. In order to keep the same coated-carbon content in the final
products, the added CMC amount was 15 wt% for LVP/C(A) and
18 wt% LVP/C(B). The overall synthesis process for the hierarchi-
cally sphere-shaped LVP/C composites is schematically illustrated
in Fig. 1.
X-ray diffraction patterns were obtained on a X’Pert Pro diffrac-
tometer with Cu-k� radiation (� = 1.5406 A) (XRD, X’Pert Pro,
PANalytical B.V.). The morphology and element distribution were
obtained with a scanning electron microscope (SEM, Sirion 200,
Holland) coupled with an energy dispersive X-ray detector (EDX).
Tap density was measured by a tap density measurement instru-
ment (JZ-1, China). The residual carbon content was determined
with a carbon-sulfur analyzer (CS600, LECO, USA).
The working electrodes were prepared by mixing active mate-
rial with PVDF and acetylene black in a weight ratio of 75:15:10
in N-methyl pyrrolidinone. The slurry of mixture was coated on
an aluminum foil (20 �m in thickness) using an automatic film-
coating equipment. The resulting film was dried under an infrared
Fig. 1. Schematic illustration of synthesis process for (a) LVP/C(A) and (b) LVP/C(B).
light to remove volatile solvent, punched into discs of 14 mm diam-
eter, and then pressed under a pressure of 6 MPa. After being dried
at 120 ◦C for 12 h in vacuum, the discs were transferred into an
argon-filled glove box (Super 1220/750, Mikrouna) and assem-
bled as working electrodes in 2025 coin cell using Celgard 2400
as the separator and lithium foil as counter and reference elec-
trodes. A solution of 1 mol L−1 LiPF6 in EC: DMC (LB-301, China)
was employed as the electrolyte. The cells were cycled between
3.0 and 4.8 V on cell testing instruments (LAND CT2001A, China).
Cyclic voltammetry (CV) tests were performed on an electrochem-
ical working station (PARSTAT 2273, Princeton Applied Research,
USA). CV curves were monitored at a scanning rate of 0.05 mV s−1
within a voltage range of 3.3–4.8 V.
3. Results and discussion
Fig. 2 shows the XRD patterns of the two samples prepared by
two different spray-drying processes. For the two samples, the main
diffraction peaks can be indexed as monoclinic structure of LVP
with a space group of P21/n, but some minor impurity peaks are also
observed and they can be attributed to Li4(P2O7), Li2NaV2(PO4)3,
and Na3V2(PO4)3 impurities, as reported by other groups [55,56].
From Fig. 2, we can see that the LVP/C(A) sample exhibits better
crystallization than LVP/C(B). The patterns do not display diffrac-
tion peaks of carbon, indicating that the pyrolytic carbon derived
from CMC is in amorphous form or the concentration of the residual
L.-L. Zhang et al. / Electrochimica Acta 90 (2013) 433– 439 435
Fig. 2. XRD patterns of LVP/C(A) and LVP/C(B) samples.
carbon is too low to be detected. In our case, the amount of residual
carbon in the two LVP/C samples is approximately 3.3 wt%, deter-
mined by carbon-sulfur analyzer. Here, the CMC can not only act as
spray granulating agent, but also as carbon source to improve the
electronic conductivity of LVP as well as reductive agent to reduce
V5+ to V3+.
Fig. 3 shows the SEM images of the as-prepared LVP/C sam-
ples. Both of the two samples present spherical shape with a wide
size distribution ranging from 8 �m to 35 �m. As shown in Fig. 3b
and d, the spherical particles for LVP/C(A) and LVP/C(B) are actu-
ally an aggregation of some smaller particles of several hundred
nanometers linked by the pyrolytic carbon. However, Fig. 3a and
c shows that the particles of LVP/C(A) and LVP/C(B) are in solid
and hollow sphere forms, respectively. The different morphologies
are schematically illustrated in Fig. 1. For LVP/C(A), since the raw
material does not contain CMC, only small amount of H2O, CO2, NH3
and other gaseous molecules are produced and released during the
pre-sintering process. The addition of CMC after pre-sintering only
produces much less amount of gaseous molecules. Thus, the final
product has a solid sphere-shaped morphology. Compared with the
precursor, there is only a very smaller volume contraction after sin-
tering at 700 ◦C (see Fig. 1a). For LVP(B), in contrast, since the raw
material is dispersed in CMC emulsion, large amount of H2O, CO2,
NH3 and other gaseous molecules can be produced and released
during the sintering process, resulting in a hollow sphere-shaped
morphology (see Fig. 1b). Thereby, compared with the volume of
the precursor materials, there is a much large volume contraction
for the final product. The EDX spectrum displayed in the insert of
Fig. 3a clearly shows the existence of sodium in the sample. In order
to investigate the distribution of the component elements in the
particles, the elemental mappings of V, C and Na of a spherical par-
ticle in LVP/C(A) sample were explored by EDX. As shown in Fig. 4,
a uniform distribution of V, C, Na and a uniformly carbon-coated
LVP spherical structure containing Na are confirmed. Tap density is
an important parameter for the electrode materials. The measured
tap density for LVP/C(A) is 1.07 g cm−3, which is much higher than
that (0.63 g cm−3) for LVP/C(B). Obviously, hollow spherical shape
leads to low tap density.
Fig. 5 shows the initial charge/discharge profiles and cycle
performance of LVP/C(A) and LVP/C(B) electrodes at 0.1 C. For the
two electrodes, in the first cycle (Fig. 5a), four characteristic charge
plateaus at voltages around 3.6, 3.7, 4.1 and 4.55 V are observed,
which correspond to four Li+ ions extraction steps from Li3V2(PO4)3 (Li3V2(PO4)3 → Li2.5V2(PO4)3 → Li2V2(PO4)3 → LiV2(PO4)3
→ V2(PO4)3). In addition, another charge plateau at voltage around
3.8 V is surprisingly detected, which is basically consistent
with the charge plateau of Li2NaV2(PO4)3 cathode material
reported by Cushing and Goodenough [55]. In Fig. 5a, a visi-
ble discharge plateau at about 3.9 V is observed, which is also
close to that of Li2NaV2(PO4)3 [55], but very different from
Fig. 3. SEM images of (a and b) LVP/C(A) and (c and d) LVP/C(B) samples. Inset of (a) is the EDX of LVP/C(A).
436 L.-L. Zhang et al. / Electrochimica Acta 90 (2013) 433– 439
Fig. 4. Elemental EDX mapping images for LVP/C(A) sample.
the typical discharge plateau of Li3V2(PO4)3 described else-
where [1–5,7–9,12–14,16–18,22,24–26,28]. Obviously, CMC as
the carbon source has a noticeable effect on electrochemical
behavior of Li3V2(PO4)3, which is attributed to the formation of
Fig. 5. (a) The initial charge/discharge profiles and (b) cycle performance for
LVP/C(A) and LVP/C(B) electrodes cycled at 0.1 C.
Li3−xNaxV2(PO4)3 or some other electrochemically active compos-
ites containing Na+. Kuang et al. [36] observed a positive effect of
low-level Na-doping on the electrochemical performance in LVP/C,
and found that Na-doping can shorten Li–Li distance and widen
Li–O contact, leading to improvement in the electrochemical
performance of Li3V2(PO4)3. In Fig. 5a, the LVP/C(A) electrode
delivers an initial specific charge capacity of 172.3 mAh g−1 and a
corresponding discharge capacity of 154.4 mAh g−1 with a coulom-
bic efficiency of 89.6% at 0.1 C, whereas LVP/C(B) only exhibits
an initial discharge capacity of 132.4 mAh g−1 with a coulombic
efficiency of 80.7%. From Fig. 5b, we can see that the LVP/C(A)
electrode also maintains a higher discharge capacity at 0.1 C than
LVP/C(B) over cycling. Fig. 6a shows the initial discharge profiles
at different C-rates and Fig. 6b shows the rate performance of
LVP/C(A) and LVP/C(B), which is cycled by a mode of charging
under a small current density of 0.1 C to 4.8 V and discharging at
different C-rate to 3.0 V. With the progressive discharging current
density, the plateaus gradually become indistinct and the capacity
decreases, implying the increasing polarization at higher current
density and corresponding electrolyte decomposition at high
operate voltage. Compared to LVP/C(B) electrode, LVP/C(A) elec-
trode shows better electrochemical performance at higher C-rate
from 0.5 C to 5.0 C. The LVP/C(A) delivers an average discharge
capacity of 140.5 mAh g−1 and 106.2 mAh g−1 at 0.5 C and 2.0 C,
respectively, which are much higher than that of LVP/C(B) (i.e.,
only 132.5 mAh g−1 at 0.5 C and 83.9 mAh g−1 at 2.0 C). Obviously,
the LVP/C(A) sample prepared by adding CMC after pre-sintering
shows better electrochemical performance than the LVP/C(B)
prepared by adding CMC before pre-sintering. Here, it should be
pointed out that the capacities for LVP/C(A) and LVP/C(B) are not
so high. This may be due to the large size of the spherical particles.
According to “radial model” and “mosaic model” reported by
Andersson and Thomas [57], the smaller the particle, the faster the
lithium ions and electrons extract, and hence the higher capacity.
Therefore, the capacity can be further enhanced by reducing the
particle size.
To further investigate the effect of CMC adding sequence
on electrochemical behavior of LVP/C(A) and LVP/C(B), cyclic
L.-L. Zhang et al. / Electrochimica Acta 90 (2013) 433– 439 437
Fig. 6. (a) The discharge profiles and (b) rate performance at various C-rates from
0.5 C to 5.0 C each for 10 cycles for LVP/C(A) and LVP/C(B) electrodes.
voltammogram (CV) tests were conducted at a slow scanning rate
of 0.05 mV s−1. Since structural change and solid electrolyte inter-
phase (SEI) formation of electrode are usually completed in the
second cycle due to penetration of electrolyte into the electrode
[58], the second cycle was chosen for comparison. As seen in
Fig. 7, for the two LVP/C electrodes, four typical anodic peaks of
Li3V2(PO4)3 at the voltages around 3.6, 3.7, 4.1 and 4.55 V are
observed, which corresponds to the extraction of three lithium
ions from Li3V2(PO4)3 by a sequence of phase transition pro-
cesses between the phases at different x values of LixV2(PO4)3
(x = 3.0, 2.5, 2.0, 1.0 and 0), associated with V3+/V4+ and V4+/V5+
Fig. 7. CV profiles of LVP/C(A) and LVP/C(B) electrodes at a slow scanning rate of
0.05 mV s−1 within potential window of 3.3–4.8 V (vs. Li+/Li).
redox couples. The result agrees well with the previous reports
for Li3V2(PO4)3 cathode materials [2,7–9,13,14,18,22]. It should be
noted that another oxidation peak around 3.8 V is also detected,
and the corresponding cathodic peak clearly appears around 3.7 V,
which is consistent with the charge/discharge result (Fig. 5a) dis-
cussed previously. Compared with LVP/C(B), the LVP/C(A) electrode
shows sharper CV peaks and higher peak current, indicative of
faster lithium-ion diffusion. Apparently, CMC as the carbon source
indeed shows a notable influence on electrochemical behavior of
Li3V2(PO4)3.
Since CMC serves as the source not only for C-coating but
also for Na-doping, the amount of added CMC definitely influ-
ences the contents of coated carbon and doped Na+, and hence
the electrochemical performance. For the LVP/C samples pre-
pared by adding 12, 15 and 18 wt% CMC after pre-sintering, the
residual carbon contents are 2.4, 3.3 and 4.8 wt%, respectively.
For the typical LVP/C sample with 15 wt% CMC, i.e., LVP/C(A),
the doped Na+ content is 1.76 at% determined by EDX. Fig. 8a
shows the initial charge/discharge profiles for the above LVP/C
samples. Four characteristic charge plateaus are observed at vol-
tages around 3.6, 3.7, 4.1 and 4.55 V, corresponding to four Li+
ions extraction steps from Li3V2(PO4)3. The new charge plateau
around 3.8 V and the corresponding discharge plateau at about
3.9 V appear for all samples, consistent with those reported in
Li2NaV2(PO4)3 [55]. Our Na-incorporated LVP samples show differ-
ent discharge plateaus as compared with the reported Li3V2(PO4)3
[1–5,7–9,12–14,16–18,22,24–26,28], which further confirms that
Na+ is doped into LVP. From Fig. 8a–c, it can be clearly seen that
the capacity of the LVP/C prepared with 15 wt% CMC is highest
especially at high C-rates. If more CMC is added, more residual
carbon will be coated; at the same time, more impurity phases
such as Li4P2O7, Li2NaV2(PO4)3 or Na3V2(PO4)3 will be formed.
Since Li4P2O7 has lower electronic conductivity (∼10−20 S cm−1)
and lithium-ion conductivity (∼10−21 S cm−1) than Li3V2(PO4)3
[59], it should have a negative effect on the electrochemical
performance if it exists in Li3V2(PO4)3. For other two impuri-
ties, Na3V2(PO4)3 is electrochemically inactive for lithium storage,
while Li2NaV2(PO4)3 delivers lower capacity as compared with
Li3V2(PO4)3 [55]. If excessive Na is introduced, more Li2NaV2(PO4)3
and/or Na3V2(PO4)3 impurity phases will be formed, leading to a
decreased capacity for Li3V2(PO4)3. Therefore, the amount of the
added CMC should be appropriate by comprehensively consider-
ing the effects of carbon coating and impurities. Fig. 8d shows
CV curves for the three LVP/C electrodes. Besides the four typi-
cal anodic peaks of Li3V2(PO4)3 at 3.6, 3.7, 4.1 and 4.55 V, a new
couple of redox peaks at 3.7 and 3.8 V are observed, consistent
well with the charge/discharge profiles in Fig. 8a. In addition,
the LVP/C with 15% CMC shows stronger and well-defined peaks
than the other two LVP/C samples, which agrees with its bet-
ter electrochemical performance. Therefore, the carbon source
CMC shows a notable influence on electrochemical behavior of
Li3V2(PO4)3.
In order to study the structural stability of the as-prepared
LVP/C material, XRD tests were performed for LVP/C(A) elec-
trodes under three conditions: before cycling, charged to 4.8 V,
and charged to 4.8 V followed by discharged to 3.0 V. Fig. 9
shows that the peaks of the electrode charged to 4.8 V shifts
slightly toward higher 2� from that of other two electrodes
and the peaks can be indexed to the V2(PO4)3 structure, which
has the same monoclinic structure and space group as that of
LVP material. Compared with Fig. 2, there is no obvious change
between the powder and the electrode before cycling and dis-
charging to 3.0 V. This result indicates that Na-incorporation has
no influence on the structural stability, and thus the monoclinic
structure of Li3V2(PO4)3 remains after cycling between 3.0 and
4.8 V.
438 L.-L. Zhang et al. / Electrochimica Acta 90 (2013) 433– 439
Fig. 8. The electrochemical performance of LVP/C samples prepared by adding different amount of CMC after pre-sintering.
Fig. 9. XRD patterns of LVP/C(A) electrodes before cycling, charging to 4.8 V and
charging to 4.8 V followed by discharging to 3.0 V.
4. Conclusions
Spherical Li3V2(PO4)3/C composites were successfully synthe-
sized via two different spray-drying processes using CMC as spray
granulating agent and as carbon source. Particle morphology can
be well controlled by changing the sequence of CMC addition.
Adding CMC after pre-sintering gives rise to solid spherical par-
ticles (LVP/C(A)), while adding CMC before pre-sintering yields
hollow sphere structure (LVP/C(B)). LVP(A) presents higher tap
density and better electrochemical performance at any C-rate
than LVP/C(B). Interestingly, a new charge/discharge plateau or
anodic/cathodic peak around 3.85 V was detected for both LVP/C(A)
and LVP/C(B) electrodes, which is attributed to the formation of
Li3−xNaxV2(PO4)3 or some other electrochemically active com-
pounds containing Na+. XRD results show that Na-incorporation
does not change the structural stability of LVP. Thus, CMC as carbon
source has a notable influence on electrochemical behavior of LVP
cathode material, but not on the monoclinic structure of LVP. The
present work using CMC as carbon source provides a new approach
for those Na-doped cathode materials with poor electronic conduc-
tivity.
Acknowledgements
This work was supported by the NSFC under Grant nos.
50825203 and 21175050, and the MOST of China under Grant nos.
2011DFB70020 and 2011AA11290; US National Science Foundation
under Grant no. CHE-0718482, an award from Research Corpora-
tion for Science Advancement, and an ERG grant from Sam Houston
State University. In addition, the authors thank the Analytical and
Testing Center of Huazhong University of Science and Technology
for providing XRD and SEM measurements.
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