Fabrication of One-Dimensional Mesoporous CoP Nanorods as Anode Materials for Lithium-Ion Batteries

Article abstract of DOI:10.1002/ejic.201700616

One-dimensional mesoporous CoP nanorods have been successfully synthesized via a facile hydrothermal method and subsequent low-temperature thermal phosphorization treatment. At a current density of 500 mA g^–1, CoP nanorods as anode materials for lithium ion batteries deliver a high discharge capacity of 894 mAh g^–1 after 300 cycles, with a coulombic efficiency of over 99 %. Even at a high current rate of 4000 mA g^–1, the discharge capacity of the CoP electrode can still retain 467 mAh g^–1. The results suggest that the introduction of cobalt and the special mesoporous nanorods play important roles in enhancing the electrochemical properties. Therefore, this rodlike CoP electrode is competent as a promising anode material for high-performance lithium-ion batteries.

Full text of DOI:10.1002/ejic.201700616

A Journal of
Accepted Article
Title: Fabrication of one-dimensional mesoporous CoP nanorods as
anode materials for lithium-ion batteries
Authors: Bei Wang, Qiang Ru, Qing Guo, Xiaoqiu Chen, Zhen Wang,
Xianhua Hou, and Shejun Hu
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To be cited as: Eur. J. Inorg. Chem. 10.1002/ejic.201700616
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10.1002/ejic.201700616
European Journal of Inorganic Chemistry
FULL PAPER
Fabrication of one-dimensional mesoporous CoP nanorods as
anode materials for lithium-ion batteries
Bei Wang,[a,b,c] Qiang Ru,*[a,b,c] Qing Guo,[a,b,c] Xiaoqiu Chen,[a,b,c] Zhen Wang,[a,b,c] Xianhua Hou,[a,b,c] and
Shejun Hu,[a,b,c]
Abstract: One-dimensional mesoporous CoP nanorods have been
successfully synthesized via a facile hydrothermal method and
subsequent low temperature thermal phosphorization treatment. At a
current density of 500 mA g−1, CoP nanorods as anode materials for
lithium ion batteries deliver a high discharge capacity of 894 mAh g−1
after 300 cycles with a coulombic efficiency over 99%. Even at a
high current rate of 4000 mA g-1, the discharge capacity of the CoP
electrode can still retain 467 mAh g-1. The results suggest that the
introduction of Co element and the special mesoporous nanorods
play important roles in enhancing the electrochemical property.
Therefore, this rod-like CoP electrode is competent as promising
anode materials for high-performance lithium-ion batteries.
good rate capability is the critical factor for the development of
LIBs.
In recent years, phosphorus-based anodes have aroused
extensive interest due to their promising features of abundant
resource, suitable redox potential and high specific theoretical
capacity.[14-15] Among them, non-toxic, inexpensive and
chemically durable red phosphorus (R-P) exhibits a high
theoretical capacity of 2595 mA h g−1. Nevertheless, the defects
of intrinsically low electrical conductivity (<1.0 × 10−14 S cm−1)
as well as severe volume expansion (>300%) commonly cause
serious pulverization of the electrode and deteriorated
electrochemical performance,[16-18] which definitely hinders the
practical applications for LIBs. [19-20] Some effective attempts to
address those problems have been focused on designing
diversified phosphides by introducing metal elements (Co, Mn,
Ni, Cu, Fe, Sn, Mo etc.) and synthesizing various nanostructures
(nanorod, nanowire, nanosphere, peapoded shape and so on).
[21-27] For example, Kwon et al. prepared CoxP compounds with a
good cycling durability of 407 mA h g-1 after 200 cycles. [28] Bai et
al. reported that peapod-like Ni2P shows a high reversible
capacity of 628 mAh g-1 after 200 cycles at a current density of
100 mA g-1.[29] Kim et al. synthesized teardrop-shaped SnP0.94
with a reversible capacity of 618 mA h g-1 after 100 cycles at 120
mA g-1.[30] In addition, porous nanostructures are also in favor of
lithium ions storage.[31] The results explicated that these methods
are conducive to improving the electrochemical properties of
LIBs. Besides, metal phosphides also have a good development
prospect in electrocatalytic field.[32]
Introduction
At present, continuous development of the economy companied
with the fossil fuel consumption of the industrialization has
brought about increasingly serious environment and energy
crisis.[1-3] To deal with these dilemmas, eco-friendly and
sustainable energy sources have attracted worldwide concern. [4-
6]
Currently, as one of the promising energy storage systems,
lithium-ion batteries (LIBs) have been intensively employed in a
variety of application fields from mobile devices to transportation
industries owing to its desirable energy density, high potential,
light weight and environmental friendliness.[7-10] However,
considering connatural disadvantages of relatively low specific
capacity (372 mAh g-1) and safety issue, commercial graphite
anodes fail to satisfy further application requirements for next-
generation high performance LIBs.[11-13] Thus, exploring novel
candidates with high power density, excellent cycle stability and
Enlightened by above-mentioned approaches, we
successfully synthesized one dimensional (1D) mesoporous
CoP nanorods by a facile hydrothermal method and subsequent
low temperature thermal phosphorization treatment. In particular,
this strategy is much more controllable and rational by using
cost-effective raw materials instead of hypertoxic and costly
organophosphorus sources. This 1 D mesoporous nanorods not
only provide more active positions and enough free space to
mitigate the volume expansion, but also shorten the diffusion
path to facilitate fast transport of electron and Li+. Thus, as-
synthesized CoP electrode as anode materials exhibits long
cyclic stability and good rate performance.
B. Wang, Prof. Ru, Q. Guo, X.Q. Chen, Z. Wang, Prof. Hou and
Prof. Hu
[a]
Guang dong Provincial Key Laboratory of Quantum Engineering and
Quantum Materials, School of Physics and Telecommunication
Engineering, South China Normal University, Guangzhou 510006,
China.
E-mail addresses: rq7702@yeah.net (Q. Ru)
[b]
[c]
Guangdong Engineering Technology Research Center of Efficient
Green Energy and Environmental Protection Materials, South China
Normal University, Guangzhou 510006, P. R. China.
Engineering Research Center of Materials and Technology for
Electrochemical Energy Storage (Ministry of Education), Guangzhou
510006, P. R. China.
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10.1002/ejic.201700616
European Journal of Inorganic Chemistry
FULL PAPER
R-P particles present large size above 50 µm, as depicted R-P
in Figure S2 (supporting information). Compared with large-
sized R-P material, the nanosized of CoP particles will help to
promote electrochemical lithium storage capability in terms of
more active sites, convenient ion diffusion pathways and good
penetration of the electrolyte. [5,34-38]
Results and Discussion
Figure 1. shows XRD pattern of the obtained CoP nanorods,
this product conforms to the characteristic of orthorhombic CoP
phase (JCPDS 29-0497). Main diffraction peaks centered at
31.6°, 32.0°, 36.3°, 36.7°, 46.2°, 48.1°, 48.4°, 52.3°, 56.0° and
56.8°, can be well indexed to (011), (002), (111), (102), (112),
(211), (202), (103), (020) and (301) planes, respectively. The
absent peaks of metallic Co, P and other impurities also indicate
a high level of purity in phosphorization process. Moreover,
broad peaks with low intensity suggest that as-prepared sample
has
a
fine particle size,[33] which is beneficial to the
electrochemical properties. As a comparison, the XRD pattern of
commerical red phosphorus (R-P) is also investigated. As shown
in Figure S1 (Supporting Information), R-P represents three
peaks centered at about 15°, 33°, and 56°, which are well
matched with previous report.[19]
Figure 2. SEM images of (a) the Co- precursor and (b) CoP nanorods under
different magnifications( with insert of magnification, inset scale bar:100 nm) ,
(c) TEM and (d) HRTEM images of CoP
Moreover, porous properties were tested by N2 adsorption-
desorption isotherm at 77 K based on Brunauer-Emmett-Teller
(BET) method. The isotherm in Figure 3 (a) belongs to type IV
category with a noticeable hysteresis loop at the P/Porange of
0.70-0.95,[39] and BET surface area is estimated to be 16.74
m²/g. Besides, the pore size distribution in Figure 3 (b) was
measured by Barrett-Joyner-Halenda (BJH) method, mesopores
are mainly situated in the range of 3-9 nm. 1D CoP nanorods
with high surface area and sufficient pores could not only afford
more electrochemical active sites but also facilitate charge
transfer, thus resulting in enhanced lithium-storage capability.
Figure 1. XRD spectra of CoP nanorods with inset of crystal structure.
The SEM images present morphological aspects of the Co-
precursor and CoP nanorods under different magnifications. As
shown in Figure 2 (a), The precursor displays well-defined 1D
(one-dimensional) shape with smooth outside surface (the
inserted image). The morphology of final product CoP shown in
Figure 2 (b), manifests rod-like fashion. In detail, these nanorods
changes partially with rough surface composed of many
nanosized particles (the inserted image) due to the thermal
decomposition of the precursor and the recrystallization of the
phosphorization process. To further explore nanorod features of
CoP, TEM image shown in Figure
2 (c) reveals that
nanocrystallites assemble together to generate nanorods.The
corresponding HRTEM image shown in Figure 2 (d) exhibits a
lattice fringe with a d-spacing value of 0.25 nm, the result is in
good agreement with the (111) plane of the CoP phase. While,
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10.1002/ejic.201700616
European Journal of Inorganic Chemistry
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Figure 3. (a) the BET curve and (b) BJH porsize distribution of CoP
nanorods
Figure 4. High resolution XPS spectra of the CoP (a) Co 2p and (b) P 2p.
X-ray photoelectron spectroscopy was carried out to
elucidate more detailed information about valence states of the
CoP. Figure 4 (a) demonstrates a high-resolution Co 2p
spectrum, two spin-orbit peaks centered at binding energy of
778.8 and 793.9 eV are ascribed to Co 2p3/2 and Co 2p1/2 of CoP
phase, respectively. And two peaks at 781.8 and 798.1 eV are
corresponding to oxidized Co species (Co 2p3/2 and Co 2p1/2),
respectively. While the other two peaks (flagged as “Sat.”) at
786.5 and 803.2 eV are assigned to satellites due to shake up
excitation of the high-spin Co2+.[40] Figure 4 (b) shows a high-
resolution P 2p spectrum, two peaks are mainly identified as Co-
P and P-O chemical bonds. Two peaks at 129.6 and 130.4 eV
are attributed to P 2p3/2 and P 2p1/2 of the CoP phase. While the
peak at 133.9 eV puts down to the oxidized surface [41]. The
oxidized signals could be assigned to the inescapable surface
oxidation when exposed in air, which is the common problem of
metal phosphide surface appearing in previous reports. [27, 42-44]
To best understand lithium storage capability of CoP
nanorods, electrochemical measurements were conducted.
Figure 5 (a) and (b) present cyclic voltammetry (CV) curves of
CoP and R-P in the first five cycles at a scan rate of 0.2 mV s-1
between 0.01 and 3.0 V, respectively. For CoP, it is noted that
the redox peaks of the first cycle are visibly different from the
following CV curves, especially in the cathodic branch. A broad
irreversible reduction peak located at ~0.40 V could be related to
the lithium intercalation of the CoP and the formation of solid
[21,
electrolyte interphase (SEI) film
45], as well as other
irreversible reaction In the anodic process during the first cycle,
two peaks at ~1.05 V and ~1.16 V are ascribed to continuous
lithium extraction. While in the second cycle, the previous
cathodic peak (~0.4 V) shifts to 0.6 V, this phenomenon is
probably caused by the structural rebuilding during the activation
process. For R-P, in the initial cathodic scan, a broad peak at
around 0.57 V can be attributed to the generation of SEI film and
insertion of Li+. In the anodic process, the peak at around 1.15
V resulted from the lithium extration reaction.[14] In subsequent
cathodic/anodic cycles, R-P electrode shows continuous lithium
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10.1002/ejic.201700616
European Journal of Inorganic Chemistry
FULL PAPER
insertion/extraction process without apparent peaks. Compared
with R-P, the CV profiles of CoP overlap better after the initial
cycle, it suggests that the introduce of Co element is helpful to
improve the electrochemical stability, charge transfer kinetics
and coulombic efficiency.
Figure
5
(c) and (d) show the Galvanostatic
charge/discharge profiles of the CoP and R-P electrodes for the
1st, 2nd, and 100th cycle at a current density of 500 mA g-1. At
the 1st cycle of CoP, it is observed that there is a sloping
potential plateau around ~0.40 V, followed by slowly translating
into the cutoff voltage of ~0.01 V. In the latter cycles, the
discharge potential plateau rises to ~ 0.6 V, this changing trend
is in keeping with the CV curve. Furthermore, the
charge/discharge specific capacities are 825.7 and 956.8 mAh g-
1, respectively, showing an initial columbic efficiency of 86%.
Compared with the theoretical capacity (894 mAh g-1), the extra
capacity could be attributed to the formation of SEI film during
the initial charge /discharge process, and that is common
phenomenon of anode materials reported in previous
literature.[23,29,46-47] At
the
2nd
cycle,
the
specific
charge/discharge capacities of 721 and 769 mAh g-1 are
observed, and the columbic efficiency reaches 93%. Up to the
100th cycle, a high discharge capacity of 655 mAh g-1 is still
maintained, and the columbic efficiency is almost above 99%,
while commerical R-P only delivers the first charge/discharge
capacity of 155/1131 mAh g-1 with a very low coulombic
efficiency of ~13.7% on account of poor electrical conductivity
and huge volume expansion. After 100 cycles, the capacity
retention of R-P is only 137 mAh g-1. The result that the CoP
electrode has better cycling reversibility and stabliity than that of
R-P would be ascribed to the special mesoporous structure
which provides big buffer space to alleviate volume change
during the charge and discharge process.
.
Figure 5. Electrochemical features: (a) and (b) Cyclic Voltammetry curves of
the 1 D CoP and R-P in the first five cycles at a scan rate of 0.2 mV s-1
between 0.01 and 3.0 V. (c) and (d) Galvanostatic charge/discharge profiles of
the CoP and R-P for the 1st, 2nd, and 100th cycle at a current density of 500
mA g-1.
Figure 6 (a) displays long cyclic performance of as-prepared
CoP nanorods and commercial R-P at a constant current density
of 500 mA g-1. Compare with R-P, CoP nanorods show excellent
cyclic capacity, the discharge capacity of 894 mA h g−1 is still
retained after 300 cycles, corresponding to ~93% of the initial
capacity. And during 10-300 cycles, the columbic efficiency of
CoP electrode consistently sustains above 98%, indicating a
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10.1002/ejic.201700616
European Journal of Inorganic Chemistry
FULL PAPER
good electrochemical stability and reversible capacity. The
capacity increasing after 40 cycles could be attribute to the
activation process of materials during the charge discharge
process. In addition, we compared the discharge capacity of
CoP nanorods with previously reported metal phosphide anodes.
As shown in table 1, rod-like CoP electrode shows high lithium
strorage capability and good cycling stability, which will be an
attractive anode material for lithium ion batteries.In conclusion,
the reasons for CoP nanorods with achieved electrochemical
properties may be explained as follows: (1) The introduction of
metallic Co promotes the electronic conductivity; (2) Large
specific surface and high porosity offer additional lithium storage
active sites and sufficient free space, which is conducive to
buffering the dramatic volumetric expansion and restraining the
pulverization of the electrode; (3) 1D nanosized architecture
effectively shortens the diffusion path, facilitating fast transport
of electrons and Li+ ions.
Figure 6. (a) Cycling performance of the CoP and R-P at a constant current
density of 500 mA g-1. (b) Rate performance of the CoP at various current
densities from 200 to 4000 mA g-1.
Table 1. Comparison of discharge capacity of CoP nanorods in this work and
the previously reported metal phosphide anodes.
Initial
Reversible
capacity/
cycles
discharge
capacity
(mAh g-1)
Current
density
This special architecture also plays an important role in
ameliorating rate performance of the CoP electrode. It was
evaluated at different current densities ranging from 200 to 4000
mA g-1. As shown in Figure 5 (d), the CoP electrode shows
admirable rate capability even at large current density, yielding
average discharge capacities of 856, 690, 624, 565, 527 and
467 mAh g-1 with gradually increasing current densities of 200,
400, 800, 1000, 2000 and 4000 mA g-1, respectively. During
following cycles, the specific capacities become 549, 602, 655
and 726 mAh g-1 as altering current densities back to 2000, 1000,
800 and 400 mA g-1. Particularly, the reversible capacity can
rebound to 818 mAh g-1, nearly approximating its theoretical
capacity when the current density returns to 200 mAg-1 after 110
cycles. All results clearly indicate good rate performance and
high cycling stability.
Materials
Ref.
CoP nanorods
MnP
956.8
894 /300
100 mA g-1
This work
1104
973.9
1027
287/50
450/50
630/200
50 mA g-1
54.2 mA g-1
100 mA g-1
[22]
[48]
[29]
Ni2P/Graphene
Peapod-like Ni2P
1055.7
986
788/25
5 µA cm-2
30 mA g-1
[21]
[49]
CoP thin film
Nanorod-FeP@C
480/200
To futher explore the influences of introduction of Co
element and mesoporous nanorods on the charge transfer
kinetics of electrode, the electrochemical impedance spectro-
scopy (EIS) was performed, the Nyquist plots are shown in
Figure 7. It can obviously observerd that both the Nyquist plots
are composed of semicircle in the middle-high frequency rang
and inclined line in low-frequency areas. The diameter of
semicircle is related to the charge-transfer impedance (Rct).The
inclined line is associated with warburg impendence (Wo), which
is associate with the diffusive resistance of lithium ions. the
diameter of CoP is obviously smaller than commercial R-P,
indicating lower Rct and good electron transport in CoP
electrode. The improved charge transfer could be attributed to
the introduction of Co element enhancing the electricity
conductivity of the electrode, and the mesoporous nanorod could
shorten the pathway of electron transmission.
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10.1002/ejic.201700616
European Journal of Inorganic Chemistry
FULL PAPER
after 300 cycles at a current density of 500 mA g-1. Even at a
current density of 4000 mA g-1, the rate capacity still retains 467
mAh g-1. Consequently, CoP nanorods may be promising
applications in LIBs.
Experimental Section
Analytic grade chemicals purchased from Aladdin Ltd. (Shanghai, China)
including Cobalt nitrate hexahydrate (Co(NO3)2•6H2O), urea (CO(NH2)2),
ammonium fluoride (NH4F), sodium hypophosphite (NaH2PO2), red
phosphorus, were used without further purification.
Preparation of Co-precursor and mesoporous CoP nanorods:
Figure 7. Nyquist plots of the CoP and R-P bef ore cy cles in the frequency
range from 100 KHz to 0.01 Hz.
The 1D co-precursor was fabricated by a facile hydrothermal route. 1.02
g of Co(NO3)2•6H2O, 0.33 g of NH4F and 1.05 g of CO(NH2)2 were
uniformly dissolved in 80 mL deionized water, then the solution was
transferred to a 100 mL Teflon-lineds autoclave for following thermal
treatment at 120 °C for 6 h. When cooled naturally, the pink precipitation
was washed several times and dried in a vacuum oven at 80 °C over
night. In order to synthesize cobalt phosphide, the subsequent
phosphorization treatment was conducted in a tube furnace. In details, 2
g of NaH2PO2 and as-prepared Co-precursor were placed into porcelain
crucible at the upstream and the downstream position, separately.
Whereafter, the reactants were heated to 350 °C at the heating rate of
1 °C min-1 under Ar atmosphere for 2 h and then cooled to ambient
temperature. The final product of mesoporous CoP nanorods was
harvested.
In order to further understand the influence of special 1D
architecture on electrochemical performance. The SEM images
of the CoP electrode was tested after 100 cycles at the current
density of 500 mA g-1. As shown in Figure 8, although the
texture of CoP nanorods are maintained in some degree, it is
apparent that pristine CoP nanorods transform into coral-like
nanorods with much coarser surface due to the partial
pulverization during charge/discharge process. Meanwhile, there
are also numerous tiny nanoparticles on the surface of the
electrode, caused by repetitive lithium intercalation/extraction.
These morphological changes may provide more contact areas
of electrode/electrolyte and more active sites as well as enough
free space, which will help to enhance lithium storage capability
and alleviate severe volume expansion.
Material characterizations
Crystal phase identification was determined by powder X-ray diffraction
(XRD) using PAN alytical X’Pert PRO diffractometer with Cu/Kα radiation
and λ=1.5406 Å. The morphological features were measured by scanning
electron microscope (SEM, ZEISSULTRA55) and transmission electron
microscope (TEM, JEM-2100HR). The specific Brunauer-Emmett-Teller
(BET) surface area was carried out on a Coulter SA 3100 surface area
analyzer. X-ray photoelectron spectroscopy (XPS) measurment was
carried out on PHI 5800 ESCA system to reveal the surface chemical
valence state with Al Kα (150 W, 1486.6 eV) radiation as the probe beam.
Figure 8. SEM images of the CoP electrode after 100 cycles at a current
density of 500 mA g-1
Electrochemical measurements
Conclusions
CR2430 coin-type cells were assembled in an agron-filled glove box to
evaluate electrochemical performance. The working electrode consisted
of CoP nanorods or red phosphorus, super-P and LA 133 with the weight
ratio of 7:2:1. The average mass loading of active material each
electrode was about 1 mg. Metallic lithium foil was utilized as the counter
and the reference electrode, Celgard 2400 film was used as the
separator and commercial electrolyte was 1 M LiPF6 in the solution of
ethylene carbonate, diethyl carbonate, and ethyl methyl carbonate (1: 1 :
1 by volume). Cyclic voltammetry test was carried out with the scan rate
1D mesoporous CoP nanorods were successfully synthesized
and evaluated as anode materials for LIBs. The CoP electrode
delivers high specific capacity, good cycling stability and rate
capability. The excellent electrochemical property is due to the
unique architecture with additional storage sites, convenient
diffusion channels and enough free space. For example, a
reversible specific capacity of 894 mAh g−1 can be maintained
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10.1002/ejic.201700616
European Journal of Inorganic Chemistry
FULL PAPER
of 0.2 mV s-1 on solartron 1470 electrochemical workstation.
Galvanostatic charge/discharge data was executed on NEWARE battery
testing equipment between 0.01 and 3.0 V at various current densities.
The electrochemical impedance spectroscopy (EIS) measurement was
performed from the CHI604D electrochemistry system in the frequency
ranging from 0.01 Hz to 100 KHz.
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10.1002/ejic.201700616
European Journal of Inorganic Chemistry
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10.1002/ejic.201700616
European Journal of Inorganic Chemistry
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Key Topic*The synthesized 1D
One-dimensional mesoporous CoP nanorods
mesoporous CoP anode materials
have enhanced electrochemical
performances of lithium-ion batteries
were synthesized by
a facile hydrothermal
method and subsequent low temperature
thermal phosphorization treatment. when
used as an anode material for lithium ion
Bei Wang,[a] Qiang Ru,*[a] Qing Guo,[a]
Xiaoqiu Chen,[a] Zhen Wang,[a] Xianhua
Hou,[a] and Shejun Hu,[a]
battery, CoP electrode delivers
a
high
discharge capacity of 894 mAh g−1 after 300
cycles at a current density of 500 mA g-1.
Even at a current density of 4000 mA g-1, the
rate capacity of CoP electrode still retains 467
mAh g−1, showing high reversible capacity,
good cycling stability, and rate capability.
Page No.1 – Page No.6
Title: Fabrication of one-dimensional
mesoporous CoP nanorods as anode
*one or two words that highlight the emphasis of the paper or the field of the study
mesoporous CoP nanorods, battery.
This article is protected by copyright. All rights reserved.