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Phosphorus–carbon nanocomposite anodes for

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lithium-ion and sodium-ion batteries

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Cite this: J. Mater. Chem. A, 2015, 3,

5572
Thrinathreddy Ramireddy,a Tan Xing,a Md Mokhlesur Rahman,a Ying Chen,a
Quentin Dutercq,ab Daniel Gunzelmanna and Alexey M. Glushenkov*ac
With the expected theoretical capacity of 2596 mA h g1, phosphorus is considered to be the highest
capacity anode material for sodium-ion batteries and one of the most attractive anode materials for
lithium-ion systems. This work presents a comprehensive study of phosphorus–carbon nanocomposite
anodes for both lithium-ion and sodium-ion batteries. The composite electrodes are able to display high
initial capacities of approximately 1700 and 1300 mA h g1 in lithium and sodium half-cells, respectively,
when the cells are tested within a larger potential windows of 2.0–0.01 V vs. Li/Li+ and Na/Na+. The level
of demonstrated capacity is underpinned by the storage mechanism, based on the transformation of
phosphorus to Li3P phase for lithium cells and an incomplete transformation to Na3P phase for sodium
cells. The capacity deteriorates upon cycling, which is shown to originate from disintegration of
Received 14th November 2014
Accepted 3rd February 2015
electrodes and their delamination from current collectors by post-cycling ex situ electron microscopy.
Stable cyclic performance at the level of 700 and 350–400 mA h g1 can be achieved if the potential
DOI: 10.1039/c4ta06186a
windows are restricted to 2.0–0.67 V vs. Li/Li+ for lithium and 2–0.33 vs. Na/Na+ for sodium half-cells.
www.rsc.org/MaterialsA The results are critically discussed in light of existing literature reports.
operation in a lithium-ion battery, the practical electrochemical

Introduction performance of bulk red or black phosphorus has been found
Phosphorus is a non-metallic element, which is known to have unsatisfactory, with either poor reversibility and Coulombic
three common allotropes – white, red and black.1 White phos- efficiency4–6 or problematic cyclic stability.7 The current
phorus is volatile and unstable; it bursts into ames when it is consensus opinion is that phosphorus-based battery anodes
exposed to natural atmosphere. Red phosphorus is usually should be prepared in the form of nanocomposites in which the
amorphous in nature and is widely commercially available. phosphorus component is nely dispersed in the carbon
Black phosphorus is a crystalline phase, thermodynamically component.4,5,8–11 Composites of amorphous phosphorus8 as
stable below 550 C and transforming to red (amorphous) well as red4,9 and black5,8,10 crystalline forms with carbon have
phosphorus at higher temperature.1,2 Among various applica- been demonstrated. Reasonably stable capacity retention over
tions, the use of phosphorus in anodes of lithium-ion and up to 100 cycles with high Coulombic efficiencies has been
sodium-ion batteries attracts attention due to its high theoret- reported by Wang et al.11 and Qian et al.8 These two recent
ical capacity (2596 mA h g1).3 Specically, red and black forms manuscripts claim the stable capacity in the phosphorus
of phosphorus have been considered as candidates for anode component of the composites in excess of 2000 mA h g1, uti-
materials.4–11 lising 92.8 and 90.7% of the theoretical capacity of phosphorus,
In lithium-ion batteries phosphorus is considered as a respectively. Sun et al. have suggested that the formation of
possible high capacity alternative to the conventional graphitic stable P–C bonds may be responsible for the stability of ball
anode (theoretical capacity of only 372 mA h g1). The theo- milled phosphorus–carbon nanocomposites in lithium-ion
retical capacity of phosphorus is much higher than that and is battery anodes.13
inferior only to Si (4200 mA h g1)3,12 among the materials that In sodium-ion batteries the anode materials conventionally
can electrochemically alloy with lithium. Due to the limitations considered for lithium-ion batteries such as graphite, Ge or Si
of electronic conductivity and signicant volume changes upon are either inactive or able to display only small capacities.14 As a
result, Sb, Sn and P have emerged as possible high-capacity
a
Institute for Frontier Materials, Deakin University, Waurn Ponds, 3216 Victoria,
anode materials operating via an alloying–dealloying mecha-
Australia. E-mail: [email protected] nism.15–18 Among them, phosphorus has the highest theoretical
b
Université de Nantes, Polytech Nantes, Institut des Matériaux Jean Rouxel, CNRS, Rue capacity, which makes it a very interesting material to study.
Christian Pauc, BP 50609, 44306 Nantes Cedex 3, France Recently, phosphorus has been tested as an anode for Na-ion
c
Melbourne Centre for Nanofabrication, 151 Wellington Rd, Clayton, VIC 3168, battery. Kim et al. have estimated that amorphous red
Australia
5572 | J. Mater. Chem. A, 2015, 3, 5572–5584 This journal is © The Royal Society of Chemistry 2015
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Paper Journal of Materials Chemistry A
phosphorus–carbon composite could deliver a capacity of 1890 Characterization

mA h g1 at a current rate of 143 mA g1 (ref. 18) at a slightly
X-ray diffraction (XRD) patterns of materials and electrodes
elevated temperature of 30 C. Qian et al. have reported amor-
were obtained by using a PANalytical X'Pert Pro instrument with
phous phosphorus–carbon composite with a capacity of 1750
a Cu Ka radiation source (l ¼ 1.54181 Å). The XRD patterns were
mA h g1 at a current rate of 250 mA g1 at room temperature.19
collected over the range of 20–80 by keeping the step size of
Subsequently, Li et al. have prepared red phosphorus–carbon
0.02 at a scan rate of 2 s per step. The phases in the obtained
nanotube composite by hand grinding in an agate mortar, and
patterns were analysed using X'Pert High Score Plus soware.
the composite demonstrates an initial reversible capacity of The cycled electrodes for the XRD analysis were covered with
1530 mA h g1 when tested at current density of 143 mA g1.20
Kapton tape to prevent reacting with moisture and oxygen aer

The capacity was monotonously deteriorating upon cycling, in
being extracted from the lithium and sodium half-cells in an Ar-
contrast to the previous report,19 in which deterioration initi-

lled glove box. The TEM characterization was done using a
ated aer the rst 40 cycles of stable performance. Black
JEOL JEM-2100F instrument operated at 200 kV. Energy-ltered
phosphorus–carbon composites have not been studied much in
TEM (EFTEM) elemental maps were obtained using a Gatan
conjunction with sodium-ion batteries, with only limited data
Quantum ER 965 Imaging Filter and the three-window method.
presented in Supporting Information of paper by Qian et al.19
Raman spectroscopic characterisation was performed using
Phosphorus-based electrodes for sodium-ion batteries have also a Renishaw inVia micro-Raman system. A laser with 514 nm
been assessed by Yabuuchi et al.,21 and it has been revealed that wavelength was used during the experiment. The power of laser
adding uoroethylene carbonate to the electrolyte is critical for
was 2.5 mW (5% of max power) and the accumulation time was
the stability of phosphorus-based anodes.
60 s. 20 lens was used in the experiment. The nal spectra
Herein we present the synthesis of phosphorus–carbon nano-
were formed by accumulating two scans.
composites and their systematic evaluation as lithium-ion and
Solid-state NMR spectra were acquired using Bruker Avance3
sodium-ion anode materials. The structural analysis indicates
300 and 500 spectrometers, operating at 7.05 and 11.4 T. All
that the composites contain black (orthorhombic) phosphorus
samples were handled and packed into standard zirconia magic
either in the form of crystalline nanoparticles or in signicantly angle spinning (MAS) rotors in a glove box with argon atmo-
disordered state. Discussion of data and correlation with previ- sphere. The samples of red and black P were packed into 2.5
ously published results are presented. Phase changes in the
mm MAS rotors, mounted into a triple resonance MAS probe
electrode upon discharge and charge of lithium and sodium half-
and measured under magic-angle-spinning (MAS) at a speed of
cells are analysed, and the structural integrity of phosphorus-
32.5 kHz and a resonance frequency of 202.4 MHz. Due to
based electrodes cycled within full (2.0–0.01 V vs. Li/Li+ or Na/Na+)
problems with achieving comparable spinning speeds the
or restricted potential windows is studied. We expect that our
nanocomposite samples were packed into 4 mm zirconia MAS
results will stimulate further important developments of phos-
rotors and measured at 6 kHz spinning speed at 121.5 MHz
phorus-based anode materials for metal-ion batteries. resonance frequency. Spectra were acquired using a Solid-Echo
pulse sequence with excitation frequencies of 102–143 kHz. All
Experimental 31
P shis are given relative to 85% H3PO4 solution. The recycle
Material synthesis delays were set to 4T1, long enough to guarantee a full spin
relaxation according to the T1 relaxation time constants, which
Red phosphorus powder (100 mesh, 98.9% purity, Alfa Aesar) was were measured independently for each sample. The spectrum of
used as a starting material. Black phosphorus was prepared by
red P was acquired by sampling 64 scans with a recycle delay of
milling 6 grams of red phosphorus in a stainless steel jar using
360 s. The spectrum of black P was acquired by sampling 32
Fritsch Pulverisette 5 planetary ball mill for 25 h under Ar atmo- scans with a recycle delay of 40 s. The spectrum of composite
sphere (200 kPa excess pressure above atmospheric). The ball to C-1 was acquired by sampling 64 scans with a delay of 3 s. The
powder ratio was 110 : 1 (ten balls with a diameter of 25.4 mm composite C-2 was acquired by sampling 320 scans with 180 s
were used). Rotation speed was 200 rpm. The obtained black recycle delay.
phosphorus was mixed with graphite (Sigma Aldrich, 282863, <20 Scanning electron microscopy (SEM) imaging has been done
mm) in a 7 : 3 weight ratio and the mixture was milled in two types with a Supra 55VP eld emission scanning electron microscope.
of ball mills. Phosphorus–carbon composite C-1 was produced by
The accelerating voltage was 5 kV and the working distance was
milling 6 g of the mixture for 25 h in Fritsch Pulverisette 5 plan-
about 5 mm. An In-lens detector was used during the experi-
etary ball mill under the conditions similar to those used for ment to provide images with good signal/noise ratio. The elec-
preparing black phosphorus. Phosphorus–carbon composite C-2 trodes for SEM imaging were extracted from lithium and
was produced by milling 5 g of the mixture in a magneto-ball sodium half-cells aer cycling for a large number of cycles.
mill.22 Four stainless steel balls (25.4 mm in diameter) were
loaded into the vial, and the milling was conducted for 100 h at
160 rpm. The milling was performed under Ar atmosphere at a Electrochemical characterization
pressure of 100 kPa above atmospheric in the presence of an The composite materials were mixed with Super P Li™ (Timcal
external magnet at a 45 position. The milling mode is similar to Ltd.) and sodium carboxymethyl cellulose (CMC) binder (in a
the ball milling mode C described in ref. 23. The ball to powder weight ratio of 80 : 10 : 10) in de-ionized water to form a
ratio in this experiment was 52.8 : 1. homogenous slurry. The slurry was then coated onto copper foil
This journal is © The Royal Society of Chemistry 2015 J. Mater. Chem. A, 2015, 3, 5572–5584 | 5573
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Journal of Materials Chemistry A Paper
substrates and heated in vacuum overnight at 90 C. All elec-

trodes had a standard size of 1 1 cm2 and the weight of active
material (phosphorus–carbon composite) was controlled in the
range between 0.92 and 1.05 mg. Lithium and sodium half-cells
were assembled in the form of CR2032 coin cells inside the Ar-
lled glove box (Innovative Technology, USA) using a CR2032
coin cell. Li and Na metal pieces were used as a counter elec-
trodes. The electrolyte for lithium half-cells was 1 M LiPF6 in a
1 : 1 : 1 (by volume) mixture of ethylene carbonate (EC), diethyl
carbonate (DEC) and dimethyl carbonate (DMC). The electrolyte

for sodium half-cells was 1 M NaClO4 in propylene carbonate

(PC) with 2% uoroethylene carbonate (FEC) additive. Poly-
ethene separators (MTI Corp., USA) and Whatman GF/F
microber glass separators (Sigma Aldrich) were used for
lithium and sodium cells, respectively. The lithium half-cells
were galvanostatically charged–discharged between 2.0–0.01 or
2.0–0.67 V vs. Li/Li+ at a current rate of 100 mA g1 using LAND Fig. 1X-ray diffraction patterns: (a) red P, (b) black P, (c) phosphorus–
carbon composite C-1 and (d) phosphorus–carbon composite C-2
battery testers (Wuhan LAND Corporation, China). The sodium
(arrows indicate the positions of the strongest peaks of black
half-cells were galvanostatically charged–discharged between phosphorus).
2.0–0.01 or 2.0–0.33 V vs. Na/Na+ using the same instruments.
All capacities were calculated per total weight of the composites
(including both phosphorus and carbon components). Fig. 2a shows the Raman spectra of the red phosphorus and
mechanochemically obtained black phosphorus. The Raman
signature of the red amorphous phosphorus is consistent with
Results and discussion that in other reports.8,11,18 Aer ball milling, three unambiguous
Raman bands appear at about 363, 438 and 467 cm1, which are
Black phosphorus used for the preparation of the composites
the typical Raman ngerprints of black phosphorus7,13 corre-
was synthesized mechanochemically in our laboratory from
sponding to the A1g, B2g and A2g modes. These results are
commercially available red amorphous phosphorus, similarly to
consistent with the XRD data and conrm that mechano-
the previously used approach.5 Two phosphorus–carbon
chemical treatment of red amorphous phosphorus resulted in
composites were prepared by high energy ball milling of
the formation of the black, orthorhombic phase of phosphorus.
mixtures of as-produced black (orthorhombic) phosphorus and
Fig. 2b shows the Raman spectra of ball milled phosphorus–
graphite using two ball mills, a planetary one and a magneto-
carbon composites C-1 and C-2. The phosphorus bands cannot
ball mill. For the purpose of clarity, we refer to the composite
be seen in either sample. The carbon component shows two
prepared by the planetary ball mill as C-1 and the composite
strong bands at about 1350 and 1600 cm1, typically referred to
prepared by a magneto-ball mill as C-2.
in the literature as D and G bands of graphite,24 in both nano-
composites. The D and G bands in the composite C-2 have
much larger FWHMs comparing with those in the composite C-
Characterisation of samples
1, which reveals a more disordered in-plane structure.25,26 For
The XRD patterns of red and black phosphorus and the phos- example, the FWHM of the D band is 120 cm1 for the
phorus–carbon composites are shown in Fig. 1. Red P is composite C-2, comparing with only 70 cm1 in the composite
amorphous, as expected (Fig. 1a). Its XRD pattern is dominated C-1, indicating a much higher degree of in-plane distortion and
by two broad humps at 25–38 and 47–65 degrees. In contrast, disordering in the graphitic structure in the composite C-2.
the XRD pattern of black P (Fig. 1b) displays a number of The 31P NMR spectra of red amorphous phosphorus, black
crystalline peaks, consistent with a standard powder diffraction phosphorus and phosphorus–carbon composites C-1 and C-2
le (JCPDS #00-009-0020). Similar diffraction patterns for black are shown in Fig. 3. The spectra of red phosphorus (Fig. 3a)
phosphorus obtained by ball milling were reported previously shows very broad signals around d ¼ 80, +60 and +150 ppm,
by Park and Sohn.5 The composite C-1 (Fig. 1c) retains the same indicating a highly inhomogeneous, amorphous environment
crystalline nature of the phosphorus component that can be for the 31P nuclei in this material. The measured chemical shis
seen in Fig. 1b for the pure black phase. The phosphorus in the match the shis of red and violet phosphorus samples observed
composite C-2 is clearly more disordered, displaying broad by Bytchkov et al.27 The black P (Fig. 3b) spectrum shows a
X-ray signals (Fig. 1d). A very weak increase in intensities strong signal at d ¼ 22 ppm with a weaker, broad shoulder at
around the positions of the three strongest peaks of the black about 10-0 ppm. The observed chemical shi is in agreement
orthorhombic P (highlighted with arrows) can, however, still be with a black phosphorus spectrum acquired by Lange et al.28
noticed, indicating that some nanocrystalline black P may whereas the smaller line width indicates a more homogeneous
remain in the composite. The graphitic peaks are not visible in environment for the 31P nuclei in this material with a higher
the XRD patterns of either composites C-1 or C-2.
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31
Fig. 3 P solid-state NMR spectra of red amorphous phosphorus (a),
mechanochemically produced black phosphorus (b), phosphorus–
carbon composite C-1 (c) and phosphorus–carbon composite C-2 (d).
carbon elemental maps are depicted in Fig. 4d and g, and the

phosphorus elemental maps are depicted in Fig. 4e and h.
There is a clear difference between the carbon and phosphorus
maps of the composite C-1. These maps are not identical, and,
furthermore, nanoparticles can be observed in the phosphorus
elemental map of C-1 (some of them highlighted with white
arrows in Fig. 4e). Aer a careful inspection of the elastic image
(Fig. 4c), the same nanoparticles can be seen as the areas with
darker contrast (highlighted with arrows). Taking into account
the nanocrystalline peaks of orthorhombic phosphorus in the
XRD pattern of C-1 (Fig. 1c), the TEM data are consistent with
the presence of crystalline phosphorus nanoparticles in the
carbon host in the composite C-1.
In contrast, the elastic image, carbon and phosphorus maps
of the composite C-2 (Fig. 4f–h) are essentially identical. No
Fig. 2 Raman spectra of samples of red and black phosphorus (a) and clear nanoparticles are visible in Fig. 4h, and the phosphorus
phosphorus–carbon composites C-1 and C-2 (b). and carbon maps repeat each other. It can be concluded that the
phosphorus and carbon are distributed much more homoge-
neously in the composite C-2. As the spacial resolution of the
crystallinity when compared to the red phosphorus sample. A EFTEM technique is 1–2 nm, our interpretation of the acquired
similar trend can be observed for the respective phosphorus– data suggests the presence of very small nanoparticles or
carbon nanocomposites, but with the main signal in the nanoclusters of phosphorus with a typical size of 1 nm or less,
composite C-2 (Fig. 3d) showing a very broad signal shied to homogeneously distributed within the carbon component of
around d ¼ 10 ppm, very similar to the signal of composite C-1 the composite C-2. In accordance with the XRD and NMR data,
(Fig. 3c). The even broader line width of C-2 is also indicating a these nanoclusters are signicantly disordered but may retain
very inhomogeneous, amorphous environment, but with the the local environment of the black orthorhombic phosphorus.
chemical shi and thus an electronic environment and struc- It is worthwhile to compare our characterisation results with
ture closer to black P. those of other groups for phosphorus–carbon nanocomposites
The results of TEM analysis of phosphorus and composite prepared by ball milling.5,8,13,18,19 The differences and similari-
samples are shown in Fig. 4. The electron diffraction pattern of ties in the composition and structure of the composites may
the commercial red phosphorus (Fig. 4a; a bright-eld image is shed light on the differences and similarities in their electro-
also shown as an inset) displays only diffuse rings, consistent chemical performance. As we pointed out, the phosphorus in
with the amorphous nature of this sample. In contrast, the the composites C-1 and C-2 described here is in the form of
diffraction pattern of black phosphorus (Fig. 4b) displays a set black, orthorhombic phase (either crystalline or somewhat
of polycrystalline rings that can be indexed in accordance with disordered). This is likely to originate from the “history” of
the expected orthorhombic phase. In particular, rings corre- preparation because the powder of black phosphorus was
sponding to the (012), (004), (016) and (121) lattice planes can be initially produced and subsequently used for preparing the
distinguished. composites. It is likely that the phosphorus component in the
Energy-ltered TEM was employed to understand the composites inherits at least the local environments of the black,
differences in the structure of the composites C-1 and C-2. orthorhombic parent phase. It is important to note that the
Fig. 4c and f show elastic images of the two composites, their composites prepared by Qian et al.8,19 for both lithium-ion and
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Fig. 4 TEM analysis of phosphorus and phosphorus–carbon samples. (a and b) Selected area electron diffraction patterns of the red and black
phases of phosphorus (bright-field images are shown as insets); (c–e) an elastic image, carbon and phosphorus energy-filtered elemental maps
of the composite C-1; (f–h) an elastic image, carbon and phosphorus energy-filtered elemental maps of the composite C-2 (colour scheme:
green – carbon, red – phosphorus).
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sodium-ion anodes were also produced via the formation of an Electrochemical performance in the 2.0–0.01 V potential
intermediate black phase of phosphorus in the composite (refer window vs. Li/Li+ and Na/Na+
to the manuscripts and related Supporting Information).
The electrochemical performance of the phosphorus–carbon
Although these authors have described their composites as
nanocomposites in lithium half-cells is shown in Fig. 5. The
“amorphous phosphorus/carbon nanocomposites”, it seems
initial discharge capacity (1930 mA h g1) and Coulombic effi-
that at least some of their materials may be still in the form of
ciency (86.9%) of the composite C-1 are quite attractive,
black phosphorus (which is evident from the presence of crys-
although the capacity declines monotonously in the following
talline spots in electron diffraction patterns (ref. 19 and Fig. 1b)) cycles (Fig. 5a). The discharge capacities measured in the
and weak Raman bands at 466 and 437 cm1 (ref. 8 and Fig. 1b).
second, seventh and 50th cycles are 1654, 1446 and 349 mA h
Due to the similarity of preparation method and the presence of
g1, respectively. The electrochemical stability of the composite
the intermediate black phase, the structure of their material

C-2 is inferior to that of the composite C-1 (Fig. 5b). Specically,
may be close to the structure of our composite C-2 although
the electrode of C-2 demonstrates a steep decline in capacity,
differences in Raman signatures exist (next paragraph). We
with discharge capacities of 1995, 1642, 748 and 49 mA h g1
believe that our another composite, C-1, is, on the other hand,
measured in the rst, second, seventh and 50th cycles, respec-
structurally similar to that produced by Park and Sohn,5 who
tively. An interesting observation in the composite C-2 was a
ball milled carbon black and black phosphorus directly to sudden drop of capacity in the tenth cycle, in which the charge
prepare a composite. capacity was dramatically lower than the discharge capacity.
As explained, the Raman spectra do not reveal the presence
The initial Coulombic efficiency of the composite C-2 in the rst
of the phosphorus bands for the composites C-1 and C-2.
cycle was similar to that of C-1 (85.5%). Overall, both compos-
Similar lack of Raman signatures has been observed by Kim
ites demonstrate declining capacities upon progressive cycling,
et al.18 Qian et al.,8,19 in contrast, have observed weak bands at
while the decline appears to be gradual for the composite C-1
437 and 466 cm1, typical for black phosphorus in the Raman
and quite abrupt for the composite C-2.
spectra of their composites. Sun et al.13 have also detected the
The charge–discharge curves of the composites C-1 and C-2
presence of Raman bands of black phosphorus in their are shown in Fig. 5c and d. The rst discharge curves of the
composite. The presence or lack of phosphorus Raman composites are different from the subsequent ones and have an
signals may reect some differences in the structure of these
irreversible hump at about 1.3–0.95 and 1.2–0.85 V vs. Li/Li+, for
composites. A Raman feature at about 600–750 cm1 was
the composites C-1 and C-2, respectively. A similar irreversible
assigned to P–C bonds by Sun et al.13 This Raman signature as
hump at around the same potentials was observed for the
well as a high-resolution TEM image of a phosphorus–carbon
phosphorus–carbon composites by Park and Sohn5 and Qian
boundary and some XPS data have been used by these
et al.8 Similarly to the previous reports, composites C-1 and C-2
researchers as evidence for the presence of phosphorus–
uptake most of lithium within potential windows 0.95–0.45 V
carbon bonds, which, according to the manuscript, lead to an and 0.85–0.4 V vs. Li/Li+, respectively. In the course of the charge
improved performance of the material in the lithium-ion of the half-cells the composites C-1 and C-2 release most of
battery. Although the formation of phosphorus–carbon bonds
lithium within the potential windows of 0.9–1.25 V and 0.8–1.2
or compounds is indeed possible in nanocomposites and is
V vs. Li/Li+. Polarisation of the charge–discharge curves
an important consideration, further research is warranted in
increases rapidly upon cycling for both composites, and this
this area to conrm conclusions about the formation of
phenomenon is more pronounced for the composite C-2.
phosphorus–carbon bonding or any phosphorus–carbon
Before discussing the electrochemical results in lithium cells
phases.
and comparing them with literature, it is important to mention
Information on the distribution of phosphorus in the that different authors calculate the reported capacity differently,
composites is currently limited. Efforts in systematic mapping and this complicates the process of comparing data. In partic-
of phases by transmission electron microscopy techniques are
ular, some authors neglect the capacity of the carbon compo-
required to understand this further. Kim et al.18 have presented
nent completely (all measured capacity was attributed to the
energy-dispersive X-ray maps of phosphorus and carbon but the
phosphorus component),4,8,10 some estimated the capacity of
resolution of the scans was somewhat limited to pinpoint the
the phosphorus component11 and some measured the capacity
differences in the distribution of elements. Another possible
per total mass of the composite (this work and ref. 11 and 13).
problem with the energy-dispersive X-rays maps is a low sensi-
Another important consideration is the use of different active
tivity of this method to light elements. Mapping methods based material loadings in the electrodes by different authors, and the
on the energy loss of electrons could be more suitable due to electrodes with thinner coating of active materials might be, in
their higher sensitivity to C and P. In this work, we have used
general, showing better electrochemical performances. In some
energy-ltered elemental mapping and were able to demon-
case, the active material loadings have not been reported. The
strate that the distributions of the phosphorus component in
available experimental results for the phosphorus–carbon
the composite C-1 and C-2 are quite different. Further efforts in
composites are summarised in Table 1.
characterising the composites may be focused on the applica-
The results reported in the literature for lithium cells can be
tions of electron energy loss spectrum imaging in the scanning
broadly classied into two groups. One group of results suggests
TEM mode. a gradual and signicant deterioration in the performance in
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Fig. 5 Electrochemical performance of the phosphorus–carbon composites in lithium half-cells within the potential window of 2.0–0.01 V vs.
Li/Li+ at a current rate of 100 mA g1: (a and b) cyclic performance of the composites C-1 and C-2, respectively; (c and d) galvanostatic charge–
discharge profiles of the composites C-1 and C-2.
phosphorus–carbon composites. For example, activated amor- prepared by Wang et al.11 has demonstrated capacity retention
phous phosphorus–carbon composite with the component ratio of 87% at the end of 55th cycle. However, the phosphorus
of 1 : 1 synthesised by Marino et al. displayed capacity retention content in the composite was around 32.6%, very low, which
of 64.9% at the end of 20th cycle.4 The capacity of black phos- might be a reason behind the excellent cycling stability of the
phorus–acetylene black electrode in a solid-state cell declined electrodes in this work.11 Due to the high content of the carbon
from 1746 to about 500 mA h g1 aer 150 cycles.10 The capacity component, the capacity per total weight of the composite was
of black phosphorus–carbon composite prepared by ball moderate, only at a level of 740–840 mA h g1. Sun et al.13 have
milling by Park and Sohn5 dropped from 1814 to about 200 mA reported 80% retention of capacity in the ball milled black
h g1 aer 30 cycles within a potential window of 2.0–0.01 V vs. phosphorus–graphite composite, while Qian et al.8 have repor-
Li/Li+. The latter material, as we expect, is structurally similar to ted 90% retention of capacity in their amorphous phosphorus–
our composite C-1. In the case of our C-1 composite, the cyclic carbon composite (both aer 100 cycles). The last two reports
behaviour was similar at a qualitative level to that for the demonstrate signicantly better cyclic performance of the
composite in ref. 5 but a better capacity retention was observed phosphorus–carbon nanocomposites prepared by ball milling.
(349 mA h g1 aer 50 cycles). This can be correlated with a It is not clear at this stage what leads to such an improvement.
lighter active material loading (1 mg cm2 instead of 2.5 mg Sun et al. have suggested that the formation P–C bonds in their
cm2) and a more suitable binder (sodium carboxymethyl composite played an important role in the improvement of
cellulose instead of polyvinylidene uoride). Taking these cyclic stability, and the cyclic performance was also a function
difference into account, the behaviour of our composite C-1 was of the carbon material used as a precursor to create a
consistent with the behaviour of the black P–carbon composite composite.13 Qian et al. have indicated that the milling time was
reported by Park and Sohn.5 an important parameter for the performance of their compos-
Three other reports have claimed only moderate declines ites. The composites milled for either 6 and 12 h have shown
in capacity and attractive cyclic stabilities over many deteriorating cyclic performance with increasing polarisation in
cycles. Nanostructured phosphorus–porous carbon composite the charge–discharge curves while the composite milled for 24 h
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Table 1 Electrochemical performance of phosphorus–carbon composites in lithium half-cells
Active material loading, Initial discharge/charge

Sample mg cm2 capacity, mA h g1 Cyclic performance Reference
C-1 0.92–1.05 1930/1677a Declining gradually. This work

Capacity of 349 mA h g1 in
the 50th cycles.
C-2 0.92–1.05 1995/1706a Declining more abruptly. This work

Capacity of only 49 mA h g1
in the 50th cycle.

Amorphous phosphorus– 3 2651/2355b Minor decline. 90% of 8

carbon composite capacity is reported to
remain aer 100 cycles
Activated phosphorus– Not reported 3289/1385b Declining. 900 mA h g1 4

carbon composite capacity aer 20 cycles
Black phosphorus–acetylene About 3.1c 1962/1746b Declining. Capacity of about 10

black mixture in a solid-state 500 mA h g1 aer 150 cycles
cell
Black phosphorus–carbon 2.5 2010/1814a Declining. Capacity of about 5

composite 200 mA h g1 aer 30 cycles
Nanostructured red Not reported 1200/840a Relatively stable capacity. 11

phosphorus–carbon Minor decline. 745 mA h g1
composite aer 50 cycles
Black phosphorus–graphite 2.0–2.8 2786/2382a Minor decline. 80% Of 13

composite capacity is reported to
remain aer 100 cycles
a
Capacity is calculated per total weight of the phosphorus–carbon composite. b All capacity is assigned to the phosphorus component, the capacity
of carbon components is neglected as minor contribution. c Estimated. Working electrode was prepared by mixing black phosphorus, acetylene
black and solid electrolyte.
has demonstrated dramatically improved cyclic performance. The charge–discharge curves of the composites C-1 and C-2
The preparation methods used in this work and in ref. 5, 8 and are shown in Fig. 6c and d. The rst discharge curves of the
13 are quite similar. Further research will be required to composites are different from the subsequent ones and have an
understand the origin of signicant differences observed in the irreversible hump at about 1.1–0.65 and 0.95–0.65 V vs. Na/Na+,
electrochemical performances. for the composites C-1 and C-2, respectively. The second and
The electrochemical performance of the phosphorus–carbon subsequent discharge curves of the composites were different to
nanocomposites C-1 and C-2 in sodium half-cells is shown in the rst discharge. There are three voltage regions in the cor-
Fig. 6. The initial discharge capacity of the composite C-1 was responding discharge cycle (i) a sharp slope down to 0.5 V vs.
1530 mA h g1 and its measured Coulombic efficiency was Na/Na+, (ii) a sloping plateau (or, possibly, a series of plateaus)
86.4%. Aer a minor decline in capacity in the rst 15 cycles to in the range of 0.5–0.15 V vs. (Na/Na+), and (iii) a minor plateau
1193.9 mA h g1, the capacity drop accelerates aerwards and a at around 0.07–0.11 V vs. Na/Na+, which disappears aer a few
capacity of 187 mA h g1 can be measured in the 50th cycle cycles. Most of sodium release takes place between 0.4–0.8 V vs.
(Fig. 6a). The cyclic performance of the composite C-2 is again Na/Na+. The observed behaviour of the charge–discharge curves
inferior to that of C-1. The electrode demonstrates a steeper is similar to that observed elsewhere.18,19 Aer comparing the
decline in capacity (Fig. 6b), and the discharge capacities exact behaviour of the composites C-1 and C-2, we can also note
measured in the rst, second, tenth and 50th cycles are 1427, the appearance of a small plateau, which disappears aer a few
1321, 991 and 119 mA h g1. The initial Coulombic efficiency cycles, at about 0.6 V vs. Na/Na+ during charging of the half cell
was 89.9%. The high Coulombic efficiency emphasises that, in with the composite C-1.
principle, the studied phosphorus–carbon composites may be Literature data on the performance on phosphorus–carbon
highly reversible sodium anodes if the deciencies in their composite electrodes are presented in Table 2. Promising
cyclic performance are addressed. performance of phosphorus–carbon nanocomposites has been
previously highlighted by Kim et al.18 and Qian et al.19 The
View Article Online

Fig. 6 Electrochemical performance of the phosphorus–carbon composites in sodium half-cells within the potential window of 2.0–0.01 V vs.
Na/Na+ at a current rate of 100 mA g1: (a and b) cyclic performance of the composites C-1 and C-2, respectively; (c and d) galvanostatic
charge–discharge profiles of the composites C-1 and C-2.
former report demonstrates the electrochemical performance at with other reports, where high capacity could be sustained for a
a slightly elevated temperature of 30 C and relatively stable number of cycles and accelerated degradation was observed
cyclability (with only 7% of capacity drop) is shown for 30 cycles. aerwards.
It is not clear if the performance remains stable aer 30 cycles While discussing the performance of phosphorus–carbon
in this report. In the latter report,19 the cyclic performance has composites in sodium half-cells, it is important to point out that
been evaluated for 60 cycles and, although stable for the rst 35 various researchers use different electrolytes (salts and solvents)
cycles, the capacity has been found to decline dramatically for testing as there is still no commonly accepted electrolyte for
between 35th and 60th cycles. These authors have also reported this new type of batteries. We used 1 M NaClO4 in propylene
that the addition of 10% of uoroethylene carbonate (FEC) to carbonate (PC) with 2% FEC in this work. Similar electrolyte was
the electrolyte is capable of improving the cyclic performance, used by Yabuuchi et al.21 A combination of ethylene carbonate
and electrochemical performance with slow continuous decline (EC) and diethyl carbonate (DEC) as a solvent with either NaPF6
in capacity for 140 cycles has been demonstrated. Similar of NaClO4 salt and with or without FEC was used by Li et al.,20
observation about the role of FEC has been reported by Kim et al.18 and Qian et al.19
Yabuuchi et al.,21 suggesting that the addition of FEC improves Another important variable that affects the cyclic perfor-
electrode reversibility. Declining cyclic performance has been mance in both lithium and sodium cells is obviously the choice
reported by Li et al.20 In their work, the reversible capacity has of a binder used in the electrodes. Polyvinylidene uoride
been shown to decline 23.4% aer only 10 cycles but the (PVDF),5,13,21 (sodium) carboxymethyl cellulose (CMC),4,8,9,19
composite was prepared by simple grinding of red phosphorus polyacrylic acid (PAA),18 polyacrylonitrile11 and sodium poly-
and carbon nanotubes by hand. Our results indicate that the acrylate (PANa)21 were used in phosphorus–carbon composite
composite C-1 is capable of sustaining high capacity for the rst electrodes in lithium and sodium cells. CMC was used as a
15 cycles, with accelerating decline aerwards (the electrolyte binder in the present work. Future systematic study is required
with 2% FEC in it was used). It seems to be generally consistent to understand the most suitable binder for this type of electrode
View Article Online
Table 2 Electrochemical performance of phosphorus–carbon composites in sodium half-cells
Active materials Initial discharge/charge

Sample loading, mg cm2 capacity, mA h g1 Cyclic performance Reference
C-1 0.92–1.05 1530/1322a Slowly declining in the rst This work

15 cycles and faster
aerward. Capacity of 187
mA h g1 in the 50th cycle
1427/1283a
C-2 0.92–1.05 Declining. Capacity of 119 This work

mA h g1 in the 50th cycles
Amorphous red 1.4–2.1 2223/1890b Minor decline. 93% of 18

phosphorus–carbon capacity is retained aer 30
composite cycles
Amorphous carbon– 3 2015/1764b Stable cyclic performance for 19

phosphorus composite 35 cycles with accelerating
decline aerwards.
Monotonous slow decline in
the electrolyte with added
FEC
Red phosphorus–carbon Not reported 2210/1675b Declining. 76.6% Of capacity 20

nanotube composite is retained aer 10 cycles
Red phosphorus–acetylene 0.4–0.46 Reversible capacity of about Declining. Capacity of about 21

black mixture 2150b 800 remains aer 10 cycles
a
Capacity is calculated per total weight of the phosphorus–carbon composite. b All capacity is assigned to the phosphorus component, the capacity
of carbon components is neglected as minor contribution.
material, the available information is not adequate to choose change is signicantly reduced, leading to a stable capacity of
the optimal binder reliably. The general view is that the the electrode.5 We have attempted to re-check these nding for
conventional PVDF is a poor choice of a binder for phosphorus- the lithium cells and evaluate if similar stabilisation of capacity
based electrodes and gives inferior performance. For example, may happen in the case of sodium half-cells.
an electrode with PANa binder has been shown to provide a Fig. 7a shows the cycling stability of the composite C-1 in the
much better performance than that of the electrode with PVDF potential window of 2.0–0.67 V vs. Li/Li+ in a lithium half-cell.
binder in sodium cells in ref. 21. Intriguingly, one of the best Relatively stable capacity of slightly above 700 mA h g1 can be
electrochemical performances in lithium cells13 was claimed in observed. Some variations in the capacity visible in the graphs
a study using PVDF as a binder. in Fig. 7 are due to the temperature variations in our laboratory
over the course of an Australian winter. It can be concluded
from the measured data that, in line with earlier ndings by
Electrochemical performance in the restricted potential
Park and Sohn5 stable capacity can be achieved in black phos-
windows vs. Li/Li+ and Na/Na+
phorus–carbon composites in a restricted potential window in
It is commonly accepted that the deteriorating cyclic perfor- lithium half-cells. The measured capacity in this study was
mance observed within the potential window of 2.0–0.01 V vs. somewhat higher than that in the previous work
Li/Li+ or Na/Na+ (Fig. 5 and 6) is likely to originate from (600 mA h g1)5 because of a lower cut-off potential used in the
signicant volume changes during the lithium and sodium present work.
alloying and de-alloying processes in the phosphorus compo- Our measurements indicate (Fig. 7b and c), that similar
nent.5,8,19,21 For example, volume change of almost 300% (ref. stable cyclic behaviour can be achieved in sodium half-cells if
21) is expected in phosphorus in the course of its reaction with the potential window is restricted to 2.0–0.33 V vs. Na/Na+.
sodium. The dramatic volume change may impact the integrity Indeed, both composite C-1 (Fig. 7b) and composite C-2 (Fig. 7c)
of the electrodes during the repetitive cycling. Park and Sohn5 are able to demonstrate rather stable capacity of about 400 mA h
have previously pointed out that a stable cyclic behaviour in g1. The cut-off potential used for sodium cells is lower than
electrodes based on black phosphorus can be achieved in a that for lithium half-cells as the electrochemical reactivity of
lithium half-cell if the operating potential window is restricted phosphorus-based electrodes with sodium happens at lower
(to 2.0–0.78 V vs. Li/Li+ in their case). If the operating potential potentials. To sum up, phosphorus–carbon electrodes were able
is restricted to 2.0–0.78 V vs. Li/Li+, black phosphorus trans- to deliver stable capacities (approximately 700 and 400 mA h
forms reversibly into the LiP phase, and the associated volume
View Article Online

Fig. 7 Electrochemical performance of the electrodes cycled within restricted potential windows at 100 mA g1; (a) cyclic performance of the
composite C-1 between 2.0 and 0.67 V vs. Li/Li+; (b and c) cyclic performance of the phosphorus–carbon composites C-1 and C-2 between 2.0
and 0.33 V vs. Na/Na+.
g1) in lithium and sodium half-cells in restricted potential

windows.
Insights into the charge storage and failure mechanisms

In order to investigate the charge storage mechanisms, ex situ
XRD measurements were conducted on the C-1 composite
electrodes extracted from lithium or sodium half-cells aer
their rst discharge to 0.01 V vs. Li/Li+ or Na/Na+. Fig. 8a shows
that Li3P phase forms aer the rst discharge of the C-1 elec-
trode in a lithium-cell. There are no peaks of black P observed in
Fig. 8a, suggesting that almost all the phosphorus in the elec-
trode reacts with lithium to yield Li3P. Such an electrochemical
reaction agrees well with previous reports5,7,10 on the use of
black phosphorus in Li-ion systems, and the charge is suggested
to happen predominantly via a reversible phase change of P to
Li3P and back. In contrast, the XRD pattern of the C-1 electrode Fig. 8 Ex situ X-ray diffraction patterns of the electrodes discharged in
aer the discharge in a sodium half-cell indicates that two lithium and sodium half-cells to 0.01 V vs. Li/Li+ and Na/Na+,
respectively: (a) composite C-1 from a lithium cell (b) composite C-1
phases are present in the electrode (Fig. 8b). One phase corre-
from a sodium cell. The background at 20–30 is due to the Kapton
sponds to Na3P and the second phase is unidentied. The tape used to protect the sample.
authors were not able to match it with a standard powder
View Article Online
diffraction record, possibly due to the limited available

diffraction data on sodium–phosphorus compounds.
The presence of two phases in the XRD pattern is consistent
with the fact that the initial capacity of the C-1 electrode in a
sodium half-cell was well below the expected value for the
electrode. Indeed, based on the assumption of the reversible
transformation between P and Na3P and the expectation of the
capacity of carbon component of about 100 mA h g1 (measured
independently), the expected capacity of the C-1 electrode in a
sodium half-cell was 1847 mA h g1. However, the rst

discharge capacity of the cell was only 1530 mA h g1. We

estimate that not more than 2.4 sodium ions per one phos-
phorus atom (instead of 3 sodium ions) got incorporated into
the electrode during the rst discharge of the half-cell. Inter-
estingly, our results with electrodes incorporating black phos-
phorus are somewhat different from those by Yabuuchi et al.,21
who have observed a single Na3P phase forming in amorphous
phosphorus–carbon electrodes by synchrotron XRD. Their
experiment was, however, conducted with thinner electrodes.
Also, differences between the reaction mechanisms of amor-
phous phosphorus and black orthorhombic phosphorus are
possible. Kim et al. have also presented an ex situ XRD pattern of
a discharged electrode.18 Two features were resolved in the
range of 35–38 in the pattern (Fig. 3b in ref. 18) and were
assigned to be peaks of Na3P. We note however, that the right-
hand side peak is noticeably shied from the expected position
of Na3P while the le-hand side feature is unusually broad. It is,
in our view, possible that the two peaks of Na3P were not
resolved in their experiment and were recorded as one broader
feature. Consequently, the right-hand side peak may belong to
the same unexpected phase we observe at about 38 (Fig. 8b,
Fig. 9 SEM images of the C-1 and C-2 composite electrodes before
this work). and after cycling in lithium and sodium half-cells: (a and b) as-prepared
Fig. 9 depicts SEM images of the as-prepared C-1 and C-2 electrodes for the composites C-1 and C-2, (c and d) C-1 and C-2
electrodes as well as SEM images of the electrodes cycled in electrodes cycled in lithium half cells within the potential window of
lithium and sodium half-cells. As-prepared electrodes C-1 and 2.0–0.01 V vs. Li/Li+ for 150 cycles, (e and f) C-1 and C-2 electrodes
cycled in lithium half-cells within a restricted potential window of 2.0–
C-2 are shown in Fig. 9a and b. There are no visible cracks on
0.67 V vs. (Li/Li+) for 70 and 62 cycles, respectively, (g and h) C-1 and
the surface of both electrodes. The electrodes cycled within the C-2 electrode cycled in sodium half-cells within a restricted potential
potential window of 2.0–0.01 V vs. Li/Li+ for a large number of window of 2.0–0.33 V vs. Na/Na+ for 100 cycles. An inset in each case
cycles (Fig. 9c and d) are obviously damaged, displaying signs of shows a higher magnification image of the corresponding electrode.
deformation and disintegration, accompanied by delamination
from the current collector. The cycled electrodes are also
covered by a kind of lm (this is particularly obvious in Fig. 9c), 0.67 V vs. Li/Li+. The surfaces of the electrodes retain their
which we assign to the solid electrolyte interface or polymeric shapes and look similar to the surfaces of the as-prepared
layers formed through the polymerisation of the electrolyte electrode with the exception of the some minor cracks and an
solvents. Fig. 9d also directly shows areas with the exposed increased roughness of the surfaces. The C-1 and C-2 electrodes
copper current collector (marked by placing white elliptical cycled in sodium half-cell within a potential window of 2.0–0.33
markers on the corresponding areas) due to the delamination of V vs. Na/Na+ display similar appearance (Fig. 9g and h).
the electrode's active layer. Similar electrode evolution aer The major difference with the lithium cells is more
signicant cycling in the broad potential window (2.0–0.01 V vs. pronounced cracking in the electrode, possibly due to a larger
Na/Na+) was detected for the electrodes extracted from sodium expansion of the lm upon sodium insertion. Another inter-
half-cells. The performance of the electrodes degrades gradually esting observation is a reduced formation of gel-like polymeric
due to their mechanical disintegration and, possibly, the insu- layers on the electrodes in sodium cells, which can be correlated
lating nature of the organic layers that build up on the electrode with a different solvent (PC) and the presence of FEC as a sta-
(contribution from such a mechanism is widely suggested for bilising additive. Despite some cracking, the electrode lms
the Si anodes for Li-ion batteries). retain good overall stability. We suggest that, similarly to the
Fig. 9e and f shows the SEM images of the C-1 and C-2 reactivity with lithium, the volume change in the electrode is
electrodes cycled within a restricted potential window of 2.0– reduced when the bottom cut-off potential is restricted to 0.33
View Article Online
vs. Na/Na+ in sodium cells, leading to an improved stability of 2 R. Hultgren, N. S. Gingrich and B. E. Warren, J. Chem. Phys.,
the electrode and attractive cyclic stability demonstrated 1935, 3, 351.
in Fig. 7. 3 C.-M. Park, J.-H. Kim, H. Kim and H.-J. Sohn, Chem. Soc. Rev.,
2010, 39, 3115.
Conclusions 4 C. Marino, A. Debenedetti, B. Fraisse, F. Favier and
L. Monconduit, Electrochem. Commun., 2011, 13, 346.
In summary, nanocomposites of black (orthorhombic) phos- 5 C. M. Park and H. J. Sohn, Adv. Mater., 2007, 19, 2465.
phorus with carbon have been evaluated in this report. It is found 6 M. C. Stan, J. v. Zamory, S. Passerini, T. Nilges and
that, based on the use of a particular ball milling unit, composites M. Winter, J. Mater. Chem. A, 2013, 1, 5293.
with either nanoparticles of black phosphorus or well-dispersed 7 L.-Q. Sun, M.-J. Li, K. Sun, S.-H. Yu, R.-S. Wang and
phosphorus in a signicantly disordered state can be manufac- H.-M. Xie, J. Phys. Chem. C, 2012, 116, 14772.
tured. The composites have been subsequently assessed in both 8 J. Qian, D. Qiao, X. Ai, Y. Cao and H. Yang, Chem. Commun.,
lithium and sodium electrochemical half-cells. It is found that the 2012, 48, 8931.
composites can display impressive initial capacities at the level of 9 C. Marino, L. Boulet, P. Gaveau, B. Fraisse and
approximately 1700 and 1300 mA h g1 (per total weights of the L. Monconduit, J. Mater. Chem., 2012, 22, 22713.
composites) for lithium and sodium cells, respectively, and the 10 M. Nagao, A. Hayashi and M. Tatsumisago, J. Power Sources,
capacity gradually deteriorates when the cycling is performed 2011, 196, 6902.
within potential windows of 2.0–0.01 V vs. Li/Li+ or Na/Na+. The 11 L. Wang, X. He, J. Li, W. Sun, J. Gao, J. Guo and C. Jiang,
composite with crystalline nanoparticles of black P displays a Angew. Chem., Int. Ed., 2012, 51, 9034.
better cyclic stability. Attractive stable cyclic performances at the 12 W.-J. Zhang, J. Power Sources, 2011, 196, 13.
level of 700 (lithium cells) and 350–400 mA h g1 (sodium cells) 13 J. Sun, G. Zheng, H.-W. Lee, N. Liu, H. Wang, H. Yao,
can be observed if the potential windows are restricted to 2.0–0.67 W. Yang and Y. Cui, Nano Lett., 2014, 14, 4573.
vs. Li/Li+ and 2.0–0.33 V vs. Na/Na+. Ex situ XRD and SEM analyses 14 V. L. Chevrier and G. Ceder, J. Electrochem. Soc., 2011, 158,
have been performed to provide insights into the charge storage A1011.
and failure mechanisms of electrodes. The XRD studies demon- 15 Y. Xu, Y. Zhu, Y. Liu and C. Wang, Adv. Energy Mater., 2013, 3,
strate that the redox chemistry of phosphorus in lithium half-cells 128.
is based on the reversible transformation to the Li3P phase while 16 Y. Xu, J. Guo and C. Wang, J. Mater. Chem., 2012, 22, 9562.
the transformation to Na3P phase in sodium half-cells is incom- 17 A. Darwiche, C. Marino, M. Sougrati, B. Fraisse, L. Stievano
plete, leading to a smaller than expected practical capacity and L. Monconduit, J. Am. Chem. Soc., 2012, 134, 20805.
observed in the experimental tests. The post-cycling SEM studies 18 Y. Kim, Y. Park, A. Choi, N.-S. Choi, J. Kim, J. Lee, J. H. Ryu,
reveal that electrodes gradually disintegrate and delaminate from S. M. Oh and K. T. Lee, Adv. Mater., 2013, 25, 3045.
current collectors when the electrochemical testing is done within 19 J. Qian, X. Wu, Y. Cao, X. Ai and H. Yang, Angew. Chem., Int.
larger potential windows of 2.0–0.01 V vs. Li/Li+ or Na/Na+. Such Ed., 2013, 52, 4633.
an effect is absent for the restricted potential windows of 2.0–0.67 20 W.-J. Li, S.-L. Chou, J.-Z. Wang, H.-K. Liu and S.-X. Dou, Nano
vs. Li/Li+ and 2.0–0.33 V vs. Na/Na+, leading to stable cyclic Lett., 2013, 13, 5480.
performances for all tested electrodes in these restricted potential 21 N. Yabuuchi, Y. Matsuura, T. Ishikawa, S. Kuze, J.-Y. Son,
windows. Y.-T. Cui, H. Oji and S. Komaba, ChemElectroChem, 2014,
1, 580.
Acknowledgements 22 A. Calka and A. P. Radlinski, Mater. Sci. Eng., A, 1991, 134,
1350.
Financial support from Central Research Grants Scheme of 23 T. Ramireddy, M. M. Rahman, T. Xing, Y. Chen and
Deakin University and a Discovery grant of the Australian A. M. Glushenkov, J. Mater. Chem. A, 2014, 2, 4282.
Research Council is acknowledged. The Australian Research 24 S. Reich and C. Thomsen, Philos. Trans. R. Soc., A, 2004, 362,
Council is also acknowledged for funding Deakin University's 2271.
Magnetic Resonance Facility, JEOL JEM-2100F transmission 25 T. Xing, L. H. Li, L. Hou, X. Hu, S. Zhou, R. Peter, M. Petravic
electron microscope and combined FTIR/Raman micro- and Y. Chen, Carbon, 2013, 57, 515.
spectroscopic instrument through LIEF grants LE110100141, 26 A. C. Ferrari, Solid State Commun., 2007, 143, 47.
LE100100195 and LE120100166. The authors thank Timcal Ltd. 27 A. Bytchkov, F. Fayon, D. Massiot, L. Hennet and D. L. Price,
for providing a sample of Super P Li™ carbon black and Phys. Chem. Chem. Phys., 2010, 12, 1535.
acknowledge the use of facilities in the Victorian Node of the 28 S. Lange, P. Schmidt and T. Nilges, Inorg. Chem., 2007, 46,
Australian National Fabrication Facility (ANFF). 4028.
Notes and references

1 Chemistry of the Elements, ed. N. N. Greenwood and A.
Earnshaw, Butterworth Heinemann, 1997.

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Phosphorus–carbon nanocomposite anodes for

lithium-ion and sodium-ion batteries

Cite this: J. Mater. Chem. A, 2015, 3,

operation in a lithium-ion battery, the practical electrochemical

Paper Journal of Materials Chemistry A

phosphorus–carbon composite could deliver a capacity of 1890 Characterization

Kapton tape to prevent reacting with moisture and oxygen aer

contrast to the previous report,19 in which deterioration initi-

Journal of Materials Chemistry A Paper

substrates and heated in vacuum overnight at 90 C. All elec-

carbonate (DEC) and dimethyl carbonate (DMC). The electrolyte

for sodium half-cells was 1 M NaClO4 in propylene carbonate

Paper Journal of Materials Chemistry A

carbon elemental maps are depicted in Fig. 4d and g, and the

Journal of Materials Chemistry A Paper

Paper Journal of Materials Chemistry A

the intermediate black phase, the structure of their material

Journal of Materials Chemistry A Paper

Paper Journal of Materials Chemistry A

Table 1 Electrochemical performance of phosphorus–carbon composites in lithium half-cells

Active material loading, Initial discharge/charge

C-1 0.92–1.05 1930/1677a Declining gradually. This work

C-2 0.92–1.05 1995/1706a Declining more abruptly. This work

in the 50th cycle.

Amorphous phosphorus– 3 2651/2355b Minor decline. 90% of 8

Activated phosphorus– Not reported 3289/1385b Declining. 900 mA h g1 4

Black phosphorus–acetylene About 3.1c 1962/1746b Declining. Capacity of about 10

Black phosphorus–carbon 2.5 2010/1814a Declining. Capacity of about 5

Nanostructured red Not reported 1200/840a Relatively stable capacity. 11

Black phosphorus–graphite 2.0–2.8 2786/2382a Minor decline. 80% Of 13

Journal of Materials Chemistry A Paper

Paper Journal of Materials Chemistry A

Table 2 Electrochemical performance of phosphorus–carbon composites in sodium half-cells

Active materials Initial discharge/charge

C-1 0.92–1.05 1530/1322a Slowly declining in the rst This work

C-2 0.92–1.05 Declining. Capacity of 119 This work

Amorphous red 1.4–2.1 2223/1890b Minor decline. 93% of 18

Amorphous carbon– 3 2015/1764b Stable cyclic performance for 19

Red phosphorus–carbon Not reported 2210/1675b Declining. 76.6% Of capacity 20

Red phosphorus–acetylene 0.4–0.46 Reversible capacity of about Declining. Capacity of about 21

Journal of Materials Chemistry A Paper

g1) in lithium and sodium half-cells in restricted potential

Insights into the charge storage and failure mechanisms

Paper Journal of Materials Chemistry A

diﬀraction record, possibly due to the limited available

sodium half-cell was 1847 mA h g1. However, the rst

discharge capacity of the cell was only 1530 mA h g1. We

Journal of Materials Chemistry A Paper

Notes and references

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