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REVIEW
Cite this: J. Mater. Chem. A, 2016, 4,
14915
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Nanostructured metal phosphide-based materials
for electrochemical energy storage
Xia Wang, Hee-Min Kim, Ying Xiao and Yang-Kook Sun*
The development of electrochemical materials for advanced energy storage devices such as lithium/
sodium-ion batteries (LIBs/SIBs) and supercapacitors is essential for a sustainable future. Nanostructured
materials have been widely studied in energy storage due to their advantages including high transport
rates of Li+/Na+ and electrons, short charge diffusion paths and high surface areas. Metal phosphides are
promising candidates for advanced energy storage devices, stemming from low-cost, high volumetric
and gravimetric capacities. In this review, we offer a brief summary of the synthesis and electrochemical
performance of metal phosphide nanostructures and metal phosphide-based nanocomposites,
Received 5th August 2016
Accepted 16th August 2016
associated with corresponding applications in LIBs/SIBs and supercapacitors. In addition, we discuss
DOI: 10.1039/c6ta06705k
the relationship between nanostructures and electrochemical performances, together with the related
Li+/Na+ storage mechanism. At the end, we provide the challenges and prospects of future research
www.rsc.org/MaterialsA
trends of nanostructured metal phosphides.
1. Introduction
To reduce society's dependence on fossil fuels, it is urgent to
develop renewable and sustainable energy sources, such as
solar, geothermal, tidal, and wind power. Electrochemical
energy storage devices, including rechargeable batteries and
supercapacitors, have garnered widespread attention and have
been widely used in portable electronics and electric vehicles.1–6
Due to their high energy density, long lifespan, no memory
effect, and environmental benignity, lithium-ion batteries
(LIBs) have been considered as the dominant power source for
portable electronic devices.7–9 However, the practical application of LIBs in electric vehicles (EVs) and hybrid electric vehicles
(HEVs) needs to meet several requirements: safety, cost, lifetime, power density and energy density. The overall performance of LIBs mainly depends on the electrode material;10–14
therefore, developing highly efficient materials used as electrodes for LIBs is of importance currently.
The widespread usage of large-format LIBs drives a price rise
of Li metal because of the increasing demand for Li commodity
chemicals, along with geographically constrained Li mineral
reserves. As a potential and acceptable alternative to LIBs,
sodium-ion batteries (SIBs) have thus been attracting more
attention due to the wide availability and low cost of
sodium.15–17 The research achievements in LIBs could promote
the development of SIBs because the properties between Li and
Na are similar. However, Na+ ions are approximately 55% larger
than Li+ ions in radius, severely limiting the energy density and
Department of Energy Engineering, Hanyang University, Seoul, 04763, South Korea.
E-mail: [email protected]
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rate capability of SIBs. Ever-growing research attention is being
devoted to exploring suitable electrode materials with excellent
sodium-storage performance.
Supercapacitors, as promising electrochemical energy storage
devices, have drawn widespread hope resulting from their fast
charging/discharging rate, long cycling life, and high power
density.18 They have potential for wide use in HEVs, pacemakers,
and portable electronic devices as a complement to batteries,
offering protection against power disruption as backup power
sources.19 According to their charge storage mechanism, supercapacitors can be classied as electrochemical double layer
capacitors (EDLCs) based on ion adsorption/desorption or as
pseudocapacitors on the basis of fast surface redox reactions.
Carbon, a typical EDLC, possesses the advantages of long cycle
life and good mechanical performance but has the disadvantage
of low specic capacitance, which cannot satisfy the everincreasing requirements of EVs.20–25 Pseudocapacitors retain
high specic capacitance; however, they have low power density
and poor cycling performance. To improve the energy density,
cycling life, and power density of supercapacitors, asymmetric
supercapacitors combining these two types (EDLC as a capacitive-like electrode, i.e., power source, and pseudocapacitor as
a battery-like electrode, i.e., energy source) become an effective
alternative to both EDLCs and pseudocapacitors.26,27
Furthermore, compared with bulk materials, nanostructured
materials possess several merits when they are applied in the
energy storage area. For instance, a high surface area of nanomaterials increases the electrode/electrolyte contact area, which
facilitates higher Li+/Na+ ux across the interfaces for LIBs/SIBs to
improve rate capability. In supercapacitors, nanostructured
materials offer more ion-accumulation active sites for double-layer
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formation and redox reactions, enhancing the specic capacitances. In addition, the short ion and electron transport path in
nanostructured materials leads to a faster diffusion rate. Moreover, nanostructures can accommodate the huge volume expansion and structural distortion associated with ion insertion/
extraction, prolonging cycle life.28–39 As is well known, the relationships between the structure and performance strongly depend
on the shape, chemical composition, size of grains, and interfaces.
Thus, a great number of novel electrode materials for LIBs, SIBs,
and supercapacitors with controlled nanostructures have been
synthesized and reported, providing a signicant enhancement in
electrochemical performance.14,34,40,41
Metal phosphides lie between the more ionic metal nitrides
and the intermetallic metal antimonides in their chemistry.
Compared with metal nitrides, metal phosphides exhibit superior
chemical properties, because of the existence of multi-electron
orbitals. Therefore, metal phosphides have been widely employed
as catalysts for hydrodenitrogenation (HDN), hydrodesulfurization
(HDS), hydrogen evolution reaction (HER), and oxygen reduction
reaction (ORR).42 In 2002, Nazar and co-workers reported that
a CoP3 electrode presented promising Li-storage performance with
a conversion mechanism and drew extensive interest because of
its low-cost and high theoretical capacity.43 Since then, more metal
phosphides are used as anode materials for LIBs/SIBs. Beneting
from their high theoretical lithium/sodium-storage capacities and
low intercalation potentials, metal phosphides have become
promising candidates for LIBs/SIBs. Moreover, metal phosphides
possess the metalloid properties and high specic capacitances, so
they are widely used in supercapacitors.
Until now, numerous excellent reports and reviews on the
synthesis, performance, characterization, and design of nanostructured materials for energy storage applications have been
published.44–51 In addition, there are also some reviews on the
synthesis of nanosized metal phosphides52 and their application in hydrogen evolution reactions,42 and magnetic and
catalytic elds.53
To our knowledge, no review paper has yet examined the
recent progress and trends in nanostructured metal phosphides
for LIBs, SIBs, and supercapacitors with high energy and power
density. Therefore, we present a simple summary of the synthesis
and electrochemical performance of metal phosphide nanostructures and metal phosphide-based nanocomposites in this
review. Additionally, we concentrate on presenting them as electrode materials for LIBs, SIBs, and supercapacitors. Thereaer,
we discuss the correlation between nanostructures and electrochemical performance, together with corresponding Li+/Na+
storage mechanisms. Finally, we offer an outlook on the challenges and future directions for metal phosphides in energy
storage applications.
2. Nanostructured metal phosphidebased materials for LIBs
2.1
Lithium-storage mechanism
The Li-storage mechanisms of metal phosphide-based anodes
are complex, but they can generally be classied into two
14916 | J. Mater. Chem. A, 2016, 4, 14915–14931
Review
categories based on the character of the metal and the stability
of metal–phosphor bonds on Li insertion/extraction: intercalation reactions and conversion reactions.52
(i) Intercalation mechanism. During the reduction reaction,
metal phosphides (MPn) possess topotactic Li intercalation
associated with the destruction of P–P bonds in the metal
phosphides and the formation of LixMPn, reoxidized to MPn in
the charge process without breaking the M–P bonds. Consequently, the formation of LixMPn by the insertion reaction
results in a stable crystalline structure with good electrochemical properties. The reaction can be written as:
MPn + xLi+ + xe 4 LixMPn
(1)
In general, the existence of a di-phosphorous pair (namely,
a residual P atom directly bonded to a metal ion) leads to the
simple Li-ion intercalation mechanism.54
Nazar et al. studied the low-potential Li+ intercalation in
a solid-state MnP4 (0.57–1.70 V) and found that a topotactic
crystalline transformation at ambient temperature took place
by an electrochemical redox process: MnP4 4 Li7MnP4.55 The
P–P bonds in the MnP4 structure cleaved upon Li insertion to
form crystalline Li7MnP4 and reversed aer reoxidation, associated with the electrochemical recrystallization of MnP4.
Therefore, MnP4 acted as an electron storage reservoir. Kim
et al. investigated the Li storage mechanism of teardrop-shaped
ultrane SnP0.94 particles by X-ray diffraction (XRD) analysis
and X-ray absorption spectroscopy (XAS). The XRD showed that
the original structure of the SnP0.94 remained aer continuous
cycling. In addition, the charge compensation by Li-ion insertion occurred in the short-range-ordered structure around the
Sn and not through bulk lattice structural variation of the
layered SnP0.94. XAS spectra suggested that there is no effective
change in the Sn oxidation state and that the polymeric –[Sn–P–
P–Sn]– slabs were not broken by the Li-ion behaviour in the
SnP0.94. The SnP0.94 exhibited good electrochemical cycling
properties resulting from the structural reversibility of the
lithium intercalation/deintercalation mechanism through
molecular channels without a phase transition from SnP0.94 to
the metallic alloy LinSn.56 VP,57 FeP2,58 FeP4,59 Zn3P2,60 MoP2,61
MnP,62 and MoP63 were also found to be good intercalation
materials for LIBs.
(ii) Conversion reaction mechanism. In this electrochemical
reaction, the bonds between metal and phosphorous are
broken, resulting in the formation of nanosized metal particles
and Li-phosphides during the charge/discharge processes. The
reaction can be written in the following form:
MPn + 3nLi+ + 3ne 4 nLi3P + M
(2)
The reactivity between metal phosphides and lithium is
dominated by the redox nature of the P, and the capacities
depend on the number of electrons in the anion. In the
conversion reaction mechanisms, some metal phosphides
suffer from direct formation of metal particles and Li3P;
however, others start with intercalation and end with conversion during a continuous charge/discharge process with respect
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Review
to potential vs. Li/Li+.64,65 Gillot et al. observed that cubic NiP2
suffered from a direct conversion process during the 1st
discharge, in contrast to an intercalation process followed by
a conversion process for monoclinic NiP2. That Li-uptake
mechanism rooted in subtle structural changes was investigated through electronic structure calculations, which showed
that the cubic NiP2 was inclined to a direct conversion reaction
into Li3P and Ni because its closely packed structure hindered
any Li+ insertion. Nevertheless, some available interlayer space
in the monoclinic NiP2 accommodated Li+, favoring the formation of the monoclinic Li2.5NiP2 phase.66 The promising Li uptake
of CoP3,67 Co2P,68 CoP,69 and Cu3P70 electrodes goes through
a direct conversion mechanism. However, the reactivity of NiP3,71
CoP,72 Cu3P,73,74 FeP,75 and Sn4P376 is followed by successive
insertion and conversion during the charging/discharging
processes.
2.2
Nanostructured metal phosphides
Inexpensive metal phosphides are regarded as alternative anode
materials for LIBs because of their lower intercalation potentials and exceptionally high volumetric and gravimetric capacities compared to commercial carbonaceous materials.77 So far,
numerous phases of binary and ternary metal phosphides have
been used as negative electrodes, including MnP4,55 CoP3,43
ZnP2,78 Zn3P2,79 InP,80 GaP,81 Cu3P,74,82 VP,57 VP2,62 VP4,83 FeP,75
FeP2,58 and FeP4.59
However, like most of the metal oxides, metal phosphides
undergo poor cycling stability, mainly resulting from a dramatic
volume variation during discharge/charge processes, which leads
to pulverization, aggregation, and the loss of electric contact
between the active materials and the current collector. Downsizing the metal phosphides to the nanoscale has proved to be an
effective strategy to solve this problem beneting from a large
electrode-electrolyte contact area and short solid-state diffusion
path for both electronic and ionic transfer within nanosized
materials. Research on metal phosphides for LIBs is emerging
and it could bring new opportunities via appropriate tuning of
the nanostructure. Until now, various metal phosphide nanostructures, including nanoparticles,84 nanosheets,85 dendrites,86
nanorods,87,88 hollow spheres,89 and peapod-like structures,90
have been reported. They were synthesized by some routine
approaches, including high-energy mechanical ball-milling,85,91–94
and high-temperature decomposition of phosphorus-containing
precursors including NaH2PO2,95 (NH4)2HPO4,96 triphenylphosphine (TPP),97–100 tri-n-octylphosphine oxide (TOPO),101 and trioctylphosphine (TOP).102–106
In the following sections, we will discuss the most widely
studied metal phosphide anodes, including nickel phosphides,
iron phosphides, cobalt phosphides, copper phosphides, tin
phosphides, and molybdenum phosphides. Moreover, we
summarize other metal–phosphide anodes and their representative nanostructures, i.e., germanium phosphides and nickel
cobalt phosphides.
2.2.1 Nickel phosphides. In the family of metal phosphides, nickel phosphides, such as Ni3P,107,108 Ni2P,109 Ni12P5,110
Ni5P4,111 NiP2,66,112 and NiP3,71 are the most studied materials as
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Journal of Materials Chemistry A
anodes for LIBs because of the richness of the associated phase
diagram. Among them, phosphorus-rich phases (NiP2, and
NiP3) possess higher capacities. For example, NiP3 can deliver
an initial reversible capacity of 1475 mA h g1 because it reacts
with nine lithium per formula unit at an average potential of
0.9 V vs. Li+/Li. However, the cycling stability of such a kind of
metal phosphide is relatively poor.71 Compared with phosphorus-rich phases, metal-rich phosphides, including Ni3P,
Ni2P, Ni5P4, and Ni12P5, possess a stronger metallic character as
well as a higher proportion of Ni–Ni bonds vs. Ni–P and P–P
bonds, exhibiting lower reaction potential in average.121 Ni3P
reacts with Li to form Ni and Li3P in the potential range of 1.5 V
and 0.8 V.107 However, upon continuous cycling, both of the
phosphorus-rich and metal-rich nickel phosphides show
tendency to deteriorate rapidly in the reversible capacity
because of the volume change and detachment from the copper
foil. Thus, many efforts have been made to improve the cycling
performance of nickel phosphides and reduce the irreversible
capacity loss. To date, a variety of nickel phosphides with
unique architectures have been reported. Some of the recent
data on the Li-cycling properties of nickel phosphide are listed
in Table 1.
Designing nanostructured nickel phosphides is favourable
for improving electrochemical performance in ways that cannot
be achieved using bulk materials. In particular, the fabrication
of porous nanostructures arouses much interest because pores
can effectively accommodate the large volume changes and lead
to a short diffusion length for lithium ions during cycling.85
Xiang et al. adopted an electrodeposition method using selfassembled polystyrene spheres with different layers as
templates to grow porous nickel phosphide lms, serving as
binder-free anodes for LIBs, which sustained a specic capacity
of 557 mA h g1 at 0.2C aer 50 cycles.113
Besides, nickel phosphides possess low intrinsic electronic
conductivity, and therefore coating or compositing with carbonaceous materials, e.g., typical carbon, graphene, or carbon
nanotubes, could be a facile route to improve their lithium
storage performance. The presence of carbon can not only
accommodate the volume variation associated with lithium ion
insertion, but also effectively prevent the aggregation of the
nickel phosphide. Taking advantage of a facile organometallic
method using Ni nanosheets as templates, Lu et al. fabricated
Ni2P nanosheet-based anodes. The related results suggest that
most of those materials deliver high reversible capacities and
excellent cycling performance. Lu et al. fabricated a monophase
core–shell Ni5P4/C composite via a wet chemistry reaction using
nickel acetylacetonate (Ni(acac)2), TOP, oleic acid (OA), and trin-octylamine (TOA) as a metal precursor, phosphorus source,
surfactant agent, and solvent, respectively.63 The composites
exhibited a uniform sphere-like morphology with an amorphous carbon shell possessing a uniform thickness of approximately 10 nm, together with about 9.91 wt% in the composites
(Fig. 1a and b). The resulting core–shell Ni5P4/C composite
delivered a high capacity of 644.1 mA h g1 over 50 cycles at 0.1C
(Fig. 1c). In nickel phosphide/carbon nanostructured composites, peapod-like nanocomposites with nanoscale active nickel
phosphide encapsulated in carbon bers have attracted a great
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Table 1
Review
Summary of nanostructured nickel phosphide based anodes
Nanostructures
Methods
Current density
(mA g1)
Capacity
(mA h g1)
Hierarchical h-Ni2P spheres
Ni2P wires
Porous Ni2P nanosheets
Ni3P–Ni lms
Ordered porous Ni3P lm
Ni–P lm
NiP2 nanoparticles
Amorphous crystalline Ni–P
nanoparticles
Peapod-like Ni2P/C nanoparticles
Peapod array of Ni2P graphitized carbon
Ni2P/graphene sheets
Peapod-like Ni12P5@C composites
Ni2P@C nanoparticles
Ni2P/C nanotube
Ni5P4/C composite
Thermal decomposition of TOP
Thermal decomposition of TOP
Organometallic method
Electrodeposition
Electrodeposition
Electrodeposition
Thermal decomposition of TOP
Ionothermal process
0.5C
0.1C
0.1C
0.02 mA cm2
0.2C
54.2
0.13 mA cm2
50
365
434
380
340
557
399
750
217
50
50
50
40
50
50
10
50
114
115
85
107
113
116
117
118
Hydrothermal method and calcination
Hydrothermal method and calcination
Solvothermal method
Hydrothermal method and calcination
Thermal decomposition of TOP
Thermal decomposition of TOP
Wet-chemistry reaction and solid-state
reaction
Intercalation of surfactant and
calcination
Thermal decomposition of TOP
Electrodeposition
Hydrothermal method and calcination
Thermal decomposition of TOP
Thermal decomposition of TPP
100
200
54.2
100
C/20
5C
0.1C
630
634
450
660
200
310
644
200
300
50
100
2
100
50
90
119
120
87
121
122
65
100
635
200
123
0.1C
250
0.2C
100
0.2C
435
463.6
625
665
600
50
50
200
100
100
124
125
126
110
111
Ni3P/Ni/C nanocomposite
Ni2P@C nanocomposite
Ni–P–C lm
Sandwiched Ni2P/C
Ni12P5/CNT nanohybrids
Ni5P4@C nanoparticles
deal of interest. Their unique active surfaces/interfaces and
excellent stability make them promising anode materials for
LIBs.90 Zhang et al. prepared a peapod-like Ni12P5/C nanocomposite, using a NiNH4PO4$H2O nanorod as the precursor
that was subsequently carbonized under an Ar gas, shown in
Fig. 1 (a and b) TEM images of the Ni5P4/C, and (c) cycling performance of Ni5P4/C electrodes at 0.1C. [Reprinted with permission from
ref. 65. Copyright 2012 Wiley].
14918 | J. Mater. Chem. A, 2016, 4, 14915–14931
Cycle
number
Ref.
Fig. 2a.87 SEM images of the Ni12P5/C nanocomposite show the
uniform peapod-like structure and the Ni12P5 nanoparticles
were tightly conned in the carbon bers, (Fig. 2b). At the 1st
cycle, the obtained peapod-like Ni12P5/C nanocomposite delivered a high reversible capacity of 660 mA h g1 at 0.1 A g1, and
the capacity remained extraordinarily stable aer subsequent
cycles, with a coulombic efficiency close to 100% for each cycle.
Moreover, the reversible capacity stabilized at 660 mA h g1 at
a current density of 0.1 A g1 aer 100 cycles with excellent
retention (Fig. 2c). The excellent lithium-storage performance
was ascribed to its peapod-like structure as well as carbon
coating. The peapod-like structure, which not only accommodated the volume variation associated with Li+ insertion, but
also effectively prevented the aggregation of the active materials, can be retained without obvious breakage, thus leading
to high stability. Moreover, the carbon coating can enhance
charge transport and improve the conductivity of the nanocomposites.87 Nanopores were able to offer a large contact area
for the electrolyte/electrodes and accelerate the transfer and
immersion of the electrolyte, resulting in a fast rate capability.
Using the same procedure, Bai et al. fabricated a peapod-like
Ni2P@carbon nanocomposite with a reversible capacity of
630 mA h g1 at 0.1 A g1 aer 100 cycles with excellent cycling
performance, the reasons for such excellent performance were
attributed to the peapod-like architecture and carbon coating.90
Bai et al. also synthesized a peapod array of Ni2P@graphitized
carbon bre composites on a Ti substrate for direct use as
a binder-free electrode for LIBs (Fig. 2d).119 It exhibited a high
specic capacity of 634 mA h g1 at 200 mA g1 aer 300 cycles
with 97% capacity retention, as well as excellent rate capability
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(a) Schematic illustration of the synthetic procedure of the
peapod-like Ni12P5/C nanocomposite, (b) SEM image of the peapodlike Ni12P5/C nanocomposite and (c) cycling performance and
coulombic efficiency of the peapod-like Ni12P5/C nanocomposite at
0.1 A g1. [Reprinted with permission from ref. 87. Copyright 2014
Wiley] (d) TEM image of the Ni2P peapod array electrodes, and (e) rate
capability of the Ni2P peapod array electrodes. [Reprinted with
permission from ref. 119. Copyright 2015 Royal Society of Chemistry].
Fig. 2
with a relatively high capacity of 420 mA h g1 at 10 A g1,
conrming the 1D peapod-like structure as a promising material structure for LIBs (Fig. 2e).
Among various carbonaceous materials, carbon nanotubes
(CNTs) as unique 1D tubular architectures exhibit various
merits, including high electronic conductivity, chemical
stability, high Young's modulus, and exceptional surface properties, making them becoming ideal supporting materials.127,128
CNTs can not only serve as supports for decorating nanoparticles, but also work as a highly conductive matrix offering
good contact between the nanoparticles. Additionally, CNTs can
alleviate volume variations and hinder the aggregation of
nanoparticles during the charge/discharge processes. Moreover,
owing to their large surface-to-volume ratio and high surface
area, CNTs can offer 1D short electron transport and Li+
diffusion pathways, coupled with a large electrolyte–electrode
contact area, leading to short charge/discharge times. Consequently, a CNT-nickel phosphide composite is believed to
display excellent lithium-storage performance. Wang et al.
synthesized a unique hybrid nanostructure, Ni12P5/CNT nanohybrids, using an in situ one-pot hot-solution colloidal synthetic
strategy to decorate Ni12P5 nanocrystals onto oxidized CNTs,
displaying a high capacity of 665 mA h g1 at a current density
of 100 mA g1 aer 100 cycles and superior rate performance for
LIBs.110 Besides, graphene is an outstanding support/coating
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Journal of Materials Chemistry A
material for decorating/encapsulating active materials for LIBs
because of its superior electrical conductivity, large surface
area, pronounced chemical stability, and high exibility.129
Graphene-based sandwich-like nanomaterials, in which nanoparticles are tightly encapsulated between graphene sheets
rather than simply placed on the graphene surface, have
garnered wide attention. The sandwich structure can not only
effectively restrain the active nanoparticles from aggregating
and peeling away from the conductive substrates upon cycling,
but also suppress large volume variations during the lithiation/
delithiation processes. In addition, it can effectively shorten the
electronic paths.130 Therefore, graphene-based materials with
sandwich-like architecture possess improved reversible capacity
and excellent cycling life. Feng et al. fabricated sandwiched Ni2P
nanoparticles between graphene sheets using a sheet-like
NiNH4PO4$H2O precursor as a sacricial template.126 Molecular
glucose was placed on the template through hydrogen-bonding
action and subsequently the obtained precursor was calcined in
an H2 atmosphere, transforming the NiNH4PO4$H2O nanosheets and glucose into Ni2P nanoparticles and graphitized
carbon layers, respectively (Fig. 3a). Substantial nanoparticles
and coupled graphene layers are presented in Fig. 3b, and the
Ni2P nanoparticles were accommodated in multiple graphene
layers. The unique sandwich architecture and conductive
matrix provided conducting paths for fast charge transport,
which led to outstanding cycling stability as well as a high
reversible capacity of 625 mA h g1 at 0.2C aer 200 cycles
(Fig. 3c).
In addition to the microstructure and composition, the
electrolyte was demonstrated to have an important effect on the
electrochemical performance of nickel phosphides. Tatsumisago et al. employed Ni5P4 and NiP2 submicronic nanoparticle
Fig. 3 (a) Schematic illustration of the synthetic procedure for Ni2P
nanoparticles sandwiched between graphene sheets, (b) TEM image of
the sandwiched composite, and (c) cycling performance at 0.2C.
[Reprinted with permission from ref. 126. Copyright 2015 Wiley].
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Journal of Materials Chemistry A
aggregates as electrode materials and (Li2S)80(P2S5)20 as an
electrolyte in all-solid-state batteries to improve the Li-storage
performances of the electrodes.131
2.2.2 Iron phosphides. Owing to their low-cost and high
theoretical capacities, iron phosphides (Fe2P, FeP, FeP2, and
FeP4) have been attractive in recent years.59,132 As anode materials for batteries, Fe/P ratio, structural, electronic properties of
play important roles in inuencing their performance. Similar
to that of nickel phosphides, the phosphorus-rich iron phosphide phases exhibit higher reactivity vs. Li. For instance,
during the 1st discharge, FeP presents a potential plateau at
0.1 V, corresponding to the insertion of Li, while FeP2 and FeP4
possess a potential plateau at 0.3 and 0.5 V, respectively. In
addition, during the 1st charge, FeP and FeP2 exhibit a similar
potential plateau at 0.9 V and 1.1 V, attributed to extraction of
Li, while FeP4 possesses a single oxidation peak at 1.1 V.59
Until now, various iron phosphide-based nanomaterials have
been explored and investigated as LIB anodes. Referred materials
include FePy nanoparticles,133 amorphous FeP2,77 amorphous
FePy (0.1 < y < 0.7) thin lms,134 Fe2P on Cu substrates,135 nanorodFeP@C composites,136 Fe2P nanoparticles enveloped in sandwichlike graphite carbon sheets (Fe2P/GCSs),137 FeP2/C nanotubes,138
and Fe2P–LiFePO4 composites.139 Hall et al. synthesized amorphous FeP2 nanoparticles by reacting Fe(N(SiMe3)2)3 with PH3 in
tetrahydrofuran (THF) at 100 C.77 The resulting material presented a reversible lithiation potential at 0.56 V vs. Li/Li+ and
delithiation potential at 1.00 V during the 1st discharge. In
addition, a high reversible capacity of 906 mA h g1 aer 10 cycles
at 0.1C was delivered, corresponding to 66% of the theoretical
capacity, which was ascribed to the nanostructural and amorphous properties of the FeP2. Yang's group fabricated iron
diphosphide/carbon tube (FeP2/C) nanohybrids, in which the
nanoscale FeP2 attached on conical carbon tubes through
a pyrolysis process138 The synergetic effects of nanostructured
FeP2 and carbon tubes enhance electrical conductivity and
accommodate the volume variation upon cycling. Thus the obtained FeP2/C nanohybrids possessed a high specic capacity of
435 mA h g1 at a current density of 100 mA g1 as well as
excellent rate capability. Recently, Wang's group reported the
synthesis of Fe2P nanoparticles in sandwich-like graphited
carbon sheets (Fe2P/GCS) using FeFe2(PO4)2(OH)2 and molecular
glucose as the precursor and green carbon source, respectively.137
Glucose was decorated on the precursor through hydrogenbonding action and subsequently calcined in an H2 atmosphere.
The sandwiched Fe2P/GCS delivered a high reversible capacity of
602 mA h g1 at a current density of 100 mA g1, with excellent
cycling life as high as 200 cycles and outstanding rate performance with 362 mA h g1 even at 10 A g1.
2.2.3 Cobalt phosphides. Cobalt phosphides have been
studied as anode materials in LIBs.67–69,72,89,111,140–143 Because the
negative property of cohesive energy, Co2P, CoP, and CoP3 are
stable phases. However, the stability of cobalt phosphides
decreases with the increase of P element content. Therefore,
Co2P with an orthorhombic structure possesses the best
stability and electronic conductivity during all cobalt phosphides.140 For Co2P and CoP, conversion reactions with 3 Li+ to
form Co and Li3P take place at around 1.0 V during the 1st
14920 | J. Mater. Chem. A, 2016, 4, 14915–14931
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cycling discharge. Additionally, the decomposition from Li3P
into LiP occurs at approximately 1.5 V in the 1st charge.89 In
subsequent cycles, a redox reaction between Li3P and LiP takes
place. CoP3 reacts with Li+ at around 0.4–0.25 V by a single
extended quasi-plateau to form Co and lithium-phosphide
during the 1st discharge. In the 1st charge, Li+ can be reversibly
extracted. In the following cycles, the reaction is reversible
decomposition of Li3P to form LiP and Li+.43
The theoretical capacities of cobalt phosphides as anode
materials are higher than 500 mA h g1, depending on their
chemical and physical structures. Although their theoretical
capacity is remarkably high, the application of cobalt phosphide-based anodes in practical LIBs is still challenging
because of their poor electrical conductivity and massive
volume variation upon cycling. An effective approach to alleviate those drawbacks is using nanostructured cobalt phosphide-based anodes, such as nanocrystalline CoP thin lms,69
Co2P nanorods,89 CoP hollow nanoparticles,68 Co2P nanospheres,68 or Co2P lms.68 Yang et al. synthesized Co2P nanorods and spheres (CoP hollow nanoparticles) using a facile
thermal decomposition of the Co–TOP complex in hot oleylamine solvent by varying the thermal decomposition reaction
time (Fig. 4a).89 The TEM images in Fig. 4b clearly show that the
sample was composed of Co2P nanorods that were 50 nm long
with a diameter of 10 nm when the reaction time was 1 h. By
changing the reaction time, hollow CoP, ne CoP nanoparticles
encapsulated in the amorphous framework can be obtained
(Fig. 4c and d). When evaluated as anode materials for LIBs, the
resulting structure enables effective Li+ insertion/extraction and
suppresses the volume strain upon cycling, and the hollow CoP
(a) Schematic illustration of the synthetic procedure for cobalt
phosphides, (b–d) SEM images of Co2P nanorods (1 h), CoP hollow
nanoparticles (12 h), and CoP solid nanoparticles (20 h), respectively,
(e) cycling performance, and (f) rate capability at 0.2C. [Reprinted with
permission from ref. 89. Copyright 2013 Journal of American Chemical Society].
Fig. 4
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particles delivered the highest reversible capacity, 630 mA h g1
aer 100 cycles, corresponding to 83.3% of the 2nd discharge
capacity (Fig. 4e), associated with excellent rate capability
(Fig. 4f). Another promising method is to take advantage of
nickel phosphide/carbon-based composites as anode materials
for LIBs, because conductive carbon can enhance the conductivity of the electrode and works as a structure-buffer against
massive volume variations during cycling. For instance, Yang
et al.142 fabricated a composite of cobalt phosphide nanowires
and reduced graphene oxide (CoP/RGO) using a hydrothermal
method followed by subsequent calcinations. As shown in
Fig. 5a and b, CoP nanowires, with a diameter of 200–300 nm
and length of 10–20 mm, were evenly conned on the RGO layer.
The CoP/RGO nanocomposite displayed excellent lithium
storage performance in terms of specic capacity, cycling
stability, and long cycle-life. Specically, a high reversible
capacity up to 960 mA h g1 at a current density of 200 mA g1
aer 200 cycles was delivered (Fig. 5c), derived from a large
specic surface area and improved conductivity able to alleviate
the volume variation and to enhance charge transport.
In addition, Lu et al. reported Co2P nanorod/graphene
nanocomposites in which Co2P nanorods grew on graphene
sheets, displaying a relative reversible capacity of 888 mA h g1
aer 250 cycles at 100 mA g1 and excellent cycle stability
(Fig. 5d).140 Recently, Jiang et al. prepared CoP@C nanorods that
manifested an enhanced performance in Li-ion reversible
capacity of around 655 mA h g1 aer 100 cycles at 180 mA g1
and 530 mA h g1 aer 200 cycles at 900 mA g1, representing
good cyclic stability and excellent rate performance as a promising anode material for LIBs.111
2.2.4 Tin phosphides. Sn4P3 holds a layered structure in
which alternating P and Sn layers are organized into 7-layer
units (all P atoms are octahedrally coordinated by Sn atoms, and
50% of Sn atoms are octahedrally coordinated by P atoms) that
reproduce along the c-axis.144–146 In 1967, synthesis for Sn4P3 was
rst reported. In 2004, nanosized Sn4P3 fabricated through
a mechanochemical method was rst reported by Kim et al.76 The
material manifested a high reversible capacity of 370 mA h g1
aer 50 cycles at 0–0.72 V; however, it also displayed a large
irreversible capacity loss stemming from the formation of inactive Li3P. Increasing the Sn content in Sn4P3 could reduce the
irreversible capacity loss and improve the capacity to some
extent. Kim et al. synthesized Sn4+dP3 (0 # d # 1) through
a mechanochemical method. The resulting material possessed
a high reversible capacity above 530 mA h g1 for up to 50 cycles
at 0–0.72 V.145 Wu et al. prepared Sn4P3 thin lms by reactive
pulsed laser deposition. The lms possessed a high discharge
capacity of 550 mA h g1 aer 10 cycles at 100 mA g1.144 Liu et al.
reported Sn4P3 nanoparticles with an average size of 15 nm
fabricated through a solvothermal method at 180 C for 10 h.146
The resulting material manifested a high reversible capacity of
442 mA h g1 aer 320 cycles at 100 mA g1 and excellent cycling
performance, mainly attributed to its small size. Kim et al.
synthesized teardrop-shaped ultrane SnP0.94 nanoparticles
using a thermal decomposition approach in a mixed solution of
TOP and TOPO.56 The obtained products displayed teardrop-like
ultrane particle morphology visible in TEM images (Fig. 6a).
When evaluated as anode materials for LIBs, the teardrop-shaped
ultrane SnP0.94 nanoparticles had a reversible capacity of
681 mA h g1 aer 40 cycles at 120 mA g1 between 0 and 1.2 V,
equal to 92% of the initial charge capacity. The superior cycling
stability was ascribed to structural reversibility based on the
intercalation/deintercalation mechanism by molecular channels in the absence of phase transition. The lithium storage
mechanism was investigated by powder XRD (Fig. 6c) and XAS
spectroscopic studies revealing the Li+ intercalated in the
intermolecular channel between the SnP0.94 slabs.
(a and b) SEM and TEM images of the CoP/RGO nanocomposite, respectively, and (c) cycling performance and coulombic
efficiency at 0.2 A g1 and rate capability. [Reproduced with permission
from ref. 142. Copyright (2016) by Wiley-VCH]. (d) Cycling performance and coulombic efficiency at 0.1 A g1 of Co2P nanorod/graphene nanocomposites. [Reprinted with permission from ref. 140.
Copyright 2015 Elsevier].
Fig. 6 (a) TEM images of teardrop-shaped SnP0.94 particles. (b)
Discharge–charge curves of the teardrop-shaped SnP0.94 particles at
120 mA g1. (c) Powder XRD patterns of the as-prepared SnP0.94
particles before discharging at point (1), after fully discharging to 0 V
and 1.2 V, corresponding to points (4) and (8), and after 10 and 20
cycles (fully discharged to 0 V). [Reprinted with permission from ref. 56.
Copyright 2007 Wiley].
Fig. 5
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2.2.5 Copper phosphides. Among all the Cu–P materials,
only Cu3P remains stable in air; therefore, there have been few
reports related to the Li-storage performance investigation.147–149 Serving as an electrode material in LIBs, Cu3P has
theoretical gravimetric and volumetric capacities of 390 mA h
g1 and 3020 mA h cm3, respectively, which are higher than
those of graphite (372 mA h g1 and 830 mA h cm3).86 The 1st
discharge platform is located at 0.89–0.7 V, attributed to the
conversion reaction with 3 Li+. In the subsequent cycles, the
reaction takes place at 0.93–0.76 V.86 It is reported that pure
Cu3P anodes suffer from large volume variations during cycling.
To reduce the volume change and improve their cycling
performance, different nano/micro-structured Cu3P have been
developed, including Cu3P hierarchical dendrites,86 self-supported Cu3P/Cu nanorod electrodes,147 and thin Cu3P lms.149
Liu et al. successfully prepared well-dened Cu3P hierarchical
dendrites through a hydrothermal method.86 The material displayed a high reversible capacity of 291 mA h g1 aer 20 cycles
at 0.1C, attributed to its small size and the assembly structure of
the Cu3P particles. Besides, Villevieille et al. fabricated carbonfree self-supported Cu3P/Cu nanorod electrodes and a high
capacity of 2 mA h cm2 aer 40 cycles at C/60 was delivered by
utilizing the improved Li diffusion beneting from the electrode interface.147
2.2.6 Molybdenum phosphides. As a promising anode
material, MoP2 with a layered structure possesses a large free
volume that can work as a Li+ intercalating channel and seven P
atoms that coordinate with long bond distances around the Mo
atom can adsorb Li+. Kim et al. reported a highly reversible Li-ion
intercalating MoP2 cluster composed of approximately 10 nm
nanoparticles synthesized by a mechanochemical method.54 The
MoP2 cluster delivered initial charge and discharge capacities of
719 and 817 mA h g1, respectively, associated with a coulombic
efficiency of 88% at 160 mA g1 in 0–1.5 V. In addition, the
material displayed excellent cycling stability with a high reversible capacity of 669 mA h g1, corresponding to 93% of capacity
retention aer 60 cycles, higher than that of the obtained
product tested between 0 and 2 V. The good cycling life is
attributable to the reversible intercalation and deintercalation of
Li to form LixMP2, conrmed by XAFS experimental results, in
the absence of changes in the local crystal structure of MoP2
together with the oxidation state of the Mo ion. MoP2 can be
doped with Si, such as Mo0.8Si0.2P2, to improve the capacity
retention and rate capability through the small electronegativity
between Si and P. The 1st charge–discharge curves presented that
the original MoP2 and Mo0.8Si0.2P2 reacted with Li at below
0.65 V, but the proles were different. During the 1st charge
process, the average working voltage of Mo0.8Si0.2P2 is slightly
lower than that of original MoP2. A reversible capacity of
730 mA h g1 of the Mo0.8Si0.2P2 electrode aer 100 cycles at
0.1C was obtained, which was attributed to the decomposition
and distribution of Si atoms in Mo0.8Si0.2P2 and reaction with
Li to improve the reversible capacity.150 The morphology and
crystallinity of metal phosphides play important roles in
determining electrochemical performance. Besides, electrode
materials with three-dimensional porous nanostructures
14922 | J. Mater. Chem. A, 2016, 4, 14915–14931
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manifest intriguing properties by taking advantage of both the
nanometer size effects and the hierarchical pores, which can
offer a sufficient contact interface between the electrolyte and
the active materials and enhance the transfer and permeation
of the electrolyte, as well as supplying resistant pathways for
the ions and electrons through the porous particles. By using
SiO2 spheres as the templates, Cao et al. recently reported the
synthesis of a three-dimensional (3D) porous MoP@C hybrid
by a sol–gel method followed by an annealing treatment
(Fig. 7a).63 Well-ordered 3D porous MoP@C hybrid assemblies
with a pore size of about 220 nm formed, and the porous wall
was composed of uniform nanoparticles assembled in a loose
way with some irregular mesopores (Fig. 7b). Aer cycling at
100 for 100 cycles, the discharge capacity of the 3D porous
MoP@C hybrid remained at 1028 mA h g1 (Fig. 7c). The
excellent electrochemical performance was attributable to the
predominance of the synergistic effect of the 3D porous
structure and the carbon coating for lithium storage. XRD,
XPS, and HRTEM analyses showed that the Li-storage mechanism was an intercalation mechanism.
2.2.7 Other phosphides. Apart from the above-mentioned
ones, several other nanostructured metal phosphides have also
been reported as electrodes in LIBs, including GaP nanoparticles,151 three-dimensional single-crystalline porous InP
anodes,152 InP thin lms,153 a porous InP anode,154 MnP4,55
NiCoP hollow microspheres,155 C@NiCoP peapods,156 Ni2SnP,157
a Ni–Sn–P mesocarbon microbead composite,158 a Sn–Fe–P
alloy,159 LixTiP4,160 LixTiP4 (x ¼ 2–11),132 VP2,161 VP,57 Zn3P2,60
ZnP2/C nanocomposites,162 ZnP2,163 and layered phosphoruslike GeP5.164
GeP5, with a layered architecture analogous to that of
graphite and black P, can bond with a graphitic layer associated
with high conductivity 10 000 times higher than that of black P
and similar to that of graphite, which is propitious for Li+
storage. Zhou's group fabricated GeP5/C nanocomposites
through a mechanical ball milling method with pure Ge powder
(a) Schematic illustration of the synthetic procedure of the 3D
porous MoP@C hybrid. (b) SEM and (c) cycling performance of the 3D
porous MoP@C hybrid at 100 mA g1. [Reprinted with permission from
ref. 63. Copyright 2016 Royal Society of Chemistry].
Fig. 7
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that might not be increased signicantly because of the limitations of sodium host sites.166 Recent results show that anode
materials for SIBs evaluated on the basis of alloy-type (Sb, Sn,
SnO2) and conversion-type (Fe2O3, FeS2) possessed high initial
capacities but poor cycling stability because of the huge volume
variation and slow Na+ diffusion. Elemental P has been widely
investigated as an anode material for SIBs because it has the
highest theoretical sodium-storage capacity (2596 mA h g1);
however, low electrical conductivity (1014 S cm1) and huge
volume expansion lead to poor cycling stability. Therefore, the
synthesis of a metal–P alloy compound has been conrmed as
an effective approach to address poor cycling performance in
SIBs.167–171
3.1
Fig. 8 (a and b) SEM and TEM images of the GeP5/C nanocomposites,
respectively, and (c) cycling performance of the GeP5/C nanocomposites at 200 mA g1. [Reprinted with permission from ref. 164.
Copyright 2016 Royal Society of Chemistry]. (d) Cycling performance
of the peapod-like C@NiCoP nanocomposite at 200 mA g1.
[Reprinted with permission from ref. 156. Copyright 2016 Wiley].
Sodium-storage mechanism
According to the literature, the Na-storage mechanism is similar
to that of lithium storage, e.g. intercalation and conversion
reaction mechanisms:91,172–176
(i) Intercalation mechanism:
MPn + xNa+ + xe 4 NaxMPn
(3)
(ii) Conversion reaction mechanism:
and amorphous red P.164 The as-prepared material consisted of
many nanosized sphere-like particles assembled into microstructured particles (Fig. 8a and b). Such hierarchical GeP5/C
nanocomposites delivered an unprecedented reversible capacity
of about 2300 mA h g1 over 40 cycles at a current density of
200 mA g1, combined with a high initial coulombic efficiency of
ca. 95% (Fig. 8c). The excellent electrochemical performance of
the hierarchical GeP5/C nanocomposites results from a synergistic effect between the GeP5 and C layers that supplied
a continuous conductive network as well as good structural exibility to accommodate the volume variation upon cycling.
Considering the advantages of a hollow structure, Liu et al.
prepared NiCoP hollow microspheres using a solvothermal
approach. The obtained material manifested an initial discharge
capacity of up to 980 mA h g1; even aer 100 cycles, the capacity
remained at 325 mAh g1.155 Wang’s group fabricated a peapodlike C@NiCoP nanocomposite that displayed excellent lithium
storage properties, including the specic capacity of 670 mA h g1
at 0.2 A g1 aer 350 cycles (Fig. 8d).156
3. Nanostructured metal phosphidebased materials for SIBs
SIBs are a potential alternative to LIBs because the abundance
of the sodium makes them economical. However, the radius of
Na+ is approximately 55% larger than that of Li+, resulting in
a variety of disadvantages, including poor cycling stability and
low rate capability, caused by the massive volume variation and
slow Na+ diffusion upon cycling, respectively.165 To solve those
problems, researchers have made substantial efforts to choose
and fabricate anode materials with high capacities and excellent
cycling performance. Recent ndings suggest that carbonaceous
materials have a reversible capacity of 250–300 mA h g1. But
This journal is © The Royal Society of Chemistry 2016
MPn + 3nNa+ + 3ne 4 nNa3P + M
(4)
Until now, because the study of metal phosphides in SIBs is
just emerging, further investigations on the Na storage mechanism of metal phosphides are needed.
3.2
Tin phosphide
Tin phosphide (Sn4P3) has been a promising anode material for
SIBs owing to its theoretical capacity of 1132 mA h g1 and high
electrical conductivity of 30.7 S cm1. Moreover, it is favorable
as an anode for a full battery with a high operating voltage
owing to its relatively low redox potential (approximately 0.3 V
vs. Na/Na+).93 Nevertheless, tin phosphide, similar to alloy
electrodes, undergoes massive volume variations during
cycling. Core–shell nanostructures of Sn4P3 could be an effective strategy to address the poor cycling stability that results
from a large volume change during the charge/discharge
processes. For instance, Qian et al.91 reported the synthesis of
core–shell Sn4P3/C nanocomposites by a high-energy mechanical milling method (Fig. 9a). The electrode made of Sn4P3/C
nanocomposites showed a high reversible capacity of around
500 mA h g1 with 86% capacity retention at 0.1 A g1 for up to
150 cycles, indicating excellent cyclability (Fig. 9b), which was
attributed to a synergistic Na-storage mechanism (Sn4P3 +
24Na+ + 24e / Na15Sn4 + 3Na3P). For example, the Sn nanoparticles, as electronic channels, activate the P component;
meanwhile, the P and Na3P work as the host matrix to prevent
the aggregation of Sn particles and accommodate the volume
expansion caused by Na+ insertion (Fig. 9c and d).
To improve the rate capability, Li et al. prepared a Sn4+xP3@amorphous Sn–P composite through a facile low-energy
ball-milling approach.93 The material displayed a stable capacity
of 465 mA h g1, corresponding to 92.6% of the 2nd capacity
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Fig. 9 (a and b) TEM images of Sn4P3/C nanocomposites, (b) cycling
performance of the Sn4P3/C nanocomposites at 100 mA g1, (c) ex situ
XRD patterns of the Sn4P3/C electrode at different charge and
discharge states, and (d) schematic illustration of the Na-storage
mechanism in a Sn4P3 electrode. [Reprinted with permission from ref.
91. 2014 Journal of American Chemical Society].
aer 100 cycles at 100 mA g1. In general, uoroethylene
carbonate (FEC) as an electrolyte additive is favourable to form
a stable SEI lm and then it can improve the cycling performance of anode materials. However, it will reduce the reversible
capacity because a NaF-like thick SEI lm with a higher resistance leads to increasing the polarization.177 Therefore, by
adding 5% FEC into the electrolyte, the Sn4+xP3@amorphous
Sn–P composite achieved an outstanding rate capability with
a stable capacity of 165 mA h g1 at 5000 mA g1. Yu's group
reported uniform yolk–shell Sn4P3@C nanospheres prepared by
a multi-step reaction procedure, shown in Fig. 10a.166 As shown
in the TEM images (Fig. 10b), the yolk–shell nanospheres were
produced and one large Sn4P3 nanoparticle as well as many
small Sn4P3 nanoparticles were completely incorporated into
every carbon nanocage. The existence of free space between the
carbon shell and the Sn4P3 nanoparticles, in addition to the
void around the Sn4P3 nanoparticles, helped sustain the
unabridged carbon shell, which was favorable to the growth of
a stable solid electrolyte interface (SEI) lm and accommodated
the volume expansion. Beneting from architectural merits, the
yolk–shell Sn4P3@C nanospheres possessed a high reversible
capacity of 790 mA h g1 and outstanding rate capability and
superior cycling stability, with a high capacity of 360 mA h g1
aer 400 cycles at 1500 mA g1 (Fig. 10c).
3.3
Iron phosphide
Because P and iron can be used as an inactive and conductive
matrix to accommodate the volume variation, iron phosphides
(FeP, FeP4) have been investigated as anode materials for SIBs.
Moreover, iron phosphides with high theoretical capacities of
924 and 1789 mA h g1 for FeP and FeP4, respectively, would be
attractive anode materials for SIBs, because of the low cost and
abundance of Fe.172,173,178
14924 | J. Mater. Chem. A, 2016, 4, 14915–14931
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(a) Schematic illustration of the fabrication of uniform yolk–
shell Sn4P3@C nanospheres, (b) TEM images of the yolk–shell
Sn4P3@C nanospheres, and (c) cycling performance of the yolk–shell
Sn4P3@C nanospheres at 1500 mA g1. [Reprinted with permission
from ref. 166. 2015 Royal Society of Chemistry].
Fig. 10
Chou's group synthesized FeP nanoparticles of 30–50 nm
through a ball milling method, using metal Fe and P as raw
materials.172 The obtained FeP nanoparticles displayed an
initial high reversible capacity of 764.7 mA h g1 at 50 mA g1,
and aer 60 cycles, they maintained a capacity of 321 mA h g1
corresponding to 69% retention of the 2nd capacity using
CMC-PAA as a binder and 5% FEC additive in the electrolyte.
Moreover, they also investigated the sodium storage mechanism of FeP using ex situ XRD and TEM, and the results showed
that when the electrode was discharged to 0.4 V, the presence of
Fe and disappearance of FeP during the 1st cycle imply the
reaction of P with Na to form Na3P and Fe as an inactive buffer
matrix to accommodate the volume expansion.
To enhance the cycling performance of FeP, compositing
with carbon could be an effective strategy. Han et al. reported
a nanostructured hierarchical CNT@FeP@C composite with
sodium-ion insertion and extraction at 0.4 and 1.45 V, respectively, in the 1st cycle. The CNT@FeP@C composite possessed
improved cycling life for SIBs with a reversible capacity of
415 mA h g1 at 100 mA g1 aer 100 cycles and a capacity
retention rate of 90% over 500 cycles even at 500 mA g1.179
3.4
Other metal phosphides
In addition to tin phosphides and iron phosphides, several
other metal phosphides are also electrochemically active in
SIBs. Recently, Chou's group prepared CoP nanoparticles of
10–20 nm via a facile ball-milled strategy using metal Co and P
as raw materials.174 The material exhibited an obvious voltage
platform at 0.05 V, corresponding to a conversion reaction of
CoP to form Na3P. In addition, the material presented a high
initial capacity of 770 mA h g1 and a reversible capacity of
315 mA h g1 aer 25 cycles at a current density of 100 mA g1,
corresponding to 70% of the 2nd capacity. However, efforts
should be devoted to improving the cycling stability. Kim et al.
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4. Nanostructured metal phosphidebased materials for supercapacitors
EDLCs, based on the charge storage mechanism of physical ion
accumulation at the interface between the electrolyte and
electrode in the presence of redox reactions, have low specic
capacitance. On the other hand, pseudocapacitors, with the
charge storage mechanism of fast and reversible faradaic redox
reactions, possess higher capacitance. It is because that the
faradaic redox reactions can occur not only on the surface of
electrodes but also in their core, particularly with nanomaterials.180 Transition metal oxides, metal hydroxides, and
conducting polymers are the most commonly used electrode
materials for pseudocapacitors, but they are kinetically unfavorable for the fast electron transport required for high power
density. Metal phosphides, which have metalloid properties
and high specic capacitances, have attracted extensive interest
as electrode materials for supercapacitors.181
4.1
Fig. 11 (a) Schematic illustration of the fabrication of the CuP2/C
hybrids, and (b) cycling performance of the CuP2/C hybrids at 200 mA
g1. [Reprinted with permission from ref. 175. 2016 Royal Society of
Chemistry]. (c and d) SEM and TEM images of the CPNWs, respectively,
and (e) cycling performance of the CPNWs at 1000 mA g1. [Reprinted
with permission from ref. 176. 2016 Wiley].
reported a CuP2/C hybrid with the P–O–C chemical bond
synthesized by a high energy ball milling route using metal
copper and red phosphorus as raw materials (Fig. 11a).175 The
CuP2 nanoparticles were well distributed in the carbon conductive framework through the P–O–C bonds, which shortened the
diffusion path and enhanced the electron/ion transfer around
active particles, giving them a high capacity associated with
outstanding cycling performance (approximately 450 mA h g1
over 100 cycles at 200 mA g1) and excellent rate capability
(Fig. 11b). The differential capacity plots (DCPs) show that in the
1st discharge process, there are two peaks at around 0.3 and
0.05 V, and two obvious peaks present at about 0.55 and 0.8 V in
the charging process, which are attributed to the successive
conversion reactions between sodium and phosphorus. An
additive-free Cu3P nanowire (CPNW) anode was reported by Fan
et al. prepared by in situ phosphidation of Cu(OH)2 NW, directly
grown on the copper foil (Fig. 11c and d).176 The CPNW anode
sodiated at 0.015–0.4 V and desodiated at around 0.87 V in the
1st cycle process. In addition, the CPNW anode delivered
outstanding cycling stability with approximately 0.12% loss in
capacity per cycle even at 1000 mA g1 during 260 cycles, and
high reversible capacity with 349 mA h g1 at a current density of
50 mA g1 (Fig. 11e). The excellent sodium storage performance
was ascribed to the sufficient void space, reduced transport
paths of electrons and ions, and good structural stability in the
presence of an additive.
This journal is © The Royal Society of Chemistry 2016
Nickel phosphides
Nickel phosphides have been considered as promising candidates for pseudocapacitors because of their high theoretical
capacitance, low metallic resistivity, natural abundance, and
environmentally friendly characteristics. In fact, several nickel
phosphide-based electrode materials have been reported for
supercapacitors: amorphous Ni2P nanoparticles,182 Ni2P nanoparticles,183,184 Ni5P4 nanoparticles,183 a porous Ni2P/GS nanocomposite,185 Ni2P/RGO nanoparticles,186 Au/Ni12P5 core/shell
nanocrystals,187 a Ni foam-supported Ni2P nanosheet (Ni2P NS/
NF),188 NiP@CoAl-LDH nanotube arrays,189 and a Ni2P/Co3V2O8
nanocomposite.190 Wang et al. reported amorphous Ni2P
nanoparticles with an average size of 50–100 nm, synthesized by
a simple solvothermal method.181 They observed that an electrode made of amorphous Ni2P nanoparticles manifested a high
specic capacitance of 1597 F g1 at 0.5 A g1 as well as good
cyclability, with 28.6% capacitance loss aer 1000 cycles. The
discharge–charge curves at different current densities exhibited
slight nonlinearities, suggesting faradic reactions of amorphous Ni2P. In addition, an asymmetric capacitor employing
amorphous Ni2P nanoparticles and activated carbon as positive
and negative electrodes, respectively, displayed a large energy
density of 29.2 W h kg1 at 400 W kg1 between 0 and 1.6 V due
to the disordered crystal structure of the amorphous Ni2P
nanoparticles. To further improve the conductivity of Ni2P, An
et al. fabricated Ni2P nanoparticles on RGO that displayed the
existence of faradaic processes, a high specic capacitance of
2266 F g1 and good cycling stability.186 They also reported
a porous Ni2P/GS nanocomposite. The non linear charge/
discharge curves investigated the pseudocapacitive behaviour of
Ni2P/GS nanocomposite in a potential range of 0–0.55 V. In
addition, the porous Ni2P/GS nanocomposite manifested
improvements in specic capacitance (1912 and 888 F g1 at 5
and 50 mA cm2, respectively) and cycling performance (77.1%
capacitance retention aer 2500 cycles), using GS as a conducive buffer matrix to facilitate fast electron transfer and
accommodate the huge volume change upon cycling.185
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Journal of Materials Chemistry A
Alternatively, a reasonable architecture including heterostructured core/shell nanostructures and three-dimensional
networks of nickel phosphide on Ni foam for nickel phosphides
is expected to deliver excellent electrochemical performance for
supercapacitors. A core/shell heterostructure of Au@Ni12P5 was
fabricated by Duan and co-worker through a facile phosphorization reaction with Au–Ni heterostructures (Fig. 12a).187 There
were two evident redox peaks in every CV curve in 0–0.55 V,
suggesting the pseudo-capacitive capacitances owing to faradaic
redox reactions. In addition, the material achieved a specic
capacitance of 806.1 F g1 at 0.2 A g1, higher than that of pure
Ni12P5 (517.4 F g1) (Fig. 12b), and excellent cycle stability
(specic capacitance retention of 91.1% aer 500 cycles)
(Fig. 12c). The excellent electrochemical performance was
attributed to enhanced electric conductivity and a reduced
charge diffusion path produced by a synergistic effect between
the Au and Ni12P5 in the core/shell heterostructure. Zhou et al.
prepared Ni2P nanosheets grown on Ni foam with a 3D interconnected network by the direct phosphorization of Ni(OH)2
nanosheets (denoted as Ni2P NS/NF) into the morphology shown
in Fig. 12d.188 The Ni2P NS/NF exhibited faradic reactions due to
non-linear charge–discharge proles in the potential range of
0.1 and 0.5 V and remarkable supercapacitor performance
(high specic capacitances of 3496 and 1109 F g1 at 2.5 and
83.3 A g1, respectively, associated with maintaining a large
Review
specic capacitance of 1437 F g1 aer 5000 cycles at 10 A g1).
The excellent electrochemical performance resulted from Ni2P
with improved conductivity to accelerate electron transfer,
abundant active sites for redox reactions supplied by Ni2+ and
Ps with rich valences in Ni2P, and a 3D interconnected network
of porous nanosheets benecial for ion diffusion (Fig. 12e and f).
Wang and co-workers prepared a core/shell nanotube-array
composite of NiP@CoAl-LDH NTAs using a template-assisted
electrodeposition process.189 The material presented the faradic
behaviour through non-linear discharge CVs in the voltage range
of 0–0.6 V. Moreover, NiP@CoAl-LDH NTAs possessed a high
specic capacity (0.67 C cm2 at 1 mA cm2) together with
excellent rate capability stemming from the aligned core–shell
nanotube architecture that provided a short ion diffusion path as
well as the faradaic characteristics of NiP and CoAl-LDH. Nickel
phosphide serves as an active material as well as a conducting
additive. For instance, Hu et al. synthesized a Ni2P/Co3V2O8
nanocomposite by a high ball milling method and found that Ni2P
functioned as a conductive additive for improving the conductivity
and capacitance of the Co3V2O8 electrode with good rate capability
and cycle stability.190 They found that an electrode made of the
Ni2P/Co3V2O8 nanocomposite exhibited an obvious couple of
redox peaks in every CV curves in the potential range of 0.2 and
0.6 V, indicating the faradaic reactions of Ni2+/Ni3+ and Co2+/Co4+
associated with anions OH. Additionally, the Ni2P/Co3V2O8
nanocomposite possessed a high capacitance of 1002.5 F g1 at
1 A g1 as well as enhanced cycle stability, with only 5% capacitance loss aer 3000 cycles. The outstanding electrochemical
performance of the Ni2P/Co3V2O8 nanocomposite electrode
materials was mainly attributable to: (i) their unique architecture,
with a high surface area and various channels for redox reactions;
(ii) synergistic effects between Ni2P and Co3V2O8 and the reasonable oxidized valence of Ni2P and Co3V2O8.
4.2
Fig. 12 (a) TEM image of the Au/Ni12P5 core/shell nanocrystals, and (b
and c) rate capability and cycling performance of the Au/Ni12P5 core/
shell nanocrystals at 1 A g1, respectively. [Reprinted with permission
from ref. 187. 2014 Nature Publishing Group]. (d) SEM images of Ni2P
NS/NF and (e and f) rate capability and cycling performance of the Ni2P
NS/NF at 10 A g1, respectively. [Reprinted with permission from ref.
188. 2015 Wiley].
14926 | J. Mater. Chem. A, 2016, 4, 14915–14931
Cobalt phosphide
Wang's group applied cobalt phosphide as an electrode material for supercapacitors because of its similarity to nickel
phosphide.191 They synthesized 1D Co2P nanorods and 3D Co2P
nanoowers through a facile thermal decomposition of TPP.
The material's unique 3D architecture offered a large contact
area for ions and prevented the aggregation of active particles.
The 3D Co2P nanoowers presented better pseudocapacitive
performance obtained from GCD measurements in the potential range of 0.2 and 0.5 V. The 3D Co2P nanoower electrode
exhibited a higher specic capacitance of 416 F g1 at 1 A g1
than the Co2P nanorods (284 F g1). In addition, the asymmetric
supercapacitor with Co2P nanoowers and graphene as the
anode and cathode, respectively, manifested a high energy
density of 8.8 W h kg1 at 6 kW kg1, accompanied by excellent
cycling performance (up to 97% retention of specic capacitance aer 6000 cycles) in the potential window of 1.5 V.
5.
Conclusions and outlook
In this review article, we have presented the signicant advances
in nanostructured metal phosphides for LIBs, SIBs, and
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Review
supercapacitors. The controlled and reasonable fabrication and
design of various metal phosphide-based nanoarchitectures and
nanocomposites are favourable to resolve the severe drawbacks
present in the electrochemical reactions, which will result in
improvements in the capacity, cycling, and rate capability of
metal–phosphide electrodes. The advances have already greatly
promoted the development of metal phosphides.
A serious challenge for metal–phosphide nanostructures is
their low initial coulombic efficiency, meaning that they suffer
a relatively large irreversible capacity loss at the 1st cycle. In
other words, not every charge inserted into the electrode can
extract during subsequent Li/Na deintercalation. This is an
important factor for anode materials and is essential for
commercial batteries. Generally, the low coulombic efficiency
for the 1st cycle is attributable to the decomposition of the
electrolyte and the formation of SEI lms. Compared to bulk
materials, nanostructured electrode materials with high surface
areas and pores exhibit larger irreversible capacity loss because
of the higher contact area between the electrode and the electrolyte and more surface reactions.
Since initial capacity loss formation depletes Li ions, one
effective strategy is to supply additional Li resources such
as pre-lithiation192 or combining the anode with Li-rich
Li2.6Co0.4N.193 Li et al. used Li powder to pre-lithiate a mesoporous Si electrode and found that the initial irreversible
capacity loss was reduced to smaller than 5%.192 The Co2P
electrode was pre-lithiated in contact with metallic Li in the
presence of LiPF6 and presented an open circuit voltage at
around 1.0 V, lower than that of the Co2P electrode without prelithiatement.194 Because Li-rich Li2.6Co0.4N can be used as the Li
source for SEI formation on the active anode materials, it can be
added to active anode materials as the Li source for SEI
formation on the latter to prevent the extraction of precious Li+
from the cathode material.193
Another feasible way is to coat a protective layer on the
nanostructured metal phosphides by atomic layer deposition
(ALD) or a sol–gel method, such as Al2O3,195 TiO2196 or TiN.197
Riley et al. found that an Al2O3 surface coating is favorable to
improve electrochemical performance of the MoO3 nanoparticle electrode with high capacity as well as large volume
variation for Li-ion batteries. The initial coulombic efficiency of
the MoO3 nanoparticle electrode with Al2O3 surface coating by
the ALD technique was enhanced, because the Al2O3 layer
effectively prevents some side reactions between the electrode
and electrolyte.195 In addition, the electrolyte additive such as
uoroethylene carbonate (FEC) was used to improve the electrochemical performance of anode materials including initial
coulombic efficiency through modifying the surface chemistry.198 However, more efforts should be devoted to investigating how to fundamentally improve the initial coulombic
efficiency of nanostructured electrode materials because of its
signicance to the real application of nanostructured materials
in LIBs and SIBs.
Another challenge for nanostructured metal–phosphides is
the low volume energy density because the density of a nanostructured powder is less than the same material with
micrometer-sized particles.199 It can be alleviated by designing
This journal is © The Royal Society of Chemistry 2016
Journal of Materials Chemistry A
hierarchical micro-/nanoarchitecture with a micrometer size,
nanosized primary building blocks and well-dened internal
void space. For example, VP nanoparticles consisting of aggregated around 10–20 nm sized nanocrystallites showed a stable
capacity of about 230 mA h g1 (1150 mA h cm3) over 250 cycles
at 100 mA g1, higher than that of graphite (840 mA h cm3).57
ZnP2/C nanocomposites were composed of particles with the size
of around 200–300 nm, consisting of about 10 nm-sized ZnP2
crystallites. The nanocomposites presented relatively large capacities of around 1250 mA h cm3 over 100 cycles at 100 mA g1.162
Although the volume energy density is lower than that of
graphene/Si nanoparticles (3000 mA h cm3),200 it is still higher
than that of graphite.
Because the surface area of nanostructured materials is
relatively high, the viscosity of the slurry is too high using the
common weight ratio of active materials, carbon black, and
binder to ensure a uniform and desirable thickness when
casting anodic lms in existing industrial processes. Consequently, nding a novel casting technique for nanostructured
materials is a promising and interesting subject that needs the
collaboration of excellent multi-disciplinary researchers. In
addition, the interphase of electrode materials and associated
research on binders will be an important subject. Moreover,
further work is required to develop cost-effective and large-scale
synthesis strategies to produce metal phosphides with tailored
nanoarchitectures and excellent performance for the commercialization of metal phosphides.
The study of metal phosphides in SIBs is just emerging and it
requires further design of reasonable material structures.
Additionally, further investigations on the Na storage mechanism and the kinetic transport at the electrode/electrolyte
interface are needed, taking advantage of modern analytical
techniques. Another exciting area is the fabrication and design
of exible metal phosphide-based electrodes for LIBs, SIBs, and
supercapacitors to accelerate the development of exible
electronics.
Despite the challenges ahead, metal phosphides with optimized nanostructures and composition could offer a strategy to
solve the problems with existing electrode materials for highperformance LIBs, SIBs, and supercapacitors. Additionally,
metal phosphides with rational architectures also arouse
interest in other application areas, such as hydrogen evolution
reactions, catalysis, and magnetic utilization.
Acknowledgements
This work was mainly supported by the Global Frontier R&D
Program (2013M3A6B1078875) of the Center for Hybrid Interface Materials (HIM) funded by the Ministry of Science, ICT &
Future Planning and a National Research Foundation.
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