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Synthesis, Structure, and Na-Ion Migration in Na4NiP2O7F2: A


Prospective High Voltage Positive Electrode Material for the Na-Ion
Battery
Dipan Kundu, Rajesh Tripathi, Guerman Popov, W. R. M. Makahnouk, and Linda F. Nazar*
Department of Chemistry, University of Waterloo, 200 University Avenue West, Waterloo, Ontario, Canada N2L3G1
S Supporting Information
*

ABSTRACT: In the recent hunt for novel Na-ion cathode


hosts, a variety of sodium analogues of classic Li-ion structures
have been thoroughly explored. However, Na-ion analogues
generally possess modied structures and dissimilar Na-ion
energetics compared to their Li-ion analogues due to the large
size of Na+ (102 pm) vs Li+ (76 pm), often resulting in
sluggish Na+ kinetics. Materials development targeted toward
new and dierent specic host structures possessing optimum
properties for Na-ion migration is crucial. Here, we report the
rst sodium metal uoropyrophosphate Na-ion host with a
three-dimensional frameworkNa4NiP2O7F2which is predicted to have a high voltage (5 V) based on its Ni2+/3+/4+ redox
couple and composition. Structure solution from single crystal diraction data combined with atomistic simulation computation
suggests the presence of low activation energy Na-ion migration pathways (<0.6 eV) in all three dimensions. The particularly low
barrier of 0.36 eV calculated for migration along the [010] direction is in full accord with temperature dependent ionic
conductivity measurements that yield an experimental value of 0.32 eV. Spacious Na-ion pathways endow the material with good
ionic conductivity as determined by ac impedance spectroscopy, and facile exchange of three Na+ ions for Li+ is observed at
slightly elevated temperatures. Furthermore, the polycrystalline material exhibits excellent thermal stability under ambient
atmosphere up to 600 C, crucial for the safe operation of a Na-ion battery.

INTRODUCTION
Na-ion batteries, once sidelined in favor of their higher energy
density Li-ion battery counterparts, are winning back overwhelming interest in recent years due to their cost advantages
and the relative abundance of sodium as compared to
lithium.15 In particular, for the eective utilization of
intermittent energy sources that requires large scale grid
stationary energy storage where gravimetric energy density is
not that much of a concern, Na-ion batteries (NIBs) are indeed
a preferred option.6,7
To keep up with the growing demand and wide-ranging
requirements of energy storage, a diverse range of transition
metal (TM) materials including oxides, phosphates, silicates,
borates, pyrophosphates, uorophosphates, and uorosulfates
have been explored as positive electrode materials for Li-ion
batteries.811 The knowledge gained in these studies is now
being implemented to design novel positive electrode materials
for Na-ion batteries. In this endeavor, open framework
polyanionic materials1215along with their sodium metal
oxide cousins that include examples such as O3-type layered
NaNi 1/3 Mn 1/3 Co 1/3 O 2 16 or highly promising P2-type
Na0.67Mn0.5Fe0.5O217are garnering more attention. Studies
have focused on utilizing TMs with multiple electron redox
chemistries, tuning their redox potential by incorporating highly
electronegative uorine in the structure to further boost the
voltage and hence energy density. These materials oer a higher
2015 American Chemical Society

redox potential compared to the equivalent transition metal


oxide owing to the inductive eect of the polyanions, whose
strong covalent framework induces electron density away from
the metal center, thus increasing the operating voltage.18,19
They also present good structural and thermal stability, a atter
voltage response upon Na (de)intercalation, and better capacity
retention endowed by their structural energetics and robust
frameworks. Importantly, they lack the signicant sensitivity to
ambient atmosphere (i.e., H2O and CO2) that characterizes
some layered Na-metal oxides.20,21
Investigation of these polyanion frameworks was motivated
by early studies conducted by Hong and Goodenough et al.,
who rst showed that 3D open framework NASICON (sodium
superionic conductors) compounds possess high Na+ ion
mobility.22 They can be used as solid state electrolytes, or as
electrode materials if they encompass a transition metal (TM)
in their structure. Although the heavier framework of typical
NASICON compounds lowers their gravimetric energy density,
this can be oset by incorporating multivalent TMs that are
capable of contributing to multiple electron transfer on Na+/Li+
de(intercalation). Vanadium and nickel are two prime TM
candidates. In this context, NASICON type Na3V2(PO4)3 has
Received: November 3, 2014
Revised: January 2, 2015
Published: January 5, 2015
885

DOI: 10.1021/cm504058k
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Chemistry of Materials
shown much promise to date.23,24 Another NASICON type
material, Na3Ti2(PO4)3, is a potential anode material.25
Incorporating F into the polyanionic structure further gives
rise to a new class of structural hosts and compositions. A
variety of favorable candidates have emerged, including
NaVPO 4 F, 26 Na 3 V 2 (PO 4 ) 2 F 3 , 27 Na 1.5 VOPO 4 F 0.5 , 28 and
Na2FePO4F.29 The presence of electronegative uorine ensures
a relatively high average voltage for the V3+/V4+ redox couple in
Na-ion cells. Reversible de(intercalation) of Na+/Li+ into
layered Na2FePO4F was rst demonstrated by Ellis et al.29 A
robust framework structure along with a very small volume
change (3.7%) upon Na+ de(insertion) results in good
electrochemical reversibility.30,31 Later, Tripathi et al. used
atomistic simulation to predict high Na+ mobility (0.29 eV)
along the [100] direction in the 2D network in the ac plane of
Pnma Na2FePO4F.32 Very recently, Park et al. demonstrated
excellent electrochemical cyclability for Na1.5VPO4.8F0.7,33
which utilizes the V3.8+/V5+ redox range at an average voltage
of 3.8 V against Na+/Na. They ascribed the outstanding cycling
performance of this compound to its structural rigidity and very
low volume change (2.9%) upon Na+ de(intercalation), along
with rapid Na+ diusion (activation barrier: 0.30 eV) in the
two-dimensional ab plane of the tetragonal P42/mnm structure.
In this work, these concepts have been integrated to
synthesize a novel prospective high voltage NIB positive
electrode material, Na4NiP2O7F2 which possesses a 3D open
framework structure and low energy pathways for Na-ion
migration in all three dimensions. To gain a clear understanding
of Na+ mobility, interatomic potential based atomistic
simulation methods were applied. They suggest a very high
3D Na+ ion mobility in the structure with a lowest energy
barrier of 0.36 eV. This is similar to the values predicted for
Na2FePO4F and Na1.5VPO4.8F0.7 (see above), although these
materials are restricted to two dimensions in ion mobility. The
computational prediction is validated by temperature dependent ionic conductivity measurements that provide a low
activation energy of 0.32 eV/atom for Na+ ion migration. By
comparison to olivine LiNiPO434where high voltage of 5.2 V
vs Li is predictedand considering the electron withdrawing
eect of P2O7 and uorine on the NiO bond,35 a redox
voltage of 5 V vs Na is anticipated for Na4NiP2O7F2 and
conrmed by preliminary electrochemical studies. This would
make it suitable for high energy density batteries preferably
combined with a solid state electrolyte.

Single Crystal and Powder X-ray Diraction. A needle shaped


0.170 0.060 0.040 mm pale green crystal grown in a Na2PO3F ux
was mounted on a nylon ber with peruoropolyether oil. Data were
collected at 295 K using a Bruker APEX CCD (charge-coupled device)
platform diractometer with monochromated Mo K ( = 0.7107 )
radiation. Data collection and reduction were carried out with the
Bruker AXS SAINT and SMART5.0 programs, respectively. The nal
unit-cell parameters were determined from 4,064 reections. A total of
989 independent reections were used for the solution by least-squares
structural renement (F2) using the Bruker SHELXTL package.
Powder X-ray diraction was performed on a Bruker D8-Advance
powder diractometer equipped with a Vantec-1 detector, using Cu
K radiation ( = 1.5405 ) in the range from 10 to 80 (2) at a
step size of 0.025 using BraggBrentano geometry. X-ray data
renement was carried out by conventional Rietveld renement
method using the Bruker-AXS TOPAS 4.2 software (Bruker-AXS,
2008). The background, scale factor, zero point, lattice parameters,
atomic positions, and coecients for the peak shape function were
iteratively rened until convergence was achieved.
Scanning Electron Microscopy and Thermal Analysis.
Powder samples were gold coated and examined in a LEO 1530
eld emission scanning electron microscope (FESEM) equipped with
an energy dispersive X-ray spectroscopy (EDX) attachment. Images
were recorded at 15 kV with a backscattered electron detector.
Thermogravimetric analysis (TGA) was performed using a TA
Instruments SDT Q600 in air at a heating rate of 5 C min1.
Ionic Conductivity Measurements. The Na4NiP2O7F2 powder
was pressed into a pellet of 2.16 mm in thickness and 11.38 mm in
diameter using an uniaxial press (Carver) under a pressure of 4 ton/
cm2. The pellet was then sintered at 400 C under an argon ow for 12
h. Silver conductive paste was applied to both sides of the pellet before
mounting it in a symmetric Swagelok-type cell, sandwiched between
two stainless steel rods. The assembled cell was then heated at 100 C
for 1 day and tightened to seal it before cooling it down. The bulk
resistance of the pellet was measured using two probe ac impedance
spectroscopy (VMP3, Biologic) in a frequency range of 200 kHz to
100 mHz using a potentiostatic signal perturbation of 300 mV.
Impedance spectroscopy data were recorded in a temperature range of
50 to 200 C, in a temperature controlled oven. Bulk ionic
conductivities at dierent temperatures were obtained by tting the
Nyquist plot using EC-lab Z-t analysis software. The activation
energy for Na-ion diusion was obtained by linear tting of the ionic
conductivity values at dierent temperatures by applying the Arrhenius
equation, modied to include a temperature dependent preexponential: T = 0 exp(Ea/kbT), where is the temperature
dependent ionic conductivity, 0 is the ionic conductivity at absolute
zero temperature, Ea is the activation energy of ion migration, and kb
and T have their usual meanings.
Electrochemistry. Electrochemical properties of the material were
evaluated in Swagelok type cells against a Na metal anode using 0.5 M
NaTFSI in P13-TFSI ((N-methyl-N-propylpyrrolidinium bis(triuoromethanesulfonyl) imide) as the electrolyte. A Teon treated
carbon paper (Toray, TGP-H-030, Fuel Cell Store) was used as the
cathode current collector instead of aluminum to avoid electrochemical corrosion. For electrode fabrication, Na4NiP2O7F2 microcrystalline powder was mixed with Super P by ball milling at 400 rpm
for 5 h. The obtained mixture was mixed with PVDF as a binder in
NMP (N-methyl-2-pyrrolidone) to obtain a slurry which was doctor
bladed onto the Toray carbon paper. The weight ratio of active
material:carbon:binder in the cathode was 70:20:10. Electrodes of 1
cm2 geometric area were punched and dried at 120 C in a vacuum
oven for 12 h prior to assembly in the cell.
Computational Modeling. Atomistic scale simulations used in
the current study employ the Born model, where the ionic interactions
are divided into long-range Coulombic forces and short-range forces
representing electronelectron repulsion and van der Waals
interactions.36 Short range interactions were modeled using a two
body Buckingham potential. To account for the angle dependence of
the OPO bond in PO43, a three body potential term was used.
The well-known shell model used to account for the polarizability of

EXPERIMENTAL SECTION

Single Crystal Synthesis. Single crystals of the target compound


Na4NiP2O7F2 were recovered from a ux reaction of NiO and
Na2PO3F. A similar method was used to produce single crystals of
Na2FePO4F earlier by our group.29 In a typical procedure, NiO was
mixed and ground with an excess of Na2PO3F, poured into a gold
crucible, and placed in a silica glass tube. The reaction mixture was
held at 675 C for 8 h under ambient atmosphere and was cooled
slowly to 400 C over a period of 10 h followed by a rapid cooling to
room temperature. The ux was dissolved in water by sonication, and
crystallites were collected by ltration. Pale green crystallites of
Na4NiP2O7F2 were obtained mixed with a second phase, identied as
Na2NiPO4F.
Preparation of Single Phase Polycrystalline Powder. For the
synthesis of polycrystalline Na4NiP2O7F2, Na2PO3F (vacuum-dried at
90 C over a period of 1 week) was mixed with as-synthesized NiO
nanopowder in a 2.5:1 molar ratio. The mixture was thoroughly
ground and pelletized and then heat treated under an argon ow at
575 C for 4 h. As-obtained green pellets were ground and washed
thoroughly with deionized water to obtain phase-pure Na4NiP2O7F2.
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the charged defects, lattice relaxation around defects, and migrating
ions was calculated by implementation of the Mott-Littleton scheme
incorporated in the GULP code.37 These methods have been
described in detail elsewhere and have been extensively used for
predicting defects and ion migration in a range of oxides, phosphates,
silicates, and sulfates.3841 In the current work, all the interatomic
potentials except NiO and NiF were obtained from our earlier
work on Na2FePO4F.32 Interatomic potentials for NiO and NiF
were obtained by recursively changing the FeO and FeF potentials
used in Na2FePO4F to match the lattice parameters obtained from the
diraction pattern of Na4NiP2O7F2 until excellent agreement
(<0.05%) was obtained.

Table 1. (a) Atomic Positions and (b) Bond Lengths for


Na4NiP2O7F2 Obtained from Single Crystal Diraction Data
(a)

RESULTS AND DISCUSSION


Crystal Structure and Atomistic Modeling of Na+ ion
Mobility. The structure of the new materialNa4NiP2O7F2
determined from single crystal diraction is shown in Figure
1a,b. It crystallizes in the orthorhombic Imma space group with

atom

Ni
P
F(l)
F(2)
O(1)
O(2)
O(3)
Na(l)
Na(2)

0.5
0.40278(3)
0.5
0.25
0.40011(7)
0.6644(1)
0.5
0.23351(7)
0.11138(6)

0
0.25
0.25
0.25
0.0717(1)
0.25
0.25
0
0.25

0.5
0.78019(6)
0.3842(2)
0.25
0.6714(1)
0.9229(2)
0.8774(2)
0
0.2982(1)

(b)
Ni1F1
Ni1Ol
P1O2
P1O1
P1O3
Na1F2

1.9871(7)
2.065(1)
1.497(1)
1.521(1)
1.638(1)
2.6411(2)

Na2F1
Na2F2
Na1O1
Na1O2
Na2O1
Na2O2

2.187(1)
2.1064(8)
2.455(1)
2.414(1)
2.489(1)
2.309(2)

O3F2 share four O1F1 edges with the NiO4F2 unit, in pairs,
above and below the equatorial plane of the NiO4F2octahedron. Each pair of Na(2)O3F2 shares an F1 apex
between them and two O1 apexes with a P2O7 unit. Finally,
each [Ni2P4O14F4] layer shares the F2 apexes of the
Na(2)O3F2 polyhedra with the next layer along c to form the
3D [Na2NiP2O7F2] framework. This generates rows of ve
sided [010] tunnels undulating along c and columns of four
sided [001] tunnels running along a. The Na1 cations which
occupy these tunnels are shown to be highly mobile by
atomistic simulations (next section). They exhibit a distorted
octahedral geometry surrounded by four oxygen and two
uorine atoms, with NaO distances of 2.41 (Na1O1),
2.45 (Na1O2), and 2.64 (Na1F2).
A direct comparison of the structural parameters calculated
using atomistic simulation methods with those obtained from
X-ray diraction shows a minimal 0.05% dierence (Table S1,
Supporting Information) indicating that the potential parameters used in this study can be very reliably applied to calculate
defect formation and Na-ion migration energy barriers. The
data shown below indicate rapid Na ionic diusion is expected
in all three dimensions with a low activation barrier. To
calculate Na-ion migration in this structure, all NaNa
distances below 5 were identied. Five unique NaNa
distances (marked L1 to L5) leading to the probable Na
migration paths in the structure are shown in Figure 2a.
Lengths and corresponding activation energies associated with
these hops are summarized in Table 2a. The combination of
such hops leads to the overall picture of long-range Na ion
migration energies presented in Table 2b. Among the three
possible Na migration pathways identied (Figure 2), the path
along [010] provides the most facile channels for Na ion
migration with an activation barrier of only 0.36 eV. This is
comparable to that calculated for layered Na2FePO4F (0.3 eV).
The Na+ ions along the [001] path are relatively further apart
from each other and move in a curved trajectory through a
narrow window formed by NaO3F2 polyhedra. This results in a
higher but still very accessible activation barrier of 0.57 eV for
Na ion migration, comparable to that calculated for LiFePO4 of
0.55 eV.42 A third path along [100] is created by combination
of L1, L2, and L5 hops (Figure 2c) with an energy barrier of

Figure 1. Crystal structure of Na4NiP2O7F2 viewed along the (a)


[010] and (b) [001] direction. (c) Connectivity in the structural
building block fragment with arrows indicating dierent atomic sites.
The dotted shapes highlight the position of this structural motif in the
overall structure.

lattice parameters a = 14.9529(9), b = 7.0856(4), and c =


7.7733(5) . Polyhedral clusters consisting of a central NiO4F2octahedron edge share with four Na(2)O3F2 moities and corner
share with two diphosphate groups (P2O7), to form the basic
structural unit (Figure 1c). The clusters are connected by the
F(1) vertices of the NiO4F2 octahedron along the [010]
direction to form an open 3D framework structure that houses
the Na(1) ions in the cavities. Alternatively, the overall crystal
framework can be thought of as a pseudo-multislab structure
with mobile Na(1) ions forming Na+ layers in the bc plane in
the structure (Figure 1a,b). The atomic positions and selected
bond lengths are summarized in Table 1 and the crystallographic density is 2.92 g cm3.
The framework can also be described by the stacking of
identical [NiO4F2] layers along the a axis, parallel to (010). In
the undulating [NiO4F2] chains, the NiO4F2 octahedra are
linked to two P2O7 groups in the equatorial plane of the
octahedron. Each P2O7 unit, consisting of two PO4-tetrahedron
units bridged through O(3), shares two O(1) apexes with the
NiO4F2 octahedron. Four distorted trigonal-bipyramidal Na(2)887

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Figure 2. (a) Visualization of all unique NaNa distances (marked L1L5) and actual migration trajectory (as calculated) along L1L5 hops
represented by colored spheres. Na ion migration pathways in Na4NiP2O7F2 viewed along (b) (010), (c) (001), and (d) (100) directions. Color
scheme: L1, olive; L2, wine; L3, light green; L4, dark green; L5, golden.

that the Na ion diusion in Na4NiP2O7F2 is not impeded owing


to bottlenecks.
Synthesis of Polycrystalline Powder and Ionic
Conductivity Measurements. Single crystal synthesis of
the title compound yielded needle shaped Na4NiP2O7F2
crystals as described in the Experimental Section, along with
Na2NiPO4F as the major phase. The preparation of phase pure
polycrystalline material is vital to the exploration of physical
and electrochemical properties relevant to Na-ion battery
applications. Attempts to synthesize this material starting from
commercial microcrystalline NiO and Na2PO3F at a temperature of 550600 C resulted in incomplete reaction, where the
products consisted of Na4NiP2O7F2 and unreacted NiO.
Prolonging the reaction time or attempting the synthesis at
higher temperature (>600 C) resulted in Na2NiPO4F as a
secondary phase. This illustrates the thermodynamic metastability of Na4NiP2O7F2 and its tendency to convert to
Na2NiPO4F at elevated temperature. Apart from reaction
temperature and time, the moisture content of the precursors
was also found to have an inuence on the product
composition. In order to achieve a complete reaction of a
pure phase material in a shorter reaction time, NiO
nanopowder was synthesized and employed as the precursor
(Supporting Information Figure S1).
Successful synthesis of Na4NiP2O7F2 was conrmed by
powder X-ray diraction and Rietveld renement (Figure 3a).
The details of the data collection parameters, rened lattice
parameters, goodness of t, and comparison with the single

Table 2. (a) Hops (as described in Figure 2a) for Na-Ion


Migration: Lengths and Corresponding Activation Energy
Barrier and (b) Activation Energy Barrier for Long Range
Na-Ion Migration in Na4NiP2O7F2
(a)
hop

length ()

activation energy (eV)

LI
L2
L3
L4
L5

3.28
3.54
3.51
3.89
3.24

0.53
0.61
0.36
0.57
0.52
(b)

direction

combination of hops

activation energy (eV)

[100]
[010]
[001]

L1L2L5
L3
L4

0.61
0.36
0.57

0.62 eV for long-range Na ion diusion. These results suggest a


high Na ion mobility within the b axis channels and good
mobility within the a and c axis channels leading to 3D Naionic diusion, which is expected to be benecial for high
power energy storage. The existence of low energy ionic
diusion pathways along three dimensions further signies that
antisite defects will be of lesser signicance for Na ion
migration in Na4NiP2O7F2 than they are for 1D diusion
materials like olivine, LiNiPO4. These results also demonstrate
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Figure 3. Rietveld renement of the powder X-ray diraction pattern of the synthesized polycrystalline Na4NiP2O7F2. Data points (red circles);
calculated prole (black line); dierence prole (blue line); Bragg positions (magenta lines). (b) A typical SEM image showing the morphology of
the polycrystalline Na4NiP2O7F2.

crystal data are provided in the Supporting Information. The


typical crystallite morphology and dimensions are shown in the
representative SEM image (Figure 3b). The crystals are small,
rod-like, and faceted, with lateral dimensions ranging from 2 to
5 m. Thermogravimetric analysis was used to assess the
thermal stability of the Na4NiP2O7F2 powder sample under
ambient atmosphere (air) in a temperature window between 20
and 800 C (Supporting Information Figure S2). The material
is thermally stable below 600 C, above which a phase
transition takes place indicated by the small peak in the DTA
prole (blue curve). The DTA peak is most likely associated
with conversion of the Na4NiP2O7F2 to Na2NiPO4F, as
observed during the (unwanted) production of the former at
longer reaction times or at higher synthesis temperatures. The
observed thermal stability in air suggests a good oxidative
stability for the framework structure, which is crucial for the
stability of a high voltage cathode under overcharge. In large
part, this owes to the fact that pyrophosphates are much more
stable to oxygen loss compared to phosphates.
The activation energy for Na ion migration was experimentally determined from linear tting of the Arrhenius plot of
the bulk conductivity of a pressed powder pellet sample.
Complex plane impedance plots of the polycrystalline powder
sample were obtained at dierent temperatures ranging from 50
to 200 C. The same equivalent circuit model (Supporting
Information Figure S3) was used to t the impedance plots for
the entire temperature range, consisting of two conventional
charge transfer (Rct)/constant phase element (CPE) in series.
These two R/C components correspond to the bulk ionic
conduction and that arising from grain boundary contributions,
which are distinguished based on their frequency dependence.43
Bulk and grain boundary conductivities, denoted by b and
gb, respectively (summarized in Supporting Information), are
obtained from tting the impedance data (Supporting
Information Figure S4). As shown in Figure 4b (inset), the
bulk conductivity value increases with rise in temperature,
which is typical of a fast ion conductor. A bulk conductivity
value of 2.03 108 S cm1 is extrapolated at 298 K based on
the parameters obtained from the linear tting of the Arrhenius
plot. This is comparable to the ion conductivity of undoped
polyanion materials such as 107 S cm1 for NASICON type
Na3V2(PO4)344 and 108 S cm1 for LiZr2(PO4)3,45 or 107
S cm1 for Na3TiP3O9N,46 a recently explored Na ion cathode
compound. The bulk conductivity increases 1000-fold at 200
C. A very low activation energy of 0.32 eV/atom for bulk Na
ion migration is also obtained (Figure 4b), in very close

Figure 4. Arrhenius plot of ionic conductivity (using a temperaturedependent pre-exponential factor). Black dots represent the data
points. The activation energy for Na+ ion migration is calculated from
the slope of the tted line (red). The variation of bulk ionic
conductivity vs temperature obtained from the impedance data tting
is shown in the inset.

agreement with the energy of the least hindered Na ion


migration along the [010] crystallographic direction, obtained
by computational modeling. This provides direct experimental
evidence of a low barrier to Na ion mobility, facilitated by the
3D open framework structure. The electrical conductivity value
of Na4NiP2O7F2 is expected to be comparable to the Ni2+ based
polyanionic compound like LiNiPO4 (>109 S cm1).47
Therefore, the conductivity obtained from the ac impedance
spectroscopy measurement, which exceeds that of electrical
conductivity, is expected to be predominantly ionic in nature.
This ionic conductivity is quite substantial and can potentially
be enhanced by introducing Na ion vacancies or by substitution
at the transition metal site.
Na+/Li+-Ion Exchange of Na4NiP2O7F2. Ion exchange is
an eective way of preparing novel metastable phases that are
otherwise inaccessible via traditional synthetic routes. Moreover, successful ion exchange clearly demonstrates the presence
of mobile and replaceable ions in the structure. In this work,
Na+/Li+ ion exchange was carried out in 1 M LiBr/acetonitrile
at 70 C for 2436 h. This leads to the expulsion of about 3
Na+ for Li+ per formula unit as revealed by energy dispersive Xray spectroscopy in the SEM (Supporting Information Figures
S5 and S6). The exchange of more than two Na+ ions directly
indicates the ability to exchange both Na1 and Na2 sodium in
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Figure 5. (a) Cyclic voltammogram of 0.5 M NaTFSI in P13-TFSI with Toray paper as the working electrode at a scan rate of 1 mV/S against
metallic sodium as the counter electrode. (b) Galvanostatic chargedischarge prole of Na4NiP2O7F2 cathode against Na anode at a current density
of 5 mA/g with 0.5 M NaTFSI in P13-TFSI as the electrolyte.

phosphate polyanionic compound. Prior to our work, no Ni


pyrophosphate systems have been reported nor computationally studied. In a uoro-pyrophosphate material, the strong
inductive eect exerted by the PO moieties and uorine
atoms would aect the Ni2+/Ni4+ redox energy,35 thus
predictably increasing the average redox voltage to >5 V vs
Na. Following the initial charge region between 4.7 and 5.2 V,
the prole exhibits a steady slope which most likely represents
predominantly electrolyte decomposition catalyzed by the
cathode. Furthermore, an insignicant amount of Na+ reinserts
back in the subsequent discharge. Clearly, even for an
oxidatively stable ionic liquid electrolyte, oxidation at the
cathode surface is quite probable at high voltages50,51 and likely
aggravated by interfacial parasitic reactions at the conductive
carbon interface.52
The electrochemical performance of this material is most
likely also limited by kinetic factors, such as poor electrical
conductivity and large particle dimensions which can be
countered by synthesizing nanocrystals and/or better conductive composite formation. However, realizing the full
potential of this compound would require electrochemistry in
conjunction with electrochemically and thermally stable solid
ionic conductors in an all-solid-state battery, thus eliminating
any possibilities of cathode catalyzed liquid electrolyte
decompositions.

Na4NiP2O7F2, pointing to their mobile nature in agreement


with the computational studies. The morphology of the ion
exchanged sample remained similar to that of the pristine Na
phase, proving the physically nondestructive nature of the
process. Structural investigation of the lithiated phase was
performed using XRD and time-of-ight neutron diraction
(ND). Details are presented in the Supporting Information. In
both cases, the reections were indexed to a noncentrosymmetric space group Pna21. Although structure determination of
the lithiated phase was not possible, the change in the space
group together with the EDX data clearly indicates ion
exchange under mild conditions, conrming the presence of
mobile Na+ ions with a low activation barrier to migration. This
is a prerequisite for both Na-ion battery cathode and solid
electrolyte applications.
Electrochemical Performance of Na4NiP2O7F2. This
material is expected to undergo Ni2+/Ni4+ redox at high
potential based on its polyanionic framework as explained
above. Its electrochemical performance was therefore evaluated
against a Na metal anode using 0.5 M NaTFSI in P13-TFSI
((N-methyl-N-propylpyrrolidinium bis(triuoromethanesulfonyl) imide) as the electrolyte. The
ionic liquid (IL) based electrolyte was chosen because ILs are
theoretically predicted48 to have much higher anodic stability
(>6 V against Li+/Li) by comparison to organic carbonate
based electrolytes or even sulfones. A Teon treated carbon
paper was used as the cathode current collector to prevent
electrochemical corrosion by TFSI based salts or ionic liquids
(see details in the Experimental Section).49 Information on
overall electrolyte stability in the absence of a cathode was
deduced from cyclic voltammetry measurement in a potential
window of 3 and 5.5 V, as shown in Figure 5a. A high anodic
stability is observed without any major decomposition current
both in the oxidation and in the reduction sweep. The same
feature is reproducible over consecutive CV scans, conrming
long-term electrochemical stability of the chosen electrolyte.
Galvanostatic chargedischarge protocols were used to
measure electrochemical sodium (de)intercalation from
Na4NiP2O7F2 as shown in Figure 5b. On the basis of an
expected 2 e redox for Ni2+/Ni4+ a theoretical capacity of 150
mA h g1 is expected. In the rst electrochemical charge,
however, only about 0.35 Na+ is extracted at an average voltage
of 55.2 V. Such a high average voltage is anticipated from
the theoretically calculated voltage of LiNiPO4, namely, 5.2 V
vs lithium34 (hence 4.9 V vs sodium, accounting for a 0.3 V
dierence in the redox potential between Na+/Na and Li+/Li).
This is the only predicted value for Ni2+/Ni3+ couple in a

CONCLUSIONS
The surge of NIB research has been mainly dominated by
exploration of structural chemistries that are analogous to the
well-established Li-ion systems. Although this approach is
undoubtedly advantageous to speed up materials development,
targeted discovery of novel structural chemistries is crucial to
tap into the prospects of highly demanding applications such as
grid storage or electried transportation. In this regard, the
novel open framework Na4NiP2O7F2 with its low energy Naion conduction pathways, good sodium ionic conductivities,
and impressive thermal stability is particularly attractive as a
prospective rechargeable NIB cathode. Although investigations
with ionic liquid based electrolytes are preliminary, we note that
electrochemical activity is observed at the highest reported
operating voltage ever, inviting further exploration of this
compound in an all solid state NIB. This work is expected to
provide the impetus for the discovery of a family of new sodium
metal uoropyrophosphate compounds as novel high voltage
cathode host materials for NIBs.
890

DOI: 10.1021/cm504058k
Chem. Mater. 2015, 27, 885891

Article

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ASSOCIATED CONTENT

S Supporting Information
*

Detailed single crystal data collection, powder diraction


renement results, thermogravimetric analysis, ac impedance
spectroscopy, SEM-EDX, XRD, and neutron diraction data of
the Li-exchanged sample. This material is available free of
charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
We gratefully acknowledge NSERC for generous funding
through its Discovery Grant and Canada Research Chair
programs. Dr. Jalil Assoud in the UWaterloo Crystallographic
Laboratories is warmly acknowledged for assistance with
collection of the single crystal data and structure solution.
The neutron diraction data was collected at the Oak Ridge
National Laboratorys Spallation Neutron Source; research
sponsored by the Scientic User Facilities Division, Oce of
Basic Energy Sciences, U.S. Department of Energy.

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DOI: 10.1021/cm504058k
Chem. Mater. 2015, 27, 885891