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Cell degradation of a Na–NiCl2 (ZEBRA) battery

Article · November 2013

DOI: 10.1039/C3TA13644B

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Cell degradation of a Na–NiCl2 (ZEBRA) battery

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Cite this: J. Mater. Chem. A, 2013, 1,

14935
Received 11th September 2013
Accepted 20th September 2013
DOI: 10.1039/c3ta13644b
www.rsc.org/MaterialsA
Guosheng Li,* Xiaochuan Lu, Jin Y. Kim,* John P. Lemmon and Vincent L. Sprenkle
In this work, the parameters influencing the degradation of a Na–NiCl2 (ZEBRA) battery were investigated.
Planar Na–NiCl2 cells using the b00 -alumina solid electrolyte (BASE) were tested with different C-rates,
Ni/NaCl ratios, and capacity windows, in order to identify the key parameters for the degradation of the
Na–NiCl2 battery. The morphology of NaCl and Ni particles was extensively investigated after 60 cycles
under various test conditions using a scanning electron microscope. A strong correlation between the
particle size (NaCl and Ni) and battery degradation was observed in this work. Even though the growth
of both Ni and NaCl can influence the cell degradation, our results indicate that the growth of NaCl is a
dominant factor in cell degradation. The use of excess Ni seems to play a role in tolerating the negative
effects of particle growth on degradation since the available active surface area of Ni particles can still
be sufficient even after particle growth. For NaCl, a large cycling window was the most significant
factor, of which effects were amplified with decrease in the Ni/NaCl ratio.

Introduction electrically conducting Ni particles. Therefore, the formation of

Sodium-b00 alumina batteries such as ZEBRA (by the Zeolite
Battery Research Africa Project) and Na–S batteries share
common features, such as molten sodium on the anode and the
b00 -alumina solid electrolyte (BASE).1–3 Unlike a Na–S battery,
NaAlCl4 is typically used as the secondary liquid electrolyte
(catholyte) in a ZEBRA battery to facilitate the Na+ ion move-
ment in the cathode, providing critical advantages over a Na–S
battery including lower operating temperatures and safe cell-
failure modes. A ZEBRA battery also has benets such as higher
voltage and safe assembly in the discharged state without using
metallic sodium in the anode.4
Among ZEBRA-type batteries, sodium–nickel chloride
(Na–NiCl2) has been widely investigated as a promising energy
storage device for renewable energy applications as well as
smart grid applications.4–6 A Na–NiCl2 battery is typically oper-
ated in the temperature range between 250 and 300  C in order
to achieve adequate battery performance by improving the ionic
conductivity of the solid electrolyte and secondary liquid
electrolyte.1,5 The electrochemical reaction of a Na–NiCl2 battery
during discharging is described as follows:5
2Na + NiCl2 4 2NaCl + Ni, E0 ¼ 2.58 V (1)
The key feature of a Na–NiCl2 battery is the formation of a
poorly conductive NiCl2 layer on the surfaces of Ni particles. The
active surface area of Ni particles, which is possibly related to
particle size and Ni content, is crucial for battery performance
because the Ni redox reaction can only occur on the surface of
Pacic Northwest National Laboratory, Richland, WA 99352, USA. E-mail: Jin.Kim@
pnnl.gov; Guosheng.li@pnnl.gov; Fax: +1 509 375 2186; Tel: +1 509 375 2225
a thick, dense NiCl2 layer oen limits the charging. Prakash
et al. investigated the electrochemical performance of a
Ni–NiCl2 electrode with the NaAlCl4 catholyte at various
temperatures, as well as the solubility of NiCl2 in NaAlCl4 in the
temperature range between 200 and 400  C.7 Recently, we
reported the effects of operating temperature on the growth of
Ni and NaCl particles and the degradation of cell performance
in the range between 175 and 280  C.8 Even though the particle
growth has been considered one of the major mechanisms of
cell degradation, no detailed information on the parameters
causing particle growth has been reported. In this work, the
effects of Ni content and battery operating conditions such as
C-rate, voltage limit, and cycling capacity window on the
particle growth of Ni and NaCl were investigated in conjunction
with performance degradation. The knowledge on cell degra-
dation obtained in this work will provide helpful insights for
improving the cycle life of Na–NiCl2 batteries.
Experimental
Cathode materials and electrolyte preparation
Cathode materials used in this work consist of Ni (Novamet,
Type 255, 1–2 mm particle size), NaCl (Alfa Aesar, 99.99%), and a
small amount of additives reported in our previous publica-
tions.9,10 First, the cathode materials (Ni, NaCl, and additives)
were thoroughly mixed using a low-energy ball milling method.
Then, well-mixed cathode powders were granulated using a
granulator (Freund TF-LABO). Sodium tetrachloroaluminate
(NaAlCl4), catholyte, was prepared following the procedure
reported in our previous publications.9,10 A molar ratio of Na to
Al in the catholyte analysed by ICP was 0.51 : 0.49. An excess of
NaCl was used to prevent the formation of Lewis-acidic melts.

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Journal of Materials Chemistry A
For the typical button cells, 1 g of granules consisting of
NaCl, Ni, and additives (NaI, NaF, FeS, and Al)11 were loaded on
the cathode side and then 0.5 g of catholyte was vacuum inl-
trated at 200  C. The theoretical capacity of 1 g of granules with
a molar ratio of Ni/NaCl ¼ 1.82 is 157 mA h, which is calculated
from the capacity of NaCl. Granules with three different molar
ratios of Ni/NaCl (1.82, 1.7, and 1.5) were used to examine the
effects of Ni/NaCl ratios on cell performance. In all cases, the
theoretical capacity of each cell was xed at 157 mA h.
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Planar button cell conguration
The button cell consists of the battery case (cathode and anode
case), alpha-alumina (99.5% purity) xture, and BASE (3 cm2
active area) as reported in our previous publication.10
Composite yttria-stabilized zirconia (YSZ)/b00 alumina (BASE)
discs were fabricated adopting the vapour phase conversion
process, which has been reported in the literature.12,13 The
volume ratio of b00 alumina to YSZ in the composite BASE was
7 : 3. The thickness of the BASE disc aer conversion and creep-
attening was 500 mm. Before loading any active materials, a
BASE disc was glass-sealed to an a-alumina xture. The anode
side of the BASE disc was further treated with aqueous lead
acetate (Pb[CH3COO]2) solution and heat treated at 400  C
under nitrogen in order to improve the wettability of the
sodium melt.14
Molybdenum discs and springs were used as current
collectors for the cathode, due to the electrochemical stability of
metallic molybdenum under the operating conditions of the
cathode.15 Current collectors for the anode were made of
stainless steel discs and springs.
A button cell was then assembled using compressive sealing
with a gold O-ring (0.5 mm thick) for the cathode side and a
silver O-ring (0.5 mm thick) for the anode side in an atmo-
sphere-controlled glove box purged with argon. Aer being
assembled, the button cell was tested at 280  C in air.
Battery tests
Cell tests were carried out using an Arbin potentiostat (MSTAT
8000) controlled by vendor supplied soware (MITS Pro). The
cell was initially charged up to 2.8 V to obtain a full capacity at a
constant current of 10 mA and discharged back to 30 mA h
residual capacity (20% state of charge, SoC) at the same
current. Three different test schedules were used to identify the
effects of various parameters. First, a xed-capacity cycling test
was conducted with a xed cycling capacity window (60% of
theoretical capacity) to analyze the inuence of C-rate, Ni/NaCl
ratio, and voltage at the end of charge (EOC). Second, a deep-
cycling test was also performed between cutoff voltages of 2.4 V
and 2.7 V in order to examine the effects of large-capacity
cycling on cell degradation. Finally, a controlled discharge test
(partial discharge test) was carried out between cutoff voltages
of 2.5 V and various high limits to understand the effects of SoC
at EOC on cell performance. The same current of 30 mA (C/3,
10 mA cm2) was used for charging and discharging except for
high-rate tests at 1 C (90 mA, 30 mA cm2).
14936 | J. Mater. Chem. A, 2013, 1, 14935–14942
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Characterization
Aer cell tests, the fracture surface of the cathodes was observed
using a scanning electron microscope (SEM, JEOL JSM-5900LV)
equipped with an Oxford energy dispersive X-ray spectrometry
(EDS) system. The particle sizes of Ni and NaCl in the cathodes
were measured from SEM micrographs and elemental
mappings of Ni and Na.
Results
C-rate (xed-capacity cycling tests)
The electrochemical test results of cells that were tested at 280  C
at two different C-rates (C/3 and 1 C) with a cycling capacity of 90
mA h (20–80% SoC) are shown in Fig. 1. These cells contained the
cathode granules with a Ni/Na molar ratio of 1.82. No degradation
in capacity was observed in either C/3 or 1 C tests up to 60 cycles
(refer to Fig. 1a). The specic discharge energy density of cells
cycled with 90 mA h was 150 W h kg1, which varied slightly for
different C-rates (Fig. 1b). The overall energy efficiencies at C/3
and 1 C were 96% and 93% in Fig. 1c, respectively. Even though
energy efficiency drops slightly with C-rate, the cell tested at 1 C
still revealed high efficiency, over 90%. The voltages at the end of
charge (EOC) and the end of discharge (EOD) are shown in Fig. 1d.
Although the cells tested at C/3 and 1 C did not show any capacity
degradation over 60 cycles (Fig. 1a), the cell tested at 1 C shows a
faster increase in EOC voltage (0.8 mV per cycle) compared to the
cell tested at C/3 (0.2 mV per cycle), indicating a faster increase in
cell polarization and cell degradation.
The cells were disassembled aer 60 cycles in the glove box
and the fracture surfaces of the cathodes were examined using
SEM/EDS (refer to Fig. 2). The brighter spots appearing in back-
scattered electron images (Fig. 2a and c) represent Ni particles
according to EDS point analysis. Corresponding images of Ni
mapping are shown in Fig. 2b and d. The typical Ni particle size
for the cell tested at C/3 was 1–2 mm (Fig. 2a and b), similar to that
of raw Ni powder. However, a signicant Ni particle growth
Fig. 1 Battery testing data on cells with Ni/NaCl ¼ 1.82. (a) Capacity plot for the
button cells over 60 cycles. (b) Specific energy density (W h kg1) for cells at C/3
and 1 C rates. (c) Energy efficiency plot for button cells at C/3 and 1 C rates. (d)
Voltages for EOC and EOD on 3 cm2 button cells at C/3 (30 mA) and 1 C (90 mA)
rates.
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Paper Journal of Materials Chemistry A

consisting of the rst charging step at 90 mA (1 C) up to cutoff

voltages of 2.675 V or 2.8 V and the second charging at cutoff
voltages until reaching 82% SoC. These cells were cycled with
90 mA h cycling capacity between 22% and 82% SoC at C/3 for
discharge. The typical voltage proles vs. SoC are shown
in Fig. 4.
SEM images collected from the fracture surfaces of cathodes
aer 60 cycles are shown in Fig. 5. Both cells exhibited similar
Ni particle sizes (10 mm), indicating no signicant inuence of
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EOC voltage on Ni growth (Fig. 5a: EOC cutoff of 2.675 V and

Fig. 5b: EOC cutoff of 2.8 V). Similarly, the sizes of NaCl particles
were similar (30–50 mm) for both cells (Fig. 5c: EOC cutoff of
2.675 V and Fig. 5d: EOC cutoff of 2.8 V). These results indicate
that the EOC voltage is not a signicant factor in the particle
growth of either Ni or NaCl.

Fig. 2 (a and c) SEM images (backscattering, 1000) for cathode granules from
the cell (Ni/NaCl ¼ 1.82) tested at C/3 and 1 C rates, respectively. (b and d) Nickel Ni/NaCl ratios (xed-capacity cycling tests)
mapping on the SEM images shown in (a) and (c). To examine the effects of Ni/NaCl ratios on cell degradation,
cells with three different molar ratios of Ni to NaCl (1.82, 1.7
and 1.5) in cathode granules were tested. Cell tests were
(10 mm) was observed for the cell tested at 1 C (Fig. 2c and d). To
observe the particle size of NaCl, Na mapping was also conducted
on the fracture surfaces of cathode materials, as shown in Fig. 3.
NaCl crystals are represented by brighter areas in Na mapping
images (Fig. 3a and c) due to the higher Na density of NaCl
compared to NaAlCl4. Some dark areas shown in the Na mapping
are due to the uneven fracture surfaces. Despite the difference in
C-rates, a similar size distribution of NaCl particles (30–50 mm)
was observed on the cells tested at C/3 and 1 C. This result implies
that C-rate made no signicant impact on the growth of NaCl
particles even though there was some growth of NaCl, which had
an initial size of 10 mm. Fig. 4 Voltage profile of the 30th cycle for 1 C (90 mA) tests (1 C charge and C/3
discharge) with the voltage at EOC fixed at 2.675 V (black) and 2.8 V (red),
respectively. The charging process consists of two steps, a constant-current
EOC voltages (xed-capacity cycling tests) (90 mA) charging process followed by a constant-voltage charging process once
To identify the effects of EOC voltage on cell degradation, two the voltage reaches the voltage limits.

identical cells were tested with different charging processes

Fig. 5 SEM images of cathode granules from the cells cycled with different EOC
voltage limits. EOC voltage limit of 2.675 V: (a) Ni particles (1000) and (c) NaCl
Fig. 3 (a and c) Na mapping for the cross-section of cathode granules from cells particles (300). EOC voltage limit of 2.8 V: (b) Ni particles (1000) and (d) NaCl
tested at C/3 and 1 C rates, respectively. (b and d) SEM images of NaCl particles. particles (300).

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Journal of Materials Chemistry A Paper

performed for each cathode formula under two different test Ni/NaCl ratios (deep cycling)
schemes: (1) xed-capacity cycling tests at 30 mA (C/3) with a
Fig. 8 shows results of deep-cycling tests conducted between 2.4
cycling capacity window of 90 mA h (20–80% SoC) and (2)
and 2.7 V at a constant current of 30 mA. The initial capacity of
deep-cycling tests at 30 mA between 2.4 V (EOD) and 2.7 V
the cells run with the deep-cycling schedule was 120 mA h
(EOC).
(80% of the theoretical capacity) for all Ni/NaCl ratios. Unlike
The electrochemical behaviours of cells tested with the xed-
the cells tested with the xed cycling capacity (90 mA h, 60%
capacity cycling schedule are shown in Fig. 6. As expected,
of theoretical capacity), the cells tested for deep capacity cycles
overpotentials during charging and discharging slightly revealed clear capacity fades (Fig. 8b). The voltage proles vs.
increase with decrease in the Ni/NaCl ratio (Fig. 6a) since the
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SoC collected during the 30th cycle clearly indicate that capacity
lower Ni content in the cathode leads to higher ohmic resis-
fade is mainly due to the reduced charging capacity (Fig. 8a).
tance. No capacity fade was observed for the three cells since
The sizes of Ni and NaCl particles were also measured from
none of the cells reached the cutoff voltages of 2.8 V (for
the fracture surfaces of cathodes aer 60 cycles using SEM
charging) and 1.8 V (for discharging). The EOC and EOD volt-
(Fig. 9). As described earlier, the bright spots in Fig. 9a, c and e
ages vs. cycle numbers are shown in Fig. 6b. The cell degrada-
(back scattering, 1000 magnication) represent metallic Ni
tion rate indicated by an increase in EOC voltage is higher for a
cell with a Ni/Na ratio of 1.5, while cells with Ni/Na ratios of
1.82 and 1.7 reveal quite stable performance. As shown in
Fig. 2a, 7a and c, the average Ni particle sizes measured from
SEM analysis aer 60 cycles were 2, 2, and 5 mm for Ni/NaCl
ratios of 1.82, 1.7, and 1.5, respectively. No signicant differ-
ences in the size of NaCl crystals were observed, and the average
sizes of NaCl particles were 30–50 mm for all three cells, as
shown in Fig. 7b and d.

Fig. 8 (a) Voltage profile of the 30th charge and discharge process for Ni/NaCl ¼
1.82 (black), 1.7 (red), and 1.5 (green) in the cells under voltage cutoff cycles. The
cutoff voltage for charge and discharge was 2.7 and 2.4 V, respectively. See text
for more detailed experimental conditions. (b) Capacity plot for cells tested for
Ni/NaCl ¼ 1.82 (black), 1.7 (red), and 1.5 (green).

Fig. 6 (a) Voltage profile of the 30th cycle at C/3 rate for Ni/NaCl ¼ 1.82 (black),
1.7 (red), and 1.5 (green). (b) Voltages for EOC and EOD on 3 cm2 button cells with
C/3 (30 mA) for Ni/NaCl ¼ 1.82 (black), 1.7 (red), and 1.5 (green), respectively.

Fig. 7 (a and c) SEM (backscattering, 1000) images of Ni particles of the cells
cycled for Ni/NaCl ¼ 1.7 and 1.5, respectively. (b and d) SEM images of NaCl
particles for cells cycled between 2.4 and 2.7 V (backscattering, 300) for cells
with Ni/NaCl ¼ 1.7 and 1.5, respectively.
Fig. 9 (a, c, and e) SEM (backscattering, 1000) images of Ni particles of the cells
cycled between 2.4 and 2.7 V with Ni/NaCl ¼ 1.82, 1.7, and 1.5, respectively. (b, d,
and f) SEM images of NaCl particles for cells cycled between 2.4 and 2.7 V
(backscattering, 300, 250, and 200) for cells with Ni/NaCl ¼ 1.82, 1.7, and
1.5, respectively.

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Paper Journal of Materials Chemistry A

particles. The typical size of Ni particles for the cells tested

under deep capacity cycles is 10 mm regardless of Ni/NaCl
ratios, which is larger than the original Ni particle size (1–2 mm).
The SEM images of NaCl particles are shown in Fig. 9b
(Ni/NaCl ¼ 1.82, 300), 9d (Ni/NaCl ¼ 1.7, 250), and 9f
(Ni/NaCl ¼ 1.5, 200). The NaCl particles in the cathode tested
under deep capacity cycles exhibited signicant growth. NaCl
particle sizes aer 60 deep cycles are 50–70 mm for Ni/NaCl ¼
1.82, 70–100 mm for Ni/NaCl ¼ 1.7, and >150 mm for Ni/NaCl ¼
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1.5, which are shown in Fig. 9.

Voltage/SoC at EOC (controlled discharge test)

Button cells (Ni/NaCl ¼ 1.82) were tested under a constant
current of 30 mA by applying different cutoff voltages for
EOC. The voltage of EOD was xed at 2.5 V in order to limit
the discharge capacity (partial discharge). Fig. 10a shows
voltage proles vs. SoC for the cells cycled in three
different voltage ranges (2.5–2.65 V, 2.5–2.7 V, and 2.5–2.8 V).
The charge–discharge capacity vs. cycle number is shown
in Fig. 10b. All cycled cells revealed quite stable performance
regardless of EOC cutoff voltages, even though there was a Fig. 11 Left: SEM images (backscattering, 1000) of cathode granules from the
cell (Ni/NaCl ¼ 1.82) cycled between 2.5 and 2.65 V (a), 2.5 and 2.7 V (c), and 2.5
difference in cycling capacity (80 mA h for 2.65 V EOC,
and 2.8 V (d), respectively. Right: corresponding SEM images of NaCl shown on
95 mA h for 2.7 V EOC, and 105 mA h for 2.8 V EOC). It the left.
should be noted that these cells were discharged down only
to 33% SoC due to the high EOD cutoff voltage of 2.5 V
while the cells were discharged to 20% SoC for the deep-
cycling test, of which the EOD cutoff voltage was 2.4 V (refer Discussion
to Fig. 8).
The experimental conditions, the results of electrochemical
Fig. 11 shows SEM micrographs collected from the fracture
properties, and the corresponding particle sizes of Ni and NaCl
surfaces of cathodes aer 60 cycles under controlled discharge
are summarized in Table 1. Table 1 indicates that several
test schedules. A typical Ni particle size of the cell tested
parameters inuence Ni particle growth. First, the average Ni
between the cutoff voltages of 2.5 and 2.65 V was similar to that
particle size is around 10 mm for the 1 C test (Experiment 2),
of original Ni powder (2 mm), indicating no noticeable Ni
which is signicantly larger than the average particle size of 2
particle growth aer 60 cycles. However, a signicant particle
mm observed for the C/3 test (Experiment 1). The cell tested at a
growth of Ni was observed for the cells tested with the EOC
1 C rate experienced higher current density and higher EOC
cutoff voltages of 2.7 and 2.8 V. The typical size of Ni particles
voltage even though the cycling capacity and cycling window
was 7 and 10 mm for the cells tested with EOC cutoff voltages
were the same. When the EOC voltage was limited to 2.675 V
of 2.7 and 2.8 V, respectively. NaCl particles have grown to
(Experiment 3), a similar Ni particle size (10 mm) was observed
similar size in the range between 30 and 50 mm aer 60 cycles
as for the cell tested with a higher EOC voltage limit of 2.8 V
for all cells tested with different EOC cutoff voltages, as shown
(Experiment 4). This result implies that higher current density
in Fig. 11b, d and f, respectively.
is a major parameter that induces Ni particle growth while the
effect of higher EOC voltage is minimal on Ni particle growth.
The effects of Ni/NaCl ratios on the Ni particle size of the cells
tested at C/3 (30 mA) with the cycling capacity of 90 mA h can be
seen by comparing Experiments 1, 5 and 6. It appears that only
the cell tested with the lowest Ni/NaCl ratio of 1.5 shows some
growth of Ni particles (up to 5 mm). When the cells with various
Ni/NaCl ratios were deep cycled between 2.4 and 2.7 V (Experi-
ments 7, 8, and 9), the Ni particle size was 10 mm regardless of
Ni/NaCl ratios. Since the same current of 30 mA was used, this
seems to be related to the higher SoC at the EOC, which reached
96–97%. In order to examine the effect of SoC at EOC, the cells
Fig. 10 (a) Voltage profile of the 30th charge and discharge process for the cell
cycled between 2.5 and 2.65 V (black), 2.5 and 2.7 V (red), and 2.5 and 2.8 V
with the Ni/NaCl ratio of 1.82 were also cycled at 30 mA between
(green). (b) Capacity plot for cells cycled between 2.5 and 2.65 V (black), 2.5 and 2.5 and various EOC voltages of 2.65, 2.7, and 2.8 V (controlled
2.7 V (red), and 2.5 and 2.8 V (green). discharge tests). As expected, when higher EOC voltage was

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Table 1 Summary of effect on Ni and NaCl particle sizes for different Ni/NaCl ratios, C-rates and capacitiese

I Cycled SoC EOD SoC Degradationb

Exp. C-rate (mA) Ni/NaCl capacity (mA h) EOC (V) (EOC) (%) (V) (EOD) (%) Ni (mm) NaCl (mm) %/cycle

1 C/3a 30 1.8 90 2.65 77 2.3 20 2 30–50 0.003

2 1C 90 1.8 90 2.78 77 2.3 20 10 30–50 0.008
3 1C 90 1.8 90 2.675 82 2.5 25 10 30–50 0.004
4 1C 90 1.8 90 2.8 82 2.5 25 10 30–50 0.007
5 C/3a 30 1.7 90 2.66 77 2.3 20 2 30–50 0.006
C/3a 5
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6 30 1.5 90 2.68 77 2.3 20 30–50 0.063

7 C/3a 30 1.8 121 2.7 97 2.4 24 7 50–70 0.071
8 C/3a 30 1.7 117 2.7 96 2.4 24 10 70–100 0.176
9 C/3a 30 1.5 116 2.7 96 2.4 24 10 >150 0.655
10 C/3a 30 1.8 80 2.65 84 2.5 33 2 30–50 0.034c
11 C/3a 30 1.8 96 2.7 98 2.5 37 7 30–50 0.000d
12 C/3a 30 1.8 106 2.8 100 2.5 33 10 30–50 0.000d
a
The current for charge and discharge was 30 mA. b Degradation rate was obtained using linear tting of discharge energies during 60 cycles. c The
higher degradation rate is an artifact caused by the lower cutoff voltage of 2.65 V which is on the at voltage prole. d No degradation was observed
due to a positive slope obtained from linear tting. e C-rate (xed capacity cycling tests): Exp #1, and #2. EOC voltages (xed capacity cycling tests):
Exp #3, and #4. Ni/NaCl ratios (xed capacity cycling tests): Exp #1, #5, and #6. Ni/NaCl ratios (deep cycling): Exp #7, #8, and #9. Voltage/SoC at EOC
(controlled discharge test): Exp #10, #11, and #12.

applied, wider cycling capacity and higher SoC at EOC were
achieved while the SoC at EOD remained similar due to the
same EOD voltage limit of 2.5 V. Since the EOC voltage itself was
not a main factor in increasing the Ni particle size as mentioned
above, the increase in Ni particle growth with higher EOC
voltage seems to be closely related to higher SoC at EOC. In
summary, the current density, Ni/NaCl ratio and SoC at EOC are
parameters that inuence the growth of Ni particles.
The effects of experimental parameters on NaCl particle
growth were also examined. As can be seen in the results of
Experiments 1–6, the current density and the Ni/NaCl ratio did
not seem to inuence the growth of NaCl crystals signicantly
when the cells were tested with the same cycling capacity of
90 mA h. The most signicant NaCl particle growth was obvious
when the cells were deep cycled between 2.4 and 2.7 V (Exper-
iments 7–9). In this case, a lower Ni/NaCl ratio leads to faster
NaCl growth.
However, the effects of SoC at the EOC on NaCl growth are
marginal, unlike Ni particle growth, as shown in Experiments
10 and 11. For the particle growth of NaCl, it can be concluded
that the Ni/NaCl ratio inuences it signicantly only when the
cycling capacity window is large (deep cycling).
The particle growth of both Ni and NaCl in cathodes is
considered one of the most important factors that affect the
degradation of Na–NiCl2 battery performance. The larger the
particles of active ingredients contained in the cathode, the less
active surface area is available for electrochemical reactions.
Therefore, the particle growth of Ni and NaCl can lead to an
increase in cell polarization due to the reduced active area. Even
though growth of both particles can cause degradation in cell
performance, our controlled experiments show that only the
growth of NaCl particles leads to signicant fade. In our
experiments, Ni particles have grown up to 10 mm mainly due to
the high current density, low Ni/NaCl ratio, and high SoC at
EOC. However, this Ni growth did not induce signicant cell
degradation. This is possibly related to the use of excess Ni in
the cathode so that the available active surface area of Ni
particles can still be sufficient even aer particle growth. On the
other hand, all the cells that experienced fast degradation
revealed more growth of NaCl particles (refer to Experiments
7–9). The cells, in which the size of NaCl is larger than 50 mm,
exhibit faster degradation.
To the best of our knowledge, the detailed electrochemical
reaction mechanisms of each ingredient such as NaCl, Ni,
NiCl2, and NaAlCl4 have not been clearly reported. Even though
the overall electrochemical reaction shown in eqn (1) is quite
simple, a detailed mechanism of cell reactions can be proposed
based on correlations between particle growth (Ni and NaCl)
and cell performances. A schematic diagram of proposed
charging and discharging processes for a Na–NiCl2 battery is
shown in Fig. 11.
For the charging process, the electrochemical reduction of
Na+ (reaction (A) in Fig. 12) takes place on the anode aer Na+
ions move through the BASE. At the same time, the electro-
chemical oxidation of Ni (reaction (B) in Fig. 12) occurs on the
surface of Ni particles by consuming chloride anions to form a
NiCl2 layer. In reactions (A) and (B), Na+ and Cl ions should be
Fig. 12 Schematic diagram of charge and discharge processes for a Na–NiCl2
battery.

14940 | J. Mater. Chem. A, 2013, 1, 14935–14942 This journal is ª The Royal Society of Chemistry 2013

Paper
supplied from secondary electrolyte NaAlCl4 ((A) and (B)) since
direct contact between solid NaCl and Ni is quite limited.
Therefore, the depletion of NaCl in the catholyte can occur
locally, leading to phase shiing of the catholyte to a partially
Lewis-acidic condition to form an AlCl3-rich phase such as
NaAl2Cl7.7 Since the phase diagram of NaCl–AlCl3 has a stable
liquid phase for NaCl–AlCl3 close to 1 at 280  C,9 NaCl particles
should also be dissolved in Lewis-acidic melts to form neutral
melts (reaction (C) in Fig. 12). During the discharge process, Na+
Published on 23 September 2013. Downloaded by PNNL Technical Library on 13/03/2014 16:56:30.
and Cl ions, produced from the oxidation of liquid sodium on
the anode and the reduction of NiCl2 on the cathode, increase
the NaCl–AlCl3 ratio in the catholyte, and excessive NaCl in the
melts is precipitated out as solid NaCl crystals in order to
maintain the neutral catholyte. Based on this analysis, detailed
battery reaction mechanisms for the charge process can be
proposed as follows.
1Na+ (from NaAlCl4) + 1e / Na (l, anode) (A)
1/2Ni(s, cathode) + 1Cl (from NaAlCl4) /
1/2NiCl2 (s, cathode) + 1e (B)
2NaAlCl4(l)  Na+  Cl /
NaAl2Cl7(l) (A + B in the catholyte)
NaAl2Cl7(l) + NaCl(s, cathode) /
2NaAlCl4 (l) , in the catholyte (C)
Apparently, larger NaCl particles with smaller surface areas
can slow down the dissolution of NaCl (reaction (C)) in the
melts. This is in good agreement with our experimental obser-
vation that higher polarization (and faster degradation) was
associated with larger NaCl particles. The growth of NaCl
particles over cycles can be explained by Ostwald ripening,
which is basically a thermodynamically driven process because
larger particles are more energetically stable than smaller
particles due to the reduced surface energy.16 For charging and
discharging processes, NaCl particles undergo dissolution and
precipitation, respectively. When supersaturated NaCl is
precipitated out from melts during discharge, it has a tendency
to grow on the surfaces of larger particles. Over testing cycles,
the population of smaller NaCl particles will be decreased while
relatively larger NaCl particles grow even larger, and overall the
average NaCl particle size will increase. It is not difficult to
expect that the disappearance of smaller NaCl particles in the
cathode is greater for tests cycled with a larger capacity window.
For instance, the average NaCl particle size increased from 30–
50 mm (with a cycling capacity of 90 mA h) to 50–70 mm (with a
cycling capacity of 121 mA h). However, high SoC at EOC (more
consumption of NaCl) has a marginal inuence on the NaCl
growth. In Experiments 7 and 11 listed in Table 1, both cells
were charged to a similar SoC (96–98%), but they revealed quite
different NaCl growth and cell degradation. Since the major
difference between the two experiments is that the cell of
This journal is ª The Royal Society of Chemistry 2013
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Journal of Materials Chemistry A
Experiment 7 had a larger capacity window (or cycling capacity),
it can be concluded that the major parameter in the cell
degradation is the growth of NaCl particles caused by cycling
with a large capacity window.
It was observed that larger Ni particles were correlated with
higher C-rate, higher SoC at the EOC, and lower Ni/NaCl ratio.
However, it is not clear how Ni particles grow during the cell
cycling. A few mechanisms for Ni particle growth in different
applications, such as solid oxide fuel cells (SOFCs)17,18 and
catalysis,19 have been proposed: (1) Ostwald ripening, where Ni
atoms migrate from smaller particles to larger particles and (2)
vapor transport between Ni particles. However, neither of the
above mechanisms could be directly adopted for the case of the
Na–NiCl2 battery, due to a signicantly lower operating
temperature (280  C) compared to SOFCs (800  C) and catal-
ysis (500  C). Any direct migration of Ni particles, Ni atoms, and
Ni vapors is unlikely to happen in a ZEBRA battery.
One feasible mechanism of Ni particle growth is Ostwald
ripening which occurs by the migration of Ni2+ ions through
dissolved NiCl2 in the melts. When NiCl2 layers are produced on
the surfaces of Ni particles during the charge process, it is likely
to facilitate Ostwald ripening through dissolved Ni2+ species in
the melts. However, the Ni particle growth through Ostwald
ripening should be much slower than the NaCl growth
mentioned earlier because of the lower solubility of NiCl2
compared to NaCl in the melts. The detailed study of NiCl2
solubility in NaCl-saturated NaAlCl4 (basic melts) has been
previously reported for the temperature range between 200 and
400  C.7 The reported level of Ni in the basic melts was lower
than 5 ppm with the presence of additives at a temperature
lower than 300  C.7 A slower Ni particle growth was also
reported at lower temperatures where the solubility of NiCl2 is
further limited.7 In the case of higher rate tests, the more acidic
melts (AlCl3-rich phase) can present locally on the Ni surface
due to high current densities. In a locally acidic environment,
the level of Ni2+ could be increased by forming nickel tetra-
chloroaluminate according to the reaction below under the
battery operating conditions.20
NiCl2 + 2AlCl3 / Ni(AlCl4)2 (2)
The process of Ostwald ripening will be pronounced with an
enhanced Ni2+ level in the acidic melts. This is consistent with
our experimental results (Experiments 2–4) where a faster
growth of Ni particles was observed for higher C-rate tests. To
maintain the basicity of the melts, it is necessary to have an
excess amount of solid NaCl in the cathode at all times. At high
SoC at EOC, most of the small NaCl particles in the cathode
should be dissolved in the melts, and melts can be more acidic
due to the sluggish dissolution of larger NaCl particles. As a
consequence of the acidic environment, a faster growth of Ni
particles is expected for the battery tests with higher SoC at
EOC, which is in good agreement with the experimental results
(Experiments 7, 8, 9, 11, and 12). For cells having lower Ni ratios
(Experiments 6, 8, and 9), the available active surface area of the
Ni electrode is relatively small. Thus, a higher current density
on Ni particles is expected for a cell with a lower Ni/NaCl ratio
J. Mater. Chem. A, 2013, 1, 14935–14942 | 14941

Journal of Materials Chemistry A
despite the same overall cell current density. A faster growth of
Ni particles observed for the cells having lower Ni ratios can also
be attributed to a higher local current density.
Conclusions
The Na–NiCl2 battery was tested to determine the effects of
various parameters such as C-rate, Ni/NaCl ratio, cutoff voltage,
and capacity windows on particle growth and cell performance
Published on 23 September 2013. Downloaded by PNNL Technical Library on 13/03/2014 16:56:30.
degradation. For Ni, higher current density, higher SoC at EOC,
and lower Ni/NaCl ratio are the main parameters that lead to
faster particle growth. In the case of NaCl, signicant growth
was detected only when the cells were cycled with a large cycling
capacity window. With a large cycling window, the growth of
NaCl particles was accelerated with a decrease in the Ni/NaCl
ratio. Even though the growth of both Ni and NaCl can inuence
the cell degradation, our results indicate that the growth of
NaCl is a dominant factor affecting cell degradation. The use of
excess Ni seems to play a role in tolerating the negative effects
of particle growth of Ni since the available active surface area of
Ni particles can still be sufficient even aer particle growth.
Acknowledgements
This work is supported by the Laboratory-Directed Research and
Development Program of Pacic Northwest National Laboratory
(PNNL) and the Office of Electricity Delivery and Energy Relia-
bility's storage program. PNNL is a multiprogram laboratory
operated by Battelle Memorial Institute for the Department of
Energy under Contract DE-AC05-76RL01830.
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