Journal of The Electrochemical Society, 164 (13) A3349-A3356 (2017) A3349

Using the Charge-Discharge Cycling of Positive Electrode

Symmetric Cells to Find Electrolyte/Electrode Combinations with
Minimum Reactivity
Chongheng Shen,a,b Deijun Xiong,c L. D. Ellis,c Kevin L. Gering,d Ling Huang,a,z
and J. R. Dahnb,c,∗,z
a Department of Chemistry, Xiamen University, Xiamen, 361005, People’s Republic of China
b Department of Physics and Atmospheric Science, Dalhousie University, Halifax B3H 3J5, Canada
c Department of Chemistry, Dalhousie University, Halifax B3H 4R2, Canada
d Idaho National Laboratory, Idaho Falls, Idaho 83415, USA

The effects of solvents, salts, electrolyte additives and surface coatings on LiNi0.4 Mn0.4 Co0.2 O2 (NMC442) or LiNi0.6 Mn0.2 Co0.2 O2
(NMC622) have been probed using positive electrode Li-ion symmetric cells coupled with dV/dQ analysis. A robust symmetric cell
design is presented which prevents hardware corrosion for over at least 800 hours of testing to 4.5 V vs. Li/Li+ at 40◦ C. Positive
electrode symmetric cells using uncoated positive electrode materials and 1M LiPF6 EC:EMC 3:7 or 1M LiPF6 EMC electrolyte
rapidly developed high impedance and showed poor capacity retention. However, if 1% pyridine boron trifluoride (PBF) was added
to these electrolytes, cell performance was dramatically improved. Replacing LiPF6 by LiBF4 in the electrolytes above, with or
without PBF, yielded positive electrode symmetric cells with good capacity retention. Two types of surface coatings were explored on
NMC622 positive electrodes. Cells using surface-coated positive electrodes demonstrated better capacity retention for all electrolytes
compared to cells without surface coatings. This work can be used as a guide by those attempting to find electrolyte/electrode pairs
suitable for use in NMC/graphite cells that can operate with long lifetime to 4.5 V.
© The Author(s) 2017. Published by ECS. This is an open access article distributed under the terms of the Creative Commons
Attribution 4.0 License (CC BY, http://creativecommons.org/licenses/by/4.0/), which permits unrestricted reuse of the work in any
medium, provided the original work is properly cited. [DOI: 10.1149/2.1711713jes] All rights reserved.

Manuscript submitted August 28, 2017; revised manuscript received October 16, 2017. Published November 2, 2017.

Lithium ion batteries with LiNi1-y-z Mny Coz O2 (NMC) positive
electrodes are used in electric vehicles, power tools and energy storage
systems.1–4 The energy density of NMC/graphite cells can be easily
improved if the cells can be charged to higher potential, for example
to 4.4 or 4.5 V at which point the positive electrode is at about 4.48 or
4.58 V vs. Li/Li+ . However, charging NMC/graphite cells to such po-
tentials normally leads to impedance growth and a reduction in cycle
and calendar life.5,6
Increasing the charging cutoff voltage to 4.40 V can cause some
problems:
1) Parasitic reactions like electrolyte oxidation can create harmful
products and damage the surface of the electrodes.7,8 In addition,
in some cases, thick SEI layers on the positive electrode can be
created.
2) The layered surface structure of NMC (R3m) can change into a
spinel-like framework (Fd3m) and then to the disordered rock-
salt structure (Fm3m).9,10 This is thought to be one cause of
impedance growth at the positive electrode.
3) The unit cell volume of most NMC materials begins to contract
rapidly, by about 4%, when the potential is raised above 4.4 V vs
Li/Li+ as the lithium content is decreased below about z = 0.25
in Lix Ni1-y-z Mny Coz O2 . This could induce a detachment between
binder and active particles along with cracks forming inside the
secondary particles.11,12
A number of strategies have been used to protect the positive
electrode surface from parasitic reactions. These include the use of
electrolyte additives, different salts, different solvents and electrode
material coatings. Some of these strategies will be used in the work
here. For example, Petibon et al. and Ma et al.13,14 showed that ethylene
carbonate (EC)-free electrolytes, like 1M LiPF6 in 95% ethyl methyl
carbonate with 5% fluoroethylene carbonate was very effective in
allowing NMC/graphite cells to operate to 4.4 V. EC-free electrolytes
will be explored in this preliminary work.
Electrolyte additives like pyridine boron trifluoride (PBF) and pyri-
dine phosphorus pentafluoride (PPF) have been reported to provide
∗ Electrochemical Society Fellow.
z
E-mail: jeff.dahn@dal.ca; huangl@xmu.edu.cn
better capacity retention during high-voltage and high temperature
cycling of NMC/graphite cells.15,16 Their use will be explored in this
preliminary work.
The electrolyte salt LiBF4 has a less labile B-F bond than the
P-F bond of LiPF6 , has been found to improve hydrolytic and ther-
mal stability of electrolytes.17 LiBF4 has been reported to help re-
duce the parasitic currents in cells caused by aluminum current
collector corrosion at high voltages.18 The use of LiBF4 in car-
bonate electrolytes can improve elevated temperature cycling of
Li1+y Mn1.5 Ni0.5 O4-x Fx /Li4 Ti5 O12 cells in comparison to cells with
LiPF6 salt.19 Ellis et al.20 showed that NMC/graphite cells tested to
4.4 V at 40◦ C using 1M LiBF4 in EC:EMC and no electrolyte ad-
ditives had greater columbic efficiency and smaller charge end point
capacity slippage than corresponding cells using LiPF6 . This suggests
less parasitic reactions at the positive electrode when LiBF4 is used.
The use of LiBF4 will be explored in this preliminary work.
A coating of Al2 O3 on NMC442 was reported to prevent the surface
from severe electrolyte side reactions at 4.40 V by protecting the very
active nickel oxide sites and lowering the charge transfer resistance
growth.21,22 Arumugam et al. showed the benficial impact of an Al2 O3
coating on NMC622 in cells tested to 4.4 V.23 In all electrolytes
tested, cells with the Al2 O3 -coated NMC622 had larger coulombic
efficiency, lower charge end point capacity slippage and better capacity
retention than cells using uncoated NMC622. The impact of two
different coatings on NMC622 will be explored in this preliminary
work.
How can academic researchers, normally without access to facili-
ties to prepare and test hundreds or thousands of reliable and repeatable
Li-ion cells, make a credible contribution with so many variables, i.e.
solvents, salts, electrolyte additives, electrode coatings to evaluate?
It is our opinion that studies using a test vehicle that allows only
the positive electrode/electrolyte interaction to be evaluated are ex-
tremely valuable. If a positive electrode/electrolyte pair can be found
that is stable at 4.5 V and at elevated temperature, there is a good
chance that this pairing can work well in a full Li-ion cell. Recently
Xiong et al.24 introduced the so-called “pouch bag” method where a
charged positive electrode and electrolyte sealed inside a pouch bag
can be monitored during and after storage at elevated temperature.
This method proved extremely valuable for examining the effects of
new electrolyte additives and electrode coatings at high voltage by

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 A3350 Journal of The Electrochemical Society, 164 (13) A3349-A3356 (2017)

eliminating the interaction from negative electrode.24 However, the
electrode in the pouch bag cannot be charged and discharged which
limits the utility of the test.
Symmetric cells constructed initially from one charged pos-
itive electrode and one discharged positive electrode allow the
electrodes to be charged and discharged and also eliminate the
graphite or lithium negative electrode. Such symmetric cells allow
the positive electrode/electrolyte interaction to be carefully probed.
When coupled with advanced techniques like ultra high precision
coulometry,25 isothermal microcalorimetry26 and differential volt-
age analysis (dV/dQ analysis),27 it is believed that the use of pos-
itive/positive symmetric cells can lead to the identification of opti-
mized electrolyte/electrode pairings for further testing in full Li-ion
cells. The purpose of this paper is to demonstrate an effective posi-
tive/positive symmetric cell test vehicle for NMC electrodes that can
be cycled at least up to 4.5 V vs. Li/Li+ and to show the results of
preliminary tests that demonstrate its effectiveness.
As evidenced by many previous reports,28–30 symmetric cells are
often built to study the impedance changes, without confusion, that oc-
cur at both the positive electrode (using a positive/positive symmetric
cell) or the negative electrode (using a negative/negative symmet-
ric cell) of a full Li-ion cell using electrochemical impedance spec-
troscopy (EIS).31,32 Burns et al. and Krause et al.33,34 have shown that
negative/negative symmetric cells can also be charged and discharged
effectively and are very useful to learn about parasitic reactions and
SEI growth at the negative electrode. By contrast, positive/positive
symmetric cells built for such impedance testing normally are not
charge-discharge cycled as it has proven difficult to obtain good ca-
pacity retention from such cells. The successful and sustainable cy-
cling of positive/positive symmetric cells at high voltage has only been
reported for Li(Ni0.8 Co0.15 Al0.05 )O2 (NCA) symmetric cells35 to the
best of our knowledge. Some of the authors of Reference 29 are also
authors of this paper and at the time of the work of Reference 29 the
production and evaluation of NMC111 and NMC442 positive elec-
trode symmetric cells was attempted. Unsatisfactory charge-discharge
cycling results were obtained even though many experiments were
tried.
The goals of this paper are:
1) Demonstrate an effective test vehicle for positive/positive sym-
metric cells using NMC positive electrodes;
2) Use dV/dQ vs Q analysis to demonstrate that the high voltage
electrode in NMC positive/positive symmetric cells charged to
±0.9 V is reaching 4.5 V vs Li/Li+ ;
3) Explore the impact of EC-free electrolytes;
4) Explore the impact of the PBF and PPF electrolyte additives;
5) Explore the impact of using LiBF4 instead of using LiPF6 ;
and
6) Explore the impact of coatings on the NMC positive electrode
material.
It is emphasized that this is preliminary work which is being dis-
seminated so that other researchers can adopt these methods to assist
in the quest for long-lived NMC/graphite cells that can operate while
being charged to 4.4 V and above. As such, this paper does not eluci-
date failure mechanisms. That will be the focus of further studies.
Experimental
Electrode materials.—Commercial Li[Ni0.4 Mn0.4 Co0.2 ]O2 (called
NMC442), Al2 O3 -coated Li[Ni0.6 Mn0.2 Co0.2 ]O2 (called NMC622A)
and “high-voltage” coated Li[Ni0.6 Mn0.2 Co0.2 ]O2 (called NMC622B)
were all obtained from Umicore (Cheonan, Korea). The NMC442
was not coated. The details of the production and coating of the
NMC622A material are given in Reference 23 and references therein.
These materials were used in 402035-size Li-ion pouch cells produced
by Li-Fun Technology (Zhuzhou City, Hunan Province, PRC). The
same artificial graphite material was used in all the pouch cells.
Pouch cells.—The pouch cells were vacuum-sealed without elec-
trolyte at Li-Fun and shipped to our laboratory in Canada. After cut-
ting open the heat seal, the pouch cells were vacuum-baked at 80◦ C
for 14 hours to eliminate possible residual moisture and then di-
rectly transferred (no air exposure) into an argon-filled glove box for
electrolyte injection. All NMC442/graphite, NMC622A/graphite and
NMC622B/graphite pouch cells were filled with 0.76 mL electrolyte.
The pouch cells were vacuum-sealed under a gauge pressure of −90
kPa and using a compact vacuum sealer (MSK-115A, MTI Corp.).
Then the sealed pouch cells were held at 1.5V for 24 hours to allow
electrolyte to permeate throughout the jelly roll of the cell. After wet-
ting the cells were charged to 3.5 V using a C/20 current (about 10 mA
for these cells) at 40◦ C. After holding for 1 hour at 3.50 V, the charged
pouch cells were moved into the argon-filled glove box, degassed and
vacuum sealed again. The pouch cells were then charged to 4.40 V
(cells with LiPF6 salt) or 4.35 V (cells with LiBF4 salt) at C/20 and
held for 1 hour. The difference in upper cutoff voltage during forma-
tion is not expected to be significant, but was made based on work
reported by Ellie et al.,20 which showed larger amounts of gas genera-
tion when NMC442/graphite cells with LiBF4 were charged above 4.4
V. After this step, cells were degassed a second time as some gas from
the positive electrode/electrolyte interaction is released during the first
charge above 4.3 V.36 Finally, the pouch cells were programmed to
charge-discharge at 40◦ C (C/20) between 2.8 V and 4.40 V (cells with
LiPF6 ) or 4.35 V (cells with LiBF4 ) for two cycles. Some cells were
then charged to the upper cutoff and held for 30 hours. Others were
discharged to 2.8 V and held for 10 hours. Figure 1 shows a schematic
of the cycling protocol. It is important to build the symmetric cells
using one fully charged electrode and one fully discharged electrode.

Extract positive electrodes

Punch coin cell electrodes

from single side coated region
in outer turn of jelly roll
Assemble symmetric cells
Figure 1. A flow chart for the construction
Aluminum-coated stainless steel cap of positive/positive symmetric cells.
Polypropylene gasket seal
Aluminum spacer
Aluminum spacer
Working electrode (face down)
Separator
Working electrode (face up)
Aluminum-coated stainless steel can

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 Journal of The Electrochemical Society, 164 (13) A3349-A3356 (2017)
Table I. Symmetric cell hardware designs tried in this study. All results reported in this work are from design III.
Hardware component Design I
Cell cap 300-series stainless steel (Kaga Steel)
sputter-coated in-house with 5 μm of Aluminum
Space filler 1 disk spring (17–4 stainless steel, 18 mm in
diameter, 0.40 mm in thickness, 6.20 mm hole,
Key Bellevilles, Leechburg, PA)
Space filler 2 stainless steel spacer (304 stainless steel, 17.98
mm in diameter, 0.81 mm in thickness, Bokers,
Minneapolis, MN), USA
Cell Base 400-series stainless steel (Kaga Steel)
sputter-coated in-house with 5 μm of Aluminum
Comments This design showed severe green discolorations
and green deposits in cells after testing. Capacity
retention for +/+ symmetric cells was always
poor. Electrolyte in direct contact with 304 SS
spacer.
This was deemed easier to do than trying to locate the point where the
positive electrodes were exactly at 50% state of charge for the poten-
tial window selected and building symmetric cells from electrodes at
the same 50% state of charge. Each experimental result in this report
was based on a minimum of two brother pouch and/or symmetric
cells.
Electrolyte.—LiPF6 (BASF, 99.94%, water content<14ppm) and
LiBF4 (BASF, 99.9%) were used as electrolyte salts. The solvents
used were EC:EMC (3:7 wt% ratio, BASF, 99.99%, water content
< 20 ppm), EMC (BASF, 99.99%, water content < 20 ppm) and
vinylene carbonate (VC, BASF, 99.97%). Electrolyte additives used
were pyridine boron trifluoride (PBF) (3M Co., > 99%) and pyridine
phosphorus pentafluoride (PPF) (3M Co., 99.5%).15
Symmetric cell hardware.—Several types of coin cell hardware,
labelled I, II and III were tested in these experiments as indicated
in Table I. After a series of initial testing, the hardware labelled III
in the right most column of Table I, and indicated in Figure 1 was
selected for use. This is because any steel components in hardware
sets I and II became corroded and created green discolored regions
in the symmetric cells after testing for 800 hours at 40◦ C. Only all-
aluminum hardware was deemed suitable in the end for these high
voltage symmetric cell studies (up to and above 4.5 V vs. Li/Li+ ) in
agreement with previous work by Sinha et al.37
The symmetric cells used polypropylene blown microfiber (called
BMF, obtained from 3M Co., 0.275 mm in thickness, 3.2 mg/cm2 ) as
the separator. This is a thick compliant separator which ensures some
stack pressure on the electrodes in design III where there is no spring
being used.
Symmetric cells.—After the positive electrodes were prepared in
their lithiated (2.80 V) and delithiated (4.40 V/4.35 V) states, the
pouch cells were opened inside an argon-filled glove box and the
electrodes were extracted. A precision punch (1.14 cm in diameter,
1.02 cm2 in area) was used to punch electrodes from the single-side
coated regions of the positive electrode (at the outer wrap of the jelly
roll). Typically, it was possible to obtain 6 disc shaped single-side
coated electrodes from each pouch cell. Usually, the employed elec-
trolyte in the pouch cells was the same as that planned corresponding
symmetric cells. However, when 2M salts concentrations were used in
the symmetric cells, the disc shaped electrodes were soaked in DMC
to remove the 1M electrolyte. Electrodes were the dried in the glove
box and then 2M electrolyte was added during symmetric cell con-
struction. Figure 1 shows the way the design III symmetric cells were
constructed.
Electrochemical cycling test.—Symmetric cells were charge-
discharge tested using an ultra high precision charger (UHPC)38 sys-
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A3351
Design II Design III
Same as design I Same as design I
Same as design I Aluminum spacer of same size as
design I (Bokers).
Aluminum spacer of same Same as design II
size as design I (Bokers).
Same as design I Same as designs I and II
Better than design I but still No discoloration of hardware and
poor as electrolyte contacted no deposits of unwanted material.
disc spring causing green Possible to obtain excellent
deposits capacity retention for appropriate
electrolyte/electrode pairs.
tem or an E-One Moli Energy tester. These systems were selected
because they allow noise free dQ/dV vs V and noise-free dV/dQ vs
Q data to be collected. This was important to determine the voltages
vs. Li/Li+ which the electrodes reached during testing using dV/dQ
analysis.39 In addition, dQ/dV vs. V plots as a function of cycle num-
ber were used to probe the stability of a particular cell chemistry. The
symmetric cells were tested using a current of C/10 (190 μA) at 40◦ C.
The test voltage range was set to −0.9∼0.9 V, which will be shown to
correspond to about 3.6 V to 4.5 V for each electrode in the symmetric
cell vs. Li/Li+ .
Reference V-Q curves for dV/dQ analysis.—Li/NMC coin type
half cells were constructed from fresh single-side coated electrodes
extracted from the dry (no electrolyte) pouch cells. These were tested
at C/10, C/20 and C/40 between 2.8 and 4.6 V vs Li/Li+ at 40◦ C. These
V-Q curves (predominantly the C/20 curves) were used as reference
curves in the dV/dQ analysis software.39
Results and Discussion
Figure 2 shows typical positive/positive symmetric cell testing
results for NMC442 electrodes with 1M LiPF6 in EC:EMC 3:7, 1M
LiPF6 in EMC, 1M LiPF6 in EC:EMC 3:7 with 1% PPF and 1M LiPF6
in EC:EMC 3:7 with 1% PBF electrolytes. Figure 2a shows that cells
with EC:EMC or EMC solvent and no electrolyte additives retain
about 60% capacity after 20 cycles using currents corresponding to
C/10 at 40◦ C. Figure 2b shows V, the difference between the average
charge and discharge voltages of the cells vs. cycle number. Figure
2b shows that cells without PBF or PPF rapidly gain impedance with
cycling as can also be gleaned from the shifts in dQ/dV vs V near the
beginning of charge and near the beginning of discharge in Figures
2f and 2g. By contrast, cells with PBF or PPF show smaller increases
in V during cycling (Figure 2b) and only small changes in dQ/dV
vs. V as shown in Figures 2h and 2i. Figures 2c and 2d show smaller
capacity fade per cycle and better columbic efficiency for the cells
with PBF and PPF additives as well. Finally, Figure 2e summarizes
the capacity retention after the 20 cycles.
The results in Figure 2, which use the same NMC442 positive
electrodes in all the cells, demonstrate the poor symmetric cell perfor-
mance when uncoated positive electrodes and no electrolyte additives
are employed. This is consistent with the work of Xiong et al.24 who
showed that the impedance of charged (4.4 V) NMC442 positive elec-
trodes stored in 1M LiPF6 EC:EMC 3:7 electrolyte, in the absence of a
negative electrode, increased dramatically. Figure 2 also suggests that
the reason for cell failure is not mechanical disconnect due to parti-
cle cracking since the cells that incorporated PBF electrolyte additive
showed quite good capacity retention.
 A3352 Journal of The Electrochemical Society, 164 (13) A3349-A3356 (2017)

Figure 2. Typical results for positive/positive electrode symmetric cells. a) cell capacity vs. cycle number (C/10, 40◦ C, ± 0.9 V); b) V vs. cycle number; c)
capacity fade per cycle; d) coulombic efficiency; e) percent capacity retained after 20 cycles. Panels f), g), h) and i) show dQ/dV versus V for all 20 tested cycles
for cells with the electrolytes indicated. Only the cell depicted in Figure 2i) shows relatively stable cycling.

It is important to understand the potential range, vs. Li/Li+ , to
which the electrodes were tested. This can be done using dV/dQ vs.
V analysis as described by Dahn et al.39
Figure 3 shows the steps in the dV/dQ analysis of the charge-
discharge cycling data of the cell with 1M LiPF6 in EMC + 1% PBF
that was shown in Figure 2 and featured in Figure 2i. Once the dV/dQ
vs Q curve is fit well as in Figures 3m, 3n and 3o, it is possible to then
determine the potential of each electrode versus lithium metal. Figure
4 shows the results of dV/dQ vs Q analysis for the cells reported in
Figure 2.
The results in Figure 4 can be used to determine the potential
of each electrode vs. Li/Li+ when the symmetric cells reach ±0.9
V. The electrodes in the cells with 1M LiPF6 in EC:EMC 3:7 reach
about 4.3 V (Figures 4a and 4e), those in the cells with 1M LiPF6 in
EMC reach about 4.3 V (Figures 4b and 4f), those in the cells with
1M LiPF6 in EC:EMC 3:7 + 1%PPF reach about 4.4 V (Figures 4c
and 4g) and those in the cells with 1M LiPF6 in EMC + 1% PBF
also reach about 4.4 V. The cells described by Figures 4a, 4e, 4b and
4f show large capacity loss which originates from relative slippage
between the voltage capacity curves of the two electrodes and also
from active material loss. By contrast, the cells described by Figures
4c, 4d, 4g and 4h show little relative slippage and little active material
loss. Figure 4 demonstrates the effectiveness of the PPF and PBF
electrolyte additives on the NMC442 positive electrode.
It was interesting to then examine the impact of different electrolyte
salts and different positive electrode materials on the performance of
positive/positive symmetric cells. Figure 5 shows a summary of the
percent capacity retention for a number of cells, including those from
Figures 2 and 4 for comparison. All cells were tested between ±0.9
V at C/10 and at a temperature of 40◦ C..
There are some very interesting trends in Figure 5. First, the
NMC622 cells, which have coated positive electrode materials, per-
form much better with 1M LiPF6 in EC/EMC than the cells which have
uncoated NMC442. This suggests that the coatings help mitigate pos-
itive electrode/electrolyte reactions, consistent with many literature
reports. Second, NMC442 cells without electrolyte additives, perform
much better with LiBF4 than they do with LiPF6 . This agrees with
the work of Ellis et al.20 which suggests that electrolytes with LiBF4
are more oxidatively stable in full cells charged to 4.4 V (4.48 V vs
Li/Li+ ) than those with LiPF6 when no additives are incorporated.
Third, the NMC622 cells with both coatings perform extremely well
with either 1M LiBF4 and electrolyte additives or 2M LiBF4 with no
additives.
It is important to examine the results of dV/dQ analysis for the
best performing cells in Figure 5.
Figure 6 shows the results for symmetric cells with each of the
three different positive electrodes in the case where all cells have
2M LiBF4 EC:EMC 3:7 electrolyte. Figure 6 shows that each of the
positive electrodes in these cells initially reached 4.5 V vs. Li/Li+
during the first cycle. Both cells with NMC442 electrodes show some
capacity loss due to relative electrode slippage. By contrast, the cells
with NMC662A and NMC622B electrodes showed virtually no ca-
pacity loss, virtually no relative electrode slippage and extremely
stable cycling. This suggests that positive/positive symmetric cells
using NMC622A or NMC622B with 2M LiBF4 in EC:EMC 3:7 elec-
trolyte could have extremely long cycle life even though the positive
electrodes are being pushed as high as 4.5 V every cycle at 40◦ C.
Figure 7 shows the results for symmetric cells with each of the
three different positive electrodes in the case where all cells have
1M LiBF4 EC:EMC 3:7 + 1% PBF electrolyte. Figure 7 shows that
each of the positive electrodes in these cells initially reached 4.5 V vs.
Li/Li+ during the first cycle. Both cells with NMC442 electrodes show
some capacity loss due to relative electrode slippage. By contrast, the
cells with NMC662A and NMC622B electrodes showed less capacity

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 Journal of The Electrochemical Society, 164 (13) A3349-A3356 (2017) A3353

Figure 3. dV/dQ vs. Q curves for the NMC442 symmetric cell with 1 M LiPF6 in EMC+1% PBF during manipulation of the dV/dQ analysis program at the 1st
(a, d, g, j, m), 10th (b, e, h, k, n) and 20th (c, f, i, l, o) cycles. The full and dashed lines represent for the measured and calculated curves, respectively. The changes
to the parameters at each step of the program are described in Reference 39.

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 A3354 Journal of The Electrochemical Society, 164 (13) A3349-A3356 (2017)

Figure 4. Voltage (vs. Li/Li+ )-capacity plots for each of the electrodes in the NMC442 symmetric cells of Figure 2 as determined from dV/dQ analysis for the 1st ,
10th and 20th cycles. The symmetric cell voltage capacity plot is shown in the bottom of each panel. The zero of the capacity axis is the point where the symmetric
cell reaches −0.9 V. The results for two pair cells are shown in each column to demonstrate repeatability of the methods.

loss, little relative electrode slippage and relatively stable cycling. The molarity increases. The values in Figure 8 must be multiplied by the
results in Figure 7 for the NMC622 cells are less impressive than those molarity to get the total binding of the solvent to the anions. Thus, even
in Figure 6, which suggests that more highly concentrated LiBF4 is though the binding energy per mole of anion decreases for the curves
more effective than adding 1% PBF. shown in Figure 8, the total binding energy of the solvent to the anions
Gering’s Advanced Electrolyte Model (AEM) version 2.17340 was increases with molarity. It is suggested here that this increased binding
used to calculate the average solvent binding energy to the PF6 − makes it more difficult for the solvent to be oxidized in 2M LiBF4
and BF4 − anions as a function of salt molarity. Figure 8 shows that solutions than in 1M LiBF4 solutions which is responsible for the
the solvent binding to the anion becomes much stronger as the salt improved performance of the symmetric cells in Figure 6 compared
to those in Figure 7. Figure 8 also shows that the binding energy
of the solvent to the BF4 − anion is much stronger than to the PF6 −
NMC622B with LiBF4
anion. This can explain why symmetric cells with LiBF4 have better
NMC622B with LiPF6 performance than those with LiPF6 when no electrolyte additives are
NMC622A with LiBF4 used as demonstrated in Figure 4. This is an important observation for
NMC622A with LiPF6 the design of high voltage Li-ion cells.
NMC442 with LiBF4
NMC442 with LiPF6
Percent Capacity Retained (20 cycles)

100 Conclusions
A robust test vehicle for positive/positive symmetric cells of NMC
electrodes has been developed. This test vehicle has aluminum sur-
faces and no other metals in contact with the electrolyte. Aluminum is
90 essential if the symmetric cells are to be operated at potentials corre-
sponding to about 4.5 V vs. Li/Li+ at elevated temperatures. Including
stainless steel parts leads to corrosion issues and poor performance of
symmetric cells.
1M LiBF4 in EC/EMC + 1%PBF

1M LiBF4 in EC/EMC + 1%PBF

1M LiBF4 in EC/EMC + 1%PBF

Uncoated NMC442 symmetric cells had poor performance when

1M LiBF4 in EMC + 1% PBF

80
1M LiPF6 in EMC + 1% PBF
1M LiPF6 in EMC + 1% PPF

1M LiPF6 electrolytes without electrolyte additives were used. The

same cells performed much better when LiBF4 salt was used. In
2M LiBF4 in EC/EMC

2M LiBF4 in EC/EMC
1M LiBF4 in EC/EMC

2M LiBF4 in EC/EMC

1M LiPF6 in EC/EMC

1M LiPF6 in EC/EMC
1M LiPF6 in EC/EMC

the presence of PPF or PBF electrolyte additives uncoated NMC442

1M LiBF4 in EMC
1M LiPF6 in EMC

70 symmetric cells performed quite well with either LiPF6 or LiBF4 salts.
Al2 O3 -coated NMC622A and coated NMC622B symmetric cells
performed much better than uncoated NMC442 symmetric cells when
LiPF6 -based electrolytes without additives were used. This result
points to the usefulness of the coatings.
60 The NMC622 cells showed excellent performance with LiBF4
Symmetric cell type electrolyte salt, much better than with LiPF6 salt, either with or without
1% PBF electrolyte additive. In fact, the NMC622 cells with 2M LiBF4
Figure 5. Percent capacity retention for symmetric cells as described by the and no electrolyte additives showed the best performance of the cells
legend after 20 cycles at C/10 and at 40◦ C. The symmetric cells were charged tested. It is believed this is due to the stronger binding between BF4 −
and discharged between ±0.9 V. dV/dQ vs Q analysis was used to determine
and the electrolyte solvents compared to PF6 − .
the potential ranges of the electrodes versus Li/Li+ as is shown in Figures 4, 6
and 7. Duplicate cells were used for each measurement and the average result is We believe that positive/positive symmetric cell testing of the type
plotted in the bar chart. The error bars indicate the range of the measurements shown here can help with the development of electrolyte/electrode
for the two cells. pairings suitable for high voltage operation in NMC Li-ion cells.

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 Journal of The Electrochemical Society, 164 (13) A3349-A3356 (2017) A3355

Figure 6. Voltage (vs. Li/Li+ )-capacity plots for each of the electrodes in some of the symmetric cells of Figure 5 that contain 2M LiBF4 in EC:EMC 3:7 as
determined from dV/dQ analysis for the 1st , 10th and 20th cycles. The symmetric cell voltage-capacity plot is shown in the bottom of each panel. The zero of the
capacity axis is the point where the symmetric cell reaches −0.9 V. The results for two pair cells are shown in each column to demonstrate repeatability of the
methods. Testing was at 40◦ C and C/10.

Figure 7. Voltage (vs. Li/Li+ )-capacity plots for each of the electrodes in some of the symmetric cells of Figure 5 that contain 1M LiBF4 in EC:EMC 3:7 + 1%
PBF as determined from dV/dQ analysis for the 1st , 10th and 20th cycles. The symmetric cell voltage-capacity plot is shown in the bottom of each panel. The zero
of the capacity axis is the point where the symmetric cell reaches −0.9 V. The results for two pair cells are shown in each column to demonstrate repeatability of
the methods. Testing was at 40◦ C and C/10.

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 A3356 Journal of The Electrochemical Society, 164 (13) A3349-A3356 (2017)

140
Energy to Anion (kJ/Mole)
Average Solvent Binding

120

100 Figure 8. Average binding energy of the solvent to the anion for LiPF6 and
LiBF4 solutions as calculated using Gering‘s Advanced Electrolyte Model
LiBF4 version 2.17.3. More positive values mean stronger binding.

80
LiPF6

60
0 1 2 3
LiBF4 Molarity (M)

Acknowledgments
The authors thank NSERC, 3M Canada and Tesla Motors for
the funding of this work under the auspices of the Industrial Chairs
program. Chongheng Shen acknowledges the generous support of
the China Scholarship Council. Leah Ellis acknowledges scholarship
support from NSERC and the Walter Sumner Foundation.
References
1. J. Jiang, K. W. Eberman, L. J. Krause, and J. R. Dahn, Journal of The Electrochemical
Society, 152, A1874 (2005).
2. Naoki Nitta, Feixiang Wu, Jung Tae Lee, and Gleb Yushin, Materials Today, 18, 252,
(2015).
3. Chong S. Yoon, Moon Ho Cho, Byung-Beom Lim, Eung-Ju Lee, and Yang-Kook Sun,
Journal of the Electrochemical Society, 162, A2483 (2015).
4. D. Stevens, R. Ying, R. Fathi, J. Reimers, J. Harlow, and J. Dahn, Journal of The
Electrochemical Society, 161, A1364 (2014).
5. D. Abarbanel, K. Nelson, and J. Dahn, Journal of The Electrochemical Society, 163,
A522 (2016).
6. K. Nelson, G. d’Eon, A. Wright, L. Ma, J. Xia, and J. Dahn, Journal of The Electro-
chemical Society, 162, A1046 (2015).
7. S. Li, C. Chen, X. Xia, and J. Dahn, Journal of The Electrochemical Society, 160,
A1524 (2013).
8. L. Yang, B. Ravdel, and B. L. Lucht, Electrochemical and Solid-State Letters, 13,
A95 (2010).
9. W. Liu, P. Oh, X. Liu, M. J. Lee, W. Cho, S. Chae, Y. Kim, and J. Cho, Angewandte
Chemie, 54, 4440 (2015).
10. F. Lin, I. M. Markus, D. Nordlund, T. -C. Weng, M. D. Asta, H. L. Xin, and
M. M. Doeff, Nat Commun, 5 (2014).
11. H. Liu, J. M. Foster, A. Gully, S. Krachkovskiy, M. Jiang, Y. Wu, X. Yang, B. Protas,
G. R. Goward, and G. A. Botton, J. Power Sources, 306, 300 (2016).
12. S. Hwang, W. Chang, S. M. Kim, D. Su, D. H. Kim, J. Y. Lee, K. Y. Chung, and
E. A. Stach, Chemistry of Materials, 26, 1084 (2014).
13. J. Xia, R. Petibon, D. Xiong, L. Ma, and J. R. Dahn, Journal of Power Sources, 328,
124 (2016).
14. L. Ma, S. Glazier, R. Petibon, J. Xia, J. M. Peters, Q. Liu, J. Allen, R. Doig, and
J. Dahn, Journal of The Electrochemical Society, 164, A5008 (2017).
15. M. Nie, J. Xia, and J. R. Dahn, Journal of the Electrochemical Society, 162, A1186
(2015).
16. D. S. Hall, M. Nie, L. D. Ellis, S. L. Glazier, S. Hyatt, R. Petibon, A. Xiao,
W. M. Lamanna, K. Smith, I. G. Hill, and J. R. Dahn, Journal of The Electrochemical
Society, 163, A773 (2016).
17. T. Jow, M. Ding, K. Xu, S. Zhang, J. Allen, K. Amine, and G. Henriksen, J. Power
Sources, 119, 343 (2003).
18. S. S. Zhang, K. Xu, and T. R. Jow, Journal of The Electrochemical Society, 149,
A586 (2002).
19. N. Pereira, M. C. Ruotolo, M. Y. Lu, F. Badway, and G. G. Amatucci, J. Power
Sources, 338, 145 (2017).
20. L. D. Ellis, J. Xia, A. J. Louli, and J. R. Dahn, Journal of The Electrochemical Society,
163, A1686 (2016).
21. A. M. Wise, C. Ban, J. N. Weker, S. Misra, A. S. Cavanagh, Z. Wu, Z. Li,
M. S. Whittingham, K. Xu, and S. M. George, Chemistry of Materials, 27, 6146
(2015).
22. D. Mohanty, K. Dahlberg, D. M. King, L. A. David, A. S. Sefat, D. L. Wood,
C. Daniel, S. Dhar, V. Mahajan, M. Lee, and F. Albano, Scientific reports, 6, 26532
(2016).
23. R. S. Arumugam, L. Ma, J. Li, X. Xia, J. Paulsen, and J. Dahn, Journal of The
Electrochemical Society, 163, A2531 (2016).
24. D. J. Xiong, R. Petibon, M. Nie, L. Ma, J. Xia, and J. R. Dahn, Journal of The
Electrochemical Society, 163, A546 (2016).
25. A. Smith, J. Burns, S. Trussler, and J. Dahn, Journal of The Electrochemical Society,
157, A196 (2010).
26. L. Downie and J. Dahn, Journal of The Electrochemical Society, 161, A1782
(2014).
27. A. J. Smith, J. C. Burns, and J. R. Dahn, Electrochemical and Solid-State Letters, 14,
A39 (2011).
28. R. Petibon, C. P. Aiken, N. N. Sinha, J. C. Burns, H. Ye, C. M. VanElzen, G. Jain,
S. Trussler, and J. R. Dahn, Journal of the Electrochemical Society, 160, A117
(2012).
29. R. Petibon, E. C. Henry, J. C. Burns, N. N. Sinha, and J. R. Dahn, Journal of the
Electrochemical Society, 161, A66 (2013).
30. R. Petibon, N. N. Sinha, J. C. Burns, C. P. Aiken, H. Ye, C. M. VanElzen, G. Jain,
S. Trussler, and J. R. Dahn, J. Power Sources, 251, 187 (2014).
31. C. Chen, J. Liu, and K. Amine, J. Power Sources, 96, 321 (2001).
32. J. C. Burns, L. J. Krause, D. -B. Le, L. D. Jensen, A. J. Smith, D. Xiong, and
J. R. Dahn, Journal of The Electrochemical Society, 158, A1417 (2011).
33. J. Burns, L. Krause, D. -B. Le, L. Jensen, A. Smith, D. Xiong, and J. Dahn, Journal
of The Electrochemical Society, 158, A1417 (2011).
34. L. Krause, L. Jensen, and J. Dahn, Journal of The Electrochemical Society, 159, A937
(2012).
35. P. Ping, Q. S. Wang, J. H. Sun, X. Xia, and J. R. Dahn, Journal of the Electrochemical
Society, 159, A1467 (2012).
36. J. Self, C. Aiken, R. Petibon, and J. Dahn, Journal of The Electrochemical Society,
162, A796 (2015).
37. N. N. Sinha, J. Burns, R. Sanderson, and J. Dahn, Journal of The Electrochemical
Society, 158, A1400 (2011).
38. T. M. Bond, J. C. Burns, D. A. Stevens, H. M. Dahn, and J. R. Dahn, Journal of The
Electrochemical Society, 160, A521 (2013).
39. H. M. Dahn, A. Smith, J. Burns, D. Stevens, and J. Dahn, Journal of The Electro-
chemical Society, 159, A1405 (2012).
40. K. L. Gering, Electrochimica Acta, 51, 3125 (2006).

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