Review

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Methods and Protocols for Electrochemical Energy Storage Materials

Research
Elahe Talaie,† Patrick Bonnick,† Xiaoqi Sun,† Quan Pang,† Xiao Liang,† and Linda F. Nazar*
Department of Chemistry and the Waterloo Institute of Nanotechnology, University of Waterloo, 200 University Avenue, Waterloo,
Ontario N2L 3G1, Canada
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ABSTRACT: We present an overview of the procedures and methods to prepare and evaluate materials for electrochemical cells
in battery research in our laboratory, including cell fabrication, two- and three-electrode cell studies, and methodology for
evaluating diffusion coefficients and impedance measurements. Informative characterization techniques employed to assess new
materials for batteries are also described, including operando XRD, pair-distribution function analysis, X-ray photoelectron
spectroscopy, and operando X-ray absorption spectroscopy. Examples of insightful information that each technique has provided
in the research areas of Li-S, Na-ion, and Mg batteries are presented along with excellent references for detailed descriptions of
the theory, experimental procedures, and various designs, as well as methods for data processing and analysis.

■ INTRODUCTION
Development of high-performance and cost-effective energy
storage technologies is an attractive subject of research today
due to the growing energy demand and the necessity of
providing it from clean and renewable sources. Efficient use of
electricity generated from renewable energy sources relies on
the development of sustainable and low-cost energy storage
systems to integrate the energy from intermittent sources, such
as wind and solar energy, into the electrical grid; electro-
chemical energy storage systems, and in particular batteries,
have emerged as promising candidates to meet this demand.1,2
Lithium-ion batteries are extensively employed in portable
electronic devices, and their application has expanded to the
electric vehicle market, which is expected to increase rapidly.3
Today, various battery technologies beyond Li-ion batteries,
such as lithium-sulfur (Li-S),4−6 sodium-ion (Na-ion),7−10 and
magnesium (Mg)11−13 batteries, have gained much attention
from the research community due to their advantageous
sustainability, cost-effectiveness and/or high capacity, although
many challenges have to be overcome for them to compete
with state-of-the-art Li-ion batteries. Development of high-
performance battery systems requires the exploration of new
promising materials and an in-depth understanding of the
science underlying these devices, such as the redox reactions,
the interaction of the electrodes with the electrolyte, and aging
mechanisms of each cell component. Characterization of the
chemical composition, morphology, crystal structure, and the
electronic structure of electrode materials, and monitoring the
evolution of those properties during the operation of the
electrochemical cell provide a comprehensive evaluation of new
electrode materials.
Considering the inevitable importance of advanced character-
ization techniques for battery technology research and
development, this paper presents an introduction to some of
the most important characterization techniques commonly
employed for battery evaluation. This paper is not a detailed or
comprehensive description of the characterization techniques of
interest; instead, the goal of this Review is to present a
resourceful starting point for researchers new to the field.
Electrode preparation, coin cell assembly, electrochemical
evaluation techniques, operando X-ray diffraction, operando
pair distribution function analysis, operando X-ray absorption
spectroscopy, and X-ray photoelectron spectroscopy techniques
are discussed, and an example of the application of each
characterization technique in our research is presented.
■ ELECTROCHEMISTRY
Electrode Preparation. Depending on the active material
properties and the experiment purposes, electrode preparation
can be carried out by either doctor blading or drop casting.
Special Issue: Methods and Protocols in Materials Chemistry
Received: July 4, 2016
Revised: August 30, 2016
Published: September 4, 2016

© 2016 American Chemical Society 90 DOI: 10.1021/acs.chemmater.6b02726

Chem. Mater. 2017, 29, 90−105
Chemistry of Materials
Doctor blading requires at least one hundred milligrams of
active material and gives a more homogeneous coating, whereas
drop casting can be done with 10 times less material and is
normally used for early-stage testing of new materials. Both
procedures are described in detail below.
During either method of electrode preparation, additives
binder are mixed together with the active material in order to
increase the conductivity, elasticity, and viscidity. A common
initial weight ratio of these three components is active material:
carbon:binder = 8:1:1. However, these numbers should be
modified based on the specific properties of the active material;
for example, more carbon can be added to aid non-conductive
active materials. A slurry is made by grinding the above mixture
in a solvent that has a high solubility for the binder. N-Methyl-
2-pyrrolidone (NMP) is normally used with polyvinylidene
fluoride (PVDF) binder, for instance. For the doctor blading
procedure, the slurry should be relatively “thick”, with a 25−
30:1 weight ratio of solvent to the binder as a good starting
point. The homogeneous mixture is then cast by depositing a
“tooth-shaped puddle” onto a large piece of metal or carbon foil
that serves as the current collector, and gliding a doctor blade
over the puddle and down the foil to spread out the slurry.14
The foil is then placed in an oven at, for example, 60 °C for 2 h
to evaporate the solvent. Afterward, the cast spread can be
further pressed by passing it through a cold or hot roller press
to achieve better contact.14 Finally, small electrodes are cut
from the cast spread, usually by using an electrode “punch” to
punch out circular electrode disks. The active material loading
of each electrode is determined by weighing “blank” disks of the
current collector foil without “electrode material” on them and
finding the average mass. Then this average current collector
mass is subtracted from the mass of an electrode to determine
the mass of electrode material present. That mass is then
multiplied by the percentage of the electrode material that is
active material (80% in our example 8:1:1 mixture) to
determine the active material loading.20
For drop casting, the slurry is added dropwise to the
individual pre-cut current collectors. Thus, the weight of each
current collector can be weighed beforehand to acquire an
accurate loading. Almost all of the slurry can be transferred to
the current collectors during drop casting so that only a small
amount of active material is required. For example, if one
intends to make a batch of 10 electrodes with a loading of ∼5
mg/electrode, only ∼50 mg of active material powder is
needed. The slurry is relatively “thin” for drop casting, meaning
that more solvent is needed compared to the doctor blading
method. Typically 5−6 drops are required for a 16 mm
diameter current collector, which means ∼80 μL of slurry/
electrode. However, this value will fluctuate based on the
solvent and pipet type. The electrodes are then dried in an oven
to remove solvent and moisture. Note that it is relatively
complicated to pass the small electrodes through a roller press,
thus this step is normally omitted for drop casting.
A very important consideration for handling and storage of
materials and preparing the electrodes is their air stability. For
some materials, the reactivity with ambient atmosphere impacts
various properties, including the electrochemical performance.
Layered sodium transition metal oxides, in particular, are
known to be unstable in air; insertion of water molecules,
uptake of oxide ions, and reactivity with carbon dioxide are
different reported mechanisms.15−19 In order to prepare air-
protected samples in our Na-ion battery research, the as-
prepared powder samples, which are synthesized in air, are
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subjected to a heat treatment (at 600 °C for Na0.67[Mn0.5Fe0.5]-
O2) under vacuum or an inert atmosphere and then are
transferred to an argon-filled glovebox. All the steps of the
electrode preparation and the cell assembly are performed
within the glovebox.
Coin Cell Assembly. In addition to their application as
commercial primary batteries, coin cells have been used for
research on rechargeable Li and Li-ion batteries for the last 30
years. Their benefits include being small, fast and easy to
assemble, and the feasibility of testing of small amounts of
novel active materials.20 Therefore, coin cells have been used
for initial work to identify high-performing materials, in
addition to modifying the compositions, fabrication parameters,
and cycling conditions in laboratories.21 There are many types
of coin cells. Their number is based on their dimensions; e.g.,
CR2325 represents a cell with a 23 mm diameter and a 2.5 mm
thickness. For the purposes of consistency, all the cells used in
our laboratory are of the CR2325 type.
Figure 1 is a schematic representation of a typical coin cell
assembly in our laboratory. The cell caps and spacers are made
Figure 1. Schematic representation of a coin cell.
from 430 BA stainless steel (NRC, Canada). Using a non-
corrodable stainless steel for the casing and the spring is
extremely important. The spring is made from 301 SS,
providing loading forces of up to 12 pounds at a deflection
of 1 mm. The separator is either Celgard 3501, made from
microporous polypropylene monolayer membrane, or glass
fiber. The anode material used in our studies includes Li, Na or
Mg metal, depending on the cathode active materials. Both the
anode and cathode are punched to discs with 16 mm or 11 mm
in diameter. Precise control of the electrolyte volume is
necessary due to the limited space in the coin cell (the
electrolyte volume should be less than 100 μL according to our
experience). Particularly for the Li-S battery, the performance is
highly affected by the amount of the electrolyte. The electrolyte
measured by a micropipette is dropped on the separator before
the anode is placed in the cell. The coin cells are sealed by a
crimping machine (MTI Corporation) in an Ar-filled golvebox
after all the components are stacked and aligned as shown in
Figure 1. Cells should be conditioned for at least 2 h in a static
state at room temperature prior to electrochemical inves-
tigation, enabling the electrolyte to wet the electrodes and
separator.
Electrochemical Performance Evaluation. Electro-
chemically charging and discharging a new electrode material
is the most common and important experiment carried out in
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Chem. Mater. 2017, 29, 90−105
Chemistry of Materials
the pursuit of better batteries and is generally the first
experiment that researchers look for when reading a paper
about a new material. Charging an electrode and then
discharging it comprises one cycle, with either the charge
step or discharge step being referred to as a half-cycle. In the
laboratory, cycling is usually carried out using a constant
current (i.e., galvanostatically), although other charging
methods exist that are more appropriate in certain situations.22
Any charge or discharge half-cycle must be terminated after a
certain amount of time (or charge) or when the working
electrode reaches a particular potential. If a time (or charge)
limit is used, overcharging or overdischarging commonly occurs
after several cycles; over(dis)charging is the continuation of
(dis)charge past the point where all of the active material has
been (dis)charged, and some other cell component, like the
electrolyte, starts to break down in order to absorb or provide
electrons. When using non-aqueous electrolytes, potential
limits are usually used to avoid overcharging or overdischarging
since this usually reduces the state of health of the cell (i.e., how
many cycles it is still capable of). In aqueous cells overcharging
or overdischarging usually consumes H2O to produce either H2
or O2 gas, which can be safely vented, thereby allowing time (or
capacity) limits to be used.20
The term “C-rate” is commonly used in the battery research
community to represent a constant current. The C-rate is the
expected capacity, C, of the working electrode divided by the
desired number of hours to fully (dis)charge that capacity (i.e.,
a half-cycle). The expected capacity can be calculated using the
mass of active material in the electrode and multiplying by the
specific capacity (mAh/g) of the active material, or measured
by cycling the cell once or twice and then declaring the ‘initial’
discharge capacity to be the expected capacity (at a specific
rate). Researchers can use either, but they must define in their
publications which method they have used. As an example, a
working electrode with a mass of active material corresponding
to 2 mAh that is to be discharged in 4 h would be discharged at
a C/4 rate, which is equal to 2 mAh/4 h = 0.5 mA in this case.
The cell might finish discharging in only 3 h (conveying
instantly to the reader that it achieved 75% of its expected
capacity) but it is still understood to have been discharged at a
C/4 rate by the definition chosen in this case. Reporting
currents in C-rates aids readers by inherently compensating the
current for the capacity of the electrode. Note that a C-rate is
effectively the same as mA/gactive material. Currents can also be
reported in mA/cm2, which is appropriate when the surface
area of the electrode is a parameter being varied, or a
particularly large or small surface area is being used.
The primary figure that readers are usually interested in is the
discharge/charge curve, which is a plot of potential vs time,
specific capacity or a stoichiometric variable, such as x in
MgxTi2S4. An example is shown in Figure 2.23 The length of
this curve is a measure of the charge or discharge capacity and,
for a particular material, is dependent on the temperature, rate
(/cm2) and state of health of the electrode (i.e., history). The
C-rates in Figure 2 were calculated using the mass of active
material in the electrodes and the assumption that 1 Mg2+ per
Ti2S4 unit could be intercalated. Figure 2 shows that higher
capacities are achieved at higher temperatures, lower rates, and
lower cycle numbers. Reporting the effect of each of these three
parameters on the capacity and shape of the potential curve is
recommended for a new material. The shape of this curve is
determined by both the thermodynamics and kinetics of solely
the working electrode in a three-electrode cell, or both the
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Figure 2. First and second cycles of spinel MgxTi2S4/APC/Mg coin
cells at various current rates, and either 60 or 20 °C. The discharge
half-cycles are the bottom half of each “loop” and begin at the top left
of the plot, progressing down toward the bottom right. Charge half-
cycles are the upper half of each “loop” and begin at the bottom right,
progressing up toward the top left. Adapted from ref 23.
working and counter electrode in a two-electrode cell (see
below). It is best to know what the potential curve of each
electrode looks like individually, so at least one three-electrode
measurement of a new electrode is recommended unless the
counter electrode in the two-electrode cell is highly non-
polarizable. In general, a flat plateau in the potential curve
signifies a two phase reaction (with a constant chemical
potential), whereas a sloped “plateau” (i.e., changing chemical
potential) signifies a change in solution concentration (e.g., the
solid solution formed via intercalation of Mg2+ in Ti2S4 in
Figure 2). A steep decline (or rise) in the potential signifies the
kinetic limit at which a reaction is no longer capable of
absorbing the constant current being forced out of (or into) the
electrode.24 Two types of transitions are common in
intercalation materials: ordering25,26 and staging.27,28 Some-
times a slight drop in potential between two sloped plateaus,
like the drop at about 110 mAh/g in Figure 2a, is due to an
order/disorder transition in an otherwise solid solution.
These distinct features in the potential curve are more easily
seen in a differential capacity (dQ/dV) plot, which is the
inverse of the derivative of the potential vs specific capacity
curve discussed above, plotted against the potential. An
example for a LixMn2O4 electrode is shown in Figure 3.29
Plateaus in the V vs Q curve appear as peaks in the dQ/dV plot;
the flatter the plateau, the narrower the dQ/dV peak. Each peak
feature represents a different chemical reaction or intercalation
environment (in the case of ordering and staging) and the area
under the peak is the capacity of that particular process. To
those familiar with cyclic voltammograms (CV) this may sound
similar, and in fact, a CV yields the same information but under
different circumstances. The y-axis in a typical CV is current, I,
which can be converted to dQ/dV by dividing by the sweep rate
(ν = dV/dt):
I dQ /dt dQ
= =
ν dV /dt dV (1)
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Chem. Mater. 2017, 29, 90−105
Chemistry of Materials
Figure 3. (a) Potential curves of LixMn2O4+δ vs Li metal. (b) Differential capacity plot derived from the potential curves in (a) and a cyclic
voltammogram (CV) of the same electrode. Constant current experiment: C/8 = 0.33 mA/cm2. CV: 0.04 mV/S (sweeps up and down in 6.9 h).
Adapted from ref 29.
The difference between the methods is that the differential
capacity is collected at a constant current, which gives the
various electrochemical processes more time to reach
completion, whereas a CV is collected with a constant potential
sweep rate (i.e., μV/s). This forced change in the potential,
regardless of the state of charge of the electrode, can increase
the current beyond the kinetic limit of the cell, thereby
preventing some capacity from being accessed. Additionally, the
IR drop of the cell remains unchanged throughout the constant
current scan but varies throughout a CV sweep, which alters the
peak shape. These effects combine to produce the two curves in
Figure 3 from the same electrode. Note the superior resolution
of the dQ/dV plot in comparison to the CV. The advantage of a
CV is that it contains rate information about the full cell, so this
method might be preferred by researchers testing electrolytes,
separators or electrode architectures, for example. Researchers
focused on electrode materials usually use constant current
differential capacity plots. When converting a V vs Q plot into a
dQ/dV vs V plot, it is common to end up with “noisy” data. To
collect smoother data, try (1) tightly controlling the temper-
ature of the cell, (2) collecting a data point only every few mV
as opposed to either every few mV or every few min, and (3)
cycling at a very slow rate (e.g., C/100).
Another important measurement to perform when character-
izing a new electrode material is the cycle life, which compares
charge and discharge capacities to the cycle number as shown
in Figure 4a.30 In cases like this example where the charge and
discharge capacities overlap for the entire plot, it is acceptable
to omit the charge data. A cell is considered to be at the end of
its cycle life when its discharge capacity sinks below a critical
threshold, which is up to the researcher but is usually 80% of its
initial discharge capacity,31 ignoring the first cycle if a notable
drop in discharge capacity occurs from the first to second cycle.
For example, the Li-S cell in Figure 4a has a first discharge
capacity of 1100 mAh/g and a second cycle discharge capacity
of 850 mAh/g. The first discharge capacity was ignored, and so
this cell reached the end of its cycle life when it delivered <680
mAh/g around cycle 420. In the case of Li-S cells, performing
the first cycle at a very slow rate (C/20 to C/50) improves the
cycle life.30 Other cell chemistries like Ni-Zn also benefit from
performing the first few cycles of the regime differently than the
rest,20 but this is chemistry-specific and so a complete list of
recommendations is not possible here. When reporting the
cycle life, as in Figure 4, all cycles up to the 80% end of life
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Figure 4. Example cycle life plot featuring a Li-S cell cycled at a C/2
rate between 1.8 and 3.0 V, at 20 ± 2 °C. Only every fifth data point is
shown for clarity. Adapted from ref 30. Panel b shows the same CE
data as in a, but with the right y-axis magnified to the point of
usefulness.
threshold should be reported. Some researchers only report the
cycles where the cell is healthy and performing well, but
reporting all of the cycles collected better reflects the
limitations of the cell design. Two final thoughts on cycle life
measurements: (1) Electrolyte loss (evaporation) through the
seals of the cell is one of many possible causes of cell failure, but
this one is commonly overlooked and can be identified by
weighing cells before and after cycling. (2) The stability and
value of the temperature at which the cell was cycled can be
important and should be reported (the temperature range can
be conveyed with a ± as in the caption of Figure 4).
Figure 4 also shows the Coulombic efficiency (CE), which is
the discharge capacity divided by the preceding charge capacity
or sometimes vice versa (CE = QD/QC, or sometimes QC/
QD).32,33 The CE generally reveals the presence of parasitic
reactions that siphon charge away from the intended reaction,
i.e., charging the electrode.33 The exact cause of a CE ≠ 100%
varies from system to system, but a large departure (|100% −
CE| ≳ 2%) is alarming since either the electrode or the
electrolyte is being consumed at a likely unsustainable rate,
although cells with aqueous electrolytes can withstand higher
departures since H2O can be replaced. In the case of Li-ion cells
with a limited supply of Li+ ions, to deliver 3000 cycles before
reaching a 50% end of cycle life limit the CE must be ≥99.98%
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Chem. Mater. 2017, 29, 90−105
Chemistry of Materials
(CE3000 = 50%), while 500 cycles still require a CE ≥ 99.86%
(assuming an exponential capacity loss with cycle number)
since Li lost to parasitic reactions permanently reduces the
capacity of the cell.33 As such, a plot of CE vs cycle with a y-axis
scale ranging from 0% to 100% (or similar) hides the true
expected cycle life of the cell since 99.86% cannot be
distinguished from 99.98%, as shown in Figure 4a. Unfortu-
nately, most instruments are not accurate enough to measure
CE to ± 0.01%.32 In the absence of a high precision charger,
researchers should know the accuracy of their instruments and
temperature control, and report it in addition to using a y-axis
scale that allows the CE values to be easily determined, as
shown in Figure 4b. Researchers can also use symmetric cells to
improve the accuracy of their CE measurements as described in
ref 34.
Two-Electrode versus Three-Electrode Cells. The
electrochemical measurement can be carried out with two
electrode or three electrode configurations. In the two
electrode setup, the material of interest is assigned as the
working electrode (WE), while the other electrode serves as
both the auxiliary electrode (AE, also called counter electrode)
and the reference electrode (RE). In order to be a good RE in
addition to an AE, the AE should have a small overpotential
and a stable voltage during electrochemical processes. Lithium
and sodium metals in rechargeable Li and Na cells are good
such examples. Positive electrode materials are frequently
studied in two electrode configurations with the corresponding
metal as the AE/RE. Such a configuration also reflects the
behavior of the entire system and provides a more realistic
portrayal of the properties to be expected in a commercial
version of the cell. Thus, two electrode cells are widely used for
cycle life evaluation when the specific reactions at either
electrode are not the major concern. The readily available two-
electrode cell designs include coin cells and Swagelok cells. Due
to the easy assembly and low price of two electrode cells, they
are preferred if a separate reference electrode is not necessary.
Since the result given in the two electrode setup is a
combination of WE and AE signals, an approximation is taken
here that the electrochemical response at AE is small enough so
that the overall result represents the properties of the WE.
However, sometimes the WE signal needs to be well separated
in order to study the mechanisms in detail, or there is no
suitable material to serve as both the AE and RE. In those cases,
an individual RE is required and this can be accomplished in
the three electrode setup. A good RE material should provide a
stable and accurate voltage. Examples include the silver/silver
chloride electrode, saturated calomel electrode, and mercury/
mercury oxide electrode for aqueous systems, as well as silver/
silver nitrate, or ferrocene for non-aqueous systems. A simple
setup is obtained by immersing the three electrodes in a beaker
cell. There are also other available three-electrode cell designs,
such as the Conflat cell,35 T-shaped Swagelok cell,36 and
modified coin cell,37 where the cells are airtight and only a small
amount of electrolyte is required. Note that special care needs
to be taken for impedance measurements because the cell
geometry has a significant influence on the results.38,39
One good example for using a three electrode setup is in Mg
battery research. The limitation of available electrolytes that
both facilitate Mg deposition and stripping, and resist oxidation
at high potentials makes it problematic to couple a high voltage
oxide-based positive electrode with a Mg metal negative
electrode in a Mg full cell. As a result, new positive Mg
electrodes are commonly evaluated in cells using high surface
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area carbon as the AE. The charge transfer at the AE occurs
through the double layer capacitance mechanism, which results
in a sloping voltage curve. Therefore, a RE is required to
measure the voltage response of the positive (working)
electrode. A three-electrode Conflat cell was used for testing
MnO2 as a new Mg positive electrode.40 A passivation layer is
readily formed on the surface of Mg, so it may experience a
large overpotential (over 2 V) when plating/stripping in the
Mg(TFSI)2 in the diglyme electrolyte used in this study; this
value is largely reduced when extremely low current is involved,
nonetheless, making Mg metal a passable RE. The voltage
profile of the MnO2 WE (Figure 5a, blue) exhibits flat plateaus,
indicating a two-phase reaction mechanism, whereas the
sloping curve of the carbon AE (Figure 5a, red) confirms its
capacitive performance. Without the reference electrode, it
would be impossible to separate the contributions of either
electrode from the overall voltage response (Figure 5) or to
gain insight into the individual electrochemical mechanisms.
Another example usage of the three-electrode setup is in a
Mg-Li hybrid cell, with a Prussian blue analogue (PBA) positive
electrode and Mg metal negative electrode coupling through a
Mg-Li dual-salt electrolyte.41 In such a system, the Li
(de)intercalation into PBA (Figure 5c, blue), Mg plating/
stripping at the negative electrode (Figure 5c, red), and the
overall cell performance (Figure 5d) are examined at the same
time. Since all three sets of data are required to understand the
detailed processes of the hybrid cell, the three electrode cell is
necessary to obtain all the information.
Chemical Diffusion Coefficient Measurements. For
intercalation electrodes (e.g., AxB, where Ay+ is a mobile ion
and B is the host lattice), another useful characteristic to
measure is the chemical diffusion coefficient, D, of the ion, Ay+,
traveling through the host lattice, B. There are four different
techniques generally used to measure D: the galvanostatic
intermittent titration technique (GITT),42−44 the potentiostatic
intermittent titration technique (PITT),42−44 the charge pulse
relaxation (CPR) technique,45 and electrochemical impedance
spectroscopy (EIS).46 Here we will limit our discussion to
GITT, which provides measurements of several other quantities
like the equilibrium potential curve and partial conductivity all
in one experiment.44 The mathematics behind the theory of
these experiments were explained by Weppner, Huggins, and
Wen,42−44 and so only a brief explanation of the method is
repeated here along with a discussion of the experimental
considerations. In a GITT experiment, a three-electrode cell is
used and a constant current is applied to the working electrode
for a period of time, followed by an open circuit rest period
before repeating the current pulse and rest period many times.
An example is shown in Figure 6. These pulses are continued
until the electrode will not accept any more charge (i.e., the
potential plummets/spikes to the point where an undesirable
side reaction occurs) or a desired equilibrium potential limit is
reached. The current pulses can be short (e.g., 1/500th of
capacity) or long (e.g., 1/20th of capacity). Short pulses are
preferable when the reference electrode potential does not
change upon activation of the pulse (as it can, for instance
when using a passivation-prone quasi-reference electrode like
Mg foil), and the working electrode potential recovers quickly
during the rest period, while longer pulses can outlast transitory
behavior of the cell. One of the bonus pieces of information
collected during a GITT experiment is the equilibrium voltage
curve (V vs Q, but without electrode polarization). Theoret-
ically, the equilibrium voltage curves collected during charge
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Chemistry of Materials
Figure 5. (a,b) Voltage profiles of MnO2 vs carbon cycled in Mg(TFSI)2 in diglyme electrolyte at C/20 and the room temperature, using Mg metal
as the RE. (c,d) Voltage profiles of PBA vs Mg cycled in Mg-Li dual salt electrolyte at C/10 and the room temperature, using Mg metal as the RE.
(blue, red, and green show WE, AE, and WE − AE response, respectively). Adapted from refs 40 and 41.
and discharge would superimpose, but in practice their
proximity to one another depends on how long the rest period
is: the longer it is, the closer the two equilibrium voltage curves
will be, but the longer the experiment will be (e.g., one
discharge in 1 month). Note that very long times (e.g., 2
months)47 are required to return the potential to the “true”
equilibrium potential.48 Of primary importance to the
researcher attempting to determine D is the pulse V vs t
data. D can be determined using the following equation:43
4 ⎛ IVM ⎞ ⎡⎛⎜ dV ⎞⎟ ⎛ dV ⎞⎤
2 2
⎛ L2 ⎞
D= ⎜ ⎟ ⎢ ⎜ ⎟⎥ ⎜t ≪ ⎟
π ⎝ nFS ⎠ ⎣⎝ dx ⎠ ⎝ d t ⎠⎦ ⎝ D⎠ (2)
where I is the current, VM is the molar volume of the host
lattice, n is the oxidation state of the mobile ion, F is Faraday’s
constant, S is the electrochemically active surface area, dV/dx is
the slope of the equilibrium voltage curve at the initial value of
x in the present pulse, and dV/d√t is the slope of the V vs √t
plot formed from the V vs t data. In theory, a plot of V vs √t,
where the initial t value is reset to 0 for any pulse, as shown in
Figure 6b, should yield a straight line, as shown in Figure 6c. In
practice, it is non-linear close to t = 0 due to double layer
charging and other transitory effects, and at long times when t
≪ L2/D is no longer satisfied. L is the diffusion length, which is
basically half the thickness of the host material particles and can
be estimated using VMnAM/S = L.43 D must be found iteratively
(i.e., measure D then go back and check if t ≪ L2/D is
satisfied). If the V vs √t plot does not contain any straight
sections, the diffusion length might not be long enough. For
this reason, it is common to make pellet electrodes instead of
cast electrodes and to assume that the pellet acts as one large,
thick particle with no pores. Pellet electrodes should ideally be
95
Review
made without binders, carbon or other additives to maintain
electrode homogeneity, and minimize interfaces. The assump-
tion of a pore-free pellet can be rationalized by considering that
diffusion of active species through the electrolyte down the
pores will be slow due to the size and tortuosity of the pores. As
such, the active species in the pores will become depleted or
saturated relatively quickly when the current is switched on,
and so will ultimately only affect the electrode kinetics for a
short time before the activity of the pores is effectively shut
down. Determining the “true” surface area, S, of the sample is
also difficult and made easier by using a pellet and assuming the
geometric surface area is the true surface area. In certain
situations, it is possible to deposit a perfectly flat, pore-free, thin
layer of an active material where the true surface area is the
geometric surface area.49
As an additional check to confirm that the collected signal is
indeed reflective of diffusion, pulses with different currents, as
shown in Figure 6a, can be collected and used to form a plot of
dV/d√t vs I, as shown in Figure 6d. According to eq 1, after
some rearranging, this plot should form a straight line. Some
care should be taken to maintain the same x value when
performing these experiments, which can be accomplished by
alternating charge pulses with discharge pulses so that the ion
concentration (x) within the host lattice (B) remains constant
between pairs of pulses, as shown in Figure 6a. The slope of the
resulting dV/d√t vs I line can then be used with eq 1 to
calculate D while inherently compensating for some exper-
imental error by using a linear least-squares fit to calculate an
average D value instead of using individual data points. If the
researcher is interested in determining the migration activation
energy, Em, then the chemical diffusion coefficient, D, must be
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Figure 6. Example procedure for determining the chemical diffusion coefficient D at a particular potential (composition) using a spinel MgxTi2S4
pellet in a three-electrode cell. (a) Charge (red), discharge (blue), and open-circuit (black) time periods. (b) Expanded view of left charge curve in
(a) with the time reset to start at 0. (c) Data from (b) plotted vs √t and shifted vertically to have a 0 y-intercept for demonstration purposes. Each
line comes from fitting a charge/discharge pulse with a different current from (b). (d) The slopes of the lines in (c) plotted vs the current of those
pulses. The slope of this line can be used to calculate D.

measured at several different temperatures and then converted
to the so-called self-diffusion coefficient, DAy+, via
D = WD Ay+
where W is a thermodynamic enhancement factor that changes
based on the properties of the host lattice as described by
Weppner and Huggins.44 DAy+ is related to Em through
a 2ν −Em / kT
D Ay+ = e common electrical elements such as resistors, capacitors, and
f (4)
where a is the hop distance, ν has the dimension of a frequency,
f is the number of possible directions the ion can hop, k is
Boltzmann’s constant, and T is the temperature.50 The variables
a and f can be guessed using knowledge of the host structure
unit cell; ν can be calculated, but the slope of a plot of ln(DAy+)
vs 1/T will also yield Em and ν.
Electrochemical Impedance Spectroscopy (EIS). A high
impedance in an electrochemical cell can cause large over-
potentials (the difference between the equilibrium and
measured potentials), low energy efficiency, and low rate
capability, and can increase the risk of thermal runaway. It is
important to examine and understand the evolution of
impedance at each state of discharge/charge and over long-
term cycling. Generally, there are three sources of voltage drop:
ohmic loss, charge transfer or activation polarization, and
concentration polarization. EIS is a widely used tool to
diagnose the impedance of an electrochemical system by
recording the current response to an applied potential at
varying frequencies. Since the response of an electrochemical
system, such as a lithium-ion cell, is very non-linear, the
impedance is investigated in a perturbative manner where an
AC voltage of 1−10 mV (with frequencies between 1 mHz and
1 MHz) on top of the controlled DC voltage (usually at OCV)
is applied. Among various ways to present the spectrum, the so-
called Nyquist plot is commonly used in the battery field by
plotting the negative of the imaginary part of impedance versus
the real part for different frequencies. The Nyquist plot usually
consists of one or more semicircles at high frequencies (which
are charge-transfer processes) followed by a spike at low
(3)
frequencies (which is diffusion toward/away from the surface,
i.e., “Warburg” impedance). Note that symmetric axes should
always be used for the Nyquist plot (Figure 7a). EIS data are
commonly analyzed by fitting the curve with an equivalent
electrical circuit model to understand the contribution from
each interface or bulk process. Most of the circuit elements are
inductors. Each element in the model should have a physical
basis in the electrochemistry of the system, and the number of
elements should be minimized to be physically meaningful. Any
curve can be fit perfectly by using a large enough number of
elements (variables), but such a fit would likely be meaningless.
Practically, there can be a number of interfacial diffusional
processes (charge transfer) on both electrodes of a cell. This
can cause errors in interpreting different processes as they may
occur in an overlapping range of frequency resulting in a
depressed semicircle; therefore, a three-electrode setup as
discussed above is preferred. Porous electrodes in particular can
generate many overlapping charge-transfer processes due to
their large, inhomogeneous surface area. A pelletized electrode
with minimized surface area will be useful in this case.
Here we describe the fundamental application of the EIS
technique based on an example of a metallic phase Ti4O7 as a
sulfur host material for a lithium-sulfur battery.51 The
polysulfide shuttling remains a major problem that leads to
random precipitation of Li2S on the cathode surface, loss of
active materials, and long-term capacity fading. We reported
that by using a bifunctional high surface area Ti4O7 as the sulfur
host, the polysulfides can be effectively adsorbed and readily
reduced/oxidized on the surface over discharge/charge, leading
to a controlled precipitation of Li2S/S and thus lower
impedance of the cathode. In order to prove that, EIS analysis
was carried out after the first discharge (product: Li2S) and also
over the first 50 cycles as shown in Figure 7. The spectrum in
Figure 7a consists of depressed semicircles with a spike and was
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Chemistry of Materials Review

Figure 7. Use of EIS technique to understand the impedance of a lithium−sulfur cell using Ti4O7 as a sulfur host material. Nyquist plots of (a)
Ti4O7/S-60 and (b) VC/S-60 (VC = Vulcan Carbon, S-60 = the sulfur composite with 60 wt% of sulfur) cells at a discharged state on the first cycle
at a C/2 rate showing a dramatic difference in the impedance; and Ti4O7/S-60 at (c) discharged and (d) charged status over 50 cycles at a C/2 rate
at different cycle status. Fitted resistance values for (a) and (b) correspond to the equivalent circuit in (e) and are shown in table (f). Adapted from
ref 51.

fitted using the equivalent circuit in Figure 7e. The circuit
consists of an ohmic resistance, Rs, in series with three R||Q
elements. A constant phase element (Q) was used instead of
the capacitor to represent the non-ideal behavior of the system,
as reflected by the depressed semicircles. By referencing to the
physiochemical processes occurring in lithium sulfur cells
reported in the literature,52,53 Rs corresponds to the
uncompensated ohmic resistance (mostly the electrolyte
resistance). The R1||Q1 at the highest frequencies corresponds
to the charge transfer of polysulfide intermediates and R2||Q2 in
the middle frequencies region reflects the precipitation of
resistive Li2S/Li2S2 onto the positive electrode. Lastly, R3||Q3 in
the low frequencies is related to the diffusion of charge carriers
in the solids. We observed that the Ti4O7/S cell exhibits a
charge transfer resistance that is 2-fold lower than that of VC/S
(VC = Vulcan Carbon). This is ascribed to the enhanced
interaction of the LiPS moleculesand subsequently the
Li2Swith Ti4O7. In accord, EIS spectra of Ti4O7/S showed
negligible changes over 50 cycles, as shown in Figure 7c,d.
Operando X-ray Diffraction (XRD) Analysis. Correlation
of the electrochemical performance of electrode materials with
their structural evolution upon battery operation provides
insights necessary to understand their working mechanism,
which is an essential key to the development of high-
performance battery materials. In situ and operando X-ray
powder diffraction techniques are powerful methods to
characterize the structural evolution of battery materials during
charge/ discharge and are widely used today by the research
community.54−62 In an in situ experiment, i.e., on-site
experiment, the data are collected in the same environment
that the material is treated/reacted.63 An example of an in situ
97
experiment is the XRD analysis of an electrode material within
the electrochemical cell at the specific states of charge, whereas
an ex situ experiment involves disassembling of the cell and
extraction of the electrode for further analysis, such as XRD.
The in situ XRD analysis offers the advantage of monitoring the
structural evolution of the same electrode in the same cell
environment at different states of charge, whereas the data
collected ex situ from disassembling several cells might be
affected by the imperfect reproducibility of electrode
preparation and cell assembly. Additionally, the state of charge
can be changed due to short circuiting when disassembling the
cell. Special care should be taken in the case of air-sensitive
samples for ex situ analyses. On the other hand, ex situ analysis
usually results in higher quality data and is required prior to
conducting an in situ experiment.
The term operando (Latin for “operating”) is used when the
material is characterized in situ, simultaneous with the operation
of the reaction, under non-equilibrium and real-time con-
ditions;64 for example, the collection of XRD data from an
electrode material when the electrochemical cell is charged/
discharged. Research conducted by Rojo et al.65 nicely
demonstrated the unique ability of the operando methodology
to obtain information about non-equilibrium conditions. In that
study, a Na0.67[Mn0.8Mg0.2]O2 electrode, with an initial
hexagonal phase (P63/mmc), was charged up to 4.0 V vs Na/
Na+ and then discharged to 1.5 V, at which point the cell was
disassembled and the electrode was extracted for an ex situ
XRD analysis. Two different phases, a small amount of
hexagonal (P63/mmc) and a larger amount of orthorhombic
(Cmcm), were detected in the fully discharged electrode.
However, it was reported that operando/in situ XRD did not
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detect the orthorhombic (Cmcm) phase when the cell was

discharged to 1.5 V under the same cycling conditions (the
same voltage range and current rate) under continuous
operation. It should be noted that the electrode analyzed by
ex situ XRD was disassembled inside the glovebox, washed with
the electrolyte solvent, and protected against air during the data
collection. This observed discrepancy between the results of
these two methods indicates that the orthorhombic (Cmcm)
phase detected by ex situ XRD is formed upon relaxation,
whereas operando XRD under continuous galvanostatic cycling
conditions provides real-time information affected by the
kinetics of the phase transformations. It should be noted that
the phase transitions occurring in an electrode material during
charge and discharge highly depend on the current rate.66
Excellent reviews on various designs of in situ battery cells
have been written by Sharma et al.64 and Brant et al.67 Many
different designs based on coin cells and Swagelok cells, aimed
for reflection and transmission XRD data collection geometries,
and for using conventional diffractometers and synchrotron X-
ray sources are reported.68−77 Generally, cell design for
measurement in transmission geometry is more complicated
compared to reflection geometry. However, in the case of
transmission geometry, the data are collected from both the
positive and negative electrodes and from all the thickness of
the electrode materials. For each experiment, the in situ cell has
to be designed based on the goals of the experiment and the
available experimental setups. An essential feature of a good cell
design is that the electrochemical performance of the studied
material in the in situ cell is equivalent to that of a conventional
Figure 8. (a) Illustration of the evolution of XRD pattern of P2-
cell. A very simple design of an in situ cell is a typical coin cell at Na0.67[Mn0.65Fe0.20Ni0.15]O2 during the galvanostatic cycling at a C/20
which a hole is featured in the positive electrode casing for the rate over the voltage range of 4.3−1.5 V (left), along with a
reflection geometry, or in each stainless steel component of the demonstration of the operando experiment time vs voltage of the cell
cell in the case of transmission geometry. Kapton tape or a (right). (b) Evolution of the average interlayer distance of
beryllium window, both of which are transparent to X-rays, is Nax[Mn0.65Fe0.20Ni0.15]O2 as a function of sodium content, x. Adapted
commonly used to cover the holes. A beryllium window from ref 55.
provides a hermetic seal and a more rigid and flat surface
compared to Kapton tape; however, the latter is lower cost and of sodium content (x). The lattice parameters were calculated
safer to handle. A glassy carbon film, which is light, safe, a good using the Le Bail method.79 The interlayer distance at the high-
electrical conductor, and has good corrosion resistance, is voltage phase (red) decreases upon extraction of sodium ions,
another option for the transparent window of an in situ cell.55 It whereas the opposite trend is observed for the hexagonal (blue)
should be noted that all the window materials mentioned above and orthorhombic (green) phase regions.
cause an increase in the background at low angles and lower The interlayer spacing significantly shrinks upon trans-
stack pressure applied on the electrode under the window.64 formation from the hexagonal phase (blue) to the high voltage
Chapman et al. demonstrated the impact of cell design and also phase (red). These observations evidently indicate a significant
X-ray beam interaction on the electrochemical activity of structural modification at high voltage. Pair distribution
electrodes in a modified coin cell for operando measurements, function analysis (see below) revealed the migration of
highlighting the importance of cell design for reliable results transition metals into interlayer space initiating the high
from these experiments.78 voltage phase transition. In the same study, the deleterious
Figure 8 shows the results of a study of the structural impact of the phase transitions on the electrochemical
evolution of a positive electrode material by the operando XRD performance of the cells was demonstrated.
technique, performed by our team. 55 A sample of Pair Distribution Function (PDF) Analysis. Conventional
Na0.67[Mn0.65Fe0.20Ni0.15]O2 positive electrode material was X-ray and neutron powder diffraction analyses provide
cycled between 4.3 and 1.5 V vs Na/Na+ in the galvanostatic information about the average structure of crystalline materials.
mode with a current rate of 13 mA/g (C/20 rate) while XRD In those techniques, the information is obtained from the Bragg
patterns were collected continuously. The evolution of the peaks only, and the diffuse scattering is discarded in the form of
XRD patterns of the electrode during the first cycle reveals background. The background beneath and between the Bragg
three different phases (Figure 8a): the initial hexagonal phase, peaks in an XRD pattern includes diffuse scattering, which
P2 (blue), a low-crystalline phase at high voltage, Z (red), and contains information about the local structure. PDF analysis
an orthorhombic phase, P′2 (green), at low voltage. The extracts information from both the Bragg reflections and diffuse
reversible transition of the hexagonal phase to the high voltage scattering. The broad range of application of PDF analysis
phase occurs through a two-phase region (black). Figure 8b includes characterization of non-crystalline materials, the study
demonstrates the evolution of the average interlayer distances of disorder in crystalline materials, and research of nano-
of the layered structure Nax[Mn0.65Fe0.20Ni0.15]O2 as a function structured materials.80−85
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Chemistry of Materials Review

For an X-ray PDF analysis, X-ray powder diffraction data are
collected similar to a conventional diffraction measurement.
The diffracted data are then corrected for Compton scattering,
fluorescence, multiple scattering, and scattering from the
sample environment (sample holder, air, instrument). The
resulting coherent scattering function, Icoh(Q), is then
normalized, giving the total scattering structure function,
S(Q), as follows:86
1
S (Q ) = [I (Q ) + ⟨f (Q )⟩2 − ⟨f 2 (Q )⟩]
2 coh
N ⟨f (Q )⟩
An excellent example of the application of PDF analysis used
operando to investigate the local structure evolution of battery
electrode materials can be found in the study conducted by
Chapman et al.89 The operando PDF analysis of an iron
oxyfluoride conversion electrode, FeII(1−x)FeIIIxOxF2−x (x = 0.6),
carried out at a synchrotron, illustrates the variation of atomic
distances and local structural features of the electrode during
the first discharge/charge (Figure 9a). The initial rutile phase
(5)

where Q is the amplitude of the scattering vector (Q =

4π sin(θ)/λ, with θ the Bragg angle and λ the radiation
wavelength), f(Q) is the atomic form factor, N is the number of
atoms, and angle brackets stand for an average over atom types.
The X-ray atomic form factor, f(Q), decreases with the increase
of Q, meaning that the high-Q data information gains more
weight in the total scattering experiment compared to the
conventional XRD. The Fourier transform of the total
scattering structure functions yields the reduced PDF, G(r)80,86
2 ∞
G (r ) =
π
∫0 Q [S(Q ) − 1] sin(Qr ) dQ
(6)

The PDF gives a measure of the probability of finding two

atoms in a material separated by a distance r, as follows:

1 ⎡ bibj ⎤
G (r ) = ∑∑⎢ δ(r − rij)⎥ − 4πrρ0
r i j ⎣ ⟨b⟩2
⎦ (7)

where ρ0 is the average number density of the material; the sum

is over all pairs of atoms i and j with an interatomic distance of
rij; bi is Q-independent scattering amplitude of the atom i and is
equal to the atomic number for X-rays; ⟨b⟩ is the average
scattering length of the sample. Any two atoms in the material
results in a peak in its PDF curve in real space (G(r) versus r);
the peak positions indicate the distance of atom-pairs; the
integrated intensities of the peaks are related to the number of
neighbors in those coordination shells around the origin atoms;
and the shape of the peaks contains information about the
probability distribution of the atom-pairs.
An important requirement for PDF analysis measurement is
the collection of data over a wide range of Q, in order to obtain
high-resolution real space data. Finite Q resolution results in a
gradual decrease of peak-peak intensities and the appearance of
termination ripples (false oscillations in the data) in the
reduced PDF function, G(r). The maximum value of Q in an
XRD measurement is proportional to the maximum scattering
angle and is inversely proportional to the X-ray radiation Figure 9. (a) Evolution of the PDF curve of FeO0.6F1.4 during the first
wavelength, which is why a synchrotron source of X-ray or a discharge/charge at 50 °C and a C/30 rate. (b) Simulated PDF curves
short-wavelength X-ray source (e.g., Ag Kα radiation) in a of the pristine phase and the phases formed upon cycling. (c)
conventional diffractometer is necessary. Good statistics, low Evolution of the phase distribution. Reproduced with permission from
background scattering, and stable experimental set up are other ref 89. Copyright 2013 American Chemical Society.
requirements to ensure high-quality data for PDF analysis. The
experimental PDF can be quantitatively modeled in real-space. transforms into body-centered cubic (bcc) Fe nanoparticles
Similar to the Rietveld refinement, an initial structural model is through an intermediate rock-salt structure phase during the
given to the software, and structure- and experiment-dependent first discharge (Figure 9b). A two-phase nanocomposite
parameters are refined to obtain the best fit. PDFGetX387 and electrode, consisting of the intermediate rock salt phase and a
PDFgui88 are among the available software for reduction of poorly ordered rutile phase (referred to as amorphous rutile), is
reciprocal-space data to real-space data and for fitting the obtained during the subsequent charge. The evolution of the
structural models, respectively. Detailed information about the phase fractions during the first cycle was obtained by
theory, measurement procedure, and data processing of PDF is refinement of structural models against the PDF data (Figure
presented in ref 80. 9c).
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Chemistry of Materials Review

Figure 10. Scheme and examples for operando XAS experiments. (a) Scheme showing an example XAS spectrum that consists of three regions. (b)
Scheme showing the design of the windowed coin cell for operando XAS measurements. (c) 3D plot showing the evolution of sulfur K-edge XANES
spectra as a function of the electrochemical cycling of a lithium sulfur cell in ether-based electrolyte; the end of discharge/charge is in red. (d)
Evolution of each sulfur species (S8, Li2S6, Li2S4, Li2S) as a function of cycling, as quantified by linear combination fitting with the references. Panels
(c) and (d) reproduced with permission from ref 91. Copyright 2013 American Chemical Society.

An example of a conventional diffractometer-based X-ray galvanostatic experiments. Therefore, operando characteriza-

PDF analysis providing insightful information about a
disordered structure can be found in ref 55. In this research
conducted in our laboratory, ex situ PDF analysis along with
operando XRD, Mössbauer spectroscopy, and electrochemical
measurements was employed to understand the phase
transition that occurs in P2-Na0.67[Mn0.5Fe0.5]O2 electrode
upon charge. The high-voltage phase, Z-Na0.1[Mn0.5Fe0.5]O2,
cannot be characterized by conventional XRD due to the low
crystallinity of the structure. The PDF data from the pristine P2
phase and the high-voltage phase, obtained from the chemical
oxidation of the pristine material, was collected by a
PANalytical Empyrean using Ag Kα radiation. Modeling of
the data showed that the migration of a fraction of transition
metals from MO2 layer into the interlayer space occurs at the
beginning of the high voltage phase transition.55
Operando X-ray Absorption Spectroscopy (XAS). XAS
is a widely used technique to determine the electronic structure
and atomic geometric/bonding information of matter.90 It is
useful to examine the phase evolution of the electrode materials
during discharge/charge of the cell. Valuable information can
be obtained by examining the electrodes ex situ by dissembling
the cells at various states of charge. However, since the
electrochemical reactions always proceed in a non-equilibrium
fashion and may not be uniform across the electrodes, ex situ
measurements may not reflect the exact speciation during
100
tions are required.91
XAS is performed using synchrotron radiation sources that
are selected by the energy ranges required. The element specific
spectrum is obtained by plotting the absorption coefficient as a
function of photon energy (eV) and generally consists of three
regions: pre-edge, X-ray absorption near-edge structure
(XANES), and extended X-ray absorption fine structure
(EXAFS), as shown in Figure 10. The first two regions
correspond to the excitation of core electrons to free orbitals
and thus provide information on the electronic states; the last
region appears due to the scattering of the ejected photo-
electrons with the neighboring atoms and thus encapsulates
bonding information. It is worth noting that XAS is a bulk
(micrometer size or larger) technique rather than a surface
characterization technique, and provides information about
evolution of the electrode bulk upon the electrochemical
reaction.
We have used operando XAS to examine the sulfur speciation
in various electrolyte systems for lithium sulfur cells and the
evolution of chemical environments of transition metals in
layered oxides for sodium-host cathodes, in the Advanced
Photon Source (Chicago) and Canadian Light Source
(Saskatoon), respectively. The typical windowed coin cell
setup for the operando experiments in fluorescence mode is
shown in Figure 10. Thin aluminized Kapton film was featured
in the cell design for the penetration of X-rays. The electrodes
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Chemistry of Materials
Figure 11. Examples of XPS spectra to show the interaction between polysulfides and the sulfur host materials. (a) Polar interaction shown by Ti4O7
and Li2S4. (b) Lewis acid base interaction shown by Ti2C MXene and Li2S4. (c) Thiosulfate−polythionate conversion shown by MnO2 and Li2S4.
Adapted from refs 99, 103, and 104.
were coated on porous carbon paper and were placed in the cell
facing the window for maximum beam penetration.91
Here we show the process of operando XAS in our laboratory
using lithium−sulfur chemistry as an example;91 abundant
reports from other research groups can be found else-
where.92−94 The beam size was about 450 × 450 μm, and
the cells were cycled under constant helium flow. For sample
preparation, the 200 μm mesoporous carbon spheres infiltrated
with sulfur were used in a diluted concentration in order to
minimize self-adsorption (for the S K-edge). Linear combina-
tion fitting using synthesized pure (poly)sulfides/sulfur
references on properly normalized spectra was carried out to
quantify the fractions of each species at each stage of cycling.
Figure 10c shows the evolution of the XANES spectra as a
function of electrochemical cycling, which nicely suggests the
consumption of sulfur and formation of polysulfide inter-
mediates in addition to the final product Li2S. Quantitative
analysis enables some conclusions on the sulfur speciation in
ether based electrolytes and the mechanisms that govern the
dissolution/deposition of the redox end members, S8 and Li2S.
For example, we found evidence that upon discharge the rapid
disproportionation of S82‑ by S82−→S62− + 1/4 S80 reaction can
lead to the widely reported discharge capacity of only 75% of
the theoretical value (1675 mAh/g). We have also examined
other electrolyte systems including a polysulfide nonsolvent
(acetonitrile based solvate) and a high donor pair solvent
(dimethylacetamide), where S3•− radical was identified as an
intermediate product.
X-ray Photoelectron Spectroscopy (XPS). The surface
chemistry of the material and the electrode interface influences
the overall performance of the battery; therefore understanding
the interface phenomenon is obviously necessary.95 For
example, the solid−electrolyte interphase (SEI) generated
because of the electrolyte instability with respect to the
anode chemical potential, plays a very important role in the cell
performance.96 Slow and continuous SEI growth leads to
capacity fading and increased cell resistance. XPS is one of the
most powerful analytical tools for studying the chemical
composition of the material and the oxidation state of the
ions near the surface. Note that although the X-ray beam used
for XPS analysis can penetrate to a depth of ∼1 mm, only the
electrons from the top 5−10 nm can escape from the surface.
Depth profiling by argon ion sputtering can burrow below the
surface layer; however, the etch rate is typically only 1−2 nm/
min.97 In contrast to XRD and XAS techniques, XPS is typically
operated under ultrahigh vacuum, therefore, it is difficult to
measure liquid battery systems in operando or in situ mode.
101
Review
Near-ambient pressure X-ray photoelectron spectroscopy
(NAP-XPS) in the pressure range of millibar can be conducted
in operando mode, however,98 as it relies on advanced vacuum
and analyzer technologies, but is not a mainstream technique.
In our research, we have used XPS, for example, to
characterize the surface chemistry of a wide range of sulfur
host materials and to probe their interactions with polysulfides.
Chemisorption of the soluble polysulfides by host materials is
one of the promising approaches to enable spatially located Li2S
precipitation on the host surface, and thus to stabilize the
cycling performance of Li-S batteries.4 These chemical
interactions usually take place on the surface of the sulfur
host materials, accompanied by electron transitions or
coordination, and should be characterizable using XPS. In the
research studies conducted by our team, modifications of the
XPS spectra of the sulfur host materials caused by the reaction
with polysulfides were investigated. The reactions were
conducted in the electrolyte solvent to simulate the cell
environment. XPS analysis can also be applied to cycled
electrodes. The preparation of the sample is identical to that of
the ex situ XRD characterization. Note that the sample cleaning
process is very important as artifacts may be introduced.
Solvents that could react with the sample should not be used,
obviously. The electrolyte solvent for processing of a cycled
electrode is a good choice. We use CasaXPS software with
Gaussian−Lorentzian functions and a Shirley-type background
to fit the spectrum. The binding energies are calibrated using
the C 1s peak at 285.0 eV. The energy separation of doublet
pairs depends on both the principal and angular momentum
quantum numbers of the core level electrons; for example, the
S2p3/2 spin−orbit doublet is 1.2 eV lower than the S2p1/2 spin−
orbit doublet (Figure 11a,c). This powerful analytical technique
is widely accepted by the Li-S battery research community to
reveal the surface chemistry of the cathode materials. Polar
interactions with shifting binding energies (see Figure
11a),99−102 and Lewis acid−base interactions with the new
chemical bond formation (Figure 11b)103 were reported to
entrap the polysulfides in the cathode. By using XPS, we also
detected the thiosulfate−polythionate conversion (Wacken-
roder’s reaction) phenomena when MnO2 was employed as the
sulfur host for a Li-S battery (Figure 11c). 104 The
Wackenroder’s reaction, discovered in 1845, was based in
aqueous solutions,105 but our results show the reaction also
occurs in an organic solvent.
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Chemistry of Materials
■ SUMMARY
This Review presents the procedures and methods to prepare
and evaluate electrochemical cells in battery research. Some of
the most informative characterization techniques employed to
assess new materials for batteries are described here, and
examples of insightful information that each technique has
provided in the research areas of Li-S, Na-ion, and Mg batteries
are presented; excellent references for detailed description of
the theory, experimental procedures, various designs, and data
processing and analysis methods are included.
Galvanostatic charge/discharge analysis is the first step in
characterizing the electrochemical performance of a new
electrode material; the delivered capacity and energy, voltage-
composition curve, cycle life, and columbic efficiency are
among the most important pieces of information that can be
obtained for a new material. Chemical diffusion coefficient
measurements and EIS are more advanced characterization
techniques that provide information about the transport
properties and the possible aging mechanisms of electrode
materials. Operando XRD analysis can illustrate the evolution of
crystal structure of electrode materials during cell operation.
Real-time and non-equilibrium data are revealed by an operando
methodology, whereas an ex situ experiment, which is carried
out after a relaxation period, characterizes the stable state of the
material. PDF analysis is a powerful tool to provide insights
into the structure of low-crystalline and disordered materials.
XAS techniques, which employ synchrotron X-ray radiation, are
broadly used to investigate the electronic state and local
structure of the atoms. Identifying the redox active atoms and
monitoring the evolution of their oxidation states and local
environment in the electrode materials during the cell charge/
discharge processes could be realized by operando XAS. XPS is
an effective technique to understand the surface chemistry of
battery materials, e.g., to study the electrode/electrolyte
interphase.
Electron microscopy,106−108 Mössbauer spectroscopy,109,110
nuclear magnetic resonance spectroscopy,111,112 and online
electrochemical mass spectrometry113−115 are among many
other advanced characterization techniques for battery research
but are beyond the scope of this paper. A broad range of
characterization of different battery components shapes our
picture of the reaction mechanisms, transport properties,
structural stability, thermal stability, and chemical stability of
each part, paving the way for the development of high-
performance batteries. Last but not least, we note the role of
theoretical studies is gaining increasing importance providing
not only an understanding of how battery materials function at
the atomic level, but also in being a vital predictive tool in the
search for new materials.116,117 Increasing effort at combining
theory and experiment is clearly to the benefit of both.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: lfnazar@uwaterloo.ca.
Author Contributions
†
The paper was written with the active contribution of all co-
authors except for L.F.N., who primarily oversaw the
conception of the Review and content, and its final stage
editing.
Notes
The authors declare no competing financial interest.
102
Review
■ ACKNOWLEDGMENTS
L.F.N. and her team gratefully acknowledge past and current
research support from BASF (SE and Canada) through their
Academic Battery and Electrochemistry International Network;
the Joint Centre for Energy Storage Research, a Hub funded by
the Department of Energy, USA; NSERC through their
Discovery, Research Chair programs and student fellowship
programs; and Natural Resources Canada. The Waterloo
Institute for Nanotechnology and the Ontario Government
are thanked for scholarships to some co-authors of this work.
■
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105 DOI: 10.1021/acs.chemmater.6b02726

Chem. Mater. 2017, 29, 90−105