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 Journal of The Electrochemical Society, 2021 168 120503

Galvanostatic Intermittent Titration Technique Reinvented: Part II.

Experiments
Stephen Dongmin Kang,1,z Jimmy Jiahong Kuo,1,2 Nidhi Kapate,1 Jihyun Hong,3
Joonsuk Park,1 and William C. Chueh1
1
Stanford University, Stanford, California 94305, United States of America
2
Northwestern University, Evanston, Illinois 60208, United States of America
3
Korea Institute of Science and Technology, Seoul, Republic of Korea

Following a critical review of the galvanostatic intermittent titration technique in Part I, here we experimentally demonstrate how
to extract chemical diffusivity with a modified method. We prepare dense bulk samples that ensure diffusion-limitation. We utilize
the scaling with t relax + τ − trelax (trelax: relaxation time; τ: pulse duration), avoiding problems with composition-dependent
overpotentials. The equilibrium Nernst voltage is measured separately using small porous particles. This separation between the
diffusion measurement and the titration procedure is critical for performing each measurement in a reliable setting. We report the
chemical diffusion coefficients of LixNi1/3Mn1/3Co1/3O2 and their activation energy. We extract ionic conductivity and compare it
with total conductivity to confirm ion-limitation in chemical diffusion. The measurements suggest that the time scale for diffusion
in typical Li-ion battery particles could be much shorter than that of the intercalation/deintercalation processes at the particle
surface (Biot number less than 0.1).
© 2021 The Author(s). Published on behalf of The Electrochemical Society by IOP Publishing Limited. 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/
1945-7111/ac3939]

Manuscript submitted September 10, 2021; revised manuscript received October 16, 2021. Published December 3, 2021.

The conventional practices1–5 of the galvanostatic intermittent
titration technique (GITT) have produced drastically inconsistent
chemical diffusion coefficients in the literature. The inconsistency not
only ranges over many orders in magnitude but also shows conflicting
dependencies on composition. In Part 16 of this series contribution, we
have identified multiple systematic error sources responsible for the
inconsistency. We have also proposed how to eliminate or mitigate
such errors by modifying the GITT method. The modification is largely
two-fold: preparation of extremely diffusion-limited samples and
utilization of the trelax + τ − trelax time scale during relaxation (τ
is pulse duration; trelax is time with 0 defined at current interruption). In
this sequel contribution, we experimentally demonstrate how to
implement our modified GITT method, following the steps outlined in
Part 1.6 Using LiNi1/3Mn1/3Co1/3O2 (NMC111) as a model system, we
obtain chemical diffusion coefficients (chemical diffusivities), their
activation energies, and ionic conductivity as a function of Li
composition.
Preparation of Closed-Pore Bulk Samples
Enlarging the sample dimension is the most effective way to
ensure that experiments are conducted in a diffusion-controlled
regime. When the experiment is conducted using liquid electrolytes,
the effective sample size depends on whether liquid can penetrate the
sample. In porous materials, the effective length scale subject to
diffusion could be much smaller than the exterior dimensions of the
active material. The ideal sample is therefore a bulk sample with a
density high enough to prevent macroscopic penetration of the liquid
through open pores. Liquid penetration into bulk samples can be
evaluated by comparing the exterior-volume density (apparent
density) with Archimedes density. Density measured with the
Archimedes method is also called “true” density, but this termi-
nology could be misleading in the present context because an
Archimedes density that is 100% of the theoretical value could
indicate an open-pore structure, which is an undesirable sample
geometry.
The challenge in consolidating electrochemical battery materials
is to achieve high exterior-volume density (>90%) while avoiding
the loss of volatile species. Oxygen (and also Li for some
compositions) tends to have high vapor pressures near the sintering
z
E-mail: Stephen.D.Kang@gmail.com
temperature for layered oxides.7,8 One must therefore find optimum
recipes that consolidate the powder material while preserving the
composition.
Here we demonstrate the consolidation of NMC111 as a model
composition. We start with commercially available powder of NMC111
porous agglomerates (Toda) with a size of approximately 10 μm,
consisting of many sub-micron primary particles. We pulverize the
agglomerates by mechanical ball milling. The powder was placed in a
zirconia jar together with 5 mm zirconia balls, and the jar was rotated
on a planetary ball mill (PM 100, Retsch) at 400 rpm for a total active
milling time of 80 min. The pulverized powder was placed in a graphite
die, padded with flexible graphite foil to accommodate thermal
expansion and contraction. The graphite die was rapidly heated in an
induction furnace (ramp rate >50 K min−1) under Ar atmosphere while
applying uniaxial pressure (40–50 MPa). We found that the sintering
temperature was in the range 750 °C–800 °C for this material. Thus, we
hot-pressed at 800 °C for a minimal amount of time (10 min) to
minimize material loss. This process limited the oxygen loss (perhaps
keeping oxygen trapped inside the bulk), allowing for a post-annealing
recovery in stagnant air (800 °C, 1 h). We could not detect Li loss under
these conditions.
Bulk samples consolidated with this recipe had high exterior-
volume density while maintaining identical crystallographic char-
acteristics of the starting powder material. The consolidated sample
shown in Figs. 1a–1b had an exterior-volume density of 93%
(measured using the exterior dimensions of the sample) while
having an Archimedes density of 95% (measured using a He gas
pycnometer, which yields a value equivalent to the upper bound of
an Archimedes measurement), relative to the crystallographic
theoretical value. The measurements indicate that 5% of the volume
corresponds to closed-pores, while only 2% of the volume corre-
sponds to open-pores exposed on the surface. This measurement is in
contrast to the near 100% Archimedes density reported from some
cold-press sintering processes.9,10 For reference, our attempts on
cold-press sintering (while not introducing sintering-aid impurities
and limiting the maximum temperature to 800 °C) typically resulted
in NMC111 pellets with 100% Archimedes density and 70%
exterior-volume density. The powder XRD investigation shown in
Fig. 1c indicates that the hot-press and post-annealed samples have
lattice parameters and Ni-Li antisite defects identical to that of the
starting powder, indicating minimal material loss. Note that more
aggressive pressing or sintering conditions11,12 have been reported to
alter the diffraction patterns.12
 Journal of The Electrochemical Society, 2021 168 120503

Figure 1. Consolidation of NMC111 powder into a closed-pore bulk sample. (a) Photograph of a consolidated bulk pellet with a diameter of 12 mm. Density
measurements indicate that the majority of the pores are closed pores. (b) TEM bright field image of the consolidated bulk sample. (c) Synchrotron powder XRD
comparing the starting powder (above) to that obtained from grinding the bulk sample (below). Powder from the bulk sample was diluted with silica powder to
limit the total absorbance of the specimen. Parameters obtained from Rietveld refinement were identical for both samples (R 3̄ m, a = 2.864 Å; c = 14.25 Å; O
position (z) = 0.259; Ni defects on Li site = 3%).

Minimizing the time and temperature of the hot-press and post-
annealing in air were important in preserving the sample composi-
tion after the consolidation process. After the 10 min 800 °C hot
press, surface XRD from the as-pressed pellet indicated lattice
parameter shifts and peak broadening. However, after post-annealing
in air at the identical temperature, we were able to recover the
composition profile. Other possible routes of consolidation include:
hot-pressing in an oxygen environment (although with challenges
due to thermal expansion problems of oxygen-compatible dies);
using sintering aids to facilitate consolidation without pressure;12
increasing the ramp rate to minimize the sintering time.13
The Li composition of the bulk was controlled electrochemically
using 316 stainless steel coin cells. The consolidated bulk samples
were cut into smaller flat pieces typically with a thickness less than
0.5 mm. The flat sample was sandwiched between porous carbon
sheets and placed in a coin cell. A stack of glass fiber filter sheets
was used as the separator, also serving as a compression element
instead of a wave spring. Li metal was used as the counter electrode,
and an ethylene carbonate/diethylene carbonate (1:1 vol.) mixture
with 1 M of LiClO4 salt was used as the electrolyte. This
construction allowed the coin cell to be disassembled safely without
breaking the bulk sample. After delithiating the bulk sample by a
target capacity, the sample was retrieved from the cell, rinsed several
times in dimethyl carbonate, and annealed in Ar at 85 °C–95 °C for
7+ days (measured temperature; not setting temperature). The
delithiation-annealing process was repeated in small steps (5 to 10
percent of the total Li in one step) to avoid cracking of the bulk
sample. The identical coin cell structure was used for pulse-
relaxation experiments as well. We confirmed with a three-electrode
cell that the counter electrode contribution was negligible in this
bulk-sample setting using a Li metal counter, which is attributed to
the minimal surface area of the bulk sample dominating the overall
cell impedance.
GITT Experiment
Pulse-relaxation experiment.—The pulse-relaxation experiment
for measuring chemical diffusivity is designed according to the
principles established in Part I.6 Each current pulse is designed to
have a minimal magnitude, a duration (τ) that is short enough to
ensure minimal perturbation of the surface composition, but still
long enough to see the time-dependency originating from the bulk
process. Whether the pulse duration is within an acceptable range
has to be later checked after chemical diffusivity values are extracted
from the measurement.
Here, we demonstrate an example GITT pulse-relaxation se-
quence (Fig. 2). Starting with a homogenized bulk sample, a
lithiation current pulse is applied (10 min), followed by a long
relaxation period (5 h). This current pulse is extremely short
considering the sample geometry: our sample thickness (typically
about 0.5 mm) is 50 times larger than the size of agglomerate
particles used in porous electrodes, so the current pulse of 10 min is
equivalent to a diffusion duration of 0.24 s in an agglomerate particle
(diffusion time is length squared). In both the lithiation curve (violet
in Fig. 2a) and relaxation curve (turquoise in Fig. 2a), two distinct
regions are observed. This behavior resembles the “early transient
 Journal of The Electrochemical Society, 2021 168 120503

Figure 2. Example of a GITT sequence on a NMC111 bulk sample. (a) A 10 min lithiation pulse (violet, bottom axis, left to right for time progression) is
applied, followed by a 5 hour relaxation (turquoise, top axis, right to left for time progression). Because of the small number of charges passed through the pulse
relative to the sample capacity, the net composition shift is negligible as indicated from the absence of net change in open-circuit voltage. (b) At least three pulse-
relaxation sequences are repeated, varying the current pulse magnitude. The slope of interest is that related to the bulk relaxation process (chemical diffusion),
rather than the initial transient related to the surface. (c) By plotting the bulk relaxation slope obtained from (b) as a function of current pulse magnitude, one can
separate the Faradaic current from parasitic contributions.

effects” discussed in Part I, and thus we attribute the initial slope to a

surface property and the later slope to a bulk property. To separate
the Faradaic current from the parasitic current, the pulse-relaxation
is repeated at least three times with varying pulse magnitudes
(Fig. 2b). By plotting how the bulk relaxation slope
dV
( d ( t + τ − t ) ) changes with the applied current pulse magnitude
relax relax
(Ictrl), as shown in Fig. 2c, we find the linear scaling factor:
eq
dV 2 v M ∂VLi 1
= (−Ictrl + Ipar ). [1]
d ( t relax +τ − t relax ) π FS ∂xLi D˜

The x-axis intercept gives an estimation of the non-Faradaic parasitic

current (Ipar), the opposite sign of the Faradaic current with a
magnitude <0.5 μA in this example case. Sample surface area S can
be estimated from the sample geometry, F is the Faraday constant,
and the molar volume vM can be taken as the volume of one chemical
unit of LixNi1/3Mn1/3Co1/3O2 if we let xLi represent the Li content x
in this formula. Then, the only factor remaining to be determined is
∂V eq
the Nernst voltage dependency on Li content ( ∂xLi ), discussed in the
Li
next subsection.

Nernst voltage determination.—The Nernst voltage derivative

eq
∂VLi
∂xLi
is needed for converting GITT measurements to chemical
diffusivity. To facilitate equilibration of the Li composition,
agglomerate particles (≈10 μm, Toda) were used rather than bulk
samples. Composite electrodes were made with a dilute content of
active material, consisting of a weight ratio of 6:2:2 for NMC111,
carbon black, and polyvinylidene fluoride (minimizing electrolyte
effects). The final thickness of the electrode was <40 μm (excluding
the aluminum current collector) after fully drying the N-Methyl-2-
pyrrolidone solvent in a vacuum oven overnight at 60 °C.
The Nernst voltage curve obtained using half-cells with GITT is
shown in Fig. 3a, and the derivative with respect to Li composition
eq
∂VLi
yields the ∂xLi
curve shown in Fig. 3b. It is seen that the obtained
charging curves are identical for the 1st, 2nd, and 3rd cycles; the
starting Li composition was “reset” after each cycle by a long 2.5 V Figure 3. Determining the derivative of the Nernst potential (a) Open circuit
hold at the end of discharge for full lithiation.14 voltages obtained using GITT on NMC111 porous electrodes at 30 °C . The
The Nernst voltage curve can also be used to calibrate the solid markers represent the first charging curve. Using two other cells from a
different electrode, GITT open circuit voltages were also measured from the
composition of the bulk samples. To confirm the validity of this second cycle (+ markers) and third cycle (× markers). For these later-cycle
approach, we estimated the Li composition of annealed bulk samples cells, the cells were discharged with a long voltage hold at 2.5 V to return the
using the open-circuit voltage (OCV) and the calibration curve in starting composition to Li fraction 1.0. 14 The curves are identical within
Fig. 3a. Then, we pulverized the sample into powder with a mortar experimental resolution. (b) Derivative of the Nernst voltage curve obtained
and pestle (in an Ar-filled glove box) and made a capillary X-ray in (a).
 Journal of The Electrochemical Society, 2021 168 120503
Figure 4. Chemical diffusivity of lithium extracted from GITT measure-
ments on NMC111 bulk samples at 30 °C . Each marker color represents a
different bulk sample. The dashed line is a guide representing the trend of the
compiled data. The shaded area is the 0.95 confidence interval (t-distribution)
for the trend line.
Figure 5. Arrhenius activation energy for chemical diffusion, extracted from
GITT measurements on NMC111 bulk samples. Error bars represent the
linear fitting errors from a log DT vs 1/T analysis.
diffraction sample. The Li composition was then estimated using the
lattice parameters and the calibration curve reported in Ref. 14. For a
bulk sample with an OCV-estimated Li fraction of 0.78, the XRD-
estimated Li fraction was 0.76. In another sample, the two estima-
tions were 0.54 and 0.58, respectively. This consistency indicates the
Li composition can be inferred from OCV with reasonable un-
certainty.
Diffusivity extraction.—We do pulse-relaxation experiments
(Fig. 2) on bulk samples of various Li compositions, as prepared
through the procedures in section “Preparation of Closed-Pore Bulk
Samples”. Then, using the Nernst voltage derivative curve in Fig. 3b,
chemical diffusivities are extracted from Eq. 1. The results are
plotted in Fig. 4. Note that the relation between D̃ vs Li composition
displayed in Fig. 4 is qualitatively different than any other literature
report compiled in Fig. 1 of Part 1.6
Figure 6. Ionic conductivity calculated from chemical diffusivity measure-
ments on NMC111 bulk samples at 30 °C . Ionic conductivity is extracted
assuming an ion-limited case, Eq. 2. Plotted together is the total conductivity
measured using a four-probe method on bulk samples, confirming the ion-
limited assumption.
Next, we check the validity of the semi-infinite diffusion
condition.6 By taking the upper bound of the D̃ values from Fig. 4 as
2 × 10−9 cm2 s−1, size of the thinnest sample used in the experi-
ment as 2L = 0.426 mm, and the pulse duration τ = 10 min, the
D̃τ
upper bound of the dimensionless pulse duration τ̂ = L2 evaluates to
3 × 10−3. This value is 2 orders of magnitude smaller than the
criterion for 1D planar systems (τ̂ < 0.25), confirming the correct
design of the sample and pulse duration.
Activation Energies
At each Li composition, we do pulse-relaxation experiments at
three different temperatures (15 °C, 30 °C, and 45 °C) to extract the
Arrhenius activation energy for chemical diffusion. The differential
Nernst voltage curve (Fig. 3b) obtained from 30 °C can be used
identically at other measurement temperatures without introducing
meaningful errors. The temperature sensitivity of Nernst voltages
(VLieq ) at near full-lithiation (3.6 V vs Li) and half-lithiation (4 V vs
Li) is only different by 0.1–0.2 mV K−1. Therefore, the Li composi-
∂V eq
tion derivative ( ∂xLi ) will only change by <1% for a temperature
Li
change as big as 20 K.
Activation energies are obtained by assuming an Arrhenius
relation for DT, as shown in Fig. 5. This procedure is in anticipation
that the activation energy of chemical diffusion will correspond to
that of a partial conductivity (ionic in this case, as will be confirmed
in the next section). Applying the Arrhenius relation to DT instead of
D yields activation energies about 26 meV larger.
Insight from Measurement Results
Ionic vs electronic conductivity.—Chemical diffusion is an
ambipolar process where charge neutrality requires the concurrent
diffusion of two oppositely charged species. Using the chemical
diffusivity of NMC111, we can infer whether the Li ions or the
electronic species are limiting for this bulk transport process. We
assume that the ionic species are limiting for chemical diffusion, and
verify whether this assumption holds. When Li ions are limiting,
chemical diffusivity can be expressed as (derived in the Appendix of
Part I):
 Journal of The Electrochemical Society, 2021 168 120503
σ ⎛ v ∂V ⎞
eq
σ ∂μ
D˜ = i2 Li = i ⎜ M Li ⎟, [2]
F ∂c Li F ⎝ F ∂xLi ⎠
where σi is the ionic conductivity from Li ions, μLi is the chemical
potential of neutral Li species, and cLi is the volumetric density of Li
species. Using this equation, ionic conductivity is calculated from
the chemical diffusivity and plotted in Fig. 6. To test the validity of
the ion-limitation assumption, we also measure the total conductivity
of bulk samples. We use a four-probe method to exclude contribu-
tions from contact resistances15 (two-probe measurements under-
estimate electronic conductivity by orders of magnitude). The
measured bulk total conductivity is plotted together in Fig. 6.
Total conductivity is found to be much larger than the ionic
conductivity at all Li compositions where D̃ was measured. This
confirmation validates the conversion of chemical diffusivity to ionic
conductivity using Eq. 2. It also indicates that the total conductivity
measurement is practically equivalent to an electronic conductivity
measurement. Chemical diffusion in NMC111 is therefore limited
by ionic rather than electronic conduction.
Is the activation energy from ion hopping?.—From the many
factors that contribute to Li chemical diffusivity in NMC, which one
determines the temperature dependency? From the partial conduc-
tivity investigation, we can first rule out the contribution from
electronic conductivity, leaving only the factors in Eq. 2. Then, we
∂μ
can also rule out ∂c Li because of its minimal temperature dependency
Li
(see subsection “Activation Energies”). Therefore, the activation
energy in chemical diffusion can be attributed to that of ionic
conductivity.
The Nernst-Einstein relation between conductivity and self-
diffusivity suggests that the activation energy be analyzed with
D̃T or σiT:
zF 2
D˜ (T ) ∝ σi (T ) = Dc, [ 3]
RT
where z, D, c are the formal charge, self-diffusivity, and volumetric
concentration of the species responsible for the ionic conduction.
The activation energies in Fig. 5b can now be attributed to the sum
of the formation energy of an ionic species and the diffusion barrier
for that same species.
If we decide to describe the regular Li ions, then cLi is virtually
fixed with respect to temperature, and the activation energy can be
entirely attributed to the self-diffusivity of regular Li ions (D Li+ ).
However, this designation does not offer much mechanistic insight,
because it is simply a nominal value ignorant of the mobile defect
species. Describing the mobile defect responsible for the Li ion self-
diffusivity provides better insight, but this process requires knowledge
about the mobile defect (which is often a minority species). From
computational studies16–18 it has been suggested that divacancies are
responsible for most of the ionic conductivity in layered oxides. The
simplest treatment of this case is to count the divacancy concentration,
say cVV, treat it as z = − 2, and account for the self-diffusivity of the
divacancies DVV. The activation energy for ion hopping in this
divacancy description has been calculated to be a monotonically
decreasing function with respect to delithiation, primarily correlated
with the inter-slab distance between layers. However, the measured
activation energy for chemical diffusion is not monotonic upon
delithiation, and the trend is opposite from Li fraction 1.0 to 0.7. If
one were to reconcile this observation with the divacancy model, this
non-monotonic trend of activation energy indicates that the formation
energy of divacancies, rather than that of ion hopping, dominates the
activation energy at Li fraction from 1.0 to 0.7. Alternatively, a
different defect model might be necessary to describe diffusion.
Overall, explaining chemical diffusion only with ion hopping does
not seem to be justified based on our experimental measurements.
Sluggish kinetics near full lithiation?.—It has been argued in
the literature that the sluggish kinetics near full lithiation in layered
oxides is due to the slow chemical diffusion in those
compositions,19–21 apparently supported by selected (conventional)
GITT measurements compiled in Fig. 1 of Part I.6 Although this
view has been refuted through the demonstration of reaction-
limitation for standard particle sizes,14 questions remain whether
sluggish chemical diffusion can be completely ruled out. Our
chemical diffusivity measurements shown in Fig. 4 reveal that
chemical diffusion is not the slowest near full-lithiation. Although
ionic conductivity does seem to trend toward a minimum near full-
lithiation, the enhancement factor (thermodynamic factor) in Fig. 3b
dominates the trend of chemical diffusivity in this composition
range. This observation is consistent with what is expected from
thermodynamics. Although Fick’s law seemingly suggests that
concentration gradients drive diffusion, it is the chemical potential
gradient that constitutes the real thermodynamic driving force. Near
full-lithiation, a given concentration gradient translates to a much
larger driving force (hence the term “enhancement factor”). Overall,
our chemical diffusion measurements provide further evidence that
chemical diffusion is not responsible for the sluggish kinetics and the
limited access of capacity (i.e. kinetic capacity loss19,21,22) near full-
lithiation. Meanwhile, charge transfer resistance of the intercalation/
deintercalation reaction plummets exponentially as Li composition
approaches full occupancy,14 further suggesting that the sluggish
kinetics at this composition is charge-transfer limited. In the next
section, we quantitatively assess the rate-limiting step.
Is chemical diffusion a limiting process?.—Of high interest in
the battery research community is whether chemical diffusion is a
limiting factor for the electrochemical reaction of active particles.
Inter-particle inhomogeneity discovered in porous electrodes14
indicates that Li insertion and desertion in typical battery particles
are limited by the surface rather than bulk processes. However, the
uncertainty in diffusivity values and particle geometries have made it
difficult to understand whether the limiting kinetic process would
change by tuning the particle size or surface properties. We address
this question using our measured chemical diffusivity values.
The ratio between a surface reaction rate and bulk diffusion rate
is a convenient metric for quantitatively assessing interface- and
bulk-limited regimes in transport problems. If we let L describe the
size of the bulk in a planar system and h describe a mass transfer
coefficient at the surface (in the units of length per time), the surface
reaction rate can be expressed as h/L (units of inverse time). The rate
for diffusion can be expressed as D/L2 (units of inverse time), where
hL
D is diffusivity. The ratio of these rates is the Biot number, Bi = D ,
a dimensionless metric. By expressing h in terms of area-specific
exchange-current density j0 (as in the Butler-Volmer (BV) relation),
we can use Bi for electrochemical reactions. In the linear BV regime
for Li intercalation,
j0 L ∂VLieq
Bi = . [4]
D˜ Li RT ∂c Li
Here, diffusivity has been replaced with the chemical diffusivity, VLieq
is the Nernst voltage, and cLi is the concentration of the neutral Li
species in the units of moles per volume. To apply Bi to porous
electrode measurements, in which mass-specific exchange current is
measured, we reformulate Bi by assuming spherical particles of
radius r:
j0 ′MM ∂VLieq
Bi = r 2 . [ 5]
3D˜ Li RT ∂xLi
Here, j0′ is in the units of current per mass, MM is the molar mass of
the chemical formula corresponding to xLi = 1, and xLi is the Li
fraction (selecting r as the length scale for Bi results in a similar Bi
criteria as in a planar problem).
 Journal of The Electrochemical Society, 2021 168 120503
Figure 7. Biot number for NMC111 agglomerate particles, comparing
different assumptions about the effective particle radii. The lower and upper
limits of the effective particle size are determined by the physical size of the
primary and agglomerate particles, respectively. Because of partial electro-
lyte penetration, the realistic effective size is in the intermediate range. A
large Biot number (red shade) indicates that the kinetics are limited by
chemical diffusion, whereas a small number (green shade) indicates that the
kinetics are limited by the intercalation/deintercalation reaction. We use the
2nd-cycle mass-specific exchange current density as reported in Ref. 14,
where j0′ is measured with an LP40 electrolyte in the limit of a thin
(≈20 μm) and dilute (40 wt.% active mass) electrode.
Using the j0′ values for the Li intercalation/deintercalation reaction,
reported from porous electrodes made with agglomerate particles,14
we calculate the Biot number with three different assumptions about
the effective particle radius: r = 0.1 μm (approximate primary particle
radius); r = 5 μm (approximate secondary particle radius); r = 0.5 μm
(intermediate, assuming partial electrolyte penetration). The curves
plotted in Fig. 7 show that even under the unlikely assumption23–25
that no electrolyte penetration or particle cracking occurs during the
forming cycle (the r = 5 μm assumption), the kinetics would not have
been controlled by diffusion near full lithiation (Li fraction near 0.9 or
above). For a realistic assumption about the effective radius, kinetics
in these agglomerate particles would be either reaction-limited or mix-
controlled in the entire composition range. We note that mix-
controlled kinetics also behave qualitatively similar to reaction-limited
cases in terms of inter-particle inhomogeneity development.14
Therefore, we conclude that interface engineering26–34 either on the
particle side or electrolyte side26,27 should be an effective strategy for
improving kinetics and rate capability. Both sides of the interface
control the exchange-current density.35,36 Our analysis also suggests
that many studies aiming to improve the kinetics with the intention of
engineering bulk diffusion properties may have succeeded due to a
correlation between bulk and surface properties.
Summary and remarks.—We have demonstrated that preparing
dense bulk samples is an effective strategy for ensuring diffusion-
limitation and improving the reliability of chemical diffusion
measurements. On the other hand, the titration process for measuring
the equilibrium Nernst voltages works better with smaller particles
(as in porous electrodes for battery devices) where the time for
equilibration is much shorter. Because these two measurements
(transient diffusion vs equilibration) have opposite sample geometry
requirements, it is easier to optimize two different types of samples
for each measurement.
For the transient diffusion measurement, we have demonstrated
how one can take advantage of the relaxation time variable
trelax + τ − trelax . This approach avoids the non-constant over-
potential contribution to transient voltages. This relaxation analysis
method also explicitly accounts for the chemical profiles developed
during the current pulse.
Summarizing the steps for chemical diffusivity measurements:
• Prepare bulk samples dense enough to prevent electrolyte
penetration and large enough to ensure diffusion limitation.
• Electrochemically set the bulk composition to the target
composition and anneal the sample to ensure homogenization.
• Confirm that the bulk sample preserves the chemistry, crystal
structure, and phase of interest.
• Repeat pulse-relaxation experiments for a given composition
and extract the long time-scale relaxation slopes through a V vs
trelax + τ − trelax analysis.
• Pulse duration should be kept short, but long enough to observe
the bulk-transport limited relaxation regime. As in Fig. 2a, the
portion representing the “bulk” should be visible in the relaxation
curve.
• A series of pulse-relaxation measurements should be conducted
with varied pulse magnitude or direction, so that one can use the
scaling relation in Eq. 1.
• To determine the Nernst voltage as a function of composition,
a separate sample maximizing surface area and minimizing particle
size should be prepared (i.e. ensure short equilibration times). Pulse-
relaxation experiments should be repeated, similar to conventional
titration measurements, not to extract time-dependency but to only
extract the equilibrium voltages at each composition.
• Combining the Nernst voltage derivative and the bulk relaxa-
tion slopes, extract the chemical diffusion coefficient.
• With the measured diffusivity, iteratively check for the validity
of the experimental design, including diffusion limitation in the bulk
sample and pulse duration.
Chemical diffusivity, ionic conductivity, and activation energies
of NMC111 were measured using this modified GITT scheme.
Measurement results appear to be consistent with a recent study on
inter-particle inhomogeneity14 indicating that chemical diffusion is
not the most limiting process in battery electrodes. In other words,
the time scale for the intercalation/deintercalation reaction at the
surface is longer than that of the bulk diffusion time scale (Bi < 0.1).
The remaining questions include how the polycrystalline micro-
structure such as grain size or grain boundary structure influences the
bulk chemical diffusion. The methodology proposed and demon-
strated in this work could help study more advanced questions37–42
about chemical diffusion in electrochemically intercalating
materials.
Acknowledgments
This work was supported by the Toyota Research Institute
through the Accelerated Materials Design and Discovery program.
The authors would like to thank: Devi Ganapathi and Xiao Cui for
contributing to improving the clarity of the manuscript; Kipil Lim
for assistance in XRD.
ORCID
Stephen Dongmin Kang https://orcid.org/0000-0002-7491-7933
Jimmy Jiahong Kuo https://orcid.org/0000-0002-3434-1984
Nidhi Kapate https://orcid.org/0000-0002-5286-3663
Jihyun Hong https://orcid.org/0000-0001-7210-2901
William C. Chueh https://orcid.org/0000-0002-7066-3470
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