batteries

Article
Effect of Si Content on Extreme Fast Charging Behavior in
Silicon–Graphite Composite Anodes
Zhenzhen Yang *, Stephen E. Trask , Xianyang Wu and Brian J. Ingram 1

Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue,
Lemont, IL 60439, USA
* Correspondence: yangzhzh@[Link]

Abstract: Commercial Li-ion batteries typically incorporate a small amount of high-capacity silicon
(Si)-based materials in the composite graphite-based anode to increase the energy density of the
battery. However, very little is known about the effects of Si on the fast-charging behavior of
composite anodes. Herein, we examine the effects of the Si/graphite ratio in the composite anode on
the fast-charging behavior of full cells. We show that addition of Si increases the rate capability from
1C to 8C and improves the capacity retention in early cycles at 6C due to reduced overpotential in
constant current charging cycles. The impacts of Si content on fast-charging aging were identified by
Post-Test characterization. Despite realizing benefits of available capacity and reduced Li plating
at 6C, silicon–electrolyte interactions lead the time-dependent cell performance to fade quickly in
the long term. The Post-Test analysis also revealed the thickening of the electrode and nonuniform
distribution of electrolyte decomposition products on the Si-containing anodes, as well as the organic-
rich solid electrolyte interphase (SEI), which are the factors behind cell degradation. Our study
sheds insight on the advantages and disadvantages of Si/graphite composite anodes when they are
used in fast-charging applications and guides further research in the area by designing an optimized
composition of Si incorporated in a mature graphite matrix.

Keywords: extreme fast charging (XFC); Si content; silicon–graphite (Si–Gr) composite anodes;
SEI formation; anode degradation

Citation: Yang, Z.; Trask, S.E.; Wu, X.;

Ingram, B.J. Effect of Si Content on
1. Introduction
Extreme Fast Charging Behavior in
Silicon–Graphite Composite Anodes. In the last few years, there has been a sharp growth in demand for the creation of
Batteries 2023, 9, 138. https:// fast-charging capabilities for electric vehicles (EVs) powered by Li-ion batteries. Due to
[Link]/10.3390/batteries9020138 their limited driving ranges, the consumer preference for a rapid charging (<2 h) capability
is driving cars with the EV battery design; therefore, presenting future EVs to the market
Academic Editor: Hirotoshi Yamada
requires extreme fast charging (XFC) at rates between 4.8 and 6 C, which can restock 80% of
Received: 13 January 2023 the pack capacity from 12.5 to 10 min. In addition to the high performance expectations of
Revised: 8 February 2023 established battery technologies, faster charging poses difficulties for today’s batteries due
Accepted: 13 February 2023 to rapid battery aging and safety issues such lithium plating [1], the loss of active material
Published: 16 February 2023 particles [2], and impedance growth [2].
The negative electrode, a predominately graphite-based (Gr) material in current
lithium-ion batteries (LIBs), is considered to be the component limiting the control of
how quickly the battery can be charged during XFC [3,4]. Silicon (Si) is a promising alterna-
Copyright: © 2023 by the authors.
tive anode materials for LIBs due to its high theoretical gravimetric capacity (3579 mAh g−1
Licensee MDPI, Basel, Switzerland.
for Li15 Si4 ) relative to that of commercial graphite anodes (372 mAh g−1 for LiC6 ) [5]. The
This article is an open access article
higher lithium-alloying potential of Si (0.22 V vs. Li/Li+ ) relative to a low discharge poten-
distributed under the terms and
tial of Gr (0.08 V vs. Li/Li+ ) can mitigate Li plating, which is particularly important for fast
conditions of the Creative Commons
Attribution (CC BY) license (https://
charging [6,7]. Commercializing silicon anodes particularly for XFC applications is not an
[Link]/licenses/by/
easy task due to significant limitations including their poor electrical conductivity, high
4.0/).
volume expansion, cracking and pulverization, and unstable solid–electrolyte interface

Batteries 2023, 9, 138. [Link] [Link]

Batteries 2023, 9, 138 2 of 12

(SEI) [5,8]. Structural design strategies can increase the stability of the silicon anode and
partially mitigate the challenges stated above. For example, Si nanostructures, such as
nanotubes [9], nanoparticles [10], nanowires [11], and core–shell structure [5] proved to be
effective at achieving the enhanced transfer of lithium, an improved cycle life, and enabled
free space volume to accommodate the volume expansion and reduce the material stress
during lithiation [12]. Despite their benefits, nanostructure designs present challenges
to XFC operation. They are susceptible to increased side reactions with electrolytes and
charge transfer resistance due to high surface areas. Additionally, the cost and complexity
currently hinder the cost-effective implementation of nanostructural silicon in industrial
manufacturing processes.
A practical solution is to develop silicon in graphite matrix composite anodes, taking
advantage of graphite’s low surface area, electrical conductivity, and stability and silicon’s
high capacity. Indeed, the co-utilization of Si-Gr in composite anodes is reported to meet
capacity and cycling stability requirements, as well as cost-effective, large-scale indus-
trial production [13,14]. Relative to graphite electrodes, however, they represent unique
degradation processes. For example, Ruther et al. identified that composite anodes are
heterogeneous with separated graphite-rich and silicon-rich phase regions with lithiation
by Raman mapping [15]. Kirkaldy et al. found that the loss of active silicon in Si-Gr
composites is the major cell fading factor under operating conditions [16]. More recently,
Lee et al. reported that the self-discharge rate increases preferentially in Si by interfacial
side reactions and results in electron energy imbalance between Si and Gr in the composite
anode [17]. These reports mostly focused on the evaluation of cell performance and the
identification of degradation mechanisms with Si-Gr anodes under mild cycling conditions.
Si-containing electrodes designed and used to attain fast-charging characteristics further
aggravate the typical degradation mechanisms. Mechanistic insights for the aging behavior
of composite anodes under XFC cycling conditions is needed to understand the aging
effect, predict and mitigate degradation, and improve cell performance [18–20]. Hence, a
thorough understanding of the obstacles of fast charging is essential to reveal the aging
mechanisms of Si-Gr composites and develop strategies to reduce degradation and produce
XFC technologies containing Si-based anodes.
In this work, we provide a systematic investigation of the effect of Si on fast charging
and degradation mechanisms contributing to the capacity fade in the composite anodes.
For this purpose, we evaluated the performance of the electrodes’ containing various Si and
Gr concentrations in full cells versus that of NMC811 under XFC conditions. Since carbon
additives and binders also play significant role in the conductivity, interphase chemistry,
and mechanical integration of the Si-Gr composites, as reported [21], we maintained
a constant ratio of carbon additives and binders to active material in this study. We
present the impact of XFC charge protocols at charging rates of 1C-8C and long-term
aging at 6C. We couple cell performance to the evolution of the bulk electrode structure
and interface, including morphology and compositional changes by Scanning Electron
Microscopy (SEM/EDS) and SEI composition by X-ray Photoelectron Spectroscopy (XPS).
The analysis of these relations provides clarity on the relative benefits of Si in XFC cells
and the trade-off between a greater capacity and a shorter lifetime. Our findings of the
Si-Gr interfacial structure provide further predictive control of the Si interface chemistry
through surface modifiers, such as electrolyte additives or coatings, which are critical for
next-generation cell discovery and design.

2. Materials and Methods

Materials. In this work, all of the electrode laminates used were provided by the Cell
Analysis, Modeling, and Prototyping (CAMP) Facility at Argonne National Laboratory.
The compositions and properties of the NMC811 positive electrode and the Si-Gr negative
electrode with different Si contents are given in Table 1. For a fair comparison, the amounts
of binder and carbon additive were the same for all three composite anodes, and only the
Si and Gr contents changed. The NMC811 electrode were cut into 14 mm dia disks, and the
Batteries 2023, 9, 138 3 of 12

negative laminate was cut into 15 mm dia disks. The disks were dried in active vacuum
oven in the glovebox at 110 ◦ C overnight for NMC811 and at 140 ◦ C for Si-Gr anodes prior
to cell assembly. Sixteen mm dia disks of Celgard 2320 separator sheet were used in the
coin cells. As the electrolyte in the cell, 1.2 M LiPF6 in ethyl methyl carbonate:ethylene
carbonate (7:3 by wt%) with 3 wt% fluoroethylene carbonate (FEC) was used.

Table 1. Composition of electrodes used in this work. Copper foil thickness was 10 µm. Aluminum
foil thickness was 20 µm.

Cathode Si-Gr Composite Anode

Composition NMC811 00Si 15Si 30Si
0 wt% Paraclete 15 wt% Paraclete 30 wt% Paraclete
90 wt% NMC811 Energy Si, Energy Si, Energy Si,
active material
(Targray) 88 wt% Hitachi MagE3 73 wt% Hitachi MagE3 58 wt% Hitachi MagE3
graphite graphite graphite
5 wt% poly(vinylidene
10 wt% lithium 10 wt% lithium 10 wt% lithium
binder fluoride) (PVDF,
polyacrylate (LiPAA) polyacrylate (LiPAA) polyacrylate (LiPAA)
Solvay 5130)
5 wt% Timcal C45 2 wt% Timcal C45 2 wt% Timcal C45 2 wt% Timcal C45
conducting agent
carbon carbon carbon carbon
loading density
9.08 6.4 3.0 2.32
(mg/cm2 )
coating thickness (µm) 33 48 27 22
N/P ratio ~1.33 ~1.31 ~1.36

Electrochemical testing. With the Si-Gr/NMC811 full cell, rate capability tests were
carried out at constant C-rates from 1 to 8C, with a subsequent constant voltage hold
of 4.1 V until the current fell below 0.2C. All of the C-rates were calculated based on
the measured discharge capacity during the formation process at 0.05C. All of the elec-
trochemical experiments were run on an MACCOR Series 4000 battery cycler in tripli-
cate. The long-term fast-charging aging tests used the following protocol proceeded as
such: the cells were first tap charged to 1.5 V, and this was held for 15 min, then left to
rest at an open circuit voltage (OCV) for 12 h. Then, the cells were formed at the C/10
rate for 3 cycles, followed by C/1 rate for another 2 cycles, with cutoff voltage between
3.0 and 4.1 V. Since most current commercial fast chargers employ the constant current-
constant voltage (CC-CV) charging protocol, it was adopted for the aging analysis in this
work. The aging protocol was performed by cycling the cells at C/20 rate for 2 cycles
first, and then charging them at 6C (CC-CV with 10 min total time limit) and discharg-
ing them at C/2 (CC) for 100 cycles between 3.0 and 4.1 V. Reference performance tests
(RPTs) were performed at every 25 intervals, including C/20 CC charge and discharge tests
between 3 and 4.1 V.
Scanning Electron Microscopy (SEM). The cells were dissembled, and the electrodes
were harvested in the glovebox. The anode materials were rinsed twice with excess
dimethyl carbonate (DMC) for 1 min each time. Then, the samples were transferred from
glovebox into the SEM column without air exposure using a vacuum-sealable transfer
holder that was described in our previous work [22]. SEM/EDS data were collected using
a JEOL JSM-6610LV/coupled with an EDS detector (Oxford) at 20 kV.
X-ray Photoelectron Spectroscopy (XPS). XPS measurements on washed electrodes
were taken in a Physical Electronics PHI 5000 VersaProbe II system photoelectron spec-
trometer operating in a high vacuum with typical pressures of under 1 × 10−7 Torr. The
samples were transferred into the XPS analysis chamber through the glovebox without
being exposed to ambient air because the apparatus was coupled to the Ar atmosphere
glovebox. With 25 W anode power, the Al K X-ray monochromator (hv = 1486.6 eV) was put
to use. The charge neutralizer was applied to counterbalance the charging of the sample.
 samples were transferred into the XPS analysis chamber through the glovebox without
being exposed to ambient air because the apparatus was coupled to the Ar atmosphere
glovebox. With 25 W anode power, the Al K X-ray monochromator (hv = 1486.6 eV) was
Batteries 2023, 9, 138 put to use. The charge neutralizer was applied to counterbalance the charging of the 4sam-
of 12
ple. The sample surface normal was oriented at 45° to both the X-ray source and photoe-
lectron spectrometer. The elemental high-resolution spectra were collected at pass 23.5 eV
of energy through a 100 μm × 100 μm area. The LiF peak at 684.8 eV was used to calibrate
The sample surface normal was oriented at 45◦ to both the X-ray source and photoelectron
the spectra. All of the spectra were processed using Physical Electronics’ Multipack soft-
spectrometer. The elemental high-resolution spectra were collected at pass 23.5 eV of energy
ware, which included Shirley background subtraction and curve fitting of multiple Gauss-
through a 100 µm × 100 µm area. The LiF peak at 684.8 eV was used to calibrate the spectra.
ian peaks.
All of the spectra were processed using Physical Electronics’ Multipack software, which
included Shirley background subtraction and curve fitting of multiple Gaussian peaks.
3. Results and Discussion
3.1. Electrochemical
3. Results Performance of Initial Rate Capability Characterization
and Discussion
3.1. Electrochemical Performance
Cells containing of Initial(referred
pure Gr anodes Rate Capability Characterization
to as 00Si), 15 wt% Si (referred to as 15Si),
and 30 wt%
Cells Si (referred
containing pureto Gras 30Si) (referred
anodes are compared throughout
to as 00Si), 15 wt% Sithis [Link]
(referred the
15Si), and
transport
30 wt% Si constraints
(referred tofor safe cell
as 30Si) are operation
comparedand to assist this
throughout in protocol
paper. To development, follow-
assess the transport
ing two initial
constraints for 0.05
safe C forming
cell operation cycles,
andrate capability
to assist tests between
in protocol development, 1C andfollowing
8C with fourtwo
initial at
cycles 0.05 C forming
each cycles, by
rate separated ratea capability
C/10 cycle tests
werebetween 1C on
carried out anda 8C withoffour
subset coincycles at
cells, as
each rate
shown in separated
Figure 1a,b. by As
a C/10 cycle were
expected, both thecarried out on
specific a subsetand
discharge of coin cells,
charge as shown
declined within
Figure
an 1a,b. in
increase Astheexpected,
C-rates both
up tothe6Cspecific discharge polarization,
due to increased and charge declined
regardless withofantheincrease
anode
in the C-ratesBetween
composition. up to 6Cfastduecharging
to increasedat 6Cpolarization, regardless ofdecrease
and 8C, an insignificant the anode in composition.
cell capacity
Between
was fast charging
measured. However,at 6Ctheand 8C, an
effect of insignificant
the Si content decrease
on the in cellcapability
rate capacity wascan measured.
clearly be
observed at high currents (Figure 1a). The 30Si cells exhibit better capacity retention asat
However, the effect of the Si content on the rate capability can clearly be observed a
high currents
function (Figure
of charge rate1a). The 30Si
compared tocells exhibit better
the dramatic drop capacity
observedretention
in the 00Si as cells
a function
with the of
charge rate
increase compared
in the C-rates. toThe the dramatic
30Si drop~74%
cell retains observed
of theincapacity
the 00Siatcells with the
a 6C-rate increase
relative to a
in therate,
C/10 C-rates.
whichThe is in30Si cell retains
contrast ~74% of retention
to the capacity the capacity at a
of the 6C-rate
00Si and 15Sirelative
cells to
(40%a C/10
and
rate, which
63%, is in contrast
respectively) to therates.
at the same capacity
As aretention
result, Siof the 00Siinand
addition the15Si cells (40%
composite andbene-
brings 63%,
fits to the rate capability. Hamzelui et al. also observed an enhanced rate capability asto
respectively) at the same rates. As a result, Si addition in the composite brings benefits a
the rate
result ofcapability.
the co-useHamzelui
Si-Gr andetappropriate
al. also observed an enhancedofrate
dose optimization capability
a mixture as a result
of polymeric
of the co-use
binders Si-Gr andregulating
(for example, appropriate thedose
ratiooptimization
between LiPAA of a mixture
and CMC of with
polymeric
specificbinders
com-
(for example, regulating
patibility to Si and Gr) [23]. the ratio between LiPAA and CMC with specific compatibility to
Si and Gr) [23].

Figure 1. Rate capability tests at several (C-rates)

(C-rates) for (a) 00Si, (b)15Si, and (c) 30Si electrodes in the
potential
potential range
range of
of 3.0–4.1
3.0–4.1 V
V versus
versus those
those of
of NMC811.
NMC811. TheThe measured
measured specific
specific capacities
capacities are
are shown
shown in
in
in charge (black square symbols) and discharge (red circle symbols).
in charge (black square symbols) and discharge (red circle symbols).

Additionally, during the CC charging, a considerable discrepancy in the high-rate

charge acceptance
acceptance across
across the three cells is observed. As As reported
reported inin our
our previous
previous work,
work,
reducing the
the time
timeand
andcapacity
capacitywhen
whenthe thecell
cellisisclose
closetotothe
theupper
upper voltage
voltage limit
limit oror decreas-
decreasing
ing
the the
CV CV portion
portion for for Li-ion
Li-ion cells
cells is crucial
is crucial under
under XFC XFC to capture
to capture high-rate
high-rate behavior
behavior with-
without
Li plating
out [3]. Figure
Li plating 2 compares
[3]. Figure 2 compares the voltage
the voltageprofiles during
profiles the charge
during process
the charge for each
process for
C-rateC-rate
each and anode composition.
and anode For 00Si
composition. Forcells,
00Si Vmax (4.1 V)(4.1
cells, Vmax wasV)reached within within
was reached 10 min 10
at
C-rates greater than two. This indicates the charge overpotential increased quickly and
constrained the capacity that was reached during the CC charging cycle. In other words,
most of the charge capacity was obtained during the 4.1 V CV hold stage for 00Si anodes
following applied current densities greater than 2C. In contrast, anodes with Si showed less
charge overpotential, leading to approximately 50% of the total charging capacity being
achieved during the CC step up to 3C and 4C for 15Si and 30Si, respectively. The potential
of Li plating is reduced under CC charging, resulting in a higher capacity. The voltage
 min at C-rates greater than two. This indicates the charge overpotential increased quickly
and constrained the capacity that was reached during the CC charging cycle. In other
words, most of the charge capacity was obtained during the 4.1 V CV hold stage for 00Si
anodes following applied current densities greater than 2C. In contrast, anodes with Si
Batteries 2023, 9, 138 showed less charge overpotential, leading to approximately 50% of the total charging 5 ofca-
12
pacity being achieved during the CC step up to 3C and 4C for 15Si and 30Si, respectively.
The potential of Li plating is reduced under CC charging, resulting in a higher capacity.
The voltage profiles revealed that Si can facilitate Li+ diffusion in the bulk of the composite
profiles revealed that Si can facilitate Li+ diffusion in the bulk of the composite anodes,
anodes, particularly during constant charging process.
particularly during constant charging process.

Figure
Figure 2.2. Cell
Cell voltage
voltage as
as aa function
function of
of charge
charge capacity
capacity upon
upon charge
charge process
process during
during rate
rate capability
capability
test for (a) 00Si, (b) 15Si, and (c) 30Si electrodes in the potential range of 3.0–4.1 V versus
test for (a) 00Si, (b) 15Si, and (c) 30Si electrodes in the potential range of 3.0–4.1 V versus those of
those
NMC811.
of NMC811.

Lithium-ion
Lithium-ion (Li(Li++)) insertion/extraction
insertion/extractionredox
redoxreactions,
reactions,along
along with
with contributions
contributions from
from
Li ++ diffusion across solid-state interphases (SEI and CEI), Li++ diffusion in the bulk of the
Li diffusion across solid-state interphases (SEI and CEI), Li diffusion in the bulk of the
materials,
materials, overpotential,
overpotential, and and other
other factors
factors determine
determine the the rate
rate capability
capability ofof the
the entire
entire full
full
cell.
cell. Heubner
[Link]
reported on an
on extensive investigation
an extensive on a on
investigation “model-like blended
a “model-like Si-Gr
blended
electrode,” and found
Si-Gr electrode,” that thethat
and found silicon’s contribution
the silicon’s dominates
contribution during lithiation
dominates at rates
during lithiation
of
at higher
rates ofthan 2C. than
higher This [Link] most
Thislikely duelikely
is most to better
due reaction
to betterkinetics
reactioninkinetics
Si [24]. Yao
in Siet[24].
al.
demonstrated in operando
Yao et al. demonstrated X-ray diffraction
in operando experiments
X-ray diffraction that siliconthat
experiments addition
siliconhas a ten-
addition
dency to reducetothe
has a tendency overpotential
reduce of lithium–graphite
the overpotential phase formation
of lithium–graphite during charging
phase formation during
[25]. Thus,[25].
charging our Thus,
resultsour of results
the rateofcapability of the full of
the rate capability cells
thewith Si-composite
full cells anodes is
with Si-composite
consistent with previously
anodes is consistent reported work.
with previously reported work.

3.2. Electrochemical
3.2. Electrochemical Performance
Performance of of Long-Term
Long-Term XFC XFC Aging
Aging
To further evaluate the XFC capability performance
To further evaluate the XFC capability performance of of Si-Gr-based
Si-Gr-based fullfull cells,
cells, more
more
investigations at
investigations at 6C
6C were
were conducted
conducted for for the
the three
three anode
anode compositions
compositions for for the
the long-term
long-term
aging analysis.
aging analysis. Figure
Figure33displays
displaysthe thecapacity
capacity fade
fadeand other
and otherpertinent
pertinentcycle life life
cycle characteris-
charac-
tics over 100 cycles using our XFC testing protocols described in the
teristics over 100 cycles using our XFC testing protocols described in the experimental experimental section.
Figure 3a shows that the accumulated irreversible capacity fade
section. Figure 3a shows that the accumulated irreversible capacity fade was higher was higher (~30%) at the
very beginning for 00Si, most likely due to significant Li loss from the
(~30%) at the very beginning for 00Si, most likely due to significant Li loss from the plat- plating. Then, it
showed a distinctly stable and much suppressed decay as the cycling
ing. Then, it showed a distinctly stable and much suppressed decay as the cycling pro- progressed, with
lower cell-to-cell
gressed, with lower variability. In variability.
cell-to-cell contrast, the Inrate of thethe
contrast, capacity
rate offade in 15Si and
the capacity fade 30Si was
in 15Si
much lower in the beginning, but they showed a nearly linear increase
and 30Si was much lower in the beginning, but they showed a nearly linear increase dur- during later cycles.
As alater
ing result, both
cycles. Asofa result,
them showed a higher
both of them capacity
showed fadecapacity
a higher than 00Si did
fade after
than 00Si100didcycles,
after
indicating that the benefit of adding Si in the Gr matrix is limited to early
100 cycles, indicating that the benefit of adding Si in the Gr matrix is limited to early XFC XFC cycles.
To assess the viability of anode materials, Coulombic efficiency (CE) is a useful metric
cycles.
to designate the rate of deterioration and loss of Li inventory due to side reactions inside
To assess the viability of anode materials, Coulombic efficiency (CE) is a useful metric
a cell. The CEs presented in Figure 3b were calculated using the fast charge and slow
to designate the rate of deterioration and loss of Li inventory due to side reactions inside
discharge (C/2) capacities cycle by cycle during 100 XFC cycles. In Figure 3b, the overall
a cell. The CEs presented in Figure 3b were calculated using the fast charge and slow dis-
CEs are lower than 100% for all three types of cells, which is usually associated with
charge (C/2) capacities cycle by cycle during 100 XFC cycles. In Figure 3b, the overall CEs
continuous cyclable Li loss through parasitic reactions on both the anodes and cathodes.
are lower than 100% for all three types of cells, which is usually associated with
Before obtaining efficiencies ~99.9%, the 00Si and 15Si cells exhibited a severe drop in CE
during the early cycles (<10 cycles). Tanim et al. and Yang et al. suggested that CE can be
utilized in a fast-charging test to signal Li plating as a global electrochemical signature [26].
Thus, the primary cause for such a low CE is attributed to the considerable Li loss due to Li
plating in the first ten cycles in addition to the expected SEI formation. In comparison to
the 00Si and 15Si, the greater CE values in the 30Si cell suggest significantly less or no Li
plating over the first few cycles, which is consistent with what can be seen in Figure 4 in the
 Before obtaining efficiencies ~99.9%, the 00Si and 15Si cells exhibited a severe drop in CE
during the early cycles (<10 cycles). Tanim et al. and Yang et al. suggested that CE can be
utilized in a fast-charging test to signal Li plating as a global electrochemical signature
[26]. Thus, the primary cause for such a low CE is attributed to the considerable Li loss
Batteries 2023, 9, 138 due to Li plating in the first ten cycles in addition to the expected SEI formation. In 6com- of 12
parison to the 00Si and 15Si, the greater CE values in the 30Si cell suggest significantly less
or no Li plating over the first few cycles, which is consistent with what can be seen in
Figure 4 in the cell tear-down photographs. In the following cycles, the CE stays relatively
cell tear-down photographs. In the following cycles, the CE stays relatively steady in 00Si
steady
cells, in 00Si cells, demonstrating
demonstrating less parasitic
less parasitic interactions interactions
and, hence, lessand, hence, less
irreversible irreversible
active lithium
active lithium loss as the cycling progresses. A slightly lower CE was still seen
loss as the cycling progresses. A slightly lower CE was still seen throughout subsequent throughout
subsequent
cycles cycles
for 15Si and for
30Si,15Si andis30Si,
which which of
indicative is continuous
indicative ofSEI
continuous
developmentSEI development
on the anode
on the anode with the presence of an unstable
with the presence of an unstable Si surface. Si surface.

3. Average
Figure 3. Averageelectrochemical
electrochemicalperformance
performanceofof00Si,
00Si,15Si,
15Si, and
and 3030
Si Si paired
paired with
with NMC
NMC 811811 cath-
cathode
ode charged
charged at 6-C
at 6-C (CC-CV)
(CC-CV) andand discharged
discharged at 0.5-C
at 0.5-C (CC)
(CC) forfor 100
100 [Link]
cycles. Eachcomposition
compositionhas
has three
three
Batteries 2023, 9, x FOR PEER REVIEW
duplicate cells.
cells. The 7 of 13
duplicate The plots
plots show
show (a)
(a) relative
relative discharge
discharge capacity
capacity lossloss at
at 6C,
6C, (b)
(b) coulombic
coulombic efficiencies,
efficiencies,
(c) and relative discharge capacity loss at C/20 over every RPT cycles.
(c) and relative discharge capacity loss at C/20 over every RPT cycles.

Figure 4. SEM images of morphology of anodes at selected spots: (a) 00Si without Li plating, (b)
Figure
00Si with4. LiSEM images
plating, of morphology
(c) 15Si, of anodes at selected
(d) 30Si, (e) cross-sectional spots:
images of 00Si, (a) 00Si without Li
(f) cross-sectional plating,
images of
(b) 00Si
15Si, andwith Li plating, (c) 15Si,
(g) cross-sectional (d) of
images 30Si, (e)Inset
30Si. cross-sectional images
pictures are of 00Si,
the optical (f) cross-sectional
images taken from theimages
aged
of 15Si, and (g) cross-sectional images of 30Si. Inset pictures are the optical images taken from the
anodes.
aged anodes.
For XFC cells, it is important to include the Reference Performance Test (RPT) at
much slower rate to assess the battery degradation during its testing. Utilization of the
electrodes is relatively low under XFC, such that fading at a high C-rate does not neces-
sarily reflect the real degradation behavior and electrode damage that are occurring.
Therefore, we performed a discharge capacity test measured at C/20 during RPTs at an
Batteries 2023, 9, 138 7 of 12

For XFC cells, it is important to include the Reference Performance Test (RPT) at
much slower rate to assess the battery degradation during its testing. Utilization of the
electrodes is relatively low under XFC, such that fading at a high C-rate does not necessarily
reflect the real degradation behavior and electrode damage that are occurring. Therefore,
we performed a discharge capacity test measured at C/20 during RPTs at an interval of
25 every cycles to assess the capacity fading relative to the beginning of life value. As
indicated in Figure 3c, the real capacity fade follows the same trend as the XFC conditions.
The rate of real capacity fade is higher up to cycle 25, at which point, a marked decrease
in fade is apparent during subsequent cycles. Conversely, both of the Si-containing cells
exhibit a lower fade in early cycles, but a faster decay afterward. The 30Si cells showed
lower fade compared to that of the 15Si up to cycle 75, and then, they overlapped with
15Si after 100 cycles, implying that the Si content indeed affect the cycle life performance
in a nonlinear pattern. A higher Si content improves the rate capability for short-term
cycling due to its better reaction kinetics with Li+ and reduced overpotential during the
charging step, as discussed in Figures 1 and 2. However, its merits were inevitably offset
due to continuous parasitic reactions from the enlarged surface area and unstable interface
of Si during long-term cycling. Furthermore, the nonlinear correlation between cycle life
performance and Si content demonstrate silicon and graphite can interact electrochemically.
We cannot rule out other interactions between silicon and graphite besides preferential
lithiation, as reported elsewhere [27]. The nature of silicon and graphite electrochemical
interactions during CC-CV fast charging and the relative contribution to the overall capacity
deserve a future detailed study.

3.3. Morphology and Composition of Aged Anodes

The SEM images of the Si-Gr anodes in Figure 4 reveal the morphological changes that
result from XFC cycling. The optical picture in the inset of Figure 4a shows areas with an
uneven metallic coloration across the surface of the 00Si anode. Not surprisingly, the SEM
images show distinct surface differences for the 00Si sample. In the black area of electrode’s
edge, graphite particles are still observable, but a thin passivation film is present (Figure 4a).
On the area with metallic coloration, there is complete coverage of the graphite particles by
a combination of dense, thick, rod-like Li dendrite structures and the products formed by
reactions of the plated lithium with the electrolyte (Figure 4b). The SEM results revealed
the local heterogenous Li plating behavior on 00Si anode, which is consistent with our
previous work [2,3]. Figure 4c shows a section of a 15Si composite depicting the presence
of a micro-cluster of Si/SiOx nanoparticles entrapped in the graphite matrix. As seen in
the SEM images (Figure 4d), the composite anode prepared with 30Si demonstrates a more
uniform Si distribution than the anode containing 15% of it does. As expected, cracks
are observed in the 30Si anode due to the volume change in Si during cycling. It is also
important to note that these images show the minimum Li deposits on the Si containing
electrodes, while 00Si showed significantly more Li plating on the surface. This is most
likely due to the electrode thickness variations, besides the reduced overpotential with Si
discussed above. The 00Si electrode thickness (~48 µm) is almost twice that of the other
two anodes (22~27 µm). It was reported that thicker electrodes increase the possibility of
there being lithium plating on the graphite surface during fast charging, owing to the ion
depletion and limited mass transport in electrolytes in thick anodes [3,28]. Thus, in this
regard, the thinner Si-Gr composite electrode would take advantage of the added capacity
that silicon provides, while avoiding some of the issues with Li plating.
The cross-sectional SEM image in 4e shows that the average thickness of the 00Si anode
is 54 µm after cycling, corresponding to a ~12% irreversible increase in thickness. The
observation is consistent with previous electrochemical dilatometry experiments for pure
graphite electrode thickness changes during fast charging [29]. In contrast, Figure 4f shows
that the 15Si anode is 40 µm thick after 100 XFC cycles, corresponding to a 48% end-of-life
swelling rate (compared to the 27 µm thick as-prepared electrode). The thickness of the
30Si electrode expands from 22 µm to 30 µm, resulting in a 36% swelling rate (Figure 4g).
 Batteries 2023, 9, 138 8 of 12

In addition, the cycled 30 Si anode coating shows some cracks, which extend from the
surface to the copper current collector. In contrast, the 15Si anode shows no obvious particle
boundaries and cracks throughout the depth, indicating that the graphite could buffer the
volume changes in Si and maintain the structural integrity of the electrode during cycling
to some extent.
The spatial distribution of electrolyte decomposition species including carbon, silicon,
fluorine, oxygen, and phosphorus was determined with EDS elemental mapping using
the SEM images in Figure 4, and the results are shown in Figure 5. The spot without Li
plating on the 00Si electrode (Figure 5a) contains a uniform distribution of carbon, with
some fluorine and phosphorus (arising from the electrolyte decomposition) dispersed
throughout the ensemble. Oxygen was more obvious on the edge of the graphite particles.
On the spot with Li plating (Figure 5b), the carbon signal was greatly reduced, while
the signatures including those from fluorine, oxygen, and phosphorus in the spectra
were increased significantly and distributed uniformly. The difference in the EDS maps
reveals heterogeneity in the chemical composition even on the same electrode when Li
plating occurred. More importantly, the top layer with Li metal promoted electrolyte
decomposition due to its reactivity. There being much less carbon and more fluorine
content suggest that more inorganic compounds such as LiF, Lix O, and lithium (oxy)fluoro-
Batteries 2023, 9, x FOR PEER REVIEW phosphate (Lix POy Fz ) exist in this layer, which is consistent with the results reported 9byof 13
Yang et al. [3] From the map in Figure 5c,d, it can be seen fluorine distribution accumulated
on the Si aggregates rather than on the Gr particles, indicating that the Si particles favor the
SEI growth with salt decomposition, which is consistent with the previous report [30]. The
inhomogeneity of the electrolyte decomposition products distribution in an Si-Gr compo-
inhomogeneity of the electrolyte decomposition products distribution in an Si-Gr composite
site anode
anode affect
affect the the properties
properties and functions
and functions of SEI of SEIWe
layer. layer. We this
suggest suggest
playsthis plays
a major a major
role in
role in cell degradation.
cell degradation.

Figure
Figure5. 5.
Corresponding
CorrespondingEDS EDSmapping for the
mapping for theSEM
SEMimages
imagesininFigure
Figure4. 4.
(a)(a) 00Si
00Si without
without Li plating,
Li plating,
(b)(b)
00Si with Li plating, (c) 15Si, (d) and 30Si. The column from left to right is the elemental mapping
00Si with Li plating, (c) 15Si, (d) and 30Si. The column from left to right is the elemental mapping
result for C, Si, F, O, and P. The scale bar is 25μm.
result for C, Si, F, O, and P. The scale bar is 25µm.

3.4. SEI Composition of the Aged Anodes

For the aforementioned anodes harvested from dissembled cells, the XPS analysis
determined the impact of the Si effect on the SEI evolution and composition. Deconvolu-
 Batteries 2023, 9, 138 9 of 12

3.4. SEI Composition of the Aged Anodes

For the aforementioned anodes harvested from dissembled cells, the XPS analysis deter-
mined the impact of the Si effect on the SEI evolution and composition. Deconvolutions of
the XPS spectra distinguish the contributions by various compounds. The anodes’ measured
(dotted line) and curve-fitted (solid line) XPS spectra for C 1s, O 1s, F 1s, and P 2p are shown
in Figure 6a after 100 XFC cycles. The integrated peak intensities are correlated with the
Batteries 2023, 9, x FOR PEER REVIEW atomic concentrations so that the relative proportions of the individual components/bonding 10 of 13
states in the surface layer can be calculated using the atomic sensitivity factors. Figure 6b
shows the relative atomic concentrations for each component for three electrodes.

Figure 6. (a) XPS spectra of C 1s, O 1s, F 1s, and P 2p core peaks of cycled Si-Gr graphite anodes
Figure 6. (a) XPS spectra of C 1s, O 1s, F 1s, and P 2p core peaks of cycled Si-Gr graphite anodes
paired NMC 811 cathodes after 100 XFC cycles. (b) The atomic percentage (at%) of the major SEI
paired NMC
components 811 cathodes
determined after
by the 100 XFC
curve fittingcycles.
in the(b) The atomic percentage
spectroscopy. (at%)
The bar plot of not
does the display
major SEIthe
components determined by the
atomic part that is smaller than 2%. curve fitting in the spectroscopy. The bar plot does not display the
atomic part that is smaller than 2%.
A lithiated graphite peak (LixC6) is observable at the lowest photon energy value
A lithiated graphite peak (Lix C6 ) is observable at the lowest photon energy value
(~283eV). In the
(~283 eV). In C1s spectra
the C1s in Figure
spectra 6a, therefore,
in Figure the the
6a, therefore, SEI SEI
layer is confirmed
layer to be
is confirmed to thin
be
enough
thin enough to emit photoelectrons from the underlying graphite particles. From 00Si30Si,
to emit photoelectrons from the underlying graphite particles. From 00Si to to
the30Si,
surface
the concentration of the lithiated
surface concentration graphitegraphite
of the lithiated increases from 3 from
increases at% to 11 at%,
3 at% respec-
to 11 at%,
tively. The SEI isThe
respectively. much
SEI thinner
is muchfor the 30
thinner forSithe
anode
30 Sicompared to thosetoofthose
anode compared otheroftwo anodes,
other two
considering the LixC6 signal.
anodes, considering the LixThe fraction
C6 signal. of fraction
The bulk characteristic C–C peakC–C
of bulk characteristic and peak
hydrocar-
and
bons feature (-CH2-) at 284.4 eV for the SEI is higher in 30Si, but they are almost the same
for 00 Si and 15Si. Several other carbonaceous species in the C 1s spectra at binding ener-
gies of above 285 eV are related to the breakdown of the EC solvent and are present in
every anode SEI layer [2,22]. The peak at 286.2 eV increases from 00Si to 30Si cells, which
is attributed to alcohols (C-OH), esters (C-O-C=O), and organic/semi-organic carbonates
Batteries 2023, 9, 138 10 of 12

hydrocarbons feature (-CH2 -) at 284.4 eV for the SEI is higher in 30Si, but they are almost
the same for 00 Si and 15Si. Several other carbonaceous species in the C 1s spectra at
binding energies of above 285 eV are related to the breakdown of the EC solvent and are
present in every anode SEI layer [2,22]. The peak at 286.2 eV increases from 00Si to 30Si
cells, which is attributed to alcohols (C-OH), esters (C-O-C=O), and organic/semi-organic
carbonates (C-O-C(=O)O). The peak at 290.2 eV ascribed to a carbon atom bonded with
three oxygen atoms (OC(=O)O), e.g., Li2 CO3 and organic carbonates, is less than 2 at%,
and these peaks are comparable between each anode. The total carbon content in the SEI is
sensitive and proportional to the Si content in the Si-Gr composite.
Accordingly, significant differences in the O 1s spectra peak shape are observed be-
tween the anodes. The mixture of C-O- and C=O-containing species typical of lithium
acetate, lithium alkyl carbonates, and Li2 CO3 was confirmed by a broad peak that domi-
nates the O1s spectrum and is centered at about 531 eV. This major peak moves to higher
binding energies from 15Si to 00Si. The peak at 533 eV is assigned to C–OH and F–P–O
compounds. When Si increases to 30 wt%, the dominant environment changes, in which
the contribution of C–O and F–P–O species is higher than those in the C=O environment.
The decomposition of the LiPF6 salt is indicated by the presence of Px Oy Fz - and LiF
signals in the F 1s and P 2p spectra. The F1s spectra show that the relative intensities of
the LiF and Lix POy Fz are also affected by the Si content in the anode. Without Si in the
anode, both LiF and Lix POy Fz are major components with a slightly higher LiF ratio (16:11).
However, Lix POy Fz becomes the dominant compound, and the ratio of LiF: Lix POy Fz
decreases from 1:7 to 1:14 as the Si content increases from 15 to 30. With respect to the
P2p spectra, some tiny differences were observed when we were comparing the anodes.
Although Lix POy Fz is the major phosphorus-containing component, a higher binding
energy feature at ≈137 eV was detected in 15Si and 30 Si anodes, which is close to the
value for the LiPF6 residue. It implies that due to the extensive solvent breakdown in
the electrolyte, some LiPF6 salt was not completely removed by rinsing it with dimethyl
carbonate (DMC), with some of it lingering in the SEI or trapped in pores on the Si-
containing cells after prolonged cycling.
The overview spectra provided in Figure 6 confirm a considerable change in the ele-
mental distribution of SEI for the cycled Si–Gr electrodes. Based on the analytical results,
we can state that the Si content impacts the SEI composition of the Si-Gr composite. The
baseline 00Si anode generated fewer organic species, indicating less electrolyte decomposi-
tion. Additionally, the total lithium atomic concentration is much higher for 00Si compared
to those of other two anodes. However, by adding Si to the anode, SEI had higher organic
contents (high C and O) due to severe electrolyte decomposition and LiPF6 hydrolysis.
We believe that the resultant organic-rich SEI with Si governs the main components of
the interphase layer. Consequently, the interfacial stability, ion-transport capabilities, and
mechanical properties of the electrode would be affected by this organic-rich SEI, con-
tributing to a large capacity fade [31]. As discussed in the introduction, another significant
obstacle for Si-based LIB cells is their fragile and unstable surface because Si is sensitive
to impurities in electrolytes such as water, carbon dioxide, and HF. The F content was
the highest at the SEI in 15Si, implying more salt decomposition at this surface. Again,
this trend implies that Si and Gr can potentially interact chemically during SEI formation,
beside electrochemically [32]. Besides the major SEI species with C, O, F, and P, the strong
Ni 2p signal found on all of the anode surfaces suggest Ni dissolution and deposition from
the NMC 811 cathode. Its concentrations are similar in 00Si and 15Si, but they are smaller
in 30Si. However, no clear Mn and Co signals were observed on the surface by XPS, which
is consistent with our previous work when NMC811 was used as cathode. In future work,
it is important to consider Ni’s function as a prominent contaminant in the SEI.
Batteries 2023, 9, 138 11 of 12

4. Conclusions
We systematically studied the effects of the Si content by employing Si-Gr composite
negative electrodes and NMC811 positive electrodes in full cells using accelerated XFC
aging protocols. Increasing the Si amount in the composite anode improved the rate
capabilities, specific capacity, and cyclability of the cells in early XFC aging cycles. The
loss of active Li due to continuous SEI reactions within the Si-Gr negative electrode likely
caused an increase in the capacity fade in long term. The post-mortem analysis of electrode
morphology showed electrode thickening and agglomerates of nonuniformly distributed
SEI components throughout the electrode with Si added to the anode. The addition of Si was
shown to reduce the possibilities of Li plating when a thin electrode was used to maintain
a similar capacity compared to that of the Gr-only electrode. A mechanism showing the
increase in organic components in the SEI layer because of electrolyte decomposition
was also presented with the addition of Si for capacity decay. We further emphasize the
importance of efforts to mitigate the degradation and aging of Si-based anodes in order to
capture the potential benefits to XFC capabilities, as identified here. This work advances
future work on fine-tuning the compositions and optimization of Si-Gr composites as
negative electrodes, in terms of high energy density and the high stability of Li-ion batteries.

Author Contributions: Conceptualization, Z.Y.; Data curation, Z.Y.; Formal analysis, Z.Y.; Investi-
gation, Z.Y.; Methodology, Z.Y., S.E.T. and X.W.; Project administration, B.J.I.; Resources, S.E.T. and
X.W.; Visualization, B.J.I.; Writing—review and editing, Z.Y.; Writing—review and editing, Z.Y. and
B.J.I. All authors have read and agreed to the published version of the manuscript.
Funding: The authors gratefully acknowledge support from the U.S. Department of Energy (DOE),
Vehicle Technologies Office, specifically from Brian Cunningham and David Howell. Argonne
National Laboratory is operated for DOE Office of Science by UChicago Argonne, LLC, under
Contract Number DE-AC02-06CH11357. The electrodes used in this article were made by Argonne’s
Cell Analysis, Modeling, and Prototyping (CAMP) Facility, which was supported by the Applied
Battery Research for Transportation Program.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author. The data are not publicly available due to confidentiality.
Conflicts of Interest: The authors declare no conflict of interest.

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