Paper 2023

MATRYOSHKA DUAL-SHELLED LITHIUM-SULFUR BATTERY 1
Bulk Scale Synthesis of a Novel Dual Core-Shelled Sulfur Cathode Composite
for High-Power Lithium-Sulfur Batteries With Application for use in Electric Vehicles
Bianca J. Turner
Oak Park and River Forest High School
Illinois - Chicago J.S.H.S. Regional Symposium
January 21, 2023

Table of Contents
List of Tables and Figures............................................................................................................. 3
Materials and Methods of Prototyping........................................................................................ 14
Initial Conductive Layer.................................................................................................. 17
Encapsulating Layer........................................................................................................ 18
TiO2 Coating.................................................................................................................... 18
Thermal Reduction.......................................................................................................... 18
PANI Coating.................................................................................................................. 19
Sulfur Infiltration and PANI Vulcanization..................................................................... 19
Slurry Preparation............................................................................................................ 20
Casting............................................................................................................................. 20
Coin Cell Construction.................................................................................................... 21
Testing............................................................................................................................. 22
Results......................................................................................................................................... 24
Discussions.................................................................................................................................. 29
Statistical Analyses.......................................................................................................... 29
Characterization............................................................................................................... 30
Limitations and Future Research..................................................................................... 31
Conclusions and Applications..................................................................................................... 33
References................................................................................................................................... 35
Raw Cycling Data for Cell BTA1............................................................................................... 40

List of Tables and Figures
Figure 1 Matryoshka Nesting Doll Comparison to Cathode Structure................................ 7
Figure 2 Lithium-Sulfur Battery Cell Chemistry................................................................. 8
Figure 3 Structure of Novel Cathode Material................................................................... 13
Figure 4 Flow Chart of Fabrication Process....................................................................... 16
Figure 5 Cathode 2 Material Structure Synthesis............................................................... 17
Figure 6 Casting of Material Using “Doctor Blade”.......................................................... 21
Figure 7 Cell Preparation and Assembly in Glove Box..................................................... 21
Figure 8 LSB Coin Cell...................................................................................................... 22
Figure 9 Data Input (a) and Cell Testing (b)....................................................................... 22
Figure 10 TGA Analysis....................................................................................................... 23
Figure 11 SEM Material Input.............................................................................................. 23
Figure 12 XRD Machine....................................................................................................... 23
Figure 13 Initial Capacities................................................................................................... 25
Figure 14 Capacities After 95 Cycles................................................................................... 25
Figure 15 TGA of BT Material............................................................................................. 25
Figure 16 TGA of BTA Material.......................................................................................... 25
Figure 17 SEM of BT Material………................................................................................. 26
Figure 18 SEM of BTA Material.......................................................................................... 26
Figure 19 Merged EDS of BT Material................................................................................ 26
Figure 20 Merged EDS of BT Material……….................................................................... 26
Figure 21 XRD of BTA Material.......................................................................................... 27

Table 1 F-test for Variances.............................................................................................. 27
Table 2 ANOVA Test........................................................................................................ 27
Table 3 Descriptive Statistics........................................................................................... 28
Table 4 Power Analysis.................................................................................................... 28
Table 5 t-test Assuming Unequal Variance...................................................................... 28
Table 6 Bonferroni, Spearman, and Cohen’s d Tests....................................................... 28
Figure 22 Individual Capacities.......................................................................................... 28
Figure 23 Means With 95% CI Error Bars.......................................................................... 28
Figure 24 Capacity and Coulombic Efficiency of BTA1.................................................... 28

Bulk Scale Synthesis of a Novel Dual Core-Shelled Sulfur Cathode Composite
for High-Power Lithium-Sulfur Batteries With Application for Use in Electric Vehicles
As a result of efforts to reduce vehicle carbon emissions, there is much interest in the
electric vehicle (EV) industry. The global electric car market is expected to reach over 1103.7
billion USD by 2030 (Allied Market Research, 2022; Precedence Research, 2021). High-power
energy storage devices satiate the global need for sustainable, affordable energy devices.
Currently, lithium-ion batteries (LIBs) are the most commercialized battery utilized in
EVs. However, despite their enormous use and commercialization, two main problems exist;
their use of expensive materials and suboptimal performance (Brehm et al., 2022; Grand View
Research, 2021; Markets and Markets, 2022; Yang et al., 2020). LIBs have reached their
maximum calculated performance, leaving little room for improved cell energy densities and
capacities. LIBs–though superior compared to other EV batteries–do not meet the increasing
standards of energy output for modern electric car demands (Kweon & Kim-Shoemaker, 2022;
Wang et al., 2021; Yang et al., 2020). The use of expensive materials and the low energy
density/capacities of LIBs leave much to be explored including various alternatives such as
lithium-sulfur batteries (LSBs) (Cheng et al., 2022; Li et al., 2021; Zhang et al., 2021; Zhao et
al., 2020). Due to the many issues with LIBs, most notably the high price (12,000-15,000 USD
per EV battery pack) and limited material utilization (through energy density), LSBs are
currently being explored as a viable solution (for example LSBs are approximately 30% cheaper
per kilowatt-hour compared to LIBs) (Huerte, 2022; Merrifield, 2020). With their inexpensive
material selection, environmentally friendly fabrication process, and outstanding performance
potential, scientists have attempted to commercialize LSBs for over 50 years (Li et al., 2021; Pai
et al., 2022; Wang et al., 2021; C. Zhao et al., 2020).

Because of the considerable issues with LSB chemistry, commercialization continues to
be an enormous challenge, one large issue is the polysulfide shuttle effect, which occurs during
cycling when intermediate lithium polysulfides are dissolved in the electrolyte leading to a
significant loss in capacity. Additionally, sulfur in the battery cell can expand up to 80%,
rendering the structure of the cathode and stability of the cell unstable, or broken in some cases.
The low conductivity of sulfur also poses an issue as conductive materials need to be
added–which can decrease the energy density of the cell. Successful LSB performance has
typically relied on processes including nanofabrication, which involves individually modifying
particles. As a result of these issues, few batteries have been developed that reach the potential of
LSBs without using expensive and complicated fabrication processes, which make LSBs an
unattainable option (Han et al., 2022; Yang et al., 2020; C. Zhao et al., 2020).
There is a gap in current research between the theoretical attributes of LSBs and the
practical realization of a high-cycling battery cell engineered with an inexpensive, applicable
fabrication process. The purpose and relevance of developing a high-power LSB cell involves
producing a less expensive battery that can be utilized in EVs–with the ultimate application of
decreasing carbon emissions from the wider availability of EVs.
Creating a less expensive EV battery would likely decrease the price of the EVs (the
average price of an EV as of 2022 is over 66,000 USD) and make them more accessible, which
in turn may reduce greenhouse gas emissions (Han et al., 2022; Kelley Blue Book, 2022; Yang et
al., 2020). In 2022, there was a reported peak carbon dioxide measurement at 421 ppm,
compared to the 280 ppm that remained constant for over 6,000 years of initial human
civilization. Combustion engine vehicles contribute a significant portion of carbon dioxide
emissions (National Oceanic and Atmospheric Administration, 2022; United States

Environmental Protection Agency, 2022). Using economic and environmentally friendly
batteries such as LSBs in EVs could significantly reduce transportation carbon emissions by
replacing combustion engine vehicles (International Energy Agency, 2022; U.S. EPA, 2022).
This experiment used a novel, dual-shelled, matryoshka nesting doll-like structured cathode
constructed of conductive/polysulfide absorbing materials fabricated in a bulk synthesis (Figure
1). The application of this novel cathode material for practical commercialization has an overall
goal of advancing LSB research in achieving an economic, high-cycling LSB. The encapsulating
nature of the matryoshka structured cathode allows for improved efficiency as well as stronger
interactions between materials.
Figure 1
Matryoshka Nesting Doll Comparison to Cathode Structure
Though they use lithium, the abundant, inexpensive material sulfur (with conductive
additives) is used as the cathode in LSBs (Chien et al., 2022; Lee et al., 2020; Zhu et al., 2019).
A lithium-sulfur battery cell contains a lithium-metal anode, a sulfur cathode (with a conductive
carbon host), an electrolyte (lithium bis(trifluoromethanesulfonyl) imide in
dioxolane/dimethoxyethane (LiTSFI-DOL/DME)), and a polymer separator (Figure 2) (Lin et
al., 2021; Pai et al., 2022; Wang et al., 2021).

Figure 2
Lithium-Sulfur Battery Cell Chemistry
LSBs rely on the multiple redox
reactions of the sulfur cathode and
lithium anode. Active sulfur is reduced
to form lithium polysulfides (LiPS) and
then reduced again to form insoluble
LiPS, Li2S2/Li2S. The reduction of
sulfur is accompanied by the reduction
of the anode where lithium ions are
formed that move toward the cathode
and balance their charge (Huang et al.,
2016; Yang et al., 2020).
LSBs have a high energy density at a maximum of 2600 Wh kg⁻¹ vs. 270 Wh kg⁻¹ in
LIBs (Jian et al., 2016; Lai et al., 2020; Li et al., 2021; Wang et al., 2021; Zhang et al., 2021).
With a low energy density, LIBs do not use the material efficiently compared to the charge given
(Dragonfly Energy, 2021; Epec Engineered Technologies, 2022). LSBs have a maximum
capacity of 1675 mAh g⁻¹, which is >6 times higher than the capacity of LIBs at 150-200 mAh
g-1, demonstrating that LSBs can store more energy. Recently, research by Cheng et al. (2022)
achieved a high specific energy density of 695 Wh kg-1 and an ultrahigh-specific capacity of
1563 mAh g⁻¹ in a pouch cell (a cell that further tests LSBs performance for practical
application). Though the cell died after several cycles, the results demonstrate that achieving
applicable results is possible.

LSBs use non-toxic materials ensuring an environmentally safe fabrication process (Li et
al., 2021; Lin et al., 2021; Tian et al., 2021). Expensive materials such as cobalt, nickel, and
manganese commonly used in lithium-ion cathodes are not used in LSBs. Sulfur as of 2022 costs
183 USD which is a huge decrease compared to the prices of cobalt (51,195 USD as of
10/13/22), nickel (21,915 USD/ as of 10/11/22), and lithium-iron-phosphate LIB materials
(20,657.67 USD as of 10/10/22) (Apodaca, 2022; Farchy et al., 2022; Huerte, 2022; Jaskula,
2022; London Metal Exchange, 2022; Shandong Longshong Information Technology
Corporation Limited, 2022; Trading Economics 2022; Tycorun Energy, 2022). With the high
cost of LIB materials, the importance of exploring LSB technology is ever more necessary.
LSBs are a competitive alternative as they utilize less expensive materials in their
fabrication process, offer higher capacities and energy densities, and use environmentally safe
materials/procedures. Despite the advantages, the many problems with LSB chemistry
demonstrate room for future commercialization.
During charge/discharge reactions, the polysulfide shuttle effect occurs, where sulfur
reduces to form multiple lithium polysulfide intermediates and is dissolved in the electrolyte
before reaching its insoluble form of Li2S2 and Li2S. This leads to an irreversible loss of sulfur
and reduces capacity and Coulombic efficiency within the cell. A fast conversion of LiPS before
they become irreversibly reduced and/or the employment of polysulfide-absorbing material is
needed in the battery (Cavers et al., 2020; Zhang et al., 2021; C. Zhao et al., 2020; Zhen et al.,
2022). Sulfur and charge/discharge reaction products are insulating, as a result, these factors
render the battery low conductivity and sluggish kinetics. Conductive materials need to be added
on the cathode side to boost the kinetics of sulfur (Chien et al., 2022; Wang et al., 2021; Zhao et
al., 2020). Because of sulfur expansion (80%), vacant spaces also need to be considered in the
structure of the cathode material (Lee et al., 2020; Li et al., 2021; Wei Seh et al., 2013).
In a lithium-sulfur pouch cell, there are additional issues that are not present in
commonly tested coin cells–which are small single-shelled batteries. In a pouch cell, saturated
and premature precipitate lithium polysulfides block the electron pathway on the conductive
cathode matrix structure. The early precipitation exerts greater pressure on the electrochemical
kinetics which can lead to rapid battery failure. This issue is very different in coin cell
conditions. The failure of the lithium metal anode also poses an issue. In pouch cells, the
depletion of lithium metal is after only a few cycles, as the anode displays uneven morphology
and corrosion. Anode depletion is the main cause of pouch cell battery failure. However, before
developing a pouch cell for the practical testing of LSBs, a high-cycling stable cathode material
needs to be produced (Cheng et al., 2022; Chien et al., 2022; C. Zhao et al., 2020). There have
been many efforts to commercialize LSBs employing different structures and materials, however
due to the multiple challenges they have been largely unsuccessful (Kweon & Kim-Shoemaker,
2022; Li et al., 2021; Yang et al., 2020).
Scientists have been working for over 40 years on addressing the issues with LSBs.
Specifically, carbon nanotubes (CNT), and graphene oxide (GO) have demonstrated positive
results when used as conductive hosts. Huang et al. (2016) used multiwalled CNT/GO composite
films as an interlayer to add conductivity and offer pathways for electron/ion transfer–while also
blocking polysulfides. The results offered an initial specific capacity of 1370 mAh g⁻¹,
demonstrating that both CNT and GO are beneficial additions to LSBs. Specifically, CNT has
high conductivity and more advantages than other nanostructured materials because of its unique
structure with gaps and pathways for ions to transfer and excellent flexibility/stability (Lee et al.,
2020; Lin et al., 2021; Wei et al., 2020). In 2021, Zhang et al. (2021) developed a TiO2-TiN
three-dimensional CNT coaxial sponge LSB. The performance of the cell gave 1289 mAh g⁻¹
capacity with a retention of 85% after 500 cycles. The results from this experiment both
reinforce the conductivity that CNTs bring in LSBs and note that TiO2 can absorb and limit
polysulfides. Using an encapsulating structure, Wei Seh et al. (2013) achieved competitive
results using a titanium dioxide yolk shell-like coating that accounted for sulfur expansion and
trapped polysulfides. The cell had an initial capacity of 1030 mAh g⁻¹ and a .033% decay per
cycle after 100 cycles. TiO2 can bring stability into LSBs, prolong cycling life, and address the
polysulfide shuttle effect within the battery. Insoluble polysulfide absorption and extended
cycling life are significant requirements in LSBs, as a result, TiO2 is explored as a beneficial
material.
Materials such as GO and reduced graphene oxide (RGO) also provide conductivity. Tian
et al., (2021) describe that graphene has gained attention for its high conductivity, high specific
surface area of 2630 m²g⁻¹, electron mobility of 15,000 cm2V-1S-1, and excellent flexibility.
Graphene as a matrix material can provide a beneficial conductive framework for the sulfur
cathode and improve sulfur utilization. RGO is a form of graphene oxide where oxygen content
is minimized. RGO is very similar to graphene (which is difficult to work with in LSBs due to its
properties), aside from slight oxygen functional groups. RGO has a large surface area and is
conductive making it successful in LSBs (Azizghannad & Mitra, 2018; Tian et al., 2021).
Using nanoparticles of sulfur and employing a porous host, there is faster electrochemical
reaction kinetics in the cell as ions are able to transfer faster and LiPS avoid being reduced (Han
et al., 2022; Zhang et al., 2020; Zhen et al., 2022). Additionally, polyaniline (PANI), a polymer,
has been used to crosslink itself with sulfur, allowing the sulfur to be accessed more easily, and
in addition, to address polysulfides (Kweon & Kim-Shoemaker, 2022; Li et al., 2022).
Conductive, polysulfide absorbing materials and a porous space-containing matrix
accommodating sulfur expansion along with electron/ion transfer are requirements that need to
be considered for high-power stable LSBs.
Fabricating a high-cycling cathode that meets requirements in addressing large issues
with LSB chemistry is needed for long-life/stable lithium-sulfur batteries. Due to the numerous
applications and benefits of lithium-sulfur technology in electric vehicle battery applications, the
goal of this experiment was to develop a novel cathode structure utilizing many materials and a
design wherein sulfur nanoparticles were surrounded by multiple layers of RGO and CNT for a
conductive layered matrix with spaces accommodating ion/electron transfer for a matryoshka
structured lithium-sulfur coin cell battery.
In this experiment, a novel cathode material was synthesized utilizing much trial and
error, cast onto aluminum foil, and then manufactured into coin cells which was a necessary first
step to testing the performance of the cathode. This experiment was completed at the Illinois
Institute of Technology and guided by the methods of previous experiments, including
Azizghannad and Mitra (2018), Brehm et al. (2022), Kweon and Kim-Shoemaker (2022), Lin et
al. (2021), Long et al. (2021), Tian et al. (2021), Tsao et al. (2018), Wang et al. (2021), Wei Seh
et al. (2013), and Zhen et al. (2022). The reason for conducting the experiment is the
combination of the gap in research with respect to the lack of commercially applicable LSB
cathodes and the established benefits of LSB technology for commercial application in EVs. An
individual group in the final matryoshka dual-shelled structured material is shown in Figure 3.
Figure 3
Structure of Novel Cathode Material
This experiment
addressed the gap in research by
testing 1) a novel fabricated
cathode material and 2) an
optimized structural design of a
high-power LSB cathode
through the inclusion of a
layered CNT/RGO matrix,
linked sulfur nanoparticles, and
a polysulfide absorbing TiO2 coating. Currently, this novel design using an encapsulating
structure with utilized materials has not been tested or fabricated in published research. The
independent variable in this experiment was the specific fabricated cathode material and the
dependent variable was its performance in the constructed coin cells quantified by coin cell
cycling. The cathode material itself was characterized by X-ray diffraction (XRD), scanning
electron microscopy (SEM), energy dispersive spectroscopy (EDS) (through SEM), and
thermogravimetric analysis (TGA) to determine elemental content and visual structure.
The results from this experiment contribute to the large research field of LSBs and
demonstrate the benefits of employing the novel Matryoshka-structured cathode material. By
developing and testing an untested cathode material, the field of high-power technology and
lithium-sulfur research is furthered. LSBs are less expensive with their material usage (estimated
30% less kilowatt-hour than LIBs), utilize an environmentally friendly fabrication process, and
have significantly higher energy densities and capacities. With less expensive batteries in EVs,
the prices of the cars themselves decrease and become accessible to the broader public. The
larger availability of EVs leads to reduced transportation emissions, which contribute to the
overall decrease of greenhouse gasses in the atmosphere (Kweon & Kim-Shoemaker, 2022; Long
et al., 2022; Merrifield, 2020; Yang et al., 2020; Zhen et al., 2022).
Developing a high-power, stable and conductive cathode is important in realizing the
potential of LSBs for further commercialization. This experiment applied a novel design for
synthesizing a cathode for LSB coin cells by employing a matryoshka nesting doll-like
dual-encapsulated structure that expands the research field of high-power energy storage devices.
Materials and Methods of Fabrication
This experiment was conducted over a six-month period of time, involving a conservative
estimate of 150+ hours of lab time plus additional time outside of the lab. The methods
followed standard school, state, and local safety regulations, as well as protocols suggested by
product suppliers. This experiment was conducted in the Mandal and Segre labs at the Robert A.
Pritzker Science Center at the Illinois Institute of Technology. Due to the nature of the cathode
and coin cell fabrication the procedures used and the structure of the cathode material itself were
under constant iteration based on much trial and error. In the end, 2 different iterations of the
cathode structure were created, 4 coin cells were constructed and tested with coin cell
cycling–collecting long-term data on 2 cells, and 2 different cathode materials were characterized
through TGA, EDS, SEM, and XRD. The independent variable for this experiment was the novel
fabricated cathode material while the dependent variable was its performance in constructed coin
cells quantified through coin cell cycling–to quantify the capacity/Coulombic efficiency at
different cycling numbers. The performance of the cells was compared to nickel manganese
cobalt (NMC) (highest capacity) LIB coin cell cycling data from a study by Lai et al. (2020), as
the control. The experimental hypothesis (HE) stated that by utilizing the fabricated cathode
material, performances of fabricated LSB coin cells would be increased. The null hypothesis (H0)
stated that there would be no statistically significant difference between the means of the control
and experimental groups. This experiment utilized the randomization method for data collection
to ensure there wasn't any bias in choosing samples and in data collection. This procedure differs
from other experiments in that it encompasses many different methods and the structure of the
utilized materials has not been done before. Additionally, the processes used are inexpensive and
applicable for practical implementation on a bulk scale.
The process for the iterated cathode material and cell construction took place in 11 main
stages: 1) formation of the conductive CNT/edge-functionalized graphene oxide (EFGO–a
precursor to RGO) matrix. 2) encapsulation layer formation of CNT/EFGO over the initial layer,
giving a matryoshka dual-shelled structure. 3) TiO2 coating over all components in the structure.
4) reduction of EFGO to form RGO. 5) PANI coating over all components in the structure. 6)
sulfur infiltration. 7) PANI vulcanization–meaning it crosslinked itself with sulfur. 8) preparation
of slurry. 9) casting of material. 10) coin cell construction. 11) device testing of the material and
coin cells: material samples were characterized using XRD, TGA, EDS, and SEM. Coin cells
were tested by coin cell cycling on an MTI 8 Channel Battery Analyzer. Figure 4 depicts an
outline of the experimental process and the reiterations of the LSB cathode design.
All the chemicals used in this experiment were >99% grade purity. Each of these phases
were iterated in the process as well as adjusted for the ongoing changes in the structure design
itself. By employing this structure and design for the cathode, LSBs can be applicable for
practical applications that achieve competitive results. The structure of the finalized cathode
material during different stages is shown in Figure 5.
Figure 4
Flow Chart of Fabrication Process

Figure 5
Cathode 2 Material Structure Synthesis
The initial coin cell featuring the BT material had the same structural design as BTA
without a PANI coating; the methods for both iterations were the same except for the PANI
stages. In this experiment, all chemicals were massed in a Mettler Toledo Balance (0.1 mg).
Initial Conductive Layer
In a 100 ml beaker, 20 mg of CNT, 350 mg of Triton X-100 (dispersion agent), and 50 ml
of deionized cold water were measured and sequentially mixed with a Faithful Magnetic Stirrer
for 30 minutes at medium speed. In another 100 ml beaker, 50 mg of EFGO and 50 ml of cold
water were sequentially mixed with a magnetic stirrer for 30 minutes at medium speed and low
heat. Half of the CNT beaker and half of the EFGO beaker were added into a 150 ml beaker and
stirred for 5 minutes. 100 mg of C6H8O6 and 100 mg of SnClH2O were then added. The mixture
was stirred for 10 minutes. Originally the mixing process was intended to be via digital
sonication, however, it did not disperse very well thus the product was sequentially mixed with a
magnetic stirrer instead.

Encapsulating Layer
The discarded halves of the CNT and EFGO mixtures were added to the CNT/EFGO
composite beaker and stirred for 5 minutes with a magnetic stirrer. Another 100 mg of both
C6H8O6 and SnClH2O were added and stirred for 5 minutes. The mixture was then digitally
sonicated for 10 minutes using a Branson Digital Sonicator at 20 kHz frequency and centrifuged
using a Wanlecy Electric Lab Benchtop Centrifuge LD-3 for 30 minutes at 2,500 RPM. The
temperatures for all of the processes during this stage were 60-70°C.
TiO2 Coating
For the third stage, a TiO2 coating was made around the structure. The resulting
dual-shelled product from the second phase was transferred into a 50 ml Deschem
polytetrafluoroethylene lined hydrothermal synthesis reactor stainless steel digestion vessel
(Teflon bomb) using 25 ml of cold ethanol. 2 ml of H20 was added to a separate container along
with 639 mg of titanium IV butoxide (Ti(C4H9O)4). The solution was digitally sonicated using a
Branson Digital Sonicator at 20 kHz frequency and added to the contents inside the Teflon bomb.
The Teflon bomb was put in a Fisher Scientific Muffle Furnace at 85°C for 4 hours.
Thermal Reduction
After the TiO2 coating was obtained, the fourth stage of thermal reduction was
completed. The material was taken out of the muffle furnace and pestled 5 times using a 150 ml
mortar and pestle and scraped with a Thomas Scientific chemical scoop. The black fine powder
product was combined with 100 mg of polyvinyl alcohol (PVA) solution and 100 mg of I2 and
placed in a Teflon bomb in an oven at 80°C overnight. Two-stage heating was then done with the
resulting product. For this, the product was placed overnight on a ceramic dish inside a
Thermolyne 79400 Tube Furnace–which dries material in a sealed setting with an inputted gas.
The first stage of heating was at 250°C in ambient air with a rate increase of temperature at
5°C/min for 2 hours. The second stage of heating was at 850°C in argon gas at a rate increase of
temperature at 5°C/min for 2 hours. The EFGO was reduced to form RGO through the thermal
method used in this phase.
PANI Coating
With the material from stage 4, aniline was added in a one-to-one ratio. The mixture was
put into a small beaker with 2.28 g of H20, 327.5 g of aniline, 200 mg of H2SO4, and 3 zirconium
balls. The beaker was put in a Benchmark BeadBug 6 machine (homogenizer) for 1 cycle of 5,
90-second intervals with 30 seconds of rest in between. The beaker was then placed in a fridge at
4°C for 15 minutes. 0.80 g of ammonium persulfate and 2 g of H2O were added into the beaker
and left in the fridge at 4°C for 5 minutes. With the ammonium persulfate initiator, the aniline
formed into polyaniline. The mixture was placed in the Benchmark BeadBug 6 machine and was
run for 5 cycles of 5, 90-second intervals with 30 seconds of rest in between. The beaker was
finally placed in an OHAUS Mini Pulsing Vortex Mixer and vortexed at maximum speed for 2
hours. The polyaniline coated all components of the cathode material after this step. For the BT
material this stage did not happen–there was no PANI in the structure at all–as the addition of
PANI was an iteration based on trial and error from the first coin cell fabrication using BT.
Sulfur Infiltration and PANI Vulcanization
The coated cathode material was filtered and washed with water and ethanol. It was then
dried using a vacuum pump at 80°C. 484 mg of sulfur was added to 435.2 mg of the product and
ground 5 times using a 150 ml mortar and pestle. Half of the product was added to a Teflon
bomb and then placed in the tube furnace for two-stage heating at 155°C for 12 hours and then at
280°C for 12 hours in argon gas. During this process, the seventh stage was also completed,
wherein PANI was vulcanized (sulfur cross-linked PANI). In the fabrication of the BT material,
instead of the two-stage heating process, the product was placed in a Teflon bomb in a muffle
furnace at 155°C overnight.
Slurry Preparation
After all the other stages were complete, the material was then prepared into a slurry
(semi-liquid mixture). The composite cathode material was combined in an 80:10:10 ratio, where
80% was the fabricated material, 10% was the Super P additive (carbon black), and the other
10% was the polyvinylidene fluoride (PVDF) additive. 120 mg of the fabricated material was
used, 15 mg of Super P was used, and 15 mg of PVDF was used. Additionally, 620 mg of NMP
solvent was added. The prepared slurry was mixed with 3 small zirconium beads and put in a
Benchmark BeadBug 6 machine for 5 cycles of 5, 90-second intervals with 30 seconds of rest in
between.
Casting
In the ninth phase, the slurry was cast onto Al foil by taping the foil onto glass, pouring
the slurry on top, and then using a metal “doctor blade” device to smooth the material. A “doctor
blade” device is a piece of equipment that holds a sharp metal blade at a fixed distance over a
material and uses the blade itself to create a smooth and consistent coating of a substance over a
surface (as shown in Figure 6 wherein the device is used to coat Al foil with the cathode
material). The casted Al foil was then dried in the oven. Using a hammer to hit a circle puncher
(a metal device with a sharp hollow cylindrical blade at the end), circle disks of the casted
material were punched at the exact circumference of the coin cell casing.
Figure 6
Casting of Material Using a “Doctor Blade”
Coin Cell Construction
For the tenth stage in
this experiment, coin cells
were constructed. Coin cells
were built in an argon
atmosphere glove box–as
lithium is very reactive with
oxygen (Chien et al., 2022;
Yang et al., 2020; Zhao et al.,
2020). The glove box is shown in Figure 7.
Figure 7
Cell Assembly in Glove Box
The cells were assembled
using a LiTSFI DME/DOL
electrolyte. Li foil was used as the
anode. A stainless steel spring,
stainless steel current collectors, and
standard polymer separators were
used in the cell. All coin cells were
constructed with the structure shown
in Figure 8. BT material cells were labeled BT1 and BT2, and BTA cells, BTA1 and BTA2.
Figure 8
LSB Coin Cell
Testing
The performance
of the cells were measured
using coin cell cycling.
Coin cells were attached to
an MTI 8 Channel Battery
Analyzer that shows the
capacity and Coulombic
efficiency relative to different cycling numbers through a computer. The sulfur content and data
about the cells were entered into a MTI Channel Analyzer Program on a computer as shown in
Figure 9(a). The cells were placed in channels as shown in Figure 9(b).
Figure 9
Data Input (a) and Cell Testing (b)
To characterize the
fabricated cathode materials,
TGA (Figure 10), SEM (Figure
11), and XRD (Figure 12) were
performed. It is worth noting
that XRD was only performed
on the iterated material, BTA.

Figure 10
TGA Analysis
Thermogravimetric analysis was
performed using a Mettler Toledo TGA
Machine taking a small unused portion of the
cathode material sample and placing it on a
balance where the machine measured the
amount of material lost and correlated it with
a specific percentage of sulfur.
Figure 11 Figure 12
SEM Material Input XRD Machine
Scanning electron microscopy was done on the cathode material by using the Phenom
ProX desktop SEM. The sample was placed onto a carbon adhesive which was then fixed in a
canister below the microscope lens as depicted in Figure 11. The SEM displayed the microscope
image of the material on a computer screen. Through SEM, EDS was done to identify elemental
components of the structure. Using a ThermoARL XRD machine (Figure 12), XRD was
performed. The XRD was set up by placing a small amount of the cathode material sample into a
canister and allowing light to pass through.
Results
Upon initial cycling, the BT1 cell, due to an undetectable/unpreventable construction
error, short-circuited, as a result, there is no cycling data for that individual cell. The full data for
cell BT2 was lost due to an error in the data-collecting software, consequently, there is no
quantitative data for every run cycle. Based on the cell data the estimated energy density was
calculated by multiplying the initial discharge capacity by the estimated voltage (2.1V). The
initial capacity of the BT2 cell was 760 mAh g-1, it ran for 400 cycles until it fell below 385 mAh
g-1. At cycle 95 the capacity was 520 mAh g-1. The estimated energy density was 1596 Wh/kg
(maximum is 2600 Wh/kg for LSBs). The BTA2 cell displayed an initial specific capacity of 823
mAh g-1 but was taken off of cycling after 10 cycles due to limited channel space. At cycle 10
this cell displayed a capacity of 530 mAh g-1. The estimated energy density was 1728 Wh/kg.
The BTA1 cell ran for 95 cycles with an initial capacity of 1137 mAh g-1. At cycle 95 the
capacity of this cell was 607 mAh g-1. The estimated energy density was 2387 Wh/kg. Figure 13
shows a graph of the initial capacities of BTA1, BT2, and a LIB coin cell (control group). Figure
14 shows a graph of the capacities of BTA1, BT2, and the LIB coin cell after 95 cycles.
Figure 13 Figure 14
Initial Capacities Capacities After 95 Cycles
The TGA of BT (Figure 15) and BTA (Figure 16) is shown where the step percentage
relates to the percentage of sulfur. The SEM of BT (Figure 17) and BTA (Figure 18) are both at
the same scale of 200 μm. The merged EDS of BT (Figure 19) and BTA (Figure 20) show the
highest abundance of material in small sections under a key of either sulfur (S), titanium (Ti), or
carbon (C). The XRD of the BTA material is shown in Figure 21.
Figure 15 Figure 16
TGA of BT Material TGA of BTA Material

Figure 17 Figure 18
SEM of BT Material SEM of BTA Material
Figure 19 Figure 20
Merged EDS of BT Material Merged EDS of BTA Material
Note. The material is shaded according to the most abundant Note. For this EDS, the most abundant material was sulfur in
material, with a key of sulfur (S), titanium (Ti), and Carbon (C). all sections of the material, as a result, it is the only shade shown.
Figure 21
XRD of BTA Material
Statistical tests were used to analyze the full cycling
data of the BTA1 cell, using it as the experimental group. An
F-test (Table 1), an ANOVA test (Table 2), and a t-test (Table
5) were performed to test variance. Based on initial F-test
results, it was determined that an unequal variance t-test was
the most appropriate statistical test. Descriptive statistics were
calculated, displaying the standard deviation, standard error of
the mean, and 95% confidence intervals (95% CI) of both
control (capacity of LIB coin cell) and experimental (capacity
of BTA1 coin cell) groups (Table 3). Power Analysis (Table 4),
Bonferroni Correction, Spearman Correlation, and Cohen’s d (Table 6) were calculated. The data
was also represented for individual cycles (Figure 22) and for mean capacities across 95 cycles
with 95% CI error bars (Figure 23). For all statistical analyses, an n-value of 95 was used,
relating to the 95 cell cycles of BTA1 and the LIB coin cell. The capacity and Coulombic
efficiency of cell BTA1 is shown in Figure 24.
Table 1 Table 2
F-test for Variances ANOVA Test

Table 3 Table 4 Table 5
Descriptive Statistics Power Analysis t-test Assuming Unequal Variance
Table 6
Bonferroni, Spearman, and Cohen’s d tests Figure 22
Individual Capacities
Figure 23
Means With 95% CI Error Bars
Figure 24
Capacity and Coulombic Efficiency of BTA1

Discussions
Statistical Analyses
To analyze the data and determine its significance, first, an F-test (Table 1) for variance
was calculated revealing an F-critical value (1.406) smaller than the F-value (953.910), therefore
deducing that a t-test assuming unequal variances was necessary. Then a single-factor ANOVA
test (Table 2) was calculated, (p-value <.0001). An unequal variance t-test was performed
yielding a t-test p-value also <.0001 (Table 5). The standard deviation, standard error of the
mean, and 95% confidence intervals were also calculated. A Bonferroni Correction was
conducted in order to prevent a Type I error (rejecting the null hypothesis when it is true–as it
accounts for multiple groups and divides alpha (typical 0.05) by that number). The calculated
t-test p-value is considered significant if it falls below the Bonferroni corrected alpha. This
experiment had 2 total groups–control and experimental, therefore the Bonferroni corrected
alpha was 0.025, and the t-test p-value, as well as the ANOVA p-value, were well below the
corrected alpha. Based on this result, the probability of a Type I error in this experiment is less
than 0.1%. It was concluded that there was a clear difference between the control and
experimental groups. Power Analysis was calculated to reduce the chances of a Type II error
(accepting the null hypothesis when it is false). The Power value is the probability of not making
a Type II error, the closer the power is to 1, the closer the ability to detect a false null hypothesis.
Using the mean of the value needed to accept the null hypothesis, the standard deviation of the
control, the sample size, the sample mean, the standard error of the mean, and the critical value,
the beta value was calculated. One was subtracted by the calculated beta value to get the power
value. The calculated beta value for this experiment was 0, and the power value was 1 (Table 4).
The result from this analysis indicates that the probability of finding a true difference in capacity
by analyzing the data if one exists is extremely close to 100%. The effect size was calculated as
well to determine the significance of the data. A large effect size demonstrates that a research
finding has practical significance. The effect size (Cohen’s d) for this experiment was 11.508
(Table 6). Using Cohen’s d value to classify effect size, a d value larger than 0.8 is considered a
large effect size. The Cohen’s d/effect size value for this experiment is much larger than 0.8 thus
there is a large effect size, emphasizing the statistical significance of the results. The Spearman
Correlation was calculated to be a value of 0.950 (Table 6), suggesting a positive correlation
between the experimental and control groups, meaning as one increases the other also tends to
increase. In the scope of this experiment, based on the positive correlation assumed by the
Spearman correlation, as the cycling number increases, if the capacities of one group fade, the
capacities of the other group will also fade in most cases. Given the statistical significance
demonstrated by the ANOVA, F-test, t-test, Bonferroni Correction, Power, Cohen’s d, and
Spearman Correlation, the fabricated cell and novel cathode design were successful on this scale.
Additionally, the initial capacity of the BTA1 cell demonstrates the ability to achieve competitive
results with studies employing nanofabrication while employing a bulk-scale synthetic
method–demonstrating that a LSB cell can store high amounts of energy while being easier and
less expensive to construct (Kweon & Kim-Shoemaker, 2022; Yang et al., 2020; Zhao et al.,
2020).
Characterization
Several characterization tests were performed on the BT and BTA materials to compare
and comprehend their contents. Based on TGA results the sulfur percentage of the BT material
was 68.29%. The sulfur percentage of the BTA material was 39.65% supporting the existence of
PANI crosslinked sulfur, as there are equal amounts of sulfur in both materials, the 39.65%
relating to loose unlinked sulfur in the material. The SEM results of the BT and BTA materials
are drastically different at the same scale, the BTA sample appearing more uniformly distributed
(without any large chunks), demonstrating structural change resulting from iterated steps and the
introduction of PANI. The EDS image of the BT material illustrates the majority of carbon,
sulfur, and titanium in different areas of the material. There is no uniform dispersion of material
shown in this result however it shows the existence of TiO2 from evidence of Ti abundance in
areas of the sample shown in the merged EDS image. The merged EDS of BTA shows only
sulfur as the predominant material in all sections of the sample, demonstrating a uniformly
distributed structure. The XRD of BTA supports the presence of TiO2 in the material as the
EDS–because there were no sections where TiO2 was the majority–did not detect titanium. The
characterization of the BT and BTA materials demonstrates the existence of PANI cross-linked
sulfur and illustrates an improvement in the overall structure from material BT to BTA (Kweon
& Kim-Shoemaker, 2022; Li et al., 2022).
Limitations and Future Research
Though the results of this experiment indicate proof-of-concept for the iterated
Matryoshka dual-shelled structured BTA cathode, this experiment had several limitations with
additional opportunities for future research. Due to the nature of this experiment, there are both
small iterations that could be made to the design of the cathode material and larger structural
changes that could open up avenues for new experiments.
The next primary goal of this experiment is to further test the BTA cathode material by
optimizing the design of the cathode material and creating more coin cells. A significant
limitation of this experiment was the limited channel availability to test and run coin cells, as
only 4 could be constructed because of this issue. Out of the 4 cells constructed, 1 failed due to a
construction error and another had to be removed after 10 cycles due to limited channel space.
Steps for cathode design optimization include shifting amounts of chemicals used, exploring new
chemicals to improve interactions within the cell, and utilizing different methods of synthesis to
further decrease the cost and ease the construction process.
An obstacle in this research was the limited cell cycling data, by creating more cells and
analyzing their results, this research can be further supported. Another future goal would be to
test cells with cyclic voltammetry and electrochemical impedance spectroscopy to understand the
redox reactions within the cell and how the cell reacts to various electrical currents respectively.
Learning this information is important in further understanding the interactions in the cell to
further improve and make iterations based on the results. The BTA1 cell began with a high
capacity of 1137 mAh g-1, after 10 cycles it faded to a capacity of 771 mAh g-1. The BTA2 cell
started off with a capacity of 823 mAh g-1 after 10 cycles faded to 530 mAh g-1. Using
information from additional tests could help determine and explain the reason why the capacity
faded so fast in a small number of cycles. Using that information, the design can be modified to
include strategies to address noted problems. In this experiment estimated energy densities were
calculated, for the BT2, BTA1, and BTA2 cells, giving estimated values of 1596 Wh/kg, 2387
Wh/kg, and 1728 Wh/kg. Completing approximate energy density calculations is important in
providing more accurate information about the cells and the qualities of fabricated materials.
There is also a future opportunity of creating a pouch cell to test the practicality of the
BTA cathode–after it has been optimized. Using the optimized design of the cathode in the pouch
cell research can then venture into addressing issues with the anode specifically in pouch cells.
Exploring other battery types such as sodium-ion batteries or thermal energy storage devices and
applying the same structural designs could also be a possibility for future research.
Overall, the data from this experiment allow the rejection of the null hypothesis via the
cycling data for the BTA1 cell and the cycling data for the LIB coin cell control. The immense
increase in capacity for the fabricated LSB cell in the experimental group (difference initial
capacity of 972 mAh g-1) is indicative of improved functionality compared to the performance of
the LIB coin cell. This novel design and fabrication method has applications to future LSBs that
can be developed and optimized more extensively.
Conclusions and Applications
The novel cathode design and cell created in this experiment demonstrate promise as a
practical and applicable high-performing LSB using an efficient, environmental, and less
expensive method in comparison to LIBs. Existing research groups have been able to create
high-performing LSBs with immensely successful results, however, there is a visible gap in the
development of a high-performing LSB and an applicable process of fabrication (Cheng et al.,
2022; Yang et al., Zhu et al., 2019). Both the environmental and public demands for electric cars
are increasing. LSBs are explored as a solution, being less expensive, higher performing, and
more environmentally friendly than currently used LIBs (Li et al., 2021; Zhao et al., 2020; Zhen
et al., 2022). However, LSBs are far from commercialization due to the many issues with
chemical interactions within the cell. To address these issues research strategies usually rely on
expensive and complicated processes–which limit their commercial applicability. The need for a
LSB cathode design that both addresses issues with the chemistry and is synthesized using a
method applicable for commercialization is shown in the established benefits of LSBs and their
positive impact on society in replacing LIBs. This experiment hypothesized that by utilizing the
fabricated cathode material, performances of fabricated LSB coin cells would be increased. The
null hypothesis (H0) stated that there would be no statistically significant difference between the
means of the control and experimental groups. The cathode design was fabricated by building a
conductive double-layered matrix out of CNT and EFGO that was reduced to RGO, TiO2 coated
the structure, and sulfur nanoparticles were infiltrated into the structure. The novel cathode
material was tested through coin cell construction and cycling. After the initial cycling results of
the first iteration of coin cells, a second iteration of the structure was fabricated utilizing PANI to
create PANI-crosslinked sulfur. The second iteration used the same structure as the previous one
except for a PANI coating then sulfur infiltration and finally PANI vulcanization. Cells were
built using the second iteration of the cathode material. Cycling data was collected and after
statistical tests were performed, it was concluded that the null hypothesis could be rejected and
the success of the novel design and bulk synthetic fabrication method could be established.
However, this also does not equate to a complete success of the hypothesis, since additional cells
using the same controls have not been fabricated to assert the promise of this cathode design and
fabrication method. The cycling data for the BTA1 cell indicates that the cell design shows
promise for a viable LSB. further research and development are needed to reach a more
advanced cell with optimized components.
Further prototyping will consist of creating a LSB cell designed in a practical manner that
could replace LIBs in EVs, reducing the prices of the vehicles and in turn, reducing transmission
carbon emissions from the wider availability of EVs. This cathode design needs significantly
more optimization and reiteration before reaching a commercial stage, however, the strategies of
fabrication and cycling results of cells BTA1 and BTA2 demonstrate that achieving competitive
results while using an inexpensive, environmentally, viable process is possible.

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Appendix A
Raw Cycling Data for Cell BTA1
Cycle RCap_DChg(mAh/g) Efficiency(%) Cycle RCap_DChg(mAh/g) Efficiency(%) Cycle RCap_DChg(mAh/g) Efficiency(%)
1 1137.257 0 33 755.022 98.74 65 687.177 97.17
2 823.757 74.82 34 746.77 98.15 66 679.651 97.74
3 759.555 94.98 35 740.65 98.19 67 680.12 98.44
4 748.125 97.59 36 739.908 98.73 68 669.53 97.21
5 788.238 103.24 37 737.868 98.61 69 672.637 99.13
6 778.681 97.73 38 736.848 98.59 70 674.377 98.58
7 773.027 97.48 39 730.914 98.26 71 671.889 98.22
8 773.891 98.47 40 726 98.5 72 669.741 98.21
9 776.659 99 41 722.106 98.38 73 665.019 97.73
10 770.712 98.23 42 723.497 99 74 659.734 97.96
11 778.361 99.77 43 721.457 98.56 75 653.94 97.79
12 771.165 98.17 44 720.344 98.83 76 654.629 98.68
13 775.902 99.39 45 716.635 98.22 77 697.551 104.82
14 777.483 99.8 46 715.987 98.58 78 716.483 91.59
15 785.565 98.98 47 717.38 99.05 79 685.636 94.84
16 778.787 97.99 48 719.906 99.01 80 672.703 96.49
17 766.895 97.3 49 719.586 98.67 81 662.952 97.08
18 781.296 99.95 50 716.98 98.51 82 654.064 97.37
19 781.203 98.65 51 712.282 98.36 83 648.567 97.84
20 774.8 98.28 52 707.301 98.27 84 646.62 98.41
21 775.101 98.6 53 709.592 99.16 85 643.339 98.59
22 779.897 98.99 54 714.33 99.13 86 639.993 98.19
23 782.132 98.55 55 711.703 98.36 87 634.593 97.87
24 783.898 99.19 56 708.218 98.31 88 630.539 98.21
25 798.606 99.78 57 708.509 98.73 89 627.997 98.28
26 798.114 99.03 58 704.855 98.16 90 627.824 98.59
27 796.441 98.89 59 706.595 99 91 621.171 97.67
28 790.824 98.65 60 705.852 98.36 92 618.233 98.19
29 780.056 97.99 61 704.459 98.49 93 614.938 98.12
30 766.426 97.78 62 700.843 98.05 94 610.039 98.09
31 755.578 97.92 63 699.923 98.39 95 607.02 98.22
32 752.518 97.92 64 698.629 98.33

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MATRYOSHKA DUAL-SHELLED LITHIUM-SULFUR BATTERY 1

Bulk Scale Synthesis of a Novel Dual Core-Shelled Sulfur Cathode Composite

Oak Park and River Forest High School

Illinois - Chicago J.S.H.S. Regional Symposium

January 21, 2023

List of Tables and Figures............................................................................................................. 3

Materials and Methods of Prototyping........................................................................................ 14

Initial Conductive Layer.................................................................................................. 17

Sulfur Infiltration and PANI Vulcanization..................................................................... 19

Coin Cell Construction.................................................................................................... 21

Limitations and Future Research..................................................................................... 31

Conclusions and Applications..................................................................................................... 33

Raw Cycling Data for Cell BTA1............................................................................................... 40

List of Tables and Figures

Figure 1 Matryoshka Nesting Doll Comparison to Cathode Structure................................ 7

Figure 2 Lithium-Sulfur Battery Cell Chemistry................................................................. 8

Figure 3 Structure of Novel Cathode Material................................................................... 13

Figure 4 Flow Chart of Fabrication Process....................................................................... 16

Figure 5 Cathode 2 Material Structure Synthesis............................................................... 17

Figure 6 Casting of Material Using “Doctor Blade”.......................................................... 21

Figure 7 Cell Preparation and Assembly in Glove Box..................................................... 21

Figure 8 LSB Coin Cell...................................................................................................... 22

Figure 9 Data Input (a) and Cell Testing (b)....................................................................... 22

Figure 10 TGA Analysis....................................................................................................... 23

Figure 11 SEM Material Input.............................................................................................. 23

Figure 12 XRD Machine....................................................................................................... 23

Figure 13 Initial Capacities................................................................................................... 25

Figure 14 Capacities After 95 Cycles................................................................................... 25

Figure 15 TGA of BT Material............................................................................................. 25

Figure 16 TGA of BTA Material.......................................................................................... 25

Figure 17 SEM of BT Material………................................................................................. 26

Figure 18 SEM of BTA Material.......................................................................................... 26

Figure 19 Merged EDS of BT Material................................................................................ 26

Figure 20 Merged EDS of BT Material……….................................................................... 26

Figure 21 XRD of BTA Material.......................................................................................... 27

Table 1 F-test for Variances.............................................................................................. 27

Table 2 ANOVA Test........................................................................................................ 27

Table 3 Descriptive Statistics........................................................................................... 28

Table 4 Power Analysis.................................................................................................... 28

Table 5 t-test Assuming Unequal Variance...................................................................... 28

Table 6 Bonferroni, Spearman, and Cohen’s d Tests....................................................... 28

Figure 22 Individual Capacities.......................................................................................... 28

Figure 23 Means With 95% CI Error Bars.......................................................................... 28

Figure 24 Capacity and Coulombic Efficiency of BTA1.................................................... 28

Bulk Scale Synthesis of a Novel Dual Core-Shelled Sulfur Cathode Composite

density/capacities of LIBs leave much to be explored including various alternatives such as

material selection, environmentally friendly fabrication process, and outstanding performance

et al., 2022; Wang et al., 2021; C. Zhao et al., 2020).

Because of the considerable issues with LSB chemistry, commercialization continues to

typically relied on processes including nanofabrication, which involves individually modifying

practical realization of a high-cycling battery cell engineered with an inexpensive, applicable

decreasing carbon emissions from the wider availability of EVs.

civilization. Combustion engine vehicles contribute a significant portion of carbon dioxide

emissions (National Oceanic and Atmospheric Administration, 2022; United States

Environmental Protection Agency, 2022). Using economic and environmentally friendly

constructed of conductive/polysulfide absorbing materials fabricated in a bulk synthesis (Figure

interactions between materials.

Matryoshka Nesting Doll Comparison to Cathode Structure

carbon host), an electrolyte (lithium bis(trifluoromethanesulfonyl) imide in

dioxolane/dimethoxyethane (LiTSFI-DOL/DME)), and a polymer separator (Figure 2) (Lin et

al., 2021; Pai et al., 2022; Wang et al., 2021).

Lithium-Sulfur Battery Cell Chemistry