FACULTY OF MINING AND MINERAL PROCESSING

DEPARTMENT OF MINING ENGINEERING

NAME : EMMANUEL MUSUNGATAI

LEVEL 5.1

HMINE 502 FUELS AND ENERGY

ASSIGNMENT ONE
Q: Discuss the advances and challenges in lithium battery usage 40

Lithium-ion batteries (LIBs) power electric vehicles and electronics. With the prevalence of
these set to increase, efforts have been directed towards improving the performance and
longevity of LIBs. Now researchers have shown that adding a specific polymer composite
binder to the silicon anode of LIBs can improve its structural stability significantly, making it
viable for much more powerful, long-lasting LIBs, and changing the future of the
technologies it drives.

Any typical lithium-ion battery today consists of a positive electrode (cathode) made up of a
lithium-containing compound, a negative electrode (anode) made up of graphite, and
electrolyte -- the layer in between the electrodes through which ions flow. When a battery is
charged, lithium ions flow from the cathode to the anode, where they are stored. During the
discharge process, the lithium is ionized and moves back to the cathode

USE OF SILICON ANODE

Recently, there has been a growing interest in using silicon as the anode material because it
is more abundant, and therefore cheap, and has a higher theoretical discharge capacity than
graphite. However, it has a key disadvantage: repeated charging and discharging causes the
silicon particles to expand and rupture. This results in the formation of a thick solid-
electrolyte interface (SEI) between the electrolyte and the anode, which hinders the
movement of lithium ions between the electrodes.

To improve the performance of silicon anodes in LIBs, a team led by Professor Noriyoshi
Matsumi, and also including Dr. Agman Gupta and Senior Lecturer Rajashekar Badam, from
Japan Advanced Institute of Science and Technology (JAIST), has developed a binder for the
silicon particles, which can improve their stability and maintain a thin SEI layer. Now, in
contrast to a thick SEI layer, a thin one is beneficial because it prevents the anode and
electrolyte from spontaneously reacting with each other. The results of the study are
published in ACS Applied Energy Materials.

The binder is a polymer composite consisting of an n-type conducting polymer

poly(bisiminoacenaphthenequinone) (P-BIAN) and a carboxylate-containing polymer
poly(acrylic acid) (PAA), each linked to the other via hydrogen bonds. The composite
polymer structure holds the silicon particles together like a net and prevents them from
rupturing. The hydrogen bonds between the two polymers permit the structure to self-
repair, as the polymers can reattach themselves if they break away at any point. Moreover,
the n-doping ability of P-BIAN improves the conductivity of the anode and maintains a thin
SEI by limiting the electrolytic decomposition of the electrolyte on the anode.

To test the binder, the researchers constructed an anodic half-cell consisting of silicon
nanoparticles with graphite (Si/C), the binder (P-BIAN/PAA) and an acetylene black (AB)
conductive additive. The Si/C/(P-BIAN/PAA)/AB anode was put through a repeated charge-
discharge cycle. The P-BIAN/PAA binder was observed to stabilize the silicon anode and
maintain a specific discharge capacity of 2100 mAh g-1 for over 600 cycles. In contrast, the
capacity of the bare silicon-carbon anode dropped to 600 mAh g-1 within 90 cycles.

After the test, the researchers disassembled the anode and examined the material for any
cracks that might have resulted from silicon rupture. A spectroscopic and microscopic
examination after 400 cycles revealed a smooth structure with only a few microcracks
indicating that the addition of the binder was able to improve the structural integrity of the
electrode and maintain a uniform SEI.

The results demonstrate that the addition of the binder can improve the characteristics of
the silicon anode and make it practically feasible. The design and application of novel
polymer composites comprising n-type conducting polymers (CPs) and proton donating
polymers with hydrogen bonded networks, like P-BIAN/PAA, hold a promising future in high-
capacity electrode materials.

As the demand for lithium-ion batteries increases, silicon, which is the eighth-most abundant
material on earth, will be a promising environment-friendly alternative to graphite. The
improvements to its structural stability and its conductivity with the use of binders will make
it more suitable for use in future lithium-ion batteries. This composite binder design
principle will enable wider diffusion of EVs, creation of other battery driven vehicles, and
drones, which requires a higher energy density for advanced performance.

USE OF SULFUR IN LITHIUM BATTERIES

At the heart of most electronics today are rechargeable lithium-ion batteries (LIBs). But their
energy storage capacities are not enough for large-scale energy storage systems (ESSs).
Lithium-sulfur batteries (LSBs) could be useful in such a scenario due to their higher
theoretical energy storage capacity. They could even replace LIBs in other applications like
drones, given their light weight and lower cost.

But the same mechanism that is giving them all this power is keeping them becoming a
widespread practical reality. Unlike LIBs, the reaction pathway in LSBs leads to an
accumulation of solid lithium sulfide (Li2S6) and liquid lithium polysulfide (LiPS), causing a
loss of active material from the sulfur cathode (positively charged electrode) and corrosion
of the lithium anode (negatively charged electrode). To improve battery life, scientists have
been looking for catalysts that can make this degradation efficiently reversible during use.

In a new study published in ChemSusChem, scientists from Gwangju Institute of Technology

(GIST), Korea, report their breakthrough in this endeavor. "While looking for a new
electrocatalyst for the LSBs, we recalled a previous study we had performed with cobalt
oxalate (CoC2O4) in which we had found that negatively charged ions can easily adsorb on
this material's surface during electrolysis. This motivated us to hypothesize that CoC2O4
would exhibit a similar behavior with sulfur in LSBs as well," explains Prof. Jaeyoung Lee
from GIST, who led the study.

To test their hypothesis, the scientists constructed an LSB by adding a layer of CoC2O4 on
the sulfur cathode.

Observations and analyses revealed that CoC2O4's ability to adsorb sulfur allowed the
reduction and dissociation of Li2S6 and LiPS. Further, it suppressed the diffusion of LiPS into
the electrolyte by adsorbing LiPS on its surface, preventing it from reaching the lithium
anode and triggering a self-discharge reaction. These actions together improved sulfur
utilization and reduced anode degradation, thereby enhancing the longevity, performance,
and energy storage capacity of the battery.

Charged by these findings, Prof. Lee envisions an electronic future governed by LSBs, which
LIBs cannot realize.Lithium Sulfur Batteries can enable efficient electric transportation such
as in unmanned aircrafts, electric buses, trucks and locomotives, in addition to large-scale
energy storage devices," he observes.

CHANGING OF ELECTROLYTES IN LITHIUM BATTERIES

For the first time, researchers who explore the physical and chemical properties of electrical
energy storage have found a new way to improve lithium-ion batteries. They successfully
increased not only the voltage delivery of a lithium-ion battery but also its ability to suppress
dangerous conditions that affect the current range of batteries. This improved lithium-ion
battery could make longer journeys in electric vehicles possible and lead to the creation of a
new generation of home energy storage, both with improved fire safety.

Researchers at the Graduate School of Engineering and Graduate School of Science at the
University of Tokyo came up with a way to improve safety and provide more charge.A
battery's voltage is limited by its electrolyte material. The electrolyte solvent in lithium-ion
batteries is the same now as it was when the batteries were commercialized in the early
1990s. A new fluorinated cyclic phosphate solvent (TFEP) electrolyte was made and greatly
improves upon existing ethylene carbonate (EC), which is widely used in batteries today.

Ethylene Carbonate is notoriously flammable and is unstable above 4.3 volts; TFEP, on the
other hand, is nonflammable and can tolerate greater voltages of up to 4.9 volts. This extra
voltage in an otherwise identically sized package can mean the batteries can last longer
before they need another charge. As lithium ion-powered electric vehicles proliferate, this
extra range and safety would no doubt prove extremely useful.

When temperatures fall below freezing, cellphones need to be recharged frequently, and
electric cars have shorter driving ranges. This is because their lithium-ion batteries' anodes
get sluggish, holding less charge and draining energy quickly. To improve electrical
performance in the extreme cold, researchers reporting in ACS Central Science have
replaced the traditional graphite anode in a lithium-ion battery with a bumpy carbon-based
material, which maintains its rechargeable storage capacity down to -31 F. Recently,
scientists determined that the flat orientation of graphite in the anode is responsible for the
drop in a lithium-ion battery's energy storage capacity in the cold. So, Xi Wang, Jiannian Yao
and colleagues wanted to modify the surface structure of a carbon-based material to
improve the anode's charge transfer process.

To create the new material, the researchers heated a cobalt-containing zeolite imidazolate
framework (known as ZIF-67) at high temperatures. The resulting 12-sided carbon
nanospheres had bumpy surfaces that demonstrated excellent electrical charge transfer
capabilities. Then the team tested the material's electrical performance as the anode, with
lithium metal as the cathode, inside a coin-shaped battery. The anode demonstrated stable
charging and discharging at temperatures from 77 F to -4 F and maintained 85.9% of the
room temperature energy storage capacity just below freezing. In comparison, lithium-ion
batteries made with other carbon-based anodes, including graphite and carbon nanotubes,
held almost no charge at freezing temperatures. When the researchers dropped the air
temperature to -31 F, the anode made with bumpy nanospheres was still rechargeable, and
during discharge, released nearly 100% of the charge put into the battery. Incorporating the
bumpy nanosphere material into lithium-ion batteries could open up the possibilities for
using these energy sources at extremely low temperatures, the researchers say.

Conventional lithium ion batteries, such as those widely used in smartphones and
notebooks, have reached performance limits. Materials chemist Freddy Kleitz from the
Faculty of Chemistry of the University of Vienna and international scientists have developed
a new nanostructured anode material for lithium ion batteries, which extends the capacity
and cycle life of the batteries. Based on a mesoporous mixed metal oxide in combination
with graphene, the material could provide a new approach how to make better use of
batteries in large devices such as electric or hybrid vehicles.

High energy density, extended cycle life and no memory effect: Lithium ion batteries are the
most widespread energy storage devices for mobile devices as well as bearers of hope for
electro mobility. Researchers are looking for new types of active electrode material in order
to push the batteries at the next level of high performance and durability, and to make them
better usable for large devices. The 2D/3D nanocomposite based on a mixed metal oxide
and graphene, developed by the two scientists and their teams, seriously enhances the
electrochemical performance of lithium ion batteries. "In our test runs, the new electrode
material provided significantly improved specific capacity with unprecedented reversible
cycling stability over 3,000 reversible charge and discharge cycles even at very high current
regimes up to 1,280 milliamperes," says Department Head Freddy Kleitz. Today's lithium ion
batteries lose their performance after about 1,000 charging cycles.

Development of extremely fast charging lithium batteries

With the climate change concerns, an ever-increasing number of researchers are currently
focusing on improving electric vehicles (EVs) to make them a more attractive alternative to
conventional gas cars. The battery improvement of EVs is a key issue to attract more drives.
In addition to safety, autonomy, and durability, most people want quickness in charging.
Currently, it takes 40-minute with state-of-the-art EVs while gas cars can be 'recharged' in no
longer than five minutes. The charging time needs to be below 15 minutes to be a viable
option.

Unsurprisingly, lithium-ion batteries (LIBs), which are used everywhere with portable
electronic devices, have been recognized as an option in the field of EVs, and new strategies
are always being sought to improve their performance. One way to shorten the charging
time of LIBs is to increase the diffusion rate of lithium ions, which in turn can be done by
increasing the interlayer distance in the carbon-based materials used in the battery's anode.
While this has been achieved with some success by introducing nitrogen impurities
(technically referred to as 'nitrogen doping'), there is no method easily available to control
interlayer distance or to concentrate the doping element.

Against this backdrop, a team of scientists from Japan Advanced Institute of Science and
Technology (JAIST) recently developed an approach for anode fabrication that could lead to
extremely fast-charging of LIBs.Their strategy constitutes a relatively simple,
environmentally sound, and highly efficient way to produce a carbon-based anode with very
high nitrogen content. The precursor material for the anode is poly (benzimidazole), a bio-
based polymer that can be synthesized from raw materials of biological origin. By calcinating
this thermally stable material at 800 °C, the team managed to prepare a carbon anode with
a record-setting nitrogen content of 17% in weight. They verified the successful synthesis of
this material, and studied its composition and structural properties using a variety of
techniques, including scanning electron tunneling microscopy, Raman spectroscopy, and X-
ray photoelectron spectroscopy.

To test the performance of their anode and compare it with the more common graphite, the
researchers built half-cells and full-cells, and conducted charge-discharge experiments. The
results were very promising, as the proposed anode material proved suitable for fast
charging, thanks to its enhanced lithium-ion kinetics. Moreover, durability tests showed that
the batteries with the proposed anode material retained about 90% of its initial capacity
even after 3,000 charge-discharge cycles at high rates, which is considerably more than the
capacity retained by graphite-based cells.

Another notable advantage of the proposed anode material is the use of a bio-based
polymer in its synthesis. As a low-carbon technology, the material naturally leads to a
synergistic effect that reduces CO2 emissions further. Additionally, as Professor Matsumi
remarks, The use of the approach will advance the study of structure-property relationships
in anode materials with rapid charge-discharge capabilities.
Modifications to the structure of the polymer precursor could lead to even better
performance, which might be relevant for the batteries not only of EVs, but also of portable
electronics. Finally, the development of highly durable batteries will decrease the global
consumption of rare metals, which are non-renewable resources.

Lithium-ion batteries are ubiquitous in the world of electric vehicles. However, a significant
challenge encountered with their use is their low battery life and slow charging capability.
Recent studies suggest two-dimensional (2D) nanomaterials to be a strong candidate for
enhancing their performance. Recently, a collaborative research team from Japan and India
demonstrated the efficacy of using 2D titanium diboride nanosheets in lithium-ion batteries.
Their findings could have far-reaching consequences in the field of electric vehicles and
other electronics.

As the electric vehicle (EV) industry is advancing, so are the efforts in the research and
development of superior lithium (Li)-ion batteries to power these vehicles. Exploring and
expanding rapid charge-discharge technology and extended battery life are critical
challenges in their development. A few factors, such as the diffusion of Li ions,
characteristics of the electrode-electrolyte interface, and electrode porosity, can help
overcome these issues achieve extreme fast charging and ultralong life.

In recent years, two-dimensional (2D) nanomaterials, which are thin sheet-like structures
with a thickness of a few nanometers, have emerged as potential anode materials for Li-ion
batteries. These nanosheets possess a high aspect ratio and high density of active sites,
which enables fast charging and superior cycling performance. In particular, 2D
nanomaterials based on transition-metal diborides (or TMDs) have piqued the interest of
researchers. TMDs have been found to have a high rate and long cycling stability for Li ion
storage, owing to their honeycomb planes of boron and multivalent transition-metal atoms.

Recently, a group of scientists led by Prof. Noriyoshi Matsumi from the Japan Advanced
Institute of Science and Technology (JAIST) and Prof. Kabeer Jasuja from the Indian Institite
of Technology (IIT) Gandhinagar set out to further explore the potential of TMDs for energy
storage. The team conducted the first experimental study on the storage potential of
titanium diboride (TiB2)-based hierarchical nanosheets (THNS) as an anode material for Li-
ion batteries. The THNS were developed by oxidizing TiB2 powder with hydrogen peroxide,
followed by centrifuging and freeze-drying the solution. "What makes our work stand out is
the scalability of the method developed for synthesizing these TiB2 nanosheets. For any
nanomaterial to translate into a tangible technology, scalability is the limiting factor. Our
synthesis method only requires stirring and no sophisticated equipment. This is on account
of the dissolution and recrystallization behavior exhibited by TiB2, a serendipitous discovery
that makes this work a promising bridge from lab to the field," explains Prof. Kabeer.
Thereafter, the team constructed an anodic Li-ion half-cell using the THNS as active anode
material. The team studied the charge-storage characteristics of the THNS-based anodes.

The team found that the THNS-based anode showed a high discharge capacity of 380 mAh/g
with a current density of just 0.025 A/g. Furthermore, they saw that a discharge capacity of
174 mAh/g could be obtained for a high current density of 1 A/g, with a charge time of 10
min and a capacity retention of 89.7% after 1,000 cycles. Additionally, the THNS-based Li-ion
anode could sustain very high current rates, in the order of 15 to 20 A/g facilitating ultrafast
charging in about 9 to 14 seconds. Under the high current rate, with a capacity retention
greater than 80% was observed after 10,000 cycles.

The results of this study indicate the suitability of the 2D TiB2 nanosheets as a candidate for
fast-charging and long-life Li-ion batteries. They also highlight the advantage of nano-scaling
bulk materials, like TiB2, to attain promising properties, including pseudocapacitive charge
storage, excellent high-rate capability, and superior cyclability. Explaining the potential long-
term effects of their research, Prof. Matsumi says, "Such quick-charging technology can
accelerate the diffusion of EVs and significantly decrease waiting times for charging various
mobile electronic devices. We hope our findings can stimulate more research in this field,
which can eventually lead to the convenience of EV users, lesser air pollution in cities, and
less stressful mobile life in order to enhance the productivity of our society."

Researchers from Carnegie Mellon University's Mellon College of Science and College of
Engineering have developed a semiliquid lithium metal-based anode that represents a new
paradigm in battery design. Lithium batteries made using this new electrode type could have
a higher capacity and be much safer than typical lithium metal-based batteries that use
lithium foil as anode.The interdisciplinary research team published their findings in the
current issue of Joule.Lithium-based batteries are one of the most common types of
rechargeable battery used in modern electronics due to their ability to store high amounts of
energy. Traditionally, these batteries are made of combustible liquid electrolytes and two
electrodes, an anode and a cathode, which are separated by a membrane. After a battery
has been charged and discharged repeatedly, strands of lithium called dendrites can grow on
the surface of the electrode. The dendrites can pierce through the membrane that separates
the two electrodes. This allows contact between the anode and cathode, which can cause
the battery to short circuit and, in the worst case, catch fire.

Incorporating a metallic lithium anode into lithium-ion batteries has the theoretical potential
to create a battery with much more capacity than a battery with a graphite anode.

REPLACEMENT OF THE VOLATILE LIQUID ELECTROLYTE

One proposed solution to the volatile liquid electrolytes used in current batteries is to
replace them with solid ceramic electrolytes. These electrolytes are highly conductive, non-
combustible and strong enough to resist dendrites. However, researchers have found that
the contact between the ceramic electrolyte and a solid lithium anode is insufficient for
storing and supplying the amount of power needed for most electronics.

Sipei Li, a doctoral student in Carnegie Mellon's Department of Chemistry, and Han Wang, a
doctoral student in Carnegie Mellon's Department of Materials Science and Engineering,
were able to surmount this shortcoming by creating a new class of material that can be used
as a semiliquid metal anode.

Working with the Mellon College of Science's Matyjaszewski, and Jay Whitacre, Trustee
Professor in Energy in the College of Engineering and director of the Wilton E. Scott Institute
for Energy Innovation at Carnegie Mellon, who is renowned for his work in developing new
technologies for energy storage and generation, Li and Wang created a dual-conductive
polymer/carbon composite matrix that has lithium microparticles evenly distributed
throughout. The matrix remains flowable at room temperatures, which allows it to create a
sufficient level of contact with the solid electrolyte. By combining the semiliquid metal
anode with a garnet-based solid ceramic electrolyte, they were able to cycle the cell at 10
times higher current density than cells with a solid electrolyte and a traditional lithium foil
anode. This cell also had a much longer cycle-life than traditional cells.

The researchers believe that their method could have far reaching impacts. For example, it
could be used to create high capacity batteries for electric vehicles and specialized batteries
for use in wearable devices that require flexible batteries. They also believe that their
methods could be extended beyond lithium to other rechargeable battery systems, including
sodium metal batteries and potassium metal batteries and might be able to be used in grid-
scale energy storage.

Challenges

1. Thermal Runway

Li-ion batteries are temperature and voltage-sensitive. The safe zone is the temperature
ranging from 10 °C to +55 °C. The primary hazard in a lithium-ion battery is the electrolyte,
which at its core, is flammable. As the battery temperature rises to above ~80°C, the
exothermic reaction rate inside the battery increases.

There are various causes of overheating, such as overcharging, exposure to over/under

temperature, external or internal short circuits. An internal shorting is one of the primary
reasons for thermal runaway.
If this goes unchecked, it could further lead to an exponential rise in cell temperature,
ultimately losing stability. This leads to all remaining thermal and electrochemical energy
being released to the environment.

2. Voltage Limits

Lithium-ion cells are vulnerable to stress by voltage ranges outside of safe ones between 2.5
and 3.65/4.1/4.2 or 4.35V – (depending on the chemistry of the cell). Exceeding this voltage
range leads to premature ageing and in safety risks, thanks to the reactive components
within the cells.

When stored for long periods, the tiny current draw of the protection circuitry may drain the
battery below its shutoff voltage. Regular chargers may then be of no use since the battery
management system may record this battery (or charger) ‘failure.’ Many sorts of lithium-ion
cells can’t be charged safely below 0 °C, as this will end in lithium plating and can cause
complications like internal short-circuit paths.

3. Internal Short Circuits

Rough handling and overcharging can cause internal short circuits. As the battery becomes
stuffed with lithium ions, it expands. Too much lithium can mechanically stress the battery
and compromise the internal insulation. In some cases, overcharging can result in electron-
conducting metallic deposits between the electrodes.

4. Charging Problems

The battery should be charged only at a temperature of +5°C to +45°C. Li-ion batteries, when
overheated or overcharged, could suffer severe damages like thermal runaway and cell
rupture. Overcharge will end in the decomposition of cathode materials, thus the oxidation
of the electrolyte.

Over-discharge will cause the decomposition of SEIs on the anode and copper foil oxidation.
Charging a battery cell too quickly could also result in a short circuit.

5. Faulty Chargers
Faulty chargers can affect the security of the battery as they will destroy the battery’s
protection circuit. While charging at temperatures below 0 °C, the negative electrode of the
cells gets plated with pure lithium, which may compromise the entire pack’s security.