POLITECNICO DI MILANO

School of industrial and information engineering

Master of Science in Electrical Engineering

Thesis Topic: Batteries and Charging Method

Supervisor: Prof. Brenna Morris

Author:
Noman Mohammad
Matr. 10421881

Academic year
2018-2019

I
Acknowledgement
I would like to thank Dr. Morris Brenna and his assistant Leone Carola for their support in this thesis
process, because I’m also working and trying to do my best to complete my studies , I want to say thanks
to my parents for supporting me in this long journey.

II
 Abstract
Nowadays many devices are fed by batteries, especially li-ion based batteries. Some examples are like
smartphones, smartwatches, laptops, electrical vehicles. And in this document, I will try to describe the
type of battery used now and their application, the most promising technology is based on Li-ion battery,
used in EVs, there will be a chapter on the batteries used in EVs and comparison between them.
Obviously the best one is Li-ion based battery, charging and discharging of li-ion batteries is typically
faster than the others.
What will be the future development of the batteries, the battery technology is top of the priority list for
many players, the companies try to build a key position in the market.
I will describe the future development and what is needed to improve the lifetime of a battery and
obviously they must assure the safety in every circumstance. Most important in EVs usage. The study
will focus on silica anodes, advanced cathodes and solid-state electrolytes.
In the last one there is a little chapter on fast charging and the problems due to it, like the temperature
and the lithium deposition.

II
Table of Content
Sommario
Acknowledgement ................................................................................................................................. I
Abstract ................................................................................................................................................. 3
Table of Content .................................................................................................................................. iv
List of Tables......................................................................................................................................... 7
1 Introduction ....................................................................................................................................... 1
1.1 THE CELL ...................................................................................................................................... 2
1.2 ELECTRODES ................................................................................................................................ 2
1.3 ELECTROLYTE ............................................................................................................................. 3
1.1 Type of existing batteries and main application .................................................................... 4
1.1.1 Primary Batteries ....................................................................................................................... 4
1.1.2 Secondary Batteries ...................................................................................................................... 5
1.1.2.1 Lithium-ion Batteries ................................................................................................................ 7
1.1.2.2 Nickel-Cadmium Batteries ........................................................................................................ 8
1.1.2.3 Nickel-Metal Hydride Batteries ................................................................................................ 9
1.1.2.4 Lead-Acid Batteries ................................................................................................................. 10
2 EV batteries (Li-ion) ....................................................................................................................... 11
2.1 Hybrid/Electric Vehicle Designs ................................................................................................... 12
2.2 Available Batteries for EV ............................................................................................................ 15
2.2.1 Lead-acid battery ........................................................................................................................ 16
2.2.2 Nickel Metal Hydride Battery .................................................................................................... 19
2.2.3 Lithium-ion Battery .................................................................................................................... 20
2.2.4 Lithium Polymer Battery ............................................................................................................ 22
3 Future Developments ...................................................................................................................... 23
3.1 Challenges is Lithium-ion battery ................................................................................................ 25
3.2 Silica anodes .................................................................................................................................. 26
3.2.1 The solutions for Si anode practical application ...................................................................... 27
3.2.2 Silicon-carbon anode ................................................................................................................. 28
3.2.3 Vapor deposition ......................................................................................................................... 28
3.2.4 High temperature solid phase synthesis .................................................................................... 28
3.2.5 Mechanical alloying ................................................................................................................... 29
3.2.6 Electrostatic electrospinning ...................................................................................................... 29
3.2.7 Modification of silicon–carbon anode materials ...................................................................... 29
3.2.8 Structural modification of silicon–carbon anode materials ..................................................... 29
3.2.9 Silicon–carbon nanowires .......................................................................................................... 30

III
3.2.10 Silicon-carbon nanofibers ........................................................................................................ 31
3.2.11 Silicon–carbon nanotubes ........................................................................................................ 33
3.2.12 Silicon-carbon nanosphere ...................................................................................................... 34
3.2.13 Doping modification of silicon–carbon anode materials ........................................................ 34
3.2.14 Si/nitrogen-doped carbon anode materials ............................................................................. 34
3.2.15 Compound modification of silicon–carbon anode materials .................................................. 35
3.2.16 Si/carbon/graphite anode materials ......................................................................................... 36
3.2.17 Si/carbon/graphene anode materials ....................................................................................... 36
3.2.18 Conclusion and perspective ...................................................................................................... 37
3.3 Advanced cathodes ........................................................................................................................ 38
3.3.1 Challenges of Li-Ion and Li-S Battery Cathodes ...................................................................... 38
3.3.2 Methods for Making 3D Porous Li-Ion Battery Cathodes ....................................................... 39
3.3.3 Sol-Gel Method ........................................................................................................................... 41
3.3.4 Methods for Constructing 3D Porous Li-S Battery Cathodes and Their Comparison............ 43
3.3.5 Brief Comparison between Li-Ion and Li-S Batteries .............................................................. 45
3.4 Solid-state electrolytes ................................................................................................................... 45
3.4.1 Thin Film Solid State Batteries.................................................................................................. 46
3.4.1.2 Moving to 3D Architectures .................................................................................................... 48
3.4.1.3 Electrode Selection .................................................................................................................. 49
3.4.2 The Fabrication of All-Solid-State Lithium-Ion Batteries via Spark Plasma Sintering ......... 51
3.4.2.1 Materials and Methods ............................................................................................................ 52
3.4.2.2 Results and Discussion ............................................................................................................ 54
4 Problems which born from the fast charge ................................................................................... 58
4.1 Li-ion battery Fast charging fundamentals ................................................................................. 60
4.1.2 Li-ion battery fast charging techniques ..................................................................................... 60
4.2 Temperature................................................................................................................................... 64
4.3 Lithium deposition ......................................................................................................................... 66
Bibliography ....................................................................................................................................... 68

III
 List of Figures
Figure 1 .................................................................................................................................................... 2
Figure 2 .................................................................................................................................................... 2
Figure 3 .................................................................................................................................................... 4
Figure 4 .................................................................................................................................................... 5
Figure 5 .................................................................................................................................................... 7
Figure 6 .................................................................................................................................................... 8
Figure 7 .................................................................................................................................................... 9
Figure 8 .................................................................................................................................................. 10
Figure 9 .................................................................................................................................................. 13
Figure 10 ................................................................................................................................................ 13
Figure 11 ................................................................................................................................................ 14
Figure 12 ................................................................................................................................................ 14
Figure 13 ................................................................................................................................................ 17
Figure 14 ................................................................................................................................................ 17
Figure 15 ................................................................................................................................................ 18
Figure 16 ................................................................................................................................................ 18
Figure 17 ................................................................................................................................................ 20
Figure 18 ................................................................................................................................................ 21
Figure 19 ................................................................................................................................................ 21
Figure 20 ................................................................................................................................................ 25
Figure 21 ................................................................................................................................................ 27
Figure 22 ................................................................................................................................................ 27
Figure 23 ................................................................................................................................................ 31
Figure 24 ................................................................................................................................................ 32
Figure 25 ................................................................................................................................................ 33
Figure 26 ................................................................................................................................................ 34
Figure 27 ................................................................................................................................................ 35
Figure 28 ................................................................................................................................................ 36
Figure 29 ................................................................................................................................................ 37
Figure 30 ................................................................................................................................................ 40
Figure 31 ................................................................................................................................................ 40
Figure 32 ................................................................................................................................................ 46
Figure 33 ................................................................................................................................................ 47
Figure 34 ................................................................................................................................................ 52
Figure 35 ................................................................................................................................................ 53
Figure 36 ................................................................................................................................................ 55
Figure 37 ................................................................................................................................................ 56
Figure 38 ................................................................................................................................................ 57
Figure 39 ................................................................................................................................................ 61
Figure 40 ................................................................................................................................................ 62
Figure 41 ................................................................................................................................................ 63
Figure 42 ................................................................................................................................................ 67

IV
 List of Tables
Table 1 .................................................................................................................................................... 15
Table 2 .................................................................................................................................................... 20
Table 3 .................................................................................................................................................... 23
Table 4 .................................................................................................................................................... 24
Table 5 .................................................................................................................................................... 28
Table 6 .................................................................................................................................................... 30
Table 7 .................................................................................................................................................... 35
Table 8 .................................................................................................................................................... 42
Table 9 .................................................................................................................................................... 44
Table 10 .................................................................................................................................................. 54
Table 11 .................................................................................................................................................. 55
Table 12 .................................................................................................................................................. 64

V
 1 Introduction
The purpose of this chapter is to introduce and explain the basic theory and characteristics of
batteries. The batteries which are discussed and illustrated have been selected as representative of many
models and types which are used in many applications today. No attempt has been made to cover every
type of battery in use, however, after completing this chapter you will have a good working knowledge
of the batteries which are in general use.
A battery is a collection of one or more cells that go under chemical reactions to create the flow of
electrons within a circuit. There is lot of research and advancement going on in battery technology, and
as a result, breakthrough technologies are being experienced and used around the world currently.
Batteries came into play due to the need to store generated electrical energy. As much as a good amount
of energy was being generated, it was important to store the energy so it can be used when generation is
down or when there is a need to power standalone devices which cannot be kept tethered to the supply
from the mains. Here it should be noted that only DC can be stored in the batteries, AC current can’t be
stored.
First, you will learn about the building block of all batteries, the Cell. We will explore the physical
makeup of the cell and the methods used to combined cells to provide useful voltage, current and power,
we will discuss also about the chemistry of the cell and ow chemical action is used to convert chemical
energy to electrical energy.
Batteries are widely used as sources of direct-current electrical energy in automobiles, boats, aircraft,
ships, portable electric/electronic equipment, and lighting equipment. In some instances, they are used
as the only source of power; while in others, they are used as a secondary or standby power source.
A battery consists of several cells assembled in a common container and connected together to
function as a source of electrical power.

Battery cells are usually made up of three main components:

1. The Anode (Negative electrode)

2. The Cathode (Positive electrode)
3. The electrolytes

The anode is a negative electrode that produces electrons to the external circuit to which the battery is
connected. When batteries are connected, an electron build up is initiated at the anode which causes a
potential difference between the two electrodes. The electrons naturally then try to redistribute
themselves, this is prevented by the electrolyte, so when an electrical circuit is connected, it provides a
clear path for the electrons to move from the anode to the cathode thereby powering the circuit to which
it is connected. Anode and cathode are separated by a porous barrier.

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1.1 THE CELL

A cell is a device that transform chemical energy into electrical energy. The simplest cell known as
either a galvanic or voltaic cell, is shown in figures 1-1. It consists of a piece of carbon (C) and a piece
of Zinc (Zn) suspended in a jar that contains a solution of water (H2O) and sulfuric acid (H2SO4)
called the electrolyte.

Fig 1-1: Simple voltaic or galvanic cell.

Figure 1

The cell is the fundamental unit of the battery. A simple cell consists of two electrodes placed in a
container that holds the electrolyte. In some cells the container acts as one of the electrodes and, in this
case, is acted upon by the electrolyte.

1.2 ELECTRODES
The electrodes are the conductors by which the current leaves or return to the electrolyte. In the simple
cell, they are carbon and zinc strips that are placed in the electrolyte; while in the dry cell (fig. 1-2), they
are the carbon rode in the center and zinc container in which the cell is assembled.

Fig 1-2: Dry cell, cross-sectional view

Figure 2

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1.3 ELECTROLYTE

The electrolyte is the solution that acts upon the electrodes. The electrolyte, which provides a path
for electron flow, may be a salt, an acid, or an alkaline solution. In the simple galvanic cell, the
electrolyte is in a liquid form. In the dry cell, the electrolyte is a paste.

CONTAINER
The container which may be constructed of one of many different materials provides a means of
holding (containing) the electrolyte. The container is also used to mount the electrodes. In the voltaic
cell the container must be constructed of a material that will not be acted upon by the electrolyte.

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1.1 Type of existing batteries and main application
Batteries generally can be classified into different categories and types, ranging from chemical
composition, size, form factor and use cases, but under all of these are two major battery types;

1. Primary Batteries
2. Secondary Batteries

A primary cell is one in which the chemical action eats away one of the electrodes, usually the
negative electrode. When this happens, the electrode must be replaced, or the cell must be discarded. In
the galvanic-type cell, the zinc electrode and the liquid electrolyte are usually replaced when this
happens. In the case of the dry cell, it is usually cheaper to buy a new cell.

A secondary cell is one in which the electrodes and the electrolyte are altered by the chemical action
that takes place when the cell delivers current. These cells may be restored to their original condition by
forcing an electric current through them in the direction opposite to that of discharge. The automobile
storage battery is a common example of the secondary cell.

1.1.1 Primary Batteries

Primary batteries are batteries that cannot be recharged once depleted. Primary batteries are made of
electrochemical cells whose electrochemical reaction cannot be reversed. Primary batteries exist in
different forms ranging from coin cells to AA batteries. They are commonly used in standalone
applications where charging is impractical or impossible. A good example of which is in military grade
devices and battery powered equipment. It will be impractical to use rechargeable batteries as recharging
a battery will be the last thing in the mind of the soldiers. Primary batteries always have high specific
energy and the systems in which they are used are always designed to consume low amount of power to
enable the battery last if possible.

Figure 3 Fig 1-3: Primary Batteries

Some other examples of devices using primary batteries include; Pacemakers, Animal trackers, Wrist
watches, remote controls and children toys to mention a few. The most popular type of primary batteries
are alkaline batteries. They have a high specific energy and are environmentally friendly, cost-effective
and do not leak even when fully discharged. They can be stored for several years, have a good safety
record and can be carried on an aircraft without being subject to UN Transport and other regulations.
The only downside to alkaline batteries is the low load current, which limits its use to devices with low
current requirements like remote controls, flashlights and portable entertainment devices.

4
1.1.2 Secondary Batteries

Secondary batteries are batteries with electrochemical cells whose chemical reactions can be reversed
by applying a certain voltage to the battery in the reversed direction. Also referred to as rechargeable
batteries, secondary cells unlike primary cells can be recharged after the energy on the battery has been
used up.
They are typically used in high drain applications and other scenarios where it will be either too
expensive or impracticable to use single charge batteries. Small capacity secondary batteries are used to
power portable electronic devices like mobile phones, and other gadgets and appliances while heavy-
duty batteries are used in powering diverse electric vehicles and other high drain applications like load
levelling in electricity generation. They are also used as standalone power sources alongside Inverters
to supply electricity. Although the initial cost of acquiring rechargeable batteries is always a whole lot
higher than that of primary batteries but they are the most cost-effective over the long-term.
A secondary cell or battery is one that can be electrically recharged after use to their original pre-
discharge condition, by passing current through the circuit in the opposite direction to the current during
discharge. The following graphic evidences the recharging process.

Fig 1-4: Recharging a Cell

Figure 4

Secondary batteries fall into two sub-categories depending on their intended applications.

• Cells that are utilized as energy storage devices, delivering energy on demand. Such cells are
typically connected to primary power sources to be fully charged on demand. Examples of these
type of secondary cells include emergency no-fail and standby power sources, aircraft systems
and stationary energy storage systems for load-leveling.

• Cells that are essentially utilized as primary cells but are recharged after use rather than being
discarded. Examples of these types of secondary cells primarily include portable consumer
electronics and electric vehicles.

5
The following table summarizes the pros and cons of primary and secondary batteries:

Secondary batteries can be further classified into several other types based on their chemistry. This is
very important because the chemistry determines some of the attributes of the battery including its
specific energy, cycle life, shelf life, and price to mention a few.

There are basically four major chemistries for rechargeable batteries;

1. Lithium-ion (Li-ion)
2. Nickel Cadmium (Ni-Cd)
3. Nickel-Metal Hydride (Ni-MH)
4. Lead-Acid

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1.1.2.1 Lithium-ion Batteries
Lithium ion batteries are one of the most popular types of rechargeable batteries. They are found in
different portable appliances including mobile phones, smart devices and several other battery
appliances used at home. They also find applications in electro vehicles, aerospace and military
applications due to their lightweight nature.

Figure 5 Fig 1-5: Lithium-Ion Battery

Lithium-ion batteries are a type of rechargeable battery in which lithium ions from the
negative electrode migrate to the positive electrode during discharge and migrate back to the negative
electrode when the battery is being charged. Li-ion batteries use an intercalated lithium compound as
one electrode material, compared to the metallic lithium used in non-rechargeable lithium batteries.

Lithium-ion batteries generally possess high energy density, little or no memory effect and low self-
discharge compared to other battery types. Their chemistry alongside performance and cost vary across
different use cases for example, Li-ion batteries used in handheld electronic devices are usually based
on lithium cobalt oxide (LiCoO2) which provides high energy density and low safety risks when
damaged while Li-ion batteries based on Lithium iron phosphate which offer a lower energy density are
safer due to a reduced likelihood of unfortunate events happening are widely used in powering electric
tools and medical equipment. Lithium ion batteries offer the best performance to weight ratio with the
lithium Sulphur battery offering the highest ratio.

Some of the attributes of lithium ion batteries are listed below;

• Specific Energy: 100: 265W-h/kg

• Energy Density: 250: 693 W-h/L
• Specific Power: 250: 340 W/kg
• Charge/discharge percentage: 80-90%
• Cycle Durability: 400: 1200 cycles
• Nominal cell voltage: NMC 3.6/3.85V

7
1.1.2.2 Nickel-Cadmium Batteries
The nickel–cadmium battery (NiCd battery or NiCad battery) is a type of rechargeable battery which is
developed using nickel oxide hydroxide and metallic cadmium as electrodes. Ni-Cd batteries excel at
maintaining voltage and holding charge when not in use. However, NI-Cd batteries easily fall a victim
of the dreaded “memory” effect when a partially charged battery is recharged, lowering the future
capacity of the battery.

Figure 6 Fig 1-6: Lithium-Ion Battery

In comparison with other types of rechargeable cells, Ni-Cd batteries offer good life cycle and
performance at low temperatures with a fair capacity, but their most significant advantage will be their
ability to deliver their full rated capacity at high discharge rates. They are available in different sizes
including the sizes used for alkaline batteries, AAA to D. Ni-Cd cells are used individual or assembled
in packs of two or more cells. The small packs are used in portable devices, electronics and toys while
the bigger ones find application in aircraft starting batteries, Electric vehicles and standby power supply.

Some of the properties of Nickel-Cadmium batteries are listed below.

• Specific Energy: 40-60W-h/kg

• Energy Density: 50-150 W-h/L
• Specific Power: 150W/kg
• Charge/discharge efficiency: 70-90%
• Self-discharge rate: 10%/month
• Cycle durability/life: 2000cycles

8
1.1.2.3 Nickel-Metal Hydride Batteries
Nickel metal hydride (Ni-MH) is another type of chemical configuration used for rechargeable batteries.
The chemical reaction at the positive electrode of batteries is similar to that of the nickel–cadmium
cell (NiCd), with both battery type using the same nickel oxide hydroxide (NiOOH). However, the
negative electrodes in Nickel-Metal Hydride use a hydrogen-absorbing alloy instead of cadmium which
is used in NiCd batteries.

Figure 7 Fig 1-7: Nickel-Metal Hydride Batteries

NiMH batteries find application in high drain devices because of their high capacity and energy density.
A NiMH battery can possess two to three times the capacity of a NiCd battery of the same size, and
its energy density can approach that of a lithium-ion battery. Unlike the NiCd chemistry, batteries based
on the NiMH chemistry are not susceptible to the “memory” effect that NiCads experience.

Below are some of the properties of batteries based on the Nickel-metal hydride chemistry;

• Specific Energy: 60-120h/kg

• Energy Density: 140-300 Wh/L
• Specific Power: 250-1000 W/kg
• Charge/discharge efficiency: 66% - 92%
• Self-discharge rate: 1.3-2.9%/month at 20oC
• Cycle Durability/life: 180 -2000

9
1.1.2.4 Lead-Acid Batteries
Lead acid batteries are a low-cost reliable power workhorse used in heavy duty applications. They are
usually very large and because of their weight, they’re always used in non-portable applications such as
solar-panel energy storage, vehicle ignition and lights, backup power and load levelling in power
generation/distribution. The lead-acid is the oldest type of rechargeable battery and still very relevant
and important into today’s world. Lead acid batteries have very low energy to volume and energy to
weight ratios, but it has a relatively large power to weight ratio and as a result can supply huge surge
currents when needed.
These attributes alongside its low cost makes these batteries attractive for use in several high current
applications like powering automobile starter motors and for storage in backup power supplies.

Figure 8 Fig 1-8: Lead-Acid Batteries

A third battery category is commonly referred to as the reserve cell. What differentiates the reserve cell
from primary and secondary cells in the fact that a key component of the cell is separated from the
remaining components, until just prior to activation. The component most often isolated is the
electrolyte. This battery structure is commonly observed in thermal batteries, whereby the electrolyte
remains inactive in a solid state until the melting point of the electrolyte is reached, allowing for ionic
conduction, thus activating the battery. Reserve batteries effectively eliminate the possibility of self-
discharge and minimize chemical deterioration. Most reserve batteries are used only once and then
discarded. Reserve batteries are used in timing, temperature and pressure sensitive detonation devices
in missiles, torpedoes, and other weapon systems.

Reserve cells are typically classified into the following 4 categories.

• Water activated batteries.

• Electrolyte activated batteries.
• Gas activated batteries.
• Heat activated batteries.

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 2 EV batteries (Li-ion)
In this chapter we will focus our attention on electrical vehicles batteries, based on Lithium-ion
technology. During the past few decades, the atmospheric CO2 concentration has dramatically increased
resulting in global warming and significant climate change. The global price of crude oil is increasing
day by day, therefor also the ownership of Internal Combustion Engine (ICE) vehicles continue to
increase, which is paving the way for alternative technologies such as EVs. EVs have gained acceptance
as low or zero emission means of transportation and for low noise, the energy required by EVs can be
supplied by clean renewable energy sources. In addition, EVs have the ability to recover energy that
otherwise would be lost during braking, known as Regenerative braking.
The initiative to move away from using fossil fuels as the energy source for transport use, therefore,
arises from the need to address the following concerns:

• Energy security: reduce dependence on foreign oil and to sustain development while facing
decreasing available resources.

• Environmental conservation: sustain development without negatively impacting the

environment.

• Revenue protection: maintain profitability and reduce the operating costs by insulating
against fluctuating fuel prices.

To address these issues, various green technologies, such as EVs, battery technology, and alternative
propulsion systems have gained prominence. The development has been most obvious in the automotive
industry, due to the need to improve vehicle fuel efficiency and to satisfy increasingly stringent emission
standards. Spurred by the feasibility of hydrogen fuel cells and development of higher energy density
batteries, EVs have been demonstrated as possible successors of traditional vehicles operating with
an internal combustion engine (ICE). One of the main advantages of electric-powered vehicles is the
significantly lower operating costs compared to ICE powered vehicles.
While EVs do not produce any in-situ pollutants, the electricity powering the vehicle is a formed of
processed energy that has to be produced off-site. In terms of emissions produced, an EV is only as clean
as the method used to produce the electricity.

Battery powered EVs can be categorized based on the power level:

1. Light electrical vehicles (LEV) such as electrical bikes, scooters and motorcycles
with a power demand of less than several kilowatts

2. Sedan vehicles, which includes sedan hybrid electrical vehicles (HEV) and full electrical
vehicles up to 100 kW

3. Sedan vehicles, which includes sedan hybrid electrical vehicles (HEV) and full electrical
vehicles up to 100 kW

Currently, EVs face multiple challenges which are the prohibiting factors for mass deployment and
commercialization. High initial costs, limited lifetime and relatively poor performance at low
temperature are often cited as the most important issues, with the latter three directly involving the
energy storage system (ESS) and battery management system (BMS) of the vehicle.
The average lifetime of batteries in EVs is approximately 8 to 10 years, in practice, the lifetime of the
battery is reduced due to the high-power profile of the vehicle during acceleration and braking, which
11
can be much more than 10× higher than the average power.
An electrical vehicle generally contains the following major components an electric motor, a motor
controller, a traction battery, a battery management system, a plug-in charger that can be operated
separately from the vehicle, a wiring system, a regenerative braking system, a vehicle body and a
frame. The battery management system is one of the most important components, especially when using
lithium-ion batteries.
Many kinds of batteries exist, and as new systems are developed to commercial maturity, they have been
applied to the problem of electrified transportation.

2.1 Hybrid/Electric Vehicle Designs

EVs exists for more than a century by now. In 1899, there was a Belgian electric car powered by lead-
acid battery, that was able to reach 30 m/s. However, the lack of progress in batteries prevents the
development of EVs, but recently electric and hybrid vehicles re-emerged.
EVs are powered entirely by electric propulsion systems, while hybrid vehicles have two or more power
sources—normally an ICE coupled to an electric motor/generator powered by an electric energy storage
system. A useful way to define the powertrain characteristics of such vehicles is to use degree of
hybridization (DOH), which is defined as:

𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝑚𝑜𝑡𝑜𝑟 𝑝𝑜𝑤𝑒𝑟

𝐷𝑂𝐻 =
𝑒𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝑚𝑜𝑡𝑜𝑟 𝑝𝑜𝑤𝑒𝑟 + 𝐼𝐶 𝑒𝑛𝑔𝑖𝑛𝑒 𝑝𝑜𝑤𝑒𝑟

Depending on the DOH of the vehicle, a hybrid vehicle can be classified into the following groups:

• Mild hybrid: vehicles which rely on secondary energy storage systems to assist ICE. A moderately-
sized battery is normally used as the second power source. The battery has limited
discharge range, low power output, and it offers slight fuel economy improvement.
This type of vehicle requires little modification to the existing vehicles and incur the
lowest incremental cost among the hybrid options. Vehicles belonging to this
category of hybrids include Toyota Prius.

• Plug-in hybrid: vehicles with all-electric driving range. An ICE or turbine is available for extended
range or to recharge the battery. They use a large battery pack with high power
output that can be charged directly from the grid. Such vehicles offer significant
fuel savings and reduced GHG emissions for short commutes. However, large
battery packs incur significant additional vehicle costs and weight. GM’s Chevrolet
Volt and Ford C-Max Energy are two of the commercially available plug-in hybrid
electric vehicle (PHEV)s.

• Electric vehicle: vehicles with only all-electric driving capability. These use an extremely large
battery pack and can only be recharged with electricity from the grid. These
vehicles have zero in-situ emissions, but they are currently either much more
expensive than conventional vehicles or have very limited range. Nissan Leaf and
Model S are both EVs that contain large lithium-ion battery packs to provide all
the onboard energy.

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 There are various ways to configure the drivetrain components of a hybrid vehicle:

The series connection, the electric motor is the only component connected directly to the drivetrain.
The decoupling of the engine from the wheels means it can always operate at an optimum torque and
speed regime. It performs best for low-speed, high-torque applications, such as buses or other urban
work vehicles. However, it is less efficient, as mechanical energy from the ICE needs to be converted
to electrical energy in the generator and then converted back to mechanical energy again. The electric
energy is provided by a generator connected to a prime mover ICE and to a storage system.

AC
ICE G
DC
DC
M
AC
DC
Storage
DC

Figure 9 Fig 2-1: Series configuration

The parallel configuration allows wheel to be driven by either the electric motor, the ICE, or both. The
benefit of this system is redundancy, which is important for both civilian and military vehicles. However,
direct connection between the engine and the wheel means that the ICE may not operate at its most
efficient regime, thereby limiting its efficiency. Alternatively, a power-split configuration can be
employed in which neither the ICE nor the electric motor are directly connected to the drivetrain. A
planetary gear is used to transfer power from either the ICE or the motor to power the vehicle. Such a
system offers increased efficiency and reduced emissions over the previous two systems. However,
design complexity due to the coupling of the various sub-systems adds to the cost and control strategies
required. There are various parallel hybrid configurations depending on the DOH of the vehicle. In any
case, the traction power is provided both from ICE and an electric motor supplied from a storage system.

Figure 10 Fig 2-2: parallel configuration

13
Series-Parallel configuration, depending on the working mode, the vehicle can have series
configuration or parallel one or both at the same time.

Figure 11 Fig 2-3: series-parallel configuration

A Ragone plot of some of the more common battery technologies is shown: comparison of different
battery technologies in terms of Volumetric (Volumetric energy density - how much energy a system
contains in comparison to its volume) and Gravimetric (how much energy a system contains in
comparison to its mass) energy density, metal hydride and Li-ion batteries have high energy densities
and are the most promising classes of modern rechargeable batteries. Li-ion batteries are very attractive
for modern portable electronic devices, modern hybrid vehicles and nickel metal hydride (NiMH)
batteries remains the most suitable technology for high power application. On the x-axis we have the
gravimetric energy density (Wh/kg), and on the y-axis we have the volumetric energy density (Wh/L).
To a high value of energy densities correspond a small and light battery.

Figure 12 Fig 2-4: Ragone plot

The current predominant battery energy storage technology for EVs is the Li-ion battery.

14
2.2 Available Batteries for EV
An EV battery is a battery used to power the propulsion of battery electric vehicles. Vehicle batteries
are usually a secondary (rechargeable) battery. EV batteries are designed to give power over sustained
periods of time. Batteries for EV’s are characterized by their relatively high power-to-weight ratio,
specific energy and energy density; smaller, lighter batteries reduce the weight of the vehicle and
improve its performance. A cell of a battery is consisting of an anode and a cathode and all the chemical
process happen between those two. Other than the electrodes a battery has separators, terminals,
electrolyte and a case. A battery has one negative terminal and a one positive terminal. The electrolyte
can be a gel, solid or liquid according to the battery type and it can be acidic or alkaline.
For an example electrolyte of a lead-acid battery is sulphuric acid and the negative terminal is made by
pure lead and the positive terminal is made by lead-dioxide. Electric vehicle batteries should have some
special properties rather than the normal batteries like laptop and cell phone batteries. The battery should
have high energy density to travel long range. The battery should give a stable output with different
acceleration and it should have a higher C rate (discharge current is often expressed as a C-rate in
order to normalize against battery capacity, which is often very different between batteries. A C-rate is
a measure of the rate at which a battery is discharged relative to its maximum capacity. A 1C rate means
that the discharge current will discharge the entire battery in 1 hour). Long life cycle is more important
for electric vehicle battery and the maintenance cost also should be low. Also, the battery must be
environmentally friendly and recycling must be possible.
Rechargeable batteries used in electric vehicles include lead–acid, NiCd, nickel–metal hydride,
lithium-ion, Li-ion polymer, and, less commonly, zinc–air and molten-salt batteries. The most
common battery type in modern electric cars are lithium-ion and Lithium polymer battery, because of
their high energy density compared to their weight. The amount of electricity (i.e. electric charge) stored
in batteries is measured in ampere hours or in coulombs, with the total energy often measured in watt
hours.
Battery characteristic of some batteries displayed in below table. Referring the table, we can see that Li-
polymer has the highest energy density with respect to the Li-ion but considering the battery safety Li-
polymer is dangerous to use in electric vehicle because in a collision the battery can be exploded.

Table 1

Energy Energy Power

Type Cycle life Self-
Efficiency Density Density
(Cycles) discharge
(%) (Wh/kg) (W/kg)
Lead-acid 70 - 80 20 – 35 25 200 – 2000 Low
Ni-Cd 60 – 90 40 – 60 140 – 180 500 – 2000 Low
NI-MH 50 – 80 60 – 80 220 3000 High
More than
Li-ion 70 – 85 100 – 200 360 Medium
2000
More than
Li-polymer 70 200 250 – 1000 Medium
1200
More than
Fuel Cell 50 - 80 250 - 350 800 – 1200 Negligible
2000
Super More than
95 0.3 – 0.5 2500 high
Capacitors 30 000

Tabel 2-1: different types of batteries and their data

15
Super capacitors are also a good type of an energy storage although the self-discharging characteristic
is quite high in capacitors it cannot be used as electric vehicle energy storage. Capacitors can store
instantaneous energy so they can be used to store the regenerative energy of the car.
Under development of EV technology today many batteries are used gel, paste or resin as the electrolyte.
Future batteries may have different chemistry than present batteries, but the temperature effects will be
their also. Every battery has an operating temperature range and when discharging or charging battery
temperature rise. If we can minimize the temperature of batteries a large energy can be saved. There are
a vast range of EV vehicle battery available on the market. Most of the electric
vehicle manufacturers are using Li-ion or Ni-MH batteries for their EV’s. Normally NiMH battery is
used in electric vehicles as a secondary power source. Ni-MH batteries are safer than the Li-ion battery,
but Li-ion is preferred as the power source of electric vehicles.
we are going to discuss characteristics of some battery type that can use as electric vehicle batteries.
They are listed as follows:
1. Lead-acid battery

2. Nickel metal hydride battery (NI-MH)

3. Lithium ion battery (Li-ion)

4. Lithium polymer battery (Li-Po)

2.2.1 Lead-acid battery

Lead-acid batteries are the cheapest and in past most common traction batteries available, while the most
widely used type in automobiles for over a century, have lower energy density when compared to other
more modern battery types. There are four types of lead-acid batteries available on the market.

i. Flooded battery.

▪ This is the traditional lead-acid battery. In this type of a battery liquid electrolyte is
free to move in the cell compartment

▪ Can add distilled water as the battery dries out by accessing to the individual cells.

ii. Sealed battery

▪ This is seal type of battery and the user doesn’t have access to cells. This battery is
only a slight modification of the flooded lead-acid battery

iii. Valve regulated lead-acid battery. (VRLA)

▪ This is also a sealed type battery and by the valve regulating mechanism allow
hydrogen and oxygen to outflow safely while charging.

iv. Absorbed glass matte battery. (AGM)

▪ The charging and discharging efficiencies have increased in this type of lead-acid
batteries by the absorbed glass matte construction theory.

▪ This type of batteries are now using for power sport and in many engine
start applications.
16
Lead and lead-dioxide are good electric conductors, so they are taken as the anode and the cathode of
the lead-acid battery respectively. As the electrolyte Sulphuric acid and the water is used.
During charging water in the electrolyte solution is broken down by electrolysis. Connection of an
electrical power source forces electrons to flow from positive to negative.

Structure:

- Anode: Pb
- Cathode: PbO2
- Electrolyte: H2SO4
- Proper spacers prevent
cathode-anode contact

Figure 13 Fig 2-5: lead-acid battery

The cathodic and anodic reactions are expressed as follows:

• At the anode

𝑃𝑏𝑆𝑂4 + 2𝐻 + + 2𝑒 − → 𝑃𝑏 + 𝐻2𝑆𝑂4

• At the cathode

𝑃𝑏𝑆𝑂4 + 2𝐻2 𝑂 → 𝑃𝑏𝑂2 + 𝐻2 𝑆𝑂4 + 2𝐻 + + 2𝑒 −

Figure 14 Fig 2-6: Pb-acid battery

During discharge electrons move from negative electrode Positive electrode through an external load.
This process reduces the charge and the voltages at the electrodes. When the battery is discharged, a
coating can see around the surfaces of two electrodes.
The cathodic and anodic reactions when discharging displayed below:

• At the anode

𝑃𝑏 + 𝐻2𝑆𝑂4 → 𝑃𝑏𝑆𝑂4 + 2𝐻 + + 2𝑒 −
➢ This reaction releases E0 = 0.356 𝑒𝑉 of energy
17
 • At the cathode

𝑃𝑏𝑂2 + 𝐻2𝑆𝑂4 + 2𝐻 + + 2𝑒 − → 𝑃𝑏𝑆𝑂4 + 2𝐻2𝑂

➢ This reaction releases a net energy of 𝐸0 = 1.685 𝑒𝑉

Voltage of the battery cell depends on the temperature. So, at the 298° K the battery cell voltage of a
lead-acid battery is,

V𝑜𝑐 = 0.356 + 1.685 = 2.041 𝑉

When a lead-acid battery discharge at some point the electrode sulfation builds where it becomes
difficult to recharge. So, battery should not be over discharged. In this figure we can see the Voltage of
lead-acid electrochemical cell vs. electrolyte concentration, we have an usable range and when the
battery is completely discharged, we need to recycle it.

Fully charged

Figure 15 Fig 2-7: Battery molality vs battery cell voltage

Normally lead-acid batteries are rated at room temperature and operates well around this temperature.
Low temperatures result in performance decline while high temperature cause shortened in battery life.
Typically, the lower operating temperature of the lead-acid battery is -40 °C and the upper temperature
range is 50 to 60 °C.

Figure 16 Fig 2-8: Power vs Temperature

18
2.2.2 Nickel Metal Hydride Battery
Ni-MH battery came to use from 1950s, until now it has developed dramatically, passing decades. Ni-
MH batteries are widely used for laptops, camcorders and mobile phones. However, today over 95% of
HEV’s are using Ni-MH batteries because they have low maintenance cost, design flexibility, High
power and energy density. In addition, Ni-MH batteries are safer than Li-ion batteries. However, for
electric vehicles Li-ion are most preferred than the Ni-MH because of fast charging.
General characteristics of a Ni-MH battery listed as follows:

i. Can be recharged around hundred times.

ii. Efficient at high rate discharges.

iii. Has higher capacity than nickel-cadmium batteries.

iv. The life expectancy would be about 2 – 5 years.

v. Operates well at a wide range of temperatures. 0 °C to 50 °C

temperature range for both charging and discharging.

The electrochemistry of the Ni-MH battery on charging shown below:

• At the negative electrode

𝐴𝑙𝑙𝑜𝑦 + 𝐻2 𝑂 + 𝑒 ↔ 𝐴𝑙𝑙𝑜𝑦 (𝐻) + 𝑂𝐻 −

• At the positive electrode

𝑁𝑖(𝑂𝐻)2 + 𝑂𝐻 − ↔ 𝑁𝑖𝑂𝑂𝐻 + 𝐻2 𝑂 + 𝑒

The electrochemistry of discharge as follows:

• At the negative electrode

𝐴𝑙𝑙𝑜𝑦(𝐻) + 𝑂𝐻 − ↔ 𝐴𝑙𝑙𝑜𝑦 + 𝐻2 𝑂 + 𝑒

• At the positive electrode

𝑁𝑖𝑂𝑂𝐻 + 𝐻2 𝑂 + 𝑒 ↔ 𝑁𝑖(𝑂𝐻)2 + 𝑂𝐻 −

Electrolyte of nickel-metal hydride battery is alkaline. As the separator to allow efficient ionic diffusion
non-woven polyolefin is used.

19
2.2.3 Lithium-ion Battery
‘Lithium is the metal with highest negative sub-atomic particles and lowest atomic weight’
Lithium metal is a highly reactive metal with air and most liquid electrolytes. So graphitic carbon
intercalated with Lithium metal are used. Lithium-ion and NiMH batteries produced equivalent
amount of energy. But rather than NiMH batteries Lithium-ion batteries are smaller and half weight.
Charging and discharging of Li-ion batteries is typically faster than Pb-acid and NiMH batteries. Li-ion
batteries are lighter and have more power and storage capacity than lead acid and nickel metal hybrid
batteries. Lithium batteries perform well if they are operated using an effective battery management
system. Li-ion cells available in market today have the highest energy and power density and their
performance is also better than the other available batteries. There are four types of cells available in the
market considering the shape. They are small and large cylindrical shape, prismatic and pouch.

Figure 17 Fig 2-9: Li-ion battery varieties

As the anode material carbon, particularly graphite and hydrogen-containing carbon materials are
generally used. Cobalt, Nickel and manganese are used usually as the cathode material, but cobalt oxide
is the material which is preferred by technically. For the electrolyte liquid material is used contain with
lithium hexafluoro-phosphate. Nominal voltage, energy and power density varies with the using
materials and their chemistry. Liquid Li-ion batteries were in the global market for several years then
in 1995 the solid-state Li-ion batteries were introduced. Then the energy density increased up to
100Wh/kg and the operating temperature also increased -20 °C to 60 °C. By modifying a special
manganese oxide spinel structure with a specific capacity almost equal to the cobalt oxide spinal a
battery has developed with a specific energy of 115 Wh/kg and with a 60 Ah rate.
Table 2

Year Cathode Anode Electrolyte Battery

system
LiCoO2, Li/MoO2,
1980 – 1990 LiWO2
LiNiO2 Polymer LiVOx
1990 – 2000 LiC6 LiMn2O4 C/LiMn2O4
Tabel 2-2: Development of LI-based battery system

Li-ion cells should be operated with in a safe operating voltage range and if the limitations are exceeded
the battery can be damaged, also fire will generate. So, to avoid damage and fire Li-ion cells should not
charge exceeding the save voltage limit or discharge beneath the limited voltage. Also, the cells should
be operated between the given temperature range to increase the lifetime.

20
 Figure 18 Fig 2-10: Safe operating area charging and discharging

Normally Li-ion cells are discharged in constant current. Without damaging the cell, Li-ion can
discharge to 20% of SOC (state of charge) by a constant current rate but after that, the discharging should
do by using constant voltage. Charging voltage is large than the discharging voltage generally and
because of that all charging energy does not involve when discharging.

Figure 19 Fig 2-11: Charging and Discharging of Li-ion batteries

The electrochemistry of the Li-ion battery on charging shown below:

• At the negative electrode

𝐿𝑖𝑥 𝐶6 + 𝑥𝐿𝑖 + + 𝑥𝑒 − → 𝐿𝑖𝐶6

• At the positive electrode

𝐿𝑖𝐶𝑜𝑂2 → 𝑥𝐿𝑖 + 𝑥𝑒 − + 𝐿𝑖(1 − 𝑥)𝐶𝑜𝑂2

21
The electrochemistry of discharge as follows:

• At the negative electrode

𝐿𝑖𝐶6 → 𝐿𝑖𝑥 𝐶6 + 𝑥𝐿𝑖 + + 𝑥𝑒 −

• At the positive electrode

𝑥𝐿𝑖 + 𝑥𝑒 − + 𝐿𝑖(1 − 𝑥)𝐶𝑜𝑂2 → 𝐿𝑖𝐶𝑜𝑂2

Modern Li-ion storage batteries are powerful and light, even though relatively expansive. They do not
contain metallic lithium, but ions only. They hold their charge. A lithium-ion battery pack loses only
about 5 percent of its charge per month, compared to a 20 percent loss per month for NiMH batteries.
They have no memory effect, which means that you do not have to completely discharge them before
recharging, as with some other battery chemistries. Lithium-ion batteries can handle hundreds of
charge/discharge cycles.
Pros: Lithium has the lowest standard reduction potential, which makes it a very good anode. E.m.f. =
3 V, lightness and no memory effect; no decrease of potential of discharge since during process of both
discharge and recharge (intercalation and de-intercalation of lithium ions) modification neither of grains
dimensions nor crystalline structure of electrodic materials occurs.
Cons: Rather expensive; solvent can be flammable. Reliability and durability needs to be improved.
They start degrading as soon as they leave the factory. They will only last two or three years from the
date of manufacture whether you use them or not. They are extremely sensitive to high temperatures.
There is a small chance that, if a lithium-ion battery pack fails, it will burst into flame.

2.2.4 Lithium Polymer Battery

Li-Polymer batteries placed in fourth as electric vehicle batteries. Nevertheless, because of safety
purposes Li-polymer batteries are not use for commercial purpose. Anodes of the Li-Po battery made of
using Lithium or Carbon intercalated with Lithium. The battery chemistry of Li-Po has increased the
specific energy and power of the Lipolymer battery than other available batteries. Because of the battery
electrode’s kinetics, the ability to absorb and release ions have limited the specific power and the life
cycle.
Electrochemistry of the Li-Polymer battery displayed as follows:

• Cathodic reaction when charging and discharging

𝐿𝑖𝑥 𝑀𝑋 ↔ ∆𝑥𝐿𝑖 + + ∆𝑥𝑒 − + 𝐿𝑖𝑥−∆𝑥 𝑀𝑋

• Anodic reaction When charging and discharging

𝐶6 + ∆𝑥𝐿𝑖 + + ∆𝑥𝑒 − ↔ 𝐿𝑖∆𝑥 𝐶6

22
3 Future Developments
Battery technologies are central to delivering significant advances in a wide range of industries, from
electric vehicles to renewable power. This has catapulted battery technology to the top of the priority
list for many players, leading to a huge boom in investment, as companies try to build key positions in
the market. However, this investment frenzy threatens to lead companies to rush forward without asking
themselves key questions. What will the landscape look like when the dust settles? Which technology
will dominate the battery space in the future, and what are the potential scenarios for future growth?
How do I (as a chemical company, utility, investor, battery manufacturer, automotive manufacturer,
mobility provider or government / regulator) prepare for the future and position myself to benefit? There
is no simple answer to these questions, as they depend on a range of factors, from the speed of innovation
to the ability to reduce costs of existing technologies.
Battery technologies are an essential catalyst to unlock growth and new advances in sectors such as
electric vehicles (EVs), electronic devices and battery energy storage (BES) for renewable energy. The
increasing reliance on battery storage is driving enormous demand – overall, battery applications are
expected to become a $90 billion-plus market by 2025, up from $60 billion in 2015.
Lithium-ion (Li-ion) batteries, have seen rapid improvements in performance and cost due to a
combination of greater economies of scale and research and development. However, there are still
burning unmet needs to be solved. Next-generation technologies are required to deliver a step-change in
performance of key battery characteristics. Much of the development in this area is being led by
ambitious start-ups, working in both the Li-ion market (such as on silica anodes, solid-state electrolytes
and advanced cathodes) and in alternative technologies, such as flow and zinc-air batteries.
We can identify multiple types of operating models for batteries in energy-storage applications,
including at grid scale and for residential storage, in which it can be linked to wind turbines and rooftop
solar panels. Based on their needs from batteries, these operating models can be divided across two axes:
1) frequency of discharge and 2) length of discharge. The applications and key needs of each quadrant
are shown in Table 3-1.
Table 3

Table 3-1: Summary of key needs per application in battery

energy storage

23
From the previous table we can see:

1) Frequency of discharge high and length of discharge high, the battery should have high energy
and have low cost per cycle.

2) Frequency of discharge high and length of discharge low, it has low cost per cycle, fast charging
and high power.

3) Frequency of discharge low and length of discharge high, it has low capital cost and high energy.

4) Frequency of discharge low and length of discharge low, it has low capital cost and high power.

Li-ion batteries have improved dramatically over the past 25 years, enabling improved performance in
consumer electronics and the introduction of new applications such as drones and EVs. However, to
accelerate these and other applications, new innovation is vital – a step-change in performance is
required. As table 3 below demonstrates, there are still major unmet needs in each application – such as:

• Cost, reliability and charging time for EVs

• Cycle lifetime and cost for high-frequency stationary battery

energy storage

• Safety across multiple applications

Table 4

Table 3-2: Battery applications and unmet requirements

24
From the table we can see the unmet requirements for the batteries, like for EVs are the capital cost,
charging time and reliability.
A lot is happening in next-generation technologies. A host of battery technologies using alternative
materials are being developed by ambitious start-ups, while there is increasing innovation within the Li-
ion space primarily focusing on three areas: silica anodes, advanced cathodes and solid-state
electrolytes.
we will focus our attention on the future of Li-ion batteries applying the three above innovations and
obviously the batteries must fulfill the unmet requirements like the capital cost, charging time and
reliability in terms of security “less fire more power”.

3.1 Challenges is Lithium-ion battery

Despite of the development over two decades of LIB industry, the relatively low specific capacity of
current commercial cathode (lithium cobalt oxide, 140-170mAh/g) and anode (graphite, 370mAh/g)
materials limits the specific energy of LIB. Usually from the point of4 view of LIB market, 5-8%
capacity increase each year for both LIB manufacturers and customer applications. However, it is
difficult to achieve desired capacity due to the limitation of electrode materials availability in the last
few years. Some companies are looking for other options to reduce the cost of LIBs, such as longer cycle
life and higher cutoff voltage. But LIB researchers and scientists are still facing the problem of
improving energy density for next generation LIBs. Changing the active materials for both cathode and
anode electrodes is the key to improve the battery performance. Great effort had been made for synthesis
new materials with higher specific capacities, such as Lix Niy Co1-y O2 for cathode and Silicon for anode.
Figure 1.3 shows potential electrode materials for LIBs and many works are going on these projects
which could lead us to next generation advanced LIBs.

Figure 20 Fig 3-1: Potential materials for cathode and anode

Furthermore, safety of LIB is also a critical issue for large scale applications, especially in EVs and grid
energy system, which demand higher capacities by using battery packs. The Battery Management
System (BMS) has been invented to reduce the potential of any accident and minimize the damage
before it happens. Several accidents involving LIBs have been reported in elsewhere. The last challenge
for LIBs industry is the manufacturing cost due to its complicated production processes. Basically,

25
current LIBs have three types of format, cylindrical cell, prismatic cell and pouch cell. All of them have
mature manufacturing processes, and cylindrical cells (18650 format) have highest production efficiency
and lowest cost since fully automatic production line is available. Moreover, cylindrical cells provide
consistent performance and no swelling which make them more reliable for battery packs. This is part
of the reason for Tesla to choose cylindrical battery types for their EV application. Prismatic cells were
the main power source for cell phones, but pouch cells have been rapidly seizing market share in the last
few years, especially smart phone, tablet and other small portable devices. One of the main advantages
is the diversity of cell shape which can provide more freedom for those who design new devices.
Furthermore, pouch cell has excellent safety since the battery will not explode in extreme situations.
However, compared with cylindrical and prismatic cell, the cost is much expensive due to more
processes and production efficiency. It is also difficult to have a full automatic production line as the
cell shapes will be changed regularly.

3.2 Silica anodes

Silicon, graphene, and sometimes the two of them combined together have all been suggested as
potential replacements for graphite (negative electrode anode) in the electrodes of lithium-ion batteries.
Silica has higher energy capacity than graphite, the normal material for anodes. This is leading to it
being blended through graphite anodes, with the aim of eventually moving towards full silica anodes.
These can offer theoretical increases in energy density of up to 40 percent. However, for this to
happen, issues in cycle lifetime have to be overcome, in which the anode pulverizes itself upon its 300
percent volume expansion while charging. Ongoing innovations use only minor silica concentrations,
limiting potential density increases to 10–20 percent. While all three of these options bring attractive
properties to the table—most importantly, a very high theoretical capacity—those properties are lost in
the real world. Silicon electrodes crack and break after just a short number of charge/discharge cycles.
Meanwhile, the use of graphene on electrodes is limited because graphene’s attractive surface area is
only possible in single stand-alone sheets, which don’t provide enough volumetric capacitance. Layer
the graphene sheets on top of each other to gain that volumetric capacity, and you begin to lose that
attractive surface area.
Now researchers at Kansas State University (KSU) claim to have developed a technique that uses silicon
oxycarbide that makes the combination of silicon and graphene achieve its expected greatness as an
electrode material. It is better to use silicon combined with graphene than a bulk silicon electrode, but
nano-silicon/graphene electrodes fail to satisfy key requirements for any practical applications and they
have poor volumetric capacity, high cost, and low cycling efficiency—too much lithium is lost
irreversibly with each charge-discharge cycle. What’s more, their mechanical and chemical instability
that can lead to rapid capacity decay. To overcome this, the KSU researchers turned to the high
temperature glass ceramic, silicon oxycarbide. the KSU team created a self-standing anode material
consisting of silicon oxycarbide glass particles embedded into a chemically modified graphene oxide
matrix. A heated silicon resin decomposes so that “the constituent silicon, carbon, and oxygen atoms are
arranged in a random 3-D structure, and any excess carbon precipitates out into string-like or cellular
regions. Such an open 3-D structure renders large sites for reversible lithium storage and smooth
channels for solvated lithium-ion transportation from the electrolyte.” This stands in stark contrast to
crystalline silicon, which undergoes an alloying reaction with lithium that results in enormous volume
changes and also an irreversible reaction with the electrolyte that leads to chemical instability and fading
capacity as the charge-discharge cycles add up. The KSU researchers claim that the electrode has a
capacity of approximately 600 mA/g or 400 mA/h per cubic centimeter of the electrode after 1020
cycles. The researchers expect that the power density (the maximum amount of power that can be
supplied per unit mass) will be more than three times that of today’s Li-ion batteries.

26
 Figure 21 Fig 3-2: Glass nanoparticles embedded in graphene (3-D structure)

3.2.1 The solutions for Si anode practical application

Based on the requirement of current LIB market, it is quite clear that finding new active materials for
next generation LIB is the priority. The development of cathode is mainly focusing on “Li-rich NMC”
which combine the beneficial effects of Ni, Co and Mn with6 some Li in the transition metal layers and
demonstrate a higher capacity exceeding 280 mAh/g. For anode part, according to Table 1.1, Si anode
has been considered as one of the most promising anode candidates due to its super high specific capacity
(4200mAh/g), which is ten times higher than graphite anode (372mAh/g). Nevertheless, the key problem
for Silicon based anode is its huge volume change (420%) during lithiation/delithiation process, which
leads to rapid pulverization and mechanical integrity damage of Si electrode, resulting loss of electrical
contact and rapid capacity fading (Figure 3-3). In addition, binders and electrolyte are also crucial to
address the key problem of Si-based electrode during cycling based on mechanical and electrochemical
properties.

Figure 22 Fig 3-3 Silicon anode and electrode failure mechanism in Lithium Ion Battery

27
Si anode materials:
Table 5

Table 3-3 Comparison of various anode materials (all the capacity numbers are based
on materials in the delithiated state except lithium metal)

Generally, there are two solutions to overcome huge volume change of silicon anode: preparation of
nanoscale materials and make porous Si anode. Nano-structured Silicon anode can dramatically reduce
the volume effect during charging/discharging, which minimizes the electrode swelling thereby
improves the cycle stability. Many efforts have been devoted to design various Si nano structures during
last 10 years, such as Si nanoparticles (SiNPs), Si nanowires (SiNWs), Si hollow nanotubes (SiHNTs),
Si core-shell, Si/C composite and SiOx.

3.2.2 Silicon-carbon anode

The Si–C anode materials are usually prepared by methods such as vapor deposition, high temperature
solid phase synthesis, mechanical alloying, electrostatic electrospinning; the latter three methods require
high temperature treatment. The methods mentioned above are the most widely used and easiest to
implement.

3.2.3 Vapor deposition

Vapor deposition includes chemical vapor deposition (CVD) and physical vapor deposition (PVD).
CVD is a chemical process used to produce high quality, high performance solid materials. The process
is often used in the semiconductor industry to produce thin films. CVD is widely used in
microfabrication processes to deposit materials in various forms, including monocrystalline,
polycrystalline, amorphous and epitaxial. These materials include: silicon (SiO2, germanium, carbide,
nitride and oxynitride), carbon (fiber, nanofibers, nanotubes, diamond and graphene), fluorocarbons,
filaments, tungsten, titanium nitride and various high-k dielectrics. Chemical vapor deposition (CVD)
in which hydrocarbons are decomposed over a substrate is perhaps the most popular route since it is a
technique commonly adopted by the semiconductor industry and it is also relatively facile to set up in
research laboratories. PVD describes a variety of vacuum deposition methods, which can be used to
produce thin films and coatings. PVD is characterized by a process in which the material goes from a
condensed phase to a vapor phase and then back to a thin film condensed phase. The most common PVD
processes are sputtering and evaporation. PVD is applied in the manufacture of items that require thin
films for mechanical, optical, chemical or electronic functions. Common industrial coatings applied by
PVD are titanium nitride, zirconium nitride, chromium nitride and titanium aluminum nitride. Of the
two vapor depositions, CVD is often used to prepare silicon–carbon composite materials.

3.2.4 High temperature solid phase synthesis

High temperature solid phase synthesis refers to a method that under high temperature (1000–1500°C)
and through contact with a solid interface, reaction, nucleation and crystal growth response generates a
large number of compound oxides. High temperature solid phase synthesis could be a common method
to prepare Si/C composite materials, and in order to prevent the inert phase of Si/C the reaction
temperature is often controlled under 1200°C.

28
3.2.5 Mechanical alloying
In contrast to high temperature solid phase synthesis, the materials prepared by mechanical alloying
often have smaller particles, larger specific surface area and more uniform structures. Mechanical
alloying (MA) is a solid-state powder processing technique involving repeated cold welding, fracturing
and re-welding of blended powder particles in a high-energy ball mill to produce a homogeneous
material. MA is now shown to be capable of synthesizing a variety of equilibrium and non-equilibrium
alloy phases starting from blended elemental or pre-alloyed powders.

3.2.6 Electrostatic electrospinning

Electrospinning is a fiber production method, which uses electric force to draw charged threads of
polymer solutions or polymer melts up to fiber diameters in the order of some hundred nanometers.
Electrospinning shares characteristics of both electros spraying and conventional solution dry spinning
of fibers. The process does not require the use of coagulation chemistry or high temperatures to produce
solid threads from solution. This makes the process particularly suited to the production of fibers using
large and complex molecules. Electrospinning from molten precursors is also practiced and this method
ensures that no solvent can be carried into the final products. Electrospinning is a particularly low cost,
simple and versatile method to produce nanofibers from various kinds of materials, and the improved
coaxial electrospinning can fabricate nanotubes and core–shell structural nanofibers.

3.2.7 Modification of silicon–carbon anode materials

The main problems of silicon–carbon anode materials, such as low first discharge efficiency, poor
conductivity and poor cycling performance need to be improved. When studying the modification of
silicon–carbon anode materials, we usually take the following three aspects into consideration:

1) Use different nanostructures to buffer the volume change of silicon, avoid the damage of
generated SEI film on the electrode surface and avert the explosion of new surface during the
process of circulation, in order to reduce the irreversible capacity loss and improve the cycling
stability;
2) We can significantly change the carbon material elements and the surface activity and improve
the electrochemical properties through heteroatom doping, including non-metallic elements
(boron, nitrogen, sulfur, phosphorus) and metal elements (K, Al, Ga, V, Ni, Co, Cu, Fe)
3) Apply compound modification treatment by combining different forms of carbon with silicon to
form uniform conductive network structures and to prepare silicon–carbon composite materials
with good electrical conductivity, good adhesion and high chemical stability.

3.2.8 Structural modification of silicon–carbon anode materials

Carbon-based nanomaterials have unique properties that make them useful for many technical
applications, including lightweight construction, electronics, energy generation, environmental
technology and medicine. Nanomaterials exhibit physical and chemical properties that are different
from, and normally much better than, those of the bulk forms. These outstanding properties are often
determined by the microstructure. Carbon materials with excellent mechanical flexibility, high
electronic conductivity and chemical stability in electrolytes have drawn much attention for the
development of binder-free and lightweight electrodes. The most recent advance in the applications of
nanowires (NWs), nanofibers (NFs), nanotubes (NTs) and nanospheres (NSs) in the structure of silicon–
carbon nanomaterials in LIBs are often mentioned. Table 3-4 lists some studies using combinations of
Si–C anode materials (NWs, NFs, NSs), in the form of material structures and electrochemical
properties. From these studies it can be seen clearly that anode materials with nanostructures can
29
significantly improve the electrochemical cycling performance of lithium ion batteries.
Table 6

Tabel 3-4: Electrical properties of silicon–carbon anodes with different structures. Qr1,the first reversible capacity;
CE,coulombicefficiency; QdN(N), discharge capacity in Nth cycle; C.R.N., capacity retention in Nth cycle. NWs,
nanowires; NFs, nanofibres; NTs, nanotubes; NSs, nanospheres.

3.2.9 Silicon–carbon nanowires

Nanowires are needed in many nanoscale applications. Various types of nanowires have been produced,
including some with diameters ranging from about 50 to 100 nm. The process of a novel design of
carbon–silicon core–shell nanowires for high power and long-life lithium-ion battery electrodes is
schematically illustrated in figure 3-4. Amorphous silicon was coated onto carbon nanofibers to form a
core–shell structure and the resulting core–shell nanowires showed great performance as anode material.
They show a high charge storage capacity of about 2000 mAh/g and good cycling life. They also have
a high coulombic efficiency of 90% for the first cycle and 98–99.6% for the following cycles. Bogart’s
group reported a solution-based synthesis of Si nanowires with a conductive carbon skin. Electrodes
made with Si nanowires coated by pyrolyzed carbon shells exhibited high capacities of over 2000 mAh/g
30
for 100 cycles when cycled slowly at 0.1 C and over 1200 mAh/g when cycled quickly at 1.0 °C.
Uniform and complete carbon coatings were also found to prevent complete nanowire expansion needed
for full lithiation of the nanowire.

Figure 23
Fig 3-5: Schematic illustration of Si coating onto carbon nanofibres. (a) Bare CNFs. (b) C–Si core–shell NWs

3.2.10 Silicon-carbon nanofibers

The attractive properties of catalytically grown carbon nanofibres (CNFs) have been known for decades.
They can be mass-produced inexpensively, and have excellent mechanical strength and high thermal
and electrical conductivity. The hybrid nanostructured Si/CNFs anodes exhibited superior device
performance to that of materials used in previous studies, in terms of both specific capacity and cycle
life. The CNFs provide not only a good strain/stress relaxation layer but also a conductive electron
pathway. It is developed hollow carbon nanofibres/Si composites by a facile CVD technique with iron
nitrate as the catalyst source and acetylene as the carbon source. They show excellent rate capability as
anode materials for lithium batteries. The initial discharge and charge capacities of the CNFs/Si
composites at 0.60 C are 1197.8 and 941.4 mAh/g, respectively. A reversible charge capacity of 733.9
mAh g−1 can be delivered at 0.60 C after twenty cycles and the capacity retention is as high as 77.9%.
It is found that CNFs/Si composites show superior electrochemical properties as anode materials for
lithium batteries. They not only provide electronic conducting bridges between Si particles and the
current collector for electron transportation but also act as a buffer to suppress the volume expansion of
Si particles during lithiation and delithiation reactions. A novel flexible three-dimensional (3-D) Si/C
fibre paper electrode is synthesized by simultaneously electrospraying nano-Si-PAN (polyacrylonitrile)
clusters and electrospinning PAN fibres followed by carbonization. The flexible 3-D Si/C fibre paper
electrode demonstrate a very high overall capacity of about 1600 mAh/g with capacity loss less than
0.079% per cycle for 600 cycles and excellent rate capability. It is developed a new porous composite
nanofibres manufacturing route, combining electrospinning and foaming processes (illustrated in figure
3-6). After 20 cycles ,when all these batteries reach stable charging/discharging rate, the discharging
capacity shows as 1045 mAh/g for porous C/Si/AACA composite nanofibres. And introduced a 3-D
paper-type Si–carbonb nanofibre-composite electrode (Si/CNF–P) as a binder/current collector-free
anode for LIBs that was prepared using an electrospinning method. Figure 3-7 shows Nyquist plots of
the electrodes after the 1st, 5th and 100th cycles. Si–NP and Si/CNF–G exhibited a sharp deterioration
in the discharge capacity, which might be due to a serious volumetric expansion by the alloy/dealloy
process during the cycling. However, the Si/CNF–P exhibited a high initial capacity of 1957 mAh/g at
2 A/g and maintained 1187 mAh/g (retention rate of 60.6%) for 400 cycles. The enhanced cycling
performance of Si/CNF–P might result from the suppression of the volumetric expansion of Si and
facilitation of Li-ion transport. Si–NP and Si/CNF–G showed a severe increment of the charge transfer
resistance (Rct) due to increased interface resistance after the cycling process, whereas Si/CNF–P
showed a relatively slight increment of Rct due to the stable electrode structure containing Si on CNF
with voids, which could effectively release the volumetric expansion. These results confirm that the
31
combination of CNFs and Si dramatically improves the electric conductivity and reduces the total cell
resistance, which leads to the good performance of Si/CNF nanocomposite electrodes.

Figure 24

Fig 3-6: (a) Schematic of the electrospinning/foaming process in the manufacture of mesoporous C/Si/AACA composite
nanofibres and (b) optical images of the C/Si/AACA composite nanofibres under mechanical deformation (folding and
spiral-wound bending) and after bending.

32
Figure 25

Fig 3-7: Nyquist plots of (a) Si–NP, (b) Si/CNF–P and (c) Si/CNF–G,
and (d) the Rct numbers measured after the 1st, 5th and 100th cycles.

3.2.11 Silicon–carbon nanotubes

Among all the conducting carbon materials, the carbon nanotube (CNT) is a one-dimensional material
with a hollow tube including a curled graphene structure and an end cap with a hemispherical fullerene
structure. CNTs, an allotrope of graphite, have been reported to show much improved lithium storage
capacity compared with graphite, because of their unique structures and properties. CNTs have been
reported to display conductivities as high as 106 S/mand 105 S/m for single-walled carbon nanotubes
(SWCNTs) and multiwalled carbon nanotubes (MWCNTs), respectively. Recently, many investigations
have focused on CNT-based anodes for LIBs with varying success, depending on the treatments
employed. Most previous reports on CNT-containing Si anode materials mainly emphasized the
electrical connection of Si with the CNT exterior surface by simple mechanical mixing, growth of CNTs
on Si, anchoring Si on the CNT surface, and deposition of Si on a CNT film to form a Si/CNT composite
paper. However, the confinement effect of CNTs is not satisfactory due to the inhomogeneous
distribution of Si particles and the fact that they are not strongly confined by the CNT network within a
nanospace. Nanostructures of Si nanobeads strung by CNTs and Si nanotubes confined in CNTs were
proposed to accommodate huge volume changes of Si during lithiation and delithiation without
appreciable mechanical failure. Chen’s group demonstrate the synthesis of uniform MWCNT@Si
nanocomposites via the magnesiothermic reduction of pre-synthesized MWCNT@SiO2 nanocables.
The uniform MWCNT@Si nanocomposite electrode shows a capacity of approximately 900 mAh/g at
200 mA/g. When the current density is reset to 400 mAh/g, a capacity of 680 mAh/g can be retained,
which indicates the good rate capability of the as-prepared uniform MWCNT@Si nanocomposite
electrode.

33
3.2.12 Silicon-carbon nanosphere
Carbon nanospheres consist of graphite layers distributed discontinuously in the graphite structure with
a state of glass phase. Since the carbon nanospheres have high specific surface, excellent chemical
stability and thermal stability, etc., they can be applied to preparation of high strength and high density
C/C composite materials, high performance liquid chromatographic columns, high specific surface area
activated carbon materials, LIB anode materials and a series of high-performance carbon materials.
Carbon microspheres have a strong adsorption capacity and they can be used repeatedly.

Figure 26 Fig 3-8: The schematic fabrication of mesoporous Si@C microspheres

3.2.13 Doping modification of silicon–carbon anode materials

Heteroatom doping can significantly change the carbon material elements, its surface activity and
improve its electrochemical properties. Non-metallic elements (boron, nitrogen, sulfur, phosphorus) and
metal elements (K, Al, Ga, V, Ni, Co, Cu, Fe) are often applied in doping modification of silicon– carbon
materials. Among the heteroatoms, the atomic radius of the nitrogen atom is closer to that of the carbon
atom than any other atoms, which makes it easier to replace carbon atoms in the atomic lattice of carbon
materials to form the N-doped carbon material. A nitrogen atom has one more extranuclear electron than
a carbon atom, and with the very high electron affinity it can offer carbon atoms adjacent to the nitrogen
atom a higher positive charge density. At the same time, there is a conjugate effect between lone pair
electrons of nitrogen atoms and the big pi bond of the carbon atomic lattice. As a result, the nitrogen-
doped carbon materials display excellent electrochemical properties and catalytic properties. Nowadays,
the doping modification methods of silicon–carbon materials are mainly dependent on nitrogen doping.

3.2.14 Si/nitrogen-doped carbon anode materials

The N-doped carbon layer with multiple type nitrogen is believed to deliver high electronic conductivity
and electrochemical activity and help transport lithium ions in the interface due to defects caused by
nitrogen doping. Among heteroatoms for various doping sources, e.g. nitrogen or boron, nitrogen is the
most attractive dopant in the carbon network, because the atomic size of nitrogen is comparable to that
of carbon and its five valence electrons are available to form strong valence bonds with carbon atoms.

34
The nitrogen atoms incorporated into carbon networks should lead to the formation of stronger
interactions between the nitrogen-doped carbon layer and lithium, which might be favorable for lithium
insertion. The N-doped layer could prevent direct contact between the electrode material and electrolyte.
In addition, it is beneficial to improving the electronic conductivity of the composite and lithium ion
transmission at the interface of the electrode and electrolyte. Nitrogen doped carbon-coating layers play
a critical role in promoting and preserving the stable SEI layers and providing an efficient transport
pathway for the electrons. In table 3-5, we can see clearly that nitrogen-doped carbon materials
significantly improve the conductivity and coulombic efficiency.
Table 7

Table 3-5: Electrical properties of nitrogen-doped silicon–carbon composite anodes. Qr1, the first reversible capacity; CE,
coulombic efficiency; QdN(N), discharge capacity in Nth cycle; C.R.N., capacity retention in Nth cycle. NC, nitrogen-
doped carbon; SPs, spheres; RGO, reduced graphene oxide.

Figure 27 Fig 3-9: Schematic illustration of the synthesis process of Si@C and Si@N-doped carbon. IL, ionic liquid

3.2.15 Compound modification of silicon–carbon anode materials

Within the mixed silicon and carbon anode materials, silicon and carbon are closely combined to form
a stable and uniform system. In the process of charging and discharging, silicon is the active center of
electrochemical reaction and the carbon carrier has the effect of lithiation and delithiation. Besides, the
carbon carrier can also be an electron transport channel and structural support. Through making
compound modification by combining different series of carbon materials with silicon, composite

35
materials with uniform conductive network structures, good electrical conductivity, good adhesion and
high chemical stability can be prepared. From table 3, we can clearly see that the silicon–carbon
composite anode materials with different components can significantly improve the electrochemical
cycling performance of LIBs.

3.2.16 Si/carbon/graphite anode materials

The biggest problem for using silicon as anode is the huge volumetric expansion up to 300% when
silicon is maximally lithiated. One of the ways to reduce the large volumetric expansion effect and make
great use of the large specific capacity of silicon is blending graphite and silicon. Graphite is a good
candidate for a new anode material because it has great advantages of stability and cheaper cost as well
as low working voltage. We may use a composite of graphite, carbon and silicon to provide affordable
anode capacity with minimized anode volume expansion. A silicon/graphite/amorphous carbon (Si/C)
composite with a low silicon content in a core–shell structure was synthesized by the spray drying
method. The combination of the core–shell structure for the composite and a porous carbon-coating layer
accommodates the large volume change of the silicon during the lithium intercalation/extraction process,
thus stabilizing the electrode structure during discharge/charge cycles. The as-obtained Si/C composite
demonstrates high capacity and excellent cycle stability with an initial specific discharge capacity of
approximately 723.8 mAh/g and a reversible specific capacity of approximately 600 mAh/g after 100
cycles at a constant density of 100 mA/g.

Figure 28 Fig 3-10: Schematic illustration of the synthesis procedures of G/Si@C

3.2.17 Si/carbon/graphene anode materials

The isolation of a single layer of graphite, known today as graphene, not only demonstrated amazing
new properties but also paved the way for a new class of materials often referred to as two dimensional
(2-D) materials. Graphene has either planar or 3-D morphology. Graphene in 2-D planar form has been
intensively explored in fundamental physics and surface chemistry, electronics and (b) optoelectronics,
but it is less studied in energy, environmental and biomedical applications. Three-dimensional
nanostructured graphene can be used as a replacement or enrichment material. One of the more common
routes to fabricate graphene is by CVD, which has emerged as the dominant synthesis route since it is
already a well-established process in both industry and laboratories. In recent years, graphene has been
proposed as one of the best active carbon sources to prepare silicon-based composite anodes due to its
excellent properties such as high conductivity, high mechanical strength, high chemical stability, super-
high specific surface area and open porous structure. Graphene plays a flexible confinement function
for tolerating volume changes to the composite in LIBs. Since graphene has large surface area, high
electrical conductivity and discharge capacity, it is an attractive carbon material to improve the
electrochemical performance of the Si-based composite electrodes, leading to a more enhanced cycle
Ability at large current densities.
36
Figure 29 Fig 3-11: Schematic fabrication process of the sandwiched Si/CNFs@rGO composite

3.2.18 Conclusion and perspective

In general, the research on silicon–carbon anode materials are mainly aimed at the development of a
higher energy density, greater charge–discharge performance, stable cycle performance and higher
safety performance aspects, and the development of large-scale preparations of low cost, stable
performance silicon–carbon composite materials. Methods such as structural modification can
effectively increase the surface area, thus the first reversible capacity of the silicon–carbon anode
material is improved. Heteroatomic doping can change the conductivity of the material and has
effectively improved the coulomb efficiency of silicon–carbon anode materials. Through combination
with carbon materials with excellent mechanical flexibility, high electronic conductivity and chemical
stability in the electrolyte, we can clearly find that the cycling stability of silicon–carbon anode materials
is greatly improved. In addition, research on the mechanism of lithiation–delithiation and the exploration
of adhesives and electrolytes that are more compatible with the silicon–carbon materials will also be hot
topics in the following 50 years.

37
3.3 Advanced cathodes
Many advanced-cathode chemistries exist that have higher energy capacities and voltages, such as
lithium nickel manganese oxide (LNMO). These high-voltage cathode materials are currently facing
issues with the liquid electrolyte used in common battery systems, which breaks down at voltages above
4.5 V.
Among many types of batteries, Li-ion and Li-S batteries have been of great interest because of their
high energy density, low self-discharge, and non-memory effect, among other aspects. Emerging
applications require batteries with higher performance factors, such as capacity and cycling life, which
have motivated many research efforts on constructing high-performance anode and cathode materials.
Herein, recent research about cathode materials are particularly focused on. Low electron and ion
conductivities and poor electrode stability remain great challenges. Three-dimensional (3D) porous
nanostructures commonly exhibit unique properties, such as good Li+ ion diffusion, short electron
transfer pathway, robust mechanical strength, and sufficient space for volume change accommodation
during charge/discharge, which make them promising for high-performance cathodes in batteries. A
comprehensive summary about some cutting-edge investigations of Li-ion and Li-S battery cathodes is
presented. As demonstrative examples, LiCoO2, LiMn2O4, LiFePO4, V2O5, and LiNi1−x−yCoxMnyO2 in
pristine and modified forms with a 3D porous structure for Li-ion batteries are introduced, with a
particular focus on their preparation methods. Additionally, S loaded on 3D scaffolds for Li-S batteries
is discussed. In addition, the main challenges and potential directions for next generation cathodes have
been indicated, which would be beneficial to researchers and engineers developing high-performance
electrodes for advanced secondary batteries.
Currently, cathode materials are one of the key points for the development of high-performance Li-ion
batteries and Li-S batteries. Many cathode materials, almost with porous characteristics, have the
advantages of enlarged surface area, increased specific capacity, and are able to overcome volume
variation. Among various structures, three-dimensional (3D) porous structures are considered ideal and
promising.
It is necessary to improve the kinetics of the extraction/insertion process of Li ion in Li-ion batteries and
the reaction between Li ions and S in Li-S batteries, which can be facilitated by constructing a 3D porous
morphology. In addition, 3D porous structures have several void spaces, which are able to improve the
contact with electrolytes. However, a part of the electrolyte is needed to wet the active materials during
the charge/discharge process, therefore the 3D structure would consume more electrolytes. In addition,
the reduced material loading within the 3D electrode also needs to be improved for practical applications.
Both the advantages and drawbacks of the 3D porous electrodes make it an attractive field for intensive
study. Herein, we focus on the 3D porous cathode materials used in both Li-ion and Li-S batteries and
their preparation methods.

3.3.1 Challenges of Li-Ion and Li-S Battery Cathodes

Performances of Li-ion batteries are partly dependent on the intrinsic property of the materials used in
the cathodes. For cathode materials, high specific capacity, high potential, large ionic and electronic
transport rate, and long life are preferred. Nowadays, most of the cathode materials are Li-based
intercalation compounds. The available compounds, such as LiNiO2, LiCoO2, and LiMnO2, are
investigated for cathode applications. To achieve a high energy-density, some compounds composed of
multiple metal atoms, such as LiNi1/3Co1/3Mn1/3O2 (NCM), are expected to replace part of the single
metal compounds. Compounds with MO6 octahedra (where M is Fe, Mg, or V) and XO4 n– tetrahedral
anions (where X is Si or P) are of interest because these structures can tune transition metal redox
potentials, such as Fe3+/Fe2+. However, these kinds of compounds have a common and fundamental
problem in that the conductivity is poor, which reduces the electrochemical performance. Compared to
Li-ion batteries, Li-S batteries have a much higher theoretical energy density (2600 Wh/g) and better
capacity (1672 mAh/g). However, severe issues of sulfur need to be addressed.
38
At first, elemental sulfur is a natural insulator (5 × 10−30 S/cm), which absolutely restricts the movements
of electrons. The long-chain lithium polysulfide formed during the discharge process tends to dissolve
in the organic electrolytes. When these polysulfides diffuse to the anode through the electrolytes, and
react with the lithium anode, the reactions are named as shuttle mechanisms. During the transition
between long-chain and short-chain lithium polysulfides, partial electrical energy is consumed, and this
unexpected phenomenon restricts the electrical efficiency. Meanwhile, an unstable film will be
generated because of such uncontrolled reactions. As a result, the instability of solid electrolyte interface
(SEI) film has a negative effect on the cycling stability of Li-S batteries. It is mentioned that the mass
density of sulfur (2.03 g/cm) is about 20% larger than that of Li2S (1.67 g/cm), which causes the non-
ignorable shrink and expansion during charge and discharge. Last but not least, the morphology of the
lithium electrode is changeable due to the deposition of lithium ions from electrolytes. Dendrites of
lithium growing on the surface of the electrode should be removed to ensure battery safety.

3.3.2 Methods for Making 3D Porous Li-Ion Battery Cathodes

Hydrothermal methods include the various techniques for crystallizing materials from high-temperature
aqueous solutions at high vapor pressures. Compared with several other types of crystal growth, the
hydrothermal approach is able to create crystalline phases that are not stable at the melting point. In
addition, materials that have a high vapor pressure near their melting points can be grown by the
hydrothermal method. These advantages make the hydrothermal method suitable for constructing many
3D electrodes for batteries. This section will mainly focus on the hydrothermal methods.
The conventional LiFePO4 cathode has a poor electronic conductivity (~10−9 S/cm) and slow lithium
ion diffusion, which restricts its wide application. Several methods have been performed to enhance the
electric conductivity and the rate of ion transport, including reducing the size of LiFePO4 to the
nanometer scale, coating particles with conductive materials, or expanding surface areas through
structure manufacture. A 3D current collector of carbon layer coated LiFePO4 was constructed, in order
to improve the high-rate discharge capacity compared to conventional cells using the foil current
collector. Furthermore, the carbon layer on LiFePO4 nanoparticles with a diameter between 70 nm and
100 nm protects these particles and also contributes to conductivity enhancement. In addition, the porous
substrates made of nickel and chromium not only improve electric conductivity but also produce a large
surface area.
Li3V2(PO4)3, with the crystal structure of monocline, is promising for the cathode material in Li-ion
batteries because of its inherent characteristics of a high working potential of 4.8 V, theoretical capacity
of 197 mAh/g, and higher energy density of 800 Wh/kg. Li3V2(PO4)3 phase consists of a 3D framework
of slightly distorted VO6 octahedra- and PO4 tetrahedra-sharing oxygen vertexes, which host Li ions in
relatively large interstitial sites, leading to fast ionic transport. Cui et al. prepared carbon-coated
Li3V2(PO4)3 nanocrystals that were modified by graphene nanosheets and carbon nanotubes through a
hydrothermal method, as shown in Figure 3-12. The graphene nanosheets and the carbon nanotubes are
interconnected to form a 3D conductive network, which also support Li3V2(PO4)3 particles. When using
graphene sheets, the aggregated Li3V2(PO4)3/C nanoparticles load on graphene sheets, forming a 3D
layered structure. When the carbon nanotubes were also used, the interconnection between each
graphene layer was improved. The carbon nanotubes enhance the structure strength and provide
pathways for electron transfer. Considering the shaggy structure of the composites, the composite
exhibits a remarkably high rate capability and long cycle stability. An initial discharge capacity of 147.5
mAh/g at 20 °C at a potential range of 3.0–4.8 V is obtained. The capacity retention is 82.7% after 2000
cycles.

39
 Fig 3-12: Schematic illustration of preparing nanosized Li3V2(PO4)3/C (C-LVP), carbon nanotube modified Li3V2(PO4)3/C
(C-LVP/GNS), graphene nanosheet, and carbon nanotube co-modified Li3V2(PO4)3/C (C-LVP/(GNS+CNT)) composites
Figure 30 via a hydrothermal-assisted sol-gel route.

Vanadium pentoxide (V2O5) is a typical intercalation compound. It possesses a layered structure that
can accept more than one electron and lithium ion through the reaction:

➢ V2O5 + xLi+ + xe− ↔LixV2O5.

However, V2O5 has shortcomings, with a moderate electrical conductivity of 10−4–10−5 S/cm and low
Li+ diffusion coefficient of 10−12 cm2/s. As is known, binder-free technology loads active materials on
the current collector without any binders and conductive adhesives, enabling a simplified electrode for
batteries. Many free-standing 3D porous V2O5 electrodes have been reported. In addition, 3D
hierarchical nanostructures are widely applied in electrodes because such structures suppress the
agglomeration and improve the diffusion of lithium ions.
There has been presented a facile method for manufacturing 3D structural electrodes by integrating
active materials and graphene. As displayed in Figure 3-13, a sandwich-like structure of
V2O5@graphene@V2O5 was fabricated for the cathode based on the 3D inverse opal template. At first,
a Ni inverse opal was electrodeposited on a polystyrene opal template, on which graphene was then row
via chemical vapor deposition. After a Ni etching process, a layer of V2O5 was grown onto the external
surface of graphene. Then, another layer of V2O5 was grown into the inner layer of graphene, forming
the 3D V2O5@graphene@V2O5 composite. The cathode provided a full electrode basis capacity of about
230 mAh/g at 5 C after 200 cycles, and 203 mAh/g after 2000 cycles, along with a Coulombic efficiency
of 99.7%.

Figure 31
Fig 3-13: Schematic illustration for the fabrication of the 3D sandwich-structured V2O5@graphene@V2O5 cathode.
40
3.3.3 Sol-Gel Method
Another widely used method for preparing 3D electrodes is sol-gel. For example, there is a sol-gel
method with polystyrene beads as templates to prepare 3D LiMn2O4 thin films. A monolayer of
polystyrene microspheres was first deposited on the surface of the substrates, which was the basis or
manufacturing an open volume without overlaps in the perpendicular direction. Subsequently, the
prepared solvents containing precursor materials were dipped onto the substrates. After the calcination
of deposited films, the polystyrene template was removed by the thermal decomposition. The precursor
was converted to LiMn2O4. At last, a 3D spherical porous structure with an inverse-opal was formed. It
was found that discharge capacity was associated with the annealing temperature, which has strong
effects on the stable structure. Zhang et al. successfully encapsulated Li3V2(PO4)3 nanoparticles in
amorphous carbon via a facile sol-gel method. The presence of thin carbon layer and carbon network
benefit Li+ transport and electron conductivity. Applied as the cathode, this material exhibits a capacity
of 85 mAh/g at a high rate of 30 C. The sol-gel method is commonly low-cost and simple, which make
it appropriate for preparing electrodes with a large yield. Particularly, their industrial manufacture
always contains a sol-gel preparation.

Other Methods: Differing from the methods shown above, there are some other preparation approaches
for making 3D cathodes for Li-ion batteries, including freeze-drying, chemical vapor deposition,
vacuum filtration, and solid based approach.
More details about the comparison with some 3D Li-ion battery cathodes are listed in Table 3-6.

41
Table 8

Table 3-6: Comparison on the performance of three-dimensional Li-ion battery cathodes.

42
3.3.4 Methods for Constructing 3D Porous Li-S Battery Cathodes and Their
Comparison
3D Porous S Cathodes for Li-S Batteries

There are several reasons that the elemental sulfur itself cannot be fabricated as the cathode in Li-S
batteries. One is that the sulfur is insulative and does not have a firm crystal to form a solid structure. In
this case, after sulfur reacts with lithium ions, the resultant Li2S cannot be fixed in situ. The alternative
method is to combine sulfur with other conductive materials. A frame strategy is promising and viable
for solving the issues of elemental sulfur by coating sulfur onto a frame that has good conductivity, a
large surface, and a porous structure. Until now, carbon materials, conductive polymers, and metal or
metal oxides have been studied for sulfur-based cathode materials.
The energy stored in Li-S batteries is closely related to the mass of the sulfur. As such, 3D porous
structures are desired to increase the mass loading.
Various kinds of carbon matrices, including carbon nanotubes, graphene, carbon nanofibers, carbon
spheres, and mesoporous carbon, have been chosen to act as a frame for Li-S batteries. For example,
reported an approach to assemble a sulfur-graphene sponge with sulfur uniformly distributed into the
pores of a graphene sponge. The graphene sponge framework can not only improve the electronic
conductivity but also accommodate the volume change in the charge and discharge process. The
electrochemical measurement showed a high areal specific capacity of 4.53 mAh/cm after 300 cycles
and a slow decay rate of 0.08% per cycle after 300 cycles at 0.1 C. To some extent, the interlaced
graphene layer can absorb the polysulfides intermediate product. More performance comparison about
3D S cathodes are listed in Table 3-7.
A wood-inspired multi-channel tubular graphene architecture prepared by chemical vapor deposition
was also studied. This unique structure provides a large interior space that accommodates sulfur and
fixes the generated polysulfide. Meanwhile, the 3D multi-channel network also promotes mass transport
and ion diffusion. The benefit from these properties is that the MCTG/S cathode for Li-S batteries
delivers a discharge capacity of 1390 mAh/g at 0.1 C.
The in-situ construction method was also used for preparing oxide-based composites. Several oxide-
based cathodes were reported to possess the adsorptive capability towards polysulfides, including Li2S2,
Li2S4, and Li2S6. It is necessary to reduce the shuttle effect of a Li-S battery, leading to improved
stability. In contrast, the sulfur-based cathodes commonly suffer from loss of active materials because
of the dissolving and transferring of polysulfides. The relatively high loading is more attractive for
sulfur-based cathodes, as the oxide hosts are usually of large weight and volume compared to the active
component sulfur within the electrodes. As for the preparation of Li-S battery cathode, many techniques
used for making Li-ion battery cathodes are also applicable. Some methods are summarized in Table 3-
7. However, what should be noted is that the low melting point of sulfur makes the high-temperature
treatment unsuitable.

43
Table 9

Tabel 3-7: Comparison on the performance of 3D cathodes in Li-S batteries.

44
3.3.5 Brief Comparison between Li-Ion and Li-S Batteries
As for the Li-ion batteries, they are advantageous as they show good safety, high working voltage, good
specific capacity at low cycling rate, long cyclic performance, and low self-discharge. In parallel, for
the Li-S batteries, capacities are commonly from 700 to 1500 mAh/g, which are competitive with some
other batteries. Nevertheless, there are some challenges for Li-S batteries, such as the dissolution of
polysulfide in electrolyte, poor conductivity of sulfur, and the damage to the active materials caused
from volume change. For example, the conductivity of S means it needs more conductive carbon and
polymer binder in the cathode, which decreases the mass content of active materials within the electrode.
Therefore, improving the capacity of the Li-ion battery and increasing the loading of sulfur in the Li-S
battery are necessary to achieve a good energy density in practice.
However, many energy storage devices based on combustible organic solvents inevitably carry the risks
of leakage, heavier packaging and related hazards. A liquid electrolyte is volatile at high temperature
when the battery is charged or discharged quickly, or packs of car batteries are damaged in accidents.
Against inherent disadvantages of liquid electrolytes, solid electrolytes of nonflammable polymers and
all-solid-state batteries using inorganic materials have been developed. When a battery releases power,
Li ions move from the anode through the electrolyte to the cathode. In this point, more conductive
electrolyte generates better battery performance. Therefore, the promise of Li ion solid-state batteries is
the replacement of the heavy and sometimes dangerous liquid electrolyte with lighter, more versatile
and solid alternatives. Although finding a solid electrolyte with conductivity comparable to liquids has
been still a challenge, the solid electrolyte batteries are popular. They are safer because flammable
components are removed and deliver more power by replacing the carbon-based anodes with Li metal.
This leads to a higher energy density and cycle life with less weight and cost. In addition, without a need
to struggle to safely pack a liquid electrolyte in a shape, all-solid-state batteries can be fabricated in more
versatile shapes, reducing manufacturing costs. This could make electric cars a more enticing
proposition with longer running distance and a lower purchase price. In many ways, all-solid-state
constructions certainly enhance the overall performance of energy storage and conversion.

3.4 Solid-state electrolytes

When we are talking about ‘solid state’ batteries we are talking about batteries that use a solid electrolyte
instead of the liquid one, Wide range of different potential ‘solid state’ materials and Various kinds of
dry polymer, silicates, metals crystals, mineral composites, glass, etc. Solid-state batteries have found
use in pacemakers, RFID and wearable devices. They are potentially safer, with higher energy densities,
but at a much higher cost.
Advantages over liquid electrolytes:

• Safety, would eliminate the thermal runway, Liquid electrolyte is flammable and
becomes flammable gas-critical safety element in Li-Ion and Moving to solid state
significantly changes these properties

• Performance, high voltage possible, increases because solid state material can be 80- 90%
thinner than separator plus electrolyte and Energy density potentially doubles if we use
lithium metal as anode

• Many additional benefits are possible, but depends greatly on formulation of solid-state
solution

• Lifetime, charge rates, stability at high voltage, lithium anodes, lithium-air feasibility

45
Disadvantages over liquid:

• Cost, traditionally very expensive to make

• Temperature sensitive, low temperature can be a challange

There is different solid-state solution under development, many different kinds materials under
investigation: Li-Halide, Perovskite, Li-Hydride, NASICON-like, Garnet, Argyrodite, LiPON, and
LISICON-like, Difficult to say what’s going on behind closed doors but LiPON and Garnet cells are
perhaps the most promising,
LiPON (sulfide-based thin film) is usually made with lithium anode:

• Great benefits for lifetime, also weight, thickness and flexibility

• Total energy capacity and conductivity are rather poor and thus can’t be scaled up as
easily

Figure 32 Fig 3-14: conventional battery and solid-state battery

Garnet-oxide (LLZO) electrolytes have a high ionic conductivity at room temperature, only just less
than liquid lithium-ion electrolytes:

• Garnet requires expensive sintering process for fabrication

• Garnet is also stable in air and water, making it a potential enabler of Li-Air batteries

3.4.1 Thin Film Solid State Batteries

Thin-film solid state batteries (TSSBs), which have been under development for several decades and
have been commercialized, promise to solve some of the issues with conventional Li-ion cells. SSBs are
fabricated using traditional semiconductor manufacturing methods and replace the liquid electrolyte
with an inert lithium-conducting glass typically a member of the lithium phosphorus oxynitride (LiPON)
family. The use of a solid electrolyte renders the batteries nonflammable and tolerant to high
temperatures, and the additional chemo-mechanical stability imparted by the use of LiPON allows
TSSBs to operate for thousands of cycles. TSSBs are also geometrically optimal, in the sense that they
are effectively one-dimensional structures which minimize inhomogeneous internal current distributions
and require ionic and electronic transport length scales on the order of a few micrometers at most. In

46
addition, using mature semiconductor manufacturing methods allows for the straightforward fabrication
of batteries with sub-mm lateral dimensions, and the solid electrolyte can readily have submicron
thickness to minimize internal resistance. However, the use of nonconformal, line-of sight physical
vapor deposition (PVD) to deposit the battery components critically limits the form factor of TSSBs to
planar substrates, which in turn limits TSSBs to capacities on the order of 0.1 mAh/cm 2. On a planar
substrate, the cathode cannot easily be made more than ~5-10 μm thick before film stress results in
delamination and cracking. In addition, in a planar geometry, there is a fundamental tradeoff between
the deliverable areal power density and energy density- the only method available to PVD to improve
the energy density is to increase the cathode thickness, but a thicker electrode cannot deliver its full
capacity at high power due to the increased diffusion length for Li ions.

Figure 33

Fig 3-15: Methods of improving energy storage metrics for thin film solid state batteries. Increasing the electrode thickness
scales energy density at the expense of power density due to the rapid increase in the characteristic diffusion time for ions
in the thick electrode. Fabricating TSSBs in a 3D structure both increases areal material loading and increases power
performance through a decrease in the internal current density due to the larger internal surface area.

47
3.4.1.2 Moving to 3D Architectures
While battery performance can be incrementally improved through materials development, i.e. through
the use of higher capacity/voltage electrodes, enabling TSSB fabrication on 3D substrates, analogous to
the strategies now employed to improve transistor and NAND flash memory areal packing density in
semiconductor devices, would be a more fundamentally enabling approach. By simply increasing the
surface area upon which a TSSB is grown, the areal capacity can be improved while maintaining optimal
(usually nanoscale) electrode thicknesses and locally 1-D current distributions for high specific power
densities (Figure 3-15). 3D TSSBs were first proposed in detail in 2004 and have been a goal of the
energy storage community since at least that time, with several subsequent reports outlining the benefits
of the architecture. While conceptually simple, the experimental realization of such 3D TSSBs has been
stymied by the need for extremely conformal deposition techniques for the active layers of a battery,
and only a handful of examples of working cells have been reported. Arguably the most successful
design was described by Peled et al., who developed Li-ion full cells formed in microchannel plates
using a mixture of electrodeposition and physical impregnation steps. While the device performance
was impressive, this method may be difficult to scale down and does not achieve ideal layer self-
alignment. Talin et al. have shown the 3D TSSBs can be fabricated over 3D scaffolds of modest aspect
ratio using RF sputtering, but in two reports such cells actually performed worse than planar analogues
due to electrical leakage and inhomogeneous current distributions, again because the active layers did
not have a uniform thickness.
A better approach to fabricating full cells with uniform thickness in high aspect ratio 3D structures is to
use vapor-phase chemistry methods such as chemical metalorganic chemical vapor deposition (CVD)
or atomic layer deposition (ALD). ALD in particular is capable of uniform growth in structures with
aspect ratios in the hundreds and works at temperatures low enough (generally below 300C) to enable
deposition on flexible polymeric substrates. Importantly, ALD and CVD are both mature techniques
integrated with existing semiconductor manufacturing. Yet, there are no published examples of full
solid-state batteries in which all active components are grown via a conformal vapor-phase deposition
technique such as CVD or ALD, despite significant work exploring the growth and electrochemical
performance of individual battery components in isolation. Growing thin film materials with vapor phase
chemistry is generally more complicated than by PVD, as each process involves a carefully designed
surface-mediated chemical reaction in contrast to ablating and re-depositing material from a
prefabricated target. This leads to a limited selection of high-quality electrode materials, discussed
further below. Conformal inorganic solid electrolytes are even more limited, and include CVD lithium
phosphate, ALD LiPON variants, and a few mixed lithium metal oxides. ALD-grown electrolytes are
particularly attractive because of their unique ability to realize complete electrical isolation in full cells
at thicknesses below 50nm, reducing cell size, resistance, and fabrication time. An additional
complication for growing batteries with vapor-phase deposition arises from the need for each layer to
be stable in the deposition conditions of subsequent layers, and each electrode/electrolyte interface must
not be damaged by incoming reactive species, as can sometimes occur with plasma radicals or strongly
reducing/oxidizing precursors. Finally, the exceptional conformality of ALD/CVD becomes a double-
edged sword when it comes to patterning multi-layer active devices such as full batteries. While PVD-
grown TSSBs can be patterned via simple shadow-masking lithography, more conformal techniques
require subtractive approaches in order to define batteries of a specific size without electrically shorting
the anode and cathode.
Now, we will describe the successful fabrication of a 3D solid state thin film Li-ion battery comprised
of 5 conformal layers. The electrochemical couple is formed by a LiV2O5 cathode and a SnxN anode,
each paired with a current collector (Ru and TiN, respectively). For the solid-state electrolyte, we utilize
a previously described ALD lithium polyphosphazene (LPZ) film, which is a polymorph of LiPON. We
take a stepwise approach to measuring intrinsic materials properties, mutual materials compatibility, and
the effects of cell geometry on performance.

48
 • First, we construct planar solid-state half-cells comprised of either the anode or cathode
paired with LPZ and a thin film Li metal anode in order to assess operating potential
range and electrochemical kinetics of each electrode, as well as the mutual compatibility
of the electrode and ALD electrolyte.

• We then develop a finite-element simulation of the cathode based on half-cell data in

order to predict performance scaling for planar vs. 3D devices.

• Next, we fabricate planar full cells using vapor-phase grown materials in order to assess
the kinetics and stability of the full cell chemistry, as well as optimal capacity matching
for the electrodes. Optimized all-ALD full cells exhibit excellent cycling stability and
reach 37 μAh/cm2· μm normalized to the cathode thickness.

• Finally, we successfully integrate the full cell film stack with 3D-structured substrates
and demonstrate the simultaneous upscaling of both areal capacity and rate performance.
Demonstrated benefits of 3D structuring include an order-of-magnitude improvement in
areal capacity, improved rate performance, and improved round-trip efficiency.

3.4.1.3 Electrode Selection

Conformal battery materials were primarily chosen based on three criteria: (1) ability to be synthesized
at moderate or low temperatures (≤ 250C) in the active phase to enable growth on a broad variety of
substrates, (2) minimal complexity of fabrication to reduce production time (i.e. avoiding more than two
precursors per ALD process), and (3) mutual compatibility with regard to both synthesis conditions and
electrochemical stability.
The selection of developed cathode and anode materials available for growth via ALD is limited because
of the difficulty in growing crystalline, Li-containing multicomponent oxides without a high temperature
annealing step. In the case of multicomponent oxides, it has been reported that common Li precursors
(including LiOtBu) frequently do not exhibit self-limiting growth on oxide surfaces due to their tendency
to directly reduce metal ions as a side-reaction,30 analogous to direct chemical lithiation. Li-containing
ALD-grown crystalline cathodes require a high-temperature annealing step. Materials reported to be
grown by ALD in this manner include LiCoO2, LiFePO4, and LiMn2O4, reaching varying levels of
performance relative to bulk synthesis methods as a result of impurity inclusion from nonstoichiometric
Li incorporation. Another disadvantage to growing cathode films via multicomponent ALD processes
is the increase in deposition time; adding an additional Li-incorporating sub cycle to a binary ALD
process roughly halves the growth rate.

1) Cathode: To avoid these issues, we have taken a simpler approach to synthesizing a

conformal prelithiated cathode. The ALD reaction between VO(OC3H7)3 (VTOP) and O3
produces crystalline V2O5 at 170 °C. We then employ electrochemical lithiation as a
conformal technique to rapidly transform the deposited V2O5 through the reaction V2O5
+ Li+ + e- → LiV2O5 in a LiClO4/propylene carbonate electrolyte, which can then be
incorporated into a full solid-state battery. At 3.4 V vs Li/Li+, the potential of the lithium
intercalation reaction is within the electrochemical stability window of the electrolyte,
resulting in minimal surface contamination. Orthorhombic V2O5 is a commonly
employed TSSB cathode material exhibiting multiple lithium intercalation phase
transitions, and when cycled in the one Li per unit cell electrochemical window, exhibits
an acceptable capacity (49 μAh/cm2·μm), high voltage (> 3V vs. Li/Li+), and excellent
cycling stability. The primary downside of the material is a limited rate capability due to
a relatively low average chemical diffusion coefficient for Li (≈ 10-13 cm2/s), although
as we will show this problem can be partially mitigated using nanoscale films and 3D
49
 structuring.

2) Anode: On the anode side, the use of Li metal is currently ruled out for lack of a plausible
ALD process. Thus, any all-ALD conformal SSB will be a Li-ion cell. ALD processes
for single element alloying type anodes such as Si, Sn or Al are also yet to be developed,
although relatively low temperature and conformal CVD processes are available for Si
in particular. Conversion-type anodes, which undergo a first-cycle irreversible
transformation into an active phase, are a promising alternative and are readily made via
vapor phase chemistry. For the batteries in this paper, we utilize a novel ALD process for
amorphous tin nitride (SnNx) grown using tetrakisdimethylamidotin (TDMASn) and a
N2 plasma, which will be described fully in a separate publication. This process produces
an amorphous material with a temperature-dependent composition of approx. SnNx (x ≈
2 at 200 °C) plus a small amount of carbon and oxygen incorporation. Tin nitride, which
has been utilized previously in lithium-ion configuration planar thin film SSBs,4 was
chosen for its low electrochemical potential (operating below 1V vs. Li/Li+) and use of
nitrogen as the oxidant, which was expected to be less damaging to the electrolyte/anode
interface than H2O.

3) Current Collectors: A conformal battery also requires conformal current collectors in

intimate contact with both electrodes. In this work, we utilize ALD Ru as the cathode
current collector and ALD TiN as the anode collector, which has been previously shown
to be a good conductive Li diffusion barrier.

3D structuring of thin film solid state batteries is a promising method of producing high-performance,
intrinsically safe energy storage devices with exceptional areal energy and power densities. For the first
time, we have established a set of materials (a prelithiated LiV2O5 cathode, a SnNx anode, and a lithium
polyphosphazene solid electrolyte) which are mutually compatible, are grown in the active phase at
temperatures ≤ 250C, and can be reliably made using conventional ALD deposition tools which are now
common in industrial and university settings. 3D cells can be successfully fabricated through deposition
in micromachined silicon substrates followed by masked etching, and full electrical isolation between
anode and cathode can be achieved with solid electrolytes ≤ 100nm in thickness in structures with an
AEF of up to 10. Solid state batteries made from the LiV2O5-SnNx couple exhibit stable capacities of
2.6 μAh/cm2, (37 μAh/cm2·μm normalized to the cathode thickness) for hundreds of cycles. The areal
discharge capacity of16 these cells can be scaled up to 9.3x that of planar cells through integration with
3D substrates, though at present 3D cells suffer from additional anomalous capacity loss that should be
addressed through better cell encapsulation. Most importantly, 3D structuring improved the rate
performance and RTE of the cells while simultaneously increasing the areal capacity. This beneficial
combination was measured in a range of current densities (if : ≥ 100 μA/cm2) which was indicated by
simulation to be a power regime in which such scaling was not possible for planar cells. Future
development of 3D TSSBs can utilize a “mix-and-match” strategy for materials selection combined with
the fabrication scheme developed in this work, though at the present time the ALD LPZ electrolyte is
probably the best conformal inorganic electrolyte available. While the use of LiV2O5 may continue to
be appropriate for integration with temperature-sensitive substrates such as polymer films, matching and
exceeding the performance of conventional Li-ion cells will likely require its replacement with a cathode
material with a higher chemical diffusion constant for Li, such as LiCoO2. It would also be interesting
to explore the integration of the conformal TSSBs described here with more extensively three-
dimensional substrates, such as fabrics, fibers, conductive metal foams, which could form the basis of
multifunctional energy-storing materials and composites.

50
3.4.2 The Fabrication of All-Solid-State Lithium-Ion Batteries via Spark Plasma
Sintering
Spark plasma sintering (SPS) has been successfully used to produce all-solid-state lithium-ion batteries
(ASSLibs). Both regular and functionally graded electrodes are implemented into novel three-layer and
five-layer battery designs together with solid-state composite electrolyte. The electrical capacities and
the conductivities of the SPS-processed ASSLibs are evaluated using the galvanostatic charge-discharge
test. Experimental results have shown that, compared to the three-layer battery, the five-layer battery is
able to improve energy and power densities. Scanning electron microscopy (SEM) is employed to
examine the microstructures of the batteries especially at the electrode–electrolyte interfaces. It reveals
that the functionally graded structure can eliminate the delamination effect at the electrode–electrolyte
interface and, therefore, retains better performance. However, current solid-state batteries have
significantly lower power and energy densities than their liquid-state counterparts, making them less
practical for industrial and commercial applications. Therefore, most of the studies regarding all-solid-
state lithium-ion batteries (ASSLibs) are revolving around improving the power and energy densities of
the cells. Polymeric electrolytes were considered as they are easy to fabricate and flexible in some
applications. However, they have relatively low ionic conductivity and tend to oxidize when contacting
electrodes. Moreover, polymeric electrolytes are not stable at high temperature regimes. Extensive
research has been conducted on different ceramic materials for use as electrolytes, and three crystal
structures have been shown to facilitate high total (bulk and grain boundary) ionic conductivity.
Perovskite-structured electrolytes (Li3xLa2/3−xTiO3 or LLTO) have been found to have high ionic
conductivity, which is comparable to that of liquid electrolytes. However, this type of electrolyte also
showed low redox potential vs. Li/Li+. Garnet-structured electrolytes such as Li7La3Zr2O12 (LLZO) have
exhibited high ionic conductivity and stable electrochemical properties. However, sintering temperature
and the moisture resistance of LLZO should be taken into account. Two commonly studied NASICON-
structured electrolytes are LiTi2(PO4)3 (LTP) and LiGe2(PO4)3 (LGP). Both of them have shown high
ionic conductivities. Substituting Al for Ti in LTP forms Li1+xAlxTi2−x(PO4)3 (LATP). This doped
composite has higher ionic conductivity, lower sintering temperature, and higher crystalline stability
than the un-doped one and is also stable against moisture.
The main drawback of the ceramic electrolyte materials is their high reactivity with electrode materials
during heat treatment and reduction on contact with lithium. If these electrolytes are to be used,
appropriate electrodes need to be selected to avoid adverse reactions at the electrolyte–electrode
interfaces during heat treatment, charging and discharging. The anode should have low potential, while
the cathode should have high potential vs. Li/Li+, and neither of them should cause electrolyte
decomposition. One optimal anode material is Li4Ti5O12 (LTO) with a potential of 1.55 V vs. Li/Li+;
this material does not react with LATP electrolyte. The most promising cathode materials are the olivine-
structured compounds such as LiMPO4 (M = Fe, Mn, Ni, Co, etc.), providing high structural stability
and low capacity loss. Sintering techniques have been widely applied to produce ASSLibs including the
most attractive spark plasma sintering (SPS) thanks to its coupled electro-thermal mechanical features.
The present study aims at investigating the effect of regular and functionally graded electrodes on the
power density and the interface quality of ASSLibs produced by the SPS technique. Electrodes with
various concentrations of active materials were developed while focusing on increasing the power
capacity. Keeping the same amount of composite ceramic electrolyte, three-layer and five-layer batteries
were fabricated by consolidating electrode and electrolyte powders together in one SPS operation. The
SPS-processed batteries were subjected to galvanostatic charge-discharge and electrical conductivity
tests to determine the effect of electrode compositions on the relative energy and power density.
Microstructural analyses were conducted to examine the electrolyte–electrode interfaces as he battery
structure changed in correspondence to the evolution of its electrical properties.

51
3.4.2.1 Materials and Methods
Commercially available Li1.4Al0.4Ti1.6(PO4)3 powder (LATP, NEI Corp., Somerset, NJ, USA) was
selected to build the electrolyte as it appears to be the most compatible one among all the ceramic
electrolyte materials discussed in previous. In order to offset the thermal mismatch between electrolyte
and electrode, LATP was also used in the electrodes. The active material in the anode was LTO (NEI
Corp., Somerset, NJ, USA), while LiCoPO4 (LCP, NEI Corp., Somerset, NJ, USA) was added to the
cathode, as both of these materials do not react with LATP. To enhance the conductivity of ASSLibs,
acetylene black (AB, MTI Corp., Richmond, CA, USA) powder was used as a part of the composite
electrodes. The morphologies of all the employed raw powders were examined by SEM (Quanta 450,
FEI Co., Hillsboro, OR, USA) and are shown in Figure 3-16. As one can see, these as-received powders
have uniform particle size distribution with an average size in the nano range (different scales are used
to properly exhibit the morphology). Additionally, the XRD analyses (X’Pert Pro, PAnalytical B.V.,
Almelo, The Netherlands) have confirmed that the raw powders are very close to their stoichiometry.

Figure 34

Fig 3-16: SEM images of (a) Li1+xAlxTi2−x(PO4)3 (LATP), (b) LiCoPO4 (LCP), (c) Li4Ti5O12 (LTO), and (d)
acetylene black powders.

For the three-layer battery, as shown in Figure 3-17a, the regular electrodes consisted of 40 wt % (a unit
used to measure weight) LATP, 30 wt % active material (LTO or LCP), and 30 wt % acetylene black as
they were able to be consolidated in one sintering operation according to Reference [33]. However, to
create the functionally graded electrodes, different compositions were developed. A 60 wt % LATP, 10
wt % LTO, and 30 wt % acetylene black composition was implemented as a part of the functionally
graded anode. One can see from Figure 3-17b that these secondary compositions served as an
intermediate layer between the primary anode and the electrolyte, which had a higher LATP content,
thereby reducing the difference in sintering temperature between the different layers. At the same time,
on the cathode side, a layer of 20 wt % LATP, 50 wt % LCP, and 30 wt % acetylene black was primarily
52
used to increase the energy density of the battery as it contained more active materials. These graded
compositions were determined based on the analysis of the three-layer battery interface.

Figure 35 Fig 3-17: Schematics of (a) regular three-layer and (b) functionally graded five-layer batteries.

Once the raw materials were characterized and the electrode compositions were determined, the next
step was to create the composite powders. Selected powders were put together according to the
predetermined weight percentages and ball-milled in a 95% ethanol solution at 60 RPM for 24 h. The
ball milling was carried out in an 80 mL nylon jar with 1 mm tungsten carbide balls, and the weight ratio
of balls to powder was set to 10:1. After the powders were homogenized, the mixture was placed on a
hot plate and heated to 98 °C until the solvent evaporated. The remaining material was then brushed
through a sieve to yield the composite electrode powders. The weighted electrode powder and electrolyte
powder were loaded into 10 mm graphite tooling (I-85 graphite, Electrodes Inc., Santa Fe Springs, CA,
USA). Graphite paper with a thickness of 0.15 mm (Fuji Electronic Industrial Co., Ltd., Kawasaki,
Japan) was inserted between tooling components to make the ejection process after sintering simpler.
All the battery layers were pressed down in the die and the entire tooling setup was pre-compacted at
room temperature under 3 kN.
The SPS runs were conducted using Dr. Sinter SPSS-515 furnace (Fuji Electronic Industrial Co., Ltd.,
Kawasaki, Japan) with a pulse duration of 3.3 ms and on/off pulse intervals of 12:2. The maximum
processing temperature during the SPS process ranged from 650 to 850 °C with the holding time spanned
from 5 to 30 min. The heating rate was set to 100 °C/min. An axial pressure of 45–60 MPa was applied
at the start of heating and held consistently until the end of each experiment. During each SPS process,
a K-type thermal couple was used to monitor the temperature evolution at the graphite die. All the real
time processing parameters were automatically logged by the device. Every individual experiment was
repeated at least twice to ensure the reproducibility of the results. To test the electrical properties of the
obtained batteries, a galvanostatic charge–discharge tester (PGSTAT204, Metrohm Autolab B.V.,
Utrecht, The Netherlands) was first used to evaluate the electrical capacity. In these tests, the cells were
charged and discharged with a constant rate of 20 µA/cm2. For both three-layer and five-layer batteries,
the charge time was 60 min, and the tests were conducted until the batteries were fully discharged, as
shown by a drop-off in cell potential. The energy and the power density of the cells were compared by
examining the achieved potential level for the total charge-discharge cycle and the specific capacities at
given period of time for each battery. The electrical conductivities of the batteries were evaluated by a
digital multimeter (HDM4100, Commercial Electric Inc., Taiwan) after the batteries have been
discharged. The resistivity, r, and the conductivity, s, were calculated using Equation (1), where l is the
length of the battery in cm, A is the cross-sectional area of the battery in cm2, and R is the measured
53
resistance in ohms. In order to properly conduct these electrical tests, two thin tin plates were fabricated
to clamp onto both ends of the batteries serving as current collectors.

𝐴 𝑙
1) 𝜌 = 𝑅 ⋅ 𝑎𝑛𝑑 𝜎 =
𝑙 𝑅𝐴

After the electrical tests, the obtained batteries were cut into halves on a precision diamond saw to have
their cross sections exposed. The samples were then ground and polished using SiC grinding papers with
increasing grit size on an automatic polishing machine. Once the samples were well polished, they were
examined using SEM for microstructure observation.

3.4.2.2 Results and Discussion

The completeness of the batteries consolidation under various SPS conditions is indicated in Table 3-8.
One can see that the batteries processed at 825 °C under an 80 MPa pressure with a 30 min holding time
delivered the highest densification level and the best joining interface between electrodes and electrolyte.
The others either had no fully consolidated electrodes or contained nearly melted components, although
the electrolyte was always consolidated. Therefore, the above-mentioned processing parameters were
considered to be the most efficient under the studied SPS processing regimes and the comparison
between the regular three-layer and the functionally graded five-layer batteries was mainly conducted
for the specimens processed by applying these conditions.

Experiment stopped when melting occurred at the beginning of holding time.

Table 10

Table 3-8: Completeness of batteries consolidation under different spark plasma sintering
(SPS) conditions.

The galvanostatic charge–discharge tests determined whether or not the implementation of the
functionally graded electrodes improved the electrochemical performance of the batteries. Figure 3-18
shows the results of these tests. The average charge potential of the five-layer battery is higher than that
of the three-layer one (Figure 3-18a), resulting in an increase in the discharge capacity and the average
discharge potential in the five-layer battery (Figure 3-18b). This observation indicates that both the
energy density and power density of the cell was improved by implementing the functionally graded
electrodes. However, it is important to note that both of the batteries produced in this study show
significantly lower specific capacities than the battery constructed in Reference. There are a number of
possible reasons for this:

(i) the materials used for battery components;

(ii) possible contamination of battery materials during preparation (ball milling, baking, etc.),
reducing their abilities to conduct lithium ions;

(iii) different battery dimensions (i.e., electrode and electrolyte thicknesses).

54
The main conclusions to draw from this test are:

(i) the implementation of functionally graded electrodes improves both the energy and
power densities of ASSLibs;

(ii) these fabrication techniques used in the present study can be generally transferred to
the production of other types of ASSLibs with achieving high capacities.

Figure 36 Fig 3-18: Galvanostatic test results: (a) charge curves; (b) discharge curves

Table 3-9 shows the resistivity and conductivities of both three- and five-layer batteries. The
conductivities of their constituent powders are also included as a reference (note that the conductivity
of acetylene black was provided in the material manufacturer data sheet). As one can see, the resistivity
of the battery with functionally graded electrodes is lower than that of the battery without. This is most
likely due to the reduced delamination at the anode–electrolyte interface that comes from the
introduction of the functionally graded electrodes. It is worth noting that, although the LATP powder
owns the highest conductivity, the conductivities of the fabricated batteries are limited by those of their
constituent materials. In addition, the existence of interfacial imperfections between electrodes and
electrolyte also appears to be a factor lowering the conductivity. As a result, the conductivities of both
batteries are lower compared to the raw materials, but they are still within the expected range based on
the literature. Since the resistances of the ASSLibs were measured with a digital multimeter, the
diffusion resistance was not taken into account. To have more accurate measurements, it is better to
apply AC impedance method to separate the intrinsic resistances.
Table 11

Table 3-9: Resistivity and conductivities of batteries, conductivities of the constituent materials that make
up the battery.

55
Figure 3-19 shows the micrographs of the electrode–electrolyte interfaces in the three-layer battery. It
shows that the cathode–electrolyte interface has no evidence of delamination, while the anode electrolyte
interface does. The delamination was not complete, so the battery was able to remain intact, but as
mentioned previously, the presence of delamination at the electrode–electrolyte interface is a major
contributor to interfacial resistance. The manner in which the functionally graded electrodes were
constructed was determined based on these images. It was clear that the original cathode composition
and electrolyte consolidated well (see Figure 3-19c), meaning that this composition could be used as the
intermediate cathode layer and a new composition with a higher concentration of LCP could be used as
the primary cathode. However, the cracking seen at the anode–electrolyte interface is indicative of
thermal mismatch (see Figure 3-19c). Therefore, a new anode composite with a higher concentration of
LATP needed to be implemented as an intermediate layer between the electrolyte and the original
composite anode.

Figure 37
Fig 3.19: SEM images of the interfaces in the three-layer battery: (a) electrolyte–cathode;
(b) anode–electrolyte; (c) anode–electrolyte at higher magnification.

Figure 3-20 shows the SEM images of the various interfaces in the functionally graded five-layer battery.
One can see that the interfaces on the cathode side of the battery still exhibit no signs of delamination
or cracking (see Figure 3-20 a, b). Moreover, the introduction of the intermediate anode layer eliminated
the cracking that occurred at the anode side as in the three-layer battery (see Figure 3-20 c, e). These
images indicate that introducing functionally graded electrodes can improve the interface quality of
ASSLibs and the power density accordingly. The comparison between Figures 3-19 and 3-20 also shows
that the implementation of the functionally graded electrodes enhances the structural integrity of the
fabricated ASSLib, so the five-layer battery retains better performance.
56
 Figure 38

Fig 3-20: SEM images of the interfaces in the five-layer battery: (a) cathode–intermediate cathode;
(b) intermediate cathode–electrolyte; (c) electrolyte–intermediate anode; (d) electrolyte–intermediate
anode at higher magnification; (e) intermediate anode–anode.

The ability of SPS to fabricate functionally graded components of all-solid-state Lithium-ion batteries
has been investigated in the present study. Two types of ASSLibs have been successfully produced and
tested. The first one employed the traditional design with regular electrodes. The second employed a
novel design implementing functionally graded electrodes. The second design allowed the battery to
maintain high-quality interfaces between each component and to contain a more active electrode
material. The electrical properties and the microstructures of the SPS-processed batteries were evaluated
comparatively. It was shown that the functionally graded electrodes were able to eliminate the
delamination at the component interfaces and to result in higher energy and power densities. Both
theoretical and experimental advantages of this novel battery design have been validated. The obtained
results are of importance for tailoring and optimizing ASSLibs via SPS technique.

57
 4 Problems which born from the fast charge
Fast charging for Li-ion battery is crucial for our everyday use of electronic devices and transportation.
However, Li-ion batteries still have some serious drawbacks especially for fast charging protocols. Many
of the problems can be related for one part to surface phenomena occurring on the negative and positive
electrodes and for another part to structural modifications (expansion-contraction, crystal disorder), in
simpler words, internal degradations of active materials. Moreover, safety protocol is also the main
concern during the manipulation of this type of battery especially during high temperature elevation
because of its high specific energies. In regards of fast charging process, the high temperature elevation
is something that is unavoidable. Thus, reliable indicators and reliable fast-charging protocols have to
be developed and improved to properly charge the battery until a certain state of charge and monitor the
state of health of the battery.
Something about standard charging method, Generally, the charging process of a Li-ion battery is
divided into 2 charging stages; these are the constant current stage (CC) and constant voltage stage (CV).
During the CC stage, the battery is charged at a chosen constant current (i.e. charging rate) until a certain
upper voltage limit 𝑈𝑓 is reached before switching to CV stage. The upper voltage limit 𝑈𝑓 is
predetermined by the manufacturer; it is designed to ensure longer battery life-span by avoiding side
reactions. During the CV stage, the battery is normally charged more slowly with a degrading current to
maintain the battery at a constant voltage until the current limit called 𝐼 cut-off, is attained. Even though
the CV stage is slow, it allows the relaxation of the species concentrations inside the electrolyte and
electrode materials. The duration of the total charging period depends on the charging rate applied during
the CC stage.
In the context of EV applications, Li-ion batteries are faced with reliability and durability issues.
Nevertheless, it is a mandatory requirement in EV applications to minimize the battery charging time;
so, a fast-charging method must be developed properly. If fast-charging is applied, theoretically the
battery can be recharged in a shorter period, which is not the case for current EVs.

What’s the difference between conventional, opportunity, and fast charging?

Conventional Charging:

• Batteries are charged at rates of 16-18 A / 100 Ahrs

• Takes about 8-10 hours to fully recharge the battery
• A battery is charged using the 8-8-8 rule: the battery charges over an 8-10 hour period,
rests and cools down for another 8 hours, and is used (discharged) over an 8 hour shift.
• This makes conventional charging ideal for one shift operations. For multi-shift
operations (2 or 3 shifts), more than one battery per truck is needed. This means changing
batteries every 8 or so hours, requiring labor, time and risk of injury.
• Conventional chargers always charge the battery to a 100% state of charge (SOC) on a
daily basis, a process that involves considerable gassing to bring the battery to name
plate specific gravity. This entails placing chargers in centralized charging areas to
maintain hydrogen concentrations well below OSHA limits.

Opportunity Charging:

• Batteries are charged at rates of 25 A / 100 Ahrs at every possible opportunity (i.e. lunch
breaks, between shifts)
• Opportunity charging is a good choice for extended shift operations where battery
changing can be eliminated.
• In addition, opportunity charging extends the run time of aging batteries and recoups the
58
 lost capacity that comes with age. Note: the battery’s end of life criteria is when the
battery capacity reaches 80% of its new value.
• Due to the frequent charging and in order to limit battery gas generation, opportunity
chargers are normally set to charge a battery up to 80%-85% SOC throughout the day
and back to 100% only once a day (i.e. during night hours).
Fast Charging

• Batteries are charged at rates of 40+ A / 100 Ahrs at every possible opportunity. This
includes breaks within and in-between shifts, as well as lunch breaks.
• With brief and frequent charge intervals, a single battery per truck can be used thus
eliminating the need for additional batteries as well as eliminating all battery changing
between shifts.
• Batteries are charged to 80%-85% SOC on a daily basis thus eliminating any
unnecessary gassing. The battery is required to be finish charged and equalized (100%
SOC) at least once a week, which is normally done on weekends.

Although fast charging has become a mainstream charging technology, there are still negative
impressions about this technology. One of the most common misconceptions is that “fast charging is not
good for the battery”. Some claim that the higher temperature the battery experiences due to the high
rate of charge leads to shorter battery life. In fact, many go further to conclude that the expected battery
life in fast charging is three years or less as compared to five years in standard charging applications. At
a first look, these comments are sound and reasonable given that some of these claims used to be true.
Due to advancing technology, however, these claims are no longer accurate. A high-performance
charging system is required to recharge any battery quickly and reliably. The following system
parameters should be considered in order to ensure a reliable, cost-effective solution. It cannot be
stressed enough that over charging is the Achilles' heel of Li-Ion cells. Accurate charge termination
methods are essential for a safe, reliable, charging system.

59
4.1 Li-ion battery Fast charging fundamentals
Nowadays, the United States Advanced Battery Consortium (USABC) is the only organization that
proposes a fast charging test oriented towards EV applications. The USABC goal of fast charging (for
batteries capable of such usage) is defined as when a battery is able to return 40% of the SOC within 15
min. This is approximately a charging rate of ~2C. However, the USABC does not include specifications
on fast charge aging, safety, or protocol development, to name a few. Still, a good fast charging process
shall be quick and simple, adding the minimal detrimental effects to the battery. Here we present the
fundamentals of fast charging.
Li-ion battery architecture design for fast-charging:

The LIB architecture design plays a significant role to achieve fast charging. The key factor to achieve
high power performance in LIBs is to decrease the polarization resistances, so energy can rapidly be
extracted. From the different electrode materials and battery configurations of choice, high power (HP)
batteries accommodate best for fast charging. The choice of the HP battery considers the design of the
cell from an engineering and basic science level. Fundamental engineering considerations include the
design of cylindrical cells with large electrode area and reduced thickness of the electrodes, an even tab
distribution, and sufficient amount and area of active material on the negative electrode to avoid Li
plating. From a basic science design perspective, high ionic conductivity and reduced charge transfer
potentials can optimize the performance of HP cells. Additional factors must be considered, namely the
use of materials optimized for high rate operation, microstructural cell design, the use of nanomaterials
in the electrodes, and/or the use of conductive additives. Active material chemistries with high power
properties such as fast kinetics and low resistivity are ideal for its use in HP cell designs. In some cases,
even active materials (such as LFP) with low electronic conductivity can take advantage of the use of
nanomaterial and microstructure techniques to remarkably enhance its conductive properties.
Nowadays, high power LIB technologies that permit fast charging are available on the market. For
example, nanophosphates with coating layers show good overall performance in terms of intrinsic safety,
high cycle-life time, high-power capability, flat voltage profile, reliability and low toxicity. The main
drawback is the relatively low specific energy. Similarly, high power anode-based titanium batteries
(LTO) are commercially available and show excellent charging capabilities (up to 6C) and long cycle–
lifetime (over 5,000 cycles). Still, the main drawbacks of LTO are low specific energy and high cost,
which are two major impediments for its applicability on EVs. In the research field, efforts in
nanostructured materials are showing promising results on high power, laboratory-scaled LIBs.

4.1.2 Li-ion battery fast charging techniques

To achieve effective fast charging, the selected battery architecture has to be complemented with the use
of an optimum charging protocol. The charging protocol should aim to shorten the charging time,
improve charging efficiency, minimize any performance attenuation and sustain a safe operation of the
tested battery. This section provides an overview of the most commonly used charging techniques in
LIBs.
Constant current-constant voltage (CC-CV): The most common process to charge LIBs is through a
consecutive two-step constant current constant voltage process (i.e. CC–CV), as seen in Fig.4-1. The
current rate of the CC stage and the predefined cut-off voltage strongly depend on the LIB chemistry;
these parameters are specified by the battery manufacturer to operate the battery under standard charging
conditions. Similarly, most LIB manufacturers recommend a current below C/20 in the CV stage to
reach full charge. Since the CC–CV method is easy to implement, performs efficient charges and is
reliable at mid to low charging rates, it has often been denoted as the standard charging method for LIB
batteries.

60
 Figure 39
Fig 4-1: Charging CC–CV protocol at 0.5C (current-blue, cell voltage-red and state of charge in green)

Despite its advantages, one major drawback of the CC–CV method is that it takes long time to fully
charge the battery. Charging times of over 2 hours are common using the CC–CV method. The CV stage
prolongs the charging time, as current decays, but is necessary to prevent overcharging, achieve full
charge and reduce temperatures. To reduce the charging time, high charging rates are required. However,
high currents decrease the charging efficiency due to Joule heating, and may cause Li deposition at the
end of the CC stage. Additionally, increasing the charging rate above a certain level does not reduce the
charging time. This is because the increase of polarization reduces the charged capacity during the CC
stage, which is the quickest charging stage.

Constant voltage (CV): The constant voltage (CV) charging method was developed as the simplest
strategy to reduce the charging time of the CC–CV standard method. The CV method starts charging the
battery directly at CV, to terminate the charging process when the current drops below a certain level.
Regardless of its simplicity, the main disadvantage is that demands very high initial charging currents.
Moreover, charging continuously at the cut off voltage is highly detrimental to the battery due to
electrolyte oxidation. Therefore, CV method rapidly decreases the life of the battery. Limiting the
charging current and charging at the pre-determined cut-off voltage may help to reduce both the charging
time and aging effects. Still, this charging protocol is not recommended to be carried out on a regular
basis.

Multistage charging method (MCM): The multistage charging method (MCM) proposes different
charging stages, with stepwise descending and/or ascending currents, taking into account characteristics
of the selected battery. Ideally, parameters such as the internal resistance (IR) evolution, temperature
evolution and current rate dependencies shall be considered to design an optimal MCM. Similarly,
currents over the maximum rates or voltages out of the stablished limits cannot be exceeded. Situations
which lead to premature capacity fade must be avoided, mainly large currents at high SOCs which may
lead to Li plating. To avoid electrolyte oxidation, long time CV stages at high SOCs shall be reduced.
Several MCM strategies have been proposed. Recently, a new multistage charging strategy was
proposed by Vo et al. The battery technology selected was lithium manganese oxides (LMO) that permits
maximum charging rates of 2C. The proposed strategy is based on a four stage constant current (FSCC)
pattern, where each charging stage is set to 25% SOC (see Fig. 4-2). A mathematical approach was
61
developed to select the optimal current rates and to estimate the SOC of the cell to set the boundaries of
the steps. The results shows that the FSCC has better performance than to standard CCCV, with a
reduction of charging time of ~20%, and a slightly higher energy efficiency (1.5%).

Figure 40
Fig 4-2: Four stage constant current (FSCC) charging methods

To sum up, the MCM has important advantages to achieve both healthy and quick recharges, when is
properly designed. Maximum charging rates and IR evolution with the SOC are key parameters in the
design. Similarly, the current rate and length of the charging steps has to be determined through either
experimental approaches or mathematical modeling.
Varying current method (VCM): The varying current method (VCM) consists in continuously
modifying the charging current as the battery is being charged, based on several assumptions to optimize
the charging process, including the lithium concentration levels in the electrolyte and impedance
evolution. Proper design is required to avoid risk of overvoltage and/or the long charging periods within
the cut-off voltage value, which lead to premature capacity fade and impedance increase. Recently, Guo
et al. proposed a strategy based on impedance evolution with SOC, coupled with a current decaying
profile to accommodate the polarization variations with SOC (see Fig. 4-3). The charging parameters
were derived from equivalent circuit modelling and algorithm optimization, showing better charging
efficiency and cycle life than standard charging. In this type of methods, the main problem is that
complex charging profiles are difficult to implement in practical chargers. Advanced techniques can be
used to improve charging capabilities. Battery chargers may include on-line IR and SOC calculations to
evaluate the SOH, and automatically modify the charging profiles as the cell ages. However, this
adaptive method can be achieved at the expenses of adding complexity to the LIB system and increasing
previous research time and experimental resources.

62
Figure 41 Fig 4-3: Charging current as a function of time using modified varying current method

Pulse charging: The pulse charging method consists in using short rest periods in the charging process,
which can be accompanied by short discharge pulses. This method is intended to eliminate concentration
polarization at the electrode/electrolyte interface, to reduce the risk of Li deposition while fast charging.
Due to its potential advantages, several experiments have been carried out. It was found that the pulse
charging method only induces better results in some cases, depending on the battery technology and the
profile of charging pulse. Hence, although this method can reduce charging time and energy losses,
improvements can be only achieved by trial-and-error or by empirical methodologies, which may not
always provide the expected results and can be time consuming and complex.

63
4.2 Temperature
The temperature range over which a Li-Ion battery should be charged is 0°C to 45°C, typically. Charging
the battery at temperatures outside of this range may cause the battery to become hot. During a charge
cycle, the pressure inside the battery increases causing the battery to swell. Temperature and pressure
are directly related. As the temperature rises, the pressure can become excessive. This can lead to a
mechanical breakdown inside the battery or venting. Charging the battery outside of this temperature
range may also harm the performance of the battery or reduce the battery’s life expectance. Generally,
thermistors are included in Lithium-Ion battery packs in order to accurately measure the battery
temperature. The charger measures the resistance value of the thermistor between the thermistor terminal
and the negative terminal. Charging is inhibited when the resistance, and therefore the temperature, is
outside the specified operating range.
Table 12

Table 4-1: Permissible temperature limits for various batteries. Batteries can be discharged over a large temperature range,
but the charge temperature is limited. For best results, charge between 10°C and 30°C (50°F and 86°F). Lower the charge
current when cold.

Lithium-ion batteries have very good coulombic cycling efficiencies, as high as 99.5%. The small drop
in efficiency is often traced back to a mismatch of properties among the different components (e.g.,
differences in the rate of transport of electrons versus the ions) and manifests itself in the form of heat.
Heat generated within the battery is usually classified into reversible entropic heats and irreversible
losses due to low conversion rates for the chemical reactions, or poor transport properties resulting in
some polarization losses. Some of these losses are minimized by suitable design changes to the cells.
One example is matching the porosity of the electrodes to that of the separator membrane. Mitigation of
other types of losses may involve changes to the chemistry of the electrode or the composition of the
electrolyte. Tracing back the efficiency losses at the cell level to the relevant contribution from each
source will enable battery manufacturers to evaluate tradeoffs between the efficiency improvements and
cost of redesigning the cells.

64
Heat Generation from Joule Heating: Joule heating losses within a cell arise primarily from poor
electronic conductivities within the solid phase of the cell, low electrolyte conductivities, contact
resistances at the junctions between cell components, or formation of a resistive film on the electrode
surface from electrolyte decomposition reactions. Ohmic losses are a function of the C-rate, size, and
age of the cells. Ohmic losses can constitute up to 50% of the heat budget.

Heat Generation from Electrode Reactions: Electrochemical reactions taking place within the cells
involve transfer of charge at the interface between the electrodes and the electrolyte when the circuit is
closed. The mobilities of the bulkier ions are about seven orders of magnitude smaller than those of the
electrons, and the difference in the electrochemical potentials for lithium ions within the host lattice at
the electrode and within the electrolyte governs the rate of charge transfer. Transfer of charge across the
energy barrier at the interface results in loss of a part of the kinetic energy associated with these reactions.
Heat losses due to the charge transfer process are measured as the difference in free energies across the
two sides of the interface. Whereas sluggish kinetics have been known to limit efficiencies in some
chemistries (e.g., in some phosphate-based cathodes), activation barriers usually contribute to 30%–40%
of the heat losses under practical operating cases.

Entropic Heat Generation: Insertion and de-insertion of lithium ions in and out of the electrodes result
in entropic changes within the electrodes. Ideally, such changes are reversible under very slow rates of
charge and discharge; however, from a practical perspective, there is some energy loss associated with
these phenomena. Usually, the entropic losses in an electrode take place at well-defined voltage
windows. Such entropic losses constitute the reversible portion of heat generation. Whereas these
changes can be as low as 5%–10% of the total heat budget, changes to the entropy of the host lattice are
often accompanied by additional limitations such as changes to mechanical properties or phase changes,
which complicate the analysis of the impact of such losses on the durability of the cell.

Lithium-ion battery life also varies greatly with cell temperature, maximum and minimum SOC, all of
which are impacted by XFC (extreme fast charging). Charging C-rate is also a factor in aging; however,
in test data that exists to date, it is difficult to decouple the impact of charging C-rate from coupled
factors of elevated cell temperature and accelerated frequency of charge/discharge cycles per day. It
would be possible to design experiments that decouple each of these factors. Different cell chemistries
and power-to-energy ratio designs would respond differently to these factors.

65
4.3 Lithium deposition
Lithium deposition forms if the charge rate exceeds the ability by which lithium can be intercalated into
the negative graphite electrode of Li-ion. A film of metallic lithium forms on the negative electrode that
spreads uniformly over the host material or gravitates to one region in planar, mossy or dendritic format.
The dendritic form is of concern because it may increase self-discharge that in extreme case can create
a short and lead to venting with flame.
Environmental conditions affect the deposition of lithium as follows:

1. Lithium deposit grows when Li-ion is ultra-fast charged at low temperature

2. Deposition develops if Li-ion is ultra-fast charged beyond a given state-of-charge level

3. The buildup is also said to increase as Li-ion cells age due to raised internal resistance.

Consumers demand fast charging at low temperature, and this is especially critical with the electric
vehicle. Solutions include special electrolyte additives and solvents, optimal negative to positive
electrode ratios, and special cell design. Lithium plating. Lithium ions (Li+) are transported from the
positive to the negative electrode during charge. These ions then reach the interface between the
electrolyte and the negative electrode. Under normal operating conditions, lithium (Li+ plus an electron
from the external circuit) intercalates, as in the case of graphite, into the negative electrode material in
stages, filling the space between the graphite layers (galleries) in a step-wise fashion. However,
intercalation is a diffusion-limited process, only a certain amount of lithium can enter the galleries per
unit time at a given temperature. As the galleries fill, the rate at which more lithium can enter decreases.
If lithium transport to the surface of the negative electrode is faster than it can intercalate, lithium metal
can plate on the surface of the negative electrode. Lithium plating can occur when the local potential at
the negative electrode is below 0 V (vs. Li/Li+). This can happen when the net cell voltage is about 4 V
or greater in a capacity balanced cell system (negative-to-positive ratio near 1.1). Lithium plating was
reported to increase with increasing current density and with decreasing temperatures. Plating can occur
at charge rates as low as about C/6 at ~20°C. Additionally, there is a report that defects can cause lithium
plating. Defects, “such as pore closure [in the separator], create local, high currents and overpotentials.
If the overpotential exceeds the equilibrium potential in the negative electrode, plating can occur. As
lithium deposits on the surface of the negative electrode, its quantity tends to depend on capacity loading
in the electrode, as shown in Fig. 4-5. In the best case, the deposited lithium will be removed during the
following discharge subcycle. However, in the work of Gallagher et al, even slow discharges before cell
disassembly failed to remove the lithium deposits to any noticeable extent. This finding suggests that
the lithium deposits are not electronically connected to the graphite electrode. Under other
circumstances, it can affect the performance and life of the cell.

66
Figure 42

Fig 4-5: Evidence of increasing lithium deposition (metallic gray) on graphite electrodes as a
function of capacity loading.

67
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