Lithium‑Ion Batteries: History and Trends

Hello, today's lecture will be an overview of the lithium-ion batteries in courses such as the battery engineering,

the electrochemistry. So we have explored not only the battery themselves, but also detailed the electrochemical processes. However, in this chapter, we will focus more specifically on lithium-ion batteries, briefly covering their history, characteristics, and the developed trends. First of all, as many of you already know that the demand for the lithium-ion batteries has

been skyrocketing every year. Originally, lithium-ion batteries were mainly using the small size applications like a smartphone or smartwatch like this one. But their application have expanded into automobiles, air sprays, the like as aircraft flight

chips and many other fields. As a result, not only has demand increased, but the requirement battery format and the specifications have also diversified. In particular, by around 2030, the demand for the battery in the transportation is expected to become extremely large.

Looking at this sector, we can see that the China-based companies such as CATL, BYD still supply a significant share of the battery. However, since the adoption of electric vehicles in Korea is steadily increased, I believe the Korean battery industry like Samsung, LG, SK, and Samsung.

will soon show a stronger position as well. Now let's take a look at the history of battery. Although the exact year is uncertain more than 1,000 or 2,000 years ago, we can find these kinds of batteries. It's called the Baghdad batteries, which was a Terracut jar based on the battery. These kinds of Terracut jar containing copper cylinder,

separated from the iron rolled by the conductive stuffer and filled with the electrolyte. Like this kind of design. Right in the 18th, Alexandru the Volta created a famous battery. The name is Voltaic Pile. The Voltaic cell was made using the zinc and the copper.

immersed in the salt water. Following that we see the development of the tanyan cell and lead-acid cell is one of the first recharge of battery and then zinc carbon cell. After that the development of the modern the lithium-ion battery began in the 1970s by the professor Stanley Wittgenheim which

The Williams battery, the first lithium intercoloration battery, was developed in Aksun in 1972 using titanium disulfide. Like this one. The Dachyon, good enough. Good enough. And the research fellow, Mizushima, began researching the lithium intercoloration battery. By 1980, they had improved the Wittinger's design.

replacing titanium lysofite with the lithium cobalt oxide.

The new chemistry boosts the battery's voltage by another two-third to the four-volt. And then the rate 1980s by Dr. Akira Yoshino. Yoshino's battery developed as the Asahi chemical combined the John Goodenough cathode with the pattern cork anode like this kind of the system. And then Sony and Asahi group have the credit for the making lithium battery.

household name the world first commercialized lithium-ion battery in the 1991. These batteries were first used in the Sony camcorder followed by the mobile phones. The Sony cell consists of the lithium cobalt oxide is the same as a good enough cell and in In case of the anode, it's carbon, the electrolyte,

LiPF6-Litium-salt in the diethylene carbonate-forflane carbonate blend dissolvent. Interestingly, these kinds of configuration is still in use today. In this way, three scientists who complete the foundation of the modern lithium battery, Professor Sany Wittgenheim, Professor John Guttenhoff and Dr. Kira Yoshinov were awarded the Nobel Prize in chemistry in 2019.

the hydrogen-1 battery which first had gone down in modern form in the 1970s began the nobel raining filter after 50 years one also become ever more integrated into our daily lives so so there are many some good some talks so i would also like to share a remark by the professor Saifu Islam at University of Oxford most people probably saw the nobel files used on the device powered by the

lithium battery. In my view, this award is long-overviewed. Interestingly, the professor Saif Islam also holds the Guinness World Record for creating the lemon battery. Maybe you can find like a Guinness record lemon battery by Saif Islam on the internet website. Generally, in order to be awarded the Nobel Prize, the research must not only demonstrate the groundbreaking scientific innovation but also prove its industry of the capability and its impact on the humanity.

Therefore, to carry out the meaningful research in the future, we need to consider not only scientific insight but also how our work can truly improve people's lives, like industry, so our lives. So, well, shall we take a closer look at the battery technologies? If

particular when we talk about battery one of the most important question is how long they can last in this page the concept of the energy density is very important in case of the energy density there are two types one is gravimetric energy density second or metric energy density

A battery with a high gravimetric battery, it means this battery is lightweight but can last a long time. While a battery with a high volumetric density, at the time this battery is compact, yet still provides long uses. If you look at this kind of mapping, of this property, the idea by tree.

The ideal battery would be one that achieves both high gravity and the volumetric energy density. Currently the current currently the rich amount battery we use today already reaches these levels like a lithium ion, graphite and the transition metal oxide like as nickel mangan cobalt or lithium cobalt oxide.

or LIPF or LFP. However, as you look at the next generation batteries such as the lithium metals and the lithium sulfur and the lithium L battery, we see the potential for even more ideal configurations like this way. So let's look at the different the representative battery cell types. One is the primary cell and

Another is the secondary cell. So secondary cell already we know there is the recharge of a battery. First the primary battery cells are the battery cells that can be used only once. So once the chemical reaction inside are finished, they cannot be recharged. A common example is this possible alkaline battery. We often use in the remote control or some word clouds.

Primary cells are convenient, inexpensive, and have long shelf life, but they are not environmentally friendly because they must be discarded after use. Like this one. On the other hand, secondary cells are rechargeable.

battery after they are discharged the chemical reaction inside can be reversed by applying an extra extra the external current so they can be used many times the ligament battery in your the smartphone and the nickel metal hybrid hydride the battery in the hybrid car or even the read-add-seed.

In the tradition of the movies are all the good example of the secondary batteries. So let's look at the lithium-ion batteries that we commonly use. The primary components of the lithium-ion batteries are the anode record in Korean, and cathode, electrolyte, and cell.

separate the polymer. Together these materials are often referred to as the electrode winding or stack up. During the operation, lithium ion intercalate and the intercalate between the anode and cathode. Intercalation means the insertion and extraction of the lithium ion between the rayed structure.

of the electric material. The ions travel through the separator which is ionically conductive but electrically insulating. This ensures ion transport while preventing internal short circuit that is the direct contact between the electrodes. We deny electron flow externally through the circuit providing usable electrical and

But maybe we can cover the new cathode or new anode system at a time the system is not intercalate, it's a conversion type. The material also we can use it. To properly evaluate and understand the battery, we need to be familiar with several key performance.

the matrix. The first of these is the battery capacity called 용량 in Korean. Battery capacity represents the total amount of electrical energy. A battery can store and it is typically measured in the ampere hour or watt hour. In simple term, capacity indicates the maximum amount of the energy that can be extracted from the battery under

certain specific pipe conditions. When the express the ampere hour, that is a unicell that tells us how much current battery can provide for one hour. Mathematically, capacity is to calculate as the product of the current ampere unit and time

The time represents the duration for which the battery delivers the current. For example, a battery with a capacity of 2Ah can supply a current of 2Ah for 1 hour, after which it would need to be recharged. Let's try an example. The problem one, if a battery allows current.

7 ampere to go for the eight hours calculate in the storage capacity in ampere hour already we know that capacity is the current and the time so that means 7 multiplied 8 56 ampere hour this is very simple and then problem 2 a battery has a storage capacity

70 ampere hour and give a constant current 4 ampere how long will the battery last already we know that according to these kinds of equations 4 ampere and the time is divided by 4

70.5 hour is very easy. Now let's move on the concept of the energy density. Korean word energy. Mildo. So which is another key factor in the evaluating battery. Energy density tells us the how much energy A battery can store relative to its weight.

The volume is critical of the parameter because it directly impacts the efficiency and performance. Practically, the energy storage system causes many different kinds of deflacation. The higher energy density, the more compact, long-lasting and environment-friendly the battery can be. The next generation, the system.

Let's look at the energy density. Why is the energy density important? First, efficiency. A higher energy density means more energy can be stored in the smaller space or the lighter weight. This is crucial for portable devices and the solar system since you want them to be efficient and easy to carry. And then the second thing, range and endurance,

Long range is very important for transportation like electric vehicles or the boat or the flight. Energy density directly determines how far or how long the vehicle can run before recharging. For example, electric vehicles depending heavily on the high energy density to increase the driving range. sometimes we call the mileage.

The third space constraint. In many situations, space is limited. Think of a camper van or a tiny home. In such a case, a high energy battery allows for longer use without taking up more rooms. This is one reason a little battery They packed more energy into smaller size compared to the old technology.

Thus, the cost effect means it is just money. The energy density also influences the cost. Lithium-ion batteries today have energy density about 200-260 Watt-alpha kg, while the lead-oxid batteries are only 50 or 70 Watt-alpha kg. That means the lithium-ion battery are about 305 Watt-alpha kg.

times more energy dense. To achieve the same capacity with the liquid-oxid battery, you would need several times more batteries which increase the cost and space requirement. Next, environmental impact. Finally, high energy density has to reduce environmental impact since few materials are needed to store the same amount of energy like this one. Just the maximizing energy density.

Productions like a disposal can be more resource efficient or sustainable. So when you look at the next generation and the modern energy strategy, the maximizing energy density is the key. Some factors that involve performance, but also for cost reduction and environmental benefits.

The third key parameter is the power we call the trigger. Battery power refers to the rate at which a battery delivers energy to a device. It is the amount the electrical energy provides for a unit of time. And it usually measures watts. The watt is the current and the voltage. So in terms of being the higher...

that means the faster the battery can perform well.

So let's look at a simple example. A mobile phone charger might operate at 5V and 2A. That means 10W power. A power tool like a drill might be 20V 5A is 100W power. As you can see, devices with a higher power requirement need batteries that can deliver both higher voltage and higher performance.

Now, coming back to the energy density, there is also important concept called the power density. Energy density already know that tell us how much total energy the battery can store, store relative to its weight or the volume. In contrast, the power density describes how quickly that stored energy

delivery to the device. To make this clear, let's compare the two. Energy density is the size of car fuel tank. A bigger tank means the car can drive for longer distance with refueling. Power density, the size of the car

engine the more powerful engine can deliver the energy much faster allowing the car to accelerate quickly in battery a higher the energy density means that the device can run for a long time when a single charge while a high power density means the device can release and is very rapidly when needed

For example, a smartphone battery is designed for the high energy density. So it can last all day even though it doesn't need to traverse the power. A power pool or a tool or a hybrid vehicle battery is designed with a higher power density. So it can deliver quickly.

first of the energy for drilling or accelerations even if it doesn't last as long as the EV battery. So ultimately the ideal battery is the balance, both higher energy density and power density, but in reality there is usually a trade-off and the design depends on the intended applications. Next let's talk about the psych life.

So we call the sumyeong.

So cycle life refers to the number of charge and discharge cycles a battery can undergo before its capacity discards to certain predefined ladders, often around 80% of its original capacity. Its simple term is how many times you can recharge and use your battery before its starting using the significant efficiency. Now you might notice that even from the very first use, when you discharge and recharge the battery, it may not return the 100%.

This does not mean the battery has reached the end of its life. Instead, manufacturer defines the acceptable performance range and capacity reduction, as we heard before officially, declaring the cycle life of the battery. There is a single universal standard for this, but general rule terms is the cycle life battery is the number of the cycle

can complete before its maximum capacity below the 80% of the original value. We can express this with a simple formula equation for the capacity retention. The capacity retention usually we have a unit percent, the capacity after n cycle by the capacity at the initial cycle and then multiply 100%.

so if after 500 cycles the battery that can only hold the 80 percent of the energy if they did at the beginning we say that is the cycle life is the 500 the cycles

Now let's consider another important concept in the understand battery capacity, the depth of discharge, or so-called DOD. The depth of discharge refers to the percentage of the battery total capacity that has been used relative to its full capacity. like this one. For example,

If you use half of the battery's charge, the corresponding up to 50% BOD, generally the deeper discharge, the more stress it applies on the battery, which can shorten its cycle life. So, this naturally brings us to the question, how can we extend the lifetime of our batteries? There are several key practices on things prefer charging habits.

One of the most effective ways to extend the battery cycle light is to maintain good charging behavior. Avoid the overcharging device and unplug down once they reach full charge. But on these days, some smartphone has special functions so the

which can inhibit the overcharging. So don't worry about that. And then second thing, ideal overation temperature. Batteries work best within a specific temperature range. Extreme heat or extreme cold can negatively impact the cyclite. So keeping device or the vehicle within the recommended temperature window as the pressure battery has.

Third, use quality charger. I think everyone knows that. And the full storage condition is quite similar to the concept with ideal operation temperature. Third, partial discharges. The rigid-mine battery in particular perform the battery with the partial discharge. In other words, you don't need a fully drained battery before recharging. In fact, the frequent full recharge actually shouldn't cycle life.

So that means the managing of the battery, the cycling, the performance. Considering the DOD, the practical, the proper charging, controlling temperature. So using this one, you can significantly extend the useful life of modern lithium-ion battery. Here is a typical graph that you might see in the battery research paper like this one. Let's try calculating the capacity retention.

the this cell if you look at the green curve the initial the capacity is 250 milli ampere hour after 100 cycle it looks like it goes to drop to the 150 milli ampere hour so what is the capacity retention already know that the capacity after

n cycle and capacitor at initial so like this one initial 250 and after 150 and the multiply 100 that means is close the 60 percent capacity retention so the using this kind of thing we can compare so of the each cells like this one and this one so which is better one two three might be one is the the best

the capacity retention the performance. Next about the C rate or we can call the current density. So what does it mean to know the C rate in the using battery? First, the charge C rate helps users to understand how long it will take to fully charge. The battery will charge their battery. For example, when you see a battery level that is chargeable at 10C, means the battery can be charged at the current.

current of 10 times of the battery capacity and it takes at least 6 minutes to be currently charged. Second, discharge C-rates have used the expected limit of the product proponents. For example, drones like some aircraft to require light weight and the small battery in order to fly. A battery with the raw discharge C-rate may not be able to offer the high enough current needed for doing some tweaks. But the high C-rate battery discharges faster and elements such, so don't worry.

also we can explain the C rate charging or discharging current ampere divided weight battery capacity so 1C means the charging and discharging time just for one hour but 2C is the half one 30mm 10C is 6 meaning discharging or charging 0.1C means 10 hour charging or discharging

So let's think about the C rate and how it differs depending on the applications. As you can see from the illustrations, the C rate is high. It is similar to having a fast fluid flow and the C is delivered quickly. So this is the essential in the applications like as the power tool like this high C rate.

On the other hand, in many general applications, energy demand is lower and more gradual. In these cases, slower, discharging, the rate is perfectly acceptable and it is enough to meet the requirement of performance at the moderate C-rate. For electric vehicles, ideally we would like to have batteries that can support both high C-rate, like this the creek

charging, quick acceleration, long cycle life. However, achieving this balance is a challenge. As higher feed rates can compromise stability and safety, this is why further research is still required in this field. Next is about the several important indicators that can be observed from the battery discharge.

curve. First open circuit voltage. We will see the voltage between battery terminal when there is no road in the battery. Just like we can see this kind of curve. Time voltage. We connected the battery with some electric application without any the current

or voltage, they show this one. There is the open circuit voltage. Terminal voltage is the voltage measured between the battery terminal when no load is connected. It represents the resting potential of the battery. And some things cut off the voltage VCO. This is the voltage at which the battery is considered fully discharged.

Even though some charge may remain, discharging below this level can damage the battery and shorten its lifespan. State of charge already is quite thin, similar to the discharge of the depth of discharge. The source expressed the remaining capacity of the battery as a percentage of its maximum capacity. When the source reaches zero,

and the terminal voltage which the VCO there is still the small amount of the charge left but using it further would cause permanent damage. Depths of the charge already we know that but with the state of charge they have these kinds of the relationship DOD is the 100 minus SOC and then end of light the battery which is end of light when it can no longer perform according to its minimum requirements

specifications often defined as retaining only 80% of each initial capacity. And state of house measures the overall condition of the battery express the percentage of usable life remaining before the battery reaches. Battery discharge curves are based on the battery polarization that occurred during the discharge. The amount of energy that battery can supply corresponding to the area under the discharging curve is strongly related to operation conditions such as

C-Rate, temperature, pressure. During the discharge, the battery experiences a drop of the voltage like this one. The voltage drop is related to several factors. First thing, IR drop, the drop in the cell voltage due to the current flowing across the battery internal

resistance, the inner-to-release factor increased mostly linear slope at high discharge rate at a constant temperature. Second, activation polarization refers to the various retarding factor inherent to the kinetics of electrochemical reaction.

So like the work function, ion must overcome the junction between the electrode and electrolyte. But concentration, polarization, this factor consider resistance based by the mass transfer like diffusion. So already you know that we have a cathode, anode, the lithium ions is moving here.

In this system, we can consider the mass transfer, the diffusion, the process. This factor dominates as a RB fully discharged, while the slope of the curve becomes very stiff. Discharge curve for RB below shows that the effective capacity is reduced if the cell is discharged at very high C-rate. high C-rate.

This is called capacity offset and this kind of effect is common to the most cell chemistry. Operating the chemistry is an important parameter impacting the battery for months. At a very low temperature, battery with the accuracy electrolyte may freeze, placing a low limit on the operating temperature range. Lithium ion battery undergo lithium plating of the anodes at a low temperature, permanently reducing capacity. At a high temperature, chemicals can be used.

break down and the battery ceases to function. In between freezing and the chemical destruction, battery performance typically vary by the temperature. So one of the case electric vehicle, so when we drive with the electric vehicle we can call the winter and the summer. They have a different mileage. So for example the summer mileage is the

charging 500 km. But then in winter we can go 350 or 400 km. Because of their slow electrochemical kinetics that everything is related to their temperature. The crackle load show impact on the vitamin batteries at varying the temperature.

so already know that the at the very low temperature the performance can be greatly reduced this one is capacity is by row capacity row means in the electric vehicle the mile distance in row for example the further offering temperature and battery from the room temperatures

The more the cycle life degrades, a complete analysis of the all factors impacting the stability of the various battery chemistry for specific applications is beyond the scope of this look into the battery cycle. Let's take a look at the characteristics of the real battery. The example here is the Panasonic battery

NCR18650B, commonly used in the cylindrical lithium-ion battery cell. Our question is what is the energy value and the energy density of the cell. Using the chamform law we already discussed earlier, we can calculate for the cell the energy is nominal voltage and the capacity.

the watt hour the what is staying the nominal average voltage is 6.6 volt so 6.6 3.6 volt multiply capacity typical that this one or this one for the easy the calculator 3.2 ampere hour so when you multiply 11.52 watt hour

things of the energy value. Now to calculate energy density, what is the energy density? We can calculate energy, divide, mass or weight. So put in here like 11.5 and

So calculated, so 237 watt hour per kilogram. That means there are some energy density. This example shows how the radiomino battery achieved relatively high energy compared to old battery chemistry, which is one of the key reasons they dominate in the portable electronics and then the electrical vehicles.

second some example the ANR 266.5M1 cells which is often used for low-cost applications so question is again energy value and density we already know that nominal capacity and value like this one they put in here

7.59 watt hour so that is the energy value and the energy density 7 gram converted to kilograms so we can calculate it that is a significant lower than the Panasonic stats previously which I introduced but then that there are some these kinds of things is quite the

lower energy density but it is still useful in the applications where cost and safety are prioritized over the compact size or the maximum energy storage.