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Abstract: The Lithium-ion battery is one of the most common batteries used in Electric Vehicles (EVs) due to the specific features of high energy density, power density, long life span and environment friendly. With the development of lithium-ion battery technology, different materials have been adopted in the design of…
Omkar Kudalkar
updated on 14 Dec 2021
Abstract:
The Lithium-ion battery is one of the most common batteries used in Electric Vehicles (EVs) due to the specific features of high energy density, power density, long life span and environment friendly. With the development of lithium-ion battery technology, different materials have been adopted in the design of the cathodes and anodes in order to gain a better performance. LiMn2O4, LiN iMnCoO2, LiN iCoAlO2, LiF eP O4 and Li4T i5O12 are five common lithium-ion batteries adopted in commercial EVs nowadays. The characteristics of these five lithium ion batteries are reviewed and compared in the aspects of electrochemical performance and their practical applications.
Introduction:
With increasing public concerns about rising gasoline prices and climate change, battery electric, hybrid electric, and plug-in hybrid electric vehicles offer substantial promise of reducing fuel consumption and the impact of transportation on the environment, without the need for a large new alternative fuel infrastructure. While their use is promising, battery and hybrid electric vehicles also present significant engineering challenges. High-voltage battery vehicles must meet stringent safety requirements and yet achieve the driving range, reliability, and cost targets expected by consumers.
Current vehicle manufacturers are developing and commercializing all-electric and range extended plug-in vehicles. These BEVs and PHEVs plug directly into the electrical grid to charge the propulsion battery. When compared to current commercial hybrid vehicles, which use a combination of battery and internal combustion engine, the BEVs and PHEVs require greatly improved battery systems. The improved battery systems need between 15 and 50 times the amount of energy storage and must allow for greater depth of discharge of the battery during operation. One of the leading battery types possessing the performance characteristics needed to enable the BEVs and PHEVs is lithium-ion. The performance characteristics of large battery systems are determined by the basic electrochemistry that occurs at the interfaces of the system components at the cell level. The main electrochemical interfaces in the cell are between the anode, electrolyte, and cathode. The choice of the anode and cathode determines the voltage, capacity, and specific energy. The performance requirements of the automotive drive train that uses the Li-ion battery will determine what specific embodiment of the battery is needed. This section of the report discusses Li-ion battery electro chemistries that are available or in development that might be considered for Li-ion battery vehicles. This section also identifies candidate materials used for the anode, cathode, and electrolyte and their electrochemical interactions, and it describes electrical performance of different cell chemistries and failure modes and hazards at the electrochemical level.
A “cell” is the fundamental building block of an electrochemical system. Cells are built up to battery modules, and modules are built up to battery packs and battery systems, as illustrated in Figure:
Cells are made up of the following subcomponents.
For each subcomponent, there are numerous variations both in commercially available cells and those still under research. Each combination of cathode chemistry, anode chemistry, electrolyte composition and additives, and separator type provides a range of power densities, charge regimes, capacities, charge management techniques, and safety concerns and challenges.
Summary of lithium-ion battery advantages and disadvantages.
1.Prepare a table which includes materials & chemical reactions occurring at the anode and cathode of LCO, LMO, NCA, NMC, LFP and LTO type of lithium ion cells.Give your detailed explanation on it.
During battery operation (i.e., charging and discharging), ions move back and forth between the cathode and anode through the electrolyte, and electrons move through the external circuit. During cell discharging, the anode oxidizes (loses electrons) and the cathode experiences a reduction (gains electrons). While this is occurring, Li+ ions are transferred through the electrolyte from the anode to the cathode. During charging, this process is reversed. The electrochemical process that occurs during charge and discharge is an “intercalation” process, in which Li-ions become temporary “guests” to the host electrodes without any major structural change to the electrodes. The majority of what happens during this process is reversible.
Cathode :
The cathode is a host structure, where lithium-ions can be reversibly inserted and removed. Beside a high specific capacity, a high and stable voltage versus lithium metal; A cathode in an electrochemical cell accepts electrons and ions during discharge of a cell. The active material of a cathode in a Li-ion cell is made from a combination of a lithium metal oxide or lithium metal phosphate, a polymer binder (polyvinylidene fluoride [PVDF], carboxymethylecellulose or styrene/butadiene rubber) and conductive filler (carbon black). These materials are made using standard inorganic material manufacturing processes. The active materials adhere to a metallic current collector.
Structure | Cathode Type | Chemistry | Details |
Layered |
Li-Cobalt LCO |
LiCoO2 | The majority of portable chemistries use this cathode material, along with a graphite carbon anode. This combination provides for high energy density and a long run time. However, the chemistry provides a relatively low discharge current. It has been reported that, after 24 to 36 months of cycling, the pack often becomes unserviceable due to a large voltage drop under load that is caused by high internal resistance. |
Layered | Lithium Nickel Cobalt Aluminum Oxide NCA |
LiNiCoAlO2 | Reports suggest that NCA is somewhat safer than LiCoO2, largely by virtue of the fact that it has a slightly lower voltage at full charge and therefore a larger margin to accept overcharge. It has been further suggested that NCA also has far superior life characteristics, both on float and in cycling, and is therefore the positive material of choice for many automobile manufacturers for the next generation of hybrid electric vehicles. |
Spinel |
Li-Manganese |
LiMn2O4 | The manganese possesses a three dimensional spinel structure that improves the ion flow between the electrodes. High ion flow lowers the internal resistance and increases loading capability. The resistance stays low with cycling;however, the battery does age and the overall service life is similar to that of cobalt. It has been reported that Spinel has an inherently high thermal stability and needs less safety circuitry than a cobalt system. Low internal cell resistance is the key to high rate capability. One of the shortcomings of this system is the lower capacity compared to the cobalt-based system. Spinel provides a capacity that is about half that of the cobalt equivalent. But, spinel still provides an energy density that is about 50%higher than that of a nickel-based equivalent. |
Spinel | Lithium Nickel Manganese Cobalt NMC |
LiNiMnCoO2 | Tends to be more stable, and therefore more resistant to overcharging, than LCO. Rapidly loses capacity through cycling. |
Spinel | Lithium Nickel Manganese Oxide |
LiNi0.5Mn1.5 O4 | Its primary advantage is that it can reach an operating voltage of 5V, which leads to a significant increase in energy density. An obstacle to its practical use is that organic carbonate electrolytes typically used in Li-ion batteries are not compatible with voltages approaching 5V. |
Olivine | Li-Phosphate LFP (Lithium Iron Phosphate) |
LiFePO4 | Exception to the rule that a cathode material must have high ionic and electronic mobility. This material achieves adequate lithium transport by using electrode materials withnano-sized particles. For a significant improvement in safety in a positive electrode material, it has been suggested to move away from oxide materials to ones based on phosphates. Phosphate bonds are much stronger than those in oxides, with the result that when abusively overcharged, LiFePO4 cells release very little energy. Cells using LiFePO4 have reasonable calendar life and excellent cycling, characteristics as long as they are operated at moderate temperatures. It has been further suggested, however, that there is a tradeoff between the added safety and lower energy density. |
Anode :
An anode in an electrochemical cell loses electrons and ions during the discharge of the cell. The anodes in Li-ion cells are typically carbon-based materials. A wide variety of carbons are used as negative electrodes today. Common forms include graphene, graphite, and carbon black. These forms can be oriented as planar, whiskers, or spherules. Graphite is one of the most commonly used anode materials. It stores lithium well within its structure and maintains stability over a long cycle life.
Solid electrolyte interface (SEI) Layer :
During the first cycle in Li-ion batteries, a semi-permanent coating layer is formed on the anode and cathode, called the solid electrolyte interface (SEI). This layer is a significant enabling feature of Li-ion technology. This is because the graphite electrode potential is so negative that the Li-ions between the carbon layers would be expected to react immediately with the solvent of the electrolyte. The SEI is permeable to Li-ions but not to the electrolyte, and its stability is an important requirement for long operating life.
In some instances, lithium titanate is used as the active material in the anode. It has a less negative voltage than the graphite anodes. This enables the Li-ions to be more stable and less likely to react with the electrolyte. For lithium titanate, no SEI is formed and the cell is more stable at higher voltages. Table below outlines some of the anode materials in use or under development. The majority of cells use a carbon based anode, and the other three outlined are still primarily in the research phase of development.
Anode Type | Chemistry | Details |
Carbon | C → CxLix | The most common form of anode, carbon electrodes provide a stable surface morphology that stores lithium well within its structure and maintains stability over a long cycle life. A wide variety of carbons are used as negative electrodes today. Common forms include graphene, graphite, and carbon black. These forms can be oriented as planar, whiskers, or spherules. |
Lithium Titanate LTO |
Li4Ti5O12 | Lithium titanate negative material operates at a higher (less negative) voltage, at which Li-ions are stable with respect to the electrolyte. The higher negative electrode voltage leads to lower cell voltage, so energy and power density suffer accordingly. An SEI does not form and the overheating problem (for the anode) is eliminated, allowing cells to be charged at a much higher rate, sometimes in as little as 5 minutes. |
Sn-Co-C ternary alloy |
Scrosati and Garche (2010) suggest that this material is already in use as an anode material in a commercial battery. | |
Silicon | Si | Silicon achieves a 20 to 30% increase in specific energy at the cost of lower load currents and reduced cycle life due to the large volume change upon lithiation. |
Electrolyte:
The electrolyte is the physical medium that allows ionic transport between the electrodes during charging and discharging of a cell. Electrolytes in Li-ion batteries may either be a liquid or a gel. Lithium batteries use non-aqueous electrolytes because of reactivity of lithium with aqueous electrolytes and the inherent stability of non-aqueous electrolytes at higher voltages. Liquid electrolytes are a combination of a solution of solvents and lithium salts, as well as additives that improve the cell performance. The liquid electrolyte in Li-ion cells is typically lithium hexafluorophosphate (LiPF6) dissolved in a mixture of organic solvents (mainly carbonates), which must be formulated to match the electrode materials used. With gel electrolytes, also known as lithium polymer cells, a monomer is added to the electrolyte during the assembly of the cell and is thermally activated. This reaction creates a polymer electrolyte that encompasses the entire internal geometry of the cell.
Separator:
The separator is a microporous, electrically insulating material that is positioned between the anode and the cathode. The separator performs two critical roles. First, it prevents internal short circuiting between the anode and cathode by providing a physical, non-electrically conductive barrier. Second, it provides a path for ionic transport.
Lithium Battery Technologies:
Lithium Ion Battery technology is based on Intercalation, which is actually the addition of lithium ions into a host material without significantly changing the host's structure. During a discharge cycle, lithium atoms in the anode are ionized and separated from their electrons. The lithium ions move from the anode via electrolyteas medium and pass through micro-permeable separator which is in between anode and cathode until they reach the cathode, where they recombine with their electrons. The lithium ions are small enough (third only to hydrogen and helium), which translates into faster charge/discharge capabilities and high charge storage capability per unit mass and unit volume. The single cell voltage in Li-ion battery is difference in the energy between the Li+ ions that are present in the crystalline structure of the two electrodes.
Apart from three vital ingridents namely Cathode, Anode,and an electrolyte, an electronic controller, which regulates power, discharge flows, and moniters battery temperature is also an important and integral part of Lithium-Ion Battery. This incorporation of electronics takes care of special safety precautions need to be taken in order to ensure that the operating conditions of the lithium battery are kept in between the safety limits, because of the high reactivity of Lithium-Ion Batteries.
Lithium Cobalt Oxide (LCO): Lithium Cobalt Oxide (LiCoO2) is a mature battery technology, characterized by a long cycle life and high energy densities. The cathode consists of a cobalt oxide and anode is of graphite carbon. The cathode has a layered structure and during discharge, lithium ions move from the anode to the cathode. The flow reverses on charge. The drawback of Li-cobalt is a relatively short life span, low thermal stability and limited load capabilities (specific power).
Typical Specifications of LCO with Graphite anode
Lithium Manganese (LMO): Lithium Manganese (LiMn2O4) battery cell's cathode is made out of lithium manganese oxide. It forms a three-dimensional spinel structure which improves ion flow on the electrode, which results in lower internal resistance and improved current handling, in comparsion with Cobalt based batteries. This three dimensional spinel architecture also exhibits high thermal stability and enhanced safety, but at the cost of cycle, calendar life, and energy density. Pure Li-manganese batteries are no longer commonly, they may only be used for special applications. Recent trends indicate that most Li-manganese batteries are blended with lithium nickel manganese cobalt oxide (NMC) to improve the specific energy and prolong the life span, and is popular in most Electric Vehicles.
Typical Specifications of LMO with Graphite anode
Lithium Nickel Cobalt Aluminum Oxide (NCA): Lithium Nickel Cobalt Aluminum Oxide (LiNiCoAlO2) cathode material is highly thermally stable cathode material, doping the lithium nickel cobalt oxide with aluminum both stabilizes its thermal and charge transfer resistance. NCA shares similarities with NMC in offering high specific energy, reasonably good specific power and a long life span.
High energy and power densities, as well as good life span, make NCA a candidate for EV powertrains.
Typical Specifications of NCA with Graphite anode
Lithium Nickel Manganese Cobalt oxide (NMC): Lithium Nickel Cobalt Manganese (Li(NiCoMn)O2) batteries are made of cathode materials which is combination of nickel, manganese and cobalt, typically one-third nickel, one-third manganese and one-third cobalt, also known as 1-1-1. Similar to Li-manganese, NMC can be tailored to serve as Energy Cells or Power Cells, like other lithium-ion battery varieties, NMC batteries can have either a high specific energy density or a high specific power. They however cannot have both properties in the same pack. For example, NMC in an 18650 cell for moderate load condition has a capacity of about 2,800mAh andcan deliver 4A to 5A. NMC in the same cell size can be optimized for specific power with capacity of about 2000mAh, but capable of delivering a continuous discharge current of 20A.
Typical Specifications of NMC with Graphite anode
Lihium Ion Phosphate (LFP): In Lithium Iron Phosphate (LiFePO4) Batteries phosphate is used as cathode material, Li-phosphate offers good electrochemical performance with low resistance. This nano-scale phosphate material for cathode in Lithium Ion batteries is most viable option because of its low cost,environmental friendliness, long cycle and calendar lives (chemical stability) and good capacity (170 mAh/g). Doping with transition metals results in reduction of internal impedance. LiFePO4 batteries are incombustible in case of misuse during charging or discharging, they are more stable during overcharge or short circuit conditions and they can withstand high temperatures without decomposing. LFP is more tolerant to full charge conditions and is compartively less vunerable to stress even if kept at high voltage for a prolonged time.
Typical Specifications of LFP with Graphite anode
Lithium Titanate (LTO): Lithium Titanate ((Li2TiO3)) battery is a modified Li Ion battery in which the graphite in the anode is replaced by Li-titanate which forms a spinel structure. The cathode can be lithium manganese oxide orNMC or LFP, or other lithium battery Chemistry. LTO has a nominal cell voltage of 2.40V, can be fast charged and can deliver a high discharge current of 10C. Even the cycle life is higher than regular Li-ion batteries. LTO exhibits excellent low-temperature discharge characteristics (capacity of 80 percent at –30°C). Thermal stability under high temperature is comparitively better, highly tolerant to operational abuses and can comfortably perform up to 55 °C and can go up to 65 °C.
Typical Specifications of LTO (Li2TiO3) as Anode and LMO or NMC as Cathode
Types | Chemical Name | Cathode Material | Chemical Reaction at the cathode(discharge) | Anode material | Chemical Reaction at the anode(discharge) | Overall Reaction |
Lithium Cobalt Oxide (LCO) | LiCoO2LiCoO2 | Lithium Cobalt oxide | CoO2+Li++e−_↔LiCoO2CoO2+Li++e_↔LiCoO2 | Graphite Carbon | LiC6↔C6+Li++e−LiC6↔C6+Li++e- | LiCoO2+C6↔LiC6+C02LiCoO2+C6↔LiC6+C02 |
Lithium-ion mangenese oxide | LiMn2O2LiMn2O2 | Lithium mangenese oxide | MnO2+Li++e−_↔LiMnO2MnO2+Li++e_↔LiMnO2 | Graphite Carbon | LiC6↔C6+Li++e−LiC6↔C6+Li++e- | LiCo2+C6↔LiC6+CoO2LiCo2+C6↔LiC6+CoO2 |
Lithium Nickel cobalt aluminium oxide(NCA) | LiNiCoAlO2LiNiCoAlO2 | Lithium Nickel cobalt aluminium oxide | NiCoAlO2+Li++e−_↔LiNiCoAlO2NiCoAlO2+Li++e_↔LiNiCoAlO2 | Graphite Carbon | LiC6↔C6+Li++e−LiC6↔C6+Li++e- | LiCoO2+C6↔Lic6+CoO2LiCoO2+C6↔Lic6+CoO2 |
Lithium Nickel Mangenese Cobalt Oxide(NMC) | LiNiMnCoO2LiNiMnCoO2 | Lithium Nickel Mangenese Cobalt Oxide | NiMnCoO2+Li++e−_↔LiNiMnCoO2NiMnCoO2+Li++e_↔LiNiMnCoO2 | Graphite Carbon | LiC6↔C6+Li++e−LiC6↔C6+Li++e- | LiCoO2+C6↔LiC6+CoO2LiCoO2+C6↔LiC6+CoO2 |
Lithium Iron Phosphate(LFP) | LiFePO4LiFePO4 | Lithium Iron Phosphate | FePO4+Li++e−_↔LiFePO4FePO4+Li++e-_↔LiFePO4 | Graphite Carbon | LiC6↔C6+Li++e−LiC6↔C6+Li++e- | LiCoO2+C6↔LiC6+CoO2LiCoO2+C6↔LiC6+CoO2 |
Lithium Titanate oxide(LTO) | Li2TiO3Li2TiO3 | Manganese oxide | 4Mn2PO4+PO4+4Li++e−_↔4LiMn2O44Mn2PO4+PO4+4Li++e_↔4LiMn2O4 | Lithium Titanium Oxide | Li4Ti5O12+4Li++4e−_↔4LIMn2O4Li4Ti5O12+4Li++4e_↔4LIMn2O4 | 4Mn2O4+Li4Ti5O12↔4LiMn2O4+Ti4O124Mn2O4+Li4Ti5O12↔4LiMn2O4+Ti4O12 |
2.Compare the differences between each type of Li+ion batteries based on their characteristics.
https://www.ionenergy.co/resources/blogs/lithium-ion-battery-types/
Types of Lithium ion batteries:
Before choosing the type of battery there are some important points to be considered which affects the battery performance.
The following differences between each type of Li+ion batteries based on their characteristics are given below:
Types of Li-ion Batteries |
Specific Power |
Specific Energy |
Safety |
Lifespan |
Cost |
Perfomance |
Voltage |
Application |
Lithium Cobalt Oxide |
Low |
High |
Low |
Low |
Low |
Medium |
3.60V nominal; typical operating range 3.0-4.2V/cell |
Cell Phone, Camera & Laptops |
Lithium Manganese Oxide |
Medium |
Medium |
Medium |
Low |
Low |
Low |
3.70,3.80V nominal; typical operating range 3.0-4.2V/cell |
Power tools, Medical, Electric Vehicles. |
Lithium Nickel Manganese Cobalt Oxide |
Medium |
High |
Medium |
Medium |
Low |
Medium |
3.60/3.70V nominal; typical operating range 3.0-4.2V/cell or higher |
Power tools, Medical, Electric Vehicles. |
Lithium Iron Phosphate |
High |
Low |
High |
High |
Low |
Medium |
3.20,3.30V nominal; typical operating range 2.5-3.65V/cell |
Power tools, Medical, Electric Vehicles. |
Lithium Nickel Cobalt Aluminium Oxide |
Medium |
High |
Low |
Medium |
Medium |
Medium |
3.60V nominal; typical operating range 3-4.2V/cell |
Grid storage and Electric vehicles |
Lithium Titanate |
Medium |
Low |
High |
High |
High |
High |
2.40V nominal; typical operating range 1.8-2.85V/cell |
Grid storage and Electric vehicles |
The table above compares the voltages and typical applications of the six basic lithium battery chemistries. Other characteristics of these batteries include:
Conclusion:
Reference:
1. https://www.youtube.com/watch?v=no4vRKvKxcU
2. https://www.youtube.com/watch?v=fo3DMXwD9ig
3. https://www.batterypowertips.com/difference-between-lithium-ion-lithium-polymer-batteries-faq/
4.https://www.ionenergy.co/resources/blogs/lithium-ion-battery-types/
5. https://www.batterypowertips.com/difference-between-lithium-ion-lithium-polymer-batteries-faq/
7. https://mediatum.ub.tum.de/doc/1356293/1356293.pdf
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