Week 1 Understanding Different Battery Chemistry
Aim:
To prepare a table that includes materials & chemical reactions occurring at the anode and cathode of LCO, LMO, NCA, NMC, LFP, and LTO type of lithium-ion cells. Also compare the differences between each type of Li+ion batteries based on their characteristics.
Theory And Solution:
Battery is a source of electric power consisting of one or more electrochemical cells with external connections for powering electrical devices such as flashlights, mobile phones, and electric cars. When a battery is supplying electric power, its positive terminal is the cathode and its negative terminal is the anode. The terminal marked negative is the source of electrons that will flow through an external electric circuit to the positive terminal. When a battery is connected to an external electric load, a redox reaction converts high-energy reactants to lower-energy products, and the free-energy difference is delivered to the external circuit as electrical energy. Historically the term "battery" specifically referred to a device composed of multiple cells, however the usage has evolved to include devices composed of a single cell.
A battery consists of some number of voltaic cells. Each cell consists of two half-cells connected in series by a conductive electrolyte containing metal cations. One half-cell includes electrolyte and the negative electrode, the electrode to which anions (negatively charged ions) migrate; the other half-cell includes electrolyte and the positive electrode, to which cations (positively charged ions) migrate. Cations are reduced (electrons are added) at the cathode, while metal atoms are oxidized (electrons are removed) at the anode.[14] Some cells use different electrolytes for each half-cell; then a separator is used to prevent mixing of the electrolytes while allowing ions to flow between half-cells to complete the electrical circuit.
Each half-cell has an electromotive force (emf, measured in volts) relative to a standard. The net emf of the cell is the difference between the emfs of its half-cells. Thus, if the electrodes have emfs in other words, the net emf is the difference between the reduction potentials of the half-reactions.
Types of Lithium Ion batteries
Lithium Cobalt Oxide (LiCoO2) — LCO
Its high specific energy makes Li-cobalt the popular choice for mobile phones, laptops and digital cameras. The battery consists of a cobalt oxide cathode and a graphite carbon anode. 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). Figure 1 illustrates the structure.
The drawback of Li-cobalt is a relatively short life span, low thermal stability and limited load capabilities (specific power). Like other cobalt-blended Li-ion, Li-cobalt has a graphite anode that limits the cycle life by a changing solid electrolyte interface (SEI), thickening on the anode and lithium plating while fast charging and charging at low temperature. Newer systems include nickel, manganese and/or aluminum to improve longevity, loading capabilities and cost.
Li-cobalt should not be charged and discharged at a current higher than its C-rating. This means that an 18650 cell with 2,400mAh can only be charged and discharged at 2,400mA. Forcing a fast charge or applying a load higher than 2,400mA causes overheating and undue stress. For optimal fast charge, the manufacturer recommends a C-rate of 0.8C or about 2,000mA. (See BU-402: What is C-rate). The mandatory battery protection circuit limits the charge and discharge rate to a safe level of about 1C for the Energy Cell.
The drawback of Li-cobalt is a relatively short life span, low thermal stability and limited load capabilities (specific power). Like other cobalt-blended Li-ion, Li-cobalt has a graphite anode that limits the cycle life by a changing solid electrolyte interface (SEI), thickening on the anode and lithium plating while fast charging and charging at low temperature. Newer systems include nickel, manganese and/or aluminum to improve longevity, loading capabilities and cost.
Li-cobalt should not be charged and discharged at a current higher than its C-rating. This means that an 18650 cell with 2,400mAh can only be charged and discharged at 2,400mA. Forcing a fast charge or applying a load higher than 2,400mA causes overheating and undue stress. For optimal fast charge, the manufacturer recommends a C-rate of 0.8C or about 2,000mA. (See BU-402: What is C-rate). The mandatory battery protection circuit limits the charge and discharge rate to a safe level of about 1C for the Energy Cell.
Lithium Manganese Oxide (LiMn2O4) — LMO
Li-ion with manganese spinel was first published in the Materials Research Bulletin in 1983. In 1996, Moli Energy commercialized a Li-ion cell with lithium manganese oxide as cathode material. The architecture forms a three-dimensional spinel structure that improves ion flow on the electrode, which results in lower internal resistance and improved current handling. A further advantage of spinel is high thermal stability and enhanced safety, but the cycle and calendar life are limited.
Low internal cell resistance enables fast charging and high-current discharging. In an 18650 package, Li-manganese can be discharged at currents of 20–30A with moderate heat buildup. It is also possible to apply one-second load pulses of up to 50A. A continuous high load at this current would cause heat buildup and the cell temperature cannot exceed 80°C (176°F). Li-manganese is used for power tools, medical instruments, as well as hybrid and electric vehicles.
Figure 4 illustrates the formation of a three-dimensional crystalline framework on the cathode of a Li-manganese battery. This spinel structure, which is usually composed of diamond shapes connected into a lattice, appears after initial formation.
The cathode crystalline formation of lithium manganese oxide has a three-dimensional framework structure that appears after initial formation. Spinel provides low resistance but has a more moderate specific energy than cobalt.
Lithium Nickel Manganese Cobalt Oxide (LiNiMnCoO2) — NMC
One of the most successful Li-ion systems is a cathode combination of nickel-manganese-cobalt (NMC). Similar to Li-manganese, these systems can be tailored to serve as Energy Cells or Power Cells. For example, NMC in an 18650 cell for moderate load condition has a capacity of about 2,800mAh and can deliver 4A to 5A; NMC in the same cell optimized for specific power has a capacity of only about 2,000mAh but delivers a continuous discharge current of 20A. A silicon-based anode will go to 4,000mAh and higher but at reduced loading capability and shorter cycle life. Silicon added to graphite has the drawback that the anode grows and shrinks with charge and discharge, making the cell mechanically unstable.
The secret of NMC lies in combining nickel and manganese. An analogy of this is table salt in which the main ingredients, sodium and chloride, are toxic on their own but mixing them serves as seasoning salt and food preserver. Nickel is known for its high specific energy but poor stability; manganese has the benefit of forming a spinel structure to achieve low internal resistance but offers a low specific energy. Combining the metals enhances each other strengths.
NMC is the battery of choice for power tools, e-bikes and other electric powertrains. The cathode combination is typically one-third nickel, one-third manganese and one-third cobalt, also known as 1-1-1. This offers a unique blend that also lowers the raw material cost due to reduced cobalt content. Another successful combination is NCM with 5 parts nickel, 3 parts cobalt and 2 parts manganese (5-3-2). Other combinations using various amounts of cathode materials are possible.
Battery manufacturers move away from cobalt systems toward nickel cathodes because of the high cost of cobalt. Nickel-based systems have higher energy density, lower cost, and longer cycle life than the cobalt-based cells but they have a slightly lower voltage.
New electrolytes and additives enable charging to 4.4V/cell and higher to boost capacity. Figure 7 demonstrates the characteristics of the NMC.
Lithium Iron Phosphate(LiFePO4) — LFP
In 1996, the University of Texas (and other contributors) discovered phosphate as cathode material for rechargeable lithium batteries. Li-phosphate offers good electrochemical performance with low resistance. This is made possible with nano-scale phosphate cathode material. The key benefits are high current rating and long cycle life, besides good thermal stability, enhanced safety and tolerance if abused.
Li-phosphate is more tolerant to full charge conditions and is less stressed than other lithium-ion systems if kept at high voltage for a prolonged time. (See BU-808: How to Prolong Lithium-based Batteries). As a trade-off, its lower nominal voltage of 3.2V/cell reduces the specific energy below that of cobalt-blended lithium-ion. With most batteries, cold temperature reduces performance and elevated storage temperature shortens the service life, and Li-phosphate is no exception. Li-phosphate has a higher self-discharge than other Li-ion batteries, which can cause balancing issues with aging. This can be mitigated by buying high quality cells and/or using sophisticated control electronics, both of which increase the cost of the pack. Cleanliness in manufacturing is of importance for longevity. There is no tolerance for moisture, lest the battery will only deliver 50 cycles. Figure 9 summarizes the attributes of Li-phosphate.
Li-phosphate is often used to replace the lead acid starter battery. Four cells in series produce 12.80V, a similar voltage to six 2V lead acid cells in series. Vehicles charge lead acid to 14.40V (2.40V/cell) and maintain a topping charge. Topping charge is applied to maintain full charge level and prevent sulfation on lead acid batteries.
With four Li-phosphate cells in series, each cell tops at 3.60V, which is the correct full-charge voltage. At this point, the charge should be disconnected but the topping charge continues while driving. Li-phosphate is tolerant to some overcharge; however, keeping the voltage at 14.40V for a prolonged time, as most vehicles do on a long road trip, could stress Li-phosphate. Time will tell how durable Li-Phosphate will be as a lead acid replacement with a regular vehicle charging system. Cold temperature also reduces performance of Li-ion and this could affect the cranking ability in extreme cases.
Lithium Nickel Cobalt Aluminum Oxide (LiNiCoAlO2) — NCA
Lithium nickel cobalt aluminum oxide battery, or NCA, has been around since 1999 for special applications. It shares similarities with NMC by offering high specific energy, reasonably good specific power and a long life span. Less flattering are safety and cost. Figure 11 summarizes the six key characteristics. NCA is a further development of lithium nickel oxide; adding aluminum gives the chemistry greater stability.
Lithium-titanate-oxide (LTO) battery
The lithium-titanate-oxide (LTO) battery is a type of rechargeable battery that has the advantage of being faster to charge than other lithium-ion batteries, but the disadvantage of having a much lower energy density.
A lithium-titanate battery is a modified lithium-ion battery that uses lithium-titanate nanocrystals, instead of carbon, on the surface of its anode. This gives the anode a surface area of about 100 square meters per gram, compared with 3 square meters per gram for carbon, allowing electrons to enter and leave the anode quickly. This makes fast recharging possible and provides high currents when needed. Lithium-titanate cells also last for 3000 to 7000 charge cycles; one source claims a cycle life of ~1000 cycles before reaching 80% capacity when charged and discharged at 55 °C (131 °F), rather than the standard 25 °C (77 °F).
A disadvantage of lithium-titanate batteries is that they have a lower inherent voltage (2.4 V), which leads to lower specific energy (about 30–110 Wh/kg) than conventional lithium-ion battery technologies, which have an inherent voltage of 3.7 V, although some lithium-titanate batteries are reported to have an energy density of up to 177 Wh/L
Batteries with lithium titanate anodes have been known since the 1980s. Li-titanate replaces the graphite in the anode of a typical lithium-ion battery and the material forms into a spinel structure. The cathode can be lithium manganese oxide or NMC. Li-titanate has a nominal cell voltage of 2.40V, can be fast charged and delivers a high discharge current of 10C, or 10 times the rated capacity. The cycle count is said to be higher than that of a regular Li-ion. Li-titanate is safe, has excellent low-temperature discharge characteristics and obtains a capacity of 80 percent at –30°C.
2.Compare the differences between each type of Li+ion batteries based on their characteristics
| Lithium Cobalt Oxide: LiCoO2 cathode (~60% Co), graphite anode Short form: LCO or Li-cobalt. Since 1991 |
|
| Voltages | 3.60V nominal; typical operating range 3.0–4.2V/cell |
| Specific energy (capacity) | 150–200Wh/kg. Specialty cells provide up to 240Wh/kg. |
| Charge (C-rate) | 0.7–1C, charges to 4.20V (most cells); 3h charge typical. Charge current above 1C shortens battery life. |
| Discharge (C-rate) | 1C; 2.50V cut off. Discharge current above 1C shortens battery life. |
| Cycle life | 500–1000, related to depth of discharge, load, temperature |
| Thermal runaway | 150°C (302°F). Full charge promotes thermal runaway |
| Applications | Mobile phones, tablets, laptops, cameras |
Characteristics of Lithium Manganese Oxide( LMO)
| Lithium Manganese Oxide: LiMn2O4 cathode. graphite anode Short form: LMO or Li-manganese (spinel structure) |
|
| Voltages | 3.70V (3.80V) nominal; typical operating range 3.0–4.2V/cell |
| Specific energy (capacity) | 100–150Wh/kg |
| Charge (C-rate) | 0.7–1C typical, 3C maximum, charges to 4.20V (most cells) |
| Discharge (C-rate) | 1C; 10C possible with some cells, 30C pulse (5s), 2.50V cut-off |
| Cycle life | 300–700 (related to the depth of discharge, temperature) |
| Thermal runaway | 250°C (482°F) typical. High charge promotes thermal runaway |
| Applications | Power tools, medical devices, electric powertrains |
| Comments | High power but less capacity; safer than Li-cobalt; commonly mixed with NMC to improve performance. |
Characteristics of Lithium Nickel Cobalt Aluminum Oxide(NCA)
| Lithium Nickel Cobalt Aluminum Oxide: LiNiCoAlO2 cathode (~9% Co), graphite anode Short form: NCA or Li-aluminum. |
|
| Voltages | 3.60V nominal; typical operating range 3.0–4.2V/cell |
| Specific energy (capacity) | 200-260Wh/kg; 300Wh/kg predictable |
| Charge (C-rate) | 0.7C charges to 4.20V (most cells), 3h charge typical, fast charge possible with some cells |
| Discharge (C-rate) | 1C typical; 3.00V cut-off; high discharge rate shortens battery life |
| Cycle life | 500 (related to the depth of discharge, temperature) |
| Thermal runaway | 150°C (302°F) typical, High charge promotes thermal runaway |
| Cost | ~$350 per kWh |
| Applications | Medical devices, industrial, electric powertrain (Tesla) |
| Comments | Shares similarities with Li-cobalt. Serves as Energy Cell. Mainly used by Panasonic and Tesla; growth potential. |
Characteristics of lithium nickel manganese cobalt oxide (NMC)
| Lithium Nickel Manganese Cobalt Oxide: LiNiMnCoO2. cathode, graphite anode Short form: NMC |
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| Voltages | 3.60V, 3.70V nominal; typical operating range 3.0–4.2V/cell, or higher |
| Specific energy (capacity) | 150–220Wh/kg |
| Charge (C-rate) | 0.7–1C, charges to 4.20V, some go to 4.30V; 3h charge typical. Charge current above 1C shortens battery life. |
| Discharge (C-rate) | 1C; 2C possible on some cells; 2.50V cut-off |
| Cycle life | 1000–2000 (related to the depth of discharge, temperature) |
| Thermal runaway | 210°C (410°F) typical. High charge promotes thermal runaway |
| Cost | ~$420 per kWh |
| Applications | E-bikes, medical devices, EVs, industrial |
| Comments | Provides high capacity and high power. Serves as Hybrid Cell. Favourite chemistry for many uses; market share is increasing. |
Characteristics of lithium iron phosphate(LFP)
| Lithium Iron Phosphate: LiFePO4 cathode, graphite anode Short form: LFP or Li-phosphate. LIP is also common. |
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| Voltages | 3.20, 3.30V nominal; typical operating range 2.5–3.65V/cell |
| Specific energy (capacity) | 90–120Wh/kg |
| Charge (C-rate) | 1C typical charges to 3.65V; 3h charge time typical |
| Discharge (C-rate) | 1C, 25C on some cells; 40A pulse (2s); 2.50V cut-off (lower than 2V causes damage) |
| Cycle life | 2000 and higher (related to the depth of discharge, temperature) |
| Thermal runaway | 270°C (518°F) Very safe battery even if fully charged |
| Cost | ~$580 per kWh |
| Applications | Portable and stationary needing high load currents and endurance |
| Comments | Very flat voltage discharge curve but low capacity. One of safest Li-ions. Used for special markets. Elevated self-discharge. |