Week 1 Understanding Different Battery Chemistry
Now a day, Lithium-ion batteries are incredibly popular. We can find them in laptops, cell phones and i Pods. They are so popular because, they are the most energetic rechargeable batteries. Lithium-ion batteries power the lives of millions of people each day.
Working:-
The rechargeable Lithium Ion Battery is made of one or more power-generating compartments called cells. Each cell has essentially three components.- positive electrode, negative electrode and electrolyte.
A positive electrode connects to the battery's positive or + terminal. A negative electrode connects to the negative or − terminal. And a chemical called an electrolyte in between them.
The positive electrode is typically made from a chemical compound called LCO, LMO, NCA, NMC, LFP and LTO. The negative electrode is generally made from carbon (graphite). The electrolyte varies from one type of battery to another.
The electrolyte carries positively charged lithium ions from the anode to the cathode.The movement of the lithium ions creates free electrons in the anode which creates a charge at the positive current collector. The electrical current then flows from the current collector through a device being powered (cell phone, computer, etc.) to the negative current collector. The separator blocks the flow of electrons inside the battery.
While the battery is discharging and providing an electric current, the anode releases lithium ions to the cathode, generating a flow of electrons from one side to the other. When plugging in the device, the opposite reaction happens, the cathode releases lithium ions and anode receives them. This is how the Lithium-ion battery works.
In this battery, the energy density and power density are most common things of the battery. Generally, the energy density measures in watt-hours per kilogram (wh/kg) and is the amount of energy the battery can store with respect to its mass. Power density measures in watts per kilogram (W/kg) and is the amount of power of battery with respect to its mass.
Lets get some information about the different cathode composition which are used in today's world for the Lithium Ion battery:-
i) 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).
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.
| Lithium Cobalt Oxide: LiCoO2 cathode (~60% Co), graphite anode Short form: LCO or Li-cobalt. Since 1991 |
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| 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 |
ii) Lithium Manganese Oxide (LiMn2O4) — LMO
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.
Li-manganese has a capacity that is roughly one-third lower than Li-cobalt. Design flexibility allows engineers to maximize the battery for either optimal longevity (life span), maximum load current (specific power) or high capacity (specific energy). 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
| Lithium Manganese Oxide: LiMn2O4 cathode. graphite anode Short form: LMO or Li-manganese (spinel structure) Since 1996 |
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| 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 depth of discharge, temperature) |
| Thermal runaway | 250°C (482°F) typical. High charge promotes thermal runaway |
| Applications | Power tools, medical devices, electric powertrains |
iii) Lithium Nickel Manganese Cobalt Oxide (LiNiMnCoO2) — NMC:-
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.
| Lithium Nickel Manganese Cobalt Oxide: LiNiMnCoO2. cathode, graphite anode Short form: NMC (NCM, CMN, CNM, MNC, MCN similar with different metal combinations) Since 2008 |
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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 depth of discharge, temperature) |
| Thermal runaway | 210°C (410°F) typical. High charge promotes thermal runaway |
| Cost | ~$420 per kWh[1] |
| Applications | E-bikes, medical devices, EVs, industrial |
iv) Lithium Iron Phosphate(LiFePO4) — LFP
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.
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.
| Lithium Iron Phosphate: LiFePO4 cathode, graphite anode Short form: LFP or Li-phosphate Since 1996 |
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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 that 2V causes damage) |
| Cycle life | 2000 and higher (related to depth of discharge, temperature) |
| Thermal runaway | 270°C (518°F) Very safe battery even if fully charged |
| Cost | ~$580 per kWh[1] |
| Applications | Portable and stationary needing high load currents and endurance |
v) Lithium Nickel Cobalt Aluminum Oxide (LiNiCoAlO2) — NCA
Lithium nickel cobalt aluminum oxide battery shares similarities with NMC by offering high specific energy, reasonably good specific power and a long life span. Less flattering are safety and cost.
| Lithium Nickel Cobalt Aluminum Oxide: LiNiCoAlO2 cathode (~9% Co), graphite anode Short form: NCA or Li-aluminum. Since 1999 |
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| 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 depth of discharge, temperature) |
| Thermal runaway | 150°C (302°F) typical, High charge promotes thermal runaway |
| Cost | ~$350 per kWh[1] |
| Applications | Medical devices, industrial, electric powertrain (Tesla) |
vi) Lithium Titanate (Li2TiO3) — LTO
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 (–22°F).
LTO (commonly Li4Ti5O12) has advantages over the conventional cobalt-blended Li-ion with graphite anode by attaining zero-strain property, no SEI film formation and no lithium plating when fast charging and charging at low temperature. Thermal stability under high temperature is also better than other Li-ion systems; however, the battery is expensive.
| Lithium Titanate: Cathode can be lithium manganese oxide or NMC; Li2TiO3 (titanate) anode Short form: LTO or Li-titanate Commercially available since about 2008. |
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| Voltages | 2.40V nominal; typical operating range 1.8–2.85V/cell |
| Specific energy (capacity) | 50–80Wh/kg |
| Charge (C-rate) | 1C typical; 5C maximum, charges to 2.85V |
| Discharge (C-rate) | 10C possible, 30C 5s pulse; 1.80V cut-off on LCO/LTO |
| Cycle life | 3,000–7,000 |
| Thermal runaway | One of safest Li-ion batteries |
| Cost | ~$1,005 per kWh[1] |
| Applications | UPS, electric powertrain (Mitsubishi i-MiEV, Honda Fit EV), solar-powered street lighting |
Let us see the Radar plot demonstrating the relative qualities of different classes of cathode material:-
Future Batteries:-
- Solid-state Li-ion: High specific energy but poor loading and safety.
- Lithium-sulfur: High specific energy but poor cycle life and poor loading
- Lithium-air: High specific energy but poor loading, needs clean air to breath and has short life.