Lithium-ion batteries find extensive applications, ranging from powering smartphones to serving in renewable energy storage systems and electric vehicles. Therefore, researchers are working to develop their performance and overcome challenges related to them, such as storage capacity, safety, and problems related to the environment.
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Researchers have given significant attention to the development of cathode materials, as they have a pivotal role in achieving high-performance lithium-ion batteries (LIBs). Among the materials integrated into cathodes, manganese stands out due to its numerous advantages over alternative cathode materials within the realm of lithium-ion batteries, as it offers high energy density, enhancing safety features, and cost-effectiveness.
In this article, we will explore the role of manganese in lithium-ion batteries, its advantages, limitations, and new research.
Lithium Manganese Oxide (LMO) Batteries
Lithium manganese oxide (LMO) batteries are a type of battery that uses MNO2 as a cathode material and show diverse crystallographic structures such as tunnel, layered, and 3D framework, commonly used in power tools, medical devices, and powertrains.
Advantages
LMO batteries are known for their fast charging and discharging capabilities, providing a high operating voltage and energy output. Moreover, they have good thermal stability, reducing the risk of overheating and enhancing safety features.
Furthermore, manganese, the main component, is relatively inexpensive, making LMO batteries cost-effective.
Disadvantages and Limitations
LMO batteries exhibit certain drawbacks, notably rapid capacity fading resulting from the loss of electrical connections between nanoparticles and the current collector.
Additionally, they may have a limited energy density compared to certain lithium-ion chemistries, affecting their ability to store large amounts of energy.
Despite their good thermal stability, LMO batteries can be sensitive to extreme temperatures.
Nickel Manganese Cobalt Oxide (NMC) Batteries
Nickel Manganese Cobalt Oxide (NMC) Batteries NMC is one of the lithium batteries in which manganese is used as one of the components of the cathode, which also consists of nickel and cobalt oxide typically denoted as LiNiMnCoO2. This formula signifies an equal ratio of metals but this ratio may change based on the required performance characteristics.
NMC batteries are widely used in electric vehicles as they provide a balance between energy density, cost-effectiveness, and long drive range; moreover, they provide a high current required during acceleration.
Advantages
NMC batteries offer a relatively high energy density, allowing them to store a substantial amount of energy in a compact space.
The incorporation of manganese contributes to the thermal stability of NMC batteries, reducing the risk of overheating during charging and discharging.
NMC chemistry allows for variations in the nickel, manganese, and cobalt ratios, providing flexibility to tailor battery characteristics based on specific application requirements.
NMC batteries exhibit good cycling performance, allowing for a high number of charge and discharge cycles with minimal degradation in capacity. This is crucial for long-lasting and reliable energy storage.
Disadvantages and Limitations
Although NMC batteries are less expensive than other cathode materials, they are still relatively expensive due to the presence of cobalt as one of their components. For this reason, researchers are working to reduce or replace cobalt.
NMC batteries are generally considered safer than some alternatives, but there is still a risk of thermal runaway and overheating, especially in situations of overcharging or physical damage. Thermal management systems are essential to mitigate this risk such as air cooling, liquid cooling, and phase change materials.
Over time, NMC batteries might undergo voltage fade, resulting in a reduction in their voltage levels during cycling. This occurrence has the potential to influence the overall performance and efficiency of the battery.
Lithium Manganese Spinel
The cathode known as lithium manganese spinel, denoted as LiMn2O4, adopts a spinel crystal structure that consists of a cubic close-packed arrangement of oxygen ions. Within this structure, lithium ions are situated in tetrahedral sites, whereas manganese ions occupy octahedral sites.
Lithium Manganese Spinel is used in various applications such as electric vehicles, portable electronics, and grid-level energy storage.
Advantages
Lithium Manganese Spinel has a good cycling performance due to several factors such as structure stability, manganese ion fast diffusion, and balanced electrochemical performance.
Manganese is the key component of these batteries, which contributes to lowering their overall cost.
LMS batteries have good thermal stability, which is a crucial factor for ensuring safety and reliability.
Disadvantages and Limitations
Overcharging lithium manganese spinel cathodes can result in the formation of manganese ions in higher oxidation states, leading to increased susceptibility to dissolution. This can compromise the structural integrity of the cathode.
Cycling stability can be affected when the battery is operated over its full voltage range. Extended cycling within the upper and lower voltage limits may contribute to capacity fade and reduced overall performance.
Voltage fade is another issue observed in lithium manganese spinel cathodes, where the operating voltage of the battery may decrease over time. This can affect the energy density and efficiency of the battery.
Lithium Iron Manganese Phosphate (LiFeMnPO4)
The cathode in these batteries is composed of iron, manganese, lithium, and phosphate ions; these kinds of batteries are used in power tools, electric bikes, and renewable energy storage.
Advantages
LiFeMnPO4 batteries are known for their enhanced safety characteristics, including resistance to thermal runaway and reduced risk of overheating and fires.
The combination of iron, manganese, and phosphate contributes to the stability of the cathode material, leading to a longer cycle life and improved performance.
The absence of hazardous materials like cobalt in their composition makes them environmentally friendly.
Disadvantages and Limitations
LiFeMnPO4 batteries may have a lower energy density compared to some other lithium-ion batteries; this means that they may not be the best choice for high-energy-demand scenarios, such as electric vehicles.
The cost of manufacturing LiFeMnPO4 batteries can be higher compared to certain lithium-ion batteries, affecting their widespread usage.
New Research
Surface Coatings and Functionalization
Researchers have explored various surface coatings to enhance the stability and reactivity of manganese-rich cathodes. Thin film coatings, chemical grafting, and protein immobilization are commonly used methods.
Achieving uniform and conformal coverage on electrode surfaces is critical for optimal sensor and biomedical applications.
Morphological and Structural Advancements
The performance of manganese-based cathodes is significantly influenced by their morphology and crystal structure.
Researchers have explored layered structures with adjustable interlayer spacing, enabling better lithium diffusion and increased capacity. Additionally, tunnel structures offer excellent rate capability and stability.
Integration of Manganese in Next-Generation Battery Technologies
Manganese is emerging as a promising metal for affordable and sustainable battery production, and manufacturers like Tesla and Volkswagen are exploring manganese-rich cathodes to reduce costs and improve scalability.
Volkswagen’s versatile “unified cell” design aims to use multiple cathode materials, including manganese, to achieve cost-effective and high-performance batteries.
Conclusion
Manganese continues to play a crucial role in advancing lithium-ion battery technology, addressing challenges, and unlocking new possibilities for safer, more cost-effective, and higher-performing energy storage solutions. ongoing research explores innovative surface coatings, morphological enhancements, and manganese integration for next-gen batteries. These developments aim to address challenges such as capacity fading, voltage fade, and manufacturing costs, fostering a sustainable, efficient, and environmentally friendly future.
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References and Further Reading
Li, H., Zhang, W., Sun, K., Guo, J., Yuan, K., Fu, J., Zhang, T., Zhang, X., Long, H., Zhang, Z., Lai, Y., & Sun, H. (2021). Manganese-Based Materials for Rechargeable Batteries beyond Lithium-Ion. Advanced Energy Materials. [Online] Available at: https://onlinelibrary.wiley.com/doi/full/10.1002/aenm.202100867.
Nunez, C. (2020, June 4). Researchers eye manganese as key to safer, cheaper lithium-ion batteries. Argonne National Laboratory. [Online] Available at: https://www.anl.gov/article/researchers-eye-manganese-as-key-to-safer-cheaper-lithiumion-batteries.
Kour, S., Tanwar, S., & Sharma, A. L. (2022). A review on challenges to remedies of MnO2 based transition-metal oxide, hydroxide, and layered double hydroxide composites for supercapacitor applications. Materials Today Communications. [Online] Available at: https://www.sciencedirect.com/science/article/abs/pii/S2352492822008868.
Capasso, C., Iannucci, L., Patalano, S., Veneri, O., & Vitolo, F. Battery Thermal Management Systems: A Case Study on Li-NMC storage systems for electric vehicles. [Online] Available at: https://ieeexplore.ieee.org/abstract/document/10114867.
Heng, Y.-L., Wu, X.-L., et al. (2022). Research progress on the surface/interface modification of high-voltage lithium oxide cathode materials. Energy Materials. [Online] Available at: https://www.oaepublish.com/articles/energymater.2022.18.
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