Lithium hybrid organic battery

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Lithium hybrid organic batteries are an energy storage device that combines lithium with an organic polymer. For example, polyaniline vanadium (V) oxide (PAni/V2O5) can be incorporated into the nitroxide-polymer lithium iron phosphate battery, PTMA/LiFePO4. Together, they improve the lithium ion intercalation capacity, cycle life, electrochemical performances, and conductivity of batteries.

Contents

PAni/V2O5

Oxides, like V2O5, are used as cathodes in rechargeable lithium batteries. Crystalline V2O5 has a weaker rechargeability or cyclability than amorphous V2O5 because the crystal structure is damaged during discharge/charge cycles. [1] However, amorphous oxides, in particular the V2O5 xerogel, allows lithium ions to diffuse faster and thus have a better cyclability. Hybrid is formed by combining a conducting organic polymer (e.g. polyaniline) with an oxide (e.g. V2O5).

Figure 1: Diagram of charging and discharging of hybrid battery First Figure.png
Figure 1: Diagram of charging and discharging of hybrid battery
Figure 3: Exact protocol for V2O5 gels Third Figure.png
Figure 3: Exact protocol for V2O5 gels
Figure 2: Polyaniline/V2O5, where V2O5 is represented in black and polyaniline is represented in red Second Figure.png
Figure 2: Polyaniline/V2O5, where V2O5 is represented in black and polyaniline is represented in red

V2O5 gels are prepared using the ion-exchange method. [2] Vanadium (V) polymerizes aniline. Before synthesis of a hybrid battery, potentiometric titration of V2O5 gel with is carried out; this determines the amount of V(V) present in the gel. Aniline solution is slowly added onto the gel. The following procedure is demonstrated in Figure 3.

V2O5 is used because of its high specific capacity, high thermal stability, and high structural flexibility with lithium. [3] Up to three moles of lithium ions can be added into the V2O5 lattice to create different structures. [4] The structures created give the hybrid a long battery life. However, the intercalation capacity depends on the moderate electrical conductivity and low diffusion coefficient of the lithium ions in the vanadium oxide matrix. [5]

Polyaniline is easily produced to have controlled structural and electronic properties. [6] Polyaniline eliminates the coordinated water of the V2O5 xerogel, so more lithium ions can be integrated into the structure. The organic part of the PAni/V2O5 hybrid degrades with the increase of temperature. [7]

V(V) is reduced to V(IV), and aniline is oxidized to polyaniline. [8] Re-oxidizing V(IV) to a higher oxidation state of V(V) increases initial cell voltage and specific capacity. Since polyaniline is an electrochemically active component, it improves the specific charge of the hybrid material.[ citation needed ] Combining polyaniline with V2O5 yields a larger specific charge difference. Thus, a greater total capacity contribution than V2O5 alone. Furthermore, the hybrid has a higher specific capacity than that of the V2O5 xerogel. Electrical conductivity is as high as 0.09 S/cm for 15 days. [9]

As a result, PAni/V2O5 hybrid is a conducting network and an electroactive material in the composites, which improves electrochemical behavior. It also prevents the irreversible structural changes made by redox cycling when the lithium ions enter the lattice. Moreover, this hybrid also has a high specific capacity and improved cyclability without capacity deterioration.

PTMA/LiFePO4

PTMA is an organic nitroxide radical electrode-active polymer, and LiFePO4 is the inorganic electrode-active material. PTMA is used because it has a high capacity and a long cycle life. [10] To synthesize organic radical-inorganic hybrid electrodes, electrode environments for each component must be optimized. PTMA and LiFePO4 were combined with entire PTMA and LiFePO4 electrode with different weight ratios: 25/75, 50/50, and 75/25. [11]

Figure 4: Synthesis of PTMA- MTMP monomer (2,2,6,6-tetramethylpiperidine methacrylate) Fourth Figure.png
Figure 4: Synthesis of PTMA- MTMP monomer (2,2,6,6-tetramethylpiperidine methacrylate)

The cell was prepared by using a working electrode to assemble a half-cell configuration dry glove box with Li metal as an anode, ethyl carbonate/dimethyl carbonate as an electrophile, and a Celgard 3501 membrane as a separator. Using Arbin BT-200 Battery Tester, the cell was electrochemically cycled at room temperature. By using a Solarton workstation, the cyclic voltammetry and electrochemical impedance spectroscopy of cells were performed. A focus ion beam-scanning electron microscope was used to determine the morphology of the electrodes before and after the high rate pulse discharge (HRPD) cycling. [12]

After testing, pure PTMA and LiFePO4 electrode give a sharp redox peak and decrease the voltage gap between oxidation and reduction. [13] Therefore, PTMA and LiFePO4 improve the rate and reversibility of the redox couples. Furthermore, the hybrid cathodes have a lower charge-transfer resistance, allowing easier migration of Li ions through the electrode interface. Moreover, PTMA/LiFePO4 has a longer life cycle compared to pure LiFePO4 or PTMA systems.

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A lithium-ion or Li-ion battery is a type of rechargeable battery that uses the reversible intercalation of Li+ ions into electronically conducting solids to store energy. In comparison with other commercial rechargeable batteries, Li-ion batteries are characterized by higher specific energy, higher energy density, higher energy efficiency, a longer cycle life, and a longer calendar life. Also noteworthy is a dramatic improvement in lithium-ion battery properties after their market introduction in 1991: over the following 30 years, their volumetric energy density increased threefold while their cost dropped tenfold.

<span class="mw-page-title-main">Lithium polymer battery</span> Lithium-ion battery using a polymer electrolyte

A lithium polymer battery, or more correctly, lithium-ion polymer battery, is a rechargeable battery of lithium-ion technology using a polymer electrolyte instead of a liquid electrolyte. Highly conductive semisolid (gel) polymers form this electrolyte. These batteries provide higher specific energy than other lithium battery types. They are used in applications where weight is critical, such as mobile devices, radio-controlled aircraft, and some electric vehicles.

<span class="mw-page-title-main">M. Stanley Whittingham</span> British-American chemist

Sir Michael Stanley Whittingham is a British-American chemist. He is a professor of chemistry and director of both the Institute for Materials Research and the Materials Science and Engineering program at Binghamton University, State University of New York. He also serves as director of the Northeastern Center for Chemical Energy Storage (NECCES) of the U.S. Department of Energy at Binghamton. He was awarded the Nobel Prize in Chemistry in 2019 alongside Akira Yoshino and John B. Goodenough.

<span class="mw-page-title-main">Lithium iron phosphate battery</span> Type of rechargeable battery

The lithium iron phosphate battery or LFP battery is a type of lithium-ion battery using lithium iron phosphate as the cathode material, and a graphitic carbon electrode with a metallic backing as the anode. Because of their low cost, high safety, low toxicity, long cycle life and other factors, LFP batteries are finding a number of roles in vehicle use, utility-scale stationary applications, and backup power. LFP batteries are cobalt-free. As of September 2022, LFP type battery market share for EVs reached 31%, and of that, 68% were from EV makers Tesla and BYD alone. Chinese manufacturers currently hold a near monopoly of LFP battery type production. With patents having started to expire in 2022 and the increased demand for cheaper EV batteries, LFP type production is expected to rise further and surpass lithium nickel manganese cobalt oxides (NMC) type batteries in 2028.

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<span class="mw-page-title-main">Nanobatteries</span> Type of battery

Nanobatteries are fabricated batteries employing technology at the nanoscale, particles that measure less than 100 nanometers or 10−7 meters. These batteries may be nano in size or may use nanotechnology in a macro scale battery. Nanoscale batteries can be combined to function as a macrobattery such as within a nanopore battery.

<span class="mw-page-title-main">Lithium iron phosphate</span> Chemical compound

Lithium iron phosphate or lithium ferro-phosphate (LFP) is an inorganic compound with the formula LiFePO
4
. It is a gray, red-grey, brown or black solid that is insoluble in water. The material has attracted attention as a component of lithium iron phosphate batteries, a type of Li-ion battery. This battery chemistry is targeted for use in power tools, electric vehicles, solar energy installations and more recently large grid-scale energy storage.

<span class="mw-page-title-main">Lithium-ion capacitor</span> Hybrid type of capacitor

A lithium-ion capacitor is a hybrid type of capacitor classified as a type of supercapacitor. It is called a hybrid because the anode is the same as those used in lithium-ion batteries and the cathode is the same as those used in supercapacitors. Activated carbon is typically used as the cathode. The anode of the LIC consists of carbon material which is often pre-doped with lithium ions. This pre-doping process lowers the potential of the anode and allows a relatively high output voltage compared to other supercapacitors.

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<span class="mw-page-title-main">Sodium-ion battery</span> Type of rechargeable battery

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A lithium ion manganese oxide battery (LMO) is a lithium-ion cell that uses manganese dioxide, MnO
2
, as the cathode material. They function through the same intercalation/de-intercalation mechanism as other commercialized secondary battery technologies, such as LiCoO
2
. Cathodes based on manganese-oxide components are earth-abundant, inexpensive, non-toxic, and provide better thermal stability.

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<span class="mw-page-title-main">Pseudocapacitance</span> Storage of electricity within an electrochemical cell

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<span class="mw-page-title-main">History of the lithium-ion battery</span> Overview of the events of the development of lithium-ion battery

This is a history of the lithium-ion battery.

References

  1. Ng, S. H., Chew, S. Y., Wang, J., Wexler, D., Tournayre, Y., Konstantinov, K., & Liu, H. K. (2007). Synthesis and electrochemical properties of V 2 O 5 nanostructures prepared via a precipitation process for lithium-ion battery cathodes. Journal of Power Sources, 174(2), 1032-1035.
  2. Liu, D., Liu, Y., Garcia, B. B., Zhang, Q., Pan, A., Jeong, Y. H., & Cao, G. (2009). V2O5 xerogel electrodes with much enhanced lithium-ion intercalation properties with N 2 annealing. Journal of Materials Chemistry, 19(46), 8789-8795. doi:10.1039/b914436f.
  3. Chao, D., Xia, X., Liu, J., Fan, Z., Ng, C. F., Lin, J., ... & Fan, H. J. (2014). A V2O5/Conductive‐Polymer Core/Shell Nanobelt Array on Three‐Dimensional Graphite Foam: A High‐Rate, Ultrastable, and Freestanding Cathode for Lithium‐Ion Batteries. Advanced Materials, 26(33), 5794-5800. doi:10.1002/adma.201400719.
  4. Swider-Lyons, K. E., Love, C. T., & Rolison, D. R. (2002). Improved lithium capacity of defective V2O5 materials. Solid State Ionics, 152, 99-104. doi:10.1016/S0167-2738(02)00350-8.
  5. Li, G., Lu, Z., Huang, B., Huang, H., Xue, R., & Chen, L. (1995). An evaluation of lithium intercalation capacity into carbon by XRD parameters. Solid state ionics, 81(1), 15-18. doi:10.1016/0167-2738(95)00166-4.
  6. Molapo, K. M., Ndangili, P. M., Ajayi, R. F., Mbambisa, G., Mailu, S. M., Njomo, N., ... & Iwuoha, E. I. (2012). Electronics of conjugated polymers (I): polyaniline.International Journal of Electrochemical Science, 7(12).
  7. Lira-Cantu, M., Gomez-Romero, P. (1999), The Organic-Inorganic Polyaniline/V2O5 System: Application as a High Capacity Hybrid Cathode for Rechargeable Lithium Batteries. Journal of the Electrochemical Society, 146(6): 2029-2033. doi:10.1149/1.1391886.
  8. Lira-Cantu, M., Gomez-Romero, P. (1999), The Organic-Inorganic Polyaniline/V2O5 System: Application as a High Capacity Hybrid Cathode for Rechargeable Lithium Batteries. Journal of the Electrochemical Society, 146(6): 2029-2033. doi:10.1149/1.1391886.
  9. Park, K., Song, H., Kim, Y., Mho, S., Cho, W., and Yeo. I. (2009), Electrochemical Preparation and Characterization of V2O5 / Polyaniline composite Film Cathodes for Li Battery. Electrochimica Acta: Emerging Trends and Challenges in Electrochemistry, 55(27): 8023-8029. doi:10.1016/j.electacta.2009.12.047.
  10. Guo, W., Yin, Y., Xin, S., Guo Y., and Wan, L. (2011), Superior Radical Polymer Cathode Material with a Two-electron Process Redox Reaction Promoted by Graphene. Energy and Environmental Science, 5(1): 5221-5225. doi: 10.1039/c1ee02148f.
  11. Huang, Q., Cosimbescu, L., Koech, P., Choi, D., and Lemmon, J. (2013), Composite Organic Radical-Inorganic Hybrid Cathode for Lithium-Ion Batteries. Journal of Power Sources, 233(3): 69-73. doi:10.1016/j.jpowsour.2013.01.076.
  12. Huang, Q., Cosimbescu, L., Koech, P., Choi, D., and Lemmon, J. (2013), Composite Organic Radical-Inorganic Hybrid Cathode for Lithium-Ion Batteries. Journal of Power Sources, 233(3): 69-73. doi:10.1016/j.jpowsour.2013.01.076.
  13. Vlad, A., Singh, N., Rolland, J., Melinte, S., Ajayan, P. M., & Gohy, J. F. (2014). Hybrid supercapacitor-battery materials for fast electrochemical charge storage.Scientific reports, 4. doi:10.1038/sren04315.