Amino Acid-Assisted Solvothermal Synthesis of LiFePO4 Cathode Materials

Document Type : UFGNSM Conference

Authors

School of Metallurgy & Materials Engineering, Iran University of Science and Technology (IUST), Narmak, Tehran, Iran.

Abstract

In the energy storage field, lithium-ion batteries were known to be the most important approach for mitigating the environmental impacts of fossil fuels. Cathode materials are the crucial part of a lithium-ion battery, and LiFePO4 (LFP) cathode material was selected for its high voltage (3.45 V vs. Li+/Li), high theoretical capacity (170 mAh.g-1), significant cyclic stability, and environmental friendliness. On the contrary, the main downside of LFP materials is their one-dimensional lithium-ion diffusion channel at the crystallographic direction of [010]. These channels can be blocked by antisite defects, plunging the specific capacity of LFP materials. Thus, in order to reduce such impacts, having sheet-like morphologies with a significant crystallographic plane of (010) is essential. A great deal of research has been performed using a solvothermal method for the synthesis of LFP materials, and factors - as precursors, pH of the solution, temperature, time, and additives - were known to have significant roles in the structural as well as electrochemical properties of LFP materials. In this study, different amounts of the amino acids, namely glycine, and glutamic acid, were introduced in the solvothermal synthesis of LFP materials, and their respective roles in morphology and electrochemical characteristics were investigated. The self-assembled morphology of LFP particles using glycine was discussed by the formation of peptide bonds. Additionally, having another carboxylic acid group in the molecular structure of glutamic acid sustained a low pH in the solvothermal solution; therefore, the formation of self-assembled morphology could not occur during the synthesis process. Additionally, the specific capacity of the LFP/C materials after the heat treatment was discussed by Rietveld refinement investigations for determining the antisite defects.

Keywords


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    1. Liu S, Kang L, Hu J, Jung E, Zhang J, Jun SC, et al. Unlocking the Potential of Oxygen-Deficient Copper-Doped Co3O4 Nanocrystals Confined in Carbon as an Advanced Electrode for Flexible Solid-State Supercapacitors. ACS Energy Letters. 2021;6(9):3011-9.
    2. Liu S, Kang L, Jun SC. Challenges and Strategies toward Cathode Materials for Rechargeable Potassium‐Ion Batteries. Advanced Materials. 2021;33(47):2004689.
    3. Andre D, Kim S-J, Lamp P, Lux SF, Maglia F, Paschos O, et al. Future generations of cathode materials: an automotive industry perspective. Journal of Materials Chemistry A. 2015;3(13):6709-32.
    4. Liu S, Kang L, Zhang J, Jun SC, Yamauchi Y. Carbonaceous Anode Materials for Non-aqueous Sodium- and Potassium-Ion Hybrid Capacitors. ACS Energy Letters. 2021;6(11):4127-54.
    5. Liu S, Kang L, Zhang J, Jung E, Lee S, Jun SC. Structural engineering and surface modification of MOF-derived cobalt-based hybrid nanosheets for flexible solid-state supercapacitors. Energy Storage Materials. 2020;32:167-77.
    6. Sławiński WA, Playford HY, Hull S, Norberg ST, Eriksson SG, Gustafsson T, et al. Neutron Pair Distribution Function Study of FePO4 and LiFePO4. Chemistry of Materials. 2019;31(14):5024-34.
    7. Manthiram A. An Outlook on Lithium Ion Battery Technology. ACS Cent Sci. 2017;3(10):1063-9.
    8. Malik R, Burch D, Bazant M, Ceder G. Particle Size Dependence of the Ionic Diffusivity. Nano Letters. 2010;10(10):4123-7.
    9. Eftekhari A. LiFePO4/C nanocomposites for lithium-ion batteries. Journal of Power Sources. 2017;343:395-411.
    10. Sharikov FY, Drozhzhin OA, Sumanov VD, Baranov AN, Abakumov AM, Antipov EV. Exploring the Peculiarities of LiFePO4 Hydrothermal Synthesis Using In Situ Calvet Calorimetry. Crystal Growth & Design. 2018;18(2):879-82.
    11. Jiang Y, Tian R, Liu H, Chen J, Tan X, Zhang L, et al. Synthesis and characterization of oriented linked LiFePO4 nanoparticles with fast electron and ion transport for high-power lithium-ion batteries. Nano Research. 2015;8(12):3803-14.
    12. Benedek P, Wenzler N, Yarema M, Wood VC. Low temperature hydrothermal synthesis of battery grade lithium iron phosphate. RSC Advances. 2017;7(29):17763-7.
    13. Huang X, Zhang K, Liang F, Dai Y, Yao Y. Optimized solvothermal synthesis of LiFePO4 cathode material for enhanced high-rate and low temperature electrochemical performances. Electrochimica Acta. 2017;258:1149-59.
    14. Cho M-Y, Kim H, Kim H, Lim YS, Kim K-B, Lee J-W, et al. Size-selective synthesis of mesoporous LiFePO4C microspheres based on nucleation and growth rate control of primary particles. J Mater Chem A. 2014;2(16):5922-7.
    15. Chen M-m, Ma Q-q, Wang C-y, Sun X, Wang L-q, Zhang C. Amphiphilic carbonaceous material-intervened solvothermal synthesis of LiFePO4. Journal of Power Sources. 2014;263:268-75.
    16. Fischer MG, Hua X, Wilts BD, Castillo-Martínez E, Steiner U. Polymer-Templated LiFePO4C Nanonetworks as High-Performance Cathode Materials for Lithium-Ion Batteries. ACS Applied Materials & Interfaces. 2018;10(2):1646-53.
    17. Zhao Y, Peng L, Liu B, Yu G. Single-Crystalline LiFePO4 Nanosheets for High-Rate Li-Ion Batteries. Nano Letters. 2014;14(5):2849-53.
    18. Li W, Wei Z, Huang L, Zhu D, Chen Y. Plate-like LiFePO 4 /C composite with preferential (010) lattice plane synthesized by cetyltrimethylammonium bromide-assisted hydrothermal carbonization. Journal of Alloys and Compounds. 2015;651:34-41.
    19. Martinez PS, Lima E, Ruiz F, Curiale J, Moreno MS. Morphology and Electrochemical Response of LiFePO4 Nanoparticles Tuned by Adjusting the Thermal Decomposition Synthesis. The Journal of Physical Chemistry C. 2018;122(33):18795-801.
    20. Zhu J, Fiore J, Li D, Kinsinger NM, Wang Q, DiMasi E, et al. Solvothermal Synthesis, Development, and Performance of LiFePO4 Nanostructures. Crystal Growth & Design. 2013;13(11):4659-66.
    21. Sarmadi A, Masoudpanah SM, Alamolhoda S. L-Lysine-assisted solvothermal synthesis of hollow-like structure LiFePO4/C powders as cathode materials for Li-ion batteries. Journal of Materials Research and Technology. 2021;15:5405-13.
    22. Toby BH, Von Dreele RB. GSAS-II: the genesis of a modern open-source all purpose crystallography software package. Journal of Applied Crystallography. 2013;46(2):544-9.
    23. Whittingham MS. Ultimate Limits to Intercalation Reactions for Lithium Batteries. Chemical Reviews. 2014;114(23):11414-43.
    24. Liu Y, Zhang J, Li Y, Hu Y, Li W, Zhu M, et al. Solvothermal Synthesis of a Hollow Micro-Sphere LiFePO₄/C Composite with a Porous Interior Structure as a Cathode Material for Lithium Ion Batteries. Nanomaterials (Basel). 2017;7(11):368.
    25. Lu Z, Chen H, Robert R, Zhu BYX, Deng J, Wu L, et al. Citric Acid- and Ammonium-Mediated Morphological Transformations of Olivine LiFePO4 Particles. Chemistry of Materials. 2011;23(11):2848-59.