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Lithium iron phosphate cathode material for the synthesis and modification of polymer -coated
Author: ZuoYi
Tutor: TangXinCun
School: Central South University
Course: Polymer Chemistry and Physics
Keywords: cathode material solvothermal LiFePO4 sphere PPy
CLC: TM912
Type: Master's thesis
Year: 2011
Downloads: 360
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Abstract
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Lithium ion batteries are favorable because of the properties of high voltage, high energy density, long cycling life, little local action, non-memory effect and pollution-free. Olivine LiFePO4 is acknowledged to be the most promising cathode material in HEV for its high theoretical capacity, brillianit cyele stability, cost effective raw materials and non-toxicity. But the low eleetrical conduetivity and low tap-density obstructs its’proeess of commereialization. To cope with this problem, researchers try to improve the eleetrochemical properties and enhance the tap-density of LiFePO4 powders. Aiming at solving the problem mentioned above, we started works as the follows:(1) The olivine lithium ion phosphate (LiFePO4) was prepared via solvothermal reaction using ethanol, ethylene glycol(EG), and glycerol-water as solvents respectively. The crystalline structure, particle morphology, and surface microstructure were characterized by high-energy synchrotron XRD, SEM and FTIR spectroscopy. The effects of different solvents on the morphologies and structurtes were investigated in detail. The electrochemical properties were also investigated by charge/discharge test, cyclic voltammetry (CV). The results showed that LiFePO4 nanosheet obtained by using EG as solvent has smaller size, thin features, such a structure reduced the lithium ion diffusion distance and favors the improvement of electrochemical performance. It can deliver a initial discharge capacities of 161.5mAh·g-1 at 0.1 C,132.6mAh·g-1 at 1C and the cycling capacity retention rate reaches 98.02% over 50 cycles at 0.1C.(2) LiFePO4 sphere with hierarchical microstructure self-assembled by nanoplates has been successfully synthesized via a low-temperature solvothermal reaction followed by high-temperature treatment. These resulting sphere show a uniform size distribution of~8um and are hierarchically constructed with two-dimensional nanoplates with~20nm thicknesses, while these tiny plates are densely aggregated in an ordered fashion. The hierarchical structure gives a relatively high tap density of 1.6g.cm-3, and simultaneously, the primary nanoplates could provide a huge electrochemically available surface for enhancing the rate capability of the lithium insertion/deinsertion reaction.The presence of urea and citric play an important role in the formation of nanoplates and construction of hierarchically self-assembled microsphere. A reasonable formation mechanism is proposed on the basis of the result of time-dependent experiments. The materials’ physical properties were further characterized by SEM, TEM, XRD, BET and Raman spectroscopy. The charge-discharge test showed that the hierarchical microspheres as a cathode-active material demonstrated high reversible capacity (93.6mAh·g-1 at 10C) and excellent cycle stability.(3) A simple chemical oxidative polymerization of pyrrole directly onto the surface of LiFePO4 particles was applied to the synthesis of polypyrrole-LiFePO4 (PPy-LiFePO4) powder. The LiFePO4 sample without carbon coating was synthesized by a solvothermal method. The dodecyl benzenesulfonic acid, sodium salt (SDBS) was used as additive during PPy polymerization for improving the homogeneous distribution of the coating and conductivity of PPy-LiFePO4. Physical properties of resulting LiFePO4, PPy-LiFePO4 and PPy/SDBS-LiFePO4 were characterized by XRD, SEM, TG. The electrochemical behavior of the samples was examined against lithium counter electrode by galvanostatic charge/discharge measurements. Carbon-free LiFePO4 coated with PPy/SDBS hybrid film exhibited good electrode kinetics and a stable discharge capacity of 142.7mAh·g-1 at 0.1C. Impedance measurements showed that the PPy/SDBS coating decreased the charge-transfer resistance of the corresponding LiFePO4 cathode material very effectively, which was attributed to a homogeneous coating and doped effction.
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