Excellent electrochemical performance of LiFe0.4Mn0.6PO4 microspheres produced using a double carbon coating process

Composite LiFe0.4Mn0.6PO4/C microspheres are considered advanced cathode materials for electric vehicles and other high-energy density applications due to their advantages of high energy density and excellent cycling stability. LiFe0.4Mn0.6PO4/C microspheres have been produced using a double carbon coating process employing traditional industrial techniques (ball milling, spray-drying and annealing). The obtained LiFe0.4Mn0.6PO4 microspheres exhibit a high discharge capacity of around 166 mA h g-1 at 0.1 C and excellent rate capabilities of 132, 103, and 72 mA h g-1 at 5, 10, and 20 C, respectively. A reversible capacity of about 152 mA h g-1 after 500 cycles at a current density of 1 C indicates an outstanding cycling stability. The excellent electrochemical performance is attributed to the micrometer-sized spheres of double carbon-coated LiFe0.4Mn0.6PO4 nanoparticles with improved electric conductivity and higher Li ion diffusion coefficients, ensuring full redox reactions of all nanoparticles. The results show that the advanced high-energy density cathode materials can be produced using existing industry techniques.

Effect of different carbon-coating ways on the microstructure and electrochemical performance of LiFePO4/C cathodes

Through comparative studying on LiFePO4/C preparation process of adding carbon source in precursor and pre-sintered material, marked as LFP-1 (in-situ carbon coating) and LFP-2 respectively, by means of C-S test, XRD, SEM, BET, Raman, the effects of carbon content, morphology, particle size and surface carbon structure on the electrochemical performance of LiFePO4/C cathodes were investigated. SEM images showed that particle sizes of LFP-1 and LFP-2 are about 10μm and 100nm respectively. The EIS and galvnostatic charge-discharge tests indicated that LFP-1 has lower charge transfer resistance (Rct), better rate and cycle performance than that of LFP-2, which can be attributed to the different microstructure and the higher degree of graphitized carbon of LiFePO4/C. Raman spectroscopic analysis showed that the ratio of the ID/IG and Asp3/Asp2 of LFP-1 is lower that of LFP-2, which means the degree of graphitized carbon of LFP-1 is higher than that of LEP-2. These results have important significance for improving the overall performance of olivine cathode materials for lithium ion batteries.

Electrochemical performance of LiFe1-xMnxPO4/C materials prepared by ball milling

LiFe1-xMnxPO4/C composite materials as cathode materials in Li-ion batteries have been synthesised and their electrochemical properties have been investigated. The samples were synthesised by using high energy ball milling of commercially available precursors (Li2C2O4, FeC2O4.2H2O, MnC2O4.2H2O, NH4H2PO4) and then heated at 600°C. The morphology and structure of the heated samples were analysed by means of SEM and X-ray diffraction. The olivine structure of the LiFe1-xMnxPO4/C composite was obtained. A slight shift of the peaks to smaller 2θ angles with the increasing Mn/Fe ratios is observed due to the increase in lattice parameters. The influence of different Mn/Fe ratios on electrical and electrochemical performances were studied by charge-discharge and cyclic voltammetry (CV) testing. The CV curves of the pure LiFePO4 and LiMnPO4 show the expected Fe2+/Fe3+ peak around 3·5 V and Mn2+/Mn3+ peak around 4·1 V, respectively. The addition of manganese increases the discharge voltage from 3·5 to 4·1 V.

Effect of sintering temperature on electrochemical performance of LiFe0·4Mn0·6PO4/C cathode materials

Carbon coated LiFe0·4Mn0·6PO4 (LiFe0·4Mn0·6PO4/C) was synthesised using high energy ball milling and annealing processes. The starting materials of Li2C2O4, FeC2O4.2H2O, MnC2O4.2H2O, NH4H2PO4 were firstly milled for 40 h, and followed by further milling for 5 h after adding glucose solution. The milled sample was heated at different temperatures (550, 600, 650 and 700°C) for 10 h to produce LiFe0·4Mn0·6PO4/C composites. The structure and morphology of the samples were investigated using X-ray diffraction, field emission scanning electron microscopy, and high resolution electron microscopy. The phase of samples annealed at 550 and 600°C mainly consists of olivine type LiFePO4, but a small amount of Fe2P impurity phase is formed in the samples annealed at 650 and 700°C. Electrochemical analysis results show that LiFe0·4Mn0·6PO4/C synthesised at 600°C exhibits the best performance with the initial discharge capacity of 128 mAh g-1 at 0·1 C, and 109 mAh g-1 at 1 C after 500 cycles. The LiFe0·4Mn0·6PO4/C exhibits excellent electrochemical properties for high energy density lithium ion batteries.