Li Fe PO4/C was prepared via solid state reaction and characterized with X-ray powder diffraction and charge–discharge test. As-prepared Li Fe PO4/C has a triphylite structure and exhibits an excellent rate capability and capacity retention. Electrochemical impedance spectroscopy(EIS) was applied to investigate LixFe PO4/C(0
The influence of sintering temperature, carbon content and dispersive agent in bail-milling was investigated on the properties of LiFePO4/C prepared using Fe2O3, NH4H2PO4, Li2CO3 and glucose via solid state reaction. X-ray powder diffraction, scanning electron microscopy and charge-discharge test were applied to the characterization of the LiFePO4/C samples synthesized under different conditions. Sintering temperature affects the crystallite/ particle size and degree ofcrystallinity of LiFePO4, formation of Fe2P and maintenance of carbon in LiFePO4/C. Car- bon maintenance is favored by low sintering temperature, and 700 ℃ is optimum for synthesis of LiFePO4/C with superior electrochemical performance. A higher carbon content in the range of 4.48%-11.03% results in a better rate capability for LiFePO4/C. The dispersive agent used in ball-milling impacts the existent state of carbon in the final product which subsequently determines its charge-discharge behavior. The sample prepared at 700 ℃ by using acetone as the dispersive agent in ball-milling exhibits an excellent rate capability and capacity retention without any fade at 0.1 C, 1C and 2C, with corresponding average discharge capacities of 153.8, 128.3 and 121.0 mA·h·g-1. rest2ectivelv, in the first 50 cvcles.
A novel synthesis of LiFePO4/C from Fe2O3 with no extra carbon or carbon-containing reductant was introduced： Fe2O3 （＋NH4H2PO4）→Fe2P2O7（＋Li2CO3＋glucose）→LiFePO4/C. X-ray diffractometry （XRD）, Fourier transform infrared spectroscopy （FTIR） and scanning electron microscopy （SEM） were utilized to characterize relevant products obtained in the synthetic procedure. The reaction of Fe2P2O7 and Li2CO3 was investigated by thermo-gravimetric and differential thermal analysis （TGA-DTA）. Fe2O3 is completely reduced to Fe2P2O7 by NH4H2PO4 at 700 ℃ and Fe2P2O7 fully reacts with Li2CO3 to form LiFePO4 in the temperature range of 663.4-890 ℃. The primary particles of LiFePO4/C samples prepared at 670, 700 and 750 ℃ respectively exhibit uniform morphology and narrow size distribution, 0.5-3 μm for those obtained at 670 and 700 ℃ and 0.5-5 μm for those obtained at 750 ℃. LiFePO4/C （carbon content of 5.49%, mass fraction） made at 670 ℃ shows an appreciable average capacity of 153.2 mA·h/g at 0.1C in the first 50 cycles.
LiNi0.8Co0.1Mn0.1O2 cathode was synthesized using transition metal acetates under different synthesis conditions. Simultaneous thermogravimetric–differential scanning calorimetry–derivative thermogravimetric analysis was applied to investigating the mixture of transition metal acetates. X-ray powder diffraction and charge–discharge test were adopted to characterize the as-prepared LiNi0.8Co0.1Mn0.1O2. The mixture of transition metal acetates undergoes dehydration and decomposition during heating. All the examined LiNi0.8Co0.1Mn0.1O2 samples have a layered structure with R3 m space group. LiNi0.8Co0.1Mn0.1O2 samples prepared with different lithium sources under different synthesis conditions exhibit very different charge–discharge performances. The sample synthesized via the procedure of sintering at 800 °C after heating lithium carbonate and transition metal acetates at 550 °C achieves a highest capacity of 200.8 m A·h/g and an average capacity of 188.1 mA ·h/g in the first 20 cycles at 0.2C.
The anoxic decomposition and influence of carbon precursors on the properties of LiFePO_4/C prepared by using Fe_2O_3 were investigated.X-ray powder diffractometry,Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM) and carbon content and charge–discharge tests were applied to the characterization of the as-synthesized cathodes.Partial carbon is lost in the anaerobic decomposition of organic precursors and a high hydrogen content leads to a high residual carbon rate.Pyromellitic anhydride and citric acid participate in reactions before and in ball-milling.All the chosen carbon precursors are capable of producing LiFePO_4 with high degree of crystallinity and purity.The carbon derived from α-D-glucose,pyromellitic anhydride,soluble starch,citric acid and polyacrylamide has a loose and porous texture in LiFePO_4/C which forms conduction on and between LiFePO_4 particles.LiFePO_4/C prepared by using α-D-glucose,pyromellitic anhydride,citric acid and sucrose exhibits appreciable electrochemical performance.Graphite alone is able to enhance the electrochemical performance of LiFePO_4 to a limited extent but incapable of preparing practical cathode.
A facile and practical route was introduced to prepare LiFePO4/C cathode material with nano-sized primary particles and excellent electrochemical performance. LiH2PO4 was synthesized by using H3PO4 and LiOH as raw materials. Then, as-prepared LiH2PO4, reduced iron powder andα-D-glucose were ball-milled, dried and sin-tered to prepare LiFePO4/C. X-ray diffractometry was used to characterize LiH2PO4, ball-milled product and LiFePO4/C. Differential scanning calorimeter-thermo gravimetric analysis was applied to investigate possible reac-tions in sintering and find suitable temperature for LiFePO4 formation. Scanning electron microscopy was em-ployed for the morphology of LiFePO4/C. As-prepared LiH2PO4 is characterized to be in P21cn（33） space group, which reacts with reduced iron powder to form Li3PO4, Fe3（PO4）2 and H2 in ball-milling and sintering. The appro-priate temperature for LiFePO4/C synthesis is 541.3-976.7 ℃. LiFePO4/C prepared at 700 ℃ presents nano-sized primary particles forming aggregates. Charge-discharge examination indicates that as-prepared LiFePO4/C displays appreciable discharge capacities of 145 and 131 mA·h·g^-1 at 0.1 and 1 C respectively and excellent discharge ca-pacity retention.
