Microwave-assisted polyol synthesis of LiMnPO4/C and its use as a cathode material in lithium-ion batteries

We synthesized LiMnPO4/C with an ordered olivine structure by using a microwave-assisted polyol process in 2：15 （v/v） water-diethylene glycol mixed solvents at 130℃ for 30min. We also studied how three surfactants-hexadecyltrimethylammonium bromide, polyvinylpyrrolidone k30 （PVPk30）, and polyvinylpyrrolidone k90 （PVPk90）-affected the structure, morphology, and performance of the prepared samples, characterizing them by using X-ray diffraction, scanning electron microscopy, trans- mission electron microscopy, charge/discharge tests, and electrochemical impedance spectroscopy. All the samples prepared with or without surfactant had orthorhombic structures with the Pnmb space group. Surfactant molecules may have acted as crystal-face inhibitors to adjust the oriented growth, morphol- ogy, and particle size of LiMnPO4. The microwave effects could accelerate the reaction and nucleation rates of LiMnPO4 at a lower reaction temperature. The LiMnPO4/C sample prepared with PVPk30 exhib- ited a flaky structure coated with a carbon layer （-2 nm thick）, and it delivered a discharge capacity of 126 mAh/g with a capacity retention ratio of -99.9% after 50 cycles at 1C. Even at 5C, this sample still had a high discharge capacity of 110 mAh/g, demonstrating good rate performance and cycle performance. The improved performance of LiMnPO4 likely came from its nanoflake structure and the thin carbon layer coating its LiMnPO4 particles. Compared with the conventional polyol method, the microwave-assisted polyol method had a much lower reaction time.

Influence of cerium doping on structure and electrochemical properties of LiNi0.5Mn1.5O4 cathode materials

Pristine LiNi_（0.5）Mn_（1.5）O_4 and cerium doped LiCe_xNi_（0.5–x）Mn_（1.5）O_4（x=0.005, 0.01, 0.02） cathode materials were synthesized by solid-state method. The effect of Ce doping content on structure and electrochemical properties of LiNi_（0.5）Mn_（1.5）O_4 cathode material was systematically investigated. The samples were characterized by X-ray diffraction（XRD）, Fourier transformation infrared spectrometer（FT-IR）, scanning electron microscopy（SEM）, electrochemical impedance spectroscopy（EIS）, cyclic voltammetry（CV） and constant-current charge/discharge tests. The results showed that Ce doping did not change the cubic spinel structure with Fd3m space group, but effectively restrained the formation of Li_xNi_（1–x）O impurity phase. Appropriate Ce doping（x=0.005） could decrease the extent of confusion between lithium ions and transition metal ions, increase the lattice parameter and Ni/Mn disordering degree（Mn^（3＋） content）. The synergic effects of the above factors led to the optimal electrochemical performance of LiCe_（0.005）Ni_（0.495）Mn_（1.5）O_4 sample. The discharge capacity at 10 C rate could reach 115.4 mAh/g, 94.82% of that at 0.2C rate, and the capacity retention rate after 100 cycles at 1C rate could reach 94.51%. However, heavier Ce doping had an adverse effect on the electrochemical properties, which might be due to the lower disordering degree and existence of more CeO_2 secondary phase.

Nanocomposite LiFePO_4·Li_3V_2(PO_4)_3/C synthesized by freeze-drying assisted sol-gel method and its magnetic and electrochemical properties

Nano-sized LiFePO_4·Li_3V_2（PO_4）_3/C was synthesized via a sol-gel route combining with freeze-drying. X-ray diffraction results show that this composite mainly consists of olivine Li Fe PO4 and monoclinic Li3 V2（PO4）3 phases with small amounts of V-doped LiFePO_4 and Fe-doped Li_3V_2（PO_4）_3. The magnetic properties of LiFePO_4·Li_3V_2（PO_4）_3/C are significantly different from LiFePO_4/C. Trace quantities of ferromagnetic impurities and Fe_2P are verified in LiFePO_4/C and LiFePO_4·Li_3V_2（PO_4）_3/C by magnetic tests, respectively. LiFePO_4·Li_3 V_2（PO_4）_3/C possesses relatively better rate capacities and cyclic stabilities, especially at high charge-discharge rates.The initial discharge capacities are 136.4 and 130.0 mA h g^（-1）,and the capacity retentions are more than 98% after 100 cycles at 2C and 5C, respectively, remarkably better than those of LiFePO_4/C. The excellent electrochemical performances are ascribed to the mutual doping of V^（3＋）and Fe^（2＋）, complementary advantages of LiFePO_4 and Li_3V_2（PO_4）_3 phases, the residual high-ordered carbon and Fe_2P with outstanding electric conductivity in the nanocomposite.

Pressure-induced polymerization of butyndioic acid and its Li^＋ salt

Conductive organic polymers with carbonyl groups are considered as potential cathode materials of the Li^＋ battery. Driven by extremely high pressure, 2-butyndioic acid and its Li~＋ salt polymerize at around 4 and 10 GPa, respectively, which demonstrates that pressure-induced polymerization is a robust method for synthesizing substituted polyacetylene-like conductors.