Preparation of spherical spinel LiCr_(0.04)Mn_(1.96)O_4 cathode materials based on the slurry spray drying method

Regular spherical chromium doped spinel lithium manganese oxides （LiCr0.04Mn1.96O4） with an average particle size of about 20μm were prepared by the slurry spray drying process. The materials were compared with non-spherical LiCr0.04Mnl.96O4 materials prepared by the common drying process, and all materials were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, laser particle analyzer and Brunaner-Emmett-Teller （BET） specific surface area test. Electrochemical performances of these cathode materials were studied by cyclic voltammetry （CV）, electrochemical impedance spectroscopy （EIS） and Li/LiCr0.04Mn1.9604 battery test. The results show that the spherical active material is single spinel structure, compact, and with narrow particle size distribution and low BET specific surface area. Compared with the non-spherical material, the spherical material prepared by the spray drying process shows a lower electrochemical impedance, a fewer electrochemical polarization and a better charge/discharge rate capability and capacity retention at elevated temperatures.

Surface modification and characterization of F-Co doped spinel LiMn_2O_4

Spinel LiCo0.09Mn1.91O3.92F0.08 as cathode material was modified with LiCoO2 by the sol-gel method, and the crystal structure, morphology and electrochemical performance were characterized with XRD, SEM, EDS, AAS and charge-discharge test in this paper. The results show that a good clad coated on parent material can be synthesized by the sol-gel method, and the materials with modification have perfect spinel structure. LiCo0.09Mn1.91O3.92F0.08 materials coated by LiCoO2 improve the stability of crystal structure and decrease the dissolution of Mn into electrolyte. With the LiCoO2 content increasing, the specific capacity and cycle performance of samples are improved. The capacity loss is also suppressed distinctly even at 55 ℃.

Controllable Preparation and Superior Rate Performance of Spinel LiMn2O4 Hollow Microspheresas Cathode Material for Lithium-ion Batteries

Spinel LiMn2O4 microspheres and hollow microspheres with adjustable wall thickness have been prepared using controllable oxidation of MnCO3 microspheres precursors and following solid reactions with lithium salts. Scanning electron microscopy （SEM） investigations demonstrate that the microsphere morphology and hollow structure of precursors are inherited. The effect of hollow structure properties of as-prepared LiMn2O4 on their performance as cathode materials for lithium-ion batteries has been studied. Electrochemical performance tests show that LiMn2O4 hollow microspheres with small wall thickness exhibit both superior rate capability and better cycle performance than LiMn2O4 solid microspheres and LiMn2O4 hollow microspheres with thick wall. The LiMn2O4 hollow microspheres with thin wall have discharge capacity of 132.7 mA.h-g^-1 at C/10 （14.8 mA.g^-1） in the first cycle, 94.1% capacity retention at C/10 after 40 cycles and discharge capacity of 116.5 mAh-gq at a high rate of 5C. The apparent lithium-ion diffusion coefficient （Dapp） of as-prepared LiMn2O4 determined by capacity intermittent titration technique （CITT） varies from 10-11 to 10-8.5 cm2.s^-1 showing a regular ＂W＂ shape curve plotted with test voltages. The D app of LiMn2O4 hollow microspheres with thin wall has the largest value among all the prepared samples. Both the superior rate capability and cycle stability of LiMn2O4 hollow microspheres with thin wall can be ascribed to the facile ion diffusion in the hollow structures and the robust of hollow structures during repeated cycling.

A Raman Study of Spinel LiMn_2O_4

A Raman study was carried out for LiMn 2O 4, which was synthesized via the mixture of Mn 3O 4 and LiNO 3 sintered at different temperatures. It is shown that there are two kinds of Raman spectra for LiMn 2O 4 at different sintering temperatures, while the X-ray diffraction patterns of LiMn 2O 4 sintered at different temperatures are the same. Five Raman bands observed for the materials sintered below 500 ℃ are consistent with the theoretical prediction for spinel structure based on the group theory. Only two Raman bands were observed for the materials sintered at temperatures higher than 500 ℃. The best preparation condition for obtaining a good spinel LiMn 2O 4 is suggested based on the Raman study.

Impedance Studies of Spinel LiMn_2O_4 Electrode/electrolyte Interfaces

The formation process of solid electrolyte interphase（SEI） film on spinel LiMn2O4 electrode surface was studied by electrochemical impedance spectroscopy（EIS） during the initial storage in 1 mol/L LiPF6-EC：DMC：DEC electrolyte and in the subsequent first charge-discharge cycle. It has been demonstrated that the SEI film thickness increased with the increase of storage time and spontaneous reactions occurring between spinel LiMn2O4 electrode and electrolyte can be prevented by the SEI film. In the first charge-discharge cycle succeeding the storage, the electrolyte oxidation coupled with Li-ion insertion is evidenced as the main origin to increase the resistance of SEI film. The results also confirm that the variations of the charge transfer resistance（Rot） with the electrode potential（E） can be well described using a classical equation.

尖晶石型LiMn_(2-x)Ga_xO_4的合成及电化学性能研究

为了提高锂离子电池尖晶石锰酸锂正极材料的循环性能和倍率性能,采用柠檬酸辅助溶胶-凝胶法制备了LiMn2–xGaxO4(x=0,0.02,0.05,0.07)正极材料。研究了Ga掺杂对所制材料性能的影响。结果表明:制得的LiMn2–xGaxO4具有单一的尖晶石结构。当Ga3+掺杂量为x=0.05时,LiMn2–xGaxO4首次放电比容量为117.1 mAh/g,经过95次循环后,放电容量保持率高达97.9%;在高倍率4C条件下,首次放电比容量为100.9 mAh/g,30次循环后放电比容量为102.4 mAh/g,具有优异的倍率性能。

LiCoO_2对LiMn_2O_4改性过程的研究

Modified lithium manganese oxides were prepared by using LiMn 2 O 4 and LiCoO 2 as precursors by solid state reaction.A study has been carried out by TG - DSC,XRD and FTIR to analyze the reaction process and structural characterization of products.The results showed that the LiMn 2 O 4 reacted chemically with LiCoO 2 at high temper - ature.Li and Co atom could insert into the LiMn 2 O 4 crystal lattice and obtained the Cobalt - Doped spinel com - pound.The results of constant - current cyclic test showed that the cyclic stability of the products are increased with the amount of doped LiCoO 2 ,while their initial capacity is decreased.

Mg2+掺杂锰酸锂的第一性原理研究

利用基于密度泛函理论的第一性原理平面波超软赝势法对Mg^2+掺杂锰酸锂的晶格常数与能带结构、态密度、键布居进行计算和分析,计算结果表明:掺杂Mg^2+后将会促使Mn、O原子的电荷重新分布且其相互作用加强,能带带隙减小,费米能级附近的带数增加,费米能由-1.29 eV增加到-1.02 eV,Mn、O、Mg在总态密度中贡献比较大,锂离子贡献比较小且峰型尖锐局域化严重,提高了Li^+的扩散效率,Mn—O键变短,共价性增强,形成的共价键较稳定,其相互作用形成的骨架较稳定不易坍塌.从而提高了材料的循环充放电性能和电池使用寿命.

Electrochemical Performance of Surface-Modified LiMn_2O_4 Prepared by a Melting Impregnation Method

The surface of as-prepared LiMn2O4 was modified with ZnO, Al2O3, CoO and LiCoO2 using a simple nitrate melting impregnation method. Transmission electron microscopy （TEM） studies indicated that oxide nano- particles in the range of 10～50 nm are coated on the surface of the spinel. The surface modified samples show better capacity retention than the unmodified LiMn2O4 spinel at both room temperature and 55℃. Among these samples, the ZnO-modified LiMn2O4 shows the best combination of a high capacity and a low capacity fading rate of 0.036% per cycle at room temperature and 0.064% per cycle at 55℃. The improvement for surface modified LiMn2O4 can be attributed to the inhibition of Mn dissolution and O losses on the surface.

Synthesis and Properties of the Modification of Micro-Crystal LiMn_(2-x)Al_xO_4 Cathode Material for Li-Ion Batteries

The micro-single crystal material spinel LiMn2-xAlxO4 was prepared by a sol-gel procedure and modified by alumina; the electrochemical measurements show that the performances and characteristics of modified LiMn2-xAlxO4 electrode material are better than those of LiMn204. Hence, the modified LiMn2- AlxO4 is a good cathode material for lithium batteries. This can be explained that the size of the modified particle is larger than that of unmodified material, so electrons can be easily transported between the particles.

Synthesis and Characterization of LiCo_xMn_(2-x)O_4 Cathode Materials

LiCoxMn2.04 cathode materials for lithium ion batteries were synthesized by mechanical activation-solid state reaction at 750 ℃ for 24 h in air atmosphere, and their crystal structure, morphology, element composition and electrochemical performance were characterized with XRD, SEM, ICP-AES and charge-discharge test. The experimental results show that all samples have a single spinel structure, well formed crystal shape and uniformly particle size distribution. The lattice parameters of LiCo Mn2-xO4 decrease and the average oxidation states of manganese ions increase with an increase in Co content. Compared with pure LiMn2O4, the LiCo Mn2xO4 （x=0.03-0.12） samples show a lower special capacity, but their cycling life are improved. The capacity loss of LiCo009Mn191O4 and LiCo0.1Mn1.88O4 is only 1.85% and 0.95%, respectively, after the 20th cycle. The improvement of the cycle performance is attributed to the substitution of Co at the Mn sites in the spinel structure, which suppresses the Jahn-Teller distortion and improves the structural stability.

Preparation of modified LiMn_2O_4 by solid-state reaction

Modified lithium manganese oxides were prepared by solid-state reaction of LiMn2O4 and LiCoO2 as raw materials. A study was carried out by TG-DSC, XRD, DSC and electrochemical to analyse the reaction process and structural characterization of products. The results show that the LiMn2O4 reacts chemically with LiCoO2 at high temperature. All of Li and partial Co atoms can insert into the LiMn2O4 crystal lattice and a newly formed spinel phase-modified LiMn2O4 was obtained. The distribution of Co content is even in modified LiMn2O4 compound. The modified LiMn2O4 compound exhibits improved cycling stability at room and elevated temperature in comparison with the pure LiMn2O4.

Influences of Sintering Process of Sprayed Precursors on the Struc-ture and Electrochemical Properties of LiMn_2O_4 Cathode Material

Well-defined spinel LiMn2O4 powders were synthesized via sintering a precursor, which was prepared by spraydrying method. The effects of sintering process on the structure and electrochemical properties of LiMn2O4 were discussed. It was found that a single sintering could not synthesize a pure LiMn2O4 compound, while two-step sintering procedure consisting of decomposing sprayed precursors at 350℃ and further sintering at an elevated temperature leads to the formation of a single-phased LiMn2O4 with homogeneous particle size distribution. As compared to that sintered in air, the two-step sintered LiMn2O4 in oxygen shows tighter structure and more uniform particle size, as well as better electrochemical properties. It delivers an initial discharge capacity of 131 mAh·g^-1 （1/10C）, and still has excellent cycling stability at higher rate （1/5C）.

Structure characteristics and electrochemical properties of LiMn_2O_4 modified by LiCoO_2

In order to improve the cycle performance of LiMn2O4, the modified LiMn,O4 was prepared by solid-state reactions using LiMn2O4 and LiCoO2 as precursors. XRD and EDS were used to study the structure properties of the modified LiMn2O4. The electrochemical properties of the modified LiMn2O4 were also investigated. The results show that Li and Co atoms could insert into the LiMn2O4crystal lattice and a newly formed spinel phase, modified LiMn2O4 was obtained. The modified LiMn2O4 exhibits excellent cycle ability at room and elevated temperatures compared to pure LiMn2O4. The improved electrochemical stability of the modified LiMn2O4 attributes to the entrance of Li and Co ions inserted into the spinel crystal structure.

Electrochemical properties of niobium and phosphate doped spherical Li-rich spinel LiMn2O4 synthesized by ion implantation method

Spherical Li-rich lithium manganese oxide（LMO） spinel material was synthesized by an ion implanted method assisted by polyalcohol doped with Niobium and Phosphate simultaneously.The material was characterized by scanning electron microscopy,X-ray diffraction and BET specific surface area analysis.The electrochemical performances were investigated with galvanostatic techniques and cyclic voltammetry.The synthesis process was investigated with TG/DSC.The results show that the lithium ion can be immersed into the pore of manganese dioxide at a low temperature with the ion implanted method.The prepared materials have a higher discharge capacity and better crystallization than those prepared by solid phase method.The doped Nb can improve the capacity of the Li-rich LMO spinel and reinforce the crystal growth along（111） and（400） planes.The crystal grains show circular and smooth morphology,which makes the specific surface area greatly decreased.Phosphate-doped LMO spinel exhibits good high-rate capacity and structure stability.The prepared Li（1.09）Mn（1.87）Nb（0.031）O（3.99）（PO4）（0.021）delivers a discharge capacity of 119mAhg^-1 at 0.2C（1C=148mAg^-1） and 112.8 mAhg^-1 at 10 C,the discharge capacity retention reaches 98% at 1 ℃ after 50 cycles at 25 ℃ and 94% at 55 ℃.