LiAl0.05Mn1.95O4正极材料锂离子嵌脱动力学研究

采用超声辅助溶胶凝胶法成功制备了LiAl0.05Mn1.95O4正极材料,并利用循环伏安和电化学阻抗谱研究了不同合成方法对LiAl0.05Mn1.95O4正极材料锂离子嵌脱动力学的影响.结果表明:超声辅助溶胶凝胶法制备的尖晶石材料具有更好的可逆性和最小的电荷转移电阻;LiMn2O4(sol-gel)、LiAl0.05Mn1.95O4(sol-gel)和LiAl0.05Mn1.95O4(UASG)的交换电流密度分别为2.57×10-2、4.16×10-2、5.08×10-2mA.cm-2,固相锂离子扩散系数分别为3.27×10-10、4.94×10-10、6.91×10-10cm2.s-1,表明超声辅助溶胶凝胶法制备的样品具有较好的锂离子嵌脱动力学.     

Electrochemical properties of spinel LiMn2O4 and LiAl0.1Mn1.9O3.9F0.1 synthesized by solid-state reaction

Two types of spinel cathode powders, LiMn2O4 and LiAl0.1Mn1.9O3.9F0.1, were synthesized by solid-state reaction. X-ray diffraction (XRD) patterns of the prepared samples were identified as the spinel structure with a space group of Fd 3 m. The cubic lattice parameter was determined from least-squares fitting of the XRD data. The LiAl0.1Mn1.9O3.9F0.1 sample showed a little lower initial capacity, but better cycling performance than the LiMn2O4 sample at both room temperature and an elevated temperature. The Vanderbilt method was used to test the electrochemical conductivity of the LiMn2O4 samples. The electrochemical impedance spec-troscopy (EIS) method was employed to investigate the electrochemical properties of these spinel LiMn2O4 samples.     

Structure and electrochemical properties of La, F dual-doped LiLa0.01Mn1.99O3.99F0.01 cathode materials

The cathode materials LiMn2O4 and rare earth elements La-doped or La and F dual-doped spinel lithium manganese oxides were synthesized by the citric acid-assisted sol-gel method. The synthesized samples were investigated by differential thermal analysis (DTA) and thermogravimetry (TG) measurements, X-ray diffraction (XRD), scanning electronic microscope (SEM), cyclic voltammetry (CV), and charge-discharge test. XRD data shows that all the samples exhibit the same pure spinel phase, and the LiLa0.01Mn1.99O3.99F0.01 and LiLa0.01Mn1.99O4 samples have smaller lattice parameters and unit cell volume than LiMn2O4. SEM indicates that LiLa0.01Mn1.99O3.99F0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution. The charge-discharge test reveals that the initial capacities of LiMn2O4, LiLa0.01Mn1.99O4, and LiLa0.01Mn1.99O3.99F0.01 are 129.9, 122.8, and 126.4 mAh·g-1, and the capacity losses of the initial values after 50 cycles are 14.5%, 7.6%, and 8.0%, respectively. The CVs show that the La and F dual-doped spinel displays a better reversibility than LiMn2O4.     

Structure and electrochemical properties of LiLaxMn2-xO4 cathode material by the ultrasonic-assisted sol-gel method

Powders of spinel LiLaxMn2_xO4 were successfully synthesized by the ultrasonic-assisted sol-gel (UASG) method.The structure and properties of LiLaxMn2_xO4 were examined by X-ray diffraction (XRD),Fourier transform infrared (FT-IR) spectros-copy,scanning electronic microscopy (SEM),galvanostatic charge-discharge test,and cyclic voltammetry (CV).XRD results showthat the La3+ can partially replace Mn3+ in the spinel and the doped materials with La3+ have a larger lattice constant compared with pristine LiMn2O4.FT-IR indicates that the absorption peak of Mn3+-O and Mn4+-O bonds has a red and blue shift with the increase of doping lanthanum in LiLaxMn2_xO4,respectively.The charge-discharge test exhibits that the initial discharge capacity of LiLaxMn2_xO4 drops off,and the capacity retention increases gradually at C/5 discharge rate with the increase of doping lanthanum,and LiLa0.01Mn1.99O4 has a higher discharge capacity and a better cycling performance at 1C discharge rate.CV reveals that the dop-ing La3+ is beneficial to the reversible extraction and intercalation of Li+ ions.     

尖晶石型锰酸锂的复合掺杂改性

以固相烧结法制备的尖晶石型锰酸锂为基础,对其结构中掺杂复合非金属元素B和F,合成了B、F掺杂的尖晶石。通过X射线衍射、扫描电镜、电化学分析方法对试样的晶体结构、表面形貌及电化学性能进行表征。结果表明,采用B、F包覆的锰酸锂与纯锰酸锂的X射线衍射结果相似,波峰尖锐且峰值高;随着B的掺入,尖晶石作为正极材料充放电的循环性能得到了提高,但是其初始容量较低,仅为102.3mA·h/g。随着加入复合非金属元素B和F,样品的初始容量提高到了110.9mA·h/g,50次循环后的容量保持率为83.14%。实验结果表明,复合掺杂有效提高了锰酸锂的电化学性能。     

锂离子电池正极材料LiCexNdxMn2-2xO4（x=0～0.018）的Pechini合成及表征

采用X射线衍射仪、电池测试系统等,研究了采用Pechini法合成的锂离子电池正极材料LiCexNdxMn2-2xO4（x=0、0.012、0.014、0.016、0.018）的组织结构、首次充放电性能、循环稳定性能等。结果表明：当稀土元素掺入量较少（x≤0.014）时,样品由尖晶石型LiMn2O4相组成,否则,样品中将出现微量的杂质相（CeO2、Nd2O3）;适量的稀土元素掺杂将使LiMn2O4样品的初始容量减小、循环稳定性能增加。LiCe0.014Nd0.014Mn1.972O4样品具有较好的循环稳定性能,其初始放电容量为124.8 mAh/g,经30次循环充放电后的容量保持在116.3 mAh/g,容量保持率为93.2%。     

Preparation and characterization of LiAlxMn2-xO4 for a supercapacitor in aqueous electrolyte

LiAlxMn2-xO4(0≤x≤0.5) was synthesized by high temperature solid-state reaction. The structure and morphology of LiAlxMn2-xO4 were investigated by X-ray diffraction and scanning electron microscopy(SEM) . The results indicate that all samples show spinel phase. The polyhedral particles turn to club-shaped,then change to small spherical,and finally become agglomerates with increasing Al content. The supercapacitive performances of LiAlxMn2-xO4 were studied by means of galvanostatic charge-discharge,cyclic vol...     

微波合成LiMn2O4正极材料及其电化学性能的研究

本文以Li2CO3 、MnO2为原料,采用微波热处理合成锂离子电池正极材料LiMn2O4,研究了热处理温度,Li/Mn摩尔比对产物结构和电化学性能的影响,同时研究了微波热处理和传统热处理两种加热方式的差别.通过X射线衍射（XRD）、扫描电镜（SEM）、恒电流充放电测试分别对产物的结构、形貌及电化学性能进行表征,结果表明：采用微波法在750℃保温15 min,快速地制备出尖晶石型LiMn2O4,纯度高,尺寸分布均匀,约100-300 nm;于0.1C倍率下,以微波法制备的正极材料首次放电比容量可达112.38 mA·h/g,1C倍率充放电50次循环后,容量保持率为91.6％;以传统方法制备的正极材料0.1C倍率下首次放电比容量为94.07 mA·h/g,1C倍率充放电50次循环后,容量保持率为71.4％     

尖晶石型锰酸锂制备及其电化学性能

锰酸锂被认为是取代商品锂离子电池正极材料的LiCoO2候选材料.以二氧化锰、醋酸锰及氢氧化锂为原料,蒸馏水为分散剂,在空气气氛下进行分段烧结,控制烧结温度和时间,制备了锂离子电池正极材料锰酸锂.用X射线衍射仪,电子扫描电镜对产物的结构特征、微观表面形貌和恒流充放电性能进行了表征.结果表明:所制得正极材料为尖晶石型锰酸锂,结晶度高,无杂质相,材料颗粒的粒径均匀,首次放电比容量为117.3 mAh/g(0.5 mA/cm2,2.8~4.4 V,vs.Li+/Li);50次循环后,放电比容量为107.9 mAh/g,不可逆容量损失为9.4 mAh/g,比容量保持率为92.0%.得到了很好的综合电化学性能.     

5V锂离子电池正极材料的制备和电化学性能研究

用液相法合成出用锂和镍取代的尖晶石锂锰氧化物正极材料.用XRD和FTIR对其进行了表征,并探讨了其在有机电解液的电化学性能.研究结果表明:在锂锰氧化物掺入适量的镍(锰∶镍的摩尔比为1.4∶0.6)可以改善尖晶石LiMn2O4的循环性能,提高放电平台,使其大部分容量往高电位方向移动,电池的放电电压提高,这样的材料适合做5V电池的正极材料.     

溶胶-凝胶法制备尖晶石结构镍锰氧化物型锂离子筛

采用溶胶-凝胶法,以乙酸锂、乙酸镍和乙酸锰为主要原料,通过正交试验得到制备镍锰氧化物型锂离子筛LiNixMn2-xO4的适宜条件:x=0.05,柠檬酸作螯合剂,焙烧温度700℃,焙烧时间8 h。用0.5 mol.L-1过硫酸铵作抽锂剂,Mn2+的溶出率较低,仅为0.31%。通过X射线衍射分析证明所合成的锂离子筛为尖晶石结构,每克离子筛对Li+的饱和交换容量达36.72 mg。     

以Mn3O4为锰源合成高性能LiMn2O4正极材料

以Mn3O4为锰源,采用固相反应法,在较低的温度(650℃)制得尖晶石LiMn2O4正极材料。采用X射线衍射(XRD)、扫描电镜(SEM)、循环伏安和恒流充放电等技术对其相组成、微结构和电化学性能进行表征。结果表明该正极材料结晶良好,一次粒径约为150 nm。它的电化学性能,尤其是循环性能,明显优越于在较高温度合成的LiMn2O4。在电流密度为74 mA?g-1时,测得比容量为128 mAh?g-1,在1 480 mA?g-1时,比容量为105 mAh?g-1;在室温、148 mA?g-1充放电200次循环后,容量保持率为93%。     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi0. 45 Co0. 10 Mn0. 4sO2 was synthesized from Li2CO3 and a triple oxide of nickel, cobalt and manganese at 950 ℃ in air. The structures and characteristics of LiNi0. 45 Co0.10 Mn0. 45 O2, LiCoO2 and LiMn2 O4 were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi0.4s Co0.10 Mn0. 45 O2 has a layered structure with hexagonal lattice. The commercial LicoO2 has sphere-like appearance and smooth surfaces, while the LiMn2 O4 and LiNi0.45 Co0. 10 Mn0. 45 O2 consist of cornered and uneven particles. LiNi0. 45 Co0.10 Mn0. 45 O2 has a large disLiMn2 O4 and LiCoO2, respectively. LiCoO2 and LiMn2 O4 have higher discharge voltage and better rate-capability than LiNi0. 45Co0.10 Mn0. 45 O2. All the three cathodes have excellent cycling performance with capacity retention of above 89.3 % at the 250th cycle. Batteries with LiMn2 O4 or LiNi0.45 Co0.10 Mn0. 45 O2 cathodes show better safety performance under abusive conditions than those with LiCoO2 cathodes.     

锂离子电池高电压正极材料LiNi_（0.5）Mn_（1.5）O_4的合成与性能

采用镍锰氢氧化物和碳酸锂为原料,在高温下合成LiNi0.5Mn1.5O4正极材料。系统地研究了不同的退火工艺对LiNi0.5Mn1.5O4结构与电化学性能的影响。研究发现,合成的样品都具有标准的尖晶石结构和规则的八面体外形。电化学测试结果表明,在700℃下退火12h得到的样品电化学性能最佳。首次放电容量达到141mAh/g,40次循环后容量保持率为99.2%,5C放电时容量仍然达到122mAh/g。     

Synthesis and characterization of spinel Li_(1.05)Cr_(0.1)Mn_(1.9)O_(4-z)F_z as cathode materials for lithium-ion batteries

Samples with the nominal stoichiometry Li_(1.05)Cr_(0.1)Mn_(1.9)O_(4-z)F_z(z=0,0.05,0.1,0.15,and 0.2) were synthesized via the solid-state reaction method and characterized by X-ray powder diffraction(XRD),scanning electron microscopy(SEM),galvanostatic charge/discharge, and slow rate cyclic voltammetry(SSCV) techniques.The results show that the pure spinel phase indexed to Fd3m can be obtained when z=0, 0.05,and 0.1.The substitution of F for O with z≤0.1 contributes to the increase of initial capacity c...     

Structure and Electrochemical Properties of LiMn_2O_(4-x)F_x

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尖晶石LiMn2O4的容量衰减与性能改进

尖晶石LiMn2O4是制作锂离子电池正极的很有希望的材料。但研究中发现,LiMn2O4在高温下和循环过程中,存在着容量衰减现象。它是目前制约尖晶石LiMn2O4走向商品化生产的关键性因素。综述了LiMn2O4容量衰减的原因和抑制措施,分析出容量衰减的原因,主要包括活性物质的化学稳定性和LiMn2O4结构稳定性两个方面。其中HF造成的锰的溶解是主要原因。采取掺杂富锂核与富锂相结合的措施,可以有效地抑制LiMn2O4的容量衰减,改善其循环性能。     

Comparative experiment on layered Li（Ni1/3Co1/3Mn1/3）O2 as the alternative material for LiCoO2

This work was financially supported by the National Natural Science Foundation of China （No.50472093）.     

共沉淀法制备LaF_3表面修饰LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2及性能研究

以LiNi1/3Co1/3Mn1/3O2为正极材料,采用共沉淀合成方法制备LaF3表面修饰LiNi1/3Co1/3Mn1/3O2正极材料,利用X射线衍射(XRD)、扫描电镜(SEM)和电化学测试等方法对合成材料的结构、形貌以及电化学性能进行表征。结果表明:经过LaF3表面修饰的LiNi1/3Co1/3Mn1/3O2材料保持了LiNi1/3Co1/3Mn1/3O2层状结构,其中LaF3表面修饰量为0.59%时,在电压为2.75～4.50V范围内,以0.3mA/cm2电流密度下经恒电流充放电测试,其首次放电比容量为172.7mAh/g,经过50周充放电循环后放电比容量为163.5mAh/g,表现出较高的初始放电比容量和良好的抗过充电性能。     

锂离子电池正极材料LiMn2O4掺杂及对其性能的影响

综述了近年来掺杂锂离子正极材料尖晶石LiMn2O4的元素及方法，阐述了在锂离子正极材料LiMn2O4中掺杂钴、铬、镍、铝、稀土、钒后对材料性能的影响．结果表明，掺杂均不同程度地改善材料的循环稳定性，但对容量大都产生不利影响．