球形高电压LiNi0.5Mn1.5O4的制备及其电化学性能

以化学共沉淀法制备的球形Ni0.25Mn0.75CO3为前驱体合成高电压正极材料LiNi0.5Mn1.5O4,探讨用前驱体与Li2CO3直接反应和用前驱体分解后的氧化物与Li2CO3反应两种工艺路线对LiNi0.5Mn1.5O4形貌和电化学性能的影响。用扫描电镜(SEM)和X射线衍射(XRD)对Ni0.25Mn0.75CO3前驱体和LiNi0.5Mn1.5O4样品进行表征,用充放电测试和循环伏安法对LiNi0.5Mn1.5O4样品进行电化学性能研究。结果表明:两种方法合成的LiNi0.5Mn1.5O4均具有尖晶石型结构。但以前驱体Ni0.25Mn0.75CO3直接与Li2CO3反应合成的LiNi0.5Mn1.5O4的一次粒子颗粒较大,形貌较差,性能也较差;而以前驱体分解后的氧化物与Li2CO3反应合成的LiNi0.5Mn1.5O4的形貌及性能均较好。在3.0~4.9 V的电压范围内,1C倍率下电池的放电比容量达到136.3 mA.h/g,循环100次仍有126.5 mA.h/g,且材料具有较好的倍率性能;5C倍率下的首次放电比容量高达120.7 mA.h/g。     

5 V正极材料LiNi0.5Mn1.5O4的草酸共沉淀法合成及性能

通过草酸共沉淀法成功合成了5 V正极材料LiNi0.5Mn1.5O4,采用XRD、SEM、充放电试验和循环伏安法对合成产物进行表征。XRD和SEM分析结果表明,所合成的正极材料LiNi0.5Mn1.5O4具有立方尖晶石结构（空间群为Fdˉ3 m）,结晶度高,粒度适中且比较均匀。电化学测试结果表明,合成产物具有优良的电化学性能,它仅在4.7 V附近有一个放电平台,0.1 C的放电容量高达133 mAh/g,50次循环后放电容量仍保持在128 mAh/g以上,1和3 C的放电容量在30次循环后也分别保持在122和101 mAh/g以上     

LiMgxNi0.5-xMn1.5O4的制备和电化学性能

为改善LiNi0.5Mn1.5O4的电化学性能,采用流变相法合成掺镁的锂离子电池正极材料LiMgxNi0.5-xMn1.5O4(x=0,0.05,0.1)。XRD测试结果表明所得材料仍为尖晶石结构。电化学性能测试结果显示:当x取值0.1,在3.5～4.9V电压范围内进行充放电循环时,材料LiMg0.1Ni0.4Mn1.5O4具有较好的循环性能,1C充放电时,初始放电比容量可达110.22mAh/g,30次循环后容量衰减率仅为7.7%。     

LiNi_(0.5)Mn_(1.5)O_4/Ag复合材料的制备及其电化学性能

采用流变相法合成LiNi0.5Mn1.5O4粉末。以甲醛为还原剂,采用化学镀法制备LiNi0.5Mn1.5O4/Ag复合材料。通过X射线衍射分析、扫描电镜分析以及电化学测试等手段对LiNi0.5Mn1.5O4/Ag的微观结构、表面形貌和电化学性能进行研究。结果表明:在LiNi0.5Mn1.5O4/Ag中,LiNi0.5Mn1.5O4表面被包覆一层分散均匀且颗粒大小均匀的Ag,Ag颗粒的大小为200～300nm。Ag颗粒的存在增加LiNi0.5Mn1.5O4颗粒之间的电子导电性,降低电池的极化作用,减少锰的溶解,使得LiNi0.5Mn1.5O4/Ag具有比LiNi0.5Mn1.5O4更高的可逆容量、更稳定的循环性能和更好的倍率性能。以0.2C放电时,LiNi0.5Mn1.5O4/Ag的首次放电容量达到143.8mA·h/g;而经100次循环后,以0.2C和2.0C放电时,LiNi0.5Mn1.5O4/Ag的容量保持率分别达到99.2%和86.8%。     

Influence of Cr-Substitution on the Electrochemical Performance of LiNi0.5Mn0.5O2 Cathode Material for Lithium Ion Batteries

采用低温燃烧法合成了锂离子电池正极材料LiNi0.5Mn0.5-xCrxO2(x=0,0.01,0.02,0.05,0.1),研究了Cr取代部分Mn对其结构和电化学性能的影响。充放电测试结果表明:Cr取代部分Mn对正极材料LiNi0.5Mn0.5-xCrxO2的电化学性能有重要的影响,用适量的Cr取代Mn(x=0.02)能够提高正极材料的放电比容量和循环稳定性。X射线衍射(XRD)分析和循环伏安(CV)测试显示,Cr对Mn的适量取代能抑制正极材料中的阳离子混排,降低电极材料的极化,改善其可逆性能。LiNi0.5Mn0.48Cr0.02O2在2.5~4.6 V之间以0.1 C速率充放电,首次放电容量为179.9 mAh/g,第50次循环放电容量仍保有171.0 mAh/g,容量保持率达到95.1%     

掺Cr对锂离子电池正极材料LiNi_(0.5)Mn_(0.5)O_2电化学性能的影响(英文)

采用低温燃烧法合成了锂离子电池正极材料LiNi0.5Mn0.5-xCrxO2(x=0,0.01,0.02,0.05,0.1),研究了Cr取代部分Mn对其结构和电化学性能的影响。充放电测试结果表明:Cr取代部分Mn对正极材料LiNi0.5Mn0.5-xCrxO2的电化学性能有重要的影响,用适量的Cr取代Mn(x=0.02)能够提高正极材料的放电比容量和循环稳定性。X射线衍射(XRD)分析和循环伏安(CV)测试显示,Cr对Mn的适量取代能抑制正极材料中的阳离子混排,降低电极材料的极化,改善其可逆性能。LiNi0.5Mn0.48Cr0.02O2在2.5~4.6 V之间以0.1 C速率充放电,首次放电容量为179.9 mAh/g,第50次循环放电容量仍保有171.0 mAh/g,容量保持率达到95.1%     

初始Li/(Mn+Ni)摩尔比对LiNi0.5Mn0.5O2电化学性能的影响

以Li2CO3,MnCO3和Ni(OH)2为原料,采用一步固相反应制备锂离子电池层状结构正极材料LiNi0.5-Mn0.5O2,采用X射线衍射和扫描电镜对其结构和形貌进行表征,并研究配料时不同初始Li/(Mn Ni)摩尔比(1.0,1.05,1.1,1.2,1.5)对LiNi0.5Mn0.5O2电化学性能的影响。X射线衍射结果表明,在600℃预烧12 h而后800℃烧结24 h的条件下各样品结晶完整,初始Li/(Mn Ni)摩尔比为1.5时样品有未知相杂质生成。扫描电镜分析表明,随着初始Li/(Mn Ni)摩尔比的增大,颗粒团聚加剧。电化学测试结果表明,随着初始Li/(Mn Ni)摩尔比(≥1.05)的提高,初始容量有下降趋势。初始Li/(Mn Ni)摩尔比为1.05和1.1时样品首次放电容量分别为167.0 mA.h/g和147.2 mA.h/g,循环20次后容量保持率分别为88.2%和97.8%。     

Al离子掺杂对LiNi0.5Mn1.5O4高电压材料性能的影响

用固相法合成了Al掺杂的高电压LiNi0.5Mn1.5-xAlxO4材料,研究了材料晶胞参数、材料可逆比容量、放电电压及循环性能随掺Al量的变化规律。结果表明,随着掺Al量的增加,材料的可逆比容量在逐渐减小;当Al掺杂量为0.06(LiNi0.5Mn1.44Al0.06O4)时,样品具有最佳的循环性能,100周的容量保持率在97%左右。与此同时,使用以Al掺杂量为0.06的样品为正极,石墨为负极组装的全电池显示了良好的循环性能。     

锂离子电池正极材料LiNi0.5Co0.2Mn0.3O2的制备及电化学性能

采用液相共沉淀法和固相烧结法分别制备镍钴锰复合氢氧化物(Ni0.5Co0.2Mn0.3(OH)2)和LiNi0.5Co0.2Mn0.3O2正极材料。通过X射线衍射和电化学性能测试对所得样品的结构及电化学性能进行了表征。结果表明:LiNi0.5Co0.2Mn0.3O2具有很好的α-NaFeO2层状结构,以20 mA/g的电流密度在2.5～4.3 V的电压区间充放电时,最高首次放电比容量达175 mA.h/g,首次库伦效率在89%～90%之间。当首次放电比容量为160～170 mA.h/g时,30循环未见容量衰减。锂含量对其电化学性能影响的结果表明:锂含量(n(Li)/n(Ni+Co+Mn))在1.03～1.09的范围内,随着锂含量的增加,放电比容量略有减小,但循环性能、中值电压以及平台性能都得到提高;当锂含量超过1.09时,循环性能、中值电压以及平台性能开始降低。     

正极材料LiNi0.8Co0.1Mn0.1O2的合成及电化学性能

将液相共沉淀法制备的Ni0.8Co0.iMn0.1(OH)2与LiOH·H2O混合,固相烧结合成微米级的LiNi0.8Co0.1Mn0.1O2正极材料.XRD谱表明,合成的LiNi0.8Co0.1Mn0.1O2正极材料为典型的α-NaFeO2层状结构,无杂质峰;从SEM像可以看出,产物颗粒为类球形,分散性好,由一次粒子紧密堆积而成,平均粒径为3 μm;电化学测试结果表明,在2.8～4.3 V电压范围内,750℃焙烧15h合成的LiNi0.8Co0.1Mn0.1O2材料的电化学性能最优,0.1C时,其首次放电容量为186.748mA·h/g,分别高于700和800℃时的首次放电容量172.947和180.235mA·h/g.材料在0.5和2C时循环40次后,容量保持率分别为98.32％和88.72％,循环性能良好.     

Al2O3包覆LiNi0.03Co0.05Mn1.92O4正极材料的制备及其电化学性能

以Al(NO3)3?9H2O为包覆原料，通过燃烧法制备得到LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料。通过X射线衍射(XRD)，场发射扫描电子显微镜(FESEM)和透射电镜(TEM)等表征手段对材料的结构和形貌进行分析，并通过恒电流充放电、循环伏安(CV)、交流阻抗(EIS)等测试分析材料的电化学性能。结果表明，Al2O3包覆没有改变LiNi0.03Co0.05Mn1.92O4的尖晶石型结构，包覆层厚度约10.6nm。LiNi0.03Co0.05Mn1.92O4@Al2O3正极材料电化学性能得到了明显改善，1 C和10 C倍率下初始放电比容量分别为119.9 mAh?g-1和106.3 mAh?g-1，充放电循环500次后容量保持率分别为88.4%和78.2%，而未包覆的LiNi0.03Co0.05Mn1.92O4在1 C和10 C倍率下初始放电比容量分别为121.2 mAh?g-1和104.0 mAh?g-1，500次循环后容量保持率分别为84.1%和67.6%。LiNi0.03Co0.05Mn1.92O4@Al2O3活化能为32.92 kJ?mol-1，而未包覆材料的活化能为36.24 kJ?mol-1，包覆有效降低了材料Li+扩散所需克服的能垒，提高了材料的电化学性能。     

Synthesis and electrochemical properties of Th-doped LiMn2O4 powders for lithium-ion batteries

To improve the cycle performance of eco-friendly and cost-effective spinel LiMN2O4 as the Li secondary batteries, the Th-doped LiThxMn1-xO4 spinel powers were synthesized by solid-state method. The starting materials, Li2CO3,MnO2 and Th(NO3)4·4H2O, were mixed uniformly using a traditional ball milling, which resulted in a uniform particle size distribution in the mixed powers. Tests of X-ray diffraction, SEM, impedance spectra and charge-discharge were carried out for LiThxMn1-xO4 cathode materials. Results show that the synthesized LiTh0.01Mn1.99O4 material exhibits standard spinel structure, regular particle morphology and excellent property of charge-discharge for big current. The capacity retention of the material modified by doping Th is more than 85.1% of the first discharge specific capacity of 111.5 mAh·g -1 after 20 cycles at the current rate 1C, while the pristine LiMN2O4 is only 57% of the first discharge specific capacity of 110.2 mAh·g-1 after the same cycles at the same current rate.     

锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2的制备及性能研究

采用溶胶-凝胶法制备了锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2,并考察了烧结温度对材料结构、表面形貌和电化学性能的影响.XRD和SEM测试结果表明,900℃下烧结得到的样品是粒径在0.3～0.5 μm范围的球形粒子,具有最佳的阳离子有序度;充放电测试结果表明,其在0.1C倍率下首次放电容量达到148.8...     

Synthesis and electrochemical performance of 5V spinel LiNi0.5Mn1.5O4 prepared by solid-state reaction

Spinel compound LiNi0.5Mn1.5O4 with high capacity and high rate capability was synthesized by solid-state reaction. At first, MnCl2·4H2O and NiCl2·6H2O were reacted with (NH4)2C2O4·H2O to produce a precursor via a low-temperature solid-state route, then the precursor was reacted with Li2CO3 to synthesize LiNi0.5Mn1.5O4. The effects of calcination temperature and time on the physical properties and electrochemical performance of the products were investigated. Samples were characterized by thermal gravimetric analysis(TGA), scanning electron microscopy(SEM), X-ray diffractometry(XRD), charge-discharge tests and cyclic voltammetry measurements. Scanning electron microscopy(SEM) image shows that as calcination temperature and time increase, the crystallinity of the samples is improved, and their grain sizes are obviously increased. It is found that LiNi0.5Mn1.5O4 calcined at 800 ℃ for 6 h exhibits a typical cubic spinel structure with a space group of Fd3m. Electrochemical tests demonstrate that the sample obtained possesses high capacity and excellent rate capability. When being discharged at a rate as high as 5C after 30 cycles, the as-prepared LiNi0.5Mn1.5O4 powders can still deliver a capacity of 101 mA-h/g, which shows to be a potential cathode material for high power batteries.     

尖晶石LiNi_(0.5)Mn_(1.5)O_4中掺杂Fe的作用机理

利用湿化学法结合固相反应法制备了尖晶石LiNi_(0.5)Mn_(1.5)O_4和掺杂Fe的LiNi_(0.45)Fe_(0.1)Mn_(1.45)O_4材料,从晶体结构、表面形貌、充放电曲线特点、倍率性能等方面比较了掺杂Fe以后对材料的影响,并结合热重实验,通过测试失重量,进而分析了材料中的氧缺陷含量,推导出掺杂Fe的作用机理:尖晶石LiNi_(0.5)Mn_(1.5)O_4材料中掺杂Fe元素,能够使材料晶体中保持一定的氧缺陷,从而使得材料含有一定量的Mn~(3+),提高了材料充放电倍率性能。     

Effects of synthesis conditions on the structural and electrochemical properties of layered LiNi1/3Co1/3Mn1/3O2 cathode material via oxalate co-precipitation method

The uniform layered LiNi1/3Co1/3Mn1/3O2 cathode material for lithium ion batteries was prepared by using (Ni1/3Co1/3Mn1/3)C2O4 as precursor synthesized via oxalate co-precipitation method in air. The effects of calcination temperature and time on the structure and electrochemical properties of the LiNi1/3Co1/3Mn1/3O2 were systemically studied. XRD results revealed that the optimal calcination conditions to prepare the layered LiNi1/3Co1/3Mn1/3O2 were 950°C for 15 h. Electrochemical measurement showed that the sample prepared under the such conditions has the highest initial discharge capacity of 160.8 mAh/g and the smallest irreversible capacity loss of 13.5% as well as stable cycling performance at a constant current density of 30 mA/g between 2.5 and 4.3 V versus Li at room temperature.