Ni-Cu掺杂诱导制备两类截角八面体LiMn2O4材料及其电化学性能

结合元素掺杂和晶面调控策略制备了同时包含(111)、(110)和(100)三个晶面和包含(111)和(100)两个晶面的两类截角八面体形貌的LiNi_0.03Cu_0.06Mn_1.91O₄正极材料,并研究了其电化学性能。结果表明：Ni-Cu共掺杂有效抑制了尖晶石LiMn₂O₄的Jahn-Teller效应,促进了其晶体发育和晶面的择优生长,但部分晶面发育较不完善,与一般情况不同的是Ni-Cu共掺后LiNi_0.03Cu_0.06Mn_1.91O₄正极材料的颗粒粒径显著增大;形成的截角八面体形貌中高暴露(111)面降低了Mn的溶解,少部分(110)和(100)晶面增加了Li⁺的扩散通道。恒电流充放电测试结果表明：在5 C和10 C倍率下,LiNi_0.03Cu_0.06Mn_1.91O₄     

低温电解法制备球形尖晶石LiMn2O4及性能研究

采用MnSO4-H2SO4混合溶液作电解液，高纯铅板作电极，控制电解池温度为0～10℃，低温电解制取球形MnO2微粒；将其用一定浓度硝酸锂溶液浸渍，经过520℃低温合成、760℃高温结晶获得球径较为均一的球形尖晶石锰酸锂锂离子电池正极材料。通过XRD和SEM对其进行了相结构表征和表面形貌观察。组装试验电池，测得材料初始容量约为105mAh·g^-1，6次循环放电后循环过程趋于稳定，第30次循环充电容量保持在98．1mAh·g^-1，放电容量保持在95．0mAh·g^-1，表现出良好的充放电循环性能。     

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。     

掺杂Pr3+的尖晶石LiPrxMn2-xO4的合成及电化学性能

采用溶胶凝胶法合成掺杂稀土镨离子的锂锰尖晶石LiPrxMn2-xO4,并对其结构和电化学性能进行初步研究.结果表明,当掺入的Pr3+含量较低(x≤0.02)时,得到的产物能保持完整的尖晶石结构,并表现出极佳的电化学性能.Pr3+的掺入使材料的循环稳定性能大幅度提高,而这种提高是源于Pr3+对尖晶石结构的稳定作用.电极材料LiPr0.02Mn1.98O4显示了最优的电化学性能,在0.2 C放电速率下,其初始放电容量为118 mAh·g-1,100次循环后仍能保持初始容量的98%.     

尖晶石LiMn2O4和LiCoO2与电解液的相容性

研究锂离子电池正极活性材料尖晶石LiMn2O4和LiCoO2与6种电解液充、放电时的相容性。用X射线衍射检测自制的LiCoO2试样和尖晶石LiMn2O4试样的结构；用粉末微电极循环伏安法测定6种电解液在导电剂乙炔黑表面的氧化电位；将制得的尖晶石LiMn2O4试样和LiCoO2试样在上述电解液中进行恒电流充放电实验。结果表明：充电至高电位3．3～4．3V（vs Li／Li^＋）时，如果正极活性材料表面与电解液发生不可逆反应并在其上覆盖一薄层电子不可导的钝化膜，则将导致活性材料的充、放电效率降低，放电容量减少，即正极活性材料与电解液的相容性差；反之，则相容性好；尖晶石LiMn2O4与上述6种电解液的相容性都很好，普适性强；LiCoO2与上述6种电解液的相容性差别较大，呈选择性。     

尖晶石型LiNixMn2-xO4锂离子正极材料的电化学性能

采用Pechini法在800℃空气中焙烧6h制备LiNixMn2-xO4试样(x＝0，0．05，0．1，0.2，0．3，0．4，0．5)。经XRD测试表明除LiNi0.5Mnl．5O4以外，其它的试样均为纯净的尖晶石结构。尖晶石LiNixMn2-xO4试样电极在3．3—4．5V以及4．5—4．8V范围内的电化学性能测试表明：在3．3—4．5V范围内，试样初始充放电容量随Ni元素掺杂比例的增加而降低；在4．5—4．8V范围内，试样初始充放电容量随Ni元素掺杂比例的增加而增大；在3．3—4．8V范围内，试样总的初始容量基本不变；在3．3—4．5V范围内，试样的循环性能随Ni元素掺杂比例的增加而提高。     

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。     

LiMn2L(Ac)2热分解制备的尖晶石LiMn2O4及其电化学性能

通过XRD、SEM及电化学测试等手段研究了前驱体LiMn2L(Ac)2(L为柠檬酸根)的焙烧工艺条件对尖晶石LiMn2O4产物的结构、形貌及电化学性能的影响.结果表明:提高前驱体的焙烧温度有利于获得晶相结构、微观形貌及电化学性能均较好的LiMn2O4样品.在500℃焙烧2 h再于750℃下保温8～16 h的分段焙烧工艺所得样品的初始容量达到126.0 mAh/g,循环50次后容量衰减了14.5%.     

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。     

尖晶石型LiNi_xMn_(2-x)O_4锂离子正极材料的电化学性能

采用Pechini法在 80 0℃空气中焙烧 6h制备LiNixMn2 -xO4试样 (x =0 ,0 .0 5 ,0 .1,0 .2 ,0 .3,0 .4 ,0 .5 )。经XRD测试表明除LiNi0 .5Mn1.5O4以外 ,其它的试样均为纯净的尖晶石结构。尖晶石LiNixMn2 -xO4试样电极在 3.3～ 4 .5V以及 4 .5～ 4 .8V范围内的电化学性能测试表明 :在 3.3～ 4 .5V范围内 ,试样初始充放电容量随Ni元素掺杂比例的增加而降低 ;在 4 .5～ 4 .8V范围内 ,试样初始充放电容量随Ni元素掺杂比例的增加而增大 ;在 3.3～ 4 .8V范围内 ,试样总的初始容量基本不变 ;在 3.3～ 4 .5V范围内 ,试样的循环性能随Ni元素掺杂比例的增加而提高     

电解二氧化锰预处理对制备锰酸锂性能的影响(英文)

分别采用酸洗、预烧、浸渍掺铬的方式对电解二氧化锰(EMD)进行预处理,研究EMD预处理对制备锰酸锂性能的影响。采用XRD、ICP等手段对预处理的EMD及制备的锰酸锂进行表征,并通过Li/LiMn2O4电池的充放电测试对其电化学性能进行评估。结果表明,酸洗后EMD中的钠、硫等无机杂质含量显著降低;预烧能够有效去除EMD吸附的水分和有机杂质,扩大孔径,增多反应活性位点;对EMD进行浸渍掺铬的预处理,能够得到更加均质的掺铬锰酸锂材料LiCr0.05Mn1.95O4,并表现出较好的结构稳定性及容量保持率。     

Electrochemical performance of SrF2-coated LiMn2O4 cathode material for Li-ion batteries

SrF2-coated LiMn2O4 powders with excellent electrochemical performance were synthesized. The electrochemical performance of SrF2-coated LiMn2O4 electrodes was studied as function of the level of SrF2 coating. With increasing the amount of the coated-SrF2 to 2.0% （molar fraction）, the discharge capacity of LiMn2O4 decreases slightly, but the cycleability of LiMn2O4 at elevated temperature is improved obviously. In view of discharge capacity and cycleability, the 2.0% （molar fraction） coated sample shows optimum cathodic behaviors. When being cycled at 55 ℃, as-repared LiMn2O4 remains only 79% of its initial capacity after 20 cycles, whereas the 2.0% （molar fraction） coated sample shows initial discharge capacity of 108 mA-h/g, and 97% initial capacity retention.     

耐久型高倍率性能锰酸锂微球的合成(英文)

以Mn2+和NH4HCO3为原料,通过控制结晶法合成球形MnCO3前驱体模板。以LiNO3和MnCO3为原料,按照一定的摩尔比机械混合,在700°C下煅烧8h,合成高倍率性能和长循环性能的球形尖晶石LiMn2O4材料。分别考查原料的摩尔比、反应时间以及反应温度对前驱体MnCO3形貌和产率的影响。采用X射线粉末衍射和扫描电镜对合成的MnCO3和LiMn2O4进行表征,对LiMn2O4样品进行室温条件下的充放电性能测试。电化学测试结果表明:尖晶石锰酸锂微球在10C的放电倍率下的首次放电容量达90mA·h/g(1C放电容量为148mA/g),800次循环后容量保持率达到75%。该方法合成的LiMn2O4微球作为高功率型锂离子电池的正极材料有着较好的应用前景。     

Structure and electrochemical performance of spinel LiMn2O4 synthesized by mechanochemical process

1　INTRODUCTIONLithium ion battery was used in many areasbecause of its high voltage, high energy densityand long cycle life and so on. Spinel lithium man ganese oxide was one of the most promising mate rials in term of its environmental benign, low cost,easy preparation and temperature safety. Mainproblem is the poor cycle life. As we all know thatboth the structure and electrochemical performanceof material strongly depended on the preparingmethod and starting…     

Effect of calcination temperature on characteristics of LiNi1/3Co1/3Mn1/3O2 cathode for lithium ion batteries

LiNi1/3Co1/3Mn1/3O2 was synthesized by sol-gel method and effect of calcination temperature on characteristics of LiNi1/3Co1/3Mn1/3O2 cathode was investigated. The structure and characteristics of LiNi1/3Co1/3Mn1/3O2 were determined by XRD, SEM and electrochemical measurements. The results show that the compound LiNi1/3Co1/3Mn1/3O2 has layered structure with hexagonal lattice. With the increase of calcination temperature, the basicity of the material decreases, and the size of primary particle rises. The LiNi1/3Co1/3Mn1/3O2 calcined at 900 ℃ for 12 h shows excellent electrochemical performances with large reversible specific capacity of 157.5 mA-h/g in the voltage range of 2.75-4.30 V and good capacity retention of 94.03% after 20 charge/discharge cycles. Capacity of LiNi1/3Co1/3Mn1/3O2 increases with enhancement of charge voltage limit, and specific discharge capacities of 179.4 mA.h/g, 203.1 mA.h/g are observed when the charge voltages limit are fixed at 4.50 V and 4.70 V, respectively.     

F-掺杂LiMn2O4的合成及电化学性能

采用溶胶-凝胶法合成掺杂F^-的LiMn2O4。通过XRD、SEM对掺杂F-的LiMn2O4材料的组成、结构、微观形貌等进行分析与表征,测试不同F^-掺杂量的LiMn2O4在常温（20℃）、高温（55℃）下的电化学性能。结果表明：所合成的材料具有良好的尖晶石立方结构,无杂相;F^-的掺杂提高了材料的比容量,增强了材料的稳定性,改善了其在高温下的循环性能。当F^-的掺入量x由0增加到0.1时,材料的比容量由119.7 mA.h/g增加到124.9 mA.h/g,高温下充放电30个循环后容量保持率由79.4%增加到84.4%。     

Surface modification and characterization of F-Co doped spinel LiMn2O4

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 materialswith 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 ℃.     

Surface modification of spherical LiNi1/3Co 1/3 Mn1/3O2 with Al2O3 using heterogeneous nucleation process

To improve the cycle stability at high voltage and high charge/discharge rate, spherical LiNi1/3Co1/3Mn1/3O2 was coated with Al2O3 by using heterogeneous nucleation process, and the physical and electrochemical properties were studied. The SEM images show that there is a uniform coating on the modified spherical LiNi1/3Co1/3Mn1/3O2. The electrochemical tests indicate that the properties of LiNi1/3Co1/3Mn1/3O2 coated with 0.5% aluminum oxide are the best. The initial capacities are 150 and 173 mA.h/g at the rate of I C in the voltage range of 2.7-4.3 V and 2.7-4.6 V, respectively, and the discharge capacities maintain about 99% and 85% after 30 cycles, respectively. While those of the bare LiNi1/3Co1/3Mn1/3O2 are only 90% and 75%, respectively. The CV tests of LiNi1/3Co1/3Mn1/3O2 show that Al203-coating can restrain the oxide-reduction peak currents fading during the charge/discharge course.     

Synthesis and performance of Li3V2(PO4)3/C composites as cathode materials

Carbon-coated Li₃V₂(PO₄)₃ cathode materials for lithium-ion batteries were prepared by a carbon-thermal reduction (CTR) method using sucrose as carbon source. The Li₃V₂(PO₄)₃/C composite cathode materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical measurement. The results show that the Li₃V₂(PO₄)₃ samples synthesized using sucrose as carbon source have the same monoclinic structure as the Li₃V₂(PO₄)₃ sample synthesized using acetylene black as carbon source. SEM image exhibits that the particle size is about 1 μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of Li₃V₂(PO₄)₃ powders is 122 mAh·g⁻¹ at the rate of 0.2C, and the capacity retains 111 mAh−g⁻¹ after 50 cycles.