锂离子电池正极材料Li1+xV3O8合成及电化学性能的研究

利用液相沉淀法合成得到超细、粒径分布窄的球形V2O5,以该V2O5和LiOH*H2O为原料在较低温度下煅烧得到棒状Li1+xV3O8颗粒.采用XRD、SEM对样品的结构和形貌分别进行了表征.并在电压为1.8～3.8V范围,放电倍率为0.2C对制备的电极材料进行了电池性能测量.结果表明,采用比传统固相法低的温度和时间可以获得单斜晶系的纯相Li1+xV3O8.450℃合成的Li1+xV3O8首次放电比容量达到275mAh/g,550℃合成的Li1+xV3O8在循环15次后的比容量保持率为85%.     

锂离子电池正极材料Li1+xV3O8合成技术研究进展

层状的Li1 xV3O8电池正极材料具有比容量高、循环寿命长、价格便宜等优点，有望成为新一代锂离子二次电池的正极材料。综述了层状的Lil xV3O8正极材料的结构、性质、制备技术、掺杂技术、电化学性能以及影响电极材料性能的各因素。其中重点总结了Li1 xV3O8正极材料的制备技术，包括高温固相合成技术、低温合成技术和掺杂技术。指出溶胶-凝胶法和经脱水处理的电极材料在综合性能上取得了一定突破，有望实现产业化生产。     

溶胶-凝胶法合成锂离子电池正极材料Li_(1+x)V_3O_8的初步探讨

采用溶胶-凝胶法合成锂离子电池正极材料Li1+xV3O8,并用X射线衍射、扫描电镜观察、充放电循环测试、循环伏安法扫描等,研究了Li1+xV3O8的物相结构、表面形貌以及电化学性能等,并探索了合成工艺条件对材料的电化学性能的影响。结果表明,温度为400℃时合成的Li1+xV3O8晶粒较为细小均匀,粒径大小相对较为均一,颗粒大小在0.5—1.0μm左右,这些小晶粒将有效地增加其比表面积,同时电化学性能较好,10mA/g的电流密度下首次放电容量为230 mAh/g,20次循环之后容量仍能达到180 mAh/g,循环性能较好。随着合成温度增高,首次放电容量减小,循环效率降低。     

Li1.104Mn0.56Ni0.24O2富锂锰基材料Al3+掺杂研究

针对富锂锰基材料容量保持率不高,倍率性能不好等问题,以Al2O3作为Al源,通过高温固相法制备A13+掺杂的Li1.104-3xAlxMn0.56Ni0.24O2（0≤x≤0.01）正极材料。XRD结果表明掺杂的Al3+成功代替部分Li+进入到富锂锰基正极材料的晶格中。电化学性能测试表明A13+掺杂抑制了Li1.104Mn0.56Ni0.24O2材料在循环过程中电压衰减,同时提高了它的循环性能和倍率性能。Li1.0965Al0.0025Mn0.56Ni0.24O2材料在0.2 C电流密度下循环100次后,放电比容量为234.42 mA·h/g,其容量保持率高达86.32%,而未掺杂的Li1.104Mn0.56Ni0.24O2材料容量保持率仅为67.27%。     

Al3+掺杂对Li1.02Mn2O4结构和电化学性能的影响

用固相法合成了Li1.02AlxMn2-xO4(x=0.0,0.05,0.10,0.15,0.20,0.30)锂离子电池正极材料,研究了Al3+对尖晶石型Li1.02Mn2O4的结构及电化学性能的影响.结果表明,当掺杂量x小于0.2时,没有出现杂相,掺杂量为0.3时,出现杂相Al2O3;Al3+的掺入能稳定晶体结构,使材料在充放过程中很好地保持稳定,减弱Li+的能级分裂,改善材料的耐过充性能.当x=0.15时,初始最高容量为118.7 mAh·g-1,160次循环容量衰减至113.8 mAh·g-1,容量保持率为95.8%.Al3+的加入使材料的电导率降低,但材料结构更加稳定,循环性能变得更好.     

溶胶-凝胶-微波法制备Li1＋xV3O8及其性能研究

直接利用微波将溶胶一凝胶制备的干凝胶前驱体于450℃下快速合成了纯相、晶粒发育度较低的层状Li1 xV3O8.通过XRD、C-V和循环充放对样品的电化学性能进行了测试,结果表明,(100)晶面取向显著降低,2.5V放电平台明显.室温下,截止电压4～2V范围内,首次放电比容量迭318mAh/g.各项性能均优于传统固相法合成的材料.     

锂离子电池正极材料Li1+xV3O8的改性研究进展

目前锂离子电池正极材料的研究主要集中在过渡金属氧化物上,其中Li1 xV3O8成为了最具有发展前景和研究较多的正极材料之一.为了提高其电化学性能,人们开展大量的研究来对其进行改性处理.从电化学性能的角度出发,针对合成技术、离子取代、引入第二相和颗粒形貌处理等方面对Li1 xV3O8进行的改性研究和现状进行了详细的综合评述,并对各种改性机理进行了阐述.     

掺杂球形Li1+xV3O8的制备及其电化学性能研究

采用溶胶-凝胶和喷雾干燥相结合的方法合成了掺杂Mn和Co的球形Li1 xV3O8材料．选取Mn和Co作为掺杂元素，并且通过实验确定掺杂的量以1％为最佳．考察了不同热处理温度对掺杂Li1 xV3O8晶体结构与电化学性能的影响．对掺杂后的样品进行了XRD、SEM及电化学性能测试研究．结果表明，掺杂对样品的形貌和结构没有产生影响，350℃热处理温度下制备的掺杂Li1 xV3O8样品在常温下的循环性能有了较大的改善，其中掺CO后的样品性能改善最为显著．     

尖晶石型Li1-xMgxMn2O4正极材料的制备和性质

采用高温固相分段反应法制备了尖晶石LiMn2O4和Mg2 掺杂的Li1-xMgxMn2O4(x=0.05、0.1)材料,对材料进行了XRD结构分析和电化学性能等测试,结果表明:Mg2 掺杂样品Li1-xMgxMn2O4(x=0.05、0.1)仍保持尖晶石相Fd3m结构;循环性能明显改善,室温条件下50次循环后,样品Li0.9Mg0.1Mn2O4的放电容量为100mAh/g,容量保持率为9.9%,而LiMn204容量衰减率仅为18.1%.     

纳米Al2O3掺杂对LiNi1/3Co1/3Mn1/3O2性能的影响

为提高LiNi1/3Co1/3Mn1/3O2正极材料的循环性能和倍率性能,采用在底液中添加纳米Al2O3的方法,在氢氧化物共沉淀法制备前驱体过程中进行铝元素掺杂,并考察了铝掺杂量对材料形貌和电化学性能的影响。电化学性能测试结果表明,当铝掺杂量为0.02(n Al:∶n Li=0.02)时,在电压范围2.7~4.2V和0.2C倍率下,循环50次后容量保持率高达95.7%,高于未掺杂的81.5%,同时材料的倍率性能也明显提高。     

锂离子电池正极材料Li3V2-2x/3Mnx（PO4）3的溶胶凝胶法合成和电化学性能

以CH3COOLi·2H2O、V2O5、Mn(CH3COO)2·4H2O、(NH4)2HPO4和蔗糖为原料,采用溶胶–凝胶法合成了掺锰磷酸钒锂/碳(Li3V2-2x/3Mnx(PO4)3/C)复合正极材料,用XRD、XPS、SEM、电化学性能对样品进行了表征.测试结果表明,少量锰的掺杂并未改变Li3V2(PO4)3/C的单斜结构,Li3V1.94Mn0.09(PO4)3中的Mn和V分别以+2和+3价存在,其颗粒类似球形,直径比较均匀且小于200 nm,并表现出良好的电化学性能.在0.1C倍率和3.0～4.8 V电压内,该样品的首次充、放电容量分别为182.1和168.8 mAh/g,放电效率高达92.69%,而且100次循环后,其放电比容量仍是首次放电容量的77.4%.     

Characterization of the electrochemical reactions in the Li(1+x)V3O8/Li cell by soft X-ray absorption spectroscopy and two-dimensional correlation analysis

We applied soft X-ray absorption spectroscopy (XAS) and two-dimensional (2D) correlation analysis to the first lithium insertion-extraction cycle in a Li(1+x)V3O8/Li cell in order to investigate the electrochemical reactions of lithium with the Li(1+x)V3O8 electrode. The V L(II,III)-edge and O K-edge spectra of the Li(1+x)V3O8 electrode were obtained for varying electrode lithium content. The insertion of lithium leads to the reduction of the V5+ species present in the pristine Li(1+x)V3O8 electrode, and to the red shift and the broadening of the spectral features of the V L(II,III) edge compared to those of the pristine electrode. In the extraction process, the main spectral features at the highest value of the extraction of lithium show some differences compared to the features of the pristine electrode spectrum due to the residual lithium ions in the Li(1+x)V3O8 structure. The O K-edge spectra revealed that the insertion of lithium mainly affects the V 4sp-O 2p bonds and consequently induces a change in bonding geometry. The 2D correlation analysis of these spectra clearly shows that V-O bonds are significantly perturbed by the insertion-extraction of lithium into the Li(1+x)V3O8 electrode.     

Electrochromic Properties of Sol-gel Deposited V2O5 and TiO2-V2O5 Binary Thin Films

Transparent mixed phase (1- x)V205-xTiO2 (x=0,0.1,0.2,0.3,0.4) thin films were prepared on indium tin oxide (ITO) coated glass via sol-gel process. The films were characterized by cyclic voltammetry, optical spectroscopy, scanning electron microscopy, IR and X-ray diffractometer.     

富锂正极材料Li1+x[Ni0.36Mn0.64]1-xO2的制备及电化学性能研究

采用氢氧化物共沉淀-高温固相焙烧法合成了富锂正极材料Li1+x[Ni0.36Mn0.64]1-xO2(x=0.12,0.15,0.18,0.2)。采用XRD表征其结构,SEM表征其形貌,恒电流充放电和循环伏安测试其电化学性能。其中,XRD结果表明各样品都具有α-NaFeO2型层状结构。结果表明:室温下以30mA/g的电流密度,在4.6~2.75V的电压范围内充放电,x=0.15的首次放电比容量为237.9mAh/g,经50次循环后容量保持率为98%。研究发现,层状富锂镍锰正极材料中的Li2MnO3组分在充放电过程中会逐渐向尖晶石相转变,这是容量衰减的主要原因。     

Synthesis and electrochemical properties of modification LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion battery

The layered LiNi1/3CO1/3Mn1/3-xMg(x)O2 (x = 0, 0.01, 0.03, 0.05) cathode materials were prepared by solid state reaction, then copper oxide was coated on the product. The structures, morphologies and electrochemical properties of the LiNi1/3Co1/3Mn1/3-xMg(x)O2 and CuO-coated LiNi1/3Co1/3Mn1/3-xMg(x)O2 were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), and electrochemical tests. The results showed that the electrochemistry properties and cycle performance of magnesium doped LiNi1/3Co1/3Mn1/3O2 and CuO-coated LiNi1/3Co1/3Mn1/3-xMg(x)O2 materials were improved. The optimal doping content of Mg was x = 0.03 in the LiNi1/3Co1/3Mn1/3-xMg(x)O2 samples to achieve high discharge capacity and good cyclic stability, and the first discharge special capacity was 158.5 mAh/g at 0.2 C in the voltage of 2.5-4.3 V, then CuO-coated LiNi1/3Co1/3Mn1/3-0.03Mg0.03O2 was investigated. The electrode reaction reversibility and electronic conductivity were enhanced through Mg-doped and CuO-coated.     

Maximizing ionic transport of Li1+xAlxTi2-xP3O12 electrolytes for all-solid-state lithium-ion storage: A theoretical study

The concept of all-solid-state batteries provides an efficient solution towards highly safe and long-life energy storage,while the electrolyte-related challenges impede their practical application.Li1+xAlxTi2-xP3O12 (0 ≤ x ≤ 1) with superior Li ionic conductivity holds the promise as an ideal solidstate electrolyte.The intrinsic mechanism to reach the most optimum ionic conductivity in Al-doped Li1+xAlxTi2-xP3O12,however,is unclear to date.Herein,this work intends to provide an atomic scale study on the Li-ion transport in Li1+xAlxTi2-xP3O12 electrolyte to rationalize how Al-dopant initiates interstitial Li activity and facilitate their easy mobility combining Density Functional Theory (DFT) and ab initio Molecular dynamics (AIMD) simulations.It is discovered that the interstitial Li ions introduced by Al dopants can effectively activate the neighboring occupied intrinsic Li-ions to induce a long-range mobility in the lattice and the maximum Li ionic conductivity is achieved at 0.50 Al doping concentration.The Li-ion migration paths in Li1+xAlxTi2-xP3O12 have investigated as the degree of distortion of[PO4]tetrahedra and[TiO6]octahedra resulted by different Al doping concentrations.The asymmetry of the surrounding distorted[PO4]and[TiO6]polyhedrons play a critical role in reducing the migration barrier of Li ions in Li1+xAlxTi2-xP3O12.The flexible[TiO6]polyhedrons with a capacity to accommodate the structural distortion govern the Li ionic conductivity in Li1+xAlxTi2-xP3O12.This work rationalizes the mechanism for the most optimum Li ionic conductivity in Al-doped LiTi2P3O12 electrolyte and,more importantly,paves a road for exploring novel all-solid-state lithium battery electrolytes.     

溶液法合成锂离子电池的阴极材料LiZnxNi0.5-xMn1.5O4及其电化学性质研究

采用共沉淀法及溶胶-凝胶法合成了锂离子电池的阴极材料LiZnxNi0.5-xMn1.5O4 (0.01≤x≤0.09) .结构研究结果表明用这些方法可以在比固相反应低得多的温度下得到单相的尖晶石.Li/LiZnxNi0.5-xMn1.5O4半电池在1mol/L LiPF6/EC DEC DMC(1:1:1)中于2.8～4.9V间进行充放电测试的结果表明充放电平台仅出现在4.7V附近,因此在充放电过程中仅发生Ni2 Ni4 的价态变化,该半电池以0.05mA/cm2的电流密度进行充放电的首次充电比容量高达理论值并随着x值的增大而减小,测试结果还表明合成方法及热处理过程对材料的性能有决定性的影响.     

Synthesis of Li(1+x)V3O8 by chemical route and its characterization

Lithium trivanadate (Li(1+x)V3O8) nanorods have been synthesized by the simple polymer precursor route using the polymer, polyvinyl pyrrolidone (PVP) as the complexing agent. Thermal behavior of the precursor has been studied by the differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and differential thermal analysis (DTA) techniques. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) studies confirm the formation of the compound. High resolution scanning electron microscopy (HRSEM) analysis reveals the synthesized Li1.2V3O8 particles to be nanorods with an average diameter of 50 nm.     

Li2M4O9-石墨烯复合材料的制备及其电化学性能研究

采用溶胶凝胶法制备Li2M4O9,将其与氧化石墨烯在不同溶剂中进行溶剂热反应,以制备Li2M4O9墨烯复合材料,通过x射线衍射（XRD）、扫描电镜（SEM）进行表征,并对其进行一系列的电化学性能测试,包括充放电、循环伏安、循环效率、循环性能和交流阻抗测试。Li2M4O9-墨烯复合材料首次放电比容量由144．6mAh/gr提高至212．8mAh／g,50次充放电循环后,库仑效率保持在95％以上,电化学性得到提高。