水热法制备尖晶石LiMn2O4正极材料的研究进展

介绍了近年来国内外有关水热法合成锂离子电池正极材料尖晶石LiMn2O4的研究工作,从锰源的选取对尖晶石锂锰氧化物的水热制备方法中存在的优缺点进行了比较和评述。对今后LiMn2O4水热合成研究以及发展方向等方面做了阐述。     

Li-Ni共掺尖晶石型LiMn2O4单晶多面体材料的制备及电化学性能

采用无焰燃烧法在500℃反应3 h,然后分别在600、650、700和750℃二次焙烧6 h制备了尖晶石型Li_1.02Ni_0.05Mn_1.93O₄正极材料。结果表明,不同焙烧温度制备的Li-Ni共掺材料没有改变LiMn₂O₄的立方尖晶石结构,且随着焙烧温度的升高,颗粒尺寸变大,结晶性提高。二次焙烧温度为700℃的Li_1.02Ni_0.05Mn_1.93O₄单晶多面体晶粒正极材料具有{111}、{110}和{100}面,且电化学性能较优,在1 C倍率下初始放电比容量为108.2 mA·h·g?1,循环500次后的容量保持率为76.8%;在5 C下首次放电比容量可达到99.0 mA·h·g?1,1000次循环后,仍能维持72.1%的容量保持率;在10 C下仍显示出71.3 mA·h·g?1的首次放电比容量及经500次循环后86.4%的容量保持率。并且其具有较大的Li+扩散系数和较小的表观活化能。Li-Ni共掺LiMn₂O₄单晶多面体材料能够有效抑制Jahn-Teller效应,减小Mn的溶解及增加Li+扩散通道,使材料的晶体结构稳定,提高倍率性能和循环性能。      

温度对燃烧包覆LiMn2O4/ZnO及其电性能的影响

通过葡萄糖辅助低温燃烧制备ZnO包覆型LiMn2O4,利用X射线衍射仪、扫描电子显微镜、循环伏安、交流阻抗以及恒流充放电测试等手段,研究了温度对产物晶体结构、微观形貌及电化学性能的影响。XRD结果表明所有产物均为单相尖晶石型LiMn2O4结构。SEM结果表明产物的颗粒尺寸随温度的升高而增大。电化学性能测试表明400℃和500℃制备的LiMn2O4/ZnO具有相对优异的电化学性能,室温1C条件下首次放电比容量分别为119.3mAh/g、116.3mAh/g,循环100次后容量保持率分别85.6%、87.8%。尖晶石LiMn2O4电极的阻抗谱特征与温度有关,电池的电化学性能主要受电荷转移电阻(Rct)影响。     

焙烧温度对醋酸盐体系液相燃烧合成尖晶石型LiMn2O4的影响

以醋酸锂、醋酸锰为原料，尿素为燃料，用液相燃烧合成方法制备尖晶石型LiMn2O4物质，考察了焙烧温度（300-800℃焙烧5h）对产物的组成结构、晶粒大小及电化学性能的影响。实验结果表明，未焙烧产物中主晶相为LiMn2O4及少量Mn2O3，但在300-800℃焙烧5h后都可得到单相的LiMn2O4粉体材料，焙烧温度为900℃时，LiMn2O4部分分解为Mn3O4；产物颗粒随焙烧温度升高而长大，≤600℃时，产物颗粒〈100nm，≥700℃时产物颗粒〉100nm，可观察到LiMn2O4的特征八面体结构；在焙烧温度800℃以下，产物的电化学性能随焙烧温度的升高而增加。当电流密度为C/3时，焙烧温度为800℃的首次放电容量为105mAh／g，但循环性能较差，30次循环后仅剩83％。     

柠檬酸络合无焰燃烧法制备尖晶石型LiMn2O4

采用柠檬酸络合无焰燃烧法制备锂离子电池正极材料尖晶石型LiMn2O4，颗粒大小只有10－100nm，晶型完整，电化学性能与国内外商品化的同种材料相当。直流电阻实验显示该材料在低于室温处存在一个相变。采用柠檬酸络合无焰燃烧法可以简化柠檬酸络合反应法的制备工艺，降低其成本。     

尖晶石型LiMn2O4酸洗提锂机理研究

以高温固相法合成的尖晶石型LiMn2O4前驱体为研究对象,通过对离子筛和离子筛吸附产物的化学分析、X射线衍射图谱分析、热重分析、红外分析和滤液中锂交换量与锰损失量分析,提出并验证了离子筛和吸附产物化学组成式可由LixMn2O4(0≤x≤1)表达,其结构依然保持尖晶石结构,阐明了以盐酸为洗脱剂离子筛提锂过程的氧化还原反应机理,给出了完善的洗脱过程与吸附过程反应式。实验结果表明,洗脱和吸附过程不彻底是导致离子筛吸附量与饱和吸附量相差较大的原因,离子筛中Mn3+歧化是离子筛发生溶损的主因;提出了关于尖晶石型离子筛提锂深入研究关键问题的建议。     

溶胶-凝胶法制备尖晶石型锰酸锂的研究进展

尖晶石型锰酸锂具有独特的三维锂离子扩散通道,作为锂离子电池正极材料具有良好的充放电循环性能,且具有原材料价格便宜,对环境无污染等优点,使其成为最有希望替代LiCoO2的正极材料。尖晶石型LiMn2O4的制备方法成为近年来研究的重点,其中溶胶-凝胶法具有突出的优越性。简述了溶胶-凝胶法的基本原理,综述了溶胶-凝胶法在锰酸锂的制备及改性上的研究进展。     

熔盐燃烧法制备Ni-Cr共掺LiMn2O4正极材料及电化学性能研究

采用熔盐燃烧法和不同焙烧温度处理制备了一系列尖晶石型LiNi_0.05Cr_0.05Mn_1.90O₄(LNCMO)正极材料,研究了焙烧温度对LNCMO的结构、微观结构形貌、电化学性能和动力学性能等的影响。结果表明,所制备样品都归属于LiMn₂O₄立方晶系Fd3m空间群,随焙烧温度升高,样品颗粒逐渐增大,其中550℃制备的为纳米级颗粒,其余为亚微米级。其中600℃焙烧温度制备的LNCMO样品展现出最佳的电化学性能,在5C倍率下,其首次放电比容量为109.1mAh/g, 500次循环容量保持率为75.7%。电流密度增大到15C和30C时,经800次循环后该样品仍有64.4%和60.6%的容量保持率,并且其具有最大的Li⁺扩散系数(6.31×10^-16cm²/s)和最小的电荷转移电阻(89.0Ω)。Ni-Cr共掺有效抑制了Jahn-Teller效应,适宜的二次焙烧温度有利于稳定材料的晶体结构,从而提高...     

尖晶石LiMn2O4的掺杂研究进展

相对LiCoO2来说，价廉、低毒的尖晶石LiMn2O4作为高能锂离子电池最有潜力的正极材料已经成为市场研究的热点。但是，在充放电过程中其结构的不稳定制约了它的应用前景。为了得到结构稳定的尖晶石，许多研究小组通过掺杂其它元素来改性LiMn2O4。综述了近几年来在这方面的研究进展。     

锂离子电池正极材料尖晶石型LiMn2O4的制备与掺杂研究

综述了近年来有关锂离子电池正极材料尖晶石型LiMn2O4的制备与性能研究进展,重点讨论了尖晶石型LiMn2O4正极材料掺杂的最新研究现状,分析了该类材料的研究内容以及发展.     

Syntheses of Mn3O4 and LiMn2O4 nanoparticles by a simple sonochemical method

Mn₃O₄ and LiMn₂O₄ nanoparticles were prepared by a simple sonochemical method which is environmentally benign. First, Mn₃O₄ nanoparticles were prepared by reacting MnCl₂ and NaOH in water at room temperature through a sonochemical method, operated at 20 kHz and 220 W for 20 min. Second, LiOH was coated onto the resulting Mn₃O₄ under the same sonochemical conditions as above. The thickness of coated LiOH on Mn₃O₄ obtained from the reaction ratio of 3:1 between LiOH and Mn₃O₄ was about 4.5–5.5 nm range. Then, by heating those LiOH-coated Mn₃O₄ particles at the relatively low temperature of 300–500 °C for 1 h, they were transformed into phase-pure LiMn₂O₄ nanoparticles of about 50 to 70 nm size in diameter.     

基于离子交换机理的尖晶石型LiMn2O4脱/嵌锂模拟

基于离子交换机理,以ICSD(The Inorganic Crystal Structure Database)中LiMn_2O_4的结构数据为基础,利用Materials Studio软件包中Visualizer模块和CASTEP模块构建并优化了尖晶石型LiMn_2O_4和HMn_2O_4以及λ-MnO_2的晶体结构,并通过对比涉及各自晶体结构的系统能值、晶胞参数、键长及键角等的变化,初步验证了离子筛提锂过程是自发吸热过程;分别通过对LiMn2O4和HMn2O4添加H和Li,模拟考察了脱锂和嵌锂(即酸洗和吸附)过程中的活性原子位及H和Li的迁移轨迹,得出8a位置Li和H的离子性较强,脱锂为H置换四面体8a位置Li,并与邻近位置O形成键长约为0.098 9nm的O-H键;嵌锂为Li取代8a-16c-8a孔道中8a位置H的动力学过程。研究结果对锰基离子筛提锂的后续工作具有一定的指导意义。     

Electrochemical extraction of lithium from LiMn2O4

Lithium has been removed electrochemically at 15 μA/cm² from LiMn₂O₄ (spinel) to yield single phase Li_1?xMn₂O₄ for 0 < × ? 0.60. The electrochemical curve suggests that beyond x = 0.60 an electrochemical process other than lithium extraction occurs. Powder X-ray-diffraction spectra indicate that during the extraction process the [Mn₂]O₄ framework of the spinel structure remains intact. Previous results have shown that 1.2 Li⁺ ions can also be inserted into LiMn₂O₄, which suggests that lithium may be cycled in and out of the [Mn₂]O₄ framework of the spinel structure over a wide range of x, at least from Li_0.4Mn₂O₄ to Li₂Mn₂O₄. Discussion of the mechanism of formation of λ-MnO₂ in an acidic environment is extended.     

LiMn2O4纳米晶的低温水热法合成及表征

以KMnO4、LiOH、环己酮为原料在120℃,10h用水热法直接合成了LiMn2O4纳米晶.通过XRD,FTIR,TEM测试表明产物为纯相尖晶石LiMn2O4纳米颗粒.电化学性能初步测试表明所得LiMn2O4纳米颗粒具有良好的电化学性能.     

Preparation of LiMn2O4 thin films by aqueous solution deposition

Cathode material LiMn₂O₄ thin films were prepared by aqueous solution deposition using lithium acetate and manganese acetate as starting materials. The structures, morphologies, and the first discharge specific capacity of the thin films were investigated as a function of annealing temperature and time. The cycling properties of the thin films were also examined. The results show that LiMn₂O₄ thin films prepared by this method are homogenous and crack-free. The thin film annealed at 750°C for 30 min has good rechargeability. The capacity loss per cycle is about 0.05% after being cycled 100 times.     

硅元素掺杂改性尖晶石型锰酸锂的研究进展

尖晶石锰酸锂(LiMn₂O₄)具有理论比容量高、热稳定性高、价格低廉、循环性能良好等特点,深受研究者的亲睐,目前已有固相法、燃烧合成法和共沉淀等多种制备方法。为了进一步改善该材料的循环性能,研究者提出了元素掺杂的策略,元素掺杂改性是基于改变材料的晶体结构或材料中部分元素的平均价态来提高材料的电化学性能和结构的稳定性。Si⁴⁺掺杂可以取代材料中的部分Mn⁴⁺,从而使材料产生Jahn-Teller效应的离子数降低和尖晶石锰酸锂的八面体体积扩大,提高电化学性能。为此,综述了近几年来单一硅元素掺杂及硅与其他元素复合掺杂改性尖晶石型锰酸锂正极材料的研究进展。     

不同锰源对尖晶石型锰酸锂性能影响的研究

分别以自制锰源和工业用电解二氧化锰为原料,采用固相合成法,将锰源和碳酸锂的混合物合成尖晶石型锰酸锂.通过扫描电子显微镜、X射线衍射的方法研究了不同锰源合成的尖晶石型锰酸锂之间形貌和结构的区别,通过电性能测试研究了不同锰酸锂对锂离子电池电性能的影响.结果表明：合成的锰酸锂都有良好的尖晶石型立方结构,以碳酸锰为原料的自制三...     

Structural and electrochemical performance of three-dimensional LiMn2O4 thin film

LiMn₂O₄ thin films with three-dimensional (3D) structure were prepared by the sol–gel method. Polystyrene beads (300 nm) were dispersed in the form of monolayers on Pt/Ti/SiO₂/Si substrates, which were then used as templates for fabricating three-dimensionally ordered electrodes. A coating solution prepared from acetylacetonate sources was dropped on the template-deposited substrates, which were then calcinated at 400 °C. The templates were removed by calcinations, and a 3D structure was formed through an annealing process. The discharge capacity of the 3D LiMn₂O₄ films was 1.63–3.03 μAh cm⁻². The capacity loss over 100 cycles was approximately 18%, however, the 3D structure was not destroyed during cycling.     

Alanine-assisted low-temperature combustion synthesis of nanocrystalline LiMn2O4 for lithium-ion batteries

Nanocrystalline LiMn₂O₄ powders have been synthesized by combustion process in a single step using a novel fuel, l-alanine. Thermogravimetric analysis and differential thermal analysis of the gel indicate a sharp combustion at a temperature as low as 149 °C. Quantitative phase analysis of X-ray diffraction data shows about 97% of phase purity in the as-synthesized powder, which on further calcination at 700 °C becomes single phase LiMn₂O₄. High Brunauer, Emmett, and Teller surface area values obtained for ash (53 m²/g) and calcined powder (23 m²/g) indicate the ultrafine nature of the powder. Average crystallite size is found to be ∼60-70 nm from X-ray diffraction analysis and transmission electron microscopy. Fourier transformed infra-red spectrum shows two strong bands at 615 and 511 cm⁻¹ originating from asymmetrical stretching of MnO₆ octahedra. A nominal composition of Li_0.88 Mn₂O₄ is calculated from the inductive coupled plasma analysis. From UV-vis spectroscopy, an optical band gap of 1.43 eV is estimated which is assigned to a transition between t_2g and e_g bands of Mn 3d. Electrochemical charge-discharge profiles show typical LiMn₂O₄ behavior with a specific capacity of 76 mAh/g.