LiNiyCo0.1－yMn1.9O4正极材料的沉淀法制备及其结构与电化学性能

采用沉淀法制备了尖晶石型LiMn₂O₄和LiNi_yCo_0.1－yMn_1.9O₄ (y=0, 0.05, 0.1)正极材料. 应用FT-IR、XRD和SEM技术对不同掺杂样品的相结构与形貌进行了表征, 并用恒电流充放电测试和电化学阻抗技术研究了样品的电化学行为. FT-IR、XRD和SEM结果显示: 随着掺杂型LiNi_yCo_0.1－yMn_1.9O₄ 样品中Ni含量的减少, 位于519 cm^-1处的红外峰向高频方向移动; Ni、Co 或Ni/Co的掺杂降低了LiMn₂O₄的晶格参数; 掺杂型 LiNi_yCo_0.1－yMn_1.9O₄ 样品具有更好的分散度和小的粒径. 电化学实验结果表明, 不同成分的掺杂导致电化学性能改善的原因不尽相同. 其中LiNi_0.05Co_0.05Mn_1.9O₄样品因其较低的电化学极化和较大的Li⁺扩散系数而具有较好的电化学性能.     

LiAl0.03Mn1.97O4的流变相辅助微波合成以及电化学性能

采用一种特殊微波合成法，流变相辅助微波合成法，制备了结晶度好、纯度高的尖晶石相的锂离子电池正极材料LiAl0.03Mn1.97O4。对其进行了XRD分析和SEM研究，并就结构、形貌与传统固相法制备的LiMn2O4、LiAl0.03Mn1.97O4进行了比较。采用这种流变相辅助微波合成法制备的LiAl0.03Mn1.97O4具有优良的电化学性能，电化学性能测试表明，这种材料具有比较高的首次放电容量（115mAh／g）以及良好的可逆性、优异的循环性能，25次循环结束比容量几乎不变，保持在115mAh／g左右，衰减性得到很好的改善。     

Role of local and electronic structural changes with partially anion substitution lithium manganese spinel oxides on their electrochemical properties: X-ray absorption spectroscopy study

The electronic and local structures of partially anion-substituted lithium manganese spinel oxides as positive electrodes for lithium-ion batteries were investigated using X-ray absorption spectroscopy (XAS). LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) (η = 0, 0.018, 0.036, 0.055, 0.073, 0.110, 0.180) were synthesized by the reaction between LiMn(1.8)Li(0.1)Ni(0.1)O(4) and NH(4)HF(2). The shift of the absorption edge energy in the XANES spectra represented the valence change of Mn ion with the substitution of the low valent cation as Li(+), Ni(2+), or F(-) anion. The local structural change at each compound with the amount of a Jahn-Teller Mn(3+) ion could be observed by EXAFS spectra. The discharge capacity of the tested electrode was in the order of LiMn(2)O(4) > LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) (η = 0.036) > LiMn(1.8)Li(0.1)Ni(0.1)O(4) while the cycleability was in the order of LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) (η = 0.036) ≈ LiMn(1.8)Li(0.1)Ni(0.1)O(4) > LiMn(2)O(4). It was clarified that LiMn(1.8)Li(0.1)Ni(0.1)O(4-η)F(η) has a good cycleability because of the anion doping effect and simultaneously shows acceptable rechargeable capacity because of the large amount of the Jahn-Teller Mn(3+) ions in the pristine material.     

锂离子电池正极材料LiMn_(2-2x)Sm_xSr_xO_4的合成及电化学性能

采用高温固相反应合成了一系列的LiMn2-2xSmxSrxO4正极材料(0≤x≤0.1);采用X射线衍射仪分析了合成产物的晶体结构;利用充放电试验测定了产物的电化学性能,利用电化学阻抗谱分析了产物的电化学循环机理.结果表明,所合成的LiMn2-2xSmxSrxO4(x=0,0.01,0.02,0.03,0.04,0.05)样品均保持尖晶石相,属于Fd3m空间群.LiMn1.9Sm0.05Sr0.05O4的电化学性能最佳,首次放电容量为96.8 mAh/g,在3.0~4.4 V区间内50次循环后容量保持率超过96%.与此同时,LiMn2O4和LiMn1.90Sm0.05Sr0.05O4的电极阻抗变化不同,进而影响其电化学性能.     

钕, 铈掺杂的正极材料尖晶石型LiMn2O4的制备及性能

通过掺杂不同含量的Ｎｄ,Ｃｅ制备ＬｉＭｎ２－ｘＲＥｘＯ４（ＲＥ＝Ｃｅ,Ｎｄ;ｘ＝０,０．０５,０．１,０．１５,０．２）锂离子电池正极材料,研究稀土元素拓杂对尖晶石ＬｉＭｎ２Ｏ４正极材料电化学性质的影响。掺杂Ｎｄ,Ｃｅ后ＬｉＭｎ２Ｏ４正极材料更适合于锂离子的嵌入和脱出,电池的循环性能提高,但充放电容量随掺杂量的增加而下降。Ｘ射线光电子能谱分析表明掺杂Ｎｄ,Ｃｅ的ＬｉＭｎ２Ｏ４正极材料,其Ｍｎ＾４＋     

B掺杂尖晶石型LiMn2O4正极材料的制备及长循环电化学性能

采用固相燃烧法制备了单晶多面体尖晶石型LiMn1.94B0.06O4正极材料,利用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)以及充放电测试等手段,对其晶体结构和电化学性能等进行了表征。结果表明,B掺杂没有改变尖晶石型LiMn2O4的晶体结构,促进了(440)和(400)晶面的优先生长,形成了高暴露的(111)晶面及少部分(110)和(100)晶面的单晶多面体LiMn1.94B0.06O4晶粒,减少了Mn的溶解和提供了更多的锂离子扩散通道,其晶粒尺寸在160~350 nm之间。在10C、25℃的条件下,LiMn1.94B0.06O4电极的首次放电比容量可达到103.0 mAh·g^-1,2000次循环后,表现出较好的容量保持率(57.7%);在15C高倍率下,LiMn1.94B0.06O4仍然保持了67.1 mAh·g^-1的首次放电比容量,1500次循环后,仍能维持46.2%的容量保持率;在1C、55℃的条件下,其初始放电比容量高达125.2 mAh·g^-1,表现出良好的高温性能。B掺杂能够有效提高尖晶石型LiMn2O4的高倍率性能和循环寿命,稳定晶体结构,抑制Jahn?Teller效应和缓解Mn的溶解。     

锂离子电池正极材料LiMn2O4的合成与晶体结构（英）

Spinel LiMn₂O₄ powders were prepared using two-step synthesis method consisting of solid-state reaction method and citrate modified sol-gel method. The effects of the calcination temperature and the Li/Mn ratio of raw materials were studied on the physicochemical and electrochemical properties of the spinel LiMn₂O₄ powders, such as crystallinity, lattice constant and density. The title compound was characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Polycrystalline LiMn₂O₄ powers calcined at 750 ℃ were found to be composed of very uniformly-sized microcrystal with an average particle size of 300 nm. The improvement in electrochemical properties was mainly attributed to the process of re-grinding by absolute alcohol.     

Synthesis and electrochemical properties of chemically substituted LiMn2O4 prepared by a solution-based gel method

Lithium manganese oxide, LiMn(2)O(4), and its substituted samples LiM(0.05)Mn(1.95)O(4) (M=Al, Co, and Zn) were first prepared by a cost-saving and effective new solution-based gel method using a mixture of acetate and ethanol as the chelating agent. The physical properties of the synthesized samples were investigated by thermogravimetry/differential thermal analysis, X-ray diffraction, and scanning electronic microscopy. The as-prepared powders were used as positive materials for a lithium-ion battery, whose charge/discharge properties and cycle performance were examined. The results revealed that all the substituted samples had better cycle performance than pure LiMn(2)O(4). Among these synthesized materials, the LiCo(0.05)Mn(1.95)O(4) sample had the best cycle performance. After 30 cycles, its capacity loss was only 3%. Therefore, cyclic voltammetry and electrochemical impedance spectroscopy were employed to characterize the reactions of Li ion insertion into and extraction from LiCo(0.05)Mn(1.95)O(4) electrodes.     

LiMn_2O_4的高温比容量衰减研究

采用高温固相法合成了LiMn2 O4电极材料 ,运用电化学和阴极膜X射线衍射等方法研究了LiMn2 O4在高温 (≥ 50℃ )下 ,循环时比容量衰减的现象及其衰减机理。结果表明 ,温度越高 ,LiMn2 O4的自放电越严重 ;贮存时间越长 ,LiMn2 O4的可逆容量损失越大 ,平均放电电压越低 ;高温下LiMn2 O4中Mn的溶解是造成比容量衰减的重要原因。通过掺杂微量元素的方法能有效地改善尖晶石LiMn2 O4的高温循环性能     

类溶胶-凝胶法制备LiMn_2O_(4-δ)Cl_δ正极材料

本文以水合氢氧化锂 (LiOH .H2 O)、水合硝酸锰 (Mn(No3) 2 .6H2 O) ,水合氯化锂 (LiCl.H2 O)为原料 ,用类溶胶 凝胶法制备了LiMn2 O4 δClδ,并且以此作正极进行了电化学测试 .结果表明 ,掺氯的尖晶石LiMn2 O4 正极材料具有优异的稳定性 ,且循环稳定后 ,容量几乎没有衰减 .     

尖晶石型LiMn1.9Al0.1O3.95F0.05材料的制备及其增强的倍率性能

通过溶胶-凝胶和高温固相掺杂反应可控合成了形貌均匀、结晶性好的尖晶石型LiMn_1.9Al_0.1O_3.95F_0.05正极材料,探究了Al部分取代Mn、F部分取代O后对结构的影响,测试并比较了电极材料的倍率性能和循环充放电性能. 结果表明,尖晶石型LiMn_1.9Al_0.1O_3.95F_0.05和LiMn₂O₄有同样的晶型,但电极较传统的LiMn2O4电极倍率稳定性有显著提高. 在连续混合（如0.1C、0.5C和1C）充放电150次后,LiMn_1.9Al_0.1O_3.95F_0.05电极的容量仍能保持90%以上.     

氢氧化物共沉淀法制备LiMn0.45Ni0.45Co0.1O2正极材料的反应条件

通过氢氧化物共沉淀法制备了Mn0.45Ni0.45Co0.1(OH)2, 研究了反应条件对产物形貌特征的影响, 重点研究了F-离子对产物形貌特征、振实密度的影响. 利用前述产物通过高温固相合成法制备了高密度的LiMn0.45Ni0.45Co0.1O2和LiMn0.45Ni0.45Co0.1O1.96F0.04正极材料, 并研究了F元素掺杂对循环性能的影响. 结果表明, 在沉淀体系中加入F-, 可以改善产物的形貌特征和振实密度. SEM 测试结果表明, 产物具有良好的形貌; XRD测试表明, 产物具有良好的层状结构, 无杂质相存在. 在充放电电压区间为2.8-4.4 V, 电流密度为30 mA·g-1 时, LiMn0.45Ni0.45Co0.1O2和LiMn0.45Ni0.45Co0.1O1.96F0.04首次放电容量均为157 mAh·g-1, 经过50 次循环, 放电容量保持率分别为72.6%和86.0%, F元素的掺杂可以明显改进材料的循环性能.     

四元尖晶石相Li——M——Mn——O(M=Ni,Cr,Mo,V)嵌入电极的研究

制备了用不同价态的几种金属阳离子(Ni2^+,Cr3^+,V5^+,Mo6^+)修饰的尖晶石LiMn~2O~4嵌入化合物作为锂二次电池的阴极材料,对Li/LiM~yMn~2~-~yO~4电池进行了电化学和X射线衍射研究.结果表明,其它离子的掺杂使标准尖晶石LiMn~2O~4电极对锂的反复脱嵌和嵌入有了更强的承受力,但在不同程度上降低了其初始容量.循环性能的提高归于掺杂的金属阳离子使尖晶石结构趋于更稳定.同时还讨论了修饰离子对尖晶石相在充放电时5V电压平台出现的影响。     

喷墨打印制备LiMn2O4薄膜电极及其电化学性能

通过溶胶-凝胶法制备了尖晶石LiMn2O4. 用分散剂Lormar D, 经超声分散制得了含LiMn2O4粒子的打印“墨水”, 并使用计算机喷墨打印的方法制得LiMn2O4薄膜电极. 薄膜电极的厚度约为1.8 μm. 用XRD、TG-DTA、SEM、循环伏安、电化学阻抗谱和充放电等方法对材料和电极的性能进行了表征. 结果表明, 在较大电流100 μA·cm-2 (2C)的充放电情况下, 电极能保持好的稳定性,其首次放电容量为109 mAh·g-1, 充放电54次后, 其容量仍可保持97.4%, 为105 mAh·g-1, 这可归因于薄膜电极中尖晶石LiMn2O4的晶型完整, LiMn2O4粒子小以及稳定的超薄电极结构.     

合成条件对尖晶石LiMn_2O_4的电化学性能的影响

以Li2 CO3、LiOH、LiNO3以及电解MnO2 (EMD)作原料 ,用固相反应法合成了尖晶石LiMn2 O4 .结果表明 ,反应物种类及合成条件对LiMn2 O4 的电化学性质有很大的影响 .其中以LiNO3和EMD为合成原料制得的LiMn2 O4 性能最佳 .其制备条件分两步 :先在 2 80℃加热 6h ,使熔融的LiNO3渗入EMD微孔 ,然后在 75 0℃下焙烧合成     

长寿命、高倍率(Li4Ti5O12-AC)/( LiMn2O4-AC)电池电容的制备及性能研究

以商业微米级锰酸锂(LiMn2O4)为正极,钛酸锂(Li4Ti5O12)为负极,分别与商业活性炭(AC)复合,组装成软包装电池电容样品并进行电化学测试。测试结果表明：当样品正负极均复合AC时,其电化学性能要优于只有正极复合AC和未复合AC的样品。其中,正负极活性炭复合比例为5 wt.%,负极与正极的理论容量比(N/P)为1.01时,电池电容样品拥有良好的倍率性能,且其在0.5 C时的放电比容量为56.4 mAh/g,5 C时的容量保持率为0.5 C的72.2%。此外,与未复合AC的样品相比,单体在5 C倍率下经2000次循环后的容量保持率仍有77.5%,远高于前者的30.4%。     

锂离子电池掺钴正极材料电子结构的DV-Xα研究

The electronic structures of electrode material LiMn2O4 and Li5Mn7CoO8 for the lithium ion battery are studied by employing an ab initio “atomic-basis + norm-conserving non-local pseudopotentias” method. The calculation results of the electronic structure of an ode material LiMn2O4 show that the valence band of LiMn2O4 are mainly made up of 3d atomic orbtics of Mn(8) and Mn(9), and 2 p atomic orbits of O(7), O(6) and O(4), while the conduction band contains essentially 3d orbits of Mn (8) and Mn (9), and 2p atomic orbits of O(7). At the same time, the computing results of electronic structure of electrode material Li5Mn7CoO8 indicate that the reversible capacity of the electrode can decrease and discharge voltage reduces in the cycling, and the net charge of partial lithium ions of the active electrode material and the interaction between lithium ions and oxygen ions increase. While the cycling performance of the anode can improve due to the structural stabilization of the material Li5Mn7CoO8 corresponding to the decrease of the valence band width and enhancement of the Co-O bond.     

Temperature effects on the electrochemical behavior of spinel LiMn(2)O(4) in quaternary ammonium-based ionic liquid electrolyte

Temperature dependence of the physiochemical characteristics of a room-temperature ionic liquid consisting of trimethylhexylammonium (TMHA) cation and bis(trifluoromethane) sulfonylimide (TFSI) anion containing different concentrations of LiTFSI salt was examined. Electrochemical properties of a spinel LiMn(2)O(4) electrode in 1 M LiTFSI/TMHA-TFSI ionic electrolyte were investigated at different temperatures by using cyclic voltammetry, galvanostatic measurements, and electrochemical impedance spectroscopy. The Li/ionic electrolyte/LiMn(2)O(4) cell exhibited satisfactory electrochemical properties with a discharge capacity of 108.2 mA h/g and 91.4% coulombic efficiency in the first cycle under room temperature. At decreased temperature, reversible capacity of the cell could not attain a satisfactory value due to the high internal resistance of the cell and the large activation energy for lithium ion transfer through the electrode/electrolyte interface. Anodic electrolyte oxidation results in the decrease of coulombic efficiency with increasing temperature. Irreversible structural conversion of the spinel LiMn(2)O(4) in the ionic electrolyte, possibly associated with the formation of TMHA intercalated compounds and/or Jahn-Teller distortion, was considered to be responsible for the electrochemical decay with increasing cycles.     

LiMn2O4正极在高温下性能衰退现象的研究

采用恒流充放电方法测量了温度升高导致ＬｉＭｎ２Ｏ４正极容量衰减的情况。发现当环境温度上升到５０℃时,ＬｉＭｎ２Ｏ４电极出现严重的容量损失和性能衰退,充电态的电极受影响的程度最为严重。对电解液的原子发射和红外光谱分析,电极晶相结构Ｘ－射线衍射及循环伏安实验速增加,电解液出现催化氧化是导致容量不可逆衰砬的原因。采用富锂尖晶石材料是抑制ＬｉＭｎ２Ｏ４高温性能下降的一种有效方法。     

Relationship between the electrochemical behavior and Li arrangement in Li(x)M(y)Mn(2-y)O4 (M = Co, Cr) with spinel structure

The relationship between the electrochemical behavior and the arrangement of lithium/vacancies has been investigated with electrochemical Li removal in Li(x)M(y)Mn(2-y)O4 (x < or = 1.0, 0.0 < or = y < or = 0.3, M = Co, Cr). It was shown that the electrochemical removal proceeds via two voltage regions: (1) approximately 3.9 V at x > or = approximately 0.5 and (2) approximately 4.2 V at x < or = approximately 0.5. To understand the stepwise behavior, entropy measurement of reaction, DeltaS(obs), was performed by using the electrochemical methods. The changes of the sign in deltaS(obs) from negative to positive at the composition x approximately 0.50 in Li(x)M(y)Mn(2-y)O4 indicated that the ordered arrangement of Li/vacancies was formed with electrochemical Li removal. Moreover, such an ordering was suppressed by the substitution of Co3+ and Cr3+ for Mn3+. To clarify the nature and origin of Li/vacancy ordering, the Monte Carlo simulation was performed in view of Coulombic interaction. The simulation reproduced the formation of a new phase arising from Li/vacancy ordering at x = 0.50 in Li(x)Mn2O4. In addition, the ordered arrangement of Li/vacancy at x = 0.5 was perturbed by the trivalent M3+ replacement in spinel structure due to the local clustering of Li+ around M3+. Consequently, the electrochemical behavior in spinel LiMn2O4 was deeply related to the Coulombic interactions, proved by the fact that experimentally observed changes in entropy agreed well with Monte Carlo simulation based on the Coulombic interaction.