重质化学二氧化锰制备尖晶石锰酸锂

采用重质二氧化锰制备尖晶石LiMn2O4。采用X射线衍射、扫描电镜、恒电流充放电等技术对合成产物进行物相、形貌和电化学分析。结果表明：采用重质化学二氧化锰与电解二氧化锰制备的LiMn2O4粉末具有相似的X射线衍射结果。采用重质化学二氧化锰制备的LiMn2O4在0.2C、0.5C、1C、2C及3C放电倍率下放电比容量分别为108.5 mAh/g、104.7mAh/g、97.3mAh/g、86.5 mAh/g和70.7 mAh/g,以电解二氧化锰为原料制备的LiMn2O4放电比容量则分别为106.1 mAh/g、103.4mAh/g、99.1mAh/g、89.2mAh/g和75.5mAh/g。两种原料制备的LiMn2O4在不同倍率下的比容量和充放电循环性能差别不大,采用重质化学二氧化锰制备的锰酸锂电化学性质可以达到或超过采用电解二氧化锰制备的锰酸锂。     

合成原料对LiMn2O4电化学性能的影响研究

采用固相法分别以不同原料合成尖晶石LiMn2O4。采用X射线衍射、扫描电子显微镜、循环伏安及恒电流充放电等技术检测和分析合成产物的物相、形貌及电化学性能。研究表明,与采用电解MnO2为原料合成的LiMn2 O4相比,采用Mn3 O4为原料合成的LiMn2 O4粉末X射线衍射峰强度更大,室温下以0.2 C倍率充放电循环30次时,首次放电比容量和容量保持率分别为128.7 mA.h/g和98.4%,高于以电解MnO2为原料合成LiMn2 O4的123.7 mA.h/g和85.0%。55℃循环时,采用Mn3 O4为原料合成的LiMn2 O4容量保持率比采用电解MnO2为原料合成LiMn2O4的高10.7%。     

中空八面体锂离子电池正极材料LiFePO_4的制备及电化学性能

以醋酸锂、磷酸、七水合硫酸亚铁为原料,聚乙二醇为分散剂,通过一步水热法制备得到中空八面体LiFePO_4锂离子电池正极材料。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学性能测试仪对样品晶型、形电化学性能进行了表征测试。研究结果表明,在2.5~4.2 V电压范围内,以0.1 C(17 mA/g)倍率进行充放电,样品首次放电比容量为129.6 mA·h/g;0.2、0.5、1、2和5 C的充放电倍率时,首次放电比容量分别达到123.6、119.7、114.1、99.5g和90.6 mA·h/g。10 C的充放电倍率时首次放电比容量为84.3 mA·h/g,说明中空八面体LiFePO_4在高倍率下表现出优异的电化学性能。     

LiNi_(0.5)Mn_(1.5)O_4正极材料制备及其电化学性能研究

以二氧化锰、氧化镍和碳酸锂为原料,采用二次焙烧工艺制备了尖晶石型镍锰酸锂(LiNi0.5Mn1.5O4)正极材料。采用X射线衍射(XRD)、扫描电镜(SEM)、交流阻抗测试(EIS)和充放电测试对LiNi0.5Mn1.5O4正极材料进行了表征。结果表明,合成的材料晶体结构完整,形貌规则,并且表现出优异的电化学性能,其0.2 C首次放电容量为134.6 mA·h/g,5 C首次放电容量为112.9 mA·h/g,5 C循环34次后容量保持率为103.3%。     

不同锰源制备尖晶石LiMn_2O_4及电化学性能研究

分别用化学二氧化锰、电解二氧化锰、MnCO_3和Mn_3O_4为锰源,通过高温固相法合成尖晶石LiMn_2O_4。采用X射线衍射仪、扫描电子显微镜、恒电流充放电技术、交流阻抗及电位阶跃法,对合成的尖晶石LiMn_2O_4物相、形貌以及电化学性能进行检测分析。结果表明,由Mn_3O_4制备的LiMn_2O_4的X射线衍射峰强度最大且粒度较为均匀。在室温条件下,以0.2C倍率充放电循环20次,Mn_3O_4制备的LiMn_2O_4首次充放电比容量为128.3 mA·h/g,容量保持率为97.1%,优于另外三种锰源作为原料合成的尖晶石LiMn_2O_4。化学二氧化锰、电解二氧化锰、MnCO_3、Mn_3O_4合成尖晶石LiMn_2O_4电极材料的扩散系数DLi+分别为2.26×10~(-11),4.54×10~(-11),0.83×10~(-11),8.25×10~(-11)cm~2/s。     

化学二氧化锰改性处理对锰酸锂性能的影响

将化学二氧化锰进行高温烧结改性处理后制备锰酸锂,与未经改性处理的化学二氧化锰制备的锰酸锂进行性能比较。通过XRD、SEM考察了改性处理对锰酸锂的结构及形貌的影响,通过充放电性能检测分析了改性处理对锰酸锂电化学性能的影响。结果表明,制备的锰酸锂均为规则的尖晶石结构,在850℃下改性处理的化学二氧化锰制备的锰酸锂晶体结构最稳定,颗粒大小分布均匀,电化学性能最佳,首次放电比容量为118.4 mA·h/g,循环100次后容量保持率为92.74%。     

Li_2FeSiO_4/C复合材料的制备及电化学性能

以CH3COOLi、FeC2O4、纳米SiO2为原料,葡萄糖为碳源,超导碳为微波耦合剂,采用微波加热法合成了Li2FeSiO4/C材料。考察了不同微波时间对材料室温下电化学性能的影响,并通过X射线衍射、扫描电子显微镜、透射电子显微镜和X射线能谱对样品的晶型结构、表面形貌和组成进行表征分析。结果表明,微波合成法可以快速制备Li2FeSiO4/C材料,微波时间16min所得样品具有最好的电化学性能。室温下以C/16倍率进行充放电测试,放电容量为111.5mA·h/g;以0.2C进行充放电循环,首次放电容量为96.7mA·h/g,19次循环后容量仍有95.2mA·h/g。     

掺杂与表面包覆对尖晶石型LiMn2O4电化学性能的影响

用固相法制备了Cr3 和F-同时掺杂的尖晶石型LiMn2O4正极材料,并对掺杂材料进行氧化铝表面包覆改性,用扫描电子显微镜和X射线衍射研究了材料的表面形貌和晶体结构,用充放电实验和交流阻抗技术测试了材料的电化学性能。结果表明:LiMn2O4在掺杂Cr3 和F-及表面包覆氧化铝后仍为尖晶石型结构,随掺杂和包覆量的增加,材料首次放电容量降低,但循环性能明显改善,其中未掺杂、掺杂量为0.10和表面包覆0.3%的氧化铝的材料室温首次放电容量分别为125.3 mA·h/g、117.5 mA·h/g和113.7 mA·h/g,循环25次后容量保持率分别为82.7%、91.5%和93.6%,而55℃下25次循环后放电容量及其保持率以表面包覆氧化铝的最佳,分别达到104.2 mA·h/g和92.1%。     

玉米棒状LiFePO4正极材料的离子热法制备及性能

以自制离子液体为反应介质,FeSO4·7H2O、(NH4)2HPO4和LiOH·H2O为原料,采用离子热法制备了LiFePO4,并经过热处理覆炭制备出LiFePO4/C复合材料。利用X射线衍射、扫描电子显微镜、透射电子显微镜表征了材料的结构和形貌,采用恒电流充放电测试其充放电性能。结果表明:常压低温下所制备的LiFePO4正极材料和经热处理制备的LiFePO4/C都具有橄榄石晶体结构,呈玉米棒状形貌,并表现出优良的充放电性能。室温下,0.1C倍率下LiFePO4和LiFePO4/C首次放电比容量分别为140.7 mA·h/g和162.5 mA·h/g。LiFePO4/C在0.1、1 C和5 C倍率下循环30次均无明显衰减。     

LiMn2O4空心多孔正极材料的制备

以水热法所制碳球为模板,采用溶胶?凝胶法制备LiMn2O4空心多孔颗粒(PLMO),研究了煅烧温度和碳球加入量对样品相演化和表面形貌的影响,比较了PLMO和未加入碳球的LiMn2O4 (LMO)的电化学性能. 结果表明,650?750℃煅烧12 h可制得蜂窝状孔型结构的PLMO;在放电倍率0.5C下循环50次,PLMO的放电容量从126 mA?h/g降至111 mA?h/g,均高于相应LMO的放电容量. 在5C放电倍率下,PLMO的首次放电容量可达89 mA?h/g,较LMO提高约39%.     

Al_2O_3包覆锂电池正极材料LiMn_2O_4的合成及电化学性能研究

研究了在锂离子电池尖晶石Li Mn2O4正极材料上包覆Al2O3来改善材料在循环过程中的容量衰减问题。通过SEM和X射线衍射研究材料的表观形貌和晶体结构。在电化学性能测试中,发现包覆Al2O3可以减少材料与电解液的直接接触,阻止了电解液对尖晶石的侵蚀,最终有效地改进锂电池正极材料Li Mn2O4的电化学性能。     

尖晶石锰酸锂表面化学镀钴研究

表面化学镀钴对LiMn2O4进行改性,X射线衍射、扫描电子显微镜、交流阻抗及恒电流充放电等技术检测和分析合成产物的物相、形貌及电化学性能。研究表明,与未镀钴的LiMn2O4相比,镀钴LiMn2O4粉末的X射线衍射峰强度有所变弱,样品颗粒表面粗糙,有许多小孔。化学镀钴后的LiMn2O4放电容量由改性前的123mA.h/g下降到改性后的112mA.h/g,室温下经20次循环后的容量保持率为96.8%,高于未镀钴的85.8%。55℃经20次高温循环后的比容量保持率为91.7%,远高于未镀钴的76.2%。表面镀钴后LiMn2O4的循环性能得到了显著改善。     

Examinations on 2.5 V Li[Li1/3Ti5/3]O4/Li[Li0.1Al0.1Mn1.8]O4 cells at −10, 25, and 55 °C for the first-generation 12 V lead-free batteries

Electrochemical behaviors of 2.5 V Li[Li_1/3Ti_5/3]O₄ (LTO)/Li[Li_0.1Al_0.1Mn_1.8]O₄ (LAMO) cells for the first-generation 12 V lead-free battery were examined at −10, 25, and 55 °C. The LTO/LAMO cells showed the same rechargeable capacity in temperature ranging from −10 to 55 °C when the cells were examined at 0.5 mA cm⁻² in cell potential ranging from 0 to 3.0 V. Capacity fading after 250 cycles was negligibly small at −10 °C. Rechargeable capacities, however, faded 5% at 25 °C and 15% at 55 °C after 250 cycles. In the discharged LTO/LAMO cell after 250 cycles at 55 °C, the state of charge (SOC) of the positive electrode was 16% while SOC of the negative electrode was 0%, indicated that the capacity fading was due to an imbalance in SOC between the positive and negative electrodes. To understand the progress of an imbalance in SOC, the LTO/LAMO cell with a lithium auxiliary electrode was fabricated and examined at 55 °C for 400 cycles, and the possible origin of capacity fading was discussed.     

一种新型电极材料—锰酸锂

介绍了九十年代国外兴起的一种锂离子电池用新型电极材料－锰酸锂，综述了其生产工艺、技术现状、发展前景及国外开展其研究开发的优势。     

Comparison of structure and electrochemistry of Al- and Fe-doped LiNi1/3Co1/3Mn1/3O2

LiNi_1/3Co_1/3−xM_xMn_1/3O₂ (M = Fe and Al; x = 0, 1/20, 1/9 and 1/6) have been synthesized by firing the co-precipitates of metal hydroxides. The impacts of Fe and Al doping on the structure and electrochemical performances of LiNi_1/3Co_1/3Mn_1/3O₂ are compared by means of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and galvanostatic charge/discharge test as cathode materials for lithium ion batteries. These materials keep the same layered structure as the LiNi_1/3Co_1/3Mn_1/3O₂ host. It is found that Fe- and Al-doped LiNi_1/3Co_1/3Mn_1/3O₂ show different characteristics in lattice parameter and cycling voltage plateau with increasing dopant dose. More interestingly, low Al doping (x < 1/20) improves the structural stability while Fe doping does not have such effect even at low Fe content.     

Improvement of electrochemical properties of LiNi0.5Mn1.5O4 spinel prepared by radiated polymer gel method

LiNi_0.5Mn_1.5O₄ as a 4.7 V-class cathode material was prepared through the radiated polymer gel method that allowed homogeneous mixing of starting materials at the atomic scale. After calcinations of the polymer gels containing the metal salts at different temperatures from 750 to 1150 °C, powders of a pure LiNi_0.5Mn_1.5O₄ phase were obtained. X-ray diffraction and transmission electron microscopy were used to characterize the structures of the powders. Galvanostatic cell cycling and a simultaneous DC resistance measurement were performed on Li/LiNi_0.5Mn_1.5O₄ cells. It is found that the powder calcined at 950 °C shows the best electrochemical performance with the initial discharge capacity of 139 mAh g⁻¹ and 96% retention after 50 cycles. Adopting a slow cooling procedure for the powder calcination can increase the capacity of LiNi_0.5Mn_1.5O₄ at the 4.7 V plateau. Besides, a “w”-shape change of the DC resistance of Li/LiNi_0.5Mn_1.5O₄ cells is a good indication of the structural change of LiNi_0.5Mn_1.5O₄ electrode during charge and discharge courses.     

Thin films of lithium manganese oxide spinel as cathode materials for secondary lithium batteries

The miniaturization of rechargeable lithium-ion batteries requires high quality thin-film electrodes. Electrostatic spray deposition (ESD) technique was used to fabricate LiMn₂O₄ thin-film electrodes with three different morphologies: sponge-like porous, fractal-like porous, and dense structures. X-ray diffraction (XRD) and scanning electron microscopy were used to analyze the structures of the electrodes. These electrodes were made into coin cells against metallic lithium for electrochemical characterization. Galvanostatic cycling of the cells revealed different rate capability for the cells with LiMn₂O₄ electrodes of different morphologies. It is found that the cells with LiMn₂O₄ electrodes of porous, especially the sponge-like porous, morphology better rate capability than those with dense LiMn₂O₄ electrodes. Electrochemical impedance spectroscopy (EIS) study indicates that the large surface area of the porous electrodes should be attributed to the smaller interfacial resistance and better rate capability.     

Study of LiNi0.5Mn1.5O4 synthesized via a chloride-ammonia co-precipitation method: Electrochemical performance, diffusion coefficient and capacity loss mechanism

LiNi_0.5Mn_1.5O₄ powders are prepared via a new co-precipitation method. In this method, chloride salts are used as precursors and ammonia as a precipitator. The impurity of chlorine can be removed via a thermal decomposition of NH₄Cl in the subsequent calcination. X-ray diffraction pattern reveals that the final product is a pure spinel phase of LiNi_0.5Mn_1.5O₄. Scanning electron microscopy shows that the powders have an octahedron shape with a particle size of about 2 μm. Electrochemical test shows that the LiNi_0.5Mn_1.5O₄ powders exhibit an excellent cycling performance and after 300 cycles, the capacity retention is 83%. The lithium diffusion coefficient is measured to be 5.94 × 10⁻¹¹ cm² s⁻¹ at 4.1 V, 4.35 × 10⁻¹⁰ cm² s⁻¹ at 4.75 V and 7.0 × 10⁻¹⁰ cm² s⁻¹ at 4.86 V. The mechanism of capacity loss is also explored. After 300 cycles, the cell parameter ‘a’ decreases by 0.54% for the quenched sample (LiNi_0.5Mn_1.5O_4−δ) and by 0.42% for the annealed sample (LiNi_0.5Mn_1.5O₄). Besides, it is the first time to identify experimentally that the Ni and Mn ions dissolved in the electrolyte can be further deposited on the surface of anode.