PPy含量对Fe_2O_3/PPy锂离子电池负极材料性能的影响

为研究聚吡咯(PPy)含量对Fe_2O_3/PPy负极材料电化学性能的影响,以FeCl_2·4H_2O为Fe源,采用水热法合成Fe_2O_3纳米片,用原位聚合法合成不同PPy含量的Fe_2O_3/PPy复合材料,并通过X-射线衍射和扫描电子显微镜对合成的材料进行表征;将材料组装成扣式电池,采用恒流充放电、循环伏安法和交流阻抗测试进行电化学性能表征.结果表明:PPy的加入改善了Fe_2O_3的循环稳定性,其中PPy质量分数为5.0%的Fe_2O_3/5.0%PPy负极材料的循环性能最好,在200 mA/g的电流密度下,首次放电比容量为1 342.3 mA·h/g,首次库仑效率达到75.1%;经过100次循环,其放电比容量保持为487.4 mA·h/g,高于Fe_2O_3/2.5%PPy、Fe_2O_3/7.5%PPy和Fe_2O_3的放电比容量.     

LiNi0.4Co0.2Mn0.4O2与LiMn2O4共混正极材料电化学性能

为开发具有优良循环性能和安全性能的大型锂离子电池的正极材料,将不同比例的LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和Li Mn2O4材料进行共混,研究了LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和Li Mn2O4共混以及共混比例(10∶0、8∶2、7∶3、6∶4、5∶5、0∶10)对锂离子电池的首次放电性能、循环性能和倍率性能以及交流阻抗和循环伏安曲线的影响,并采用扫描电镜对电极材料进行了表征.研究结果表明,共混比例会影响材料的电化学性能,8∶2,7∶3和6∶4配比的混合材料的体积比容量、循环性能和倍率性能要好于纯LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和Li Mn2O4材料.其中,8∶2配比的材料性能最好.     

二氧化钛/石墨烯复合材料的合成及电化学性能

为了提高TiO_2的导电性和材料的分散性,进而提高材料的倍率性能和循环性能,将二氧化钛与石墨烯复合,通过水热法合成了二氧化钛/石墨烯(TiO_2/rGO)复合材料,并对材料的形貌进行了表征,测试了材料用于锂离子电池的电化学性能.结果表明:与石墨烯复合后材料的比容量和倍率性能均升高,在电流密度为0.1C(C=150 mA/g)下,初始放电容量为374 mAh/g,50周后的放电比容量仍保持在165 mAh/g,循环保持率为44%,远高于同种方法下合成的二氧化钛样品50周后的比容量50 mAh/g和保持率17%.     

双层碳包覆Li4Ti5O12的合成和电化学性能研究

采用固相合成方法制备了双层碳包覆Li_4Ti_5O_(12)复合材料.通过X射线衍射、扫描电子显微镜、循环伏安、电化学阻抗和恒流充放电分析等测试,研究了产物的结构、形貌及电化学性能.结果表明:通过碳包覆改性后,Li_4Ti_5O_(12)的容量可明显提高,碳的包覆对Li_4Ti_5O_(12)的结构没有影响;2 C倍率下首次放电比容量为118.8 mAh/g,300次循环后放电比容量仍为108.5 mAh/g,容量保持率为91.3%,具有非常好的电化学性能.     

MoS2/石墨烯纳米复合材料的制备及其锂电性能研究

采用一种简单的水热法制备MoS2/石墨烯纳米复合材料,通过XRD,SEM,TEM,XPS等对合成的复合材料的结构和形貌进行表征,在充放电电压为0.001～3V,恒电流密度为100 mA/g条件下对MoS2和MoS2/石墨烯复合材料的电化学性能进行测试和分析.通过对比发现,MoS2/石墨烯复合材料首次充放电容量分别677.6 mAh/g和835 mAh/g,库伦效率为81％,40次循环后其放电容量仍维持在753 mAh/g,较单纯的MoS2具有更高的可逆容量和更好的循环稳定性.对MoS2/石墨烯复合材料在不同电流密度下的充放电测试发现,即使在大电流条件下充放电,电极仍能保持稳定的循环行为,表明MoS2/石墨烯复合材料具有良好的倍率性能.     

碳纳米管-介孔碳/硫复合材料的制备及其电化学性能

以碳纳米管作为基体、葡萄糖作为水热碳源,制备具有介孔结构的同轴碳纳米管-碳材料,再将硫负载到该碳基材料后得到碳纳米管-碳/硫复合材料,然后将其用作锂硫电池正极材料。利用SEM、TEM、XRD、TGA、BET等对该碳材料进行形貌结构表征。结果表明:该材料具有介孔结构,将其作为锂硫电池正极材料可有效地限制活性物质的损失。对所制备电池进行电化学测试,在0.2 C的倍率下碳纳米管-碳/硫电极首圈放电比容量为1295 mAh/g,经循环200圈后的放电比容量为653 mAh/g,每圈容量衰减率为0.24%;当充放电倍率增加到1.0 C时,首圈放电比容量为823 mAh/g,循环200圈后放电比容量高达569 mAh/g,表明该材料作为锂硫电池正极具有优异的高倍率性能。采用该方法制备的介孔碳材料有效地缩短了离子和电子的传输路径,为实现大倍率充电、降低活性物质损失提供了新的解决思路。     

rGO量对SnO_2-Fe_2O_3/rGO锂离子电池负极材料性能的影响

为改善SnO_2-Fe_2O_3的电化学性能,通过一步水热法合成SnO_2-Fe_2O_3/rGO纳米复合材料,采用XRD、SEM、电化学工作站和蓝电电池测试系统,研究rGO加入量对SnO_2-Fe_2O_3/rGO复合材料的结构和电化学性能的影响.结果表明:rGO的掺入能很好地提高SnO_2-Fe_2O_3循环稳定性和倍率性能;对于SnO_2-Fe_2O_3/rGO50复合材料,在160 m A/g的电流密度下,100次循环后,放电比容量仍然保持596.9 m Ah/g,库仑效率为98%;即使在1 A/g的电流密度下,依然有366.6 m Ah/g的平均放电比容量.     

Sn4P3-G@C负极在锂离子电池中的应用

磷化锡(Sn₄P₃)作为锂离子电池负极材料,虽然理论比容量(1.255×10³ m A·h/g)较高,但是在充放电过程中会产生巨大的体积膨胀和颗粒团聚现象,导致容量衰减严重。将石墨烯作为骨架、无定形碳材料作为包覆层,成功地制备了碳包覆Sn₄P₃-石墨烯复合材料(Sn₄P₃-G@C)。Sn₄P₃-G@C在电流密度为0.05 A/g时,循环70次后放电比容量可达0.521×10^-3 m A·h/g;在电流密度为0.10 A/g时,循环150次后放电比容量可达0.433×10^-3m A·h/g;在电流密度为0.50 A/g时,稳定循环300次,放电比容量可达0.330×10^-3 m A·h/g。片层石墨烯和碳包覆层的共同存在不仅使Sn₄P₃的结构更加稳定且导电性提升,而且有效缓解体积膨胀,...     

γ-Fe_2O_3/C复合纳米材料的制备及其储钠性能研究

环境问题和能源问题使当下社会对高效友好的储能器件的研究越来越紧迫。储量丰富且安全无毒的钠离子电池引起人们的注意。金属氧化物因其较高的理论容量、丰富的储存和低廉的成本而成为应用前景极广的钠离子电池负极材料。通过液相合成法制备出对苯二甲酸铁前驱体,结合后续的真空退火成功地制备出纳米级γ-Fe_2O_3/C。用制备的γ-Fe_2O_3/C作钠离子电池电极材料时,该电极表现出良好的电化学性能,在电流密度为50 mA/g时,经过100次充放电循环后可逆容量高达277.67 mAh/g,容量保持率为74.63%;在经过高倍率放电-充电循环,电流密度再次降到50 mA/g时,可逆容量可恢复到305.54 mAh/g,容量保持率为93.77%,库伦效率为99.6%。说明在γ-Fe_2O_3作为钠离子电池负极电极材料时,通过碳材料的包覆以及纳米化可以优化其循环性能,为后续研究电极材料的合成方法和储钠性能提供可行的途径。     

一步固相法制备高性能Li_2MnSiO_4/C锂离子电池正极材料

采用一步固相法合成了Li_2MnSiO_4/C正极材料,利用XRD,EIS和循环伏安测试对该材料进行了结构和电化学性能表征.研究了一步固相法中添加不同比例的葡萄糖对Li_2MnSiO_4材料性能的影响.结果表明:葡萄糖作碳源复合可以提高Li_2MnSiO_4正极材料的充放电比容量和循环性能,同时在一步固相合成法中还能细化Li_2MnSiO_4正极材料颗粒.葡萄糖添加量为6%时,制备得到的Li_2MnSiO_4/C正极材料首次可逆放电比容量为213.1 mAh/g.     

Preparation of LiFePO4 for lithium ion battery using Fe2P2O7 as precursor

In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy（SEM） were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the Cl space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0 μm. During the Li^＋ ion chemical intercalation, radical P2O7^4- is disrupted into two PO4^3- ions in the presence of O^2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.     

Controlled synthesis and magnetic properties of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> walnut spherical particles and octahedral microcrystals

Magnetite Fe₃O₄ walnut spherical particles and octahedral microcrystals were successfully synthesized from K₄ [Fe (CN)₆], K₃ [Fe (CN)₆] and NaOH reagents via a simple hydrothermal process. And the uniform morphology of octahedral microcrystals was obtained in the presence of ethylene glycol. The morphology and structure of products were characterized by powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The results showed that the Fe₃O₄ walnut spherical particles and octahedral microcrystals were single crystals with the face-center cubic structure and with size distributions from 2.2 to 8.6 μm and 1.6 to 12.5 μm, respectively. Their magnetic properties were detected by a vibrating sample magnetometer at room temperature. The walnut spherical particles exhibited a ferromagnetic behavior with the coercive force (Hc), saturation magnetization (Ms) and remanent magnetization (Mr) being 150.57 Oe, 97.634 and 12.05 emu/g, respectively. For the octahedral microcrystals they were 75.28 Oe, 101.90 and 6.69 emu/g, respectively. Different sizes of walnut spherical particles were controlled synthesized through adjusting the NaOH concentration. It was found that ethylene glycol molecules have a significant effect on the formation of Fe₃O₄ octahedra. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ products. Supported by Fund of weinan Teachers University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

In situ prepared Al-Si alloy matrix composites reinforced by γ-Al2O3p

A γ-Al2O3 particles reinforced Al-Si alloy matrix composite was fabricated by adding NH4Al（SO4）2 to molten aluminum alloy. TEM observation shows that in-situ γ-Al2O3 particles are generally spherical and uniformly distributed in the matrix. The results of dry sliding wear tests show that the wear resistance of the composites increases with increasing mass fraction, and the volume loss is considerably lesser than that of the matrix and is lesser than that of the composites by adding γ-Al2O3 particles directly.     

Kinetics of Fe3O4 formation by air oxidation

The kinetics of Fe₃O₄ formation by air oxidation of slightly acidic suspension of Fe(OH)₂ was studied. The effects of initial concentration of Fe(II), temperature, partial pressure of oxygen, air flow rate and stirring rate on the oxidation rate were investigated. The results show that Fe₃O₄ formation is composed of two-step reaction, the first step is the formation of Fe(OH) ₂ ⁺ by oxidation of Fe(OH)⁺ complex ions, the second step is the formation of magnetite by dehydration and deprotonation of Fe(OH)⁺ and Fe(OH) ₂ ⁺ . The oxidation reaction is zero-order with respect to the concentration of Fe(II) and around 0.5-order with respect to partial pressure of oxygen, and oxygen transfer process is rate-limiting step of oxidation reaction with apparent activation energy of 2.74 kJ · mol⁻¹.     

Modification of LiCo1/3Ni1/3Mn1/3O2 cathode material by CeO2-coating

LiCo_1/3Ni_1/3Mn_1/3O₂ was coated by a layer of 1.0 wt% CeO₂ via sol-gel method. The bared and coated LiMn_1/3Co_1/3Ni_1/3O₂ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammogram (CV) and galvanotactic charge-discharge test. The results show that the coating layer has no effect on the crystal structure, only coating on the surface; the 1.0 wt% CeO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ exhibits better discharge capacity and cycling performance than the bared LiCo_1/3Ni_1/3Mn_1/3O₂. The discharge capacity of 1.0 wt% CeO₂-coated cathode is 182.5 mAh·g⁻¹ at a current density of 20 mA·g⁻¹, in contrast to 165.8 mAh·g⁻¹of the bared sample. The discharge capacity retention of 1.0 wt% CeO₂-coated sample after 12 cycles reaches 93.2%, in comparison with 86.6% of the bared sample. CV results show that the CeO₂ coating could suppress phase transitions and prevent the surface of cathode material from direct contact with the electrolyte, thus enhance the electrochemical performance of the coated material.     

Synthesis and characterization of Mg3(PO4)2-coated Li1.05Ni1/3Mn1/3Co1/3O2 cathode material for Li-ion battery

Mg₃(PO₄)₂-coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), charge/discharge cycling and differential scanning calorimeter (DSC). SEM analysis shows that Mg₃(PO₄)₂-coating changes the morphologies of their particles and increases the grains size. XRD and CV results show that Mg₃(PO₄)₂-coating powder is homogeneous and has better layered structure than the bare one. Mg₃(PO₄)₂-coating improved high rate discharge capacity and cycle-life performance. The reason why the cycling performance of Mg₃(PO₄)₂-coated sample at 55 °C was better than that of room temperature was the increasing of lithium-ion diffusion rate and charge transfer rate with temperature rising. Mg₃(PO₄)₂-coating improved the cathode thermal stability, and the result was consistent with thermal abuse tests using Li-ion cells: the Mg₃(PO₄)₂ coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode did not exhibit thermal runaway with smoke and explosion, in contrast to the cells containing the bare Li_1.05Ni_1/3Mn_1/3Co_1/3O₂. Funded by the National Natural Science Foundation of China (No. 20273047)     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi_0.45Co_0.10Mn_0.45O₂ was synthesized from Li₂CO₃ and a triple oxide of nickel, cobalt and manganese at 950 °C in air. The structures and characteristics of LiNi_0.45Co_0.10Mn_0.45O₂, LiCoO₂ and LiMn₂O₄ were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi_0.45Co_0.10Mn_0.45O₂ has a layered structure with hexagonal lattice. The commercial LiCoO₂ has sphere-like appearance and smooth surfaces, while the LiMn₂O₄ and LiNi_0.45Co_0.10Mn_0.45O₂ consist of cornered and uneven particles. LiNi_0.45Co_0.10Mn_0.45O₂ has a large discharge capacity of 140.9 mA · h/g in practical lithium ion battery, which is 33.4% and 2.8% above that of LiMn₂O₄ and LiCoO₂, respectively. LiCoO₂ and LiMn₂O₄ have higher discharge voltage and better rate-capability than LiNi_0.45Co_0.10Mn_0.45O₂. All the three cathodes have excellent cycling performance with capacity retention of above 89.3% at the 250th cycle. Batteries with LiMn₂O₄ or LiNi_0.45Co_0.10Mn_0.45O₂ cathodes show better safety performance under abusive conditions than those with LiCoO₂ cathodes. Foundation item: Project(50302016) supported by the National Natural Science Foundation of China; Project(2005037698) supported by the Postdoctoral Science Foundation of China     

球形LiMn1.5Ni0.5O4材料的嵌脱动力学

为明晰Li Mn1.5Ni0.5O4正极材料的动力学性能,采用水热辅助共沉淀法合成了尖晶石Li Mn1.5Ni0.5O4正极材料,并采用扫描电镜(SEM)、X射线粉末衍射(XRD)和电化学阻抗(EIS)研究了材料的结构和锂离子嵌脱动力学.实验结果表明:共沉淀法制备的Li Ni0.5Mn1.5O4材料颗粒呈均匀球形,且平均粒径较小,粒度分布较窄.在循环过程中,Li Ni0.5Mn1.5O4的电荷转移电阻增大,锂离子扩散系数减小,进而电子电导率和离子电导率下降.温度升高后,Li Ni0.5Mn1.5O4材料的溶液电阻变化不大,但是电荷转移电阻逐渐增大,锂离子扩散系数逐渐减小;此外,随着温度的升高,Li Ni0.5Mn1.5O4材料的溶解速度加快,从而导致SEI膜的厚度增大.Li Ni0.5Mn1.5O4材料的嵌脱锂动力学与温度和循环次数有密切关系.     

Cu2O/Cu2S 复合材料制备及可见光催化降解甲基橙的研究

通过水热法制备Cu₂O/Cu₂S 复合材料对甲基橙(MO) 进行光催化降解实验。在Cu₂O 中引入S 元素, 通过 改变Cu/S 投加摩尔比, 从而得到不同Cu/S 的复合材料。利用XRD、SEM、UV-vis、EIS 等手段对材料进行表征, 并 对MO 进行光催化降解实验。XRD 结果表明, 随着S 含量的增多, Cu₂S 的衍射强度逐渐上升, Cu₂O 的f111g 晶面 衍射强度逐渐降低。SEM 结果表明Cu₂S 能较好地包覆在Cu₂O 八面体的表面。通过UV-vis 和EIS 结果计算得知, 复合材料带隙为1.49 eV, 电荷转移电阻大幅降低。降解实验结果表明复合材料最佳Cu/S 投加摩尔比为15 : 1, 其在 100 min 时对MO (100 mL, 10 mg/L) 降解率达到91.4%, 明显高于纯Cu₂O 对于MO 的降解率(60.3%)。猝灭实验表 明了?OH 和 ?O₂ ^-在光催化过程中起到主要作用。