基于不同碳源的LiFePO4／C的合成及电化学性能研究

以不同有机碳(月桂酸、葡萄糖和柠檬酸)为碳源合成了橄榄石型LiFePO4/C锂离子电池复合正极材料.研究了不同碳源对LiFePO4/C复合材料的结构、形貌及其电化学性能的影响.结果表明用不同碳源合成的LiFePO4/C复合材料的形貌及颗粒大小不同,影响其电化学性能.其中以葡萄糖作为碳源合成的复合正极材料粒径细小,分布均匀,具有最好的电化学性能,在0.1 C放电电流下,首次放电比容量达143.1 mAh/g,接近LiFePO4的理论比容量(170 mAh/g).     

镁离子掺杂对LiFePO4材料性能的影响

为了提高LiFePO4的电化学性能,用Mg2 对LiFePO4进行掺杂,以Li3PO4为锂源、Mg(OH)2为掺杂源,采用固相法合成锂离子电池正极材料Li1-xMgxFePO4(x=0.005、0.01、0.02和0.03).通过X射线衍射分析及电化学测试,研究了Mg掺杂对材料的结构和电化学性能的影响.实验研究表明,掺入少量的Mg2 ,可以减小晶胞体积,提高LiFePO4的循环性能和比容量.当Mg的掺入量为2 mol%时,以0.1C倍率充放电,Li0.98Mg0.02FePO4最大放电容量为123.6 mAh/g.     

掺钴对富锂磷酸亚铁锂大电流放电性能的影响

采用固相法制备了具有橄榄石型结构的微米Li1.12Fe0.98Co0.02PO4/C样品.通过充放电循环、循环伏安实验、交流阻抗、XRD衍射、红外光谱、扫描电镜等现代技术研究了制备的样品的电化学性能.研究表明,在2 C倍率电流下,制备的Li1.12FePO4/C和Li1.12Fe0.98Co0.02PO4/C样品第1循环的放电容量分别为64.8和108.9 mAh.g-1,第30循环的放电容量分别为67.3和110.1 mAh.g-1.因此,掺钴的富锂Li1.12Fe0.98Co0.02PO4/C样品具有明显改善的大电流放电性能.     

Mn2+掺杂对LiFePO4正极材料结构、性能及嵌锂动力学的影响

为了改善橄榄石型LiFePO4正极材料的性能,采用高温固相法合成了Mn掺杂的LiMnxFe1-xPO4(x=0,0.10,0.25,0.40,0.50)材料.采用X射线粉末衍射、扫描电子显微镜、充放电测试、循环伏安和电化学阻抗谱研究了材料的结构、电化学性能和锂离子嵌脱动力学.结果表明,锰掺杂的LiFePO4样品颗粒分布比较均匀,具有较小的平均粒径和窄的粒度分布,LiMnxFe1-xPO4是纯相的橄榄石结构.在不同倍率下,LiMn0.4Fe0.6PO4具有最高的放电容量和最好的动力学性能.Mn的掺杂提高了LiFePO4材料的可逆性、锂离子扩散系数和放电容量,减小了电荷转移电阻,进而提高了其动力学性能.     

高温固相法制备LiFePO4／C正极材料及其性能研究

以Fe2O3,LiH2PO4,乙炔黑和蔗糖为原料,采用高温固相合成方法制备LiFePO4／C复合正极材料。利用X射线衍射（XRD）、扫描电镜（SEM）和电化学测试等方法对合成材料的结构、形貌以及电化学性能进行表征。结果表明,合成材料为单一晶相正交晶系结构,在电压为2．50～4．20V（vs．Li^＋／Li）,以0．1mA／cm^2电流密度下经恒电流充放电测试,其首次放电比容量为156．3mAh／g,经过30周充放电循环后放电比容量为157．7mAh／g,表现出较大的初始放电比容量和优异的循环性能。     

高温固相法合成尖晶石型Li4Ti5O12及其性能研究

以Li2CO3和TiO2为原料,以乙醇为分散剂,采用高温固相方法合成Li4Ti5O12锂离子电池负极材料,利用XRD、SEM和电化学测试等方法对合成材料的结构、形貌以及电化学性能进行了表征。系统考察了热处理温度对Li4Ti5O12负极材料结构及电化学性能的影响,同时也研究了锂的投料量对Li4Ti5O12电化学性能的影响。在1.0~2.2 V（vs.Li/Li＋）范围内,以0.1 mA/cm2的电流密度对最佳工艺条件下合成的Li4Ti5O12负极材料进行了恒电流充放电测试。其首次放电比容量为167 mAh/g,经过30周充放电循环后放电比容量几乎没有衰减,表现出较大的初始放电比容量和良好的循环性能。     

Mg2+掺杂的LiFePO4材料的共沉淀合成与表征

提出了一种采用共沉淀法合成镁掺杂的锂离子正极材料LiFePO4的新方法,研究了合成条件,采用XRD,SEM,循环伏安测定,电化学阻抗谱分析,以及充放电测试对合成的材料作了表征分析．结果表明,采用共沉淀合成方法可以获得性能良好的LiFePO4;Mg^2＋掺杂对LiFePO4结构没有产生明显的影响,但掺杂量的大小对LiFePO4的放电性能有较大影响．     

Cu微粒包覆Cu/LiFePO4正极材料的制备及性能研究

用高温固相反应法制备Cu微粒包覆的锂离子电池正极材料Cu/LiFePO4。采用X射线衍射、场发射扫描电镜对材料的物相结构和颗粒形貌进行分析和观察,采用恒流充放电、慢扫描循环伏安法和电化学阻抗谱法测试材料的电化学性能。结果表明,Cu微粒包覆使复合材料颗粒分散更均匀,结晶更明显;Cu/LiFePO4（n（Cu）∶n（Li）=1∶15）正极材料首次放电比容量最高为142.8 mA.h/g,与纯LiFePO4正极材料的对应值151.7 mA.h/g相比有所下降;虽然Cu微粒的加入在一定程度上能够提高材料的电子导电率,但在第一周充电时Cu即发生不可逆氧化,导致该复合材料具有较低的放电比容量和较大的首次不可逆容量损失。     

双碳源在LiFePO4/C微波固相合成中的协同效应

以Li2CO3,FeC2O4·2H2O和NH4 H2 PO4为前驱体,分别以葡萄糖和葡萄糖/乙炔黑为碳源,利用微波加热合成了LiFePO4/C正极材料.用X射线粉末衍射（XRD）和扫描电镜（SEM）对材料进行了表征,用四探针法测定了材料的电导率.研究了碳源与微波温度对材料微结构和电化学性能的影响,发现由于乙炔黑的协同效应,用双碳源在600℃反应即可得到最佳电化学性能的LiFePO4/C,而仅用葡萄糖作碳源反应需要在较高温度（如700℃）下进行.     

双碳源在LiFePO4/C微波固相合成中的协同效应

以Li2CO3,FeC2O4·2H2O和NH4H2PO4为前驱体,分别以葡萄糖和葡萄糖/乙炔黑为碳源,利用微波加热合成了LiFePO4/C正极材料.用X射线粉末衍射(XRD)和扫描电镜(SEM)对材料进行了表征,用四探针法测定了材料的电导率.研究了碳源与微波温度对材料微结构和电化学性能的影响,发现由于乙炔黑的协同效应,用双碳源在600℃反应即可得到最佳电化学性能的LiFePO4/C,而仅用葡萄糖作碳源反应需要在较高温度(如700℃)下进行.     

Effects of different iron sources on the performance of LiFePO_4/C composite cathode materials

Olivine LiFePO4/C composite cathode materials were synthesized by a solid state method in N2 + 5vo1% H2 atmosphere.The effects of different iron sources,including Fe(OH)3 and FeC2O4·2H2O,on the performance of as-synthesized cathode materials were investigated and the causes were also analyzed.The crystal structure,the morphology,and the electrochemical performance of the prepared samples were characterized by X-ray diffractometry (XRD),scanning electron microscopy (SEM),laser particle-size distribution measurement,and other electrochemical techniques.The results demonstrate that the LiFePO4/C materials obtained from Fe(OH)3 at 800℃ and FeCeO4·2H2O at 700℃ have the similar electrochemical performances.The initial discharge capacities of LiFePO4/C synthesized from Fe(OH)3 and FeC2O4·2H2O are 134.5 mAh·g-1 and 137.4 mAh.g-1 at the C/5 rate,respectively.However,the tap density of the LiFePO4/C materials obtained from Fe(OH)3 are higher,which is significant for the improvement of the capacity of the battery.     

化学研磨法制备磷酸铁锂正极材料的结构性能研究

磷酸铁锂被认为是最有可能应用于锂离子动力电池的正极材料.采用化学研磨法制备了磷酸铁锂,并对其结构和电化学性能进行了研究.结果表明：相对于传统高温固相法,化学研磨法可以有效细化磷酸铁锂的颗粒和晶粒,所得材料0.1 C放电容量为132 mAh/g,明显高于传统固相法112 mAh/g的容量.     

热还原法制备LiFePO4／C复合材料的电化学性能

使用廉价的三价铁Fe2O3为铁源,以蔗糖为还原剂和导电剂,通过热还原法制备了LiFePO4／C复合材料。运用TGA—DAT曲线对反应机制进行了分析,利用X射线衍射（XRD）、扫描电镜（SEM）、恒流充放电和循环伏安测试等测试手段对不同覆碳量合成材料进行了表征和电化学性能检测。结果表明：所合成的LiFePO4均为纯相,其中含碳1．07％的样品0．2C倍率下的放电比容量为143．32mAh／g。     

锂离子电池正极材料Li0.97Re0.01FePO4的合成及性能

采用固相反应法合成了锂离子电池正极材料Li0.97Re0.01FePO4(Re=Er,Y,Gd,Nd,La),采用X射线衍射、恒电流充放试验对掺杂试样的微观结构和电化学性能进行测试。试验结果表明:掺杂稀土金属离子对LiFePO4的晶体结构没有影响,与LiFePO4相比,掺杂Er3+,Y3+,Gd3+的试样具有优良的循环性能和倍率性能,而掺杂Nd3+,La3+的试样的循环性能和倍率性能较差。掺杂试样中,Li0.97Gd0.01FePO4的电化学性能最佳,在C/10和1C(1C=120 mA.g-1)倍率下放电容量均最大。     

Synthesis and performance of carbon-modified LiFePO4 using an in situ PVA pyrolysis procedure

LiFePO4/carbon composite cathode material was prepared by granulating and subsequent pyrolysis processing in N2 atmosphere with polyvinyl alcohol (PVA) as the carbon source. The influences of carbon content on the microstructure and battery performance were investigated. Single LiFePO4 phase and amorphous carbon can be found in the products. A special micro-morphology perature dependence of its electrochemical characteristic was evaluated by using AC impedance spectroscopy. A new equivalent circuit based on the charge and mass transfer control process in an electrode was proposed to fit the obtained AC impedance spectra.The tendency of every element in the equivalent circuit was used to interpret the temperature dependence of the capacity of the optimum cathode.     

Synthesis and performance of carbon-modified LiFePO_4 using an in situ PVA pyrolysis procedure

LiFePO4/carbon composite cathode material was prepared by granulating and subsequent pyrolysis processing in N2 at- mosphere with polyvinyl alcohol (PVA) as the carbon source. The influences of carbon content on the microstructure and battery performance were investigated. Single LiFePO4 phase and amorphous carbon can be found in the products. A special mi- cro-morphology of the optimum sample was observed. The discharge capacity of the cell with the optimum cathode was 135 mAh·g?1, close to the charge capacity of 153 mAh·g?1 at 17 mA·g?1. The influence of ambient temperature on the cell capacity was investigated. The temperature dependence of its electrochemical characteristic was evaluated by using AC impedance spectroscopy. A new equivalent circuit based on the charge and mass transfer control process in an electrode was proposed to fit the obtained AC im- pedance spectra. The tendency of every element in the equivalent circuit was used to interpret the temperature dependence of the ca- pacity of the optimum cathode.     

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 c1 space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0μm. During the Li ion chemical intercalation, radical P2O4-O7 is disrupted into two PO3-4 ions in the presence of O2-, 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.     

离子掺杂和碳修饰对Li_2FeSiO_4结构和性能的影响

采用高温固相反应方法合成锂离子电池正极Li_2Fe_(1-x-y)Mn_xNi_ySiO_4/C复合材料,并采用X-ray线衍射、扫描电子显微镜和电化学分析方法,研究了Ni和Mn离子共掺杂及碳修饰复合改性对复合材料结构和性能的影响。结果表明,复合改性没有对材料的晶体结构造成改变,镍锰离子共掺杂和表面碳包覆能有效提高材料的比容量和循环性能;以C/32倍率充放电,复合掺杂得到的Li_2Fe_(0.6)Mn_(0.2)Ni_(0.2)SiO_4/C材料样品的电化学性能最优,根据实测结果,该复合材料的首次放电比容量达到149 m Ah·g~(-1),充放电循环10次以后容量保持率仍有95.3%。