不同有机-水混合溶剂的Li3V2（PO4）3/C合成及其性能

以有机-水为混合溶剂,采用溶胶-凝胶法制备锂离子电池正极材料Li3V2(PO4)3/C。通过X射线衍射(XRD)、扫描电镜(SEM)、恒流充放电以及循环伏安(CV)测试等方法,研究产物的结构形貌及电化学性能。结果表明:溶剂对材料的晶型结构没有影响,对颗粒的形貌影响较大;以1,2-丙二醇-水为溶剂的样品呈薄片状和针状;在3.0～4.5 V电压范围内,Li3V2(PO4)3/C的0.1C首次放电比容量为132.89 mA.h/g,10C首次放电比容量达125.42 mA.h/g,循环700周后容量保持率为95.79%,具有良好的倍率性能与循环性能;而在3.0～4.8 V电压范围内倍率性能较差。     

Ni2+掺杂对Li3V2（PO4）3电化学性能的影响

采用X射线衍射(XRD)、透射电镜(TEM)和电化学方法,研究Ni2+掺杂对正极材料Li3V2(PO4)3的结构、形貌和电化学性能的影响。结果表明:掺杂适量的Ni2+不会改变Li3V2(PO4)3的单斜晶系结构,但可提高材料的电导率,抑制电池在充放电过程的极化。在室温下,Li3(Ni0.05V0.95)2(PO4)3以0.1C倍率放电的初始比容量为115mA.h/g,放电倍率从0.1C增加到0.4C循环60次后,比容量衰减率仅为2.7%,而未掺杂原样Li3V2(PO4)3的初始比容量为129 mA.h/g,60次循环后比容量衰减率约为30.3%;当放电倍率增至1C时,80次循环后,Li3(Ni0.05V0.95)2(PO4)3比容量为99.8 mA.h/g,而原样的比容量为84.1 mA.h/g;当放电倍率增至5C时,循环120次后,Li3(Ni0.05V0.95)2(PO4)3比容量为67.7 mA.h/g,而原样的比容量降为0。循环伏安和交流阻抗测试表明,Li3(Ni0.05V0.95)2(PO4)3的可逆性明显优于Li3V2(PO4)3的可逆性。     

介孔Li3V2（PO4）3正极材料的研磨溶胶凝胶法合成和电化学性能（英文）

以V2O5·nH2O、LiOH·H2O、NH4H2PO4和蔗糖为原料,采用研磨溶胶凝胶技术制备了无定形Li3V2(PO4)3前驱体,再经过焙烧获得具有单斜结构的介孔Li3V2(PO4)3正极材料,并用XRD、SEM、TEM、比表面积和电化学性能测试来表征材料的性能。研究表明,在700°C下焙烧的样品具有良好的介孔结构、最大的比表面积(188cm2/g)和最小的孔径(9.3nm)。在0.2C倍率下,该介孔样品的首次放电容量达155.9mA·h/g,经过50次循环后其容量仍然可达154mA·h/g,表现出非常稳定的放电性能。     

Li3Ni0.1V1.9（PO4）3的电化学性能研究

采用X射线衍射和电化学方法,研究了正极材料Li3Ni0.1V1.9(PO43)的结构和电化学性能。结果表明:Li3Ni0.1V1.9(PO43)具有单斜晶系结构。在室温下,以0.1C倍率放电时Li3Ni0.1V1.9(PO4)3的初始比容量为115mAh/g,从0.1C增加到0.4C经过60次循环后,比容量保持率为97.3%,而未掺杂镍的Li3V2(PO4)3,初始比容量为129mAh/g,60次循环后,比容量保持率仅为69.7%。循环伏安和交流阻抗测试表明,Li3Ni0.1V1.9(PO4)3有较低的极化电阻和较好的可逆性。     

焙烧温度对Li2FeSiO4前驱体Li2SiO3性能的影响（英文）

以Li2CO3,HNO3,Si(OC2H5)4为原材料,采用溶胶-凝胶和高温焙烧法合成Li2SiO3;研究焙烧温度和回流系统对硅酸锂组分和性能的影响;利用TGA/DTA,XRD,SEM和粒径分析等手段对样品进行表征;采用Li2SiO3和Fe2C2O4.2H2O固相反应制备Li2FeSiO4。XRD结果表明,在溶胶-凝胶制备过程中使用回流系统能减少Li2SiO3样品中Li2SiO5和Li4SiO4杂质。焙烧结温度对Li2SiO3的性能有重要的作用,当温度为700℃时,Li2SiO3前驱体材料样品纯度为97%,并具有良好的形貌;它是由粒径为1～3μm的一次粒子组成,一次粒子束形成疏松、多孔的团聚体。     

固相-水热法制备LiFePO4-Li3V2（PO4）3复合材料及其电化学性能（英文）

分别采用固相-水热法和球磨法制备磷酸亚铁锂-磷酸钒锂复合正极材料(LiFePO4-Li3V2(PO4)3)。电化学性能测试表明,LiFePO4-Li3V2(PO4)3复合正极材料的电化学性能远远高于 LiFePO4和 Li3V2(PO4)3单独作为正极材料的性能,并且以固相-水热法制备的复合材料性能优于以球磨法制得的复合材料。研究发现 LiFePO4-Li3V2(PO4)3复合材料有 4 个氧化还原峰,相当于 LiFePO4 和 Li3V2(PO4)3 氧化还原峰的叠加。采用固相-水热法制备的LiFePO4-Li3V2(PO4)3 复合材料形貌较为规则,且有新相物质产生,这是导致其电化学性能较好的原因。     

合成温度对正极材料Li3V2（PO4）3/C性能的影响

以V2O5、NH4H2PO4、Li2CO3和C6H8O7·H2O为原料,采用溶胶-凝胶法在600～800℃下合成了锂离子电池正极材料Li3V2(PO4)3/C,利用XRD和蓝电测试系统对材料进行表征,研究了合成温度对材料电化学性能的影响。结果表明:650℃下合成产物中开始出现Li3V2(PO4)3相,700、750和800℃下合成纯相的Li3V2(PO4)3正极材料;750℃合成的样品在放电电流密度为0.1C下首次放电容量为123.5mAh·g-1,并且随电流密度增大到10C时也有较好的循环稳定性。     

Li3V2(PO4)3/C复合结构正极材料的制备和电化学性能

以柠檬酸为螯合剂和碳源,采用溶胶凝胶法在强弱不同条件下制备锂离子正极材料Li3V2(PO4)3/C.利用XRD、SEM和恒电流充放电等进行测试和表征.结果表明,所有样品为纯相的单斜Li3V2(PO4)3,制备条件的不同不会影响Li3V2(PO4)3正极材料的晶型结构和晶胞参数,但对材料颗粒尺寸有较大影响,加入蔗糖可以抑制颗粒的长大和团聚,从而影响电化学性能;在3.0～4.3 V电压,由于Li3V2(PO4)3结构的稳定性,在低倍率下表现出优异的循环性能;随着颗粒的变大和团聚,材料的倍率性变差,在高倍率下充放电容量衰减快.     

钇掺杂LiFePO4锂离子电池正极材料的制备与性能

用固相法合成LiFe1-xYxPO4 (x=0, 0.01, 0.02, 0.03, 0.04)锂离子电池正极材料,采用X射线衍射仪、扫描电子显微镜、粉末比电阻法和充放电性能测试表征材料的晶体结构、微观形貌、电子电导率和电化学性能。结果表明,少量的钇掺杂并未改变材料的晶体结构,但改善了材料的微观结构,提高其电子电导率,改善可逆容量和电化学性能。在10 mA/g的电流密度下,LiFe0.97Y0.03PO4首次放电容量可达146.54 mAh/g。     

影响锂离子电池正极材料LiMn2O4性能的因素

介绍了锂离子电池正极材料LiMn2O4的制备方法，并以柠檬酸体系溶胶一凝胶法合成LiMn2O4为例，从溶液pH值及含水量、Li的含量及酸与金属离子摩尔比、合成温度及时间、冷却速度及粒度等方面阐述了影响LiMn2O4性能的因素。实验表明，体系溶液最好为饱和溶液，pH值应控制在6．5左右；锂盐略为过量，柠檬酸与金属离子摩尔比为1：1。最佳烧结温度为750℃。8000℃，并合理控制冷却速率，合理控制烧结时间及烧结温度，从而控制粒子半径。     

Electrochemical performance of Al-substituted Li_3V_2(PO_4)_3 cathode materials synthesized by sol-gel method

The effect of Al-substitution on the electrochemical performances of Li3V2(PO4)3 cathode materials was studied.Samples with stoichiometric proportion of Li3AlxV2-x(PO4)3(x=0,0.05,0.10)were prepared by adding Al(NO3)3 in the raw materials of Li3V2(PO4)3.The XRD analysis shows that the Al-substituted Li3V2(PO4)3 has the same monoclinic structure as the un-substituted Li3V2(PO4)3.The SEM images show that Al-substituted Li3V2(PO4)3 has regular and uniform particles.The electrochemical measurements show that Al-substitution can improve the rate capability of cathode materials.The Li3Al0.05V1.95(PO4)3 sample shows the best high-rate performance.The discharge capacity at 1C rate is 119 mA·h/g with 30th capacity retention rate about 92.97%.The electrode reaction reversibility and electronic conductivity are enhanced,and the charge transfer resistance decreases through Al-substitution.The improved electrochemical performances of Al-substituted Li3V2(PO4)3 cathode materials offer some favorable properties for their commercial application.     

Li_3V_2(PO_4)_3溶胶-凝胶-微波合成工艺优化及性能研究

用溶胶-凝胶-微波法制备了锂离子电池正极材料Li3V2(PO4)3样品,用正交试验法考察了影响样品性能的因素,分析并优化了工艺。XRD、SEM和电化学测试表明:该方法所制备的样品为单斜结构,粒径尺寸0.2～1μm,颗粒分布比较均匀。锂源为Li2CO3、反应物摩尔比为Li∶V=3.0∶2.0、微波时间为25 min时,为最佳合成工艺条件。在此优化条件下,3.0～4.3 V区间内0.2 C放电比容量达到106 mAh/g,交换电流密度高达6.17×10-6 A/cm2。     

微波法一步合成锂离子电池正极材料Li_3V_2(PO_4)_3的研究(英文)

以NH4H2PO4、Li2CO3和V2O5为原料,采用微波法快速合成了锂离子电池正极材料Li3V2(PO4)3。考察了微波功率、加热时间及产品中的理论碳含量对材料物理及电化学性能的影响。添加的乙炔黑具有还原剂、微波吸收体及导电剂的多重作用。XRD测试表明采用该法可以获得单相的Li3V2(PO4)3。电化学测试表明含2%C的Li3V2(PO4)3具有较好的充放电性能,充放电电流密度为7mA·g-1时,首次放电比容量为115.7mAh·g-1,20次循环后容量保持率为87.5%。与传统方法相比,微波法具有工艺简单,效率高,经济性好的优点。     

Synthesis and performance of Li3V2（PO4）3/C composites as cathode materials

Carbon-coated Li3V2(PO4)3 cathode materials for lithium-ion batteries were prepared by a carbon-thermal reduction (CTR) method using su- crose as carbon source. The Li3V2(PO4)3/C composite cathode materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical measurement. The results show that the Li3V2(PO4)3 samples synthesized using sucrose as carbon source have the same monoclinic structure as the Li3V2(PO4)3 sample synthesized using acetylene black as carbon source. SEM image exhib- its that the particle size is about 1 μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of Li3V2(PO4)3 powders is 122 mAh·g-1 at the rate of 0.2C, and the capacity retains 111 mAh·g-1 after 50 cycles.     

Synthesis and electrochemical performance of Li3V2(PO4)3 by optimized sol-gel synthesis routine

Li₃V₂(PO₄)₃ samples were synthesized by sol-gel route and high temperature solid-state reaction. The influence of Li₃V₂(PO₄)₃ as cathode materials for lithium-ion batteries on electrochemical performances was investigated. The structure of Li₃V₂(PO₄)₃ as cathode materials for lithium-ion batteries and morphology of Li₃V₂(PO₄)₃ were characterized by X-ray diffractometry (XRD) and scanning electron microscopy (SEM). Electrochemical performances were characterized by charge/discharge and AC impedance measurements. Li₃V₂(PO₄)₃ with smaller grain size shows better performances in terms of the discharge capacity and cycle stability. The improved electrochemical properties of Li₃V₂(PO₄)₃ are attributed to the refined grains and enhanced electrical conductivity. AC impedance measurements also show that the Li₃V₂(PO₄)₃ synthesized by sol-gel route exhibits significantly decreased charge-transfer resistance and shortened migration distance of lithium ions.     

Preparation and characteristics of Li2FeSiO4/C composite for cathode of lithium ion batteries

A Li2FeSiO4/C composite cathode for lithium ion batteries was synthesized at 650 ℃ by solid-state reaction. The effects of carbon sources and carbon content on the properties of the Li2FeSiO4/C composites were investigated. The crystalline structure, morphology, carbon content and charge/discharge performance of Li2FeSiO4/C composites were determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), carbon/sulfur analyzer and electrochemical measurements. As carbon content increases in the range of 5%-20%, the amount of Fe3O4 impurity phase decreases. The SEM micrographs show that the addition of the carbon is favorable for reducing the Li2FeSiO4 grain size. Using sucrose as carbon source, the Li2FeSiO4/C composite with 14.5% carbon synthesized at 650 ℃ shows good electrochemical performance with an initial discharge capacity of 144.8 mA-h/g and a capacity retention ratio of 94.27% after 13 cycles.     

新型锂离子电池正极材料Li3V2(PO4)3的合成及其性能

以LiOH·H2O、V2O5和NH4H2PO4为原料,C为还原剂,采用高温固相法合成了锂离子电池正极材料磷酸钒锂(Li3V2(PO4)3).考察了合成温度等条件对产物组成和晶相的影响.结果表明:随着焙烧温度的升高,杂相的衍射峰相对强度逐渐减弱,当煅烧温度达到800℃时,杂相衍射峰消失,所得样品为纯相的Li3V2(PO4)3样品;按Li、V、P的摩尔比为3:2:3将原料在800℃下焙烧24 h,合成得到正极材料.该材料在0.1 C充放电制度下,首次充电比容量达到135 mA·h/g,首次放电比容量130 mA·h/g,充放电效率达96.3%;经过20次循环后,放电容量仍然高达110 mA·h/g.对经过20次循环后的样品进行了X射线衍射分析,结果发现,经过20次循环后样品仍然具有单斜晶体结构,样品各主要衍射峰强度都急剧减弱,说明样品在充放电过程中晶体结构发生了变化;采用最小二乘法对样品充放电前后的晶胞参数进行了计算,发现样品在经过充放电循环后晶胞参数都有不同程度的增加,晶胞体积增大0.6%左右.     

不同碳源对Li3V2（PO4）3正极材料性能的影响

通过碳热还原法合成掺碳锂离子电池正极材料单斜Li3V2(PO4)3,用XRD、SEM及电化学测试等方法对材料的结构、形貌和电化学性能进行表征和测试,探讨石墨、乙炔黑以及蔗糖3种碳源对材料性能的影响,并分析不同碳源对材料性能影响的原因。结果表明,碳源的选择对产物的结构和电化学性能有很大的影响。以蔗糖为碳源制备的单斜Li3V2(PO4)3正极材料具有粒径小、电荷转移阻抗小等优点,获得了较好的电化学性能,当电压范围为3.0～4.3和3.0～4.8V时,其初始容量分别为127.8和166.2mA·h/g,30次循环后放电比容量分别为124.2和143.3mA·h/g。