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.     

LiFePO4／C的电化学性能

采用固相烧结法,在惰性气氛下制备了橄榄石型LiFePO4／C正极材料．通过充放电循环实验、循环伏安实验、交流阻抗、拉曼光谱等现代手段,研究了样品的优化制备条件与电化学性能的关系．研究表明,在720℃烧结的样品以1C倍率电流充放电时,首次放电容量为113mAh／g,50循环的放电容量为116mAh／g,表现出优秀的循环稳定性．锂离子扩散系数为1．56×10^-8cm^2／s．在30循环内,样品的电荷传递阻抗随着充放电循环的进行逐渐减小．     

锂摩尔分数对合成LiFePO_4/C的组织结构及电化学性能的影响

在不同Li/Fe配比、合成工艺相同条件下,采用Sol-gel液相合成法合成LiFePO4/C正极材料。利用XRD衍射分析和SEM扫描电镜对合成的粉体进行物相表征,通过交流阻抗测试和充放电对材料进行电化学性能研究。结果表明,Li、Fe物质的量比为1.05时合成的LiFePO4/C结晶度最优,交流阻抗曲线显示该材料具有较小的内部阻抗,极化现象小,在0.2C倍率放电下首次放电比容量为127.5mA·h/g,电化学性能较佳。     

锂离子电池正极材料LiFePO4的合成及其改性

采用共沉淀法合成了锂离子正极材料LiFePO4,考察了不同合成条件对材料结构及性能的影响.研究结果表明:通过碳包覆改性后,LiFePO4的容量可明显提高,SiO2的掺杂对LiFePO4的结构没有影响.同时讨论了上述两种改性方法对材料性能的影响机制.     

Synthesis of Li2Fe0.9Mn0.1SiO4/C composites using glucose as carbon source

Li2Fe0.9Mn0.1SiO4/C composites were synthesized by using glucose as carbon source. The samples were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and electrochemical measurements. All Li2Fe0.9Mn0.1SiO4/C composites are of the similar crystal structure. With increasing the carbon content in the range of 5%-20% (mass fraction), the diffraction peaks in XRD patterns broaden and the particle sizes and the tap density of samples decrease. The Li2Fe0.9Mn0.1SiO4/C composites with carbon content of 14.12% show excellent the capacity retention remains 92.2% after 30 cycles.     

Effect of cooling modes on microstructure and electrochemical performance of LiFePO4

LiFePO4 was prepared by heating the pre-decomposed precursor mixtures sealed in vacuum quartz-tube. Three kinds of cooling modes including nature cooling, air quenching, and water quenching were applied to comparing the effects of cooling modes on the microstructure and electrochemical characteristics of the material. The results indicate that the water quenching mode can control overgrowth of the grain size of final product and improve its electrochemical performance compared with nature cooling mode and air quenching mode. The sample synthesized by using water quenching mode is of the highest reversible discharge specific capacity and the best cyclic electrochemical performance, demonstrating the first discharge capacity of 138.1 mA·h/g at 0.1C rate and the total loss of capacity of 3.11% after 20 cycles.     

Synthesis and characterization of triclinic structural LiVPO4F as possible 4.2 V cathode materials for lithium ion batteries

A potential 4.2 V cathode material LiVPO4F for lithium batteries was prepared by two-step reaction method based on a carbon-thermal reduction （CTR） process. Firstly, V2O5, NH4H2PO4 and acetylene black are reacted under an Ar atmosphere to yield VPO4. The transition-metal reduction is facilitated by the CTR based on C→CO transition. These CTR conditions favor stabilization of the vanadium as V^3＋ as well as leaving residual carbon, which is useful in the subsequent electrode processing. Secondly, VPO4 reacts with ElF to yield LiVPO4F product. The property of the LiVPO4F was investigated by X-ray diffractometry （XRD）, scanning electron microscopy （SEM） and electrochemical measurement. XRD studies show that LiVPO4F synthesized has triclinic structure（space group p I ）, isostructural with the naturally occurring mineral tavorite, EiFePO4-OH. SEM image exhibits that the particle size is about 2μm together with homogenous distribution. Electrochemical test shows that the initial discharge capacity of LiVPO4F powder is 119 mA·h/g at the rate of 0.2C with an average discharge voltage of 4.2V （vs Ei/Li^＋）, and the capacity retains 89 mA·h/g after 30 cycles.     

掺铌硅酸亚铁锂正极材料的电化学性能

采用固相烧结法,以LiOH、FeC2O4.2H2O、Nb2O5、正硅酸四乙酯和蔗糖为原料制备出单斜结构的Li2.05FexNb2(1-x)/3SiO4/C(x=1,0.99,0.98,0.96,0.94,0.92,0.90)系列样品.通过红外光谱、X射线衍射、扫描电镜、恒电流充放电测试、交流阻抗和循环伏安法等方法研究了制备样品的结构及电化学性能.实验结果表明,颗粒尺寸介于0.2～1.5μm之间的Li2.05Fe0.96Nb0.026 7SiO4/C的充放电性能最好,在0.3C倍率电流下,第1次循环的放电容量为116.6 mAh/g,第30循环的放电容量为78.3 mAh/g.掺铌减少了样品的电荷传递阻抗,提高了锂离子的扩散系数.     

磷酸铁锂电池内阻分量快速检测方法

为了实现锂离子电池（LIB）内阻分量快速检测,提出通过直流内阻（DCR）测试及交流内阻测试,辨识各内阻分量的方法. 以磷酸铁锂电池为研究对象,分别采用Bulter-Volmer方程和二阶等效电路模型,模拟研究表征界面电荷转移、浓差极化过程等效电路的时间常数. 由于电荷转移速度足够快,采用直流脉冲测试获得的瞬时响应内阻通常由欧姆内阻和电化学极化内阻组成,结合交流内阻测试仪内阻检测结果,可以计算得到电化学极化内阻分量. 实验结果显示,该内阻分量测试方法不仅操作简便且具有较高的可靠性,电化学极化内阻辨识结果与电化学阻抗测试结果的最小误差小于5%.     

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.     

Effect of baking processes on properties of TiB2/C composite cathode material

Pitch and TiB₂/C green composite cathode material were respectively analyzed with simultaneous DSC-TGA, and effects of three baking processes of TiB₂/C composite cathode material, i.e. K25, K5 and M5, on properties of TiB₂/C composite cathode material were investigated. The results show that thermogravimetric behavior of pitch and TiB₂/C green composite cathode is similar, and appears the largest mass loss rate in the temperature range from 200 to 600°C. The bulk density variation of sample K5 before and after baking is the largest (11.9%), that of sample K25 is the second, and that of sample M5 is the smallest (6.7%). The crushing strength of sample M5 is the biggest (51.2 MPa), that of sample K25 is the next, and that of sample K5 is the smallest (32.8 MPa). But, the orders of the electrical resistivity and electrolysis expansion of samples are just opposite with the order of crushing strength. The heating rate has a great impact on the microstructure of sample. The faster the heating rate is, the bigger the pore size and porosity of sample are. Compared with the heating rate between 200 and 600° of samples K25 and K5, that of sample M5 is slower and suitable for baking process of TiB₂/C composite cathode material. Foundation item: Project (2005CB623703) supported by the Major State Basic Research and Development Program of China; Project (2008AA030502) supported by the National High-Tech Research and Development Program of China     

Technical optimization of LiFeP04 preparation by water quenching treatment

A technique of combination of vacuum firing and water quenching was applied to the synthesis of LiFePO4 powder. The sample was prepared by heating the pre-decomposed precursor mixtures sealed in vacuum quartz-tube, followed by water quenching at the sintering temperature. The synthetic conditions were optimized by orthogonal experiment. The results indicate that the fast quenching treatment can avoid the overgrowth of single crystal and improve its availability ratio of active material. The sintering temperature has the greatest effect on the electrochemical performance of sample. Next is the molar ratio of Li to Fe and the sintering time, respectively. The samples prepared in the optimized technical condition has the highest reversible discharge specific capacity of 149.8 mA·h/g.     

Effects of carbon sources on electrochemical performance of Li4Ti5O12/C composite anode materials

Li₄Ti₅O₁₂/C composite materials were synthesized by two-step solid state reaction method with glucose, sucrose, and starch as carbon sources, respectively. The effects of carbon sources on the structure, morphology, and electrochemical performance of Li₄Ti₅O₁₂/C composite materials were investigated by SEM, XRD and electrochemical tests. The results indicate that carbon sources have almost no effect on the structure of Li₄Ti₅O₁₂/C composite materials. The initial discharge capacities of the Li₄Ti₅O₁₂/C composite materials are slightly lower than those of as-synthesized Li₄Ti₅O₁₂. However, Li₄Ti₅O₁₂/C composite materials show better electrochemical rate performance than the as-synthesized Li₄Ti₅O₁₂. The capacity retention (79%) of the Li₄Ti₅O₁₂/C composite materials with starch as carbon source, is higher than that of Li₄Ti₅O₁₂/C composite materials with glucose and sucrose as carbon source at current rate of 2.0C.     

Vinylene carbonate additive for EMITFSI-based electrolyte for Li/LiFePO4 batteries

Ionic liquids have been paid much attention and are considered to replace the conventional organic electrolyte and solve the safety issues by virtue of nonvolatility,non-flammability,high ionic conductivity and extended electrochemical steady window.The paper introduces ionic liquids electrolyte on basis of 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMITFSI),which shows a wide electrochemical window (0.5-4.5 V vs.Li+/Li),and is theoretically feasible as an electrolyte for Li/LiFePO4batteries to improve the safety.Linear sweep voltammetry (LSV) was performed to investigate the electrochemical stability window of the polymer electrolyte.Interfacial resistance for Li/electrolyte/Li symmetric cells and Li/electrolyte/LiFePO4 cells were studied by electrochemical impedance spectroscopy (EIS).The results showed that additive vinylene carbonate (VC) enhances the formation of solid electrolyte interphase film to protect lithium anodes from corrosion and improves the compatibility of ionic liquid electrolyte towards lithium anodes.Accordingly,Li/LiFePO4cells delivers the initial discharge capacity of 124 mAh g-1 at a current rate of 0.1C in the ionic liquid electrolyte (EMITFSI+0.8 mol L-1LiTFSI+5 wt%VC),and shows better cyclability than in the ionic liquid electrolyte without VC.     

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.     

流变相法制备LiFe_(1-x)Mg_xPO_4/C正极材料

通过Mg+金属掺杂及流变相制备方法来改善橄榄石结构的LiFePO4的电化学性能.研究了不同掺杂量和不同制备方法对材料结构性能和电化学性能的影响.SEM,XRD,以及电化学测试结果表明,Mg掺杂可以较大程度提高材料电化学性能;0.1 C倍率下首次充电容量达到140.7 mAh/g.利用流变相法制备的材料粒度更小,其电化学性能得到进一步提高,0.1 C时放电比容量达到了147.5 mAh/g.     

水解法制备掺氟硅酸亚铁锂正极材料

采用水解法制得纯相掺氟硅酸亚铁锂正极材料.通过XRD衍射、充放电实验、交流阻抗谱、红外光谱、热重等现代手段,研究了所制备的样品的电化学性能.研究表明,通过400、600℃两步烧结可制得具有单斜结构(空间群P21/n)的Li2.05FeSiO4F0.02/C.制备的扣式电池在55℃下,分别以0.3C、1C、2C倍率电流连续充放电30循环时,第1循环的容量分别为116.8、106.5、99.2 mAh.g-1.掺氟改善了硅酸亚铁锂的电化学性能.     

Structure and electrochemical properties of La, F dual-doped iLa0.01Mn1.99O3.99F0.01 cathode materials

The cathode materials LiMn₂O₄ and rare earth elements La-doped or La and F dual-doped spinel lithium manganese oxides were synthesized by the citric acid-assisted sol-gel method. The synthesized samples were investigated by differential thermal analysis (DTA) and thermogravimetry (TG) measurements, X-ray diffraction (XRD), scanning electronic microscope (SEM), cyclic voltammetry (CV), and charge-discharge test. XRD data shows that all the samples exhibit the same pure spinel phase, and the LiLa_0.01Mn_1.99O_3.99F_0.01 and LiLa_0.01Mn_1.99O₄ samples have smaller lattice parameters and unit cell volume than LiMn₂O₄. SEM indicates that LiLa_0.01Mn_1.99O_3.99F_0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution. The charge-discharge test reveals that the initial capacities of LiMn₂O₄, LiLa_0.01Mn_1.99O₄, and LiLa_0.01Mn_1.99O_3.99F_0.01 are 129.9, 122.8, and 126.4 mAh·g⁻¹, and the capacity losses of the initial values after 50 cycles are 14.5%, 7.6%, and 8.0%, respectively. The CVs show that the La and F dual-doped spinel displays a better reversibility than LiMn₂O₄.     

LiFePO4/石墨烯复合材料的电化学性能比较

分别以水热合成的石墨烯（H-Gr）和商业化石墨烯（C-Gr）为载体,以溶胶-凝胶法合成的LiFePO4（S-LFP）和商业化的LiFePO4（C-LFP）为活性组分,通过固相法制备了4个LiFePO4/石墨烯复合物。采用X射线粉末衍射（XRD）、扫描电镜（SEM）和电化学性能测试,对上述LiFePO4/石墨烯复合物进行了对比研究。实验结果表明,C-LFP/H-Gr显示了最高的可逆放电容量,0.1C倍率下,达到155.0mA.h.g-1,其次是C-LFP/C-Gr（144.6mA.h.g-1）和S-LFP/H-Gr（131.5mA.h.g-1）,S-LFP/C-Gr的性能最差,仅为119.6mA.h.g-1。C-LFP/H-Gr较高的电化学容量,一方面可归结于商业化的LiFePO4较小的粒径和良好的晶型结构;另一方面水热合成的石墨烯小的片层结构对LiFePO4的良好包覆,不仅增强了材料导电性,而且提高了活性物质LiFePO4的利用率。     

磷酸铁的湿法磷酸制备及其对合成的磷酸铁锂性能的影响

以湿法磷酸和硫酸亚铁分别为磷源和铁源,通过合成、沉淀过程制备磷酸铁,研究了不同摩尔投料比对合成磷酸铁质量的影响,并以制备的磷酸铁为磷源和铁源采用溶胶凝胶法制备了磷酸铁锂材料.采用了X射线衍射、扫描电子显微镜等手段对合成的磷酸铁锂材料结构和微观形貌进行表征,同时考察了其电化学性能.结果表明：在湿法磷酸和硫酸亚铁摩尔比为1∶1时合成出的磷酸铁中磷质量分数为16.38％,铁质量分数为29.30％,得到的产物最为接近二水磷酸铁;用该磷酸铁制备的磷酸铁锂正极材料在0.1C倍率下充放电,其首次放电比容量达144.4 mAh/g,40次充放电循环后放电容量能达到141.6 mAh/g,衰减率为1.94％,循环倍率性能优良.