Synthesis of LiFePO4 nanoparticles by solvothermal process using various polyol media and their electrochemical properties

Olivine structured LiFePO4 samples were synthesized by solvothermal process using various polyol media of ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG), and tetraethylene glycol (TTEG) without any heating as a post procedure. The X-ray diffraction patterns of the samples prepared in EG and DEG showed the crystalline peaks with well-fitted to the positions on the basis of an olivine type structure without any impurities. In order to determine the unit cell parameters, synchrotron powder XRD patterns were fitted with whole-pattern profile matching method using FULLPROF program. The obtained samples exhibited well dispersed nanoplate morphologies excepting for the sample prepared in EG. The samples prepared in EG, DEG, TEG, and TTEG showed the reversible capacity of 118, 167, 90, and 105 mAh/g at current density of 0.1 mA/cm2, respectively. Among them, the samples reacted in DEG and TTEG showed good performances at high rate of 16C with high capacities retention.     

A polyol-mediated synthesis of titania-based nanoparticles and their electrochemical properties

Ti-based nanoparticles were prepared in polyol mediums of EG (ethylene glycol) and TEG (triethylene glycol), with heating treatment. Ti-based materials of dried power and heated samples showed average sizes of 4, 10, 3, and 8 nm with spherical shapes and monodispersed state, respectively. The XRD patterns of TiO2 and Li4Ti5O12 materials of dried powder and heated samples were indexed to anatase phase TiO2 (space group: I4(1)/amd) and the spinel phase (space group: Fd3m) except for the dried powder sample of Li4Ti5O12, which was corresponded with amorphous-like characteristics from the X-ray diffraction and electron diffraction pattern of Field emission-TEM analysis. The TiO2 and Li4Ti5O12 samples after heat-treated at 500 degrees C exhibited excellent high rate capabilities at a current density of 0.4 mA/cm2 during extended cycles due to their electrochemically beneficial highly crystalline characteristics, nano-sized (approximately 10 nm), and uniform distributions state.     

锂源对LiFePO4组织结构及电化学性能的影响

利用不同的锂化合物Li2CO3、LiOH.H2O、LiNO3、LiF作为锂源,采用二步固相法合成了LiFePO4/C,研究了不同锂源对LiFePO4组织结构和电化学性能的影响。结果表明,在相同的合成工艺条件下,采用4种不同锂源合成的LiFePO4的电化学性能表现出明显差异。采用LiOH.H2O合成的LiFe-PO4的电化学性能最佳,0.1C下的放电比容量为161mAh/g,1C下的放电比容量达117mAh/g,且0.5C下循环容量无衰减。采用不同锂源合成的LiFePO4电化学性能差异的原因与LiFePO4的颗粒大小、粒径分布、团聚程度及是否存在杂相有直接关系。     

Synthesis and electrochemical performance of nano-metastructured LiFePO4/C cathode material

The nano-metastructured LiFePO4/C composites were synthesized by carbothermal reduction method using starch gel as carbon source and dispersing media to obtain high tap density LiFePO4 with excellent electrochemical performance. The raw materials were coated by starch gel as compact precursors, which was sintered at 750 degrees C for 8 h to obtain high-density LiFePO4/C composite aggregated with nano-sized particles. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations showed that the primary particles had an average size of about 50-80 nm and the aggregates had a homogeneous particle size distribution of about 400 nm. The asprepared samples had a shortened lithium-ion diffusion length but with higher tap density, thus leading to the excellent electrochemical performance of the cathode materials. Electrochemical results showed that the samples delivered high discharge capacities of 155.6 and 120.7 mAh/g at 0.2C and 5C rates, respectively, with excellent cycling performance.     

Nanosized LiFePO4 cathode materials for lithium ion batteries

In this study, we prepared nano-particles of LiFePO4 as cathode material for lithium ion batteries by the solid-state reaction. A simple one-step heat treatment has been employed with control of heating temperature and heated LiFePO4 at 650 degrees C exhibited higher 125 mA h/g of the discharge capacity than 600 degrees C, 700 degrees C. To improve conductivity of the inter-particle, carbon coating was carried out by raw carbon or pyrene as carbon sources and their morphological properties of particles on the carbon coating was compared with by FE-SEM, TEM. From the FE-SEM results, the particles of carbon added LiFePO4 have much smaller size than LiFePO4 as below 300 nm. When adding pyrene (10 wt%), the carbon surrounded non-uniformly with surface of the particles compared with adding raw carbon which wrapped uniformly with carbon web and it was exhibited 152 mA h/g of the discharge capacity on LiFePO4/C composite cells at 10th cycle.     

机械活化辅助固相法合成LiFePO4-C材料及性能

为研究机械活化处理对原料形貌和终产物电化学性能的影响,通过机械化学活化辅助固相法,以碳酸锂(Li2CO3)、磷酸二氢铵(NH4H2PO4)和草酸亚铁(FeC2O4·2H2O)为原料,蔗糖为碳源,合成LiFePO4-C复合材料.利用X射线衍射、扫描电镜、LAND电池测试系统等对合成材料进行表征和电化学性能检测.结果表明,通过机械活化,原料达到微米级的均匀混合和充分接触,提高了反应活性,利于传质过程和高温固相反应,获得颗粒细小均匀、结晶良好的LiFePO4-C材料,放电比容量为146.93 mA·h/g(充放电倍率为0.2 C),40次循环后放电比容量为143.40 mA·h/g,容量保持率为97％.     

两步掺杂合成法制备LiFePO4-C复合材料及其性能

通过两步掺杂碳采用高温固相反应法合成了锂离子电池正极LiFePO4-C复合材料.利用SEM、XRD、TG/DTA等方法对该正极材料的晶体结构、表面形貌、粒径大小和热反应进行了分析研究.实验结果表明,LiFePO4-C具有单一的橄榄石结构,前驱体掺杂14%(质量分数)、预分解后掺杂6%(质量分数)葡萄糖合成的材料具有良好的充放电性能和循环稳定性能.在0.1C倍率下进行充放电测试,首次放电比容量可达158.5mA·h/g,具有良好的电化学性能.     

NaFeTiO4 nanorod/multi-walled carbon nanotubes composite as an anode material for sodium-ion batteries with high performances in both half and full cells

NaFeTiO4 nanorods of high yields (with diameters in the range of 30-50 nm and lengths of up to 1-5 μm) were synthesized by a facile sol-gel method and were utilized as an anode material for sodium-ion batteries for the first time.The obtained NaFeTiO4 nanorods exhibit a high initial discharge capacity of 294 mA·h·g-1 at 0.2 C (1 C =177 mA·g-1),and remain at 115 mA·h·g-1 after 50 cycles.Furthermore,multi-walled carbon nanotubes (MWCNTs) were mechanically milled with the pristine material to obtain NaFeTiO4/MWCNTs.The NaFeTiO4/MWCNTs electrode exhibits a significantly improved electrochemical performance with a stable discharge capacity of 150 mA·h·g-1 at 0.2 C after 50 cycles,and remains at 125 mA·h·g-1 at 0.5 C after 420 cycles.The NaFeTiO4/MWCNTs//Na3V2(PO4)3/C full cell was assembled for the first time;it displays a discharge capacity of 70 mA·h·g-1 after 50 cycles at 0.05 C,indicating its excellent performances.X-ray photoelectron spectroscopy,ex situ X-ray diffraction,and Raman measurements were performed to investigate the initial electrochemical mechanisms of the obtained NaFeTiO4/MWCNTs.     

复合正极材料LiFePO4/Al/C的制备及性能研究

采用二步固相法制备了LiFePO4/Al/C复合正极材料.利用X射线衍射仪、扫描电镜和透射电镜表征样品的晶体结构、形貌、粒径和包覆状态,并研究了铝粉加入量对复合材料电化学性能的影响.结果表明,金属Al与LiFePO4发生了界面反应,生成多种副产物,并在LiFePO4的表面形成钝化膜.在LiFePO4颗粒的表面包覆有不规则形状的金属铝和1～2 nm的碳层.当铝粉加入量为3wt%时,LiFePO4/Al/C复合材料的电化学性能最佳,室温10C倍率下放电克容量为117.8 mAh/g;样品在20℃下,0.1C放电克容量为105.6 mAh/g,相对于常温的放电容量比率为73.8%.     

电化学合成磷酸铁锂正极材料的前驱体

以NH4H2PO4、锂盐和纯铁为主要原料,采用电化学法合成磷酸锂铁前驱体,再通过磷酸锂铁前驱体合成锂离子电池正极材料LiFePO4/C。通过X射线衍射(XRD)、扫描电镜(SEM)及充放电性能测试等方法对其晶体结构、微观形貌和电化学性能进行分析研究。结果表明,LiFePO4/C具有单一的橄榄石型晶体结构。其中在无水乙醇溶剂中合成的LiFePO4/C正极材料粒径细小且分布均匀,具有最好的电化学性能,在0.2C的放电电流下,首次放电比容量达到142.3mAh/g,充放电循环30次后放电比容量仍保持在141.2mAh/g。     

Micro-nano structured VNb9O25 anode with superior electronic conductivity for high-rate and long-life lithium storage

The oxygen vacancies and micro-nano structure can optimize the electron/Li+migration kinetics in anode materials for lithium batteries(LIBs).Here,porous micro-nano structured VNb9O25 composites with rich oxygen vacancies were reasonably prepared via a facile solvothermal method combined with annealing treatment at 800℃for 30 h(VNb9 O25-30 h).This micro-nano structure can enhance the contact of active material/electrolyte,and shorten the Li+diffusion distance.The introduction of oxygen vacancies can further boosts the intrinsic conductivity of VNb9O25-30 h for achieving excellent LIB performance.The as-prepared VNb9O25-30 h anode showed advanced rate capability with reversible capacity of 122.2 mA h g-1 at 4 A g-1,and delivered excellent capacity retention of～100％after 2000 cycles.Meanwhile,VNb9O25-30 h provides unexpected long-cycle life(i.e.,reversible capacity of 165.7 mA h g-1 at 1 A g-1 with a high capacity retention of 85.6％even after 8000 cycles).Additionally,coupled with the LiFePO4 cathode,the LiFePO4//VNb9O25-30 h full cell delivers superior LIB properties with high reversible capacities of 91.6 mA h g-1 at 5C for 1000 cycles.Thus,such reasonable construction method can assist in other high-performance niobium-based oxides in LIBs.     

钛离子掺杂对LiFePO4结构和性能的影响

为提高LiFePO4的充放电性能，用Ti（Ⅳ）对LiFePO4进行掺杂．用电化学方法测量了Li1-xTixFePO4的充放电性能，用X射线衍射和里特沃尔特方法表征了掺杂LiFePO4的晶体结构．固相反应可以制备单相Li1-xTixFePO4（x=0．00、0．01、0．02、0．03、0．05和0．07，摩尔分数），其中Li0．98Ti0．02FePO4具有更好的电化学性能，在80mA／g的充放电电流下，第2次的放电比容量为136．606mAh／g，循环20次后为128．388mAh／g．研究表明，少量钛离子掺杂不仅改变了原子间距和位置、引起晶胞收缩，而且增加了LiFePO4中Fe^3＋／Fe^2＋共存态的浓度，提高了材料的导电能力，从而能有效地提高LiFePO4的比容量和循环性能．     

锂离子电池正极材料Li(MnxFe1-x)PO4的合成及电化学性能的研究

采用高温固相法合成了组成为Li（MnxFe1-x）PO4（x=0、0．2、0．4、0．6、0．8、1．0）的锂离子电池正极材料。通过对合成样品的XRD、SEM及电化学性能（循环性能,大电流放电性能）的研究表明,少量Mn的掺杂未影响到LiFePO4的晶体结构,但显著改善了它的电化学性能。Li（Mn0.2Fe0.8）PO4与LiFePO4材料相比有更好的电化学性能,在低放电倍率（电流密度为20mA／g）时,放电容量为150mAh／g,当放电倍率提高到2C时,放电容量仍可达113mAh／g,且循环性能良好。     

表面活性剂对溶胶-凝胶法合成LiFePO4电化学性能的影响

以不同锂盐与柠檬酸铁为原料,采用溶胶-凝胶法制备LiFePO4,并讨论在前躯体中加入表面活性剂对LiFePO4性能的影响.结合XRD、SEM和充放电测试等手段对材料性能进行表征.结果表明,表面活性剂可以抑制杂质相Li4P2O7的出现,得到颗粒尺寸较小的LiFePO4,在0.1C倍率下其首次放电比容量可达123.5mAh/g,循环10次后容量仅衰减2.4%.     

氢气还原法制备LiFePO_4及其电化学性能的研究

在溶液中制备FePO_4·2H_2O前驱体,利用氢气还原法于650℃制得了锂离子电池正极材料LiFePO_4,并对其进行了包覆和掺杂.采用X射线衍射法(XRD)、扫描电镜法(SEM)、循环伏安法(C-V)、交流阻抗法(EIS)及充放电测试对材料进行了结构表征和电化学性能测试.结果表明,该方法制得的材料具有单一的橄榄石结构,样品形貌规则、颗粒均匀.包覆碳和掺镁后,材料具有较低的阻抗及较高的首次放电比容量,LiFePO_4、LiFePO_4/C、LiMg_(0.01)Fe_(0.99)PO_4/C的首次放电比容量分别为125.09mA·h/g、139.17mA·h/g、146.97mA·h/g.     

聚吡咯/磷酸铁锂复合正极材料的制备与表征

采用化学氧化法, 以吡咯为单体、 三氯化铁为氧化剂、 苯磺酸钠为掺杂剂在磷酸铁锂颗粒表面进行原位聚合, 制备了聚吡咯/磷酸铁锂(PPy/LiFePO₄)复合材料。用FTIR、 XRD和SEM对PPy/LiFePO₄复合材料进行了结构与形貌表征。用电化学工作站和充放电测试系统对复合材料的电化学性能进行了表征。结果表明: PPy/LiFePO₄复合材料作锂二次电池正极具有良好的充放电循环性能。当PPy质量分数为17%, 充放电电流为0.1 mA时, PPy/LiFePO₄复合材料最高放电比容量达163 mAh·g^-1, 50次循环之后放电比容量仍为初始时的94.9%; 与LiFePO₄相比, 当PPy的含量适当时, PPy/LiFePO₄复合正极材料的放电比容量会有明显提高。PPy的加入提高了LiFePO₄的电子电导率, 从而提高了活性物质有效利用率, 因此PPy/LiFePO₄复合材料的比容量和循环性能均得到了提升。     

无定形SnO2-C复合纤维及其电化学性能研究

以2-乙基己酸亚锡为原料, 通过静电纺丝以及随后在惰性气氛中煅烧成功制备出电化学性能优良的SnO₂-C复合纤维。X射线衍射(XRD)、拉曼光谱(Raman)、X射线光电子能谱(XPS)、热重分析(TGA)、扫描电镜(SEM)和透射电镜(TEM)的分析结果表明: SnO₂-C复合纤维具有无定形结构, 直径为100~300 nm, 含碳量约38%。电化学测试结果表明: 在50 mA/g的电流密度下, 无定形SnO₂-C复合纤维的首次放电比容量、充电比容量和库仑效率分别为1370.1 mAh/g、757.5 mAh/g和55.28%; 在50 mA/g的电流密度下循环80次后, SnO₂-C复合纤维的比容量为611.6 mAh/g, 没有出现明显的容量衰减。SnO₂-C复合纤维高的比容量和良好的循环性能归因于其SnO₂均匀分布的SnO₂-C复合一维结构。     

ZnFe2O4锂离子电池负极材料的制备及电化学性能研究

以ZnCl₂和FeCl₃.6H₂O为原料, 通过溶剂热法制备了尖晶石型ZnFe₂O₄材料, 通过X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅立叶红外光谱(FT-IR)和恒流充放电测试技术对材料的结构、形貌及电化学性能进行了表征。结果表明, 合成的材料为纳微多孔结构, 其颗粒粒径约为250 nm, 以50 mA/g的电流密度充放电时, 可逆比容量为933.1 mAh/g, 经过100次循环后, 比容量为813.5 mAh/g, 比容量保持率高达87.2%, 表现出优异的循环稳定性能。当电流密度增大到400 mA/g时, 其比容量约为355 mAh/g, 表现出较高的倍率性能。采用该法制备得到的纳米ZnFe₂O₄具有比容量高、循环稳定好等优点, 是一种具有较强应用前景的锂离子电池负极材料。     

纳米FePO4的合成及其正极材料LiFePO4/C的电化学性能研究

以Fe3+为铁源,采用控制结晶技术合成了纳米FePO4.xH2O,将FePO4.xH2O于500℃热处理4 h后得到纳米FePO4前驱体,然后通过碳热还原在不同温度下煅烧合成橄榄石结构的纳米LiFePO4/C样品.采用差热/热重、X射线衍射、扫描电镜、比表面测试、电化学性能测试等分析测试方法对纳米FePO4.xH2O、FePO4前驱体及不同煅烧温度下制得的纳米LiFePO4/C样品进行表征.研究结果表明,700℃烧结10 h合成LiFePO4/C样品的粒径在40~100 nm左右,比表面积为79.8 m2/g;700℃煅烧合成样品在电压2.5~4.2 V,倍率为0.1C、1C、5C、10C、15C时的放电比容量分别达到156.5、134.9、105.8、90.3和80.9 mAh/g,具有较好的倍率性能;样品还表现出较好的容量保持率.     

碳热还原法合成Mg掺杂LiFePO4/C正极材料及电化学性能研究

利用碳热还原法合成了Li1-xMgxFePO4/C(x=0.00、0.01、0.02、0.03、0.04、0.05、0.1)正极材料,通过XRD、SEM、BET、CV、EIS和恒流充放电实验研究了不同掺杂量对产物结构和电化学性能的影响。结果表明少量Mg的掺杂未影响到LiFePO4的晶体结构,但显著改善了其电化学性能。其中,Li0.98Mg0.02FePO4/C材料具有更好的电化学性能,0.1C倍率放电时,首次放电容量达到165.2mAh/g,且循环性能良好。另外,对合成材料的红外光谱进行了研究和指认。