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.     

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.     

一种合成LiFePO4的新方法

结合共沉淀原理和腐蚀电化学原理,提出了一种合成LiFePO4的新方法.对新方法合成路线中的反应物、添加物以及热处理条件作了实验分析,并用XRD分析了LiFePO4的晶体结构和晶粒尺寸分布,用SEM分析了形貌,用充放电测试技术分析了材料的比容量及其电化学性能.结果表明:新方法在合成中不引入其它杂质离子,避免了常规共沉淀合成工艺中过滤.洗涤等过程对LiFePO4前驱体的不利影响.用新方法制备的LiFePO4晶粒分布在20-70 nm,在0.1C下首次放电容量为147 mAh/g.新方法有利于对LiFePO4的Mg2 掺杂改性,明显地提高LiFe1-xMgxPO4的电化学性能.     

溶胶机械活化及其溶剂对LiFePO4/C结构和电化学性能的影响

本文在溶胶凝胶法制备碳包覆LiFePO4/C锂离子电池正极材料的基础上,对溶胶进行机械球磨活化以进一步优化LiFePO4/C复合材料的结构和形貌,并通过原位引入Fe2P等方法,提高其高倍率性能。采用XRD、SEM、元素分析等材料结构测试分析方法和恒电流充放电及电化学阻抗谱电化学测试技术,对溶胶机械活化及不同溶胶溶剂对LiFePO4/C材料结构和电化学性能的影响进行了研究。研究结果表明,机械活化能有效减小LiFePO4/C颗粒的尺寸及改善其分散性,并能改变Fe2P相的含量。溶胶机械活化处理后的LiFePO4/C在不同倍率下的放电容量明显增加。相对于蒸馏水,乙醇作为溶胶溶剂获得的LiFePO4/C材料具有更好的倍率性能,其在1C和10C的容量分别达到136mAh/g和90mAh/g。     

过渡金属离子掺杂对磷酸铁锂性能的影响

以碳酸锂、草酸亚铁、磷酸二氢铵、葡萄糖为原料,添加不同的过渡金属乙酸盐(乙酸锰、乙酸钴、乙酸镍、乙酸锌),在氩气保护下采用高温固相法制备LiFePO4/C复合材料.采用X射线衍射、扫描电子显微镜、同步热分析、恒电流充放电、电化学阻抗、循环伏安等方法研究掺杂金属离子及掺杂量对LiFePO4/C晶体结构和电化学性能的影响.结果表明,LiFe0.9M0.1PO4/C(M=Mn、Co、Ni、Zn)样品的晶体结构均与橄榄石型LiFePO4相同.掺杂过渡金属阳离子可以提高LiFeP04/C的还原电位,降低氧化电位,缩小氧化还原峰间距,提高化学反应的可逆性.掺杂后的样品在5C下的放电性能较好,以LiFe0.9Ni0.1PO4/C的放电容量最高,达到89 mAh/g.     

Facile Synthesis of NiFe_2O_4/Reduced Graphene Oxide Hybrid with Enhanced Electrochemical Lithium Storage Performance

In this work, a facile, one-pot route has been applied to synthesize nanohybrids based on mixed oxide Ni Fe2O4 and reduced graphene oxide(r GO). The hybrid is constructed by nanosized Ni Fe2O4 crystals confined by fewlayered r GO sheets. The formation mechanism and microstructure of the hybrids have been clarified by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, and transmission electron microscopy.Electrochemical tests show that the performance of Ni Fe2O4 can be considerably improved by r GO incorporation. The performance improvement can be attributed to the two-dimensional conductive channels and the unique hybrid structure r GO constructed. The easy synthesis and good electrochemical performance of Ni Fe2O4/r GO hybrid make it a promising anode material for Li-ion batteries.     

Development of bimetal-grown multi-scale carbon micro-nanofibers as an immobilizing matrix for enzymes in biosensor applications

This study describes the development of a novel bimetal (Fe and Cu)-grown hierarchical web of carbon micro-nanofiber-based electrode for biosensor applications, in particular to detect glucose in liquids. Carbon nanofibers (CNFs) are grown on activated carbon microfibers (ACFs) by chemical vapor deposition (CVD) using Cu and Fe as the metal catalysts. The transition metal-fiber composite is used as the working electrode of a biosensor applied to detect glucose in liquids. In such a bi-nanometal-grown multi-scale web of ACF/CNF, Cu nanoparticles adhere to the ACF-surface, whereas Fe nanoparticles used to catalyze the growth of nanofibers attach to the CNF tips. By ultrasonication, Fe nanoparticles are dislodged from the tips of the CNFs. Glucose oxidase (GOx) is subsequently immobilized on the tips by adsorption. The dispersion of Cu nanoparticles at the substrate surface results in increased conductivity, facilitating electron transfer from the glucose solution to the ACF surface during the enzymatic reaction with glucose. The prepared Cu-ACF/CNF/GOx electrode is characterized for various surface and physicochemical properties by different analytical techniques, including scanning electron microscopy (SEM), electron dispersive X-ray analysis (EDX), Fourier-transform infrared spectroscopy (FTIR), BET surface area analysis, and transmission electron microscopy (TEM). The electrochemical tests show that the prepared electrode has fast response current, electrochemical stability, and high electron transfer rate, corroborated by CV and calibration curves. The prepared transition metal-based carbon electrode in this study is cost-effective, simple to develop, and has a stable immobilization matrix for enzymes.     

Synthesis and Electrochemical Properties of Carbon-Mixed LiEr_(0.02)Fe_(0.98)PO_4 Cathode Material for Lithium-ion Batteries

LiEr0.02Fe0.98PO4/C composite cathode was synthesized by a simple solution method with polyethylene glycol (PEG) as the reductive agent and carbon source. The effect of erbium doping on the electrochemical behavior of LiFePO4 was studied in this paper. The samples were characterized by X-ray powder diffraction and scanning electron microscopy and the electrochemical properties were investigated by the charge-discharge test. An initial discharge capacity of 149 mAh·g-1 was achieved for the LiEr0.02Fe0.98PO4/C composite cathode with a rate of 0.1 C. The electronic conductivity of Er doped LiFePO4/C was measured as 10-2 S·cm-1. The results indicated that erbium doping did not destroy the lattice structure of LiFePO4 and enlarge the lattice volume. These changes are beneficial to the improvement of the electrochemical performance of the LiFePO4 cathode.     

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．     

超临界水热制备LiFePO4及煅烧碳包覆改性研究

本文以FeSO_4、H_3PO_4和LiOH为原料,采用超临界水热过程制备了亚微米级LiFePO_4颗粒.在此基础上,为了提升制备的LiFePO_4正极材料的物理和电化学性能,对其进行了后续煅烧碳包覆改性研究.同时,通过XRD、SEM、充放电测试、CV和EIS测试手段,对LiFePO_4正极材料改性前后的结构、形貌和电化学性能进行了表征.结果表明:后续固相煅烧碳包覆改性能够显著改善LiFePO_4的结晶性能,减小颗粒粒径,降低电荷传递阻抗,以及大幅度地提升放电容量和循环性能;以PVP为模板剂、蔗糖为碳源,700℃煅烧1 h得到的LiFePO_4/C颗粒粒径小、分布均一,室温0.2 C倍率的首圈放电比容量为153.1 mAh/g,1 C倍率充放电时,放电比容量可保持在144.2 mAh/g,1 C循环50次,容量保持率达到97.1%.     

聚噻吩/活性炭复合材料作为超级电容器电极材料的电性能

采用原位聚合的方法在活性炭表面引发噻吩聚合,制备不同配比的聚噻吩/活性炭复合材料作为超级电容器电极材料,并研究了不同配比对材料电性能及结构的影响.采用傅里叶红外光谱及场发射扫描电镜研究了材料的化学结构及表面形态.采用循环伏安,恒流充放电等方法评价了材料电性能.结果表明,当活性炭与噻吩的摩尔比为10:1时,复合材料呈蓬松...     

烧结方式对LiFePO4/C复合正极材料电化学性能的影响

对LiFePO4/C复合前驱体,分别采用静态氮气气氛,动态氮气气氛及静态真空三种烧结方式进行碳热还原合成LiFePO4/C复合正极材料.采用XRD、SEM、CV和充放电循环测试等方法分析和表征材料的结构、形貌和电化学性能.结果表明,烧结方式对所得材料的结晶度、晶粒大小、碳含量、合成温度以及电化学性能均有显著影响.真空烧结所得材料结晶度高,而动态气氛烧结对材料颗粒细化及均匀化都有积极影响,同时也能有效促进锂离子扩散动力学.动态气氛烧结可将材料的烧结温度降低到500℃,且所得材料表现出优异的电化学性能.0.5C倍率下循环首次放电比容量达到163.4 mAh/g,50次循环后容量保持率为99.02%.     

催化裂解天然气于碳毡内低成本合成碳纳米管

基于制备碳/碳(C/C)复合材料的等温化学气相渗透(ICVI)技术,在1010～1100℃用Fe催化裂解工业天然气可在碳毡内原位合成出碳纳米管(CNTs).扫描电镜(SEM)观察结果表明,1060℃合成的CNTs具有较好的覆盖形貌和均匀管径(110～120nm)且纯净度高.高分辨率透射电镜(HRTEM)和Raman光谱测试结果进一步表明,该温度下合成的CNTs结晶度高,与碳纤维间结合力强.     

The microstructure and electrochemical characteristics of LiFePO4/carbon-network composite

LiFePO4/carbon-network composite was synthesized by a high temperature solid-state method using the natural sawdust as carbon precursor. The microstructure of the as-synthesized sample was characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM), respectively. The results revealed that the LiFePO4 particles with diameters ranging from 30 to 150 nm were well connected by carbon networks. The electrochemical performance of the composite was characterized using galvanostatic charge-discharge technique. The initial discharge capacity of LiFePO4/carbon-network cathode reached 126 mAh x g(-1) with 0.2 C rate.     

Y掺杂Mn3O4/石墨烯复合材料的电化学性能

通过水热法在不同反应温度、一定反应时间条件下制备用于超级电容器的Mn3O4,同时实现Y的掺杂和复合石墨烯。通过X射线衍射(XRD)、扫描电子显微镜(SEM)和电化学工作站对样品的形貌、结构与电化学性能进行分析,发现其与标准PDF卡89-4837相吻合,为单一相的Mn3O4,属四方晶系,空间群为I41/amd(No.141)。所制得Mn3O4为棒状颗粒。Y掺杂含量为5%时Y-Mn3O4的比电容可以达到89 F·g^-1,Y-Mn3O4/石墨烯复合材料的比电容可达到267F·g^-1,并且它们的循环伏安曲线为矩形形状,说明Y的掺杂和石墨烯的负载协同提高了Mn3O4的电化学性能。     

银的添加方式对LiFePO_4性能的影响

以化学镀(ELP)和真空热分解(VTD)工艺制得了LiFePO4/Ag复合材料,采用X射线衍射、扫描电镜对样品进行了表征,同时对样品进行了交流阻抗、循环伏安和恒流充放电等电化学性能测试.结果表明,与纯LiFe-PO4相比,复合材料的首次不可逆容量有所降低,比容量增加.真空热分解所制得的银颗粒更小且分布更均匀.该复合材料在0.2C下首次放电容量为143.1mAh/g,库仑效率为90.6%;在1C下循环30次后仍能释放出116.6mAh/g的可逆容量.     

SnO2/还原氧化石墨烯/聚吡咯三元复合物的合成及其电化学电容性能

采用两步法制备出均匀分散的SnO2/还原氧化石墨烯(SnO2/RGO)二元复合物,再以二元复合物为模板,通过化学氧化法聚合吡咯(Py)单体,制备出SnO2/还原氧化石墨烯/聚吡咯(SnO2/RGO/PPy)三元复合材料。利用红外光谱(FTIR)、X射线衍射(XRD)和场发射扫描电镜(FESEM)对复合材料结构和形貌进行物性表征,利用循环伏安、恒电流充放电和交流阻抗对复合材料进行电化学性能研究,并讨论了不同含量的PPy对复合材料的结构和性能的影响。结果表明,所合成的三元复合材料的比电容随PPy含量的增加而增大,最大达到305.3F/g。三元复合物电容性能增强源于SnO2、RGO与PPy三者的相互协同作用,以及材料层状结构和大的比表面积。     

LiFe_(1-x)Ni_xPO_4复合正极材料的制备及性能研究

采用两步固相原位烧结掺杂法制备了一系列镍掺杂的锂离子电池正极材料LiFe1-xNixPO4(x=0、0.03、0.05、0.07、0.10、0.15).Ni替代部分Fe,改变了LiFePO4的晶胞参教,细化了晶粒.充放电实验研究表明,低放电倍率(0.1C)时,LiFe0.095Ni0.05PO4的首次放电容量最大,为155mAh/g,较LiFePO4增加了22.8%;0.5C时,其容量为132mAh/g,较LiFePO4增加了14.7%;放电倍率增加为1C时,其容量也能达到122mAh/g,较LiFePO4增加了16.1%.适量掺杂Ni可提高LiFePO4的充放电比容量,改善其高倍率充放电性能.     

LiFePO4-LiNi1/3Co（1/3）Mn1/3O2混合材料对锂离子电池性能的影响

通过流变相辅助高温固相碳热还原法及碳酸共沉淀法合成了LiFePO4/C复合材料及三元系锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2。将二者按一定比例经强力搅拌混合均匀,获得均匀的共混锂离子电池用正极材料。通过循环充放电测试、交流阻抗测试等研究了混合比例对混合材料电化学性能的影响。实验结果表明LiFePO4与LiNi1/3Co1/3Mn1/3O2通过混合,二者之间产生较强的协同作用,从而实现二者之间的优势互补。并且当混合比例为1∶2时,混合电极具有较好的低温性能、倍率性能及循环稳定性和较高的平均放电平台电压及比能量密度。