3D amorphous carbon and graphene co-modified LiFePO4 composite derived from polyol process as electrode for high power lithium-ion batteries

Amorphous carbon and graphene co-modified LiFePO_4 nanocomposite has been synthesized via a facile polyol process in connection with a following thermal treatment.Various characterization techniques,including XRD.Mossbauer spectra,Raman spectra,SEM,TEM,BET,O_2-TPO,galvano charge-discharge,CV and EIS were applied to investigate the phase composition,carbon content,morphological structure and electrochemical performance of the synthesized samples.The effect of introducing way of carbon sources on the properties and performance of LiFePO_4/C/graphene composite was paid special attention.Under optimized synthetic conditions,highly crystalized olivine-type LiFePO_4was successfully obtained with electron conductive Fe_2P and FeP as the main impurity phases.SEM and TEM analyses demonstrated the graphene sheets were randomly distributed inside the sample to create an open structured LiFePO_4 with respect to graphene,while the glucosederived carbon mainly coated over LiFeP04 particles which effectively connected the graphene sheets and LiFePO_4 particles to result in a more efficient charge transfer process.As a result,favorable electrochemical performance was achieved.The performance of the amorphous carbon-graphene co-modified LiFePO_4 was further progressively improved upon cycling in the first 200 cycles to reach a reversible specificcapacity as high as 97 mAh·g~(-1) at 10 C rate.     

石墨烯掺杂LiFePO4电极材料的合成及其电化学性能

采用水热辅助法合成石墨烯改性的LiFePO4多孔微球电极材料.并对材料进行了X射线衍射(XRD),扫描电子显微镜(SEM),透射电子显微镜(TEM),傅里叶变换红外(FT-IR)光谱,充放电等表征.从结果可以看出在2 mol·L-1LiNO3电解液体系中单纯包碳的LiFePO4微球在1C、50C倍率时的比容量分别为137、64 mAh·g-1,而石墨烯改性的LiFePO4微球的比容量分别为141、105 mAh·g-1,表现出较好的倍率特性.恒流循环充放电测试60次后两种材料容量保持率分别为70.2％、83.7％.说明掺杂石墨烯构成的三维导电网络能明显改善LiFePO4的电化学性能.     

控制结晶-微波碳热还原法制备高密度LiFePO4/C

应用控制结晶法从溶液相制备球形FePO4.xH2O,再高温烧结得到FePO4前驱体,最后用微波碳热还原法合成高密度L iFePO4/C.由XRD和SEM表征该材料的结构、形貌,并测试其电化学性能.     

LiFePO4 doped with magnesium prepared by hydrothermal reaction in glucose solution

Lithium iron phosphate （LiFePO4） doped with magnesium was hydrothermally synthesized from commercial LiOH, FeSO4, H3PO4 and MgSO4 with glucose as carbon precursor in aqueous solution. The samples were characterized by X-ray powder diffraction, scanning electron microscopy and constant charge-discharge cycling. The results show that the synthesized powders have been in situ coated with carbon precursor produced from caramel reaction of glucose. At ambient temperature （28±2℃）, the electrochemical performances of LiFePO4 prepared exhibit the high discharge capacity of 135 mAh g^-1 at 5C and good capacity retention of 98% over 90 cycles. The excellent electrochemical performances should be correlated with the intimate contact between carbon and LiFePO4 primary and secondary particles, resulting from the in situ formation of carbon precursor/carbon, leading to the increase in conductivity of LiFePO4.     

Electrochemical and magnetic characterization of LiFePO<Subscript>4</Subscript> and Li<Subscript>0.95</Subscript>Mg<Subscript>0.05</Subscript>FePO<Subscript>4</Subscript> cathode materials

A series of lithium iron phosphates was synthesized via the sol–gel route. Iron phosphides, which are electronic conductors, were formed when sintered at 850°C. Magnetic susceptibility measurements on the samples show antiferromagnetic behaviour with T _N=50±2 K for LiFePO₄ and Li_0.95Mg_0.05PO₄ sintered at temperatures below 850°C. The LiFePO₄ and Li_0.95Mg_0.05FePO4 cathodes show a stable electrochemical capacity in the range of 150–160 mA h/g on cycling. The cyclability deteriorates with increasing sample sintering temperature due to the increased crystal size and impurities.     

溶胶-凝胶法制备多孔LiMnPO4/MWCNT复合材料及其电化学性能

以柠檬酸为络合剂, 采用溶胶-凝胶法制备了多孔LiMnPO4和LiMnPO4/MWCNT(多壁碳纳米管)复合材料. 用X射线衍射(XRD)、场发射扫描电镜(FE-SEM)、N2吸脱附等温曲线(BET)和透射电镜(TEM)对其晶体结构与微观形貌进行了表征. 结果表明, 得到的样品具有橄榄石晶体结构, 物相较纯; 两种材料均具有丰富的多级孔道LiM结n构PO, 孔4中径形在成介了孔高范导围电内性分的布三集维中网, 比络表. 恒面流积充分放别电为测73试.7表、6明9.,9 与 m纯2·gL-iM1; n碳P纳O4米相管比以, 复嵌合入材或料包具埋有的更形高式的在放多孔电比容量, 在0.05C、2C倍率下的放电容量分别为108.8、33.2 mAh·g-1. 电化学交流阻抗谱(EIS)表明MWCNT可以有效提高LiMnPO4的电子导电性. LiMnPO4/MWCNT复合材料具有较优的电化学性能可归因于增强的电子导电性, 连接的孔道结构和高的比表面积.     

Hydrous manganese oxide/carbon nanotube composite electrodes for electrochemical capacitors

A novel type of composite electrode based on hydrous manganese oxide and a single-walled carbon nanotube has been prepared and used in electrochemical capacitors. Cyclic voltammetry, galvanostatic charging/discharging tests and electrochemical impedance measurements were applied to investigate the performance of the composite electrodes with different ratios of hydrous manganese oxide and single-walled carbon nanotube. For comparison, the performance of pure hydrous manganese oxide and pure carbon nanotubes was also studied. In this way, the composite electrode with a 6:4 ratio of hydrous manganese oxide to carbon nanotube was found to be the most promising active material for an electrochemical capacitor, which shows both good capacitance and power characteristics.     

Lithium insertion into chemically etched multi-walled carbon nanotubes

Lithium insertion (deinsertion) into (from) chemically etched multi-walled carbon nanotubes (c-MWNTs) has been investigated using various electrochemical techniques such as chronopotentiometry, chronoamperometry, and electrochemical impedance spectroscopy. The results indicate that not only the reversible capacity but also the rate capability was improved by a chemical etching (shortening) of the nanotubes. The observed enhancement in capability at high-rate lithium insertion/deinsertion is attributed to the increased electrochemically active area and reduced lithium diffusion length along the nanotubes, resulting from the structural defects and open ends of the c-MWNTs.     

Preparation and Electrochemical Performance of V2O3-C Dual-Layer Coated LiFePO4 by Carbothermic Reduction of V2O5

The V₂O₃-C dual-layer coated LiFePO₄ cathode materials with excellent rate capability and cycling stability were prepared by carbothermic reduction of V₂O₅. X-ray powder diffraction, elemental analyzer, high resolution transmission electron microscopy and Raman spectra revealed that the V₂O₃ phase co-existed with carbon in the coating layer of LiFePO₄ particles and the carbon content reduced without graphitization degree changing after the carbothermic reduction of V₂O₅. The electrochemical measurement results indicated that small amounts of V₂O₃ improved rate capability and cycling stability at elevated temperature of LiFePO₄/C cathode materials. The V₂O₃-C dual-layer coated LiFePO₄ composite with 1wt% vanadium oxide delivered an initial specific capacity of 167 mAh/g at 0.2 C and 129 mAh/g at 5 C as well as excellent cycling stability. Even at elevated temperature of 55 oC, the specific capacity of 151 mAh/g was achieved at 1 C without capacity fading after 100 cycles.     

高比能LiFePO4的制备及性能研究

应用液相沉淀法-固相烧结法制备高密度的LiFePO4/C及纯相LiFePO4.X射线衍射、扫描电镜、傅立叶红外光谱仪、电化学性能测试表明:该样品具有单一的橄榄石结构和3.4 V左右的放电平台,掺碳的LiFe-PO4具有更优良的性能,粒度较小粒径分布均匀,振实密度达1.46 g/cm3,0.1C首次放电比容量为144.6mAh/g,循环20次后容量保持率为93.2%,1C倍率首次放电比容量为133.5 mAh/g,循环20次后容量下降8.76%.     

新方法合成LiFePO4/C

以Fe(NO3)3·9H2O、LiNO3、NH4H2PO4和蔗糖为原料,在超临界CO2流体中反应合成,进而经二次焙烧制得LiFePO4/C。 结果表明,在超临界CO2流体中经50 ℃反应24 h,在350和600 ℃焙烧后制得粒径分布在0.5~1.0 μm的纯LiFePO4/C,该材料作为锂离子电池正极的放电比容量达156.6 mA·h/g,经50次循环后容量几乎没有衰减。     

Selectivity of a Lithium‐Recovery Process Based on LiFePO4

The demand for lithium will increase in the near future to 713,000 tonnes per year. Although lake brines contribute to 80% of the production, existing methods for purification of lithium from this source are expensive, slow, and inefficient. A novel electrochemical process with low energy consumption and the ability to increase the purity of a brine solution to close to 98% with a single‐stage galvanostatic cycle is presented.     

微米橄榄石型LiFePO4的水热合成优化

为深入研究大颗粒磷酸铁锂(LiFePO₄)锂离子电池正极材料的性能衰退机理并据此改善其体积能量密度和功率密度, 进而切实推进该材料在电动汽车、混合动力汽车和电站储能等领域的高效广泛应用, 本文通过优化水热合成条件制备了粒径为2 μm的均匀微米LiFePO₄颗粒粉末. 在未经任何改性(包覆或掺杂)的情况下,该材料表现出本征大颗粒LiFePO₄典型的充放电和循环性能, 可作为后续研究的代表样品进一步考察大颗粒材料相对纳米材料性能衰退的机制和根本原因, 最终通过有的放矢地改性手段获得高密度、高能量和高功率的LiFePO₄ 正极材料. 实验结果表明, 增加反应物浓度、水热温度和保温时间以及降低溶液pH 值均有利于LiFePO₄颗粒的长大. 通过比较不同粒径的LiFePO₄的电化学性能确证了其随颗粒尺寸的增大而衰退. 当颗粒大小由0.7 μm增加到16.5 μm时, LiFePO₄在0.1C倍率下的放电比容量由152 mAh·g^-1下降至80 mAh·g^-1.同时, 1C倍率下的循环测试结果表明, 颗粒尺寸越大, LiFePO₄的容量衰减愈严重.     

水热-溶胶-凝胶法合成多壁碳纳米管-Na3V2（PO4）3复合物及其作为锂离子电池正极材料的性能

采用水热和溶胶-凝胶相结合的方法,制备了具有良好电化学性能的新型多壁碳纳米管-Na₃V₂（PO₄）₃（MWCNT-NVP）复合材料（MWCNT的质量分数为8.74%）. 通过场发射扫描电子显微镜表征可知,MWCNT分散在NVP纳米颗粒之间,并起到“电子导电线”的作用. 与纯Na₃V₂（PO₄）₃相比,MWCNT-NVP具有更高的比容量和更优异的循环性能. 在0.2C（35.2 mA·g^-1）的电流密度下,3.0-4.5 V的电压范围内,MWCNT-NVP的初始比容量为82.2 mAh·g^-1. 循环100次以后,比容量为72.3 mAh·g^-1. 在1.0-3.0 V充放电时,MWCNT-NVP的初始容量为100.6 mAh·g^-1. 100次循环以后,其容量保持率高达90%. 同时,交流阻抗测试表明,由于MWCNT的存在,MWCNT-NVP的导电性有了显著的提高. 以上结果表明,MWCNT-NVP是一种良好的锂离子电池电极材料.     

Fabrication of carbon microcapsules containing silicon nanoparticles-carbon nanotubes nanocomposite by sol-gel method for anode in lithium ion battery

Carbon microcapsules containing silicon nanoparticles (Si NPs)-carbon nanotubes (CNTs) nanocomposite (Si-CNT@C) have been fabricated by a surfactant mediated sol-gel method followed by a carbonization process. Silicon nanoparticles-carbon nanotubes (Si-CNT) nanohybrids were produced by a wet-type beadsmill method. To obtain Si-CNT nanocomposites with spherical morphologies, a silica precursor (tetraethylorthosilicate, TEOS) and polymer (PMMA) mixture was employed as a structure-directing medium. Thus the Si-CNT/Silica-Polymer microspheres were prepared by an acid catalyzed sol-gel method. Then a carbon precursor such as polypyrrole (PPy) was incorporated onto the surfaces of pre-existing Si-CNT/silica-polymer to generate Si-CNT/Silica-Polymer@PPy microspheres. Subsequent thermal treatment of the precursor followed by wet etching of silica produced Si-CNT@C microcapsules. The intermediate silica/polymer must disappear during the carbonization and etching process resulting in the formation of an internal free space. The carbon precursor polymer should transform to carbon shell to encapsulate remaining Si-CNT nanocomposites. Therefore, hollow carbon microcapsules containing Si-CNT nanocomposites could be obtained (Si-CNT@C). The successful fabrication was confirmed by scanning electron microscopy (SEM) and X-ray diffraction (XRD). These final materials were employed for anode performance improvement in lithium ion battery. The cyclic performances of these Si-CNT@C microcapsules were measured with a lithium battery half cell tests.     

Synthesis and Electrochemical Property of Flowerlike LiFePO4 by Poly(ethylene glycol)-assisted Hydrothermal Process

Flowerlike LiFePO4 particles self-assembled by plate-like crystals with about 200 nm thickness were prepared by the poly(ethylene glycol)-assisted hydrothermal synthesis. Poly(ethylene glycol) in the hydrothermal system played an important role in reducingthe thickness of the plate-like LiFePO₄ crystals as a co-solvent and forming the flower-like structure as a soft template. The flowerlike LiFePO₄ exhibits high discharge capacity of 140 mAh/g and shows quite good cycling performance in the lithium-ion batteries. Con-sidering that the conductive carbon in the obtained LiFePO₄ is negligible, the excellent cellperformance suggests that the flowerlike LiFePO₄ is a promising cathode material for the lithium-ion batteries.     

High performance lithium-sulfur batteries by facilely coating a conductive carbon nanotube or graphene layer

A dual-layer cathode electrode is constituted by facilely coating a conductive carbon nanotube or graphene layer on the pristine sulfur cathode electrode. The conductive layer can effectively improve the conductivity and suppress the polysulfide diffusion, giving rise to an enhanced electrochemical performance for Li-S batteries.     

Magnetic loading of carbon nanotube/nano-Fe3O4 composite for electrochemical sensing

An electrochemical sensing platform was developed based on the magnetic loading of carbon nanotube (CNT)/nano-Fe₃O₄ composite on electrodes. To demonstrate the concept, nano-Fe₃O₄ was deposited by the chemical coprecipitation of Fe²⁺ and Fe³⁺ in the presence of CNTs in an alkaline solution. The resulting magnetic nanocomposite brings new capabilities for electrochemical devices by combining the advantages of CNT and nano-Fe₃O₄ and provides an alternative way for loading CNT on electrodes. The fabrication and the performances of the magnetic nanocomposite modified electrodes have been described. Cyclic voltammetry (CV) and constant potential measurement indicated that the incorporated CNT exhibited higher electrocatalytic activity toward the redox processes of hydrogen peroxide. In addition, chitosan (CTS) has also been introduced into the bulk of the CNT/nano-Fe₃O₄ composite by coprecipitation to immobilize glucose oxidase (GOx) for sensing glucose. The marked electrocatalytic activity toward hydrogen peroxide permits effective low-potential amperometric biosensing of glucose, in connection with the incorporation of GOx into CNT/Fe₃O₄/CTS composite. The accelerated electron transfer is coupled with surface renewability. TEM images and XRDs offer insights into the nature of the magnetic composites. The concept of the magnetic loading of CNT nanocomposites indicates great promise for creating CNT-based biosensing devices and expands the scope of CNT-based electrochemical devices.     

LiFePO_4新型正极材料电化学性能的研究

采用固相反应结合高速球磨法,合成了锂离子电池新型正极材料LiFePO4,并对该材料进行碳包覆处理;采用XRD、SEM、元素分析以及价态化学分析等方法对样品进行表征.实验表明,LiFePO4具有3.4V的放电电压平台,而且包覆碳后的磷酸铁锂具有更好的电化学性能,首次放电容量达147mAh/g,充放电循环100次后容量只衰减9.5%.