Preparation and electrochemical properties of Co3O4/graphite composites as anodes of lithium ion batteries

Co3O4/graphite composites were synthesized by precipitation of cobalt oxalate on the surface of graphite and pyrolysis of the precipitate, and the effects of graphite content and calcination temperature on the electrochemical properties of the composites were investigated. The samples were characterized by thermogravimetry and differential thermal analysis (TG/DTA), X-ray diffractometry (XRD), scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and charge/discharge measurements. With increasing the graphite content, the reversible capacity of the Co3O4/graphite composites decreases, while cycling stability improves dramatically, and the addition of graphite obviously decreases the average potential of lithium intercalation/deintercalation. The reversible capacity of the composites with 50% graphite rises from 583 to 725 mAh/g as the calcination temperature increases from 300 to 500 ℃, and the Co3O4/graphite composites synthesized at 400 ℃ show the best cycling stability without capacity loss in the initial 20 cycles. The CV profile of the composite presents two couples of redox peaks, corresponding to the lithium intercalaction/deintercalation for graphite and Co3O4, respectively. EIS studies indicate that the electrochemical impedance decreases with increasing the graphite content.     

Soft chemical synthesis and electrochemical properties of tin oxide-based materials as anodes for lithium ion batteries

1　INTRODUCTIONWiththedevelopmentoflithiumionbatteries ,thereisanincreasingdemandforelectrodematerialspossessinghighcapacity .Muchresearchwasunder takentosearchfornewanodematerialsin placeofcarbon (theoreticalmaximumcapacityof 372mA·h·g- 1)toimproveenergydensityforrechargeablelithi umionbatteries[110 ] .Notably ,tinoxide basedmate rials ,aspossiblecandidatesforthenextgenerationanodematerialsforLi ionbatteriesduetotheirhighlithiumstoragecapacityandlow potentialoflithiumionintercalation ,…     

Structure characterization and electrochemical properties of new lithium salt LiODFB for electrolyte of lithium ion batteries

Lithium difluoro（axalato）borate （LiODFB） was synthesized in dimethyl carbonate （DMC） solvent and purified by the method of solventing-out crystallization. The structure characterization of the purified LiODFB was performed by Fourier transform infrared （FTIR） spectrometry and nuclear magnetic resonance （NMR） spectrometry. The electrochemical properties of the cells using 1 mol/L LiPF6 and 1 mol/L LiODFB in ethylene carbonate （EC）/DMC were investigated, respectively. The results indicate that LiODFB can be reduced at about 1.5 V and form a robust protective solid electrolyte interface （SEI） film on the graphite surface in the first cycle. The graphite/LiNi1/3Mn1/3Co1/3O2 cells with LiODFB-based electrolyte have very good capacity retention at 55 ℃, and show very good rate capability at 0.5C and 1C charge/discharge rate. Therefore, as a new salt, LiODFB is a most promising alternative lithium salt to replace LiPF6 for lithium ion battery electrolytes in the future.     

5V锂离子电池正极材料的制备和电化学性能研究

用液相法合成出用锂和镍取代的尖晶石锂锰氧化物正极材料.用XRD和FTIR对其进行了表征,并探讨了其在有机电解液的电化学性能.研究结果表明:在锂锰氧化物掺入适量的镍(锰∶镍的摩尔比为1.4∶0.6)可以改善尖晶石LiMn2O4的循环性能,提高放电平台,使其大部分容量往高电位方向移动,电池的放电电压提高,这样的材料适合做5V电池的正极材料.     

Preparation and electrochemical performance of MWCNTs@MnO2 nanocomposite for lithium ion batteries

Tubular nanocomposite with interconnected MnO2 nanoflakes coated on MWCNTs(MWCNTs@MnO2)was fabricated by an aqueous solution method at 80°C.Scanning electron microscopy,X-ray diffraction and galvanostatic charge-discharge tests were used to characterize the structures and electrochemical performances of the as-prepared nanocomposite.The capacity reaches 1233.6 mA h g-1 at a current density of 100 mA g-1 for the first discharge,and it can still maintain a capacity of 633.1mA h g-1 after 100 charge-discharge cycles.The results show that MWCNTs with good electrical conductivity as anchors of MnO2 can provide fast electron transport channels for MnO2 in the electrochemical reactions,and the as-prepared MWCNTs@MnO2 nanocomposite is a potential anode material for lithium ion batteries.     

Z-CoS2-MoS2/rGO的合成及电化学储锂性能

为了研发比容量高和循环性能稳定的电化学储锂电极材料,用二甲基咪唑钴(ZIF-67)作为Co源前驱体,通过一步水热法制备Z-CoS₂-MoS₂/rGO(还原氧化石墨烯)复合材料,研究微观结构和电化学储锂性能. 结果表明,与采用CoCl₂作为钴源制得的CoS₂-MoS₂/rGO相比,Z-CoS₂-MoS₂/rGO复合材料中CoS₂粒子有着更加细小和较均匀的粒径,很好地分散在MoS₂和rGO表面,形成了相应的异质结构. 作为电化学储锂电极材料,Z-CoS₂-MoS₂/rGO的可逆比容量可以达到1 092 mA·h/g,经900次循环后在500 mA/g电流密度下保持了941 mA·h/g的储锂可逆比容量,显示了稳定的充放电循环性能. Z-CoS₂-MoS₂/rGO优异的电化学储锂性能主要归因于该双金属硫化物复合材料具有较多的电化学储锂电极反应电对以及复合材料中CoS₂纳米颗粒、MoS₂纳米片和rGO之间均匀的复合及所形成的异质结构.     

Electrochemical properties of spinel LiMn2O4 and LiAl0.1Mn1.9O3.9F0.1 synthesized by solid-state reaction

Two types of spinel cathode powders, LiMn2O4 and LiAl0.1Mn1.9O3.9F0.1, were synthesized by solid-state reaction. X-ray diffraction (XRD) patterns of the prepared samples were identified as the spinel structure with a space group of Fd 3 m. The cubic lattice parameter was determined from least-squares fitting of the XRD data. The LiAl0.1Mn1.9O3.9F0.1 sample showed a little lower initial capacity, but better cycling performance than the LiMn2O4 sample at both room temperature and an elevated temperature. The Vanderbilt method was used to test the electrochemical conductivity of the LiMn2O4 samples. The electrochemical impedance spec-troscopy (EIS) method was employed to investigate the electrochemical properties of these spinel LiMn2O4 samples.     

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.     

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.     

Characteristics of LiCoO2, LiMn2O4 and LiNi0.45Co0.1Mn0.45O2 as cathodes of lithium ion batteries

LiNi_0.45Co_0.10Mn_0.45O₂ was synthesized from Li₂CO₃ and a triple oxide of nickel, cobalt and manganese at 950 °C in air. The structures and characteristics of LiNi_0.45Co_0.10Mn_0.45O₂, LiCoO₂ and LiMn₂O₄ were investigated by XRD, SEM and electrochemical measurements. The results show that LiNi_0.45Co_0.10Mn_0.45O₂ has a layered structure with hexagonal lattice. The commercial LiCoO₂ has sphere-like appearance and smooth surfaces, while the LiMn₂O₄ and LiNi_0.45Co_0.10Mn_0.45O₂ consist of cornered and uneven particles. LiNi_0.45Co_0.10Mn_0.45O₂ has a large discharge capacity of 140.9 mA · h/g in practical lithium ion battery, which is 33.4% and 2.8% above that of LiMn₂O₄ and LiCoO₂, respectively. LiCoO₂ and LiMn₂O₄ have higher discharge voltage and better rate-capability than LiNi_0.45Co_0.10Mn_0.45O₂. All the three cathodes have excellent cycling performance with capacity retention of above 89.3% at the 250th cycle. Batteries with LiMn₂O₄ or LiNi_0.45Co_0.10Mn_0.45O₂ cathodes show better safety performance under abusive conditions than those with LiCoO₂ cathodes. Foundation item: Project(50302016) supported by the National Natural Science Foundation of China; Project(2005037698) supported by the Postdoctoral Science Foundation of China     

Synthesis of Li-doped Co3O4 truncated octahedra with improved performances in CO oxidation and lithium ion batteries

Single-crystalline Li-doped Co3O4 truncated octahedra with different doping contents were synthesized by a simple combustion method with the fuel of multi-walled carbon nanotubes(MWCNTs).Controlled experiments showed that the pristine well-defined Co3O4 octahedra were obtained with exposed surfaces of {111} planes without lithium doping.In comparison with the octahedra,the truncated Co3O4 octahedra were composed of original {111} planes and extra {100} planes.It could be attributable to the selective adsorption of lithium ions on the {100} planes,making these planes with higher surface energy coexist with the crystal faces of {111}.Furthermore,the Li-doped truncated octahedra and undoped octahedra were used as catalysts in CO oxidation and as anode materials for Li-ion batteries(LIBs).The measurements exhibited that the Li-doped octahedra with added {100} crystal faces showed improved catalytic activity and electrochemical property because of the exposure of the higher energy faces of {100} and enhanced conductivity by Li doping.     

Preparation of LiFePO4 for lithium ion battery using Fe2P2O7 as precursor

In order to obtain a new precursor for LiFePO4, Fe2P2O7 with high purity was prepared through solid phase reaction at 650 ℃ using starting materials of FeC2O4 and NH4H2PO4 in an argon atmosphere. Using the as-prepared Fe2P2O7, Li2CO3 and glucose as raw materials, pure LiFePO4 and LiFePO4/C composite materials were respectively synthesized by solid state reaction at 700 ℃ in an argon atmosphere. X-ray diffractometry and scanning electron microscopy（SEM） were employed to characterize the as-prepared Fe2P2O7, LiFePO4 and LiFePO4/C. The as-prepared Fe2P2O7 crystallizes in the Cl space group and belongs to β-Fe2P2O7 for crystal phase. The particle size distribution of Fe2P2O7 observed by SEM is 0.4-3.0 μm. During the Li^＋ ion chemical intercalation, radical P2O7^4- is disrupted into two PO4^3- ions in the presence of O^2-, thus providing a feasible technique to dispose this poor dissolvable pyrophosphate. LiFePO4/C composite exhibits initial charge and discharge capacities of 154 and 132 mA·h/g, respectively.     

碳包覆石墨作为锂离子电池负极材料的研究

将天然石墨(NG)用浓HNO3氧化处理后,在其表面包覆柠檬酸,在惰性气体气氛下700℃处理18h,制得了包覆改性石墨.采用XRD及电化学测试等手段对材料进行了结构表征和性能测试.考察了不同包覆比例对材料充放电性能的影响.XRD结果表明包覆改性对石墨的结构并没有明显的影响.充放电测试表明,与天然石墨相比,包覆改性石墨具有更好的电化学性能,其中又以石墨与柠檬酸质量比为2∶1时性能最好,其首次放电容量为345.1 mA h g1,经20次循环后容量仍保持在305 mA h g1以上,容量衰减率仅为11.01%.     

Layer by layer synthesis of Sn-Co-C microcomposites and their application in lithium ion batteries

Alloy anodes were studied for pursuing Sn-based microcomposite synthesis, assembly and performance for lithium ion batteries. The self-assembled Sn-Co-C composites with nano-scaled microstructures were prepared via solution method and carbothermal technology. The morphology and physical structure were investigated with scanning electron microscope (SEM) and X-ray diffraction (XRD). The as-prepared materials were assembled to half cell coin for the purpose of discussing the galvanostatic cycling, cyclic voltammetry and rate-capability performance. Results reveal that nanoscaled CoSn 2 alloys covered with Sn and C layer by layer are wrapped by cross-linked porous carbon network to form spherical microstructure. This distinguishing feature of Sn-Co-C composites provides a possible solution to the problems of Sn particle aggregation and poor electron transport, and has strong effect on improving electrochemical performance.     

Synthesis and electrochemical properties of LiNi0.8Al0.2-xTixO2 cathode materials by an ultrasonic-assisted co-precipitation method

A new co-precipitation route was proposed to synthesize LiNi0.8Al0.2-xTixO2 (x=0.0-0.20) cathode materials for lithium ion batteries, with Ni(NO3)2, Al(NO3)3, LiOH.H2O, and TiO2 as the starting materials. Ultrasonic vibration was used during preparing the precursors, and the precursors were protected by absolute ethanol before calcination in the air. The influences of doped-Ti content, calcination temperature and time, additional Li content, and ultrasonic vibration on the structure and properties of LiNi0....     

均相沉淀法制备Zn Fe2 O4负极材料及其储锂性能

采用均相沉淀法制备了ZnFe2 O4前驱体,探索了烧结温度对ZnFe2 O4结构和电化学性能的影响。用X射线衍射（XRD）和场发射扫描电子显微镜（FESEM）表征了材料的微观结构和形貌;采用循环伏安（CV）、电化学交流阻抗谱（EIS）和充放电测试了ZnFe2 O4作为锂离子电池负极材料的储锂性能。结果表明：随着烧结温度的升高,样品粒径增大;当烧结温度达到900℃时可以得到纯相尖晶石型ZnFe2 O4,其中在900℃下烧结的ZnFe2 O4样品具有最高的嵌锂活性、最好的电化学反应可逆性、最低的电化学反应阻抗和优良的倍率性能。     

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.     

锂离子电池负极材料 Na2Li2Ti6O14的嵌脱锂过程动力学研究

为了研究钛酸钠锂(Na2Li2Ti6O14)负极材料嵌脱锂的动力学行为,用溶胶-凝胶法合成 Na2Li2Ti6O14负极材料,采用 X 射线衍射法(XRD)和电子显微镜(SEM)分别对材料进行物相分析和微观形貌的观察.采用恒流充放电测试、循环伏安法(CV)和恒电流间歇滴定法(GITT)研究了 Na2Li2Ti6O14的电化学性能和嵌脱锂过程动力学.研究结果表明,制备的 Na2Li2Ti6O14材料纯度高,结晶度良好,循环稳定性好;由不同扫描速率的循环伏安法测出的 Na2Li2Ti6O14中锂离子在氧化、还原峰对应的化学扩散系数 Da和 Dc分别为7.3×10-11和7.8×10-11cm2/s;由恒电流间歇滴定技术测得的锂离子在 Na2Li2Ti6O14电极中的扩散系数为10-11~10-8cm2/s.