Enhanced low-temperature performance of slight Mn-substituted LiFePO<Subscript>4</Subscript>/C cathode for lithium ion batteries

Low temperature performance of LiFePO₄/C cathode was remarkably improved by slight Mn-substitution. Electrochemical measurements showed that about 95% of the discharge capacity of LiFe_0.98Mn_0.02PO₄/C cathode at 20°C was obtained at 0°C, compared to 85% of that of LiFePO₄/C cathode. The LiFe_0.98Mn_0.02PO₄/C sample also presented enhanced rate performance at −20°C with the discharge capacities of 124.4 mA h/g (0.1C), 99.8 mA h/g (1C), 80.7mAh/g (2C) and 70 mA h/g (5C), respectively, while pristine LiFePO₄/C only delivered capacities of 120.5 mA h/g (0.1C), 90.7 mA h/g (1C), 70.4 mA h/g (2C) and 52.2 mA h/g (5C). Cyclic voltammetry measurements demonstrated an obvious improvement of the lithium insertion-extraction process of the LiFePO₄/C cathode by slight Mn-substitution. The results of FSEM observation and electrical conductivity measurement indicated that slight Mn-substitution minimized the particle size of LiFe_0.98Mn_0.02PO₄/C and also obviously improved the electrical conductivity of the compound, thus obviously enhances the interface reaction process on the cathode.     

锂离子电池正极材料LiFePO4/C的制备与表征

采用溶胶-凝胶法合成了LiFePO₄/C复合材料,利用元素分析、X射线衍射（XRD）、扫描电镜（SEM）等方法对其进行了表征,将其组装成模拟电池测试了其电化学性能.结果表明：LiFePO₄/C具有单一的橄榄石型晶体结构,碳粒子平均颗粒大小在1μm左右.LiFePO₄/C复合材料在3.4 V处具有很好的充放电电压平台,与LiFePO₄相比,具有更高的放电比容量和更好的循环性能,在60 ℃时的首次放电容量达到133 mAh/g,经20次循环后的容量保持率为93.8%.     

锂离子电池正极材料LiFePO4的合成及电化学性能

采用固相合成法在不同温度制度下合成掺杂碳的LiFePO4正极材料,计算出各样品的结构参数并对各样品进行电化学测试·结构参数的计算结果表明:合成温度升高,样品的结晶程度更好,结构更紧凑,更趋稳定·电化学测试结果说明:700℃合成的产物具有良好的电化学性能,在0 1C倍率下放电,其室温初始放电容量为140 4mAh/g,循环10次后容量衰减较小·此条件合成的LiFePO4放电容量与目前工业化生产的LiCoO2相当,具有良好的应用前景·     

Low temperature hydrothermal synthesis and electrochemical performances of LiFePO4 microspheres as a cathode material for lithium-ion batteries

Mesoporous LiFePO4 microspheres were simply synthesized by a low temperature(130℃),template-free hydrothermal route using low cost LiOH,Fe(NO3)3 and NH4H2PO4 as starting raw materials.These microspheres are composed of densely aggregated LiFePO4 nanoparticles and filled with interconnected mesochannels,which demonstrates not only a high tap density(≥1.4 g cm-3),a high capacity of 150 mAh g-1(～90% of its theoretical capacity) at 0.5 C rate,but also a ≥ 80% utilization of its theoretical capacity at a high rate of 1 C.In addition,the hydrothermal synthesis developed in this work is simple and cost-effective,it may provide a new route for production of the LiFePO4 material in battery applications.     

Synthesis of LiFePO4 in situ vapor-grown carbon fiber （VGCF） composite cathode material via microwave pyrolysis chemical vapor deposition

One of the most important factors that limits the use of LiFePO 4 as cathode material for lithium ion batteries is its low electronic conductivity.In order to solve this problem,LiFePO 4 in situ vapor-grown carbon fiber (VGCF) composite cathode material has been prepared in a single step through microwave pyrolysis chemical vapor deposition.The phase,microstructure,and electrochemical performance of the composites were investigated.Compared with the cathodes without in situ VGCF,the initial discharge capacity of the composite electrode increases from 109 to 144 mA h g-1 at a 0.5-C rate,and the total electric resistance decreases from 538 to 66.The possible reasons for these effects are proposed.     

Pathway for high-energy density LiMnFePO4 cathodes

Polyanion cathodes are credited for its thermal stability and better safety, no matter in lithium ion batteries or sodium ion batteries. Polyanion oxides with phosphate groups came to the public's attention in 1997, and the representative material is LiFePO₄, which has been widely applied and plays a huge role in the field of powder batteries and energy storage system. However, owing to the low lithiation potentials and storage sites, the energy densities of polyanion cathodes have been restricted, resulting of low-endurance and limited application scenarios. Accordingly, here, we use cheap and environmental friendly raw materials as precursors to synthesis high energy density LiMn_0.6Fe_0.4PO₄@C cathode by a simple spray-drying and high temperature calcination process. The self-designed liquid polyacrylonitrile (LPAN) is added for the intention of nanoparticle coating, conductive network construction and particle granulation. The low-cost and carbon-coated LiMn_0.6Fe_0.4PO₄ cathode exhibits excellent reversible capacity, low electrochemical polarization and excellent rate capacity, which maintains 93.5% capacity retention after cycling 1000 times at 5C. The work introduces a new avenue to fabricate olivine structure cathodes with outstanding electrochemical performance for the high energy density lithium ion batteries.     

电动汽车用锰酸锂与磷酸铁锂动力电池性能比较分析

尖晶石锰酸锂和橄榄石磷酸铁锂离子电池是当前电动汽车用动力电池的主体,采用实验比较研究的方法,对比了两种动力电池正极材料电化学特性,研究了两种材料制备成动力电池的能量密度、功率密度、温度特性、循环寿命以及应用特性.结果表明:除低温性能和功率密度外,磷酸铁锂动力电池在其他方面的性能均优于锰酸锂动力电池.     

Morphological evolution and kinetic enhancement of Li2FexMn1-xSiO4/C cathodes for Li-ion battery

Li_2MnSiO_4-based cathode materials possess reasonable work potentials and high theoretical capacities,while the practical energy/power densities are constrained by their inferior kinetics of Li~+ diffusion.In this work,the Pmn2_1-structure Li_2Fe_xMn_(1-x)SiO_4/C materials were synthesized via a solvothermal method and evaluated as Liion cathode materials,with notable morphological evolutions and tunable crystallographic habits observed after solvothermal process.The Li_2Fe_(0.33)Mn_(0.67)SiO_4/C material delivers an initial reversible capacity of 250.2mAh g~(-1)at 0.1 C(～1.51 Li~+insertion/extraction,1 C=166 mA g~(-1)),excellent high-rate capability(52.2 mAh g~(-1)at 5 C),and good long-term cyclability(64.6%after 196 cycles at 2 C).The enhanced electrochemical properties are attributed to the boosted ion/electron transports induced by preferred morphological and structural characteristics of Li_2Fe_(0.33)Mn_(0.67)SiO_4/C.     

Preparation and electrochemical properties of carbon-coated LiFePO4 hollow nanofibers

Carbon-coated LiFePO₄ hollow nanofibers as cathode materials for Li-ion batteries were obtained by coaxial electrospinning. X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–Teller specific surface area analysis, galvanostatic charge–discharge, and electrochemical impedance spectroscopy (EIS) were employed to investigate the crystalline structure, morphology, and electrochemical performance of the as-prepared hollow nanofibers. The results indicate that the carbon-coated LiFePO₄ hollow nanofibers have good long-term cycling performance and good rate capability: at a current density of 0.2C (1.0C = 170 mA·g-1) in the voltage range of 2.5–4.2 V, the cathode materials achieve an initial discharge specific capacity of 153.16 mAh·g-1 with a first charge–discharge coulombic efficiency of more than 97%, as well as a high capacity retention of 99% after 10 cycles; moreover, the materials can retain a specific capacity of 135.68 mAh·g-1, even at 2C.     

Synthesis, Characterization and Properties of LiFePO4/C Cathode Material

Lithium iron phosphate coated with carbon (LiFePO₄/C) was synthesized by improved solid-state reaction using comparatively lower temperature and fewer sintering time. The carbon came from citric acid, which acted as a new carbon source. It was characterized by thermogravimetry and differential thermal analysis (TG/DTA), X ray diffractometer (XRD), Element Analysis (EA) and Scanning electron microscope (SEM). We also studied the electrochemical properties of the material. The first discharge capacity of the LiFePO₄/C is 121 mAh·g⁻¹ at 10 mA·g⁻¹, at room temperature. When the current density increased to 100 mA·g⁻¹, the first discharge capacity decreased to 110 mAh·g⁻¹ and retained 95% of the initial capacity after 100 cycles. The LiFePO₄/C obtained shows a good electrochemical capacity and cycle ability at a large current density. Foundation item: Supported by the National Natural Science Foundation of China (20071026) Biography: ZHOU Xin-wen (1980-), male, Master, research direction: inorganic material chemistry.     

碳包埋固相法制备LiFePO4及其电化学性能研究

用石墨粉包埋取代保护性气氛,一步固相法制备LiFePO4.采用XRD,FTIR,SEM和恒电流充放电等方法对材料结构、形貌和电化学性能进行了表征.利用循环伏安法研究了Li+在LiFePO4中的嵌/脱过程.结果表明,这种改进的固相法可以合成亚微米级纯相橄榄石结构LiFePO4,所得材料具有良好的倍率性能和循环稳定性,在0.1C和1C倍率首次放电比容量分别为148.3和131.9mAh.g-1,1C和5C倍率下循环50次容量保持率分别为96%和90%.由循环伏安法计算得到阳极峰和阴极峰处Li+的表观扩散系数分别为1.64×10-13和1.94×10-13cm2.s-1.     

Comparative study of different membranes as separators for rechargeable lithium-ion batteries

Membranes of polypropylene (PP), PP coated with nano-Al₂O₃, PP electrospun with polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP), and trilayer laminates of polypropylene-polyethylene-polypropylene (PP/PE/PP) were comparatively studied. Their physical properties were characterized by means of thermal shrinkage test, liquid electrolyte uptake, and field emission scanning electron microscopy (FESEM). Results show that, for the different membranes as PP, PP coated with nano-Al₂O₃, PP electrospun with PVdF-HFP, and PP/PE/PP, the thermal shrinkages are 14%, 6%, 12.6%, and 13.3%, while the liquid electrolyte uptakes are 110%, 150%, 217%, and 129%, respectively. In addition, the effects on the performance of lithium-ion batteries (LiFePO₄ and LiNi_1/3Co_1/3Mn_1/3O₂ as the cathode material) were investigated by AC impedance and galvanostatic charge/discharge test. It is found that PP coated with Al₂O₃ and PP electrospun with PVdF-HFP can effectively increase the wettability between the cathode material and liquid electrolyte, and therefore reduce the charge transfer resistance, which improves the capacity retention and battery performance.     

MgFeSiO4 prepared via a molten salt method as a new cathode material for rechargeable magnesium batteries

Well-crystallized MgFeSiO₄ microparticles were synthesized at different temperatures by a simple molten salt method using KCl flux. As a new cathode for rechargeable magnesium batteries, the material shows a reversible Mg²⁺ intercalation-deintercalation process. In 0.25 mol/L Mg(AlCl₂EtBu)₂/THF electrolyte, MgFeSiO₄ synthesized at 900??C can deliver a 125.1 mAh/g initial discharge capacity and a 91.4% capacity retention on the 20th cycle at a rate of 0.1C (about 15.6 mA/g). The results show that MgFeSiO₄ could be a good host for Mg²⁺ intercalation, and a potential cathode material for high-energy rechargeable magnesium batteries.     

Ce-doped LiNi1/3Co（1/3-x/3）Mn1/3Cex/3O2 cathode materials for use in lithium ion batteries

LiNi1/3Co1/3Mn1/3O2 and Ce-doped LiNi1/3Co1/3Mn1/3O2 cathode materials were synthesized by a co-precipitation method and solid phase synthesis and characterized using X-ray diffraction(XRD) and scanning electron microscopy(SEM).The results indicated that the resultant cathode materials with different Ce content all had a good layer structure and high crystallinity.Electrochemical performance testing of the cathode materials showed that the discharge capacity increased with increasing Ce content while the initial reversible capacity attenuation decreased with Ce doping.When the Ce content of the cathode materials is x=0.2,and the current charge and discharge rate is a constant 0.2 C,the discharge capacity maintained 91% of its initial capacity after cycling 50 times.     

First principles studies on the electronics structures of (Li<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Me<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)FePO<Subscript>4</Subscript> (Me=Na and Be)

Based on density functional theory (DFT) of the first-principle for cathode materials of lithium ion battery, the electronic structures of (Li_1?x Me _x )FePO₄ (Me=Na and Be, x=0–0.40) are calculated by plane wave pseudo-potential method using Cambridge serial total energy package (CASTEP) program. The calculated results show that Li-site doping can improve the electronic conductivity enormously. Doping with Na has a noticeable effect on improving its electrical conductivity. However, serious structural distortion will occur when its doping density is beyond 0.25. In view of this, the best density of doping Na is less than 0.25. Doping with Be has an inconspicuous effect on increasing its electrical conductivity and has good cyclical stability, but it cannot achieve as good results as when it is doped with Na. Therefore we cannot find a middle ground between the two proposals. Considering cost and environmental protection, it is ideal to choose Na. So this method gives a reasonable prediction to the improvement of electronic conductivity through Li-site doping in LiFePO₄ material.     

石墨相氮化碳表面包覆改善锂离子电池正极材料LiCoO2电化学性能的研究

通过简单的固相法和液相法,分别制备出石墨相氮化碳（g-C₃N₄）表面改性的商品化LiCoO₂复合材料,采用扫描电子显微镜观察改性后的材料,发现g-C₃N₄都均匀地包裹在LiCoO₂表面。两种g-C₃N₄-LiCoO₂复合材料被用作锂离子电池的正极材料,电化学测试结果显示,固相法制得的g-C₃N₄-LiCoO₂复合材料在0.2 C的倍率下充放电测试,首次比容量达167 mA·h·g^-1,循环80次后,比容量仍达132 mA·h·g^-1,高于未经g-C₃N₄包裹的纯LiCoO₂（98 mA·h·g^-1）;液相法制得的Y-C₃N₄-LiCoO₂复合材料循环稳定性明显优于同类材料,循环80次后容量保持率均在95%以上。试验证实,g-C₃N₄表面改性的策略具有一定的实用价值,改性后,材料优异的电化学性能归因于g-C₃N₄的包裹处理,这不仅增强了固体电解质界面（SEI）的稳定性,也抑制了锂离子嵌入/脱出电极材料时引起LiCoO₂体积的变化。     

<Emphasis Type="Italic">Ab initio</Emphasis> study of the effects of Ag/Mn doping on the electronic structure of LiFePO<Subscript>4</Subscript>

Based on density functional theory （DFT） of the first-principle for the cathode materials of lithium ion battery, the electronic structures of Li（Fe1-x）PO4 （Me = Ag/Mn, x = 0-0.40） are calculated by plane wave pseudo-potential method using Cambridge serial total energy package （CASTEP） program. The calculated results show that the Fermi level of mixed atoms Fe1-xAgx moves into its conduction bands （CBs） due to the Ag doping. The Li（Fe1-xAgx）PO4 system displays the periodic direct semiconductor characteristic with the increase of Ag-doped concentration. However, for Fe1-xMnx mixed atoms, the Fermi level is pined at the bottom of conduction bands （CBs）, which is ascribed to the interaction between Mn（3d） electrons and Fe（4s） electrons. The intensity of the partial density of states （PDOS） near the bottom of CBs becomes stronger with the increase of Mn-doped concentration. The Fermi energy of the Li（Fe1-xMnx）PO4 reaches maximum at x = 0.25, which is consistent with the experimental value of x = 0.20. The whole conduction property of Mn-doped LiFePO4 is superior to that of Ag-doped LiFePO4 cathode material, but the structural stability is reverse.     

Fabrication and electrochemical properties of 3D nano-network LiFePO_4@multiwalled carbon nanotube composite using risedronic acid as the phosphorus source

LiFePO_4@multiwalled carbon nanotubes(LFP@MWCNTs) nanocomposite has been fabricated using risedronic acid(RDA) as a new eco-friendly phosphorus source. Microscopic, spectroscopic, and electrochemical characterization demonstrate that the MWCNTs are in the form of coiled and cross-linking nanoribbon, which wrapped and encrusted around LiFePO_4 particles to form a three-dimensional(3D) nano-network composite.This microstructure of 3D nano-network is obtained due to the reactions between RDA's special functional groups with Fe~(2+) and C-OH,-C=O or-COOH on the surface of the functionalized MWCNTs. The results also show that the particle size of the fabricated LiFePO_4@MWCNTs composite is below 300 nm with the pure crystal of olivine. This nanocomposite indicates an enhanced reversible capacity of 162.2 mAh g~(-1) at 0.2C, and high capacity retention of 76.5% even at 10C after the 800 th cycles. The electric conductivity and Li~+ diffusion coefficient(D_(Li)~+) of the LiFePO_4@MWCNTs are 3.79 × 10~(-2)S cm~(-1) and 4.46 × 10~(-11) cm~2s~(-1), respectively.These improved electrochemical parameters can be attributed to the nano-sized effect of particles, MWCNTs' wrapping effect and 3D nano-network microstructure of the LFP@MWCNTs resulted from using RDA as a new phosphorus source.     

基于Li2MnO3的富锂类高比容量锂离子电池正极材料的研究进展

综述了近几年来基于Li2MnO3的高比容量二元和三元富锂类锂离子电池正极材料的研究进展.重点讨论了富锂材料zLi2MnO3.(1-z)LiMO2(0相似文献   

A study on nano-sized NiO electrodes doping with C and Co prepared by electrochemical deposition-sintering processes and their capacitance performance

In the present work, it was studied that nanoosized NiO electrodes doping with C and Co were prepared by electrochemical deposition in an ethanol solution containing nickel nitrate and cobalt nitrate and sintering processes. The capacitance performance of such electrodes was also studied. The results reveal that samples obtained by electrochemical deposition first on a porous nickel cathode in an ethanol solution contain 0.5 mol/L nitrates, in which Ni(NO3)2 and Co(NO3)2 were mixed in a molar proportion of 8 : 2. After sintering at 300℃ for 2 h, they exhibited the best performance. XRD analysis illustrates that the essential phase of the product is NiO doping with certain content of C and Co. The particles of product imaged a spherical morphology with sizes of 20---30 nm in diameter, and with an average crystal size of 4--5 nm. The capacitance measurement of the simulating C/NiO capacitors indicates that a single electrode can reach as high as 410.0 F/g, and still maintain the value of 323 F/g after 30 recycles showed as a stabilized value with increasing recycles, when it was discharged at a current of 5 mA.