Uniform AlF3 thin layer to improve rate capability of LiNi1/3Co1/3 Mn1/3O2 material for Li-ion batteries

LiNi1/3Co1/3Mn1/3O2 was coated with uniform nano-sized AlF3 layer by chemical precipitation method to improve its rate capability. The samples were characterized by X-ray diffractometry (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), charge-discharge cycling, cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). Uniform coated layer with a thickness of about 3 nm was observed on the surface of LiNi1/3Co1/3Mn1/3O2 particle by TEM. At 0.5C and 2C rates, 1.5% (mass fraction) AlF3-coated LiNi1/3Co1/3Mn1/3O2/Li in 2.8-4.3 V versus Li/Li+ after 80 cycles showed less than 3% of capacity fading, while those of the bare one were 16.5% and 45.9%, respectively. At 5C rate, the capacity retention of the coated sample after 50 cycles maintained 91.4% of the initial discharge capacity, while that of the bare one decreased to 52.6%. EIS result showed that a little change of charge transfer resistance of the coated sample resulting from uniform thin AlF3 layer was proposed as the main reason why its rate capability was improved obviously. CV result further indicated a greater reversibility for the electrode processes and better electrochemical performance of AlF3-coated layer.     

Powder electrochemical properties with different particle sizes of spinel LiAl0.05Mn1.95O4 synthesized by sol-gel method

An Al-doped spinel lithium manganese oxide was prepared by the adipic acid-assisted sol-gel method at 800℃, and the cathode materials （Liml0.05Mnl.9504） with different particle sizes were obtained through ball milling. The effects of particle size on the electrochemical performance of LiAl0.05Mnl.9504 samples were investigated by differential thermal analysis and thermogravimetry, X-ray diffraction, galvanostatic charge-discharge test, cyclic voltammetry, and electrochemical impedance spectroscopy. The results indicate that all samples with different particle sizes show the same pure spinel phase and good crystal structure; LiAlo.osMnl.9504 with Dso = 17.3 μm shows better capacity retention; LiAlo.osMnl.gsO4 cathode materials with small particle size have a bigger resistance of charge transfer than the large one, and the particle size has significant effects on the electrochemical performance of Al-doped spinel LiMn2O4 cathode materials.     

Synthesis and electrochemical performance of 5V spinel LiNi0.5Mn1.5O4 prepared by solid-state reaction

Spinel compound LiNi0.5Mn1.5O4 with high capacity and high rate capability was synthesized by solid-state reaction. At first, MnCl2·4H2O and NiCl2·6H2O were reacted with (NH4)2C2O4·H2O to produce a precursor via a low-temperature solid-state route, then the precursor was reacted with Li2CO3 to synthesize LiNi0.5Mn1.5O4. The effects of calcination temperature and time on the physical properties and electrochemical performance of the products were investigated. Samples were characterized by thermal gravimetric analysis(TGA), scanning electron microscopy(SEM), X-ray diffractometry(XRD), charge-discharge tests and cyclic voltammetry measurements. Scanning electron microscopy(SEM) image shows that as calcination temperature and time increase, the crystallinity of the samples is improved, and their grain sizes are obviously increased. It is found that LiNi0.5Mn1.5O4 calcined at 800 ℃ for 6 h exhibits a typical cubic spinel structure with a space group of Fd3m. Electrochemical tests demonstrate that the sample obtained possesses high capacity and excellent rate capability. When being discharged at a rate as high as 5C after 30 cycles, the as-prepared LiNi0.5Mn1.5O4 powders can still deliver a capacity of 101 mA-h/g, which shows to be a potential cathode material for high power batteries.     

Preparation of LiNi1/3Co1/3Mn1/3O2 cathode materials from spent Li-ion batteries

A recycling process including separation of electrode materials by ultrasonic treatment, acid leaching, Fe-removing, precipitation of cobalt, nickel, manganese and lithium has been applied successfully to recycle spent lithium-ion batteries and to synthesize LiNi1/3Co1/3Mn1/3O2. When ultrasonic treatment with 2-nitroso-4-methylphenol（NMP） at 40 ℃ for 15 min, the electrode materials are separated completely. Above 99% of Co, Ni, Mn and Li, 95% of Fe in the separated electrodes are acid-leached in the optimized conditions of 2 mol/L H2SO4, 1：2 H2O2：H2SO4 （molar ratio）, 70 ℃, 1：10 initial S：L ratio, and l h. 99.5% of Fe and less than 1% of Co, Ni, Mn in the leaching solution can be removed in the conditions of initial pH value 2.0-2.5 adjusted by adding 18% Na2CO3, 90 ℃ and stirring time 3 h. After adjusted to be equal by adding NiSO4, COSO4 and MnSO4 solution, 97.1% of Ni, Co, Mn in the Fe-removing surplus leaching solution can be recovered as Ni1/3Co1/3Mn1/3（OH）2. 94.5% of Li in the surplus filtrate after the deposition of Co, Ni and Mn can be recovered as LiECO3. The LiNi1/3Co1/3Mnl/3O2, prepared from the recovered compounds, is found to have good characteristics of the layered structure and elecrtochemical performance.     

Supercritical-hydrothermal accelerated solid state reaction route for synthesis of LiMn2O4 cathode material for high-power Li-ion batteries

Synthesis of the spinel structure lithium manganese oxide (LiMn₂O₄) by supercritical hydrothermal (SH) accelerated solid state reaction (SSR) route was studied. The impacts of the reaction pressure, reaction temperature and reaction time of SH route, and the calcination temperature of SSR route on the purity, particle morphology and electrochemical properties of the prepared LiMn₂O₄ materials were studied. The experimental results show that after 15 min reaction in SH route at 400 °C and 30 MPa, the reaction time of SSR could be significantly decreased, e.g. down to 3 h with the formation temperature of 800 °C, compared with the conventional solid state reaction method. The prepared LiMn₂O₄ material exhibits good crystallinity, uniform size distribution and good electrochemical performance, and has an initial specific capacity of 120 mA·h/g at a rate of 0.1C (1C=148 mA/g) and a good rate capability at high rates, even up to 50C.     

Synthesis of LiNi1/3CO1/3Mn1/3O2 cathode material via oxalate precursor

Using oxalic acid and stoichiometrically mixed solution of NiCl2, CoCl2, and MnCl2 as starting materials, the triple oxalate precursor of nickel, cobalt, and manganese was synthesized by liquid-phase co-precipitation method. And then the LiNi1/3Co1/3Mn1/3O2 cathode materials for Li-ion battery were prepared from the precursor and LiOH-H2O by solid-state reaction. The precursor and LiNi1/3Co1/3Mn1/3O2 were characterized by chemical analysis, XRD, EDX, SEM and TG-DTA. The results show that the composition of precursor is Ni1/3Co1/3Mn1/3C2O4·2H2O. The product LiNi1/3Co1/3Mn1/3O2, in which nickel, cobalt and manganese are uniformly distributed, is well crystallized with a-NaFeO2 layered structure. Sintering temperature has a remarkable influence on the electrochemical performance of obtained samples. LiNi1/3Co1/3Mn1/3O2 synthesized at 900 ℃ has the best electrochemical properties. At 0.1C rate, its first specific discharge capacity is 159.7 mA·h/g in the voltage range of 2.75-4.30 V and 196.9 mA·h/g in the voltage range of 2.75-4.50 V; at 2C rate, its specific discharge capacity is 121.8 mA·h/g and still 119.7 mA·h/g after 40 cycles. The capacity retention ratio is 98.27%.     

Synthesis and characterization of LiNi0.45Co0.10Mn0.45O2 cathode for lithium ion batteries

1INTRODUCTIONAdvanced rechargeable lithium ion batteriesare attractive for use in consumer electronic andelectric vehicle(EV)application because of a fa-vorable combination of voltage,energy density,cycling performance,and have been developed rap-idly worldwide during the past decade[1,2].LiCoO2has been widely used as a cathode material in com-mercial lithiumion battery because it is reasonableeasy to synthesize and shows a stable discharge ca-pacity[3].But due to its high cost and toxic…     

锂离子电池正极材料LiNi0.5Mn0.5O2的循环性能

采用共沉淀法可以制备出首次放电容量高达210 mA.h/g的LiNi0.5Mn0.5O2材料(2.8~4.5 V,电流密度30 mA/g),但材料循环性能受制备过程中的处理工艺影响很大,处理不严格将导致材料循环性能严重下降。围绕材料的循环性问题,对其机理进行了分析并在此基础上对制备工艺进行了进一步改善:分别从配锂方式,烧结过程中的升降温速率以及烧结的保温制度进行了系统研究。结果表明:采用改进配锂方式,缓慢升温速率(2℃/min),高低温结合的烧结制度和快速风冷工艺所制备的材料首次放电容量达到188 mA.h/g,30个循环后仍保持在174 mA.h/g,循环效率有了明显的提高。     

模拟废旧锂离子电池湿法冶金浸出液再生铝掺杂LiNi0.5Co0.2Mn0.3O2正极材料

采用共沉淀法制备均相Al掺杂的LiNi0.5Co0.2Mn0.3O2正极材料,以利用Al对再生镍钴锰(NCM)正极材料的正面改性作用,并改善锂离子电池回收过程中繁琐和高成本的除杂过程.当浸出液中的Al3+含量为过渡金属(Ni、Co和Mn)总量的1％(摩尔分数)时,制备的Al掺杂NCM正极材料中晶格氧和Ni2+的浓度增加...     

Effect of annealing treatment on electrochemical property of LiNi0.5Mn1.5O4 spinel

LiNi0.5Mn1.5O4 was prepared under different cooling conditions. The electrochemical properties of LiNi0.5Mn1.5O4 prepared under different cooling conditions were investigated. The results show that LiNi0.5Mn1.5O4 synthesized with or without annealing treatment has similar X-ray diffraction patterns that can be indexed to cubic spinel structure. The mass loss occurring above 650℃ during the heating process can be mostly gained during the cooling process. LiNi0.5Mn1.5O4 synthesized with an annealing treatment exhibits almost one voltage plateau at around 4.7 V and higher capacity with a quick fading upon cycling, whereas LiNi0.5Mn1.5O4 synthesized without annealing treatment shows two voltage plateaus at around 4.1 and 4.7 V and superior capacity retention upon cycling both at rates of 1/7C and 1 C, though the capacity is not high.     

Surface modification of LiCo0. 05Mn1.95O4 cathode by coating with SiO2-TiO2 composite

1　INTRODUCTIONSincethefirstcommercializationbySonyCorpo rationintheearly 1990s ,thelithium ionbattery(LIB)hasbecomeamajorproducttodominatethemarketforsmallrechargeablebatteries .Further more ,Li ionbatteriesareexpectedtobeusedasalarge scaleenergystoragedeviceforelectricvehices(EV ) [1] .ThoughvarioustypesofcathodematerialssuchasLiCoO2 ,LiNiO2 ,LiMn2 O4 ,andsubstitutedtran sitionmetaloxidesarecurrentlyusedincommercial izedLi ionbatteries[2 ,3] ,LiCoO2 inthesecathodematerialsismost…     

Synthesis and electrochemical performances of spherical LiFePO4 cathode materials for Li-ion batteries

Spherical LiFePO4 and LiFePO4/C composite powders for lithium ion batteries were synthesized by a novel processing route of co-precipitation and subsequent calcinations in a nitrogen and hydrogen atmosphere. The precursors of LiFePO4, LiFePO4/C composite and the resultant products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and the electrochemical performances were investigated by galvanostatic charge and discharge tests. The precursors composed of amorphous Fe3(PO4)2·xH2O and crystalline Li3PO4 obtained in the co-precipitation processing have a sphere-like morphology. The spherical LiFePO4 derived from the calcinations of the precursor at 700 ℃ for 10 h in a reduction atmosphere shows a discharge capacity of 119 mAh·g -1 at the C/10 rate, while the LiFePO4/C composite with 10wt.% carbon addition exhibits a discharge capacity of 140 mAh·g -1.The electrochemical performances indicate that the LiFePO4/C composite has a higher specific capacity and a more stable cycling performance than the bare olivine LiFePO4 due to the carbon addition enhancing the electronic conductivity.     

LiNi0.7Co0.15Mn0.15O2 microspheres as high-performance cathode materials for lithium-ion batteries

Advanced uniform LiNi0.7Co0.15Mn0.15O2 microspheres were successfully synthesized and examined as cathode materials for lithium-ion batteries. The structure,morphology, and electrochemical performance of LiNi0.7-Co0.15Mn0.15O2 calcined at different temperatures ranging from 650 to 900 °C were systematically investigated. The XRD results show that the material has a well-ordered layered structure with small amount of cation mixing. A distinct spherical morphology of the obtained powders prepared at different temperatures can be seen from the SEM images. The as-synthesized LiNi0.7Co0.15Mn0.15O2 powders have a very high-tap density of about 2.37 g·cm^-3. Among all the samples,the sample calcined at 750 °C exhibits the best electrochemical performance with an initial discharge capacity of185.2 mAh·g^-1（3.0–4.3 V, 0.2C rate） and capacity retention〉94.77 %after50cycles.Moreover,thismaterialshowshighspecific capacity and good cycling stability. The LiNi0.7-Co0.15Mn0.15O2 microspheres with high-specific capacity and high-tap density are promising to use as cathode materials for next-generation high-energy-density lithium-ion batteries.     

Effects of chromium doping on performance of LiNi0.5Mn1.5O4 cathode material

In order to improve the cycle and rate performance of LiNi_0.5Mn_1.5O₄, LiCr_2YNi_0.5–YMn_1.5–YO₄ (0≤Y≤0.15) particles were synthesized by the sucrose-aided combustion method. The effects of Cr doping in LiNi_0.5Mn_1.5O₄ on the structures and electrochemical properties were investigated. The samples were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), cyclic voltammetry (CV), galvanostatic charge-discharge test and electrochemical impedance spectrum (EIS). The results indicate that the LiCr_2YNi_0.5–YMn_1.5–YO₄ possess a spinel structure and small particle size, and LiCr_0.2Ni_0.4Mn_1.4O₄ exhibits the best cyclic and rate performance. It can deliver discharge capacities of 143 and 104 mA·h/g at 1C and 10C, respectively, with good capacity retention of 96.5% at 1C after 50 cycles.     

正极材料LiNi0.4Co0.2Mn0.4O2阴离子掺杂改性研究

采用溶胶-凝胶法合成了层状LiNi0.4Co0.2Mn0.4O1.97X0.03(X=O,F,Cl)正极材料。以XRD、SEM、CV、EIS和充放电测试等手段对材料的晶体结构、表观形貌和电化学性能进行表征。XRD结果显示F-和Cl-掺杂没有改变晶体的六方单层状结构;CV结果表明掺杂提高了材料的可逆性;充放电测试表明,F-和Cl-掺杂均提高了材料的放电容量,并改善了材料的循环性能;EIS测试结果发现,F-和Cl-掺杂均有效地抑制其在循环过程中电化学反应阻抗的增加。     

Effect of ball milling and electrolyte on properties of high-voltage LiNi_(0.5)Mn_(1.5)O_4 spinel

1 INTRODUCTIONRecently ,several research groups have repor-ted transition-metal-substituted spinel materials(Li MxMn2 -xO4, M: Cr , Co , Fe , Ni , Cu) withhigh-voltage plateaus above 4 .5 V[1 5]. Amongthese materials ,Li Ni0 .5Mn1 .5O4is the most prom-ising and attractive one because of its good cyclicproperty and relatively high capacity with a plateauat around 4 .7 V[3 ,6].Now, a variety of methods were used forpreparation of Li Ni0 .5Mn1 .5O4,such as solid-statereaction[4 ,7 ,8]…     

LiFePO4/C锂离子电池正极材料的电化学性能

以碳凝胶作为碳添加剂,采用固相法制备了复合型LiFePO4/C锂离子电池正极材料.研究了不同掺碳量对样品性能的影响.利用X射线衍射仪、扫描电镜和碳硫(质量分数)分析方法对所得样品的晶体结构、表面形貌、含碳量进行分析研究.结果表明:样品中的碳含量(质量分数)分别为0%、5%、10%、22%,所得样品均为单一的橄榄石型晶体结构,碳的加入使LiFePO4颗粒粒径减小.另外,碳分散于晶体颗粒之间,增强了颗粒之间的导电性.合成样品的电化学性能测试结果表明,掺碳后的LiFePO4放电比容量和循环性能都得到显著改善.其中,含碳量为22%的LiFePO4/C在0.1 C倍率下放电,首次放电容量达143.4 mA·h/g,充放电循环6次后电容量为142.7 mA·h/g,容量仅衰减0.7%.     

Surface composition and electrochemical behavior of LiNi1/3Co1/3Mn1/3O2 cathode material with copper additive

LiNi_1/3Co_1/3Mn_1/3O₂（NCM） cathode material containing copper was prepared by co-precipitation method.The material was characterized by X-ray photoelectron spectroscopy（XPS） and galvanostatic cycling.XPS data indicate that surface compositions of the samples containing copper are different from the bare NCM.Copper on surface of particles was enriched,while nickel and lithium content was reduced.The electrochemical performance of NCM was affected by the change of surface compositions.Cycling performance charged to the cutoff voltage of 4.6 V was improved by introducing copper into the material.The effects of copper content on electrochemical behaviors of NCM at 4.5 V were discussed.