Tuning Li_3PO_4 modification on the electrochemical performance of nickel-rich LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2

Surface deterioration occurs more easily in nickel-rich cathode materials with the increase of nickel content. To simultaneously prevent deterioration of active cathode materials and improve the electrochemical performance of the nickel-rich cathode material, the surface of nickel-rich LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2 cathode material is decorated with the stable structure and conductive Li_3PO_4 by a facile method. The LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2–1 wt%, 2 wt%, 3 wt%Li_3 PO_4 samples deliver a high-capacity retention of more than 85% after 100 cycles at 1 C under a high voltage of 4.5 V. The effect of different coating amounts(0–5 wt%) for the LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2 cathode is analyzed in detail. Results show that 2 wt% coating of Li_3PO_4 gives better performance compared to other coating concentrations. Detailed analysis of the structure of the samples during the charge-discharge process is performed by in-situ X-ray diffraction. It is indicated that the modification for LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2 cathode could protect the well-layered structure under high voltages. In consequence, the electrochemical performance of modified samples is greatly improved.     

Electrochemical performance of a nickel-rich LiNi<Subscript>0.6</Subscript>Co<Subscript>0.2</Subscript>Mn<Subscript>0.2</Subscript>O<Subscript>2</Subscript> cathode material for lithium-ion batteries under different cut-off voltages

A spherical-like Ni_0.6Co_0.2Mn_0.2(OH)₂ precursor was tuned homogeneously to synthesize LiNi_0.6Co_0.2Mn_0.2O₂ as a cathode material for lithium-ion batteries. The effects of calcination temperature on the crystal structure, morphology, and the electrochemical performance of the as-prepared LiNi_0.6Co_0.2Mn_0.2O₂ were investigated in detail. The as-prepared material was characterized by X-ray diffraction, scanning electron microscopy, laser particle size analysis, charge-discharge tests, and cyclic voltammetry measurements. The results show that the spherical-like LiNi_0.6Co_0.2Mn_0.2O₂ material obtained by calcination at 900℃ displayed the most significant layered structure among samples calcined at various temperatures, with a particle size of approximately 10 μm. It delivered an initial discharge capacity of 189.2 mAh·g-1 at 0.2C with a capacity retention of 94.0% after 100 cycles between 2.7 and 4.3 V. The as-prepared cathode material also exhibited good rate performance, with a discharge capacity of 119.6 mAh·g-1 at 5C. Furthermore, within the cut-off voltage ranges from 2.7 to 4.3, 4.4, and 4.5 V, the initial discharge capacities of the calcined samples were 170.7, 180.9, and 192.8 mAh·g-1, respectively, at a rate of 1C. The corresponding retentions were 86.8%, 80.3%, and 74.4% after 200 cycles, respectively.     

LiNi_(0.8)Co_(0.2)O_2的表面修饰及性能

锂离子电池正极材料和电解液之间的恶性相互作用引起正极材料和电池性能的劣化。将 L i Ni0 .8Co0 .2 O2 ,L i OH.H2 O和 H3BO3以摩尔比 10 0 :1:2均匀混合 ,5 0 0℃热处理 10 h,在 L i Ni0 .8Co0 .2 O2 表面包覆上一层 L i2 O- 2 B2 O3玻璃层。用 X光电子能谱、扫描电镜和 X光衍射分析对包覆前后 L i Ni0 .8Co0 .2 O2 的结构进行了表征。结果表明 ,表面修饰有效地抑制了 L i Ni0 .8Co0 .2 O2 和电解液之间的恶性相互作用 ,材料的实际比容量提高 ,充放电循环稳定性改善 ,自放电速率减小。表面修饰处理是改善锂离子电池正极材料综合性能的有效途径     

Synthesis and characterization of LiNi_(0.95-x)Co_xAl_(0.05)O_2 for lithium-ion batteries

Synthesis and characterization of LiNi_(0.95-x)Co_xAl_(0.05)O_2 for lithium-ion batteries     

融盐包裹法合成球形正极材料LiNi_(0.7)Co_(0.2)Al_(0.1)O_2(英文)

以球形Ni(OH)2为核心原料,Al(NO3)3.9H2O、Co(NO3)2.6H2O和LiNO3为包裹原料,采用融盐包裹法在空气中煅烧合成了单相固溶体LiNi0.7Co0.2Al0.1O2。用XRD研究了合成产物的物相和结构,用SEM研究了合成产物的形貌,用电池性能测试仪研究了合成产物的电化学性能。实验结果表明,合成产物具有α-NaFeO2型层状有序结构、球状形貌和良好的电化学性能。     

葡萄糖的添加对富锂锰基正极材料Li1.2Ni0.2Mn0.6O2的影响

采用溶胶凝胶法制备合成富锂锰基正极材料Li_1.2Ni_0.2Mn_0.6O₂,在前期配制金属离子溶液时,通过添加不同量的葡萄糖（葡萄糖添加量分别为试剂总质量的0,6%,12%,36%,48%）来分析其对Li_1.2Ni_0.2Mn_0.6O₂的结构、形貌、电化学性能以及倍率性能的影响.恒流充放电测试结果显示,少量葡萄糖（6%,12%）加入,可以明显提高材料首次放电比容量.0.05C首次放电比容量由未加入葡萄糖材料的174 mAh/g提升至添加12%葡萄糖材料的265.9 mAh/g.倍率性能测试结果显示,葡萄糖的加入可以明显提高材料倍率性能.其中葡萄糖添加量为48%的材料倍率性能最好,首次放电比容量达到141 mAh/g,经过0.05C,0.1C,0.2C,0.5C,1C循环测试后再进行0.1C循环测试30次,放电比容量为110 mAh/g,容量保持率为78%.     

Synthesis and characterization of spinel Li_(1.05)Cr_(0.1)Mn_(1.9)O_(4-z)F_z as cathode materials for lithium-ion batteries

Samples with the nominal stoichiometry Li_1.05Cr_0.1Mn_1.9O_4−z F _z (z=0, 0.05, 0.1, 0.15, and 0.2) were synthesized via the solid-state reaction method and characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), galvanostatic charge/discharge, and slow rate cyclic voltammetry (SSCV) techniques. The results show that the pure spinel phase indexed to Fd3m can be obtained when z=0, 0.05, and 0.1. The substitution of F for O with z≤0.1 contributes to the increase of initial capacity compared with Li_1.05Cr_0.1Mn_1.9O₄ spinels. However, when the F-dopant content is designed to be 0.15 and 0.2, the Li_1.05Cr_0.1Mn_1.9O_4−z F _z samples deliver relatively low capacity and poor cycling properties at 55°C.     

Optimizing the Synthetic Conditions of LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2 from a Carbonate Co-precipitation Method

1 Introduction As a promising cathode material for lithium ion batteries,LiNi1/3Co1/3Mn1/3O2 attracted intensive attentions.Owing to high specific capacity,long circle life and excellent safety,it may be an alternative candidate for LiCoO2.As a complex composite,however,it is difficult to synthesize phase-pure LiNi1/3Co1/3Mn1/3O2 by a simple mixed calcination method[1].From this concern,carbonate co-precipitation method,which can prepare homogeneous LiNi1/3Co1/3Mn1/3O2 with typical layered structure,bec...     

钙钛矿型复合氧化物催化剂La_(0.4)Sr_(0.6)Mn_(0.6)Co_(0.4)0_3上CO氧化动力学

常压下,采用内循环无梯度反应器在160～200℃温度范围内考察了钙钛矿型复合氧化物催化剂 Lao_(0.4)Sr_(0.6)Mn_(0.6)Co_(0.4)O_3上一氧化碳氧化动力学.实验数据经多元线性加权最小二乘法拟合.其结果为一氧化碳氧化速率对 CO 和氧分压分别呈0.49级和0.48级的动力学行为.反应的表观活化能为64.0 kJ/mol.并根据动力学行为讨论了该催化剂上 CO 氧化的可能机理.     

高密度球形LiNi_(0.8)Co_(0.2)O_2的制备及性能

采用控制结晶法合成球形 β- Ni0 .8Co0 .2 (OH) 2 ,与L i OH.H2 O 混合 ,在 75 0℃通 O2 热处理 8h 合成球形L i Ni0 .8Co0 .2 O2 粉末。用 X光衍射和扫描电镜分析对 β- Ni0 .8Co0 .2 (OH) 2 和 L i Ni0 .8Co0 .2 O2 粉末的结构进行了表征。充放电测试表明该球形 L i Ni0 .8Co0 .2 O2 正极材料具有优良的电化学性能 :首次充电比容量为 2 17m A.h.g- 1 ,放电比容量为172 m A.h.g- 1 ,5 0次充放电循环后保持初始放电比容量的97.5 %。该球形 L i Ni0 .8Co0 .2 O2 粉末的振实密度高达 2 .8g.cm- 3,远高于一般非球形 L i Ni0 .8Co0 .2 O2 正极材料。高密度球形 L i Ni0 .8Co0 .2 O2 正极材料用于锂离子电池可以显著提高电池的能量密度。     

Tuning Li3PO4 modification on the electrochemical performance of nickel-rich LiNi0.6Co0.2Mn0.2O2

Surface deterioration occurs more easily in nickel-rich cathode materials with the increase of nickel content. To simultaneously pre-vent deterioration of active cathode materials and improve the electrochemical performance of the nickel-rich cathode material, the surface of nickel-rich LiNi0.6Co0.2Mn0.2O2 cathode material is decorated with the stable structure and conductive Li3PO4 by a facile method. The LiNi0.6Co0.2Mn0.2O2–1wt％, 2wt％, 3wt％Li 3PO4 samples deliver a high-capacity retention of more than 85％ after 100 cycles at 1 C under a high voltage of 4.5 V. The effect of different coating amounts (0–5wt％) for the LiNi0.6Co0.2Mn0.2O2 cathode is analyzed in detail. Results show that 2wt％ coating of Li3PO4 gives better performance compared to other coating concentrations. Detailed analysis of the structure of the samples during the charge?discharge process is performed by in-situ X-ray diffraction. It is indicated that the modification for LiNi0.6Co0.2Mn0.2O2 cathode could protect the well-layered structure under high voltages. In consequence, the electrochemical performance of modified samples is greatly improved.     

Coupling effect of the conductivities of Li ions and electrons by introducing LLTO@C fibers in the LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 cathode

To probe the coupling effect of the electron and Li ion conductivities in Ni-rich layered materials(LiNi_(0.8)Co_(0.1)5 Al_(0.05)O_2,NCA),lithium lanthanum titanate(LLTO) nanofiber and carbon-coated LLTO fiber(LLTO@C) materials were introduced to polyvinylidene difluoride in a cathode.The enhancement of the conductivity was indicated by the suppressed impedance and polarization.At 1 and 5 C,the cathodes with coupling conductive paths had a more stable cycling performance.The coupling mechanism was analyzed based on the chemical state and structure evolution of NCA after cycling for 200 cycles at 5 C.In the pristine cathode,the propagation of lattice damaged regions,which consist of high-density edge-dislocation walls,destroyed the bulk integrity of NCA.In addition,the formation of a rock-salt phase on the surface of NCA caused a capacity loss.In contrast,in the LLTO@C modified cathode,although the formation of dislocation-driven atomic lattice broken regions and cation mixing occurred,they were limited to a scale of several atoms,which retarded the generation of the rock-salt phase and resulted in a pre-eminent capacity retention.Only NiO phase pitting occurred.A mechanism based on the synergistic transport of Li ions and electrons was proposed.     

4 V级锂离子电池用橄榄石型LiMnPO4的电化学性能

对反应物与中间产物进行球磨, 采用固相反应法在600 ℃合成了掺碳的橄榄石型LiMnPO4. 通过XRD表征样品的晶体结构, 采用SEM观察样品的微观形貌, 利用电化学手段测试样品的充放电性能, 并对样品进行交流阻抗和扩散系数的测定. 研究结果表明, 得到的样品物相较纯, 粒径小(100～200 nm)且分布均匀, 首次放电容量接近100 mA·h·g-1, 但样品循环容量衰减快, 大电流放电性能较差. 通过对样品的交流阻抗测试发现, 电化学反应阻抗随放电的进行而不断增大, 说明材料的荷电量越高, 界面电化学反应速度越快. 扩散系数的测量结果表明, 充电态和放电态的扩散系数分别1.2×10-12和5×10-13 cm2·s-1, 表明晶格中锂离子的浓度越高, 越容易脱出.     

Facile synthesis of nanostructured LiFePO4/C cathode material for lithium-ion batteries

Nanostructured LiFePO4/C cathode material was prepared by FePO4·2H2O/C precursor by in situ restriction reaction.The synthesized LiFePO4/C cathode material presents a narrow distribution of nano-sized particles and exhibits an excellent electrochemical property with various rates.The facile synthesis route for the preparation of nano-sized LiFePO4 material has the particular advantage of simple synthesis process and low synthesis cost.     

Electrochemical properties of CoFe3Sb12 as potential anode material for lithium-ion batteries

A skutterudite-related antimonide, CoFe3Sb12,was prepared with vacuum melting.XRD analysis showed the material contained Sb, FeSb2, CoSb2 and CoSb3 phases.The electrochemical properties of the ball-milled CoFe3Sb12-10wt% graphite composite were studied using pure lithium as the reference electrode. A maximal lithium inserting capacity of about 860 mAh/g was obtained in the first cycle.The reversible capacity of the material was about 560mAh/g in the first cycle and decreased to ca.320 mAh/g and 250 mAh/g after 10 and 20 cycles respectively.Ex-situ XRD analyses showed that the antimonides in the pristine material were decomposed after the first discharge and that antimony was the active element for lithium to insert into the host material.     

中空TiO2/S复合物的制备及作为高性能锂硫电池正极材料

以C球为模板,通过水热反应制备中空结构TiO_2;并通过液相渗入法与单质S复合,制备出锂硫电池正极材料TiO_2/S复合物。利用透射电子显微镜(TEM)、X-射线衍射(XRD)、热重分析(TG)测试手段对复合物进行形貌、结构及不同组分含量确定的表征;利用循环伏安法(CV)、电化学阻抗谱(EIS)、恒电流充放电测试方法对其进行电化学性能表征。结果证明,单质S与中空TiO_2成功复合;中空结构的TiO_2不仅提高了S正极的导电性,还能有效控制单质S的利用,以及缓解多硫化合物的"穿梭效应",进而大大提高电池的库伦效率和循环性能。     

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.     

La_(0.8)Sr_(0.2)Mn_(0.98-x)Fe_xCo_(0.02)O_3微波吸收特性研究

用溶胶-凝胶法制备La_(0.8)Sr_(0.2)Mn_(0.98-x)Fe_xCo_(0.02)O_3(x=0.08、0.10、0.12、0.14)晶粉,用场发射扫描电子显微镜和XRD表征其微观形貌和晶体结构,用微波网络矢量分析仪测量样品在2~18 GHz频率范围内的复介电常数和复磁导率,根据测量数据计算微波反射率与频率的关系曲线.研究结果表明:900℃煅烧3 h的La_(0.8)Sr_(0.2)Mn_(0.98-x)Fe_xCo_(0.02)O_3粉晶平均粒径约100 nm,晶体结构为钙钛矿型;在测试范围内,样品都有一个吸收峰,峰高及频率位置随x不同而异;厚度2 mm,x=0.08、0.10、0.14,大于10dB的吸收带宽达到4 GHz以上,样品既有介电损耗又有磁损耗,但介电损耗要大于磁损耗.     

Effect of Na~+ in situ doping on LiFePO_4/C cathode material for lithium-ion batteries

Li_1-XNaXFePO₄(X = 0, 0.01 or 0.05) composite cathode materials were synthesized by the simple solvothermal method. SEM images showed that Na doping had little effect on the morphology of particles, which provided a guarantee for its excellent electrochemical performance. Charge/discharge data revealed that an appropriate amount of doped Na could improve electrochemical performance. Li_0.99Na_0.01FePO₄ showed excellent rate capacity and cycle s...     

LiFePO_4锂电池正极材料的共碳包覆和Mn掺杂的改性

采用高能球磨辅助固相法制备碳包覆并掺杂Mn的LiFePO4正极材料LiFe1-xMnxPO4(x=0.04、0.05、0.06和0.07)。通过X线衍射光谱仪(XRD)、场发射扫描电子显微镜(FESEM)、比表面积(BET)及恒流充放电等测试手段考察Mn的掺杂量及碳的包覆量对LiFePO4的结构、形貌及电化学性能的影响,最终确定优化条件。结果表明:Mn掺杂量x=0.06及碳的前驱体(蔗糖)添加量为LiFe0.94Mn0.06PO4质量的2.5%(碳最终质量分数为1.26%)时,所获得的碳包覆和Mn掺杂的LiFePO4正极材料的电化学性能最优异,其0.1C倍率的放电比容量为165.1 mA·h/g,10C倍率的放电比容量仍达92.4 mA·h/g,50次循环后容量保持率分别为96.7%及89.2%。