Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2正极材料的制备及其电化学性能

采用一步草酸盐法制备Li_(1.2)Mn_(0.54)Ni_(0.13)Co_(0.13)O_2富锂层状正极材料,采用X射线衍射、感应耦合等离子炬(ICP)发射光谱仪、场发射扫描电镜、透射电镜和电化学分析技术对材料的组成、结构和电化学性能进行表征与分析。结果表明:制得的富锂层状正极材料呈不规则棒状,长度为2~4 mm,直径约200 nm;其化学计量精确、层状结构发育良好、阳离子分布混合度较低;在电流密度为20 m A/g条件下,其首次放电比容量为242.4 m A·h·g-1,首次库仑效率为74.9%;当电流密度增大到1 000 m A/g时,放电容量仍可高达98.8 m A·h·g-1;在电流密度为200 m A/g充放电100个循环后,其容量保持率为76.8%。     

ZrO_2包覆对LiNi_(0.8)Co_(0.2)O_2结构和性能的影响

为提高锂离子电池正极材料LiNi_(0.8)Co_(0.2)O_2的综合电化学性能,采用高温固相法对其表面进行ZrO_2包覆。以X射线衍射、扫描电子显微镜、电化学阻抗和电化学充放电等方法对材料进行表征。结果显示,ZrO_2可均匀分布在LiNi_(0.8)Co_(0.2)O_2表面而不影响其晶体结构,但对电化学性能影响明显,即首次放电容量略有降低,由168.25 mAh/g降到157.43 mAh/g;1C、2C倍率性能有较大改善,循环性能的提高尤其突出,在100周循环内,LiNi_(0.8)Co_(0.2)O_2的容量保持率从90.68%提高到97.70%。其原因是:(1)包覆层有效避免了电解液与正极材料直接接触、抑制副反应的发生;(2)包覆过程中生成的Li_2ZrO_3提高了材料的离子导电性。该研究结果为改善锂离子电池正极材料综合电化学性能提供了简便、有效的方法。     

LiNi0.4Co0.2Mn0.4O2与LiMn2O4共混正极材料电化学性能

为开发具有优良循环性能和安全性能的大型锂离子电池的正极材料,将不同比例的LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和Li Mn2O4材料进行共混,研究了LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和Li Mn2O4共混以及共混比例(10∶0、8∶2、7∶3、6∶4、5∶5、0∶10)对锂离子电池的首次放电性能、循环性能和倍率性能以及交流阻抗和循环伏安曲线的影响,并采用扫描电镜对电极材料进行了表征.研究结果表明,共混比例会影响材料的电化学性能,8∶2,7∶3和6∶4配比的混合材料的体积比容量、循环性能和倍率性能要好于纯LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2和Li Mn2O4材料.其中,8∶2配比的材料性能最好.     

富镍三元正极材料的改性研究进展

随着便携式电子产品和电动车领域的高速发展,对高能量密度锂离子电池的性能提出了更高的要求。相比传统的钴酸锂正极材料,富镍层状金属氧化物具有较高能量密度和较低的原料成本,被视为理想的锂离子电池正极材料。然而,其结构缺陷和不稳定的表面化学特性会恶化材料的电化学性质、热力学稳定性和安全性能。本文主要回顾了近年来关于富镍三元正极材料的改性研究进展,旨在为今后富镍三元正极材料的设计提供重要思路,并实现其工业化应用。首先,介绍了富镍正极材料本身存在的固有缺陷和电化学性能衰减机制。然后,讨论了通过调控界面结构提升富镍材料性能的改性策略,包括包覆电化学惰性物质、设计元素全浓度梯度及核壳结构、构筑核壳异质结构和调控包覆物质厚度等。再然后,总结了通过元素的体相掺杂提升富镍正极材料性能的策略,包括碱金属位掺杂、过渡金属位掺杂、氧位掺杂和复合共掺杂。最后,我们对该领域的未来发展进行了总结和展望,希望能激发更多创新性的见解和策略,以促进富镍三元正极材料的实际应用。     

一步固相法制备高性能Li_2MnSiO_4/C锂离子电池正极材料

采用一步固相法合成了Li_2MnSiO_4/C正极材料,利用XRD,EIS和循环伏安测试对该材料进行了结构和电化学性能表征.研究了一步固相法中添加不同比例的葡萄糖对Li_2MnSiO_4材料性能的影响.结果表明:葡萄糖作碳源复合可以提高Li_2MnSiO_4正极材料的充放电比容量和循环性能,同时在一步固相合成法中还能细化Li_2MnSiO_4正极材料颗粒.葡萄糖添加量为6%时,制备得到的Li_2MnSiO_4/C正极材料首次可逆放电比容量为213.1 mAh/g.     

醋酸对Li_(1.42)Ni_(0.08)Mn_(0.70)Co_(0.08)O_(2.00)固溶体正极材料电化学性能的影响

以Li_2CO_3、NiCO_3·2Ni(0H)_2·4H_20、MnC0_3、Co(CH_3COO)_2·4H_20、醋酸溶液和聚乙烯醇为原料,制备出具有α-NaFeO_2层状结构的Li_(1.42)Ni(0.08)Mn_(0.7)Co_(0.08)O_(2.00)富锂固溶体正极材料.通过红外光谱、X射线衍射、恒电流充放电测试、交流阻抗和循环伏安法等方法研究了制备样品的结构及电化学性能.研究表明:按0.707 5 mol碳酸锂比例加入2.5 g醋酸时制备得到的正极材料充放电性能最好,在1C条件下,首次放电容量93.2 mAh/g,30次循环后容量达到177.2 mAh/g.     

LiCoO_2包覆LiNi_(0.78)Co_(0.2)Zn_(0.02)O_2锂离子电池正极材料

采用共沉淀法制备了LiCoO2包覆LiNi0.78Co0.2Zn0.02O2锂离子电池正极材料,对材料进行XRD、SEM的分析结果表明,该材料具类α-NaFeO2(R-3 m)结构,而且微观颗粒大小均匀.电化学测试结果表明,用LiCoO2进行表面包覆后比未包覆材料的初期放电比容量略有降低,但是材料的循环性能明显提高.包覆材料的首次恒流(60 mA.cm2,3.0~4.2 V,vs.Li /Li)充、放电比容量分别为243.63 mAh.g-1和204.58 mAh.g-1,首次循环效率为83.97%,200次循环后比容量仍为197.06 mAh.g-1,不可逆容量损失仅为7.52 mAh.g-1,容量保持率达到96.0%以上,具有很好的循环性能.     

SOC状态对LiNi_(0.5)Mn_(1.5)O_4材料电化学性能的影响

采用溶胶-凝胶自蔓延燃烧合成法,制备5 V级高电位的镍锰酸锂正极材料.利用X射线衍射仪、扫描电子显微镜(SEM)、能谱仪(EDS)进行表征测试,电化学工作站测试材料的电化学性能,研究尖晶石LiNi_(0.5)Mn_(1.5)O_4材料在不同SOC状态下对电极交流阻抗谱特征的影响.结果表明,LiNi_(0.5)Mn_(1.5)O_4材料是尖晶石结构,样品微观形态为八面体的结构,粒径分布均匀.CV测试表明:LiNi_(0.5)Mn_(1.5)O_4材料放电平台在4.6 V和3.9 V,在SOC为60%~80%时,电池的组合电阻呈现相对比较低的状态,得到放电过程电化学特征与SOC的关系.     

反应温度对LiNi_(0.4)Co_(0.2)Mn_(0.4)O_2组织结构及电化学性能的影响

在共沉淀法合成Ni0.4Co0.2Mn0.4(OH)2的基础上制备了锂离子电池正极材料LiNi0.4Co0.2Mn0.4O2.通过XRD,SEM和电化学测试对不同反应温度下LiNi0.4Co0.2Mn0.4O2正极材料的结构、形貌及电化学性能进行了测试和表征.测试表明随着反应温度的提高,c/a和I(003)/I(104)值也在增加,表明温度的升高可以减少锂镍离子的混排,使层状结构更加完整,进而电化学性能也更优异.900℃下反应所得到的样品,以0.2C放电,其首次放电容量为148.3mAh/g,库伦效率最高可达9.8%.循环40个周期后容量保持率为93.9%,具有较好的电化学性能.     

热处理对TiO2/AC电极材料结构及电化学性能的影响

为了研究不同热处理温度对Ti O2/AC电极材料结构及电化学性能的影响,采用溶胶-凝胶法制备该电极材料,通过扫描电子显微镜(SEM)、热重分析仪(TG-DTG)、比表面积及孔径分析仪(BET)、X射线衍射光谱仪(XRD)和电化学工作站对其微观结构和电化学性能进行表征分析.结果表明:热处理使Ti O2呈絮状或颗粒状附着于活性炭表面及孔道中;随着热处理温度升高,Ti O2/AC比表面积先增大后减小,晶型由锐钛型逐渐向金红石型转变,晶粒尺寸也逐步增大,比电容值先增大后减小;当热处理温度为450℃时,Ti O2/AC电极材料的晶型呈锐钛型且晶粒尺寸适中、有效比表面积最大、电化学性能最优.     

Modification of LiCo1/3Ni1/3Mn1/3O2 cathode material by CeO2-coating

LiCo_1/3Ni_1/3Mn_1/3O₂ was coated by a layer of 1.0 wt% CeO₂ via sol-gel method. The bared and coated LiMn_1/3Co_1/3Ni_1/3O₂ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammogram (CV) and galvanotactic charge-discharge test. The results show that the coating layer has no effect on the crystal structure, only coating on the surface; the 1.0 wt% CeO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ exhibits better discharge capacity and cycling performance than the bared LiCo_1/3Ni_1/3Mn_1/3O₂. The discharge capacity of 1.0 wt% CeO₂-coated cathode is 182.5 mAh·g⁻¹ at a current density of 20 mA·g⁻¹, in contrast to 165.8 mAh·g⁻¹of the bared sample. The discharge capacity retention of 1.0 wt% CeO₂-coated sample after 12 cycles reaches 93.2%, in comparison with 86.6% of the bared sample. CV results show that the CeO₂ coating could suppress phase transitions and prevent the surface of cathode material from direct contact with the electrolyte, thus enhance the electrochemical performance of the coated material.     

Corrosion resistance of plasma sprayed NiCrAl+(ZrO2+Y2O3) thermal barrier coating on 18-8 steel surface

The corrosion resistance of NiCrAl+(ZrO₂+Y₂O₃) thermal barrier coating, formed with the plasma spraying technique, on the 18 - 8 steel surface was investigated. The phase structure and morphology of the coating were analyzed by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical corrosion behavior of the coating in 1.0 mol/L H₂SO₄ solution was studied by using electrochemical measurement methods. The results show that the gradient plasma spraying coating is composed of the NiCrAlY coating and the (ZrO₂+Y₂O₃) top coating, and the coating thickness is 360 μm. The microhardness of coating reaches 1 100 HV. The corrosion resistance of the plasma sprayed coating of the 18 - 8 steel surface is about 5 times as great as that of the original pattern. The corrosion resistance of the coating is enhanced notably. Foundation item: Project (5040202140) supported by Scientific Research Common Program of Beijing Municipal Commission of Education     

Synthesis and characterization of Mg3(PO4)2-coated Li1.05Ni1/3Mn1/3Co1/3O2 cathode material for Li-ion battery

Mg₃(PO₄)₂-coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode materials were synthesized via co-precipitation method. The morphology, structure, electrochemical performance and thermal stability were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry(CV), electrochemical impedance spectroscopy(EIS), charge/discharge cycling and differential scanning calorimeter (DSC). SEM analysis shows that Mg₃(PO₄)₂-coating changes the morphologies of their particles and increases the grains size. XRD and CV results show that Mg₃(PO₄)₂-coating powder is homogeneous and has better layered structure than the bare one. Mg₃(PO₄)₂-coating improved high rate discharge capacity and cycle-life performance. The reason why the cycling performance of Mg₃(PO₄)₂-coated sample at 55 °C was better than that of room temperature was the increasing of lithium-ion diffusion rate and charge transfer rate with temperature rising. Mg₃(PO₄)₂-coating improved the cathode thermal stability, and the result was consistent with thermal abuse tests using Li-ion cells: the Mg₃(PO₄)₂ coated Li_1.05Ni_1/3Mn_1/3Co_1/3O₂ cathode did not exhibit thermal runaway with smoke and explosion, in contrast to the cells containing the bare Li_1.05Ni_1/3Mn_1/3Co_1/3O₂. Funded by the National Natural Science Foundation of China (No. 20273047)     

Kinetic study of LiMn2O4 in process of lithium intercalation

Exchange current density of spinel LiMn₂O₄ was studied by linear polarization. The relationship of the kinetic property with the structure of spinel LiMn₂O₄ was investigated by studying the effect of the doping and surface coating on the kinetic properties of electrode material. The results show that the exchange current density of spinel LiMn₂O₄ electrode increases with the increase of the amount for lithium intercalation at first, and then decreases. The maximal exchange current density appeares at the 80%–90% lithium intercalation. The similar phenomenon was observed on the doped spinel LiMn₂O₄ electrode. Doping can enhance the exchange current density of spinel LiMn₂O₄ material. However, the degree of the doping effect varies with the doped element varying. Surface coating can also enhance the exchange current density of spinel material, and the increment of value is higher than that of doped ones. Foundation item: Project(50302016) supported by the National Natural Science Foundation of China     

球形LiMn1.5Ni0.5O4材料的嵌脱动力学

为明晰Li Mn1.5Ni0.5O4正极材料的动力学性能,采用水热辅助共沉淀法合成了尖晶石Li Mn1.5Ni0.5O4正极材料,并采用扫描电镜(SEM)、X射线粉末衍射(XRD)和电化学阻抗(EIS)研究了材料的结构和锂离子嵌脱动力学.实验结果表明:共沉淀法制备的Li Ni0.5Mn1.5O4材料颗粒呈均匀球形,且平均粒径较小,粒度分布较窄.在循环过程中,Li Ni0.5Mn1.5O4的电荷转移电阻增大,锂离子扩散系数减小,进而电子电导率和离子电导率下降.温度升高后,Li Ni0.5Mn1.5O4材料的溶液电阻变化不大,但是电荷转移电阻逐渐增大,锂离子扩散系数逐渐减小;此外,随着温度的升高,Li Ni0.5Mn1.5O4材料的溶解速度加快,从而导致SEI膜的厚度增大.Li Ni0.5Mn1.5O4材料的嵌脱锂动力学与温度和循环次数有密切关系.     

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     

Modification of nano-TiO2 by Al2O3 in-situ coating

A novel technology of in-situ coating Al₂O₃ on the surface of H₄TiO₄ was developed to prevent the aggregation of nano-TiO₂ powders and improve the dispersibility and thermal stability in the way of forming a uniform coating layer. The heterogeneous nucleation was conducted to prepare the precursor of nano-TiO₂ and then Al₂O₃ was coated on the surface of precursor. The effects of Al₂O₃ in-situ coating on the properties of nano-TiO₂ were investigated. The results show that H₄TiO₄ can be dispersed well under alkaline condition (pH 8.5) and the heterogeneous nucleation can be controlled easily. The optimized uniform coating layer is obtained by adding 5% (mass fraction) and 10% of Al₂O₃ and the aggregation of nano-TiO₂ powders is effectively inhibited and the dispersibility is obviously improved. The crystal sizes of TiO₂ powders are 12.3, 11.4 and 8.7 nm after coating 0,5% and 10% of Al₂O₃ respectively. Al₂O₃ on the surface of particulates in amorphous phase could increase the thermal stability of nano-particles after calcined at 550 °C. Foundation item: Project(04GK2007) supported by Hunan Industrial Key Project of Science and Technology     

Properties of plasma sprayed NiCrAlY+(ZrO2+Y2O3) coating on refractory steel surface

NiCrAlY+(ZrO₂+Y₂O₃) thermal barrier coating was prepared on the surface of refractory steel 1Cr18Ni9Ti with plasma spraying technique. The phases and microstructure of the thermal barrier coating were determined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results show that the bonding between thermal barrier coating and substrate is sound. The surface hardness of 1Cr18Ni9Ti reaches up to 1 000 HV, but that of substrate is only 300 HV. The patterns sprayed with CoNiCrAlY+(ZrO₂+Y₂O₃) ceramic coating have a good heat insulation effect at 800 °C for heat insulation temperature difference reaches 54 °C, which increases the operating temperature and service life of refractory steel. Foundation item: Project (5040202140) supported by Scientific Research Common Program of Beijing Municipal Commission of Education     

Antibiotic properties of Al2O3 doping silver

The preparation technique and properties of Ag-type inorganic antibiotic material carried by Al₂O₃ were studied. The results show that the material has good antibiotic and safety properties, the acute toxicity taken by stomata is LD ₅₀>8 000 mg/kg (little and big white rats), and the normal quantity in subacute toxicity test is 80 mg/(kg · d). The better mass fraction of doping Ag₂O in antibiotic material carried by Al₂O₃ is 4%–8%, and the optimal sintering temperature is from 1 000 °C to 1 100 °C. Foundation item: Project (2002AA327090) supported by National High Technology Research and Development Program of China