锂离子电池正极材料LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2的LaF_3包覆改性研究

通过沉淀法对高镍LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2正极材料进行了LaF_3包覆,采用了X射线衍射(XRD)、扫描电子显微镜(SEM)、X射线能谱仪(EDS)、恒流充放电测试和电化学交流阻抗(EIS)对材料的结构、形貌、成分和电化学性能进行了表征,系统的研究了LaF_3包覆对材料的性能影响。结果表明,LaF_3在Li Ni0.6Co0.2Mn0.2O2材料表明形成了均匀的包覆层,LaF_3包覆后未影响主体材料的晶体结构。LaF_3包覆后的材料倍率性能和循环性能均优于未包覆的原材料。在3.0~4.6 V电压范围和170 m A·g-1的电流密度下循环100周后,包覆量为1.0 wt%的材料容量保持率为84.6%,而未包覆的材料容量保持率仅为66.7%。包覆层的存在避免了电解液和主体材料的直接接触,减少了电解液的氧化和HF的腐蚀,稳定了材料的结构,极大的减小了电极极化程度,从而提高了材料的电化学性能。     

钴掺杂对Li1.2Mn0.6Ni0.2O2电化学性能的影响

利用共沉淀法制备了锂离子电池正极材料Li1.2Mn0.6Ni0.2O2和Li1.2Mn0.588Ni0.196Co0.016O2,并利用XRD、SEM和充放电测试对其晶体结构、形貌和电化学性能进行了表征.XRD结果表明:掺杂钴材料后,材料的层状结构保持完整,阳离子混排程度降低.电化学性能测试结果表明:掺钴材料的首次充放电效率和倍率放电性能明显优于Li1.2Mn0.6Ni0.2O2,且表现出较优的循环性能,其1、2、5C放电比容量分别为230.3、215.6、155.6 mA·h/g,1 C下循环50次的容量保持率为90.9％.     

锌掺杂对LiNi_(0.6)Co_(0.2)Mn_(0.2)O_2正极材料结构和电化学性能的影响

采用草酸盐共沉淀法制备出锌掺杂的锂离子电池正极材料,结合X射线衍射(XRD)、扫描电镜(SEM)、EDS能谱(EDS mapping)、恒电流充放电和电化学阻抗(EIS)测试,研究Zn2+掺杂对材料晶体结构、形貌及电化学性能的影响。实验结果表明,Zn2+掺杂可抑制高镍材料中的离子混排,形成多孔结构,缩短Li+的扩散路径,从而改善材料的倍率和循环性能。在2.7~4.3 V电压范围内,10 C倍率下Li(Ni_(0.6)Co_(0.2)Mn_(0.2))0.99Zn0.01O2表现出87.8 m Ah·g-1的放电比容量,比LiNi_(0.6)Co_(0.2)Mn_(0.2)O2提高了37.0%,1 C倍率下循环100圈后,Li(Ni_(0.6)Co_(0.2)Mn_(0.2))0.99Zn0.01O2的容量保持率为84.7%,比未掺杂的材料提高了12%。EIS测试结果则进一步验证锌掺杂有效降低了材料的电荷传质阻抗。     

锂盐用量对Li1.2Mn0.6Ni0.2O2材料电化学性能的影响

以球形前驱体Mn0.6Ni0.2(OH)1.6及碳酸锂为原料,通过高温固相法合成富锂锰基正极材料Li1.2Mn0.6Ni0.2O2。通过X射线衍射(XRD)、扫描电子显微镜(SEM)对不同锂盐用量条件下得到的Li1.2Mn0.6Ni0.2O2的结构和形貌进行了表征,并对其进行了电化学性能测试。结果表明:当锂盐用量过量4%时,合成的Li1.2Mn0.6Ni0.2O2的晶体结构最完整、球形形貌更规则、电化学性能优异。在0.2 C和1.0 C下首次放电比容量可达250.7、235.2 m A·h/g;1.0 C下循环50次后,容量保持率为86.86%。     

基于分级共沉淀法制备锂离子电池LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2正极材料

通过分级共沉淀(分级进料)方法,结合高温热处理合成了金属元素(Ni,Mn)浓度从中心到表面呈梯度分布(中心富Ni,表面富Mn)的球形三元正极材料LiNi_(0.5)Co_(0.2)Mn_(0.3)O_2。利用X射线衍射(XRD)、场发射扫描电镜(FESEM)、能谱仪(EDS)和电感耦合等离子质谱仪(ICP-MS)等表征了所制备材料的成分、形貌和元素分布。通过恒流充放电和循环伏安、交流阻抗等方法对材料的电化学性能进行测试。结果表明,与传统的一级共沉淀方法相比,分级共沉淀所制备材料展现出更高的倍率性能(20 C放电比容量为104.1 m Ah·g~(-1))、循环保持率(0.5 C循环200次容量保持率为95.8%)和快速充放电性能(20 C/20 C放电比容量为85.4 m Ah·g~(-1))。这种分级进料制备技术可以有效提高共沉淀法制备锂离子电池三元正极材料的电化学性能。     

钕表面修饰对三元锂离子电池正极材料Li[Ni_(0.6)Co_(0.2)Mn_(0.2)]O_2性能的影响

三元正极材料在高能量密度和低成本方面表现出吸引人的性能。然而,这些材料容易在颗粒表面发生降解。所以,在这项工作中选用氧化钕作为涂层包覆在三元正极材料Li[Ni_(0.6)Co_(0.2)Mn_(0.2)]O_2表面,并进行了一系列表征测试。测试结果显示包覆前后材料具有相同的物相与相似的形貌。当Nd_2O_3的包覆量为x=0.03时,Li[Ni_(0.6)Co_(0.2)Mn_(0.2)]O_2的电化学性能得到提高,即使在5C倍率下,放电容量仍能达到113.2 mAh·g~(-1)。在0.2C下100次循环后容量保持率为88.2%。因此通过氧化钕的包覆可以提高材料的结构稳定性以及电化学动力学。     

ZnF_2包覆对锂离子电池正极材料LiNi_(0.5)Mn_(1.5)O_4性能的影响

采用溶胶-凝胶法制备了LiNi_(0.5)Mn_(1.5)O_4正极材料,并利用Zn F2对其表面进行包覆改性。XRD、SEM和TEM测试表明,包覆处理不影响材料的晶体结构,2%(质量分数,以LiNi_(0.5)Mn_(1.5)O_4质量计,下同)的Zn F2在LiNi_(0.5)Mn_(1.5)O_4表面形成了约7 nm厚均匀包覆层。对未包覆的LiNi_(0.5)Mn_(1.5)O_4和1%、2%、3%的Zn F2包覆后的LiNi_(0.5)Mn_(1.5)O_4的电化学性能进行了考察,发现Zn F2包覆能够减弱电解液与LiNi_(0.5)Mn_(1.5)O_4正极材料之间的相互作用,稳定电极表面,提高材料的电化学性能。其中,2%Zn F2包覆样品表现出最佳的循环性能和倍率性能,0.2C电流倍率下循环200圈后,其放电比容量维持在109.0 m A·h/g,保持率为79.7%;5 C电流倍率下循环500圈后,放电比容量维持在94.2 m A·h/g,保持率为85.6%。     

Al_2O_3包覆对三元正极材料结构和性能的影响

为考察Al2O3包覆改性对三元正极材料结构及电性能的影响,在三元正极材料表面沉积了Al(OH)3胶体,制得了系列Al2O3包覆的三元正极材料。对所得产品进行XRD、SEM、TEM表征和电性能测试,并探讨了不同Al2O3包覆量对产物的影响。结果表明,少量的包覆不会影响材料的层状结构,包覆量为0.5%时,正极材料最高放电比容量达到182.0 m Ah·g-1,且循环稳定性佳,重复30次充电、放电,放电比容量仍稳定在175.0 m Ah·g-1左右。     

不同镍钴锰比对xLi_2MnO_3-(1-x)LiMO_2正极材料的结构和电化学性能的影响

以Na OH和NH3·H2O为沉淀剂,采用共沉淀法成功合成富锂锰基层状正极材料。通过X射线粉末衍射(XRD)、拉曼光谱、扫描电子显微镜(SEM)、循环伏安法(CV)、电化学阻抗谱(EIS)和充放电测试等研究手段,重点探讨了不同镍钴锰比对富锂锰基层状正极材料的结构、形貌以及电化学性能的影响。其中Li1.2Mn0.54Ni0.13Co0.13O2正极材料结晶度高,粒度分布均匀,无明显团聚现象。在0.1C倍率下首次放电比容量为247.9 m A·h·g-1,首次库仑效率为75.1%。在1C倍率下首次放电比容量为236.2 m A·h·g-1,经过50次充放电循环后放电比容量为218.4 m A·h·g-1,容量保持率为88.3%,展现出较好的循环稳定性。     

FeF_3表面包覆Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2正极材料的制备和电化学性能

采用典型的湿化学法制备了2%(wt)FeF_3包覆的Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2材料,并且通过XRD,SEM及TEM等技术来分析材料的微观结构和形貌。结果显示,在Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2材料表面包覆着一层5~20 nm厚的FeF_3薄膜。通过电化学性能测试发现,2%(wt)FeF_3@Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2样品的首次库伦效率更高,高倍率性能更佳,循环性能更加稳定。在0.5C倍率下循环100次后,其容量保持率仍有94.2%,放电比容量为190.6 m Ah×g~(-1)。同时电化学阻抗结果表明,FeF_3包覆层能够抑制Li[Li_(0.2)Mn_(0.54)Ni_(0.13)Co_(0.13)]O_2和电解液之间的副反应,稳定材料的层状结构。     

Effect of Li2O excess in Li6.4Ga0.2La3Zr2O12 electrolyte for all-solid-state Li-ion batteries

Li₇La₃Zr₂O₁₂ is a promising material used as solid electrolyte in all-solid-state lithium batteries. However, the lithium ionic conductivity of LLZO is limited, and the cycling stability of lithium symmetric battery based on LLZO is not good. In this research, different Ga-doped LLZO samples were prepared by adding different excess amounts of Li₂O, and the effect of excess amount of Li₂O on the structure and performance of LLZO have been researched. The results show that with the rise of the amount of Li₂O, the lithium ionic concentration increases gradually, and the lithium ionic conductivity and the ratio of grain resistance to total resistance rise first and then drop. When the excess amount of Li₂O is 10 wt.%, the sample exhibits the highest lithium ionic conductivity of 1.36 mS/cm, and the lithium symmetric battery exhibits the most stable operation.     

铝掺杂富锂锰基正极材料Li1.2Ni0.2Mn0.6O2的研究

针对无钴锰基富锂材料Li_1.2Ni_0.2Mn_0.6O₂固有的循环稳定性差、循环电压衰减严重等问题,研究了铝掺杂结合固相煅烧法对该材料在微观形貌及结构、电化学性能等方面的影响。研究结果显示,铝掺杂不仅能促使该材料的表层形貌更加致密,而且可以为该材料带来更稳定的晶体结构,这有利于该材料在长充放电循环中抵抗因结构降级带来的一系列不利因素,最终致使其电化学性能更加优异。此外,当铝掺杂量为1%（物质的量分数）时该材料在高倍率下的放电比容量、循环稳定性、电压保持率等均达到最优效果,在2.0~4.8 V电压区间内0.1C倍率下首圈放电比容量高达248.8 mA·h/g,200圈循环充放电后其放电比容量保持率由未掺杂时的57.9%提升至77.6%,循环电压保持率也由84.2%提升至85.6%。以上结果充分显示了1%铝掺杂对锰基富锂材料Li_1.2Ni_0.2Mn_0.6O₂具有优异的改良效果。     

Formation and properties of Ca2+ substituted (Ce0.2Zr0.2Ti0.2Sn0.2Hf0.2)O2 high-entropy ceramics

Five equimolar multicomponent oxides were synthesized by replacing one of five cations in (Ce_0.2Zr_0.2Ti_0.2Sn_0.2Hf_0.2)O₂ with Ca²⁺. The results reveal that except for the one in which Ce⁴⁺ replaced by Ca²⁺, the other four components can form single-phase high-entropy fluorite oxides (HEFOs) at different temperatures, which indicates that Ce⁴⁺ is very important for the formation of single-phase HEFOs. The sintering behavior, lattice parameter and properties containing density, porosity, flexural strength and thermal conductivity of the four single-phase HEFOs were investigated. With the change of substituted ions, grain size, relative density, flexural strength and thermal conductivity of the materials vary greatly, which are correlated to the size disorder and mass disorder of these materials. The results of this paper provide a reference for the composition designing and performance tailoring of equimolar HEFOs.     

Characterization of novel high-entropy (La0.2Nd0.2Sm0.2Dy0.2Yb0.2)2Zr2O7 electrospun ceramic nanofibers

We present a simple way to fabricate high-entropy (La_0.2Nd_0.2Sm_0.2Dy_0.2Yb_0.2)₂Zr₂O₇ (HE-RE₂Zr₂O₇) ceramic nanofibers using the electrospinning and annealing processing in this work. The microstructure of nanofibers was characterized by thermal gravity-differential scanning calorimetry (TG-DSC), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), respectively. Meanwhile, the diameter and grain growth of HE-RE₂Zr₂O₇ nanofibers under 1000 °C was analyzed. Results indicate that HE-RE₂Zr₂O₇ nanofibers can be prepared at temperatures above 400 °C and the crystallite size can be controlled by annealing temperature. Both diameter and the grain growth of HE-RE₂Zr₂O₇ nanofibers are lower than that of La₂Zr₂O₇ nanofibers, attributed to the sluggish diffusion effect. The advantages of HE-RE₂Zr₂O₇ nanofibers can further enlarge the application of nanofibers in the aspect of high-temperature thermal insulation materials.     

High-entropy (Ho0.2Y0.2Dy0.2Gd0.2Eu0.2)2Ti2O7/TiO2 composites with excellent mechanical and thermal properties

High-performance ceramics with low thermal conductivity, high mechanical properties, and idea thermal expansion coefficients have important applications in fields such as turbine blades and automotive engines. Currently, the thermal conductivity of ceramics has been significantly reduced by local doping/substitution or further high-entropy reconfiguration of the composition, but the mechanical properties, especially the fracture toughness, are insufficient and still need to be improved. In this work, based on the high-entropy titanate pyrochlore, TiO₂ was introduced for composite toughening and the high-entropy (Ho_0.2Y_0.2Dy_0.2Gd_0.2Eu_0.2)₂Ti₂O₇-xTiO₂ (x = 0, 0.2, 0.4, 1.0 and 2.0) composites with high hardness (16.17 GPa), Young's modulus (289.3 GPa) and fracture toughness (3.612 MPa·m^0.5), low thermal conductivity (1.22 W·m⁻¹·K⁻¹), and thermal expansion coefficients close to the substrate material (9.5 ×10⁻⁶/K) were successfully prepared by the solidification method. The fracture toughness of the composite toughened sample is 2.25 times higher than that before toughening, which exceeds most of the current low-thermal conductivity ceramics.     

Improved electrochemical performance of layered LiNi0.4Co0.2Mn0.4O2 via Li2ZrO3 coating

A Li₂ZrO₃ coating technique was successfully applied to layered lithium transition metal mixed oxide LiNi_0.4Co_0.2Mn_0.4O₂ to enhance its electrochemical performance using Zr(NO₃)₄·5H₂O and CH₃COOLi·2H₂O as coating reagents. The existence of Li₂ZrO₃ coating layer was identified by X-ray diffraction (XRD), Environmental scanning electron microscopy (ESEM), Transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The Li₂ZrO₃ shell decreased the exposed area of electrode core to electrolyte, and thus suppressed the dissolution of transition metal and side reaction between them. In addition, coating with Li₂ZrO₃ improved the ion transportation characteristics. As a result, an enhanced electrochemical performance in terms of discharge capacity, rate performance, and capacity retention were obtained, especially at higher temperature of 50 °C. Analysis of electrochemical impedance spectra (EIS) showed that the coated material exhibited lower charge transfer resistance (R_ct) with less variation during cycling, which indicated the electrode/electrolyte interface of coated material was more favorable and stable for electrochemical reaction.     

Phase evolution and thermophysical properties of high-entropy RE2(Y0.2Yb0.2Nb0.2Ta0.2Ce0.2)2O7 oxides

Pursuing novel thermal barrier–coating materials with lower thermal conductivity and high-temperature stability can simultaneously improve the working efficiency and service temperature of a gas turbine. In this study, a series of high-entropy RE₂(Y_0.2Yb_0.2Nb_0.2Ta_0.2Ce_0.2)₂O₇ (RE = La, Nd, Sm, Gd, Dy, and Er) oxides were prepared though solid-state reaction. Through tuning the rare-earth cations, an order–disorder transition occurs from certain partially ordered weberite structure (C222₁) to disordered defective fluorite structure (Fm$\overline{3}$m). All the high-entropy RE₂(Y_0.2Yb_0.2Nb_0.2Ta_0.2Ce_0.2)₂O₇ oxides possess low thermal conductivity in the range of 0.91–1.34 W m⁻¹ K⁻¹ at room temperature, which can be attributed to increased lattice anharmonicity and disorder, resulting in additional phonon scattering. Herein, we proved that the incorporation of heterovalent cations at B-sites in high-entropy A₂B₂O₇ crystals is an effective strategy to reduce the thermal conductivity without compromising the decrease of oxygen vacancy. Moreover, the high-entropy RE₂(Y_0.2Yb_0.2Nb_0.2Ta_0.2Ce_0.2)₂O₇ oxides show the relatively higher thermal expansion coefficients of 10.3–10.7 × 10⁻⁶°C⁻¹ and excellent phase stability at elevated temperatures.     

Effect of molybdenum substitution on electrochemical performance of Li[Li0.2Mn0.54Co0.13Ni0.13]O2 cathode material

Molybdenum doping is introduced to improve the electrochemical performance of lithium-rich manganese-based cathode material. X-ray diffraction (XRD) results illustrate that the crystallographic parameters a, c and lattice volume V become larger with the increase of Mo content. The scanning electron microscope (SEM) shows that the molybdenum substitution increases the crystallinity of the primary particles. When evaluated as cathode material, the as-prepared Li[Li_0.2Mn_0.54-x/3Ni_0.13-x/3Co_0.13-x/3Mo_x]O₂ (x = 0.007) delivers a discharge capacity of 155.5 mA h g⁻¹ at 5 C (1 C = 250 mA g⁻¹) and exhibits the capacity retention of 81.8% at 1 C after 200 cycles. The results of cyclic voltammetry (CV) and electronic impedance spectroscopy (EIS) tests reflect that the molybdenum substitution is able to significantly reduce the electrode polarization and lower the charge-transfer resistance. Within appropriate amount of Mo doping, the lithium ion diffusion coefficient of the material can reach to 8.92 × 10^–15 cm² s⁻¹, which is ~ 30 times higher than that of pristine materials (2.65 × 10^–16 cm² s⁻¹).     

Li2O excess (Na0.51K0.47Li0.02)(Nb0.8Ta0.2)O3 lead free piezoelectric ceramics

1 mol% Li₂O excess (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ ceramics were prepared by the conventional mixed oxide method and sintered from 950 to 1200 °C. Also, Li₂O was employed as a sintering aid for high densification and low temperature sintering process. X-ray diffraction results of 1 mol% Li₂O excess (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ lead free piezoelectric ceramics indicated that the specimens were well crystallized and have tetragonal structure. The specimens which sintered at 1050 °C showed the highest piezoelectric properties compared with others. The measured piezoelectric constant and electromechanical coupling coefficient were 231 pC/N and 38.9%, respectively. Curie temperature of (Na_0.51K_0.47Li_0.02)(Nb_0.8Ta_0.2)O₃ ceramics was 344.32, 344.4 and 344.5 °C at 1, 10 and 100 kHz, respectively.     

Ultrafast densification of high-entropy oxide (La0.2Nd0.2Sm0.2Eu0.2Gd0.2)2Zr2O7 by reactive flash sintering

Pyrochlore-type high-entropy oxides (HEOs) are usually sintered at high temperatures for a long time to achieve full density. Herein, we synthesized pyrochlore-structured (La_0.2Nd_0.2Sm_0.2Eu_0.2Gd_0.2)₂Zr₂O₇ HEOs with densities up to 99 % at a furnace temperature of 1200 °C in seconds via reactive flash sintering (RFS). The resultant HEOs achieved compositional uniformity at the atomic level and exhibited superior modulus, hardness and fracture toughness compared to the counterparts prepared by conventional solid-state sintering (at 1600 °C for 6 h). The underlying mechanisms for the ultrafast densification of the RFSed-HEOs were addressed in view of the roles of electric field, rapid heating, external pressure and internal reactions.