锂离子电池正极材料LiNi_(0.8)Co_(0.2)O_2的制备与表征

用2次干燥化学共沉淀法制得高密度前驱体Ni0.8Co0.2(OH)2,使之与LiOH.H2O混合经过2个恒温阶段烧结(600℃恒温6 h、850℃恒温24 h)得到LiNi0.8Co0.2O2材料,探讨了镍源、Li/(Ni+Co)摩尔比、合成温度、合成时间等因素对产品的影响,从而优化了LiNi0.8Co0.2O2的合成工艺.所得非球形LiNi0.8Co0.2O2粉末振实密度高达2.94 g/cm3,X射线衍射分析表明该材料具有规整的层状NaFeO2结构,充放电测试表明材料具有良好的电化学性能.     

熔融盐法合成球形锂离子电池正极材料LiNi_(0.8)Co_(0.2)O_2

采用热分析法对不同组成的LiOH-LiNO3二元体系进行研究,绘制了具有最低共熔点的该二元体系T-x相图,该体系的最低共熔点为175.7℃.利用低共熔混合物LiNO3-LiOH为锂盐,与前驱体球形Ni0.8Co0.2(OH)2混合烧结制备出了球形锂离子电池正极材料LiNi0.8Co0.2O2.探讨了Li/(Ni+Co)摩尔比、合成温度、合成时间等因素对产品的影响.X射线衍射分析表明合成的材料具有规整的层状NaFeO2结构,SEM表明所得材料为球形.充放电测试表明在3.0~4.3的电压范围内,首次放电比容量可达170 mAh.g-1,充放电效率为95.5%.结果表明采用该工艺可以制备出电化学性能良好的LiNi0.8Co0.2O2正极材料.     

高密度锂离子正极材料前驱体Ni_(0.8)Co_(0.2-x)Al_x(OH)_2的制备

采用二次干燥的化学共沉淀法制备出了Co-Al共掺杂的高密度锂离子电池正极材料前驱体Ni0.8Co0.2-xAlx(OH)2(X=0,0.05,0.1,0.15,0.2).研究了不同Co-Al的掺杂比例,NaOH溶液的浓度、滴定速率、烘干方式等因素对前驱体振实密度的影响.XRD分析表明,不同掺杂比例的Ni0.8Co0.2-xAlx(OH)2均为六方层状的β型结构,晶型结构规整.充放电测试表明以此前驱体与LiNO3反应制得的LiNi0.8Co0.15Al0.05O2材料具有良好的电化学性能.     

AlPO4包覆LiNi1/3Co1/3Mn1/3O2的制备与电化学性能

采用高温固相法制备LiNi_1/3Co_1/3Mn_1/3O₂,溶胶-凝胶法制备AlPO₄包覆LiNi_1/3Co_1/3Mn_1/3O₂材料(AlPO₄-coated LiNi_1/3Co_1/3Mn_1/3O₂).并用XRD、SEM检测等对材料进行了表征,用X-射线衍射、扫描电镜分析以及电化学测试等手段对样品的微观结构、表面形貌和电化学性能进行了研究.结果表明：在AlPO₄-coated LiNi_1/3Co_1/3Mn_1/3O₂中,AlPO₄以无定形态包覆于的表面;AlPO₄的存在,阻止了电极与电解质溶液之间的副反应,降低了电极的表面膜阻抗和电荷转移阻抗,加快了锂离子的扩散速度,使得LiNi_1/3Co_1/3Mn_1/3O₂的循环性能和倍率性能显著改善.     

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.     

Ni/Co比例对LiCoxNi1-xO2电化学性能的影响

采用固相反应法合成了一系列LiCoxNi1-xO2(0≤x≤1)材料,用XRD和电化学实验方法研究了Co3+取代Ni3+对LiNiO2材料电化学性能的影响.结果表明,当Ni/Co比例为8:2时材料具有最好电化学性能,比容量可以达到170～180mAh/g,并且具有好的抗过充性能.     

Ti掺杂对正极材料LiNi1/3Co1/3Mn1/3O2结构和电化学性能的影响

为研究离子掺杂对锂离子正极材料LiNi1/3Co1/3Mn1/3O2的影响,采用氢氧化物共沉淀法制备了Ti4+掺杂改性的锂离子正极材料LiNi1/3-1/40Co1/3Mn1/3Ti1/40O2、LiNi1/3-Co1/3-1/40Mn1/3Ti1/40O2和LiNi1/3Co1/3Mn1/3-1/40Ti1/40O2,并运用X射线衍射仪和扫描电子显微镜对Ti掺杂改性后正极材料的晶型和微观结构进行表征,通过高精度电池性能检测系统对正极材料的电化学性能进行检测.结果表明:Ti分别取代Ni、Co和Mn对三元复合正极材料进行掺杂改性后,改性材料都保持典型的α-NaFeO2层状结构,且晶型良好;LiNi1/3-Co1/3Mn1/3-1/40Ti1/40O2轮廓最分明,且形貌均一;3种改性材料的电化学性能均有一定程度的提高,其中LiNi1/3Co1/3Mn1/3-1/40Ti1/40O2提高最为明显,在0.1 C、1.0 C和2.0 C倍率下其首次放电比容量分别为145.35、140.79和125.60 mA.h/g,1.0 C倍率下循环30次后的容量保持率为88.06%.     

高温固相法合成锂离子电池正极材料LiNi0.8Co0.2O2研究

研究了高温固相法合成锂离子电池正极材料LiNi0.8Co0.2O2时原材料、气氛、温度、时间、Li:(Ni Co)化学计量比例、氧气流量、二次烧结等参数对制备电极活性材料结构和电性能的影响，使用其优化后的工艺参数，制备出容量为170mAb/g的LiNi0.8Co0.2O2,并对此正极材料组成的电池性能进行了测试。     

LiNi0.85-xCoxMn0.15O2电化学性能的第一性原理研究

采用基于密度泛函理论的第一性原理平面波赝势方法计算了空间群为R-3M,具有层状结构的LiNi0.85-xCoxMn0.15O2的带隙、分波态密度、嵌锂形成能和晶胞体积.计算结果表明LiNi0.65Co0.2Mn0.15O2具有较高的可逆容量,又具有较好的电池性能,为该系列金属氧化物中较为理想的锂离子电池正极材料,与文献的结果相比较,我们发现理论计算结果与实验结果有较好的一致性.本文采用CASTEP中原子混合实现镍钴含量的变化后,分析了LiNi0.85-xCoxMn0.15O2的物理性质及电化学性质.揭示了镍钴含量变化对材料作为锂离子电池正极材料的性能的影响,进而为寻找新的正极三元材料提供理论指导.     

Na+掺杂CoCr2O4尖晶石制备及其光催化性能

由于CoCr2O4尖晶石纳米粉体对二氧化碳和水合成甲酸具有光催化作用,采用溶胶凝胶法制备了Co0.8Na0.2Cr2O4尖晶石纳米粉体,用X射线衍射光谱仪(XRD)、紫外-可见光漫反射(UV-Vis DRS)、扫描电镜(SEM)对其成晶温度、晶体结构和光响应性能进行了表征。结果表明:CoCr2O4掺杂金属Na制备的Co0.8Na0.2Cr2O4属尖晶石结构,掺杂后晶格略有膨胀,禁带宽度变宽,吸光性能增强。在175 W高压汞灯照射下,Co0.8Na0.2Cr2O4比CoCr2O4对光催化还原CO2制取甲酸活性高。     

Hydrogen storage and low-temperature electrochemical performances of A2B7 type La-Mg-Ni-Co-Al-Mo alloys

The effect of Mo-addition on hydrogen storage and low-temperature electrochemical performances of La-Mg-Ni-Co-Al alloys is investigated. The alloys were synthetized via vacuum induction melting followed by annealing treatment at 1123 K for 8 h. The major phases in the annealed alloys are consisted of (La, Mg)2Ni7, (La, Mg)5Ni19 and LaNi5 phases. Mo-addition facilitates phase transformation of LaNi5 into (La, Mg)2Ni7 and (La, Mg)5Ni19 phases. Hydrogen absorption/desorption PCI curves indicates that the hydrogen storage capacity of the alloy increases remarkably with the addition of Mo. Furthermore, the La0.75Mg0.25Ni3.05Co0.2Al0.05Mo0.2 alloy shows excellent hydriding/dehydriding kinetics with a higher capacity, requiring only 100 s to reach its saturated hydrogen capacity of 1.58 wt% at low temperature of 303 K, and releasing 1.57 wt% hydrogen within 400 s at 338 K. Electrochemical experiments manifest that the Mo-added alloy electrode has perfect activation properties and the maximum discharge capacity. The low-temperature dischargeability shows that the La0.75Mg0.25Ni3.05Co0.2Al0.05Mo0.2 alloy exhibits the excellent low-temperature discharge performance, and the maximum discharge capacity is improved from 231.0 to 334.6 mAh/g at 253 K. The HRD property of the alloy electrode is enhanced, suggesting that Mo enhances the kinetic ability at low-temperature.     

低温熔盐法合成球形LiNi_(1/3)Co_(1/3)Mn_(1/3)O_2研究

采用低温熔盐法合成了锂离子电池正极材料Li Ni1/3Co1/3Mn1/3O2,并就低温熔盐0.62xLi NO3-0.38xLi OH-(1-x)CH3COOLi.2 H2O的具体比例、焙烧温度和焙烧时间对材料的影响进行了对比研究.XRD结果表明以x=0.6的低温共熔盐,经3阶段温度烧结(200℃,3 h;600℃,制备的样品的α-NaFeO2层状结构发育的较为完备.SEM扫描显示材料是由许多片状晶体构成的球形颗粒.材料在2.8～4.3 V范围内充放电,倍率为0.2 C时,首次放电比容量为173.6 mA.h.g-1,循环20次后容量保留97.4%;倍率为1 C时,首放126.0 mA.h.g-1,循环20次后容量保留94.1%.     

化学镀铜对A2B7型贮氢合金电极电化学性能的影响

以A2B7型贮氢合金La0.75Mg0.25Ni3.44Al0.06为对象,系统研究了合金覆铜后进行不同温度退火处理的电极电化学性能。结果表明,表面包覆Cu及退火处理后的贮氢合金电极的活化性能及循环稳定性有所提高。线性极化扫描和电化学阻抗图谱分析结果表明,包覆Cu及退火处理后提高了合金电极的交换电流密度I0,降低了电化学阻抗,说明包覆处理改善了合金表面的电催化活性,加快了合金表面电荷的迁移速率,从而提高了高倍率放电能力。     

Coupling effect of the conductivities of Li ions and electrons by introducing LLTO@C fibers in the LiNi0.8Co0.15Al0.05O2 cathode

To probe the coupling effect of the electron and Li ion conductivities in Ni-rich layered materials(LiNi0.8Co0.15Al0.05O2,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.     

Microstructural evolution and performance of hydrogen storage and electrochemistry of Co-added La0.75Mg0.25Ni3.5−xCox (x = 0, 0.2, 0.5 at%) alloys

Microstructure, hydrogen storage and electrochemical performances of Co-added La_(0.75)Mg_(0.25)Ni_(3.5_x)Co_x(x = 0,0.2, 0.5 at%) alloys are studied. XRD and rietveld refinement results suggest that the samples are mainly composed of(LaMg)Ni_3,(LaMg)_2Ni_7 and LaNi_5 phases, Co substitution for Ni changes the phase abundance,but not the phase composition. With the rising of Co content, the amount of(LaMg)_2 Ni_7 phase decreases, but the amount of LaNi_5 phase increases, while the amount of(LaMg)Ni_3 phase firstly increases and then decreases.The alloys reversibly absorb and desorb hydrogen at 298 K smoothly. When Co content is 0.2 at%, the hydrogen absorption capacity reaches the maximum value of 1.14 H/M, and the absorption capacities reach 1.09 H/M and 1.03 H/M in the first minute at 298 K and 323 K, respectively. Electrochemical performance measurement results show that La_(0.75)Mg_(0.25)Ni_(3.5-x)Co_x alloys are completely activated within 2 cycles, and the cyclic stability of La_(0.75)Mg_(0.25)Ni_(3.3)Co_(0.2) alloy approaches 63.7% after 100 charge/discharge cycles, which is higher than that(S_(100) = 60%) of La_(0.75)Mg_(0.25)Ni_(3.0)Co_(0.5) alloy. Thus, the La_(0.75)Mg_(0.25)Ni_(3.3)Co_(0.2) alloy exhibits optimum comprehensive properties of hydrogen storage and electrochemistry.     

钴含量对锂离子电池正极材料LiNi0.5-xCo2xMn0.5-XO2的性能影响

采用共沉淀-喷雾法合成出层状LiNi0.5-xCo2xMn0.5-xO2(x=0,0.075,0.15)正极材料,研究了不同掺钴量对材料的结构和电化学性能的影响,并用XRD、SEM及电性能测试考察了所得材料的结构、形貌与电化学性能;XRD分析表明,LiNi0.5-xCo2xMn0.5-xO2具有α-NaFeO2层状结构,Co3+的掺入可促进层状结构的生成,有效减少阳离子混排。电性能测试结果显示,LiNi0.5-xCo2xMn0.5-xO2随着掺钴量的增大,放电容量提高,循环性能变好;样品LiNi0.35Co0.3Mn0.35O2表现出最好的电化学性能,其首次放电效率充放电效率达90%,首次放电容量为172.8 mAh/g,40次循环容量无明显衰减。     

不同锂源对富锂锰基Li1.133Mn0.466Ni0.2Co0.2O2正极材料性能的影响研究

采用共沉淀的方法将含有一定比例的镍、钴、锰的金属醋酸盐溶液均匀混合,然后加入适当的沉淀剂Na2CO3制备前驱体Mn0.466Ni0.2Co0.2CO3,最后分别与不同锂源（Li2CO3、LiOH）混合煅烧得到富锂锰基Li1.133Mn0.466Ni0.2Co0.2O2正极材料。采用XRD和SEM分别对不同锂源制备的Li1.133Mn0.466Ni0.2Co0.2O2的结构和表面形貌进行表征,采用恒电流充放电和循环伏安法测试对不同锂源制备的Li1.133Mn0.466Ni0.2Co0.2O2的电化学性能进行测试。结果表明,以LiOH为锂源合成的样品在0.1C倍率下首次充、放电比容量分别为330.1mAh/g和218.6mAh/g,首次库仑效率为66.23%,在1C倍率内表现为优秀的稳定循环比容量特性,但是在2C以及2C以上高倍率循环稳定性不及以Li2CO3为锂源合成的样品性能。     

尖晶石型LiMn1.925Co0.025Ti0.025Sn0.025O4的合成及性能研究

利用高温固相法制备了尖晶石型LiMn2O4、LiMn1．925Co0．075O4、LiMn1．925Co0.0375Ti0.0375O4、LiMn1．925Co0．025Ti0.025Sn0.025O4锂离子电池正极材料，并用XRD、充放电测试、循环伏安、电化学阻抗测试等研究了其结构和电化学性能．结果表明：掺杂样品均为单一尖晶石结构，在0．2C和3．0-4．2V条件下恒流充放电，发现掺杂后材料的循环性能有很大改善，其中LiMn1．925Co0．025Ti0．025Sn0．025O4具有较高的放电容量，50次循环后容量衰仅为7．97％．活性物质在不同的电位下具有不同的电化学特性，电化学阻抗谱明显不同，并对其进行了解释．     

氟化锂及氮化亚铜人工固态电解质膜对锂离子电池正极三元材料的改性

在锂离子电池充放电过程中,电解液与电极材料发生反应,形成的固态电解质膜(solid electrolyte interphase,SEI)随着充放电次数的增加而变厚,这将降低电池的循环稳定性。所制备的人工固态电解质膜(a-SEI)可改善锂离子电池的循环稳定性,其主要成分为使用液相法制备的氟化锂(LiF)、氮化亚铜(Cu 3N)纳米颗粒。通过两种不同路径,将两种纳米颗粒先后在锂离子电池正极三元材料LiNi 0.8 Co 0.1 Mn 0.1 O 2(NCM811)电极片表面和活性材料颗粒表面涂覆生成一层a-SEI。使用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、电化学阻抗谱(EIS)等材料表征和电化学分析方法,解析a-SEI对锂离子电池循环稳定性的影响。结果表明,NCM811材料表面包覆Cu 3N作为a-SEI的电化学性能最好,相比纯NCM811材料,50周循环后的容量保持率可提升26.5%。     

α-Ni_(0.8)Co_xAl_(0.2-x)(OH)_(2.2-0.5y)(CO_3)_y·zH_2O配位沉淀法合成和电化学性能

为了改善铝代α-Ni(OH)2的电化学性能,用共沉淀法合成了含不同配比Al3+、Co3+的Ni(OH)2.样品经CT、XRD、FTIR、SEM等表征为α-Ni0.8CoxAl0.2-x(OH)2.2-0.5y(CO3)y.zH2O.恒电流充放电和微电极CV等测试表明:Co3+的摩尔分数在0.02~0.04时,合成的样品作为氢镍电池的正极材料,在放电比容量、电极可逆性和稳定性等方面均得到改善.Co3+发挥了稳定α相结构、增强导电性等多重作用.