A series of solid solutions with high content of Tb_(2)O_(3)-(Tb_(x)Ti_(1−x))4O_(8−2x)(x=0.667-0.830)are synthesized in the Tb_(2)O_(3)-TiO_(2)system via co-precipitation and/or mechanical activation.This is followed ...A series of solid solutions with high content of Tb_(2)O_(3)-(Tb_(x)Ti_(1−x))4O_(8−2x)(x=0.667-0.830)are synthesized in the Tb_(2)O_(3)-TiO_(2)system via co-precipitation and/or mechanical activation.This is followed by high-temperature annealing for 4-22 h.The X-ray diffrac-tion method showed that the fluorite structure was realized for(Tb_(x)Ti_(1−x))4O_(8−2x)(x=0.75-0.817).The solid solution Tb_(3.12)Ti_(0.88)O_(6.44)(64mol%Tb_(2)O_(3)(x=0.78))with a fluorite structure exhibited a maximum hole conductivity of~22 S/cm at 600℃.To separate the ionic component of the conductivity in the electronic conductor Tb_(3.12)Ti_(0.88)O_(6.44),its high entropy analogue,(La_(0.2)Gd_(0.2)Tm_(0.2)Lu_(0.2)Y_(0.2))_(3.12)Ti_(0.88)O_(6.44),was synthesized in which all rare-earth elements(REE)cations exhibited valency of+3.Consequently,the contribution of ionic(proton)conductivity(~7×10^(−6)S/cm at 600℃)was revealed with respect to the background of dominant hole conductivity.The proton conduct-ivity of high-entropy oxide(HEО)(La_(0.2)Gd_(0.2)Tm_(0.2)Lu_(0.2)Y_(0.2))_(3.12)Ti_(0.88)O_(6.44)was confirmed by the detection of the isotope effect,where the mobility of the heavier O-D ions was lower than that of the O-H hydroxyls,resulting in lower conductivity in D_(2)O vapors when com-pared to H_(2)O.展开更多
LiCoO2 gradient coated LiNi0.96Co0.04O2 material and iso-structure LiNi0.8Co0.2O2 material (the same molar ratio 8/2 of Ni/Co in the two materials) as cathode for lithium-ion batteries were synthesized with a co-preci...LiCoO2 gradient coated LiNi0.96Co0.04O2 material and iso-structure LiNi0.8Co0.2O2 material (the same molar ratio 8/2 of Ni/Co in the two materials) as cathode for lithium-ion batteries were synthesized with a co-precipitation method. Microstructure of iso-structure LiNi0.8Co0.2O2 were about the same as that of LiNiO2, and the structure of the coated material was much more similar to that of LiCoO2 based on the X-ray diffraction patterns. The cycling voltammetry and galvanostatic cycle tests show that the properties of the coated material were improved significantly. The first specific charge and discharge capacity for the coated material was 249.20 mAh·g-1 and 207.90 mAh·g-1 respectively, and the specific discharge capacity for the 100th cycle was still 186.02 mAh·g-1 with an irreversible loss of only 21.1 mAh·g-1. This showed that the new material had a good lithium intercalation-deintrercalation performance. Meanwhile, the mechanism of the sintering reaction was proposed. During the sintering reaction of the precursor with LiOH, the Li+-ion permeated into the body of precursors because the shape of the precursor particles was not changed basically based on scanning electronic microscopy. So, the layer microstructure of the precursor is important for the layer microstructure of lithium nickel cobalt oxides electrode material.展开更多
Pure, layered compounds of overlithiated Li1＋xNi0.8Co0.2O2（x = 0.05 and 0.1） were successfully prepared by a modified combustion method. XRD studies showed that cell parameters of the material decreased with increa...Pure, layered compounds of overlithiated Li1＋xNi0.8Co0.2O2（x = 0.05 and 0.1） were successfully prepared by a modified combustion method. XRD studies showed that cell parameters of the material decreased with increasing the lithium content. SEM revealed that the morphology of particles changed from rounded polyhedral-like crystallites to sharp-edged polyhedral crystals with more doped lithium. EDX showed that the stoichiometries of Ni and Co agrees with calculated synthesized values. Electrochemical studies revealed the overlithiated samples have improved capacities as well as cycling behavior. The sample with x = 0.05 shows the best performance with a specific capacity of 113.29 mA.h.g-1 and the best capacity retention of 92.2% over 10 cycles. XPS results showed that the binding energy of Li ls is decreased for the Li doped samples with the smallest value for the x = 0.05 sample, implying that Li＋ ions can be extracted more easily from Li1.05Ni0.8Co0.2O2 than the other stoichiometries accounting for the improved performance of the material. Considerations of core level XPS peaks for transition metals reveal the existence in several oxidation states. However, the percentage of the＋3 oxidation state of transition metals for the when x = 0.1 is the highest and the availability for charge transition from the ＋3 to＋4 state of the transition metal during deintercalation is more readily available.展开更多
基金the state assignment on the topic“Interdisciplinary approaches to the creation and study of micro-/nanostructured systems”(No.125012200595-8)Conductivity measurements of the samples were performed in accordance with the state task for FRC PCP and MC RAS(No.124013000692-4).
文摘A series of solid solutions with high content of Tb_(2)O_(3)-(Tb_(x)Ti_(1−x))4O_(8−2x)(x=0.667-0.830)are synthesized in the Tb_(2)O_(3)-TiO_(2)system via co-precipitation and/or mechanical activation.This is followed by high-temperature annealing for 4-22 h.The X-ray diffrac-tion method showed that the fluorite structure was realized for(Tb_(x)Ti_(1−x))4O_(8−2x)(x=0.75-0.817).The solid solution Tb_(3.12)Ti_(0.88)O_(6.44)(64mol%Tb_(2)O_(3)(x=0.78))with a fluorite structure exhibited a maximum hole conductivity of~22 S/cm at 600℃.To separate the ionic component of the conductivity in the electronic conductor Tb_(3.12)Ti_(0.88)O_(6.44),its high entropy analogue,(La_(0.2)Gd_(0.2)Tm_(0.2)Lu_(0.2)Y_(0.2))_(3.12)Ti_(0.88)O_(6.44),was synthesized in which all rare-earth elements(REE)cations exhibited valency of+3.Consequently,the contribution of ionic(proton)conductivity(~7×10^(−6)S/cm at 600℃)was revealed with respect to the background of dominant hole conductivity.The proton conduct-ivity of high-entropy oxide(HEО)(La_(0.2)Gd_(0.2)Tm_(0.2)Lu_(0.2)Y_(0.2))_(3.12)Ti_(0.88)O_(6.44)was confirmed by the detection of the isotope effect,where the mobility of the heavier O-D ions was lower than that of the O-H hydroxyls,resulting in lower conductivity in D_(2)O vapors when com-pared to H_(2)O.
文摘LiCoO2 gradient coated LiNi0.96Co0.04O2 material and iso-structure LiNi0.8Co0.2O2 material (the same molar ratio 8/2 of Ni/Co in the two materials) as cathode for lithium-ion batteries were synthesized with a co-precipitation method. Microstructure of iso-structure LiNi0.8Co0.2O2 were about the same as that of LiNiO2, and the structure of the coated material was much more similar to that of LiCoO2 based on the X-ray diffraction patterns. The cycling voltammetry and galvanostatic cycle tests show that the properties of the coated material were improved significantly. The first specific charge and discharge capacity for the coated material was 249.20 mAh·g-1 and 207.90 mAh·g-1 respectively, and the specific discharge capacity for the 100th cycle was still 186.02 mAh·g-1 with an irreversible loss of only 21.1 mAh·g-1. This showed that the new material had a good lithium intercalation-deintrercalation performance. Meanwhile, the mechanism of the sintering reaction was proposed. During the sintering reaction of the precursor with LiOH, the Li+-ion permeated into the body of precursors because the shape of the precursor particles was not changed basically based on scanning electronic microscopy. So, the layer microstructure of the precursor is important for the layer microstructure of lithium nickel cobalt oxides electrode material.
文摘Pure, layered compounds of overlithiated Li1＋xNi0.8Co0.2O2（x = 0.05 and 0.1） were successfully prepared by a modified combustion method. XRD studies showed that cell parameters of the material decreased with increasing the lithium content. SEM revealed that the morphology of particles changed from rounded polyhedral-like crystallites to sharp-edged polyhedral crystals with more doped lithium. EDX showed that the stoichiometries of Ni and Co agrees with calculated synthesized values. Electrochemical studies revealed the overlithiated samples have improved capacities as well as cycling behavior. The sample with x = 0.05 shows the best performance with a specific capacity of 113.29 mA.h.g-1 and the best capacity retention of 92.2% over 10 cycles. XPS results showed that the binding energy of Li ls is decreased for the Li doped samples with the smallest value for the x = 0.05 sample, implying that Li＋ ions can be extracted more easily from Li1.05Ni0.8Co0.2O2 than the other stoichiometries accounting for the improved performance of the material. Considerations of core level XPS peaks for transition metals reveal the existence in several oxidation states. However, the percentage of the＋3 oxidation state of transition metals for the when x = 0.1 is the highest and the availability for charge transition from the ＋3 to＋4 state of the transition metal during deintercalation is more readily available.
