采用高温固相法成功合成了新型钛基负极材料Na_2Li_2Ti_6O_(14),并研究了其结构及电化学性能。利用高分辨透明电镜(HRTEM)、X射线衍射(XRD)及其Rietveld精修、扫描电子显微镜(SEM)及能谱分析(EDS)表征分析了材料的物相和显微结构。结果...采用高温固相法成功合成了新型钛基负极材料Na_2Li_2Ti_6O_(14),并研究了其结构及电化学性能。利用高分辨透明电镜(HRTEM)、X射线衍射(XRD)及其Rietveld精修、扫描电子显微镜(SEM)及能谱分析(EDS)表征分析了材料的物相和显微结构。结果表明,合成的Na_2Li_2Ti_6O_(14)负极材料为纯相,具有Fmmm空间群结构;Na_2Li_2Ti_6O_(14)颗粒约为500~800 nm,Na、Ti和O三种元素分布均匀。循环伏安(CV)、充放电及电化学阻抗谱(EIS)测试表明,材料具有较好的锂离子脱嵌可逆性,较好的倍率性能和循环稳定性。钛电流密度为500 m A/g充放电时,Na_2Li_2Ti_6O_(14)材料的首次脱锂(充电)容量为180 m A·h/g,100次循环后可逆容量为136 m A·h/g;100次循环后,Na_2Li_2Ti_6O_(14)材料的电荷转移电阻增加,锂离子扩散系数略有下降,表明Na_2Li_2Ti_6O_(14)材料在循环后SEI膜的生成,降低了材料的电化学活性。展开更多
A series of Ba Li_(2-x)NaxTi_6O_(14)(0≤x≤2) compounds as lithium storage materials were synthesized by a facile solidstate method. X-ray diffraction Rietveld refinement shows that the Bragg positions correspon...A series of Ba Li_(2-x)NaxTi_6O_(14)(0≤x≤2) compounds as lithium storage materials were synthesized by a facile solidstate method. X-ray diffraction Rietveld refinement shows that the Bragg positions correspond to the Ba Li_2Ti_6O_(14), indicating a successful preparation. The Na+ions doped Ba Li_2-Ti_6O_(14) compounds have larger unit-cell volume than the pristine one because ionic radius of Na+ion is 55% larger than that of Li+ion. SEM shows that the Ba Li_2-xNaxTi_6O_(14)(x=0, 0.5 and1) powders show similar irregular shaped particles between500 and 1000 nm. However, Ba Li_2-xNaxTi_6O_(14)(x=1.5 and 2)powders show similar rod-like shape. CV reveals that the passivating film is mainly formed during the first insertion process, and the solid electrolyte interface film on the surface of Ba Li_2-xNaxTi_6O_(14)(0≤x≤2) is formed below 0.7 V in the first cycle. Compared with other samples, Ba Li_0.5Na1.5Ti_6O_(14) exhibits higher reversible capacity, better rate capability and superior cyclability. Ba Li_0.5Na1.5Ti_6O_(14) delivers the delithiation capacities of 162.1 mAhg^-(1)at 50 m A g^-(1), 158.1 mAhg^-(1)at 100 m A g^-(1), 156.7 mAhg^-(1)at 150 m A g^-(1), 152.2 mAhg^-(1)at 200 m A g^-(1), 147.3 mAhg^-(1)at 250 m A g^-(1)and 142 mAhg^-(1)at 300 m A g^-(1), respectively. An interesting thing is that Ba Na2Ti_6O_(14) as anode also shows an acceptable electrochemical performance. All these improved electrochemical performances of Ba Li_0.5Na1.5Ti_6O_(14) are attributed to the lowest polarization and the highest lithium ion diffusion coefficient among all samples.Hence, Ba Li_0.5Na1.5Ti_6O_(14) with excellent cycling performance,simple synthesis route and wide discharge voltage range can be a possible anode candidate for lithium-ion batteries.展开更多
Relying on a solvent thermal method, spherical Na2Li2Ti6O14 was synthesized. All samples prepared by this method are hollow and hierarchical structures with the size of about 2-3 μtm, which are assembled by many prim...Relying on a solvent thermal method, spherical Na2Li2Ti6O14 was synthesized. All samples prepared by this method are hollow and hierarchical structures with the size of about 2-3 μtm, which are assembled by many primary nanoparticles (-300nm). Particle morphology analysis shows that with the increase of temperature, the porosity increases and the hollow structure becomes more obvious. Na2Li2Ti6Ol4 obtained at 800℃ exhibits the best electro- chemical performance among all samples. Charge-discharge results show that Na2Li2Ti6O14 prepared at 800℃ can delivers a reversible capacity of 220.1, 181.7, 161.6, 144.2, 118.1 and 97.2 mA h g-1 at 50, 140, 280, 560, 1400, 2800 mA g-1. How- ever, Na2Li2Ti6O4-bulk only delivers a reversible capacity of 187, 125.3, 108.3, 88.7, 69.2 and 54.8 mA h g-1 at the same current densities. The high electrochemical performances of the as-prepared materials can be attributed to the distinctive hollow and hierarchical spheres, which could effectively reduce the diffusion distance of Li ions, increase the con- tact area between electrodes and electrolyte, and buffer the volume changes during Li ion intercalation/deintercalation processes.展开更多
文摘采用高温固相法成功合成了新型钛基负极材料Na_2Li_2Ti_6O_(14),并研究了其结构及电化学性能。利用高分辨透明电镜(HRTEM)、X射线衍射(XRD)及其Rietveld精修、扫描电子显微镜(SEM)及能谱分析(EDS)表征分析了材料的物相和显微结构。结果表明,合成的Na_2Li_2Ti_6O_(14)负极材料为纯相,具有Fmmm空间群结构;Na_2Li_2Ti_6O_(14)颗粒约为500~800 nm,Na、Ti和O三种元素分布均匀。循环伏安(CV)、充放电及电化学阻抗谱(EIS)测试表明,材料具有较好的锂离子脱嵌可逆性,较好的倍率性能和循环稳定性。钛电流密度为500 m A/g充放电时,Na_2Li_2Ti_6O_(14)材料的首次脱锂(充电)容量为180 m A·h/g,100次循环后可逆容量为136 m A·h/g;100次循环后,Na_2Li_2Ti_6O_(14)材料的电荷转移电阻增加,锂离子扩散系数略有下降,表明Na_2Li_2Ti_6O_(14)材料在循环后SEI膜的生成,降低了材料的电化学活性。
基金supported by the National Natural Science Foundation of China(51404002)Anhui Provincial Natural Science Foundation(1508085MB25)+1 种基金the Natural Science Foundation of Guangdong Province(2016A030310127)Anhui Provincial Science Fund for Excellent Young Scholars(gxyq ZD2016066)
文摘A series of Ba Li_(2-x)NaxTi_6O_(14)(0≤x≤2) compounds as lithium storage materials were synthesized by a facile solidstate method. X-ray diffraction Rietveld refinement shows that the Bragg positions correspond to the Ba Li_2Ti_6O_(14), indicating a successful preparation. The Na+ions doped Ba Li_2-Ti_6O_(14) compounds have larger unit-cell volume than the pristine one because ionic radius of Na+ion is 55% larger than that of Li+ion. SEM shows that the Ba Li_2-xNaxTi_6O_(14)(x=0, 0.5 and1) powders show similar irregular shaped particles between500 and 1000 nm. However, Ba Li_2-xNaxTi_6O_(14)(x=1.5 and 2)powders show similar rod-like shape. CV reveals that the passivating film is mainly formed during the first insertion process, and the solid electrolyte interface film on the surface of Ba Li_2-xNaxTi_6O_(14)(0≤x≤2) is formed below 0.7 V in the first cycle. Compared with other samples, Ba Li_0.5Na1.5Ti_6O_(14) exhibits higher reversible capacity, better rate capability and superior cyclability. Ba Li_0.5Na1.5Ti_6O_(14) delivers the delithiation capacities of 162.1 mAhg^-(1)at 50 m A g^-(1), 158.1 mAhg^-(1)at 100 m A g^-(1), 156.7 mAhg^-(1)at 150 m A g^-(1), 152.2 mAhg^-(1)at 200 m A g^-(1), 147.3 mAhg^-(1)at 250 m A g^-(1)and 142 mAhg^-(1)at 300 m A g^-(1), respectively. An interesting thing is that Ba Na2Ti_6O_(14) as anode also shows an acceptable electrochemical performance. All these improved electrochemical performances of Ba Li_0.5Na1.5Ti_6O_(14) are attributed to the lowest polarization and the highest lithium ion diffusion coefficient among all samples.Hence, Ba Li_0.5Na1.5Ti_6O_(14) with excellent cycling performance,simple synthesis route and wide discharge voltage range can be a possible anode candidate for lithium-ion batteries.
基金supported by the National Natural Science Foundation of China (21301052 and 51404002)Natural Science Foundation of Heilongjiang Province (E2016056)+2 种基金Specialized Research Fund for the Doctoral Program of Higher Education (20132301120001)Postdoctoral Science-Research Developmental Foundation of Heilongjiang Province (LBH-Q13138)Applied Technology Research and Development Program of Harbin (2015RAQXJ032)
文摘Relying on a solvent thermal method, spherical Na2Li2Ti6O14 was synthesized. All samples prepared by this method are hollow and hierarchical structures with the size of about 2-3 μtm, which are assembled by many primary nanoparticles (-300nm). Particle morphology analysis shows that with the increase of temperature, the porosity increases and the hollow structure becomes more obvious. Na2Li2Ti6Ol4 obtained at 800℃ exhibits the best electro- chemical performance among all samples. Charge-discharge results show that Na2Li2Ti6O14 prepared at 800℃ can delivers a reversible capacity of 220.1, 181.7, 161.6, 144.2, 118.1 and 97.2 mA h g-1 at 50, 140, 280, 560, 1400, 2800 mA g-1. How- ever, Na2Li2Ti6O4-bulk only delivers a reversible capacity of 187, 125.3, 108.3, 88.7, 69.2 and 54.8 mA h g-1 at the same current densities. The high electrochemical performances of the as-prepared materials can be attributed to the distinctive hollow and hierarchical spheres, which could effectively reduce the diffusion distance of Li ions, increase the con- tact area between electrodes and electrolyte, and buffer the volume changes during Li ion intercalation/deintercalation processes.