Polyol-mediated synthesis of Li4Ti5O12 nanoparticle and its electrochemical properties

Li₄Ti₅O₁₂ nanoparticles were precipitated from ethylene glycol solution of titanium tetra isopropoxide (Ti(O-iPr)₄) and Li₂O₂ by refluxing at 197 °C for 12 h. The obtained particles were filtered and dried at 100 °C for 12 h, and the dried powder samples were heated at 320, 500 and 800 °C for 3 h. The X-ray diffraction patterns of the obtained samples exhibited a good fit with the spinel phase. The field emission-SEM images of the dried powder sample and the samples heated at 320, 500 and 800 °C for 3 h showed a uniform spherical morphology with a particle size of 5, 8, 10 and 400 nm, respectively. According to the results of electrochemical testing, the dried powder sample and the samples heated at 320, 500, and 800 °C for 3 h showed initial capacities of 200, 310, 320, and 260 mA h/g, respectively, at a current density of 0.05 mA/cm². Nanosized (6–8 nm) particles with good crystallinity were obtained by controlling the synthesis conditions. The sample heated at 500 °C for 3 h exhibited a high capacity and an excellent rate capability over 60 cycles.     

三维尖晶石Li4Ti5O12纳米丝网状电极的构置与电化学性能

首次采用电纺丝技术结合高温退火成功地构置了含尖晶石Li₄Ti₅O₁₂的纳米纤维丝三维(3D)网状结构，并测量了三维电池的充放电性能。X射线衍射谱(XRD)、扫描电子显微镜(SEM)和电池循环性能测试等方法表征纤维丝3D结构和电化学性能。研究结果表明了Li₄Ti₅O₁₂纳米丝的零应变特性、构建的3D阵列的结构稳定性和在大电流密度下较好的充放电性能。显示了Li₄Ti₅O₁₂可作为3D电池的电极材料。     

尖晶石Li4Ti5O12中锂离子的化学扩散系数的研究

A relatively simple galvanostatic method was used for the evaluation on the average chemical diffusion coefficient of lithium-ion in spinel Li₄Ti₅O₁₂ prepared by solid-state reaction technique. The diffusion coefficient of lithium-ion was estimated to be 2.8×10^-13 cm²·s^-1 and 1.3×10^-13 cm²·s^-1 for charge and discharge， respectively.     

离子交换法合成纳米级锂离子电池负极材料Li_4Ti_5O_(12)

用钛酸纳米管和LiOH溶液进行离子交换法得到了水合钛酸锂前驱体,进而在不同温度热处理制备了Li4Ti5O12。通过X射线衍射(XRD)、扫描电镜(SEM)、热分析(TG-DSC)和恒电流充放电测试对反应产物进行了研究。结果表明所得前驱体在500～700℃热处理可得到纳米结构的纯相Li4Ti5O12。所得Li4Ti5O12的可逆容量约为160mAh·g-1,循环稳定性随热处理温度的提高而增强,并因具有较短的锂离子扩散距离表现出极佳的倍率性能,在1600mA·g-1(约10C)的电流密度下放电下还保持140mAh·g-1的容量。     

新型Li_4Ti_5O_(12)@石墨烯的微波辅助合成及电化学性能研究

将钛酸四丁酯和氧化石墨超声分散于叔丁醇,微波辐射下加入醋酸锂溶液制备尖晶石Li4Ti5O12(LTO)前驱体/氧化石墨烯。一方面,微波作用促进了钛酸四丁酯水解,前驱体的形成能在15 min内完成。另一方面,叔丁醇的"软模板"限域作用导致形成粒子极小且形貌单一的LTO前驱体。同时,细小的LTO前驱体粒子通过二次团聚将氧化石墨烯纳米片完全包埋。最后,LTO前驱体/氧化石墨烯在800℃下煅烧8 h得到尖晶石LTO@石墨烯(LTO@G)。研究表明,LTO@G晶体尺寸在0.2~1.5μm之间,其振实密度达到1.7 g·cm-3。石墨烯位于晶体内部,并显著提高了材料的电子传导性。LTO@G的电导率为1.84×10-3 S·m-1,远高于纯相LTO(1.1×10-7 S·m-1)。1C和4C下,LTO@G首次充放电容量分别是170.1和97.5 m Ah·g-1。可见,LTO@G具有高倍率性能和振实密度,可广泛应用于各种商品锂离子电池。     

Effect of surface fluorination on the electrochemical behavior of petroleum cokes for lithium ion battery

Surface structure change and electrochemical behavior of fluorinated petroleum coke samples (petroleum cokes: petroleum coke and those heat-treated at 1860 °C, 2300 °C and 2800 °C, abbreviated to PC, PC1860, PC2300 and PC2800, respectively) have been investigated. Surface oxygen of petroleum coke was decreased by the fluorination using elemental fluorine. Raman and EPR spectroscopies revealed that surface fluorination increased surface disorder and lattice defects. ¹⁹F NMR spectrum suggests that distribution of fluorine atoms in PC fluorinated 300 °C was similar to that in graphite fluoride with covalent CF bonds. Surface areas of fluorinated petroleum cokes were nearly the same as those of non-fluorinated ones or only slightly increased by fluorination, except PC fluorinated at 300 °C. It is noted that first coulombic efficiencies of PC2300 and PC2800 were highly increased to 80-84% by the fluorination at 300 °C. These values of 80-84% were 12-18% higher than those of non-fluorinated PC2300 and PC2800.     

Li4Ti5O12溶胶-凝胶法合成及其机理研究

The precursors of Li₄Ti₅O₁₂ were prepared from tetrabutyl titanate and lithium acetate by sol-gel process. The Li₄Ti₅O₁₂ samples were synthesized by calcining the gel precursors at 400～900 ℃ in air for 6～20 h. Its reaction mechanism was investigated by infrared spectroscopy(IR), thermogravimetry(TG) and X-ray diffraction(XRD). The effects of sinter-temperature, calcination-time and thermal-treatment for the products were discussed. The samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM). The results showed that the single-phase products were obtained by calcining the gel precursors at 800 ℃ in air for 20 h, the sinter-temperature was lower than that of solid-state method, the particles were narrowly distributed, well crystallized with a size range from 0.3μm to 0.5 μm.     

三维连续结构Li4Ti5O12/石墨烯纳米复合材料:制备和其锂离子电池超长循环性能

利用具有三维连续纳米孔结构的热剥离石墨烯为骨架制备Li₄Ti₅O₁₂/石墨烯纳米复合材料。通过乙醇挥发法在热剥离石墨烯的纳米孔道内引入前驱物, 进一步高温热处理, 在热剥离石墨烯的孔道内原位形成Li₄Ti₅O₁₂纳米粒子。利用复合材料作为锂离子电池电极材料。电化学反应过程中, 热剥离石墨烯的三维连续结构确保了Li₄Ti₅O₁₂纳米粒子与石墨烯在长循环过程中的有效接触。因此, 复合材料表现出优异的循环稳定性。在5C下, 5 000次循环后, 其容量保持率高达94%。     

三维连续结构Li4Ti5O12/石墨烯纳米复合材料：制备和其锂离子电池超长循环性能

利用具有三维连续纳米孔结构的热剥离石墨烯为骨架制备Li4Ti5O12/石墨烯纳米复合材料。通过乙醇挥发法在热剥离石墨烯的纳米孔道内引入前驱物,进一步高温热处理,在热剥离石墨烯的孔道内原位形成Li4Ti5O12纳米粒子。利用复合材料作为锂离子电池电极材料。电化学反应过程中,热剥离石墨烯的三维连续结构确保了Li4Ti5O12纳米粒子与石墨烯在长循环过程中的有效接触。因此,复合材料表现出优异的循环稳定性。在5C下,5 000次循环后,其容量保持率高达94%。     

LiMn2O4表面包覆Li4Ti5O12的制备及倍率特性

采用固相法合成了尖晶石型LiMn₂O₄，并通过溶胶-凝胶法制备了不同物质的量的百分比含量Li₄Ti₅O₁₂包覆的正极材料。X-射线衍射和扫描电镜结果表明，Li₄Ti₅O₁₂微粒包覆在LiMn₂O₄的表面没有产生晶体结构的变化。实验电池在室温下，以1C，2C和5C倍率作充放电循环测试；结果表明，与未包覆的LiMn₂O₄相比，表面包覆Li₄Ti₅O₁₂微粒的正极材料在高倍率下具有更好的循环稳定性。     

Li4Ti5O12-聚苯胺复合材料的合成与表征

以醋酸锂和钛酸四丁酯为原料，以乙醇为溶剂，采用溶胶-凝胶法制备Li₄Ti₅O₁₂;以苯胺、过硫酸铵为原料，以盐酸为溶剂，采用原位聚合法合成Li₄Ti₅O₁₂-聚苯胺复合材料。采用X-射线衍射、红外光谱和电化学测试等对复合材料进行了表征。结果表明，聚苯胺的加入明显提高了Li₄Ti₅O₁₂的电子导电性能，Li₄Ti₅O₁₂-PAn复合材料具有比Li₄Ti₅O₁₂更好的高倍率性能和循环稳定性。0.1C和2.0C放电时Li₄Ti₅O₁₂-PAn的放电容量达到了191.3和148.9 mAh·g^-1，经80次循环后二者平均每次循环容量衰减率分别为0.13%和0.61%。     

新型Li4Ti5O12@石墨烯的微波辅助合成及电化学性能研究

将钛酸四丁酯和氧化石墨超声分散于叔丁醇,微波辐射下加入醋酸锂溶液制备尖晶石Li₄Ti₅O₁₂（LTO）前驱体/氧化石墨烯。一方面,微波作用促进了钛酸四丁酯水解,前驱体的形成能在15min内完成。另一方面,叔丁醇的“软模板”限域作用导致形成粒子极小且形貌单一的LTO前驱体。同时,细小的LTO前驱体粒子通过二次团聚将氧化石墨烯纳米片完全包埋。最后,LTO前驱体/氧化石墨烯在800℃下煅烧8h得到尖晶石LTO@石墨烯（LTO@G）。研究表明,LTO@G晶体尺寸在0.2~1.5μm之间,其振实密度达到1.7g·cm^-3。石墨烯位于晶体内部,并显著提高了材料的电子传导性。LTO@G的电导率为1.84×10^-3S·m^-1,远高于纯相LTO（1.1×10^-7S·m^-1）。1C和4C下,LTO@G首次充放电容量分别是170.1和97.5mAh·g^-1。可见,LTO@G具有高倍率性能和振实密度,可广泛应用于各种商品锂离子电池。     

Li ion diffusion in Li4Ti5O12 thin film electrode prepared by PVP sol-gel method

Li₄Ti₅O₁₂ thin films for rechargeable lithium batteries were prepared by a sol-gel method with poly(vinylpyrrolidone). Interfacial properties of lithium insertion into Li₄Ti₅O₁₂ thin film were examined by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and potentiostatic intermittent titration technique (PITT). Redox peaks in CV were very sharp even at a fast scan rate of 50 mV s⁻¹, indicating that Li₄Ti₅O₁₂ thin film had a fast electrochemical response, and that an apparent chemical diffusion coefficient of Li⁺ ion was estimated to be 6.8×10⁻¹¹ cm² s⁻¹ from a dependence of peak current on sweep rates. From EIS, it can be seen that Li⁺ ions become more mobile at 1.55 V vs. Li/Li⁺, corresponding to a two-phase region, and the chemical diffusion coefficients of Li⁺ ion ranged from 10⁻¹⁰ to 10⁻¹² cm² s⁻¹ at various potentials. The chemical diffusion coefficients of Li⁺ ion in Li₄Ti₅O₁₂ were also estimated from PITT. They were in a range of 10⁻¹¹-10⁻¹² cm² s⁻¹.     

锂离子电池用Li4Ti5O12-碳复合材料的制备与电化学性能

Li₄Ti₅O₁₂-C composite was prepared by sol-gel method using ethyl alcohol as solvent, lithium acetate and tetrabutyl titanate as raw materials, and graphite as carbon source. Li₄Ti₅O₁₂-C composites were characterized by thermogravimertric(TG) analysis and differential thermal analysis(DTA), X-ray diffraction(XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and electrochemical tests. Results show that Li₄Ti₅O₁₂-C composite with 5% carbon containing can be obtained by annealing the precursor at 600 ℃ for 6 h in N₂ atomsphere. The composites can deliver a specific capacity of 167.1 mAh·g^-1, 99.0% and 105.1% of the capacity can be retained after discharged for 80 times at 0.1C and 2.0C, respectively. Compared with pure Li₄Ti₅O₁₂, Li₄Ti₅O₁₂-C composite shares larger discharge capacity, better cyclability and rate performance.     

Li4Ti5O12/(Ag+C)电极材料的固相合成及电化学性能

以Li₂CO₃,TiO₂为原料,葡萄糖为碳源,采用固相煅烧工艺合成了亚微米级的Li₄Ti₅O₁₂/C复合负极材料。并将之与AgNO₃复合,采用固相方法制备出了Ag表面修饰的Li₄Ti₅O₁₂/(Ag+C)复合材料。采用XRD、SEM和TEM测试方法对材料的微结构进行了表征。结果表明,C的存在对Ag单质在Li₄Ti₅O₁₂/C颗粒表面的大量形成起到了积极的促进作用,从而很大程度地提高了Li₄Ti₅O₁₂/C的电导率,因此有效地改善了其电化学性能。在1C倍率下,Li₄Ti₅O₁₂/(Ag+C)复合材料的首次放电容量达到了164 mAh·g^-1。     

Kinetic analysis of the thermal stability of lithium silicates (Li4SiO4 and Li2SiO3)

The kinetics describing the thermal decomposition of Li₄SiO₄ and Li₂SiO₃ have been analysed. While Li₄SiO₄ decomposed on Li₂SiO₃ by lithium sublimation, Li₂SiO₃ was highly stable at the temperatures studied. Li₄SiO₄ began to decompose between 900 and 1000 °C. However, at 1100 °C or higher temperatures, Li₄SiO₄ melted, and the kinetic data of its decomposition varied. The activation energy of both processes was estimated according to the Arrhenius kinetic theory. The energy values obtained were −408 and −250 kJ mol⁻¹ for the solid and liquid phases, respectively. At the same time, the Li₄SiO₄ decomposition process was described mathematically as a function of a diffusion-controlled reaction into a spherical system. The activation energy for this process was estimated to be −331 kJ mol⁻¹. On the other hand, Li₂SiO₃ was not decomposed at high temperatures, but it presented a very high preferential orientation after the heat treatments.     

非整比Li4-xTi5SnyO12化合物的合成及电化学性能的研究

采用流变相法合成了锡掺杂的非整比锂钛氧尖晶石化合物,并研究了不同比例的Sn髧离子掺杂对锂钛氧尖晶石结构及性能的影响。采用XRD、SEM技术对合成材料的晶体结构和微观形貌进行表征,采用恒流充、放电系统及交流阻抗测试法对合成材料的电化学性能进行了测试,结果表明:Sn髧离子掺杂在一定程度上改善了锂钛氧尖晶石作为负极材料时,不同的掺杂量,对材料的电化学性能影响不同,其中Li4-xTi5Sn0·3O12材料的性能为最佳,当电池在较低电流密度下(50 mA·g-1)充、放电时,Li4-xTi5Sn0·3O12材料的首次放电比容量为236 mAh·g-1,在随后提高充、放电倍率过程中(由1C增到4C进行充、放电),当循环105次后,Li4-xTi5Sn0·3O12材料的放电比容量仍保持在109.8 mAh·g-1,与纯样品或其它非整比掺杂样品锂钛氧尖晶石比较,Li4-xTi5Sn0·3O12表现优良的电化学循环性能。本文还对锡掺杂导致锂钛尖晶石材料性能改善的原因也进行了初步探索。     

Li4Ti5O12/(Cu+C)复合材料的制备及电化学性能

以Li₄Ti₅O₁₂,Cu(CH₃COO)₂·H₂O和C₆H₁₂O₆为前驱体,化学沉积与热分解结合合成锂离子电池负极材料Li₄Ti₅O₁₂/(Cu+C)。采用X-射线衍射(XRD)、扫描电子显微镜(SEM)、恒流充放电、循环伏安和电化学阻抗方法表征样品的结构、形貌和电化学性能。结果表明,Li₄Ti₅O₁₂表面包覆的Cu与C提高了Li₄Ti₅O₁₂电极材料的导电率,其循环性能和倍率性能得到有效地改善。在0.5C、1C和3C倍率下,经过50次充放电循环,放电比容量分别为168.2、160、140.6 mAh·g^-1,其容量保持率分别为88.7%、84.4%、71.2%。电化学阻抗测试表明,表面包覆的Cu与C使其电荷转移阻抗大幅度减少。     

高倍率尖晶石型Li_4Ti_5O_(l2)/TiN锂离子电池负极材料的合成及其电化学性能

以乙酰丙酮(ACAC)为螯合剂、聚乙二醇(PEG)为分散剂,采用溶胶-凝胶法合成了尖晶石型Li4Ti5Ol2/TiN材料.考察了TiN膜对尖晶石型Li4Ti5Ol2锂离子电池负极材料电化学性能的影响.利用X射线光电子能谱(XPS)对Li4Ti5O12表面的TiN膜进行了分析.X射线衍射(XRD)和扫描电子显微镜(SEM)分析表明,Li4Ti5Ol2/TiN材料为结晶良好的亚微米纯相尖晶石型钛酸锂.电化学性能测试表明,该材料的首次放电比容量为173.0mAh·g-1,并且具有良好的循环性能,以0.2C、1C、2C、5C倍率放电进行测试,10次循环后比容量分别为170.6、147.6、135.6、111.0mAh·g-1,较之表面无TiN膜的钛酸锂材料表现出更好的倍率特性.循环伏安曲线(CV),交流阻抗图谱(EIS)进一步论证了TiN膜改善了尖晶石型Li4Ti5Ol2锂离子电池负极材料的电化学性能.     

Raman scattering investigations on lanthanum-doped Bi4Ti3O12-SrBi4Ti4O15 intergrowth ferroelectrics

The ferroelectric ceramics of Bi₄Ti₃O₁₂, SrBi₄Ti₄O₁₅, and lanthanum-doped Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅ were synthesized, and their Raman spectra were investigated. La-doping resulted in the enlargement of remnant polarization of Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅. The structure of the Bi₂O₂ layers and TiO₆ octahedra of the intergrowth was found to be different from those of Bi₄Ti₃O₁₂ and SrBi₄Ti₄O₁₅. La³⁺ ions exhibit pronounced selectivity for the occupation of A site as La content is lower than 0.50, and tend to be incorporated into Bi₂O₂ layers when the La content is higher than 0.50. Lanthanum substitution brings about the structural phase transition in Bi₄Ti₃O₁₂-SrBi₄Ti₄O₁₅. The variation of ferroelectric property may be attributed to combined contribution from the decreasing of the oxygen vacancies, the relaxation of the lattice distortion, the destroying of the insulation and the space charge compensation effects of the Bi₂O₂ slabs.