掺铬锂电池正E极材料 Li1+xCryMn2-y-xO4的合成及其结构性能的研究

利用液相合成法把掺元元素锂和铬同时均匀地掺入到主尖晶石相中,制得了颗粒细小、分布均匀及电化学性能优良的锂电池活性材料,利用X射线粉末衍射仪、Fourier变换红外分光光度计及电子显微镜对所合成成掺杂材料的结构进行表征,结果表明掺杂后晶胞发生收缩、Mn-O键增强、材料结构稳定、结晶性能好,电化学性能测试结果表明：混合掺杂锂铬元素可更好地改善材料的结构稳定性能,并获得较好初始容量及循环稳定性能。     

元素掺杂对镁基储氢合金电化学性能的影响

利用氢化燃烧合成复合高能球磨法制备镁基储氢电极合金Mg2NiH4,并对合金进行不同元素(Cr、Co、Nb、Ti和V)掺杂处理。使用X线衍射仪(XRD)和电化学工作站对材料结构性能进行表征,并考察不同元素掺杂对电极合金的结构和电化学性能的影响。结果表明:少量金属元素掺杂处理并没有改变合金的主相结构。元素掺杂降低了合金电极的最大放电容量和动力学性能,但是合金电极的电化学循环稳定性均得到不同程度的提高,其中Ti掺杂处理对于改善合金电极电化学循环性能最为明显。     

锂离子蓄电池正极材料Li_(1+δ)M_xV_(3-x)O_8的合成与电化学性能研究

锂钒氧化物Li1+δV3O8具有比容量高、循环寿命长、价格低等优点,因此它是一种非常有应用前景的锂离子蓄电池正极材料。作者采用传统的高温固相反应法合成了Ti、Fe、Ni、Co4种过渡金属元素部分取代Li1+δV3O8中钒的掺杂产物Li1+δMxV3-xO8,研究了不同掺杂元素及其掺杂量对材料电化学性能的影响。结果表明,掺杂Ti元素且掺杂量x≤0.1时,掺杂对材料的性能有一定的改善。掺杂没有提高其放电电压平台,降低了其比容量。但掺杂对其循环性能没有明显影响。综合考虑电化学性能,掺杂少量Ti比较适宜。     

掺杂型尖晶石Li_(1.05)Mg_xMn_(2-x)O_4的合成及性能研究

采用高温固相法制备了尖晶石正极材料L iMxMn2-xO4(X=0.04,0.06,0.08,0.10),并用XRD、SEM、ICP-AES、充放电测试等手段研究了其组成、结构、表观形貌和电化学性能。结果表明:该法制备的尖晶石正极材料L iMxMn2-xO4为单一尖晶石结构,粒径分布均匀,其比容量和循环性能较未掺杂尖晶石L iMn2O4有显著的提高。     

Fe(Ⅲ)和Al(Ⅲ)复合掺杂非晶态Ni(OH)_2的电极材料及性能

采用快速冷冻沉淀法首次成功制备出Fe(Ⅲ)和Al(Ⅲ)复合掺杂非晶态Ni(OH)2粉体材料。通过XRD、SAED、SEM、IR、Raman光谱及DSC-TG等对样品粉体的结构形态进行表征和分析,同时将样品合成电极材料并组装成MH/Ni模拟电池进行电化学性能测试,结果表明,样品材料内部结构缺陷多、无序性强、材料微粒大小比较均匀,并具有较好的分散性,结合水含量较多。将复合掺杂Fe(Ⅲ)5%和Al(Ⅲ)8%的样品材料制备镍正极并组装成MH/Ni模拟电池,在以80 mA·g-1恒流充电5.5 h,40 mA·g-1恒流放电,终止电压1.0 V的充放电制度下,进行充放电性能、比容量及其循环性能等电化学性能的测试,放电平台平稳,工作电压高达1.30 V,放电比容量达到357.6 mAh·g-1,且在电极过程中材料的稳定性增强、电化学阻抗较小,循环可逆性较好。     

Li1+xNiyMn2-x-yO4材料的结构特征及电化学性能的研究

采用溶液相合成工艺在主尖晶石相锰酸锂中，掺入镍并对掺镍材料 电化学循环稳定性能进行了研究。利用扫描电镜，粉末X射线衍射仪，红外光谱仪以及阻抗分析仪对材料形貌及结构特征进行研究。结果表明掺杂镍可提高材料的结构稳定性能，增大材料的颗粒尺寸，减少材料的比表面积并能提高材料的结晶性能。掺杂镍可增强Mn-O键弱化Li-O键以减小锂离子在尖晶石相中的迁移电阻。电化学循环稳定性能测试表明在尖晶石相材料中掺杂镍可改善材料的循环稳定性能。     

亚微米LiCu0.1Mn1.9O3.9F0.1电极活性材料的合成与性能

采用溶胶-凝胶法制备了F-和Cu2＋复合掺杂的LiCu0.1Mn1.9O3.9F0.1锂离子电池正极材料. XRD和SEM表征表明合成产物具有良好的尖晶石结构,样品粒度为亚微米级,且分布均匀;电化学性能测试结果表明,掺杂后样品的电化学阻抗较小,首次放电容量达112 mA×h/g,充放电循环50次后,容量保持率为89.1%,电极材料具有较好结构稳定性和电化学性能. 同时还探讨了LiCu0.1Mn1.9O3.9F0.1的合成及掺杂机理.     

亚微米LiCu0.1Mn1.9O3.9F0.1电极活性材料的合成与性能

采用溶胶-凝胶法制备了F-和Cu2 复合掺杂的LiCu0.1Mn1.9O3.9F0.1锂离子电池正极材料.XRD和SEM表征表明合成产物具有良好的尖晶石结构,样品粒度为亚微米级,且分布均匀;电化学性能测试结果表明,掺杂后样品的电化学阻抗较小,首次放电容量达112mA·h/g,充放电循环50次后,容量保持率为89.1%,电极材料具有较好结构稳定性和电化学性能.同时还探讨了LiCu0.1Mn1.9O3.9F0.1的合成及掺杂机理.     

Co~(3+)掺杂对LiNi_(0.5)Mn_(1.5)O_4导电性和倍率性能的影响研究

采用聚合物辅助法制备了Co~(3+)掺杂的LiNi_(0.5)Mn_(1.5)O_4正极材料,并用X射线衍射(XRD)分析了材料的结构。XRD图谱表明,Co~(3+)掺杂的材料仍具有Fd3m尖晶石结构。随着Co~(3+)掺杂量的增多,Li_xNi_(1-x)O杂质相逐渐消失。采用恒流充放电试验和电化学阻抗谱(EIS)研究了电化学性能。电化学测试结果表明,随着Co~(3+)掺杂量的增加,电荷转移电阻显著降低,同时锂离子扩散系数明显增强、倍率放电性能得到有效改善。     

Fe(Ⅲ)和Al(Ⅲ)复合掺杂非晶态Ni(OH)2的电极材料及性能

采用快速冷冻沉淀法首次成功制备出Fe(Ⅲ)和Al(Ⅲ)复合掺杂非晶态Ni(OH)₂粉体材料。通过XRD、SAED、SEM、IR、Raman光谱及DSC-TG等对样品粉体的结构形态进行表征和分析,同时将样品合成电极材料并组装成MH/Ni模拟电池进行电化学性能测试,结果表明,样品材料内部结构缺陷多、无序性强、材料微粒大小比较均匀,并具有较好的分散性,结合水含量较多。将复合掺杂Fe(Ⅲ) 5%和Al(Ⅲ) 8%的样品材料制备镍正极并组装成MH/Ni模拟电池,在以80 mA·g^-1恒流充电5.5 h,40 mA·g^-1恒流放电,终止电压1.0 V的充放电制度下,进行充放电性能、比容量及其循环性能等电化学性能的测试,放电平台平稳,工作电压高达1.30 V,放电比容量达到357.6 mAh·g^-1,且在电极过程中材料的稳定性增强、电化学阻抗较小,循环可逆性较好。     

尖晶石型锂锰氧化物的掺杂研究及其进展

综述了不同掺杂元素对尖晶石型锂锰氧化物电化学性质的影响。将掺杂元素按其掺入后的作用可以分为改善尖晶石锂锰氧化物循环性能的掺杂元素和提高其比容量的掺杂元素,并对尖晶石型锂锰氧掺杂研究工作进行了评述。     

负极材料Li4-xMg-Ti5-yCoyO12的合成及其电化学性能

以Mg(CH3 COO)2·4H2O,CO(CH3 COO)2-4H2O作为Mg2+和CO2+的掺杂源,以乙醇为溶剂,C6H15 NO3作为络合剂,CH3,COOLi·2H2O和Ti(OC4 H9)4作为原料,利用溶胶-凝胶法制备复合掺杂2种金属的Li4-xMg-Ti5-yCoyO12材料,并对其进行了X射线衍射(XR...     

溶胶-凝胶-微波法制备Li_(1+x)Mn_2O_y

以LiNO3和MnNO3为原料,溶胶凝胶法制备前驱体后,利用微波加热法,在750℃条件下保温20min,合成了Li1+xMn2Oy。利用XRD和FTIR分析手段,研究了锂掺杂量对材料结构的影响,利用恒电流充放电法,研究了材料的电化学性质。XRD和FTIR实验说明,适量的锂离子掺杂不改变材料的立方尖晶石结构;充放电实验显示,Li1.04Mn2O4.056是比较理想的电极材料,其首次放电比容量达到118.6mAh/g,5次循环后的容量损失率也仅为1.9%。     

Ultrasonic spray pyrolysis of nano crystalline spinel LiMn2O4 showing good cycling performance in the 3 V range

Spherical lithium manganese oxide spinel was synthesized by an ultrasonic spray pyrolysis method, and has been characterized using X-ray diffraction, scanning electron microscopy, transimission electron microscopy and electrochemical cycling at 3 V regions. The LiMn₂O₄ powders were composed of about 10 nm-sized primary particles. The delivered discharge capacity of the synthesized nano-material was 125 mAh g⁻¹ between 2.4 and 3.5 V and its retention was about 96% upon 50 cycling. From the high resolution transmission electron microscopic study, it was found that structural transition of the parent material did not occur even after the 50th electrochemical cycling on the 3 V region. It seems that the reversible structural change is possible for nanocrystalline LiMn₂O₄ as observed by the X-ray diffraction and transition electron microscopic observations.     

Niobium doping of Li1.2Mn0.54Ni0.13Co0.13O2 cathode materials with enhanced structural stability and electrochemical performance

Lithium-rich layered oxides with high energy density have been intensively investigated as advanced lithium-ion batteries cathode materials. However, capacity degradation and voltage decay caused by irreversible lattice oxygen loss and structural transformation during cycling restrict their application. Herein, we proposed a high valance cations Nb⁵⁺ doping strategy and synthesized a series of Li_1.2Mn_0.54-x/3Ni_0.13-x/3Co_0.13-x/3Nb_xO₂ (x = 0, 0.01, 0.02 and 0.03) cathode materials. The effects of Nb⁵⁺ doping on crystallographic structure and electrochemical property were systematically studied. In virtue of the large ionic radii and strengthened Nb–O bonds, the doped samples present commendable structural stability and expanded interlayer spacing for Li-ions migration, which ensures the upgraded cyclic stability and rate performance. In particular, the electrode with x = 0.02 delivers a discharge specific capacity of 265.8 mAh g^-1 at 0.2 C with decelerated voltage decay, while 86.9% capacity are remained after long-term cycles. Moreover, excellent discharge specific capacity of 153.4 mAh g⁻¹ is still attained at 5 C accompanied with enhanced Li-ion diffusion kinetics.     

碳包覆对LiNi_(0.5)Mn_(1.5)O_4电化学性能的影响

以蔗糖为碳源,采用溶液沉积-真空热解法制备了LiNi_(0.5)Mn_(1.5)O_4/C复合材料。用热重与差热分析、X射线衍射分析、扫描电镜分析及电化学测试等手段对LiNi_(0.5)Mn_(1.5)O_4/C的微观结构、表面形貌和电化学性能进行了研究。结果表明,蔗糖热分解后在LiNi_(0.5)Mn_(1.5)O_4颗粒的表面包覆形成了一层无定形碳。无定形碳可以有效阻止LiNi_(0.5)Mn_(1.5)O_4颗粒的聚集,增加电极的导电面积,降低电池极化,从而改善LiNi_(0.5)Mn_(1.5)O_4的电化学性能。与未包覆的LiNi_(0.5)Mn_(1.5)O_4粉末相比,LiNi_(0.5)Mn_(1.5)O_4/C复合材料具有更高的可逆容量、更稳定的循环性能和更好的倍率性能。0.2C放电时,LiNi_(0.5)Mn_(1.5)O_4/C复合材料的首次放电容量达到144.8mA.h.g-1,经60次循环后平均每次循环的容量损失仅为0.0081%。而1.0C和2.0C放电时,LiNi_(0.5)Mn_(1.5)O_4/C复合材料的首次放电容量分别保持在131.9mA.h.g-1和122.4mA.h.g-1。     

Temperature and Composition‐Induced Structural Transitions in Bi1−xLa(Pr)xFeO3 Ceramics

Bi_1?xLa_xFeO₃ and Bi_1?xPr_xFeO₃ ceramics of the compositions near the morphotropic phase boundary have been studied by X‐ray and neutron diffraction techniques and differential thermal analysis. The structural phases characterized by the long‐range polar, antipolar, and nonpolar ordering as well as the phase coexistence regions have been identified using the diffraction data depending on the dopant concentration and temperature. As a result of these studies the three phase region has been observed for the Pr‐doped compounds and the phase diagrams have been constructed. The detailed evolution of the structural parameters permitted to itemize the factors affecting the structural phase transitions and clarify the origin of the enhanced electromechanical properties in these materials. The performed structural analysis disclosed different character of the chemical bonds in the La‐ and Pr‐doped BiFeO₃ compounds. Further, the role of the rare‐earth ions in the covalency of the chemical bonds is discussed.     

Enhanced electrochemical performance of Li1.2(Ni0.17Co0.07Mn0.56)O2 via constructing double protection layers by facile phytic acid treatment

As one of the most promising cathode materials for next-generation of lithium-ion batteries, Li-rich Mn-based oxides are still hindered by inferior cycling properties and poor rate performance. Surface modification is proved to be feasible to tackle these problems. Herein, we chose phytic acid to construct spinel and Li₃PO₄ double protection layers on the Li_1.2(Ni_0.17Co_0.07Mn_0.56)O₂ cathode material via a simple synchronous approach. The 3 wt% phytic acid treated sample achieves markedly enhanced electrochemical performance, such as elevated initial Coulombic efficiency reaching 90.0%, increased capacity retention of 87.8% after 150 cycles at 1 C and alleviated average discharge voltage drop of 1.63 mV per cycle. These impressive electrochemical properties can be ascribed to the designed hierarchical interface, which not only can synergistically retain structural stability but also provide fast Li⁺ transport channels. Taken together, this work employs a facile and novel route to enhance the electrochemical performance of Li_1.2(Ni_0.17Co_0.07Mn_0.56)O₂, which may afford inspiration to the commercialization of Li-rich cathode materials.     

Structural,microstructural and electrochemical studies on LiMn2-x(GdAl)xO4 with spinel structure as cathode material for Li-ion batteries

Gd and Al co-doped LiMn_2-x(GdAl)_xO₄ (x?=?0, 0.01, 0.02, 0.03, 0.04 and 0.05) materials with spinel structure were synthesized by sol–gel method. Powder X-ray diffraction results confirm the formation of cubic spinel structure and average particle sizes are found to be between 80 and 110?nm from FE-SEM and TEM analysis. Decrease in peak potential difference as a function of doping in Cyclic Voltammetry results establishes enhancement in Li⁺ intercalation and de-intercalation. Electrochemical Impedance Spectroscopy (EIS) results showed that accumulation of charges on electrode has improved with doping over pristine samples. At a doping of x?=?0.02 charge transfer resistance values were found to be least. First cycle charge–discharge profiles for LiMn_1.96(GdAl)_0.02O₄ shows 139.2?mAh/g discharge capacity over other doped derivatives and pure LiMn₂O₄ (119.6?mAh/g) in aqueous Li₂SO₄ electrolyte. Doping of x?=?0.02 exhibit good cycling performance with only a total 4% capacity loss after 30 cycles.     

掺杂型尖晶石LiMn2-xMgxO3.97F0.03(x=0.05,0.1)的合成与性能研究

采用"熔融浸渍法"合成了Mg和F共掺杂的不同温度下的锂离子电池正极材料Li Mn2-xMgxO3.97F0.03(x=0.05,0.1);煅烧温度为700,750和800°C。通过XRD对样品进行测试,样品为单一尖晶石结构的物相;并用SEM测试,对样品进行了形貌研究。用所制备的材料作为正极材料组装了模拟锂离子电池;在室温下进行恒电流充-放电性能测试,测试条件为3.3~4.3 V和0.2mA/cm2电流密度。随着材料制备温度的升高,电池的初始放电容量有逐渐增加的趋势,但充放电循环的容量损失也逐渐增加;氟掺杂量一定,镁掺杂量较多时,对应温度下煅烧的样品的结晶程度较好,样品的电化学性能也较好。在800下°C样品Li Mn1.9Mg0.1O3.97F0.03初始容量高达108 mAh/g,60次充放电循环后,其容量保持率高达81%,具有优良的循环稳定性能。