添加Mg2+和PO43-非晶态氢氧化镍电极活性材料的性能

采用快速冷冻沉淀法制备添加PO43-和 Mg2+阴阳离子的非晶态氢氧化镍电极活性粉体材料,对其微结构和电化学性能进行研究。结果表明：添加5%PO43-（质量分数,下同）和2% Mg2+的非晶态样品粉体形貌为无规则,微结构无序性强,含有较多的结晶水,达31%。其作为MH-Ni电池正极活性材料,放电容量为347 mAh·g-1,中值电压达1.29 V,放电倍率对样品电极的放电比容量影响不大;充放电循环50次,容量衰减为3.5%,具有较好的稳定性;质子扩散系数达9.22×10-10 cm2·s-1,并具有较小电化学阻抗。与β-Ni(OH)2材料相比,其电化学性能明显提高。     

Al-Ni掺杂改性LiMn2O4正极材料合成及电化学性能

采用固相燃烧法快速合成了单晶多面体LiAl0.08Ni0.03Mn1.89O4 (LANMO)锂离子电池正极材料,其单晶颗粒暴露面包含{111}、{110}和{100}晶面。研究结果表明,LANMO材料为单相尖晶石型结构,属于Fd3m空间群,结晶性好,颗粒尺寸200-300 nm。在1 C和5 C倍率下LANMO的初始放电比容量分别为110.6和96 mAh·g-1,循环1000次后容量保持率都达到70%以上;在高温(55 ℃)1 C条件下,LANMO材料也具有114.2 mAh·g-1初始放电比容量,表现出优良的电化学性能。动力学性能测试表明,LANMO样品有较高的Li+离子扩散系数1.58×10-11 cm2·s-1和较低的表观活化能23.89 kJ?mol-1。Al-Ni协同改性提高了单晶多面体尖晶石型LiMn2O4材料的晶体结构稳定性,有效抑制了Jahn-Teller效应及降低Mn溶解和增加Li+扩散通道,增大了Li+扩散速率和电极可逆性,提升了其倍率性能和循环寿命。     

以NH4FePO4·H2O为前驱体微波法合成LiFePO4及其性能研究

用FeSO4、H3PO4、(NH4)2HPO4、NH3·H2O为原料合成NH4FePO4·H2O前驱体,再与LiCO3和蔗糖均匀混合,烘干后埋入活性炭粉中,在最大功率为800 W的家用微波炉中以320～640 W功率加热一定时间,获得LiFePO4.用扫描电镜和X射线衍射分析对NH4FePO4.H2O和LiFePO4的形貌结构进行了表征.研究了微波输入功率、加热时间对LiFePO4结构和电化学性能的影响.研究表明,在320 W下微波加热15 min得到的LiFePO4材料,具有良好的电化学性能.在0.05 C放电倍率下可达到156 mAh/g的放电比容量,在0.5 C放电倍率下仍可达到115 mAh/g的放电比容量.     

碳包覆镍掺杂LiFePO4正极材料的合成与电化学性能

采用水热法在160℃下合成了单相橄榄石结构的LiFePO4和LiFe0.95Ni0.05PO4。经550℃聚丙稀裂解碳包覆后得到LiFePO4／C的颗粒尺寸在200nm左右，碳包覆镍掺杂LiFe0.95Ni0.05PO4/C的颗粒尺寸在100nm以下。电化学测试结果表明：LiFePO4/C和LiFe0.95PO4／C的0．1C首次充放电可逆容量分别达到154mAh·g^-1和149mAh·g^-1，但掺镍的LiFe0.95Ni0．05PO4／C具有更优异的大电流充放电循环特性，0．5C和1C充放电100次后的放电容量分别达到147mAb·g^-1和134mAh·g^-1。     

钛掺杂LiFePO4的还原插锂合成及其性能

用共沉淀法制备掺钛前驱体FePO4·2H2O,对FePO4·2H2O经常温还原插锂合成LiFePO4的前驱混合物,后经热处理得橄榄石型LiFePO4;用SEM,XRD和恒流充放电等对样品进行表征,考察Ti掺杂和合成温度对LiFePO4的物理和电化学性能的影响.研究结果表明,在600 ℃时合成的Ti掺杂样品具有优异的电化学性能,该样品在0.1C,1C和2C倍率下的首次放电比容量分别为150,130和125 mA·h/g,循环40次后的放电比容量均无衰减.     

Ni2+替代对LiFePO4正极材料电化学性能的影响

利用炭热还原法合成了橄榄石型LiFe1-xNixPO4/C (x=0.0,0.1,0.3,0.5) 正极材料,并系统研究了Ni2+替代对材料电化学性能的影响。充放电循环、循环伏安和交流阻抗测试,结果表明Ni2+替代部分Fe2+可以显著改善LiFePO4材料的电化学性能。在0.2 C (1 C=170.0 mA·g-1)电流密度下,LiFe0.9Ni0.1PO4/C的放电比容量达到160 mAh·g-1。LiFe1-xNixPO4/C电化学性能的改善归因于材料电导率的提高和电荷传输电阻的降低。利用第一性原理对LiFe1-xNixPO4/C的电子结构进行了研究,结果表明Ni2+的铁位替代能够提高体系的电子电导性。LiFe0.875Ni0.125PO4的结构最稳定,带隙最小,导电性能最好     

化学计量比对贮氢合金电极特性的影响

研究了化学计量比对AB4.8~AB5.2贮氢合金电化学性能的影响。结果表明:在本实验研究范围内,当x=0.1时,贮氢合金电极的0.2C,1C和5C放电容量、高倍率放电特性及3C循环寿命分别达到324mAh·g-1,301mAh·g-1,263mAh·g-1,0.81和530次。此外,化学计量比对贮氢合金的活化性能和温度特性均有较大的影响,当x分别为–0.2,–0.1,0.0,0.1和0.2时,贮氢合金电极在0.2C充放电的条件下活化次数分别为3次、4次、7次、5次和6次,且随着x的增大,贮氢电极的高温(45℃,1C)和常温(25℃,1C)放电效率下降,低温(–18℃,1C)放电效率则有增大的趋势。从合金活化性能、大电流充放电特性和循环稳定性来看,x=0.1时(AB5.1),能得到具有较佳的电化学性能的贮氢材料。     

熔融盐法合成高密度锂离子电池正极材料LiNi0.8Co0.2-xTixO2

利用具有低共熔组成的LiOH-LiNO3混合锂盐体系,与高密度前驱体掺杂Co的Ni(OH)2,TiO2粉末混合,经3阶段温度烧结制备出高密度Co-Ti共掺杂的锂离子电池正极材料LiNi0.8Co0.2-xTixO2（0≤x≤0.1）。XRD分析表明,合成的LiNi0.8Co0.2-xTixO2具有规整的层状α-NaFeO2结构。LiNi0.8Co0.2-xTixO2颗粒均匀,平均粒度为1~5 μm,随掺Ti量的增加而减小,LiNi0.8Co0.15Ti 0.05O2的振实密度达3.17 g·cm-3。电性能测试表明,在0.2 C放电倍率和3.0~4.3 V的电压范围内,LiNi0.8Co0.15Ti0.05O2首次放电比容量达169 mAh·g-1,且具有良好的循环性能和高倍率放电性能。     

Ti4＋掺杂对Li2FeSiO4／C电化学性能的影响

用溶胶-凝胶法制备Ti4＋掺杂的Li2FeSiO4／C正极材料。用XRD、HRTEM和电化学方法研究了该材料的结构、形貌和电化学性能。结果表明,掺杂适量的Ti4＋不会改变Li2FeSiO4／C的正交晶系结构,可以稳定材料的结构,改善高倍率充放电性能。在室温下,Li2Fe0.97Ti0.03SiO4/C以0．1c倍率放电的首次放电比容量为149．1mA·h／g,20次循环后放电比容量为127．3mA·h／g,且不同倍率下的电化学性能明显优于未掺杂的Li2FeSiO4／C。交流阻抗谱研究表明,适量的Ti4＋掺杂,减小了正极材料在充放电过程中的电荷传递电阻,增加了材料的电子电导率,改善了材料的电化学性能。     

固相法合成原位碳包覆LiFePO4复合正极材料及其性能

以LiH2PO4和FeC2O4.2H2O为原料,聚乙烯醇为碳源,通过机械化学活化辅助固相法合成原位碳包覆的LiFePO4材料;考察合成温度对LiFePO4/C材料晶体结构、物理和电化学性能的影响。结果表明:700℃下处理的产物结晶良好、分布均匀、颗粒细小;在最佳的热处理条件下,热解碳在LiFePO4颗粒表面形成了良好的纳米导电层,LiFePO4/C材料在0.1C、0.5C、1C和2C倍率下放电比容量分别为155.7、150.1、140.1和130 mA.h/g,且材料在0.1～2C范围内充放电都有很平稳的平台,极化小,并具有较高的高倍率(2C)放电比容量和较好的循环性能。     

The surface morphology of Li metal electrode

Surface morphological changes of Li powder compacted electrodes were investigated and compared with extruded Li foil electrodes during the dissolution (discharge)/deposition (charge) process. The area of dendrite growing surfaces was reduced remarkably for Li powder compacted electrodes. Impedance measurements showed that Li compacted powder electrodes had a lower resistance than Li foil electrodes. This is presumed to be related with resistance reduction due to increasing ion conductivity in the SEI (solid electrolyte interface) formed on the surface along with the increase of the reaction area for the powder electrode.     

锂蓄电池正极材料LiV3O8的合成和充放电性能

采用一种液相反应的方法合成LiV3O8化合物 ,首先由NH3·H2 O ,LiOH与V2 O5反应合成含有Li和V的反应前驱产物 ,然后在 180℃的真空环境中进行干燥处理 ,最后将此物质在 5 80℃温度下煅烧成最终产物。采用热重分析试验分析了反应的机理。X射线衍射结果显示得到的物质与用传统合成方法得到的LiV3O8化合物的结构相比 ,在 (10 0 )方向上的衍射峰强度降低很多。在室温、恒电流为 3A/m2 条件下进行充放电试验 ,在 1.8～4.0V范围内 ,首次放电容量达到 2 30Ah/kg ,15周后仍能达到 2 10Ah/kg。     

锂钛氧嵌锂负极材料的研究进展

目前锂离子电池主要受制于安全性能、大功率性能和制造成本,新型高性能锂钛氧基负极材料有望解决这些问题,在动力型和储能型锂离子电池中获得应用。本文对Li4Ti5O12、Li Ti2O4、Li2Ti3O7、Li2Ti6O13等系列锂钛氧嵌锂化合物的晶体结构、电化学性能、制备方法、化学改性、应用研究等方面的重要成果进行了较全面的阐述,并指出了未来研究发展方向。     

Improving the electrochemical performance of LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/graphite batteries using LiF additive during fabrication

LiMn2O4/graphite batteries using LiF additive were fabricated and their electrochemical performance including discharge,cycling and storage performances were tested and compared with LiF-free LiMn2O4/graphite batteries.The LiMn2O4/graphite battery with LiF added shows better capacity (107.5 mAh/g),cycling performance (capacity retention ratio of 93% after 100 cycles),and capacity recovery ratio (98.1%) than the LiF-free battery.The improvement in electrochemical performance of the LiF-added LiMn2O4/graphite...     

Heat treatment effect on electrochemical properties of spinel Li4Ti5O12

Anode material Li4Ti5O12 was prepared at 800℃ by a solid-state reaction, followed by heat-treatment at 600℃ for different times （0, 2, 8, and 12 h）. The effects of heat-treatment time on the particle morphology, rate-capability, and electrode kinetic process of the Li4Ti5O12 electrode, and on the lithium ion diffusion coefficient inside the Li4Ti5O12 electrode were investigated. Proper heat treatment could smoothen the particle surface of Li4Ti5O12 particles and increase the rate-capability of the electrode. Overlong heat treatment might cause particle aggregation and hence result in a poor electrode kinetic process. A sample with 8 h of heat treatment showed the best rate-capability and the lowest electrode reaction resistance. Heat treatment for 2-8 h does not significantly change the lithium ion diffusion coefficient inside the Li4Ti5O12 electrode, whereas, 12-h treatment results in a lower lithium ion diffusion coefficient.     

一种新型的锂离子电池正极材料——LiFePO4

介绍了1种新型的锂离子电池正极活性材料LiFePO4并解释了材料的结构特征和电化学过程。LiFePO4具有较高的比容量和良好的循环稳定性等优良的电化学性能,但是目前还存在着制约容量释放的锂离子扩散系数小以及材料导电性能不太好等问题。在回顾该材料研究状态的基础上,说明了只要通过选取适当的制备工艺和进行合适的表面改性可以制备出具有优良电化学性能的LiFePO4粉体。这种粉体具有环境相容性、便宜以及资源丰富等诸多优点,是1种颇具潜力的锂离子电池正极替代材料。     

化学沉淀法制备磷酸铁锂正极材料的研究进展

磷酸铁锂(LiFePO4)是一种非常有应用前景的锂离子电池正极材料,化学沉淀法是制备这种材料的理想方法。本文从不同的前驱体合成路线角度出发,针对金属离子掺杂和表面碳包覆这两种改性手段,对化学沉淀法制备LiFePO4正极材料国内外的研究进行综述,对当前研究过程中存在的问题和未来的研究方向进行了评论和展望,为LiFePO4正极材料的研究提供了参考。     

锂产业技术经济综合分析

本文对锂的资源概况、锂的技术概况、锂的产业概况、锂的市场概况等方面进行了综述,希望对锂产业技术经济等方面有一个全面了解。     

Electrochemical behavior of Li+, Mg2+, Na+ and K+ in LiFePO4/ FePO4 structures

Besides Li⁺ and Mg²⁺, the electrochemical behavior of Na⁺ and K⁺ in LiFePO₄/ FePO₄ structures was studied since they naturally coexist with Li⁺ and Mg²⁺ in brine. The cyclic voltammogram (CV) results indicated that Na⁺ exhibits some reversibility in LiFePO₄/FePO₄ structures. Its reduction peak appears at ?0.511 V, more negative than that of Li⁺ (?0.197 V), meaning that a relatively positive potential is beneficial for decreasing Na⁺ insertion. The reduction peak of K⁺ could not be found clearly, indicating that K⁺ is difficult to insert into the FePO₄ structure. Furthermore, technical experiments using real brine with a super high Mg/Li ratio (493) at a cell voltage of 0.7V showed that the final extracted capacity of Li⁺, Mg²⁺ and Na⁺ that can be attained in 1 g LiFePO₄ is 24.1 mg, 7.32 mg and 4.61 mg, respectively. The Mg/Li ratio can be reduced to 0.30 from 493, and the Na/Li ratio to 0.19 from 16.7, which proves that, even in super high Mg/Li ratio brine, if a cell voltage is appropriately controlled, it is possible to separate Li⁺ and other impurities effectively.     

Synthesis and physicochemical properties of LiLa0.01Mnt.99O3.99F0.01 cathode materials for lithium ion batteries

Spinel lithium manganese oxide cathode materials were synthesized using the ultrasonic-assisted sol-gel method.The synthesized samples were investigated by differential thermal analysis (DTA) and thermogravimetry (TG),powder X-ray diffraction (XRD),scanning electron microscopy (SEM),cyclic voltammetry (CV),and the charge-discharge test.TG-DTA shows that significant mass loss occurs in two temperature regions during the synthesis of LiLa0.01Mn1.99O3.99F0.01.XRD data indicate that all samples exhibit the same pure spinel phase,and LiLa0.01Mn1.99O3.99F0.01 and LiLa0.01Mn1.99O4 samples have a better crystallinity than LiMn2O4. SEM images indicate that LiLa0.01Mn1.99O3.99F0.01 has a slightly smaller particle size and a more regular morphology structure with narrow size distribution.The charge-discharge test reveals that the initial capacities of LiMn2O4,LiLa0.01Mn1.99O4,and LiLa0.01Mn1.99O3.99F0.01 are 130,123,and 126 mAh·g-1,respectively,and the capacity retention rates of the initial value,after 50 cycles,are 84.8%,92.3%,and 92.1%,respectively.The electrode coulomb efficiency and CV reveal that the electrode synthesized by the ultrasonic-assistexi sol-gel (UASG) method has a better reversibility than the electrode synthesized by the sol-gel method.