球磨对磷酸铁锂正极材料性能的影响

采用高温固相合成法制备锂离子正极材料磷酸铁锂,在合成过程中分别采用湿法球磨和干法球磨,讨论了球磨时间对合成磷酸铁锂电化学性能的影响。用扫描电镜对合成材料进行表征,并对磷酸铁锂正极材料进行电化学性能测试。结果表明,相对于干法球磨,湿法球磨制备的磷酸铁锂样品具有更好的电化学性能。湿法球磨10 h所得的材料电化学性能最好,0.1 C下首次放电比容量为114 mA·h/g。     

镁离子掺杂磷酸铁锂的制备及其电化学性能

通过简单水热反应制备磷酸铁锂前驱体,并结合后期热处理过程制备了镁离子掺杂碳包覆的磷酸铁锂正极材料。利用X射线衍射（XRD）、扫描电镜（SEM）和透射电镜（TEM）等表征了镁离子掺杂磷酸铁锂的成分、形貌和结构。元素分布结果证明镁离子均匀掺杂在磷酸铁锂材料中。通过恒流充放电和循环伏安、交流阻抗等方法对材料的电化学性能进行测试。结果表明,镁离子掺杂后的磷酸铁锂材料具有较高的放电比容量（0.1C放电比容量为 160.1 mA·h/g）和优越的倍率性能（20C放电比容量为77.2 mA·h/g）,同时减小了极化和电荷迁移电阻。这条合成路线是提高水热法制备磷酸铁锂正极材料电化学性能的有效方法。     

磷酸铁锂正极材料的制备及性能强化研究进展

橄榄石型磷酸铁锂是目前应用十分广泛的锂离子电池正极材料之一,具有成本低、安全性高、环境友好、循环寿命长和工作电压稳定的特点。近年来,随着CTP技术、刀片电池技术等取得的突破性进展,磷酸铁锂的商业化程度得到了大幅提高。但磷酸铁锂存在电子导电性较差和离子扩散系数低的缺陷,严重限制了锂离子电池的电化学容量,因此开展磷酸铁锂制备工艺和性能强化研究对磷酸铁锂的性能提升具有重要意义。对比了磷酸铁锂电池与其他正极材料锂离子电池的性能差异和发展现状,系统总结了磷酸铁锂正极材料制备与强化的改性方法及相关研究进展与挑战,并提出了未来的发展方向与研究思路。     

我国磷酸铁锂改性技术的进展与应用前景

介绍了新型锂离子电池正极材料磷酸铁锂制备与改性技术,特别介绍了我国磷酸铁锂纳米化、离子掺杂、碳包覆等改性技术和水热合成、溶胶—凝胶法等磷酸铁锂制备技术,阐明了改性技术有利于进一步改进电池电化学性能,以适应混合动力汽车与电动汽车动力电池和风能、太阳能储能设备等对锂离子电池要求。基于磷酸铁锂正极材料发展前景,提出了我国传统磷化工行业调整产品结构,对接新能源材料的发展思路。     

采用氧化控制结晶-碳热还原制备球形磷酸铁锂的方法

本发明公开了属于能源材料制备技术领域的一种采用氧化控制结晶一碳热还原制备球形磷酸铁锂的方法。其制备方法是,先将二价铁盐与磷酸混合水溶液、氨水溶液和氧化剂反应,通过氧化控制结晶过程合成球形水合磷酸铁前驱体,洗涤、干燥、预烧脱水后,再与碳酸锂、碳源均匀混合,在惰性或还原气氛保护下,经过高温碳热还原得到磷酸铁锂。     

磷酸铁锂正极材料的合成与表征技术

橄榄石型磷酸铁锂正极材料具有原料来源丰富、价廉、无毒、环境友好、理论容量高、热稳定性和循环性能好等特点,有望成为新一代锂离子电池正极材料.综述了高温固相反应法、溶胶-凝胶法、微波合成法、水热合成法和共沉淀法制备磷酸铁锂的方法.并详细说明了磷酸铁锂的红外光谱、扫描电镜、X射线衍射和电化学性能研究等表征技术.     

反应溶液浓度对合成磷酸铁锂粉体形貌的影响

磷酸铁锂作为锂离子电池的正极材料,安全性能与循环寿命极佳.实验研究了采用微波水热法合成磷酸铁锂时,反应溶液浓度对磷酸铁锂形貌的影响,并对磷酸铁锂的物相组成、形貌以及晶体结构进行了分析.实验结果表明,采用微波溶剂热合成磷酸铁锂,温度在180℃时,物相较纯;且随着反应溶液浓度的增加,粉体团聚现象减弱,晶粒棱角更加清晰,结晶...     

前驱体磷酸铁的制备及其对磷酸铁锂电化学性能的影响

以Fe3+为铁源,采用均相沉淀法制备前驱体磷酸铁,通过碳热还原法制得磷酸铁锂正极材料,研究其电化学性能。结果表明,以优化条件下所得磷酸铁为前驱体制备的磷酸铁锂,在0.1 C充放电倍率下,其首轮放电比容量达154 mA.h/g,充电比容量为156 mA.h/g,首轮充放电效率达98.9%,循环倍率性能优良。     

掺杂改性LiFePO_4正极材料制备及表征

采用微波热合法制备了掺杂LiFePO4锂电池用正极材料。通过XRD、SEM表征了材料的晶体结构和形貌,采用恒电流充放电法研究了材料的电化学性能。XRD结果表明,掺杂后的材料晶相为橄榄石型磷酸铁锂;SEM测试结果表明,加热时间延长促使材料颗粒团聚长大,且结晶完整,颗粒分布均匀。对电池的电化学测试表明,制备的掺杂LiFePO4材料表现出优良倍率性能和循环稳定性,充放电比容量分别为131.7 mAh/g和123.8 mAh/g,10次循环后比容量没有明显衰减。     

锂离子电池正极材料磷酸铁锂的研究进展

橄榄石结构的LiFePO4因为其有高比容量、低成本、环保等优点而被认为最有前景的锂离子电池正极材料,但是其电导率和锂离子扩散速率比较慢.本文综迷了磷酸铁锂作为锂离子电池正极材料在应用方面的优缺点,近几年来磷酸铁锂常用的制备方法,各种制备方法的优缺点以及对磷酸铁锂在电化学方面的改性研究,并指出今后研究的重点是对磷酸铁锂在...     

LiFePO4锂离子电池的数值模拟：正极材料颗粒粒径的影响

LiFePO₄（LFP）作为正极材料时,锂离子电池安全性高且循环寿命长,是目前应用最广泛的正极材料,但其电池倍率性能较差。提升倍率性能的有效手段之一是将LFP材料颗粒纳米化,但材料纳米化过程中颗粒粒径减小对于锂离子电池充放电过程中锂在固液相的扩散及表面电化学反应的影响机制仍缺乏清晰的认识。采用锂离子电池的准二维模型,模拟锂离子电池的放电过程,定量研究了正极材料颗粒粒径对锂离子电池倍率性能的影响,分析了固液相扩散速率与电化学反应速率受LFP材料颗粒粒径的影响程度。研究结果表明：电极材料中固相扩散阻力是锂离子电池电化学性能的主要限制因素。小粒径的LFP作为正极材料时,电极材料内的金属锂的迁移路径较短,同时颗粒与电解液的接触面积增加,界面的电化学反应速率较快,放电倍率对于锂离子电池性能影响较小;大粒径的LFP作为正极材料时,电极材料内的金属锂扩散路径的增加和较高的固相扩散阻力限制了界面的电化学反应速率,导致锂离子电池的倍率性能显著降低。LFP材料的纳米化可以有效减小固相扩散阻力,提升锂离子电池的倍率性能。     

锂离子电池异构建模及内部传质机理探究：粒径分布的影响

锂离子电池是目前应用较广的储能设备,具有能量密度高、使用寿命长等特点。随着锂离子电池正极材料实际能量密度接近理论值,电池组装工艺参数的优化成了提升其性能的重要途径,其中电极颗粒粒径及分布是十分重要的参数。因此,本文针对石墨-LiFePO₄体系锂离子电池,利用异构模型构建单粒径和双粒径电极的几何结构,再结合Newman模型模拟其放电过程,定量研究了正极材料粒径分布对锂离子电池性能的影响,探究了存在粒径分布的电极中不同粒径的颗粒在充放电过程的作用机制。模拟结果表明,粒径的减小可以减小固相扩散系数对电池性能的影响,但会增加液相扩散阻力;而粒径的分布可以促进锂离子在电解液中的扩散,提高小粒径颗粒的锂嵌入量,但会引起极化增大,导致大颗粒的锂嵌入量降低。粒径分布宽度越大,总体粒度越大,锂离子电池的能量密度越小。选择合适的粒径分布宽度,适当减小总体粒度的大小,能有效提升电极的能量密度。研究结果对于锂离子电池电极活性材料颗粒粒径分布的选择提供了有益的基础知识和指导。     

Comparative study on the electrochemical performance of LiFePO4 cathodes fabricated by low temperature 3D printing,direct ink writing and conventional roller coating process

Electrodes for lithium-ion batteries can be fabricated in many ways including conventional roller coating and 3D printing. Roller coating is a standardized process in current lithium-ion battery industry, while 3D printing has been used to fabricate three-dimensional (3D) unconventional electrodes with tailored geometries. Our previous study proposed a low temperature 3D printing process to fabricate highly-porous LiFePO₄ (LFP) electrodes. However, there still lack a study on the comparison of electrochemical performance of LFP electrodes fabricated via the three different fabrication processes including low temperature direct writing-based 3D printing (LTDW), room temperature direct ink writing (DIW) and roller coating process. In this study, we fabricated LFP cathodes using these three fabrication processes from LFP inks with different solid contents. By varying the solid content, LFP electrodes with different geometries (including width and thickness), morphologies and porous microstructures were obtained via LTDW and DIW. Mercury porosimetry was performed to examine the differences of the three types of LFP electrodes in porous microstructures. Electrochemical performance including charge/discharge, rate performance, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) of the three types of electrodes were measured and compared. Results showed that electrode fabrication processes have important effects on the electrochemical performance of LFP electrodes depending on the ink solid content. LTDW-fabricated electrodes had the best performance at high solid content (≥0.467 g/mL) and conventional roller coated electrodes performed better at low solid content (≤0.356 g/mL). Relationships between ink solid content, fabrication process, resulting porous microstructures and electrochemical performance were discussed. Finally, an optimal specific capacity of ∼82 mAh.g-1 @ 10C was achieved at a solid content of 0.467 g/mL by LTDW process.     

Aqueous processing based novel composite electrode for Li-ion batteries using an environmentally benign binder

Along with the high energy density and safer battery materials, easy and environment benign electrode processing is also one of the major concerns for the battery manufacturing industries. Therefore, herein, water-based electrode processing is used which reduces manufacturing cost and makes easy and cost-effective recycling of discarded batteries. In addition, the increasing use of Li-ion batteries from portable electronics to electric vehicles has imposed a threat to the environment due to hazardous materials used. The present study also focuses on the replacement of polyvinylidene difluoride (PVDF) non-conducting binder dissolves in toxic solvent N-methyl 2-pyrrolidone with water-soluble poly (3,4-ethylene dioxythiophene): poly (styrene sulfonate) (PEDOT:PSS) conducting binder. The entire study is performed on the synergistic effect of PEDOT:PSS with multi-walled carbon nanotubes (MWCNTs or MC) and carbon black (CB) on Li-ion battery performance using LiFePO₄ cathode active material. The discharge capacities were found 144 mAh g⁻¹ and 160 mAh g⁻¹ at 0.1C for composite electrodes LFP/CB-9P and LFP/MC-9P, respectively having 9 wt% PEDOT:PSS. Whereas the composite electrodes LFP/CB-10PV and LFP/MC-10PV having 10 wt% PVDF binder show only capacities 117 mAh g⁻¹ and 134 mAh g⁻¹, respectively. The composite electrode LFP/MC-9P shows the highest capacities up to 20C rate and maximum retention capacity of 84% at 5C after 500 cycles among all samples studied. Whereas electrodes prepared with PVDF binder could not perform well at more than 5C current rate, capacity retention is also found nearly 0% after 500 cycles. Therefore, superior results of PEDOT:PSS and MWCNTs with LiFePO₄ propose an environmentally benign composite electrode of next generation Li-ion batteries for electric vehicles.     

LiFePO4锂离子动力电池45℃容量衰减机理

以电动汽车的方型LiFePO₄/石墨动力实验电池为研究对象,探究其在45℃恒温箱下1C充放电循环的失效机理。通过对电池进行解剖,系统分析了电池循环前后正负极片的厚度、形貌、结构和克容量的变化。随着电池在45℃高温下循环,电解液分解以及Fe溶出损失、SEI膜再生长,消耗大量的活性锂,交流内阻增加导致电化学极化增大,活性锂消耗引起负极容量损失为6.7%,负极结构变化造成的容量损失为22.64%。结果表明石墨负极动力学性能的衰减是电池失效的主要因素。     

Design and performance of an optimized electrical diffusion battery

Standard aerosol instruments to measure particle size distributions in the ultrafine size range are large and heavy. We built a small electrical diffusion battery, which can be carried in a backpack and thus makes size-resolved short-term personal aerosol exposition measurements possible. The instrument was designed for maximal measurable particle size range and long maintenance intervals. The optimum number of stages for the diffusion battery was found with a Monte-Carlo simulation. To assess the instrument's performance, we compared size distributions measured with the electrical diffusion battery to those obtained with standard aerosol instruments (the scanning mobility particle sizer and the fast mobility particle sizer of TSI Inc.). In general, the readings of the electrical diffusion battery and those of standard instruments agree well (to within 10–20%).     

Electrochemical performance of in situ LiFePO4 modified by N-doped graphene for Li-ion batteries

LiFePO₄ modified by N-doped graphene (NG) with a three-dimensional conductive network structure was synthesized via a one-step in situ hydrothermal method. The effects of N amount of NG on the phase structure, morphology, and electrochemical properties of LiFePO₄ are investigated in this study. X-ray diffraction (XRD) results show that doping suitable N amounts in NG do not alter the crystal structure of LiFePO_4, and scanning electron microscopy (SEM) images show that NG can slightly reduce the particle size of LiFePO₄. The high-resolution transmission electron microscopy (HRTEM) results show that the LiFePO₄ particles are well covered and connected by NG. The electrochemical performance confirms that LiFePO₄ modified by 20% N-doped graphene (named LFP/NG-4) displays a perfect specific capacity of 166.6 mAh·g^?1 at a rate of 0.2C and can reach 125 mAh·g^?1 at a rate of 5 C. Electrochemical impedance spectroscopy (EIS) results illustrate that the charge transfer resistance value of the LFP/NG-4 composite is only 58.6 Ω, which is very low compared with LiFePO₄. Cyclic voltammetry (CV) tests indicate that the addition of 20% N-doped graphene can effectively reduce electrode polarization and improve reversibility. The LFP/NG-4 composite with a three-dimensional conductive network structure can be regarded as a promising cathode material for Li-ion batteries.     

Enhanced electrochemical performance of garnet-based solid-state lithium metal battery with modified anodic and cathodic interfaces

Due to high ionic conductivity and wide electrochemical window, the garnet solid electrolyte is considered as the most promising candidate electrolyte for solid-state lithium metal batteries. However, the high contact impedance between metallic lithium and the garnet solid electrolyte surface seriously hampers its further application. In this work, a Li-(ZnO)_x anode is prepared by the reaction of zinc oxide with metallic lithium and in situ coated on the surface of Li_6.8La₃Zr_1.8Ta_0.2O₁₂(LLZTO). The anode can be perfectly bound to the surface of LLZTO solid electrolyte, and the anode/electrolyte interfacial resistance was reduced from 2319 to 33.75 Ω·cm². The Li-(ZnO)_0.15|LLZTO|Li-(ZnO)_0.15 symmetric battery exhibits a stable Li striping/plating process during charge-discharging at a constant current density of 0.1 mA·cm^-2 for 100 h at room temperature. Moreover, a Li-(ZnO)_0.15|LLZTO-SPE|LFP full battery, comprised of a polyethylene oxide-based solid polymer electrolyte (SPE) film as an interlayer between LiFePO₄ (LFP) cathode and LLZTO solid electrolyte, presents an excellent performance at 60 ℃. The discharge capacity of the full battery reaches 140 mA·h·g^-1 at 0.1 C and the capacity attenuation is less than 3% after 50 cycles.     

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。     

球形磷酸铁锂材料的制备及其18650电池的测试

采用高能球磨和喷雾干燥法制备了球形磷酸铁锂材料LFP-1,并制作18650实装电池,测试电极片的压实密度,同时选择一种商业化磷酸铁锂材料LFP-2作为对比。测试结果显示,2种LFP材料均由平均粒径为300~500 nm的一次颗粒组成,比表面积为13~15 m²/g,碳质量分数为1.5%左右。通过CR2032纽扣型电池充放电测试表明,在0.2C时,LFP-1的比放电容量约为165 mA·h/g,与商业化磷酸铁锂材料LFP-2相近。制备18650电池的结果表明,商业化磷酸铁锂LFP-2材料制备的电极片的最高压实密度可以达到2.52 g/cm³,显著高于实验室制得的磷酸铁锂材料LFP-1的最高压实密度2.25 g/cm³,这可能与材料的颗粒粒度分布不同有关。