LiFePO_4/PANI复合材料的制备及电化学性能

通过原位聚合法,制备一系列的导电聚合物(Polyaniline,PANI)的LiFePO4/PANI复合材料。单用傅里叶红外光谱(FTIR)和高分辨透射电镜(HRTEM)表征PANI与LiFePO4之间的相互作用以及PANI对LiFePO4的包覆状况。采用四探针、电化学阻抗谱及恒电流充放电测试复合材料的电导率及其电化学性能。结果表明:当PANI含量为6.75%(质量分数)时,能在LiFePO4的表面形成均匀的包覆层,试样具有最佳的电化学性能,电荷转移电阻较小,交换电流较大,C/12倍率下首次放电容量为151.97mA·h/g,并具有较好的循环性能及倍率性能。     

一步固相合成Nb掺杂LiFePO4/C及其电化学性能

用廉价的三价铁离子化合物为铁源,以聚丙烯为还原剂和碳源,在一步固相法合成Nb掺杂LiFePO4的同时实现颗粒表面碳导电膜的原位包覆。结果表明:一步固相合成的Nb掺杂LiFePO4/C具有完整的橄榄石型LiFePO4晶体结构和近似球状的颗粒形貌,颗粒尺寸为100~500 nm;聚丙烯分解后在颗粒表面和颗粒之间形成连通的网络状碳膜。电化学测试结果表明,当Nb的掺入量为1.0%(摩尔分数)时具有最好的倍率放电性能和循环性能;在2C充放电时具有130 mA.h/g的放电容量,循环100次容量无衰减,在4C充放电时仍具有105 mA.h/g的放电容量。     

锂离子电池正极材料LiFePO_4的水热合成及其性能

以H_3PO_4、FeSO_4·7H_2O和LiOH·H_2O为原料,石墨烯为碳源,采用水热合成法制备锂离子电池正极材料LiFePO_4,考察水热反应温度和后期的焙烧温度等工艺条件对合成产物结构、形貌及电化学性能的影响。结果表明,水热反应温度和焙烧温度对合成的LiFePO_4形貌结构与电化学性能均有显著的影响,石墨烯的掺入可明显改善材料的电化学性能。当水热温度为150℃、焙烧温度为700℃、石墨烯的掺入量为3%(质量分数)时,制备的样品具有相对较好的电化学性能,0.1C倍率下首次放电比容量为134.0 mA·h/g,经过20次循环后的比容量为131.3 mA·h/g,容量衰减率仅为2.02%。     

热解碳结构对LiFePO_4/C复合电极性能的影响

分别以5种含碳有机物为碳源,通过固相热裂解法制备了5种LiFePO_4/C复合正极粉体材料,利用XRD和拉曼光谱表征了复合粉体中碳的结构.复合材料含有单一的磷酸铁锂相,裂解碳以无定型形式存在.不同裂解碳D、G拉曼峰的强度有所不同,其比值R反映了石墨化程度的强弱.对于石墨化程度高的LiFePO_4/C复合正极材料,其电子电导性能高,反映在电池容量性质上就是电池容量高.比较不同有机前驱体对复合正极材料的作用效果,聚乙烯醇是较佳的选择.     

合成温度对LiFePO_4/C复合材料电化学性能的影响

以FePO4为铁源、Li2CO3为锂源、聚丙烯为还原剂和碳源,采用一步固相法合成原位碳包覆磷酸亚铁锂(LiFePO4/C)复合材料,研究合成温度对材料LiFePO4/C复合材料电化学性能的影响。采用X射线衍射、扫描电镜和拉曼光谱技术对合成产物的晶体结构、表面形貌和碳结构进行表征,通过电化学阻抗谱(EIS)和充放电测试对材料的电化学性能进行测试和分析。结果表明:在600～750℃温度范围内都可合成纯LiFePO4/C复合材料,随着合成温度的升高,材料颗粒尺寸和石墨化程度都将增大;600℃保温8h合成的材料颗粒尺寸为100～500nm,其1C放电比容量达到144.2mA·h/g,5C放电比容量达到119mA·h/g。     

固相法合成LiFePO4/C正极材料的电化学性能

以廉价原材料FeSO4·7H2O为铁源,以蔗糖为碳源,采用固相法合成了锂离子电池正极材料--LiFePO4/C复合材料.用X射线衍射(XRD)、扫描电镜(SEM)和电化学测试技术对不同铁源合成的LiFePO4/C复合材料的结构、形貌和电化学性能进行研究.结果表明:合成的样品具有均一的橄榄石型结构,以FeSO4·7H2O为铁源合成的LiFePO4/C复合材料的循环性能和高倍率放电性能均优于以FeC2O4·2H2O为铁源合成的LiFePO4/C复合材料的;由FeSO4·7H2O合成的LiFePO4/C复合材料的5C倍率放电比容量为105.9 mA-h/g,经循环30次后,容量仍高达105.2 mA-h/g.     

Optimized synthesis technology of LiFePO4 for Li-ion battery

The influence of factors of the carbon black content, sintering temperature, sintering time, molar ratio of Li to Fe, as well as the electrochemical properties of LiFePO4 for lithium ion battery were studied. The only technology was obtained by using range analysis through Latin orthogonal experiment of L4^4 (16). The results show that the optimization synthesis technology of LiFePO4 is content of 5% doping carbon, sintering temperature of 700℃,molar ratio of Li to Fe of 1.03 : 1 and sintering time of 16 h. The optimized cathode synthesis techniques can make LiFePO4 have good electrochemical properties.     

Nb5+掺杂LiFePO4/C的反应挤出合成

以LiOH.H2O、FeC2O4.2H2O和P2O5为原料,以草酸铌为添加剂,采用反应挤出法合成Li1 5xNbxFePO4/C材料;采用X射线衍射(XRD)、扫描电镜(SEM)、循环伏安(CV)和充放电测试研究不同Nb5+掺杂量对Li1 5xNbxFePO4/C材料结构、形貌以及电化学性能的影响。结果表明,适量的Nb5+掺杂不会改变材料的结构和形貌;Nb5+掺杂可以有效减小电极的极化,其中Li0.97Nb0.006FePO4/C表现出最佳的电化学性能,在0.2C、0.5C、1C和2C倍率下的首次放电比容量分别为162.9、148.9、141.7和137.1 mA.h/g;材料循环性能良好,经10次循环后,材料的放电比容量都保持在99%以上。     

液氮淬火法制备高性能锂离子电池正极材料LiFePO4/C

以FePO4、Li2CO3和葡萄糖为原料,用液氮急速淬火法制备单一橄榄石结构的锂离子电池正极材料LiFePO4/C。结果表明:淬火使得LiFePO4晶格中产生Li空位,有利于提高其电子导电性。淬火样品的一次颗粒细小(100~500 nm),无明显团聚,并形成多孔结构;该样品在1C、2C和4C倍率下的首次放电比容量分别为151.4、138.0和116.7 mA.h/g,循环100次后的容量保持率高达99.3%、98.6%和94.5%。     

LiFePO_4/CNT复合正极材料的制备与性能研究

以柠檬酸为碳源和螯合剂,通过溶胶-凝胶法制备了LiFePO_4/CNT复合正极粉体材料.利用XRD和SEM表征了复合粉体的结构.复合材料含有单一的磷酸铁锂相,碳纳米管在正极材料中将颗粒与颗粒相连,为颗粒之间提供了附加的导电通路.通过添加碳纳米管的方法对正极材料导电通路进行改善.在低速率下容量可以达到135 mAh/g,在1 C充放电速率下容量保持在110 mAh/g,2 C时容量保持在80 mAh/g.随着碳纳米管含量的增加,锂离子电池的容量也增加.     

固相法制备Y3+掺杂LiFePO4/C的反应机理及其电化学性能

以Fe2O3为铁源,采用高温固相法制备了Y3+掺杂的LiFePO4/C复合材料。利用TG-DSC、XRD、SEM、恒电流充放电等手段对材料的合成反应历程、粉体颗粒形貌以及电化学性能进行了研究。结果表明:Fe3+在300～550℃间被还原为Fe2+,经过650℃煅烧后,形成晶型单一的橄榄石结构晶体。LiFe0.98Y0.02PO4/C样品在0.2 C倍率下的首次放电比容量达到了151.6 mA.h/g。     

Electrochemical performances of LiFePO4/C composites prepared by molten salt method

LiFePO4/C composites were synthesized by a molten salt (MS) method using the mixture of LiCl,LiOH and NaCl.The prepared LiFePO4/C composites are characterized by X-ray diffractometry (XRD),field emission scanning electron microscopy (FESEM) and charge-discharge test.XRD patterns indicate that LiFePO4 prepared in the temperature range of 550-700 ℃ crystallizes well in an olivine-type structure.Through FESEM images,the sphere-like and homogeneous particles of 0.2 μm can be observed.The charge-discharge test shows that the materials prepared at 600 ℃ for 12 h have good electrochemical performance.At the rates of 0.2C (34 mA/g) and 0.5C,the discharge capacities are 144.6 and 122.3 mA·h/g,respectively,together with good cycle performances.     

Electrochemical performance of Ti4+-doped LiFePO4 synthesized by co-precipitation and post-sintering method

Ti4+-mixed FePO4·xH2O precursor was prepared by co-precipitation method,with which Ti4+ cations were added in the process of preparing FePO4·xH2O to pursue an effective and homogenous doping way.Ti4+-doped LiFePO4 was prepared by an ambient-reduction and post-sintering method using the as-prepared precursor,Li2CO3 and oxalic acid as raw materials.The samples were characterized by scanning electron microscopy (SEM),X-ray diffractometry (XRD),electrochemical impedance spectroscopy (EIS),and electrochemical charge/discharge test.Effects of Ti4+-doping and sintering temperature on the physical and electrochemical performance of LiFePO4 powders were investigated.It is noted that Ti4+-doping can improve the electrochemical performance of LiFePO4 remarkably.The Ti4+-doped sample sintered at 600 ℃ delivers an initial discharge capacity of 150,130 and 125 mA·h/g with 0.1C,1C and 2C rates,respectively,without fading after 40 cycles.     

LiFePO4/C via fluoride doping

Non-stoichiometric compound fluoride-doped LiFePO4/C cathode materials were synthesized via solid-state reaction using MgF2 and AlF3 as dopant. The fluoride-doped LiFePO4/C samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical testing. The results show that the materials are well crystallized and fluoride doping cannot change the space structure of LiFePO4. Slight amounts of Fe2O3 with no fluoride impurity were ...     

用β-环糊精制备LiFePO4/C锂离子电池正极材料

采用高温固相法制备了β-环糊精为碳源前驱体、具有橄榄石结构的LiFePO4/C复合正极材料.与采用相同工艺制备的LiFePO4和以碳黑作为碳源制备的LiFePO4/C产物比较,该复合材料粉体粒度小,电化学性能优良,体现在:占体积分数为26.88%的产物粒度小于1 μm;0.1C放电比容量可达到147 mA·h·g-1,相对纯净LiFePO4提高66 mA·h·g-1.此外,初步分析了β-环糊精在制备过程中细化颗粒的机理.     

溶胶-凝胶法制备LiFePO_4/C复合材料及其性能

为了提高LiFePO4的电化学性能,以柠檬酸为络合剂和碳源,采用溶胶-凝胶法制备LiFePO4/C复合正极材料。采用FTIR和XRD等对前驱体及产物进行表征,并测试样品的电化学性能。结果表明:经700℃烧结10h所得产物具有单一的橄榄石型晶体结构,碳含量为10.81%(质量分数)。样品在0.1C下首次放电比容量为127.1mA·h/g,在0.2C、0.5C、1C下首次放电比容量分别为106.1、83.3、70.6mA·h/g。该样品在0.1C下经过20次循环后,容量还保持为126.3mA·h/g,衰减仅为0.035%。循环伏安和交流阻抗测试表明该材料具有较好的电化学性能。     

Synthesis of porous nano/micro structured LiFePO4/C cathode materials for lithium-ion batteries by spray-drying method

In order to enhance electrochemical properties of LiFePO₄ (LFP) cathode materials, spherical porous nano/micro structured LFP/C cathode materials were synthesized by spray drying, followed by calcination. The results show that the spherical precursors with the sizes of 0.5–5 μm can be completely converted to LFP/C when the calcination temperature is higher than 500 °C. The LFP/C microspheres obtained at calcination temperature of 700 °C are composed of numerous particles with sizes of ～20 nm, and have well-developed interconnected pore structure and large specific surface area of 28.77 m²/g. The specific discharge capacities of the LFP/C obtained at 700 °C are 162.43, 154.35 and 144.03 mA·h/g at 0.5C, 1C and 2C, respectively. Meanwhile, the capacity retentions can reach up to 100% after 50 cycles. The improved electrochemical properties of the materials are ascribed to a small Li⁺ diffusion resistance and special structure of LFP/C microspheres.     

Co掺杂LiFePO4/C的共沉淀——微波合成及电化学性能

采用共沉淀-微波法制备了Co掺杂的锂离子电池正极材料LiFe1-xCoxPO4/C(x=0.00、0.01、0.03、0.05、0.07、0.09).研究了微波时间、柠檬酸量、掺Co量等因素对材料结构、形貌和电性能的影响.XRD、SEM和电化学测试表明:该方法制备的样品为橄榄石型非晶结构,粒径尺寸为0.5～5 μm,颗粒分布比较均匀.微波15 min、柠檬酸量为20wt％时,LiFePO4/C电化学性能最优,0.1C倍率放电可达124 mA·h/g,第20次循环的比容量为117mA·h/g.掺杂Co在很大程度上可以提高LiFePO4/C的电化学性能,当Co含量为5wt％时,LiFe0.95Co0.05PO4/C的比容量为最大值,0.1C倍率放电可达136 mA·h/g,第20次循环的比容量为125 mA· h/g,容量保持率为91.9％.     

Synthesis of Porous LiFePO4/C Composite Materials by CCVD Method

以C2H2为碳源,Fe为催化剂,纳米FePO4为原料,采用催化化学气相沉积法(CCVD)合成多孔LiFePO4/C正极材料。经BET、SEM、CHON有机元素分析仪、XRD等手段对复合材料进行结构分析表征。结果表明,该复合材料具有连续贯通的三维导电网络结构,大的比表面积以及多重孔隙的类球形结构,含碳量为4.42%(质量分数),低于传统碳热还原法所制备的材料。电化学测试表明,该材料在0.1、1、5、10 C倍率下,放电比容量分别为147,141,126,110 m Ah·g-1,高倍率充放电性能大大提高,另外,该材料1 C循环80次后,放电比容量基本没有降低,显示了良好的循环稳定性能。