溶胶碳热还原法制备LiFePO4/C及其性能研究

以廉价的Fe3 为铁源,通过溶胶和碳热还原两步法制备出锂离子正极材料LiFePO4,用XRD、SEM、交流阻抗和恒流充放电方法表征了材料的结构、形貌和电化学性能.结果表明,合成的材料具有橄榄石型晶体结构;碳可以抑制材料颗粒的团聚,降低电极反应阻抗;在0.1 C的放电倍率下,LiFePO4首次放电容量为103.3 mA·h/g,LiFePO4/C在放电倍率0.1 C、0.2 C和0.5 C下的首次放电容量分别为147.9 mA·h/g、133.3 mA·h/g和122.1 mA·h/g, 20次循环后容量衰减率分别为3.0 %、2.7%和2.4%.     

热处理对橄榄石型磷酸铁锂电化学性能的影响

以FeSO4.7H2O和NH4H2PO4为原料,H2O2为氧化剂,通过液相沉淀法制备前驱体FePO4,然后通过碳热还原法合成LiFePO4;研究降温速度对产物晶型结构、形貌以及电化学性能的影响。从LiFePO4的扫描照片可以看出,随着降温速度的变慢,样品的粒径逐渐增大。电化学性能研究表明:降温速度不宜过大或过小,最适宜的降温速度为2℃/min。该条件下合成的材料以0.1C倍率充放电时其首次放电容量为153 mA.h/g,以1C倍率充放电时其首次放电容量达136 mA.h/g,且循环性能好。     

磷酸铁锂在不同醇溶液中的溶剂热合成及其电化学性能

分别以乙醇、乙二醇以及丙三醇/水为溶剂,采用溶剂热法合成橄榄石结构的磷酸亚铁锂(LiFePO4)。运用XRD,SEM和FTIR等手段,对产物晶体结构、颗粒形貌和表面微观结构进行表征,探讨溶剂热合成LiFePO4时不同溶剂对产物形貌和结构的影响,同时运用恒流充放电测试和循环伏安方法对所得产物的电化学性能进行研究。研究结果表明:以乙二醇为溶剂合成的LiFePO4呈均匀片状结构,具有粒度小、厚度薄的特点,这种结构缩短了锂离子的扩散距离,有利于电化学性能的提高,其0.1C倍率放电比容量达到161.7 mA.h/g,1C倍率放电时容量仍保持132.6 mA.h/g;在0.1C倍率下,50次循环后容量保持率为98.02%。     

胶晶模板法制备尖晶石型正极材料LiMn2O4

通过聚甲基丙烯酸甲酯(PMMA)胶晶模板法制备尖晶石型LiMn2O4材料,并探讨焙烧温度对材料性能的影响.运用热重分析(TG)、X线衍射(XRD)、扫描电镜(SEM)、充放电测试和循环伏安测试等方法对LiMn2O4样品的结构、形貌以及电化学性能进行表征和测试.研究结果表明:在不同温度下制备的LiMn2O4样品均具有较好的尖晶石型结构,且粒径分布均匀:在700℃时制备的LiMn2O4样品(S-700)具有最佳的电化学性能,在3.0～4.4 V时,0.2C倍率首次放电比容量为130.9 mA·h/g; 0.5C倍率首次放电比容量为126.4 mA·h/g,50次循环之后容量仍有102.7 mA·h/g,具有良好的循环稳定性.     

LiNi1/3Co1/3Mn1/3O2正极材料的制备及其表征

利用机械球磨对前驱体进行活化处理.在940℃于空气气氛中烧结12 h制备层状结构LiNi1/3Co1/3Mn1/3O2正极材料.通过XRD,SEM和电化学性能测试对所制备材料的结构、形貌及电化学性能进行表征.结果表明,所合成的材料为单相的六方层状结构;产物一次粒子粒径均匀,为1～2 μm,二次团聚颗粒平均粒径为10 μm左右;在2.75～4.3 V电压区间,所制备的LiNi1/3Co1/3Mn1/3O2以0.2C(C为充放电倍率)进行恒电流充放电,首次放电容量达146.3 mA·h·g-1;在倍率为0.4C,0.8C,1.6C和2.0C时的放电容量分别为135.2,130.1,125.8和114.7mA·h·g-1,倍率放电性能优良;在倍率为0.2C时经过30次循环,材料放电容量和容量保持率分别为143.3 mA·h·g-1和98%,循环稳定性好.     

单分散花状分级结构LiFePO_4的合成及其电化学性能

以乙二醇为溶剂,尿素为添加剂,采用溶剂热法制备锂离子电池正极材料磷酸铁锂(LiFePO4)。采用XRD,BET,SEM和TEM等对产物的结构和形貌进行表征,运用恒流充放电测试对LiFePO4/C复合材料的电化学性能进行研究。研究结果表明:花状分级结构的LiFePO4由单晶纳米片组成,且具有开放多孔的特性,其单分散性良好,粒径约为8μm,振实密度达1.2g/cm3。LiFePO4/C样品的首次放电比容量达152.4mA·h/g;在0.2C,1C和2C倍率下比容量分别为134.3,118.5和103.7mA·h/g;当放电倍率为2C时,经过5个循环后,容量保持在100.1mA·h/g,容量保持率为96.7%。     

锂离子电池正极材料LiNi0.3Co0.4Mn0.3O2的制备及性能

采用共沉淀法制备前驱体,并采用高温固相法合成单相层状结构LiNi0.3Co0.4Mn0.3O2 材料(R-3m 空间群).用X 射线衍射、恒电流充放电方法对所合成材料与LiNi1/3Co1/3Mn1/3O2 材料进行结构和电化学性能对比分析.研究结果表明,LiNi0.3Co0.4Mn0.3O2 具有有序的二维层状结构,在2.75～4.3 V 电压区间以0.1C 倍率进行充放电,首次放电容量、效率分别为152.3 mA·h/g 和84.4%,LiNi0.3Co0.4Mn0.3O2 具有更高的放电平台率,首次放电时3.6 V平台率为95.0%;以0.2C 倍率进行30 次充放电循环后,放电容量保持率为初始容量的97.4%.     

煅烧温度对尖晶石型Li4Ti5O12负极材料的影响

采用溶胶凝胶法合成了Li4Ti5O12负极材料,讨论了合成温度对Li4Ti5O12负极材料的影响。利用X线衍射分析(XRD)、扫描电镜(SEM)和恒流充放电测试对合成材料进行结构表征和电化学性能测试。结果表明:煅烧温度为800℃时,样品为颗粒分布均匀,结晶度良好的Li4Ti5O12;1C倍率时,首次放电容量达到154.6 mA·h/g,循环50次后,容量仍保持在141.8 mA·h/g。     

共沉淀-微波法合成LiFePO4/C正极材料

采用共沉淀-微波法,利用自制加料装置合成了橄榄石型LiFePO4/C. 利用SEM、交流阻抗及恒流充放电技术对样品进行形貌表征和电化学性能测试. 结果表明微波8min样品具有均匀结构和较好电化学性能;0.2 C充放电表明,首次放电比容量157.81 mAh/g,53周循环后仍为156.15 mAh/g,材料具有良好的循环性能;1C充放电时,第一次放电容量为136.30 mAh/g,经20周循环后容量没有明显衰减,材料的倍率性能较佳.     

MnO@CoMn_2O_4/N-C纳米线复合材料的制备及其作为锂离子电池阳极材料的电化学性能

过渡金属氧化物作为锂离子电池(lithium-ion batteries,LIBs)阳极材料时具有较高的理论容量,但因其电导率低,以及充放电过程中的体积膨胀效应常会导致容量的快速衰减.碳包覆是提升金属氧化物导电性的有效方法,二者之间的协同效应也可以有效提升材料的电化学性能.以MnO_2纳米线为模板制备出MnO_2@ZIF-67有机-无机杂化纳米结构,再通过退火处理合成了氮掺杂碳包覆的MnO@CoMn_2O_4纳米线复合材料(MnO@CoMn_2O_4@N-C).ZIF-67的有机配体在高温煅烧过程中发生碳化反应,产生了氮掺杂碳,提升了导电性.当作为锂离子电池阳极材料时,MnO@CoMn_2O_4/N-C纳米线复合材料在0.1 A/g电流密度下的首次放电比容量为1 594.6 mA·h/g,并且在100次充放电循环后的放电比容量仍保持在925.8 mA.h/g,在0.5 A/g电流密度下经200次充放电循环后的放电比容量仍维持在837.6 mA·h/g,同时具有优异的倍率循环性能.这种优异的电化学储能特性主要来源于复合材料的特殊结构,以及氮掺杂碳的包覆.     

锂离子电池正极材料Li2FeSiO4的改性

采用高温固相反应法在氩气气氛下合成锂离子电池正极材料Li2FeSiO4、Li2FeSiO4/C和Li2Fe0.9Mn0.1SiO4/C,并采用X线衍射、扫描电镜和电化学方法研究材料的结构与性能.研究结果表明:改性后的Li2FeSiO4/C和Li2Fe0.9Mn0.1SiO4/C材料与Li2FeSiO4具有相同的晶体结构,锰离子掺杂和表面碳包覆有效地提高了材料的比容量和循环性能.以C/16倍率充放电,Li2FeSiO4/C的首次放电容量为112mA·h/g,Li2Fe0.9Mn0.1SiO4/C材料首次放电容量达122 mA·h/g,充放电循环30次后容量衰减仅为9％.     

Enhanced low-temperature performance of slight Mn-substituted LiFePO<Subscript>4</Subscript>/C cathode for lithium ion batteries

Low temperature performance of LiFePO₄/C cathode was remarkably improved by slight Mn-substitution. Electrochemical measurements showed that about 95% of the discharge capacity of LiFe_0.98Mn_0.02PO₄/C cathode at 20°C was obtained at 0°C, compared to 85% of that of LiFePO₄/C cathode. The LiFe_0.98Mn_0.02PO₄/C sample also presented enhanced rate performance at −20°C with the discharge capacities of 124.4 mA h/g (0.1C), 99.8 mA h/g (1C), 80.7mAh/g (2C) and 70 mA h/g (5C), respectively, while pristine LiFePO₄/C only delivered capacities of 120.5 mA h/g (0.1C), 90.7 mA h/g (1C), 70.4 mA h/g (2C) and 52.2 mA h/g (5C). Cyclic voltammetry measurements demonstrated an obvious improvement of the lithium insertion-extraction process of the LiFePO₄/C cathode by slight Mn-substitution. The results of FSEM observation and electrical conductivity measurement indicated that slight Mn-substitution minimized the particle size of LiFe_0.98Mn_0.02PO₄/C and also obviously improved the electrical conductivity of the compound, thus obviously enhances the interface reaction process on the cathode.     

以竹纤维为模板制备微米管状Li4Ti5O12负极材料

以竹纤维为模板,Ti(OC4H9)4和Li(Ac).2H2O为原料,用模板法制备锂离子电池微米管状Li4Ti5O12负极材料。采用XRD,SEM,BET,充放电实验和交流阻抗等对合成材料的结构、形貌和电化学性能进行表征。研究结果表明:制备的微米管状Li4Ti5O12负极材料由尖晶石型纳米Li4Ti5O12颗粒构成,具有较大的比表面积,该材料具有良好的电化学性能,在0.5~3.0 V,0.1C倍率下的首次放电比容量为178 mA.h/g,充放电循环100次后放电比容量仍保留162 mA.h/g,且倍率性能优异。     

Li4Ti5O12作为锂离子电池负极材料电化学性能

采用固相法合成了锂钛复合氧化物Li4Ti5O12,研究了保温时间对其结构及电化学性能的影响.结果表明,保温时间为2,4h时样品的循环性能比较好,在80mA/g充放电下,30次循环后的比容量可高达159mAh/g.     

从磷酸二异辛酯-煤油体系反萃制备纳米β-Ni(OH)_2

以磷酸二异辛酯-煤油为萃取体系,通过水热反萃法制备球形纳米级β-Ni(OH)2.采用XRD、TEM和FTIR对样品的物相和形貌进行表征.结果表明,水热反萃法能够制备出均匀分散的球形β-Ni(OH)2,粒径在20~80,nm之间.用制备的β-Ni(OH)2作为镍氢电池正极材料,其电化学测试表明,在室温0.2C下首次放电比容量为285.6,(m A·h)/g;高倍率下具有高的比容量保持率和稳定的循环性,1.0C首次放电的比容量为259.1,(m A·h)/g,是0.2C放电比容量的90.7%,在循环58次后比容量为252.1,(m A·h)/g.     

Recovery and regeneration of LiFePO4 from spent lithium-ion batteries via a novel pretreatment process

The recycling of spent LiFePO4 batteries has received extensive attention due to its environmental impact and economic benefit. In the pretreatment process of spent LiFePO4 batteries, the separation of active materials and current collectors determines the difficulty of the re-covery process and product quality. In this work, a facile and efficient pretreatment process is first proposed. After only freezing the electrode pieces and immersing them in boiling water, LiFePO4 materials were peeled from the Al foil. Then, after roasting under an inert atmosphere and sieving, all the cathode and anode active materials were easily and efficiently separated from the Al and Cu foils. The active materials were subjected to acid leaching, and the leaching solution was further used to prepare FePO4 and Li2CO3. Finally, the battery-grade FePO4 and Li2CO3 were used to re-synthesize LiFePO4/C via the carbon thermal reduction method. The discharge capacities of re-synthesized LiFePO4/C cathode were 144.2, 139.0, 133.2, 125.5, and 110.5 mA·h·g?1 at rates of 0.1, 0.5, 1, 2, and 5 C, which satisfies the requirement for middle-end LiFePO4 batteries. The whole process is environmental and has great potential for industrial-scale recycling of spent lithium-ion batteries.     

锂离子电池正极材料Li1-xVxFePO4/C的制备及电化学性能

采用高温固相法合成了Li1-xVxFePO4/C（x=0,0.01,0.02,0.03,0.04,0.05,0.10）锂离子电池正极材料,通过XRD,SEM,CV,EIS和恒流充放实验研究了不同掺杂量对产物结构和电化学性能的影响。结果表明,少量V的掺杂未影响到LiFePO4的晶体结构,但显著改善了其电化学性能。其中,Li0.98V0.02FePO4/C材料以0.1 C倍率放电时,首次放电容量达到160.9 mAh·g^-1,且循环性能良好。     

Anion-immobilized solid composite electrolytes based on metal-organic frameworks and superacid ZrO2 fillers for high-performance all solid-state lithium metal batteries

Anion-immobilized solid composite electrolytes (SCEs) are important to restrain the propagation of lithium dendrites for all solid-state lithium metal batteries (ASSLMBs). Herein, a novel SCEs based on metal-organic frameworks (MOFs, UiO-66-NH2) and superacid ZrO2 (S-ZrO2) fillers are proposed, and the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS), thermo-gravimetric analyzer (TGA) and some other electrochemical measurements. The –NH2 groups of UiO-66-NH2 combines with F atoms of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) chains by hydrogen bonds, leading to a high electrochemical stability window of 5 V. Owing to the incorporation of UiO-66-NH2 and S-ZrO2 in PVDF-HFP polymer, the open met-al sites of MOFs and acid surfaces of S-ZrO2 can immobilize anions by strong Lewis acid-base interaction, which enhances the effect of im-mobilization anions, achieving a high Li-ion transference number (t+) of 0.72, and acquiring a high ionic conductivity of 1.05×10–4 S·cm–1 at 60°C. The symmetrical Li/Li cells with the anion-immobilized SCEs may steadily operate for over 600 h at 0.05 mA·cm–2 without the short-circuit occurring. Besides, the solid composite Li/LiFePO4 (LFP) cell with the anion-immobilized SCEs shows a superior discharge specific ca-pacity of 158 mAh·g–1 at 0.2 C. The results illustrate that the anion-immobilized SCEs are one of the most promising choices to optimize the performances of ASSLMBs.     

锂离子电池材Li1＋xZnxMn2-xO4电化学性质研究

采用溶胶-凝胶法合成了Zn^2＋取代的锂离子电池正极材料Li1＋xZnxMn2-xO4。结构研究结果表明,用这种方法可以在比固相反应低得多的温度下得到单相的尖晶石且制得的材料粒度均匀,粒径大多在150nm左右。半电池循环测试结果表明,起始组成为x=0．06的样品性能最佳,其与锂片组成的半电池在3．0V-4．6V间,以0．10mA／cm^2的电流密度进行充放电的首次充、放电容量分别为131．4mAh／g和129．2mAh／g,经35次循环后容量仍保持在100mAh／g。