高振实密度圆饼状LiFePO_4/C的制备及电化学性能

以乙二醇为溶剂,采用溶剂热法一步合成圆饼状LiFePO_4,然后以葡萄糖为碳源与合成的LiFePO_4前躯体高温烧结得到碳包覆的LiFePO_4/C复合材料,其振实密度高达1.3 g·cm~(-3)。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对LiFePO_4/C复合材料进行了物相和形貌表征,研究结果表明制备得到的LiFePO_4呈圆饼状,且生成的圆饼是由单晶LiFePO_4纳米片堆积而成。此外,LiFePO_4颗粒表面碳层包覆均匀。将制备的LiFePO_4/C用作锂离子电池正极材料,电化学性能测试表明其具有高的充放电比容量(在0.1C时放电,其初始放电比容量为157.7 mAh·g~(-1))与良好的循环性能(500次循环后容量保持率为82.4%)。     

锂离子电池正极材料LiFePO4电化学性能

分别采用蔗糖和乙炔黑作为碳添加剂,高温固相法合成LiFePO_4复合物,利用X射线衍射、扫描电子显微镜和充放电等测试技术对其晶体结构、表观形貌和电化学性能进行了研究。结果表明,合成的LiFePO_4均为单一的橄榄石型晶体结构。采用蔗糖包覆的LiFePO_4具有更好的电化学性能,以0．2 C充放电,首次放电比容量为148．6 mA·h/g,20次循环后放电容量仍为140．3 mA·h/g。     

石墨烯修饰改性制备锂离子电池LiFePO4/LiNi0.8Co0.15Al0.05O2复合正极材料及其性能

采用两步干混-球磨方法制备了石墨烯掺杂改性的锂离子电池LiFePO_4/LiNi_(0.8)Co_(0.15)Al_(0.05)O_2复合正极材料,实现LiNi_(0.8)Co_(0.15)Al_(0.05)O_2材料的高容量和高安全性。借助X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、X射线光电子能谱(XPS)以及电化学测试等表征手段对材料的晶体结构、微观形貌和电化学性能进行了较系统的研究。结果表明,石墨烯的存在实现了Li Fe PO4材料在LiNi_(0.8)Co_(0.15)Al_(0.05)O_2材料表面的完全包覆,形成致密的包覆层,进一步抑制LiNi_(0.8)Co_(0.15)Al_(0.05)O_2与电解液之间的副反应,提高活性材料利用率和循环性能。三者之间构成导电网络,加快电子渗透和传输,提高倍率性能。Li Fe PO4质量分数为20%的Li Fe PO4-Graphene/LiNi_(0.8)Co_(0.15)Al_(0.05)O_2样品具有最佳的容量性能和长循环性能,0.1C时放电容量达到202.5 m Ah·g~(-1),3C时放电容量仍然可保持在160.5 m Ah·g~(-1)。50℃在2.8~4.3 V,0.5C下循环100次后,容量保持率为91.9%,优于LiNi_(0.8)Co_(0.15)Al_(0.05)O_2和LiFePO_4/LiNi_(0.8)Co_(0.15)Al_(0.05)O_2样品的72.9%和82.0%。     

以Fe_2P_2O_7为前驱体制备LiFePO_4及其电化学性能（英文）

以磷铁废渣(Fe1.5P)和温室效应气体CO_2为原料,以磷酸为补充磷源合成磷酸铁锂(LiFePO_4)的前驱体Fe_2P_2O_7,并研究了其合成过程对LiFePO_4正极材料储能性能的影响。采用SEM观察了LiFePO_4的表面形貌,采用XRD分析了LiFePO_4和Fe_2P_2O_7的晶体结构。进一步对该方法进行优化,发现Fe1.5P与磷酸混合物(nFe1.5P∶nH3PO4=1∶1)在800℃热处理6 h合成的Fe_2P_2O_7对应的LiFePO_4/C电化学性能最好,在0.1C,0.2C,0.5C和1C倍率下的容量分别可达130,126,117和108 m Ah·g~(-1)。     

流变相法制备倍率性能优异的LiFePO4/C复合材料

以月桂酸为碳源和表面活性剂,氢氧化锂、碳酸锂和醋酸锂为锂源,采用流变相法制备LiFePO4/C复合材料。运用X射线衍射(XRD)、扫描电子显微镜(SEM)、粒度分析、恒流充放电测试、循环伏安以及交流阻抗测试等方法对复合材料进行表征。结果表明,不同的锂源对LiFePO4/C复合材料的结构和电化学性能均有很大影响,以氢氧化锂为锂源合成的LiFePO4/C材料展示出最佳的循环性能和倍率性能。该材料在0.1C下放电比容量为153.4 mAh.g-1,在大倍率10 C下,容量保持率仍可达76%,甚至10C下循环800次后,容量衰减率仅有4%,SEM结果显示该材料具有较小的粒径(～200 nm),且分布集中,有效提高了电子迁移速率,从而改进了LiFePO4/C的倍率性能。     

水系锂离子电池负极材料LiTi_2(PO_4)_3/C的合成与电化学性能

采用Pechini法合成了纳米LiTi2(PO4)3,以聚乙烯醇(PVA)为碳源,探讨了不同碳源分散方式下制备的碳包覆LiTi2(PO4)3电极电化学性能的影响因素.结果表明,纳米LiTi2(PO4)3的电化学性能主要取决于本身晶相的纯度和结晶度,其次为LiTi2(PO4)3颗粒表面碳包覆层的均匀程度.采用旋转蒸发的碳源分散方式制得的纳米LiTi2(PO4)3晶相纯度高,结晶度好,LiTi2(PO4)3颗粒表面碳包覆层均匀,电化学性能最优.4C倍率下首次放电容量达到123mA·h/g,充放电循环200次容量保持率在85%以上.     

锂离子电池负极材料Li4Ti5O12的半固相法制备及碳包覆改性

由半固相法制得锂离子电池负极材料Li4Ti5O12,并研究了Li4Ti5O12的碳包覆改性.采用XRD、SEM、TEM以及HRTEM观察和分析产物的相结构与形貌.采用恒流充放电、循环伏安法和交流阻抗技术测试了材料的电化学性质.结果表明,Li4Ti5O12因颗粒团聚电化学性能严重下降,该电极在0.1C和0.5C首周期放电容量分别为121.7和87.6 mAh·g-1;碳包覆Li4Ti5O12/C材料呈球形分布,能抑制颗粒团聚,该电极倍率<0.5C时的放电比容量大于180 mAh·g-1,超过Li4Ti5O12的理论放电比容量(175 mAh·g-1);在1C、5C和10C倍率下,其容量仍保持在136、79.9和58.3 mAh·g-1,碳包覆改性材料具有优异的循环寿命和高倍率性能.     

LiFePO4纳米晶的尺寸、形貌调控及锂电池性能研究

由于材料的电化学性能与其尺寸、形貌和结构密切相关,本文围绕乙二醇体系制备LiFePO_4纳米晶展开了材料的尺寸和形貌调控合成探索,并对材料进行了锂电池性能表征。改变体系的反应物浓度,LiFePO_4纳米晶的尺寸明显发生变化,当体系中FeSO_4的浓度为0.15mol/L时,得到的LiFePO_4纳米晶尺寸最小,其锂离子电池的容量稍高于其他尺寸的LiFePO_4纳米晶。葡萄糖的添加量对LiFePO_4纳米晶的形貌会产生影响,但对锂离子电池性能影响不大。     

碳包覆硅/石墨复合材料的制备及其电化学性能

本文以工业硅粉(600目)为原料,通过高能球磨和热解包碳方法制备了碳包覆纳米硅,在此基础上采用简单的机械球磨方法制备了碳包覆/石墨复合材料,并系统研究了碳包覆量及硅/石墨比例对碳包覆硅/石墨复合材料电化学性能的影响.与商业纳米硅粉/石墨复合材料相比,工业硅粉/石墨复合材料的循环性能及倍率性能均得到改善.通过高能球磨和热处理法得到的碳包覆材料为无定形碳和晶态硅材料的复合,所获碳包覆硅材料一次颗粒的粒径在100～200 nm左右.碳包覆量对材料的电化学性能有着重要影响,Si/C-2-1复合材料表现出高的可逆比容量、良好的倍率性能和循环稳定性,在0.1C倍率下,可逆比容量高达492.6 mA h·g~(-1),循环100周后容量保持率达85.8%,1C电流密度下放电比容量达369.7 mAh·g~(-1),为0.1C的73.9%.提高碳包覆硅/石墨复合材料中硅含量的比例可以提升其比容量,当硅含量达到20%时,Si/C-2-3复合材料在0.1C倍率下可逆比容量达到600.4 mAh·g~(-1),但材料循环性能有所下降,说明石墨在稳定硅/碳复合材料循环性能方面发挥着非常重要的作用.     

LiFePO4的软化学合成及锂快离子导体修饰

采用溶剂热法制备正极材料LiFePO_4,采用溶胶凝胶法制备Li_(0.5)La_(0.5)TiO_3(LLTO)粉体,并通过酒精悬浮法对LiFePO_4进行修饰,修饰量为LiFePO_4质量的1%~4%,获得了薄壁蜂窝状自组装结构的LiFePO_4上修饰有球状LLTO纳米颗粒的复合正极材料。通过进行充放电测试、交流阻抗测试及循环伏安测试,研究了不同修饰量对电池的充放电比容量、循环性能及可逆性的影响,发现当LLTO含量为3%(w/w)时,以2C和5C倍率放电相对于没有修饰LLTO的LiFePO_4的比容量分别提高29.7%和31.6%,30次循环之后,容量损失率较未改性前减小4.13%,循环伏安曲线上氧化还原峰之间的电位差仅为0.117 V,以3%的LLTO修饰改性的LiFePO_4显著提高了电池的倍率性能、循环性能和低温性能。     

Effects of molecular weight,heating rate,synthetic temperature and sintering duration on electrochemical properties of a LiFePO<Subscript>4</Subscript>/C cathode material pyrolyzed from lithium polyacrylate

A LiFePO₄/C composite was obtained by a polymer pyrolysis reduction method, using lithium polyacrylate (LiPAA) as carbon source and fractional lithium source, and FePO₄·2H₂O as iron and phosphorus source. The structure of the LiFePO₄/C composites was investigated by X-ray diffraction (XRD). The micromorphology of the precursors and LiFePO₄/C powders was observed using scanning electron microscopy (SEM). Laser particle analyzer and BET were also used to characterize the materials. It was found that the micromorphology, particle size distribution and specific surface area of LiFePO₄/C composites were greatly influenced by the molecular weight of LiPAA. The electrochemical properties of the LiFePO₄/C composites were evaluated by cyclic voltammograms (CVs), electrochemical impedance spectra (EIS) and constant current charge/discharge cycling tests. The results showed that the molecular weight of LiPAA, heating rate, synthetic temperature and sintering duration directly affected the electrochemical properties of LiFePO₄/C composites. The sample with the optimized electrochemical properties were obtained in the following conditions, i.e., LiPAA with the molecular weight of 20,000, heating rate of 10 °C min⁻¹, synthetic temperature of 700 °C and sintering duration of 15 h.     

高振实密度圆饼状LiFePO4/C的制备及电化学性能

以乙二醇为溶剂,采用溶剂热法一步合成圆饼状LiFePO₄,然后以葡萄糖为碳源与合成的LiFePO₄前躯体高温烧结得到碳包覆的LiFePO₄/C复合材料,其振实密度高达1.3 g·cm^-3。采用X射线衍射(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对LiFePO₄/C复合材料进行了物相和形貌表征,研究结果表明制备得到的LiFePO₄呈圆饼状,且生成的圆饼是由单晶LiFePO₄纳米片堆积而成。此外,LiFePO₄颗粒表面碳层包覆均匀。将制备的LiFePO₄/C用作锂离子电池正极材料,电化学性能测试表明其具有高的充放电比容量(在0.1C时放电,其初始放电比容量为157.7 mAh·g^-1)与良好的循环性能(500次循环后容量保持率为82.4%)。     

两种方法制备的磷酸铁锂/石墨烯复合材料的性能对比

以FeSO₄·7H₂O、NH₄H₂PO₄、H₂O₂、Li₂CO₃、C₆H₁₂O₆和自制的氧化石墨烯(GO)为原料,分别采用原位包覆法和非原位包覆法制备了石墨烯磷酸铁锂样品:LiFePO₄/C/G-1和LiFePO₄/C/G-2。用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、交流阻抗(EIS)和充放电测试研究了两种包覆方法制备的样品的晶体结构、形貌和电化学性能。结果表明原位法包覆所得复合材料LiFePO₄/C/G-1具有更优秀的电性能:在2.5~4.1V充放电,0.1C和1C首次放电比容量分别为158.15和150.5mAh·g^-1,在1C倍率下循环500次后容量保持率达到98.3%。     

Li<Subscript>0.99</Subscript>Ti<Subscript>0.01</Subscript>FePO<Subscript>4</Subscript>/C composite as cathode material for lithium ion battery

Three kinds of LiFePO₄ materials, mixed with carbon (as LiFePO₄/C), doped with Ti (as Li_0.99Ti_0.01FePO₄), and treated both ways (as Li_0.99Ti_0.01FePO₄/C composite), were synthesized via ball milling by solid-state reaction method. The crystal structure and electrochemical behavior of the materials were investigated using X-ray diffraction, SEM, TEM, cyclic voltammetry, and charge/discharge cycle measurements. It was found that the electrochemical behavior of LiFePO₄ could be increased by carbon coating and Ti-doping methods. Among the materials, Li_0.99Ti_0.01FePO₄/C composite presents the best electrochemical behavior, with an initial discharge capacity of 154.5 mAh/g at a discharge rate of 0.2 C, and long charge/discharge cycle life. After 120 cycles, its capacity remains at 92% of the initial capacity. The Li_0.99Ti_0.01FePO₄/C composite developed here can be used as the cathode material for lithium ion batteries.     

New solid-state synthesis routine and mechanism for LiFePO4 using LiF as lithium precursor

Li₂CO₃ and LiOH·H₂O are widely used as Li-precursors to prepare LiFePO₄ in solid-phase reactions. However, impurities are often found in the final product unless the sintering temperature is increased to 800 °C. Here, we report that lithium fluoride (LiF) can also be used as Li-precursor for solid-phase synthesis of LiFePO₄ and very pure olivine phase was obtained even with sintering at a relatively low temperature (600 °C). Consequently, the product has smaller particle size (about 500 nm), which is beneficial for Li-extraction/insertion in view of kinetics. As for cathode material for Li-ion batteries, LiFePO₄ obtained from LiF shows high Li-storage capacity of 151 mAh g⁻¹ at small current density of 10 mA g⁻¹ (1/15 C) and maintains capacity of 54.8 mAh g⁻¹ at 1500 mA g⁻¹ (10 C). The solid-state reaction mechanisms using LiF and Li₂CO₃ precursors are compared based on XRD and TG-DSC.     

Effects of carbon sources and carbon contents on the electrochemical properties of LiFePO4/C cathode material

LiFePO₄/C composites are prepared by using two types of carbon source: one using polymer (PAALi) and the other using sucrose. The physical characteristics of LiFePO₄/C composites are investigated by X-ray diffraction), scanning electron microscopy, BET, laser particle analyzer, and Raman spectroscopy. Their electrochemical properties are characterized by cyclic voltammograms, constant current charge–discharge, and electrochemical impedance spectra. These analyses indicate that the carbon source and carbon content have a great effect on the physical and electrochemical performances of LiFePO₄/C composites. An ideal carbon source and appropriate carbon content can effectively increase the lithium-ion diffusion coefficient and exchange current density, decrease the charge transfer resistance (R _ct), and enhance the electrochemical performances of LiFePO₄/C composite. The results show that PAALi is a better carbon source for the synthesis of LiFePO₄/C composites. When the carbon content is 4.11 wt.% (the molar ratio of PAALi/Li₂C₂O₄ was 2:1), as-prepared LiFePO₄/C composite shows the best combination between electrochemical performances and tap density.     

Inorganic-based sol–gel synthesis of nano-structured LiFePO4/C composite materials for lithium ion batteries

An inorganic and non-toxic compounds combination of FeCl₂·4H₂O, Li₂CO₃ and H₃PO₄ was chosen to synthesize homogeneous nano-structured LiFePO₄/C composite material via a simplified sol–gel route. The dependency of the physicochemical properties and the corresponding electrochemical responses on the residual carbon content were investigated in details. Rietveld refinement of X-ray diffraction measurement and X-ray photoelectron spectroscopy analysis confirmed the feasibility of preparing pure LiFePO₄ phase via this approach. With increasing amount of residual carbon, the particles size gradually decreased and the bulk electrical conductivity monotonically increased. However, the higher level of residual carbon would bring disadvantageous impact on the lithium ion diffusion. Due to high electrical conductivity, controlled particle size and suitable microstructure, the sample with 4.5 wt.% residual carbon exhibited stable cycling performance and delivered high discharge capacity of 163, 119 and 108 mA h g⁻¹ at 0.1 C, 5 C and 10 C, respectively.     

共聚物模板辅助合成高倍率性能多孔Li2FeSiO4@C/CNTs纳米复合正极材料

通过溶胶-凝胶法制备了Li₂FeSiO₄@C/CNTs(LFS@C/CNTs)纳米复合材料,其中三嵌段共聚物P123用作结构导向剂和碳源,碳纳米管作为导电线提高材料的导电性。LFS@C/CNTs不仅具有海绵状纳米孔,能够与电解液充分接触改善锂离子的传输路径,同时由非晶碳和碳纳米管构成的三维桥联导电网络利于电子的快速传递,提高了材料大电流充放电能力和循环稳定性。复合后的LFS@C/CNTs的高倍率性能相比LFS@C明显提高, 当CNTs的掺量为4%,电压窗口为1.5~4.5 V,0.1C电流密度下放电比容量为182 mAh·g^-1。在10C经70次循环后该材料的放电比容量能保持在117 mAh·g^-1,是LFS@C放电比容量(55 mAh·g^-1)的两倍。